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WO2019031116A1 - Matériau de revêtement pour former un film de revêtement pourvu d'une aptitude d'enlèvement de taches et feuille décorative obtenue à l'aide de celui-ci - Google Patents

Matériau de revêtement pour former un film de revêtement pourvu d'une aptitude d'enlèvement de taches et feuille décorative obtenue à l'aide de celui-ci Download PDF

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Publication number
WO2019031116A1
WO2019031116A1 PCT/JP2018/025321 JP2018025321W WO2019031116A1 WO 2019031116 A1 WO2019031116 A1 WO 2019031116A1 JP 2018025321 W JP2018025321 W JP 2018025321W WO 2019031116 A1 WO2019031116 A1 WO 2019031116A1
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Prior art keywords
mass
parts
meth
acrylate
polyfunctional
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Ceased
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PCT/JP2018/025321
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English (en)
Japanese (ja)
Inventor
宮川　浩
茂一 伊藤
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Riken Technos Corp
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Riken Technos Corp
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Priority to JP2019535031A priority Critical patent/JP7157060B2/ja
Publication of WO2019031116A1 publication Critical patent/WO2019031116A1/fr
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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
    • 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
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • 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
    • C09D7/42—Gloss-reducing agents

Definitions

  • the present invention relates to paints. More specifically, the present invention relates to a paint capable of forming a coating film having excellent stain removability (hereinafter sometimes referred to as "stain removability coating film”), and a decorative sheet using the same.
  • stain removability coating film a paint capable of forming a coating film having excellent stain removability
  • a decorative sheet is used by laminating a decorative sheet on the surface of a base material formed of a metal material such as iron or aluminum.
  • the coating film having excellent stain removability is a coating formed using a paint containing a compound having at least one anionic hydrophilic group selected from the group consisting of a sulfonic acid group, a carboxyl group, and a phosphoric acid group.
  • Membranes have been proposed (see, for example, Patent Document 1).
  • the decorative sheet having the stain removing coating film formed by these techniques has insufficient bending resistance, and has a disadvantage that it is difficult to apply to so-called 2D molding such as lapping molding.
  • An object of the present invention is to provide a paint capable of forming a coating film excellent in stain removability, and a decorative sheet using the same.
  • the further subject of this invention can form the coating film excellent in dirt removal property and bending resistance, and provides the paint which can give a matte design, and a matte decorative sheet using the same. It is to do.
  • Another further subject of the present invention is a paint capable of forming a coating film excellent in dirt removing property and scratch resistance and capable of giving a matte design, and a matte decorative sheet using the same. It is to provide.
  • the above (A) polyfunctional (meth) acrylate is derived from one or more types of polyol compounds selected from the group consisting of polyester polyols and polycarbonate polyols, with the total of structural units derived from polyol compounds being 100% by mass.
  • (A1) multifunctional urethane (meth) acrylate containing 50% by mass or more of the constituent units in an amount of 10 to 90% by mass, based on 100% by mass of the total of (A) polyfunctional (meth) acrylates Including paint.
  • a decorative sheet comprising a coating film formed from the paint according to any one of the above items [1] to [3]. [5].
  • the water contact angle of the surface of the above-mentioned coating film is 15 degrees or less;
  • the decorative sheet whose value of a mandrel test is 10 mm or less.
  • the coating film formed from the paint of the present invention is excellent in the dirt removability.
  • the coating film formed from the coating material of the present invention according to one aspect is excellent in dirt removing property and bending resistance, and has a matte design. Therefore, the decorative sheet provided with stain removability using the paint of the present invention according to this aspect has a matte design and can be applied to so-called 2D molding such as lapping molding.
  • the coating film formed from the paint of the present invention according to another aspect is excellent in the stain removability and scratch resistance and has a matte design. Therefore, the decorative sheet provided with stain removability using the paint of the present invention according to this aspect has a matte design and is excellent in scratch resistance.
  • film is used interchangeably or interchangeably with “sheet”.
  • sheet is used in what can be industrially rolled up.
  • plate is used for those which can not be rolled up industrially.
  • resin is used as a term also including a resin mixture containing two or more resins, and a resin composition containing components other than resins.
  • sequentially stacking one layer and another layer means directly laminating those layers, and interposing one or more other layers such as an anchor coat between the layers. Including both stacking.
  • the term “over” in the numerical range is used in the sense of a certain numerical value or a certain numerical value.
  • 20% or more means 20% or more than 20%.
  • the term "or less” in relation to a numerical range is used to mean a certain numerical value or less than a certain numerical value.
  • 20% or less means 20% or less than 20%.
  • the symbol “to” relating to a numerical range is used in the meaning of a certain numerical value, more than a certain numerical value and less than another certain numerical value, or some other numerical value.
  • some other numerical value is larger than a certain numerical value.
  • 10-90% means 10%, more than 10% and less than 90%, or 90%.
  • Paint The paint of the present invention has (A) polyfunctional (meth) acrylate; and (B) at least one anionic hydrophilic group selected from the group consisting of a sulfonic acid group, a carboxyl group, and a phosphoric acid group. Contains the compound.
  • the paint of an embodiment of the present invention is at least one anionic hydrophilic group selected from the group consisting of (A) polyfunctional (meth) acrylate; and (B) sulfonic acid group, carboxyl group, and phosphoric acid group.
  • the paint of the present invention does not contain inorganic particles.
  • the polyfunctional (meth) acrylate of the component (A) includes a polyfunctional urethane (meth) acrylate including a structural unit derived from one or more types of polyol compounds selected from the group consisting of polyester polyols and polycarbonate polyols.
  • the polyfunctional (meth) acrylate of the component (A) is one or more polyol compounds selected from the group consisting of polyester polyols and polycarbonate polyols, with the total of structural units derived from polyol compounds being 100% by mass.
  • (A1) multifunctional urethane (meth) acrylate which contains the structural unit derived from (A1) in the quantity of 50 mass% or more.
