JP2009209182A - Aqueous resin composition and coated article - Google Patents

Abstract

An aqueous resin composition having excellent adhesion, adhesion, and warm water resistance and a coated product thereof are provided.
A composition (I) containing an acid-modified polyolefin (A), an organic solvent (B), a vinyl monomer (C), an emulsifier (D), water (E) and a polymerization initiator (F). Is a composition obtained by emulsion polymerization and solvent removal, wherein (A) comprises a polyolefin (a1), a sorbitol (a2), an alkyl alkylate, an alkylene glycol alkyl ether alkylate and a dialkylene glycol alkyl. In the presence of an organic solvent (a3) having a boiling point of 250 ° C. or lower and at least one selected from the group consisting of ether alkylates, (meth) acrylic acid alkyl ester (a4), α, β-unsaturated carboxylic acid and / or Alternatively, an aqueous resin composition which is an acid-modified polyolefin obtained by adding an acid anhydride (a5) thereof using an organic peroxide (a6), and Paintings.
[Selection figure] None

Description

  The present invention relates to an aqueous resin composition and a coated product, and can be used mainly as a paint, a primer, an ink, an adhesive, and a sealing agent. In particular, it is possible to form coatings and adhesive layers with excellent adhesion to polyolefin substrates with non-polar surfaces, hot water adhesion, coating materials for automobile parts materials, polyolefin films, polyolefin moldings, primers, Useful as a resin for inks, sealants and adhesives.

  In general, polyolefins are widely used as materials for automobile parts, electrical parts, building materials, packaging films and the like because they are relatively inexpensive and excellent in chemical resistance, water resistance, heat resistance and the like. However, since polyolefin is crystalline and nonpolar, it is difficult to coat or bond.

  For the coating and adhesion of such a polyolefin substrate, an aqueous resin composition using a chlorinated polyolefin having strong adhesion to the polyolefin, for example, a chlorinated polyolefin having a chlorination degree of 5 to 50% by mass, It is known to use an aqueous resin composition obtained by emulsion-polymerizing a composition comprising an organic solvent, a vinyl monomer, a surfactant, water and a polymerization initiator and then removing the solvent (for example, patents). Reference 1).

However, since the aqueous resin composition described in Patent Document 1 contains chlorine atoms, there is a problem that it is not preferable from the environment because of the generation of chlorine-based harmful substances that accompany incineration. Development of a halogen-free aqueous resin composition that does not generate chlorine-based harmful substances is desired.
Japanese Patent Laid-Open No. 11-263802

  The problem to be solved by the present invention is a halogen-free aqueous resin composition capable of forming a coating or adhesive layer having good adhesion and adhesion to various plastic substrates, particularly polyolefin substrates, and excellent resistance to hot water. It is another object of the present invention to provide a coated product obtained by coating a product and the aqueous resin composition on a plastic substrate and drying the product.

  In order to solve the above-mentioned problems, the present inventors have intensively and researched. As a result, instead of chlorinated polyolefin, polyolefin (a1) containing ethylene and propylene as structural units, sorbitols (a2) and In the presence of an organic solvent (a3) having at least one selected from the group consisting of alkyl alkylates, alkylene glycol alkyl ether alkylates and dialkylene glycol alkyl ether alkylates and having a boiling point of 250 ° C. or lower, (meth) Acrylic acid alkyl ester (a4) and α, β-unsaturated carboxylic acid and / or its acid anhydride (a5) [excluding (meth) acrylic acid alkyl ester (a4). ] Is added with an organic peroxide (a6), and the aqueous resin composition obtained using the acid-modified polyolefin (A) is adhesive to various plastic substrates, particularly polyolefin substrates. It is a halogen-free aqueous resin composition that can form a coating or adhesive layer that has excellent (primary adhesion) and adhesiveness, and excellent warm water-resistant adhesion (secondary adhesion). It is found that by coating on a material and drying, it is possible to easily obtain a coated product having a coating having excellent adhesion to and adhesion to various plastic substrates, particularly polyolefin substrates, and excellent hot water adhesion. The present invention has been completed.

  That is, the present invention contains an acid-modified polyolefin (A), an organic solvent (B), a vinyl monomer (C), an emulsifier (D), water (E) and a polymerization initiator (F), and An aqueous resin composition obtained by emulsion-polymerizing a vinyl monomer (C) in a composition (I) obtained by dissolving the acid-modified polyolefin (A) in an organic solvent (B) and then removing the solvent. The acid-modified polyolefin (A) is a polyolefin (a1) containing ethylene and propylene as structural units, a sorbitol (a2), an alkyl alkylate, an alkylene glycol alkyl ether alkylate and a dialkylene glycol alkyl ether alkyl. In the presence of an organic solvent (a3) that is at least one selected from the group consisting of chelates and has a boiling point of 250 ° C. or lower, an alkyl (meth) acrylate is used. Except ester (a4), alpha, beta-unsaturated carboxylic acid and / or its acid anhydride (a5) [where the (meth) acrylic acid alkyl ester (a4). Is an acid-modified polyolefin obtained by adding an organic peroxide (a6) to provide an aqueous resin composition.

  In addition, the present invention provides a coated product characterized in that the aqueous resin composition is coated on a plastic substrate and dried.

  Although the aqueous resin composition of the present invention is a halogen-free aqueous resin composition, it has good adhesion and adhesion to various plastic substrates, particularly polyolefin substrates, and is a film having excellent warm water resistance. And an adhesive layer can be formed, which is useful as a paint, primer, ink, adhesive, sealing material, etc. on various plastic substrates.

Details of the present invention will be specifically described below.
Examples of the acid-modified polyolefin (A) used in the present invention include polyolefin (a1) containing ethylene and propylene as structural units, sorbitols (a2), alkyl alkylate, alkylene glycol alkyl ether alkylate and dialkylene glycol alkyl. (Meth) acrylic acid alkyl ester (a4) and α, β-unsaturated carboxylic acid in the presence of an organic solvent (a3) having at least one selected from the group consisting of ether alkylates and having a boiling point of 250 ° C. or lower. Acid and / or its anhydride (a5) [excluding (meth) acrylic acid alkyl ester (a4). ] Is an acid-modified polyolefin obtained by adding an organic peroxide (a6).

  The polyolefin (a1) is an α-olefin copolymer containing at least ethylene and propylene. Examples of the α-olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-hexene, Examples include heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-dodecadecene, 4-methyl-1-pentene and the like. Examples of the copolymer include a random copolymer, a block copolymer, a graft copolymer, and a mixture thereof.

The density of the polyolefin (a1) is preferably 0.85 to 0.89 g / cm ³ or less. In addition, the molecular weight of the polyolefin (a1) is preferably a weight average molecular weight of 10,000 to 200,000, and in particular, adhesion to a polyolefin substrate and adhesiveness are good, and warm water resistance is excellent. Since an aqueous resin composition capable of forming a film or an adhesive layer is obtained, it is particularly preferable that the acid-modified polyolefin having a weight average molecular weight of 50,000 to 150,000 is obtained.

  Examples of the sorbitols (a2) include sorbitol, sorbitol monofatty acid ester, sorbitol difatty acid ester, sorbitol trifatty acid ester, sorbitol monoalkyl ether, sorbitol dialkyl ether, sorbitol trialkyl ether, and the like. preferable.

  The use of the sorbitols (a2) is necessary to obtain an acid-modified polyolefin having a high graft ratio of α, β-unsaturated carboxylic acid and / or acid anhydride thereof as compared with the conventional production method. The amount of use can suppress the generation of by-products, and can produce an acid-modified polyolefin having a high graft ratio of α, β-unsaturated carboxylic acid and / or acid anhydride thereof. Since an aqueous resin composition capable of forming a film or adhesive layer having good adhesion and adhesiveness and excellent in hot water resistance is obtained, 0.01 to 2 parts by mass with respect to 100 parts by mass of polyolefin (a1). It is preferable that it is 0.03-0.5 mass part especially.

  The organic solvent (a3) is at least one selected from the group consisting of alkyl alkylates, alkylene glycol alkyl ether alkylates and dialkylene glycol alkyl ether alkylates, and has an boiling point of 250 ° C. or lower. Well, specifically, alkyl alkylates such as ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, propyl propionate, butyl propionate, ethyl butyrate, propyl butyrate, butyl butyrate, ethylene glycol monoethyl ether acetate, ethylene Alkylene glycol alkyl ether alkylates such as glycol monobutyl ether acetate and propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol Dialkylene glycol alkyl ethers alkylate etc. such as Chi glycol monobutyl ether acetate and the like, may be used at least one compound selected from these. Among these, butyl propionate having a boiling point of 130 to 250 ° C., butyl butyrate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, It is preferable because a reaction at a high temperature can be performed to facilitate the grafting reaction by drawing hydrogen, and further, butyl propionate and propylene glycol monomethyl ether acetate having a boiling point of 130 to 150 ° C. are easily removed by distillation. More preferred.

