JPS637207B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides an aqueous 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 they often peel or blister, especially in wet conditions or at high temperatures, which is a serious drawback. It had 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 intensive studies to find an aqueous polymer dispersion that exhibits high adhesiveness on wet surfaces and at high temperatures, and as a result, they have arrived at 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 compound having at least one quaternary ammonium group in the molecule obtained by reacting a condensate of a compound having a phenolic OH group with epichlorohydrin and a tertiary amine; and (C) a condensate of a compound having a phenolic OH group and epichlorohydrin, wherein component (B) is added to 100 parts by weight of component (A).
and component (C) in a total amount of 10 to 1000 parts by weight. The aqueous dispersion of the present invention will be explained in detail below. 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. The epoxy compound of component (C) and the epoxy compound as the starting material of component (B) may be the same or different, but it is preferable that they are the same. Tertiary amines as component (B) used in the present invention include, for example, trialkylamines such as trimethylamine, triethylamine, and tripropylamine; dimethylalkylamines such as dimethylethylamine, dimethylpropylamine, and dimethyllaurylamine; trimethanol; Trialkanolamines such as amines and triethanolamine; dimethylalkanolamines such as dimethylmethanolamine and dimethylethanolamine; methyldialkalamines such as methyldimethanolamine and methyldiethanolamine; dimethylbenzylamine, tetramethylethylenediamine, and tetramethylpropylenediamine , pentamethyldiethylenetriamine, N-methylmorpholine, N-ethylmorpholine; polyoxyethylene laurylamine, polyoxyethylene stearylamine, and the like. Preferred is dimethylethanolamine. The reaction between a compound having an epoxy group and a tertiary amine can be achieved by heating in the presence of water for 10 minutes to 20 hours at a temperature range of 40°C to 100°C with or without the addition of an acid. It will be done. At this time, the tertiary amino group is mixed in a ratio of 0.1 to 1.0 equivalent, preferably 0.5 equivalent, per 1 equivalent of epoxy group. Water is 1 to 10 per equivalent of tertiary amino group.
It may be used in moles, preferably 2 to 4 moles. The acid used in the present invention is acetic acid, lactic acid, lactic acid, etc., and the amount of acid added is preferably equal to or less than the tertiary amine used in the reaction. The aqueous dispersion of the present invention can be obtained by uniformly mixing the above components (A), (B) and (C) in an aqueous medium. A coating film having sufficient hardness and adhesion cannot be obtained with only component (A) and component (B), and a stable aqueous dispersion cannot be obtained with only component (A) and 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 dispersion of the present invention includes the following steps:
A method in which the ethylenic monomer (A) is subjected to emulsion polymerization to obtain an aqueous dispersion of the polymer, to which component (B) and component (C) are sequentially or simultaneously added, and the mixture is forcibly stirred using a high-speed stirrer. , a method of preparing an emulsified dispersion by adding a surfactant, water, and an organic solvent as desired to component (B) and component (C), and mixing this with an aqueous polymer dispersion of component (A), etc. There is. However, a more preferred method is to uniformly mix the monomer of component (A) and components (B) and (C), and add a surfactant, a dispersant, a protective colloid, etc., water, a polymerization initiator, Furthermore, this is a method in which an organic solvent and other additives are added as necessary to form an emulsion dispersion, and emulsion polymerization is carried out. 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. According to this method, not only the working process of emulsion polymerization is simplified, but also an aqueous dispersion having uniform components and stability can be obtained. Emulsion polymerization for obtaining the aqueous dispersion of the present invention is carried out by conventionally known methods. That is, the surfactants, dispersants, and protective colloids necessary to provide a site for emulsion polymerization and maintain the dispersion stability of the produced polymer particles include, for example, fatty acid soaps, alkyl sulfate ester salts, and alkylbenzene sulfones. acid salt, dialkyl sulfosuccinate ester salt,
