Coating composition and laminate

Abstract

This emulsion type coating composition does not deteriorate performances of an emulsion of a vinyl chloride resin, an acrylic resin, and a urethane resin, imparts performances inherent to a silicone resin, and solves the problem related to cost. The coating composition contains the following component (I) and component (II). (I): An emulsion of a vinyl chloride resin, an acrylic resin, and / or a urethane resin. (II): A vinyl chloride-silicone graft copolymer resin emulsion which is a polymer formed by (A) an organopolysiloxane and (B) vinyl chloride at a mass ratio of (A):(B)=5:95 to 95:5.

Description

Coating composition and laminate

[0001] The present invention relates to a coating composition, more specifically to an emulsion-type coating composition that can maintain transparency and impart sliding properties when coated on a substrate surface. The present invention also relates to a laminate having a coating film formed thereon using the coating composition.

[0002] In recent years, in the field of coating agents, there has been a shift in dispersion media from organic solvents to aqueous systems due to environmental concerns. Emulsions of vinyl chloride resins, acrylic resins, and urethane resins have excellent film-forming properties and have been widely used as coating agents.

[0003] Silicone resins are known to be capable of imparting sliding properties to substrates, but when used as coating agents, they can cause problems such as whitening of the coating film.

[0004] Known silicone-modified resin emulsions include copolymer emulsions such as acrylic silicone emulsions and urethane silicone emulsions. While these emulsions can impart the weather resistance, heat resistance, cold resistance, water repellency, gas permeability, and sliding properties of silicone to the performance of acrylic or urethane resin emulsions, they also have the disadvantages of being costly due to the copolymers and of reducing the advantages of the resin before modification.

[0005] Therefore, attempts have been made to use a method in which an emulsion of a vinyl chloride resin, an acrylic resin, or a urethane resin, which has film-forming ability, is mixed with a silicone resin to form a coating agent, but the mixing has sometimes resulted in the silicone resin not exhibiting its sliding properties or in the performance of the original urethane resin, acrylic resin, or vinyl chloride resin being reduced, making it impossible to achieve satisfactory performance.

[0006] For example, Japanese Patent Laid-Open No. 2013-067787 (Patent Document 1) and Japanese Patent Laid-Open No. 2020-090596 (Patent Document 2) disclose that a coating agent obtained by mixing an emulsion of a vinyl chloride resin, an acrylic resin, or a urethane resin with a silicone resin can impart water repellency and transparency to a substrate. However, there is room for improvement in terms of transparency, water repellency, sliding properties, and cost of silicone resins.

[0007] JP 2013-067787 A JP 2020-090596 A

[0008] Therefore, an object of the present invention is to provide an emulsion-type coating composition that imparts the performance of silicone resins without reducing the performance of emulsions of vinyl chloride resins, acrylic resins, and urethane resins, and that also solves the cost issue, and a laminate having a coating film formed from said composition.

[0009] As a result of extensive research conducted by the present inventors to achieve the above-mentioned object, they discovered that the above-mentioned problems can be solved by a coating composition comprising (I) at least one resin emulsion selected from the group consisting of a vinyl chloride resin emulsion, an acrylic resin emulsion, and a urethane resin emulsion, and (II) a vinyl chloride-silicone graft copolymer resin in a predetermined ratio, and thus completed the present invention.

[0010] That is, the present invention provides the following coating composition, coating film thereof, and laminate.

[0011] [1] A coating composition comprising the following components (I) and (II): (I) at least one emulsion selected from vinyl chloride resin emulsions, acrylic resin emulsions, and urethane resin emulsions: 60 to 99 mass % in terms of solid content, and (II) a vinyl chloride-silicone graft copolymer resin emulsion (A), which is a graft copolymer of (A) an organopolysiloxane represented by the following formula (1) and (B) vinyl chloride, in which the mass ratio of the organopolysiloxane (A) to the vinyl chloride (B) is (A):(B) = 5:95 to 95:5: 1 to 40 mass % in terms of solid content. (In formula (1), R1 are the same or different substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, and R 2 is a radical reactive functional group. X is the same or different, substituted or unsubstituted, monovalent hydrocarbon group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, or hydroxyl group. Y is X or -[O-Si(X)] d -X. 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 a number from 0 to 10,000, b is a number from 100 to 10,000, c is a number from 0.0001 to 100, and d is a number from 1 to 1,000.) [2] A cured product of the coating composition according to [1]. [3] The cured product according to [2], wherein the cured product is a coating film. [4] A laminate having the cured product according to [2]. [5] A laminate having the cured product according to [3].

[0012] The coating composition of the present invention has excellent transparency, water repellency, and sliding properties, and can maintain high abrasion resistance without impairing the appearance of a laminate having a coating film formed from the coating composition. Furthermore, since the dispersion medium of the coating composition of the present invention is aqueous, it has great advantages in terms of workability and the environment.

[0013] The emulsion (I) selected from vinyl chloride resin emulsions, acrylic resin emulsions, and urethane resin emulsions may be used alone or in combination of two or more. The emulsion of component (I) may be synthesized by a known method, for example, emulsion polymerization using an anionic surfactant or a nonionic surfactant, or a commercially available product. The emulsion has film-forming ability. Film-forming ability refers to the ability to eliminate particle-like properties on the coating surface after drying at a certain temperature or higher and to prevent fine cracks from forming during drying. The drying temperature range for film formation is not particularly limited, but is preferably 30 to 150°C, more preferably 100 to 150°C. The drying time is also not particularly limited, but is preferably about 1 second to 10 hours.

[0014] In order for the emulsion of component (I) selected from vinyl chloride resin emulsions, acrylic resin emulsions, and urethane resin emulsions to have film-forming ability, the average particle size of the emulsion is preferably 10 to 500 nm. The average particle size is measured using a dynamic light scattering particle size distribution analyzer. The viscosity (25°C) of the emulsion of component (I) is preferably 10 to 500 mPa·s. The viscosity can be measured using a rotational viscometer. The glass transition temperature (hereinafter sometimes referred to as Tg) of the emulsion of component (I) is 120°C or lower, preferably 60°C or lower, and more preferably 30°C or lower. The lower limit of the glass transition temperature is preferably -50°C. The glass transition temperature can be measured in accordance with JIS K7121.

