WO2018181972A1 - Composition de résine durcissable par rayonnement d'énergie active et agent de revêtement - Google Patents

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

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Publication number
WO2018181972A1
WO2018181972A1 PCT/JP2018/013806 JP2018013806W WO2018181972A1 WO 2018181972 A1 WO2018181972 A1 WO 2018181972A1 JP 2018013806 W JP2018013806 W JP 2018013806W WO 2018181972 A1 WO2018181972 A1 WO 2018181972A1
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meth
acrylate
mixture
pentaerythritol
acrylates
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PCT/JP2018/013806
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English (en)
Japanese (ja)
Inventor
祐太 石川
幸宗 神田
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日本合成化学工業株式会社
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Priority to CN201880014095.9A priority Critical patent/CN110382575B/zh
Priority to KR1020197025035A priority patent/KR102445218B1/ko
Publication of WO2018181972A1 publication Critical patent/WO2018181972A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
    • 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
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings

Definitions

  • the present invention relates to an active energy ray-curable resin composition containing a urethane (meth) acrylate-based composition and a coating agent, and more particularly, since curling shrinkage is small when a cured coating film is formed.
  • the present invention relates to an active energy ray-curable resin composition that can form a coating film that is difficult to resist and has excellent hardness and flexibility, and a coating agent using the same.
  • the active energy ray-curable resin composition is completely cured by irradiation with an active energy ray such as radiation or ultraviolet rays for a very short time, so that it can be used as a coating agent or adhesive on various substrates, or an anchor coating agent, etc.
  • an active energy ray such as radiation or ultraviolet rays
  • urethane (meth) acrylate compounds and polyfunctional monomers are used as the curing component.
  • the active energy ray-curable resin composition is used as a coating agent, particularly as a coating agent for a hard coat, there is a problem that the shrinkage of the coating film occurs and the cured coating film tends to curl. Difficult things are needed.
  • the coating agent for hard coat is also used as a protective film in bent parts of molded products, displays, etc., it is required to be flexible so that cracks do not easily occur even when a plastic film with a cured coating film is bent. Yes.
  • a curable resin composition in which inorganic fine particles are added to a curable resin for example, refer to Patent Document 1
  • a high molecular weight urethane as a curing component in order to suppress curing shrinkage.
  • a curable resin composition containing (meth) acrylate (see, for example, Patent Document 2), a hydroxyl group in a (meth) acrylic acid adduct of pentaerythritol having a hydroxyl value of 130 mgKOH / g or more,
  • a curable resin composition containing urethane (meth) acrylate obtained by reacting an isocyanate group of a polyvalent isocyanate compound for example, see Patent Document 3 has been proposed.
  • a resin composition containing dipentaerythritol hexaacrylate and tripentaerythritol octaacrylate is used to obtain a triacetyl cellulose having a thickness of 80 ⁇ m.
  • a technique is known in which a film having a pencil hardness of about 5H can be obtained by applying a film having a thickness of 12 ⁇ m on a film and curing the film (see, for example, Patent Document 4).
  • Patent Document 1 has a problem that the organic solvent that can be used is limited in consideration of the compatibility between the inorganic fine particles and the curable resin, and the possibility that the surface abnormality of the coating film increases. Furthermore, since inorganic fine particles are generally expensive, resins and paints containing them are also expensive, and practically, the use of the curable resin is limited to special applications.
  • Patent Document 3 can provide a cured coating film having a small curing shrinkage and curling suppressed, but is insufficient in terms of hardness.
  • urethane that can form a coating film that is difficult to curl due to small curing shrinkage and that has excellent hardness and flexibility.
  • An active energy ray-curable resin composition containing a (meth) acrylate composition and a coating agent using the same are provided.
  • the reaction product of at least one of pentaerythritol and dipentaerythritol and (meth) acrylic acid exhibits a hydroxyl value in a specific range
  • a urethane (meth) acrylate-based composition obtained by reacting a hydroxyl group of (meth) acrylate in the reaction product with a polyvalent isocyanate By using a urethane (meth) acrylate-based composition obtained by reacting a hydroxyl group of (meth) acrylate in the reaction product with a polyvalent isocyanate, curling shrinkage is small and hardness and flexibility are low. It was also found that an excellent cured coating film can be obtained.
  • the first gist of the present invention is that (meth) acrylate (a1) in a mixture (A) of the following (meth) acrylates (a1) to (a4) which is a reaction product of pentaerythritol and (meth) acrylic acid. ) To (a3) and a urethane (meth) acrylate composition [I] obtained by reacting polyisocyanate (CA), and the mixture (A) has a hydroxyl value of 200 mgKOH / g or more.
  • the present invention relates to an energy ray curable resin composition.
  • the second gist of the present invention is the urethane (meth) acrylate-based composition [I] and the following (meth) acrylate (b1) to (reaction product of dipentaerythritol and (meth) acrylic acid).
