WO2024034555A1 - 化粧シート用樹脂組成物、化粧シート及び化粧材 - Google Patents

化粧シート用樹脂組成物、化粧シート及び化粧材 Download PDF

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Publication number
WO2024034555A1
WO2024034555A1 PCT/JP2023/028700 JP2023028700W WO2024034555A1 WO 2024034555 A1 WO2024034555 A1 WO 2024034555A1 JP 2023028700 W JP2023028700 W JP 2023028700W WO 2024034555 A1 WO2024034555 A1 WO 2024034555A1
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Prior art keywords
layer
decorative sheet
decorative
resin
resin composition
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PCT/JP2023/028700
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English (en)
French (fr)
Japanese (ja)
Inventor
義昭 根津
圭佑 風間
雅貴 和田
淳一 田向
智美 中島
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大日本印刷株式会社
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Priority to JP2024540453A priority Critical patent/JPWO2024034555A1/ja
Publication of WO2024034555A1 publication Critical patent/WO2024034555A1/ja

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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
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F15/00—Flooring
    • E04F15/02—Flooring or floor layers composed of a number of similar elements

Definitions

  • the present invention relates to a resin composition for a decorative sheet, a decorative sheet, and a decorative material.
  • decorative sheets have been laminated on the surfaces of various articles in order to impart design properties.
  • decorative sheets are laminated on a base material and used as decorative materials for building floors, table tops, counters, and the like.
  • the above-mentioned decorative sheet is also an excellent decorative sheet and can be used as a decorative sheet without any problems, but there is room for further improvement in so-called heat and humidity resistance. That is, since the ionomer resin has a low melting point, when it comes into contact with a heat source such as boiling water at about 100° C., the gloss of the surface of a decorative sheet formed using the ionomer resin may change. Therefore, when it is used as a decorative sheet, the areas where it can be used are limited, so it is required to have heat and humidity resistance.
  • Examples of methods for improving heat and humidity resistance include crosslinking of ionomer resins by electron beam irradiation, polymer blending with other resins, multilayer film formation, and addition of inorganic fillers.
  • polymer blends and multilayer coatings have problems such as peeling (delami) and whitening due to the compatibility between the ionomer resin and the resin used, resulting in poor appearance and poor scratch resistance. There is a problem that whitening occurs during processing.
  • the ability to prevent the fire from spreading in the event of a fire is an important performance factor in ensuring evacuation time. It is. Therefore, the decorative sheet is required to have characteristics that suppress the expansion of the area of the decorative sheet that is on fire in the event of a fire, and prevent the fire from spreading easily.
  • Flame retardants are useful in imparting properties to decorative sheets that prevent fire from spreading.
  • the decorative sheet contains a flame retardant
  • problems such as peeling (delami) and whitening due to low compatibility between the resin used in the decorative sheet and the flame retardant, resulting in poor appearance and poor scratch resistance.
  • whitening occurs during processing such as bending whitening and stretching whitening. It is difficult to provide a decorative sheet with both these properties and the property that fire does not easily spread.
  • a resin composition for a decorative sheet that can form a decorative sheet that has excellent scratch resistance and heat and humidity resistance, suppresses whitening, and has excellent resistance to the spread of fire, and the resin composition
  • the development of decorative sheets using materials is desired.
  • the present invention provides a resin composition for a decorative sheet, which can produce a decorative sheet that has excellent scratch resistance and heat and humidity resistance, suppresses whitening, and is resistant to the spread of fire. With the goal.
  • Another object of the present invention is to provide a decorative sheet and decorative material that have excellent scratch resistance and heat and humidity resistance, are inhibited from whitening, and are highly resistant to the spread of fire.
  • the present invention relates to the following resin composition for decorative sheets, decorative sheets, and decorative materials.
  • a resin composition for a decorative sheet comprising a (meth)acrylic acid copolymer and a phosphinate metal salt compound.
  • the resin composition for a decorative sheet according to item 1 wherein the (meth)acrylic acid copolymer is at least one selected from the group consisting of an ethylene-(meth)acrylic acid copolymer and an ionomer. thing.
  • Item 3 The resin composition for a decorative sheet according to Item 1 or 2, wherein the phosphinate metal salt compound is an aluminum phosphinate compound. 4.
  • a decorative sheet comprising a resin composition for decorative sheets containing a metal salt compound. 6.
  • the content of the phosphinate metal salt compound in the layer containing the (meth)acrylic acid copolymer and the phosphinate metal salt compound is 100% of the (meth)acrylic acid copolymer.
  • Item 5 The decorative sheet according to Item 5, wherein the part by mass is 5 parts by mass or more and 20 parts by mass or less. 7.
  • Item 7. The decorative sheet according to item 5 or 6, wherein the transparent resin layer has a thickness of 60 ⁇ m or more and 300 ⁇ m or less. 8.
  • Item 8 The decorative sheet according to any one of Items 5 to 7, which has a surface protective layer on the outermost surface and has an uneven shape on the surface protective layer side. 9. Item 9.
  • the resin composition for a decorative sheet of the present invention can produce a decorative sheet that has excellent scratch resistance and heat and humidity resistance, suppresses whitening, and is highly resistant to the spread of fire.
  • the decorative sheet and decorative material of the present invention are manufactured using the resin composition for decorative sheets, they have excellent scratch resistance and heat and humidity resistance, are inhibited from whitening, and are resistant to the spread of fire. Excellent in difficulty.
  • FIG. 2 is a schematic diagram showing a test method for determining the difficulty of fire spread.
  • FIG. 2 is a schematic diagram showing a test method for determining the difficulty of fire spread.
  • the surface opposite to the side on which the decorative sheet is laminated with the base material is the so-called "front surface", which is the surface that is visually recognized when applied to a floor etc. . Therefore, in this specification, the direction of the surface of the decorative sheet opposite to the side where it is laminated with the base material is referred to as "top”, and the direction of the opposite side, that is, the side where it is laminated with the base material, is referred to as "top”. It is called ⁇ Ura'' or ⁇ Bottom''. Similarly, in this specification, the direction of the surface of the decorative material on the decorative sheet side is referred to as "upper”, and the direction of the opposite side, that is, the surface on the base material side, is referred to as "back” or “lower”.
  • (meth)acrylic acid refers to acrylic acid and methacrylic acid
  • the (meth)acrylic acid-based copolymer refers to an acrylic acid-based copolymer and/or a methacrylic acid-based copolymer. Indicates a copolymer.
  • Resin composition for decorative sheets contains a (meth)acrylic acid copolymer and a phosphinate metal salt compound. It is characterized by The resin composition of the present invention having the above characteristics contains a (meth)acrylic acid copolymer and a phosphinate metal salt compound. A pseudo-crosslinking reaction occurs in which the system compound appears to be crosslinked. Therefore, when a layer such as a transparent resin layer of a decorative sheet is formed using the resin composition for a decorative sheet of the present invention, the scratch resistance and moist heat resistance of the decorative sheet are improved, and whitening is suppressed.
  • the phosphinate metal salt compound is incorporated into the (meth)acrylic acid copolymer, making it difficult to be visually recognized as particles, and whitening during processing is suppressed.
  • the resin composition of the present invention contains a (meth)acrylic acid-based copolymer and a phosphinate metal salt-based compound, so that it has excellent flame resistance and is highly resistant to the spread of fire. Decorative sheets can be manufactured.
  • the (meth)acrylic acid copolymer is not particularly limited as long as it has an acrylic acid structural unit, and examples thereof include ethylene-(meth)acrylic acid copolymers, ionomers, and the like.
  • the (meth)acrylic acid copolymers include ethylene-(meth)acrylic acid copolymers such as ethylene-acrylic acid copolymers (EAA) and ethylene-methacrylic acid copolymers (EMAA).
  • EAA ethylene-acrylic acid copolymers
  • EMA ethylene-methacrylic acid copolymers
  • EAA ethylene-acrylic acid copolymers
  • EMA ethylene-methacrylic acid copolymers
  • EAA ethylene-acrylic acid copolymers
  • EMA ethylene-methacrylic acid copolymers
  • Ionomers such as an ionomer of ethylene-acrylic acid copolymer and an ionomer of ethylene-methacrylic acid copolymer can be used.
  • the above (meth)acrylic acid copolymers may be used alone or in combination of two or more.
