JPS6390509A - Cationic aqueous resin dispersion and cationic aqueous resin composition produced therefrom - Google Patents

Abstract

PURPOSE:To obtain the titled aqueous resin dispersion giving a coating film having high strength and water-resistance, by reacting a polyamine compound with a specific polyoxyalkylene compound and a polymerizable unsaturated compound and emulsion-polymerizing a monomer using the obtained reactive surfactant as an emulsifier. CONSTITUTION:The objective cationic aqueous resin dispersion is produced by (1) reacting (A) a polyamine compound having >=2 primary and/or secondary amino groups in the molecule with (B) a compound of formula I (R is 4-28C hydrocarbon group; A is 2-4C alkylene; n is 0 or integer of 1-30; X is atomic group having a functional group reactive with amino group) and (C) a compound of formula II (R' is atomic group having polymerizable unsaturated group) to obtain a reactive surfactant and (2) carrying out emulsion polymerization of a polymerizable monomer component composed of polymerizable monomers in an aqueous medium in the presence of the above reactive surfactant as an emulsifier.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel cationic aqueous resin dispersion and a cationic aqueous resin composition using the same. More specifically, various properties including water resistance can be obtained by using a reactive surfactant that has excellent emulsifying power and has two different types of reactive groups: a polymerizable unsaturated group and an amino group. Related to a cationic aqueous resin dispersion capable of forming films and coatings with excellent physical properties, and a cationic aqueous resin composition comprising the cationic aqueous resin dispersion and a compound having a functional group capable of reacting with an amino group. It is.

The cationic aqueous resin dispersion of the present invention and the cationic aqueous resin composition using the same have cationic particle charges, and therefore have excellent adsorption, adhesion, and adhesion to various substances. In addition, the cationic aqueous resin dispersion and the cationic aqueous resin composition using the same use a reactive surfactant having two different reactive groups, a polymerizable unsaturated group and an amino group, as an emulsifier. Therefore, the emulsifier is not only grafted onto the polymer produced by emulsion polymerization, but also the amino groups of the emulsifier can be used to make the film take on a crosslinked structure. Therefore, not only is there less foaming compared to those obtained using known cationic emulsifiers, but the film obtained by splashing water is highly strong and has good water resistance. It is useful in a wide variety of fields including glass fiber processing, leather processing, and coating and adhesion to various wireless and organic materials such as glass, metal, cement, plastic, etc.

(Conventional technology) Conventionally, dodecyltrimethylammonium chloride,
Cationic aqueous resin dispersions obtained by emulsion polymerization of vinyl compounds in the presence of quaternary ammonium salts such as stearyltrimethylammonium chloride are well known, and are used for various purposes due to their cationic nature. However, due to the water-soluble quaternary ammonium salt, the water resistance and strength of the film obtained by splashing water are poor.

(Problems to be Solved by the Invention) The present invention is intended to solve the above-mentioned problems that conventional cationic aqueous resin dispersions have, and therefore, its purpose is to improve the coating film obtained by splashing water. An object of the present invention is to provide a cationic aqueous resin dispersion having excellent water resistance and strength, and a cationic aqueous resin composition using the same.

(Means and effects for solving the problem) The present inventors have discovered that a reactive surfactant obtained by introducing a hydrophobic group and a polymerizable unsaturated group into a hydrophilic polyamine compound has excellent emulsifying power. When emulsion polymerization of polymerizable monomer components is carried out using the reactive surfactant as an emulsifier, the emulsifier is grafted onto the resulting polymer, and the film obtained by sprinkling water on it has good uniformity. Furthermore, it was discovered that the 7-mino group derived from the emulsifier on the surface of the polymer particles produced by emulsion polymerization has crosslinking properties with a compound having a specific functional group. That is, when a polymerizable monomer component containing a polymerizable monomer having reactivity with an amino group is subjected to emulsion polymerization using the reactive surfactant as an emulsifier, a cationic aqueous resin dispersion with good stability during polymerization can be obtained. can be produced, and from the obtained cationic aqueous resin dispersion, a film having a crosslinked structure with excellent water resistance and strength can be formed, and a functional group that can react with the cationic aqueous resin dispersion and amino groups. The present invention was achieved by discovering that a cationic aqueous resin composition comprising a compound having the following formula forms a film with even higher strength and excellent water resistance.

