JP7331651B2 - Ink composition for decorative material and decorative material - Google Patents

Description

The present invention relates to an ink composition for decorative materials and a decorative material.

Decorative materials are produced by forming a pattern such as a wood grain pattern on a base material such as a wood base material or a steel plate using printing ink or the like, and are used for buildings, outer walls, and the like. Depending on the embodiment, it is also called a decorative sheet or a decorative board.

Since decorative materials are often used for a long period of time, the inks that make up the pattern layer or the pattern layer need to have physical properties such as initial adhesion to substrates and ink printability, as well as light resistance, weather resistance, and moisture resistance. Various durability such as heat resistance is required. In particular, when used for semi-exterior applications that are moderately exposed to outside light and air, and for exterior applications that are used outdoors, they are exposed to sunlight, high temperature, and high humidity for a longer period of time. If the pattern layer composed of is insufficient in weather resistance and moist heat resistance, defects due to peeling may occur in the decorative sheet or board.

In order to solve the above problems, for example, in Patent Document 1, an example in which an acrylic polyol and a polypropylene-based emulsion are used in combination as an ink to impart moist heat resistance is studied, but since polypropylene is easily decomposed by light, light resistance was insufficient. In Patent Document 2, a copolymer of polycarbonate-based urethane and acrylic polyol and polyester-based urethane are used together as ink in order to achieve both substrate adhesion and weather resistance. There were concerns about the durability and moist heat resistance.

Japanese Patent Application Laid-Open No. 2014-080010 JP-A-2010-82905

An object of the present invention is to provide an ink composition for a decorative material and a method for producing a decorative material, which have excellent adhesion to a substrate and durability such as excellent weather resistance and resistance to moist heat.

As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved by using the ink composition for decorative materials and the method for producing a decorative material described below, and have completed the present invention.

That is, the present invention provides a method for producing a decorative material having a base material, a pattern layer and a surface protective layer in this order,
A step of printing an ink composition for decorative material on a base material 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.
The present invention relates to a method for producing a decorative material, wherein a film made of the ink composition is formed and cured, and the cured film has a storage elastic modulus at 140° C. of 1.0×10 5 to 1.0×10 9 Pa.

The present invention also relates to the method for producing the decorative material, wherein the polyisocyanate contains an isocyanurate-based polyisocyanate and/or an adduct-based polyisocyanate.

The present invention also relates to the method for producing the decorative material, wherein the acrylic polyol has a weight average molecular weight of 30,000 to 150,000.

The present invention also relates to a method for producing the decorative material, wherein the mass ratio of acrylic polyol and polyisocyanate is 100:5 to 100:80.

The present invention also relates to a method for producing the decorative material, further comprising the step of forming a surface protective layer by printing a thermosetting resin and/or an ionizing radiation-curable resin on the picture layer by a printing method. .

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide an ink composition for a decorative material, a decorative material, and a method for producing a decorative material, which have excellent adhesion, weather resistance, and resistance to moist heat.

Embodiments of the present invention will be described in detail below, but the description of the constituent elements described below is an example (representative example) of embodiments of the present invention, and the present invention does not exceed the gist thereof. Content is not limited.

The present invention relates to an ink composition for a decorative material for forming the pattern layer of a decorative material having a base material, a pattern layer, and a surface protective layer in this order, and the ink composition comprises a specific acrylic polyol and a poly It contains isocyanate.
In the ink composition for decorative materials, the acrylic polyol has a hydroxyl value of 10 to 120 mgKOH/g and a glass transition temperature of 30 to 70° C., and the film formed by the ink composition for decorative materials is formed under arbitrary conditions. When the cured film has a storage elastic modulus of 10 ⁵ to 10 ⁹ Pa at 140° C., the required properties can be satisfied. These requirements act integrally in the ink composition for decorative materials, and the decorative materials having the above-described structure satisfy adhesion to substrates, weather resistance, resistance to moist heat, and the like.

