JP2009185160A - Coating material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous coating material exhibiting excellent adhesiveness to a sheet of varied resin consisting of polyolefin such as polypropylene, synthetic rubber, unsaturated polyester, epoxy resin, urethane resin and the like, to a molded product and the like, to a steel plate, and to metal such as aluminum by solving conventional problems. <P>SOLUTION: The coating material comprises an aqueous resin composition of a thermoplastic elastomer (A-1), an aqueous resin composition of an urethane resin (B-1), and/or an aqueous resin product of a resin (B-2) consisting of copolymerizable monomers comprising a monomer having α,β-monoethylenically unsaturated group and other copolymerizable monomers, and/or an aqueous resin composition of a polyester (B-3), and/or an aqueous resin composition of an epoxy resin (B-4), and an aqueous resin compositions of a modified amino resin (C). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention is excellent as a paint and primer for various resin sheets or molded articles made of polyolefin such as polypropylene, synthetic rubber, unsaturated polyester, epoxy resin, urethane resin, etc., or for metals such as steel plate and aluminum. It is related with the coating material used as a coating material and a primer which expresses very close_contact | adherence.

Polyolefin resins generally have many advantages such as high productivity and excellent moldability, light weight, rust prevention, and impact resistance. Widely used as 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. In addition, a method of treating the surface of a base material such as a molded product with a primer is used. For example, a composition in which maleic acid is introduced into a polyolefin (Patent Document 1), or a composition mainly composed of a chlorinated modified polyolefin ( Patent Document 2) has also 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, a coating with a thick coating film or a modified propylene-ethylene copolymer (Patent Document 3) formed by graft copolymerization with maleic acid or its anhydride is used. ing. However, these contain organic solvents such as toluene and xylene, and there are concerns about problems such as safety and environmental pollution. Therefore, a composition containing chlorinated modified polyolefin as a main component is dispersed in water (Patent Document 4), and is composed of an olefin polymer and a petroleum hydrocarbon resin (Patent Document 5). ) Etc. have been proposed.

However, since these use a large amount of a surfactant to form an aqueous system, there arises a problem that the water resistance of the coating film and the adhesion to the substrate are lowered, or the surface is bleed out to cause stickiness. If the amount of the surfactant that causes these problems is reduced, problems such as inability to form an aqueous system or poor stability of the aqueous resin composition occur. Moreover, many of these also have the problem that sufficient adhesiveness with respect to a base material is not expressed.
Japanese Patent Publication No. 62-21027 Japanese Patent Publication No. 50-10916 Japanese Patent Publication No. 6-057809 JP-A-1-256556 JP 2004-27055 A

  An object of the present invention is an improvement of the above-mentioned problems, such as polyolefin sheets such as polypropylene, synthetic rubber, unsaturated polyester, epoxy resin, urethane resin, various resin sheets, molded articles, steel sheets, aluminum, etc. An object of the present invention is to provide a water-based coating material that exhibits excellent adhesion to the above metal.

  As a result of intensive studies and studies to achieve the above object, the inventors of the present invention have found that an aqueous resin composition of the thermoplastic elastomer (A-1) and an aqueous resin composition of the urethane resin (B-1). And / or water-based resin product of resin (B-2) comprising a copolymerizable monomer comprising a monomer having an α, β-monoethylenically unsaturated group and other copolymerizable monomer, and / or A coating material comprising an aqueous resin composition of polyester (B-3) and / or an aqueous resin composition of epoxy resin (B-4) and an aqueous resin composition of a modified amino resin (C). The present inventors have found that it is extremely effective for achieving the above-mentioned goal, and have completed the present invention.

That is,
[1] Water-based resin composition of thermoplastic elastomer (A-1), water-based resin composition of urethane resin (B-1) and / or monomer having an α, β-monoethylenically unsaturated group and others Resin (B-2) aqueous resin composition and / or polyester (B-3) aqueous resin composition and / or epoxy resin (B-4) comprising a copolymerizable monomer comprising a copolymerizable monomer A coating material comprising: a water-based resin composition, and a water-based resin composition of a modified amino resin (C).
[2] A coating material comprising an aqueous resin composition of a modified thermoplastic elastomer (A-2) and an aqueous resin composition of a modified amino resin (C).
[3] An aqueous resin composition of a modified thermoplastic elastomer (A-2), an aqueous resin composition of a urethane resin (B-1) and / or a monomer having an α, β-monoethylenically unsaturated group, and In addition, an aqueous resin composition of a resin (B-2) and / or an aqueous resin composition of a polyester (B-3) and / or an epoxy resin (B-4) comprising a copolymerizable monomer comprising a copolymerizable monomer ) And an aqueous resin composition of a modified amino resin (C).
[4] Water-based resin composition of thermoplastic elastomer (A-1) and modified thermoplastic elastomer (A-2), water-based resin composition of urethane resin (B-1) and / or α, β-monoethylenic An aqueous resin composition of resin (B-2) and / or an aqueous resin composition of polyester (B-3) comprising a copolymerizable monomer comprising a monomer having an unsaturated group and another copolymerizable monomer And / or an aqueous resin composition of epoxy resin (B-4) and an aqueous resin composition of modified amino resin (C).
[5] 10 to 95 parts by weight of the aqueous resin composition of the thermoplastic elastomer (A-1) and / or the modified thermoplastic elastomer (A-2), the aqueous resin composition of the urethane resin (B-1) and / or An aqueous resin composition and / or polyester (B-) of a resin (B-2) comprising a copolymerizable monomer comprising a monomer having an α, β-monoethylenically unsaturated group and another copolymerizable monomer 3) aqueous resin composition and / or epoxy resin (B-4) aqueous resin composition 0-70 parts by weight and modified amino resin (C) aqueous resin composition 5-50 parts by weight, (A -1) and / or (A-2), (B-1) and / or (B-2) and / or (B-3) and / or (B-4), and the sum of (C) A coating material, which is mixed so as to be 100 parts by weight.

  The present invention is an aqueous system that exhibits excellent adhesion to various resins such as polyolefin, such as polypropylene, synthetic rubber, unsaturated polyester, epoxy resin, urethane resin, or molded articles, and steel, steel, and other metals. Coating material.

  The coating material of the present invention can be obtained by mixing an aqueous resin composition obtained by the following method.

Thermoplastic elastomer (A-1)
Examples of the thermoplastic elastomer (A-1) 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, propylene / 1-butene copolymer, represented by ethylene / propylene / 1-butene copolymer, ethylene, propylene, Α such as 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-hexene, 1-octene, 1-decene, 1-dodecene, etc. -The thermoplastic elastomer of the olefin single or 2 or more types of copolymers is mentioned. In addition, polymers containing alicyclic structures such as norbornene polymers, monocyclic cyclic polyolefin polymers, cyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers, and hydrogenated products thereof should also be used. Can do.

  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. The weight average molecular weight can be measured by, for example, gel permeation chromatography (GPC) using polystyrene as a standard) is usually 10,000 to 700, 000, preferably 30,000 to 500,000.

In addition, examples of the thermoplastic elastomer (A-1) include a hydrogenated product of a styrene-conjugated diene block copolymer, a hydrogenated product of a styrene-conjugated diene random copolymer, and the like. Examples of the composition of the combined hydrogenated product include a hydrogenated product of a styrene-conjugated diene diblock copolymer, a hydrogenated product of a styrene-conjugated diene-styrene triblock copolymer, and the like. Examples of the conjugated diene used here include butadiene and isoprene. Among these, a hydrogenated product of a styrene-isoprene-styrene triblock copolymer and a hydrogenated product of a random copolymer of styrene-butadiene are preferable.
The thermoplastic elastomer used here has a styrene content of usually 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 10,000 to 700,000, and the hydrogenated product of styrene-isoprene-styrene copolymer is preferably 15,000 to 500,000. Moreover, in the hydrogenated product of a styrene-butadiene copolymer, 10,000-700,000, Furthermore, 50,000-500,000 are preferable. Said thermoplastic elastomer can be used individually or in combination of 2 or more types.

Modified thermoplastic elastomer (A-2)
The modified thermoplastic elastomer (A-2) used in the present invention is obtained by modifying the materials described below into the above-described thermoplastic elastomer (A-1) alone or a mixture of two or more thereof. be able to. For example, a method of removing a solvent after reacting a thermoplastic elastomer (A-1) and a copolymerizable monomer in the presence of a polymerization initiator in an organic solvent, or a thermoplastic elastomer (A-1) and an acrylic resin in an organic solvent. Alternatively, a method of removing the solvent after reacting the urethane resin in the presence of a polymerization initiator, or reacting an acrylic resin or urethane resin having a functional group capable of reacting with the thermoplastic elastomer (A-1) grafted with the functional group. A method in which the thermoplastic elastomer (A-1) is melted by heating, a method in which a copolymerizable monomer, an acrylic resin, or a urethane resin and a polymerization initiator are reacted with stirring, A mixture of a plastic elastomer (A-1) and a copolymerizable monomer, an acrylic resin, or a urethane resin and a polymerization initiator is supplied to an extruder and added. De be mentioned a method in which the reaction is performed while kneading, no problem include those that do not react in a part.

As the copolymerizable monomer composed of a monomer having an α, β-monoethylenically unsaturated group and other copolymerizable monomers used here, methyl (meth) acrylate, ethyl (meth) acrylate, Propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-amyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) Acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, stearyl (meth) acrylate, tridecyl (meth) acrylate, lauroyl (meth) Acrylate, Cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylamino (Meth) acrylic acid esters such as ethyl (meth) acrylate, hydroxyethyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, lactone-modified hydroxyethyl (meth) Hydroxyl group-containing vinyls such as acrylate, 2-hydroxy-3-phenoxypropyl acrylate, acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, ω- Carboxyl group-containing vinyls such as ruboxoxy-polycaprolactone monoacrylate and phthalate monohydroxyethyl acrylate, and monoesters thereof, epoxy group-containing vinyls such as glycidyl (meth) acrylate and methylglycidyl (meth) acrylate, vinyl isocyanate , Vinyls containing isocyanate groups such as isopropenyl isocyanate, aromatic vinyls such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, acrylamide, methacrylamide, N-methylolmethacrylamide, N-methylolacrylamide Amides such as diacetone acrylamide and maleic acid amide, vinyl esters such as vinyl acetate and vinyl propionate, N, N-dimethylaminoethyl (meth) acrylate, N N-diethylaminoethyl (methacrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-dipropylaminoethyl (meth) acrylate, N, N-dibutylaminoethyl (meth) acrylate, N, N-dihydroxy Aminoalkyl (meth) acrylates such as ethylaminoethyl (meth) acrylate, unsaturated sulfonic acids such as styrenesulfonic acid, sodium styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, mono (2-methacryloyloxy) Unsaturated phosphoric acids such as ethyl) acid phosphate and mono (2-acryloyloxyethyl) acid phosphate, other acrylonitrile, methacrylonitrile, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, ethylene _Propylene, C 4 of _{-C 20} alpha-olefin, 1,2,2,6,6-pentamethyl-4-piperidyl (meth) acrylate, 2,2,6,6-tetramethyl-4-piperidyl (meth) acrylate , 2- (2′-hydroxy-5′-methacryloyloxyethylphenyl) -2H-benzotriazole and the like. 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.
Examples of the organic solvent that can be used here include aromatic hydrocarbons such as xylene, toluene, and ethylbenzene, aliphatic hydrocarbons such as hexane, heptane, octane, decane, isooctane, and isodecane, cyclohexane, cyclohexene, methylcyclohexane, and ethylcyclohexane. Alicyclic hydrocarbons, ethyl acetate, n-butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ester solvents such as 3 methoxybutyl acetate, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, etc. These organic solvents can be used, and a mixture of two or more of these may be used. Among these, aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons are preferable, and aliphatic hydrocarbons and alicyclic hydrocarbons are more preferably used.

