JP4357329B2 - Method for producing aqueous dispersion composition - Google Patents

Description

The present invention relates to an aqueous resin composition of a polyolefin-based resin composition modified with at least one copolymerizable monomer selected from a monomer having an α, β-monoethylenically unsaturated group and a carboxylic anhydride. More specifically, the present invention relates to paints, adhesives, primers, binders for inorganic materials, binders for inks, and additives for various materials.

  Conventionally, materials such as plastic, metal, paper, wood, fiber, leather, glass, rubber, ceramic, concrete, and asphalt have been used for various industrial products. Many of these have formed composite materials that combine two or more types of materials to achieve high functionality and cost reduction. Such materials require techniques such as paintability to materials and adhesion of different materials. As industrial materials are widely put into practical use, the types of materials have been diversified and various performances have been required. Among them, polyolefin resins are generally highly productive and excellent in various moldability, and also have many advantages such as light weight, rust prevention, and impact resistance. Widely used as home appliances, furniture, miscellaneous goods, building materials, etc.

  Such polyolefin-based resin molded products are generally non-polar and crystalline, unlike synthetic resins having polarity typified by polyurethane resins, polyamide resins, acrylic resins, and polyester resins. For this reason, it is very difficult to perform coating and adhesion to a general-purpose resin composition.

  For this reason, when coating or adhering to a polyolefin resin molded product, the surface adhesion is improved by activating the surface with chromic acid, flame, corona discharge, plasma, solvent, etc. I have been. For example, in automotive bumpers, the surface is etched with a halogen-based organic solvent such as trichloroethane to improve adhesion to the coating film, or after pretreatment such as corona discharge treatment, plasma treatment, or ozone treatment. However, the purpose of painting and bonding has been made.

  However, in the painting and adhesion using these conventionally known general-purpose resin compositions, not only a great equipment cost is required, but also the construction takes a long time, and the finish is not uniform, the surface treatment state This is the cause of the difference.

  Therefore, conventionally, in order to improve the above-mentioned problems, a method of treating the surface of a substrate such as a molded product with a primer has been employed. For example, a composition in which maleic acid is introduced into a polyolefin (Japanese Patent Publication No. Sho 62-21027) In addition, compositions such as a composition mainly composed of chlorinated modified polyolefin (Japanese Patent Publication No. 50-10916) have been proposed.

Metals such as steel plates are also used in a wide range of fields such as interiors and exteriors of automobiles and ships, home appliances, furniture, sundries, and building materials. The steel sheet surface is painted mainly for the purpose of improving the appearance and imparting anticorrosion properties. In particular, it is important to suppress corrosion and cracking by suppressing deformation and peeling of the coating film due to deformation by external force and collision of objects. At present, in order to suppress these, coating with a modified propylene-ethylene copolymer (Japanese Patent Publication No. 6-057809) or the like obtained by increasing the coating film thickness or graft copolymerizing maleic acid or its anhydride. Is used.
Japanese Patent Publication No. 62-21027 Japanese Patent Publication No. 50-10916 Japanese Patent Publication No. 6-057809

  However, these surface treatment agents also contain insoluble components, do not have sufficient adhesion strength, or have poor solubility in solvents, so that sufficient smoothness cannot be obtained on the coating film surface, There was a problem of a decrease in gloss. Moreover, the compatibility with a pigment and other resin and a dispersibility were not good from the composition, and it increased the viscosity during storage and reduced coating workability. Furthermore, since these surface treatment agents are used in a form dissolved in an organic solvent, there is also a problem that the working environment during production and painting is deteriorated. The object of the present invention is an improvement of the above-mentioned problems, and various materials comprising materials such as plastic, metal, paper, wood, fiber, leather, glass, rubber, ceramic, concrete, and asphalt, especially polyolefin resins such as polypropylene. Excellent adhesion to material films, sheets, or molded products, and excellent adhesion when added to paint, primer or adhesive, and performance as a binder for inorganic and ink materials It is an object to provide an aqueous dispersion composition that expresses the above.

The present inventors have made conducted extensive research and studies in order to achieve the above object, a thermoplastic elastomer and alpha, is selected from a monomer and carboxylic anhydrides having a β- monoethylenically unsaturated group that after producing the tree fat was reacted been a polymer composed of at least one copolymerizable monomer, the aqueous dispersion composition obtained by dispersing in water in the presence of surfactant, the goals Therefore, the present invention has been found to be extremely effective, and the present invention has been completed.

That is, the present invention is specified by the following (1) to (7).
(1) At least one copolymerizable monomer (B) selected from a monomer having an α, β-monoethylenically unsaturated group and a carboxylic anhydride in the thermoplastic elastomer (A) in an organic solvent. After producing a resin obtained by reacting the polymer (C) with a radical generated at a weight ratio of (A) / (C) = 5/95 to 90/10, a surfactant and water are added. A method for producing an aqueous dispersion composition, characterized by comprising:
(2) The method for producing an aqueous dispersion composition according to (1), wherein a part of the thermoplastic elastomer (A) is modified with a functional group.
(3) The coating material containing the aqueous dispersion composition manufactured by the manufacturing method as described in (1) or (2).
(4) An aqueous dispersion composition produced by the production method according to (1) or (2) or a coating film obtained by applying the paint according to (3).
(5) An aqueous dispersion composition having an active hydrogen and / or a hydroxyl group, produced by the production method according to (1) or (2) or a main agent containing the paint according to (3), active hydrogen and / or Or the coating material containing the hardening | curing agent which can react with a hydroxyl group.
(6) A coating film obtained by curing the paint according to (3) .
(7) An adhesive, a primer, an inorganic material binder, and an ink binder containing the aqueous dispersion composition produced by the production method according to (1) or (2).

According to the method for producing the composition of the present invention, or the composition obtained by the method for producing the composition of the present invention, a mixture of active hydrogen and / or a curing agent capable of reacting with a hydroxyl group, the aqueous dispersion is separated. From materials such as plastic, metal, paper, wood, fiber, leather, glass, rubber, ceramic, concrete, and asphalt that can be used as they are without causing any phenomenon, especially polyolefin resin such as polypropylene Conventionally, as paints and primers or adhesives for films and sheets of various materials, or moldings, as additives and adhesion promoters for paints and primers or adhesives, or as binders for inorganic materials and ink materials Has no working effect.

  Details of the present invention will be described below.

  The aqueous dispersion composition of the present invention is a method of emulsifying a resin or resin solution obtained by the following method by mixing ion-exchanged water and a surfactant together, and a resin solution and an interface obtained by the following method. It can manufacture by the method of removing an organic solvent, after mixing an activator and ion-exchange water.

The resin or the resin solution is obtained by adding at least one copolymerizable monomer (B) selected from a monomer having an α, β-monoethylenically unsaturated group and a carboxylic anhydride to the thermoplastic elastomer (A). Or at least one copolymer selected from thermoplastic elastomer (A), a monomer having an α, β-monoethylenically unsaturated group, and a carboxylic anhydride After the polymerization is carried out while feeding a polymerization initiator to the polymerizable monomer (B), it can be produced by a method in which a radical is further generated to carry out the reaction. Further, a polymer comprising a thermoplastic elastomer (A) and at least one copolymerizable monomer (B) selected from a monomer having an α, β-monoethylenically unsaturated group and a carboxylic anhydride. After adding (C), it can also manufacture by the method of generating a radical and reacting, These can also be manufactured in organic solvent presence. The latter is preferred as the method for obtaining the aqueous dispersion composition of the present invention. Furthermore, at least one copolymer selected from a monomer having an α, β-monoethylenically unsaturated group and a carboxylic anhydride is obtained by modifying a part of the thermoplastic elastomer (A) with a functional group. Polymerization is carried out while feeding the polymerizable monomer (B) and the polymerization initiator, or a part of the thermoplastic elastomer (A) is modified with a functional group and a monomer having an α, β-monoethylenically unsaturated group. It can be produced by a method of polymerizing at least one copolymerizable monomer (B) selected from a monomer and carboxylic anhydrides while feeding a polymerization initiator. The product thus obtained can be produced by further generating radicals and reacting with it, and the α, β-monoethylenic unsaturation is obtained by modifying a part of the thermoplastic elastomer (A) with a functional group. A process comprising adding a polymer (C) composed of at least one copolymerizable monomer (B) selected from a monomer having a group and a carboxylic anhydride , followed by generating radicals and reacting them. These can also be produced in the presence of an organic solvent. The latter is preferred as the method for obtaining the aqueous dispersion composition of the present invention.

