JPH0229703B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a novel cationic aqueous film-forming agent. More specifically, we use an aqueous resin dispersion obtained using a modified polyamine having excellent emulsifying power and crosslinking reactivity as an emulsifier, and a specific functional group that can react with the modified polyamine in the molecule.
The present invention relates to a cationic aqueous film-forming agent that is capable of forming a film having excellent water resistance and other physical properties, and is made of a compound having at least 100% of the total number of compounds. The cationic aqueous film-forming agent of the present invention has a cationic particle charge, so it has excellent adsorption and adhesion to various substances, and it foams better than those using known emulsifiers commonly 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 to 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 has been used for various purposes by taking advantage of its characteristics, it has the disadvantage that the film has poor water resistance and strength. [Problems to be Solved by the Invention] The present invention solves the above-mentioned problems that conventional cationic emulsions have, and therefore, the purpose is to provide a cationic emulsion with excellent water resistance and strength. An object of the present invention is to provide an aqueous film-forming agent. [Means and effects for solving the problem] The present inventors have developed a hydrophilic polyamine and/or
Or, a hydrophobic group or a hydrophobic group and a hydrophilic group are introduced into a derivative thereof via a reactive group such as an epoxy group or an isocyanate group, and if necessary, quaternization reaction is performed to make it more hydrophilic and to make it more reactive. A cationic modified polyamine made by reacting epihalohydrin to introduce groups exhibits excellent emulsifying power,
Furthermore, it has been found that modified polyamines have crosslinking properties with compounds having specific functional groups. 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 film-forming agent made of a compound having two or more specific functional groups forms a strong film with excellent water resistance, and furthermore, because it is cationic, it has good adhesion to various materials. It has been discovered that a good film can be formed, and the present invention has been achieved. That is, the present invention provides polyamines and/or derivatives thereof having the general formula R-(OA-) _o X (wherein R represents a hydrocarbon group having 4 to 28 carbon atoms,
represents an alkylene group having 2 to 4 carbon atoms, X represents an atomic group having an epoxy group, a carboxyl group, a vinyl group or an isocyanate group, or a halogen atom, and n represents an integer from 1 to 30. ) and, if necessary, epihalohydrin, using a modified polyamine as an emulsifier.
An aqueous resin dispersion (A) obtained by emulsion polymerization of a polymerizable monomer in an aqueous medium and an aqueous resin dispersion (A) obtained from the group consisting of a hydroxyl group, an epoxy group, an amino group, an alkoxysilyl group, an aziridinyl group, and an oxazoline group in the molecule. The compound (B) contains as an essential component a compound (B) having two or more functional groups capable of reacting with the modified polyamine to be used, and 0.1 to 1000 parts by weight of the compound (B) per 100 parts by weight of the nonvolatile content of the aqueous resin dispersion (A). of the cationic aqueous film forming agent. 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 amino groups. Examples of polyamines include polyalkyleneimines obtained by polymerization or copolymerization of alkyleneimines such as polyalkyleneimines obtained by polymerization of ethyleneimine; ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, (Poly)alkylene polyamines such as pentaethylenehexamine; polyamide polyamines obtained by condensation of polyalkylene imines and/or (poly)alkylene polyamines with polybasic acids such as adipic acid; polyalkylene imines and/or (poly) Examples include polyurea polyamines obtained by reacting alkylene amines and/or alkylene imines with urea; and polyamide polyester polyamines obtained by copolymerizing alkylene imines with acid anhydrides such as phthalic 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. General formula used in the present invention: R-(OA-) _o X (wherein, R, A, X and n are the same as above)
The compound represented by (hereinafter referred to as compound (1))
In the formula, the hydrocarbon group having 4 to 28 carbon atoms corresponding to R in the formula includes a linear or branched alkyl group having 4 to 28 carbon atoms, an (alkyl)aryl group, and a hydrogenated (alkyl) group. Examples include aryl groups and (alkyl)aralkyl groups. the compound
Examples of (1) include n-octyl polyoxyalkylene glycidyl ether having an added mole number of alkylene oxide such as ethylene oxide, propylene oxide, and isobutylene oxide from 1 to 30;
