Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
  • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
  • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
• • 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
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
• • 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
  • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
  • C09D163/10—Epoxy resins modified by unsaturated compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • 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
  • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal 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
  • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
• • 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 an active energy ray-curable composition and a method for producing a matte coating film using the composition.
• “decorative sheets” are used for furniture, housing interiors, vehicle interior materials, etc., as materials that can give an appearance (design) close to natural materials by laminating them on the surface of base materials. .
• a coating agent constituting the outermost layer of the decorative sheet matting (sometimes referred to as low gloss) for preventing reflection of lighting fixtures and reproducing a wooden surface, and a base material / decorative layer
• physical properties such as good viscosity are required in terms of scratch resistance, stain resistance, and workability to protect the
• most of the current coating agents are two-component curable paints containing organic solvents, but in recent years attention has been paid to active energy ray-curable solventless paints from the viewpoint of environmental friendliness.
• a coating agent added with an electron beam curing type (sometimes referred to as EB curing type) or ultraviolet curing type (sometimes referred to as UV curing type) matting agent is applied onto the base material. It is known (see, for example, Patent Document 1).
• an electron beam curing type sometimes referred to as EB curing type
• ultraviolet curing type sometimes referred to as UV curing type
• JP-A-2002-69332 Japanese Patent Application Laid-Open No. 2001-87703
• the problem to be solved by the present invention is an active energy ray-curable composition having a viscosity that can be applied as a coating agent, a low glossiness that provides a matting effect, stain resistance, and scratch resistance, and the active energy
• An object of the present invention is to provide a method for producing a matte coating film using a ray-curable composition.
• an active energy ray-curable composition containing a specific amount of a specific active energy ray-curable compound, a photopolymerization initiator, and a specific amount of a matting agent having a specific particle size solves the above problems. found to do.
• the present invention is an active energy ray-curable composition containing an active energy ray-curable compound, a photopolymerization initiator, and a matting agent, characterized by satisfying (1) and (2).
• an active energy ray-curable composition containing an active energy ray-curable compound, a photopolymerization initiator, and a matting agent, characterized by satisfying (1) and (2).
• an active energy ray-curable composition 10 to 50% by mass of ethylene oxide-modified 1,6-hexanediol diacrylate based on the total mass of the active energy ray-curable compound, and ethylene oxide-modified trimethylolpropane triacrylate as the active energy. It is contained in an amount of 10 to 50% by mass based on the total mass of the ray-curable compound.
• the matting agent has a particle diameter of 1 to 10 ⁇ m, and contains 5 to 20% by mass of the matting agent based on the total mass of the active energy ray-curable compound.
• the present invention contains 1 to 20% by mass of dipentaerythritol hexaacrylate with respect to the total mass of active energy ray-curable compounds, and 1 to 20% by mass of ethoxyethoxyethanol acrylic acid multimer ester with respect to the total mass of active energy ray-curable compounds.
• an active energy ray-curable composition containing 30% by mass.
• At least one (meth)acrylic oligomer selected from the group consisting of urethane (meth)acrylate, epoxy (meth)acrylate, and acrylic (meth)acrylate is added to the total mass of the active energy ray-curable compound.
• an active energy ray-curable composition containing 1 to 20% by mass.
• the present invention includes a step (I) of forming a coating film of an active energy ray-curable composition on a substrate, a step (II) of irradiating ultraviolet rays on the coating film in the atmosphere, and the coating film and a step (III) of irradiating an active energy ray, in this order, wherein the active energy ray-curable composition is a method for producing a matte coating film.
• the active energy ray-curable composition is a method for producing a matte coating film.
• the active energy ray-curable composition of the present invention can have a viscosity that can be applied as a coating agent even without a solvent, a low glossiness that provides a matting effect, stain resistance, and scratch resistance.
• the active energy ray-curable composition of the present invention is an active energy ray-curable composition containing an active energy ray-curable compound, a photopolymerization initiator, and a matting agent, comprising (1) and (2) is characterized by satisfying (1) As the active energy ray-curable compound, 10 to 50% by mass of ethylene oxide-modified 1,6-hexanediol diacrylate based on the total mass of the active energy ray-curable compound, and ethylene oxide-modified trimethylolpropane triacrylate as the active energy. It is contained in an amount of 10 to 50% by mass based on the total mass of the ray-curable compound. (2)
• the matting agent has a particle diameter of 1 to 10 ⁇ m, and contains 5 to 20% by mass of the matting agent based on the total mass of the active energy ray-curable compound.
