KR0170629B1 - Novel vinyl-terminated carbamylmethylated nitrogen-containing heterocyclic compounds - Google Patents

Abstract

The present invention relates to vinyl-terminated polyurethane / polyamide polymers and to coating / sealing and adhesive compositions comprising them. The vinyl-terminated polyurethane / polyamide polymer is prepared by reacting vinyl acid, vinyl alcohol or vinyl amide with polyisocyanate, and then reacting the reaction product with a high molecular weight polyol, having a molecular weight of 3,000 to 80,000, It is characterized by containing two or more vinyl end groups.

In addition, the curable coating / sealing composition of the present invention comprises (A) 30 to 90% by weight of a vinyl-terminated polyurethane / polyamide polymer having a molecular weight of 3,000 to 80,000; (B) 5 to 70 weight percent of at least one nitrogen-containing heterocyclic compound comprising at least one carbamylmethyl group and at least two vinyl-terminated organic groups as a reactor; (C) 2 to 30% by weight of a polymerizable diluent; And (D) 0.5 to 5% by weight free-radical catalyst, wherein the sum of components (A), (B), (C) and (D) does not exceed 100% by weight) Is in addition to the components (A), (B), (C) and (D) of the coating / sealing composition (E) 0.5-10% by weight (E), , (C), (D) and (E) do not exceed 100% by weight).

Description

Vinyl-terminated Poriethane / Polyamide Polymers and Coating / Sealing and Adhesive Compositions Comprising the Same

The present invention relates to novel nitrogen-containing heterocyclic compounds containing reactive functional groups, including vinyl-terminus groups and carbamylmethyl groups, which are generally used as monomers and crosslinkers, and at least two vinyl end groups having a molecular weight of about 3,000-80,000. A novel vinyl-terminated polyurethane / polyamide polymer containing The present invention also includes a coating / adhesive composition prepared from (i) the new and old nitrogen containing heterocyclic compounds of the invention and (ii) the novel vinyl terminated polyurethane / polyamide polymers of the invention and having low temperature curability.

The prior art describes curable compositions containing melamine and benzoguanamine derivatives as crosslinkers.

US Pat. Nos. 4,708,984 and 4,710,542 describe beta-hydroxyalkylcarbamylmethylated aminotriazines and alkalcarbamylmethylated aminotriazine containing curable compositions, respectively. These hardeners generally exhibit good detergency and salt spray resistant properties and are preferably cured at temperatures of 150 ° C. to about 200 ° C.

US Pat. Nos. 4,230,740 and 4,230,550 describe melamine compounds having vinyl end groups and those compounds used in radiation cured coatings.

U.S. Patent No. 4,295,909 discloses adhesive compounds using prepolymers that are polycapped with urethane acrylates based on polyols or polyamines.

US Patent No. 3,855,379 describes vinyl-terminated polyurethane polymers having a molecular weight of 2,000-about 10,000 in the binding composition.

Although the prior art describes melanin compounds with carbamylmethyl groups or melanin compounds with vinyl-terminated groups, both types of groups of the melanin type nucleus, or groups of both types combined with methylol / alkoxymethyl groups It is not disclosed about melamine compounds having both. In addition, the prior art does not disclose the use of a melanin compound having a vinyl-terminated polyurethane / polyamide and a vinyl-terminated group / carbamylmethyl group in an adhesive and coating composition.

Now, novel compounds having a wide variety of useful functionalities are essential pendant reactors containing (i) at least two vinyl-terminated organic groups and (ii) nitrogen-containing heterocyclic compounds having at least one carbamylmethyl group. Turned out. Typically nitrogen containing heterocyclic compounds containing these groups are selected from melamine, oligomers of melamine, benzoguanamine, oligomers of benzoguanamine, glycoluril, oligomers of glycoluril, and mixtures thereof. .

Another finding of the present invention is that when a novel vinyl-terminated polyurethane / polyamide polymer of molecular weight of about 3,000 to about 80,000 containing at least two vinyl end groups is used in combination with the nitrogen-containing heterocyclic compound of the present invention, It has a property.

It is a finding of the present invention that the novel heterocyclic nitrogen compounds and vinyl-terminated urethane compounds described in the above paragraphs are useful as essential components in new and improved low temperature cure tack and coating compositions. The invention provides little or no surface pretreatment with glass to glass, steel to steel, steel to glass, and plastic materials such as fiber-reinforced sheet molding compounds (SMC) to the same plastic. It provides an adhesive suitable for bonding.

Chapter I-New Nitrogen-Containing Heterocyclic Compounds:

The novel compounds of the present invention are nitrogen containing heterocyclic compounds containing at least two vinyl-terminated substituents and at least one carbamylmethyl substituent. Also novel are compositions of matter containing predominant proportions of at least one novel compound according to the invention.

The nucleus of the nitrogen-containing heterocyclic compound of the present invention is preferably selected from melamine, oligomer of melamine, oligomer of benzoguanamine, oligomer of glycoluril and glycoluril. Preference is given to nuclei derived from melamine, oligomers of melamine, benzoguanamine or oligomers of benzoguanamine. Most preferred are nuclei derived from melamine or oligomers of melamine.

The oligomers of melamine, benzoguanamine and glycoluril as used herein refer to amino resins produced by the reaction of these compounds with aldehydes such as formaldehyde.

The portion of the nitrogen-containing heterocyclic compound nucleus not occupied by the vinyl-terminated chelating agent or carbamylmethyl substituent may be occupied by any non-interfering substituent, but such non-interfering substitution It is preferable that I is a methylol and / or an alkalized methylol group. Novel compounds based on melamines or oligomers:

The novel melamine type compounds of the present invention are represented by the following general formula (I):

Wherein a = 3 to 6 and

Or a substituent selected from mixtures thereof, wherein Z is CH ₂ CH ₂ -O- or

ego,

R ⁴ is hydrogen or a C ₁ -C ₁₈ alkyl radical,

R ² is a general formula

Wherein R ⁵ is a carbamyl radical of C ₁ -C ₁₈ alkyl, alicyclic, hydroxyalkyl, alkoxyalkyl or an aromatic radical, and R ³ is —OR ⁶ where R ⁶ is hydrogen or C ₁ -C ₁₈ aliphatic, cycloaliphatic or aromatic radical, provided that m is at least 2, n is at least 1, and the sum of (m + n) is at least 3.

Preferred nitrogen-containing heterocyclic compounds of the present invention may alternatively be represented by the following general formula (II).

Wherein the substituent R is defined below.

