KR910008304B1 - Hydroxyalkyl carbamate - Google Patents

Abstract

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Description

Thermosetting Coating Compositions Containing Hydroxy Alkyl Carbamate

The present invention relates to a novel hydroxyalkyl carbamate having one or more secondary amine groups on the molecule, the preparation thereof and the thermosetting coating composition containing the same.

Reactions of propylene carbonate with primary and secondary amines to produce the corresponding 2-hydroxypropyl carbamate are known in the art (Comp. Rend, 1142, 1954).

Similar reactions of ethylene carbonate are exemplified in the literature (“Preparation of Polymerizable and Cyclic Urethanes and Ureas from Ethyl Carbonate and Amines”, by Elizabeth Dyer and Harvey Scott, J.A.C.S. (1956) pp.672-675). See another document (“Polyurethane Elastomers Obtained Without Diisocyanate”) by L. Ya. Rappoport, GN Petrov, II Trostyanskaya and OPD Gavrilova in International Polymer Science and Technology, 8, No. 1, 1981. can do. The Dier-Scott literature states that polyurethanes can be prepared by removing ethylene glycol from 2- (hydroxyethyl) -carbamate, thereby avoiding the use of diisocyanates. Lapportport et al. Generally refer to reactions in which a cyclic carbonate is reacted with an amine to produce a polyurethane elastomer. Thus, the prior art refers to the reaction of amines with, for example, propylene carbamate, to produce the corresponding hydroxy alkyl carbamate. Another route for producing saturated and unsaturated polyurethanes, including polycondensation of glycol bis (chloropromate) with diamines, is known in the literature (Journel of Polymer Science, Vol. 7. 899 916 (1969)). Topic "Novel methods for preparing saturated and unsaturated aliphatic polyurethanes" by Y. Mizake, S. Ozaki and Y. Hirata, p899-915).

The reaction of diamine with ethylene carbonate followed by a catalytic exchange ester reaction with glycol or macroglycol to produce bis (2- hydroxyethyl) carbamate is shown in the following document ("thermoplastic polyurethane elastomer", by Richard D. Cowell, Journal of Elastomers and Plastics, Vol. 14, (October, 1982), p195-203).

A product sold under the trade name Jeffamine D2000 consisting of two types of multiamines, namely 1, 4 cyclohexane-bis- (methyl-amine) and polyamines with polyoxypropylene backbone, was used.

Coating compositions comprising backbone polymers and crosslinkers, which react with the crosslinkers at high temperatures to form crosslinked polymers but which contain relatively stable sites at ambient temperatures, are also known in the art. One problem with such compositions is that the backbone polymers that are commonly used have high viscosity and high softening temperatures and therefore require the use of solvents that lower the polymer viscosity. The solvent must be volatilized after applying the coating composition and heat curing it, which causes environmental, health and processing problems.

It is known to use high boiling point diols or polyols in the composition as reaction diluents to obtain high solids containing coating compositions. However, in the case of coating compositions or amino catalyst paints containing amino crosslinkers, the presence of diols or polyols reduces the shelf life of the coating composition because the hydroxyl groups on the polymer react with the amino crosslinkers.

It is known in the art to use, as crosslinking agents, protected isocyanates which are non-reactive or stable with respect to functional groups such as hydroxy or amine groups at room temperature and which crosslink and react with them at high temperatures. For example, US Pat. No. 3,984,299 (Robert D. Jerabek) discloses electrodepositable compositions consisting of amine addition products of epoxy group containing resins, protected organic polyisocyanates and optionally urethane formation reaction catalysts. Protected isocyanates are shown to be any isocyanates if the isocyanate group is reacted with a compound such as an aliphatic, cycloaliphatic, aromatic alkyl monoalcohol or phenolic compound.

It is generally indicated in the art to use protected isocyanates as crosslinking agents in coatings such as powder coatings, electrodepositable coatings, aqueous and organic solvent containing coatings. Protected isocyanates are generally prepared by reacting protective agents such as monoalcohols, phenols, lactams, oximes, beta-dicarbonyl compounds, triazoles, hydroxamic acid esters with aliphatic or aromatic polyisocyanates. Reference can be made to the literature (eg Progress in Organic Coatings Review, 9, 1981 Z. Wicks).

One disadvantage associated with the use of protected isocyanate compounds is the need to store and handle these toxic compounds. Another difficulty is that suitable isocyanate compounds are relatively expensive compared to the compounds used in the present invention.

Electrodepositable resin compositions are also well known in the art. For example, cationic electrodepositable compositions of amine adducts of organic polyisocyanates and epoxy resins protected in US Pat. No. 4,031,050 are known. As shown in this patent, electrodeposition of such compounds, which may optionally contain a urethane-forming reaction catalyst, can be performed to result in a coating having desirable properties on the conductive substrate. Reference may also be made to US Pat. Nos. 3,984,299 and 4,031,050. However, isocyanate compounds are toxic and very reactive and care must be taken to handle and store them.

US Pat. No. 4,017,438 discloses cationic electrodepositable resins derived from epoxy resins which are enhanced by introducing primary amine groups in the resin molecule by reacting some polyamine compounds having primary amine groups protected by ketamine. Ketimine groups decompose upon contact with water to provide primary amine functionality as is known in the art.

Protected isocyanates are known, along with amine-resin adducts, to provide cationic electrodepositable resin systems with suitable catalysts.

The electrodeposited coating is generally crosslinked through urethane, hydroxy and amino groups when heated to a high temperature, generally in the presence of a crosslinking catalyst.

As is known, "protected" isocyanates react with hydroxyl and amino groups under high temperature to form urethane and urea crosslinks.

Coating systems based on organic solvent bases, such as isocyanate systems, provide high performance urethane crosslinked coatings, but use volatile or toxic organic solvents, causing fire hazards and environmental damage. Commercially available isocyanate compounds are usually toxic and very reactive and require proper care in handling and storing them.

Aqueous polyurethane solutions or dispersions are known as coating agents, but these known systems usually require a high curing temperature of 176-315 ° C. to achieve cross-linking through urethane groups. Although low temperature or room temperature curable aqueous solutions or dispersions of polyurethanes that do not contain isocyanates are available, these coatings do not crosslink through urethane groups, so they do not appear to meet the standard performance achieved by urethane crosslinking coatings. .

Aqueous acid solutions of polyurethanes are most often obtained by adding acids to form cationic dispersions, bases to form anionic dispersions, or by adding surfactants, all of which additives are detrimental to the properties of the cured film obtained therefrom. It should not affect. Aqueous cationic-, anionic- or surfactant-dispersed isocyanate-based polyurethanes, for example, often suffer from a lack of safety as they age.

If a -NCO group is present, the reaction between water and isocyanate takes place in about 3-20 hours at room temperature. Thus, isocyanate-based polyelectrolytes that are completely soluble in water are easily hydrolyzed in water or become brittle and hygroscopic after removing water. Because of these problems caused by the high content of ionic groups in these materials, they are generally of no practical importance in the field of coatings and plastics.

One class of nonionic aqueous solutions of polyurethanes is based on the incorporation of polyester glycol or polyether glycol segments. However, polyester-glycols are very sensitive to hydrolytic denaturation, while the water solubility of polyether glycol-based resins is isocyanate-dependent. Moreover, both types tend to form cured films that are excessively sensitive to water, ie swell, turbid (turn white), soften and sticky when exposed to water.

In polyfunctional amines which now contain at least one primary amine group and at least one hindered secondary amine group, the primary amine groups react selectively with cyclic carbonates while one or more secondary amine groups are non- The reaction remained unexpectedly found to result in hydroxy alkyl carbamate. The resulting hydroxy alkyl carbamate contains at least one unreacted secondary amine group and is useful as an intermediate to prepare a crosslinked polymer via hydroxy alkyl carbamate groups.

In general, a first feature of the present invention is to provide a polymer compound composed of at least one hydroxy alkyl carbamate group and at least one unreacted secondary amine group and a process for the preparation thereof.

The compounds of the present invention are further described by the following general formulas and special structural formulas and should be considered to include their isomers and mixtures thereof.

A second feature of the invention is a self crosslinkable polymer containing at least two hydroxy alkyl carbamate groups per molecule and at least one hydroxy alkyl carbamate group and polymerized to form a self crosslinkable polymer. It relates to a monomer that can be.

A third feature of the present invention is (1) reactive diluents useful in coating compositions obtained by reacting carbonates with primary amines to produce hydroxy alkyl carbamates, and (2) one or more hydroxyalkyl carbamate compounds as reactive diluents. It is to provide a composition containing.

A fourth aspect of the invention relates to a coating composition composed of a hydroxyl group-containing polyurethane or polyurea compound and an amino crosslinker.

A fifth feature of the invention is (a) a crosslinker containing at least two hydroxy alkyl carbamate groups obtainable as a reaction product of amines and cyclic carbonates, and (b) containing two or more active functional groups. A thermosetting composition consisting of a polymer and (c) optionally a crosslinking catalyst, wherein the crosslinker (a) and the polymer (b) are stable to each other at ambient temperature and reactive to each other at high temperatures.

A sixth aspect of the present invention is to provide a negative electrodepositable self crosslinkable polymer containing at least one tertiary amine group and a hydroxy alkyl carbamate group per molecule.

The polymer comprises (a) an epoxy resin having an average epoxy equivalent of about 300-10,000, preferably about 1000-4000, and (b) at least one hydroalkyl carbamate or precursor thereof and at least one secondary amine group. It can be obtained as a reaction product with one or more amines.

A seventh feature of the present invention is one of alkyl alkyl carbamate groups obtained by capping the reaction product of (a) (i) hydroxyalkyl carbamate and (ii) cyclic carbonate (such as ethylene carbonate or propylene carbonate) with polyamine Or a hydrophobic crosslinker having at least two carbamate groups selected from the class consisting of both, (b) water-soluble and hydrophobic amino group-containing polymers, and (c) polymers (b) to provide cationic groups such that the polymer is water-dispersible An acid dispersant (such as an inorganic acid or a hydrophilic organic acid) effective to achieve this, and (d) optionally a negative electrode electrocoating composition consisting of a crosslinking catalyst, wherein the crosslinker (a) and polymer (b) in the composition are at ambient temperature. Stable to each other, but reactive at high temperatures

An eighth feature of the present invention is to provide a hydrophilic substantially epoxy-free self-crosslinkable polymer containing hydroxy alkyl carbamate groups and one or more tertiary amine groups.

It is a ninth aspect of the present invention to provide a self crosslinkable acrylic polymer containing at least two hydroxy alkyl carbamate groups per molecule.

A tenth aspect of the present invention provides an adhesive system for bonding a product surface composed of a structural adhesive between a primer coating and a primer coating on a product surface, wherein the primer coating comprises a hydroxy alkyl carbamate group and at least one tertiary amine. It consists of a cured polymer crosslinked by the reaction of hydroxy alkyl carbamate groups with groups.

In general, compounds of the first aspect of the invention are prepared by reacting one or more amines with a cyclic carbamate to produce the compound of formula (1).

Wherein R is an organic component having at least one unreacted secondary amine group, and R ₁ , R ₂ and R ₃ are each independently H or C ₁ -C ₂₀ alkyl, cycloalkyl or alkyl aromatic components or at least one Any such component containing one or more hetero atoms in addition to the above carbon atoms, n is 0 or 1. R may also contain one or more hetero atoms. Such components containing one or more hetero atoms include, for example, those containing ether groups, thio groups and organo-silicon components.

Cyclic carbonates that react with the polyfunctional amine include any suitable cyclic carbonate, including biscarbonates that are reactive with one or more of the primary amine groups of the polyfunctional amine.

In general, when compared with hexagonal cyclic organic carbonates, five-membered cyclic organic carbonates are preferred because hexagonal cyclic organic carbonates are relatively more expensive and difficult to manufacture. Therefore, the cyclic carbonate which can be preferably used has the following structural formula.

Wherein R _a and R _b are the same or different and may be composed of H or C ₁ -C ₈ aliphatic, cycloaliphatic, aromatic or heterocyclic compounds, respectively. Ethylene carbonate (dioxolan-2-one), i.e., Ra and Rb are both H and propylene carbonate (4-methyl dioxolan-2-one), i.e., R _a = H and R _b = CH ₃ admit.

The polyfunctional amine contains at least one secondary amine group that is masked in view of the reaction of the cyclic carbonate with the at least one primary amine group. As used herein and in the claims, "polyfunctional amine" means an amine containing at least one primary amine group and at least one masked secondary amine group, and (b) a "shielded secondary amine group" Refers to such secondary amine groups in which the reaction with cyclic carbonates has been stericly and electrically blocked under such conditions in which primary amine groups react. Surprisingly, it has been found that the reactivity of primary and secondary amines with cyclic carbonates is selectively high for primary groups for certain polyfunctional amines.

In other words, certain polyfunctional amines have such secondary amine groups that are blocked stericly or otherwise from reaction with cyclic carbonates but are reactive with epoxy or other functional groups that may be on the main chain polymer. Found out. Thus, masked secondary amine groups contained in polyfunctional amines may form hydroxy alkyl carbamates with one or more cyclic carbonates, in which case secondary amine groups remain unreacted and react with epoxy or other active groups. Can be. This allows the composition to act effectively as a means of immobilizing hydroxy alkyl carbamate groups by reacting the composition with an epoxy or other active group on the backbone polymer. For example, when ethylene and propylene carbonate react with diethylene triamine, they selectively react with the primary amine groups of the triamine to form carbamate groups while the secondary amine groups remain unreacted. These secondary amine groups can then be reacted, for example, with epoxy groups on the main chain polymer without affecting the carbamate groups.

These compounds can also be used to prepare hydroxy alkyl carbamate group containing polymers that can be self-crosslinked to produce thermoset polyurethanes suitable for various applications in the coatings field. Self-crosslinking reactions can be base or tin catalyzed and are advantageous over conventional amino resin systems that required acidic catalysts. The present invention thus enables the use of a system that does not contain formaldehyde, which can prevent hardening inhibition in the presence of a shielded amine UV stabilizer.

Prior to discussing the preparation of the hydroxy alkyl carbamate-containing compounds of the present invention in detail, their use can be illustrated as follows. The hydroxy alkyl carbamate-containing compounds can react with any suitable "backbone" polymer containing an active group such as, for example, an epoxy group, in which case the reaction can be represented as follows.

In the above scheme, R _h represents a segment of an epoxy-containing resin, and R _i and R _j represent a segment of a hydroxy alkyl carbamate-containing amine or polyamine compound of the present invention. The reaction generally occurs at room temperature or slightly higher temperatures and is often exothermic. The reaction can be carried out without solvent or else use of aprotic or alcoholic solvents. Various backbone polymers having various reactive functional groups can also be used as described in detail below. Representative polymers having, for example, one or more of the compositions of the invention immobilized thereon may have the following structure.

The resulting polymer can be crosslinked upon heating and optionally in the presence of a suitable crosslinking catalyst, via one or more mechanisms, for example by crosslinking via backbone hydroxyl groups such as (5),

For example, by crosslinking by self condensation as shown in (6),

및

And

For example, it may be crosslinked by crosslinking through a main chain amine group such as (7).

R _k in the scheme is hydrogen or main chain polymer segment.

In addition to being useful as intermediates in the preparation of self-crosslinkable polymers, the compounds of the present invention can be used to form such tacky films that self-condense in the absence of a backbone polymer, which has poor resistance to water but excellent resistance to organic solvents.

A wide variety of polyfunctional amines can be used in the present invention for reaction with cyclic carbonates, where it is necessary for the polyfunctional amine to contain at least one primary amine and at least one masked secondary amine. . For example, one class of polyfunctional amines that can be used in the present invention can be represented by the following formula.

R _c- (NH-R _d ) _{n 2} -NH-R _e

Wherein n ₂ is 0-5, R _c , R _d and R _e are each independently a straight or branched chain hydrocarbon segment containing 2-6 carbon atoms, and at least one of R _c and R _e is a primary It contains an amine group.

Suitable amine class structures can only be derived by substituting only -NH ₂ for the hydroxy alkyl carbamate component of the compounds represented by the following structural formulas (8) to (11).

Wherein A is [NH (CH ₂ ) n] NH, n is 0-10, x is independently 2-6, preferably 6, and R ₁ and R ₂ are each independently H or C ₁ -C ₂₀ alkyl or alkyl aromatic component, preferably H or CH ₃ .

It is preferable that n is 10 or less, and it is more preferable that it is 0-6 especially 0-4. Compositions where x is 2 or 6 may be prepared from various available reactants such as diethylenetriamine and dihexamethylene triamine, with some preference.

Another suitable class of compounds can be represented by the following structures.

Wherein y is 2 or 3, R ₁ and R ₂ can be defined as above, and R _m is C ₁ -C ₂₀ alkyl, cycloalkyl or alkyl aromatic component or at least one carbon atom or Any such component containing more heteroatoms. Starting materials that provide C ₂₀ or more alkyl, cycloalkyl or alkyl aromatic components in this class of compounds are not readily available. Some preference is given to C ₁ -C ₂₀ alkyl, cycloalkyl or alkyl aromatics and slightly shorter chains such as C ₁ -C ₁₈ alkyl or aromatics in all of the above-mentioned formulas.

Another class of suitable compounds is represented by the following structure:

Wherein R ₁ and R ₂ are as defined above, R ₄ and R ₆ are each independently H or C ₁ -C ₄ alkyl, and R ₅ and R ₇ are each independently C ₁ -C ₄ alkyl .

It is preferable that R ₁ and R ₂ are independently H or CH ₃ , and R ₄ , R ₅ , R ₆ and R ₇ are each CH ₃ .

Another suitable class of compounds according to the invention has the structure

Wherein R ₁ and R ₂ are the same as defined above, and R ₈ is each independently C ₂ -C ₆ alkylene, and it is preferable that they are-(CH ₂ ) ₂ -or-(CH ₂ ) _6- .

As noted above, the polymers of the present invention can be prepared by reacting monomers or backbone polymers containing suitable functional groups with primary or secondary amines or precursors thereof containing one or more hydroxy alkyl carbamate groups.

If monomers are used they are polymerized by reaction with amines followed by homopolymerization or copolymerization with other monomers to give the polymers of the invention. As used herein, "suitable" functional group means only functional groups such as epoxy, isocyanato, methylol, etc., which are reactive with primary or secondary amine groups of hydroxy alkyl carbamate-containing amines. For example, hydroxy alkyl carbamate-containing monomers can be prepared by reacting glycidyl methacrylate with hydroxy alkyl carbamate-containing secondary amines.

The resulting monomer can then be homopolymerized or copolymerized to provide the polymer of the invention.

The repeating units that make up a polymer can be divided into two classes, one of which contains appropriate amine-reactive functional groups, and the other of which is the encapsulation properties desired for the polymer and processed coatings or other products made therefrom, or It consists of units of change selected for the purpose of imparting other properties. Any suitable repeating unit or desired combination in the polymer may be used so long as the reactive functional group suitable for attaching the primary or secondary amine used in the reaction to it is present in the polymer.

In another method of making the polymers of the present invention, a monomeric or backbone resin can be substituted for all or part of hydroxy alkyl carbamate, in whole or in part, with a protected primary amine group that can be hydrolyzed in addition to one or more secondary amine groups. It reacts with the amine which it contains. The secondary amine group is reacted with a reactive functional group as described above to leave the amine group attached to the monomer or backbone resin and then hydrolyzed to the protected primary amine group which can be hydrolyzed to obtain the free amine group, for example one or more suitable cyclic groups. Carbonate is added to the mixture to allow it to react with the resulting free amine groups. Thus the polyfunctional amines that can be used to form hydroxyalkyl carbamates contain hydrolyzable protected primary amine groups that can be converted into amine groups that can react with cyclic carbonates or amine groups that can react with cyclic carbonates. have.

A wide variety of suitable monomers containing sites or functional groups reactive with primary or secondary amines can be used for reaction with hydroxyalkyl carbamate-containing amines, resulting in the formation of monomers containing hydroxycarbamate groups. . Such monomers include, for example, glycidyl methacrylate, glycidyl acrylate, isocyanate ethyl methacrylate maleic anhydride, methacryloyl chloride, n-methyloylacrylamide, 1- (1-isocyanato-1 -Menylethyl) -3- (1-methyleneethenyl) benzene, 1- (1-isocyanato-1-methylethyl) -4- (1-methylethenyl) benzene, methyl acrylamidoglycolate, Methyl acrylamiglycolate methyl ether, acrylol chloride and chloromethyl styrene, including but not limited to. The repeat units of the polymer may thus be derived from one or more of the foregoing monomers, which may provide one or more functional groups of the polymer as described below.

Various backbone polymers containing suitable functional groups can also be used to react with hydroxyalkyl carbamate-containing amines to provide the polymers of the invention. The choice of suitable monomers or polymers depends on the properties desired in the final coating or other product. Among the suitable backbone polymers are epoxy resins including polybutadiene-modified epoxy resins, acrylic resins, polybutadiene resins and polyester resins.

In order to provide a site for the amine to be immobilized on the monomer or the backbone resin, each such backbone resin or monomer may contain at least one reactive site capable of reacting with a secondary amine group of the hydroxyalkyl carbamate-containing amine of the present invention. Should have more than Such reactive sites include, but are not limited to, one or more of the following groups.

