ES2249285T3

Cured coatings having improved scratch resistance and coated substrates

Abstract

A cured coating comprising a plurality of particles throughout the coating, the concentration of particles within the surface region of the coating being greater than the concentration of particles within the volume region of the coating, the cured coating being formed from a curable coating composition comprising: (a) at least one film forming material having at least one reactive functional group; (b) a plurality of particles; and (c) at least one surfactant.

ES2249285T3, drawing sheet 1 — Sheet 1 of 12

Term

Term ended

Projected expiry passed 31 July 2020, 6.1 years ago.

57 claims: 7 independent, 50 dependent

1
ES 2 249 285 T3 REIVINDICACIONES 1. Un recubrimiento curado que comprende una pluralidad de partículas en todo el recubrimiento, siendo la concentración de partículas dentro de la región superficial del recubrimiento superior a la concentración de partículas dentro de la región de volumen del recubrimiento, estando formado el recubrimiento curado a partir de una composición de recubrimiento curable que comprende:(a) al menos un material de formación de película que tiene al menos un grupo funcional reactivo;(b) una pluralidad de partículas;y (c) al menos un agente tensioactivo.
2
El recubrimiento curado de la reivindicación 1, en el que la composición de recubrimiento comprende además (d) al menos un reactivo.
3
El recubrimiento curado de cualquiera de las reivindicaciones anteriores, en el que el agente tensioactivo se selecciona entre al menos un polisiloxano y al menos un fluoropolímero.
4
El recubrimiento curado de la reivindicación 3, en el que el agente tensioactivo se selecciona entre un polisiloxano que tiene al menos un grupo funcional reactivo.
5
El recubrimiento curado de la reivindicación 4, en el que dicho polisiloxano comprende al menos dos grupos con función reactiva.
6
El recubrimiento curado de la reivindicación 4, en el que dicho grupo funcional reactivo se selecciona entre un grupo hidroxilo, un grupo carboxilo, un grupo isocianato, un grupo poliisocianato bloqueado, un grupo amina primaria, un grupo amina secundaria, un grupo amida, un grupo carbamato, un grupo urea, un grupo uretano, un grupo vinilo, un grupo éster insaturado, un grupo maleimida, un grupo fumarato, un grupo anhídrido, un grupo hidroxil alquilamida, y un grupo epoxi.
7
El recubrimiento curado de la reivindicación 6, en el que dicho grupo funcional reactivo se selecciona entre un grupo hidroxilo y un grupo carbamato.
8
El recubrimiento curado de la reivindicación 6, en el que dicho grupo funcional reactivo es un grupo que comprende al menos dos grupos funcionales reactivos seleccionados entre un grupo hidroxilo y un grupo carbamato.
9
El recubrimiento curado de la reivindicación 4, en el que dicho grupo funcional reactivo es un grupo que comprende un grupo oxalquileno y al menos dos grupos hidroxilo.
10
El recubrimiento curado de la reivindicación 3, en el que dicho polisiloxano tiene al menos una de las siguientes unidades estructurales (I):R 1 nR 2 mSiO(4-n-m)2 (I) en la que los R 1 , que pueden ser idénticos o diferentes, representan H, OH, un grupo hidrocarburo monovalente, un grupo siloxano monovalente;cada R 2 , que pueden ser idénticos o diferentes, representa un grupo que comprende al menos un grupo funcional reactivo, cumpliendo m y n las premisas de que 0 n 4, 0 m 4 y 2 (m+n) 4.
11
El recubrimiento curado de la reivindicación 10, en el que cada R 2 , que pueden ser idénticas o diferentes, representa un grupo que comprende al menos un grupo funcional reactivo seleccionado entre un grupo hidroxilo, un grupo carboxilo, un grupo isocianato, un grupo poliisocianato bloqueado, un grupo amina primaria, un grupo amina secundaria, un grupo amida, un grupo carbamato, un grupo urea, un grupo uretano, un grupo vinilo, un grupo éster insaturado, un grupo maleimida, un grupo fumarato, un grupo anhídrido, un grupo hidroxi alquilamida y un grupo epoxi.
12
El recubrimiento curado de la reivindicación 13, en el que dicho polisiloxano tiene la siguiente estructura (II) ó (III):R R R R I I I I R - Si - O - (- Si - O -)n - (Si - O)m - Si - R II II R R R a R (II) o ES 2 249 285 T3 R R R R II II R-Si-O-(-Si-O-) n , - (Si - O)m' -Si-R II II R a R R a R a (II) en las que: m tiene un valor de al menos 1;m' oscila entre 0 y 75;n oscila entre 0 y 75;n' oscila entre 0 y 75;cada R, que pueden ser idénticas o diferentes, se selecciona entre H, OH, o un grupo hidrocarburo monovalente, un grupo siloxano monovalente, y mezclas de ellos;y -R a comprende la siguiente estructura (IV): -R 3 -X (IV) en la que -R 3 se selecciona entre un grupo alquileno, un grupo oxialquileno, un grupo alquilen arilo, un grupo alquenileno, un grupo oxialquenileno, y un grupo alquenilen arilo;y X representa un grupo que comprende al menos un grupo funcional reactivo seleccionado entre un grupo hidroxilo, un grupo carboxilo, un grupo isocianato, un grupo poliisocianato bloqueado, un grupo amina primaria, un grupo amina secundaria, un grupo amida, un grupo carbamato, un grupo urea, un grupo uretano, un grupo vinilo, un grupo éster insaturado, un grupo maleimida, un grupo fumarato, un grupo anhídrido, un grupo hidroxi alquilamida y un grupo epoxi.
13
El recubrimeinto curado de la reivindicación 4, en el que al menos un polisiloxano es el producto de reacción de al menos uno de los siguientes reactivos:(i) al menos un polisiloxano de fórmula (VI): R R R I I I R - Si - O - (- Si - O -) n -Si-R I I I R R R (VI) en la que cada grupos sustituyente R, que puede ser idénticos o diferentes, representa un grupo seleccionado entre H, OH, un grupo hidrocarburo monovalente, un grupo siloxano, y mezclas de ellos;al menos uno de los grupos representados por R es H, y n' oscila entre 0 y 100, de manera que el porcentaje de contenido en Si-H del polisiloxano oscila entre 2 y 50 por ciento;y (ii) al menos una molécula que comprende al menos un grupo hidroxilo primario y al menos un enlace insaturado capaz de experimentar una reacción de hidrosililación.
14
El recubrimiento curado de la reivindicación 1, en el que las partículas tienen un tamaño de partícula medio inferior a 100 micrómetros antes de la incorporación en la composición.
15
El recubrimiento curado de la reivindicación 14, en el que las partículas tienen un tamaño de partícula medio inferior a 50 micrómetros antes de la incorporación en la composición.
16
El recubrimiento curado de la reivindicación 1, en el que las partículas tienen un tamaño de partícula medio comprendido entre 1 y menos de 1000 nanómetros antes de la incorporación en la composición.
17
El recubrimeinto curado de la reivindicación 15, en el que las partículas tienen un tamaño de partícula medio comprendido entre 1 y 100 nanómetros antes de la incorporación en la composición.
18
El recubrimiento curado de la reivindicación 17 en el que las partículas tienen un tamaño de partícula medio comprendido entre 5 y 50 nanómetros antes de la incorporación en la composición.
19
El recubrimiento curado de la reivindicación 1, en el que las partículas, cuando se añaden a los demás componentes que forman la composición de recubrimiento, están presentes en la composición de recubrimiento en una cantidad comprendida entre 0,01 y 75 por ciento en peso en función del peso total de los sólidos de resina de los componentes que forman la composición de recubrimiento. ES 2 249 285 T3
20
El recubrimiento curado de la reivindicación 19, en el que las partículas están presentes en una cantidad de al menos 0,1 por ciento en peso.
21
El recubrimiento curado de la reivindicación 19, en el que las partículas están presentes en una cantidad de al menos 0,5 por ciento en peso.
22
El recubrimiento curado de la reivindicación 19, en el que las partículas están presentes en una cantidad de al menos 5 por ciento en peso.
23
El recubrimiento curado de la reivindicación 19, en el que las partículas están presentes en una cantidad inferior a 10 por ciento en peso.
24
El recubrimiento de la reivindicación 1, en el que la pluralidad de partículas se selecciona entre partículas inorgánicas, partículas compuestas y mezclas de ellas.
25
El recubrimiento curado de la reivindicación 24, en el que las partículas se seleccionan entre sílice ahumada, sílice amorfa, sílice coloidal, alúmina, alúmina coloidal, dióxido de titanio, óxido de cesio, óxido de itrio, itria coloidal, zirconia, zirconia coloidal y mezclas de cualquiera de ellos.
26
El recubrimiento curado de la reivindicación 24, en el que las partículas se tratan superficialmente.
27
El recubrimiento curado de la reivindicación 1, en el que dicho material de formación de película comprende al menos un grupo funcional reactivo seleccionado entre un grupo hidroxilo, un grupo carbamato, un grupo epoxi, un grupo isocianato y un grupo carboxilo.
28
El recubrimiento curado de la reivindicación 27 en el que dicho material de formación de película comprende al menos un grupo funcional reactivo seleccionado entre un grupo hidroxilo y un grupo carbamato.
29
El recubrimiento curado de la reivindicación 4, en el que el material de formación de película se selecciona entre un polímero, en adición y que es diferente a dicho polisiloxano, que comprende al menos un grupo funcional reactivo que es reactivo con el grupo funcional del polisiloxano.
30
El recubrimiento curado de la reivindicación 2 y 4, en el que dicho reactivo comprende al menos un grupo funcional que es reactivo con al menos un grupo funcional reactivo del polisiloxano.
31
El recubrimiento curado de la reivindicación 2, en el que el reactivo se selecciona entre al menos un agente de curado.
32
El recubrimiento curado de la reivindicación 31, en el que el agente de curado se selecciona entre una resina de aminoplasto, un poliisocianato, un isocianato bloqueado, un poliepóxido, un poliácido y un polialcohol.
33
El recubrimiento curado de la reivindicación 32, en el que el agente de curado se selecciona entre una resina de aminoplasto y un poliisocianato.
34
El recubrimiento curado de la reivindicación 31, en el que el agente de curado, cuando se añade a los demás componentes que forman la composición de recubrimiento, está presente en una cantidad comprendida entre 2 por ciento en peso a 65 por ciento en peso en función del peso total de sólidos de resina de los componentes que forman la composición de recubrimiento.
35
El recubrimiento curado de la reivindicación 34, en el que el agente de curado está presente en una cantidad de al menos 5 por ciento en peso.
36
El recubrimiento curado de la reivindicación 34, en el que el agente de curado está presente en una cantidad de al menos un 10 por ciento en peso.
37
El recubrimiento curado de la reivindicación 2, en el que el reactivo comprende al menos un material que tiene al menos un grupo funcional reactivo que está bloqueado con un grupo sililo.
38
El recubrimiento curado de la reivindicación 37 en el que el grupo de bloqueo de sililo tiene la siguiente estructura (IX):R 1 I - Si - R2 I R3 (IX) ES 2 249 285 T3 en la que R1, R2 y R3, que pueden ser idénticos o diferentes, representa un grupo alquilo que tiene de 1 a 18 átomos de carbono, un grupo fenilo o un grupo alilo.
39
El recubrimiento curado de la reivindicación 37, en el que el grupo funcional reactivo se selecciona entre un grupo hidroxilo, un grupo carbamato, un grupo carboxilo y un grupo amida.
40
El recubrimiento curado de la reivindicación 37, en el que los compuestos que se pueden hacer reaccionar con el grupo funcional para formar el grupo sililo se seleccionan entre hexametildisilazano, trimetilclorosilano, trimetilsilildietilamina, cloruro de t-butil dimetilsililo, cloruro de difenil metilsililo, hexametil disililazida, hexametil disiloxano, triflato de trimetilsililo, hexametildisilil acetamida y mezclas de ellos.
41
El recubrimiento curado de la reivindicación 37, en el que el reactivo tiene una cadena principal que comprende al menos una unión seleccionada entre una unión éster, una unión uretano, una unión urea, una unión amida, una unión siloxano, y una unión éter o un polímero como poliéster, un polímero acrílico, un poliuretano, un poliéter, una poliurea, una poliamida, y copolímeros de cualquiera de ellos.
42
El recubrimiento curado de la reivindicación 37, en el que dicho material comprende al menos un compuesto que presenta la siguiente estructura (X):
43
El recubrimiento curado de cualquiera de las reivindicaciones anteriores en el que la composición de recubrimiento comprende adicionalmente al menos un catalizador.
44
El recubrimiento curado de la reivindicación 43, en el que el catalizador es un catalizador ácido.
45
El recubrimiento curado de la reivindicación 44, en el que el catalizador se selecciona entre un fosfato ácido, un ácido sulfónico sustituido y un ácido sulfónico sin sustituir.
46
El recubrimiento curado de la reivindicación 45, en el que el catalizador es fosfato de ácido fenílico.
47
El recubrimiento curado de la reivindicación 44, en el que el catalizador está presente durante la formación de la composición en una cantidad suficiente como para acelerar la reacción entre el grupo funcional del reactivo y el grupo funcional reactivo del polisiloxano.
48
El recubrimiento curado de la reivindicación 47, en el que el catalizador está presente en una cantidad comprendida entre 0,1 y 5 por ciento en peso en función del peso total de los sólidos de resina de los componentes que forman la composición de recubrimiento.
49
El recubrimiento curado de cualquiera de las reivindicaciones anteriores, en el que la composición curada se cura térmicamente o se cura por exposición a radiación ionizante o radiación actínica, o se cura por exposición a (a) radiación ionizante o radiación actínica y (b) energía térmica. ES 2 249 285 T3
50
El recubrimiento curado de cualquiera de las reivindicaciones anteriores, seleccionándose el recubrimiento entre una capa superior de monocapa, una capa superior transparente aplicada sobre al menos una porción de una capa base y un recubrimiento formado a partir de una composición de recubrimiento electrodepositable.
51
Una composición de recubrimiento compuesta de varios componentes que comprende una capa base depositada desde una composición de recubrimiento pigmentada, y un recubrimiento curado según cualquiera de las reivindicaciones 1 a 50 aplicada sobre al menos una porción de la capa base.
52
El recubrimiento compuesto de varios componentes según la reivindicación 51 siendo la composición curada una capa superior.
53
El recubrimiento compuesto de varios componentes según la reivindicación 51 en el que la composición curada es transparente.
54
El sustrato revestido que comprende un sustrato y un recubrimiento curado según cualquiera de las reivindicaciones 1 a 50 o un recubrimiento compuesto múltiple según cualquiera de las reivindicaciones 51 a 53 depositado sobre al menos una porción del sustrato.
55
Un sustrato revestido según la reivindicación 54, siendo el sustrato un sustrato de automóvil.
56
El sustrato de automóvil revestido según la reivindicación 55, siendo el sustrato de automóvil un parachoques, un capó, una puerta, un protector o una carcasa de espejo.
57
Un recubrimiento curado que es el resultado de una composición en polvo formada de componentes que consisten en:(a) al menos un agente tensioactivo que comprende: (i) al menos un polisiloxano que comprende al menos un grupo funcional reactivo, comprendiendo el polisiloxano al menos una de las siguientes unidades estructurales (I): R 1 nR 2 mSiO(4- n - m )2 (I) en la que los R 1 , que pueden ser idénticos o diferentes, representan H, OH, un grupo hidrocarburo monovalente, un grupo siloxano monovalente;cada R 2 , que pueden ser idénticos o diferentes, representa un grupo que comprende al menos un grupo reactivo, cumpliendo m y n las premisas de que 0 n 4, 0 m 4 y 2 (m+n) 4;y (ii) al menos un agente tensioactivo de poliacrilato que tiene al menos un grupo funcional seleccionado entre una funcionalidad amino e hidroxilo, funcionalidad ácido y funcionalidad ácido e hidroxilo;y (b) una pluralidad de partículas, siendo la concentración de partículas presentes en una región superficial de la composición curada superior a la concentración de partículas presentes en las regiones de volumen de la composición curada.

Independent claims57

622 paragraphs in 44 sections, as filed

ES 2 249 285 T3

DESCRIPTION

Hardened coatings with improved scratch resistance and coated substrates.

The present invention relates to cured coatings in which the concentration of particles within the surface region of the cured composition is greater than the concentration in the volume region of the cured composition, to a multi-component composite coating comprising the coating of the present invention, to coated substrates and to a cured coating resulting from a powder composition.

Background of the invention

Color-plus-transparent coating systems that involve the application of a colored or pigmented base coat over a substrate followed by the application of a clear or colorless coat over at least a portion of the base coat are becoming increasingly common. popular as original finishes for a number of consumer products including, for example, motor vehicles. More transparent color coating systems have outstanding appearance properties, such as gloss and image sharpness, largely thanks to the clear coat. Such color more transparent coating systems have become popular for use with motor vehicles, aerospace applications, floor coverings such as ceramic tiles and wood floors, container coatings, and the like.

Typically, a harder, more highly crosslinked film may have better scratch resistance, but is less flexible and much more susceptible to peeling and / or thermal cracking as a result of film embrittlement due to high crosslinking density. . A softer, less cross-linked film, while not prone to flaking or thermal cracking, is susceptible to scratching, water staining, and acid etching as a result of the low cross-link density of the cured film.

Also, typically, elastomer auto parts and accessories are coated, eg, elastomer bumpers and hoods "off site" and shipped to auto assembly plants. Coating compositions that are applied to such elastomeric substrates are typically formulated to be highly flexible so that the coating can bend or flex with the substrate without cracking. To achieve the necessary flexibility, coating compositions for use on elastomeric substrates are often formulated to produce coatings with lower crosslink densities or to include flexing aids that act to reduce the overall film glass transition temperature (Tg). While acceptable flexibility properties can be achieved with these formulation techniques, they can also result in softer films that are susceptible to scratching. Accordingly, great expense and care needs to be addressed to packaging the coated parts to prevent scratching of the coated surfaces during shipment to automobile assembly plants.

There is a series of patents that instruct on the use of a coating consisting of a colloidal silica dispersion in an alcohol-water solution of a partial condensate of a silanol of formula RSi (OH)3 wherein at least 70 weight percent of the partial condensate is the CH partial condensate3Yes (OH)3. Representative non-limiting examples include those described in US Patent Nos. 3,986,997; 4,027,073; 4,239,738; 4,310,600 and 4,410,594.

The use of a vinyl functional silane in an aqueous radiation curable coating composition consisting of: (a) 50 to 85 percent by weight, based on total weight of the dispersion, of a vinyl functional silane, (b) from 15 to 50 percent by weight, based on the total weight of the dispersion of a multifunctional acrylate and (c) optionally from 1 to 3 percent by weight of a photoinitiator. Vinyl-functional silane is the partial condensate of silica and a silane, so that at least 60% of the silane is a vinyl-functional silane corresponding to formula (R)toSir')b(R ")c R being allyl or vinyl functional alkyl; R 'is hydrolyzable alkoxy or methoxy; R "is siloxy, phenyl or saturated non-hydrolyzable alkyl, such that a + b + c = 4; ya> 1; b> 1; c> 0. The patent discloses that these coating compositions can be applied to plastic materials and cured by exposure to ultraviolet or electron beam irradiation to form a substantially transparent, abrasion resistant layer.

A polishing formulation consisting of a reactive amine functional silicone polymer and at least one other ingredient commonly used in polishing formulations is disclosed in US Patent No. 5,154,759. Ingredients disclosed in the patent include an abrasive that is instructed to be aluminum silicate, diatomaceous earth, pumice stone, fuller's earth, bentonite, silica, tripoli, hydrated calcium silicate, chalk, colloidal clay, oxide. magnesium, red iron oxide or tin oxide.

Modified particles comprising inorganic magnetic and / or colored particles as core particles, and at least one polysiloxane modified with at least one organic group coating the surface of the core particles are described in US Patent No. 5,686,012. The patent also describes a water-based paint consisting of a paint-based material and the modified particles as pigment, as well as a process for the production of the modified particles.

ES 2 249 285 T3

In US Patent No. 5,853,809 transparent coatings in color-more-transparent systems are described, which have better scratch resistance thanks to the inclusion in the coating composition of inorganic particles such as colloidal silicas whose surface has been modified with a reactive coupling agent through covalent bonding.

Despite recent improvements in color-more-transparent systems, there is still a need within the automotive coatings specialty for top coats that have good initial scratch resistance as well as better retained scratch resistance without that the embrittlement of the film occurs as a consequence of a high crosslinking density. On the other hand, it would be advantageous to provide top layers of elastomeric substrates used in the automotive industry that are both flexible and scratch resistant. Compendium of the invention

The present invention relates to cured coatings as defined in claim 1.

Such cured coatings typically have a 20 ° gloss greater than 70. Preferably, the initial scratch resistance such that, after the scratch test, more than 40 percent of an initial 20 ° gloss is retained, and the strength The scratch retained is such that after the scratch test more than 30 percent of said initial gloss is maintained at 20 °.

Additionally, a coated substrate comprising a substrate and a cured coating covering at least a portion of the substrate is disclosed in accordance with the present invention. The substrate can be metallic, in particular an automobile substrate.

Also provided are multi-component composite coating compositions consisting of a base coat deposited from a pigmented coating composition, and any of the above cured coatings in accordance with the present invention formed as a top coat over at least a portion of the base coat.

In another embodiment of the invention, methods are provided for improving the scratch resistance of a polymeric substrate or a polymeric coating consisting of forming on the polymeric substrate or polymeric coating any of the cured compositions mentioned in accordance with the present invention. Likewise, methods are described for retaining the gloss of a polymeric substrate or polymeric coating over time consisting of forming on at least a portion of the polymeric substrate or polymeric coating any of the cured compositions mentioned in accordance with the present invention. Also provided are methods for revitalizing the gloss of a polymeric substrate or a polymeric coating consisting of forming on at least a portion of the polymeric substrate or the polymeric coating of any of the cured compositions mentioned in accordance with the present invention.

Detailed description of the graphics

Figure 1 is a transmission electron micrograph (30,000 x magnification) of a cross section of a cured clear topcoat composition of the present invention containing both colloidal silica and polysiloxane;

Figure 2 is a transmission electron micrograph (30,000 x magnification) of a cross section of a comparative example of a clear topcoat composition containing colloidal silica but not polysiloxane.

Figure 3 is a transmission electron micrograph of a cross section of the cured clear topcoat composition of Figure 1 but viewed at 54,000 x magnification;

Figure 4 is a transmission electron micrograph (105,000 x magnification) of a cross section of a cured clear topcoat composition according to the present invention, including a pre-formed dispersion of colloidal silica and polysiloxane;

Figure 5 is a graph of scratch depth versus load over a given scratch distance indicating the scratch or wear resistance of a commercial two-component polyurethane coating; Y

Figure 6 is a graph of scratch depth versus load over a given scratch distance indicating the scratch or wear resistance of a two-component coating containing colloidal silica and polysiloxane according to the present invention .

