JP2016215548A - Decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet capable of more suppressing white turbidness.SOLUTION: A decorative sheet 20 comprises, on a substrate layer 2, a symbol pattern layer 3, a gloss moderation layer 4 in which a gloss moderator is added to a transparent resin, and salient parts 5 arranged in synchronization with the symbol pattern layer 3 in the order. The gloss moderator is contained by 20 mass parts or more and 30 mass parts or less in a shape of granular particles whose particle diameter is 10 μm or less, to 100 mass% of the resin forming the gloss moderation layer 4, in the decorative sheet 20. The granular particles forming the gloss moderator are formed of two kinds of granular particles, namely, first granular particles whose particle diameter is 3 μm or less and second granular particles whose particle diameter is 5 μm or more.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a decorative sheet that can be used on surfaces of interiors, exteriors, furniture, joinery, vehicle interiors, and the like of buildings, and can give uneven feel and three-dimensionality to the surface. In particular, it is an effective technique for a decorative sheet that has excellent various resistances such as contamination resistance on the surface and has excellent design on the surface having irregularities synchronized with the pattern.

  As a decorative sheet having irregularities formed on the surface, there are decorative sheets described in Patent Documents 1 to 3, for example.

JP 2008-087158 A Japanese Patent No. 4690071 JP2013-123863A

However, in the conventional decorative sheet, there is a possibility that white turbidity visually confirmed may occur on the surface.
The present invention has been made paying attention to the above points, and an object of the present invention is to provide a decorative sheet capable of suppressing white turbidity.

In order to solve the problems, a decorative sheet according to one embodiment of the present invention is provided with a pattern layer on a base layer, a gloss adjustment layer in which a gloss adjusting agent is added to a transparent resin, and the above pattern layer. The convex portions arranged in this order are decorative sheets formed in this order, and the gloss adjusting agent is in the form of granular particles having a particle size of 10 μm or less with respect to 100 parts by mass of the resin constituting the gloss adjusting layer. The granular particles that contain 20 parts by mass or more and 30 parts by mass or less and constitute the gloss adjusting agent are two types: a first granular particle having a particle size of 3 μm or less and a second granular particle having a particle size of 5 μm or more. It is characterized by comprising the following granular particles.
Here, in this specification, the particle size refers to the average particle size.

According to the aspect of the present invention, it is possible to suppress the occurrence of white turbidity in the gloss adjusting layer by not using particles having a particle size larger than 3 μm and less than 5 μm as the granular particles of the gloss adjusting agent.
Here, although only the first granular particles having a relatively small particle diameter can prevent white turbidity, the gloss is too high. For this reason, when the particle size is within 10 μm, the first granular particles and the second granular particles separated from each other are contained, thereby preventing the occurrence of white turbidity while performing necessary gloss adjustment.

It is sectional drawing explaining the decorative sheet which concerns on embodiment based on this invention.

Next, embodiments of the present invention will be described with reference to the drawings.
Here, the drawings are schematic, and the relationship between the thickness and the planar dimensions, the ratio of the thickness of each layer, and the like are different from the actual ones. Further, the embodiment described below exemplifies a configuration for embodying the technical idea of the present invention, and the technical idea of the present invention is that the material, shape, structure, etc. of the component parts are as follows. It is not something specific. The technical idea of the present invention can be variously modified within the technical scope defined by the claims described in the claims.

As shown in FIG. 1, the decorative sheet 20 of the present embodiment is configured by forming a pattern layer 3, a transparent gloss adjusting layer 4, and a convex portion 5 in this order on a base material layer 2. A transparent contamination-resistant resin layer (not shown) may be provided as appropriate at the portion between the convex portions 5. The thickness of the contamination-resistant resin layer is preferably lower than the height of the convex portion 5 in terms of forming a three-dimensional effect due to the convex portion 5. The back surface primer layer 1 may be provided on the back surface of the base material layer 2.
Here, in the present embodiment, the term “transparent” refers to a degree of transparency that allows the pattern pattern of the lower pattern pattern layer 3 to be visually recognized from the surface of the decorative sheet 20.

