KR20220112689A - Coating composition, coating film, and an article comprising the film - Google Patents

Abstract

The present invention provides a coating composition which is a polymer comprising a mixture containing (A) following component of (a1) an organopolysiloxane represented by a specific formula and (a2) two or more acrylic monomers and contains a silicone acrylic copolymer resin from which the acrylic monomer of a component (a2) is prepared and (B) at least one organic solvent selected from a specific group such that a glass transition temperature (Tg) of the acrylic polymer obtained by polymerizing (a2) the component is less than 60℃ from the Tg calculated using Fox formula from the glass transition temperature (Tg) of the homopolymer of each acrylic monomer, a coating film, and a synthetic leather or resin article having the coating film. According to the present invention, when the coating composition is used as a coating film, excellent tactile feel and gloss can be imparted, and even when the article having the coating film is pulled, whitening does not occur and the appearance is not damaged.

Description

Coating composition, coating film, and article having the coating film

The present invention relates to a coating composition containing a silicone acrylic copolymer resin, a coating film formed by drying the composition, and an article having the film. More specifically, by coating on the surface of a base material such as leather or resin, excellent tactile feel and gloss can be imparted, and the coating composition, which does not impair the appearance even when an article having a coating film is pulled, has a coating film and a coating film having the film It's about goods.

DESCRIPTION OF RELATED ART Conventionally, silicone resin is used for the purpose of providing slidability to base materials, such as leather and resin. As a method of improving the abrasion resistance and activity of leather, it is known to knead a silicone component such as silicone oil or silicone powder into a resin when manufacturing leather. For example, in Japanese Patent Application Laid-Open No. 2007-138326 (Patent Document 1), which manufactures synthetic leather by kneading acryl-silicone copolymer particles with a urethane-based elastomer, improvement of abrasion resistance has been successful. However, in this case, since the powder is kneaded into the resin, the manufacturing process is complicated. In addition, in order to obtain abrasion resistance performance, it is necessary to increase the amount of the acryl-silicon copolymer particles added.

In order to solve this problem, there is a method of coating a resin or the like on the surface of leather such as natural leather or synthetic leather. Japanese Patent Laid-Open No. 2007-314919 (Patent Document 2) discloses improving abrasion resistance by coating an artificial leather with a surface finishing agent obtained by adding a crosslinking agent and polyether-modified silicone to an aqueous polyurethane resin. However, in this case, since the hydrophilicity of the surface finishing agent becomes stronger, for example, when a drink or liquid with a dark color such as coffee adheres, the color transfers to the leather, and the color of the fiber transfers to the leather when the clothing rubs. There is concern that the antifouling property of the leather surface will be lost.

Also, as a method of improving the antifouling property of leather, a method of coating a resin or the like on the surface of the leather is known. Japanese Patent Application Laid-Open No. 2010-241963 (Patent Document 3) discloses that an acrylic resin, an acrylic silica resin, an acrylic polysiloxane resin, and a silicone-based tactile agent are blended and coated on natural leather. Japanese Patent Laid-Open No. 2008-308785 (Patent Document 4) discloses forming a silicone resin film on the surface of synthetic leather containing a urethane resin. However, in the water-based coating agent, the performance of water resistance and antifouling|stain-resistant property was inadequate.

International Publication No. 2019/244321 (Patent Document 5) discloses a synthetic leather coated with a treatment solution in which a base resin and a silicone acrylic resin are dissolved in an organic solvent. Although the antifouling property is improved compared with the conventional method, this method has a problem of whitening when the coated leather is pulled, and there is room for improvement.

Japanese Patent Laid-Open No. 2007-138326 Japanese Patent Laid-Open No. 2007-314919 Japanese Patent Laid-Open No. 2010-241963 Japanese Patent Laid-Open No. 2008-308785 International Publication No. 2019/244321

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a coating composition having excellent tactile feel and gloss, a coating film that does not whiten even when pulled, and an article having the film.

As a result of intensive studies to achieve the above object, the present inventors have found that, in a coating composition containing a silicone acrylic copolymer resin, homopolymers of two or more acrylic monomers used for grafting to an organopolysiloxane (silicone resin) are homopolymers of each monomer. An acrylic monomer whose Tg (hereinafter referred to as "calculated Tg"), which is calculated by the predetermined formula, is within a predetermined range, is used, and a specific silicone acrylic copolymer resin, which is a polymer containing these acrylic monomers and organopolysiloxane, is organic It has been discovered that, by dissolving in a solvent, the coating composition not only has excellent tactile feel and gloss, but also does not whiten and does not impair the appearance even when a coating film containing the coating composition and an article having the coating are pulled, and the present invention has come to achieve

Accordingly, the present invention provides a coating composition containing a silicone acrylic copolymer resin, a coating film formed by drying the composition, and an article having the coating film.

1. (A) (a1) a polymer comprising 50 to 99 parts by mass of an organopolysiloxane represented by the following general formula (1) and 1 to 50 parts by mass of a mixture containing (a2) two or more acrylic monomers, ( a2) so that the glass transition temperature (Tg) of the acrylic polymer obtained by polymerizing the component is less than 60° C. as Tg calculated using the Fox equation from the homopolymer glass transition temperature (Tg) of each acrylic monomer (a2) ) silicone acrylic copolymer resin in which the acrylic monomer of the component is prepared, and

(B) at least one organic solvent selected from the group consisting of amide compounds, ether compounds, ketone compounds, aromatic hydrocarbons and acetate esters;

A coating composition comprising:

(Wherein, R ¹ is the same or different unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ² is an alkyl group having 1 to 6 carbon atoms substituted with a mercapto group, acryloxy group or methacryloxy group. X is the same or different unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, alkoxy group or hydroxyl group having 1 to 20 carbon atoms, Y is X or -[O-Si(X) ₂ ] _d - is the same or different groups represented by X, and at least two of X and Y are hydroxyl groups. Z is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group. a is 0 to 1,000 is a positive number, b is a positive number from 100 to 10,000, c is a positive number from 1 to 10, and d is a positive number from 1 to 1,000.)

2. The organic solvent of component (B) is N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,4-dioxane, 1,3-dioxolane, The coating composition according to 1 above, selected from the group consisting of tetrahydrofuran, methyl ethyl ketone, cyclopentanone, cyclohexanone, toluene, xylene, ethyl acetate and propylene glycol monoethyl ether acetate.

3. The coating composition according to 1 or 2, wherein the silicone acrylic copolymer resin as component (A) is an emulsion graft polymer of a mixture of component (a1) and component (a2).

4. The organopolysiloxane represented by the formula (1) is represented by a cyclic organosiloxane, α,ω-dihydroxysiloxane oligomer, α,ω-dialkoxysiloxane oligomer or alkoxysilane, and the following general formula (2) The coating composition according to any one of 1 to 3 above, which is a polymer with a silane coupling agent to be used.

R ³ _(4-ef) R ⁴ _f Si(OR ⁵ ) _e (2)

(Wherein, R ³ is an alkyl group having 1 to 6 carbon atoms substituted with a mercapto group, acryloxy group or methacryloxy group, R ⁴ is an alkyl group having 1 to 4 carbon atoms, R ⁵ is an alkyl group having 1 to 4 carbon atoms, e is 2 or 3, f is 0 or 1, e+f is 2 or 3.)