Figure 7 is a transmission electron micrograph (105,000 x magnification) of a cross section of a cured clear topcoat composition according to the present invention taken generally perpendicular to the surface of the coating that included a pre-formed polysiloxane dispersion comprising a 2% colloidal silica.

ES 2 249 285 T3

Figure 8 is a transmission electron micrograph (105,000 x magnification) of a cross section of a cured clear topcoat composition according to the present invention taken at an angle to the surface of the coating that included a pre-formed polysiloxane dispersion that it comprised 2% colloidal silica.

Figure 9 is a transmission electron micrograph (105,000 x magnification) of a cross section of a cured clear topcoat composition according to the present invention taken perpendicular to the surface of the coating that included a preformed polysiloxane dispersion comprising 8.5 % colloidal silica.

Figure 10 is a transmission electron micrograph (105,000 x magnification) of cross section of a cured clear coating composition according to the present invention taken at an angle to the surface of the coating that included a pre-formed polysiloxane dispersion comprising 8 , 5% colloidal silica.

Detailed description of the preferred embodiments

In one embodiment, the present invention relates to coatings consisting of a plurality of particles, the first portion of the particles being present in a surface region of the cured coating at a concentration that is greater than the concentration of the second portion of particles that are present in the volume region of the cured coating.

As used herein, the term "cured" as used in connection with a composition, eg, "a cured composition" will mean that at least a portion of the crosslinkable components that make up the composition are at least partially crosslinked. In certain embodiments of the present invention, the crosslinking density of the crosslinking components, that is, the degree of crosslinking, ranges from 5% to 100% of complete crosslinking. In other embodiments, the crosslinking density ranges from 35% to 85% of full crosslinking. In other embodiments, the crosslinking density ranges from 50% to 85% of full crosslinking. Those skilled in this field will understand that the presence and degree of crosslinking, that is, the crosslinking density, can be determined through various methods, such as dynamic mechanical thermal analysis (DMTA) using a DMTA DMA analysis apparatus. 2980 from TA Instruments performed under nitrogen, as described. With this method, the glass transition temperature and the crosslinking density of loose films of coatings or polymers are determined. These physical properties of a cured material are related to the structure of the crosslinked network.

As used herein "surface region" of the cured coating means the region that is generally parallel to the air-exposed surface of the coated substrate and that has a thickness that normally extends in a perpendicular direction from the surface of the cured coating to a depth comprised between at least 20 nanometers and 150 nanometers below the exposed surface. In certain embodiments, this thickness of the surface region ranges from at least 20 nanometers to 100 nanometers, and can range from at least 20 nanometers to 50 nanometers. As used herein, "volume region" of the cured composition refers to the region that extends below the surface region and is generally parallel to the surface of the coated substrate. The volume region has a thickness that extends from its interface with the surface region through the cured coating to the substrate or coating layer beneath the cured composition.

In embodiments of the present invention in which the particles have a mean particle size greater than 50 nanometers, the thickness of the surface region typically extends in a perpendicular direction from the surface of the cured coating to a depth equivalent to three times plus the mean particle size of the particles, and this surface can be extended to a depth equivalent to two times the mean particle size of the particles.

The concentration of the particles in the cured composition can be characterized in a number of ways. For example, the number average particle density (ie, the average number or population of particles per unit volume) in the surface region is greater than the number average density in the bulky region. Alternatively, the mean volume fraction (i.e. the volume occupied by particles / total volume) or the percentage mean weight per unit volume, i.e. ((the weight of particles within a unit volume of the cured coating) / (total weight of unit volume of cured coating)) x 100% of the particles in the surface region is greater than the mean volume fraction or weight average percentage of the particles within the volume region.

The concentration of particles (as characterized above) present in the surface region of the cured coating can be determined, if desired, through various surface analysis techniques well known in the art, such as Transmission Electron Microscopy ( "TEM"), Surface Scanning Electron Microscopy ("X-SEM"), Atomic Force Microscopy ("AFM"), and X-ray Photoelectron Spectroscopy.

For example, the concentration of particles present in the surface region of the cured coating can be determined through transverse transmission electron microscopy techniques. A method of electron microscopy4

ES 2 249 285 T3 useful transmission is the one described below. A coating composition is applied to a substrate and cured under conditions appropriate to the composition and the substrate. Cured coating samples are then removed or peeled from the substrate and embedded in a cured epoxy resin using techniques known in the art. The embedded samples can then be microtomized at room temperature using techniques well known in the art, such as by forming a block face. Sections can be cut using a 45 ° diamond blade edge mounted on a handle with a “boat bore” to retain water. During the cutting process, the sections float to the surface of the water in the ship cavity. Once slices reach a bright to dark gold interference color (i.e., approximately 100 to 150 nanometers thick), individual samples are typically collected on a carbon-coated rack and dried at room temperature on a slide. of glass. The samples are then placed on a suitable transmission electron microscope such as Philips CM12 TEM, and examined at various magnifications, such as 105,000 x magnification, to obtain documentation of the concentration of particles in the surface region, through of electron micrography. The concentration of particles in a surface region of a cured coating can be determined by visual inspection of the electron micrograph.

It should be understood that the particles may be present in the surface region so that a portion of the particles protrudes at least partially above the surface of the cured coating, essentially without protection from an organic coating layer. Alternatively, the particles may be present in the surface region so that said organic coating layer falls between the particles and the air-exposed surface interface of the surface region.

Coatings according to the present invention may have outstanding appearance properties and initial scratch (wear) resistance properties, as well as retained or after exposure scratch (wear) resistance, which can be evaluated by measuring gloss. of coated substrates before and after abrasion of the coated substrates.

The initial 20 ° gloss of the substrate coated in accordance with the present invention can be measured with a NOVO-GLOSS 20 20 ° statistical gloss meter, available from Gardner Instrument Company, Inc. The coated substrate may be scratch-tested by linear scratching of the coating or substrate with a weighted abrasive paper for ten double rubs using an Atlas AATCC Scratch Test Apparatus, Model CM-5, distributed by Atlas Electrical Devices Company of Chicago, Illinois. The abrasive paper consists of sheets of 3M 281Q WETORDRY ™ PRODUCTION ™ 9 micron sandpaper, commercially available from the 3M Company of St. Paul, Minnesota. The panels are then rinsed with tap water and carefully dried with a paper towel. The 20 ° gloss is measured in the scratched area of each test panel. The number that is recorded is the percentage of the initial gloss retained after the scratch test, ie 100% x scratched gloss / initial gloss. The test method is fully described in the examples below.

In one embodiment, cured coatings are provided having an initial gloss at 20 ° (as measured using a NOVO-GLOSS 20 statistical gloss measuring apparatus at 20, distributed by Gardner Instrument Company, described above). of more than 50, or of more than 70, the coatings being any of the above compositions according to the present invention. On the other hand, in another embodiment, cured coatings are provided that have a scratch resistance value after the weather test or "held" sufficient that, after the scratch test, more than 50 percent or more is retained. more than 70 percent of initial gloss at 20 °.

On the other hand, the cured top coat of the present invention may have a retained scratch resistance (as measured by applying the scratch test method described above after subjecting the unscratched test panels to simulated weathering conditions by exposure QUV to UVA-340 bulbs in an outdoor cabinet distributed by Q Panel Company) so that more than 50 percent of the initial brightness at 20 ° is retained after outdoor conditions.

In certain embodiments, the cured coating of the present invention has an initial gloss at 20 ° (as measured using a NOVO-GLOSS 20 at 20 ° statistical gloss meter, distributed by Gardner Instrument Company) of greater than 70, it can be greater than 75, and frequently is greater than 80. This high gloss composition can be cured under ambient or thermal conditions or through radiation curing techniques, such as actinic radiation. In one embodiment, the high gloss composition can be cured under ambient or thermal conditions.

In one embodiment, the present invention relates to coatings cured as described above, in which the particles have an average particle size of less than 100 microns prior to incorporation into the coating composition, and may have a mean particle size less than 50 microns prior to incorporation into the coating composition. In another embodiment, the mean particle size of the coatings ranges from 1 to less than 1000 nanometers prior to incorporation into the coating composition, or from 1 to 100 nanometers prior to incorporation into the coating composition.

In another embodiment, the particles have a mean particle size between 5 and 50 nanometers before incorporation into the composition, or have a mean particle size between 5 and

ES 2 249 285 T3 nanometers prior to incorporation into the composition. The particle size can be between any combination of these values, including the values cited.

In an embodiment in which the mean particle size of the particles is greater than one micron, the mean particle size can be measured according to known laser scattering techniques. For example, the mean particle size of these particles is measured using a Horiba Model LA 900 laser diffraction particle size instrument, using a helium-neon laser with a wavelength of 633 nm. to measure particle size, assuming that the particle has a spherical size, ie "particle size" refers to the smallest sphere that completely encloses the particle.

In one embodiment of the present invention, in which the particle size is less than or equivalent to one micrometer, the mean particle size can be determined by examining an electron micrograph of a transmission electron microscope image with the naked eye ( "TEM"), measuring the diameter of the particles in the image and calculating the mean particle size as a function of the magnification of the TEM image. Persons skilled in this field will know how to prepare such a TEM image, one of these methods being described in the examples below. In a non-limiting embodiment of the present invention, a TEM image is produced at a magnification of 105,000 x, and a conversion factor is obtained by dividing the magnification by 1000. After examination with the naked eye, the diameter of the particles is measured in millimeters, and the measurement is converted to nanometers using the conversion factor. The diameter of the particle refers to the smallest diameter sphere that completely encloses the particle.

The shape (or morphology) of the particles may vary depending on the specific embodiment of the present invention and its intended application. For example, generally spherical morphologies (such as solid beads, microbeads, or hollow spheres) as well as particles that are cubic, laminar, or acicular (elongated or fibrous) can be used. Additionally, the particles may have an internal structure that is hollow, porous or non-vacuum, or a combination of any of the above, eg a hollow core with solid or porous walls. For more information on suitable particle characteristics see H. Katz et al. (Ed.), Handbook of Fillers and Plastics (1987) at pages 9-10.

Those skilled in the art will recognize that mixtures of one or more particles with different particle sizes can be incorporated into compositions according to the present invention to impart desired properties and characteristics to the compositions. For example, particles of various particle sizes can be used in compositions according to the invention.

The particles can be formed from materials selected from polymeric and non-polymeric inorganic materials, polymeric and non-polymeric organic materials, composite materials, and mixtures thereof. As used herein "formed of" means within the open language of the claims, eg, "comprising". Accordingly, the composition "formed from" a list of cited components is intended to be a composition comprising at least three of the cited components, and may further include other non-cited components, during composition formation. Additionally, as used herein, the term "polymer" is intended to encompass oligomers and to include without limitation both homopolymers and copolymers.

As used herein, the term "polymeric inorganic material" means a polymeric material having a backbone repeating unit based on an element or elements other than carbon. For more information, see James Mark et al., Inorganic Polymers, Prentice Hall Polymer Science and Engineering Series (1992) on page 5. On the other hand, as used herein, the term "polymeric organic materials" means synthetic polymeric materials, semi-synthetic polymeric materials, and natural polymeric materials, all of which have a carbon-based backbone repeating unit.

An "organic material" as used herein refers to carbon-containing compounds, in which carbon is typically attached to itself or hydrogen, and frequently to other elements as well, and excludes binary compounds such as carbon oxides, carbides , carbon disulfide, etc .; ternary compounds such as metal cyanides, metal carbonyls, phosgene, carbonyl sulfide, etc. and carbon-containing ionic compounds such as metal carbonates, such as calcium carbonate and sodium carbonate. See R. Lewis, Sr., Hawley's Condensed Chemical Dictionary (12to ed. 1993) at pages 761-762, and M. Silberberg, Chemistry The Molecular Nature of Matter and Change (1996) at page 586.

As used herein, the term "inorganic material" refers to any material that is not an organic material.

As used herein, the term "composite material" refers to a combination of two or more different materials. Particles formed from composite materials generally have a hardness on their surface that is different from the hardness of the internal portions of the particle below the surface. More specifically, the surface of the particle can be modified according to any other way known in the art, including, but not limited to, the chemical or physical change of its surface characteristics by applying techniques known in the art.

ES 2 249 285 T3

For example, a particle can be formed from a primary material that is coated, coated, or encapsulated with one or more secondary materials to form a composite particle that has a softer surface. In another more alternative embodiment, the particles formed from composite materials can be configured from a primary material that is coated, coated or encapsulated with a different shape from the primary material. For more information on particles useful in the present invention consult G. Wypych, Handbook of Fillers, 2to ed. (1999) at pages 15-202.

Particles suitable for use in the coating compositions of the invention may comprise inorganic elements or compounds known in the art. Suitable particles can be formed from ceramic materials, metallic materials, and mixtures of any of them. Suitable ceramic materials include metal oxides, metal nitrides, metal carbides, metal sulfides, metal silicates, metal borides, metal carbonates, and mixtures of any of these. Specific non-limiting examples of metal nitrides include, for example, boron nitride; Non-limiting examples of metal oxides include, for example, zinc oxide; Non-limiting examples of suitable metal sulfides include, for example, molybdenum disulfide, tantalum disulfide, tungsten disulfide, and zinc sulfide; Non-limiting examples of metal silicates include for example aluminum silicates and magnesium silicates such as vermiculite.

The particles may comprise, for example, a core of essentially a single inorganic oxide such as silica in colloidal, fumed or amorphous form, alumina or colloidal alumina, titanium dioxide, cesium oxide, yttrium oxide, colloidal yttrium, zirconia, eg, colloidal or amorphous zirconia and mixtures of any of them; or an inorganic oxide of one type on which an organic oxide of another type is deposited. It should be understood that when the cured composition of the invention is employed as a clear topcoat, eg, as a clearcoat in a multi-component composite coating composition, the particles should not seriously interfere with the optical properties of the cured composition. As used herein, "transparent" means that the cured coating has a BYK Haze Index of less than 50, as measured using a BYK / Haze Gloss instrument.

Non-polymeric inorganic materials useful in the particle formation of the present invention comprise inorganic materials selected from graphite, metals, oxides, carbides, nitrides, borides, sulfides, silicates, carbonates, sulfates, and hydroxides. A non-limiting example of a useful inorganic oxide is zinc oxide. Non-limiting examples of suitable inorganic sulfides include molybdenum disulfide, tantalum disulfide, tungsten disulfide, and zinc sulfide. Non-limiting examples of useful inorganic silicates include aluminum silicates and magnesium silicates such as vermiculite. Non-limiting examples of suitable metals include molybdenum, platinum, palladium, nickel, aluminum, copper, gold, iron, silver, alloys, and mixtures of any of these.

In one embodiment, the present invention relates to coatings cured as described above in which the particles are selected from fumed silica, amorphous silica, colloidal silica, alumina, colloidal alumina, titanium dioxide, cesium oxide, yttrium oxide, colloidal yttria, zirconia, colloidal zirconia, and mixtures thereof. In another embodiment, the present invention relates to coatings cured as described above in which the particles include colloidal silica. As described above, these materials can be surface-treated or untreated.

The coating composition may comprise suitable precursors to form silica particles in situ through a sol-gel process. The coating composition according to the present invention may comprise alkoxy silanes which can be hydrolyzed to form silica particles in situ. For example, tetraethylorthosilicate can be hydrolyzed with an acid such as hydrochloric acid and condensed to form silica particles. Other suitable particles include surface modified silicas such as those described in US Patent No. 5,853,809, at column 6, line 51 to column 8, line 43.

In one embodiment of the present invention, the particles have a hardness value greater than the hardness value of materials that can wear away a polymeric coating or a polymeric substrate. Examples of materials that can abrade the polymeric coating or polymeric substrate include, but are not limited to, dirt, sand, rocks, glass, car wash brushes, and the like. The hardness values of the particles and materials that can wear away the polymeric coating or polymeric substrate can be determined through any of the conventional hardness measurement methods, such as Vickers or Brinell hardness, although preferably determined according to the original Mohs hardness scale which indicates the relative scratch resistance of the surface of a material on a scale of one to ten. Mohs hardness values for various non-limiting examples of particles formed of inorganic materials suitable for use in the present invention are given in Table A below.

ES 2 249 285 T3

TABLE A

<td>Particle material</td><td>Mohs hardness (natural scale)</td>

<td>Boron nitride</td><td> 21</td>

<td>Graphite</td><td> 0,5-11 2</td>

<td>Molybdenum disulfide</td><td> 13</td>

<td>talcum powder</td><td> 1-1,54</td>

<td>Kaolinite</td><td> 2,0-2,56</td>

<td>Calcite (calcium carbonate)</td><td> 38</td>

<td>Calcium fluoride</td><td> 49</td>

<td>Zinc oxide</td><td> 4,510 11</td>

<td>Aluminum</td><td> 2,511</td>

<td>Copper</td><td> 2,5-312</td>

<td>Nickel</td><td> 515</td>

<td>Palladium</td><td> 4,816</td>

<td>Platinum</td><td> 4,317</td>

<td>Silver</td><td> 2,5-418</td>

<td>Zinc sulfide</td><td> 3,5-419</td>

1 K. Ludema, Friction, War, Lubrication (1996) at page 27.

2 R. Weast (Ed.), Handbook of Chemistry and Physics, CRC Press (1975), at page F-22.

3 R. Lewis, Sr, Hawley's Condensed Chemical Dictionary, (12to ed. 1993), on page 793.

4 Hawley's Condensed Chemical Dictionary, (12to ed, 1993) on page 1113.

5 Hawley's Condensed Chemical Dictionary, (12to ed. 1993) on page 784.

6 Handbook of Chemistry and Physics on page F-22.

7 Handbook of Chemistry and Physics on page F-22.

8 Friction, Wear, Lubrication on page 27.

9 Friction, Wear, Lubrication on page 27.

10 Friction, Wear, Lubrication on page 27 11 Friction, Wear, Lubrication on page 27.

12 Handbook of Chemistry and Physics on page F-22.

13 Handbook of Chemistry and Physics on page F-22.

14 Handbook of Chemistry and Physics on page F-22.

15 Handbook of Chemistry and Physics on page F-22.

16 Handbook of Chemistry and Physics on page F-22.

17 Handbook of Chemistry and Physics on page F-22.

18 Handbook of Chemistry and Physics on page F-22.

19 R. Weast Handbook of Chemistry and Physics CRC Pres (71to ed. 1990) on page 158.

ES 2 249 285 T3

In one embodiment, the Mohs hardness value of the particles is greater than 5. In certain embodiments, the Mohs hardness value of the particles such as silica is greater than 6.

As mentioned above, the Mohs hardness scale refers to a material's resistance to scratching. The present invention therefore further contemplates particles having a hardness on their surface that is different from the hardness of the internal portions of the particle below their surface. More specifically, as described above, the surface of the particle can be modified in a manner known in the art, including, but not limited to, the chemical change of the surface characteristics of the particle using techniques known within the specialty, so that the hardness of the surface of the particle is higher than the hardness of materials that can wear away the polymeric coating or polymeric substrate, at the same time that the hardness of the particle below the surface is less than the hardness of materials that can abrade the polymeric coating or polymeric substrate.

Alternatively, a particle can be formed from a primary material that is coated, coated, or encapsulated with one or more secondary materials to form a composite material having a harder surface. Alternatively, a particle can be formed from a primary material that is coated, coated, or encapsulated in a different shape than the primary material to form a composite material that has a harder surface.

In one example, and without limiting the present invention, an inorganic particle formed from an inorganic material such as silicon carbide or aluminum nitride can be provided with a coating of silica, carbonate, or nanoclay to form a useful composite particle. In another non-limiting example, a silane coupling agent with alkyl side chains can interact with the surface of an inorganic particle formed from an inorganic oxide to provide a useful composite particle having a "softer" surface. Other examples include the coating, encapsulation or coating of particles formed of polymeric or non-polymeric materials with different polymeric or non-polymeric materials. A specific non-limiting example of such composite particles is DUALITE ™, which is a synthetic polymeric particle coated with calcium carbonate available commercially from Pierce and Stevens Corporation of Buffalo, NY.

In a non-limiting embodiment of the invention, the particles are formed from solid lubricating materials. As used herein, the term "solid lubricant" means any solid used between two surfaces to provide protection against damage during relative motion and / or to reduce friction or wear. In one embodiment, the solid lubricants are inorganic solid lubricants. As used herein, "inorganic solid lubricant" means that solid lubricants have a characteristic crystalline habit that causes them to shear mix into thin flat plates that easily slide over each other to thereby produce an anti-friction lubricating effect. See R. Lewis, Sr, Hawley's Condensed Chemical Dictionary, (12to ed. 1993) on page 712. Friction is the resistance to sliding of one solid over another. F. Clauss, Solid Lubricants and Self-Lubricating Solids (1972) at page 1.

In a non-limiting embodiment of the invention, the particles have a lamellar structure. Particles having a laminar structure are composed of sheets or plates of atoms in a hexagonal arrangement, with strong bonds within the sheet and weak van der Waals bonds between the sheets, thus providing low shear strength between the sheets. A non-limiting example of a lamellar structure is a hexagonal crystal structure. Inorganic solid particles having a lamellar fullerene (ie, soccer ball) structure are also useful in the present invention.

Non-limiting examples of suitable materials having laminar structure that are useful in forming the particles of the present invention include boron nitride, graphite, metal dicalcogenides, mica, talc, gypsum, kaolinite, calcite, cadmium iodide, sulfide. silver and mixtures of them. Suitable metal dichalcogenides include molybdenum disulfide, molybdenum diselenide, tantalum disulfide, tantalum diselenide, tungsten disulfide, tungsten diselenide, and mixtures thereof.

The particles can be formed from non-polymeric organic materials. Non-limiting examples of non-polymeric organic materials useful in the present invention include, but are not limited to, stearates (such as zinc stearate and aluminum stearate), diamond, carbon black, and steamide.

The particles can be formed from inorganic polymeric materials. Non-limiting examples of useful inorganic polymeric materials include polyphosphazenes, polysilanes, polysiloxane, polygeremans, polymeric sulfur, polymeric selenium, silicones, and mixtures thereof. A specific non-limiting example of a particle formed from an inorganic polymeric material suitable for use in the present invention is TOSPEARL20, which is a particle formed from cross-linked siloxanes and is commercially available from Toshiba Silicones Company, Ltd. of Japan.

The particles can be formed from synthetic organic polymeric materials. Non-limiting examples of suitable organic polymeric materials include, but are not limited to, thermosetting materials and thermoplastic materials. As used herein, a "thermoplastic" material is a material that softens when exposed to heat and returns to its original state when cooled to room temperature. Non-limiting examples of suitable thermoplastic materials include thermoplastic polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polycarbonates, polyolefins such as polyethylene, 20 see RJ Perry

ES 2 249 285 T3 "Applications for Cross Linked Siloxane Particles" Chemtech, February 1999 at pages 39-44. polypropylene and polyisobutene, acrylic polymers such as copolymers of styrene and acrylic acid monomer, and polymers containing methacrylate, polyamides, thermoplastic polyurethanes, vinyl polymers, and mixtures of any of them.

