GB2035340A

GB2035340A - Coating composition comprising polymers of amino acids

Info

Publication number: GB2035340A
Application number: GB7934803A
Authority: GB
Original assignee: Nippon Paint Co Ltd
Current assignee: Nippon Paint Co Ltd
Priority date: 1978-10-06
Filing date: 1979-10-08
Publication date: 1980-06-18
Also published as: GB2066254A; DE2940509A1; GB2066254B; GB2035340B; DE2940509C2

Abstract

A coating composition comprises a polymer obtained by solution polymerization of at least one of polymerizable amino acids of the formulae: <IMAGE> wherein R1, R2, R3 and R4 are each hydrogen, methyl or ethyl, R5 is hydrogen or C1-C20 alkyl optionally having -SO-, -COO- or -O- therein, R6 is C1-C12 alkylene optionally substituted with -OH, -SH or -SR7 (R7 being C1-C4 alkyl) and/or optionally substituted with C1-C4 alkyl or phenylene optionally substituted with C1-C4 alkyl and A is -COOH or -SO3H, or of the formula: <IMAGE> wherein R8, R9 and R10 are each hydrogen or C1-C6 alkyl, R11 is hydrogen or C1-C20 alkyl optionally having -SO-, -COO- or -O- therein, or a group of the formula: <IMAGE> (R8, R9 and R10 being each as defined above), R12 is C2-C12 alkylene optionally substituted with C1-C6 alkyl or phenylene optionally substituted with C1-C4 alkyl, and A is as defined above, with or without at least one of other polymerizable monomer.

Description

SPECIFICATION Polymeric resin and coating composition comprising same The present invention relates to a polymeric resin and a coating composition comprising the same. More particularly, it relates to a polymeric resin obtained by polymerization of a polymerizable amino acid compound with or without any other polymerizable monomer and a coating composition comprising such polymeric resin as a main component.

In this specification, the terms "dispersing" and "dispersion" are used in their broad sense and include "dissolving" and "solution".

As the result of an extensive study, it has been found that a polymeric resin obtained by solution polymerization of a certain specific polymerizable amino acid compound with or without any other polymerizable monomer has an excellent pigment dispersibility and is usabie as a resin for dispersing a pigment to provide a coating composition. It has also been found that when a hydroxyl group-containing polymerizable monomer is used as the other polymerizable monomer, a composition comprising the resulting polymeric resin and an aminoplast resin can be readily cured at a low temperature within a short period of time. It has further been found that when a carboxyl group-containing poiymerizable monomer is used as the other polymerizable monomer, the resultant polymeric resin is dispersible in water to give a stable resinous dispersion.It has furthermore been found that a composition comprising such resinous dispersion and an aminoplast resin can afford a coating film having excellent physical properties. The present invention is based on these findings.

The most characteristic feature of the present invention resides in the use of certain specific polymerizable amino acid compounds for production of polymeric resins, which are employed as the main component in a coating composition. Such polymerizable amino acid compounds are representable by either one of the following formulas::

wherein R1, R2, R3 and R4 are each hydrogen, methyl or ethyl, Re is hydrogen or C1-C20 alkyl optionally having -SO-, -COO- or -0-therein, Re is C1-C12 alkylene optionally substituted with -OH, -SH or-SR7 (R7 being C1-C4 alkyl) and/or optionally substituted with C1-C4 alkyl or phenylene optionally substituted with C1-C4 alkyl and A is -COOH or -SO3H, and

wherein, Re, Re and R10 are each hydrogen or C1-Cs alkyl, R11 is hydrogen or C1-C20 alkyl optionally having -SO-, -COO- or -0-therein, or a group of the formula::

R12 is C2-C12 alkylene optionally substituted with C1-C6 alkyl or phenylene optionally substituted with C1-C4 alkyl, and A is as defined above.

As the structurally similar compounds to the said polymerizable amino acid compounds, there are known those of the formula:

and of the formuia: CH2=CH-CeH4-CH(NH2)-CO2M wherein M is a cation such as hydrogen, ammonium or metal are known (Japanese Patent Publication (examined) No. 11651/1967); U.S. patent 2,840,603).

The compounds of the formula (la) wherein Re is C1-C12 alkylene optionally substituted with -OH, -SH or -SR7 and/or optionally substituted with C1-C4 alkyl (hereinafter referred to as "the compounds (la')") and the compounds of the formula (Ib) wherein R12 is C2-C12 alkylene optionally substituted with C-C6 alkyl and A is -SO3H (hereinafter referred to as "the compounds (lib')") are novel, and they are included within scope of the present invention.

In the above polymerizable amino acid compounds, the basic group (i.e. amino) and the acidic group (i.e.

-COOH or -SO3H) may be considered to be present in a tautomeric state or in a mixture of tautomers. For instance, in case of the compounds (la), the tautomerism is representable by the following partial formulas:

wherein B-H represents COO-H or SO3-H. Depending on the conditions, the tautomerism is varied as shown in the following partial formulas:

Thus, by controlling appropriately the conditions such as degree of hydrophilic property and pH, the ionic portions of the said compounds can take an optional form, on which the corresponding characteristic properties are exerted.

The polymerizable amino acid compounds of the present invention may be produced in the processes as shown below.

(A) Production of the compounds (la'): The compounds (la') can be produced by reacting an oxirane compound with an amino acid compound having a primary or secondary amino group. The reaction is preferably carried out under a basic condition. A typical procedure comprises reacting the oxirane compound with the amino acid compound in the presence of a basic substance (e.g. alkali metal hydroxides, ammonia, organic amines) in a solvent such as alcohols, ethylene glycol monoalkyl ethers, dimethylformamide, dimethylsulfoxide or water, or their mixtures at a temperature of 0 to 15000 under an atmospheric or elevated pressure for a period of 10 minutes to 48 hours, usually while stirring.

As the oxirane compound, there may be employed the one representable by the formula:

wherein R1, R2, R3 and R4 are each as defined above. Specific examples of allyl glycidyl ether, methallyl glycidyl ether, allyl methylglycidyl ether, methallyl methylglycidyl ether, etc.

As the amino acid compound, there may be employed the one representable by the formula:

wherein R5, Re and A are each as defined above. Specific examples are glycine, alanine, ss-alanine, Eaminocaproic acid, sarcosine, threonine, cysteine, methionine, taurine, 2-aminopropanesulfonic acid-(1), 1 -aminopropanesulfonic acid-(2), 3-aminobutanesulfonic acid-(2), 2-aminobutanesulfonic acid-( 1), 1 -amino- 2-methylpropanesulfonic acid-(2), 3-aminopentanesulfonic acid-(2), 4-amino-2-methylpentanesulfonic acid (3), 3-aminopropanesulfonic acid-(1), 4-amino-butanesulfonic acid-(2), 4-aminobutanesulfonic acid-(3), 5-aminopentanesulfonic acid-(1), 1 û-aminodecanesulfonic acid-(1), N-methyltaurine, N-ethyltaurine, N- isopropyltaurine, N-butyltaurine, N-heptyltaurine, N-dodecyltaurine, N-heptadecyltaurine, N-(2 octadecylsulfinethyl)taurine, N-(2-stearoyloxymethyl)taurine, 2-methylaminopropanesulfonic acid-(1), 2dodecylaminopropanesulfonic acid-(1), 2-octadecylaminopropanesulfonic acid-(1), 1 -methylamino-2- methvlcrnpanesulfonic acid-(2), 3-methylaminopropanesulfonic acid-(1), etc.

The compounds of the formula:

wherein R13 is hydrogen, methyl or ethyl and R1, R2, R3, R4, R5 and A are each as defined above can be produced also in either one of the following processes (a) and (b).

Process (a) According to this process, an oxyamine compound having a primary or secondary amino group and an ct,ss- unsaturated acid are subjected to addition reaction. A typical procedure comprises reacting them in a solvent such as alcohols, ethylene glycol monoalkyl ethers, dimethylformamide, dimethylsulfoxide or water, or their mixtures at a temperature of 0 to 15000 under an atmospheric or elevated pressure for a period of 10 minutes to 48-hours, if necessary, while stirring.