R is acrylamido, methacrylamido, acrylate, methacrylate, -OR ⁶ (wherein R ⁶ is as defined above) or carbamyl, provided that at least one R substituent is carmil, at least The two R substituents are acrylamido, methacrylic amido, allyloxy, metalyloxy, acryloiloxy, acryloiloxy alkoxy, methacrylic amido, allyloxy, metalyloxy, acryloiloxy, acryloiloxy Alkoxy, methacryloyloxyalkoxy and methacryloyloxy.

Illustrative melamine type compounds of the present invention are as follows.

And mixtures thereof.

General formula (I) corresponds to the melamine type compound of this invention when n is at least 2, n is at least 1, and the sum of (m + n) is at least 3.

The novel melamine compounds of the present invention include oligomer forms of melamine of the general formula (III) below.

In the above formula, the degree of polymerization p is 2-10, preferably 2-5. Melamine oligomer is CYMEL of American Cyanamide Company, Wayne City, New Jersey, USA. Commercially available as 300 series resins. Melamine oligomers are typically bound by said bond L, where L is a -CH ₂ -or -CH ₂ OCH ₂ -bond which occupies a position in the melamine nucleus, but the remaining reaction sites on the oligomer nucleus are at least two The general requirement that vinyl-terminated substituents and at least one carbamyl substituent be present should be met.

Novel compounds based on benzoguanamine and benzoguanamine oligomers:

The novel benzoguanamine type compound of this invention is represented by following General formula (IV).

Wherein b is 3 to 4, and R ¹ , R ² , R ³ , m and n are as defined above.

Oligomer forms of benzoguanamine having at least two vinyl groups and at least one carbamyl group are also compounds within the scope of the present invention.

Novel compounds based on glycoluril and glycoluril oligomers:

The novel glycoluril compound of the present invention is represented by the following general formula (V).

Wherein c is 3-4 and R ¹ , R ² , R ³ , n and m are as defined above.

Oligomer forms of glycoluril having at least two vinyl-substituents and at least one carbamyl group are compounds within the scope of the present invention.

Common points about the novel nitrogen-containing heterocyclic compounds of the present invention:

Although vinyl groups have been described in the general sense, they may also be mentioned as substituents derived from unsaturated alcohols, acids and amides. Examples of compounds suitable for the second stage of vinyl-terminated oligomer preparation include allyl alcohol, hydroxy ethylhexyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxy propyl methacrylate, hydroxylauryl methacrylate , 2-hydroxyethyl acrylate, acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, methacrylamide, N-hydroxy acrylamide, N-hydroxy methacrylamide, acrylamide and mixtures thereof.

Carbamylmethyl groups are described in the general sense but may also be mentioned as substituents derived from alkyl and hydroxy alkyl carbamates of 1-18 carbon atoms. Examples of suitable carbamate reactants used to prepare carbamylmethyl substituents of the present invention are as follows: methyl carbamate, ethyl carbamate, propyl carbamate, butyl carbamate, beta-hydroxy alkyl Carbamate, 2-ethylhexyl carbamate and beta-alkoxy alkyl carbamate.

The minimum number of vinyl-terminated substituents and carbamylmethyl substituents were referred to as 2 and 1, respectively. However, it is generally beneficial to have a plurality of vinyl-terminated and carbamylmethyl substituted pens in the compounds of the present invention. In the case of melamine systems, each N-containing heterocyclic ring preferably contains at least three or more vinyl groups and one or more carbamal groups, wherein the heterocyclic ring has 3-5 vinyl groups and 1-3 Must contain carbamyl groups.

Process for preparing novel nitrogen-containing heterocyclic compounds of the present invention:

The novel compounds of the present invention are reactants (B) consisting of (i) alkylcarbamates and (ii) unsaturated acids, alcohols or amides, and alkoxymethylated or methylolated nitrogen-containing heterocyclic compounds (A) It can be prepared by the reaction of.

The nitrogen containing heterocyclic component (A) may be combined with the reactants (B) (i) and (B) (ii) or in any order. Thus, the reaction with the alkyl carbamate may proceed first, followed by the reaction with the vinyl-terminated compound, or vice versa. According to the invention, the starting material is reacted with an alkyl carbamate, such as methyl carbamate or propyl carbamate, in the presence of an acid catalyst. Illustrative responses are represented by the following formula (for melamine type compounds).

Wherein vinyl is as defined above, R ⁵ and R ⁶ are as previously defined, and m is the preferred degree of carbamylmethylation. The reaction is typically carried out at 80 ° C.-150 ° C. by heating in a melt or solution such as toluene in the presence of catalytic amounts of acids such as para-toluenesulfonic acid, nitric acid, sulfuric acid and the like. By measuring the amount of alcohol and / or water released, the degree of completion of the reaction can be determined. Typically, m is 2-4 for carbamylmethylation of melamine and m is 2 for carbamylmethylation of benzoguanamine or glycoluril. Methods of placing carbamylmethyl substituents on nitrogen containing heterocyclic nuclei are generally described in columns 3 and 4 of US Pat. No. 4,710,542.

The positioning of vinyl-terminus groups in nitrogen-containing heterocyclic compounds has been described by A. Gams, G. Widmer and G. Widmer, who demonstrate etheretherification to prepare allyl termination forms. Helv Chim Acta 24,318 E, (1941) of Flux. Fish (W, Fisch) and US Pat. No. 3,020,255, which discloses an ethier exchange reaction to prepare acrylic terminated derivatives. In carrying out the ether exchange reaction, the degree of substitution of the vinyl-terminus group n is typically adjusted to 2-4 for melamine and n is 2-3 for benzoguanamine or glycoluril. Suitable vinyl reactants are acrylamide, methacrylic acid, methacrylamide, acrylic acid and hydroxy tubes selected from monomers such as hydroxy alkyl acrylates and hydroxy alkyl methacrylates. The disclosures in US Pat. No. 3,020,255, columns 4 to 5 are incorporated herein by reference.

The reactions required to place the vinyl-terminus and carbamyl groups on the alkylmethylolated methylolated hetirocyclic nuclei can be carried out simultaneously or separately and in any desired order.

According to the process for the preparation of the novel nitrogen-containing heterocyclic compounds of the invention as described above, a mixture of products in which the vinyl-terminated substituents and the carbamylmethyl substituents are statistically distributed is obtained. Typically, at least the predominant parts by weight of the reaction product contain a novel nitrogen containing heterocyclic compound having at least two vinyl-terminated substituents and at least one carbamylmethyl substituent.

The novel compounds of the present invention have general use as resin precursors for forming objects and coatings, but the above-described nitrogen-containing heterocyclic compounds containing both vinyl-terminated substituents and kirbamylmethyl substituents are novel adhesives, noses Has particular utility in preparing casting and sealing compositions. In addition, compositions of matter that are mixtures of the novel nitrogen-containing heterocyclic compounds of the present invention (eg, those prepared by the process) have particular applicability in preparing novel coating agents, adhesives and sealants.

