WO2014081004A1 - Composition de résine durcissable par rayonnement d'énergie active, composition d'agent de revêtement et stratifié - Google Patents

Composition de résine durcissable par rayonnement d'énergie active, composition d'agent de revêtement et stratifié Download PDF

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WO2014081004A1
WO2014081004A1 PCT/JP2013/081484 JP2013081484W WO2014081004A1 WO 2014081004 A1 WO2014081004 A1 WO 2014081004A1 JP 2013081484 W JP2013081484 W JP 2013081484W WO 2014081004 A1 WO2014081004 A1 WO 2014081004A1
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meth
acrylate
compound
active energy
urethane
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PCT/JP2013/081484
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English (en)
Japanese (ja)
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篤志 辻本
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日本合成化学工業株式会社
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Priority claimed from JP2013241245A external-priority patent/JP6359265B2/ja
Application filed by 日本合成化学工業株式会社 filed Critical 日本合成化学工業株式会社
Priority to KR1020157012605A priority Critical patent/KR20150090061A/ko
Priority to CN201380059384.8A priority patent/CN104797613A/zh
Publication of WO2014081004A1 publication Critical patent/WO2014081004A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • 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
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • 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
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/757—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing at least two isocyanate or isothiocyanate groups linked to the cycloaliphatic ring by means of an aliphatic group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
    • C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
    • C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
    • C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
    • C08G18/8025—Masked aliphatic or cycloaliphatic polyisocyanates
    • 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

Definitions

  • the present invention relates to an active energy ray-curable resin composition, a coating agent composition, and a laminate, and more specifically, has a moist touch feeling called soft feel and soft touch when used as a cured coating film, and Active energy ray-curable resin composition for forming a cured coating film excellent in appearance and high quality, a coating agent composition using the same, and further a substrate and a coating layer comprising the coating agent composition It is related with the laminated body which has.
  • polyurethane coating agents containing organic fine particles have been used as coating agents for interior parts such as plastic panels in automobiles in order to give a high-class feeling and a moist touch feeling.
  • a polyurethane-based coating agent is a thermosetting type coating agent obtained by reacting a polyol component and an isocyanate component. Since the reactivity of the polyol component and the isocyanate component is high, it is usually used in two liquids. Since both were mixed immediately before application to the material, the workability and productivity were inferior.
  • Patent Document 1 discloses a first urethane resin obtained by a reaction between a polycarbonate-based polyol and a polyisocyanate.
  • a second urethane resin obtained by the reaction of a polyether polyol and a polyisocyanate, a crosslinking agent containing two or more carbodiimide groups in one molecule, urethane beads, and surface modification that is an organosilicon compound.
  • Patent Document 1 has been devised to extend the pot life as a paint by using an aqueous dispersion of carbodiimide as a crosslinking agent in order to control the reactivity in an aqueous coating solution.
  • an aqueous dispersion of carbodiimide as a crosslinking agent
  • it takes several days in a humidity control atmosphere so the solution stability (workability) is improved to some extent.
  • productivity was still not satisfactory.
  • Patent Document 2 Although the technique disclosed in Patent Document 2 is considered to have improved durability of various coating layers as a solvent-based coating liquid, the stability of the coating liquid in which isocyanate and polyol are mixed is sufficient. However, it was thought that this was not the case, and there were still problems in workability.
  • the present invention is a one-part curable resin composition excellent in workability under such a background, and has a soft and soft touch when used as a coating layer. It is another object of the present invention to provide an active energy ray-curable resin composition excellent in workability during coating and productivity during curing, and a coating agent composition using the same.
  • thermosetting urethane resin as a resin component in a coating composition obtained by adding a fine synthetic resin filler to a resin component.
  • urethane (meth) acrylate having active energy ray curability
  • an active energy ray curable resin composition excellent in workability during coating and productivity during curing can be obtained and cured.
  • the present invention was completed by finding that the coating film (coating layer) obtained later had a moist and soft touch feeling.
  • the gist of the present invention relates to an active energy ray-curable resin composition comprising a urethane (meth) acrylate compound (A) and a fine particle synthetic resin filler (B).
  • the present invention also provides a coating composition comprising the active energy ray-curable resin composition, and a laminate having a substrate and a coating layer comprising the coating composition. .
  • the active energy ray-curable resin composition of the present invention when used as a coating agent, becomes an active energy ray-curable resin composition excellent in workability during coating and productivity during curing, and
  • the coating layer obtained after curing has an effect of having a moist and soft touch feeling and is particularly useful as a coating agent.
  • the active energy ray-curable resin composition of the present invention comprises a urethane (meth) acrylate compound (A) and a fine synthetic resin filler (B).
  • (meth) acryl means acryl or methacryl
  • (meth) acryloyl means acryloyl or methacryloyl
  • (meth) acrylate means acrylate or methacrylate.
  • the content of the ethylenically unsaturated group of the urethane (meth) acrylate compound (A) used in the present invention is preferably 2 to 10, particularly preferably 2 to 6. If the number of such ethylenically unsaturated groups is too large, the crosslinking density after curing becomes too large, and the coating film tends to be too hard and it is difficult to obtain a moist soft feeling. Since it cannot be obtained, there is a tendency that the surface of the cured coating film is sticky or various durability performances are deteriorated.
  • the weight average molecular weight of the urethane (meth) acrylate compound (A) used in the present invention is preferably 1,000 to 50,000, particularly preferably 1,500 to 40,000, particularly preferably 2. , 5,000 to 35,000. If the weight average molecular weight is too small, the crosslink density is relatively increased, so that the surface of the cured coating film is too hard and it is difficult to obtain a moist soft feeling. If it is too large, the viscosity of the curable resin composition is low. There is a tendency to become too high, a sufficient crosslinking density cannot be obtained, the surface of the cured coating film becomes sticky, and various durability tends to decrease.
  • said weight average molecular weight is a weight average molecular weight by standard polystyrene molecular weight conversion, a column is put into a high performance liquid chromatography (Nippon Waters Co., Ltd., "Waters 2695 (main body)” and “Waters 2414 (detector)”).
  • Shidex GPC KF-806L exclusion limit molecular weight: 2 ⁇ 10 7 , separation range: 100 to 2 ⁇ 10 7 , theoretical plate number: 10,000 plates / piece, filler material: styrene-divinylbenzene copolymer, filler
  • the viscosity of the urethane (meth) acrylate compound (A) at 60 ° C. is preferably 1,000 to 100,000 mPa ⁇ s, and particularly preferably 1,500 to 50,000 mPa ⁇ s. When the viscosity is out of the above range, the coatability tends to be lowered.
  • the measuring method of a viscosity is based on an E-type viscometer.
  • the urethane (meth) acrylate compound (A) used in the present invention is obtained by reacting a hydroxyl group-containing (meth) acrylate compound (a1), a polyvalent isocyanate compound (a2) and a polyol compound (a3).
  • a urethane (meth) acrylate compound (A2) obtained by reacting a urethane (meth) acrylate compound (A1) or a hydroxyl group-containing (meth) acrylate compound (a1) and a polyvalent isocyanate compound (a2).