  • a urethane (meth) acrylate-based composition [II] obtained by reacting (meth) acrylates (b1) to (b5) in the mixture (B) of (b6) with the polyvalent isocyanate (CB);
  • the present invention relates to an active energy ray-curable resin composition having a hydroxyl value of 40 mgKOH / g or more in the mixture (B).
  • B1 Dipentaerythritol mono (meth) acrylate (b2) Dipentaerythritol di (meth) acrylate (b3) Dipentaerythritol tri (meth) acrylate (b4) Dipentaerythritol tetra (meth) acrylate (b5) Dipentaerythritol Penta (meth) acrylate (b6) Dipentaerythritol hexa (meth) acrylate
  • the third gist of the present invention is the following [ ⁇ ] (meth) acrylates (a1) to (a3), the following [ ⁇ ] (meth) acrylates (b1) to (b5), and
  • the present invention relates to an active energy ray-curable resin composition comprising a urethane (meth) acrylate composition [III] reacted with polyisocyanate (CC).
  • the mixture (A) of the following (meth) acrylates (a1) to (a4), which is a reaction product of [ ⁇ ] pentaerythritol and (meth) acrylic acid, has a hydroxyl value of 200 mgKOH / g or more, and the mixture (A) (Meth) acrylates (a1) to (a3).
  • the present invention also provides a coating agent comprising the active energy ray-curable resin composition.
  • the active energy ray-curable resin composition according to the first aspect of the present invention is less likely to curl due to small curing shrinkage, and can form a cured coating film having excellent hardness and flexibility, and further, before curing. Even a coating film can form a tack-free coating surface and is particularly useful for various applications such as a hard coating agent.
  • the active energy ray-curable resin composition according to the second aspect of the present invention has a small cure shrinkage, and is difficult to curl and can form a cured coating film having excellent hardness and flexibility.
  • it is useful for various applications such as a coating agent for hard coating.
  • the active energy ray-curable resin composition according to the third aspect of the present invention forms a cured coating film that is difficult to curl due to small curing shrinkage and that is excellent in hardness, flexibility, and scratch resistance.
  • it is useful for various applications such as a coating agent for hard coating.
  • the weight average molecular weight of the urethane (meth) acrylate composition [I] is 1,000 to 20,000, the active energy ray-curable resin composition is easily handled.
  • the active energy ray-curable resin composition is excellent in handleability.
  • the weight average molecular weight of the urethane (meth) acrylate composition [III] is 1,000 to 20,000, the active energy ray-curable resin composition is more easily handled.
  • (meth) acryl means acryl or methacryl
  • (meth) acryloyl means acryloyl or methacryloyl
  • (meth) acrylate means acrylate or methacrylate.
  • the active energy ray-curable resin composition of the present invention includes the following urethane (meth) acrylate-based composition [I], urethane (meth) acrylate-based compositions [I] and [II], and urethane (meth) acrylate-based It is characterized in that it contains any one urethane (meth) acrylate composition selected from the group consisting of the composition [III], and there are three embodiments.
  • the urethane (meth) acrylate-based composition [I] is a (meth) acrylate in a mixture (A) of the following (meth) acrylates (a1) to (a4), which is a reaction product of pentaerythritol and (meth) acrylic acid. ) Acrylate (a1) to (a3) and polyvalent isocyanate (CA) are reacted, and the hydroxyl value of the mixture (A) is 200 mgKOH / g or more.
  • the urethane (meth) acrylate-based composition [II] is a mixture of the following (meth) acrylates (b1) to (b6) (B), which is a reaction product of dipentaerythritol and (meth) acrylic acid.
  • the (meth) acrylates (b1) to (b5) are reacted with the polyvalent isocyanate (CB), and the hydroxyl value of the mixture (B) is 40 mgKOH / g or more.
  • B1 Dipentaerythritol mono (meth) acrylate (b2) Dipentaerythritol di (meth) acrylate (b3) Dipentaerythritol tri (meth) acrylate (b4) Dipentaerythritol tetra (meth) acrylate (b5) Dipentaerythritol Penta (meth) acrylate (b6) Dipentaerythritol hexa (meth) acrylate
  • the urethane (meth) acrylate-based composition [III] refers to (meth) acrylates (a1) to (a3) which are the following [ ⁇ ], and (meth) acrylates (b1) to (b1) which are the following [ ⁇ ]: b5) and a polyisocyanate (CC) are reacted.
  • the urethane (meth) acrylate composition [I] will be described.
  • the hydroxyl value of the mixture (A) of the (meth) acrylates (a1) to (a4) obtained by reacting the pentaerythritol with (meth) acrylic acid is 200 mgKOH / g or more.
  • Necessary preferably 210 to 380 mg KOH / g, particularly preferably 230 to 320 mg KOH / g.