Part II-New Vinyl-terminated Polyurethane / Polyamide Polymers

The adhesive composition of the present invention contains about 30-90% by weight of vinyl-terminated polyurethanes having a molecular weight of about 3,000- about 80,000, preferably 3,000-7,000, containing at least two vinyl end groups.

The novel vinyl-terminated polyurethane / polyamide component of the present invention may be prepared by a second reaction in which first reaction of vinyl acid, vinyl alcohol or amide with polyisocyanate, and the product of the first reaction with a high molecular weight polyol .

Isocyanates used to prepare isocyanate terminated polyurethane resins include aliphatic, cycloaliphatic, and aromatic diisocyanates such as 2,4-tolylene diisocyanate, metaphenylene diisocyanate, 2,6 tolylene diisocyanate, p , p'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, phenyl diisocyanate, dianisidine diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diphenyl ether diisocyanate, p-phenyl Ethylene diisocyanate, 4,4'-dicyclo-hexylmethane diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, cyclohexylene diisocyanate, tetrachlorophenylene diisocyanate, isophorone diisocyananeite, 2 , 6-diethyl-p-phenylenediisocyanate, 3,5-diethyl-4,4'-diisocyanatodi0phenyl-methane, toluene diiso Cyanato-4,4'-diphenyl diisocyanate, phenylene diisocyana art, octamethylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, hexamethylene diisocyanate, tetra Methyl xylylene diisocyanate (ie, TMXDI, available from Wayne Si, American Siyanamide Company, New Jersey, USA) Polyisocyanate). Preferred isocyanates include tetramethyl xylylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (2,4-TDI or 2,6-TDI), 4,4'-diphenylmethane diisocyanate (MDI) , Isophorone diisocyanate (IPDI) and hexamethylene diisocyanate (HMDI).

Compounds suitable for carrying out the first reaction include vinyl alcohol, vinyl acid and vinylamide, hydroxy acrylate, hydroxy alkyl acrylate and mixtures thereof. Examples of compounds suitable for the first step of vinyl-terminated oligomer preparation are allyl alcohol, hydroxy ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxy propyl methacrylate, 2 Hydroxypropyl acrylate, 2-hydroxybutyl acrylate, w-hydroxybutyl acrylate, p-hydroxyphenyl acrylate, hydroxylauryl methacrylate, 2-hydroxypropyl methacrylate, 3- Hydroxypropyl methacrylate, hydroxyhexyl acrylate, hydroxyoctyl methacrylate, monoacrylate or monomethacrylate ester of bisphenol A, fully hydrogenated derivative of bisphenol A, polyethylene glycol methacrylate, acrylic acid, meta Krillic acid, ethylacrylic acid, crotonic acid, methacrylamide, acrylamide and mixtures thereof.

The high molecular weight polyol reactants of the second stage are typically polycaprolactone diols, hydroxy terminated polybutadiene polymers, hydroxy terminated poly (butadiene-acrylonitrile) polymers, hydroxy terminated poly (butadiene-styrene) polymers suitable for the present invention. And polyhydroxy functional polymer materials, including but not limited to, a plurality of polyester polyols and polyether polyols. The choice of optimal polyol depends on the particular end-user's use. Preferred polyols, for example for plastic substrates (eg SMC), are hydroxy-terminated polybutadiene and poly (butadiene-acrylonitrile) copolymers.

It is also possible to change the reaction sequence used in the preparation of the vinyl-terminated polyurethane / polyamide polymers. Therefore, the polyisocyanate compound is reacted with the high molecular weight polyol in the first stage reaction. The first stage reaction product is then reacted with vinylic acid, vinyl alcohol or vinyl amide to produce a vinyl-terminated polyurethane / polyamide polymer that is substantially free of unreacted isocyanate substituents. The final vinyl-terminated polyurethane may also preferably be further vinyl substituted at the internal position of the structure.

The molar ratio of isocyanate group to active hydrogen group (e.g. -NH ₂ ; -OH; -COOH) in the first stage reaction is 1: 1-1,1: 1, and isocyanate group to active hydrogen combined in the first and second stages. The ratio is preferably 1: 1.

In general, each of the two reaction steps is carried out at 50 ° C.-125 ° C. for 0.5-4 hours. Preferred conditions are 2-3 hours at 60-95 ° C. The method can be carried out batchwise or continuously.

Chapter III-New Coating, Sealing and Adhesive Compositions:

The compositions of the present invention have general utility as coatings, sealants and tackifiers. All compositions of the present invention contain the following essential ingredients.

(a) at least one nitrogen containing heterocyclic compound having at least two vinyl terminated organic groups and at least one carbamylmethyl group as a reactor;

(b) at least one vinyl-terminated polyurethane / polyamide polymer having a molecular weight of about 3,000 to about 80,000 as described in Chapter II.

The coating composition and the sealing composition of the present invention have the following essential components (A), (B), (C) and (D):

(A) about 5-70% by weight of a vinyl-terminated, carbamylmethylated nitrogen-containing heterocyclic compound of the present invention;

(B) about 30-90 weight percent of a vinyl-terminated polyurethane / polyamide polymer having a molecular weight of about 3,000-80,000;

(C) about 2-30% by weight of a polymerizable diluent;

(D) about 0.5-5% by weight free-radical catalyst.

Here, the sum of component (A), (B), (C) and (D) is 100 weight% or less. Preferably, the weight percent limitation of the necessary coating / sealing composition components is as follows;

(A) 15-40% by weight of vinyl-terminated, carbamylmethylated nitrogen-containing heterocyclic compound;

(B) 50-70% by weight vinyl terminated polyurethane / polyamide polymer;

(C) 5-15% by weight of polymerizable diluent;

(D) 0.5-3.0% by weight free-radical catalyst.

The adhesive composition of this invention has the following essential components (A), (B), (C), (D) and (E).

(A) about 5-about 70% by weight of the vinyl-terminated, carbamylmethylated nitrogen-containing heterocyclic compound of the present invention;

(B) a vinyl-terminated polyurethane / polyamide polymer having a molecular weight of about 30 to about 90 weight percent of about 3,000 to about 80,000;

(C) about 2-about 30 weight percent polymerizable diluent;

(D) about 0.5 to about 5 weight percent free-radical catalyst;

(E) about 0.5 to about 10 weight percent of an adhesion promoter / coupling agent.

Here, the sum of components (A), (B), (C), (D) and (E) is 100% by weight or less. Preferably, the weight percent summer of the essential adhesive compositions (A), (B), (C) and (D) is as described for the coating / sealing composition. The preferred content of component E, namely adhesion promoter, is 2-7% by weight.

