JPS637209B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides an aqueous resin dispersion that has excellent performance as a basic composition for paints, adhesives, and the like. Polymer dispersions obtained by emulsion polymerization, such as acrylic, acrylic-styrene, vinyl acetate, and ethylene-vinyl acetate, are widely used in industrial applications such as paints and adhesives. However, the films formed from these conventional polymer dispersions have insufficient adhesion to metals, wood, cured cement, plastics, etc., and often cause serious problems such as peeling and blistering, especially in wet conditions or at high temperatures. It had a defect. In order to improve such defects, JP-A-55-3481 discloses a technique for reducing water-sensitive substances such as surfactants and protective colloids contained in polymer dispersions. .
Further, US Pat. No. 4,021,396 attempts to introduce a functional group into a polymer skeleton to form a crosslinked structure. However, the current situation is that sufficient effects have not been achieved. The present inventors have conducted extensive studies to find an aqueous polymer dispersion that exhibits high adhesiveness on wet surfaces and at high temperatures, and as a result, they have accomplished the present invention. That is, the present invention provides at least one member selected from the group consisting of (A) α,β-unsaturated carboxylic acid, α,β-unsaturated carboxylic acid ester, α,β-unsaturated carboxylic acid amide, and aromatic vinyl compound. (B) a condensate of a compound having a phenolic OH group and epichlorohydrin, and at least one kind selected from the group of a primary amino group, a secondary amino group, and a phenolic OH group; A compound having at least one carboxyl group in one molecule obtained by reaction with a compound having at least one carboxyl group in one molecule as a functional group, and (C) a compound having a phenolic OH group. and a condensate of epichlorohydrin, and an aqueous resin dispersion in which the total amount of component (B) and component (C) is in the range of 10 to 1000 parts by weight based on 100 parts by weight of component (A). It is related to. Hereinafter, the aqueous resin dispersion of the present invention will be explained in detail. Examples of the α,β-unsaturated carboxylic acid of component (A) used in the present invention include acrylic acid and methacrylic acid, and examples of the α,β-unsaturated carboxylic acid ester include methyl acrylate and acrylic acid. ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and methacrylic esters corresponding to the above acrylic esters,
Examples of α,β-unsaturated carboxylic acid amides include acrylamide, methacrylamide, N-methylolacrylamide, dimethylolacrylamide, N-butoxymethylacrylamide, etc. Examples of aromatic vinyl compounds include glycidyl methacrylate, etc. Examples include styrene, α-methylstyrene, and vinyltoluene. The epoxy compounds that are the starting materials for component (C) and component (B) used in the present invention include phenolic
A condensate of a compound having an OH group and epichlorohydrin, such as 2,2'-bis(4,4'-hydroxyphenyl)propane (commonly known as bisphenol A),
Halogenated bisphenol A, 2,2'-bis(4,4'-hydroxyphenyl)methane (commonly known as bisphenol F), resorcinol, tetrahydroxyethane, phenol or novolac type polyfunctional phenol condensed with cresol and formalin. and epichlorohydrin. Preferred is a condensate of bisphenol A and epichlorohydrin having an epoxy equivalent of 180 to 3,000. Compounds used as component (B) of the present invention include monoamino monocarboxylic acids such as glycine, alanine, parine, leucine, isoleucine, etc. as compounds having a carboxyl group and a primary amino group or a secondary amino group. , oxyamino acids such as serine and threonine, ion-containing amino acids such as cysteine, cystine, and methionine, monoaminodicarboxylic acids such as aspartic acid and glutamic acid,
Diaminomonocarboxylic acids such as lysine and arginine, aromatic amino acids such as phenylalanine, tyrosine, anthranilic acid, m-aminobenzoic acid, p-aminobenzoic acid, proline, oxyproline,
Examples include heterocyclic amino acids such as histidine and tryptophan. Examples of compounds having a carboxyl group and a phenolic OH group include salicylic acid and salicyloylsalicylic acid. Preferred as component (B) are alanine and p-aminobenzoic acid. The compound of component (B) is a compound having a carboxyl group and a primary amino group, a secondary amino group, or a phenolic OH group per equivalent of the epoxy group of the epoxy compound, and a compound having an active hydrogen group of the amino group. , or added in a range of 0.1 to 1 equivalent of phenolic OH group,
Obtained by reacting at 40-100°C for 10 minutes to 24 hours. When the same epoxy compounds are used as components (B) and (C), the desired amount of carboxyl groups and primary and secondary epoxy compounds are added to the total amount of epoxy compounds required for components (B) and (C). A compound having an amino group or a phenolic OH group may be reacted. These compounds of component (B) can be neutralized with an alkaline compound, which is preferred. This alkaline substance includes ammonia,
Methylamine, ethylamine, dimethylamine,
Diethylamine, diethanolamine, etc. can be used. For neutralization, a total of 1 carboxyl group and phenolic OH group of the product compound of component (B) is required.