  • the weight average molecular weight of the urethane (meth) acrylate-based composition [III] decreases, so that the curing shrinkage at the time of curing increases, so that it tends to be easily curled.
  • the flexibility tends to decrease.
  • the viscosity increases with increasing molecular weight, which tends to be difficult to handle.
  • the hydroxyl value in the present invention can be determined by a method according to JIS K 0070 1992.
  • the content of pentaerythritol di (meth) acrylate (a2) in the mixture (A) of the (meth) acrylates (a1) to (a4) is 10 to 50% by weight. And is preferably in terms of both flexibility and flexibility, particularly preferably 15 to 45% by weight, more preferably 20 to 40% by weight. If the content is too small, the flexibility tends to decrease, and if it is too large, the hardness tends to decrease or the viscosity increases.
  • the content ratio of pentaerythritol di (meth) acrylate (a2) with respect to the total of the (meth) acrylates (a1) to (a3) is preferably 15 to 55% by weight in terms of both hardness and flexibility,
  • the amount is particularly preferably 20 to 50% by weight, more preferably 25 to 45% by weight. If the content is too small, the flexibility tends to decrease, and if it is too large, the hardness tends to decrease or the viscosity increases.
  • pentaerythritol and (meth) acrylic acid are reacted to prepare an (meth) acrylic acid adduct of pentaerythritol, but the reaction of pentaerythritol and (meth) acrylic acid is carried out by a known general method. be able to.
  • pentaerythritol mono (meth) acrylate (a1) in which one (meth) acrylic acid is added to pentaerythritol
  • a mixture (A) containing erythritol tri (meth) acrylate (a3) and four-added pentaerythritol tetra (meth) acrylate (a4) is obtained, and a mixture (A) having the above hydroxyl value as a whole is obtained. be able to.
  • the mixture (A) may contain a side reaction product such as a Michael adduct of acrylic acid.
  • the hydroxyl value can be adjusted, for example, by adjusting the content ratio of (meth) acrylates (a1) to (a4).
  • the polyvalent isocyanate (CA) reacts with the (meth) acrylates (a1) to (a3).
  • the (meth) acrylates (a1) to (a3) Specifically, for example, tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate.
  • Aromatic polyisocyanates such as modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylene diisocyanate, naphthalene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate Hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone dii Cycloaliphatic polyisocyanates such as cyanate and norbornene diisocyanate; or trimer compounds or multimeric compounds of these polyisocyanates, allophanate polyisocyanates, burette polyisocyanates, water-dispersed polyisocyanates (for example “ Aquanate 105 ",” Aquanate 120 ",” Aquanate 210 ",
  • alicyclic polyisocyanates and aromatic polyisocyanates are preferable from the viewpoint of strength, and isophorone diisocyanate, hydrogenated xylylene diisocyanate, xylylene diisocyanate, and tolylene diisocyanate are particularly preferable.
  • the urethane (meth) acrylate composition [I] includes the hydroxyl groups of (meth) acrylates (a1) to (a3) in the mixture (A) of the above (meth) acrylates (a1) to (a4) and It can be obtained by reacting with the isocyanate group of the polyvalent isocyanate (CA).
  • the urethane (meth) acrylate composition [I] is obtained by reacting (meth) acrylate (a1) and polyvalent isocyanate (CA), (meth) acrylate (a2) and polyvalent isocyanate (CA).
  • the (meth) acrylate (a3) and the polyvalent isocyanate (CA) are reacted.
  • the (meth) acrylates (a1) to (a3) are not contained in the system.
  • the reaction product and (meth) acrylate (a4) which does not participate in the reaction are also contained.
  • the reaction molar ratio of the charge of the polyvalent isocyanate (CA) and the mixture (A) of (meth) acrylates (a1) to (a4) is, when the polyisocyanate (CA) has two isocyanate groups,
  • the polyvalent isocyanate (CA) :( meth) acrylate mixture (A) is preferably from 1: 1 to 1: 5, particularly preferably from 1: 1 to 1: 3, more preferably from 1: 1 to 1: 2. It is.
  • the ratio of the mixture (A) is too large, the amount of low molecular weight monomers increases, and the shrinkage of curing increases, so that the curl tends to increase. If the ratio of the mixture (A) is too small, unreacted polyvalent isocyanate. (CA) remains, and the stability and safety of the cured coating film tend to decrease.
  • reaction between the (meth) acrylates (a1) to (a3) and the polyvalent isocyanate (CA) in the (meth) acrylate mixture (A) is usually performed by reacting the above mixture (A) and the polyvalent isocyanate (CA). What is necessary is just to make it react to the vessel collectively or separately.
  • a catalyst for the purpose of accelerating the reaction.
  • a catalyst include dibutyltin dilaurate, dibutyltin diacetate, trimethyltin hydroxide, tetra-n-butyltin, bisacetylacetonate.