  Examples of the thermoplastic elastomer (A) used in the present invention include polyethylene, polypropylene, poly-1-butene, poly-3-methyl-1-butene, poly-3-methyl-1-pentene, and poly-4-methyl- 1-pentene, ethylene / propylene copolymer, ethylene / 1-butene copolymer, represented by propylene / 1-butene copolymer, ethylene, propylene, 1-butene, 3-methyl-1-butene, 4 Of α-olefin such as methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-hexene, 1-octene, 1-decene and 1-dodecene, or a copolymer of two or more kinds thereof A thermoplastic elastomer is mentioned. Among these, an ethylene-butene copolymer, an ethylene-propylene copolymer, an ethylene-octene copolymer, an ethylene-propylene-butene copolymer, a propylene-butene copolymer, and a propylene-octene copolymer are preferable. These may be used alone or in combination of two or more. The weight average molecular weight (hereinafter abbreviated as Mw) is in the range of 5,000 to 700,000, preferably 10,000 to 500,000, and more preferably 40,000 to 400,000. That is, when the Mw is less than 5,000, the adhesiveness to the material tends to be poor, and when the Mw exceeds 700,000, it is difficult to stably exist in the solvent.

  In addition, examples of the thermoplastic elastomer (A) include a hydrogenated product of a styrene-conjugated diene block copolymer, which includes a hydrogenated product of a styrene-conjugated diene diblock copolymer, and a styrene-conjugated diene. -Hydrogenated styrene triblock copolymer. Examples of the conjugated diene include butadiene and isoprene.

  Among these, a hydrogenated styrene-isoprene-styrene triblock copolymer, a hydrogenated styrene-butadiene-styrene triblock copolymer, and a hydrogenated styrene-butadiene random copolymer are preferred. .

  The thermoplastic elastomer used here has a styrene content of 2 to 60% by weight, more preferably 3 to 45% by weight.

  The weight average molecular weight (hereinafter abbreviated as Mw) is preferably in the range of 5,000 to 700,000, and a hydrogenated product of a styrene-isoprene-styrene triblock copolymer and a styrene-butadiene-styrene triblock copolymer. In the case of a polymer hydrogenated product, it is preferably 5,000 to 500,000, more preferably 1 to 400,000. The hydrogenated product of a random copolymer of styrene-butadiene is 1 to 500,000, more preferably 5 to 500,000. That is, when the Mw is less than 5,000, the adhesiveness to the material tends to be poor, and when the Mw exceeds 700,000, it is difficult to stably exist in the solvent.

Said thermoplastic elastomer can be used individually or in combination of 2 or more types. A part of the thermoplastic elastomer (A) of the present invention modified with a functional group is an α, β- containing the functional group described below in the thermoplastic elastomer described above or a mixture of two or more thereof. Although it can be obtained by reacting a monomer having a monoethylenically unsaturated group and at least one copolymerizable monomer selected from carboxylic anhydrides, it does not pose any problem even if it contains one that does not react partially.

As the at least one copolymerizable monomer selected from a monomer having a functional group-containing α, β-monoethylenically unsaturated group and carboxylic anhydrides used herein, hydroxyethyl acrylate, 2-hydroxy Hydroxyl-containing vinyls such as ethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, lactone-modified hydroxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, acrylic acid, methacrylic acid, maleic acid, Carboxyl group-containing vinyls such as itaconic acid, ω-carboxy-polycaprolactone monoacrylate, phthalic acid monohydroxyethyl acrylate, nitrogen compounds such as acrylamide, methacrylamide, methylolacrylamide, and methylolmethacrylamide Maleic anhydride, include carboxylic anhydrides such as citraconic anhydride, it alone, can be used even more. The addition amount of the monomer having an α, β-monoethylenically unsaturated group containing the functional group and at least one copolymerizable monomer selected from carboxylic anhydrides is 0. 0 of the weight of the thermoplastic elastomer. It is 5 to 20% of range, more preferably 1 to 15%.

  In addition to the above, the composition of the present invention or the composition of the present invention mixed with a curing agent capable of reacting with active hydrogen and / or a hydroxyl group is not limited to the above, but includes an aqueous epoxy resin, aqueous acrylic resin, A polyester resin, a water-based alkyd resin, a water-based urethane resin, or a paint containing these resins can be mixed and used.

In particular, the composition of the present invention or the composition of the present invention mixed with a curing agent capable of reacting with active hydrogen and / or a hydroxyl group is made into an untreated polyolefin resin film or sheet or molded product by forming a coating film. It can be used as a paint and a primer or an adhesive for a metal or the like, or as a paint and a primer or an adhesive for a metal such as a steel plate or aluminum. Listed below are at least one copolymerizable monomer (B) selected from monomers having an α, β-monoethylenically unsaturated group and carboxylic anhydrides .

  As monomers having α, β-monoethylenically unsaturated groups, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate , Tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, tridecyl (meth) acrylate, lauroyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth ) Acrylate, dimethylaminoethyl (meth) acrylate, (meth) acrylic acid esters such as diethylaminoethyl (meth) acrylate, hydroxyethyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydride Hydroxyl group-containing vinyls such as loxypropyl (meth) acrylate and lactone-modified hydroxyethyl (meth) acrylate, carboxyl group-containing vinyls such as acrylic acid, methacrylic acid, maleic acid and itaconic acid, and monoesterified products thereof, glycidyl ( Epoxy group-containing vinyls such as meth) acrylate and methylglycidyl (meth) acrylate, isocyanate group-containing vinyls such as vinyl isocyanate and isopropenyl isocyanate, styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, etc. Aromatic vinyl, other acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, acrylamide, methacrylamide, methylol acrylamide, and methylol methacrylamide, ethylene, propylene Emissions include α- olefins such as the C4-C20. Moreover, the macromonomer etc. which have the said monomer or its copolymer in a segment, and have a vinyl group at the terminal can also be used.

Further, as the copolymerizable monomer of the carboxylic anhydrides used in the present invention, maleic anhydride, citraconic anhydride and the like. Moreover, description like the methyl (meth) acrylate described here shows methyl acrylate and methyl methacrylate.

It is preferable to use a monomer having an α, β-monoethylenically unsaturated group as a main component. Further, a monomer having an α, β-monoethylenically unsaturated group as a main component and other copolymerizable monomers can be used in combination. The polymer (C) used in the present invention is composed of at least one copolymerizable monomer (B) selected from the following monomer having an α, β-monoethylenically unsaturated group and carboxylic anhydrides. Composed.

The thermoplastic elastomer (A) in the present invention, at least one copolymerizable monomer (B) selected from a monomer having an α, β-monoethylenically unsaturated group and a carboxylic anhydride, or a combination thereof. The ratio of the combined (C) is (A) / (B) = 5/95 to 90/10, or (A) / (C) = 5/95 to 90/10, preferably (A) / (B) = 10/90 to 80/20, or (A) / (C) = 10/90 to 80/20.