  • the multi-functional (meth) acrylate of the component (A) is a (meth) acrylate having two or more (meth) acryloyl groups in one molecule.
  • the component (A) has two or more (meth) acryloyl groups in one molecule, and thus functions to form a coating film by polymerization and curing by active energy rays such as ultraviolet rays and electron rays and heat. .
  • polyfunctional (meth) acrylate examples include diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, (Meth) acryloyl group-containing bifunctional reaction such as 2'-bis (4- (meth) acryloyloxypolyethyleneoxyphenyl) propane and 2,2'-bis (4- (meth) acryloyloxypolypropyleneoxyphenyl) propane Monomers; (meth) acryloyl group-containing trifunctional reactive monomers such as trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, and pentaerythritol tri (meth) acrylate; (Meth) acryloyl group-containing tetrafunctional reactive monomers such as tall tetra (meth) acrylate;
  • polyfunctional (meth) acrylate For example, polyurethane (meth) acrylate, polyester (meth) acrylate, polyacryl (meth) acrylate, epoxy (meth) acrylate, polyalkylene glycol poly (meth) acrylate, and polyether Mention may be made of (meth) acryloyl group-containing prepolymers or oligomers such as (meth) acrylates and having two or more (meth) acryloyl groups in one molecule.
  • (meth) acrylates other than the said component (A1)
  • these 1 type (s) or 2 or more types of mixtures can be used.
  • (meth) acrylate means acrylate or methacrylate.
  • (A1) Multifunctional Urethane (Meth) Acrylate is a compound having a urethane structure (—NH—CO—O—), or a derivative thereof, and it is preferable to use two or more ) An urethane (meth) acrylate having an acryloyl group and satisfying the following characteristics (a1).
  • the constituent unit derived from one or more types of polyol compounds selected from the group consisting of a polyester polyol and a polycarbonate polyol is mainly (usually 50% by mass with respect to 100% by mass of the constituent units derived from a polyol compound) Or more, preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and most preferably 95% by mass or more.
  • the polyfunctional urethane (meth) acrylate of the component (A1) mainly contains, as a structural unit derived from a polyol compound, a structural unit derived from at least one polyol compound selected from the group consisting of a polyester polyol and a polycarbonate polyol. By including, the miscibility with other components is improved.
  • polyester polyol examples include, but are not limited to, for example, poly (ethylene adipate), poly (butylene adipate), poly (neopentyl adipate), poly (hexamethylene adipate), poly (butylene azelaate), poly (butylene adipate) Sebacate), and polycaprolactone etc. can be mentioned.
  • the polycarbonate polyol is not particularly limited, and examples thereof include poly (butanediol carbonate), poly (hexanediol carbonate), and poly (nonanediol carbonate).
  • polyol compounds selected from the group which consists of said polyester polyol and a polycarbonate polyol, these 1 type, or 2 or more types of mixtures can be used.
  • the polyfunctional urethane (meth) acrylate of the component (A1) is not particularly limited, as long as it does not violate the object of the present invention, but is not particularly limited to polyester polyol and polycarbonate polyol, for example, structural units derived from polyether polyol It may be included.
  • polyether polyols examples include polyalkylene glycols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol; polyalkylene oxides such as polyethylene oxide and polypropylene oxide; copolymers of ethylene oxide and propylene oxide; ethylene A copolymer of an oxide and tetrahydrofuran; a copolymer of a dihydric phenol compound and a polyoxyalkylene glycol; and an alkylene oxide having a carbon number of 2 to 4 (for example, ethylene oxide, propylene oxide, 1, 2) -Butylene oxide, and copolymers with one or more of 1,4-butylene oxide etc. can be mentioned.
  • polyalkylene glycols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol
  • polyalkylene oxides such as polyethylene oxide and polypropylene oxide
  • copolymers of ethylene oxide and propylene oxide ethylene A copolymer of an oxide and t
  • polyol compounds other than the said polyester polyol and polycarbonate polyol 1 type, or 2 or more types of mixtures of these can be used.
  • the compound having two or more isocyanate groups in one molecule is not particularly limited, and, for example, one molecule such as diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, and methylene bis (4-cyclohexyl isocyanate) Mention may be made of compounds having two isocyanate groups therein.
  • Examples of the compound having two or more isocyanate groups in one molecule include a trimethylolpropane adduct of tolylene diisocyanate, a trimethylolpropane adduct of hexamethylene diisocyanate, a trimethylolpropane adduct of isophorone diisocyanate, and a tolylene compound. Mention may be made of polyisocyanates such as isocyanurate of isocyanate, isocyanurate of hexamethylene diisocyanate, isocyanurate of isophorone diisocyanate and biuret of hexamethylene diisocyanate.
  • the compound having two or more isocyanate groups in one molecule a mixture of one or more of them can be used.
  • the hydroxyl group-containing (meth) acrylate is not particularly limited, and examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate.
  • Hydroxyalkyl (meth) acrylates such as acrylate, 6-hydroxyhexyl (meth) acrylate, and 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate; dipropylene glycol (meth) acrylate, polyethylene glycol mono (Meth) acrylates and glycol-based (meth) acrylates such as polypropylene glycol mono (meth) acrylate; glycerin-based (meth) acrylates such as glycerin di (meth) acrylate; Fatty acid-modified glycidyl (meth) acrylates such as glycidyl (meth) acrylate; phosphorus atom-containing (meth) acrylates such as 2-hydroxyethyl acryloyl phosphate; 2- (meth) acryloyloxyethyl 2-hydroxypropyl phthalate and the like Esters or ester derivatives of (meth) acrylic acid adduct
  • hydroxyl-containing (meth) acrylate 1 type (s) or 2 or more types of mixtures of these can be used.
  • the number of (meth) acryloyl groups contained in the polyfunctional urethane (meth) acrylate of the component (A1) is two or more from the viewpoint of the scratch resistance of the resulting coating film.