  As the polymerization initiator used in the present invention, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxybenzoate) hexyne- Peroxides such as 3,1,4-bis (tert-butylperoxyisopropyl) benzene, persulfates such as ammonium persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide, the polymerization initiator described above, Alternatively, redox initiators by combining these with metal ions such as iron ions and sodium sulfoxylate, formaldehyde, sodium pyrosulfite, sodium hydrogen sulfite, L-ascorbic acid, Rongalite, etc. Species or two or more types can be used

Thermoplastic elastomer, water-based resin composition of modified thermoplastic elastomer The thermoplastic elastomer (A-1) and / or modified thermoplastic elastomer (A-2) obtained above is an acid-modified polyolefin salt and / or higher fatty acid. Can be dispersed in water by the following method.

Examples of the salt of the acid-modified polyolefin used in the present invention include a carboxylic acid salt group bonded to a polymer chain of the polyolefin (including a carboxylic acid group in the case of a partially neutralized product or a partially saponified product), 1 gram of resin. It is an olefin resin containing 0.05 to 5 mmol, preferably 0.1 to 4 mmol as —COO— groups.
The acid-modified polyolefin is, for example, a polyolefin composed of α-olefin, a monomer having a neutralized or non-neutralized carboxylic acid group, and / or a saponified or unsaponified carboxylic acid. A monomer having an acid ester can be obtained by graft copolymerization.
As for the molecular weight of the acid-modified polyolefin, an α-olefin alone or a copolymer of two or more types having a weight average molecular weight (Mw) measured by GPC in the range of 1000 to 50000 is preferable. Specific examples of the α-olefin include ethylene, propylene, butene, pentene, hexene, octene and the like. Among these, ethylene homopolymer, propylene homopolymer, and ethylene-propylene copolymer are particularly preferable.
Examples of the monomer having a neutralized or non-neutralized carboxylic acid group and the monomer having a saponified or non-saponified carboxylic acid ester group include, for example, ethylenically unsaturated carboxylic acid , Anhydrides thereof or esters thereof.

Examples of the ethylenically unsaturated carboxylic acid (meth) acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic ^TM (Endoshisu as its anhydride -Bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid), maleic anhydride, citraconic anhydride, and the like, as unsaturated carboxylic acid ester, methyl of the above ethylenically unsaturated carboxylic acid, Examples include monoesters or diesters such as ethyl or propyl. These monomers can be used alone or in combination.

In order to produce a modified product by graft copolymerization of a graft monomer selected from the above monomers with a grafted polymer, various conventionally known methods can be employed. Examples thereof include a method of melting a grafted polymer and adding a graft monomer and graft copolymerizing, or a method of dissolving in an organic solvent and adding a graft monomer and graft copolymerizing. In any case, in order to efficiently graft copolymerize the graft monomer, it is preferable to carry out the reaction in the presence of a polymerization initiator.
The grafting reaction is usually performed at a temperature of 60 to 350 ° C. The ratio of the polymerization initiator used is usually in the range of 0.01 to 20 parts by weight with respect to 100 parts by weight of the grafted polymer. Examples of the polymerization initiator include the polymerization initiators described above. Among these polymerization initiators, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 2,5-dimethyl-2,5- ( Dialkyl peroxides such as tert-butylperoxy) hexane and 1,4-bis (tert-butylperoxyisopropyl) benzene are preferred.

The basic substance used for neutralization and saponification is not particularly limited, but alkali metals such as sodium and potassium, inorganic amines such as hydroxylamine and ammonium hydroxide, N, N-dimethylethanolamine , Alkanolamines such as N, N-diethylethanolamine, N-methylmorpholine, N-ethylmorpholine, pyridine, N-methylimidazole, tertiary amines such as ammonia, trimethylamine and triethylamine, tetramethylammonium hydroxide Quaternary ammonium compounds such as sodium oxide, sodium peroxide, alkali metal and alkaline earth metal oxides, hydroxides such as lithium hydroxide, potassium hydroxide, sodium hydroxide, calcium hydroxide, magnesium hydroxide , Hydride, charcoal Include the alkali metal and alkaline earth metal weak acid salts such as sodium, these compounds may be used alone, or two or more thereof.
The carboxylic acid group or carboxylic acid ester group neutralized or saponified with a basic substance is preferably an alkali metal salt of carboxylic acid or an amine salt of carboxylic acid.

The salt of higher fatty acid used in the present invention is preferably a salt of a fatty acid having 25 to 60 carbon atoms, more preferably an alkali metal salt, alkaline earth metal salt or amine salt of a fatty acid having 25 to 40 carbon atoms. Preferred are alkali metal salts of montanic acid and oleic acid.
Furthermore, the salt of higher fatty acid may contain a higher fatty acid and / or an ester of higher fatty acid in addition to the salt of higher fatty acid. The alcohol residue constituting the ester preferably has 2 to 30 carbon atoms, and particularly preferably 6 to 20 carbon atoms. Residues can be linear or branched. A mixture of different carbon numbers may be used. Specific examples of the alcohol residue include residues of higher alcohols such as cetyl alcohol, stearyl alcohol, and oleyl alcohol. Montanic acid ester wax and montan wax are particularly suitable.

A salt of a higher fatty acid can be obtained by neutralizing the higher fatty acid and / or saponifying the higher fatty acid ester. In this case, it may be a partially neutralized product or a partially saponified product in which fatty acids or fatty acid esters not neutralized or saponified coexist. Examples of the basic substance that can be used for neutralization and saponification are the same as those mentioned for the acid-modified polyolefin salt.
Furthermore, various surfactants can be used to improve the dispersion stability in water. For example, alkylnaphthalene sulfonates, anionic surfactants such as metal soaps (Zn, Al, Na, K salts), nonionic surfactants such as fatty acid monoglycerides, alkylammonium chlorides, amphoteric surfactants, and Examples include water-soluble polyvalent metal salts. These surfactants can be used alone or in combination of two or more.
The amount of the surfactant used is 0 with respect to a resin comprising a copolymerizable monomer comprising a thermoplastic elastomer, a monomer having an α, β-monoethylenically unsaturated group, and other copolymerizable monomers. About 0.05 to 40% by weight is preferable, 0.1 to 20% by weight is more preferable, and 0.1 to 10% by weight is particularly preferable.

  In the water-based resin composition of the thermoplastic elastomer (A-1) and / or the modified thermoplastic elastomer (A-2) used in the present invention, it is preferable that the respective components are contained in a certain quantitative ratio range. That is, with respect to 100 parts by weight of the thermoplastic elastomer (A-1) and / or the modified thermoplastic elastomer (A-2), the salt of the acid-modified polyolefin and / or the salt of the higher fatty acid is 0.5 to 30 parts by weight, Preferably it is 1 to 20 parts by weight.

Further, the surfactant added as desired is 0.1 to 40 parts by weight, particularly 0.2 to 20 parts per 100 parts by weight of the thermoplastic elastomer (A-1) and / or the modified thermoplastic elastomer (A-2). It is good to mix between parts by weight.
The water content is 1 to 25% by weight, preferably 1 to 20% by weight, based on the thermoplastic elastomer (A-1) and / or the modified thermoplastic elastomer (A-2). If the water content is less than 1% by weight, phase inversion (the resin solid content is changed from a continuous phase to a dispersed phase by water) hardly occurs, and a suitable aqueous dispersion cannot be obtained. Moreover, when it exceeds 25 weight%, an aqueous resin composition will come to have fluidity | liquidity. That is, by setting the content in the range of 1 to 25%, an apparently solid aqueous resin composition can be obtained.

  The water-based resin composition as described above includes the thermoplastic elastomer (A-1) and / or the modified thermoplastic elastomer (A-2), the acid-modified polyolefin and / or the higher fatty acid, for example, the thermoplastic elastomer (A-1). ) And / or the modified thermoplastic elastomer (A-2) and the acid-modified polyolefin and / or the fatty acid and / or the fatty acid ester are melt-kneaded, a basic substance and water are added thereto, and then melt-kneaded. A method of neutralization and / or saponification and dispersion (phase inversion) of the thermoplastic elastomer (A-1) and / or modified thermoplastic elastomer (A-2) in an aqueous phase, Water is added as a basic substance to the acid-modified polyolefin and / or the fatty acid and / or the fatty acid ester, neutralized and / or saponified, After melt-kneading with the plastic elastomer (A-1) and / or the modified thermoplastic elastomer (A-2), water is further added, and melt-kneading is performed to perform the thermoplastic elastomer (A-1) and / or modification. The thermoplastic elastomer (A-2) is preferably produced by a method of dispersing (phase inversion) in the aqueous phase.

The former method is preferred because it is simple and a uniform particle size can be obtained. The melt kneading means used for phase inversion may be any known means, but preferably a kneader, a Banbury mixer, or a multi-screw extruder can be exemplified.
The ratio of the basic substance addition amount for neutralization or saponification is 60 to 200%, preferably 80 to 170% of the total carboxylic acid or carboxylic acid ester.

The water-based resin composition obtained by melt-kneading and phase inversion contains 1 to 25% of water, but this water content can be maintained as it is or by adding water to this to lower the viscosity.
In addition to the above, a modified thermoplastic elastomer containing an acid group can obtain an aqueous resin composition by the following method.
For example, the basic substance which can be dissolved in an organic solvent and can neutralize acid groups is added in an amount capable of neutralizing 50 to 100% of the total carboxylic acid, and water or water and a surfactant are added to the water. The aqueous resin composition can also be obtained by a method of removing the organic solvent after the dispersion.

Urethane Resin (B-1) Aqueous Resin Composition Polyfunctional isocyanate compounds that are components of the urethane resin (B-1) aqueous resin composition used in the present invention include, for example, ethylene diisocyanate and trimethylene diisocyanate. Various aliphatic polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate and octamethylene diisocyanate, alicyclic polyisocyanates such as isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, 4,4′-dicyclohexylmethane diisocyanate, Aromatic polyisocyanates such as phenylene diisocyanate, tolylene diisocyanate, 4,4'-diisocyanate, sulfur-containing aliphatic isocyanates such as thiodiethyl diisocyanate, di Aromatic sulfide isocyanates such as phenyl sulfide-2,4′-diisocyanate, aliphatic disulfide isocyanates such as diphenyl disulfide-4,4′-diisocyanate, and aromatics such as diphenylsulfone-4,4′-diisocyanate. Sulfonate isocyanate, 4-methyl-3-isocyanatobenzenesulfonyl-4′-isocyanatophenol ester, etc., sulfonate ester isocyanate, 4,4′-dimethylbenzenesulfonyl-ethylenediamine-4,4′-diisocyanate, etc. And sulfur-containing heterocyclic compounds such as aromatic sulfonic acid amide isocyanates and thiophene-2,5-diisocyanates.

