Coating composition for furniture and architectural interiors, and laminate

Abstract

A coating composition for furniture or interior building decoration, comprising: (A) an emulsion of a silicone acrylate copolymer resin, which is a copolymer of 60 to 99 parts by mass of a polyorganosiloxane represented by the general formula (1) and 1 to 40 parts by mass of an acrylate monomer and / or a methacrylate monomer (the total of the components (a1) and (a2) is 100 parts by mass), (B) a resin emulsion other than the component (A) selected from an acrylic resin emulsion, a urethane resin emulsion, and an alkyd resin emulsion, (C) a pigment, and (D) a flame retardant. The coating composition of the present invention forms a film having excellent touch feeling, abrasion resistance, stain resistance, flame retardancy, and weather resistance.

Description

Technical Field

[0001] The present invention relates to a coating composition used in furniture and interior building materials. More specifically, it is an aqueous coating composition that can be applied to the surfaces of substrates such as wood, resin, metal, and ceramics, and can endow excellent touch, abrasion resistance, stain resistance, flame retardancy, and weather resistance while maintaining the original design of the substrate. In addition, the present invention relates to a laminate having a coating film formed from the coating composition. Background Art

[0002] In recent years, in the field of furniture and interior building material coatings, from the aspect of environmental problems, the dispersion medium has shifted from an organic solvent system to an aqueous system. In particular, volatile organic compounds may cause sick building syndrome, so there is a strong expectation for the use of aqueous coatings. As the binder resin used in aqueous coating applications, acrylic resins, polyurethane resins, alkyd resins, etc. have excellent film-forming ability and are thus widely used. In addition, silicone resins are known as resins that can impart lubricity and water repellency to substrates.

[0003] For example, in Japanese Patent Laid-Open No. 2006-341163 (Patent Document 1), a topcoat paint for interior building use containing a mixture of a silicone emulsion and a synthetic resin emulsion other than it is disclosed. However, when a silicone emulsion is added to the paint, sometimes the target coating film cannot be obtained due to a decrease in touch, abrasion resistance, and adhesion to the substrate caused by oil bleeding. In addition, there are disadvantages that dirt easily adheres and is also difficult to remove.

[0004] In addition, in the publication of Japanese Patent Laid-Open No. 2011-213941 (Patent Document 2), an aqueous coating composition containing a hydroxy-containing (meth)acrylic polymer emulsion and a silicone resin aqueous dispersion is disclosed. It is disclosed that the water resistance becomes good by mixing an acrylic emulsion and a silicone emulsion, but in this aqueous coating composition, it is considered that it is also difficult to obtain excellent touch and stain resistance.

[0005] The present inventors disclosed in the publication of Japanese Patent Laid-Open No. 2013-67787 (Patent Document 3) that a coating agent obtained by mixing urethane-based, acrylic-based, vinyl chloride-based emulsions and a silicone-based resin can impart water repellency to substrates. However, when using this coating agent, the lubricity is insufficient, so there is room for improvement in terms of touch, and in addition, the abrasion resistance is also insufficient, so there is room for improvement.

[0006] Prior Art Documents

[0007] Patent Document 1: Japanese Patent Laid-Open No. 2006-341163

[0008] Patent Document 2: Japanese Unexamined Patent Application Publication No. 2011-213941

[0009] Patent Document 3: Japanese Unexamined Patent Application Publication No. 2013-67787 Summary of the Invention

[0010] Problems to be Solved by the Invention

[0011] In view of the above circumstances, the object of the present invention is to provide a coating composition for furniture and architectural interiors that imparts excellent touch, abrasion resistance, stain resistance, flame retardancy, and weather resistance to a substrate, as well as a laminate, furniture, and architectural interior material having a coating film containing the coating composition.

[0012] Means for Solving the Problems

[0013] As a result of intensive studies by the inventors of the present invention to achieve the above object, it has been found that a coating composition containing (A) a specific silicone acrylate copolymer emulsion, (B) a specific resin emulsion other than the aforementioned (A), (C) a pigment, and (D) a flame retardant in a specified ratio, and a coating film using the coating composition are most suitable as coatings for furniture and architectural interiors, and the above problems have been solved, thereby completing the present invention.

[0014] That is, the present invention provides a coating composition for furniture or architectural interiors, which contains the following components (A) to (D).

[0015] (A) An emulsion of a silicone acrylate copolymer, which is a copolymer of (a1) 60 to 99 parts by mass of a polyorganosiloxane represented by the following general formula (1) and (a2) 1 to 40 parts by mass of an acrylate monomer and / or a methacrylate monomer (the total of the components (a1) and (a2) is 100 parts by mass): 0.5 to 20 parts by mass based on the solid content.

[0016] [Chemical Formula 1]

[0017]

[0018] (In the formula, R 1 are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms (excluding the groups defined by R 2 described later and phenyl), R 2 are each independently an alkenyl group having 2 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms in which a part of the hydrogen atoms bonded to the carbon atom is replaced by a mercapto group, a vinyl group, an acryloyloxy group, or a methacryloyloxy group, R 3 are each independently a phenyl group or the group defined by the above R 1 , and two R 3At least one of them is phenyl, Xs are each independently 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, a, b, c, and d are real numbers, and relative to the total of a, b, c, and d, a is a number such that 0.11 ≤ a / (a + b + c + d) < 1, b is a number such that 0.00001 ≤ b / (a + b + c + d) ≤ 0.05, c is a number such that 0 ≤ c / (a + b + c + d) ≤ 0.6, and d is a number such that 0.000001 ≤ d / (a + b + c + d) ≤ 0.24);

[0019] (B) At least one resin emulsion selected from an acrylic resin emulsion, a urethane resin emulsion, and an alkyd resin emulsion other than the component (A) above: 20 to 80 parts by mass in terms of the solid content,

[0020] (C) Pigment: 1 to 50 parts by mass, and

[0021] (D) Flame retardant: 1 to 10 parts by mass

[0022] (wherein, the total of the solid content of the component (A), the solid content of the component (B), the component (C), and the component (D) is 100 parts by mass).

[0023] Advantages of the Invention

[0024] The coating composition of the present invention forms a film having excellent touch, abrasion resistance, stain resistance, flame retardancy, and weather resistance. While maintaining the original design of the substrate, this film imparts excellent touch, abrasion resistance, stain resistance, flame retardancy, and weather resistance to the substrate. In addition, since the coating composition of the present invention is aqueous, it has great advantages in terms of operation and environment. The aqueous coating composition of the present invention is suitable as an aqueous coating for furniture and interior decoration of buildings. Detailed Description of Embodiments

[0025] Hereinafter, each component will be described in detail.

[0026] (A) Emulsion of silicone acrylate copolymer resin

[0027] (A) The component is an emulsion of a silicone acrylate copolymer, which is a copolymer of (a1) 60 to 99 parts by mass of a polyorganosiloxane represented by the following general formula (1) and (a2) 1 to 40 parts by mass of an acrylate monomer and / or a methacrylate monomer (the total of the components (a1) and (a2) is 100 parts by mass).

