JPS62215605A - Cationic aqueous resin dispersion - Google Patents

Abstract

PURPOSE:The titled dispersion capable of forming a film having improved water resistance and high strength, by subjecting a polymerizable monomer to emulsion polymerization by the use of a specific modified polyamine having improved emulsifying power and crosslinking reactivity as an emulsifying agent. CONSTITUTION:One or more polymerizable monomers (e.g., acrylic acid, etc.) are subjected to emulsion polymerization in an aqueous medium by the use of a modified polyamine obtained by reacting a polyamine (e.g. ethylenediamine, etc.) and/or a derivative thereof with usually 0.01-1 molecule based on one amine hydrogen of the polyamine(derivative) of a compound (e.g. ethylene oxide, etc.) shown by the formula R-(OA)n-X (R is 4-28C hydrocarbon; A is 2-4C alkylene; X is atomic group containing epoxy group, carboxyl group, vinyl group or isocyanate group or halogen; n is 0-30) as an emulsifying agent to give the aimed dispersion. USE:Useful for coating or adhesion in fiber processing, leather processing, etc.

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a novel cationic aqueous resin dispersion. More specifically, it relates to a cationic aqueous resin dispersion that can form a film with excellent physical properties including water resistance, which is obtained by using a cationic emulsifier that has excellent emulsifying power and crosslinking reactivity. be. The cationic aqueous resin dispersion of the present invention has cationic particle charges, so it has excellent adsorption and adhesion to various substances, and it foams better than those using known emulsifiers that are 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 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 emulsifiers such as dodecyltrimethylammonium chloride and stearyltrimethylammonium chloride, and cationic emulsions obtained by emulsion polymerization of vinyl compounds in the presence of these emulsifiers have been known. Although it has been used for various purposes to take advantage of this fact, 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, its purpose is to provide a film with excellent water resistance and strength and emulsification. An object of the present invention is to provide a cationic aqueous resin dispersion having excellent stability during polymerization and stability during storage. (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 its derivative by adding an epoxy group, a carboxyl group, or an isocyanate group. It has been discovered that a cationic modified polyamine introduced through a reactive group such as a group exhibits excellent emulsifying power, and that the modified polyamine also has crosslinking properties with a compound having a specific functional group. Ta. Furthermore, when the modified polyamine is used as an emulsifier in emulsion polymerization of polymerizable monomers, an aqueous resin dispersion can be produced with good stability during polymerization, and the obtained aqueous resin dispersion has excellent stability during storage. The present inventors have discovered that it 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, and has thus arrived at the present invention. That is, the present invention provides polyamines and/or derivatives thereof,
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 an isocyanate group, or a halogen atom, and n represents 0 or an integer from 1 to 30. ) A cationic aqueous resin dispersion obtained by emulsion polymerization of one or more polymerizable monomers in an aqueous medium using a modified polyamine obtained by reacting a compound represented by the following as an emulsifier. . 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 polyethyleneimine obtained by polymerization or copolymerization of alkyleneimines such as polyethyleneimine obtained by polymerization of ethyleneimine; ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc. (Poly)alkylene polyamines such as; 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) alkylene polyamines and/ Or polyurethane obtained by reaction of alkyleneimine and urea: Polyamine:
Examples include polyamide polyester polyamines obtained by copolymerization of alkylene imine and 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)) represented by the general formula % formula %) (in which R, A, X and n are the same as above) used in the present invention, OR in the formula Corresponding hydrocarbon groups having 4 to 28 carbon atoms include linear or branched alkyl groups having 4 to 28 carbon atoms, (alkyl)aryl groups, (alkyl)hydrogenated aryl groups, (alkyl)aralkyl groups, etc. can be mentioned. As the compound (1), the number of moles of alkylene oxide added is 1 to 3, such as ethylene oxide, propylene oxide, isobutylene oxide, etc.