That is, the present invention provides polyamine compounds having two or more primary and/or secondary amino groups in the molecule with the general formula % (wherein R represents a hydrogenated group having 4 to 28 carbon atoms). , A represents an alkylene group having 2 to 4 carbon atoms, and n is O or 1 to 3
represents an integer of 0, and X represents an atomic group having a functional group that can react with an amino group.
represents an atomic group having a functional group that can react with an amine group,
Emulsifying a component for polymerizability consisting of one or more polymerizable monomers (A) in an aqueous medium using a reactive surfactant obtained by reacting with a compound represented by , ) as an emulsifier. The present invention relates to a cationic aqueous resin dispersion obtained by polymerization, and a cationic aqueous resin composition comprising the cationic aqueous resin dispersion and a compound (B) having a functional group capable of reacting with an amino group.

The polyamine compounds having two or more primary and/or secondary amine groups in the molecule used in the present invention are amines having two or more primary and/or secondary amino groups in the molecule. or its derivatives, such as polyalkyleneimines obtained by polymerization or copolymerization of alkyleneimines such as polyethyleneimine obtained by polymerization of edylenimine; ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc. (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 Examples include polyurea polyamine obtained by reacting with urea and polyamide polyamide polyamine obtained by copolymerizing an alkylene imine with an acid anhydride such as phthalic acid. Examples of polyamine derivatives include α,β-unsaturated acid amide compounds such as fullylene oxides such as ethylene oxide and propylene oxide, (meth)acrylic acid esters such as butyl acrylate and methyl methacrylate, and acrylamide. Examples include those obtained by addition reaction. In the present invention, it is preferable to use polyethyleneimine or a derivative thereof as the polyamine compound in order to obtain excellent surface activity. Further, in consideration of the water solubility of the resulting reactive surfactant, the viscosity of the solution, and the surfactant ability, it is preferable to use polyethyleneimine having a molecular weight of 5000 or less.