Non-limiting examples of suitable thermosetting materials include thermosetting polyesters, vinyl esters, epoxy materials, phenolics, aminoplasts, thermosetting polyurethanes, and mixtures thereof. A specific non-limiting example of a synthetic polymeric particle formed from an epoxy material is an epoxy microgel particle. As used herein, a "thermoset" material is a material that irreversibly solidifies or "stabilizes" when heated. A thermosetting material has a cross-linked network formed. As used herein, a polymeric material "cross-links" when it at least partially forms a polymeric network. Those skilled in this field will understand that the presence and degree of crosslinking (crosslinking density) can be determined through a variety of methods, such as dynamic mechanical thermal analysis (DMTA) using a TA Instruments DMA 2980 DMTA analyzer set up. carried out under nitrogen. This method determines the glass transition temperature and crosslink density of loose films of coatings or polymers. These physical properties of a cured material refer to the structure of the crosslinked network.

According to this method, first the length, width and thickness of a sample to be analyzed are measured; The sample is hermetically mounted in the Polymer Laboratories MK III apparatus, and the dimensional measurements are entered into the apparatus. A thermal scan is started at a heating rate of 3 ° C / min, a frequency of 1 Hz, a tension of 120%, and a static force of 0.01 N, with sample measurements being produced every two seconds. The strain mode, glass transition temperature, and crosslink density of the sample can be determined according to this method. Higher crosslink density values indicate a higher degree of crosslinking in the coating.

The particles can also be hollow particles formed from materials selected from polymeric and non-polymeric inorganic materials, polymeric and non-polymeric organic materials, composite materials, and mixtures of any of them. Non-limiting examples of suitable materials from which the hollow particles can be formed include those described above. In one embodiment, the hollow particles are hollow glass spheres.

In one embodiment, the particles, when added to the other components that make up the composition, are present in the composition in an amount ranging from 0.01 to 75 percent by weight based on the total weight of the resin solids. of the components that make up the composition. In another embodiment, the particles, when added to other components that make up the composition, are present in the composition in an amount of at least 0.1, in an amount greater than 0.5 or in an amount greater than 5 percent by weight based on the total weight of the resin solids of the components that make up the composition.

In another embodiment, the particles, when added to the other components that make up the composition, are present in the composition in an amount less than 75, less than 50, less than 20%, or less than 10% by weight in a function of the total weight of the resin solids of the components that make up the composition. The amount of particles can range from any combination of these values including the quoted values.

As used herein "based on the total weight of resin solids" of the components that make up the composition means that the amount of the component that is added during composition formation is based on the total weight of the solids (not volatiles) of the polysiloxane, film-forming components, curing agents present during composition formation, and silyl-blocked materials, but not including particulates, solvents, or additive solids such as hindered amine stabilizers, catalysts, pigments, including pigments and stretch fillers, photoinitiators, flow additives, and UV light absorbers.

Before incorporation, a class of particles that can be used in accordance with the present invention includes sols, such as organosol, of the particles. These sols can consist of a wide variety of small particle colloidal silicas having a mean particle size within the ranges identified above.

Colloidal silicas can be surface modified during or after initial particle formation. These surface-modified silicas may contain chemically bonded carbon-containing moieties on their surface, as well as groups such as SiO groups.2 anhydrides and SiOH groups, various physically associated or chemically bound ionic groups within the surface of the silica, adsorbed organic groups, or combinations thereof, depending on the characteristics of the particular silica desired. Such surface modified silicas are described in detail in US Patent No. 4,680,204.

Such materials can be prepared through various techniques in different ways, non-limiting examples including organosols and mixed sols. As used herein the term "mixed sols" includes colloidal silica dispersions in which the dispersion medium comprises both organic liquid and water. Said colloidal silicas with small particles are readily available, are essentially colorless and have refractive indices that allow their inclusion in compositions which, without additional pigments or components known in the art to color and / or reduce the transparency of said compositions, have as a result colorless clear coatings.

ES 2 249 285 T3

Suitable non-limiting examples of particles include colloidal silicas, such as those sold commercially by Nissan Chemical Company under the trademark ORGANOSILICASOLS ™ as ORGANOSILICASOL ™ MT-ST, and by Clariant Corporation as HIGHLINK ™; colloidal aluminas as commercially available from Nalco Chemical under the trademark NALCO 8676®; and colloidal zirconias as commercially available from Nissan Chemical Company under the trademark HIT-32M®.

The particles can be incorporated into the compositions of the invention in the form of a stable dispersion. When the particles are in a colloidal form, dispersions can be prepared by dispersing the particles in a stirred vehicle and the solvent present can be removed under vacuum, at room temperature. In certain embodiments, the carrier may be a material other than solvent, such as the surfactants described in detail below, including but not limited to, a polysiloxane containing reactive functional groups, including but not limited to only he, at least one polysiloxane (a).

Alternatively, dispersions can be prepared as described in US Patent Nos. 4,522,958 or 4,526,910. The particles can be "cold mixed" with at least one polysiloxane prior to incorporation into compositions of the invention. Alternatively, the particles can be subsequently added to a mixture of the remaining composition components (including, but not limited to, at least one polysiloxane (a)) and dispersed therein using dispersion techniques known in the art.

When the particles are in a form other than colloidal, for example, but not limited only to it, in agglomerate form, dispersions can be prepared by dispersing the agglomerate in the vehicle, for example but not limited to it, at least a polysiloxane (a), to stably disperse the particles therein. Dispersion techniques such as grinding, grinding, microfluidization, ultrasound or any other pigment dispersion technique known in the art of coating formulation may be employed. Alternatively, the particles can be dispersed by any other dispersion technique known in the art. If desired, the particles in other than colloidal form can be subsequently added to the mixture of the other composition components and dispersed therein using any of the dispersion techniques known in the art.

The particles according to the present invention that are applied to the polymeric substrate or polymeric coating, for example but not limited to it, the electrodeposited coating, the primer coating or the top coat, may be present in a dispersion, suspension or emulsion in a vehicle. Non-limiting examples of suitable carriers include but are not limited to water, solvents, surfactants, or a mixture thereof. Non-limiting examples of suitable solvents include, but are not limited to, mineral oil, alcohols such as methanol or butanol, ketones such as methyl ethyl ketone, aromatic hydrocarbons such as xylene, glycol ethers such as ethylene glycol monobutyl ether, esters, aliphatics, and mixtures of them.

In accordance with the present invention, at least one surfactant is present during formation of the compositions as described above. Said surfactant can be selected from anionic, nonionic and cationic surfactants.

As used herein, by "surfactant" is meant a material that tends to lower the surface tension or solid surface energy of the cured composition or coating. That is, the cured coating formed from the composition comprising the surfactant has a lower surface tension or surface energy of the solid than the coating formed from an analogous composition that does not contain the surfactant.

For the purposes of the present invention, solid surface tension can be measured according to the OwensWendt method using a Rame-Hart Contact Angle Goniometer with distilled water and methylene iodide as reagents. Generally, a 0.02 cc drop of a reagent is placed on the surface of the cured coating and the contact angle and its complement are measured using a standard microscope equipped with a goniometer. The contact angle and its complement are measured for each of the three drops. The process is then repeated using the other reagent. The mean value for the six measurements is calculated for each of the reagents. The solid surface tension is then measured using the Owens-Wendt equation:

{yl (1 + cosO)} / 2 = (y1dYsd)1/2 + (y1pY..:) 'where yl is the surface tension of the liquid (methylene iodide = 50.8, distilled water = 72.8) and yd yyP are the dispersion and the polar components (methylene iodide andd = 49.5, andp = 1.3; distilled water andd = 21.8, andp = 51.0); the values for Φ are measured and the cosOs are determined. Next, two equations are established, one for methylene iodide and one for water. The only unknowns are ysd and ysp. The two equations are then solved to determine both unknowns. The two components combined represent the total solid surface tension.

The surfactant may be selected from amphiphilic reactive group-containing polysiloxanes, amphiphilic fluoropolymers, and mixtures of any of these. As regards water-soluble or water-dispersible amphiphilic materials, the term "amphiphilic" means a polymer having a generally hydrophilic polar end and a generally water-insoluble hydrophobic end. Non-limiting examples of functional group-containing polysiloxanes adduced for use in surfactants include the polysiloxanes described below. Non-limiting examples of suitable amphiphilic fluoropolymers include11

ES 2 249 285 T3 and in alternate alkyl vinyl ether-fluoroethylene copolymers (such as those described in US Pat. No. 4,345,057) distributed by Asahi Glass Company under the trademark LUMIFLON; fluorosurfactants, such as the fluoroaliphatic polymeric esters available commercially from 3M of St Paul, Minnesota under the trademark FLUORAD; functionalized perfluorinated materials such as 1H, 1H-perfluoro-nonanol available commercially from FluoroChem USA; and perfluorinated (meth) acrylate resins.

Non-limiting examples of other surfactants useful for use in the cured composition or coating of the present invention may include anionic, nonionic, cationic surfactants.

Non-limiting examples of suitable anionic surfactants include sulfates or sulfonates. Specific non-limiting examples include alkyl mononuclear aromatic sulfonates such as the higher alkyl benzene sulfonates containing from 10 to 16 carbon atoms in the alkyl group and straight or branched chain, eg, sodium salts of decyl benzene sulfonates, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl or hexadecyl and the alkyl, toluene, xylene and phenol sulfonates; alkyl naphanel sulfonate and sodium naphthelane dinonyl sulfonate. Other non-limiting examples of suitable anionic surfactants include olefin sulfonates, including long chain alkylene sulfonates, long chain hydroxyalkane sulfonates, and mixtures thereof. Non-limiting examples of other sulfate or sulfonate detergents include paraffin sulfonates such as the reaction products of alpha olefins and bisulfites (eg, sodium bisulfite). Also included are higher alcohol sulfates such as sodium lauryl sulfate, sodium tallow alcohol sulfate, or fatty acid mono- or diglyceride sulfates (eg, stearic monoglyceride monosulfate), poly (ethoxy) ether alkyl sulfates, including, but not limited to to them, the sulfates of the condensation products of ethylene oxide and lauryl alcohol (normally they have 1 to 5 ethenoxy groups per molecule); lauryl ether sulfonates and other higher alkyl glyceryls; Aromatic poly (ethenoxy) ether sulfates including, but not limited to, the sulfates of the condensation products of ethylene oxide and nonyl phenol (typically have 1 to 20 oxyethylene groups per molecule).

Other non-limiting examples include salts of sulfated aliphatic alcohol, alkyl ether sulfate and / or alkyl aryl ethoxy sulfate distributed by Rhone-Poulenc under the trademark ABEX. Anionic surfactants of the mono- or di-ester phosphate type can also be used. These anionic surfactants are well known in the art and are commercially available under the general trademark GAFAC from GAF Corporation and under the general trademark TRITON from Rohm & Haas Company.

Non-limiting examples of nonionic surfactants suitable for use in the composition or cured coating of the present invention include those containing ether linkages and which are represented by the following general formula: RO (R'O)nH; when the substituent group R represents a hydrocarbon group containing 6 to 60 carbon atoms, the substituent group R 'represents an alkylene group containing 2 to 3 carbon atoms, and mixtures of any of them, and n is an integer that it is between 2 and 100, including the mentioned values.

Such nonionic surfactants can be prepared by treating fatty alcohols or alkyl substituted phenols with an excess of ethylene or propylene oxide. The alkyl carbon chain can contain from 14 to 40 carbon atoms and can be derived from a long calendared fatty alcohol such as oleyl alcohol or stearyl alcohol. Nonionic poolioxyethylene surfactants of the type represented by the above formula are commercially available under the general trademark SURFYNOL from Air Products Chemicals, Inc .; PLURONIC or TETRONIC from BASF Corporation; TERGITOL from Union Carbide; and SURFONIC from Huntsman Corporation. Other non-limiting examples of suitable nonionic surfactants include ethylene oxide and propylene oxide block compolymers based on a glycol such as ethylene glycol or propylene glycol including, but not limited to, those distributed by BASF Corporation under the trademark general commercial PLURONIC.

As noted above, cationic surfactants can also be used. Non-limiting examples of suitable cationic surfactants for use in the compositions and cured coatings of the present invention include acidic salts of alkyl amines such as ARMAC HT, acetic acid salt of n-alkyl amine available from Akzo Nobel Chemicals; imidazoline derivatives such as CALGENE C-100 distributed by Calgene Chemicals Inc .; ethoxylated amines or amides such as DETHOX Amine C-5, a cocoamine ethoxylate distributed by Deforest Enterprises; ethoxylated fatty amines such as ETHOX TAM available from Ethox Chemicals, Inc., and glyceryl esters such as LEXEMUL AR, a glyceryl stearate / stearataidoethyl diethylamine available from Inolex Chemical Co.

Other examples of suitable surfactants can include polyacrylates. Non-limiting examples of suitable polyacrylates include homopolymers and copolymers of acrylate monomers, such as polybutylacrylate and copolymers derived from acrylate monomers (such as ethyl (meth) acrylate, 2-ethylhexacrylate, butyl (meth) acrylate, and acrylate. isobutyl, and hydroxyethyl (meth) acrylate and (meth) acrylic acid monomers. In one embodiment, the polyacrylate can have amino and hydroxy functionality. Examples of suitable amino and hydroxyl functional acrylates are included in US Patent No. 6,013,733 and Example 26 below. Another example of a useful amino hydroxyl functional copolymer is a copolymer of hydroxy ethyl acrylate, 2-ethylhexylacrylate, isobutyl acrylate, and dimethylamino ethylmethacrylate. In another embodiment, the polyacrylate may have acid functionality, which can be provided, for example, by including acid functional monomers such as (meth) acrylic acid in the components used to prepare the polyacrylate. In another embodiment,

ES 2 249 285 T3 The polyacrylate can have acid functionality and hydroxyl functionality, which can be provided, for example, by including acid-functional monomers, such as (meth) acrylic acid and hydroxyl-functional monomers, such as hydroxyethyl (meth) acrylate in the components used to prepare the polyacrylate.

In an embodiment of the present invention, the surfactant is selected from at least one polysiloxane comprising at least one group with reactive function, the polysiloxane comprising at least one of the following structural units (I):

R1nR2mSiO (4-nm) 2 (I) in which the R1, which may be identical or different, represent H, OH, a monovalent hydrocarbon group, a monovalent siloxane group; each R2, which may be identical or different, represents a group comprising at least one group with reactive function.

In another embodiment, the present invention relates to a cured coating resulting from a powder composition made up of components consisting of:

(a) at least one surfactant comprising:

(i) at least one polysiloxane comprising at least one group with reactive function, said polysiloxane comprising at least one of the following structural units (I):

R1nR2mSiO (4-nm) 2 (I) in which the R1 , which may be identical or different, represent H, OH, a monovalent hydrocarbon group or a monovalent siloxane group; each R2, which may be identical or different, represents a group comprising at least one reactive functional group, m and n fulfilling the premises that 0 <n <4, 0 <m <4 and 2 <(m + n) <4; and (ii) at least one polyacrylate surfactant having at least one functional group selected from amino and hydroxyl functionality, acid functionality, and acid and hydroxyl functionality; and (b) a plurality of particles, the concentration of particles present in a surface region of the cured composition being greater than the concentration of particles present in the volume regions of the cured composition.

It should be understood that the "at least one polysiloxane having at least one structural unit (I)" mentioned is a polymer containing at least two Si atoms per molecule. As indicated, the term "polymer" encompasses oligomers and includes without limitation both homopolymers and copolymers. It should be understood that the at least one polysiloxane can include linear, branched, dendritic, or cyclic polysiloxanes.

Also, as used herein, the term "reagent" refers to a functional group that forms a covalent bond with another functional group under conditions sufficient to cure the composition.

Each m and n represented in the structural unit (I) above satisfies the premises that 0 <n <4, 0 <m <4 and 2 <(m + n) <4. When (m + n) is 3, the value represented by n can be 2 and the value represented by m is 1. Likewise, when (m + n) is 2, the value represented by each n and m is 1.

As used herein, "a monovalent hydrocarbon group" means a monovalent group having an exclusively carbon-based backbone repeating unit. As used herein "monovalent" refers to a substituent group that, as a substituent group, forms only a single covalent bond. For example, a monovalent group on the polysiloxane will form a single covalent bond with a silicon atom in the main chain of the polysiloxane polymer. As used herein "hydrocarbon groups" encompasses both branched and unbranched hydrocarbon groups.

Thus, when speaking of a "monovalent hydrocarbon group", the hydrocarbon group can be branched or unbranched, acyclic or cyclic, saturated or unsaturated, or aromatic and can contain from 1 to 24 (or in the case of an aromatic group 3 to 24) carbon atoms. Non-limiting examples of such hydrocarbon groups include alkyl, alkoxy, aryl, alkaryl, and alkoxyaryl groups. Non-limiting examples of lower alkyl groups include, for example, methyl, ethyl, propyl, and butyl groups. As used herein "lower alkyl" refers to alkyl groups having 1 to 6 carbon atoms. One or more of the hydrogen atoms of the hydrocarbon may be substituted with heteroatoms. As used herein "heteroatoms" refers to elements other than carbon, such as oxygen, nitrogen and halogen atoms.

As used herein, "siloxane" means a group comprising a backbone comprising two or more -SiO groups. For example, the siloxane groups represented by R1, explained above, and R, described below, can be branched or unbranched, and be linear or cyclic. Siloxane groups can be sus13

ES 2 249 285 T3 titrated with pendant organic substituent groups, such as alkyl, aryl and alkaryl groups. Organic substituent groups can be substituted with heteroatoms, such as oxygen, nitrogen and halogen atoms, reactive functional groups, such as the aforementioned reactive functional groups in relation to R2 and mixtures of them.

In another embodiment, each of the substituent groups R2, which may be identical or different, represents a group comprising at least one reactive functional group selected from a hydroxyl group, a carboxyl group, an isocyanate group, a blocked polyisocyanate group, a primary amine group, a secondary amine group, a group amide, a carbamate group, a urea group, a urethane group, a vinyl group, an unsaturated ester group such as an acrylate group and a methacrylate group, a maleimide group, a fumarate group, an onium salt group such as a sulfonium group and an ammonium group, an anhydride group, a hydroxyalkylamide group, an epoxy group; where m and n satisfy the premises 0 <n <4, 0 <m <4 and 2 <(m + n) <4.

In one embodiment, the present invention relates to a cured coating as described above, in which at least one polysiloxane comprises at least two groups with reactive function. The polysiloxane can have a reactive group equivalent weight of between 50 and 1000 mg per gram of the polysiloxane. In one embodiment, the polysiloxane has a hydroxyl group equivalent weight of between 50 and 1000 mg KOH per gram of the polysiloxane. In another embodiment, the polysiloxane has an equivalent weight of the hydroxyl group comprised between 100 and 300 mg KOH per gram of the polysiloxane, while in another embodiment, the equivalent weight of the hydroxyl group ranges between 100 and 500 mg KOH per gram. .

In another embodiment, the present invention relates to a coating cured as described, in which at least one R group2 represents a group comprising at least one reactive functional group selected from a hydroxyl group and a carbamate group. In yet another embodiment, the invention relates to a coating cured as described, in which at least one R group2 represents a group comprising at least two reactive functional groups selected from a hydroxyl group and a carbamate group. In another embodiment, the present invention relates to a coating cured as described, in which at least one R group2 represents a group comprising an oxyalkylene group and at least two hydroxyl groups.

In one embodiment, the present invention relates to a cured coating as described above in which the polysiloxane comprises reactive functional groups that are thermally curable functional groups. In an alternative embodiment, at least one of the reactive functional groups of the polysiloxane can be cured by ionizing radiation or actinic radiation. In another alternative embodiment, the polysiloxane may comprise at least one functional group that can be cured by thermal energy and at least one functional group that can be cured by ionizing radiation or actinic radiation.

As used herein "ionizing radiation" means high energy radiation or the secondary energies that result from the conversion of this energy from electrons or other particles to neutrons or gamma radiation, said energies being at least 30,000 electron volts and may be of 50,000 to 300,000 electron volts. While various types of ionizing radiation are suitable for this purpose, such as X-rays, gamma rays and beta rays, radiation produced by high energy accelerated electrons or electron beam devices is preferable. The amount of ionizing radiation in rads for curing compositions according to the present invention may vary depending on factors such as the components of the coating formulation, the thickness of the coating on the substrate, the temperature of the coating composition, and the like. Generally, a 1 mil (25 microns) thick wet film of the coating composition of the present invention can cure in the presence of oxygen through its thickness to a tack free state upon exposure to 0.5-5 megarads of ionizing radiation.

"Actinic radiation" is light with electromagnetic radiation wavelengths in the ultraviolet ("UV") range, through the visible light range, and up to the infrared range. Actinic radiation that can be used to cure the coating compositions of the present invention generally has wavelengths of electromagnetic radiation in the range 150 to 2,000 nanometers (nm), can range from 180 to 1,000 nm, and can also range from 200 to 500 nm. Examples of suitable ultraviolet light sources include mercury arcs, carbon arcs, low, medium, or high pressure mercury lamps, turbulent flow plasma arcs, and ultraviolet light emitting diodes. Preferable ultraviolet light emitting lamps are medium pressure mercury vapor lamps having outputs ranging from 200 to 600 watts per inch (79 to 237 watts per centimeter) along the length of the lamp tube. Generally, a 1 mil (25 cm) wet thick film of the coating composition according to the present invention can be cured through its thickness to a tack-free state upon exposure to actinic radiation by passing the film at a speed of 20 at 1000 feet per minute (6 to 300 meters per minute) under four medium pressure mercury vapor lamps exposing 200 to 1000 millijoules per square centimeter of the wet film.

Useful radiation curable groups that may be present as reactive functional groups on the polysiloxane include unsaturated groups such as vinyl groups, vinyl ether groups, epoxy groups, maleimide groups, fumarate groups, and combinations thereof. In one embodiment, the UV curable groups can include acrylate groups, maleimides, fumarates, and vinyl ethers. Vinyl groups include those with unsaturated ester groups and vinyl ether groups, as described below.