Astheoxyamine compound, there may be employed the one representable by the formula:

wherein R1, R2, R3, R4 and Rg are each as defined above. Specific examples of allyl 3-amino-2-hydroxypropyl ether, methallyl 3-amino-2-hydroxypropyl ether, allyi 3-amino-3-methyl-2-hydroxypropyl ether, methallyl 3-amino-3-methyl-2-hydroxypropyl ether, allyl 3-(N-methylamino)-2-hydroxypropyl ether, methallyl 3-(Nmethylamino)-2-hydroxypropyl ether, allyl 3-(N-methylamino)-3-methyl-2-hydroxypropyl ether, methallyl 3-(N-methylamino)-3-methyl-2-hydroxypropyl ether, allyl 3-(N-ethylamino)-2-hydroxypropyl ether, allyl 3-(N-butylamino)-2-hydroxypropyl ether, allyl 3-(N-hexylamino)-2-hydroxypropyl ether, allyl 3-(Noctylamino)-2-hydroxypropyl ether, methally 3-(N-octylamino)-2-hydroxypropyl ether, allyl 3-(Noctylamino)-3-methyl-2-hyd roxypropyl ether, methallyl 3-(N-octylamino)-3-methyl-2-hydroxypropyl ether, allyl 3-(N-decylamino)-2-hydroxypropyl ether, allyl 3-(N-dodecylamino)-2-hydroxypropyl ether, allyl 3-(N heptadecylam i no)-2-hyd roxypropyl ether, allyl 3-[N-(2-octadecyisulfinethyl )amino3-2-hydroxypropyl ether, ally 3-[N-(2-stearoyloxyethyl)amino]-2-hydroxypropyl ether, etc.

The a,gunsaturated acid may be represented by the formula:

wherein R13 and A are each as defined above, and its specific examples include acrylic acid, methacrylic acid, vinylsulfonic acid, etc.

When the a,ss-unsaturated acid is used, the existence of a base such as an alkali metal, ammonia or an organic amine in the reaction system is preferred. For this purpose, the a,(3-unsaturated acid may be employed in the form of a salt with the base.

Process (bl According to this process, the oxyamine compound (V) and an a,p-unsaturated acid ester are subjected to addition reaction, followed by hydrolysis of the product in the presence of a basic catalyst.

As the a,ss-unsaturated acid ester, there may be used the one of the formula:

wherein R15 is C1-C14 alkyl optionally substituted with -OH and A' is -COO- or-SOs-, and R13 is as defined above. Specific examples are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, dodecyl acrylate, dodecyl methacrylate, 2-hydroxyethyl acrylate, 2hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, methyl vinylsulfonate, ethyl vinylsulfonate, n-butyl vinylsulfonate, 2-ethylhexyl vinylsulfonate, decyl vinylsulfonate, 2-hydroxyethyl vinylsulfonate, etc.

Examples of the compounds (la) are as follows: N-(2-hydroxy-3-allyloxypropyl)taurine, 2-[N-(2-hydroxy-3 allyloxypropyl)amino]propanesulfonic acid-(1), 1 -[N-(2-hydroxy-3-allyloxypropyl)amino]propanesulfonic acid-(2), 3-[N-(2-hydrnxy-3-allyloxyprnpyl)aminojbutanesulfonic acid-(2), 2-[N-(2-hydroxy-3 allyloxypropyl)aminojbutanesulfonic acid-(1), 1 -[N-(2-hydroxy-3-allyloxypropyl)amino]-2methylpropanesulfonic acid-(2), 3-[N-(2-hydroxy-3-allyloxypropyl)amino]pentanesulfonic acid-(2), 4-[N-(2hydroxy-3-allyloxypropyl )amino]-2-methyl pentanesulfonic acid-(3), 3-[N-(2-hydroxy-3 allyloxypropyl)aminolpropanesulfonic acid-(1), 4-[N-(2-hydroxy-3-allyloxypropyl)aminojbutanesulfonic acid-(2), 4-[N-(2-hydroxy-3-allyloxypropyl)aminolbutanesulfonic acid-(1), 5-[N-(2-hydroxy-3allyloxypropyl)amino]pentanesulfonic acid-(1), 1 O-[N-(2-hydroxy-3-allyloxypropyl)aminojdecanesulfonic acid-( 1), N-methyl-N-(2-hydroxy-3-al lyloxypropyl)taurine, N-ethyl-N-(2-hydroxy-3-allyloxypropyl )taurine, Npropyl-N-(2-hydroxy-3-allyloxypropyl)taurine,N-butyl-N-(2-hydroxy-3-allyloxypropyl)taurine,N-heptyl-N-(2hydroxy-3-al Iyioxypropyl)taurine, N-dodecyl-N-(2-hydroxy-3-allyloxypropyl )taurine, N-heptadecyl-N-(2 hydroxy-3-al lyloxypropyl)tau rine, N-(2-octadecylsulfinethyl)-N-(2-hydroxy-3-allyloxypropyl)tau rine, N-(2stearoyloxyethyl)-N-(2-hydroxy-3-allyloxypropyl)taurine,N-(2-hydroxy-3-methallyloxypropyl)taurine,N-(1 methyl-2-hydroxy-3-allyloxypropyl )taurine, N-(2-hydroxy-3-allyloxypropyl )glycine, N-(2-hydroxy-3methallyloxypropyl)glycine, N-(2-hydroxy-3-methallyloxyprnpyl )sarcosine, N-(2-hydroxy-3allyloxypropyl)alanine,N-(2-hydroxy-3-allyloxypropyl)-ss-alanine,N-methyl-N-(2-hydroxy-3-allyloxypropyl) ss-alanine,N-ethyl-N-(2-hydroxy-3-allyloxypropyl)-ss-alanine,N-butyl-N-(2-hydroxy-3-allyloxypropyl)-ssalanine,N-heptyl-N-(2-hydroxy-3-allyloxypropyl)-ss-alanine,N-dodecyl-N-(2-hydroxy-3-allyloxypropyl)-ssalanine, N-heptadecyl-N-(2-hydroxy-3-allyloxypropyl)-P-alanine, N-(l -methyl-2-hydroxy-3-allyloxypropyl )-P- alanine, N-(2-hydroxy-3-allyloxypropyl )-s-aminocaprnnic acid, N-(2-hydroxy-3-al lyloxypropyl )threonine, N (2-hydroxy-3-allyloxypropyl )cysteine, N-(2-hydroxy-3-allyloxypropyl )methionine, N-(2-hydroxy-3allyloxypropyl)anthranilic acid, N-(2-hydroxy-3-allyloxypropyl)-m-aminobenzoic acid, N-(2-hydroxy-3allyloxypropyl)-p-aminobenzoic acid,l N-(2-hydroxy-3-ailyloxypropyl)orthanilic acid, N-(2-hydroxy-3 allyloxypropyl)metanilic acid, N-(2-hydroxy-3-allyloxypropyl)sulfanilic acid, etc.

(B) Production of the compounds (Ib'): The compounds (Ib') can be produced by reacting a benzyl halide compound with an aminosulfonic acid compound having a primary or secondary amino group. The reaction is preferably carried out under a basic condition. A typical procedure comprises reacting the benzyl halide compound with the aminosulfonic acid compound in the presence of a basic substance (e.g. alkali metal hydroxides, ammonia, organic amines) in a solvent such as alcohols, ethylene glycol monoalkyl ethers, dimethylformamide, dimethylsulfoxide or water, or their mixtures at a temperature ofO to 15000 under an atmospheric or elevated pressure for a period of 10 minutes to 48 hours, usually while stirring.

As the benzyl halide compound, there may be employed the one representable by the formula:

wherein X is a chlorine or bromine and R8, R9 and R10 are each as defined above. Specific examples are vinylbenzyl chloride, vinylbenzyl bromide, isopropenylbenzyl chloride, isopropenylbenzyl bromide, etc.