In the compound (hereinafter referred to as compound (I)) represented by the general formula % formula % (in the formula, R2Δ, X and n are the same as above) used in the present invention, J5 corresponds to R in the formula Examples of 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 7-aryl groups, (alkyl)aralkyl groups. etc. can be mentioned. As the compound <1), for example, n-
Octyl polyoxyalkylene glycidyl ether, n
-Nonyl polyoxyalkylene glycidyl ether, lauryl polyoxyalkylene glycidyl ether, stearyl polyoxyalkylene glycidyl ether, 2-
Primary alkyl polyoxyalkylene glycidyl ethers such as ethylhexyl polyoxyalkylene glycidyl ether: those obtained by adding 1 to 30 moles of alkylene oxide to a mixture of secondary alcohols having 12 to 14 carbon atoms and further converting the mixture into glycidyl ether, carbon number 10
Secondary alkyl polyoxyalkylene glycidyl ethers, such as those obtained by adding 1 to 30 moles of fullkylene oxide to a mixture of 1 to 12 secondary alcohols and further glycidyl etherification; the number of moles of alkylene oxide added is 1 to 30 Alkylphenyl polyoxyalkylene glycidyl ethers such as octylphenyl polyoxyalkylene glycidyl ether, nonylphenylborioxyalkylene glycidyl ether, lauryl phenyl polyoxyalkylene glycidyl ether, and stearyl phenyl polyoxyalkylene glycidyl ether: Number of moles of alkylene oxide added is 1 to 30
octylcyclopentyl polyoxyalkylene glycidyl ether, octylcyclohexyl polyoxyalkylene glycidyl ether, nonylcyclopentyl polyoxyalkylene glycidyl ether, nonylcyclohexyl polyoxyalkylene glycidyl ether, laurylcyclopentyl polyoxyalkylene glycidyl ether, laurylcyclohexyl polyoxyalkylene glycidyl ether, stearyl Alkylcycloalkyl polyoxyalkylene glycidyl ethers such as cyclopentyl polyoxyalkylene glycidyl ether and stearyl cyclohexyl polyoxyalkylene glycidyl ether: the number of moles of alkylene oxide added is 1
30 alkylbenzyl polyoxyethylene glycidyl ethers such as octylbenzyl polyoxyalkylene glycidyl ether, nonylbenzyl polyoxyalkylene glycidyl ether, laurylbenzyl polyoxyalkylene glycidyl ether, and stearylbenzyl polyoxyalkylene glycidyl ether; octyl glycidyl ether, lauryl glycidyl ether,
Glycidyl ethers of higher alcohols such as stearyl glycidyl ether and 2-ethylhexyl glycidyl ether; glycidyl ethers of alkylphenols such as octylphenyl glycidyl ether, nonylphenyl glycidyl ether, lauryl phenyl glycidyl ether, and stearyl phenyl glycidyl ether;
Alkylcyclo such as octylcyclopentylglycidyl ether, octylcyclohexylglycidyl ether, nonylcyclopentylglycidyl ether, nonylcyclohexylglycidyl ether, laurylcyclopentylglycidyl ether, laurylcyclohexylglycidyl ether, stearylcyclopentylglycidyl ether, stearylcyclohexylglycidyl ether Glycidyl ethers of flucanol: glycidyl ethers of alkylbenzyl alcohols such as octylbenzylglycidyl ether, nonylbenzylglycidyl ether, laurylbenzylglycidyl ether, and stearylbenzylglycidyl ether; carbon number 12
or 1,2-epoxy alkanes such as 14 α-olefin epoxides and α-olefin epoxides having 16 or 18 carbon atoms; alkyl isocyanates such as octyl isocyanate, decyl isocyanate, and octadecyl isocyanate; octatool, lauryl alcohol, stearyl alcohol;・Monoisocyanate compounds obtained by reacting alcohols such as coal or alkylene oxide adducts of these alcohols with diisocyanates such as tolylene diisocyanate; Alcohols such as octatool, lauryl alcohol, and stearyl alcohol, or these alcohols Halides in which the terminal hydroxyl group of alkylene oxide adducts 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; nioleic acid, linoleic acid, lylunic acid, Unsaturated fatty acids such as eleostearic acid = 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, (
Examples include (meth)acrylic esters such as stearyl meth)acrylate, and one or more selected from these groups can be used. The amount of compound (I) to be used is not particularly limited, but in order to develop sufficient surface activity, 0.01 to 0.9 molecules of compound (I) should be used per active amine hydrogen of the polyamine compound.
) is preferably used.

In the compound (IJ, hereinafter referred to as compound (IF)) represented by the general formula (wherein R" and X are the same as above) used in the present invention, the atom corresponding to R' in the formula Examples of the compatible unsaturated group in the group include (meth)acryloyl group, (meth)allyl group, vinyl group, etc. As the compound (II), (meth)acrylic M2-chloroethyl, (meth)acrylic M2-chloroethyl, ( (meth)acrylic acid esters having a group that reacts with an amino group in the molecule such as glycidyl acrylate, (methaneac 911M2-incyanate ethyl): vinyl ethers such as chloroethyl vinyl ether; (meth)allyl chloride, (meth) ) allyl bromide, (meta)
Allyl isothiocyanate, allyl (meth)acrylate, half ester of (meth)allyl alcohol and dicarboxylic acid anhydride such as phthalic anhydride or anphosuccinic acid,
(meth)allyl compounds such as (meth)allyl glycidyl ether; styrene derivatives having a group that reacts with an amino group in the molecule such as chloromethylstyrene and α-methylchloromethylstyrene; Examples include vinyl esters of acids having a group that reacts with an amino group, and 1 selected from these groups.
A species or two or more species can be used. In order to obtain a reactive surfactant in a good yield, it is preferable to use vinyl ethers, (meth)allyl compounds, styrene derivatives, and acid vinyl esters as the compound (If). Also, o per active amine hydrogen of the compound NI),
It is preferable to set it as oi~0.9 molecules.

The reaction conditions for obtaining the reactive surfactant used in the present invention are not particularly limited. For example, the polyamine compound, compound (I), and compound (ffl) are preferably used as they are, or diluted with a solvent as necessary. is room temperature~20
It can be synthesized by reaction at a temperature of 0°C, more preferably 50 to 100°C.