Component (a)-nitrogen-containing heterocyclic compound:

The vinyl-terminated carbamylmethylated nitrogen-containing heterocyclic compounds of the invention are described in Chapter 1-New Nitrogen-containing Heterocyclic Compounds. These novel compounds can be used separately or in combination as component (a) of the pressure-sensitive adhesive composition described herein. In particular it can be used separately or in combination as component (a). In particular, component (a) may be a composition of matter containing predominantly weight parts of a novel nitrogen-containing heterocyclic compound of the present invention, wherein said compound comprises at least two vinyl-terminated substituents and at least one carr Has a barylmethyl substituent. Novel compounds based on melamine and oligomers of melamine are particularly preferred for the combination of the composition according to the invention.

Component (b)-New Vinyl-terminated Polyurethanes / Polyamides:

The vinyl-terminated polyurethane / polyamide components of the present invention are described in Chapter 2-Novel Vinyl-terminated Polyurethane / polyamide Polymers above. Such novel compounds are used as component (b) of the compositions described herein.

Component (c)-Polymerizable Diluent:

The composition of the present invention includes a polymerizable diluent that does not need to be removed during use or curing. The diluent participates in the formulation of the coating agent, the sealant and the adhesive and is substantially integrated into the curable composition.

Examples of reaction diluents useful in the practice of the present invention are ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, trimethylol propane triacrylate, trimethylol propane tri Methacrylate, pentaerythritol triacrylate, pentaerythritol tetramethacrylate, 1,6-hexanediol dimethacrylate, pentaerythritol triacrylate, neopentyl glycol diacrylate, isobutoxy methacrylate Acrylate (IBMA), styrene, vinyl pyrrolidone, alpha methylstyrene, meta-diisopropenylbenzene, para-diisopropenylbenzene and mixtures thereof. Particularly preferred as reaction diluents are styrene and vinyl pyrrolidone.

The proportion of polymerizable diluent is not critical, although it usually constitutes 2-30% by weight, preferably 5-15% by weight of the adhesive composition. The proportion of polymerizable diluents can be adjusted to achieve the desired viscosity in the adhesive composition.

The polymerizable diluent is also preferably a solvent for the other components of the adhesive composition. As used herein, the term solvent means that the other components are dissolved under the conditions of use of the composition.

Component (D)-free-radical catalyst:

Catalysts useful in the practice of the present invention are selected from conventional free radical catalysts that decompose by heating. Generally suitable catalysts are peroxide or azo catalysts. Exemplary peroxide free-radacyl generators are benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, octanoyl peroxide, isetyl peroxide, di-t-butyl Dialkylperoxides such as peroxides, dicumyl peroxides, ketone peroxides such as methylethylketone peroxide, and easily decomposed peresters such as t-butyl peracetate, tertiary butyl perbenzo Ate, di-tert-butyl diperphthalate, t-butyl peroxyisobutyrate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5- Bis (tertiarybutylperoxy) hexane-3, n-butyl-4,4-bis (tertiary butylperoxy) valerate, including but not limited to. Another useful class of catalysts are peroxy compounds such as organic hydroperoxides, such as Couman hydroperoxide, cyclohexanone peroxide, methylethyl kenone hydroperoxide, tertiary butyl hydroperoxide.

The catalyst system can optionally contain accelerators / promoters such as condensation products of diethylaniline, dimethylaniline, aldehydes and primary or secondary amines; Metal salts of octylic acid, stearic acid, oleic acid, linoleic acid, naphthenic acid and rosin acid (the metal is selected from chromium, iron, cobalt, nickel, manganese and lead), lauroylmeraptan, thio It may contain urea. Typically, 0.1-5% by weight of accelerator / promoter is used.

Particularly preferred catalysts of the present invention are azo type AU radical catalysts such as alpha-alpha azo-di-isobutylronitrile.

Preferred azo polymerization initiators have the following molecular structure.

Where R is methyl, ethyl or isobutyl, and

Typically, the free-radical catalyst comprises about 0.5-about 10.0 weight percent of the composition. The activity of the catalyst, measured by half-life, is a useful indicator of its suitability as a free radical generator for a particular application. The availability of a particular free radical catalyst can be determined by mixing it with the other components of the composition of the present invention and measuring the resulting shelf-life and degree of cure at service temperature. The catalyst can be used in microencapsulated form if desired.

Component (E)-Adhesion Promoter / Coupling Agent:

The adhesive composition of the present invention contains a component for enhancing the bonding force to substrates such as steel, glass and plastic.

Useful adhesion promoters include silane compounds and organic anhydrides.

Silane coupling agents improve moisture resistance, adhesion, and durability of the adhesive or coating compositions produced in the present term. As the silane coupling agent for the present invention, conventional silane coupling agents can be used. Such a material is preferably a silane coupling agent having a vinyl group because it participates in the polymerization reaction for curing the composition of the present invention. Silane compounds are typically used at a concentration of about 0.5- about 10.0% by weight of the composition. The silane compound of the following general formula is preferable.

Wherein X is NH ₂ and R is C ₂ H ₅ or X is CH ₂ = C (CH ₃ ) CO ₂ and R is CH ₃ .

Examples of suitable silane coupling agents are methacryloxypropyltrimethoxysilane, vinyltriethoxy silane, vinyltriethoxy silane, vinyltris (beta-methoxyethoxy) silane and mixtures thereof.

If a silane compound is used in the composition without pretreatment of the substrate surface, there must be a stoichiometric amount of water relative to the hydrolyzable alkoxysilane.

Adhesion promoters include succinic anhydride, maleic anhydride, alkyl / alkenyl succinic anhydrides (such as dodecenyl succinic anhydride), tetrahydrophthalic anhydride, hexahydrophthalic anhydride, phthalic anhydride, glutaric anhydride, 1,4,5 , 6,7,7-hexachlorobicyclo- [2.2.1] -5-heptene-2,3-dicarboxylic anhydride, tetrachlorophthalic anhydride, 3,3 ', 4,4'-benzophenone tetra Anhydrides such as carboxylic acid dianhydrides, polyazelaic acid dianhydrides, pyromellitic dianhydrides, pyromellitic dianhydride-glycol adducts, 1,2,3-cyclopentane-tertiary dianhydrides and mixtures thereof Can be. Anhydrides are particularly useful adhesion promoters when used with SMC.

Optional Ingredients:

Additives such as stabilizers, accelerators, active agents, flame retardants, pigments, plasticizers, surface active agents, pigments, inert fillers, and other ingredients that do not adversely affect, may be incorporated into the compositions.