ES 2 249 285 T3

In one embodiment, the present invention relates to coatings cured as described, in which the polysiloxane has the following structure (II) or (III):

RR

II

R - Yes - O - (- Yes - O -)n II

RR

II

- (Si - O) m - Si - R

II

Rto R (II)

RR

II

R - Si - O - (-Si-O-) „, II

Rto R

RR

- (Yes - O)m- - Yes - R Rto Ra (II) in which: m has a value of at least 1; m 'ranges from 0 to 75; n ranges from 0 to 75; n 'ranges from 0 to 75; each R, which may be identical or different, is selected from H, OH, a monovalent hydrocarbon group, a monovalent siloxane group, and mixtures thereof; and -Rto comprises the following structure (IV):

-R3-X (IV) where -R3 selected from an alkylene group, an oxyalkylene group, an alkylene aryl group, an alkenylene group, an oxyalkenylene group, and an alkenylene aryl group; and X represents a group comprising at least one reactive functional group selected from a hydroxyl group, a carboxyl group, an isocyanate group, a blocked polyisocyanate group, a primary amine group, a secondary amine group, an amide group, a carbamate group, a urea group, a urethane group, a vinyl group, an unsaturated ester group, such as an acrylate group and a methacrylate group, a maleimide group, a fumarate group, an onium salt group such as a sulfonium group or an ammonium group, an anhydride group, a hydroxy alkylamide group, and an epoxy group.

As used herein, "alkylene" refers to a cyclic acyclic saturated hydrocarbon group having a carbon chain length of C2 to C25. Non-limiting examples of suitable alkylene groups include but are not limited to propenyl, 1-butenyl, 1-pentenyl, 1-decenyl and 1-heneicosenyl derivatives, such as (CH2) 3, (CH2) 4, (CH2) 5, (CH2) 10 and (CH2) 23 respectively, as well as isoprene and myrcene.

As used herein, "oxyalkylene" refers to an alkylene group containing at least one oxygen atom attached to, or interposed between, two carbon atoms and having a C2 to C25 alkylene carbon chain length. Non-limiting examples of suitable oxyalkylene groups include the derivatives of trimethylol propane monoallyl ether, trimethylol propane diallyl ether, pentaerythritol monoallyl ether, polyethoxylated allyl alcohol, and polypropoxylated allyl alcohol, such as - (CH2)3OCH2C (CH2OH)2(CH2CH2-).

As used herein, "alkylene aryl" refers to an acyclic alkylene group substituted with at least one aryl group, eg, phenyl, having an alkylene carbon chain length of C2 to C25. The aryl group may itself be substituted, if desired. Non-limiting examples of suitable substituent groups for the aryl group include, but are not limited to, hydroxyl groups, benzyl groups, carboxylic acid groups, and aliphatic hydrocarbon groups. Non-limiting examples of suitable alkylene aryl groups include, but are not limited to, the styrene and isocyanate derivatives of 3-isopropenyl-α, α-dimethylbenzyl, such as - (CH2)2C6H4- and -CH2 (CH (CH3) C6H3 (C (CH3) 2 (NCO). As used herein, "alkylene" refers to an acyclic or cyclic hydrocarbon group that has one or more double bonds and that has a carbon chain length C2 to C15 alkylene Non-limiting examples of suitable alkenylene groups include derivatives of propargyl alcohol and acetylenic diols, such as 2,4,7,9-tetramethyl-5-decine-4,7-diol which It is distributed commercially by Air Products and Chemicals, Inc. from Allentown, Pennsylvania as SURFYNOL 104.

Formulas (II) and (III) are diagrammatic and are not intended to imply that the portions in parentheses are necessarily blocks, although it is possible to use blocks, where desired. In some cases the polysiloxane may comprise a number of siloxane units. This is increasingly true as the number of siloxane units employed increases, and is especially true when mixtures of a number of different siloxane units are used. In cases where a plurality of siloxane units are used and it is desirable to form blocks, oligomers can be formed which can be linked to form the block compound. In judiciously selecting reagents, compounds with an alternate structure or blocks of alternate structure can be used.

In one embodiment, the present invention relates to a cured coating as described above in which the substituent group R3 represents an oxyalkylene group. In another embodiment, R3 represents an oxyalkylene group, and X represents a group comprising at least two reactive functional groups.

ES 2 249 285 T3

In another embodiment, the polysiloxane has the structure (II) or (III) described above, in which (n + m) ranges between 2 and 9 or between 2 and 3. In another embodiment, the polysiloxane has a structure (II) or (III) described, in which (n '+ m') oscillates between 2 and 9, or between 2 and 3.

In one embodiment, X represents a group comprising at least one reactive functional group selected from a hydroxyl group and a carbamate group. In another embodiment, X represents a group comprising at least two hydroxyl groups. In yet another embodiment, the present invention relates to a coating cured as described above, wherein X represents a group comprising at least one group selected from H, a monohydroxy-substituted organic group, and a group which has the following structure (V):

R4 - (-CH2 - OH)P (V) in which the substituent group R4 represents -CH2 - C - R3 when p is 2 and the substituent group R3 represents an alkyl group from Ci to C4, or the substituent group R4 represents -CH2 - C - when p is 3, wherein at least a portion of X represents a group having structure (V). In another embodiment, the present invention relates to a coating cured as described in which m is 2 and p is 2.

In one embodiment of the present invention, the polysiloxane is not reactive with the particles. In yet another embodiment, the present invention relates to a cured coating as described above, in which the particles are different from polysiloxane. In yet another embodiment, the present invention relates to a cured coating, as described above, in which the particles have an average particle size of less than 100 nanometers prior to incorporation into the cured composition. Methods known to those of skill in this field for measuring mean particle size are described in more detail below.

In one embodiment, the present invention relates to a cured coating as described above comprising at least one polysiloxane having structure (II) or (III), in which, if no agent is present cured, and if the polysiloxane is a partial condensate of a silanol, then less than 70% by weight of the partial condensate is the partial CH3Si (OH) 3 condensate. These components used in the various embodiments can be selected from the coating components described above.

In one embodiment, the present invention relates to coatings cured as described above in which the polysiloxane, when added to the other component (s) of the coating composition, is present in the coating composition in an amount between 0.01 and 90 percent by weight based on the total weight of the resin solids of the components that make up the coating composition. In another embodiment, the polysiloxane, when added to the other components of the coating composition, is present in the coating composition in an amount of between at least 2, or at least 5, or at least 10 percent by weight based on the total weight of resin solids of the components that make up the coating composition.

In one embodiment, the present invention relates to coatings cured as described above in which the polysiloxane, when added to the other components of the coating composition, is present in the coating composition in a lower amount. at 90, less than 80, less than 65 or less than 30 percent by weight based on the total weight of the resin solids of the components that make up the coating composition. The amount of the polysiloxane can range from any combination of these values including the values cited.

In another embodiment, the present invention relates to a cured composition, as described above, in which the polysiloxane is the reaction product of at least one of the following reagents: (i) at least one polysiloxane of formula (VI):

RRR

III

R - Yes - O - (- Yes - O -)n - Yes - RIII

RRR (VI)

ES 2 249 285 T3 in which each substituent group R, which may be identical or different, represents a group selected from H, OH, a monovalent hydrocarbon group, a monovalent siloxane group, and mixtures thereof; at least one of the groups represented by R is H, and n 'ranges from 0 to 100, it also ranges from 0 1 to 10 and can also range from 0 to 5, so that the percentage of SiH content of the polysiloxane ranges from 2 to 50 percent, and can range from 5 to 25; and (ii) at least one molecule comprising at least one functional group selected from a hydroxyl group, a carboxyl group, an isocyanate group, a blocked polysiloxane group, a primary amine group, a secondary amine group, an amide group, a group carbamate, urea group, urethane group, vinyl group, unsaturated ester group such as acrylate group and methacrylate group, maleimide group, fumarate group, onium salt group such as, for example, a sulfonium group and an ammonium group, an anhydride group, a hydroxy alkylamide group and an epoxy group and at least one unsaturated bond capable of undergoing a hydroxylation reaction. In another embodiment, said functional group is selected from hydroxyl groups.

It should be appreciated that the various R groups may be the same or different and, in certain embodiments, the R groups may be entirely monovalent hydrocarbon groups or be a mixture of different groups such as monovalent hydrocarbon groups and hydroxyl groups.

In another embodiment, this reaction product is ungelled. As used herein "ungelled" refers to a reaction product that is substantially free of crosslinking and has an intrinsic viscosity when dissolved in a suitable solvent, as determined for example according to ASTM-D 1795 or ASTM -D4243. The intrinsic viscosity of the reaction product is an indication of its molecular weight. A gelled reaction product, on the other hand, since it has an extremely high molecular weight, will have too high an intrinsic viscosity to be measured. As used herein, a reaction product that is "substantially free of crosslinking" refers to a reaction product that has a weight average molecular weight (Mw), as determined by gel permeation chromatography, of less than 1,000. .000.

It should be noted that the level of unsaturation contained in reagent (ii) above can be selected to obtain an ungelled reaction product. That is, when using a silicon hydride-containing polysiloxane (i) having a higher average Si-H functionality value, the reagent (ii) may have a lower unsaturation level. For example, the silicon hydride-containing polysiloxane (i) may be a low molecular weight material in which n 'ranges from 0 to 5 and the mean value of Si-H functionality is two or less. In this case, the reagent (ii) may contain two or more unsaturated bonds capable of undergoing hydrosilylation without gelation occurring.

Non-limiting examples of polysiloxanes containing silicon hydride (i) include 1,1,3,3-tetramethyl disiloxane in which n 'is 0 and the average Si-H functionality is two; and polymethyl polysiloxane containing silicon hydride in which n 'ranges from 4 to 5 and the average Si-H functionality is approximately two, as for example that commercially available from BASF Corporation as MASILWAX BASE®.

Materials for use as reagent (ii) mentioned may include hydroxyl functional group containing allyl esters such as, for example, those selected from trimethylolpropane monoallyl ether, pentaerythritol monoallyl ether, trimethylolpropane diallyl ether, polyoxyalkylene alcohols such as polyethoxylated alcohol, polypropoxylated alcohol and polybutoxylated alcohol, undecylenic acid-epoxy adducts, allyl glycidyl ether-carboxylic acid adducts, and mixtures thereof. Mixtures of hydroxyl-functional polyallyl ethers with hydroxyl-functional monoallyl ethers or allyl alcohols are also suitable. In certain cases, reagent (ii) may contain at least one unsaturated bond in a terminal position. The reaction conditions and the ratio of reagents (i) and (ii) is selected so that the desired functional group is formed.

The hydroxyl-functional group-containing polysiloxane can be prepared by reacting a hydroxyl-functional group-containing polysiloxane with an anhydride to form the semi-ester acid group under reaction conditions that favor only the reaction of the anhydride and hydroxyl-functional groups, and prevent further esterification from occurring. Non-limiting examples of suitable anhydrides include hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, phthalic anhydride, trimellitic anhydride, succinic anhydride, chloréndic anhydride, alkenyl succinic anhydride, and mixtures of substituted octenyl succinic anhydrides and alkenyl anhydrides.

The half-ester group-containing reaction product thus prepared can be further reacted with a monoepoxide to form a polysiloxane containing secondary hydroxyl group (s). Non-limiting examples of suitable monoepoxides include glycidyl phenyl ether, glycidyl n-butyl ether, glycidyl cresyl ether, glycidyl isopropyl ether, glycidyl versatate, for example CARDURA E available from Shell Chemical Co., and mixtures thereof.

In another embodiment, the present invention relates to coatings cured as described above in which the polysiloxane is a carbamate-functional group-containing polysiloxane comprising the reaction product of at least the following reagents:

(i) at least one silicon hydride-containing polysiloxane of structure (VI) mentioned above in which R and n 'are as described for said structure;

ES 2 249 285 T3 (ii) at least one hydroxyl functional group containing material having one or more bonds capable of undergoing hydrosilation reaction as described above, and (iii) at least one weight carbamate functional material low molecular weight comprising the reaction product of an alcohol or glycol ether and a urea.

Examples of such "low molecular weight carbamate functional material" include, but are not limited to, alkyl carbamate and hexyl carbamates, and the glycol ether carbamates described in US Patent No. 5,922. 475 and 5,976,701, which are incorporated herein by reference.

Carbamate functional groups can be incorporated into the polysiloxane by reacting the hydroxyl functional group containing polysiloxane with the low molecular weight carbamate functional material through a "transcarbamoylation" process. The low molecular weight carbamate function material, which can be derived from an alcohol or glycol ether can react with free hydroxyl groups of a polysiloxane polyalcohol, that is, a material that has an average of two or more hydroxyl groups per molecule, producing a carbamate functional polysiloxane and the parent alcohol or glycol ether. The reaction conditions and the ratio of reactants (i), (ii) and (iii) are selected to form the desired groups.

Low molecular weight carbamate functional material can be prepared by reacting alcohol or glycol ether with urea in the presence of a catalyst such as butyl stanoic acid. Non-limiting examples of suitable alcohols include low molecular weight aliphatic, cycloaliphatic, and aromatic alcohols, such as methanol, ethanol, propanol, butanol, cyclohexanol, 2-ethylhexanol, and 3-methylbutanol. Non-limiting examples of suitable glycol ethers include ethylene glycol methyl ether and propylene glycol methyl ether. Incorporation of carbamate functional groups into the polysiloxane can also be achieved by reacting isocyanic acid with free hydroxyl groups on the polysiloxane.

As mentioned above, in addition to or in relation to the hydroxyl and / or carbamate functional groups, the polysiloxane may comprise one or more additional reactive functional groups such as, for example, carboxyl groups, isocyanate groups, blocked isocyanate groups, carboxylate, primary amine groups, secondary amine groups, amide groups, urea groups, urethane groups, epoxy groups, and mixtures thereof.

When at least one polysiloxane group contains functional carboxyl groups, the polysiloxane can be prepared by reacting at least one hydroxyl-functional group-containing polysiloxane, as described above, with a polycarboxylic acid or anhydride. Non-limiting examples of polycarboxylic acids suitable for use include adipic acid, succinic acid, and dodecanedioic acid. Non-limiting examples of suitable anhydrides include those described above. The reaction conditions and the ratio of reagents are selected to form the desired functional groups.

In the case where the polysiloxane contains one or more isocyanate functional groups, the polysiloxane can be prepared by reacting at least one hydroxyl functional group containing polysiloxane, as described above, with a polyisocyanate, such as diisocyanate. Non-limiting examples of suitable polyisocyanates include aliphatic polyisocyanates, such as aliphatic diisocyanates, such as 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate; cycloaliphatic polyisocyanates, such as 1,4-cyclohexyl diisocyanate, isophorone diisocyanate and α, α-xylene diisocyanate; and aromatic polyisocyanates, such as 4,4'-diphenylmethane diisocyanate, 1,3-phenylene diisocyanate and tolylene diisocyanate. All of these polyisocyanates along with other suitable ones are described in greater detail in US Patent No. 4,046,729 at column 5, line 26 to column 6, line 28. The reaction conditions and the ratio of the reagents are selected so that the desired functional groups are formed.

The substituent group X in structure (IV) may consist of a polymeric urethane or urea-containing material that is terminated with isocyanate, hydroxyl, primary or secondary amine functional groups or mixtures thereof. When the substituent X consists of said functional groups, the polysiloxane can consist of the reaction product of at least one polysiloxane polyalcohol as described, one or more polyisocyanates and, optionally, one or more compounds having at least two atoms of Active hydrogen per molecule selected from hydroxyl groups, primary amine groups, and secondary amine groups.

Non-limiting examples of suitable polyisocyanates include those described above. Non-limiting examples of compounds having at least two active hydrogen atoms per molecule include polyalcohols and polyamines that contain primary and / or secondary amine groups.

Non-limiting examples of suitable polyalcohols include polyalkylene ether polyalcohols, including thioethers; polyester polyalcohols; including polyhydroxy polyesteramides; and hydroxyl-containing polycaprolactones and hydroxy-containing acrylic interpolymers. Also useful are polyether polyalcohols formed by oxyalkylation of various polyalcohols, such as glycols such as ethylene glycol, 1,6-hexanediol, Bisphenol A, and the like, or higher polyalcohols such as trimethylolpropane, pentaerythritol, and the like. Polyester polyalcohols can also be used. In US Patent No. 4,046,729 at column 7, line 52 to column 8, line 9; column 8, line 29 to column 9, line 66; and in US Pat. No. 3,919,315 at column 2, line 64 to column 3, line 33, these and other suitable polyalcohols are described.

ES 2 249 285 T3

Non-limiting examples of suitable polyamines include primary and secondary diamines or polyamines in which the groups attached to the nitrogen atoms can be saturated or unsaturated, aliphatic, alicyclic, aromatic, aliphatic substituted aliphatic, aliphatic substituted aromatic and heterocyclic. . Suitable examples of aliphatic and alicyclic diamines include 1,2-ethylene diamine, 1,2-propylene diamine, 1,8-octane diamine, isophorone diamine, propane-2,2-cyclohexyl amine, and the like. Aromatic diamines include phenylene diamine and toluene diamines, such as o-phenylene diamine p-tolylene diamine. These and other suitable polyamines are described in greater detail in US Patent No. 4,046,729 at column 6, line 61a column 7, line 26.

In one embodiment, the substituent group X of structure (IV) may consist of a polymeric ester-containing group that is terminated with hydroxyl or carboxylic acid functional groups. When X is said or group, at least one of the polysiloxanes may consist of the reaction product of one or more polysiloxane polyalcohols, as described above, one or more materials having at least one carboxylic acid functional group and one or more organic polyalcohols. Suitable non-limiting examples of materials having at least one carboxylic acid functional group include carboxylic acid group containing polymers known in the art, such as carboxylic acid group containing acrylic polymers, polyester polymers and polymers. of polyurethane, such as those described in US Patent No. 4,681,811. Non-limiting examples of suitable organic polyalcohols include those described above.

To form the polysiloxane containing epoxy groups, at least one polysiloxane containing hydroxyl functional groups can be further reacted, as described above, with a polyepoxide. The polyepoxide can be an aliphatic or cycloaliphatic polyepoxide or mixtures thereof. Non-limiting examples of suitable polyepoxides for use include epoxy functional acrylic copolymers prepared from at least one ethylenically unsaturated monomer having at least one epoxy group, such as glycidyl (meth) acrylate and allyl glycidyl ether, and one or more ethylenically unsaturated monomers that do not have epoxy functionality. The preparation of such epoxy functional acrylic copolymers is described in detail in US Pat. No. 4,681,811 at column 4, line 52 to column 5, line 50. The reaction conditions and the ratio of the reactants are selected to form the desired functional groups.

In yet another embodiment, the present invention relates to cured compositions, as described, in which at least one reagent is present during formation of the coating composition. As used herein, the term "at least one reagent" refers to any material that comprises a functional group that is reactive with at least one functional group selected from at least one functional group of the polysiloxane and at least one functional group of the material. . In one of the embodiments, said reagent can be selected from at least one curing agent.

In accordance with the present invention, the coating compositions that have been described are formed from components comprising at least one film-forming material having at least one reactive functional group. If the polysloxane is present, the film-forming material can have at least one functional reactive group with at least one functional group of the polysiloxane and the curing agent, if present. In one embodiment, said film-forming material can have at least one reactive functional group selected from a hydroxyl group, a carbamate group, an epoxy group, an isocyanate group, and a carboxyl group. In another embodiment, the film-forming material may have at least one reactive functional group selected from a hydroxyl group and a carbamate group.

The film-forming material can contain one or more reactive functional groups selected from hydroxyl groups, carbamate groups, epoxy groups, isocyanate groups, carboxylic acid groups, and mixtures of any of them.

Non-limiting examples of additional suitable hydroxyl group-containing polymers include acrylic polyalcohols, polyester polyalcohols, polyurethane polyalcohols, polyether polyalcohols, and mixtures thereof. The additional polymer can be an acrylic polyol that can have a hydroxyl equivalent weight of between 1000 and 100 grams per solid equivalent, including the mentioned values.

Acrylic polymers containing suitable hydroxyl group and / or carboxyl groups can be prepared from polymerizable ethylenically unsaturated monomers and can consist of copolymers of (meth) acrylic acid and / or hydroxyalkyl esters of (meth) acrylic acid with one or more polymerizable ethylenically unsaturated monomers such as (meth) acrylic acid alkyl esters including methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and 2-ethyl hexylacrylate and vinyl aromatic compounds such as styrene, alpha-methyl styrene and vinyl toluene. As used herein "(meth) acrylate" and like terms are intended to include both acrylates and methacrylates.

The acrylic polymer can be prepared from ethylenically unsaturated beta-hydroxy ester functional monomers. Such monomers can be derived from the reaction of an ethylenically unsaturated acid functional monomer such as monocarboxylic acids such as acrylic acid and an epoxy compound that does not participate in free radical initiated polymerization with the unsaturated acid monomer. Non-limiting examples of such epoxy compounds include glycidyl ethers and esters. Non-limiting examples of suitable glycidyl ethers include glycidyl ethers of alcohols and phenols such as glycidyl butyl ether, glycidyl octyl ether, glycidyl phenyl ether, and the like. Among the non-limiting examples of glycidyl esters

Suitable ES 2 249 285 T3 include those distributed commercially by Shell Chemical Company under the trademark CARDURA and by Exxon Chemical Company under the trademark GLYDEXX-10. Alternatively, beta-hydroxy ester functional monomers are prepared from an ethylenically unsaturated epoxy functional monomer, such as glycidyl (meth) acrylate and allyl glycidyl ether and saturated carboxylic acid, such as saturated monocarboxylic acid, as acid. isostearic.

Epoxy functional groups can be incorporated into the polymer prepared from polymerizable ethylenically unsaturated monomers by copolymerizing oxirane group-containing monomers, such as glycidyl (meth) acrylate and glycidyl allyl ether, with other polymerizable ethylenically unsaturated monomers such as those that have been described above. The preparation of such epoxy functional acrylic polymers is described in detail in US Pat. No. 4,001,156 in columns 3 to 6.

Carbamate functional groups can be incorporated into the polymer prepared from ethylenically unsaturated monomers polymerizable by copolymerization, for example the above-described ethylenically unsaturated monomers with a carbamate functional vinyl monomer such as carbamate functional methacrylic acid alkyl ester. Useful carbamate functional alkyl esters can be prepared by reacting, for example, a hydroxyalkyl carbamate (which may be the reaction product of ammonia and ethylene carbonate or propylene carbonate) with methacrylic anhydride.

Other useful carbamate functional vinyl monomers include for example the reaction product of hydroxyethyl methacrylate, isophorone diisocyanate and hydroxypropyl carbamate; or the reaction product of hydroxypropyl methacrylate, isophorone diisocyanate; and methanol. Other carbamate-functional vinyl monomers such as the reaction product of isocyanic acid (HNCO) with a hydroxyl-functional acrylic or methacrylic monomer such as hydroxyethyl acrylate, and the monomers described in US Patent No. 3,479,328.

Carbamate functional groups can also be incorporated into the acrylic polymer by reacting a hydroxyl functional acrylic polymer with a low molecular weight alkyl carbamate such as methyl carbamate. Pendent carbamate groups can also be incorporated into the acrylic polymer through a "transcarbamoylation" reaction, whereby a hydroxyl functional acrylic polymer is reacted with a low molecular weight carbamate derived from an alcohol or a glycol ether. The carbamate groups can be exchanged with the hydroxyl groups to produce the acrylic polymer with carbamate function and the parent alcohol or glycol ether. Also, hydroxyl functional acrylic polymers can be reacted with isocyanic acid to provide pendant carbamate groups. Similarly, hydroxyl functional acrylic polymers can be reacted with urea to provide pendant carbamate groups.