In addition, these alkyl-substituted products, alkoxy-substituted products, nitro-substituted products, prepolymer-modified products with polyhydric alcohols, carbodiimide-modified products, urea-modified products, burette-modified products, dimerization or trimerization reaction products are also used. However, polyfunctional isocyanate compounds other than the above compounds may be used. Moreover, these polyfunctional isocyanate compounds can also be used by 1 type, or 2 or more types of mixtures.
Of the above-mentioned compounds, aliphatic polyisocyanates and alicyclic polyisocyanate compounds are preferred from the viewpoint of yellowing resistance, thermal stability, and light stability of the obtained coating film. Among them, hexamethylene diisocyanate, isophorone diisocyanate, Particularly preferred are 4,4'-dicyclohexylmethane diisocyanate, 2,5-bisisocyanatomethylnorbornane, 2,6-bisisocyanatomethylnorbornane and derivatives thereof.

Examples of the active hydrogen compound having at least two active hydrogen groups capable of reacting with the polyfunctional isocyanate compound per molecule include the following. Various polyol compounds: aliphatic polyols such as ethylene glycol, propylene glycol, pentaerythritol and sorbitol, aromatic polyols such as dihydroxynaphthalene and trihydroxynaphthalene, halogenated polyols such as dibromoneopentyl glycol, polyester polyol, polyethylene glycol , Polyether polyols, polythioether polyols, condensation products of organic acids such as oxalic acid and adipic acid and the polyols, addition reaction products of the polyols with alkylene oxides such as ethylene oxide and propylene oxide, alkylene Addition reaction product of polyamine and alkylene oxide, 2,2-dimethylollactic acid, 2,2-dimethylolpropionic acid, caprolactone modified product, 2- Mercaptoethanol, 3-mercapto-1,2-propanediol.
In addition, polyamino compounds such as ethylenediamine and diethylenetriamine, and α-amino acids such as serine, lysine and histidine can also be used.

Further, in order to stabilize the aqueous resin composition of the urethane resin (B-1) used in the present invention, it is preferable that the molecule has at least one carboxyl group, sulfonyl group and ethylene oxide group. It is more preferable to have at least one group and / or sulfonyl group. Examples of constituents for introducing these atomic groups include 2,2-dimethylol lactic acid, 2,2-dimethylol propionic acid, 2,2-dimethylol butanoic acid, 2,2-dimethylol valeric acid, 3,4- Examples include, but are not limited to, diaminobutanesulfonic acid, 3,6-diamino-2-toluenesulfonic acid, polyethylene glycol, polyaddition product of ethylene oxide and propylene oxide, and a polymer of ethylene glycol and the active hydrogen compound. It is not something. By introducing these atomic groups into the molecule, the mechanical stability of the resin and the miscibility with other components tend to be improved.
The preferred amount when using the carboxyl group and / or sulfonyl group-containing compound is such that the acid value in terms of solid content of the aqueous resin composition of the urethane resin is in the range of 2 to 35 KOHmg / g, more preferably 3 to 30 KOHmg / g. Is within. If the acid value is less than the above range, the mechanical stability of the resin tends to be high.

  Although the manufacturing method of the aqueous resin composition of urethane resin (B-1) is not specifically limited, For example, the following methods are mentioned as an example. For example, a polyfunctional isocyanate compound, a compound having an active hydrogen group capable of reacting with an isocyanate group in the active hydrogen compound, an active hydrogen group capable of reacting with an isocyanate group in the compound, and a carboxyl in the molecule At least one compound having a group, sulfonyl group or ethylene oxide group is reacted in an equivalent ratio such that an excess of isocyanate groups is present in the presence or absence of a suitable organic solvent to have an isocyanate group at the molecular end. Then, the urethane prepolymer having a carboxyl group and / or a sulfonyl group in the prepolymer is neutralized with a neutralizing agent such as a tertiary amine, and then this neutralized prepolymer is converted into a chain extender. If the system contains an organic solvent after it has been reacted in the aqueous solution, A method that can be removed, a method in which an unneutralized urethane prepolymer obtained by the above method is introduced into an aqueous solution containing a neutralizer and a chain extender, and reacted, or the above method In the neutralized urethane prepolymer obtained in step 1, an aqueous solution having a chain extender is added and reacted, and the neutralized urethane prepolymer obtained by the above method contains a neutralizer. And an aqueous solution having a chain extender is added and reacted to obtain an aqueous resin composition.

Although it does not restrict | limit especially as a neutralizing agent used for this invention, The basic substance as described in a thermoplastic elastomer (A-1) can be used.
Examples of the chain extender used in the present invention include water, ethylenediamine, diethylenetriamine, NBDA (trade name, manufactured by Mitsui Chemicals), N-methyl-3,3′-diaminopropylamine, and diethylenetriamine and acrylate. Polyamines such as adducts or hydrolysis products thereof are suitable.

  Moreover, the aqueous resin composition of the urethane resin (B-1) used by this invention can be used also as a modified body by making it react with other components, such as another monomer and a resin component. Further, in the aqueous resin composition of the urethane resin (B-1) obtained in the present invention, acrylic acid, acrylic ester, methacrylic acid, methacrylic ester, acrylamide, methacrylamide, styrene, acrylonitrile, butadiene, vinyl acetate , Ethylene, propylene, itaconic acid, maleic acid and the like can be used as a composite obtained by polymerizing at least one monomer.

Water-based resin composition of resin (B-2) comprising a copolymerizable monomer comprising a monomer having an α, β-monoethylenically unsaturated group and another copolymerizable monomer α used in the present invention As a copolymerizable monomer constituting an aqueous resin composition of a resin (B-2) comprising a copolymerizable monomer comprising a monomer having a β-monoethylenically unsaturated group and other copolymerizable monomers Examples thereof include the copolymer monomers described in Modified Thermoplastic Elastomer (A-2).

  The aqueous resin composition of resin (B-2) comprising a copolymerizable monomer comprising a monomer having an α, β-monoethylenically unsaturated group and other copolymerizable monomers used in the present invention The production method is not particularly limited. For example, a basic substance and ion-exchanged water are added to a resin solution obtained by polymerizing a copolymerizable monomer and a polymerization initiator in an organic solvent. After the addition, it can be produced by a known method such as a method of removing the organic solvent or an emulsion polymerization method of polymerizing a copolymerizable monomer in the presence of a surfactant or a polymerization initiator in water.

As the polymerization initiator and organic solvent used in the present invention, those described in the modified thermoplastic elastomer (A-2) can be used.
As the basic substance and the surfactant used in the present invention, those described in the water-based resin composition of thermoplastic elastomer can be used.
An aqueous resin composition of a resin comprising a copolymerizable monomer comprising a monomer having an α, β-monoethylenically unsaturated group and other copolymerizable monomers used in the present invention is adhered to the substrate. In view of this, the Tg measured by DSC is preferably -60 ° C to 70 ° C, more preferably -30 ° C to 50 ° C. Moreover, the weight average molecular weight by GPC is preferably 5,000 to 500,000, and more preferably 10,000 to 400,000.

Aqueous resin composition of polyester (B-3) Examples of the polyester (B-3) used in the present invention include aromatic polyesters, aliphatic polyesters, saturated polyesters and unsaturated polyesters. These are mainly polycondensates of an acid component monomer and an alcohol component monomer.

  Examples of the acid component monomer include terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acids, 4,4′-diphenyldicarboxylic acid, trimellitic acid, trimesic acid, pyromellitic acid, benzoic acid, p-oxybenzoic acid, p- (hydroxyethoxy) benzoic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, glutaric acid, suberic acid, brassic acid, dodecanedicarboxylic acid, fumaric acid, maleic acid, itaconic acid, 1,4-cyclohexanedicarboxylic acid Acid, 1,3-cyclohexanedicarboxylic acid, hexahydroorthophthalic acid, tricyclodecanedicarboxylic acid, tetrahydroterephthalic acid, tetrahydroorthophthalic acid, or the like, methyl esters of these acids, or anhydrides can also be used. . Among these, terephthalic acid, isophthalic acid, adipic acid, sebacic acid, trimellitic anhydride are preferably used, and these acid component monomers can be used alone or in combination.

  As alcohol component monomers, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4- Butanediol, 1,2-butanediol, 1,5-pentanediol, 2-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-2-butyl-1,3 -Propanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 2,2,4-trimethyl-1,3-pentanediol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol , Trimethylol group Bread, trimethylolethane, glycerin, pentaerythritol, bisphenol-based ethylene oxide adduct, bisphenol-based propylene oxide adduct, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,3-cyclohexanedimethanol, 1, 3-cyclohexanediol, hydrogenated bisphenol A, spiroglycol, tricyclodecanediol, tricyclodecane dimethanol, resorcinol, 1,3-bis (2-hydroxyethoxy) benzene, etc. are used, among which ethylene glycol, diethylene glycol, tri Ethylene glycol, 1,4-butanediol and neopentyl glycol are preferably used, and these alcohol component monomers should be used alone or in combination. It can be.

The polyester used in the present invention can be produced by a known method such as a melt polymerization method, a solution polymerization method, or a solid phase polymerization method. The method of dispersing the obtained polyester in water is not particularly limited, but the polyester containing a functional group that can be neutralized with a basic substance such as an acid is dissolved in an organic solvent, and the medium is mixed with the basic substance. After mixing, the method of removing the organic solvent, dissolved in the organic solvent, mechanically sheared in the presence of the emulsifier and dispersed in water, then the method of removing the organic solvent, melt-kneaded with the emulsifier, Examples thereof include a method of adding water or an aqueous solution of a basic substance to disperse the resin raw material in water, or a method similar to the method of obtaining an aqueous dispersion of the various elastomers.
As the organic solvent used in the present invention, those described in the modified thermoplastic elastomer (A-2) can be used, and a mixture of two or more of these may be used.

The sulfonate-containing polyester used in the present invention is mainly a polycondensate of an acid component monomer and an alcohol component monomer, but is a polyester containing a sulfonate salt bonded to a polymer. As the sulfonic acid-containing component monomer, 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, 5- (p-sulfophenoxy) isophthalic acid, 5- (sulfopropoxy) isophthalic acid, 4-sulfonaphthalene-2, 7-dicarboxylic acid, sulfopropylmalonic acid, sulfosuccinic acid, 2-sulfobenzoic acid, 3,2-sulfobenzoic acid, 5-sulfosalicylic acid and methyl esters of these carboxylic acids, and metal salts and ammonium salts of these sulfonic acids Among them, sodium salt of 5-sulfoisophthalic acid or sodium salt of dimethyl 5-sulfoisophthalic acid is preferably used.
The melt-kneading means used in the present invention may be any known means, but preferred examples include a kneader, a Banbury mixer, a single-screw extruder, and a twin-screw extruder.

Aqueous resin composition of epoxy resin (B-4) The epoxy resin (B-4) used in the present invention may be one having two or more epoxy groups in one molecular chain. For example, bisphenol A -Diglycidyl ether, ε-caprolactone ring-opening adduct of bisphenol A-diglycidyl ether, bisphenol F-diglycidyl ether, bisphenol S-diglycidyl ether, novolac glycidyl ether, hexahydrophthalic acid diglycidyl ester, diglycidyl dimer Ester, tetraglycidylaminodiphenylmethane, 3,4-epoxy-6-methylcyclohexylmethylcarboxylate, triglycidyl isocyanurate, 3,4-epoxycyclohexylmethylcarboxylate, polypropylene diglycidyl acetate Le, a both ends diglycidyl ether-modified products of polybutadiene or polysulfide, preferably bisphenol A- diglycidyl ether, bisphenol F- diglycidyl ether.