At this time, it is preferable that the solvent used if necessary be capable of dissolving the polyamine compound, compound (1) and compound (II), and be inert to them. Further, during the reaction, a catalyst may be freely used to promote the reaction.

The reactive surfactant thus obtained can be mixed with an acid to form a salt. It is preferable to use a salt because it improves solubility in water. Acids that can be blended include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; formic acid, acetic acid and (
Examples include organic acids such as meth)acrylic acid.

The reactive surfactant thus obtained has excellent emulsifying power and can stably carry out emulsion polymerization of a wide variety of polymerizable monomers, and therefore has various physical properties such as water resistance and strength of the present invention. It is possible to stably provide a cationic aqueous resin dispersion that can form a film with excellent properties and a cationic aqueous resin composition using the dispersion.

The polymerizable monomer (A) used in the polymerizable monomer component in the present invention is not particularly limited as long as it contains a polymerizable unsaturated group, but examples include (meth)acrylic acid. Straight-chain or branched aliphatic alkyl alcohols or fats having 1 to 18 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, octyl, 2-ethyl, isyl, lauryl, stearyl, or cyclohexyl esters. Cyclic alkyl alcohol and (
(Meth)acrylic acid esters which are ester compounds with meth)acrylic acid; such as (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, itaconic acid or monoesters of maleic acid or fumaric acid, etc. Polymerizable unsaturated carboxylic acids and their salts; Polymerizable unsaturated sulfonic acids such as vinyl sulfonic acid, styrene sulfonic acid, (meth)acrylic sulfoethyl, and their salts: (meth)aminoedyl acrylate, dimethylamino (meth)acrylate Basic unsaturated monomers such as ethyl, dimethylaminoethyl (meth)acrylamide, vinylpyridine, vinylimidazole, vinylpyrrolidone; hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, (meth)acrylic acid Hydroxyl group-containing unsaturated monomers such as monoesters of and polypropylene glycol or polyethylene glycol; Epoxy group-containing unsaturated monomers such as glycidyl (meth)acrylate; (meth)acrylic PIi2-hydroxy-3 - Unsaturated single solids containing halohydrin groups such as chloropropyl; unsaturated single solids containing blocked isocyanate groups such as phenolic adducts of isocyanatoethyl (meth)acrylate = (meth)acryloyl aziridine, (meth)acryloyl Unsaturated monomers containing an aziridinyl group such as oxyethylaziridine: Unsaturated monomers containing an oxazoline group such as 2-propenyl-2-oxazoline and 2-vinyl-2-oxazoline; (meth)
Polymerizable unsaturation in molecules such as esters of acrylic acid and polyhydric alcohols such as ethylene glycol, 1,3-butylene glycol, 1,6-hexane glycol, neopentyl glycol, polyethylene glycol, polypropylene glycol, and trimethylolpropane. Polyfunctional (meth)acrylic acid esters containing two or more groups=
(Meth)acrylamides such as (meth)acrylamide, methylolated (meth)acrylamide, and alkoxymethylolated (meth)acrylamide having 1 to 4 carbon atoms; vinyltrimethoxysilane, γ-(meth)acryloxypropyltrimethoxysilane , allyltriethoxysilane, organosilicon monomers such as trimethoxysilylpropylallylamine, and styrene, vinyltoluene,
Examples include vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, ethylene, propylene, butadiene, isoprene, dicyclopentadiene, divinylbenzene, diallyl phthalate, etc. One type or a mixture of two or more types selected from these groups can be used.

The cationic aqueous resin dispersion of the present invention uses the above-mentioned reactive surfactant as an emulsifier, and the polymerizable monomer (A)
It is obtained by emulsion polymerization of one or more polymerizable monomer components 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 grade of the reactive surfactant used as an emulsifier during emulsion polymerization is not particularly limited, but polymerizable monomer 100
It is preferable to use it in a range of 0.5 to 200 parts by weight.