  • only one type may be used alone, or two or more types may be used in combination.
  • the urethane (meth) acrylate compound (A1) is obtained by reacting the hydroxyl group-containing (meth) acrylate compound (a1), the polyvalent isocyanate compound (a2), and the polyol compound (a3). .
  • the hydroxyl group-containing (meth) acrylate compound (a1), polyvalent isocyanate compound (a2), and polyol compound (a3), which are compounds for obtaining the urethane (meth) acrylate compound (A1), will be described below in order. .
  • hydroxyl group-containing (meth) acrylate compound (a1) examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth).
  • hydroxyalkyl (meth) acrylates such as 6-hydroxyhexyl (meth) acrylate, 2-hydroxyethyl acryloyl phosphate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, caprolactone-modified 2-hydroxyethyl (meth) ) Acrylate, dipropylene glycol (meth) acrylate, fatty acid modified-glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) Acrylate, 2-hydroxy-3- (meth) acryloyloxy propyl (meth) acrylate, containing one ethylenically unsaturated group such as (meth) acrylate compound; (Meth) acrylate compounds containing two ethylenically unsaturated groups such as glycerin di (meth) acrylate, 2-hydroxy-3-acryloyl-oxypropy
  • polyvalent isocyanate compound (a2) examples include aromatics such as tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate.
  • Polyisocyanate Aliphatic polyisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate; Cycloaliphatic polyisocyanates such as hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane; Alternatively, trimer compounds or multimeric compounds of these polyisocyanates, allophanate type polyisocyanates, burette type polyisocyanates, water-dispersed polyisocyanates (for example, “Aquanate 100”, “Aquanate 110” manufactured by Nippon Polyurethane Industry Co., Ltd., "Aquanate 200", “Aquanate 210", etc.).
  • the polyol compound (a3) may be any compound containing two or more hydroxyl groups.
  • an aliphatic polyol, an alicyclic polyol, a polyether polyol, a polyester polyol, a polycarbonate polyol, a polyolefin polyol examples thereof include polybutadiene-based polyols, polyisoprene-based polyols, (meth) acrylic polyols, and polysiloxane-based polyols.
  • the weight-average molecular weight of the polyol compound (a3) is preferably 60 to 20,000, particularly preferably 100 to 15,000, and further preferably 150 to 8,000. If the weight-average molecular weight of the polyol-based compound (a3) is too large, a sufficient crosslinking density cannot be obtained at the time of curing, the cured coating film surface tends to be sticky, and various durability tends to decrease. The curable resin composition tends to be highly viscous and difficult to handle. Moreover, when the weight average molecular weight of a polyol type compound (a3) is too small, the softness
  • the polyol compound (a3) contains a polyol compound (a3-1) having a weight average molecular weight of less than 500 and a polyol compound (a3-2) having a weight average molecular weight of 500 to 20,000. From the viewpoint of sex.
  • the weight average molecular weight of the polyol compound (a3-1) is less than 500, preferably 60 to 450, particularly preferably 60 to 400, and further preferably 100 to 300.
  • the weight average molecular weight of the polyol compound (a3-1) is too large, when it is used as a blended composition, the hydrogen bond pseudo-crosslinking degree peculiar to the urethane bond is lowered, so that durability such as chemical resistance of the cured coating film is reduced. There is a tendency to decrease.
  • the weight average molecular weight of the polyol compound (a3-2) is 500 to 20,000, preferably 2,000 to 15,000, and particularly preferably 3,000 to 8,000. If the weight average molecular weight of the polyol compound (a3-2) is too small, the molecular weight of the urethane (meth) acrylate compound (A) becomes relatively small. When it is too large, the coating film made of a resin solution that is blended to form an active energy ray-curable composition tends to be sticky. Further, since the polyol compound (a3-2) has a large weight average molecular weight, the reactivity at the time of synthesis becomes poor, so that the reaction time becomes extremely long, and this is not practically preferable as a synthesis condition.
  • the difference between the polyol compound (a3-1) and the polyol compound (a3-2) is preferably 400 or more, particularly preferably 800 or more, more preferably 1,200 or more. Particularly preferred is 2,000 or more. If the difference is too small, the balance between chemical resistance and elasticity of the cured coating film tends to be inferior, making it difficult to achieve both functions.
  • Examples of the polyol compound (a3-1) having a weight average molecular weight of less than 500 include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, dimethylolpropane, neopentyl glycol, 1,2-hexanediol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-tetramethylenediol, 1,3-tetramethylenediol, 2-methyl-1, 3-trimethylenediol, 1,5-pentamethylenediol, 1,6-hexamethylenediol, 3-methyl-1,5-pentamethylenediol, 2,4-diethyl-1,5-pentamethylenediol, 1, 9-nonanediol, 2-methyl-1,8-o Aliphatic alcohols such as tandiol, ditrimethylo
  • Examples of the polyol compound (a3-2) having a weight average molecular weight of 500 to 20,000 include aliphatic polyols, alicyclic polyols, polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, Examples include polybutadiene polyols, (meth) acrylic polyols, and polysiloxane polyols.
  • aliphatic polyol examples include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, dimethylolpropane, neopentyl glycol, 2,2-diethyl-1,3-propanediol, and 2-butyl- 2-ethyl-1,3-propanediol, 1,4-tetramethylenediol, 1,3-tetramethylenediol, 2-methyl-1,3-trimethylenediol, 1,5-pentamethylenediol, 1,6 -Hexamethylenediol, 3-methyl-1,5-pentamethylenediol, 2,4-diethyl-1,5-pentamethylenediol, pentaerythritol diacrylate, 1,9-nonanediol, 2-methyl-1,8 -Two hydroxyl acids such as octanediol , Aliphatic alcohols containing 3
  • alicyclic polyol examples include cyclohexanediols such as 1,4-cyclohexanediol and cyclohexyldimethanol, hydrogenated bisphenols such as hydrogenated bisphenol A, and tricyclodecane dimethanol. Two or more species can be used in combination.
  • polyether polyol examples include, for example, polyether glycols containing alkylene structures such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene glycol, polypentamethylene glycol, polyhexamethylene glycol, and the like. A random or block copolymer is mentioned.
  • polyester-based polyol examples include three types of components: a condensation polymer of a polyhydric alcohol and a polycarboxylic acid; a ring-opening polymer of a cyclic ester (lactone); a polyhydric alcohol, a polycarboxylic acid, and a cyclic ester. And the like.
  • polyhydric alcohol examples include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylene diol, 1,3-tetramethylene diol, 2-methyl-1,3-trimethyl.
  • Methylene diol 1,5-pentamethylene diol, neopentyl glycol, 1,6-hexamethylene diol, 3-methyl-1,5-pentamethylene diol, 2,4-diethyl-1,5-pentamethylene diol, glycerin , Trimethylolpropane, trimethylolethane, cyclohexanediols (such as 1,4-cyclohexanediol), bisphenols (such as bisphenol A), sugar alcohols (such as xylitol and sorbitol)
  • polyvalent carboxylic acid examples include aliphatic dicarboxylic acids such as malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid; -Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, paraphenylenedicarboxylic acid, trimellitic acid, and the like.
