Epoxy resin curing agent for enhanced wear resistance and weatherability of cured materials

DESCRIPTION

EPOXY RESIN HARDENING AGENT FOR IMPROVED WEAR RESISTANCE AND ATMOSPHERIC CONDITIONS OF HARDENED MATERIALS

The invention relates to an epoxy resin hardener which produces materials with very high color stability, abrasion resistance, scratch resistance and chemical resistance. The invention also relates to a method for hardening an epoxy resin using such hardener as well as to a hardened epoxy resin material manufactured in this manner.

BACKGROUND OF THE INVENTION

Commercially available epoxy resins in combination with commercially available hardeners produce widely applicable materials such as corrosion protection coatings, composite material components and as molding plastics. In addition to the basic components of epoxy resin and hardener, the starting materials may contain dyes, pigments, fillers, reactive and nonreactive diluents, volatile solvents, stabilizing agents and additives.

Epoxy resins typically contain more than

ΡΕ1556438 one 1,2-epoxy group per mole and may be based on saturated, unsaturated, aliphatic, cycloaliphatic or heterocyclic structures.

Hardeners are usually selected from the following groups of chemical compounds: aromatic, aliphatic, cycloaliphatic or heterocyclic amines, amine adducts, polyamides, polyamide amides, Mannich bases, ketimines or carboxylic acid derivatives. Mercaptans compounds may also be used as active compounds within the hardener.

Fillers include titanium dioxide, silica, various silicates, minerals or carbon black.

Stabilizers include anti-oxidants, radical scavengers or UV absorbers.

Additives include plasticizers, hardening reaction catalysts, rheology modification additives or surfactants.

Reactive diluents are often epoxy compounds of considerably lower viscosity than epoxy resins.

The color stability of materials made from commercially available epoxy resins and hardeners is often known to be poor because

ΡΕ1556438 hardeners or combination of hardener, resin and additives, have a strong tendency to yellowing, also after hardening. A known method for reducing yellowing is the use of amine based hardeners with aliphatic or cycloaliphatic structures, because in the presence of light the yellowing of cycloaliphatic amines is significantly lower than that of aromatic amines.

The disadvantage of using aliphatic or cycloaliphatic amines as hardeners or hardeners is that the abrasion and scratch resistance of the resulting materials is often weaker than for aromatic amines.

It is also known that abrasion resistance, scratch resistance and chemical resistance of hardened epoxy resins can be significantly improved by using fillers such as silica (US 3794609). The disadvantage, however, is that the transparency of the hardened epoxy resin is considerably reduced, which is perceived as harmful, especially when the material is intended for use as a coating.

One method of producing hardened epoxy resins with high color stability, abrasion resistance, scratch resistance and chemical resistance, and acceptable transparency may therefore be the use of aliphatic or cycloaliphatic amine-based hardeners with low bias. yellowing together with silica-based nanoparticles as an additive. An example of silica-based nanoparticles is the Aerosil® product line from Degussa AG, Germany. From EP 0774443 A1 it is known that nanodisperse titanium dioxide is suitable for improving the color stability of, among others, polymer-based formulations.

An alternative method for the preparation of coatings with good abrasion resistance, scratch resistance and chemical resistance together with acceptable transparency is based on inorganic polymer-forming organic components containing particles or particle formers where the particle size is between 1 and 150 nm. The coating is generally hardened by applying the mixture of organic and inorganic components on a surface and drying with the aid of heat and / or UV-VIS radiation. Such coating forming mixtures may contain epoxy resins or compounds with epoxy groups. There are a large number of patents and publications describing the preparation of such organic-inorganic hybrid materials and possible applications: JP 09132637, US 5618860, US 5804616, WO 9832792, EP 496552, KR 2000059589, JP 2001288401 and Milena Spirkova et al., Hybrid Organic-Inorganic Epoxide-Based Coatings Prepared by SolGel Process, Proceedings of 6th Numberg Congress on Creative Advances in Coatings Technology, paper 12 (2001).

Thermosetting plastics as epoxy resins

ΡΕ1556438 can also be modified with nanodisperse inorganic particles for applications other than coatings. DE 19860691 A1 describes a magnetic paste containing nanocrystals. WO 9631572 A1 discloses polymerizable nanoparticles containing formulations which, among others, are based on acrylic or epoxy resins and which may be used to construct or join optoelectronic elements. WO 0130304 A1 describes materials that are based on organic thermosetting resins and nanoparticles-containing inorganic components or which form nanoparticles. The materials are used as dental replacement materials. In addition, several scientific publications describe the modification of thermosetting plastics as epoxy resins with nanoparticulate or nanoparticulate mixtures (eg, Soo-Jin Park et al., Surface

Modification of Montmorillonite on surface Acid-Base

Characteristics of clay and Thermal Stability of Epoxy / Clay Nanocomposites, Journal of Colloid and Interface Science, 251,160-165 (2002)).