0 n-octyl polyoxyalkylene glycidyl ether, n-nonyeloxyalkylene glycidyl ether, lauryl polyoxyalkylene glycidyl ether, stearyl polyoxyalkylene glycidyl ether, 2-ethylhexyl polyoxyalkylene glycidyl ether, etc. Alkyl polyoxyalkylene glycidyl ethers; mixtures of secondary alcohols having 12 to 14 carbon atoms added with 1 to 30 moles of alkylene oxide and further glycidyl etherified; mixtures of secondary alcohols having 10 to 12 carbon atoms; Secondary alkyl polyoxyalkylene glycidyl ethers, such as those obtained by adding 1 to 30 moles of alkylene oxide to and further glycidyl etherification: Octylphenyl polyoxyalkylene glycidyl ethers with an added mole of alkylene oxide of 1 to 30. , nonylphenyl polyoxyalkylene glycidyl ether, lauryl phenyl polyoxy alkylene glycidyl ether, stearyl phenyl polyoxyalkylene glycidyl ether, etc.; Octylshift tetrapentyl polyoxyalkylene glycidyl ether, octylcyclohexyl polyoxyalkylene glycidyl ether, nonylcyclopentyl polyoxyalkylene glycidyl ether, nonylcyclohexyl polyoxyalkylene glycidyl ether, 2urylcyclopentyl polyoxyalkylene glycidyl ether, laurylcyclohexyl polyoxyalkylene glycidyl ether Alkylcycloalkyl polyoxyalkylene glycidyl ethers such as ether, stearyl cyclopentyl polyoxyalkylene glycidyl ether, stearyl cyclohexyl polyoxyalkylene glycidyl ether; octylbenzyl polyoxyalkylene glycidyl ether having an additional mole number of alkylene oxide of 1 to 30; Alkylbenzyl polyoxyethylene glycidyl ethers such as nonylbenzyl polyoxyalkylene glycidyl ether, laurylbenzyl polyoxyalkylene glycidyl ether, stearylbenzyl polyoxyalkylene glycidyl ether; octyl glycidyl ether, lauryl glycidyl ether, stearyl glycidyl ether, 2 - glycidyl ethers of higher alcohols such as ethylhexyl glycidyl ether;
Octylphenyl glycidyl ether, nonylphenyl glycidyl ether, 7')! Glycidyl ethers of alkylphenols such as J ruphenylcricidyl ether, stearyl phenylglycidyl ether, etc.; octylcyclopentylglycidyl ether, octylcyclohexylglycidyl ether, nonylcyclohentylglycidyl ether, nonylcyclohexylglycidyl ether, 2urylcyclopentylglycidyl ether Glycidyl ethers of cycloalkanols in alkali such as ether, lauryl cyclohexyl glycidyl ether, stearyl cyclopentyl glycidyl ether, stearyl cyclohexyl glycidyl ether, etc.;
Glycidyl ethers of alkylbenzyl alcohols such as octylbenzylglycidyl ether, nonylbenzylglycidyl ether, laurylbenzylglycidyl ether, stearylbenzylglycidyl ether; α-olefin epoxides having 12 or 14 carbon atoms;
1,2-epoxyalkanes such as α-olefin epoxides having 16 or 18 carbon atoms; alkyl isocyanates such as octyl isocyanate, decyl isocyanate, octadecyl isocyanate, etc.; such as octatool, lauryl alcohol, stearyl alcohol, etc. Monoisocyanate compounds obtained by reacting alcohols or alkylene oxide adducts of these alcohols with diisocyanates such as tolylene diisocyanate; alcohols such as octatool, lauryl alcohol, stearyl alcohol, etc.