(산할로겐화물, 여기서 X는 할로겐, 바람직하게는 Cl, Br 또는 I이다)

(Acid halide, where X is halogen, preferably Cl, Br or I)

(할로겐화지방족, 여기서는 X는 할로겐, 바람직하게는 Cl,Br 또는 I이다)

(Halogenated aliphatic, where X is halogen, preferably Cl, Br or I)

(무수물)

(anhydride)

(알파, 베타 불포화에스테르)

(Alpha, beta unsaturated esters)

(알파, 베타 불포화케톤)

(Alpha, beta unsaturated ketones)

(N-메틸롤아미드)

(N-methylolamide)

(메틸롤화 페놀)

(Methylolated phenol)

(에폭사이드)

(Epoxide)

(이소시아네이트)

(Isocyanate)

(N-메틸롤 카바메이트)

(N-methylol carbamate)

(여기서 X는 할로겐 바람직하게는 Cl, Br 또는 I이다)

Where X is halogen preferably Cl, Br or I

One suitable class of reactive sites on monomers or polymers is epoxy groups, e.g. suitable resins are those derived from the reaction of epichlorohydrin with bisphenol-A or from the reaction of epichlorohydrin with phenolformaldehyde resins. It is an epoxy resin or an acrylic resin containing a hanging glycidyl ether group. Polybutadiene resins with suspended epoxy groups are also suitable for immobilizing hydroxyalkyl carbamate-containing amines thereon to prepare the crosslinkable polymers of the present invention.

Reaction of the monomer or polymer containing the secondary amine group of the hydroxyalkyl carbamate containing amine with the functional group as shown in (12)-(22) as a result forms the following groups at the functional group portion.

(a)

(b)

(c)

(d)

(e)

(r)

(g)

(h)

(i)

(j)

In the above structures, R _p is H or C ₁ -C ₈ alkyl; R _q and R _r are the same or different and are amine residues containing a hydroxyalkyl carbamate component.

The polymer containing the functional moiety may also comprise modifying units as described above, which may include one or more of acrylic acid, methacrylic acid, butadiene, styrene, alpha-methylstyrene, methyl methacrylate, butylacrylic And acrylonitrile, hydroxy ethylacrylate, glycidine methacrylate, acrylamide, methacrylamide, vinyl chloride and vinylidene chloride.

Any suitable epoxide material may be used in the backbone resin according to the present invention and includes, for example, an epoxy-containing monomer or polymer, preferably a resinous polyepoxide material containing two or more epoxy groups per molecule.

Among the known epoxides found to be useful as backbone resins in the practice of the present invention are polyglycidyl ethers of polyphenols such as bisphenol A, or generally reaction products of epichlorohydrin and polyhydric phenols. As used herein, "polyphenol" means a compound such as bisphenol-A, bisphenol-F and bisphenol-S.

Such epoxides can also be modified by reaction with carboxylate containing polybutadiene polymers or other modifiers.

Polyepoxides prepared from polyhydric phenol resins, such as novalac resins, constitute one suitable group of compounds. Polyglycidyl esters of polycarboxylic acids such as reaction products of epichlorohydrin or other similar epoxy compounds with reactants such as terephthalic acid, glucaric acid, succinic acid, oxalic acid may also be used.

The polyfunctional amines as mentioned above can be reacted with polyepoxides having one of the following structural formulas (a)-(d):

(a)

In which R ₉ represents a repeating segment of the structure

n ₁ is 0-12, such as 0-2.

(b)

In the above formula, R 'is hydrogen or methyl group, R ₁₀ is a hydrogen atom or glycidyl group, n is 0-12.

(c)

(d)

In formulas (c) and (d), n ₃ is each 0-4, and R ₁₁ is a hydrogen atom or a glycidyl group.

If it is desired that the polymer of the present invention has good water solubility / reducibility, it is important to select a low molecular weight (equivalent) monofunctional epoxide or a low equivalent difunctional or polyfunctional epoxide as the main chain polymer.

In order to obtain a water-soluble or reducing coating having excellent performance, bi- or polyfunctional epoxides are preferred. The use of such di- or polyfunctional epoxides can give hydroxyalkyl carbamate groups to the epoxide in high proportions, resulting in a hydrophilic resin such as a resin that can be dissolved or reduced in water. In addition to the epoxides described above, the resins of the following structural formulas (e)-(f) have been shown to be suitable for preparing such water-soluble / reducing resins:

(e) tris (hydroxyphenyl) methane base resin;

Wherein R = -CH ₂ -CH-CH ₂ , n is 0-about 5, preferably about 0-0.7 on average.

(f) Triglycidyl isocyanurate polyepoxy resin

As used herein and in the claims, "tris (hydroxyphenyl) methane-based resin" means a resin of formula (e) wherein n is 0-5 and "triglycidyl isocyanurate polyepoxy resin" It means resin of structural formula (f).

Ideally, all reactive epoxy groups are reacted with secondary amines to attach the amine to the epoxide to obtain a polymer substantially free of epoxy. However, this is less important for electrodepositable polymers, since it is possible to consume a slight excess of secondary amine groups by reacting the polymer with a mono-epoxide and to consume a slight excess of epoxy groups by reacting the polymer with a suitable amine. to be.

The carboxylic acid-terminated polybutadiene may be reacted with an epoxy resin to obtain a butadiene-modified epoxy resin that can be used as a main chain resin for preparing the polymer of the present invention. Such butadiene-modified epoxy resins are described in the literature ( SAMPLE Quarterly , vol, 6, NO.4 1975).

Any suitable acrylic resin may be used as the backbone resin according to the present invention. Any one of various monomers may be used to prepare the acrylic resin, and at least one of the monomers used preferably contains at least one epoxy group. These monomers include styrene, substituted styrene, alphamethylstyrene, alkyl acrylates such as butyl acrylate, butyl methacrylate, ethyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, Acrylamide, methyl methacrylate, acrylonitrile, glycidyl methacrylate, glycidyl acrylate, vinyl acetate, and the like, which are shown for the purpose of illustration and not limitation.

The backbone resin may have other functional moieties such as, for example, epoxy, hydroxy and amide groups. The polymers and backbone resins of the invention preferably have an acid content as low as possible to facilitate low temperature curing of hydroxyalkyl such as hydroxypropyl and / or hydroxyethyl, polymers containing carbamate groups.

The polymers of the present invention can be modified by reacting them with selected organic secondary amines (in addition to hydroxyalkyl carbamate-containing amines) such as diethylamine, morpholine, n-methylaniline. The choice and combination of specific modified secondary amines will of course depend on the end use of the polymer. For example, in preparing a water-reducing polymer, several functional sites on the backbone resin can be reacted with one or more hydrophilic secondary amines to enhance the hydrophilicity of the polymer. Conversely, in applications where hydrophobic polymers are desired, for example electrodepositable coatings, it may be desirable or necessary to react one or more secondary amines with the backbone resin to impart the desired degree of hydrophobicity to the polymer. In general, the polymers of the present invention are suitable for use in the coating field, in which case they have a molecular weight of about 300-100,000. The urethane-crosslinkable polymers of the present invention are suitable for a variety of applications in the field of coatings, such as solvent based or water based coatings, powder coatings, electrocoating compositions, spray rollers and immersion coatings and the like. These coatings are usually applied to substrates such as metals, textiles, plastics or paper. The thermosetting resin of the present invention can be used to prepare urethane coatings and adhesives and laminating resins resistant to organic solvents, abrasion and water.

The composition of the third aspect of the present invention consists of three essential ingredients and one optional ingredient, which have a good shelf life at room temperature and can be applied to the product or substrate by conventional methods such as brush, spray, roller or dipping method. The applied coating is then heated to a high temperature for a time sufficient to cure it by crosslinking reaction between the composition components.

As mentioned above, the essential components of the coating composition are polymers containing (a) hydroxyalkyl carbamate compounds (b) amino crosslinkers and (c) active sites reactive with amino crosslinkers. Optional component is (d) acid catalyst.

A compound generally used in the third aspect of the present invention is a hardyalkylalkyl carbamate compound of formula (23).

Wherein R is a C ₁ -C ₂₀ organic component which may contain one or more heteroatoms and / or one or more hydroxyl groups, and R ₁ , R ₂ and R ₃ are each independently H or CH ₃ to be. Compounds of the type illustrated in Structural Formula (23) are obtained by reacting a hexagonal carbonate with a primary amine.

A preferred class of hydroxyalkyl carbamate compounds useful as reactive diluents in the third aspect of the invention has the structure (24)

Another suitable class of hydroxyalkylcarbamate compounds that can be used as reactive diluents according to the present invention have the following structural formulas (25) and (26).

Wherein R is a C ₂ -C ₂₀ aliphatic, cycloaliphatic or aromatic component containing those heteroatoms described above, wherein R ₁ is H or CH ₃ .

Wherein R is C ₂ -C ₆ alkyl and R ₁ is H or CH ₃ .

Suitable reactive diluents prepared according to the invention and used in coating compositions include the following (A)-(D).

(A)

(B)

(C)

(D)

Compounds of formulas (A)-(D) are prepared by reacting a suitable amine (having a formula that is readily distinguishable from the above) with a suitable cyclic carbonate.

The amino crosslinker may be any of a variety of known amino crosslinking compounds, including crosslinking agents based on melamine, glucoluril, guanamines such as benzoguanamine, urea, substituted ureas, and the like. The term "amino crosslinker" as used herein is to be interpreted to include any suitable aminoplast. One such suitable class of materials is modified amino flask resin compositions consisting of modified amino-triazine-aldehyde resins as known from aminoplast resin compositions US Pat. No. 3,082,180. Another suitable class of aminocrosslinkers that can be used as a component of the present invention consists of a fully methylated, fully methylolated melamine composition, the preparation of which is known from US Pat. No. 4,293,692. Another suitable class of amino crosslinkers is known from US Pat. No. 4,105,708, which consists of substantially fully mixed-alkylated and substantially fully methylolated glycoluril derivatives such as dimethoxymethyl diepoxymethyl glycoluril. Glycoluril is also known as acetylene urea and is obtained by reacting two moles of urea with one mole of glyoxal. Its correct chemi-immune tetrahydroimidazo- (4, 5-d) -imidazole 2.5 (1H, 3H) -dione. U.S. Patents 3,082,180, 4,293,692 and 4,105,708, respectively, are incorporated herein by reference.

Particularly suitable classes of aminocrosslinkers are melamine-formaldehyde resins and glycoluril-formaldehyde resins, which in each case are partially or fully alkylated and methylolated, for example at least partially. For example, as known in US Pat. No. 4,293,692, melamine may be methylolated by reaction with formaldehyde. Melamine is fully methylolated to form hexamethylrollmelamine or partially methylolated to produce pentamethylrollmelamine, tetramethylrollmelamine, or the like, or a mixture of two or more of the foregoing. Subsequently, at least partially methylolated melamine (or glycoluril) is reacted with an alcohol such as methanol to completely or partially methylolated melamine or glycoluril completely methylated and fully alkylated melamine (hexamethoxymethyl-melamine) It is sold under the brand name CYMEL 303 from the cyanamide company. For reference, the "melamine-formaldehyde" and "glycoluril-formaldehyde" resins in the present specification and claims include resins derived from any suitable melamine or glycoluril that can be used as crosslinkers in coating compositions. Similarly, "urea-formaldehyde" and "benzoguanamine-formaldehyde" resins include resins derived from the corresponding urea and benzoguanamines.

Any of a variety of polymers containing active sites reactive with aminocrosslinkers and / or hydroxyalkylcarbamate groups at high temperatures can be used in the present invention. There is a wide spectrum of such compositions, which can be selected to provide the desired quality for the cured coating. This class of polymers, shown below, illustrate those that can be used in the present invention.

Any suitable resin can be used, such as any resin containing at least one acrylic component. Acrylic resins generally consist of copolymers of unsaturated carboxylic acids, esters of carboxylic acids with one or more ethylene unsaturated monomers. The acid can be acrylic acid, methacrylic acid or other ethylenically unsaturated mono- or dicarboxylic acid.

Alkylacrylates, alkyl-methacrylates and vinyl aromatic hydrocarbons such as styrene and vinyltoluene can be used as monomer components of the copolymer. Examples of suitable acrylic resins include one or more of hydroxyethyl acrylate, maleic anhydride, n-methylol acrylamide, hydroxypropyl acrylate, acrylamide, acrylic acid, methacrylic acid, methyl acrylamido glycolate, It is made of a copolymer containing methyl acrylamido glycolate methyl ether and the like. Polymeric structures include one or more butadiene, styrene, alpha-methylstyrene, methyl methacrylate, butyl acrylate, acrylonitrile, hydroxyethyl acrylate, glycidyl methacrylate, acrylamide, methacrylamide, vinyl chloride And modified units derived from vinylidene chloride.

Similarly any suitable polyester resin can be used as the polymer of the composition of the present invention. Such polymers generally consist of the reaction product of one or more glycols with dicarboxylic acids. For example, polyester resins are glycols such as ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propylene glycol, tetramethylene glycol, 2, 3-butylene glycol, pentamethylene glycol, malonic acid, maleic acid succinic acid, It can be prepared by reacting with dicarboxylic acids such as adipic acid, pimelic acid, sebacic acid, oxalic acid, phthalic acid, terephthalic acid, hexahydroterephthalic acid, para-phenylene, diacetic acid, decamethylene dicarboxylic acid. Polyesters are formed by the ester reaction of polyhydric alcohols and acids. Modified resins such as polyester amide resins having terminal hydroxyl groups can also be used. Alkyd resins can be similarly produced by the reaction of polybasic acid anhydrides with polyhydric alcohols, for example by reaction of isophthalic acid, succinic acid, maleic acid or pyromellitic anhydride with ethylene or propylene glycol or pentaerythritol.

Any of various epoxy resins may be used as the polymer in the coating composition. For example polyglycidyl esters of polycarboxylic acids, ie epichlorohydrin or pseudoepoxy compounds and for example cyanuric acid, terephthalic acid, glucaric acid, succinic acid, adipic acid, phthalic acid, oxalic acid, dimerized linoleic acid, Polyphenol resins derived from reaction products of aliphatic or aromatic polycarboxylic acids with bisphenols such as bisphenol-A, bisphenol-F, bisphenol-S, phenol-formaldehyde-acetone condensates can also be used.

The acid catalyst optionally used to lower the curing temperature may consist of any suitable acid mentioned above. In general, any material that meets the definition of Lewis acid or Bronsted acid, does not interfere with the crosslinking reaction and does not adversely affect stability at ambient temperature. Suitable acid catalysts include aromatic sulfonic acid compounds, phosphoric acid or alkylsulfonic acids, dinonylnaphthalenesulfonic acid, paratoluenesulfonic acid, such as n-dodecylbenzenesulfonic acid and nitric acid, sulfuric acid, phosphoric acid and the like as known in US Pat. No. 3,960,688. Alkyl esters of inorganic acids such as hydrohalic acid. Catalysts in the form of phosphate esters sold under the name CYCAT by the American Cyanamide Company may be suitably used.

The hydroxyl group-containing polyurethane polymer of the fourth aspect of the present invention can be produced by self-condensation of a poly-dihydroxyalkyl compound or by condensation thereof with a polyol. The polyol used in the latter condensation reaction may be any suitable polyol, and may be polyol, polyether polyol, polyester polyol, alkyd polyol, phenol formaldehyde condensation product, bisphenol-A, bisphenol-F, polyether resin, bisphenol ethylene oxide Or propylene oxide condensation products, polyether resins, dihydroxypolybutadiene and the like.

Typical polyetherdiols or polyols suitable for use in the present invention can be prepared from the reaction of diols, polyols or amines with such mixtures of ethylene oxide, propylene oxide, styrene oxide or other epoxides having a carbon content of C ₂ -C ₁₈ . Derived polyesters or polyethers derived from tetrahydrofuran.

Typical polyetherdiols or polyols suitable for use in the present invention can be prepared by condensing diols, triols or polyols with mixtures of mono, di, tri or poly base carboxylic acids by known methods. Typical diols or polyols are ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1, 3-butanediol, 1, 6-hexanediol, neopentylglycol, cyclohexane-dimethanol, trimethylpentanediol, trimethylolpropane penta Erythritol.

Typical carboxylic acids are C ₈ -C ₁₈ fatty acids, dimerized fatty acids, C ₇ -C ₁₀ aliphatic dibasic acids and aromatic monocarboxylic acids and polycarboxylic acids such as benzoic acid, phthalic acid and trimellitic acid.

Preference is given to polyols or mixtures of polyols having an average functionality of 2-3.

Although more functional polyols can be reacted with polyhydroxyalkylcarbamate compounds, the ratio of the polyol to carbamate and the resulting reaction must be controlled to prevent gelation. The choice of appropriate reactants and conditions to prevent gelation can be readily determined by those of ordinary skill in the art by conventional methods. Condensation of a poly-hydroxyalkyl carbamate compound with a polyol can be represented by the following scheme (27).

In the formulas R 'and R' 'are the same or different and may be composed of any suitable organic component.

Reaction (27) shows that the hydroxyl group-terminated polyurethane polymer and one 1,2-diol leaving group are formed.

The reaction of the poly-hydroxyalkyl carbamate with the polyol can be effected only by heating or in the presence of a suitable exchange ester reaction catalyst such as tin compound. The reaction may also take place in a solvent medium. Diols removed during the condensation reaction can be removed continuously by azeotropic distillation using a suitable solvent or by vacuum distillation.

The hydroxyl group-containing polyurethane polymer having a high urethane content can be obtained by self-condensation of a poly-hydroxyalkyl carbamate compound represented by the following (28);

Wherein R 'and R' 'are the same or different and are composed of suitable organic components. The reaction of the poly-hydroxyalkylcarbamate with the polyamine can be carried out in the presence of a suitable catalyst. Suitable catalysts include dialkyl tin compounds such as organotin compounds such as dibutyltin dilaurate, organic zinc compounds such as zinc octoate, zinc butyrate and some organic titanium compounds and other suitable catalysts known in the art.

The following hydroxy group-containing polyurea polymer can be obtained by condensing a poly-hydroxyalkyl carbamate compound with a suitable polyamine as shown in the following (29).

Wherein R 'and R' 'are the same or different and may be composed of any suitable organic component.

Some polyols may be substituted with polyamines, for example, one or more polyols and one or more polyamines may be co-condensed with poly-hydroxyalkylcarbamate to incorporate both urea and urethane bonds in the polymer. For example, adding urea bonds during polyurethane polymerization is often desirable to improve hardness and increase solvent resistance.

The above polyurea or polyurethane polymers can be used as thermoplastics for use in elastomers such as coatings or adhesives for casting compounds, metals, plastics, fabrics, and adhesives, and for their crosslinking with different hydroxyl functional groups and urethane bonds or unsaturation in the main chain. Can be.

Hydroxy functional groups can be crosslinked with amino formaldehyde resins or isocyanates and unsaturated bonds can be used for air oxidative curing or sulfur curing. Compositions well suited for obtaining thermoset coating compositions can be prepared using amino crosslinkers in combination with polyurethane, polyurea or polyurethane-polyurea polymers.

Any suitable solvent or excipient such as ethylene glycol monoethyl ether (cellosolve) may be used to transport the polymer, crosslinker and any catalyst.

The catalyst optionally used in the composition may consist of any suitable acid catalyst. In general, any material that conforms to the definition of Lewis and Bronsted Acid and does not interfere with the crosslinking reaction can be used. Among the suitable acid catalysts are aromatic sulfonic acid compounds, phosphoric acid or alkylphosphonic acids, dinonylnaphthalenesulfonic acid, paratoluenesulfonic acid, n-dodecylbenzenesulfonic acid, and the like, and nitric acid, sulfuric acid, phosphoric acid and halogenated hydrogen acids as mentioned in US Pat. No. 3,960,688. Alkyl esters of the same inorganic acid. Catalysts in the form of phosphate esters sold under the trademark CYCAT by the American Cyanamide Company may be suitably used.

As is well known in the art, other additives such as pigments, modifiers and the like may be included in the composition.

The composition according to the fifth aspect of the invention, which contains a crosslinker, a polymer and optionally a catalyst, is heated to a high temperature in use when the hydroxyalkylcarbamate groups of the crosslinker react with the active functional groups of the polymer to crosslink the polymer and produce a low toxicity diol. Leaving groups such as propylene glycol or ethylene glycol are produced. A typical reaction sequence of a polymer containing a hydroxy functional group is shown in Scheme (30) below, and a polymer containing an amine function is shown in Scheme (31).

In the case of carboxyl functional polymers, amide groups are formed during the reaction and the reaction product of the crosslinking reaction is CO ₂ and the corresponding 1,2-diol. Generally the groups liberated during the crosslinking reaction are low toxic diols as described above such as propylene glycol or ethylene glycol. Attempts to produce the hydroxyalkyl carbamate compounds described above by reaction of diisocyanates with diols or polyols are impossible or difficult because polyurethane polymers are formed.

As described above, the crosslinking agent may be obtained by reaction of a cyclic carbonate with an amine.

It will be appreciated by those skilled in the art that a wide variety of aliphatic amines can be used in the present invention.