  In the present invention, aromatic hydrocarbons such as xylene, toluene and ethylbenzene, aliphatic hydrocarbons such as hexane, heptane, octane and decane, alicyclic hydrocarbons such as cyclohexane, cyclohexene and methylcyclohexane, ethyl acetate and n-acetic acid Organic solvents such as ester solvents such as butyl, cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and 3 methoxybutyl acetate, and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone can be used. It may be a mixture of more than seeds. Among these, aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons are preferable, and aliphatic hydrocarbons and alicyclic hydrocarbons can be more preferably used. The amount of the organic solvent can be used in such a range that the nonvolatile content when the thermoplastic elastomer (A) is dissolved in the organic solvent is 5 to 60% by weight. Examples of the polymerization initiator used in the present invention include di-tert-butyl peroxide, tert-butyl peroxy-2-ethylhexanoate, benzoyl peroxide, dicumyl peroxide, lauroyl peroxide, and tert-butyl peroxybenzo. Eight, organic peroxides such as cumene hydroperoxide, azobisisobutyronitrile, 4,4′-azobis (4-cyanopentanoic acid), 2,2′-azobis (2-methyl-N- (2-hydroxy) And azo compounds such as ethyl) propioamide). These can be used alone or in combination of two or more.

  Further, the radical generation method in the case of performing the reaction by further generating radicals uses a known method such as a method of irradiating light in the presence of a photopolymerization initiator or a method of adding an organic peroxide. can do. Examples of the photopolymerization initiator include benzophenone, diacetyl, benzyl, benzoin, 2-methylbenzoin, ω-bromoacetophenone, chloroacetone, acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone. 2-hydroxy-2-methylpropiophenone, 2-chlorobenzophenone, p-dimethylaminopropiophenone, p-dimethylaminoacetophenone, p, p'-bisdiethylaminobenzophenone, 3,3'-4,4'- Tetra-benzophenone, Michler's ketone, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin-n-butyl ether, 2,4,6-trimethylbenzoyldiphenylphosphineoxy Carbonyls such as benzyl dimethyl ketal and methyl benzoyl formate, sulfides such as diphenyl disulfide, dibenzyl disulfide, tetramethyl thiuram monosulfide, quinones such as benzoquinone, anthraquinone, chloroanthraquinone, ethyl anthraquinone, butyl anthraquinone, thioxanthone, Examples thereof include thioxanthones such as 2-methylthioxanthone and 2-chlorothioxanthone, but these may be used alone or in combination of two or more. These photopolymerization initiators include amines such as triethylamine, trimethylamine, triethanolamine, dimethylaminoethanol, pyridine, quinoline, trimethylbenzylammonium chloride, allylphosphines such as triphenylphosphine, and β-thiodiglycol. A thiol ether such as the above may be used in combination. The amount of the photopolymerization initiator used is usually 0.01 to 10% by weight based on the total weight of the thermoplastic elastomer (A) and the copolymerizable monomer (B) or polymer (C). Preferably, a great effect on the stability appears when used in the range of 0.1 to 5% by weight. When the amount of the photopolymerization initiator used is less than 0.01%, no significant improvement is confirmed in the stability of the obtained aqueous dispersion composition, and gelation occurs when the added amount exceeds 10% by weight. It becomes easy.

  Organic peroxides include di-tert-butyl peroxide, tert-butylperoxy-2-ethylhexanoate, benzoyl peroxide, dioctyl having a tert-butyl group and / or a benzyl group in the molecule. Milperoxide, tert-butylperoxybenzoate, lauroyl peroxide, cumene hydroperoxide and the like can be mentioned. These can be used alone or in admixture of two or more.

  In the present invention, among the above-mentioned organic peroxides, di-tert-butyl peroxide and tert-butyl peroxy-2-ethylhexanoate are more preferably used. That is, an organic peroxide having a tert-butyl group and / or a benzyl group in the molecule has a relatively high hydrogen abstraction ability, and has an effect of improving the graft ratio with polyolefin.

  The amount of the organic peroxide used is usually 2 to 50% by weight, more preferably 3 to the total weight of the thermoplastic elastomer (A) and the copolymerizable monomer (B) or polymer (C). When used in the range of 30% by weight, a great effect on stability appears. In this case, when the amount of the organic peroxide used is less than 2% by weight, the stability of the obtained aqueous dispersion composition is not greatly improved, and conversely, the amount used exceeds 50% by weight. In some cases, the gelation during the reaction or the adhesion to the material due to the decrease in molecular weight becomes poor, and therefore it is preferable to use an organic peroxide in the above-mentioned range. Moreover, it is preferable to add this organic peroxide little by little as much as possible. That is, depending on the amount used, in general, when the organic peroxide is added all at once, the reaction solution is relatively easily gelled. It is preferable to add in small portions separately. Examples of the surfactant used in the present invention include compounds having both a hydrophobic group and a hydrophilic group in the same molecule, and examples thereof include nonionic and anionic surfactants.

  Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene sorbitan ester, polyoxyethylene alkylamine ether, and the like.

  Examples of the anionic surfactant include fatty acid salts, higher alcohol sulfates, alkylbenzene sulfonic acid soda, potassium oleate, naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl ether sulfate, and particularly alkyl benzene sulfonic acid soda, Potassium oleate is preferred.

The amount of the surfactant used is a resin composed of at least one copolymerizable monomer selected from a thermoplastic elastomer, a monomer having an α, β-monoethylenically unsaturated group, and a carboxylic anhydride . About 0.05-40 weight% is preferable, 0.1-20 weight% is further more preferable, and 0.1-10 weight% is especially preferable.

  In addition, this resin solution can be used as a resin from which the solvent during synthesis is removed, or as a resin solution in which an arbitrary solvent is added and dissolved and dispersed after removing the solvent. The resin solution in which the resin is dissolved or dispersed, or the resin solution in which the resin is dispersed in the resin solution is also an embodiment of the resin of the present invention and is included in the present invention.

  In addition, a resin solution in which a resin is dissolved or dispersed, or a resin solution in which a resin is dispersed in a resin solution, obtained by synthesis in an organic solvent is also included in the present invention. Optional solvents include methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, 2-butyl alcohol, benzyl alcohol, cyclohexanol and other alcohols, acetone, methyl ethyl ketone, methyl isobutyl ketone and other ketones, methyl cellosolve And hydrophilic organic solvents such as ethers such as ethyl cellosolve, butyl cellosolve, methyl carbitol, ethyl carbitol, and butyl carbitol. These can be used alone or in combination of two or more. In producing the resin, at least one selected from the group consisting of fats and oils, derivatives of fats and oils, epoxy resins, and polyester resins can be used as the third component. Examples of the fats and oils used as the third component include linseed oil, soybean oil, castor oil, and purified products thereof. Oils and fats used as the third component are short oil alkyds obtained by modifying polybasic acids such as phthalic anhydride and polyhydric alcohols such as glycerin, pentaerythritol and ethylene glycol with oils (fatty acids). Resin, medium oil alkyd resin, long oil alkyd resin, etc., or rosin modified alkyd resin modified with natural resin, synthetic resin and polymerizable monomer, phenol modified alkyd resin, epoxy modified alkyd resin, acrylated alkyd resin, urethane modified Examples include alkyd resins.