  The use amount of the organic solvent (a3) suppresses the generation of by-products, and produces an acid-modified polyolefin having a high graft ratio of α, β-unsaturated carboxylic acid and / or acid anhydride (a5) thereof. From the fact that an aqueous resin composition capable of forming a coating film or adhesive layer having good adhesion and adhesion to a polyolefin substrate and excellent in hot water resistance can be obtained. 5 to 50 parts by mass, and more preferably 10 to 30 parts by mass.

  The (meth) acrylic acid alkyl ester (a4) is an acrylic acid alkyl ester and / or a methacrylic acid alkyl ester, preferably with a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms. Esters are methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, (meth) acrylic acid i. -Butyl, 2-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, (meth) acryl Acid n-dodecyl, n-octadecyl (meth) acrylate, etc. are mentioned, among others, added to polyolefin (a1) Since the reaction proceeds easily to a boiling point of 0.99 ° C. or higher in a number of 4 or more linear, esters of alcohols with (meth) acrylic acid having a branched chain or cyclic alkyl group is more preferable.

  The amount of the (meth) acrylic acid alkyl ester (a4) used is such that the generation of by-products is suppressed and the α, β-unsaturated carboxylic acid and / or acid anhydride (a5) has a high graft ratio. The polyolefin (a1) can be produced from a water-based resin composition that can produce a modified polyolefin, and can form a coating or adhesive layer that has good adhesion and adhesion to a polyolefin substrate and is excellent in hot water resistance. It is preferable that it is 0.5-30 mass parts with respect to 100 mass parts, and it is more preferable that it is 1-20 mass parts.

  The α, β-unsaturated carboxylic acid and / or acid anhydride (a5) thereof is an unsaturated carboxylic acid and / or acid anhydride thereof excluding the (meth) acrylic acid alkyl ester (a4), preferably Unsaturated monobasic acids such as (meth) acrylic acid, crotonic acid and cinnamic acid, unsaturated dibasic acids such as fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid and citraconic anhydride Unsaturated dibasic acid and methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, 2-butanol, t-butanol, cyclohexanol, 2-ethylhexanol, n-octanol, n-dodecyl Alcohol, n-octadecyl alcohol, ethylene glycol monoethyl ether, ethylene glycol mono- monoesters with i-propyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tritylene glycol monoethyl ether or tritylene glycol monobutyl ether, unsaturated dibasic acid and methylamine, dimethylamine, ethylamine Monoamine with diethylamine, n-propylamine, i-propylamine, n-butylamine, cyclohexylamine, 2-ethylhexylamine, n-octylamine, n-dodecylamine, n-octadecylamine, aniline or benzylamine, etc. Among them, maleic acid and / or maleic anhydride is particularly preferable because of poor homopolymerization and easy grafting reaction.

  The amount of the α, β-unsaturated carboxylic acid and / or acid anhydride (a5) used is such that generation of by-products is suppressed, and α, β-unsaturated carboxylic acid and / or acid anhydride ( An acid-modified polyolefin having a high graft ratio of a5) can be produced, and an aqueous resin composition capable of forming a coating film and an adhesive layer having good adhesion and adhesion to a polyolefin substrate and excellent in warm water resistance can be obtained. Therefore, the amount is preferably 0.1 to 10 parts by mass, more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the polyolefin (a1).

  As the use ratio of the (meth) acrylic acid alkyl ester (a4) and the α, β-unsaturated carboxylic acid and / or the acid anhydride (a5), copolymerization and grafting of these both occur efficiently, Production of an acid-modified polyolefin having a high graft ratio of α, β-unsaturated carboxylic acid and / or acid anhydride (a5) thereof, with improved grafting efficiency and suppression of by-product generation Since the water-based resin composition that can form a coating film or an adhesive layer that has good adhesion and adhesion to a polyolefin substrate and is excellent in hot water resistance can be obtained, the molar ratio (a4 / a5) is 0. 0.5 to 2.0 is preferable.

  The organic peroxide (a6) is not particularly limited as long as it is a peroxide having a carbon atom in the skeleton, but is preferably a peroxide capable of generating a radical having a hydrogen abstraction effect, for example, ketone peroxide, Examples include peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates, and alkyl peroxycarbonates. Specific examples thereof include diisobutyryl peroxide, cumyl peroxyneodecanate, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, 1,1,3 , 3-tetramethylbutylperoxyneodecanate, di (4-t-butylcyclohexyl) peroxydicarbonate, 1-cyclohexyl-1-methylethylperoxyneodecanate, di (2-ethoxyethyl) peroxydi Carbonate, di (2-ethylhexyl) peroxydicarbonate, t-hexylperoxyneodecanate, dimethoxybutylperoxydicarbonate, t-butylperoxyneodecanate, t-hexylperoxypivalate, t-butylper Oxypi Rate, di (3,3,5-trimethylhexanoyl) peroxide, di-n-octanoyl peroxide, dilauroyl peroxide, distearoyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2 -Ethyl hexanate, disuccinic acid peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexanate, di (4-methylbenzoyl) Peroxide, t-butylperoxy-2-ethylhexanate,

Dibenzoyl peroxide, t-butylperoxyisobutyrate, 1,1-di (t-butylperoxy) -2-methylcyclohexanate, 1,1-di (t-butylperoxy) -3,3 , 5-trimethylcyclohexanate, 1,1-di (t-butylperoxy) cyclohexane, 1,1-di (t-hexylperoxy) cyclohexane, 2,2-di (4,4-di- (t -Butylperoxy) cyclohexane) propane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,3,5-trimethylhexanate, t-butylperoxylaurate 2,5-dimethyl-2,5-di (3-methylbenzoylperoxy) hexane, t-butylperoxyisopropyl Monomonocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, 2,2 -Di- (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl 4,4-di- (t-butylperoxy) valerate, di (2-t-butylperoxyisopropyl) benzene, Dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, p- Menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3 3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t- butyl hydroperoxide, and the like. These may be used alone or in a combination of two or more.

  In addition, the organic peroxide (a6) produces acid-modified polyolefin having a high graft ratio of α, β-unsaturated carboxylic acid and / or acid anhydride (a5) thereof, in which generation of by-products is suppressed. It is possible to obtain a water-based resin composition capable of forming a coating or adhesive layer having good adhesion and adhesion to a polyolefin base material and excellent in hot water resistance, so that it has a structure not containing a hydroxyl group and an aromatic ring. Preferably there is. Furthermore, as the organic peroxide (a6), one having a one-hour half-life decomposition temperature of 110 to 160 ° C. is preferable because degradation of the polyolefin (a1) generated in the production of the acid-modified polyolefin can be suppressed. Particularly preferred are organic peroxides having a one-hour half-life decomposition temperature in the range of 110 to 160 ° C., such as t-butylperoxy 2-ethylhexyl monocarbonate, di-t-hexyl peroxide, and di-t-butyl peroxide. .

  The amount of the organic peroxide (a6) used improves the efficiency of the addition reaction of the (meth) acrylic acid alkyl ester (a4) and the α, β-unsaturated carboxylic acid and / or its acid anhydride (a5). And the generation of low molecular weight components and by-products due to the cleavage of the polyolefin chain are suppressed, and the acid modification with a high graft ratio of α, β-unsaturated carboxylic acid and / or its acid anhydride (a5) is suppressed. Polyolefin (a1) 100 mass because a polyolefin can be produced, and an aqueous resin composition capable of forming a coating film and an adhesive layer having good adhesion and adhesion to a polyolefin substrate and excellent in hot water resistance can be obtained. The amount is preferably 0.1 to 10 parts by mass, and more preferably 0.2 to 5 parts by mass with respect to parts.

  The reaction conditions for obtaining the acid-modified polyolefin (A) are preferably a reaction temperature of 120 to 200 ° C. and a reaction time of 1 to 5 hours, and a reaction temperature of 130 to 180 ° C. and a reaction time of 2 to 4 hours. Is particularly preferred.