Aliphatic and cycloaliphatic amines readily react with cyclic carbonates to form the hydroxyalkyl carbamate compounds used in the present invention.

Aromatic amines generally require suitable catalysts to facilitate the reaction with cyclic carbonates and can be referred to, for example, US Pat. No. 4,268,684 (Arthur E. Gurgiolo). Aromatic amines known herein are suitable for use in the present invention. These include amines represented by the following structural formula.

Wherein each R is independently hydrogen or a hydrocarbyl or hydrocarboxy group up to C ₈ , preferably up to C ₄ ; A is C ₁ - ₁₀ and preferably C ₁ - is a divalent hydrocarbon of _6, n is 0 or 1, x has an average value of about 1.1 to 10, preferably from about 2-4.

Particularly suitable aromatic amines include aniline, 0-, m-, or p-toluidine, 2,4-xyldine, 3,4-xyldine, 2,5-xyldine, 4-ethylaniline, 3-propyl Aniline, 1,3-diaminobenzene, 2,4-diaminotoluene, 2,6-diaminotoluene, 4,4'-diaminodiphenylmethane, 2,4,4'-triamino-diphenyl ether , 2,6-diaminonaphthalene, 4,4'-bismethylenebiphenylamine and their 0-, m- or p-anisidine mixtures, such as but not limited to those shown for illustrative purposes.

In an embodiment of the present invention, the crosslinking agent has the following structural formula (33).

+

+

Wherein R ₁ is an aliphatic, cycloaliphatic, heterocyclic polyurethane or polyurea containing two or more carbon atom components, and R is independently H or C _1-6 alkyl or arylalkyl.

Bi- or polyfunctional hydroxyalkyl carbamate compounds containing urethane and / or urea components in the chain by self-condensation of the compounds of formula (33) above or by condensation of such compounds with polyols and / or polyamines Is generated. Condensation with a polyol can be represented, for example, by Scheme 34 below;

R1 in the above scheme should contain a hydroxyalkyl carbamate group of the structure:

The crosslinking agent can be appropriately modified for a given application by selecting a suitable polyol and / or polyamine in the above-mentioned condensation reaction. Physical properties such as flowability, solubility and melting point and hydrophobicity and functionality can be easily adjusted by appropriate choice.

For example, 3 moles of biscarbamate prepared by reacting 1,6-hexanediamine and propyl carbonate as in reaction (30) are condensed with 1 mole of trimethylolpropane to be suitable as a cationic electrocoating agent, so that liquid, organic solvent-soluble trifunctional Crosslinkers can be prepared. The starting material, biscarbamate, is a water soluble difunctional crystalline material. Its water solubility impairs its use in cationic electrocoatings because it is not co-deposited with the resin. Modification of the biscarbamate with a polyol yields a hydrotropic composition suitable for use in cathodic electrodeposition.

Preferred crosslinkers of the invention are monomers or oligomers which are at least difunctional. Higher molecular weight carbamate-containing crosslinkers may be used for certain purposes. The molecular weight is, for example, as low as 236 for bishydroxyethyl tilcarbamate of ethylenediamine. In the case of the polymerizable polyurea or polyurethane containing hydroxyalkyl carbamate, the average molecular weight is 2,000 or more. Those skilled in the art can easily select the optimum equivalents, functionality, solubility and melting point required for a given application.

Typical properties of the hydroxyalkyl carbamate-containing crosslinkers used in various applications are shown in the table below.

The amount of hydroxyalkyl carbamate selected from typical formulations will of course depend on the desired crosslink density. Usually the proportions and composition of the resin and crosslinker are chosen such that about 0.2-5 moles of hydroxy alkyl carbamate groups per mole of active functional group on the polymer. If a larger proportion of the crosslinker carbamate group is used at the site of the polymeric functional group, the crosslinker also causes some self-condensation as in Scheme 35 below.

The crosslinkable resin which can be used in the present invention may be composed of a suitable polymer having an appropriate functional group which reacts with an active functional group such as the hydroxyalkyl carbamate crosslinker of the present invention when heated, preferably in the presence of a catalyst. have. Such active groups consist of hydroxyl, amine and carboxyl groups, and therefore resins containing such groups can be used to practice the present invention. The functional groups of the polymers used may be as low as 2 but preferably 3 or more and have a molecular weight of, for example, about 300-100,000. Acrylic polymers useful in the present invention, for example, generally have a molecular weight of about 1,000-50,000.

Typical functional group contents in, for example, hydroxyl resins that may be used in the present invention are about 0.5-4 meq of hydroxyl per gram of resin.

Examples of polymers that can be usefully used in the present invention include, but are not limited to, acrylics, polyesters, vinyls, epoxies, polyurethanes, polyamides, celluloses, alkyds and silicone resins. Acrylic resins useful in the present invention may be derived from acrylic acid or methacrylic acid esters of C ₁ -C ₁₈ aliphatic alcohols. Any acrylonitrile, styrene or substituted styrene can be incorporated into the polymer. Another comonomer suitable for this use is maleic acid or fumaric acid esters or semiesters thereof. The functional group can be derived from hydroxyalkyl esters of acrylic acid, methacrylic acid, maleic acid or fumaric acid. Carboxylic functional groups can be derived from alpha and beta unsaturated carboxylic acids as mentioned below.

Polyester and alkyd resins suitable for use as hydroxyalkylcarbamate-containing amine crosslinkers can be derived from diols, polyols, mono-di- and polybasic acids. Such suitable diols or polyols include, for example, ethylene glycol, propylene glycol, 1,3-butylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, trimethylpentanediol, cyclohexanedimethanol, trimethylolpropane, trimethylol ethane and Glycerin pentaerythritol. Typical carboxylic acids useful for preparing hydroxy and carboxyl functional polyesters include C ₈ -C ₁₈ aliphatic monocarboxylic acids, C ₄ -C ₁₀ aliphatic dicarboxylic acids, aromatic mono-di- and tricarboxylic acids such as benzoic acid, o-, m-, p Phthalic acid or trimellitic acid dimerized fatty acids and hydroxycarboxylic acids such as dimethylolpropionic acid or caprolactone.

Particularly suitable vinyl polymers for use in the present invention are hydroxy and carboxyl functional group-containing polymers containing vinyl chloride or vinyl acetate as one comonomer.

Particularly suitable epoxy resins for use in the present invention are hydroxy or amine functional resins. These are generally derived from bisphenol-A, bisphenol-F or phenol formaldehyde resins and epichlorohydrin. Epoxy resins can also be formed from cycloaliphatic epoxides.

Particularly suitable polyurethanes for use in the present invention may be hydroxyl, carboxyl or amine functional and may be derived from polyester or polyetherpolyols and polyisocyanates.

Particularly suitable polyamides for use in the present invention are amine or carboxyl functionalities which can be prepared by condensation of polybasic acids with polyamines or by condensation of caprolactone by conventional methods.

Cellulose-based hydroxyl functional resins such as cellulose acetobutyrate and hydroxyethyl cellulose can also be reacted with the hydroxyalkylcarbamate-containing amines of the present invention. Hydroxy functional silicones may also be crosslinked with hydroxyalkylcarbamate crosslinkers and are therefore suitable for the present invention.

All of the above-mentioned active functional group-containing resins can be used as a solid powder in an organic solvent solution or as a dispersion in water or in an organic cosolvent solution. Depending on the resin structure, these uncrosslinked polymers are preferably used in one of the forms mentioned above. Mixtures of two or more of the above polymers may also be used. The polymer and carbamate crosslinker mixtures may also be colored by known methods to give a coating of the desired appearance.

Depending on the application method, the solid powder or liquid is applied onto the substrate to be coated and then the solvent present is evaporated and the system is cured at a temperature sufficient to cure, for example at about 93-204 ° C., for example a few minutes.

Crosslinking catalysts can be used to promote crosslinking of the thermoset compositions of the present invention. The catalyst may be an external catalyst or may be incorporated according to a known method as an internal catalyst during the production of the functional group-containing resin. For example, quaternary ammonium hydroxide groups can be added to the resin. Any suitable crosslinking catalyst can be used (known metal-containing catalysts such as tin, zinc and titanium compounds as well as tertiary or quaternary compounds as mentioned below).

Benzyltrimethylammonium hydroxide, dibutyltin dilaurate and similar compounds are good catalysts for crosslinking for a few seconds to about 30 minutes at high temperatures of about 100-175 ° C. The catalyst may be present in the composition in an amount of about 0.1-10% by weight, preferably about 1-5% by weight of the polymer.

The catalyst may be a tertiary or quaternary catalyst such as known compounds of the following structural formula.

Wherein R _p , R _q , R _r and R _s are the same or different and may be C ₁ -C ₂₀ aliphatic, aromatic, benzyl, cycloaliphatic, and M is nitrogen, phosphorus or arsenic (each quaternary ammonium) , Phosphonium or alsonium compounds), S is sulfur (a tertiary sulfonium compound is obtained) and X- is hydroxy, alkoxide, bicarbonate, carbonate, formate, acetate, lactate and other volatile organics Carboxylates derived from such as carboxylic acids. Such salts of carboxylic acids are effective in promoting low temperature cure as long as the carboxylic acid portion of the salt is volatile.

The composition of the present invention is stable at ambient temperature and must be heated to high temperature in order to allow crosslinking to occur above a certain rate. In general, a high temperature of about 93 ° C. or higher is necessary to cause the crosslinking reaction to occur at a rate that is perceptible. Desired rate as used herein and in the claims refers to a temperature sufficient to cure the deposited composition by allowing the crosslinking reaction to occur at a rate sufficient to cure generally within 1 hour-3 hours or faster. Say.

The hydroxyalkylcarbamateamines as shown in structural formulas (36) and (37) are acidified following reaction with a suitable epoxy resin and then acidified after they are sufficiently hydrophobic and cationic to be electrodeposited by conventional methods. It is useful as a cathode electrodepositable self-crosslinkable polymer in character.

In some cases, in order to obtain a polymer having the required degree of hydrophobicity, as described in detail below, some of the available epoxy sites must be reacted with a hydrophobic amine to incorporate the hydrophobic amine into the polymer. Di- and polyamines useful for the production of hydroxyalkylcarbamateamines as described above include those in formula (36) wherein each R independently represents a bond containing H or a C _1-50 straight or branched chain hydrocarbon or one of them. Compound is included. Useful amines in formula (37) include those in which n is 0- about 5, Re, Rf and Rg are straight or branched chain hydrocarbon segments having 1 to about 6 carbon atoms and Re, Rf and Rg may also contain ether groups. Such is included. The Z group can be selected from hydrogen, hydroxyl, C _1-20 alkoxy, C _1-20 secondary amine or primary-NH ₂ groups. In the latter case, the primary amine group Z can be converted to a hydroxyalkyl carbamate group if sufficient (excess) cyclic carbonate is used to produce the hydroxyalkyl carbamate amine (or polyamine) compound.

The resulting hydroxyalkyl carbamate containing amine is reacted with a water insoluble epoxide containing "backbone" compound.

A typical polymer according to the sixth aspect of the present invention may have the following structure 38:

The resulting polymer is optionally crosslinked via main chain hydroxyl groups, crosslinked by self-condensation or crosslinked via a main chain amine group, when heated in the presence of a suitable crosslinking catalyst.

In all crosslinking reactions, the water-sensitive hydroxyalkyl moiety of the carbamate group is lost as glycol. Thus, the crosslinked film not only exhibits mechanical properties and solvent resistance during curing but also resists water.

Generally the polyfunctional amines used in the sixth aspect of the invention contain at least one secondary amine group and at least one primary amine group which are masked for reaction with cyclic carbonates. As used herein and in the claims, (a) "multifunctional amine" refers to an amine having at least one primary amine group (which may be a protected primary amine group as described below) and at least one masked secondary amine group. (B) "shielded secondary amine group" means a secondary amine group whose reaction with cyclic carbonates has been inhibited by steric, electrical or otherwise under the conditions in which the primary amine group reacts. Secondary amine groups, which have been stericly or otherwise prevented from reacting with cyclic carbonates, remain unreacted to form carbamate and exhibit reactivity with the epoxy groups on the polymer.

The definition of "polyfunctional amine" mentioned above includes protected primary amine groups, such as ketimines, which can be deprotected to form primary amine groups. As described in detail below, the polyfunctional amines may optionally react with epoxides prior to the formation of hydroxyalkyl carbamate groups since they have primary amine groups in the form of protected primary amines, such as ketimines. After reacting with the epoxide, the ketimine group can be hydrolyzed to the primary amine group and then reacted with the cyclic carbonate. Thus such protected primary amine groups are referred to herein as "precursors" of hydroxyalkyl carbamate groups.

The amines used in accordance with the sixth aspect of the present invention, which react with one or more cyclic carbonates to form hydroxyalkylcarbamate-containing amine groups, can be one of a variety of compounds and are generally straight or branched chain alkyl, cycloalkyl, It may consist of an alkylaromatic component, most preferably a C ₁ -C ₂₀ alkyl, cycloalkyl or alkylaromatic moiety and a polyfunctional amine containing such a component containing at least one heteroatom in addition to at least one carbon. . Such components containing one or more heteroatoms include, for example, those containing ether groups, thio groups and organo-silicon components. Representatives of the preferred class of amines include those of the following structural formulas (a) and (c).

(a) H ₂ N (CH ₂ ) _X [NH (CH ₂ ) _X ] _n NH (CH ₂ ) _X NH ₂

Wherein X is independently 2-6 and n is 0-4.

(b) R ₂ NH (CH ₂ ) _y NH ₂

Wherein R ₃ is a C ₁ -C ₂₀ alkyl, cycloalkyl or alkylaromatic component, y is 2 or 3;

Wherein R ₄ and R ₆ are each independently H or C ₁ -C ₄ alkyl, and R ₅ and R ₇ are each independently C ₁ -C ₄ alkyl.

Suitable amines include fatty acid diamines of the general formula RNHCH ₂ CH ₂ CH ₂ NH ₂ , where R is a C ₁ -C ₂₀ organic component such as hydrogenated resin diamine, rooleudidiamine cocodiamine, oleyl diamine, etc .; Etherdiamine of the general formula R′OCH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ NH ₂ , wherein R ′ is a C ₁ -C ₁₅ organic component; And silylamine of the general formula (C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ NH ₂ .

로 전환된 구조를 갖는 하이드록시알킬카바메이트 함유아민 수지가 얻어지게 된다. (상기 구조에서 R₁과 R₂는 각기 독립적으로 H 또는 C₁-C₂₀알킬, 사이클로알킬 또는 알킬방향족 성분이다)As described above, when the primary amine group of one or more amines reacts with the cyclic carbonate, an amine containing at least one hydroxyalkyl carbamate group in addition to the unreacted secondary amine is produced. Thus, in the above structural formula -NH ₂ group

A hydroxyalkyl carbamate-containing amine resin having a structure converted to is obtained. (Wherein R ₁ and R ₂ are each independently H or C ₁ -C ₂₀ alkyl, cycloalkyl or alkylaromatic components)

For example, hydroxyalkyl carbamate group-containing amines that have been shown to be useful in preparing electrodepositable polymers in accordance with the present invention are propylene carbonates containing N, N-bis (6-aminohexyl) -2- [6-aminohexyl) amino] butanediamine. It is obtained by reaction with and has the following structure.

Wherein R ₁ and R ₂ are the same as described above and R ₈ is each C ₆ alkylene. Other useful amines of this type can also be prepared in which each R ₈ is independently C ₂ -C ₆ alkyllane.

Preferred polyfunctional amines for reaction with cyclic carbonates include, for example, diethylenetriamine and triethyltetramine.

When using polyamines, reactants and conditions that can prevent gelation in the production of polymers may be appropriately selected by those skilled in the art.

The appropriate polyepoxide is reacted with about 1 equivalent of the amine described above containing one or more secondary amine groups. The equivalent ratio of amines to epoxy groups should be about 1: 1. Ideally, all reactive epoxy groups react with secondary amine groups to attach the amine to the epoxy polymer. However, it may be acceptable to have a slight or insufficient epoxy group after reaction with the secondary amine group, followed by addition of some monoepoxide (if the secondary amine group is excessive) or amine (if the epoxy is excessive). You can. Each of the amine groups contains one or more hydroxyalkyl carbamates formed thereon by reaction of the primary amine group of the polyfunctional amine with the cyclic carbonate, resulting in a self-crosslinkable polymer. Sufficient amine groups can be attached to the polymer to impart electrodeposition to it by cationic electrodeposition.

Another method for preparing the electrodepositable polymer of the present invention includes an amine further containing a ketimine group instead of the hydroxyalkyl carbamate group mentioned above in addition to one or more secondary amine groups capable of reacting epoxide with an epoxy group. To react. As mentioned above, when the epoxy group and the secondary amine group are reacted, the amine group is attached to the main chain epoxy polymer, and then the acid is polymerized and water is added thereto.

In this case, the ketimine group is reacted to form a free amine group, and when cyclic carbonate is added to the mixture, it reacts with the free amine group on the amine component to which it is attached. The polyfunctional amines used to form hydroxyalkyl carbamates thus contain amine groups that can react with cyclic carbonates or contain amine groups that can be converted to amine groups that can react with cyclic carbonates. As used herein, the term “precursor” of a carbamate group refers to a ketimine group as mentioned above.

As will be appreciated by those skilled in the art, the electrodepositable polymer should be somewhat hydrophobic. In the case of epoxide resins having high epoxy functionality such as novalac resin, it is necessary or preferable to react the polymer with a hydroxyalkyl carbamate group or a precursor thereof, amine containing a ketamine group, and other hydrophobic amines. The amount with the hydrophobic amine selected is chosen to give the hydroxyalkyl carbamate-containing electrodepositable resin as much hydrophobicity as necessary to overcome the hydrophilicity of the hydroxyalkyl carbamate group.

The amount of the hydrophobic amine is preferably used in an amount sufficient to impart the desired degree of hydrophobicity to the carbamate polymer. The reason is that such hydrophobic amines occupy reactive epoxy sites instead of hydroxyalkyl carbamate-containing amines, thereby limiting the number of available crosslinking sites. Inadequate crosslinking sites will of course result in the cured film obtained from these figures not having the desired properties that can be obtained by having a sufficient degree of crosslinking.

Preference is given to using hydrophobic secondary amines to increase the hydrophobicity of the epoxy carbamate resins. Although primary amines and primary / secondary polyamines may be used, as will be appreciated by those skilled in the art, gelation may occur as a result of the reaction of these amines with polyepoxy resins. To prevent this gelation, specific reactants and conditions can be selected. In general, however, it is preferable to use an amine of the following structural formula.

R _d and R _e are each independently an aliphatic C ₄ -C ₂₀ component, cycloaliphatic, heteroaliphatic or aromatic component, provided that the resulting amines are hydrophobic.

A preferred class of secondary hydrophobic amines are those amines in which R _d is an aromatic group and R _e is an acrylaliphatic alkyl, cycloaliphatic, alkylaromatic or alkylheterocyclic group. Such preferred secondary amines include N-methylaniline, N-ethylaniline, N-propylaniline, N-butylaniline, N-benzylaniline and the like.

The weight percentage of hydrophobic amine (the weight of hydrophobic amine divided by the sum of the weight of hydrophobic amine and carbarate polymer, all based on 100% resin solids) is preferably 10-80%, preferably 10-40% by weight. Do. Most preferred is to obtain a carbamate polymer containing such hydrophobic secondary amines from the furnace bottom epoxy resin. However, when using a high equivalent weight of bisphenol-A resin as the main chain resin, only the terminal segment of the bisphenol-A epoxy resin contains an epoxy group and the middle part is a repeating hydrophobic segment to overcome the hydrophilic nature of the resin. There is no use of hydrophobic amines.

In preparing the electrodeposition bath according to the invention, the polymer is dispersed in water by partial acidification with an acid such as formic acid, and when an external catalyst is used, a catalyst such as dibutyltin dilaurate or quaternary ammonium is added. It is also possible to add the above catalyst to the main chain polymer to provide an internal catalyst. Any suitable acid may be used to disperse the self-crosslinking resin of the present invention, such as hydrochloric acid nitric acid, sulfuric acid, phosphoric acid or other inorganic and formic acid (preferred), acetic acid, lactic acid, propionic acid, butyric acid, pentanic acid, citric acid and polycarboxylic acid. Water soluble organic acids such as, for example, oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid can be used.

The negative electrode coating composition of the seventh aspect of the present invention consists of three essential components and one optional component. These compositions have good bath stability at ambient temperature and can be electrodeposited onto the substrate in a conventional manner by heating to a high temperature for a time sufficient to cure by crosslinking reactions between the components of the composition.

As mentioned above, the essential components of the electrodeposition composition diluted in water to form the electrodeposition bath include (a) a protected or unprotected hydroxyalkyl carbamate crosslinker, (b) an ungelled polymer and (c) There are acid solubilizers or dispersants that give the polymer water dispersibility. Optional component (d) is a crosslinking catalyst.

Hydroxyalkylcarbamate containing compounds can be used in the seventh aspect of the invention if they are hydrophobic enough to be co-deposited with the cationic polymer by conventional methods. In some cases, hydroxy groups can be reacted with other hydrophobic protecting agents to obtain a crosslinker with the required degree of hydrophobicity and added to the crosslinker.

