GB2066254A

GB2066254A - N-(Vinylbenzyl)aminoalkylsulphonic acid

Info

Publication number: GB2066254A
Application number: GB8101941A
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: 1981-07-08
Also published as: GB2066254B; DE2940509C2; GB2035340B; DE2940509A1; GB2035340A

Abstract

Compounds 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 may be solution polymerised with (a) at least one carbonyl group containing monomer and (b) at least one other polymerisable monomer to obtain a resin having a number average molecular weight of 1,000-50,000 and a glass transition point in the range - 40 DEG C- + 100 DEG C inclusive, which resin can be employed in cooling compositions.

Description

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1 GB2 066254A:1 .DTD:

SPECIFICATION .DTD:

Polymeric resin and coating composition comprising same The present invention relates to a polymeric resin and a coating composition comprising-'the. 5 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 an' a. " coating composition comprising such polymeric resin as a main component...

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In this specification, the terms "dispersing" and "dispersion" &re used in their broadisense:.

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and include "'dissolving" and "solution"ò'"%,.,...., 10 As the result of an extensive study, it has been found that a polymeric resin obtained iby'' solution polymerization of a certain specific polymerizable amino acid compound with or without any other pol,/merizable monomer has an excellent pigment dispersibility and is usable as a resin for dispersing a pigment to provide a coating composition. It has also been found that Wh.'en a hydroxyl group-containing polymerizable monomer is used as the other polymerizable monomer, 15 a composition comprising the resulting polymeric resin and an aminoplast. resin can be l'e&dily- cured at a low temperature within a short period of time. It has further been found that when a carboxyl group-containing polymerizable monomer is used as the other polymerizable monomer, the resultant polymeric resin is dispersible in water to give a stable resinous dispersionòIt has furthermore been found that a composition comprising such resinous dispersion and an,' 20 aminoplast resin can afford a coating film having excellent physical propertiesòThe present invention is based on these findingsòThe 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 compositionòSuch polymerizable amino acidcompoundsare 25 representable by either one of the following formulas: '-.

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R R2 Rs R5 " ' I I I I CH2 = C-CH2-O-CH2-C- C-N-Ro-A (la) 30 OH a4 wherein R, R2, R3 and R4 are each hydrogen, methyl or ethyl, R5 is hydrogen or C1-C2o alkyl 35 optionally having -SO-, -COO- or -0- therein, R6 is C1-C2 alkylene optionally substituted with -OH, -SH or -SR7 (R7 being C1-C4 alkyl) and/or optionally substituted with C-C4 alkyl or phenylene optionally substituted with C-C4 alkyl and A is -COOH or -S03H, and R9 RI I_I CH2 = C-CoH4-C- N-RI2-A (Ib) J Rio wherein R8, R9 and Rto are each hydrogen or C1-C6 alkyl, R is hydrogen or C-C2o alkyl optionally having -SO-, -CO0- or -0- therein, or a group of the formula:

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CH2 R8 R9 I I = 6-C6H4-C- I (Rs, Rg and Ro being each as defined above), R2 is C=-C2 alkylene optionally substituted with C-C6 alkyl dr phenylene optionally substituted with C-C4 alkyl, and A is as defined above.

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As the structurally similar compounds to the said polymerizable amin:o acid compound's, there are known those of the formula:

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CH2 CHs CH3 I I = C-CO0-(-CH=-)2-N + _(_CH2_)3_S03- CH3 2 GB2066 254A 2 and of the formula:

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CH= = CH-C6H4-CH(NH2)-COM wherein M is a cation such as hydrogen, ammonium or metal are known (Japanese Patent 5 Publication (examined) No. 11651/1967); U.S. Patent 2,840,603).

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The compounds of the formula (la) wherein R6 is C-C12 alkylene optionally substituted with -OH, -SH or -SR7 and/or optionally substituted with C1-C4 alkyl (hereinafter referred to as "the conpounds (la')") and the compounds of the formula (Ib) wherein R12 is C2-C12 alkylene optionally substituted with C-C6 alkyl and A is -S03H (hereinafter referred to as "the 10 compounds (Ib')") are novel, and they are included within scope of the present invention.

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In the above polymerizable amino acid compounds, the basic group (i.e. amino) and the acidic group (i.e. -COOH or -S03H) 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 represent&ble-by the following partial formulas: 15 I I N R6BH., ""N R6 B I 20...... 20 wherejn B-H represents CO0-H or S03-H. Depending on the conditions, the tautomerism is varied;as shown in the following partial formulas:

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I 1 " I 25 N R6--B--H., " -NNR6-B,, " --N--R6--B I I H H Thus, by controlling appropriately the conditions such as degree of hydrophilic property and pH, 30 the ionic portions of the said compounds can take an optional form, on which the corresponding characteristic properties are exerted.

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

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(A) Production of the compounds (la'):- 35 The Co'pounds (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, 40 dimethylformamide, dimethylsulfoxide or water, or their mixtures at a temperature of 0 to 150"C under an atmospheric or elevated pressure for a period of 10 minutes to 48 hours, usually while stirring.

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

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t i2 45 CH2C CH2OCH2 C C R4 \o/ 50, 50 wherein R1, R=, R3, R4 and Rs ape each as defined above. Specific examples are allyl glycidyl ethers. Oqt.hallyl glycidyl ether, allyl methylglycidyl ether, methallyl methylglycidyl ether, etc.

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

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Rs-N,Ie-. A - (IV) 55 H wherein Rs, R6 and A are each as defined above. Specific examples are glycine, alanine,/- alanine, -aminocaproic acid, sarcosine, thúeonine, cysteine, methionine, taurine, 2-aminopropanesulfonic acid-(1), 1-aminopropanesulfo'nic acid-(2), 3aminobutanesulfonic acid-(2), 2-amino- butanesuffonic acid-(1), 1-amino-2-methylpropanesulfonic acid-(2), 3- aminopentanesulfonic acid(2), 4-amino-2-methyipentanesulfonic acid-(3), 3-aminopropanesulfonic acid-(1), 4-aminobutane- sulfonic acid-(2), 4-aminobutanesulfonic acid-(3), 5-aminopentanesulfonic acid-(1), 10-aminode- canesulfonic acid-(1), N-methyltaurine, N-ethyltaurine, N- isopropyltaurine, N-butyltaurine, N- 65 3 GB2066 254A 3 heptyltaurine, N-dodecyltaurine, N-heptadecyltaurine, N-(2- octadecylsulfinethyl)taurine, N-(2stearoyloxymethyl)-taurine, 2- methylaminopropanesulfonic acid-(1), 2-dodecylaminopropanesulfonic acid- (1), 2-octa decylaminopropanesulfonic acid-(1), 1-methylamino-2- methylpropanesulfonic acid-(2), 3-methylaminopropanesulfonic acid-(1), etc.