<Base material layer 2>
As the base material layer 2, a conventionally known material can be used as long as it is possible to provide the pattern layer 3 by printing or the like and has processing suitability as the decorative sheet 20. The base material layer 2 is preferably a polyester resin sheet, a polyolefin resin sheet, or the like, for example, without using vinyl chloride. Various additives such as conventionally known fillers, foaming agents, flame retardants, lubricants, antioxidants, ultraviolet absorbers, and light stabilizers may be added to the base material layer 2 as necessary. The thickness of the base material layer 2 is preferably 50 μm or more and 100 μm or less, although it depends on applications.

<Pattern pattern layer 3>
The design pattern layer 3 is provided in order to impart design properties to the decorative sheet 20 by a design. The pattern layer 3 is generally formed using, for example, a gravure printing method or an offset printing method using a printing ink or a paint obtained by dissolving or dispersing a colorant such as a dye or a pigment in a suitable diluent solvent together with a suitable binder resin. It is formed by various printing methods such as a method and various coating methods such as a gravure coating method or a roll coating method. As the binder resin, for example, urethane resin, acrylic resin, vinyl chloroacetate resin, polyimide resin, nitrified cotton, or a mixture thereof is often used, but it is not limited thereto. The type of the pattern can be arbitrarily set as desired, for example, a wood grain pattern, a stone pattern, a cloth pattern, an abstract pattern, a geometric pattern, a character or a symbol, a combination thereof, or may be a solid color. In addition, in order to improve the concealing property of the decorative sheet 20, a concealing layer made of an opaque printing ink or paint containing a large amount of an opaque pigment such as titanium dioxide or iron oxide may be provided on the back side of the pattern layer 3. is there.

<Gloss adjustment layer 4>
The gloss adjusting layer 4 is formed to adjust the gloss of the surface. The gloss adjusting layer 4 has a gloss adjusting agent added to at least a transparent resin. Further, in order to improve the stain resistance, it is preferable to contain a reactive silicone resin.
As the transparent resin, a transparent thermoplastic resin layer such as an acrylic resin can be used.

For example, the gloss adjusting layer 4 is made of a thermoplastic acrylic resin containing acrylic rubber and an acrylic resin, and the mass ratio of the acrylic rubber to the acrylic resin is 30:70 to 60:40. Further, the thickness of the gloss adjusting layer 4 is preferably in the range of 20 μm to 55 μm from the viewpoint of nonflammability. An additive such as a known ultraviolet absorber may be added as appropriate.
By making the mass ratio of the acrylic rubber and the acrylic resin 30:70 to 60:40, the decorative sheet 20 and a substrate made of metal are attached by a corn calorie combustion test based on ISO5660-1. When the total calorific value with respect to time of the decorative board and the heat generation rate with respect to time were determined, (i) the total calorific value for 20 minutes after the start of heating was 8 MJ / m ² or less, and (ii) the maximum for 20 minutes after the start of heating. It is possible to ensure non-flammability satisfying the fact that the heat generation rate does not exceed 200 kW / m ² continuously for 10 seconds or more and (iii) there are no cracks and holes penetrating to the back side which is harmful for fire prevention for 20 minutes after the start of heating. .

  Here, if the mass ratio is smaller than 30:70, that is, the amount of the acrylic rubber is too small, excellent nonflammability cannot be obtained, and bending workability is deteriorated. On the other hand, if the mass ratio is larger than 60:40, that is, the amount of the acrylic rubber is too large, it is difficult to form the gloss adjusting layer 4 and the weather resistance is lowered. From such a viewpoint, the mass ratio between the acrylic rubber and the acrylic resin is preferably 30:70 to 60:40.

By including acrylic rubber, excellent bending workability can be obtained.
Thermoplastic acrylic resins include, for example, (meth) acrylate esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, ethylhexyl (meth) acrylate, etc. It is a thermoplastic resin obtained by singly or copolymerizing a main monomer as a main component. For example, acrylic monomers such as (meth) acrylonitrile and (meth) acrylic acid, styrene, α- Aromatic monomers such as methylstyrene and vinyltoluene are added as copolymerization components. For example, styrene-butadiene copolymer, methyl methacrylate-butadiene copolymer, methyl methacrylate-styrene-butadiene copolymer A rubber component such as a blend may be graft copolymerized, block copolymerized or blended. Among them, those having methyl methacrylate as a main component are most desirably used in terms of various physical properties such as weather resistance, transparency, workability, mechanical properties, and surface properties.