In the following description, "ink composition for decorative materials" may be abbreviated as "ink for decorative materials" or "ink composition", but they have the same meaning. Moreover, "(meth)acryl" represents "methacryl" and "acryl", and "(meth)acrylate" represents "methacrylate" and "acrylate".

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

The acrylic polyol has a hydroxyl value of 10 to 120 mgKOH/g, preferably 15 to 100 mgKOH/g, more preferably 20 to 80 mgKOH/g. When the hydroxyl value is 10 mgKOH/g or more, substrate adhesion, weather resistance, and moist heat resistance are good. When the hydroxyl value is 120 mgKOH/g or less, the ink stability is good even when blended with polyisocyanate. be. The hydroxyl value acts and cures with the polyisocyanate described below to promote the improvement of properties.

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 substrate adhesion is good.

The acrylic polyol has a weight average molecular weight of 30,000 to 150,000, preferably 50,000 to 100,000. When the weight average molecular weight is 30,000 or more, substrate adhesion, weather resistance, and moist heat resistance are good, and when the weight average molecular weight is 150,000 or less, ink stability when blended with a polyisocyanate curing agent is good. . In addition, a weight average molecular weight says the measured value by GPC (gel permeation chromatography).

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

The acrylic monomer constituting the acrylic polyol is not particularly limited as long as it satisfies the hydroxyl value of 10 to 120 mgKOH/g and the glass transition temperature of 30°C 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 DSC measurement is the glass transition temperature.
As an example of the acrylic monomer, a copolymer of a hydroxyl group-containing (meth)acrylic monomer and a hydroxyl group-free (meth)acrylic monomer is preferably used. The hydroxyl group-containing (meth)acrylic monomer may be a monomer containing one (meth)acryloyl group and one or more hydroxyl groups in one molecule.

Examples of acrylic monomers containing a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate. , 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate and other hydroxyalkyl (meth)acrylates , glycol mono(meth)acrylates such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, caprolactone-modified (meth)acrylate, hydroxyethylacrylamide, etc. is mentioned. 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.

Examples of hydroxyl-free acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and (meth) acrylic hexyl acid, cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, methyl cyclohexyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, (meth) ) dicyclopentanyl acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, tetradecyl (meth)acrylate, (meth)acrylic acid hexadecyl, octadecyl (meth)acrylate and the like. The acrylic polyol preferably contains structural units derived from methyl methacrylate. The content of structural units derived from methyl methacrylate is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, based on the total mass of the acrylic polyol. Moreover, the acrylic polyol preferably has a structural unit derived from butyl methacrylate. The content of structural units derived from butyl methacrylate is preferably 30 to 70% by mass based on the total mass of acrylic polyol.

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, and the like.

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

Amide bond group-containing acrylic monomers include, for example, N-isopropyl(meth)acrylamide and N,N-diethylacrylamide.

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

Examples of alkylene oxide group-containing acrylic monomers include 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-phenoxyethyl acrylate, methoxypolyethylene glycol (meth)acrylate, ethoxypolyethyleneglycol (meth)acrylate, and methoxypolypropylene glycol. (Meth)acrylates, ethoxypolypropyleneglycol (meth)acrylates, phenoxypolyethyleneglycol (meth)acrylates, phenoxypolypropyleneglycol (meth)acrylates and the like.

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.

<Polyisocyanate>
The polyisocyanate acts with the acrylic polyol in the ink composition for decorative materials of the present invention, and is necessary for imparting adhesion to the substrate layer, weather resistance, and moist heat resistance. There are no particular restrictions on the form of polyisocyanate blending, and it may be blended in advance with the ink composition for decorative materials, or in the process of laminating the pattern layer and the surface protective layer, the pattern layer may be added to another layer containing polyisocyanate. Polyisocyanate may be supplied by contact with, as a result, the isocyanate group reacts with the hydroxyl group and cures, and the storage elastic modulus of the pattern layer becomes the above storage elastic modulus, and the same effect is required. .