• the matte coating film of the present invention is a matte coating film comprising a cured product of a coating agent comprising an active energy ray-curable composition.
• the coating agent comprising the active energy ray-curable composition used in the present invention is referred to as "active energy ray-curable matte coating agent”.
• active energy ray-curable matte coating agent refers to one or both of acrylate and methacrylate.
• the active energy ray-curable compound used in the present invention includes ethylene oxide-modified 1,6-hexanediol diacrylate in an amount of 10 to 50% by mass based on the total mass of the active energy ray-curable compound, and ethylene oxide-modified trimethylolpropane triacrylate. should be contained in an amount of 10 to 50% by mass based on the total mass of the active energy ray-curable compound. If the ethylene oxide-modified 1,6-hexanediol diacrylate is 10% by mass or more relative to the total mass of the active energy ray-curable compound, low glossiness tends to be maintained, and if it is 50% by mass or less, scratch resistance is improved.
• ethylene oxide-modified trimethylolpropane triacrylate is 10% by mass or more relative to the total mass of the active energy ray-curable compound, scratch resistance tends to be maintained, and if it is 50% by mass or less, low gloss tends to be maintained. Become.
• the amount of alkylene oxide added in the modification is preferably 1 to 2 mol.
• the amount of alkylene oxide added in the modification is preferably 1 to 3 mol, more preferably 2 to 3 mol.
• the active energy ray-curable compound used in the present invention contains 1 to 20% by mass of dipentaerythritol hexaacrylate based on the total mass of the active energy ray-curable compound, and an ethoxyethoxyethanol acrylic acid multimeric ester as an active energy. It may be contained in an amount of 1 to 30% by mass based on the total mass of the ray-curable compound.
• dipentaerythritol hexaacrylate is 1% by mass or more relative to the total mass of the active energy ray-curable compound, stain resistance tends to be maintained, and when it is 20% by mass or less, low gloss tends to be maintained.
• (meth)acrylic oligomer may be used as necessary.
• (Meth)acrylic oligomers include urethane (meth)acrylate, acrylic (meth)acrylate, epoxy (meth)acrylate, amine-modified polyether acrylate, amine-modified epoxy acrylate, amine-modified aliphatic acrylate, amine-modified polyester acrylate, amino ( Examples include amine-modified acrylates such as meth)acrylates, polyester (meth)acrylates, polyether (meth)acrylates, polyolefin (meth)acrylates, polystyrene (meth)acrylates, and the like. Urethane (meth)acrylate, epoxy (meth)acrylate, and acrylic (meth)acrylate are preferable among them. It is more preferable in that it can be done.
• the (meth)acrylic oligomer preferably has a number average molecular weight of 150 to 100,000, more preferably 200 to 10,000.
• At least one (meth)acrylic oligomer selected from the group consisting of urethane (meth)acrylate, epoxy (meth)acrylate, and acrylic (meth)acrylate is used in an amount of 1 to 20 with respect to the total mass of the active energy ray-curable compound. It is preferable to contain in mass %.
• the scratch resistance tends to be maintained. tend to hold
• the active energy ray-curable composition of the present invention usually uses a photopolymerization initiator.
• a photopolymerization initiator used at this time a known one may be used.
• radical polymerization type photopolymerization initiators are preferable, and examples include ⁇ -hydroxyalkylketone photopolymerization initiators that do not cause discoloration of the solution when the active energy ray-curable compound is dissolved and that cause little yellowing over time.
• ⁇ -hydroxyalkylketone photopolymerization initiators include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-(4-i-propylphenyl)-2-hydroxy-2-methylpropane, -1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenylketone and the like.
• Phenylglyoxolate-based photopolymerization initiators are also preferred.
• Examples of phenylglyoxolate-based photopolymerization initiators include methylbenzoyl formate and the like. Among them, 1-hydroxycyclohexylphenyl ketone is preferred.
• monoacylphosphine oxide photopolymerization initiators having absorption wavelengths in the long wavelength region of ultraviolet rays may be used in appropriate combination.
