JPS62223275A - Cationic aqueous resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which gives a film having excellent strength, water resistance and adhesion, consisting of a specified e.g. resin dispersion and a compd. having at least two functional groups capable of reacting with a modified polyamine. CONSTITUTION:A polyamine (derivative) (e.g., a polyalkyleneimine) is reacted with a compd. having the formula (wherein R is a 4-28C hydrocarbon group; A is a 2-4C alkylene; X is epoxy, carboxyl, vinyl, isocyanate or halogen; and n is a number of 0-30) and optionally an epihalohydrin to obtain an emulsifier composed of a modified polyamine. 100pts.wt. polymerizable monomer [e.g., methyl (meth)acrylate] is emulsion-polymerized in the presence of 0.5-200pts.wt. said emulsifier in an aq. medium to obtain an aq. resin dispersion (A). 100pts.wt. (on a solid basis) component A is blended with 0.1-1,000pts.wt. compd. (B) having at least two functional groups capable of reacting with the modified polyamine (e.g., maleic anhydride).

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a novel cationic aqueous resin composition. More specifically, it is a water-resistant resin dispersion obtained by using a modified polyamine having excellent emulsifying power and crosslinking reactivity as an emulsifier, and a compound having two or more functional groups capable of reacting with the modified polyamine in its molecule. The present invention relates to a cationic aqueous resin composition capable of forming a film having excellent physical properties including properties. Since the cationic aqueous resin composition of the present invention has cationic particle charges, it has excellent adsorption and adhesive properties to various substances, and has a higher foaming property than those using known emulsifiers widely used in the industry. Since it can form a strong film with low water resistance and good water resistance, it is suitable for fiber processing, glass fiber processing, leather processing, and coating and adhesion on various inorganic and organic materials such as glass, metal, cement, plastic, etc. It is useful in a wide range of fields such as (Prior Art) Cationic emulsions obtained by emulsion polymerization of polymerizable monomers in the presence of cationic emulsifiers such as dodecyltrimethylammonium chloride and stearyltrimethylammonium chloride have been known. Although it is used for various purposes due to its cationic nature, it has the disadvantage that the film has poor water resistance and strength. (Problems to be Solved by the Invention) The present invention aims to solve the above-mentioned problems that conventional cationic emulsions had, and therefore, its purpose is to:
It is an object of the present invention to provide a cationic aqueous resin composition having a film having excellent water resistance and strength. (Means and effects for solving the problem) The present inventors added a hydrophobic group or a hydrophobic group and a hydrophilic group to a hydrophilic polyamine and/or a derivative thereof using an epoxy group, an incyanate group, etc. A cationic modified polyamine that is introduced through a reactive group, made more hydrophilic by a quaternization reaction if necessary, and reacted with shrimp halohydrin to introduce a reactive group exhibits excellent emulsifying power. Furthermore, it has been found that the modified polyamine has crosslinkability with a compound having a specific functional group. Furthermore, when the modified polyamine is used as an emulsifier in the emulsion polymerization of polymerizable monomers, an aqueous resin dispersion can be produced with good stability during polymerization, and the resulting aqueous resin dispersion reacts with the modified polyamine in its molecules. The cationic aqueous resin composition, which is composed of a compound having two or more functional groups, forms a film with excellent water resistance and high strength, and furthermore, because it is cationic, it forms a film with good adhesion to various materials. The present invention was achieved based on the discovery that That is, the present invention provides polyamines and/or derivatives thereof with the general formula % formula % (wherein R represents a hydrocarbon group having 4 to 28 carbon atoms, A represents an alkylene group having 2 to 4 carbon atoms, X is an epoxy group,
