Decorative material, and method for producing decorative material

Abstract

This decorative material has at least an intermediate layer and a surface protection layer in that order on a base material. The intermediate layer is formed from an intermediate layer-forming resin composition containing at least one type selected from the group consisting of an acrylic resin, a urethane resin and an active energy ray-curable monomer. The surface protection layer contains fine particles and a cured product of a (meth)acrylate. The decorative material satisfies at least one of requirements (I) and (II). (I) In the surface protection layer, the (meth)acrylate includes a (meth)acrylate having a biomass-derived structure, and the (meth)acrylate having a biomass-derived structure has a structure derived from at least one type selected from the group consisting of a fatty acid, glycerin, a terpene and a sugar. (II) In the intermediate layer, the intermediate layer-forming resin composition includes a material having a biomass-derived structure.

Description

Cosmetic material and manufacturing method of cosmetic material

[0001] FIELD OF THE INVENTION Embodiments of the present invention relate to a cosmetic material and a method for making a cosmetic material.

[0002] Decorative materials are widely used to enhance the design of architectural interiors and the surfaces of furniture, fixtures, and the like. Typically, decorative materials are required to have not only appearance properties such as matte finish, but also surface protection properties such as stain resistance, weather resistance, solvent resistance, and abrasion resistance. To meet these requirements, a surface protective layer is typically provided on the surface of a substrate. From the standpoints of environmental and productivity, active energy ray-curable coating agents are preferably used as materials for the surface protective layer. Furthermore, such coating agents generally contain matting agents such as silica, primarily for the purpose of enhancing matte finish by reducing gloss. However, the use of matting agents can cause a decrease in leveling ability and a decrease in other surface protective layer properties such as stain resistance. Therefore, studies have been conducted to achieve low gloss without using matting agents (e.g., Patent Document 1).

[0003] Furthermore, in recent years, there has been an increasing demand for a lower gloss appearance (commonly referred to as high matte) in pursuit of a luxurious feel. Therefore, in the field of decorative materials, there is a demand for decorative materials that combine the desired matte properties with printability (leveling properties) and the properties of a surface protection layer (hereinafter referred to as surface properties) specific to decorative materials, such as abrasion resistance.

[0004] In response to this, Patent Document 1 describes an electron beam-curable matte coating agent containing a compound (A) having 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 is difficult to achieve a sufficiently satisfactory level of matteness, and improvements are needed.

[0005] Furthermore, Patent Document 2 describes the use of a coating agent containing an ionizing radiation-curable resin to form a surface protective layer in a decorative sheet having at least an intermediate layer and a surface protective layer on a substrate in that order. The coating agent contains a mixed resin of a tetrafunctional acrylate and a difunctional acrylate, a thermoplastic resin, and silica. However, the decorative material obtained using the coating agent does not achieve fully satisfactory levels of properties in terms of both matte finish and surface characteristics, and further improvements are required.

[0006] Furthermore, Patent Document 3 describes the use of an active energy ray-curable composition containing an active energy ray-curable compound, a photopolymerization initiator, and a matting agent as a coating agent. This coating agent is characterized by containing specific amounts of ethylene oxide-modified 1,6-hexanediol diacrylate, ethylene oxide-modified trimethylolpropane triacrylate, and an ethoxyethoxyethanol acrylic acid polymer ester as the active energy ray-curable compounds, and the average particle size of the matting agent is 1 to 10 μm. However, even with this coating agent, it is difficult to achieve a fully satisfactory level of matting properties and surface characteristics, and further improvements are required.

[0007] JP 2023-166728 A JP 2014-198440 A International Publication No. 2022 / 224830 Pamphlet

[0008] As described above, decorative materials having a surface protective layer formed using a conventional active energy ray-curable composition are not fully satisfactory in both low gloss (mattness) and surface properties. Furthermore, when a coating agent containing a matting agent is used as a material for forming the surface protective layer, it is difficult to achieve a balance between low gloss (mattness) and leveling properties, so there is a demand for improved leveling properties. Furthermore, while water resistance and oil resistance are essential specifications required by furniture manufacturers, the water resistance and oil resistance of decorative materials using paper substrates are not at a fully satisfactory level, and further development is desired.

[0009] Meanwhile, in recent years, from the viewpoint of environmental compatibility, for example, in the field of packaging materials, there has been growing interest in carbon neutrality and biomass, and various products that meet these requirements have been proposed. However, in the field of cosmetic materials, no products have been proposed that meet the demand for environmental compatibility and are fully satisfactory in terms of various properties. In particular, cosmetic materials using aqueous biomass resins are inferior in water resistance and oil resistance compared to conventional representative cosmetic materials, and improvements are required.

[0010] Therefore, in view of the above-mentioned circumstances, one embodiment of the present invention provides a decorative material that has low gloss and excellent surface properties such as leveling ability, and that has excellent water resistance and oil resistance even when it has a paper substrate, and is environmentally friendly. Another embodiment of the present invention provides an active energy ray-curable coating agent used to form a surface protective layer of a decorative material, which has excellent leveling ability, abrasion resistance, matte properties, and long-run suitability, and contributes to carbon neutrality.

[0011] That is, embodiments of the present invention relate to the following. However, the present invention is not limited to the following embodiments and includes various embodiments. <1> A decorative material having at least an intermediate layer and a surface protective layer formed in this order on a substrate, wherein the intermediate layer is formed from a resin composition for forming an intermediate layer containing at least one selected from the group consisting of acrylic resins, urethane resins, and monomers curable with active energy rays, and the surface protective layer contains fine particles and a cured product of a (meth)acrylate, and the decorative material satisfies at least one of the following requirements (I) and (II): (I) In the surface protective layer, the (meth)acrylate contains a (meth)acrylate having a structure derived from biomass, and the (meth)acrylate having a structure derived from at least one selected from the group consisting of fatty acids, glycerin, terpenes, and sugars. (II) In the intermediate layer, the resin composition for forming an intermediate layer contains a material having a structure derived from biomass. <2> The decorative material according to <1> above, which satisfies requirement (I). <3> The decorative material according to <1> or <2> above, which satisfies requirement (II) and wherein the material having a biomass-derived structure comprises at least one selected from the group consisting of a resin having a biomass-derived structure and a (meth)acrylate having a biomass-derived structure. <4> The decorative material according to any one of <1> to <3> above, wherein the substrate is a paper substrate. <5> The decorative material according to any one of <1> to <4> above, wherein the fine particles have a D50 of 2 to 12 μm and a D95 / D50 ratio of 2.5 or less. <6> The decorative material according to any one of <1> to <5> above, wherein the fine particles comprise silica fine particles. <7> The decorative material according to any one of <1> to <6> above, wherein the 60° gloss value is 2 to 30.<8> A method for producing a decorative material having at least an intermediate layer and a surface protective layer formed in this order on a substrate, the method comprising the steps of: forming an intermediate layer on the substrate using a resin composition for forming an intermediate layer, the resin composition comprising at least one selected from the group consisting of an acrylic resin, a urethane resin, and a monomer curable with active energy rays; and applying an active energy ray-curable coating agent containing fine particles and a (meth)acrylate to form a coating film on the intermediate layer formed on the substrate, and irradiating with active energy rays to cure the coating film, thereby forming a surface protective layer, the method satisfying at least one of the following requirements (I) and (II): (I) In the active energy ray-curable coating agent, the (meth)acrylate comprises a (meth)acrylate having a structure derived from biomass, and the (meth)acrylate having a structure derived from at least one selected from the group consisting of fatty acids, glycerin, terpenes, and sugars; or (II) The resin composition for forming an intermediate layer comprises a material having a structure derived from biomass. <9> The method for producing a decorative material according to the above item <8>, wherein the active energy ray-curable coating agent contains a (meth)acrylate having a functionality of 3 or more, and the content of the (meth)acrylate having a functionality of 3 or more is 50 mass % or more based on the total mass of the coating agent. <10> The method for producing a decorative material according to the above item <8> or <9>, wherein the active energy ray is an electron beam.

[0012] According to an embodiment of the present invention, a decorative material having low gloss and excellent surface properties such as leveling properties can be provided, and even if the decorative material has a paper substrate, the decorative material has excellent water resistance and oil resistance and is environmentally compatible. Also, an active energy ray-curable coating agent used to form a surface protective layer of a decorative material can be provided, which has excellent leveling properties, abrasion resistance, matte properties, and long-run suitability, and contributes to carbon neutrality.

[0013] Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the embodiments described below, and may include various modifications without departing from the spirit of the present invention.

[0014] 1. One embodiment of the present invention relates to a decorative material. The decorative material of this embodiment has at least an intermediate layer and a surface protective layer, in that order, on a substrate. In this decorative material of this embodiment, the intermediate layer is formed using a resin composition for forming an intermediate layer, which includes at least one selected from the group consisting of acrylic resins, urethane resins, and monomers curable with active energy rays. The surface protective layer includes fine particles and a cured product of a (meth)acrylate, and is characterized by satisfying at least one of the following requirements (I) and (II). That is, this decorative material of this embodiment is characterized in that at least one of the intermediate layer and the surface protective layer has a biomass-derived structure. (I) In the surface protective layer, the (meth)acrylate includes a (meth)acrylate having a biomass-derived structure, and the (meth)acrylate having a biomass-derived structure has a structure derived from at least one selected from the group consisting of fatty acids, glycerin, terpenes, and sugars. (II) In the intermediate layer, the resin composition for forming an intermediate layer includes a material having a biomass-derived structure.

[0015] In this specification, "(meth)acrylate" means acrylate and / or methacrylate. Furthermore, "(meth)acrylic acid" means acrylic acid and / or methacrylic acid. The composition of the decorative material will be specifically described below. <Substrate> In this embodiment, the substrate is not particularly limited as long as it can be used in a decorative material. Examples include paper substrates (hereinafter referred to as paper substrates) and film substrates composed of olefin resins such as polypropylene, polyethylene terephthalate, triacetyl acetate, and other resins. From the viewpoint of environmental compatibility, paper substrates are preferred. (Paper Substrate) Examples of paper substrates include tissue paper, reinforced paper, kraft paper, fine paper, linter paper, baryta paper, parchment paper, and Japanese paper. These may be used alone or in combination of two or more. The paper substrate should preferably have a basis weight of 20 g / m ２ ~150g / m ２ It is preferable that the density is 30 to 100 g / m ２The thickness of the paper substrate is preferably 20 μm to 200 μm. In some embodiments, tissue paper can be suitably used.

