JP2008260851A - Method for producing resin composition for coating and coating material containing the resin composition for coating - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a resin composition for coating, exhibiting excellent adhesiveness to various substrates, especially plastic substrates, and forming a coating film having excellent water-resistance, alcohol resistance and chemical resistance. <P>SOLUTION: The method for producing a resin composition for coating contains a step to perform the emulsion polymerization of (a) monomers comprising (a<SB>1</SB>) 50.0-99.9 mass% vinyl monomer containing a cyano group and (a<SB>2</SB>) 0.1-50.0 mass% other copolymerizable vinyl monomer and a step to add (b) monomers comprising (b<SB>1</SB>) 40.0-99.0 mass% aromatic vinyl monomer, (b<SB>2</SB>) 0.1-10.0 mass% vinyl monomer containing an acid group and (b<SB>3</SB>) 0.9-59.9 mass% other copolymerizable vinyl monomer to the above emulsion polymerization product and perform emulsion polymerization of the monomers. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention is, for example, the production of a resin composition for paints that can form a coating film that has excellent adhesion to substrates such as metal, wood, paper, and plastic, and that is also excellent in water resistance, alcohol resistance, and chemical resistance. The present invention relates to a method and a coating material containing the coating resin composition produced by the method.

  A substrate such as metal, wood, paper, or plastic is generally coated for the purpose of protecting the surface or maintaining aesthetics. Conventionally, various solvent-based paints are generally used for coating. However, solvent-based paints have problems such as occupational safety and health, health problems, and pollution because they have the possibility of being flammable or toxic. Therefore, a shift from solvent-based paints to water-based paints is desired.

  When a solvent-based paint is applied on a substrate, the adhesion between the coating film formed on the substrate and the substrate is improved because the solvent contained in the solvent-based paint is cured after the substrate is attacked. I was able to expect that. However, since such an effect cannot be expected in the case of a water-based paint, the adhesion between the coating film and the substrate by the water-based paint has not been sufficient. In particular, when a water-based paint is used for a plastic substrate, the adhesion between the coating film and the substrate is insufficient.

  Therefore, various studies have been made so far to solve such problems. For example, an aqueous emulsion resin composition having a two-layer structure obtained by polymerizing an aqueous vinyl monomer component to a seed resin composition containing (meth) acrylonitrile (Patent Document 1) is shown. However, the coating film formed using the aqueous emulsion resin composition of Patent Document 1 may not have sufficient adhesion with a plastic substrate. Also, water resistance and alcohol resistance are not sufficient.

In addition, it has a layer structure obtained by emulsion polymerization of a monomer containing a conjugated diene monomer and then emulsion polymerization by adding a monomer containing a cyano group-containing ethylenically unsaturated monomer. An aqueous dispersion of a colored resin is shown (Patent Document 2). However, even a coating film formed from this aqueous dispersion may not have sufficient adhesion with a plastic substrate. Also, chemical resistance is not sufficient.
Therefore, for example, a resin composition for paints that can form a coating film having adhesion, water resistance, alcohol resistance, and chemical resistance on various substrates such as metal, wood, paper, and plastic, especially plastic substrates. Things are desired.
JP 2000-27097 A JP 05-255567 A

  In the present invention, there is provided a method for producing a resin composition for coatings, which is excellent in adhesion to various substrates, particularly plastic substrates, and can form a coating film having water resistance, alcohol resistance and chemical resistance.

In the present invention, 50.0 to 99.9% by mass of a cyano group-containing vinyl monomer (a ₁ ) and 0.1 to 50.0% by mass of another copolymerizable vinyl monomer ( a step of polymerizing the monomer (a) composed of a ₂ ), and thereafter, 40.0 to 99.0% by mass of the aromatic vinyl monomer (b ₁ ), and 0.1 to 10. A monomer comprising 0% by mass of an acid group-containing vinyl monomer (b ₂ ) and 0.9 to 59.9% by mass of another copolymerizable vinyl monomer (b ₃ ) ( A method for producing a resin composition for coating, comprising the step of adding b) and polymerizing.

Moreover, in the manufacturing method of the resin composition for coating materials of this invention, mass ratio of a monomer (a) and a monomer (b) is set to [mass ratio of a monomer (a)] / [monomer. It is preferable that the mass ratio of (b)] = 10/90 to 90/10.
Moreover, in this invention, the coating material containing the resin composition for coating materials obtained by the said manufacturing method is provided.

  According to the method for producing a resin composition for paints of the present invention, a film having excellent adhesion to various substrates, particularly plastic substrates, and having water resistance, alcohol resistance, and chemical resistance is formed. A resin composition for coating can be produced.

