JP2009108128A - Aqueous dispersion - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous coating material exhibiting excellent adhesiveness with molded products of various resins including polyolefin such as polypropylene, synthetic rubber, unsaturated polyester, epoxy resin and urethane resin, with a steel plate, and with metal such as aluminum. <P>SOLUTION: The aqueous dispersion comprises a propylene-based resin A modified by a polymer of copolymerizable monomers E consisting of a monomer having an α,β-monoethylenically unsaturated group and other copolymerizable monomers, a propylene-based resin D containing carboxylic acid bonded to a polymer chain or a group of carboxylic acid salt at a concentration of 0.05-5 millimole equivalent in terms of the group represented by formula 1 per 1 g resin, an anionic and/or nonionic surface active agent F, and water G. The copolymerizable monomers E include at least one kind of (meth)acrylic ester and/or an aromatic vinyl compound. In this way, the coating material can be directly used without causing a separation phenomenon, and a paint and a primer allowing spray coating and exhibiting excellent adhesiveness with various resin molded products of polyolefin, synthetic rubber, and the like, with a steel plate, and with metal such as aluminum are provided. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an aqueous dispersion and use thereof, in particular, a monomer having an α, β-monoethylenically unsaturated group containing at least one (meth) acrylic acid ester and / or an aromatic vinyl compound, and From propylene resin (A) modified with a polymer of copolymerizable monomer (E) consisting of other copolymerizable monomers, and propylene resin (D) containing a carboxylic acid or salt thereof in the polymer chain Relates to an aqueous dispersion and its use.

Conventionally, polyolefin resins are generally productive and excellent in various moldability, and have many advantages such as light weight, rust prevention, and impact resistance. Therefore, interior and exterior of automobiles and ships, and home appliances. It is 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 thickened coating film or a modified propylene-ethylene copolymer (patent document 3) formed by graft copolymerization of maleic acid or its anhydride is used. It has been. 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

  The subject of the present invention is an improvement of the above-mentioned problems, such as molded products of various resins consisting of polyolefin such as polypropylene, synthetic rubber, unsaturated polyester, epoxy resin, urethane resin, etc., and metals such as steel plates and aluminum, An object of the present invention is to provide a water-based coating material that exhibits excellent adhesion.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that the following aqueous dispersion is extremely excellent for achieving the above-mentioned problems, and have completed the present invention.

That is, the aqueous dispersion of the present invention is
[1] (A) a propylene-based resin modified with a polymer of a copolymerizable monomer (E) comprising a monomer having an α, β-monoethylenically unsaturated group and another copolymerizable monomer; ,
(D) A group of a carboxylic acid or a salt thereof bonded to a polymer chain is represented by the formula (1) —C—O— per gram of resin.
・ ・ ・ (1)
O
A propylene-based resin containing at a concentration of 0.05 to 5 mmol equivalent in terms of a group represented by:
(F) an anionic and / or nonionic surfactant, and
(G) including water,
An aqueous dispersion, wherein the copolymerizable monomer (E) contains at least one (meth) acrylic acid ester and / or an aromatic vinyl compound.
[2] (A) a propylene resin modified with a polymer of a copolymerizable monomer (E) comprising a monomer having an α, β-monoethylenically unsaturated group and another copolymerizable monomer; ,
(C) an unmodified propylene resin;
(D) A group of a carboxylic acid or a salt thereof bonded to a polymer chain is represented by the formula (1) —C—O— per gram of resin.
・ ・ ・ (1)
O
A propylene-based resin containing at a concentration of 0.05 to 5 mmol equivalent in terms of a group represented by:
(F) an anionic and / or nonionic surfactant, and
(G) including water,
An aqueous dispersion, wherein the copolymerizable monomer (E) contains at least one (meth) acrylic acid ester and / or an aromatic vinyl compound.
[3] (B) Copolymer comprising propylene-based resin (b) modified with acid or hydroxyl group, comprising a monomer having an α, β-monoethylenically unsaturated group and another copolymerizable monomer The aqueous dispersion according to [1], comprising a propylene-based resin modified with a polymer of the polymerizable monomer (E) and (D), (F), (G).
[4] (B) Copolymer comprising propylene-based resin (b) modified with acid or hydroxyl group comprising a monomer having an α, β-monoethylenically unsaturated group and another copolymerizable monomer The aqueous dispersion according to [2], comprising a propylene-based resin modified with a polymer of the polymerizable monomer (E) and (C), (D), (F), (G).
[5] (D) is 0.3 to 60 parts by weight and (F) is 100 parts by weight of the resin comprising (A), (B), or (A) or (B) and (C). 0.5 to 40 parts by weight, characterized in that it contains 3 to 90% by weight of (G), and the content of (C) relative to (A) or (B) is 0 to 98% by weight The water dispersion according to any one of [1] to [4].
[6] Further comprising an aqueous dispersion of petroleum hydrocarbon resin (H) and / or rosin resin (I) and / or terpene resin (J) [1] to [ [5] The water dispersion according to any one of [5].
[7] (A), (B), (A) or (B), (C) 20 to 100 parts by weight, petroleum hydrocarbon resin (H) and / or rosin resin (I) and / or Or it consists of 0 to 50 parts by weight of terpene resin (J) and 0 to 80 parts by weight of polyester (K) and / or acrylic resin (L) and / or urethane resin (M), and (A) or (B ), Or (A) or (B) and (C), (H) and / or (I) and / or (J), (K) and / or (L) and / or (M) The water dispersion according to any one of [1] to [6], which is 100 parts by weight.
[8] The propylene-based resin used in (A), (B) and (C) has a molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) in the range of 1 to 3. The water dispersion according to any one of [1] to [7].
[9] A paint, primer, adhesive, additive, binder, film containing the water dispersion according to any one of [1] to [8].
[10] The aqueous dispersion according to any one of [1] to [8], wherein the copolymerizable monomer (E) contains a copolymerizable monomer having active hydrogen and / or a hydroxyl group.
[11] A paint, primer, adhesive, additive, binder, film containing the aqueous dispersion described in [10] and a curing agent capable of reacting with active hydrogen and / or a hydroxyl group.

  According to the present invention, the coating material can be used as it is without causing a separation phenomenon, and is a paint and primer that can be spray-coated, various resin molded products such as polyolefin and synthetic rubber, and metal such as steel plate and aluminum. It is a completely water-based coating material that has an unprecedented effect of being excellent in adhesion to water. Moreover, it is suitable for the use of the coating material and primer which can use the hardening | curing agent which can react with active hydrogen and / or a hydroxyl group.

  Hereinafter, the present invention will be specifically described.

<Propylene-based resin>
Examples of the propylene resin used in the present invention include polypropylene, an ethylene / propylene copolymer, a propylene / 1-butene copolymer, a resin having a propylene skeleton such as an ethylene / propylene / 1-butene copolymer, or propylene. , Ethylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-hexene, 1-octene, 1-decene, 1-dodecene And a resin obtained by copolymerizing one or more α-olefins such as.
Among these, the weight average molecular weight (hereinafter abbreviated as Mw. The weight average molecular weight can be measured, for example, by gel permeation chromatography (GPC) using polystyrene as a standard) is usually 10,000 to. The range is 500,000, preferably 30,000 to 400,000.

<(A) Propylene Resin Modified with Polymer of Copolymerizable Monomer (E) Consisting of Monomer having α, β-Monoethylenically Unsaturated Group and Other Copolymerizable Monomer>
The propylene-based resin modified with the copolymerizable monomer (E) used in the present invention is the above-described propylene-based resin alone or a mixture of two or more of the above-mentioned copolymerizable monomers. Although it can be obtained by modifying the polymer of (E), there is no problem even if some of them are not modified.

Examples of monomers having an α, β-monoethylenically unsaturated group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) ) Acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, tridecyl (meth) acrylate, lauroyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (Meth) acrylates such as (meth) acrylate, dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate; hydroxyethyl acrylate, 2-hydroxyethyl (meth) acrylate Hydroxyl group-containing vinyls such as 2-hydroxypropyl (meth) acrylate, lactone-modified hydroxyethyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl acrylate; acrylic acid, methacrylic acid, maleic acid, itaconic acid, Carboxy group-containing vinyls such as ω-carboxy-polycaprolactone monoacrylate and phthalic acid monohydroxyethyl acrylate; monoesterified products of these carboxyl group-containing vinyls; epoxy groups such as glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate -Containing vinyls; isocyanate group-containing vinyls such as vinyl isocyanate and isopropenyl isocyanate; styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, etc. Other examples include (meth) acrylonitrile, vinyl acetate, vinyl propionate, (meth) acrylamide, methylol (meth) acrylamide, and α-olefin having 2 to 20 carbon atoms. In addition, macromonomers having the above-mentioned monomer or copolymer thereof in the segment and having a vinyl group at the terminal can also be used.
Other copolymerizable monomers include, for example, carboxylic anhydrides such as maleic anhydride and citraconic anhydride.

The copolymerizable monomer (E) used in the present invention is characterized in that it contains at least one copolymerizable monomer selected from the group consisting of (meth) acrylic acid esters and / or aromatic vinyl compounds.
Moreover, description like the methyl (meth) acrylate described here shows methyl acrylate and methyl methacrylate.

The amount of modification of the polymer of the copolymerizable monomer (E) used in the present invention is 1 to 90 parts by weight of the copolymer of the copolymerizable monomer (E) with respect to 99 to 10 parts by weight of the propylene-based resin. The total of the functional monomer (E) and the propylene-based resin is 100 parts by weight) is preferable in terms of adhesion to various base materials.
The propylene resin modified with the copolymer of the copolymerizable monomer (E) used in the present invention can be obtained by various methods. For example, the propylene resin and the copolymerizable monomer (E) are mixed in an organic solvent. After reacting in the presence of a polymerization initiator, the solvent is removed to form a powder, and this can be modified by adding the polymerization initiator and a propylene resin into an extruder to modify under heating, or by heating and melting the propylene resin. A method in which the above-mentioned copolymerizable monomer (E) and the polymerization initiator are modified while reacting with stirring, or a mixture of the copolymerizable monomer (E), the polymerization initiator and a propylene resin is extruded into the melt. And a method of denatured while reacting while heating and kneading.

  Examples of organic solvents 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, Alcohols such as isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, methyl cellosolve, cellosolve (ethyl cellosolve), butyl cellosolve Methyl carbitol, ethyl carbitol, can be an organic solvent ether such as butyl carbitol, also may be a mixture of two or more thereof. Among these, aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons are preferable, and aliphatic hydrocarbons and alicyclic hydrocarbons are more preferably used.