Polymers prepared from polymerizable ethylenically unsaturated monomers can be prepared through solution polymerization techniques that are well known among those skilled in this field, in the presence of suitable catalysts such as organic peroxides or azo compounds, such as for example benzoyl peroxide or N, N-azobis (isobutyronitrile). The polymerization can be carried out in an organic solution in which the monomers are soluble through conventional techniques within the art. Alternatively, these polymers can be prepared through aqueous emulsion or dispersion polymerization techniques that are known in the art. The ratio of reagents and reaction conditions are selected to result in an acrylic polymer with the desired pendant functionality.

Polyester polymers are also useful in the coating compositions of the invention as an additional polymer. Useful polyester polymers may include the condensation products of polyhydric alcohols and polycarboxylic acids. Non-limiting examples of suitable polyhydric alcohols include ethylene glycol, neopentyl glycol, trimethylol propane, and pentaerythritol. Non-limiting examples of suitable polycarboxylic acids include adipic acid, 1,4-cyclohexyl dicarboxylic acid, and hexahydrophthalic acid. In addition to the above-mentioned polycarboxylic acids, functional equivalents of the acids, such as anhydrides, where they exist, or lower alkyl esters of the acids, such as methyl esters, can be used. Also, small amounts of monocarboxylic acids such as stearic acid can be used. The ratio of reagents and reaction conditions are selected to result in a polyester polymer with the desired pendant functionality, ie, carboxyl or hydroxyl functionality.

For example, hydroxyl group-containing polyesters can be prepared by reacting a dicarboxylic acid anhydride such as hexahydrophthalic anhydride with a diol such as neopentyl glycol in a 1: 2 molar ratio. When it is desired to improve air drying, suitable drying oil fatty acids can be used, including derivatives of linseed oil, soybean oil, tall oil, dehydrated castor oil and tung oil.

Carbamate functional polyesters can be prepared by first forming a hydroxyalkyl carbamate that can react with the polyacids and polyalcohols used in forming the polyester. Alternatively, terminal carbamate functional groups can be incorporated into the polyester by reacting isocyanic acid with a hydroxy functional polyester. Also, carbamate functionality can be incorporated into the polyester by reacting a hydroxyl polyester with a urea. Additionally, carbamate groups can be incorporated into the polyester by transcarbamoylation reaction. The preparation of suitable carbamate functional group containing polyesters include those described in US Patent No. 5,593,733 at column 2, line 40 to column 4, line 9.

ES 2 249 285 T3

Polyurethane polymers containing terminal isocyanate or hydroxyl groups can also be used as additional polymer in the coating compositions of the invention. The polyurethane polyalcohols or NCO-terminated polyurethanes that can be used are those prepared by reacting polyalcohols, including polymeric polyalcohols, with polyisocyanates. Polyureas containing terminal isocyanate or primary and / or secondary amine groups that can also be used may consist of those prepared by reacting polyamines, including, but not limited to, polymeric polyamines with polyisocyanates.

The hydroxyl / isocyanate or amine / isocyanate equivalent ratio can be adjusted and the reaction conditions can be selected to obtain the desired end groups. Non-limiting examples of suitable polyisocyanates include those described in US Patent No. 4,046,729, at column 5, line 26 to column 6, line 28. Non-limiting examples of suitable polyalcohols include described in US Pat. No. 4,046,729 at column 7, line 52 to column 10, line 35, part of which is incorporated herein by reference. Non-limiting examples of suitable polyamines include those described in US Patent No. 4,046,729 at column 6, line 61 to column 7, line 32 and in US Patent No. 3,799,854 in column 3, lines 13 to 50.

Carbamate functional groups can be introduced into polyurethane polymers by reacting a polyisocyanate with a polyester having hydroxyl functionality and containing pendant carbamate groups. Alternatively, the polyurethane can be prepared by reacting a polyisocyanate with a polyester polyol and a hydroxyalkyl carbamate or isocyanic acid as separate reagents. Non-limiting examples of suitable polyisocyanates include aromatic isocyanates (such as 4,4'-diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, and toluene diisocyanate) and aliphatic polyisocyanates (such as 1,4-tetramethylene diisocyanate and 1,4-tetramethylene diisocyanate). 1,6-hexamethylene). Cycloaliphatic diisocyanates can be used, for example 1,4-cyclohexyl diisocyanate and isophorone diisocyanate.

Non-limiting examples of suitable polyether polyalcohols include polyalkylene ether polyalcohols such as those having the following structural formulas (VII) or (VIII):

wherein the substituent group R represents hydrogen or a lower alkyl group of 1 to 5 carbon atoms including mixed substituents, n has a value between 2 and 6, and m has a value between 8 and 100 or more. Non-limiting examples of polyalkylene ether polyalcohols include poly (oxytetramethylene) glycols, poly (oxytetraethylene) glycols, poly (oxy-1,2-propylene) glycols, and poly (oxy-1,2-butylene) glycols.

Also useful may be polyether polyalcohols formed from the oxyalkylation of various polyalcohols, such as, but not limited to, ethylene glycol, 1,6-hexanediol, Bisphenol A and the like, or other higher polyalcohols such as trimethylolpropane, pentaerythritol and the like. . Polyalcohols of higher functionality that can be used, as indicated, can be obtained for example by oxyalkylation of compounds such as sucrose or sorbitol. One oxyalkylation method that can be used is the reaction of a polyol with an alkylene oxide, including, but not limited to, propylene or ethylene oxide, in the presence of an acidic or basic catalyst. Specific non-limiting examples of polyethers include those distributed under the trademarks TERATHANE and TERACOL, distributed by EI duPont de Nemours and Co., Inc.

In one embodiment, the present invention relates to a cured composition as described above in which at least one of the film-forming materials comprises reactive functional groups that are thermally curable functional groups. In an alternative embodiment, at least one of

ES 2 249 285 T3 the reactive functional groups of the film-forming material can be curable by ionizing radiation or actinic radiation. In another alternative embodiment, the film-forming material may consist of at least one functional group that can be thermally cured and at least one functional group that can be cured by ionizing radiation or actinic radiation.

Useful radiation curable groups that may be present as reactive functional groups on the polysiloxane include unsaturated groups such as vinyl groups, vinyl ether groups, epoxy groups, maleimide groups, fumarate groups, and combinations thereof. In one embodiment, the UV curable groups can include acrylate groups, maleimides, fumarates, and vinyl ethers. Suitable vinyl groups include those with unsaturated ester groups and vinyl ether groups, as explained below.

In one embodiment, the additional polymer may have a weight average molecular weight (Mw) of between 1000 and 20,000, as determined by gel permeation chromatography using a polystyrene standard. In another embodiment, the Mw of the additional polymer ranges from 1500 to 15,000 and can range from 2000 to 12,000 as determined by gel permeation chromatography using a polystyrene standard, including the quoted values.

It should be mentioned that in the embodiments in which at least one polysiloxane and at least one additional polymer are present during formation of the coating composition, the reactive functional groups of the polysiloxane and the additional polymer may be the same or different, although each of them must be reactive with at least the functional group of the curing agent if used. Non-limiting examples of reactive functional groups include hydroxyl groups, carboxylic acid groups, isocyanate groups, carboxylate groups, primary amine groups, secondary amine groups, amide groups, carbamate groups, and epoxy groups.

In one embodiment of the present invention, the additional polymer having at least one reactive functional group is generally present, if used, when added to the other components of the coating composition, in an amount of at least 2 percent by weight. The additional polymer may be present in an amount of at least 5 percent by weight and is typically present in an amount of at least 10 percent by weight based on the total weight of the resin solids of the components that make up the coating composition. Also, the additional polymer, having at least one reactive functional group, if employed, is generally present, when added to the other components of the coating composition, in an amount of less than 80 percent by weight. It may be present in an amount of less than 60 percent by weight, and is typically present in an amount of less than 50 percent by weight based on the total weight of the resin solids of the components that make up the coating composition. The amount of additional polymer having at least one reactive functional group present in the coating compositions can range from any combination of these values including the quoted values.

In yet another embodiment, said reagent is selected from at least one curing agent. Said curing agent can be selected from an aminoplast resin, a polyisocyanate, a blocked isocyanate, a polyepoxide, a polyacid, a polyol, and mixtures thereof.

In another embodiment, the present invention relates to compositions such as those described in which the curing agent is an aminoplast. Aminoplast resins comprising phenoplasts, as curing agents for materials containing hydroxyl, carboxylic acid and carbamate functional group are well known in the art. Suitable aminoplasts, such as those mentioned above, are known to those skilled in the art. Aminoplasts can be obtained by condensation reaction of formaldehyde with an amine or amide. Non-limiting examples of amines or amides include melamine, urea, or benzoguanamine. Condensates with other amines or amides can be used; for example, glucoluryl aldehyde condensates, which give a high melting point crystalline product useful in powder coatings. Although the aldehyde used is most often formaldehyde, other aldehydes such as acetaldehyde, crotonaldehyde and benzaldehyde can be used.

The aminoplast contains imino and methylol groups and in certain cases at least a portion of the methylol groups are etherified with an alcohol to modify the cure response. Any monohydric alcohol can be used for this purpose including methanol, ethanol, n-butyl alcohol, isobutanol, and hexanol.

Non-limiting examples of aminoplasts include melamine-, urea-, or benzoguanamine condensates, in certain cases monomeric and at least partially etherified, with one or more alcohols containing one to four carbon atoms. Non-limiting examples of suitable aminoplast resins include those distributed, for example, by Cytec Industries, Inc. under the trademark CYMEL® and by Solutia, Inc. under the trademark RESIMENE®.

In another embodiment, the present invention relates to compositions such as those described above in which the curing agent, when added to the other components that make up the coating composition, is generally present in an amount comprised between 2 percent by weight and 65 percent by weight based on the total weight of the resin solids of the components that make up the coating composition. The amount of curing agent can range from any combination of these values including the quoted values.

ES 2 249 285 T3

Other suitable curing agents for use include, but are not limited to, polyisocyanate curing agents. As used herein, the term "polyisocyanate" is intended to include blocked (or capped) polyisocyanates as well as unblocked polyisocyanates. The polyisocyanate can be an aliphatic or aromatic polyisocyanate, or a mixture thereof. Diisocyanates can be used although higher polyisocyanates are often used as isocyanurates of diisocyanates. Higher polyisocyanates can also be used in combination with diisocyanates. Isocyanate prepolymers can also be used, such as the reaction products of polyisocyanates with polyalcohols. Mixtures of polyisocyanate curing agents can also be used.

If the polyisocyanate is blocked or capping, any suitable aliphatic, cycloaliphatic or aromatic alkyl monoalcohol known to those skilled in the art can be used as a capping agent for the polyisocyanate. Other suitable capping agents include oximes and lactams. When used, the polyisocyanate curing agent is typically present, when added to the other components of the coating composition, in an amount between 5 and 65 percent by weight, it may be present in an amount between 10 and 45 percent by weight, and is often present in an amount between 15 and 40 percent by weight based on the total weight of the resin solids of the components that make up the coating composition.

Other useful curing agents include blocked polyisocyanate compounds such as the tricarbamoyl triazine compounds described in detail in US Patent No. 5,084,541. When used, the blocked isocyanate curing agent may be present, when added to the other components of the coating composition, in an amount of up to 20 percent by weight, and may be present in an amount from 1 to 20 percent by weight, based on the total weight of the resin solids of the components that make up the coating composition.

Anhydrides as curing agents for hydroxyl functional group-containing materials are also well known in the art and can be employed in the present invention. Non-limiting examples of anhydrides suitable for use as curing agents in the coating compositions of the invention include those having at least two carboxylic acid anhydride groups per molecule that are derived from a monomer mixture comprising an anhydride of ethylenically unsaturated carboxylic acid and at least one vinyl comonomer, such as styrene, alpha methyl styrene, vinyl toluene, and the like. Non-limiting examples of suitable ethylenically unsaturated carboxylic acid anhydrides include maleic anhydride, citraconic anhydride, and itaconic anhydride. Alternatively, the anhydride may be an anhydride adduct of a diene polymer such as maleinized polybutadiene or a maleinized butadiene copolymer, such as a butadiene / styrene copolymer. These anhydride and other suitable curing agents are described in US Pat. No. 4,798,746 at column 10, lines 16-50 and in US Patent No. 4,732,790 at column 3, lines 41-57.

Polyepoxides as curing agents for carboxylic acid functional group containing materials are known in the art. Non-limiting examples of suitable polyepoxides for use in the coating compositions of the present invention include polyglycidyl ethers of polyhydric phenols and of aliphatic alcohols, which can be prepared by etherification of polyhydric phenol, or aliphatic alcohol with an epihalohydrin such as epichlorohydrin. in the presence of an alkali. These suitable polyepoxides and others are described in US Pat. No. 4,681,811 at column 5, lines 33 through 58, which are incorporated herein by reference.

Suitable curing agents for epoxy functional group containing materials include polyacid curing agents, such as acid group containing acrylic polymers prepared from an ethylenically unsaturated monomer containing at least one carboxylic acid group and at least one ethylenically monomer. unsaturated that is free of carboxylic acid groups. Such acid-functional acrylic polymers can have an acid number of between 30 and 150. Acid functional group containing polyesters can also be used. The polyacid curing agents that have been described are described in greater detail in US Patent No. 4,681,811 at column 6, line 45 to column 9, line 54.

Also known in the art as curing agents for isocyanate-functional group-containing materials are polyalcohols, that is, materials having two or more hydroxyl groups per molecule. Non-limiting examples of such materials suitable for use in the coating compositions of the invention include polyalkylene ether polyalcohols including thio ethers; polyester polyalcohols, including polyhydric polyesteramides; and hydroxyl-containing polycaprolactones and hydroxy-containing acrylic interpolymers. Also useful are polyether polyalcohols formed from the oxyalkylation of various polyalcohols, for example glycols such as ethylene glycol, 1,6-hexanediol, Bisphenol A and the like, or higher polyalcohols such as trimethylol propane, pentaerythritol and the like. Polyester polyalcohols can also be used. These polyol curing agents and other suitable ones are described in US Pat. No. 4,046,729 at column 7, line 52 to column 8, line 9; column 8, line 29 to column 9, line 66, and in patent No. 3,919,315 at column 2, line 64 to column 3, line 33.

Polyamines can also be used as curing agents for isocyanate-functional group-containing materials. Non-limiting examples of suitable polyamine curing agents include primary or secondary diamines or polyamines in which the radicals attached to the nitrogen atoms may be saturated or

ES 2 249 285 T3 unsaturated, aliphatic, alicyclic, aromatic, aromatic substituted aliphatic, aliphatic substituted aromatic and heterocyclic. Non-limiting examples of suitable aliphatic and alicyclic diamines include 1,2-ethylene diamine, 1,2-propylene diamine, 1,8-octane diamine, isophorone diamine, propane-2,2-cyclohexyl amine, and the like. Non-limiting examples of suitable aromatic diamines include phenylene diamines and toluene diamines, such as o-phenyl diamine and p-tolylene diamine. These polyamines and other suitable polyamines are described in detail in US Patent No. 4,046,729 at column 6, line 61 to column 7, line 26.

When desired, appropriate mixtures of curing agents can be used. It should be mentioned that the coating compositions can be formulated as a one-component coating composition in which the curing agent, such as an aminoplast resin and / or blocked isocyanate as described above, is mixed with other components of the coating composition. The one-component coating composition can be stably stored as formulated. Alternatively, the coating compositions can be formulated as a two-component coating composition to which a polyisocyanate curing agent, such as those described, can be added to a preformed mixture of the other components of the coating composition. immediately before application. The preformed mixture may consist of curing agents, such as aminoplast resins and / or a blocked isocyanate as described above.

In another embodiment in which the coating is cured by actinic radiation or the combination of actinic radiation and thermal energy, the components from which the coating composition is formed may further include at least one curing agent that is a photoinitiator or a photosensitizer that provides free radicals or cations to initiate the polymerization process. Useful photoinitiators have an absorption within the range of 150 to 2,000 nm. Non-limiting examples of useful photoinitiators include benzoin, benzophenone, hydroxy benzophenone, anthraquinone, thioxanthone, substituted benzoins, such as butyl isomers of benzoin ethers, α, α-diethoxyacetophenone, α, α-dimethoxy-α-phenylacetophenone , 2-hydroxy-2-methyl-1-phenyl propane 1-one and 2,4,6-trimethyl benzoyl diphenyl phosphine oxide.

In an alternative embodiment, the reagent may include at least one material that has at least one reactive functional group that is blocked with a silyl group. The silyl blocked material is different from the polysiloxane (a) described above. Hydrolysis of the silyl group regenerates the reactive functional group on the material that is available for further reaction with the curing agent.

A non-limiting example of silyl blocking groups include those with the following structure (IX):

I

- Yes - R2 I R3 (IX) in which R1, R2 and R3, which may be identical or different, represent an alkyl group having 1 to 18 carbon atoms, a phenyl group or an allyl group.

Non-limiting examples of suitable functional groups that can be blocked by the silyl group include hydroxyl groups, carbamate groups, carboxyl groups, amide groups, and mixtures thereof. In one embodiment, the functional groups are hydroxyl groups.

Non-limiting examples of suitable compounds that can be reacted with the functional group to form the silyl group include hexamethyldisilazane, trimethylchlorosilane, trimethylsilyldiethylamine, t-butyl dimethylsilyl chloride, diphenyl methylsilyl chloride, hexamethyl disilazide, hexamethylsiloxane, trimethylsiloxane, trimethylsiloxane, trimethylsiloxane hexamethyldisilyl acetamide, N, N'-bis [trimethylsilyl] -urea, and mixtures of any of them.

Other examples of suitable compounds for silylation reactions, and suitable reaction conditions and reagents for trimethylsilylation reactions are described in Example 28, below, and in T. Greene et al., Protective Groups in Organic Synthesis (2nd ed. 1991) on pages 68-86 and 261-263.

The main chain of the material can consist of a compound comprising at least one linkage selected from an ester linkage, a urethane linkage, a urea linkage, an amide linkage, a siloxane linkage, and an ether linkage or a polymer such as, for example, a polyester, an acrylic polymer, a polyurethane, a polyether, a polyurea, a polyamide and copolymers of any of them.

Suitable compounds or polymers having at least one ester linkage and at least one reactive functional group include half-esters formed by reacting at least one polyol with at least one 1,2-anhydride. Half esters are suitable as they have a relatively low molecular weight and are quite reactive with epoxy functionality.

ES 2 249 285 T3

The half-ester is obtained for example by reacting a polyol and a 1,2-anhydride under conditions sufficient to open the anhydride ring to form the half-ester without substantially occurring polyesterification. These reaction products have a relatively low molecular weight with narrow molecular weight distributions and low viscosity. The term "without substantially occurring polyesterification" means that the carboxyl groups formed by reaction of the anhydride do not subsequently esterify the polyol in a recurring manner. Also in this embodiment, less than 10, typically less than 5 weight percent of the high molecular weight polyester is formed based on the resin solids of the components that make up the coating composition.

The 1,2-anhydride and the polyol can be mixed and the reaction can be carried out in the presence of an inert atmosphere, such as nitrogen, and a solvent such as ketone or aromatic hydrocarbon to dissolve the solid ingredients and / or decrease the viscosity of the reaction mixture. In one embodiment, a 1,2-dicarboxylic anhydride can be used for the desired ring opening reaction and the formation of the half ester to take place. Reaction of a polyol with a carboxylic acid instead of an anhydride would require condensation esterification and removal of water by distillation, and such conditions would favor undesirable polyesterification. According to the present invention, the reaction temperature can be low, that is, lower than 135 ° C and typically can range between 70 ° and 135 ° C. The reaction time can vary somewhat depending on the reaction temperature and generally ranges from 10 minutes to 24 hours.

The equivalent ratio of anhydride to hydroxyl in the polyol can be at least 0.8: 1 (considering the anhydride monofunctional) to obtain a maximum conversion to the desired half-ester. Ratios less than 0.8: 1 can be employed although such ratios can result in increased formation of lower functional half esters.

Useful anhydrides include aliphatic, cycloaliphatic, olefinic, cycloolefinic, and aromatic anhydrides. Substituted aliphatic and aromatic anhydrides are also useful as long as the substituents do not adversely affect the reactivity of the anhydride or the properties of the resulting polyester. Examples of substituents include chlorine, alkyl, and alkoxy. Examples of anhydrides include succinic anhydride, anhydride methylsuccinic anhydride, dodecenyl succinic anhydride, octadecenyl, phthalic anhydride, tetrahydrophthalic anhydride, anhydride methyltetrahydrophthalic, hexahydrophthalic anhydride, alkyl anhydrides hexahydrophthalic as methylhexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylene tetrahydrophthalic anhydride, chlorendic anhydride itaconic, citraconic anhydride and maleic anhydride.

Polyalcohols that can be used include simple polyalcohols, that is, those containing from 2 to 20 carbon atoms, and polymeric polyalcohols such as polyester polyalcohols, polyurethane polyalcohols, and acrylic polyalkols.

Simple polyalcohols that can be used include diols, triols, tetrols, and mixtures thereof. Non-limiting examples of polyalcohols include those containing from 2 to 10 carbon atoms as aliphatic polyalcohols. Specific examples include, but are not limited to, the following compositions: di-trimethylol propane (bis (2,2-dimethylol) dibutyl ether); pentaerythritol; 1,2,3,4-butanetetrol; sorbitol; trimethylolpropane; trimethylolethane; 1,2,6-hexanetriol; glycerin; trishydroxyethyl isocyanurate; dimethylol propionic acid; 1,2,4butanetriol; 2-ethyl-1,3-hexanediol; TMP / epsilon-caprolactone triols; ethylene glycol, 1,2-propanediol; 1,3-propanediol; 1,4-butanediol; 1,5-pentanediol; 1,6-hexanediol; neopentyl glycol; diethylene glycol; dipropylene glycol; 1,4-cyclohexanedimethanol and 2,2,4-trimethylpentane-1,3 diol.

As regards oligomeric polyalcohols, suitable polyalcohols that can be used include polyalcohols obtained by reacting diacids with triols, such as trimethylol propane / cyclohexane diacid and trimethylol propane / adipic acid.

As regards polymeric polyalcohols, polyester polyalcohols can be prepared by esterification of an organic polycarboxylic acid, or anhydride thereof, with organic polyalcohols and / or an epoxide. Typically, polycarboxylic acids and polyalcholes are aliphatic or aromatic dibasic acids or acid anhydrides and diols.

Polyalcohols that can be used to make the polyester include trimethylol propane, di-trimethylol propane, alkylene glycols such as ethylene glycol, neopentyl glycol and other glycols such as hydrogenated bisphenol A, cyclohexanediol, cyclohexanedimethanol, the reaction products of lactones and diols, such as for example the reaction product of epsilon-caprolactone and ethylene glycol, hydroxy-alkylated bisphenols, polyester glycols, as for example, poly (oxytetramethylene) glycol and the like.

