Two-component curing coating composition and decorative material

Abstract

The present invention provides a coating composition that has a good tactile feel, excellent storage stability, and simultaneously offers resistance to staining and solvent rubbing. [Solution] The above problem is solved by a two-component curable coating composition comprising a polyol composition (X) and a curing agent composition (Y) containing a curing agent, wherein the polyol composition (X) comprises an acrylic polyol resin (A), acrylic beads (B), and a silicone additive (C), the average particle size of the acrylic beads (B) is 10 to 30 μm, the abundance ratio of the crystalline phase component by pulsed NMR spectroscopy is 80% or more, and the content of the acrylic beads (B) relative to the non-volatile component of the acrylic polyol resin (A) is 10 to 30% by mass.

Description

Technical Field

[0001] The present invention relates to a two-component curable coating composition and a decorative material.

Background Art

[0002] For the surfaces of architectural 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 order to improve durability, a two-component curable coating agent has been studied. In recent years, a more excellent design, that is, reproduction of a woody texture, has been demanded. In order to reproduce the woody texture, a rough touch (tactile sensation) is imparted to the coating layer. As one of the methods, it is known to add organic fine particles typified by acrylic beads to the coating agent. However, there are problems such as the coating agent becoming easily thickened, poor storage stability occurring, and the beads detaching due to solvent rubbing and the tactile sensation being lost. In addition, at present, a coating agent that兼备 all physical properties such as clarity that does not cause the printed pattern to become blurred and stain resistance that can easily wipe off attached contaminants has not been obtained.

[0003] In Patent Document 1, there is disclosed a decorative film having a base film, a thermoplastic resin layer, and a top coat layer in this order, wherein the top coat layer contains silica particles and resin beads in a urethane resin, and the resin beads contain at least one of acrylic beads and urethane beads. However, there is concern about the storage stability of the coating agent constituting the top coat layer, and the solvent rubbing resistance is also insufficient.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

[0005] In view of the foregoing, the problem that the present invention aims to solve is to provide a coating composition that has a good tactile feel, excellent storage stability, and can also achieve both stain resistance and solvent rubbing resistance. [Means for solving the problem]

[0006] The present invention comprises a polyol composition (X) and a curing agent composition (Y) containing a curing agent. The polyol composition (X) comprises an acrylic polyol resin (A), acrylic beads (B), and a silicone additive (C). The average particle size of the acrylic beads (B) is 10 to 30 μm, and the abundance ratio of the crystalline phase component determined by pulsed NMR is 80% or more. The content of the acrylic beads (B) relative to the non-volatile components of the acrylic polyol resin (A) is 10 to 30% by mass. The above-mentioned problems are solved by a two-component curing coating composition. [Effects of the Invention]

[0007] The two-component curable coating composition of the present invention has a good tactile feel, excellent storage stability, and can achieve both stain resistance and solvent rubbing resistance, 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 ×× or less". In this invention, (meth)acrylate means acrylate or methacrylate. In the present invention, the average particle diameter of the acrylic beads (B) is the average particle diameter measured by the Coulter counter method in accordance with JIS Z 8832:2010 "Method for measuring particle size distribution - Electrical detection zone method".

[0009] <Two-component curing coating composition> The two-component curable coating composition of the present invention comprises a polyol composition (X) and a curing agent composition (Y) containing a curing agent, wherein the polyol composition (X) comprises an acrylic polyol resin (A), acrylic beads (B), and a silicone additive (C).

[0010] <Acrylic polyol resin (A)> The acrylic polyol resin (A) contained in the polyol composition (X) is obtained by copolymerizing a compound (a1) having a hydroxyl group and a polymerizable unsaturated group with another (meth)acrylic compound or an ester thereof. Examples of the compound (a1) having the hydroxyl group and polymerizable unsaturated group include aliphatic (meth)acrylate compounds such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerin di(meth)acrylate, trimethylolpropane di(meth)acrylate, and pentaerythritol tri(meth)acrylate; 4-hydroxyphenyl acrylate, β-hydroxyphenethyl acrylate, 4-hydroxyphenethyl acrylate, 1-phenyl-2-hydroxyethyl acrylate, 3-hydroxy-4-acetylphenyl acrylate, 2 Examples include aromatic ring-containing (meth)acrylate compounds such as hydroxy-3-phenoxypropyl acrylate; polyether-modified (meth)acrylate compounds obtained by ring-opening polymerization of the (meth)acrylate compound with various cyclic ether compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether; and lactone-modified (meth)acrylate compounds obtained by polycondensation of the (meth)acrylate compound with lactone compounds such as ε-caprolactone. These compounds having hydroxyl groups and polymerizable unsaturated groups can be used alone or in combination of two or more. Among these, 2-hydroxyethyl (meth)acrylate is preferred because it provides excellent stain resistance.