[0016] <Intermediate Layer> In this embodiment, the intermediate layer is a resin layer provided between the substrate (preferably a paper substrate) and the surface protective layer. The intermediate layer functions as a primer layer that improves adhesion between the substrate and the surface protective layer. The intermediate layer also prevents excessive penetration of the coating agent into the substrate, such as a paper substrate, during the formation of the surface protective layer. Furthermore, the intermediate layer imparts a desired hue to the decorative material. The intermediate layer may be a patterned layer or a solid layer. Alternatively, multiple intermediate layers with different configurations may be laminated.

[0017] In this embodiment, the intermediate layer can be formed using a resin composition containing a binder resin known in the art. Specifically, the binder resin includes at least one selected from the group consisting of acrylic resins, urethane resins, and monomers curable with active energy rays, and may further include other resins different from these, as necessary. In some embodiments, the binder resin may include at least one selected from the group consisting of acrylic resins and urethane resins. In other embodiments, the binder resin may include the acrylic resin and / or urethane resin, and, as necessary, a resin other than the acrylic resin and urethane resin (referred to as other resins) and / or a monomer curable with active energy rays. In still other embodiments, the binder resin may include a monomer curable with active energy rays.

[0018] The intermediate layer is preferably a layer (coating film or cured film) formed using a composition containing at least one binder resin selected from the group consisting of acrylic resin, urethane resin, and active energy ray-curable monomer. The intermediate layer may also be a layer (cured film) formed using a composition containing only active energy ray-curable monomers as the binder resin. In some embodiments, the intermediate layer may be a colored layer, and may have a single color or a pattern (design) composed of multiple colors. In some embodiments, the resin composition forming the intermediate layer (hereinafter referred to as the intermediate layer-forming resin composition or resin composition) may suitably be an ink containing a binder resin and, if necessary, a colorant such as a pigment and various additives. The ink may be a colored ink such as a clear ink or a white ink.

[0019] The intermediate layer can be formed by applying the ink to a substrate using a printing method known in the art. The ink that can be used as the resin composition for forming the intermediate layer may further contain various additives such as wax, dispersant, and defoamer, as necessary.

[0020] In one example of the decorative material of this embodiment, from the viewpoint of environmental compatibility, the intermediate layer is preferably formed from a resin composition for forming an intermediate layer that includes a material having a biomass-derived structure. The material having a biomass-derived structure may be a binder resin, a pigment, various additives, or other components, but the above materials refer to the solid components that actually constitute the intermediate layer. In some embodiments, a resin having a biomass-derived structure can be suitably used as the binder resin. The resin composition for forming an intermediate layer will be specifically described below.

[0021] (Binder Resin) The acrylic resin refers to a polymer primarily composed of a structure derived from (meth)acrylic acid or a (meth)methacrylic acid ester, and any compound known in the art as an acrylic resin can be used. In some embodiments, the acid value of the acrylic resin may be preferably 300 KOH mg / g or less, more preferably 270 KOH mg / g or less, and even more preferably 240 KOH mg / g or less. In some embodiments, the acid value of the acrylic resin may be 0 KOH mg / g.

[0022] In some embodiments, the acrylic resin is preferably used in the form of an acrylic emulsion, an acrylic solution, or an acrylic dispersion. Acrylic emulsions, acrylic solutions, and acrylic dispersions can be produced according to methods well known in the art. Acrylic resins that can be suitably used in this embodiment are also commercially available. Examples of acrylic emulsions include JONCRYL FLX5000, JONCRYL 77, JONCRYL BRC 6824, and JONCRYL BRC 6855, all manufactured by BASF Corporation, and SP-7450, manufactured by Covestro. Examples of acrylic solutions include JONCRYL 60J and JONCRYL MB HPD496, all manufactured by BASF Corporation. Examples of acrylic dispersions include SETAQUA 8800, SETAQUA 8802, SETAQUA 8804, and SETAQUA BB8850 manufactured by Allnex, and SP-6200 manufactured by Covestro.

[0023] The urethane resin is a polymer having a urethane bond formed by the reaction of an isocyanate group with a hydroxyl group, and any urethane resin known in the art can be used. In some embodiments, the urethane resin may preferably be an aqueous urethane resin. An aqueous urethane resin is a urethane resin dispersed in an aqueous medium, and can be produced according to methods known in the art. Aqueous urethane resins that can be suitably used in this embodiment are also commercially available. Examples include Takelac W-6110 manufactured by Mitsui Chemicals, Inc., Superflex 150 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., and NeoRad R-449 manufactured by Covestro.

[0024] In the resin composition for forming an intermediate layer (clear ink), the content of the acrylic resin or urethane resin may be preferably 30% by mass or more, more preferably 50% by mass or more, based on the total mass of the solid components of the resin composition. Furthermore, in the resin composition for forming an intermediate layer (color ink), such as a white ink, the content of the acrylic resin or urethane resin may be preferably 30% by mass or more, more preferably 50% by mass or more, based on the total mass of the solid components of the resin composition. When an acrylic emulsion or an aqueous urethane resin is used, the content of the acrylic resin or urethane resin corresponds to the content of the solid components (also referred to as the solid component amount), respectively.

[0025] In some embodiments, the binder resin used in the resin composition for forming the intermediate layer may further contain, in addition to an acrylic resin and / or a urethane resin, other resins different from these. Examples of other resins include acrylic polyol 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. The resins exemplified as other resins may be used alone or in combination of two or more. In some embodiments, the binder resin may be obtained by adding a curing agent such as an isocyanate-based curing agent or an epoxy-based curing agent to the above-mentioned resins and crosslinking and curing them.

[0026] In some embodiments, the binder resin used in the resin composition for forming the intermediate layer may contain a monomer curable with active energy rays. Although not particularly limited, a monomer curable with electron beams can be preferably used. Among the above-mentioned monomers, compounds having an unsaturated double bond group such as a vinyl group and a (meth)acrylic group are preferred, and (meth)acrylates can be preferably used. Specific examples of the monomer include the same monomers as those in the "active energy ray-curable coating agent" described below. That is, in some embodiments, the above-mentioned monomer may be either a (meth)acrylate having a biomass-derived structure or a (meth)acrylate not having a biomass-derived structure, but a (meth)acrylate having a biomass-derived structure can be preferably used.

[0027] In the resin composition for forming an intermediate layer (clear ink), the content of the active energy ray-curable monomer such as (meth)acrylate may be preferably 30 mass% or more, more preferably 50 mass% or more, based on the total mass of the solid components of the resin composition. Also, in the resin composition for forming an intermediate layer (color ink), for example, white ink, the content of the active energy ray-curable monomer such as (meth)acrylate may be preferably 30 mass% or more, more preferably 50 mass% or more, based on the total mass of the solid components of the resin composition.

[0028] In some embodiments, in the case of a clear ink, the content of the binder resin, based on the total mass of the solid components in the ink, is preferably 25% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and may even be 100% by mass. On the other hand, in the case of a colored ink such as a white ink, the content of the binder resin, based on the total mass of the solid components in the ink, may be preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more. The content of the binder resin may preferably be 65% by mass or less, more preferably 60% by mass or less. Here, the content of the binder resin refers to the total amount of at least one resin selected from the group consisting of acrylic resins, urethane resins, and monomers curable with active energy rays, and other resins different from the above resins that are used as needed.

[0029] In the decorative material of this embodiment, from the viewpoint of environmental compatibility, the intermediate layer is preferably formed using a material having a biomass-derived structure. Therefore, a resin having a biomass-derived structure (structural unit) and a (meth)acrylate having a biomass-derived structure can be suitably used as the binder resin constituting the resin composition for forming the intermediate layer. For example, in the case of an acrylic resin, a resin having a biomass-derived structure can be obtained by using a biomass-derived monomer as at least a portion of the raw material (meth)acrylic monomer. Furthermore, in the case of a urethane resin, a resin having a biomass-derived structure can be obtained by using a biomass-derived compound as at least a portion of the raw material polyol and / or polycarboxylic acid. Resins or monomers having a biomass-derived structure can also be commercially available. Specific examples include BRC 6824 (acrylic emulsion, solid content 45%, acid value of solid content 32 KOH mg / g, content of biomass-derived structural units 23% by mass) manufactured by BASF Corporation, BRC 6896 (acrylic solution, solid content 40%, acid value of solid content 87 KOH mg / g, content of biomass-derived structural units 24% by mass) manufactured by BASF Corporation, SARBIO 5201 (1,10-decanediol diacrylate, content of biomass-derived structures 60% by mass) manufactured by ARKEMA Corporation, and SARBIO 5101NS (lauryl acrylate, content of biomass-derived structures 80% by mass) manufactured by ARKEMA Corporation.

[0030] (Solvent) The resin composition for forming an intermediate layer may further contain a solvent. For example, it may contain water and an organic solvent such as isopropyl alcohol, butyl diglycol, propylene glycol, ethylene glycol, methyl alcohol, or ethyl alcohol. On the other hand, in some embodiments, the resin composition for forming an intermediate layer preferably does not substantially contain an organic solvent. As used herein, "substantially does not contain an organic solvent" means that no organic solvent is intentionally added to the resin composition, but the resin composition may contain an organic solvent that has been mixed in during the resin manufacturing process, etc. Based on the total mass of the resin composition for forming an intermediate layer, the content of the organic solvent is preferably 5% by mass or less, more preferably 2% by mass or less, even more preferably 0.5% by mass or less, and may even be 0% by mass. (Additives) The resin composition may further contain various additives as needed. Examples of additives include wax, film-forming aids, polymerization inhibitors, pigment dispersants, wetting agents, and defoamers. Suitable waxes include, but are not limited to, DEUREX X 2010M (amide wax, particle size ≦10 μm) manufactured by DEUREX Co., Ltd., and CERAFLOUR 1000 (micronized modified biopolymer, D90: 11 μm) and CERAFLOUR 1001 (micronized modified biopolymer, D90: 7 μm) manufactured by BYK-Chemie Co., Ltd. Suitable dispersants include DISPERBYK-192 (modified polyether) and DISPERBYK-108 (hydroxyl group-containing carboxylic acid ester) manufactured by BYK-Chemie Co., Ltd. As the defoaming agent, Tego Foamex 8820, Tego Foamex 832, and Tego Foamex 8850 (all hydrophobic organic polymers) manufactured by EVONIK Corporation can be used.