As the aminosulfonic acid compound, there may be employed the one representable by the formula:

wherein R11 and R12 are each as defined above. Specific examples are taurine, 2-aminopropanesulfonic acid-(1), 1 -aminopropanesulfonic acid-(2), 3-aminobutanesulfonic acid-(2), 2-aminobutanesulfonic acid-)1), 1 -am ino-2-methylpropanesu If onic acid-(2), 3-aminopentanesulfonic acid-(2), 4-amino-2methylpentanesulfonic acid-(3), 3-aminopropanesulfonic acid-(1), 4-aminobutanesulfonic acid-(2), 4aminobutanesulfonic acid-(1), 5-aminopentanesulfonic acid-(1), 1 0-aminodecanesulfonic acid-(1), Nmethyltaurine, N-ethyltaurine, N-isopropyltaurine, N-butyltaurine, N-heptyltaurine, N-dodecyltaurine, Nheptadecylaurine, N-(2-octadecylsulfinethyl )taurine, N-(2-stearoyloxyethyl )taurine, 2methylaminopropanesulfonic acid-(1), 2-dodecylaminopropanesulfonic acid-(1), 2octadecylaminopropanesulfonic acid-(1), 1-methylamino-2-methylpropanesulfonic acid-(2), 3methylaminopropanesulfonic acid-(1), etc. The compounds of the formula:

wherein R14 is hydrogen, methyl or ethyl, and Re, Re, Rlo and R11 are each as defined above can be produced also in either one of the following processes (c) and (d).

Process (c) 3 According to this process, a benzylamine compound and an a,ss-unsaturated sulfonic acid are subjected to addition reaction. A typical procedure comprises reacting them in a solvent such as alcohols, ethylene glycol monoalkyl ethers, dimethylformamide, dimethylsulfoxide or water, or their mixtures at a temperature of O to 1500C under an atmospheric or elevated pressure for a period of 10 minutes to 48 hours, if necessary, while stirring.

) As the benzylamine compound, there may be employed the one representable by the formula:

wherein Re, Rs, R10 and R11 are each as defined above. Specific examples are (vinylbenzyl)amine, (isopropenylbenzyl)amine, (vinylbenzyl)methylamine, (isopropenylbenzyl)methylamine, (vinylbenzyl)ethy lamine, (isopropenylbenzyl)ethylamine, (vinylbenzyl)propylamine, (isopropenylbenzyl)propylamine, (vinyl benzyl)butylamine, (isopropenylbenzyl)butylamine,(vinylbenzyl)heptylamine,(isopropenylbenzyl)heptyla mine, (vinylbenzyl)dodecylamine, (isopropenylbenzyl)dodecylamine, (vinylbenzyl)heptadecylamine, (isop ropenylbenzyl )heptadecylamine, etc.

The α,ss-unsaturated sulfonic acid may be represented by the formula:

) wherein R14 is as defined above, and its specific examples include vinylsulfonic acid.

When the a,-unsaturated sulfonic acid is used, the existence of a base such as an alkali metal, ammonia or an organic amine in the reaction system is preferred. For this purpose, the a,ss-unsaturated sulfonic acid may be employed in the form of a salt with the base.

Process (d) According to this process, the benzylamine compound (X) and an a,ss-unsaturated sulfonic acid ester are subjected to addition reaction, followed by hydrolysis of the product in the presence of a basic catalyst.

As the a,ss-unsaturated sulfonic acid ester, there may be used the one of the formula:

wherein RIB is 01-014 alkyl optionally substituted with -OH and R14 is as defined above. Specific examples are methyl vinylsulfonate, ethyl vinylsulfonate, n-butyl vinylsulfonate, 2-ethylhexyl vinylsulfonate, dodecyl vinylsulfonate, 2-hydroxyethyl vinylsulfonate, etc.

Examples of the compounds (Ib) are as follows: N-(vinylbenzyl)taurine, N-(isopropenylbenzyl)taurine, 2-(N-vinylbenzylamino)propanesulfonic acid-(1), 2-(N-isopropenylbenzylamino)propanesulfonic acid-81), 1- (N-vinylbenzylamino)propanesulfonic acid-(2), 1-(N-isopropenylbenzylamino)propanesulfonic acid-(2), 3-(N I vinylbenzylamino)butanesulfonic acid-(2), 3-(N-isopropenylbenzylamino)butanesulfonic acid-(2), 2-(N vinylbenzylamino)butanesulfonic acid-(1), 2-(N-isopropenylbenzylamino)butanesulfonic acid-(1), I -(N- vinylbenzylamino)-2-methylpropanesulfonic acid-(2), 1-(N-isopropenylbenzylamino)-2- methylpropanesulfonic acid-(2), 3-(N-vinylbenzylamino)pentanesulfonic acid-(2), 3-(N isopropenylbenzylamino)pentanesulfonic acid-(2), 4-(N-vinylbenzylamino)-2-methylpentanesulfonic acid (3), s(N-isopropenyibenzyiamino)-2-methyipentanesulfonic acid-(3), 3-(N vinylbenzylamino)propanesulfonic acid-(1), 3-(N-isopropenyibenzylamino)propanesulfonic acid-( 1), 4-(N vinylbenzylamino)butanesulfonic acid-(2), 2-(N-isopropenylbenzylamino)butanesulfonic acid-(2), 4-(N vinylbenzylamino)butanesulfonic acid-(1 ), 4-(N-isopropenylbenzylamino)butanesulfonic acid-(1), 5-( N vinylbenzylamino)pentanesulfonic acid-( 1), 5-(N-(isopropenylbenzylamino)pentanesulfonic acid-( 1), 1 0-(N I vinylbenzylamino)decanesulfonic acid-(1), 1 0-(N-isopropenylbenzylamino)decanesulfonic acid-(1), N methyl-N-vinylbenzyltaurine, N-methyl-N-isopropenylbenzyltaurine, N-ethyl-N-vinylbenzyltaurinej N-ethyl N-isopropenylbenzyltaurine, N-propyl-N-vinylbenzyltaurine, N-propyl-N-isopropenylbenzyltaurine; N-butyl N-vinylbenzyltaurine, N-butyl-N-isopropenylbenzyltaurine, N-heptyl-N-vinylbenzyltaurine, N-heptyl-N isopropenylbenzyltaurine, N-dodecyl-N-vinyl benzyltaurine, N-dodecyi-N-isopropenylbenzyitauri ne, N heptadecyl-N-vinylbenzyltaurine, N-heptadecyl-N-isopropenylbenzyltaurine, N-(2-octadecylsulfimethyl)-N vinylbenzyltaurine, N-(2-octadecylsulfinethyl)-N-isopropenylbenzyltaurine, N-(2-stearoyloxyethyl)-N- vinylbenzyltaurine, N-(2-stearoyloxyethyl )-N-isopropenyibenzyltaurine, 2-(N-vinylbenzyl-Nmethylamino)propanesulfonic acid-(1), 2-(N-isopropenylbenzyl)-N-methylamino)propanesulfonic acid-(1), 2-(N-dodecyl-N-vinylbenzylamino)propanesulfonic acid-(1), 2-(N-dodecyl-N isopropenyl benzylam ino)pro panesu Ifon ic acid-(1), 2-(N-octadecyl-N-vinylbenzylam ino)propanesulfonic acid-(1), 2-(N-isopropenylbenzyl-N-octadecylamino)propanesulfonic acid-(1), 1-(N-methyi-N- vinylbenzylamino)-2-methylpropanesulfonic acid-(2), 1 -(N-isopropenylbenzyl-N-methylamino)-2 methylpropanesulfonic acid-(2), 3-(N-methyl-N-vinylbenzylamino)propanesulfonic acid-(1), 3-(Nisopropenylbenzyl-N-methylamino)propanesulfonic acid-(1), N-(vinylbenzyi)anthranilic acid, N (vinylbenzyl)-m-aminobenzoic acid, N-(vinylbenzyi)-p-aminobenzoic acid, N-(vinylbenzyl)orthanilic acid, N-(vinylbenzyl)metanilic acid, N-(vinylbenzyl)sulfanilic acid, etc.

The polymerizable amino acid compounds of the present invention have advantageous reactivity, surface activity, electrochemical properties, biologicai properties, etc. They can be introduced, for instance, into high molecular substances with imparting zwitterion characteristics thereto. Particularly, the amino acid compounds wherein the acidic group is a sulfonium group show a pKa value of 1 or less and behave as strongly acidic inner salt compounds. For instance, when such amino acid compounds are copolymerized in small amounts to produce acrylic resins, coating compositions comprising the resultant acrylic resins and aminoplast resins can be cured at low temperatures.Besides, the amino acid compounds of the formula (la') wherein R5 is alkyl having not less than 9 carbon atoms or its modified group or of the formula (Ib') wherein R11 is alkyl having not less than 9 carbon atoms or its modified group exert remarkable surface activity.