[0011] Other (meth)acrylic compounds include, for example, alkyl esters of (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, neopentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, cetyl (meth)acrylate, lauryl (meth)acrylate, etc.; 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 1H,1H,5H-octafluoropentyl (meth)acrylate, 2-(perfluorooctyl)ethyl (meth)acrylate (Meth)acrylic compounds having a fluorine atom, such as phosphate; (meth)acrylic compounds having an alicyclic structure, such as isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, sidiclopentanyl (meth)acrylate, and dicyclopentenyloxyethyl (meth)acrylate; (meth)acrylic compounds having an ether group, such as polyethylene glycol mono(meth)acrylate, methoxyethyl (meth)acrylate, methoxybutyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, and methoxypolyethylene glycol (meth)acrylate; and styrene, benzyl (meth)acrylate, 2-ethyl-2-methyl-[1,3]-dioxolan-4-yl-methyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, etc. can be used. These (meth)acrylic compounds may be used alone or in combination of two or more. Among these, it is preferable to use one or more (meth)acrylic compounds selected from the group consisting of styrene, methyl (meth)acrylate, and n-butyl (meth)acrylate, from the viewpoint of suppressing bead detachment.

[0012] The weight-average molecular weight of the acrylic polyol resin (A) is preferably in the range of 5,000 to 200,000, and more preferably in the range of 10,000 to 60,000, in order to obtain even better solvent rubbing resistance. The weight-average molecular weight of the acrylic polyol resin (A) is shown as the value measured by gel permeation chromatography (GPC).

[0013] The glass transition temperature of the acrylic polyol resin (A) is preferably 30 to 100°C, and more preferably 40 to 80°C, in order to obtain even better stain resistance, flexibility, and adhesion. The glass transition temperature of the acrylic polyol resin (A) is shown as the value measured by DSC in accordance with JIS K7121-1987. Specifically, the polyacrylic polyol resin (A) is placed in a differential scanning calorimeter, heated to (Tg + 50°C) at a heating rate of 10°C / min, held for 3 minutes, then rapidly cooled, and the midpoint glass transition temperature (Tmg) read from the obtained differential thermal curve is shown.

[0014] The hydroxyl value (measured according to JIS K-1557) of the acrylic polyol resin (A) is preferably 5 to 300 mg KOH / g, and more preferably 5 to 100 mg KOH / g. A coating layer obtained using an acrylic polyol with a hydroxyl value of 5 mg KOH / g or more has a suitable crosslinking density and readily provides sufficient solvent resistance. Furthermore, a hydroxyl value of 300 mg KOH / g or less tends to result in a more favorable flexibility of the coating layer.

[0015] The method for producing the acrylic polyol resin (A) is not particularly limited and can be produced by known methods. For example, one method is to copolymerize the compound (a1) with another (meth)acrylic compound or its ester in the presence of a polymerization initiator.

[0016] Various conditions in the production of the acrylic polyol resin (A) can be appropriately set according to the raw materials used and their amounts. For example, a method of adding some raw materials into the reaction vessel first, heating to 80°C to 160°C, and then carrying out a polymerization reaction while dropping the remaining raw materials over 2 to 8 hours; a method of adding an organic solvent to the reaction vessel, heating to 80°C to 160°C, and then carrying out a polymerization reaction while dropping a mixture of raw materials used in the reaction over 2 to 8 hours; a method of adding an organic solvent to the reaction vessel, heating to a temperature above the boiling point of the organic solvent under sealed pressure conditions, and then carrying out a polymerization reaction while dropping a mixture of raw materials used in the reaction over 2 to 8 hours, etc. can be mentioned.