5. The mixture of the component (a2) is at least two kinds of a monomer having a glass transition temperature (Tg) of 50°C or higher of the homopolymer and a monomer having a glass transition temperature (Tg) of less than 50°C of the homopolymer. The coating composition according to any one of 1 to 4 above, containing the above monomers.

6. The coating composition according to any one of 1 to 5, wherein the organopolysiloxane weight average molecular weight of the component (a1) is 100,000 to 500,000.

7. A coating film formed by drying the coating composition according to any one of 1 to 6.

8. A synthetic leather or resin article having the coating film according to 7 above.

By dissolving a specific silicone acrylic copolymer resin in an organic solvent, the coating composition of the present invention can impart excellent feel and gloss when the coating composition is used as a coating film, and whitening does not occur even when an article having a coating film is pulled. does not damage the appearance.

The coating composition of this invention contains (A) specific silicone acrylic copolymer resin and (B) organic solvent.

Hereinafter, each component is demonstrated in detail.

The silicone acrylic copolymer resin as component (A) is a polymer of an organopolysiloxane and an acrylic monomer represented by a specific formula, preferably (a1) an organopolysiloxane represented by the following general formula (1), (a2) It is obtained by emulsion graft polymerization of the mixture containing two or more types of acrylic monomers.

Here, (a1) the organopolysiloxane is represented by the following general formula (1).

(Wherein, R ¹ is the same or different unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ² is an alkyl group having 1 to 6 carbon atoms substituted with a mercapto group, acryloxy group or methacryloxy group. X is the same or different unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, alkoxy group or hydroxyl group having 1 to 20 carbon atoms, Y is X or -[O-Si(X) ₂ ] _d - is the same or different groups represented by X, and at least two of X and Y are hydroxyl groups. Z is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group. a is 0 to 1,000 is a positive number, b is a positive number from 100 to 10,000, c is a positive number from 1 to 10, and d is a positive number from 1 to 1,000.)

Here, R ¹ is the same or different unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, Alkyl groups such as nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, cycloalkyl group such as cyclopentyl group, cyclohexyl group, cycloheptyl group, alkenyl group such as vinyl group and allyl group Aryl groups such as phenyl group, tolyl group and naphthyl group, alkenylaryl groups such as vinylphenyl group, aralkyl groups such as benzyl group, phenylethyl group and phenylpropyl group, alkenyl aralkyl groups such as vinylbenzyl group and vinylphenylpropyl group, etc. However, some or all of the hydrogen atoms of these groups are halogen atoms such as fluorine, bromine, chlorine, acryloxy group, methacryloxy group, carboxyl group, alkoxy group, alkenyloxy group, amino group, alkyl or alkoxy or (meth)acryl group and those substituted with an oxy-substituted amino group or the like. As R ¹ , it is preferably a methyl group.

R ² is an alkyl group having 1 to 6 carbon atoms substituted with a mercapto group, an acryloxy group, or a methacryloxy group. Specifically, a mercaptopropyl group, an acryloxypropyl group, a methacryloxypropyl group, etc. are preferable.

X is the same or different unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or a hydroxyl group, and as an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, Examples similar to those exemplified by R ¹ can be exemplified, and as the alkoxy group having 1 to 20 carbon atoms, specifically, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a hexyloxy group, a heptyloxy group, an octyloxy group , a decyloxy group, a tetradecyloxy group, and the like. As X, Preferably they are a hydroxyl group, a methyl group, a butyl group, and a phenyl group.

Y is the same or different group represented by X or -[O-Si(X) ₂ ] _d -X. d is a positive number from 1 to 1,000, preferably a positive number from 1 to 200. Further, in the present invention, from the viewpoint of crosslinking properties, it has at least two, preferably 2 to 4 hydroxyl groups in one molecule, that is, among the above X and Y, and it is preferable to have it at both terminals.

Z is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group, preferably a hydroxyl group or a methyl group.

When a is greater than 1,000, the strength of the obtained cured product becomes insufficient, so it becomes a positive number of 0 to 1,000, preferably a positive number of 0 to 200, b is less than 100, the cured product lacks flexibility, and when it is greater than 10,000, the cured product obtained Since the tear strength falls, it becomes a positive number of 100-10,000, Preferably it becomes a positive number of 1,000-5,000. c is a positive number of 1 to 10, and when it exceeds 10, gelling particles are likely to form during the reaction. In addition, the arrangement of the repeating units may be a block or may be random.

It is preferable that such (a1) organopolysiloxane is used in the form of an emulsion, and a commercial item may be used and may be synthesize|combined. In the case of synthesis, it can be carried out by a known emulsion polymerization method, for example, having a halogen atom such as a fluorine atom, a (meth)acryloxy group, a carboxyl group, an alkoxy group, an alkenyloxy group, a hydroxyl group, an amino group, etc. cyclic organosiloxane, α,ω-dihydroxysiloxane oligomer, α,ω-dialkoxysiloxane oligomer, alkoxysilane, etc., and a silane coupling agent represented by the following general formula (2) using a surfactant After emulsification-dispersing in water, it can synthesize|combine easily by adding catalysts, such as an acid, as needed, and performing a polymerization reaction.

R ³ _(4-ef) R ⁴ _f Si(OR ⁵ ) _e (2)

(Wherein, R ³ is an alkyl group having 1 to 6 carbon atoms substituted with a mercapto group, acryloxy group or methacryloxy group, R ⁴ is an alkyl group having 1 to 4 carbon atoms, R ⁵ is an alkyl group having 1 to 4 carbon atoms, e is 2 or 3, f is 0 or 1, e+f is 2 or 3.)

Specific examples of the cyclic organosiloxane include hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), 1,1 -diethylhexamethylcyclotetrasiloxane, phenylheptamethylcyclotetrasiloxane, 1,1-diphenylhexamethylcyclotetrasiloxane, 1,3,5,7-tetravinyl tetramethylcyclotetrasiloxane, 1,3,5, 7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetracyclohexyltetramethylcyclotetrasiloxane, tris(3,3,3-trifluoropropyl)trimethylcyclotrisiloxane, 1,3,5,7 -tetra(3-methacryloxypropyl)tetramethylcyclotetrasiloxane, 1,3,5,7-tetra(3-acryloxypropyl)tetramethylcyclotetrasiloxane, 1,3,5,7-tetra(3- Carboxypropyl)tetramethylcyclotetrasiloxane, 1,3,5,7-tetra(3-vinyloxypropyl)tetramethylcyclotetrasiloxane, 1,3,5,7-tetra(p-vinylphenyl)tetramethylcyclotetra Siloxane, 1,3,5,7-tetra[3-(p-vinylphenyl)propyl]tetramethylcyclotetrasiloxane, 1,3,5,7-tetra(N-acryloyl-N-methyl-3- aminopropyl)tetramethylcyclotetrasiloxane, 1,3,5,7-tetra(N,N-bis(lauroyl)-3-aminopropyl)tetramethylcyclotetrasiloxane, and the like are exemplified. Preferably, octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane are used.