Primary alkyl polyoxyalkylene glycidyl ethers such as n-nonyl polyoxyalkylene glycidyl ether, lauryl polyoxyalkylene glycidyl ether, stearyl polyoxyalkylene glycidyl ether, and 2-ethylhexyl polyoxyalkylene glycidyl ether; having 12 to 14 carbon atoms; Adding 1 to 30 moles of alkylene oxide to a mixture of secondary alcohols,
Further glycidyl etherification, carbon number 10
Secondary alkyl polyoxyalkylene glycidyl ethers, such as those obtained by adding 1 to 30 moles of alkylene oxide to a mixture of 1 to 12 secondary alcohols and further glycidyl etherification; Alkylphenyl polyoxyalkylene glycidyl ethers such as octylphenyl polyoxyalkylene glycidyl ether, nonylphenyl polyoxyalkylene glycidyl ether, lauryl phenyl polyoxyalkylene glycidyl ether, stearyl phenyl polyoxyalkylene glycidyl ether; Octylcyclopentyl polyoxyalkylene glycidyl ether, octylcyclohexyl polyoxyalkylene glycidyl ether, nonylcyclopentyl polyoxyalkylene glycidyl ether, nonylcyclohexyl polyoxyalkylene glycidyl ether, laurylcyclopentyl polyoxyalkylene glycidyl ether, laurylcyclopentyl polyoxyalkylene glycidyl ether, with an addition mole number of 1 to 30. Alkylcycloalkyl polyoxyalkylene glycidyl ethers such as polyoxyalkylene glycidyl ether, stearyl cyclopentyl polyoxyalkylene glycidyl ether, and stearyl cyclohexyl polyoxyalkylene glycidyl ether; the number of moles of alkylene oxide added is from 1 to
30 alkylbenzyl polyoxyalkylene glycidyl ethers such as octylbenzyl polyoxyalkylene glycidyl ether, nonylbenzyl polyoxyalkylene glycidyl ether, laurylbenzyl polyoxyalkylene glycidyl ether, stearylbenzyl polyoxyalkylene glycidyl ether; octyl glycidyl ether, lauryl glycidyl ether Glycidyl ethers of higher alcohols such as ether, stearyl glycidyl ether, 2-ethylhexyl glycidyl ether; glycidyl ethers of alkyl phenols such as octylphenyl glycidyl ether, nonylphenyl glycidyl ether, lauryl phenyl glycidyl ether, stearyl phenyl glycidyl ether Glycidyl ethers of alkylcycloalkanols such as octylcyclopentylglycidyl ether, octylcyclohexylglycidyl ether, nonylcyclopentylglycidyl ether, nonylcyclohexylglycidyl ether, laurylcyclopentylglycidyl ether, stearylcyclopentylglycidyl ether, stearylcyclohexylglycidyl ether; octylbenzylglycidyl ether , nonylbenzyl glycidyl ether, lauryl benzyl glycidyl ether,
Glycidyl ethers of alkylbenzyl alcohols such as stearyl benzyl glycidyl ether; 1,2-epoxy alkanes such as α-olefin epoxides having 12 or 14 carbon atoms and α-olefin epoxides having 16 or 18 carbon atoms; octyl isocyanate, octadecyl isocyanate , alkyl isocyanates such as octadecyl isocyanate; monoisocyanate compounds obtained by reacting alcohols such as octanol, lauryl alcohol, stearyl alcohol, or alkylene oxide adducts of these alcohols with tolylene diisocyanate; octanol, lauryl alcohol , alcohols such as stearyl alcohol, or halides in which the terminal acid group of the alkylene oxide adduct of these alcohols is substituted with a halogen atom such as chlorine, bromine, or iodine; lauric acid, myristic acid, palmitic acid, stearic acid, etc. of saturated fatty acids;
Unsaturated fatty acids such as oleic acid, linoleic acid, linolenic acid, eleostearic acid; acrylic acid 2
- Acrylic acid alkyl esters such as -ethylhexyl, lauryl acrylate, and stearyl acrylate can be mentioned, and one or more types selected from these groups can be used. The amount of the above 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 preferable to use 0.01 to 1 molecule of compound (1) per amine hydrogen in the polyamine and/or its derivative. Furthermore, the modified polyamine obtained by the above reaction can be further reacted with epihalohydrin if necessary. Epihalohydrins that can be used include epichlorohydrin, epibromohydrin,
Examples include epiiodohydrin, but epichlorohydrin is preferable. When 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 from 0.1 to 1 per amine hydrogen in the polyamine and/or its derivative 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 the polyamine and/or
or a derivative thereof, may be appropriately selected depending on the properties and reactivity of compound (1) and epihalohydrin, and if necessary, an appropriate catalyst may be used. It is also possible to adjust the pH by adding an acid to the obtained modified polyamine. The above acids include hydrochloric acid, sulfuric acid,
Inorganic acids such as phosphoric acid, formic acid, acetic acid, acrylic acid,
Organic acids such as 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, thus forming a cationic aqueous film having excellent performance according to the present invention. The present invention provides an aqueous resin dispersion (A) which is the first component constituting the forming agent. The polymerizable monomer used in the present invention is not particularly limited as long as it has 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, isopropyl, 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 (meth)acrylamide, vinylpyridine, vinylimidazole, Basic unsaturated monomers such as vinylpyrrolidone; (meth)acrylic acid and ethylene glycol, 1,3-butylene glycol, 1,