  As a polymerization initiator used in the present invention, di-tert-butyl peroxide, tert-butyl peroxy-2-ethylhexanoate, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, lauroyl peroxide, tert-Butylperoxybenzoate, 2,5-dimethyl-2,5-di (peroxybenzoate) hexyne-3, 1,4-bis (tert-butylperoxyisopropyl) benzene, lauroyl peroxide, tert-butylperoxide Acetate, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 2,5-dimethyl-2,5-di (tert-butylperoxide) hexane, tert-butylbenzoate, tert -Butylperphenyla Organic peroxides such as tate, tert-butyl perisobutyrate, tert-butyl per-sec-octoate, tert-butyl perpivalate, cumene hydroperoxide, azobisisobutyronitrile, 4,4′-azobis Examples include azo compounds such as (4-cyanopentanoic acid) and 2,2′-azobis (2-methyl-N- (2-hydroxyethyl) propioamide). These can be used alone or in admixture of two or more.

<Copolymerizable monomer comprising (B) a monomer having an α, β-monoethylenically unsaturated group and another copolymerizable monomer from propylene resin (b) modified with acid or hydroxyl group Propylene Resin Modified with Polymer (E)>
The propylene-based resin (b) modified with an acid or a hydroxyl group used in the present invention is the above-described propylene-based resin alone or a mixture of two or more of the above-described acids or hydroxyl group-containing copolymers. Although it is obtained by modifying with a functional monomer, there is no problem even if some of them are not modified.

Examples of the acid or hydroxyl group-containing copolymerizable monomer used here include hydroxyethyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, and lactone-modified hydroxyethyl (meta). ) Hydroxyl group-containing vinyls such as acrylate and 2-hydroxy-3-phenoxypropyl acrylate, carboxyl such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, ω-carboxy-polycaprolactone monoacrylate, monohydroxyethyl acrylate phthalate Examples thereof include carboxylic anhydrides such as group-containing vinyls, maleic anhydride, and citraconic anhydride, and these can be used alone or in combination of two or more.
The amount of the acid or hydroxyl group-containing copolymerizable monomer used in the propylene-based resin (b) modified with an acid or a hydroxyl group is generally 0. 0% of the weight of the propylene-based resin in terms of adhesion to various substrates. The range is 5 to 20% by weight, more preferably 0.5 to 15% by weight.

  The propylene resin (b) modified with an acid or a hydroxyl group used in the present invention can be obtained by various methods. For example, the propylene resin and the above acid and hydroxyl group-containing copolymerizable monomer in an organic solvent. A method of removing the solvent after modification in the presence of a polymerization initiator, a method of modifying an acid, a hydroxyl group-containing copolymerizable monomer and a polymerization initiator with stirring into a melt obtained by heating and melting a propylene-based resin, Examples thereof include a method in which a mixture of a propylene-based resin, the above acid, a hydroxyl group-containing copolymerizable monomer, and a polymerization initiator is supplied to an extruder and modified while heating and kneading.

  Copolymer comprising propylene-based resin (b) modified with acid or hydroxyl group, which is used in the present invention, comprising a monomer having an α, β-monoethylenically unsaturated group and other copolymerizable monomers. The propylene-based resin modified with the polymer of the polymerizable monomer (E) is a propylene-based resin modified with the above-mentioned acid or hydroxyl group alone, or a mixture of two or more of the above-described monomers of the copolymerizable monomer (E). Although it can be obtained by modifying the coalescence, there is no problem even if some of them are not modified.

  The propylene resin obtained by modifying the propylene resin (b) modified with the acid or hydroxyl group used in the present invention with the copolymerizable monomer (E) can be obtained by various methods. A method in which the propylene resin (b) modified with an acid or a hydroxyl group in an organic solvent and the above copolymerizable monomer (E) are modified in the presence of a polymerization initiator and then desolvated, or modified with an acid or a hydroxyl group A method of modifying the above-mentioned copolymerizable monomer (E) and the polymerization initiator with stirring into a melt obtained by heating and melting the propylene-based resin (b), or a propylene-based modified with an acid or a hydroxyl group A method in which a mixture of the resin (b), the above copolymerizable monomer (E) and a polymerization initiator is supplied to an extruder and modified while heating and kneading, or contains an acid-modified propylene resin and a hydroxyl group You And a method of heating under denaturing the copolymerizable monomer include methods for heating under denaturing copolymerizable monomers containing modified propylene resin and an acid with a hydroxyl group or the like.

<(C) Unmodified propylene resin>
As the propylene-based resin used in the present invention, those described in the above <Propylene-based resin> excluding the above (A) and (B) can be used.

<Propylene resin used in (A), (B) and (C)>
Among the propylene resins used in (A), (B) and (C) of the present invention, those having a molecular weight distribution (Mw / Mn) in the range of 1 to 3 determined by gel permeation chromatography (GPC) Is preferable from the viewpoint of reducing the particle size of the aqueous dispersion.

<(D) Propylene-based resin containing a group of carboxylic acid or a salt thereof bonded to a polymer chain at a concentration of 0.05 to 5 mmol equivalent in terms of group represented by the formula (1) per gram of resin>
(D) The carboxylic acid or salt group bonded to the polymer chain used in the present invention per gram of resin
Formula (1) -C-O-
・ ・ ・ (1)
O
As a propylene-based resin containing 0.05 to 5 mmol equivalent in terms of a group represented by the formula: acrylic acid, methacrylic acid, maleic acid, itaconic acid, ω-carboxy-polycaprolactone monoacrylate And those modified with carboxyl group-containing vinyls such as monohydroxyethyl acrylate phthalate, and carboxylic anhydrides such as maleic anhydride and citraconic anhydride. There is no problem even if these acid groups are partially or wholly saponified.
The concentration of the carboxylic acid or salt group bonded to the polymer chain is 0.05 to 5 mmol equivalent in terms of dispersibility in water.
The propylene-based resin used in the present invention includes the propylene-based resin, and those having a weight average molecular weight of 500 to 500,000 can be used.

<(F) Anionic and / or Nonionic Surfactant>
As the anionic surfactant and nonionic surfactant used in the present invention, known ones are used without limitation.

  Known anionic surfactants can be used. For example, primary higher fatty acid salts, secondary higher fatty acid salts, primary higher alcohol sulfates, and secondary higher alcohol sulfates. Salt, primary higher alkyl sulfonate, secondary higher alkyl sulfonate, higher alkyl disulfonate, sulfonated higher fatty acid salt, higher fatty acid sulfate ester salt, higher fatty acid sulfate sulfonate salt, higher alcohol ether Examples include sulfuric acid sulfonates, higher alcohol ether sulfonates, higher fatty acid amide alkylol sulfates, alkylbenzene sulfonates, alkylphenol sulfonates, alkylnaphthalene sulfonates, and alkylbenzimidazole sulfonates. .

  Among these anionic surfactants, particularly preferred are higher fatty acid salts, particularly alkali metal salts of saturated or unsaturated higher fatty acids having 10 to 20 carbon atoms, such as capric acid, Unsaturated fatty acids such as undecanoic acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, etc. Mention may be made of alkali metal salts of fatty acids or mixtures thereof.

As the nonionic surfactant, known ones can be used. For example, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene fatty acid amide ether, polyhydric alcohol fatty acid Examples include esters, polyoxyethylene polyhydric alcohol fatty acid esters, fatty acid sucrose esters, alkylolamides, polyoxyalkylene block copolymers, and the like.
As the surfactant, an anionic surfactant and a nonionic surfactant can be used alone, or a plurality of surfactants can be used in combination.

<Production of water dispersion>
In the present invention, methods for dispersing a resin comprising (A), (B), or (A) or (B) and (C) in water are disclosed in, for example, Japanese Patent Publication No. 7-008933, Japanese Patent Publication No. 7- No. 096647, Japanese Patent Publication No. 5-039995 and the like.

  In the present invention, the amount of (D) used is (A), (B), or (A) or (B) and (C) 100 parts by weight of resin, and (D) is added to water. From the viewpoint of dispersibility, 0.3 to 60 parts by weight is preferable, and 0.5 to 50 parts by weight is more preferable.

  In the present invention, the amount of (F) used is the dispersibility in water with respect to 100 parts by weight of the resin comprising (A), (B), or (A) or (B) and (C). The amount is preferably 0.5 to 40 parts by weight, more preferably 1 to 30 parts by weight.

  In the present invention, the amount of (G) water used is preferably from 3 to 90 parts by weight based on the resin comprising (A), (B), or (A) or (B) and (C). .

  Examples of the basic compound used in the present invention include ethylamine, propylamine, butylamine, benzylamine, triethylamine, monoethanolamine, diethylamine, diethanolamine, trimethylamine, triethylamine, triisopropylamine, dimethylethanolamine, triethanolamine, and methyl. Examples include amines such as diethanolamine, diethylenetriamine and ethylaminoethylamine, ammonia, and alkaline earth metal hydroxides and alkali metal salts such as sodium hydroxide and calcium hydroxide. Two or more of these may be used in combination.

<Petroleum hydrocarbon resin (H)>
Examples of the petroleum hydrocarbon resin (H) used in the present invention include an aliphatic petroleum resin whose main raw material is a C5 fraction of tar naphtha, an aromatic petroleum resin whose main raw material is a C9 fraction, and their Copolymeric 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.

<Rosin resin (I)>
Examples of the rosin resin (I) 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.

<Terpene resin (J)>
Examples of the terpene resin (J) used in the present invention include resins composed of α-pinene, β-pinene, limonene, dipentene, terpene phenol, terpene alcohol, terpene aldehyde, and the like. Α-pinene, β-pinene, Examples thereof include aromatic-modified terpene resins obtained by polymerizing aromatic monomers such as styrene on limonene, dipentene, and the like, and hydrogenated products thereof can also be mentioned. Among these, terpene phenol resins, aromatic modified terpene resins, and hydrogenated products thereof are preferable.

  In the present invention, petroleum hydrocarbon resin (H), rosin resin (I), and terpene resin (J) can be used in combination.

<Polyester (K)>
Examples of the polyester (K) used in the present invention include polyesters such as 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.