As the silane coupling agent, specifically, γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane, γ-(meth)acryloxypropyltripropoxysilane, γ- (meth)acryloxypropyltriisopropoxysilane, γ-(meth)acryloxypropyltributoxysilane, γ-(meth)acryloxypropylmethyldimethoxysilane, γ-(meth)acryloxypropylmethyldiethoxysilane acrylsilanes such as , γ-(meth)acryloxypropylmethyldipropoxysilane, γ-(meth)acryloxypropylmethyldiisopropoxysilane, and γ-(meth)acryloxypropylmethyldibutoxysilane; Mercaptosilanes, such as (gamma)-mercaptopropylmethyldimethoxysilane and (gamma)-mercaptopropyl trimethoxysilane, etc. are mentioned. Alternatively, the oligomer obtained by polycondensation of these may be more preferable because the generation of alcohol is suppressed. Here, (meth)acryloxy represents acryloxy or methacryloxy.

It is preferable to use 0.01-20 mass parts of these silane coupling agents with respect to 100 mass parts of cyclic organosiloxane, α,ω-dihydroxysiloxane oligomer, α,ω-dialkoxysiloxane oligomer, or alkoxysilane, 0.01 to The use of 5 parts by mass is more preferable.

By copolymerizing a silane coupling agent, it becomes organopolysiloxane which has the siloxane unit of c in Formula (1), and the effect of grafting the monomer of (a2) component is acquired.

The said reaction WHEREIN: As a catalyst used for superposition|polymerization, what is necessary is just to use a well-known polymerization catalyst. Among these, a strong acid is preferable, and hydrochloric acid, sulfuric acid, dodecylbenzenesulfonic acid, citric acid, lactic acid, and ascorbic acid are exemplified. Preferably it is dodecylbenzenesulfonic acid which has emulsifying ability.

The amount of the acid catalyst used is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 10 parts by mass based on 100 parts by mass of the cyclic organosiloxane, α,ω-dihydroxysiloxane oligomer, α,ω-dialkoxysiloxane oligomer or alkoxysilane. It is 0.2-2 mass parts.

Examples of the surfactant used for polymerization include sodium lauryl sulfate, sodium laureth sulfate, N-acylamino acid salt, N-acyl taurine salt, aliphatic soap, and alkyl phosphate salt. It is easy to melt|dissolve in , and it is preferable that it does not have a polyethylene oxide chain. More preferably, they are N-acylamino acid salt, N-acyl taurine salt, an aliphatic soap, and an alkyl phosphate, Especially preferably, they are sodium lauroyl methyl taurine, myristoyl methyl taurine sodium, and sodium lauryl sulfate.

The amount of the anionic surfactant used is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the cyclic organosiloxane, α,ω-dihydroxysiloxane oligomer, α,ω-dialkoxysiloxane oligomer or alkoxysilane. Preferably it is 0.5-10 mass parts.

The polymerization temperature is preferably 50 to 75°C, the polymerization time is preferably 10 hours or more, and more preferably 15 hours or more. In addition, it is particularly preferable to aging at 5 to 30° C. for 10 hours or more after polymerization. Moreover, it is preferable that the pH of the obtained polymerization solution is 6-8.

It is preferable that the weight average molecular weights of the obtained (a1) organopolysiloxane are 100,000 - 500,000, More preferably, it is 150,000 - 450,000. By setting it as this weight average molecular weight, the coating agent (coating composition) which provides favorable lubricity peculiar to silicone is obtained. In the present invention, the weight average molecular weight (Mw) can be calculated from the specific viscosity ηsp (25°C) of the organopolysiloxane toluene solution having a concentration of 1 g/100 ml.

ηsp=(η/η0)-1

(η0: viscosity of toluene η: viscosity of solution)

ηsp=[η]+0.3[η] ²

[η]=2.15×10 ^-4 M ^0.65

Specifically, 20 g of the emulsion is mixed with 20 g of IPA (isopropyl alcohol), the emulsion is broken, the IPA is discarded, and the remaining rubbery organopolysiloxane is dried at 105° C. for 3 hours. Let this be organopolysiloxane toluene solution with a concentration of 1 g/100 ml, and measurement is performed at 25° C. with an Ubbelode viscometer. The molecular weight can be obtained by substituting the viscosity into the above formula (References: Nakamuta, Nikka, 77 858 [1956], Doklady Akad. Nauk. U.S.S.R. 89 65 [1953]).

In the above reaction, for example, when octamethyltetrasiloxane is used as the cyclic organosiloxane and γ-methacryloxypropylmethyldimethoxysilane is used as the silane coupling agent, it is as follows.

The component (a2) of this invention is a mixture containing 2 or more types of acrylic monomers. Here, acrylic acid, methacrylic acid, acrylic acid ester, and methacrylic acid ester are mentioned as an acryl-type monomer (Hereinafter, it may call an "acrylic component"). It is preferable that they are acrylic acid ester and methacrylic acid ester. Specifically, methyl methacrylate, ethyl methacrylate, butyl methacrylate, allyl methacrylate, t-butyl methacrylate, glycidyl methacrylate, cyclohexyl methacrylate, lauryl methacrylate, methacrylate Stearyl acrylate, behenyl methacrylate, urea methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, isobutyl acrylate, t-butyl acrylate, glycidyl acrylate, isodecyl acrylate, hexyl acrylate , lauryl acrylate, dodecyl acrylate, stearyl acrylate, hydroxypropyl acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, ethyldiglycol acrylate, dihydrocyclopentadiethyl acrylate, and the like. . Two or more types can be used for these. In particular, it is preferable to select 3 or more and 10 or less acrylic monomers.

With respect to the component (a2), the glass transition temperature (Tg) of the acrylic polymer obtained by polymerizing the acrylic component of the component (a2) (referred to as “the polymer of the acrylic component”) is the homopolymer glass transition temperature of each acrylic monomer. The kind and compounding quantity of the acrylic monomer in the said (a2) component are selected suitably so that it may become less than 60 degreeC in Tg calculated using Fox formula from (Tg). (Tg) calculated using the polymer of this acrylic component and Fox's formula specifically means the glass transition temperature calculated|required by the following formula.

That is, the polymer glass transition temperature (K) of the acrylic component is Tg, and in the n types of acrylic monomers used, the homopolymer glass transition temperature (K) of each acrylic monomer is Tg1, Tg2, ... Tgn, When content (mass %) of each acrylic monomer is made into P1, P2, ... Pn, it will show by following formula (I).

(P1+P2+…Pn)/Tg=(P1/Tg1)+(P2/Tg2)+…+(Pn/Tgn) (I)

In addition, it is P1+P2+...Pn=100 (mass %), and the homopolymer glass transition temperature (K) of each said acrylic monomer can be measured based on JISK7121.

In the present invention, it is characterized in that the glass transition temperature (hereinafter, simply referred to as "calculated Tg") calculated by the formula (I) is less than 60°C, more preferably 55°C or less, still more preferably It is preferably below 50°C. On the other hand, as the lower limit, Preferably it is 30 degreeC or more, More preferably, it is 40 degreeC or more. When the calculated Tg exceeds 60° C., the coating film is whitened when pulled, and the effect of the present invention cannot be obtained.