It is also known to prepare basic nitrogen-containing hardeners or hardeners with hydrolysable silane compounds for thermoset resins such as epoxy resins. US 4988778 describes hardeners which are prepared by partial alcohololysis / aminolysis of γ-aminopropyltrimethoxy silane with diisopropyl amine, but without the addition of water. JP 04366159 describes a product which is prepared by reacting γ-glycidopropyltrimethoxy silane with water and small amounts of

ΡΕ1556438 is an amidine 1,8-diazabicyclo [5.4.0] undec-7-ene compound which is used as a subcomponent for hardening an epoxy-containing thermosetting mixture. The basic amidine compound however constitutes less than 62 ppm by weight of the silane / water mixture, so the product itself has to be considered as unsuitable as a hardener for epoxy resins.

It is also demonstrated in PCT / N02001 / 00287 that an existing organic lacquer or gel coat can be modified with suitable nanoparticle mixtures to, among other things, impart improved scratch resistance. Here a stable nanoparticles containing sun is prepared which is added to the existing organic lacquer or gelcoat as needed.

However, it is believed that the use of sol-gel mixtures, which are prepared by controlled hydrolysis / condensation of γ-aminopropyltrialkoxy silane or other nitrogen-containing silanes and / or mercaptosilanes as a hardener for epoxy resins.

Sol-gel process is a simple way to prepare nanoparticles based mixtures. The solgel process is based on controlled hydrolysis / condensation of eg silane alkoxides. The process is described in PCT / NO2001 / 00287 and produces gels that can be relatively easily mixed into polymeric and / or polymerizable organic formulations.

ΡΕ1556438

An example is soles which are prepared by controlled hydrolysis / condensation of γ-aminopropyltrialkoxy silane. The sol-gel process in this case is particularly simple because no external catalyst is required and because the process can be performed at room temperature or under gentle heating.

known for 4,4'-diaminodiphenylmethane (I) epoxy resins

Amine-based hardeners such as meta-xylylenediamine (II) are or

<img file="PT1556438E_D0001.tif" />

The amines react with epoxy resins by crosslinking with two or more polymer chains of epoxy resins. This leads to solidification (hardening) of the two component system consisting of amine and epoxy resin hardener and the formation of a relatively abrasion resistant material. The disadvantage of amine-based hardeners is that the hardened material turns relatively quickly yellowish due, among other things, to the oxidative degradation of the amine-based hardener components.

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In addition, the abrasion / scratch resistance of the hardened material is often too low for the material to be used for demanding applications.

It is an object of the present invention to provide a hardener for epoxy resins which provides hardened epoxy materials with high abrasion resistance and photostability.

It is another object to provide a hardener as mentioned above which provides materials with high transparency and clarity.

It is a further object of the invention to provide such a hardening agent which is easy to manufacture on an industrial scale, has a long shelf life and is capable of readily curing epoxy resins under normal conditions.

The invention

In a first aspect, the invention relates to an epoxy resin hardener defined by the features set forth in the characterizing part of claim 1.

According to a second aspect, the invention

51556438 refers to a cured epoxy resin as defined by claim 18.

According to a third aspect, the invention relates to a method for curing epoxy resins as defined by claim 19.

Preferred embodiments of the invention are disclosed in the dependent claims.

The first aspect of the invention relates to sol-gel hardeners which may be used for hardening epoxy resins. In a first step a controlled hydrolysis / condensation sol of prepared hydrolyzable and condensable amine-containing silane compounds is prepared. Suitable hydrolyzable and condensable amine-containing silane compounds are those comprised in the formula (XB-C &lt;1ί · Υ;₄.It) where g = 1 or 2, X = SH, -N = C = O or NRxig. NR x R 2 is selected from hydrogen, saturated or unsaturated C 1 -C 6 alkyl, substituted or unsubstituted aryl, formyl, aliphatic or aromatic carbonyl, carbamoyl, sulfonyl, sulfoxyl, phosphonyl, sulfinyl, phosphinyl, wherein the carbon chains of said compounds may be optionally contain one or more of the oxygen, nitrogen, sulfur, phosphorus, silicon and boron elements, and / or optionally containing one or more hydrolysable silane units, or R1,

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R₂ are selected from condensation products or addition products of one or more types of chemical compounds such as acids, alcohols, phenols, amines, aldehydes or epoxides.

A simple way to prepare nanoparticle based compositions is the sol-gel process. The sol-gel process is based on controlled hydrolysis / condensation of eg silane oxides. The process is described in PCT / NO2001 / 00287 and results in gels that are comparatively easy to mix with polymer-containing or polymerizable organic formulations. An example is the preparation of sols by controlled hydrolysis / condensation of γ-aminopropyl trialkoxysilane. In this case the sol-gel process is particularly simple as no catalyst is required and the process can be performed at room temperature or only with slight heating.