The polymeric resin of the invention may be produced by subjecting at least one of the polymerizable amino acid compounds (i.e. at least one of the compounds (la) and (Ib)) with or without at least one of the other polymerizable monomers to solution polymerization in an organic solvent according to a per se conventional radical polymerization procedure.

When the other polymerizable monomers are used, the amount of the polymerizable amino acid compound may be varied depending on the desired properties and the intended purposes of the resulting polymeric resin. Usually, its amount may be from 0.1 to 50 % by weight, preferably from 0.2 to 30 % by weight based on the total weight of the polymerizable monomeric compounds. In case of the amount being lower than 0.1 % by weight, the characteristic properties of the polymerizable amino acid compound will not be exerted. In case of the amount being higher than 50 % by weight, the water resistance of the coating film produced from the resulting polymeric resin will be lowered.

As the other polymerizable monomers to be polymerized with the said polymerizable amino acid compounds for production of the polymeric resin of the invention there may be used any monomeric compounds having an ethylenic unsaturation. Examples ofthem are as follows: hydroxyl group-containing monomers (e.g. 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 3hydroxypropyl methacrylate, 3-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl alcohol, methallyl alcohol), carboxyl group-containing monomers (e.g. acrylic acid, methacrylic acid, protonic acid, itaconic acid, maleic acid, fumaric acid), glycidyl group-containing monomers (e.g. glycidyl acrylate, glycidyl methacrylate), alkyl acrylates and alkyl methacrylates (e.g. methyl acrylate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate), nitrogen-containing alkyl acrylates and nitrogen-containing alkyl methacrylates (e.g. N,N-dimethylaminoethyl acrylate, N,N dimethylamirloethyl methacrylate), polymerizable amides (e.g. acrylamide, methacrylamide, nbutoxymethylacryiamide), polymerizable nitriles (e.g. acrylonitrile, methacrylonitrile), polymerizable aromatic compounds (e.g. styrene, a-methylstyrene, vinyltoluene, t-butylstyrene), a-olefinic compounds (e.g.

ethylene, propylene), vinylic compounds (e.g. vinyl acetate, vinyl propioriate), diene compounds (e.g.

butadiene, isoprene), etc.

As the radical initiator for the solution polymerization, there may be used any conventional one. Specific examples are peroxides (e.g. benzoyl peroxide, di-t-butyl peroxide, cumene hydroperoxide), azo compounds (e.g. azobis-isobutyronitrile, 2,2'-azobis(2,4-dimethyl)valeronitrile, 4,4'-azobis 4-cyanovaleric acid), etc. It may be employed usually in an amount of from 0.05 to 5 % by weight, preferably from 0.1 to 4 % by weight based on the total weight of the polymerizable monomeric compounds. In addition, any convëntional chain-transfer agent such as mercaptans (e.g. laurylmercaptan, hexylmercaptan) may be employed when desired.

As the organic solvent, there may be employed any conventional one, of which examples are alcohols having not more than 6 carbon atoms (e.g. methanol, ethanol), diols (e.g. ethylene glycol, propylene glycol, butylene glycol), ketones (e.g. acetone, methylethylketone, methylisobutylketone), etheric alcohols (e.g.

ethylene glycol monomethyl ethel, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, 3-methyl-3-methoxybutanol), aromatic hydrocarbons (e.g. benzene, xylerie, toluene), etc. The solution polymerization may be carried out by a per se conventional radical polymerization procedure.

For instance; the polymerizable monomeric compounds are subjected to polymerization in the presence of a radical initiator in an organic solvent by elevating the temperature to a desired polymerization temperature.

(usually from 40to 250"C). Alternatively, forjnstance, the polymen'zable' monomen'c compounds are- - - dropwise added to. an organic solvent maintained at a desired polymerization temperature, followed by- aging: A radical initiator may be included in the polymerizable monomeric compounds a'nd,'O'rthe inorganic solvent.The polvmerization is usually completed within 0.5 to 20 hours. '; The thus prepared polymeric resin is ordinarily available in the form of a solution having a solid content of 5 to 80 % by weight and a viscosity of A to Z6 (according to the Gardner indication). The number average molecular weight (Mn) of the polymeric resin determined by GPC is normally from 1,000 to 50,000.

The coating composition of the invention comprises the polymeric resin as prepared above as a main component. Such composition may additionally comprise an organic or inorganic pigment, a crosslinking agent (particularly an aminoplast resin), a filler, a surfactant, an organic solvent, etc. Since the polymeric resin has an excellent pigment dispersibility, its mixture with an organic or inorganic pigment affords a stable and uniform pigment paste.

Particularly when the polymeric resin is the one prepared by the use of a hydroxyl group-containing polymerizable monomer (usually in an amount of not more than 30 % by weight based on the total weight of the polymerizable monomeric compounds) as the other polymerizable monomer, it is preferably employed in a composition with an aminoplast resin. The aminoplast resin may be any conventional one, of which examples are melamine resins, urea resins, guanamine resins, etc. On the use, the aminoplast resin may be previously dissolved in an organicsolventsuch as ethylene glycol monoalkyl etherordiethyleneglycol monoalkyl ether, if necessary. The amount of the aminoplast resin is usually from 5 to 100 % by weight (in terms of solid weight) on the basis of the polymeric resin.The composition comprising the polymeric resin and the aminoplast resin is characteristic in being curable at a low temperature (e.g. 60 to 2000C) within a short period of time (e.g 30 seconds to 60 minutes).

When the polymerizable amino acid compound is polymerized with a carboxyl group-containing polymerizable monomer (and any other polymerizable monomer), there is obtainable a polymeric resin which is easily dispersible in an aqueous medium.

As the carboxyl group-containing polymerizable monomer,there may be speciflcally employed acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, etc. These monomers may be used alone or in combination. As the other polymerizable monomer, there may be used any ordinary one having an ethylenic unsaturation. Examples of hydroxyl group-containing monomers, alkyl acrylates and alkyl methacrylates, nitrogen-containing alkyl acrylates and nitrogen-containing alkyl methacrylates, polymerizable amides, polymerizable nitriles, polymerizable aromatic compounds, a-olefinic compounds, vinylic compounds, diene compounds, etc. These may be used alone or in combination.

The amounts of the polymerizable amino acid compound(s) and the carboxyl group-containing polymerizable monomer(s) may be respectively from 0.1 to 50 % by weight and from 3 to 30 % by weight based on the total weight of the polymerizable monomeric compounds. When the polymerizable amino acid compound(s) are less than 0.1 % by weight, their characteristic properties are not exerted in the resulting polymeric resin. When the polymerizable amino acid compound(s) are more than 50 % by weight, the water-philic property of the produced polymeric resin is increased so that the water resistance of the coating film formed thereby will be lowered.In case of the carboxyl group-containing polymerizabie monomer being less than 3 % by weight, the water-philic property of the resulting polymeric resin is insufficient so that the water dispersibility is much deteriorated. In case of the carboxyl group-containing polymerizable monomer being more than 30 % by weight, the water resistance of the coating film formed by the resultant polymeric resin will be inferior.

For production of the said polymeric resin excellent in dispersibility into an aqueous medium, at least one of the polymerizable amino acid compounds and at least one of the carboxyl group-containing polymerizable monomers with or without at least one of the other polymerizable monomers may be subjected to solution polymerization as hereinbefore explained. The polymerization product is then neutralized, for instance, with a basic substance and dispersed into an aqueous medium to make an appropriate concentration of the polymeric resin.Examples of the basic substances are ammonia, amines (e.g. trimethylamine, diethylamine, triethylamine, tributylamine, diethanolamine, dimethylethanolamine, diethylethanolamine, 2-amino-2-methyl-1-propanol, morphoiine, pyridine), inorganic alkaline substances (e.g, potassium hydroxide, sodium hydroxide, lithium hydroxide, calcium hydroxide), etc. The amount of the basic substance may be usually from 0.1 to 2. molar equivalents to the total acid amount in the polymeric resin.

The thus obtained polymeric resin dispersion in an aqueous medium is ordinarily available in the form of a dispersion having a non-volatile component content of 5 to 80 % by weight The polymeric resin itself has a number average molecularweightof 1,000 to 50,000 and a glass transition point of -40 to +100 C.