  Although it does not restrict | limit especially as a manufacturing method of the aqueous resin composition of the epoxy resin (B-4) used for this invention, For example, an epoxy resin (B-4) is an aprotic water-soluble organic solvent. The ratio of the number of moles of epoxy groups to the number of moles of active hydrogen in the polyfunctional amine [(number of moles of epoxy group) / (number of moles of active hydrogen in the polyfunctional amine)] is greater than 0. In addition, a polyfunctional amine is added in a range smaller than 1. The method of adding carboxylic anhydride to the obtained thing is mentioned.

  The polyfunctional amine used in the present invention is an amine having two or more active hydrogens in one molecule. For example, isopropanolamine, monopropanolamine, monobutanolamine, monoethanolamine, diethylenetriamine, ethylenediamine, butylamine, propylamine, isophoronediamine, tetrahydrofurfurylamine, xylenediamine, diaminediphenylmethane, diaminosulfone, octylamine, metaphenylenediamine, amylamine Hexylamine, decylamine, triethylenetetramine, tetramethylenepentamine, dimethylaminopropylamine, N-aminoethylpiperazine, metacenediamine, diaminodiphenylsulfone and the like. Of these, alkanolamines are preferably used. The carboxylic anhydride used here may be an anhydride of a compound having two or more carboxyl groups in one molecule. For example, succinic anhydride, itaconic anhydride, maleic anhydride, citraconic anhydride, phthalic anhydride Examples thereof include acid and trimellitic anhydride.

Aqueous Resin Composition of Modified Amino Resin (C) The aqueous resin composition of the modified amino resin (C) used in the present invention includes an aqueous resin composition of an amino resin modified with a urethane resin, and an amino resin modified with an acrylic resin. Examples thereof include an aqueous resin composition of a resin, an amino resin having an acid functional group, or an aqueous resin composition of an amino resin modified with an amide compound having an acid functional group.

[Aqueous resin composition of amino resin modified with urethane resin]
The method for producing a composite resin of a urethane resin and an amino resin is to produce a urethane resin having hydroxyl groups at both ends of a polymer molecule when an oxycarboxylic acid having two or more hydroxyl groups is subjected to a urethanization reaction. Furthermore, an amino resin obtained by addition dehydration condensation from an amino compound, aldehyde, and alcohol is subjected to a complex reaction. At this time, the compound is efficiently advanced by using an alcohol different from the alcohol which is a raw material of the alkyl ether contained in the amino resin as a solvent.

Examples of amino compounds that are raw materials for amino resins include urea, melamine, benzoguanamine, and other triazine compound amino compounds. In addition, formaldehyde can be used as the aldehyde, and alcohol represented by the following formula CnH2n + 1OH (8 ≧ n ≧ 1) can be used as the alcohol. The alcohol can be linear or branched, and can be combined with a urethane resin that continues. Equally complex and aqueous are possible.
As the isocyanate or the polyol as the raw material of the urethane resin, those described in the urethane resin (B-1) can be used.

  Any oxycarboxylic acid having two or more hydroxyl groups can be used as long as it imparts a branched carboxylic acid in the urethane resin molecule. To increase the carboxylic acid content in the urethane resin, A branched one having at least one carboxyl group and having a low molecular weight of 3 to 10 carbon atoms is preferred, and for example, 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid are preferred.

As the solvent used for producing the urethane resin of the present invention, an organic solvent usually used for producing a urethane resin can be used. Examples thereof include methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, isopropyl alcohol, toluene, xylene, isobutyl acetate, butyl acetate, acetone, dimethylformamide, N-methyl-2-pyrrolidone, and diethylene glycol dimethyl ether.
Alcohols added as a reaction solvent in the compounding step of a compound resin of amino resin and urethane resin are, for example, isopropyl alcohol, 2-butyl alcohol, tert-butanol, cyclobutanol, cyclopentanol, cyclohexanol, pinacol, Examples include secondary and tertiary alcohols such as cycloheptanol, 2-ethyl-1-hexanol, and diacetone alcohol, or alcohols that are significantly different in solubility from alcohols used in amino resin production. The amount used is 10 parts by weight to 60 parts by weight with respect to 100 parts by weight of the total amount of amino resin and urethane resin used for the complexing reaction. If it is 60 parts by weight or more, the composite is difficult to proceed due to the high dilution rate. More preferably, it is 20 to 40 parts by weight.

  When the amino resin and the urethane resin are combined, the amount of the amino resin used is preferably 30 to 90 parts by weight with respect to 100 parts by weight of the total amount of the amino resin and the urethane resin used for the combining reaction. If it is less than 30 parts by weight, the terminal hydroxyl group of the urethane resin that does not contribute to the curing reaction with the main agent becomes excessive, and the water resistance decreases. If it is 90 parts by weight or more, the uncombined amino resin becomes excessive, and it becomes difficult to make it water-based after complexing. More preferably, it is 50 to 85 parts by weight.

Moreover, in compounding the amino resin and urethane resin of the present invention, the amount of urethane resin used is in the range of 3 to 70 parts by weight with respect to 100 parts by weight of the total amount of amino resin and urethane resin used in the complexing reaction. Preferably there is. If it is less than 3 parts by weight, the expected flexibility is lowered, and if it exceeds 70 parts by weight, water resistance and coating film hardness are lowered. More preferably, it is 10 to 55 parts by weight.
Furthermore, as the base for neutralizing the composite resin, those described in the thermoplastic elastomer (A-1) can be used.

[Amino resin aqueous resin composition modified with acrylic resin]
A method for producing a composite resin of an acrylic resin and an amino resin includes a monomer having an α, β-monoethylenically unsaturated group containing a hydroxyl group and an acid group, which is an acrylic resin, and other copolymerizable monomers. A resin composed of a copolymerizable monomer is produced, and an amino resin obtained by addition dehydration condensation from an amino compound, an aldehyde, and an alcohol is subjected to a composite reaction. At this time, the compound is efficiently advanced by using an alcohol different from the alcohol which is a raw material of the alkyl ether contained in the amino resin as a solvent.
Examples of amino compounds that are raw materials for amino resins include urea, melamine, benzoguanamine, and other triazine compound amino compounds. Further, formaldehyde can be used as the aldehyde, and alcohol represented by the following formula CnH (2n + 1) -OH (8 ≧ n ≧ 1) can be used as the alcohol. By compounding with the resin, it is possible to equalize and make it water-based.

For example, isopropyl alcohol, 2-butyl alcohol, tert-butanol, cyclobutanol, cyclopentanol, cyclohexanol, and pinacol are alcohols added as a reaction solvent in the compounding step of a composite resin of an amino resin and an acrylic resin. , Cycloheptanol, 2-ethyl-1-hexanol, secondary acetone, etc. such as diacetone alcohol, or alcohols that are greatly different in solubility from alcohols used for amino resin production.
When the amino resin and the acrylic resin are combined, the amount of the amino resin used is preferably 30 to 90 parts by weight with respect to 100 parts by weight of the total amount of the amino resin and the acrylic resin used in the composite reaction. If it is less than 30 parts by weight, the terminal hydroxyl group of the acrylic resin that does not contribute to the curing reaction with the main agent becomes excessive, and the water resistance decreases. If it is 90 parts by weight or more, the uncombined amino resin becomes excessive, and it becomes difficult to make it water-based after conjugation. More preferably, it is 50 to 85 parts by weight.

Further, when the amino resin and the acrylic resin of the present invention are combined, the amount of the acrylic resin used is in the range of 3 to 70 parts by weight with respect to 100 parts by weight of the total amount of the amino resin and the acrylic resin used for the composite reaction. It is preferable that If it is less than 3 parts by weight, the expected flexibility is lowered, and if it exceeds 70 parts by weight, water resistance and coating film hardness are lowered. More preferably, it is 10-55 weight part. The amount of the basic substance used for neutralizing the material for compounding the amino resin and the acrylic resin of the present invention is preferably 50 to 100 mol% of the carboxyl group. Two or more of these basic substances may be used in combination.
As a basic substance used for this invention, the thing as described in manufacture of the water-based resin composition of a thermoplastic elastomer (A-1) can be used.
The method for producing the acrylic resin used in the present invention is not particularly limited. For example, a resin solution obtained by solution polymerization in which a copolymerizable monomer and a polymerization initiator are polymerized in an organic solvent. In addition, after adding a basic substance and ion-exchanged water, it can be produced by a known method such as a method of removing an organic solvent.
In addition, the thing as described in a modified thermoplastic elastomer (A-2) can be used for a copolymerization monomer and a polymerization initiator.

[Amino resin modified with amino compound having acid functional group or amide compound having acid functional group]
In the method for producing an amino resin modified with an amino compound having an acid functional group or an amide compound having an acid functional group, an amino compound, formaldehyde and alcohol are alkyl etherified using an acid as a catalyst. To this, an amino compound having an acid functional group or an amide compound having an acid functional group and water are added and reacted with an amino resin, neutralized with a basic compound, and a part of excess alcohol and water are removed. An amino resin can be obtained.

In addition, an amino compound having an acid functional group or an amide compound having an acid functional group can be added before the completion of alkyl etherification, and an amino compound having an acid functional group or an amide compound having an acid functional group is previously basic. It can also be added in the state neutralized with the compound.
As the amino compound used here, an amino compound selected from melamine, benzoguanamine, and urea, which are generally used as raw materials for amino resins, can be used, but melamine is preferred from the viewpoint of physical properties.

Examples of amino compounds having an acid functional group or amide compounds having an acid functional group include amino acids such as glycine and alanine, o, m, p-aminobenzoic acid, o, m, p-aminomethylbenzoic acid, 3-aminopropionic acid, 4-aminobutanoic acid, DL-aminoisobutanoic acid, 4-aminocrotonic acid, 4-amino-3-hydroxybutanoic acid, glycylglycine, aminomethanesulfonic acid, 2-aminoethanesulfonic acid, 3 -Aminopropanesulfonic acid, o, m, p-sulfanilic acid, 1-amino-4-naphthalenesulfonic acid and its positional isomers, oxamic acid, aminomalonate, succinamic amide, maleamate, o, m, p- Examples thereof include phthalamic acid and N- (2-acetamido) -2-aminoethanesulfonic acid.
Formaldehyde may be an aqueous solution or solid paraformaldehyde. Paraformaldehyde having a non-volatile content of 80% or more is desirable from the viewpoint of economy.

  The alcohol which is a raw material of the amino resin is one having the following formula CnH (2n + 1) -OH (8 ≧ n ≧ 1), and the structure thereof may be linear or branched. When n is 9 or more, self-crosslinking may proceed during the production process due to overheating in the solvent removal process. From the viewpoint of economy and coating film performance, n is preferably 4 ≧ n ≧ 1. Further, in order to improve the hydrophilicity of the resulting amino resin, it is desirable that the value of n is small, and conversely, in order to improve the hydrophobicity, it is desirable that the value of n is large. The value of n is selected depending on the form of paint used and the compatibility with the main agent.

  An amino resin modified with an amino compound having an alcohol and an acid functional group or an amide compound having an acid functional group is preferably neutralized with a basic compound because a self-crosslinking reaction proceeds under acidic conditions. Also, before modifying an amino compound having an acid functional group or an amide compound having an acid functional group into a methylolated amino compound, neutralization with a basic compound in advance, followed by a modification reaction to a methylolated amino resin Is also possible. When the molar ratio of the acid functional groups contained in the amino resin is 1.0, it is desirable to neutralize at a molar ratio of 0.8 to 1.2 times. More preferably, it is 0.9 to 1.1 times. Specifically, an alkali metal hydroxide or ammonia such as sodium hydroxide or potassium hydroxide as an inorganic base, or an alkanolamine such as monoethanolamine, dimethylethanolamine, or triethanolamine as an organic base, Examples include amines such as amine morpholine.