Hereinafter, the manufacturing method of the resin composition for coating materials of this invention is demonstrated.
The method for producing a resin composition for paint according to the present invention comprises a monomer (a) comprising a cyano group-containing vinyl monomer (a ₁ ) and another copolymerizable vinyl monomer (a ₂ ). Polymerizing the aromatic vinyl monomer (b ₁ ), the acid group-containing vinyl monomer (b ₂ ), and other copolymerizable vinyl monomers (b ₃ ) Adding a monomer (b) consisting of and polymerizing.

Hereinafter, the monomer (a) will be described.
The monomer (a) of the present invention comprises a cyano group-containing vinyl monomer (a ₁ ) and another copolymerizable vinyl monomer (a ₂ ).
[Cyano group-containing vinyl monomer (a ₁ )]
Examples of the cyano group-containing vinyl monomer (a ₁ ) include acrylonitrile and methacrylonitrile. The content of the monomer (a) cyano group-containing vinyl monomer in _{(a 1)} is a 50.0 to 99.9 wt%. The content in the monomer (a) is preferably 50.0 to 90.0% by mass, and more preferably 60.0 to 90.0% by mass. When the content of the cyano group-containing vinyl monomer (a ₁ ) is 50.0% by mass or more, the adhesion of the coating film to the substrate is increased, and the chemical resistance of the coating film is also increased. In addition, by cyano group-containing vinyl monomer content of (a ₁₎ and 99.9% or less, the adhesiveness between the substrate and the coating film becomes high.

[Other copolymerizable vinyl monomers (a ₂ )]
Examples of other copolymerizable vinyl monomers (a ₂ ) (hereinafter referred to as vinyl monomers (a ₂ )) include alkyl (meth) acrylates and carboxyl group-containing vinyl monomers. , Hydroxy group-containing vinyl monomers, maleimide derivatives, aldehyde group or carbonyl group-containing vinyl monomers, amide group-containing vinyl monomers, aromatic vinyl monomers, olefin monomers, in the molecule And monomers having two or more polymerizable unsaturated double bonds.
Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl ( Examples include meth) acrylate, n-lauryl (meth) acrylate, n-stearyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and isobornyl (meth) acrylate.
Examples of the carboxyl group-containing vinyl monomer include (meth) acrylic acid, itaconic acid, citraconic acid, maleic acid, monomethyl maleate, monobutyl maleate, monomethyl itaconate, monobutyl itaconate, vinyl benzoic acid, and oxalic acid. Monohydroxyethyl (meth) acrylate, monohydroxyethyl (meth) acrylate of tetrahydrophthalate, monohydroxypropyl (meth) acrylate of tetrahydrophthalate, monohydroxyethyl (meth) acrylate of 5-methyl-1,2-cyclohexanedicarboxylic acid, phthalate Acid monohydroxyethyl (meth) acrylate, monohydroxypropyl (meth) acrylate phthalate, monohydroxyethyl (meth) acrylate maleate, hydroxypropyl maleate (meth) Acrylate, tetrahydrophthalic acid mono-hydroxybutyl (meth) acrylate.
Examples of the hydroxy group-containing vinyl monomer include hydroxyalkyl (2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, alkyl (meth) acrylate) and the like. And a meta) acrylate or an adduct of these with ε-caprolactone.
Examples of maleimide derivatives include N-cyclohexylmaleimide and N-butylmaleimide.
Examples of the aldehyde group- or carbonyl group-containing vinyl monomer include acrolein, diacetone acrylamide, formylstyrene, vinyl alkyl ketone, (meth) acrylamide pivalin aldehyde, diacetone (meth) acrylate, acetonyl acrylate, 2 -Hydroxypropyl acrylate acetyl acetate, acetoacetoxyethyl (meth) acrylate, butanediol-1,4-acrylate-acetyl acetate, acrylamide methyl anisaldehyde and the like.
Examples of the amide group-containing vinyl monomer include (meth) acrylamide, crotonamide, N-methylolacrylamide and the like.
Examples of the aromatic vinyl monomer include epoxy group-containing vinyl monomers such as allyl glycidyl ether and glycidyl (meth) acrylate, styrene, and α-methylstyrene.
Examples of the olefin monomer include butadiene.
Examples of the monomer having two or more polymerizable unsaturated double bonds in the molecule include divinylbenzene, diallylbenzene, diallylbenzene, ethylene glycol di (meth) acrylate, 1,4-butanediol di ( (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) Examples include acrylate, allyl (meth) acrylate, methylene bis (meth) acrylamide, triallyl cyanurate, and the like.
These vinyl monomers may be used alone or in combination of two or more. From the viewpoints of adhesion and water resistance, it is preferable to use alkyl (meth) acrylates and aromatic vinyl monomers.