[0017] The polyol composition (X) may contain other resins other than the acrylic polyol resin (A). Specifically, for example, a vinyl chloride-vinyl acetate copolymer resin, an acrylic resin, a urethane resin, an acrylic urethane resin, nitrocellulose, polyvinyl alcohol, polyvinyl acetal, a cellulose derivative, a polycarbonate resin, a polyamide resin, a polyester resin, a butyral resin, an epoxy resin, etc., or a mixture of one or more of these resins can be used. Among them, an acrylic resin and a urethane resin are preferred.

[0018] The polyol composition (X) may contain a resin having a radically polymerizable unsaturated group. For example, urethane (meth)acrylate, acrylic (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, etc. can be mentioned. Among them, urethane (meth)acrylate and acrylic (meth)acrylate have the physical properties as a coating agent and are preferred. Also, as a reactive diluent, an acrylate monomer, an acrylate oligomer, etc. can also be used.

[0019] Components constituting the urethane (meth)acrylate include a polyfunctional alcohol component, a compound having one or more alcoholic hydroxyl groups and one or more (meth)acrylate esters or (meth)acrylamides in the molecule, and a polyisocyanate compound. 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, 1,6-hexanediol, 1,2-hexanediol, 1,8-octanediol, and 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[5.5) 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, refined castor oil, etc. are mentioned, and one or more compounds selected from these compounds can be used alone or, if necessary, two or more can be mixed in any ratio.

[0020] Among the components of the urethane (meth)acrylate, examples of the compound for imparting a terminal radically polymerizable unsaturated bond include compounds having one or more alcoholic hydroxyl groups and one or more (meth)acrylic acid esters or (meth)acrylamides in the molecule. 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 referred to as epoxy acrylates, 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, and poly(propylene glycol) diglycidyl ether with (meth)acrylic acid, can be used. One or more compounds selected from this group can also be used as compounds having 2-hydroxyl(meth)acrylic acid ester structures at both ends to introduce radically polymerizable unsaturated bonds into the urethane resin skeleton.

[0021] Examples of monomer components constituting the acrylic (meth)acrylate include monofunctional monomers such as ethyl (meth)acrylate, ethylhexyl (meth)acrylate, styrene, methylstyrene, and N-vinylprolidone, as well as polyfunctional monomers, such as 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, and neopentyl glycol (meth)acrylate.

[0022] The double bond equivalent of the 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, volume shrinkage during curing is suppressed, reducing the possibility of cracking due to bending or distortion of the coating film, and making it less likely for the processability to deteriorate due to dense crosslinking to occur. When it is 750 g / mol or less, the physical properties such as hardness after the reaction are favorable due to sufficient reactive groups. This range is more preferably 200 to 400 g / mol, and even more preferably 200 to 300 g / mol. Furthermore, the weight-average molecular weight of the acrylic (meth)acrylate is preferably in the range of 10,000 to 100,000. If the weight-average molecular weight of the acrylic (meth)acrylate is 10,000 or more, the tackiness of the coating film is suppressed, and tack-free coating is possible through the drying process alone. If it is 100,000 or less, the viscosity of the composition can be kept within an appropriate range, maintaining the dilution ratio during coating and ensuring a sufficient coating amount. Moreover, the range from 100,000 to 50,000, 100,000, and 10,000 to 30,000 are even more preferable.

[0023] The glass transition temperature (Tg) of the acrylic (meth)acrylate is preferably in the range of 40 to 130°C. If it is 40°C or higher, sufficient strength tends to be obtained after curing when it is made into a coating film, and if it is 130°C or lower, brittleness is less likely to occur when it is 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 mg KOH / g. A value of 5 mg KOH / g or higher allows for good bead dispersion and achieves low gloss, while a value of 300 mg KOH / g or lower results in good performance in terms of stain resistance and other properties.

[0024] Furthermore, a monomer having a (meth)acryloyl group may be used as a reactive diluent. The monomer having a (meth)acryloyl group is not particularly limited, and any monomer having a (meth)acryloyl group that can be cured with known active energy rays (hereinafter sometimes 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.

[0025] 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.

[0026] 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.

[0027] 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.

[0028] 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.

[0029] The polyol composition (X) may contain 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.

[0030] The content of the acrylic polyol resin (A) in the polyol composition (X) is preferably 30 to 85% by mass, and more preferably 40 to 70% by mass, relative to the total mass of the polyol composition (X). When the content of the acrylic polyol resin (A) is within this range, a suitable tactile feel can be achieved while improving scratch resistance and abrasion resistance. Note that the resin content refers to the amount of non-volatile components, i.e., active ingredients. Furthermore, the acrylic polyol resin (A) may be a combination of multiple resins, in which case the content of acrylic polyol resin (A) refers to the total content of non-volatile components of all resins.