It represents an atomic group having a carboxyl group, a vinyl group or a vincyanate group, or a halogen atom, and n represents O or an integer from 1 to 30. ) and an aqueous resin dispersion (A) obtained by emulsion polymerization of a polymerizable monomer in an aqueous medium using a modified polyamine obtained by reacting a compound represented by (A) with Chebihalohydrin if necessary as an emulsifier; The compound (B) having two or more functional groups capable of reacting with the modified polyamine in the molecule is not included as an essential component, and the aqueous resin dispersion (
Compound (B) 0 per 100 parts by weight of non-volatile content of A)
．． It relates to a cationic aqueous resin composition in a proportion of 1 to 1000 parts by weight. The polyamine and/or its derivative used in the present invention has at least two nitrogen atoms in the molecule and also has at least two primary and/or secondary amine groups. Examples of polyamines include polyalkyleneimines obtained by polymerization or copolymerization of alkyleneimines such as polyethyleneimine obtained by polymerization of ethyleneimine; poly)
Alkylene polyamine; polyamide polyamine obtained by condensation of polyalkylene imine and/or (poly) alkylene polyamine with polybasic acid such as adipic acid; polyalkylene imine and/or (poly) alkylene polyamine and/or alkylene imine and urea and polyamide polyester polyamines obtained by copolymerizing an alkylene imine with an acid anhydride such as heptatalic acid. Examples of polyamine derivatives include those obtained by addition-reacting the polyamine with an alkylene oxide such as ethylene oxide or propylene oxide, or an α,β-unsaturated acid amide compound such as acrylamide. In the compound (hereinafter referred to as compound (1)) used in the present invention represented by the general formula Rtama OA-Xn (in the formula, R, A, X and n are the same as above), the formula Examples of the hydrocarbon group having 4 to 28 carbon atoms to be replaced by R include a straight or branched alkyl group having 4 to 28 carbon atoms, an (alkyl)aryl group, a (alkyl)hydrogenated aryl group, Examples include (alkyl)°aralkyl groups. Examples of the compound (1) include n-octyl polyoxyalkylene glycidyl ether, n-nonyl polyoxyalkylene glycidyl ether, and lauryl polyoxyalkylene glycidyl ether having an additional mole number of 1 to 30 alkylene oxides such as ethylene oxide, propylene oxide, and imbutylene oxide. Primary alkyl polyoxyalkylene glycidyl ethers such as oxyalkylene glycidyl ether, stearyl polyoxyalkylene glycidyl ether, and 2-ethylhexyl polyoxyalkylene glycidyl ether; secondary alkyl polyoxy, such as those obtained by adding 1 to 30 moles of alkylene oxide to a mixture of secondary alcohols having 10 to 12 carbon atoms and further glycidyl etherification, etc. Alkylene glycidyl ethers; octylphenyl polyoxyalkylene glycidyl ether, nonylphenyl polyoxyalkylene glycidyl ether, lauryl phenyl polyoxyalkylene glycidyl ether, stearyl phenyl polyoxyalkylene glycidyl ether with an added mole number of alkylene oxide from 1 to 30 Alkylphenyl polyoxyalkylene glycidyl ethers such as; octylcyclopentyl polyoxyalkylene glycidyl ether with an addition mole number of alkylene oxide of 1 to 30, octylcyclohexyl polyoxyalkylene glycidyl ether, nonyl Schifta pentyl polyoxyalkylene glycidyl ether, nonyl cyclohexyl poly Alkyl cycloalkyl polyoxyalkylene glycidyl ethers such as oxyalkylene glycidyl ether, lauryl cyclopentyl polyoxyalkylene glycidyl ether, lauryl cyclohexyl polyoxyalkylene glycidyl ether, stearyl cyclopentyl polyoxyalkylene glycidyl ether, and stearyl cyclohexyl polyoxyalkylene glycidyl ether: alkylene Alkylbenzyl polyoxyethylene glycidyl ether such as octylbenzyl polyoxyalkylene glycidyl ether, nonylbenzyl polyoxyalkylene glycidyl ether, laurylbenzyl polyoxyalkylene glycidyl ether, and stearylbenzyl polyoxyalkylene glycidyl ether, with an added mole number of oxide from 1 to 30. Glycidyl ethers of higher alcohols such as octyl glycidyl ether, lauryl glycidyl ether, stearyl glycidyl ether, 2-ethylhexyl glycidyl ether; octylphenyl glycidyl ether, nonylphenyl glycidyl ether, lauryl phenyl glycidyl ether, stearyl phenyl glycidyl ether, etc. glycidyl ethers of alkylphenols; octylcyclopentyl glycidyl ether,
