Ink composition for decorative materials and decorative materials

Abstract

To provide an ink composition for a decorative material which has durability such as excellent weather resistance and moist heat resistance in addition to excellent adhesion to a substrate, and to provide a decorative material manufacturing method.SOLUTION: The ink composition for a decorative material is used to constitute a pattern layer of a decorative material including a substrate, the pattern layer, and a surface protective layer in this order. The ink composition contains an acrylic polyol and a polyisocyanate. The acrylic polyol has a hydroxyl value of 10-120 mg KOH / g and a glass transition temperature of 30-70°C. A cured film obtained by forming a film composed of the ink composition and curing it has a storage modulus at 140°C of 1.0×105-1.0×109 Pa.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an ink composition for a decorative material and a decorative material. [Background technology]

[0002] Decorative materials are produced by forming a pattern such as a wood grain pattern using printing ink or the like on a substrate such as a wooden substrate or a steel plate, and are used for buildings, exterior walls, etc. Depending on the embodiment, they are also called decorative sheets or decorative boards.

[0003] Because decorative materials are often used over long periods of time, the ink that composes the design layer or the design layer itself is required to have various durability properties such as light resistance, weather resistance, and moist heat resistance, in addition to physical properties such as initial substrate adhesion and ink printability. In particular, when used in semi-exterior applications that are moderately exposed to external light and air, or in exterior applications used outdoors, the materials are exposed to sunlight and high temperature and humidity environments for longer periods of time, so if the weather resistance and moist heat resistance of the design layer made of printing ink are insufficient, there is a risk of defects due to peeling in the decorative sheet or decorative board.

[0004] To solve the above problems, for example, Patent Document 1 considers the use of an acrylic polyol and a polypropylene emulsion in combination as an ink to impart moist heat resistance, but polypropylene is easily decomposed by light, and therefore the light resistance is insufficient. Patent Document 2 uses a copolymer of polycarbonate urethane and acrylic polyol, and a polyester urethane in combination as an ink to achieve both substrate adhesion and weather resistance, but polyester urethane is easily hydrolyzed, and there are concerns about weather resistance and moist heat resistance. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2014-080010 [Patent Document 2] Japanese Patent Application Laid-Open No. 2010-82905 Summary of the Invention [Problem to be solved by the invention]

[0006] The present invention provides an ink composition for decorative materials that has excellent durability such as excellent weather resistance and moist heat resistance in addition to excellent substrate adhesion, and a method for producing a decorative material. [Means for solving the problem]

[0007] As a result of extensive research into the above-mentioned problems, the present inventors have found that the problems can be solved by using the ink composition for decorative materials and the method for producing decorative materials described below, and have thus completed the present invention.

[0008] That is, the present invention provides a method for producing a decorative material having a substrate, a pattern layer, and a surface protective layer in this order, comprising: The method includes a step of printing an ink composition for a cosmetic material on a substrate by a printing method to form a pattern layer, The ink composition contains an acrylic polyol and a polyisocyanate, and the acrylic polyol has a hydroxyl value of 10 to 120 mgKOH / g and a glass transition temperature of 30 to 70°C; A film made of the ink composition is formed and cured, and the cured film has a storage modulus at 140°C of 1.0 x 10 5 ~ 1.2 x10 9 The present invention relates to a method for producing a cosmetic material.

[0009] The present invention also provides the decorative material, wherein the polyisocyanate includes an isocyanurate polyisocyanate and / or an adduct polyisocyanate. Manufacturing method Regarding.

[0010] The present invention also provides the cosmetic material, wherein the weight average molecular weight of the acrylic polyol is 30,000 to 150,000. Manufacturing method Regarding.

[0011] The present invention also provides the decorative material, wherein the mass ratio of the acrylic polyol to the polyisocyanate is 100:5 to 100:80. Manufacturing method Regarding.

[0012] The present invention also provides The method for producing the decorative material further comprises a step of printing a thermosetting resin and / or an ionizing radiation curable resin on the pattern layer by a printing method to form a surface protective layer. Regarding. [Effects of the Invention]

[0013] The present invention makes it possible to provide an ink composition for decorative materials, a decorative material, and a method for producing a decorative material, which have excellent adhesion, weather resistance, and moist heat resistance. DETAILED DESCRIPTION OF THE INVENTION

[0014] The following describes in detail the embodiments of the present invention. However, the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention, and the present invention is not limited to these contents as long as it does not exceed the gist of the present invention.

[0015] The present invention relates to an ink composition for a decorative material, which is used to form a pattern layer of a decorative material having a substrate, a pattern layer, and a surface protective layer in this order, and the ink composition contains a specific acrylic polyol and a polyisocyanate. The ink composition for decorative materials is an ink composition for decorative materials, in which the hydroxyl value of the acrylic polyol is 10 to 120 mgKOH / g and the glass transition temperature is 30 to 70°C, and a film formed from the ink composition for decorative materials is cured under optional conditions, and the cured film has a storage modulus at 140°C of: 10 5 ~10 9 The required properties can be satisfied by the ink composition having a Pa. These requirements act together in an ink composition for decorative materials, and the decorative material having the above-mentioned composition satisfies the substrate adhesion, weather resistance, moist heat resistance, etc.