The compounds of the formula:

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R1 R2 R3 R5 R13 I I I I 1 CH2 = C-CH2-O-CH2-C- C-N-CH2-CH-A (lla) I I OH R4 wherein R3 is hydrogen, methyl or ethyl and R, 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).

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Process (a) According to this process, an oxyamine compound having a primary or secondary amino group and an o,/Y-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 150 C under an atmospheric or elevated pressure for a period of 10 minutes to 48 hours, if necessary, while stirring.

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

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R2 R3 R5 1 1 I CH2 = C-CH2-O-CH2-C- C-N-H (V) I f OHR4 wherein RI, R2, R3, R4 and R5 are each as defined above. Specific examples are allyl 3-amino-2- hydroxypropyl ether, methallyl 3-amino-2-hydroxypropyl ether, allyl 3- amino-3-methyl-2-hydroxy- propyl ether, methallyl 3-amino-3-methyl-2-hydroxypropyl ether, allyl 3- (N-methylamino)-2-hydroxypropyl ether, methallyl 3-(N-methylamino)-2-hydroxypropyl ether, allyl 3-(N-methylamino)- 3-methyl-2-hydroxypropyl ether, methallyl 3-(N-methylamino)-3-methyl-2- hydroxypropyl ether, 35 allyl 3-(N-ethylamino)-2-hydroxypropyl ether, allyl 3-(N-butylamino)-2hydroxypropyl ether, allyl 3-(N-hexylamino)-2-hydroxypropyl ether, allyl 3-(N-octylamino)-2- hydroxypropyl ether, methallyl 3-(N-octylamino)-2-hydroxypropyl ether, allyl 3-(N-octylamino)-3-methyl-2hydroxypropyl ether, methallyl 3-(N-octylamino)-3-methyl-2-hydroxypropyl ether, allyl 3-(N- decylamino)-2-hydroxypro- pyl ether, allyl 3-(N-dodecylamino)-2-hydroxypropyl ether, allyl 3-(Nheptadecylamino)-2-hydroxy- 40 propyl ether, allyl 3-[N-(2octadecylsulfinethyl)amino]-2-hydroxypropyl ether, allyl 3[N-(2stearoyloxyethyl)amino]-2-hydroxypropyl ether, etc.

The o,/-unsaturated acid may be represented by the formula:

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R13 45 CH2 = C-A (Vl) wherein R3 and A are each as defined above, and its specific examples include acrylic acid, methacrylic acid, vinylsulfonic acid, etc.

When the x,/-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,/unsaturated acid may be employed in the form of a salt with the base.

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

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As the c,/-unsaturated acid ester, there may be usecl the one of the formula:

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R13 I CH2 = C-A'-Rls (VII) wherein R15 is C-C4 alkyl optionally substituted with -OH and A' is -CO0- or -S03-, and R13 65 4 GB2066 254A 4 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, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, methyl vinylsulfonate, ethyl vinylsulfonate, n-butyl vinylsulfonate, 2-ethylhexyl vinylsulfonate, decyl vinylsulfonate, 2-hydroxyethyl vinylsulfonate, etc. 5 Examples of the compounds (la) are as follows: N-(2-hydroxy-3- allyloxypropyl)taurine, 2-[N-(2hydroxy-3-allyloxypropyl)amino]propanesulfonic acid-(1), 1-[N-(2-hydroxy3-allyloxypropyl)ami- no]propanesulfonic acid-(2), 3-[N-(2-hydroxy-3allyloxypropyl)amino]butanesulfonic acid-(2), 2[N-(2-hydroxy-3-allyloxypropyl)amino]butanesulfonic acid-(1), 1-[N-(2hydroxy-3-allyloxypropy- I)amino]-2-methylpropanesulfonic acid-(2), 3-[N-(2-hydroxy-3- allyloxypropyl)amino]pentanesul- 10 fonic acid-(2), 4-[N-(2-hydroxy-3-allyloxypropyl)amino]-2- methylpentanesulfonic acid-(3), 3-[N-(2- hydroxy-3-allyloxypropyl)amino]propanesulfonic acid-(1), 4-[N-(2-hydroxy- 3-allyloxypropyl)amino- ]butanesulfonic acid-(2), 4-[N-(2-hydroxy-3- allyloxypropyl)amino]butanesulfonic acid-(1), 5-[N-(2hydroxy-3-allyloxypropyl)amino]pentanesulfonic acid-(1), 10-[N-(2-hydroxy3-allyloxypropyl)ami- no]-decanesulfonic acid-(1), N-methyl-N-(2-hydroxy-3- allyloxypropyl)taurine, N-ethyI-N-(2-hydroxy-3-allyloxypropyl)taurine, N-propyI-N-(2-hydroxy-3allyloxypropyl)taurine, N-butyI-N-(2-hy- droxy-3-allyloxypropyl)taurine, N-heptyI-N-(2-hydroxy-3- allyloxypropyl)taurine, N-dodecyI-N-(2-hydroxy-3-allyloxypropyl)taurine, N-heptadecyI-N-(2-hydroxy-3allyloxypropyl)taurine, N-(2-octadecylsulfinethyl)-N-(2-hydroxy-3-altyloxypropyl)taurine, N-(2stearoyloxyethyl)-N-(2-hydroxy-3-ally- loxypropyl)-taurine, N-(2-hydroxy-3-methallyloxypropyl)taurine, N-(1methyl-2-hydroxy-3-allyloxy- 20 propyl)taurine, N-(2-hydroxy-3-allyloxypropyl)glycine, N-(2-hydroxy-3methallyloxypropyl)glycine, N-(2-hydroxy-3-methallyloxypropyl)sarcosine, N-(2-hydroxy-3- allyloxypropyl)alanine, N-(2-hydroxy-3-allyloxypropyl)-/-alanine, N-methyI-N-(2-hydroxy-3allyloxypropyl)-/-alanine, N-ethyi-N(2-hydroxy-3-allyloxypropyl)-/-alanine, N-ethyI-N-(2-hydroxy-3allyloxypropyl)-/-alanine, N-butylN-(2-hydroxy-3-allyloxypropyl)-/-alanine, N-heptyI-N-(2-hydroxy-3allyloxypropyl)--alanine, N-dodecyI-N-(2-hydroxy-3-allyloxypropyl)-/-alanine, N-hepta decyI-N-(2-hyd roxy-3-allyloxypropyl)-/3- alanine, N-(1-methyl-2-hydroxy-3-'allyloxypropyl)-/J-alanine, N-(2hydroxy-3-allyloxypropyl)--ami- nocapronic acid, N-(2-hydroxy-3-allyloxypropyl)-threonine, N-(2-hydroxy-3allyloxypropyl)cys- teine, N-(2-hydroxy-3-allyloxypropyl)methionine, N-(2-hydroxy-3- allyloxypropyl)anthranilic acid, N-(2-hydroxy-3-allyloxypropyl)-m-aminobenzoic acid, N-(2-hydroxy-3allyloxypropyl)-p-aminoben- 30 zoic acid, N-(2-hydroxy-3-allyloxypropyl)orthanilic acid, N-(2-hydroxy-3allyloxypropyl)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 35 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 of 0 to 150 C under an atmospheric or elevated pressure for a period of 10 40 minutes to 48 hours, usually while stirring.