Octylcyclohexylglycidyl ether, nonylcyclopentylglycidyl ether, nonylcyclohexylglycidyl ether, laurylcyclopentylglycidyl ether, laurylcyclohexylglycidyl ether, stearylcyclopentylglycidyl ether,
Glycidyl ethers of alkylcycloalkanols such as stearylcyclohexylglycidyl ether; cricidyl ethers of alkylbenzyl alcohols such as octylbenzylglycidyl ether, nonylbenzylglycidyl ether, laurylbenzylglycidyl ether, and stearylbenzylglycidyl ether; carbon number 12 or 14 α-olefin epoxide, 1 carbon number
1,2- such as 6 or 18 α-olefin epoxides
Epoxyalkanes; Alkylinocyanates such as octyl isocyanate, decyl isocyanate, and octadecyl incyanate; Alcohols such as octanol, lauryl alcohol, and stearyl alcohol, or alkylene oxide adducts of these alcohols and diisocyanates such as tolylene diincyanate; Monoisocyanate compounds obtained by the reaction of octatool, lauryl alcohol, stearyl alcohol, etc. or alkylene oxide adducts of these alcohols, the terminal hydroxyl group of which is replaced with a halogen atom such as chlorine, bromine, or iodine. Substituted halides; Saturated fatty acids such as lauric acid, ξristic acid, palmitic acid, and stearic acid; Unsaturated fatty acids such as nioleic acid, linoleic acid, lylunic acid, and eleostearic acid; Acrylic acid 2-
Examples include acrylic acid alkyl esters such as ethylhexyl, lauryl acrylate, and stearyl acrylate, and one or more types selected from these groups can be used. The amount of the compound (1) used to obtain the modified polyamine used in the present invention is not particularly limited, but in order to develop sufficient surface activity, it is necessary to It is preferred to use from .01 to 1 molecule of compound (1). Furthermore, the modified polyamine obtained by the above reaction can be further reacted with epihalohydrin if necessary. Examples of epihalohydrin that can be used include epichlorohydrin, epibromohydrin, and ebiodohydrin, but epichlorohydrin is preferred. In obtaining the modified polyamine used in the present invention, the amount of epihalohydrin used is not particularly limited, but in order to develop sufficient curability, it is necessary to use the amount per amine hydrogen in the polyamine and/or its derivative. 90.1
Preferably, two molecules of epihalohydrin are used. The reaction conditions for obtaining the modified polyamine used in the present invention are not particularly limited and may be appropriately selected depending on the properties and reactivity of the polyamine and/or its derivative compound (1) and epihalohydrin. Other catalysts may also be used. Also, add acid to the obtained modified polyamine to adjust the pH! You can also make adjustments. As the acid, inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, and organic acids such as formic acid, acetic acid, acrylic acid, and methacrylic acid can be used. The modified polyamine thus obtained has excellent emulsifying power and can stably carry out emulsion polymerization of a wide variety of polymerizable monomers. Therefore, the cationic aqueous resin composition of the present invention has excellent performance. It provides an aqueous resin dispersion (A) which is the first component constituting the product. The polymerizable monomer used in the present invention is not limited to % as long as it contains a polymerizable unsaturated group, but examples include methyl (meth)acrylate. A linear or branched aliphatic alkyl alcohol or alicyclic alkyl alcohol having 1 to 18 carbon atoms, such as ethyl, propyl, inglovil, butyl, isobutyl, octyl, 2-ethylhexyl, lauryl, stearyl, or cyclohexyl ester; (Meth)acrylic acid esters which are ester compounds with meth)acrylic acid; (meth)aminoethyl acrylate, dimethylaminoethyl (meth)acrylate, dimethylaminoethyl (
Basic unsaturated monomers such as meth)acrylamide, vinylpyridine, vinylimidazole, vinylpyrrolidone; (meth)acrylic acid and ethylene glycol, 1.3-
Polyfunctional products containing two or more polymerizable unsaturated groups in the molecule, such as polyesters with polyhydric alcohols such as butylene glycol, 1゜6-hexane glycol, neopentyl glycol, polyethylene glycol, polypropylene glycol, and trimethylolpropane. (Meth)acrylic acid esters; (meth)acrylamide, methylolated (meth)acrylamide, alkoxymethylolated (meth)acrylamide having 1 to 4 carbon atoms, etc.
