JP2004307848A - Aqueous resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an aqueous resin composition capable of exhibiting performance as a coating material and a primer or an adhesive for a material, such as plastic, metal, paper, wood, fiber, leather, glass, rubber, ceramic, concrete and asphalt, especially for a film, a sheet and a molded product of various kinds of materials formed out of polyolefin-based resins including polypropylene, as an additive and an adhesion-imparting agent for the coating material and the primer or the adhesive, or as a binder for an inorganic material and an ink material. <P>SOLUTION: This aqueous resin composition contains a resin, a basic substance and water as components, wherein the resin is formed out of a thermoplastic elastomer and a copolymerizable monomer component composed of a monomer having an α,β-monoethylenic unsaturated group and another copolymerizable monomer and has an acid value of ≥25 in terms of solid. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an aqueous resin composition of a polyolefin-based resin composition modified with a copolymerizable monomer comprising a monomer having an α, β-monoethylenically unsaturated group and another copolymerizable monomer. 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 form composite materials that combine two or more types of materials to achieve higher functionality and lower costs. 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 painting 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 of the bumper 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 a solvent, so that sufficient smoothness cannot be obtained on the surface of the coating film. There was a problem of lowering. 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 in providing the aqueous resin composition which expresses.

  As a result of intensive studies and studies to achieve the above object, the present inventors have found that a thermoplastic elastomer, a monomer having an α, β-monoethylenically unsaturated group, and other copolymerizable monomers. A composition obtained by neutralizing a resin having a solid acid value of 25 or more by reacting with a copolymerizable monomer consisting of a monomer with a basic compound and making it water-based is extremely effective for achieving the above target. As a result, the present invention has been completed.

That is, the present invention is specified by the following (1) to (12).
(1) A thermoplastic elastomer (A) and a copolymerizable monomer (B) comprising a monomer having an α, β-monoethylenically unsaturated group and another copolymerizable monomer (A) / (B) = Aqueous resin composition comprising a resin (D) having a solid acid value of 25 or more as a result of reaction at a weight ratio of 5/95 to 90/10, a basic substance and water as components. .
(2) An aqueous resin composition comprising the resin (D) according to (1), an organic solvent, a basic substance, and water as components.
(3) Resin (D) as described in (1) can be copolymerized with a monomer having an α, β-monoethylenically unsaturated group in the presence of the thermoplastic elastomer (A) in an organic solvent A resin obtained by polymerizing a copolymerizable monomer (B) composed of monomers at a weight ratio of (A) / (B) = 5/95 to 90/10, and further generating radicals and reacting them. The aqueous resin composition according to (1) or (2).
(4) Resin (D) according to (1) is a thermoplastic elastomer (A) in an organic solvent, a monomer having an α, β-monoethylenically unsaturated group, and other copolymerizable monomers. Resin obtained by reacting a polymer (C) composed of a copolymerizable monomer (B) consisting of a polymer with radicals generated at a weight ratio of (A) / (C) = 5/95 to 90/10 The aqueous resin composition according to (1) or (2).
(5) The resin (D) according to (1) has an α, β-monoethylenically unsaturated group in which a part of the thermoplastic elastomer (A) is modified with a functional group in an organic solvent. A resin obtained by polymerizing a copolymerizable monomer (B) composed of a monomer and other copolymerizable monomers at a weight ratio of (A) / (B) = 5/95 to 90/10 (1 Or the aqueous resin composition according to (2).
(6) The resin (D) according to (1) has a part of the thermoplastic elastomer (A) modified with a functional group in an organic solvent and an α, β-monoethylenically unsaturated group. After the monomer and other copolymerizable monomer (B) are polymerized at a weight ratio of (A) / (B) = 5/95 to 90/10, radicals are further added. The aqueous resin composition according to (1) or (2), which is a resin generated and reacted.
(7) The resin (D) according to (1) has an α, β-monoethylenically unsaturated group in which a part of the thermoplastic elastomer (A) is modified with a functional group in an organic solvent. A polymer (C) composed of a copolymerizable monomer (B) composed of a monomer and another copolymerizable monomer, and a weight of (A) / (C) = 5/95 to 90/10 The aqueous resin composition according to (1) or (2), which is a resin obtained by generating radicals and reacting at a ratio.
(8) A paint containing the aqueous resin composition according to (1) or (2).
(9) A coating film formed by applying the aqueous resin composition according to (1) or (2) or the paint according to (8).
(10) Curing capable of reacting with active hydrogen and / or hydroxyl group, and main agent containing the aqueous resin composition according to (1) or (2) having active hydrogen and / or hydroxyl group or the coating material according to (8) Paint containing agent.
(11) A coating film obtained by curing the paint according to (10).
(12) An adhesive, a primer, a binder for inorganic materials, a binder for ink, and an additive containing the aqueous resin composition according to (1) or (2).