Suitable polyisocyanates include isocyanurate-based polyisocyanates, adduct-based polyisocyanates, biuret-based polyisocyanates, and allophanate-based polyisocyanates. It is more preferable to use an isocyanurate-based polyisocyanate and/or an adduct-based polyisocyanate.
The isocyanurate-based polyisocyanate refers to a polyisocyanate having a cyclized structure formed by trimerization of diisocyanate. The adduct-type polyisocyanate refers to a polyisocyanate having a structure in which a diisocyanate is added to the hydroxyl group of a compound having a hydroxyl group such as ethylene glycol, glycerin and trimethylolpropane.
Examples of the diisocyanate include 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-trimethylcyclohexyl 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, etc. aliphatic diisocyanates, 1,3-phenylene diisocyanate, 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-triisocyanatotoluene, 1,3,5-triisocyanatobenzene, dianisidine diisocyanate, 4,4′-diphenyl ether diisocyanate, 4,4′,4″-triphenyl methane triisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, ω,ω'-diisocyanate-1,4-diethylbenzene, 1,4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, etc. Aromatic diisocyanates are mentioned.
Preferably, it is at least one selected from hexamethylene diisocyanate, an isocyanurate polyisocyanate of isophorone diisocyanate, an adduct polyisocyanate consisting of an adduct compound of hexamethylene diisocyanate, isophorone diisocyanate, and trimethylolpropane of xylylene diisocyanate.

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

In order to achieve the effect of the present invention, a film is formed from an ink composition for decorative materials containing acrylic polyol and polyisocyanate, and the cured film obtained by curing the film has a storage modulus of 1.0 at 140°C. ×10 ⁵ to 1.0×10 ⁹ Pa is required. If it is 1.0×10 ⁵ Pa or more, weather resistance and moist heat resistance will be good, and if it is 1.0×10 ⁹ or less, substrate adhesion will be good. The storage modulus is preferably 1.0×10 ⁶ to 1.0×10 ⁹ Pa, more preferably 1.0×10 ⁶ to 1.0×10 ⁸ Pa. The term "cured film" as used herein refers to a state in which the reaction of the polyisocyanate in the film is approximately complete, and the storage elastic modulus (140 ° C.) of the cured film is sufficient as long as it is in a constant state without change. The conditions are not particularly limited, but in the present specification, curing conditions of 40° C. and 48 hours were used when measuring the storage modulus.
In order to keep the storage elastic modulus at 140°C of the cured film formed from the ink composition for decorative materials within the above range, in one embodiment, the acrylic polyol has a hydroxyl value of 10 to 120 mgKOH/g, preferably 10 to 80 mgKOH. /g, the acrylic polyol and polyisocyanate mass ratio (acrylic polyol:polyisocyanate) is preferably 100:5 to 100:80, preferably 100:10 to 100:60. It is also preferable that the acrylic polyol has a hydroxyl value of 20 to 70 mgKOH/g, and that the acrylic polyol/polyisocyanate ratio is 100:10 to 100:50.
In order to make the storage elastic modulus at 140° C. of the cured film formed from the ink composition for decorative material within the above range, in one embodiment, in addition to the above, the glass transition temperature of the acrylic polyol is 30 to 70° C. The temperature is preferably 40 to 60° C., and the weight ratio (acrylic polyol:pigment) of the following pigments to be blended is preferably 100:20 to 100:250. It is more preferably 100:30 to 100:200.

<Pigment>
The cosmetic ink preferably contains a pigment. Either an inorganic pigment or an organic pigment can be used as the colorant, and there is no particular limitation, but good effects can be obtained by using an organic pigment. Examples of organic pigments include, but are not limited to, soluble azo, insoluble azo, azo, phthalocyanine, halogenated phthalocyanine, anthraquinone, anthrone, dianthraquinonyl, anthrapyrimidine, perylene, perinone, quinacridone, thioindigo, dioxazine, isoindolinone, quinophthalone, azomethineazo, flavanthrone, diketopyrrolopyrrole, isoindoline, indanthrone, carbon black, etc. pigments. Also, for example, Carmine 6B, Lake Red C, Permanent Red 2B, Disazo Yellow, Pyrazolone Orange, Carmine FB, Chromophtal Yellow, Chromophtal Red, Phthalocyanine Blue, Phthalocyanine Green, Dioxazine Violet, Quinacridone Magenta, Quinacridone Red, Indance Ron blue, pyrimidine yellow, thioindigo bordeaux, thioindigo magenta, perylene red, perinone orange, isoindolinone yellow, aniline black, diketopyrrolopyrrole red, daylight fluorescent pigments, and the like.