  • the number of (meth) acryloyl groups contained in the component (A1) is usually 12 or less, preferably 6 or less, more preferably 4 or less, further preferably from the viewpoint of bending resistance of the obtained coating May be 3 or less, most preferably 2 or less.
  • the mass average molecular weight of the polyfunctional urethane (meth) acrylate of the component (A1) is preferably 3,000 or more, more preferably 5,000 or more, still more preferably 6 from the viewpoint of the stain removability of the resulting coating film. It may be over 1,000, most preferably over 7,000. On the other hand, the mass average molecular weight of the polyfunctional urethane (meth) acrylate of the component (A1) may be preferably 50,000 or less, more preferably 30,000 or less, from the viewpoint of the curability of the paint.
  • the mass average molecular weight of the polyfunctional urethane (meth) acrylate of the component (A1) is preferably 3,000 or more and 50,000 or less, more preferably 3,000 or more and 30,000 or less, 5,000 ⁇ 50,000 or less, 5,000 to 30,000 or less, 6,000 to 50,000 or less, 6,000 to 30,000 or less, 7,000 to 50,000 or less, or 7,000 to 30,000 It may be the following.
  • the mass average molecular weight is a polystyrene-equivalent mass average determined from a differential molecular weight distribution curve (hereinafter sometimes abbreviated as GPC curve) measured by gel permeation chromatography (hereinafter sometimes abbreviated as GPC). It is molecular weight.
  • GPC curve differential molecular weight distribution curve
  • GPC gel permeation chromatography
  • the measurement of GPC is a system including Tosoh high performance liquid chromatography system "HLC-8320" (trade name) (a system including a degasser, a liquid feed pump, an autosampler, a column oven and an RI (differential refractive index) detector) 2 columns of GPC column "KF-806L” (trade name) of Shodex Co., Ltd. and a total of 1 each of "KF-802" (trade name) and "KF-801” (trade name) Connect four KF-806L, KF-806L, KF-802, and KF-801 in this order from the upstream side; Tetrahydrofuran for high-performance liquid chromatography by Wako Pure Chemical Industries, Ltd.
  • flow rate 1.0 ml / min, column temperature 40 ° C, sample concentration 1 mg / ml, and sample injection volume 00 can be carried out under the conditions of a micro liter.
  • the elution amount in each holding volume can be determined from the detection amount of the RI detector, assuming that there is no molecular weight dependence of the refractive index of the measurement sample.
  • the calibration curve from the retention volume to the polystyrene equivalent molecular weight is the standard polystyrene “EasiCal PS-1” (trade name) of Agilent Technology Co., Ltd.
  • the polyfunctional (meth) acrylate of the component (A) contains the polyfunctional urethane (meth) acrylate of the component (A1).
  • the polyfunctional (meth) acrylate of the component (A) is preferably 10 to 90 mass% of the polyfunctional urethane (meth) acrylate of the component (A1), wherein the total of the components (A) is 100 mass%, More preferably, it is contained in an amount of 15 to 85% by weight, even more preferably 15 to 75% by weight.
  • the amount of the component (A1) in the component (A) is the stain removability and scratch resistance of the coating film obtained when the paint of the present invention is used for a decorative sheet for so-called 2D molding such as lapping molding And from the viewpoint of bending resistance, it may be preferably 50 to 85% by mass, more preferably 60 to 75% by mass. In one embodiment, this amount may be 50 to 75 wt%, or 60 to 85 wt%. In addition, the amount of the component (A1) in the component (A) is the stain removability of the coating film obtained when the paint of the present invention is used for a decorative sheet for so-called 1D molding such as flat sticking molding. From the viewpoint of bending resistance and scratch resistance, it may be preferably 10 to 40% by mass, more preferably 15 to 25% by mass. In one embodiment, this amount may be 10-25% by weight, or 15-40% by weight.
  • the component (B) having an anionic hydrophilic group is at least one anionic hydrophilic group selected from the group consisting of a sulfonic acid group, a carboxyl group, and a phosphoric acid group.
  • a compound having The component (B) is typically a compound described as compound (I) in International Publication WO 2007/064003. The above compound (I) is described in detail in International Publication WO 2007/064003, and is incorporated herein by reference in its entirety.
  • the compound (I) is a compound represented by the following general formula (1).
  • s represents 1 or 2.
  • L represents 1 or 2;
  • m represents 0 or 1;
  • M 1 and M 2 each represent a hydrogen ion, an ammonium ion, an alkali metal ion, or an alkaline earth metal ion.
  • M 1 and M 2 may be the same or different.
  • X represents one selected from hydrophilic group-containing moieties represented by the following general formulas (1-1) to (1-4).
  • J and J ′ each represent H or CH 3 .
  • J and J ' may be the same or different.
  • n represents 0 or 1;
  • R and R 'each represents an aliphatic hydrocarbon group having 1 to 600 carbon atoms, preferably 2 to 100 carbon atoms, and more preferably 2 to 20 carbon atoms.
  • the aliphatic hydrocarbon group may be linear or branched, and may further contain an aromatic ring, an aliphatic cyclic group, an ether group, or an ester group.
  • R and R ′ may be the same or different.
  • the aliphatic hydrocarbon group may have any substituent. In that case, the total number of carbon atoms including the substituent may be within the above range.
  • the compound having an anionic hydrophilic group of the component (B) has a hydrophilic group-containing portion represented by the above general formula (1-1) from the viewpoint of the stain removability of the obtained coating film.
  • the compound represented by the said General formula (1) is preferable.
  • the compounding amount of the compound having an anionic hydrophilic group of the component (B) is usually from the viewpoint of the stain removing property of the obtained coating film with respect to 100 parts by mass of the polyfunctional (meth) acrylate of the component (A). It is 5 parts by mass or more, preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and still more preferably 30 parts by mass or more.