[0016] In the following description, "ink composition for decorative materials" may be abbreviated as "ink for decorative materials" or "ink composition," but these terms have the same meaning. Furthermore, "(meth)acrylic" refers to "methacrylic" and "acrylic," and "(meth)acrylate" refers to "methacrylate" and "acrylate."

[0017] <Acrylic polyol> The decorative ink of the present invention uses an acrylic polyol as a binder resin. A binder resin is a thermoplastic resin soluble in an organic solvent that provides the binding function in the ink. Examples of binder resins other than acrylic polyol include urethane resin, polyester resin, nitrocellulose resin, and vinyl chloride-vinyl acetate copolymer resin. In the present invention, it is desirable to use an acrylic polyol as the main binder from the viewpoint of durability, such as weather resistance and moist heat resistance. Furthermore, in order to satisfy the required physical properties, the following requirements for the properties of the acrylic polyol (hydroxyl value, glass transition temperature, molecular weight, etc.) contribute to performance.

[0018] The hydroxyl value of the acrylic polyol is 10 to 120 mgKOH / g, preferably 15 to 100 mgKOH / g, and more preferably 20 to 80 mgKOH / g. When the hydroxyl value is 10 mgKOH / g or more, the adhesion to substrates, weather resistance, and moist heat resistance are good, and when the hydroxyl value is 120 mgKOH / g or less, when blended with polyisocyanate, The hydroxyl value reacts with and cures the polyisocyanate described below, promoting improved properties.

[0019] The acrylic polyol has a glass transition temperature of 30 to 70° C., preferably 40 to 60° C. When the glass transition temperature is 30° C. or higher, the weather resistance, moist heat resistance, and blocking resistance are good, and when it is 70° C. or lower, the adhesion to the substrate is good.

[0020] The weight-average molecular weight of the acrylic polyol is 30,000 to 150,000, and preferably 50,000 to 100,000. A weight-average molecular weight of 30,000 or more provides good substrate adhesion, weather resistance, and moist heat resistance, while a weight-average molecular weight of 150,000 or less provides good ink stability when blended with a polyisocyanate-based curing agent. The weight-average molecular weight is measured by GPC (gel permeation chromatography).

[0021] The method for synthesizing the acrylic polyol is not particularly limited, and known methods such as anionic polymerization in the presence of an organic solvent, living anionic polymerization, cationic polymerization, living cationic polymerization, radical polymerization, and living radical polymerization can be used.

[0022] The acrylic monomer constituting the acrylic polyol is not particularly limited, and may be any monomer that satisfies the above-mentioned hydroxyl value of 10 to 120 mgKOH / g and glass transition temperature of 30 to 70° C. In the present invention, the glass transition temperature refers to a value measured by a differential scanning calorimeter (DSC), and the temperature at the inflection point of the baseline shift in the DSC measurement is the glass transition temperature. Examples of the acrylic monomer include hydroxyl group-containing (meth)acrylic monomers and hydroxyl group-containing (meth)acrylic monomers. A copolymer of a (meth)acrylic monomer containing no hydroxyl group is preferably used. The hydroxyl group-containing (meth)acrylic monomer may be any monomer containing one (meth)acryloyl group and one or more hydroxyl groups in one molecule.

[0023] Examples of hydroxyl group-containing acrylic monomers include (meth)acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 8-hydroxyoctyl (meth)acrylate; glycol mono(meth)acrylates such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and 1,4-cyclohexanedimethanol mono(meth)acrylate; caprolactone-modified (meth)acrylate; and hydroxyethyl acrylamide. The acrylic polyol preferably contains 1 to 30% by mass of structural units derived from hydroxyl group-containing acrylic monomers based on the total mass of the acrylic polyol.

[0024] Examples of acrylic monomers not containing a hydroxyl group include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, cyclopentyl (meth)acrylate, methylcyclohexyl (meth)acrylate, bornyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, tetradecyl (meth)acrylate, hexadecyl (meth)acrylate, and octadecyl (meth)acrylate. The acrylic polyol preferably contains a structural unit derived from methyl methacrylate. The content of the structural unit derived from methyl methacrylate is preferably 5 to 60 mass% of the total mass of the acrylic polyol. It is more preferably 10 to 50% by mass. The acrylic polyol preferably has a structural unit derived from butyl methacrylate. The content of the structural unit derived from butyl methacrylate is preferably 30 to 70% by mass of the total mass of the acrylic polyol.

[0025] The acrylic monomer may also contain a carboxyl group-containing acrylic monomer, an amide bond group-containing acrylic monomer, an amino group-containing acrylic monomer, an alkylene oxide group-containing acrylic monomer, an epoxy group-containing acrylic monomer, or the like.

[0026] Examples of carboxyl group-containing acrylic monomers include (meth)acrylic acid, monohydroxyethyl succinate (meth)acrylate, monohydroxyethyl phthalate (meth)acrylate, monohydroxyethyl hexahydrophthalate (meth)acrylate, p-carboxybenzyl (meth)acrylate, ethylene oxide-modified (number of moles added: 2 to 18) phthalic acid (meth)acrylate, monohydroxypropyl phthalate (meth)acrylate, β-carboxyethyl (meth)acrylate, and 2-(4-benzoyl-3-hydroxyphenoxy)ethyl (meth)acrylate.