  • the content of the (meth)acrylic acid copolymer in the resin composition for decorative sheets of the present invention is preferably 83% by mass or more, more preferably 89% by mass or more, based on 100% by mass of the resin composition for decorative sheets. It is preferably 91% by mass or more, and more preferably 91% by mass or more. Further, the content of the (meth)acrylic acid copolymer in the resin composition is preferably 95% by mass or less, more preferably 94% by mass or less, and 93% by mass or less, based on 100% by mass of the resin composition. More preferred. When the lower limit of the content of the (meth)acrylic acid copolymer is within the above range, the scratch resistance of the decorative sheet formed using the resin composition is further improved. In addition, since the upper limit of the content of the (meth)acrylic acid copolymer is within the above range, the decorative sheet formed using the resin composition has better moist heat resistance, whitening resistance, and difficulty in spreading fire. improves.
  • the phosphinate metal salt compound is not particularly limited as long as it has a phosphinate metal salt structure in its molecule.
  • Such a phosphinate metal salt compound can form a pseudo-crosslink with the (meth)acrylic acid copolymer described below, and can exhibit flame retardancy. Therefore, as the phosphinate metal salt compound, those used as phosphinate metal salt flame retardants can be used.
  • phosphinate metal salt-based compounds examples include phosphinate metal salts and/or diphosphinate metal salts (hereinafter also referred to as "phosphinate metal salts").
  • Examples of the phosphinate metal salt include the following general formula (1): Examples include compounds represented by:
  • diphosphinate metal salt for example, the following general formula (2): Examples include compounds represented by:
  • R 1 , R 2 , R 3 and R 4 each independently represent an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aryl group having 6 to 12 carbon atoms. selected from the group consisting of 7 to 20 arylalkyl groups.
  • R 5 is selected from the group consisting of an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an alkylarylene group having 7 to 20 carbon atoms, and an arylalkylene group having 7 to 20 carbon atoms.
  • M is a metal, preferably at least one metal selected from the group consisting of calcium (ion), magnesium (ion), aluminum (ion), and zinc (ion). Further, p is 2 or 3, m is 2 or 3, n is 1 or 3, and x is 1 or 2.
  • examples of the phosphinate metal salt include a compound represented by the following general formula (1-1).
  • examples of the phosphinate metal salt include a compound represented by the following general formula (1-2).
  • examples of the diphosphinic acid metal salt include a compound represented by the following general formula (2-1).
  • examples of the diphosphinic acid metal salt include a compound represented by the following general formula (2-2).
  • the above alkyl group includes a straight chain or branched saturated aliphatic group.
  • Examples of the above aryl group include aromatic groups having 6 to 20 carbon atoms, which are unsubstituted or substituted with various substituents. Specific examples of such groups include phenyl group, benzyl group, o-tolyl group, 2,3-xylyl group, and the like.
  • phosphinic acid metal salts include phosphinic acid and metal carbonates, metal hydroxides, metal oxides, etc., as described in European Patent Application Publication No. 699708, JP-A-8-73720, etc. It can be produced in an aqueous solution using the following metal components. These are essentially monomeric compounds, but depending on the reaction conditions, in some circumstances also polymeric phosphinate metal salts with a degree of condensation of 1 to 3 are included.
  • the phosphinic acid and diphosphinic acid that form the phosphinic acid metal salt are not particularly limited, and include, for example, dimethylphosphinic acid, ethylmethylphosphinic acid, diethylphosphinic acid, methyl-n-propylphosphinic acid, methanedi(methylphosphinic acid), and benzene. -1,4-di(methylphosphinic acid), methylphenylphosphinic acid, diphenylphosphinic acid and the like.
  • the metal component forming the phosphinate metal salt is not particularly limited, and examples thereof include calcium ions, magnesium ions, aluminum ions, zinc ions, and the like. Among these, aluminum ions are preferred, that is, the phosphinate metal salt compound is preferably an aluminum phosphinate compound.
  • the metal phosphinate is not particularly limited, and includes, for example, calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum phosphinate, aluminum dimethylphosphinate, zinc phosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, and ethylmethylphosphine.
  • phosphinate metal salt compounds may be used alone or in combination of two or more.
  • the content of the phosphinate metal salt compound in the resin composition is preferably 5 parts by mass or more and 20 parts by mass or less, and 7 parts by mass or more and 12 parts by mass or less, based on 100 parts by mass of the (meth)acrylic acid copolymer. More preferably, it is 8 parts by mass or more and 11 parts by mass or less.
  • the lower limit of the content of the phosphinate metal salt compound is within the above range, the moist heat resistance, whitening resistance, and difficulty in spreading of fire of the decorative sheet formed using the resin composition are further improved.
  • the upper limit of the content of the phosphinate metal salt compound is within the above range, the transparency of the decorative sheet formed using the resin composition is further improved.
  • the resin composition of the present invention can be used to form a decorative sheet using the resin composition of the present invention as described below.
  • the decorative sheet of the present invention has a base sheet and/or a transparent resin layer, and at least one layer selected from the group consisting of the base sheet and the transparent resin layer is made of (meth)acrylic acid.
  • the present invention is characterized by comprising a resin composition for a decorative sheet containing a phosphinate metal salt-based compound and a phosphinate metal salt-based compound.
  • at least one layer selected from the group consisting of a base sheet and a transparent resin layer contains a (meth)acrylic acid copolymer and a phosphinate metal salt compound.
  • the resin composition for decorative sheets of the present invention described above is comprised of the above-mentioned resin composition for decorative sheets of the present invention
  • a pseudo-crosslinking reaction occurs in which the (meth)acrylic acid copolymer and the phosphinate metal salt compound become crosslinked.
  • the decorative sheet of the present invention has improved scratch resistance and moist heat resistance by having a layer such as a transparent resin layer formed using the above-described resin composition for decorative sheets of the present invention. and whitening is suppressed.
  • the phosphinate metal salt compound is incorporated into the (meth)acrylic acid copolymer, making it difficult to be visually recognized as particles, and whitening during processing is suppressed.
  • the decorative sheet of the present invention has a base sheet and/or a transparent resin layer formed using the resin composition for decorative sheets of the present invention described above, it has excellent flame resistance and is fire resistant. It has excellent resistance to the spread of flame.
  • the decorative sheet of the present invention is not limited in its layer structure as long as it has a base sheet and/or a transparent resin layer.
  • the layer structure of the decorative sheet of the present invention as shown in FIG. 16 in this order (layer structure including a base sheet and a transparent resin layer).
  • the decorative sheet of the present invention has a pattern layer 13 (solid ink layer 131 and pattern ink layer 132), a transparent resin layer 14, a primer layer 15, and a surface protection layer 16 in this order. (a layered structure without a base sheet).
  • the decorative sheet of the present invention may have a layer structure including a back primer layer 11, a base sheet 12, a primer layer 15, and a surface protection layer 16 in this order, as shown in FIG. ).
  • At least one layer selected from the group consisting of a base sheet and a transparent resin layer contains a (meth)acrylic acid copolymer and a phosphinate metal salt compound.
  • the resin composition for decorative sheets of the present invention contains a (meth)acrylic acid copolymer and a phosphinate metal salt compound.
  • the transparent resin layer is a layer formed of the resin composition of the present invention.
  • the base sheet is a layer formed of the resin composition of the present invention.
  • the content of the phosphinate metal salt compound in the layer containing the (meth)acrylic acid copolymer and the phosphinate metal salt compound is It is preferably 5 parts by mass or more and 20 parts by mass or less, more preferably 7 parts by mass or more and 12 parts by mass or less, and even more preferably 8 parts by mass or more and 11 parts by mass or less, based on 100 parts by mass of the polymer.
  • the lower limit of the content of the phosphinate metal salt compound is within the above range, the heat and humidity resistance, whitening resistance, and difficulty in spreading of fire of the decorative sheet are further improved.
  • the upper limit of the content of the phosphinate metal salt compound is within the above range, the transparency of the decorative sheet is further improved.
  • each layer constituting the decorative sheet of the present invention will be specifically explained using the decorative sheet having the layer structure shown in FIG. 1 as a representative example.
  • the transparent resin layer contains a (meth)acrylic acid copolymer and a phosphinate metal salt compound.
  • This layer is made of a resin composition for decorative sheets.
  • the resin composition for decorative sheets the above-mentioned resin composition of the present invention can be used.
  • the transparent resin layer is a layer formed of the resin composition of the present invention.
  • the transparent resin layer may be formed of a resin composition other than the resin composition of the present invention.
  • the transparent resin layer formed from the above-mentioned other resin composition is not particularly limited, and for example, a transparent resin layer containing at least one resin selected from the group consisting of polyolefin resins and polyester resins may be used. Can be mentioned.
  • polyolefin resin a polyolefin thermoplastic resin is preferable, and an olefin thermoplastic elastomer is more preferable in that it further suppresses the whitening of the resin sheet upon bending.