  Among such acid-modified polyolefins (A) used in the present invention, an aqueous resin composition capable of forming a coating or adhesive layer excellent in adhesion to a polyolefin substrate, in particular, a polypropylene substrate, and adhesion to warm water is obtained. Therefore, an acid-modified polyolefin having a graft ratio of 75 to 100% by mass represented by the following formula (G) of the α, β-unsaturated carboxylic acid and / or acid anhydride thereof is preferable, and the graft ratio is 84 to 100% by mass. % Acid-modified polyolefin is more preferable, and acid-modified polyolefin having a graft ratio of 90 to 100% by mass is most preferable.

Graft ratio = [(amount of grafted α, β-unsaturated carboxylic acid and / or acid anhydride thereof)
/ (Amount of α, β-unsaturated carboxylic acid and / or acid anhydride thereof)] × 100
.... Formula (G)
[In the formula (G), the amount of the grafted α, β-unsaturated carboxylic acid and / or acid anhydride thereof is obtained by dissolving 5 g of the acid-modified polyolefin (A) after completion of the reaction in 100 g of xylene and heating 500 g of acetone. The precipitate was filtered and dried to obtain a purified product of the acid-modified polyolefin (A), and then ¹ H-NMR measurement was performed on the purified product of the acid-modified polyolefin (A) to obtain α, β-unsaturation. By comparing the amount of protons in the vicinity of the carbonyl group of the carboxylic acid and / or its acid anhydride with the amount of protons derived from the polyolefin, the α, β-unsaturated carboxylic acid in the acid-modified polyolefin (A) and / or its acid The molar ratio of anhydride was calculated, and the amount was determined from the yield of the resulting acid-modified polyolefin (A). ]

  The weight average molecular weight of the acid-modified polyolefin (A) is preferably 50,000 to 150,000, and preferably 70,000 to 130, since an aqueous resin composition having excellent hot water adhesion can be obtained. Is more preferable.

  The acid value of the acid-modified polyolefin (A) is preferably 18 to 45 mgKOH / g, particularly 20 to 40 mgKOH / g since an aqueous resin composition having excellent hot water adhesion can be obtained. More preferably.

  The organic solvent (B) used in the present invention is required to be an organic solvent capable of dissolving the acid-modified polyolefin (A). For example, aromatic organic solvents such as toluene and xylene, cyclohexane, methylcyclohexane, etc. Aliphatic organic solvents such as ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, propyl propionate, butyl propionate, ethyl butyrate, propyl butyrate, butyl butyrate, ethylene glycol monoethyl ether acetate, Examples include glycol organic solvents such as ethylene glycol monobutyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate. But high solubility of the acid-modified polyolefin (A), since the solvent removal is easy, toluene, xylene, cyclohexane, methylcyclohexane or butyl acetate preferred.

  As the usage-amount of the said organic solvent (B), since the fluidity | liquidity of the organic solvent solution of acid-modified polyolefin (A) becomes favorable, it is 100-900 mass with respect to 100 mass parts of said acid-modified polyolefin (A). Part is preferable, and 100 to 400 parts by mass is more preferable.

  Examples of the vinyl monomer (C) used in the present invention include various vinyl monomers capable of emulsion polymerization, and are not particularly limited. Among them, various plastic substrates, particularly polyolefin substrates, are coated. In this case, the balance between adhesion and hot water adhesion is good, and a coating film having a higher level of hot water adhesion can be formed, so that the homopolymer has a glass transition point of 60 to 200 ° C. Vinyl monomer mixture containing monomer (c1), hydroxyl group-containing vinyl monomer (c2) and other copolymerizable vinyl monomer (c4), or the alicyclic vinyl A vinyl type containing a monomer (c1), a hydroxyl group-containing vinyl monomer (c2), an alkoxysilyl group-containing vinyl monomer (c3), and another copolymerizable vinyl monomer (c4) Is a monomer mixture The alicyclic vinyl monomer (c1), the hydroxyl group-containing vinyl monomer (c2), the alkoxysilyl group-containing vinyl monomer (c3), and other copolymerizable vinyl monomers. A vinyl monomer mixture containing the monomer (c4) is more preferable.

  The alicyclic vinyl monomer (c1) is not particularly limited as long as it is an alicyclic vinyl monomer having a glass transition point of a homopolymer of 60 to 200 ° C. For example, cyclohexyl Methacrylate (glass transition point of homopolymer: 70 ° C.), isobornyl methacrylate (glass transition point of homopolymer: 155 ° C.) and the like.

  The amount of the alicyclic vinyl monomer (c1) used is an aqueous resin composition capable of forming a coating or adhesive layer having excellent adhesion to a polyolefin substrate, particularly a polypropylene substrate, and excellent hot water adhesion. Since it is obtained, it is preferably 30 to 95 parts by weight, more preferably 40 to 80 parts by weight, and 50 to 80 parts by weight with respect to 100 parts by weight of the vinyl monomer (C). Most preferably.

  Next, the hydroxyl group-containing vinyl monomer (c2) is not particularly limited as long as it is a vinyl monomer containing a hydroxyl group, and examples thereof include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl. (Meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl ( Hydroxyl group-containing (meth) acrylates such as (meth) acrylate; di-2-hydroxyethyl fumarate, mono-2-hydroxyethyl-monobutyl fumarate; polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate or these And ε-ca Adducts of Rorakuton, "PLACCEL FM or FA Monomer" [Daicel Chemical Co., Ltd. caprolactone addition monomer] and the like. Among these, 2-hydroxyethyl (meth) acrylate is particularly preferable because the hydroxyl value of the vinyl copolymer obtained by emulsion polymerization can be easily adjusted within the following range.

  The amount of the hydroxyl group-containing vinyl monomer (c2) used is an aqueous resin composition capable of forming a film or adhesive layer excellent in oil resistance, adhesion to a polyolefin substrate, particularly a polypropylene substrate, and excellent hot water adhesion. Since the product is obtained, the vinyl copolymer obtained by emulsion polymerization preferably has a hydroxyl value of 10 to 100 mgKOH / g, and more preferably 20 to 80 mgKOH / g. Particularly preferred.

  Furthermore, the alkoxysilyl group-containing vinyl monomer (c3) is not particularly limited as long as it is a vinyl monomer containing an alkoxysilyl group. For example, vinyltriethoxysilane, γ- (meth) Acryloxybutylphenyldimethoxysilane, γ- (meth) acryloxybutylphenyldiethoxysilane, γ- (meth) acryloxybutylphenyldipropoxysilane, or the following general formula (1)

（式中、Ｒ_１、Ｒ_２、Ｒ_３はそれぞれ独立にメチル基、エチル基、プロピル基、メトキシ基、エトキシ基又はプロポキシ基であって、かつ、少なくとも１個がメトキシ基、エトキシ基又はプロポキシ基であり、Ｒ_４は水素原子又はメチル基であり、ｎは０〜４の整数を表す。）
で示される、ケイ素原子にアルコキシ基が１〜３個結合したアルコキシシリル基を含有するビニル系単量体が挙げられる。

(Wherein R ₁ , R ₂ and R ₃ are each independently a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group or a propoxy group, and at least one of them is a methoxy group, an ethoxy group or a propoxy group) R ₄ is a hydrogen atom or a methyl group, and n represents an integer of 0 to _4. )
And a vinyl monomer containing an alkoxysilyl group in which 1 to 3 alkoxy groups are bonded to a silicon atom.

  Specific examples of the vinyl monomer represented by the general formula (1) include γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acrylic. Roxypropyltripropoxysilane, γ- (meth) acryloxypropylmethoxydiethoxysilane, γ- (meth) acryloxypropylmethoxydipropoxysilane, γ- (meth) acryloxypropyldimethylmethoxysilane, γ- (meth) acryl Examples include loxypropyldimethylethoxysilane.

  Among the alkoxysilyl group-containing vinyl monomers (c3), a vinyl resin represented by the general formula (1) is obtained because an aqueous resin composition having high curability and excellent resistance to warm water and oil is obtained. A vinyl monomer containing an alkoxysilyl group in which three alkoxy groups are bonded to a silicon atom is preferable.

  The amount of the alkoxysilyl group-containing vinyl monomer (c3) used depends on the type of the alkoxysilyl group-containing vinyl monomer, but is excellent in oil resistance and is suitable for polyolefin substrates, particularly polypropylene substrates. Since an aqueous resin composition capable of forming a film and an adhesive layer excellent in adhesion and heat-resistant water adhesion is obtained, 0.3 to 5.0 with respect to 100 parts by mass of the vinyl monomer (C). It is preferable that it is a mass part, and it is especially preferable that it is 0.4-2.0 mass part.