[0028] [Chemical Formula 2]

[0029]

[0030] (In the formula, R 1are independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms (wherein R 2 phenyl), R 2 are independently an alkenyl group having 2 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms in which a portion of hydrogen atoms bonded to carbon atoms is replaced by a mercapto group, a vinyl group, an acryloyloxy group or a methacryloyloxy group, R 3 are independently phenyl or the above R 1 The defined group, two R bonded to the same silicon atom 3 At least one of them is phenyl, X is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxy group, a, b, c, and d are real numbers, and relative to the total of a, b, c, and d, a is a number such that 0.11≤a / (a+b+c+d)<1, b is a number such that 0.00001≤b / (a+b+c+d)≤0.05, c is a number such that 0≤c / (a+b+c+d)≤0.6, and d is a number such that 0.000001≤d / (a+b+c+d)≤0.24).

[0031] More specifically, it is an emulsion of a silicone acrylic copolymer resin obtained by emulsifying and graft-polymerizing (a1) a polyorganosiloxane represented by the general formula (1) and (a2) an acrylate monomer and / or a methacrylate monomer.

[0032] The mixing ratio of component (a1) to component (a2) is preferably 60 to 99 parts by mass of component (a1) and 1 to 40 parts by mass of component (a2) relative to 100 parts by mass of the total amount of component (a1) and component (a2). Preferably, component (a1) is 70 to 95 parts by mass and component (a2) is 5 to 30 parts by mass.

[0033] [Chemistry 3]

[0034]

[0035] R 1 Each of them is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. For example, alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, and octadecyl, cycloalkyl groups such as cyclopentyl, cyclohexyl, and cycloheptyl, aryl groups such as tolyl and naphthyl, alkenylaryl groups such as vinylphenyl, aralkyl groups such as benzyl, phenylethyl, and phenylpropyl, and alkenylaralkyl groups such as vinylbenzyl and vinylphenylpropyl. Groups in which a part or all of the hydrogen atoms of these groups are replaced by halogen atoms such as fluorine, bromine, and chlorine, carboxyl groups, alkoxy groups, alkenyloxy groups, and amino groups can be mentioned. As R 1, preferably an unsubstituted alkyl group having 1 to 6 carbon atoms, more preferably a methyl group.

[0036] R 2 Each independently is an alkenyl group having 2 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms in which a part of the hydrogen atoms bonded to the carbon atom is replaced by a mercapto group, a vinyl group, an acryloyloxy group or a methacryloyloxy group. Examples of the alkenyl group having 2 to 6 carbon atoms include a vinyl group and an allyl group. R 2 Preferably an alkyl group having 1 to 6 carbon atoms having an acryloyloxy group or a methacryloyloxy group. The alkyl group is preferably a methyl group, an ethyl group or a propyl group. R 3 Each independently is a phenyl group or the group defined by the above R 1 , and at least one of the two R 3 bonded to the same silicon atom is a phenyl group.

[0037] X is each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms, or a hydroxyl group. Examples of the unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms include the groups exemplified for the above R 1 . Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy, ethoxy, propoxy, butoxy, hexyloxy, heptyloxy, octyloxy, decyloxy, tetradecyloxy and the like. As X, a hydroxyl group, a methyl group, a butyl group and a phenyl group are preferred.

[0038] a, b, c and d are real numbers. With respect to the total count of a to d, a is a number such that 0.11 ≤ a / (a + b + c + d) < less than 1 (for example, 0.999999 or less), preferably a number such that 0.59 ≤ a / (a + b + c + d) ≤ 0.99998. b is a number such that 0.00001 ≤ b / (a + b + c + d) ≤ 0.05 with respect to the total count of a to d, preferably a number such that 0.00001 ≤ b / (a + b + c + d) ≤ 0.01. c is a number such that 0 ≤ c / (a + b + c + d) ≤ 0.6 with respect to the total count of a to d, preferably a number such that 0 ≤ c / (a + b + c + d) ≤ 0.30. d is a number such that 0.000001 ≤ d / (a + b + c + d) ≤ 0.24 with respect to the total count of a to d, preferably a number such that 0.00001 ≤ d / (a + b + c + d) ≤ 0.1. If b is greater than 5% by mass, the improvement in the touch feeling of the coating film cannot be observed and the antifouling property is also reduced. If d is greater than 24.0% by mass, the weight average molecular weight becomes small and the improvement in the touch feeling cannot be observed, so it is not preferred. c is the number of siloxane units having a phenyl group. Having within the above range is preferred in terms of transparency and heat resistance.

[0039] (a1) The weight-average molecular weight of the polyorganosiloxane is 5,000 to 500,000, preferably 8,000 to 450,000, more preferably 100,000 to 450,000, and even more preferably 150,000 to 400,000. By having this weight-average molecular weight, a coating agent that imparts the excellent lubricity peculiar to silicone can be obtained.

[0040] Here, the molecular weight of the polyorganosiloxane can be calculated from the specific viscosity ηsp (25 °C) of a toluene solution of the organopolysiloxane at a concentration of 1 g / 100 ml.

[0041] ηsp = (η / η0) - 1

[0042] (η0: viscosity of toluene, η: viscosity of the solution)

[0043] ηsp = [η] + 0.3[η]², [η] = 2.15×10 -4 M 0.65 .

[0044] Specifically, 20 g of the emulsion is mixed with 20 g of IPA (isopropyl alcohol). After destroying the emulsion, the IPA is discarded, and the remaining rubbery organopolysiloxane is dried at 105 °C for 3 hours. It is made into a toluene solution of the organopolysiloxane at a concentration of 1 g / 100 ml and measured at 25 °C using an Ubbelohde viscometer. By substituting the viscosity into the above formula, the molecular weight can be determined (reference: Nakamuta, Nippon Kagaku, 77858

[1956] , Doklady Akad. Nauk. U.S.S.R. 8965

[1953] ).

[0045] Such (a1) polyorganosiloxane is preferably used in the form of an emulsion, and commercially available products can be used, or it can be synthesized. In the case of synthesis, it can be carried out by a known emulsion polymerization method. For example, a cyclic organosiloxane or an α,ω-dihydroxy siloxane oligomer, an α,ω-dialkoxy siloxane oligomer, an alkoxysilane, etc. optionally having a fluorine atom, a (meth)acryloyloxy group, a carboxyl group, a hydroxyl group, or an amino group, and a silane coupling agent represented by the following general formula (2) are emulsified and dispersed in water using an anionic surfactant, and then, if necessary, an acid or the like is added as a catalyst to carry out a polymerization reaction, thereby easily synthesizing it. R 5 (4-e-f) R 6 f Si(OR 7 ) e (2)

[0046] (In the formula, R 5 represents a monovalent organic group having a polymerizable double bond, particularly an alkyl group having 1 to 6 carbon atoms substituted with an acryloyloxy group or a methacryloyloxy group. R 6 represents an alkyl group having 1 to 4 carbon atoms, and R 7represents an alkyl group having 1 to 4 carbon atoms, e represents an integer of 2 to 3, f represents an integer of 0 to 1, and e + f = 2 to 3).

[0047] 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, 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)tetramethylcyclotetrasiloxane, 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(lauryl) - 3 - aminopropyl)tetramethylcyclotetrasiloxane, etc. Octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane are preferably used.