The acid component of the polyester comprises monomeric carboxylic acids or anhydrides having 2 to 18 carbon atoms per molecule. Acids that can be used include phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, glutaric acid, chlorindic acid, tetrachlorophthalic acid and other acids. dicarboxylics of various types. Also, higher polycarboxylic acids such as trimellitic acid and tricarbalilic acid can be used.

ES 2 249 285 T3

In addition to the polyester polyalcohols formed from polybasic acids and polyalcohols, it is also possible to use polyesters of the polylactone type. These products can be formed from the reaction of a lactone such as epsilon-caprolactone and a polyol such as ethylene glycol, diethylene glycol, and trimethylolpropane.

In addition to the polyester polyalcohols, it is possible to use polyurethane polyalcohols such as, for example, polyester-urethane polyalcohols which can be formed by reacting an organic polyisocyanate with a polyester polyol as described above. The organic polyisocyanate can be reacted with a polyalcohl so that the OH / NCO equivalent ratio is greater than 1: 1 so that the resulting product contains free hydroxyl groups. The organic polyisocyanate that can be used for the preparation of the polyurethane polyalcohols can be an aliphatic or aromatic polyisocyanate or a mixture. Diisocyanates can be used, although higher polyisocyanates can also be used as triisocyanates, although they result in higher viscosities.

Examples of suitable diisocyanates include 4,4'-diphenylmethane diisocyanate, 1,4-tetramethylene diisocyanate, isophorone diisocyanate, and 4,4'-methylenebis (cyclohexyl isocyanate). Examples of suitable higher functional polyisocyanates include phenol polymethylene polyisocyanates.

At least a portion can be silylated, and in certain cases the entire group with acid function. Alternatively, at least a portion, and in certain cases all acid functional groups, can be converted to hydroxyl groups by reaction with an epoxide.

Useful epoxy functional materials include epoxy functional monomers such as glycidyl methacrylate, ethylene oxide, butylene oxide, propylene oxide, cyclohexene oxide; glycidyl ethers such as glycidyl phenyl ether, glycidyl n-butyl ether, glycidyl cresyl ether; isopropyl glycidyl ether; glycidyl esters such as glycidyl versatate; for example CARDURA E distributed by Shell Chemical Co. and mixtures of any of them. Other useful epoxy functional materials include polymers that comprise at least two epoxide or oxirane groups per molecule. These materials are often referred to as di- or polyepoxides.

The equivalent ratio of epoxy groups to acid groups in the ester generally ranges from 0.1: 1 to 2: 1, can range from 0.5: 1 to 1: 1, typically ranges from 0.8: 1 to 1: 1 , including the cited values.

Useful aliphatic diols include diols containing a primary hydroxyl such as 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,2-pentanediol, 1,4-pentanediol, 1,2-hexanediol, 1,5-hexanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, 2,2,4-trimethyl-1,3-pentanediol and 3,3-dimethyl- 1,2-butanediol.

In one embodiment, the present invention relates to coating compositions such as those described above in which the material comprises at least one compound having the following structure (X):

ES 2 249 285 T3

Other useful materials having a linkage selected from an ester linkage, a urethane linkage, a urea linkage, an amide linkage, a siloxane linkage, and an ether linkage and at least one reactive functional group that are useful for silylation are those that are have been described above in the discussion of suitable additional polymers.

Alternatively, useful reagents include acrylic polymers containing hydroxyl groups blocked with hydrolyzable siloxy groups (polymerized for example from vinyl monomers and trimethylsiloxy methyl methacrylate) as described in I. Azuma et al., "Acrylic Oligomer for High Solid Automotive Top Coating System Having Excellent Acid Resistance ”, Progress in Organic Coatings 32 (1997) 1-7.

In one embodiment, the present invention relates to compositions such as those described in which the silyl-blocked reagent, when added to the other components that make up the coating composition, is present in the composition in an amount between 0 , 1 and 90 percent by weight based on the total weight of the resin solids of the components that make up the coating composition. In another embodiment, the present invention relates to compositions such as those described in which the silyl-blocked reagent, when added to the other components that make up the coating composition, is present in the coating composition in an amount of at least 0.1, at least 1 or at least 5 percent by weight based on the total weight of the resin solids of the components that make up the coating composition.

In yet another embodiment, the present invention relates to compositions such as those described in which the silyl-blocked reagent, when added to the other components that make up the coating composition, is present in the coating composition in an amount less than 60, less than 30 or less than 10 percent by weight based on the total weight of the resin solids of the components that make up the coating composition. The amount of the silyl blocked reagent can range from any combination of these values including those cited.

The coating compositions of the present invention may consist of solvent-based coating compositions, water-based coating compositions, in the form of solid particles, i.e., a powder coating composition, or in the form of a slurry in powder or aqueous dispersion. The components of the present invention used to form the cured compositions according to the present invention can be dissolved or dispersed in an organic solvent. Non-limiting examples of suitable organic solvents include alcohols such as butanol; ketones such as methyl amyl ketone; aromatic hydrocarbons such as xylene; and glycol ethers, such as ethylene glycol monobutyl ether; other solvents and mixtures of them.

In solvent-based compositions, the organic solvent is generally present in amounts between 5 and 80 percent by weight based on the total weight of the resin solids of the components that make up the composition and may be present in an amount between 30 and 50 percent by weight, including the cited values. The compositions as described have a total solids content between 40 and 75 percent by weight based on the total weight of resin solids of the components that make up the composition and can have a total solids content between 50 and 70 percent by weight, including the values cited. Alternatively, the compositions of the invention may be in solid particulate form suitable for use as a powder coating, or suitable for dispersion in a liquid medium such as water for use as a powdered slurry.

In another embodiment in which the cured compositions as described are formed from at least one reagent, additionally a catalyst is present during the formation of the cured composition. In one embodiment, the catalyst is present in an amount sufficient to accelerate the reaction between at least one reactively functional group of the reagent and at least one reactively functional group of at least one polysiloxane (a).

Non-limiting examples of suitable catalysts include acidic materials, such as acidic phosphates, such as phenyl acid phosphate, and substituted and unsubstituted sulfonic acids, such as dedecylbenzene sulfonic acid or paratoluene sulfonic acid. Non-limiting examples of suitable catalysts for reactions between isocyanate groups and hydroxyl groups include tin catalysts such as dibutyl tin dilaurate. Non-limiting examples of epoxy acid-based catalysts include tertiary amines such as N, N'-dimethyldodecyl amine catalysts. In another embodiment, the catalyst can be a phosphatized polyester or a phosphatized epoxy. In this embodiment, the catalyst can be, for example, the reaction product of phosphoric acid and a diglycidyl ether of Bisphenol A having two hydrogenated phenolic rings, such as DRH-151, which is commercially available from Shell Chemical Co. The catalyst may be present, when added to the other components that make up the coating composition in an amount between 0.1 and 5.0 percent by weight and is typically present in an amount between 0.5 and 1, 5 percent by weight based on the total weight of the resin solids of the components that make up the coating composition. The amount of catalyst can range from any combination of these values including the quoted values.

In another embodiment, additional components may be present during formation of the coating compositions, as described above. These additional components include, but are not limited to, flexibilizers, plasticizers, surfactants as described herein (such as polysiloxanes), thixotropic agents, anti-gassing agents, organic cosolvents, flow control agents, light stabilizers. of hindered amine, anti-oxidants, UV light absorbing agents, coloring agents or dyes, and similar additives conventional in this field, as well as mixtures thereof, that can be included in the composition

ES 2 249 285 T3 coating. These additional ingredients may be present, when added to the other components that make up the coating composition, in an amount of up to 40 percent by weight based on the total weight of resin solids of the components that make up the coating composition. .

The amount of coating composition applied to the substrate can vary depending on factors such as the type of substrate and the intended use of the substrate, i.e. the environment in which the substrate is to be placed and the nature of the substrate materials. Contact.

In yet another embodiment, the present invention relates to a coated substrate comprising a substrate and a coating composition that covers at least a portion of the substrate, the coating composition being selected from any of the aforementioned coating compositions . In yet another embodiment, the present invention relates to a method of coating a substrate that comprises applying a coating composition to at least a portion of the substrate, the coating composition being selected from any of the compositions that have been mentioned.

In another embodiment, the present invention relates to a method of coating a substrate that further comprises a step of curing the coating composition after application to the substrate. The components used to form the coating compositions in these embodiments can be selected from the components that have been described, and the additional components can also be selected from those already mentioned.

As used herein a composition "on at least a portion of a substrate" refers to a composition that is applied directly to at least a portion of the substrate, as well as a composition that is applied on a coating material that has already been applied. previously applied to at least a portion of the substrate.

The coating compositions of the present invention can be applied to virtually any substrate including wood, metals, glass, fabric, plastic, foam, polymeric substrates, such as elastomeric substrates, and the like. In one embodiment, the present invention relates to a coated substrate as described, the coated substrate being a flexible substrate. In another embodiment, the present invention relates to a coated substrate as described, the coated substrate being a rigid substrate.

In another embodiment, the present invention relates to coated substrates, as described above, the coated substrate being a ceramic substrate. In yet another embodiment, the present invention relates to coated substrates, as described, the coated substrate being a polymeric substrate. In another embodiment, the present invention relates to a coated metal substrate comprising a metal substrate and a cured composition that covers at least a portion of the metal substrate, the cured composition being selected from any of the aforementioned compositions. The components used to form the cured compositions of these embodiments can be selected from the aforementioned components, and the additional components can also be selected from those mentioned.

In yet another embodiment, the present invention relates to a coated automobile substrate comprising an automobile substrate and a cured composition coating at least a portion of the automobile substrate, the cured composition being selected from any of the aforementioned compositions. In yet another embodiment, the present invention relates to a method for manufacturing a coated automobile substrate consisting of providing an automobile substrate and applying to at least a portion of the automobile substrate a coating composition selected from any of the following: previous compositions. Also in this case, the components used to form the cured compositions in these embodiments can be selected from the components described above, and the additional components can also be selected from those mentioned above.

Suitable flexible elastomeric substrates can include any of the thermoplastic or thermoset synthetic materials known in the art. Non-limiting examples of suitable flexible elastomeric substrate materials include polyethylene, polypropylene, thermoplastic polyolefin ("TPO"), reactive injection molded polyurethane ("RIM"), and thermoplastic polyurethane ("TPU").

Non-limiting examples of thermosets useful as substrates in connection with the present invention include polyesters, epoxides, phenolics, polyurethanes such as "RIM" thermosets, and mixtures thereof. Non-limiting examples of suitable thermoplastic materials include thermoplastic polyolefins such as polyethylene, polypropylene, polyamides such as nylon, thermoplastic polyurethanes, thermoplastic polyesters, acrylic polymers, vinyl polymers, polycarbonates, acrylonitrile-butadiene-rubber-styrene copolymers ("ABS"), of ethylene-propylene-diene tertpolymer ("EPDM"), copolymers and mixtures thereof.

Non-limiting examples of suitable metal substrates include ferrous metals (eg, iron, steel, and alloys thereof), non-ferrous metals (eg, aluminum, zinc, magnesium, and alloys thereof), and mixtures of any of them. In the concrete use of automobile components, the substrate can be formed of cold rolled steel, electrogalvanized steel such as hot dip electrogalvanized steel, electrogalvanized iron-zinc steel, aluminum and magnesium.

ES 2 249 285 T3

When the substrates are used as components to make motor vehicles (including but not limited to automobiles, trucks and tractors) they can be of any shape and selected from the metallic and flexible substrates that have been described. Typical forms of automobile body components may include automobile bodies (frames), hoods, doors, guards, mirror housings, bumpers, and trims.

In yet another aspect, the present invention relates to coated automotive substrates, as described, with the coated automotive substrate being a hood. In another embodiment, the present invention relates to coated automotive substrates as described, the coated automotive substrate being a door. In another embodiment, the present invention relates to coated automotive substrates, as described above, wherein the coated automotive substrate is a shield. In another embodiment, the present invention relates to coated automotive substrates, as described, the automotive substrate being a mirror housing. In another embodiment, the present invention relates to coated automotive substrates, as described above, with the coated automotive substrate being a side panel. The components used to form the cured compositions used to coat the automotive substrates in these embodiments can be selected from the components described above.

In embodiments of the present invention which relate to automotive applications, the cured compositions may consist of, for example, the electrodeposition coating, the primer coating, the base coat coating and / or the top coat coating. Suitable topcoats include monolayers and basecoat / clearcoat composites. Monolayers are formed from one or more layers of a colored coating composition. Basecoat / clearcoat composites consist of one or more layers of a colored basecoat composition, and one or more layers of clearcoat composition, the basecoat composition having at least one component that is different from the composition of the clear coat. In embodiments of the present invention that relate to automotive applications, the clear coat may be transparent after application.

In another embodiment, the present invention relates to cured compositions of a multi-component composite material consisting of a base coat deposited from a pigmented coating composition and a top coat composition that is applied over at least a portion of the base coat, the composition of the top coat being selected from any of the compositions described above.

In one embodiment, the present invention relates to a cured multi-component composite composition as described, the topcoat composition being clear after curing and being selected from any of the cured compositions described above. The components used to form the topcoat composition in these embodiments can be selected from the coating components that have been described, and the additional components can also be selected from those mentioned above.

The basecoat and clear topcoat compositions (i.e., the colorless layer) used in the cured compositions of the multi-component composite of the present invention can in certain cases be formulated into solid compositions with high liquid content, i.e. say compositions containing 40 percent, or more than 50 percent by weight resin solids including the values cited. The solids content can be determined by heating a sample of the cured composition at 105-110 ° C for 12 hours to remove volatile material, and then measuring the relative weight loss. As mentioned, although cured compositions can be formed from liquid coating compositions, they can also be formed from coating compositions formulated as powder coating compositions.

The basecoat coating composition in the color-more-transparent system can be any of the compositions useful in coating applications, particularly automotive applications. The basecoat coating composition can be formed from components comprising a resinous binder and a colorant-acting pigment. Non-limiting examples of the resinous binder include acrylic polymers, polyesters, alkyds, and polyurethanes.

The resinous binders for the base coat can be organic solvent-based materials such as those described in US Patent No. 4,220,679, note column 2, line 24 continuing through column 4, line 40, part being incorporated. herein for reference. Also, the water-based coating compositions described in US Patent No. 4,403,003; 4,147,679 and 5,071,904 as binder in the base coat composition.

The basecoat composition can comprise one or more pigments as colorants. Non-limiting examples of suitable metallic pigments include aluminum flakes, bronze and copper flakes, and metal oxide coated mica.

In addition to metallic pigments, basecoat compositions may contain non-metallic colored pigments conventionally used in surface coatings such as inorganic pigments such as

ES 2 249 285 T3 titanium dioxide, iron oxide, chromium oxide, lead chromate and carbon black; and organic pigments such as phthalocyanine and phthalocyanine green.

Optional ingredients in the basecoat composition may include those which are known in the art of surface coating formulation and may include surfactants, flow control agents, thixotropic agents, fillers, anti-gassing agents, co -organic solvents, catalysts and other common auxiliaries. In US patents. No. 4,220,679; 4,403,003; 4,147,769 and 5,071,904, which are incorporated herein by reference, describe non-limiting examples of these materials.

Basecoat compositions can be applied to the substrate via any of the conventional coating techniques such as brushing, spraying, dipping, or flow. The spraying techniques and equipment for air spraying, airless spraying and electrostatic spraying can be applied, either by manual or automatic methods, known in the art.

During application of the base coat to the substrate, the thickness of the base coat film formed on the substrate can range from 0.1 to 5 mils (2.24 to 112 pm). In another embodiment, the film thickness of the base layer formed on the substrate can range from 2.24 to 22.4 pm (0.1 to 1 mils) and can be 9 pm (0.4 mils).

After the formation of a basecoat film on the substrate, the basecoat may be cured or alternatively a drying step in which solvent is removed from the basecoat film by heating, or a drying period may be applied. to air prior to application of clear coat. Suitable drying conditions will depend on the composition of the particular base coat, and on the ambient humidity if the composition is supported on water, although a curing period of 1 to 15 minutes at a temperature of 24 ° C to 93 ° C (75 ° to 200 ° F) may be suitable.

The clear or colorless topcoat composition can be applied over the basecoat via any of the conventional coating techniques, including, but not limited to, compressed air spraying, electrostatic spraying, and both manual and automated methods. Clear Topcoat can be applied over a cured or dried basecoat before the basecoat has cured. In the latter case, the two coatings can then be heated to cure both coating layers simultaneously. Typical cure conditions can range from 50 ° F to 475 ° F (10 ° C to 246 ° C) for 1 to 30 minutes. Alternatively, the transparent top layer can be cured by ionizing or actinic radiation or the combination of thermal energy and ionizing or actinic radiation as described in detail above. Clearcoat thickness (dry film thickness) can range from 1 to 6 mils (22.4 to 134.4 µm).

A second topcoat coating composition can be applied over the first topcoat to form a "clear-on-clear" topcoat. The first topcoat coating composition can be applied over at least a portion of the basecoat as described above. The second top coat coating composition can be applied over a dried or cured first top coat before the base coat and first top coat have cured. The base coat, the first top coat, and the second top coat can be heated to cure all three coats simultaneously.

It should be understood that the coating compositions of the second clear topcoat and the first clear topcoat may be the same or different as long as, when applied wet-on-wet, one topcoat substantially interferes with the cure of the other, thereby for example, by inhibiting solvent / water evaporation from the lower layer. On the other hand, the first top layer, the second top layer, or both may consist of the cured composition of the present invention. The first clear coat composition can be virtually any clear top coat composition known to those skilled in the art. The first clear topcoat composition may be water-based or solvent-borne or, alternatively, it may be in the form of solid particles, ie, a powder coating.

Non-limiting examples of suitable first topcoat compositions include crosslinkable coating compositions consisting of at least one thermoset coating material and at least one curing agent. Suitable water-based clearcoats are described in US Patent No. 5,098,947, and are based on water-soluble acrylic resins. In US Pat. Nos. 5,196,485 and 5,814,410 disclose solvent-borne clearcoats, and include polyacid and polyepoxide curing agents. Suitable powder clear coatings are disclosed in US Patent No. 5,663,240 and include epoxy functional acrylic copolymers and polycarboxylic acid curing agents.

Typically, after the formation of the first top coat on at least a portion of the base coat, a drying step is applied on the first top coat in which the solvent is removed from the film by heating or, alternatively, a period of air drying or a curing step, prior to the application of the second top coat. Suitable drying conditions will depend on the composition of the particular first top coat and on the ambient humidity if the composition is supported on water but, in general, a curing period of 1 to 15 minutes at a temperature of 24 ° will be adequate. C to 93 ° C (75 ° to 200 ° F).

ES 2 249 285 T3

The polysiloxane-containing second topcoat coating composition of the present invention can be applied as described for the first topcoat through any of the coating application techniques. Curing conditions can be as described above for the top coat. The dry film thickness of the second top layer can range from 0.1 to 3 mils (7.5 microns to 75 microns).

It should be mentioned that polysiloxane-containing coating compositions can advantageously be formulated as a "monolayer" which is a coating that essentially forms a coating layer when applied to a substrate. The monolayer coating composition can be pigmented. Non-limiting examples of suitable pigments include those mentioned above. When used as a monolayer, the polysiloxane-containing coating compositions of the present invention can be applied (via any of the aforementioned application techniques) in two or more successive layers and, in certain cases, can be applied with a single period of ambient conditioning between both layers. Multilayers, when cured, can essentially form a cover layer.

In another embodiment, the present invention relates to a method for manufacturing a multi-component composite material consisting of (a) applying a pigmented composition onto a substrate to form a base coat; and (b) applying a topcoat composition over at least a portion of the basecoat to form a topcoat on top, the topcoat composition being selected from any of the compositions that have been described. The components used to form the topcoat composition in this embodiment can be selected from the coating components that have been described, and the additional components can also be selected from those mentioned.

The coatings formed from the compositions according to the present invention can exhibit outstanding appearance properties, initial scratch resistance (wear) properties as well as "retained" scratch (wear) resistance, or after exposure to the elements, which can be evaluated by measuring the gloss of the coated substrates before and after abrasion of the coated substrates.

In one embodiment, the present invention relates to methods for improving the scratch resistance of a substrate comprising the application to the substrate of any of the compositions of the invention described for the substrate. In another embodiment, the present invention relates to a method for improving the soil repellency of a substrate comprising the application of any of the compositions of the invention described to the substrate.

In another embodiment, the present invention relates to a method for retaining the gloss of a substrate over time that comprises applying to the substrate comprising any of the compositions of the invention described for the substrate. In another embodiment, the present invention relates to a method for revitalizing the gloss of a substrate comprising the application to the substrate of any of the compositions of the invention described for the substrate.

In another embodiment, the cured compositions of the present invention may also be useful as decorative or protective coatings for plastic substrates (elastomers), pigmented as described above, or mold-color ("MIC") plastic substrates. In these applications, the compositions can be applied directly to the plastic substrate or can be included in the molding matrix. Optionally, the adhesion promoter can first be applied directly to the plastic or elastomeric substrate and the composition applied as a top coat on top. The compositions of the present invention can also be suitably formulated as pigmented coating compositions for use as primer coats, as base coats in multi-component composite coatings, and as monolayer top coats including pigments and colorants. The components used to form the compositions in these embodiments can be selected from the coating components described above, and the additional components can also be selected from those mentioned above.

In yet another embodiment of the present invention, a cured composition consisting of particles is provided in a cured composition consisting of one or more thermoplastic materials. As described above, the concentration of the particles is higher in the surface region than in the volume region. The cured composition can be derived from a thermoplastic resinous coating composition. Non-limiting examples of suitable thermoplastic materials include acrylic polymers, polyolefin polymers, polyamide polymers, and high molecular weight polyester polymers (i.e., Mw greater than 20,000, greater than 40,000, or greater than 60,000) suitable for use. in lacquered drying systems. A non-limiting example of a class of thermoplastic materials from which the cured composition can be derived is fluoropolymer-acrylic copolymers such as those prepared from polyvinylidene fluoride, for example KYNAR 500 (distributed by Ausimont USA, Inc.) and Thermoplastic acrylic copolymers, such as ACRYLOID B44 (65% methyl methacrylate and 35% ethyl acrylate) distributed by Dock Resin.

Also described is a method of retaining the gloss of a polymeric substrate or polymer coated substrate after a predetermined period of time comprising application to the substrate comprising any of the compositions of the invention that have been described for the substrate. Said predetermined period of time can generally be at least 6 months and can be at least one year. In another embodiment, the present31

ES 2 249 285 T3 The invention relates to a method for revitalizing the gloss of a polymeric substrate or a substrate coated with polymer comprising the application to the substrate of any of the compositions of the invention described above.