[0031] Although not particularly limited, an example of the resin composition for forming an intermediate layer (clear ink) is an ink containing an acrylic resin and / or a urethane resin as a binder resin, and more specifically, it may contain 95 parts by mass or more of an acrylic emulsion and / or an aqueous urethane resin (solid content of 40% by mass or more) and a total amount of various additives such as a thickening aid of 5 parts by mass or less (which may be 0 parts by mass). Another example is a white ink containing an acrylic resin and / or a urethane resin as a binder resin, and more specifically, the ink may contain 50 to 60 parts by mass of an acrylic emulsion and / or an aqueous urethane resin (solid content of 40% by mass or more), 20 to 40 parts by mass of titanium oxide, 20 to 80 parts by mass of water, and 0 to 10 parts by mass of various additives.

[0032] Another example is a clear ink containing a (meth)acrylate as a binder resin. More specifically, this ink may contain one or more binder resins selected from the group consisting of 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, trimethylolpropane EO-modified triacrylate, dodecyl acrylate, glycerin propoxy triacrylate, and diglycerin EO-modified tetraacrylate in a total amount of 95 parts by mass or more, and fine particles and various additives in a total amount of 5 parts by mass or less (which may be 0 parts by mass). Another example is a white ink containing a (meth)acrylate as a binder resin. More specifically, this ink may contain one or more binder resins selected from the group consisting of 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, trimethylolpropane EO-modified triacrylate, dodecyl acrylate, glycerin propoxy triacrylate, and diglycerin EO-modified tetraacrylate in a total amount of 5 parts by mass or less (which may be 0 parts by mass).

[0033] The combination of two or more of the above (meth)acrylates is not particularly limited, and examples thereof include 1,6-hexanediol diacrylate / dodecyl acrylate / glycerin propoxy triacrylate / diglycerin EO-modified tetraacrylate, tripropylene glycol diacrylate / glycerin propoxy triacrylate, glycerin propoxy triacrylate / diglycerin EO-modified tetraacrylate, tripropylene glycol diacrylate / diglycerin EO-modified tetraacrylate, tripropylene glycol diacrylate / trimethylolpropane EO-modified triacrylate, and 1,6-hexanediol diacrylate / glycerin propoxy triacrylate.

[0034] <Surface protective layer> The surface protective layer in the decorative material can be formed using an active energy ray-curable coating agent containing fine particles and a monomer that can be cured with active energy rays, such as (meth)acrylate. From the viewpoint of environmental compatibility, the surface protective layer in the decorative material of this embodiment is preferably formed using an active energy ray-curable coating agent containing fine particles and a monomer that can be cured with active energy rays, such as (meth)acrylate, and has a structure derived from biomass. That is, in this embodiment, the surface protective layer contains a cured product of an active energy ray-curable coating agent that contains fine particles and a monomer such as (meth)acrylate that has a structure derived from biomass.

[0035] Hereinafter, an active energy ray-curable coating agent that can be suitably used to form a surface protective layer in this embodiment will be specifically described. (Active Energy Ray-Curable Coating Agent) In this embodiment, the surface protective layer can be formed by applying an active energy ray-curable coating agent (hereinafter also referred to as coating agent) onto an intermediate layer provided on a substrate by any printing method to form a coating film, and then irradiating this coating film with active energy rays to cure the coating film. By irradiating with active energy rays, a monomer contained in the coating agent is cured to form a cured film. In this specification, "monomer" means a monomer containing an unsaturated double bond group that can be cured by active energy rays.

[0036] The content of the monomer in the total mass of the coating agent is preferably 70 to 90% by mass, more preferably 70 to 85% by mass, and even more preferably 75 to 85% by mass. The unsaturated double bond group in the monomer may have a structure such as a vinyl group or a (meth)acrylic group, with a (meth)acrylic group being preferred. In some embodiments, the monomer contained in the coating agent preferably contains a (meth)acrylate having the above-described biomass-derived structure (hereinafter also referred to as a biomass-derived (meth)acrylate). The monomer contains a biomass-derived monomer and may further contain a non-biomass-derived monomer as needed. In other embodiments, when the coating agent does not contain a biomass-derived monomer, the intermediate layer-forming resin composition constituting the intermediate layer contains a material having a biomass-derived structure. Below, biomass-derived monomers and non-biomass-derived monomers will be described separately.

[0037] (Biomass-derived monomer) From the viewpoint of environmental compatibility such as carbon neutrality, it is preferable that the coating agent uses a biomass-derived monomer. In this specification, "biomass-derived monomer" refers to a polymerizable compound produced using biomass-derived raw materials as part or all of the raw materials, 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 biomass alcohol-derived monomer is preferable. In some embodiments, the monomer is preferably a biomass monoalcohol-derived and / or biomass polyol-derived monomer, and more preferably contains at least a biomass polyol-derived monomer.

[0038] In the biomass alcohol, examples of biomass monoalcohols include methanol, ethanol, butanol, dodecanol, tetradecanol, and hexadecanol. Of these, dodecanol, tetradecanol, and hexadecanol are preferred. In addition, in the biomass alcohol, examples of biomass polyols include ethylene glycol, glycerin, 1,4-butanediol, 1,10-decanediol, and polytetramethylene glycol. Of these, glycerin and 1,10-decanediol are preferred.

[0039] The biomass alcohol-derived monomer may be a reaction product of the biomass alcohol with a compound having a functional group reactive with a hydroxyl group in the biomass alcohol and an unsaturated double bond group. In some embodiments, the biomass alcohol-derived monomer may be a reaction product of the biomass alcohol with (meth)acrylic acid, such as 1,10-decanediol diacrylate, glycerin propoxy triacrylate, or glycerin triacrylate. In some embodiments, it is preferable to use a biomass-derived monomer having a glycerin-derived structure, such as glycerin propoxy triacrylate or glycerin triacrylate. When a biomass-derived monomer having a glycerin-derived structure is used, the dispersibility of fine particles is improved, and good sedimentation stability is easily achieved. Therefore, good long-run suitability tends to be easily achieved in the process of printing a coating agent to form a surface protective layer.

[0040] Specific examples of biomass-derived monomers that can be suitably used in this embodiment are shown below. Examples of biomass-derived monomers with 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.

[0041] Examples of biomass-derived monomers having two functional groups include decanediol di(meth)acrylate, polyethylene glycol dimethacrylate, glycerin diacrylate, and isosorbide diacrylate.

[0042] Examples of biomass-derived monomers having three functional groups include glycerin triacrylate and glycerin propoxy triacrylate.

[0043] An example of a biomass-derived monomer having four functional groups is diglycerin tetraacrylate.

[0044] In some embodiments, the biomass-derived (meth)acrylate preferably has a structure derived from at least one selected from the group consisting of fatty acids, glycerin, terpenes, and sugars. More specifically, the structure is as follows.

[0045] The biomass-derived monomer having a structure derived from a fatty acid may be, for example, a (meth)acrylate obtained by acrylating a higher alcohol derived from a fatty acid having six or more carbon atoms. Among such biomass-derived (meth)acrylates having a structure derived from a fatty acid, examples of compounds having one functional group include dodecyl acrylate, octadecyl methacrylate, 2-hexyldecyl acrylate, 2-octyl acrylate, n-hexyl acrylate, and 2-hexyl acrylate. Examples of compounds having two functional groups include 1,10-decanediol diacrylate.

[0046] The biomass-derived monomer having a structure derived from glycerin may be, for example, a (meth)acrylate obtained by acrylation of glycerin. Among such biomass-derived (meth)acrylates having a structure derived from glycerin, examples of compounds having one functionality include glycerin carbonate acrylate. Examples of compounds having two functionality groups include glycerin diacrylate. Examples of compounds having three functionality groups include glycerin propoxy triacrylate and glycerin triacrylate. Examples of compounds having four functionality groups include diglycerin tetraacrylate and diglycerin EO (ethylene oxide)-modified tetraacrylate. These may be used alone or in combination of two or more. When a biomass-derived monomer having a structure derived from glycerin is used, the dispersibility of fine particles is improved and sedimentation stability is favorable, making it easier to improve long-run suitability during printing.

[0047] The biomass-derived monomer having a terpene-derived structure may be, for example, a (meth)acrylate obtained by acrylating menthol. Among such biomass-derived (meth)acrylates having a terpene-derived structure, an example of a compound having one functional group is L-menthyl acrylate.

[0048] The biomass-derived monomer having a structure derived from sugar may be a (meth)acrylate obtained by acrylating a sugar alcohol produced from starch or sugar derived from plants such as corn and wheat, or an alkylene oxide-modified product thereof. Among the biomass-derived (meth)acrylates having a structure derived from sugar, an example of a compound having two functional groups is isosorbide diacrylate having a structure derived from sugar (corn starch).

[0049] In addition to the above, biomass-derived monomers having a structure derived from natural products can also be used, such as compounds obtained by acrylate of rosin, which is known as a natural resin like terpenes. Rosin having an acrylic group obtained by reacting rosin with glycidyl acrylate is preferably used.

[0050] Based on the total mass of the solid components in the coating agent, the content of the biomass-derived monomer may preferably be 40% by mass or more, 55% by mass or more, 60% by mass or more, or 65% by mass or more. In some embodiments, based on the total mass of the monomers in the coating agent, the content of the biomass-derived monomer is preferably 55% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more.

[0051] (Biomass Degree) In this embodiment, the biomass degree refers to the mass ratio (%) of the biomass-derived structure based on the total mass of the solid components in the coating agent excluding inorganic matter (i.e., the total mass of the organic matter in the solid components). That is, the biomass degree is a value represented by the following formula (I). The mass of the biomass-derived structure is calculated by multiplying the "amount of compound having a biomass-derived structure" by the "proportion of the biomass-derived structure in the compound". Formula (I): Biomass degree = (total mass of biomass-derived structures / mass of all solid components in the coating agent) x 100

[0052] In this embodiment, from the viewpoint of environmental compatibility, the biomass content of the coating agent is preferably 3% by mass or more, more preferably 5% by mass or more, and even more preferably 8% by mass or more.