  As other copolymerizable vinyl monomers (c4), copolymerizable vinyl monomers other than the vinyl monomers (c1), (c2) and (c3) are not particularly limited. Any of them can be used, for example, styrene monomers such as styrene, vinyl toluene, p-methyl styrene, ethyl styrene, propyl styrene, isopropyl styrene, p-tert-butyl styrene, benzyl (meth) acrylate, etc. (Meth) acrylates containing no functional group in the side chain, aromatic vinyl compounds such as vinyltoluene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, iso (i) -propyl (meth) ) Acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, tert-butyl (Meth) acrylate, sec-butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, “acrylate ester SL” [Mitsubishi Rayon Co., Ltd. 13 methacrylate mixtures], alkyl (meth) acrylates such as stearyl (meth) acrylate, carboxyl groups or acid anhydride group-containing vinyl monomers such as acrylic acid, methacrylic acid, itaconic acid, maleic anhydride,

Monofunctional (meth) acrylates having functional groups such as diethylaminoethyl (meth) acrylate, (methyl) glycidyl (meth) acrylate, acrylamide, ethylene glycol di (meth) acrylate, 1,6-hexadiol di (meth) acrylate, Multifunctional (meth) acrylates such as trimethylolpropane tri (meth) acrylate, alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, methoxybutyl (meth) acrylate, vinyl acetate Vinyl esters such as vinyl benzoate, “Beoba” (a vinyl ester of a branched (branched) aliphatic monocarboxylic acid manufactured by Shell of the Netherlands), diallyl phthalate, divinylbenzene, allyl acrylate, etc. Such as a monomer having two or more unsaturated bonds in the molecule are mentioned, it is possible to use one or more vinyl monomers from these alone or in combination.

  Among the other copolymerizable vinyl monomers (c4), since an aqueous resin composition having excellent water dispersion stability can be obtained, carboxyls such as acrylic acid, methacrylic acid, itaconic acid, maleic anhydride and the like can be obtained. It is preferable to use a vinyl monomer having a group or an acid anhydride group as a part or all of the vinyl monomer (c4).

  The amount of the other copolymerizable vinyl monomer (c4) used is from the vinyl monomer (C) to the alicyclic vinyl monomer (c1) and a hydroxyl group-containing vinyl monomer. The total amount excluding (c2) and the alkoxysilyl group-containing vinyl monomer (c3), but containing a carboxyl group or an acid anhydride group as a part or all of the other copolymerizable vinyl monomer (c4) When a vinyl monomer is used, the amount used thereof is an aqueous resin composition having further excellent water dispersion stability by neutralizing with a basic compound after emulsion polymerization of the vinyl monomer (C). Since the product is obtained, it is preferable that the acid value of the vinyl copolymer obtained by emulsion polymerization of the vinyl monomer (C) is 3 to 60 mgKOH / g, especially 5 to 30 mgKOH / g. It is particularly preferable that the amount is g. Arbitrariness.

  As a usage-amount of the basic compound used for neutralization of a carboxyl group or an acid anhydride group, it is preferable that it is the quantity from which the pH of an aqueous resin composition will be 7.5-9.5. Examples of the basic compound used for neutralization include ammonia (water); primary to tertiary amines such as ethylamine, diethylamine, and triethylamine. Among them, aqueous ammonia is preferable.

  Although the amount of the vinyl monomer (C) used is not particularly limited, an aqueous resin composition excellent in oil resistance, dispersion stability and adhesion to a polyolefin substrate such as a polypropylene substrate can be obtained. , Preferably 100 to 1,900 parts by weight, more preferably 100 to 1,000 parts by weight, and particularly preferably 100 to 500 parts by weight with respect to 100 parts by weight of the acid-modified polyolefin (A). preferable.

  As the emulsifier (D) used in the present invention, various emulsifiers can be used, and among them, an anionic emulsifier and / or a nonionic emulsifier is preferable because a stable aqueous resin composition can be produced by emulsion polymerization. Examples of the anionic emulsifier include alkylbenzene sulfonates, alkylene disulfonates, alkyl diphenyl ether disulfonates, alkyl sulfate esters, polyoxyethylene alkylphenyl sulfonates, polyoxyethylene alkylphenyl ether sulfate esters, polyoxyethylene Alkyl ether sulfates, polyoxyethylene polycyclic phenyl ether sulfates, dialkyl succinate sulfonates, monoalkyl succinate sulfonates, salts of naphthalene sulfonate formalin condensate, etc. For example, polyoxyethylene alkyl ether, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene alkyl ether, Reoxyalkylene glycols, polyoxyethylene alkates, sorbitan alkates, polyoxyethylene sorbitan alkates, polyoxyethylene polycyclic phenyl ethers, polyoxyalkylene alkyl phenyl ethers, polyoxyethylene-polyoxypropylene block copolymers, etc. Can be mentioned.

  Examples of the anionic emulsifier that is generally commercially available as the emulsifier (D) include New Coal 707SF manufactured by Nippon Emulsifier Co., Ltd., Latemul E-118B manufactured by Kao Co., Ltd., and the nonionic emulsifier includes, for example, Japan Examples include New Coal 707 manufactured by Emulsifier Co., Ltd. and Neugen TDS-200D manufactured by Daiichi Kogyo Seiyaku Co., Ltd.

  Furthermore, as the emulsifier (D), a reactive emulsifier can be used. Examples of the reactive anionic emulsifier include vinyl sulfonates, (meth) acryloyloxy polyoxyethylene sulfate esters, (meth) Acryloyloxy polyoxyethylene sulfonates, polyoxyethylene alkenyl phenyl sulfonates, polyoxyethylene alkenyl phenyl ether sulfates, sodium allyl alkyl sulfosuccinate, (meth) acryloyloxy polyoxypropylene sulfonates, etc. Examples of the reactive nonionic emulsifier include polyoxyethylene alkenyl phenyl ether and polyoxyethylene methacryloyl ether. Of course, a plurality of these emulsifiers can be used, and the non-reactive emulsifier and the reactive emulsifier can be used in combination.

  Examples of commercially available reactive emulsifiers include, for example, Aqualon KH-1025, HS-1025, Aqualon KH-10, HS-10, New Frontier A-229E [above, Daiichi Kogyo Seiyaku Co., Ltd. )], Adeka Soap SE-3N, SE-5N, SE-10N, SE-20N, SE-30N [above, manufactured by Asahi Denka Kogyo Co., Ltd.], AntoxMS-60, MS-2N, RA-1120, RA-2614 [above, manufactured by Nippon Emulsifier Co., Ltd.], Eleminol JS-2, RS-30 [above, manufactured by Sanyo Chemical Industry Co., Ltd.], LATEMUL S-120A, S-180A, S-180 [above, Kao Co., Ltd.] and other reactive anionic emulsifiers, Aqualon RN-20, RN-30, RN-50 New Frontier N-177E (above, Daiichi Kogyo Seiyaku Co., Ltd.), Adekari Soap ER-10, ER-20, ER-30, ER-40 [above, manufactured by Asahi Denka Kogyo Co., Ltd.], RMA-568, RMA-1114 [above, manufactured by Nippon Emulsifier Co., Ltd.], NK ester M- Examples thereof include reactive nonionic emulsifiers such as 20G, M-40G, and M-230G (manufactured by Shin-Nakamura Chemical Co., Ltd.).

About the kind of emulsifier (D), it is not restrict | limited to an above-described thing, It can select suitably and can use and can use what is generally marketed.
From the viewpoint of environmental protection and occupational health, it is preferable to use an emulsifier having no alkylphenol skeleton.

  The amount of the emulsifier (D) used is a vinyl monomer (C) because an aqueous resin composition capable of forming a coating or adhesive layer having high dispersion stability of resin particles and excellent hot water adhesion is obtained. ) Is preferably in the range of 0.2 to 10 parts by mass, particularly preferably in the range of 0.5 to 5 parts by mass.

  Examples of the polymerization initiator (F) used in the present invention include various radical polymerization initiators such as persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate, azobisisobutyronitrile and its hydrochloride, , 2'-azobis (2-amidinopropane) dihydrochloride, 4,4'-azobis (4-cyanovaleric acid) and other azo polymerization initiators, hydrogen peroxide, tertiary butyl hydroperoxide, cumene hydroper Examples thereof include peroxide-based polymerization initiators such as oxides. The amount of the polymerization initiator (F) used is preferably in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the vinyl monomer (C), and 0.3 to 3 parts by mass. More preferably, it is the range.