  Examples of the epoxy resin used as the third component include an epoxy resin obtained by glycidyl etherification of bisphenol A, bisphenol F, novolak, etc., an epoxy resin obtained by adding propylene oxide or ethylene oxide to bisphenol A, and the like. be able to. Moreover, you may use the amine modified epoxy resin etc. which added the polyfunctional amine to the epoxy group. Furthermore, an aliphatic epoxy resin, an alicyclic epoxy resin, a polyether type epoxy resin, etc. are mentioned.

  The polyester resin used as the third component is obtained by condensation polymerization of a carboxylic acid component and an alcohol component. Examples of the carboxylic acid component include terephthalic acid, isophthalic acid, phthalic anhydride, naphthalenedicarboxylic acid, succinic acid, and glutar Acid, adipic acid, azelaic acid, 1,10-decanedicarboxylic acid, cyclohexanedicarboxylic acid, polycarboxylic acid such as trimellitic acid, maleic acid, fumaric acid and its lower alcohol ester, hydroxycarboxylic acid such as paraoxybenzoic acid, Monovalent carboxylic acids such as benzoic acid can be used, and two or more kinds can be used in combination.

  Examples of the alcohol component include ethylene glycol, diethylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10 -Decanediol, 3-methyl-pentanediol, 2,2'-diethyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, neopentyl glycol, trimethylolethane, trimethylolpropane, glycerin, Pentaerythritol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, ethylene oxide adduct of hydrogenated bisphenol A, propylene oxide adduct of hydrogenated bisphenol A, etc. It is also possible to use them together.

  Moreover, the resin which contained the polymerizable unsaturated bond in the molecule | numerator obtained by adding the carboxylic anhydride which has a polymerizable unsaturated bond in a molecule | numerator to the said polyester resin which has a hydroxyl group can also be used.

  The third component can be used alone or in combination of two or more. Further, it can be added while being fed into the reactor, or it can be first charged into the reactor and used. The amount of the third component added is usually 0.5 to 60% by weight, preferably 2 to 40% by weight, based on the resin component.

  In particular, the aqueous dispersion composition using fats and oils and derivatives of fats and oils as the third component has particularly good stability, good compatibility with other resins, and markedly improved peel strength. In particular, those containing castor oil are highly effective.

  Among the compositions of the present invention, the composition containing hydroxyethyl acrylate, 2-hydroxyethyl (meth) acrylate, acrylic acid, methacrylic acid, etc. as a structural unit, and having active hydrogen and / or hydroxyl group is active hydrogen and A curing agent capable of reacting with a hydroxyl group can be used. For example, it can be used as a paint having a urethane bond, a primer, and an adhesive by mixing with a curing agent having an isocyanate group in the molecule. Examples of the curing agent include Takenate WB series (made by Mitsui Takeda Chemical Co., Ltd.), Elastron BN in which an isocyanate group is treated with a blocking agent such as oximes, lactams, and phenols in water. Series (Daiichi Kogyo Seiyaku Co., Ltd.) etc. are mentioned. A resin synthesized from at least one of melamine, urea, benzoguanamine, glycoluril, and formaldehyde and formaldehyde, for example, a part of a methylol group by a lower alcohol such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, etc. Alternatively, amino resins which are all alkyl etherified can also be used as the curing agent. Furthermore, an oxazoline compound can also be used as a curing agent. Examples of the curing agent include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2- Examples thereof include isopropenyl-4-methyl-2-oxazoline.

  The curing agent capable of reacting with the active hydrogen and / or hydroxyl group of the composition of the present invention can be used in an arbitrary ratio. When the curing agent capable of reacting with active hydrogen and / or hydroxyl group is a curing agent having an isocyanate group, the mixing ratio of active hydrogen and isocyanate group is 0.5: 1.0 to 1.0: The range of 0.5 is preferable, and the range of 0.8: 1.0 to 1.0: 0.8 is more preferable. Further, when the curing agent capable of reacting with active hydrogen and / or hydroxyl group is an amino resin, it is preferably used in the range of 95/5 to 20/80 by weight ratio of the composition / amino resin solid of the present invention. The range of 90/10 to 60/40 is more preferable. Furthermore, when the curing agent capable of reacting with active hydrogen and / or a hydroxyl group is an oxazoline compound, the weight ratio of the composition / amino resin solid of the present invention is 95/5 to 20/80. The range of 90/10 to 60/40 is more preferable. The mixture of the curing agents described above can be applied and cured as it is, but a reactive catalyst can be used in combination as required.

  The composition of the present invention obtained above or the composition of the present invention mixed with a curing agent capable of reacting with active hydrogen and / or a hydroxyl group can be used as it is, but further, an antioxidant as required. In addition, components such as various stabilizers such as a weather resistance stabilizer and a heat resistance inhibitor, a colorant such as an inorganic pigment and an organic pigment, and a conductivity imparting agent such as carbon black and ferrite can be contained. The coating method of the composition of the present invention, or a mixture of the composition of the present invention mixed with a curing agent capable of reacting with active hydrogen and / or hydroxyl group is not particularly limited, but is preferably performed by spray coating, For example, it can be applied by spraying on the surface to be coated with a spray gun. The application can usually be carried out easily at room temperature, and the drying method after application is not particularly limited, and it can be dried by an appropriate method such as natural drying or heat forced drying. The thickness of the coating layer is not particularly limited because it is appropriately selected depending on the use of the laminate. In addition to the above, the composition of the present invention or the composition of the present invention mixed with a curing agent capable of reacting with active hydrogen and / or a hydroxyl group is not limited to the above, but includes an aqueous epoxy resin, aqueous acrylic resin, A polyester resin, a water-based alkyd resin, a water-based urethane resin, or a paint containing these resins can be mixed and used.

  The composition of the present invention or the composition of the present invention mixed with a curing agent capable of reacting with active hydrogen and / or hydroxyl group is made of plastic, metal, paper, wood, fiber, glass, rubber, ceramic, concrete, asphalt It can be used as a paint and primer or adhesive for various materials such as. Examples of the shape include a film, a sheet, a plate, a fiber, and various molded products, but are not particularly limited. The composition of the present invention or the composition of the present invention mixed with a curing agent capable of reacting with active hydrogen and / or a hydroxyl group is an aqueous epoxy resin, aqueous acrylic resin, aqueous polyester resin, aqueous alkyd resin, aqueous urethane resin. Alternatively, it can be used as an additive or adhesion imparting agent that can be mixed with a paint containing these resins, and can also be used as various binders that can be mixed with various materials such as inorganic materials and ink materials.

  Examples of the plastic include olefin resins such as polyethylene and propylene, acetal, acrylic, methyl methacrylate, acetyl cellulose, nitrocellulose, ethylene / acrylic, fluororesin, polyacrylonitrile, polyamide such as nylon, polybutadiene / acrylonitrile, polybutadiene / Saturated polyester such as styrene, polycarbonate, polyethylene, polyethylene terephthalate, polyhydroxy ether, polyimide, polyphenylene oxide, polypropylene, polystyrene and copolymers thereof, polysulfone, polyvinyl acetate, ethylene / vinyl acetate copolymer, polyvinyl alcohol, polyvinyl alkyl Ether, polyvinyl butyral, polyvinyl chloride, polyvinyl methyl ether, polyureta , Alkyd, casein, cyanoacrylate, diallyl phthalate, epoxy and its modified products, furan, melamine formaldehyde, phenol formaldehyde, phenol furfural, unsaturated polyester, polysulfide, resorcinol / phenol formaldehyde, silicone, urea formaldehyde, etc. , Epoxy-novolac, epoxy-phenolic, epoxy-polysulfide, epoxy-silicone, phenolic-butyral, phenolic-nitrile, phenolic-polyamide, polyamide-epoxy, polyimide-epoxy, silicone-vinylphenolic, silicone-phenolic, vinyl formal-phenolic And alloys such as vinyl butyral-phenolic Addition to these, various stabilizers such as antioxidants, weather resistance stability, heat-proofing agents, colorants such as inorganic pigments and organic pigments, conductivity imparting agents such as carbon black and ferrite, and other inorganic and organic additives It can also be used for those added with agents.