Package of Ingredients:

The compositions of the present invention have utility in that they can be formulated as one-package systems with acceptable shelf life and can be used on their own when coating or sticking is required by the user. Typically, the one-package system consists of a mixture of essential ingredients (A, B, C, D for coating compositions, A, B, C, D, E for adhesive compositions) as described above.

It is useful for the mixture of essential ingredients of the composition of the invention to be in the form of a solution, in which the components are typically mutually soluble under conditions of use. However, it is also possible to use the curable compositions of the invention in the form of suspensions if the components are uniformly dispersed with one another under the conditions of use.

One-package systems may also contain stabilizers to slow down or prevent crosslinking of the composition components during transport or storage. Stabilizers useful in the present invention include hydroquinones, p-benzoquinones, anthraquinones, naphthaquinones, phenanthraquinones and substituted compounds of these compounds. In addition, various phenols may be used, such as 1,6-di-tert-butyl-4-methyl phenol, 4-methoxy phenol, 3,5-di-tert-butyl-hydroxytoluene.

However, the composition of the present invention can be formulated as a bicomponent package system. Typically, this two-package system will consist of a first package containing a free-radical initiator and a second package containing an accelerator / promoter for the selected free-radical catalyst. Two-package adhesive formulations are used by combining packages in close proximity to use.

How to use:

The sticking, sealing and coating compositions of the present invention are applied by conventional methods such as brushing, spraying, dipping, padding or injection. The composition is typically cured by reverse application such as a convection oven, microwave heating or infrared radiation. Curing is generally carried out at 60 ° C.-150 ° C. with conventional free-radical catalysts. In the case of bonding transparent substrates (eg glass, certain plastics), curing can be carried out by radiation such as ultraviolet radiation or a combination of heat and ultraviolet radiation. In typical surface coating applications, curing can be performed by radiation using a radiation-sensitive catalyst. Such radiation-sensitive catalysts include camphorquinone (1,7,7-trimethyl-2,3-diketo dicyclo (2,2,1-heptane)), benzyl dimethyl ketal (BDMK) benzophenone (BP), die Oxyacetophenone (DEAP), hydroxycyclohexyl phenyl ketone (HCPK), benzyl diethyl ketal (2,2-diethoxy-2-phenyl acetophenone), 2-isopropylthioxanthone, 2 Chlorothioxanthone, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, di-secondary-butoxy acetophenone, benzoin isopropyl ether, methyl phenyl glyoxylate, 2-hydroxy-2,2-di-methyl acetophenone, benzoin isobutyl ether.

A preferred method for curing the composition of the present invention is by application of heat. The curing time depends on the specific catalyst used, but it is generally desirable to allow partial curing to develop within one minute.

A particular advantage of the pressure-sensitive adhesive composition of the present invention is that it can be applied and bonded to a substrate without special surface preparation. Typically, methylene chloride wipes or photowear can be used for standard surface preparation. In many cases, the adhesive composition of the present invention is applied to stained surfaces to yield acceptable results.

Object formed by the composition of the present invention:

The compositions of the present invention are useful for the formation of composites, fiber-reinforced composite laminates, adhesive interlayers, sealants, coatings, films, and solid materials. The most common use is for the formation of sticky interlayers and topcoatings.

Illustrated by the following examples of the invention.

Chapter 1-Preparation of New Heterocyclic Nitrogen Compounds of the Invention, Component (A)

Example 1

This example illustrates the preparation of novel compounds of the invention.

The two liter flask was flushed with a dry mill and filled with the following ingredients.

158.4 g of hexamethoxymethylmelamine (CYMEL 300, United States, New Jersey, Wayne City American Cynamide Co., Ltd.)

210.9 g of 2-ethylhexylcarbamate

86.4 g of acrylamide

1.35 g hydroquinone

600 milliliters of cyclohexane

The reaction flask was equipped with a cooler and a trap. The flask contents were first heated in a 90 ° C. bath until it was clear, and 4.5 g of p-toluenesulfonic acid was added to the flask.

The reaction is monitored by observing methanol, a byproduct that accumulates in the trap. When methanol collection stopped, it was removed from the methanol trap and weighed.

The reaction was terminated when the amount of methanol collected reached approximately the theoretical methanol yield. The theoretical methanol yield for this reaction was obtained after about three and a half hours after the addition of p-toluenesulfonic acid.

Cyclohexane was removed by rotary evaporator and the flask contents were reconstituted with 500 milliliters of CH ₂ CL ₂ . The p-toluenesulfonic acid was then neutralized with 100 milliliters of 5 wt% sodium bicarbonate solution. The organic layer was separated and dried over anhydrous potassium carbonate. Finally, the product was filtered and the solvent removed under vacuum (10 mmHg, 30 ° C.) to give the final product of melamine atrylamide carbamate (hereinafter referred to as compound M).

The product yield was 350 grams consisting mainly of melamine (tris-2-ethylhexyl-carbamylmethyl, tris-acrylamide methyl melamine) substituted with three carbamethyl substituents and three acrylamide substituents.

Example 2

250 ml flasks are flushed with dry air and 19.5 g of Cymel 300, 21.6 g of 2-ethylhexyl carbamate and 0.012 g of phenothiazine were charged and heated to 95 ° C. for 15 minutes to obtain a clear solution. Thereafter, 0.28 g of p-toluenesulfonic acid was added and heating continued for 15 minutes. The pressure was gradually lowered to 50 mm Hg to collect MeOH distillate. When the theoretical amount of distillate was collected, the reaction mixture was cooled to 65 ° C. and 15.0 g of 2-hydroxyethyl acrylate was added to the reactor by stirring. The pressure was lowered to 50 mm Hg and MeOH byproducts were collected. After 45 minutes, no more MeOH was produced and the reaction stopped. 100 ml CH ₂ Cl ₂ was added to the cooled reaction product. To neutralize p-toluenesulfonic acid was washed twice with 25 ml each with 5 wt% Na ₂ CO ₃ solution. The organic layer was separated and dried over anhydrous K ₂ CO ₃ . The mixture was filtered and the solvent removed to give the final product of 42 g melamine acrylate carbamate (hereinafter referred to as compound M1).

Example 3

39 g of Cymel in a 250 ml three-necked round bottom flask 300, 0.018 g phenothiazine and 30 g 2-hydroxyethylacrylate were charged. A distillation head and a mechanical stirrer were connected to the flask. The system was flushed with dry air.