Further, although it is preferable to use the reactive surfactant alone as an emulsifier, it is also possible to use a conventionally known emulsifier in combination to the extent that the characteristics of the present invention are not impaired. Furthermore, after emulsion polymerization, if necessary, a PH regulator, a curing catalyst,
A diluent etc. can also be added.

The cationic aqueous resin dispersion of the present invention thus obtained has little foaming and excellent long-term stability, and the film formed by volatilizing water from the aqueous resin dispersion can be used in various ways. It has good adsorption, adhesion and adhesion to substances, and because the reactive surfactant used in the emulsifier is grafted with the polymer produced by emulsion polymerization, it has excellent physical properties such as water resistance and strength. However, the polymerizable monomer component used in emulsion polymerization is a polymerizable monomer having a functional group capable of reacting with at least one amino group (△-1
), the above characteristics are more clearly exhibited.

Examples of functional groups that can react with the amino group of the reactive surfactant include carboxyl group, sulfonic acid group, aziridinyl group, oxazoline group, hydroxyl group, epoxy group,
Examples of the polymerizable monomer (A-1) having these functional groups include a herohydrin group, a blocked isocyanate group, and an alkoxysilyl group. Carboxylic acids, polymerizable unsaturated sulfonic acids, aziridinyl group-containing unsaturated monomers, oxazoline group-containing unsaturated monomers, hydroxyl group-containing unsaturated monomers, halohydrin group-containing unsaturated ω-forms,
Examples include blocked isocyanate group-containing unsaturated monopendicular monomers, epoxy group-containing unsaturated monomers, and monotonic silicon monomers.

In particular, when it is desired to use the cationic aqueous resin dispersion at room temperature or lower temperatures, at least 51 types of epoxy groups and oxazoline groups that can react at low temperatures with the amino groups of the reactive surfactants used as emulsifiers are recommended. , an aziridinyl group (A-1>) has good storage stability, and has a crosslinked structure at low temperatures and is strong and water resistant. This is preferred because it provides a good film.

A cationic aqueous resin composition comprising the cationic aqueous resin dispersion and a compound (B) having a functional group that reacts with an amino group (hereinafter referred to as compound (B)), which is the second invention of the present invention. In the process of forming a film, compound (B) undergoes a crosslinking reaction with the amino group of the reactive surfactant used as an emulsifier during the production of the cationic aqueous resin dispersion, resulting in improvements in water resistance and other properties. This brings about improvements in physical properties. Compounds (B) that bring about such effects include those that have two or more functional groups that can react with an amino group in the molecule, or those that have a functional group that can react with an amino group and a crosslinking-reactive functional group in the molecule. For example, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerol diglycidyl ether , diglycidyl ethers such as bisphenol A diglycidyl ether, diglycidyl nisdels such as disuccinic acid diglycidyl ester and adipic acid diglycidyl ester; glycerol triglycidyl ether, diglycerol polyglycidyl ether, phenol novolak type epoxy resin, cresol Polyglycidyl ethers such as novolac type epoxy resins: Glycidyl amines such as tetraglycidyldiaminodiphenylmethane and diglycidyldimethylhydantoin: T-glycidoxyprobyltrimethoxysilane, γ-glycidoxyprobyl], ethoxysilane, etc. glycidylsilane compounds; blocked isocyanates which are adducts of diisocyanate compounds such as hexamethylene diisocyanate, tolylene diisocyanate, and isophorone diisocyanate and phenol; trimedylolbroban tri(meth)acrylate, hexamethylene di(meth)acrylate , pentaerythritol hexa(meth)
Acrylate, dipentaerythritol hexa(meth)
Polyvalent (meth)acrylates such as acrylates: 2 moles of ethyleneimine adduct of hexamethylene diisocyanate, 3 moles of ethyleneimine adduct of trimethylolpropane triacrylate, tris(1-aziridinyl)
Polyfunctional aziridine compounds such as phosphine oxyto and tris(1-aziridinyl)triazine; bis(2-
A xacilinyl) diethyl ether, bis(2-oxazolinyl) diethylthioether, m-phenylenedi
Polyfunctional oxazoline compounds such as 2-oxazoline) can be mentioned, and one or more types selected from these groups can be used.