• monoacylphosphine oxide-based photopolymerization initiator 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,6 -dimethoxybenzoyl-diphenylphosphine oxide, 2,6-dichlorobenzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoyl-phenylphosphine acid methyl ester, 2-methylbenzoyl-diphenylphosphine oxide, pivaloyl Examples include monoacylphosphine oxides such as phenylphosphinic acid isopropyl ester, and particularly, among these, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide has an emission wavelength of 385 nm or 3
• the photopolymerization initiators described above may be used alone, or two or more of them may be used in combination.
• the total amount of the photopolymerization initiator added is preferably in the range of 0.01 to 5.0% by mass based on the total amount of the active energy ray-curable composition. Good curability can be obtained if it is 0.01% by mass or more.
• the photopolymerization initiator is generally added in an amount of 5.0 to 10.0% by mass based on the total solid content of the coating agent. , In the present invention, by making it 5.0% by mass or less, the fluidity as a coating agent can be maintained, and workability and workability can be maintained.
• the coating film surface of the matting coating film tends to be in a semi-cured state, and the fine particles of the matting agent are efficiently arranged by the surface orientation, so that the matting effect can be easily obtained.
• the curing speed can be increased by adding a tertiary amine compound selected from aliphatic amine derivatives and/or benzoic acid amine derivatives as a sensitizer.
• a tertiary amine compound selected from aliphatic amine derivatives and/or benzoic acid amine derivatives as a sensitizer.
• Tertiary amine compounds are known to increase reactivity and prevent reaction inhibition by oxygen.
• Suitable tertiary amine compounds include, for example, free alkylamines such as triethylamine, methyldiethanolamine, triethanolamine, aromatic amines such as 2-ethylhexyl-4-dimethylaminobenzoate, ethyl-4-dimethylaminobenzoate, and polymeric Actinic radiation-polymerizable compounds, such as polyunsaturated amines (e.g., (meth)acrylated amines), exhibit reduced yellowing due to their low odor, low volatility, and ability to be incorporated into polymer matrices upon curing. It is considered preferable because it has the property of
• the tertiary amine compound can be used in an amount of preferably 0.1 to 10% by mass, more preferably 0.3 to 3% by mass, based on the total amount of the paint containing the organic solvent.
• matting agent with an average particle size of 1 to 10 ⁇ m Any known matting agent having an average particle size of 1 to 10 ⁇ m may be used in the present invention, and organic and/or inorganic matting agents may be used alone or in combination without particular limitation. Specifically, for example, silica, titanium oxide, alumina particles (aluminum oxide), calcium carbonate, barium sulfate, inorganic particles such as glass, or organic particles such as acrylic resin, urethane resin, polycarbonate resin, silicone resin, polystyrene resin, silicone Beads or the like can be used.
• Inorganic fine particles such as silica and aluminosilicate beads, and organic fine particles such as acrylic resin beads, urethane resin beads, silicone beads, etc., are preferable as those from which a high matting effect can be expected.
• the amount of the matting agent to be added is preferably 5 to 20% by mass, more preferably 10 to 18% by mass, based on the total mass of the active energy ray-curable compound. When the content is 5% by mass or more, a sufficient matting effect can be obtained, and when the content is 20% by mass or less, the viscosity and scratch resistance that can be applied as a coating agent tend to be maintained.
• Silica used in the present invention is not particularly limited as long as it has an average particle size in the range of 1 to 10 ⁇ m, and known silica can be used. Let the average particle diameter be the value measured by the laser diffraction method in this invention. More specifically, amorphous silica is more preferred as silica. Examples of the amorphous silica include diatomaceous earth, activated clay, and the like. Among amorphous silica, dry silica, wet silica, silica gel, and the like can be used as synthetic amorphous silica. Among them, wet silica produced by neutralization or decomposition reaction of an aqueous solution of sodium silicate with an acid or an alkali metal salt is preferred.
• the wet silica may be surface-treated.
• the method for surface-treating the silica particles is not particularly limited, and any known method may be used. Examples include those surface-treated with wax or silane coupling agents.
• Wet silica may be used by mixing a plurality of the above-mentioned surface-treated and non-surface-treated silicas.
• the average particle size of wet silica used as the matting agent is 1 to 10 ⁇ m, more preferably 1.5 to 8 ⁇ m. If the average particle size is less than 1 ⁇ m, the viscosity increases significantly, making it difficult to obtain a viscosity suitable for coating. On the other hand, if the average particle size is more than 10 ⁇ m, the effect of orienting the silica on the surface layer of the coating film is lost, resulting in insufficient matt feeling.
