Active energy ray-curable coating agent and decorative material using same

Abstract

To provide an active energy ray-curable coating agent excellent in leveling property, abrasion resistance, matting property and long-run suitability.SOLUTION: An active-energy-ray-curable coating agent used for a surface-protecting layer of a decorative material comprising a substrate, an intermediate layer, and the surface-protecting layer, the coating agent comprising a monomer and fine particles, the fine particles having a D50 of 2 to 15 μm and a D95 / D50 of 2.3 or less, the coating agent having a content of the fine particles of 4 to 30% by mass relative to the total mass of the coating agent.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an active energy ray-curable coating agent used for a surface protective layer of a decorative material. [Background technology]

[0002] Decorative materials are widely used in the interior and surface decoration of buildings such as furniture and fixtures. They typically require surface protection properties, such as matte finish, as well as stain resistance, weather resistance, solvent resistance, and abrasion resistance. To meet these requirements, a surface protection layer is applied to the surface of the substrate. From the viewpoints of environmental friendliness and productivity, active energy ray-curable coating agents are preferably used as the surface protection layer. These coating agents typically contain a matting agent such as silica, primarily for the purpose of reducing gloss and enhancing matte finish. However, because matting agents can affect leveling properties or cause a decrease in various physical properties such as stain resistance, research has also been conducted into reducing gloss without the use of matting agents (Patent Document 1).

[0003] Furthermore, in recent years, there has been a growing demand for a lower gloss appearance (high matte) in pursuit of a more luxurious feel, and there is a need for a material that combines the desired matte finish, printability (leveling), and the surface protection properties unique to decorative materials. Furthermore, increasing the amount of matting agent to achieve low gloss can lead to issues such as unstable gloss during long-run printing. Furthermore, successfully maintaining low gloss while achieving long-run printing presents significant technical hurdles.

[0004] Meanwhile, in recent years, from the perspective of environmental compatibility, there has been growing interest in carbon neutrality and biomass in the field of packaging materials, for example, but no such compatible products have yet appeared in the field of cosmetic materials.

[0005] Patent Document 1 describes an electron beam-curable matte coating agent containing a compound (A) with a weight-average molecular weight of 2000 or more and a bifunctional (meth)acrylic monomer (B). However, because this coating agent does not contain fine particles, it does not have both the desired matte and leveling properties, and improvements have been sought.

[0006] Furthermore, Patent Document 2 describes a decorative sheet having at least an intermediate layer and a surface protective layer in this order on a substrate, in which the surface protective layer is formed using a mixed resin of a tetrafunctional acrylate and a difunctional acrylate, a thermoplastic resin, and an ionizing radiation curable resin containing silica. However, this coating agent does not provide the desired matte properties and surface protective properties, and improvements have been sought.

[0007] Patent Document 3 also describes an active energy ray-curable composition containing an active energy ray-curable compound, a photopolymerization initiator, and a matting agent, the composition containing specific amounts of ethylene oxide-modified 1,6-hexanediol diacrylate, ethylene oxide-modified trimethylolpropane triacrylate, and ethoxyethoxyethanol acrylic acid polymer ester, and the matting agent having an average particle size of 1 to 10 μm. However, this coating agent does not provide the desired matting properties and surface protection properties, and improvements were needed. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent Application Publication No. 2023-166728 [Patent Document 2] Japanese Patent Application Laid-Open No. 2014-198440 [Patent Document 3] International Publication No. 2022 / 224830 Brochure Summary of the Invention [Problem to be solved by the invention]

[0009] The present invention aims to provide an active energy ray-curable coating agent for use in a surface protective layer of a decorative material, which has excellent leveling properties, abrasion resistance, matte finish, and long-run suitability. Another object of the present invention is to provide an active energy ray-curable coating agent for a decorative material that contributes to carbon neutrality. [Means for solving the problem]

[0010] The present invention provides an active energy ray-curable coating agent used to form a surface protective layer of a decorative material having a substrate, an intermediate layer, and a surface protective layer, the coating agent comprising: the coating agent includes a monomer and a fine particle; The particle size distribution of the fine particles has a D50 value of 2 to 15 μm, and the D95 / D50 value of the fine particles is 2.3 or less; The present invention relates to an active energy ray-curable coating agent, wherein the content of the fine particles is 4 to 30 mass % based on the total mass of the coating agent.

[0011] The present invention relates to the active energy ray-curable coating agent, wherein the content of the organic solvent in the total mass of the coating agent is 1000 ppm or less.

[0012] The present invention relates to the active energy ray-curable coating agent, wherein the fine particles are silica fine particles.

[0013] The present invention relates to the active energy ray-curable coating agent, wherein the oil absorption of the silica fine particles is 100 to 400 ml / g.

[0014] The present invention relates to the active energy ray-curable coating agent, wherein the monomer comprises a biomass-derived monomer.

[0015] The present invention relates to the active energy ray-curable coating agent, wherein the biomass-derived monomer has a structure derived from glycerin.

[0016] The present invention relates to the active energy ray-curable coating agent, wherein the content of the biomass-derived monomer is 60 mass % or more based on the total mass of the monomers.