[0031] <Acrylic beads (B)> The acrylic beads (B) contained in the polyol composition (X) have an average particle size of 10 to 30 μm, and the abundance ratio of the crystalline phase component determined by pulsed NMR is 80% or more. The acrylic beads (B) are not particularly limited, and known acrylic resin beads can be used. Specifically, examples include polymethyl methacrylate, polybutyl methacrylate, polymethacrylate esters, copolymers of polystyrene and polymethyl methacrylate, copolymers of polystyrene and polybutyl methacrylate, copolymers with other resins, and crosslinked products thereof (e.g., crosslinked polymethyl methacrylate, crosslinked polybutyl methacrylate, crosslinked polymethacrylate esters, etc.). Among these, crosslinked polymethyl methacrylate is preferred because it has better storage stability and rubbing resistance. Furthermore, ethylene glycol dimethacrylate crosslinking agent is preferred as the crosslinking agent for obtaining the crosslinked product.

[0032] The acrylic beads (B) have an average particle size of 10 to 30 μm. A good tactile feel is obtained when the particle size is within this range. From the viewpoint of balancing tactile feel and storage stability, the average particle size is preferably 12 to 30 μm, more preferably 18 to 30 μm, and even more preferably 18 to 25 μm.

[0033] The aforementioned acrylic beads (B) have a crystalline phase component ratio of 80% or more, as determined by pulsed NMR (pulsed NMR (nuclear magnetic resonance) measurement). Adding such acrylic beads (B) improves solvent rubbing resistance and storage stability. The reason for this is not clear, but the inventor speculates as follows. The pulsed NMR method described above measures molecular mobility, and the "crystalline phase" refers to a region where molecular mobility is reduced due to factors such as cross-linking of molecules or high cohesive force, corresponding to a highly crystalline region. When the proportion of this crystalline phase component is 80% or more, the low molecular mobility makes it difficult for the beads to swell due to solvents, resulting in good solvent rubbing properties. Furthermore, the beads do not swell during storage of the polyol composition (X), resulting in good storage stability. The method for measuring the crystalline phase components using pulsed NMR will be described in the examples below.

[0034] The upper limit for the abundance of the crystalline phase component of the acrylic beads (B) as determined by the pulsed NMR method is 100%. Furthermore, in order to achieve both superior solvent rubbing resistance and storage stability, the abundance of the crystalline phase component is preferably 90% or more, and more preferably 90-95%.

[0035] Acrylic beads (B) having a crystalline component ratio of 80% or more as determined by the pulsed NMR method can be obtained by appropriately selecting monomers, polymerization methods, polymerization conditions, additives, etc. For example, the crystalline component ratio can be increased by using methyl methacrylate, a highly crystalline monomer; by polymerizing under appropriate conditions using anionic polymerization to create an isotactic structure; by adding nucleating agents or crosslinking agents as additives; or by combining these methods.

[0036] In the polyol composition (X), the content of the acrylic beads (B) relative to the non-volatile component of the acrylic polyol resin (A) is 10 to 30% by mass. When the content of the acrylic beads (B) relative to the non-volatile component of the acrylic polyol resin (A) is within this range, a suitable tactile feel and clarity can be obtained. Furthermore, this range is preferably 12 to 30% by mass, and more preferably 12 to 25% by mass. Furthermore, the acrylic beads (B) are preferably contained in the polyol composition (X) in an amount of 3 to 15% by mass, and more preferably in an amount of 5 to 12% by mass. When the content of the acrylic beads (B) is within this range, good tactile properties and storage stability can be achieved.