• the silica content is preferably 5 to 20% by mass, more preferably 10 to 18% by mass, of the total mass of the active energy ray-curable compound.
• the silica content is less than 5% by mass, a sufficient matting effect cannot be obtained, and when the content exceeds 20% by mass, it tends to be difficult to maintain the viscosity that allows coating as a coating agent and the scratch resistance, which is preferable. do not have.
• beads When beads are used in the present invention, known beads can be used without any particular limitation. Specifically, acrylic resin beads, silicone beads, glass beads, aluminosilicate beads, and the like can be used. By further adding beads to silica as the matting agent, it is possible to improve the scratch resistance of the coated surface in addition to moderately low luster. Beads as a matting agent are required in a larger amount than silica, but there is an advantage in that it is easy to finely adjust the degree of glossiness by adjusting the amount of beads added. Among them, acrylic resin beads are preferred.
• the active energy ray-curable composition of the present invention is preferably used without a solvent from the viewpoint of environmental friendliness in recent years, but an organic solvent may be added as necessary.
• Organic solvent any solvent can be used as long as it dissolves the active energy ray-curable composition to be used.
• aromatic hydrocarbons such as toluene and xylene
• aliphatic or alicyclic hydrocarbons such as n-hexane, cyclohexane, methylcyclohexane, and ethylcyclohexane
• esters such as ethyl acetate, butyl acetate, and propyl acetate
• Alcohols such as ethanol, isopropyl alcohol and n-butanol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone
• alkylene glycol monoalkyl ethers such as ethylene glycol monoethyl ether and propylene glycol monomethyl ether
• propylene glycol monomethyl ether Ether esters such as acetate and the like are included.
• the active energy ray-curable composition of the present invention is preferably adjusted to a viscosity that allows coating in the method for producing a matte coating film of the present invention, which will be described later.
• the viscosity is preferably adjusted to 300 to 10000 mPa ⁇ s, more preferably 2000 to 5000 mPa ⁇ s.
• Most of the active energy ray-curable compounds generally have low molecular weights, and if the viscosity can be adjusted without dilution with an organic solvent, there is no need to dilute with an organic solvent.
• the viscosity can be adjusted by diluting with an organic solvent or heating.
• the active energy ray-curable composition used in the present invention may optionally contain a polymerization inhibitor, a leveling agent, a thixotropic agent, a wax, a desiccant, a thickener, an anti-sagging agent, a plasticizer, a dispersant, Anti-settling agents, anti-foaming agents, ultraviolet absorbers, light stabilizers and the like can be contained.
• the active energy ray-curable composition of the present invention can be produced by mixing, kneading, and dispersing an active energy ray-curable compound, a photopolymerization initiator, a matting agent, and various other additives.
• the active energy ray-curable composition of the present invention can be adjusted by appropriately adjusting the size of the grinding media of the disperser, the filling rate of the grinding media, the dispersion treatment time, and the like.
• As the dispersing machine commonly used roller mills, ball mills, pebble mills, attritors, sand mills and the like can be used. If air bubbles or unexpectedly large particles are contained in the coating agent, it is preferable to remove them by filtration or the like, as they lower the quality of the coated product.
• a conventionally known filter can be used.
• the active energy ray-curable composition of the present invention can form a coating film by a known coating/printing method.
• coating methods include roll coater, gravure coater, gravure offset coater, flexo coater, air doctor coater, blade coater, air knife coater, squeeze coater, impregnation coater, transfer roll coater, kiss coater, and curtain coater.
• a cast coater, a spray coater, a die coater, an offset printer, a screen printer, and the like can be used as appropriate.
• the matte coating film formed by the above formation method can be obtained by drying the solvent in a drying oven or the like and then curing it with active energy rays to obtain a cured coating film. can be done, but it is not necessary in the case of solvent-free.
• the substrate used in the present invention can be used without any particular limitation as long as it is a substrate for which a matte design is desired.
• a general-purpose base sheet used for decorative sheets can be used as the base material.
• the base sheet is not particularly limited, and a general decorative sheet (film) made of a general-purpose thermoplastic resin or paper is used.