  Further, a base material comprising 5 to 80% by weight of at least one metal hydroxide selected from magnesium and aluminum as an olefin resin and 5 to 80% by weight of other inorganic fillers, and a foam thereof is a flooring material. It is preferably used as wallpaper. Examples of metals include iron, carbon steel, cast iron, galvanized steel sheet, Zn-Fe-based, Zn-Ni-based alloy-plated steel sheet, organic composite-plated steel sheet, stainless steel, aluminum and its alloys, copper and its alloys, titanium And alloys thereof. Examples of the paper include glassine paper, high-quality paper, craft paper, newsprint paper, base paper for impregnation processing, thin paper, imitation paper, board paper, tissue paper, and the like. Examples of wood tree species include fir, todomatsu, shirabe, taiwan hinoki, hinoki, sawara, cedar, larch, spruce, spruce, red pine, Japanese pine, black pine, hiba, tsuga etc., coniferous wood, itaya maple, tochinoki, mizume, makanba, Examples include broad-leaved wood such as wig, camphor, cypress, beech, onigurumi, tub, honoki, dronoki, linden, yachidamo, bark, giraffe, mizunara, haruni, zelkova, red oak, and Philippine timber. Examples of fibers include cellulosic regenerated fibers such as rayon and cupra, cellulose synthetic fibers such as acetate, semi-synthetic fibers such as promix proteins, polyamides such as nylon, polyvinyl alcohols, polyvinylidene chlorides, and polyvinyl chlorides. , Polyester, polyacrylonitrile, polyethylene, polypropylene, polyurethane, polyalkylene paraoxybenzoate, phenol and other synthetic fibers, glass fibers, carbon fibers and other inorganic fibers, cotton, flax, linseed, jute, etc. Examples thereof include plant fibers, animal fibers such as wool and silk, and mineral fibers such as asbestos.

  Examples of the glass include borosilicate glass, lead glass, soda lime glass, zinc glass, and quartz glass. Examples of the rubber include silicone rubber, butyl rubber, ethylene-propylene terpolymer, natural rubber, butadiene rubber, styrene butadiene rubber, chloroprene rubber, nitrile rubber, polysulfide rubber, epichlorohydrin rubber, acrylic rubber, and urethane rubber. Examples of the ceramic include alumina, steatite, forsterite, zircon, beryllia, zirconia, silicon nitride, aluminum nitride, silicon carbide, and the like. Examples of the concrete include ordinary concrete, lightweight concrete, heavy concrete, crushed concrete, AE concrete, watertight concrete, cement mortar, lightweight cellular concrete, carbon fiber reinforced concrete, and glass fiber reinforced concrete. Examples of the paint include water-based epoxy resins, water-based acrylic resins, water-based polyester resins, water-based alkyd resins, and water-based urethane resins. Examples of inorganic materials and ink materials used in binder applications include inorganic pigments such as titanium oxide, molybdenum and carbon black, organic pigments such as azo pigments and phthalocyanine blue, and colorants such as dyes such as azo dyes and anthraquinone dyes. And inks made of acrylic, polyester, polyamide, polycarbonate, polyvinyl alcohol, polyvinyl acetate, rosin resin, alkyd resin, phenol resin, coumarone resin, ketone resin, cellulosic resin, alumina, steatite, forsterite, zircon , Ceramics made of beryllia, zirconia, silicon nitride, aluminum nitride, silicon carbide, etc., metal powder, magnetic powder, or a mixture thereof.

  The use of the composition of the present invention, or a mixture of the composition of the present invention mixed with a curing agent capable of reacting with active hydrogen and / or a hydroxyl group is not particularly limited, for example, plywood, Wood materials such as laminated timber, single-layer laminates, building materials such as floors, walls, ceilings, interior tiles, bricks, etc., road pavements, waterproofing, repairing, repairing and reinforcing foundations, joints, and steel structures Civil engineering materials such as automobile materials, automobile interior parts, exterior parts, automobile parts such as engine parts and brake parts, and vehicle materials such as vehicle roofs, windways, decorative panels, heat insulating materials, windows, floors, doors, etc., and Aviation and space materials, mainly aluminum, titanium alloy, FRP and other structural materials, semiconductors, batteries, cable materials, magnetic disks and tapes, small motors, piezoelectric elements, conductive materials, sensors, photosensitive materials, terminals ( phone , Facsimile, etc.) materials, electrical and electronic materials such as copper beam laminates, and communication equipment materials mainly optical parts such as optical fibers, cameras, digital cameras, watches, measuring instruments, copiers, mobile phones, Precision used in car navigation, personal computers, OA equipment materials, ski, snowboard, archery, golf, tennis and other sports equipment materials, shoe uppers, bottoms, shin materials, heels, top lifts, insoles, etc. Footwear materials, fiber flocking materials such as flocking binders, and packaging materials that use paper, plastic, aluminum foil, etc. as the base film of the laminate, and bookbinding materials such as covers, turnovers, backs, and pianos, Electone, musical instrument materials such as electronic musical instruments, furniture materials such as chests, shelves, desks, chairs, sofas, cosmetic containers, miscellaneous goods such as toys, artificial joints, artificial bones Vascular adhesion of the skin, sutures, dental orthodontic, prostheses, and medical materials for use in areas such as storage.

  Hereinafter, the production method of the composition of the present invention and various test examples will be given and further described. In the following, parts and percentages are by weight unless otherwise specified.

[ Reference Example 1]
A four-necked flask equipped with a stirrer, a thermometer, a reflux cooling device, and a nitrogen introduction tube was charged with 120 parts of Bestplast 750 and 400 parts of Isopar C as a thermoplastic elastomer, and heated to 97 ° C while purging with nitrogen. . Next, in this, 98 parts of methyl methacrylate, 42 parts of ethyl acrylate, 28 parts of isobutyl methacrylate, 28 parts of 2-hydroxyethyl methacrylate, 42 parts of Plaxel FM-3 and 42 parts of methacrylic acid as polymerizable monomers As a polymerization initiator, a mixed solution of 2.8 parts of tert-butylperoxy-2-ethylhexanoate (hereinafter abbreviated as PBO) was fed over 4 hours. 200 parts of Isopar C was added 1 hour after the end of the feed, 1.4 parts of PBO was added, and 1.4 parts of PBO was further added after 1 hour. One hour after the addition of PBO, 12 parts of PBO was added, and 8 parts were further added after 1 hour, and 8 parts were further added after 1 hour. The reaction was allowed to stand at 97 ° C. for 2 hours after the last addition of PBO. 500 g of the obtained resin solution, 500 g of ion-exchanged water, and 5 g of sodium dodecylbenzenesulfonate (manufactured by Kao Corporation) were stirred and mixed at a rotational speed of 10,000 rpm for 30 minutes. Next, 1 g of polyacrylic acid was added and mixed by stirring to obtain an emulsion. Isopar C in the obtained emulsion was removed under reduced pressure with an evaporator to obtain an aqueous dispersion composition having a nonvolatile content of 40% by weight. Of the raw materials used above, Bestplast 750 (trade name, manufactured by Huls Japan Co., Ltd.) used as a thermoplastic elastomer is a copolymer of propylene-ethylene-butene, and Isopar C used as a solvent is Exxon Chemical Co., Ltd. is an isoparaffinic organic solvent, and Plaxel FM-3 used as a polymerizable monomer is an unsaturated fatty acid hydroxyalkyl ertel-modified epsilon-caprolactone manufactured by Daicel Chemical Industries. The polyacrylic acid to be added was manufactured by Wako Pure Chemical Industries, Ltd.
[ Reference Example 2]
Synthesis was performed in the same manner as in Reference Example 1 except that sodium dodecylbenzenesulfonate was changed to potassium oleate (Kanto Chemical Co., Ltd.) to obtain an aqueous dispersion composition.
[ Reference Example 3]
Initially charged Bestplast 750 and Isopar C into 200 parts and 500 parts, respectively, and the mixed liquid to be fed is 70 parts of methyl methacrylate, 30 parts of ethyl acrylate, 20 parts of isobutyl methacrylate, 20 parts of 2-hydroxyethyl methacrylate and Plaxel FM. -3 to 30 parts and 30 parts of PBO2 parts of methacrylic acid, 100 parts of Isopar C added after completion of feeding, the the same manner as in example 1 except for changing the PBO are added 1.4 parts of 1 part Synthesis was performed by the method to obtain an aqueous dispersion composition.