  • the compounding amount of the compound having an anionic hydrophilic group of the component (B) is usually 100 parts by mass or less, preferably 70 parts by mass or less, from the viewpoint of the curability of the paint and the scratch resistance of the obtained coating film. More preferably, it is 60 parts by mass or less, still more preferably 50 parts by mass or less.
  • the compounding quantity of the compound which has an anionic hydrophilic group of the said component (B) is 5 mass parts or more and 100 mass parts or less normally, Preferably, 5 mass parts or more and 70 mass parts or less, 5 mass parts or more and 60 mass parts or less 5 parts by mass to 50 parts by mass, 10 parts by mass to 100 parts by mass, 10 parts by mass to 70 parts by mass, 10 parts by mass to 60 parts by mass, 10 parts by mass to 50 parts by mass, 20 parts by mass 100 parts by mass or less, 20 parts by mass to 70 parts by mass, 20 parts by mass to 60 parts by mass, 20 parts by mass to 50 parts by mass, 30 parts by mass to 100 parts by mass, 30 parts by mass to 70 parts by mass, 30 parts by mass or more and 60 parts by mass or less, or 30 parts by mass or more and 50 parts by mass or less.
  • An embodiment of the paint of the present invention contains resin particles of the component (C) having an average particle diameter of 1 to 100 ⁇ m.
  • the component (C) functions to make the coating film a matte design.
  • silicone resin, styrene resin, acrylic resin, fluorine resin, polycarbonate resin, ethylene resin, urethane resin, and amino compound And resin particles such as a cured resin of formaldehyde and the like.
  • particles of silicone resin, acrylic resin, urethane resin and fluorine resin are preferable from the viewpoint of low specific gravity, lubricity, dispersibility and solvent resistance. Also, from the viewpoint of making the light diffusibility good and making it easy to give a matt design, a spherical one is preferable.
  • These resin particles may have reactive functional groups such as carbon / carbon double bonds, (meth) acryloyl groups, and isocyanate groups on the surface. Thereby, the scratch resistance of the obtained coating can be improved.
  • these 1 type (s) or 2 or more types of mixtures can be used as a resin particle of the said component (C).
  • the acrylic resin or urethane resin used as the resin particle of the component (C) is the above component depending on the presence or absence of solubility in an organic solvent or the presence or absence of a particle shape having an average particle diameter within the specific range. It distinguishes from the polyfunctional (meth) acrylate of (A) or the polyfunctional urethane (meth) acrylate of the said component (A1).
  • the average particle diameter of the resin particle of the component (C) may be usually 1 ⁇ m or more, preferably 2 ⁇ m or more, more preferably 3 ⁇ m or more, and still more preferably 4 ⁇ m or more from the viewpoint of giving a matte design.
  • the average particle diameter of the resin particles of the component (C) is usually 100 nm or less, preferably 60 nm or less, more preferably 30 ⁇ m from the viewpoint of preventing the coating film from having cloudiness and reducing designability. Or less, more preferably 20 ⁇ m or less.
  • the average particle diameter of the resin particle of the component (C) is usually 1 ⁇ m to 100 nm, preferably 1 ⁇ m to 60 nm, preferably 1 ⁇ m to 30 ⁇ m, 1 ⁇ m to 20 ⁇ m, 2 ⁇ m to 100 nm, 2 ⁇ m to 60 nm, 2 ⁇ m or more 30 ⁇ m or less, 2 ⁇ m to 20 ⁇ m, 3 ⁇ m to 100 nm, 3 ⁇ m to 60 nm, 3 ⁇ m to 30 ⁇ m, 3 ⁇ m to 20 ⁇ m, 4 ⁇ m to 20 nm, 4 ⁇ m to 100 nm, 4 ⁇ m to 60 nm, 4 ⁇ m to 30 ⁇ m, or 4 ⁇ m to 20 ⁇ m You may
  • the average particle size of the resin particles is the smaller of the particles in the particle size distribution curve measured using a laser diffraction / scattering particle size analyzer “MT3200II” (trade name) of Nikkiso Co., Ltd.
  • the particle size is 50% by mass of the accumulation from
  • the compounding quantity of the resin particle of the said component (C) is based also on the level of the matte design which it is going to give with respect to 100 mass parts of polyfunctional (meth) acrylates of the said component (A), normally 5 mass parts
  • the amount may be 20 parts by mass or more, more preferably 30 parts by mass or more, and still more preferably 40 parts by mass or more.
  • the compounding amount of the resin particle of the component (C) is usually 200 parts by mass or less, preferably 150 parts by mass or less, more preferably 100 parts by mass from the viewpoint of scratch resistance and bending resistance of the obtained coating film. It may be at most parts, more preferably at most 80 parts, most preferably at most 70 parts.
  • the compounding amount of the resin particle of the component (C) is usually 5 parts by mass or more and 200 parts by mass or less, preferably 5 parts by mass or more and 150 parts by mass or less, 5 parts by mass or more and 100 parts by mass or less, 5 parts by mass or more and 80 parts 5 parts by weight or more and 70 parts by weight or less, 20 parts by weight or more and 200 parts by weight or less, 20 parts by weight or more and 150 parts by weight or less, 20 parts by weight or more and 100 parts by weight or less, 20 parts by weight or more and 80 parts by weight or less Parts to 70 parts by weight, 30 parts to 200 parts by weight, 30 parts to 150 parts by weight, 30 parts to 100 parts by weight, 30 parts to 80 parts by weight, 30 parts to 70 parts by weight 40 parts by mass to 200 parts by mass, 40 parts by mass to 150 parts by mass, 40 parts by mass to 100 parts by mass, 40 parts by mass to 80 parts by mass, or 40 parts by mass to 70 parts by mass It may be lower.
  • the ratio of the average particle size C1 of the larger average particle size to the average particle size C2 of the smaller average particle size (C1 / C2) Is preferably 1.2 to 10, more preferably 1.5 to 4. In one embodiment, this ratio may be 1.2-4, 1.5-10.