  According to 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, the aqueous resin can be used as it is without causing a separation phenomenon. For materials such as plastic, metal, paper, wood, fiber, leather, glass, rubber, ceramic, concrete, and asphalt that can be painted, especially films and sheets of various materials made of polyolefin resin such as polypropylene. As a paint and primer or adhesive, or as an additive or adhesion imparting agent for paint, primer or adhesive, or as a binder for inorganic materials or ink materials, it has an unprecedented effect.

  Details of the present invention will be described below.

  The aqueous resin composition of the present invention is obtained by adding a basic substance after dissolving or diluting a resin or resin solution obtained by the following method with a hydrophilic organic solvent, or by partially or completely replacing the solvent at the time of synthesis. Then, neutralization can be performed, and ion-exchanged water can be added for production.

  The above resin or resin solution comprises a copolymerizable monomer (B) comprising a monomer having an α, β-monoethylenically unsaturated group and another copolymerizable monomer in the thermoplastic elastomer (A). Copolymerizable monomer comprising polymerizing while feeding a polymerization initiator, or comprising a thermoplastic elastomer (A) and a monomer having an α, β-monoethylenically unsaturated group and other copolymerizable monomers. (B) can be produced by a method in which a polymerization initiator is fed while being polymerized and then a radical is further generated to react. In addition, a polymer composed of a copolymerizable monomer (B) composed of a monomer having an α, β-monoethylenically unsaturated group and another copolymerizable monomer (B) on the thermoplastic elastomer (A) ( After adding C), it can also be produced by a method in which a reaction is performed by generating radicals, and these can also be produced in the presence of an organic solvent. The latter is preferred as a method for obtaining the aqueous resin composition of the present invention.

  Further, a copolymerization property consisting of a monomer having an α, β-monoethylenically unsaturated group and another copolymerizable monomer in which a part of the thermoplastic elastomer (A) is modified with a functional group A monomer (B) is polymerized while feeding a 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, and In addition, it can be produced by a method of polymerizing a copolymerizable monomer (B) comprising a copolymerizable monomer 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. It can also be produced by adding a polymer (C) composed of a copolymerizable monomer (B) composed of a monomer having a group and other copolymerizable monomers, and then generating radicals for reaction. These can also be produced in the presence of an organic solvent. The latter is preferred as a method for obtaining the aqueous resin 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, hydrogenated products of styrene-isoprene-styrene triblock copolymer, hydrogenated products of styrene-butadiene-styrene triblock copolymer, and hydrogenated products of random copolymer of styrene-butadiene are preferable. .

  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) described in the present invention is modified with a functional group, and the above-described thermoplastic elastomer or a mixture of two or more of them contains α, β containing the following functional groups: -It can be obtained by reacting a monomer having a monoethylenically unsaturated group and other copolymerizable monomer, but there is no problem even if it contains a non-reacting monomer.

  Examples of the copolymerizable monomer comprising a monomer having an α, β-monoethylenically unsaturated group containing a functional group and other copolymerizable monomers used herein include hydroxyethyl acrylate, 2-hydroxyethyl Hydroxyl-containing vinyls such as (meth) acrylate, 2-hydroxypropyl (meth) acrylate, lactone-modified hydroxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, acrylic acid, methacrylic acid, maleic acid, itacon Acid, ω-carboxy-polycaprolactone monoacrylate, carboxyl group-containing vinyls such as monohydroxyethyl acrylate phthalate, nitrogen compounds such as acrylamide, methacrylamide, methylolacrylamide, methylolmethacrylamide, maleic anhydride , Include carboxylic anhydrides such as citraconic anhydride, it alone, can be used even more.

  The amount of the copolymerizable monomer comprising the above-mentioned functional group-containing monomer having an α, β-monoethylenically unsaturated group and other copolymerizable monomers is such that the weight of the thermoplastic elastomer is 0.5. It is -20% of range, More preferably, it is 1-15%. Examples of the copolymerizable monomer (B) composed of a monomer having an α, β-monoethylenically unsaturated group and other copolymerizable monomers used in the present invention are given below.

  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-containing vinyls such as loxypropyl (meth) acrylate, lactone-modified hydroxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, acrylic acid, methacrylic acid, maleic acid, itaconic acid, ω-carboxy-poly Carboxyl group-containing vinyls such as caprolactone monoacrylate and monohydroxyethyl phthalate, and monoesterified products thereof, epoxy group-containing vinyls such as glycidyl (meth) acrylate and methylglycidyl (meth) acrylate, vinyl isocyanate, isopropenyl Isocyanate group-containing vinyls such as isocyanate, aromatic vinyls such as styrene, α-methylstyrene, vinyltoluene and t-butylstyrene, other acrylonitrile, methacrylonitrile And vinyl acetate, vinyl propionate, acrylamide, methacrylamide, methylol acrylamide, and methylol methacrylamide, ethylene, propylene, and C4-C20 α-olefins. 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.