  The acrylic rubber is not particularly limited, but is preferably a synthetic rubber made of a polymer having at least a (meth) acrylic acid ester monomer as a structural unit. The acrylic rubber preferably contains 60% by mass or more of the structural unit, more preferably 70% by mass or more, and still more preferably 80% by mass or more. Examples of the (meth) acrylic acid ester monomer include (meth) acrylic acid alkyl ester, (meth) acrylic acid alkoxyalkyl ester, and the like.

  The (meth) acrylic acid alkyl ester is preferably an ester of an alkanol having 1 to 8 carbon atoms and (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n- (meth) acrylic acid. Propyl, n-butyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, etc. Is mentioned. Of these, ethyl (meth) acrylate and n-butyl (meth) acrylate are preferred.

  The (meth) acrylic acid alkoxyalkyl ester is preferably an ester of an alkoxyalkanol having 2 to 8 carbon atoms and (meth) acrylic acid, (meth) acrylic acid methoxymethyl, (meth) acrylic acid ethoxymethyl, (meth) 2-ethoxyethyl acrylate, 2-butoxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, (meth) Examples include 4-methoxybutyl acrylate. Among these, 2-ethoxyethyl (meth) acrylate and 2-methoxyethyl (meth) acrylate are preferable. Moreover, a polyfunctional (meth) acrylic acid ester monomer is also preferably exemplified as the (meth) acrylic acid ester monomer.

  Examples of the polyfunctional (meth) acrylic acid ester monomers include esters of unsaturated monocarboxylic acids such as (meth) acrylic acid and unsaturated alcohols such as allyl alcohol, unsaturated monocarboxylic acids and ethylene glycol, Preferable examples include diesters with glycols such as butanediol and hexanediol, and esters of dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and maleic acid with the unsaturated alcohol. More specifically, allyl (meth) acrylate, methallyl (meth) acrylate, allyl cinnamate, methallyl cinnamate, diallyl maleate, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, divinylbenzene, ethylene glycol di (Meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate and the like.

  The acrylic rubber is preferably a copolymer containing a structural unit having a crosslinking point. Since a rubber composition using such a copolymer as an acrylic rubber can be effectively crosslinked during molding, an elastic crosslinked product can be obtained. Examples of the structural unit having a crosslinking point include those having a carboxyl group, a halogen atom, an epoxy group, or a hydroxyl group.

  The shape of the acrylic rubber is not particularly limited, but a particulate shape is preferable in consideration of workability. When the acrylic rubber is in the form of particles, the average particle size is preferably 30 to 150 nm, more preferably 40 to 120 nm, considering the moldability of the transparent acrylic resin layer. The acrylic resin used in the acrylic resin layer is not particularly limited, but is preferably a polymer having at least a (meth) acrylic acid ester monomer as a structural unit. More specifically, a homopolymer of (meth) acrylate monomer, a copolymer of two or more different (meth) acrylate monomers, or a copolymer of (meth) acrylate monomers with other monomers. Polymers are preferred.

  Here, examples of the (meth) acrylate monomer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, cyclohexyl (meth) acrylate, and normal butyl (meth) acrylate. , Isobutyl (meth) acrylate, secondary butyl (meth) acrylate, tertiary butyl (meth) acrylate, isobonyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2- Adamantyl (meth) acrylate and the like are preferable, and methyl (meth) acrylate is more preferable in consideration of bending workability and weather resistance.

Examples of the copolymer of two or more different (meth) acrylic acid ester monomers include a copolymer of two or more (meth) acrylic acid esters selected from those exemplified above, and these copolymers May be a random copolymer or a block copolymer.
The other monomer that forms a copolymer with the (meth) acrylic acid ester monomer is not particularly limited as long as it is copolymerizable with the (meth) acrylic acid ester, but in the present invention, (meth) acrylic acid, Styrene, maleic anhydride, fumaric acid, divinylbenzene, vinylbiphenyl, vinylnaphthalene, diphenylethylene, vinyl acetate, vinyl chloride, vinyl fluoride, vinyl alcohol, acrylonitrile, acrylamide, butadiene, isoprene, isobutene, 1-butene, Alicyclic olefin monomers such as 2-butene, N-vinyl-2-pyrrolidone, dicyclopentadiene, ethylidene norbornene, norbornene, vinylcaprolactam, citraconic anhydride, maleimides such as N-phenylmaleimide, vinyl ethers, etc. It is preferably exemplified, in particular styrene and (anhydrous) maleic acid is preferable as a copolymerization component. That is, a binary copolymer of (meth) acrylic acid ester and styrene or (anhydrous) maleic acid, or a terpolymer of (meth) acrylic acid ester, styrene and (anhydrous) maleic acid is preferable. In addition, the copolymer of (meth) acrylic acid ester and another monomer may be a random copolymer or a block copolymer.

