WO2020067565A1 - Decorative sheet - Google Patents

Decorative sheet Download PDF

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Publication number
WO2020067565A1
WO2020067565A1 PCT/JP2019/038477 JP2019038477W WO2020067565A1 WO 2020067565 A1 WO2020067565 A1 WO 2020067565A1 JP 2019038477 W JP2019038477 W JP 2019038477W WO 2020067565 A1 WO2020067565 A1 WO 2020067565A1
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WO
WIPO (PCT)
Prior art keywords
resin
protective layer
decorative sheet
surface protective
layer
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Application number
PCT/JP2019/038477
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French (fr)
Japanese (ja)
Inventor
真友子 小紫
脩 後藤
沙織 宮▲崎▼
Original Assignee
大日本印刷株式会社
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Application filed by 大日本印刷株式会社 filed Critical 大日本印刷株式会社
Priority to JP2020549512A priority Critical patent/JP7351309B2/en
Publication of WO2020067565A1 publication Critical patent/WO2020067565A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic

Definitions

  • the present disclosure is mainly used for a building interior member and a building exterior member, and relates to a decorative sheet having a resin base material and a surface protective layer, and having excellent long-term weather resistance.
  • Patent Document 1 discloses a coating agent used for manufacturing a decorative sheet having a surface protective layer as an outermost surface layer on a substrate sheet, wherein the surface protective layer is a cured coating film of the coating agent,
  • the agent contains silica and an ionizing radiation-curable resin, and the silica has a pore volume of 1.8 mL or more and 3.0 mL or less, and an apparent specific gravity of 0.05 g / mL or more and 0.22 g / mL or less.
  • a coating agent characterized by having an oil absorption of 300 mL / 100 g or more. The document describes that the use of matting silica having the above pore volume, apparent specific gravity and oil absorption makes it difficult for sedimentation and convection of matting silica to occur in a coating agent and a coating film of the coating agent. ing.
  • Patent Document 2 discloses a gel-processed silica having a BET specific surface area of 250 to 350 m 2 / g and an average particle size of 1 ⁇ m by a Coulter counter method.
  • a matte silica for a top coat characterized in that coarse particles having a size of 2 to 1.8 ⁇ m and not having a size of 8 ⁇ m or more are present and particles having a size of 1 ⁇ m or less account for 10 to 30% of the whole.
  • the document states that the use of the matte silica for a top coat can provide a top coat having excellent dispersibility and a high matting effect, and thus having an excellent coating film appearance.
  • Patent Document 3 discloses an active energy ray-curable oligomer (excluding silicone (meth) acrylate) and / or an active energy ray-curable monomer, a silicone (meth) acrylate, and an oil absorption of 95 to 250 mL / 100 g.
  • a decorative sheet using an active energy ray-curable composition containing certain surface-untreated silica as a surface protective layer is disclosed. This document describes effects that are excellent in cellophane tape peeling resistance, solvent resistance, chemical resistance, and stain resistance.
  • Patent Literature 1 has no description about deterioration of the design property over time.
  • Patent Document 2 points out that the use of silica makes the coating film whitish, it does not disclose any study on the temporal change in the transparency of the coating film.
  • Patent Literature 3 evaluates the appearance of the coating liquid after one week has passed (Table 1), but does not mention any change with time in the design properties after processing into a decorative sheet (see Tables 2 and 3). .
  • the present disclosure has been achieved in view of the above-mentioned circumstances regarding the long-term weather resistance of a decorative sheet, and has a resin substrate and a surface protective layer, has an excellent matting effect, and hardly causes whitening in the surface protective layer. It is intended to provide a decorative sheet.
  • the decorative sheet of the present disclosure includes a resin substrate, and a surface protection layer on at least one surface side of the resin substrate, wherein the surface protection layer is a cured product of a curable resin, and is manufactured by a gel method, Further, it is characterized by containing silica fine particles having an oil absorption of 100 mL / 100 g or more and 280 mL / 100 g or less.
  • the particle diameter (D50) of the silica fine particles may be 1 ⁇ m or more and 20 ⁇ m or less.
  • the surface protective layer contains silica fine particles produced by a gel method and having a specific range of oil absorption, a decorative sheet capable of achieving both excellent matting effect and whitening suppression effect after long-term use. Is obtained.
  • FIG. 1 is a schematic cross-sectional view of a first embodiment of a decorative sheet of the present disclosure. It is a cross section of a 2nd embodiment of the decorative sheet of this indication. It is a cross section of a 3rd embodiment of a decorative sheet of the present disclosure.
  • the decorative sheet of the present disclosure includes a resin substrate, and a surface protection layer on at least one surface side of the resin substrate, wherein the surface protection layer is a cured product of a curable resin, and is manufactured by a gel method, Further, it is characterized by containing silica fine particles having an oil absorption of 100 mL / 100 g or more and 280 mL / 100 g or less.
  • the present inventors have discovered, for the first time, a problem that the surface protective layer containing silica whitens due to long-term use.
  • the present disclosure relates to a decorative sheet that can solve such a problem of long-term weather resistance.
  • An outline of the solution mechanism is to combine an excellent matting effect and an effect of suppressing whitening after long-term use by blending silica fine particles produced by a gel method and having an oil absorption in the above specific range into the surface protective layer. That is.
  • the configuration of the decorative sheet will be described in detail.
  • Resin base material The resin base material is not particularly limited as long as it has a strength capable of maintaining the shape of the decorative sheet.
  • the resin contained in the resin substrate include polyolefin resins such as polyethylene, polypropylene, olefin-based thermoplastic elastomers and ionomers; vinyl resins such as vinyl chloride resin, vinylidene chloride resin, polyvinyl alcohol, and ethylene-vinyl alcohol copolymer.
  • Polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene glycol-terephthalic acid-isophthalic acid copolymer, polyester-based thermoplastic elastomer; polymethyl methacrylate, polymethyl methacrylate, polymethacrylic acid Acrylic resins such as ethyl; polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS resin), cellulose triacetate, polycarbonate and the like.
  • ABS resin acrylonitrile-butadiene-styrene copolymer
  • the resin base material may have been subjected to corona treatment on one surface or both surfaces in advance.
  • a plasticizer used for the purpose of imparting flexibility to the resin base material and controlling its hardness.
  • phthalic acid esters such as dioctyl phthalate, trimellitic acid esters such as trioctyl trimellitate, adipic acid esters, adipic acid polyesters, phthalic polyesters, phosphorus Acid esters, citrates, benzoates, terephthalates, epoxidized vegetable oils, chlorinated paraffins and the like can be mentioned.
  • the content of the plasticizer is not particularly limited, and may be, for example, 5 to 60 parts by mass, preferably 15 to 35 parts by mass with respect to 100 parts by mass of the resin constituting the resin base material.
  • the resin base material may contain a coloring agent.
  • the colorant causes at least one surface of the resin substrate to be colored to a desired hue.
  • coloring agents include inorganic pigments such as titanium white, zinc white, red petals, vermilion, ultramarine blue, cobalt blue, graphite, titanium yellow, and carbon black, isoindolinone, Hansa Yellow A, quinacridone, permanent red 4R, and phthalocyanine blue.
  • Azomethine azo compounds, perylene compounds, organic pigments or dyes such as nickel azo complexes, metal pigments composed of metal foil powders such as aluminum and brass, pearl luster composed of foil powders such as titanium dioxide-coated mica and basic lead carbonate
  • a conventionally known coloring pigment such as a pigment) is used.
  • the coloring may be either transparent coloring or opaque (concealing) coloring. In general, opaque coloring is good for concealing the adherend.
  • the content of the coloring agent is not particularly limited as long as the decorative sheet of the present disclosure has mechanical properties such as processability
  • the resin base material further contains a heat stabilizer, a flame retardant, a radical scavenger, an ultraviolet absorber, and the like, if necessary.
  • the heat stabilizer is a known one such as a phenol type, a sulfite type, a phenylalkane type, a phosphite type, and an amine type, and is used for further improving the prevention of deterioration such as thermal discoloration during thermal processing.
  • the flame retardant powders such as aluminum hydroxide and magnesium hydroxide are used, and these are added when it is necessary to impart flame retardancy.
  • radical scavenger examples include bis- (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis- (N-methyl-2,2,6,6-tetramethyl-4-piperidyl)
  • a hindered amine radical scavenger such as sebacate is used.
  • Examples of the ultraviolet absorber include 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-dimethylphenyl) -s-triazine and 2- (2-hydroxy-4-hexyloxyphenyl) ) -4,6-diphenyl-s-triazine and other triazines, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditertiary) Benzotriazoles such as (butylphenyl) -5-chlorobenzotriazole, benzophenones, benzoates and the like are used.
  • the content of these additives is, for example, preferably 1 to 50 parts by mass, more preferably 10 to 25 parts by mass, per 100 parts by mass of the resin constituting the resin base material.
  • a resin base material is obtained by forming a film of a mixture of a resin and, if necessary, additives such as a plasticizer by a conventional method such as a calendering method.
  • the thickness of the obtained resin base material can be appropriately set according to the material so that the strength and heat resistance are appropriate, and is generally about 1 ⁇ m to 1,000 ⁇ m, preferably 10 ⁇ m to 500 ⁇ m. .
  • the method of measuring the thickness of each layer (the resin base material and the surface protection layer, and, if necessary, the picture layer, the transparent resin layer, etc.) constituting the decorative sheet of the present disclosure is as follows. First, the cross section of the decorative sheet is observed with an optical microscope or an electron microscope. The thickness of the layer to be measured is measured at about 3 to 10 places, and the average of the calculated thickness is defined as the thickness of the layer.
  • the surface protective layer contains a cured product of a curable resin and specific silica fine particles.
  • the curable resin that can be used for the surface protective layer include a thermosetting resin and an ionizing radiation curable resin, and these may be used in combination. After applying a composition containing these resins and specific silica fine particles described below to the surface of the resin substrate, or the surface of a laminate including the resin substrate, curing the resin by applying heat or irradiating with ionizing radiation. Thereby, a surface protective layer can be formed. From the viewpoint of increasing the crosslink density of the resin forming the surface protective layer and improving the scratch resistance and abrasion resistance of the surface protective layer surface, ionizing radiation-curable resins are preferred.
  • an electron beam-curable resin is more preferable because it can be applied without a solvent and is easy to handle.
  • a thermosetting resin for example, a urethane resin, an epoxy resin, a polysiloxane resin, or the like can be used.
  • a two-part curable urethane resin having good properties such as flexibility of the obtained coating film and durability such as chemical resistance is particularly preferable.
  • the two-component curable urethane resin is a urethane resin having a polyol as a main component and an isocyanate as a crosslinking agent (curing agent), and the polyol is a compound having two or more hydroxyl groups in a molecule.
  • polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, polyether polyol, polycarbonate polyol, polyurethane polyol and the like are used.
  • isocyanate a polyvalent isocyanate having two or more isocyanate groups in a molecule is used.
  • aromatic isocyanates such as 2,4-tolylene diisocyanate, xylene diisocyanate, and 4,4'-diphenylmethane diisocyanate, or 1,6-hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, etc.
  • (Or alicyclic) isocyanates of the formula (1) there are adducts or multimers of the above-mentioned various isocyanates, for example, adducts of tolylene diisocyanate, trimers of tolylene diisocyanate, and the like.
  • the ionizing radiation-curable resin include radically polymerizable unsaturated groups such as a (meth) acryloyl group, a (meth) acryloyloxy group, and an epoxy group in a molecule as conventionally used as an ionizing radiation-curable resin.
  • polymerizable monomers and polymerizable oligomers (or prepolymers) having a cationic polymerizable functional group and the like examples include monofunctional (meth) acrylates such as methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and phenoxyethyl (meth) acrylate, and diethylene glycol di ( (Meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropanetetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipenta And polyfunctional (meth) acrylates such as erythritol
  • Examples of the polymerizable oligomer having a (meth) acryloyl group in the molecule include urethane (meth) acrylate oligomer, epoxy (meth) acrylate oligomer, polyester (meth) acrylate oligomer, polyether (meth) acrylate oligomer, and acryl (meth) ) Acrylate oligomers and the like.
  • (meth) acrylate” means acrylate or methacrylate.
  • prepolymer having a cationically polymerizable functional group in the molecule examples include bisphenol epoxy resins, epoxy resins such as novolak epoxy compounds, and prepolymers of vinyl ether resins such as fatty acid vinyl ethers and aromatic vinyl ethers.
  • ionizing radiation means electromagnetic waves or charged particles having energy capable of polymerizing and curing molecules, such as all ultraviolet rays (UV-A, UV-B, UV-C), visible light, and gamma rays. , X-rays, electron beams and the like.
  • the silica fine particles contained in the surface protective layer are manufactured by a gel method and have an oil absorption of 100 mL / 100 g or more and 280 mL / 100 g or less.
  • amorphous synthetic silica is roughly classified into wet-process silica and dry-process silica according to the production method.
  • the wet process silica includes silica produced by a precipitation method (hereinafter sometimes referred to as precipitation silica) and silica produced by a gel method (hereinafter sometimes referred to as gel silica).
  • the precipitated silica generally refers to silica obtained by allowing a chemical reaction of the following formula (I) to proceed under basic conditions.
  • the growth of primary particles of silica is promoted under basic conditions.
  • precipitated silica (nSiO 2 ) is generated. At that time, the aggregate becomes floc-like (cotton-like) and settles at the bottom of the reaction mixture.
  • the gel method silica generally refers to silica obtained by allowing the chemical reaction of the above formula (I) to proceed under acidic conditions.
  • the growth of primary particles of silica is suppressed under acidic conditions.
  • gel silica nSiO 2
  • the entire reaction mixture becomes gel-like due to the strong three-dimensional network structure formed by the aggregates.
  • secondary particles having a stronger cohesive force between the primary particles than in the sedimentation method silica are formed due to the production method.
  • the difference between the precipitated silica and the gel silica can be roughly distinguished by, for example, SEM photographs of these silicas.
  • the outer shapes of both silicas are compared. Since the precipitated silica has a floc-like (cotton-like) structure, its outer shape is often rounded.
  • the outer shape of the gel silica is usually square due to its manufacturing method. Therefore, by specifying the outer shape of the silica from the SEM photograph, it may be possible to determine whether the silica is precipitated silica or gel silica.
  • the internal structure and strength of both silicas are compared. Precipitated silica has a relatively small density and tends to be brittle because the cohesive force between primary particles is weak.
  • gel silica has a relatively high density and a tendency to be hard because the cohesive force between primary particles is strong.
  • the curable resin or a cured product thereof enters the interior of the precipitated silica.
  • the inside of the gel method silica has a relatively high density, the hardening resin does not easily enter.
  • the oil absorption of the silica fine particles is usually from 100 mL / 100 g to 280 mL / 100 g, preferably from 110 mL / 100 g to 275 mL / 100 g, more preferably from 120 mL / 100 g to 270 mL / 100 g, and particularly preferably. Is 150 mL / 100 g or more and 270 mL / 100 g or less.
  • the oil absorption of the silica fine particles is 100 mL / 100 g or more, a sufficient matting effect can be obtained.
  • silica fine particles having a high oil absorption have a better matting effect than silica fine particles having a low oil absorption.
  • the magnitude of the matting effect is determined by how many secondary particles of the silica fine particles are included in the surface protective layer.
  • the finer silica particles having a higher oil absorption amount contain more voids inside the secondary particles, and the number of secondary particles of the silica fine particles per unit mass is larger. Therefore, with the same mass, the silica fine particles having a higher oil absorption can use a larger number of secondary particles of the silica fine particles as compared with the silica fine particles having a lower oil absorption, thereby improving the matting effect. Can be done.
  • the oil absorption of the silica fine particles is 280 mL / 100 g or less
  • the effect of preventing whitening of the surface protective layer after a long period of time is excellent.
  • One of the causes of whitening of the surface protective layer is cracking of silica fine particles and change in surface shape after long-term use. If the oil absorption of the silica fine particles is too high, the surface of the silica fine particles after use for a long period of time becomes severe, the internal voids increase, and the silica particles are easily broken.
  • silica fine particles having an oil absorption of 280 mL / 100 g or less do not originally have too many surface irregularities or too many internal voids.
  • the decorative sheet of the present disclosure sets the oil absorption of the silica fine particles in an appropriate range of 100 mL / 100 g or more and 280 mL / 100 g or less to prevent the surface protective layer from matting and prevent whitening after long-term use.
  • the effect is to balance the two effects.
  • the particle size (D50) of the silica fine particles is preferably from 1.0 ⁇ m to 20 ⁇ m, more preferably from 2.0 ⁇ m to 18 ⁇ m, and still more preferably from 3.0 ⁇ m to 15 ⁇ m.