Polyfunctional (meth)acrylic acids containing two or more polymerizable unsaturated groups in the molecule, such as polyesters with polyhydric alcohols such as 6-hexane glycol, neopentyl glycol, polyethylene glycol, polypropylene glycol, and trimethylolpropane. Esters; (meth)acrylamide,
Methylolated (meth)acrylamide, 1 carbon number
(meth)acrylamides such as alkoxymethylol (meth)acrylamide; unsaturated monocarboxylic acids and their salts such as (meth)acrylic acid and crotonic acid; unsaturated polyesters such as itaconic acid, maleic acid, and fumaric acid; carboxylic acids,
Its salts and monoester compounds of the acid; vinyl sulfonic acid, styrene sulfonic acid, (meth)
Polymerizable unsaturated sulfonic acids and their salts such as sulfoethyl acrylate; hydroxyl groups such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and monoesters of acrylic acid or methacrylic acid with polypropylene glycol or polyethylene glycol Containing unsaturated monomers; Epoxy group-containing unsaturated monomers such as glycidyl (meth)acrylate; Halohydrin group-containing unsaturated monomers such as 2-hydroxy-3-chloropropyl (meth)acrylate ;
Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxyethoxysilane, γ
- Organosilicon monomers such as (meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane, γ-(meth)acryloxypropylmethyldimethoxysilane, allyltriethoxysilane, trimethoxysilylpropylallylamine, etc. unsaturated monomers containing blocked isocyanate groups such as phenol adducts of isocyanate ethyl (meth)acrylate; unsaturated monomers containing aziridinyl groups such as (meth)acryloylaziridine and (meth)acryloyloxyethylaziridine; oxazoline group-containing unsaturated monomers such as 2-isopropenyl-2-oxazoline and 2-vinyl-2-oxazoline; and styrene, vinyltoluene, vinyl chloride, vinylidene chloride, vinyl fluoride, and fluoride. vinylidene, acrylonitrile, methacrylonitrile, vinyl acetate, ethylene, propylene, butadiene,
Examples include isoprene, dicyclopentadiene, divinylbenzene, diallyl phthalate, etc., and one type or a mixture of two or more types selected from these groups can be used. The aqueous resin dispersion (A), which is the first component constituting the cationic aqueous film-forming agent 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 limit to the amount of modified polyamine used during emulsion polymerization, but it is 0.5 to 100 parts by weight of the polymerizable monomer.
200 parts by weight is preferred. Moreover, it is preferable to use the emulsifier made of the modified polyamine alone,
Conventional known emulsifiers can also be used in combination, as long as they do not impair the features of the present invention. 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 of the polymerizable monomers is a compound having a functional group that can react with the modified polyamine used as an emulsifier in the present invention, the resulting aqueous resin dispersion
This is preferable because the performance of (A) can be further improved. Functional groups that can react with modified polyamines include:
Examples include carboxyl group, sulfonic acid group, hydroxyl group, epoxy group, halohydrin group, amino group, alkoxysilyl group, blocked isocyanate group, aziridinyl group, and oxazoline group. 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, hydroxyl group-containing unsaturated monomers, epoxy group-containing unsaturated monomers, halohydrin group-containing unsaturated monomers, basic unsaturated monomers, organosilicon monomers, Mention may be made of unsaturated monomers containing blocked isocyanate groups, unsaturated monomers containing aziridinyl groups, and unsaturated monomers containing oxazoline groups. The second component constituting the cationic aqueous film-forming agent of the present invention is a compound (B) having two or more specific 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. It brings about improvements in various physical properties including water resistance. Examples of functional groups that can react with modified polyamines in the present invention include hydroxyl groups, epoxy groups, amino groups, alkoxysilyl groups, aziridinyl groups, and oxazoline groups. Compounds having two or more of these functional groups in the molecule include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polyethylene glycol, polypropylene glycol, and ethylene oxide-propylene oxide block copolymer. , ethylene oxide-propylene oxide-ethylene oxide block copolymer, diols such as hexanediol, octanediol, and decanediol; polyols such as saponified polyvinyl acetate; ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol Diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerol diglycidyl ether, bisphenol A diglycidyl ether, tetrapromobisphenol A diglycidyl ether, etc. diglycidyl ethers; diglycidyl esters such as succinic acid diglycidyl ester and adipic acid diglycidyl ester; glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, 3-methylpentanetriol triglycidyl ether,