In order to illustrate the invention, the following examples are offered which should not however be construed as limiting the invention in their details. Unless otherwise indicated, all parts and percentages in these examples, as well as throughout the specification are by weight.

Examples

Example A describes the preparation of a polysiloxane polyalcohol which is the hydrosilylation reaction product of a pentasiloxane containing silicon hydride and trimethylolpropane monoallyl ether.

Example 1 describes the preparation of clear topcoat coating compositions according to the present invention (Examples 23A-23C) that were applied to the corresponding substrates for further evaluation using a transmission electron microscope.

Example 2 describes the preparation of coating compositions according to the present invention containing various polysiloxanes in combination with inorganic particles in the form of colloidal silica. The coating composition was applied to a basecoat substrate and evaluated against a commercial two-component isocyanate clearcoat with similar application (comparative example) to determine penetration (scratch depth) as a function of distance and loading of the scratching to determine the critical load at which coating failure occurs.

Example 3 describes the preparation of coating compositions according to the present invention containing various levels of polysiloxane polyol from Example A (Examples 3B to 3G) in combination with various levels of inorganic particles in the form of colloidal silica. Comparative Example 3 contains polysiloxane polyol but no colloidal silica.

Example 4 describes the preparation of a clear topcoat coating composition according to the present invention.

Example 5 describes the preparation of coating compositions according to the present invention.

Example 6 describes the preparation of coating compositions according to the present invention.

Polysiloxanes

Example A

This example describes the preparation of a polysiloxane polyalcohol, a product of the hydrosilylation of pentasilixan with an approximate degree of polymerization of 3 to 4, that is, (Si-O)3 a (Si-O)4. The polysiloxane polyalcohol was prepared from the following mixture of ingredients:

<td>Ingredients</td><td>Equivalent weight</td><td>Equivalents</td><td>parts by weight (kg)</td>

<td>Trimethylolpropane Monoallyl Ether</td><td> 174,0</td><td> 756,0</td><td> 131,54</td>

<td>Charge II:</td><td></td><td></td><td></td>

<td>MASILWAX BASE1</td><td> 156,72</td><td> 594,8</td><td> 93,21</td>

<td>Letter III:</td><td></td><td></td><td></td>

<td>Chloroplatinic acid</td><td></td><td>10 ppm</td><td></td>

<td>Toluene</td><td></td><td></td><td> 0,23</td>

<td>Isopropanol</td><td></td><td></td><td> 0,07</td>

1 Polysiloxane-containing silicon hydride, commercially available from BASF Corporation.

2 Equivalent weight based on mercuric dichloride determination.

ES 2 249 285 T3

Charge I and an amount of sodium bicarbonate equivalent to 20 to 25 ppm of total monomer solids were placed in a suitable reaction vessel equipped with a means to maintain a nitrogen atmosphere, under ambient conditions, and the temperature was gradually increased. at 75 ° C under a nitrogen atmosphere. At this temperature, 5.0% of Charge II was added, with stirring, followed by the addition of Charge III, equivalent to 10 ppm of active platinum based on total monomer solids. The reaction was then allowed to heat up at 95 ° C during which time the remainder of Charge II was added at a rate sufficient so that the temperature did not exceed 95 ° C. After the addition was complete, the reaction temperature was maintained at 95 ° C and monitored by infrared spectroscopy to determine the disappearance of the silicon hydride absorption band (Si-H, 2150 cm-1).

Example 1

This example describes the preparation of clear topcoat coating compositions which, after application and curing, were evaluated through surface characterization techniques with a transmission electron microscope. Example 1 describes the preparation of a clear topcoat composition according to the present invention containing inorganic particles in the form of colloidal silica in combination with the polysiloxane polyalcohol of Example A, both added as separate components. Comparative Example 1 describes the preparation of a comparative clear topcoat composition containing inorganic particles in the form of colloidal silica but not polysiloxane. Example 1 describes the preparation of a clear topcoat composition according to the present invention in which inorganic particles in the form of colloidal silica were dispersed in the polysiloxane polyalcohol of Example A prior to incorporation into the composition.

Each of the compositions described below was prepared.

Example 1A

<td>Description</td><td>Solid</td><td>Total weight</td>

<td>Methyl amyl ketone</td><td> -</td><td> 66,6</td>

<td>Tinuvin 928</td><td> 3,0</td><td> 3,0</td>

<td>Colloidal silica1</td><td> 5,0</td><td> 16,7</td>

<td>Cymel 202</td><td> 15,0</td><td> 18,8</td>

<td>Polysiloxane polyalcohol example A</td><td> 2,0</td><td> 2,0</td>

<td>Acrylic polyol1 2</td><td> 63,0</td><td> 106,1</td>

<td>Tinuvin 123</td><td> 1,0</td><td> 1,0</td>

<td>Butyl polycrylate</td><td> 0,3</td><td> 0,5</td>

<td>Catalyst from Example 12</td><td> 1,0</td><td> 1,3</td>

<td>Desmodur N-33903</td><td> 20,0</td><td> 22,2</td>

1 ORGANOSILICASOL MT-ST distributed by Nissan Chemicals.

2 Polymerization reaction product prepared from the following monomer composition in Dowanol PM acetate, using VAZO 67 (azo bis-2,2 = -2-methylbutyronitrile), 4.9% on the total monomer charge as initiator): 39.4 parts of hydroxyethyl methacrylate, 2 parts of acrylic acid, 57 parts of isobutyl methacrylate and 1.6 parts of α-methylstyrene dimer. The polymer solution exhibited the following properties. 60% solids content; 82.4 OH value, molecular weight: 7410 (Mw).

3 Hexamethylene diisocyanate polyisocyanate crosslinking agent, 100% solids, distributed by Bayer Corporation.

ES 2 249 285 T3

Example 1B

<td>Description</td><td>Solid</td><td>Total weight</td>

<td>Methyl amyl ketone</td><td> -</td><td> 66,2</td>

<td>Tinuvin 928</td><td> 3,0</td><td> 3,0</td>

<td>ORGANOSILICASOL MT-ST</td><td> 5,0</td><td> 16,7</td>

<td>Cymel 202</td><td> 15,0</td><td> 18,8</td>

<td>Acrylic polyol example 23A</td><td> 65,7</td><td> 110,7</td>

<td>Tinuvin 123</td><td> 1,0</td><td> 1,0</td>

<td>Butyl polyacrylate</td><td> 0,3</td><td> 0,5</td>

<td>Catalyst from Example 12</td><td> 1,0</td><td> 1,3</td>

<td>Desmodur N-33903</td><td> 19,3</td><td> 21,4</td>

Example 1C

<td>Description</td><td>Solid</td><td>Total weight</td>

<td>Methyl amyl ketone</td><td> --</td><td> 25,0</td>

<td>Silica dispersion1</td><td> 6,7</td><td> 8,6</td>

<td>Tinuvin 928</td><td> 3,0</td><td> 3,0</td>

<td>Acrylic polyol1 2 3</td><td> 35,9</td><td> 65,3</td>

<td>Tinuvin 292</td><td> 0,5</td><td> 0,5</td>

<td>Butyl polyacrylate</td><td> 0,3</td><td> 0,5</td>

<td>Polysiloxane polyalcohol example A</td><td> 15,3</td><td> 15,3</td>

<td>Cymel 202</td><td> 15,0</td><td> 18,8</td>

<td>Catalyst from Example 12</td><td> 0,5</td><td> 0,7</td>

<td>Desmodur N-33003</td><td> 29,1</td><td> 29,1</td>

1 Colloidal silica dispersion in polysiloxane prepared as follows:

A 4 necked reaction vessel equipped with vacuum distillation was leveled with N2. 3151.4 g of polysiloxane polyol from Example A, 4501.9 of colloidal silica (ORGANOSILICASOL MT-ST, distributed by Nissan Chemicals) and 1440.6 g of methyl amyl ketone were introduced into the reaction vessel. The resulting mixture was vacuum distilled.

2 VK-114, an acrylic polyol having the following properties: 55% solids, Mw 4000 and an OH 101 number, distributed by PPG Industries, Inc.

3 Hexamethylene diisocyanate polyisocyanate crosslinking agent, 100% solids, distributed by Bayer Corporation.

ES 2 249 285 T3

Preparation of test panel for examples 1A and 1B

A black basecoat, SMARAGDSCHWARZ MICA, distributed by PPG (B&K) Germany, was applied over steel test panels (4 "x 12" panels commercially available from ACT Laboratories, Inc. of Hillsdale, Michigan) that had been coated with one layer of ED-5000 electrocoat primer and one surface layer of GPXH-5379 primer (both commercially available from PPG Industries, Inc.) using spraying. Basecoat was applied in two coats with no conditioning between coats followed by a five minute heat condition at 93 ° C (200 ° F) prior to applying clearcoats. The base coat had a dry film thickness of 0.47 mils (11.75 microns). The coating compositions of Examples 1A and 1B were spray applied over the cured basecoats in two coats with a 60 second conditioning between coats followed by a 5 minute room conditioning prior to cure for 30 minutes at 140.6 ° C. (285 ° F). Each of the clear layers had a dry film thickness of approximately 2.1 mils (54.5 microns).

Preparation of test panel for example 1C

A black basecoat, OBSIDIAN SCHAWARTZ, distributed by PPG (B&K) Germany, was spray applied and cured as described immediately above Examples 1A and 1B. The coating composition from Example 1C was applied over the base coat as a clear coat and cured using the procedure described above for the clear coats from Example 1A and 1B. The base coat had a dry film thickness of 0.5 mils (12.5 microns) and the clearcoat had a dry film thickness of 1.44 mils (36 microns).

Transverse transmission electron microscope

Samples of cured coating were peeled from the substrate and embedded in epoxy using EPONATE 812 epoxy embedding kit available from Ted Pella's Inc. in a polyester bottle cap mold. Once the heat was adjusted, the samples were removed from the molds and cut using an X-ACTO blade saw, extra fine tooth # 75350 to a size of approximately 1.5 cm x 1 cm. Samples cut to size were microtomized at room temperature using an RMC MY6000XL microtomizer using a forceps specimen holder. Microtome sections were cut using a 45 ° diamond blade flange mounted on a handle with a water-filled ship cavity. Slices were made to a color interference from bright to dark gold (approximately 100 nanometers to 150 nanometers), then individual cut specimens were collected on the formwar-carbon TEM coated grid. Excess water was removed with filter paper and the sections were then air dried at room temperature on a glass microscope slide. The sections were classified according to the interference of the color thickness. The coating specimens were oriented on the glass slides to allow for an on-axis tilt, so that the perpendicular cross section could be observed. The samples were placed in a Philips CM-12 TEM apparatus operating at an acceleration voltage of 100 KV, in a transmission mode using a standard tungsten filament and examined at different magnifications to document the surface morphologies of the coating and the concentration. of the particles by visual observation. Kodak SO-163 electronic imaging film was used to create electron micrograph negatives and the negatives were then developed.

Figure 1 is an electron micrograph of a transmission electron microscope image (30,000X magnification) of a cross section of a cured clear topcoat composition from Example 1 containing colloidal silica and polysiloxane added as separate components. Upon examination with the naked eye, it can be seen that the concentration of particles in the form of colloidal silica 1b present in the surface region of the cured composition, that is, a region extending from the air-exposed surface interface 1a, a depth of cured coating of 20 to 25 nanometers (1 millimeter = approximately 30 nanometers) below the exposed surface is greater than the concentration of colloidal silica 1c present in the volume region of the cured composition. It should be noted that particles 1b and 1c exist as agglomerates within the polymer matrix, rather than as separate mono-dispersed particles.

Figure 2 is a transmission electron microscope image micrograph (magnification 30,000X) of a cross section of a cured comparative clear topcoat coating composition of Example 1B containing colloidal silica but not polysiloxane. Upon examination with the naked eye, it can be seen that the concentration of inorganic particles in the form of colloidal silica 2b present in the surface region of the comparative cured composition, i.e., a region extending from the air-exposed surface interface 2a to a cured coating depth of 20 to 25 nanometers (1 millimeter = approximately 30 nanometers) below the exposed surface is less than the concentration of colloidal silica 2c within the volume region of the cured composition. In fact, essentially no colloidal silica is observed in the surface region. It should be noted that particles 2b and 2c appear as agglomerates within the polymer matrix, rather than as discrete monodispersed particles.

ES 2 249 285 T3

Figure 3 is an electron micrograph of a transmission electron microscope image of a cross section of the clear topcoat coating composition of Example 1A (see Figure 1) viewed at 54,000 x magnification.

Figure 4 is a transmission electron microscope electron micrograph image (105,000 x magnification) of a cross section of a cured clear topcoat coating composition of the present invention containing a preformed dispersion of a colloidal silica and polysiloxane. . Upon visual examination, it can be clearly seen that the concentration of the colloidal silica particles 4b present in the surface region of the cured composition, i.e., a region extending from the air-exposed surface interface 2a to a depth of cured coating 20 to 25 nanometers below the exposed surface is greater than the concentration of colloidal silica 4c within the volume region of the cured composition. It should be noted that particles 4b and 4c appear as discrete monodispersed particles distributed within the polymer matrix, rather than as agglomerated particles (compare Figures 1 and 2).

Example 2

In this example, a coating composition according to the present invention containing inorganic particles in the form of colloidal silica predispersed in a functional group-containing polysiloxane was evaluated against a comparative commercial two-component isocyanate clearcoat to determine the penetration of the coating. (scratch depth) depending on the load and scratch distance.

Example 2A

The coating composition of the present invention was prepared from a mixture of the following ingredients:

<td>Ingredient</td><td>Solid</td><td>Total weight (grams)</td>

<td>Methyl amyl ketone</td><td> --</td><td> 25,0</td>

<td>Silica dispersion from Example 23C</td><td> 6,7</td><td> 8,6</td>

<td>TINUVIN 928</td><td> 3,0</td><td> 3,0</td>

<td>Example 23C acrylic polyol</td><td> 40,9</td><td> 74,4</td>

<td>TINUVIN 292</td><td> 0,5</td><td> 0,5</td>

<td>Butyl Polyacrylate Flow Additive</td><td> 0,3</td><td> 0,5</td>

<td>Polysiloxane polyalcohol example A</td><td> 10,3</td><td> 10,3</td>

<td>CYMEL 202</td><td> 15,0</td><td> 18,8</td>

<td>Catalyst example 12</td><td> 0,5</td><td> 0,7</td>

<td>DESMODUR N-3300</td><td> 29,1</td><td> 29,1</td>

ES 2 249 285 T3

Example 2B

A black water supported base coat was prepared from a mixture of the following ingredients:

<td>Ingredients</td><td>Solids (grams)</td><td>Total weight (g)</td>

<td>PROPASOL B1</td><td> --</td><td> 45,0</td>

<td>CYMEL 3272</td><td> 35,0</td><td> 38,9</td>

<td>TINUVIN 11303</td><td> 3,2</td><td> 3,2</td>

<td>Phosphated epoxy4</td><td> 0,5</td><td> 0,8</td>

<td>Dimethylethanolamine (50% in water)</td><td> --</td><td> 2,0</td>

<td>Latex5</td><td> 46,5</td><td> 109,4</td>

<td>Mineral spirits</td><td> --</td><td> 8,0</td>

<td>Water reducible urethane6</td><td> 10,0</td><td> 42,6</td>

<td>Black pigment dispersion7</td><td> 11,5</td><td> 47,6</td>

<td>Dimethylethanolamine (50% in water)</td><td> --</td><td> 1,0</td>

<td>Deionized water</td><td> --</td><td> 57,5</td>

1 N-butoxypropanol distributed by Chemcentral Corporation, Chicago.

2 Methylated melamine-formaldehyde resin distributed by Cytec Corporation.

3 Substituted hydroxyphenyl benzotriazole UV light stabilizer available from Ciba Geygy Corporation.

4 Proprietary phosphatized epoxy resin (EPON 828 from Shell Company) from PPG Industries, Inc.

5 Acrylic-polyester latex owned by PPG Industries, Inc.

6 Proprietary water borne polyurethane, PPG Industries, Inc.

7 Proprietary Carbon Black Dispersion in Water Dispersed Acrylic Resin, PPG Industries, Inc.

Test panel preparation

Steel substrate test panels (distributed by ACT Laboratories, Inc.) were coated with a layer of ED-5000 electrocoat primer (distributed by PPG Industries Inc). The base coat from Example 2B above was spray applied over the primed panels in two successive coats with no conditioning period between coats. Basecoat coated panels were heat conditioned for 5 minutes at 93 ° C (200 ° F) prior to application of clearcoats. The dry film thickness of the base coat was 0.4 mils (10 microns). The coating composition from Example 2A above and the commercial two-component clearcoat (TKU-1050 distributed by PPG Industries, Inc.) were spray-applied onto the basecoat panels in two layers with a 60 second conditioning between coats. , followed by a 10 minute ambient conditioning prior to curing for 30 minutes at 140.6 ° C (285 ° F). The clearcoat dry film thickness was 1.6 mils for each example (40 microns).

Test panels prepared as described were tested by the MTS Corporation of Oak Ridge, Tennessee for surface penetration (or scratch depth) as a function of applied load at a given speed over a given distance. The Nano Indenter XP system was employed using a cube corner indenter, at a scoring speed of 20 pm / s, using a normal loading ramp of 1000 pN / s up to a maximum load of 25 mN over a scoring length of 500 pm.

Figure 5 is a graph (scratch depth versus scratch distance) of coating surface penetration relative to loading for commercial two-component polyurethane coating (comparative example) using nano-indenter techniques described above. The critical load determined for this composition is 5.62 mN. As used herein, the term "critical load" is defined from the onset of catastrophic crack, ie failure of the coating.

Figure 6 is a graph (scratch depth versus scratch distance) of coating surface penetration in relation to loading of the two-component coating of Example 2A of the present invention described above using the nano-indenter techniques described. previously. The determined critical load

ES 2 249 285 T3 for the composition of the invention is 11.74. The coating composition of the present invention required higher force to cause coating failure relative to commercial control under the same conditions. Example 3

This example describes the preparation of a series of coating compositions according to the present invention (Examples 25B-25G) containing increasing amounts of particles in the form of colloidal silica. Comparative Example 3 describes a coating composition that does not contain particles. The test results in Table 5 below illustrate the effect of silica filler on the retained scratch resistance properties of cured coating compositions.

Coating composition without inorganic particles

A coating composition was prepared by mixing with gentle agitation the following components: 35.9 weight percent acrylic polyol from Example 3C; 29.1 percent by weight of DESMODUR N-3300; 20 weight percent of the polyol siloxane from Example A (this amount includes the polyol siloxane incorporated as a silica dispersion), 15 weight percent CYMEL 202; 3 weight percent TINUVIN 98, 0.3 weight percent butyl polyacrylate flow additive; and 0.5 percent by weight of the catalyst of Example 12, the weight percentages being based on the weight of total resin solids of the components that make up the coating composition. The particles are incorporated at levels between 0 and 8.5 weight percent in the composition just described in the form of the colloidal silica dispersion of Example 19.

The compositions of Example 3A-3G were applied to test panels as described for Example 2. The coated panels were then tested for initial and retained scratch resistance properties as described. Table 5 shows the results.

TABLE 5

<td>Example 3</td><td>% Silica **</td><td colspan="2" rowspan="2">Initial scratch resistance Gloss 20 ° Initial retention% gloss</td><td colspan="2">Scratch resistance after 148 hours of exposure QUV 20 ° gloss</td>

<td></td><td></td><td>Initial Withholding</td><td>% brightness</td>

* Comparative Example ** Percentage by weight based on the weight of total resin solids in the silica composition incorporated as the silica dispersion of Example 19.

The test data recorded in Table 5 above illustrates the significant improvement in the retained scratch resistance by incorporating even low levels (eg, 0.25%) of silica in the coating compositions of the invention. Also, the data illustrates that initial and retained scratch resistance results obtained using coating compositions that have low levels of silica (i.e., 2.0% or less) are similar to results obtained using coating compositions that have higher levels of silica.

Figures 7 and 8 are electron micrographs of a transmission electron microscope image (magnification 105,000 x) of a cross section of the coating composition according to Example 3E, and Figures 9 and 10 are electron micrographs of an image of Transmission electron microscope (105,000 x magnification) of a cross section of the coating composition according to Example 3G.

ES 2 249 285 T3

Example 4

A coating composition according to the present invention was prepared from a mixture of the following ingredients:

<td>Ingredients</td><td>Resin solids (%)</td><td>Total weight (grams)</td>

<td>Methyl amyl ketone</td><td> --</td><td> 45,0</td>

<td>Tinuvin 928</td><td> 3,0</td><td> 3,0</td>

<td>Silica dispersion example 1C</td><td> 4,67</td><td> 8,8</td>

<td>Polysiloxane polyalcohol example A</td><td> 10,33</td><td> 10,33</td>

<td>Cymel 202</td><td> 15,0</td><td> 18,75</td>

<td>Acrylic polyol example 23C</td><td> 43,10</td><td> 69,68</td>

<td>Tinuvin 292</td><td> 0,5</td><td> 0,5</td>

<td>Catalyst example 12</td><td> 0,5</td><td> 0,67</td>

<td>DESMODUR N3300</td><td> 23,4</td><td> 23,4</td>

<td>DESMODUR Z4470</td><td> 3,5</td><td> 5,0</td>

A base coat, Azuritblau, distributed by PPG (B% K) Germany was applied over a primed steel automotive substrate. The basecoat was built to a film thickness of 12-15 microns, followed by a 5 minute heat conditioning at 80 ° C prior to application of the coating composition of Example 4. The coating composition of Example 4 wet-on-wet was spray applied to the base coat to build a clear coat film thickness of between 35 and 45 microns. The coating was then cured for 30 minutes at 130 ° C.

Example 5

A polysiloxane polyol was prepared which was the hydrosilylation product of a reactive silicone fluid with an approximate degree of polymerization of 3 to 7, that is, (Si-O)3 a (Si-O)7. The polysiloxane polyalcohol was prepared from a proportionally larger batch with the following mixture of ingredients in the ratios indicated.

<td>Ingredients</td><td>Equivalent weight</td><td>Equivalents</td><td>Parts by weight (kg)</td>

<td>Trimethylolpropane Monoallyl Ether</td><td> 174,0</td><td> 756,0</td><td> 131,54</td>

<td>Charge II</td><td></td><td></td><td></td>

<td>MASILWAX BASE1</td><td> 156,72</td><td> 594,8</td><td> 93,21</td>

<td>Charge III:</td><td></td><td></td><td></td>

<td>Chloroplatinic acid</td><td></td><td>10 ppm</td><td></td>

<td>Toluene</td><td></td><td></td><td> 0,23</td>

<td>Isopropanol</td><td></td><td></td><td> 0,07</td>

1 Polysiloxane-containing silicon hydride, available from BASF Corporation.

2 Equivalent weight based on mercuric dichloride determination.

ES 2 249 285 T3

Charge I and an amount of sodium bicarbonate equivalent to 20-25 ppm of total monomer solids under ambient conditions were added to a suitable reaction vessel equipped with a means to maintain a nitrogen atmosphere, and the temperature was gradually increased to 75 ° C under a nitrogen atmosphere. At that temperature, 5.0% of Charge II was added with stirring, followed by the addition of Charge III, equivalent to 10 ppm of active platinum based on total monomer solids. The reaction was then allowed to heat up at 95 ° C during which time the remainder of Charge II was added at a rate sufficient for the temperature not to exceed 95 ° C. After completion of this addition, the reaction temperature was maintained at 95 ° C and monitored by infrared spectroscopy to determine the disappearance of the silicon hydride absorption band (Si-H, 2150 cm-1).