[0017] The present invention relates to the active energy ray-curable coating agent, wherein the monomer contains a monomer having three or more functional groups, and the content of the monomer having three or more functional groups in the total mass of the active energy ray-curable coating agent is 50 mass% or more.

[0018] The present invention relates to the active energy ray-curable coating agent which is substantially free of a polymerization initiator.

[0019] The present invention relates to a decorative material having a substrate, an intermediate layer, and a surface protective layer formed from the active energy ray-curable coating agent.

[0020] The present invention relates to the decorative material, wherein the substrate is a paper substrate.

[0021] In the present invention, the mass per unit area of ​​the surface protective layer is 2 to 15 g / m 2 The present invention relates to the cosmetic material, wherein

[0022] The present invention relates to the decorative material, wherein the 60° gloss value measured from the surface protective layer side is 2 to 30.

[0023] The present invention provides a method for producing a decorative material having a substrate, an intermediate layer, and a surface protective layer, comprising: The method includes the steps of forming an intermediate layer on a substrate, applying an active energy ray-curable coating agent containing a monomer and fine particles to form an uncured layer, and then irradiating the uncured layer with active energy rays to form the surface protective layer, The particle size distribution of the fine particles has a D50 value of 2 to 15 μm, and the D95 / D50 value of the fine particles is 2.3 or less; A method for producing a cosmetic material, wherein the content of the fine particles is 4 to 30% by mass based on the total mass of the coating agent. [Effects of the Invention]

[0024] The present invention has made it possible to provide an active energy ray-curable coating agent that is excellent in leveling property, abrasion resistance, matte property and long-run suitability, and also to provide an active energy ray-curable coating agent for decorative materials that contributes to carbon neutrality. DETAILED DESCRIPTION OF THE INVENTION

[0025] The following examples are provided to explain the embodiments of the present invention in detail, but the matters described below are examples or representative examples of the embodiments of the present invention, and the present invention is not limited to these contents as long as they do not deviate from the gist of the invention.

[0026] In the present invention, "(meth)acrylate" refers to both acrylate and / or methacrylate. In addition, "active energy ray-curable coating agent" may be simply referred to as "coating agent," but these terms have the same meaning.

[0027] According to the present invention, there is provided an active energy ray-curable coating agent for use in the surface protective layer of a decorative material having a substrate, an intermediate layer, and a surface protective layer. This active energy ray-curable coating agent comprises a monomer and fine particles, the fine particles having a particle size distribution D50 of 2 to 15 μm and a D95 / D50 of 2.3 or less, and the content of the fine particles in the total mass of the coating agent is 4 to 30 mass %, so that the effect of the monomer and the fine particles makes the coating agent suitable for long-run printing, and the surface protective layer using this coating agent has good abrasion resistance and matte properties. Furthermore, the coating agent has an organic solvent content of 1000 ppm or less based on the total mass of the coating agent, which not only reduces the volatile organic compounds (VOCs) emitted during solvent drying but also further improves leveling properties. Furthermore, it is preferable that the fine particles are silica fine particles. For example, if the silica fine particles have an oil absorption of 100 to 400 ml / g, the leveling property and abrasion resistance can be further improved. Furthermore, if the monomer contains a biomass-derived monomer, and the biomass-derived monomer has a structural unit derived from glycerin, the dispersibility of the fine particles is improved and the sedimentation stability is good, thereby further improving the suitability for long-run printing. Furthermore, when the monomer contains a monomer having three or more functional groups and the content of the monomer having three or more functional groups in the total mass of the coating agent is 50 mass % or more, the abrasion resistance can be further improved. A decorative material having a surface protective layer formed using this active energy ray-curable coating agent has excellent abrasion resistance and matte finish. However, the present invention is not limited by the above considerations and mechanisms.

[0028] (Active energy ray curable coating agent) The active energy ray-curable coating agent of the present invention contains a monomer and fine particles. The monomer preferably contains a biomass-derived monomer.

[0029] (monomer) The monomer refers to a monomer containing an unsaturated double bond group that can be cured by active energy rays. The content of the monomer in the total mass of the coating agent is preferably 70 to 90 mass%, more preferably 70 to 85 mass%, and even more preferably 75 to 85 mass%. Suitable examples of the unsaturated double bond group include a (meth)acrylic group. Below, explanations will be given separately for biomass-derived monomers and non-biomass-derived monomers.

[0030] (Biomass-derived monomers) It is preferable to use a biomass-derived monomer from the viewpoint of environmental compatibility such as carbon neutrality, etc. In the present invention, the biomass-derived monomer refers to a monomer produced using biomass-derived raw materials as part or all of the raw materials, and having a biomass-derived structure and an unsaturated double bond group that can be cured with active energy rays. Although known biomass-derived monomers can be used, a monomer derived from a biomass alcohol is preferred, a monomer derived from a biomass monoalcohol and / or a biomass polyol is preferred, and a monomer containing a structure derived from a biomass polyol is more preferred.

[0031] (Biomass alcohol) Suitable examples of biomass monoalcohols as the biomass alcohol include methanol, ethanol, butanol, dodecanol, tetradecanol, and hexadecanol, and preferably include dodecanol, tetradecanol, and hexadecanol. Suitable examples of biomass polyols as the biomass alcohol include ethylene glycol, glycerin, 1,4-butanediol, 1,10-decanediol, and polytetramethylene glycol, and preferably include glycerin and 1,10-decanediol.