  • polyolefin resins include polyethylene, ethylene- ⁇ olefin copolymer, polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, and ethylene-vinyl acetate copolymer. , saponified ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester copolymer, and the like. Among these, polypropylene is preferred.
  • polyester thermoplastic resins can be used, such as polyethylene terephthalate, polyalkylene terephthalate with high heat resistance [for example, polyethylene in which a portion of ethylene glycol has been replaced with 1,4-cyclohexanedimethanol, diethylene glycol, etc.
  • polyethylene terephthalate so-called PET-G (trade name, manufactured by Eastman Chemical Company)
  • PET-G trade name, manufactured by Eastman Chemical Company
  • polybutylene terephthalate polyethylene naphthalate
  • polyethylene naphthalate-isophthalate copolymer and the like.
  • polyalkylene terephthalate which has high heat resistance, is preferred.
  • the transparent resin layer may be colored as long as it has transparency.
  • a coloring agent may be added to the thermoplastic resin.
  • the coloring agent pigments or dyes used in the picture pattern layer can be used.
  • the transparent resin layer contains various substances such as fillers, matting agents, foaming agents, lubricants, antistatic agents, antioxidants, ultraviolet absorbers, light stabilizers, radical scavengers, and soft components (e.g., rubber). It may also contain additives.
  • the filler is not particularly limited as long as it does not impair the transparency of the transparent resin layer, and examples thereof include inorganic fillers such as silica, calcium carbonate, talc, and clay.
  • the filler is not limited to the transparent resin layer, and may be contained in the transparent resin layer and/or the base sheet.
  • the transparent resin layer further contains an inorganic filler having a polar group on the surface.
  • the transparent resin layer containing the phosphinate metal salt-based compound contains an inorganic filler having a polar group on the surface, the flame retardance of the resin sheet and the difficulty in spreading of fire are further improved. This is because the polar moiety of the phosphinate metal salt compound is attracted to the polar group on the surface of the inorganic filler having a polar group, and the presence of the phosphinate metal salt compound on the surface improves dispersibility. it is conceivable that.
  • a hydrophilic inorganic filler can be used, such as an inorganic filler having a hydroxyl group such as a silanol group on the surface, and more specifically, hydrophilic silica can be used. Can be done.
  • the silica used as a filler may be either a natural product or a synthetic product, and may be either crystalline or amorphous.
  • the synthetic amorphous silica may be prepared by either a wet method or a dry method.
  • the method for preparing the synthetic wet method silica prepared by a wet method is not particularly limited, and examples thereof include a precipitation method, a gel method, and the like.
  • the method for preparing synthetic dry process silica prepared by a dry process is not particularly limited, and examples thereof include a combustion process, an arc process, and the like.
  • silica silica having a small average particle size is preferable from the viewpoint of further improving the sharpness of the decorative sheet, and fumed silica obtained by a combustion method and hydrophilic fumed silica are more preferable.
  • the BET specific surface area of the filler such as hydrophilic fumed silica is preferably 50 m 2 /g or more, more preferably 130 m 2 /g or more, and even more preferably 200 m 2 /g or more. Since the lower limit of the BET specific surface area of the filler is within the above range, the average particle size is small, and in the case of hydrophilic fumed silica, the amount of silanol increases, so adding the filler increases the transparency of the transparent resin layer. In addition, the dispersibility of the phosphinate metal salt compound is further improved, and the sharpness and flame retardance of the resin sheet are further improved. Moreover, since the lower limit of the BET specific surface area of the filler is within the above range, the flame retardance of the decorative sheet is improved and the content of the phosphinate metal salt compound can be reduced.
  • the BET specific surface area is a BET specific surface area measured by a nitrogen adsorption method according to a measurement method based on DIN66131.
  • a commercially available hydrophilic fumed silica can be used as a filler.
  • Examples of such commercially available products include AEROSIL 50, AEROSIL 130, AEROSIL 200, AEROSIL 300, and AEROSIL 380 manufactured by Nippon Aerosil Co., Ltd.
  • the content of the filler in the transparent resin layer is 100 mass of the phosphinate metal salt compound in the transparent resin layer.
  • the amount is preferably 50 parts by mass or more, more preferably 100 parts by mass or more, and even more preferably 200 parts by mass or more.
  • the content of the filler in the transparent resin layer is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and still more preferably 10 parts by mass or less, based on 100 parts by mass of the resin component in the transparent resin layer. preferable.
  • the thickness of the transparent resin layer is preferably 60 ⁇ m or more, more preferably 80 ⁇ m or more. Moreover, the thickness of the transparent resin layer is preferably 300 ⁇ m or less, more preferably 200 ⁇ m or less.
  • the scratch resistance and abrasion resistance of the decorative sheet are further improved.
  • the upper limit of the thickness of the transparent resin layer is further improved.
  • the surface of the transparent resin layer may be subjected to surface treatment such as corona discharge treatment, ozone treatment, plasma treatment, ionizing radiation treatment, dichromic acid treatment, etc., as necessary.
  • the surface treatment may be performed according to a conventional method for each treatment.
  • Primer layer A primer layer (a primer layer for facilitating the formation of a surface protective layer) may be formed on the surface of the transparent resin layer.
  • the primer layer can be formed by applying a known primer agent to the transparent resin layer.
  • the primer include urethane resin primers made of acrylic-modified urethane resins, resin-based primers made of block copolymers of acrylic and urethane, and the like.
  • the thickness of the primer layer is not particularly limited, but is usually about 0.1 to 10 ⁇ m, preferably about 1 to 5 ⁇ m.
  • the base sheet contains a (meth)acrylic acid-based copolymer and a phosphinate metal salt-based compound.
  • This layer is made of a resin composition for decorative sheets.
  • the resin composition for decorative sheets the above-mentioned resin composition of the present invention can be used.
  • the base sheet is a layer formed of the resin composition of the present invention.
  • the base sheet may be formed of a resin composition other than the resin composition of the present invention.
  • the base sheet formed from the above other resin composition is not particularly limited, and includes, for example, a base sheet containing at least one resin selected from the group consisting of polyolefin resins and polyester resins. .
  • polyolefin resin a polyolefin thermoplastic resin is preferable, and an olefin thermoplastic elastomer is more preferable in that it further suppresses the whitening of the resin sheet upon bending.
  • polyolefin resins include polyethylene, ethylene- ⁇ olefin copolymer, polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, and ethylene-vinyl acetate copolymer. , saponified ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester copolymer, and the like. Among these, polypropylene is preferred.
  • polyester thermoplastic resins can be used, such as polyethylene terephthalate, polyalkylene terephthalate with high heat resistance [for example, polyethylene in which a portion of ethylene glycol has been replaced with 1,4-cyclohexanedimethanol, diethylene glycol, etc.
  • polyethylene terephthalate so-called PET-G (trade name, manufactured by Eastman Chemical Company)
  • PET-G trade name, manufactured by Eastman Chemical Company
  • polybutylene terephthalate polyethylene naphthalate
  • polyethylene naphthalate-isophthalate copolymer and the like.
  • polyalkylene terephthalate which has high heat resistance, is preferred.
  • the base sheet may contain magnesium hydroxide.
  • the base sheet contains magnesium hydroxide, the flame retardancy of the decorative sheet and the difficulty in spreading of fire are further improved.
  • Magnesium hydroxide is not particularly limited, and particulate magnesium hydroxide can be used.
  • the shape of the magnesium hydroxide particles is not particularly limited, and may be spherical, flaky, acicular, etc., and spherical particles are preferably used.
  • Magnesium hydroxide may be surface-treated with a fatty acid, a silane coupling agent, etc. in order to further improve its affinity with the resin contained in the base sheet.
  • those surface-treated with fatty acids are preferred.
  • magnesium hydroxide As magnesium hydroxide, commercially available products can be used. Commercially available magnesium hydroxide products include, for example, Mugsys N, Mugsys S, Mugsys EP, Mugsys W (manufactured by Kamishima Chemical Industries, Ltd.), ECOMAG, etc. (manufactured by Tateho Chemical Industries, Ltd.), Kisuma 5, Kisuma 8, etc. Among these, Mugsys N (Magsies N-6) (trade name, manufactured by Kamishima Chemical Industries, Ltd.) can be preferably used.
  • the average particle diameter of magnesium hydroxide is preferably 0.1 to 5 ⁇ m, more preferably 0.1 to 1 ⁇ m.
  • the lower limit of the average particle diameter is within the above range, the dispersibility into the base sheet is improved and the flame retardance is further improved. If it is smaller than the lower limit, the kneading torque increases during kneading with the resin, which tends to cause agglomeration and may reduce dispersibility.