Specific examples of preferable organic pigments are shown below with generic names of the color index. At least one or two or more selected from the group consisting of black pigments, indigo pigments, red pigments, purple pigments, yellow pigments, and brown pigments shown below are preferred.

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

On the other hand, 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, the use of titanium oxide is particularly preferred. Titanium oxide exhibits a white color and is preferable from the viewpoints of coloring power, hiding power, chemical resistance and weather resistance. From the viewpoint of printing performance, the titanium oxide is preferably treated with silica and/or alumina.

Inorganic pigments other than white include, for example, aluminum particles, mica (mica), bronze powder, chrome vermilion, yellow lead, cadmium yellow, cadmium red, ultramarine blue, Prussian blue, red iron oxide, yellow iron oxide, iron black, zinc oxide, and the like. Although aluminum is powder or paste, it is preferable to use it in paste form from the viewpoint of handling and safety, and whether to use leafing or non-leafing is appropriately selected from the viewpoint of brightness and density. be.

The amount of the pigment is sufficient to ensure the concentration and coloring power of the ink for decorative materials, that is, 1 to 50% by mass of the total mass of the ink composition, and the solid content mass ratio in the ink composition is 10 to 50% by mass. It is preferably contained at a rate of 90% by mass. Moreover, these pigments can be used individually or in combination of 2 or more types.

<Additive>
The ink for cosmetic materials of the present invention can contain known additives as appropriate, and in the production of 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, weathering agents, silane coupling agents and the like can be used.

In order to stably disperse the pigment, the dispersant may be used in combination. Anionic, nonionic, cationic, and amphoteric surfactants can be used as dispersants. From the viewpoint of the storage stability of the ink, the dispersant is preferably contained in the ink in an amount of 0.1 to 10.0% by mass in the ink composition.

<Production of ink composition for decorative 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, and dispersed in an organic solvent to produce a pigment dispersion. A cosmetic ink can be produced by blending an acrylic polyol, an organic solvent, or, if necessary, other resins and additives. In addition, the particle size distribution of the pigment dispersion is adjusted by appropriately adjusting the size of the grinding media of the disperser, the filling rate of the grinding media, the dispersion processing time, the ejection speed of the pigment dispersion, the viscosity of the pigment dispersion, and the like. be able to. As the dispersing machine, generally used roller mills, ball mills, pebble mills, attritors, sand mills and the like can be suitably used.

<Viscosity>
The viscosity of the cosmetic ink produced by the above method is 40 at 25 ° C. with a Brookfield viscometer in order to support high-speed printing (50 to 300 m / min) such as flexographic printing and gravure printing. A viscosity range of ~500 cps is preferred. More preferably 50 to 400 cps. This viscosity range corresponds to a viscosity of about 9 seconds to 40 seconds in a Zahn cup #4. The viscosity of the cosmetic ink can be adjusted by appropriately selecting the types and amounts of raw materials used, such as organic pigments, acrylic polyols, and organic solvents. Also, the viscosity of the ink can be adjusted by adjusting the particle size and particle size distribution of the organic pigment in the ink.

The method for producing the cosmetic material of the present invention will be described below. The decorative material is a laminate having a layer structure having a base material, a pattern layer, and a surface protective layer in this order. The substrate, pattern layer, and surface protective layer may be provided in this order, and other layers may be provided. Other layers include a primer layer on the back surface of the substrate, a thermoplastic resin layer between the pattern layer and the surface protective layer, an anchor coat layer, and the like.

