Additive for primer compositions

(54) Title: METHOD FOR CONNECTING A FIRST SUBSTRATE TO A SECOND SUBSTRATE AND PANEL SET (30) Unionist Priority: 24/04/2007 us 60 / 913,703 (73) Holder (s): Dow Global Technologies Inc.

(72) Inventor (s): dirk schwoeppe, stefan schmatloch (74) Attorney (s): ANTONIO MAURÍCIO PEDRAS ARNAUD (86) International Order: pct us2008054509 of 02/21/2008 (57) Summary: method for connecting a first SUBSTRATE TO A SECOND SUBSTRATE AND PANEL SET. A composition and method for bonding a substrate. In general, a primer composition that includes an adhesion promoter, which is an adduct prepared by the reaction of at least one aromatic polyisocyanary compound, with a portion containing active hydrogen from an organofunctional silane, and a prepolymer derived will be applied to a substrate. from the reaction of at least one aliphatic polyisocyanate and a polyol, and reacts at least partially with a portion containing active hydrogen from an organofunctional silane.

(87) International Publication: wo 2oos / i34U2de 06/11/2008

METHOD FOR CONNECTING A FIRST SUBSTRATE TO A SECOND SUBSTRATE AND PANEL SET.

Field of invention

This invention relates to the bonding of substrates and more specifically to the bonding of substrates in automotive vehicle applications, such as one or more of substantially transparent substrates, cured polyurethane adhesives, encapsulated panels, electrostatically coated substrates, painted substrates, or the like.

History of the invention

When properly prepared, the glass substrates are installed in an opening of an automotive vehicle structure by applying one or more layers of primer on the glass substrate, over the layer of burnt ceramic enamel, applying an adhesive between the primer and the vehicle structure and placing the glass substrate in the opening.

Despite the commercial availability of excellent primers having wide spread applicability (for example, BETAPRIME ™ 5500 and 5404,

Dow Chemical Company), remains the convenience of such primers obtainable from the desire to expand to additional applications.

Examples of efforts to improve primer composition performance are illustrated in EP 1382625^THE1, WO 2006/042305 and US Patent No. 6,976,500, all of which are incorporated herein by reference.

Summary of the invention

The invention satisfies such a desire by providing a composition and method for bonding. In general, a primer composition, which will be applied to a substrate, reaction of (1) a composition specifically a one-step primer) including a prepolymer with a free isocyanate content, which reacts at least partially with the active hydrogen of a silane organofunctionality of an amino-silane with a group includes a primer product (and more secondary or primary amino, a mercapto-silane, or a combination thereof, (2) an adhesion promoter prepared by reacting (a) at least one aromatic polyisocyanate with the active hydrogen of an organofunctional silane selected from amino-silane with a secondary or primary amino group, a mercapto-silane, or a combination thereof ; and (3) optionally, an isocyanate-functional prepolymer with an isocyanate content greater than about 1%, and being the reaction product of a polyol and an aromatic polyisocyanate. In a more particular aspect, (a) the aromatic polyisocyanate of the adhesion promoting compound includes a thiophosphate, a phosphate, a thiophosphate moiety or any combination thereof (for example, very particularly a tris (p-isocyanate-phenyl) thiophosphate); (b) the amino functionality silane of the primer composition and the adhesion promoter includes at least one silicon atom, two or three methoxy and / or ethoxy groups, attached to at least one of the silicon atoms, a secondary hindered amino group or any combination thereof; or (c) a combination of (a) and (b); and / or the isocyanate-functional prepolymer with an isocyanate content greater than about 1% is the reaction product of a polyol having a functionality greater than about 2 and a molecular weight (M_n) greater than about 300 and an aromatic polyisocyanate. Another aspect of the invention relates to an additive that can be incorporated into a base primer composition that includes a polymeric prepolymer with a free isocyanate content, and more specifically, at least one prepolymer (derived from the reaction of at least an aliphatic polyisocyanate and a polyol), which reacts at least partially with an amino group of an aminosilane, the aminosilane including a plurality of alkoxy groups bonded to silicon. When used, the additive improves the ability of a primer to which it is added to bond to a variety of substrates, and particularly improves adhesion to metal surfaces, glass surfaces, polymeric surfaces, any coating on them or differently. More particularly, as discussed herein, the invention relates to a method for attaching a first substrate to a second substrate, including the steps of: (a) applying a primer composition on one or both substrates (I) it includes an adhesion promoter, which is an adduct prepared by the reaction of at least one aromatic polyisocyanate compound (for example, a trifunctional isocyanate), with an active hydrogen from an organofunctional silane; (II) a prepolymer derived from the reaction of at least one aliphatic polyisocyanate and a polyol, and reacts at least partially with the active hydrogen of an organofunctional silane; and optionally (III) a solvent; (b) applying an adhesive to at least one of the substrates; and (c) joining the two substrates.

In general, as will be described, the aromatic polyisocyanate compound will include a thiophosphate, a phosphate, and a thiophosphane moiety, or any combination thereof. For example, the aromatic polyisocyanate can include tris thiophosphate (isocyanate-phenyl).

A particular composition may further include at least one isocyanate-functional prepolymer with an isocyanate content greater than about 1%. Accordingly, such a prepolymer will be the reaction product of a polyol having a functionality greater than about 2 and a molecular weight (M_n) greater than about 300 and an aromatic polyisocyanate. For example, it can be a reaction product of a triol and a diisocyanate that includes MDI.