Tens of thousands of such as 4, 4'-diamino-dicyclohexylmethane, 4, 4'-diaminodicyclohexylpropane and hexamethylenediamine can be used to produce carbamate crosslinkers by reaction with cyclic carbonates. Can be. Suitable polyamines include, but are not limited to, the polyamines of formula (39) below for purposes of illustration.

(39) R ₁ HN-R ₂ -NHR ₃

Wherein R ₁ is independently H, CH ₃ or C ₂ -C ₂₀ alkyl, R ₂ is independently —CH ₂ or C ₂ -C ₂₀ alkyl segment which may contain an aromatic ring or a saturated ring, wherein R ₁ , R ₂ and R ₃ may also contain other functional groups that do not interfere with the amine-carbonate reaction such as esters, amides, nitriles, ethers, hydroxy, phenols, ketone groups and the like, and R ₃ is independently H , CH ₃ or C ₂ -C ₂₀ alkyl.

Suitable classes of monomers / polymers that may be used to react with cyclic carbonates to form carbamate-containing crosslinkers include vinyl / polyvinyl, acrylic / polyacryl, methacryl / polymethacryl, ester / polyester, amide / polyamide, Or mixtures or copolymers of imides / polyimides, ethers / polyethers or those containing at least two branched amine groups on a molecular weight average.

As mentioned above, since the negative electrodepositable material such as the crosslinking agent used in the present invention needs to have some hydrophobicity, the resulting carbamate crosslinker after the reaction with the cyclic carbonate is insoluble in water or only in water. Preference is given to selecting polyamines which are only slightly soluble (polyamines also include diamines). However, the water soluble carbamate crosslinker may be suitably modified to be insoluble in water or partially dissolved. This can be accomplished by reacting them with a suitable capping agent to protect the hydroxyalkyl carbamate group, which enters the crosslinking reaction upon heat curing the deposited composition. Generally, the protecting agent can be any reagent that reacts with the hydroxy group of the hydroxyalkyl carbamate to form esters, urethane, thiocarbamate, sulfonic acid esters, sulfonamate esters, ethers, etc. Becomes insoluble. Some of the suitable protective agents are shown in the table below and the components resulting from protecting the hydroxy portion of the hydroxyalkyl group of the hydroxyalkyl carbamate are also shown in the table below.

The protective agents in the above table are shown for the purpose of illustration and are not limited thereto. For example, alcohols, mercaptans, amines and polyamines including diols and polyols (Example 4 below) may be used as protective agents to impart water insolubility to the hydroxyalkyl carbamate crosslinkers.

For example, the process of protecting the hydroxyalkyl carbamate component of the crosslinking agent with a polyol can be represented by the following scheme.

R ₁ in the reaction should contain the following hydroxyalkyl carbamate groups.

Condensation of 3 moles of biscarbamate prepared by reacting 1,6-hexanediamine with propylene carbonate as shown in Scheme (40) with 1 mole of trimethylolpropane is used in the cationic electrocoating composition according to the present invention. Suitable liquid organic solvent soluble trifunctional crosslinkers are prepared. The starting material, biscarbamate, is a water soluble, difunctional, crystalline material. Because of its water solubility, it does not co-deposit with the resin and therefore cannot be used for cationic electroplating. The protection of biscarbamate with polyols results in a hydrophobic composition suitable for use in the present invention.

The amino group containing polymer used with the hydroxyalkyl carbamate crosslinker mentioned above is a cationic water dispersible non-gelling polymer. The polymeric material may contain several different types of functional groups, such as the presence of hydroxyl groups in the polymeric material is highly desirable for reaction with carbamate crosslinkers. However, carbamate-containing crosslinkers may also be crosslinked via amine groups. Many different types of amino group-containing polymers are suitable for use as cationic polymers as long as they do not gel, are water dispersible, polymerizable and have a cationic charge. The electrical current between the cathode composed of the metal surface and the anode impregnated in the electrodeposition bath is used to co-deposit these polymers onto the metal surface together with the carbamate-containing crosslinker and any crosslinking catalyst (if used). need. Heat can be applied in this way to convert the electrodeposition composition into a crosslinked state. Cationic polymers as described in US Pat. No. 4,026,855, cationic polymers A-F, may be used as the amino group-containing polymers of the present invention. Generally, in addition to the bisphenol-A base epoxy cationic material, a nobarak epoxy group cationic material can also be used.

Acid solubilizers or dispersants may be composed of one or more organic or inorganic acids that are water soluble or at least water dispersible and convert the amino group containing polymer into a cationic charge water dispersible material. Acid solubilizers are water-soluble (or at least water-dispersible) substances, the counterions formed when acid is added to the cationic polymer facilitate the water dispersibility or solubility of the cationic polymer. In general, the acid solubilizer can be any suitable acid that imparts a cationic charge to the polymer while not interfering with the stability or crosslinking reaction of the composition.

Suitable acid solubilizers include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid or polyacids such as acetic acid, butyric acid, pentanic acid, formic acid, lactic acid, citric acid or adipic acid, oxalic acid, malonic acid, succinic acid, maleic acid, or fumaric acid. Carboxylic acid.

Optional catalysts are effective at lowering the curing temperature of other components of the composition after they have been electrodeposited onto the substrate. Therefore, the catalyst must be co-deposited with other components in the cathodic electrodeposition method. Usually suitable crosslinking catalysts lower the curing temperature of the electrodeposited material from about 204-316 ° C. to about 93-204 ° C. without the catalyst. In order to sufficiently co-deposit the crosslinking catalyst with the other components of the electrodeposition composition, it is preferred that the crosslinking catalyst is water soluble or at most partially soluble in water. It is also preferred that the catalyst be at least partially dissolved in the crosslinker and the amino group-containing polymer in order to effectively co-deposit the catalyst. Typical catalysts include organotin compounds such as dibutyltin dilaurate, organozinc compounds, organotitanium compounds, quaternary ammonium compounds, quaternary phosphonium and arsonium compounds and tertiary sulfonium compounds. Other suitable catalysts include organic tin compounds such as dialkyltin compounds (eg dibutyltin dilaurate), organic zinc compounds such as zinc octoate, zinc butyrate, some organic titanium compounds and tetraalkylammonium compounds, where The alkyl group is chosen such that the quaternary ammonium compound is water soluble (or at most water dispersible) and can be co-deposited with the other components of the composition.

Catalysts are generally chosen to be hydrophobic enough to co-deposit with carbamate crosslinkers and amino group containing polymer components in an amount sufficient to lower the curing temperature of the electrodeposited composition. As is known in the art, catalysts can be incorporated into the backbone of polymer (b) during the polymer preparation process. Generally, a sufficient amount of catalyst is co-deposited to lower the curing temperature from about 204-316 ° C. to 93-204 ° C. or below, for example, 93-121 ° C.

Hydroxyalkyl carbamate amines are useful in the eighth aspect of the present invention if the resins can react with the hydroxyalkyl carbamate containing amines and then they can impart water solubility / water dilution to the water insoluble epoxy resin.

The epoxide material used according to the invention may be a monomer or polymer epoxy containing material, preferably a resinous polyepoxide material containing two or more epoxy groups per molecule.

Suitable polyepoxides as described above are reacted with about 1 equivalent of amine compound containing one or more secondary amine groups. The equivalent ratio of amines to epoxy groups should be about 1: 1.

Ideally, all reactive epoxy groups are reacted with secondary amine groups to attach the amine to the epoxide to obtain a polymer substantially free of epoxy.

Another method of preparing the polymer is to react the epoxide with an amine which further contains a catamine group in place of all or part of the hydroxyalkyl carbamate group in addition to one or more secondary amine groups. The secondary amine group can be reacted with an epoxy group to allow the amine group to be attached to the main chain epoxy polymer and then hydrolyze the catamine group to form a free amine group, which is then added to the mixture by adding one or more suitable cyclic carbonates to the resulting free amine group. Can be reacted with. The polyfunctional amines used to form hydroxyalkyl carbamates therefore contain amine groups that can react with cyclic carbonates or catamine groups that can be converted to amine groups that are reactive with cyclic carbonates.

Water-containing coating compositions according to the invention are prepared by adding water and optionally a catalyst and / or cosolvent to the polymer. Depending on the specific hydroxy alkyl carbamate-containing polymer and the amount of cosolvent used, the solubility of the polymer can vary from fully water soluble to water dilutable. Even in the case of the resin having the lowest dilution with water, only 20-30% of the cosolvent can be used to obtain a clear solvent having a low solid content of 10-20%. These cosolvents may also be such as alcohols and glycols. In many cases coating compositions with operable viscosities with high solids content (60-90%) can be obtained without cosolvents.

In preparing the coating composition according to the eighth aspect of the present invention, a hydrophilic polymer is dissolved or dispersed in an aqueous medium, optionally containing a suitable cosolvent, and dibutyltin dilaurate or quaternary ammonium when an external catalyst is used. Add a catalyst like compound. Generally external quaternary or tertiary catalysts are chosen to make them water soluble or water dispersible. Organic solvents usually comprise up to about 20-40% and sometimes up to 10% of the composition. Strong bases such as alkali metal hydroxides (KOH, NaOH, LiOH, etc.) may be included as catalysts in the composition.

In general, a hydroxyalkyl carbamate-containing amine can be reacted with a suitable acrylic backbone resin containing sites reactive with primary or secondary amines (or both) to obtain the ninth feature of the acrylic polymer. The polyfunctional amine used to prepare the hydroxyalkyl carbamate contains secondary amine groups and at least one primary amine group that are masked in terms of reaction with the cyclic carbonate.

These secondary amine groups can then be reacted with epoxy groups on the acrylic polymer without affecting the carbamate groups. The resulting hydroxyalkyl carbamate-containing acrylic polymer of the present invention can be self-crosslinked into a thermosetting acrylic resin suitable for various applications such as coating applications. Self-crosslinking reactions may be base or tin catalyst reactions, which have significant advantages over conventional amino resin systems that required acid catalysts. Thus, the present invention can utilize systems that do not contain formaldehyde and avoid cure inhibition in the presence of shielded amine ultraviolet stabilizers.

At least one mole of reactive moiety capable of reacting with the secondary amine of the hydroxyalkyl carbamate-containing amine of the present invention per mole of such main chain resin is provided to provide a moiety for the amine to be immobilized on the main chain resin. Such reactive sites include, but are not limited to, for example, one or more of the following groups.

As described above, as a result of the reaction of the functional group-containing acrylic polymer with the hydroxyalkyl carbamate-containing amine secondary amine group, the following groups are formed at the functional group site.

(b)

(c)

(a)

(b)

(c)

(e)

(d)

(e)

In instrument tanks R _p is H or C ₁ -C ₈ alkyl; R _q and R _r are the same or different and are amine residues containing a hydroxyalkyl carbamate component.

The repeating units that make up the polymer are divided into two classes, one consisting of units containing suitable amine-reactive functional groups as described above and the other forming the desired film for the polymer and processed coatings or other products made therefrom. It consists of a reforming unit selected to impart a characteristic or other characteristics. In general, any suitable repeating unit or desired combination in the polymer can be used as long as it is present in the polymer with a reactive functional group suitable for the attachment of the primary or secondary amine used in the reaction. Polymer backbones include one or more glycidyl methacrylates, glycidyl acrylates, isocyanate ethyl methacrylates, maleic anhydride, methacryl chloride, n-methyltolacrylamide, 1- (1-isocysyl) Anato-1-methylethyl) -3- (1-methylethenyl) benzene, 1- (1-isocyanato-1-methylethyl) -4- (1-methylethenyl) benzene, methyl acrylamide Amine-reactive repeat units derived from do-glycolate, methyl acryl amido glycolate methyl ether, acrylol chloride and chloromethyl styrene. The polymer backbone also contains one or more acrylic acid, methacrylic acid, butadiene, styrene, alpha-methylstyrene, methyl methacrylate, butyl acrylate, acrylate, acrylonitrile, hydroxyethyl acrylate, glycidyl meta It may also contain modified units derived from acrylates, acrylamides, methacrylamides, vinyl chlorides and vinylidene chlorides.

The use of hydroxyalkyl carbamate-containing amines for producing the acrylic polymer of the present invention can be represented as follows. The hydroxy alkyl carbamate containing compound can be reacted with any suitable acrylic backbone polymer containing, for example, epoxy groups, in which case the reaction can be represented as follows.

In the above scheme, R _h is a segment of epoxy-containing acrylic resin and R _i and R _j are segments of hydroxyalkyl carbamate-containing amine or polyamine compound of the present invention. The reaction generally occurs at room temperature or slightly higher temperatures and is often exothermic. The reaction can be carried out without solvent or an aprotic solvent or alcohol solvent can be used. Various types of acrylic backbone polymers having various reactive functional groups may also be used as follows. For example, a typical polymer having one or more compositions of the invention immobilized thereon may have the following structural formula.

The resulting polymer is crosslinked, optionally upon heating in the presence of a suitable crosslinking catalyst.

Another method of preparing the acrylic polymer is to provide a backbone resin in addition to the primary or secondary amine groups with amines containing protected primary amine groups such as ketimine groups which can be hydrolyzed instead of all or part of the hydroxyalkyl carbamate groups. To react. As described above, when a primary or secondary amine group is reacted with an epoxy group, for example, an amine group adheres to the main chain resin, and then hydrolyzes a ketamine group, a free primary amine group is formed, and then one or more suitable cyclic carbomates are added to the mixture. To react with the resulting free amine groups. The polyfunctional amines used to form hydroxyalkyl carbamate containing amines therefore contain groups such as amine groups that can react with cyclic carbonates or ketimine groups that can be converted to amine groups that can react with cyclic carbonate groups.

A wide variety of acrylic backbone resins containing amine reactive sites can be used for the reaction with hydroxyalkyl carbamate containing amines, depending on the final coating or the desired properties of the product. The secondary amine reactive group of the acrylic resin provides the site where the amine will be attached on the backbone resin. The hydroxyalkyl carbamate-containing resin should contain no more than one secondary amine group per molecule because gelation occurs when more than one such secondary amine group is present per molecule.

Any suitable acrylic resin can be used as the backbone resin according to the present invention. Any one or more monomers may be used to prepare the acrylic resin, but at least one of the monomers used should contain at least one secondary amine reactive group. Such monomers include alkyl acrylates such as butyl acrylate, butyl methacrylate, ethyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, acrylamide, methyl methacrylate, acrylo Nitrile, glycidyl methacrylate, glycidyl acrylate, vinyl acetate, styrene, substituted styrene, alpha methyl styrene, and the like are included for illustrative purposes and are not limited thereto. Generally preferred classes of acrylic resins contain attached glycidyl ether groups.

The acrylic resin has an active site of 0.5-7 mep per gram of acrylic polymer before the reaction with the secondary amine containing a hydroxyalkyl carbamate group (or a precursor thereof). The backbone resin may also contain other functional moieties such as hydroxy and amide groups. The polymers and backbone resins of the present invention preferably have an acid content as low as possible to facilitate low temperature curing of hydroxypropyl such as hydroxypropyl and / or hydroxyethyl carbamate group containing polymers. The monomer from which the acrylic resin is produced may be contaminated, for example, about 0.3-1% by weight with an acid such as methacrylic acid or propionic acid.

The acid content of the polymers of the invention is preferably no more than about 0.1% by weight of the polymer in order to obtain relatively low temperature cure. The acrylic polymer itself may also have 0.5-10 mep of attached or terminal hydroxy alkyl such as hydroxypropyl and / or hydroxyethyl, carbamate groups per gram.

The acrylic polymers of the present invention can be modified by reacting them with selected organic secondary amines (in addition to hydroxyalkyl carbamate containing amines) such as diethylamine, dibutylamine, morpholine, n-methylaniline. The choice and combination of specific modified secondary amines, of course, depends on the intended use of the polymer. For example, in preparing a water dilutable polymer, several functional sites on the backbone resin can be reacted with one or more hydrophilic secondary amines to increase the hydrophilicity of the polymer. On the contrary, when it is preferable that the polymer is hydrophobic, for example, when used in electrodeposition coating, it is necessary or preferable to react the main chain resin with one or more hydrophobic secondary amines to impart the desired degree of hydrophobicity to the polymer. In general, the polymers of the present invention are suitable for use in the field of coatings, in which case it is desirable to have a molecular weight of about 1000-50000, more preferably about 2000-20,000. The urethane crosslinkable polymers of the present invention are particularly suitable for use in coating applications such as solvent or water based coatings, powder coatings, electrocoating compositions, spray rollers and dip coatings. Such coatings are usually applied to substrates such as metals, textiles, plastics or paper. The thermosetting resins of the present invention can be used to prepare adhesives and laminating resins as well as urethane coatings that are resistant to organic solvents and water and wear.

The coating composition containing the acrylic polymer of the present invention can be modified by incorporating other additives in the composition, such as aminoformaldehyde resins, reactive diluents and the like, which alter the physicochemical and mechanical properties of the resulting coating.

The acrylic polymer of the present invention is particularly useful as a binder in conventional solvent-based coating, electrocoating, powder coating and the like and can be formulated with or without a catalyst.

Generally, the tenth characteristic of the present invention is the primer coating, which can be applied to various structural materials including aluminum, aluminum alloy, titanium, titanium alloy, steel, glass, natural and synthetic rubber, synthetic organic polymer or mixtures thereof. If primer coatings need to be heated to cure, they must be able to withstand the temperatures required to cure the deposited coating as well as the structural materials to which they are applied. The curing temperature may be 204 ° C. or higher but in some cases a low temperature of about 93-121 ° C. may be used and a curing time of up to about 1 hour may be used, for example about 30 minutes.

The adhesive used as the coupling means in the present invention may be composed of any suitable structural adhesive. Examples of suitable structural adhesives are described, for example, in the following references (Adhesives for Metals-Theory and Technology by Nicholas J. De Lollis, Industrial Press Inc., New York, 1970, at page 81 et seq). In general, copolymers of phenols with materials such as epoxy adhesives, neopretenes, nitrile rubbers (Buna N), vinyls such as polyvinyl butyral, or novel high temperature resistant condensation or addition polyimide adhesives are commonly used for this purpose. A class of structural adhesives particularly suitable for the present invention is epoxy resin adhesives comprising phenolic copolymers with epoxy resins. Epoxyphenols generally have good resistance to high temperatures, so they are suitable for use on airplane surfaces exposed to high temperatures at high speeds. Epoxyphenolic structural adhesives meet federal standard limits for prolonged exposure to 148-260 ° C. Such adhesives generally consist of epoxy resins, phenolic resins and other optional additives such as aluminum powders that act as oxygen "getters" with amine curing agents.

Another suitable adhesive class is condensation or addition polyimide. They exhibit excellent thermal and oxidant stability (review article by J. R. Fowler in Materials and Design, Vol. 3, December 1982, pp 602-607). These polyimide adhesives usually have a service life of thousands of hours at 250-300 ° C.

Metals or other surfaces on which primer coatings are deposited are usually cleaned well by known methods prior to depositing the primer coating. The coating can then be cured, air dried or oven dried to handle the parts. In assembly, a thin film-like adhesive supported on the peelable carrier material is applied on the primercoated surface, and then peeling off the carrier material leaves an adhesive layer. The parts are then placed in position and held together so that there is an adhesive layer between the primer-coated surfaces and then heated to cure the adhesive layer and the primer coating (if not already cured) to form a single structural bond. In the aircraft industry, protective primer corning is widely used with epoxy, nitrile rubber phenolic, nylon epoxy, condensation and addition polyimides, and epoxyphenol adhesives.

Primer coating in the present invention is prepared from a polymer composed of a hydroxyalkyl carbamate-containing amine that is crosslinked under curing conditions to obtain a coating composition that is stably attached. The hydroxyalkyl carbamate containing polymer may be a hydrophobic polymer that is electrodeposited on the member to be bonded. The coating may also be of a hydrophilic polymer applied from an aqueous medium.

The hydroxyalkyl carbamate-containing amines are reacted with the water-insoluble epoxide-containing "backbone" compound as previously mentioned after preparation.

The epoxide material available may be any suitable monomer or polymer epoxy containing material and is preferably a resinous polyepoxide material containing two or more epoxy groups per molecule. In addition to the epoxides described above, resins of the following structural formulas (a) and (b) were found to be suitable for the present invention:

(a)

Wherein R = CH ₂ -CH-CH ₂ , n is on average 0 to about 5, preferably on average about 0-0.7.

(b) Triglycidyl isocyanurate polyepoxy resin

As used herein, "tris (hydroxyphenyl) methane base resin" means a resin in which n is 0-5 in the structural formula (a), and "triglycidyl isocyanurate resin" refers to a resin of the structural formula (b). it means.

The secondary amines which react with the epoxy resins to produce the polymers of the present invention include cyclic carbonates with at least one primary amine group (which may be a protected primary amine group as described above) and at least one masked secondary amine. Prepared by reaction with a polyfunctional amine containing a group.

In this case, the secondary amine groups remain unreacted in the carbonate reaction to react with the active epoxy sites of the epoxide to form a self-crosslinkable polymer which is deposited on the member and then cured to form a primer coating. .

The effects of the present invention are shown in the following preferred embodiments. Examples 1 and 2 illustrate the preparation of carbamate and ketimine group-containing amines and carbamate-containing amines, respectively.