  • aliphatic dicarboxylic acids such as malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid
  • -Alicyclic dicarboxylic acids such as
  • cyclic ester examples include propiolactone, ⁇ -methyl- ⁇ -valerolactone, and ⁇ -caprolactone.
  • polycarbonate polyol examples include a reaction product of a polyhydric alcohol and phosgene; a ring-opening polymer of a cyclic carbonate (such as alkylene carbonate).
  • polyhydric alcohol examples include polyhydric alcohols exemplified in the description of the polyester-based polyol, and examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, hexamethylene carbonate, and the like. It is done.
  • the polycarbonate-based polyol may be a compound having a carbonate bond in the molecule and having a hydroxyl group at the end, and may have an ester bond together with the carbonate bond.
  • polyolefin-based polyol examples include those having a saturated hydrocarbon skeleton having a homopolymer or copolymer such as ethylene, propylene and butene, and having a hydroxyl group at the molecular end.
  • polybutadiene-based polyol examples include those having a butadiene copolymer as a hydrocarbon skeleton and having a hydroxyl group at the molecular end.
  • the polybutadiene-based polyol may be a hydrogenated polybutadiene polyol in which all or part of the ethylenically unsaturated groups contained in the structure thereof are hydrogenated.
  • polyisoprene-based polyol examples include those having a copolymer of isoprene as a hydrocarbon skeleton and a hydroxyl group at the molecular end.
  • the polyisoprene-based polyol may be a hydrogenated polyisoprene polyol in which all or part of the ethylenically unsaturated groups contained in the structure is hydrogenated.
  • Examples of the (meth) acrylic polyol include those having at least two hydroxyl groups in the molecule of the polymer or copolymer of the (meth) acrylic ester.
  • polysiloxane polyol examples include dimethyl polysiloxane polyol and methylphenyl polysiloxane polyol.
  • aliphatic polyols and alicyclic polyols are preferably used in terms of suppressing stickiness when it becomes a cured coating film, and polyester polyols, polyether polyols, and polycarbonate polyols are preferred in terms of imparting flexibility. Preferably used.
  • the production method of the urethane (meth) acrylate compound (A1) is usually a reaction of the hydroxyl group-containing (meth) acrylate compound (a1), the polyvalent isocyanate compound (a2), and the polyol compound (a3) with a reactor.
  • the reaction product obtained by reacting the polyol-based compound (a3) and the polyvalent isocyanate-based compound (a2) in advance may be added to the hydroxyl group-containing (meth) acrylate-based compound ( The reaction of a1) is useful in terms of reaction stability and reduction of byproducts.
  • the reaction between the polyol compound (a3) and the polyvalent isocyanate compound (a2) known reaction means can be used.
  • the molar ratio of the isocyanate group in the polyvalent isocyanate compound (a2) to the hydroxyl group in the polyol compound (a3) is usually about 2n: (2n-2) (n is an integer of 2 or more).
  • the addition reaction of the reaction product obtained by reacting the polyol compound (a3) and the polyvalent isocyanate compound (a2) in advance with the hydroxyl group-containing (meth) acrylate compound (a1) is also a known reaction. Means can be used.
  • reaction In the addition reaction between the reaction product and the hydroxyl group-containing (meth) acrylate compound (a1), the reaction is terminated when the residual isocyanate group content in the reaction system is 0.5% by weight or less. A (meth) acrylate compound (A1) is obtained.
  • Metal salts such as stannic chloride, triethylamine, benzyldiethylamine, 1,4-diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [5,4,0] undecene, N, N, N ′
  • Amine catalysts such as N'-tetramethyl-1,3-butanediamine and N-ethylmorpholine, bismuth nitrate, bibromide
  • organic bismuth compounds such as dibutyl bismuth dilaurate and dioctyl bismuth dilaurate, bismuth 2-ethylhexanoate, bismuth naphthenate, bismuth isodecanoate, bismuth neodecanoate, lauryl Organic acid bismuth such as bismuth acid salt, bismuth maleate, bismuth stea
  • Organic solvents having no functional group for example, esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and organic solvents such as aromatics such as toluene and xylene can be used.
  • the reaction temperature is usually 30 to 90 ° C., preferably 40 to 80 ° C.
  • the reaction time is usually 2 to 10 hours, preferably 3 to 8 hours.
  • the polyol compound (a3) constituting the urethane (meth) acrylate compound (A1) a polyol compound (a3-1) having a weight average molecular weight of less than 500 and a polyol compound (a3) having a weight average molecular weight of 500 to 20,000 are used.
  • the urethane (meth) acrylate compound (A1) preferably has a weight average molecular weight of 2,500 to 50,000, particularly preferably 2,500 to 40,000, More preferably, it is 3,500 to 30,000.
  • the weight average molecular weight is too small, the unsaturated group equivalent in the compounding will increase relatively, and when it is a cured coating film, the hardness difference from the fine synthetic resin filler (B) becomes remarkable, and the external The stress of the curable resin composition tends to be damaged due to the stress that cannot be released, and if it is too large, the viscosity of the curable resin composition tends to be too high, and a sufficient crosslinking density cannot be obtained. There is a tendency that the surface becomes sticky and various durability tends to decrease.
  • the viscosity of the urethane (meth) acrylate compound (A1) at 60 ° C. is preferably 1,000 to 100,000 mPa ⁇ s, particularly preferably 1,500 to 50,000 mPa ⁇ s. When the viscosity is out of the above range, the coatability tends to be lowered. The viscosity is measured by an E-type viscometer as described above.
  • the content of ethylenically unsaturated groups in the urethane (meth) acrylate compound (A2) used in the present invention is preferably 2 to 10, particularly preferably 2 to 6. If the number of such ethylenically unsaturated groups is too large, the crosslinking density after curing becomes too large, and the coating film tends to be too hard and it is difficult to obtain a moist soft feeling. Since it is difficult to obtain, the surface of the cured coating film tends to be sticky or the durability performance tends to deteriorate.
  • the hydroxyl group-containing (meth) acrylate compound (a1) and the polyvalent isocyanate compound (a2) may be appropriately selected and used.
  • a hydroxyl group-containing (meth) acrylate compound (a1) having three ethylenically unsaturated groups and using a diisocyanate compound as the polyvalent isocyanate compound (a2) urethane (meth) acrylate
  • the number of ethylenically unsaturated groups in the compound (A2) is 6.
  • the reaction molar ratio between the polyvalent isocyanate compound (a2) and the hydroxyl group-containing (meth) acrylate compound (a1) is, for example, that the polyisocyanate compound (a2) has two isocyanate groups and has a hydroxyl group content ( When the meth) acrylate compound (a1) has one hydroxyl group, the polyvalent isocyanate compound (a2): hydroxyl group-containing (meth) acrylate compound (a1) is about 1: 2, and the polyisocyanate compound When the compound (a2) has three isocyanate groups and the hydroxyl group-containing (meth) acrylate compound (a1) has one hydroxyl group, the polyvalent isocyanate compound (a2): hydroxyl group-containing (meth) acrylate compound (A1) is about 1: 3.