In a particular aspect, one or more of the organofunctional silanes can include two or three methoxy and / or ethoxy groups attached to each of at least one silicon atom. It can include a mercapto group, an amino group (for example, a secondary amino group), or a combination thereof.

Here, the compositions may further include diethyl malonate, an acid (e.g., phosphoric acid), a film-forming resin, a pigment or a catalyst or a combination thereof.

Generally, the adhesion promoter is present in a weight ratio of about 1: 100 to about 2: 1 (and more specifically about 2:35 to about 7:25) parts of adhesion promoter for the prepolymer of aliphatic isocyanate. When used, the isocyanate-functional prepolymer with an isocyanate content greater than about 1% is present in a weight ratio of about 1: 140 to about 1: 1 (and more specifically about 2:55 to about 7:45) adhesion promoter parts for the isocyanate functional prepolymer. The solvent can be present in an amount of about 40 to about 80%, preferably about 50 to about 70% by weight. If used, diethyl malonate can be present in an amount of about 0.1 to about 0.5% by weight; the acid can be present in an amount of about 0.01 to about 0.05% by weight, or both. The invention also considers assemblies prepared according to the steps described above. Any of a number of substrates can be employed, such as glass, enamel, cured polyurethane, glass encapsulation materials, electrocoating, galvanic zinc coatings, aluminum, steel, paint, plastics, hard coated organic glazing. The invention also considers kits that include the primer described herein and at least one adhesive.

Detailed Description

Unless presented differently (for example, as a weight ratio), all parts by weight are based on 100 parts by weight of the mentioned composition. In the case of the resulting composition, this means that the weights are based on 100 parts by weight of the overall resulting composition. It will be understood that concentrates or dilutions of the quantities mentioned herein can be used. In general, the relative proportions of the ingredients mentioned will remain the same. Thus, as an example, if the teachings require 30 parts by weight of a Component A, and 10 parts by weight of a Component Β, the skilled technician will recognize that such teachings are also a teaching of the use of Component A and Component B for a reason relative ratio of 3: 1.

In general here, the compositions are based on the combination of an adhesion promoter with a primer-base that includes at least one prepolymer derived from the reaction of at least one polyisocyanate and at least one polyol, and particularly one that will have a content of free isocyanate. In a more particular aspect, the base primer includes an isocyanate-functional prepolymer derived from the reaction of an aliphatic polyisocyanate and a polyol. In a very specific embodiment, the base primer includes an isocyanate-functional prepolymer derived from the reaction of an aliphatic polyisocyanate and a polyol, and reacts at least partially with an amino group of a silane, and particularly an aminosilane (for example, a secondary aminosilane), where aminosilane includes a plurality of alkoxy groups attached to one or more silicon atoms (for example, two or three methoxy groups attached to silicon, two or three silicon-linked ethoxy groups, a combination of the same or similar). Examples of commercially obtainable primers that can be used in accordance with the present teaching include, without limitation, BETAPRIME ™ 5500 or BETAPRIME ™ 5404, commercially obtainable from The Dow Chemical Company.

Without claiming to be bound by theory, it is believed that the compositions here advantageously employ a particular molecular structure in which at least a portion of the molecule includes silicon (for example, it is silane), and a portion of the molecule includes functionality, such as as an isocyanate functionality, which is capable of binding with a primer-base such as through the molecular network of the primer-base.

In a specific aspect, the invention considers the use of a composition that includes a prepolymer that derives from the reaction of at least one aliphatic polyisocyanate and a polyol, and reacts at least partially with the active hydrogen of an organofunctional silane. The prepolymer can be part of a primer-base composition.

It is not necessary for any of such a primer-base composition to include such a polymer. In fact, more generally, the compositions are considered to include an isocyanate reaction product, and an isocyanate reactive compound.

The isocyanates useful here can be selected from diisocyanates, triisocyanates or any combination thereof. Suitable isocyanates can include an aliphatic, cycloaliphatic, araliphatic, heterocyclic, aromatic isocyanate, or any combination thereof. Particular examples may include an isocyanate selected from hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 4,4'-diphenyl methylene diisocyanate (MDI) or any combination thereof, and even more particularly one selected from isophorone diisocyanate (IPDI), 4,4'-diphenyl methylene diisocyanate (MDI), toluene diisocyanate (TDI), or any combination thereof. As noted, the polymeric derivatives of any of the isocyanates are also considered here.

Typically, isocyanates can have an amount

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Preferably, the isocyanates used have an average isocyanate functionality of at least about 2.0 and an equivalent weight of at least about 80. Preferably, the isocyanate functionality of the polyisocyanate is at least about 2.0, more preferably at least least about 2.2, and a lot

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cured is very brittle. Preferably, the equivalent weight of the polyisocyanate is at least about 100, more preferably at least about 110, and most preferably it is at least about 120; and preferably it is not greater than about 300, more preferably it is not greater than about 250, and most preferably it is not greater than about 200.

Exemplary isocyanate reactive compounds can be organic compounds having at least two isocyanate reactive moieties, such as a compound containing an active hydrogen moiety, or a compound with imino functionality (iminofunctional compound). For the purposes of this invention, a portion containing active hydrogen refers to a portion containing a hydrogen atom which, because of its position in the molecule, exhibits significant activity according to the Zerewitnoff test described by Wohler in the Journal of the American Chemical Society, volume 49, page 3181 (1927). Examples of such plots with active hydrogen are: -COOH, -OH, -NH₂, -NH-, -CONH₂, -SH, and -CONH-. Preferred compounds containing active hydrogen include polyols, polyamines, polymercaptan and polyacids. Suitable immunofunctional compounds are those that have at least one terminal imino group per molecule, as described, for example, in US Patent No. 4,910,279, which is incorporated herein by reference in its entirety.