Acrylamides; (meth)acrylic acid, crotonic acid, and other unsaturated monocarboxylic acids and their salts; itaconic acid, maleic acid, fumaric acid, and other unsaturated polycarboxylic acids, their salts, and nucleic acid monoester compounds; vinyl sulfone Polymerizable unsaturated sulfonic acids such as styrene sulfonic acid, sulfoethyl (meth)acrylate, and their salts; hydroxyethyl (meth)acrylate, hydroxyglobyl (meth)acrylate, acrylic acid or methacrylic acid and polytetrapyrene Hydroxyl group-containing unsaturated monomers such as monoesters with glycol or polyethylene glycol; Epoxy group-containing unsaturated monomers such as glycybalate (meth)acrylate; (meth)
Halohydrin group-containing unsaturated monomers such as 2-hydroxy-3-chloropropyl acrylate; vinyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxyethoxysilane, r-(meth)acryloxypropyltriethoxysilane, Organosilicon monomers such as 7-(meth)acryloxypropyltriethoxysilane, r-(meth)acryloxyglobylmethyldimethoxysilane, allyltriethoxysilane, trimethoxysilylglopylarylamine: (meth)acrylic acid Blocked incyanate group-containing unsaturated monomers such as phenolic adducts of incyanatoethyl; aziridinyl group-containing unsaturated monomers such as (meth)acryloylaziridine and (meth)acryloyloxyethylaziridine; 2- Oxazoline group-containing unsaturated monomers such as propenyl-2-oxazoline and 2-vinyl-2-oxazoline; and histyrene, vinyltoluene, vinyl chloride, vinylidene chloride,
Vinyl fluoride, vinylidene fluoride, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, ethylene, propylene, butadiene, isoprene, dicyclopentadiene, divinylbenzene, diallylphthalate, etc. can be mentioned, and from these groups Selected 1
Species or mixtures of two or more species can be used. The aqueous resin dispersion (A), which is the first component constituting the cationic aqueous resin composition of the present invention, is obtained by emulsion polymerization of the polymerizable monomer in an aqueous medium using the modified polyamine as an emulsifier. It is something. There is no particular restriction on the amount of modified polyamine used during emulsion polymerization, but it is 0.5 to 20 parts by weight per 100 parts by weight of the polymerizable monomer.