The aqueous dispersion of the polymeric resin is usable as a coating composition, particularly in the form of a composition admixed with an aminoplast resin. Examples and use modes of the aminoplast resin are as hereinabove stated. The amount of the aminoplast resin to be incorporated is not limitative but may be usually from 5 to 100 parts by weight, preferablyfrom 10 to 50 parts by weight (in terms of solid) to 100 parts by weight of the polymeric resin in the aqueous dispersion. When the aminoplast resin is less than the lower limit, the curing is insufficient. When more than the upper limit, the coating film formed from the resulting composition will be too brittle..

In addition to the polymeric resin and the amino plast resin, there may be optinally incorporated any conventional additive such as organic or inorganic pigments, fillers, thickening agents, surfactants, pH ! t regulators, waterand organic solvents..The incorporation can be easily effected by mixation at room . - ..". ., ?hickness of5to The coating composition of the invention is usually applied to a substrate to 500 microns, followed by baking (e.g. at 60 to 200 C for 30 seconds to 60 minutes) to afford a coating film having good appearance and excellent physical properties. It is notable that the coating composition has a good storage stability and a easy curability.It is also notable that the coating film formed with such coating composition is excellent in various physical characteristics such as water resistance, solvent resistance, corrosion resistance, hardness and surface gloss.

This invention will be illustrated in details with reference to Examples and Comparative Examples as shown below, part(s) and (%) are by weight unless otherwise indicated.

Example I Into a 2 liter volume flask equipped with a stirrer, taurine (125 g), sodium hydroxide (40 g), deionized water (200 g) and ethylene glycol monoethyl ether (600 g) were charged. The contents were maintained at 60 C while stirring, and a mixture of allyl g iycidyl ether (114 g) and p-nitroso-phenol (0.1 g) was dropwise added thereto in 20 minutes. Thereafter, stirring was continued for 2 hours. The reaction mixture of pH 9 was treated with an ionic exchange resin (Amberlite IR-120) to eliminate Nat ion, whereby a solution of pH 4 was obtained. The solution was concentrated in a rotary evaporator to make a 7/10 volume so that needle crystals were precipitated. These crystals were identified to unreacted taurina by NMR and IR.The filtrate was poured into a 3 time volume of acetone to precipitate brown oily materials. The oily materials were collected and dried in vacuo to give N-(2-hydroxy-3-allyloxypropyl)taurine (96 g). Identification was made by NMR and IR.

The NMR chart measured in D20 is shown in Figure 1.

Example Il In the same manner as in Example I but using methallyl glycidyl ether in place of allyl glycidyl ether, the reaction was carried outto obtain N-(2-hydroxy-3-methallyloxypropyl)taurine (108 g).

Exampleslll-X In the same manner as in Example I but using an amino acid compound in place of taurine, the reaction was carried out to give a polymerizable amino acid compound as shown in Table 1. The NMR charts of the products in Examples V, VII, IX and X measured in D20 are shown in Figures 2 to 5, respectively.

TABLE 1 Example Amino acid compound Amount Polymerizable amino acid compound Yield (g used (g) III 4-Aminobutanesul- 153 4-[N-(2-Hydroxy-3-allyloxyproyl)amino]- 79 fonic acid-(1) butanesulfonic acid-(1) IV 1 0-Aminodecanesul- 237 4-[N-(2-Hydroxy-3-allyloxypropyl)aminol- 107 fonic acid-(1) decanesulfonic acid-(1) V N-Methyltaurine 139 N-Methyl-N-(2-hydroxy-3-allyloxypropyl)- 60 taurine Vl N-Dodecyltaurine 294 N-Dodecyl-N-(2-hydroxy-3-allyloxypropyl)- 120 taurine VII Glycine 75 N-(2-Hydroxy-3-ailyloxypropyl)glycine 39 Vlil a-Alanine 89 N-(2-Hydroxy-3-allyloxypropyl)-a- 51 alanine IX B-Alanine 89 N-(2-Hydrnxy-3-allyloxyprnpyl)-f3- 82 alanine X #-Aminocaproic acid 131 N-(2-Hydroxy-3-allyloxypropyl)-#- 110 aminocaproic acid Example Xl Into a 2 liter volume flask equipped with a stirrer, allyl 3-amino-2-hydroxypropyl ether (131 g), deionized water (100 g), ethylene glycol monomethyl ethyl (300 g) and p-nitrosophenol (0.13 g) were charged. The contents were maintained at 70"C while stirring, and a solution of sodium vinylsulfonate (130 g) in deionized water (360 g) was dropwise added thereto in 2 hours. Thereafter, stirring was continued for 3 hours. The reaction mixture was concentrated in a rotary evaporator to make a 5/10 volume so that white solids were precipitated. These solids were ide7ntified to unmacted sodium vinylsulfonate by NMR and IR.The filtrate: was treated with an ionic exchange resin (Amberlite IR-120) to eliminate Na+ ion and further treated with acetone to give brown oily materials (220 g). The oily materials were identified to N-(2-hydroxy-3allyloxypropyl)taurine by NMR and IR.

Example Xll In the same manner as in Example XI but using allyl 3-(N-methylamino)-2-hydroxypropyl ether (145 g) in place of allyl 3-amino-2-hydroxypropyl ether, the reaction was carried outto obtain N-methyl-N-(2-hydroxy3-allyloxypropyl)taurine (243 g).

Example Xlil In the same manner as in Example Xl but using allyl 3-(N-heptadecylamino)-2-hydroxypropyl ether (383 g) in place of allyi 3-amino-2-hydroxypropyl ether, the reaction was carried out to obtain N-heptadecyl-N-(2hydroxy-3-allyloxypropyl)taurine (255 g).

Example XIV Into a 2 litervolume flask equipped with a stirrer, allyl 3-amino-2-hydroxypropyl ether (131 g), ethylene glycol monoethyl ether (400 g) and p-nitrosophenol (0.13 g) were charged. The contents were maintained. at 5000 while stirring, and a mixture of ethyl acrylate (100 g), ethylene glycol monoethyl ether(100 g) and p-nitrosophenol (0.1 g) was dropwise added thereto in 2 hours. Thereafter, stirring was continued for 3 hours.. Sodium hydroxide (60 g) and deionized water (200 g) were added to the resulting mixture, the temperature was elevated to 90"C, and stirring was continued for 2 hours. The reaction mixture was concentrated in a rotary evaporatorto make a 5f10 volume.The concentrated solution was treated with an ionic exchange resin (Amberlite IR-120) and furthertreated with acetone to give transparent oily materials (193 g), which was identified to N-(2-hydroxy-3-allyloxypropyl)-ss-alanine Example XV In the same manner as in Example XIV but using allyl 3-(N-dodecylamino)-2-hydroxypropyl ether (297 e in place of allyl 3-amino-2-hydroxypropyl ether, the reaction was carried out to obtain N-dodecyl-N-(2-hydroxy 3-allyloxypropyl)-P-alanine (359 g).

Example XVI In the same manner as in Example XIV but using ethyl vinylsulfonate in place of ethyl acrylate, the reaction was carried out to obtain N-(2-hydroxy-3-allyloxypropyl)taurine (228 g).

Example XVII The product in Example VI, XIII or XV was dissolved in deionized water containing an equimolar amount of N,N-di-methylethanol to make a 0.3 % aqueous solution. The surface tension of the aqueous solution was 30, 28 or 34 dyne/cm. Thus, it is understood that the products in the Examples have a surface activity.

Example XVIII Into a 2 liter volume flask equipped with a stirrer, taurine (250 g), sodium hydroxide (80 g), deionized water (500 g and ethylene glycol monomethyl ether (400 g) were charged. The contents were maintained at 70"C while stirring, and a mixture of vinylbenzyl chloride (153 g), ethylene glycol monomethyl ether (250 g) and p-nitrosophenol (0.1 5 g) was dropwise added thereto in 1 hour, during which sodium hydroxide (each 8 g) was added thereto 6 times with intervals of 10 minutes. Thereafter, stirring was continued for 4 hours. To the reaction mixture, conc. hydrochloric acid (220 g) was added, whereby white solids (Product 1) (57 g) were precipitated. The filtrate was concentrated in a rotary evaporator to make a 3/10 volume, and the precipitated solids were extracted with a 4 time volume of hot acetone.The extract was cooled,.and the precipitated white solids (Product II) (126 g) were collected and dried in vacuo. The Products I and II were respectively identified to N,N-di(vinylbenzyl)taurine and N-vinylbenzyltaurine by NMR and IR..The NMR charts of Products I and II measured in CD3OD/D2O = (NaOD added) are shown in Figures 6 and 7, respectively.