The properties of compound (B) are not particularly limited, and it can be used, for example, as a liquid, solid, or aqueous dispersion. Compound (B) is preferably used in an amount of 0.1 to 1000 times the amount of the reactive surfactant used as an emulsifier. If the amount of compound (B) used is less than 0.1 times the amount of the reactive surfactant used as an emulsifier, the crosslinking of the film obtained from the cationic aqueous resin composition will not be sufficient, and various aspects of the film will be affected. No improvement in physical properties can be expected; on the contrary, 10
If the cationic aqueous resin composition is increased in content by a factor of 00, the storage stability of the cationic aqueous resin composition will decrease, which is not preferable.

(Effect of the invention) The cationic aqueous resin dispersion of the present invention and the cationic aqueous resin composition using the same have a reactive interface having two different types of reactive groups, a polymerizable unsaturated group and an amine group. The feature is that the activator is used as an emulsifier, and the emulsifier is not only grafted onto the polymer produced by emulsion polymerization via the polymerizable unsaturated group, but also creates a crosslinked structure using the amino group of the emulsifier. It is possible to form a film with Therefore, using a known cationic emulsifier, 1!
There is less foaming compared to the aqueous resin dispersion prepared by I.
The film obtained by dispersing it has good water resistance and high strength, so it is suitable for various S machines and organic materials such as fiber processing, glass fiber processing, leather processing, glass, metal, cement, plastic, etc. It is useful in a wide range of fields such as coatings and adhesives.

(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 actual IM examples, unless otherwise specified, "%" means % by weight, and "parts" means 8 parts by weight.

Reference Example 1 Polyethyleneimine (
Evomin 5P-006, manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd., average molecular weight 600) 100 parts, α- with 12 and 14 carbon atoms
Olefin epoxide mixture (AOE-X24, manufactured by Daicel Chemical Industries, Ltd., average molecular weight 196.3) 65.
4 parts of allyl glycidyl ether and 76 parts of allyl glycidyl ether were added thereto and heated to 80° C. with stirring under a nitrogen stream. Stirring was continued for 4 hours at the same temperature to complete the reaction, and the reactive surfactant (1)
I got it.

Reference Examples 2 to 4 In Reference Example 1, the reactive interface was prepared in the same manner as in Reference Example 1, except that the type of polyamine compound and the usage ratio of Compound (I) and Compound (I) were as shown in Table 1. Activators (2) to (4) were obtained.

Reference Example 5 In a reaction vessel similar to Reference Example 1, 100 parts of polyethyleneimine (Evomin) SP-012 (manufactured by Nippon Shokubai Chemical Co., Ltd., average molecular weight 1200), and 80 parts of lauryl acrylate were added.
and 74.7 parts of allyl acrylate were heated slowly while stirring under a nitrogen stream, and the temperature was increased from room temperature to 8.5 parts at 1 fTf.
The temperature was raised to 0°C. Stirring was continued for 1 hour at the same temperature to complete the reaction, and a reactive surfactant (5) was obtained. The properties of this product were as shown in Table 1.

Reference Example 6 In a reaction vessel similar to Reference Example 1, 100 parts of polyethyleneimine (Evomin 5P-012), 65.4 parts of α-olefin epoxide (AOE-X24), 30.5 parts of chloromethylstyrene, and as a polymerization inhibitor were added. Add 0.015 part of P-methoxyphenol, and add 0.015 part of P-methoxyphenol, and add 8
The temperature was raised to 0°C.

Stirring was continued at the same rate for 30 hours to complete the reaction, and a reactive surfactant (6) was obtained. The properties of this product were as shown in Table 1.

Example 1 In a flask equipped with a dropping funnel, a stirrer, a nitrogen inlet tube, a thermometer, and a reflux condenser, 197 parts of pure water, 3 parts of the reactive surfactant (1) obtained in Reference Example 1, and as a PH adjuster were added. 1.9 parts of acetic acid was charged, and the mixture was heated to 65° C. while slowly blowing nitrogen gas.