  The polymerization initiator (F) can be used in combination with a reducing agent. Examples of the reducing agent that can be used in combination include sodium sulfooxylate formaldehyde, sodium pyrosulfite, and L-ascorbic acid. Further, when a reducing agent is used in combination, a compound that generates a so-called polyvalent metal salt ion represented by iron ions, copper ions, or the like can be used in combination as an accelerator. The amount of the polymerization initiator (F) and the reducing agent used is preferably in the range of 0.1 to 10 parts by mass independently of 100 parts by mass of the vinyl monomer (C). The range of 0.3 to 3 parts by mass is more preferable.

  In addition, a chain transfer agent can be used to control the degree of polymerization in the emulsion polymerization of the vinyl monomer (C). Examples of the chain transfer agent include alkyl mercaptans such as n-butyl mercaptan, n-octyl mercaptan and n-lauryl mercaptan, thioglycolic acid esters such as butyl thioglycolate and octyl thioglycolate, thiomalic acid, 3- Examples thereof include water-soluble mercaptans such as mercaptopropionic acid and thioglycolic acid, and alcohols such as isopropyl alcohol.

  The aqueous resin composition of the present invention comprises an acid-modified polyolefin (A) having a weight average molecular weight of 50,000 to 150,000 and an acid value of 18 to 45 mgKOH / g, an organic solvent (B), a vinyl monomer (C), A vinyl-based monomer in the composition (I) containing an emulsifier (D), water (E) and a polymerization initiator (F), and wherein the acid-modified polyolefin (A) is dissolved in an organic solvent (B). An aqueous resin composition obtained by removing the solvent after emulsion polymerization of the monomer (C) may be used, and the production method thereof is not limited. However, during the emulsion polymerization of the vinyl monomer (C), an acid is used. An aqueous resin composition in which resin particles mixed with a vinyl copolymer obtained by emulsion polymerization of a modified polyolefin (A) and a vinyl monomer (C) are dispersed in water in the presence of an emulsifier (D). Can be easily produced, the acid-modified polyolefin ( ) Is dissolved in an organic solvent (B), an acid-modified polyolefin solution (AB), the vinyl monomer (C), an emulsifier (D), and water (E) are mixed to obtain an emulsified dispersion ( After II), a method of adding a polymerization initiator (F) and emulsion-polymerizing the vinyl monomer (C) and then removing the solvent is preferred. As the acid-modified polyolefin solution (AB), an acid-modified polyolefin solution obtained by acid-modifying polyolefin in an organic solvent can be used as it is.

  In the method for producing the aqueous resin composition, first, an acid-modified polyolefin solution (AB) obtained by dissolving the acid-modified polyolefin (A) in an organic solvent (B), the vinyl monomer (C), and an emulsifier (D) and water (E) are mixed to obtain an emulsified dispersion (II). As these mixing methods, uniform fine particles can prevent generation of aggregated particles, settling of polymer particles, and the like. A method of mechanically mixing and emulsifying and dispersing is preferable, and examples thereof include a method of emulsifying and dispersing using a mechanical emulsifying and dispersing device such as a homomixer.

  In the method for producing the aqueous resin composition, the vinyl monomer (C) in the emulsion dispersion (II) is subjected to emulsion polymerization while stirring in a nitrogen atmosphere in the presence of a polymerization initiator (F). To do. The reaction temperature at that time is preferably 40 to 100 ° C., and the reaction time is preferably 2 to 6 hours, particularly preferably 3 to 5 hours. The polymerization initiator (F) may be added in advance in the reaction kettle, or may be added sequentially as the polymerization reaction proceeds.

  The aqueous resin composition of the present invention is obtained by removing the solvent after emulsion polymerization of the vinyl monomer (C) in the composition (I), and the method for removing the solvent is not particularly limited. The solvent is preferably removed by distillation under reduced pressure. As conditions for distillation under reduced pressure, a temperature of 30 to 80 ° C. and a degree of vacuum of 0.0008 to 0.04 MPa are preferable.

  The average particle size of the particles dispersed in the aqueous resin composition of the present invention and the aqueous resin composition obtained by the method for producing the aqueous resin composition of the present invention includes generation of aggregated particles and sedimentation of polymer particles. Since it can prevent, it is preferable that it is 0.05-1.0 micrometer, and it is more preferable that it is 0.05-0.5 micrometer. Furthermore, the vinyl copolymer obtained by emulsion polymerization of the vinyl monomer (C) has a carboxyl group or an acid anhydride group neutralized with a basic compound, so that the dispersion of the particles It is preferable because of its excellent stability.

  The aqueous resin composition of the present invention and the aqueous resin composition obtained by the method for producing the aqueous resin composition of the present invention have a film excellent in adhesion, hot water resistance, and oil resistance to a polyolefin substrate having a nonpolar surface. Since it can be formed, it can be used as a coating agent for polyolefin films and sheets and polyolefin moldings in a wide range of fields such as automotive parts materials, electrical and electronic parts materials, civil engineering and building materials.

  When the aqueous resin composition of the present invention and the aqueous resin composition obtained by the method for producing the aqueous resin composition of the present invention are used as paints, for example, either clear or colored paints containing pigments are used. It may be in the form of In addition to various organic pigments, the pigment includes various inorganic pigments such as titanium oxide, iron oxide, aluminum flakes, titanium coat mica, and the like.

  As a method for forming a dry film, various coating methods such as an air spray method, an airless spray method, a brush coating or a roll coating method can be used on a plastic substrate such as a polyolefin substrate.

  As the drying method, depending on the drying property of the aqueous resin composition of the present invention and the aqueous resin composition obtained by the method of producing the aqueous resin composition of the present invention or the heat resistance of the substrate, the respective uses can be further determined. Depending on the above, it is possible to set a wide range of drying conditions, such as drying at room temperature for about 1 day to 2 weeks or drying in a temperature range of about 40 to 120 ° C.

  Next, although a reference example, an example, and a comparative example are shown and the present invention is explained still in detail, the present invention is not limited to this. In addition, unless otherwise indicated, the part and% in an example are a mass reference | standard.

Reference Example 1 [Production Example of Acid-Modified Polyolefin (A-1)]
In a 3 liter reaction vessel equipped with a stirrer, a thermometer and a condenser, an ethylene / propylene / 1-butene copolymer having a weight average molecular weight of 92,000 [ethylene / propylene / 1-butene (mass ratio) = 65/24 / 11] 1,000 g, sorbitol 1 g, Irganox 1010 {pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]} (hereinafter abbreviated as Irganox 1010) manufactured by Ciba Geigy. 1 g, 1 g of Irgafos 168 [Tris (2,4-di-tert-butylphenyl) phosphite] (hereinafter abbreviated as Irgafos 168) and 200 g of propylene glycol monomethyl ether acetate were put in a nitrogen atmosphere at 140 ° C. Kept It was dissolved in a bath, the reaction vessel while stirring to adjust the temperature of the oil bath to be 130 ° C.. Next, 31 g of n-butyl methacrylate (hereinafter abbreviated as nBMA), 31 g of maleic anhydride and 5 g of di-tertiary butyl peroxide are added with stirring, and the reaction vessel is kept at 130 ° C. for 3 hours. After the reaction, while reducing the pressure in the flask with an aspirator, propylene glycol monomethyl ether acetate, unreacted maleic anhydride, nBMA, di-tertiary butyl peroxide, and di-tertiary butyl peroxide are decomposed. The low molecular weight compound was removed for 1 hour, and after completion of the decompression, the reaction product was taken out and cooled to obtain an acid-modified polyolefin (A-1). The molar ratio of nBMA and maleic anhydride (nBMA / maleic anhydride) used in this reaction is 0.69.

  The weight average molecular weight of the obtained acid-modified polyolefin (A-1) [measured using gel permeation chromatography (HLC-8120GPC manufactured by Tosoh Corporation, standard material: polystyrene). Hereinafter, the weight average molecular weight was determined in the same manner. ] Was measured to be 90,000.

After 5 g of the obtained acid-modified polyolefin (A-1) was dissolved in 100 g of xylene by heating, it was added to 500 g of acetone, and the precipitate was filtered and dried to obtain a purified product of acid-modified polyolefin (A-1). The purified product of the resulting acid-modified polyolefin (A-1) was subjected to ¹ H-NMR measurement to determine the graft ratio (hereinafter, the graft ratio was determined in the same manner). The graft ratio of maleic anhydride was as follows. It was 91 mass%. Moreover, the acid value of acid-modified polyolefin (A-1) was 30 mgKOH / g.