  • the ratio (Ca / Cb) (mass ratio) of the compounding amount Ca of a large average particle diameter to the compounding amount Cb of a small average particle diameter is preferably 0.1 to 6, more preferably 0.3 to 2, More preferably, it may be 0.4 to 1.5. In one embodiment, the ratio is 0.1 to 2, 0.1 to 1.5, 0.3 to 6, 0.3 to 1.5, 0.4 to 6, or 0.4 to 2. May be there.
  • the paint of the present invention does not contain inorganic particles.
  • inorganic particles eg, silica (silicon dioxide); metal oxide particles such as aluminum oxide, zirconia, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide, antimony oxide, and cerium oxide);
  • Metal fluoride particles such as magnesium fluoride and sodium fluoride; metal sulfide particles; metal nitride particles; metal particles etc.
  • inorganic particles eg, silica (silicon dioxide); metal oxide particles such as aluminum oxide, zirconia, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide, antimony oxide, and cerium oxide
  • Metal fluoride particles such as magnesium fluoride and sodium fluoride; metal sulfide particles; metal nitride particles; metal particles etc.
  • the interaction between the inorganic particles and the resin component such as the component (A) is weak, which causes the scratch resistance and the bending resistance of the resulting coating film to be insufficient. Therefore, in the present invention, by using resin particles instead of inorganic particles as particles for giving a matte design, it is possible to favorably maintain the scratch resistance and bending resistance of the coating film.
  • does not contain inorganic particles means that it does not contain a significant amount of inorganic particles.
  • a significant amount of inorganic particles is usually about 1 part by mass or more with respect to 100 parts by mass of the component (A) from the viewpoint of providing a matte design. Therefore, “does not contain” inorganic particles means that the amount of inorganic particles is usually 0 parts by mass or more and less than 1 part by mass, preferably 0.5 parts by mass or less, relative to 100 parts by mass of the component (A).
  • Examples of the compound having two or more isocyanate groups in one molecule include methylene bis 4-cyclohexyl isocyanate; trimethylol propane adduct of tolylene diisocyanate, trimethylol propane adduct of hexamethylene diisocyanate, triol of isophorone diisocyanate.
  • Methylol propane adducts isocyanurates of tolylene diisocyanate, isocyanurates of hexamethylene diisocyanate, isocyanurates of isophorone diisocyanate, polyisocyanates such as biuret of hexamethylene diisocyanate; and block type isocyanates of the above polyisocyanates Urethane crosslinking agent etc. can be mentioned.
  • a catalyst such as dibutyltin dilaurate or dibutyltin diethyl hexoate may be added, if necessary.
  • the compounding amount of the compound having two or more isocyanate groups in one molecule is from the viewpoint of the adhesion between the coating and the substrate and the surface hardness of the coating with respect to 100 parts by mass of the component (A). Usually, it may be 30 parts by mass or less, preferably 20 parts by mass or less, more preferably 10 parts by mass or less.
  • the compounding amount of the compound having two or more isocyanate groups in one molecule is usually 0.1 parts by mass or more, preferably 0.5 parts by mass or more, more preferably from the viewpoint of reliably obtaining the use effect. May be 1 part by mass or more, more preferably 2 parts by mass or more.
  • the compounding amount of the compound having two or more isocyanate groups in one molecule is usually 0.1 parts by mass or more and 30 parts by mass or less, preferably 0.1 parts by mass or more and 20 parts by mass or less.
  • photopolymerization initiator examples include benzophenone, methyl-o-benzoylbenzoate, 4-methylbenzophenone, 4,4'-bis (diethylamino) benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl Benzophenone compounds such as -4'-methyl diphenyl sulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethyl benzophenone; benzoin, benzoin methyl ether, benzoin Benzoin compounds such as ethyl ether, benzoin isopropyl ether, benzyl methyl ketal; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone Acetophenone compounds; anthraquinone compounds such as methyl anthraquino
  • the compounding amount of the photopolymerization initiator is usually 10 parts by mass or less, preferably 7 parts by mass from the viewpoint of preventing the formed coating from becoming yellowed and colored with respect to 100 parts by mass of the component (A). It may be at most parts by mass, more preferably at most 5 parts by mass. On the other hand, the compounding amount of the photopolymerization initiator is usually 0.1 parts by mass or more, preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and still more preferably from the viewpoint of obtaining the use effect reliably. It may be 2 parts by mass or more.
  • the compounding amount of the photopolymerization initiator is usually 0.1 parts by mass or more and 10 parts by mass or less, preferably 0.1 parts by mass or more and 7 parts by mass or less, 0.1 parts by mass or more and 5 parts by mass 0.5 parts by weight or more and 10 parts by weight or less 0.5 parts by weight or more and 7 parts by weight or less 0.5 parts by weight or more and 5 parts by weight or less, 1 parts by weight or more and 10 parts by weight or less, 1 parts by weight or more and 7 parts by weight Or less, 1 to 5 parts by weight, 2 to 10 parts by weight, 2 to 7 parts by weight, or 2 to 5 parts by weight.
  • an antistatic agent if desired, an antistatic agent, a surfactant, a leveling agent, a thixotropic agent, a stain inhibitor, a printability improver, an antioxidant, as long as the object of the present invention is not violated.
  • One or two or more additives such as a weather resistant stabilizer, a light resistant stabilizer, an ultraviolet light absorber, a heat stabilizer, and an organic coloring agent can be contained.
  • the paint of the present invention may optionally contain a solvent in order to dilute it to an easy-to-coat concentration.
  • the solvent is not particularly limited as long as it does not react with the components (A), (B), and other optional components, or catalyze (reduce) the self reaction (including deterioration reaction) of these components. I will not.
  • the solvent include 1-methoxy-2-propanol, ethyl acetate, n-butyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, and acetone.
  • 1 type (s) or 2 or more types of mixtures of these can be used.