In addition, from the viewpoint of versatility of bonding with various transparent thermoplastic resin layers, deformation followability when the decorative sheet 20 is bent into the conduit groove, and scratch resistance, the resin component (binder resin) is two-component cured. Type urethane resin is preferred.
The two-component curable urethane resin is a urethane resin mainly composed of polyol and isocyanate as a crosslinking agent (curing agent). As the polyol, one having two or more hydroxyl groups in the molecule, for example, polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, polyether polyol, polycarbonate polyol, polyurethane polyol and the like are used. As the isocyanate, a polyvalent isocyanate having two or more isocyanate groups in the molecule is used. For example, aromatic isocyanates such as 2,4-tolylene diisocyanate, xylene diisocyanate, 4,4'-diphenylmethane diisocyanate, or 1,6-hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, etc. Aliphatic (or alicyclic) isocyanates are used. Alternatively, adducts or multimers of the above various isocyanates can be used. For example, there are tolylene diisocyanate adducts, tolylene diisocyanate trimers, and the like. Of the above-mentioned isocyanates, aliphatic (or alicyclic) isocyanates are preferred in that they can be well weathered and heat-resistant yellowed. Specifically, for example, 1,6-hexamethylene diisocyanate can be used.

  The gloss adjusting agent is also called a matting agent or a matting agent, and is added according to the gloss given to the surface of the decorative sheet 20. Examples of the gloss adjusting agent include inorganic substances such as silica, alumina (α-alumina, etc.), calcium carbonate, barium sulfate, kaolinite, aluminosilicate, and organic (resin) fine particles such as polycarbonate, nylon, and urethane resin. Of these, silica is preferred.

The average particle size of the gloss adjusting agent is preferably 1 μm or more and 10 μm or less. The addition amount of the gloss adjusting agent is appropriately selected according to the desired gloss, but usually 20 parts by mass in the form of granular particles having a particle size of 10 μm or less with respect to 100 parts by mass of the resin constituting the gloss adjusting layer 4. It is added in the range of 30 parts by mass or less.
In the present embodiment, two types of granular particles, a first granular particle having a particle size of 3 μm or less and a second granular particle having a particle size of 5 μm or more, are used as the granular particles constituting the gloss adjusting agent. .

That is, the first granular particles having a relatively small particle size and the second granular particles having a relatively large particle size are used.
In addition, the mixing ratio of the first granular particles and the second granular particles is such that the first granular particles are relatively larger. The blending ratio between the first granular particles and the second granular particles is preferably in the range of 6: 4 to 8: 2.

Here, the inventors have confirmed the following and arrived at the present invention.
That is, when the particle size of the gloss adjusting agent is reduced to 3 μm or less, white turbidity in the gloss adjusting layer 4 can be suppressed, and the more the gloss adjusting agent having a particle size larger than 3 μm and less than 5 μm, the more white turbidity occurs. Confirmed that it was easy. For this reason, in this embodiment, in order to suppress the gloss adjusting agent having a particle size larger than 3 μm and less than 5 μm, the first granular particles having a particle size of 3 μm or less as the gloss adjusting agent, Two types of granular particles are used together with second granular particles having a particle size of 5 μm or more. However, since it is an average particle diameter, there is a possibility that a gloss adjusting agent having a particle diameter larger than 3 μm and smaller than 5 μm may be mixed, but by using the above two kinds of granular particles, It is possible to greatly reduce the gloss adjusting agent having a diameter larger than 3 μm and smaller than 5 μm.

  Moreover, although it discovered that there was an effect of cloudiness, so that there were many 1st granular particles, since it also confirmed that only the 1st granular particle glossed too much, from a viewpoint of performing desired gloss adjustment, it is relative. Also contained second granular particles having a large particle size. However, it mix | blends so that the 1st granular particle may increase. Furthermore, it is preferable to set the blending ratio of the first granular particles and the second granular particles in the range of 6: 4 to 8: 2. Here, it is preferable in terms of design that a gloss adjusting agent is added so that the gloss of the mat portion is about 3 to 5 in terms of the reflection gloss coefficient.