halides in which the terminal hydroxyl group of alkylene oxide adducts of these alcohols is substituted with halogen atoms such as chlorine, bromine, and iodine; saturated fatty acids such as lauric acid, myristic acid, palmitic acid, and stearic acid; niolein acids, unsaturated fatty acids such as linoleic acid, lylunic acid, eleostearic acid, etc. Niacrylic 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 above-mentioned compound used to obtain the modified polyamine used in the present invention is not particularly limited, but in order to develop sufficient surface activity, K is 0 to 0 per amine hydrogen in the polyamine and/or its derivative. It is preferable to use one molecule of compound (1) from 01. There are no particular restrictions on the reaction conditions for obtaining the modified polyamine used in the present invention, and the properties and reaction of compound (1) with the polyamine and/or its derivatives are not particularly limited. The acid may be selected as appropriate depending on the properties, and if necessary, an appropriate catalyst may be used.Furthermore, it is also possible to add Shun to the obtained modified polyamine to adjust the pH.As the above acid, hydrochloric acid Inorganic acids such as sulfuric acid, phosphoric acid, etc., and organic acids such as formic acid, acetic acid, acrylic acid, methacrylic acid, etc. can be used.The emulsifier made of the modified polyamine thus obtained has excellent emulsifying power, The present invention provides a wide variety of polymerizable fat dispersions.The polymerizable monomer used in the present invention is not particularly limited as long as it contains a polymerizable unsaturated group, but examples include: C 1 to 18 linear or branched aliphatic such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, octyl, 2-ethylhexyl, diuryl, stearyl or cyclohexyl esters of acrylic or methacrylic acid; (Meth)acrylic acid esters which are ester compounds of alkyl alcohol or alicyclic alkyl alcohol and acrylic acid or methacrylic acid: (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, itaconic acid or maleic acid. Polymerizable unsaturated carboxylic acids and their salts, such as acid or monoesters of fumaric acid; Polymerizable unsaturated sulfonic acids and their salts, such as vinyl sulfonic acid, styrene sulfonic acid, sulfoethyl (meth)acrylate, etc.; (meth)aminoethyl acrylate, (
Basic unsaturated monomers such as dimethylaminoethyl meth)acrylate, dimethylaminoethyl (meth)acrylamide, vinylpyridine, vinylimidazole, vinylpyrrolidone, etc.; hydroxyethyl (meth)acrylate, (meth)acrylic acid Hydroxyl group-containing unsaturated monomers such as hydroxypropyl, monoesters of acrylic acid or methacrylic acid and polypropylene glycol or polyethylene glycol; epoxy group-containing unsaturated monomers such as glycidyl (meth)acrylate, etc.
rJ 凰8 (k German: r ivy) Ryoroku 11 layer 9-reo Unsaturated monomers containing a halohydrin group such as roxy 3-chloropropyl; phenolic adduct of incyanatoethyl (meth)acrylate Blocked isocyanate group-containing unsaturated monomers such as (meth)acryloylaziridine, (meth)acryloyloxyethylaziridine, etc.; aziridinyl group-containing unsaturated monomers such as 2-propenyl-2-oxatholine , 2-vinyl-2
- Unsaturated monomers containing oxazoline groups, such as oxazoline; toethylene glycol acrylic or methacrylate, 1.3-7" ethylene glycol, 11/, 1
．． 6-hexane glycol, neopentyl glycol,
Contains two or more polymerizable unsaturated groups in the molecule, such as diesters with dihydric alcohols such as polyethylene glycol and polypropylene glycol, triesters between acrylic acid or methacrylic acid and trihydric alcohols such as trimethylolpropane, etc. Polyfunctional (meth)acrylic acid esters: (meth)acrylamide, methylolated (meth)acrylamide, alkoxymethylolated (meth)acrylamide having 1 to 4 carbon atoms, etc.
meth)acrylamides; vinyltrimethoxysilane,
Organosilicon monomers such as r-(,meth)acryloxypropyltrimethoxysilane, allyltriethoxysilane, trimethoxysilylpropylallylamine, etc.; and styrene, vinyltoluene, vinyl chloride, vinylidene chloride, vinyl fluoride, Vinylidene fluoride, acrylonitrile, methasilylnitrile, vinyl acetate, vinyl propionate, ethylene, propylene, butadiene, imbrene,
Dicyclobentadiene, divinylbenzene, diallyl phthalate, etc. can be mentioned, and 1111 selected from these groups or a mixture of two or more types can be used. The cationic aqueous resin dispersion of the present invention uses the above-mentioned modified polyamine as an emulsifier to obtain 1 al of the polymerizable monomer.