Reference Example 2 [Production Example of Acid-Modified Polyolefin (A-2)]
Acid-modified polyolefin (A-2) was obtained in the same manner as in Reference Example 1, except that 31 g of maleic anhydride was changed to 33 g and 31 g of nBMA were changed to 33 g, and the inside of the reaction vessel was further adjusted to 150 ° C. The molar ratio of nBMA and maleic anhydride (nBMA / maleic anhydride) used in this reaction is 0.69.

  The resulting acid-modified polyolefin (A-2) had a weight average molecular weight of 75,000, a maleic anhydride graft ratio of 85% by mass, and an acid value of 30 mgKOH / g.

Reference Example 3 [Production Example of Acid-Modified Polyolefin (A-3)]
Instead of ethylene / propylene / 1-butene copolymer [ethylene / propylene / 1-butene (mass ratio) = 65/24/11] having a weight average molecular weight of 92,000, ethylene / propylene having a weight average molecular weight of 75,000 1-Butene copolymer [ethylene / propylene / 1-butene (mass ratio) = 65/24/11] was used, and 31 g of maleic anhydride was changed to 33 g and 31 g of nBMA was changed to 33 g. The acid-modified polyolefin (A-3) was obtained in the same manner as in Reference Example 1 except that the temperature was adjusted to 150 ° C. The molar ratio of nBMA and maleic anhydride (nBMA / maleic anhydride) used in this reaction is 0.69.

  The resulting acid-modified polyolefin (A-3) had a weight average molecular weight of 65,000, a grafting ratio of maleic anhydride of 85% by mass, and an acid value of 30 mgKOH / g.

Reference Example 4 [Production Example of Acid-Modified Polyolefin (A-4)]
Instead of ethylene / propylene / 1-butene copolymer having a weight average molecular weight of 92,000 [ethylene / propylene / 1-butene (mass ratio) = 65/24/11], ethylene / propylene having a weight average molecular weight of 118,000 1-Butene copolymer [ethylene / propylene / 1-butene (mass ratio) = 65/24/11], maleic anhydride 31 g to 40 g, nBMA 31 g to 40 g, propylene glycol monomethyl ether acetate 200 g 100 g The acid-modified polyolefin (A-4) was obtained in the same manner as in Reference Example 1 except that the temperature was changed to 180 ° C. The molar ratio of nBMA and maleic anhydride (nBMA / maleic anhydride) used in this reaction is 0.69.

  The resulting acid-modified polyolefin (A-4) had a weight average molecular weight of 90,000, a maleic anhydride graft ratio of 88% by mass, and an acid value of 38 mgKOH / g.

Reference Example 5 [Production Example of Acid-Modified Polyolefin (A-5)]
An acid-modified polyolefin (A-5) was obtained in the same manner as in Reference Example 1, except that 31 g of maleic anhydride was changed to 23 g and 31 g of nBMA was changed to 23 g. The molar ratio of nBMA and maleic anhydride (nBMA / maleic anhydride) used in this reaction is 0.69.

  The resulting acid-modified polyolefin (A-5) had a weight average molecular weight of 90,000, a maleic anhydride graft ratio of 91% by mass, and an acid value of 23 mgKOH / g.

Reference Example 6 [Production Example of Comparative Acid-Modified Polyolefin (A-6)]
In a 3 liter reaction vessel equipped with a stirrer, a thermometer and a condenser, an ethylene / propylene / 1-butene copolymer having a weight average molecular weight of 92,000 [ethylene / propylene / 1-butene (mass ratio) = 65/24 / 11] 1000 g, 1 g of Irganox 1010, 1 g of Irgafos 168 and 1,000 g of xylene are dissolved in an oil bath maintained at 140 ° C. in a nitrogen atmosphere, and then the inside of the reaction vessel becomes 130 ° C. while stirring. The oil bath temperature was adjusted as follows. Next, while stirring, 45 g of nBMA, 45 g of maleic anhydride and 10 g of di-tertiary butyl peroxide were added, and the reaction was carried out for 3 hours while maintaining the inside of the reaction vessel at 130 ° C. While removing xylene and unreacted maleic anhydride, nBMA, di-tertiary butyl peroxide, and low molecular weight compounds decomposed by di-tertiary butyl peroxide for 1 hour The product was taken out and cooled to obtain a comparative acid-modified polyolefin (A-6). The molar ratio of nBMA and maleic anhydride (nBMA / maleic anhydride) used in this reaction is 0.69.

  The comparative acid-modified polyolefin (A-6) obtained had a weight average molecular weight of 90,000, a maleic anhydride graft ratio of 62% by mass, and an acid value of 30 mgKOH / g.

Reference Example 7 [Production Example of Comparative Acid-Modified Polyolefin (A-7)]
Comparative acid-modified polyolefin (A-7) was obtained in the same manner as in Reference Example 6 except that 45 g of maleic anhydride was changed to 31 g and 45 g of nBMA was changed to 31 g. The molar ratio of nBMA and maleic anhydride (nBMA / maleic anhydride) used in this reaction is 0.69.

  The comparative acid-modified polyolefin (A-7) obtained had a weight average molecular weight of 90,000, a grafting ratio of maleic anhydride of 64% by mass, and an acid value of 22 mgKOH / g.

Reference Example 8 [Production Example of Comparative Acid-Modified Polyolefin (A-8)]
Instead of ethylene / propylene / 1-butene copolymer having a weight average molecular weight of 92,000 [ethylene / propylene / 1-butene (mass ratio) = 65/24/11], ethylene / propylene having a weight average molecular weight of 118,000 A comparative acid-modified polyolefin (A-8) was prepared in the same manner as in Reference Example 6 except that 1-butene copolymer [ethylene / propylene / 1-butene (mass ratio) = 65/24/11] was used. Obtained. The molar ratio of nBMA and maleic anhydride (nBMA / maleic anhydride) used in this reaction is 0.69.

  The obtained acid-modified polyolefin (A-8) for comparison had a weight average molecular weight of 125,000, a grafting ratio of maleic anhydride of 62% by mass, and an acid value of 30 mgKOH / g.

Reference Example 9 [Production Example of Comparative Acid-Modified Polyolefin (A-9)]
Instead of ethylene / propylene / 1-butene copolymer having a weight average molecular weight of 92,000 [ethylene / propylene / 1-butene (mass ratio) = 65/24/11], ethylene / propylene having a weight average molecular weight of 118,000 Reference Example 6 except that a 1-butene copolymer [ethylene / propylene / 1-butene (mass ratio) = 65/24/11] was used and maleic anhydride 45 g was changed to 33 g and nBMA 45 g was changed to 33 g. In the same manner, a comparative acid-modified polyolefin (A-9) was obtained. The molar ratio of nBMA and maleic anhydride (nBMA / maleic anhydride) used in this reaction is 0.69.

  The comparative acid-modified polyolefin (A-9) obtained had a weight average molecular weight of 125,000, a maleic anhydride graft ratio of 64% by mass, and an acid value of 23 mgKOH / g.

Example 1
To 666.7 parts of a 30% toluene solution of an acid-modified polyolefin (A-1) having an acid value of 30 mgKOH / g and a weight average molecular weight of 90,000 obtained in Reference Example 1, cyclohexyl methacrylate (hereinafter abbreviated as CHMA). ) 300.0 parts, methyl methacrylate (hereinafter abbreviated as MMA) 345.0 parts, 2-hydroxyethyl methacrylate (hereinafter abbreviated as β-HEMA) 140.0 parts, SZ-6030 [Toray Dow Corning Co., Ltd. Γ-methacryloxypropyltrimethoxysilane) 5.0 parts, methacrylic acid (hereinafter abbreviated as MAA) 10.0 parts, lauryl mercaptan 5.0 parts as a chain transfer agent, Aqualon KH-1025 Reactive anionic emulsifier manufactured by Ichi Kogyo Seiyaku Co., Ltd., 25% aqueous solution] and 60.0 parts Adekaria Soap ER-20 (Asahi Denka) 10.0 parts of nonionic emulsifier manufactured by Kogyo Co., Ltd.) dissolved in 500.0 parts of water is stirred and mixed with a glass rod to obtain a coarse emulsion, and the coarse emulsion is further homogenizer [special machine Emulsified at 9,000 rpm for 30 minutes using a TK auto homomixer manufactured by Chemical Industry Co., Ltd. to obtain an emulsified dispersion (II-1).