[0037] <Silicone additive (C)> The polyol composition (X) contains a silicone additive (C). When the two-component curable coating composition of the present invention is coated onto a substrate, the silicone additive (C) quickly orients on the surface, contributing to improved stain resistance. It also functions as a good lubricant on the surface, thereby improving the abrasion resistance of the decorative sheet surface, and particularly when the edges and corners, which are wrapped, come into frequent contact with people or objects, exhibiting good abrasion resistance and stain resistance. Examples of the silicone additive (C) include various silicone oils. Various addition polymerization type silicone oils and condensation polymerization type silicone oils can be used as the silicone oil, but condensation polymerization type silicone oil is preferred. Specifically, as silicone oils, amino-modified silicone oil, carbinol-modified silicone oil, carboxyl-modified silicone oil, phenol-modified silicone oil, alcohol-modified silicone oil, vinyl-modified silicone oil, urethane-modified silicone oil, epoxy-modified silicone oil, polyester-modified silicone oil, polyether-modified silicone oil, polyester-modified silicone oil, acrylic-modified silicone oil, aralkyl-modified silicone oil, and amide-modified silicone oil can be used, but among these, amino-modified silicone oil and carboxyl-modified silicone oil are preferred due to their good reactivity, and amino-modified silicone oil is more preferred. By using these in combination with the acrylic polyol resin (A), excellent stain resistance can be provided.

[0038] The content of the silicone additive (C) in the polyol composition (X) is preferably 0.1 to 5% by mass, more preferably 0.5 to 3% by mass, and even more preferably 1 to 3% by mass, based on the total amount of the polyol composition (X). When the content is within this range, an excellent balance of stain resistance and storage stability is achieved.

[0039] The silicone additive (C) may be added immediately before coating, rather than being added internally to the polyol composition (X). In this case, the formation of gel-like reactants can be suppressed by mixing the silicone additive with the polyol composition (X) and stirring it uniformly before mixing with the curing agent composition (Y). Even in this case, the silicone additive is still included in the formulation of the polyol composition (X).

[0040] (Solvent (D)) The polyol composition (X) may, preferably, further contain a solvent (D). The solvent (D) dilutes the coating composition, maintaining its fluidity and improving its storage stability. Examples of solvents (D) 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. Among these, ester solvents are preferred from the viewpoint of improving the working environment.

[0041] The content of the solvent (D) 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.

[0042] (Other ingredients) The polyol composition (X) may further contain, as an optional component, a matting agent, a wax, a plasticizer, a leveling agent, a surfactant, a dispersant, an antifoaming agent, an ultraviolet absorber, a light stabilizer, a polymerization inhibitor, a drying agent, a thixotrope, a filler, and the like.

[0043] (Method for producing polyol composition (X)) The polyol composition (X) can be produced by stirring and dispersing an acrylic polyol resin (A), acrylic beads (B), a silicone additive (C), and other solvents (D) and various additives, and / or by dispersing them in a paste-like mixture. The polyol composition (X) can be prepared by appropriately adjusting the size of the grinding media in the disperser, the packing 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 polyol composition (X) 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 material. Conventional known filters can be used.

[0044] <Curing agent composition (Y)> The present invention provides a two-component curable coating composition comprising a polyol composition (X) and a curing agent composition (Y) containing a curing agent. The curing agent reacts with an acrylic polyol resin (A) to improve coating performance. Examples of curing agents include isocyanate compounds, melamine compounds, epoxy compounds, amine compounds, and alkyl silicate compounds. Among these, isocyanate compounds are preferred as curing agents.

[0045] 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. The hardener is not included as a non-volatile component of the acrylic polyol resin (A).

[0046] The content of the isocyanate compound in the acrylic polyol resin (A) and other resins can be set arbitrarily, but it is preferable that the hydroxyl group / isocyanate equivalent ratio is 1 / 0.5 to 1 / 3. Furthermore, it is preferable that the curing agent is contained in an amount of 20 to 60% by mass relative to the nonvolatile components of the acrylic polyol resin (A).

[0047] If the polyol composition (X) contains a resin having radically polymerizable unsaturated groups, a photopolymerization initiator may be added to the curing agent composition (Y). 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.

[0048] When ultraviolet light is used as the active energy ray, known and used photopolymerization initiators can be used as curing agents for the two-component curable coating composition of the present invention, and the photopolymerization initiator can be added to the curing agent composition (Y). 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.

[0049] 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.

[0050] 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 nonvolatile components of the resin having radically polymerizable unsaturated groups. 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.

[0051] 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 curing agent composition (Y) 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.

[0052] 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 nonvolatile components of the resin in the coating composition.

[0053] The curing agent composition (Y) may further contain a solvent, and one of the solvents exemplified in solvent (D) may be used. Furthermore, the solvent (D) of the polyol composition (X) and the solvent of the curing agent composition (Y) may be different, but it is preferable to use the same solvent.