[0032] Examples of the biomass alcohol-derived monomer include 1,10-decanediol diacrylate, glycerin propoxy triacrylate, glycerin triacrylate, etc. When a biomass-derived monomer having a glycerin-derived structure such as glycerin propoxy triacrylate or glycerin triacrylate is used, the dispersibility of the fine particles improves and the sedimentation stability improves, resulting in good suitability for long-run printing.

[0033] Specific examples of biomass-derived monomers are shown below.

[0034] Examples of biomass-derived monomers having one functionality include tetrahydrofuryl acrylate, isobornyl (meth)acrylate, dodecyl acrylate, octadecyl methacrylate, glycerin carbonate acrylate, 2-hexyldecyl acrylate, 2-octyl acrylate, and n-hexyl acrylate.

[0035] Examples of biomass-derived monomers having two functional groups include decanediol di(meth)acrylate, polyethylene glycol dimethacrylate, glycerin diacrylate, and isosorbide diacrylate.

[0036] Examples of biomass-derived monomers having three functional groups include glycerin triacrylate and glycerin propoxy triacrylate.

[0037] An example of a biomass-derived monomer having four functional groups is diglycerin tetraacrylate.

[0038] The content of biomass-derived monomers in the total mass of the coating agent is preferably 60% by mass or more, more preferably 65% ​​by mass or more, and even more preferably 70% by mass or more.The content of biomass-derived monomers in the total mass of monomers is preferably 60% by mass or more, more preferably 65% ​​by mass or more, and even more preferably 70% by mass or more.

[0039] (Biomass ratio) In the present invention, the biomass degree refers to the mass ratio (%) of biomass-derived structures in the total solid mass of the coating agent. That is, the biomass degree is a value expressed by the following formula (1). Formula (1) Biomass degree = (total mass of biomass-derived structures / total solid mass of coating agent) × 100

[0040] In the present invention, from the viewpoint of environmental compatibility, the biomass ratio is preferably 3% by mass or more, more preferably 5% by mass or more, and even more preferably 8% by mass or more.

[0041] (non-biomass-derived monomers) In the present invention, a non-biomass-derived monomer can be used. As the non-biomass-derived monomer, a known monomer can be used.

[0042] Specific examples of non-biomass-derived monomers are shown below.

[0043] Examples of non-biomass-derived monomers with one functionality include butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, stearyl (meth)acrylate, tetradecyl (meth)acrylate, hexadecyl (meth)acrylate, acryloylmorpholine, and 4-hydroxylbutyl acrylate.

[0044] Examples of non-biomass-derived monomers having two functional groups include 1,6-hexanediol diacrylate, dipropylene glycol diacrylate, 3-methyl-1,5-pentanediol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, bisphenol A diacrylate, and tricyclodecane dimethanol diacrylate.

[0045] Examples of non-biomass-derived monomers having three functional groups include trimethylolpropane tri(meth)acrylate and pentaerythritol tri(meth)acrylate, and among these, it is preferable to use trimethylolpropane tri(meth)acrylate.

[0046] Examples of non-biomass-derived monomers having four functional groups include pentaerythritol tetra(meth)acrylate and ditrimethylolpropane tetra(meth)acrylate, and among these, it is preferable to use pentaerythritol tetra(meth)acrylate.

[0047] Examples of non-biomass-derived monomers having five or six functional groups include dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate.

[0048] The (meth)acrylates exemplified above, whether derived from biomass or non-biomass, are preferably modified with alkylene oxide, such as ethylene oxide (EO) or propylene oxide (PO).

[0049] (Number of functional groups of the monomer) In the present invention, the functionality of a monomer refers to the number of polymerizable (meth)acrylate groups in the monomer. While the number of functional groups is not particularly limited, it is preferably 1 to 6, and more preferably 2 to 4. By keeping the number within the above range, it is possible to achieve both abrasion resistance and matte properties. It is also preferable to use a monomer having 1 to 2 functional groups in combination with a monomer having 3 to 6 functional groups. By using a monomer having 1 to 2 functional groups, good matte properties are achieved, and by using a monomer having 3 to 6 functional groups, good abrasion resistance is achieved. By using a monomer having 1 to 2 functional groups in combination with a monomer having 3 to 6 functional groups, it is easy to achieve both abrasion resistance and matte properties. Furthermore, by using derived monomers having different numbers of functional groups in combination, it is easy to adjust the viscosity of the coating agent and improve leveling properties.

[0050] From the above viewpoints, the content of monomers having three or more functional groups in the total mass of the coating agent is preferably 50 to 85 mass%, more preferably 52 to 80 mass%, and even more preferably 55 to 75 mass%.

[0051] (Other resin components) In the present invention, resin components other than the above-mentioned monomers may be contained within a range that does not impair the effects of the present invention. Examples of such resins include, but are not limited to, polymerizable compounds such as urethane acrylate and epoxy acrylate, and thermoplastic resins. It is also preferable to use a resin containing a biomass-derived component. The resin components other than the above-mentioned monomers preferably account for 10% by mass or less, more preferably 7% by mass or less, even more preferably 5% by mass or less, and particularly preferably 2% by mass or less of the total mass of the active energy ray-curable coating agent excluding fine particles.