  • the upper limit of the average particle diameter is within the above range, the surface properties of the resin sheet are improved, and the quality of designs such as printed patterns formed on the surface of the resin sheet is further improved. When the upper limit is exceeded, particles and particle-induced aggregates are likely to be formed on the sheet surface, and the design quality may be likely to deteriorate.
  • the content of magnesium hydroxide in the base sheet is preferably 10% by mass or more, and more preferably 15% by mass or more, based on 100% by mass of the base sheet. Further, the content of magnesium hydroxide in the base sheet is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less, based on 100% by mass of the base sheet.
  • the flame retardancy of the decorative sheet is further improved. Further, by setting the upper limit of the magnesium content within the above range, stability (thickness, width, etc.) during film formation of the decorative sheet can be ensured.
  • the thickness of the base sheet is preferably 20 to 300 ⁇ m, more preferably 40 to 200 ⁇ m.
  • the base sheet may be colored if necessary.
  • the surface may be subjected to surface treatment such as corona discharge treatment, plasma treatment, ozone treatment, etc., or may be coated with a primer, which is a base paint for improving adhesion with adjacent layers.
  • a back primer layer may be provided on the back surface of the base sheet, if necessary. For example, it is advantageous when bonding a base sheet and an adherend to produce a decorative material such as a decorative floor material.
  • the back primer layer can be formed by applying a known primer agent to the back surface of the base sheet.
  • the primer include urethane resin primers made of acrylic modified urethane resin (acrylic urethane resin), urethane-cellulose resins (for example, resins made by adding hexamethylene diisocyanate to a mixture of urethane and nitrified cotton) ), and resin-based primers made of block copolymers of acrylic and urethane.
  • additives may be added to the primer.
  • additives include fillers such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, ultraviolet absorbers, and light stabilizers. The blending amount of the additive can be appropriately set depending on the product characteristics.
  • the thickness of the back primer layer is not particularly limited, but is usually about 0.1 to 10 ⁇ m, preferably about 1 to 5 ⁇ m.
  • the pattern layer is composed of a pattern ink layer and/or a solid ink layer.
  • the pattern layer can be formed by known printing methods such as gravure printing, offset printing, silk screen printing, and inkjet printing. Examples of the patterns of the pattern ink layer include wood grain patterns, stone grain patterns, cloth grain patterns, skin pattern patterns, geometric patterns, letters, symbols, line drawings, various abstract patterns, flower patterns, landscapes, characters, and the like.
  • the solid ink layer is obtained by solid printing with colored ink.
  • the pattern layer is composed of one or both of a pattern ink layer and a solid ink layer.
  • the ink used for the pattern layer includes, as a vehicle, a chlorinated polyolefin such as chlorinated polyethylene or chlorinated polypropylene, polyester, polyurethane consisting of isocyanate and polyol, polyacrylic, polyvinyl acetate, polyvinyl chloride, vinyl chloride-vinyl acetate.
  • An ink made by using one or a mixture of copolymers, cellulose resins, polyamide resins, etc. and adding pigments, solvents, various auxiliary agents, etc. can be used.
  • one type or a mixture of two or more types of resins such as polyester, polyurethane consisting of isocyanate and polyol, polyacrylic, polyamide resin, etc. are preferable from the viewpoint of environmental issues, adhesion to the printing surface, etc.
  • the thickness of the picture pattern layer is not particularly limited and can be set as appropriate depending on the product characteristics, but the layer thickness is approximately 0.1 to 10 ⁇ m.
  • Transparent adhesive layer A transparent adhesive layer is provided between the picture pattern layer and the transparent resin layer, if necessary.
  • the transparent adhesive layer can be obtained, for example, by applying and drying a known dry lamination adhesive such as a two-component curable urethane resin.
  • the thickness of the transparent adhesive layer after drying is preferably about 0.1 to 30 ⁇ m, more preferably about 1 to 5 ⁇ m.
  • the decorative sheet of the present invention may have a surface protective layer (transparent surface protective layer).
  • the surface protective layer is provided to impart surface properties such as scratch resistance, abrasion resistance, water resistance, and stain resistance required to the decorative sheet.
  • the decorative sheet of the present invention preferably has a surface protective layer on the side opposite to the base sheet of the transparent resin layer, such as the outermost surface.
  • a surface protective layer on the outermost surface, and in combination with the fact that the surface protective layer contains at least one type of curable resin as described below, the surface protective layer can be used to prevent the decomposition of the resin in the layer below the surface protective layer in the event of a fire, etc.
  • the surface protective layer delays the generation of combustion gas, further improving the difficulty of fire spreading.
  • the decorative sheet of the present invention preferably has a surface protective layer on the outermost surface and an uneven shape on the surface protective layer side.
  • the resin forming the surface protective layer preferably contains at least one type of curable resin such as a thermosetting resin or an ionizing radiation curable resin. Further, as the resin forming the surface protective layer, a thermosetting resin and an ionizing radiation curable resin may be mixed and used as necessary. Furthermore, the surface protective layer may be formed by laminating a thermosetting resin layer and an ionizing radiation curing resin layer in this order from the transparent resin layer side, or by laminating multiple resin layers made of the same type of resin. It may also be formed by Furthermore, the surface protection layer includes, from the transparent resin layer side, a first surface protection layer formed by mixing a thermosetting resin and an ionizing radiation curable resin, and a second surface formed of an ionizing radiation curable resin.
  • the structure may include a protective layer, and specifically, from the transparent resin layer side, a first surface protective layer formed by mixing a thermosetting resin and an ultraviolet curable resin, and an ultraviolet curable resin.
  • the structure may include a second surface protective layer formed by.
  • the total thickness of the surface protective layer is the same as the thickness of the surface protective layer described later.
  • the resin forming the surface protective layer ionizing radiation-curable resins are particularly preferred from the viewpoints of high surface hardness, productivity, and the like. Furthermore, from the viewpoint of further improving weather resistance, electron beam curable resins are most preferred.
  • ionizing radiation curing which is a curable resin with a high crosslink density among curable resins.
  • Type resins are preferred, and electron beam curable resins are more preferred.
  • thermosetting resins include unsaturated polyester resins, polyurethane resins (including two-component curing polyurethanes), epoxy resins, aminoalkyd resins, phenolic resins, urea resins, diallyl phthalate resins, melamine resins, guanamine resins, and melamine.
  • examples include urea cocondensation resins, silicone resins, and polysiloxane resins.
  • a crosslinking agent, a curing agent such as a polymerization initiator, and a polymerization accelerator can be added to the resin.
  • a curing agent such as a polymerization initiator
  • a polymerization accelerator can be added to the resin.
  • curing agents isocyanates, organic sulfonates, etc. can be added to unsaturated polyester resins, polyurethane resins, etc., organic amines, etc. can be added to epoxy resins, peroxides such as methyl ethyl ketone peroxide, azoisobutyl nitrile, etc.
  • Radical initiators can be added to unsaturated polyester resins.
  • thermosetting resin examples include a method in which a solution of a thermosetting resin is applied by a coating method such as a roll coating method or a gravure coating method, and then dried and cured.
  • the coating amount of the solution is approximately 5 to 50 ⁇ m in terms of solid content, preferably about 5 to 40 ⁇ m.
  • the ionizing radiation curable resin is not limited as long as it is a resin that undergoes a crosslinking polymerization reaction upon irradiation with ionizing radiation and changes into a three-dimensional polymer structure.
  • one or more of prepolymers, oligomers, and monomers having a polymerizable unsaturated bond or epoxy group in the molecule that can be crosslinked by irradiation with ionizing radiation can be used.
  • Examples include acrylate resins such as urethane acrylate, polyester acrylate, and epoxy acrylate; silicon resins such as siloxane; polyester resins; and epoxy resins.
  • Examples of ionizing radiation include visible light, ultraviolet rays (near ultraviolet rays, vacuum ultraviolet rays, etc.), X-rays, electron beams, ion beams, etc. Among these, ultraviolet rays and electron beams are preferable, and electron beams are more preferable.
  • ultra-high pressure mercury lamps high-pressure mercury lamps, low-pressure mercury lamps, carbon arc lamps, black light fluorescent lamps, and metal halide lamps can be used.
  • the wavelength of ultraviolet rays is approximately 190 to 380 nm.
  • various electron beam accelerators such as a Cockcroftwald type, Vandegraft type, resonant transformer type, insulated core transformer type, linear type, Dynamitron type, and high frequency type can be used.
  • the energy of the electron beam is preferably about 100 to 1000 keV, more preferably about 100 to 300 keV.
