KR20000052900A - Liquid cross-linker compositions containing 1,3,5-triazine carbamate/aminoplast resin mixtures - Google Patents

Abstract

PURPOSE: High solids, liquid cross-linker compositions based on mixtures of 1,3,5-triazine carbamates and aminoplast resins and processes for preparing it are provided. CONSTITUTION: A aforementioned industry need by providing a crosslinker composition comprises a liquid, substantially homogenous mixture of: (i) a 1,3,5-triazine carbamate, (ii) an aminoplast resin and (iii) optionally an organic solvent, the crosslinker composition having a solids content of at least about 65 wt% based on the total weight of the crosslinker composition, the combination of (i) and (ii) comprising at least 50 wt% based on the total weight of the crosslinker composition, and the weight ratio of (i):(ii) being in the range of from 1:99 to 99:1. In addition to the above three components, the inventive crosslinker compositions may also contain other optional ingredients, for example, cure catalysts, light stabilizing additives, antioxidants, anitfoaming agents and other additives and adjuvants normal to the particular chosen end use of the crosslinker composition, to the extent that the crosslinker composition remains within the parameters.

Description

LIQUID CROSS-LINKER COMPOSITIONS CONTAINING 1,3,5-TRIAZINE CARBAMATE / AMINOPLAST RESIN MIXTURES} 1,3,5-triazine carbamate / aminoplast resin mixture

Various derivatives of amino-1,3,5-triazines are described in the literature as having a wide variety of uses. Aminoplast resins comprising certain of these derivatives, such as alkoxymethyl derivatives of melamine and guanamine, are useful as crosslinkers or reactive modifiers in curable compositions containing resins having active hydrogen groups. For example, US4064191, US4081426, US4101520, US4118437, US4129681, US4243705, US4271277, US4276212, US4330458, US4374164, US4433143, US4425466, US4873298, US5155201, US5256713 and WO96, all of which are hereby incorporated by reference for the purposes herein. See / 41826.

Although alkoxymethylated melamine and guanamine provide good results in many embodiments, they also have the disadvantage of releasing formaldehyde as volatile byproducts under curing conditions. Particularly advantageous and highly preferred are crosslinkers which minimize the release of formaldehyde but also retain the advantageous performance properties of alkoxymethylated melamine and guanamine.

One promising non-formaldehyde release alternative is US4939213, US5084541, US5288865, US5556971, US5565243, US5574103, EP-A-0624577, EP-A-0649842, WO96 / 04258, which are incorporated herein by reference for the purposes as if fully described. Is a class of isocyanate and carbamate functional 1,3,5-triazine crosslinkers described in WO96 / 11915, WO96 / 15186 and WO97 / 08235. The above has been found to be particularly useful as crosslinking agents in coating compositions based on active hydrogens and / or epoxies containing compounds having a broad range of desirable properties.

In many of the references cited above, it is understood that curable compositions containing multifunctional active hydrogen and / or epoxy compounds and 1,3,5-triazine carbamate crosslinkers can be applied for use in organic solvent based coating compositions. It is described. For example, US 5574103, cited above, describes organic solvent based coatings prepared from organometallic, base or acid catalyst systems using 1,3,5-triazine carbamate crosslinkers. It is also combined with conventional aminoplast resin crosslinkers to improve acid etch resistance and lower formaldehyde release of traditional organic solvent based aminoplast crosslinking systems as 1,3,5-triazine carba as a co-crosslinker. The use of mate is described herein.

Solvent based coating compositions are typically prepared by mixing a substantially homogeneous solution of crosslinker in a suitable organic solvent with the remaining components. However, due to the generally low solubility of 1,3,5-triazine carbamate crosslinkers in most common organic solvents, only relatively low solid solutions of 1,3,5-triazine carbamate precipitate during storage. Can be used without problems.

When such a low solid solution is used to formulate the coating composition, a large amount of unnecessary organic solvent can be introduced into the coating formulation, and the end result is that the organic solvent content of the final coating can be increased. Due to the increasing interest in organic solvent release, this result is undesirable. Since the 1,3,5-triazine carbamate crosslinker imparts desirable properties to the final crosslinked film, lower organic solvents containing alternatives for use in formulation will be highly desirable.

An alternative approach is the use of 1,3,5-triazine carbamate in the solid state to prepare the coating composition directly without first producing a homogeneous 1,3,5-triazine carbamate solution. However, this is generally more difficult to deliver solids than homogeneous liquids, and thus has the disadvantage of being inconvenient to use. Solid 1,3,5-triazine carbamate is also expensive to prepare. In addition, generally solid 1,3,5-triazine carbamate, and especially mixed solid 1,3,5-triazine carbamate, may tend to agglomerate on storage, making delivery or dissolution particularly difficult. .

Given the inverse environmental impact of VOC emissions and the difficulties associated with the use of 1,3,5-triazine carbamate in solid form, it provides an end-user with the flexibility to use a number of conventional coating solvents. High solids and low VOCs that can be conveniently prepared and used in curable compositions such as coating compositions that can be adapted for application by conventional spraying techniques commonly used in OEM (OEM) and other related applications. -Contains a liquid, liquid 1,3,5-triazine carbamate crosslinker composition. The present invention provides such liquid crosslinker compositions.

The present invention

(i) 1,3,5-triazine carbamate,

(ii) aminoplast resins and

(iii) a liquid crosslinker, optionally comprising a substantially homogeneous mixture of organic solvents (the crosslinker composition has a solids content of at least about 65% by weight, based on the total weight of the crosslinker composition, of (i) and (ii) The formulation comprises at least 50% by weight, based on the total weight of the crosslinker composition, wherein the weight ratio of (i) :( ii) ranges from 1:99 to 99: 1) to meet the above-mentioned industrial needs. . In addition to the three components mentioned above, the crosslinker composition of the present invention is also conventional for particularly selected end use of other optional components, such as curing catalysts, light weight stabilizing additives, antioxidants, antifoaming agents and other additives and crosslinker compositions. The phosphorus adjuvant may be contained to such an extent that the crosslinker composition is maintained within the above parameters.

The present invention also provides a substantially homogeneous liquid crosslinker having 1,3,5-triazine carbamate, an aminoplast resin and optionally an organic solvent having a solids content of at least about 65% based on the total weight of the crosslinker composition. Substantially homogeneous liquid phase crosslinker comprising the step of mixing at a temperature and time sufficient to produce (the crosslinker composition has a solids content of at least about 65% by weight based on the total weight of the crosslinker composition, (i) and ( the blend of ii) comprises at least 50% by weight, based on the total weight of the crosslinker composition, wherein the weight ratio of (i) :( ii) ranges from 1:99 to 99: 1). .