[0027] Examples of amide bond group-containing acrylic monomers include N-isopropyl(meth)acrylamide and N,N-diethylacrylamide.

[0028] Examples of amino group-containing acrylic monomers include monomethylaminoethyl (meth)acrylate, monoethylaminoethyl (meth)acrylate, monomethylaminopropyl (meth)acrylate, and monoethylaminopropyl (meth)acrylate.

[0029] Examples of alkylene oxide group-containing acrylic monomers include 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-phenoxyethyl acrylate, methoxypolyethylene glycol (meth)acrylate, ethoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, ethoxypolypropylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, and phenoxypolypropylene glycol (meth)acrylate.

[0030] Examples of epoxy group-containing acrylic monomers include glycidyl (meth)acrylate, α-methylglycidyl acrylate, α-methylglycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, and 3,4-epoxycyclohexylmethyl methacrylate.

[0031] <Polyisocyanate> In the ink composition for decorative materials of the present invention, the polyisocyanate acts with the acrylic polyol and is necessary for imparting adhesion to the substrate layer and weather resistance and moist heat resistance. There are no particular limitations on the form in which the polyisocyanate is blended, and it may be blended in advance in the ink composition for decorative materials, or the polyisocyanate may be supplied by the design layer coming into contact with another layer containing polyisocyanate during the lamination process of the design layer and the surface protective layer, so that the isocyanate groups react with the hydroxyl groups and harden, resulting in the storage modulus of the design layer becoming the above-mentioned storage modulus, and the same effect may be achieved.

[0032] Suitable examples of polyisocyanates include isocyanurate polyisocyanates, adduct polyisocyanates, biuret polyisocyanates, and allophanate polyisocyanates. In the present invention, isocyanurate polyisocyanates and / or adduct polyisocyanates are used from the viewpoints of substrate adhesion, weather resistance, and moist heat resistance. It is more preferable to use Isocyanurate polyisocyanates are polyisocyanates that have a structure in which diisocyanates are cyclized as trimers. Adduct polyisocyanates are polyisocyanates that have a structure in which diisocyanates are added to the hydroxyl groups of compounds with hydroxyl groups, such as ethylene glycol, glycerin, and trimethylolpropane. The diisocyanate may be trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexane, Hexyl isocyanate (isophorone diisocyanate), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane Aliphatic diisocyanates such as methyl cyclohexane, 1,3-phenylenediisocyanates Examples of the aromatic diisocyanates include 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4',4"-triphenylmethane triisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, ω,ω'-diisocyanato-1,4-diethylbenzene, 1,4-tetramethylxylylene diisocyanate, and 1,3-tetramethylxylylene diisocyanate. Preferably, it is at least one selected from the group consisting of isocyanurate polyisocyanates of hexamethylene diisocyanate and isophorone diisocyanate, and adduct polyisocyanates consisting of adduct compounds of hexamethylene diisocyanate, isophorone diisocyanate, and xylylene diisocyanate with trimethylolpropane.

[0033] In the ink composition for decorative materials of the present invention, the mass ratio of the acrylic polyol to the polyisocyanate-based curing agent (acrylic polyol:polyisocyanate-based curing agent) is 100:5 to 100:80, and preferably 100:10 to 100:60. When the mass ratio of the acrylic polyol to the polyisocyanate-based curing agent is 100:5 to 100:80, the substrate adhesion, weather resistance, moist heat resistance, ink stability, and blocking resistance are excellent.

[0034] In order to achieve the effects of the present invention, a coating is formed from an ink composition for decorative materials containing an acrylic polyol and a polyisocyanate, and the cured coating obtained by curing the coating has a storage modulus at 140°C of 1.0 x 10 5 ~ 1.0 x10 9 It is necessary to make the pressure so that it is 1.0×10 Pa. 5 If it is above 1 Pa, it has good weather resistance and humidity and heat resistance. 1.0 x10 9 If the storage modulus is 1.0×10 or less, the adhesion to the substrate is good. 6 ~1.0×10 9 Pa, and preferably 1.0×10 6 ~1.0×10 8 It is more preferable that the cured film has a temperature of 40°C and a curing time of 48 hours. The cured film referred to here is one in which the reaction of the polyisocyanate in the film has been nearly completed, and it is sufficient if the storage modulus (140°C) of the cured film remains constant and unchanged. There are no particular restrictions on the actual curing conditions, but in this specification, when measuring the storage modulus, curing conditions of 40°C and 48 hours were used. In one embodiment, to ensure that the storage modulus at 140°C of a cured film formed from the decorative ink composition falls within the above range, it is suitable to combine an acrylic polyol having a hydroxyl value of 10 to 120 mgKOH / g, preferably 10 to 80 mgKOH / g, with an acrylic polyol to polyisocyanate mass ratio (acrylic polyol:polyisocyanate) of 100:5 to 100:80, preferably 100:10 to 100:60. It is also preferable that the hydroxyl value of the acrylic polyol be 20 to 70 mgKOH / g, and that the acrylic polyol / polyisocyanate ratio be 100:10 to 100:50. In one embodiment, in order to set the storage modulus at 140°C of the cured film formed from the ink composition for decorative materials within the above range, in addition to the above, it is suitable to set the glass transition temperature of the acrylic polyol to 30 to 70°C, preferably 40 to 60°C, and the mass ratio (acrylic polyol:pigment) of the pigments described below to be blended is preferably 100:20 to 100:250, and more preferably 100:30 to 100:200.