  Examples of the copolymerizable monomer comprising other copolymerizable monomers used in the present invention include carboxylic anhydrides such as maleic anhydride and citraconic anhydride. 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 a copolymerizable monomer (B) comprising a monomer having an α, β-monoethylenically unsaturated group described below and another copolymerizable monomer. Is done.

  Copolymerizable monomer (B) comprising the thermoplastic elastomer (A) of the present invention, a monomer having an α, β-monoethylenically unsaturated group and other copolymerizable monomers, or a polymer thereof The ratio of (C) is (A) / (B) = 5/95 to 90/10 by weight ratio, or (A) / (C) = 5/95 to 90/10, preferably (A) / ( B) = 10/90 to 80/20, or (A) / (C) = 10/90 to 80/20.

  The acid value of the resin of the present invention is 25 mgKOH / g or more, preferably 30 mgKOH / g or more. When the acid value is 25 mgKOH / g or less, the hydrophilicity becomes low and it becomes difficult to make it water-based. The acid value described above is a value in a resin (solid) excluding a solvent.

  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 and 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 resin composition, and gelation tends to occur when the addition amount exceeds 10% by weight. Become.

  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, there is no significant improvement in the stability of the obtained aqueous resin composition. Conversely, when the amount used exceeds 50% by weight. Is inferior in adhesion to the material due to gelation or molecular weight reduction during the reaction, it is preferable to use an organic peroxide in the above range. Moreover, it is preferable to add this organic peroxide little by little as much as possible. That is, depending on the amount used, generally when adding an organic peroxide in a batch, the reaction solution is relatively easy to gel, so take a small amount of time or divide it many times. It is preferable to add little by little.

  The resin of the present invention can be used as a resin from which the solvent during the reaction 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 obtained by conducting the reaction in an organic solvent and having the resin dissolved or dispersed, or a 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.

  Examples of the hydrophilic organic solvent used in the present invention 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 the like. Examples include ketones, ethers such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl carbitol, ethyl carbitol, and butyl carbitol. These can be used alone or in combination of two or more. The amount of the hydrophilic organic solvent to be contained is preferably 50% or more, more preferably 70% or more of the total solvent amount of the resin solution.

  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, novolac, 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, a resin composition using oils and fats and derivatives of oils and fats 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.

  Basic compounds include ethylamine, propylamine, butylamine, benzylamine, triethylamine, monoethanolamine, diethylamine, diethanolamine, trimethylamine, triethylamine, triisopropylamine, dimethylethanolamine, triethanolamine, methyldiethanolamine, diethylenetriamine, ethylaminoethylamine. Amines such as ammonia, alkaline earth metal hydroxides such as ammonia, sodium hydroxide and calcium hydroxide, and alkali metal salts. The addition amount is neutralized at 50 to 100 mol% of the carboxyl group. Two or more of these may be used in combination.

  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. 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, an aqueous acrylic resin, an aqueous 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 plastics include olefin resins such as polyethylene and propylene, acetal, acrylic, methyl methacrylate, acetylcellulose, nitrocellulose, ethylene / acrylic, fluororesin, polyacrylonitrile, polyamides 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.

[Example 1]
A four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube was charged with 60 parts of Best Plast 750 and 200 parts of Shellsol TG as a thermoplastic elastomer and heated to 130 ° C while purging with nitrogen. did. Next, in this, 49 parts of methyl methacrylate, 21 parts of ethyl acrylate, 14 parts of isobutyl methacrylate, 14 parts of 2-hydroxyethyl methacrylate, 21 parts of Plaxel FM-3 and 21 parts of methacrylic acid as polymerizable monomers As a polymerization initiator, a mixed solution of 1.4 parts of di-tert-butyl peroxide (hereinafter abbreviated as PBD) was fed over 4 hours. 30 minutes after the end of feeding, the temperature was raised to 135 ° C., and further 30 minutes later, 100 parts of Shellsol TG was added, 0.7 part of PBD was added, and 0.7 part of PBD was further added after 1 hour. 30 minutes after the addition of PBD, the temperature was raised to 160 ° C., 30 parts after that, 6 parts of PBD was added, 4 parts were added after 1 hour, and 4 parts were added after 1 hour, and reacted. The reaction was allowed to stand at 160 ° C. for 2 hours after the last addition of PBD to obtain a resin solution having a solid acid value of 68 mgKOH / g. The obtained resin solution was heated to 130 ° C., and 250 parts of the solvent was removed under reduced pressure. To this, 100 parts of butyl cellosolve was added and dissolved, then neutralized with triethylamine to theoretically 100%, adjusted with deionized water so that the non-volatile content was 40%, and an aqueous resin composition was prepared. Obtained.