In the present invention, a terpene resin, a rosin resin, and a petroleum hydrocarbon resin can be used in combination.
Examples of the terpene resin used in the present invention include resins comprising α-pinene, β-pinene, limonene, dipentene, terpene phenol, terpene alcohol, terpene aldehyde, and the like. Α-pinene, β-pinene, limonene, dipentene An aromatic-modified terpene resin obtained by polymerizing an aromatic monomer such as styrene, etc., and hydrogenated products thereof can also be mentioned. Among these, terpene phenol resins, aromatic modified terpene resins, and hydrogenated products thereof are preferable.
Examples of the rosin resin used in the present invention include modified rosin modified with natural rosin, polymerized rosin, maleic acid, fumaric acid, (meth) acrylic acid and the like. Examples of the rosin derivative include esterified products, phenol-modified products and esterified products of the above rosins, and hydrogenated products thereof can also be mentioned.

Examples of the petroleum hydrocarbon resin used in the present invention include an aliphatic petroleum resin mainly containing a C5 fraction of tarnaphtha, an aromatic petroleum resin mainly containing a C9 fraction, and a copolymer thereof. It is alicyclic. C5 petroleum resin (resin obtained by polymerizing C5 fraction of naphtha cracked oil), C9 petroleum resin (resin obtained by polymerizing C9 fraction of naphtha cracked oil), C5C9 copolymerized petroleum resin (C5 fraction of naphtha cracked oil) C9 fraction copolymerized resin), styrene, indene, coumarone, coumarone indene resin containing dicyclopentadiene, etc., and condensation of ρ-tertiarybutylphenol and acetylene. Examples thereof include alkylphenol resins typified by products, xylene resins obtained by reacting o-xylene, ρ-xylene, and m-xylene with formalin. These can be used alone or in combination of two or more. Among these, petroleum hydrocarbon resins having a weight average molecular weight of 1,000 to 50,000 as measured by GPC are preferable, and 1,500 to 30,000 are particularly preferable. Moreover, what has a polar group in these resin is still more preferable.
In the present invention, a mixture of two or more terpene resins, rosin resins, and petroleum hydrocarbon resins can be used.

Moreover, what was disperse | distributed to water by the well-known method can also be mixed and used, but thermoplastic elastomer (A-1), modified thermoplastic elastomer (A-2), urethane resin (B-1) , A resin (B-2), a polyester (B-3), an epoxy resin (B-2) comprising a monomer having an α, β-monoethylenically unsaturated group and other copolymerizable monomers It can also be used after being mixed with B-4) and dispersed in water.
The present invention includes 10 to 95 parts by weight of the thermoplastic elastomer (A-1) and / or modified thermoplastic elastomer (A-2) described above, urethane resin (B-1), and / or α, β. -Resin (B-2) and / or polyester (B-3) and / or epoxy comprising a copolymerizable monomer comprising a monomer having a monoethylenically unsaturated group and other copolymerizable monomers It consists of 0 to 70 parts by weight of the aqueous resin composition of the resin (B-4) and 5 to 50 parts by weight of the aqueous resin composition of the modified amino resin (C), and (A-1) and / or (A-2) And (B-1) and / or (B-2) and / or (B-3) and / or (B-4) and (C) are preferably mixed so that the total of 100 parts by weight. .
Moreover, when using a terpene resin, a rosin resin, or a petroleum hydrocarbon resin, 5 parts per 100 parts by weight of the thermoplastic elastomer (A-1) and / or the modified thermoplastic elastomer (A-2). It can be used in the range of ˜100 parts by weight.

In order to further improve the stability to water, the water-based resin composition used in the present invention, for example, anionic surface activity such as alkyl naphthalene sulfonate and metal soap (Zn, Al, Na, K salt) Agents, nonionic surfactants such as fatty acid monoglycerides, alkylammonium chlorides, amphoteric surfactants, and water-soluble polyvalent metal salts can be used. These surfactants can be used alone or in combination of two or more. There is no problem whether this is added to either after being dispersed in water but before being dispersed.
The shape of the substrate used in the present invention is not particularly limited, but at least one is preferably a sheet or a molding material.

Other slipperiness imparting agents (for example, synthetic wax, natural wax, etc.), tackiness imparting agents, crosslinking agents, film forming aids, leveling agents, viscoelasticity modifiers, wetting agents, flame retardants (if necessary) For example, phosphorus-containing resins such as ammonium polyphosphate, phosphate esters, melamine, zinc borate, magnesium hydroxide, etc.), stabilizers, rust inhibitors, fungicides, UV absorbers, weathering stabilizers, heat stabilizers , Foaming agent, antifoaming agent, wetting agent, coagulant, gelling agent, anti-aging agent, softening agent, plasticizer, flavoring agent, anti-sticking agent, mold release agent, anti-settling agent, antioxidant, charging Inhibitors, dyes, pigments (eg, titanium white, bengara, phthalocyanine, carbon black, permanent yellow, etc.), fillers (eg, calcium carbonate, magnesium carbonate, barium carbonate, talc, aluminum hydroxide, calcium sulfate) Additives such as kaolin, mica, asbestos, mica, calcium silicate), organic solvents, oils (mineral lubricants, mineral oils, synthetic oils, vegetable oils, etc.) are added to the extent that the object of the present invention is not impaired. May be.
These additives may be used alone or in combination of two or more. Such an additive may be used when the various elastomers obtained above are dispersed in water, or may be added after being dispersed in water.

The method for applying the material of the present invention is not particularly limited, and can be performed by a method such as spraying, curtain coater, flow coater, roll coater, gravure coater, brush coating, or dipping. 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.
These coating materials of the present invention are excellent for polyolefins such as polypropylene, synthetic rubber, unsaturated polyester, epoxy resin, urethane resin, various resin sheets, molded products, etc., and steel plates, metals such as aluminum. In particular, it exhibits excellent adhesion to a material made of polyolefin.

  Hereafter, the manufacturing method of the composition of this invention and various test examples are given and demonstrated further. In the following, parts and percentages are by weight unless otherwise specified.

[Production Example 1]
Thermoplastic elastomer (A-1)
After charging 2,000 ml of hexane, 50 g of 1-butene and triisobutylaluminum (1.0 mmol) in a 2000 ml polymerization apparatus sufficiently purged with nitrogen at room temperature, the temperature inside the polymerization apparatus was raised to 70 ° C. and propylene was used. The pressure was increased to 0.7 MPa. Subsequently, diphenylmethylene (3-t-butyl-5-methylcyclopentadienyl) 2,7-di-t-butylfluorenylzirconium dichloride (0.002 mmol) and 0.6 mmol methylaluminoxane (Tosoh Finechem) in terms of aluminum Was added to the polymerization vessel and polymerized for 30 minutes while maintaining an internal temperature of 70 ° C. and a propylene pressure of 0.7 MPa, and 20 ml of methanol was added to terminate the polymerization. After depressurization, the polymer was precipitated from the polymerization solution in 2 L of methanol and dried under vacuum at 130 ° C. for 12 hours. The obtained polymer was 11.5 g, butene content was 16.9 mol%, the melting point of the polymer was 86.3 ° C., the intrinsic viscosity [η] was 2.11 dl / g, and the molecular weight distribution Mw / Mn was It was 2.09.

[Production Example 2]
Water-based resin composition of thermoplastic elastomer (A-1) 100 g of thermoplastic elastomer (A-1), acid-modified polypropylene wax (manufactured by Mitsui Chemicals, high wax NP0555A: acid graft amount 3 wt%) and potassium oleate A mixture of 3 g is supplied at a rate of 3000 g / hr from a hopper of a twin screw extruder (Ikegai Iron Works Co., Ltd., PCM-30, L / D = 40), and provided at the vent portion of the extruder. From a supply port, a 20% aqueous solution of potassium hydroxide was continuously supplied at a rate of 90 g / hour and continuously extruded at a heating temperature of 210 ° C. The extruded resin mixture could be cooled to 110 ° C. with a jacketed static mixer installed at the extruder port and further poured into 80 ° C. warm water. The resulting aqueous resin composition had a solid content concentration of 45% and a pH of 11.

[Production Example 3]
A water-based resin composition of the modified thermoplastic elastomer (A-2) 100 g of the thermoplastic elastomer (A-1) was changed to 100 g of the thermoplastic elastomer (A-2) modified with maleic anhydride. A water-based resin composition was obtained in the same manner. The resulting aqueous resin composition had a solid content concentration of 45% and a pH of 11.
In addition, what was obtained with the following method was used for the thermoplastic elastomer (A-2) modified with maleic anhydride. 96 g of the thermoplastic elastomer described in Production Example 1, 4 g of maleic anhydride and 0.4 g of perhexi 25B as a polymerization initiator were mixed into a twin screw extruder (Ikegai Iron Works Co., Ltd., PCM-30, L / D = 40) was used for modification at a heating temperature of 220 ° C. and 16 kg / hour to obtain a thermoplastic elastomer containing a carboxylic acid group bonded to a polymer chain.

[Production Example 4]
Production Example Except that 100 g of the thermoplastic elastomer (A-1) of the thermoplastic resin (A-2) modified with the modified thermoplastic elastomer (A-2) is changed to 100 g of the thermoplastic elastomer (A-2) modified with hydroxyethyl acrylate. A water-based resin composition was obtained in the same manner as in 2. The resulting aqueous resin composition had a solid content concentration of 45% and a pH of 11.
The thermoplastic elastomer (A-2) modified with hydroxyethyl acrylate was obtained by the following method. A twin screw extruder (Ikegai Iron Works Co., Ltd., PCM-) prepared by mixing 92 g of the thermoplastic elastomer described in Production Example 1 with 8 g of hydroxyethyl acrylate and 0.6 g of perhexi25B in the polymerization initiator. 30 and L / D = 40) at a heating temperature of 220 ° C. and 16 kg / hour to obtain a thermoplastic elastomer containing a hydroxyl group bonded to a polymer chain.

[Production Example 5]
100 g of the thermoplastic elastomer described in Production Example 1 and 400 g of methylcyclohexane were charged into the water-based resin composition autoclave of the modified thermoplastic elastomer (A-2), and heated to 130 ° C. while purging with nitrogen. Next, 30 g of methyl methacrylate, 25 g of ethyl acrylate, 15 g of 2-hydroxyethyl acrylate, 10 g of Plaxel FM-3, 20 g of methacrylic acid and di-tert-butyl peroxide as a polymerization initiator 1 g of a mixed solution (hereinafter abbreviated as PBD) was fed over 4 hours. The temperature was raised to 135 ° C. 30 minutes after the end of the feed, 0.5 g of PBD was added 30 minutes later, and 0.5 g of PBD was added 1 hour later. The temperature was raised to 140 ° C. 30 minutes after the addition of PBD, and 4 g of PBD was added 30 minutes later, and 2 g was added after 1 hour, and 2 g was added after 1 hour, and reacted. The reaction was allowed to stand at 140 ° C. for 2 hours after the last addition of PBD to obtain a resin solution having a solid acid value of 65 mgKOH / g. The obtained resin solution was heated to 100 ° C., and 400 g of the solvent was removed under reduced pressure. To this, 100 g of butyl cellosolve was added, neutralized with triethylamine so as to be theoretically 100%, 3 g of potassium oleate was added, and the solid content concentration was adjusted with deionized water to 40%. This was stirred at a rotational speed of 10,000 rpm for 15 minutes to obtain an aqueous resin composition.
As the raw material used above, Plaxel FM-3 used as a polymerizable monomer was unsaturated fatty acid hydroxyalkyl ertel modified epsilon-caprolactone manufactured by Daicel Chemical Industries, Ltd.