Examples of the organic solvent used in the present invention include aromatic hydrocarbons such as xylene, toluene, and ethylbenzene, ethyl acetate, n-butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and 3-methoxybutyl acetate. Organic solvents such as ester solvents, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone can be used, and a mixture of two or more of these may be used.
In the method of neutralizing these acids and the like with a basic substance, the acid value of the polyester is preferably 1 to 80 KOHmg / g, more preferably 3 to 70 KOHmg / g.
In addition, in a method using an emulsifier in the presence of an organic solvent or a method of melt-kneading with an emulsifier, the amount of the emulsifier is preferably in the range of 0.1 to 25 parts by weight, more preferably 0.5 to 20 parts by weight. A range is preferred.
Examples of the emulsifier used here include a propylene resin (D) containing a carboxylic acid bonded to a polymer chain, a surfactant, carboxymethyl cellulose, polyacrylic acid, polyvinyl alcohol, a sulfonate-containing polyester, and the like. Two or more of these may be used in combination.

  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 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, a sodium salt of 5-sulfoisophthalic acid or a sodium salt of dimethyl 5-sulfoisophthalic acid is preferably used.

In addition, these sulfonic acid-containing component monomers are used in an amount corresponding to that the sulfonate-containing polyester is contained at a concentration of 0.1 to 1.5 mmol equivalent in terms of —SO ₃ ^— group per gram of polymer. It is preferable to use an amount corresponding to containing at a concentration of 0.2 to 1.0 mmol equivalent.
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.

<Acrylic resin (L)>
The acrylic resin (L) used in the present invention is a resin comprising a copolymerizable monomer comprising a monomer having an α, β-monoethylenically unsaturated group and another copolymerizable monomer, As these copolymerizable monomers, 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, (meth) acrylic acid esters such as diethylaminoethyl (meth) acrylate, hydroxyethyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, Hydroxyl group-containing vinyls such as 4-hydroxybutyl acrylate, lactone-modified hydroxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, Carboxylic group-containing vinyls such as crylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, ω-carboxy-polycaprolactone monoacrylate, phthalic acid monohydroxyethyl acrylate, and monoesterified products thereof, glycidyl (meth) acrylate , Epoxy group-containing vinyls such as methyl glycidyl (meth) acrylate, isocyanate group-containing vinyls such as vinyl isocyanate and isopropenyl isocyanate, aromatics such as styrene, α-methylstyrene, vinyltoluene and t-butylstyrene Vinyls, acrylamides, methacrylamides, N-methylol methacrylamides, N-methylol acrylamides, diacetone acrylamides, maleic amides and other amides, vinyl acetates, vinyl propionates, etc. Esters, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (methacrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-dipropylaminoethyl (meth) acrylate, Aminoalkyl (meth) acrylates such as N, N-dibutylaminoethyl (meth) acrylate, N, N-dihydroxyethylaminoethyl (meth) acrylate, styrene sulfonic acid, sodium styrene sulfonate, 2-acrylamido-2-methyl Unsaturated sulfonic acids such as propanesulfonic acid, unsaturated phosphoric acids such as mono (2-methacryloyloxyethyl) acid phosphate, mono (2-acryloyloxyethyl) acid phosphate, other acrylonitrile, methacrylonitrile, 2-methyl Carboxyethyl acrylate, 2-ethoxyethyl acrylate, ethylene, _propylene, alpha-olefin C 4 _{-C 20,} 1,2,2,6,6-pentamethyl-4-piperidyl (meth) acrylate, 2,2,6, Examples include 6-tetramethyl-4-piperidyl (meth) acrylate and 2- (2′-hydroxy-5′-methacryloyloxyethylphenyl) -2H-benzotriazole. 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.

  As a method for producing an aqueous dispersion 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, Although not limited, for example, after adding a basic substance and ion-exchanged water to a resin solution obtained by polymerizing a copolymerizable monomer and a polymerization initiator in an organic solvent, the organic solvent is added. It can be produced by a known method such as a removal method or an emulsion polymerization method in which a copolymerizable monomer is polymerized in water in the presence of a surfactant or a polymerization initiator.

The method for obtaining a resin comprising a copolymerizable monomer comprising a monomer having an α, β-monoethylenically unsaturated group and other copolymerizable monomers according to the present invention. The monomer must contain an acidic group that can be neutralized with a basic substance. Specifically, the acid value of the resin using the carboxyl group-containing vinyls described in the copolymerizable monomer is preferably 4 KOHmg / g or more, and more preferably 7 KOHmg / g or more. When the acid value is less than 4 KOHmg / g, the hydrophilicity becomes low and it becomes difficult to make it water-based. The acid value described above is a value in a resin (solid) excluding a solvent.
It is used to synthesize a resin comprising a copolymerizable monomer comprising a monomer having an α, β-monoethylenically unsaturated group of the present invention and other copolymerizable monomers.

Examples of the polymerization initiator include persulfates such as ammonium persulfate, potassium persulfate, and sodium persulfate, hydrogen peroxide, the polymerization initiator described above, or metal ions such as iron ions and sodium sulfoxylate. , Redox initiators in combination with reducing agents such as formaldehyde, sodium pyrosulfite, sodium hydrogen sulfite, L-ascorbic acid, Rongalite, etc., and one or more of these can be used.
The amount of these polymerization initiators used is usually 0.1 to 10% by weight based on the total amount of monomers.
Furthermore, in order to improve the stability to water, said surfactant can be used.

  As 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, the Tg measured by DSC is −60 ° C. -80 degreeC is preferable, More preferably, it is -30 degreeC-50 degreeC. Further, the weight average molecular weight by GPC is preferably 1000 to 500000, and more preferably 5000 to 200000.

<Urethane resin (M)>
Examples of the polyfunctional isocyanate compound that is a component constituting the urethane resin (M) used in the present invention include various aliphatic polyisocyanates such as ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, and octamethylene diisocyanate. Isocyanate, isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, 4,4′-dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane diisocyanate, 2,2-dimethyldicyclohexylmethane diisocyanate, bis (4-isocyanato- n-butylidene) pentaerythritol, diisocyanate dimate Such as alicyclic polyisocyanate, phenylene diisocyanate, tolylene diisocyanate, ethylphenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, polymeric MDI, naphthalene triisocyanate, diphenylmethane -2,4,4'-triisocyanate, hexahydrodiphenylmethane-4,4'-diisocyanate, diphenyl ether diisocyanate, and other aromatic polyisocyanates, thiodiethyl diisocyanate, thiopropyl diisocyanate, thiodihexyl diisocyanate, dimethylsulfone diisocyanate, etc. Sulfur-containing aliphatic isocyanate, diphenyl sulfide-2,4'-diisocyanate, diph Aromatic disulfide isocyanates such as phenyl sulfide-4,4'-diisocyanate, aliphatic disulfide isocyanates such as diphenyl disulfide-4,4'-diisocyanate, 2,2'-dimethyldiphenyl disulfide-5,5'-diisocyanate Aromatic sulfone isocyanate such as diphenylsulfone-4,4′-diisocyanate, diphenylsulfone-3,3′-diisocyanate, 4-methyl-3-isocyanatobenzenesulfonyl-4′-isocyanatophenol ester, etc. Sulfonic acid ester isocyanate, 4,4'-dimethylbenzenesulfonyl-ethylenediamine-4,4'-diisocyanate, 4,4'-dimethoxybenzenesulfonyl-ethylenediamine-3,3'-diisocyanate And sulfur-containing heterocyclic compounds such as thiophene-2,5-diisocyanate, 1,4-dithian-2,5-diisocyanate, and the like.

  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 compounds, the obtained resin, and the yellowing resistance, thermal stability, light stability of the film after coating it and forming a film, or the availability of a polyfunctional isocyanate compound From the aspect, aliphatic polyisocyanates and alicyclic polyisocyanate compounds are preferable, and among them, hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 2,5-bisisocyanate methylnorbornane, 2,6- Bisisocyanatomethylnorbornane and derivatives thereof are particularly preferred.

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. Polyol compound: ethylene glycol, diethylene glycol, triethylene glycol, 1,4-butanediol, 1,3-butanediol, propylene glycol, dipropylene glycol, butylene glycol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, Pentaerythritol, dipentaerythritol, sorbitol, erythritol, hexanetriol, triglycerose, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, cyclopentanediol, cyclohexanediol, tricyclo [5.2.1.0 ^2,6 ] Aliphatic polyols such as decane-dimethanol, bicyclo [4.3.0] -nonanediol, dicyclohexanediol , Aromatic polyols such as dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxybenzene, benzenetriol, biphenyltetraol, bisphenol S, halogenated polyols such as dibromoneopentyl glycol, polyester polyol, polyethylene glycol, polyether polyol, Polythioether polyols, polyacetal polyols, polycarbonate polyols, polycaprolactone polyols, silicon polyols, flanged methanol, and condensation reactions of organic acids such as oxalic acid, adipic acid, acetic acid, phthalic acid, isophthalic acid, and pyromellitic acid with the above polyols Product, addition reaction between the polyol and alkylene oxide such as ethylene oxide or propylene oxide Product, addition reaction product of alkylene polyamine and alkylene oxide, 2,2-dimethylol lactic acid, 2,2-dimethylol propionic acid, 2,2-dimethylol butanoic acid, 2,2-dimethylol valeric acid, 3 1,4-diaminobutanesulfonic acid, 3,6-diamino-2-toluenesulfonic acid, and their caprolactone-modified products, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, and the like.

  In addition, polyamino compounds such as ethylenediamine, diethylenetriamine, triethylenetetramine, propylenediamine, hexamethylenediamine, cyclohexylenediamine, phenylenediamine, tolylenediamine and xylenediamine, and α-amino acids such as serine, lysine and histidine should also be used. Can do.

  In the present invention, the active hydrogen compound is preferably a straight-chain compound having no branched skeleton, and further, a polyester polyol, polyether polyol, polycarbonate polyol having a melting point (Tm) of 40 ° C. or lower, It is preferable to use 50 parts by weight or more and 98 parts by weight or less of polycaprolactone polyol, polyolefin polyol and copolymers or mixtures thereof in 100 parts by weight of all active hydrogen compounds. When the amount is less than 50 parts by weight, the texture of the film obtained from the aqueous coating material tends to deteriorate, and when it exceeds 98 parts by weight, the film strength and hardness tend to decrease. These compounds may be used alone or in combination of two or more.