Alternatively, it is obtained by emulsion polymerization of 2 or more parts in an aqueous medium. Emulsion polymerization can be carried out according to a known method using a known polymerization initiator and various other additives if necessary. The amount of the modified polyamine used as an emulsifier during emulsion polymerization is not particularly limited, but it is preferably used in the range of 0.5 to 200 parts by weight per 100 parts by weight of the polymerizable monomer. Further, although it is preferable to use the emulsifier such as the modified polyamine alone, it is free to use conventionally known emulsifiers in combination to the extent that the characteristics of the present invention are not impaired. Furthermore, after emulsion polymerization, a pH adjuster, a curing catalyst, a diluent, etc. can be added if necessary. The cationic aqueous resin dispersion of the present invention thus obtained has characteristics such as excellent adsorption and adhesion to various substances, low foaming, and excellent long-term emulsion stability. However, if at least one of the polymerizable monomers used to prepare the thionic aqueous resin dispersion is a compound having a functional group that can react with the modified polyamine used in the present invention, This is preferred because the performance of the resulting cationic aqueous resin dispersion can be further improved. Examples of functional groups that can react with modified polyamines include carboxyl groups, sulfonic acid groups, aziridinyl groups, oxazoline groups, hydroxyl groups, epoxy groups, halohydrin groups, blocked isocyanate groups, and alkoxysilyl groups. Examples of the compound having a functional group include polymerizable unsaturated carboxylic acids, aziridinyl group-containing unsaturated monomers, oxazoline group-containing unsaturated monomers, and hydroxyl group-containing unsaturated monomers among the polymerizable monomers. monomers, halohydrin group-containing unsaturated monomers, blocked isocyanate group-containing unsaturated monomers, epoxy group-containing unsaturated monomers, and organosilicon monomers. (Effects of the Invention) The cationic aqueous resin dispersion of the present invention has excellent stability during storage and uses a crosslinking emulsifier, so it forms a film with excellent water resistance and high strength. Because of its high adhesion properties, 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 resin dispersion of the present invention can be used in paper processing, textiles, glass fibers, leather, civil engineering and construction,
It is useful in a wide range of fields such as adhesives and paints. (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. In the examples, unless otherwise specified, "limitations" and "parts" indicate weight % and parts, respectively. Reference Example 1 45 parts of polyethyleneimine (Epomin 5P-006, manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd., average molecular weight approximately 600) was 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 having 12 and 14 carbon atoms (AOE-X24, Daicel Chemical Co., Ltd.) was charged, heated to 80°C while gently blowing nitrogen gas, and reacted for 2 hours. Emulsifier (1) was obtained. Reference Examples 2 to 6 Emulsifier (2) was obtained by repeating the same operation 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 4 hours. After the reaction is complete, xylene is distilled off and the emulsifier (7
) was obtained. 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 charged, and heated to 200° C. while slowly blowing nitrogen gas, and complete dehydration condensation was carried out over 4 hours. After cooling, add α-olefin epoxide (AOE-
39.2 parts of 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, 60 parts of polyethyleneimine (Evomin 5P-006) and 19.6 parts of α-olefin epoxide (AOE-X24) were charged, and reacted in the same manner as in Reference Example 1. Ta. After cooling, 179.2 parts of water was added and stirred to obtain a homogeneous aqueous solution, which was then poured into a dropping funnel with the previously prepared acrylamide 49.8
An acrylamide aqueous solution consisting of 112.1 parts and 112.1 parts of water was added dropwise and reacted at 50°C for 4 hours to reduce the nonvolatile content to 30.7 parts.