Triglycidyl ethers such as triglycidyl ether of glycerin ethylene oxide adduct;
Polyglycidyl ethers such as diglycerol polyglycidyl ether, sorbitol polyglycidyl ether, polyglycerin polyglycidyl ether, phenol novolac type epoxy resin, cresol novolac type epoxy resin; tetraglycidyl diaminodiphenylmethane, diglycidyl dimethyl hydantoin, etc. Glycidylamines; Polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine, polyamide polyamine which is a condensation product of adipic acid and diethylenetriamine; tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyl Alkoxysilane compounds such as triethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, or partially hydrolyzed condensates thereof; 2-mole ethyleneimine adduct of hexamethylene diisocyanate, diphenylmethane diisocyanate 2 mole adduct of ethyleneimine, 3 ethyleneimine of trimethylolpropane triacrylate
Polyfunctional aziridine compounds such as molar adducts, tris(1-aziridinyl)phosphine oxide, tris(1-aziridinyl)triazine; bis(2-oxazolinyl) diethyl ether, bis(2-oxazolinyl) diethylthioether,
Examples include polyfunctional oxazoline compounds such as m-phenylene 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. Compound (B)
is used in an amount of 0.1 to 1000 parts by weight based on 100 parts by weight of nonvolatile content of the aqueous resin dispersion (A). Compound
If the amount of (B) used is less than 0.1 parts by weight, the crosslinking reaction of the cationic aqueous film-forming agent will not be sufficient, so improvements in the physical properties of the film such as water resistance cannot be expected; If the amount is too large, disadvantages such as a decrease in storage stability of the cationic aqueous film forming agent occur, which is not preferable. A cationic aqueous film-forming agent consisting of the aqueous resin dispersion (A) and a compound (B) having two or more specific functional groups capable of reacting with a modified polyamine in its molecule,
It may be used as it is for various purposes, and if necessary, a PH regulator, curing catalyst, diluent, etc. may be added. [Effects of the Invention] The cationic aqueous film-forming agent of the present invention contains as essential components an aqueous resin dispersion (A) and a compound (B) having two or more specific functional groups capable of reacting with a modified polyamine in its molecule. Because 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 furthermore, the cationic Because it is a gender,
It forms films with excellent adhesion to various inorganic and organic materials such as metals, glass, cement, plastics, and various textile products. Because of these features, the cationic aqueous film-forming agent of the present invention is useful in a wide range of fields such as paper processing, fibers, glass fibers, leather, civil engineering and construction, adhesives, paints, etc. [Examples] The present invention will be explained in detail with reference to Examples below, but the scope of the present invention is not limited only to these Examples. In the examples, % means % by weight and parts means parts by weight unless otherwise specified. Reference Example 1 Polyethyleneimine (Epomin SP-006, Nippon Shokubai Chemical Co., Ltd.) was placed in a flask equipped with a dropping funnel, a stirrer, an inert gas inlet tube, a thermometer, and a reflux condenser
Co., Ltd., average molecular weight approximately 600) 45 parts, carbon numbers 12 and 14
A mixture of α-olefin epoxides (AOE-
14.7 parts of
The reaction was carried out for 2 hours to obtain emulsifier (1). Reference Examples 2 to 6 Emulsifiers (2) to (6) were obtained by repeating the same operations as in Reference Example 1, except that the polyamine and compound (1) were as shown in Table 1. Reference Example 7 Into the same flask as used in Reference Example 1, 100 parts of polyethyleneimine (Epomin SP-012, manufactured by Nippon Shokubai Chemical Co., Ltd., average molecular weight approximately 1200), 50 parts of stearic acid, and 70 parts of xylene were charged. , heat to 140℃ while gently blowing nitrogen gas,
Dehydration condensation was carried out over time. After the reaction was completed, xylene was distilled off to obtain emulsifier (7). Reference Example 8 Into the same flask as used in Reference Example 1, 146.1 parts of adipic acid, 112.5 parts of diethylenetriamine, and 50 parts of water were charged, heated to 200°C while gently blowing nitrogen gas, and dehydrated and condensed over 4 hours. I went. After cooling, 39.2 parts of α-olefin epoxide (AOE-X24) was added dropwise from the dropping funnel.
Emulsifier (8) was obtained by reacting at 120°C for 3 hours. 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 and reacted in the same manner as in Reference Example 1. After cooling, 238.8 parts of water was added and stirred to obtain a homogeneous 20% aqueous solution, and then 97.2 parts of epichlorohydrin was added dropwise thereto from 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%.