  • the viscosity of the urethane (meth) acrylate compound (A2) at 60 ° C. is preferably 1,000 to 30,000 mPa ⁇ s, particularly preferably 1,000 to 20,000 mPa ⁇ s. When the viscosity is out of the above range, the coatability tends to be lowered. The viscosity is measured by an E-type viscometer as described above.
  • Examples of the fine particle synthetic resin filler (B) in the present invention include nitrogen atom-containing synthetic resin fillers such as nylon filler, polyurethane filler, polyurea filler, polyamideimide filler, polyacrylamide filler; Polyolefin resin fillers such as polyethylene filler and polypropylene filler; Poly (meth) acrylic filler, polybutyl (meth) acrylic filler, (meth) acrylic group-containing synthetic resin filler consisting of a single polymerization component such as polystyrene filler, (meth) acrylic group-containing synthetic resin consisting of two or more polymerization components (Meth) acrylic synthetic resin fillers such as fillers; Sulfur atom-containing synthetic resin filler such as polyphenylene sulfide filler and polyethersulfone filler; Fluorine atom-containing synthetic resin filler such as polytetrafluoroethylene filler; An epoxy group-containing synthetic resin filler comprising an epoxy resin; Polycarbon
  • Nitrogen atom-containing synthetic resin filler preferably has excellent affinity with urethane (meth) acrylate compound (A), particle aggregation stability, sedimentation stability, moist soft coating and elasticity It is a polyurethane filler because it is easy to do, and a polyethylene filler is preferable as the polyolefin resin filler. Furthermore, in order to give a moist touch feeling to the cured coating film, it is preferable to use the polyurethane filler and the polyethylene filler in combination.
  • nylon filler examples include those manufactured by Toray Industries, Inc. (trade names: “SP-10”, “SP-500”, “TR-1”, “TR-2”, “842-P48”, “842-P70”). , “842-P80”).
  • polyurethane filler examples include cross-linked urethane beads manufactured by Negami Kogyo Co., Ltd. (trade names: “Art Pearl C Series”, “Art Pearl P Series”, “Art Pearl JB Series”, “Art Pearl U Series”, “Art” “Pearl CE Series”, “Art Pearl AK Series”, “Art Pearl HI Series”, “Art Pearl MM Series”, “Art Pearl FF Series”, “Art Pearl TK Series”, “Art Pearl C-TH Series”, “ Art Pearl RW-Z series ",” Art Pearl RU-V series “,” Art Pearl BP series “).
  • transparent fine particles are preferable as those capable of obtaining a transparent to white coating film as a cured coating film without impairing photocurability, and those having a white appearance as a fine particle appearance are preferable.
  • polyamideimide resin filler examples include those manufactured by Toray Industries, Inc. (trade name: “Trepearl PAI”).
  • the polyethylene filler is preferably a solvent-dispersed polyethylene filler.
  • polyethylene wax and modified polyethylene wax (trade names; “Micro Flat UN-8”, “Micro Flat PEX-101” manufactured by Koyo Chemical Co., Ltd.) , “Micro Flat B-501”), polyethylene wax manufactured by Big Chemie Japan, and modified polyethylene wax (trade names; “CERAFLOUR928”, “CERAFLOUR950”, “CERAFLOUR988”, “CERAFLOUR990”, “CERAFLOUR991”, “CERAFLOUR995”) ”,“ CERACOL39 ”,“ CERAFAK111 ”,“ CERAMAT250 ”,“ CERAMAT258 ”,“ MINERPOL221 ”), and the like.
  • the above-mentioned polypropylene filler is preferably a solvent dispersion type, and examples thereof include a polypropylene wax manufactured by Big Chemie Japan, a modified polypropylene wax (trade name “CERAFLOUR970”), and the like.
  • Examples of the (meth) acrylic group-containing synthetic resin filler include acrylic beads manufactured by Negami Kogyo Co., Ltd. (trade names; “Art Pearl GR Series”, “Art Pearl SE Series”, “Art Pearl G Series”, “Art Pearl” GS series “,” Art Pearl J series “,” Art Pearl MF series “,” Art Pearl BE series “).
  • transparent fine particles are preferable as those capable of obtaining a transparent to white coating film as a cured coating film without impairing photocurability, and those having a white appearance as a fine particle appearance are preferable.
  • sulfur atom-containing synthetic resin filler examples include polyphenylene sulfide resin fine particles (trade name: “Trepearl PPS”), polyethersulfone resin (trade name: “Trepearl PES”) manufactured by Toray Industries, Inc.
  • fluorine atom-containing synthetic resin filler examples include polyethylene manufactured by Koyo Chemical Co., Ltd., and polytetrafluoroethylene mixed wax (trade name: “Micro-flat PF-8”), manufactured by Big Chemie Japan Co., Ltd.
  • Fluoroethylene wax (trade names; “CERAFLOUR980”, “CERAFLOUR981”), polyethylene-polytetrafluoroethylene mixed wax (trade name; “CERAFLOUR997”), polytetrafluoroethylene-modified polyethylene wax (trade name; “CERAFLOUR998”, “CERACOL607”), polytetrafluoroethylene microparticles manufactured by Kitamura (trade names: "KTL-8N", “KTL-8F”, “KTL-9S”, “KTL-10N”, “KTL-20N”) It is done.
  • epoxy group-containing synthetic resin filler examples include those manufactured by Toray Industries, Inc. (trade name: “Trepearl EP”).
  • polycarbonate resin filler examples include those manufactured by Koyo Chemical Co., Ltd. (trade name: “Micro-flat MA-07N”).
  • the average particle size of the fine particle synthetic resin filler (B) in the present invention is preferably 1 to 30 ⁇ m, particularly preferably 2 to 20 ⁇ m, and further preferably 4 to 15 ⁇ m. If the average particle size is too small, the gloss of the cured coating film tends to be high, and there is a tendency that it is difficult to feel a high-grade appearance, and if it is too large, the wear contact becomes large and wear resistance decreases, and the cured surface Since the unevenness becomes large and rough, it tends to be difficult to obtain a moist and soft touch feeling.
  • the particle diameter can be determined using a sphere as a basic shape, and generally the number average particle diameter, length average particle diameter, area average Although there are particle diameter, volume average particle diameter, etc., the average particle diameter of the present invention is a volume average particle diameter usually used, and the volume average particle diameter is measured by a laser diffraction / scattering type particle size distribution meter. .
  • the true specific gravity of the fine synthetic resin filler (B) is preferably 0.8 to 2.3, particularly preferably 0.8 to 2, and further preferably 0.8 to 1.5. If the true specific gravity is too large, fine particles will settle in the drying step after coating and tend not to appear as surface irregularities. If it is too small, mixing of the urethane (meth) acrylate compound (A) tends to be difficult. .
  • Examples of the method for producing the fine particle synthetic resin filler (B) include a method for directly producing a fine particle synthetic resin by polymerizing a monomer by suspension polymerization, emulsion polymerization, seed polymerization, and the like, and various methods. There is a method of mechanically pulverizing a normal synthetic resin produced by the above method into fine particles. Among these, the polymerization method is preferable in that fine particles having a uniform shape, particularly spherical particles having excellent fluidity and dispersibility can be obtained.