  • the amount of electron beam irradiation is preferably about 20 to 150 KGy.
  • Ionizing radiation-curable resins are sufficiently cured by irradiation with electron beams, but when curing by irradiation with ultraviolet rays, it is preferable to add a photopolymerization initiator (sensitizer).
  • a photopolymerization initiator sensitizer
  • photopolymerization initiators include, for example, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether, Michler benzoyl benzoate, Michler ketone, diphenyl sulfide, dibenzyl disulfide. , diethyl oxide, triphenylbiimidazole, and isopropyl-N,N-dimethylaminobenzoate.
  • a resin system having a cationic polymerizable functional group for example, at least one of aromatic diazonium salts, aromatic sulfonium salts, metallocene compounds, benzoin sulfonic acid esters, freeloxysulfoxonium diallylodosyl salts, etc. can be used.
  • the amount of the photopolymerization initiator added is not particularly limited, but is generally about 0.1 to 10 parts by weight per 100 parts by weight of the ionizing radiation curable resin.
  • a solution of the ionizing radiation-curable resin may be applied by a coating method such as a gravure coating method or a roll coating method.
  • the coating amount of the solution is approximately 10 to 50 ⁇ m in terms of solid content, preferably about 15 to 40 ⁇ m.
  • the thickness of the surface protective layer is preferably 4 ⁇ m or more, more preferably 8 ⁇ m or more, even more preferably 10 ⁇ m or more, and particularly preferably 12 ⁇ m or more. Moreover, the thickness of the surface protective layer is preferably 50 ⁇ m or less, more preferably 40 ⁇ m or less, even more preferably 30 ⁇ m or less, and particularly preferably 20 ⁇ m or less.
  • the lower limit of the thickness of the surface protective layer is within the above range, the scratch resistance and abrasion resistance of the decorative sheet are further improved.
  • the upper limit of the thickness of the surface protective layer is further improved, and appropriate rigidity is obtained, so that the handleability of the decorative sheet is improved.
  • each layer explained above can be carried out, for example, by forming a picture pattern layer (solid ink layer, pattern ink layer) on one side of the base sheet by printing, and then applying a known material such as a two-component curing type urethane resin onto the picture pattern layer.
  • a picture pattern layer solid ink layer, pattern ink layer
  • This can be carried out by laminating transparent resin layers using a dry lamination adhesive by dry lamination, T-die extrusion lamination, or the like, and then forming a surface protective layer.
  • the total thickness of the decorative sheet is preferably 110 ⁇ m or more, more preferably 120 ⁇ m or more. Further, the total thickness of the decorative sheet is preferably 400 ⁇ m or less, more preferably 250 ⁇ m or less.
  • the scratch resistance and abrasion resistance of the decorative sheet are further improved.
  • the difficulty of fire spreading in the decorative sheet is further improved.
  • An uneven shape may be formed on the decorative sheet by embossing it from the transparent resin layer side (the upper side of the decorative sheet).
  • the resin sheet of the present invention may have an uneven shape on the side opposite to the base sheet of the transparent resin layer.
  • the uneven shape can be formed by heat pressing, hairline processing, etc.
  • Examples of the uneven shape include wood grain conduit grooves, stone plate surface unevenness, cloth surface texture, satin finish, sand grain, hairline, parallel grooves, and the like.
  • the decorative sheet may have a synthetic resin backer layer within a range that does not impede properties such as flame retardancy. By including the synthetic resin backer layer, the impact resistance of the decorative sheet is further improved.
  • Examples of the resin constituting the synthetic resin backer layer include polypropylene, ethylene-vinyl alcohol copolymer, polymethylene, polymethylpentene, polyethylene terephthalate, and highly heat-resistant polyalkylene terephthalate [for example, a portion of ethylene glycol , polyethylene terephthalate substituted with 4-cyclohexanedimethanol or diethylene glycol, so-called PET-G (manufactured by Eastman Chemical Company)], polybutylene terephthalate, polyethylene naphthalate, polyethylene naphthalate-isophthalate copolymer, Examples include polycarbonate, polyarylate, polyimide, polystyrene, polyamide, ABS, and the like. These resins can be used alone or in combination of two or more.
  • the synthetic resin backer layer may be colored similarly to the transparent resin layer.
  • a coloring agent may be added to the synthetic resin.
  • the coloring agent pigments or dyes used in the picture pattern layer can be used.
  • the synthetic resin backer layer contains fillers, matting agents, foaming agents, lubricants, antistatic agents, antioxidants, ultraviolet absorbers, light stabilizers, radical scavengers, soft ingredients ( For example, various additives such as rubber), flame retardants, etc. may be included.
  • fillers examples include inorganic fillers such as silica, calcium carbonate, talc, and clay.
  • the flame retardant is not particularly limited and can be used regardless of whether it is inorganic or organic.
  • the thickness of the synthetic resin backer layer is preferably 0.1 to 0.6 mm, more preferably 0.15 to 0.45 mm, and even more preferably 0.20 to 0.40 mm.
  • the thickness of the synthetic resin backer layer is preferably 0.1 to 0.6 mm, more preferably 0.15 to 0.45 mm, and even more preferably 0.20 to 0.40 mm.
  • the various additives (magnesium hydroxide contained in the base sheet, the phosphinate metal salt compound contained in the transparent resin layer, etc.) added to the above-mentioned layers of the decorative sheet of the present invention may be added to the vesicles.
  • the method for forming various additives into vesicles is not particularly limited, and may be formed by any known method, and among them, supercritical reverse phase evaporation is preferred.
  • the supercritical reverse phase evaporation method is a method in which water-soluble or hydrophilic substances are uniformly dissolved in carbon dioxide in a supercritical state or at a temperature or pressure above the supercritical point.
  • an aqueous phase containing various additives as an encapsulating substance is added to form a capsule-shaped vesicle containing various additives as an encapsulating substance in a single layer of membrane.
  • carbon dioxide in a supercritical state means carbon dioxide in a supercritical state at a critical temperature (30.98°C) and a critical pressure (7.3773 ⁇ 0.0030 MPa) or higher;
  • Carbon dioxide under pressure conditions means carbon dioxide under conditions where only the critical temperature or only the critical pressure exceeds the critical condition.
  • the above phospholipids include phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiolipin, egg yolk lecithin, hydrogenated yolk egg lecithin, soybean lecithin, glycerophospholipids such as hydrogenated soybean lecithin, and sphingomyelin. , ceramide phosphorylethanolamine, ceramide phosphorylglycerol, and other sphingophospholipids.
  • a dispersant such as a nonionic surfactant or a mixture of this and cholesterol or triacylglycerol can be used.
  • nonionic surfactants examples include polyglycerin ether, dialkylglycerin, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, polyoxyethylene polyoxypropylene copolymer, and polybutadiene.
  • polyoxyethylene copolymer polybutadiene-poly2-vinylpyridine, polystyrene-polyacrylic acid copolymer, polyethylene oxide-polyethylethylene copolymer, polyoxyethylene-polycaprolactam copolymer, etc. The above can be used.
  • the above-mentioned cholesterols include one or more of cholesterol, ⁇ -cholestanol, ⁇ -cholestanol, cholestane, desmosterol (5,24-cholestadien-3 ⁇ -ol), sodium cholate, cholecalciferol, etc. Can be used.
  • the outer membrane of the liposome may be formed from a mixture of a phospholipid and a dispersant.
  • the outer membrane in the decorative sheet of the present invention, by forming the outer membrane as a liposome formed from phospholipid, it is possible to improve the compatibility between the resin composition, which is the main component of each layer, and various additives.
  • the decorative sheet of the present invention may contain a NOR type hindered amine compound in at least one layer selected from the group consisting of the base sheet and the transparent resin layer.
  • NOR type hindered amine compounds can trap radicals generated from organic matter during combustion and make it difficult to continue combustion. Therefore, at least one layer selected from the group consisting of a base sheet and a transparent resin layer contains a hindered amine compound. By containing it, the amount of heat generated can be further reduced in the heat generation test based on ISO5660-1.
  • the decorative sheet of the present invention preferably has a structure in which the phosphinate metal salt compound and the NOR type hindered amine compound are contained in the same layer, from the viewpoint of further improving the above-mentioned effects.
  • NOR type hindered amine compound for example, a compound represented by the following general formula (3) can be used.
  • R 5 to R 8 each represent a hydrogen atom or an organic group of the following general formula (4). At least one of R 5 to R 8 is an organic group represented by the following general formula (4).
  • R 9 represents an alkyl group having 1 to 17 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, a phenyl group, or a phenylalkyl group having 7 to 15 carbon atoms
  • R 10 , R 11 , R 12 and R 13 each represent an alkyl group having 1 to 4 carbon atoms.