0 parts by weight is preferred. Further, although it is preferable to use the emulsifier such as the modified polyamine alone, conventionally known emulsifiers may be used in combination as long as the features of the present invention are not impaired. Emulsion polymerization can be carried out according to a known method using a known polymerization initiator and various additives if necessary. When obtaining this aqueous resin dispersion (A), if at least one kind of polymerizable monomer is a compound having a functional group that can react with the modified polyamine used as an emulsifier in the present invention, the obtained aqueous resin dispersion ( This is preferable because the performance of A) can be further improved. Examples of functional groups that can react with modified polyamines include carboxyl groups, sulfonic acid groups, hydroxyl groups, epoxy groups, halohydrin groups, amine groups, alkoxysilyl groups, blocked incyanate groups, aziridinyl groups, and oxazoline groups. I can do it. Compounds having these functional groups include polymerizable unsaturated monocarboxylic acids, polymerizable unsaturated polycarboxylic acids, monoester compounds of polymerizable unsaturated polycarboxylic acids, and polymerizable unsaturated monocarboxylic acids among the above polymerizable monomers. Saturated sulfonic acids, hydroxy group-containing unsaturated monomers, epoxy group-containing unsaturated monomers, halohydrin group-containing unsaturated monomers, basic unsaturated monomers,
Organosilicon monomers, blocked incyanate group-containing unsaturated monomers, aziridinyl group-containing unsaturated monomers and oxazoline group-containing unsaturated monomers can be mentioned. The second component constituting the cationic aqueous resin composition of the present invention is a compound (B) having two or more functional groups capable of reacting with the modified polyamine in its molecule. In the process of forming a film, the compound (B) undergoes a crosslinking reaction with the modified polyamine contained in the aqueous resin dispersion (A), which is the first component constituting the resin composition, to form a cured film. K, it brings about improvements in various physical properties including water resistance. Examples of functional groups that can react with modified polyamines include carboxyl groups, sulfonic acid groups, hydroxyl groups, epoxy groups, amino groups, alkoxysilyl groups, blocked incyanate groups, aziridinyl groups, and oxazoline groups. Compounds having two or more of these functional groups in the molecule include dicarboxylic acids or their salts such as maleic anhydride, phthalic anhydride, polyethylene glycol carboxylated at both ends; polyacrylic acid, polymethacrylic acid, and styrene-maleic anhydride. Polycarboxylic acids such as acid copolymers or their salts: Polysulfonic acids such as polyvinyl sulfonic acid and polystyrene sulfonic acid or their salts; ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polyethylene glycol , polypropylene glycol, ethylene oxide-propylene oxide block copolymer, ethylene oxide-propylene oxide-ethylene oxide block copolymer, diols such as hexanediol, octanediol, decanediol; polyols such as saponified products of polyvinyl acetate; ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether,
Triethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, phlopylene gelicol diglycidyl ether, dipropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerol sifulidyl ether, bisphenol A diglycidyl ether, tetrabromobisphenol A Diglycidyl ethers such as diglycidyl ether: succinic acid diglycidyl ester,
Diglycidyl esters such as adipic acid diglycidyl ester; triglycidyl ethers such as glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, 3-methylpentanetriol triglycidyl ether, triglycidyl ether of glycerin ethylene oxide adduct; diglycerol Polyglycidyl ethers such as polyglycidyl ether, sorbitol polyglycidyl ether, polyglycerin polyglycidyl ether, phenol novolac type epoxy resin, cresol novolac type epoxy resin; glycidyl amines such as tetraglycidyl diaminodiphenylmethane and diglycidyl dimethyl hydantoin; ethylene diamine, Polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine, polyamide polyamine which is a condensation product of adipic acid and diethylenetriamine; tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, r- Amitsub is alkoxysilane compounds such as pyrutriethoxysilane and r-glycidoxyglobyltriethoxysilane, or partially hydrolyzed condensates thereof: hexamethylene diisocyanate, tolylene diisocyanate, inphorone diisocyanate, the above diols and tolylene diisocyanate. Blocked diisocyanates such as phenol adducts of diisocyanate compounds such as reactants; 2 moles of ethyleneimine adduct of hexamethylene diisocyanate, 2 moles of ethyleneimine adduct of diphenylmethane diisocyanate, 3 moles of ethyleneimine adduct of trimethylolpropane triacrylate polyfunctional aziridine compounds such as tris(1-aziridinyl)phosphine oxide, tris(1-aziridinyl)triazine; bis(2-oxazolinyl) diethyl ether, bis(2-oxazolinyl) diethyl ether,