  • the glass transition temperature (Tg) of the fine particle synthetic resin filler (B) in the present invention is preferably ⁇ 140 to 40 ° C., particularly preferably ⁇ 135 to 20 ° C., more preferably ⁇ 130 to 0 ° C. is there. If the glass transition temperature is too low, the coating surface tends to be too sticky, and if it is too high, a rubbery and moist soft feeling tends to be hardly obtained on the coating surface.
  • the glass transition temperature can be measured by using a temperature modulation DSC (DSC2920 manufactured by TA Instruments). Measurement conditions are such that a sample of about 1 to 5 mg is enclosed in a dedicated aluminum pan, and the temperature is raised within a range of ⁇ 100 ° C. to 100 ° C. and 3 ° C./min.
  • DSC2920 manufactured by TA Instruments
  • the content (solid content) of the particulate synthetic resin filler (B) in the present invention is preferably 25 to 400 parts by weight with respect to 100 parts by weight of the urethane (meth) acrylate compound (A).
  • the amount is particularly preferably 30 to 350 parts by weight, and further preferably 35 to 250 parts by weight. If the content of the fine-particle synthetic resin filler (B) is too large, the wear of the cured coating film tends to be extremely lowered, and the coating surface tends to be rough. There is a tendency that a touch feeling is difficult to obtain.
  • the content (solid content) of the polyurethane filler is preferably 25 to 400 parts by weight, particularly preferably 30 to 300 parts by weight, with respect to 100 parts by weight of the urethane (meth) acrylate compound (A). More preferably, it is 35 to 250 parts by weight. If the polyurethane filler content is too high, the wear of the cured coating film tends to be extremely reduced, the surface of the coating film tends to be rough, and the amount is too small. There is.
  • the polyethylene filler is 0.1 to 70 parts by weight with respect to 100 parts by weight of the polyurethane filler.
  • the amount is preferably 0.5 to 50 parts by weight, more preferably 1 to 30 parts by weight. If the content of the polyethylene filler in the polyurethane filler is too small, the softness of the coating film is lowered, and the glossiness tends to be impaired due to the increase in gloss, and if it is too much, the scratch resistance performance of the cured coating film is reduced. It tends to be easier.
  • the fine particle synthetic resin filler (B) is a dispersion such as a solvent, it is specified as a weight in terms of solid content.
  • the active energy ray-curable resin composition of the present invention contains the urethane (meth) acrylate compound (A) and the fine particle synthetic resin filler (B) as essential components.
  • A urethane
  • B fine particle synthetic resin filler
  • the ethylenically unsaturated monomer (C) may be any ethylenically unsaturated monomer (excluding the urethane (meth) acrylate compound (A)) having one or more ethylenically unsaturated groups in one molecule. , For example, a monofunctional monomer, a bifunctional monomer, a trifunctional or higher monomer.
  • the monofunctional monomer may be any monomer containing one ethylenically unsaturated group.
  • Michael adduct of acrylic acid or 2-acryloyloxyethyl dicarboxylic acid monoester examples include acrylic acid dimer, methacrylic acid dimer, acrylic acid trimer. Methacrylic acid trimer, acrylic acid tetramer, methacrylic acid tetramer and the like.
  • 2-acryloyloxyethyl dicarboxylic acid monoester which is a carboxylic acid having a specific substituent include 2-acryloyloxyethyl succinic acid monoester, 2-methacryloyloxyethyl succinic acid monoester, and 2-acryloyloxyethyl.
  • Examples thereof include phthalic acid monoester, 2-methacryloyloxyethyl phthalic acid monoester, 2-acryloyloxyethyl hexahydrophthalic acid monoester, and 2-methacryloyloxyethyl hexahydrophthalic acid monoester. Furthermore, oligoester acrylate is also mentioned.
  • the bifunctional monomer may be any monomer containing two ethylenically unsaturated groups.
  • the tri- or higher functional monomer may be any monomer containing three or more ethylenically unsaturated groups.
  • ethylenically unsaturated monomers (C) may be used alone or in combination of two or more.
  • the ethylenically unsaturated monomer (C) may be separately added to the urethane (meth) acrylate compound (A) or the fine particle synthetic resin filler (B), or may be urethane (meth) acrylate.
  • a part of the compound (A) may be left in the system during production.
  • ethylenically unsaturated monomers (C) monofunctional monomers and bifunctional monomers are preferable, there is no aromatic ring, yellowing of the coating film can be suppressed, and cyclohexyl (meth) acrylate and isobornyl are highly versatile.
  • a hydroxyl group-containing ethylenically unsaturated monomer examples include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meta) because they have no aromatic ring and suppress yellowing of the coating film.
  • the content of the ethylenically unsaturated monomer (C) is preferably 0 to 500 parts by weight, particularly 5 to 500 parts by weight with respect to 100 parts by weight of the urethane (meth) acrylate compound (A). It is preferably 350 parts by weight, more preferably 10 to 150 parts by weight. If the content of the ethylenically unsaturated monomer (C) is too large, in the case of a monofunctional monomer, the coated film becomes sticky, and in the case of a monomer having two or more functions, the cured film becomes too hard. There is a tendency that it is difficult to obtain a moist and soft touch feeling.
  • Photopolymerization initiator (D) In the present invention, in addition to the urethane (meth) acrylate compound (A) and the fine synthetic resin filler (B), a photopolymerization initiator (D) is added in order to efficiently cure with active energy rays. It is preferable to contain.
  • Examples of the photopolymerization initiator (D) include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2- Hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholino) Acetophenones such as phenyl) butanone and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomers; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether Benzoi etc.
  • Benzophenone methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 2 , 4,6-Trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethananium bromide, (4-benzoylbenzyl) trimethylammonium chloride
  • Benzophenones such as 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy) -3,4 Thiox
  • auxiliary agents include triethanolamine, triisopropanolamine, 4,4′-dimethylaminobenzophenone (Michler ketone), 4,4′-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, 4-dimethylaminobenzoic acid.
  • Ethyl, ethyl 4-dimethylaminobenzoate (n-butoxy), isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone Etc. can be used in combination.
  • benzyl dimethyl ketal 1-hydroxycyclohexyl phenyl ketone, benzoin isopropyl ether, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 2-hydroxy-2-methyl-1- It is preferable to use phenylpropan-1-one.
  • a photoinitiator (D) As content of a photoinitiator (D), it is 0.1 with respect to 100 weight part of urethane (meth) acrylate type-compounds (A) (when it contains an ethylenically unsaturated monomer (C)). It is preferably ⁇ 40 parts by weight, particularly preferably 1 to 20 parts by weight, particularly preferably 2 to 20 parts by weight. If the content of the photopolymerization initiator (D) is too small, curing tends to be poor, and if it is too much, the solution stability tends to decrease such as precipitation when used as a coating agent, and embrittlement or coloring may occur. Problems tend to occur.
  • a curable resin composition is obtained, a leveling agent (E), a surface conditioner, a polymerization inhibitor, etc. can be further added as needed.