  Further, 5.0 parts of tertiary butyl hydroperoxide was dissolved in an aqueous emulsifier solution of 5.0 parts Newcol 707SF (anionic emulsifier manufactured by Nippon Emulsifier Co., Ltd.) and 100.0 parts ion-exchanged water, and a polymerization initiator was obtained. An aqueous solution (1) was obtained. Further, 3.0 parts of Redol CP [Mitsubishi Chemical Corporation sodium sulfooxylate formaldehyde] was dissolved in 100.0 parts of ion-exchanged water to obtain an aqueous reducing agent solution (1).

  In a 2 liter reaction vessel equipped with a stirrer, a thermometer and a cooler, 500 parts of ion-exchanged water was charged, and the temperature was raised to 70 ° C. while stirring while introducing nitrogen gas. After sufficiently purging the inside of the reaction vessel with nitrogen, the emulsion dispersion (II-1) was dropped into the reaction vessel over 3 hours, and an aqueous polymerization initiator solution and an aqueous reducing agent solution were added dropwise over 3.5 hours. During the reaction, stirring was continued while maintaining the inside of the reaction vessel at 70 ° C. After completion of the dropwise addition of the polymerization initiator aqueous solution and the reducing agent aqueous solution, the mixture was kept at 70 ° C. while stirring for 30 minutes, cooled to 25 ° C., and adjusted to pH 9 with 12.5% aqueous ammonia. Further, the obtained aqueous resin composition was distilled off under reduced pressure at 0.007 MPa and 42 ° C. for 1 hour with a water flow decompressor [AS-3 manufactured by Tokyo Riken Co., Ltd.]. Thereafter, the pH and nonvolatile content concentration were adjusted with 12.5% ammonia water and ion-exchanged water to obtain an aqueous resin composition having a nonvolatile content concentration of 42.9%, a viscosity of 350 mPa · s and a pH of 9.3. It was 0.29 micrometer when the particle diameter of the emulsion in the obtained aqueous resin composition was measured with the particle diameter measuring device [The Nikkiso Co., Ltd. product Microtrac particle size analyzer 9340UPA].

(Addition of film-forming aid)
The obtained aqueous resin composition was stirred with a disper. In this state, 60 parts of diethylene glycol dibutyl ether was added to 100 parts of resin solids in the aqueous resin composition, and then stirred with a disper for 10 minutes. Thus, an aqueous one-component coating agent comprising an aqueous resin composition was obtained.

(Coating test plate creation method)
Each of the polypropylene base material (A) [polypropylene base material manufactured by Nippon Test Panel Co., Ltd.] and the polypropylene base material for automobile interior (B) is sprayed with the aqueous one-component coating agent to give a dry film thickness of 15 μm. After coating for 5 minutes and setting for 5 minutes, it was dried at 80 ° C. for 30 minutes using a hot air dryer, and further dried at room temperature for 5 days to obtain a test plate for evaluation. Using the obtained test plate, an adhesion (primary adhesion) test to a substrate and a hot water resistant adhesion (secondary adhesion) test were performed as follows. The results are shown in Table 1.

Adhesion test: 10 × 10 cuts with 2 mm squares were made with a cutter on the coating surface of the test plate, and a peel test with cellophane tape (number of samples: 5) was performed from the four corners. The first decimal place was rounded off.) Was evaluated according to the following evaluation criteria.
Evaluation criteria ◎◎: 100
◎: 99-95
◎-○: 94-85
○: 84-65
Δ: 64-45
X: 44-30 pieces
XX: 29 or less

  Warm water adhesion test: after immersing the test plate in warm water at 40 ° C. for 24 hours, taking it out and drying at room temperature for 2 hours, and then performing a peel test with cellophane tape as in the above adhesion test, Was evaluated according to the same evaluation criteria as in the adhesion test.

Example 2
Instead of CHMA 300.0 parts, MMA 345.0 parts, β-HEMA 140.0 parts, SZ-6030 5.0 parts, MAA 10.0 parts and lauryl mercaptan 5.0 parts, CHMA 300.0 parts, MMA 350.0 parts, An aqueous resin having a non-volatile content concentration of 42.7%, a viscosity of 400 mPa · s, and a pH of 9.4, except that 140.0 parts of β-HEMA, 10.0 parts of MAA, and 5.0 parts of lauryl mercaptan were used. A composition was obtained. It was 0.28 micrometer when the particle diameter of the emulsion in the obtained aqueous resin composition was measured with the particle diameter measuring device.

  Except that the obtained aqueous resin composition was used, the adhesion (primary adhesion) test to the base material and the hot water resistant adhesion (secondary adhesion) test were conducted in the same manner as in Example 1. The results are shown in Table 1.

Example 3
Instead of CHMA 300.0 parts, MMA 345.0 parts, β-HEMA 140.0 parts, SZ-6030 5.0 parts, MAA 10.0 parts and lauryl mercaptan 5.0 parts, CHMA 300.0 parts, MMA 350.0 parts, Except for using 140.0 parts of isobutyl methacrylate (hereinafter abbreviated as IBMA), 10.0 parts of MAA, and 5.0 parts of lauryl mercaptan, the non-volatile concentration was 42.9% and the viscosity was 280 mPa · s. An aqueous resin composition having a pH of 9.1 was obtained. It was 0.26 micrometer when the particle diameter of the emulsion in the obtained aqueous resin composition was measured with the particle diameter measuring device.

  Except that the obtained aqueous resin composition was used, the adhesion (primary adhesion) test to the base material and the hot water resistant adhesion (secondary adhesion) test were conducted in the same manner as in Example 1. The results are shown in Table 1.

Example 4
Instead of 30% toluene solution of acid-modified polyolefin (A-1), 30% toluene solution of acid-modified polyolefin (A-2) having an acid value of 30 mgKOH / g and a weight average molecular weight of 75,000 obtained in Reference Example 2 In the same manner as in Example 1 except that was used, an aqueous resin composition having a nonvolatile content concentration of 42.7%, a viscosity of 400 mPa · s, and a pH of 9.4 was obtained. It was 0.28 micrometer when the particle diameter of the emulsion in the obtained aqueous resin composition was measured with the particle diameter measuring device.

  Except that the obtained aqueous resin composition was used, the adhesion (primary adhesion) test to the base material and the hot water resistant adhesion (secondary adhesion) test were conducted in the same manner as in Example 1. The results are shown in Table 1.

Example 5
Instead of 30% toluene solution of acid-modified polyolefin (A-1), 30% toluene solution of acid-modified polyolefin (A-3) having an acid value of 30 mgKOH / g and a weight average molecular weight of 65,000 obtained in Reference Example 3 In the same manner as in Example 1 except that was used, an aqueous resin composition having a nonvolatile content concentration of 42.9%, a viscosity of 310 mPa · s, and a pH of 9.1 was obtained. It was 0.26 micrometer when the particle diameter of the emulsion in the obtained aqueous resin composition was measured with the particle diameter measuring device.

  Except that the obtained aqueous resin composition was used, the adhesion (primary adhesion) test to the base material and the hot water resistant adhesion (secondary adhesion) test were conducted in the same manner as in Example 1. The results are shown in Table 1.

Example 6
Instead of 30% toluene solution of acid-modified polyolefin (A-1), 30% toluene solution of acid-modified polyolefin (A-4) having an acid value of 38 mgKOH / g and a weight average molecular weight of 90,000 obtained in Reference Example 4 In the same manner as in Example 1 except that was used, an aqueous resin composition having a nonvolatile content concentration of 42.9%, a viscosity of 380 mPa · s, and a pH of 9.4 was obtained. It was 0.27 micrometer when the particle diameter of the emulsion in the obtained aqueous resin composition was measured with the particle diameter measuring device.

  Except that the obtained aqueous resin composition was used, the adhesion (primary adhesion) test to the base material and the hot water resistant adhesion (secondary adhesion) test were conducted in the same manner as in Example 1. The results are shown in Table 1.

Example 7
Instead of 30% toluene solution of acid-modified polyolefin (A-1), 30% toluene solution of acid-modified polyolefin (A-5) having an acid value of 23 mgKOH / g and a weight average molecular weight of 90,000 obtained in Reference Example 5 In the same manner as in Example 1 except that was used, an aqueous resin composition having a nonvolatile content concentration of 43.0%, a viscosity of 440 mPa · s, and a pH of 9.2 was obtained. It was 0.28 micrometer when the particle diameter of the emulsion in the obtained aqueous resin composition was measured with the particle diameter measuring device.