The content of the monomer (a) in the vinyl monomer _{(a 2)} is a 0.1 to 50.0 wt%. The content of the vinyl monomer (a ₂ ) is preferably 10.0 to 50.0% by mass, and more preferably 10.0 to 40.0%. When the content of the vinyl monomer (a ₂ ) is 0.1% by mass or more, the adhesion between the substrate and the coating film and the water resistance of the coating film are increased. Also, if a vinyl monomer content of (a ₂₎ and 50 wt% or less, the higher the adhesion between the substrate and the coating, decrease in chemical resistance of the coating film can be prevented.

Hereinafter, the monomer (b) will be described. The monomer (b) of the present invention comprises an aromatic vinyl monomer (b ₁ ), an acid group-containing monomer (b ₂ ), and other copolymerizable vinyl monomers (b ₃ ) Consists of.
[Aromatic vinyl-based monomer (b ₁ )]
Examples of the aromatic vinyl monomer (b ₁ ) include styrene monomers, alkyl vinyl benzenes, and polycyclic aromatic vinyl monomers.
Examples of the styrene monomer include styrene, α-methylstyrene, chlorostyrene, and the like. Examples of the alkyl vinyl benzene include vinyl toluene and ethyl vinyl benzene. Examples of the polycyclic aromatic vinyl monomer include vinyl naphthalene. Of these, styrene is preferably used. These aromatic vinyl monomers may be used alone or in combination of two or more.

The content of the monomer (b) an aromatic vinyl monomer in _{(b 1)} is used at 40.0 to 99.0 wt%. The content of the aromatic vinyl monomer (b ₁ ) is preferably 50.0 to 98.6% by mass, and more preferably 60.0 to 80.0% by mass. When the content of the aromatic vinyl monomer (b ₁ ) is 40.0% by mass or more, the adhesion between the substrate and the coating film and the alcohol resistance of the coating film are increased. Further, if the aromatic vinyl monomer content of (b ₁₎ and 90.0 wt% or less, the adhesiveness between the substrate and the coating film becomes high.

[Acid group-containing monomer (b ₂ )]
Examples of the acid group-containing monomer (b ₂ ) include (meth) acrylic acid, itaconic acid, citraconic acid, maleic acid, monomethyl maleate, monobutyl maleate, monomethyl itaconate, monobutyl itaconate, vinylbenzoic acid, Oxalic acid monohydroxyethyl (meth) acrylate, tetrahydrophthalic acid monohydroxyethyl (meth) acrylate, tetrahydrophthalic acid monohydroxypropyl (meth) acrylate, 5-methyl-1,2-cyclohexanedicarboxylic acid monohydroxyethyl (meth) acrylate , Monohydroxyethyl phthalate (meth) acrylate, monohydroxypropyl phthalate (meth) acrylate, monohydroxyethyl (meth) acrylate maleate, hydroxypropyl (meth) acrylate maleate DOO, tetrahydrophthalic acid mono-hydroxybutyl (meth) acrylate. One or more of these can be appropriately selected and used as necessary. As the acid group-containing monomer (b ₂ ), it is preferable to use (meth) acrylic acid from the viewpoint of adhesion between the substrate and the coating film.

The content of the monomer (b) an acid group-containing monomer in _{(b 2)} is 0.1 to 10.0 wt%. Further, the content of the acid group-containing monomer (b ₂ ) is preferably 0.5 to 8.0% by mass, and more preferably 1.0 to 7.0% by mass. When the content of the acid group-containing monomer (b ₂ ) is 0.1% by mass or more, the adhesion between the substrate and the coating film is increased. Further, if the acid group-containing monomer content of (b ₂₎ and 10.0 wt% or less, water resistance and alcohol resistance of the coating film becomes high.

[Other copolymerizable vinyl monomers (b ₃ )]
Other copolymerizable vinyl monomers (b ₃ ) (hereinafter referred to as vinyl monomers (b ₃ )) include alkyl (meth) acrylates, hydroxy group-containing vinyl monomers, and maleimides. Derivatives, aldehyde group or carbonyl group-containing vinyl monomers, amide group-containing vinyl monomers, epoxy group-containing vinyl monomers, nitrile group-containing vinyl monomers, olefin monomers, Examples include monomers having two or more polymerizable unsaturated double bonds.
Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl ( Examples include alkyl (meth) acrylates such as (meth) acrylate, n-lauryl (meth) acrylate, n-stearyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and isobornyl (meth) acrylate.
Examples of the hydroxy group-containing vinyl monomer include hydroxyalkyl (2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, alkyl (meth) acrylate) and the like. And a meta) acrylate or an adduct of these with ε-caprolactone.
Examples of maleimide derivatives include N-cyclohexylmaleimide and N-butylmaleimide.
Examples of the aldehyde group- or carbonyl group-containing vinyl monomer include acrolein, diacetone acrylamide, formylstyrene, vinyl alkyl ketone, (meth) acrylamide pivalin aldehyde, diacetone (meth) acrylate, acetonyl acrylate, 2 -Hydroxypropyl acrylate acetyl acetate, acetoacetoxyethyl (meth) acrylate, butanediol-1,4-acrylate-acetyl acetate, acrylamide methyl anisaldehyde and the like.
Examples of the amide group-containing vinyl monomer include (meth) acrylamide, crotonamide, N-methylolacrylamide and the like.
Examples of the epoxy group-containing vinyl monomer include allyl glycidyl ether and glycidyl (meth) acrylate.
Examples of the olefin monomer include butadiene.
Examples of the monomer having two or more polymerizable unsaturated double bonds in the molecule include divinylbenzene, diallylbenzene, diallylbenzene, ethylene glycol di (meth) acrylate, 1,4-butanediol di ( (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) Examples include acrylate, allyl (meth) acrylate, methylene bis (meth) acrylamide, triallyl cyanurate, and the like.
These vinyl monomers may be used alone or in combination of two or more. From the viewpoint of water resistance and alcohol resistance of the coating film, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-lauryl ( It is preferable to use alkyl (meth) acrylates having 4 or more carbon atoms in the alkyl group such as (meth) acrylate and n-stearyl (meth) acrylate.