  In addition, as a raw material used above, the thermoplastic elastomer is a copolymer of propylene-ethylene-butene of Best Plast 750 (product name manufactured by Huls Japan), and the solvent is Shellsol TG (Shell Japan). Plaxel FM-3 using an isoparaffinic organic solvent (product name) as a polymerizable monomer was unsaturated fatty acid hydroxyalkyl ertel modified epsilon-caprolactone manufactured by Daicel Chemical Industries.

[Example 2]
The liquid mixture to be fed was a mixture of 14 parts of methyl methacrylate, 28 parts of styrene, 42 parts of isobutyl methacrylate, 14 parts of 2-hydroxyethyl methacrylate, 21 parts of Plaxel FM-3, 21 parts of methacrylic acid and 1.4 parts of PBD. The aqueous resin composition was obtained by synthesizing in the same manner as in Example 1 except that the acid value in the solid was changed to 68 mgKOH / g.

[Example 3]
100 parts and 250 parts of Bestplast 750 and Shellzol TG charged initially, respectively, 35 parts of methyl methacrylate, 15 parts of ethyl acrylate, 10 parts of isobutyl methacrylate, 10 parts of 2-hydroxyethyl methacrylate and Plaxel 15 parts of FM-3, 15 parts of methacrylic acid and 1 part of PBD, 50 parts of Shellsol TG added after the end of feeding, and 0.5 part of PBD added 0.7 parts (acid in solid) A water-based resin composition was obtained by synthesis in the same manner as in Example 1 except that the value was 50 mgKOH / g).

[Example 4]
Initially charged Bestplast 750 and Shellsol TG are 18 parts and 200 parts, respectively, and the mixed liquid to be fed is 63.7 parts methyl methacrylate, 27.3 parts ethyl acrylate, 18.2 parts isobutyl methacrylate and 2-hydroxy. Add 18.2 parts of ethyl methacrylate, 27.3 parts of Plaxel FM-3, 27.3 parts of methacrylic acid and 1.82 parts of PBD, and add 0.7 parts of Shellsol TG added after the feed to 100 parts. Synthesis was carried out in the same manner as in Example 1 except that the PBD was changed to 0.91 part (the acid value in the solid was 89 mgKOH / g) to obtain an aqueous resin composition.

[Example 5]
Feed the best plast 750 and shell sol TG initially charged to 160 parts and 250 parts, respectively, and feed the mixed liquid to 12 parts methyl methacrylate, 4 parts Plaxel FM-3, 24 parts methacrylic acid and 0.4 parts PBD. The same method as in Example 1 except that 50 parts of Shellsol TG to be added after completion and 50 parts of PBD to which 0.7 parts were added were changed to 0.2 parts (the acid value in the solid was 78 mgKOH / g). And an aqueous resin composition was obtained.

[Example 6]
The mixture to be fed was mixed with 28 parts of methyl methacrylate, 14 parts of ethyl acrylate, 14 parts of isobutyl methacrylate, 14 parts of 2-hydroxyethyl methacrylate, 21 parts of Plaxel FM-3, 21 parts of methacrylic acid and 1.4 parts of PBD. The aqueous resin composition was obtained by synthesizing in the same manner as in Example 1 except that the three components, olester C1000, were changed to a mixed solution of 28 parts (the acid value in the solid was 68 mgKOH / g).

[Example 7]
All solvents were changed to methylcyclohexane, polymerization initiator was changed to tert-butylperoxy-2-ethylhexanoate (hereinafter abbreviated as PBO), and the temperature in the system was changed to 97 ° C. in all steps (acid value in solid) Was synthesized in the same manner as in Example 1 except that it was 68 mgKOH / g) to obtain an aqueous resin composition.

[Example 8]
Synthesis was performed in the same manner as in Example 1 except that the thermoplastic elastomer was changed to Septon 2002 (the acid value in the solid was 68 mgKOH / g) to obtain an aqueous resin composition. Note that Septon 2002, which is the thermoplastic elastomer used above, is a hydrogenated styrene isoprene block copolymer manufactured by Kuraray Co., Ltd.

[Example 9]
A thermoplastic elastomer was synthesized by the same method as in Example 1 except that 48 parts of Bestplast 750 and 12 parts of Septon 2002 were changed (solid acid value was 68 mgKOH / g). A composition was obtained.

[Example 10]
A four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube was charged with 60 parts of Bestplast 750 as thermoplastic elastomer and 100 parts of Shellsol TG, and heated to 130 ° C while purging with nitrogen. did. Next, it is composed of a copolymerizable monomer (B) comprising a monomer having an α, β-monoethylenically unsaturated group obtained in the following resin production example 1 and other copolymerizable monomers. 280 parts of the polymer (C) was fed over 4 hours. After the end of feeding, 6 parts of PBO was added, 4 parts were added after 1 hour, and 4 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 to obtain a resin solution having a solid acid value of 68 mgKOH / g. The obtained resin solution was decompressed while maintaining at 130 ° C. to remove 190 parts of the solvent. To this, 100 parts of butyl cellosolve was added and dissolved, then neutralized with triethylamine to theoretically 100%, adjusted with deionized water so that the non-volatile content was 40%, and an aqueous resin composition was prepared. Obtained.