[0035] <Pigments> It is preferable that the cosmetic ink contains a pigment. Either inorganic or organic pigments can be used as the colorant, and although there are no particular limitations, the use of organic pigments provides good results. Examples of organic pigments include, but are not limited to, soluble azo pigments, insoluble azo pigments, azo pigments, phthalocyanine pigments, halogenated phthalocyanine pigments, anthraquinone pigments, anthanthrone pigments, dianthraquinonyl pigments, anthrapyrimidine pigments, perylene pigments, perinone pigments, quinacridone pigments, thioindigo pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments, azomethine azo pigments, flavanthrone pigments, diketopyrrolopyrrole pigments, isoindoline pigments, indanthrone pigments, and carbon black pigments. Further examples include carmine 6B, lake red C, permanent red 2B, disazo yellow, pyrazolone orange, carmine FB, cromophtal yellow, cromophtal red, phthalocyanine blue, phthalocyanine green, dioxazine violet, quinacridone magenta, quinacridone red, indanthrone blue, pyrimidine yellow, thioindigo bordeaux, thioindigo magenta, perylene red, perinone orange, isoindolinone yellow, aniline black, diketopyrrolopyrrole red, and daylight fluorescent pigments.

[0036] Specific examples of preferred organic pigments are shown below by their generic names in the Color Index. At least one or more selected from the group consisting of black pigments, indigo pigments, red pigments, purple pigments, yellow pigments, and brown pigments are preferred.

[0037] <Black pigment> Specifically, among the black pigments of CI Pigment Black 1 to 34, black pigments that are organic compounds or organometallic complexes are preferred, for example: Examples include CI Pigment Black 1, CI Pigment Black 6, CI Pigment Black 7, CI Pigment Black 9, and CI Pigment Black 20. <Indigo pigment> Specifically, among the indigo pigments of CI Pigment Blue 1 to 80, indigo pigments that are organic compounds or organometallic complexes are preferred, for example: Examples of pigments include CI Pigment Blue 15, CI Pigment Blue 15:1, CI Pigment Blue 15:2, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:5, CI Pigment Blue 15:6, CI Pigment Blue 16, CI Pigment Blue 17:1, CI Pigment Blue 22, CI Pigment Blue 24:1, CI Pigment Blue 25, CI Pigment Blue 26, CI Pigment Blue 60, CI Pigment Blue 61, CI Pigment Blue 62, CI Pigment Blue 63, CI Pigment Blue 64, CI Pigment Blue 75, CI Pigment Blue 79, and CI Pigment Blue 80. <Red pigment> Specifically, among the red pigments of CI Pigment Red 1 to 279, organic compounds or organic compounds Red pigments that are organometallic complexes are preferred, and from the viewpoint of weather resistance, for example, Examples of pigment red include CI Pigment Red 122, CI Pigment Red 146, CI Pigment Red 166, CI Pigment Red 170, CI Pigment Red 177, CI Pigment Red 185, CI Pigment Red 187, CI Pigment Red 202, CI Pigment Red 254, and CI Pigment Red 264. <Yellow pigment> Specifically, among the yellow pigments of CI Pigment Yellow 1 to 219, yellow pigments that are organic compounds or organometallic complexes are preferred, and more preferably, from the viewpoint of weather resistance, for example, Examples of pigments include CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 120, Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 151, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 173, CI Pigment Yellow 174, CI Pigment Yellow 180, CI Pigment Yellow 185, and CI Pigment Yellow 213. <Purple pigment> Specifically, among the purple pigments of CI Pigment Violet 1 to 50, purple pigments that are organic compounds or organometallic complexes are preferred, and more preferably, from the viewpoint of weather resistance, for example, Examples include CI Pigment Violet 19, CI Pigment Violet 23, and CI Pigment Violet 29. <Brown pigment> Examples include CI Pigment Brown 23, CI Pigment Brown 25, and CI Pigment Brown 26.

[0038] On the other hand, examples of inorganic pigments include white inorganic pigments such as titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, and silica. Among inorganic pigments, titanium oxide is particularly preferred. Titanium oxide exhibits a white color and is preferred in terms of coloring power, hiding power, chemical resistance, and weather resistance. From the viewpoint of printing performance, titanium oxide that has been treated with silica and / or alumina is preferred.

[0039] Examples of inorganic pigments other than white include aluminum particles, mica, bronze powder, chrome vermilion, yellow lead, cadmium yellow, cadmium red, ultramarine, Prussian blue, red iron oxide, yellow iron oxide, iron black, and zinc oxide. Aluminum is in powder or paste form, but it is preferably used in paste form from the standpoints of handleability and safety, and whether leafing or non-leafing aluminum is used is selected appropriately from the standpoints of brightness and concentration.