The main difference of this invention with respect to the inventions in the above mentioned patents and the results

<td>of publications</td><td>above</td><td>is</td><td>as if</td><td>follows: No</td>

<td>first step,</td><td>a</td><td>Sun</td><td>stable</td><td>by hydro-</td>

<td>lysis / condensation</td><td>controlled by</td><td>one</td><td>compound</td><td>of silane</td>

appropriate, possibly modified accordingly. When stored under favorable conditions, the product may be stable for six months or more. In the second step the sun is mixed with suitable epoxy resins to give hardened materials with improved color stability, abrasion resistance and scratch resistance and chemical resistance.

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As the inventors know, the state of the art does not describe stable solids with long term stability as hardeners for two or more component epoxy resins.

Controlled hydrolysis / condensation of compounds as described in the characterizing part of claim 1 of the patent generally results in a sun in which the particulate or oligomeric condensate products have various more or less free amino groups on the surface. Thus, these particles or oligomers may react with thermosetting resins such as epoxy resins by crosslinking with two or more polymer chains of the thermosetting resin in the same manner as known amine (I) and (II) hardeners. A corresponding hardening reaction is possible with soles prepared by controlled hydrolysis / condensation of other nitrogen-containing or mercaptosilane silane compounds, provided that the sun contains particles or oligomers with a sufficiently large number of more or less free amino groups and / or mercaptan groups. . Generally, sol-gel process reaction products such as alcohol or excess water must be removed before the sun can be used as a hardener or as a component of an epoxy resin hardener.

The crosslinking reaction and therefore the hardening reaction between particle forming condensate products with more or less amino groups

Livres1556438 surface free and an epoxy resin can be described as (IV):

<img file="PT1556438E_D0002.tif" />

(IV)

Sometimes the stability of the sun may be very short, especially after sol-gel reaction products such as alcohols or excess water have been removed. In addition, the rate of the hardening reaction between the sun and the epoxy resin may be far from optimized so the hardening reaction may be too fast or too slow. Adjustment of the hardening reaction rate in such cases is desirable. There may also be cases where the compatibility and therefore miscibility of the sun and epoxy resin are not good enough which may eg result in inadequate material properties in the hardened material. In addition, in these cases it is necessary

ΡΕ1556438 a compatibility adjustment. Modification of the sun prepared by an appropriate chemical conversion may therefore be advantageous.

Chemical conversions suitable for modifying the prepared sun are intended to more or less modify the free amino groups on the surface of the particle forming condensation product. Such conversions are performed between more or less free amino groups on the surface of a particle-forming condensation product and reactive compounds which preferably react quantitatively with more or less free amino groups at temperatures t &lt;470 K and pressures of P &lt;0.3. MPa. Particularly suitable reactive compounds are epoxides, acid derivatives, blocked and unblocked isocyanates and RX compounds consisting of

a) a suitable atom or group of atoms X and

b) a group R wherein RX is capable of reacting with more or less free amino groups in a substitution reaction whereby an atom or group of atoms X is replaced by an amino group (Endre Berner, Laerebok i organisk kjemi, Aschehoug &amp; Co., Oslo (1964), pages 144-147) and wherein the group R is selected from C 1 -C₂4 unsubstituted saturated or unsaturated alkyl, C1-C24 substituted saturated or unsaturated alkyl, substituted or unsubstituted aryl, carbonyl

If1556438 aliphatic or aromatic, wherein the carbon chains of said compounds may optionally include one or more of the oxygen, nitrogen, sulfur, silicon and boron elements, or selected groups of condensation products or addition products of one or more types of compounds. chemicals such as acids, alcohols, phenols, amines, aldehydes or epoxides, and the atom or group of atoms X is preferably selected from halogen, substituted or unsubstituted alkoxy, phenoxy, amine, carboxylate, sulfonate, sulfinate, phosphonate or phosphinate.

Examples of suitable epoxides are monoglycidyl compounds which may be described as wherein R1 is selected from groups such as hydrogen, unsubstituted saturated or unsaturated C1 -C24 alkyl, substituted or unsaturated C1 -C24 alkyl, substituted or unsubstituted aryl, aliphatic or aromatic carbonyl, wherein the carbon chains of said compounds may optionally include one or more of the oxygen, nitrogen, sulfur, silicon and boron elements, or R1 is selected from condensation products and addition products of one or more types of chemical compounds such as acids, alcohols, phenols, amines, aldehydes or epoxides.

ΡΕ1556438

Examples of suitable epoxides are further compounds with epoxidized C = C double bonds which may be described as

<img file="PT1556438E_D0003.tif" />

where R₄-R₄ are chosen from groups such as hydrogen, C₄-Ç₂₄ unsubstituted saturated or unsaturated alkyl, C₄-Ç₂₄substituted or unsaturated alkyl substituted or unsubstituted aryl, aliphatic or aromatic carbonyl, wherein the carbon chains of said compounds may optionally include one or more of the elements oxygen, nitrogen, sulfur, silicon and boron, or R₄ It is selected from condensation products or addition products of one or more types of chemical compounds such as acids, alcohols, phenols, amines, aldehydes or epoxides. Examples of suitable acid derivatives are