[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 70 parts of xylene and 30 parts of anone, and heated to 100 ° C. while purging with nitrogen. Next, in this, a mixed solution of 35 parts of methyl methacrylate, 15 parts of ethyl acrylate, 10 parts of isobutyl methacrylate, 10 parts of 2-hydroxyethyl methacrylate, 15 parts of Plaxel FM-3, 15 parts of methacrylic acid and 1 part of PBO was added. Feeded over time. One hour after the end of feeding, 0.5 part of PBO was added. After an additional hour, 0.5 part of PBO was added, and after 1 hour, the temperature in the reactor was raised to 110 ° C. and left to react for 1 hour to obtain a polymer.

[Example 11]
A four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube was charged with 60 parts of Bestplast 750 and 100 parts of Shellsol TG as a thermoplastic elastomer and heated to 130 ° C while purging with nitrogen. Warm up. Next, 3 parts of Plaxel FM-3 was added and dispersed therein as a polymerizable monomer having a functional group, and then 3 parts of PBD was added and reacted for 2 hours. Thereafter, 120 parts of Shellsol TG 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 130 ° C., 49 parts of methyl methacrylate, 21 parts of ethyl acrylate, 14 parts of isobutyl methacrylate, 14 parts of 2-hydroxyethyl methacrylate, and Plaxel FM-3 were used as polymerizable monomers. A mixed solution of 21 parts, 21 parts of methacrylic acid and 1.4 parts of PBD was fed over 4 hours. 30 minutes after the end of feeding, the temperature was raised to 135 ° C., and further 30 minutes later, 50 parts of Shellsol TG was added, 0.7 part of PBD was added, and 0.7 part of PBD was further added after 1 hour. 30 minutes after the addition of PBD, the temperature was raised to 160 ° C., and the mixture was further allowed to react for 1 hour to obtain a resin solution having a solid acid value of 67 mgKOH / g. The obtained resin solution was heated to 130 ° C., and 220 parts of the solvent was removed under reduced pressure. To this, 100 parts of butyl cellosolve was added and dissolved, then neutralized with triethylamine to theoretically 100%, adjusted with deionized water so that the non-volatile content was 40%, and an aqueous resin composition was prepared. Obtained.

[Example 12]
The mixture to be fed was mixed with 28 parts of methyl methacrylate, 14 parts of ethyl acrylate, 14 parts of isobutyl methacrylate, 14 parts of 2-hydroxyethyl methacrylate, 21 parts of Plaxel FM-3, 21 parts of methacrylic acid and 1.4 parts of PBD. The aqueous resin composition was obtained by synthesis in the same manner as in Example 11 except that olester C1000, which is a three-component, was changed to a mixed solution of 28 parts (the acid value in the solid was 67 mgKOH / g).

[Example 13]
Synthesis was carried out in the same manner as in Production Example 11 except that the solvent was all methylcyclohexane, the polymerization initiator was PBO, and the temperature in the system was changed to 97 ° C. in all steps (the acid value in the solid was 67 mgKOH / g). An aqueous resin composition was obtained.
[Example 14]
A four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube was charged with 60 parts of Bestplast 750 and 100 parts of Shellsol TG as a thermoplastic elastomer and heated to 130 ° C while purging with nitrogen. Warm up. Next, 3 parts of Plaxel FM-3 as a polymerizable monomer having a functional group was added and dispersed therein, and then 3 parts of PBD was added and reacted for 2 hours. Thereafter, 120 parts of Shellsol TG 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 130 ° C., 49 parts of methyl methacrylate, 21 parts of ethyl acrylate, 14 parts of isobutyl methacrylate, 14 parts of 2-hydroxyethyl methacrylate, and Plaxel FM-3 were used as polymerizable monomers. A mixed solution of 21 parts, 21 parts of methacrylic acid and 1.4 parts of PBD was fed over 4 hours. 30 minutes after the end of feeding, the temperature was raised to 135 ° C., and further 30 minutes later, 50 parts of Shellsol TG was added, 0.7 part of PBD was added, and 0.7 part of PBD was further added after 1 hour. 30 minutes after the addition of PBD, the temperature was raised to 160 ° C., 30 parts after that, 6 parts of PBD was added, 4 parts were added after 1 hour, and 4 parts were added after 1 hour, and reacted. The reaction was allowed to stand at 160 ° C. for 2 hours after the last addition of PBD to obtain a resin solution having a solid acid value of 67 mgKOH / g. The obtained resin solution was heated to 130 ° C., and 220 parts of the solvent was removed under reduced pressure. To this, 100 parts of butyl cellosolve was added and dissolved, then neutralized with triethylamine to theoretically 100%, adjusted with deionized water so that the non-volatile content was 40%, and an aqueous resin composition was prepared. Obtained.