  Moreover, in order to disperse | distribute the urethane resin (M) used for this invention stably to water, although a well-known material and stabilization technique can be used, a carboxyl group, a sulfonyl group, and ethylene oxide group are 1 type in a molecule | numerator. It preferably has at least one, and more preferably has at least one carboxyl 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 urethane resin aqueous dispersion is in the range of 2 to 35 KOHmg / g, more preferably 3 to 30 KOHmg / g. It is. 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 a urethane resin (M) is not specifically limited, The following methods are mentioned. 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 group in the molecule; Urethane having an isocyanate group at the molecular end by reacting at least one compound having a sulfonyl group or an ethylene oxide group at an equivalent ratio such that the isocyanate group is excessive in the presence or absence of a suitable organic solvent. A prepolymer is produced, and then the prepolymer having a carboxyl group and / or a sulfonyl group is neutralized with a neutralizing agent such as a tertiary amine, and then this neutralized prepolymer is added with a chain extender-containing agent. After putting it into an aqueous solution and reacting it, if the system contains an organic solvent, it can be removed. Obtained by the above method, the method obtained by reacting the unneutralized urethane prepolymer obtained by the above method with an aqueous solution containing a neutralizing agent and containing a chain extender, and the above method In the neutralized urethane prepolymer, an aqueous solution having a chain extender is added and reacted, or in the unneutralized urethane prepolymer obtained by the above method, a neutralizing agent is contained, and There is a method of adding an aqueous solution having a chain extender and reacting to obtain an aqueous dispersion.

  The neutralizing agent used in the present invention is not particularly limited, but alkanolamines such as N, N-dimethylethanolamine and N, N-diethylethanolamine, N-methylmorpholine, and N-ethyl. Tertiary amines such as morpholine, pyridine, N-methylimidazole, ammonia, trimethylamine, triethylamine, alkali metals such as lithium hydroxide, potassium hydroxide, sodium hydroxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide Examples of the compound include quaternary ammonium compounds such as tetramethylammonium hydroxide, and these compounds can be used alone or as a mixture of two or more.

  The use amount of the neutralizing agent is preferably 0.5 to 3 equivalents, more preferably 0.7 to 1 with respect to 1 equivalent of carboxyl group and / or sulfonyl group in the polyurethane resin having the carboxyl group and / or sulfonyl group. .5 equivalents. If it is less than the above range, the stability of the urethane resin (M) in water tends to be lowered.

  Examples of the chain extender used in the present invention include water, ethylenediamine, diethylenetriamine, triethylenetetramine, propylenediamine, butylenediamine, hexamethylenediamine, cyclohexylenediamine, piperazine, 2-methylpiperazine, phenylenediamine, and tolylenediamine. , Xylenediamine, α, α′-methylenebis (2-chloroaniline), 3,3′-dichloro-α, α′-biphenylamine, m-xylenediamine, isophoronediamine, NBDA (trade name, Mitsui Chemicals, Inc.) N-methyl-3,3'-diaminopropylamine, and polyamines such as an adduct of diethylenetriamine and acrylate or a hydrolysis product thereof are suitable.

  Examples of the solvent used for obtaining the aqueous dispersion of the urethane resin (M) include ketones such as methyl ethyl ketone and acetone, esters such as methyl acetate and ethyl acetate, tetrahydrofuran, and the like. The solvent is not particularly limited as long as it is not higher than ° C. These solvents can be used alone or in a mixed state of two or more. Use of a solvent having a boiling point exceeding 100 ° C., that is, exceeding the boiling point of water, makes it difficult to completely remove only the solvent from the solution after forming the aqueous dispersion, and the high boiling point solvent remains in the film. When it is unavoidably used for performance, it is preferably used in an amount of 10 parts by weight or less with respect to 100 parts by weight of the aqueous dispersion of the urethane resin (F).

The aqueous dispersion of urethane resin (M) used in the present invention can also be used as a modified product by reacting with other components such as other monomers and resin components. Furthermore, in the aqueous dispersion of the urethane resin (F) obtained in the present invention, acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, acrylamide, methacrylamide, styrene, acrylonitrile, butadiene, vinyl acetate, ethylene, It can also be used as a composite obtained by polymerizing at least one monomer such as propylene, itaconic acid, maleic acid and the like.
Among the aqueous dispersions of the urethane resin (M) thus obtained, the elongation at break is preferably 0.1 to 800%. Furthermore, in order to improve the stability to water, said surfactant can be used.

  In the present invention, the propylene resin (A) modified with a copolymer of the copolymerizable monomer (E), or the propylene resin (b) modified with an acid or a hydroxyl group is converted into an α, β-monoethylenic resin. Propylene resin (B) modified with a polymer of a copolymerizable monomer (E) comprising a monomer having an unsaturated group and other copolymerizable monomers, or (A) or (B) and unmodified 20 to 100 parts by weight of propylene resin (C), petroleum hydrocarbon resin (H) and / or rosin resin (I) and / or terpene resin (J) 0 to 50 parts by weight, polyester (K ) And / or acrylic resin (L) and / or urethane resin (M) 0 to 80 parts by weight, (A) or (B), or (A) or (B) and (C), (H ) And / or (I) and / or It is more preferable to mix so that the total of (J), (K) and / or (L) and / or (M) is 100 parts by weight.

As the curing agent used in the present invention, Takenate WB series in which an isocyanate group is treated with a blocking agent such as oximes, lactams and phenols is present in water (manufactured by Mitsui Takeda Chemical Co., Ltd.) Elastron BN series (Daiichi Kogyo Seiyaku Co., Ltd.) can be used.
A resin synthesized from at least one of melamine, urea, benzoguanamine, glycoluril and the like and formaldehyde, for example, a part of methylol group by lower alcohol such as methanol, ethanol, propanol, isopropanol, butanol and isobutanol. Alternatively, amino resins which are all alkyl etherified can also be used as the curing agent.

  In a system containing water as a solvent, an oxazoline compound can also be used as a curing agent. Examples of the curing agent include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline and 2 -Isopropenyl-4-methyl-2-oxazoline can also be used as a curing agent.

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

  The aqueous dispersion of the present invention obtained above or a mixture of the aqueous dispersion of the present invention mixed with a curing agent capable of reacting with active hydrogen and / or a hydroxyl group, if necessary, is an organic compound such as an azo pigment and phthalocyanine blue. Pigments; dyes such as azo dyes and anthraquinone dyes; binder resins such as inorganic chemicals such as aluminum oxide, calcium carbonate, calcium hydroxide, magnesium hydroxide, silica and barium titanate; inorganics such as titanium oxide, molybdenum and carbon black Colorants such as pigments; various stabilizers such as antioxidants, weathering stabilizers and heat resistance inhibitors; antifoaming agents, thickeners, dispersants, surfactants, antifungal agents, antibacterial agents, antiseptics, catalysts, Components such as a filler, a wax, an antiblocking agent, a plasticizer, and a leveling agent can be contained.

  The coating method of the aqueous dispersion of the present invention or a mixture of the aqueous dispersion of the present invention mixed with a curing agent capable of reacting with active hydrogen and / or a hydroxyl group is not particularly limited, but is preferably performed by spray coating. Yes, for example, it can be applied by spraying on the surface to be coated with a spray gun. The application can usually be easily performed at normal temperature, and the drying method after application is not particularly limited, and can be dried by an appropriate method such as natural drying or forced heating drying.

  In addition, the water dispersion of the present invention or the water dispersion of the present invention mixed with a curing agent capable of reacting with active hydrogen and / or a hydroxyl group is characterized by polyolefins such as polyethylene and polypropylene, and ethylene-propylene copolymer. Molded products made of olefin copolymers such as polymers, ethylene-butene copolymers, propylene-butene copolymers, ethylene-propylene-butene copolymers, and molded products made of polypropylene and rubber components, polyamide resins, Saturated polyester, polycarbonate, epoxy resin, urethane resin, steel plate, electrodeposited steel plate, etc. can be suitably used as a primer, an adhesive. In addition, paints mainly composed of urethane paints, polyester paints, melamine paints, and epoxy paints can be used for the top coating, improving the adhesion to the surface of various objects to be coated, and improving the vividness. It can also be used to form a coating film.

  In addition, the water dispersion of the present invention, or the mixture of the water dispersion of the present invention mixed with a curing agent capable of reacting with active hydrogen and / or a hydroxyl group, is characterized by the fact that metals, polyolefins, or metals and polyolefins As an adhesive or heat sealant, the coating film has no stickiness and exhibits excellent adhesion performance and adhesion performance. In heat sealing, the aqueous dispersion of the present invention exhibits its performance at a low temperature, and can be used as an adhesive for PTP packaging and an adhesive for laminating.

  The aqueous dispersion of the present invention obtained above, or a mixture of the aqueous dispersion of the present invention mixed with a curing agent capable of reacting with active hydrogen and / or a hydroxyl group, was applied to a release film and peeled off. The film is excellent in flexibility, impact resistance, stretchability, transparency, gloss, blocking resistance and design, so it can be used for clothing, various packaging materials, medical equipment, sanitary products, various molded products, and display panel surfaces. It can be used for applications such as members and optical materials. Further, the light transmission can be controlled by expansion and contraction, and the transmitted light can be scattered, so that it can be used as an optical material such as a light shielding film and a light amount control film.

  In addition, the water dispersion of the present invention obtained above or the water dispersion of the present invention mixed with a curing agent capable of reacting with active hydrogen and / or a hydroxyl group is also used as a primer for strippable paint and traffic paint. can do.

EXAMPLES Next, although an Example is shown and this invention is demonstrated further in detail, this invention is not limited by these.
<Stability of water dispersion>
The aqueous dispersions obtained in Examples and Comparative Examples were allowed to stand for 1 month under the respective conditions of nonvolatile content of 30%, room temperature and 40 ° C., and the liquid state was evaluated. After the elapse of one month, the water dispersion, in which neither separation nor precipitation was confirmed, was evaluated as ○, while separation and / or precipitation was observed and was easily dispersible by stirring. Or the thing which cannot be disperse | distributed easily by stirring by which precipitation was observed was set as x.
<Sprayability of water dispersion>
Using a coating gun (Wider spray gun manufactured by Iwata Coating Machine Co., Ltd. (trade name: W-88-13H5G)), atomizing pressure of 4 kg / cm ² , opening of the nozzle one rotation, at a coating booth temperature of 30 ° C. The aqueous dispersions obtained in Examples and Comparative Examples were sprayed to observe whether or not stringing occurred, and those that did not occur were marked with ◯, and those that occurred even with one were marked with X.
<Physical properties of coating film>
The aqueous dispersion used for the evaluation was added with 3 parts of 50% aqueous solution of Orphine E1010 (manufactured by Nissin Chemical Industry Co., Ltd.) as a wetting agent to the resin of the aqueous dispersion obtained in each Example and Comparative Example And adjusted.