[0052] Examples of resins containing biomass-derived components include urethane acrylate and polyester acrylate containing biomass-derived components, and cellulose-based resins such as cellulose acetate butyrate and cellulose acetate propionate.

[0053] (fine particles) The fine particles used in the present invention not only have the effect of imparting matte properties to the surface protective layer of the present invention, but also have the effect of improving durability such as abrasion resistance. As the fine particles, known organic fine particles and / or inorganic fine particles can be used. Examples of the organic fine particles include synthetic resin beads such as acrylic resin, urethane resin, and polyethylene resin, and examples of the inorganic fine particles include fine particles of silica, calcium carbonate, barium sulfate, and alumina. Among these, from the viewpoint of reducing gloss, it is preferable to use inorganic fine particles, and silica fine particles are more preferable. The fine particles may be used alone or in combination of two or more kinds.

[0054] The content of the fine particles is 4 to 30% by mass, preferably 8 to 25% by mass, and more preferably 10 to 20% by mass, based on the total mass of the active energy ray-curable coating agent. A content of 4% by mass or more improves the matte finish, while a content of 30% by mass or less improves the leveling properties and transparency of the surface protective layer. Furthermore, abrasion resistance is improved by being within the above range.

[0055] The average particle diameter D50 of the fine particles is appropriately selected depending on the film thickness of the surface protective layer and the desired gloss value from the viewpoint of matting properties, and is 2 μm to 15 μm, preferably 3 μm to 12 μm, more preferably 4 μm to 10 μm, and particularly preferably 5 μm to 10 μm. A diameter within this range enhances the matting (low gloss) effect. Here, the average particle diameter D50 refers to the D50 value in the particle size distribution measured by the light scattering method, and can be measured using, for example, a Microtrac-Bell T330EXII.

[0056] In the present invention, the D95 / D50 of the fine particles is 2.3 or less, preferably 2.1 or less, and more preferably 1.9 or less. Being within this range improves long-run suitability. Here, D95 refers to the D95 value in particle size distribution determined by light scattering, and a larger D95 / D50 value indicates the presence of coarse particles with a particle size larger than the average particle size D50. D95 can be measured using a Microtrac-Bell T330EXII or similar device, similar to the above-mentioned D50.

[0057] (Silica fine particles) The silica microparticles are not particularly limited in terms of manufacturing method or shape, and known silica particles can be used, but from the viewpoint of matte finish, it is preferable to use amorphous silica microparticles.In addition, silica microparticles include those whose surfaces are physically or chemically treated with a surface treatment agent (organic or inorganic) such as a silane coupling agent, microcrystalline, alumina, wax, etc., and untreated ones, and both can be used in the present invention.The term "treated" refers to coating with a surface treatment agent or having a chemical bond with a surface treatment agent, and "untreated" refers to the absence of the coating or chemical bond.

[0058] The average particle diameter D50 of the silica fine particles is the same as the average particle diameter of the above-mentioned fine particles, and when it is in this range, the matte (low gloss) effect is enhanced, and furthermore, the abrasion resistance is improved. The average particle diameter D50 is the D50 value in the particle size distribution measured by the light scattering method, as described above.

[0059] The oil absorption of the silica fine particles is preferably 100 to 400 ml / g, more preferably 150 to 350 ml / g, and even more preferably 200 to 300 ml / g. Within this range, the viscosity of the coating agent does not become too high, and the leveling properties are good. The oil absorption is measured in accordance with JIS K5101-13-1.

[0060] Specific examples of silica fine particles include Sylysia 370, 380, 440, and 450 (manufactured by Fuji Silysia Chemical Ltd.), ACEMATT790 (manufactured by Evonik Japan Ltd.), SYLOIDRAD2105, SYLOIDC907, and SYLOIDMX307 (manufactured by WR GRACE & Co.).

[0061] The preferred range of the content of silica fine particles is the same as the content of the above fine particles. When the content is 4% by mass or more, the durability and matte property of the surface protective layer are improved, and when the content is 30% by mass or less, the leveling property and transparency of the coating film are improved.

[0062] (Other additives) If necessary, other additives can be blended into the present invention to the extent that they do not impair the effects of the present invention. Examples of other additives include dispersants, antifoaming agents, leveling agents, release agents (tape release agents), scratch-resistant agents, polymerization initiators, polymerization inhibitors, UV absorbers, light stabilizers, antioxidants, sensitizers, antibacterial and antifungal agents, etc. It is preferable to include a dispersant, an antifoaming agent, and a leveling agent. Furthermore, from the viewpoint of environmental compatibility, it is preferable to use additives made from biomass-derived raw materials.