A polymerizable monomer component consisting of 55 parts of butyl acrylate and 45 parts of methyl methacrylate was prepared in a dropping funnel, and 10 parts of the component was dropped into the flask. Subsequently, a 5% aqueous solution of 2,2'-azobis(2-amidinopropane) dihydrochloride6
part was injected. After 20 minutes, dropping of the remaining chassis I1 component was started, and the dropping was completely completed in 1.5 hours. During the dropwise addition, the temperature was maintained at 65 to 70°C, and after the completion of the dropwise addition, the polymerization was completed by stirring at the same temperature for 1 hour.
8%, cationic aqueous resin dispersion with Pi-1=5.1 [
1] was obtained.

Examples 2 to 6 In Example 1, the type of reactive surfactant, P)-I
am preparation 0th generation and type, type of polymerizable single F component
Cationic aqueous resin dispersions [2] to [6] were obtained by repeating the same operations as in Example 1, except as shown in the table. The results are summarized in Table 2.

Comparative Examples 1 to 2 In Example 1, the same operations as in Example 1 were repeated, except that the commercially available cationic emulsifier shown in Table 2 was used instead of the reactive surfactant as the emulsifier. Comparative cationic aqueous resin dispersions [1-] to [2'] were obtained. The results are summarized in Table 2.

Example 7 Using the same apparatus as in Example 1, add 197 ml of pure water to a flask.
parts, 3 parts of the reactive surfactant (1) obtained in Reference Example 1,
1.9 parts of acetic acid was added as a pH adjuster, and the mixture was heated to 65° C. while slowly blowing nitrogen gas. A polymerizable monomer component (1) consisting of 18 parts of 2-ethylhexyl acrylate and 12 parts of glycidyl methacrylate was injected therein. followed by 2,2'-azobis(2-amidinopropane)
Polymerization was initiated by adding 6 parts of a 5% aqueous solution of dihydrochloride.

After 40 minutes of incubation, dropwise addition of the polymerizable monomer component (2) consisting of 35 parts of butyl acrylate and 35 parts of methyl methacrylate was started and was completed in 1.5ff5. During dripping, keep the temperature at 65-7.
The temperature was maintained at 0°C, and after the completion of the dropwise addition, stirring was continued at the same temperature for 1 hour to complete the polymerization, resulting in a non-volatile content of 33.8% and a pH of 5.4.
A cationic aqueous resin dispersion [7] was obtained.

Examples 8 to 10 In Example 7, the same operation as in Example 7 was performed, except that the type of reactive surfactant and the polymerizable monomer component (1) used were as shown in Table 3. The steps were repeated to obtain cationic aqueous resin dispersions [8] to [10]. The results are summarized in Table 3.

Comparative Examples 3 to 6 Comparative cation Aqueous resin dispersions [3'j to [6'] were obtained. The results are summarized in Table 3.

Example 11 Ethylene glycol diglycidyl ether ( Bunacol EX-810, Nagase Kasei (
Co., Ltd.) was added and mixed to obtain a cationic aqueous resin composition <1>.

Examples 12 to 16 In Example 11, the same operations as in Example 11 were repeated except that the cationic aqueous resin dispersion and the type and amount of compound (B) were as shown in Table 4. Aqueous resin compositions 2> to 6 were obtained.

Comparative Example 7 Cationic aqueous resin dispersion prepared in Comparative Example 1 [1'
5 parts of ethylene glycol diglycidyl ether (Bunacol EX-810) were added and mixed to 100 parts of the solid content of ] to prepare a comparative cationic aqueous resin composition <1'>.
I got it.

Comparative Example 8 In Example 7, the cationic aqueous resin dispersion [3'1
A comparative cationic aqueous resin composition 2' was obtained by carrying out the same operation as in Comparative Example 7, except for using the following.

Table 4 (manufactured by Nagase Kasei Co., Ltd.) (manufactured by Toshiba Silicone Co., Ltd.) Example 17 Cationic aqueous resin dispersions [1] to [101, for comparison] obtained in Examples 1 to 16 and Comparative Examples 1 to 8 Cationic aqueous resin dispersions [1'] to [6'] and cationic aqueous resin compositions 1 to 6, comparative cationic aqueous resin compositions 1 to 2' was cast on a Teflon plate so that the dry film thickness was 0.2 to 0.3 a1m, dried by heating at 80°C for 15 minutes to form a film, and then heated at 120°C for 10 minutes to create a test film. did.