[0040] The pigment is preferably contained in an amount sufficient to ensure the concentration and coloring strength of the cosmetic ink, i.e., 1 to 50% by mass of the total mass of the ink composition, or 10 to 90% by mass in terms of the solid content ratio in the ink composition. These pigments can be used alone or in combination of two or more.

[0041] <Additives> The ink for decorative materials of the present invention may contain known additives as appropriate, and in producing the ink composition, known additives such as pigment derivatives, extender pigments, dispersants, wetting agents, adhesion aids, silica particles, leveling agents, antifoaming agents, antistatic agents, trapping agents, antiblocking agents, wax components, weather resistance agents, and silane coupling agents may be used as needed.

[0042] The dispersant can be used in combination to stably disperse the pigment. Examples of dispersants that can be used include anionic, nonionic, cationic, and amphoteric surfactants. From the viewpoint of ink storage stability, the dispersant is preferably contained in the ink composition in an amount of 0.1 to 10.0% by mass.

[0043] <Production of Ink Composition for Cosmetic Materials> The cosmetic ink of the present invention can be produced by dissolving and / or dispersing an acrylic polyol and a pigment in an organic solvent. Specifically, for example, an organic pigment is mixed with an acrylic polyol and, if necessary, the dispersant, to produce a pigment dispersion dispersed in an organic solvent. The resulting pigment dispersion can then be further blended with a polyisocyanate, an acrylic polyol, an organic solvent, and, if necessary, other resins and additives to produce the cosmetic ink. The particle size distribution of the pigment dispersion can be adjusted by appropriately adjusting the size of the grinding media in the disperser, the grinding media filling rate, the dispersion treatment time, the discharge rate of the pigment dispersion, the viscosity of the pigment dispersion, and the like. Commonly used dispersers, such as roller mills, ball mills, pebble mills, attritors, and sand mills, can be suitably used.

[0044] <Viscosity> The viscosity of the ink for decorative materials produced by the above method is preferably in the range of 40 to 500 cps at 25°C as measured by a Brookfield viscometer to accommodate high-speed printing (50 to 300 m / min) using methods such as flexographic printing and gravure printing. A viscosity of 50 to 400 cps is more preferred. This viscosity range corresponds to a viscosity of approximately 9 to 40 seconds using a Zahn cup #4. The viscosity of the ink for decorative materials can be adjusted by appropriately selecting the types and amounts of raw materials used, such as the amounts of organic pigment, acrylic polyol, and organic solvent. The viscosity of the ink can also be adjusted by adjusting the particle size and particle size distribution of the organic pigment in the ink.

[0045] The decorative material of the present invention will be described below, along with a manufacturing method. The decorative material is a laminate having a layer structure in which a substrate, a design layer, and a surface protective layer are present in this order. The substrate, design layer, and surface protective layer only need to be present in this order, and other layers may also be present. Examples of other layers include a primer layer on the back surface of the substrate, a thermoplastic resin layer between the design layer and the surface protective layer, and an anchor coat layer.

[0046] <Base material layer> Examples of substrates that can be used in the present invention include polyolefin substrates such as polyethylene and polypropylene, polyester substrates such as polyethylene terephthalate and polylactic acid, polycarbonate substrates, acrylic substrates such as polymethyl methacrylate, polyamide substrates such as 6-nylon and 6,6-nylon, cellulose substrates such as cellulose acetate, cellulose propionate, and nitrocellulose, chlorine-based substrates such as polyvinyl chloride and polyvinylidene chloride, fluorine-based resin polystyrene substrates such as polytetrafluoroethylene and polyvinylidene fluoride, and polystyrene substrates such as AS resin and ABS resin. These substrates are preferably in the form of a film or sheet. The substrate layer can be obtained using one or a mixture of two or more of these thermoplastic resins. The substrate layer may be a laminate. It may also be subjected to a surface treatment such as corona treatment. A colored substrate in which a colorant is kneaded into the thermoplastic resin may also be used. The colorant is not particularly limited, and the above-mentioned organic pigments, inorganic pigments, etc. can be used as appropriate. In one embodiment, a substrate containing a colorant is also preferred.

[0047] <Pattern layer> The design layer can be obtained by forming the ink composition for decorative materials of the present invention on the substrate using a rotary printing method such as gravure printing or flexographic printing. For example, the ink composition is diluted with an organic solvent to a viscosity and concentration suitable for gravure printing, and polyisocyanate is added, mixed, and then supplied to each printing unit for printing. The printing method is not particularly limited, and suitable examples include screen printing, gravure printing, flexographic printing, offset printing, and inkjet printing, with gravure printing and flexographic printing being particularly preferred. In the production of the decorative material of the present invention, a polyisocyanate is used when forming a design layer, i.e., in the printing process. Specifically, a predetermined amount of polyisocyanate is blended when printing an ink composition for decorative materials. At this time, an ink composition containing an acrylic polyol having a hydroxyl value of 10 to 120 mg KOH / g and a glass transition temperature of 30 to 70°C is mixed with a cured product of the polyisocyanate blended during printing, and the mixture is coated and dried to form a cured film. The storage modulus at 140°C was measured in advance and found to be 1.0 x 10 5 ~ 1.0 x10 9 It is preferable to know which combination of fluororesin and fluororesin is to be used in printing. That is, the storage modulus at 140°C of the cured film formed by the ink composition for decorative materials used in printing is 1.0 × 10 5 ~ 1.0 x10 9 It is preferable that the composition is blended so that Pa.