  • the thickness may be particularly preferably 3.0 ⁇ m or more and 9.0 ⁇ m or less.
  • the particle diameter (D50) of the silica fine particles in the present disclosure means a median diameter on a volume basis of the silica fine particles.
  • the particle diameter (D50) of the silica fine particles is 1.0 ⁇ m or more, a sufficient matting effect can be exhibited.
  • the particle size (D50) of the silica fine particles is 20 ⁇ m or less, transparency can be enhanced in the surface protective layer after coating, and the design of the decorative sheet to be obtained is not impaired.
  • the silica fine particles either untreated surface silica or surface-treated silica can be used.
  • the silica fine particles of the present disclosure may be surface-treated silica.
  • the surface treatment method of the silica fine particles may be either an inorganic treatment or an organic treatment, and a conventionally known method can be used.
  • Examples of the surface treatment method of the silica fine particles include a method of impregnating and coating the surface of the silica fine particles with a surfactant, a polymer compound, a hydrophilic resin, a wax, and an inorganic compound; a radical reaction with active groups and the like on the surface of the silica fine particles; Topochemical modification methods using chelate reaction, coupling reaction, sol adsorption, etc .; mechanochemical modification methods using a pulverization active surface and an organic compound, an inorganic compound adsorption reaction, etc .; .
  • the content of the silica fine particles in the surface protective layer is preferably from 1 part by mass to 30 parts by mass, more preferably from 5 parts by mass to 25 parts by mass, and more preferably 10 parts by mass, based on 100 parts by mass of the cured product of the curable resin. It is particularly preferably at least 20 parts by mass and at most 20 parts by mass.
  • the content of the silica fine particles is 1 part by mass or more, there is an advantage that a sufficient matting effect can be imparted to the surface protective layer.
  • the content of the silica fine particles is 30 parts by mass or less, the viscosity of the resin composition for the surface protective layer is less likely to be too high even during the formation of the surface protective layer.
  • the layer can maintain moderate flexibility and coating strength.
  • the surface protective layer may contain an additive in order to achieve the purpose of protecting the surface of the decorative sheet.
  • the additive include an ultraviolet absorber, a light stabilizer and the like.
  • the weathering agent such as an ultraviolet absorber and a light stabilizer is for imparting better weather resistance (light resistance) to the surface protective layer.
  • Examples of the ultraviolet absorber include 2- [4- ⁇ (2-hydroxy-3-dodecyloxypropyl) oxy ⁇ -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3, 5-triazine, 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-dimethylphenyl) -s-triazine, 2- (2-hydroxy-4-hexyloxyphenyl)- Hydroxyphenyltriazine compounds such as 4,6-diphenyl-s-triazine, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-ditertiary compound
  • organic UV absorbers such as benzotriazole compounds such as (butylphenyl) -5-chlorobenzotriazole, benzophenone compounds, and salicylate compounds Particle size 0.2 ⁇ m or less particulate zinc oxide, cerium oxide, can be
  • Examples of the light stabilizer include bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis- (2,2,6,6-tetramethyl-4-piperidyl) sebacate, A hindered amine radical scavenger such as-(N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate can be used.
  • the content of the ultraviolet absorber is preferably 0.01 to 10 parts by mass based on 100 parts by mass of the curable resin.
  • the content of the light stabilizer is preferably 0.01 to 10 parts by mass based on 100 parts by mass of the curable resin.
  • a resin composition for a surface protective layer containing the curable resin, silica fine particles, and additives such as an ultraviolet absorber and a light stabilizer may be prepared.
  • the formation of the surface protective layer using the resin composition for a surface protective layer will be described later.
  • the thickness of the surface protective layer is usually about 1 to 20 ⁇ m, preferably about 2 to 10 ⁇ m.
  • a primer layer may be provided between the resin substrate and the surface protective layer or between the laminate including the resin substrate and the surface protective layer.
  • the adhesion between the resin base material (or the laminate including the resin base material) and the surface protective layer can be improved, the processability can be improved, and blocking can be prevented in the manufacturing process.
  • the primer layer is composed of, for example, a resin composition containing a binder resin (hereinafter, sometimes referred to as a primer layer-forming resin composition).
  • a binder resin for example, urethane resin, acrylic resin, urethane / acrylic copolymer, polyester resin, epoxy resin, vinyl chloride / vinyl acetate copolymer, chlorinated polypropylene resin, chlorinated polyethylene resin, etc.
  • urethane resin acrylic resin, urethane / acrylic copolymer
  • polyester resin epoxy resin
  • vinyl chloride / vinyl acetate copolymer chlorinated polypropylene resin
  • chlorinated polyethylene resin etc.
  • a urethane resin an acrylic resin, a urethane / acrylic copolymer, and a polyester resin
  • one or more selected from the group consisting of a urethane / acrylic copolymer and a polyester resin Is more preferred.
  • a two-component curable resin containing the above resin as a main component and a curing agent such as isocyanate is preferable.
  • isocyanate curing agent a conventionally known compound may be appropriately used, and examples thereof include aromatic compounds such as 2,4-tolylene diisocyanate (TDI), xylene diisocyanate (XDI), naphthalene diisocyanate, and 4,4′-diphenylmethane diisocyanate.
  • Polyisocyanates or poly (alicyclic) isocyanates such as 1,6-hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), methylene diisocyanate (MDI), hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, etc. Isocyanates are used.
  • Adducts or multimers of these various isocyanates for example, adducts of tolylene diisocyanate, trimers of tolylene diisocyanate, and the like are also used.
  • the thickness of the primer layer is usually about 0.5 to 20 ⁇ m, preferably 1 to 10 ⁇ m. When the thickness of the primer layer is within the above range, excellent adhesion can be obtained.
  • Embodiments of the formation of the primer layer and the step of forming the surface protective layer on the primer layer are as follows.
  • the method for forming the primer layer and the surface protective layer in the present disclosure is not necessarily limited to the following embodiments.
  • a primer layer is formed by applying a primer layer-forming resin composition to the surface of a resin base material or a laminate including the resin base material by a gravure printing method.
  • an uncured resin layer is formed by applying a resin composition for a surface protective layer on the primer layer. Thereafter, the uncured resin layer is cured by, for example, irradiating the uncured resin layer with an electron beam or heating the uncured resin layer to form a surface protective layer.
  • FIG. 1 is a schematic cross-sectional view of the first embodiment of the decorative sheet of the present disclosure.
  • a surface protection layer 2 is provided on one surface of the resin substrate 1.
  • FIG. 2 is a schematic cross-sectional view of a decorative sheet according to a second embodiment of the present disclosure.
  • the picture layer 3 is provided between the resin substrate 1 and the surface protective layer 2.
  • FIG. 3 is a schematic cross-sectional view of a decorative sheet according to a third embodiment of the present disclosure.
  • a pattern layer 3, an adhesive layer 5, a transparent resin layer 6, a primer layer 7, and a surface protection layer 2 are provided in this order on one surface of the resin substrate 1, and the other side of the resin substrate 1 is provided.
  • the back surface primer layer 4 is provided on the surface.
  • one or two or more layers may be provided between the resin base material and the surface protection layer, or the resin base material may be provided on the surface protection layer.
  • One or more layers may be provided on the surface opposite to the facing side.
  • one or two or more layers may be provided on the surface of the surface protective layer opposite to the side facing the resin substrate. Note that the decorative sheet of the present disclosure is not limited to only the layer configurations shown in FIGS.
  • the decorative sheet of the present disclosure may include a pattern layer.
  • the picture layer may be arranged, for example, between the resin base material and the surface protection layer.
  • As the pattern formed by the picture layer a pattern pattern imitating the surface appearance of a natural product such as wood grain, stone grain, cloth grain, an abstract pattern pattern such as a polka dot pattern, a striped pattern, a geometric pattern, a pattern including letters or numbers Etc. can be exemplified.
  • the picture layer may be a picture or a picture that is reproduced by a combination of a plurality of colors, or may be a picture itself.
  • Examples of the material for forming the picture layer include a metal thin film and an ink in which the above-mentioned coloring agent is dispersed in a binder.
  • Examples of the metal thin film include thin films of metals such as aluminum, chromium, gold, silver, and copper. These metal thin films are formed by a method such as vacuum evaporation or sputtering.
  • Examples of the binder used in the ink include chlorinated polyolefins such as chlorinated polyethylene and chlorinated polypropylene, polyester resins, urethane resins, acrylic resins, polyvinyl acetate, vinyl chloride-vinyl acetate copolymers, and cellulosic resins.
  • binders may be used alone or as a mixture of two or more.
  • the binder in which two or more kinds of resins are mixed include, for example, a two-component curable acrylic-urethane resin.
  • a material in which the above-mentioned coloring agent is added to such a binder is used as a picture layer ink.
  • the pattern layer ink is directly printed on the resin base material, it is preferable to use a mixture of an acrylic resin and a vinyl chloride-vinyl acetate copolymer or a urethane resin as a binder from the viewpoint of adhesiveness.
  • the picture layer may be provided only on one side of the resin substrate, or may be provided on both sides.
  • the thickness of the picture layer can be appropriately set according to the contents of the decoration and the type of the color pattern, and is generally about 0.1 ⁇ m to 20 ⁇ m, preferably 0.5 ⁇ m to 10 ⁇ m.
  • the decorative sheet of the present disclosure may include a transparent resin layer.
  • the transparent resin layer may be disposed, for example, between the resin substrate and the surface protection layer.
  • the picture layer When the picture layer is exposed to the atmosphere, the picture layer may be deteriorated by water (rain), air (particularly oxygen), ultraviolet rays, and heat, and may peel off. Further, the same problem may occur when the resin base material containing the colorant is exposed to the atmosphere. Therefore, in order to prevent the deterioration of the picture layer and the fading of the resin substrate, and to protect the entire laminate, it is preferable to cover at least the surface of the laminate including the resin substrate with the transparent resin layer.
  • the material used for the transparent resin layer is not particularly limited as long as it can prevent the above-described physical damage or chemical deterioration of the laminate, and examples thereof include an acrylic resin and an olefin resin.
  • Acrylic resins include polyacrylates (polymethyl acrylate, polyethyl acrylate, polypropyl acrylate, polybutyl acrylate, etc.), polymethacrylates (polymethyl methacrylate, polyethyl methacrylate, Propyl methacrylate, polybutyl methacrylate, etc.), and copolymers thereof.
  • the olefin resin include polypropylene, polyethylene, polybutene, and ethylene-propylene copolymer.
  • the transparent resin layer may contain an additive in order to reinforce at least a function required as a layer covering the surface of the resin base material.
  • the additive include a plasticizer, an ultraviolet absorber, a light stabilizer, a heat stabilizer, an antioxidant, an antistatic agent, and a flame retardant.
  • the weathering agent such as an ultraviolet absorber and a light stabilizer is the same as that for the surface protective layer described above.
  • a mixture of the above-mentioned materials for the transparent resin layer is formed into a film by a conventional method such as a calendar method to obtain a transparent resin film.
  • This transparent resin film is used for forming a transparent resin layer.
  • the thickness of the transparent resin film is about 50 to 100 ⁇ m, preferably about 80 ⁇ m.
  • the method for forming the transparent resin layer is not particularly limited. For example, there is a method in which a transparent resin film is attached to one surface side of a resin substrate or a laminate including the resin substrate via an adhesive layer or the like. Further, there is also a method in which a raw material for a transparent resin film is directly heated and melt-extruded on one surface side of a resin substrate or a laminate including the resin substrate via an adhesive layer or the like.
  • a method in which a pattern layer is applied and formed on one side of a transparent resin film, and the transparent resin film is pasted on one side of a resin base material may be used.
  • the raw material of the adhesive layer include a transparent polyurethane resin-based adhesive.
  • the thickness of the adhesive layer is, for example, 1 to 5 ⁇ m.
  • a back primer layer may be further provided on the front surface of the resin base material.
  • the back primer layer is a layer that normally functions as a base for improving the adhesion between the resin substrate and the surface of the member when the decorative sheet of the present disclosure is bonded to the surface of another member.
  • the resin used for the backside primer layer examples include a two-component curable urethane-nitrified cotton mixed resin (hardening agent: hexamethylene diisocyanate, etc.), a polyester / urethane resin mixed resin, an acrylonitrile-butadiene-styrene copolymer resin (ABS type) Resins), polyolefin-based resins, styrene-based resins, acrylic resins, vinyl chloride-based resins, polycarbonate-based resins, and the like, and one or more of these can be used in combination.
  • ABS type acrylonitrile-butadiene-styrene copolymer resin
  • the resin used for the backside primer layer particularly preferably includes a polyester / urethane resin mixed resin and a vinyl chloride resin, and most preferably includes a polyester / urethane resin mixed resin.
  • the thickness of the back primer layer is preferably from 0.1 to 10.0 ⁇ m, more preferably from 0.5 to 3.0 ⁇ m.
  • a method for forming the backside primer layer for example, a known method such as a gravure printing method can be used.
  • the thickness of the decorative sheet is not particularly limited.
  • the thickness of the decorative sheet may be, for example, 10 ⁇ m to 1,000 ⁇ m, and is preferably 50 ⁇ m to 300 ⁇ m.
  • the characteristic evaluation of the decorative sheet is performed by, for example, a gloss evaluation test and a weather resistance evaluation test.
  • Examples of the test method of the gloss evaluation test are as follows.
  • the gloss value of the sample is measured by a method according to JIS Z8741-1997 using a gloss meter ("Micro Gloss" manufactured by BYK Gardner) at an angle of 60 °. The measurement is performed at any five places on the surface protective layer, and the average of the obtained measured values is used for evaluation of the sample.
  • Gloss evaluation method Next, the upper limit value of the content (or content ratio) of the silica fine particles in the surface protective layer in the decorative sheet is set.
  • the gloss evaluation of the decorative sheet is performed based on whether the gloss value of the decorative sheet obtained by the above-described gloss measuring method is equal to or less than a specified value.
  • evaluation A it can be evaluated that the gloss of the decorative sheet can be suppressed, that is, the content of the silica fine particles can be adjusted so that the decorative sheet has a sufficient matting effect.
  • evaluation F since the gloss value is large despite the large content of silica fine particles, it is evaluated that the matting effect is insufficient.
  • the gloss value of the obtained decorative sheet is equal to or less than the specified value.
  • the upper limit of the content (or content ratio) of the silica fine particles may be set to 20 parts by mass with respect to 100 parts by mass of the cured product of the curable resin in the surface protective layer.
  • the prescribed value of the gloss value of the decorative sheet may be, for example, 10.
  • the weather resistance evaluation test is performed using, for example, a weather resistance acceleration tester.
  • the details of the test method of the weather resistance evaluation test are as follows, for example.
  • the weather resistance evaluation test based on the following tester and test conditions is also abbreviated as “S-UV test”.
  • -Weathering Acceleration Testing Machine Eye Super UV Tester (trade name, model number: SUV-W261, manufactured by Iwasaki Electric Co., Ltd., hereinafter abbreviated as "S-UV”) ⁇ Test conditions Temperature: 63 ° C Humidity: 50% RH UV illuminance: 100 mW / cm 2
  • Test method After irradiating ultraviolet rays for 20 hours continuously, the test environment is kept in a dew condensation state for 4 hours.
  • the surface protective layer of the decorative sheet was observed 300 hours and 500 hours after the start of the test, and evaluated as follows. In the case of evaluation A, it can be evaluated that the surface protective layer of the decorative sheet has excellent long-term weather resistance. A: No whitening of the surface protective layer is observed. B: Slight whitening is observed on the surface protective layer. F: Remarkable whitening is observed in the surface protective layer.
  • the decorative sheet of the present disclosure has an excellent matting effect and has a long-lasting weather resistance, so that the surface protective layer is hardly whitened. Therefore, specific applications are mainly used for decoration of architectural interior members and architectural exterior members, for example, for exterior materials of buildings such as outer walls, walls, roofs, etc .; buildings such as walls, floors, ceilings, etc. For window frames, door frames, handrails and other fittings; for interior materials or exterior materials of vehicles such as automobiles;
  • Example 1 As a resin base material, a polypropylene sheet (thickness: 80 ⁇ m) having both surfaces subjected to corona treatment was prepared. On one surface of the resin substrate, a printing ink using a two-component curable acrylic-urethane resin as a binder was applied by a gravure printing method to form a wood-grained pattern layer (thickness: 3 ⁇ m).
  • a back primer layer (thickness: 3 ⁇ m) was formed on the other surface of the resin substrate.
  • An adhesive layer (thickness after drying: 3 ⁇ m) was formed by applying a transparent polyurethane resin-based adhesive on the surface of the picture layer opposite to the side in contact with the resin substrate.