[0063] (dispersant) In the present invention, it is preferable to use a dispersant. By using a dispersant, it is possible to suppress the increase in viscosity of the coating agent that occurs with the addition of fine particles. There are no particular limitations on the dispersant, and known dispersants can be used. Furthermore, when silica fine particles are used, it is preferable that the dispersant has an amine value. Furthermore, it may also have a carboxyl group. The amount of dispersant added is preferably 0.1 to 10 mass% of the total mass of the coating agent, and more preferably 0.5 to 7 mass%. If it is less than 0.1 mass%, the effect of suppressing the increase in viscosity is low, and if it is 10 mass% or more, the degree of crosslinking of the coating film decreases, and the physical properties of the coating film deteriorate. Furthermore, when silica fine particles are used as the fine particles, the amount of dispersant added is preferably 3 to 12 mass% of the total mass of the silica fine particles, and more preferably 5 to 10 mass%.

[0064] (Antifoaming agent) In the present invention, it is preferable to use an antifoaming agent. The compound constituting the antifoaming agent is not particularly limited, and known compounds can be used. Examples include acrylic resins, vinyl ether resins, butadiene resins, silicone resins, fluorine-based resins, and modified resins thereof, with silicone resins being preferred. The amount of antifoaming agent added is preferably 0.05 to 3 mass % of the total mass of the coating agent, and more preferably 0.1 to 2 mass %.

[0065] (Leveling agent) In the present invention, it is preferable to use a leveling agent. The leveling agent is not particularly limited, and any known agent can be used as long as it provides the desired leveling effect, i.e., the effect of suppressing coating defects such as cissing and pinholes during coating and the effect of smoothing the surface of the layer to be formed. Examples of the leveling agent include silicone-based leveling agents, fluorine-based leveling agents, acrylic-based leveling agents, siloxane-modified acrylic-based leveling agents, and vinyl-based leveling agents. The amount of the leveling agent added is preferably 0.05 to 3 mass % of the total mass of the coating agent, and more preferably 0.1 to 2 mass %.

[0066] (Polymerization initiator) In the present invention, a polymerization initiator can be used as needed. As the polymerization initiator, it is preferable to use a radical polymerization initiator, and it is more preferable to use a photopolymerization initiator. The polymerization initiator in the present invention is a compound that undergoes a chemical change through the action of light or through interaction with the electronically excited state of the sensitizing dye, thereby generating, for example, radicals. Among these, a photoradical polymerization initiator is preferable from the viewpoint that polymerization can be initiated by exposure to light. However, when the active energy ray is an electron beam (EB) or the like, a polymerization initiator may not be required.

[0067] In the present invention, the photoradical polymerization initiator is not particularly limited, and known initiators can be used. Specific examples include benzophenone compounds, dialkoxyacetophenone compounds, α-hydroxyalkylphenone compounds, α-aminoalkylphenone compounds, acylphosphine oxide compounds, and thioxanthone compounds. Among these, acylphosphine oxide compounds and thioxanthone compounds are preferred. The polymerization initiators may be used alone or in combination of two or more.

[0068] The amount of polymerization initiator added is preferably 0.5 to 20% by mass, more preferably 1 to 10% by mass, of the total mass of the coating agent. When the coating agent is an EB-curable type, it is preferable that the polymerization initiator is substantially absent. That is, the amount is preferably less than 0.5% by mass, or less than 0.3% by mass, of the total mass of the coating agent, and may be 0% by mass.

[0069] (organic solvent) The active energy ray-curable coating agent of the present invention preferably contains no solvent or has a solvent content of 1000 ppm or less, more preferably 600 ppm or less, based on the total mass of the coating agent. Being solvent-free or containing a solvent within the above range improves surface properties such as abrasion resistance. Furthermore, since a drying process is not required, not only is the energy cost associated with printing reduced, but emissions of volatile organic compounds (VOCs) can also be reduced, making it preferable from the standpoint of environmental compatibility.

[0070] (Viscosity of active energy ray curable coating agent) The viscosity of the active energy ray-curable coating agent of the present invention, measured with a Brookfield viscometer at 25°C, 6 rpm, and rotor No. 3, is preferably 200 to 2000 mPa·s, more preferably 250 to 1500 mPa·s, and even more preferably 300 to 1000 mPa·s. Having a viscosity within the above range not only improves leveling properties, but also prevents excessive penetration into the substrate when applied by printing or other methods, thereby achieving a uniform matte finish.

[0071] (Production of active energy ray curable coating agents) In one embodiment, the active energy ray-curable coating agent can be produced by blending 50 to 80 parts by mass of glycerin propoxy triacrylate, 5 to 30 parts by mass of 1,10-decanediol diacrylate, 10 to 30 parts by mass of fine particles, and 0.2 to 2 parts by mass of a dispersant or antifoaming agent as appropriate, as biomass-derived monomers, and stirring and mixing the mixture using a bladed mixer (disper) or the like for approximately 30 minutes to 3 hours.

[0072] If the active energy ray-curable coating agent of the present invention contains unexpected coarse particles or the like, these particles will deteriorate the quality, so it is preferable to remove them by filtration, etc. Conventional known filters can be used.

[0073] (base material) The substrate used in the present invention is not particularly limited as long as it can be used for a decorative material, and examples thereof include paper substrates such as tissue paper, reinforced paper, kraft paper, fine paper, linter paper, baryta paper, parchment paper, and Japanese paper, and film substrates such as olefin resins such as polypropylene, polyethylene terephthalate, and triacetyl acetate. Paper substrates are preferred.