An aqueous solution of emulsifier (9) was obtained. Example 1 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.
It was diluted 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, heated to 55°C while gently blowing nitrogen gas, and stirred to form a uniform aqueous solution. A monomer mixture consisting of 50 parts of methyl methacrylate and 50 parts of butyl acrylate, which had been prepared in advance through a dropping funnel, was added dropwise thereto over a period of 2 hours at 55 to 60°C. Then, maintain the temperature at 55-60°C,
After stirring for an additional hour, the non-volatile content was 39.8% and the pH was 5.
A cationic aqueous resin dispersion [1] of , 3 was obtained. The same operations as in Examples 2 to 9 were repeated to prepare a cationic aqueous resin dispersion [
2]～

[9] was obtained. Example 10 Into the same flask as used in Example 1, 16.3 parts of the aqueous solution of emulsifier (9) obtained in Reference Example 9 and 90 parts of water were charged and stirred to make a homogeneous aqueous solution, and the pH was 4.5. After adjusting the pH with acetic acid so that the result was as follows, it was diluted with water so that the total amount was 167 parts. 2,2'-azobis(
Add 3 parts of a 10% aqueous solution of 2-methylpropanediamine) dihydrochloride, and add 3 parts of a 10% aqueous solution of 2-methylpropanediamine) dihydrochloride.
A monomer mixture consisting of 10 parts of glycidyl methacrylate, 45 parts of methyl methacrylate, and 45 parts of butyl acrylate was heated to 5°C and stirred to form a homogeneous aqueous solution, and then added through a dropping funnel. was added dropwise at 55 to 60°C over 2 hours. After that, the temperature was maintained at 55-60°C and stirred for an additional 1 hour to achieve a non-volatile content of 39.9%%p.
A cationic aqueous resin dispersion [10] of H5,2 was obtained. Comparative Example 1 The same procedure as in Example 1 was performed, except that an aqueous emulsifier solution obtained by dissolving 5 parts of dodecyltrimethylammonium chloride in 162 parts of water was used instead of the pH-adjusted aqueous solution of emulsifier (1) in Example 1. Repeat to reduce the non-volatile content to 39.
A comparative aqueous resin dispersion [1] having a pH of 9% and s was obtained. Comparative Example 2 Same as Comparative Example 1, polyoxyethylene nonylphenyl ether (Nonipol 200, manufactured by Yokasei Kogyo ■)
The same procedure as in Example 1 was repeated except for using an aqueous emulsifier solution obtained by dissolving 5 parts in 162 parts of water to obtain a nonvolatile content of 4 parts.
A comparison aqueous resin dispersion [2] with a pH of 6.3 and a pH of 6.3 was obtained. Example 11 The cationic aqueous resin dispersions [1] to [10] obtained in Examples 1 to 10 and Comparative Examples 1 to 2 and the comparative aqueous resin dispersions [1] to [2] were placed on a Teflon plate. Casting was carried out so that the dry film thickness was 0.2 to 0.3 cm, and
A test film was prepared by heating and drying at 120° C. for 15 minutes to form a film, and then heating at 120° C. for 10 minutes. The following performance tests were conducted on the obtained films to evaluate the performance of each aqueous resin dispersion. The evaluation results are shown in Table 3. 1. Water resistance: Approximately 2c of test film! It was cut into an IL angle and weighed (Wo). The film was immersed in deionized water for 3 days, pulled out, and the moisture on the film surface was gently wiped off before being weighed (Wl). Further, the film was dried at 100°C for 1 hour. The water resistance of the ilm was evaluated. Water absorption rate (chi) - W, -W, ×100 elution rate (chi +