  • a transparent polypropylene resin was heated and melt extruded by a T-die extruder to form a transparent resin layer (thickness: 80 ⁇ m).
  • the primer layer resin composition was applied by a gravure printing method to form a primer layer (thickness after drying: 4 ⁇ m).
  • a resin composition for a surface protective layer containing the following ionizing radiation-curable resin, silica fine particles, an ultraviolet absorber, and a light stabilizer was prepared.
  • Resin composition for surface protective layer -Ionizing radiation curable resin: 100 parts by mass of urethane acrylate oligomer (weight average molecular weight: 4,000, number of functional groups: 3)-Silica fine particles (production method: gel method, oil absorption: 180 mL / 100 g, particle size (D50): 4.4 ⁇ m) 17 parts by mass, UV absorber: 2- [4- ⁇ (2-hydroxy-3-dodecyloxypropyl) oxy ⁇ -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) ) -1,3,5-Triazine [TINUVIN 400 (trade name), manufactured by BASF Japan Ltd.] 1 part by mass.Light stabilizer: hindered amine light stabilizer (bis (1-octyloxy
  • Example 1 the addition amount of the silica fine particles was adjusted so that the gloss value (60 °) of the obtained decorative sheet became 10, and as a result, 17 parts by mass with respect to 100 parts by mass of the ionizing radiation-curable resin. It was decided.
  • An uncured resin layer was formed by applying the resin composition for a surface protective layer on the primer layer. Thereafter, the uncured resin layer was cured by irradiating an electron beam (applied voltage: 175 KeV, 5 Mrad (50 kGy)) to form a surface protective layer (thickness: 5 ⁇ m).
  • an electron beam applied voltage: 175 KeV, 5 Mrad (50 kGy)
  • a laminate having a seven-layer structure surface protective layer / primer layer / transparent resin layer / adhesive layer / picture layer / resin base material / backside primer layer
  • Example 1 FIG. 3
  • Examples 2 to 4 Comparative Examples 1 to 3
  • the types and addition amounts of the silica fine particles were changed as shown in Table 1 below, and as in Example 1, Examples 2 to 4 and The decorative sheets of Comparative Examples 1 to 3 were produced.
  • the gloss evaluation of the decorative sheet was performed based on whether or not the gloss value of the decorative sheet obtained by the above-described gloss measuring method was 10 or less when the amount was given by mass.
  • silica content (parts by mass) means the content (parts by mass) of silica fine particles with respect to 100 parts by mass of the ionizing radiation-curable resin in the resin composition for a surface protective layer. As described above, the content of the silica fine particles is an amount adjusted so that the gloss value (60 °) of the obtained decorative sheet becomes 10.
  • S-UV 300h means the evaluation 300 hours after the start of the S-UV test
  • S-UV 500h means the evaluation 500 hours after the start of the S-UV test. means.
  • the weather resistance of Comparative Example 2 was not evaluated.
  • the decorative sheet of Comparative Example 1 contains silica fine particles having an oil absorption of 300 mL / 100 g. From the above Table 1, in Comparative Example 1, the weather resistance evaluation 300 hours after the start of the S-UV test is B, and the weather resistance evaluation 500 hours after the start of the S-UV test is F. Therefore, when silica fine particles having an oil absorption of more than 280 mL / 100 g are used for the surface protective layer, it is understood that the long-term weather resistance is not sufficient.
  • the decorative sheet of Comparative Example 2 contains silica fine particles having an oil absorption of 90 mL / 100 g.
  • the gloss evaluation of Comparative Example 2 is F. That is, in Comparative Example 2, the gloss exceeded 10 even when the silica fine particles were added in an amount of 20 parts by mass or more. Therefore, when the silica fine particles having an oil absorption of less than 100 mL / 100 g are used for the surface protective layer, the matting effect of the surface protective layer is not sufficient.
  • the decorative sheet of Comparative Example 3 contains precipitated silica. From Table 1 above, in Comparative Example 3, the weather resistance evaluation 300 hours after the start of the S-UV test is B, and the weather resistance evaluation 500 hours after the start of the S-UV test is F. Therefore, it is understood that when the precipitated silica is used for the surface protective layer, the long-term weather resistance is not sufficient.
  • the decorative sheets of Examples 1 to 4 have an oil absorption of 180 mL / 100 g or more and 270 mL / 100 g or less and contain silica fine particles produced by a gel method. From Table 1, in Examples 1 to 4, the gloss evaluation and the weather resistance evaluation 300 hours after the start of the S-UV test were all A, and the weather resistance evaluation 500 hours after the start of the S-UV test was B. That is all. Therefore, a decorative sheet produced by the gel method and containing silica fine particles having an oil absorption of 100 mL / 100 g or more and 280 mL / 100 g or less in the surface protective layer has an excellent matting effect in the surface protective layer and long-term use. It was proved that the effect of suppressing the later whitening can be compatible.

Abstract

The present invention provides a decorative sheet which exhibits excellent matting effects, while being not susceptible to whitening of a surface protective layer. A decorative sheet which comprises a resin base material and a surface protective layer that is arranged on at least one surface of the resin base material, and which is characterized in that the surface protective layer contains a cured product of a curable resin and silica fine particles that are formed by a gel method and have an oil absorption of from 100 mL/100 g to 280 mL/100 g (inclusive).

Description

化粧シートDecorative sheet
　本開示は、主に建築内装部材及び建築外装部材に使用されるものであって、樹脂基材及び表面保護層を備え、長期耐候性に優れる化粧シートに関する。 The present disclosure is mainly used for a building interior member and a building exterior member, and relates to a decorative sheet having a resin base material and a surface protective layer, and having excellent long-term weather resistance.
　化粧シートにおいて、観察者に対し落ち着いた印象を与えるため、その表面に艶消しを施す技術が知られている。従来、化粧シートに艶消しを施す場合、艶消し効果が大きいこと及びコストを低く抑えられることから、化粧シートの表面保護層にシリカを添加する技術が知られている。
　特許文献１には、基材シート上に最表面層として表面保護層を備える化粧シートの製造に用いるコーティング剤であって、前記表面保護層は、前記コーティング剤の硬化塗膜であり、前記コーティング剤は、シリカと電離放射線硬化型樹脂とを含有し、前記シリカは、細孔容量が１．８ｍＬ以上３．０ｍＬ以下であり、みかけ比重が０．０５ｇ／ｍＬ以上０．２２ｇ／ｍＬ以下であり、吸油量が３００ｍＬ／１００ｇ以上であることを特徴とするコーティング剤が開示されている。当該文献には、上記細孔容量、みかけ比重及び吸油量の艶消しシリカを用いることにより、コーティング剤及び当該コーティング剤の塗膜中において艶消しシリカの沈降や対流が生じ難いという効果が記載されている。 2. Description of the Related Art In a decorative sheet, in order to give a calm impression to an observer, a technique of matting the surface thereof is known. BACKGROUND ART Conventionally, when a decorative sheet is matted, a technique of adding silica to a surface protective layer of the decorative sheet is known because the matting effect is large and the cost can be kept low.
Patent Document 1 discloses a coating agent used for manufacturing a decorative sheet having a surface protective layer as an outermost surface layer on a substrate sheet, wherein the surface protective layer is a cured coating film of the coating agent, The agent contains silica and an ionizing radiation-curable resin, and the silica has a pore volume of 1.8 mL or more and 3.0 mL or less, and an apparent specific gravity of 0.05 g / mL or more and 0.22 g / mL or less. There is disclosed a coating agent characterized by having an oil absorption of 300 mL / 100 g or more. The document describes that the use of matting silica having the above pore volume, apparent specific gravity and oil absorption makes it difficult for sedimentation and convection of matting silica to occur in a coating agent and a coating film of the coating agent. ing.
　特許文献２には、ゲル法シリカであり、ＢＥＴ比表面積が２５０～３５０ｍ２／ｇであり、コールターカウンター法による平均粒径がｌ．２～１．８μｍで、かつ８μｍ以上の粗粒子が存在せずｌμｍ以下の粒子が全体の１０～３０％であることを特徴とするトップコート用艶消しシリカが開示されている。当該文献には、前記トップコート用艶消しシリカを使用することにより、分散性に優れ且つ艶消し効果が高いために塗膜外観に優れたトップコートが得られるとの記載がある。 Patent Document 2 discloses a gel-processed silica having a BET specific surface area of 250 to 350 m 2 / g and an average particle size of 1 μm by a Coulter counter method. Disclosed is a matte silica for a top coat, characterized in that coarse particles having a size of 2 to 1.8 μm and not having a size of 8 μm or more are present and particles having a size of 1 μm or less account for 10 to 30% of the whole. The document states that the use of the matte silica for a top coat can provide a top coat having excellent dispersibility and a high matting effect, and thus having an excellent coating film appearance.
　また、艶消しとは異なる効果を期待して、化粧シートの表面保護層にシリカを配合する技術も知られている。
　特許文献３には、活性エネルギー線硬化性オリゴマー（但し、シリコーン（メタ）アクリレートを除く）及び／又は活性エネルギー線硬化性モノマーと、シリコーン（メタ）アクリレートと、吸油量が９５～２５０ｍＬ／１００ｇである表面未処理シリカとを含有してなる活性エネルギー線硬化型組成物を表面保護層とする化粧シートが開示されている。当該文献には、耐セロハンテープ剥離性、耐溶剤性、耐薬品性、及び耐汚染性に優れる効果が記載されている。 There is also known a technique of blending silica in a surface protective layer of a decorative sheet in expectation of an effect different from matting.
Patent Document 3 discloses an active energy ray-curable oligomer (excluding silicone (meth) acrylate) and / or an active energy ray-curable monomer, a silicone (meth) acrylate, and an oil absorption of 95 to 250 mL / 100 g. A decorative sheet using an active energy ray-curable composition containing certain surface-untreated silica as a surface protective layer is disclosed. This document describes effects that are excellent in cellophane tape peeling resistance, solvent resistance, chemical resistance, and stain resistance.
特開２０１６－１４５３６８号公報JP 2016-145368 A 特開平８－１７００３０号公報JP-A-8-170030 特開２００７－１６１３９号公報JP 2007-16139 A
　近年、長期耐候性に優れる化粧シートの需要、特に、優れた意匠性を長期間保持可能な化粧シートの需要が高まっている。本発明者らは、シリカを含む表面保護層は長期間の使用により白化するという問題があり、これにより化粧シートの意匠性が大きく損なわれることを発見した。
　一方、特許文献１には、経時的な意匠性の悪化に関する記載は一切ない。特許文献２には、シリカを使用すると塗膜が白っぽくなるという指摘はあるものの、塗膜の透明性の時間変化に関する検討は一切開示されていない。特許文献３には、１週間経過後の塗液の外観の評価はあるものの（表１）、化粧シートに加工した後の意匠性の経時変化に関する記載は一切ない（表２及び表３参照）。
　本開示は、化粧シートの長期耐候性に関する上記実状を鑑みて成し遂げられたものであり、樹脂基材及び表面保護層を備え、優れた艶消し効果を奏し、かつ表面保護層における白化が生じにくい化粧シートを提供することを目的とする。 In recent years, demand for a decorative sheet excellent in long-term weather resistance, particularly demand for a decorative sheet capable of maintaining excellent design properties for a long time, has been increasing. The present inventors have found that the surface protective layer containing silica has a problem of whitening due to long-term use, and has found that the design of the decorative sheet is greatly impaired.
On the other hand, Patent Literature 1 has no description about deterioration of the design property over time. Although Patent Document 2 points out that the use of silica makes the coating film whitish, it does not disclose any study on the temporal change in the transparency of the coating film. Patent Literature 3 evaluates the appearance of the coating liquid after one week has passed (Table 1), but does not mention any change with time in the design properties after processing into a decorative sheet (see Tables 2 and 3). .
The present disclosure has been achieved in view of the above-mentioned circumstances regarding the long-term weather resistance of a decorative sheet, and has a resin substrate and a surface protective layer, has an excellent matting effect, and hardly causes whitening in the surface protective layer. It is intended to provide a decorative sheet.
　本開示の化粧シートは、樹脂基材、及び当該樹脂基材の少なくとも一方の面側に表面保護層を備え、前記表面保護層が、硬化性樹脂の硬化物、及び、ゲル法により製造され、かつ、吸油量が１００ｍＬ／１００ｇ以上２８０ｍＬ／１００ｇ以下であるシリカ微粒子を含有することを特徴とする。 The decorative sheet of the present disclosure includes a resin substrate, and a surface protection layer on at least one surface side of the resin substrate, wherein the surface protection layer is a cured product of a curable resin, and is manufactured by a gel method, Further, it is characterized by containing silica fine particles having an oil absorption of 100 mL / 100 g or more and 280 mL / 100 g or less.
　本開示において、前記シリカ微粒子の粒径（Ｄ５０）は１μｍ以上２０μｍ以下であってもよい。 In the present disclosure, the particle diameter (D50) of the silica fine particles may be 1 μm or more and 20 μm or less.
　本開示によれば、表面保護層が、ゲル法により製造されかつ特定範囲の吸油量を有するシリカ微粒子を含有するため、優れた艶消し効果及び長期間使用後の白化抑制効果を両立できる化粧シートが得られる。 According to the present disclosure, since the surface protective layer contains silica fine particles produced by a gel method and having a specific range of oil absorption, a decorative sheet capable of achieving both excellent matting effect and whitening suppression effect after long-term use. Is obtained.
本開示の化粧シートの第１の実施形態の断面模式図である。1 is a schematic cross-sectional view of a first embodiment of a decorative sheet of the present disclosure. 本開示の化粧シートの第２の実施形態の断面模式図である。It is a cross section of a 2nd embodiment of the decorative sheet of this indication. 本開示の化粧シートの第３の実施形態の断面模式図である。It is a cross section of a 3rd embodiment of a decorative sheet of the present disclosure.
　次に、本開示の実施の態様について詳細に説明するが、本開示は以下の実施の態様に限定されるものではなく、その趣旨の範囲内で種々変形して実施することができる。 Next, embodiments of the present disclosure will be described in detail. However, the present disclosure is not limited to the following embodiments, and can be implemented with various modifications within the scope of the gist.
　本開示の化粧シートは、樹脂基材、及び当該樹脂基材の少なくとも一方の面側に表面保護層を備え、前記表面保護層が、硬化性樹脂の硬化物、及び、ゲル法により製造され、かつ、吸油量が１００ｍＬ／１００ｇ以上２８０ｍＬ／１００ｇ以下であるシリカ微粒子を含有することを特徴とする。 The decorative sheet of the present disclosure includes a resin substrate, and a surface protection layer on at least one surface side of the resin substrate, wherein the surface protection layer is a cured product of a curable resin, and is manufactured by a gel method, Further, it is characterized by containing silica fine particles having an oil absorption of 100 mL / 100 g or more and 280 mL / 100 g or less.
　上述したように、本発明者らは、シリカを含む表面保護層が長期間の使用により白化するという問題を今回初めて発見した。
　本開示は、このような長期耐候性の問題を解決できる化粧シートに関する。その解決メカニズムの概要は、ゲル法により製造されかつ上記特定範囲の吸油量を有するシリカ微粒子を表面保護層に配合することにより、優れた艶消し効果及び長期間使用後の白化抑制効果を両立するというものである。
　以下、化粧シートの構成の詳細を説明する。 As described above, the present inventors have discovered, for the first time, a problem that the surface protective layer containing silica whitens due to long-term use.
The present disclosure relates to a decorative sheet that can solve such a problem of long-term weather resistance. An outline of the solution mechanism is to combine an excellent matting effect and an effect of suppressing whitening after long-term use by blending silica fine particles produced by a gel method and having an oil absorption in the above specific range into the surface protective layer. That is.
Hereinafter, the configuration of the decorative sheet will be described in detail.