Here, it is preferable that the oil absorption rate of the first granular particles is relatively higher than the oil absorption rate of the second granular particles.
Oil absorption is realizable by using porous, that is, porous granular particles. The oil absorption rate increases as the aperture ratio per unit area increases.
And when the founders confirmed, since it confirmed that the one where the oil absorption rate of the 1st granular particle is relatively higher than the oil absorption rate of the 2nd granular particle has contributed to white turbidity prevention, it is the above-mentioned. It was prescribed as follows.

The gloss adjusting layer 4 preferably contains 10 to 50 parts by mass of a reactive silicone resin with respect to 100 parts by mass of the resin. The gloss adjusting layer 4 includes a reactive silicone resin, thereby providing stain resistance.
Examples of the reactive silicone resin include materials having a silicon skeleton in the main chain, silicone oil used for a mold release agent, etc., and in particular, the side chain has a silicon skeleton in terms of contamination resistance. UV effect acrylate resins are preferred. If the content of the reactive silicone resin is less than 10 parts by mass, the stain resistance tends to deteriorate, and if it exceeds 50 parts by mass, problems such as poor adhesion to the base material layer 2 due to silicone bleed out may occur. There is sex.

Here, the inventors have confirmed that when the reactive silicone resin is not evenly mixed in the gloss adjusting layer 4 and is segregated and mixed, it tends to be cloudy. Therefore, when the reactive silicone resin is well stirred and the reactive silicone resin is dispersed and mixed in the gloss adjusting layer 4 at a dispersion ratio of 70% or more, preferably 80% or more, the reactive silicone resin is obtained. It was confirmed that the segregation of the water was suppressed and contributed to the suppression of white turbidity.
In addition, glass beads having a particle size of 10 μm or less may be appropriately mixed in order to ensure the hardness as a flooring material. The same applies to the convex portion 5 described later.

<Convex part 5>
The convex portion 5 is made of an ionizing radiation curable resin such as an ultraviolet curable resin. The protrusions 5 are formed so that the height is 30 μm or more and 100 μm or less and the distance between the protrusions 5 is in the range of 1 mm or more and 2 mm or less. Moreover, what contains 20-30 mass parts of granular particles with a particle size of 3-10 micrometers with respect to 100 mass parts of ionizing radiation-curable resins of the said convex part 5 is used.

The convex portion 5 may adjust the gloss similarly to the gloss adjusting layer 4.
Ionizing radiation curable resins include those having energy quanta capable of crosslinking and polymerizing molecules in electromagnetic waves or charged particle beams, that is, resin compositions that are crosslinked and cured by irradiation with ultraviolet rays or electron beams. Point to. Specifically, it can be appropriately selected from polymerizable monomers and polymerizable oligomers or prepolymers conventionally used as ionizing radiation or ultraviolet curable resin compositions.

  Typically, a (meth) acrylate monomer having a radical polymerizable unsaturated group in the molecule is suitable as the polymerizable monomer, and among them, a polyfunctional (meth) acrylate is preferable. Here, “(meth) acrylate” means “acrylate or methacrylate”. The polyfunctional (meth) acrylate is not particularly limited as long as it is a (meth) acrylate having two or more ethylenically unsaturated bonds in the molecule. Specifically, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meta) ) Acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified diphosphate ( (Meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylo Propane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris ( Acryloxyethyl) isocyanurate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, etc. Is mentioned. These polyfunctional (meth) acrylates may be used singly or in combination of two or more.

  Along with the polyfunctional (meth) acrylate, a monofunctional (meth) acrylate can be appropriately used in combination as long as the object of the present invention is not impaired for the purpose of reducing the viscosity. Examples of monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl ( Examples include meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and isobornyl (meth) acrylate. These monofunctional (meth) acrylates may be used alone or in combination of two or more.

  Examples of the polymerizable oligomer include oligomers having a radical polymerizable unsaturated group in the molecule, such as epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, and polyether (meth) acrylate. Can be mentioned. Here, the epoxy (meth) acrylate oligomer can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it. . Further, a carboxyl-modified epoxy (meth) acrylate oligomer obtained by partially modifying this epoxy (meth) acrylate oligomer with a dibasic carboxylic acid anhydride can also be used. The urethane (meth) acrylate oligomer can be obtained, for example, by esterifying a polyurethane oligomer obtained by reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid. Polyester (meth) acrylate oligomers include, for example, esterifying hydroxyl groups of polyester oligomers having hydroxyl groups at both ends obtained by condensation of polycarboxylic acid and polyhydric alcohol with (meth) acrylic acid, It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide to a carboxylic acid with (meth) acrylic acid. The polyether (meth) acrylate oligomer can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid.