Carboxylic Acid Derivatives

Sulfonic Acid Derivatives

O

<img file="PT1556438E_D0004.tif" />

ΡΕ1556438

Sulfuric acid derivatives

O

<img file="PT1556438E_D0005.tif" />

wherein R1 is selected from groups such as hydrogen, unsubstituted saturated or unsaturated C1 -C24 alkyl, substituted saturated or unsaturated C1 -C24 alkyl, substituted or unsubstituted aryl, aliphatic or aromatic carbonyl, wherein the carbon chains of said compounds may optionally include one or more of the elements oxygen, nitrogen, sulfur, silicon and boron, or R1 is selected from condensation products and addition products of one or more types of chemical compounds such as acids, alcohols, phenols, amines, aldehydes or epoxides, and

X is a suitable leaving group such as halogen, substituted or unsubstituted alkoxy, phenoxy, amine, carboxylate, sulfonate, sulfinate, phosphonate or phosphinate.

Examples of suitable isocyanates may be described as

O = C == N \

wherein R 1 is selected from groups such as hydrogen, unsubstituted saturated or unsaturated C 1 -C 24 alkyl, C 1 -C 24

641556438 substituted or unsaturated alkyl substituted or unsubstituted aryl, aliphatic or aromatic carbonyl, wherein the carbon chains of said compounds may optionally include one or more of the oxygen, nitrogen, sulfur, silicon and boron elements, or Rx is selected from condensation products and addition products of one or more types of chemical compounds such as acids, alcohols, phenols, amines, aldehydes or epoxides, and wherein the isocyanate group may be blocked by known chemical substances.

In the crosslinking process and thus in the process of hardening between particle forming condensation products and more or less free amino groups on the surface of epoxy resins, addition products of the following type are formed:

R »

NH OH

R 2 NH 4 J

Laughs

R, —R₃ r₄

-Re

R₂ r₄

Similarly addition products are formed when more or less free amino groups are converted with isocyanates:

R₄—NH

R,

R, -NH₂ + O == C = N — R₂ \ / Λ-NH

Thus, condensation products forming

Particles with more or less free amino groups on the surface can also be used in the crosslinking process and thus in the process of hardening isocyanate-based resins, which leads to the formation of so-called polyurethanes.

Preferred Embodiments

A preferred embodiment of the invention is a hardener as defined by (III) wherein X = NR₂R₂R1 is hydrogen and R₂ is H- (HN-CH₂-CH₂-) _m where m = 0-6, B is propylene, η = 1 and Y is ethoxy or methoxy.

Another preferred embodiment of the invention is a hardener as defined by (III) wherein X = NR₂R₂, R₂is hydrogen and R₂ is phenyl, B is propylene, η = 1 and Y is ethoxy or methoxy.

Still another preferred embodiment of the invention is a hardener as defined by (III) wherein X = NR₂R₂R1 is hydrogen and R₂ is carbamoyl, B is propylene, n = 1 and Y is ethoxy or methoxy.

Still another preferred embodiment of the invention is a hardener as defined by (III) wherein X = SH, B is propylene, η = 1 and Y is ethoxy or methoxy.

Still another preferred embodiment of the invention is a hardener as defined by (III) wherein X = N = C = O, B is propylene, η = 1 and Y is ethoxy or methoxy.

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Yet another preferred embodiment of the invention is a hardener as defined by (III) wherein the sun is prepared wholly or partially by controlled hydrolysis and condensation of bis (γ-trialcoxysilylpropyl) amine.

Yet another preferred embodiment of the invention is a hardener as defined by (III) wherein the sun is prepared wholly or partially by controlled hydrolysis and condensation of tris [3-trialcoxysilylpropyl] isocyanurate.

The hardener of the invention may, as appropriate, also include at least one UV absorber, at least one radical scavenger, at least one antioxidant, at least one dye or pigment, at least one filler and / or at least one additive.

According to another aspect the invention may also comprise mixtures comprising at least one of the sol-gel hardeners according to one of the above aspects of the invention, epoxy resins and optionally additives such as antioxidants, light absorbing agents ( UV absorbers), radical scavengers, acid controllers, dyes, pigments, fillers and / or other additives.

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Examples

Particle Forming Condensation Product Preparation

1. 250 g of γ-aminopropyl triethoxysilane (γ-APS, Crompton Corporation, USA) is placed in a 1000 mL round bottom flask with condenser and magnetic stirrer. A mixture of 73.5 g of butyldiglycol (BDG) and 28.5 g of water is added. The mixture was heated in an oil bath to

110 ° C at reflux for 45 minutes. The condenser is replaced by a distillation column and volatile reaction products are removed at an oil bath temperature of 110 ° C and a vacuum gradient of 1000 mbar-20 mbar. Distillation is terminated when the pressure in the round bottom flask has reached 20 mbar or less for 10 minutes. About 175 mL of distillate was collected. The reaction product is a clear, colorless Gardner &lt;1 color (according to Gardner / ASTM D 1544 color scale) and a viscosity &lt;400 mPas. Titration with 4dodecylbenzene sulfonic acid in ethanol / water (96% by volume ethanol) showed that about 75% of the amino groups in the original γ-APS are available for protonation with 4dodecylbenzene sulfonic acid.