[0053] (Non-biomass-derived monomer) In some embodiments, the monomer in the active energy ray-curable coating agent may contain a non-biomass-derived monomer. Known monomers can be used as the non-biomass-derived monomer. Specific examples of the non-biomass-derived monomer are shown below.

[0054] Examples of non-biomass-derived monomers having 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.

[0055] 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.

[0056] 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.

[0057] 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.

[0058] Examples of non-biomass-derived monomers having five or six functional groups include dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate.

[0059] The (meth)acrylates exemplified above are preferably alkylene oxide-modified compounds, regardless of whether they are derived from biomass or non-biomass. Suitable alkylene oxides include ethylene oxide (EO) and propylene oxide (PO).

[0060] (Number of Functional Groups of Monomer) In this embodiment, the number of functional groups 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 having the number of functional groups within the above range, it is possible to achieve both abrasion resistance and matte properties. In some embodiments, it is 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 two or more monomers with different numbers of functional groups in combination, it is easy to adjust the viscosity of the coating agent and easily obtain good leveling properties.

[0061] 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% by mass, more preferably 52 to 80% by mass, and even more preferably 55 to 75% by mass. The content of monomers having three or more functional groups refers to the total amount of biomass-derived monomers having three or more functional groups and / or non-biomass-derived monomers having three or more functional groups. In some embodiments, the coating agent preferably contains a biomass-derived (meth)acrylate having three or more functional groups. Among biomass-derived (meth)acrylates having three or more functional groups, glycerin triacrylate and glycerin propoxy triacrylate can be suitably used. In some embodiments, the content of biomass-derived (meth)acrylates having three or more functional groups is preferably 50 to 80% by mass, more preferably 50 to 70% by mass, and even more preferably 50 to 60% by mass.

[0062] (Other Resin Components) In this embodiment, the coating agent may further contain resin components other than the above-mentioned monomers (hereinafter referred to as other resin components) to the extent that the desired effect is not reduced. Examples of other resin components that can be added 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 content of the other resin components may be preferably 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, based on the total mass of solid components excluding fine particles and colorants from the total mass of the active energy ray-curable coating agent.

[0063] Examples of resins containing biomass-derived components include urethane acrylate and polyester acrylate, which contain biomass-derived components, and cellulose-based resins such as cellulose acetate butyrate and cellulose acetate propionate.

[0064] In some embodiments, the monomer contained in the coating agent includes at least (1) a biomass-derived monomer and may further include (2) a non-biomass-derived monomer as needed. The monomer contained in the coating agent is preferably a combination of (1) and (2) above, and the monomer is preferably a (meth)acrylate. More specifically, (1) above preferably includes at least one selected from the group consisting of 2-hexyl acrylate, 1,10-decanediol diacrylate, L-menthyl acrylate, isosorbide diacrylate, glycerin propoxy triacrylate, glycerin triacrylate, and diglycerin EO (ethylene oxide)-modified tetraacrylate. (2) above preferably includes at least one selected from the group consisting of 1,6-hexanediol diacrylate, trimethylolpropane EO-modified triacrylate, and dipentaerythritol hexaacrylate. Based on the total mass of the monomers, the content of the biomass-derived monomer (1) is preferably 55% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more, and may be 100% by mass.

[0065] (Fine Particles) In this embodiment, the fine particles used in the coating agent not only impart a matte appearance to the surface protective layer, but also have the effect of improving durability such as abrasion resistance. Known organic fine particles and / or inorganic fine particles can be used as the fine particles. Examples of organic fine particles include resin beads such as acrylic resin, urethane resin, and polyethylene resin. Examples of inorganic fine particles include fine particles of silica, calcium carbonate, barium sulfate, and alumina. Among these, from the viewpoint of achieving low gloss (mattness), 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 types.

[0066] Based on the total mass of the solid components in the active energy ray-curable coating agent, the content of the microparticles may be preferably 4 to 30 mass%, more preferably 8 to 25 mass%, and even more preferably 10 to 20 mass%. When the content of the microparticles is 4 mass% or more, good matting properties are achieved. When the content of the microparticles is 30 mass% or less, excellent leveling properties can be easily achieved, and the transparency of the surface protective layer can be improved. Furthermore, when the content of the microparticles is adjusted within the above range, good abrasion resistance can be easily achieved.

[0067] From the viewpoint of matting properties, the average particle diameter D50 of the fine particles is preferably selected appropriately depending on the film thickness of the surface protective layer and the desired gloss value. In some embodiments, the average particle diameter D50 of the fine particles may be preferably 2 μm to 15 μm, more preferably 3 μm to 12 μm, even more preferably 4 μm to 10 μm, and particularly preferably 5 μm to 10 μm. When the average particle diameter D50 of the fine particles is adjusted to fall within the above range, the matting (low gloss) effect can be easily improved. 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 T330EXII manufactured by Microtrac-Bell Corporation.

[0068] In this embodiment, the D95 / D50 of the fine particles contained in the coating agent is preferably 2.5 or less, more preferably 2.3 or less, even more preferably 2.1 or less, and most 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 diameter larger than the average particle diameter D50. D95 can be measured using a Microtrac-Bell T330EXII or similar device, similar to the D50 described above.

[0069] (Silica microparticles) As silica microparticles, there is no particular limitation on manufacturing method and shape etc., and known silica microparticles 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 surface is physically or chemically treated with surface treatment agent (organic or inorganic substance) such as silane coupling agent, microcrystalline, alumina, wax, etc., and those that are untreated, but both can be used in this embodiment.The term "treated" refers to being coated with surface treatment agent or having chemical bond with surface treatment agent, and "untreated" refers to not having the above-mentioned coating or chemical bond.

[0070] The average particle diameter D50 of the silica fine particles is the same as that of the above-mentioned fine particles, and when it is in this range, the matte (low gloss) effect is enhanced and the abrasion resistance is also improved. Note that the average particle diameter D50 is the D50 value in the particle size distribution measured by the light scattering method as described above.

[0071] 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. By being in this range, the viscosity of the coating agent does not become too high, and leveling properties are improved. The oil absorption is measured in accordance with JIS K5101-13-1.

[0072] Specific examples of silica microparticles include Sylysia 370, 380, 440, and 450 (manufactured by Fuji Silysia Chemical Ltd.), ACEMATT 790 (manufactured by Evonik Japan Ltd.), SYLOIDRAD 2105, SYLOIDC 907, and SYLOIDMX 307 (manufactured by W.R. GRACE & Co.). Silica microparticles often undergo secondary particle aggregation, resulting in an inappropriate particle size distribution. Therefore, in order to disperse the silica with an appropriate particle size distribution during the preparation of a coating agent, it is preferable to pretreat the silica by stirring with a disperser. For example, during the preparation of a coating agent, it is preferable to mix binder resins such as monomers, then gradually add the pretreated silica while stirring with a disperser, and then continue stirring for an appropriate period of time (e.g., 30 minutes). If a dispersant is used, it is preferable to add it before adding the silica (i.e., add it when mixing the monomers, etc.), and then thoroughly stir with a disperser.

[0073] The preferred range of the content of silica fine particles is the same as the content of the above-mentioned 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.

[0074] (Other Additives) If necessary, other additives can be blended into the coating agent to the extent that they do not impair the effects obtained by the present invention. Examples of other additives include film-forming aids, 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. In some embodiments, the coating agent preferably contains a film-forming aid, dispersant, antifoaming agent, and leveling agent. Furthermore, from the viewpoint of environmental compatibility, it is preferable to use additives made from biomass-derived raw materials.

[0075] (Dispersant) In this embodiment, the coating agent preferably contains a dispersant. The use of a dispersant can suppress the increase in viscosity of the coating agent associated 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, dispersants with an amine value are preferred. The dispersant may have a carboxyl group in addition to the amine value. The amount of dispersant added is preferably 0.1 to 10 mass% and more preferably 0.5 to 7 mass% based on the total mass of the solid components in the coating agent. When the amount of dispersant added is 0.1 mass% or more, the viscosity increase suppression effect can be easily achieved. When the amount of dispersant added is 10 mass% or more, the degree of crosslinking of the coating can be easily suppressed, and deterioration of the coating properties can be easily suppressed. When silica fine particles are used as the fine particles, the amount of dispersant added is preferably 3 to 12 mass% and more preferably 5 to 10 mass% based on the total mass of the silica fine particles.

[0076] (Antifoaming Agent) In this embodiment, the coating agent preferably contains an antifoaming agent. There are no particular limitations on the compounds constituting the antifoaming agent, and known compounds can be used. Examples include acrylic resins, vinyl ether resins, butadiene resins, silicone-based resins, fluorine-based resins, and modified resins thereof, with silicone-based resins being preferred. The amount of antifoaming agent added is preferably 0.05 to 3 mass %, and more preferably 0.1 to 2 mass %, based on the mass of the solid components of the coating agent.

[0077] (Leveling Agent) In this embodiment, the coating agent preferably contains a leveling agent. The leveling agent is not particularly limited as long as it provides the desired leveling effect, i.e., the effect of suppressing the occurrence of coating defects such as cissing and pinholes during coating, and the effect of smoothing the surface of the layer to be formed, and any known leveling agent can be used. 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 %, and more preferably 0.1 to 2 mass %, based on the total mass of the solid components of the coating agent.

[0078] (Polymerization Initiator) In this embodiment, the coating agent may contain a polymerization initiator as needed depending on the type of active energy ray used to cure the coating agent. As the polymerization initiator, it is preferable to use a radical polymerization initiator, and it is more preferable to use a photopolymerization initiator. In this specification, the polymerization initiator refers to a compound that undergoes a chemical change through the action of light or through interaction with the electronically excited state of a sensitizing dye, thereby generating, for example, radicals. Among these, a photoradical polymerization initiator is preferable from the viewpoint of being able to initiate polymerization by exposure to light.