  • the paint of the present invention can be obtained by mixing and stirring these components.
  • the method in particular of forming a coating film using the coating material of this invention is not restrict
  • the thickness of the coating film formed using the paint of the present invention is not particularly limited, but may be usually 1 ⁇ m or more, preferably 2 ⁇ m or more, more preferably 3 ⁇ m or more from the viewpoint of scratch resistance.
  • the thickness of the coating film may be preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, still more preferably 30 ⁇ m or less, and most preferably 15 ⁇ m or less, from the viewpoint of bending resistance.
  • the thickness of the coating is 1 to 100 ⁇ m, 1 to 50 ⁇ m, 1 to 30 ⁇ m, 1 to 15 ⁇ m, 2 to 100 ⁇ m, 2 to 50 ⁇ m, 2 to 30 ⁇ m, 2 to 15 ⁇ m. 3 ⁇ m to 100 ⁇ m, 3 ⁇ m to 50 ⁇ m, 3 ⁇ m to 30 ⁇ m, or 3 ⁇ m to 15 ⁇ m.
  • the decorative sheet of the present invention is a decorative sheet having a coating film formed using the coating of the present invention.
  • the coating film formed using the paint of the present invention is usually formed as a surface protective layer on the front surface (the surface on the side that is usually viewed in actual use) of the decorative sheet of the present invention.
  • the actual use state refers to a state in which the decorative sheet is used for making and decorating the surface of various articles.
  • the decorative sheet of the present invention is not particularly limited.
  • a decorative sheet having a coating film formed using the paint of the present invention on the front surface side of a thermoplastic resin film A printing layer may be provided on the surface which becomes the front side, and a decorative sheet having a coating film formed using the paint of the present invention on the surface of the printing layer may further be mentioned.
  • thermoplastic resin film is a layer used as the base material of a decorative sheet.
  • the above-mentioned thermoplastic resin film is usually colored from the viewpoint of designability and works to hide the adherend.
  • thermoplastic resin film examples include polyvinyl chloride resins; polyester resins such as aromatic polyesters and aliphatic polyesters; polyolefin resins such as polyethylene, polypropylene and polymethylpentene; acrylic resins; polycarbonate resins Poly (meth) acrylimide resins; polystyrene, acrylonitrile / butadiene / styrene copolymer resin (ABS resin), styrene / ethylene / butadiene / styrene copolymer, styrene / ethylene / propylene / styrene copolymer, and styrene ⁇ Styrene-based resins such as ethylene / ethylene / propylene / styrene copolymers; Cellulose-based resins such as cellophane, triacetyl cellulose, diacetyl cellulose, and acetyl cellulose butyrate;
  • the coloring agent in particular in the case of coloring the said thermoplastic resin film is not restrict
  • the colorant include titanium oxide and carbon black.
  • 1 type (s) or 2 or more types of mixtures of these can be used.
  • the compounding amount of the coloring agent is usually about 0.1 to 40 parts by mass, depending on the kind of the coloring agent and the desired hiding property, with 100 parts by mass of the base resin used for the thermoplastic resin film. .
  • the thickness of the thermoplastic resin film is not particularly limited, but may be preferably 50 ⁇ m or more, more preferably 75 ⁇ m or more from the viewpoint of handleability at the time of producing a decorative sheet. On the other hand, it may be 300 ⁇ m or less, preferably 250 ⁇ m or less, from the viewpoint of workability at the time of attaching the decorative sheet to the article. In one embodiment, the thickness of the thermoplastic resin film may be 50 ⁇ m to 300 ⁇ m, 50 ⁇ m to 250 ⁇ m, 75 ⁇ m to 300 ⁇ m, or 75 ⁇ m to 250 ⁇ m.
  • the said printing layer is provided in order to provide high designability, and can be formed by printing arbitrary patterns using arbitrary ink and arbitrary printing machines.
  • the print layer can be applied entirely or partially on the front side surface of the thermoplastic resin film directly or through an anchor coat.
  • metal patterns such as hairlines, grain patterns, stone patterns that imitate the surface of rocks such as marble, cloth patterns that imitate cloth or cloth patterns, tile patterns, brick pile patterns, parquet patterns, And patchwork.
  • a mixture of a binder, a pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent and the like as appropriate can be used as appropriate.
  • binder examples include polyurethane resins, vinyl chloride / vinyl acetate copolymer resins, vinyl chloride / vinyl acetate / acrylic copolymer resins, chlorinated polypropylene resins, acrylic resins, polyester resins, and polyamides.
  • Resins such as system resin, butyral resin, polystyrene resin, nitrocellulose resin, and cellulose acetate resin, and these resin compositions can be used.
  • aluminum, tin, titanium, indium, oxides thereof, etc., directly or through an anchor coat are entirely or entirely on the surface of the thermoplastic resin film. It may be partially deposited by known methods.
  • the method of forming a coating film directly or through an anchor coat on the surface of the printing layer formed on the front surface of the thermoplastic resin film using the paint of the present invention is particularly limited.
  • known web application methods can be used. Examples of the method include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating.
  • the thickness of the coating film formed using the paint of the present invention is not particularly limited, but from the viewpoint of scratch resistance, it is usually 1 ⁇ m or more, preferably 2 ⁇ m or more, more preferably 3 ⁇ m or more Good. Further, the thickness of the coating film in the decorative sheet is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, still more preferably 30 ⁇ m or less, from the viewpoint of the secondary processability and web handling properties of the decorative sheet of the present invention. It may be 15 ⁇ m or less.
  • the thickness of the coating film in the decorative sheet is 1 ⁇ m to 100 ⁇ m, 1 ⁇ m to 50 ⁇ m, 1 ⁇ m to 30 ⁇ m, 1 ⁇ m to 15 ⁇ m, 2 ⁇ m to 100 ⁇ m, 2 ⁇ m to 50 ⁇ m, 2 ⁇ m to 30 ⁇ m, 2 ⁇ m It may be 15 ⁇ m or more, 3 ⁇ m to 100 ⁇ m, 3 ⁇ m to 50 ⁇ m, 3 ⁇ m to 30 ⁇ m, or 3 ⁇ m to 15 ⁇ m.