[ Reference Example 4]
Initially charged Bestplast 750 and Isopar C are 36 parts and 400 parts, respectively, and the mixed liquid to be fed is 127.4 parts of methyl methacrylate, 54.6 parts of ethyl acrylate, 36.4 parts of isobutyl methacrylate and 2-hydroxyethyl. PBO with 36.4 parts of methacrylate, 54.6 parts of Plaxel FM-3, 54.6 parts of methacrylic acid and 3.64 parts of PBO, 200 parts of Isopar C added after the end of feeding, and 1.4 parts of PBO The composition was synthesized in the same manner as in Reference Example 1 except that the amount was changed to 1.82 parts to obtain an aqueous dispersion composition.

[ Reference Example 5]
Feed the best plast 750 and Isopar C to 320 parts and 500 parts respectively, and feed the mixed liquid into 32 parts of methyl methacrylate, 8 parts of Plaxel FM-3, 40 parts of methacrylic acid and 0.8 parts of PBO. Synthesis was carried out in the same manner as in Reference Example 1 except that Isopar C added later was changed to 100 parts and PBO added to 1.4 parts was changed to 0.4 parts to obtain an aqueous dispersion composition.

[ Reference Example 6]
The mixed liquid to be fed was mixed with 56 parts of methyl methacrylate, 28 parts of ethyl acrylate, 28 parts of isobutyl methacrylate, 28 parts of 2-hydroxyethyl methacrylate, 42 parts of Plaxel FM-3, 42 parts of methacrylic acid and 2.8 parts of PBO. An aqueous dispersion composition was obtained by synthesis in the same manner as in Reference Example 1 except that olester C1000, which is a three-component, was changed to a mixed solution of 56 parts.

[ Reference Example 7]
Synthesis was performed in the same manner as in Reference Example 1 except that the solvent was changed to methylcyclohexane to obtain an aqueous dispersion composition.

[ Reference Example 8]
An aqueous dispersion composition was obtained by synthesis in the same manner as in Reference Example 1 except that the thermoplastic elastomer was changed to Septon 2002. Note that Septon 2002, which is the thermoplastic elastomer used above, is a hydrogenated styrene isoprene block copolymer manufactured by Kuraray Co., Ltd.
[ Reference Example 9]
An aqueous dispersion composition was obtained by synthesizing the thermoplastic elastomer in the same manner as in Reference Example 1 except that 96 parts of Bestplast 750 and 24 parts of Septon 2002 were changed.
[Example 1]
A four-necked flask equipped with a stirrer, a thermometer, a reflux cooling device, and a nitrogen introduction tube was charged with 120 parts of Best Plast 750 and 200 parts of Isopar C as a thermoplastic elastomer and heated to 97 ° C. while replacing with nitrogen. . Next, it is composed of at least one copolymerizable monomer (B) selected from monomers having an α, β-monoethylenically unsaturated group and carboxylic anhydrides obtained in Resin Production Example 1 below. 560 parts of the polymer (C) thus obtained was fed over 4 hours. After the end of feeding, 12 parts of PBO was added, 8 parts were added after 1 hour, and 8 parts were added after 1 hour, and reacted. The reaction was allowed to stand at 130 ° C. for 2 hours after the last addition of PBO. 500 g of the obtained resin solution, 500 g of ion-exchanged water, and 5 g of sodium dodecylbenzenesulfonate (manufactured by Kao Corporation) were stirred and mixed at a rotational speed of 10,000 rpm for 30 minutes. Next, 1 g of polyacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirred to obtain an emulsion. Isopar C in the obtained emulsion was removed under reduced pressure with an evaporator to obtain an aqueous dispersion composition having a nonvolatile content of 40% by weight.

[Resin production example 1]
A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube was charged with 280 parts of toluene and 120 parts of ethyl acetate, and heated to 100 ° C. while purging with nitrogen. Next, in this, a mixed solution of 140 parts of methyl methacrylate, 60 parts of ethyl acrylate, 40 parts of isobutyl methacrylate, 40 parts of 2-hydroxyethyl methacrylate, 60 parts of Plaxel FM-3, 60 parts of methacrylic acid and 4 parts of PBO was added. Feeded over time. Two parts of PBO was added 1 hour after the end of the feed. Further 1 hour later, 2 parts of PBO was added, and then allowed to react for 2 hours to obtain a polymer.

[ Reference Example 1 0 ]
A four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube is charged with 120 parts of Bestplast 750 and 200 parts of Isopar C as a thermoplastic elastomer, and heated to 97 ° C while purging with nitrogen. did. Next, 6 parts of Plaxel FM-3 was added and dispersed therein as a polymerizable monomer having a functional group, and then 6 parts of PBO was added and reacted for 2 hours. Thereafter, 240 parts of Isopar C was added to obtain a resin in which a part of the thermoplastic elastomer was modified with a functional group. Next, while maintaining the inside of the reactor at 97 ° C., 98 parts of methyl methacrylate, 42 parts of ethyl acrylate, 28 parts of isobutyl methacrylate, 28 parts of 2-hydroxyethyl methacrylate and Plaxel FM-3 were used as polymerizable monomers. A mixed solution of 42 parts, 42 parts of methacrylic acid and 2.8 parts of PBO was fed over 4 hours. One hour after the end of the feed, 100 parts of Isopar C was added, 1.4 parts of PBO was added, and 1.4 parts of PBO was added after another hour. The reaction was allowed to stand for 2 hours from the addition of PBO. 500 g of the obtained resin solution, 500 g of ion-exchanged water, and 5 g of sodium dodecylbenzenesulfonate (manufactured by Kao Corporation) were stirred and mixed at a rotational speed of 10,000 rpm for 30 minutes. Next, 1 g of polyacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirred to obtain an emulsion. Isopar C in the obtained emulsion was removed under reduced pressure with an evaporator to obtain an aqueous dispersion composition having a nonvolatile content of 40% by weight.

[ Reference Example 1 1 ]
The mixed liquid to be fed was mixed with 56 parts of methyl methacrylate, 28 parts of ethyl acrylate, 28 parts of isobutyl methacrylate, 28 parts of 2-hydroxyethyl methacrylate, 42 parts of Plaxel FM-3, 42 parts of methacrylic acid and 2.8 parts of PBO. 3 except that I Star C1000 is a component was changed to a mixture of 56 parts to obtain an aqueous dispersion composition synthesis was performed in the same manner as in reference example 1 0.