  Other polymerizable oligomers include polybutadiene (meth) acrylate oligomers with high hydrophobicity that have (meth) acrylate groups in the side chain of polybutadiene oligomers, silicone (meth) acrylate oligomers with polysiloxane bonds in the main chain, small Aminoplast resin (meth) acrylate oligomer modified by aminoplast resin with many reactive groups in the molecule, or novolak type epoxy resin, bisphenol type epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc. There are oligomers having a polymerizable functional group.

Moreover, various additives can be mix | blended with the convex part 5 which consists of ionizing radiation curable resin according to a desired physical property. Examples of this additive include a weather resistance improver, an abrasion resistance improver, a polymerization inhibitor, a crosslinking agent, an infrared absorber, an antistatic agent, an adhesion improver, a leveling agent, a thixotropic agent, a coupling agent, A plasticizer, an antifoamer, a filler, a solvent, a coloring agent, etc. are mentioned.
The shape of the convex portion 5 is not particularly limited, and may be a regular shape such as a regular array of circles, squares, and hexagons, an irregular pattern, or a tactile sensation when the pattern is irregular. Further, it is preferable because it is excellent in mat feeling, glossiness and design. Moreover, a real feeling is acquired by synchronizing the convex part 5 with the pattern pattern layer 3. FIG.

  It is preferable to contain 10 to 50 parts by mass of reactive silicone resin in the convex part 5. Examples of the reactive silicone resin include materials having a silicon skeleton in the main chain, silicone oil used for a mold release agent, etc., and in particular, the side chain has a silicon skeleton in terms of contamination resistance. UV effect acrylate resins are preferred. If the content of the reactive silicone resin is less than 10 parts by mass, the stain resistance tends to deteriorate, and if it exceeds 50 parts by mass, problems such as poor adhesion to the substrate due to bleed out of silicon may occur. is there. Or if it is the same as resin used for the antifouling thin film coating resin layer mentioned later, the surface will consist of the same resin, and will become preferable.

<Contamination-resistant thin film coating resin layer>
The contamination-resistant thin film coating resin layer is composed of a contamination-resistant material having a layer thickness of 0.5 to 1.5 μm. Although it does not specifically limit as resin used for an antifouling thin film coating resin layer, A blocked isocyanate hardening type urethane system resin is used suitably. If the layer thickness is less than 0.5 μm, a sufficient anti-contamination effect cannot be obtained, and if the layer thickness is more than 1.5 μm, the three-dimensional effect and the design are impaired.

<Backside primer layer 1>
The back primer layer 1 may not be provided.
The decorative sheet 20 is used by being attached (laminated) to the surface of various base materials such as a woody base material and an inorganic base material. An appropriate adhesive such as urethane or vinyl acetate is used. At this time, depending on the material of the base material layer 2 (for example, when it is an olefin resin film), the adhesiveness with the general adhesive for laminating may be insufficient. In such a case, it is preferable to provide the back surface primer layer 1 made of a resin composition excellent in adhesiveness with a general laminating adhesive on the back surface of the base material layer 2.

  As the backside primer layer 1, various primer agents such as urethane-based, polycarbonate-based resin, acrylic-based, ethylene-vinyl acetate copolymer system, vinyl chloride-vinyl acetate copolymer system are known. What is necessary is just to select and use the thing match | combined with the material of the base material layer 2. FIG. In addition, when powders, such as a silica, an alumina, a calcium carbonate, barium sulfate, are added to the back surface primer layer 1, the surface of the back surface primer layer 1 will be roughened, and when the decorative sheet 20 is wound and stored, for example. In addition to preventing blocking, it is possible to improve the adhesiveness with the laminating adhesive due to the anchoring effect.

  In the decorative sheet 20 of the present embodiment, the gloss adjusting layer 4 is provided on the pattern layer 3 in order to make it appear uneven after the pattern layer 3 having a touch feeling is provided by printing or the like. The three-dimensional effect was given by providing. Furthermore, in the decorative sheet 20 of this embodiment, the convex part 5 synchronized with the design pattern is provided by engraving printing or the like to form physical irregularities to give a more three-dimensional effect.