With respect to the mixture of the component (a2), two or more types of a monomer having a glass transition temperature (Tg) of 50° C. or higher of a homopolymer and a monomer having a glass transition temperature (Tg) of a homopolymer of less than 50° C. It is preferable to contain As the reason, by using a monomer having a Tg of the homopolymer of 50 ° C. or higher, the fluidity of the powder when dried and powdered is secured, and flexibility is given to the polymer by using a monomer having a Tg of the homopolymer of less than 50 ° C. Even after being dissolved in a solvent and coated on a substrate, there is a tendency that the coating film containing the coating composition and the article having the coating film are not whitened and the appearance is not impaired even if the article is pulled.

Examples of the acrylic monomer having a homopolymer Tg of 50°C or higher include methyl methacrylate (105°C), acrylic acid (106°C), acrylonitrile (105°C), methacrylic acid (185°C), and allyl methacrylate (52°C). ), 2-hydroxyethyl methacrylate (55°C), isobornyl acrylate (97°C), and ethyl methacrylate (65°C). It is preferable that Tg of a homopolymer contains at least methyl methacrylate as an acryl-type monomer 50 degreeC or more.

On the other hand, as the monomer having a Tg of less than 50°C of the homopolymer, ethyl acrylate (-22°C), butyl acrylate (-52°C), 2-ethylhexyl acrylate (-70°C), isobutyl acrylate (-40°C), acrylic acid and methyl (8°C), n-butyl methacrylate (20°C), isobutyl methacrylate (48°C), and lauryl acrylate (15°C).

The mixing ratio of the monomer having a Tg of 50° C. or higher of the homopolymer and the monomer having a temperature of less than 50° C. is not particularly limited as long as the calculated Tg is designed to be less than 60° C., and in particular, 50 to 99 parts by mass of a monomer having a Tg of the homo polymer of 50° C. or higher. With respect to it, it is preferable that it is 1-50 mass parts of monomers below 50 degreeC. More preferably, it is 20-50 mass parts of monomers whose Tg of a homopolymer is less than 50 degreeC with respect to 50-80 mass parts of monomers 50 degreeC or more.

The organopolysiloxane of the formula (1) obtained as described above preferably has 2 to 10 crosslinking points, preferably 2 to 6 points, per 1 mole of the polymer, and to induce graft polymerization with the component (a2) It is possible.

The silicone acrylic graft copolymer resin, which is the component (A), first graft-polymerizes the (a2) acrylic monomer to the (a1) organopolysiloxane obtained as described above. In this case, it is suitable for (a2) component to carry out emulsion graft polymerization to (a1) component.

In this case, the mass ratio of the organopolysiloxane of Formula (1) to the acrylic monomer at the time of graft polymerization is 50:50-99:1, Preferably it is 60:40-99:1. When the silicone component is less than 50 by mass ratio, sufficient friction resistance may not be expressed.

Moreover, it is preferable to use 1-100 mass parts of said (a2) component with respect to 100 mass parts of said (a1) components, It is more preferable to use 10-100 mass parts, It is to use 20-100 mass parts more preferably.

Here, examples of the radical initiator used for graft polymerization include persulfates such as potassium persulfate and ammonium persulfate, aqueous hydrogen persulfate, t-butyl hydroperoxide, and hydrogen peroxide. If necessary, a redox system in which a reducing agent such as acid sodium sulfite, rongalite, L-ascorbic acid, tartaric acid, saccharides or amines is used in combination can also be used. 0.1-5 mass % of the total amount of (a2) component is preferable, and, as for the usage-amount of a radical initiator, 0.5-3 mass % is more preferable.

When the organopolysiloxane has already been prepared, graft polymerization is sufficiently possible with the surfactant contained in the emulsion, but for stability improvement, as an anionic surfactant, sodium lauryl sulfate, sodium laureth sulfate, N-acylamino acid salt, N- An acyl taurine salt, an aliphatic soap, an alkyl phosphate, etc. can be added. Moreover, nonionic emulsifiers, such as polyoxyethylene lauryl ether and polyoxylentridecyl ether, can also be added. As for the usage-amount in the case of adding surfactant, 0.1-5 mass % of (a2) component is preferable.

In addition, a chain transfer agent may be added in order to adjust the molecular weight of the graft polymer and the graft rate.

The graft polymerization temperature is preferably 25 to 55°C, more preferably 25 to 40°C. Moreover, 2 to 8 hours are preferable and, as for polymerization time, 3 to 6 hours are more preferable.

The silicone acrylic copolymer resin obtained in this way turns into a polymer in which the component (a2) is randomly grafted to the component (a1).

Moreover, it is preferable that the silicone acrylic copolymer resin obtained above is 30-50 mass % as solid content in an emulsion. Moreover, 10-5,000 mPa*s is preferable and, as for the viscosity (25 degreeC) of this emulsion, 50-1,000 mPa*s is more preferable. Viscosity can be measured with a rotational viscometer. The average particle diameter of this emulsion is preferably 1 µm or less, and preferably 0.1 µm (100 nm) to 0.3 µm (300 nm). As for pH, 6-8 are preferable. In addition, an average particle diameter can be measured with a laser diffraction/scattering type particle diameter distribution measuring apparatus.

Since the obtained silicone acrylic graft copolymer resin is in the form of an emulsion, the dispersion is concentrated by methods such as heating dehydration, filtration, centrifugation, decantation, etc. Moisture is removed by heat drying, spray drying in which the dispersion is sprayed in an air stream, heat drying using a fluidized heat medium, or the like, and once dried and powdered. Moreover, as for a drying temperature, 50-200 degreeC is preferable. When the obtained powder is slightly agglomerated, it may be pulverized by appropriately using a pulverizer such as a jet mill, a ball mill, or a hammer mill.

It may wash|clean in order to remove the cyclic organosiloxane and surfactant which remained in the obtained silicone acrylic graft copolymer resin. The solvent in that case is preferably an alcohol-based organic solvent or a hydrocarbon-based organic solvent, and includes a lower alcohol having 1 to 4 carbon atoms and an aliphatic hydrocarbon having 5 to 20 carbon atoms, and specifically, methanol, ethanol, iso Propyl alcohol, hexane and isododecane are more preferred. The washing method collects 100 mass parts of powder in a beaker, adds the said solvent 5 times or more of the mass, for example, stirs for several hours, and carries out suction filtration. After that, washing with the same solvent or washing with a solvent that dissolves in water such as alcohol is more effective. In this case, it is usually carried out at room temperature (25° C.), but may be heated in some cases.

In the case of washing, it is re-dried to form powder, but the filtered powder is simply dried at a temperature of 40°C or higher and 200°C or lower with a dryer for several hours, or a fluidized dryer or the like may be used.

As for the silicone acrylic copolymer resin obtained in this way, it is preferable that an average particle diameter is 100 micrometers or less, especially 10-50 micrometers. In addition, the said average particle diameter means the particle diameter measured by the dynamic light scattering method.