Examples include polyfunctional oxazoline compounds such as -oxazolinyl) diethylthioether and m-7 enylene di(2-oxazoline), and one or more selected from these groups can be used. The property of compound (B) is not particularly limited, and it can be used, for example, as a liquid, solid, or aqueous dispersion. The compound (B) is used in an amount of 0.1 to 1000 parts by weight based on 100 parts by weight of the nonvolatile content of the aqueous resin dispersion (A). If the amount of compound (B) used is less than 0.1 part by weight, the crosslinking reaction of the cationic aqueous resin composition will not be sufficient, so improvements in the physical properties of the film such as water resistance cannot be expected; So I don't like it. The cationic aqueous resin dispersion comprising the aqueous resin dispersion (A) and the compound (B) having two or more functional groups capable of reacting with the modified polyamine in the molecule may be used as is for various purposes, If necessary, add a pH adjuster, curing catalyst,
A diluent or the like may be added. (Effects of the Invention) The cationic aqueous resin composition of the present invention comprises as essential components an aqueous resin dispersion (A) and a compound (B) having two or more functional groups capable of reacting with a modified polyamine in its molecule. In addition, since the modified polyamine component contained in the dispersion (A) and the compound (B) have crosslinking reactivity, a film with excellent water resistance and high strength is formed, and it also has cationic properties. Therefore, it forms a film with excellent adhesion to inorganic and organic materials such as metal, glass, cement, plastic, and various textile products. Because of these features, the cationic aqueous resin composition of the present invention is useful in the field of floorboards, such as paper processing, textiles, glass fibers, leather, civil engineering and construction, adhesives, paints, etc. . (Examples) The present invention will be described in detail below with reference to Examples, but the scope of the present invention is not limited only to these Examples. Unless otherwise specified, D%? "wt%" and "parts" indicate parts by weight, respectively. Reference Example 1 45 parts of polyethyleneimine (Epomin 5P-006, manufactured by Nippon Shokubai Chemical Co., Ltd., average molecular weight approximately 600) and carbon were placed in a flask equipped with a dropping funnel, a stirrer, an inert gas inlet tube, a thermometer, and a reflux condenser. 14.7 parts of a mixture of α-olefin epoxides numbered 12 and 14 (AOE-X24, manufactured by Daicel Chemical ■) was charged, heated to 80'C while slowly blowing nitrogen gas, and reacted for 2 hours to form an emulsifier ( 1) was obtained. Reference Examples 2 to 6 Emulsifier (2) was prepared by repeating the same procedure as in Reference Example 1, except that the polyamine and compound (1) were as shown in Table 1.
~(6) was obtained. Reference Example 7 In the same flask as used in Reference Example 1, 100 parts of polyethyleneimine (Evomin 5P-012, manufactured by Nippon Shokubai Chemical Co., Ltd., average molecular weight approximately 1200) and 50 parts of stearic acid were added.
and 70 parts of xylene were heated to 140° C. while slowly blowing nitrogen gas, and dehydration condensation was carried out over a period of 4 hours. After the reaction is complete, xylene is distilled off and the emulsifier (
I gained power. Reference Example 8 In the same flask as used in Reference Example 1, add 1 adipic acid.
46.1 parts of diethylenetriamine, 112.5 parts of diethylenetriamine, and 50 parts of water were heated to 200° C. while slowly blowing nitrogen gas, and dehydration condensation was carried out over 4 hours. After cooling, α-olefin epoxide (AOE
-X24) was added dropwise and reacted at 120°C for 3 hours to obtain emulsifier (8). Reference Example 9 Into the same flask as used in Reference Example 1, 45 parts of polyethyleneimine (SP-006) and 14.7 parts of α-olefin epoxide (AOE-X24) were charged.
reacted in the same way. After cooling, 238.8 parts of water was added and stirred to obtain a homogeneous 20% aqueous solution, and then 97.2 parts of siepichlorohydrin was added dropwise thereto through a dropping funnel. Thereafter, the temperature was maintained at 80° C. and the reaction was carried out for 3 hours to obtain an aqueous solution of emulsifier (9) with a non-volatile content of 38.5%. Reference Example 10 The emulsifier obtained in Reference Example 1 (1
) and 100 parts of water, stirred to make a homogeneous aqueous solution, and adjusted the pH with acetic acid so that the pH was 4.5.
A solution of emulsifier (1) was prepared by diluting the emulsifier (1) with water so that the total amount was 167 parts. Three parts of a 10'% aqueous solution of 2,2'-azobis(2-methylpropanediamine) dihydrochloride as a polymerization catalyst was charged therein, and heated to 55°C while gently blowing nitrogen gas.