  • leveling agent (E) a known general leveling agent can be used as long as it has an action of imparting wettability to fine particles when the fine particles are wetted and dispersed in a solution such as a solvent. Silicone-modified resins, fluorine-modified resins, alkyl-modified resins, and the like can be used.
  • leveling agent (E) Commercially available products of the leveling agent (E) include, for example, Megafac series manufactured by DIC (MCF350-5, F472, F476, F445, F444, F443, F178, F470, F475, F479, F477, F482, F486, TF1025, F478, F178K, etc.); X22-3710, X22-162C, X22-3701E, X22160AS, X22170DX, X224015, X22176DX, X22-176F, X224272, KF8001, X22-2000, etc. manufactured by Shin-Etsu Chemical Co., Ltd .; FM4421, FM0425, FMDA26, FS1265, etc.
  • Examples of the surface conditioner include alkyd resins and cellulose acetate butyrate. Such alkyd resin and cellulose acetate butyrate have an effect of imparting a film-forming property at the time of coating and a solution viscosity adjusting effect.
  • polymerization inhibitor examples include p-benzoquinone, naphthoquinone, tolquinone, 2,5-diphenyl-p-benzoquinone, hydroquinone, 2,5-di-t-butylhydroquinone, methylhydroquinone, hydroquinone monomethyl ether, mono-t- Examples thereof include butyl hydroquinone and pt-butyl catechol.
  • the active energy ray curable resin composition of the present invention includes oil, antioxidant, flame retardant, antistatic agent, stabilizer, reinforcing agent, abrasive, inorganic fine particles, polymer compound (acrylic resin, polyester resin). , Epoxy resin, etc.) can also be blended.
  • the active energy ray-curable resin composition of the present invention is also preferably used by blending an organic solvent (F) and adjusting the viscosity.
  • organic solvent (F) include alcohols such as methanol, ethanol, propanol, n-butanol and i-butanol, ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone and cyclohexanone, cellosolves such as ethyl cellosolve, Aromatics such as toluene and xylene, glycol ethers such as propylene glycol monomethyl ether, acetates such as methyl acetate, ethyl acetate and butyl acetate, and diacetone alcohol. These organic solvents may be used alone or in combination of two or more.
  • the active energy ray-curable resin composition of the present invention can be usually diluted to 3 to 60% by weight using the organic solvent (F) and applied to a substrate.
  • the active energy ray-curable resin composition of the present invention is effectively used as a curable resin composition for coating film formation having a moist and soft touch feeling to various base materials, and active energy ray curing After applying the functional resin composition to the substrate (after further drying if the composition diluted with an organic solvent is applied), it is cured by irradiation with active energy rays.
  • the coating method is not particularly limited, and examples thereof include wet coating methods such as spraying, showering, dipping, flow coating, gravure coating, roll coating, spin coating, dispenser, ink jet, and screen printing. .
  • rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, electromagnetic waves such as X rays and ⁇ rays, electron beams, proton rays, neutron rays, etc.
  • Curing by ultraviolet irradiation is advantageous from the viewpoint of easy availability and price.
  • electron beam irradiation it can harden
  • a high pressure mercury lamp that emits light in a wavelength range of 150 to 450 nm
  • an ultrahigh pressure mercury lamp a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrodeless discharge lamp, an LED, etc.
  • Irradiation of about 30 to 3,000 mJ / cm 2 may be performed.
  • heating can be performed as necessary to complete the curing.
  • the coating film thickness (film thickness after curing) is usually preferably 1 to 50 ⁇ m, particularly preferably 2 to 40 ⁇ m, more preferably 5 to 30 ⁇ m.
  • Examples of the base material to which the active energy ray-curable resin composition of the present invention is applied include polyolefin resins, polyester resins, polycarbonate resins, acrylonitrile butadiene styrene copolymers (ABS), polystyrene resins, and polyamides. Resins, etc. and their molded products (films, sheets, cups, etc.), metal substrates (metal deposition layers, metal plates (copper, stainless steel (SUS304, SUSBA, etc.), aluminum, zinc, magnesium, etc.)), glass, etc. , And those composite substrates.
  • the active energy ray-curable resin composition comprising the urethane (meth) acrylate compound (A) of the present invention and the fine particle-like synthetic resin filler (B) has a moist touch feeling called soft feel and soft touch.
  • a moist touch feeling called soft feel and soft touch.
  • the active energy ray-curable resin composition of the present invention is very useful as a coating agent (painting in the non-optical field), and has improved workability (solution storage stability) and productivity (production speed) during coating. Has an excellent effect and is very useful.
  • the coating agent composition preferably contains 2 to 60% by weight of urethane (meth) acrylate compound (A), particularly preferably 3 to 40% by weight, and more preferably 5 to 30% by weight of the entire coating agent composition. % By weight.
  • the coating agent composition may or may not contain an organic solvent. If the content of the urethane (meth) acrylate compound (A) is too small, it tends to be difficult to obtain a moist and soft touch feeling, and if it is too much, the wear property of the cured coating film tends to be extremely lowered. is there.
  • B-1 Polyurethane fine particles (average particle size 6.2 ⁇ m: glass transition temperature ⁇ 52 ° C.)
  • B-2 Polyurethane fine particles (average particle size 16.7 ⁇ m: glass transition temperature ⁇ 34 ° C.)
  • B-3 polyurethane fine particles (average particle size 6.5 ⁇ m: glass transition temperature ⁇ 34 ° C.)
  • B-4 polyurethane fine particles (average particle size 13.5 ⁇ m: glass transition temperature ⁇ 13 ° C.)
  • B-5 Polyethylene wax (particle size 5-10 ⁇ m)
  • Example 1 100 parts of the bifunctional urethane (meth) acrylate compound (A1-1) obtained in Production Example 1 above, 65.9 parts of fine synthetic resin filler (B-1), fine synthetic resin filler (B- 5) 0.5 parts (solid content), 6.8 parts of photopolymerization initiator (D-1), and 2.7 parts of leveling agent (E-1) are mixed to a solids concentration of 50% using ethyl acetate. Thus, an active energy ray-curable resin composition was obtained.
  • Example 2 100 parts of the bifunctional urethane (meth) acrylate compound (A1-2) obtained in Production Example 2 above, 67.0 parts of fine particle synthetic resin filler (B-3), fine particle synthetic resin filler (B- 5) 2.6 parts (solid content), 6.9 parts of photopolymerization initiator (D-1), and 2.7 parts of leveling agent (E-1) are mixed to a solids concentration of 50% using ethyl acetate. Thus, an active energy ray-curable resin composition was obtained.
  • Example 3 100 parts of bifunctional urethane (meth) acrylate compound (A1-3) obtained in Production Example 3 above, 65.9 parts of fine particle synthetic resin filler (B-1), fine particle synthetic resin filler (B- 5) 0.5 parts (solid content), 6.8 parts of photopolymerization initiator (D-1), and 2.7 parts of leveling agent (E-1) are mixed to a solids concentration of 50% using ethyl acetate. Thus, an active energy ray-curable resin composition was obtained.