Suitable polyols can include, for example, polyether polyols, polyester polyols, poly (alkylene carbonate) polyols, polyethers, polymeric polyols, and mixtures thereof. Polyether polyols can include, for example, one or more diols, triols or tetrols based on polyoxyethylene, polyoxypropylene, polyoxybutylene, and / or polytetramethylene ether. In general, polyether polyols are prepared by polymerizing alkylene oxides in the presence of an initiator compound containing active hydrogen. However, polyols capped with alkylene oxide are most preferred. Preferably, the isocyanate-reactive compound has a functionality of at least about 2.0, more preferably at least about 3.0, and preferably is not greater than about 5.0, mp is not greater than about 4 , 5, and most preferably it is not greater than about 4.0. Preferably, the equivalent weight of the isocyanate-reactive compound is at least about 200, more preferably at least about 500, and most preferably it is at least about 1,000; and preferably it is not greater than about 5,000, more preferably it is not greater than about 3,000, and most preferably it is not greater than about 2,500. A particular example employs an isocyanate-reactive polyol compound that has an equivalent weight of about 100 to about 1500, and more specifically about 300 to about 1000.

The isocyanate and the isocyanate-reactive compound can react in the presence of an appropriate catalyst. Catalysts for use here can include, for example, a metal complex such as a stannous or a stannous compound. Examples include a stannous salt of a carboxylic acid (eg stannous octoate, stannous oleate, stannous acetate, and stannous laurate), a trialkyl tin oxide, a tin dialkyl oxide (eg, dibutyl tin dilaurate, diacetate tin dibutyl tin, diethyl tin diacetate, and dihexyl tin diacetate), a dialkyl tin dihalide, or a dialkyl tin oxide, such as 2-ethylhexyl tin oxide or dioctyl tin oxide, a tertiary amine, or a tin mercaptid. Other catalysts can also be used. For example, tertiary amine catalysts include trialkylamines (e.g., trimethylamine, heterocyclics such as, N-methyl-morpholine, triethylamine), amines

N-alkyl-morpholines (for N-ethyl-morpholine, dimethyldiamino-diethyl ether, etc.), 1,4-dimethyl-piperazine, triethylenediamine, etc. As catalysts, aliphatic polyamines, such as Ν, Ν, Ν ', Ν'tetramethyl-1,3-butanediamine, can also be used. A most preferred catalyst includes a dibutyltin compound, and more specifically, it includes or consists essentially of dibutyltin dilaurate.

The isocyanate and the isocyanate-reactive compound can also react in the presence of an appropriate silane (for example, an aminosilane) to introduce silicon into the primer-base.

Here, the compositions can include one or more other ingredients, such as, a solvent, a stabilizer, a film former, a colorant (e.g. carbon black, e.g. RAVEN 420), a filler, an ultraviolet protector , or any combination thereof.

As an example, the solvent component of the primer composition is generally volatile and preferably is a solvent that will dissolve and / or disperse the components at a temperature in the range of about -10 ° C to about 100 ° C, more preferably about 0 ° C to about 40 ° C. Preferably, the solvent is anhydrous in order to help prevent the isocyanate from reacting prematurely with water. Examples of such solvents include xylene, ethyl benzene, toluene, ethyl acetate, propyl acetate, butyl acetate, butanol, propanol, isopropanol, ethanol, butoxy, 2-butoxy-ethanol, 3-methoxy-butyl acetate, NMP , n-heptane, kerosene, acetone, and methyl ethyl ketone, or any combination thereof, and is preferably butoxy, methyl ethyl ketone or a mixture thereof. The solvent will comprise the balance of any of the intermediate or resulting compositions and is preferably used in an amount of at least about 50%, more preferably at least about 55%, and most preferably at least about 60%; and preferably it is not greater than about 90%, more preferably it is not greater than about 85%, and most preferably it is not greater than about 80%, based on the weight of the total primer composition.

Here, the compositions may include one or more film-forming resins, which contain one or more portions capable of polymerizing, curing to form a continuous coating and which is resistant to many environmental forces. In a preferred embodiment, the film-forming resin preferably polymerizes when exposed to free radicals or cationic reaction conditions. In a specific aspect, the film-forming resin is a resin curable by exposure to irradiation, such as UV radiation or an electron beam. The film-forming resin may contain functional groups that polymerize when exposed to free radicals, such as portions containing vinyl, acrylate, styrene, diene, methacrylate, ally, thiolene, vinyl ether, unsaturated ester, imide, N-vinyl, acrylamide, mixtures of the same or similar. In a more preferred embodiment, the functional groups in the film-forming resin are acrylic and / or methacrylic portions. In many embodiments, the film-forming resin is an oligomer or prepolymer having the functional portions described. Preferred types of oligomers and prepolymers include urethane acrylates, such as aliphatic and aromatic urethane acrylates, epoxy acrylates, melamine acrylates, polyester acrylates, polyether acrylates, silicone acrylates, dendritic acrylates, polybutylene acrylates, amine, acrylic acrylates, spiro ortho carbonate esters and starch or mixtures thereof. A specific class of oligomers and prepolymers includes aliphatic urethane acrylates.