[0074] (Paper base material) The paper base material has a basis weight of 20 g / m 2 ~150g / m 2 It is preferable that the density is 30 to 100 g / m 2 The thickness of the paper substrate is preferably 20 μm to 200 μm, and the paper substrate is preferably thin paper.

[0075] (decorative materials) The decorative material of the present invention has a substrate, an intermediate layer, and a surface protective layer, in this order. The intermediate layer is formed on the substrate, and then an active energy ray-curable coating agent is printed or applied to form a layer, followed by curing by irradiation with active energy rays, to form the surface protective layer. There are no particular limitations on the printing or coating method, and known methods can be used, including, for example, roll coaters, gravure coaters, flexo coaters, air doctor coaters, blade coaters, air knife coaters, squeeze coaters, impregnation coaters, transfer roll coaters, kiss coaters, curtain coaters, cast coaters, die coaters, offset printing, gravure / offset printing, gravure printing, flexo printing, and screen printing. Among these, gravure / offset printing and gravure printing are preferred.

[0076] The active energy rays used to cure the coating agent include far ultraviolet rays, ultraviolet rays, near ultraviolet rays, electron beams (EB), and proton rays. Of these, electron beams (EB) and proton rays are preferred because they can cure the coating agent without using a polymerization initiator.

[0077] When curing with electron beams, a conventionally known curing device can be used, and the exposure dose is preferably 10 kGy to 200 kGy, more preferably 30 kGy to 100 kGy. An exposure dose of 10 kGy or more prevents poor curing, while an exposure dose of 200 kGy or less minimizes the impact on the substrate. The acceleration voltage is set depending on the thickness and density of the coating film, and is preferably 50 kV to 250 kV, more preferably 75 to 125 kV.

[0078] (mass per unit area of ​​surface protection layer) The mass per unit area of ​​the surface protection layer is 2 to 15 g / m 2 It is preferable that the density is 4 to 12 g / m 2 More preferably, it is 6 to 10 g / m 2 It is more preferable that the density is 2 g / m 2 Abrasion resistance is improved by 15g / m or more. 2 The mass per unit area of ​​the surface protective layer is a value calculated from the mass of the cured surface protective layer. The mass per unit area of ​​the surface protective layer can be adjusted by the coating amount, and for example, the coating amount is 6 to 10 g / m. 2 It is preferable that the range is:

[0079] (gloss value) The 60° gloss value of the surface protective layer is preferably 35 or less, more preferably 30 or less, and even more preferably 25 or less. Depending on the application, it is preferably 2 or more, more preferably 5 or more. The 60° gloss value is determined by applying an active energy ray curable coating agent to the intermediate layer with a bar coater #4 in an amount of 8 g / m. 2The 60° gloss value of the cured surface protective layer was measured using a Micro-TRI-glossmeter manufactured by BYK-Gardner. The gloss value was measured in accordance with JIS Z 8741:1997, 60° specular gloss (Gs(60°)). In order to make the 60° gloss value of the surface protective layer 35 or less, preferably 30 or less, the content of fine particles in the surface protective layer is preferably 4 to 30 mass%, more preferably 8 to 25 mass%, even more preferably 10 to 23 mass%, and particularly preferably 12 to 20 mass%.

[0080] (middle class) The intermediate layer is provided between the substrate and the surface protective layer to improve adhesion between the substrate and the surface protective layer, to prevent excessive penetration of the coating agent into the substrate when applied, and to impart a desired hue to the decorative material. The intermediate layer may be a patterned layer or a solid layer. It is also possible to laminate multiple different intermediate layers. The intermediate layer may be a colored layer, and may have a single color or a pattern (design) composed of multiple colors. The intermediate layer may also be formed by printing or the like using ink. For example, an ink containing a binder resin and a colorant such as a pigment can be used.

[0081] (Transparent resin layer) The decorative material of the present invention can have a transparent resin layer between the intermediate layer and the surface protective layer. The transparent resin layer can be formed by coating, printing, or the like using a varnish containing a binder resin. The transparent resin layer improves adhesion between the intermediate layer and the surface protective layer, improving durability such as abrasion resistance.

[0082] Preferred examples of binder resins used in the intermediate layer and / or transparent resin layer include urethane resins, acrylic polyol resins, acrylic resins, ester resins, amide resins, butyral resins, styrene resins, urethane-acrylic copolymers, vinyl chloride-vinyl acetate copolymer resins, vinyl chloride-vinyl acetate-acrylic copolymer resins, chlorinated propylene resins, nitrocellulose resins (nitrocellulose), and cellulose acetate resins. These may be used alone or in combination of two or more. Furthermore, the binder resin may be a resin obtained by adding a curing agent such as an isocyanate-based curing agent or an epoxy-based curing agent to the resin and crosslinking and curing it. From the viewpoint of environmental adaptability, it is also possible to use resins containing structural units derived from biomass.

[0083] The intermediate layer and / or transparent resin layer can be provided on the substrate by a known method, specifically, comma coating, gravure coating, reverse coating, roll coating, lip coating, spray coating, silk screen printing, offset printing, gravure printing, etc. Among these, gravure printing is preferred.