The contents of the reaction flask were heated at 65 ° C. and 0.35 g of p-toluenesulfonic acid (p-TSA) was immediately added thereto. The reaction was carried out at 65 ° C. under vacuum pressure of 30 mmHg to remove byproduct methanol. After 45 minutes, 8.6 g of methanol was collected and the reaction stopped. 50 ml of CH ₂ CL ₂ was added to the cooled reaction product, and the product was washed twice with 25 ml of a 5 wt% NaCO ₃ solution. The CH ₂ CL ₂ solution of the product was dried over anhydrous K ₂ CO ₃ . The solid was filtered off and the solvent was removed to give 48 g of melamine acrylate product (hereinafter referred to as compound M2). The product consisted mainly of melamine substituted with three ethylacrylate substituents and without carbamate groups.

Example 4

This example illustrates the preparation of novel compounds of the invention.

Three liter flasks were flushed to dry run and filled with the following ingredients:

823.5 g hexamethoxymethylmelamine (CYMEL 300, United States, New Jersey, Wayne City American Cyanamide Company)

316.5 g of methyl carbamate

0.36 g phenothiazine

The reaction flask was equipped with a cooler and a trap. The flask contents were first heated in a 75 ° C. bath for 15 minutes to obtain a clear solution, then 10.6 g of p-toluenesulfonic acid was added to the flask.

The reaction pressure was gradually lowered from 200 to 50 mmHg to allow methanol distillate to collect. After a theoretical amount of methanol distillate was collected (after about 60 minutes), the submerged oil bath around the flask was cooled to 65 ° C. Thereafter, 979 g of 2-hydroxyethyl acrylate was added to the reaction mixture by stirring. The pressure was gradually lowered back to 200 to 25 mmHg and methanol byproducts were collected.

The reaction flask was cooled and 1200 ml CH ₂ Cl ₂ was added to the contents. 20 g of sodium bicarbonate dissolved in 300 ml of water was added to the flask contents to neutralize the remaining p-toluesulfonic acid. The resulting organic reaction layer was separated and dried over anhydrous potassium carbonate.

The dry product was filtered off and the solvent was removed by vacuum distillation at 30 ° C. to 40 ° C. at a pressure of 1 mmHg to give the final product of melamine acrylate carbamate (hereinafter referred to as compound M3).

The product yield was 1851 g consisting mainly of melamine (bis-carbamylmethyl, tetrakis (2-acryloyloxyethoxy) -methyl melamine) substituted with two carbamylmethyl substituents and four ethylacrylate substituents.

Example 5

1 liter flask was flushed with dry air and 205.8 g of Cymel 300, 295 g of 2-hydroxypropylmethacrylate (HPMA, Rocryl 410 from Roam and Haas Co.) and 0.1 g of phenothiazine were charged and heated to 75 ° C. for 15 minutes to give a clear solution. 2.6 g of p-tolfuenesulfonic acid was added and heating continued for 15 minutes. The pressure was lowered to 50 mm Hg to collect MeOH byproducts. The reaction was cooled to 65 ° C. when the theoretical amount of distillate was collected. 79 g of netyl carbaate were charged and the reaction mixture was stirred by stirring in 75 ° C., 50 mm Hg vacuum to collect MeOH. After 90 minutes, no more MeOH was generated and the reaction stopped. 300 ml of CH ₂ Cl ₂ was added to the cooled reaction product. P-TSA was neutralized by washing twice with 50 ml of a 5 wt% Na ₂ CO ₃ solution. The organic layer was separated and dried over anhydrous K ₂ CO ₃ . Filtration and removal of solvent gave a final product of 370 g of melamine methacrylate carbamate (hereinafter referred to as compound M4).

Other examples of resins containing carbamylmethyl and vinyl groups based on alkylated formaldehyde derivatives of melamine, benzoguanamine and glycoluril are given in Examples 6-17. The preparation in these examples is based on the general method described below.

Common way

The round bottom reaction flask was equipped with a mechanical stirrer and the trap with a cooler suitable for vacuum distillation was filled with the reactants, the reaction mixture was heated in an 80 ° C. oil bath until the reactants melted, and an acid catalyst (1-2% by weight). H ₂ CO ₄ ) was added.

The reaction was monitored by collecting alcohol via successive vacuum distillation. The reaction was over when the alcohol distillation stopped. If the amount of alcohol collected was less than the theoretical amount, it was preferred to add the catalyst second.

Since the reactivity of the carboxylic acid is low compared to the carbamate and the alcohol, it is preferable to use 20% -40% excess of the carboxylic acid. Unreacted material could be removed by increasing the vacuum before the reaction was over.

After the contents of the reaction flask were cooled to near room temperature, 350 ml of CH ₂ Cl ₂ was added during the preparation of the product. The methylene chloride solution was slowly washed with a 5% sodium bicarbonate solution in a separating funnel to neutralize and extract the acid. The organic phase was separated and dried over anhydrous sodium sulfate until the solution was clear. Finally the solution was vacuum filtered through a Buchner funnel and the solvent was removed on a rotary evaporator.

Chapter 2-Preparation of New Vinyl-terminated Oligomers (Component B) of the Invention

Example 18

This example illustrates the preparation of vinyl terminated oligomers used in the preparation of the compositions of the present invention.

One liter of glass reactor was flushed with dry air and filled with the following phases:

0.02 g phenothiazine

140.6 g of meta-tetramethylxylylene diisocyanate

The contents of the reaction flask were heated at 80 ° C. for 10 minutes and 0.15 g of T-12 (dibutyltin dilaurate) catalyst was added. Thereafter, 73.4 g of 2-hydroxyethyl acrylate was gradually added for 30 minutes, and the reaction mixture was stirred by stirring at 80 ° C. for 1 hour.

143 g of polycaprolactone diol polymer (CAPA 200 diol, molecular weight 550; product of Interlox Chemicals) was added to the reaction mixture in four portions for 30 minutes. The reaction mixture was continued to stir at 80 ° C. for 1½ hours.

320 g of the reaction product of urethane acrylate were collected and named H oligomer.

Example 19

This example illustrates the preparation of vinyl-terminated oligomers used in the preparation of the compositions of the present invention.

The 500 ml glass reactor was flushed with dry air and filled with the following ingredients:

0.02 g of benzoquinone

14.6 g of meta-tetramethyl xylylene diisocyanate

The contents of the reaction flask were heated at 80 ° C. for 10 minutes and 0.10 g of T-12 (dibutyltin dilaurate) catalyst was added. Thereafter, 7.66 g of 2-hydroxyethyl acrylate was gradually added for 30 minutes and the reaction mixture was stirred by stirring at 80 ° C. for 1 hour.

90 g of poly (butadiene-acrylonitrile) copolymer (Hycar HTBN 1300x 29, product of Goodrich Tire Company) was added to the reaction mixture in 6 minutes for 30 minutes. The reaction mixture was continued to stir at 80 ° C. for 1½ hours.