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

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R8 R9 45 I I CH2-- C-C6H4-C-X (VIII) I Rio wherein X is chlorine or bromine and R8, R9 and Rio 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 55 formula:

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Rll I H- N-R12-SO3H (IX) wherein R and R12 are each as defined above. Specific examples are taurine, 2-aminopropanesulfonic acid-(1), 1-aminopropanesulfonic acid-(2), 3-aminobutanesulfonic acid-(2), 2-aminobutanesuifonic acid-(1), 1-amino- 2-methylpropanesulfonic acid-(2), 3-aminopentanesulfonic acid- (2), 4-amino-2-methylpentanesulfonic acid-(3), 3-aminopropanesulfonic acid-(1), 4-aminobutane65 sulfonic acid-(2), 4-aminobutanesulfonic acid- (1), 5-aminopentanesulfonic acid-(1), lO-aminode- GB 2 066 254A 5 canesulfonic acid-(1), N-methyltaurine, N-ethyltaurine, N- isopropyltaurine, N-butyltaurine, Nheptyltaurine, N-dodecyltaurine, N- heptadecyltaurine, N-(2-octadecylsulfinethyl)taurine, N- (2stearoyloxyethyl)taurine, 2-metholaminopropanesulfonic acid-(1), 2- dodecylaminopropanesulfonic acid-(1), 2-octadecylaminopropanesulfonic acid-(1), 1-methylamino-2-methylpropanesulfonic acid-(2), 3-methylaminopropanesulfonic acid-(1), etc.

The compounds of the formula:

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Re R9 Rll R14 I I I I OH2= C-CeH4-C- N-CH2-CH-SO.H (lib) I Ro wherein RI4 iS hydrogen, methyl or ethyl, and R8, Rg, R10 and RI are each as defined above can be produced also in either one of the following processes (c) and (d).

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Process (c) According to this process, a benzylamine compound and an e,/-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 0 to 150 C under an atmospheric or elevated pressure for a period of 10 minutes to 48 hours, if necessary, while stirring.

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

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R8 R9 Rll I t t OH2 = C-C6H4-C- N-H (X) Ro wherein R8, R9, R,o and RI are each as defined above. Specific examples are (vinylbenzyl)amine, (isopropenylbenzyl)amine, (vinylbenzyl)methylamine, (isopropenylbenzyl)methylamine, (vinylbenzyl)ethylamine, (isopropenylbenzyl)ethylamine, (vinylbenzyl)propylamine, (isopropenylbenzyl)propylamine, (vinylbenzyl)butylamine, (isopropenylbenzyl)butylamine, (vinylbenzyl)heptylamine, (isopropenylbenzyl)heptylamine, (vinylbenzyl)dodecylamine, (isopropenylbenzyl)dodecylamine, (vinylbenzyl)heptadecylamine, (isopropenylbenzyl) heptadecylamine, etc.

The ',/%unsaturated sulfonic acid may be represented by the formula:

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wherein Rf 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. 60 Exanples of the compounds (Ib) are as follows: N-(vinylbenzyl)taurine, N(isopropenylbenzyl)- taurine, 2-(N-vinylbenzylamino)propanesulfonic acid-(1), 2-(N- isopropenylbenzylamino)propane- sulfonic acid-(1), 1-(N-vinylbenzylamino)propanesulfonic acid-(2), 1-(Nisopropenylbenzylamino- propanesulfonic acid-(2), 3-(N-vinylbenzylamino)butanesulfonic acid-(2), 3-(N-isopropenylbenzylamino)butanesulfonic acid-(2), 2-(N-vinylbenzylamino)butanesulfonic acid(1), 2-(N-isopropenyl- 65 R14 55, 55 CH., = C-SOR, (Xll) Process (d) According to this process, the benzylamine compound (X) and an,punsaturated sulfonic acid ester are subjected to addition reaction, followed by hydrolysis of the product in the 50 presence of a basic catalyst.

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

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wherein R4 iS as defined above, and its specific examples include vinylsulfonic acid.

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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 45 c,/Y-unsaturated sulfonic acid may be employed in the form of a salt with the base.