  • Example 5 100 parts of urethane (meth) acrylate compound (A1-5) obtained in Production Example 5 above, 67.2 parts of fine particle synthetic resin filler (B-2), fine particle synthetic resin filler (B-5) 3.3 parts (solid content), 6.9 parts of photopolymerization initiator (D-1), and 2.2 parts of leveling agent (E-1) were adjusted to a solid content concentration of 50% using ethyl acetate.
  • the active energy ray-curable resin composition was obtained by blending.
  • Example 6 100 parts of urethane (meth) acrylate compound (A1-5) obtained in Production Example 5 above, 67.2 parts of fine particle synthetic resin filler (B-3), fine particle synthetic resin filler (B-5) 3.3 parts (solid content), 6.9 parts of photopolymerization initiator (D-1), and 2.2 parts of leveling agent (E-1) were adjusted to a solid content concentration of 50% using ethyl acetate.
  • the active energy ray-curable resin composition was obtained by blending.
  • Example 7 100 parts of urethane (meth) acrylate compound (A2-1) obtained in Production Example 6 above, 67.2 parts of fine synthetic resin filler (B-1), fine synthetic resin filler (B-5) 3.3 parts (solid content), 6.9 parts of photopolymerization initiator (D-1), and 2.2 parts of leveling agent (E-1) were adjusted to a solid content concentration of 50% using ethyl acetate.
  • the active energy ray-curable resin composition was obtained by blending.
  • Example 8 100 parts of urethane (meth) acrylate compound (A2-1) obtained in Production Example 6 above, 67.2 parts of fine synthetic resin filler (B-2), fine synthetic resin filler (B-5) 3.3 parts (solid content), 6.9 parts of photopolymerization initiator (D-1), and 2.2 parts of leveling agent (E-1) were adjusted to a solid content concentration of 50% using ethyl acetate.
  • the active energy ray-curable resin composition was obtained by blending.
  • Example 9 100 parts of urethane (meth) acrylate compound (A2-1) obtained in Production Example 6 above, 67.2 parts of fine particle synthetic resin filler (B-1), photopolymerization initiator (D-1) 6.
  • a leveling agent (E-1) were blended using ethyl acetate to a solid content concentration of 50% to obtain an active energy ray-curable resin composition.
  • Example 10 100 parts of urethane (meth) acrylate compound (A2-2) obtained in Production Example 7 above, 65.9 parts of fine particle synthetic resin filler (B-1), fine particle synthetic resin filler (B-5) 0.5 parts (solid content), 6.8 parts of photopolymerization initiator (D-1), and 2.7 parts of leveling agent (E-1) were adjusted to a solid content concentration of 50% using ethyl acetate.
  • the active energy ray-curable resin composition was obtained by blending.
  • Example 11 100 parts of urethane (meth) acrylate compound (A2-3) obtained in Production Example 8 above, 65.9 parts of fine synthetic resin filler (B-1), fine synthetic resin filler (B-5) 0.5 parts (solid content), 6.8 parts of photopolymerization initiator (D-1), and 2.7 parts of leveling agent (E-1) were adjusted to a solid content concentration of 50% using ethyl acetate.
  • the active energy ray-curable resin composition was obtained by blending.
  • Example 5 In Example 5, the fine synthetic resin fillers (B-2) and (B-5) and the leveling agent (E-1) were not blended, and the blending amount of the photopolymerization initiator (D-1) was 4 An active energy ray-curable resin composition was obtained in the same manner as in Example 5 except that the parts were changed to parts.
  • Example 7 the synthetic resin fillers (B-1) and (B-5) in fine particles and the leveling agent (E-1) were not blended, and the blending amount of the photopolymerization initiator (D-1) was 4
  • An active energy ray-curable resin composition was obtained in the same manner as in Example 7 except that the part was changed to part.
  • Example 3 Fine synthetic resin fillers (B-1) and (B-5) were changed to 6.2 parts of (B′-1), and the blending amount of the photopolymerization initiator (D-1) was changed to 4.3 parts and the amount of the leveling agent (E-1) was changed to 1.8 parts to obtain an active energy ray-curable resin composition in the same manner as in Example 3.
  • the active energy ray-curable resin compositions obtained in Examples 1 to 11 and Comparative Examples 1 to 3 are polycarbonate substrates (manufactured by Nippon Test Panel Co., Ltd.) so that the cured coating film has a thickness of 10 ⁇ m using an applicator. After drying at 90 ° C. for 3 minutes, using a high pressure mercury lamp lamp 80W and one lamp, UV irradiation of 2 passes at a conveyor speed of 3.4 m / min from a height of 18 cm (accumulated dose 800 mJ / cm 2 ) to obtain a cured coating film.
  • the soft film properties, substrate adhesion, and surface hardness of the cured coating film were evaluated as follows.
  • the active energy ray-curable resin compositions obtained in the above Examples and Comparative Examples were prepared by using an easy-adhesion PET (manufactured by Toyobo Co., Ltd .; trade name “Cosmo Sunshine A4300”) so that the cured coating film had a thickness of 10 ⁇ m with an applicator. After coating at a film thickness of 125 ⁇ m and drying at 90 ° C.
  • polyol compound (a3) which is one of the components for obtaining the urethane (meth) acrylate compound (A1)
  • a polyol compound (a3-1) having a weight average molecular weight of less than 500 and a weight average molecular weight of 500 to 20
  • An example containing 000 polyol compounds (a3-2) will be described below.
  • 2-hydroxyethyl acrylate ( a1) 6.0 g (0.052 mol) was charged and reacted at 60 ° C. for 3 hours. The reaction was terminated when it became 3% or less, and an ethyl acetate solution (A1-7) of urethane (meth) acrylate compound (weight average molecular weight (Mw); 14,000) (solid content concentration 70%, viscosity) (20 ° C.) 53,000 mPa ⁇ s) was obtained.
  • Mw weight average molecular weight
  • 14,000 solid content concentration 70%, viscosity
  • B-1 Polyurethane fine particles (average particle size 6.2 ⁇ m: glass transition temperature ⁇ 52 ° C.)
  • B-5 Polyethylene wax (particle size 5-10 ⁇ m)
  • (D-1) 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF Japan, “Irgacure 184”)
  • Example 12 27.0 parts of urethane (meth) acrylate compound (A1-6) obtained in Production Example 9 above, 12.7 parts of fine synthetic resin filler (B-1), fine synthetic resin filler (B- 5) 4.9 parts, 1.3 parts of photopolymerization initiator (D-1), 0.5 parts of leveling agent (E-1), 35.9 parts of organic solvent (F-1), organic solvent (F- 2) Using 17.7 parts, it mix
  • Example 13 27.0 parts of urethane (meth) acrylate compound (A1-7) obtained in Production Example 10 above, 12.7 parts of fine particle synthetic resin filler (B-1), fine particle synthetic resin filler (B- 5) 4.9 parts, 1.3 parts of photopolymerization initiator (D-1), 0.5 parts of leveling agent (E-1), 35.9 parts of organic solvent (F-1), organic solvent (F- 2) Using 17.7 parts, it mix
  • Example 14 27.0 parts of urethane (meth) acrylate compound (A1-8) obtained in Production Example 11 above, 12.7 parts of fine particle synthetic resin filler (B-1), fine particle synthetic resin filler (B- 5) 4.9 parts, 1.3 parts of photopolymerization initiator (D-1), 0.5 parts of leveling agent (E-1), 35.9 parts of organic solvent (F-1), organic solvent (F- 2) Using 17.7 parts, it mix
  • the active energy ray-curable resin compositions obtained in Examples 12 to 14 were applied to a polycarbonate substrate (manufactured by Nippon Test Panel Co., Ltd.) with an applicator so that the cured coating film had a thickness of 10 ⁇ m, and 90 ° C. After drying for 3 minutes at a high pressure mercury lamp lamp 80W, a single lamp is used to irradiate with 2 passes of ultraviolet light (accumulated dose of 800 mJ / cm 2 ) at a conveyor speed of 3.4 m / min from a height of 18 cm to cure. A coating film was obtained.