[Production Example 6]
In a four-necked flask equipped with a water-based resin composition stirrer, thermometer, reflux condenser, and nitrogen inlet tube of a modified thermoplastic elastomer (A-2), 60 g of toluene, PTG2000 (product of Hodogaya Chemical Co., Ltd.) Name) 46.3 g, 1,6-hexanediol 1.2 g, 2,2-dimethylolbutanoic acid 3.1 g, 1,6-hexamethylene diisocyanate 9.3 g, dibutyltin laurate 0.09 g Then, a urethane resin solution was obtained by reacting at 90 ° C. for 8 hours in a nitrogen gas atmosphere.
A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube is charged with 140 g of the maleic anhydride-modified thermoplastic elastomer described in Production Example 3 and 700 g of toluene, heated and dissolved, and then the urethane described above. 200 g of resin solution was slowly added over 1 hour. This was mixed with 2 g of sodium dodecylbenzenesulfonate and 500 g of ion-exchanged water, and stirred at a rotational speed of 10,000 rpm for 15 minutes to obtain an emulsion. Toluene in this emulsion was distilled off under reduced pressure with an evaporator to obtain an aqueous resin composition having a solid content concentration of 40%.

[Production Example 7]
Thermoplastic elastomer (A-1) / modified thermoplastic elastomer (A-2) water-based resin composition Thermoplastic elastomer (A-1) 100 g out of 10 g modified with maleic anhydride described in Production Example 3 An aqueous resin composition was obtained in the same manner as in Production Example 2, except that the plastic elastomer (A-2) was changed. The resulting aqueous resin composition had a solid content concentration of 45% and a pH of 11.

[Production Example 8]
Thermoplastic elastomer (A-1) / Modified thermoplastic elastomer (A-2) aqueous resin composition Of 100 g of thermoplastic elastomer (A-1), 10 g was modified with the hydroxyethyl acrylate described in Production Example 4. A water-based resin composition was obtained in the same manner as in Production Example 2, except that the thermoplastic elastomer (A-2) was changed. The resulting aqueous resin composition had a solid content concentration of 45% and a pH of 11.

[Production Example 9]
Polytetramethylene ether glycol (manufactured by Hodogaya Chemical Co., Ltd., PTG2000SN) is added to a four-necked flask equipped with a water-based resin composition stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube of urethane resin (B-1). 399.5 g, 2,2-dimethylolbutanoic acid 21.0 g, 1,4-butanediol 12.4 g, hexamethylene diisocyanate 96.3 g, and methyl ethyl ketone 374.0 g were charged at 90 ° C. for 6 hours in a nitrogen gas atmosphere. Reacted. Then, it cooled to 60 degreeC, 13.3 g of triethylamine was added, and it mixed for 30 minutes under this temperature. The obtained prepolymer was mixed and stirred with 1275.7 g of 0.86% hexamethylenediamine aqueous solution, and then methylethylketone was removed at 60 ° C. under reduced pressure to obtain an aqueous resin composition of urethane resin having a solid content concentration of 30% and pH 8. I got a thing.

[Production Example 10]
Aqueous resin composition stirrer, thermometer, reflux cooling of resin (B-2) comprising copolymerized monomer comprising monomer having α, β-monoethylenically unsaturated group and other copolymerizable monomer To a four-necked flask equipped with an apparatus and a nitrogen introduction tube, 500 g of toluene and 100 g of ethyl acetate were charged, and the temperature was raised to 85 ° C. in a nitrogen gas atmosphere. Next, a mixture of 150 g of methyl methacrylate, 100 g of ethyl acrylate, 30 g of 2-hydroxyethyl acrylate, 20 g of methacrylic acid and 3 g of polymerization initiator (hereinafter abbreviated as PBO) is fed over 4 hours. Reacted. After 1 hour and 2 hours from the end of the feed, 0.2 g of PBO was added and reacted for 2 hours from the last addition to obtain a resin solution. By neutralizing the resulting resin solution with triethylamine so that it is theoretically 100%, adding deionized water so that the nonvolatile content becomes 40%, and then removing toluene and ethyl acetate under reduced pressure. An aqueous resin composition having a solid content concentration of 40% and a pH of 8 was obtained.

[Production Example 11]
Aqueous resin composition stirrer, thermometer, reflux cooling of resin (B-2) comprising a copolymerized monomer comprising a monomer having an α, β-monoethylenically unsaturated group and other copolymerizable monomers An apparatus and a reaction vessel equipped with a nitrogen introduction tube were charged with 300 g of ion-exchanged water and 1 g of sodium lauryl sulfate, and the temperature was raised to 75 ° C. while purging with nitrogen under stirring. The internal temperature is maintained at 75 ° C., 2 g of potassium persulfate is added as a polymerization initiator, and after dissolution, 250 g of ion exchange water, 1 g of sodium lauryl sulfate, 9 g of acrylamide, 200 g of styrene, 220 g of 2-ethylhexyl acrylate, 9 g of methacrylic acid Was added dropwise to the reaction vessel over 6 hours to polymerize the emulsion. After completion of dropping, the mixture was aged and neutralized for 5 hours to obtain an aqueous resin composition. The obtained aqueous resin composition had a solid content of 40% and a pH of 8.

[Production Example 12]
Into a flask equipped with an aqueous resin composition stirrer of polyester (B-3), a thermometer, a reflux cooling device, and a nitrogen introduction tube, 300 g of toluene and 300 g of polyester (manufactured by Toyobo Co., Ltd., Byron 500) were charged. Dissolved by heating. 500 g of this solution, 375 g of distilled water, and 1.5 g of sodium dodecylbenzenesulfonate (manufactured by Kao Corporation, Neopelex F-25) were mixed and stirred at a rotational speed of 10,000 rpm for 15 minutes to obtain an emulsion. Toluene in the emulsion was distilled off under reduced pressure using an evaporator to obtain a polyester-based aqueous resin composition having a solid content concentration of 45% and a pH of 7.

[Production Example 13]
An epoxy resin (B-4) aqueous resin composition stirrer, thermometer, reflux cooling device, and a four-necked flask equipped with a nitrogen inlet tube were charged with 60.0 g of diglyme and a bisphenol A type epoxy resin (Epomic R302: Mitsui Chemicals). 100 g was added and stirred while heating up to 70 ° C., and it was confirmed that the epoxy resin was completely dissolved. Here, 7.0 g of monoethanolamine (number of moles of active hydrogen (B) = 0.23 mole) (ratio of mole number of epoxy group (A) and mole number of active hydrogen in polyfunctional amine (B) ( A) / (B) = 0.70) was added and reacted at 100 ° C. for 6 hours. Subsequently, the mixture was cooled to 70 ° C., 19.7 g of succinic anhydride was added thereto, the temperature was raised again to 95 ° C. and reacted for 1 hour, and an epoxy resin having a carboxyl group in the side chain of the polyfunctional amine-modified epoxy resin A diglyme solution was obtained. The resin solution was cooled to 60 ° C., 11.5 g of 29% ammonia water was added, and the mixture was stirred for 30 minutes while maintaining the temperature at 60 ° C. Here, 175.6 g of ion-exchanged water was dropped over 30 minutes to obtain an aqueous resin composition having a solid content concentration of 33%.

[Production Example 14]
Modified Amino Resin (C) Aqueous Resin Composition (Amino Resin Aqueous Resin Composition Modified With Urethane Resin)
196 g of paraformaldehyde (containing 92% formaldehyde), 126 g of melamine, and 519 g of n-butanol were added to a reactor equipped with a thermometer, a stirrer, a reflux condenser and a solvent by-product recovery device, and 10% of phosphoric acid was stirred while stirring. The aqueous solution was added to adjust the pH of the reaction solution to 5.0. Heat to reflux temperature to dissolve. Then, after maintaining the temperature of a reaction liquid at 90 degreeC and continuing reaction for 4 hours, triethylamine was added and pH in a system was adjusted to 7.0. The mixture was cooled to 70 ° C., and excess n-butanol was removed from the system so that the solid content concentration of the resin became 70% while maintaining the temperature in the system at 70 ° C. or lower under reduced pressure to obtain an amino resin.
A four-necked flask equipped with a stirrer, thermometer, reflux cooling device, and nitrogen inlet tube was charged with 40 g of 2,2-dimethylolpropionic acid, 25 g of neopentyl glycol, 35 g of polypropylene glycol, and 45 g of toluene. While introducing nitrogen, the temperature was raised to 110 ° C. to dissolve the contents. Next, toluene of the solvent was removed while raising the temperature to 135 ° C., 75 g of MEK was added, and the internal temperature was lowered to 35 degrees. When the internal temperature dropped to 35 ° C., dropping was performed over 2 hours while maintaining 60 g of hexamethylene diisocyanate at 55 ° C. or less to obtain a urethane resin.
A reactor equipped with a thermometer, a stirrer, a reflux condenser and a solvent by-product recovery device was charged with 100 g of the amino resin, 20 g of urethane resin, and 30 g of isopropyl alcohol, and the temperature was raised to 90 ° C. for 3 hours. Went. Later, 3 g of N, N-dimethylaminoethanol was added and diluted with 15 g of water. Excess organic solvent was removed under reduced pressure to obtain a composite resin of an amino resin and a urethane resin having a solid content of 59% and a pH of 6.5.

[Production Example 15]
Modified Amino Resin (C) Aqueous Resin Composition (Amino Resin Aqueous Resin Composition Modified With Acrylic Resin)
A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube was charged with 30 g of butyl cellosolve and 70 g of isopropyl alcohol, and heated to 85 ° C. in a nitrogen gas atmosphere. Next, a mixture of 20 g of styrene as a copolymerization monomer, 40 g of lauryl methacrylate, 23 g of hydroxyethyl methacrylate, 13 g of acrylic acid and 3 g of polymerization initiator (hereinafter abbreviated as PBO) is fed and reacted over 4 hours. It was. After 1 hour and 2 hours from the end of the feed, 0.2 g of PBO was added and reacted for 2 hours from the last addition to obtain a resin solution. Neutralize the resulting resin solution with triethylamine to theoretically 100%, add deionized water to a solid content concentration of 40%, and then remove toluene and ethyl acetate under reduced pressure. As a result, an acrylic resin having a solid concentration of 40% and a pH of 8 was obtained.
A reactor equipped with a thermometer, a stirrer, a reflux condenser, and a solvent byproduct recovery device was charged with 100 g of the amino resin described in Production Example 14, 20 g of the acrylic resin, and 30 g of isopropyl alcohol, up to 90 ° C. The temperature was raised and a complexing reaction was carried out for 3 hours. Later, 3 g of N, N-dimethylaminoethanol was added and diluted with 15 g of water. Excess organic solvent was removed under reduced pressure to obtain a composite resin of an amino resin and an acrylic resin having a solid concentration of 55% and a pH of 7.