Example 1

A solution of 51 g (0.5 mole) of diethylenetriamine in 150 ml of methanol was added to 168 g (1.65 mole) of propylene carbonate at 15 ° C. After the addition was completed the material was allowed to react at 25 ° C for 24 hours. Potentiometric titration revealed the presence of free secondary amines. The reaction mixture was then heated to 70 ° C. and left at that temperature for 3 hours. Another potentiometric titration showed that the free amine content remained almost unchanged. After removing the methanol from the reaction mixture, a syrupy liquid consisting of about 72% solids containing bis (2-hydroxy-1-methylethyl) (iminodiethylene) biscarbamate remained.

Example 2

103 g (1 mol) of diethylene triamine and 200 g of methanol were added to the three-necked flask with a stirrer and a thermometer installed suitably. 184.8 g (2.1 mol) of ethylene carbonate was added little by little to the methanol solution of the resulting diethylenetriamine. After the addition of ethylene carbonate was completed, the reaction temperature was raised from room temperature to 65 ° C. The reaction mixture was allowed to react for several hours without external heat supply. After distillation removed methanol, the residue was left to solidify. The solid residue was recrystallized from ethanol to give a white solid in 90% yield. The product was identified by I.R., N, M, R and potentiometric titration to find that it was bis (2-hydroxyethyl) (iminodiethylene) biscarbamate (melting point 98 ° C).

Example 3

408 g (4 mol) of propylene carbonate and 300 g of methanol were placed in a three-necked flask equipped with a stirrer and a thermometer. 292 g (2 mol) of triethylenetetramine were added slowly, maintaining the temperature at 15-30 degreeC by external cooling under a nitrogen blanket. After the addition was completed, the reaction mixture was heated to 80 ° C. for about 8 hours. After this time, the reaction mixture was identified by I.R. and almost all of the propylene carbonate was reacted. Methanol was then distilled off. The product was solidified to a low melting waxy solid by standing at room temperature. The product was confirmed by IR and potentiometric titration, and the same as the following bishydroxypropyl carbamate structure. The amine equivalent was 210 (calculated, 175).

Example 4

206 g (2 mol) of diethylenetriamine and 600 g of methanol were added to a suitable reactor. 612 g (6 moles) of propylene carbonate, consisting of 2 moles excess of stoichiometric amount, was slowly added to the reactor while maintaining the reaction temperature at 15-20 ° C. under ice blanket cooling under a nitrogen blanket. After the addition was completed, the mixture was stirred at room temperature for 8 hours. The methanol was then removed while heating in a steam bath using a water pump vacuum. The resulting product solution consisted of diethylenetriamine bishydroxypropyl carbamate, containing 73% solids (75% theory) of propylene carbonate and 2.16 meq / g of secondary amine (73% solids). 2.37 meq / g) and specific bands of hydroxypropyl carbamate groups appear in IR.

Example 5

206 grams (2 moles) of diethylenetriamine was added to a suitable reactor with a nitrogen gas introduction tube and an oblique trap in the distillate recovery line. After cooling the reactor in an ice bath, the mixture was stirred well and propylene carbonate (306, 3 mol) was slowly added while maintaining the temperature below 40 ° C. After the addition was completed, the reactor was heated and stirred at 80 ° C. for 2 hours, and then IR analysis showed no unreacted propylene carbonate. Then 300 g (3 mol) of methyl isobutyl ketone (MIBK) were added to the reactor and the contents were refluxed. After refluxing for about 2 hours, the theoretical amount of water was collected in an inclined trap and the reactor was cooled. The resulting product, consisting of a carbamate / ketamine mixture of diethylenetriamine, had a 73% solids content in MIBK (74.8% theory). As a result of the non-aqueous potential titration, the secondary amine content was 2.58 meq / g amine (2.46 meq / g theoretical at 73% solids), and IR showed a specific band of hydroxypropyl carbamate and ketamine group.

Example 6

Preparation of N, N-bis (6-aminohexyl) -2-[(6-aminohexyl) amino] butanediamine

Dimethyl maleate (72 g, 0.5 mole) was added to a solution in 360 g of 1,6-hexanediamine 174 g (1.5 mole) of toluene at 75-80 ° C. over 2-3 hours. Under reflux, the reaction temperature rose from 80 ° C to 110 ° C. After the addition was completed the methanol was distilled off at 120-125 ° C. Toluene was further added (320 g) to maintain the reaction capacity. Amine titration or 1H NMR spectra confirmed that the methyl ester disappeared during the reaction. After the reaction was completed, toluene was removed in vacuo (50-70 ° C., 15-20 mmHg) to obtain a viscous liquid, which was left to solidify. Potentiometric titration showed that the ratio of primary amine to secondary amine was 3/1. NMR and IR spectra were found to match the desired N, N-bis (6-aminohexyl) -2 [(6-aminohexyl) amino] butanediamide structure.

The following examples illustrate the preparation of tris (hydroxyalkyl carbamate) compounds of the present invention using the diamides of Example 6.

Example 7

To 100 g (0.125 mol) of a 50% solution of the diamide of Example 6 in ethanol was added 36 g (0.32 mol) of propylene carbonate and 35 g of ethanol. The reaction mixture was reacted overnight at 25 ° C. The titration of the reaction mixture showed that all primary amine groups reacted and the secondary amine groups remained unreacted. After removing the solvent, a syrup-like product mainly composed of a compound having the following structure was obtained.

Example 8

A. The self-crosslinking Novarac hydroxypropylcarbamate-containing resin, which can be at least 12% replacement by water, was obtained as a clear solution with a total amount of cosolvent of 20% from the following components.

* The reaction product of Shivagaigi Corporation with epichlorohydrin and phenol-formaldehyde condensate

The carbamate-containing amines of EPN 1139 and Example 4 were added to a suitable reactor equipped with a Cowels high speed stirrer under nitrogen if necessary to control the exotherm by external cooling. The solids content of the final product was 80%.

B. 100 parts of the Novarac-hydroxypropyl carbamate-containing resin of A was dissolved in 100 parts of deionized water and 15.4 parts of 1M tetrabutyl ammonium hydroxide catalyst to prepare a sprayable aqueous composition. The resulting clear solution contained only 9% organic solvent and 39% solids. After spraying on an aluminum panel, and baked at 121 ℃ 20 minutes. The resulting cured cured coating had a thickness of 0.5-0.6 mils, a pencil hardness of 4H, passed an in-lb reversal impact test, and resisted more than 300 times of double rubbing with MEK and water.

Example 9

A. A self-crosslinked negative electrode electrodeposition composition containing tertiary amine groups and ketimine groups was prepared from the following components.

* Trade name for Shell Caical Corporation, consisting of a reaction product of epichlorohydrin and bisphenol-A.

** Trade name of propoxy propanol product of Union Carbide Corporation.

B. Epoxy 1004F and MIBK were placed in a suitable reactor under nitrogen and heated to reflux with stirring to remove the water present. The carbamate-containing amine of Example 5 was added at 80 ° C., followed by EPON 1001F and ½ volume of propasol P. After stirring the mixture, the mixture was left at 80 ° C for 2 hours, and then diethylamine dissolved in the remaining propasol P was added slowly to prevent volatilization. The mixture was then stirred and heated at 85 ° C. for 8 hours. Propasol P150g was added and then removed by vacuum distillation (flask temperature 110-120 ° C.). This process was repeated with the addition of 150 g of Profasol P-. The resulting product consists of 76% by weight resin and 0.91 meq of amine (based on 100% resin).

C. 50 g of the self-crosslinkable negative electrode electroplating resin obtained from B is reacted with 5 g of hexyl cellosolve and 5 g of benzylhydroxycarbamate (1 equivalent of benzylamine after reacting with 1 equivalent of propylene carbonate, Reactive diluent-fluid agent prepared by removing this with acidic ion exchange resin); An electrodeposition bath was prepared by mixing with 10 g of EPON 828 (Shell Chemical Corporation), 1.54 g of 89.9% formic acid and 1.63 g of dibutyltin dilaurate. Then, 376 g of deionized water was slowly added while vigorously mixing with a Cowell stirrer to prepare a bath containing about 12% of solids. The pH of the bath was 4.4, the conductivity was 1300 MΩcm ^{-1 and the} breakdown voltage was 270 volts.

D. The bath material obtained from C was applied to an aluminum panel serving as a cathode at 75 V for 20 seconds by electrodeposition to deposit a thin resin coating on the panel. The panel was then baked at 175 ° C. for 20 minutes to obtain a 0.4 mil thick film. The film was smooth, flexible, had a 4H pencil hardness, passed a 40 in-lb impact test, and resisted more than 200 methylethylketone double frictions.

Example 10

A sprayable composition was prepared by dissolving 100 parts of the hydroxyalkyl carbamate-containing amine of Example 3 in 100 parts of deionized water and then adding 11.6 parts of 1M tetrabutylammonium hydroxide catalyst. The resulting solution, 48% solids in water, was sprayed onto an aluminum panel to deposit a coating thereon. The panels thus coated were cured at 149 ° C. for 20 minutes. The thickness of the cured film was 0.3-0.4 mils. The coating was a bit hazy but smooth and had a F pencil texture, passed the 40 in-lb impact test, and was resistant to 300 MEK double frictions. However, after 40 rubs with water, the film was removed from the panel.

Example 11

184.8 g (2.1 mole) of ethylene carbonate was slowly added to a suitable reactor containing 103 g (1 mole) of diethylenetriamine and 300 g of solvent methanol under bilso atmosphere. Cooling in an ice bath kept the temperature at 15-20 ° C. After the addition was complete the mixture was stirred at rt overnight. The water pump was then vacuumed and heated in a steam bath to remove methanol.

The resulting product solidifies into a white crystal mass at melting point 82-88 ° C. upon cooling. Recrystallization from ethanol yielded a pure product with a fusion of 96-97 ° C. in almost quantitative yield. This product was in full agreement with the IR and NMR spectra of bis-hydroxyethylcarbamate of diethylene triamine, such as diethylenetriamine-bis-hydroxymethylcarbamate.

Example 12A

13.7 g of the hydroxyalkyl carbamate of Example 11 and 7.1 g of glycidyl methacrylate were added to 24 g of 1, 2- dimethoxyethanes. The reaction mixture was heated to 85 ° C. for 4 hours and distilled off 1,2-dimethoxy ethanol under reduced pressure. The resulting white product was viscous and glassy and contained 0.3 mmol / g of free epoxy groups. Mass Spectrum Results The main peak was consistent with the mass spectrum of the desired product of the following structure.

Example 12B

20.8 g of 1- (1-isocyanato-1-methylethyl) -3-1 (1-methylethenyl) benzene was added to a suspension in 100 g of t-butanol of 27.9 g of hydroxyalkyl carbamate of Example 11. Added. The reaction mixture was stirred with a high speed stirrer. After two hours, most of the solids were dissolved and a small amount of unreacted isocyanate was observed in I.R. The reaction mixture was stirred overnight and then filtered to remove traces of insoluble matter and t-butanol was distilled off from the filtrate under reduced pressure. The resulting product was transferred to N.M.R. The results showed that the following structural formula.

Example 12-A-1

50 g of 2-epoxyethanol was added to a suitable three-necked flask with a stirrer and a thermometer. At reflux, a mixture of 60 g of N-butylacrylate, 20 g of styrene, 59 g of monomer of Example 12A, 1 g of N-dodecyl mercaptan, and 50 g of 2-ethoxyethanol of 2 g of dicumylperoxide was added to the flask over 2 hours. . The reaction mixture was kept at 145 ° C. for 2 hours. The resulting 58% solids resin had a basic nitrogen content of 1 meq per gram of resin and a hydroxyethyl carbamate content of 2 meq per gram of resin.

Example 12B-1

175 g of toluem was added to a suitable triplet flask with stirrer and thermometer. At reflux temperature, a monomer mixture consisting of 58.9 g of N-butylacrylate, 45 g of methyl methacrylate, and 71.2 g of the hydroxypropyl carbamate-containing monomer of Example 12B was added to toluene together with 4 g of t-butylperbenzoate as initiator. . After 4 hours reflux, a hydroxypropyl carbamate group-containing resin was obtained. The resin consisted of 50% solids and contained 1.65 meq of hydroxy propyl carbamate per gram of resin.

Example 13

A. Self-linked bisphenol-A hydroxypropyl carbamate-containing resins, which can be reduced by at least 15% of solids by water, are prepared as clear solutions containing only 20% of the co-solvent of the total composition from the following components: did.

* Reaction product of epichlorohydrin and BP-A (manufactured by Sbell Chemical Co.)

The carbamate-containing amines of EPON 828 and Example 4 were added under nitrogen to a suitable reactor with a Cowells stirrer. After stirring, the temperature was raised to 100 ° C. (exothermic reaction), and the temperature was maintained for 1 hour by external cooling. The mixture was then stirred and heated at 70 ° C. for at least 4 hours. The solids content of the final product was 80%.

B. A sprayable aqueous composition was prepared by mixing 191.4 parts of resin obtained from A, 191.4 parts of deionized water, and 15.3 parts of ethylene glycol monobutyl ether cosolvent. The resulting clear solution contained only 13.5% of the organic cosolvent in total weight and had a solids content of 38.5%.

14.5 parts of 1 M aqueous tetrabutylammonium hydroxide catalyst was added to this solution, and the contents were stirred well. This composition was spray applied onto an aluminum panel. Subsequently, the panel was baked at 121 ° C. for 20 minutes and cured, and the film thickness was 0.3-0.4 mil. The coating was smooth, glossy, had a 4H pencil hardness, passed the 40 in-lb reversal impact test, and resisted more than 300 times with water and methyl ethyl ketone (MEK).

Example 14

A. A self-crosslinked bisphenol-A hydroxyethylcarbamate-containing resin, which can be reduced by at least 10% solids by water, was prepared as a clear solution containing 20% by weight of cosolvent from the following components.

* Monobutyl ether of ethylene glycol

Epon 828, the carbamate-containing amine of Example 11, and butyl cellosolve were mixed and reacted as in Example 13. The solids content of the final product was 80%.

B. A spray composition was prepared by dissolving 100 parts of BP-A hydroxyethyl carbamate of A in 100 parts of deionized water and 7.7 parts of 1M tetrabutylammonium hydroxide catalyst. The resulting clear solution contained only 10% organic cosolvent and 39% solids.

The film thickness was 0.3-0.4 mils after spraying on an aluminum panel and baking at 121 ° C. for 20 minutes. The coating was smooth and glossy, had a 4H pencil hardness, passed 40 in-lb reversal impact tests, and resisted more than 300 times of double friction with MEK and water.

Example 15

A. Self-crosslinking saturated hydroxyethylcarbamate-containing resins containing 20% by weight of cosolvent, which can reduce solids content by at least 20%, were prepared from the following components.

Eponex DRH 151-Shell Chemical Corporation, hydrogenated BP-A epichlorohydrin product Eponex DRH 151 and the carbamate containing amine of Example 2 were externally cooled if necessary in the same manner as described in Example 4. The exothermic reaction was controlled by adjusting carefully. The final product was 100% solids. This product was reduced to 80% solids by ethylene glycol monobutyl ether.

B. A sprayable composition was prepared by mixing 100 parts of saturated hydroxyethyl carbamate of A together with 100 parts of deionized water and 15.4 parts of 1M tetrabutylammonium hydroxide catalyst. The resultant solid solution containing 39% solids and 9% organic cosolvent was sprayed onto an aluminum panel and cured at 131 ° C. for 20 minutes to obtain a 0.4-0.5 mil thick film. The coatings were smooth, glossy, had a 3H pencil hardness, passed 40 in-lb reverse impact tests, and resisted 200 and 300 times, respectively, when rubbed with MEK and water.

Example 16

A. The acrylic urethane polymer was prepared as follows. 100 g of 2-ethoxyethanol was added to a three-necked flask appropriately equipped with a stirrer, thermometer and cooler and heated to 135 ° C. A mixture of 60 g n-butylacrylate, 20 g styrene, 20 g glycidyl methacrylate, 2 g dicumylperoxide, and 1 g n-dodecyl mercaptan over 2 hours was added to heated 2-ethoxyethanol. After adding the monomer mixture containing the initiator and the chain transfer agent, the reaction temperature was kept at 140 ° C. for 2 hours. A nitrogen blanket was maintained in the reactor through the polymerization. The resulting resin had a solids content of 47% and an epoxy content of 0.64 meq per gram.

B. To the acrylic resin obtained in A, 36 g (0.13 mol) of diethylenetriamine bishydroxyethyl carbamate derivative (hydroxy alkyl carbamate of Example 2) was added and the mixture was heated to 80 deg. C for 2 hours and 120 deg. Heated for 2 hours. The resulting resin had the following characteristics: solid: 56.5%, viscosity: U-V, Gardner color: 5-6, basic nitrogen content: 0.51 meq / g, epoxy content: 0.05 meq / g or less.

Four clear coating compositions were prepared by mixing the polymer of Example 16 with the various catalysts listed in Table 1 below. These coating compositions were cast on cold rolled steel panels pretreated with zinc phosphate and cured at high temperatures.

Curing conditions and film characteristics are shown in Table II. The results shown in Table II showed that the polymer of Example 16 self-crosslinked within 20 minutes at a temperature as low as 125 ° C. The tin catalyst crosslinked acrylic-urethane film showed excellent humidity resistance and salt spray resistance. All self-crosslinked films showed excellent resistance to methyl ethyl ketone double friction. The use of hydrophobic quaternary catalysts such as methyltricaprylylammonium hydroxide results in self-crosslinking films having superior humidity and salt spray resistance than those obtained from compositions containing hydrophobic quaternary benzyltriethylammonium hydroxides. Is obtained.

TABLE I

TABLE II

Example 17

70 g of the polymer of Example 16 was emulsified to 10% solids with deionized water in the presence of 1 g of dibutyltin dilaurate catalyst and 1.1 g of acetic acid to prepare a clear electrocoating system. The pH and conductivity of the electrocoated emulsion, 10% solids, were 4.8 and 175 microohms cm ^-1, respectively. Cold-rolled steel panels pretreated with zinc phosphate were electroplated at 100 volts for 30 seconds and then washed with deionized water. The electroplating panels were cured for 20 minutes at 150 and 175 ° C, respectively. The resulting film has excellent organic solvent resistance and rain acid hardness as shown below.

In general, the polymers of the invention can be heat cured after being applied onto a substrate in a suitable manner. It was heat cured at a temperature of about 93-205 ° C. using a suitable crosslinking catalyst as described above. The application composition may consist of a polymer, a suitable catalyst and a liquid excipient such as an aqueous or organic solvent excipient.

Example 18-22

The coating compositions of the following examples consist of compositions prepared by mixing the following ingredients and then diluting the mixture to a Podcup # 4 viscosity of 41-43 seconds using Cellosolve Acetate.

TABLE I

(1) Acrylic resins sold under the trade name ACRYLOID AT-400 may be used.

(2) Crosslinkers sold by the American Cyanamide Company under the trade name CYMEL 303 may be used.

(3) See 1) in Table II below.

(4) A 40% solution in isopropanol of 1% TRS gas PTSA sold by American Cyanamide Company under the trade name CYCAT 400-A is available (PTSA = paratoluene sulfonic acid)

TABLE II

(*) The reactive diluents of the structures (A)-(D) described above were used in the compositions of Examples 19, 20, 21 and 22, respectively.

NV = non-volatile in 3), 4) and 6)

The compositions were applied to a zinc phosphate treated cold rolled steel substrate and heat cured at 125 ° C. for 20 minutes.

Film coatings obtained from the compositions of the examples exhibited the properties of Table III below.

TABLE III

Example 23

32 g (0.10 M) of polytetramethylene glycol (trade name Terracol 650) in a flask equipped with a suitable apparatus; Polyetherpoly by adding 78 g (0.12 M) of hexamethylenebis (hydroxypropyl) carbamate and 0.6 g of dibutyltin dilaurate prepared according to Bull, Chim. Soc. Fr. 1142, 1954 Urethanediol was prepared. The reaction mixture was heated to 175 ° C. under reduced pressure.

Distillates distilled under reduced pressure were mainly propylene glycol and small amounts of propylene carbonate. About 12 g of distillate was collected after 2 hours before the reaction was completed. When cooled, 75 g of cellosolve was added to the resulting product and I.R. analysis showed urethane bonds and very few urea bonds. The resulting resin solids was 57 ± 2% by weight, and the resin showed a very high viscosity.

Example 24

A polyesterpolyurethanediol was prepared following the procedure of Example 23 except that 53g (0.1M) of PCP polyol 0200 was used instead of terracol 650polytetramethylene glycol. I.R. analysis of the product showed the presence of ester and urethane bonds. There was no urea bond or amide bond. The final resin product was diluted with 25 g of cellosolve. The final resin solid content and the Gardner-Holdt viscosity were 51 ± 2% by weight and A-B, respectively.

Example 25-30

The urethane group-containing resin of Example 25-30 was combined with methylated melamine-formaldehyde resin in the presence of a phosphate ester catalyst to prepare a coating composition as shown in the following table.

* Sold under the brand name CYMEL 325 by the American Cyanamide Company. Solid content is 85 ± 2% by weight.