2. 250 g of γ-aminopropyl triethoxysilane (γ-APS, Crompton Corporation, USA) is placed in a 1000 ml round bottom flask with condenser and magnetic stirrer. A mixture of 73.5 g of butyl glycol (BDG) and

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28.5 g of water and 0.73 g of Tinuvin 123 (Ciba Specialty Chemicals, Switzerland). The composition is heated in an oil bath at 110 ° C at reflux for 45 minutes. The round bottom flask is replaced by a distillation column and the volatile components are removed at an oil bath temperature of 110 ° C and a vacuum gradient of about 1000 mbar-20 mbar. Distillation is terminated when the pressure in the round bottom flask has reached 20 mbar or less for 10 minutes. About 172 mL of distillate was collected. The reaction product is a clear, colorless liquid with Gardner color = 1 (according to Gardner / ASTM D 1544 color scale) and viscosity &lt;400 mPas. Titration with 4dodecylbenzene sulfonic acid in ethanol / water (96% ethanol) showed that 75% of the original amino groups are available for protonation with 4-dodecylbenzene sulfonic acid.

3 250 g of γ-aminopropyl triethoxysilane (γ-APS, Crompton Corporation, USA) is placed in a 1000 ml round bottom flask with condenser and magnetic stirrer. A mixture of 73.5 g of butyl glycol (BDG) and 28.5 g of water and 0.73 g of Tinuvin 123 (Ciba Specialty Chemicals, Switzerland) is added. The composition is heated in an oil bath at 110 ° C at reflux for 45 minutes. The condenser is replaced by a distillation column and volatile components are removed at an oil bath temperature of 110 ° C and a vacuum gradient of about 1000 mbar-20 mbar. Distillation is terminated when the pressure in the round bottom flask has reached 20 mbar or less for 10

51556438 minutes. About 175 mL of distillate was collected. To the still hot reaction product is added a heated solution of 1.0 g Cyasorb UV-1164 (Cytec Inc., USA) in 10 mL cyclohexane (Cytek Inc., USA). Further distillation is performed as described above until the pressure in the round bottom flask has reached 20 mbar or less for 10 minutes. The reaction product is a clear yellow liquid, Gardner color = 3 (according to Gardner Color Chart / ASTM D 1544) and a viscosity &lt;400 mPas at 50 ° C. At 10 ° C the reaction product is a yellow crystalline wax-like mass.

4 885.6 g of γ-aminopropyl triethoxysilane (γAPS, Crompton Corporation, USA) is placed in a 1000 mL round bottom flask with condenser and magnetic stirrer. A mixture of 389.3 g of butyl glycol (BDG) and 93.6 g of water and 12.0 g Tinuvin 123 (Ciba Specialty Chemicals, Switzerland) is added. The composition is heated in an oil bath at 110 ° C at reflux for 45 minutes. The condenser is replaced by a distillation column and volatile components are removed at an oil bath temperature of 110 ° C and a vacuum gradient of about 1000 mbar-20 mbar. Distillation is terminated when the pressure in the round bottom flask has reached 20 mbar or less for 10 minutes. About 536 g of distillate was collected. To the still hot reaction product is added a heated solution of 12.0 g Cyasorb UV-1164 and 12.0 g Cyasorb UV-2908 (Cytec Inc., USA) dissolved in 94 mL of toluene. Then another distillation is performed as described above until the pressure in the round bottom flask has reached 20 ° C.

ΡΕ1556438 mbar or less for 10 minutes. The reaction product is a clear yellow liquid with Gardner color = 3 (according to Gardner Color Chart / ASTM D 1544) and a viscosity &lt;400 mPas at 50 ° C. At 10 ° C the reaction product is a waxy yellow crystalline mass.

5 597.8 g of γ-aminopropyl triethoxysilane (γAPS, Crompton Corporation, USA) is placed in a 1000 mL round bottom flask with condenser and magnetic stirrer. A mixture of 262.5 g of butyl glycol (BDG) and 63.2 g of water and 8.1 g of Tinuvin 123 (Ciba Specialty Chemicals, Switzerland) is added. The composition is heated in an oil bath at 110 ° C at reflux for 45 minutes. The condenser is replaced by a distillation column and volatile components are removed at an oil bath temperature of 110 ° C and a vacuum gradient of about 1000 mbar-20 mbar. Distillation is terminated when the pressure in the round bottom flask has reached 20 mbar or less for 10 minutes. About 536 mL of distillate was collected. To the still warm reaction product is added a heated solution of 12.0 g of Cyasorb UV-1164 (Cytec Inc., USA) dissolved in 36 mL of toluene. Further distillation is performed as described above until the pressure in the round bottom flask has reached 20 mbar or less for 10 minutes. The reaction product is a clear yellow liquid with Gardner color = 3 (according to Gardner Color Chart / ASTM D 1544) and viscosity &lt;400 mPas at 50 ° C. At 10 ° C, the reaction product is a yellow crystalline mass similar to wax.