[0084] (Manufacturing of cosmetic materials) The method for producing a decorative material is not particularly limited, as long as it has a surface protective layer formed on a substrate using the active energy ray-curable coating agent of the present invention. Alternatively, the decorative material may be produced by forming an intermediate layer made of a printing ink composition on a substrate, printing and applying the active energy ray-curable coating agent of the present invention onto the intermediate layer to form an uncured layer, and then irradiating the intermediate layer with active energy rays to form a surface protective layer. A transparent resin layer may also be formed between the intermediate layer and the surface protective layer. The intermediate layer enhances the matte properties of the decorative material, and the transparent resin layer is expected to improve adhesion between the active energy ray-curable coating agent and the intermediate layer and relieve stress during curing by active energy rays. The intermediate layer may also have the effect of a transparent resin layer. Furthermore, by laminating the substrate side to a wood substrate such as particle board or plywood, a decorative board for use in furniture, etc., can be produced.

[0085] Specific examples of the composition of the decorative material are shown below. Base material / intermediate layer (white layer) / surface protective layer Base material / Intermediate layer 1 (white layer) / Intermediate layer 2 (pattern layer) / Surface protection layer Base material / intermediate layer 1 (white layer) / intermediate layer 2 (pattern layer) / transparent resin layer / surface protection layer Base material / Intermediate layer 1 (white layer) / Transparent resin layer / Surface protection layer (Example)

[0086] 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.

[0087] (Average particle size) The average particle size is the D50 value in the particle size distribution determined by the light scattering method, and was measured using a Microtrack Bell T330EXII.

[0088] Example 1 22 parts by mass of 1,6-hexanediol diacrylate, 55.8 parts by mass of glycerin propoxy triacrylate, 20 parts by mass of silica microparticles A (average particle diameter 8 μm, oil absorption 220 mL / 100 g), 1.5 parts by mass of dispersant, 0.5 parts by mass of leveling agent, and 0.2 parts by mass of antifoaming agent were added to a mixer equipped with stirring blades, and the mixture was stirred and mixed for 50 minutes to obtain active energy ray-curable coating agent S1.

[0089] (Examples 2 to 18, Comparative Examples 1 to 6) Using the formulations shown in Tables 1 and 2, active energy ray-curable coating agents S2 to 18 and T1 to 6 were obtained in the same manner as in Example 1.

[0090] Base material: 30g / m 2 A printed matter with an intermediate layer was obtained by gravure printing water-based ink (50 parts of acrylic emulsion (manufactured by Toyo Ink Co., Ltd., solids content 25%, acid value 150 mgKOH / g), 5 parts of titanium oxide, 44 parts of water) on tissue paper. The active energy ray curable coating agents S1 to 18 and T1 to 6 obtained in the examples and comparative examples were applied to the intermediate layer of the printed matter in an amount of 8 g / m using a bar coater #4. 2 The printed matter of coating agents S1 to 14, S16 to 18, and T1 to 6 was irradiated with electron beams, and the printed matter of example S15 was irradiated with ultraviolet light under the following conditions to form a surface protective layer, thereby obtaining a decorative material. Electron beam irradiation conditions: 125kV-30kGy-20m / min. UV irradiation conditions: 120W-200mJ / cm 2

[0091] The raw materials used in the examples and comparative examples are as follows. (Biomass-derived monomers) 1,10-Decanediol diacrylate (functional group number 2, biomass-derived structural unit content 60%) Glycerin propoxytriacrylate (functional group number 3, biomass-derived structural unit content 14%) Glycerin triacrylate (functional group number 3, biomass-derived structural unit content 37%) (non-biomass-derived monomers) 1,6-Hexanediol diacrylate (functional groups: 2) Trimethylolpropane EO modified triacrylate (functional group number 3) Dipentaerythritol hexaacrylate (functional group number 6) (fine particles) ·Silica fine particles A: average particle diameter 8.4μm, D95 / D50 1.6, oil absorption 220mL / 100g Silica microparticles B: average particle size 7.5 μm, D95 / D50 1.7, oil absorption 300 mL / 100 g, organically treated silica Silica microparticle C: average particle size 4.3 μm, D95 / D50 2.1, oil absorption 120 mL / 100 g, organically treated silica ·Silica fine particles D: average particle diameter 3.9μm, D95 / D50 2.3, oil absorption 250mL / 100g ·Silica fine particles E: average particle diameter 11μm, D95 / D50 1.9, oil absorption 90mL / 100g ·Silica fine particles F: average particle diameter 2.7μm, D95 / D50 2.4, oil absorption 170mL / 100g Resin beads A: average particle size 6 μm, D95 / D50 1.6, oil absorption 40 mL / 100 g Resin beads B: average particle size 1.7 μm, D95 / D50 1.6 Resin beads C: average particle size 16 μm, D95 / D50 1.5 Dispersant: Polyester resin Leveling agent: acrylic resin Antifoaming agent: silicone resin Polymerization initiator: Photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone)

[0092] The decorative materials S1 to 18 and T1 to 6, which were made using the active energy ray-curable coating agents S1 to 18 and T1 to 6 obtained in the Examples and Comparative Examples, were evaluated for leveling ability, abrasion resistance, matte finish, and long-run suitability using the methods described below. The evaluation results are shown in Tables 1 and 2.