The content of the vinyl monomer in the monomer _(b) (b ₃₎ is 0.9 to 59.9 wt%. The content of the vinyl monomer _{(b 3)} is preferably set to 0.9 to 45.5 wt%, and more preferably 13.0 to 39.0 wt%. When the content of the vinyl monomer (b ₃ ) is 0.9% by mass or more, the water resistance and alcohol resistance of the coating film are increased. Further, by the vinyl monomer content of (b ₃₎ and 59.9 wt% or less, it improves adhesion between the substrate and the coating film.

In the method for producing a resin composition for paints of the present invention, the monomer (a) is used as a first-stage polymerizable monomer component to carry out a polymerization reaction, and then a second-stage polymerizable monomer component is used as a single monomer. By using a multistage polymerization method in which the body (b) is added and a polymerization reaction is performed, a resin composition for coating having a two-layer structure is obtained. The coating resin composition having this two-layer structure can provide adhesion to various substrates, water resistance, alcohol resistance, and chemical resistance, which cannot be obtained with a single layer structure.
The mass ratio of the monomer (a) and the monomer (b) used in the method for producing a resin composition for paints of the present invention is [mass ratio of monomer (a)] / [monomer (b ) Mass ratio] = 10/90 to 90/10. The mass ratio of the monomer (a) to the monomer (b) is [mass ratio of monomer (a)] / [mass ratio of monomer (b)] = 15 / 85-85. / 15, more preferably [mass ratio of monomer (a)] / [mass ratio of monomer (b)] = 25/75 to 75/25.
Further, the polymerization rate in the polymerization reaction of the monomer (a) in the first stage is preferably 80.0% or more, more preferably 90% or more, and further preferably 95% or more. .

In the method for producing a resin composition for paints of the present invention, the polymerization reaction in the first and second stages is performed by, for example, polymerizing the monomer (a) or the monomer (b) in the presence of a surfactant. A known method can be used in which the emulsion polymerization is carried out using a radical polymerization initiator.
As the radical polymerization initiator, those generally used for radical polymerization can be used, and examples thereof include persulfates, oil-soluble azo compounds, water-soluble azo compounds, and organic peroxides.

Examples of persulfates include potassium persulfate, sodium persulfate, and ammonium persulfate.
Examples of the oil-soluble azo compound include azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2 Examples include '-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile and the like.
As the water-soluble azo compound, 2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2′-azobis {2-methyl -N- [2- (1-hydroxyethyl)] propionamide}, 2,2′-azobis {2-methyl-N- [2- (1-hydroxybutyl)] propionamide}, 2,2′-azobis [2- (5-Methyl-2-imidazolin-2-yl) propane] and its salts, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] and its salts, 2,2 ′ -Azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane] and its salts, 2,2'-azobis {2- [1- (2-hydroxyethyl) -2-imidazoline- 2-il] Lopan} and its salts, 2,2′-azobis (2-methylpropionamidine) and its salts 2,2′-azobis (2-methylpropyneamidine) and its salts, 2,2′-azobis [N- ( 2-carboxyethyl) -2-methylpropionamidine] and salts thereof.
Examples of organic peroxides include benzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, t-butyl peroxy-2-ethylhexanoate, and t-butyl peroxyisobutyrate. It is done.
These radical polymerization initiators may be used alone or in combination of two or more. When acceleration of the polymerization rate and low temperature polymerization at 70 ° C. or lower are desired, for example, a reducing agent such as sodium bisulfite, Rongalite, ferrous sulfate, ascorbate is used in combination with the radical polymerization catalyst. And is advantageous.

  The addition amount of the radical polymerization initiator used in the first stage and the second stage is usually the total monomer (hereinafter simply referred to as the total monomer) of the monomer (a) and the monomer (b). )) To 0.01 to 10% by mass. Moreover, it is preferable that the addition amount of a radical polymerization initiator shall be 0.05-5 mass% from a viewpoint of progress and control of a polymerization reaction.