* Sold under the tradename CYCAT 296-9 by American Cyanamide Company.

The compositions were applied on a Bondide 100 support using No. 46 wirecatter and left for 10 minutes. The coating so applied was cured at 125 ° C. for 20 minutes. The properties of the cured coatings thus obtained are shown in the table below.

[table]

As shown in the table above, compositions containing urethane / amine resins in 65-35 weight ratios (Examples 27 and 28) showed optimum film properties after curing them. All films showed good MEK friction resistance and good flexibility.

Example 31

Cationic polymers suitable for cathodic electrocoating were prepared from bisphenol-A epoxy resins sold by Shell Company under the trade name EPON 1004 according to the methods described in the literature (US Pat. No. 3,984,299 column 7, line 65-column 8, line 11). 1830 parts (weight parts) (2 equivalents) of polyglycidyl ether (EPON 1004) of bisphenol-A with an epoxy equivalent of 915 was carried out to remove water that was not known even if present using an inclined trap in the distillate recovery line. It was heated to reflux at 캜 and dissolved in 353.2 parts of methylbutyl ketone. When cooled to 80 ° C. under a dry nitrogen blanket, 52 parts (0.1 equivalents) of diketimine obtained from 1 mole of diethylenetriamine and 2 moles of methyl isobutyl ketone (1.9 equivalents) are added together with 138.8 parts of diethylamine and placed in a batch. After heating to 120 degreeC and leaving for about 2 hours, it diluted with 326 parts propylene glycol monomethyl ether. The resulting poly tertiary amine cationic resin contains a precursor of a primary amine group that can be obtained from the ketimine component upon addition of water. The resulting cationic resin has a calculated solids content of 74.8%. The t-amine group content is 2 meq per gram of resin. Primary NH ₂ is 0.19 meq per gram of resin and hydroxy content is 4 meq per gram of resin.

Example 32

Hexamethylenebis (hydroxypropyl) carbamate was prepared by reacting 2 moles of propylene carbonate with 1 mole of hexamethylenediamine according to the method described by Bull.Chim. Soc.Fr., 1142 (1954). Hydroxypropyl carbonate has a melting point of 70 ° C. and has the following structure.

Example 33

23 parts by weight of the cationic resin of Example 31 and 7.5 parts by weight of hydroxypropyl carbamate of Example 32 were mixed together, and then heated to 60 ° C. to obtain a homogeneous mixture. 0.6 parts by weight of dibutyltin dilaurate catalyst was added to the mixture. The composition was applied onto an aluminum panel and the resulting film was baked at 175 ° C. for 20 minutes. The baked film (about 1 mil thick) was robust and resistant to organic solvents such as methylethyltetone.

Example 33A (Comparative)

The procedure of Example 33 was repeated except that hydroxypropyl carbamate was excluded to obtain a baked film from the cationic resin and the catalyst. The resulting film was not solvent resistant.

Example 34

26 parts by weight of branched polyester (hydroxy equivalent of 522) commercially available from Mobé Chemical Corporation under the trade name Multron 221-75 was added 8 parts by weight of hydroxypropyl carbamate of Example 32 and di It was mixed with 0.6 part by weight of a butyltin dilaurate catalyst. The film applied on the aluminum panel from the composition was baked at 175 ° C. for 20 minutes. The resulting film was robust and resistant to organic solvents.

Example 35

10 parts by weight of the cationic resin of Example 31 (solid basis) were mixed with 30 parts by weight of an isomeric mixture of bis (2-hydroxy-1-methylethyl) (methylenedi-4, 1-1-cyclohexanediyl) biscarbamate. The biscarbamate was prepared from propylene carbonate and hydrogenated methylene dianiline (4, 4'-diaminodicyclohexylmethane). The composition was catalyzed with 2 parts by weight of dibutyltin dilaurate catalyst and neutralized to 70% with lactic acid. The mixture was emulsified in water to a solid content of 10% and then electrodeposited on an aluminum panel. After curing at 175 ℃ for 20 minutes, the film was smooth, pencil hardness was over 2H, reverse impact resistance was over 60in-lbs and methyl ethyl ketone solvent resistance was over 200MEK friction.

Example 36

A commonly used bifunctional terephthalic acid containing a powdered polyester resin having an average molecular weight of 2800 and a glass electrical temperature of 65 ° C. was melt mixed with 13% biscarbamate of Example 32 and then colored with titanium dioxide.

The composition was catalyzed using 3% by weight of dibutyltin dilaurate based on the weight of the binder. The solidified melt was ground to a powder of 25-100 microns in size and then electrostatically coated. The resulting electrocoated film was baked at 200 ° C. for 20 minutes.

The resulting cured film had a thickness of 1.5 mils, a pencil hardness of 2H or more, a reverse impact strength of over 140 in-lb on steel substrates, and a 20 ° gloss of 80% on untreated steel. The salt spray resistance on iron phosphate steel was excellent.

Example 37

292 g (2 moles) of triethylenetetramine were slowly added to a suitable reactor containing 408 g (4 moles) of propylene carbonate and 300 g of methanol solvent while maintaining the temperature at 15-30 ° C by ice bath cooling. After completion of the addition, the mixture was heated to 80 ° C. for about 3 hours and checked by IR to show only a trace of propylene carbonate. The solvent methanol was then distilled off and heated in a steam bath to remove the last traces at 5 mm pressure. Upon standing at room temperature, the product composed of triethylenetetramine bishydroxypropyl carbamate solidified to a low melting paste. The product was found to be 98% non-volatile, titrated with phenol red indicator in water, with only one amine group per molecule titrated and equivalent to 367 (when corrected to 98% solids). Theoretical molecular weight is 357). When potentiometric titration using HClO ₄ in acetic acid was carried out, the equivalent weight was 210, which is closer to the theoretical value. The infrared spectrum resulted in a perfectly consistent structure and did not cause any problems when the theoretical equivalent of 175 was used.

Example 38

A. A self crosslinking negative electrode electrocoating composition containing a tertiary amine group was prepared from the following components.

* Trade name of Shell Chemical Company product consisting of the reaction product of epichlorohydrin and bisphenol-A.

* Trade name of propoxypropanol from Union Carbide Corporation.

B. EPON 1004 and MIBK were placed in a suitable reactor under nitrogen as described in Example 5. The mixture was stirred under heating to remove the water present. After cooling to 80 ° C., the carbamate-containing amine of Example 4 was added and the temperature was raised to 90 ° C. (weak exothermic reaction). After the addition was completed the mixture was heated and left at 100 ° C. for 2 hours. Then, diethylamine dissolved in propasol P was added slowly so as not to lose diethylamine by volatilization. After addition the mixture was heated at 85 ° C. for 2 h more. Propasol P250 was added to remove residual free amine, and the same amount was removed by vacuum distillation at 110-125 ° C. The resulting product consists of 76% by weight resin solids and 0.79 meq of amines (based on 100% resin) per gram.

C. 50 g of the self-crosslinking negative electrode electrocoated resin obtained in B was mixed with 10 g of hexyl cellosolve (ethylene glycol monohexyl ether-flowing agent), 1.2 g of 89.9% formic acid, and 1.3 g of dibutyltin dilaurate (urethane catalyst). To prepare an electrodeposition bath. 398 g of deionized water was added slowly while rapidly mixing with a Cowells stirrer to prepare a bath containing about 10% solids. The resulting electrodeposition bath had a pH of 4.6, a conductivity of 1800 microoum cm ^-1 , and a burst voltage of 180 volts.

D. The bath material obtained in C was applied to an aluminum panel serving as a cathode at 75V for 20 seconds by electrodeposition to deposit a thin resin coating on the panel. The panel was then baked at 175 ° C. for 20 minutes to form a coarse film 0.2-0.4 mil thick. During the electrodeposition, the surface was slightly roughened because of the slight outgassing due to the conductivity of the emulsion. This problem can be easily overcome by improving the manufacturing technique to remove residual free amines. All panels exhibited 4H pencil hardness and resistance to methyl ethyl ketone double friction was more than 200 times.

Example 39

A. Self-crosslinking negative electrode electroplating compositions containing tertiary amines, ketimines and on average a large proportion of carbamate crosslinkers were prepared from the following components.

* Same as in Example 38.

** Monobutyl ether of ethylene glycol.

B. Water was removed from EPON 1004F after adding MIBK under nitrogen as in Example 38. The carbamate-containing amine of Example 3 dissolved in butyl cellosolves at 85 ° C. was added and the mixture was stirred for 1 hour. At the same temperature, the carbamate-containing amine of Example 2 was added and the mixture was further stirred for 8 hours. The styrene oxide was then dissolved in the remaining butyl cellosolve, and then the whole was added at 90 ° C. and stirred for another 4 hours. The resulting product consists of 69% by weight resin and contains 1,10 meq of amine per gram based on 100% resin.

C. 50 g of the self-crosslinking negative electrode electrocoated resin obtained in the above B was hexyl cellosolve 3g, benzylhydroxypropyl carbamate 5g, EPON 828.7g, 89.9% formic acid 1.26g, dibutyltin dilaurate 1.4g (urethane catalyst) Was mixed with to prepare an electrodeposition bath. 475 g of deionized water was added slowly with vigorous stirring with a Cowells stirrer to prepare a bath containing about 10% solids. The pH of the electrodeposition bath was 4.1, the conductivity was 1050 microohms cm ^-1 , and the bursting strength was 400 volts.

D. The bath material obtained in C was electrodeposited on an aluminum panel acting as a cathode at 100 V for 20 seconds to deposit a thin resin coating on the panel. After the coated panel was baked at 175 ° C. for 20 minutes, the film thickness of the panel was 0.3 mil. The coating was shiny and smooth, flexible to 4H pencil hardness, passed 40 in-lb impact test and resistant to more than 400 methylethylketone double frictions.

Example 40

A. A self crosslinking negative electrode electrocoating composition containing tertiary amine, ketimine and alkyl groups was prepared from the following components.

As in Example 38

B. Water was removed from EPON 834 by charging MIBK as in Example 38 and refluxing under nitrogen. After cooling to 80 ° C., dodecylamine dissolved in 50 parts of butyl cellosolve was gradually added to bring the temperature to 115 ° C. (heat of exothermic reaction). The carbamate-containing amine of Example 37 dissolved in 50 parts of butyl cellosolve was then added, and the mixture was allowed to cool slowly, followed by stirring for 1 hour. Then, the carbamate-containing amine of Example 5 dissolved in 100 parts of butyl cellosolve at 90 ° C. was added, and the mixture was stirred for 5 hours at 90 ° C. Thereafter, styrene oxide dissolved in the remaining butyl cellosolve was added, and then the mixture was stirred and heated at 90 ° C. for another 12 hours. The resulting product consists of a 70% by weight resin solid and 1.89 meq of amine per 100% resin.

C. An electrodeposition bath was prepared by mixing 50 g of the self-crosslinking negative electrode electrocoated resin obtained from B above with 5 g of hexyl cellosolve, 1.37 g of 89.9% formic acid and 1.2 g of dibutyl tin dilaurate (urethane catalyst). Subsequently, 320 g of deionized water was added slowly while vigorously mixing with a Cowells stirrer to obtain a bath containing about 10% solids.

The pH of the electrodeposition bath is 4.6, the conductivity is 1050 microohms cm ^-1 and the burst voltage is 300 volts.

D. The composition obtained from C was electrodeposited on aluminum and untreated steel panel, which acted as a cathode at 100V for 20 seconds, to deposit a thin resin film, and then cured at 175 ° C. for 20 minutes to film 0.4 mil on aluminum and steel A film having a thickness of 0.55 mil was obtained. The coatings were all polished, smooth, flexible, had 4H pencil strength, passed 40 in-lb impact tests on aluminum and 150 in-lb impact tests on steel, and resisted more than 100 methylethylketone double frictions. After 200 hours of exposure in a salt spray cabinet, the coating on the untreated steel was drawn 6 mm from the scribe and showed little rust (grade 9 in ASTM 0610-68).

Example 41

A. A composition consisting of the above components 1: 1 mixture was prepared from the following components to prepare an electrocoating composition having both the advantages of both the self-crosslinking resin of Example 39 and the self-crosslinking resin of Example 40. .

B. All of the above components except water were mixed to prepare an electrodeposition bath, and then a bath containing about 10% solids was prepared by slowly adding water while mixing vigorously with a Cowells stirrer. The pH of the electrodeposition bath was 4.3, the conductivity was 1100 macroohm cm ^-1 , and the burst voltage was 340 volts.

C. The bath material of B was electrodeposited on aluminum, untreated steel, and zinc phosphate treated steel panels serving as cathodes at 100 V for 20 seconds to deposit a thin coating, and then baked at 175 ° C. for 20 minutes, each 0.4 mil (aluminum) in thickness. , 0.55 mils (untreated steel), and 0.5 mils (zinc phosphated steel) were obtained. All coatings were smooth, shiny, flexible and resistant to over 400 methylethylketone double frictions. Coatings on aluminum panels had a 4H pencil hardness and passed 40 in-lb impact tests, while coatings on steel substrates had a 5H pencil hardness and passed 140 in-lb tests. After 100 hours of exposure in a salt spray cabinet, the coating on the untreated steel showed a draw of 7 mm from the scribe and was free of rust. After exposure to 1000 hours of salt spray test, the zinc phosphate panels were drawn 3 mm from the scribe, leaving only traces of rust (grade 8 in ASTM 0610-68). Coatings on aluminum also passed a 30-day resistance test (Boeing Material Specification 5-89D) against aerospace fluid Skydroll (Boeing Material Specification 3-11 Fluid), with only one unit of pencil hardness. After 60 days of exposure to the salt spray test, there was no change in the appearance of the coated aluminum panel and no damage to the scribe brain was observed.

Example 42

A. A ketamine group-containing electrocoated backbone resin initially devoid of carbamate groups, which was subsequently converted to a self-crosslinking negative electrode electrocoating composition by reaction with alkylene carbonate, was prepared from the following components.

As in Example 38.

B. Water was removed from EPON 1004 by reflux with MIBK under nitrogen as in Example 38. The mixture was then cooled to 80 ° C. and diketimine (derived from 1 mole of diethylenetriamine and 2 moles of MIBK as in US Pat. No. 3,523,925) and 80 parts of propasol P were added. After about 30 minutes diethylamine in the remaining propasol P was added and the mixture was allowed to react at 80 ° C. for 1 hour and at 120 ° C. for 2 hours. The resulting product consists of 74.6 wt% resin and 2.24 meq of amine per 100 g resin.

C. The resin obtained in B was converted to a self crosslinking cathode electrocoating composition as follows. To 50 g of resin, 5 g of hexyl cellosolve, 1.2 g of 89.9% formic acid, 1.2 g of dibutyltin dilaurate, and 6.86 g of propylene carbonate were added. While stirring rapidly using a Cowell stirrer, 403 g of deionized water was added slowly to obtain an electric coating bath containing about 10% solids. There was no sign of unstable after aging the bath for 4 days with stirring. The pH of this bath was 6.6, the conductivity was 1900 microoum cm ^-1 and the burst voltage was 120 volts.

D. A thin resin coating was deposited by applying the composition obtained in C to an aluminum panel which serves as a cathode for 20 seconds at 75V. After curing for 20 minutes at 175 ℃ to form a film of about 0.2-0.4 mils thick on the panel. All coatings had a rough surface due to the gases produced during electrodeposition. This problem can be overcome by improving the manufacturing process so that residues such as free residual low molecular weight amines that result in extremely high emulsion conductivity can be removed.

All panels exhibited 4H pencil hardness and were resistant to at least 100 methylethylketone double frictions.

A significant advantage of the composition of the present invention as mentioned above is that it provides an electrodepositable coating that can be cured at low temperatures such as about 93-121 ° C. Examples 43 and 44 below are examples of engineered coatings obtained for such low temperature curing.

Example 43

A. A self crosslinking negative electrode electrocoating composition was prepared from the following components.

As in Example 38.

** Monobutyl ether of ethylene glycol.

B. EPON 1001F and MIBK were charged to a suitable reactor under nitrogen and then water was removed as in Example 38. The carbamate-containing amine and dodecylamine of Example 37 were added at about 85 ° C. in about 20 minutes, followed by 100 parts of butyl cellosolve. After stirring this mixture, it heated at 85 degreeC for 1 hour, and the carbamate containing amine of Example 5 was added with 100 parts of butyl cellosolves. The mixture was stirred at 85 ° C. for 8 hours, heated, styrene oxide dissolved in the remaining butyl cellosolve was added, and the whole was heated and stirred at 95 ° C. for 4 hours. The final electrocoated resin had a 69% solids content and a total amine content of 1.32 meq / g when calibrated to 100% solids.

C. 50 g of the self-crosslinking cathode electrocoating resin obtained from B was ion exchanged in methanol with 5 g of hexyl cellosolve, 1.52 g of 89.9% formic acid and 1.94 g of 72% methyl tricaprylyl ammonium hydroxide catalyst. And methanol prepared by evaporation under reduced pressure) to prepare an electrodeposition bath suitable for low temperature curing. Then 314 g of deionized water was added with vigorous stirring with a Cowells stirrer to obtain a bath containing about 10% solids. Methyl tricaprylyl ammonium hydroxide catalyst was converted to the formate form in this composition. The resulting electrodeposition bath had a pH of 3.9, a conductivity of 1000 microoum cm ^-1 and a burst contact pressure of 220 volts.

C. The composition of C was applied to an aluminum panel serving as a cathode by electrodeposition at 75 V for 30 seconds to deposit a thin resin film on the panel. The coated panel was baked at 121 ° C. for 20 minutes and a 0.4-0.5 mil thick film was formed. The coatings were all smooth but had some graininess. The coating was well cured, exhibited a 4H pencil hardness, passed a 40 in-lb impact test, and was not removed after 200 rubs with methyl ethyl ketone (MEK).

Example 44

A. The self-crosslinking negative electrode electrocoated resin of Example 43B was used in the electroplating composition cured at 120 ° C. below.

B. The procedure of Example 43 was repeated except that 2.04 g of 99.8% acetic acid was used instead of formic acid to prepare an electrocoating bath. The catalyst in the composition is methyltricaprylyl ammonium acetate obtained by replacing the hydroxide counterion with acetate ions. The pH of the electrodeposition bath was 4.2, the conductivity was 450 microocm cm ^-1 and the burst voltage was 280 volts.

C. The thin resin film of B was electrodeposited at 100V for 30 seconds on an aluminum panel serving as a cathode. The coated panel was baked at 121 ° C. for 20 minutes to obtain a film of 0.35-4 mils in thickness. The coating was smooth but had a slight grain, had a 4H pencil hardness, passed a 40 in-lb impact test, resisted 100 MEK friction, and removed the film at 200 MEK friction.

In general, the polymer of the present invention, consisting of the reaction product of bisphenol-A with an amine as described above, consists of 0.5-4 meq, preferably 0.7-2.5 meq, of amine per gram of resin solid. When using Novarac epoxy resins to form the polymers of the present invention, hydrophobic amines are often added as described above, and the polymers are preferably composed of amines of preferably 0.5-5 meq, more preferably 0.7-3 meq per gram of resin. . If hydrophobic amines are used as described above they constitute 10-80% by weight (hydrophobic amine and hydroxyalkyl carbamate-containing amine), preferably 10-40% by weight of the total amine added to the reaction. The amine containing a hydroxyalkyl carbamate group is preferably a hydrophilic amine such as diethylene triamine bishydroxyethyl carbamate and the carbamate of Examples 1 and 3. Polymers derived from bisphenol-A are sufficiently hydrophobic to overcome the effects of hydroxyalkyl carbamate groups as long as the epoxy equivalents are high enough. Low molecular weight bisphenol-A epoxy resins can be lengthened by primary or di-secondary amines, and the reactants and conditions must be carefully selected to avoid gelation.

Example 45

618 g (6 moles) of diethylenetriamine were added to a suitable reactor. 1836 g (18 moles) of propylene carbonate, 6 molar excess of stoichiometric amount, was added to the reactor under a blanket of nitrogen while maintaining the reactant temperature at 15-20 ° C. by ice cooling. After the addition was completed, the mixture was stirred at room temperature for 8 hours. The resulting product solution consists of diethylene triamine bishydroxy propyl carbamate and has a solids content of 75.2% (theoretical: 75%) and a secondary amine content of 2.51 meq / g in propylene carbonate. 2.45 meq / g at 75.2%), showing a specific band of the hydroxypropyl carbamate group in the infrared spectrum.

Example 46

Novarak-based hydroxyalkyl carbamate electrocoating resins

A. A self-crosslinking negative electrode electrocoating composition based on a nobarak-hydroxyalkyl carbamate resin was prepared from the following components.

Dow Chemical's epoxy novalac resin.

** Monobutyl ether of ethylene glycol.

B. DEN 485 and MIBK were charged under nitrogen to a suitable reactor with gradient traps in the distillate recovery line. The mixture was heated to reflux with stirring to remove any water present. After cooling to 100 ° C., N-methylaniline was added to 40 parts of butyl cellosolve and the stirred mixture was heated and placed at 140-145 ° C. for 2 hours. The mixture was then cooled to 90 ° C. and the carbamate containing amine of Example 45 and the remaining butyl cellosolve were added. The mixture was stirred and heated at 90 ° C. for 2.5 hours, then styrene oxide was added and the temperature was left at 90-100 ° C. for 2 hours. Analysis of the final electrocoated resin showed 1.81 meq / g of amine. The solids content of the resin was 75%.