100 g of the reaction product of urethane acrylate were collected and named HT-M oligomer.

Example 20

One liter flask was flushed with dry air and filled with 0.06 g benzoquinone and 43.8 g tetramethylxylene diisocyanate. The mixture was stirred at 80 ° C. for 10 minutes to mix. 0.3 g of T-12 (dibutyltin dilaurate) was added to the reaction mixture and immediately 26.6 g of hydroxypropyl methacrylate was added for 30 minutes. The reaction mixture was stirred for 1 hour at 80 ° C. and 270 g of Hycar HTBN 1300 × 29 (polybutadiene-acrylonitrile) copolymer was added in 6 minutes within 30 minutes. Stirring was continued for 1½ hours at 80 ° C.

The reaction was then stopped and the reaction product was poured into a hot suitable reactor. 330 g of the reaction product of urethane methacrylate were collected and named HT-MM oligomer.

Chapter 3-Gradual Characterization of the Compositions of the Invention Single Component System.

Example 21

The base material adhesive was prepared with 70 parts of HT-M (product of Example 19), 25 parts of M3 (product of Example 4), 5 parts of N-vinylpyrrolidone (NVP), 5 parts of succinic anhydride and 30 parts of IMSIL. Prepared from a mixture of 15 silicas (product of Illinois Minerals Company). Several original package blends of the above materials, various initiators and stabilizers, were used to bond the Rockwell 9468 polyester plastic panels SMC. The parts were press heated at 250 ° F. (121.1 ° C.) for 2 minutes and the cooled parts were postbaked at 110 ° C. for 30 minutes. The wedge test for the base material adhesive was performed as follows.

Combination of SMC and SMC

The following test procedure was used to evaluate the cohesive bonding of SMC and SMC for all of the following examples.

Commercial polyester plastic SMC panels (supplied from suppliers of Rockwell International, Div. Tech, etc.) were cut into 1 inch × 4 inch (2.54 cm × 10.16 cm) coupons for bonding tests. The binding site of the coupon was wiped off with a dry cloth without pretreatment. Sufficient adhesive was applied to cover the overlap area of 1 inch x 1 inch (2.54 cm x 2.54 cm). 30 mils (0.762 mm) of glass beads were sprinkled onto the surface of the adhesive (by an amount not covering more than 1% of the surface area). 30 mil spacer (0.762 mm) (metal shim or Teflon Strips) were used at one end of the test part to achieve a constant 30 mil (0.762 mm) adhesive bond line. Separation parts with spacers inserted and surrounded by a protective Mylar film net are prepared to be placed in a heated press. The parts were heated under pressure at 250 ° F. for 1-2 minutes. Preferred pressures are generally 8-10 psi (6.56-0.70 kg / cm ² ). After the first 1-2 minutes of heating, the assembled coupons are allowed to cool to room temperature and tested for green strength, and then the coupons are shaken by hand to ensure that they are not easily separated (pass the test). Thereafter, the spacer was removed and excess adhesive was removed from the ends. Finally, the combined parts were transferred by postheat treatment at 300 ° F. (148.9 ° C.) for 30 minutes and then cooled. A 45 ° angular separation test of the parts was performed to determine the type of cohesive failure pattern. Types of destruction have been reported as follows. Fiber tear (FT), cohesive failure (AF), cohesive failure (CF), stock break (SB).

For the lap shear test, a lap arrangement of parts was used. The adhesive bond was 1 inch x 1 inch (2.54 cm x 2.54 cm) with a 30 mil (0.76 mm) spacer. The parts were press heated at 250 ° F. (121.1 ° C.) for 1-2 minutes to observe green intensity. The parts were moved and cooled. Lap shear measurements with an Instron machine were performed at a crosshead speed of 0.05 inches / minute (1.27 cm / minute) by ASTM method D-1002.

The test results obtained from the single component system of Example 21 are shown in the table below.

Example 22

The blends 21A-E were kept at room temperature storage. The aged adhesive was then checked by the same method as in Example 42. The results of the separation test of the Rockwell 9468 SMC-to-SMC binding test obtained for Formulation 21A-E are reported below. The results show that the adhesive blend is stable up to 90 days at room temperature.

Example 23

The following adhesives with different compositions were used to bond the SMC coupons (wipe only with a cloth). The parts were press heated at 250 ° F. (121.1 ° C.) for 1 minute. The cooled parts were post-heat treated at 300 ° F. (148.9 ° C.) for 30 minutes. The separation test results are shown in the table below.

Essential components of the present invention for A, B, C, D, E-adhesive compositions as defined in the text, Chapter 3

S.A. = Succinic anhydride

M.A. = Maleic Acid Accompany

p-BQ = p-benzoquinone

NVP = N-Vinyl Pyrrolidone

STY = styrene

Cab-o-sil , Fumed Silica, Cabot Corporation Imsil , Silica, Illinois Minerals Company

Example 24

Formulations 23A and 23B described above were used to combine Rockwell 9468 SMC coupons. The pressure-sensitive adhesive was cured in the same manner as in Example 23. Lap shear measurements of the cured parts were performed at 180 ° F. (82.2 ° C.). The data is recorded below.

Example 25

The combinations 23A and 23B were used to combine Rockwell 9468 SMC coupons. The adhesive was cured in the same manner as in Example 23. The cured parts were infiltrated with deionized water at 54 ° C. for 7 days. After 7 days, the parts were allowed to air dry and subjected to separation test and lap shear measurements at room temperature and at room temperature. The results are tabulated below.

Binary system

Example 26-38

Two basic standard adhesives, 26A and 26B, were formulated according to the following composition.

HT-M is a vinyl-terminated polyurethane / polyamide oligomer prepared by the method of Example 19.

M3 is a melamine derivative prepared by the method of Example 4.

Two-component tack systems consist of A with an initiator (such as hydroperoxide or peroxide) and B with an accelerator / accelerator (such as transition metal complex or tertiary aromatic amine).

Several bi-component adhesives have been formulated using base adhesives 26A and 26B with different initiator / promoter bonds. The same weight blend of A and B was mixed thoroughly. The well mixed tack was applied to Rockwell 9468 SMC coupons. Curing conditions were the same as in Example 23. The result of the separation test of the resulting pot-life and assemblies of the mixed adhesive is tabulated below.