Moreover, when forming emulsion particle | grains by multistage emulsion polymerization of a monomer (a) and a monomer (b), in order to adjust the molecular weight of each copolymer, a molecular weight modifier can be added.
Examples of the molecular weight modifier include mercaptans such as n-dodecyl mercaptan, t-dodecyl mercaptan, n-octyl mercaptan, n-tetradecyl mercaptan, n-hexyl mercaptan; halogen compounds such as carbon tetrachloride and ethylene bromide; A known chain transfer agent such as α-methylstyrene dimer may be used. From the viewpoint of weather resistance, the chain transfer agent is preferably used in an amount of 1% by mass or less based on the mass of all monomers.

  Moreover, it is preferable that the manufactured emulsion particle contains 0.1-10.0 mass parts of surfactant, when the mass part of all the monomers is 100 mass parts. When the surfactant contained in the emulsion particles is 0.1 parts by mass or more, the polymerization stability and storage stability of the emulsion are improved. Moreover, if the surfactant contained in the emulsion particles is 10 parts by mass or less, blending stability and stability over time can be maintained when forming a paint without impairing water resistance. The surfactant contained in the emulsion particles is preferably 0.5 to 8.0 parts by mass.

  Examples of the surfactant include various anionic, cationic or nonionic surfactants, and polymer emulsifiers. A reactive emulsifier having an ethylenically unsaturated bond in the surfactant component can also be used. Among these, from the viewpoint of weather resistance and water resistance of the coating film, it is preferable to use a reactive emulsifier.

The emulsion obtained by emulsion polymerization can be improved in stability by adding a basic compound to the pH range of 6.5 to 10.0 after the emulsion polymerization. Especially, it is preferable to adjust to pH 8.5-10.0 from a viewpoint of the outstanding freeze-thaw stability.
Examples of basic compounds include ammonia, triethylamine, propylamine, dibutylamine, amylamine, 1-aminooctane, 2-dimethylaminoethanol, ethylaminoethanol, -2-diethylaminoethanol, 1-amino-2-propanol, 2 -Amino-1-propanol, 2-amino-2-methyl-1-propanol, 3-amino-1-propanol, 1-dimethylamino-2-propanol, 3-dimethylamino-1-propanol, 2-propylaminoethanol , Ethoxypropylamine, aminobenzyl alcohol, morpholine, sodium hydroxide, potassium hydroxide and the like.

Moreover, it is preferable that the average particle diameter of the emulsion particle | grains used by this invention is 20-300 nm, It is more preferable that it is 30-200 nm, It is further more preferable that it is 40-100 nm. If the average particle diameter of the emulsion particles is 20 nm or more, the solid content of the paint during coating is improved. Moreover, if the average particle diameter of the emulsion particles is 300 nm or less, the appearance of the coating film is improved. Furthermore, if the average particle diameter of the emulsion particles is 100 nm or less, the film forming property of the coating film is improved.
As described above, the resin composition for coatings of the present invention has a two-layer structure by using a multistage polymerization method, adhesion to various substrates, particularly plastic substrates, water resistance of the formed coating film, Combines alcohol resistance and chemical resistance.

  The paint containing the resin composition for paints of the present invention usually has a solid content of the resin composition for paints of 10.0 to 80.0% by mass. In addition, various pigments, antifoaming agents, pigment dispersants, leveling agents, anti-sagging agents, matting agents, ultraviolet absorbers, antioxidants, heat resistance improvers, slip agents are used to develop advanced performance as coating materials. May also contain preservatives. Moreover, you may mix and use hardening agents, such as another emulsion resin, water-soluble resin, a viscosity control agent, and melamines.

  Moreover, the coating material containing the resin composition for coatings of this invention can be apply | coated to base materials, such as a hard-to-paint plastic, by the various coating method well-known. The coating resin composition of the present invention is excellent in adhesion, water resistance, alcohol resistance, and chemical resistance, for example, by heating at 60 to 90 ° C. for 10 to 30 minutes after application to the substrate. Form a coating film.