<Base material layer>
Examples of base materials that can be used in the present invention include polyolefin base materials such as polyethylene and polypropylene, polyester base materials such as polyethylene terephthalate and polylactic acid, polycarbonate base materials, and acrylic base materials such as polymethyl methacrylate. - Polyamide base materials such as nylon and 6,6-nylon; cellulose base materials such as cellulose acetate, cellulose propionate and nitrocellulose; chlorine base materials such as polyvinyl chloride and polyvinylidene chloride; Examples thereof include fluororesin polystyrene base materials such as ethylene and polyvinylidene fluoride, polystyrene base materials such as AS resins and ABS resins, and the like, preferably in the form of a film or a sheet. The base material layer is obtained using one or a mixture selected from two or more of these thermoplastic resins. The base layer may be a laminate. In addition, surface treatment such as corona treatment may be applied. Further, a colored base material in which a coloring agent is kneaded with the thermoplastic resin may be used. The coloring agent is not particularly limited, and the above organic pigments, inorganic pigments, and the like can be used as appropriate. It is also preferred if in one embodiment the substrate comprises a colorant.

<Pattern layer>
The pattern layer can be obtained by applying the ink composition for decorative materials of the present invention on the substrate by a rotary printing method such as gravure printing or flexographic printing to form a pattern layer. For example, it is diluted with an organic solvent to a viscosity and concentration suitable for gravure printing, mixed with polyisocyanate, mixed, and supplied to each printing unit for printing. Although the printing method is not particularly limited, screen printing, gravure printing, flexographic printing, offset printing, inkjet printing, and the like are preferred, and gravure printing and flexographic printing are preferred.
Further, in the production of the decorative material of the present invention, polyisocyanate is used at the time of pattern layer formation, that is, in the printing process. Specifically, printing is carried out by adding a predetermined amount of polyisocyanate when printing the ink composition for decorative materials. At this time, an ink composition containing an acrylic polyol having a hydroxyl value of 10 to 120 mgKOH/g and a glass transition temperature of 30 to 70° C. is mixed with a cured polyisocyanate compounded at the time of printing, coated, dried, and cured. It is preferable that the film is prepared, and that the storage elastic modulus at 140° C. is 1.0×10 ⁵ to 1.0×10 ⁹ Pa by measurement in advance, and that combination is used in printing.
That is, the composition is blended so that the storage elastic modulus at 140° C. of the cured film formed from the cosmetic ink composition used during printing is 1.0×10 ⁵ to 1.0×10 ⁹ Pa. It is preferable that

<Surface protective layer>
The surface protective layer is formed on the picture layer before or after the picture layer is cured. The surface protective layer is formed to impart properties such as scratch resistance, stain resistance, chemical resistance, and weather resistance to the decorative material. A curable resin such as resin is used. A mixture of acrylic polyol and polyisocyanate is suitable as the thermosetting resin. The ionizing radiation-curable resin is not particularly limited as long as the number of functional groups of the polyfunctional acrylate monomer is 2 or more, but from the viewpoint of adhesion and scratch resistance, it is preferable to use urethane acrylate and other polyfunctional acrylate oligomers together.
Further, a thermoplastic resin layer may be formed between the pattern layer and the surface protective layer in order to impart further weather resistance, scratch resistance, and the like. For the thermoplastic resin layer, for example, polypropylene resin, polyethylene resin, polyethylene terephthalate resin, polyvinyl chloride resin, etc. can be used. different resins may be mixed. These thermoplastic resins are formed, for example, by a method of extruding the thermoplastic resin from a T-die as a molten resin and laminating it, or by placing a film or sheet made of the thermoplastic resin on the pattern layer and thermocompression bonding. You can also get

EXAMPLES The present invention will be described in detail below with reference to Examples, but the present invention is not limited to these Examples. Parts and % in the present invention represent parts by mass and % by mass unless otherwise specified. A pattern layer formed from the ink composition for decorative materials of the present invention is printed on a base material, and the material before forming a surface protective layer is abbreviated as a printed matter.