• Sheets (films) formed of thermoplastic resins include, for example, polyethylene, ethylene- ⁇ -olefin copolymer, polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, ethylene- Polyolefin resins such as vinyl acetate copolymer, ethylene-vinyl acetate copolymer saponified product, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester copolymer, polyvinyl chloride, polyethylene terephthalate (PET), polybutylene terephthalate, polyamide, polycarbonate, polyethylene naphthalate, ionomer, acrylic acid ester polymer, methacrylic acid ester polymer, and the like.
• the base sheet may be formed by using these resins alone or in combination of two or more.
• the base sheet may be colored, and if necessary, fillers, matting agents, foaming agents, flame retardants, lubricants, antistatic agents, antioxidants, ultraviolet absorbers, light stabilizers, etc. may contain various additives.
• the thickness of the base sheet can be appropriately set according to the application of the final product, the method of use, etc., but is generally preferably 20 to 300 ⁇ m.
• One side or both sides of the base sheet may be subjected to surface treatment such as corona discharge treatment, ozone treatment, plasma treatment, ionizing radiation treatment, dichromic acid treatment, etc., if necessary.
• surface treatment such as corona discharge treatment, ozone treatment, plasma treatment, ionizing radiation treatment, dichromic acid treatment, etc.
• the surface tension of the substrate sheet surface should be 30 dyne or more, preferably 40 dyne or more.
• the surface treatment may be carried out according to a conventional method for each treatment.
• Examples of types of paper substrates for decorative sheets include thin paper, plain paper, reinforced paper, paper sheets such as resin-impregnated paper, titanium paper, and the like.
• a wooden decorative board or the like which is widely used as a decorative board, may be used as the base material.
• the wooden base material for the wooden decorative board include known materials such as plywood, particle board, hardboard, MDF, etc., which have conventionally been used as wooden base materials for decorative boards, furniture, building members, and the like. Moreover, it does not matter what kind of manufacturing method these known base materials are obtained.
• noncombustible materials that can be used as base materials include gypsum board, gypsum board, perforated board building materials made of calcium silicate board, etc.; , galvanized steel plate, polyvinyl chloride sol-coated steel plate, aluminum plate, copper plate and the like.
• Step (I) A coating film is formed on a substrate selected from the substrates according to the purpose of use, using any of the coating methods described above, using the described active energy ray-curable composition.
• Step (II) it is preferable to irradiate the coating film with ultraviolet rays in the atmosphere.
• ultraviolet irradiation under the atmosphere can be performed by a known method.
• germicidal lamp, ultraviolet fluorescent lamp, ultraviolet light emitting diode (UV-LED), carbon arc, metal halide lamp, xenon lamp, chemical lamp, low pressure mercury lamp, high pressure mercury lamp for copying, medium or high pressure mercury lamp, ultra high pressure mercury lamp, Ultraviolet rays are irradiated using an electrodeless lamp, a metal halide lamp, natural light, or the like as a light source.
• the cumulative amount of UV light in step (2) is preferably in the range of 20 to 1000 mJ/cm 2 in order to maximize the effects of the present invention.
• the integrated amount of light is in the range of 40 to 800 mJ/cm 2 . If it is 20 mJ/cm 2 or more, the curing efficiency is good, and if it is 1000 mJ/cm 2 or less, it is possible to prevent damage to the substrate due to heat generation.
• the matting effect can be efficiently obtained due to the surface orientation of the matting agent. A matte effect similar to that of conventional paints can be obtained.
• the matte coating film is completely cured in step (III) of irradiating with active energy rays.
• the active energy ray may be an electron beam or an ultraviolet ray.
• the atmosphere having an oxygen concentration of less than 5% means an atmosphere filled with an oxygen-containing inert gas and having an oxygen concentration of less than 5%.
• the inert gas one or a mixture of a plurality of gases such as nitrogen gas, carbon dioxide gas, and argon gas may be used. In addition, there is no problem even if a small amount of gas such as carbon dioxide contained in the air is contained.
• UV light in step (III) is preferably in the range of 20 to 1000 mJ/cm 2 in order to maximize the effects of the present invention. Among them, it is more preferable that the integrated amount of light is in the range of 40 to 800 mJ/cm 2 .
• an electron beam irradiation device is used.
• the irradiation dose is preferably about 10 to 230 kGy, more preferably about 10 to 100 kGy.
• the atmosphere for electron beam irradiation preferably has an oxygen concentration of 2% or less.
• the thickness of the coating film thus obtained is preferably in the range of 0.1 to 100 ⁇ m, most preferably in the range of 0.5 to 50 ⁇ m. By setting the film thickness within this range, the effects of the present invention can be maximized.