  • R 14 represents a hydrogen atom or a straight or branched alkyl group having 1 to 12 carbon atoms.
  • the alkyl group having 1 to 17 carbon atoms that is R 9 is preferably a methyl group or an octyl group.
  • the cycloalkyl group having 5 to 10 carbon atoms is preferably a cyclohexyl group.
  • the phenyl group or the phenylalkyl group having 7 to 15 carbon atoms is preferably a phenyl group.
  • the alkyl group having 1 to 4 carbon atoms represented by R 10 to R 13 is preferably a methyl group.
  • the linear or branched alkyl group having 1 to 12 carbon atoms, which is R 14 is preferably an n-butyl group.
  • R 5 , R 6 , and R 7 are organic groups represented by general formula (4), or R 5 , R 6 , and R 8 are organic groups represented by general formula (4).
  • R 5 , R 6 , and R 8 are organic groups represented by general formula (4).
  • NOR-type hindered amine compounds include N,N',N'''-tris ⁇ 2,4-bis[(1-hydrocarbyloxy-2,2,6,6-tetramethylpiperidin-4-yl) ) alkylamino]-s-triazin-6-yl ⁇ -3,3'-ethylenediiminodipropylamine, N,N',N''-tris ⁇ 2,4-bis[(1-hydrocarbyloxy-2 ,2,6,6-tetramethylpiperidin-4-yl)alkylamino]-s-triazin-6-yl ⁇ -3,3'-ethylenediiminodipropylamine and its crosslinked derivatives, bis(1-octyl Oxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)adipate, bis(1-cyclohex
  • the NOR type hindered amine compounds may be used alone or in combination of two or more.
  • the content of the NOR type hindered amine compound in each layer of the thermoplastic resin layer containing the NOR type hindered amine compound is preferably 0.2 to 5% by mass, and 0.5% by mass, with the layer containing the NOR type hindered amine compound being 100% by mass. -3% by mass is more preferable.
  • the decorative sheet when a decorative sheet is laminated on a base material with low thermal conductivity, the decorative sheet becomes easily flammable.
  • the reason may be as follows.
  • a base material with low thermal conductivity makes it difficult for heat from the front surface to be transmitted to the back surface of the base material, and the amount of heat applied to the base material surface remains on the base material surface;
  • thermal conductivity is low.
  • Low density base materials tend to have low density and tend to contain air layers.
  • the decorative sheet of the present invention has the above-described configuration, even when laminated on a base material with low thermal conductivity, fire hardly spreads.
  • the decorative sheet of the present invention can be particularly suitably used as a decorative sheet for interior materials and a decorative sheet for floors.
  • the decorative material of the present invention is a decorative material having the above-mentioned decorative sheet on an adherend.
  • the decorative sheet of the present invention As the decorative sheet constituting the decorative material of the present invention, the decorative sheet of the present invention described above can be used.
  • the material of the adherend is not particularly limited, and inorganic adherends such as galvanized steel plates, metal plates such as aluminum plates, and silica plates may be used, or synthetic resins containing fillers such as inorganic substances may be used.
  • a resin-based adherend may also be used.
  • a wood-based adherend may be used, in which a surface material is laminated on a wood board that is commonly used for decorative materials such as decorative materials for floors.
  • the surface material is not particularly limited, and examples thereof include cork, awl, plywood, medium density fiberboard (MDF), high density fiberboard (HDF), etc., and combinations of these may also be used.
  • the thickness of the surface material is not particularly limited, and is preferably 1.0 to 5.0 mm, more preferably 1.0 to 2.5 mm.
  • the wood board is not particularly limited, and examples thereof include medium density fiberboard (MDF), high density fiberboard (HDF), plywood, and the like. Among these, plywood is preferably used.
  • MDF medium density fiberboard
  • HDF high density fiberboard
  • plywood is preferably used.
  • the thickness of the wood board is not particularly limited, and is preferably 4.0 to 15.0 mm, more preferably 5.0 to 10.0 mm.
  • the method of laminating the surface material and the wooden board is not particularly limited, and can be laminated by a conventionally known method such as laminating with an adhesive.
  • the adhesive is not particularly limited, and a wide variety of known woodworking adhesives can be used.
  • adhesives include polyvinyl acetate, polyvinyl chloride, urethane, acrylic, acrylic urethane, vinyl chloride-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ionomer, butadiene-acrylonitrile rubber, neoprene rubber,
  • Examples include adhesives containing natural rubber or the like as an active ingredient.
  • thermosetting adhesives include melamine-based, phenol-based, and urea-based adhesives (vinyl acetate-urea, etc.).
  • the adherend constituting the decorative material of the present invention may have a thermal conductivity of less than 0.1 W/(m ⁇ K) on the side to which the decorative sheet is attached.
  • the thermal conductivity of an adherend is a thermal conductivity measured by the following measuring method.
  • the material forming the layer on the side of the adherend to which the resin sheet is attached is cut out into a circle with a diameter of 40 mm to prepare a measurement sample.
  • the measurement samples are stacked in the thickness direction, and an even number of samples are stacked so that the thickness exceeds 15 mm.
  • a sensor is placed between half of the laminated measurement samples, and the thermal conductivity is measured by the hot disk method in accordance with ISO 22007-2:2008. Note that when the measurement samples are stacked, it is assumed that the air layer included between adjacent measurement samples can be ignored.
  • a cork with a diameter of 40 mm and a thickness of 1.5 mm is prepared as a measurement sample. Thirty measurement samples are stacked so that the total thickness exceeds 15 mm when the measurement samples are stacked. This results in a 45 mm laminate. Next, a sensor was sandwiched between the 15th and 16th measurement samples (at a position of 22.5 mm), which is half the thickness of the laminate, and a hot disk was placed in accordance with ISO 22007-2:2008. Thermal conductivity is measured by the method.
  • the thickness of the laminate will be 40 mm, so if you insert the sensor between the 10th and 11th measurement samples, good.
  • the thickness of the laminate will be 40 mm, so if you insert the sensor between the 20th and 21st measurement samples, good.
  • the method of laminating the decorative sheet on the front surface of the adherend is not particularly limited, and conventionally known methods such as forming an adhesive layer on the front surface of the adherend and laminating the decorative sheet can be used. Can be stacked.
  • the thickness of the adhesive layer is not particularly limited, and the thickness after drying is preferably 0.1 to 100 ⁇ m, more preferably 0.1 to 30 ⁇ m, and even more preferably 1 to 20 ⁇ m.
  • Examples of adhesives used in the adhesive layer include water-soluble emulsion adhesives, polyester adhesives, acrylic adhesives, urethane adhesives, and the like.
  • the adhesive can be used alone or in combination of two or more.
  • the decorative material of the present invention has the above-mentioned structure, it has excellent scratch resistance and heat and humidity resistance, suppresses whitening, and is excellent in preventing the spread of fire. Therefore, the decorative material of the present invention can be used for decorative boards, decorative members, decorative molded products, etc., and can be suitably used as decorative boards for interior materials, especially decorative boards for floors.
  • Example 1 (Preparation of resin composition) A methacrylic acid copolymer and a phosphinate metal salt compound were mixed in the following formulation and melt-kneaded at 200°C to prepare a resin composition.
  • ⁇ Phosphinate metal salt compound aluminum phosphinate flame retardant (product name: Exolit OP-945) (manufactured by Clariant Japan Co., Ltd.): 10 parts by mass
  • a 60 ⁇ m thick opaque colored polypropylene film was prepared as a base sheet.
  • a back primer layer (thickness: 2 ⁇ m) of two-component curable urethane resin is formed on the back side of the base sheet, and the front side of the base sheet is
  • a pattern layer was formed on the surface by gravure printing using a curable printing ink containing an acrylic urethane resin.
  • a transparent adhesive layer was formed by applying a two-component curable urethane resin adhesive onto the picture pattern layer. Further, on the adhesive layer, the resin composition prepared as described above was heat-melted and extruded using a T-die extruder using a thermal lamination method to form a thermoplastic transparent resin layer (thickness: 100 ⁇ m).
  • a primer layer (thickness: 2 ⁇ m) of a two-component curable urethane resin was formed on the transparent resin layer. Furthermore, after coating and drying an electron beam curable resin composition containing a urethane (meth)acrylate oligomer on the primer layer by a gravure coating method, irradiation with an electron beam is performed under the conditions of an acceleration voltage of 165 keV and an absorbed dose of 30 kGy. A surface protective layer was formed to have a thickness of 15 ⁇ m.