[0079] In this embodiment, 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. Of these, acylphosphine oxide compounds and thioxanthone compounds are preferred. The polymerization initiators may be used alone or in combination of two or more.

[0080] When ultraviolet (UV) rays are used as the active energy rays, i.e., when preparing a UV-curable coating agent, it is preferable to contain a photopolymerization initiator. The content of the photopolymerization initiator is preferably 0.5 to 20 mass %, and more preferably 1 to 10 mass %, based on the total mass (total solid components) of the UV-curable coating agent.

[0081] On the other hand, when using electron beams (EB) as the active energy rays, i.e., when preparing an EB-curable coating agent, it is preferable that the EB-curable coating agent is substantially free of a polymerization initiator. In this specification, "substantially free of a polymerization initiator" means that a polymerization initiator is not intentionally added during the preparation of the coating agent, and the coating agent may contain a polymerization initiator that has been mixed in as an impurity during the production process of raw materials, etc. In some embodiments, the content of the polymerization initiator, based on the total mass (total solid components) of the EB-curable coating agent, is preferably less than 0.5 mass%, more preferably less than 0.3 mass%, and may even be 0 mass%.

[0082] (Organic Solvent) The active energy ray-curable coating agent used in the present invention preferably does not contain a solvent, or the solvent content is preferably 1000 ppm or less, more preferably 600 ppm or less, based on the total mass of the coating agent. By not containing a solvent, or by having the solvent content within the above range, surface properties such as abrasion resistance are improved. In addition, since a drying process is not required, not only can the energy cost related to printing be reduced, but also the emission of volatile organic compounds (VOCs) can be reduced, which is preferable from the viewpoint of environmental compatibility.

[0083] The viscosity of the active energy ray-curable coating agent used in this embodiment may be preferably 80 to 3200 mPa·s, more preferably 100 to 2500 mPa·s, and even more preferably 200 to 2000 mPa·s at 25°C. The viscosity is measured using a Brookfield viscometer at 25°C, 6 rpm, and rotor No. 3. In some embodiments, the viscosity of the coating agent may be preferably 250 to 1500 mPa·s, more preferably 300 to 1000 mPa·s at 25°C. Having the viscosity of the coating agent within this range not only improves leveling properties, but also prevents excessive penetration of the coating agent into the substrate when applied by a method such as printing. This allows for easy development of a uniform matte finish.

[0084] (Production of Active Energy Ray-Curable Coating Agent) The method for producing the active energy ray-curable coating agent is not particularly limited. The coating agent can be produced according to a method well known to those skilled in the art. In some embodiments, the coating agent can be produced by blending 50 to 90 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 as biomass-derived monomers, and 0.2 to 2 parts by mass of additives such as a dispersant and an antifoaming agent, as appropriate, and stirring and mixing them for about 30 minutes to 3 hours using a bladed mixer (disper) or the like.

[0085] If the active energy ray-curable coating agent used in this embodiment contains unexpected coarse particles, this can cause a deterioration in the quality of the coating film. Therefore, it is preferable to remove the coarse particles by filtration or the like. A conventionally known filter can be used.

[0086] <Transparent Resin Layer> In the decorative material of this embodiment, a transparent resin layer can be provided between the intermediate layer and the surface protective layer. The transparent resin layer can be formed by applying a varnish containing a binder resin, or by printing, etc. The transparent resin layer improves the adhesion between the intermediate layer and the surface protective layer, and can easily improve durability such as abrasion resistance.

[0087] The binder resin used in the transparent resin layer may be any of the resins exemplified above as binder resins in the resin composition for forming the intermediate layer. Specific examples 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 resins 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 the resin. Furthermore, from the standpoint of environmental compatibility, it is also possible to use a resin containing a structural unit derived from biomass.

[0088] The decorative material of this embodiment has a structure of paper substrate / intermediate layer / surface protective layer, and may further have a transparent resin layer between the intermediate layer and the surface protective layer as necessary. More specifically, the decorative material may have the following configuration: Paper substrate / intermediate layer 1 (pattern layer) / intermediate layer 2 (transparent resin layer) / surface protective layer paper substrate / intermediate layer (white layer) / surface protective layer paper substrate / intermediate layer 1 (white layer) / intermediate layer 2 (pattern layer) / surface protective layer paper substrate / intermediate layer 1 (white layer) / intermediate layer 2 (pattern layer) / transparent resin layer / surface protective layer paper substrate / intermediate layer 1 (white layer) / transparent resin layer / surface protective layer

[0089] (Gloss Value) The 60° gloss value of the decorative material of this embodiment is preferably 35 or less, more preferably 30 or less, and even more preferably 25 or less. Here, the gloss value refers to the value measured from the surface protective layer side of the decorative material. Depending on the application, the 60° gloss value of the decorative material is preferably 2 or more, more preferably 5 or more. The 60° gloss value is the gloss value measured with incident light at 60° using a Micro-TRI-glossmeter manufactured by BYK-Gardner. The gloss value can be measured in accordance with the method described in JIS Z 8741:1997 for 60° specular gloss (Gs(60°)). As a sample used for measurement, an active energy ray-curable coating agent was applied to the intermediate layer with a bar coater #4 at a rate of 8 g / m. ２A decorative material is used having a surface protective layer formed from a cured film obtained by applying a coating so that the coating film has a 60° gloss of 35 or less, and then curing the coating film. In some embodiments, from the viewpoint of achieving a 60° gloss value of 35 or less, preferably 30 or less, it is preferable to adjust the content of the fine particles to 4 to 30% by mass based on the total mass of the surface protective layer (total mass of solid components in the coating agent). The content of the fine particles may be preferably 8 to 25% by mass, more preferably 10 to 23% by mass, and even more preferably 12 to 20% by mass.

[0090] 2. Manufacturing Method of a Decorative Material The decorative material of this embodiment has a substrate, an intermediate layer, and a surface protective layer in this order. One embodiment of the present invention relates to a manufacturing method of a decorative material having the above configuration. The manufacturing method of this embodiment is not particularly limited, but includes a step of forming an intermediate layer on the substrate (one side of the substrate, preferably the surface of a paper substrate), and then a step of forming a surface protective layer on the intermediate layer, and may optionally include a step of forming a transparent resin layer on the intermediate layer before the step of forming the surface protective layer.

[0091] In some embodiments, the intermediate layer can be formed by coating a resin composition (ink) on a substrate and drying the coating. In other embodiments, the intermediate layer can be formed by coating a resin composition (ink) on a substrate and irradiating the coating with active energy rays such as electron beams or ultraviolet rays to cure the coating. In still other embodiments, the intermediate layer can be formed by coating a resin composition (ink) on a substrate, subsequently applying a coating agent wet-on-wet, and then irradiating with active energy rays to simultaneously cure the coating. The intermediate layer can be formed on a paper substrate using known ink coating methods. Examples include comma coating, gravure coating, reverse coating, roll coating, lip coating, spray coating, silk screen printing, offset printing, and gravure printing. Among these, gravure printing is preferred. A similar method can also be used for the transparent resin layer, which is provided as needed.

[0092] The surface protective layer can be formed by forming an intermediate layer on a paper substrate, applying an active energy ray-curable coating agent on the intermediate layer to form a coating film (uncured layer), and then irradiating the coating film with active energy rays to cure the coating film. If a transparent resin layer is provided between the intermediate layer and the surface protective layer, the surface protective layer can be formed after the transparent resin layer is formed. 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, a decorative material for use in furniture, etc., can be constructed by bonding the paper substrate side (the back side of the paper substrate) to a wood substrate such as particle board or plywood.

[0093] The method for forming the surface protective layer using a coating agent is not particularly limited, and any known method for applying a coating agent can be used. Examples include a roll coater, gravure coater, flexo coater, air doctor coater, blade coater, air knife coater, squeeze coater, impregnation coater, transfer roll coater, kiss coater, curtain coater, cast coater, die coater, offset printing, gravure / offset printing, gravure printing, flexo printing, and screen printing. Among these, gravure / offset printing and gravure printing are preferred.

[0094] The active energy rays used to cure the coating film of the coating agent include far ultraviolet rays, ultraviolet rays, near ultraviolet rays, electron beams (EB), and proton beams. Of these, electron beams (EB) and proton beams are preferred because they can cure the coating film of the coating agent without using a polymerization initiator.

[0095] When curing a coating film by electron beam irradiation, a conventionally known curing device can be used. The electron beam irradiation dose is preferably 10 kGy to 200 kGy, more preferably 30 kGy to 100 kGy. When the irradiation dose is adjusted to 10 kGy or more, poor curing can be suppressed and curing can proceed smoothly. Furthermore, when the irradiation dose is adjusted to 200 kGy or less, the impact on the paper substrate can be easily suppressed. The acceleration voltage of the electron beam is preferably set according to the thickness and density of the coating film. In some embodiments, the acceleration voltage is preferably 50 kV to 250 kV, more preferably 75 to 125 kV.

[0096] In some embodiments, the surface protective layer has a mass per unit area of ​​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 mass of the surface protective layer is 2 g / m ２ When the mass of the surface protective layer is 15 g / m or more, the abrasion resistance tends to be good. ２ When the surface protective layer has a mass per unit area of ​​6000 kJ / cm or less, the matte property tends to be good. The mass per unit area of ​​the surface protective layer is a value calculated from the mass of the coating film (surface protective layer) after curing. The mass per unit area of ​​the surface protective layer can be adjusted by the amount of coating agent applied. As an example, the amount of coating agent applied is 6 to 10 g / m. ２ It is preferable to adjust the temperature to within the range of

[0097] Representative embodiments of the present invention include, for example, the following. <1A> A decorative material having at least an intermediate layer and a surface protective layer formed in this order on a paper substrate, wherein the intermediate layer contains a resin, and the resin contains at least one selected from the group consisting of acrylic resins and urethane resins, and the surface protective layer contains fine particles and a cured product of a (meth)acrylate, and the (meth)acrylate contains a biomass-derived (meth)acrylate. <2A> The decorative material according to <1A> above, wherein the fine particles have a D50 of 2 to 12 μm and a D95 / D50 ratio of 2.5 or less. <3A> The decorative material according to <1A> or <2A> above, wherein the resin contained in the intermediate layer contains a biomass-derived structural unit. <4A> The decorative material according to any one of <1A> to <3A> above, wherein the biomass-derived (meth)acrylate has a structure derived from at least one selected from the group consisting of fatty acids, glycerin, terpenes, and sugars. <5A> The decorative material according to any one of <1A> to <4A> above, wherein the fine particles comprise silica fine particles. <6A> The decorative material according to any one of <1A> to <5A> above, wherein the 60° gloss value is 2 to 30. <7A> A method for producing a decorative material having at least an intermediate layer and a surface protective layer, in that order, on a paper substrate, the method comprising the steps of: forming, on the paper substrate, an intermediate layer comprising at least one resin selected from the group consisting of acrylic resins and urethane resins; and applying, on the intermediate layer formed on the paper substrate, an active energy ray-curable coating agent comprising fine particles and a biomass-derived (meth)acrylate to form a coating film, and irradiating with active energy rays to cure the coating film and form a surface protective layer. <8A> The method for producing a decorative material according to <7A> above, wherein the active energy rays are electron beams.