[0054] (Manufacturing of coating compositions) The two-component curable coating composition of the present invention can be manufactured by stirring and / or dispersing the polyol composition (X) and the curing agent composition (Y) in a paste. Since the curing reaction begins when the polyol composition (X) and the curing agent composition (Y) are mixed, the manufacturing of the coating composition is performed immediately before application.

[0055] (Coating of coating compositions) The two-component curable coating composition of the present invention can be applied to the surface of a substrate. Specific examples of application 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 composition. Examples of drying methods include, but are not limited to, natural drying, heat drying, hot air drying, ultraviolet drying, infrared drying, and oven drying.

[0056] Furthermore, the curing method for the two-component curable coating composition of the present invention is not particularly limited and can be cured by known heating methods.

[0057] (Coating layer) The two-component curable coating composition of the present invention can be applied to the surface of a substrate by coating or printing, and then undergoing drying and curing steps as necessary to form a coating layer.

[0058] The thickness of the coating layer after drying is preferably in the range of 1 to 20 μm, more preferably in the range of 2 to 15 μm, and even more preferably in the range of 3 to 10 μm. This thickness range allows the acrylic beads (B) to be efficiently exposed on the surface, maximizing the effects of the present invention.

[0059] The coating layer is formed by the non-volatile components of the two-component curable coating composition of the present invention. The coating layer preferably contains 30 to 80% by mass of components derived from acrylic polyol resin (A) (i.e., components obtained by curing acrylic polyol resin (A) with a curing agent), and more preferably 50 to 80% by mass. The coating layer also preferably contains 3 to 20% by mass of acrylic beads (B), and more preferably 6 to 18% by mass.

[0060] <Decorative materials> Examples of decorative materials coated with the two-component curing 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. The decorative sheet is constructed by forming a pattern layer on a substrate such as paper by printing or applying 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 two-component curing coating composition of the present invention forms the topcoat layer.

[0061] (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.

[0062] The 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.

[0063] One or both sides of the 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.

[0064] A decorative sheet using the two-component curing 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.

[0065] The 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-based 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.

[0066] The aforementioned pattern layer provides decorative appeal to the decorative sheet with a desired pattern, 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, abstract patterns, etc. Furthermore, the method of forming the pattern layer is not particularly limited, and it may be formed by printing methods using colored inks, coating agents, etc., obtained by dissolving (or dispersing) a known coloring agent (dye or pigment) 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.

[0067] The transparent adhesive layer is not particularly limited as long as it is transparent, and is not particularly limited to adhesives that include colorless transparent, colored transparent, or translucent. Adhesives known in the field of decorative sheets can be used, such as thermoplastic resins such as polyamide resin, acrylic resin, and 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.

[0068] 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.

[0069] Furthermore, various coating compositions can be applied to the entire surface or partially to form two to three overlapping coating layers. For example, by applying a known matte coating composition to the entire surface and then partially applying the two-component curing coating composition of the present invention in accordance with the pattern layer, a more realistic wood texture can be achieved.

[0070] Taking a decorative sheet using the two-component curing coating composition of the present invention as an example, a pattern layer is formed on the substrate by printing or applying known printing inks or paints such as acrylic, cellulose, vinyl, chlorinated polyolefin, chlorinated rubber, or urethane. Then, as described above, the two-component curing coating composition of the present invention is applied to form a coating layer to manufacture the decorative sheet. Alternatively, multiple coating layers may be formed on the pattern layer before applying the two-component curing coating composition of the present invention.

[0071] As described above, the two-component curing coating composition of the present invention is formed by appropriately employing a roll coater, gravure coater, flexo coater, air doctor coater, blade coater, air knife coater, squeeze coater, impregnation coater, transfer roll coater, kiss coater, curtain coater, cast coater, spray coater, die coater, offset printing press, screen printing press, etc.

[0072] The aforementioned decorative panel can be obtained by coating a wood-based decorative panel, etc., commonly used for decorative panels, with the two-component curing 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]

[0073] The present invention will be described in more detail below with reference to examples. In the following examples, "parts" refers to mass percent.

[0074] The weight-average molecular weight (in polystyrene equivalent) was measured using GPC with 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.

[0075] The glass transition temperature (Tg) was measured using a differential scanning calorimeter (DSCQ100, 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.

[0076] 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.