[0048] <Surface protective layer> The surface protective layer is formed on the design layer before or after the curing process of the design layer. The surface protective layer is formed to impart properties such as scratch resistance, contamination resistance, chemical resistance, and weather resistance to the decorative material, and a curable resin such as a thermosetting resin or an ionizing radiation curable resin is used to satisfy the above surface properties. A mixture of an acrylic polyol and a polyisocyanate is suitable as the thermosetting resin. The ionizing radiation curable resin is not particularly limited as long as the polyfunctional acrylate monomer has two or more functional groups, but it is preferable to use a urethane acrylate or other polyfunctional acrylate oligomer in combination from the viewpoint of adhesion and scratch resistance. Furthermore, a thermoplastic resin layer may be formed between the design layer and the surface protective layer to further impart weather resistance, scratch resistance, etc. Examples of thermoplastic resin layers that can be used include polypropylene resin, polyethylene resin, polyethylene terephthalate resin, and polyvinyl chloride resin. They may be copolymerized with acrylic, styrene, or other monomers, or may be a mixture of different resins. These thermoplastic resins can be obtained, for example, by forming the thermoplastic resin as a molten resin through a T-die by extrusion lamination, or by placing a film or sheet made of the thermoplastic resin on the design layer and thermocompressing it. [Example]

[0049] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In the present invention, parts and % represent parts by mass and % by mass unless otherwise noted. Furthermore, a printed matter is a material obtained by printing a design layer formed from the ink composition for decorative materials of the present invention on a substrate and before forming a surface protective layer.

[0050] (Hydroxyl value) The hydroxyl value is the amount of hydroxyl groups in 1 g of resin calculated by esterifying or acetylating the hydroxyl groups in the resin with an excess of anhydrous acid and back-titrating the remaining acid with an alkali, converted into mg of potassium hydroxide, and is a measurement value according to JIS K0070.

[0051] (Weight average molecular weight) The weight average molecular weight was determined as a polystyrene-equivalent molecular weight by measuring the molecular weight distribution using a GPC (gel permeation chromatography) device (Shodex GPC System-21 manufactured by Showa Denko KK). The measurement conditions are as follows: Column: The following multiple columns are connected in series. Tosoh Corporation, TSKgel SuperAW2500, Tosoh Corporation, TSKgel SuperAW3000, Tosoh Corporation, TSKgel SuperAW4000, TSKgel guardcolumn SuperAWH, manufactured by Tosoh Corporation Detector: RI (differential refractometer), Measurement conditions: column temperature 40°C, Eluent: tetrahydrofuran Flow rate: 1.0mL / min

[0052] (storage modulus) The cured film was cut into a 0.5cm x 2.5cm piece and the storage modulus at 140°C was measured using a dynamic viscoelasticity measuring device (IT Measurement Control Co., Ltd., Model DVA-200). Measurements were performed under the following conditions: clamp distance 15mm, frequency 10Hz, heating rate 4°C / min, starting temperature 30°C, ending temperature 150°C.

[0053] (glass transition temperature) The glass transition temperature (Tg) was determined by differential scanning calorimetry (DSC) using a Rigaku Corporation DSC8231 measuring instrument, with a measurement temperature range of −70 to 250°C, a heating rate of 10°C / min, and the midpoint between the endothermic start and end temperatures due to the glass transition in the DSC curve.

[0054] (Synthesis Example 1) [Acrylic polyol AP1] A reaction vessel was charged with 60 parts methyl methacrylate (MMA), 3 parts 2-hydroxyethyl methacrylate (2-HEMA), 36 parts butyl methacrylate (BMA), 1 part acrylic acid (AA), 125 parts ethyl acetate, 125 parts methyl ethyl ketone (MEK), and 0.4 parts azobisisobutyronitrile (AIBN). The resulting mixture was polymerized under a nitrogen atmosphere at 70°C for 8 hours to yield acrylic polyol AP1. The resulting resin solution had a solids content of 40%, a hydroxyl value of 13 mgKOH / g, a glass transition temperature of 68°C, and a weight-average molecular weight of 78,000.

[0055] (Synthesis Examples 2 to 8) [Acrylic Polyols AP2 to AP6] Acrylic polyols AP2 to AP6 were obtained in the same manner as in Synthesis Example 1, except for using the raw materials listed in Table 1. The amount of AIBN added was adjusted as needed to adjust the weight average molecular weight.

[0056] (Comparative Synthesis Examples 1 to 4) [Acrylic Polyols AP7 to AP10] Acrylic polyols AP7 to AP10 were obtained in the same manner as in Synthesis Example 1, except for using the raw materials listed in Table 2. The amount of AIBN added was adjusted as appropriate to adjust the weight average molecular weight.

[0057] (Example 1) [Preparation of cosmetic ink composition S1] 60 parts of acrylic polyol AP1 (solid content 40%), 10 parts of CI Pigment Yellow 110 (BASF, Irgazin Yellow L2060), and 30 parts of a 50 / 50 ethyl acetate / MEK solution were mixed and dispersed in an Eiger mill for 30 minutes to obtain an ink for decorative materials. In addition, 1.6 parts of Takenate D-170N (an isocyanurate compound of hexamethylene diisocyanate, manufactured by Mitsui Chemicals, Inc.) and 0.4 parts of Takenate D-110N (a trimethylolpropane adduct compound of xylylene diisocyanate, manufactured by Mitsui Chemicals, Inc.) were mixed as polyisocyanates to form decorative ink composition S1.

[0058] (Examples 2 to 12) [Preparation of cosmetic ink compositions S2 to S12] Except for using the raw materials listed in Table 3, the same mixing method as in Example 1 was used to obtain ink compositions for decorative materials S2 to S12. Takenate D-160N: Mitsui Chemicals, Inc., hexamethylene diisocyanate trimethylolpropane adduct compound Takenate D-165N: Manufactured by Mitsui Chemicals, a biuret compound of hexamethylene diisocyanate

[0059] (Comparative Examples 1 to 5) [Preparation of Ink Compositions T1 to T5 for Cosmetic Materials] Ink sets for decorative materials T1 to T5 were obtained in the same manner as in Examples 1 to 12 above, except that the raw materials listed in Table 4 were used.

[0060] (Example 1) [Preparation of cured film of decorative ink composition S1] The above-obtained ink composition S1 for decorative materials was applied to a petri dish to form a layer of the ink for decorative materials so that the dried film thickness was 50 μm, and then the layer was dried by heating to obtain a film. The storage modulus was evaluated after the film was cured by holding the film at 40° C. for 48 hours.

[0061] (Examples 2 to 12) [Preparation of cured films of decorative ink compositions S2 to S12] Films of each of the ink compositions for decorative materials S2 to S12 were obtained in the same manner as the method for producing the cured film of S1 above, except that ink compositions for decorative materials S2 to S12 were used. The storage modulus was evaluated after the formation of the cured film by holding the film at 40°C for 48 hours, and the results are shown in Table 3.

[0062] [Preparation of cured films of decorative ink compositions T1 to T5] Films of each of the ink compositions for decorative materials T1 to T5 were obtained in the same manner as the method for producing the cured film in S1 above, except that ink compositions for decorative materials T1 to T5 were used. The storage modulus was evaluated after the formation of the cured film by holding the film at 40°C for 48 hours, and the results are shown in Table 4.

[0063] [Printed matter and decorative material using ink composition S1 for decorative material] The cosmetic ink composition S1 obtained above was diluted and mixed with a mixed solvent (ethyl acetate / MEK = 50 / 50) to a viscosity of 16 seconds (25°C, Zahn cup No. 3), and printed using Helio 175 line (press type compressed, 100% to 3% gradation pattern) at a printing speed of 150 m / min on the corona-treated surface of a 60 μm thick polypropylene resin substrate (Futamura Chemical Co., Ltd., product name: FOS) to obtain a print of cosmetic ink composition S1. Blocking resistance and substrate adhesion were evaluated after the print was kept at 40°C for 48 hours to form a cured film.

[0064] <Printing of surface protection layer> 100 parts of surface protective varnish (YL454UR, acrylic resin varnish manufactured by Toyo Ink Co., Ltd.) was mixed with 10 parts of Takenate D-170N, then diluted and mixed with a mixed solvent (ethyl acetate / MEK = 50 / 50) to a viscosity of 10 seconds (25°C, Zahn cup No. 4). This was then gravure printed onto the printed layer of the printed material obtained above (printed material of decorative material ink composition S1) at a printing speed of 80 m / min to a film thickness of 6 μm after drying, yielding a decorative material. Evaluation of weather resistance and moist heat resistance was performed after the decorative material was kept at 40°C for 48 hours to form a cured film. Note that "varnish" refers to a resin solution.

[0065] [Cosmetic ink compositions S2 to S12 and printing of surface protective layer] Using the ink compositions for decorative materials S2 to S12 obtained above, printed matter C2 to C9 and decorative materials D2 to D9 were obtained in the same manner as for the printed matter and decorative material using S1. Evaluation of weather resistance and humidity resistance was carried out by storing the printed material at 40°C for 48 hours after the formation of a cured film.

[0066] [Ink compositions T1 to T5 for decorative materials and printed matter and decorative materials with surface protective layers] Using the decorative ink compositions T1 to T5 obtained above, the corresponding printed matter and decorative material were obtained in the same manner as above. Evaluations of blocking resistance and substrate adhesion were carried out after the printed matter was kept at 40°C for 48 hours and a cured film was formed. Evaluations of weather resistance and moist heat resistance were carried out after the decorative material was kept at 40°C for 48 hours and a cured film was formed.

[0067] The ink composition for decorative materials, the cured film made of the ink composition for decorative materials, the printed matter, and the decorative material obtained above were evaluated as follows. The results are shown in Tables 3 and 4.

[0068] <Ink stability> Cosmetic ink compositions S1 to S12 (Examples) and T1 to T5 (Comparative Examples) were diluted and mixed with a mixed solvent (ethyl acetate / MEK = 50 / 50) to a viscosity of 16 seconds (25°C, Zahn cup No. 3), and then stored at 25°C for 24 hours. The viscosity was then measured to evaluate the change in viscosity from before storage. The viscosity was measured at 25°C in seconds until the composition flowed out of a Zahn cup No. 3. A. Viscosity difference is 0 to less than 5 seconds (Excellent) B. Viscosity difference is more than 5 seconds but less than 10 seconds (good) C. Viscosity difference is more than 10 seconds but less than 15 seconds (acceptable) D. Viscosity difference is more than 15 seconds but less than 20 seconds (not acceptable) E. Viscosity difference exceeds 20 seconds or gelation occurs (poor) A, B, and C are within the range where there are no practical problems.

[0069] <Blocking resistance> The printed matter was cut into 4cm x 4cm pieces, and the polypropylene resin substrate cut to the same size was placed on top of each other and weighed at 5kg / cm. 2 After applying a load and leaving the sample to stand for 24 hours in an atmosphere of 40°C and 80% RH, the printed surface and film were peeled off and the degree of ink film removal was visually determined. A. The ink film does not peel off at all (Excellent) B. Ink film peeling of 0% to less than 5% (Good) C. Ink film peeling of 5% to less than 10% (acceptable) D. Ink film peeling of 10% to less than 30% (unacceptable) E. Ink film peels off by 30% or more, or adheres completely and cannot be peeled off (poor) A, B, and C are ranges that pose no practical problems.

[0070] <Adhesion to substrate> Cellophane tape was applied to the printed surface of the above printed matter and then quickly peeled off. The adhesiveness of the ink to the film was evaluated by comparing the area where the tape was applied with the area where the ink peeled off from the film. A. The ink film does not peel off at all (Excellent) B. The area of ​​the ink film that has peeled off from the film is 0% to less than 10% of the tape adhesive area (good). C. The area where the ink film has peeled off from the film is 10% or more but less than 30% of the tape adhesive area (acceptable) D. The ink film peeled off from the film by 30% to less than 50% of the adhesive area of ​​the tape (unacceptable) E. The ink film has peeled off from the film by 50% or more of the tape adhesive area. (poor) A, B, and C are ranges that pose no practical problems.

[0071] <Weather resistance> The above decorative materials were exposed to light for 20 hours (black panel temperature 53°C, 50% RH, illuminance 70W / m 2 After 20 cycles of accelerated testing, each cycle consisting of a 4-hour shower, a 4-hour rest (temperature inside the bath: 35°C, 98% RH), and a 30-second shower, adhesion and color change were evaluated. Adhesion was evaluated using the same evaluation method and criteria as for substrate adhesion described above. Color change was measured using a spectrophotometer under conditions of D50 light source, a 2° viewing angle, and status E. A. ΔE is less than 1.0 (Excellent) B. ΔE is 1.0 or more and less than 2.0 (good) C. ΔE is 2.0 or more and less than 4.0 (acceptable) D. ΔE is between 4.0 and 6.0 (unacceptable) E. ΔE is 6.0 or more (poor) A, B, and C are ranges that pose no practical problems.

[0072] <Moisture and heat resistance> The decorative material was stored at 85°C and 85% RH for one month, and then evaluated for adhesion and color change. Both adhesion and color change were evaluated using the same method and criteria as in the evaluation of weather resistance described above.

[0073] [Table 1]

[0074] [Table 2]

[0075] [Table 3]

[0076] [Table 4]

[0077] From the evaluation results, it was found that the present invention has excellent substrate adhesion, weather resistance, moist heat resistance, and good ink stability. It has been found that the ink composition for a decorative material, the decorative material, and the method for producing the decorative material are also excellent in blocking resistance.

Claims

1. A method for producing a decorative material having a substrate, a pattern layer, and a surface protective layer in this order, comprising: The method includes a step of printing an ink composition for a cosmetic material on a substrate by a printing method to form a pattern layer, the ink composition comprises an acrylic polyol and a polyisocyanate, the acrylic polyol having a hydroxyl value of 10 to 120 mgKOH / g and a glass transition temperature of 30 to 70°C; A film made of the ink composition is formed and cured, and the cured film has a storage modulus at 140°C of 1.0 x 10 ５ ~1.2 × 10 ９ A method for producing a cosmetic material,

2. The method for producing a decorative material according to claim 1, wherein the polyisocyanate includes an isocyanurate polyisocyanate and / or an adduct polyisocyanate.

3. 3. The method for producing a decorative material according to claim 1, wherein the weight-average molecular weight of the acrylic polyol is 30,000 to 150,000.

4. 4. The method for producing a decorative material according to claim 1, wherein the mass ratio of the acrylic polyol to the polyisocyanate is 100:5 to 100:

80.

5. The method for producing a decorative material according to any one of claims 1 to 4, further comprising a step of printing a thermosetting resin and / or an ionizing radiation curable resin on the design layer by a printing method to form a surface protective layer.

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