[0015] Vinyl chloride resin emulsion The vinyl chloride resin emulsion of component (I) may be not only an emulsion of a homopolymer of vinyl chloride monomer, but also an emulsion of a copolymer (copolymer resin) of vinyl chloride monomer and vinyl acetate monomer or vinyl chloride monomer and an acrylic monomer used in the acrylic resin emulsion described below.

[0016] Acrylic Resin Emulsion The acrylic resin emulsion of component (I) is an emulsion of a copolymer (copolymer resin) obtained by mixing one or more of the following monomers. Examples of the acrylic resin monomer include (meth)acrylic acid esters with alcohols having an alkyl group having 1 to 18 carbon atoms, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, glycidyl (meth)acrylate, allyl (meth)acrylate, ethylene glycol di(meth)acrylate, and diethylene glycol di(meth)acrylate. Note that (meth)acrylate is a general term for acrylate and methacrylate. In addition to the above, the following monomers may also be used in combination. Examples of such monomers include acrylonitrile, vinyl acetate, vinyl propionate, styrene, acrylic acid, methacrylic acid, (meth)acrylamide, N-methylol (meth)acrylamide, and N-methoxymethyl (meth)acrylamide.

[0017] Urethane-based resin emulsion The urethane-based resin emulsion may be not only a homopolymer consisting of molecules having a urethane bond or an isocyanurate bond, but also an emulsion of a copolymer (copolymer resin) with an acrylic monomer, a silane monomer, an epoxy monomer, a polyester polymer, or a urea polymer.

[0018] Specific examples of the emulsion include vinyl chloride resin emulsions using vinyl chloride, vinyl chloride / vinyl acetate, vinyl chloride / (meth)acrylic acid, or esters thereof, and acrylic resin emulsions and urethane resin emulsions using (meth)acrylic monomers such as (meth)acrylic acid and (meth)acrylic acid esters.

[0019] An example of a commercially available vinyl chloride resin emulsion is Vinyblan manufactured by Nissin Chemical Industry Co., Ltd. Furthermore, an example of a commercially available acrylic resin emulsion is Vinyblan manufactured by Nissin Chemical Industry Co., Ltd., Yodozole manufactured by Henkel Japan, and Aron manufactured by Toagosei Co., Ltd. An example of a commercially available urethane resin emulsion is Adekabontiter HUX series manufactured by ADEKA Corporation, WLS series manufactured by DIC Corporation, and U-Coat manufactured by Sanyo Chemical Industries, Ltd.

[0020] The blending amount of the emulsion selected from vinyl chloride resin emulsion, acrylic resin emulsion, and urethane resin emulsion of component (I) in the coating composition is 60 to 99 mass %, preferably 65 to 95 mass %, in terms of solids content. If the emulsion is less than 60 mass %, the coating properties such as abrasion resistance may be deteriorated, while if it exceeds 99 mass %, the surface may not be smooth, resulting in a poor feel to the touch.

[0021] (II) Vinyl chloride-silicone graft copolymer resin emulsion is a vinyl chloride-silicone graft copolymer resin emulsion obtained by graft copolymerizing (A) an organopolysiloxane represented by the following general formula (1) with (B) vinyl chloride, in which the mass ratio of the organopolysiloxane (A) to the vinyl chloride (B) is (A):(B)=5:95 to 95:5:

[0022] The organopolysiloxane (A) in the present invention is represented by the following formula (1). (In formula (1), R 1 are the same or different substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, and R 2 is a radical reactive functional group. X is the same or different, substituted or unsubstituted, monovalent hydrocarbon group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, or hydroxyl group. Y is X or -[O-Si(X)] d -X, which may be the same or different. 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 a number from 0 to 10,000, b is a number from 100 to 10,000, c is a number from 0.0001 to 100, and d is a number from 1 to 1,000.

[0023] Here, R 1 are the same or different substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, and specifically include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, and octadecyl groups; cycloalkyl groups such as cyclopentyl, cyclohexyl, and cycloheptyl groups; alkenyl groups such as vinyl and allyl groups; aryl groups such as phenyl, tolyl, and naphthyl groups; Examples of such groups include alkenylaryl groups such as a phenyl group, aralkyl groups such as a benzyl group, a phenylethyl group, and a phenylpropyl group, and alkenylaralkyl groups such as a vinylbenzyl group and a vinylphenylpropyl group, as well as groups in which some or all of the hydrogen atoms have been substituted with a halogen atom such as a fluorine, bromine, or chlorine atom, an acryloxy group, a methacryloxy group, a carboxyl group, an alkoxy group, an alkenyloxy group, an amino group, or an alkyl-, alkoxy-, or (meth)acryloxy-substituted amino group. 1 is preferably a methyl group.

[0024] R 2 is a radical reactive functional group, and examples thereof include a mercapto group or an alkyl group having 1 to 8 carbon atoms substituted with an ethylenic double bond-containing group, a vinyl group, or a styryl group. Specific examples of the alkyl group having 1 to 8 carbon atoms substituted with a mercapto group or an ethylenic double bond-containing group include mercapto groups, vinyl groups, styryl groups, mercapto groups, and alkyl groups having 1 to 8 carbon atoms substituted with an acryloxy group or methacryloxy group. R 2 Examples of the radical reactive functional group represented by the formula (I) include a vinyl group, a styryl group, an octenyl group, a methacryloxyoctyl group, a mercaptopropyl group, an acryloxypropyl group, a methacryloxypropyl group, and a methacryloxyoctylvinyl group.