[Example 15]
A four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube was charged with 60 parts of Bestplast 750 and 100 parts of Shellsol TG as a thermoplastic elastomer and heated to 130 ° C while purging with nitrogen. Warm up. Next, 3 parts of Plaxel FM-3 is added and dispersed therein as a polymerizable monomer having a functional group, and then 3 parts of PBD is added and reacted for 2 hours, so that a part of the thermoplastic elastomer is functional group. A modified resin was obtained. Next, the reactor was heated to 110 ° C., and a copolymer comprising a monomer having an α, β-monoethylenically unsaturated group obtained in Resin Production Example 1 described in Example 9 and other copolymerizable monomers was used. 280 parts of the polymer (C) composed of the polymerizable monomer (B) was fed over 4 hours. After the end of feeding, 6 parts of PBO was added, 4 parts were added after 1 hour, and 4 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 to obtain a resin solution having a solid acid value of 67 mgKOH / g. The obtained resin solution was decompressed while maintaining at 130 ° C. to remove 190 parts of the solvent. To this, 100 parts of butyl cellosolve was added and dissolved, then neutralized with triethylamine to theoretically 100%, adjusted with deionized water so that the non-volatile content was 40%, and an aqueous resin composition was prepared. Obtained.
[Comparative Example 1]
Initially charged Bestplast 750 and Shellsol TG are 8 parts and 150 parts, respectively, and 67.2 parts of methyl methacrylate, 28.8 parts of ethyl acrylate, 19.2 parts of isobutyl methacrylate and 2-hydroxy are fed. Add 19.2 parts of ethyl methacrylate, 28.8 parts of Plaxel FM-3, 28.8 parts of methacrylic acid and 1.92 parts of PBD, 150 parts of Shellsol TG added after the feed is completed, and 0.7 parts. Aqueousization was carried out in the same manner as in Example 1 except that the PBD was changed to 0.96 parts (the acid value in the solid was 94 mgKOH / g).

[Comparative Example 2]
182 parts and 350 parts of Bestplast 750 and Shellzol TG charged initially, 8 parts of methyl methacrylate, 10 parts of methacrylic acid, and 0.18 part of PBD, respectively, and the feed time of this mixture is 1 hour In addition, the shell sol TG added after the feed is finished is changed to 0 parts, 0.7 parts added PBD is changed to 0.1 parts, and the amount of solvent removed under reduced pressure is changed to 300 parts (the acid value of the solid is , 33 mgKOH / g), and the aqueous solution was formed in the same manner as in Example 1.

[Comparative Example 3]
70 parts of methyl methacrylate, 28 parts of ethyl acrylate, 35 parts of isobutyl methacrylate, 2.8 parts of 2-hydroxyethyl methacrylate, 2.8 parts of Plaxel FM-3, 1.4 parts of methacrylic acid and PBD1 Aqueousization was carried out in the same manner as in Example 1 except that the amount was changed to 4 parts (the acid value of the solid was 5 mgKOH / g).

[Comparative Example 4]
Copolymerizability consisting of monomers having α, β-monoethylenically unsaturated groups and other copolymerizable monomers to be fed to 8 parts and 30 parts of Bestplast 750 and Shellzol TG charged initially, respectively. The same as Example 10, except that the polymer (C) composed of the monomer (B) was changed to 384 parts and the amount of the solvent to be removed under reduced pressure was changed to 172 parts (the acid value in the solid was 94 mgKOH / g). Aqueous formation was carried out by the method.

[Comparative Example 5]
Copolymerizability consisting of monomers having α, β-monoethylenically unsaturated groups and other copolymerizable monomers to be fed to 182 parts and 300 parts of Bestplast 750 and Shellsol TG charged initially, respectively. The polymer (C) composed of the monomer (B) is added to the resin solution obtained in the following resin production example 2, the amount thereof is 90 parts, the feed time of this resin solution is 1 hour, under reduced pressure. Aqueousization was performed in the same manner as in Example 10 except that the amount of solvent to be removed was changed to 322 parts (the acid value in the solid was 35 mg KOH / g).

[Resin production example 2]
A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube was charged with 120 parts of xylene and 40 parts of butyl acetate, and heated to 100 ° C. while replacing with nitrogen. Next, a mixed solution of 16 parts of methyl methacrylate, 24 parts of methacrylic acid and 0.2 part of PBO was fed into this over 4 hours. One hour after the end of the feed, 0.1 part of PBO was added. After further 1 hour, 0.1 part of PBO was added, and after 1 hour, the temperature in the reactor was raised to 110 ° C. and allowed to react for 1 hour to obtain a polymer.