[0077] The crystalline phase component ratio was measured using a pulsed NMR spectrometer (Bruker Minispec mq20) with the following settings: nuclide: 1H, measurement: T2, pulse sequence: Solid echo method, measurement temperature: 40°C, repetition time: 3 seconds, and number of integrations: 32. The obtained spin-spin relaxation free induction decay curve of 1H was separated into two waveforms, one originating from the crystalline phase and the other from the amorphous phase. The ratio of each component was determined from the two component curves obtained from each measurement. The average value obtained from five identical measurements was used as the measurement result.

[0078] [Preparation of polyol composition (X) (Example 1)] A total of 101 parts of the following were mixed in a stirrer for 30 minutes: 40 parts of "Acrylic Polyol 1 (weight-average molecular weight: 14,000, Tg: 50℃, hydroxyl value: 95 mg KOH / g)" as acrylic polyol resin (A), 40 parts of "Acrylic Polyol 2 (weight-average molecular weight: 12,000, Tg: 75℃, hydroxyl value: 10 mg KOH / g)" as acrylic polyol resin (A), 6 parts of "Acrylic Beads 1 (average particle size: 15 μm, pulsed NMR crystal phase component: 90%)" as acrylic beads (B), 2 parts of "Amino-modified silicone oil" as silicone additive (C), and 13 parts of "Butyl acetate" as solvent (D). A polyol composition (X) (Example 1) was prepared by stirring these together in a stirrer.

[0079] [Preparation of polyol composition (X) (Examples 2-13, Comparative Examples 1-8)] Polyol compositions (X) (Examples 2-13, Comparative Examples 1-8) were prepared according to the formulations shown in Tables 1-2, using the same procedure as in Example 1.

[0080] [Preparation of cosmetic materials for evaluation (Examples 1-13, Comparative Examples 1-8)] For the prepared polyol compositions (X) (Examples 1-13, Comparative Examples 1-8), a curing agent composition (Y) consisting of 15 parts of the isocyanate curing agent "Desmodule N-3300A" and 10 parts of ethyl acetate was added and stirred until homogeneous to prepare a two-component curing type coating composition. For evaluation, 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 decorative materials (Examples 1-13, Comparative Examples 1-8). By mass measurement, the coating amount of the cured coating film of the coating composition was determined to be 4-6 g / m². 2 I confirmed that this was the case.

[0081] [Evaluation Method] The prepared polyol composition (X) and the cosmetic material for evaluation were evaluated according to the following method.

[0082] (Storage stability) The polyol composition (X) was placed in a glass bottle, and its viscosity was measured using a Type B rotational viscometer in accordance with JIS K7117-1 at an environment of 25°C (η 0 ). Subsequently, the glass bottle was left to stand at room temperature for 14 days, and the viscosity was measured again using the same method (η 1 The viscosity change rate was calculated according to the following formula. Viscosity change rate (%) = (viscosity after standing still (η 1 )-Initial viscosity (η 0 )) / Initial viscosity(η 0 ) A lower viscosity change rate indicates less thickening and better storage stability of the composition.

[0083] (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 Z 8781. A lower clarity L value indicates a better design with less blurring of the underlying pattern.

[0084] (Touch) We compared the tactile feel of a decorative material used for evaluation and a standard piece of wood (cedar) whose surface had been smoothed with medium-grit sandpaper. The evaluation was conducted on 10 subjects, and the results were recorded according to the following criteria. (〇) 7 to 10 people answered that it had a texture similar to real wood. (△) Four to six people answered that it had a texture similar to real wood. (×) Three or fewer people answered that it had a texture similar to real wood.

[0085] (Solvent-resistant rubbing) For the evaluation material, a cotton cloth soaked in methyl ethyl ketone was attached to a jig with a 1.5 kg load, and the coating film was rubbed back and forth 50 times to observe changes in tactile sensation. The results were recorded according to the following criteria. (〇) There was no change in texture. (×) There was a change in texture.

[0086] (Stain resistance) For the cosmetic material used for evaluation, a contaminant (oil-based black marker) was applied to the surface of the coating film. After standing for 4 hours, the surface was wiped with an alcohol-containing cloth, and the amount of remaining contaminant was visually observed. The results were recorded according to the following criteria. (○) No residual contaminants were found. (×) Residual contamination was observed.

[0087] Tables 1 and 2 show the formulation and storage stability of each polyol composition (X), as well as the evaluation results for clarity, tactile feel, solvent rubbing resistance, and stain resistance of the cosmetic material used for evaluation. Note that all values ​​in the table are in parts by mass or mass%, and blank spaces indicate that the composition was not included.

[0088] [Table 1]

[0089] [Table 2]

[0090] The abbreviations used in the table are shown below. • "Acrylic Polyol 1": Acrylic polyol resin (glass transition temperature: 50℃, Mw: 14000, hydroxyl value: 95mgKOH / g) • "Acrylic Polyol 2": Acrylic polyol resin (glass transition temperature: 75℃, Mw: 12000, hydroxyl value: 10mgKOH / g) • "Acrylic Beads 1": GR-400 polymethyl methacrylate acrylic beads (15μm) manufactured by Negami Kogyo Co., Ltd., refractive index: 1.49, heat resistance: 245℃, pulsed NMR - crystalline phase composition: 90% • "Acrylic Beads 2": Polymethyl methacrylate acrylic beads (20 μm), pulsed NMR - crystalline phase component: 92% • "Acrylic Beads 3": MB20X-30 polymethyl methacrylate acrylic beads (30μm), manufactured by Sekisui Chemical Co., Ltd., refractive index: 1.49, heat resistance: 250~270℃, pulsed NMR - crystalline phase composition: 92% • "Acrylic Beads 4": GB-22S polybutyl methacrylate acrylic beads (22 μm) manufactured by Aica Kogyo Co., Ltd., pulsed NMR - crystalline phase composition: 54% • "Acrylic Beads 5": Polymethyl methacrylate acrylic beads (20 μm), pulsed NMR - crystalline phase composition: 71% • "Acrylic Beads 6": ARX-8 polyacrylic acid ester acrylic beads (8μm) manufactured by Sekisui Chemical Co., Ltd., refractive index: 1.49, heat resistance: 230~250℃, pulsed NMR - crystalline phase composition: 50% • "Acrylic Beads 7": MBX-50 polymethyl methacrylate acrylic beads (50 μm) manufactured by Sekisui Chemical Co., Ltd., refractive index: 1.49, heat resistance: 250~270℃, pulsed NMR - crystalline phase composition: 72% • "Desmodule N-3300A": Isocyanate curing agent, manufactured by Sumika Covestro Urethane Co., Ltd.

[0091] The evaluation results showed that the decorative materials using the two-component curing coating composition of the present invention all exhibited a good tactile feel similar to real wood, and had excellent clarity, stain resistance, and solvent rubbing resistance. Furthermore, the storage stability of the polyol composition (X) was also good. On the other hand, Comparative Example 1, in which the ratio of acrylic beads (B) to the non-volatile components of acrylic polyol resin (A) was low, and Comparative Example 5, in which the average particle size of acrylic beads (B) was small, had a weak tactile feel and did not provide a sufficient wood-like texture. Comparative Example 2, in which the acrylic beads (B) had a higher content ratio relative to the non-volatile components of the acrylic polyol resin (A), exhibited inferior clarity and insufficient storage stability. Comparative Examples 3 and 4, which used acrylic beads with a low crystalline phase component in pulsed NMR, exhibited insufficient rubbing resistance or storage stability. Comparative Example 6, in which the average particle size of the acrylic beads (B) was large, had an overly strong tactile feel and failed to achieve a wood-like texture. Comparative Example 7, which did not contain silicone additive (C), was not sufficiently stain-resistant because contaminants penetrated it. Comparative Example 8, in which no hardening agent was added, lacked sufficient crosslinking properties for the coating film, resulting in poor solvent rubbing resistance and stain resistance.

Claims

1. The product comprises a polyol composition (X) and a curing agent composition (Y) containing a curing agent. The polyol composition (X) comprises an acrylic polyol resin (A), acrylic beads (B), and a silicone additive (C). The average particle size of the acrylic beads (B) is 10 to 30 μm, and the abundance ratio of the crystalline phase component determined by pulsed NMR is 80% or more. The content of the acrylic beads (B) relative to the nonvolatile components of the acrylic polyol resin (A) is 10 to 30% by mass. A two-component curing type coating composition.

2. The silicone additive (C) is an amino-modified silicone. The coating composition according to claim 1.

3. The glass transition temperature of the acrylic polyol resin (A) is 30 to 100°C. The coating composition according to claim 1.

4. The polyol composition (X) further comprises a solvent (D). 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.

Images