Also included are liquid curable compositions comprising a substantially homogeneous mixture of (I) a poly (active hydrogen and / or epoxy) compound and (II) a substantially homogeneous liquid crosslinker composition. These curable compositions according to the present invention can be used in a wide variety of fields, as described in a number of previously cited references. Particularly preferred terminal uses are one- or two-component spray coatings for elevated temperature curing applications, for example production (OEM) pigmented basecoats and clearcoats of automobiles.

These and other features and advantages of the present invention will be more readily understood by those skilled in the art from the reading of the following detailed description.

FIELD OF THE INVENTION The present invention generally relates to crosslinker compositions and methods for the preparation thereof that contain substantially homogeneous mixtures of 1,3,5-triazine carbamate and aminoplast resins. The invention also relates to a process for preparing the curable coating composition derived from the crosslinker composition of the invention and to a method for coating the substrate.

Crosslinker composition

The crosslinker composition of the present invention is a substantially homogeneous liquid composition comprising 1,3,5-triazine carbamate, aminoplast and optionally an organic solvent. The crosslinker compositions according to the invention can be prepared using formulations and / or ratios of the above components, provided that such formulations produce a composition of substantially homogeneous liquid that meets the above parameters.

For classification purposes, the term "liquid" as used in the context of the present invention is defined as a mixture which can be followed at room temperature. Preferably such mixtures have a viscosity of about 32,000 centipoise (cps) or less at 25 ° C. or less, and about 16,000 centipoise (cps) or less at 25 ° C. as measured by a Brookfield viscometer according to ASTM D2196.

The crosslinker composition of the present invention is determined by ASTM D4713 (method B) of at least about 65% by weight, more preferably at least about 70% by weight and especially at least about 75% by weight based on the total weight of the crosslinker composition It is a high solid composition containing a solid.

In a preferred embodiment, the crosslinker composition of the invention is substantially free of organic solvents (at least 95% by weight, and preferably essentially 100% by weight solids content), and the aminoplast resin is a liquid flask resin, The weight ratio of 1,3,5-triazine carbamate to aminoplast resin is about 1:99 to about 80:20 and more preferably about 1:99 to about 50:50, especially about 5:95 to about 25 : 75.

In another preferred embodiment, the crosslinker composition of the present invention comprises an organic solvent and 1,3,5-triazine carbamate and aminoplast resin in an amount of about 35% by weight or less (more preferably about 10 to about 30% by weight). A blend of about 50 to about 90 weight percent (more preferably about 65 to about 90 weight percent), wherein the weight ratio of 1,3,5-triazine carbamate to aminoplast resin is about 20:80 to about 99: 1 and more preferably about 25:75 to about 90:10.

1,3,5 triazine carbamate

1,3,5-triazine carbamate suitable for use in the present invention is described in US4939213, US5084541, US5288865, US5556971, US5565243, US5574103, EP-A-0624577, EP-A-0649842, WO96 / 04258, WO96 / 11915, WO96 / 15186 and WO97 / 08235. 1,3,5-triazine carbamate of Formula 1 and oligomers thereof are preferred for use in the present invention.

In the above formula,

R is selected from the group consisting of -NHCOOR ³ , hydrogen, hydrocarbyl, hydrocarbyloxy, hydrocarbylthio, amido, sulfonamido, amino, hydrocarbylamino, dihydrocarbylamino and hydrocarbyleneamino (cyclic amino) Selected,

Each of R ¹ , R ² and R ³ is independently selected from hydrocarbyl groups.

Within the context of the present invention and in the above formula the term "hydrocarbyl" means a group containing at least carbon and hydrogen atoms and includes, for example, aliphatic, cycloaliphatic, aromatic and mixed property groups. "Hydrocarbyl" includes, for example, alkyl, cycloalkyl, aryl, aralkyl, alkaryl, alkenyl and cycloalkenyl, preferably having up to 20 carbon atoms. As illustrated below, these groups may contain heteroatoms in the chain, such as oxygen, sulfur or nitrogen.

In a more preferred embodiment, R is -NHCOOR ³ ; Hydrogen; Hydrocarbyl having 1 to 20 carbon atoms; Hydrocarbyloxy having 1 to 20 carbon atoms (eg, methoxy and phenoxy); Hydrocarbylthio (eg, methylthio and phenylthio) having 1 to 20 carbon atoms; Amido groups having 1 to 20 carbon atoms (eg, acetamido); Sulfonamido (eg, benzene sulfonamido) having 1 to 20 carbon atoms; Amino group; Hydrocarbylamino groups having 1 to 20 carbon atoms (eg, methylamino, butylamino, methylamino, methoxymethylamino and butoxymethylamino); Each hydrocarbyl group having 1 to 20 carbon atoms (dimethylamino, dibutylamino, methylbutylamino, dimethylolamino, dimethoxymethylamino, dibutoxymethylamino, (methylol) ( Methoxymethyl) amino and (methoxymethyl) (butoxymethyl) amino); And cyclic amino groups having 3 to 20 carbon atoms (eg, pyrrolidino, piperidino, morpholino and azefino). Preferred hydrocarbyls (as part of these or other groups, as -oxy and -amino groups) are alkyl having 1 to 20 carbon atoms (eg methyl and butyl), aryl having 6 to 20 carbon atoms (eg Phenyl), cycloalkyl having 4 to 20 carbon atoms (eg cyclohexyl), alkenyl having 2 to 20 carbon atoms (eg vinyl) and 7 to 20 carbon atoms Having aralkyl (eg benzyl).

R is —NHCOOR ³ , hydrogen, alkyl of 1 to 20 carbon atoms, cycloalkyl of 5 to 20 carbon atoms, alkenyl of 3 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, 7 to 20 Even more preferred is selected from aralkyl and amino groups of carbon atoms. Particular preference is given when R is -NHCOOR ³ .

Preferred groups R ¹ , R ² and R ³ , for example hydrocarbyl groups having 1 to 20 carbon atoms, for example alkyl (eg methyl and butyl), aryl (eg phenyl) Cycloalkyl (eg cyclohexyl), alkenyl (eg vinyl), aralkyl (eg methyl phenyl), alkaryl (eg phenylmethyl), hydroxyalkyl (eg For example, methylol), hydroxyaryl (eg hydroxyphenyl), alkoxyalkyl (eg methoxymethyl and butoxymethyl), aryloxyalkyl (eg phenoxymethyl), hydroxy Alkoxyalkyl (eg hydroxypropoxymethyl) and hydroxyaryloxyalkyl (eg hydroxyphenoxymethyl) may be mentioned.