(B) Examples of the organic solvent include amide compounds such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; ether compounds such as 1,4-dioxane, 1,3-dioxolane, and tetrahydrofuran; ketone compounds such as methyl ethyl ketone, cyclopentanone, and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; Acetic acid esters, such as ethyl acetate and a propylene glycol monoethyl ether acetate, are mentioned. The organic solvent may be used independently and may be mixed and used for it.

(A) Although the compounding quantity of a specific silicone acrylic copolymer resin will not be specifically limited if it is an amount which can melt|dissolve in (B) organic solvent, 1-60 mass parts is preferable with respect to 100 mass parts of (B) organic solvents, and it is preferable Preferably it is 10-50 mass parts.

The coating composition of this invention is obtained by mixing and dissolving (A) silicone acrylic copolymer resin and (B) organic solvent by well-known mixing preparation methods, such as a propeller type stirrer, a homogenizer, a ball mill, and a bead mill.

In addition, in the coating composition of the present invention, to the extent that the performance is not affected, resins, pigments, matting agents, antioxidants, ultraviolet absorbers, anti-freezing agents, pH adjusters, preservatives, defoamers, antibacterial agents, molds other than component (A) You may add organic solvents, such as an antioxidant, a light stabilizer, an antistatic agent, a plasticizer, a flame retardant, a thickener, surfactant, and a film forming aid, other resin, etc.

When the coating composition of the present invention obtained in this way is applied, immersed, and dried (room temperature to 150° C.) on one or both surfaces of a base material such as synthetic leather or resin, excellent tactile feel and gloss can be imparted, and articles having a coating film It is characterized in that it does not damage the appearance even when pulled.

Here, the synthetic leather is one in which a vinyl chloride-based resin and polyurethane are formed on the base material, and the resin base material is poly(meth)acrylic acid ester such as polymethyl methacrylate, polycarbonate, polystyrene, polyethylene terephthalate, polyvinyl chloride. , polyester, cellulose, diethylene glycol bisallyl carbonate polymer, acrylonitrile-butadiene-styrene polymer, polyurethane, and epoxy resin are used. As a method of drying, although a method of leaving to stand at room temperature for 1 to 10 days is mentioned, From a viewpoint of advancing hardening rapidly, the method of heating at the temperature of 20-150 degreeC for 1 second to 10 hours is preferable. In addition, when the resin substrate includes a material that is liable to cause deformation or discoloration by heating, drying is preferably performed at a relatively low temperature of 20 to 100°C.

The method of applying the coating composition of the present invention to the substrate is not particularly limited, but for example, a gravure coater, a bar coater, a blade coater, a roll coater, an air knife coater, a screen coater, application by various coaters such as a curtain coater Method, spray application|coating, immersion, brush application, etc. are mentioned.

The coating amount of the coating composition of the present invention to the substrate is not particularly limited, but usually in terms of solid content from the viewpoint of antifouling properties, construction workability, etc., preferably 1 to 300 g/m 2 , more preferably 5 to 100 g/m 2 What is necessary is just to form it in the range of m<2> or thickness 1 to 500 micrometers, preferably 5 to 100 micrometers, and just to form a film by natural drying or heating-drying at 100-200 degreeC.

The coating composition of the present invention is characterized in that it can impart excellent tactile feel and gloss by using it for synthetic leather or resin products, and does not impair its appearance even when an article having a coating film is pulled.

Although the base material to which the coating composition of this invention is coated is not specifically limited, By setting it as synthetic leather or resin product with a thickness of 0.1-10 mm, which is a well-known film thickness range, the performance of not impairing an external appearance even if pulling is effectively exhibited. do.

Example

Hereinafter, production examples, examples and comparative examples are shown and the present invention will be specifically described, but the present invention is not limited to the following examples. In addition, in the following example, a part and % represent a mass part and mass %, respectively.

[Production Example 1]

(a1) Preparation of emulsion composition containing organopolysiloxane

828 g of octamethylcyclotetrasiloxane, 0.7 g of 3-methacryloxypropyldimethoxysilane, 8.3 g of sodium lauryl sulfate dissolved in 75 g of pure water, and 8.3 g of dodecylbenzenesulfonic acid dissolved in 75 g of pure water were placed in a 2L polyethylene beaker. After pouring in and uniformly emulsifying with a homomixer, 629 g of pure water was gradually added and diluted, and passed twice through a high-pressure homogenizer at a pressure of 300 kgf/cm 2 to obtain a uniform white emulsion. This emulsion was transferred to a 2L glass flask equipped with a stirring device, a thermometer, and a reflux condenser, polymerized at 55 ° C. for 24 hours, aged at 15 ° C. for 24 hours, and then neutralized to pH 6-8 with 27 g of 10% sodium carbonate aqueous solution. , to obtain a silicone emulsion composition. This emulsion had a non-volatile content of 45.4% after drying at 105°C for 3 hours, and the organopolysiloxane in the emulsion was in the form of a non-flowing soft gel. The structure of the organopolysiloxane obtained by the polymerization reaction is ¹ H-NMR (frequency 600 MHz, room temperature, integration number 128) and ²⁹ Si-NMR (frequency 600 MHz, room temperature, integration number 5,000 times) (device name: JNM) -ECA600, measurement solvent: CDCl ₃ ) was confirmed. In addition, the weight average molecular weight (Mw) of organopolysiloxane (a1) was measured as mentioned above, and is shown in Table 1.

Preparation of (A) silicone acrylic graft copolymer resin of Preparation Example 1

Methyl methacrylate (MMA), butyl acrylate (BA), and allyl methacrylate (AMA) were added to the silicone emulsion composition obtained above in a ratio of MMA/BA/AMA=75.8/24/0.2 (%) of 3 to 5 While dripping over time, a peroxide and a reducing agent were added at room temperature to carry out a redox reaction, and acrylic graft copolymerization was performed to obtain about 45% acrylic silicone resin emulsion (acrylic modified organopolysiloxane) containing silicone acrylic graft copolymer resin. . The average particle diameter of this emulsion was 280 nm. In addition, the calculated Tg of the acrylic component is methyl methacrylate (homopolymer Tg: 105°C), butyl acrylate (homopolymer Tg: -52°C), and allyl methacrylate (homopolymer Tg: 52°C) by the above mass The ratio was 50°C as calculated using the above-mentioned formula. In addition, the said Tg is a measured value based on JISK7121. By spray-drying this, silicone acrylic copolymer resin powder (Production Example 1) was obtained. In addition, although the weight average molecular weight (Mw) of (a1) is shown in Table 1, this Mw was measured by the said method.

[Production Example 2]

(a1) Preparation of emulsion composition containing organopolysiloxane

828 g of octamethylcyclotetrasiloxane, 0.7 g of 3-methacryloxypropyldimethoxysilane, 8.3 g of sodium lauryl sulfate dissolved in 75 g of pure water, and 8.3 g of dodecylbenzenesulfonic acid dissolved in 75 g of pure water were placed in a 2L polyethylene beaker. After pouring in and uniformly emulsifying with a homomixer, 629 g of pure water was gradually added and diluted, and passed twice through a high-pressure homogenizer at a pressure of 300 kgf/cm 2 to obtain a uniform white emulsion. This emulsion was transferred to a 2L glass flask equipped with a stirring device, a thermometer, and a reflux condenser, polymerized at 55 ° C. for 24 hours, aged at 15 ° C. for 24 hours, and then neutralized to pH 6-8 with 27 g of 10% sodium carbonate aqueous solution. , to obtain a silicone emulsion composition. This emulsion had a non-volatile content of 45.4% after drying at 105°C for 3 hours, and the organopolysiloxane in the emulsion was in the form of a non-flowing soft gel.