[0025] X is the same or different, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group. The unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms is preferably R 1Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy, ethoxy, propoxy, butoxy, hexyloxy, heptyloxy, octyloxy, decyloxy, and tetradecyloxy. Of these, hydroxyl, methyl, butyl, and phenyl are preferred. Y is X or -[O-Si(X)2] d -X is the same or different group. Examples of X include the same groups as those exemplified above.

[0026] Z is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group, and is preferably a hydroxyl group or a methyl group.

[0027] a is a number from 0 to 10,000, preferably a number from 0 to 1,000, and more preferably a number from 0 to 200. When a units are included, the lowest limit is preferably 0.5. If a is greater than 10,000, the strength of the resulting coating may be insufficient when a composition containing component (A) is used as a coating film. b is a number from 100 to 10,000, preferably a number from 1,000 to 5,000. If b is less than 100, the coating may have poor flexibility, and if it is greater than 10,000, its tear strength may be reduced. c is a number from 0.0001 to 100, and if it exceeds 100, the sliding effect may not be achieved. Here, c / (a+b+c)×100 is preferably 0.0001 to 10, more preferably 0.001 to 10. d is a number from 1 to 1,000, preferably a number from 1 to 200.

[0028] The organopolysiloxane represented by formula (1) is preferably used in the form of an emulsion, and may be a commercially available product or may be synthesized. When synthesized, it can be easily synthesized by a known emulsion polymerization method, for example, by emulsifying and dispersing a cyclic organosiloxane, an α,ω-dihydroxysiloxane oligomer, an α,ω-dialkoxysiloxane oligomer, an alkoxysilane, or the like, and a silane coupling agent represented by formula (2) below in water using an anionic surfactant, and then adding a polymerization catalyst such as an acid as needed to carry out a polymerization reaction. The cyclic organosiloxane may have a fluorine atom, a (meth)acryloxy group, a carboxyl group, a hydroxyl group, or an amino group. (In formula (2), R 3 is a radical reactive functional group, particularly an acryloxy group, a methacryloxy group, a vinyl group, or a mercapto group-substituted alkyl group having 1 to 8 carbon atoms, or a styryl group or a vinyl group. 4 is an alkyl group or a hydroxy group having 1 to 4 carbon atoms, and R 5 is an alkyl group having 1 to 4 carbon atoms, e is 2 or 3, f is 0 or 1, and e+f is 2 or 3.

[0029] 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-tetravinyltetramethylcyclotetrasiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetracyclohexyltetramethylcyclotetrasiloxane, tris(3,3,3-trifluoropropyl)trimethylcyclotrisiloxane, and 1,3,5,7-tetra(3-methacryloxypropyl)tetramethylsiloxane. Examples include chlorotetrasiloxane, 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)tetramethylcyclotetrasiloxane, 1,3,5,7-tetra[3-(p-vinylphenyl)propyl]tetramethylcyclotetrasiloxane, 1,3,5,7-tetra(N-acryloyl-N-methyl-3-aminopropyl)tetramethylcyclotetrasiloxane, and 1,3,5,7-tetra(N,N-bis(lauroyl)-3-aminopropyl)tetramethylcyclotetrasiloxane. Octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane are preferred.

[0030] Specific examples of the silane coupling agent include vinyl silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrippropoxysilane, vinyltriisopropoxysilane, vinylmethyldimethoxysilane, and vinylmethyldiethoxysilane; γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane, γ-(meth)acryloxypropyltripropoxysilane, γ-(meth)acryloxypropyltriisopropoxysilane, and γ-(meth)acryloxypropyltributoxysilane; Examples of suitable silanes include acrylic silanes such as γ-(meth)acryloxypropylmethyldimethoxysilane, γ-(meth)acryloxypropylmethyldiethoxysilane, γ-(meth)acryloxypropylmethyldipropoxysilane, γ-(meth)acryloxypropylmethyldiisopropoxysilane, and γ-(meth)acryloxypropylmethyldibutoxysilane; mercaptosilanes such as γ-mercaptopropylmethyldimethoxysilane and γ-mercaptopropyltrimethoxysilane; and styrylsilanes such as styryltrimethoxysilane. Oligomers obtained by condensation polymerization of these silanes may be more preferred because they suppress the generation of alcohol. Here, (meth)acryloxy refers to acryloxy or methacryloxy. These silane coupling agents are preferably used in an amount of 0.01 to 20 parts by mass, and more preferably 0.01 to 5 parts by mass, per 100 parts by mass of cyclic organosiloxane, α,ω-dihydroxysiloxane oligomer, α,ω-dialkoxysiloxane oligomer, alkoxysilane, or the like.

[0031] By copolymerizing a cyclic organosiloxane, an α,ω-dihydroxysiloxane oligomer, an α,ω-dialkoxysiloxane oligomer, an alkoxysilane, or the like with a silane coupling agent, a unit having a repeating number c in the above formula (1) ([Si(R 2 )(Z)O]), which can be graft-polymerized with vinyl chloride (B).

[0032] Any known polymerization catalyst may be used as the polymerization catalyst. Among these, strong acids are preferred, such as hydrochloric acid, sulfuric acid, dodecylbenzenesulfonic acid, citric acid, lactic acid, and ascorbic acid. Dodecylbenzenesulfonic acid, which has surfactant properties, is preferred. The amount of polymerization catalyst used is preferably 0.01 to 10 parts by mass, and more preferably 0.2 to 2 parts by mass, per 100 parts by mass of the cyclic organosiloxane, α,ω-dihydroxysiloxane oligomer, α,ω-dialkoxysiloxane oligomer, alkoxysilane, or the like.

[0033] Furthermore, preferred anionic surfactants include sodium lauryl sulfate, sodium laureth sulfate, N-acyl amino acid salts, N-acyltaurate salts, aliphatic soaps, alkyl phosphates, sodium lauroyl methyl taurine, sodium myristoyl methyl taurine, etc. More preferred are N-acyl amino acid salts, N-acyltaurate salts, aliphatic soaps, alkyl phosphates, sodium lauroyl methyl taurine, and sodium myristoyl methyl taurine, and particularly preferred are sodium lauroyl methyl taurine, sodium myristoyl methyl taurine, and sodium lauryl sulfate.