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4

Mixing of particulate former with commercial hardeners and converting the mixture with commercial epoxy resins for test plate preparation.

6 100 g of epoxy resin (commercially available reaction product from the conversion of 2,2-bis (4-hydroxyphenyl) propane and epichlorohydrin, CY 219, Vantico AG, Switzerland) was weighed into a beaker of an accuracy of 0 0.1 g. Then 50 g of hardener (1: 1 v / v mixture of experiment 1 and HY 5160 from Vantico AG, Switzerland) was added and the mixture was carefully stirred by hand. The resin was preheated to 40 ° C while the hardener was at room temperature, ie about 23 ° C. The mixture was then placed in a chamber heated to 40 ° C to facilitate the removal of air from the epoxy composition, ie the removal of small air bubbles. After a few minutes, the mixture was transferred to a 60 mL disposable syringe and subsequently transferred to 87 and 137 mm internal diameter petri dishes. The plates had been waxed with a layer of QV 5110 Vantico slip wax. Following this transfer caps were placed in the Petri dishes. The samples were hardened for one day (24 h) at room temperature. Then the samples were demolded and post-hardened for about 17 h at 70 ° C. The samples were wrapped in paper and placed in plastic bags equipped with zip fasteners.

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7 Different hardener compositions were prepared between 3-5-particle-forming condensation products and a phenol-free, low-viscosity, modified cycloaliphatic polyamine hardener commercially available for epoxy resins (Aradur 2965, Vantico AG, Switzerland). The different compositions are listed in table 1.

Table 1

<td>Charged</td><td>Condensation Product</td><td>% by weight of product of</td><td>% by weight of</td>

<td>hardener</td><td>particle former,</td><td>condensation forming</td><td>Aradur 2965 on</td>

<td>no^and</td><td>prepared in Example N-</td><td>particles in the ocposition</td><td>ocposition</td>

<td>I.</td><td> 3</td><td> 100</td><td> 0</td>

<td>II.</td><td> 11</td><td> 67</td><td> 33</td>

<td>III.</td><td> 11</td><td> 33</td><td> 67</td>

<td>IV.</td><td> 12</td><td> 50</td><td> 50</td>

<td>v.</td><td> —</td><td> 0</td><td> 100</td>

The hardener compositions thus prepared were mixed with epoxy resins (commercially available reaction products of the conversion of 2,2-bis- (4-hydroxyphenyl) propane and epichlorohydrin (Araldite GY 250,

Vantico AG, Switzerland) as in Example 6. The compositions were cured in layers about 2 mm thick in PVDF (polyvinylene fluoride) plates. The mixing ratios are shown in table 2.

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Table 2

<td>Sample / Plate n^and</td><td>Composition of hardener n^and</td><td>% by weight of decomposition hardener on mixture</td><td>% by weight of Araldite Gi 250 at mixture</td>

<td>P I.</td><td>I.</td><td> 33</td><td> 67</td>

<td>P II.</td><td>II.</td><td> 33</td><td> 67</td>

<td>P III.</td><td>III.</td><td> 33</td><td> 67</td>

<td>P IV.</td><td>IV.</td><td> 33</td><td> 67</td>

<td>P V.</td><td>V.</td><td> 33</td><td> 67</td>

Conversion of particle former condensation product with commercially available epoxy resins for sample / plate preparation

8 100 g of epoxy resin (commercially available reaction product of the conversion of 2,2-bis (4-hydroxyphenyl) propane and epichlorohydrin, CY 219, Vantico AG Switzerland) was weighed into a beaker with an accuracy of 0, 1 g. Then 50 g of hardener (sol prepared in Example 1) was added and the mixture was thoroughly shaken by hand. The resin was preheated to 40 ° C while the hardener was at room temperature, ie about 23 ° C. The mixture was then placed in a chamber heated to 40 ° C to facilitate the removal of air from the epoxy composition, ie, the removal of small air bubbles. After a few minutes the mixture was transferred to a 60 ml disposable syringe and subsequently transferred to 87 and 137 mm internal diameter petri dishes. The plates had been waxed with a layer of

Ant1556438 QV 5110 Vantico slip. Following this transfer, lids were placed on the Petri dishes. The samples were hardened for one day (24 h) at room temperature. Then the samples were demolded and post-hardened for about 17 h at 70 ° C. Finally, the samples were wrapped in paper and placed in plastic bags equipped with zip fasteners.

9 100 g of epoxy resin (commercially available reaction product of the conversion of 2,2-bis (4-hydroxyphenyl) propane and epichlorohydrin, CY 219, Vantico)

AG, Switzerland) in a beaker with an accuracy of 0,1 g. Then 50 g of hardener (sol prepared in Example 2) was added and the mixture was stirred well by hand. The resin was preheated to 40 ° C while the hardener was at room temperature, ie about 23 ° C. The mixture was then placed in a chamber heated to 40 ° C to facilitate the removal of air from the epoxy composition, ie, the removal of small air bubbles. After a few minutes the mixture was transferred to a 60 ml disposable syringe and subsequently transferred to 87 and 137 mm internal diameter petri dishes. The plates had been waxed with a layer of QV 5110 Vantico slip wax. Following this transfer caps were placed on the Petri dishes. The samples were hardened for one day (24 h) at room temperature. Then the samples were demolded and post-hardened for about 17 h at 70 ° C. Finally, the samples were wrapped in paper and placed in plastic bags equipped with zip fasteners.