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14 I 40 CH2 = C-S03H (Xl) 6 GB2066254A 6 benzylamino)butanesulfonic acid-(1), 1-(N-vinylbenzylamino)-2- methylpropanesulfonic acid-(2), 1(N-isopropenylbenzylamino)-2-methylpropanesulfonic acid-(2), 3-(Nvinylbenzylamino)pentanesul- fonic acid-(2), 3-(N-isopropenylbenzylamino-pentanesulfonic acid-(2), 4(N-vinylbenzylamino)-2- methylpentanesulfonic acid-(3), 4-(N-isopropenylbenzylamino)-2- methylpentanesulfonic acid-(3), 3-(N-vinylbenzylamino-propanesulfonic acid-(1), 3-(Nisopropenylbenzylamino-propanesulfonic 5 acid-(1), 4-(N-vinylbenzylamino)butanesulfonic acid-(2), 4-(Nisopropenylbenzylamino)butanesul- fonic acid-(2), 4-(N-vinylbenzylamino)butanesulfonic acid-(1), 4-(Nisopropenylbenzylamino)bu- tanesulfonic acid-(1), 5-(N-vinylbenzylamino)pentanesulfonic acid-(1), 5(N-(isopropenylbenzylam- ino)pentanesulfonic acid-(1), 10-N-vinylbenzylamino)decanesulfonic acid- (1), 10-(N-isopropenylbenzylamino)decanesulfonic acid-(1), N-methyI-N-vinylbenzyltaurine, NmethyI-N-isopropenylben- 10 zyltaurine, N-ethyI-N-vinylbenzyltaurine, N-ethyI-N- isopropenylbenzyltaurine, N-propyI-N-vinylben- zyltaurine, N-propyI-N-isopropenylbenzyltaurine, N-butyl-N- vinylbenzyltaurine, N-butyI-N-isopro- penylbenzyltaurine, N-heptyI-N-vinylbenzyltaurine, N-heptyI-N- isopropenylbenzyltaurine, N-dode- cyI-N-vinylbenzyltaurine, N-dodecyI-N-isopropenylbenzyltaurine, N- heptadecyI-N-vinylbenzyltaurine, N-heptadecyI-N-isopropenylbenzyltaurine, N-(2-octadecylsulfinethyl)N-vinylbenzyltaurine, N- 15 (2-octadecylsulfinethyl)-N-isopropenylbenzyltaurine, N-(2stearoyloxyethyl)-N-vinylbenzyltaurine, N-(2-stearoyloxyethyl)-N-isopropenylbenzyltaurine, 2-(N-vinylbenzyI-Nmethylamino)propanesul- fonic acid-(1), 2-(N-isopropenylbenzyI-N-methylamino)propanesulfonic acid- (1), 2-(N-dodecyI-N- vinylbenzylamino)propanesulfonic acid-(1), 2-(N-dodecyI-Nisopropenylbenzylamino)propanesul- fonic acid-(1), 2-(N-octadecyI-N-vinylbenzylamino)propanesulfonic acid- (1), 2-(N-isopropenylben- 20 zyI-N-octadecylamino)propanesulfonic acid-(1), 1-(N-methyI-N- vinylbenzylamino)-2-methylpropan- esulfonic acid-(2), 1 (N-isopropenylbenzyI-N-methylamino)-2- methylpropanesulfonic acid-(2), 3(N-methyI-N-vinylbenzylamino)propanesulfonic acid-(1), 3-(NisopropenylbenzyI-N-methylamino)- propanesulfonic acid-(1), N-(vinylbenzyl)anthranilic acid, N- (vinylbenzyl)-m-aminobenzoic acid, N(vinylbenzyl)-p-aminobenzoic acid, N-(vinylbenzyl)orthanilic acid, N(vinylbenzyl)metanilic acid, N- 25 (vinylbenzyl)sulfanilic acid, etc.

The polymerizable amino acid compounds of the present invention have advantageous reactivity, surface activity, electro-chemical properties, biological 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 30 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 R is alkyl having not less than 9 carbon atoms or its modified group or of the formula (Ib') wherein 35 Rll is alkyl having not less than 9 carbon atoms or its modified group exert remarkable surface activity.

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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 40 organic solvent according to a per se conventional radical polymerization procedure.

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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 45 monomeric compounds. In case of the amount being lower than O. 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.

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As the other polymerizable monomers to be polymerized with the said polymerizable amino 50 acid compounds for production of the polymeric resin of the invention, there may be used any monomeric compounds having an ethylenic unsaturation. Examples of them are as follows:

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hydroxyl group-containing monomers (e.g. 2-hydroxyethyl acrylate, 3hydroxypropyl acrylate, 2- hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 3-hydroxybutyl acrylate, 4-hydroxybu- tyl methacrylate, allyl alcohol, methallyl alcohol), carboxyl group- containing monomers (e.g. 55 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,Ndimethylaminoethyl 6(3 methacrylate), polymerizable amides (e.g. acrylamide, methacrylamide, n- butoxymethylacrylam- ide), polymerizable nitriles (e.g. acrylonitrile, methacrylonitrile), polymerizable aromatic com- pounds (e.g. styrene, e-methylstyrene, vinyltoluene, t-butylstyrene), - olefinic compounds (e.g.

ethylene, propylene), vinylic compounds (e.g. vinyl acetate, vinyl propionate), diene compounds (e.g. butadiene, isoprene), etc. 65 7 GB2066 254A 7 "10 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. azobisisobutyronitrile, 2,2'-azobis(2, 4-dimethyl)valeroni- trile, 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 5 polymerizable monomeric compounds. In addition, any conventional chain- transfer agent such as mercaptans (e.g. laurylmercaptan, hexylmercaptan) may be employed when desired.

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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 ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, 3-methyl-3-methoxybutanol), aromatic hydrocarbons (e.g. benzene, xylene, 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 polymeriza- 15 tion in the presence of a radical initiator in an organic solvent by elevating the temperature to a desired polymerization temperature (usually from 40 to 250 C). Alternatively, for instance, the polymerizable monomeric 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 and/or the organic solvent. The polymerization is usually 20 completed within 0.5 to 20 hours.

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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 under average molecular weight (1 n) of the polymeric resin determined by GPC is normally from 1,000 to 50,000. 25 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 cross-linking 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. 30 Particularly when the polymeric resin is the one prepared by the use of a hydroxyl groupcontaining 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 polymeriza- ble 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 35 resins, guanamine resins, etc. On the use, the aminoplast resin may be previously dissolved in an organic solvent such as ethylene glycol monoalkyl ether or diethylene glycol 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 40 200 C) within a short period of time (e.g. 30 seconds to 60 minutes).

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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.

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As the carboxyl group-containing polymerizable monomer, there may be specifically employed 45 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 beused any ordinary one having an ethylenic unsaturation. Examples are hydroxyl group- containing monomers, alkyl acrylates and alkyl methacrylates, nitrogen- containing alkyl acrylates and nitrogen-containing alkyl methacrylates, polymerizable amides, polymerizable nitriles, polym- 50 erizable aromatic compounds, e-olefinic compounds, vinylic compounds, diene compounds, etc.