The base material water dispersion made of polypropylene was applied to a polypropylene square plate (product name: X708, manufactured by Sumitomo Mitsui Polyolefin Co., Ltd.) whose surface was wiped with isopropyl alcohol so that the film thickness after drying was 10 μm. After that, it was treated in an oven at 80 ° C. for 30 minutes. On this coating film, a white top coat paint (manufactured by Nippon Bee Chemical Co., Ltd., trade name: R278 (main agent) / R271 (curing agent) = mixed at 8/2) so that the film thickness after drying is 80 μm. A coating film was formed by coating, and allowed to stand at room temperature for 10 minutes, and then placed in an oven at 80 ° C. for 30 minutes to prepare a test piece. For these specimens, a cross-cut peel test after 24 hours, a peel strength measurement, a gloss retention after a weather resistance test and a cross-cut peel test, and an appearance and a cross-cut peel test after a hot water resistance test It was. In addition, the peel strength test is performed for those peeled by the cross-cut peel test, and the weather resistance and the warm water resistance test are performed for the peel strength after 24 hours when the strength is not 800 g / cm or more. I did not. Moreover, only the cross-cut peeling test after 24 hours was implemented about the coating film which did not apply | coat topcoat.

The steel sheet water dispersion was subjected to surface treatment (thickness: about 20 μm) with a known electrodeposition epoxy paint whose surface was wiped with isopropyl alcohol so that the film thickness after drying was 10 μm. After each coating, it was placed in an oven at 150 ° C. for 30 minutes. On this coating film, a white top coat paint (manufactured by Nippon Bee Chemical Co., Ltd., trade name: R278 (main agent) / R271 (curing agent) = mixed at 8/2) so that the film thickness after drying is 80 μm. A coating film was formed by coating, and allowed to stand at room temperature for 10 minutes, and then placed in an oven at 80 ° C. for 30 minutes to prepare a test piece. These test pieces were subjected to a cross-cut peel test after 24 hours. Moreover, the cross-cut peeling test 24 hours after was implemented about the coating film which did not apply | coat topcoat.

The aluminum foil / PP film aqueous dispersion was applied to the aluminum foil so that the film thickness after drying was 3 μm, and then treated in an oven at 100 ° C. for 10 minutes. On this coating film, a polypropylene film # 500T-T (manufactured by Tosero Co., Ltd.) was heat sealed by applying a pressure of 0.098 MPa at 100 ° C. for 1 second by a method based on JISZ1707. The peel strength was measured with the test piece thus obtained.

The PP film / PET film aqueous dispersion was applied to a PET film so that the film thickness after drying was 3 μm, and then treated in an oven at 100 ° C. for 10 minutes. On this coating film, a polypropylene film # 500T-T (manufactured by Tosero Co., Ltd.) was heat sealed by applying a pressure of 0.098 MPa at 100 ° C. for 1 second by a method based on JISZ1707. The peel strength was measured with the test piece thus obtained.

<Cross-cut peel test>
In accordance with the cross-cut peel test method described in JIS-K-5400, a test piece with a cross cut is prepared, and an adhesive tape (Nichiban Co., Ltd. product) is pasted on the cross cut, immediately. It was peeled by pulling in the direction of 90 °, and evaluation was performed by the number of grids that were not peeled out of 100 grids.
<Measurement of peel strength>
A 1 cm wide cut is made in the coating film applied to the polypropylene base material, the edge is peeled off, the edge is pulled in a 180 ° direction at a speed of 50 mm / min, and the peel strength is measured. Of 1000 g / cm or more were evaluated as ◎, those of 800 g / cm or more and less than 1000 g / cm were evaluated as ◯, and those of less than 800 g / cm were evaluated as ×.

The peel strength of the PP film / PET film was measured by cutting the test piece into a 1.5 cm strip, measuring the peel strength by pulling the end portion in the 180 ° direction at a speed of 50 mm / min, and the peel strength was 500 g / The peel strength of the aluminum foil / PP film is a 1.5 cm strip with ◎ for cm or more, ◯ for 300 g / cm or more and less than 500 g / cm, and x for less than 300 g / cm. The peel strength was measured by pulling the end portion in the direction of 180 ° at a speed of 50 mm / min, and the peel strength was 2000 g / cm or more, ◎, 1000 g / cm or more, and less than 2000 g / cm, Those less than 1000 g / cm were evaluated as x.
<Weather resistance test>
In accordance with the accelerated weather resistance test method described in JIS-K-5400, a grid-peeling test and gloss retention were evaluated for those evaluated for 1000 hours with a sunshine carbon arc lamp type.
<Measurement of gloss retention>
From the 60-degree specular gloss before and after the test (JIS-K-5400), the measured value retention rate (%) = (glossiness after test / initial glossiness) × 100 was calculated, and the gloss retention rate was 80%. In the above, the case where no discoloration was observed was evaluated as ◯, the case where the discoloration was 60% or more and less than 80% was evaluated as Δ, and the case where it was less than 60% was evaluated as ×.
<Hot water resistance test>
The test piece obtained above was immersed in warm water adjusted to 40 ° C. for 240 hours, and the appearance of the coating film and the cross-cut peel test were evaluated.
<Appearance of coating film>
About the coating film after a test, the presence or absence of a swelling is evaluated, and what has a change in coating films, such as (circle) and a swelling, is set to x.

[Example 1]
A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube was charged with 250 parts by weight of toluene and 100 parts by weight of ethyl acetate as an organic solvent, and heated to 100 ° C. while purging with nitrogen. Next, 40 parts by weight of methyl methacrylate as copolymerizable monomers, 35 parts by weight of styrene, 15 parts by weight of butyl acrylate, 10 parts by weight of hydroxyethyl acrylate, and tert-butylperoxy-2-ethylhexanoate as a polymerization initiator. 1 part by weight of an ate (hereinafter abbreviated as PBO) was fed over 4 hours. 1, 2, and 3 hours after the end of feeding, 0.2 parts by weight of PBO was added and reacted. After reacting for 2 hours after the last PBO addition, the solvent was removed under vacuum, and then the resin was pulverized to obtain a powdery acrylic resin.

A powdered acrylic resin (15 parts), a propylene-butene copolymer (85 parts by weight) and a polymerization initiator mixed with 1 part by weight of perhexy 25B were mixed into a twin screw extruder (Ikegai Iron Works). Propylene resin (A) modified with a polymer of a copolymerizable monomer (E), modified at a heating temperature of 220 ° C. and 16 kg / hour using a PCM-30, L / D = 40). Got.
As a propylene resin (D) containing 100 parts by weight of a propylene resin (A) modified with a polymer of the copolymerizable monomer obtained here and a group of a carboxylic acid or a salt thereof bonded to the polymer chain. A mixture of 10 parts by weight of wax NP0555A (manufactured by Mitsui Chemicals, acid graft amount: 3% by weight) and 3 parts by weight of potassium oleate as a surfactant (F) is a twin screw extruder (Ikegai Iron Works Co., Ltd.) It is supplied at a rate of 3000 g / hour from a hopper of PCM-30, L / D = 40), and a 20% aqueous solution of potassium hydroxide is supplied at 90 g / hour from a supply port provided in the vent portion of the extruder. The mixture was continuously supplied at a rate and continuously extruded at a heating temperature of 210 ° C. The extruded resin mixture was cooled to 110 ° C. with a jacketed static mixer installed at the extruder port, and further poured into warm water at 80 ° C. to obtain an aqueous dispersion. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.2 μm (measured by Microtrac).

[Example 2]
An aqueous dispersion was obtained in the same manner as in Example 1 except that the copolymerizable monomer (E) was changed to 75 parts by weight of methyl methacrylate, 15 parts by weight of butyl acrylate, and 10 parts by weight of hydroxyethyl acrylate. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.2 μm.
[Example 3]
An aqueous dispersion was obtained in the same manner as in Example 1, except that the propylene-based resin (D) containing a carboxylic acid or a salt group bonded to the polymer chain was changed to one synthesized below. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.3 μm.

“Synthesis of Propylene Resin (D) Containing Carboxylic Acid or its Salt Group Bonded to Polymer Chain”
A biaxial screw extruder (Ikekai Tekko Co., Ltd.) prepared by mixing 100 parts by weight of a propylene-butene copolymer, 3 parts by weight of maleic anhydride as a carboxylic acid group, and 0.3 parts by weight of perhexi 25B as a polymerization initiator. Propylene resin (D) containing a carboxylic acid or a salt thereof bonded to a polymer chain, modified at a heating temperature of 220 ° C. and 16 kg / hour using a company-made PCM-30, L / D = 40) Got.

[Example 4]
An aqueous dispersion was obtained in the same manner as in Example 1, except that the propylene-based resin (D) containing a carboxylic acid or a salt group bonded to the polymer chain was changed to one synthesized below. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.4 μm.

“Synthesis of Propylene Resin (D) Containing Carboxylic Acid or its Salt Group Bonded to Polymer Chain”
A twin screw extruder (Ikegai) was prepared by mixing 100 parts by weight of a propylene-butene-ethylene copolymer, 3 parts by weight of maleic anhydride as a carboxylic acid group, and 0.3 parts by weight of perhexi 25B as a polymerization initiator. A propylene-based resin containing a carboxylic acid or a salt group bonded to a polymer chain after modification at a heating temperature of 220 ° C. and 16 kg / hour using a steel manufacturer, PCM-30, L / D = 40). D) was obtained.
[Example 5]
An aqueous dispersion was obtained in the same manner as in Example 1 except that the propylene-based resin used for modification with the copolymerizable monomer polymer was changed to a propylene-butene-ethylene copolymer. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.5 μm.
[Example 6]
An aqueous dispersion was obtained in the same manner as in Example 1 except that the copolymerizable monomer (E) was changed to 70 parts of styrene, 15 parts by weight of butyl acrylate, 10 parts by weight of hydroxyethyl acrylate, and 5 parts by weight of methacrylic acid. It was. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.2 μm.
[Example 7]
An aqueous dispersion was obtained in the same manner as in Example 5 except that the copolymerizable monomer (E) was changed to Example 6. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.5 μm.

[Example 8]
100 parts by weight of a propylene-butene copolymer, 40 parts by weight of methyl methacrylate as a copolymerizable monomer (E), 35 parts by weight of styrene, 15 parts by weight of butyl acrylate, 10 parts by weight of hydroxyethyl acrylate and tert as a polymerization initiator A mixture of 1 part by weight of butyl peroxy-2-ethylhexanoate (hereinafter abbreviated as PBO) and 0.3 part by weight of perhexi25B is a twin screw extruder (Ikegai Iron Works, PCM -30, L / D = 40) at a heating temperature of 220 ° C. and 10 kg / hour to obtain a propylene resin (A) modified with a copolymerizable monomer polymer.