  • the active energy ray-curable resin compositions of Examples 12 to 14 in which the fine synthetic resin filler (B) is blended with the urethane (meth) acrylate compound (A1) have a soft feel. It can be seen that a cured coating film that is not only excellent in appearance but also excellent in appearance and excellent in adhesion, hardness, alkali resistance and ethanol resistance can be obtained.
  • thermosetting paints In addition, the formation of these cured coating films is clearly superior to conventional thermosetting paints in that it has low energy, high production rate, and solution stability as a coating agent.
  • an active energy ray-curable resin composition excellent in workability during coating and productivity during curing can be obtained and cured.
  • the coating layer obtained later has an effect of having a moist and soft touch feeling and is particularly useful as a coating agent in a non-optical field.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne une composition de résine durcissable par rayonnement d'énergie active, contenant (A) un composé d'uréthane-(méth)acrylate et (B) une charge de résine synthétique sous forme de fines particules, une composition d'agent de revêtement qui utilise la composition de résine durcissable par rayonnement d'énergie active et un stratifié. Selon l'invention, on décrit une composition de résine durcissable par rayonnement d'énergie active, qui forme une couche de revêtement qui présente un toucher humide et doux, tout en présentant une excellente aptitude à la mise en œuvre pendant un procédé de revêtement et une excellente productivité pendant un procédé de durcissement, une composition d'agent de revêtement qui utilise la composition de résine durcissable par rayonnement d'énergie active et un stratifié.
PCT/JP2013/081484 2012-11-22 2013-11-22 Composition de résine durcissable par rayonnement d'énergie active, composition d'agent de revêtement et stratifié WO2014081004A1 (fr)

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CN201380059384.8A CN104797613A (zh) 2012-11-22 2013-11-22 活性能量射线固化性树脂组合物、涂覆剂组合物及层叠体

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WO2015187899A1 (fr) * 2014-06-04 2015-12-10 Corning Incorporated Revêtement de fibre optique et composition
WO2016159294A1 (fr) * 2015-03-31 2016-10-06 日本合成化学工業株式会社 Composition de résine durcissable par rayons d'énergie active, composition de revêment et stratifié
JP2018501348A (ja) * 2014-12-04 2018-01-18 ペルストルプ アーベーＰｅｒｓｔｏｒｐ ＡＢ 電磁線硬化型被覆組成物
EP3740527A4 (fr) * 2018-01-15 2021-09-15 3M Innovative Properties Company Film résistant aux rayures et composition de revêtement de surface
JPWO2021201104A1 (fr) * 2020-03-31 2021-10-07
WO2021233728A1 (fr) 2020-05-19 2021-11-25 Byk-Chemie Gmbh Poudre de polymère thermodurcissable
EP3825099A4 (fr) * 2018-07-19 2022-06-15 GC Corporation Composition pour mise en forme tridimensionnelle et procédé de production d'article dentaire

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EP3192815B1 (fr) * 2014-09-11 2021-03-31 Sekisui Plastics Co., Ltd. Particules de résine à haute de la récupérabilité et utilisation de ceux-ci
JP6932960B2 (ja) * 2016-03-22 2021-09-08 東洋インキＳｃホールディングス株式会社 印刷用コート剤組成物及び印刷物
WO2020003780A1 (fr) * 2018-06-27 2020-01-02 Dic株式会社 Composition de résine d'uréthanne, agent de traitement de surface et article
JP7221383B2 (ja) * 2019-05-30 2023-02-13 中国塗料株式会社 紫外線硬化型ウレタンアクリレート樹脂、およびそれを含む紫外線硬化型樹脂組成物

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JPH02170867A (ja) * 1988-12-23 1990-07-02 Kansai Paint Co Ltd 活性エネルギー線硬化型組成物
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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015187899A1 (fr) * 2014-06-04 2015-12-10 Corning Incorporated Revêtement de fibre optique et composition
US10377915B2 (en) 2014-06-04 2019-08-13 Corning Incorporated Optical fiber coating and composition
US9708491B2 (en) 2014-06-04 2017-07-18 Corning Incorporated Optical fiber coating and composition
US10030164B2 (en) 2014-06-04 2018-07-24 Corning Incorporated Optical fiber coating and composition
JP2018501348A (ja) * 2014-12-04 2018-01-18 ペルストルプ アーベーＰｅｒｓｔｏｒｐ ＡＢ 電磁線硬化型被覆組成物
US10167359B2 (en) 2014-12-04 2019-01-01 Perstorp Ab Radiation curing coating composition
JPWO2016159294A1 (ja) * 2015-03-31 2018-01-25 日本合成化学工業株式会社 活性エネルギー線硬化性樹脂組成物、コーティング剤組成物、及び積層体
CN107428894A (zh) * 2015-03-31 2017-12-01 日本合成化学工业株式会社 活性能量射线固化性树脂组合物、涂布剂组合物、和层叠体
WO2016159294A1 (fr) * 2015-03-31 2016-10-06 日本合成化学工業株式会社 Composition de résine durcissable par rayons d'énergie active, composition de revêment et stratifié
CN107428894B (zh) * 2015-03-31 2020-12-04 三菱化学株式会社 活性能量射线固化性树脂组合物、涂布剂组合物、和层叠体
EP3740527A4 (fr) * 2018-01-15 2021-09-15 3M Innovative Properties Company Film résistant aux rayures et composition de revêtement de surface
US11904574B2 (en) 2018-01-15 2024-02-20 3M Innovative Properties Company Scratch resistant film and surface coating composition
EP3825099A4 (fr) * 2018-07-19 2022-06-15 GC Corporation Composition pour mise en forme tridimensionnelle et procédé de production d'article dentaire
JPWO2021201104A1 (fr) * 2020-03-31 2021-10-07
WO2021201104A1 (fr) * 2020-03-31 2021-10-07 東レ株式会社 Agent de revêtement pour films d'impression, stratifié, et procédé permettant de fabriquer un article imprimé
JP7416060B2 (ja) 2020-03-31 2024-01-17 東レ株式会社 印刷フィルム用コーティング剤、積層体、および印刷物の製造方法
WO2021233728A1 (fr) 2020-05-19 2021-11-25 Byk-Chemie Gmbh Poudre de polymère thermodurcissable

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