• the production method of the present invention can be widely used not only for building materials such as decorative sheets, but also for surface coating applications such as furniture, musical instruments, office supplies, sporting goods, and toys.
• the average particle size of silica was measured using a nanoparticle particle size distribution analyzer Nanotrac UPA EX-150 manufactured by Nikkiso Co., Ltd.
• Example 1 Ethylene oxide-modified 1,6-hexanediol diacrylate Miramer M202 (manufactured by MIWON) 50 parts, ethylene oxide-modified trimethylolpropane triacrylate M3130 (MIWON) 50 parts, photopolymerization initiator 1-hydroxy- Cyclohexyl-phenyl-ketone "Omnirad184" (manufactured by BASF) 1.5 parts, Nip Seal E170 (average particle size: 3 ⁇ m, manufactured by Tosoh Silica Co., Ltd.) which is an organic surface-treated silica (wet silica) as a matting agent
• the active energy ray-curable composition 1 was prepared by stirring and mixing 15 parts of total 116.5 parts with a stirrer for 1 hour.
• Examples 2 to 8 Comparative Examples 1 to 9
• Each active energy ray-curable composition was prepared in the same manner as in Example 1 according to the formulations shown in Tables 1 to 3.
• step (I) ⁇ Formation of coating film by step (I)> Using a polypropylene film (manufactured by Okamoto Co., Ltd., 0.5 mm thick) as a base material, using a bar coater (10 ⁇ m), active energy ray-curing properties prepared in Examples 1 to 8 and Comparative Examples 1 to 9 According to Tables 1 to 3, the coated article coated with each composition is subjected to step (II) of ultraviolet irradiation in the atmosphere and then step (III) of irradiation with active energy rays.
• step (II)> Using an air-cooled high-pressure mercury lamp (output 120 W / cm 1 lamp) and a UV irradiation device (GS Yuasa Corporation) equipped with a belt conveyor, the above-mentioned coated object is placed on the conveyor and directly under the lamp in the atmosphere (irradiation The coating film was semi-cured by passing through a distance of 11 cm) at a speed of 25 meters per minute. It was confirmed that the amount of ultraviolet irradiation was 55 mJ/cm 2 using an ultraviolet integrating photometer (industrial UV checker UVR-N1 manufactured by GS Yuasa Corporation).
• gloss value (gloss value) of the completely cured matte coating film surface was measured using a gloss meter (“MULTI GLOSS 268A” manufactured by Konica Minolta Co., Ltd.) in order to measure the specular glossiness according to JIS Z8741. .
• the measurement conditions for the gloss value were an incident angle of 60° and a reflection angle of 60°. (Evaluation criteria) ⁇ : Less than 10% ⁇ : 10% or more and less than 20% ⁇ : 20% or more
• Tables 1 to 3 show the composition of each active energy ray-curable composition and the evaluation results of the produced matte coating films. All numerical values in the table are parts by mass or % by mass. A blank column indicates that it is not blended. In addition, the N.V. D. indicates that the viscosity is too high to be evaluated.
• Acid multimer ester Miramer M202 MIWON ethylene oxide-modified 1,6-hexanediol diacrylate
• Miramer M220 MIWON tripropylene glycol diacrylate
• Miramer M284 MIWON polyethylene glycol diacrylate
• Miramer M3130 MIWON ethylene oxide Modified trimethylolpropane triacrylate
• Miramer M340 Pentaerythritol triacrylate manufactured by MIWON DPA600T: Dipentaerythritol hexaacrylate manufactured by Zhangjiagang East Asia Biochemical Co., Ltd.
• Omnirad184 Photopolymerization initiator manufactured by BASF 1-hydroxy-cyclohexyl- Phenyl-ketone, Nipsil E170: Silica manufactured by Tosoh Silica Co., Ltd., average particle size 3 ⁇ m ⁇ Cyloid ED-50: W. R. Grace silica, average particle size 8 ⁇ m ⁇ NIPGEL BY-001: silica manufactured by Tosoh Silica Co., Ltd., average particle size 14 ⁇ m
• the active energy ray-curable composition of the present invention maintains a viscosity that allows application as a coating agent without using an organic solvent, and at the same time has low glossiness, stain resistance, and scratch resistance that provide a matting effect. can do.

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