The following performance tests were conducted on the resulting films to evaluate the performance of each dispersion and composition. The evaluation results are shown in Table 5.

1. Water resistance: The test film was cut into a square of approximately 2 cR 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).

Furthermore, the film was dried at 100° C. for 1 hour, left to cool, and then weighed (W2).

The water absorption rate and elution rate were calculated using the following formula to evaluate the water resistance of the test film.

Wl - W2 Water absorption rate (%) = X1000 - W2 Elution rate (%) = X100O Film appearance: The transparency of the film immersed in deionized water for 3 days was evaluated.

○: No change as it remains transparent Δ: Becomes bluish ×: Becomes white 2. Film strength: The tensile strength of the film was measured based on the test method described in JIS K-6732.

Table 5 Example 18 Cationic aqueous resin dispersions [1] to [10] obtained in Examples 1 to 16 and Comparative Examples 1 to 8, comparative cationic aqueous resin dispersions [1'] to [6] '] and cationic aqueous resin compositions <1> to 6>, comparative cationic aqueous resin compositions 1' to 1', and then heated and dried at 80°C for 10 minutes,
A coated test plate was prepared. The following performance tests were conducted on the obtained test plates to evaluate the performance of each dispersion liquid and composition. The evaluation results are shown in Table 6.

1.Normal adhesion: 1n using a cutter knife on the coating film
A 10a*×10m+ grid was cut at intervals of 10a*×10m+, and a round Rohan tape was crimped and then peeled off vigorously, and the degree of peeling of the grids was graded as ◎, ○, △, and ×.

◎ means the proportion of the part that did not peel off is 90-100% O means 70-90% Δ means
40-70%X is
0-40% 2, water resistant adhesion: test plate in deionized water 1
After soaking for a day, pulling out and wiping off moisture on the surface of the coating within 1 minute, an adhesion test was conducted in the same manner as the normal adhesion described above.

Claims (4)

[Claims] (1) Polyamine compounds having two or more primary and/or secondary amino groups in the molecule have the general formula R-(OA)_
n-X (in the formula, R represents a hydrocarbon having 4 to 28 carbon atoms, A represents an alkylene group having 2 to 4 carbon atoms, and n is 0 or 1 to 30
represents an integer of , and X represents an atomic group having a functional group that can react with an amino group. ) and the general formula R'-X (wherein R' represents an atomic group having a polymerizable unsaturated group,
represents an atomic group having a functional group that can react with an amino group. ) A cationic compound obtained by emulsion polymerization of a polymerizable monomer component consisting of a polymerizable monomer (A) in an aqueous medium using a reactive surfactant obtained by reacting with a compound represented by (A) as an emulsifier. Aqueous resin dispersion. (2) The polymerizable monomer component according to claim 1, wherein the polymerizable monomer component comprises a polymerizable monomer (A-1) having a functional group capable of reacting with at least one kind of amino group. Cationic aqueous resin dispersion. (3) Polyamine compounds having two or more primary and/or secondary amino groups in the molecule have the general formula R-(OA)-
_nX (wherein R represents a hydrocarbon group having 4 to 28 carbon atoms, A represents an alkylene group having 2 to 4 carbon atoms, and n is 0 or 1 to 3
It represents an integer of 0, and X represents an atomic group having a functional group that can react with an amino group. ) and the general formula R'-X (wherein R' represents an atomic group having a polymerizable unsaturated group,
represents an atomic group having a functional group that can react with an amino group. ) A polymerizable monomer component consisting of one or more polymerizable monomers (A) is emulsified in an aqueous medium using a reactive surfactant obtained by reacting with a compound represented by (A) as an emulsifier. A cationic aqueous resin composition comprising a cationic aqueous resin dispersion obtained by polymerization and a compound (B) having a functional group capable of reacting with an amino group in its molecule. (4) Claim 3, characterized in that the polymerizable monomer component comprises a polymerizable monomer (A-1) having a functional group capable of reacting with at least one type of amino group. cationic aqueous resin composition.