[Comparative Example 6]
Initially charged Bestplast 750 and Shellsol TG are 8 parts and 30 parts, respectively, then Plascel FM-3, a polymerizable monomer having a functional group to be added, is added to 0.4 part, and then PBD is added to 0.4 parts. Parts of shell sol TG to be added to 230 parts, and 67.2 parts of methyl methacrylate, 28.8 parts of ethyl acrylate, 19.2 parts of isobutyl methacrylate, and 19.2 parts of 2-hydroxyethyl methacrylate. Parts and Plaxel FM-3 were changed to 28.8 parts, methacrylic acid 28.8 parts and PBD 1.92 parts, PBD added after the feed was finished 0.96 parts, and the amount of solvent removed under reduced pressure was 260 parts. (The acid value in the solid was 94 mg KOH / g), and the aqueous solution was formed in the same manner as in Example 11.

[Comparative Example 7]
182 parts and 300 parts of Bestplast 750 and Shellzol TG charged in the initial stage are respectively added to 9.2 parts of a polymerizable monomer having a functional group to be added, 9.1 parts, and then PBD to be added is 9.1 parts. To 50 parts of shell sol TG to be added thereafter, 8 parts of methyl methacrylate, 10 parts of methacrylic acid and 0.18 part of PBD, and 1 hour of feed time, shell sol to be added after completion of feeding Example 11 except that TG was changed to 0 parts, PBD added thereafter was changed to 0.1 parts, and the amount of solvent removed under reduced pressure was changed to 300 parts (the acid value of the solid was 31 mgKOH / g). Aqueous formation was carried out by the method.

[Comparative Example 8]
Initially charged Bestplast 750 and Shellsol TG are 8 parts and 30 parts, respectively, then Plascel FM-3, a polymerizable monomer having a functional group to be added, is added to 0.4 part, and then PBD is added to 0.4 parts. Parts of shell sol TG to be added to 230 parts, and 67.2 parts of methyl methacrylate, 28.8 parts of ethyl acrylate, 19.2 parts of isobutyl methacrylate, and 19.2 parts of 2-hydroxyethyl methacrylate. Parts and Plaxel FM-3 were changed to 28.8 parts, methacrylic acid 28.8 parts and PBD 1.92 parts, PBD added after the feed was finished 0.96 parts, and the amount of solvent removed under reduced pressure was 260 parts. (The acid value in the solid was 94 mgKOH / g), and the aqueous solution was formed in the same manner as in Example 14.

[Comparative Example 9]
182 parts and 300 parts of Bestplast 750 and Shellzol TG charged in the initial stage are respectively added to 9.2 parts of a polymerizable monomer having a functional group to be added, 9.1 parts, and then PBD to be added is 9.1 parts. To 50 parts of shell sol TG to be added thereafter, 8 parts of methyl methacrylate, 10 parts of methacrylic acid and 0.18 part of PBD, and 1 hour of feed time, shell sol to be added after completion of feeding Example 14 except that TG was changed to 0 parts, PBD added thereafter was changed to 0.1 parts, and the amount of solvent removed under reduced pressure was changed to 300 parts (the acid value of the solid was 35 mgKOH / g). Aqueous formation was carried out by the method.

[Comparative Example 11]
Initially charged Bestplast 750 and Shellsol TG are 8 parts and 30 parts, respectively, then Plascel FM-3, a polymerizable monomer having a functional group to be added, is added to 0.4 part, and then PBD is added to 0.4 parts. 384 parts of a polymer (C) composed of a copolymerizable monomer (B) comprising a monomer having an α, β-monoethylenically unsaturated group to be fed and other copolymerizable monomers In addition, the amount of the solvent to be removed under reduced pressure was changed to 172 parts (the acid value of the solid was 94 mgKOH / g).

[Comparative Example 12]
182 parts and 300 parts of Bestplast 750 and Shellzol TG charged in the initial stage are respectively added to 9.2 parts of a polymerizable monomer having a functional group to be added, 9.1 parts, and then PBD to be added is 9.1 parts. Comparative Example of Polymer (C) Consisting of Copolymerizable Monomer (B) Consisting of Monomer having Unsaturated α, β-Monoethylenically Unsaturated Group and Other Copolymerizable Monomer 4. The resin solution obtained in the resin production example 2 described in 4 was changed to 90 parts, the feed time of the resin solution was changed to 1 hour, and the amount of solvent removed under reduced pressure was changed to 322 parts (in solid form) Aqueousization was performed in the same manner as in Example 15 except that the acid value was 34 mgKOH / g.

[Evaluation and results]
《Water-based》
Those that could be made aqueous were marked with ◯, and those that could not be made water were marked with x. The results of 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 resin composition was allowed to stand for 1 month under the respective 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 are shown in Tables 1 and 2 for those obtained in Examples and Tables 3 and 4 for those obtained in Comparative Examples.

<< Sprayability of aqueous resin composition >>
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 resin composition solutions obtained in Examples and Comparative Examples was sprayed to observe whether stringing occurred or not. . The results are shown in Tables 1 and 2 for those obtained in Examples and Tables 3 and 4 for those obtained in Comparative Examples.