AA Silica Dispersion

A colloidal silica dispersion was prepared as follows. A 4 necked reaction flask equipped with vacuum distillation was leveled with N2. 1500.9 g of the above-described polysiloxane polyalcohol, 3751.1 of ORGANOSILICASOL ™ MT-ST colloidal silica, commercially available from Nissan Chemicals, and 960.4 g of methyl amyl ketone were added to the reaction flask. The resulting mixture was vacuum distilled at 70 mm Hg and 31 ° C.

Film Formation Compositions

Formulation premixes: (each of the components was successively mixed with stirring).

Example 1 (99-346-91A)

<td>Ingredient</td><td>Parts by weight (g)</td><td>Solid weights (g)</td>

<td>Methyl-n-amyl ketone</td><td> 18,0</td><td> —</td>

<td>Butyl Acetate Cellosolve®1</td><td> 18,0</td><td> —</td>

<td>Butyl Acetate Carbitol®2</td><td> 4,0</td><td> —</td>

<td>TINUVIN® 9283</td><td> 3,0</td><td> 3,0</td>

<td>TINUVIN® 2924</td><td> 0,40</td><td> 0,40</td>

1 2-Butoxyethyl acetate solvent available from Union Carbide Corp.

2 2- (2-Butoxyethoxy) ethyl acetate available from Union Carbide Corp.

3 UV absorber 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol distributed by Ciba Specialty Chemicals Corp.

4 Sterically hindered amine light stabilizer distributed by Ciba Specialty Chemicals Corp.

The ingredient premix from Example 1 was used in Examples 2 and 3. The compositions for Examples 2 and 3 are listed in Table 1 below. The amounts listed are total parts by weight in grams and the amount in parentheses. is the weight percent based on the weight of resin solids. Each of the components was mixed successively with stirring.

TABLE 13

<td>Ingredient</td><td>Example 2 (99-346-93A)</td><td>Example 3 (99-346-93B)</td>

<td>Premix example 1</td><td> 43,4 (3,4)</td><td> 43,4 (3,4)</td>

<td>AA Silica Dispersion</td><td> 10,0 (7,0)</td><td> 10,0 (7,0)</td>

<td>SUMMARY 7571</td><td> 11,8 (11,4)</td><td> 11,8 (11,4)</td>

<td>Acrylic2</td><td> 100,8 (65,5)</td><td> 74,9 (48,7)</td>

<td>Butyl polyacrylate3</td><td> 0,50 (0,30)</td><td> 0,50 (0,30)</td>

<td>Acid Catalyst Blocked4</td><td> 2,50 (1,00)</td><td> 2,50 (1,00)</td>

<td>CYLINK® 20005</td><td> 37,1 (19,1)</td><td> --</td>

ES 2 249 285 T3

TABLE 13 (continued)

<td>Ingredient</td><td>Example 2 (99-346-93A)</td><td>Example 3 (99-346-93B)</td>

<td>TRIXENE DP9B / 14945</td><td> —</td><td> 51,3 (35,9)</td>

<td>Reduction information</td><td></td><td></td>

<td>Methyl n-amyl ketone</td><td> 2,39</td><td> —</td>

<td>Butyl Acetate Cellosolve®7</td><td> 2,39</td><td> —</td>

<td>Butyl Acetate Carbitol®8</td><td> 0,53</td><td> —</td>

<td>Spray viscosity9 (sec)</td><td> 29</td><td> 26</td>

<td>Paint temperature (° F)</td><td> 73</td><td> 74</td>

1 Methylated and butylated melamine-formaldehyde resin distributed by Solutia Inc.

2 Acrylic resin (30% styrene, 19.9% hydroxyethyl methacrylate, 28.7% Cardura E (distributed by Shell Chemical Co.), 9.5% acrylic acid, and 12% ethylhexyl acrylate) at 65% solids in SOLVESSO 100 (distributed by Exxon Chemicals America).

3 A flow control agent having a Mw of 6700 and a Mn of 2600 obtained in xylene at 60% solids distributed by DuPont.

4 Dodecyl benzenesulfonic acid solution, blocked with diisopropanol amine to 91% total neutralization, 40% acid solids in ethanol.

4 Dodecyl benzene sulfonic acid solution distributed by Chemcentral.

5 Tris (alkylcarbamoyl) triazine crosslinking agent distributed by CYTEC Industries, Inc.

6 Isophorone diisocyanate blocked isocyanurate 3,5-dimethylpyrazole available from Baxenden Chemicals Limited.

7 2-Butoxyethyl acetate solvent available from Union Carbide Corp.

8 2- (2-Butoxyethoxy) ethyl acetate available from Union Carbide Corp.

9 Viscosity measured in seconds with a # 4 FORD efflux cup at room temperature.

Test

The film-forming compositions of Examples 2 and 3 were spray applied to a pigmented base coat to form color-more transparent composite coatings on primed electrocoated steel panels. The panels were cold rolled steel panels (size 4 inches x 12 inches (10.16 cm by 30.48 cm)) coated with an ED5100 electrocoat and a PCV70100M primer coat, both distributed by PPG Industries, Inc. Test panels are distributed as APR30471 by ACT Laboratories, Inc. of Hillsdale, Michigan.

A black pigmented water-based acrylic / melamine basecoat, distributed by PPG Industries, Inc. (Basecoat Z) was used. The formulation for Base Coat Z is as follows.

Base Coat Z

<td>Ingredient</td><td>Parts by weight (g)</td><td>Solid weights (g)</td>

<td>n-butoxypropanol, PNB1</td><td> 45,0</td><td> —</td>

<td>CYMEL 3272</td><td> 38,9</td><td> 35,0</td>

<td>TINUVIN 11303</td><td> 3,20</td><td> 3,20</td>

<td>Phosphated epoxy4</td><td> 0,80</td><td> 0,50</td>

<td>Amine5</td><td> 2,00</td><td> —</td>

<td>Acrylic latex5</td><td> 109,4</td><td> 46,5</td>

ES 2 249 285 T3 (Continued)

<td>Ingredient</td><td>Parts by weight (g)</td><td>Solid weights (g)</td>

<td>Odorless mineral liquor7</td><td> 8</td><td> —</td>

<td>Polyurethane acrylic8</td><td> 42,6</td><td> 10,0</td>

<td>Black dye paste9</td><td> 47,6</td><td> 11,5</td>

<td>Amine5</td><td> 1,00</td><td> —</td>

<td>Deionized water</td><td> 67,7</td><td> —</td>

1 Solvent distributed by Lyondell Petrochemical.

2 Methylated formaldehyde melamine resin distributed by Cytec Industries, Inc.

3 Substituted hydroxyphenyl benzotriazole distributed by Ciba Specialty Chemicals Corp.

4 Phosphated epoxy prepared from Epon 828, a Bisphenol A polyglycidyl ether distributed by Shell Oil and Chemical Co .; in reaction with phosphoric acid in an 83:17 weight ratio.

5 Dimethylethanolamine, 50% aqueous, distributed by Union Carbide Corp.

6 The acrylic latex was prepared as follows. The polyester was prepared in a four necked round bottom flask equipped with a thermometer, mechanical stirrer, condenser, dry nitrogen purge, and heating atmosphere. The following ingredients were used:

<td>1103.0 g</td><td>isostaric acid</td>

<td>800.0 g</td><td>pentaerythritol</td>

<td>470.0 g</td><td>crotonic acid</td>

<td>688.0 g</td><td>phthalic anhydride</td>

<td>6.1 g</td><td>dibutyltin oxide</td>

<td>6.1 g</td><td>triphenyl phosphite</td>

<td>1170.0 g</td><td>butyl acrylate</td>

<td>4.0 g</td><td>Ionol (butylated hydroxytoluene)</td>

The first six ingredients were stirred in the flask at 210 ° C until 245 ml of distillate was collected and the acid number dropped to 46. The material was cooled to 77 ° C and the last two ingredients were stirred in. The final product was a viscous yellow liquid with a hydroxyl number of 54.0, a Gardner-Holdt viscosity of Z +, a weight average molecular weight of 45,600, and a non-volatile content of 70.2%. A pre-emulsion was prepared by combining with stirring the following ingredients:

<td>286.0 g</td><td>Example III polyester</td>

<td>664.0 g</td><td>butyl acrylate</td>

<td>30.0 g</td><td>ethylene glycol dimethacrylate</td>

<td>20.0 g</td><td>acrylic acid</td>

<td>46.4 g</td><td>dodecylbenzenesulfonic acid (70% isopropanol)</td>

<td>14.3 g</td><td>dimethylethanolamine</td>

<td>1000.0 g</td><td>Water</td>

The reaction was carried out using the same procedure and materials as in latex example I. The reaction evolved heat from 23 ° C to 80 ° C. The final pH of the latex was 6.1, the non-volatile content was 42.4%, the particle size was 105 nm, and the Brookfield viscosity was 14 cps (spindle # 1.50 rpm).

7 Solvent distributed by Shell Chemical Co.

8 Polyurethane acrylic composed of 4% dimethylol propionic acid, 16% Desmodur W (distributed by Bayer), 9.3% dimethyl diisocyanate, 22.8% FORMREZ 66-56 (Witco Corp.), 5.7 % MPEG 2000 (Union Carbide Corp.), 22.6% methyl methacrylate, 15.6% butyl acrylate, 1.6% ethylene glycol dimethacrylate, 2.1% diethylene triamine, 0.3% persulfate ammonium.

9 Black pigment distributed by Cabot Corp. as MONARCH BLACK 1300 dispersed in an acrylic network vehicle (35% butyl acrylate, 30% styrene, 18% butyl methacrylate, 8.5% 2-hydroxyethyl acrylate, 8 , 5% acrylic acid) at a pigment to total binder ratio (P / B) of 0.35.

ES 2 249 285 T3

Basecoats were automatically spray applied in two coats to the electrocoated and primed steel panels at room temperature (70 ° F (21 ° C)). No conditioning was provided between the two applications of the base coat. A total dry film thickness of 0.66 mils (17 microns) was targeted. Following application of the second base coat, room temperature conditioning was provided for 1 to 10 minutes prior to force conditioning the coated base panels. Force conditioning consisted of 5 minutes at 93 ° C (200 ° F). The clear coating compositions of Examples 2 and 3 were automatically spray applied onto the coated base panel at room temperature in two coats with a room temperature conditioning of 90 seconds between applications. The total dry film thickness for the clearcoats was 1.78 mils (45 microns). All coatings were allowed to air-condition at room temperature for ten minutes. Panels prepared from each of the coatings were fired for thirty minutes at 141 ° C (285 ° F) to fully cure the coatings (s). The panels were baked in a horizontal position.

Table 14 lists the properties of the coatings.

TABLE 14

<td>Example#</td><td>Initial brightness 20o1</td><td colspan="4">Gloss Retained After Scratch Test2 Post-exposure to the elements3</td>

<td></td><td></td><td>Initial</td><td>240 hours</td><td>504 hours</td><td>1028 hours</td>

1 The gloss was measured at 20or with a Statistical Novo-Gloss 20 gloss meteror, distributed by Paul N. Gardner Company, Inc.

2 The coated panels were subjected to a linear scratch scratch test of the coated surface with a weighted abrasive paper for ten double rubs using an AATCC scratch tester, model CM-5, distributed by Atlas Electrical Devices Company of Chicago, Illinois. . The abrasive paper used consisted of 3M 281Q WETORDRY ™ PrOdUCTION ™ 9 micron sandpaper sheets, commercially available from the 3M Company of St. Paul, Minnesota. The panels were rinsed with tap water and carefully dried with a paper towel. The gloss was measured at 20or (using the same gloss meter as used for gloss at 20or initial) in the hatched area of each test panel. Using the brightness reading at 20or lowest of the scratched area, the scratch results were recorded as the percentage of the initial gloss retained after the scratch test by applying the following calculation: 100% scratched gloss = initial gloss. Higher values for the percentage of gloss retained are desirable.

3 Post-weatherability scratch resistance (retained scratch resistance) was measured using the scratch test method described after the non-scratched test panels were subjected to simulated light bulb exposure. UVA-340 in a QUV Accelerated Weathering Tester distributed by Q Panel Lab Products. The test consisted of the following: a cycle of 70or for 8 hours of exposure to UVA followed by a condensation cycle at 50orC for 4 hours without UVA (the total test period is recorded in the table). Using the brightness reading at 20or lowest from the scratched area, the scratch results were recorded as the percentage of initial gloss retained after the weathered post scratch test using the following calculation: 100% * post weathered scratched gloss = initial gloss. Higher values for the percentage of gloss retained are desirable.

Example 6

A coating composition according to the present invention was prepared from a mixture of the following ingredients.

<td>Ingredients</td><td>Resin solids (%)</td><td>Total weight (g)</td>

<td>Acetate of butilo</td><td> —</td><td> 11,1</td>

<td>Acetate DOWANOL PM</td><td> —</td><td> 28,6</td>

<td>Butyl Acetate Cellosolve</td><td> —</td><td> 4,1</td>

<td>Tinuvin 928</td><td> 3,0</td><td> 3,0</td>

ES 2 249 285 T3 (Continued)

<td>Ingredients</td><td>Resin solids (%)</td><td>Total weight (g)</td>

<td>Silica dispersion example 1C</td><td> 6,7</td><td> 8,8</td>

<td>Polysiloxane polyalcohol example A</td><td> 10,3</td><td> 10,3</td>

<td>Cymel 202</td><td> 15,0</td><td> 18,8</td>

<td>Acrylic polyol1</td><td> 22,48</td><td> 31,5</td>

<td>Tinuvin 292</td><td> 0,5</td><td> 0,5</td>

<td>Catalyst</td><td> 0,5</td><td> 0,67</td>

<td>DESMODUR N3300</td><td> 23,4</td><td> 23,4</td>

<td>DESMODUR Z4470</td><td> 3,5</td><td> 5,0</td>

1 Acrylic polyol consisting of 14.5% BA, 14.5% BMA, 27.6% IboMA, 22.6% HPMA, 20.4% HEMA, 0.4% AA.

2 Phenyl acid phosphate solution, 75% in isopropanol.

A coating composition according to the present invention was also prepared from a mixture of the following ingredients:

<td>Ingredients</td><td>Resin solids (%)</td><td>Total weight (g)</td>

<td>Ethyl 3-ethoxypropionate</td><td> --</td><td> 38,7</td>

<td>Tinuvin 928</td><td> 3,0</td><td> 3,0</td>

<td>Silica dispersion example 1C</td><td> 6,7</td><td> 8,8</td>

<td>Polysiloxane polyalcohol example A</td><td> 10,3</td><td> 10,3</td>

<td>Cymel 202</td><td> 7,5</td><td> 9,4</td>

<td>Acrylic polyol1</td><td> 39,0</td><td> 57,9</td>

<td>Tinuvin 292</td><td> 1,0</td><td> 1,0</td>

<td>Catalyst</td><td> 0,5</td><td> 0,7</td>

<td>DESMODUR N3300</td><td> 16,6</td><td> 16,6</td>

<td>DESMODUR Z4470</td><td> 21,9</td><td> 31,3</td>

1 Acrylic polyol consisting of 19% BA, 18.5% BMA, 40% HPA, 20% Styrene, 0.5% MMA, 2% AA.

2 Phenyl acid phosphate solution, 75% in isopropanol.

The compositions of the present invention can provide numerous benefits in coating applications, including but not limited to, good initial and retained wear resistance, good appearance properties such as gloss and image sharpness, and physical properties such as a good flexibility and weather resistance.

Contents44

117 members in 14 offices

This recordMember, by publication datePriority claim4 more offices are in the list below

Priority claims15

Priority claims
Document	Office	Kind	Date
19990365069	United States of America	–	1999-07-30
36506999	United States of America	A	1999-07-30
36506999	United States of America	A	1999-07-30
17189999	United States of America	P	1999-12-23
17189999	United States of America	P	1999-12-23
19990171899P	United States of America	–	1999-12-23
20000489043	United States of America	–	2000-01-21
48904300	United States of America	A	2000-01-21
48904300	United States of America	A	2000-01-21
171899P	–	–	–
36506900950897	–	–	–
489043	–	–	–
US19990171899P	–	–	–
US19990365069	–	–	–
US20000489043	–	–	–

Members117

Family members, oldest first
Document	Office	Kind
CA2380403A1	Canada	A1	2001-02-08
CA2380408A1	Canada	A1	2001-02-08
CA2380412A1	Canada	A1	2001-02-08
CA2380415A1	Canada	A1	2001-02-08
WO0109231A1	World Intellectual Property Organization (WIPO)	A1	2001-02-08
WO0109259A1	World Intellectual Property Organization (WIPO)	A1	2001-02-08
WO0109260A1	World Intellectual Property Organization (WIPO)	A1	2001-02-08
WO0109261A1	World Intellectual Property Organization (WIPO)	A1	2001-02-08
AU6392700A	Australia	A	2001-02-19
AU6392900A	Australia	A	2001-02-19
AU6504200A	Australia	A	2001-02-19
AU6615800A	Australia	A	2001-02-19
BR0013294A	Brazil	A	2002-04-02
BR0012882A	Brazil	A	2002-04-09
BR0012883A	Brazil	A	2002-04-09
BR0012875A	Brazil	A	2002-04-16
KR20020034173A	Republic of Korea	A	2002-05-08
US6387519B1	United States of America	B1	2002-05-14
EP1204701A1	European Patent Office (EPO)	A1	2002-05-15
EP1204708A1	European Patent Office (EPO)	A1	2002-05-15
EP1204709A1	European Patent Office (EPO)	A1	2002-05-15
US2002086168A1	United States of America	A1	2002-07-04
KR20020053802A	Republic of Korea	A	2002-07-05
KR20020056881A	Republic of Korea	A	2002-07-10
KR20020056882A	Republic of Korea	A	2002-07-10
WO0109259A9	World Intellectual Property Organization (WIPO)	A9	2002-07-18
EP1228155A1	European Patent Office (EPO)	A1	2002-08-07
WO0109231A9	World Intellectual Property Organization (WIPO)	A9	2002-09-06
CN1376175A	China	A	2002-10-23
CN1376186A	China	A	2002-10-23
CN1376187A	China	A	2002-10-23
CN1377392A	China	A	2002-10-30
CA2455804A1	Canada	A1	2003-02-13
CA2624864A1	Canada	A1	2003-02-13
WO03011992A2	World Intellectual Property Organization (WIPO)	A2	2003-02-13
AU2002317592A1	Australia	A1	2003-02-17
JP2003506518A	Japan	A	2003-02-18
JP2003506519A	Japan	A	2003-02-18
JP2003506520A	Japan	A	2003-02-18
JP2003508595A	Japan	A	2003-03-04
WO03011992A3	World Intellectual Property Organization (WIPO)	A3	2003-06-05
US6593417B1	United States of America	B1	2003-07-15
MXPA02001018A	Mexico	A	2003-07-21
MXPA02001019A	Mexico	A	2003-07-21
MXPA02001097A	Mexico	A	2003-07-21
MXPA02001098A	Mexico	A	2003-07-21
AU764500B2	Australia	B2	2003-08-21
US6610777B1	United States of America	B1	2003-08-26
US6623791B2	United States of America	B2	2003-09-23
US2003207985A1	United States of America	A1	2003-11-06
US2003212199A1	United States of America	A1	2003-11-13
US6657001B1	United States of America	B1	2003-12-02
AU770696B2	Australia	B2	2004-02-26
AU771279B2	Australia	B2	2004-03-18
AU771282B2	Australia	B2	2004-03-18
KR20040030907A	Republic of Korea	A	2004-04-09
EP1417273A2	European Patent Office (EPO)	A2	2004-05-12
US2004110895A1	United States of America	A1	2004-06-10
US6759478B2	United States of America	B2	2004-07-06
US2004176529A1	United States of America	A1	2004-09-09
US6803408B2	United States of America	B2	2004-10-12
US2004225057A1	United States of America	A1	2004-11-11
JP2004536947A	Japan	A	2004-12-09
CN1209427C	China	C	2005-07-06
EP1204701B1	European Patent Office (EPO)	B1	2005-09-21
AU2002317592A8	Australia	A8	2005-10-13
AT305019T	Austria	T	2005-10-15
ATE305019T1	Austria	T1	2005-10-15
US6987144B2	United States of America	B2	2006-01-17
DE60022765D1	Germany	D1	2006-02-02
US7005472B2	United States of America	B2	2006-02-28
JP2006057098A	Japan	A	2006-03-02
JP2006070278A	Japan	A	2006-03-16
ES2249285T3This record	Spain	T3	2006-04-01
US7053149B2	United States of America	B2	2006-05-30
KR20060066135A	Republic of Korea	A	2006-06-15
CN1261508C	China	C	2006-06-28
DE60022765T2	Germany	T2	2006-06-29
CN1262582C	China	C	2006-07-05
MX238958B	Mexico	B	2006-07-27
JP2006213925A	Japan	A	2006-08-17
KR100618738B1	Republic of Korea	B1	2006-08-31
KR100618737B1	Republic of Korea	B1	2006-09-01
EP1204709B1	European Patent Office (EPO)	B1	2007-02-14
AT353942T	Austria	T	2007-03-15
ATE353942T1	Austria	T1	2007-03-15
DE60033403D1	Germany	D1	2007-03-29
PT1204709E	Portugal	E	2007-05-31
CA2380415C	Canada	C	2007-07-17
KR100745875B1	Republic of Korea	B1	2007-08-02
ES2280235T3	Spain	T3	2007-09-16
KR100760067B1	Republic of Korea	B1	2007-09-18
KR100760068B1	Republic of Korea	B1	2007-09-18
KR100760069B1	Republic of Korea	B1	2007-09-18
DE60033403T2	Germany	T2	2007-10-31
MX252994B	Mexico	B	2008-01-07
MX253908B	Mexico	B	2008-01-28
CA2380408C	Canada	C	2008-04-22
JP2008111129A	Japan	A	2008-05-15
CA2455804C	Canada	C	2008-07-08

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Abstract

Term

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DESCRIPTION

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TABLE A

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RR

II

RR

RR

II

II

RR

II

RR

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RRR

III

RRR (VI)

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I

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TABLE 5

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TABLE 13

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TABLE 14

Priority claims15

Members117

Numbers

Titles2

Classification