A mixture of 100 parts by weight of the propylene resin (A) modified with the copolymerizable monomer polymer obtained above, 10 parts by weight of high wax NP0555A and 3 parts by weight of potassium oleate It is supplied at a rate of 3000 g / hour from the hopper of a screw extruder (manufactured by Ikekai Tekko Co., Ltd., PCM-30, L / D = 40), and is supplied with 20 potassium hydroxide from a supply port provided in the vent portion of the extruder. % Aqueous solution was continuously fed at a rate of 90 g / hr and continuously extruded at a heating temperature of 210 ° C. The extruded resin mixture was cooled to 110 ° C. with a jacketed static mixer installed at the extruder port, and further poured into warm water at 80 ° C. to obtain an aqueous dispersion. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.2 μm.
[Example 9]
An aqueous dispersion was obtained in the same manner as in Example 8, except that the copolymerizable monomer (E) was changed to 75 parts by weight of methyl methacrylate, 15 parts by weight of butyl acrylate, and 10 parts by weight of hydroxyethyl acrylate. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.2 μm.
[Example 10]
An aqueous dispersion was obtained in the same manner as in Example 8, except that the propylene resin (D) containing carboxylic acid bonded to the polymer chain was changed to the resin obtained in Example 3. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.3 μm.
[Example 11]
An aqueous dispersion was obtained in the same manner as in Example 8, except that the propylene resin (D) containing carboxylic acid bonded to the polymer chain was changed to the resin obtained in Example 4. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.4 μm.
[Example 12]
An aqueous dispersion was obtained in the same manner as in Example 8, except that the propylene-based resin used for modification with the copolymerizable monomer polymer was changed to a propylene-butene-ethylene copolymer. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.5 μm.

[Example 13]
10 parts by weight of the propylene-based resin (A) modified with the copolymerizable monomer polymer obtained in Example 1, and 90 parts by weight of a propylene-butene copolymer as an unmodified propylene-based resin (C); A mixture of 10 parts by weight of high wax NP0555A and 3 parts by weight of potassium oleate is 3000 g / hour from the hopper of a twin screw extruder (Ikegai Iron Works, PCM-30, L / D = 40). A 20% aqueous solution of potassium hydroxide was continuously supplied at a rate of 90 g / hour from a supply port provided in the vent portion of the extruder and continuously extruded at a heating temperature of 210 ° C. The extruded resin mixture was cooled to 110 ° C. with a jacketed static mixer installed at the extruder port, and further poured into warm water at 80 ° C. to obtain an aqueous dispersion. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.2 μm.
[Example 14]
An aqueous dispersion was obtained in the same manner as in Example 13 except that the resin used for the unmodified propylene resin (C) was changed to a propylene-butene-ethylene copolymer. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.5 μm.

[Example 15]
An aqueous dispersion was obtained in the same manner as in Example 13, except that the propylene-based resin (D) containing carboxylic acid bonded to the polymer chain was changed to the resin obtained in Example 3. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.3 μm.
[Example 16]
An aqueous dispersion was obtained in the same manner as in Example 13, except that the propylene-based resin (D) containing carboxylic acid bonded to the polymer chain was changed to the resin obtained in Example 4. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.4 μm.
[Example 17]
An aqueous dispersion was obtained in the same manner as in Example 13, except that the propylene-based resin used for modification with the copolymerizable monomer polymer was changed to a propylene-butene-ethylene copolymer. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.2 μm.

[Example 18]
An aqueous dispersion was obtained in the same manner as in Example 17, except that the resin used for the unmodified propylene resin (C) was changed to a propylene-butene-ethylene copolymer. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.5 μm.
[Example 19]
10 parts by weight of the propylene-based resin (A) modified with the copolymerizable monomer polymer obtained in Example 8, and 90 parts by weight of a propylene-butene copolymer as an unmodified propylene-based resin (C); A mixture of 10 parts by weight of high wax NP0555A and 3 parts by weight of potassium oleate is 3000 g / hour from the hopper of a twin screw extruder (Ikegai Iron Works, PCM-30, L / D = 40). A 20% aqueous solution of potassium hydroxide was continuously supplied at a rate of 90 g / hour from a supply port provided in the vent portion of the extruder and continuously extruded at a heating temperature of 210 ° C. The extruded resin mixture was cooled to 110 ° C. with a jacketed static mixer installed at the extruder port, and further poured into warm water at 80 ° C. to obtain an aqueous dispersion. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.2 μm.
[Example 20]
An aqueous dispersion was obtained in the same manner as in Example 19 except that the resin used for the unmodified propylene resin (C) was changed to a propylene-butene-ethylene copolymer. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.5 μm.
[Example 21]
An aqueous dispersion was obtained in the same manner as in Example 19 except that the propylene-based resin (D) containing carboxylic acid bonded to the polymer chain was changed to the resin obtained in Example 3. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.3 μm.

[Example 22]
An aqueous dispersion was obtained in the same manner as in Example 19 except that the propylene-based resin (D) containing carboxylic acid bonded to the polymer chain was changed to the resin obtained in Example 4. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.4 μm.
[Example 23]
An aqueous dispersion was obtained in the same manner as in Example 19 except that the propylene-based resin used for modification with the copolymerizable monomer polymer was changed to a propylene-butene-ethylene copolymer. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.2 μm.
[Example 24]
An aqueous dispersion was obtained in the same manner as in Example 23 except that the resin used for the unmodified propylene resin (C) was changed to a propylene-butene-ethylene copolymer. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.5 μm.

[Example 25]
A mixture of 15 parts of the acrylic resin powder obtained in Example 1 and 85 parts by weight of an acid-modified propylene-butene copolymer obtained by the following method was used as a twin screw extruder ( A propylene-based resin (B) modified with a copolymerizable monomer polymer was modified at a heating temperature of 220 ° C. and 10 kg / hour using Ikegai Iron Works Co., Ltd., PCM-30, L / D = 40). Obtained.
A biaxial mixture of 100 parts by weight of the propylene resin (B) modified with the copolymerizable monomer polymer obtained above, 10 parts by weight of high wax NP0555A and 3 parts by weight of potassium oleate was mixed. It is supplied at a rate of 3000 g / hour from the hopper of a screw extruder (manufactured by Ikekai Tekko Co., Ltd., PCM-30, L / D = 40). % Aqueous solution was continuously fed at a rate of 90 g / hr and continuously extruded at a heating temperature of 210 ° C. The extruded resin mixture was cooled to 110 ° C. with a jacketed static mixer installed at the extruder port, and further poured into warm water at 80 ° C. to obtain an aqueous dispersion. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.2 μm.

"Method for producing propylene-butene copolymer modified with acid group"
A twin screw extruder (Ikegai Iron Works Co., Ltd.) prepared by mixing 100 parts by weight of a propylene-butene copolymer, 3 parts by weight of maleic anhydride as an acid group, and 0.3 parts by weight of perhexi25B as a polymerization initiator. Manufactured, PCM-30, L / D = 40) at a heating temperature of 220 ° C. and 16 kg / hour to obtain a propylene-butene copolymer modified with maleic anhydride.

[Example 26]
A powdery acrylic resin was obtained in the same manner as in Example 1 except that the copolymerizable monomer (E) was changed to 75 parts by weight of styrene, 20 parts by weight of butyl acrylate, and 5 parts by weight of methacrylic acid.
A mixture of 15 parts of the powdered acrylic resin obtained here and 85 parts by weight of a propylene-butene copolymer modified with a hydroxyl group obtained by the following method was used as a twin-screw extruder (Ikekai Tekko Co., Ltd.) Using a company-made PCM-30, L / D = 40), modification was performed at a heating temperature of 220 ° C. and 10 kg / hour to obtain a propylene resin (B) modified with a copolymerizable monomer polymer.
A biaxial mixture of 100 parts by weight of the propylene resin (B) modified with the copolymerizable monomer polymer obtained above, 10 parts by weight of high wax NP0555A and 3 parts by weight of potassium oleate was mixed. It is supplied at a rate of 3000 g / hour from the hopper of a screw extruder (manufactured by Ikekai Tekko Co., Ltd., PCM-30, L / D = 40). % Aqueous solution was continuously fed at a rate of 90 g / hr and continuously extruded at a heating temperature of 210 ° C. The extruded resin mixture was cooled to 110 ° C. with a jacketed static mixer installed at the extruder port, and further poured into warm water at 80 ° C. to obtain an aqueous dispersion. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.2 μm.

"Method for producing propylene-butene copolymer modified with hydroxyl group"
A twin screw extruder (manufactured by Ikekai Tekko Co., Ltd.) prepared by mixing 100 parts by weight of a propylene-butene copolymer, 3 parts by weight of hydroxypropyl acrylate as a hydroxyl group, and 0.3 parts by weight of perhexi25B as a polymerization initiator. PCM-30, L / D = 40) was used to modify at a heating temperature of 220 ° C. and 16 kg / hour to obtain a propylene-butene copolymer modified with a hydroxyl group.
[Example 27]
An aqueous dispersion was obtained in the same manner as in Example 25 except that the propylene-based resin (D) containing carboxylic acid bonded to the polymer chain was changed to the resin obtained in Example 3. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.3 μm.
[Example 28]
An aqueous dispersion was obtained in the same manner as in Example 26 except that the propylene-based resin (D) containing carboxylic acid bonded to the polymer chain was changed to the resin obtained in Example 3. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.3 μm.
[Example 29]
An aqueous dispersion was obtained in the same manner as in Example 25 except that the propylene-based resin (D) containing carboxylic acid bonded to the polymer chain was changed to the resin obtained in Example 4. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.4 μm.

[Example 30]
An aqueous dispersion was obtained in the same manner as in Example 26 except that the propylene-based resin (D) containing carboxylic acid bonded to the polymer chain was changed to the resin obtained in Example 4. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.4 μm.
[Example 31]
An aqueous dispersion was obtained in the same manner as in Example 25 except that the propylene-butene copolymer used for modification with an acid group was changed to a propylene-butene-ethylene copolymer. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.5 μm.
[Example 32]
An aqueous dispersion was obtained in the same manner as in Example 26 except that the propylene-butene copolymer used for modification with a hydroxyl group was changed to a propylene-butene-ethylene copolymer. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.5 μm.
[Example 33]
100 parts by weight of the acid-modified propylene-butene copolymer obtained in Example 25, 40 parts by weight of methyl methacrylate as copolymerizable monomer (E), 35 parts by weight of styrene, 15 parts by weight of butyl acrylate, A mixture of 10 parts by weight of hydroxyethyl acrylate and 0.5 part by weight of PBO as a polymerization initiator is heated using a twin screw extruder (Ikegai Iron Works, PCM-30, L / D = 40). Modification was performed at a temperature of 220 ° C. and 10 kg / hour to obtain a propylene-based resin (B) modified with a copolymerizable monomer polymer.
An aqueous dispersion was obtained in the same manner as in Example 25 using the propylene resin (B) modified with the copolymerizable monomer polymer obtained here. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.2 μm.