Stir to form a homogeneous aqueous solution, and then add 55 to 60 parts of a monomer mixture consisting of 50 parts of methyl methacrylate and 50 parts of butyl acrylate prepared in advance through a dropping funnel.
The mixture was added dropwise at ℃ over 2 hours. Then increase the temperature to 55-60
℃ and further stirred for 1 hour to carry out emulsion polymerization, resulting in a non-volatile content of 39.8% and an aqueous resin dispersion of pi (5,3) [1]
I got it. Reference Examples 11 to 18 Aqueous resin dispersion [2] was prepared by repeating the same operation as in Reference Example 10, except that the monomer mixture composition, the type of emulsifier and the pn adjuster of the emulsifier were changed to the energization shown in Table 2. ~

[9] was obtained. Reference Example 19 Into the same flask as used in Example 1, 13.0 parts of the aqueous solution of the emulsifier (9) obtained in Reference Example 9 and 95 parts of water were charged and stirred to make a uniform aqueous solution, and the pH was 4.5. After adjusting the pH with acetic acid so that the pH was adjusted to 167 parts, the mixture was diluted with water to a total amount of 167 parts. Heat to 55°C while blowing 2° nitrogen gas as a polymerization catalyst, stir to obtain a homogeneous aqueous solution, and then add 10 parts of glycidyl methacrylate, 45 parts of methyl methacrylate, and acrylic acid prepared in advance through a dropping funnel. 55 to 6 parts of a monomer mixture consisting of 45 parts of butyl
The mixture was added dropwise at 0°C over 2 hours. Then increase the temperature to 55-60
℃ and further stirred for 1 hour until the non-volatile content was 40.0%.
An aqueous resin dispersion [10] of H4,8 was obtained. Example 1 Ethylene glycol diglycidyl ether (Tena;-L EX-81) was added as compound (B) to 100 parts as the nonvolatile content of the aqueous resin dispersion [1] obtained in Reference Example 10.
0, manufactured by Nagashio Kasei ■) was added to obtain a cationic aqueous resin composition. Examples 2 to 10 The aqueous resin dispersion, the type and amount of compound (B)
A cationic aqueous resin-containing acid compound was obtained by repeating the same operation as in Example 1, except as shown in the table. Comparative Example 1 In place of the solution of emulsifier (1) in Reference Example 10, 5 parts of dodecyltrimethylammonium chloride was added to 162 parts of water.
Reference Example 1 except that an aqueous emulsifier solution obtained by dissolving in
Repeating the same operation as 0, the non-volatile content was 39.9%, p
A comparative dispersion liquid [1] of H5,5 was obtained. Ethylene glycol diglycidyl ether (Denacol EX-
810. A comparative composition was obtained by adding 10 parts of Nagase Kasei (manufactured by Nagase Kasei). Comparative Example 2 Replacement of the solution of emulsifier (1) in Reference Example 10. A non-volatile To 100 parts of ethylene glycol diglycidyl ether (Tenacol EX-81
0. 10 parts of Nagase Kasei (manufactured by -) were added to obtain comparative composition (2). Example 11 Cationic water-injectable resin compositions (1) to (2) obtained in Examples 1 to 10 and Comparative Examples 1 to 2 and comparative compositions (1) to (2)
was cast on a Teflon plate so that the dry film thickness was 0.2 to 0.3 mm, dried by heating at 80°C for 15 minutes to form a film, and then heated at 120°C for 10 minutes to form a film. A test film was created. The following performance tests were conducted on the obtained films to evaluate the performance of each composition. The evaluation results are shown in Table 4. 1. Water resistance: The test film was cut into an approximately 2α angle and weighed (WO). The film was immersed in deionized water for 3 days, pulled out, and the moisture on the film surface was lightly wiped off before being weighed (Wl). Furthermore, the film was tested for 1 hour at 100° C. The water resistance of the film was evaluated. 2. Film strength: The elongation rate and tensile strength of the film were measured based on the test method described in JIS K-6732. Table 4 Example 12 The cationic aqueous resin compositions obtained in Examples 1 to 10 and Comparative Examples 1 to 2 and the comparative composition 2 were applied to glass plates, aluminum plates, and polycarbonate plates. /%1
The coating was applied using a 6-bar coater, and then heated and dried at 80° C. for 10 minutes to prepare a coated test plate. The following performance tests were conducted on the obtained test plates to evaluate the performance of each composition. The evaluation results are shown in Table 5. 1. Normal adhesion: 1. Using a cutter knife on the coating film.