　１．樹脂基材
　樹脂基材は、化粧シートの形状を保持しうる強度を有していれば特に限定されない。樹脂基材に含まれる樹脂としては、例えば、ポリエチレン、ポリプロピレン、オレフィン系熱可塑性エラストマー、アイオノマー等のポリオレフィン系樹脂；塩化ビニル樹脂、塩化ビニリデン樹脂、ポリビニルアルコール、エチレン－ビニルアルコール共重合体等のビニル系樹脂；ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、エチレングリコール－テレフタル酸－イソフタル酸共重合体、ポリエステル系熱可塑性エラストマー等のポリエステル系樹脂；ポリメタクリル酸メチル、ポリアクリル酸メチル、ポリメタクリル酸エチル等のアクリル系樹脂；ポリスチレン、アクリロニトリル－ブタジエン－スチレン共重合体（ＡＢＳ樹脂）、三酢酸セルロース、ポリカーボネート等が挙げられる。これらの中でも、耐候性、耐水性等の各種物性、印刷適性、成形加工適性、価格等の観点からポリオレフィン系樹脂、塩化ビニル樹脂、ポリエステル系樹脂、及びアクリル系樹脂が好ましく、ポリオレフィン系樹脂がより好ましい。
　樹脂基材は、予めその片面又は両面にコロナ処理を施したものであってもよい。 1. Resin base material The resin base material is not particularly limited as long as it has a strength capable of maintaining the shape of the decorative sheet. Examples of the resin contained in the resin substrate include polyolefin resins such as polyethylene, polypropylene, olefin-based thermoplastic elastomers and ionomers; vinyl resins such as vinyl chloride resin, vinylidene chloride resin, polyvinyl alcohol, and ethylene-vinyl alcohol copolymer. Polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene glycol-terephthalic acid-isophthalic acid copolymer, polyester-based thermoplastic elastomer; polymethyl methacrylate, polymethyl methacrylate, polymethacrylic acid Acrylic resins such as ethyl; polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS resin), cellulose triacetate, polycarbonate and the like. Among these, weather resistance, various physical properties such as water resistance, printing suitability, molding suitability, polyolefin resin, vinyl chloride resin, polyester resin, and acrylic resin are preferable from the viewpoint of price, etc., and polyolefin resin is more preferable. preferable.
The resin base material may have been subjected to corona treatment on one surface or both surfaces in advance.
　樹脂基材として塩化ビニル樹脂のように可塑剤添加により材料力学的特性を可変して成形加工適性等の諸特性を調整可能な樹脂を選択する場合は、必要に応じて、可塑剤を含有していてもよい。可塑剤は、当該樹脂基材に柔軟性を付与し、その硬さを制御することを目的として用いられる。
　使用される可塑剤として、塩化ビニル樹脂の場合、ジオクチルフタレート等のフタル酸エステル系、トリメリット酸トリオクチル等のトリメリット酸エステル系、アジピン酸エステル系、アジピン酸ポリエステル系、フタル酸ポリエステル系、リン酸エステル系、クエン酸エステル系、安息香酸エステル系、テレフタル酸エステル系、エポキシ化植物油系、塩素化パラフィン系などが挙げられる。
　可塑剤の含有量には特に制限はなく、例えば、樹脂基材を構成する樹脂１００質量部に対し、５～６０質量部であってもよく、１５～３５質量部であることが好ましい。 When selecting a resin such as vinyl chloride resin that can adjust various properties such as suitability for molding by changing material mechanical properties by adding a plasticizer as the resin base material, if necessary, include a plasticizer. May be. The plasticizer is used for the purpose of imparting flexibility to the resin base material and controlling its hardness.
As a plasticizer to be used, in the case of vinyl chloride resin, phthalic acid esters such as dioctyl phthalate, trimellitic acid esters such as trioctyl trimellitate, adipic acid esters, adipic acid polyesters, phthalic polyesters, phosphorus Acid esters, citrates, benzoates, terephthalates, epoxidized vegetable oils, chlorinated paraffins and the like can be mentioned.
The content of the plasticizer is not particularly limited, and may be, for example, 5 to 60 parts by mass, preferably 15 to 35 parts by mass with respect to 100 parts by mass of the resin constituting the resin base material.
　樹脂基材は、着色剤を含有していてもよい。着色剤は、樹脂基材の少なくとも一方の面を、所望の色相に着色させる。着色剤としては、チタン白、亜鉛華、弁柄、朱、群青、コバルトブルー、黄鉛、チタン黄、カーボンブラック等の無機顔料、イソインドリノン、ハンザイエローＡ、キナクリドン、パーマネントレッド４Ｒ、フタロシアニンブルー、アゾメチンアゾ化合物、ペリレン系化合物、ニッケルアゾ錯体等の有機顔料あるいは染料、アルミニウム、真鍮等の金属の箔粉からなる金属顔料、二酸化チタン被覆雲母、塩基性炭酸鉛等の箔粉からなる真珠光沢（パール）顔料等の従来公知の着色顔料が用いられる。着色は透明着色、不透明（隠蔽）着色いずれでも良いが、一般的には、被着体を隠蔽するために不透明着色が良い。
　着色剤の含有量は、本開示の化粧シートが加工性及び密着性等の機械特性を有していれば、特に限定されない。 The resin base material may contain a coloring agent. The colorant causes at least one surface of the resin substrate to be colored to a desired hue. Examples of coloring agents include inorganic pigments such as titanium white, zinc white, red petals, vermilion, ultramarine blue, cobalt blue, graphite, titanium yellow, and carbon black, isoindolinone, Hansa Yellow A, quinacridone, permanent red 4R, and phthalocyanine blue. , Azomethine azo compounds, perylene compounds, organic pigments or dyes such as nickel azo complexes, metal pigments composed of metal foil powders such as aluminum and brass, pearl luster composed of foil powders such as titanium dioxide-coated mica and basic lead carbonate A conventionally known coloring pigment such as a pigment) is used. The coloring may be either transparent coloring or opaque (concealing) coloring. In general, opaque coloring is good for concealing the adherend.
The content of the coloring agent is not particularly limited as long as the decorative sheet of the present disclosure has mechanical properties such as processability and adhesion.
　樹脂基材は、さらに必要に応じて、熱安定剤、難燃剤、ラジカル捕捉剤、紫外線吸収剤等を含有する。熱安定剤は、フェノール系、サルファイト系、フェニルアルカン系、フォスファイト系、アミン系等公知のものであリ、熱加工時の熱変色等の劣化の防止性をより向上させる場合に用いられる。難燃剤としては、水酸化アルミニウム、水酸化マグネシウム等の粉末が用いられ、これらは、難燃性を付与する必要がある場合に添加する。ラジカル捕捉剤としては、例えば、ビス－（２，２，６，６－テトラメチル－４－ピペリジル）セバケート、ビス－（Ｎ－メチル－２，２，６，６－テトラメチル－４－ピペリジル）セバケート等のヒンダードアミン系ラジカル捕捉剤が用いられる。紫外線吸収剤としては、２－（２－ヒドロキシ－４－オクトキシフェニル）－４，６－ビス（２，４－ジメチルフェニル）－ｓ－トリアジン、２－（２－ヒドロキシ－４－ヘキシルオキシフェニル）－４，６－ジフェニル－ｓ－トリアジン等のトリアジン系、２－（２’－ヒドロキシ－５’－メチルフェニル）ベンゾトリアゾール、２－（２’－ヒドロキシ－３’，５’－ジ第三ブチルフェニル）－５－クロロベンゾトリアゾール等のベンゾトリアゾール系、ベンゾフェノン系、ベンゾエート系等が用いられる。
　これら添加剤の含有量は、例えば、樹脂基材を構成する樹脂１００質量部に対し、１～５０質量部が好ましく、１０～２５質量部がより好ましい。 The resin base material further contains a heat stabilizer, a flame retardant, a radical scavenger, an ultraviolet absorber, and the like, if necessary. The heat stabilizer is a known one such as a phenol type, a sulfite type, a phenylalkane type, a phosphite type, and an amine type, and is used for further improving the prevention of deterioration such as thermal discoloration during thermal processing. . As the flame retardant, powders such as aluminum hydroxide and magnesium hydroxide are used, and these are added when it is necessary to impart flame retardancy. Examples of the radical scavenger include bis- (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis- (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) A hindered amine radical scavenger such as sebacate is used. Examples of the ultraviolet absorber include 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-dimethylphenyl) -s-triazine and 2- (2-hydroxy-4-hexyloxyphenyl) ) -4,6-diphenyl-s-triazine and other triazines, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditertiary) Benzotriazoles such as (butylphenyl) -5-chlorobenzotriazole, benzophenones, benzoates and the like are used.
The content of these additives is, for example, preferably 1 to 50 parts by mass, more preferably 10 to 25 parts by mass, per 100 parts by mass of the resin constituting the resin base material.
　樹脂、及び必要な場合には可塑剤等の添加剤を混合したものをカレンダー製法等の常用の方法により製膜することにより、樹脂基材が得られる。
　得られる樹脂基材の厚さは、その強度及び耐熱性が適切になるように材料に応じて適宜設定することができ、１μｍ～１，０００μｍ程度が一般的で、好ましくは１０μｍ～５００μｍである。 A resin base material is obtained by forming a film of a mixture of a resin and, if necessary, additives such as a plasticizer by a conventional method such as a calendering method.
The thickness of the obtained resin base material can be appropriately set according to the material so that the strength and heat resistance are appropriate, and is generally about 1 μm to 1,000 μm, preferably 10 μm to 500 μm. .
　本開示の化粧シートを構成する各層（樹脂基材及び表面保護層、並びに、必要な場合には絵柄層、透明樹脂層等）の厚さの測定方法は以下の通りである。まず、化粧シートの断面を光学顕微鏡又は電子顕微鏡などで観察する。測定対象となる層の厚さを３か所～１０か所程度測定し、算出される厚さの平均を、その層の厚さとする。 方法 The method of measuring the thickness of each layer (the resin base material and the surface protection layer, and, if necessary, the picture layer, the transparent resin layer, etc.) constituting the decorative sheet of the present disclosure is as follows. First, the cross section of the decorative sheet is observed with an optical microscope or an electron microscope. The thickness of the layer to be measured is measured at about 3 to 10 places, and the average of the calculated thickness is defined as the thickness of the layer.
　２．表面保護層
　表面保護層は、硬化性樹脂の硬化物及び特定のシリカ微粒子を含有する。
　表面保護層に使用可能な硬化性樹脂としては、熱硬化性樹脂及び電離放射線硬化性樹脂等が挙げられ、それらを併用しても良い。これらの樹脂及び後述する特定のシリカ微粒子を含む組成物を、上記樹脂基材表面、又は当該樹脂基材を含む積層体の表面に塗布した後、熱付与又は電離放射線照射により樹脂を硬化させることにより、表面保護層を形成することができる。表面保護層を形成する樹脂の架橋密度を高め、表面保護層表面の耐傷性や耐摩耗性を向上させ得るとの観点から、電離放射線硬化性樹脂が好ましい。また、無溶媒で塗布することができ、取扱いが容易との観点から、電子線硬化性樹脂がより好ましい。
　熱硬化性樹脂としては、例えば、ウレタン系樹脂、エポキシ系樹脂、ポリシロキサン系樹脂等を用いることができる。このうち、特に、得られる塗膜の可撓性や、耐薬品性等の耐久性等の諸特性が良好な２液硬化型ウレタン樹脂が好ましい。２液硬化型ウレタン樹脂は、ポリオールを主剤としイソシアネートを架橋剤（硬化剤）とするウレタン樹脂であり、ポリオールは分子中に２個以上の水酸基を有する化合物である。ポリオールとしては、例えばポリエチレングリコール、ポリプロピレングリコール、アクリルポリオール、ポリエステルポリオール、ポリエーテルポリオール、ポリカーボネートポリオール、ポリウレタンポリオール等が用いられる。また、イソシアネートとしては、分子中に２個以上のイソシアネート基を有する多価イソシアネートが用いられる。例えば、２，４－トリレンジイソシアネート、キシレンジイソシアネート、４，４’－ジフェニルメタンジイソシアネート等の芳香族イソシアネート、或いは、１，６－ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、水素添加トリレンジイソシアネート、水素添加ジフェニルメタンジイソシアネート等の脂肪族（乃至は脂環式）イソシアネートが用いられる。或いはまた、上記各種イソシアネートの付加体又は多量体、例えば、トリレンジイソシアネートの付加体、トリレンジイソシアネート３量体（ｔｒｉｍｅｒ）等がある。
　電離放射線硬化性樹脂としては、電離放射線硬化性を有する樹脂として従来慣用されているような、分子中に（メタ）アクリロイル基、（メタ）アクリロイルオキシ基等のラジカル重合性不飽和基、エポキシ基等のカチオン重合性官能基等を有する重合性モノマー及び重合性オリゴマー（乃至はプレポリマー）の中から適宜選択して用いることができる。
　分子中に（メタ）アクリロイル基を有する重合性モノマーとしては、例えば、メチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート等の単官能（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、トリメチロールプロパンテトラ（メタ）アクリレート、ジペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート等の多官能（メタ）アクリレート等が挙げられる。
　分子中に（メタ）アクリロイル基を有する重合性オリゴマーとしては、例えば、ウレタン（メタ）アクリレートオリゴマー、エポキシ（メタ）アクリレートオリゴマー、ポリエステル（メタ）アクリレートオリゴマー、ポリエーテル（メタ）アクリレートオリゴマー、アクリル（メタ）アクリレートオリゴマー等が挙げられる。尚、本開示において「（メタ）アクリレート」とは、アクリレート又はメタクリレートを意味する。
　分子中にカチオン重合性官能基を有するプレポリマーとしては、例えば、ビスフェノール型エポキシ樹脂、ノボラック型エポキシ化合物等のエポキシ系樹脂、脂肪酸系ビニルエーテル、芳香族系ビニルエーテル等のビニルエーテル系樹脂のプレポリマーが挙げられる。
　これらの重合性モノマー及び／又は重合性オリゴマー、（乃至はプレポリマー）は、以上例示した化合物の中から、単独で、又は２種以上を組み合わせて用いることができる。
　なお、電離放射線とは、分子を重合させて硬化させ得るエネルギーを有する電磁波または荷電粒子を意味し、例えば、すべての紫外線（ＵＶ－Ａ、ＵＶ－Ｂ、ＵＶ－Ｃ）、可視光線、ガンマー線、Ｘ線、電子線等が挙げられる。 2. Surface protective layer The surface protective layer contains a cured product of a curable resin and specific silica fine particles.
Examples of the curable resin that can be used for the surface protective layer include a thermosetting resin and an ionizing radiation curable resin, and these may be used in combination. After applying a composition containing these resins and specific silica fine particles described below to the surface of the resin substrate, or the surface of a laminate including the resin substrate, curing the resin by applying heat or irradiating with ionizing radiation. Thereby, a surface protective layer can be formed. From the viewpoint of increasing the crosslink density of the resin forming the surface protective layer and improving the scratch resistance and abrasion resistance of the surface protective layer surface, ionizing radiation-curable resins are preferred. In addition, an electron beam-curable resin is more preferable because it can be applied without a solvent and is easy to handle.
As the thermosetting resin, for example, a urethane resin, an epoxy resin, a polysiloxane resin, or the like can be used. Among them, a two-part curable urethane resin having good properties such as flexibility of the obtained coating film and durability such as chemical resistance is particularly preferable. The two-component curable urethane resin is a urethane resin having a polyol as a main component and an isocyanate as a crosslinking agent (curing agent), and the polyol is a compound having two or more hydroxyl groups in a molecule. As the polyol, 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 a molecule is used. For example, aromatic isocyanates such as 2,4-tolylene diisocyanate, xylene diisocyanate, and 4,4'-diphenylmethane diisocyanate, or 1,6-hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, etc. (Or alicyclic) isocyanates of the formula (1). Alternatively, there are adducts or multimers of the above-mentioned various isocyanates, for example, adducts of tolylene diisocyanate, trimers of tolylene diisocyanate, and the like.
Examples of the ionizing radiation-curable resin include radically polymerizable unsaturated groups such as a (meth) acryloyl group, a (meth) acryloyloxy group, and an epoxy group in a molecule as conventionally used as an ionizing radiation-curable resin. And the like, and can be appropriately selected from polymerizable monomers and polymerizable oligomers (or prepolymers) having a cationic polymerizable functional group and the like.
Examples of the polymerizable monomer having a (meth) acryloyl group in the molecule include monofunctional (meth) acrylates such as methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and phenoxyethyl (meth) acrylate, and diethylene glycol di ( (Meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropanetetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipenta And polyfunctional (meth) acrylates such as erythritol hexa (meth) acrylate.
Examples of the polymerizable oligomer having a (meth) acryloyl group in the molecule include urethane (meth) acrylate oligomer, epoxy (meth) acrylate oligomer, polyester (meth) acrylate oligomer, polyether (meth) acrylate oligomer, and acryl (meth) ) Acrylate oligomers and the like. In the present disclosure, “(meth) acrylate” means acrylate or methacrylate.
Examples of the prepolymer having a cationically polymerizable functional group in the molecule include bisphenol epoxy resins, epoxy resins such as novolak epoxy compounds, and prepolymers of vinyl ether resins such as fatty acid vinyl ethers and aromatic vinyl ethers. Can be
These polymerizable monomers and / or polymerizable oligomers (or prepolymers) can be used alone or in combination of two or more of the compounds exemplified above.