  • the anchor coat agent for forming the anchor coat is not particularly limited, and any anchor coat agent can be used.
  • the anchor coating agent include polyester-based, acrylic-based, polyurethane-based, acrylic urethane-based, and polyester urethane-based anchor coating agents. As the above-mentioned anchor coating agent, one or more of these can be used.
  • an antioxidant if necessary, an antioxidant, a weather resistant stabilizer, a light resistant stabilizer, an ultraviolet light absorber, a thermal stabilizer, an antistatic agent, a surfactant, as long as the object of the present invention is not violated
  • One or more additives such as a colorant, an infrared shielding agent, a leveling agent, a thixotropic agent, and a filler may be contained.
  • the method for forming the above-mentioned anchor coat using the above-mentioned anchor coat agent is not particularly limited, and known web application methods can be used. Examples of the method include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating.
  • the thickness of the anchor coat is not particularly limited, but may generally be about 0.01 to 5 ⁇ m, preferably 0.1 to 2 ⁇ m.
  • the decorative sheet of the present invention is provided on the surface opposite to the front surface side of the above-mentioned thermoplastic resin film from the viewpoint of improving the adhesion to an adherend to be decorated or decorated using this.
  • the pressure-sensitive adhesive layer or the adhesive layer may be formed directly or through an anchor coat.
  • FIG. 1 is a conceptual view of a cross section showing one non-limiting example of the decorative sheet of the present invention.
  • the coating film 1, the printing layer 2, the layer 3 of a colored thermoplastic resin film, and the pressure-sensitive adhesive layer 4 formed from the coating material of the present invention are sequentially provided from the side that is usually viewed in actual use.
  • the water contact angle of the surface of the coating film formed using the paint of the present invention of the decorative sheet of the present invention is preferably 15 degrees or less, more preferably 14 degrees or less, and still more preferably from the viewpoint of stain removability. It may be 13 degrees or less, more preferably 11 degrees or less, and most preferably 9 degrees or less.
  • the water contact angle is preferably low.
  • the value of the mandrel test of the decorative sheet of the present invention is preferably 10 mm or less, more preferably 8 mm or less, still more preferably 6 mm or less, still more preferably 4 mm or less from the viewpoint of bending resistance of the formed coating May be there.
  • V Oleic acid removability (dirt removability) Blending oleic acid (reagent grade 1) from Wako Pure Chemical Industries, Ltd. and carbon black “FW-200” (trade name) from Orion Engineered Carbons Co., Ltd. at a mass ratio of 10/1, and mixing well Contamination was created.
  • 1 mg of the contaminants obtained above was applied in a circular shape with a diameter of 20 mm to the coated surface of the decorative sheet, and then washed away with tap water. Washing with water was carried out for 20 seconds by a method in which a flow rate of 1 liter / 10 seconds was applied directly to the above-mentioned coated contamination at a position 10 cm below the water tap.
  • Mandrel test index of crack resistance and bending resistance
  • JIS K 5600-5-1 1999, using a sample collected from the decorative sheet so as to be 100 mm in the machine direction ⁇ 50 mm in the machine direction, a bending resistance test was conducted by the cylindrical mandrel method. The diameter of the mandrel with the smallest diameter among the non-breaking mandrels was determined.
  • A1 Multifunctional Urethane (Meth) Acrylate A1-1) Multifunctional Urethane (Meth) Acrylate “Art Resin UN-1255” (trade name) of Negami Industrial Co., Ltd. The number 2 of (meth) acryloyl groups. All polyol compounds are polyester polyols. Mass average molecular weight 8000.
  • A1-6 Multifunctional urethane (meth) acrylate "KY103" (trade name) of Negami Industrial Co., Ltd. The number 2 of (meth) acryloyl groups. All polyol compounds are polycaprolactones (polyester polyols). Mass average molecular weight 5500.
  • Polyol compounds are polyether polyols. Mass average molecular weight 12700.
  • C Resin particles having an average particle diameter of 1 to 100 ⁇ m.
  • C-1 Resin particles “CERAFLOUR 1000” (trade name) of BIC Chemie Japan Ltd. Average particle size 5 ⁇ m.
  • C-2) Acrylic resin particles "Art Pearl SE-010T” (trade name) of Negami Industrial Co., Ltd. Average particle size 10 ⁇ m.
  • D-1 Compound “RV2” (trade name) having two or more isocyanate groups in one molecule of Wright Chemical Industries, Ltd. Number of isocyanate groups per unit amount: 5.95 mol / kg.
  • D-2) Acetophenone photopolymerization initiator (2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl ⁇ -2-methyl-propane- of BASF AG 1-ON) "IRGACURE 127" (trade name).
  • D-3) Methanol.
  • D-4) 1-methoxy-2-propanol.
  • Anchor coating agent (P-1) 100 parts by mass of non-crystalline polyester resin "VYLON 103" (trade name) of Toyobo Co., Ltd., 10 parts by mass of hydroxyphenyl triazine ultraviolet absorber "TINUVIN 479" (trade name) of BASF, A paint obtained by mixing and stirring 3.3 parts by mass of the component (D-1), 120 parts by mass of methyl ethyl ketone, and 240 parts by mass of ethyl acetate.
  • Example 1 Preparation of paint 33 parts by mass of the component (A2-1), 67 parts by mass of the component (A1-1), 37 parts by mass of the component (B-1), 30 parts by mass of the component (C-1), the component C-2) 20 parts by mass, 6 parts by mass of the component (D-1), 3.5 parts by mass of the component (D-2), 50 parts by mass of the component (D-3), and the component (D-4) 150 parts by mass was mixed and stirred to obtain a paint.