[Production Example 16]
Water-based resin composition of modified amino resin (C) (amino resin modified with amino compound having acid functional group or amide compound having acid functional group)
196 g of paraformaldehyde (containing 92% formaldehyde), 126 g of melamine, and 481 g of n-butanol were added to a reactor equipped with a thermometer, a stirrer, a reflux condenser, and a solvent byproduct recovery device, and heated to reflux temperature conditions, It was dissolved with stirring. Next, a 10% aqueous solution of phosphoric acid was added to adjust the pH of the reaction solution to 5.0, and then the reaction was continued for 4 hours under the reflux temperature condition of the reaction solution, and then cooled to 50 ° C. 46 g of β-alanine and 100 g of water were added and stirred at 50 ° C. for 1 hour to introduce an acid functional group. After neutralizing with 46 g of dimethylethanolamine, excess water and n-butanol were removed out of the system while maintaining the temperature in the system at 50 ° C. or lower under reduced pressure to obtain an amino resin having a solid content concentration of 60%. .

[Production Example 17]
A four-necked flask equipped with a water-based resin composition stirrer of a petroleum hydrocarbon resin, a thermometer, a reflux cooling device, and a nitrogen introduction tube, 300 g of hexane, petroleum resin (manufactured by Mitsui Chemicals, Highlets T-480X) Was dissolved under heating under reflux. 500 g of this solution, 250 g of distilled water, and 1.5 g of sodium dodecylbenzenesulfonate (manufactured by Kao Corporation, Neopelex F-25) were mixed and stirred for 15 minutes at a rotational speed of 10,000 rpm. Next, 0.7 g of polyacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd., Hibiswaco 304) was added and mixed by stirring to obtain an emulsion. Hexane in this emulsion was distilled off under reduced pressure with an evaporator to obtain an aqueous resin composition of a petroleum hydrocarbon resin having a solid content concentration of 50% and a pH of 8.

[Example 1]
20 g of the thermoplastic elastomer aqueous resin composition obtained in Production Example 2, 25 g of the urethane resin aqueous resin composition obtained in Production Example 9, and the modified amino resin aqueous resin composition obtained in Production Example 14 7 g was mixed to obtain a coating material.

[Example 2]
20 g of the thermoplastic elastomer aqueous resin composition obtained in Production Example 2, 20 g of the acrylic resin aqueous resin composition obtained in Production Example 10, and the modified amino resin aqueous resin composition obtained in Production Example 14 7 g was mixed to obtain a coating material.

[Example 3]
20 g of the thermoplastic elastomer aqueous resin composition obtained in Production Example 2, 20 g of the acrylic resin aqueous resin composition obtained in Production Example 11, and the modified amino resin aqueous resin composition obtained in Production Example 14 7 g was mixed to obtain a coating material.

[Example 4]
20 g of the thermoplastic elastomer aqueous resin composition obtained in Production Example 2, 15 g of the polyester aqueous resin composition obtained in Production Example 12, and the modified amino resin aqueous resin composition obtained in Production Example 14 7 g was mixed to obtain a coating material.

[Example 5]
20 g of the thermoplastic elastomer aqueous resin composition obtained in Production Example 2, 20 g of the epoxy resin aqueous resin composition obtained in Production Example 13, and the modified amino resin aqueous resin composition obtained in Production Example 14 7 g was mixed to obtain a coating material.

[Example 6]
20 g of the thermoplastic elastomer aqueous resin composition obtained in Production Example 2, 15 g of the urethane resin aqueous resin composition obtained in Production Example 9, and the acrylic resin aqueous resin composition obtained in Production Example 11 10 g and 7 g of the aqueous resin composition of the modified amino resin obtained in Production Example 14 were mixed to obtain a coating material.

[Example 7]
20 g of the thermoplastic elastomer aqueous resin composition obtained in Production Example 2, 25 g of the acrylic resin aqueous resin composition obtained in Production Example 11, and the modified amino resin aqueous resin composition obtained in Production Example 15 8 g was mixed to obtain a coating material.

[Example 8]
20 g of the thermoplastic elastomer aqueous resin composition obtained in Production Example 2, 25 g of the acrylic resin aqueous resin composition obtained in Production Example 11, and the modified amino resin aqueous resin composition obtained in Production Example 16. 7 g was mixed to obtain a coating material.

[Example 9]
20 g of the thermoplastic elastomer aqueous resin composition obtained in Production Example 2, 25 g of the acrylic resin aqueous resin composition obtained in Production Example 11, and the modified amino resin aqueous resin composition obtained in Production Example 14 4 g of the modified amino resin aqueous resin composition obtained in Production Example 15 was mixed to obtain a coating material.

[Example 10]
20 g of the thermoplastic elastomer aqueous resin composition obtained in Production Example 3 and 3 g of the modified amino resin aqueous resin composition obtained in Production Example 14 were mixed to obtain a coating material.

[Example 11]
20 g of the thermoplastic elastomer aqueous resin composition obtained in Production Example 3 and 3 g of the modified amino resin aqueous resin composition obtained in Production Example 15 were mixed to obtain a coating material.

[Example 12]
20 g of the thermoplastic elastomer aqueous resin composition obtained in Production Example 4 and 3 g of the modified amino resin aqueous resin composition obtained in Production Example 14 were mixed to obtain a coating material.

[Example 13]
20 g of the thermoplastic elastomer aqueous resin composition obtained in Production Example 5 and 3 g of the modified amino resin aqueous resin composition obtained in Production Example 14 were mixed to obtain a coating material.

[Example 14]
20 g of the thermoplastic elastomer aqueous resin composition obtained in Production Example 6 and 3 g of the modified amino resin aqueous resin composition obtained in Production Example 14 were mixed to obtain a coating material.

[Example 15]
20 g of the thermoplastic elastomer aqueous resin composition obtained in Production Example 3, 25 g of the urethane resin aqueous resin composition obtained in Production Example 9, and the modified amino resin aqueous resin composition obtained in Production Example 14 7 g was mixed to obtain a coating material.

[Example 16]
20 g of the thermoplastic elastomer aqueous resin composition obtained in Production Example 3, 20 g of the acrylic resin aqueous resin composition obtained in Production Example 10, and the modified amino resin aqueous resin composition obtained in Production Example 14 7 g was mixed to obtain a coating material.

[Example 17]
20 g of the thermoplastic elastomer aqueous resin composition obtained in Production Example 3, 20 g of the acrylic resin aqueous resin composition obtained in Production Example 11, and the modified amino resin aqueous resin composition obtained in Production Example 14 7 g was mixed to obtain a coating material.

[Example 18]
20 g of the thermoplastic elastomer aqueous resin composition obtained in Production Example 4, 25 g of the acrylic resin aqueous resin composition obtained in Production Example 11, and the modified amino resin aqueous resin composition obtained in Production Example 14 7 g was mixed to obtain a coating material.

[Example 19]
20 g of the thermoplastic elastomer aqueous resin composition obtained in Production Example 5, 25 g of the acrylic resin aqueous resin composition obtained in Production Example 11, and the modified amino resin aqueous resin composition obtained in Production Example 14 7 g was mixed to obtain a coating material.

[Example 20]
20 g of the thermoplastic elastomer aqueous resin composition obtained in Production Example 6, 25 g of the acrylic resin aqueous resin composition obtained in Production Example 11, and the modified amino resin aqueous resin composition obtained in Production Example 14 7 g was mixed to obtain a coating material.

[Example 21]
18 g of the thermoplastic elastomer aqueous resin composition obtained in Production Example 2, 2 g of the thermoplastic elastomer aqueous resin composition obtained in Production Example 3, and the urethane resin aqueous resin composition obtained in Production Example 9 25 g and 7 g of the aqueous resin composition of the modified amino resin obtained in Production Example 14 were mixed to obtain a coating material.

[Example 22]
18 g of the thermoplastic elastomer aqueous resin composition obtained in Production Example 2, 2 g of the thermoplastic elastomer aqueous resin composition obtained in Production Example 4, and the urethane resin aqueous resin composition obtained in Production Example 9 25 g and 7 g of the modified amino resin aqueous resin composition obtained in Production Example 14 were mixed to obtain a coating material.

[Example 23]
20 g of the thermoplastic elastomer aqueous resin composition obtained in Production Example 7, 25 g of the urethane resin aqueous resin composition obtained in Production Example 9, and the modified amino resin aqueous resin composition obtained in Production Example 14 7 g was mixed to obtain a coating material.

[Example 24]
20 g of the thermoplastic elastomer aqueous resin composition obtained in Production Example 7, 20 g of the acrylic resin aqueous resin composition obtained in Production Example 10, and the modified amino resin aqueous resin composition obtained in Production Example 14 7 g was mixed to obtain a coating material.

[Example 25]
20 g of the thermoplastic elastomer aqueous resin composition obtained in Production Example 7, 20 g of the acrylic resin aqueous resin composition obtained in Production Example 11, and the modified amino resin aqueous resin composition obtained in Production Example 14 7 g was mixed to obtain a coating material.

[Example 26]
20 g of the thermoplastic elastomer aqueous resin composition obtained in Production Example 7, 15 g of the polyester aqueous resin composition obtained in Production Example 12, and the modified amino resin aqueous resin composition obtained in Production Example 14 7 g was mixed to obtain a coating material.

[Example 27]
20 g of the thermoplastic elastomer aqueous resin composition obtained in Production Example 7, 20 g of the polyester aqueous resin composition obtained in Production Example 13, and the modified amino resin aqueous resin composition obtained in Production Example 14 7 g was mixed to obtain a coating material.

[Example 28]
20 g of the thermoplastic elastomer aqueous resin composition obtained in Production Example 7, 15 g of the urethane resin aqueous resin composition obtained in Production Example 9, and the acrylic resin aqueous resin composition obtained in Production Example 11 10 g of an aqueous resin composition of the modified amino resin obtained in Production Example 14 was mixed to obtain a coating material.

[Example 29]
20 g of the thermoplastic elastomer aqueous resin composition obtained in Production Example 7, 10 g of the acrylic resin aqueous resin composition obtained in Production Example 11, and the modified amino resin aqueous resin composition obtained in Production Example 15 9 g was mixed to obtain a coating material.

[Example 30]
20 g of the thermoplastic elastomer aqueous resin composition obtained in Production Example 7, 10 g of the acrylic resin aqueous resin composition obtained in Production Example 11, and the modified amino resin aqueous resin composition obtained in Production Example 16. 7 g was mixed to obtain a coating material.

[Example 31]
20 g of the thermoplastic elastomer aqueous resin composition obtained in Production Example 7, 10 g of the acrylic resin aqueous resin composition obtained in Production Example 11, and the modified amino resin aqueous resin composition obtained in Production Example 14 4 g of the modified amino resin aqueous resin composition obtained in Production Example 15 was mixed to obtain a coating material.

[Example 32]
20 g of the thermoplastic elastomer aqueous resin composition obtained in Production Example 8, 25 g of the urethane resin aqueous resin composition obtained in Production Example 9, and the modified amino resin aqueous resin composition obtained in Production Example 14 7 g was mixed to obtain a coating material.

[Example 33]
20 g of the thermoplastic elastomer aqueous resin composition obtained in Production Example 2, 25 g of the urethane resin aqueous resin composition obtained in Production Example 9, and the modified amino resin aqueous resin composition obtained in Production Example 14 Was mixed with 4 g of Nanolet R1050 (manufactured by Yashara Chemical Co., Ltd.), which is an aqueous resin composition of a terpene resin, to obtain a coating material.