[0098] Other examples include the following. <1B> 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, wherein the coating agent comprises a monomer and fine particles, the monomer comprises a biomass-derived monomer, and the biomass-derived monomer has a structure derived from at least one selected from the group consisting of fatty acids, glycerin, terpenes, and sugars. <2B> The active energy ray-curable coating agent according to <1B> above, wherein the particle size distribution of the fine particles is D95 / D50 of 2.3 or less. <3B> The active energy ray-curable coating agent according to <1B> or <2B> above, wherein the fine particles are silica fine particles. <4B> The active energy ray-curable coating agent according to <3B> above, wherein the oil absorption of the silica fine particles is 100 to 400 ml / g. <5B> The active energy ray-curable coating agent according to any one of <1B> to <4B> above, wherein the content of biomass-derived monomers is 60% by mass or more based on the total mass of the monomers. <6B> The active energy ray-curable coating agent according to any one of <1B> to <5B> above, wherein the content of monomers having three or more functional groups is 50% by mass or more based on the total mass of the active energy ray-curable coating agent. <7B> The active energy ray-curable coating agent according to any one of <1B> to <6B> above, which is substantially free of a polymerization initiator. <8B> A decorative material having a substrate, an intermediate layer, and a surface protective layer formed from the active energy ray-curable coating agent according to any one of <1B> to <7B> above. <9B> The decorative material according to <8B> above, wherein the substrate is a paper substrate. <10B> The mass per unit area of ​​the surface protective layer is 2 to 15 g / m ２<11B> The decorative material according to any one of <8B> to <10B> above, wherein the 60° gloss value measured from the surface protective layer side is 30 or less. <12B> A method for producing a decorative material having a substrate, an intermediate layer, and a surface protective layer, comprising the steps of forming the intermediate layer on the substrate, and applying an active energy ray-curable coating agent containing monomers and fine particles to form an uncured layer, and then irradiating the uncured layer with active energy rays to form the surface protective layer, wherein the monomers comprise biomass-derived monomers, and the biomass-derived monomers have a structure derived from at least one selected from the group consisting of fatty acids, glycerin, terpenes, and sugars.

[0099] The disclosure of this application is related to the subject matter described in Japanese Patent Application No. 2024-117504 filed on July 23, 2024, and the subject matter described in Japanese Patent Application No. 2024-188448 filed on October 25, 2024, the disclosures of all of which are incorporated herein by reference.

[0100] Hereinafter, the embodiments of the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples. In the following, unless otherwise noted, the terms "parts" and "%" represent parts by mass and % by mass.

[0101] Example A (Average Particle Diameter) In this specification, the term "average particle diameter" refers to the D50 value in the particle size distribution determined by the light scattering method, and is a value measured using a T330EXII manufactured by Microtrac Bell.

[0102] <1> Preparation of Coating Agent (Example A1) 22 parts by mass of 1,6-hexanediol diacrylate, 55.8 parts by mass of glycerin propoxy triacrylate, 20 parts by mass of silica fine particles A (average particle size 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 a stirring blade, and the mixture was stirred and mixed for 50 minutes to obtain an active energy ray-curable coating agent S1. In the stirring and mixing process, silica fine particles A was prepared by mixing the 1,6-hexanediol diacrylate and glycerin propoxy triacrylate used as binder resins, followed by adding commercially available silica fine particles A little at a time as is to carry out a pre-dispersion treatment, so that the average particle size of the silica fine particles was adjusted to fall within the specified range. The same pre-dispersion treatment was also carried out for the fine particles (silica fine particles B to E, resin beads A) used in the preparation examples described below.

[0103] Examples A2 to A16, Comparative Example A1 Using the blending amounts shown in Tables A1 and A2, active energy ray-curable coating agents S2A to S16A and T1A were obtained in the same manner as in Example A1.

[0104] <2> As a substrate for producing printed matter (decorative material), a basis weight of 30 g / m ２ A printed matter having an intermediate layer A was obtained by gravure printing an aqueous ink (50 parts of an acrylic emulsion (manufactured by Toyo Ink Co., Ltd., solid content 25%, acid value 150 mgKOH / g), 5 parts of titanium oxide, and 44 parts of water) onto a thin paper of this size. The active energy ray-curable coating agents S1A to S16A and T1A obtained in the Examples and Comparative Examples were applied to the intermediate layer A with a bar coater #4 in an amount of 8 g / m. ２ Thereafter, electron beam irradiation was carried out under the following conditions to form a surface protective layer, thereby obtaining a decorative material. Electron beam irradiation conditions: 125 kV-30 kGy-20 m / min.

[0105] The raw materials used in the examples and comparative examples are as follows. (Biomass-derived monomers) 2-hexyldecyl acrylate (functional group 1, having a fatty acid-derived structure, content of biomass-derived structure 81%) 1,10-decanediol diacrylate (functional group 2, having a fatty acid-derived structure, content of biomass-derived structure 60%) L-menthyl acrylate (functional group 1, having a terpene-derived structure, content of biomass-derived structure 73%) Isosorbide diacrylate (functional group 2, having a sugar-derived structure, content of biomass-derived structure 57%) Glycerin propoxy triacrylate (functional group 3, having a glycerin-derived structure, content of biomass-derived structure 14%) Glycerin triacrylate (functional group 3, having a glycerin-derived structure, content of biomass-derived structure 37%) Diglycerin EO-modified tetraacrylate (functional group 4, having a glycerin-derived structure, content of biomass-derived structure 30%) (Non-biomass-derived monomers) 1,6-hexanediol diacrylate (functionality: 2) Trimethylolpropane EO-modified triacrylate (functionality: 3) Dipentaerythritol hexaacrylate (functionality: 6)

[0106] (Microparticles) Silica microparticles A: average particle size 8.4 μm, oil absorption 220 mL / 100 g Silica microparticles B: average particle size 7.5 μm, oil absorption 300 mL / 100 g Organically treated silica / silica microparticles C: average particle size 4.3 μm, oil absorption 120 mL / 100 g Organically treated silica / silica microparticles D: average particle size 3.9 μm, oil absorption 250 mL / 100 g Silica microparticles E: average particle size 11 μm, oil absorption 90 mL / 100 g Resin beads A: average particle size 6 μm, oil absorption 40 mL / 100 g For silica microparticles A to E, commercially available silica microparticles were pre-dispersed with a disper for 30 minutes and a binder resin such as a monomer to confirm that the average particle size was adjusted to within the specified range before use. The average particle size is the D50 value, which is the cumulative 50% of the volume-based particle size distribution function determined by the light scattering method, and is a value measured using a T330EXII manufactured by Microtrac-Bell Co., Ltd. The average particle sizes of the silica fine particles A to E described above are values ​​measured after a preliminary dispersion treatment, and it has been confirmed that the average particle size is not affected by the type of monomer under the above dispersion conditions.

[0107] Dispersant: Polyester resin Leveling agent: Acrylic resin Antifoaming agent: Silicone resin

[0108] <3> Evaluation of decorative materials The decorative materials S1A to S16A and T1A, which were made using the active energy ray-curable coating agents S1A to S16A and T1A obtained in the Examples and Comparative Examples, were evaluated for long-run suitability, leveling ability, abrasion resistance, and matte properties using the following methods. The evaluation results are shown in Tables A1 and A2.

[0109] <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 for 1 hour using a small gravure printing machine at a printing speed of 40 m / min. The printed matter was irradiated with an electron beam under the above conditions at the beginning of printing and 1 hour after the start of printing, and the 60° gloss value of the surface protective layer of the resulting decorative material was measured in the same manner as in the evaluation of matte property described above. The rate of change in gloss value between the beginning of printing and 1 hour after the start of printing was calculated for the average gloss value obtained, and evaluated according to the following criteria. The practical level is A, B, or C. (Evaluation criteria) A: 5% or less B: More than 5% and 10% or less C: More than 10% and 20% or less D: More than 20%

[0110] <Leveling properties> The uniformity of density (presence or absence of unevenness and / or pinholes) on the surface protective layer of the decorative materials S1A to S16A and T1A was visually evaluated. "Unevenness" refers to a state in which the coating film is not formed smoothly in the process from coating to curing, and minute variations in gloss appear on the surface. "Pinholes" refers to a state in which the coating film is not formed smoothly in the process from coating to curing, and minute dot-like chips appear on the surface. The evaluation criteria are as follows, and the practical levels are A, B, or C. (Evaluation criteria) A: No printing unevenness or pinholes B: Slight printing unevenness and no pinholes C: Slight printing unevenness and pinholes D: Obvious printing unevenness and pinholes

[0111] <Abrasion Resistance> An adhesive (Cevian A, manufactured by Daicel Chemical Industries, Ltd.) was applied to the entire substrate surface of decorative materials S1A to S16A and T1A, and then the materials were attached to plywood (particle board, manufactured by Takehara Kogyo Co., Ltd.), and then laminated with a mirror-finish press plate, after which evaluation was performed. An abrasion test was performed 200 times on the surface of the decorative material using a Taber abrasion tester (abrasion wheel CS-17), and the degree of removal of the intermediate layer was evaluated visually. The evaluation criteria are as follows, and the practical levels are A, B, or C. (Evaluation Criteria) A: 90% or more of the intermediate layer remains B: 70% or more but less than 90% of the intermediate layer remains C: 50% or more but less than 70% of the intermediate layer remains D: Less than 50% of the intermediate layer remains