C. 300 parts of the Novarac-hydroxypropyl carbamate electrocoating resin of B was mixed with 6.83 parts of 90.8% formic acid and 4.62 parts of dibutyltin dilaurate (urethane catalyst) to prepare an electrocoating bath. A bath containing about 10% solids was prepared by slowly adding 2046.7 parts of deionized water while rapidly mixing with a Cowell stirrer. The pH of the electrocoating bath was 4.4, the conductivity was 600 microoum cm ^-1 and the burst voltage was 210 volts.

Example 47

The electrodeposition bath of Example 46 was applied to a substrate composed of 2024T3 phosphanodized aluminum members at a voltage of 75V for 20 seconds. The resulting deposited coating was cured by heating at 175 ° C. for 5 minutes and then held at 175 ° C. for 20 minutes. A 0.35-0.4 mil thick film was obtained. The resulting coating was glossy, slightly orange peeled, exhibited a 7H pencil hardness, passed a 40 + in-lb impact test on a 0.02 inch thick substrate, and was coated even after rubbing 300+ times with methyl ethyl ketone. This has not been removed.

In general, the use of suitable tertiary or quaternary ammonium catalysts results in electrodeposited coatings that can be cured at low temperatures such as 121 ° C. If used properly, these catalysts can be successfully used at temperatures as low as 93 ° C.

The amount of such catalyst used to carry out low temperature curing is usually about 0.1-10%, preferably 1-5% by weight of the resin weight.

Example 48

Carbamate Crosslinker I

In a properly equipped flask, 436.8 g (2.1 mole) of 4, 4'-diaminodicyclohexylmethane (isomer mixture), 435.4 g (4.3 mole) of propylene carbonate and 262 g of t-butyl alcohol were charged under nitrogen. After the mixture was refluxed, the remaining amine was titrated with 0.1 N HCl using a phenol red indicator. After refluxing for 3 days, 95% was converted and the mixture was cooled to 50 ° C. and 500 ml of acetone were added. After cooling to room temperature the mixture was converted to a slurry of white crystals. The mixture was then warmed to 60 ° C. and filtered. Ethyl acetate-heptane (2: 1 volume ratio) was added to the filtrate in small portions until no more solids were separated. The solid collected by refiltration was combined with the one obtained previously and dried overnight at 40 ° C. to give 125 g (14.5%) of bis (2-hydroxy-1-methylethyl) (methylene di-4,1-cyclohexanediyl) biscarbamate A high melting point (192-198 ° C) isomer was obtained, which is called "carbamate crosslinker I" and shows satisfactory spectrum analysis results, but because of their high melting point range, it is not considered suitable for use in cathode electrocoating compositions. Do not. Thus, a sufficient amount of cation exchange resin (Dowex 50W-X8, manufactured by Dow Chemical) was added to the clear filtrate to remove all residual free amine, and the removal was determined from time to time by checking with a phenol red indicator. After removal of all free amines, the ion exchange resin was filtered off, and the solvent was distilled under vacuum while heating in a steam bath, and the last trace amount was removed under 5 mm pressure. The resulting clear pale yellow low melting semisolid showed satisfactory spectral analysis as an isomeric mixture of bacamate crosslinker I. The yield of carbamate crosslinker I was 683.1 g (80% of theory, total yield of all dicarbamate was 93.7% of theory).

Example 49

Carbamate Crosslinker II

Charge 95.36 g (0.4 mole) of 2, 2'-bis (4-aminocyclohexyl) propane, 83.72 g (0.82 mole) of propylene carbonate and 53.72 g of t-butyl alcohol under nitrogen to a suitable reactor and reflux the whole. I got it. Residual amine was titrated with 0.1 N HCl using phenol red indicator. After 3 days reflux, the viscous reaction mixture was allowed to cool to 50 ° C. and 54 g of methanol were added. The same cation exchange resin as used in Example 48 was added to remove the free amine and the solution was filtered. Isomer mixture of bis (2-hydroxy-1-methylethyl), [(1-methylethylidene) di-4, 1-cyclohexanediyl] biscarbamate after heating in a steam bath to evaporate all solvents under vacuum 163 g (91% of theory) were obtained, also referred to as "carbamate crosslinker II". Spectrum analysis confirmed the structure. Carbamate crosslinker II softens to about 60 ° C. and begins to melt at about 80 ° C.

Hexane-1, 6-bis (hydroxypropyl) carbamate as starting material for negative electrode electrocoating composition

Hexane-1, 6-bis (hydroxypropyl) carbamate is not suitable as a carbamate crosslinker for negative electrode electrocoatings because it is completely water soluble. Hexane-1, 6-bis (hydroxypropyl) carbamate is hexamethylene diamine as described in Najer, H., Chabrier, P., and Guidicelli, R., Compt. Rend. 238 690 (1954). After reacting with propylene carbonate it was completely purified to prepare. This bishydroxypropyl carbamate was then chemically modified to protect the hydroxyalkyl carbamate group to produce a water insoluble carbamate crosslinker for cathodic electrocoating as follows.

Example 50

Carbamate Crosslinker III

In a suitable reactor was charged 50.0 g anhydropydine and 8.72 g (0.04 mol) of hexane-1, 6-bis- (hydroxypropyl) carbamate prepared as described above under nitrogen. The well stirred solution was then cooled to 3 ° C. and acetic anhydride (8.98 g; 0.88 mole) was sufficiently stirred and slowly added while maintaining the temperature below 10 ° C. After the addition was complete the mixture was stirred at rt overnight. At this time, thin layer chromatography (TLC-Analtech procoated Silica Gel GF 250 micron plate 2.55 × 10 cm; eluent 10/90 V / V MeOH / CHCl ₃ followed by drying at 105 ° C. for 30 minutes to remove pyridine and pyridine acetate: Color reaction) showed only one product spot at Rf 0.73. Pure hexane-1, 6-bis (hydroxypropyl) carbamate has an Rf value of 0.53 under the same conditions. Most of the pyridine solvent was removed at about 10 mm pressure at a flask temperature of 40-80 ° C. Then, the reaction residue containing the product was dissolved in CHCl ₃ (100 ml), and then washed three times with 25 ml of 25% w / w NHCl solution, twice with 25 ml of water, and once with 25 ml of brine. The CHCl ₃ solution of the product was then dried (Na ₂ SO ₄ ), filtered and evaporated in vacuo to give 10.77 g (99%) of a light yellow liquid which solidified to a low melting solid. This product was insoluble in water and uniform by TLC, and the IR and PMR spectra were consistent with the diacetates of hexane-1, 6-bis (hydroxypropyl) carbamate, and the material was then referred to as "carbamate crosslinker III It will be referred to as ".

Example 51

Carbamate Crosslinker IV

In a properly equipped flask, trimethylol propane (13.4 g), hexane-1, 6-bis (hydroxypropyl) carbamate (96 g) and dibutyl tin dilaurate catalyst (0.6 g) prepared as above were charged. . The reaction mixture was stirred and then heated to 175-190 ° C. for about 1 hour under reduced pressure (about 20 mm Hg). About 10 g of distillate was obtained during this period, which was found to be almost propylene glycol as confirmed by GPC. The clear resin product in the flask is soluble in alcohol, cellosolves, but insoluble in water. The condensation product of hexane-1, 6-bis (hydroxypropyl) carbamate and trimethylol propane is hereinafter referred to as "carbamate crosslinker IV". The product was diluted with 20 g of cellosolve to reach 77% solids.

Example 52

Cationic Polymer V

The cationic polymer V is n-butylacrylate, styrene, N, N-dimethyl aminoethyl methacrylate, 2-hydroxyethyl acrylate, reaction product of methoxy polyethyleneglycol and acrylic acid having a molecular weight of 550, N-dodecyl mer Captans and azobis isobutyronitrile were prepared by reacting according to the methods and amounts described in the preparation of Polymer E in US Pat. No. 4,026,855. The final resin had a solids content of about 71%, a hydroxyl number of about 90 and an amine group of about 45.

Example 53

Cationic Polymer VI

The cationic epoxy resin, the cationic polymer VI, is a product of Shell Chemical consisting of the reaction product of bisphenol-A and epichlorohydrin and the reaction portion of US Pat. Prepared by reaction with diketimines of ethylenetriamine (prepared as described in US Pat. No. 3,523,925). The contents of US Pat. Nos. 3,523,925 and 3,984,299 are incorporated by reference. The solid content of the final cationic resin was 75%, the analysis value of the resin corrected to 100% solids is as follows; 5-amine: 1 meq / g, primary amine (after being watered): 0.2 meq / g, calculated hydroxy content: 3.7-4 meq / g.

Example 54

Cationic Polymeric Materials VII

Epoxy material, cationic polymer VII, was prepared according to the method described below from the following components.

A product of Shell Chemical, a reaction product of epichlorohydrin and bisphenol-A.

** Union Carbide, Propoxypropanol.

EPON 1004 and MIBK were charged under nitrogen into a suitable reactor with an oblique trap in the distillate recovery line. The mixture was heated to reflux with stirring to remove any water that may be present. After cooling to 80 ° C., propasol P was added followed by diketamine (prepared as described in US Pat. No. 3,523,925 from 1 mole of diethylene triamine and 2 moles of MIBK). The mixture was allowed to stand at 80 ° C. for 1 hour, then cooled to 60 ° C. and diethylamine was slowly added while maintaining the temperature at 65 ° C. or lower (exothermic reaction) so as not to lose diethylamine by volatilization. After the addition was completed, the mixture was refluxed for 1 hour and 100 parts of additional profasol P was added. The same amount of propasol P was then removed by vacuum distillation twice at 100 ° and 125 ° C. to remove residual free diethylamine. The final cationic resin contained 78% solids. The analytical value of resin corrected to 100% solids is as follows; -Amine, 0.84 meq / g: primary amine (after hydrolysis): 0.45 meq / g: calculated hydroxy content: 3.6-3.8 meq / g.

Example 55

A negative electrode electrocoating bath was prepared by mixing 50 parts of cationic polymer V, 15 parts of carbamate crosslinker I, 1.7 parts of 88% lactic acid and 1.5 parts of dibutyltin dilaurate in a suitable stirring vessel equipped with a Cowells stirrer. 466 parts of deionized water were added slowly while these ingredients were rapidly mixed to prepare a bath containing about 10% solids. The pH of the final cathode electrocoating bath was 4.8. After aging overnight in the bath, the composition was electrodeposited at 100V for 60 seconds on an aluminum panel acting as a cathode, then washed and cured at 175 ° C for 20 minutes to give a cured film that was smooth, glossy and had excellent solvent resistance and mechanical properties. Got it.

Example 56

The following ingredients were used and all critical procedures were repeated for Example 55.

* Monohexyl ether-flowing agent of ethylene glycol.

** Monobutyl ether co-solvent of ethylene glycol.

The final cathode electrocoating bath had a solids content of 10%, a pH of 5.8 and a conductivity of 700 microocm cm ^-1 . After aging overnight in the bath, the composition was electrodeposited at 75V for 20 seconds on an aluminum panel acting as a cathode, washed, and cured at 175 ° C. for 20 minutes to obtain a 0.2-0.25 mil film. All panels were smooth and glossy, had a 4H pencil hardness, passed 40 in-1b impact tests, and resisted more than 200 times of methyl ethyl ketone friction.

Example 57

The procedure of Example 55 was repeated with the components of Example 56 except that 15.3 parts of carbamate crosslinker II was used instead of 14.4 parts of carbamate crosslinker I. The resulting cathode electrocoating bath had a pH of 5.8, a conductivity of 700 microohms cm ^-1 , and a solids content of about 10%. After aging the bath overnight, the composition was electrodeposited at 75 V for 20 seconds on an aluminum panel serving as a cathode, washed, and cured at 175 ° C. for 20 minutes to obtain a film having a thickness of 0.2-0.5 mil. All panel coatings were smooth, glossy, had a 4H pencil hardness, passed 40 in-1b impact tests, and were resistant to more than 200 methylethylketone double frictions. The electrocoating bath was stable for more than three months when stored at ambient temperature.

Example 58

The procedure of Example 55 and the components of Example 56 were repeated except that 9.4 parts of carbamate crosslinker III were used instead of carbamate crosslinker I and 440 parts of deionized water. The resultant cathode electrocoating bath had a solids content of 10%, a pH of 5.5 and a conductivity of 780 microocm cm ^-1 . The bath was then aged overnight and the aluminum panel acting as a cathode was electrocoated at 75V for 20 seconds. This electrocoated panel was washed and cured at 175 ° C. for 20 minutes. The cured film had a thickness of 0.2-0.25 mils, had a 4H pencil hardness, passed the 40in-1b impact test, was smooth and glossy, and was resistant to more than 200 methylethylketone double frictions. The bath remained stable after three months of aging at ambient temperature.

Example 59

47 parts of cationic polymer VI, 19.5 parts of capbamate crosslinker IV, 3 parts of hexyl cellosolve, 1.2 parts of dibutyltin dilaurate, 3.6 parts of 88% lactic acid using 470 parts of deionized water using the mixing procedure of Example 55 To emulsify to 10% solids. This gave a milky white emulsion having a pH of 5.8 and a conductivity of 1225 microumium cm ^-1 . After the cathode electrocoating bath was aged overnight, an aluminum panel serving as a cathode was electrocoated at 50V and 100V for 30 seconds. The electrocoated panels were washed with water and cured at 175 ° C. for 20 minutes. After curing, the electroplated film was solvent resistant, 0.6-0.7 mil thick, passed 40 in-ib impact test, and had a pencil hardness of 4H-5H.

Example 60

184.8 (2.1 mol) of ethylene carbonate was slowly added to a suitable reactor containing 130 g (1 mol) of diethylene triamine and 300 g of methanone solvent under a stream of nitrogen. The temperature was maintained at 15-20 ° C. by ice bath cooling. After complete addition the mixture was stirred overnight at room temperature. The water pump was then vacuumed and heated in a steam bath to remove methanol. The resulting product solidified into a white crystal mass at melting point 82-88 ° C. upon cooling. Recrystallization from ethanol gave a pure product with a melting point of 96-97 ° C. in almost quantitative yield. The IR and NMR spectra of the product were in full agreement with bis-hydroxyethyl carbamate of diethylene triamine, such as diethylene triamine bishydroxyethyl carbamate.

Example 61

292 g (2 mol) of triethylenetetramine were slowly added to a suitable reactor containing 408 g (4 mol) of propylene carbonate and 300 g of methanol solvent while maintaining the temperature at 15-30 DEG C by ice bath cooling. After the addition, the mixture was heated to 80 ° C. for about 3 hours and IR spectra showed only a trace of the band of propylene carbonate. Subsequently, after removing the methanol solvent by distillation, the last trace amount was removed by heating in a steam bath under 5 mm pressure. Upon standing at room temperature the product consisting of triethylene tetramine bishydroxy propyl carbamate solidified to a low melting point paste. The product was found to be 98% nonvolatile.

Example 62

The procedure of Example 13 was repeated except adding 29 parts of catalyst (corresponding to 5% by weight solid catalyst based on solid catalyst to resin). The resulting film was cured at 104.4 ° C. for 20 minutes, showing similar properties to the cured film of Example 14. In view of the foregoing, curing for longer periods of time at lower temperatures, such as 93.3 ° C., has shown that satisfactory film properties are obtained by the suitably catalyzed polymer of the present invention.

Example 63

A. Replaced EPON 828 with 79.7 parts of EPN 1139 in Example 14, a self-crosslinking Novarachydroxyethyl carbamate-containing resin that could be diluted to 10% solids by water using only 10% by weight cosolvent It was prepared using 52.4 parts of butyl cellosolve. The solids content of the resulting product after the preparation of Example 4 was 80%.

B. 100 parts of the nobarak hydroxyethyl carbamate-containing resin obtained in the above A was dissolved in 100 parts of deionized water and 15.4 parts of 1M tetrabutylammonium hydroxide catalyst to prepare a sprayable composition. The resulting clear solution contained only 9% organic cosolvent and was 39% solids. The composition was applied onto an aluminum panel by spraying and then cured at 121 ° C. for 20 minutes. The resulting smooth, glossy coating had a 4H pencil hardness, was 0.3-0.4 days thick, passed a 40 in-1b reversal impact test and was more than 300 resistant to MEK and water double friction.

Example 64

A. A more polymerizable, self-crosslinking BP-A hydroxypropyl carbamate-containing resin, which can be reduced to at least 35% solids by water using a 25% cosolvent, was prepared from the following components:

Carbamate-containing amines and butyl cellosolves of EPON 828, Examples 4 and 61 were mixed and reacted in the same manner as in Example 61. The solids content of the very viscous product finally obtained was 80%.

B. A sprayable composition was prepared by mixing 100 parts of the polymerizable BP-A hydroxypropyl carbamate product of A together with 100 parts of 60 ° C. deionized water until a milky white suspension was obtained. The stirred suspension was cooled to room temperature and 30 parts of butyl cellosolve and 9.3 parts of tetrabutyl ammonium hydroxide catalyst were added. The resulting clear solution had a solids content of 34% and contained 25% organic cosolvent. The composition was spray applied onto an aluminum panel and then cured at 121 ° C. for 20 minutes. The cured coating had a thickness of 0.4-0.5 mil, smooth and glossy, had a 4H pencil hardness, passed the 40 in-1b reversal impact test, and resisted MEK and water double friction over 300.

Example 65

All details were repeated except for using 1 equivalent of benzyl trimethyl ammonium hydroxide as the catalyst instead of tetrabutyl ammonium hydroxide. The cured film was similar in all respects to the properties of the film tested.

Example 66

All details were repeated except for using 1 equivalent of tetramethyl ammonium acetate as the catalyst instead of tetrabutyl ammonium hydroxide. Some precipitate was formed and the solution was adjusted to 30% solids using ethylene glycol monobutyl ether. After spraying and curing the panel at 121 ° C., the coating had film properties similar to those obtained in Example 4.

Example 67

Except for using 1 equivalent of dibutyltin dilaurate (commonly used urethane catalyst) instead of tetrabutyl ammonium hydroxide as a catalyst, all details were repeated the process of Example 13. The dibutyl tindilaurate catalyst is not completely compatible with the water based system but forms a relatively stable suspension in a short time. It does not cure for 20 minutes at 121 ° C, in fact it is necessary to leave 20 minutes at 166-177 ° C. In addition, the film cured at 177 DEG C was poor in appearance and very fragile.

Since the polymer of the present invention is a water-soluble / water-dilutable group, it has a great advantage in terms of environment and safety and can be used with an organic solvent as in Example 13.

Example 68

All detailed procedures of Example 63 were repeated except that butyl cellosolve was used instead of all water solvents and the aqueous tetrabutyl ammonium hydroxide was substituted with 1 equivalent of methanolic benzyltrimethylammonium hydroxide.

After baking at 121 ° C. for 20 minutes, the films obtained as non-aqueous compositions were similar in properties to those obtained from aqueous systems.

Example 69

A. An isocyanurate hydroxypropylcarbamate containing resin was prepared from the following components:

* Shivagaigi product, reaction product of isocyanuric acid with epichlorohydrin

B. Araldite PT 810 and the carbamate-containing amine of Example 4 were added under nitrogen to a suitable reactor equipped with a Coworth high speed stirrer. Upon heating to 80 ° C., the reactant suspension slowly began to exotherm, resulting in a temperature of 113 ° C. After the exothermic reaction was stopped, the almost homogeneous solution was further heated at 115 ° C. for 4 hours. The solids content of the final product was 79%.

C. 50.0 parts of the isocyanurate hydroxypropyl carbamate-containing resin of B is dissolved in 207.3 parts of deionized water, followed by spraying by continuously adding 6.0 parts of ethylene glycol monobutyl ether and 8.5 parts of diethylene glycol monobutyl ether flow promoting solvent. An aqueous composition was prepared. A solution containing only 9.2% of organic solvent was filtered and 4.9 parts of 40% aqueous tetrabutyl ammonium hydroxide catalyst were added. The solid content of the resulting clear solution was 14.8%. This composition was applied onto an aluminum panel by spraying. The coating was cured at 121 ° C. for 60 minutes to give a film of 0.15-0.20 mils thick. The coating was smooth, glossy, had a 4H pencil strength, passed 40 in-lb impact tests, and was resistant to more than 300 MEK friction and more than 200 water frictions.

Example 70

To 168 g (1.65 mol) of propylene carbonate was added a solution in 150 ml of methanol of 51 g (0.5 mol) of diethylenetriamine at 15 ° C. After the addition was completed, the mixture was reacted at 25 ° C. for 24 hours. Potentiometric titration showed the presence of free secondary amines. The reaction mixture was heated to 70 ° C. for 3 hours. There was little change in the free amine as shown by titration. Methanol was removed from the mixture to obtain a syrup solution of 72% of a solid content liquid containing bis (2-hydroxy-1-methylethyl) (iminodiethylene) biscarbamate. Analysis of this product by FAB mass spectrum revealed that the composition consisted mainly of the compound.