EXAMPLES Hereinafter, an Example and a comparative example are shown and this invention is demonstrated. In addition, this invention is not limited by the following description. The “parts” and “%” shown below are based on mass. Table 1 shows the mass ratio of each monomer in the monomer (a) and the mass ratio of each monomer in the monomer (b) used in Examples and Comparative Examples. Table 1 shows the mass ratio between the monomer (a) and the monomer (b). In Table 1, a cyano group-containing vinyl monomer (a ₁ ) and another copolymerizable vinyl monomer (a ₂ ) are used as the monomer (a ₁ ) and the monomer (a ₂ ). And an aromatic vinyl monomer (b ₁ ), an acid group-containing monomer (b ₂ ), and another copolymerizable vinyl monomer (b ₃ ) as a monomer (b ₁ ) , Monomer (b ₂ ) and monomer (b ₃ ).
Moreover, the symbol in Table 1 shows the following meanings.
St: styrene MMA: methyl methacrylate n-BMA: normal butyl methacrylate n-BA: normal butyl acrylate LMA: lauryl methacrylate 2-EHA: 2-ethylhexyl acrylate AN: acrylonitrile MAN: methacrylonitrile GMA: glycidyl methacrylate 2-HEMA: 2 -Hydroxyethyl methacrylate MAA: Methacrylic acid AA: Acrylic acid ABS: Acrylonitrile butadiene styrene base PPO: Polyphenylene oxide base

[Example 1]
148.3 parts of deionized water was added to a reaction vessel equipped with a thermometer, thermostat, stirrer, reflux condenser, and dropping device, and the temperature was raised to 80 ° C. while mixing and stirring in a nitrogen stream.
Next, 1.5 parts of styrene, 21 parts of acrylonitrile, 7.5 parts of n-butyl acrylate, 1.0 part of Aqualon HS-10 (polyoxyethylene alkylpropenyl ether sulfate, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Adekari Soap NE-20 (α- [1-[(allyloxy) methyl] -2- (nonylphenoxy) ethyl] -ω-hydroxyoxyethylene, manufactured by Asahi Denka Co., Ltd., 80% solution) 0.5 part and deionized water 15 parts A monomer emulsion consisting of the above and an initiator solution consisting of 0.2 parts of ammonium persulfate and 10 parts of deionized water were dropped into the reaction vessel over 2 hours using a metering pump. After completion of the dropping, aging was performed at the same temperature for 2 hours.
Next, 56 parts of styrene, 8.4 parts of n-butyl acrylate, 3.5 parts of lauryl methacrylate, 2.1 parts of acrylic acid, Aqualon HS-10 (polyoxyethylene alkylpropenyl ether sulfate, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 2.0 parts, 1 part of Adeka Soap NE-20 (α- [1-[(allyloxy) methyl] -2- (nonylphenoxy) ethyl] -ω-hydroxyoxyethylene, manufactured by Asahi Denka Co., Ltd., 80% solution) And a monomer emulsion composed of 40 parts of deionized water and an initiator solution composed of 0.2 part of ammonium persulfate and 10 parts of deionized water were dropped into the reaction vessel over 4 hours using a metering pump. did. After completion of the dropping, aging was performed at the same temperature for 1 hour.
Next, the mixture was cooled to 40 ° C. while adding 10 parts of a 1% by mass dimethylaminoethanol aqueous solution, and then filtered through a 300 mesh nylon cloth.
[Mass ratio of monomer (a)] / [Mass ratio of monomer (b)] = 30/70, and a coating resin composition having an average particle size of 80 nm and a solid content of 30% by mass was obtained.

[Example 2]
148.3 parts of deionized water was added to a reaction vessel equipped with a thermometer, thermostat, stirrer, reflux condenser, and dropping device, and the temperature was raised to 80 ° C. while mixing and stirring in a nitrogen stream.
Next, 15 parts of acrylonitrile, 25 parts of methacrylonitrile, 10 parts of n-butyl acrylate, 2.0 parts of Aqualon HS-10 (polyoxyethylene alkylpropenyl ether sulfate ester, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Adecalia Soap NE- 20 (α- [1-[(allyloxy) methyl] -2- (nonylphenoxy) ethyl] -ω-hydroxyoxyethylene, manufactured by Asahi Denka Co., Ltd., 80% solution) and 25 parts of deionized water. A monomer emulsion and an initiator solution consisting of 0.2 part of ammonium persulfate and 15 parts of deionized water were dropped into the reaction vessel over 3 hours using a metering pump. After completion of the dropping, aging was performed at the same temperature for 2 hours.
Next, 30 parts of styrene, 2.5 parts of n-butyl methacrylate, 6 parts of n-butyl acrylate, 5 parts of lauryl methacrylate, 2 parts of 2-hydroxyethyl methacrylate, 2.5 parts of methacrylic acid, Aqualon HS-10 (polyoxyethylene) Alkylpropenyl ether sulfate ester (Daiichi Kogyo Seiyaku Co., Ltd.) 3.0 parts, Adekaria soap NE-20 (α- [1-[(allyloxy) methyl] -2- (nonylphenoxy) ethyl] -ω-hydroxyoxy Ethylene, 80% solution manufactured by Asahi Denka Co., Ltd.) Monomer emulsion consisting of 1 part and 25 parts of deionized water, and initiator solution consisting of 0.2 part of ammonium persulfate and 10 parts of deionized water, And dropped into the reactor over 4 hours. After completion of the dropping, aging was performed at the same temperature for 1 hour.
Next, the mixture was cooled to 40 ° C. while adding 10 parts of a 1% by mass dimethylaminoethanol aqueous solution, and then filtered through a 300 mesh nylon cloth.
[Mass ratio of monomer (a)] / [Mass ratio of monomer (b)] = 50/50, and a coating resin composition having an average particle size of 80 nm and a solid content of 30% by mass was obtained.