These may be used alone or in combination.

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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 55 polmerizable 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.

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In case of the carboxyl group-containing polymerizable monomer being less than 3% by weight, 60 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.

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For the production of the said polymeric resin excellent in dispersibility into an aqueous 65 8 GB2066 254A 8 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.

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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. 5 Examples of the basic substance are ammonia, amines (e.g. trimethylamine, diethylamine, triethylamine, tributylamine, diethanolamine, dimethylethanolamine, diethylethanolamine, 2- amino-2-methyl-l-propanol, morpholine, 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 O. 1 to 2 molar equivalents to the total acid amount in the 10 polymeric resin.

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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 molecular weight of 1,000 to 50,000 and a glass transition point of --40to +100 C. 15 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, preferably from to 50 parts by weight (in terms of solid) to 100 parts by weight of the polymeric resin in the 20 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.

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In addition to the polymeric resin and the aminoplast resin, there may be optionally incorporated any conventional additive such as organic or inorganic pigments, fillers, thickening 25 agents, surfactants, pH regulators, water and organic solvents. The incorporation can be easily effected by mixation at room temperature.

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The coating composition of the invention is usually applied to a substrate to make a film thickness of 5 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 30 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.

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This invention will be illustrated in details with reference to Examples and Comparative 35 Examples as shown below, part(s) and (%) by weight unless otherwise indicated.

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Example I .DTD:

In a 2 liter volume flask equipped with a stirrer, taurine (125 g), sodium hydroxide (40 g), 40 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 glycidyl ether (114 g) and p-nitrosophenol (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 Na + ion, whereby a solution of pH 4 was obtained. The 4.5 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 taurine 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-3allyloxypropyl)taurine (96 g). Identification was made by NMR and IR. The NMR chart measured in D20 is shown in Fig. 1.

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Example II .DTD:

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

.DTD:

Examples III-X In the same manner as in Example I but using an amino acid compound in place of taurine, the reaction was carried out togive 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 DO are shown in Figs. 2 to 5, respectively.

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9 GB2066 254A 9 Table 1 .DTD:

Amount Example Amino acid compound used (g) III 4-Aminobutanesul- fonic acid-(1) 153 IV 10-Aminodecanesul- fonic acid-(1) 237 V N-Methyltaurine 139 VI N-Dodecyltaurine 294 VII Glycine 75 oz-Alanine 89 VIII IX /-Alanine 89 X -Aminocaproic acid 131 Table 1 (continued) Example Polymerizable amino acid compound Yield (g) I I I 4-[N-2-hyd roxy-3-allyt oxypropyl)amino]butanesulfonic acid-(1) 79 IV 4-[N-(2-Hydroxy-3-allyloxypropyl)amino]decanesulfonic acid-(1) 107 V N-MethyI-N-(2-hydroxy-3- allyloxypropyl)taurine 60 VI N-DodecyI-N-(2-hydroxy-3- allyloxypropyl)taurine 120 VII N-(2-Hyd roxy-3-allyloxy- propyl)glycine 39 Vlll N-(2-Hydroxy-3-allyloxypropyl)-x-alanine 51 IX N-(2-Hydroxy-3-allyloxy- propyl)-/-alanine 82 X N-(2-Hydroxy-3-allyloxy- propyl)-aminocaproic acid 110 55 Example XI .DTD:

Into a 2 liter volume flask equipped with a stirrer, allyl 3-amino-2hydroxypropyl ether (131 g), deionized water (100 g), ethylene glycol monomethyl ether (300 g) and p-nitrophenol (0.13 60 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.

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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 identified to unreacted sodium vinylsulfonate by NMR and IR. The filtrate was treated with an 65 GB2066 254A 10 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.

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Example Xll .DTD:

In the same manner as in Example Xl but using allyl 3-(N-methylamino)-2hydroxypropyl ether (145 g) in place of allyl 3-amino-2-hydroxypropyl ether, the reaction was carried out to obtain NmethyI-N-(2-hydroxy-3allyloxypropyl)taurine (243 g).

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Example XIII .DTD:

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

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Example XIV .DTD:

Into a 2 liter volume flask equipped with a stirrer, allyl 3-amino-2hydroxypropyl ether (131 g), ethylene glycol monoethyl ether (400 g) and p-nitrosophenol (0.13 g) were charged.The contents were maintained at 50 C 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 20 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 evaporator to make a 5/10 volume. The concentrated solution was treated with an ionic exchange resin (Amberlite IR-120) and further treated with acetone to give transparent oily materials (193 g), which was identified to N-(2-hydroxy-3-allyloxypropyl)- /-alanine. 25- Example XV .DTD:

In the same manner as in Example XIV but using allyl 3-(N-dodecylamino)-2hydroxypropyl ether (297 g) in place of allyl 3-amino-2-hydroxypropyl ether, the reaction was carried out to 30 obtain N-dodecyI-N-(2-hydroxy-3allyloxypropyl)-/-alanine (359 g).

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Example XVI .DTD:

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-(2hydroxy-3-allyloxypropyl)taurine (228 g).

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Example XVII .DTD:

The product in Example VI, Xlll or XV was dissolved in deionized water containing an equimolar amount of N,N-dimethylethanol 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 40 products in the Examples have a surface activity.

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Example XVlII .DTD:

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), 45 ethylene glycol monomethyl ether (250 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, stirring was continued for 4 hours. To the reaction mixture, conc. hydrochloric acid (220 g) was added, whereby white solids (Product I) (57 g) were precipitated. The filtrate was concentrated in a rotary evaporator to make a 3/10 volume, and 50 the precipitated solids were exctracted with a 4 times volume of hot acetone. The extract was cooled, and the precipitated white solids (product II) (126 g) were collected and dried in vacuo.

.DTD:

The Products I and II were respectively identified to N,Ndi(vinylbenzyl)taurine and N-vinylben- zyltaurine by NMR and IR. The NMR charts of Products I and II measured in CD3OD/ D20 = 8/2 (NaOD added) are shown in Figs. 6 and 7, respectively. 55 Example XIX .DTD:

In the same manner as in Example XVlll but using 2-aminobutanesulfonic acid-(1) (306 g) in place of taurine, the reaction was carried out to obtain 2-(N- vinylbenzylamino)butanesulfonic 60 acid-(1)(91 g).