In addition, ionizing radiation means electromagnetic waves or charged particles having energy capable of polymerizing and curing molecules, such as all ultraviolet rays (UV-A, UV-B, UV-C), visible light, and gamma rays. , X-rays, electron beams and the like.
　本開示においては、表面保護層に含まれるシリカ微粒子が、ゲル法により製造され、かつ、吸油量が１００ｍＬ／１００ｇ以上２８０ｍＬ／１００ｇ以下であることが主な特徴の１つである。 One of the main features of the present disclosure is that the silica fine particles contained in the surface protective layer are manufactured by a gel method and have an oil absorption of 100 mL / 100 g or more and 280 mL / 100 g or less.
　一般的に、非晶質の合成シリカは、その製造方法により湿式法シリカと乾式法シリカとに大別される。湿式法シリカには、沈降法により製造されるシリカ（以下、沈降法シリカと称する場合がある。）と、ゲル法により製造されるシリカ（以下、ゲル法シリカと称する場合がある。）が存在する。
　沈降法シリカとは、一般的に、下記式（Ｉ）の化学反応を塩基性条件下で進行させることにより得られるシリカを指す。
　式（Ｉ）
　Ｎａ２Ｏ・ｎＳｉＯ２＋Ｈ２ＳＯ４→ｎＳｉＯ２＋Ｎａ２ＳＯ４＋Ｈ２Ｏ
　上記式（Ｉ）において、塩基性条件下ではシリカの一次粒子の成長が促進される。十分に成長したシリカの一次粒子同士が凝集することにより、沈降法シリカ（ｎＳｉＯ２）が生成する。その際、凝集体がフロック状（綿状）となり反応混合物の底に沈降する。 In general, amorphous synthetic silica is roughly classified into wet-process silica and dry-process silica according to the production method. The wet process silica includes silica produced by a precipitation method (hereinafter sometimes referred to as precipitation silica) and silica produced by a gel method (hereinafter sometimes referred to as gel silica). I do.
The precipitated silica generally refers to silica obtained by allowing a chemical reaction of the following formula (I) to proceed under basic conditions.
Formula (I)
Na 2 O · nSiO 2 + H 2 SO 4 → nSiO 2 + Na 2 SO 4 + H 2 O
In the above formula (I), the growth of primary particles of silica is promoted under basic conditions. By agglomeration of sufficiently grown primary particles of silica, precipitated silica (nSiO 2 ) is generated. At that time, the aggregate becomes floc-like (cotton-like) and settles at the bottom of the reaction mixture.
　一方、ゲル法シリカとは、一般的に、上記式（Ｉ）の化学反応を酸性条件下で進行させることにより得られるシリカを指す。
　上記式（Ｉ）において、酸性条件下ではシリカの一次粒子の成長が抑制される。成長途上のシリカの一次粒子同士が凝集することにより、ゲル法シリカ（ｎＳｉＯ２）が生成する。その際、凝集体が形成する強固な３次元網目構造により、反応混合物全体がゲル状となる。このように、ゲル法シリカにおいては、その製造方法に由来して、沈降法シリカよりも一次粒子同士の凝集力がより強い二次粒子が形成される。 On the other hand, the gel method silica generally refers to silica obtained by allowing the chemical reaction of the above formula (I) to proceed under acidic conditions.
In the above formula (I), the growth of primary particles of silica is suppressed under acidic conditions. By aggregating the primary particles of the growing silica, gel silica (nSiO 2 ) is generated. At this time, the entire reaction mixture becomes gel-like due to the strong three-dimensional network structure formed by the aggregates. As described above, in the gel method silica, secondary particles having a stronger cohesive force between the primary particles than in the sedimentation method silica are formed due to the production method.
　沈降法シリカとゲル法シリカとの違いは、例えば、これらのシリカのＳＥＭ写真によってもおおよその区別が可能である。
　まず、両シリカの外形を対比する。沈降法シリカはフロック状（綿状）構造を有するため、通常、その外形は丸みを帯びることが多い。一方、ゲル法シリカの外形は、その製造方法に由来して角ばっているのが通常である。したがって、ＳＥＭ写真からシリカの外形を特定することにより、沈降法シリカ又はゲル法シリカのいずれであるかの判別が可能となる場合がある。
　次に、両シリカの内部構造と強度を対比する。沈降法シリカは、一次粒子同士の凝集力が弱いため、密度が比較的小さく、もろい傾向がある。一方、ゲル法シリカは、一次粒子同士の凝集力が強いため比較的高密度であり硬い傾向がある。沈降法シリカを硬化性樹脂と併せて表面保護層に用いた場合、沈降法シリカの断面構造のＳＥＭ写真において、硬化性樹脂（又はその硬化物）が沈降法シリカ内部に入り込む様子が確認できる。これに対し、ゲル法シリカ内部は比較的高密度であるため、硬化性樹脂が入り込みにくい。したがって、ゲル法シリカを硬化性樹脂と併せて表面保護層に用いた場合の断面構造のＳＥＭ写真においては、通常、ゲル法シリカ内部には硬化性樹脂（又はその硬化物）の存在が確認されにくい。 The difference between the precipitated silica and the gel silica can be roughly distinguished by, for example, SEM photographs of these silicas.
First, the outer shapes of both silicas are compared. Since the precipitated silica has a floc-like (cotton-like) structure, its outer shape is often rounded. On the other hand, the outer shape of the gel silica is usually square due to its manufacturing method. Therefore, by specifying the outer shape of the silica from the SEM photograph, it may be possible to determine whether the silica is precipitated silica or gel silica.
Next, the internal structure and strength of both silicas are compared. Precipitated silica has a relatively small density and tends to be brittle because the cohesive force between primary particles is weak. On the other hand, gel silica has a relatively high density and a tendency to be hard because the cohesive force between primary particles is strong. When the precipitated silica is used in combination with the curable resin for the surface protective layer, it can be seen from the SEM photograph of the cross-sectional structure of the precipitated silica that the curable resin (or a cured product thereof) enters the interior of the precipitated silica. On the other hand, since the inside of the gel method silica has a relatively high density, the hardening resin does not easily enter. Therefore, in the SEM photograph of the cross-sectional structure when the gel method silica is used in combination with the curable resin for the surface protective layer, usually, the presence of the curable resin (or a cured product thereof) is confirmed inside the gel method silica. Hateful.
　後述する吸油量の値が同程度であったとしても、製造方法が異なるシリカを用いることによって長期耐候性に顕著な差が生じることは、例えば実施例２及び実施例３（ゲル法シリカを使用した実験結果）と、比較例３（沈降法シリカを使用した実験結果）との対比により明らかである。すなわち、長期耐候性試験後の断面ＳＥＭ観察の結果、比較例３においては沈降法シリカの割れや表面の荒れが確認できたものの、実施例２及び実施例３においてはゲル法シリカにつきこれらの異常は確認できなかった。このように、長期間経過後の表面保護層の白化を抑制する条件として、ゲル法シリカを用いることがまず重要である。 Even if the oil absorption values described later are substantially the same, the use of silica having a different production method causes a remarkable difference in long-term weather resistance, for example, in Examples 2 and 3 (using gel silica. This is evident from a comparison between the experimental results obtained above and Comparative Example 3 (experimental results using precipitated silica). That is, as a result of cross-sectional SEM observation after the long-term weather resistance test, cracks and surface roughness of the precipitated silica were confirmed in Comparative Example 3, but in Examples 2 and 3, these abnormalities were observed in the gel silica. Could not be confirmed. As described above, it is first important to use gel silica as a condition for suppressing the whitening of the surface protective layer after a long period of time.
　シリカ微粒子の吸油量は、通常１００ｍＬ／１００ｇ以上２８０ｍＬ／１００ｇ以下であり、好適には１１０ｍＬ／１００ｇ以上２７５ｍＬ／１００ｇ以下であり、より好適には１２０ｍＬ／１００ｇ以上２７０ｍＬ／１００ｇ以下であり、特に好適には１５０ｍＬ／１００ｇ以上２７０ｍＬ／１００ｇ以下である。
　まず、シリカ微粒子の吸油量が１００ｍＬ／１００ｇ以上であることにより、十分な艶消し効果が得られる。通常、吸油量が多いシリカ微粒子は、吸油量が少ないシリカ微粒子よりも艶消し効果に優れる。その理由は以下の通りである。艶消し効果の大小はシリカ微粒子の二次粒子の数がどのくらい多く表面保護層に含まれるかで決まると考えられる。吸油量がより多いシリカ微粒子ほどその二次粒子内部に空隙をより多く含み、単位質量当たりのシリカ微粒子の二次粒子の数がより多い。したがって、同じ質量であれば、吸油量が多いシリカ微粒子ほど、吸油量が少ないシリカ微粒子に比べて、より多くの数のシリカ微粒子の二次粒子を使用することができ、それだけ艶消し効果を向上させることができる。
　一方、シリカ微粒子の吸油量が２８０ｍＬ／１００ｇ以下であることにより、長期間経過後の表面保護層の白化を防止する効果に優れる。その理由は以下の通りである。表面保護層の白化の要因の１つとして、長期間使用後のシリカ微粒子の割れや表面形状の変化が挙げられる。シリカ微粒子の吸油量が高すぎる場合には、長期間使用後のシリカ微粒子表面の荒れは酷くなり、内部の空隙も増え、割れやすくなる。しかし、吸油量が２８０ｍＬ／１００ｇ以下のシリカ微粒子は、元々、表面の凹凸や内部の空隙が多すぎることはないため、長期間使用後であっても当該シリカ微粒子の割れや表面荒れが進行しにくく、白化防止効果に優れる。
　このように、本開示の化粧シートは、シリカ微粒子の吸油量を１００ｍＬ／１００ｇ以上２８０ｍＬ／１００ｇ以下という適切な範囲に設定することにより、表面保護層の艶消し効果と長期間使用後の白化防止効果という２つの効果のバランスを図るものである。 The oil absorption of the silica fine particles is usually from 100 mL / 100 g to 280 mL / 100 g, preferably from 110 mL / 100 g to 275 mL / 100 g, more preferably from 120 mL / 100 g to 270 mL / 100 g, and particularly preferably. Is 150 mL / 100 g or more and 270 mL / 100 g or less.
First, when the oil absorption of the silica fine particles is 100 mL / 100 g or more, a sufficient matting effect can be obtained. Usually, silica fine particles having a high oil absorption have a better matting effect than silica fine particles having a low oil absorption. The reason is as follows. It is considered that the magnitude of the matting effect is determined by how many secondary particles of the silica fine particles are included in the surface protective layer. The finer silica particles having a higher oil absorption amount contain more voids inside the secondary particles, and the number of secondary particles of the silica fine particles per unit mass is larger. Therefore, with the same mass, the silica fine particles having a higher oil absorption can use a larger number of secondary particles of the silica fine particles as compared with the silica fine particles having a lower oil absorption, thereby improving the matting effect. Can be done.
On the other hand, when the oil absorption of the silica fine particles is 280 mL / 100 g or less, the effect of preventing whitening of the surface protective layer after a long period of time is excellent. The reason is as follows. One of the causes of whitening of the surface protective layer is cracking of silica fine particles and change in surface shape after long-term use. If the oil absorption of the silica fine particles is too high, the surface of the silica fine particles after use for a long period of time becomes severe, the internal voids increase, and the silica particles are easily broken. However, silica fine particles having an oil absorption of 280 mL / 100 g or less do not originally have too many surface irregularities or too many internal voids. Difficult to whiten.
As described above, the decorative sheet of the present disclosure sets the oil absorption of the silica fine particles in an appropriate range of 100 mL / 100 g or more and 280 mL / 100 g or less to prevent the surface protective layer from matting and prevent whitening after long-term use. The effect is to balance the two effects.
　シリカ微粒子の粒径（Ｄ５０）は、好適には１．０μｍ以上２０μｍ以下であり、より好適には２．０μｍ以上１８μｍ以下であってもよく、さらに好適には３．０μｍ以上１５μｍ以下であってもよく、特に好適には３．０μｍ以上９．０μｍ以下であってもよい。なお、本開示におけるシリカ微粒子の粒径（Ｄ５０）とは、シリカ微粒子の体積基準でのメジアン径を意味する。シリカ微粒子の粒径（Ｄ５０）が１．０μｍ以上であることにより、十分な艶消し効果を発揮することができる。一方、シリカ微粒子の粒径（Ｄ５０）が２０μｍ以下であることにより、塗膜後の表面保護層において透明性を高めることができ、かつ得られる化粧シートの意匠性を損なうことがない。 The particle size (D50) of the silica fine particles is preferably from 1.0 μm to 20 μm, more preferably from 2.0 μm to 18 μm, and still more preferably from 3.0 μm to 15 μm. The thickness may be particularly preferably 3.0 μm or more and 9.0 μm or less. In addition, the particle diameter (D50) of the silica fine particles in the present disclosure means a median diameter on a volume basis of the silica fine particles. When the particle diameter (D50) of the silica fine particles is 1.0 μm or more, a sufficient matting effect can be exhibited. On the other hand, when the particle size (D50) of the silica fine particles is 20 μm or less, transparency can be enhanced in the surface protective layer after coating, and the design of the decorative sheet to be obtained is not impaired.
　シリカ微粒子は、表面未処理シリカ、表面処理済みシリカのいずれも使用できる。このうち、本開示のシリカ微粒子は、表面処理済みシリカであってもよい。
　シリカ微粒子の表面処理方法は、無機処理及び有機処理のいずれでも良く、従来公知の方法が使用できる。シリカ微粒子の表面処理方法としては、例えば、界面活性剤、高分子化合物、親水性樹脂、ワックス、無機化合物等をシリカ微粒子表面に含浸コーティングする方法；シリカ微粒子表面の活性基等とのラジカル反応、キレート反応、カップリング反応、ゾル吸着等を利用したトポケミカルな改質方法；粉砕活性面と有機化合物とのグラフト反応、無機化合物の吸着反応等を利用したメカノケミカルな改質方法；等が挙げられる。 As the silica fine particles, either untreated surface silica or surface-treated silica can be used. Among them, the silica fine particles of the present disclosure may be surface-treated silica.
The surface treatment method of the silica fine particles may be either an inorganic treatment or an organic treatment, and a conventionally known method can be used. Examples of the surface treatment method of the silica fine particles include a method of impregnating and coating the surface of the silica fine particles with a surfactant, a polymer compound, a hydrophilic resin, a wax, and an inorganic compound; a radical reaction with active groups and the like on the surface of the silica fine particles; Topochemical modification methods using chelate reaction, coupling reaction, sol adsorption, etc .; mechanochemical modification methods using a pulverization active surface and an organic compound, an inorganic compound adsorption reaction, etc .; .
　表面保護層中のシリカ微粒子の含有量は、硬化性樹脂の硬化物１００質量部に対し、１質量部以上３０質量部以下が好ましく、５質量部以上２５質量部以下がより好ましく、１０質量部以上２０質量部以下が特に好ましい。シリカ微粒子の当該含有量が１質量部以上であることにより、表面保護層に十分な艶消し効果を付与できるという利点がある。一方、シリカ微粒子の当該含有量が３０質量部以下であることにより、表面保護層の形成時においても、表面保護層用樹脂組成物の粘度が高くなりすぎることが少なく、また、得られる表面保護層が適度な柔軟性と塗膜強度を維持することができる。 The content of the silica fine particles in the surface protective layer is preferably from 1 part by mass to 30 parts by mass, more preferably from 5 parts by mass to 25 parts by mass, and more preferably 10 parts by mass, based on 100 parts by mass of the cured product of the curable resin. It is particularly preferably at least 20 parts by mass and at most 20 parts by mass. When the content of the silica fine particles is 1 part by mass or more, there is an advantage that a sufficient matting effect can be imparted to the surface protective layer. On the other hand, when the content of the silica fine particles is 30 parts by mass or less, the viscosity of the resin composition for the surface protective layer is less likely to be too high even during the formation of the surface protective layer. The layer can maintain moderate flexibility and coating strength.