[Comparative Example 1]
148.3 parts of deionized water was added to a reaction vessel equipped with a thermometer, thermostat, stirrer, reflux condenser, and dropping device, and the temperature was raised to 80 ° C. while mixing and stirring in a nitrogen stream.
Next, 44 parts of acrylonitrile, 31.2 parts of 2-ethylhexyl acrylate, 2.4 parts of 2-hydroxyethyl methacrylate, 2.4 parts of methacrylic acid, Aqualon HS-10 (polyoxyethylene alkylpropenyl ether sulfate, Daiichi Kogyo Seiyaku) 4.0 parts, Adeka soap NE-20 (α- [1-[(allyloxy) methyl] -2- (nonylphenoxy) ethyl] -ω-hydroxyoxyethylene, manufactured by Asahi Denka Co., Ltd., 80% solution ) A monomer emulsion consisting of 0.5 parts and 40 parts of deionized water, an initiator solution consisting of 0.2 parts of ammonium persulfate and 15 parts of deionized water, respectively, over a period of 4 hours using a metering pump. It was dripped in the reactor. After completion of the dropping, aging was performed at the same temperature for 2 hours.
Subsequently, 10 parts of n-butyl methacrylate, 8 parts of n-butyl acrylate, 1 part of lauryl methacrylate, 0.4 part of 2-hydroxyethyl methacrylate, 0.6 part of atacrylic acid, Aqualon HS-10 (polyoxyethylene alkylpropenyl ether sulfate) Ester, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 2.0 parts, Adekaria Soap NE-20 (α- [1-[(allyloxy) methyl] -2- (nonylphenoxy) ethyl] -ω-hydroxyoxyethylene, Asahi Denka) A monomer emulsion consisting of 1 part of an 80% solution and 10 parts of deionized water, and an initiator solution consisting of 0.2 part of ammonium persulfate and 10 parts of deionized water, using a metering pump, It dropped in each reactor over time. After completion of the dropping, aging was performed at the same temperature for 1 hour.
Next, the mixture was cooled to 40 ° C. while adding 10 parts of a 1% by mass dimethylaminoethanol aqueous solution, and then filtered through a 300 mesh nylon cloth.
[Mass ratio of monomer (a)] / [Mass ratio of monomer (b)] = 80/20, and a coating resin composition having an average particle size of 80 nm and a solid content of 30% by mass was obtained.

[Comparative Example 2]
148.3 parts of deionized water was added to a reaction vessel equipped with a thermometer, thermostat, stirrer, reflux condenser, and dropping device, and the temperature was raised to 80 ° C. while mixing and stirring in a nitrogen stream.
Next, 19.6 parts of styrene, 0.4 part of methacrylic acid, 1.0 part of Aqualon HS-10 (polyoxyethylene alkylpropenyl ether sulfate ester, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Adekaria soap NE-20 (α- [1-[(allyloxy) methyl] -2- (nonylphenoxy) ethyl] -ω-hydroxyoxyethylene (manufactured by Asahi Denka Co., Ltd., 80% solution) and a monomer emulsion consisting of 0.5 parts deionized water and 10 parts Then, an initiator solution consisting of 0.2 part of ammonium persulfate and 15 parts of deionized water was dropped into the reactor over 2 hours using a metering pump. After completion of the dropping, aging was performed at the same temperature for 2 hours.
Next, 40 parts of styrene, 14.4 parts of methyl methacrylate, 13.6 parts of methacrylonitrile, 4 parts of glycidyl methacrylate, 8 parts of methacrylic acid, Aqualon HS-10 (polyoxyethylene alkylpropenyl ether sulfate, Daiichi Kogyo Seiyaku Co., Ltd.) 4.0 parts, Adekaria soap NE-20 (α- [1-[(allyloxy) methyl] -2- (nonylphenoxy) ethyl] -ω-hydroxyoxyethylene, manufactured by Asahi Denka Co., Ltd., 80% solution) A monomer emulsion consisting of 1 part and 40 parts of deionized water and an initiator solution consisting of 0.2 part of ammonium persulfate and 10 parts of deionized water were each placed in the reactor for 4 hours using a metering pump. It was dripped in. After completion of the dropping, aging was performed at the same temperature for 1 hour.
Next, the mixture was cooled to 40 ° C. while adding 10 parts of a 1% by mass dimethylaminoethanol aqueous solution, and then filtered through a 300 mesh nylon cloth.
[Mass ratio of monomer (a)] / [Mass ratio of monomer (b)] = 80/20, and a coating resin composition having an average particle size of 80 nm and a solid content of 30% by mass was obtained.