Example XIX Inthe same manner as in Example XVIII but using 2-aminobutanesulfonic acid-(1) (306 g) in place of taurine,the reaction was carried outto obtain 2-(N-vinylbenzylamino)butanesulfonicacid-(1) (91 g).

Example XX In the same manner as in Example XVIII but using 4-aminobutanesulfonic acid (306 g) in place of taurine, 4-(N-vinylbenzylamino)butansulfonic acid (155 g).

Example XXI In the same manner as in Example XVIII but charging deionized water (200 g), sodium hydroxide (80 g),.

10-aminodecanesulfonic acid-(1) (474 g) and ethylene glycol monomethyl ether (500 g) at the initial stage, the reaction was carried out to obtain 10-(N-vinylbenzylamino)decanesulfonic acid-(1.) (180 g)..

Example XXII Into a 2 liter volume flask equipped with a stirrer, N-methyltaurine sodium salt (161 g), deionized water (400 g) and ethylene glycol monomethyl ether (300 g) were charged. The contents were maintained at 70"C while stirring, and a mixture of vinylbenzyl chloride (153 g), ethylene glycol monomethyl ether (100 g) and p-nitrosophenol (0.15 g) was dropwise added thereto in 1 hour, during which sodium hydroxide (each 8 g) was added thereto 6 times with intervals of 10 minutes. Thereafter, atirring was continued for 5 hours. To the reaction mixture, conc. hydrochloric acid (120 g) was added, and the resulting mixture was concentrated in a rotary evaporator to make a 1/3 volume. The concentrate was admixed with a 4 time volume of acetone and filtered. The filtrate was concentrated to a 3/10 volume and admixed with acetone.The precipitated yellow solids were collected and recrylstallized from deionized water to give N-methyl-N-vinylbenzyltaurine. The NMR chart measured in CD3OD/D2O = 2/1 (NaOD added) is shown in Figure 8.

Example XXIII In the same manner as in Example XXII but charging deionized water (300 g), N-dodecyltaurine sodium salt (315 g) and ethylene glycol monoethyl ether (400 g) at the initial stage and adding portionwise thereto a mixture of isopropenylbenzyl bromide (212 g), ethylene glycol monoethyl ether (200 g) and p-nitrosophenol (0.2 g) at a later stage, the reaction was carried out to obtain N-dodecyl-N-isopropenylbenzyltaurine (330 g).

Example XXIV Into a 2 litervolumeflask equipped with a stirrer, vinylbenzylamine (133 g), ethylene glycol monomethyl ether (300 g), deionized water (100 g) and p-nitrosophenol (0.12 g) were charged. The contents were maintained at 70"C while stirring, and a solution of sodium vinylsulfonate (130 g) in deionized water (360 g) was dropwise added thereto in 2 hours. Thereafter, stirring was continued for 3 hours. To the reaction mixture, conc. hydrochloric acid (100 g) was added, and the resulting mixture was concentrated in a rotary evaporator to make a 3/10 volume. The concentrate was extracted with a 4 time volume of hot acetone.The acetone extract was cooied to precipitate white solids (219 g), which were collected and dried in vacuo to give N-vinylbenzyitaurine.

Example XXV In the same manner as in Example XXIV but using (vinylbenzyl)butylamine (189 g) in place of vinylbenzylamine, the reaction was carried out to obtain N-butyl-N-vinylbenzyltaurine (264 g).

Example XXVI Into a 2 liter volume flask equipped with a stirrer, vinylbenzylamine (133 g), methanol (300 g) and hydroquinone (0.13 g) were charged. The contents were maintained at 60"C while stirring, and a solution of methyl vinylsulfonate (122 g) in methanol (100 g) was dropwise added thereto in 1 hour. Thereafter, stirring was continued for 3 hours, and methanol (300 g) was distilled out at an elevated temperature. Sodium hydroxide (80 g) and deionized water (500 g) were added thereto, and the resultant mixture was stirred at 90"C for 2 hours. To the reaction mixture, conc. hydrochloric acid (200 g) was added, and the solvent was evaporated. The residue was washed with deionized water to give white solids (226 g), which were identified to N-vinylbenzyltaurine by NMR.

Example XXVII In the same manner as in Example XXVI but using (vinylbenzyl)dodecylamine (301 g) in place of vinylbenzylamine, the reaction was carried out to obtain N-dodecyl-N-vinylbenzyltaurine (390 g).

Example XX VIII The product in Example XXI was admixed with an equimolar amount of N,N-dimethylethanolamine, and the resultant mixture was dissolved in water to make a 0.3 % aqueous solution. The surface tension of the aqueous solution was 28 dyne/cm. Thus, it is understood that the said product has surface activity.

Example I In a 2 liter volume reactor, ethylene glycol monomethyl ether (100 parts) was charged, and the temperature was elevated to 100"C. In one of two dropping funnels equipped on the reactor, ethylene glycol monomethyl ether (100 parts), N-methyl-N-(vinylbenzyl)taurine (2.5 parts) and a small amount of dimethylethanolamine as a solubilizerwere charged. In the other dropping funnel, 2-hydroxyethyl acrylate (50 parts), acrylic acid (10 parts), methyl methacrylate (115 parts), styrene (135 parts), n-butyl acrylate (197.5 parts) and laurylmercaptan (2.5 parts) were charged, and azobisisobutyronitrile (10 parts) was dissolved therein. The contents in the dropping funnels were dropwise added to the reactor in 2 hours, during whichthe temperature was maintained at 10000 and stirring was continued.Thirty minutes after completion of the dropwise addition, xylene (300 parts) was added to the reaction mixture to give a resinous solution having a solid content of 50 %, a viscosity of U and a number average molecular weight of 6,500.

By dispersing a pigment such as titanium oxide, carbon black, red iron oxide or phthalocyanine blue into the resinous solution, there was obtained a pigment paste having a high stability.

Example 2 In the same manner as in Example 1 but using the following materials, there was obtained a resinous solution having a viscosity of S and a number average molecular weight of 6,500: Part(s) N-(Vinylbenzyl)taurine 10 2-Hydroxyethyl acrylate 50 Acrylic acid 25 Methyl methacrylate 100 Styrene 100 n-ButyI acrylate 215 Laurylmercaptan 5 Azobisisobutyronitrile 10 Xylene - 250 Ethylene glycol monomethyl ether '150 Ethylene glycol monobutyl ether 100 The resinous solution (100 parts) was admixed with a butylated melamine resin ("Super Beckamin G-821" manufactured by Dainippon Ink and Chemicals, Inc.) (30 parts). The resulting composition was applied onto the surface of a metal piate and baked at 80 to 10000 for 30 minutes to give a coating film completely cured and having excellent physical properties.

Examples 3 to 12 In the same manner as in Example 1 but using the materials as shown in Table 2, there were obtained resinous solutions, of which the viscosity and the number average molecular weight are also shown in Table 2.

The obtained resinous solutions showed nearly the same level as those obtained in Examples 1 and 2 in pigment dispersibility and low temperature curing characteristics when admixed with aminoplast resins. TABLE 2 Example No. 3 4 5 6 7 8 9 10 11 12 Componenet (parts) Polymerizable amino acid 5 10 10 10 25 60 125 20 10 10 compound*) 2-Hydroxyethyl acrylate 25 - 50 - 50 50 50 - 50 50 2-Hydroxyethyl methacrylate - - - - - - - 50 - Acrylic acid 15 - - - 10 10 10 10 10 10 Methacrylic acid - 10 - - - - - - - n-Butoxymethyl acrylamide 90 - - - - - - - - N,N-Dimethylaminoethyl - - 20 - - - - - - methacrylate Glycidyl methacrylate - - - 80 - - - - - Methyl methacrylate 100 150 - 100 125 100 100 - 100 100 Styrene 125 150 150 150 - 50 75 100 100 100 Methyl acrylate - 180 - - 100 - - 320 - n-Buthyl acrylate - - - 160 90 240 - - 230 230 n-Buthyl methacrylate - - 150 - 100 100 - - - 2-Ethylhexyl acrylate 140 - 120 - - - 140 - - Laurylmercaptan 5 2.5 5 5 5 5 5 5 5 5 Azobisisobutyronitrile 10 10 10 10 10 10 10 10 10 10 Toluene - 250 - - - - - - - Xylene 250 - 250 250 200 200 200 250 250 250 Ethylene glycol 150 250 150 150 200 200 200 150 150 150 monomethyl ether Ethylene glycol 100 - 100 100 100 100 100 100 100 100 monobutyl ether Viscosity T Y S S T S X T T V Number of average molecular 6200 8800 6300 6200 6500 6000 7200 6800 6800 7000 weight (Mn) Note: *1) Examples of 3 to 6, N-methyl-N-vinylbenzyltaurine; Examples 7 to 9, N-vinylbenzyl-ss-analine; Examples 10, N-(2-hydroxy-3-allyoxypropyl)taurine; Examples 11, N-vinylbenzyl-metanilic acid; Examples 12, N-vinylbenzyl-sulfanilic acid.