(hydroxyl value)
The hydroxyl value is calculated by esterifying or acetylating the hydroxyl groups in the resin with an excess amount of acid anhydride, and then back titrating the remaining acid with an alkali, converting the amount of hydroxyl groups in 1 g of the resin into mg of potassium hydroxide. Yes, the value measured according to JISK0070.

(Weight average molecular weight)
The weight-average molecular weight was obtained by measuring the molecular weight distribution using a GPC (gel permeation chromatography) device (“Shodex GPCS System-21” manufactured by Showa Denko Co., Ltd.) and obtaining the polystyrene equivalent molecular weight.
Measurement conditions are shown below.
Column: Use the following multiple columns connected in series.
TSKgel SuperAW2500 manufactured by Tosoh Corporation,
manufactured by Tosoh Corporation, TSKgel SuperAW3000,
TSKgel SuperAW4000 manufactured by Tosoh Corporation,
TSKgel guard column Super AWH manufactured by Tosoh Corporation
Detector: RI (differential refractometer),
Measurement conditions: column temperature 40°C,
Eluent: Tetrahydrofuran Flow rate: 1.0 mL/min

(storage modulus)
The cured film was cut into a size of 0.5 cm×2.5 cm cm, and the storage modulus at 140° C. was measured using a dynamic viscoelasticity measuring device (model name: DVA-200, manufactured by IT Keisoku Co., Ltd.). The measurement was performed under conditions of a distance between clamps of 15 mm, a frequency of 10 Hz, a heating rate of 4°C/min, a measurement start temperature of 30°C, and a measurement end temperature of 150°C.

(Glass-transition temperature)
Glass transition temperatures (Tg) were determined by differential scanning calorimetry measurements (DSC). A DSC8231 manufactured by Rigaku Co., Ltd. was used as the measuring instrument, the measurement temperature range was -70 to 250°C, the temperature increase rate was 10°C/min, and the midpoint between the endothermic start temperature and the end temperature based on the glass transition in the DSC curve was set to the glass temperature. was taken as the transition temperature.

(Synthesis Example 1) [Acrylic polyol AP1]
Methyl methacrylate (hereinafter "MMA") 60 parts in a reaction vessel, 2-hydroxyethyl methacrylate (hereinafter "2-HEMA") 3 parts, butyl methacrylate (hereinafter "BMA") 36 parts, acrylic acid (hereinafter "AA ”) 1 part, 125 parts of ethyl acetate, 125 parts of methyl ethyl ketone (hereinafter “MEK”) and 0.4 parts of azobisisobutyronitrile (hereinafter “AIBN”) were added and mixed, and the mixture was placed in a nitrogen gas atmosphere at 70 ° C. for 8 hours to obtain acrylic polyol AP1. The resulting resin solution had a solid 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.

(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 that the raw materials listed in Table 1 were used. In adjusting the weight average molecular weight, the amount of AIBN added was appropriately adjusted.

(Comparative Synthesis Examples 1-4) [Acrylic polyol AP7-AP10]
Acrylic polyols AP7 to AP10 were obtained in the same manner as in Synthesis Example 1, except that the raw materials listed in Table 2 were used. In adjusting the weight average molecular weight, the amount of AIBN added was appropriately adjusted.

(Example 1) [Preparation of ink composition S1 for decorative material]
60 parts of acrylic polyol AP1 (40% solids), C.I. I. 10 parts of Pigment Yellow 110 (Irgazin Yellow L2060, manufactured by BASF) and 30 parts of a solution of ethyl acetate/MEK=50/50 were mixed and dispersed for 30 minutes with an Eiger mill to obtain a cosmetic ink.
As polyisocyanates, Takenate D-170N (manufactured by Mitsui Chemicals, isocyanurate compound of hexamethylene diisocyanate) 1.6 parts and Takenate D-110N (manufactured by Mitsui Chemicals, trimethylolpropane adduct compound of xylylene diisocyanate) 0.4 The parts were mixed to obtain ink composition S1 for decorative materials.

(Examples 2 to 12) [Preparation of ink compositions S2 to S12 for decorative materials]
Ink compositions S2 to S12 for decorative materials were obtained by mixing in the same manner as in Example 1 except that the raw materials shown in Table 3 were used.
Takenate D-160N: Mitsui Chemicals, Inc., trimethylolpropane adduct compound of hexamethylene diisocyanate Takenate D-165N: Mitsui Chemicals, Inc., burette compound of hexamethylene diisocyanate

(Comparative Examples 1 to 5) [Preparation of Ink Compositions T1 to T5 for Decorative Materials]
Cosmetic ink sets 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.

(Example 1) [Preparation of cured film of cosmetic ink composition S1]
A film was obtained by forming a layer of the decorative ink composition S1 obtained above on a petri dish so that the film thickness after drying was 50 μm, followed by heating and drying. The storage elastic modulus was evaluated after forming a cured film by holding the film at 40° C. for 48 hours.

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

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

[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) so that the viscosity was 16 seconds (25° C., Zahn cup No. 3), Helio 175 line (compressed plate, 100% to 3% gradation pattern) is used to print at a printing speed of 150 m/min on the corona-treated surface of a 60 μm-thick polypropylene resin substrate (manufactured by Futamura Chemical Co., Ltd., product name: FOS). Then, a printed matter of ink composition S1 for decorative materials was obtained. The evaluation of blocking resistance and substrate adhesion was carried out after forming a cured film by holding the printed matter at 40° C. for 48 hours.

<Printing of surface protective layer>
After blending 10 parts of Takenate D-170N with 100 parts of surface protection varnish (YL454UR, acrylic resin-based varnish manufactured by Toyo Ink Co., Ltd.), a mixed solvent (ethyl acetate / MEK = 50/50) was used to reduce the viscosity for 10 seconds ( 25° C., dilute and mix to a Zahn cup No. 4), and apply a film thickness after drying by gravure printing on the printed matter (printed matter of ink composition S1 for decorative materials) obtained above. A decorative material was obtained by printing at a printing speed of 80 m/min so as to have a thickness of 6 μm. The evaluation of weather resistance and heat and humidity resistance was carried out after forming a cured film by holding the decorative material at 40° C. for 48 hours. In addition, a "varnish" means a resin solution.

[Ink Compositions S2 to S12 for Decorative Material and Printing of Surface Protective Layer]
Printed matter C2-C9 and decorative materials D2-D9 were obtained in the same manner as the printed matter/decorative material using S1 using ink compositions for decorative material S2-S12 obtained above. The blocking resistance and adhesion to the substrate were evaluated after the printed matter was held at 40° C. for 48 hours to form a cured film. Evaluation of weather resistance and moist heat resistance was carried out after formation of a cured film by holding the decorative material at 40°C for 48 hours.

[Ink Compositions T1 to T5 for Decorative Material and Printed Matter of Surface Protective Layer and Decorative Material]
Using the ink compositions T1 to T5 for decorative materials obtained above, printed matter and decorative materials corresponding to each were obtained in the same manner as described above. The blocking resistance and adhesion to the substrate were evaluated after the printed matter was held at 40° C. for 48 hours to form a cured film. Evaluation of weather resistance and moist heat resistance was carried out after formation of a cured film by holding the decorative material at 40°C for 48 hours.

The ink composition for decorative materials, the cured film, the printed matter and the decorative material obtained above were evaluated as follows, and Tables 3 and 4 show the results.

<Ink stability>
Regarding the ink compositions for decorative materials S1 to S12 (Examples) and T1 to T5 (Comparative Examples), a mixed solvent (ethyl acetate/MEK = 50/50) increased the viscosity to 16 seconds (25°C, Zahn Cup No. 3 ), and stored at 25° C. for 24 hours. After that, the viscosity was measured to evaluate the viscosity change from before storage. The viscosity was measured at 25°C with a Zahn cup No. 3 efflux seconds were performed.
A. Viscosity difference is less than 0 seconds to 5 seconds (excellent)
B. Viscosity difference is more than 5 seconds and less than 10 seconds (good)
C. Viscosity difference is more than 10 seconds and less than 15 seconds (possible)
D. Viscosity difference is more than 15 seconds and less than 20 seconds (impossible)
E. Viscosity difference exceeds 20 seconds or gels (poor)
In addition, A, B, and C are ranges that pose no practical problems.

<Blocking resistance>
The printed material is cut into a size of 4 cm x 4 cm, and the polypropylene resin base material cut into the same size is superimposed, and a load of 5 kg/cm ² is applied, and left to stand for 24 hours in an atmosphere of 40 ° C. and 80% RH. After that, the printed surface and the film were peeled off, and the degree of removal of the ink film was visually judged.
A. No peeling of ink film (excellent)
B. 0% or more to less than 5% of the ink film peeled off (good)
C. 5% or more to less than 10% of the ink film peels off (acceptable)
D. 10% or more to less than 30% of the ink film peels off (impossible)
E. 30% or more of the ink film is peeled off, or the entire surface adheres and cannot be peeled off (poor)
Note that A, B, and C are ranges that pose no problem in practice.

<Substrate adhesion>
A cellophane tape was attached to the printed surface of the printed matter and quickly removed. The adhesion of the ink to the film was evaluated by comparing the area where the tape was applied and the area where the ink was peeled from the film.
A. No peeling of ink film (excellent)
B. 0% to less than 10% of the tape adhesion area (good)
C. The area where the ink film is peeled from the film is 10% or more to less than 30% of the tape adhesion area (acceptable)
D. The area where the ink film has peeled off from the film is 30% or more to less than 50% of the tape adhesion area (impossible)
E. The area where the ink film peeled off from the film is 50% or more of the tape adhesion area (poor)
Note that A, B, and C are ranges that pose no problem in practice.

<Weather resistance>
The decorative material was irradiated for 20 hours (black panel temperature 53° C., 50% RH, illuminance 70 W/m ² ) using an accelerated weathering tester (manufactured by Daipla Wintes, model name: KW-R6TP-A). A 20-cycle accelerated test was conducted with a 4-hour rest period (35° C., 98% RH) and a 30-second shower cycle as one cycle, and then adhesion and color change were evaluated. Adhesion was determined by the same evaluation method and evaluation criteria as those for substrate adhesion. The color change was measured using a spectrophotometer under the conditions of D50 light source, viewing angle of 2°, 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 4.0 or more and less than 6.0 (impossible)
E. ΔE is 6.0 or more (poor)
Note that A, B, and C are ranges that pose no problem in practice.

<Damp heat resistance>
After storing the decorative material at 85° C. and 85% RH for one month, adhesion and color change were evaluated. Adhesion and color change were evaluated by the same methods and evaluation criteria as those used for evaluating weather resistance.

From the evaluation results, it was found that the present invention provides an ink composition for a decorative material, a decorative material, and a method for producing a decorative material, which have excellent adhesion to substrates, weather resistance, and resistance to moist heat, as well as good ink stability and anti-blocking properties. I found out.

Claims (5)

A method for producing a decorative material having a base material, a pattern layer and a surface protective layer in this order,
A step of printing an ink composition for decorative material on a base material 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 method for producing a decorative material, wherein a storage elastic modulus at 140° C. of a cured film obtained by forming and curing a film comprising the ink composition is 1.0×10 5 to 1.0×10 9 Pa. The method for producing a decorative material according to claim 1, wherein the polyisocyanate includes an isocyanurate-based polyisocyanate and/or an adduct-based polyisocyanate. 3. The method for producing a decorative material according to claim 1, wherein the acrylic polyol has a weight average molecular weight of 30,000 to 150,000. The method for producing a decorative material according to any one of claims 1 to 3, wherein the mass ratio of acrylic polyol and polyisocyanate is 100:5 to 100:80. The decorative material according to any one of claims 1 to 4, further comprising the step of forming a surface protective layer by printing a thermosetting resin and/or an ionizing radiation curable resin on the pattern layer by a printing method. Production method.