[0112] <Matteness> The 60° gloss value of the surface protective layer was measured five times using a gloss meter ("micro-TRI-gloss μ" manufactured by BYK-Gardner), and the average value was calculated. Evaluation was performed based on the obtained average value according to the following evaluation criteria. The practical level was A, B, or C. (Evaluation criteria) A: 20 or less B: More than 20 and 30 or less C: More than 30 and 35 or less D: More than 35

[0113]

[0114]

[0115]

[0116] Example B 1 Preparation of Coating Agent and Resin Composition (Ink) for Forming Intermediate Layer 1-1 Preparation Example of Active Energy Ray-Curable Coating Agent for Forming Surface Protective Layer (Preparation Example 1) 22 parts by weight of 1,6-hexanediol diacrylate, 55.8 parts by weight of glycerin propoxy triacrylate, 20 parts by weight of silica fine particles A, 1.5 parts by weight of dispersant, 0.5 parts by weight of leveling agent, and 0.2 parts by weight of antifoaming agent were added to a mixer equipped with a stirring blade, and the mixture was stirred and mixed for 50 minutes to obtain active energy ray-curable coating agent S1B. In the stirring and mixing process, silica fine particles A were prepared by mixing the 1,6-hexanediol diacrylate and glycerin propoxy triacrylate used as binder resins, followed by the addition of commercially available silica fine particles A in small amounts as is to carry out a pre-dispersion treatment, and adjusting the average particle diameter of the silica fine particles to fall within the specified range before use. The fine particles (silica fine particles B to E, resin beads A) used in the preparation examples described below were also subjected to a similar pre-dispersion treatment. The average particle diameter of the silica fine particles described below is a value measured after the preliminary dispersion treatment.

[0117] Preparation Examples 2 to 21 Except for changing the formulation as shown in Table B1, active energy ray-curable coating agents S2B to S21B were obtained in the same manner as in Preparation Example 1 for coating agent S1B.

[0118] Details of the raw materials listed in Table B1 are as follows: (Biomass-derived monomers) 2-hexyldecyl acrylate (functionality 1, content of biomass-derived structure 81%) 1,10-decanediol diacrylate (functionality 2, content of biomass-derived structure 60%) L-menthyl acrylate (functionality 1, content of biomass-derived structure 73%) Isosorbide diacrylate (functionality 2, content of biomass-derived structure 57%) Glycerin propoxy triacrylate (functionality 3, content of biomass-derived structure 14%) Glycerin triacrylate (functionality 3, content of biomass-derived structure 37%) Diglycerin EO (ethylene oxide)-modified tetraacrylate (functionality 4, content of biomass-derived structure 30%)

[0119] (Non-biomass-derived monomers) 1,6-hexanediol diacrylate (functionality: 2) Trimethylolpropane EO-modified triacrylate (functionality: 3) Dipentaerythritol hexaacrylate (functionality: 6)

[0120] (Fine particles) Silica fine particles A: Sylysia 450 manufactured by Fuji Silysia Chemical Ltd., average particle size 8.4 μm, D95 / D50 1.6, oil absorption 220 mL / 100 g Silica fine particles B: SYLOID C907 manufactured by W. R. Grace & Company, average particle size 7.5 μm, D95 / D50 1.7, oil absorption 300 mL / 100 g, organically treated silica Silica fine particles C: W. R. Grace & Company SYLOIDRAD2105 manufactured by Grace & Company, average particle size 4.3 μm, D95 / D50 2.1, oil absorption 120 mL / 100 g, organically treated silica. Silica fine particles D: Nipsil 220 manufactured by Tosoh Silica Corporation, average particle size 3.9 μm, D95 / D50 2.3, oil absorption 250 mL / 100 g. Silica fine particles E: Sylysia 780 manufactured by Fuji Silysia Chemical Ltd., average particle size 11 μm, D95 / D50 1.9, oil absorption 90 mL / 100 g. Resin beads A: Art Pearl GR800T manufactured by Negami Chemical Industries, Ltd., average particle size 6 μm, D95 / D50 1.6, oil absorption 40 mL / 100 g. The average particle size of each type of fine particle is the D50 value, which is the cumulative 50% of the volume-based particle size distribution function measured by light scattering, and D95 ​​is the cumulative 95% value, measured using a Microtrac-Bell T330EXII. For silica fine particles A to D, commercially available silica fine particles were pre-dispersed with a binder resin such as a monomer for 30 minutes using a disper, and it was confirmed that the average particle size D50 of the silica fine particles after the treatment was 2 to 12 μm, and that the D95 / D50 ratio of the fine particles was adjusted to 2.5 or less. It was also confirmed that the average particle size and D95 / D50 were not affected by the type of monomer under the above dispersion conditions.

[0121] (Additives) Dispersant: Polyester resin (DISPERBYK-192, manufactured by BYK Japan Co., Ltd.) Leveling agent: Acetylene glycol-based (Surfynol 104PA, manufactured by EVONIK) Antifoaming agent: Hydrophobic organic polymer (TEGO Foamex 8820, manufactured by EVONIK)

[0122]

[0123]

[0124]

[0125] <1-2> Preparation of Resin Composition for Forming Intermediate Layer (Preparation Example 1) Clear Ink P1 Clear ink P1 was obtained by adding dropwise and mixing each of the raw materials listed in Table B2 while stirring with a disper.

[0126] Preparation Examples 2 to 11: Clear inks P2 to P11 Clear inks P2 to P11 were obtained in the same manner as in Preparation Example 1 for clear ink P1, except that the formulations were changed as shown in Table B2.

[0127] (Preparation Example 12) White ink P12 While stirring with a disperser, the raw materials listed in Table B2 were added dropwise and mixed, and then dispersed with a paint shaker to obtain white ink P12.

[0128] (Preparation Examples 13 to 16) White inks P13 to P17 White inks P13 to P17 were obtained in the same manner as in Preparation Example 12 of white ink P12, except that the formulation was changed to that shown in Table B2.

[0129]

[0130] Details of the raw materials listed in Table B2 are as follows: (Binder resin) (Non-biomass-derived resin) Acrylic emulsion 1: FLX5000 manufactured by BASF Corporation, acid value 100 KOH mg / g, weight average molecular weight 20 × 10 ４ Acrylic emulsion (solid content 42%) Acrylic solution 1: BASF Corporation, JONCRYL 60J, acrylic solution (solid content 34%) with an acid value of 215 KOH mg / g and a weight-average molecular weight of 8500 Water-based urethane (PUD): Mitsui Chemicals, Inc., Takelac W-6110, weight-average molecular weight 8500 (solid content 32%) Vinyl chloride emulsion: Nissin Chemical Industry Co., Ltd., Vinyblan 701, acid value 43 KOH mg / g and a solid content 30%

[0131] (Biomass-derived resin or monomer) Acrylic emulsion 2: BASF Corporation, BRC 6824, solid content 45%, acid value of solid content 32 KOH mg / g, content of biomass-derived structural units 23% by mass Acrylic solution 2: BASF Corporation, BRC 6896, solid content 40%, acid value of solid content 87 KOH mg / g, content of biomass-derived structural units 24% by mass 1,10-Decanediol diacrylate: ARKEMA Corporation, SARBIO5201, content of biomass-derived structure 60% by mass Lauryl acrylate: ARKEMA Corporation, SARBIO5101NS, content of biomass-derived structure 80% by mass

[0132] (Coloring agent) Titanium oxide: Ti-Pure R-900 manufactured by Chemours

[0133] (Additives) Film-forming aid: Cellosolve, manufactured by Sankyo Chemical Co., Ltd. Wax: CERAFLOUR 1001, manufactured by BYK Japan Co., Ltd., content of biomass-derived structural units: 100% by mass Polymerization inhibitor: methyl hydroquinone, manufactured by Seiko Chemical Co., Ltd. Dispersant: DISPER BYK192, manufactured by BYK Japan Co., Ltd., content of biomass-derived structural units: 41% by mass Wetting agent: Surfynol 104PA, manufactured by EVONIK Corporation Antifoaming agent: Tego Foamex 8820, manufactured by EVONIK Corporation

[0134] (Preparation Example 18) Clear Ink P18 While stirring with a disper, the raw materials listed in Table B2-1 were added dropwise and mixed to obtain Clear Ink P18. (Preparation Example 19) Clear Ink P19 While stirring with a disper, the raw materials listed in Table B2-1 were added dropwise, and then dispersed with a paint shaker to obtain Clear Ink P19.

[0135] (Preparation Examples 20 to 30) White inks P20 to P30 While stirring with a disperser, each of the raw materials listed in Table B2-1 was added dropwise, and then dispersed with a paint shaker to obtain white inks P20 to P30.