Example 71

To an appropriately equipped flask with a stirrer and a thermometer, 62.4 g (0.4 mol) of 4-amino-2, 2, 6, 6-tetramethylpiperidine (ATP) and 150 g of methanol were added. 52.8 g (0.6 mol) of ethylene carbonate was added to this solution, and the mixture was heated to 70 degreeC for 2 hours. The separated white solid was filtered at 25 ° C. and washed with methanol to give 63.5 g (65% of theory) of the product having a melting point of 190-192 ° C. IR, N.M.R and potentiometric titration confirmed the structure was 2-hydroxyethyl (2, 2, 6, 6-tetramethyl-4-piperidinyl) carbamate.

Example 72

To an appropriately equipped three-necked flask with a stirrer and a thermometer, 62.4 g (0.4 mol) of ATP (see Example 71) and 25 g of methanol were added followed by 61.2 g (0.6 mol) of propylene carbonate. The reaction mixture was heated to reflux for 5 hours.

After stopping at 25 ° C. overnight, the white crystalline solid was separated. The crystalline solid was filtered and washed with a small amount of methanol to give 82 g (79.4% of theory) having a melting point of 135 ° C. N.M.R analysis showed that the product was a mixture of isomeric hydroxypropyl carbamate containing primary and secondary hydroxy groups in a 2: 1 molar ratio.

Example 73

The procedure of Example 16 was repeated except that 30.2 g of hydroxypropyl carbamate of ATP of Example 77 was reacted with 93.75 g of the acrylic resin of Example 16 A (solid basis) instead of the carbamate of Example 4. The reaction was carried out at 145 ° C. for 18 hours in the presence of 53 g of 2-ethoxyethanol. The resulting acrylic polymer had the following properties.

Solid: 70%, basic nitrogen content: 0.69 meq / g, epoxy content: 0.1 meq / g.

Example 74 (Comparative Example)

33 g of 2-epoxyethanol in an appropriately equipped three-necked flask with a stirrer, thermometer and cooler were heated to 135 ° C. A mixture of 60 g of n-butyl acrylate, 20 g of styrene, 20 g of 2-hydroxyethyl methane acrylate, 1 g of dicumylphenoxide, and 1 g of n-dodecyl mercaptan was slowly added thereto over 2 hours. After the addition of the monomer mixture containing the initiator and the chain transfer agent, the reaction temperature was set at 140 ° C. for 2 hours. A nitrogen blanket was maintained in the reactor during the polymerization. The resulting resin had the following properties: solid: 75%, acid value: 0.4, hydroxy value: 85 (solid basis).

Example 75

The main film obtained from the polymer of Example 73 catalyzed with 1% tetrabutyldiacetoxystenoxane was cured at 150 ° C. for 20 minutes. The cured film had good MEK friction resistance but the film was soft. The polymer of Example 73 is also useful as a light stabilizer for amines impaired in thermosets and thermoplastics.

Example 76

74.4 g of the polymer of Example 73, 1.5 g of benzyltrimethylammonium hydroxide (40% in methanol) and 30 g of ORR 650 rutile titanium oxide pigment were dispersed in a sand mill. The filtered white enamel was injected onto a cold rolled steel panel pretreated with zinc phosphate using a wirecatter. The coated panels were cured at high temperatures resulting in a white, glossy coating that was robust, soluble, and resistant to organic solvents. Curing schedule and film characteristics are as follows.

Example 77 (Comparative Example)

A. Three compositions each of the polymers of Examples 16 and 74 and 2-ethylhexane prepared according to US Pat. No. 3,984,299 using protective toluene diisocyanate (TDI-EHA) and benzyl trimethylammonium hydroxide (BTMA) as catalyst Prepared.

The film was cast on cold rolled steel pretreated with zinc phosphate and then cured at 125 ° C. for 20 minutes. The film obtained from composition I has good MEK friction resistance, indicating that the film is crosslinked. Compositions II and III do not have MEK friction resistance, indicating that the film is not crosslinked. This indicates that hydroxyethyl carbamate behaves chemically differently from hydroxyethyl ester.

B. The following compositions were prepared using the polymer of Example 74 using dibutyl tindilaurate (DBTL) and tetrabutyldiacetoxy stanoxane (TDS) as catalysts with BTMA. The film was cast on zinc phosphate pretreated cold rolled steel and baked at 150 ° C. for 20 minutes. None of the films showed good MEK friction resistance after baking, indicating poor crosslinking. Under similar conditions the polymer of Example 16 provided a well crosslinked film.

Example 78

A. 131 g of anhydrous toluene was added to a properly equipped reactor under a blanket of nitrogen. 59 g of n-butylacrylate, 45 g of methyl methacrylate and 30.1 g of 1- (1-isocyanato-1-methylethyl) -3- (1-methylethenyl) benzene were added at 105 ° C. After the addition, 2.1 g of t-butylperbenzoate initiator was added. The reaction temperature was maintained at 105 ° C. for 3 hours. Adding 2 g of initiator further increased the reaction temperature to 116 ° C. and maintained this temperature for another 5 hours. The resulting polymer had a solids content of 50% and an NCO content of 2.5% by weight.

B. Add 44.5 g of the isocyanate group-containing polymer of A to a suitable reactor under a blanket of nitrogen followed by 10 g of an 80% solution of isobutanol of bis (2-hydroxy-1-methylethyl) (aminodiethylene) biscarbamate 10 g of isobutanol were added at ambient temperature. An initial exothermic reaction occurred and the reaction mixture was left at 30 ° C. for 2 hours. I. R. of the reaction mixture then showed no isocyanate bands and the presence of substituted urea bands. Titration of the resulting product showed no free amine.

[Coating Composition]

The polymer of Example 78 was used as a clear coating composition using dibutyltin dilaurate (DBTL), tetrabutyldiacetoxystanoxane (TDS) and benzyltri-methylammonium hydroxide (BTMA) as catalysts as follows. Formulated.

The curing schedule and film properties of the composition are as follows.

Example 79

A. A self-crosslinking negative electrode electrocoating composition containing tertiary amine, ketimine and having a hydroxyalkyl carbamate crosslinking group was prepared from the following components.

Shell chemical product, reaction product of epichlorohydrin and BP-A

** Methyl Isobutyl Ketone

*** Monobutyl ether of ethylene glycol

B. MIBK was charged under nitrogen into a suitable reactor with an inclined trap in the distillate recovery line and water was removed under reflux from EPON 1004F. After dissolving the carbamate-containing amine of Example 37 in butyl cellosolve 1/3 at 85 ° C., the mixture was stirred for 1 hour. At the same temperature, the carbamate-containing amine of Example 5 was added and the mixture was further stirred for 8 hours. The styrene oxide was then dissolved in the remaining butyl cellosolve and then added at 90 ° C. and stirred for another 4 hours. The resulting product consists of 0.1 meq of amine per gram based on 69% by weight resin and 100% resin.

Example 80

A 1: 1 mixture of the self crosslinking resin of Example 79 and the self crosslinking resin of Example 40 was prepared from the following components to produce an electrocoating composition having the advantages of both components.

* Monohexyl ether of ethylene glycol

B. All of the above components except water were mixed to prepare electrodeposition. Then water was added slowly while vigorously mixing with a Cowells stirrer. The pH of the electrodeposition bath was 4.3, the conductivity was 1100 microoum cm ^-1 and the burst voltage was 340 volts.

C. The bath material of B is electrodeposited on aluminum, untreated steel, zinc phosphate treated steel panel which serves as a cathode for 20 seconds at 100V, and then baked at 175 ° C. for 20 minutes to make the film thickness aluminum, untreated steel, and zinc phosphate treated. Thin coatings of 0.4, 0.55 and 0.5 mil, respectively, were deposited on steel. All coatings were shiny, smooth, flexible and resistant to over 400 methylethylketone double frictions. The coating on the aluminum panel had a pencil strength of 4H and passed the 40 in-lb impact test, while the coating on the steel substrate had a 5H pencil strength and passed the 140 in-lb impact test. After 100 hours of exposure to a salt spray cabinet, the coating on the untreated steel was drawn 7 mm from the scribe line and no rust was found. After 1000 hours of saline spraying, the zinc phosphate-treated steel panel was drawn 3 mm from the scribe line and only traces of rust appeared (grade 8 in ASTM 0610-68).

Example 81

The electrodeposition bath of Example 80 was applied for 20 seconds at 100 V on a substrate composed of 2024 T ₃ phosphanodized untreated aluminum members. The resulting coating was cured by heating at 170 ° C. for 20 minutes. The resulting cured film has the following properties:

The film properties show sufficient coating performance as a primer for aerospace applications. Table I below shows that the coating of Example 81 is useful for some binders. Bonding was only shown for high temperature bonding, and defects in the intermetallic test were only minimal.

The primer coating of Example 81 is used with a structural adhesive film composed of a modified epoxy adhesive sold under the tradename FM by the American Cyanamide Company. These adhesive films are supported on a polyester carrier and later peel off the carrier from the adhesive, leaving only the adhesive deposited on the primer coated substrate. The primer coating of the present invention was compared to a known corrosion resistant, organic solvent based spray primer sold under the brand name BR-127 by American Ciana Mid Company. Samples were subjected to the same test after preparing the same adhesive structure as in Example 81 using known primer coatings (control samples) instead of primer coatings according to the invention. The test results are summarized in Table I below.

TABLE I

(1) FM-73 adhesive film is an aerospace adhesive that is cured at 121.1 ° C.

(2) FM-300 adhesive film is an aerospace adhesive that is cured at 176.7 ° C.

(3) The BR-127 primer is an organic solvent based taper for aerospace that cures at 121.1 ° C.

(4) Breakage form: C = bonded, A = bonded to metal: TC = bonded thinly.

Note: The psi value is the average of two or more tests.

Example 82

618 g (6 moles) of diethylenetriamine were added to a suitable reactor. 1836 g (18 mol) of propylene carbonate, consisting of 6 molar excess of stoichiometric, was slowly added to the reactor under a blanket of nitrogen while maintaining the reaction temperature at 15-20 ° C. by ice cooling. After the addition was completed, the mixture was stirred at room temperature for 8 hours. The resulting product solution consists of diethylene triamine bishydroxypropylcarbadate with a solids content of propylene carbonate of 75.2% (theoretical 75%), a secondary amine content of 2.51 meq / g (theory at 75.2% solids). Value is 2.45 meq / g), and IR results show a specific band of the hydroxypropyl carbamate group.

Example 83

Novalak hydroxy alkyl carbamate electrocoating resin

A. A self-crosslinking negative electrode electrocoating composition based on Novarac-hydroxy alkyl carbamate resin exhibiting good high temperature binding was prepared from the following components.

* Dow Chemical Epoxy Novalac Resin

** Monobutyl ether of ethylene glycol

B. DEN 485 and MIBK were charged under nitrogen into a suitable reactor with gradient traps in the distillate recovery line. The mixture was heated to reflux with stirring to remove the water present. After cooling to 100 ° C., N-methylaniline was charged to 40 parts of butyl cellosolve and the stirred mixture was heated and placed at 140-145 ° C. for 2 hours. The mixture was then cooled to 90 ° C. and the carbamate containing amine of Example 82 and the remaining butyl cellosolve were added. The mixture was stirred, heated at 90 ° C. for 2.5 hours, styrene oxide was added, and the temperature was further set at 90-100 ° C. for 2 hours. Analysis of the final electrocoated resin showed an amine content of 1.81 meq / g. The solids content of the resin was 75%.

C. 300 parts of the Novarac-hydroxypropyl carbamate electrocoating resin of B was mixed with 6.83 parts of 90.8% formic acid and 4.62 parts of dibutyltin dilaurate (urethane catalyst) to prepare an electrocoating bath. A bath containing about 10% solids was prepared by slowly adding 2046 parts of deionized water with rapid stirring using a Cowells stirrer. The pH of the electrocoating bath was 4.4, the conductivity was 600 microohms cm ^-1 and the burst contact pressure was 210 volts.

Example 84

The electrodeposition bath of Example 83 was applied for 20 seconds at a voltage of 75 V to a substrate consisting of a 2024 T ₃ phosphano-digested untreated aluminum member. The resulting coating was cured by heating at 175 ° C. for 20 minutes. The resulting cured film has the following properties.

Film thickness, wheat: 0.35-0.4

Appearance: Glossy, slightly orange peel texture

Pencil Hardness: 7H

MEK Friction: 300+

Reverse shooting, in-lbs: 40+ at 0.02 inch thick substrate

Skydroll Resistance Test: Pass

Salt Spray Resistance Test: Passed

Table II below shows the comparative test results for the primer coating of Example 84, the results of which are similar to those reported in Table I above.

TABLE II

(1) As in Table I

Example 85

A. A self-crosslinked negative electrode electrocoating composition based on a structurally mixed aromatic nobarac bisphenol-A hydroxypropylcarbamate resin improved in terms of high temperature binding was prepared from the following components.

Celanese Corporationm: Structurally mixed aromatic Novarac bisphenol-A epoxy resin.

B. Substantially the same preparation as in Example 83B was repeated except that Epi-Rez ^R SU-8 was used instead of DEN-485 of Example 83 and the amount of other reagents was adjusted as in the table above. . The analytical value of the final electrocoating resin was 1.73 meq / g amine. The solids content of the electrocoated resin was 75%.

C. 350.0 parts of the electrocoating resin of B was mixed with 7.62 parts of 90.8% formic acid and 5.39 parts of dibutyltin dilaurate to prepare an electrocoating bath. While rapidly mixing with a Cowell stirrer, 2385 parts of deionized water was slowly added to prepare a bath having a solid content of about 10%. The pH of the electrocoating bath was 4.1, the conductivity was 550 microohms cm ^-1 and the burst voltage was 220 volts.

[86]

The electrodeposition bath of Example 83 was applied to a substrate composed of 2024T ₃ phosphanodized untreated aluminum member for 20 seconds at a voltage of 75V. The resulting deposited coating was cured by heating at 175 ° C. for 20 minutes. The resulting cured film has the following properties.

Film thickness, wheat: 0.35-0.4

Appearance: Glossy, slightly orange peel texture

Pencil Hardness: 7H

MEK Friction: 300+

Reverse shock in-lbs: on substrates 40+, 0.02 inches thick

Skydroll Resistance: Pass

Salt spray resistance: pass

Table III below shows the comparative test results for the primer coating of Example 86, the results of which are similar to those reported in the table above.

TABLE III

(1) As in Table I.

Examples 81-86 illustrate the preparation and use of hydrophobic cathodic electrodepositable coatings in the present invention. The following examples similarly illustrate the preparation and use of hydrophilic water based coatings.

Example 87

The hydroxy alkyl carbamate containing amines used in Examples 88 and 89 below were prepared using the same reactant ratios in the same manner as in Example 82 except for using methanol as the solvent (40% by weight).

After the reaction was completed (8 hours at room temperature), methanol was removed by heating in a steam bath using a water vacuum pump. The resulting product solution consists of diethylenetriamine bishydroxypropyl carbamate and has a solids content of propylene carbonate of 73% (75% of theory), a secondary amine content of 2.16 meq / g (at 73% of theory of solids). 2.37 meq / g), IR showed a specific band of the hydroxypropyl carbamate group.

Example 88

A. Self-crosslinked bisphenol-A hydroxypropyl carbamate was prepared from the following components which could be diluted by water into a clear solution containing a minimum of 15% solids and containing only 20% by weight cosolvent.

Shell chemical product, reaction product of epichlorohydrin and BP-A.

The carbamate containing amines of EPON 828 and Example 87 were added under nitrogen into a suitable reactor equipped with a Cowells high speed stirrer. After stirring, the temperature became 100 ° C. (heat of exothermic reaction) and the temperature was maintained for 1 hour at ionicity while cooling externally. Then the mixture was stirred and heated at 70 ° C. for 4 more hours. The solids content of the final product was 80%.

B. A sprayable aqueous composition was prepared by mixing 191.4 parts of the resin obtained from A above with 191.4 parts of deionized water and 15.3 parts of ethylene glycol monobutyl ether cosolvent. The resulting clear solution contained only 13.5% by weight organic cosolvent and had a solids content of 38.5%.

To this solution was added 14.5 parts of an aqueous 1M tetrabutyl ammonium hydroxide catalyst and the contents were stirred well. This composition was spray applied to an aluminum panel. The film thickness was 0.3-0.4 mils after the panel was baked and cured at 120 ° C. for 20 minutes. The coating was smooth and glossy, had a 4H pencil hardness, passed 40 in-lbs inversion impact tests, and resisted water and methyl ethyl ketone (MEK) double friction above 300.

Example 89

The composition of Example 88A was spray applied onto a substrate made of 2024T ₃ phosphanodicide untreated aluminum member. The resulting coating was cured by heating at 120 ° C. for 20 minutes.

The resulting cured film had the following properties.

Film thickness, wheat: 0.25-0.3

Appearance: smooth and glossy

Pencil Hardness: 4H

MEK Friction: 300+

Water friction: 300+

Reverse shock, in-lbs: 40+, skydroll resistance test on substrate 0.02 inches thick: Pass

Salt spray resistance test: passed

The table below shows comparative test results for the primer coating of Example 88.

Table IV

(1) As in Table I.

Example 90

A. Self-crosslinking Novarac hydroxypropyl carbamate was prepared from the following components which could be diluted with water to a clear solution containing at least 12% solids and containing 20% by weight total cosolvent.

Shivagagi products, reaction products of phenol-formaldehyde condensates with epichlorohydrin.

The carbamate-containing amine of Example 87 and EPN 1139 were reacted in the same manner as in Example 88A while controlling the exothermic reaction heat by external cooling, if necessary. The solids content of the final product was 80%.

B. 100 parts of the nobarak-hydroxypropyl carbamate of A were dissolved in 100 parts of deionized water and 15.4 parts of 1M tetrabutyl ammonium hydroxide catalyst to prepare a sprayable aqueous composition. The resulting clear solution contained only 9% organic cosolvent and had a solids content of 39%. After spraying on an aluminum panel, it was baked at 121 ° C for 20 minutes. The resulting cured coatings were 0.5-0.6 mil thick, had a 4H pencil hardness, passed a 40 in-lbs reversal impact test, smooth, glossy, and 300+ resistant to MEK and water double friction.

Example 91

The composition of Example 90 was spray applied to a substrate comprised of 2024T ₃ phosphanodized untreated aluminum members. The resulting deposited coating was cured at 121 ° C. for 20 minutes. The resulting cured film has the following properties.

Film thickness, wheat: 0.25-0.3

Appearance: smooth and glossy

Pencil Hardness: 5H

MEK Friction: 300+

Water friction: 300+

Reverse impact test, in-lbs: 40+, on 0.02 inch thick substrate

Skydroll Resistance Test: Passed

Salt spray resistance test: passed

The following table shows the comparative test results for the primer coating of Example 92.

TABLE V

(1) As in Table I.

Example 92

A. A self-crosslinking tris (hydroxyphenyl) methane base (THPM) hydroxypropyl carbamate resin showing excellent binding properties was described below. The resin was diluted with water to obtain a clear solution containing at least 10% solids and 20% by weight of auxiliary beads. This resin was prepared from the following components.

* Dow Chemical Company-THPM base epoxy resin

The carbamate-containing amines of XD 7342, OOL and Example 82 were added to a suitable reactor equipped with a Cowells high speed stirrer under nitrogen.

Upon stirring all XD7342, OOL dissolved at 60 ° C. (shear and exothermic heat) and the reactor temperature reached 80 ° C. before the exotherm was stopped. The mixture was then stirred and heated at 90 ° C. for 2 hours. The solids content of the final product was 82%.

B. A sprayable aqueous composition was prepared by mixing 316.8 parts of the resin of A with 485.3 parts of deionized water and 66.9 parts of butyl cellosolve cosolvent. The resulting clear solution contained a total of 14 wt% organic cosolvent and 30% solids. To this solution was added 19.5 parts (3% by weight of solid) of 40% aqueous tetrabutyl ammonium hydroxide catalyst and the contents were stirred well.

C. The composition of B was spray applied to a substrate composed of 2024T ₃ phosphanodized untreated aluminum members. The resulting coating was cured by heating at 121 ° C. for 20 minutes. The resulting film has the following properties.

Film thickness, wheat: 0.25-0.3

Appearance: smooth, polished

Pencil Hardness: 5H

MEK Friction: 300+

Water friction: 300+

Reversal impact, in-lbs: 40+, 0.02 inch thick substrate

Skydroll Resistance Test: Passed

Salt spray resistance test: passed

The table below shows the comparative test results for the primer coating of Example 92.

Table VI

Although the present invention has been described with reference to preferred specific examples, specific embodiments may be variously changed without departing from the spirit or scope of the present invention by those skilled in the art.

Claims (1)

(a) self-condensation of polyhydroxy alkyl carbamate, (ii) condensation of poly-hydroxy alkyl carbamate compound with polyol, and (iii) condensation of poly-hydroxy alkyl carbamate compound with polyamine A polymer selected from the group consisting of one or more hydroxy group containing polyurethanes, hydroxy group containing polyureas and hydroxy group containing polyurethanes / polyurea polymers produced across one or more reaction pathways selected from; (b) amino crosslinkers; And (c) an acid catalyst which is an optional component.