Particularly preferred groups of R ¹ , R ² and R ³ are alkyl having 1 to 8 carbon atoms, alkenyl having 2 to 8 carbon atoms, cyclic alkyl and alkenyl having 4 to 12 carbon atoms, 2 Alkoxyalkyl having from 16 to 16 carbon atoms, aryl having 6 to 18 carbon atoms, aralkyl having 7 to 20 carbon atoms and aralkyl having 7 to 20 carbon atoms. Particularly preferred examples include methyl, ethyl, propyl, n-butyl, i-butyl, t-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, ethylhexyl, allyl, ethoxyethyl, hydroxyethoxyethyl, 1- Mention may be made of methoxy-2-propyl, phenyl, 2-methyl phenyl, 3-methyl phenyl, 4-methyl phenyl and dimethylphenyl.

Particularly preferred 1,3,5-triazine carbamate crosslinkers for use in the present invention are those wherein R is -NHCOOR ³ and R ¹ , R ² and R ³ are independently alkyl having from 1 to 8 carbon atoms, preferably Preferably a compound of formula 1 which is methyl and / or butyl, tris- (butoxycarbonylamino) -1,3,5-triazine, tris- (methoxycarbonylamino) -1,3,5-tri Azine and tris- (methoxybutoxycarbonylamino) -1,3,5-triazine. Preferred examples of the latter include 1,3,5-triazine carbamate and especially in the range of about 0.65 to about 1.2, with a methyl to butyl molar ratio (measured with a nuclear magnetic resonance (NMR) spectrophotometer) in the range of about 0.50 to about 1.5 Mention may be made of having a methyl to butyl molar ratio of.

These 1,3,5-triazine carbamates are described, for example, in the methods described in US4939213, US5084541, US5288865, US5556971, EP-A-0624577, EP-A-0649842, WO96 / 04258, and WO96 / 11915. Can be prepared and will be mentioned in more detail herein.

Aminoplast resin

As suitable aminoplast resins, mention may be made of partially or substantially fully methylolated, partially or substantially fully etherified aminoplast resins based on melamine, guanamine, glycourils and urea. In general, such aminoplast resins are well known to those skilled in the art (see, eg, US5565243, US5574013, WO96 / 15183 and WO96 / 41826, cited above) and are generally commercially available. Very commonly these include melamine, guanamine, for example benzo-, aceto- and cyclohexylcarbo-guanamine, glycouril and urea and at least partially their N-alkylolated and N-alkoxyalkylated derivatives. The term "aminoplast resin" also includes oligomers thereof.

As suitable melamine based aminoplast resins, compounds of formula 2 may be mentioned.

In the above formula,

R ⁴ is independently selected from H, an alkylol group and an alkoxyalkyl group. Preferred melamines are those in which each R ⁴ is independently selected from alkoxymethyl groups having from 1 to 8 carbon atoms in H, methylol groups and alkoxy groups.

As suitable guanamine based aminoplast resins, compounds of formula 3 may be mentioned.

In the above formula,

Z is selected from H, an alkyl group of 1 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms and an aralkyl group of 7 to 20 carbon atoms,

R ⁵ is independently selected from H, an alkylol group, an alkylol group and an alkoxyalkyl group. Preferred guanamines are each independently selected from alkoxymethyl groups in which each R ⁵ is H, a methylol group and an alkoxy group having from 1 to 8 carbon atoms, in particular Z is a phenyl group (benzoguanamine), methyl group (acetogua Namin) and cyclohexyl group (cyclohexylcarboguanamine).

Suitable glycouryl based aminoplast resins include compounds of formula 4.

In the above formula,

Y is selected from H, an alkyl group of 1 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, and an aralkyl group of 7 to 20 carbon atoms,

R ⁵ is independently selected from H, an alkylol group, an alkylol group and an alkoxyalkyl group. Preferred glycouril is one in which each R ⁵ is independently selected from alkoxymethyl groups having from 1 to 8 carbon atoms in H, methylol groups and alkoxy groups.

As suitable urea based aminoplast resins, compounds of formula 5 may be mentioned.

In the above formula,

R ⁷ is independently selected from H, an alkylol group, an alkylol group and an alkoxyalkyl group. Preferred ureas are those in which each R ⁷ is independently selected from alkoxymethyl groups having 1 to 8 carbon atoms in H, methylol groups and alkoxy groups.

Specific examples of commercially available aminoplasts of this type include Cytec Industries, Inc. There are some things that may be mentioned that marketed under the trademark CYMEL ^R and the BEETLE ^R (West Paterson, New Jersey, USA).

Organic solvent

Organic solvents suitable for use in the crosslinkers of the present invention include conventional organic solvents including those described in the various references cited. As described above in US4939213, US5084541, US5565243, US5574103, WO96 / 15185 and WO97 / 08235, for example, alcohols, ketones, esters, ethers, amides, sulfones, aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons and the like. Preference is given to solvents of the type typically found in coating applications.

Particularly preferred organic solvents include ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and triethylene glycol dimethyl ether; Amides such as N, N-dimethyl acetamide; N-methyl pyrrolidone; N, N-dimethyl formamide; Hexamethyl phosphoramide; Hydrocarbons such as toluene and xylene; Sulfones such as dimethyl sulfone; Sulfonates; Esters such as methyl acetate, ethyl acetate and ethyl formate; And lower alcohols. Alcohols of 1 to 8 carbon atoms are preferred and include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, isomers thereof and mixtures thereof. Most preferred alcohol is n-butanol. Solvents having multiple functional groups are also available, such as ethylene glycol monomethyl ether, methoxypropyl acetate, hydroxypropyl acetate and the like and mixed solvents.

Any other ingredients

As noted above, the crosslinker compositions of the present invention may also be used in a variety of other optional components, such as curing catalysts, light weight stabilizing additives, antioxidants, antifoaming agents and other conventionally selected end use of crosslinker compositions. It may contain additives and auxiliaries.

For example, as exemplified by US4939213, US5084541, US5565243, US5574103, WO96 / 15185 and WO97 / 08235 cited above, the curing catalysts for 1,3,5-triazine carbamate crosslinking systems include Acidic and organometallic catalysts well known to those skilled in the art are included.

As examples of acidic catalysts, mention may be made of sulfonic acids (eg t-toluene sulfonic acid or dodecyl benzene sulfonic acid), aryl and alkyl acid-phosphates and pyrophosphates, carboxylic acids, sulfonimides and inorganic acids. Latent acid catalysts such as amine-blocking p-toluene sulfonic acid, amine-blocking dodecyl sulfonic acid, methyl p-toluenesulfonate, benzoin p-toluenesulfonate and the like are suitable at room temperature and have a very long lifetime. It is particularly useful as an acid catalyst for producing the composition.