An example of a suitable commercially obtainable trainer is PARALOID® B48N, obtainable from The Rohm &amp; Haas Company.

The film-forming resin can be present in any suitable amount. For example, it can be present in an amount of about 0.1 part by weight, about 1 part by weight, about 5 parts by weight, or even about 10 parts by weight or more, based on the weight of the composition. primer. Preferably, the film-forming resin is present in the composition in an amount of about 70 parts by weight or less based on the weight of the primer composition and more preferably about 60 parts by weight or less, more preferably about 50 parts by weight. weight or less and most preferably 40 parts by weight or less of the primer composition.

Here, the compositions may optionally include one or more other ingredients, such as one or more stabilizers to help protect the adhesive composition from moisture, thereby inhibiting development and preventing premature cross-linking of isocyanates in the adhesive formulation. Here, stabilizers known to the skilled technician for moisture curing adhesives can be used. Such stabilizers include diethyl malonate, alkyl phenol alkylates, para-toluene sulfonic isocyanates, benzoyl chloride, orthoalkyl formats or any combination thereof. Preferably, such stabilizers are used in an amount of about 0.1 part by weight or more based on the total weight of the intermediate or resulting composition, preferably about 0.5 part by weight or more and more preferably about 0.8 part by weight or more. Such stabilizers are used in an amount of about 5.0 parts by weight or less based on the total weight of the intermediate or resulting composition, more preferably about 2.0 parts by weight or less and most preferably about 1.4 parts by weight. weight or less of the intermediate or resulting composition. For example, one option is to employ diethyl malonate in an amount of up to about 2 parts by weight, and more specifically from about 0.1 to about 1 part by weight (for example, from about 0.1 to about 0.3 part by weight). Optionally, it is also possible to employ an appropriate acid, such as phosphoric acid, for example, in an amount of up to about 0.2 part by weight, and more specifically of up to about 0.1 part by weight (for example, of about from 0.01 to about 0.05 part by weight). As indicated, the present invention makes particular use of an adhesion promoter, which is generally a reaction product of an organofunctional silane and an isocyanate. More specifically, as will be treated, the adhesion promoter includes at least one aromatic polyisocyanate, which more particularly includes phosphorus.

In an embodiment, an adhesion-promoting ingredient can include an aminosilane, and more particularly a secondary aminosilane. An attractive silane includes at least two silyl groups, with three methoxy groups attached to each of the silane groups, a secondary hindered amino group or any combination thereof. An example of such a commercially obtainable aminosilane is bis (trimethoxy silyl propyl) amine, such as SILQUEST A-1170, from GE Advanced Materials-Silicones. Additional information regarding silane materials suitable for use as an adhesion promoter is found in US Patent No. 4,374,237, incorporated herein by reference. Other examples of silanes include, without limitation, (alone or combined with bis (trimethoxy silyl propyl) amine), silanes having a hydroxy functionality, a mercapto functionality, or both, such as 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3- aminopropyl tris methoxy ethoxy ethoxy silane, 3-aminopropyl methyl diethoxy silane, N-methyl-3aminopropyl-trimethoxysilane, N-butyl-3-aminopropyl13 trimethoxysilane, 3-mercapto propyl triethoxysilane, 3mercapto propyl methyl dimethoxysilane, (N-cyclohexylaminomethyl) methyl dimethoxysilane, (N-cyclohexylaminomethyl) triethoxysilane, (N-phenyl aminomethyl) methyl dimethoxysilane, (N-phenyl aminomethyl) trimethoxysilane, Netyl amino isobutyl trimethoxysilane, 4 3,3-dimethyl butyl trimethoxysilane, or any combination thereof.

The adhesion promoter also includes, as one of its ingredients, an aromatic isocyanate, and particularly, a trifunctional isocyanate. In general, an example of such an isocyanate is described in US Patent No. 6,974,500, incorporated herein by reference, and which is represented by the following Formula 1:

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A possible isocyanate is tris (p-isocyanate) thiophosphan. A particularly preferred isocyanate is a thiophosphate with an isocyanate group such as a solution of tris thiophosphate (phenyl p-isocyanate) sold under the trade name DESMODUR RFE and commercially obtainable from Bayer Corporation, Pittsburgh, Pa. Other examples of possible isocyanates (which can be used alone or combined with tris thiophosphate (phenyl p-isocyanate)) include trifunctional isocyanates, which can be aromatic or aliphatic (for example, an aliphatic polyisocyanate based on HDI, and possibly having a content of about 15 to about 25% isocyanate). Examples of suitable trifunctional isocyanates include those commercially obtainable under the designations DESMODUR N 100, DESMODUR N 3300, or TOLONATE HDT.

In general, the adhesion promoter is prepared by mixing silane with the isocyanate, particularly in an amount of about 1 mol of isocyanate with about 1 to about 3 moles of silane (for example, aminosilane, mercaptosilane, or a combination thereof) , and more specifically about 1 mole of isocyanate with about 2.3 moles of silane (e.g., aminosilane, mercaptosilane, or a combination thereof).

A particular approach to preparing the adhesion promoter is to react at least partially an aromatic polyisocyanate having a functionality greater than about 2 with a silane (for example, aminosilane (such as a silane with secondary amino functionality), mercaptosilane, or a combination thereof ), with silane including a plurality of silicon-linked alkoxy groups (for example, two or three silicon-linked methoxy groups, two or three silicon-linked ethoxy groups, a combination of the same or similar).