It is good to use 0.1 to 1 mol, preferably 0.3 to 0.7 mol, of the alkaline substance per mole. The aqueous resin dispersion of the present invention comprises the above component (A), the component
It can be obtained by uniformly mixing (B) and component (C) in an aqueous medium. A coating film with sufficient hardness and adhesion cannot be obtained with component (A) and component (B) alone, and component (A)
A stable aqueous dispersion cannot be obtained with only component (C). Further, it is not possible to obtain the flexibility and hardness of the coating film using only component (B) and component (C). The blending ratio of components (A), (B), and (C) can be arbitrarily selected taking into consideration various properties such as hardness and flexibility of the intended coating film, but 100 parts by weight of component (A) For,
The total amount of components (B) and (C) is preferably in the range of 10 to 1000 parts by weight. Also, the weight ratio of component (B) and component (C) is
It is preferably in the range of 40/60 to 80/20. The method for producing the aqueous resin dispersion of the present invention includes:
The ethylenic monomer of component (A) is emulsion polymerized to obtain an aqueous dispersion of the polymer, to which component (B) and component (C) are added sequentially or simultaneously, and the mixture is forcibly stirred using a high-speed stirrer. A method of adding a surfactant to component (B) and component (C),
There is a method of preparing an emulsified dispersion by adding water and, if desired, an organic solvent, and mixing this with an aqueous polymer dispersion of component (A). However, a more preferred method is to uniformly mix the monomer of component (A), component (B), and component (C), and then add a surfactant, a dispersant, a protective colloid, etc., water, and a polymerization initiator. This is a method in which emulsion polymerization is carried out as an emulsion dispersion by adding an organic solvent and other additives as necessary. The most preferred method is a method in which emulsion polymerization is carried out as an emulsion dispersion by the emulsifying action of the quaternary ammonium compound as component (B) without using surfactants, dispersants, etc. This method not only simplifies the process of emulsion polymerization, but also makes it possible to obtain an aqueous dispersion with uniform components and stability. Emulsion polymerization for obtaining the aqueous resin dispersion of the present invention is carried out by a conventionally known method. That is, examples of surfactants, dispersants, and protective colloids necessary to provide a site for emulsion polymerization and maintain dispersion stability of the produced polymer particles include fatty acid soaps, alkyl sulfate ester salts, and alkylbenzene sulfonic acids. salt, dialkyl sulfosuccinate salt, alkyl phosphate salt, polyoxyethylene alkyl sulfate salt, polyoxyethylene alkyl phosphate salt, alkyl diphenyl alkyl phosphate salt, alkyl diphenyl ether disulfonate, vinyl sulfone Acid salt, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenol ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, oxyethylene oxypropylene block copolymer, alkyl amine salt, quaternary grade ammonium salt,
Polyoxyethylene alkylamines, polyphosphates, polyacrylates, copolymer salts of maleic anhydride, polyvinyl alcohol, hydroxyethyl cellulose, etc. are used as polymerization initiators for ethylenic monomers, such as persulfates and persulfates. oxide,
Azobis compounds and redox systems in combination with these and reducing agents are used. Further, a PH adjuster such as sodium hydrogen phosphate or sodium hydrogen carbonate and an organic solvent are added as necessary. The water resin dispersion of the present invention is a condensation product of polyamines having primary and secondary amino groups, their adducts, compounds having active hydrogen such as polyamide polyamines, phenols such as phenols and alkylphenols, and formalin. A highly adhesive film having a crosslinked network structure is formed by adding the aminoplast resin and the aminoplast resin, mixing uniformly, drying, and heating if necessary. The film obtained from the aqueous resin dispersion of the present invention has excellent water resistance, good chemical resistance and boiling water resistance, and sufficient flexibility. The aqueous resin dispersion obtained by the present invention has a wide range of uses, including paints for metals, paints containing pigments, adhesives using tackiness, emulsions for building materials, printing inks, and treatment agents for fibers and paper. . The present invention will be specifically explained below using examples. Note that parts in the examples represent parts by weight. Example 1 In a separable flask equipped with a stirrer and a reflux device, epoxy resin A.
ER-661 (manufactured by Asahi Kasei, epoxy equivalent 465) 116
g, xylene 60g, and n-butanol 60g and mix uniformly. In this, p-aminobenzoic acid 55
g was added, and stirring was continued at 60°C for about 3 hours. After cooling this to room temperature, 24g of diethanolamine
Add. Furthermore, epoxy resin AER−661 116
g. After adding 30 g of styrene and 30 g of methyl methacrylate as polymerizable monomers and mixing them uniformly, 2.