【table】

[Table] Reference Example 10 5 parts of the emulsifier (1) obtained in Reference Example 1 and 100 parts of water were charged into a flask equipped with a dropping funnel, a stirrer, an inert gas inlet tube, a thermometer, and a reflux condenser, and the mixture was stirred. A homogeneous aqueous solution was prepared, the pH was adjusted to 4.5 with acetic acid, and then diluted with water to a total amount of 167 parts to prepare a solution of emulsifier (1). Three parts of a 10% aqueous solution of 2,2'-azobis(2-methylpropanediamine) dihydrochloride was added thereto as a polymerization solvent, heated to 55°C while gently blowing nitrogen gas, and stirred to form a homogeneous aqueous solution. Then, a monomer mixture prepared in advance consisting of 50 parts of methyl methacrylate and 50 parts of butyl acrylate was added dropwise thereto from a dropping funnel at 55 to 60°C over 2 hours.
After that, the temperature was maintained at 55-60℃ and stirred for another hour to emulsion polymerize, resulting in a non-volatile content of 39.8% and a pH of 39.8%.
Aqueous resin dispersion [1] of 5.3 was obtained. Reference Examples 11-18 Aqueous resin dispersions [2]-

[9] Obtained. Reference Example 19 Into the same flask as used in Reference 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, stirred to make a homogeneous aqueous solution, and diluted with acetic acid so that the pH was 4.5. After adjusting the pH, it was diluted with water so that the total amount was 167 parts. 2,2′-azobis(2-methylpropanediamine) dihydrochloride as a polymerization catalyst
Add 3 parts of a 10% aqueous solution, heat to 55°C while gently blowing nitrogen gas, stir to make a homogeneous aqueous solution, and then add 10 parts of glycidyl methacrylate and methyl methacrylate, which had been prepared in advance, through a dropping funnel. A monomer mixture consisting of 45 parts and 45 parts of butyl acrylate was added dropwise at 55 to 60°C over 2 hours. Thereafter, the temperature was maintained at 55 to 60°C and the mixture was further stirred for 1 hour to obtain an aqueous resin dispersion [10] with a nonvolatile content of 40.0% and a pH of 4.8. Reference Examples 20-22 Aqueous resin dispersion [11]- [13] Obtained.