The isocyanate-functional prepolymer with an isocyanate content greater than about 1% is generally the reaction product of a polyol having a functionality greater than about 2 and a molecular weight (M_n) greater than about 300 and an isocyanate, and more specifically an aromatic polyisocyanate. Here, the second prepolymer will generally be an isocyanate prepolymer and particularly a reaction product of an isocyanate and a polyol. In a specific aspect, the preferred isocyanate will be a diisocyanate, such as one having a functionality of at least about 2 (for example, a trifunctional diisocyanate). For example, the diisocyanate can be an aromatic diisocyanate, such as one selected from TDI, MDI or a combination thereof. A preferred specific diisocyanate includes MDI or a prepolymer thereof, such as one that includes approximately 97% 4,4'-diphenyl methane diisocyanate and 3% 2,4'-diphenyl methane diisocyanate. A commercially obtainable example of such an isocyanate is MDI ISONATE® M125, obtainable from The Dow Chemical Company. polyols may be preferred will be

Although others are particularly selected, one a triol, and particularly one having a hydroxyl number of at least about 200. An example of such a polyol is obtainable from The Dow Chemical Company, under the trade name VORANOL ™ CP260.

Typically, the adhesion promoter will be employed in an amount of about 20% by weight of the total composition, more specifically from about 1 to about 10% by weight, and even more specifically from about 2 to about 7 % by weight. The skilled technician will understand, particularly with respect to the amounts of adhesion promoters employed here, that greater or lesser amounts may be employed. For example, an adhesion promoter that does not use any solvent may be used in an amount less than an adhesion promoter that employs a solvent.

In turn, the primer-base will typically be used in an amount of about 30 to about 90% by weight of the total composition, more specifically from about 40 to about 80% by weight, and even more specifically from about 55 to about 65% by weight.

In turn, the isocyanate-functional prepolymer with an isocyanate content greater than about 1% will typically be employed in an amount of about 10 to about 60% by weight of the total composition, more specifically about 20 to about 50% by weight, and even more specifically from about 30 to about 40% by weight.

In general, the adhesion promoter is present in a weight ratio of about 1: 100 to about 2: 1 (and more specifically about 2:35 to about 7:25) parts of adhesion promoter for pre- aliphatic isocyanate polymer. When employed, the isocyanate-functional prepolymer with an isocyanate content greater than about 1% is present in a weight ratio of about 1: 140 to about 1: 1 (and more specifically about 2:55 to about 7:45) adhesion promoter parts for isocyanate functional prepolymer. A particular preferred composition includes the primer-base, the adhesion promoter, the isocyanate-functional prepolymer with an isocyanate content greater than about 1%, a stabilizer and an acid. More specifically, the stabilizer will include diethyl malonate, the acid will include phosphoric acid, or both. For example, the primer-base can be present in an amount of about 50 to about 65% by weight and more specifically from about 55 to about 60% by weight (for example, about 57.9% by weight) . The adhesion promoter will be present in an amount of about 2 to about 7% by weight, and more specifically about 4 to about 6% by weight (e.g., about 5.2% by weight). 0 isocyanate-functional prepolymer with an isocyanate content greater than about 1% will be present in an amount of about 30 to about 40% by weight, and more specifically from about 33 to about 38% by weight (for example , about 33.6% by weight). The composition may also include from about 0.1 to about 0.5% by weight of diethyl malonate (for example, about 0.25%) and from about 0.01 to about 0.05% by weight. weight of phosphoric acid (for example, about 0.03% by weight).

Here, primer compositions can be employed in any of a number of applications. A particular approach is to apply the primer composition (for example, as a one-part composition), using methods disclosed in the art, on a substrate for use in an automotive vehicle windshield, rear light, side window, sunroof, architectural window, skylight , hatch (porthole), door opening, display box, lens or others. Another useful application is for printing labels, packaging, containers (for example, beverage bottles), or others. Here, a preferred application is the use of primer compositions to assemble sets of substantially transparent panels. Here, the sets can be adapted for temporary or permanent assembly in a structure, they can be adapted to open, close,

The sets or move differently, for example, sliding, articulating, rotating, bending, or any combination thereof. Thus, the sets can be used in one or more applications such as taillights for automotive vehicles, side windows, sunroofs, architectural windows, skylights, hatches (portholes), door openings, display boxes, or others. Here, compositions and methods are also particularly useful in combination with pre-applied adhesive systems, on a substrate that has received an electrostatically primer (i.e., an electrocoat), a painted substrate or any combination thereof. Typically, the substrates will be substantially flat or shaped, for example, to define a curved surface. In general, the substrates will be transparent panels across at least one surface, and particularly across both opposing surfaces, at least about 25% of the surface area, and more specifically, at most (for example, at least about 60%, 75% or even 90% of the surface area). Here, the substrates will be made of a substantially amorphous material, and in particular amorphous ceramics (such as glass), plastic, or a combination thereof. Without limitation, examples of suitable substrate materials include poly (meth) acrylates, polycarbonates, vinyls (for example, poly (vinyl chlorides)), polyesters (for example, oriented polyesters), polyimides, polyolefins, polyamides, glass, any combinations of them (for example, laminated glass), or the like. In a particular example, the substrates include or even consist essentially of a material selected from glass, poly (meth) acrylates, polycarbonates or any combination thereof. The substrates can have a laminate layer, paint or any combination thereof. The substrates can also be a reaction injection molded plastic. Assemblies that include reaction injection molded parts encapsulating a panel, such as a substantially transparent panel, can be bonded according to the teachings here. An example of a possible approach to the manufacture of encapsulated panels is disclosed in US serial patent application n ° 60 / 870,643 (entitled: ENCAPSULATED PANEL ASSEMBLIES AND METHODS FOR MAKING SAME (Encapsulated panel assemblies and methods for producing them) incorporated herein by reference). Here, the compositions can also be used to bond a surface of a welded assembly by mechanical tightening.