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Example XX .DTD:

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

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11 GB2066254A 11 Example XXl .DTD:

In the same manner as in Example XVIII but charging deionized water (200 g), sodium hydroxide (80 g), lO-aminodecanesulfonic acid-(1) (474 g) and ethylene glycol monomethyl ether (500 g) at the initial stage, the reaction was carried out to obtain lO-(N-vinylbenzylamino)decanesulfonic acid-(1) (180 g).

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Example XXII .DTD:

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, stirring was continued for 5 hours. To the reacti.on 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 recrystallized from deionized water to give NmethyI-N- vinylbenzyltaurine. The NMR chart measured in CD3OD/D20 = 2/1 (NaOD added) is shown in Fig. 8.

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Example XXIII .DTD:

In the same manner as in Example XXII but charging deionized water (300 g), Ndodecyltaurine 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 25 glycol monoethyl ether (200 g) and p- nitrosophenol (0.2 g) at a later stage, the reaction was carrid out to obtain N-dodecyI-N-isopropenylbenzyltaurine (330 g).

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Example XXIV .DTD:

Into a 2 liter volume flask 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. 30 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 (1 O0 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 cooled 35 to precipitate white solids (219 g), which were collected and dried in vacuo to give N- vinylbenzyltaurine.

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Example X,V .DTD:

In the same manner as in Example XXIV but using (vinylbenzyl)butylamine (189 g) in place of 40 vinylbenzylamine, the reaction was carried out to obtain N-buty-N- vinylbenzyltaurine (264 g).

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Example XXVI .DTD:

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 45 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. 50 T.he residue was washed with deionized water to give white solids (226 g), which were identified to N-vinylbenzyltaurine by NMR.

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Example XXWI .DTD:

In the same manner as in Example XXVI but using (vinylbenzyl)dodecylamine (301 g) in place 55 of vinylbenzylamine, the reaction was carried out to obtain N-dodecyI-N- vinylbenzyltaurine (390 g).

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Example XXVIII The product in Example XXI was admixed with an equimolar amount of N,N- dimethylethano- 60 lamine, 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.

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Examp 1 65 12 GB2066 254A 12 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 solubilizer were charged. In the other dropp'ing 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 which the temperature was maintained at 100 C 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.

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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.

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Example 2 .DTD:

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:

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Part(s) N-(vinylbenzyl)tau rine 10 2-Hydroxyethyl acrylate 50 Acrylic acid 25 Methyl methacrylate 100 Styrene 100 n-Butyl acrylate 215 Laurylmercaptan 5 Azobisisobutyronitrile 10 Xylene 250 Ethylene glycol monomethyl ether 150 Ethylene glycol monobutyl ether 1 O0 Tile 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 plate and baked at 80 to 100 C for 30 minutes to give a coating film completely cured and having excellent physical properties.

.DTD:

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.

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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.

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13 GB2066254A 13 Table 2 .DTD:

Example No.

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Component (parts) 3 4 5 6 7 Polymerizable amino acid 5 10 10 10 25 compound.1) 2-Hydroxyethyl acrylate 25 -- 50 -- 50 2-Hydroxyethyl methacrylate....

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Acrylic acid 15 -- -- 10 Methacrylic acid -- 10 -- N-Butoxymethyl acrylamide 90 -- - N,N-Dimethylaminoethyl -- 20 methacrylate Glycidyl methacrylate: 80 Methyl methacrylate 100 150 100 125 Styrene 125 150 150 150 - Methyl acrylate 180 -- 100 n-Butyl acrylate -- 160 90 n-Butyl methacrylate 150 -- 100 2-Ethylhexyl acrylate 140 - 120 Laurylmercaptan 5 2.5 5 5 5 Azobisisobutyronitrile 10 10 10 10 10 Table 2 (continued) Example No.

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Component (parts) 8 9 10 11 12 Polymerizable amino acid 60 125 20 10 10 compound.1) 2-Hydroxyethyl acrylate 50 50 50 50 2-Hydroxyethyl methacrylate -- 50 -- Acrylic acid 10 10 10 10 10 Methacrylic acid -- --- n-Butoxymethyl acrylamide -- -- N, N-Dimethylaminoethyl -- -- -methacrylate Glycidyl methacrylate....

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Methyl methacrylate 1 O0 1 O0 100 1 O0 Styrene 50 75 1 O0 1 O0 1 O0 Methyl acrylate 320 -- n-Butyl acrylate 240 -- 230 230 n-Butyl methacrylate 1 O0....

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2-Ethylhexyl acrylate 140 -- -- Laurylmercaptan 5 5 5 5 5 Azobisisobutyronitrile 10 10 10 10 10 14 G82066 254A 14 Table 2 (continued) Example No.

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Component (parts) 3 4 5 6 7 5 Toluene Xylene 250 Ethylene glycol 150 monomethyl ether Ethylene glycol 100 monobutyl ether 250. -- -- -- -- 250 250 250 250 150 150 200 100 Viscosity T Y S S T Number average molecular weight (IVI n) 6200 8800 6300 6200 6500 Table 2 (continued) Component (parts) Example No.

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8 9 10 11 12 Toluene Xylene Ethylene glycol monomethyl ether Ethylene glycol monobutyl ether 250 250 250 150 150 150 100 100 100 Viscosity S X T T V Number average molecular 6000 7200 6800 6800 7000 weight (1 n) Note: "1) Examples 3 to 6, N-methyI-N-vinyl-benzyltaurine; Examples 7 to 9, Nvinylbenzyl-/-alanine; Example 10, N-(2-hydroxy-3-allyloxypropyl)taurine; Example 11, N-vinylbenzyl-metanilic acid; Example 12, Nvinylbenzylsulfanilic acid.

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Example 13 .DTD:

Into a 2 liter volume flask equipped with a stirrer, ethylene glycol monomethyl ether (61.6 45 parts) was charged, and the temperature was elevated to 110"C 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 50 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, 1 g.5 C.

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Examples 14 to 26 and Comparative Examples 1 and 2 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.