[Example 34]
20 g of the thermoplastic elastomer aqueous resin composition obtained in Production Example 2, 25 g of the urethane resin aqueous resin composition obtained in Production Example 9, and the modified amino resin aqueous resin composition obtained in Production Example 14 8 g of rosin resin and 4 g of super ester E720 (Arakawa Chemical Industries, Ltd.), which is an aqueous resin composition, were mixed to obtain a coating material.

[Example 35]
20 g of the thermoplastic elastomer aqueous resin composition obtained in Production Example 2, 25 g of the urethane resin aqueous resin composition obtained in Production Example 9, and the modified amino resin aqueous resin composition obtained in Production Example 14 8 g and 4 g of the aqueous resin composition of the petroleum resin obtained in Production Example 17 were mixed to obtain a coating material.

[Example 36]
20 g of the thermoplastic elastomer aqueous resin composition obtained in Production Example 7, 25 g of the urethane resin aqueous resin composition obtained in Production Example 9, and the modified amino resin aqueous resin composition obtained in Production Example 14 Was mixed with 4 g of Nanolet R1050 (manufactured by Yashara Chemical Co., Ltd.), which is an aqueous resin composition of a terpene resin, to obtain a coating material.

[Example 37]
20 g of the thermoplastic elastomer aqueous resin composition obtained in Production Example 7, 25 g of the urethane resin aqueous resin composition obtained in Production Example 9, and the modified amino resin aqueous resin composition obtained in Production Example 14 8 g of rosin resin and 4 g of super ester E720 (Arakawa Chemical Industries, Ltd.), which is an aqueous resin composition, were mixed to obtain a coating material.

[Example 38]
20 g of the thermoplastic elastomer aqueous resin composition obtained in Production Example 7, 25 g of the urethane resin aqueous resin composition obtained in Production Example 9, and the modified amino resin aqueous resin composition obtained in Production Example 14 8 g and 4 g of the petroleum resin aqueous resin composition obtained in Production Example 17 were mixed to obtain a coating material.

[Comparative Example 1]
20 g of the thermoplastic elastomer aqueous resin composition obtained in Production Example 2, 25 g of the urethane resin aqueous resin composition obtained in Production Example 9, and Uban 28-60 which is an amino resin (manufactured by Mitsui Chemicals, Inc.) ) 7 g was mixed to obtain a coating material.

[Comparative Example 2]
20 g of the thermoplastic elastomer aqueous resin composition obtained in Production Example 2, 25 g of the urethane resin aqueous resin composition obtained in Production Example 9, and 7 g of Uban 228 (manufactured by Mitsui Chemicals) which is an amino resin. Were mixed to obtain a coating material.

[Comparative Example 3]
20 g of the thermoplastic elastomer aqueous resin composition obtained in Production Example 7, 25 g of the urethane resin aqueous resin composition obtained in Production Example 9, and Uban 28-60 (Mitsui Chemicals, Inc.), which is an amino resin ) 7 g was mixed to obtain a coating material.

[Comparative Example 4]
20 g of the thermoplastic elastomer aqueous resin composition obtained in Production Example 7, 25 g of the urethane resin aqueous resin composition obtained in Production Example 9, and 7 g of Uban 228 (manufactured by Mitsui Chemicals) which is an amino resin. Were mixed to obtain a coating material.

[Comparative Example 5]
20 g of the thermoplastic elastomer aqueous resin composition obtained in Production Example 2 and 25 g of the urethane resin aqueous resin composition obtained in Production Example 9 were mixed to obtain a coating material.
[Evaluation and results]
<Stability of water-based resin composition>
The obtained aqueous resin composition was allowed to stand at room temperature for 30 minutes with a nonvolatile content of 30%, and the state of the solution was evaluated. After 1 week, no separation and precipitation were confirmed and no thickening was observed, ○, separation and / or precipitation was observed and Δ was easily dispersible, and separation and / or precipitation was observed Those that could not be easily dispersed by stirring were evaluated as x.

<< Sprayability of water-based resin composition >>
Spray gun (Iwata coater Kogyo Co. Wajda over spray gun (trade name; W-88-13H5G)) using, atomization pressure 4 kg / cm ^2, the nozzle 1 is opened rotating, the temperature 30 ° C. in the paint booth Each of the aqueous resin compositions obtained in Examples and Comparative Examples was sprayed to observe whether stringing occurred or not. .
<Physical properties of coating film>
The aqueous resin composition used for the evaluation is a 50% aqueous solution of Olfine E1010 (manufactured by Nissin Chemical Industry Co., Ltd.) as a wetting agent with respect to the resin of the aqueous resin composition obtained in each Example and Comparative Example. It was created by adding some parts.

<Creation and evaluation of evaluation film>
The obtained aqueous resin composition was subjected to Ford Cup No. 1 with ion-exchanged water. The dilution was adjusted so that the falling speed at 4 was 15 ± 2 seconds. Next, each of the aqueous resin compositions was spray-applied to a polypropylene plate (product name: X708) made of polypropylene whose surface was wiped with isopropyl alcohol so that the film thickness after drying was 10 μm. A coating film was formed and allowed to stand at room temperature for 10 minutes, and then treated in a 120 ° C. oven for 30 minutes to prepare a test piece (A). Further, the aqueous resin composition diluted in the same manner as described above is spray-coated on the polypropylene square plate whose surface is wiped with isopropyl alcohol so that the film thickness after drying is 10 μm. After forming the film and allowing it to stand at room temperature for 10 minutes, it is placed in an oven at 100 ° C. and treated for 5 minutes. On this coating film, a white top coat is dried so that the film thickness after drying is 80 μm. After coating and forming a coating film and leaving it to stand at room temperature for 10 minutes, it was placed in an oven at 120 ° C. and treated for 30 minutes to prepare a test piece (B).
Test piece (A): After 24 hours, the appearance of the coating film, cross-cut peel test, and pencil hardness were evaluated.

Test piece (B): After 24 hours, the appearance of the coating film, cross-cut peel test, and peel strength were evaluated. Further, after the water resistance test, the appearance evaluation of the coating film and the cross-cut peel test were performed, and after the weather resistance test, the gloss retention and the cross-cut peel test were evaluated.
In addition, about the test piece (A), the thing with a bad coating-film external appearance did not implement a cross-cut peeling test and pencil hardness evaluation. Moreover, about the test piece (B), what peeled by the cross-cut peel test or the thing which was not the strength of 600 g / cm or more by peel strength did not implement each test of a weather resistance and warm water resistance.
The top coat used here was Olester Q186 (trade name, nonvolatile content 50%, hydroxyl value 30 KOHmg / g, manufactured by Mitsui Chemicals Co., Ltd.) and UV absorber (TINUVIN327) 0.2% based on the resin content. , Disperse the antioxidant (IRGANOX1330) to 0.2% based on the resin content and the titanium oxide pigment (Tipeque-CR93 (trade name, manufactured by Ishihara Sangyo Co., Ltd.)) to 30% based on the resin content. The main agent and MT orester NM89-50G (trade name, non-volatile content 50%, NCO%: 6%, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.), which is a curing agent containing NCO, are OH / NCO = 0.95. What was mixed was used.

<Cross-cut peel test>
In the cross-cut peel test, a test piece with a cross cut is prepared according to the method described in JIS-K-5400, and Cellotape (registered trademark) (Nichiban Co., Ltd. product) is pasted on the cross cut. After that, it was quickly pulled and peeled in the 90 ° direction, and the evaluation was performed based on the number of grids that were not peeled out of 100 grids.
<Peel strength test>
In the peel strength test, a 1 cm wide cut is made in the coating film, the edge is peeled off, the edge is pulled in the direction of 180 ° at a speed of 50 mm / min, and the peel strength is 1000 g / cm or more. Evaluation was made with ◯, 600 g / cm or more and less than 800 g / cm as Δ, and less than 600 g / cm as x.
<Water resistance test>
In the water resistance test, the test piece was immersed in water adjusted to 40 ° C. for 240 hours, and then the appearance and adhesion of the coating film were evaluated.

<Pencil hardness>
The test was conducted by the method described in JIS K5600-5-4, and evaluations were made with ○ being harder than HB and × being softer than B.
<Appearance of coating film>
As for the appearance of the coating film, the coating film after coating was visually evaluated for the presence or absence of a lot, and the glossy one was marked with ◯ and the one without it was marked with ×. Moreover, about the coating film after a water-resistant test, the presence or absence of a swelling was evaluated visually, the thing which has a change in coating films, such as (circle) and a swelling, was set to x.
<Weather resistance test>
The weather resistance test was carried out according to the method of the accelerated weather resistance test described in JIS-K-5400, and evaluated the cross peel test and the gloss retention rate for those evaluated with a sunshine carbon arc lamp type for 1000 hours. .
<Measurement of gloss retention>
Gloss retention rate is calculated from 60 degree specular gloss before and after the test (JIS-K-5400), retention rate (%) of the measured value = (gloss after test / initial gloss) × 100 In addition, the case where the gloss retention was 80% or more and no discoloration was observed was evaluated as ◯, the case where it was 60% or more and less than 80% was evaluated as Δ, and the case where it was less than 60% was evaluated as ×.

  The results are shown in Table 1.

Claims (5)

Water-based resin composition of thermoplastic elastomer (A-1), water-based resin composition of urethane resin (B-1) and / or monomer having α, β-monoethylenically unsaturated group and other copolymerizable Aqueous resin composition of resin (B-2) and / or polyester (B-3) aqueous resin composition and / or epoxy resin (B-4) aqueous resin composed of copolymerizable monomers composed of various monomers A coating material comprising a composition and an aqueous resin composition of a modified amino resin (C). A coating material comprising an aqueous resin composition of a modified thermoplastic elastomer (A-2) and an aqueous resin composition of a modified amino resin (C). Water-based resin composition of modified thermoplastic elastomer (A-2), water-based resin composition of urethane resin (B-1) and / or monomer having α, β-monoethylenically unsaturated group and other copolymerization Resin (B-2) aqueous resin composition and / or polyester (B-3) aqueous resin composition and / or epoxy resin (B-4) aqueous system comprising copolymerizable monomers comprising possible monomers A coating material comprising a resin composition and an aqueous resin composition of a modified amino resin (C). Water-based resin composition of thermoplastic elastomer (A-1) and modified thermoplastic elastomer (A-2), water-based resin composition of urethane resin (B-1) and / or α, β-monoethylenically unsaturated group An aqueous resin composition of a resin (B-2) and / or an aqueous resin composition of a polyester (B-3) and / or a copolymerizable monomer comprising a monomer containing A coating material comprising an aqueous resin composition of an epoxy resin (B-4) and an aqueous resin composition of a modified amino resin (C). 10 to 95 parts by weight of the water-based resin composition of the thermoplastic elastomer (A-1) and / or the modified thermoplastic elastomer (A-2), and the water-based resin composition and / or α, β of the urethane resin (B-1). -An aqueous resin composition of resin (B-2) and / or polyester (B-3) comprising a copolymerizable monomer comprising a monomer having a monoethylenically unsaturated group and another copolymerizable monomer It comprises 0 to 70 parts by weight of an aqueous resin composition and / or an epoxy resin (B-4) and 5 to 50 parts by weight of an aqueous resin composition of a modified amino resin (C). And / or (A-2), (B-1) and / or (B-2) and / or (B-3) and / or (B-4), and (C) is 100 parts by weight in total A coating material characterized by being mixed so that