Examples of organometallic catalysts are organotin compounds such as dibutyltin di-2-ethylhexanoate, dibutyltin diisooctyl maleate, dibenzyltin di-2-ethylhexanoate, dibutyltin Dilorate, dimethyltin dilorate, tetrabutyl diacetoxy distanoxane, tetramethyl diacetoxy distanoxane, tetrapropyl diacetoxy distanoxane, dibutyltin dichloride and the like can be mentioned.

Combinations of the above mentioned catalysts are also suitable for the compositions of the present invention.

If a curing catalyst is used, it should be present in the crosslinker composition in an amount to produce a finally formulated curing system containing from about 0.001% to about 6% by weight, preferably up to about 3% by weight of the catalyst. Typically, this will result in a crosslinker composition comprising the curing catalyst in an amount ranging from about 15% by weight or less, more preferably from about 0.5% to about 10% by weight, based on the total weight of the crosslinker composition.

Any other ingredient may be further used depending on the particular application. For example, well known auxiliaries and additives typically used in the coatings industry include foam inhibitors, leveling aids, pigments, dispersants such as pigment dispersion aids, colorants, UV absorbers (hydroxy aryl triazine types (e.g. For example, CYAGARD ^R UV 1164 from Cytec Industries Inc.), including the benzotriazole type and the benzophenone type), thermal stabilizers, other stabilizing additives such as antioxidants, inhibited amine lightweight stabilizers (eg, Clariant Sanduvor ^R 3055 and 3058). Other such optional components are illustrated in a number of previously cited references and can be referenced herein for further detail. US4426471, US4344876, US4619956, US5106891, US5322868, US5461151, EP-A, incorporated herein by reference for the detailed description of stabilization of coatings and other compositions with UV absorbers, inhibited amine light stabilizers and / or other types of light stabilizers. In particular, reference may be made to -0434608, EP-A-0444323 and EP-A-0704437.

Preparation of Crosslinker Composition

The crosslinker composition of the present invention comprises a 1,3,5-triazine carbamate, an aminoplast resin and optionally an organic solvent and / or any other component at a temperature sufficient to produce such a substantially homogeneous liquid crosslinker. And mixing for a time.

In one embodiment, a solution of 1,3,5-triazine carbamate in an organic solvent and an aminoplast resin and other optional ingredients are mixed. In another embodiment, pure 1,3,5-triazine carbamate and pure aminoplast resin are mixed directly without solvent, and then the organic solvent and / or other ingredients are optionally mixed. In another embodiment, the solid 1,3,5-triazine carbamate, aminoplast resin and other optional ingredients (in addition to the solvent) are mixed, and then the organic solvent is optionally mixed. In another embodiment, a solution of aminoplast resin, 1,3,5-triazine carbamate and other optional components in an organic solvent are also mixed.

The crosslinker composition may further modify the composition to increase or decrease the concentration of one or more components, for example by mixing an additional amount of organic solvent or 1,3,5-triazine carbamate or solvent portion. Can be prepared by removing from the crosslinker composition above or by performing both mixing and removal steps to produce a higher or lower solid crosslinker composition.

Manufacturing and Use of Coatings

Substantially homogeneous crosslinker compositions of the invention are combined with reactive resins capable of forming curable compositions suitable for many uses, including, for example, the formation of crosslinked molded articles such as coatings or adhesives, decorative laminating boards, and engineering composites. Can be.

Particularly preferred uses of these curable compositions are in the field of coatings. Liquid coating compositions may be prepared in relative amounts by methods that will be recognized by those skilled in the art, depending on the particular terminal use selected. As a general rule, the reactive resin component and the crosslinker component are preferably used in the curable composition in an equivalent (equivalent of reactive functional group) ratio of about 0.5: 1 to about 2: 1, more preferably about 0.8: 1 to about 1.2: 1. It must be mixed.

A detailed description of suitable reactive resins can be found by US4939213, US5084541, US5565243, US5574103, WO96 / 15185 and WO97 / 08235 cited above.

Preferred reactive resins for use in the coating compositions are compounds containing a plurality of active hydrogens and / or epoxy functional groups (“polyfunctional (active hydrogens and / or epoxy) resins”).

Active hydrogen functional groups as used herein are, for example, carbamate groups of 1,3,5-triazine carbamate and (or functional groups that can be produced by carbamate under curing conditions, such as isocyanate functional groups). And / or a group containing active hydrogens capable of reacting with the imino, alkylol and / or alkoxymethyl groups of the aminoplast resin under the curing conditions of the coating.

Such active hydrogen functional groups are generally well known to those skilled in the art of coating and include groups such as hydroxyl, carboxyl, mercapto, amino, amido and carbamate groups. Preferred are hydroxyl, carboxyl and amino, with hydroxyl being particularly preferred. These groups are suspended from the backbone resin of the coating composition of the present invention and precipitate in the crosslinking process. Backbone resins are generally well known to those skilled in the art and are described in the previously cited US4939213, US5084541, US5565243, US5574103, WO96 / 15185 and WO97 / 08235.

Preferred active hydrogen-containing resins are hydroxy group containing materials which contain at least two, and preferably two or more, hydroxy groups per molecule. Preferred multifunctional hydroxy group containing materials are acrylic or polyester backbone resins. Illustrative examples include the addition of further vinyl compounds, for example styrene, by copolymerization of acrylic or methacryl esters with hydroxyfunctional acrylic or methacrylic esters such as hydroxyethyl acrylate or methacrylate. Acrylic resins that can be obtained by simultaneous use are included. Illustrative examples of polyfunctional hydroxy group containing materials also include polyester resins that can be obtained, for example, by reaction of polycarboxylic acids with excess polyhydric alcohols. In addition, suitable multifunctional hydroxy groups containing resins also contain epoxy prepolymers such as those produced from the reaction of amines or polyfunctional carboxylic acid derivatives with polyfunctional epoxy groups containing compounds such as polyurethane prepolymers, alkyds, and Hydroxy groups are included. In general, the hydroxyl functional groups of such resins are suspended or attached to the end, preferably having a weight average molecular weight (Mw) of about 750 to about 7000, more preferably about 2000 to about 5000, and about 20 to about 300 mg KOH / g resin and more preferably a resin of the hydroxyl number properties of about 60 to about 200 mg KOH / g resin.