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GB2066 254A 15 Table 3 .DTD:

Component (parts) Ethylene glycol monomethyl ether Isopropanol Ethylene glycol monomethyl ether Isopropanol N-(2-Hydroxy-3- allyloxypropyl)taurine N-Vinylbenzyltaurine N-Methyl-N-vinyl 20 benzyltaurine 2-Hydroxyethyl acrylate Dimethylaminoethyl methacrylate Dimethylethanolamine Styrene Methyl methacrylate n-Butyl acrylate 2-Ethylhexyl acrylate Acrylic acid Example .DTD:

14.8 93.6 93.6 124.8 L 4.8 40 0.88 100.6 100.6 134.1 8O 120 4.8 40 0.88 94.6 94.6 126.1 9.6 40 1.76 99.1 99.1 132.2 8O 120 9.6 4O 1.76 93.1 93.1 124.2 16 GB2066254A 16 Table 3 (continued) Component 5 (parts) Example .DTD:

Ethylene glycol monomethyl ether Isopropanol Ethylene glycol monomethyl ether Isopropanol N-(2-Hydroxy- 3allyloxypropyl)- taurine N-Vinylbenzyltaurine N-Methyl-N-vinyl benzyltaurine 2-Hydroxyethyl acrylate Dimethylaminoethyl methacrylate Dimethylethanol- amine Styrene Methyl methacrylate n-Butyl acrylate 2-Ethylhexyl acrylate Acrylic acid 32 8 4O 97.2 97.2 129.6 28 32 4 4O 1.4 98.4 98.4 131.2 28 4 4O 1.4 98.4 98.4 131.2 28 8O 120 4 28 1.4 102 102 136 28 32 16 4O 5.6 94.8 94.8 126.4 28 17 G82066 254A 17 Table 3 (continued) Component (parts) Ethylene glycol monomethyl ether Isopropanol Ethylene glycol monomethyl ether Isopropanol N-(2-Hydroxy-3- allyloxypropyl)taurine N-Vinylbenzyltaurine N-Methyl-N-vinyl20 benzyltaurine 2-Hydroxyethyl acrylate Dimethylaminoethyl methacrylate Dimethylethanolamine Styrene Methyl methacrylate n-Butyl acrylate 2-Ethylhexyl acrylate Acrylic acid Example .DTD:

Comparative Example 32 4 4O 26 1.4 90.6 90.6 120.8 32 4 40 1.4 98.6 98.6 102 102 136 131.2 19.6 0.8 0.28 99.4.99.4 132.5 28 96 128 18 GB2066 254A 18 Table 3 (continued) Example .DTD:

Component (parts) 14 16 17 18 Itaconic acid Azobisiso- 6 butyronitrile Laurylmercaptan Azobisiso- 5 butyronitrile Methylethylketone 12 Dimethylethanol- 34.6 amine Ethylene glycol monomethyl ether Deionized water 670 6 6 6 6 8 8 8 8 2 2 2 2 12 12 12 12 24.8 49.6 89.6 79.6 82.7 70.3 289.6 279.6 282.7 270.3 TransparencyTM Non-volatile component content (%) 33 50 50 50 50 Number average 25000 5500 5500 5500 5500 molecular weight (1 n) Glass transition 23.0 19.1 22.5 19.8 23.2 point ( C) Table 3 (continued) Example .DTD:

Component (parts) 19 20 21 22 23 Itaconic acid Azobisiso- 6 6 6 6 6 butyronitrile Laurylmercaptan 4 4 4 8 8 Azobisiso- 2 2 2 2 2 butyronitrile Methylethylketone 12 12 12 12 12 Dimethylethanol- 34.6 34.6 34.6 34.6 34.6 amine Ethylene glycol -- 182 182 -- monomethyl ether Deionized water 670 670 382 382 670 TransparencyTM A A o o / Non-volatile 33 33 33 33 33 component content (%) Number average 900 9000 8300 5500 6000 molecular weight (M n) Glass transition 21.0 20.3 20.3 21.5 22.3 point ("C) 19 GB2066 254A 19 Table 3 (continued) Component 5 (parts) Example .DTD:

19 20 21 22 23 Itaconic acid Azobisisobutyronitrile Laurylmercaptan Azobisisobutyronitrile Methylethylketone Dimethylethanol amine Ethylene glycol monomethyl ether Deionized water 7.6......

*.DTD:

6 6 6 6 6 8 8 8 8 8 2 2 2 2 2 12 12 12 12 12 34.6 34.6 34.8 24.8 49.6 184 82.7 70.3 670 670 382 282.7 270.3 Transparency.1) A A o A o Non-volatile component content (%) 33 33 33 33 33 Number average 6000 6000 5500 5500 5500 molecular weight (i n) Glass transition 20.3 1.1 19.8 point ( C) Note: "1) Transparent, o; semi-transparent, z; non-transparent, x.

Example 27 .DTD:

The resinous dispersion obtained il 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 120 C, 140 C or 160 C for 30 minutes for curing.

.DTD:

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:

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B-C Solubility (%) - X 100 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 50 sheet and the coating film after immersing and drying at 120"C for 20 minutes.

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/ POOR QUALITY GB 2 066 254A 20 Table 4 .DTD:

Temperature for baking 120 C 140 C 160 C Example .DTD:

12 2 16 45 7 0 17 24 6 3 18 22 4 0 Comparative 1 100 64.7 27,6 Example 2 100 21.6 2.7 Example 28 .DTD:

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 20 coating composition was applied onto a zinc- plated iron sheet, followed by baking at 140 C for minutes for curing.

.DTD:

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:

.DTD:

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.

.DTD:

Table 5 .DTD:

Solubility (%) Swelling (%) Example 15 7.0 7.5 16 5.8 6.3 Comparative 21.6 55.6 Example 1 .DTD:

Example 29 .DTD:

The resinous dispersion obtained in any of Examples 20 to 26, carbon black ("Mitsubishi Carbon MA-IO0" 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 120 C or 140 C for 30 minutes for curing.

.DTD:

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

.DTD:

.CLME:

Claims

CLAIMS .CLME:

1. A polymerizable aminoacid compound of the formula:

.CLME:

R8 R9 Rll I I I CH2 = C-C6H4-C- N-R12-SO3H (Ib'), I Rio wherein Re, R9 and Rio are each hydrogen or C1-C6 alkyl; RI is hydrogen or C1-C2o alkyl, 65 21 GB2066254A 21 optionally having -SO-, -CO0- or -0- therein, or a group of the formula:

.CLME:

R8 R9 I I CH2 = C-CsH4-C- 5 I Rio (R8, Rg and Rio being each as defined above); and R2 is C2-CT2 alkylene, optionally substituted " 10 by Cl-C6 alkyl. 10 2. A compound according to claim 1, wherein R8 is hydrogen.