[0048] Examples of the silane coupling agent include acrylic silanes such as γ - (meth)acryloxypropyltrimethoxysilane, γ - (meth)acryloxypropyltriethoxysilane, γ - (meth)acryloxypropyltripropoxysilane, γ - (meth)acryloxypropyltriisopropoxysilane, γ - (meth)acryloxypropyltributoxysilane, γ - (meth)acryloxypropylmethyldimethoxysilane, γ - (meth)acryloxypropylmethyldiethoxysilane, γ - (meth)acryloxypropylmethyldipropoxysilane, γ - (meth)acryloxypropylmethyldiisopropoxysilane, γ - (meth)acryloxypropylmethyldibutoxysilane, etc.; mercapto silanes such as γ - mercaptopropylmethyldimethoxysilane, γ - mercaptopropyltrimethoxysilane, etc. There is a more preferred case where the production of alcohol is inhibited by the oligomer obtained by their polycondensation. Acrylic silane series are particularly preferred. Here, (meth)acryloxy represents acryloxy or methacryloxy. These silane coupling agents are preferably used in an amount of 0.01 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, based on 100 parts by mass of the cyclic organosiloxane. If it is less than 0.01 part by mass, the transparency decreases when making a coating agent, and if it is more than 10 parts by mass, there is a possibility that the slidability cannot be exhibited.

[0049] The above silane coupling agent is copolymerized in a cyclic organosiloxane, whereby a polymerizable group (R 2 ) is introduced into the polyorganosiloxane. Thereby, the (a2) (meth) acrylate monomer can be grafted onto the (a1) polyorganosiloxane.

[0050] As the polymerization catalyst used in the polymerization, a known polymerization catalyst may be used. Among them, a strong acid is preferred, and examples thereof include hydrochloric acid, sulfuric acid, dodecylbenzenesulfonic acid, citric acid, lactic acid, and ascorbic acid. Dodecylbenzenesulfonic acid having emulsifying ability is preferred.

[0051] Regarding the usage amount of the acid catalyst, relative to 100 parts by mass of the cyclic organosiloxane, it is preferably 0.01 to 10 parts by mass, more preferably 0.2 to 2 parts by mass.

[0052] As the surfactant during polymerization, as an anionic surfactant, sodium lauryl sulfate, sodium laureth sulfate, N-acyl amino acid salt, N-acyl taurate, aliphatic soap, alkyl phosphate, etc. can be cited. Among them, a surfactant that is easily soluble in water and does not have a polyethylene oxide chain is preferred. Further preferred are N-acyl amino acid salts, N-acyl taurates, aliphatic soaps, and alkyl phosphates, and particularly preferred are sodium lauroyl methyl taurate, sodium myristoyl methyl taurate, and sodium lauryl sulfate.

[0053] Regarding the usage amount of the anionic surfactant, relative to 100 parts by mass of the cyclic organosiloxane, it is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass.

[0054] 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. Further, it is particularly preferred to age at 5 to 30 °C for 10 hours or more after polymerization.

[0055] (a2) An acrylate or methacrylate (hereinafter sometimes referred to as an acrylic component) is a linear and branched alkyl ester having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms. It may have functional groups such as an amide group, a vinyl group, a carboxyl group, and a hydroxyl group. Examples of the acrylate and methacrylate include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, etc. It is possible to copolymerize only one of them or two or more of them. Methyl acrylate, ethyl acrylate, methyl methacrylate or ethyl methacrylate is preferred. The glass transition temperature (hereinafter sometimes referred to as Tg) of the acrylate and methacrylate may be 120 °C or lower, and may be 110 °C or lower. The lower limit value is preferably -50 °C. Preferably, the component (a2) can be adjusted so that the Tg of the obtained silicone acrylate copolymer resin reaches 0 °C or higher, more preferably 5 °C or higher, and graft copolymerization is carried out. By the silicone acrylate resin having the above Tg, a resin with high antifouling performance can be obtained.

[0056] The graft copolymerization of the above (a1) polyorganosiloxane and (a2) (meth)acrylate monomer can be carried out according to a conventionally known method, for example, using a radical initiator. The radical initiator is not particularly limited, and examples include persulfates such as potassium persulfate and ammonium persulfate, persulfuric acid hydrogen water, tert-butyl hydroperoxide, and hydrogen peroxide. If necessary, a redox system using a combination of reducing agents such as sodium acid sulfite, Rongalite, L-ascorbic acid, tartaric acid, saccharides, and amines can also be used.

[0057] In order to improve the stability of the emulsion, as an anionic surfactant, sodium lauryl sulfate, sodium laureth sulfate, N-acyl amino acid salt, N-acyl taurate, aliphatic soap, alkyl phosphate, etc. can be added. In addition, nonionic emulsifiers such as polyoxyethylene lauryl ether and polyoxyethylene tridecyl ether can also be added.

[0058] Furthermore, in order to adjust the molecular weight, a chain transfer agent can be added.

[0059] (A) The solid content of the silicone acrylate copolymer resin emulsion is preferably 35 to 50% by mass. In addition, the viscosity (25 °C) is preferably 500 mPa·s or lower, more preferably 20 to 300 mPa·s. The viscosity can be measured by a rotational viscometer. The average particle size of the emulsion particles is 1000 nm or lower, preferably 100 nm to 500 nm, more preferably 150 to 350 nm. When the average particle size is too large, whitening is observed, and when it is too small, there is a problem of reduced dispersibility. The particle size of the resin emulsion is measured using JEM-2100TM manufactured by JEOL Ltd.

[0060] The silicone acrylate copolymer resin emulsion of component (A) is preferably 0.5 to 20 parts by mass, more preferably 1.5 to 15 parts by mass, and still more preferably 2 to 10 parts by mass in terms of the solid content of component (A) based on the total 100 parts by mass of the solid content of component (A), the solid content of component (B), components (C) and (D). When the solid content of component (A) is lower than the above lower limit value, the touch and stain resistance cannot be fully exerted, and when it is greater than the above upper limit value, there is a disadvantage that the coating film surface is easily soiled. In the coating composition, it can be contained in an amount of 0.1 to 9% by mass, preferably 0.5 to 7% by mass based on the solid content. The glass transition temperature (hereinafter sometimes referred to as Tg) of the (A) silicone acrylate copolymer resin is preferably 0 °C or higher, more preferably 5 °C or higher.

[0061] It should be noted that the glass transition temperature (T) of the polymer resin can be calculated by the following formula.

[0062] (Pa + Pb + Pc) / T = (Pa / Ta) + (Pb / Tb) + (Pc / Tc)

[0063] In the formula, T represents the glass transition temperature (K) of the polymer particles, Pa, Pb, and Pc respectively represent the contents (mass %) of monomers a, b, and c, and Ta, Tb, and Tc respectively represent the glass transition temperatures (K) of the homopolymers of monomers a, b, and c. The glass transition temperature can be measured based on JIS K7121.

[0064] Furthermore, the above formula can also be applied in the case of adding monomers. The glass transition temperature of the following (B) resin emulsion can also be calculated by the above formula.

[0065] (B) Resin emulsion

[0066] Component (B) is at least one resin emulsion selected from acrylic resin emulsion, urethane resin emulsion, and alkyd resin emulsion other than component (A). More specifically, it is an acrylic resin emulsion, a urethane resin emulsion, and an alkyd resin emulsion using (meth)acrylic acid and (meth)acrylate and other (meth)acrylic monomers. It can preferably be a resin emulsion having a film-forming ability. The film-forming ability refers to the property that the granularity on the surface of the dried coating film disappears above a certain temperature and no fine cracks occur during drying. The drying temperature (MFT) range for film formation is not particularly limited. The hardness of the coating film of the paint when drying the (B) resin emulsion is measured according to JIS K5400-5-4, and there is no particular limitation, and it is preferably 2B to 2H with a pencil hardness tester.