-W, -W, ×1o. O2, film strength: The elongation rate and tensile strength of the film were measured based on the test method described in JIS K-6732. Example 12 The cationic aqueous resin dispersions [1] to [10] obtained in Examples 1 to 10 and Comparative Examples 1 to 2 and the comparative aqueous resin dispersions [1] to [2] were heated to a glass plate. A coated test plate was prepared by applying the coating to a plate, an aluminum plate, and a polycarbonate plate using a KA616 bar coater, and then heating and drying at 80° C. for 10 minutes. The following performance tests were conducted on the obtained test plates to evaluate the performance of each aqueous resin dispersion. The evaluation results are shown in Table 4. 1.Normal adhesion: 1m using a cutter knife on the coating film
A 10+m×10m5 goblin was cut at m intervals, cellophane tape was crimped and then peeled off vigorously, and the degree of peeling of the goblin was graded as ◎, O1Δ, and ×. ◎ indicates the percentage of the part that did not peel off. 90-100% O is 1 70-90% Δ is
〃40~70%×
〃 0-40% 2, Water resistant adhesion: The test plate was immersed in deionized water for 1 day, pulled up and the water on the coating surface was wiped off within 1 minute, and then the adhesion test was conducted in the same manner as the normal adhesion above. I did it. Procedural amendment (voluntary) August 1986
/7th Patent Office Commissioner Kuro 1) Mr. Akio 1, Indication of the case Patent Application No. 57092 of 1988 2, Name of the invention Cationic aqueous resin dispersion 3, Person making the amendment Relationship to the case Patent applicant 5-1 Koraibashi, Higashi-ku, Osaka-shi, Osaka (462) Nippon Shokubai Kagaku Kogyo Co., Ltd. Representative Director: Jiro Nakajima 4, Agent: 1-2-2 Uchisaiwai-cho, Chiyoda-ku, Tokyo, Japan Nippon Shokubai Kagaku Kogyo Co., Ltd. Tokyo Branch Phone: 03-502-1651 5゜Section 6 of the detailed description of the invention in the specification of the application to be amended, content of the amendment +11 The following statement is added on a new line after the last line of page 23 of the specification. [Examples 11 to 13 The same operations as in Example 1 were repeated except that the monomer mixture composition, the emulsifier, and the type of pHvI4 adjuster of the emulsifier were as shown in Table 2. Resin dispersion [11
] to [13] were obtained. (2) Table 2 on page 24 of the same document is amended in 10 different ways. (3) On page 25, line 'M6 from the bottom, "Example 1
1J is corrected to "Example 14". (4) In the fifth line from the bottom of page 25, “Example 1-
10 and...'' was replaced with ``Examples 1 to 13''.
And...'' is corrected. (5) On page 25, line 4 from the bottom, “...
・Dispersions [1] to [10] and..." should be replaced with "...1, ...Dispersions (1) to [13] and..." to correct. 7 (6) Table 3 on page 27 of the same document in Attachment 2 (Document #)K
to correct. (7) In the first line of page 28, "Example 12" is amended to "Example 15." (8) In the second line of page 28, "Examples 1 to 10 and..." was replaced with "Examples 1 to 13 and..."
"..." I corrected myself. (9) On page 28, line 3 of the same paper, “…plane dispersion [1
] to [10] and...'' has been corrected to read [For dispersions [1] to [13] and...''. (10) Same name 2! Amend J page name 4 table in Attachment 3, 51;

Claims (1)

[Claims] 1. A polyamine and/or a derivative thereof having the general formula R-(OA)-_nX (wherein, R represents a hydrocarbon group having 4 to 28 carbon atoms, and A represents a hydrocarbon group having 2 to 4 carbon atoms). represents an 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. ) A cationic aqueous resin dispersion obtained by emulsion polymerization of one or more polymerizable monomers in an aqueous medium using a modified polyamine obtained by reacting a compound represented by the following as an emulsifier. 2. The cationic aqueous resin dispersion according to claim 1, wherein at least one of the polymerizable monomers is a compound having a functional group capable of reacting with a modified polyamine.