Preparation of (A) silicone acrylic graft copolymer resin of Preparation Example 2

Methyl methacrylate (MMA), butyl acrylate (BA), and allyl methacrylate (AMA) were added to the silicone emulsion composition obtained above in a ratio of MMA/BA/AMA=70.5/29.3/0.2 (%) of 3 to 5 While dripping over time, a peroxide and a reducing agent were added at room temperature to carry out a redox reaction, and acrylic graft copolymerization was performed to obtain about 45% acrylic silicone resin emulsion (acrylic modified organopolysiloxane) containing silicone acrylic graft copolymer resin. . The average particle diameter of this emulsion was 270 nm. In addition, the calculated Tg of the acrylic component is methyl methacrylate (homopolymer Tg: 105°C), butyl acrylate (homopolymer Tg: -52°C), and allyl methacrylate (homopolymer Tg: 52°C) as described above. It was 40 degreeC when calculated using the above-mentioned formula as a mass ratio. By spray-drying this, silicone acrylic copolymer resin powder (Production Example 2) was obtained.

[Production Example 3]

(a1) Preparation of emulsion composition containing organopolysiloxane

828 g of octamethylcyclotetrasiloxane, 0.7 g of 3-methacryloxypropyldimethoxysilane, 8.3 g of sodium lauryl sulfate dissolved in 75 g of pure water, and 8.3 g of dodecylbenzenesulfonic acid dissolved in 75 g of pure water were placed in a 2L polyethylene beaker. After pouring in and uniformly emulsifying with a homomixer, 629 g of pure water was gradually added and diluted, and passed twice through a high-pressure homogenizer at a pressure of 300 kgf/cm 2 to obtain a uniform white emulsion. This emulsion was transferred to a 2L glass flask equipped with a stirrer, thermometer and reflux condenser, polymerized at 55 ° C. for 24 hours, aged at 10 ° C. for 24 hours, and then neutralized to pH 6-8 with 27 g of 10% aqueous sodium carbonate solution. , to obtain a silicone emulsion composition. This emulsion had a non-volatile content of 45.4% after drying at 105°C for 3 hours, and the organopolysiloxane in the emulsion was in the form of a non-flowing soft gel.

Preparation of (A) silicone acrylic graft copolymer resin of Preparation Example 3

Methyl methacrylate (MMA), butyl acrylate (BA), and allyl methacrylate (AMA) were added to the silicone emulsion composition obtained above in a ratio of MMA/BA/AMA=75.8/24/0.2 (%) of 3 to 5 While dripping over time, a peroxide and a reducing agent were added at room temperature to carry out a redox reaction, and acrylic graft copolymerization was performed to obtain about 45% acrylic silicone resin emulsion (acrylic modified organopolysiloxane) containing silicone acrylic graft copolymer resin. . The average particle diameter of this emulsion was 280 nm. In addition, the calculated Tg of the acrylic component is methyl methacrylate (homopolymer Tg: 105°C), butyl acrylate (homopolymer Tg: -52°C), and allyl methacrylate (homopolymer Tg: 52°C) as described above. It was 50 degreeC when calculated using the above-mentioned formula as a mass ratio. By spray-drying this, silicone acrylic copolymer resin powder (Production Example 3) was obtained.

[Production Example 4]

(a1) Preparation of emulsion composition containing organopolysiloxane

828 g of octamethylcyclotetrasiloxane, 0.7 g of 3-methacryloxypropyldimethoxysilane, 8.3 g of sodium lauryl sulfate dissolved in 75 g of pure water, and 8.3 g of dodecylbenzenesulfonic acid dissolved in 75 g of pure water were placed in a 2L polyethylene beaker. After pouring in and uniformly emulsifying with a homomixer, 629 g of pure water was gradually added and diluted, and passed twice through a high-pressure homogenizer at a pressure of 300 kgf/cm 2 to obtain a uniform white emulsion. This emulsion was transferred to a 2L glass flask equipped with a stirring device, a thermometer, and a reflux condenser, polymerized at 55 ° C. for 24 hours, aged at 15 ° C. for 24 hours, and then neutralized to pH 6-8 with 27 g of 10% sodium carbonate aqueous solution. , to obtain a silicone emulsion composition. This emulsion had a non-volatile content of 45.4% after drying at 105°C for 3 hours, and the organopolysiloxane in the emulsion was in the form of a non-flowing soft gel.

Preparation of (A) silicone acrylic graft copolymer resin of Preparation Example 4

Methyl methacrylate (MMA), acrylate-2-ethylhexyl (AEH), and allyl methacrylate (AMA) were added to the silicone emulsion composition obtained above, in a ratio of MMA/AEH/AMA=79.8/20/0.2 (%) While dripping over 3 to 5 hours in a furnace, a peroxide and a reducing agent are added at room temperature to perform an acrylic graft copolymerization, followed by an acrylic graft copolymerization. An about 45% acrylic silicone resin emulsion (acrylic modified organo) containing silicone acrylic graft copolymer resin. polysiloxane) was obtained. The average particle diameter of this emulsion was 270 nm. In addition, the calculation Tg of the said acrylic component is methyl methacrylate (homopolymer Tg: 105 degreeC), acrylic acid-2-ethylhexyl (homopolymer Tg: -70 degreeC), allyl methacrylate (homopolymer Tg: 52 degreeC) ) was calculated using the above-mentioned formula as the above mass ratio, and it was 50°C. By spray-drying this, silicone acrylic copolymer resin powder (Production Example 4) was obtained.

[Production Example 5]

(a1) Preparation of emulsion composition containing organopolysiloxane

828 g of octamethylcyclotetrasiloxane, 0.7 g of 3-methacryloxypropyldimethoxysilane, 8.3 g of sodium lauryl sulfate dissolved in 75 g of pure water, and 8.3 g of dodecylbenzenesulfonic acid dissolved in 75 g of pure water were placed in a 2L polyethylene beaker. After pouring in and uniformly emulsifying with a homomixer, 629 g of pure water was gradually added and diluted, and passed twice through a high-pressure homogenizer at a pressure of 300 kgf/cm 2 to obtain a uniform white emulsion. This emulsion was transferred to a 2L glass flask equipped with a stirring device, a thermometer, and a reflux condenser, polymerized at 55 ° C. for 24 hours, aged at 15 ° C. for 24 hours, and then neutralized to pH 6-8 with 27 g of 10% sodium carbonate aqueous solution. , to obtain a silicone emulsion composition. This emulsion had a non-volatile content of 45.4% after drying at 105°C for 3 hours, and the organopolysiloxane in the emulsion was in the form of a non-flowing soft gel.