Alkyl phosphate ester salt, polyoxyethylene alkyl sulfate ester salt, polyoxyethylene alkyl phosphate ester salt, alkyl diphenyl alkyl phosphate ester salt, alkyl diphenyl ether disulfonate, vinyl sulfonate, 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, alkylamine salt, quaternary ammonium salt, polyoxyethylene alkyl Examples of polymerization initiators for ethylenic monomers include amines, polyphosphates, polyacrylates, maleic anhydride copolymer salts, polybonyl alcohol, and hydroxyethyl cellulose. Examples of polymerization initiators for ethylenic monomers include persulfates, peroxides, and azobis compounds. In addition, a redox system in which these are combined with a reducing agent is used. Further, a PH adjuster such as sodium hydrogen phosphate or sodium hydrogen carbonate and an organic solvent are added as necessary. The aqueous dispersion of the present invention includes polyamines having primary and secondary amino groups, their adducts, compounds having active hydrogen such as polyamide polyamines, and condensates of phenols such as phenols and alkylphenols with formalin. , an aminoplast resin is added, mixed uniformly, dried, and heated if necessary to form a film with excellent adhesiveness having a crosslinked network structure. The film obtained by the aqueous dispersion of the present invention has excellent water resistance, good chemical resistance, boiling water resistance,
It also has sufficient flexibility. The aqueous dispersion obtained by the present invention has a wide range of uses, including paints for metals, paints containing pigments, adhesives using tack, 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 An epoxy resin was added as an epoxy compound to a separable flask equipped with a stirrer and a reflux device.
AER-661 (manufactured by Asahi Kasei, epoxy equivalent 465)
Add 117g, xylene 60g, and n-butanol 60g and mix uniformly. To this, 50 g of diethylaminoethanol (DEAE), 30 g of lactic acid, and 60 g of water were added, and the reaction was carried out at 60°C for 3 hours. AER for this
Add 117 g of -661 and mix, then add 30 g of styrene and 30 g of methacrylic acid as polymerizable monomers, mix uniformly, and then transfer the mixed solution to beaker 2. When 400 g of water was added to this mixed solution while stirring it with a homomixer, a white aqueous dispersion A was obtained. Example 2 953 g of the aqueous dispersion A obtained in Example 1 was mixed with 500 g of water prepared separately, and 2,2'-azobis(2-amidinopropane) dihydrochloride (trade name V) as an initiator for the polymerizable monomer. -50 (manufactured by Wako Pure Chemical Industries, Ltd.) 0.3g is uniformly dissolved and dripped into an aqueous solution kept at a temperature of 80°C over about 1 hour. After the dropwise addition, the reaction was continued for about 1 hour, and then 0.3 g of V-50 was added to
The reaction was carried out at .degree. C. for 2 hours, and upon cooling to room temperature, a white aqueous dispersion B was obtained. Example 3 10 g of 65 g of Beetle (methylated urea manufactured by Mitsui Toatsu Co., Ltd.) was added to 140 g of the aqueous dispersion B of Example 2 and mixed uniformly to obtain a white aqueous dispersion C. Example 4 When dispersions A to C were spray-painted onto a mild steel plate, good films were formed in all cases. This film was heated at 200° C. for 5 minutes, and the physical properties of the baked film were measured. The results are shown in Table-1. 【table】

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 compound having at least one quaternary ammonium group in the molecule obtained by reacting a condensate of a compound having a phenolic OH group with epichlorohydrin and a tertiary amine. , and (C) a condensate of a compound having a phenolic OH group and epichlorohydrin, wherein component (B) is added to 100 parts by weight of component (A).
and component (C) in a total amount of 10 to 1000 parts by weight. 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 dispersion. 3. The condensate used for component (B) and the condensate for component (C) are condensates of epichlorohydrin and a phenolic OH group-containing compound having at least two epoxy groups. Aqueous dispersion. 4. The aqueous dispersion according to claim 2, wherein at least a portion of the quaternary ammonium groups of the compound (B) are neutralized with an acid. 5. The aqueous 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 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).