  • a vinyl chloride / vinyl acetate copolymer is formed on one side of a colored polybutylene terephthalate resin film "HR (WHT)" (trade name) with a thickness of 250 ⁇ m and white of Riken Technos Co., Ltd.
  • a printing layer having a thickness of 1 ⁇ m was formed using an ink as a medium.
  • a film mayer bar type coating apparatus is used on the surface of the printing layer formed in the above (2-1), and after curing using the above anchor coating agent (P-1)
  • the anchor coat layer was formed to have a thickness of 0.8 ⁇ m.
  • Examples 2-16, 6-1 Preparation of a decorative sheet and measurement and evaluation of physical properties were conducted in the same manner as in Example 1 except that the composition of the paint was changed to those shown in Table 1 or 2. The results are shown in Tables 1 and 2.
  • Examples 1 to 10, 13 to 16, and 6-1 were designed as so-called decorative sheets for 2D molding.
  • Examples 11 and 12 were designed as decorative sheets for so-called 1D molding.
  • the decorative sheet of the present invention which is designed for so-called 2D molding, is excellent in stain removability, heat resistance, smoothness of coated surface, and bending resistance.
  • the decorative sheet of the present invention which is designed for so-called 1D molding, is excellent in stain removability, heat resistance, smoothness of the coated surface, and scratch resistance. Moreover, this decorative sheet has bending resistance sufficient for so-called 1D molding.
  • Coating 2 Printing layer 3: Layer of colored thermoplastic resin film 4: Adhesive layer

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention concerne un matériau de revêtement qui comprend 100 parties en masse de (A) un (méth)acrylate polyfonctionnel et 5-100 parties en masse de (B) un composé comprenant au moins un groupe hydrophile anionique choisi dans le groupe constitué par un groupe acide sulfonique, un groupe carboxyle et un groupe phosphate et qui ne contient pas de particules inorganiques, le (méth)acrylate polyfonctionnel (A) comprenant un uréthane-(méth)acrylate polyfonctionnel (A1) en une quantité de 10-90 % en masse par rapport à la totalité de (méth)acrylate polyfonctionnel (A), dont la quantité est prise en tant que 100 % en masse. L'uréthane-(méth)acrylate polyfonctionnel (A1) comprend des motifs constitutifs dérivés d'un ou plusieurs composés de type polyol choisis dans le groupe constitué par les polyester-polyols et les polycarbonate-polyols en une quantité de 50 % en masse ou plus par rapport à la somme de tous les motifs constitutifs dérivés du composé de type polyol, qui est prise en tant que 100 % en masse. Le matériau de revêtement peut en outre contenir 5-200 parties en masse de particules de résine (C) présentant un diamètre moyen de particule de 1-100 µm par 100 parties en masse du (méth)acrylate polyfonctionnel (A).
PCT/JP2018/025321 2017-08-10 2018-07-04 Matériau de revêtement pour former un film de revêtement pourvu d'une aptitude d'enlèvement de taches et feuille décorative obtenue à l'aide de celui-ci Ceased WO2019031116A1 (fr)

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JP2025086429A (ja) * 2023-11-28 2025-06-09 ａｒｔｉｅｎｃｅ株式会社 活性エネルギー線硬化性組成物、およびそれを用いた積層体

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JPH07266511A (ja) * 1994-03-31 1995-10-17 Dainippon Printing Co Ltd 耐擦傷性を有する艶消し化粧シート
JPH0953025A (ja) * 1995-08-11 1997-02-25 Sanyo Chem Ind Ltd 活性エネルギー線硬化性組成物
WO2006019175A1 (fr) * 2004-08-19 2006-02-23 Kansai Paint Co., Ltd. Composition photodurcissable pour former un revêtement anti-buée
JP2007002034A (ja) * 2005-06-22 2007-01-11 Bau Japan Kk 防曇膜組成物及び防曇鏡
WO2007064003A1 (fr) * 2005-12-02 2007-06-07 Mitsui Chemicals, Inc. Film monocouche et materiau hydrophile compose de celui-ci
JP2012218276A (ja) * 2011-04-07 2012-11-12 Dainippon Printing Co Ltd 加飾シート及びそれを用いてなる加飾樹脂成形品

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JP6028660B2 (ja) 2013-03-29 2016-11-16 Toto株式会社 親水性塗料組成物、親水性塗膜、水回り物品及び親水性塗膜の製造方法
KR102436845B1 (ko) * 2015-09-10 2022-08-26 동우 화인켐 주식회사 하드코팅 조성물 및 이를 이용한 하드코팅 필름

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JPH07266511A (ja) * 1994-03-31 1995-10-17 Dainippon Printing Co Ltd 耐擦傷性を有する艶消し化粧シート
JPH0953025A (ja) * 1995-08-11 1997-02-25 Sanyo Chem Ind Ltd 活性エネルギー線硬化性組成物
WO2006019175A1 (fr) * 2004-08-19 2006-02-23 Kansai Paint Co., Ltd. Composition photodurcissable pour former un revêtement anti-buée
JP2007002034A (ja) * 2005-06-22 2007-01-11 Bau Japan Kk 防曇膜組成物及び防曇鏡
WO2007064003A1 (fr) * 2005-12-02 2007-06-07 Mitsui Chemicals, Inc. Film monocouche et materiau hydrophile compose de celui-ci
JP2012218276A (ja) * 2011-04-07 2012-11-12 Dainippon Printing Co Ltd 加飾シート及びそれを用いてなる加飾樹脂成形品

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Publication number Priority date Publication date Assignee Title
JP2025086429A (ja) * 2023-11-28 2025-06-09 ａｒｔｉｅｎｃｅ株式会社 活性エネルギー線硬化性組成物、およびそれを用いた積層体
JP7694637B2 (ja) 2023-11-28 2025-06-18 ａｒｔｉｅｎｃｅ株式会社 活性エネルギー線硬化性組成物、およびそれを用いた積層体

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