Preparation of (A) silicone acrylic graft copolymer resin of Preparation Example 5

Methyl methacrylate (MMA), ethyl acrylate (EA), and allyl methacrylate (AMA) were added to the silicone emulsion composition obtained above in a ratio of MMA/EA/AMA=65.8/34/0.2 (%) of 3 to 5 While dripping over time, a peroxide and a reducing agent were added at room temperature to carry out a redox reaction, and acrylic graft copolymerization was performed to obtain about 45% acrylic silicone resin emulsion (acrylic modified organopolysiloxane) containing silicone acrylic graft copolymer resin. . The average particle diameter of this emulsion was 270 nm. In addition, the calculated Tg of the acrylic component is methyl methacrylate (homopolymer Tg: 105°C), ethyl acrylate (homopolymer Tg: -22°C), and allyl methacrylate (homopolymer Tg: 52°C) as described above. It was 50 degreeC when calculated using the above-mentioned formula as a mass ratio. By spray-drying this, silicone acrylic copolymer resin powder (Production Example 5) was obtained.

[Comparative Preparation Example 1]

(a1) Preparation of emulsion composition containing organopolysiloxane

828 g of octamethylcyclotetrasiloxane, 0.7 g of 3-methacryloxypropyldimethoxysilane, 8.3 g of sodium lauryl sulfate dissolved in 75 g of pure water, and 8.3 g of dodecylbenzenesulfonic acid dissolved in 75 g of pure water were placed in a 2L polyethylene beaker. After pouring in and uniformly emulsifying with a homomixer, 629 g of pure water was gradually added and diluted, and passed twice through a high-pressure homogenizer at a pressure of 300 kgf/cm 2 to obtain a uniform white emulsion. This emulsion was transferred to a 2L glass flask equipped with a stirring device, a thermometer, and a reflux condenser, polymerized at 55 ° C. for 24 hours, aged at 15 ° C. for 24 hours, and then neutralized to pH 6-8 with 27 g of 10% sodium carbonate aqueous solution. , to obtain a silicone emulsion composition. This emulsion had a non-volatile content of 45.4% after drying at 105°C for 3 hours, and the organopolysiloxane in the emulsion was in the form of a non-flowing soft gel.

Preparation of (A) silicone acrylic graft copolymer resin of Comparative Preparation Example 1

Methyl methacrylate (MMA) and methacrylate-2-hydroxyethyl (2-HEMA) were added to the silicone emulsion composition obtained above in a ratio of MMA/2-HEMA = 98/2 (%) for 3 to 5 hours While dripping over the course, redox reaction was carried out by adding a peroxide and a reducing agent at room temperature to carry out an acrylic graft copolymerization, and an acrylic silicone resin emulsion (acrylic modified organopolysiloxane) of about 45% containing silicone acrylic graft copolymer resin was obtained. The average particle diameter of this emulsion was 290 nm. In addition, the calculation Tg of the acrylic component is methyl methacrylate (homopolymer Tg: 105°C) and methacrylic acid-2-hydroxyethyl (homopolymer Tg: 55°C) in the above-mentioned mass ratio. It was 104°C when calculated using By spray-drying this, silicone acrylic copolymer resin powder (comparative production example 1) was obtained.

[Comparative Preparation Example 2]

(a1) Preparation of emulsion composition containing organopolysiloxane

828 g of octamethylcyclotetrasiloxane, 0.7 g of 3-methacryloxypropyldimethoxysilane, 8.3 g of sodium lauryl sulfate dissolved in 75 g of pure water, and 8.3 g of dodecylbenzenesulfonic acid dissolved in 75 g of pure water were placed in a 2L polyethylene beaker. After pouring in and uniformly emulsifying with a homomixer, 629 g of pure water was gradually added and diluted, and passed twice through a high-pressure homogenizer at a pressure of 300 kgf/cm 2 to obtain a uniform white emulsion. This emulsion was transferred to a 2L glass flask equipped with a stirring device, a thermometer, and a reflux condenser, polymerized at 55 ° C. for 24 hours, aged at 15 ° C. for 24 hours, and then neutralized to pH 6-8 with 27 g of 10% sodium carbonate aqueous solution. , to obtain a silicone emulsion composition. This emulsion had a nonvolatile content of 45.4% after drying at 105°C for 3 hours, and the organopolysiloxane in the emulsion was in the form of a non-flowing soft gel.

Preparation of (A) silicone acrylic graft copolymer resin of Comparative Preparation Example 2

Methyl methacrylate (MMA), butyl acrylate (BA), and allyl methacrylate (AMA) were added to the silicone emulsion composition obtained above in a ratio of MMA/BA/AMA=89.8/10/0.2 (%) of 3 to 5 While dripping over time, a peroxide and a reducing agent were added at room temperature to carry out a redox reaction, and acrylic graft copolymerization was performed to obtain about 45% acrylic silicone resin emulsion (acrylic modified organopolysiloxane) containing silicone acrylic graft copolymer resin. . The average particle diameter of this emulsion was 280 nm. In addition, the calculated Tg of the acrylic component is methyl methacrylate (homopolymer Tg: 105°C), butyl acrylate (homopolymer Tg: -52°C), and allyl methacrylate (homopolymer Tg: 52°C) as described above. It was 80 degreeC when calculated using the above-mentioned formula as a mass ratio. By spray-drying this, silicone acrylic copolymer resin powder (comparative production example 2) was obtained.

[Comparative Production Example 3]

(a1) Preparation of emulsion composition containing organopolysiloxane

828 g of octamethylcyclotetrasiloxane, 0.7 g of 3-methacryloxypropyldimethoxysilane, 8.3 g of sodium lauryl sulfate dissolved in 75 g of pure water, and 8.3 g of dodecylbenzenesulfonic acid dissolved in 75 g of pure water were placed in a 2L polyethylene beaker. After pouring in and uniformly emulsifying with a homomixer, 629 g of pure water was gradually added and diluted, and passed twice through a high-pressure homogenizer at a pressure of 300 kgf/cm 2 to obtain a uniform white emulsion. This emulsion was transferred to a 2L glass flask equipped with a stirring device, a thermometer, and a reflux condenser, polymerized at 55 ° C. for 24 hours, aged at 15 ° C. for 24 hours, and then neutralized to pH 6-8 with 27 g of 10% sodium carbonate aqueous solution. , to obtain a silicone emulsion composition. This emulsion had a non-volatile content of 45.4% after drying at 105°C for 3 hours, and the organopolysiloxane in the emulsion was in the form of a non-flowing soft gel.

Preparation of (A) silicone acrylic graft copolymer resin of Comparative Preparation Example 3

Methyl methacrylate (MMA), butyl acrylate (BA), and allyl methacrylate (AMA) were added to the silicone emulsion composition obtained above in a ratio of MMA/BA/AMA=80.8/19/0.2 (%) of 3 to 5 While dripping over time, a peroxide and a reducing agent were added at room temperature to carry out a redox reaction, and acrylic graft copolymerization was performed to obtain about 45% acrylic silicone resin emulsion (acrylic modified organopolysiloxane) containing silicone acrylic graft copolymer resin. . The average particle diameter of this emulsion was 280 nm. In addition, the calculated Tg of the acrylic component is methyl methacrylate (homopolymer Tg: 105°C), butyl acrylate (homopolymer Tg: -52°C), and allyl methacrylate (homopolymer Tg: 52°C) as described above. It was 60 degreeC when calculated using the above-mentioned formula as a mass ratio. By spray-drying this, silicone acrylic copolymer resin powder (comparative production example 3) was obtained.