Although some applications may require the coating of substantially an entire surface of a substrate with the composition here, in general, the compositions will be selectively applied to the substrates, according to a predetermined pattern (for example, substantially along an edge portion of the substrate, around the periphery of the substrate, or differently). For example, one approach is to apply the composition of the substrate edge inward towards the central portion · in a width of about 2, 5, 8, or even 12 cm or more. It is possible that the composition may be applied to define one or more lines, curves, points, or other geometric configurations comprising segments of width, height, length or other constant or variable dimensions.

Any of a variety of standards disclosed in the art can be applied. The primer composition can be applied to a substrate (for example, glass or coated plastic) using any medium disclosed in the art, such as using a brush, roller, sprayed on the surface, inkjet printing, canvas printing and the like. It can be applied using robotic application devices disclosed in the art (for example, one having at least 2 axes of movement). After applying the composition to the substrate surface, it is exposed to polymerization conditions.

treated for primer composition, plasma spraying, or meanwhile, in an external treatment of

Here, the substrates will typically include at least one surface on which the composition is applied. Optionally, the surface can be improve the bond strength of the substrate, for example by flame, crown treatment, some other surface treatment, specific example, the surface substantially free of any surface. Consequently, in response to the application, the composition is in direct intimate contact with the substrate, and particularly in the substantial absence of any intermediate interfacial layer. Obviously, after applying the composition to the substrate, it is also possible to apply, on part or all of one or both of the composition and substrate, an additional layer (for example, silicone, acrylic, polyurethane, or other, to result in a protective overlay). Here, it is also possible that the composition can be used on, under, and / or adjacent to an inorganic or organic frit (for example, a frit of the type taught in serial co-pending patent application No. 11 / 472,119, filed in June 20, 2006 (priority for 60 / 692,318, deposited on June 20, 2005), by Baikerikar et al. (incorporated by reference).

Here, when applied, the composition will generally have a thickness of up to about 250 microns or more. Most commonly, it will be less than about 150 microns thick, less than about 100 microns or even less than about 50 microns (for example, about 10 to about 30 microns or less).

Examples of adhesives or sealants suitable for use in combination with the primer compositions of the present invention include, without limitation, one-part or two-part urethane compositions, which in turn can be cured wet. Particularly preferred urethanes are based on MDI, HMDI, or a combination thereof.

Examples of commercially obtainable adhesives include, without limitation, those obtainable from The Dow Chemical Company under the name BETASEAL ™ such as or more than grade No. 1759, 1841, 1843, 1965, 2002, or 2002 LVPR.

The invention also envisages kits that include an adhesive or sealant composition and one or more primer compositions. For example, such a kit may include one or more primer compositions according to the present invention, with or without the adhesive or sealant composition (for example, a one-part urethane adhesive or a two-part urethane adhesive). It is also possible to include one or more cleaners, applicators, tapes, tools or any combination thereof. Here, the compositions can be provided in a cartridge, thin sheet package, or both.

Here, the compositions provide an abrasion resistant and generally hard coating. It is also expected that the compositions will exhibit excellent adhesion performance and weather resistance. The resulting primer materials prepared recently in accordance with the teachings here are also expected to have good storage stability.

The resulting compositions have: (I) a solids content in the range of about 30 to about 50%, and more specifically about 37 to about 43% (for example, about 40.4%) (measured by ISO 3251); (II) an isocyanate content of about 1 to about 7%, and more specifically about 3.0 to about 3.6% (for example, about 3.26%) (measured by ISO 11909 ); (III) a density of about 0.92 to about 0.95 g / cm³, and more specifically from about 0.934 to about 0.944 g / cm³ (for example, about 0.939 g / cm³) (measured by ISO 2811); a silane content (e.g. trimethoxysilane) of about 1 to about 5%, more specifically about 2.4 to about 3.0% (and even more specifically, when using a trimethoxysilane group, it will be present in an amount of about 2.71%) (measured by ASTM D 6843-02, ASTM D 684402 or both); or (V) any combination of (I) to (IV).

The resulting samples show 100% cohesive failure after 7 days of aging at room temperature; more preferably, also after another 7 days subjected to immersion in water; even more preferably after aging for another 7 days at 90 ° C; even more preferably, also after another 7 days of poultice cycling. Here it is also possible that compositions will show 100% cohesive failure even after another 14 days of poultice cycling.

In general, for poultice cycling, samples are stored directly in a climatic chamber at 70 ° C, 100% relative humidity, for 7 days, or wrapped in cotton wool, moistened with enough water and closed in a polyethylene bag for thereafter be closed in an oven at 70 ° C for 7 days. Then, the samples are placed in a freezer for 16 hours at -20 ° C, after which the samples are allowed to remain at room temperature for 2 hours. The cycle is repeated several times, after which the samples are removed from the bag and subjected to the rapid knife adherence test. Desirably, there is no blistering of the primer layer and the failure is cohesive in the sealing layer.

Here, the following examples illustrate the teachings. Similar results are believed to be possible for compositions in which the amounts of the ingredients vary within the limits of about 10 or even about 25% of the amounts mentioned. Thus, the examples also teach a range of concentrations that would fall within the limits of such variation.