[0067] (B) The average particle diameter of the resin emulsion is preferably 20 nm to 1000 nm, more preferably 20 nm to 500 nm, and further preferably 20 nm to 350 nm. The particle diameter of the resin emulsion is measured using JEM-2100TM manufactured by JEOL Ltd.

[0068] The acrylic resin emulsion may be a substance synthesized by a known method such as emulsion polymerization using an anionic or nonionic emulsifier, etc., or a commercially available product may be used.

[0069] Examples of the (meth)acrylic monomer include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, acrylic acid, methacrylic acid, crotonic acid, etc. In addition, the glass transition temperature (hereinafter sometimes referred to as Tg) is 120 °C or lower, preferably 60 °C or lower, and further preferably 30 °C or lower. It should be noted that the lower limit value of the glass transition temperature is preferably -50 °C.

[0070] Examples of commercially available acrylic resin emulsions include Vinibran manufactured by Nissin Chemical Industry Co., Ltd., Yodzol manufactured by Henkel Japan Co., Ltd., and Aron manufactured by Toagosei Co., Ltd.

[0071] The urethane resin emulsion may be a substance synthesized by a known method such as emulsion polymerization using an anionic or nonionic emulsifier, etc., or a commercially available product may be used.

[0072] Examples of the urethane resin emulsion include the reaction product of polyisocyanate and polyol, and various water-soluble urethane resins such as polyether-based, polycarbonate-based, and polyester-based can be cited as the polyol used. In order for the urethane resin emulsion to have the ability to form a coating film, the particle diameter is preferably 10 to 500 nm. A urethane resin emulsion having a viscosity (25 °C) of 10 to 500 mPa·s can be used. In addition, the glass transition temperature (hereinafter sometimes referred to as Tg) is 120 °C or lower, preferably 60 °C or lower, and further preferably 30 °C or lower. It should be noted that the lower limit value of the glass transition temperature is preferably -50 °C. The glass transition temperature can be measured based on JIS K7121.

[0073] Examples of commercially available polyether-based urethane resin emulsions include Adeka Bon Titer HUX-350 manufactured by Adeka Corporation, WLS-201 and WLS-202 manufactured by DIC Corporation, Superflex E-4000 and E-4800 manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and the like. Examples of polycarbonate-based urethane resin emulsions include, for example, Hydran WLS-210 and WLS-213 manufactured by DIC Corporation, UW-1005E and UW-5502 manufactured by Ube Industries, Ltd., Permaline UA-368 manufactured by Sanyo Chemical Industries, Ltd., Superflex 460 and Superflex 470 manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and the like. Examples of polyester-based urethane resin emulsions include Adeka Bon Titer HUX-380 and HUX-540 manufactured by Adeka Corporation, Superflex 420 and Superflex 860 manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and the like.

[0074] As the alkyd resin emulsion, a substance obtained by the following method can be used: for example, a method of neutralizing an alkyd resin having a high acid value with a basic compound such as an amine compound to make it water-based; a method of introducing a hydrophilic group such as a polyoxyethylene group into the alkyd resin and self-emulsifying it in water by the action of this hydrophilic group; a method of dispersing the alkyd resin in water by forcibly stirring it in water using a high-speed stirrer such as a dispersion type stirrer in the presence of an emulsifier; a method of further making the alkyd resin a low acid value substance, improving the water dispersibility of the water-dispersed alkyd resin particles obtained by a high-speed stirrer, and in order to further uniformly reduce the particle size, using a disperser having a specific high-energy shearing ability for atomization and dispersing it in water; a method of combining these; commercially available products can also be used.

[0075] Examples of commercially available alkyd resin emulsions include, for example, the Waterzol series manufactured by DIC Corporation.

[0076] (B) The compounding amount of the resin emulsion is 20 to 80 parts by mass, preferably 30 to 78 parts by mass, and more preferably 40 to 75 parts by mass in terms of the solid content amount with respect to the total of 100 parts by mass of the solid content amount of component (A), the solid content amount of component (B), component (C) and component (D). In the coating composition, it can be contained in an amount of 10 to 35% by mass, preferably 15 to 32% by mass in terms of the solid content amount. If the resin emulsion (solid content) is lower than the above lower limit value, there is a defect that film properties such as abrasion resistance become very poor, and if it is greater than the above upper limit value, there is a defect that the touch feeling deteriorates.

[0077] (C) Pigment

[0078] (C) The pigment may be any conventionally known pigment incorporated in the coating composition, and can be either an inorganic pigment or an organic pigment. Examples of inorganic pigments include titanium oxide, red iron oxide (iron oxide red), yellow iron oxide, black iron oxide, Prussian blue, zinc white, cobalt blue, emerald green, chrome green, titanium white, etc. Examples of organic pigments include basic blue, lithol red, carmine 6B, diazo yellow, phthalocyanine blue, quinacridone red, isoindoline yellow, etc.

[0079] (C) The average particle size of the pigment is not particularly limited, preferably 5 nm to 10 μm, more preferably 10 nm to 5 μm. The average particle size of this pigment is the volume average particle size measured by a laser diffraction particle size analyzer.

[0080] (C) The amount of the pigment incorporated is 1 to 50 parts by mass, preferably 5 to 35 parts by mass, based on the total of 100 parts by mass of the solid component amount of component (A), the solid component amount of component (B), component (C), and component (D). In the coating composition, it can be contained in an amount of 0.1 to 25% by mass, preferably 0.5 to 20% by mass. If the amount of the pigment is less than the above lower limit, there is a defect that the hiding power is insufficient and the design cannot be changed. If it is greater than the above upper limit, there is a defect that the dispersibility is poor and particles are generated even after coating, which is not preferable.

[0081] (D) Flame retardant

[0082] (D) The flame retardant may be any conventionally known flame retardant incorporated in the coating composition. For example, it can be an inorganic flame retardancy-improving component, and examples include phosphorus compounds (triphenyl phosphate, tricresyl phosphate, tris(dimethylphenyl) phosphate, tris(β-chloropropyl) phosphate, tris(dichloropropyl) phosphate, condensed phosphate esters, ammonium polyphosphate), hydrated metal compounds such as aluminum hydroxide and magnesium hydroxide, zinc borate, molybdenum compounds (molybdenum trioxide), antimony compounds (antimony oxide, antimony pentoxide, sodium antimonate), etc.

[0083] (D) The amount of the flame retardant incorporated is 1 to 10 parts by mass, more preferably 1 to 5 parts by mass, based on the total of 100 parts by mass of the solid component amount of component (A), the solid component amount of component (B), component (C), and component (D). In the coating composition, it can be contained in an amount of 0.1 to 5% by mass, preferably 0.5 to 2% by mass. When it is less than the above lower limit or greater than the upper limit, the antifouling property, weather resistance, etc. decrease. The average particle size is preferably 0.5 to 20 μm. The average particle size of the flame retardant is the volume average particle size measured by a laser diffraction particle size analyzer.

[0084] (E) Matting agent

[0085] The coating composition of the present invention may further contain (E) a matting agent. As the (E) matting agent, any conventionally known matting agent incorporated in the coating composition may be used, and examples thereof include silica, crosslinked acrylic resin, crosslinked urethane resin, etc. By adjusting the amount and type of the matting agent, the appearance of the coating film can be adjusted to a matte or semi-glossy substance.

[0086] There is no particular limitation on the average particle size of the (E) matting agent, and it is preferably 0.5 μm to 30 μm, more preferably 1 μm to 15 μm. The average particle size of the matting agent is the volume average particle size measured by a laser diffraction type particle size measuring device.

[0087] The blending amount of the (E) matting agent relative to the total mass of the coating composition is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass, and still more preferably 2 to 10% by mass. If the matting agent is below the lower limit value, it may be impossible to obtain a matting effect at all. If it exceeds the above upper limit value, there is a risk of the coating composition turning white.

[0088] The coating composition of the present invention is obtained by mixing (A) a silicone acrylic copolymer emulsion, (B) a resin emulsion, a substance obtained by previously dispersing (C) a pigment in water, and a substance obtained by previously dispersing (D) a flame retardant and (E) a matting agent in water under an aqueous system by a known mixing preparation method such as a paddle mixer, a homogenizer, a ball mill, a bead mill, a dispersion mixer, etc.

[0089] For example, when the component (B) is stirred at 500 rpm by a dispersion mixer, the component (A), the aqueous dispersion of the component (C), the aqueous dispersions of the components (D) and (E) are added, and stirred at 1000 rpm for 30 minutes to obtain the coating composition of the present invention.

[0090] There is no particular limitation on the range of the drying temperature (MFT) for forming the coating film of the coating composition, and it is preferably 30°C or lower. There is no particular limitation on the hardness of the coating film, and it is preferably 2B to 4H, more preferably 2B to 2H, as measured by a pencil hardness tester. It should be noted that the hardness can be measured according to JIS K5400-5-4.

[0091] In addition, in the coating composition of the present invention, within a range that does not affect the performance, antioxidants, ultraviolet absorbers, antifreezing agents, pH regulators, preservatives, defoamers, antibacterial agents, mildew-proof agents, light stabilizers, antistatic agents, plasticizers, flame retardants, thickeners, surfactants, film-forming aids and other organic solvents, other resins, etc. can be added.

[0092] The furniture and architectural interior coating composition of the present invention obtained in such a manner is coated or impregnated on one or both sides of substrates such as wood, metal, resin, and ceramic, and dried (room temperature to 150 °C), thereby forming a coating film. The coating film containing the coating composition of the present invention can impart advantages such as water repellency, weather resistance, heat resistance, cold resistance, gas permeability, and slidability of silicone resin for a long time while maintaining the advantages of the substrate. The reason can be considered that the resin (B) having the ability to form a coating film and the curable silicone resin (A) form a firm sea-island structure.

[0093] As the wood substrate, woods such as Aceraceae, Betulaceae, Lauraceae, Fagaceae (Quercus family), Scrophulariaceae, Araucariaceae, Ulmaceae, Bignoniaceae, Rosaceae, Cupressaceae, Dipterocarpaceae, Myrtaceae, Fagaceae, Pinaceae, Leguminosae, and Oleaceae can be used. A method of hot air drying at 20 to 150 °C, particularly 50 to 150 °C for 0.5 to 5 hours is preferred. In addition, if the drying temperature is set below 120 °C, discoloration of the coating film can be avoided.

[0094] As the metal substrate, Si, Cu, Fe, Ni, Co, Au, Ag, Ti, Al, Zn, Sn, Zr, their alloys, etc. can be cited.

[0095] As the resin substrate, poly(meth)acrylates 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 can be used. As the drying method, a method of leaving at room temperature for 1 to 10 days can be cited. From the viewpoint of promoting curing rapidly, a method of heating at a temperature of 20 to 150 °C for 1 second to 10 hours is preferred. In addition, when the aforementioned resin substrate contains a material that is easily deformed or discolored by heating, drying at a lower temperature of 20 to 100 °C is preferred.

[0096] As the ceramic substrate, calcined products such as oxides, carbides, and nitrides can be cited.

[0097] The method of coating the coating composition of the present invention on the substrate is not particularly limited, and examples thereof include coating methods using various coating machines such as gravure coaters, bar coaters, knife coaters, roll coaters, air knife coaters, screen coaters, and curtain coaters, spraying, dipping, and brush coating.

[0098] The coating amount of the coating composition on the substrate is not particularly limited. Generally, from the viewpoints of antifouling property and workability, in terms of solid content conversion, it is preferably 1 to 300 g / m 2 、more preferably 5 to 100 g / m 2It is formed in a range or dry thickness of 1 to 500 μm, preferably 5 to 100 μm, and naturally dried or heat-dried to 100 to 200 °C to form a film.

[0099] The coating composition of the present invention is used for furniture and interior building materials, and imparts excellent touch, abrasion resistance, and stain resistance to the substrate. The laminate formed with the coating film using the coating composition has excellent touch, abrasion resistance, and stain resistance while maintaining the original design of the substrate.

[0100] Examples

[0101] Hereinafter, examples and comparative examples are shown to more specifically explain the present invention, but the present invention is not limited to the following examples.

[0102] It should be noted that in the following examples, "parts" and "%" represent parts by mass and mass%, respectively. The weight average molecular weight is a value calculated from the specific viscosity ηsp (25 °C) of a toluene solution of an organopolysiloxane at a concentration of 1 g / 100 ml by the aforementioned method. In addition, the particle size of each resin emulsion obtained in the following production examples and comparative production examples was measured using a JEM-2100TM manufactured by JEOL Ltd.

[0103] <Method for Measuring Solid Content>

[0104] The solid content of the resin emulsions obtained in the following production examples and comparative production examples was measured by the following method.

[0105] Approximately 1 g of each resin emulsion (sample) was accurately weighed into a dish made of aluminum foil, placed in a dryer maintained at approximately 105 °C, heated for 1 hour, taken out of the dryer, and allowed to cool in a desiccator. The weight of the sample after drying was measured, and the evaporation residue was calculated by the following formula.

[0106] [Equation 1]

[0107]

[0108] R: Evaporation residue (%)

[0109] W: Mass of the aluminum foil dish containing the sample before drying (g)

[0110] L: Mass of the aluminum foil dish (g)

[0111] T: Mass of the aluminum foil dish containing the sample after drying (g)

[0112] Dimensions of the aluminum foil dish: 70φ × 12h (mm).

[0113] (A) Manufacture of silicone acrylate copolymer resin emulsion

[0114] [Production Example 1]

[0115] 600 g of octamethylcyclotetrasiloxane, 0.48 g of γ-methacryloxypropylmethyldiethoxysilane, a substance obtained by dissolving 6 g of sodium lauryl sulfate in 54 g of pure water, and a substance obtained by dissolving 6 g of dodecylbenzenesulfonic acid in 54 g of pure water were put into a 2 L polyethylene beaker. After uniformly emulsifying with a homogenizer, 470 g of water was slowly added for dilution. At a pressure of 300 kgf / cm 2 The mixture was passed through a high-pressure homogenizer twice to obtain a uniform white emulsion. The emulsion was transferred to a 2 L glass flask equipped with a stirring device, a thermometer, and a reflux condenser, and a polymerization reaction was carried out at 55 °C for 24 hours. Thereafter, after aging at 15 °C for 24 hours, it was neutralized to near neutrality with 12 g of a 10% aqueous sodium carbonate solution.

[0116] The structure of the polyorganosiloxane obtained by the above polymerization reaction was determined by 1 H-NMR and 29 Si-NMR (apparatus name: JNM-ECA600, measurement solvent: CDCl 3、 1H frequency 600 MHz, room temperature, number of accumulation times 128 times, 29Si frequency 600 MHz, room temperature, number of accumulation times 5000 times). The result confirmed was represented by the following formula (1-1), and Mw (weight average molecular weight, measurement method as described above) was 250,000.

[0117] [Chemical formula 4]

[0118]

[0119] In formula (1-1), R 2 is γ-methacryloxypropyl, and X is a hydroxyl group or an ethoxy group. The ratios of a, b, and d are shown in Table 1.

[0120] To the above neutralized reaction solution (containing 534 g of the polyorganosiloxane obtained above), 232 g of methyl methacrylate (MMA) was added dropwise over 3 to 5 hours, and at the same time, an oxidation-reduction reaction was carried out with a peroxide and a reducing agent at 30 °C to carry out acrylic copolymerization with the above polyorganosiloxane, obtaining a silicone acrylic copolymer resin emulsion with a non-volatile content of 45.2%. The average particle diameter and solid content of the silicone acrylic copolymer resin emulsion are shown in Table 2.

[0121] [Production Example 2]

[0122] 600 g of octamethylcyclotetrasiloxane, 0.60 g of γ-methacryloxypropylmethyldiethoxysilane, a substance obtained by dissolving 6 g of sodium lauryl sulfate in 54 g of pure water, and a substance obtained by dissolving 6 g of dodecylbenzenesulfonic acid in 54 g of pure water were put into a 2 L polyethylene beaker. After uniformly emulsifying with a homogenizer, 470 g of water was slowly added for dilution, at a pressure of 300 kgf / cm 2 The mixture was passed through a high-pressure homogenizer twice to obtain a uniform white emulsion. The emulsion was transferred to a 2 L glass flask equipped with a stirring device, a thermometer, and a reflux condenser. After a polymerization reaction at 55 °C for 24 hours and aging at 5 °C for 24 hours, it was neutralized to near neutrality with 12 g of 10% aqueous sodium carbonate solution.

[0123] The structure of the polyorganosiloxane obtained by the above polymerization reaction was confirmed by NMR (equipment name: JNM-ECA600, measurement solvent: CDCl 3、 The measurement conditions were the same as those in Production Example 1). The result was that it was represented by the above formula (1-1), and Mw (weight average molecular weight, measurement method as described above) was 400,000. In the above formula (1-1), R 2 is γ-methacryloxypropyl, X is a hydroxyl group or an ethoxy group. The ratios of a, b, and d are shown in Table 1.

[0124] To the above neutralized reaction solution (containing 534 g of the polyorganosiloxane obtained above), 61 g of methyl methacrylate (MMA) was added dropwise over 3 to 5 hours, and at the same time, an oxidation-reduction reaction was carried out with a peroxide and a reducing agent at 30 °C, and acrylic copolymerization was carried out with the above polyorganosiloxane to obtain a silicone acrylate copolymer resin emulsion with a non-volatile content of 44.8%. The average particle diameter and solid content of the silicone acrylate copolymer resin emulsion are shown in Table 2.

[0125] [Production Example 3]

[0126] 300 g of octamethylcyclotetrasiloxane, 300 g of diphenyldimethylsiloxane (KF-54 manufactured by Shin-Etsu Chemical Co., Ltd.), 0.96 g of γ-methacryloxypropylmethyldiethoxysilane, a substance obtained by dissolving 24 g of 50% alkyldiphenyl ether disulfonate (Pelec SS-L, manufactured by Kao Corporation) in 45 g of pure water, and a substance obtained by dissolving 6 g of dodecylbenzenesulfonic acid in 54 g of pure water were put into a 2 L polyethylene beaker. After uniformly emulsifying with a homogenizer, 490 g of water was slowly added for dilution, at a pressure of 300 kgf / cm 2It was passed through a high-pressure homogenizer twice to obtain a uniform white emulsion. The emulsion was transferred to a 2 L glass flask equipped with a stirring device, a thermometer, and a reflux condenser. After a polymerization reaction was carried out at 55 °C for 10 to 20 hours and then aged at 10 °C for 10 to 20 hours, 12 g of a 10% aqueous sodium carbonate solution was used to neutralize the pH to near neutrality.

[0127] The structure of the polyorganosiloxane obtained by the above polymerization reaction was confirmed by NMR (apparatus name: JNM-ECA600, measurement solvent: CDCl 3、 (measurement conditions were the same as in Production Example 1). The result was that it was represented by the following formula (1-2), and Mw (weight average molecular weight, measurement method as described above) was 8,000.

[0128] [Chemical Formula 5]

[0129]

[0130] In the above formula (1-2), R 2 is γ-methacryloxypropyl, R 3 ' and R 3 ” are phenyl or methyl, at least one of R 3 ' and R 3 ” is phenyl, and X is a hydroxyl group or an ethoxy group. The ratios of a, b, c, and d are shown in Table 1.

[0131] The non-volatile content (solid content) of the emulsion obtained after the above neutralization was 47.5% after drying at 105 °C for 3 hours. To the above neutralized reaction solution (containing 534 g of the polyorganosiloxane obtained above), 242 g of methyl methacrylate (MMA) was added dropwise over 3 to 5 hours, and at the same time, an oxidation-reduction reaction was carried out with a peroxide and a reducing agent at 30 °C to carry out acrylic copolymerization with the above polyorganosiloxane to obtain a silicone acrylic copolymer resin emulsion with a non-volatile content of 45.5%. The average particle diameter and the solid content of the silicone acrylic copolymer resin emulsion are shown in Table 2.

[0132] [Production Example 4]

[0133] Repeat the above Preparation Example 1 to obtain a uniform white emulsion. Similar to Preparation Example 1, transfer this emulsion to a 2 L glass flask equipped with a stirring device, a thermometer, and a reflux condenser, and carry out a polymerization reaction at 55 °C for 24 hours. Thereafter, after aging at 15 °C for 24 hours, neutralize to near neutrality with 12 g of a 10% aqueous sodium carbonate solution. The obtained polyorganosiloxane is represented by the above formula (1-1) and has Mw (weight average molecular weight, measurement method as described above) of 250,000. To the above neutralized reaction solution (containing 534 g of the above obtained polyorganosiloxane), dropwise add 116 g of butyl acrylate (BA) and 116 g of methyl methacrylate (MMA) over 3 to 5 hours, and simultaneously carry out a redox reaction with a peroxide and a reducing agent at 30 °C to carry out acrylic copolymerization with the above polyorganosiloxane, obtaining a silicone acrylic copolymer resin emulsion with a non-volatile content of 44.9%. The average particle diameter and solid content of the silicone acrylic copolymer resin emulsion are shown in Table 2.

[0134] [Comparative Preparation Example 1]

[0135] Repeat the above Preparation Example 1 to obtain a uniform white emulsion. Similar to Preparation Example 1, transfer the emulsion to a 2 L glass flask equipped with a stirring device, a thermometer, and a reflux condenser, and carry out a polymerization reaction at 55 °C for 24 hours. After aging at 15 °C for 24 hours, neutralize to near neutrality with 12 g of a 10% aqueous sodium carbonate solution. The obtained polyorganosiloxane is represented by the above formula (1-1) and has Mw (weight average molecular weight, measurement method as described above) of 250,000.

[0136] To the above neutralized reaction solution (containing 534 g of the above obtained polyorganosiloxane), dropwise add 541 g of methyl methacrylate (MMA) over 3 to 5 hours, and simultaneously carry out a redox reaction with a peroxide and a reducing agent at 30 °C to carry out acrylic copolymerization with the above polyorganosiloxane, obtaining a silicone acrylic copolymer resin emulsion with a non-volatile content of 45.5%. The average particle diameter and solid content of the silicone acrylic copolymer resin emulsion are shown in Table 2.

[0137] [Comparative Preparation Example 2]

[0138] Repeat the above Preparation Example 1 to obtain a uniform white emulsion. Similar to Preparation Example 1, transfer the emulsion to a 2 L glass flask equipped with a stirring device, a thermometer, and a reflux condenser, and carry out a polymerization reaction at 55 °C for 24 hours. After aging at 15 °C for 24 hours, neutralize to near neutrality with 12 g of a 10% aqueous sodium carbonate solution. The obtained polyorganosiloxane is represented by the above formula (1-1) and has Mw (weight average molecular weight, measurement method as described above) of 250,000. Do not carry out acrylic polymerization and directly end. Obtain a silicone resin emulsion with a non-volatile content of 44.8%. The average particle diameter and solid content of the silicone acrylic copolymer resin emulsion are shown in Table 2.

[0139] [Comparative Production Example 3]

[0140] A substance obtained by dissolving 552 g of octamethylcyclotetrasiloxane, 48 g of γ-methacryloyloxypropylmethyldiethoxysilane, and 6 g of sodium lauryl sulfate in 54 g of pure water, and a substance obtained by dissolving 6 g of dodecylbenzenesulfonic acid in 54 g of pure water were put into a 2 L polyethylene beaker. After uniformly emulsifying with a homogenizer, 470 g of water was slowly added for dilution, and the pressure was 300 kgf / cm 2 It was passed through a high-pressure homogenizer twice to obtain a uniform white emulsion. This emulsion was transferred to a 2 L glass flask equipped with a stirring device, a thermometer, and a reflux condenser. After a polymerization reaction was carried out at 55°C for 24 hours and then aged at 15°C for 24 hours, it was neutralized to near neutrality with 12 g of a 10% aqueous sodium carbonate solution.

[0141] The structure of the polyorganosiloxane obtained by the above polymerization reaction was confirmed by NMR (equipment name: JNM-ECA600, measurement solvent: CDCl 3、 The measurement conditions were the same as those in Production Example 1). The result showed that it was represented by the following formula (1-3), and Mw (weight average molecular weight, measurement method as described above) was 250,000.

[0142] [Chemical Formula 6]

[0143]

[0144] In formula (1-3), R 2 is γ-methacryloyloxypropyl, and X is a hydroxyl group or an ethoxy group. The ratios of a, b, and d are shown in Table 1.

[0145] To the above neutralized reaction solution (containing 534 g of the polyorganosiloxane obtained above), 232 g of methyl methacrylate (MMA) was added dropwise over 3 to 5 hours, and at the same time, an oxidation-reduction reaction was carried out with a peroxide and a reducing agent at 30°C to carry out acrylic copolymerization with the above polyorganosiloxane, obtaining a silicone acrylic copolymer resin emulsion with a non-volatile content of 45.0%. The average particle diameter and solid content of the silicone acrylic copolymer resin emulsion are shown in Table 2.

[0146] [Table 1]

[0147]

[0148] D4: Octamethylcyclotetrasiloxane

[0149] KF-54: Diphenyldimethylsiloxane

[0150] Pelecs SS-L: 50% Alkyl diphenyl ether disulfonate.

[0151] [Table 2]

[0152]

[0153] [Formulation Example 1]

[0154] Preparation of aqueous dispersion containing (C) pigment

[0155] 112 parts of ion-exchanged water, 30 parts of Demol EP (a polycarboxylic acid type polymer surfactant manufactured by Kao Corporation), 50 parts of Discoat N-14 (an aqueous dispersion of an ammonium salt of a styrene-maleic acid monoester copolymer, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 25 parts of propylene glycol, 500 parts of (C) titanium oxide (Type-Peak CR-95 (rutile type titanium oxide with an average particle diameter of 0.28 μm, manufactured by Ishihara Sangyo Co., Ltd.)) and 100 parts of glass beads (diameter: 1 mm) were dispersed with a homogenizer at a rotational speed of 3000 rpm for 60 minutes, and then filtered through a 100-mesh wire net to prepare a white paste.

[0156] [Formulation Example 2]

[0157] Preparation of aqueous dispersion containing (D) flame retardant and (E) matting agent

[0158] 80 parts of ion-exchanged water, 10 parts of ALH-3L as (D) flame retardant (high heat-resistant aluminum hydroxide manufactured by Kawauchi Lime Industry Co., Ltd., average particle diameter 4.5 μm, 1% thermal decomposition temperature 280 °C), and 10 parts of Silicia 550 as (E) matting agent (average particle diameter 4 μm, pore volume 0.8 ml / g, colloidal silica manufactured by Fuji Silicia Co., Ltd.) were mixed and stirred with a dispersion mixer at 1000 rpm for 20 minutes to obtain an aqueous dispersion.

[0159] [Formulation Example 3]

[0160] Preparation of aqueous dispersion containing (D) flame retardant

[0161] 80 parts of ion-exchanged water and 20 parts of ALH-3L as (D) flame retardant (high heat-resistant aluminum hydroxide manufactured by Kawauchi Lime Industry Co., Ltd., average particle diameter 4.5 μm, 1% thermal decomposition temperature 280 °C) were mixed and stirred with a dispersion mixer at 1000 rpm for 20 minutes to obtain an aqueous dispersion.

[0162] [Formulation Example 4]

[0163] Preparation of aqueous dispersion containing (E) matting agent

[0164] 80 parts of ion-exchanged water and 20 parts of Silicia 550 as (E) matting agent (average particle diameter 4 μm, pore volume 0.8 ml / g, colloidal silica manufactured by Fuji Silicia Co., Ltd.) were mixed and stirred with a dispersion mixer at 1000 rpm for 20 minutes to obtain an aqueous dispersion.

[0165] The (B) resin emulsions used in the following Examples and Comparative Examples are as described below.

[0166] Aron A-104 (aqueous acrylic resin emulsion, manufactured by Toagosei Co., Ltd., solid content 40%)

[0167] Hydran WLF-213 (urethane dispersion, manufactured by DIC Corporation, solid content 35%, average molecular weight 150,000)

[0168] Waterzole BCD-3100 (aqueous polyester alkyd resin, manufactured by DIC Corporation, solid content 43%)

[0169] [Example 1]

[0170] As the (B) aqueous acrylic resin emulsion, the product named "Aron A-104" (viscosity 300 - 1000 mPa·s) manufactured by Toagosei Co., Ltd. was used. At the compounding amounts shown in Table 3 below, while stirring the resin emulsion, the silicone acrylic copolymer resin emulsion obtained in Production Example 1 of (A), the white paste of Preparation Example 1, and the aqueous dispersion of Preparation Example 2 were added, and further ion-exchanged water was added to adjust the solid content, and it was stirred with a ball mill for 2 hours. The balls were filtered through 100 mesh to obtain an aqueous coating composition. The solid content contained in this coating composition was about 35%. It was coated on cedar wood chips and a PET film according to the method shown below to form a coated film.

[0171] [Examples 2 - 8, Comparative Examples 1 - 10]

[0172] The composition shown in Table 3 or 4 below was used, and except for this, the steps of Example 1 above were repeated to produce an aqueous coating composition. The compounding amounts of the respective components were adjusted so that the solid content of the entire coating composition reached about 40%. This coating composition was coated on cedar wood chips and a PET film according to the method shown below to form a coated film.

[0173] [Examples 9 - 10, Comparative Examples 11 - 12]

[0174] The composition shown in Table 8 below was used, and except for this, the steps of Example 1 above were repeated to produce an aqueous coating composition. The compounding amounts of the respective components were adjusted so that the solid content of the entire coating composition reached about 40%. This coating composition was applied by painting on a SUS303 stainless steel plate to form a coated film.

[0175] <Film-forming method>

[0176] The obtained coating composition was applied onto Chinese fir chips, PET film, or SUS304 stainless steel plate using a bar coater in such a way that the dried film thickness reached 26 μm, and then left at room temperature for 2 days to form a coated film.

[0177] For the coated films formed on Chinese fir chips and SUS304 stainless steel plate, the touch feeling, static and kinetic friction coefficients, and stain resistance were evaluated by the methods shown below.

[0178] For the coated film formed on PET film, the abrasion resistance was evaluated by the method shown below.

[0179] <Measurement of static and kinetic friction coefficients and touch feeling>

[0180] Using HEIDON TYPE-38 (manufactured by Shinto Scientific Co., Ltd.), a 200 g metal indenter was vertically brought into contact with the coating films of the above examples, and the frictional force when moving at 3 cm / min was measured. The static friction coefficient and kinetic friction coefficient were calculated based on the frictional force.

[0181] In addition, when the static friction coefficient was less than 0.10, the kinetic friction coefficient was less than 0.07, and the difference between the static friction coefficient and the kinetic friction coefficient was less than 0.05, the evaluation of the touch feeling was recorded as ○.

[0182] <Abrasion resistance>

[0183] The abrasion resistance of the PET film formed with the above coated film was measured using a Gakushin abrasion tester. A weight of 100 gf was applied, and a cotton cloth was attached to the metal contact object. The number of times until the coating film was damaged was visually confirmed every 100 times. The number of times just before breakage was recorded in the table.

[0184] <Stain resistance (removability of water-based markers and crayons)>

[0185] Water-based markers and crayons were painted on the coated film in a size of 5 mm × 2 cm. After drying at room temperature for 5 minutes each, a paper towel was wetted with water and wiped thoroughly. When almost all of it could be removed (the removed area was more than 70%), it was recorded as 〇; when a little could be removed (the removed area was 10 - 30%), it was recorded as △; when none could be removed at all, it was recorded as ×, and recorded in the table.

[0186] <Combustion test>

[0187] The combustion test and weather resistance test of the coated film were evaluated by fabricating the coating film as described below.

[0188] The coating composition was cast in a PE tray and dried at 60 °C for 24 h to obtain a film of 120 cm × 1.3 cm.

[0189] Place the film on a stainless steel plate and ignite it from one end with a lighter, then measure the time it takes to burn to the other end. The longer the burning time, the better the flame retardancy.

[0190] <Weather resistance test>

[0191] Use the film obtained by the method described in the above combustion test and conduct a 500-hour accelerated weather resistance test under the conditions of JIS A5759:2008 using a weather resistance testing machine of the sunshine carbon arc lamp type specified in JIS B7753:2007. When there are no appearance changes such as swelling, cracking, and peeling in the coating films of all test pieces, it is recorded as ◎, and otherwise it is recorded as ×.

[0192] <Water contact angle>

[0193] Use an automatic contact angle measuring device DMO-601 (manufactured by Kyowa Interface Science Co., Ltd.) to measure the contact angle of a 0.2 μL water droplet of ion-exchanged water 30 seconds after it contacts each coated film.

[0194]

[0195]

[0196] [Table 5]

[0197]

[0198] [Table 6]

[0199]

[0200] [Table 7]

[0201]

[0202] [Table 8]

[0203]

[0204] (Note) The solid content amount is the solid content amount of each of the components (A) to (E) contained in the coating composition.

[0205] As shown in Tables 5 to 8 above, the coating composition of the present invention forms a coated film on various substrates, which imparts excellent touch, abrasion resistance, stain resistance, flame retardancy, and weather resistance. In addition, since the coating composition of the present invention is aqueous-based, it has great advantages in terms of operation and environment. The aqueous-based coating composition of the present invention is suitable as an aqueous-based coating for furniture and interior decoration of buildings.

Claims

1. A coating composition for furniture or interior building decoration, comprising the following components (A) to (D): (A) An emulsion of a silicone acrylate copolymer resin, which is a copolymer of (a1) 60 to 99 parts by mass of a polyorganosiloxane represented by the following general formula (1) and (a2) 1 to 40 parts by mass of an acrylate monomer and / or a methacrylate monomer: 0.5 to 20 parts by mass based on the solid content, in the copolymer, the total of the (a1) and (a2) components is 100 parts by mass, [Chemical formula 1] In the formula, R 1 each independently is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, wherein R 2 Except for the groups defined above and phenyl, R 2 are independently an alkenyl group having 2 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms in which a portion of hydrogen atoms bonded to carbon atoms is replaced by a mercapto group, a vinyl group, an acryloyloxy group or a methacryloyloxy group, R 3 are independently phenyl or the above R 1 The defined group, two R bonded to the same silicon atom 3 at least one of them is phenyl, X is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxy group, a, b, c, and d are real numbers, with respect to the total of a, b, c, and d, a is a number such that 0.11≤a / (a+b+c+d)<1, b is a number such that 0.00001≤b / (a+b+c+d)≤0.05, c=0, and d is a number such that 0.000001≤d / (a+b+c+d)≤0.24, (B) At least one resin emulsion selected from an acrylic resin emulsion, a urethane resin emulsion, and an alkyd resin emulsion other than the component (A): 20 to 80 parts by mass based on the solid content, (C) Pigment: 1 to 50 parts by mass, and (D) Flame retardant: 1 to 10 parts by mass wherein the total of the solid content of the component (A), the solid content of the component (B), the component (C), and the component (D) is 100 parts by mass.

2. The coating composition for furniture or interior decoration of buildings according to claim 1, wherein, The average particle diameter of the silicone acrylate copolymer resin emulsion particles of the foregoing (A) is 100 nm to 1200 nm.

3. The coating composition for furniture or interior building decoration according to claim 1, further comprising (E) a matting agent in an amount of 0.5 to 10% by mass based on the total mass of the coating composition.

4. The coating composition for furniture or interior decoration of buildings according to claim 1, wherein, The pigment of the foregoing (C) is titanium oxide.

5. A coated film, comprising the coating composition according to any one of claims 1 to 4.

6. The coated film according to claim 5, wherein, The difference between the static friction coefficient and the dynamic friction coefficient is less than 0.

05.

7. A laminate having a substrate and the coated film according to claim 5 formed on one or both sides of the substrate.

8. The laminate according to claim 7, wherein, The foregoing substrate is selected from wood, metal, resin, and ceramic.

9. Furniture having the laminate according to claim 7 or 8.

10. Interior building materials having the laminate according to claim 7 or 8.

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