[ Reference Example 1 2 ]
Except that all the solvent was changed to methyl cyclohexane to give the synthesis was performed in the same manner as in Reference Example 1 0 aqueous dispersion composition.
[ Reference Example 1 3 ]
A four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube is charged with 120 parts of Bestplast 750 and 200 parts of Isopar C as a thermoplastic elastomer, and heated to 97 ° C while purging with nitrogen. did. Next, 6 parts of Plaxel FM-3 was added and dispersed therein as a polymerizable monomer having a functional group, and then 6 parts of PBO was added and reacted for 2 hours. Thereafter, 240 parts of Isopar C was added to obtain a resin in which a part of the thermoplastic elastomer was modified with a functional group. Next, while maintaining the inside of the reactor at 97 ° C., 98 parts of methyl methacrylate, 42 parts of ethyl acrylate, 28 parts of isobutyl methacrylate, 28 parts of 2-hydroxyethyl methacrylate and Plaxel FM-3 were used as polymerizable monomers. A mixed solution of 42 parts, 42 parts of methacrylic acid and 2.8 parts of PBO was fed over 4 hours. One hour after the end of the feed, 100 parts of Isopar C was added, 1.4 parts of PBO was added, and 1.4 parts of PBO was added after another hour. One hour after the addition of PBO, 12 parts of PBO was added, and 8 parts were further added after 1 hour, and 8 parts were further added after 1 hour. The reaction was allowed to stand at 97 ° C. for 2 hours after the last addition of PBO. 500 g of the obtained resin solution, 500 g of ion-exchanged water, and 5 g of sodium dodecylbenzenesulfonate (manufactured by Kao Corporation) were stirred and mixed at a rotational speed of 10,000 rpm for 30 minutes. Next, 1 g of polyacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirred to obtain an emulsion. Isopar C in the obtained emulsion was removed under reduced pressure with an evaporator to obtain an aqueous dispersion composition having a nonvolatile content of 40% by weight.

[Example 2 ]
A four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube is charged with 120 parts of Bestplast 750 and 200 parts of Isopar C as a thermoplastic elastomer, and heated to 97 ° C while purging with nitrogen. did. Next, 6 parts of Plaxel FM-3 is added and dispersed therein as a polymerizable monomer having a functional group, and then 6 parts of PBO is added and reacted for 2 hours, so that a part of the thermoplastic elastomer is functional group. A modified resin was obtained. Subsequently, with the reactor kept at 97 ° C., at least one selected from the monomer having an α, β-monoethylenically unsaturated group and the carboxylic anhydrides obtained in Resin Production Example 1 described in Reference Example 9 560 parts of the polymer (C) composed of the copolymerizable monomer (B) was fed over 4 hours. After the end of feeding, 12 parts of PBO was added, 8 parts were added after 1 hour, and 8 parts were added after 1 hour, and reacted. The reaction was allowed to stand at 97 ° C. for 2 hours after the last addition of PBO. 500 g of the obtained resin solution, 500 g of ion-exchanged water, and 5 g of sodium dodecylbenzenesulfonate (manufactured by Kao Corporation) were stirred and mixed at a rotational speed of 10,000 rpm for 30 minutes. Next, 1 g of polyacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirred to obtain an emulsion. Isopar C in the obtained emulsion was removed under reduced pressure with an evaporator to obtain an aqueous dispersion composition having a nonvolatile content of 40% by weight.

[Comparative Example 1]
Initially charged Bestplast 750 and Isopar C are 16 parts and 300 parts, respectively, and the mixed liquid to be fed is 134.4 parts of methyl methacrylate, 57.6 parts of ethyl acrylate, 38.4 parts of isobutyl methacrylate and 2-hydroxyethyl. PBO containing 38.4 parts of methacrylate, 57.6 parts of Plaxel FM-3, 57.6 parts of methacrylic acid and 3.84 parts of PBO, 300 parts of Isopar C added after the feed is finished, and 1.4 parts of PBO Aqueousization was carried out in the same manner as in Reference Example 1 except that was changed to 1.92 parts.
[Comparative Example 2]
364 parts and 700 parts of the best plast 750 and Isopar C charged initially, respectively, 12 parts of methyl methacrylate, 8 parts of isobutyl methacrylate, 16 parts of methacrylic acid, and 0.36 part of PBO, Aqueous treatment was performed in the same manner as in Reference Example 1 except that the feed time was changed to 1 part, Isopar C added to 0 parts after the feed was completed, and PBO added 1.4 parts to 0.2 parts. It was.

[Comparative Example 3]
Initially charged Bestplast 750 and Isopar C at 16 parts and 60 parts, respectively, feed at least one copolymer selected from monomers having an α, β-monoethylenically unsaturated group and carboxylic anhydrides to be fed Aqueousization was performed in the same manner as in Example 1 except that the polymer (C) composed of the monomer (B) was changed to 768 parts.

[Comparative Example 5]
Initially charged Bestplast 750 and Isopar C are 16 parts and 60 parts, respectively, then Plascel FM-3, a polymerizable monomer having a functional group to be added, is added to 0.8 parts, and then PBO is added 0.8 parts. In addition, 460 parts of isopar C to be added thereafter, 134.4 parts of methyl methacrylate, 57.6 parts of ethyl acrylate, 38.4 parts of isobutyl methacrylate, 38.4 parts of 2-hydroxyethyl methacrylate, the PLACCEL FM-3 in 57.6 parts of 57.6 parts of PBO3.84 parts of methacrylic acid, except for changing the PBO added after completion of the feeding to 1.92 parts water-based in the same manner as in reference example 1 0 Was done.

[Comparative Example 6]
Initially charged Bestplast 750 and Isopar C are 364 parts and 600 parts, respectively, Plascel FM-3, a polymerizable monomer having a functional group to be added, is 18.2 parts, and then PBO is added 18.2 parts. In addition, 100 parts of Isopar C to be added thereafter, 12 parts of methyl methacrylate, 8 parts of isobutyl methacrylate, 16 parts of methacrylic acid, and 0.36 part of PBO, the feed time to 1 hour, after the end of the feed 0 parts of Isopar C to be added, was subjected to water-in the same manner as in reference example 1 0 except for changing the PBO to be added subsequently to 0.2 parts.

[Comparative Example 7]
Initially charged Bestplast 750 and Isopar C are 16 parts and 60 parts, respectively, then Plascel FM-3, a polymerizable monomer having a functional group to be added, is added to 0.8 parts, and then PBO is added 0.8 parts. In addition, 460 parts of isopar C to be added thereafter, 134.4 parts of methyl methacrylate, 57.6 parts of ethyl acrylate, 38.4 parts of isobutyl methacrylate, 38.4 parts of 2-hydroxyethyl methacrylate, the PLACCEL FM-3 in 57.6 parts of 57.6 parts of PBO3.84 parts of methacrylic acid, except for changing the PBO added after completion of the feeding to 1.92 parts water-based in the same manner as in reference example 1 3 Was done.

[Comparative Example 8]
Initially charged Bestplast 750 and Isopar C are 364 parts and 600 parts, respectively, Plascel FM-3, a polymerizable monomer having a functional group to be added, is 18.2 parts, and then PBO is added 18.2 parts. In addition, 100 parts of Isopar C to be added thereafter, 12 parts of methyl methacrylate, 8 parts of isobutyl methacrylate, 16 parts of methacrylic acid, and 0.36 part of PBO, the feed time to 1 hour, after the end of the feed 0 parts of Isopar C to be added, was subjected to water-in the same manner as in reference example 1 3 except for changing the PBO to be added subsequently to 0.2 parts.