Evaluation of adhesion, water resistance, alcohol resistance, and chemical resistance in Examples and Comparative Examples was performed by the following methods.
[Adhesion test with substrate]
133.3 g of the obtained coating resin composition was adjusted to pH 8.0, 16 g of diethylene glycol monobutyl ether was added as a film-forming aid, stirred with a disper so that the dry film thickness was 25 μm on each resin molded plate. Applied. Then, it dried for 20 minutes in 70 degreeC atmosphere, the coating film was hardened, and it was set as the test piece. Next, on the coating surface, 11 cuts were made at intervals of 1 mm in length and breadth so as to reach the substrate to make 100 grids, and an adhesive tape was attached thereon. Then, this adhesive tape was peeled off rapidly, the state of the coating film was observed, and the following reference | standard evaluated.
○: No peeling at all.
(Triangle | delta): The coating film peeled in 1-50 places.
X: The coating film was peeled off at 51 to 100 locations.

[Water resistance test]
A test piece prepared in the same manner as in the adhesion test was immersed in warm water at 40 ° C. for 3 days, and the appearance of the coating film was evaluated according to the following criteria. Moreover, the adhesiveness test was done with the evaluation method similar to the above.
Appearance state ○: No abnormality at all.
Δ: Some whitening or swelling occurs.
X: There are whitening, swelling, etc. on the entire surface.

[Alcohol resistance]
A test piece prepared in the same manner as in the adhesion test was subjected to 200 reciprocations of a 5-layer gauze impregnated with ethanol on the coating film under a load of 1 kgf / cm ^{2 to determine} the state of scratches on the coating film. Observed and evaluated according to the following criteria.
A: No scratches are observed.
○: Scratches are slightly observed.
Δ: Although scratches are observed, the substrate is not exposed.
X: The base material is exposed.

[chemical resistance]
A test piece prepared in the same manner as in the adhesion test was immersed in castor oil at 60 ° C. for 24 hours, and then the appearance of the coating film was observed and evaluated according to the following criteria.
A: No abnormality at all.
○: The coating film is slightly eluted.
(Triangle | delta): The coating film has eluted considerably.
X: The base material is exposed.
Table 2 shows the evaluation results of Examples 1-2 and Comparative Examples 1-2.

In Examples 1 and 2 which are resin compositions for paints of the present invention, the adhesion between the substrate and the coating film is high regardless of whether the substrate is ABS or PPO. Moreover, the water resistance, alcohol resistance, and chemical resistance of the formed coating film are all excellent. As described above, even if the base material is ABS or PPO, it has adhesion, water resistance, alcohol resistance, and chemical resistance.
On the other hand, in Comparative Example 1 that does not contain the aromatic vinyl monomer (b ₁ ), when the base material is ABS, the base material and the coating film show good adhesion, but the coating film is resistant to alcohol. The nature is low. Moreover, when a base material is PPO, the adhesiveness of a base material and a coating film, the water resistance of a coating film, and alcohol resistance are low. In Comparative Example 2 that does not include the cyano group-containing vinyl monomer (a ₁ ), when the base material is ABS, the adhesion between the base material and the coating film, the water resistance of the coating film, and the chemical resistance are high. Very low. When the substrate is PPO, the adhesion between the substrate and the coating film and the water resistance of the coating film are not sufficient, and the chemical resistance is low.

  According to the method for producing a resin composition for paints of the present invention, for example, it exhibits excellent adhesion to various substrates such as metal, wood, paper, and plastic, and has water resistance, alcohol resistance, and chemical resistance. A coating resin composition capable of forming an excellent coating film can be produced. Moreover, such an effect of the resin composition for coatings of the present invention is particularly effective for a plastic substrate which has been difficult with conventional water-based coatings, and is extremely effective industrially.

Claims (3)

From 50.0 to 99.9% by mass of a cyano group-containing vinyl monomer (a ₁ ) and 0.1 to 50.0% by mass of another copolymerizable vinyl monomer (a ₂ ). Polymerizing the monomer (a), followed by 40.0 to 99.0% by weight of the aromatic vinyl monomer (b ₁ ) and 0.1 to 10.0% by weight of acid. A monomer (b) comprising a group-containing vinyl monomer (b ₂ ) and 0.9 to 59.9% by mass of another copolymerizable vinyl monomer (b ₃ ); A method for producing a resin composition for coatings, comprising a step of polymerizing.   The mass ratio of the monomer (a) to the monomer (b) is [mass ratio of monomer (a)] / [mass ratio of monomer (b)] = 10/90 to 90/10. The manufacturing method of the resin composition for coating materials of Claim 1 which is.   The coating material containing the resin composition for coating materials manufactured by the manufacturing method of Claim 1 or 2.