Further, by specifying the particle size of the gloss adjusting agent to be added to the gloss adjusting layer 4, even if silica is used as the gloss adjusting agent, for example, the white turbidity due to the addition of the gloss adjusting agent is suppressed, and the transparency is improved. It is possible to ensure a three-dimensional effect without impairing the central design. That is, the occurrence of white turbidity on the sheet surface can be suppressed while ensuring a desired glossy state on the sheet surface.
Here, as described later, the inventors have confirmed that white turbidity cannot be detected by a glossiness test or a color difference test, and can be detected by a visual appearance sensory test.

Next, examples of the present invention will be described.
<Example 1>
The base material layer 2 was formed using 76.2 g / m ^{2 of} PBT (polybutylene terephthalate) resin (60OK0802 manufactured by Okura Kogyo Co., Ltd.). The thickness of the base material layer 2 is 0.06 mm.

On the base material layer 2, the pattern layer 3 was formed by printing. As a printing ink, a urethane / vinyl chloride resin (V351UR-T manufactured by Toyo Ink Co., Ltd.) was used and the ink coating amount was adjusted to 1.8 g / m ² .
Furthermore, the gloss adjusting layer 4 was formed on the pattern layer 3 (the surface of the base material layer 2 for the part having no pattern).

The gloss adjusting layer 4 is a two-part curable urethane resin G-XA manufactured by DIC Graphics, Inc. with respect to UV178 Himat (containing acrylic resin and gloss adjusting agent) manufactured by DIC Graphics Co., Ltd. A liquid containing an additive WGRNT manufactured by DIC Graphics Co., Ltd. was applied and dried at a coating amount of 4.1 g / m ² .
As described above, in the gloss adjustment layer 4 of Example 1, the mass ratio of acrylic resin: two-component curable urethane resin: glass beads was 100: 10: 5. The particle size of the glass beads is 6-7 μm.

Silica as the gloss adjusting agent is composed of only two types, A type having a particle size of 2 μm to 3 μm and B type having a particle size of 5 μm to 6 μm, and the mass ratio of A type to B type was set to 2: 1. The A type contained 8-9% and the B type contained 4-5% with respect to the whole main resin.
Here, the UV178 hi-mat constituting the gloss adjustment 4 includes 15 parts of G-UV315ST in the main resin. Further, 5 parts of additive EX40205 was added. The additive contains a reactive silicone resin and is dispersed in the gloss adjusting layer 4 at a dispersion ratio of 70% or more.

Furthermore, the convex part 5 was formed on the gloss adjustment layer 4 by raising.
Convex part 5 is UV117 gloss (acrylic resin) / UV117 Himat (acrylic resin + silica etc.) / Additive G-UV315ST (silicone-modified urethane acrylate resin etc., antifoaming agent) manufactured by DIC Graphics Co., Ltd. / Additive G-UV120GR is formed by applying a mixture of 33.3 parts by mass / 66.7 parts by mass / 10 parts by mass / 20 parts by mass at a coating amount of 1.15 g / m ^2. did.
Further, a two-component cured urethane resin (silica added) was applied to the back surface of the base material layer 2 at 1.2 g / m ² to form the back primer layer 1.

<Comparative example 1>
Except for the configuration of the gloss adjusting layer 4, it was formed in the same manner as in the first embodiment.
The gloss adjustment layer 4 of Comparative Example 1 is made of 164 Graphics UV164 Hi-Mat (including silica as an acrylic resin gloss adjustment agent) / urethane curing agent G-XA / additive G-UV315ST / additive WGRNT. Were mixed at a ratio of 100 parts by mass / 17 parts by mass / 15 parts by mass / 5 parts by mass to form a liquid, and applied and dried at an application amount of 4.1 g / m ² .

Here, the particle size of the silica contained in the gloss adjusting layer 4 of Comparative Example 1 is the A type having a particle size of 2 μm to 3 μm, the C type having a particle size of 3 to 4 μm, and the B type having a particle size of 5 μm to 6 μm. Three types are mixed, and the ratio of A: B: C is almost 1: 1: 1. In addition, it was in the state which contained about 4 to 5% of each type of silica with respect to the whole application quantity.
In addition, in the gloss adjustment layer 4 of the comparative example 1, it is estimated that the dispersion rate of the additive containing the reactive silicone resin is about 50 to 60%.