[Example 34]
100 parts by weight of the propylene-butene copolymer modified with a hydroxyl group obtained in Example 26, and 75 parts by weight of styrene, 20 parts by weight of butyl acrylate, and 5 parts by weight of methacrylic acid as a copolymerizable monomer (E) What mixed 0.5 weight part of PBO as a polymerization initiator uses a twin screw extruder (Ikegai Iron Works Co., Ltd., PCM-30, L / D = 40), heating temperature 220 degreeC, 10 kg / hour. The propylene resin (B) modified with a copolymerizable monomer polymer was obtained.
An aqueous dispersion was obtained in the same manner as in Example 26 using the propylene-based resin (B) modified with the copolymerizable monomer polymer obtained here. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.2 μm.
[Example 35]
An aqueous dispersion was obtained in the same manner as in Example 33 except that the propylene-based resin (D) containing carboxylic acid bonded to the polymer chain was changed to the resin obtained in Example 3. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.3 μm.
[Example 36]
An aqueous dispersion was obtained in the same manner as in Example 34 except that the propylene-based resin (D) containing carboxylic acid bonded to the polymer chain was changed to the resin obtained in Example 3. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.3 μm.

[Example 37]
An aqueous dispersion was obtained in the same manner as in Example 33 except that the propylene-butene copolymer used for modification with an acid group was changed to a propylene-butene-ethylene copolymer. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.5 μm.
[Example 38]
An aqueous dispersion was obtained in the same manner as in Example 34 except that the propylene-butene copolymer used for modification with a hydroxyl group was changed to a propylene-butene-ethylene copolymer. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.5 μm.
[Example 39]
10 parts by weight of the propylene-based resin (B) modified with the copolymerizable monomer polymer obtained in Example 25, and 90 parts by weight of a propylene-butene copolymer as an unmodified propylene-based resin (C); A mixture of 10 parts by weight of high wax NP0555A and 3 parts by weight of potassium oleate is 3000 g / hour from the hopper of a twin screw extruder (Ikegai Iron Works, PCM-30, L / D = 40). A 20% aqueous solution of potassium hydroxide was continuously supplied at a rate of 90 g / hour from a supply port provided in the vent portion of the extruder and continuously extruded at a heating temperature of 210 ° C. The extruded resin mixture was cooled to 110 ° C. with a jacketed static mixer installed at the extruder port, and further poured into warm water at 80 ° C. to obtain an aqueous dispersion. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.2 μm.

[Example 40]
An aqueous dispersion was obtained in the same manner as in Example 39 except that the resin used for the unmodified propylene resin (C) was changed to a propylene-butene-ethylene copolymer. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.5 μm.
[Example 41]
10 parts by weight of the propylene-based resin (B) modified with the polymer of the copolymerizable monomer obtained in Example 26, 90 parts by weight of a propylene-butene copolymer as an unmodified propylene-based resin (C), A mixture of 10 parts by weight of high wax NP0555A and 3 parts by weight of potassium oleate is 3000 g / hour from a hopper of a twin screw extruder (Ikegai Iron Works, PCM-30, L / D = 40). A 20% aqueous solution of potassium hydroxide was continuously supplied at a rate of 90 g / hour from a supply port provided in the vent portion of the extruder and continuously extruded at a heating temperature of 210 ° C. The extruded resin mixture was cooled to 110 ° C. with a jacketed static mixer installed at the extruder port, and further poured into warm water at 80 ° C. to obtain an aqueous dispersion. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.2 μm.
[Example 42]
An aqueous dispersion was obtained in the same manner as in Example 41 except that the resin used for the unmodified propylene resin (C) was changed to a propylene-butene-ethylene copolymer. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.5 μm.
[Example 43]
An aqueous dispersion was obtained in the same manner as in Example 39 except that the propylene-based resin (D) containing carboxylic acid bonded to the polymer chain was changed to the resin obtained in Example 3. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.3 μm.
[Example 44]
An aqueous dispersion was obtained in the same manner as in Example 39 except that the propylene-based resin (D) containing a carboxylic acid bonded to a polymer chain was changed to the resin obtained in Example 4. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.4 μm.

[Example 45]
An aqueous dispersion was obtained in the same manner as in Example 39 except that the propylene-butene copolymer used for modification with an acid group was changed to a propylene-butene-ethylene copolymer. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.2 μm.
[Example 46]
An aqueous dispersion was obtained in the same manner as in Example 45 except that the resin used for the unmodified propylene resin (C) was changed to a propylene-butene-ethylene copolymer. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.5 μm.
[Example 47]
An aqueous dispersion was obtained in the same manner as in Example 41 except that the propylene-butene copolymer used for modification with a hydroxyl group was changed to a propylene-butene-ethylene copolymer. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.2 μm.

[Example 48]
10 parts by weight of the propylene resin (B) modified with the copolymer of the copolymerizable monomer obtained in Example 33, 90 parts by weight of a propylene-butene copolymer as an unmodified propylene resin (C), A mixture of 10 parts by weight of high wax NP0555A and 3 parts by weight of potassium oleate is 3000 g / hour from the hopper of a twin screw extruder (Ikegai Iron Works, PCM-30, L / D = 40). A 20% aqueous solution of potassium hydroxide was continuously supplied at a rate of 90 g / hour from a supply port provided in the vent portion of the extruder and continuously extruded at a heating temperature of 210 ° C. The extruded resin mixture was cooled to 110 ° C. with a jacketed static mixer installed at the extruder port, and further poured into warm water at 80 ° C. to obtain an aqueous dispersion. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.2 μm.
[Example 49]
An aqueous dispersion was obtained in the same manner as in Example 48 except that the resin used for the unmodified propylene resin (C) was changed to a propylene-butene-ethylene copolymer. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.5 μm.
[Example 50]
10 parts by weight of the propylene-based resin (B) modified with the copolymerizable monomer polymer obtained in Example 34, 90 parts by weight of a propylene-butene copolymer as an unmodified propylene-based resin (C), A mixture of 10 parts by weight of high wax NP0555A and 3 parts by weight of potassium oleate is 3000 g / hour from the hopper of a twin screw extruder (Ikegai Iron Works, PCM-30, L / D = 40). A 20% aqueous solution of potassium hydroxide was continuously supplied at a rate of 90 g / hour from a supply port provided in the vent portion of the extruder and continuously extruded at a heating temperature of 210 ° C. The extruded resin mixture was cooled to 110 ° C. with a jacketed static mixer installed at the extruder port, and further poured into warm water at 80 ° C. to obtain an aqueous dispersion. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.2 μm.

[Example 51]
An aqueous dispersion was obtained in the same manner as in Example 48 except that the propylene-based resin (D) containing carboxylic acid bonded to the polymer chain was changed to the resin obtained in Example 3. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.3 μm.
[Example 52]
An aqueous dispersion was obtained in the same manner as in Example 48 except that the propylene-based resin (D) containing carboxylic acid bonded to the polymer chain was changed to the resin obtained in Example 4. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.4 μm.
[Example 53]
An aqueous dispersion was obtained in the same manner as in Example 48 except that the propylene-butene copolymer used for modification with an acid group was changed to a propylene-butene-ethylene copolymer. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.2 μm.
[Examples 54 to 61]
Propylene-based resin (A) or (B) modified with a polymer of a copolymerizable monomer described in Examples 13, 15, 17, 19, 39, 41, 43, and 45, and an unmodified propylene-based resin An aqueous dispersion was obtained in the same manner as in Example 13 except that the blending amount of (C) was changed to 50 parts by weight and 50 parts by weight, respectively. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.2 μm, 0.3 μm, 0.5 μm, 0.2 μm, 0.2 μm, They were 0.2 μm, 0.3 μm, and 0.5 μm.
[Example 62]
The aqueous dispersion of petroleum resin obtained in the following was added to 60 g of the aqueous dispersion 222 g obtained in Example 1 in this order under stirring and mixing to obtain an aqueous dispersion.

"Water dispersion of petroleum resin"
A four-necked flask equipped with a stirrer, a thermometer, a reflux cooling device, and a nitrogen inlet tube was charged with 300 g of hexane and 300 g of petroleum resin (manufactured by Mitsui Chemicals, Inc., Hi-Lets T-480X), and heated and dissolved 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 petroleum hydrocarbon resin (D). The obtained aqueous resin composition had a yield of 98%, a solid content concentration of 50%, a pH of 8, and an average particle size of 0.6 μm (measured by Microtrac).
[Example 63]
Super dispersion E720 (made by Arakawa Chemical Industry Co., Ltd.), which is an aqueous dispersion of rosin resin, was added dropwise to 60 g of the aqueous dispersion 222 g obtained in Example 1 with stirring and mixing, and the aqueous dispersion was obtained. Obtained.
[Example 64]
To 60 g of Nanolet R1050 (manufactured by Yasuhara Chemical Co., Ltd.) which is an aqueous dispersion of a terpene resin, 222 g of the aqueous dispersion obtained in Example 1 was sequentially added dropwise with stirring and mixing to obtain an aqueous dispersion.
[Example 65]
To 20 g of the petroleum resin aqueous dispersion obtained in Example 62, 20 g of Superester E720, 40 g of Nanolet R1050, and 222 g of the aqueous dispersion obtained in Example 1 were sequentially added dropwise with stirring and mixing. A dispersion was obtained.
[Examples 66 to 74]
While stirring and mixing to 60 g of Nanolet R1050, 222 g of the aqueous dispersion obtained in Examples 3, 5, 13, 25, 27, 31, 39, 43, and 45 were sequentially dropped and mixed to obtain an aqueous dispersion. .

[Example 75]
To 44 g of the aqueous dispersion of polyester (K) obtained below, 222 g of the aqueous dispersion obtained in Example 1 was sequentially added dropwise with stirring and mixing to obtain an aqueous dispersion.