<< 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 are shown in Tables 1 and 2 for those obtained in Examples and Tables 3 and 4 for those obtained in Comparative Examples.

"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 Tables 1 and 2 for those obtained in Examples and Tables 3 and 4 for those obtained in Comparative Examples.

さらに、実施例１、１０、１１、１４、１５で得られた水溶液については、それぞれの水溶液１００部に、タケネートＷＤ−７２０（以下、タケネートと略記する）を１５部混合したもの、或いはサイメル２３６（以下、サイメルと略記する）を１０部と触媒であるキャタリスト５００を０．８部混合したもの、或いはエポクロスＫ−２０２０Ｅ（以下、エポクロスと略記する）を２５部混合したものを作成し、下記の評価を行った。

Further, for the aqueous solutions obtained in Examples 1, 10, 11, 14, and 15, 100 parts of each aqueous solution was mixed with 15 parts of Takenate WD-720 (hereinafter abbreviated as “bakenate”), or Cymel 236. 10 parts (hereinafter abbreviated as Cymel) and 0.8 part of catalyst 500 which is a catalyst, or 25 parts of Epocross K-2020E (hereinafter abbreviated as Epocross) are prepared, The following evaluation was performed.

<< Sprayability of aqueous resin composition >>
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 resin composition solutions obtained in Examples and Comparative Examples was sprayed to observe whether stringing occurred or not. . 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 (16)

A thermoplastic elastomer (A) and a copolymerizable monomer (B) comprising a monomer having an α, β-monoethylenically unsaturated group and other copolymerizable monomers (A) / (B) = A water-based resin composition comprising a resin (D) having a solid acid value of 25 or more and a basic substance and water as components, which are reacted at a weight ratio of 5/95 to 90/10. An aqueous resin composition comprising the resin (D) according to claim 1, an organic solvent, a basic substance, and water as components. The resin (D) according to claim 1 is a monomer having an α, β-monoethylenically unsaturated group and other copolymerizable monomers in the presence of the thermoplastic elastomer (A) in an organic solvent. The copolymerizable monomer (B) becomes (A) / (B) =
The aqueous resin composition according to claim 1 or 2, which is a resin obtained by polymerizing at a weight ratio of 5/95 to 90/10 and further generating radicals and reacting. The resin (D) according to claim 1 is a copolymer comprising a thermoplastic elastomer (A), a monomer having an α, β-monoethylenically unsaturated group and another copolymerizable monomer in an organic solvent. A polymer obtained by reacting a polymer (C) composed of a polymerizable monomer (B) by generating radicals at a weight ratio of (A) / (C) = 5/95 to 90/10. 3. The aqueous resin composition according to 1 or 2. The resin (D) according to claim 1, wherein a part of the thermoplastic elastomer (A) is modified with a functional group in an organic solvent, a monomer having an α, β-monoethylenically unsaturated group, and Copolymerizable monomer consisting of other copolymerizable monomers (
The aqueous resin composition according to claim 1 or 2, which is a resin obtained by polymerizing B) at a weight ratio of (A) / (B) = 5/95 to 90/10. The resin (D) according to claim 1, wherein a part of the thermoplastic elastomer (A) is modified with a functional group in an organic solvent, a monomer having an α, β-monoethylenically unsaturated group, and Copolymerizable monomer consisting of other copolymerizable monomers (
The water-based resin according to claim 1 or 2, which is a resin obtained by polymerizing B) with a weight ratio of (A) / (B) = 5/95 to 90/10, and further generating radicals and reacting them. Composition. The resin (D) according to claim 1, wherein a part of the thermoplastic elastomer (A) is modified with a functional group in an organic solvent, a monomer having an α, β-monoethylenically unsaturated group, and Copolymerizable monomer consisting of other copolymerizable monomers (
A polymer obtained by reacting the polymer (C) constituted by B) by generating radicals at a weight ratio of (A) / (C) = 5/95 to 90/10. The aqueous resin composition as described. The coating material containing the aqueous resin composition of Claim 1 or 2. The coating film formed by apply | coating the aqueous resin composition of Claim 1 or 2, or the coating material of Claim 8. A paint containing an aqueous resin composition according to claim 1 or 2 having active hydrogen and / or a hydroxyl group or a main agent containing the paint according to claim 8 and a curing agent capable of reacting with active hydrogen and / or a hydroxyl group. . The coating film formed by hardening | curing the coating material of Claim 10. An adhesive containing the aqueous resin composition according to claim 1 or 2. A primer containing the aqueous resin composition according to claim 1. The binder for inorganic materials containing the aqueous resin composition of Claim 1 or 2. The binder for inks containing the aqueous resin composition of Claim 1 or 2. The additive containing the aqueous resin composition of Claim 1 or 2.