.CLME:

3. A compound according to claim 1, wherein R8 is methyl.

.CLME:

4. A compound according to any one of claims 1 to 3, wherein Rg and Ro are each hydrogen.

.CLME:

5. The compound according to any one of claims 1 to 4, wherein R is hydrogen. 15 6. The compound according to any one of claims 1 to 4, wherein RlI is C- C8 alkyl.

.CLME:

7. The compound according to any one of claims 1 to 4, wherein R is C9C2o alkyl, optionally having -S-, -COO- or -0- therein.

.CLME:

8. A compound according to any one of claims 1 to 4, wherein R is a group of the formula: 20 R8 R0 I J OH2 = 0-66H4-0- I 25 Rio Rs, R0 and Rio being each as defined in any one of claims 1 to 4.

.CLME:

9. A compound according.to claim 1, which is representable by the formula:

.CLME:

R8 R9 R R14 I I I I OH2 = C-CsH4-C- N-CH2-CH-SO3H Ro 35 wherein R4 is hydrogen, methyl or ethyl, and R8, R9, Ro and R are each as defined in any one of claims 1 to 8.

.CLME:

10. A compound according to any one of claims 1 to 8, wherein R2 is ethylene.

.CLME:

11. A polymeric resin prepared by solution polymerization of 40 (a) at least one polymerizable aminoacid compound of the formula:

.CLME:

R8 R9 Rli I I 1 CH2 = C-C6H4-C- N-RI-SO3H Ro (Ib'), 45 wherein R8, R9 and Ro are each hydrogen or C-C6 alkyl; Rll is hydrogen or C-C2o alkyl, 50 optionally having -SO-, -CO0- or -0- therein, or a group of the formula:

.CLME:

R8 R9 I I --- 6_06H4_C_ Rio (R8, R9 and Ro being each as defined above); R2 is C2-C2 alkylene, optionally substituted by Cl-C6 alkyl, (b) at least one carboxyl group-containing monomer, and (c) at least one other polymerizable monomer, and having a number average molecular weight of 1,000 to 50,000 and a glass transition point within the range of from 40 C to + 100 C, inclusive.

.CLME:

12. A resin according to claim 11, wherein the solution polymerization is effected in a water-miscible organic solvent.

.CLME:

22 "GB 2 066 254A 22 13. A resin according to claim 11 or 12, wherein the other polymerizable monomer(s), as 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, cx- olefinic compounds, vinylic 5 compounds and diene compounds.

.CLME:

14. A resin according to claim 11 or 12, wherein the other polymerizable monomer(s), as component (c), are hydroxyl group-containing monomers.

.CLME:

15. A dispersion of the polymeric resin according to any one of claims 11 to 14 in an aqueous medium containing non-volatile components in an amount of 5 to 80% by weight.

.CLME:

16. A process for preparing a dispersion of a polymeric resin in an aqueous medium, which comprises:

.CLME:

(i) subjecting:

.CLME:

(a) at least one polymerizable aminoacid compound of the formula:

.CLME:

R8 R9 Rli 15 I I I CH2 = C-C6H4-C- N-R12-SO3H (Ib'), I Rio wherein R8, R9 and Rio are each hydrogen or C-C6 alkyl; Rll is hydrogen or C-C2o alkyl, optonally having -SO-, -COO- or -0- therein, or a group of the formula:

.CLME:

R8 R9 I I 25 CH2 = C-C6H4-C- Rio (R8, R9 and Ro being each as defined above); 30 and R2 is C2-C12 alkylene, optionally substituted by C-C6 alkyl, (b) at least one of carboxyl group-containing monomers, and (c) at least one other polymerizable monomer, to solution polymerization in a water water- miscible organic solvent, (ii) neutralizing the polymerization product, and 35 (iii) dispersing into an aqueous medium the resulting polymeric resin having a number average molecular weight of 1,000 to 50,000 and a glass transition point within the range of from 40 C to + 100 C, inclusive.

.CLME:

17. A process according to claim 16, wherein the dispersion which is obtained contains non- volatile components in an amount of 5 to 80% by weight. 40 18. A coating composition comprising, as a main component, a polymeric resin obtained by solution polymerization of:

.CLME:

(a) at least one polymerizable aminoacid compound of the formula:

.CLME:

R8 R9 Rll 45 I I 1 CH2 = C-C6H4-C- N-R12-SO3H (Ib') 1 Rio 5O 5O wherein Rs,- R9 and Ro are each hydrogen or C-C6 alkyl; R is hydrogen or C1-C2o alkyl, optionally having -SO-, -COO- or -0- therein, or a group of the formula:

.CLME:

R8 R9 I I 55 CH2 = C-C6H4-C- I Rio (R8, R9 and Rio being each as defined above); and R2 is C2-C2 alkylene, optionally substituted by C-C6 alkyl, (b) at least one carboxyl group-containing monomers, and (c) at least one other polymerizable monomer, and having a number average molecular weight of 1,000 to 50,000 and a glass transition point within the range of from 40 C to 65 + 100 C, inclusive.

.CLME:

23 GB 2 066 254A 23 19. A compositon according to claim 18, wherein the other polymerizable monomer(s), as component (c), 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 amides, polymerizable nitriles, polymerizable aromatic compounds, x-olefinic compounds, vinylic compounds and diene 5 compounds.

.CLME:

20. A composition according to claim 18, wherein the other polymerizable monomer(s), as component (c), are hydroxyl group-contaning monomers.

.CLME:

21. A composition according to any one of claims 18 to 20, which further comprises at least one aminoplast resin. 10 22. A compound according to claim 1, substantially as herein described with reference to any one of the specific examples.

.CLME:

23. A resin according to claim 11 substantially as herein described with reference to any one of the specific examples.

.CLME:

24. A process according to claim 16 substantially as herein described with reference to any 15 one of the specific examples.

.CLME:

25. A composition according to claim 18 substantially as herein described with reference to any one of the specific examples.

.CLME:

Printed for Her Majesty's Stationery Office by Burgess 8" Son (Abingdon) Ltd.--1981.

.CLME:

Published at The Patent Office,25 Southampton Buildings, London, WC2A lAY, from which copies may be obtained.

.CLME: