Coating compositions and cosmetic materials

Abstract

The problem that the present invention aims to solve is to provide a coating composition that has a good matting effect, excellent settling stability, good fluidity, and excellent clarity. [Solution] The present invention solves the above problem with a coating composition comprising a resin (A), silica (B), nanosilica (C), and a thixotrope (D), wherein the content ratio of silica (B) to the solid content of resin (A) is 20 to 40% by mass, the content ratio of nanosilica (C) to silica (B) is 2 to 15% by mass, the content ratio of thixotrope (D) to nanosilica (C) is 30 to 80% by mass, the silica (B) is gel-processed silica, the average particle diameter of silica (B) is 0.1 to 5 μm, and the average primary particle diameter of nanosilica (C) is 0.001 to 0.1 μm.

Description

Technical Field

[0001] The present invention relates to a coating composition and a cosmetic material.

Background Art

[0002] For the surfaces of building interior materials, fixtures, and furniture, plywood with a decorative sheet printed with a wood grain pattern or the like is mainly used. A coating layer for protection and beautification is formed on the surface layer of the decorative sheet. In recent years, there has been a growing demand for a more excellent sense of luxury and reproduction of a woody texture. For this purpose, a high matting effect and clarity that prevents the printed pattern from fading are required. It is common to blend silica into the coating agent for matting. However, when a large amount of silica is blended to obtain an excellent matte surface, the sedimentation stability (storage stability) may deteriorate accordingly, and agglomerated sediment may occur over time. It is not easy to redisperse this agglomerated sediment of silica, and it is necessary to mix it with a dedicated stirrer for a sufficient time, which has been a factor reducing the production efficiency. In addition, the clarity and fluidity tend to deteriorate due to the blending of silica, and a coating agent that satisfies these requirements has been demanded.

[0003] In Patent Document 1, a decorative sheet having a surface protective layer containing silica is disclosed, and the amount of silica in the surface protective compatible resin composition is adjusted so that the gloss value becomes 10. However, when the gloss value, that is, the 60-degree surface glossiness is 10, the matting effect is insufficient, and a further matting effect is required. In addition, the evaluation of the sedimentation stability (storage stability) and fluidity of the resin composition for the surface protective layer was not considered.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] In view of the above, the problem that the present invention aims to solve is to provide a coating composition that has a good matting effect, excellent settling stability, good fluidity, and excellent clarity. [Means for solving the problem]

[0006] The present invention solves the above problems with a coating composition comprising a resin (A), silica (B), nanosilica (C), and a thixotrope (D), wherein the content ratio of silica (B) to the solid content of resin (A) is 20 to 40% by mass, the content ratio of nanosilica (C) to silica (B) is 2 to 15% by mass, the content ratio of thixotrope (D) to nanosilica (C) is 30 to 80% by mass, the silica (B) is gel-processed silica, the average particle diameter of silica (B) is 0.1 to 5 μm, and the average primary particle diameter of nanosilica (C) is 0.001 to 0.1 μm. [Effects of the Invention]

[0007] The coating composition of the present invention exhibits a good matting effect, excellent clarity, and good storage stability and fluidity, making it suitable for use as a coating composition for cosmetic materials. [Modes for carrying out the invention]

[0008] <Definition of terms> In this invention, "〇〇~××" is synonymous with "〇〇 or more and less than ××". In this invention, (meth)acrylate means acrylate or methacrylate. In this invention, the average particle diameter of silica (B) is the average secondary particle diameter of the primary particle aggregate (secondary particle structure), and is the average particle diameter measured by the Coulter counter method in accordance with JIS Z8832:2010 "Method for measuring particle size distribution - Electrical detection zone method". Furthermore, the average primary particle diameter of nanosilica (C) is the average primary particle diameter measured by SEM in accordance with JIS Z8827 "Particle size analysis - Image analysis method".

[0009] The coating composition of the present invention comprises a resin (A), silica (B), nanosilica (C), and a thixotrope (D).

[0010] <Resin (A)> The resin (A) used in the coating composition of the present invention is not particularly limited as long as it can suitably disperse silica (B), which is a matting agent, and any known resin can be used. Specifically, for example, one or more resins such as vinyl chloride acetate-vinyl copolymer resin, acrylic resin, urethane resin, acrylic urethane resin, nitrated cotton, polyvinyl alcohol, polyvinyl acetal, cellulose derivative, polycarbonate resin, polyamide resin, polyester resin, butyral resin, and epoxy resin can be used. Among these, acrylic resin and urethane resin are preferred.

[0011] Furthermore, these can also be made into a so-called two-component curing type using a curing agent. Examples of curing agents include isocyanate compounds, melamine compounds, epoxy compounds, amine compounds, and alkyl silicate compounds. Among these, it is preferable to use an isocyanate compound as the curing agent, and a two-component curing type composition may be used, which is a combination of an isocyanate group and a resin having an active hydrogen group that can react with the isocyanate group.

[0012] Examples of isocyanate compounds used as curing agents include tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI) and their hydrogenated compounds, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), and other compounds having two isocyanate groups per molecule, as well as polyisocyanates having three or more isocyanate groups per molecule synthesized by known techniques using one or more compounds selected from these. Furthermore, compositions containing a mixture of one or more of these different types of polyisocyanates can be used. Preferably, the product is a trimer type, TMP adduct type, or burette type, synthesized by known techniques from one or more compounds selected from TDI, XDI, IPDI, and HDI.

[0013] As resins having active hydrogen groups, resins having two or more of one or more functional groups in one molecule are preferred because they can form a three-dimensional crosslinked structure after curing, and resins having two or more of one or more functional groups selected from hydroxyl groups, amino groups, and carboxyl groups in one molecule are preferred. Specifically, examples include polyethylene glycol, polypropylene glycol, polyacrylic polyol, polyester polyol, polyether polyol, polycarbonate polyol, polyurethane polyol, acrylic alkyd, and other polyols. Among these, polyacrylic polyol and polyurethane polyol are preferred. Also, the hardener is not included in the solid content of resin (A).

[0014] The isocyanate compound content in the above resin can be set arbitrarily, but generally the hydroxyl group / isocyanate equivalent ratio is often 1 / 0.5 to 1 / 3.

[0015] The curing method for the two-component curing type resin composition is not particularly limited and can be cured by known heating methods.

[0016] The resin (A) used in the coating composition of the present invention may be a resin having radically polymerizable unsaturated groups, such as urethane (meth)acrylate, acrylic (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, etc. Among these, urethane (meth)acrylate and acrylic (meth)acrylate are preferred because they possess the physical properties of a coating agent. In addition, acrylate monomers, acrylate oligomers, etc. can be used as reactive diluents.

[0017] The components constituting the above-mentioned urethane (meth)acrylate include polyfunctional alcohol components, compounds having one or more alcoholic hydroxyl groups and one or more (meth)acrylic acid esters or (meth)acrylamides in the molecule, and polyisocyanate compounds. The polyfunctional alcohol components constituting the urethane (meth)acrylate resin include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propylene glycol, di(1,2-propylene glycol), tri(1,2-propylene glycol), 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1,2-pentanediol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,6-hexanediol, and 1,6-hex Sandiol, 1,2-Hexanediol, 1,8-Octanediol, 2-Methyl-1,8-Octanediol, 1,9-Nonanediol, 1,10-Decanediol, 1,12-Dodecanediol, 1,2-Bis(hydroxymethyl)cyclohexane, 1,3-Bis(hydroxymethyl)cyclohexane, 1,4-Bis(hydroxymethyl)cyclohexane, Bis(hydroxymethyl)tricyclodecane, 1,3-Bis(hydroxymethyl)adamantane, 2,3-Bis(hydroxymethyl)norbornane, 2,5-Bis(hydroxymethyl)norbornane, 2,6-Bis(hydroxymethyl)norbornane, Hydrogenated Bisphenol A, Hydrogenated Bisphenol A Ethylene Oxide Adduct, Bisphenol A Ethylene Oxide Adduct, Neopentyl Glycol Monohydroxypivalate, Spiroglycol (3,9-Bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-Tetraoxospiro[5.Examples of compounds include undecane, trimethylolethane, trimethylolpropane, ethylene oxide-modified trimethylolpropane, tris(hydroxyethyl)isocyanuric acid, glycerin, ethylene oxide-modified glycerin, propylene oxide-modified glycerin, pentaerythritol, ethylene oxide-modified pentaerythritol, propylene oxide-modified pentaerythritol, ditrimethylolpropane, ethylene oxide-modified ditrimethylolpropane, propylene oxide-modified ditrimethylolpropane, dipentaerythritol, ethylene oxide-modified dipentaerythritol, propylene oxide-modified dipentaerythritol, and refined castor oil. One or more compounds selected from these can be used individually or mixed in any ratio as needed.

[0018] The following compounds are examples of components of the above-mentioned urethane (meth)acrylate resin that impart terminal radical polymerizable unsaturated bonds, and include compounds having one or more alcoholic hydroxyl groups and one or more (meth)acrylic acid esters or (meth)acrylamides in their molecules. Examples of (meth)acrylic acid esters or (meth)acrylamides having one alcoholic hydroxyl group in the molecule include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 4-hydroxymethylcyclohexylmethyl (meth)acrylate, α-hydroxymethylacrylate, α-hydroxymethylacrylate, ε-caprolactone-modified 2-hydroxyethyl (meth)acrylate, γ-butyrolactone-modified 2-hydroxyethyl (meth)acrylate, and poly Examples include (ethylene glycol) mono(meth)acrylate, poly(propylene glycol) mono(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, 2-hydroxy-3-phenoxypropyl(meth)acrylate, glycerin(meth)acrylate stearate, glycerin(meth)acrylate oleate, glycerin di(meth)acrylate, glycerin acrylate methacrylate, bis[(meth)acryloyloxyethyl]isocyanuric acid, N-(2-hydroxyethyl)(meth)acrylamide, etc. In addition, (meth)acrylic acid esters having two or more alcoholic hydroxyl groups include glycerin (meth)acrylate, trimethylolpropane (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol di(meth)acrylate, ditrimethylolpropane di(meth)acrylate, dipentaerythritol tetra(meth)acrylate, and (meth)acryloyloxyethyl bis(hydroxyethyl)isocyanuric acid.In addition, a group of compounds generally called epoxy acrylates, which are obtained by the reaction of aliphatic diglycidyl ethers such as ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, poly(ethylene glycol) diglycidyl ether, poly(propylene glycol) diglycidyl ether, etc. with (meth)acrylic acid, can be used. One or more compounds selected from these can also be used as a compound having 2-hydroxyl(meth)acrylate ester structures at both ends to introduce a radically polymerizable unsaturated bond into the urethane resin skeleton.

[0019] As monomer components constituting the above acrylic (meth)acrylate, monofunctional monomers such as ethyl (meth)acrylate, ethylhexyl (meth)acrylate, styrene, methylstyrene, N-vinylpyrrolidone, etc., and polyfunctional monomers, for example, trimethylolpropane (meth)acrylate, hexanediol (meth)acrylate, tripropylene glycol di(meth)acrylate, diethylene glycol (meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol (meth)acrylate, etc. can be mentioned.

[0020] The double bond equivalent of the above acrylic (meth)acrylate is preferably in the range of 200 to 750 g / mol. When the double bond equivalent of the acrylic (meth)acrylate is 200 g / mol or more, the volume shrinkage during curing is suppressed, the possibility of cracks due to bending and distortion of the coating film decreases, and the decrease in processability due to dense crosslinking is less likely to occur. Also, when it is less than 750 g / mol, physical properties such as hardness after reaction become suitable due to sufficient reactive groups. This range is more preferably 200 to 400 g / mol, and even more preferably 200 to 300 g / mol. Also, the weight average molecular weight of the above acrylic (meth)acrylate is preferably in the range of 10,000 to 100,000. When the weight average molecular weight of the acrylic (meth)acrylate is 10,000 or more, the tackiness of the coating film is suppressed, and it becomes possible to achieve tack-free state only in the drying process. Also, when it is less than 100,000, the viscosity of the composition can be kept within an appropriate range, the dilution ratio during coating can be maintained, and the coating amount tends to be sufficient. Further, from 100,000, the range is more preferably 10,000 to 50,000, and even more preferably 10,000 to 30,000.

[0021] The glass transition temperature (Tg) of the above acrylic (meth)acrylate is preferably in the range of 40 to 130°C. When it is 40°C or more, sufficient strength tends to be obtained after curing when made into a coating film, and when it is less than 130°C, brittleness is less likely to appear when made into a coating film, and the processability tends to be good. The hydroxyl value of the acrylic (meth)acrylate is preferably in the range of 5 to 300 mgKOH / g. When it is 5 mgKOH / g or more, the dispersion of the matting agent is good and low gloss can be achieved, and when it is less than 300 mgKOH / g, the performance such as stain resistance becomes good.

[0022] Also, as the reactive diluent, a monomer having a (meth)acryloyl group may be used. The monomer having a (meth)acryloyl group is not particularly limited, and a monomer having a (meth)acryloyl group that can be cured by a known active energy ray (hereinafter may be simply referred to as "active energy ray curable") can be used. Examples of monofunctional (meth)acrylates include ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, hexadecyl (meth)acrylate, octadecyl (meth)acrylate, isoamyl (meth)acrylate, isodecyl (meth)acrylate, isostearyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, and nonyl Examples include phenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, glycidyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, diethylaminoethyl (meth)acrylate, nonylphenoxyethyl tetrahydrofurfuryl (meth)acrylate, caprolactone-modified tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and ethoxyethoxyethanol acrylic acid polymer esters.

[0023] Examples of difunctional (meth)acrylates include 1,4-butanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate, 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and dipropyl Examples include di(meth)acrylates of dihydric alcohols such as ethylene glycol di(meth)acrylate and tripropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, tris(2-hydroxyethyl) isocyanurate di(meth)acrylate, di(meth)acrylate of diols obtained by adding 4 moles or more of ethylene oxide or propylene oxide to 1 mole of neopentyl glycol, and di(meth)acrylates of diols obtained by adding 2 moles of ethylene oxide or propylene oxide to 1 mole of bisphenol A.

[0024] Examples of (meth)acrylates with three or more functions include poly(meth)acrylates of polyhydric alcohols with three or more functions, such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and dipentaerythritol poly(meth)acrylate; tri(meth)acrylates of triols obtained by adding 3 or more moles of ethylene oxide or propylene oxide to 1 mole of glycerin; di(meth)acrylates of triols obtained by adding 3 or more moles of ethylene oxide or propylene oxide to 1 mole of trimethylolpropane; and poly(meth)acrylates of polyoxyalkylene polyols, such as di(meth)acrylates of diols obtained by adding 4 or more moles of ethylene oxide or propylene oxide to 1 mole of bisphenol A.

[0025] In addition, a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (sometimes abbreviated as DPHA), which are bifunctional or more (meth)acrylates, ditrimethylolpropanetetraacrylate (sometimes abbreviated as DTMPTA), and trimethylolpropaneethylene oxide adduct tri(meth)acrylate, which is a triol triol obtained by adding 3 or more moles of ethylene oxide to 1 mole of trimethylolpropane, may also be used. A typical example of the aforementioned trimethylolpropaneethylene oxide adduct tri(meth)acrylate is trimethylolpropaneethylene oxide (hereafter, ethylene oxide may be referred to as "EO")-modified (n≒3) triacrylate.

[0026] Furthermore, polymerizable oligomers may be used as needed. Examples of polymerizable oligomers include urethane (meth)acrylate, amine-modified polyether acrylate, amine-modified epoxy acrylate, amine-modified aliphatic acrylate, amine-modified polyester acrylate, amino (meth)acrylate and other amine-modified acrylates, polyester (meth)acrylate, polyether (meth)acrylate, polyolefin (meth)acrylate, polystyrene (meth)acrylate, epoxy (meth)acrylate, and the like.

[0027] The resin (A) used in the coating composition of the present invention may be a resin having a cationic polymerizable functional group, and examples include epoxy resins such as bisphenol-type epoxy resins and novolac-type epoxy compounds, vinyl ether resins such as fatty acid-based vinyl ethers and aromatic vinyl ethers.

[0028] The content of resin (A) in the coating composition of the present invention is preferably 50 to 85% by mass, and more preferably 65 to 80% by mass, based on the total mass of the coating composition. When the content of resin (A) is within this range, a matte effect can be achieved while improving scratch resistance and abrasion resistance. Note that the resin content refers to the solid content, i.e., the amount of active ingredient. Furthermore, resin (A) may be a combination of multiple types of resins, in which case the content of resin (A) refers to the total content of all resin solids.

[0029] <Silica (B)> The silica (B) used in the coating composition of the present invention is gel-process silica produced by the gel method, with an average particle size of 0.1 to 5 μm. Furthermore, silica (B) has the function of imparting a matte effect to the coating composition of the present invention. Amorphous synthetic silica is classified into wet silica and dry silica depending on the manufacturing method. Wet silica includes silica produced by the sedimentation method and silica produced by the gel method. Sedimentation silica is generally obtained by carrying out the neutralization and decomposition reaction of an aqueous sodium silicate solution with an acid or alkali metal salt under basic conditions, causing the fully grown primary particles to aggregate. On the other hand, when the neutralization and decomposition reaction of an aqueous sodium silicate solution with an acid or alkali metal salt is carried out under acidic conditions, the growth of the primary silica particles is suppressed, and the primary silica particles in the process of growing aggregate, resulting in gel silica. Gel-processed silica can be identified using SEM imaging. Specifically, because gel-processed silica has an angular shape, it can be easily distinguished from sedimentation-processed silica.

[0030] In the gel-processed silica described above, primary particles of 5-55 nm, which are the smallest constituent units of the substance, fuse or chemically bond to form primary particle aggregates (secondary particle structure). These primary particle aggregates physically aggregate and exist as secondary aggregates, but the secondary aggregates can be dispersed back to primary particle aggregates (secondary particle structure) by applying physical shear force in various media. In this invention, the average particle diameter of silica (B) is the average secondary particle diameter of the primary particle aggregates (secondary particle structure).

[0031] The average particle size of silica (B) is 0.1 to 5 μm, i.e., between 0.1 μm and less than 5 μm. When the average particle size is 0.1 μm or larger, good matte finish is obtained. Furthermore, when the average particle size is less than 5 μm, good clarity can be obtained in addition to the matte finish. Furthermore, the average particle size is preferably 0.3 to 4 μm, and more preferably 0.5 to 3 μm.

[0032] The average particle size of silica (B) described above was measured according to JIS Z8832:2010 "Method for measuring particle size distribution - Electrical detection zone method". Specifically, a small amount of sample was added to a solvent and dispersed in an ultrasonic disperser for 3 minutes. The median diameter of the solution was measured using a Coulter counter particle size analyzer with a 50 μm aperture. An aqueous solution of 50 g / L trisodium phosphate dodecahydrate was used as the electrolyte solution. A COULTER ELECTRONICS INS TA-II type analyzer was used as the measuring instrument.

[0033] The pore volume of silica (B) is preferably 0.1 to 2.0 mL / g, and more preferably 1.5 to 2.0 mL / g. The apparent specific gravity is preferably 0.1 to 1.5 g / mL, and more preferably 0.1 to 0.5 g / mL. The oil absorption is preferably 50 to 400 mL / 100 g, and more preferably 200 to 400 mL / 100 g. When the pore volume exceeds 0.1 mL / g, the apparent specific gravity exceeds 0.1 g / mL, and the oil absorption exceeds 50 mL / 100 g, a sufficient matting effect can be obtained. Conversely, when the pore volume falls below 2.0 mL / g, the apparent specific gravity below 1.5 g / mL, and the oil absorption falls below 400 mL / 100 g, the matting effect is also greater, the viscosity is kept within a suitable range, and the fluidity of the coating composition can be easily adjusted.

[0034] The silica (B) used in this invention may also be surface-modified. There are no particular restrictions on the method of surface treatment of silica particles; any known method is acceptable. Examples include surface treatment with wax or silane coupling agents.

[0035] The silica (B) content used in this invention is preferably 0.1 to 15% by mass of the total amount of the coating composition. A silica (B) content of 0.1% by mass or more of the total amount of the coating composition is preferable because it provides a sufficient matting effect, while a silica (B) content of less than 15% by mass is preferable because it makes it easier to adjust the fluidity and transferability of the coating composition to a suitable range. The silica (B) content is preferably 1 to 15% by mass, and more preferably 5 to 15% by mass, relative to the total amount of the coating composition.

[0036] Furthermore, the silica (B) content used in this invention is preferably 5 to 30% by mass relative to the total amount of solids in the coating composition. A silica (B) content of 5% by mass or more relative to the total amount of solids in the coating composition provides a sufficient matting effect, while a content of less than 30% by mass is preferable because it ensures fluidity while providing good redispersibility of aggregates. The silica (B) content is preferably 10 to 30% by mass, and more preferably 18 to 30% by mass, relative to the total amount of solid matter in the coating composition. Furthermore, multiple types of silica (B) may be used in combination, in which case the silica (B) content refers to the total silica content.

[0037] <Nanosilica (C)> The nanosilica (C) used in the coating composition of the present invention has a primary particle size of 0.001 to 0.1 μm. The average primary particle size of the nanosilica (C) is the average primary particle size measured by SEM in accordance with JIS Z8827 "Particle size analysis - Image analysis method". Furthermore, the inventors speculate that nanosilica (C) contributes to improved storage stability by suppressing the aggregation of the matting agent, preventing hard cake formation, and mitigating the sedimentation rate. The nanosilica (C) is preferably fumed silica produced by burning silicon tetrachloride gas or the like in the gas phase. Adding nanosilica (C) to silica (B) as a matting agent improves the storage stability of the matting agent and increases production efficiency.

[0038] The nanosilica (C) used in this invention may also be surface-modified. There are no particular restrictions on the method of surface treatment of silica particles; any known method is acceptable. Examples include surface treatment with wax or silane coupling agents.

[0039] The average primary particle size of nanosilica (C) is preferably 0.005 to 0.05 μm, and more preferably 0.01 to 0.04 μm. When the average primary particle size of nanosilica (C) is within this range, the sedimentation stability of the coating composition can be improved together with the thixotrope described later.

[0040] The nanosilica (C) content is preferably 0.01 to 3% by mass, and more preferably 0.1 to 2% by mass, relative to the total amount of the coating composition. Furthermore, the nanosilica (C) content is preferably 0.1 to 5% by mass, and more preferably 0.5 to 4% by mass, relative to the total amount of solids in the coating composition. By setting the nanosilica (C) content within this range, it is possible to maintain desirable clarity while ensuring good storage stability. Furthermore, multiple types of nanosilica (C) may be used in combination, in which case the nanosilica (C) content refers to the total content of all nanosilica.

[0041] <Pixonotrope (D)> The thixotrope (D) used in the coating composition of the present invention has the function of maintaining good sedimentation stability even when a large amount of silica (B) is added to impart a matte effect. Examples of the thixotropizing agent (D) include fatty acid amides, organic bentonite, and oxidized polyethylene wax. Among these, fatty acid amides are preferred.

[0042] Fatty acid amides are generally obtained by condensing a fatty acid (e.g., an aliphatic monocarboxylic acid with 2 to 22 carbon atoms) with an amine. Alternatively, by using a diamine as the amine and appropriately adjusting the equivalent ratio of the fatty acid, diamide compounds containing two amide bonds in one molecule can be obtained. For example, by using hydrogenated castor oil fatty acid (main component: 12-hydroxystearic acid) as the fatty acid and a diamine such as ethylenediamine, 1,4-diaminobutane, hexamethylenediamine, or xylylenediamine, fatty acid amides (diamides) suitable for addition to paints can be obtained. Furthermore, fatty acid amides, which are oligomers or polymers, can also be obtained by condensing dicarboxylic acids such as azelaic acid and sebacic acid with diamines.

[0043] Specifically, examples of fatty acid amides include the following: Monoamides include saturated fatty acid monoamides such as laurate amide, palmitate amide, stearate amide, behenate amide, and hydroxystearate amide, as well as oleate amide, erucate amide, and ricinoleate amide. Substituted amides include N-lauryllaurate amide, N-palmitylpalmitate amide, N-stearylstearate amide, N-oleyloleate amide, N-stearyloleate amide, N-oleylstearate amide, N-stearylerucate amide, N-oleylpalmitate amide, N-12-hydroxystearylstearate amide, and N-12-hydroxystearyloleate amide. Methylolamides include methylol stearate and methylol behenate. Bisamides include methylene bis stearate, methylene bis laurate, methylene bis hydroxy stearate, methylene bis oleate, ethylene biscaprylate, ethylene bis laurate, ethylene bis stearate, ethylene bis isostearate, ethylene bis hydroxy stearate, ethylene bis behenate, hexamethylene bis behenate, hexamethylene bis stearate, hexamethylene bis hydroxy stearate, and butylene bis hydroxy stearate. These include saturated fatty acid bisamides such as amide, N,N'-distearyl adipic acid amide, and N,N'-distearyl sebacate acid amide; unsaturated fatty acid bisamides such as ethylene bisoleic acid amide, ethylene biserucic acid amide, hexamethylene bisoleic acid amide, N,N'-dioleyl adipic acid amide (melting point 119°C), and N,N'-dioleyl sebacate acid amide (melting point 115°C); aromatic bisamides such as m-xylylene bisstearate amide (melting point 123°C) and N,N'-dioleyl sebacate acid amide; and fatty acid ester amides such as ethanolamine distearate. These fatty acid amides may be used individually or in combination of two or more types.

[0044] Commercially available fatty acid amides include Disparon 6900-20X, Disparon 6900-10X, Disparon A603-20X, Disparon A603-10X, Disparon A670-20M, Disparon A671-EZ, Disparon F-9050, Disparon PFA-220, Disparon PFA-231, Disparon PFA-131, Disparon 6810-20X, Disparon 6850-20X, Disparon 6820-20M, Disparon 6820-10M, Disparon FS-6010, Disparon 3900EF, Disparon 6500, Disparon 6300, and Disparon 665. Examples include the Disparon series such as Disparon 6700 (manufactured by Kusumoto Kasei Co., Ltd.), the Flownon series such as Flownon RCM-220, Flownon RCM-230AF, Flownon SH-290, Flownon SH-2955, Flownon SH-350, Flownon SP-1000, Flownon SP-1000AF (manufactured by Kyoeisha Chemical Co., Ltd.), and the Talen series such as Talen 7200-20, Talen 8200-20, Talen 8300-20, Talen 8700-20, Talen BA-600, Talen M-1020XFS, Talen M-1021B, Talen VA-750B (manufactured by Kyoeisha Chemical Co., Ltd.).

[0045] In the coating composition of the present invention, it is preferable that the fatty acid amide is dissolved in the organic solvent, or, even if not completely dissolved in the organic solvent, dispersed in the organic solvent as particles with a particle size of 10 μm or less. This form allows the coating composition to exhibit good storage stability due to its thixotropic properties.

[0046] When the non-volatile components of fatty acid amides are measured by DSC (Differential Scanning Calorimetry), the peak top temperature of the melting peak is preferably 130°C or higher, and more preferably between 130°C and 150°C. If two or more melting peaks are observed in the DSC measurement, the peak top temperature of the lowest temperature peak is used. Using fatty acid amides with a melting peak top temperature of 130°C or higher can improve the durability of the final coating film.

[0047] The content of the quiviate (D) used in the coating composition of the present invention is preferably 0.01 to 1.0% by mass relative to the total amount of the coating composition. Furthermore, the content of the quiviate (D) is preferably 0.1 to 3.0% by mass relative to the total amount of solids in the coating composition. Within this range, sufficient storage stability can be provided.

[0048] <Solvent (E)> The coating composition of the present invention may, and preferably, further contain a solvent (E). The solvent (E) dilutes the coating composition, maintaining its fluidity favorably and also improving its storage stability. Examples of solvents (E) include aromatic hydrocarbons such as toluene and xylene, aliphatic or alicyclic hydrocarbons such as n-hexane, cyclohexane, methylcyclohexane, and ethylcyclohexane, esters such as ethyl acetate, propyl acetate, butyl acetate, and isobutyl acetate, alcohols such as methanol, ethanol, isopropyl alcohol, and n-butanol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, alkylene glycol monoalkyl ethers such as ethylene glycol monoethyl ether and propylene glycol monomethyl ether, and ether esters such as propylene glycol monomethyl ether acetate.

[0049] The content of the above solvent (E) is not particularly limited, and it should be diluted so that the viscosity of the coating composition is suitable for coating. The viscosity is preferably adjusted to 1 to 3000 mPa·s.

[0050] (Other ingredients) The coating composition of the present invention may further contain, as optional components, waxes, plasticizers, leveling agents, surfactants, dispersants, defoaming agents, ultraviolet absorbers, light stabilizers, polymerization inhibitors, drying agents, and the like. Furthermore, beads can also be added. There are no particular limitations on the beads used; any known beads can be used. Specifically, acrylic resin beads, urethane resin beads, silicone beads, glass beads, etc., can be used. By adding beads to the silica used as a matting agent, in addition to the matting effect, a good tactile feel can be provided, and the scratch resistance of the coated surface can be improved.

[0051] <Coating composition> In the coating composition of the present invention, the content ratio of silica (B) to the solid content of resin (A) is 20 to 40% by mass. When this ratio is within this range, a sufficient matte effect can be obtained, and good fluidity and storage stability are achieved. The relevant range is preferably 25-40% by mass, and more preferably 28-40% by mass, as this allows for a particularly good matte finish.

[0052] In the coating composition of the present invention, the content ratio of nanosilica (C) to silica (B) is 2 to 15% by mass. When this ratio is within this range, the sedimentation of silica (B) is suppressed and storage stability is improved. The relevant range is preferably 4 to 15% by mass to further improve settling stability, and more preferably 4 to 12% by mass to optimize fluidity.

[0053] In the coating composition of the present invention, the content ratio of the thixotropy agent (D) to the nanosilica (C) is 30 to 80% by mass. When this ratio is within this range, the thixotropy is suitably adjusted, and good fluidity and sedimentation stability can be maintained. From the viewpoint of fluidity, the relevant range is preferably 40 to 80% by mass, and more preferably 40 to 70% by mass.

[0054] The ratio of active ingredients in the coating composition of the present invention is determined by adjusting the viscosity of the coating composition, but a ratio of 30 to 60% by mass is preferable from the viewpoint of performance balance. The amount of active ingredients in the coating composition refers to the total amount of solid content (active ingredients) of resin (A), silica (B), nanosilica (C), and thixotrope (D), and does not include other additives.

[0055] (Method for manufacturing coating composition) The coating composition of the present invention can be manufactured by stirring and dispersing a resin (A), silica (B), nanosilica (C), a thixotrope (D), and other solvents (E) and various additives, and / or by dispersing them in a paste-like mixture. The coating composition of the present invention can be prepared by appropriately adjusting the size of the grinding media in the disperser, the filling rate of the grinding media, the dispersion processing time, etc. As the disperser, commonly used types such as dispersers, roller mills, ball mills, pebble mills, attritors, and sand mills can be used. If the coating composition contains air bubbles or unexpected coarse particles, it is preferable to remove them by filtration or other means to improve the quality of the coated product. Conventional filters can be used.

[0056] (Coating of coating compositions) The coating composition of the present invention can be applied to the surface of a substrate. Specific examples of coating methods include, but are not limited to, roll coaters, gravure coaters, flexographic coaters, air doctor coaters, blade coaters, air knife coaters, squeeze coaters, impregnation coaters, transfer roll coaters, kiss coaters, curtain coaters, cast coaters, spray coaters, die coaters, offset printing presses, screen printing presses, and the like. Furthermore, the coating process also includes a step of drying the applied coating agent. Examples of drying methods include, but are not limited to, natural drying, heat drying, hot air drying, ultraviolet drying, infrared drying, and oven drying.

[0057] Before coating the coating composition of the present invention, a solvent may be added to adjust its viscosity. At that time, a curing agent, a photopolymerization initiator, and a sensitizer may also be added to cure the coating composition. In other words, the coating composition of the present invention can be a coating composition to which a solvent, curing agent, photopolymerization initiator, and sensitizer have been added before coating. As the solvent, one of the solvents exemplified in solvent (E) above can be used. In addition, the solvent (E) of the coating composition and the solvent of the coating composition may be different, but it is preferable to use the same solvent.

[0058] When the coating composition of the present invention uses a two-component resin as resin (A), a curing agent may be added to the coating composition. Examples of such curing agents include isocyanate compounds, melamine compounds, epoxy compounds, amine compounds, alkyl silicate compounds, and the like. Among these, isocyanate compounds are preferred. Furthermore, the curing agent is preferably contained in an amount of 20 to 60% by mass relative to the solid content of resin (A).

[0059] When the coating composition of the present invention uses a resin having radically polymerizable unsaturated groups as resin (A), a photopolymerization initiator may be added to the coating composition. After coating the coating composition, the coating composition can be cured (dried) by irradiating it with active energy rays from a light source. Active energy rays include ionizing radiation such as ultraviolet rays, electron beams, alpha rays, beta rays, and gamma rays. Specific energy sources or curing devices include, for example, germicidal lamps, ultraviolet fluorescent lamps, ultraviolet light-emitting diodes (UV-LEDs), carbon arcs, metal halide lamps, xenon lamps, chemical lamps, low-pressure mercury lamps, high-pressure mercury lamps for copying, medium-pressure or high-pressure mercury lamps, ultra-high-pressure mercury lamps, electrodeless lamps, metal halide lamps, ultraviolet rays using natural light as a light source, or electron beams from scanning or curtain-type electron beam accelerators. Among these, ultraviolet light, electron beams, and gamma rays are preferred, with ultraviolet light or electron beams being preferred. The amount of ultraviolet light during curing is 50 mJ / cm², as mentioned above. 2 If the curing efficiency is above 300 mJ / cm², the curing efficiency is good. 2 The following conditions are preferable from the standpoint of preventing damage to the substrate due to heat. Furthermore, a method of irradiation with reduced oxygen concentration to prevent oxygen inhibition can also be used. Specifically, if nitrogen gas, carbon dioxide gas, argon gas, or other gases are mixed together with air or individually and injected into the reaction vessel, and then the coating composition is irradiated with active energy rays, the curing of the coating film obtained in the above process can be advanced more efficiently.

[0060] When ultraviolet light is used as the active energy ray, it is possible to use a known and publicly available photopolymerization initiator as the curing agent for the coating composition of the present invention, and a photopolymerization initiator can be added to the above coating composition. Among these, radical polymerization type photopolymerization initiators are preferred, and α-hydroxyalkyl ketone-based photopolymerization initiators that do not color the dissolution solution when the active energy ray-curable compound is dissolved and show little yellowing over time are particularly preferred. Examples of α-hydroxyalkyl ketone-based photopolymerization initiators include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-(4-i-propylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, and 1-hydroxycyclohexylphenyl ketone. Furthermore, phenylglyoxolate-based photopolymerization initiators are also preferred. Examples of phenylglyoxolate-based photopolymerization initiators include methylbenzoyl formate. Among these, 1-hydroxycyclohexylphenyl ketone is preferred.

[0061] Furthermore, as other radical polymerization type photopolymerization initiators, monoacylphosphine oxide-based photopolymerization initiators having absorption wavelengths in the long-wavelength region of ultraviolet light may be used in appropriate combinations. Examples of monoacylphosphine oxide-based photopolymerization initiators include monoacylphosphine oxides such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,6-dimethoxybenzoyl-diphenylphosphine oxide, 2,6-dichlorobenzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoyl-phenylphosphinate methyl ester, 2-methylbenzoyl-diphenylphosphinate isopropyl ester, and pivaloylphenylphosphinate isopropyl ester, excluding bisacylphosphine oxides which discolor when dissolved in active energy ray-curable compounds. In particular, among these, 2,4,6-trimethylbenzoyl-diphenylphosphinate is more preferable because it has a UV absorption wavelength that matches the emission wavelength range of UV-LEDs with emission wavelengths of 385 nm and 395 nm, resulting in suitable curability and less yellowing of the cured film.

[0062] The aforementioned photopolymerization initiators may be used individually or in combination of two or more. The content of the photopolymerization initiator in the coating composition is preferably in the range of 1 to 15% by mass relative to the solid content of resin (A). Adding less than 0.1% by mass makes it difficult to obtain good curability, and adding more than 10% by mass results in an excess of initiator, which impairs the fluidity of the coating composition and reduces processability and workability, so this is undesirable.

[0063] Furthermore, the curing rate can be accelerated by adding a tertiary amine compound selected from aliphatic amine derivatives and / or benzoic acid amine derivatives to the coating composition as a sensitizer. Tertiary amine compounds are known to enhance reactivity and prevent reaction inhibition by oxygen. Suitable tertiary amine compounds include, for example, free alkylamines such as triethylamine, methyldiethanolamine, and triethanolamine; aromatic amines such as 2-ethylhexyl-4-dimethylaminobenzoate and ethyl-4-dimethylaminobenzoate; and polymeric amines such as polyallylamine and its derivatives. Active energy ray polymerizable compounds such as ethylene double-bonded unsaturated amines (e.g., (meth)acrylated amines) are preferred because they have low odor, low volatility, and the ability to suppress yellowing by being incorporated into the polymer matrix upon curing.

[0064] The tertiary amine compound can be used in an amount of preferably 0.1 to 5% by mass, more preferably 0.2 to 2% by mass, relative to the solid content of resin (A).

[0065] (Coating layer) The coating composition of the present invention can be formed into a coating layer by preparing a coating composition as needed, applying or printing it to a substrate surface, and then undergoing a drying process and, if necessary, a curing process. The film thickness of the coating layer after drying is preferably in the range of 1 to 10 μm, more preferably in the range of 2 to 8 μm, and even more preferably in the range of 3 to 7 μm. Within this film thickness range, silica (B) is efficiently exposed on the surface, and the effects of the present invention can be maximized.

[0066] The coating layer is formed from the coating composition of the present invention and the solid content of the above-mentioned coating composition. The coating layer preferably contains 50 to 90% by mass of resin (A), and more preferably 50 to 85% by mass. The coating layer also preferably contains 5 to 40% by mass of silica (B), and more preferably 10 to 35% by mass. Furthermore, the coating layer preferably contains 0.05 to 6% by mass of nanosilica (C), and more preferably 0.1 to 5.5% by mass. The coating layer also preferably contains 0.05 to 15% by mass of a thixotroper (D), and more preferably 0.1 to 10% by mass.

[0067] <Decorative materials> Examples of decorative materials coated with the coating composition of the present invention on a substrate surface include decorative sheets, decorative panels, and other materials whose surfaces have been processed for decoration or protection. Naturally, decorative materials coated on a substrate surface with a coating composition obtained by adding a solvent or the like to the coating agent of the present invention are also considered decorative materials coated with the coating composition of the present invention on a substrate surface. The decorative sheet is constructed by forming a pattern layer on a substrate such as paper by printing or coating it with known printing inks or coatings such as acrylic, cellulose, vinyl, chlorinated polyolefin, chlorinated rubber, or urethane, and then providing a topcoat layer to cover this pattern layer. The coating composition of the present invention forms the topcoat layer.

[0068] (base material) Examples of substrates used for the decorative sheets include paper-based substrates such as tissue paper, plain paper, reinforced paper, and resin-impregnated paper; paper-based substrates such as titanium paper; polyolefin resins such as polyethylene, ethylene-α-olefin copolymer, polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer saponified, ethylene-(meth)acrylic acid copolymer, and ethylene-(meth)acrylic acid ester copolymer; and thermoplastic resin sheets and films such as polyvinyl chloride, polyethylene terephthalate (PET), glycol-modified polyethylene terephthalate (PETG), polybutylene terephthalate, polyamide, acrylonitrile butadiene styrene (ABS), polycarbonate, polyethylene naphthalate, ionomer, acrylic acid ester polymer, and methacrylic acid ester polymer. The base sheet may be formed by using these resins individually or in combination of two or more types.

[0069] The above-mentioned substrate may be colored, and may also contain various additives as needed, such as fillers, matting agents, foaming agents, flame retardants, lubricants, antistatic agents, antioxidants, UV absorbers, and light stabilizers. The thickness of the substrate can be set appropriately depending on the application and method of use of the final product, but is generally preferred to be 20 to 300 μm.

[0070] One or both sides of the above-mentioned substrate may be subjected to surface treatments such as corona discharge treatment, ozone treatment, plasma treatment, ionizing radiation treatment, or dichromate treatment, as needed. For example, when performing corona discharge treatment, the surface tension of the substrate sheet surface should be 30 dyne or more, preferably 40 dyne or more. Surface treatments should be carried out according to the conventional methods for each treatment.

[0071] A decorative sheet using the coating composition of the present invention may have, in addition to the coating layer formed from the coating composition, an easy-adhesion layer, a pattern layer, a transparent adhesive layer, and a transparent resin layer, which are typically provided on a decorative sheet.

[0072] The above-mentioned easy-adhesion layer is provided on the side of the substrate opposite to the side where the coating layer is provided, and is provided for the purpose of improving adhesion to wood substrates such as lauan plywood. For example, an easy-adhesion layer made of a thermoplastic resin such as polyamide resin, acrylic resin, or vinyl acetate resin can be used.

[0073] The above-mentioned patterned layer imparts a desired design to the decorative sheet, and the types of patterns are not particularly limited. Examples include wood grain patterns, stone patterns, sand patterns, tile patterns, brick patterns, fabric patterns, leather patterns, geometric figures, letters, symbols, and abstract patterns. Furthermore, the method of forming the patterned layer is not particularly limited; for example, it may be formed by printing methods using colored inks, coating agents, etc., obtained by dissolving (or dispersing) known colorants (dyes or pigments) together with a binder resin in a solvent (or dispersion medium). The patterned printing layer is usually applied to a separate sheet using a known printing method such as gravure printing, offset printing, screen printing, flexographic printing, electrostatic printing, or inkjet printing, and is then attached to the substrate via a transparent adhesive layer, as described later.

[0074] The transparent adhesive layer described above is not particularly limited as long as it is transparent, and includes colorless transparent, colored transparent, translucent, etc. The adhesive is not particularly limited, and adhesives known in the field of decorative sheets can be used, such as thermoplastic resins such as polyamide resin, acrylic resin, vinyl acetate resin, curable resins such as thermosetting urethane resin, or two-component curable polyurethane resin or polyester resin adhesives using isocyanate as a curing agent.

[0075] Furthermore, a separate transparent resin layer may be provided for the purpose of improving visibility and various strengths. The transparent resin layer can be colorless, colored, or translucent, as long as it is transparent. The resin components included in the transparent resin layer are not limited, but any thermoplastic resin is preferred, and polypropylene is particularly preferred. Additives such as fillers, flame retardants, lubricants, antioxidants, and light stabilizers (UV absorbers, radical scavengers, etc.) can also be added. Adding light stabilizers is particularly preferable to improve weather resistance.

[0076] Taking a decorative sheet using the coating composition of the present invention as an example, a pattern layer is formed on the above-mentioned substrate by printing or applying known printing inks or paints such as acrylic, cellulose, vinyl, chlorinated polyolefin, chlorinated rubber, or urethane, and then the decorative sheet is manufactured by applying the coating composition of the present invention as described above to form a coating layer.

[0077] As described above, the coating composition of the present invention can be used with various methods such as roll coaters, gravure coaters, flexo coaters, air doctor coaters, blade coaters, air knife coaters, squeeze coaters, impregnation coaters, transfer roll coaters, kiss coaters, curtain coaters, cast coaters, spray coaters, die coaters, offset printing presses, screen printing presses, etc., to form a coating film.

[0078] The above-mentioned decorative panel can be obtained by coating a wood-based decorative panel, etc., commonly used for decorative panels, with the coating composition of the present invention. Examples of wood-based substrates for wood-based decorative panels include plywood, particleboard, hardboard, MDF, etc., which have been conventionally used as wood-based substrates for decorative panels, furniture, building materials, etc. Furthermore, the method by which these known substrates were obtained is irrelevant. Furthermore, examples of non-combustible materials that can be used as base materials include perforated board building materials made from gypsum board, gypsum board, calcium silicate board, etc., ceramic sheets such as pottery, porcelain, stoneware, earthenware, glass, and enamel, and metal sheets such as iron sheets, galvanized steel sheets, polyvinyl chloride sol coated steel sheets, aluminum sheets, and copper sheets. [Examples]

[0079] The present invention will be described in more detail below with reference to examples. In the following examples, "parts" refers to mass percent.

[0080] In this invention, the weight-average molecular weight (in polystyrene equivalent) was measured by GPC using the HLC8220 system manufactured by Tosoh Corporation under the following conditions. Separation column: Four TSKgelGMHHR-N columns manufactured by Tosoh Corporation were used. Column temperature: 40°C. Mobile phase: Tetrahydrofuran manufactured by Wako Pure Chemical Industries, Ltd. Flow rate: 1.0 ml / min. Sample concentration: 1.0 wt%. Sample injection volume: 100 microliters. Detector: Differential refractometer. Furthermore, the glass transition temperature (Tg) was measured using a differential scanning calorimeter ("DSC Q100" manufactured by TA Instruments Co., Ltd.) under a nitrogen atmosphere and with a cooling device, scanning was performed within a temperature range of -80 to 450°C and a heating rate of 10°C / min. Furthermore, the hydroxyl value of the resin is calculated by back titrating the remaining acid with an alkali after acetylating the hydroxyl groups in the resin with an excess of acetyl reagent, and expressing the amount of hydroxyl groups per gram of resin in milligrams of potassium hydroxide (KOH), in accordance with JIS K0070.

[0081] [Preparation of coating composition Example 1] A coating composition (Example 1) was prepared by stirring and mixing a total of 99.5 parts of the following materials in a stirrer for 30 minutes: 50 parts of "Acrylic Polyol Resin-1 (weight-average molecular weight: 14,000, Tg: 50℃, hydroxyl value: 95 mg KOH / g)" as resin (A), 7 parts of wet gel silica "Sylysia 350 (average particle size 1.8 μm)" as silica (B), 0.5 parts of "Aerosil 50 (average primary particle size: 0.03 μm)" as nanosilica (C), 2 parts of "Flonon SP-1000AF" as a thixotrope (D), and 40 parts of "ethyl acetate" as solvent (E).

[0082] [Preparation of coating compositions: Examples 2-20, Comparative Examples 1-12] Coating compositions (Examples 2-20, Comparative Examples 1-12) were prepared using the same procedure as in Example 1, according to the formulations shown in Tables 1-4.

[0083] [Preparation of cosmetic materials for evaluation (Examples 1-17, Comparative Examples 1-8)] For each of the prepared coating compositions (Examples 1-17, Comparative Examples 1-8), 16 parts of the isocyanate curing agent "Desmodule N-3300A" (Sumika Covestro Urethane Co., Ltd.) and 20 parts of ethyl acetate were added and stirred until uniform to prepare a coating composition. For evaluation of gloss and clarity, black ink-covered paper was prepared, and each coating composition was applied using a bar coater. After solvent drying, the paper was cured at 50°C for 12 hours to obtain evaluation materials (Examples 1-17, Comparative Examples 1, 3, 4, 5, 7). By mass measurement, the coating amount of the cured coating film was determined to be 4-6 g / m². 2 I confirmed that this was the case.

[0084] [Preparation of cosmetic materials for evaluation (Examples 18-20, Comparative Examples 9-12)] To the prepared coating compositions (Examples 18-20, Comparative Examples 9-12), 4 parts of the photopolymerization initiator "Omnirad 184" (1-hydroxycyclohexyl-phenyl-ketone, manufactured by IGM Resins BV) and 15 parts of ethyl acetate were added and stirred until homogeneous to prepare the coating composition. For gloss and clarity evaluation, black ink paper was prepared, and each coating composition was applied using a bar coater. After solvent drying, the paper was irradiated with a UV irradiation device (manufactured by GS Yuasa Corporation) under a 120 W / cm air-cooled high-pressure mercury lamp at a speed of 25 m / min to obtain the evaluation decorative materials (Examples 18-20, Comparative Examples 9, 11, 12). By mass measurement, the coating amount of the cured coating was determined to be 4-6 g / m². 2 I confirmed that this was the case.

[0085] [Evaluation Method] The prepared coating compositions and the cosmetic materials used for evaluation were evaluated according to the following method.

[0086] (Settlement stability) The coating composition was placed in a glass bottle and left to stand for 30 days at 40°C. After that, it was shaken by hand for 2 minutes, and the sediment was visually observed. The easier the sediment was to redisperse, the more productive the coating composition was. The results were recorded according to the following criteria. (〇) The sediment has dispersed and disappeared. (△) Some of the sediment has loosened. (×) The sediment remained intact without breaking apart.

[0087] (Liquidity) The coating composition was placed in a glass bottle, and the liquid was visually observed at room temperature with the bottle tilted at a 45° angle to check for flow. Easier flow indicated a more productive coating composition. The results were recorded according to the following criteria. (〇) The liquid flowed in conjunction with the tilting motion. (△) The liquid flowed with a delay in response to the tilting motion. (×) The liquid did not flow at all.

[0088] (Glossy) For the decorative materials used for evaluation, the 60° gloss of the coated surface was measured using a GM-1 gloss meter manufactured by Suga Test Instruments Co., Ltd., in accordance with JIS Z8741. A lower gloss level indicates a more luxurious and superior design.

[0089] (Clarity) For the decorative materials used for evaluation, the brightness L value of the coated surface was measured using a Konica Minolta CR-400 in accordance with JIS Z8781. A lower clarity L value indicates a better design with less blurring of the underlying pattern.

[0090] Tables 1-4 show the results of the evaluation of the storage stability, fluidity, gloss (60°), and clarity (brightness L value) of each coating composition, as well as the cosmetic materials used for evaluation. Note that all values ​​in the tables are in parts by mass or mass%, and blank spaces indicate that the ingredient was not included.

[0091] [Table 1]

[0092] [Table 2]

[0093] [Table 3]

[0094] [Table 4]

[0095] The abbreviations used in the table are shown below. • "Acrylic Polyol Resin-1" Acrylic polyol resin (resin solids content: 55% by weight, weight-average molecular weight: 14,000, Tg: 50℃, hydroxyl value: 95 mgKOH / g) • "Urethane Acrylate Resin-1" Urethane acrylate resin (resin solids content: 100% by weight, weight-average molecular weight: 5000, Tg: 75℃, average double bond equivalent: 500g / mol) • "Silysia 350" wet gel silica (average particle size 1.8 μm), manufactured by Fuji Silysia Chemical Co., Ltd. • "NIPGEL AZ-200" wet gel silica (average particle size 2.4 μm), manufactured by Tosoh Silica Co., Ltd. • "Mizukasil P-705" wet gel silica (average particle size 3.0 μm), manufactured by Mizusawa Chemical Industry Co., Ltd. • "Silysia 450" wet gel silica (average particle size 5.2 μm), manufactured by Fuji Silysia Chemical Co., Ltd. • "NIPSIL E-200" precipitation-type silica (average particle size 3.3 μm), manufactured by Tosoh Silica Co., Ltd. • "Aerosil 50" fumed silica (average primary particle size 0.03 μm), manufactured by Evonik Industries AG. • "Aerosil R972" fumed silica (average primary particle size 0.016 μm), manufactured by Evonik Industries AG. • "Flonon SP-1000AF" High-grade fatty acid amide (active ingredient: 10%) Manufactured by Kyoeisha Chemical Co., Ltd. • "Tallen 7200-20" High-grade fatty acid amide (active ingredient: 20%) Manufactured by Kyoeisha Chemical Co., Ltd. • "Desmodule N-3300A" Isocyanate Curing Agent, manufactured by Sumika Covestro Urethane Co., Ltd. • "Omnirad 184" photopolymerization initiator (1-hydroxycyclohexyl-phenyl-ketone), manufactured by IGM Resins BV.

[0096] The evaluation results showed that the cosmetic materials using the coating composition of the present invention all exhibited a good matte effect and excellent clarity, and the storage stability and fluidity of the coating composition were also good. On the other hand, Comparative Examples 1, in which the silica (B) content ratio to the solid content of resin (A) was low, Comparative Examples 3 and 12, in which the average particle size of silica (B) was large, and Comparative Examples 4 and 11, in which silica (B) was not gel-processed silica, exhibited insufficient gloss and clarity. In Comparative Examples 5 and 9, where the ratio of nanosilica (C) to silica (B) was low, the precipitate aggregated, making redispersion difficult. Similarly, in Comparative Example 7, where the ratio of thixotropic agent (D) to nanosilica (C) was low, the precipitate aggregated, making redispersion difficult. Comparative Examples 2 and 10, in which the silica (B) content ratio was too high relative to the solid content of resin (A), Comparative Example 6, in which the nanosilica (C) content ratio was too high relative to silica (B), and Comparative Example 8, in which the thixotropizer (D) content ratio was too high relative to nanosilica (C), had no fluidity at all at room temperature, making it difficult to prepare the coating composition itself.

Claims

1. It contains resin (A), silica (B), nanosilica (C), and a thixotrope (D), The content ratio of the silica (B) to the solid content of the resin (A) is 20 to 40% by mass. The content ratio of nanosilica (C) to silica (B) is 2 to 15% by mass. The content ratio of the thixotrope (D) to the nanosilica (C) is 30 to 80% by mass. The silica (B) is gel-processed silica, and the average particle size of the silica (B) is 0.1 to 5 μm. The average primary particle size of the nanosilica (C) is 0.001 to 0.1 μm. Coating composition.

2. The aforementioned thixotrope (D) is a fatty acid amide. The coating composition according to claim 1.

3. Furthermore, containing solvent (E), The coating composition according to claim 1.

4. The nanosilica (C) is fumed silica. The coating composition according to claim 1.

5. A decorative material obtained by coating a substrate surface with the coating composition according to any one of claims 1 to 4.

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