[0034] The amount of the anionic surfactant used is preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the cyclic organosiloxane, α,ω-dihydroxysiloxane oligomer, α,ω-dialkoxysiloxane oligomer, alkoxysilane, or the like.

[0035] The polymerization temperature is preferably 50 to 75° C., and the polymerization time is preferably 10 hours or more, more preferably 15 hours or more. Furthermore, it is particularly preferable to age the mixture after polymerization at 5 to 30° C. for 10 hours or more.

[0036] After the polymerization reaction is completed, the reaction mixture may be neutralized to a pH of 2.5 to 14, preferably 4 to 11, using a neutralizing agent (such as a 10% aqueous sodium carbonate solution).

[0037] The weight average molecular weight (Mw) of the organopolysiloxane (A) as determined by viscosity measurement is preferably 10,000 to 1,000,000, and more preferably 100,000 to 500,000, from the viewpoint of sliding effect.

[0038] Here, the weight average molecular weight (Mw) of an organopolysiloxane determined by viscosity measurement is calculated from the specific viscosity ηsp (25°C) of a toluene solution of the organopolysiloxane at 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]=0.215×10 -4 M 0.65 Specifically, 20 g of organopolysiloxane emulsion was mixed with 20 g of IPA (isopropyl alcohol), the emulsion was broken, the IPA was discarded, and the remaining rubbery organopolysiloxane was dried overnight at 60°C. This was made into a toluene solution of organopolysiloxane at a concentration of 1 g / 100 ml, and the viscosity was measured at 25°C using an Ubbelohde viscometer. The molecular weight can be calculated by substituting the viscosity into the above formula (References: Nakamuta, Nikka, 77 858

[1956] , Doklady Akad. Nauk. U.S.S.R. 89 65

[1953] ).

[0039] The vinyl chloride-silicone graft copolymer (copolymer resin) can be obtained by graft polymerizing (A) an organopolysiloxane and (B) vinyl chloride.

[0040] The method for producing a vinyl chloride-silicone graft copolymer (copolymer resin) comprises a step of graft polymerizing an organopolysiloxane of formula (1) (component (A)) with vinyl chloride (component (B)) in a mass ratio (mass ratio of organopolysiloxane of formula (1) to vinyl chloride units) of 5:95 to 95:5, preferably 20:80 to 85:15. If the proportion of the organopolysiloxane component of formula (1) is less than 5, sliding effect may not be achieved.

[0041] Examples of radical initiators used in the production of vinyl chloride-silicone graft copolymers (copolymer resins) include persulfates such as potassium persulfate and ammonium persulfate, aqueous hydrogen persulfate, t-butyl hydroperoxide, and hydrogen peroxide. If necessary, redox compounds can be used in combination with reducing agents such as sodium sulfite, Rongalite, L-ascorbic acid, tartaric acid, sugars, and amines. The amount of radical initiator used is preferably 0.1 to 5 mass %, more preferably 0.5 to 3 mass %, of vinyl chloride (B).

[0042] The polymerization temperature for component (B) relative to component (A) is preferably 25 to 85° C., more preferably 55 to 85° C. The polymerization time is preferably 2 to 20 hours, more preferably 3 to 10 hours.

[0043] Furthermore, a chain transfer agent can be added to adjust the molecular weight and polymerization rate of the polymer. Examples of such an agent include halogenated hydrocarbons such as chloroform and carbon tetrachloride; and mercaptans such as n-dodecyl mercaptan, tert-dodecyl mercaptan, and n-octyl mercaptan. The amount of the chain transfer agent used is preferably 0.1 to 1 part by mass, and more preferably 0.3 to 0.8 parts by mass, per 100 parts by mass of the monomer (vinyl chloride).

[0044] The vinyl chloride-silicone graft copolymer (copolymer resin) obtained in this manner is a polymer in which vinyl chloride, component (B), is randomly bonded to organopolysiloxane, component (A), and is a polymer containing a mixture of many different structures, making it impossible to directly identify the product by its structure or properties.

[0045] A method for producing an emulsion of a vinyl chloride-silicone graft copolymer (copolymer resin) preferably includes a step of emulsion-polymerizing an organopolysiloxane of formula (1) (component (A)) with vinyl chloride (component (B)) in a mass ratio (mass ratio of the organopolysiloxane of formula (1) to the vinyl chloride units) of 5:95 to 95:5, preferably 20:80 to 85:15. When carrying out emulsion polymerization, the organopolysiloxane of component (A) is used in the form of an emulsion, and the surfactant contained in the organopolysiloxane emulsion is sufficient for graft polymerization. However, to improve stability, anionic surfactants such as sodium lauryl sulfate, sodium laureth sulfate, N-acylamino acid salts, N-acyltaurine salts, aliphatic soaps, and alkyl phosphates can be added. Nonionic emulsifiers such as polyoxyethylene lauryl ether and polyoxyethylene tridecyl ether can also be added. When a surfactant is added, its amount is preferably 0.1 to 5% by mass of the vinyl chloride (B). In this manner, the vinyl chloride-silicone graft copolymer obtained by emulsion polymerization can also be obtained in the form of an emulsion, i.e., as an emulsion of the vinyl chloride-silicone graft copolymer.

[0046] Furthermore, the vinyl chloride-silicone graft copolymer (copolymer resin) preferably has a solids content of 25 to 40% by mass in the emulsion. Furthermore, the viscosity of this emulsion (at 25°C) is preferably 1 to 500 mPa·s, more preferably 1 to 200 mPa·s. The viscosity can be measured using a rotational viscometer. The average particle size of the emulsion is preferably 0.1 μm (100 nm) to 0.5 μm (500 nm). The average particle size is a value measured using a dynamic light scattering particle size distribution analyzer.

[0047] The blending amount of the vinyl chloride-silicone graft copolymer resin emulsion of component (II) in the coating composition is 1 to 40 mass % in terms of solids content, and preferably 5 to 30 mass %. If the vinyl chloride-silicone graft copolymer resin emulsion is less than 1 mass %, no improvement in abrasion resistance may be observed, whereas if it exceeds 40 mass %, whitening may occur and abrasion resistance may also decrease.

[0048] The coating composition of the present invention can be obtained by mixing component (I), an emulsion selected from a vinyl chloride resin emulsion, an acrylic resin emulsion, and a urethane resin emulsion, with component (II), a vinyl chloride-silicone graft copolymer resin emulsion, in an aqueous system using a known mixing and preparation method such as a propeller stirrer or homogenizer.

[0049] Furthermore, the coating composition of the present invention may contain additives such as antioxidants, colorants, ultraviolet absorbers, light stabilizers, antistatic agents, plasticizers, flame retardants, thickeners, surfactants, organic solvents (such as film-forming aids), other resins, etc., within the range that does not affect the performance.

[0050] A laminate can be obtained by applying or immersing one or both surfaces of a substrate in the coating composition of the present invention.

[0051] In order to ensure the desired high transparency, it is preferable that the haze increase rate when the coating composition of the present invention is applied to a substrate is 1500% or less relative to the haze value of the substrate before application, and more preferably 1000% or less, depending on the type of substrate. The "haze" referred to in the present invention is HAZE (haze value) calculated from the total light transmittance and diffuse transmittance according to the following formula in accordance with the standard of JIS K7136 (2000): HAZE (haze value) = (diffuse transmittance T d / Total light transmittance T t ) × 100 (%) The haze value of the coating on the substrate can be measured, for example, by a haze meter manufactured by Nippon Denshoku Industries Co., Ltd. The haze value of the substrate before the coating composition is applied can also be measured according to the same standard as above. The "haze increase rate" referred to in the present invention is the rate at which the haze value of the substrate is increased by the H X , the haze value after coating the coating composition is H Y Then, it can be calculated from the following formula: [Increase in haze value (%)] = [(H Y -H X ) / H X ]×100

[0052] When the coating composition of the present invention is applied to one or both surfaces of a substrate, such as plastics (PET, PI, etc.), glass (general-purpose glass, SiO, etc.), metals (Si, Cu, Fe, Ni, Co, Au, Ag, Ti, Al, Zn, Sn, Zr, alloys thereof, etc.), wood, fibers (cloth, thread, etc.), paper, or ceramics (fired oxides, carbides, nitrides, etc.), and dried (room temperature to 150°C), it can impart the long-term benefits of silicone resins, such as water repellency, weather resistance, heat resistance, cold resistance, gas permeability, and sliding properties, while maintaining the advantages of acrylic resins, vinyl chloride resins, or urethane resins. Note that, in this specification, room temperature refers to 1°C to 40°C.

[0053] Examples of plastic substrates that can be used include poly(meth)acrylic acid esters such as polymethyl methacrylate, polycarbonate, polystyrene, polyethylene terephthalate, polyvinyl chloride, polyester, cellulose, diethylene glycol bisallyl carbonate polymers, acrylonitrile-butadiene-styrene polymers, polyurethane, and epoxy resins. Examples of plastic processed products include automotive interior materials, organic glass, electrical and building materials, building exterior materials, optical films used in liquid crystal displays, light diffusion films, mobile phones, and home appliances. Drying methods include leaving the substrate at room temperature for 1 to 10 days, but from the perspective of rapidly promoting curing, heating at a temperature of 20 to 150°C for 1 second to 10 hours is preferred. Furthermore, when the plastic substrate is made of a material that is prone to deformation or discoloration due to heating, drying at a relatively low temperature of 20 to 100°C is preferred.

[0054] Examples of glass substrates that can be used include soda-lime glass, quartz glass, lead glass, borosilicate glass, alkali-free glass, etc. Examples of glass processed products include architectural plate glass, glass for vehicles such as automobiles, glass for lenses, glass for mirrors, glass for display panels, glass for solar cell modules, etc. Preferred drying methods include leaving the glass at room temperature for about 1 to 10 days, or heating the glass at a temperature of 20 to 150°C, particularly 60 to 150°C, for 1 second to 10 hours.

[0055] Examples of wood substrates include wood from the families Maple, Birch, Lauraceae, Chestnut, Scrophulariaceae, Araucaria, Ulmaceae, Bignoniaceae, Rosaceae, Cupressaceae, Dipterocarpaceae, Myrtaceae, Fagaceae, Pinaceae, Fabaceae, and Oleaceae. Wood products may be selected from processed and molded products made from wood itself, plywood and laminated lumber, processed and molded products thereof, and combinations thereof. Examples include building materials, including exterior and interior materials for buildings, furniture such as desks, wooden toys, and musical instruments. Hot air drying at 20 to 150°C, particularly 50 to 150°C, for 0.5 to 5 hours is preferred. Furthermore, discoloration of the coating film can be avoided by keeping the drying temperature at 120°C or below.

[0056] Examples of fiber substrates include natural fibers such as cotton, hemp, linen, wool, silk, cashmere, and asbestos, and chemical fibers such as polyamide, polyester, viscose, cellulose, glass, and carbon. Fiber processed products include all types of woven fabrics, knitted fabrics, nonwoven fabrics, films, and papers. Preferred drying methods include leaving the material at room temperature for 10 minutes to several tens of hours, or drying at a temperature of 20 to 150°C for 0.5 minutes to 5 hours.

[0057] The viscosity (23°C) of the finally obtained composition is preferably 10 mPa·s or more and 3,000 mPa·s or less, and more preferably 20 mPa·s or more and 2,500 mPa·s or less. Note that this viscosity is measured using a Brookfield viscometer (23±0.5°C). Furthermore, by blending a basic or acidic compound, the composition can be effectively used in both alkaline and acidic environments, with a pH ranging from 2 to 12.

[0058] The method for coating the substrate is not particularly limited, but examples include direct immersion, spray coating, bar coating, roll coating, etc., and the film thickness after drying is preferably about 0.5 to 50 μm, more preferably 1 to 20 μm, taking transparency into consideration. In the case of film formation by immersion, the film is immersed for 10 seconds to 30 minutes, and then dried at room temperature to 150° C. for about 1 second to 10 days with appropriate adjustments to form a desired thickness, preferably 0.01 to 5 kg / m 2 Process it so that it becomes.

[0059] In the case of forming a film by coating, the amount of the coating composition of the present invention to be applied to a substrate is not particularly limited, but is usually preferably 1 to 300 g / m in terms of solid content from the viewpoints of antifouling properties, application workability, etc. 2 , more preferably 5 to 100 g / m 2 The film is formed by natural drying or by heating and drying at 100 to 200° C. to a thickness of 1 to 500 μm, preferably 5 to 100 μm.

[0060] The water contact angle of the obtained film is preferably 50° or more 30 seconds after contact with a 1.8 μL droplet of ion-exchanged water using an automatic contact angle meter CA-V (manufactured by Kyowa Interface Science Co., Ltd.) in an atmosphere of 23°C temperature and 45% humidity.

[0061] The present invention will be explained in detail below with reference to Production Examples, Examples, and Comparative Examples, but the present invention is not limited to the following Production Examples and Examples. Furthermore, the molecular weights shown below are weight-average molecular weights (Mw) determined by viscosity measurement from the specific viscosity of a toluene solution of the organopolysiloxane at a concentration of 1 g / 100 ml. In the following examples, parts and % represent parts by mass and % by mass, respectively.

[0062] [Production Example 1] 1200 g of octamethylcyclotetrasiloxane, 4.8 g of γ-methacryloxypropylmethyldimethoxysilane, a solution of 12 g of sodium lauryl sulfate dissolved in 108 g of pure water, and a solution of 12 g of dodecylbenzenesulfonic acid dissolved in 108 g of pure water were charged into a 4 L polyethylene beaker, and after uniformly emulsifying using a homomixer, 728 g of water was gradually added to dilute the mixture, and the mixture was stirred under a pressure of 300 kgf / cm. 2The emulsion was passed through a high-pressure homogenizer twice at 105°C, yielding a uniform white emulsion. This emulsion was transferred to a 2-L glass flask equipped with a stirrer, thermometer, and reflux condenser, and polymerized at 55°C for 24 hours. After aging at 15°C for 24 hours, it was neutralized to pH 7 with a 10% aqueous sodium carbonate solution. After drying at 105°C for 3 hours, the emulsion had a non-volatile content (solids content) of 44%, and the organopolysiloxane in the emulsion was in the form of a non-flowable soft gel. Based on the viscosity of the toluene solution, this emulsion (silicone composition) had a molecular weight of approximately 250,000 and a structure represented by the following formula (A): 2 is a γ-methacryloxypropyl group. The structure of the organopolysiloxane obtained by the above polymerization reaction is 1 H-NMR (frequency 600 MHz, room temperature, accumulation number 128) and 29 The results were confirmed by Si-NMR (frequency 60 MHz, room temperature, 5000 accumulations) (apparatus name: JNM-ECA600, measurement solvent: CDCl3). 1207 g of the emulsion was transferred to a polymerization vessel equipped with a stirrer, condenser, thermometer, and nitrogen gas inlet, and 59 g of vinyl chloride and ammonium persulfate were added. The reaction was carried out at 60°C for 8 hours to graft copolymerize vinyl chloride onto the silicone composition, yielding an emulsion of vinyl chloride-silicone graft copolymer with a nonvolatile content of 30%. The obtained vinyl chloride-silicone graft copolymer was 2 The copolymer was a vinyl chloride-silicone graft copolymer, with vinyl chloride grafted onto it.

[0063] [Preparation Example 2] An emulsion of vinyl chloride-silicone graft copolymer with a nonvolatile content of 30% was obtained in the same manner as in Preparation Example 1, except that the amount of vinyl chloride was changed to 132 g.

[0064] [Preparation Example 3] A silicone vinyl chloride graft copolymer emulsion with a nonvolatile content of 30% was obtained in the same manner as in Preparation Example 1, except that the amount of vinyl chloride was changed to 226 g.

[0065] [Production Example 4] 1200 g of octamethylcyclotetrasiloxane, 0.96 g of γ-methacryloxypropylmethyldimethoxysilane, a solution of 12 g of sodium lauryl sulfate dissolved in 108 g of pure water, and a solution of 12 g of dodecylbenzenesulfonic acid dissolved in 108 g of pure water were charged into a 4 L polyethylene beaker, and after uniformly emulsifying using a homomixer, 728 g of water was gradually added to dilute the mixture, and the mixture was stirred under a pressure of 300 kgf / cm. 2 The emulsion was passed through a high-pressure homogenizer twice at 105°C, yielding a uniform white emulsion. This emulsion was transferred to a 2-L glass flask equipped with a stirrer, thermometer, and reflux condenser, and polymerized at 55°C for 24 hours. After aging at 15°C for 24 hours, it was neutralized to pH 7 with a 10% aqueous sodium carbonate solution. After drying at 105°C for 3 hours, the emulsion had a non-volatile content (solids content) of 45%, and the organopolysiloxane in the emulsion was in the form of a non-flowable soft gel. Based on the viscosity of the toluene solution, this emulsion (silicone composition) had a molecular weight of approximately 250,000 and a structure represented by the following formula (B): 2 is a γ-methacryloxypropyl group. 1,198 g of the emulsion was transferred to a polymerization vessel equipped with a stirrer, condenser, thermometer, and nitrogen gas inlet, and 231 g of vinyl chloride and ammonium persulfate were added. The reaction was carried out at 60°C for 8 hours to graft copolymerize vinyl chloride onto the silicone composition, yielding an emulsion of vinyl chloride-silicone graft copolymer with a nonvolatile content of 30%. The obtained vinyl chloride-silicone graft copolymer was 2 The copolymer was a vinyl chloride-silicone graft copolymer, with vinyl chloride grafted onto it.