  • the surface protective layer side is heated with an infrared non-contact type heater to soften the base sheet and transparent resin layer, and then immediately embossing is performed from the surface protective layer side using heat and pressure to form an uneven shape.
  • the decorative sheet of Example 1 was manufactured (layer structure shown in FIG. 1).
  • a wood base material was prepared by laminating a 1.5 mm thick cork sheet onto a 2.5 mm thick medium density fiberboard (MDF) using an adhesive.
  • MDF medium density fiberboard
  • the base sheet side surface of the decorative sheet was bonded to the cork sheet side surface of the wooden base material via a two-component curing water-soluble emulsion adhesive.
  • the coating amount of the two-component curing water-soluble emulsion adhesive was 100 g/m 2 .
  • Example 2 (Preparation of resin composition) A methacrylic acid copolymer and a phosphinate metal salt compound were mixed in the following formulation and melt-kneaded at 200°C to prepare a resin composition.
  • ⁇ Phosphinate metal salt compound aluminum phosphinate flame retardant (product name: Exolit OP-945) (manufactured by Clariant Japan Co., Ltd.): 5 parts by mass
  • a decorative sheet was manufactured in the same manner as in Example 1 except that the resin composition of Example 2 described above was used (layer structure shown in FIG. 1), and decorative materials A and B were manufactured.
  • Example 3 (Preparation of resin composition) An acrylic acid copolymer and a phosphinate metal salt compound were mixed in the following formulation and melt-kneaded at 200°C to prepare a resin composition.
  • ⁇ Acrylic acid copolymer Ethylene acrylic acid copolymer (product name: Nucrel N1108C (manufactured by Mitsui Dow Polychemical Co., Ltd.)): 100 parts by mass
  • ⁇ Phosphinate metal salt compound aluminum phosphinate flame retardant (product name: Exolit) OP-945 (manufactured by Clariant Japan Co., Ltd.): 10 parts by mass
  • a decorative sheet was manufactured in the same manner as in Example 1 except that the resin composition of Example 3 described above was used (layer structure shown in FIG. 1), and decorative materials A and B were manufactured.
  • Example 4 (Preparation of resin composition) A resin composition of Example 4 was prepared in the same manner as Example 1.
  • thermoplastic transparent resin film (thickness 120 ⁇ m) was prepared by extruding the resin composition prepared as described above using a thermal lamination method using a T-die extruder to form a film. did.
  • a pattern printing layer is formed on the back side of the transparent resin layer by a gravure printing method using a curable printing ink containing an acrylic urethane resin, and a solid printing layer is further formed on the back side of the pattern printing layer to form a picture pattern layer. Formed.
  • a primer layer (thickness: 2 ⁇ m) of a two-component curable urethane resin was formed on the transparent resin layer. Furthermore, after coating and drying an electron beam curable resin composition containing a urethane (meth)acrylate oligomer on the primer layer by a gravure coating method, irradiation with an electron beam is performed under the conditions of an acceleration voltage of 165 keV and an absorbed dose of 30 kGy. A surface protective layer was formed to have a thickness of 15 ⁇ m.
  • the surface protective layer side was heated with an infrared non-contact type heater to soften the transparent resin layer, and then immediately embossing was performed from the surface protective layer side using heat and pressure to form an uneven shape.
  • the decorative sheet of Example 4 was manufactured (layer structure shown in FIG. 2).
  • Decorative materials A and B were produced in the same manner as in Example 1 except that the decorative sheet of Example 4 described above was used.
  • Example 5 (Preparation of resin composition) A methacrylic acid copolymer and a phosphinate metal salt compound were mixed in the following formulation and melt-kneaded at 200°C to prepare a resin composition.
  • ⁇ Phosphinate metal salt compound aluminum phosphinate flame retardant (product name: Exolit OP-945) (manufactured by Clariant Japan Co., Ltd.): 10 parts by mass
  • Colorant Titanium oxide (product name: Taipeiku CR-63 (Ishihara Sangyo Co., Ltd.)): 20 parts by mass
  • thermoplastic resin film (thickness 120 ⁇ m) and using it as a base sheet.
  • a primer layer (thickness: 2 ⁇ m) of two-component curable urethane resin is formed on the back side of the base sheet, and the front side of the base sheet is A pattern layer was formed using a gravure printing method using a curable printing ink containing an acrylic urethane resin.
  • a primer layer (thickness: 2 ⁇ m) of a two-component curable urethane resin was formed on the picture pattern layer. Furthermore, after coating and drying an electron beam curable resin composition containing a urethane (meth)acrylate oligomer on the primer layer by a gravure coating method, irradiation with an electron beam is performed under the conditions of an acceleration voltage of 165 keV and an absorbed dose of 30 kGy. A surface protective layer was formed to have a thickness of 15 ⁇ m.
  • the surface protective layer side was heated with an infrared non-contact type heater to soften the base sheet, and then immediately embossing was performed by heat and pressure from the surface protective layer side to form an uneven shape.
  • the decorative sheet of Example 5 was manufactured (layer structure shown in FIG. 3).
  • Decorative materials A and B were produced in the same manner as in Example 1 except that the decorative sheet of Example 5 above was used.
  • Example 6 (Preparation of resin composition) A resin composition of Example 6 was prepared in the same manner as Example 1.
  • Example 6 (Manufacture of decorative sheets) A decorative sheet of Example 6 was produced in the same manner as Example 1 except that the thickness of the transparent resin layer was 140 ⁇ m (layer structure shown in FIG. 1).
  • Decorative material A was produced in the same manner as in Example 1 except that the decorative sheet of Example 6 above was used. For Example 6, only the scratch resistance test (coin scratch test) was evaluated.
  • Example 7 (Preparation of resin composition) A resin composition of Example 7 was prepared in the same manner as Example 1.
  • Example 7 (Manufacture of decorative sheets) A decorative sheet of Example 7 was produced in the same manner as Example 1 except that the thickness of the transparent resin layer was 280 ⁇ m (layer structure shown in FIG. 1).
  • Decorative material A was produced in the same manner as in Example 1 except that the decorative sheet of Example 7 described above was used. For Example 7, only the scratch resistance test (coin scratch test) was evaluated.
  • Example 8 (Preparation of resin composition) A resin composition of Example 8 was prepared in the same manner as Example 1.
  • thermosetting resin U Clear manufactured by DIC Graphics Co., Ltd.
  • ultraviolet curable resin urethane manufactured by DIC Graphics Co., Ltd.
  • a mixture of acrylate resin was applied to a thickness of 10 ⁇ m.
  • an ultraviolet curable resin urethane acrylate resin manufactured by DIC Graphics Co., Ltd. was applied to a thickness of 15 ⁇ m to form a surface protection layer.
  • the mixture of the first surface protective layer is a mixture of 60% by mass of thermosetting resin and 40% by mass of ultraviolet curable resin.
  • Decorative material A was produced in the same manner as in Example 1 except that the decorative sheet of Example 8 above was used. In addition, regarding Example 8, only the scratch resistance was evaluated.
  • Comparative example 1 (Preparation of resin composition) The following acrylic acid copolymer was prepared as a resin composition.
  • a decorative sheet was manufactured in the same manner as in Example 1 except that the resin composition of Comparative Example 1 described above was used (layer structure shown in FIG. 1), and decorative materials A and B were manufactured.
  • Comparative example 2 Preparation of resin composition
  • a methacrylic acid copolymer and a phosphoric acid ester compound were mixed in the following formulation and melt-kneaded at 200°C to prepare a resin composition.
  • ⁇ Phosphate ester compound Product name: PX200 (manufactured by Daihachi Chemical Co., Ltd.): 10 parts by mass
  • a decorative sheet was manufactured in the same manner as in Example 1 except that the resin composition of Comparative Example 2 described above was used (layer structure shown in FIG. 1), and decorative materials A and B were manufactured.
  • Comparative example 3 Preparation of resin composition
  • a methacrylic acid copolymer and an inorganic filler were mixed in the following formulation and melt-kneaded at 200°C to prepare a resin composition.
  • ⁇ Methacrylic acid copolymer Ionomer (product name: Himilan 1706 (manufactured by Mitsui Dow Polychemicals Co., Ltd.)): 100 parts by mass
  • ⁇ Inorganic filler Magnesium hydroxide (product name: Magseeds N-6 (Kamishima Chemical Co., Ltd.) )): 10 parts by mass
  • a decorative sheet was manufactured in the same manner as in Example 1 except that the resin composition of Comparative Example 3 described above was used (layer structure shown in FIG. 1), and decorative materials A and B were manufactured.