　表面保護層は、化粧シートの表面保護の目的を達成するために、添加剤を含有していてもよい。添加剤としては、例えば、紫外線吸収剤、光安定剤等が挙げられる。紫外線吸収剤、光安定剤等の耐候剤は、表面保護層に対しより良好な耐候性（耐光性）を付与するためのものである。
　紫外線吸収剤としては、２－［４－｛（２－ヒドロキシ－３－ドデシルオキシプロピル）オキシ｝－２－ヒドロキシフェニル］－４，６－ビス（２，４－ジメチルフェニル）－１，３，５－トリアジン、２－（２－ヒドロキシ－４－オクトキシフェニル）－４，６－ビス（２，４－ジメチルフェニル）－ｓ－トリアジン、２－（２－ヒドロキシ－４－ヘキシルオキシフェニル）－４，６－ジフェニル－ｓ－トリアジン等のヒドロキシフェニルトリアジン化合物、２－（２’－ヒドロキシ－５’－メチルフェニル）ベンゾトリアゾール、２－（２’－ヒドロキシ－３’，５’－ジ第三ブチルフェニル）－５－クロロベンゾトリアゾール等のベンゾトリアゾール化合物、ベンゾフェノン化合物、サリチル酸エステル化合物等の有機系の紫外線吸収剤の他、粒径０．２μｍ以下の微粒子状の酸化亜鉛、酸化セリウム、酸化チタン等の無機系の紫外線吸収剤も用いることができる。
　光安定剤としては、ビス（１－オクチルオシキ－２，２，６，６－テトラメチル－４－ピペリジニル）セバケート、ビス－（２，２，６，６－テトラメチル－４－ピペリジル）セバケート、ビス－（Ｎ－メチル－２，２，６，６－テトラメチル－４－ピペリジル）セバケート等のヒンダードアミン系ラジカル捕捉剤を用いることができる。
　紫外線吸収剤の含有量は、硬化性樹脂１００質量部に対し０．０１～１０質量部であることが好ましい。光安定剤の含有量は、硬化性樹脂１００質量部に対し０．０１～１０質量部であることが好ましい。
　表面保護層の形成に当たり、上記硬化性樹脂、シリカ微粒子、並びに、紫外線吸収剤及び光安定剤等の添加剤を含む表面保護層用樹脂組成物を調製してもよい。表面保護層用樹脂組成物を用いた表面保護層の形成については後述する。
　表面保護層の厚さは、通常１～２０μｍ程度であり、２～１０μｍ程度であることが好ましい。 The surface protective layer may contain an additive in order to achieve the purpose of protecting the surface of the decorative sheet. Examples of the additive include an ultraviolet absorber, a light stabilizer and the like. The weathering agent such as an ultraviolet absorber and a light stabilizer is for imparting better weather resistance (light resistance) to the surface protective layer.
Examples of the ultraviolet absorber include 2- [4-{(2-hydroxy-3-dodecyloxypropyl) oxy} -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3, 5-triazine, 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-dimethylphenyl) -s-triazine, 2- (2-hydroxy-4-hexyloxyphenyl)- Hydroxyphenyltriazine compounds such as 4,6-diphenyl-s-triazine, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-ditertiary compound Other organic UV absorbers such as benzotriazole compounds such as (butylphenyl) -5-chlorobenzotriazole, benzophenone compounds, and salicylate compounds Particle size 0.2μm or less particulate zinc oxide, cerium oxide, can be used inorganic ultraviolet absorbers such as titanium oxide.
Examples of the light stabilizer include bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis- (2,2,6,6-tetramethyl-4-piperidyl) sebacate, A hindered amine radical scavenger such as-(N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate can be used.
The content of the ultraviolet absorber is preferably 0.01 to 10 parts by mass based on 100 parts by mass of the curable resin. The content of the light stabilizer is preferably 0.01 to 10 parts by mass based on 100 parts by mass of the curable resin.
In forming the surface protective layer, a resin composition for a surface protective layer containing the curable resin, silica fine particles, and additives such as an ultraviolet absorber and a light stabilizer may be prepared. The formation of the surface protective layer using the resin composition for a surface protective layer will be described later.
The thickness of the surface protective layer is usually about 1 to 20 μm, preferably about 2 to 10 μm.
　樹脂基材と表面保護層との間、又は樹脂基材を含む積層体と表面保護層との間にはプライマー層を設けてもよい。プライマー層を設けることで樹脂基材（又は樹脂基材を含む積層体）と表面保護層との密着性を向上させるとともに、加工性を向上させ、また製造工程においてブロッキングを防止することもできる。 プ ラ イ マ ー A primer layer may be provided between the resin substrate and the surface protective layer or between the laminate including the resin substrate and the surface protective layer. By providing the primer layer, the adhesion between the resin base material (or the laminate including the resin base material) and the surface protective layer can be improved, the processability can be improved, and blocking can be prevented in the manufacturing process.
　プライマー層は、例えばバインダー樹脂を含む樹脂組成物（以下、プライマー層形成用樹脂組成物と称する場合がある。）により構成される。バインダー樹脂としては、特に制限はないが、例えばウレタン樹脂、アクリル樹脂、ウレタン／アクリル共重合体、ポリエステル樹脂、エポキシ樹脂、塩化ビニル／酢酸ビニル共重合体、塩素化ポリプロピレン樹脂、塩素化ポリエチレン樹脂などが好ましく挙げられる。上記の中でも、ウレタン樹脂、アクリル樹脂、ウレタン／アクリル共重合体、及びポリエステル樹脂からなる群から選ばれる１種以上が好ましく、ウレタン／アクリル共重合体及びポリエステル樹脂からなる群から選ばれる１種以上がより好ましい。また、優れた密着性が得られる観点から、上記の樹脂を主剤とし、イソシアネート等を硬化剤とした２液硬化性樹脂が好ましい。 The primer layer is composed of, for example, a resin composition containing a binder resin (hereinafter, sometimes referred to as a primer layer-forming resin composition). Although there is no particular limitation on the binder resin, for example, urethane resin, acrylic resin, urethane / acrylic copolymer, polyester resin, epoxy resin, vinyl chloride / vinyl acetate copolymer, chlorinated polypropylene resin, chlorinated polyethylene resin, etc. Are preferred. Among the above, one or more selected from the group consisting of a urethane resin, an acrylic resin, a urethane / acrylic copolymer, and a polyester resin is preferable, and one or more selected from the group consisting of a urethane / acrylic copolymer and a polyester resin Is more preferred. In addition, from the viewpoint of obtaining excellent adhesion, a two-component curable resin containing the above resin as a main component and a curing agent such as isocyanate is preferable.
　イソシアネート硬化剤としては、従来公知の化合物を適宜使用すればよく、例えば、２，４－トリレンジイソシアネート（ＴＤＩ）、キシレンジイソシアネート（ＸＤＩ）、ナフタレンジイソシアネート、４，４’－ジフェニルメタンジイソシアネートなどの芳香族イソシアネート、あるいは１，６－ヘキサメチレンジイソシアネート（ＨＭＤＩ）、イソホロンジイソシアネート（ＩＰＤＩ）、メチレンジイソシアネート（ＭＤＩ）、水素添加トリレンジイソシアネート、水素添加ジフェニルメタンジイソシアネートなどの脂肪族（ないしは脂環式）イソシアネートなどのポリイソシアネートが用いられる。また、これら各種イソシアネートの付加体又は多量体、例えば、トリレンジイソシアネートの付加体、トリレンジイソシアネート３量体（ｔｒｉｍｅｒ）なども用いられる。 As the isocyanate curing agent, a conventionally known compound may be appropriately used, and examples thereof include aromatic compounds such as 2,4-tolylene diisocyanate (TDI), xylene diisocyanate (XDI), naphthalene diisocyanate, and 4,4′-diphenylmethane diisocyanate. Polyisocyanates or poly (alicyclic) isocyanates such as 1,6-hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), methylene diisocyanate (MDI), hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, etc. Isocyanates are used. Adducts or multimers of these various isocyanates, for example, adducts of tolylene diisocyanate, trimers of tolylene diisocyanate, and the like are also used.
　プライマー層の厚さは、通常０．５～２０μｍ程度であり、１～１０μｍが好ましい。プライマー層の厚さが上記範囲内であると、優れた密着性が得られる。 The thickness of the primer layer is usually about 0.5 to 20 μm, preferably 1 to 10 μm. When the thickness of the primer layer is within the above range, excellent adhesion can be obtained.
　プライマー層の形成、及びプライマー層上に表面保護層を形成する工程の実施形態は以下の通りである。なお、本開示におけるプライマー層及び表面保護層の形成方法は、必ずしも以下の実施形態に限定されるものではない。
　まず、樹脂基材又は樹脂基材を含む積層体の表面に、プライマー層形成用樹脂組成物をグラビア印刷法で塗布することにより、プライマー層を形成する。
　次に、プライマー層上に表面保護層用樹脂組成物を塗布することにより未硬化樹脂層を形成する。その後、例えば未硬化樹脂層に対し電子線を照射したり、又は未硬化樹脂層を加熱したりすることにより未硬化樹脂層を硬化させ、表面保護層を形成する。 Embodiments of the formation of the primer layer and the step of forming the surface protective layer on the primer layer are as follows. The method for forming the primer layer and the surface protective layer in the present disclosure is not necessarily limited to the following embodiments.
First, a primer layer is formed by applying a primer layer-forming resin composition to the surface of a resin base material or a laminate including the resin base material by a gravure printing method.
Next, an uncured resin layer is formed by applying a resin composition for a surface protective layer on the primer layer. Thereafter, the uncured resin layer is cured by, for example, irradiating the uncured resin layer with an electron beam or heating the uncured resin layer to form a surface protective layer.
　３．層構成
　本開示の化粧シートは、樹脂基材と表面保護層とを備えていれば、その層構成は特に限定されない。
　図１は、本開示の化粧シートの第１の実施形態の断面模式図である。化粧シート１００においては、樹脂基材１の一方の面に表面保護層２が設けられる。
　図２は、本開示の化粧シートの第２の実施形態の断面模式図である。化粧シート２００においては、樹脂基材１と表面保護層２との間に絵柄層３が設けられる。
　図３は、本開示の化粧シートの第３の実施形態の断面模式図である。化粧シート３００においては、樹脂基材１の一方の面に絵柄層３、接着剤層５、透明樹脂層６、プライマー層７及び表面保護層２がこの順に設けられ、樹脂基材１の他方の面に裏面プライマー層４が設けられる。
　図２及び図３に示すように、本開示の化粧シートにおいては、樹脂基材と表面保護層との間に１又は２以上の層を設けてもよいし、樹脂基材において表面保護層に面する側とは反対側の面に１又は２以上の層を設けてもよい。また、本開示の化粧シートにおいては、表面保護層において樹脂基材に面する側とは反対側の面に１又は２以上の層を設けてもよい。
　なお、本開示の化粧シートは、図１～図３に示す層構成のみに限定されるものではない。 3. Layer Configuration The layer configuration of the decorative sheet of the present disclosure is not particularly limited as long as it has a resin substrate and a surface protective layer.
FIG. 1 is a schematic cross-sectional view of the first embodiment of the decorative sheet of the present disclosure. In the decorative sheet 100, a surface protection layer 2 is provided on one surface of the resin substrate 1.
FIG. 2 is a schematic cross-sectional view of a decorative sheet according to a second embodiment of the present disclosure. In the decorative sheet 200, the picture layer 3 is provided between the resin substrate 1 and the surface protective layer 2.
FIG. 3 is a schematic cross-sectional view of a decorative sheet according to a third embodiment of the present disclosure. In the decorative sheet 300, a pattern layer 3, an adhesive layer 5, a transparent resin layer 6, a primer layer 7, and a surface protection layer 2 are provided in this order on one surface of the resin substrate 1, and the other side of the resin substrate 1 is provided. The back surface primer layer 4 is provided on the surface.
As shown in FIGS. 2 and 3, in the decorative sheet of the present disclosure, one or two or more layers may be provided between the resin base material and the surface protection layer, or the resin base material may be provided on the surface protection layer. One or more layers may be provided on the surface opposite to the facing side. In the decorative sheet of the present disclosure, one or two or more layers may be provided on the surface of the surface protective layer opposite to the side facing the resin substrate.
Note that the decorative sheet of the present disclosure is not limited to only the layer configurations shown in FIGS.
　図３に示すように、本開示の化粧シートは絵柄層を備えていてもよい。絵柄層は、例えば、樹脂基材と表面保護層との間に配置されていてもよい。
　絵柄層により形成される模様としては、木目、石目、布目等の天然物の表面外観を模した絵柄模様、水玉模様、縞模様、幾何学模様等の抽象柄模様、文字又は数字を含む模様等が例示できる。
　絵柄層は、複数の色彩の組み合わせによって写真や絵画を再現するものであったり、それ自体が絵画であったりしてもよい。 As shown in FIG. 3, the decorative sheet of the present disclosure may include a pattern layer. The picture layer may be arranged, for example, between the resin base material and the surface protection layer.
As the pattern formed by the picture layer, a pattern pattern imitating the surface appearance of a natural product such as wood grain, stone grain, cloth grain, an abstract pattern pattern such as a polka dot pattern, a striped pattern, a geometric pattern, a pattern including letters or numbers Etc. can be exemplified.
The picture layer may be a picture or a picture that is reproduced by a combination of a plurality of colors, or may be a picture itself.
　絵柄層を形成する材料としては、例えば、金属薄膜や、バインダーに上述した着色剤を分散させたインク等が挙げられる。
　金属薄膜としては、アルミニウム、クロム、金、銀、銅等の金属の薄膜が例示できる。これらの金属薄膜は、真空蒸着やスパッタリング等の方法で成膜される。
　インクに用いられるバインダーとして、塩素化ポリエチレン、塩素化ポリプロピレン等の塩素化ポリオレフィン、ポリエステル樹脂、ウレタン樹脂、アクリル樹脂、ポリ酢酸ビニル、塩化ビニル－酢酸ビニル共重合体、セルロース系樹脂等が挙げられる。これらバインダーは、単独で用いてもよいし、２種類以上を混合して用いてもよい。２種類以上の樹脂を混合したバインダーの例としては、例えば、２液硬化型アクリル－ウレタン樹脂が挙げられる。このようなバインダーに、上述した着色剤を添加した材料が、絵柄層用インクとして用いられる。
　樹脂基材に絵柄層用インクを直接印刷する場合は、バインダーとして、アクリル樹脂と塩化ビニル－酢酸ビニル共重合体との混合物やウレタン樹脂を採用することが、接着性の点で好ましい。 Examples of the material for forming the picture layer include a metal thin film and an ink in which the above-mentioned coloring agent is dispersed in a binder.
Examples of the metal thin film include thin films of metals such as aluminum, chromium, gold, silver, and copper. These metal thin films are formed by a method such as vacuum evaporation or sputtering.
Examples of the binder used in the ink include chlorinated polyolefins such as chlorinated polyethylene and chlorinated polypropylene, polyester resins, urethane resins, acrylic resins, polyvinyl acetate, vinyl chloride-vinyl acetate copolymers, and cellulosic resins. These binders may be used alone or as a mixture of two or more. Examples of the binder in which two or more kinds of resins are mixed include, for example, a two-component curable acrylic-urethane resin. A material in which the above-mentioned coloring agent is added to such a binder is used as a picture layer ink.
When the pattern layer ink is directly printed on the resin base material, it is preferable to use a mixture of an acrylic resin and a vinyl chloride-vinyl acetate copolymer or a urethane resin as a binder from the viewpoint of adhesiveness.
　絵柄層は、樹脂基材の一方の面の側のみに設けられていてもよく、両面側に設けられていてもよい。
　絵柄層の厚さは、装飾の内容や色柄の種類に応じて適宜設定することができ、０．１μｍ～２０μｍ程度が一般的で、好ましくは０．５μｍ～１０μｍである。 The picture layer may be provided only on one side of the resin substrate, or may be provided on both sides.
The thickness of the picture layer can be appropriately set according to the contents of the decoration and the type of the color pattern, and is generally about 0.1 μm to 20 μm, preferably 0.5 μm to 10 μm.
　図３に示すように、本開示の化粧シートは透明樹脂層を備えていてもよい。透明樹脂層は、例えば、樹脂基材と表面保護層との間に配置されていてもよい。
　絵柄層が大気に露出すると、水（雨）、空気（特に酸素）、紫外線、熱により絵柄層が劣化し、剥げ落ちる場合がある。また、着色剤を含有する樹脂基材が大気に露出する場合についても、同様の問題が生じるおそれがある。したがって、絵柄層の劣化や樹脂基材の色あせを防ぎ、積層体全体を保護するために、少なくとも樹脂基材を含む積層体表面を透明樹脂層により覆うことが好ましい。 As shown in FIG. 3, the decorative sheet of the present disclosure may include a transparent resin layer. The transparent resin layer may be disposed, for example, between the resin substrate and the surface protection layer.
When the picture layer is exposed to the atmosphere, the picture layer may be deteriorated by water (rain), air (particularly oxygen), ultraviolet rays, and heat, and may peel off. Further, the same problem may occur when the resin base material containing the colorant is exposed to the atmosphere. Therefore, in order to prevent the deterioration of the picture layer and the fading of the resin substrate, and to protect the entire laminate, it is preferable to cover at least the surface of the laminate including the resin substrate with the transparent resin layer.