10 100 g of epoxy resin (commercially available reaction product from the conversion of 2,2-bis (4-hydroxyphenyl) propane and epichlorohydrin, CY 219, Vantico AG, Switzerland) was weighed into a beaker of an accuracy of 0 0.1 g. Then 50 g of hardener (sol prepared in Example 3) was added and the mixture was thoroughly shaken by hand. The resin and hardener were preheated to 60 ° C in a heated chamber. The mixture was then transferred to a 60 ml disposable syringe and subsequently transferred to 87 and 137 mm internal diameter petri dishes. The plates had been waxed with a layer of QV 5110 Vantico slip wax. Following this transfer caps were placed on the Petri dishes. The samples were hardened for one day (24 h) at room temperature. Then the samples were demolded and post-hardened for about 17 h at 70 ° C. Finally, the samples were wrapped in paper and placed in plastic bags equipped with zip fasteners.

11 100 g of epoxy resin (commercially available reaction product of the conversion of 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis- (4-hydroxyphenyl) methane and epichlorohydrin, to which was added low viscosity epoxides for dilution (L 0166 / S700, Bakelite AG, Germany) in a beaker with an accuracy of 0.1 g.

Then, 50 g of hardener (sol prepared in Example 1) was added and the mixture was thoroughly shaken by hand. The resin was preheated to 40 ° C while the hardener was at room temperature, ie about 23 ° C. Then the mixture was placed in a chamber heated to 40 ° C to facilitate air removal from the epoxy composition, ie, removal of small air bubbles. After a few minutes the mixture was transferred to a 60 ml disposable syringe and subsequently transferred to 87 and 137 mm internal diameter petri dishes. The plates had been waxed with a layer of QV 5110 Vantico slip wax. Following this transfer caps were placed on the Petri dishes. The samples were hardened for one day (24 h) at room temperature. Then the samples were demolded and post-hardened for about 17 h at 70 ° C. Finally, the samples were wrapped in paper and placed in plastic bags equipped with zip fasteners.

Conversion of commercially available hardeners to commercially available epoxy resins for sample / plate preparation

12 100 g of epoxy resin (commercially available reaction product of the conversion of 2,2-bis (4-hydroxyphenyl) propane and epichlorohydrin, CY 219, Vantico AG, Switzerland) was weighed into a beaker with an accuracy of 0 0.1 g. Then 50 g of hardener (HY 5160, Vantico AG, Switzerland)) was added and the mixture was thoroughly stirred.

ΡΕ1556438 manually. The resin was preheated to 40 ° C while the hardener was at room temperature, ie about 23 ° C. The mixture was then placed in a chamber heated to 40 ° C to facilitate air removal from the epoxy composition, ie removal of small air bubbles. After a few minutes the mixture was transferred to a 60 ml disposable syringe and subsequently transferred to 87 and 137 mm internal diameter petri dishes. The plates had been waxed with a layer of QV 5110 Vantico slip wax. Following this transfer caps were placed on the Petri dishes. The samples were hardened for one day (24 h) at room temperature. Then the samples were demolded and post-hardened for about 17 h at 70 ° C. Finally, the samples were wrapped in paper and placed in plastic bags equipped with zip fasteners.

Modification of more or less free amino groups on the surface of particle forming condensation products

13 Heat 100 g of reaction product at 11 to 70 ° C to give a clear liquid. Then 100 g of glycidyl-2-methylphenyl ether (CAS [2210-79-9]; Araldite DY-K, Vantico AG, Switzerland) is added and the reaction mixture is kept at 70 ° C for one hour. A clear yellow product is obtained which is a viscous gel at 10 ° C and a low viscosity liquid at 80 ° C. This product reacts

51556438 significantly slower in a process of hardening with commercially available reaction products from the conversion of 2,2-bis (4-hydroxyphenyl) propane and epichlorohydrin than the reaction product of 11.

14 Heat 100 g of reaction product at 11 to 70 ° C to give a clear liquid. Then 150 g of glycidyl-2-methylphenyl ether (CAS [2210-79-9]; Araldite DY-K, Vantico AG, Switzerland) is added and the reaction mixture is kept at 70 ° C for one hour. A clear yellow product is obtained which is a viscous gel at 10 ° C and a low viscosity liquid at 80 ° C. Unlike the reaction product of 11, this product does not react in a hardening process with commercially available reaction products of the conversion of 2,2-bis (4-hydroxyphenyl) propane and epichlorohydrin.