Examples

An example primer composition is prepared by reacting: (a) about 57.9% by weight of BETAPRIME ™ 5500; (b) about 36.6% by weight of the reaction product of VORANOL ™ CP260 and an aromatic diisocyanate (for example, MDI ISONATE® M125); (c) about 5.2% by weight of the reaction product of

DEMODUR® RFE and SILQUEST® A1170; about 0.25% by weight of diethyl malonate; and about 0.03% by weight of phosphoric acid.

Several windshields from different vendors are provided, with ceramic frit applied to them. BETACLEAN ™ 3300 (obtainable from The Dow Chemical Company) is applied to clean the windshields, and rapid evaporation is allowed for about 2 minutes at about 23 ° C and about 50% relative humidity. The sample primer composition is applied and after an exposure time to air of about 15 minutes, an adhesive bead (BETASEAL ™ 1965 (obtainable from The Dow Chemical Company)) is applied and the samples are prepared for testing exfoliation described here. After seven days of aging at room temperature, samples are expected to exhibit at least 75% cohesive failure, and more specifically at least 10 %% cohesive failure for each of them. Likewise, most samples are also expected to be able to withstand 100% cohesive failure with an additional 7-day poultice cycle.

The sample primer composition for resistance to exfoliation in samples is analyzed using an injection-molded polyurethane substrate with reaction as found in an encapsulated window assembly. Just to compare, here the adhesion promoter is mixed with commercially obtainable primers (indicated as primer 1 and primer 2) from different vendors, and used with commercially obtainable sealants (indicated as adhesive 1, adhesive 2 and adhesive 3). First, the substrates are cleaned with BETACLEAN ™ 3900. Primer is applied and quickly dried in air for 15 minutes at 23 ° C and 50% relative humidity, before applying the sealant. Then, the samples are tested. The samples are expected to display the results in the following table. BM 7120 refers to BETAMATE ™ 7120, obtainable from The Dow Chemical Company, BM 2700 refers to BETAMATE ™ 2700, obtainable from The Dow Chemical Company, BS X 1502 refers to BETASEAL ™

X 1502, obtainable from The Dow Chemical Company, BP 5504 refers to BETAPRIME ™ 5504, modified in accordance with the teachings here. BETAPRIME ™ 5504 modified according to the teachings here (BP 5504) 5 is expected to allow the primer to achieve 100% cohesive failure when bonded to commercially obtainable seals from a source other than The Dow Chemical Company, when aged for 7 days at room temperature, immersion in water for another 7 days (at 23 ° C), another 7 days at 10 90 ° C and a poultice cycle of another 7 days. Table 1 below illustrates the expected results when using commercially obtainable non-modified primers (primer 1 and primer 2) from a source other than The Dow Chemical Company.

Table 1: Expected results_

<td>Cleaning</td><td>Primer</td><td>Sticker</td><td>7d. RT</td><td>+ 7d. H₂O</td><td>+ 7d. 90 ° C</td><td>+ 7d. Cat</td>

<td>BC 3900</td><td>BP 5504</td><td>Sticker 1</td><td> 5</td><td> 5</td><td> 5</td><td> 5</td>

<td>BC 3900</td><td>BP 5504</td><td>Sticker 2</td><td> 5</td><td> 5</td><td> 5</td><td> 5</td>

<td>BC 3900</td><td>BP 5504</td><td>Sticker 3</td><td> 5</td><td> 5</td><td> 5</td><td> 5</td>

<td>BC 3900</td><td>BP 5504</td><td>BS X 1502</td><td> 5</td><td>4-5a</td><td> 5</td><td>4-5a</td>

<td>BC 3900</td><td>BP 5504</td><td>BM 7120</td><td> 5</td><td> 5</td><td> 5</td><td> 5</td>

<td>BC 3900</td><td>BP 5504</td><td>BM 2700</td><td> 5</td><td> 5</td><td> 5</td><td> 5</td>

<td>BC 3900</td><td>primer 1</td><td>BS X 1502</td><td>1-a</td><td>1-a</td><td>1-a</td><td>over there</td>

<td>BC 3900</td><td>primer 1</td><td>BM 7120</td><td>1-a</td><td>1-a</td><td>3rd</td><td>over there</td>

<td>BC 3900</td><td>primer 1</td><td>BM 2700</td><td>lb</td><td>2-a</td><td>3rd</td><td>l-2a</td>

<td>BC 3900</td><td>primer 1</td><td>Sticker 1</td><td> 5</td><td>3-4a</td><td>4-5b</td><td> 5</td>

<td>BC 3900</td><td>primer 1</td><td>Sticker 2</td><td> 5</td><td>3-4ab</td><td> 5</td><td>4-5a</td>

<td>BC 3900</td><td>primer 1</td><td>Sticker 3</td><td> 5</td><td>2a</td><td>3b</td><td>3b</td>

<td>BC 3900</td><td>primer 2</td><td>BS X 1502</td><td>2-3a</td><td>2-3a</td><td>over there</td><td>1-a</td>

<td>BC 3900</td><td>primer 2</td><td>BM 7120</td><td>2-3a</td><td>2-3a</td><td>2-a</td><td>1-a</td>

<td>BC 3900</td><td>primer 2</td><td>BM 2700</td><td>2-a</td><td>2-3a</td><td>2-a</td><td>1-a</td>