[0136]

[0137] Details of the raw materials listed in Table B2-1 are as follows: (Binder resin) (Non-biomass-derived monomers) 1,6-hexanediol diacrylate (functionality: 2) Tripropylene glycol diacrylate (functionality: 2) Trimethylolpropane EO-modified triacrylate (functionality: 3) (Biomass-derived resins or monomers) Dodecyl acrylate (functionality: 1, having a fatty acid-derived structure, content of biomass-derived structure: 80%) Glycerin propoxy triacrylate (functionality: 3, having a glycerin-derived structure, content of biomass-derived structure: 14%) Diglycerin EO-modified tetraacrylate (functionality: 4, having a glycerin-derived structure, content of biomass-derived structure: 30%) (Colorant) Titanium oxide: Ti-Pure R-900, manufactured by Chemours (fine particles) Silica fine particles A: Sylysia 450 manufactured by Fuji Silysia Chemical Ltd., average particle size 8.4 μm, D95 / D50 1.6, oil absorption 220 mL / 100 g Inorganic fine particles A (mineral-based, mica, manufactured by Yamaguchi Mica Co., Ltd., Mica Powder TM-10) (additives) Wax: CERAFLOUR 1001 manufactured by BYK Japan Co., Ltd., content of biomass-derived structural units 100% by mass Dispersant: DISPER BYK192 manufactured by BYK Japan Co., Ltd., content of biomass-derived structural units 41% by mass

[0138] <3> Production of decorative material (Example B1) As a paper substrate, a basis weight of 30 g / m ２ A thin paper sheet of 100g was prepared. The surface of this thin paper sheet was gravure printed with the previously prepared clear ink P1 to form an intermediate layer. In forming the intermediate layer, the amount of ink after drying was 8g / m ２ The amount of ink applied was adjusted so that the ink was applied, and the drying conditions were 80°C for 30 seconds. The previously prepared coating agent S1B was applied to the surface of the intermediate layer of the printed matter having the tissue paper / intermediate layer (clear ink layer) configuration obtained as described above to form a coating film. Coating agent S1B was applied using bar coater #4, and the amount applied to the intermediate layer was 8 g / m. ２The printed matter having a coating film of coating agent S1B was irradiated with an electron beam at 125 kV, 30 kGy, and 20 m / min to harden the coating film and form a surface protective layer, thereby obtaining decorative material T1B. For the electron beam irradiation, an electron beam irradiation device "ELECTRONBEAM-L" manufactured by Iwasaki Electric Co., Ltd. was used. The mass per unit area of ​​the surface protective layer in decorative material T1B was 8 g / m ２ It was.

[0139] (Examples B2 to B34, Comparative Examples B1 to B3) Decorative materials T2B to T34B and T49B to T51B were obtained in the same manner as in Example B1, except that the ink forming the intermediate layer and the coating agent forming the surface protective layer were changed to the combinations shown in Table B3.

[0140] (Examples B35 to B47) In forming the intermediate layer, the ink for forming the intermediate layer was applied to form a coating film, and then the coating film was cured by irradiating it with an electron beam under conditions of 100 kV-30 kGy and 20 m / min. Except for this, decorative materials T35B to T47B were obtained in the same manner as in Example B1.

[0141] (Example B48) Coating agent S22B was prepared in the same manner as coating agent S1B used in Example B1, except that the blending amount of glycerin propoxy triacrylate in coating agent S1B used in Example B1 was changed to 52.8 parts by mass and 3 parts by mass of a polymerization initiator (Omnirad 1173 manufactured by IGM) was added. ２ A thin paper of the above formula was prepared. Gravure printing was performed on the surface of this thin paper using the previously prepared clear ink P20 to form an intermediate layer. In forming the intermediate layer, the clear ink was applied to form a coating film, and then the coating film was cured by irradiating it with an electron beam at 100 kV-30 kGy and 20 m / min. The previously prepared coating agent S22B was applied to the surface of the intermediate layer of the printed matter having the above-obtained thin paper / intermediate layer (clear ink layer) configuration to form a coating film. The coating agent S22B was applied using bar coater #4, with a coating amount of 8 g / m applied to the intermediate layer. ２The test was carried out by adjusting the amount of irradiation so that the cumulative irradiation dose was 1000 mJ / cm using a high-pressure mercury lamp on a printed matter having a coating film of coating agent S22B. ２ The coating was cured by irradiating it with ultraviolet light at a temperature of 1000 K. The coating was then cured to form a surface protective layer, thereby obtaining a decorative material T48B. Note that the high-pressure mercury lamp used was a high-pressure mercury lamp "H06-L51" manufactured by Eye Graphics Co., Ltd.

[0142] The mass per unit area of ​​the surface protective layer in the decorative materials T2B to T51B obtained as described above was 8 g / m ２ The decorative materials T2B to T24B, T30B to T33B, T35B, T36B, T49B, and T51B have a structure of thin paper / intermediate layer (clear ink layer) / surface protective layer. The decorative materials T25B to T29B, T34B, T37B to T48B, and T50B have a structure of thin paper / intermediate layer (white ink layer) / surface protective layer.

[0143] <4> Evaluation of the decorative materials The decorative materials T1B to T51B obtained in the examples and comparative examples were evaluated for various properties according to the following methods. The evaluation results are shown in Table B3.

[0144] <Matteness> The 60° gloss value of the decorative material was measured five times using a gloss meter ("micro-TRI-gloss μ" manufactured by BYK-Gardner), and the average value was evaluated as follows. The practical level is A, B, or C. The 60° gloss value is a measurement value on the surface (surface protective layer) side of the decorative material, and the value shown in Table B3 is the average value. (Evaluation criteria) A: 20 or less B: More than 20 and 30 or less C: More than 30 and 35 or less D: More than 35

[0145] <Adhesion> Crosscuts were made in the surface protective layer (cured film) of decorative materials T1B to T51B, and a cellophane tape peeling test was performed on 100 squares formed by the crosscuts in the cured film according to the method described in JIS K 5600. Of the 100 squares formed by the crosscuts, the number of squares that were not peeled off with cellophane tape (i.e., number of unpeeled squares / 100 squares) was determined and evaluated according to the following criteria. The practical level was A, B, or C. (Evaluation criteria) A: 100 unpeeled squares B: 90 to 99 unpeeled squares C: 60 to 89 unpeeled squares D: 59 or less unpeeled squares

[0146] <Leveling ability> The uniformity of density (presence or absence of unevenness and / or pinholes) in the surface protective layer of decorative materials T1B to T51B was evaluated visually. The practical level was rated as A, B, or C. Here, "unevenness" refers to a state in which the coating film is not formed smoothly in the process from coating to curing, and minute variations in gloss appear on the surface. "Pinholes" refers to a state in which the coating film is not formed smoothly in the process from coating to curing, and minute dot-like chips appear on the surface. The practical level was rated as A, B, or C. (Evaluation criteria) A: No printing unevenness or pinholes B: Slight printing unevenness and no pinholes C: Slight printing unevenness and pinholes D: Obvious printing unevenness and pinholes

[0147] <Water Resistance> The decorative materials T1B to T51B obtained in the Examples and Comparative Examples were measured according to the method related to water vapor transmission rate in the moisture permeability test of JIS Z 208, and the water resistance of the decorative materials was evaluated. The results are shown in Table B3. The evaluation criteria are as follows. The practical level is A, B, or C. (Evaluation Criteria) A: 0 to 40 g / cm ２ Less than B: 40 to 100 g / cm ２ Less than C: 100 to 400 g / cm ２ Less than D: 400 g / cm ２ End

[0148] <Oil Resistance> For the decorative materials T1B to T51B obtained in the Examples and Comparative Examples, paraffin oil was dropped onto the surface (surface protection layer) of the decorative material, and the dropped paraffin oil was wiped off after 24 hours. Next, the ratio of the area of ​​the portion of the surface protection layer where the paraffin oil had soaked into the entire surface protection layer to the area of ​​the entire surface protection layer was visually confirmed and evaluated according to the following evaluation criteria. The results are shown in Table B3. The practical level is A, B, or C. (Evaluation Criteria) A: Less than 20% B: 20% or more but less than 40% C: 40% or more but less than 80% D: 80% or more

[0149]

[0150]

[0151] As shown in Table B3, decorative materials T1B to T48B of Examples B1 to B48, which are embodiments of the present invention, are superior in various properties to comparative decorative materials T49B to T51B. Although not shown in Table 3, the abrasion resistance of decorative materials T1B to T48B of Examples B1 to B48 was evaluated, and it was confirmed that all decorative materials had abrasion resistance at or above practical levels. From these results, it can be seen that the present invention can provide decorative materials that are excellent in matte finish, adhesion, leveling, water resistance, and oil resistance.

Claims

1. A decorative material having at least an intermediate layer and a surface protective layer formed in this order on a substrate, wherein the intermediate layer is formed from a resin composition for forming an intermediate layer containing at least one selected from the group consisting of acrylic resins, urethane resins, and monomers curable with active energy rays, and the surface protective layer contains fine particles and a cured product of a (meth)acrylate, and the decorative material satisfies at least one of the following requirements (I) and (II): (I) In the surface protective layer, the (meth)acrylate contains a (meth)acrylate having a structure derived from biomass, and the (meth)acrylate having a structure derived from at least one selected from the group consisting of fatty acids, glycerin, terpenes, and sugars, and (II) In the intermediate layer, the resin composition for forming an intermediate layer contains a material having a structure derived from biomass.

2. The decorative material according to claim 1, which satisfies the above requirement (I).

3. The decorative material according to claim 1 or 2, which satisfies the requirement (II) and wherein the material having a biomass-derived structure comprises at least one selected from the group consisting of a resin having a biomass-derived structure and a (meth)acrylate having a biomass-derived structure.

4. The decorative material according to any one of claims 1 to 3, wherein the substrate is a paper substrate.

5. The decorative material according to any one of claims 1 to 4, wherein the D50 of the fine particles is 2 to 12 μm, and the D95 / D50 of the fine particles is 2.5 or less.

6. The decorative material according to any one of claims 1 to 5, wherein the fine particles include silica fine particles.

7. The decorative material according to any one of claims 1 to 6, which has a 60° gloss value of 2 to 30.

8. A method for producing a decorative material having at least an intermediate layer and a surface protective layer formed in this order on a substrate, the method comprising the steps of: forming an intermediate layer on the substrate using a resin composition for forming an intermediate layer, the resin composition containing at least one selected from the group consisting of acrylic resins, urethane resins, and monomers curable with active energy rays; and applying an active energy ray-curable coating agent containing fine particles and a (meth)acrylate to form a coating film on the intermediate layer formed on the substrate, and irradiating with active energy rays to cure the coating film and form a surface protective layer, the method satisfying at least one of the following requirements (I) and (II): (I) In the active energy ray-curable coating agent, the (meth)acrylate contains a (meth)acrylate having a structure derived from biomass, and the (meth)acrylate having a structure derived from at least one selected from the group consisting of fatty acids, glycerin, terpenes, and sugars; or (II) The resin composition for forming an intermediate layer contains a material having a structure derived from biomass.

9. A method for producing a decorative material according to claim 8, wherein the active energy ray-curable coating agent contains a (meth)acrylate having three or more functional groups, and the content of the (meth)acrylate having three or more functional groups is 50 mass% or more based on the total mass of the coating agent.

10. The method for producing a decorative material according to claim 8 or 9, wherein the active energy rays are electron beams.

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