  Except that the obtained aqueous resin composition was used, the adhesion (primary adhesion) test to the base material and the hot water resistant adhesion (secondary adhesion) test were conducted in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1
Example 1 except that the 30% toluene solution of the comparative acid-modified polyolefin (A-6) obtained in Reference Example 6 was used instead of (30% toluene solution) of the acid-modified polyolefin (A-1). Similarly, an aqueous resin composition having a nonvolatile content concentration of 42.9%, a viscosity of 380 mPa · s, and a pH of 9.4 was obtained. It was 0.27 micrometer when the particle diameter of the emulsion in the obtained aqueous resin composition was measured with the particle diameter measuring device.

  Except that the obtained aqueous resin composition was used, the adhesion (primary adhesion) test to the base material and the hot water resistant adhesion (secondary adhesion) test were conducted in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 2
Example 1 except that the 30% toluene solution of the comparative acid-modified polyolefin (A-7) obtained in Reference Example 7 was used instead of (30% toluene solution) of the acid-modified polyolefin (A-1). Similarly, an aqueous resin composition having a nonvolatile content concentration of 43.2%, a viscosity of 290 mPa · s, and a pH of 9.5 was obtained. It was 0.27 micrometer when the particle diameter of the emulsion in the obtained aqueous resin composition was measured with the particle diameter measuring device.

  Except that the obtained aqueous resin composition was used, the adhesion (primary adhesion) test to the base material and the hot water resistant adhesion (secondary adhesion) test were conducted in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 3
Example 1 except that the 30% toluene solution of the comparative acid-modified polyolefin (A-8) obtained in Reference Example 8 was used instead of (30% toluene solution) of the acid-modified polyolefin (A-1). Similarly, an aqueous resin composition having a nonvolatile content concentration of 43.0%, a viscosity of 280 mPa · s, and a pH of 9.1 was obtained. It was 0.27 micrometer when the particle diameter of the emulsion in the obtained aqueous resin composition was measured with the particle diameter measuring device.

  Except that the obtained aqueous resin composition was used, the adhesion (primary adhesion) test to the base material and the hot water resistant adhesion (secondary adhesion) test were conducted in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 4
Example 1 except that the 30% toluene solution of the comparative acid-modified polyolefin (A-9) obtained in Reference Example 9 was used instead of the (30% toluene solution) of the acid-modified polyolefin (A-1). Similarly, an aqueous resin composition having a nonvolatile content concentration of 42.7%, a viscosity of 220 mPa · s, and a pH of 9.4 was obtained. It was 0.27 micrometer when the particle diameter of the emulsion in the obtained aqueous resin composition was measured with the particle diameter measuring device.

  Except that the obtained aqueous resin composition was used, the adhesion (primary adhesion) test to the base material and the hot water resistant adhesion (secondary adhesion) test were conducted in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 5
200.0 parts of acid-modified polyolefin (A-1) having an acid value of 30 mgKOH / g and a weight average molecular weight of 90,000 obtained in Reference Example 1 were added to 300.0 parts of CHMA, 345.0 parts of MMA, and 140.0 parts of β-HEMA. Acid modified polyolefin solution dissolved in 5.0 parts of SZ-6030, 10.0 parts of MAA and 5.0 parts of lauryl mercaptan, 60.0 parts of Aqualon KH-1025 (25% aqueous solution) and Adekaria soap ER-20 A solution obtained by dissolving 20.0 parts in 500.0 parts of water is stirred and mixed with a glass rod to obtain a coarse emulsion, and the coarse emulsion is further emulsified at 9000 rpm for 30 minutes using a homogenizer. Dispersion (II′-1) was obtained.

  A non-volatile content concentration of 42.6 was obtained in the same manner as in Example 1 except that the obtained emulsified dispersion (II′-1) was used in place of the emulsified dispersion (II-1) and the vacuum distillation was omitted. %, An aqueous resin composition having a viscosity of 110 mPa · s and a pH of 9.5 was obtained. It was 0.59 micrometer when the particle diameter of the emulsion in the obtained aqueous resin composition was measured with the particle diameter measuring device.

  Except that the obtained aqueous resin composition was used, the adhesion (primary adhesion) test to the base material and the hot water resistant adhesion (secondary adhesion) test were conducted in the same manner as in Example 1. The results are shown in Table 1.

Claims (11)

  An acid-modified polyolefin (A), an organic solvent (B), a vinyl monomer (C), an emulsifier (D), water (E) and a polymerization initiator (F), and the acid-modified polyolefin (A ) Is an aqueous resin composition obtained by emulsion polymerization of the vinyl monomer (C) in the composition (I) obtained by dissolving in the organic solvent (B), and then removing the solvent. (A) is selected from the group consisting of sorbitols (a2), alkyl alkylates, alkylene glycol alkyl ether alkylates and dialkylene glycol alkyl ether alkylates for polyolefins (a1) containing ethylene and propylene as constituent units (Meth) acrylic acid alkyl ester (a4) in the presence of an organic solvent (a3) having a boiling point of 250 ° C. or lower. Except when, alpha, beta-unsaturated carboxylic acid and / or its acid anhydride (a5) [where the (meth) acrylic acid alkyl ester (a4). ] Is an acid-modified polyolefin obtained by adding an organic peroxide (a6).   The acid-modified polyolefin (A) is (meth) acrylic acid in the presence of 0.01 to 2 parts by mass of sorbitols (a2) and 5 to 50 parts by mass of an organic solvent (a3) in 100 parts by mass of the polyolefin (a1). An acid-modified polyolefin obtained by adding 0.5 to 30 parts by mass of an alkyl ester (a4) and 0.1 to 10 parts by mass of an α, β-unsaturated carboxylic acid and / or an acid anhydride (a5) thereof The aqueous resin composition according to claim 1.   The molar ratio (a4 / a5) of the (meth) acrylic acid alkyl ester (a4) to the α, β-unsaturated carboxylic acid and / or its acid anhydride (a5) is 0.5 to 2.0. Item 3. The aqueous resin composition according to Item 1 or 2.   The acid-modified polyolefin (A) is an acid-modified polyolefin having a graft ratio of 84 to 100% by mass of an α, β-unsaturated carboxylic acid and / or an acid anhydride (a5) thereof. The aqueous resin composition according to Item.   The aqueous resin composition according to any one of claims 1 to 4, wherein the acid-modified polyolefin (A) is an acid-modified polyolefin having a weight average molecular weight of 50,000 to 150,000 and an acid value of 18 to 45 mgKOH / g. .   The composition (I) contains 100 to 900 parts by weight of the organic solvent (B) and 100 to 1,900 parts by weight of the vinyl monomer (C) with respect to 100 parts by weight of the acid-modified polyolefin (A). The aqueous resin composition according to claim 1, wherein the aqueous resin composition is a composition.   The vinyl monomer (C) is a copolymer of an alicyclic vinyl monomer (c1), a hydroxyl group-containing vinyl monomer (c2) having a glass transition point of 60-200 ° C. with the homopolymer, and other copolymers. A vinyl monomer mixture containing a possible vinyl monomer (c4), or the alicyclic vinyl monomer (c1), a hydroxyl group-containing vinyl monomer (c2) and an alkoxysilyl group The aqueous resin composition according to any one of claims 1 to 6, which is a vinyl monomer mixture containing a vinyl monomer (c3) and another copolymerizable vinyl monomer (c4). object.   The other copolymerizable vinyl monomer (c4) contains a carboxyl group- or acid anhydride group-containing vinyl monomer, and the vinyl monomer in the composition (I) The aqueous resin composition according to claim 7, wherein (C) is subjected to emulsion polymerization, neutralized with a basic compound, and then desolvated.   The aqueous resin composition according to any one of claims 5 to 8, wherein the acid-modified polyolefin (A) is an acid-modified polyolefin having a weight average molecular weight of 70,000 to 130,000 and an acid value of 20 to 40 mgKOH / g. .   An acid-modified polyolefin solution (AB) obtained by dissolving the acid-modified polyolefin (A) in an organic solvent (B), a vinyl monomer (C), an emulsifier (D), and water (E) are mixed. 2. An aqueous resin composition obtained by preparing an emulsion dispersion (II), emulsion-polymerizing the vinyl monomer (C) in the presence of a polymerization initiator (F), and then removing the solvent. The aqueous resin composition of any one of -9.   A coated product obtained by coating the aqueous resin composition according to any one of claims 1 to 10 on a plastic substrate and drying it.