[0093] <Leveling ability> The uniformity of density (presence or absence of unevenness and / or pinholes) on the surface protective layer of the decorative materials S1 to 18 and T1 to 6 was evaluated visually. "Unevenness" refers to a state in which the coating film is not formed smoothly during the process from coating to curing, resulting in minute variations in gloss on the surface. "Pinholes" refers to a state in which the coating film is not formed smoothly during the process from coating to curing, resulting in minute dot-like chips on the surface. (Evaluation criteria) A: No uneven printing or pinholes B: Slightly uneven printing, no pinholes C: There are slight printing irregularities and pinholes D: There are obvious printing irregularities and pinholes The practical level is A, B or C.

[0094] <Wear resistance> An adhesive (Cevian A, manufactured by Daicel Chemical Industries, Ltd.) was applied to the entire substrate surface of decorative materials S1 to 18 and T1 to 6, and then the materials were attached to plywood (particle board, manufactured by Takehara Kogyo Co., Ltd.) and laminated with a mirror-finished press plate before evaluation. The surface of the decorative material was subjected to an abrasion test 200 times using a Taber abrasion tester (abrasion wheel CS-17), and the removal of the intermediate layer was evaluated visually. (Evaluation criteria) A: Over 90% of the middle class remains B: Between 70% and 90% of the middle class remains C: 50% to less than 70% of the middle class remains D: Less than 50% of the middle class remains The practical level is A, B or C.

[0095] <Matte finish> The 60° gloss value of the surface protective layer was measured five times using a gloss meter (BYK-Gardner "micro-TRI-gloss μ"), and the average value was evaluated as follows. A: 20 or less B: More than 20 and less than 30 C: Over 30 but below 35 D: Over 35 The practical level is A, B or C.

[0096] <Long-run suitability> The active energy ray-curable coating agents obtained in the Examples and Comparative Examples were printed on the printed matter having the above intermediate layer formed thereon using a small gravure printing machine at a printing speed of 40 m / min for 1 hour. The coated matter was irradiated with an electron beam under the above conditions at the beginning of printing and one hour after the start of printing, and the 60° gloss value of the resulting surface protective layer of the decorative material was measured in the same manner as in the evaluation of matte properties described above. The average gloss values ​​obtained were evaluated for the rate of change in gloss value between the beginning of printing and one hour after the start of printing, as follows: A: 5% or less B: More than 5% and less than 10% C: More than 10% and less than 20% D: More than 20% The practical level is A, B or C.

[0097] Table 1

[0098] Table 2

Claims

1. An active energy ray-curable coating agent used to form a surface protective layer of a decorative material having a substrate, an intermediate layer, and a surface protective layer, comprising: the coating agent includes a monomer and a fine particle; The particle size distribution of the fine particles has a D50 of 2 to 15 μm, and a D95 / D50 ratio of the fine particles of 2.3 or less; The active energy ray-curable coating agent has a content of the fine particles of 4 to 30 mass % based on the total mass of the coating agent.

2. 2. The active energy ray-curable coating agent according to claim 1, wherein the content of the organic solvent in the total mass of the coating agent is 1000 ppm or less.

3. 3. The active energy ray-curable coating agent according to claim 1, wherein the fine particles are silica fine particles.

4. 4. The active energy ray-curable coating agent according to claim 3, wherein the silica fine particles have an oil absorption of 100 to 400 ml / g.

5. The active energy ray-curable coating agent according to claim 1 or 2, wherein the monomer comprises a biomass-derived monomer.

6. The active energy ray-curable coating agent according to claim 5 , wherein the biomass-derived monomer has a structure derived from glycerin.

7. 6. The active energy ray-curable coating agent according to claim 5, wherein the content of the biomass-derived monomer is 60 mass% or more of the total mass of the monomers.

8. 3. The active energy ray-curable coating agent according to claim 1, wherein the monomer comprises a monomer having three or more functional groups, and the content of the monomer having three or more functional groups in the total mass of the active energy ray-curable coating agent is 50 mass% or more.

9. 3. The active energy ray-curable coating agent according to claim 1, which is substantially free of a polymerization initiator.

10. A decorative material comprising a substrate, an intermediate layer, and a surface protective layer formed from the active energy ray-curable coating agent according to claim 1 or 2.

11. The decorative material according to claim 10, wherein the substrate is a paper substrate.

12. The mass per unit area of ​​the surface protective layer is 2 to 15 g / m ２ The decorative material according to claim 10,

13. The decorative material according to claim 10, wherein the 60° gloss value measured from the surface protective layer side is 2 to 30.

14. A method for producing a decorative material having a substrate, an intermediate layer, and a surface protective layer, comprising: The method includes the steps of forming an intermediate layer on a substrate, applying an active energy ray-curable coating agent containing a monomer and fine particles to form an uncured layer, and then irradiating the uncured layer with active energy rays to form the surface protective layer, The particle size distribution of the fine particles has a D50 of 2 to 15 μm, and a D95 / D50 ratio of the fine particles of 2.3 or less; The method for producing a cosmetic material, wherein the content of the fine particles is 4 to 30 mass % of the total mass of the coating agent.

Images