Transfer to a beaker. When 400 g of water was added to this mixed solution while stirring it with a homomixer, a white water dispersion A was obtained. Example 2 892 g of the aqueous dispersion A obtained in Example 1 was mixed with 500 g of water prepared separately, 1 g of potassium persulfate, and 1 g of ammonium persulfate as an initiator for the polymerizable monomer.
(g) was uniformly dissolved and added dropwise into an aqueous solution maintained at a temperature of 80°C over about 1 hour. After the dropwise addition was completed, the reaction was continued for about 1 hour, and 0.5 g of potassium persulfate was further added and the reaction was carried out at 80° C. for 2 hours. When the mixture was cooled to room temperature, a white aqueous dispersion B was obtained. Example 3 10 g of hexamethoxymethylolmelamine was added to 130 g of the water dispersion B of Example 2 and mixed uniformly to obtain a white water dispersion C. Example 4 116 g of epoxy resin AER-661, 30 g of styrene, and 30 g of methacrylic acid were put into a separable flask equipped with a stirrer and a reflux device, and after uniformly dissolving and mixing, 55 g of p-aminobenzoic acid was added. Stirring was continued at 60°C for about 3 hours. After cooling this to room temperature, 24 g of diethanolamine was added. While stirring this mixed solution using a homomixer, 400 g of water was added to obtain a white water dispersion D.
In a separate container, uniformly dissolve 1 g of potassium persulfate and 1 g of ammonium persulfate in 500 g of water, and adjust the temperature to 80℃.
Keep it. The entire amount of water dispersion D was added to this aqueous solution over about 1 hour, and stirring was continued for 1 hour.
Further, 0.5 g of potassium persulfate was added and the reaction was continued for about 2 hours. Upon cooling to room temperature, water dispersion E was obtained. Add 10 g of hexamethoxymethylolmelamine to 130 g of this water dispersion E and mix uniformly.
A white aqueous dispersion F was obtained. Example 5 In Example 4, an aqueous dispersion was obtained by changing the type of epoxy resin, the carboxyl group-containing compound, the weight ratio of the carboxyl group-containing compound to the epoxy resin, and the amount of diethanolamine added. Its composition is shown in Table-1. Example 6 An aqueous dispersion was obtained by changing the type and composition of the acrylic monomer and the weight ratio of the acrylic monomer to the epoxy resin in Example 4. Its composition is shown in Table-2. Example 7 A dispersion was obtained by changing the curing agent used in Example 4. Its composition is shown in Table-3. Example 8 When dispersions A to P were spray-painted onto a mild steel plate, good films were formed in all cases. This film was heated at 180° C. for 5 minutes and its performance was then examined. The results are shown in Table-4.

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[Table] Manufactured by Honpolyurethane Co., Ltd.)

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Claims (1)

[Scope of Claims] 1 (A) At least one selected from the group of α,β-unsaturated carboxylic acids, α,β-unsaturated carboxylic acid esters, α,β-unsaturated carboxylic acid amides, and aromatic vinyl compounds. a kind of ethylenic monomer, (B) a condensate of a compound having a phenolic OH group and epichlorohydrin, and at least one member selected from the group of a primary amino group, a secondary amino group, and a phenolic OH group; at least one functional group and at least one carboxyl group in 1
A compound having at least one carboxyl group in one molecule obtained by reaction with a compound having in the molecule, and (C) a condensate of a compound having a phenolic OH group and epichlorohydrin, An aqueous resin dispersion in which the total amount of component (B) and component (C) is in the range of 10 to 1000 parts by weight based on 100 parts by weight of component (A). 2 Component (A) is α,β-unsaturated carboxylic acid, α,
Claim 1, which is a polymer of at least one ethylenic monomer selected from the group of β-unsaturated carboxylic acid ester, α,β-unsaturated carboxylic acid amide, and aromatic vinyl compound. Aqueous resin dispersion. 3 The condensate of component (B) and component (C) is at least 2
It is a condensate of a phenolic OH group-containing compound having at least 1 epoxy group and epichlorohydrin, and each molecule of component (B) contains at least one carboxyl group, a primary amino group, and a secondary amino group. ,
and a compound having at least one carboxyl group in one molecule obtained by the reaction with a compound having at least one functional group selected from the group of phenolic OH groups is an amino acid. The aqueous resin dispersion according to claim 2. 4. The aqueous resin dispersion according to claim 2 or 3, wherein at least a part of the compound of component (B) is neutralized with an alkaline substance. 5. The aqueous resin dispersion according to claim 2, 3, or 4, wherein the weight ratio of component (B) to component (C) is 40/60 to 80/20. 6. The aqueous resin dispersion according to claim 2, which is obtained by emulsion polymerization of a uniform aqueous emulsion dispersion of the monomer of component (A), component (B), and component (C).