Characterization and tests:

Sun Particle Size

The particle size of the sun was measured using the light scattering principle. A commercial instrument, Zetasizer 3 from Malvern, United Kingdom, was used to determine size distribution.

The size distribution was well defined and the average particle size was less than 5 nm for the soles prepared according to Examples 1-3.

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Abrasion Properties

The abrasion properties were tested using an Eyre / Bicere universal wear testing machine. The constant weight was 588 g (3x the load). In a plate made according to Example 9 a relatively large number of scratches were made. On a plate made according to Example 4, the scratches are barely visible.

Scratch resistance / abrasion properties determined by the Erichsen test Scratch resistance / abrasion test was investigated using an Erichsen hardness pen (Erichsen, Germany). The method is based on making a scratch with the hardness pen. The force exerted during the test is controlled by a spring. The force-related hardness value is read from the Newton hardness pen [N]. At least three parallel determinations are made for each sample. It is recorded when the force does not produce visible risks and at which force the first visible risk is obtained. The test was performed on a series of plates prepared as described in Example 8. The force required to make scratches on modified hardener plates is shown to be at least 40 times greater than the force required to scratch scratches on plates made with hardener. amine-based commercials. The results are presented in table 3.

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Table 3

<td>Plate / sample n^s</td><td>Strength [N]</td>

<td>PI.</td><td> &gt;20</td>

<td>P II.</td><td> 9-10</td>

<td>P III.</td><td> 9-10</td>

<td>P IV.</td><td> 8-9</td>

<td>P V.</td><td> 0-0,2</td>

Accelerated aging and color / brightness determination

The epoxy plates made according to Example 14 were subjected to accelerated aging according to the

ISO 4892-3 for 426 hours. The test instrument was an ATLAS UVCON climate chamber (Atlas Inc., USA) equipped with UVA-340 fluorescence lamps. The test cycle comprised 4 hours of dry-heating UV radiation at 45 ° C, 30 minutes of water spraying at 10-12 ° C and 3 hours and 30 minutes of condensation at 40 ° C.

Plate colors were determined before accelerated aging and after accelerated aging according to ASTM 2244.

Color determined by the so-called exterior light, D65, 10 °

Reference Standard White (33112035N)

CIE-lab DL, Da, Db and DE color difference

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DE total color change

Color coordinates DL (white / black), Da (red / green) and Db (yellow / blue)

Typical results of color determinations are shown in table 4.

Table 4

<td>plate / sample no</td><td>DL</td><td>Gives</td><td>DB</td><td>IN</td>

<td>P I. (after aging)</td><td> -8,36</td><td> -1, 74</td><td> 29, 42</td><td> 30,53</td>

<td>P II. (after aging)</td><td> -8,16</td><td> -1,86</td><td> 33,42</td><td> 34,45</td>

<td>P III. (after aging)</td><td> -9,17</td><td> -1,26</td><td> 44,37</td><td> 45,32</td>

<td>P IV. (after aging)</td><td> -9,14</td><td> -0,15</td><td> 38,81</td><td> 39,87</td>

<td>P V. (after aging)</td><td> -12,22</td><td> 2,56</td><td> 52,85</td><td> 54,31</td>

<td>P III. (before aging)</td><td> -1,08</td><td> -0, 72</td><td> 2,24</td><td> 2,58</td>

<td>P IV. (before aging)</td><td> -1,23</td><td> -0,99</td><td> 3,01</td><td> 3,40</td>

<td>P V. (before aging)</td><td> -2,38</td><td> -0,92</td><td> 2,97</td><td> 3,92</td>

Brightness measurements were made according to ISO 2813. Results are shown in Table 5. Brightness was measured in one place. The apparatus is a multi-brightness Byk Gardner 20 °, 60 ° and 85 °. Because the reflection of brightness at 60 ° gives more than 100% brightness, Table 5 shows the values ​​measured at an angle of incidence of 85 °. Typical results of color determinations are presented in table 5.

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Table 5

<td></td><td>Brightness before</td><td>Brightness after</td>

<td>Plate / Sample</td><td>aging</td><td>aging</td>

<td>No.</td><td>accelerated (angle of</td><td>accelerated (angle of</td>

<td></td><td>incidence of 85 °)</td><td>incidence of 85 °)</td>

<td>P I.</td><td> 99, 1</td><td> 96,3</td>

<td>P II.</td><td> 99, 4</td><td> 93,5</td>

<td>P III.</td><td> 98,9</td><td> 88,8</td>

<td>P IV.</td><td> 9 6,9</td><td> 80,0</td>

<td>P V.</td><td> 83,0</td><td> 25,6</td>

It is evident that the hardener-based epoxy plates of the system according to the present invention (Plate / Sample No. I-IV) exhibit significantly less color variation and / or gloss loss than non-base epoxy plates hardener (Plate / Sample No. V).

Brightness reduction is caused by chemical degradation of the plates. Thus, plates that subsequent to accelerated aging show little or no gloss reduction have better qualifications with respect to their ability to withstand the degradation of chemicals such as acidic or basic liquids than plates which comparatively exhibit large gloss reduction.