CHPO = Kupil Hydroperoxide

CoNaph = 50% by weight of cobalt (II) pentanedionate in NVP

CPO = di-kufil peroxide

DMA = dimethylaniline

t-BPO = di-t-butyl peroxide

BPO = benzoyl peroxide

Bonding of glass and steel

The following method was used to evaluate the adhesive of the present invention for applications in which glass is bonded to steel. Fingerboard: 1 inch × 4 inch × ¼ inch (2.54 cm × 10.16 cm × 1.27 cm) plate glass coupon and 1 inch × 4 inch (2.54 cm × 10.16 cm) ＃ 25 cold rolled GM steel coupon

The glass coupon was immersed in a silane I solution as described below for 5 minutes. The air dried coupons were baked at 110 ° C. for 12 minutes. The steel coupon was treated with tin hydrosol (described below) for 5 minutes and dried in open air. The steel coupon was then immersed in silane I solution for 5 minutes, dried in air and then baked at 110 ° C. for 12 minutes. Various formulations of adhesive were applied in overlapping portions of ½ inch by 1 inch (1.27 cm by 2.54 cm) with a thickness of 2 mils (0.051 mm). The adhesive was cured at 100 ° C for 30 minutes.

(1) Silane I solution-Prepared by adding 139.7 g of anhydrous ethanol and 74.9 g of water to a 500 ml beaker and adjusting the pH to 5 with aqueous acetic acid. 5.3 g of 3-methacryloxypropyl trimethoxysilane was added dropwise to the solution by stirring for 15 minutes. The final solution was used for pretreatment of the substrate as described above.

(2) Tin Hydrosol-Prepared by dissolving 1 g of SnClHO in thion water to obtain a 1% by weight solution. Tin chloride was then added to the resulting solution in two steps. (i) 2.5 g of SnCl was added and (ii) 1.0 g of SnCl was added. Each SnCl addition was performed at room temperature with agitation to ensure complete dissolution before the next addition. The final tin hydrosol solution was used for pretreatment of the substrate as described above. Lap shear data is reported in the table below.

The results show that the carbamylated acrylic pressure sensitive adhesive containing M (compounds I and II) and M1 (compounds J and J1) is superior to the non-carbamylated pressure sensitive adhesive containing M2 (compounds K and K1).

Glass to glass

Substrate: 1 inch × 4 inch × ¼ inch (2.54 cm × 10.16 cm × 0.635)

The glass coupon was immersed in silane I solution for 5 minutes. The air dried coupons were heat treated at 110 ° C. for 12 minutes. The electrodeposition agent was applied as a coupon cooled in 1 inch × ½ inch (2.54 cm × 1.27 cm) overlapping portion of 2 mils (0.051 mm) thickness. The adhesive was cured at 110 ° C. for 30 minutes.

Lap shear data is reported below.

The results showed that the pressure sensitive adhesives containing the crosslinkers M and M1 of the present invention had better bond strength than M2, non-carbamylated acrylmelamine.

Combination of steel and steel

Substrate: 1 inch × 4 inch (2.54 cm × 10.16 cm) ＃ 25 cold rolled GM steel coupon.

Pretreatment:

The steel coupon was degreaseed by wiping with CHCl and the coupon was immersed in silane II solution (as follows) for 5 minutes. The air dried coupons were heat treated at 110 ° C. for 12 minutes. These pretreated coupons were used for application to the adhesive. Adhesive I was applied to the pretreated steel coupon having a 1 inch x 1/2 inch (2.54 cm x 1.27 cm) overlap. The thickness of the electrodeposition agent was 5 mils (0.127 mm). The adhesive-bonded coupons were cured at 110 ° C. for 30 minutes. Tackifiers J and K were applied and cured in a similar manner.

Silane II solution-139.7 g anhydrous ethanol, 7.4 g water and 3 g It was formulated as the previous silane I solution except that aminopropyltriethoxy silane was used. The final solution is used for pretreatment of the substrate as follows.

The lap shear data of the cured coupons by Instron test is as follows.

(1) psi = pounds / inch

The results show that the bond strength of the pressure-sensitive adhesives combining vinyl-terminated carbamylalkylated melamine M and M1 is stronger than non-carbamylalkylated M2. Effect of overbake on adhesive bonds Substrate: 1 inch x 4 inches (2.54 cm x 10.16 cm) ＃ 25 cold rolled steel coupon Pretreatment:

Following the same procedure as in Example 48-50 for steel pretreatment, the adhesive was applied to an overlap of ½ inch × 1 inch (1.27 cm × 2.54 cm) of 2 mils (0.0508 mm) thick and 30 at 110 ° C. Cured for minutes. Some cured specimens were further superheated at 200 ° C. for 30 minutes. Lap shear data for a 110 ° C./30 min cure and 200 ° C./30 min superheat sample is summarized below.

The results show that after overheating at 200 ° C./30 minutes, the pressure-sensitive adhesive (M in Blend I) containing the carbamylated acrylate melamine compound of the present invention retains 95% of the original bond strength. However, the pressure-sensitive adhesive (M2 in Blend K) containing non-carbamylated acrylate melamine lost 16% of its original bond strength after overheating. These results show that the thermal stability of the pressure sensitive adhesives prepared from combining the novel and essential components used in the present invention is better than those produced from similar non-carbamylated compounds.

It is anticipated that many variations will be readily apparent to those skilled in the art upon reading this description. All such modifications will be included within the scope of the invention as defined in the appended claims.

Claims (3)

Prepared by reacting vinyl acid, vinyl alcohol or alcohol or vinyl amide with polyisocyanate in the first step, followed by reacting the reaction product of the first step with a high molecular weight polyol in the second step, having a molecular weight of 3,000 to 80,000, Vinyl-terminated polyurethane / polyamide polymers containing at least two vinyl end groups. A curable coating / sealing composition consisting of the following (A)-(D): (A) 30 to 90% by weight of a vinyl-terminated polyurethane / polyamide polymer having a molecular weight of 3,000 SOWL 80,000; (B) 5 to 70 weight percent of at least one nitrogen containing heterocyclic compound comprising at least one carbamylmethyl and at least two vinyl-terminated organic groups as a reactor; (C) 2 to 30% by weight of a polymerizable diluent; And (D) 0.5 to 5% by weight free-radical catalyst, wherein the sum of components (A), (B), (C) and (D) does not exceed 100% by weight. A curable pressure-sensitive adhesive composition comprising (A)-(E): (A) 30 to 90 weight percent of a vinyl-terminated polyurethane / polyamide polymer having a molecular weight of 3,000 to 80,000; (B) 5 to 70% by weight of one or more nitrogen-containing heterocyclic compounds comprising at least one carbamylketyl group and at least two vinyl-terminated organic groups as reactors; (C) 2 to 30% by weight of a polymerizable diluent; (D) 0.5 to 5% by weight free-radical catalyst and (E) 0.5 to 10% by weight adhesion promoter / coupling agent (wherein components (A), (B), (C), (D) and (E) Sum does not exceed 100% by weight).