[Comparative Example 9]
Initially charged Bestplast 750 and Isopar C are 16 parts and 60 parts, respectively, then Plascel FM-3, a polymerizable monomer having a functional group to be added, is added to 0.8 parts, and then PBO is added 0.8 parts. 768 parts of a polymer (C) composed of at least one copolymerizable monomer (B) selected from a monomer having an α, β-monoethylenically unsaturated group to be fed and a carboxylic anhydride Aqueousization was carried out in the same manner as in Example 2 except that the above was changed.

[Evaluation and results]
Aqueous formation was marked with ◯, and those that could not be made water with x. The results of Examples and Reference Examples are shown in Table-1 and Table-2, and the results of Comparative Examples are shown in Table-3 and Table-4.

<Stability of aqueous solution>
The obtained aqueous dispersion composition was allowed to stand for 1 month under the conditions of a nonvolatile content of 40%, room temperature and 40 ° C., and the state of the solution was evaluated. After 1 month, this aqueous solution was neither separated nor precipitated and confirmed to be thickened, ◎, neither separated nor precipitated, but changed in viscosity, or separated and / or precipitated. Of those observed that were not easily dispersible by stirring where separation and / or precipitation were observed. The results obtained in Examples and Reference Examples are shown in Table-1 and Table-2, and those obtained in Comparative Examples are shown in Table-3 and Table-4.

<< Sprayability of aqueous dispersion solution >>
Using a paint gun (Wider spray gun (product name: W-88-13H5G) manufactured by Iwata Co., Ltd.), atomizing pressure of 4 kg / cm 2, opening of the nozzle one rotation, and temperature in the coating booth at 30 ° C. Each of the aqueous dispersion composition solutions obtained in Examples , Reference Examples and Comparative Examples was sprayed, and observed whether stringing occurred or not. Was marked with x. The results obtained in Examples and Reference Examples are shown in Table-1 and Table-2, and those obtained in Comparative Examples are shown in Table-3 and Table-4.

<< Adhesion (cross-cut peel test) >>
The aqueous solution obtained was subjected to Ford Cup No. The fall speed at 4 was adjusted to 15 ± 2 seconds. Next, a square plate made of polypropylene (product name: J705, manufactured by Sumitomo Mitsui Polyolefin Co., Ltd.) whose surface was wiped with isopropyl alcohol, and a steel plate subjected to surface treatment (thickness: about 20 μm) with a known electrodeposition epoxy paint The aqueous solution was spray-coated on the surface of the electrodeposition paint so that the film thickness after drying was 10 μm to form a coating film, and the appearance and adhesion of the coating film were evaluated. In addition, about adhesiveness, according to the method of the cross-cut peel test described in JIS-K-5400, a test piece with a cross-cut is prepared, and Cellotape (registered trademark) (product of Nichiban Co., Ltd.) is used. After pasting on the grid, it was quickly pulled in a 90 ° direction to peel off, and the evaluation was made based on the number of grids that were not peeled out of 100 grids. The results obtained in Examples and Reference Examples are shown in Table-1 and Table-2, and those obtained in Comparative Examples are shown in Table-3 and Table-4.

"water resistant"
The test piece coated on the steel sheet in the adhesion test was immersed in water adjusted to 40 ° C. for 240 hours, and then the appearance and adhesion of the coating film were evaluated. The results obtained in Examples and Reference Examples are shown in Table-1 and Table-2, and those obtained in Comparative Examples are shown in Table-3 and Table-4.

Furthermore, with respect to the aqueous solutions obtained in Reference Example 1, Example 1 , Reference Example 10 , Reference Example 1 3 and Example 2 , Takenate WD-720 (hereinafter abbreviated as “Takenate”) was added to 100 parts of each of the aqueous solutions. 15 parts mixed, or Cymel 236 (hereinafter abbreviated as Cymel) 10 parts and catalyst Catalyst 500 as 0.8 parts mixed, or Epocross K-2020E (hereinafter abbreviated as Epocross). A mixture of 25 parts was prepared and evaluated as follows.

<< Sprayability of aqueous dispersion solution >>
Using a paint gun (Wider spray gun (product name: W-88-13H5G) manufactured by Iwata Co., Ltd.), atomizing pressure of 4 kg / cm 2, opening of the nozzle one rotation, and temperature in the coating booth at 30 ° C. Each of the aqueous dispersion composition solutions obtained in Examples , Reference Examples and Comparative Examples was sprayed, and observed whether stringing occurred or not. Was marked with x. The results are shown in Table-5 and Table-6.

《Adhesion》
The above aqueous solution is spray-applied to the electrodeposition paint surface of the steel sheet that has been surface-treated (thickness of about 20 μm) with a known electrodeposition epoxy paint so that the film thickness after drying is 10 μm. The appearance of the coating film and the adhesion were evaluated. In addition, about adhesiveness, according to the method of the cross-cut peel test described in JIS-K-5400, a test piece with a cross-cut is prepared, and Cellotape (registered trademark) (product of Nichiban Co., Ltd.) is used. After pasting on the grid, it was quickly pulled in a 90 ° direction to peel off, and the evaluation was made based on the number of grids that were not peeled out of 100 grids. The results are shown in Table-5 and Table-6.

  In addition, for those using Takenate as a curing agent, each of the above aqueous solutions was spray-coated on a square plate made of polypropylene (Mitsui Sumitomo Polyolefin Co., Ltd., product name: J705) so that the film thickness after drying was 10 μm. A coating film is formed by forced drying, and a test piece with a grid pattern is prepared according to the grid pattern peeling test method described in JIS-K-5400. Cellotape (registered trademark) (Nichiban Co., Ltd.) ) Was affixed on the grid, and then immediately pulled in a 90 ° direction to peel off, and the number of grids that were not peeled out of 100 grids was evaluated. The results are shown in Table-5 and Table-6.

"water resistant"
The test piece coated on the steel sheet in the adhesion test was immersed in water adjusted to 40 ° C. for 240 hours, and then the appearance and adhesion of the coating film were evaluated. The results are shown in Table-5 and Table-6.

    Paints and primers for plastics, metals, paper, wood, fibers, leather, glass, rubber, ceramics, concrete, asphalt, etc., especially films and sheets of various materials made of polyolefin resins such as polypropylene Alternatively, it can be used as an adhesive or for applications such as paints and primers or adhesive additives.

Claims (10)

In an organic solvent, the thermoplastic elastomer (A) was composed of at least one copolymerizable monomer (B) selected from monomers having an α, β-monoethylenically unsaturated group and carboxylic anhydrides. After producing a resin obtained by reacting the polymer (C) by generating radicals at a weight ratio of (A) / (C) = 5/95 to 90/10, a surfactant and water are added. A method for producing an aqueous dispersion composition. The method for producing an aqueous dispersion composition according to claim 1, wherein a part of the thermoplastic elastomer (A) is modified with a functional group. The coating material containing the aqueous dispersion composition manufactured by the manufacturing method of Claim 1 or 2. The coating film formed by apply | coating the aqueous dispersion composition manufactured by the manufacturing method of Claim 1 or 2, or the coating material of Claim 3. The aqueous dispersion composition produced by the production method according to claim 1 or 2 having active hydrogen and / or a hydroxyl group, or the main agent containing the coating material according to claim 3 can react with the active hydrogen and / or hydroxyl group. Paint containing various curing agents. A coating film obtained by curing the paint according to claim 3. The adhesive agent containing the aqueous dispersion composition manufactured by the manufacturing method of Claim 1 or 2. The primer containing the aqueous dispersion composition manufactured by the manufacturing method of Claim 1 or 2. The binder for inorganic materials containing the aqueous dispersion composition manufactured by the manufacturing method of Claim 1 or 2. The binder for inks containing the aqueous dispersion composition manufactured by the manufacturing method of Claim 1 or 2.