After cutting 10 si x 10 m grids at ms intervals, pressing the shoe keep and peeling it off vigorously, the peeling state of the grids was graded as ◎, ○, Δ, and ×. ◎ means the percentage of the part that did not peel off is 90-100% ○ means 〃 70-90 inches Δ means
〃 40~70cm× is 〃
0-40chi 2. Water resistant adhesion: The test plate was immersed in deionized water for 1 day, pulled up and the moisture on the coating surface was wiped within 1 minute, and then the adhesion test was carried out in the same manner as the normal adhesion above. I did it. Procedural amendment (voluntary) August 7, 1985 Commissioner of the Patent Office Kuro 1) Mr. Yu Akira 1, Indication of the case 1988 Patent Application No. 64792 2, Name of the invention Cationic aqueous resin composition 3, Amendment Relationship with the case of a person who does
Mr. Nakajima, 4, Agent: 1-2-2 Uchisaiwai-cho, Chiyoda-ku, Tokyo, Japan 1-2-2 Nippon Shokubai Chemical Co., Ltd., Tokyo Branch Telephone: 03-502-1651 ゛--1 5. Details of the application for withdrawal subject to amendment Section 6 of the Detailed Description of the Invention, Contents of Amendment (1) After the last line of page 29 of the specification, the following statement is added in a new line. "Reference Examples 20 to 22 Monomer mixture composition, emulsifier and emulsifier pH!!
Repeat the same operation to prepare aqueous resin dispersions [11] to [
13] was obtained. (2) Table 2 on page 30 of the same is corrected to the understatement in Attachment 1. (3) On page 31, line 7, “Examples 2 to 10”
The text has been corrected to read "Examples 2 to 13." (4) In the 11th line of page 31, "l-times" is corrected to "l-times." (5) Table 3 on page 33 of the same is corrected to the understatement in Attachment 2. (6) In the first line of page 34, "Example 11" is amended to "Example 14." (7) In the second line of page 34, "1-10" is corrected to "1-13." (8) In the third line of page 34, the phrase ``country-times'' has been amended to read ``rcn-times''. (9) Table 4 on page 36 of the same is corrected to the understatement in Attachment 3. al In the first line of page 37 of the same, the phrase "Example 12" is amended to read "Example 15." Ql) In the second line of page 37, "1-10" is corrected to "1-13." (In the 3rd line of page 37 of the same document, "l-country" is corrected to "(Xl-times"). αj Table 5 on page 38 of the same document is corrected in 40 different ways.

Claims (1)

[Claims] 1. Polyamines and/or their derivatives have general formulas ▲ mathematical formulas, chemical formulas, tables, etc. ~4 alkylene group, X is an epoxy group,
It represents an atomic group having a carboxyl group, a vinyl group or an isocyanate group, or a halogen atom, and n represents 0 or an integer from 1 to 30. ) Aqueous resin dispersion (A) obtained by emulsion polymerization of a polymerizable monomer in an aqueous medium using a modified polyamine obtained by reacting a compound represented by (A) with shrimp halohydrin if necessary as an emulsifier, and a modified polyamine in the molecule. A compound (B) having two or more functional groups capable of reacting with a polyamine is an essential component, and 0.1 to 10 parts of the compound (B) is contained per 100 parts by weight of non-volatile content of the aqueous resin dispersion (A).
00 parts by weight of a cationic aqueous resin composition.