Examples of commercially available active resin-containing resins include DORESCO ^R TA 39-21 acrylic resin (Dock Resins, Linden, NJ), JONCRYL ^R 500 acrylic resin (SC Jonson & Sons, Rassin, Wisconsin, USA), ACRYLOID ^R AT-400 acrylic resin ( Rohm & Haas, Philadelphia, Pennsylvania, CYPLEX ^R 1531 Polyester Resin (Cytec Industries, Paterson, NJ), CARGILL 3000 and 5776 Polyester Resin (Cargill, Minneapolis, MN), TONE ^R Polyester Resin (US Connecticut Dan) Union Carbide of Burley, K-FLEX ^R XM-2302 and XM-2306 Resin (King Industries, Norwalk, CT), CHEMPOL ^R 11-1369 Resin (Cook Composites and Polymers, Port Washington, Wisconsin, USA), JONCRYL ^R 540 Acrylic the emulsion polymer (wi below god ^{SC Jonson & Sons), RHOPLEX R} AC-1024 acrylic emulsion resin (Rohm & Haas of Philadelphia, PA, USA), ^R XC 4005 water reduction acrylic resin ( Cytec Industries) in the station NJ Paterson, CRYLOOAT ^R 3494 solid hydroxy terminated polyester resin (UCB CHEMICALS USA of GA Smyrna), RUCOTE ^R 101 polyester resin (Ruco Polymer, New York, USA Hicks Bill), JONCRYL ^R SCX-800 -A and SCX-800-B hydroxy functional solid acrylic resins (SC Jonson & Sons, Rassin, Wisconsin, USA), ALFTALAT ^R AN 745 hydroxy functional polyester resins of Hoechst Corporation, and the like.

The multifunctional epoxy compound usable as the resin component in the curable composition of the present invention contains an average of at least two, preferably two or more epoxy functional groups per molecule, and is a polyfunctional epoxy group containing material which is a monomer, oligomer, polymer or mixture thereof. It includes. Such multifunctional epoxy compounds are generally US2872427, US3730930, US3752870, US3781380, US3787521, US4011381, US4346144, US4607069, US4650718, US4681811, US4703101, US4764430, US4855386, US5001173, US5116892, which are hereby incorporated by reference for the purposes herein. It is well known to those skilled in the art as exemplified by US5118729, WO92 / 19660 and WO94 / 06876.

Specific examples of monomeric polyfunctional epoxy compounds include bifunctional epoxy resins (biceoxides) comprising glycidyl ethers of dihydric phenols, for example bisphenol-A / epichlorohigh, such as diglycidyl bisphenol-A. The reaction products presented; Vinyl cyclohexene diepoxides such as 4-vinyl-1-cyclohexene diepoxide; 1,2,5,6-diepoxycyclooctane; 1,2,7,8-diepoxyoctane; Dicyclopentadiene diepoxide; 1,4, -divinyl benzene diepoxide; Cyclohexene-4-methyl cyclohexene-4-carboxylate diepoxide; Glycidylated diol type polyfunctional epoxy group containing materials such as hexene diol, diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether And the like can be mentioned. Other suitable monomeric multifunctional epoxy compounds include trifunctional epoxy resins (trisepoxides) such as tri- (4-glycidyl oxyphenyl) methane and triglycidyl isocyanurate; And more expensive multifunctional epoxides such as glycidylated pentaerythritol and sorbitol. Examples of commercially available bisphenol-A / epichlorohydrin reaction products are epoxy resins marketed under the trademark Epon ^{R from} Shell Chemical Company (Houston, Texas, USA), for example Epon ^R 828 having an equivalent weight in the range of 185 to 192. This may be mentioned. As an example of a commercially available glycidylated sorbitol, a substantial monomeric glycidylated sorbitol known as Synocure® 888 (Cook Composites and Polymers Company, Port Washington, Wisconsin) may be mentioned.

Oligomeric multifunctional epoxy group containing materials include oligomeric forms of monomeric materials, oligomers of diepoxides such as low molecular weight bis-phenol-A oligomers, prepolymers thereof, reaction products of amines and diepoxides, and the like.

Polymeric multifunctional epoxy group containing materials include, for example, polymers of epoxy group containing unsaturated monomers and copolymers with unsaturated comonomers that do not contain epoxy groups thereof. As examples of epoxy group containing unsaturated monomers, mention may be made of glycidyl acrylate, glycidyl methacrylate and allyl glycidyl ether. Examples of unsaturated comonomers that do not contain epoxy groups are alkyl esters of acrylic and methacrylic acids containing from 1 to 20 carbon atoms in the alkyl group, such as methyl acrylate, ethyl acrylate, butyl acrylate, ethyl Hexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and ethylhexyl methacrylate; Vinyl aromatic compounds such as styrene, methyl styrene and vinyl toluene; Vinyl and vinylidene halides such as vinyl and vinylidene chloride, vinyl esters such as vinyl acetate; Allyl alcohol; And hydroxyalkyl acrylates and methacrylates containing 1 to 20 carbon atoms in the hydroxyalkyl group, for example hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxy Propyl methacrylate and the like can be mentioned. The copolymerization reaction can be carried out by known methods such as those described in US3787521, US4181642, EP-A-0480120 and EP-A-0256369, which are incorporated herein by reference, as various references cited above and fully described above. .

Commercially available glycidyl methacrylate copolymer type multifunctional epoxy group containing materials include Synthacryl ^R VCS 1436 resin, a product of Hoechst-Celanese Corporation, Charlotte, NC; Estron ^R GMA-252 resin (Mw: 8300; EW: 250; Tg: 36), a product of Estron Chemicals, Calvert City, Kentucky, USA; Almatex ^R PD 6100 (Mw: 12500; EW: 1030; Tg: 63), Almatex ^R PD 6300, Almatex ^R PD 7110, Almatex ^R , a product of Japan Mitsui Toatsu Company, Inc., and commercially available from Anderson Development Company, Adrian, Mich. PD 7210, Almatex ^R PD 7310, Almatex ^R PD 7610 (Mw: 7000; EW: 510; Tg: 45) and Almatex ^R PD 1700 resins; Blemmer ^R CP-15 (Mw: 12300; EW: 1000; Tg: 63), products of Nippon Oil and Fat Corporation of Japan, Blemmer ^R CP-30 P (Mw: 10300; EW: 530; Tg: 62) and Blemmer ^R CP-5 SA (Mw: 10100; EW: 3000; Tg: 96) resins.

For aqueous applications, the multifunctional material further contains an aqueous dispersion facilitating group, for example WO96 / 15185 and WO97, which are incorporated herein by reference as having a higher carboxyl or sulfone functionality and more generally a high molecular weight. / 08235, and GB1530022, EP-A-0568134, EP-A-0663413, US5075370, and US5342878.

For solventborne coatings, liquid resin components are generally preferred, but solid materials can also be used, especially when the solid is dissolved in the particular formulation in which it is used.

In addition to the resin component, 1,3,5-triazine carbamate, aminoplast resin, and any other components, the coating composition prepared by the method of the present invention may optionally include various additive components. Depending on the end use, these include other well known auxiliaries and additives typically used in the coatings industry, including, for example, bubble inhibitors, leveling aids, pigments, pigment dispersion aids, colorants, UV absorbers and other stabilizing additives. can do. Such other additives are generally described above and are well known to those skilled in the art and need not be described further.

Coatings of the present invention can be prepared by adding the components of the coating composition and optional components, if any, to organic solvents that are commonly used, in any convenient order.

Conventional types of coatings can be prepared by conventional coating methods using the coating compositions described herein, including solvent based coatings, aqueous coatings, hot coil coatings, and the like. For example, the present coating compositions may contain solvents of the type typically found in coating applications, including alcohols, ketones, esters, aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, and the like.

In liquid organic solvent based coatings, the coating composition preferably has a solids content level suitable for convenient application with minimal material loss, preferably at a solids content level in the range of about 20% to about 85% by weight, depending on the method selected. Is formulated to produce solids content levels in the range of about 45% to about 65% by weight.

As described below, the preferred method of application is by spraying, and those skilled in the art can formulate coating compositions for spraying that are applicable with the aid of the present disclosure.

Although the crosslinker composition and the active hydrogen containing material can be used in various amounts, when such components comprise the first film-forming component of the coating that is subsequently formed, the molar of the reactive functional group of the crosslinker to the reactive functional group of the resin component It is preferred to be present in the coating composition in an amount such that the ratio is in the range from about 0.5: 1 to about 2: 1, in particular in the range from about 0.8: 1 to about 1.2: 1. When a plurality of functional resins and / or crosslinkers are used, the overall reactive functional group ratio is preferably within the above range.

In practical practice, a coating composition containing a liquid medium, such as a solvent and a substrate, is contacted. The contact can be carried out by dipping, spraying, padding, brushing, flow coating, electrocoating or electrostatic spraying. After contacting, the solvent is partially evaporated to create a homogeneous coating on the substrate. The composition can then be cured by additional heat application at a temperature and for a time sufficient to produce a substantially complete cured coating.

Preferably, the curing temperature is about 25 ° C to about 450 ° C. In liquid coating applications, the curing temperature typically ranges from about 80 ° C to about 160 ° C. In coil coating applications, the curing temperature is typically from about 250 ° C to about 450 ° C. The curing time preferably ranges from about 1 second to about 30 minutes but may vary depending on the temperature selected for curing. For example, a fully cured coil coating can be obtained by curing at 260 ° C. for 1 minute or by curing at 417 ° C. for 20 seconds. Typical curing times for liquid coatings range from about 5 minutes to about 30 minutes.

Aqueous coatings can be prepared in a manner similar to that described in WO96 / 15185 and WO97 / 08235 cited above, using the high solid, homogeneous crosslinker compositions of the present invention as crosslinker components. As described herein and above, reactive resins suitable for use in aqueous coating applications include those having sufficient anionic hydrophilic functionality to render the curable coating composition water dispersible. Preferred hydrophilic groups for most applications are those which produce anions, in particular carboxyl and sulfone groups, upon neutralization. Particular preference is given to carboxyl groups.

In order for the active hydrogen containing surface active resin to be water dispersible, the anion generating groups present in the resin must be at least partially neutralized. Suitable neutralizing agents to achieve this are well known to those skilled in the art and include, for example, organic and inorganic bases such as ammonia, primary, secondary and tertiary amines. Tertiary amines are preferred.

In addition, the aqueous coating composition can be obtained by adding an aqueous dispersion promoting substance to the curable composition of the present invention. Materials that are eligible as aqueous dispersion-promoting materials can be readily identified by those skilled in the art. Preference is given to organic compounds having alkyl chains or aromatic groups substituted with hydrophilic groups. These include, for example, long chain aliphatic alcohols (e.g. ethylhexanol, octanol, dodecanol, etc.), benzyl alcohols and other aromatic alcohols, ester-alcohols (e.g., hydroxyalkyl esters of alkanoic acid) and the like. This includes. Long-chain alkyl alcohols having at least 8 carbon atoms, such as ethylhexanol, and hydroxyalkyl esters of alkanoic acids containing at least 8 carbon atoms, such as Texanol ^R , are commercially available from Eastman Chemical Company. Particular preference is given to the C ₈ -hydroxyalkyl ester of methylpropionic acid which is

Coating method

The invention further includes a substrate coating method. The coating method includes applying the coating composition to a substrate and then curing the applied coating composition to produce a cured coating and cured product.

As mentioned above, conventional coating methods, including roller-coating, dipping and spraying, can be used to prepare the coating. Particularly preferred systems according to the invention are formulated for spray application.

The coating composition of the present invention can be used in a wide variety of applications. Particularly preferred terminal uses are one- or two-component coatings for elevated temperature curing applications, for example self-propelled OEM clearcoats or colored basecoats. Other potential applications include, for example, coatings for wire appliances, furniture, pipes, machinery, and the like. Suitable substrates include glass, temperature resistant plastics and metals such as steel and aluminum.

The foregoing description of the invention will be further illustrated by the following examples which are provided by way of explanation but not as a limitation of the scope of the invention.

Example 1

Part A: Preparation of 1,3,5-triazine carbamate in n-butanol

A mixture of 22.2 wt% sodium butoxide in n-butanol (219.5 lbs) and degassed n-butanol (5 lbs) is placed in a 50 gallon glass lining reactor under nitrogen atmosphere and the n-butanol portion (22 lbs) is distilled off. Degassed dimethyl carbonate (32 lbs) is added while maintaining the temperature of the mixture at below 30 ° C. with stirring. After 1 hour, degassed melamine powder (14.5 lbs) is added and the slurry is heated at about 90 ° C. for 1 hour. The reaction mixture is then cooled to 8 ° C., the pH is adjusted to 6 using a combination of 5 N (106.5 lbs) and 2.9 N (9 lbs) and the resulting mixture is allowed to phase separate. The organic layer is filtered through a 0.5 micron filter and washed with water (2 x 125 lbs) to remove insoluble matter. Sufficient volatiles are then removed to produce a product having the following characteristics:

Solid (Pan solid method, wt%) 57.9

Color (APHA method) 500

Haze (visual inspection) transparent

Remaining dibutyl carbonate (GC, weight%) 3.2

Butyl Carbamate Content (%) 64

Methyl Carbamate Content (%) 36

The methyl and butyl carbamate content (%) of 1,3,5-triazine carbamate is calculated from HPLC / MS analysis as follows. High pressure liquid chromatography analysis (HPLC) shows seven major components (tributyl, bisbutyl-monomethyl, monobutyl-bismethyl, trismethyl, bisbutyl, monobutyl-) in 1,3,5-triazine carbamate samples. Monomethyl and bismethyl) are illustrated. Gravimetric spectrophotometry (MS) identifies the number of methyl and / or butyl groups in various components, thus the respective tris- or bis- derivatives. Normalize the sum of HPLC area% values to 100% by summing the area% values obtained from HPLC analysis and multiply each value by 1 / (total area%), and then normalize the area% value of the product and butyl for each component. The butyl content is calculated by summing the number of groups. The methyl content can similarly be calculated by summing the normalized area% value of the product with the number of methyl groups for each component. The methyl and butyl content (%) of the mixture is calculated using formulas (1) and (2): (1)% butyl = 100 x butyl / (total butyl + total methyl); (2)% methyl = 100-% butyl.

Part B: Preparation of Solid 1,3,5-triazine Carbamate

The solution of Part A is diluted 50% by weight in n-butanol and 2150 g are placed in a round bottom flask attached to a rotary evaporator. The volatiles are removed under reduced pressure at 60-70 ° C. until about 80% by weight solid residue is obtained (about 900 ml distillate is obtained). After addition of acetonitrile (8000 ml), the mixture is heated at about 90 ° C. for 2 hours, then the mixture is cooled to about 10 ° C. (ice bath, 1-2 hours), and the solids are collected by suction filtration. Washed with cooled acetonitrile (3 × 500 ml) and vacuum dried at 50 ° C. to yield 1,3,5-triazine carbamate as a white powder.

Part C. Preparation of 1,3,5-triazine carbamate (methyl: butyl ratio 40:60) in n-butanol

A mixture of 25% by weight sodium methoxide, sodium borohydride (205 g) and degassed n-butanol (3250 lbs) in methanol (1774 lbs) was placed in a 1000 gallon reactor under a nitrogen atmosphere and most of the methanol was heated under reduced pressure. Remove it. Additional amount of degassed n-butanol (3275 lbs) is added and distillation is continued until about 3075 lbs of solution is present in the reactor. Degassed dimethyl carbonate (592 lbs) is added while maintaining the temperature of the mixture at 30 ° C. or less with stirring. After 1 hour, the clear liquid is transferred to a mixing tank containing degassed melamine powder (260 lbs) to form a homogeneous slurry and then the slurry is returned to a 1000 gallon reactor and heated at about 90 ° C. for 1 hour. The reaction mixture is then cooled to 28 ° C. and the pH adjusted to 5 and allowed to phase separate. The organic layer is filtered through a 0.5 micron filter and washed with water (2 x 250 gallons) to remove insoluble matter. Sufficient volatiles are then removed to produce the following products:

Solid (Pan solid method, wt%) 50.6

Color (APHA method) 50

Haze (visual inspection) transparent

n-butanol (GC, weight percent) 46

Residual Methanol (GC,% by weight) <0.1

Remaining dibutyl carbonate (GC, weight%) 0.8

Remaining dimethyl carbonate (GC, wt%) <0.1

Remaining Methyl Butyl Ether (GC, Weight%) <0.1

Remaining dibutyl ether (GC, wt%) <0.1

Butyl Carbamate Content (%) 60

Methyl Carbamate Content (%) 40

Example 2

A homogeneous liquid crosslinker composition was prepared from a 50 wt% solution of solid 1,3,5-triazine carbamate in n-butanol (obtained from Example 1, Part B), a commercially available aminoplast resin crosslinker and an additional amount of Prepared by combining the solid 1,3,5-triazine carbamate (obtained from Example 1, Part B) in the amounts illustrated in Table 1. Apparently, the viscosity and final composition of the crosslinker composition prepared according to the invention are also illustrated in Table 1.

A B C D E 50% solution of solid 1,3,5-triazine carbamate 2.50 2.00 1.25 2.50 2.50 CYMEL ^R 303 Resin ⁽¹⁾ 1.00 1.00 1.00 ---- ---- CYMEL ^R 301 Resin ⁽²⁾ ---- ---- ---- 1.00 ---- CYMEL ^R 1135 Resin ⁽³⁾ ---- ---- ---- ---- 1.00 Solid 1,3,5-triazine carbamate 2.75 2.00 0.88 2.75 2.75 gun 6.25 5.00 3.13 6.25 6.25 Final composition (% by weight) 1,3,5-triazine carbamate 64 60 48 64 64 CYMEL ^R 303 Resin ⁽¹⁾ 16 20 32 ---- ---- CYMEL ^R 301 Resin ⁽²⁾ ---- ---- ---- 16 ---- CYMEL ^R 1135 Resin ⁽³⁾ ---- ---- ---- ---- 16 Non-volatile materials 80 80 80 80 80 Volatile substance (n-BuOH) 20 20 20 20 20 Viscosity (cps) 9000 5600 1300 8600 5600 Exterior Early Transparency Transparency Transparency Transparency Transparency After 1 month at 5 ℃ Transparency Transparency ---- Transparency Transparency ⁽¹⁾ CYMEL ^R 303 resin is a product of Cytec Industries, Western Paterson, NJ. ⁽²⁾ CYMEL ^R 301 resin is a product of Cytec Industries, Western Paterson, NJ. ⁽³⁾ CYMEL ^R 1135 resin is a product of Cytec Industries, Western Paterson, NJ.

Example 3

Two coating formulations are prepared by combining the components described below. Formula F contains 50% by weight solution of solid 1,3,5-triazine carbamate in n-butanol (obtained from Example 1, Part B) as the sole crosslinker and Formulation G is Example 2 according to the present invention. Crosslinker composition A.

Formulation F G

DORESCO ^R TA 39-21 ⁽⁵⁾ (80%) 97.32 94.54

44.29 0 of solid 1,3,5-triazine carbamate

50% solution

Crosslinker A (Example 2, Table 1) 0 30.45

CYCAT ^R 600 catalyst ⁽⁶⁾ (10% in n-butanol) 10 10

Dow Corning Paint Additives 57 (1% in n-butanol) 5 5

Arcosolv ^{R (7)} PM Acetate 10.85 15.00

Methylene Isobutyl Ketone 10.85 15.00

Xylene 10.85 15.00

n-butanol 10.85 15.00

⁽⁵⁾ DORESCO ^R TA 39-21 Acrylic resins are the product of Dock Resins in Linden, NJ.

⁽⁶⁾ CYCAT ^R 600 Catalytic Curing The catalyst is a product of Cytec Industries, West Paterson, NJ.

⁽⁷⁾ Arcosolv ^R PM Acetate is the product of Arco Chemical Company.

The coating formulation is coated by a wire former on two Bondrite ^R 1000 treated cold rolling steel sheets (Advanced Coating Technologies, Inc., Hillsdale, Michigan) and cured at 140 ° C. for 30 minutes. The resulting cured film is tested for performance. Solvent resistance is measured to "damage" and "remove" the coating by methyl ethyl ketone (MEK) double rub. Highly crosslinked coatings require 200+ (ie 200 or more) MEK rubs to break. If two solvent resistance values are exemplified, the first is the number of rubs to break the coating and the second is the number of rubs to remove the coating. If only one value is exemplified, the coating is not compromised and the exemplified number is the number of rubs to remove it. The results are illustrated in Table 2.

Physical properties of the coating F G Film thickness (mils) 1.5 1.5 Knoop Hardness 12.4 13.4 MEK double rub 200+ 200+ Cleveland humidity resistant Blistering, 2 days 10 10 Blistering, 5 days MB / D MB / F Blistering, 9 days MB / D MB / F Blistering, 15 days 5 / D 8 / F Blistering, 21 days 4 / D 8 / M Blistering, 41 days n / a 8 / D KHN25, 0 days 12.9 12.1 KHN25, 5 days 12.2 11.9 KHN25, 9 days 12.0 12.4 KHN25, 15 days n / a ⁽⁸⁾ 11.8 KHN25, 21 days n / a ⁽⁸⁾ 11.2 MEK rub, 0 days 200+ 200+ MEK rub, 9 days 10/200 + 30/200 + MEK rub, 21 days n / a ⁽⁸⁾ 20/200 + Overbaking resistance (160 ℃ / 60) KHN25, formerly 12.4 13.4 KHN25 and later 10.8 13 MEK double rub, former 200+ 200+ MEK double rub, after 20/200 + 200+ Underwater impregnation test at 60 ℃ Appearance, 15 days Transparency Transparency Blistering, 15 days 6 / F 10 MEK rub, 15 days 2/170 20/200 + 20 ° Gloss (MEK Lubbefore), 15 days 90 99 20 ° gloss (after MEK rub), 15 days 8 84 ^{(8) The} film is not smooth enough to measure its properties.

Example 4

Solid 1,3,5-triazine carbamate (obtained from Example 1, Part B) without homogeneous liquid crosslinker compositions H, I, J and K, CYMEL ^R 301 aminoplast resin (100% solids) Or CYMEL ^R 303 aminoplast resin (100% solids) or CYMEL ^R 1131 aminoplast resin (100% solids) in Table 3 with the weight percent of 1,3,5-triazine carbamate in the appearance and final composition. Prepared by combining in the amounts exemplified.

H I J K 1,3,5-triazine carbamate 1.6 1.6 1.0 1.6 CYMEL ^R 301 Resin 9.0 0 0 0 CYMEL ^R 303 Resin 0 9.0 0 0 CYMEL ^R 1131 Resin ⁽⁹⁾ 0 0 9.0 9.0 1,3,5-triazine carbamate (% by weight) 15% 15% 10% 15% Exterior Transparency Transparency Transparency Slightly blurred ⁽⁹⁾ CYMEL ^R 1131 resin is a product of Cytec Industries, Western Paterson, NJ.

Example 5

A homogeneous liquid crosslinker composition L, M and N was prepared by 50.6 wt% solution of solid 1,3,5-triazine carbamate in n-butanol (obtained from Example 1, Part C), CYMEL ^R 303 aminoplast resin (100% solids) or CYMEL ^R 1131 aminoplast resin (100% solids) or organic solvents combined. The amount used, 1,3,5-triazine carbamate (% by weight) in the final composition and the appearance of the final crosslinker composition are shown in Table 4. The initially prepared clear solution remains clear for at least one month.

L M N 1,3,5-triazine carbamate 42.5% 40% 42.5% CYMEL ^R 303 Resin 42.5% - - CYMEL ^R 1131 Resin - 40% 42.5% Volatile substance (n-BuOH) 15% 20% 15% Viscosity (cps) 9,500 500 2,415 Viscosity (G / H) -Z ₅ S Z-Z, ocean Early Transparency Transparency Transparency After 1 month at 5 ℃ Transparency Transparency Transparency

Example 6

Highly solid, homogeneous liquid crosslinker composition O with 50% by weight solution of solid 1,3,5-triazine carbamate (solid 1,3,5-triazine carbamate of Example 1, Part B) prepared from n-butanol), CYMEL ^R 303 aminoplast resin (100% solids) and additional amounts of solid 1,3,5-triazine carbamate (obtained from Example 1, Part B) as illustrated in Table 5 Prepared by combining in amounts. The appearance, viscosity and final composition of the high solid, homogeneous liquid crosslinker composition are also illustrated in Table 5.

O 1,3,5-triazine carbamate (n-BuOH) 3.33 CYMEL ^R 303 Resin 1.00 1,3,5-triazine carbamate (100% solids) 4.00 gun 8.33 Final composition (% by weight) 1,3,5-triazine carbamate 68% CYMEL ^R 303 Resin 12% Non-volatile materials 80% Volatile substance (n-BuOH) 20% Viscosity (cps) 15500 Exterior Early Transparency After 1 month at 5 ℃ Transparency

Although the present invention has been described with respect to certain preferred embodiments, changes and modifications can be made by those skilled in the art without departing from the scope of the invention as defined by the claims.

Claims (6)

(i) 1,3,5-triazine carbamate, (ii) aminoplast resins, and (iii) optionally comprising a substantially homogeneous mixture of liquid phases of the organic solvent and having a solids content of at least about 65% by weight based on the total weight of the crosslinker composition, wherein the sum of (i) and (ii) comprises At least 50% by weight based on total weight, wherein the weight ratio of (i) :( ii) is from 1:99 to 99: 1. 2. A solid according to claim 1, having a solids content of at least about 95% by weight based on the total weight of the crosslinker composition, wherein the aminoplast resin is a liquid aminoplast resin and the weight ratio of (i) :( ii) is about A crosslinker composition that is from 1:99 to about 80:20. The composition of claim 1 comprising about 10 to about 30 weight percent organic solvent and about 50 to about 90 weight percent combination of (i) and (ii), wherein the weight ratio of (i) :( ii) is about 20 : 80 to about 99: 1. The crosslinker composition of claim 1, wherein the 1,3,5-triazine carbamate is a compound of formula (I). Formula 1 In the above formula, R is selected from the group consisting of -NHCOOR ³ , hydrogen, hydrocarbyl, hydrocarbyloxy, hydrocarbylthio, amido, sulfonamido, amino, hydrocarbylamino, dihydrocarbylamino and hydrocarbyleneamino, Each of R ¹ , R ² and R ³ is independently selected from hydrocarbyl groups. A substantially homogeneous mixture of (I) a poly (active hydrogen and / or epoxy) compound and (II) crosslinker composition, characterized in that the crosslinker composition is as described in any of claims 1-4. Liquid curable composition. A substantially homogeneous mixture of (I) a poly (active hydrogen and / or epoxy) compound and (II) crosslinker composition, characterized in that the crosslinker composition is as described in any of claims 1-4. Liquid sprayable coating compositions.