The example primer composition is compared with other commercially obtainable adhesive systems (eg BETASEAL ™ 2002 and 2002 LVRP) for performance and is expected to exhibit 100% cohesive failure after aging for 7 days at room temperature (50% relative humidity ), seven more days subject to immersion in water (at 23 ° C), another 7 days at 90 ° C, and another 7 days of poultice cycling. Here, for performance analysis of primers with pre-applied adhesive systems, chrome steel substrates are provided that are cleaned with BETACLEAN ™ 3350 (obtainable from The Dow Chemical Company), and allowed to air dry for 2 minutes at 23 °. C and about 50% relative humidity. After that, the substrates receive the primer BETAPRIME ™ 17 07 (obtainable from The Dow Chemical Company). After an air drying time of 30 minutes, a pre-applied adhesive is applied over BETAPRIME ™ 1707 (for example, an adhesive such as HV3 pre-applied adhesive, obtainable from The Dow Chemical Company). The samples are then aged for 10 weeks at 32 ° C and about 80% relative humidity. The sample primer composition is then applied to the pre-applied adhesive, followed by a BETASEAL ™ 1965 bead (obtainable from The Dow Chemical Company). The samples are prepared and subjected to the exfoliation test described below, and also measured for resistance to exfoliation with a ZWART.PRO traction analyzer from Zwick / Roell. For samples using the example primer composition, they are expected to exhibit 100% cohesive failure after an additional 7 days of aging by cycling the poultice described here. They are also expected to exhibit resistance to exfoliation of at least about 19 to about 23 N / cm after 7 days of aging at room temperature. They are also expected to exhibit resistance to exfoliation of at least about 16 to about 21 N / cm after an additional 7 days of aging by cycling the poultice as described herein. For comparison, the example primer composition is replaced by a commercially available unmodified primer (BETAPRIME ™ 5404). It is expected to exhibit resistance to exfoliation after aging for 7 days at an ambient temperature of about 15 to about 23 N / cm, and from about 11 to about 19 N / cm after an additional 7 days of aging by cycling the poultice as described here. Additionally, it is expected that the commercially obtainable unmodified adhesive will exhibit about 25 to about 75% of cohesive failure after 7 days of aging at room temperature, and zero% of cohesive failure after another 7 days of aging by poultice cycling as described here.

An adhesion exfoliation test is carried out, through which an adhesive bead of about 10 to about 15 mm in height and about 100 to about 150 mm in length is applied to a substrate already primed (specifically a float glass to which the primer compositions were applied from here using a felt applicator) about 3 minutes before applying the primer. The adhesive is spread to a height of about 4 to about 6 mm with a spatula, and then aged in a climatic chamber for about 7 days at about 23 ° C and about 50% relative humidity. The set is cured for a specific time under the desired conditions. After that, the bead is peeled using pointed-nose pliers, which hold the bead and pull the bead while rotating at an angle of about 90 °. The bead is then cut with a razor blade across the primed surface, with cuts at intervals of about 1 cm. The area of ​​cohesive force is calculated based on the percentage of the total area analyzed. The degree of adherence is assessed as adhesive failure and / or cohesive failure. In the case of adhesive failure, the cured bead can be separated from the primed surface, whereas in cohesive failure, separation occurs within the seal bead as a result of cutting and pulling. Observing the failure mode, it is noted in which portion of the interfacial surface area the failure mode is observed. Primer failure is considered to have occurred if the primer delaminates the substrate (eg glass) to which it is applied.

The explanations of illustrations presented here are intended to bring together those skilled in the art with the invention, its principles, and its practical application. Those skilled in the art can adapt and apply the invention in its numerous forms, using the form most appropriate to the requirements of a particular use. Consequently, specific embodiments of the present invention shown are not intended to exhaust or limit the invention. Therefore, the scope of the invention should be determined not with reference to the above description, but instead be determined with reference to the appended claims, together with the full range of equivalents to which such claims are entitled. Disclosures of all articles and references, including publications and patent applications, are incorporated by references for all purposes. References to an acrylic or (meth) acrylic (or derived terms such as acrylate) refer to acrylics and methacrylics (and corresponding derived terms). The ingredients discussed herein can form part of the resulting composition. However, they can also form part of an additive for the resulting composition. For example, it is possible that the adhesion promoter is a vehicle for releasing an ingredient in a mixture to form the resulting composition. Unless stated otherwise, references to adhesive or sealant are interchangeable. Thus, the mention of an adhesive of a composition also covers a sealant of such a composition. Although disclosed here in the context of use in a one-step primer composition, here the adhesion promoters are not so limited. They can also be used as part of a primer system that includes multiple components, and can be added to any or all components. For example, the adhesion promoter can be incorporated into a urethane activator composition, a fry preparation composition, a fry primer composition, a PVC primer, a mechanical compression welded primer, or differently, such as one or more products from The Dow Chemical Company which were sold under the designation U413, U-555, U-4000, U-401, U-402 or similar.

The teachings here can be appropriately employed in combination with or both of co-pending provisional patent application No. 60 / 913,700 (filed April 24, 2007), (Attorney Document No.

64676: One Component Glass Primer Including Oxazolidine (One-component glass primer including oxazolidine); or Copending Provisional Patent Application No. 60 / 913,706 (filed April 24, 2007), (Attorney Document No. 65694: Improved Primer Adhesion Promoters, Compositions and Methods (Improved primer adhesion promoters,

Compositions and Methods)), both of which are incorporated herein by reference.