[0066] [Preparation Example 5] An emulsion of vinyl chloride-silicone graft copolymer with a nonvolatile content of 30% was obtained in the same manner as in Preparation Example 1, except that the amount of vinyl chloride was changed to 528 g.

[0067] [Preparation Example 6] An emulsion of vinyl chloride-silicone graft copolymer with a nonvolatile content of 30% was obtained in the same manner as in Preparation Example 1, except that the amount of vinyl chloride was changed to 1,232 g.

[0068] Comparative Production Example 1 1,200 g of octamethylcyclotetrasiloxane, 4.8 g of γ-methacryloxypropylmethyldimethoxysilane, a solution of 12 g of sodium lauryl sulfate dissolved in 108 g of pure water, and a solution of 12 g of dodecylbenzenesulfonic acid dissolved in 108 g of pure water were charged into a 4 L polyethylene beaker and homogeneously emulsified using a homomixer. After that, 728 g of water was gradually added to dilute the mixture, and the mixture was stirred under a pressure of 300 kgf / cm. 2 The emulsion was passed through a high-pressure homogenizer twice at 105°C, yielding a uniform white emulsion. This emulsion was transferred to a 2-L glass flask equipped with a stirrer, thermometer, and reflux condenser, and polymerized at 55°C for 24 hours. After aging at 15°C for 24 hours, it was neutralized to pH 7 with a 10% aqueous sodium carbonate solution. After drying at 105°C for 3 hours, the nonvolatile content (solids content) of this emulsion was 44%, and the organopolysiloxane in the emulsion was in the form of a non-flowable soft gel. Based on the viscosity of the toluene solution, this emulsion (silicone composition) had a molecular weight of approximately 250,000 and a structure represented by formula (A) above.

[0069] Comparative Production Example 2 840 g of vinyl chloride, 16.8 g of 2-hydroxyethyl methacrylate, and potassium peroxodisulfate were added to a polymerization vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen gas inlet, and the mixture was reacted for 30 hours at 45°C while adding 2530 g of vinyl chloride, thereby obtaining a copolymer emulsion with a non-volatile content of 40%.

[0070] Comparative Production Example 3 1,200 g of octamethylcyclotetrasiloxane, 0.96 g of γ-methacryloxypropylmethyldimethoxysilane, a solution of 12 g of sodium lauryl sulfate dissolved in 108 g of pure water, and a solution of 12 g of dodecylbenzenesulfonic acid dissolved in 108 g of pure water were charged into a 2-L polyethylene beaker and homogeneously emulsified using a homomixer. After that, 400 g of water was gradually added to dilute the mixture, and the mixture was stirred under a pressure of 300 kgf / cm. 2The emulsion was passed through a high-pressure homogenizer twice at 105°C, yielding a uniform white emulsion. This emulsion was transferred to a 2-L glass flask equipped with a stirrer, thermometer, and reflux condenser and polymerized at 55°C for 24 hours. After aging at 15°C for 24 hours, it was neutralized to pH 7 with a 10% aqueous sodium carbonate solution. After drying at 105°C for 3 hours, this emulsion had a non-volatile content of 45%, and the organopolysiloxane in the emulsion was in the form of a non-flowable soft gel. Based on the viscosity of the toluene solution, this emulsion (silicone composition) had a molecular weight of approximately 250,000 and a structure represented by formula (B). Furthermore, 231.4 g of methyl methacrylate was added dropwise to this emulsion over 3 to 5 hours while the reaction was carried out using t-butyl hydroperoxide at 27°C, thereby graft-copolymerizing acrylic onto the silicone composition, yielding an emulsion of acrylic-silicone graft copolymer with a non-volatile content of 44.4%.

[0071] Comparative Production Example 4 160 g of the silicone emulsion obtained in Comparative Production Example 1 above and 75 g of the vinyl chloride emulsion obtained in Comparative Production Example 2 above were mixed with stirring for 1 hour to obtain a mixed emulsion with a nonvolatile content of 42.7%.

[0072] The emulsions obtained in the above Production Examples 1 to 6 and Comparative Production Examples 1 to 4 were evaluated by the following methods. The results are shown in Tables 1 and 2.

[0073] <Method for measuring solid content> Approximately 1 g of sample was accurately weighed onto an aluminum foil dish, placed in a dryer maintained at approximately 105°C, heated for 1 hour, then removed from the dryer and allowed to cool in a desiccator. The aluminum foil dish containing the dried sample was weighed, and the solid content (evaporation residue) was calculated using the following formula. R: Solid content (evaporation residue) (%) W: Mass (g) of aluminum foil dish containing sample before drying L: Mass (g) of aluminum foil dish T: Mass (g) of aluminum foil dish containing sample after drying Dimensions of aluminum foil dish: 65φ×23h (mm)

[0074] <Viscosity Measurement Method> The liquid temperature of the sample was kept at 23±0.5° C., and the viscosity was measured using a rotational viscometer (No. 1 rotor, 6 rpm, manufactured by Toki Sangyo Co., Ltd.: trade name: VISCOMETER TVB-10).

[0075] <Average particle size> The average particle size (particle size value corresponding to 50% of the cumulative particle size distribution) was measured by weighing 0.01 g of a sample and using a laser diffraction particle size distribution analyzer (manufactured by Horiba, Ltd., product name: LA-950V2) under conditions of a circulation flow rate of 2 and a stirring speed of 2. [Measurement conditions] Measurement temperature: 25±1°C Solvent: ion-exchanged water

[0076] <Measurement of minimum film formation temperature (MFT)> The minimum film formation temperature (MFT, °C) of the emulsion was measured by a method conforming to JIS K-6828-2. Specifically, a simple film formation temperature measuring device (manufactured by Imoto Manufacturing Co., Ltd.) was used, in which a heating source and a cooling source were installed at a fixed distance. 1 μl of emulsion was applied to aluminum foil, and the state of the coating after 2 hours was observed using the device. The emulsion was dried under a temperature gradient, and the boundary temperature between the transparent part where a film was formed and the part where no film was formed was measured, and this was taken as the minimum film formation temperature (MFT, °C). Considering the drying property during coating formation, an MFT of 100°C or less is desirable.