<Comparative example 2>
It is the same as Comparative Example 1 except that the amount of the additive G-UV315ST in the liquid forming the gloss adjusting layer 4 of Comparative Example 1 is reduced by 5 parts by mass. By reducing the amount of the additive G-UV315ST by 5 parts by mass, the comparative example 2 has fewer additives including the reactive silicone resin than the comparative example 1.

<About evaluation>
The following evaluation judgment was implemented with respect to Example 1 and Comparative Examples 1 and 2.
"Surface gloss measurement>
The 60 ° surface glossiness was measured according to JIS Z 8741: 1997 “Specular Glossiness—Measurement Method”.

The measurement was performed so that the positions of the pattern patterns in Example 1 and Comparative Examples 1 and 2 were the same for each sample, and measurement was performed at 10 positions to obtain an average value.
The measurement results are shown in Table 1.

As can be seen from Table 1, no significant difference was detected in glossiness.
"Measurement of color difference"
Based on the L * a * b * color system (International Lighting Commission ICE1976), the color difference meter CR-300 was measured using a measuring head aperture of 80 mmφ.
The measurement was performed so that the positions of the pattern patterns in Example 1 and Comparative Examples 1 and 2 were the same for each sample, and measurement was performed at 10 positions to obtain an average value.
The measurement results are shown in Table 2.

As can be seen from Table 2, no significant difference was detected in the color difference.
"Visual appearance sensory test"
Ten samples were visually confirmed for each sample.
Evaluation was as follows.
○ Almost no turbidity Pass △ The cloudiness can be slightly grasped. Pass × Cloudy Evaluation results are shown in Table 3.

As can be seen from Table 3, Example 1 in which C-type silica is excluded and A-type silica is increased, can be seen that white turbidity is greatly suppressed as compared with Comparative Examples 1 and 2. Compared with Comparative Example 2, white turbidity is suppressed, which is presumed to be because the amount of silicone having a dispersion rate of 60% or less was reduced.
On the other hand, in Example 1, it turned out that white turbidity can be suppressed, without reducing the quantity of the silicone which has the effect of stain resistance.
Here, in Example 1, the blend of A type silica and B type silica was adjusted to 2: 1, but when the blend of A type silica and B type silica was 6: 4, Even in the case of 8: 2, it was confirmed that white turbidity was significantly suppressed as compared with Comparative Examples 1 and 2.

DESCRIPTION OF SYMBOLS 1 Back surface primer layer 2 Base material layer 3 Picture pattern layer 4 Gloss adjustment layer 5 Convex part 20 Cosmetic sheet

Claims (8)

On the base material layer, a design pattern layer, a gloss adjustment layer in which a gloss adjusting agent is added to a transparent resin, and a convex portion arranged in synchronization with the design pattern layer are formed in this order,
The gloss adjusting agent contains 20 parts by mass or more and 30 parts by mass or less in the form of granular particles having a particle size of 10 μm or less with respect to 100 parts by mass of the resin constituting the gloss adjustment layer.
The granular particles constituting the gloss adjusting agent are composed of two types of granular particles, a first granular particle having a particle size of 3 μm or less and a second granular particle having a particle size of 5 μm or more. Sheet.   The decorative sheet according to claim 1, wherein a blending ratio of the first granular particles to the second granular particles is in a range of 6: 4 to 8: 2.   The decorative sheet according to claim 1 or 2, wherein the oil absorption rate of the first granular particles is higher than the oil absorption rate of the second granular particles.   The decorative sheet according to any one of claims 1 to 3, wherein the gloss adjusting layer contains a two-component curable urethane resin.   The decorative sheet according to any one of claims 1 to 4, wherein the gloss adjusting layer contains 10 to 50 parts by mass of a reactive silicone resin with respect to 100 parts by mass of the resin.   The decorative sheet according to claim 5, wherein the reactive silicone resin is dispersed and mixed in the gloss adjusting layer 4 at a dispersion ratio of 70% or more.   The convex part is made of an ionizing radiation curable resin and contains 20 to 30 parts by mass of granular particles having a particle size of 3 to 10 μm with respect to 100 parts by mass of the resin constituting the convex part. The decorative sheet according to any one of claims 1 to 6. The decorative sheet according to any one of claims 1 to 7, wherein a transparent contamination resin layer is provided on a surface of the gloss adjusting layer on which the convex portion is not formed.

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