  • Comparative example 4 Preparation of resin composition
  • a polypropylene resin and a phosphinate metal salt compound were mixed in the following formulation and melt-kneaded at 200°C to prepare a resin composition.
  • ⁇ Polypropylene resin Transparent polypropylene resin: 100 parts by mass
  • ⁇ Phosphinate metal salt compound Aluminum phosphinate flame retardant (product name: Exolit OP-945 (manufactured by Clariant Japan Ltd.)): 10 parts by mass
  • a decorative sheet was manufactured in the same manner as in Example 1 except that the resin composition of Comparative Example 4 described above was used (layer structure shown in FIG. 1), and decorative materials A and B were manufactured.
  • Comparative example 5 Preparation of resin composition
  • a polypropylene resin and a phosphinate metal salt compound were mixed in the following formulation and melt-kneaded at 200°C to prepare a resin composition.
  • - Polypropylene resin Transparent polypropylene resin: 100 parts by mass
  • Phosphinate metal salt compound Aluminum phosphinate flame retardant (product name: Exolit OP-945 (manufactured by Clariant Japan Ltd.)): 5 parts by mass
  • a decorative sheet was manufactured in the same manner as in Example 1 except that the resin composition of Comparative Example 5 described above was used (layer structure shown in FIG. 1), and decorative materials A and B were manufactured.
  • Comparative example 6 (Preparation of resin composition) The following polypropylene resin was prepared as a resin composition. ⁇ Polypropylene resin: Transparent polypropylene resin: 100 parts by mass
  • a decorative sheet was manufactured in the same manner as in Example 1 except that the resin composition of Comparative Example 6 described above was used (layer structure shown in FIG. 1), and decorative materials A and B were manufactured.
  • Comparative example 7 (Preparation of resin composition) A polypropylene resin and a phosphoric acid ester compound were mixed in the following formulation and melt-kneaded at 200°C to prepare a resin composition.
  • ⁇ Polypropylene resin Transparent polypropylene resin: 100 parts by mass
  • ⁇ Phosphate ester compound Product name: PX200 (manufactured by Daihachi Chemical Industry Co., Ltd.): 10 parts by mass
  • a decorative sheet was manufactured in the same manner as in Example 1 except that the resin composition of Comparative Example 7 described above was used (layer structure shown in FIG. 1), and decorative materials A and B were manufactured.
  • Comparative example 8 Preparation of resin composition
  • a polypropylene resin and an inorganic filler were mixed in the following formulation and melt-kneaded at 200°C to prepare a resin composition.
  • ⁇ Polypropylene resin Transparent polypropylene resin: 100 parts by mass
  • ⁇ Inorganic filler Magnesium hydroxide (product name: Mugsys N-6 (manufactured by Kamishima Chemical Industry Co., Ltd.)): 10 parts by mass
  • a decorative sheet was manufactured in the same manner as in Example 1 except that the resin composition of Comparative Example 8 described above was used (layer structure shown in FIG. 1), and decorative materials A and B were manufactured.
  • Comparative example 9 Preparation of resin composition
  • a polypropylene resin and a phosphinate metal salt compound were mixed in the following formulation and melt-kneaded at 200°C to prepare a resin composition.
  • ⁇ Polypropylene resin Transparent polypropylene resin: 100 parts by mass
  • ⁇ Phosphinate metal salt compound Aluminum phosphinate flame retardant (product name: Exolit OP-945 (manufactured by Clariant Japan Ltd.)): 10 parts by mass
  • a decorative sheet was manufactured in the same manner as in Example 4 except that the resin composition of Comparative Example 9 described above was used (layer structure shown in FIG. 2), and decorative materials A and B were manufactured.
  • Haze value A decorative sheet resin composition molded into a 100 ⁇ m thick sheet was placed in a direct reading haze meter manufactured by Toyo Seiki Seisakusho Co., Ltd., and the haze value was measured. Note that if the evaluation is + or higher, it is evaluated that there is no problem in actual use. ++: Haze value is less than 20 +: Haze value is 20 or more and less than 90 -: Haze value is 90 or more
  • the decorative sheet was cut into a size of 100 mm in the MD direction (machine direction) x 50 mm in the TD direction (width direction), and used as a test piece.
  • the test piece was sharply bent at room temperature so as to form a crease in a direction parallel to the TD direction, and the appearance of the bent portion was observed. Evaluation was made according to the following evaluation criteria. +: Whitening is not confirmed -: Whitening is confirmed
  • Extension whitening (appearance) The decorative sheet was cut into a size of 100 mm in the MD direction (machine direction) x 10 mm in the TD direction (width direction), and used as a test piece. The test piece was stretched 20 mm in the MD direction at room temperature, and the appearance of the stretched portion was observed. Evaluation was made according to the following evaluation criteria. +: Whitening is not confirmed -: Whitening is confirmed
  • Decorative material B was cut out into a size of 9 cm x 30 cm and used as a test piece.
  • a rectangular metal stand 103 is placed on the stand 102 of a commercially available household heater 101 (Zaiguru Handsome SJ-100 (product name)), and a metal A test piece 105 was placed in a frame 104 made of aluminum, and a test was conducted to determine the difficulty of fire spreading under the conditions of a heater angle of 45° and a heater output dial of 4. Specifically, the test piece was preheated for 2 minutes using the household heater described above. Next, as shown in FIG.
  • the heater-side end 106 of the test piece in the longitudinal direction was heated for 1 minute with a lighter 107 to ignite it, and the flame spread in the longitudinal direction of the test piece 105 as shown in FIG. Next, the state of fire spread was visually observed, and the combustion distance (L1) and combustion duration were evaluated as follows.
  • ⁇ Combustion distance (L1)> The distance of fire spread from the initial ignition after the test piece was ignited and the lighter's flame was removed was measured and defined as the combustion distance (L1), and evaluated according to the following evaluation criteria. Note that if the evaluation is + or higher, it is evaluated that there is no problem in actual use. ++: L1 is less than 5 cm +: L1 is 5 cm or more and less than 10 cm -: L1 is 10 cm or more
  • ⁇ Burning duration> The duration of combustion from initial ignition to self-extinguishment, excluding the lighter's flame after the test piece ignited, was measured and evaluated according to the following evaluation criteria. Note that if the evaluation is + or higher, it is evaluated that there is no problem in actual use. +++: Combustion duration is less than 100 seconds or does not ignite ++: Combustion duration is 100 seconds or more and less than 300 seconds +: Combustion duration is 300 seconds or more and less than 600 seconds -: Combustion duration is 600 seconds or more (does not self-extinguish in 600 seconds)

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PCT/JP2023/028700 2022-08-10 2023-08-07 化粧シート用樹脂組成物、化粧シート及び化粧材 WO2024034555A1 (ja)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013051394A (ja) * 2011-08-03 2013-03-14 Toyo Ink Sc Holdings Co Ltd 太陽電池裏面保護シートならびに太陽電池モジュール
US20130172488A1 (en) * 2011-12-30 2013-07-04 E.I. Du Pont De Nemours And Company Compositions of Polyamide and Ionomer
JP2016500748A (ja) * 2012-11-01 2016-01-14 スリーエム イノベイティブ プロパティズ カンパニー 非ハロゲン化難燃性組成物及び物品
WO2017183515A1 (ja) * 2016-04-18 2017-10-26 日東電工株式会社 透明難燃テープおよび難燃性構造体
JP2019137010A (ja) * 2018-02-15 2019-08-22 本田技研工業株式会社 布帛
WO2021205842A1 (ja) * 2020-04-09 2021-10-14 大日本印刷株式会社 透明性樹脂フィルム、透明性樹脂フィルムの製造方法、化粧板、及び、化粧板の製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013051394A (ja) * 2011-08-03 2013-03-14 Toyo Ink Sc Holdings Co Ltd 太陽電池裏面保護シートならびに太陽電池モジュール
US20130172488A1 (en) * 2011-12-30 2013-07-04 E.I. Du Pont De Nemours And Company Compositions of Polyamide and Ionomer
JP2016500748A (ja) * 2012-11-01 2016-01-14 スリーエム イノベイティブ プロパティズ カンパニー 非ハロゲン化難燃性組成物及び物品
WO2017183515A1 (ja) * 2016-04-18 2017-10-26 日東電工株式会社 透明難燃テープおよび難燃性構造体
JP2019137010A (ja) * 2018-02-15 2019-08-22 本田技研工業株式会社 布帛
WO2021205842A1 (ja) * 2020-04-09 2021-10-14 大日本印刷株式会社 透明性樹脂フィルム、透明性樹脂フィルムの製造方法、化粧板、及び、化粧板の製造方法

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