<Measuring method of softening temperature and flow initiation temperature>

The silicone acrylic copolymer resins of Production Examples 1 to 5 and Comparative Production Examples 1 to 3 were measured by a capillary rheometer (CAPILLARY RHEOMETER) CFT-500D (manufactured by Shimadzu Corporation) with a load of 5 kgf and a temperature increase method.

About a softening temperature, it is preferable that it is 40-80 degreeC, More preferably, it is 50-70 degreeC. A soft film is obtained when the softening temperature is low, but since thermal fusion may occur when obtaining a dry film, it is preferable that it is in the said range.

Moreover, about a flow initiation temperature, it is preferable that it is 100-160 degreeC.

Tg at the time of forming the homopolymer of each acryl monomer in Table 1 is as follows.

MMA: methyl methacrylate Tg: 105°C

BA: butyl acrylate Tg: -52°C

AEH: 2-ethylhexyl acrylate Tg: -70°C

EA: ethyl acrylate Tg: -22°C

AMA: allyl methacrylate Tg: 52°C

2-HEMA: methacrylic acid 2-hydroxyethyl Tg: 55°C

[Example 1]

30 parts of toluene, 30 parts of methyl ethyl ketone, and 20 parts of N,N-dimethylformamide were mixed to prepare a mixed solvent, 20 parts of silicone acrylic copolymer resin obtained in manufacture example 1 were melt|dissolved, and the coating composition was produced. The coating composition was dried with a doctor knife to a polyurethane synthetic leather (thickness 1 mm) and applied to a thickness of about 15 µm, and dried at 120° C. for 1 minute to form a coating film on the polyurethane synthetic leather.

The method shown below evaluated the obtained coating film. The results are shown in Table 2.

<Measuring method of gloss>

The polyurethane synthetic leather on which the coating film was formed was visually evaluated.

(circle): A high-quality luster is seen.

(triangle|delta): A little glossiness is seen.

x: Most of the gloss effect is not seen.

<Measuring method of texture>

The sensory evaluation was performed by touching the polyurethane synthetic leather on which the coating film was formed.

○: There is a characteristic good slippery feeling.

(triangle|delta): There is a slightly favorable slippery feeling.

x: Resistance is felt by the finger, and there is no slippery feeling.

<Measuring method of tensile whitening>

Before water washing: A black polyurethane synthetic leather (thickness 1 mm) having a coating film was strongly pulled, and the change in color tone of the tensioned portion was visually evaluated.

After washing: Rub the black polyurethane synthetic leather with the coating film in running water for 1 minute, wash it, wipe off the moisture, dry it at room temperature for 24 hours, pull it strongly, and visually observe the change in the color tone of the tensioned part. evaluated.

(circle): Whitening is not seen.

(triangle|delta): Whitening is seen locally.

x: Whitening is seen as a whole.

<Measuring method of friction coefficient>

With HEIDON TYPE-38 (manufactured by Shinto Chemical Co., Ltd.), a 200 g metal indenter was brought into vertical contact with the polyurethane synthetic leather on which the coating film was formed, and the friction force when moved at 3 cm/min was measured, and the friction coefficient was calculated from the friction force. Calculated.

In addition, in a preferable range of the static/dynamic friction coefficient in the polyurethane synthetic leather, the static friction coefficient is 0.01 to 0.40, and the dynamic friction coefficient is 0.01 to 0.30.

[Examples 2 to 5, Comparative Examples 1 to 3]

The silicone acrylic copolymer resin and the organic solvent were mix|blended in the ratio shown in Table 2, and it evaluated similarly to Example 1. The results are shown in Table 2.

As shown in Table 2, the coating composition of the present invention (Examples 1 to 5) is a coating composition having excellent touch and gloss, and has a coating film that does not whiten even when pulled, so that the coating of synthetic leather or resin articles is optimal for

Claims (8)

(A) (a1) a polymer comprising 50 to 99 parts by mass of an organopolysiloxane represented by the following general formula (1), and (a2) 1 to 50 parts by mass of a mixture containing two or more acrylic monomers, (a2) The component (a2) above so that the glass transition temperature (Tg) of the acrylic polymer obtained by polymerizing the component is less than 60°C at the Tg calculated using the Fox formula from the homopolymer glass transition temperature (Tg) of each acrylic monomer Silicone acrylic copolymer resin to which the acrylic monomer of is prepared, and
(B) at least one organic solvent selected from the group consisting of amide compounds, ether compounds, ketone compounds, aromatic hydrocarbons and acetate esters;
A coating composition comprising:

(Wherein, R ¹ is the same or different unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ² is an alkyl group having 1 to 6 carbon atoms substituted with a mercapto group, acryloxy group or methacryloxy group. X is the same or different unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, alkoxy group or hydroxyl group having 1 to 20 carbon atoms, Y is X or -[O-Si(X) ₂ ] _d - is the same or different groups represented by X, and at least two of X and Y are hydroxyl groups. Z is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group. a is 0 to 1,000 is a positive number, b is a positive number from 100 to 10,000, c is a positive number from 1 to 10, and d is a positive number from 1 to 1,000.) The organic solvent of component (B) according to claim 1, wherein the organic solvent is N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,4-dioxane, 1,3 - Dioxolane, tetrahydrofuran, methyl ethyl ketone, cyclopentanone, cyclohexanone, toluene, xylene, selected from the group consisting of ethyl acetate and propylene glycol monoethyl ether acetate, the coating composition. The coating composition according to claim 1 or 2, wherein the silicone acrylic copolymer resin as component (A) is an emulsion graft polymer of a mixture of component (a1) and component (a2). The organopolysiloxane according to claim 1 or 2, wherein the organopolysiloxane represented by the formula (1) is a cyclic organosiloxane, α,ω-dihydroxysiloxane oligomer, α,ω-dialkoxysiloxane oligomer or alkoxysilane; The coating composition which is a polymer with the silane coupling agent represented by following General formula (2).
R ³ _(4-ef) R ⁴ _f Si(OR ⁵ ) _e (2)
(Wherein, R ³ is an alkyl group having 1 to 6 carbon atoms substituted with a mercapto group, acryloxy group or methacryloxy group, R ⁴ is an alkyl group having 1 to 4 carbon atoms, R ⁵ is an alkyl group having 1 to 4 carbon atoms, e is 2 or 3, f is 0 or 1, e+f is 2 or 3.) The mixture of the component (a2) according to claim 1 or 2, wherein the homopolymer has a glass transition temperature (Tg) of 50°C or higher, and the homopolymer has a glass transition temperature (Tg) of less than 50°C. The coating composition containing at least 2 or more types of monomers with the monomer used as this. The coating composition according to claim 1 or 2, wherein the organopolysiloxane weight average molecular weight of the component (a1) is 100,000 to 500,000. A coating film formed by drying the coating composition according to claim 1 or 2 . A synthetic leather or resin article having the coating film according to claim 7.