　透明樹脂層に使用される材料としては、上述した積層体の物理的損傷や化学的劣化を防止できるものであれば特に限定されず、例えば、アクリル系樹脂や、オレフィン系樹脂等が挙げられる。アクリル系樹脂としては、ポリアクリル酸エステル（ポリアクリル酸メチル、ポリアクリル酸エチル、ポリアクリル酸プロピル、ポリアクリル酸ブチル、等）、ポリメタクリル酸エステル（ポリメタクリル酸メチル、ポリメタクリル酸エチル、ポリメタクリル酸プロピル、ポリメタクリル酸ブチル、等）、及びこれらの共重合体等が例示できる。また、オレフィン系樹脂としては、ポリプロピレン、ポリエチレン、ポリブテン、エチレン－プロピレン共重合体等が例示できる。 材料 The material used for the transparent resin layer is not particularly limited as long as it can prevent the above-described physical damage or chemical deterioration of the laminate, and examples thereof include an acrylic resin and an olefin resin. Acrylic resins include polyacrylates (polymethyl acrylate, polyethyl acrylate, polypropyl acrylate, polybutyl acrylate, etc.), polymethacrylates (polymethyl methacrylate, polyethyl methacrylate, Propyl methacrylate, polybutyl methacrylate, etc.), and copolymers thereof. Examples of the olefin resin include polypropylene, polyethylene, polybutene, and ethylene-propylene copolymer.
　透明樹脂層は、少なくとも樹脂基材の表面を覆う層として求められる機能を補強するために、添加剤を含有していてもよい。添加剤としては、例えば、可塑剤、紫外線吸収剤、光安定剤、耐熱安定剤、酸化防止剤、帯電防止剤、難燃剤等が挙げられる。このうち、紫外線吸収剤、光安定剤等の耐候剤は、上述した表面保護層用のものと同様である。 The transparent resin layer may contain an additive in order to reinforce at least a function required as a layer covering the surface of the resin base material. Examples of the additive include a plasticizer, an ultraviolet absorber, a light stabilizer, a heat stabilizer, an antioxidant, an antistatic agent, and a flame retardant. Among them, the weathering agent such as an ultraviolet absorber and a light stabilizer is the same as that for the surface protective layer described above.
　上記透明樹脂層用材料を混合したものをカレンダー製法等の常用の方法により製膜して透明樹脂フィルムが得られる。この透明樹脂フィルムが透明樹脂層の形成に用いられる。透明樹脂フィルムの厚みは５０～１００μｍ程度、好ましくは８０μｍ程度である。
　透明樹脂層の形成方法は特に限定されない。例えば、樹脂基材又は当該樹脂基材を備える積層体の一面側に、接着層等を介して透明樹脂フィルムを貼る方法が挙げられる。また、樹脂基材又は当該樹脂基材を備える積層体の一面側に、接着層等を介して透明樹脂フィルムの原料を直接加熱溶融押出しする方法も挙げられる。また、透明樹脂フィルムの一面側に絵柄層を塗布形成したものを、樹脂基材の一面側に貼る方法も挙げられる。接着層の原料としては、例えば、透明ポリウレタン樹脂系接着剤等が挙げられる。接着層の厚さは、例えば、１～５μｍである。 A mixture of the above-mentioned materials for the transparent resin layer is formed into a film by a conventional method such as a calendar method to obtain a transparent resin film. This transparent resin film is used for forming a transparent resin layer. The thickness of the transparent resin film is about 50 to 100 μm, preferably about 80 μm.
The method for forming the transparent resin layer is not particularly limited. For example, there is a method in which a transparent resin film is attached to one surface side of a resin substrate or a laminate including the resin substrate via an adhesive layer or the like. Further, there is also a method in which a raw material for a transparent resin film is directly heated and melt-extruded on one surface side of a resin substrate or a laminate including the resin substrate via an adhesive layer or the like. Further, a method in which a pattern layer is applied and formed on one side of a transparent resin film, and the transparent resin film is pasted on one side of a resin base material may be used. Examples of the raw material of the adhesive layer include a transparent polyurethane resin-based adhesive. The thickness of the adhesive layer is, for example, 1 to 5 μm.
　図３に示すように、樹脂基材の表面に、さらに裏面プライマー層を設けてもよい。
　裏面プライマー層は、通常、本開示の化粧シートを他の部材表面に貼り合わせる際、樹脂基材と当該部材表面との密着性を向上させるための下地として機能する層である。
　裏面プライマー層に用いられる樹脂としては、２液硬化型ウレタン－硝化綿混合樹脂（硬化剤：ヘキサメチレンジイソシアネート等）、ポリエステル／ウレタン樹脂混合樹脂、アクリロニトリル－ブタジエン－スチレン系共重合体樹脂（ＡＢＳ系樹脂）、ポリオレフィン系樹脂、スチレン系樹脂、アクリル系樹脂、塩化ビニル系樹脂、ポリカーボネート系樹脂等を好ましく挙げることができ、これらのうち１種又は２種以上を組み合せて用いることができる。裏面プライマー層に用いられる樹脂としては、これらの樹脂の内、ポリエステル／ウレタン樹脂混合樹脂、塩化ビニル系樹脂を含むことが特に好ましく、ポリエステル／ウレタン樹脂混合樹脂を含むことが最も好ましい。
　接着性を確保する観点から、裏面プライマー層の厚さとしては０．１～１０．０μｍが好ましく、０．５～３．０μｍがより好ましい。
　裏面プライマー層の形成方法としては、例えば、グラビア印刷法等の公知の方法が使用できる。 As shown in FIG. 3, a back primer layer may be further provided on the front surface of the resin base material.
The back primer layer is a layer that normally functions as a base for improving the adhesion between the resin substrate and the surface of the member when the decorative sheet of the present disclosure is bonded to the surface of another member.
Examples of the resin used for the backside primer layer include a two-component curable urethane-nitrified cotton mixed resin (hardening agent: hexamethylene diisocyanate, etc.), a polyester / urethane resin mixed resin, an acrylonitrile-butadiene-styrene copolymer resin (ABS type) Resins), polyolefin-based resins, styrene-based resins, acrylic resins, vinyl chloride-based resins, polycarbonate-based resins, and the like, and one or more of these can be used in combination. Among these resins, the resin used for the backside primer layer particularly preferably includes a polyester / urethane resin mixed resin and a vinyl chloride resin, and most preferably includes a polyester / urethane resin mixed resin.
From the viewpoint of ensuring adhesiveness, the thickness of the back primer layer is preferably from 0.1 to 10.0 μm, more preferably from 0.5 to 3.0 μm.
As a method for forming the backside primer layer, for example, a known method such as a gravure printing method can be used.
　化粧シートの厚さは特に限定されない。化粧シートの厚さは、例えば１０μｍ～１，０００μｍであってもよく、好適には５０μｍ～３００μｍである。 The thickness of the decorative sheet is not particularly limited. The thickness of the decorative sheet may be, for example, 10 μm to 1,000 μm, and is preferably 50 μm to 300 μm.
　化粧シートの特性評価は、例えば、グロス評価試験及び耐候性評価試験等により行われる。
　グロス評価試験の試験方法（グロス測定方法及びグロス評価方法）の例は以下の通りである。
（グロス測定方法）
　ＪＩＳ　Ｚ８７４１－１９９７に準拠した方法により、光沢度測定器（ＢＹＫガードナー社製「マイクログロス」）を用いて角度６０°の条件によりサンプルのグロス値を測定する。測定は表面保護層の任意の５箇所について行い、得られた測定値の平均をそのサンプルの評価に供する。
（グロス評価方法）
　次に、化粧シート中の表面保護層におけるシリカ微粒子の含有量（又は含有割合）の上限値を設定する。当該上限値以下の含有量のシリカ微粒子を用いる場合、上記グロス測定方法により得られる化粧シートのグロス値が規定値以下となるか否かで、化粧シートのグロス評価を行う。評価Ａの場合には、化粧シートのグロスが抑制できる、すなわち、化粧シートが十分な艶消し効果を奏するように、シリカ微粒子の含有量を調節可能であると評価することができる。また、評価Ｆの場合には、シリカ微粒子の含有量が多量であるにもかかわらずグロス値が大きいため、艶消し効果が不十分であると評価される。
　　Ａ：シリカ微粒子の含有量が前記上限値以下において、得られる化粧シートのグロス値が規定値以下となる。
　　Ｆ：シリカ微粒子の含有量が前記上限値を超えても、得られる化粧シートのグロス値が規定値を超える。
　ここで、例えば、表面保護層中の硬化性樹脂の硬化物１００質量部に対し、シリカ微粒子の含有量（又は含有割合）の上限値を２０質量部と設定してもよい。また、化粧シートのグロス値の規定値は、例えば、１０としてもよい。 The characteristic evaluation of the decorative sheet is performed by, for example, a gloss evaluation test and a weather resistance evaluation test.
Examples of the test method of the gloss evaluation test (the gloss measurement method and the gloss evaluation method) are as follows.
(Gloss measurement method)
The gloss value of the sample is measured by a method according to JIS Z8741-1997 using a gloss meter ("Micro Gloss" manufactured by BYK Gardner) at an angle of 60 °. The measurement is performed at any five places on the surface protective layer, and the average of the obtained measured values is used for evaluation of the sample.
(Gloss evaluation method)
Next, the upper limit value of the content (or content ratio) of the silica fine particles in the surface protective layer in the decorative sheet is set. When using silica fine particles having a content equal to or less than the upper limit, the gloss evaluation of the decorative sheet is performed based on whether the gloss value of the decorative sheet obtained by the above-described gloss measuring method is equal to or less than a specified value. In the case of evaluation A, it can be evaluated that the gloss of the decorative sheet can be suppressed, that is, the content of the silica fine particles can be adjusted so that the decorative sheet has a sufficient matting effect. In addition, in the case of evaluation F, since the gloss value is large despite the large content of silica fine particles, it is evaluated that the matting effect is insufficient.
A: When the content of the silica fine particles is equal to or less than the above upper limit, the gloss value of the obtained decorative sheet is equal to or less than the specified value.
F: Even if the content of the silica fine particles exceeds the upper limit, the gloss value of the obtained decorative sheet exceeds the specified value.
Here, for example, the upper limit of the content (or content ratio) of the silica fine particles may be set to 20 parts by mass with respect to 100 parts by mass of the cured product of the curable resin in the surface protective layer. The prescribed value of the gloss value of the decorative sheet may be, for example, 10.
　耐候性評価試験は、例えば、耐候促進試験機を用いて行われる。耐候性評価試験の試験方法の詳細は、例えば以下の通りである。尚、以下の試験機及び試験条件に基づく耐候性評価試験を「Ｓ－ＵＶ試験」とも略称する。
　・耐候促進試験機：アイスーパーＵＶテスター（商品名、型番：ＳＵＶ－Ｗ２６１、岩崎電気社製、以下、「Ｓ－ＵＶ」とも略称する。）
　・試験条件
　　温度：６３℃
　　湿度：５０％ＲＨ
　　紫外線照度：１００ｍＷ／ｃｍ２
　・試験方法：２０時間連続で紫外線照射した後、試験環境を４時間結露の状態にする。これを１サイクルとして繰り返す。
　試験開始３００時間後及び５００時間後の化粧シートの表面保護層を観察し、以下の通り評価する。評価Ａであれば、化粧シートの表面保護層が優れた長期耐候性を有すると評価することができる。
　Ａ：表面保護層の白化は確認されない。
　Ｂ：表面保護層に軽微な白化が確認される。
　Ｆ：表面保護層に著しい白化が確認される。 The weather resistance evaluation test is performed using, for example, a weather resistance acceleration tester. The details of the test method of the weather resistance evaluation test are as follows, for example. The weather resistance evaluation test based on the following tester and test conditions is also abbreviated as “S-UV test”.
-Weathering Acceleration Testing Machine: Eye Super UV Tester (trade name, model number: SUV-W261, manufactured by Iwasaki Electric Co., Ltd., hereinafter abbreviated as "S-UV")
・ Test conditions Temperature: 63 ° C
Humidity: 50% RH
UV illuminance: 100 mW / cm 2
Test method: After irradiating ultraviolet rays for 20 hours continuously, the test environment is kept in a dew condensation state for 4 hours. This is repeated as one cycle.
The surface protective layer of the decorative sheet was observed 300 hours and 500 hours after the start of the test, and evaluated as follows. In the case of evaluation A, it can be evaluated that the surface protective layer of the decorative sheet has excellent long-term weather resistance.
A: No whitening of the surface protective layer is observed.
B: Slight whitening is observed on the surface protective layer.
F: Remarkable whitening is observed in the surface protective layer.
　本開示の化粧シートは、優れた艶消し効果を有し、かつ耐候性能が長期持続するため表面保護層の白化が生じにくい。そのため、具体的用途としては、主に建築内装部材及び建築外装部材の装飾の用途が挙げられ、例えば、外壁、塀、屋根等の建築物の外装材用；壁、床、天井等の建築物の内装材用；窓枠、扉枠、手摺等の建具用；自動車等の車両の内装材用又は外装材用；等が挙げられる。 化粧 The decorative sheet of the present disclosure has an excellent matting effect and has a long-lasting weather resistance, so that the surface protective layer is hardly whitened. Therefore, specific applications are mainly used for decoration of architectural interior members and architectural exterior members, for example, for exterior materials of buildings such as outer walls, walls, roofs, etc .; buildings such as walls, floors, ceilings, etc. For window frames, door frames, handrails and other fittings; for interior materials or exterior materials of vehicles such as automobiles;
　１．化粧シートの製造
　［実施例１］
　樹脂基材として、両面にコロナ処理を施したポリプロピレンシート（厚さ：８０μｍ）を用意した。
　樹脂基材の一方の面に、２液硬化型アクリル－ウレタン樹脂をバインダーとする印刷インキを、グラビア印刷法により塗布することによって、木目模様の絵柄層（厚さ：３μｍ）を形成した。
　樹脂基材の他方の面に、２液硬化型ウレタン－硝化綿混合樹脂、及び当該樹脂１００質量部に対して、硬化剤としてヘキサメチレンジイソシアネートを５質量部含む樹脂組成物を塗布することによって、裏面プライマー層（厚さ：３μｍ）を形成した。
　絵柄層において、樹脂基材と接する側とは反対側の面上に、透明のポリウレタン樹脂系接着剤を塗布することによって、接着層（乾燥後の厚さ：３μｍ）を形成した。
　接着層上に、透明なポリプロピレン樹脂をＴダイ押出機により加熱溶融押出しして、透明樹脂層（厚さ：８０μｍ）を形成した。 1. Production of decorative sheet [Example 1]
As a resin base material, a polypropylene sheet (thickness: 80 μm) having both surfaces subjected to corona treatment was prepared.
On one surface of the resin substrate, a printing ink using a two-component curable acrylic-urethane resin as a binder was applied by a gravure printing method to form a wood-grained pattern layer (thickness: 3 μm).
On the other surface of the resin substrate, a two-component curable urethane-nitrified cotton mixed resin, and a resin composition containing 5 parts by mass of hexamethylene diisocyanate as a curing agent for 100 parts by mass of the resin, A back primer layer (thickness: 3 μm) was formed.
An adhesive layer (thickness after drying: 3 μm) was formed by applying a transparent polyurethane resin-based adhesive on the surface of the picture layer opposite to the side in contact with the resin substrate.
On the adhesive layer, a transparent polypropylene resin was heated and melt extruded by a T-die extruder to form a transparent resin layer (thickness: 80 μm).
　次に、下記プライマー層用樹脂組成物を調製した。
（プライマー層用樹脂組成物）
　主剤：ポリカーボネート系ウレタン／アクリル共重合体　１００質量部
　硬化剤：１，６－ヘキサメチレンジイソシアネート　５質量部
　紫外線吸収剤：２－［４－｛（２－ヒドロキシ－３－ドデシルオキシプロピル）オキシ｝－２－ヒドロキシフェニル］－４，６－ビス（２，４－ジメチルフェニル）－１，３，５－トリアジン〔ＴＩＮＵＶＩＮ４００（商品名）、ＢＡＳＦジャパン株式会社製〕　２質量部
　光安定剤：ビス（１－オクチルオキシ－２，２，６，６－テトラメチル－４－ピペリジル）セバケート〔ＴＩＮＵＶＩＮ１２３（商品名）、ＢＡＳＦジャパン株式会社製〕　１質量部 Next, the following resin composition for a primer layer was prepared.