【table】

[Table] Example 1 Ethylene glycol diglycidyl ether (Denacol EX-810, Nagase Kasei Co., Ltd.) was added as compound (B) to 100 parts as the nonvolatile content of the aqueous resin dispersion [1] obtained in Reference Example 10. A cationic aqueous film-forming agent was obtained. Examples 2 to 13 The same operations as in Example 1 were repeated except that the aqueous resin dispersion, the type and amount of compound (B) added were as shown in Table 3, and the cationic aqueous film forming agent ~ was prepared. Obtained. Comparative Example 1 Instead of the solution of emulsifier (1) in Reference Example 10,
A comparative dispersion [1] with a non-volatile content of 39.9% and a pH of 5.5 was prepared by repeating the same operation as in Reference Example 10, except for using an aqueous emulsifier solution obtained by dissolving 5 parts of dodecyltrimethylammonium chloride in 162 parts of water. I got it.
As the non-volatile content of the obtained comparative dispersion [1]
For 100 parts, ethylene glycol diglycidyl ether (Denacol EX-810, manufactured by Nagase Kasei Co., Ltd.)
10 parts were added to obtain a comparative film former. Comparative Example 2 Instead of the solution of emulsifier (1) in Reference Example 10,
A non-volatile min 40.0
%, PH6.3 comparative dispersion [2] was obtained. To 100 parts of the nonvolatile content of the obtained comparative dispersion [2], 10 parts of ethylene glycol diglycidyl ether (Denacol EX-810, manufactured by Nagase Kasei Co., Ltd.) was added to form a comparative film forming agent. Obtained.

【table】

[Table] Example 14 The cationic aqueous film forming agents obtained in Examples 1 to 13 and Comparative Examples 1 to 2 and the comparative film forming agent were placed on a Teflon plate with a dry film thickness of 0.2.
Casting to ~0.3mm and at 80℃
A film was formed by heating and drying for 15 minutes, and then heated at 120℃ for 10 minutes.
A test film was prepared by heating for a minute. The following performance tests were conducted on the obtained films to evaluate the performance of each film forming agent. The evaluation results are shown in Table 4. 1 Water resistance: The test film was cut into approximately 2 cm square pieces and weighed (W ₀ ). The film was immersed in deionized water for 3 days, pulled out, and the moisture on the film surface was lightly wiped off before weighing (W ₁ ). Furthermore, the film was dried at 100℃ for 1 hour,
After cooling, it was weighed (W ₂ ). Calculate the water absorption rate and elution rate using the following formula,
The water resistance of the test film was evaluated. Water absorption rate (%) = W ₁ - W ₀ /W ₀ ×100 Elution rate (%) = W ₀ -W ₂ /W ₀ ×100 2 Film strength: Elongation rate of the film based on the test method described in JIS K-6732 and tensile strength was measured.

[Table] Example 15 The cationic aqueous film forming agents obtained in Examples 1 to 13 and Comparative Examples 1 to 2 and the comparative film forming agent were applied to glass plates, aluminum plates (), and polycarbonate plates. The coating was applied using a 16-bar coater, then heated and dried at 80°C for 10 minutes to form a film, and then heated at 120°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 film forming agent. The evaluation results are shown in Table 5. 1 Normal adhesion: Use a cutter knife to cut 10mm x 10mm gongs on the coating film at 1mm intervals, press cellophane tape, and then peel it off vigorously and mark the peeling status with ◎, 〇, △, and ×. Scored. ◎ indicates the percentage of the area that did not peel off is 90-100% 〇 indicates the percentage of the area that did not peel off 70-90% △ indicates the percentage of the area that did not peel off 40-70% × indicates the percentage of the area that did not peel off The ratio is 0 to 40%. 2. Water resistant adhesion: Adhesion test was conducted in the same manner as the normal adhesion described above, by immersing the test plate in deionized water for 1 day, pulling it out, and wiping off the water on the coating surface within 1 minute. I went to

【table】

Claims (1)

[Scope of Claims] 1 A polyamine and/or a derivative thereof having the general formula R-(OA-) _o X (wherein R represents a hydrocarbon group having 4 to 28 carbon atoms,
represents an alkylene group having 2 to 4 carbon atoms, X represents an atomic group having an epoxy group, a carboxyl group, a vinyl group or an isocyanate group, or a halogen atom, and n represents 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 The essential component is a compound (B) having two or more functional groups capable of reacting with a modified polyamine selected from the group consisting of a polyamine, an epoxy group, an amino group, an alkoxysilyl group, an aziridinyl group, and an oxazoline group, and is dispersed in an aqueous resin. A cationic aqueous film-forming agent containing 0.1 to 1000 parts by weight of the compound (B) per 100 parts by weight of the nonvolatile content of the liquid (A).