[0077]

[0078]

[0079] [Example 1] (I) Hydran WLS-213 (a polycarbonate-based aqueous urethane resin manufactured by DIC Corporation) was used as the urethane resin emulsion. While this resin emulsion was being stirred, the vinyl chloride-silicone copolymer resin emulsion obtained in Production Example 1 was added, and after stirring for 10 minutes or more, the mixture was filtered through an 80 mesh filter to obtain the coating composition of Example 1.

[0080] [Examples 2 to 9, Comparative Examples 1 to 7] According to the blending ratios of each component shown in Table 3 (Examples 1 to 6), Table 4 (Examples 7 to 9), Table 5 (Comparative Examples 1 to 5), and Table 6 (Comparative Examples 6 and 7), coating compositions of each example were produced in the same manner as in Example 1. The raw material ratios shown in Tables 3, 4, 5, and 6 are mass ratios of solid content.

[0081] [Example 10] (I) Vinyblan 700 (manufactured by Nissin Chemical Industry Co., Ltd.) was used as the acrylic / vinyl chloride emulsion. While this resin emulsion was being stirred, the vinyl chloride / silicone copolymer resin emulsion obtained in Production Example 3 was added, and after stirring for 10 minutes or more, the mixture was filtered through an 80 mesh filter to obtain the coating composition of Example 10 (Table 4).

[0082] [Example 11, Comparative Example 8] According to the blending ratios of each component shown in Table 4 (Example 11) and Table 6 (Comparative Example 8), coating compositions of each example were produced in the same manner as in Example 10.

[0083] The "haze value / haze increase rate" and "static / dynamic friction coefficient" of the obtained coating compositions of each Example and Comparative Example were measured. The values ​​are shown in Tables 3 to 6. The measurements were carried out as follows.

[0084] <Film Forming Method> The coating composition of each example was applied using a bar coater and dried at 105°C for 3 minutes to form a coating film on each substrate of a PET film and a soft vinyl chloride sheet so that the thickness of the coating film was approximately 10 µm when dry.

[0085] <Alcohol resistance> The coating composition of each example and comparative example was applied to a PET film using a bar coater and dried at 105°C for 3 minutes to form a coating film with a thickness of approximately 10 μm after drying. 98% ethanol was dropped onto the coating film and air-dried overnight at room temperature. The change in the coating film after air-drying was evaluated visually. ○: No change in appearance △: Traces remained but no whitening ×: Whitening

[0086] <Water Contact Angle Measurement> The coating composition of each Example and Comparative Example was applied to a PET film using a bar coater and dried at 105°C for 3 minutes to form a coating film with a dry thickness of approximately 10 μm. 2 μl of pure water was dropped onto the coating film, and the contact angle values ​​were measured after 1 second and 30 seconds using a contact angle meter CA-D model manufactured by Kyowa Interface Science Co., Ltd. Considering the prevention of water-based stains due to water repellency, a contact angle of 80° or more is preferred.

[0087] <Measurement of Haze Value> The coating composition of each Example and Comparative Example was applied to a PET film (haze value 2.20) using a bar coater, and dried at 105°C for 3 minutes to form a coating film with a dry thickness of approximately 10 µm. The haze value of the substrate having the coating film of the coating composition of each Example above was measured using a product name "Haze Meter COH400" (manufactured by Nippon Denshoku Industries Co., Ltd.).

[0088] <Measurement of static and dynamic friction coefficients> The coating composition of each example and comparative example was applied to a PET film using a bar coater and dried at 105°C for 3 minutes to form a coating film with a dry thickness of approximately 10 μm. Using a HEIDON TYPE-38 (manufactured by Shinto Scientific Co., Ltd.), a 200 g metal indenter was brought into contact with the coating film perpendicularly and moved at 3 cm / min to measure the friction force, and the friction coefficient was calculated from the friction force. Note that the preferred ranges for the static and dynamic friction coefficients under the above conditions are a static friction coefficient of 0.2 or less and a dynamic friction coefficient of 0.1 or less.

[0089] <Abrasion resistance> A coating film formed on a soft vinyl chloride synthetic leather sheet was rubbed against cotton canvas to check (visually) whether the coating film had been torn or not, based on color transfer. The friction conditions were 9.8 N and 2000 times. ◎: Excellent, ◯: Good, △: Fair, ×: Poor

[0090]

[0091]

[0092]

[0093]

Claims

1. A coating composition comprising the following component (I) and component (II). (I) At least one emulsion selected from a vinyl chloride resin emulsion, an acrylic resin emulsion, and a urethane resin emulsion: 60 to 99% by mass of solid content (II) A graft copolymer of (A) an organopolysiloxane represented by the following formula (1) and (B) vinyl chloride, wherein the mass ratio of the (A) organopolysiloxane to the (B) vinyl chloride is (A):(B) = 5:95 to 95:5, a vinyl chloride-silicone graft copolymer resin emulsion: 1 to 40% by mass of solid content (In formula (1), R 1 is the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R 2 is a radical-reactive functional group. X is the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group. Y is the same or different group represented by X or -[O-Si(X)2] d -X. 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 a number from 0 to 10,000, b is a number from 100 to 10,000, c is a number from 0.0001 to 100, and d is a number from 1 to 1,000.) 2. The cured product of the coating composition according to claim 1.

3. The cured product according to claim 2, wherein the cured product is a coating film.

4. A laminate having the cured product according to claim 2.

5. A laminate having the cured product according to claim 3.

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