(Resin composition for primer layer)
Main agent: 100 parts by mass of a polycarbonate urethane / acrylic copolymer Curing agent: 5 parts by mass of 1,6-hexamethylene diisocyanate UV absorber: 2- [4-{(2-hydroxy-3-dodecyloxypropyl) oxy}- 2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine [TINUVIN400 (trade name), manufactured by BASF Japan Ltd.] 2 parts by mass Light stabilizer: bis (1 -Octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate [TINUVIN123 (trade name), BASF Japan Ltd.] 1 part by mass
　透明樹脂層の表面にコロナ放電処理を施した後、プライマー層用樹脂組成物をグラビア印刷法で塗布することにより、プライマー層（乾燥後の厚さ：４μｍ）を形成した。 (4) After applying a corona discharge treatment to the surface of the transparent resin layer, the primer layer resin composition was applied by a gravure printing method to form a primer layer (thickness after drying: 4 μm).
　次に、下記電離放射線硬化性樹脂、シリカ微粒子、紫外線吸収剤、及び光安定剤を含む表面保護層用樹脂組成物を調製した。
（表面保護層用樹脂組成物）
・電離放射線硬化性樹脂：ウレタンアクリレートオリゴマー（重量平均分子量：４，０００、官能基数：３）　１００質量部
・シリカ微粒子（製造方法：ゲル法、吸油量：１８０ｍＬ／１００ｇ、粒径（Ｄ５０）：４．４μｍ）　１７質量部
・紫外線吸収剤：２－［４－｛（２－ヒドロキシ－３－ドデシルオキシプロピル）オキシ｝－２－ヒドロキシフェニル］－４，６－ビス（２，４－ジメチルフェニル）－１，３，５－トリアジン〔ＴＩＮＵＶＩＮ４００（商品名）、ＢＡＳＦジャパン株式会社製〕　１質量部
・光安定剤：ヒンダードアミン光安定剤（ビス（１－オクチルオシキ－２，２，６，６－テトラメチル－４－ピペリジニル）セバケート、商品名：ＴＩＮＵＶＩＮ１２３、ＢＡＳＦ社製）　１質量部
　なお、シリカ微粒子の粒径（Ｄ５０）は、体積基準でのメジアン径とした。また、実施例１において、シリカ微粒子の添加量は、得られる化粧シートのグロス値（６０°）が１０となるように調節された結果、電離放射線硬化性樹脂１００質量部に対し、１７質量部と決定された。 Next, a resin composition for a surface protective layer containing the following ionizing radiation-curable resin, silica fine particles, an ultraviolet absorber, and a light stabilizer was prepared.
(Resin composition for surface protective layer)
-Ionizing radiation curable resin: 100 parts by mass of urethane acrylate oligomer (weight average molecular weight: 4,000, number of functional groups: 3)-Silica fine particles (production method: gel method, oil absorption: 180 mL / 100 g, particle size (D50): 4.4 μm) 17 parts by mass, UV absorber: 2- [4-{(2-hydroxy-3-dodecyloxypropyl) oxy} -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) ) -1,3,5-Triazine [TINUVIN 400 (trade name), manufactured by BASF Japan Ltd.] 1 part by mass.Light stabilizer: hindered amine light stabilizer (bis (1-octyloxy-2,2,6,6-tetra) Methyl-4-piperidinyl) sebacate, trade name: TINUVIN123, manufactured by BASF) 1 part by mass The particle size of the silica fine particles (D50 ) Is the median diameter on a volume basis. Further, in Example 1, the addition amount of the silica fine particles was adjusted so that the gloss value (60 °) of the obtained decorative sheet became 10, and as a result, 17 parts by mass with respect to 100 parts by mass of the ionizing radiation-curable resin. It was decided.
　プライマー層上に表面保護層用樹脂組成物を塗布することにより未硬化樹脂層を形成した。その後、電子線（加圧電圧：１７５ＫｅＶ、５Ｍｒａｄ（５０ｋＧｙ））を照射して未硬化樹脂層を硬化させることにより、表面保護層（厚さ：５μｍ）を形成した。
　このように、７層構造（表面保護層／プライマー層／透明樹脂層／接着層／絵柄層／樹脂基材／裏面プライマー層）を有する積層体を、実施例１の化粧シートとした（図３）。 An uncured resin layer was formed by applying the resin composition for a surface protective layer on the primer layer. Thereafter, the uncured resin layer was cured by irradiating an electron beam (applied voltage: 175 KeV, 5 Mrad (50 kGy)) to form a surface protective layer (thickness: 5 μm).
Thus, a laminate having a seven-layer structure (surface protective layer / primer layer / transparent resin layer / adhesive layer / picture layer / resin base material / backside primer layer) was used as the decorative sheet of Example 1 (FIG. 3). ).
　［実施例２～実施例４、比較例１～比較例３］
　実施例１において調製される表面保護層用樹脂組成物において、シリカ微粒子の種類及び添加量を下記表１の通り変更したこと以外は、実施例１と同様に、実施例２～実施例４及び比較例１～比較例３の化粧シートを製造した。 [Examples 2 to 4, Comparative Examples 1 to 3]
In the resin composition for a surface protective layer prepared in Example 1, the types and addition amounts of the silica fine particles were changed as shown in Table 1 below, and as in Example 1, Examples 2 to 4 and The decorative sheets of Comparative Examples 1 to 3 were produced.
　２．評価方法
　（１）グロス評価
［グロス測定方法］
　以下、実施例１～実施例４及び比較例１～比較例３の化粧シートをグロス測定のサンプルとした。
　ＪＩＳ　Ｚ８７４１－１９９７に準拠した方法により、光沢度測定器（ＢＹＫガードナー社製「マイクログロス」）を用いて角度６０°の条件によりサンプルのグロス値を測定した。測定は表面保護層の任意の５箇所について行い、得られた測定値の平均をそのサンプルの評価に供した。
［グロス評価方法］
　実施例１～実施例４及び比較例１～比較例３の化粧シート製造に使用した各表面保護層用樹脂組成物において、電離放射線硬化性樹脂１００質量部に対するシリカ微粒子の含有量の上限を２０質量部としたとき、上記グロス測定方法により得られる化粧シートのグロス値が１０以下となるか否かで、化粧シートのグロス評価を行った。
　　Ａ：シリカ微粒子の当該含有量が２０質量部以下において、得られる化粧シートのグロス値が１０以下となる。
　　Ｆ：シリカ微粒子の当該含有量が２０質量部を超えても、得られる化粧シートのグロス値が１０を超える。 2. Evaluation method (1) Gloss evaluation [Gloss measurement method]
Hereinafter, the decorative sheets of Examples 1 to 4 and Comparative Examples 1 to 3 were used as gloss measurement samples.
The gloss value of the sample was measured by a method according to JIS Z8741-1997 using a gloss meter ("Micro Gloss" manufactured by BYK Gardner) at an angle of 60 °. The measurement was performed at any five places on the surface protective layer, and the average of the obtained measured values was used for evaluation of the sample.
[Gross evaluation method]
In each of the resin compositions for the surface protective layer used in the production of the decorative sheets of Examples 1 to 4 and Comparative Examples 1 to 3, the upper limit of the content of the silica fine particles to 100 parts by mass of the ionizing radiation-curable resin was 20. The gloss evaluation of the decorative sheet was performed based on whether or not the gloss value of the decorative sheet obtained by the above-described gloss measuring method was 10 or less when the amount was given by mass.
A: When the content of the silica fine particles is 20 parts by mass or less, the gloss value of the obtained decorative sheet is 10 or less.
F: Even if the content of the silica fine particles exceeds 20 parts by mass, the gloss value of the obtained decorative sheet exceeds 10.
　（２）耐候性評価
　実施例１～実施例４及び比較例１～比較例３の化粧シートについて、耐候促進試験機（Ｓ－ＵＶ）を用いた耐候性評価試験を実施した。試験の詳細は以下の通りである。
　・耐候促進試験機：アイスーパーＵＶテスター（商品名、型番：ＳＵＶ－Ｗ２６１、岩崎電気社製）
　・試験条件
　　温度：６３℃
　　湿度：５０％ＲＨ
　　紫外線照度：１００ｍＷ／ｃｍ２
　・試験方法：２０時間連続で紫外線照射した後、試験環境を４時間結露の状態にした。これを１サイクルとして繰り返した。
　試験開始３００時間後及び５００時間後の各化粧シートの表面保護層を観察し、それぞれ以下の通り評価した。
　Ａ：表面保護層の白化は確認されなかった。
　Ｂ：表面保護層に軽微な白化が確認された。
　Ｆ：表面保護層に著しい白化が確認された。 (2) Evaluation of Weather Resistance The decorative sheets of Examples 1 to 4 and Comparative Examples 1 to 3 were subjected to a weather resistance evaluation test using a weather acceleration test machine (S-UV). The details of the test are as follows.
・ Weather resistance tester: Eye Super UV Tester (trade name, model number: SUV-W261, manufactured by Iwasaki Electric Co., Ltd.)
・ Test conditions Temperature: 63 ° C
Humidity: 50% RH
UV illuminance: 100 mW / cm 2
Test method: After irradiating ultraviolet rays continuously for 20 hours, the test environment was dew-condensed for 4 hours. This was repeated as one cycle.
The surface protective layer of each decorative sheet was observed 300 hours and 500 hours after the start of the test, and evaluated as follows.
A: No whitening of the surface protective layer was observed.
B: Slight whitening was confirmed in the surface protective layer.
F: Significant whitening was confirmed in the surface protective layer.
　下記表１は、実施例１～実施例４及び比較例１～比較例３の実験結果をまとめた表である。下記表１中、「シリカ含有量（質量部）」とは、表面保護層用樹脂組成物中の電離放射線硬化性樹脂１００質量部に対するシリカ微粒子の含有量（質量部）を意味する。上述したように、シリカ微粒子の含有量は、得られる化粧シートのグロス値（６０°）が１０となるように調節された量である。
　また、下記表１中、「Ｓ－ＵＶ　３００ｈ」とは、Ｓ－ＵＶ試験開始３００時間後の評価を、「Ｓ－ＵＶ　５００ｈ」とは、Ｓ－ＵＶ試験開始５００時間後の評価を、それぞれ意味する。なお、後述するように、比較例２の化粧シート製造において、シリカ微粒子を２０質量部以上添加してもグロスが１０を超えたため、比較例２については耐候性評価を行っていない。 Table 1 below summarizes the experimental results of Examples 1 to 4 and Comparative Examples 1 to 3. In Table 1 below, “silica content (parts by mass)” means the content (parts by mass) of silica fine particles with respect to 100 parts by mass of the ionizing radiation-curable resin in the resin composition for a surface protective layer. As described above, the content of the silica fine particles is an amount adjusted so that the gloss value (60 °) of the obtained decorative sheet becomes 10.
In Table 1 below, “S-UV 300h” means the evaluation 300 hours after the start of the S-UV test, and “S-UV 500h” means the evaluation 500 hours after the start of the S-UV test. means. As will be described later, in the production of the decorative sheet of Comparative Example 2, since the gloss exceeded 10 even when silica particles were added in an amount of 20 parts by mass or more, the weather resistance of Comparative Example 2 was not evaluated.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　３．考察
　比較例１の化粧シートは、吸油量が３００ｍＬ／１００ｇのシリカ微粒子を含む。上記表１より、比較例１において、Ｓ－ＵＶ試験開始３００時間後の耐候性評価はＢであるが、Ｓ－ＵＶ試験開始５００時間後の耐候性評価はＦである。したがって、吸油量が２８０ｍＬ／１００ｇを超えるシリカ微粒子を表面保護層に使用した場合、長期耐候性が充分でないことが分かる。 3. Discussion The decorative sheet of Comparative Example 1 contains silica fine particles having an oil absorption of 300 mL / 100 g. From the above Table 1, in Comparative Example 1, the weather resistance evaluation 300 hours after the start of the S-UV test is B, and the weather resistance evaluation 500 hours after the start of the S-UV test is F. Therefore, when silica fine particles having an oil absorption of more than 280 mL / 100 g are used for the surface protective layer, it is understood that the long-term weather resistance is not sufficient.
　比較例２の化粧シートは、吸油量が９０ｍＬ／１００ｇのシリカ微粒子を含む。上記表１より、比較例２のグロス評価はＦである。すなわち、比較例２においては、シリカ微粒子を２０質量部以上添加してもグロスが１０を超えた。したがって、吸油量が１００ｍＬ／１００ｇ未満のシリカ微粒子を表面保護層に使用した場合、表面保護層の艶消し効果が充分でないことが分かる。 化粧 The decorative sheet of Comparative Example 2 contains silica fine particles having an oil absorption of 90 mL / 100 g. From the above Table 1, the gloss evaluation of Comparative Example 2 is F. That is, in Comparative Example 2, the gloss exceeded 10 even when the silica fine particles were added in an amount of 20 parts by mass or more. Therefore, when the silica fine particles having an oil absorption of less than 100 mL / 100 g are used for the surface protective layer, the matting effect of the surface protective layer is not sufficient.
　比較例３の化粧シートは、沈降法シリカを含む。上記表１より、比較例３において、Ｓ－ＵＶ試験開始３００時間後の耐候性評価はＢであるが、Ｓ－ＵＶ試験開始５００時間後の耐候性評価はＦである。したがって、沈降法シリカを表面保護層に使用した場合、長期耐候性が充分でないことが分かる。 化粧 The decorative sheet of Comparative Example 3 contains precipitated silica. From Table 1 above, in Comparative Example 3, the weather resistance evaluation 300 hours after the start of the S-UV test is B, and the weather resistance evaluation 500 hours after the start of the S-UV test is F. Therefore, it is understood that when the precipitated silica is used for the surface protective layer, the long-term weather resistance is not sufficient.
　一方、実施例１～実施例４の化粧シートは、吸油量が１８０ｍＬ／１００ｇ以上２７０ｍＬ／１００ｇ以下であり、かつゲル法により製造されたシリカ微粒子を含む。表１より、実施例１～実施例４において、グロス評価及びＳ－ＵＶ試験開始３００時間後の耐候性評価はいずれもＡであり、さらにＳ－ＵＶ試験開始５００時間後の耐候性評価はＢ以上である。したがって、ゲル法により製造され、かつ、吸油量が１００ｍＬ／１００ｇ以上２８０ｍＬ／１００ｇ以下であるシリカ微粒子を表面保護層に含有する化粧シートは、当該表面保護層における優れた艶消し効果及び長期間使用後の白化抑制効果を両立できることが実証された。 On the other hand, the decorative sheets of Examples 1 to 4 have an oil absorption of 180 mL / 100 g or more and 270 mL / 100 g or less and contain silica fine particles produced by a gel method. From Table 1, in Examples 1 to 4, the gloss evaluation and the weather resistance evaluation 300 hours after the start of the S-UV test were all A, and the weather resistance evaluation 500 hours after the start of the S-UV test was B. That is all. Therefore, a decorative sheet produced by the gel method and containing silica fine particles having an oil absorption of 100 mL / 100 g or more and 280 mL / 100 g or less in the surface protective layer has an excellent matting effect in the surface protective layer and long-term use. It was proved that the effect of suppressing the later whitening can be compatible.
　１　樹脂基材
　２　表面保護層
　３　絵柄層
　４　裏面プライマー層
　５　接着剤層
　６　透明樹脂層
　７　プライマー層
　１００，２００，３００　化粧シートの実施形態 DESCRIPTION OF SYMBOLS 1 Resin base material 2 Surface protective layer 3 Picture layer 4 Back primer layer 5 Adhesive layer 6 Transparent resin layer 7 Primer layer 100, 200, 300 Embodiment of decorative sheet

Claims (2)

  1. 　樹脂基材、及び当該樹脂基材の少なくとも一方の面側に表面保護層を備え、
    　前記表面保護層が、
    　硬化性樹脂の硬化物、及び、
    　ゲル法により製造され、かつ、吸油量が１００ｍＬ／１００ｇ以上２８０ｍＬ／１００ｇ以下であるシリカ微粒子を含有することを特徴とする化粧シート。     A resin substrate, and a surface protective layer on at least one surface side of the resin substrate,
    The surface protective layer,
    Cured product of curable resin, and
    A decorative sheet produced by a gel method and containing silica fine particles having an oil absorption of 100 mL / 100 g or more and 280 mL / 100 g or less.
  2. 　前記シリカ微粒子の粒径（Ｄ５０）は１μｍ以上２０μｍ以下である、請求項１に記載の化粧シート。 The decorative sheet according to claim 1, wherein the particle diameter (D50) of the silica fine particles is 1 µm or more and 20 µm or less.
PCT/JP2019/038477 2018-09-28 2019-09-30 Decorative sheet WO2020067565A1 (en)

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JP7324436B2 (en) 2021-03-31 2023-08-10 大日本印刷株式会社 Decorative sheet and decorative member using the same

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