Example 13 Into a 2 liter volume flask equipped with a stirrer, ethylene glycol tnonomethyl ether (61.6 parts) was charged, and the temperature was elevated to 11000 while stirring. A mixture of ethylene glycol monomethyl ether (32 parts), N-(2-hydroxy-3-allyloxypropyl)taurine (8 parts) and 2-hydroxyethyl acrylate (40 parts) and a mixture of styrene (99.6 parts), methyl methacrylate (99.6 parts), n-butyl acrylate (132.8 parts), acrylic acid (20 parts) and azobisisobutyronitrile (6 parts) were dropwise added thereto in 2.5 hours. After completion of the dropwise addition, a mixture of azobisisobutyronitrile (2 parts) and methylethylketone (12 parts) was dropwise added thereto in 30 minutes, and stirring was continued at 110"C for 1 hour.To the reaction mixture, dimethylethanolamine (17.2 parts) and then deionized water (685.2 parts) were added to give a resinous dispersion.showing a white emulsion and containing non-volatile components in an amount of 33 %. Number average:molecular weight 25,000. Glass transition point, 19.5"C.

Examples 14 to 26 and Comparative Examples 1 and2 In the same manner as in Example 13 but using the materials as shown in Table 3, there were obtained resinous dispersions, of which transparency, non-volatile component content, number average molecular weight and.glass transition point are also shown in Table 3.

TABLE 3 Component (parts) Example Comparative Example 14 15 16 17 18 19 20 21 22 23 24 25 26 1 2 Ethylene glycol 14.8 80 80 80 80 15 15 80 80 15 15 - 80 80 80 monomethyl ether Isopropanol - - - - - - - - - - - 15 - - Ethylene glycol 32 120 120 120 120 32 32 120 120 32 32 - 120 120 120 monomethyl ether Isopropanol - - - - - - - - - - - 32 - - N-(2-Hydroxy-3- 8 - - - - - - - - - - - - - allyloxypropyl)taurine N-Vinylbenzyl- - 4.8 4.8 9.6 9.6 8 - - - - - - - - taurine N-Methyl-N-vinyl- - - - - - - 4 4 4 16 4 4 0.8 - benzyltaurine 2-Hhydroxyethyl 40 40 40 40 40 40 40 40 28 40 40 40 40 40 40 acrylate Dimethylaminiethyl - - - - - - - - - - 26 - - - methacrylate Dimethylethanol- - 0.88 0.88 1.76 1.76 - 1.4 1.4 1.4 5.6 1.4 1.4 0.28 - amine Styrene 93.6 100.6 94.6 99.1 93.1 97.2 98.4 98.4 102 94.8 90.6 98.6 99.4 102 96 Methyl meth- 93.6 100.6 94.6 99.1 93.1 97.2 98.4 98.4 102 94.8 90.6 98.6 99.4 102 96 acrylate n-Butyl acrylate 124.8 134.1 126.1 132.2 124.2 129.6 131.2 131.2 136 126.4 120.8 - 132.5 136 128 2-Ethylhexyl - - - - - - - - - - - 131.2 - - acrylate Acrylic acid 40 20 40 20 40 28 28 28 28 28 28 19.6 28 20 40 Itaconic acid - - - - - - - - - - - 7.6 - - Azobisiso- 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 butyronitrile Laurylmercaptan - 8 8 8 8 4 4 4 8 8 8 8 8 8 8 Azobisiso- 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 butyronitrile Methylathylketone 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 Dimethylethanol- 34.6 20 40 24.8 49.6 34.6 34.6 34.6 34.6 34.6 34.6 34.6 34.6 24.8 49.6 amine Ethylene glycol - 89.6 79.6 82.7 70.3 - - 182 182 - - - 184 82.7 70.3 monomethyl ether Delonized water 670 289.6 279.6 282.7 270.3 670 670 382 382 670 670 670 382 282.7 270.3 Transparency*1) x # o # o # # o o # # # o # o Non-volatile 33 50 50 50 50 33 33 33 33 33 33 33 33 33 33 component content(%) Number average molecular weight 25000 5500 5500 5500 5500 9000 9000 8400 5500 6000 6000 6000 5500 5500 5500 (Mn) Glass transition point ( C) 23.0 19.1 22.5 19.8 23.2 21.0 20.3 20.3 21.5 22.3 20.3 1.1 19.8 Note:*1) Transparent, o; semi-transparent, #;non-transparent, x.

Example 27 The resinous dispersion obtained in any of Examples 15 to 18 and Comparative Examples 1 and 2 and an aminoplast resin ("Cymel 303" manufactured by Mitsui-Toatsu Co., Ltd.) were mixed together in a solid ratio of 8: 2 by weight to prepare a coating composition. The coating composition was applied onto a zinc-plated iron sheet to make a film thickness of 30 microns (after drying) and baked at 12000, 14000 or 1600C for 30 minutes for curing.

The solubility of the cured coating film in a solvent for paint (thinner) when immersed for 1 hour is shown in Table 4, wherein the solubility was calculated according to the following equation: B-C Solubility (%) = - x 100 B-A wherein A is the weight of the zinc-plated iron sheet, B is the total weight of the zinc-plated iron sheet and the coating film before immersion and C is the total weight of the zinc-plated iron sheet and the coating film after immersing and drying at 120"C for 20 minutes.

TABLE 4 Temperature for baking 1200C 140"C 16000 Example 15 45 12 2 16 45 7 0 17 24 6 3 18 22 4 0 Compara- 1 100 64.7 27.6 tive 2 100 21.6 2.7 Example Example 28 As in Example 27, the resinous dispersion obtained in Example 15 or 17 or Comparative Example 1 was admixed with an aminoplast resin to prepare a coating composition. Then, the coating composition was applied onto a zinc-plated iron sheet, followed by baking at 1400C for 30 minutes for curing.

The solubility and the swelling of the cured coating film when immersed in boiling water for 1 hour are shown in Table 5, wherein the solubility was calculated according to the equation as shown in Example 27 and the swelling was calculated according to the following equation: D-C Swelling (%) = - x 100 C-A wherein A is the weight of the zinc-plated iron sheet, C is the total weight of the zinc-plated iron sheet and the coating film after immersing for 1 hour and drying at 120 C for 20 minutes and D is the total weight of the zinc-plated iron sheet and the coating film immediately after immersing.

TABLE 5 Solubility (%) Swelling (%) Example 15 7.0 7.5 16 5,8 6.3 Comparative 21.6 55.6 Example 1 Example 29 The resinous dispersion obtained in any of Examples 20 to 26, carbon black ("Mitsubishi Carbon MA-100" manufactured by Mitsubishi Chemical Co., Ltd.) and an aminoplast resin were mixed together in a solid ratio of 85 : 2:15 by weight to prepare a black coating composition. The coating composition was applied onto a dull steel plate to make a film thickness of 30 microns (after drying) and baked at 12000 or 140 C for 30 minutes for curing.

The width of peeling by a tape after salt spraying for 96 hours examined on the cured coating film was not more than 3 mm.

Claims

1. A coating composition comprising as a main component a polymeric resin obtained by solution polymerization of at least one of polymerizable amino acid compounds of either one of the formulas:

wherein R11 R2, R3 and R4 are each hydrogen, methyl or ethyl, R5 is hydrogen or C1-C20 alkyl optionally having -SO-, -COO- or -0-therein, Re is C1-C12 alkylene optionally substituted with -OH, -SH or -SR7 (R7 being C1-C4 alkyl) and/or optionally substituted with C1-C4 alkyl or phenylene optionally substituted with C-C4 alkyl and A is -COOH or -SO3H, and

wherein R8, R9 and R10 are each hydrogen or C1-C6 alkyl, R11 is hydrogen or C1-C20 alkyl optionally having -SO-, -COO- or -0-therein, or a group of the formula::

(R8, Rg and R10 being each as defined above), R12 is C2-C12 alkylene optionally substituted with Ci-Ce alkyl. or phenylene optionally substituted with C-C4 alkyl, and A is as defined above, with or without at least one of other polymerizable monomers.

2. The composition according to claim 1, wherein the polymeric resin is the one obtained by solution polymerization of at least one of the polymerizable amino acid compounds with at least one of the other polyr,nerizable monomers.

3. The composition according to claim 2, wherein the other polymerizable monomers are hydroxyl group-containing monomers, carboxyl group-containing monomers, glycidyl group-containing monomers, alkyl acrylates and alkyl methacrylates, nitrogen-containing alkyl acrylates and nitrogen-containing alkyl methacrylates, polymerizable am ides, polymerizablei nitriles, polymerizable aromatic compounds, a-olefinic compounds, vinylic compounds and diene compounds.

4. The composition according to claim 2, wherein the other polymerizable monomers are hydroxyl group-containing monomers.

5. The composition according to any one of claims 1 to 4, which further comprises at least one aminoplast resin.

6. A polymeric resin prepared by solution polymerization of (a) at least one of polymerizable amino acid compounds of either one of the formulas:

wherein R1, R2, R3 and R4 are each hydrogen, methyl or ethyl, Rg is hydrogen or C1-C20 alkyl optionally having ,-SO-, -COO- or -O- therein, Re is C1-C12 alkylene optionally substituted with -OH, -SH or -SR7 (R7 being C1-C4 alkyl) and/or optionally substituted with G1^C4 alkyl or phenylene optionally substituted with C1-C4 alkyl and A is -COOH or -SO3H, and

wherein Re, R9 and R70 are each hydrogen or C1-C6 alkyl, R11 is hydrogen or C1-C20 alkyl optionally having -SO-, -COO- or -0-therein, or a group of the formula:

(R8, Rg and R1o being each as defined above), R12 is C2-C12 alkylene optionally substituted with C,-C6 alkyl or phenylene optionally substituted with C1-C4 alkyl, and A is as defined above, (b) at least one of carboxyl group-containing monomers and (c) at least one of other polymerizable monomers, and having a number of average molecular weight of 1,000 to 50,000 and a a glass transition point of -40 to +10000.

7. The resin according to claim 6, wherein the solution polymerization is effected in a water-miscible organic solvent.

8. The resin according to claim 6, wherein the component (a) is the polymerizable amino acid compound of the formula (Ib) wherein A is -SO3H.

9. The resin according to claim 6, wherein the other polymerizable monomers as the component (c) are hydroxyl group-containing monomers, alkyl acrylates and alkyl methacrylates, nitrogen-containing alkyl acrylates and nitrogen-containing alkyl methacrylates, polymerizable amides, polymerizable nitriles, polymerizable aromatic compounds, a-olefinic compounds, vinylic compounds and diene compounds.

10. The resin according to claim 6, wherein the other polymerizable monomers are hydroxyl group-containing monomers.

11. A dispersion of the polymeric resin according to claim 6 in an aqueous medium containing non-volatile components in an amount of 5 to 80 % by weight.

12. A process for preparing a dispersion of a polymeric resin in an aqueous medium, which comprises subjecting (a) at least one of polymerizable amino acid compounds of either one of the formulas:

wherein R1, R2, R3 and R4 are each hydrogen, methyl or ethyl, Rg is hydrogen or C,-C20 alkyl optionally having -SO-, -COO- or -0-therein, Re is C1-C12 alkylene optionally substituted with -OH, -SH or -SR7 (R7 being C1-C4 alkyl) and/or optionally substituted with C1-c4 alkyl or phenylene optionally substituted with C1-C4 alkyl and A is -COOH or -SO3H, and

wherein Re, Rg and R1O are each hydrogen or C1-Cs alkyl, R11 is hydrogen or C1'C20 alkyl optionally having -SO-, -COO- or -0-therein, or a group of the formula:

(R8, R9 and R10 being each as defined above), .R2 is C2-Cr2 alkylene optionally substituted with C,-C6 alkyl or phenylene optionally substituted with C1-C4 alkyl, and A is as defined above, (b) at least one of carboxyl group-containing monomers and (c) at least one of other polymerizable monomers to solution polymerization in a water-miscible organic solvent, neutralizing the polymerization product and dispersing the resultant polymeric resin into an aqueous medium.

13. The process according to claim 12, wherein the resultant polymeric resin has a number average molecular weight of 1,000 to 50,000 and a glass transition point of -40 to + 10048C and the obtained dispersion contains non-volatiie components in an amount of 5 to 80 % by weight

14. The process according to claim 12, wherein the component (a) is the polymerizable amino acid compound of the formula (Ib) wherein A is -SO3H.

15. A polymerizable amino acid compound of the formula:

whereinR1, R2, R3 and R4 are each hydrogen, methyl or ethyl, R5 is hydrogen or C1-C20 alkyl optionally having -SO-, -COO- or -0-therein, Re is C1-C12 alkylene optionally substituted with -OH, -SH or -SR7 (R7 being C1-C4 alkyl) and/or optionally substituted with C1-C4 alkyl and A is -COOH or -SO3H, or of the formula:

wherein Re, Rg and Rlo are each hydrogen of C1-C6 alkyl, R11 is hydrogen or C1-C20 alkyl optionally having -SO-, -COO- or -0-therein, or a group of the formula::

(R8, Re and R10 being each as defined above) and R12 is C2-C12 alkylene optionally substituted with C1-C6 alkyl.

16. The compound according to claim 15, wherein A is -COOK.

17. The compound according to claim 15, wherein A is -SO3H.

18. The compound according to claim 15, wherein R1 is hydrogen.

19. The compound according to claim 15, wherein R1 is methyl.

20. The compound according to claim 15, wherein R2, R3 and R4 are each hydrogen.

21. The compound according to claim 15, wherein at least one of R3 and R4 is methyl.

22. The compound according to claim 15, wherein Re is hydrogen.

23. The compound according to claim 15, wherein Re is C1-C8 alkyl.

24. The compound according to claim 15, wherein Re is Cg-CzO alkyl optionally having -SO-, -COO- or -O-.

25. The compound according to claim 15, which is representable by the formula:

wherein R13 is hydrogen, methyl or ethyl, and R1, R2, R3, R4, Re and A are each as defined in claim 15.

26. The compound according to claim 15, wherein Re is ethylene.

27. The compound according to claim 15, which is representable by the formula:

wherein R1, R2, R3 and R4 are each as defined in claim 15.

28. The compound according to claim 15, which is representable by the formula:

wherein R1, R2, R3 and R4 are each as defined in claim 15.

29. The compound according to claim 15, which is representable by the formula:

wherein R1, R2, R3 and R4 are each as defined in claim 15.

30. The compound according to claim 15, which is representable by the formula:

wherein R1, R2, R3 and R4 are each as defined in claim 15.

31. The compound according to claim 15, which is representable by the formula:

wherein R1, R2, R3 and R4 are each as defined in claim 15.

32. The compound according to claim 15, wherein R8 is hydrogen.

33. The compound according to claim 15, wherein R5 is methyl.

34. The compound according to claim 15, wherein R9 and R1o are each hydrogen.

35. The compound according to claim 15, wherein R11 is hydrogen.

36. 'The compound according to claim 15, wherein R11 is C1-C8 alkyl.

37. The compound according to claim 15, wherein R11 is C9-c20 alkyl optionally having -SO-, -COO- or -O-.

38. The compound according to claim 15, wherein R11 is a group of the formula:

wherein R8, R9 and R10 are each as defined in claim 15.

39. The compound according to claim 15, which is representable by the formula:

wherein R14 is hydrogen, methyl or ethyl, and R5, Rg, R10 and R11 are each as defined in claim 15.

40. The compound according to claim 15, wherein R12 is ethylene.