"Water dispersion of polyester (K)"
A flask equipped with a stirrer, a thermometer, a reflux cooling device, and a nitrogen inlet tube was charged with 300 parts by weight of toluene and 300 parts by weight of a polyester elastomer (byron 500, manufactured by Toyobo Co., Ltd.), and heated and dissolved under reflux. 500 parts by weight of this solution, 375 parts by weight of distilled water, and 1.5 parts by weight of sodium dodecylbenzenesulfonate (manufactured by Kao Corporation, Neoperex F-25) are mixed and stirred for 15 minutes at a rotational speed of 10,000 rpm to obtain an emulsion. Got. Toluene in the emulsion was distilled off under reduced pressure with an evaporator to obtain an aqueous dispersion of polyester. The obtained aqueous dispersion had a yield of 98%, a solid content concentration of 45%, a pH of 7, and an average particle size of 0.6 μm.
[Example 76]
To 50 g of the acrylic resin aqueous dispersion (L) obtained below, 222 g of the aqueous dispersion obtained in Example 1 was added dropwise and mixed with stirring to obtain an aqueous dispersion.

"Acrylic resin water dispersion (L)"
A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube was charged with 500 parts by weight of toluene and 100 parts by weight of ethyl acetate, and heated to 85 ° C. in a nitrogen gas atmosphere. Then, 150 parts by weight of methyl methacrylate, 120 parts by weight of ethyl acrylate, 30 parts by weight of 2-hydroxyethyl acrylate, 10 parts by weight of methacrylic acid and 3 parts by weight (hereinafter abbreviated as PBO) as a copolymerization monomer. The mixture was fed for 4 hours to react. After 1 hour and 2 hours from the end of the feed, 0.2 parts by weight of PBO was added and reacted for 2 hours from the last addition to obtain a resin solution. The resulting resin solution is neutralized with triethylamine to theoretically 100%, deionized water is added so that the non-volatile content is 40%, and then toluene and ethyl acetate are removed under reduced pressure. An aqueous dispersion of an acrylic resin having a solid content of 40%, a pH of 8, and an average particle size of 0.3 μm was obtained.
[Example 77]
To 67 g of the urethane resin aqueous dispersion (M) obtained below, 222 g of the aqueous dispersion obtained in Example 1 was sequentially added dropwise with stirring and mixing to obtain an aqueous dispersion.

"Water dispersion of urethane resin (M)"
In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube, 399.5 parts by weight of polytetramethylene ether glycol (Hodogaya Chemical Co., Ltd., PTG2000SN), 2,2-dimethylol 21.0 parts by weight of butanoic acid, 12.4 parts by weight of 1,4-butanediol, 96.3 parts by weight of hexamethylene diisocyanate, and 374.0 parts by weight of methyl ethyl ketone were charged and reacted at 90 ° C. for 6 hours in a nitrogen gas atmosphere. It was. Then, it cooled to 60 degreeC, 13.3 weight part of triethylamine was added, and it mixed for 30 minutes under this temperature. The obtained prepolymer was mixed and stirred with 1275.7 parts by weight of 0.86% hexamethylenediamine aqueous solution, and then methyl ethyl ketone was removed at 60 ° C. under reduced pressure to obtain a solid content of 30% and a solid content acid value of 15 KOH mg. / G, pH: 8, average particle diameter: 0.2 micrometer urethane resin aqueous dispersion was obtained.
[Examples 78 to 87]
Under agitation and mixing, 60 g of Nanolet R1050 and 33 g of an aqueous dispersion (M) of the urethane resin obtained in Example 77 were obtained in Examples 3, 5, 13, 25, 27, 31, 39, 43, and 45. The obtained aqueous dispersion 222 g was sequentially dropped and mixed to obtain an aqueous dispersion.
[Examples 88 to 97]
10 g of Takenate WD-720 (manufactured by Mitsui Chemicals Polyurethane Co., Ltd.) as a curing agent was mixed with 100 g of the aqueous dispersions of Examples 78 to 87 to obtain aqueous dispersions.
[Examples 98 to 107]
8 g of Cymel 236 (manufactured by Cytec Co., Ltd.) as a curing agent and 0.8 g of catalyst 500 as a catalyst were mixed with 100 g of the aqueous dispersion of Examples 78 to 87 to obtain an aqueous dispersion.
[Examples 108 to 117]
10 g of Epocross K-2020E (manufactured by Nippon Shokubai Co., Ltd.) as a curing agent was mixed with 100 g of the aqueous dispersions of Examples 78 to 87 to obtain aqueous dispersions.
The propylene-butene copolymer used above has a physical property of C3 / C4 = 81/19: molar ratio, Mw = 250,000, Mw / Mn = 2, specific gravity = 0.88, and propylene-butene-ethylene copolymer. As the polymer, those having physical properties of C3 / C4 / C2 = 66/23/11: molar ratio, Mw = 120,000, Mw / Mn = 5, and specific gravity = 0.87 were used.

[Comparative Example 1]
A mixture of 100 parts by weight of a propylene-butene copolymer, 10 parts by weight of high wax NP0555A and 3 parts by weight of potassium oleate was mixed with a twin screw extruder (Ikegai Iron Works, PCM-30, L / D = 40) from a hopper at a rate of 3000 g / hour, a 20% aqueous solution of potassium hydroxide is continuously fed at a rate of 90 g / hour from a feed port provided in the vent of the extruder, and heated. The extrusion was continuously performed at a temperature of 210 ° C. The extruded resin mixture was cooled to 110 ° C. with a jacketed static mixer installed at the extruder port, and further poured into warm water at 80 ° C. to obtain an aqueous dispersion. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.4 μm (measured by Microtrac).
[Comparative Example 2]
An aqueous dispersion was obtained in the same manner as in Comparative Example 1 except that the propylene-butene copolymer was changed to a propylene-butene-ethylene copolymer. The obtained aqueous dispersion had a yield of 99%, a solid content concentration of 45%, a pH of 11, and an average particle size of 0.4 μm.
The obtained results are shown in Tables 1 and 2.

Claims (21)

(A) a propylene-based resin modified with a polymer of a copolymerizable monomer (E) comprising a monomer having an α, β-monoethylenically unsaturated group and another copolymerizable monomer;
(D) A group of a carboxylic acid or a salt thereof bonded to a polymer chain is represented by the formula (1) —C—O— per gram of resin.
・ ・ ・ (1)
O
A propylene-based resin containing at a concentration of 0.05 to 5 mmol equivalent in terms of a group represented by:
(F) an anionic and / or nonionic surfactant, and
(G) including water,
An aqueous dispersion, wherein the copolymerizable monomer (E) contains at least one (meth) acrylic acid ester and / or an aromatic vinyl compound. (A) a propylene-based resin modified with a polymer of a copolymerizable monomer (E) comprising a monomer having an α, β-monoethylenically unsaturated group and another copolymerizable monomer;
(C) an unmodified propylene resin;
(D) A group of a carboxylic acid or a salt thereof bonded to a polymer chain is represented by the formula (1) —C—O— per gram of resin.
・ ・ ・ (1)
O
A propylene-based resin containing at a concentration of 0.05 to 5 mmol equivalent in terms of a group represented by:
(F) an anionic and / or nonionic surfactant, and
(G) including water,
An aqueous dispersion, wherein the copolymerizable monomer (E) contains at least one (meth) acrylic acid ester and / or an aromatic vinyl compound. (B) a copolymerizable monomer comprising a monomer having an α, β-monoethylenically unsaturated group and another copolymerizable monomer (b) modified with an acid or a hydroxyl group-modified propylene resin (b) The aqueous dispersion according to claim 1, comprising a propylene-based resin modified with the polymer of E) and (D), (F), and (G). (B) a copolymerizable monomer comprising a monomer having an α, β-monoethylenically unsaturated group and another copolymerizable monomer (b) modified with an acid or a hydroxyl group-modified propylene resin (b) The aqueous dispersion according to claim 2, comprising a propylene-based resin modified with the polymer of E) and (C), (D), (F), and (G). (D) is 0.3 to 60 parts by weight and (F) is 0.5 with respect to 100 parts by weight of the resin comprising (A), or (B), or (A) or (B) and (C). -40 parts by weight, characterized in that it contains 3 to 90% by weight of (G), and the content of (C) relative to (A) or (B) is 0 to 98% by weight. Item 5. The aqueous dispersion according to any one of Items 1 to 4.   Furthermore, an aqueous dispersion of a petroleum hydrocarbon resin (H) and / or a rosin resin (I) and / or a terpene resin (J) is contained. An aqueous dispersion described in 1.   (A), or (B), or (A) or (B) and (C) 20 to 100 parts by weight, petroleum hydrocarbon resin (H) and / or rosin resin (I) and / or terpene It consists of 0 to 50 parts by weight of resin (J) and 0 to 80 parts by weight of polyester (K) and / or acrylic resin (L) and / or urethane resin (M), and (A) or (B), or 100 parts by weight of the total of (A) or (B) and (C), (H) and / or (I) and / or (J), (K) and / or (L) and / or (M) The aqueous dispersion according to any one of claims 1 to 6, wherein   The propylene-based resin used in the (A), (B) and (C) has a molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) in the range of 1 to 3. The water dispersion according to any one of claims 1 to 7.   The coating material containing the water dispersion in any one of Claims 1-8.   The primer containing the water dispersion in any one of Claims 1-8.   The adhesive agent containing the water dispersion in any one of Claims 1-8.   The additive containing the water dispersion in any one of Claims 1-8.   The binder containing the water dispersion in any one of Claims 1-8.   The film obtained from the water dispersion in any one of Claims 1-8.   The aqueous dispersion according to any one of claims 1 to 8, wherein the copolymerizable monomer (E) contains a copolymerizable monomer having active hydrogen and / or a hydroxyl group.   A paint comprising the aqueous dispersion according to claim 15 and a curing agent capable of reacting with active hydrogen and / or a hydroxyl group.   A primer containing the aqueous dispersion according to claim 15 and a curing agent capable of reacting with active hydrogen and / or a hydroxyl group.   An adhesive comprising the aqueous dispersion according to claim 15 and a curing agent capable of reacting with active hydrogen and / or a hydroxyl group.   An additive comprising the aqueous dispersion according to claim 15 and a curing agent capable of reacting with active hydrogen and / or a hydroxyl group.   A binder containing the aqueous dispersion according to claim 15 and a curing agent capable of reacting with active hydrogen and / or a hydroxyl group.   A film containing the aqueous dispersion according to claim 15 and a curing agent capable of reacting with active hydrogen and / or a hydroxyl group.