  • Organometallic compounds such as zinc, zirconium tris (acetylacetonate) ethylacetoacetate, zirconium tetraacetylacetonate; tin octylate, tin octenoate, zinc hexanoate, zinc octenoate, zinc stearate, zirconium 2-ethylhexanoate
  • Metal salts such as cobalt naphthenate, stannous chloride, stannic chloride and potassium acetate; triethylamine, triethylenediamine, benzyldiethylamine, 1,4-diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [ 5, , 0]
  • Undecene, amine catalysts such as N, N, N ′, N′-tetramethyl-1,3-butanediamine, N-methylmorpholine, N-ethylmorpholine; bis
  • a polymerization inhibitor As the polymerization inhibitor, known general ones used as polymerization inhibitors can be used. For example, p-benzoquinone, naphthoquinone, tolquinone, 2,5-diphenyl-p-benzoquinone, hydroquinone, 2, Quinones such as 5-di-t-butylhydroquinone, methylhydroquinone and mono-t-butylhydroquinone, aromatics such as 4-methoxyphenol and 2,6-di-t-butylcresol, pt-butylcatechol Etc. Of these, aromatics are preferable, and 4-methoxyphenol and 2,6-di-t-butylcresol are particularly preferable. These may be used alone or in combination of two or more.
  • an organic solvent having no functional group that reacts with an isocyanate group for example, esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and aromatics such as toluene and xylene.
  • esters such as ethyl acetate and butyl acetate
  • ketones such as methyl ethyl ketone and methyl isobutyl ketone
  • aromatics such as toluene and xylene.
  • An organic solvent such as a family can be used. These may be used alone or in combination of two or more.
  • the reaction temperature is usually 30 to 90 ° C., preferably 40 to 80 ° C.
  • the reaction time is usually 4 to 72 hours, preferably 8 to 48 hours.
  • the urethane (meth) acrylate composition [I] preferably has a weight average molecular weight of 1,000 to 20,000, particularly preferably 2,000 to 18,000, and more preferably 3,000 to 16 , 000. If the weight average molecular weight is too small, the cured coating film tends to be brittle, and if it is too large, the viscosity tends to be high and difficult to handle.
  • the said weight average molecular weight is a weight average molecular weight by standard polystyrene molecular weight conversion, a column: ACQUITY APC XT 450, ACQUITY APC XT 200, on a high-speed liquid chromatograph (Waters, "ACQUITY APC system”). 1 and ACQUITY APC XT 45, 2 in total, and 4 in total.
  • the urethane (meth) acrylate content in the urethane (meth) acrylate composition [I] is preferably 50% by weight or more, particularly preferably 60% by weight or more, more preferably 70% by weight or more, and particularly preferably. 80% by weight or more.
  • the upper limit is usually 95% by weight.
  • the hydroxyl value of the mixture (B) of the (meth) acrylates (b1) to (b6) obtained by reacting the dipentaerythritol with (meth) acrylic acid is 40 mgKOH / g or more. Is preferably 43 to 130 mgKOH / g, particularly preferably 45 to 125 mgKOH / g, and still more preferably 70 to 120 mgKOH / g.
  • the hydroxyl value of the mixture (B) is too small, the content of dipentaerythritol hexa (meth) acrylate (b6) that has a low molecular weight and a large number of ethylenically unsaturated groups and does not react with isocyanate increases. Since cure shrinkage becomes large, it tends to curl easily, and further, flexibility tends to decrease. In general, when the hydroxyl value is too large, the viscosity increases with increasing molecular weight, which tends to be difficult to handle.
  • the hardness and the content ratio of dipentaerythritol penta (meth) acrylate (b5) in the mixture (B) of the (meth) acrylates (b1) to (b6) are 15 to 60% by weight. It is preferable from the viewpoint of coexistence of flexibility, particularly preferably 20 to 55% by weight, and further preferably 25 to 55% by weight. If the content is too small, the flexibility tends to decrease, and if it is too large, the hardness tends to decrease or the viscosity increases.
  • the content ratio of dipentaerythritol penta (meth) acrylate (b5) to the total of the above (meth) acrylates (b1) to (b5) is preferably 45 to 90% by weight, particularly in terms of both hardness and flexibility. Preferably it is 50 to 90% by weight, more preferably 55 to 90% by weight. If the content is too small, the flexibility tends to decrease, and if it is too large, the hardness tends to decrease or the viscosity increases.
  • the content ratio of dipentaerythritol tetra (meth) acrylate (b4) in the mixture (B) of the (meth) acrylates (b1) to (b6) is preferably 1 to 35% by weight from the viewpoint of flexibility, Particularly preferred is 2 to 30% by weight, and more preferred is 3 to 25% by weight. If the content is too small, the flexibility tends to decrease, and if it is too large, the hardness tends to decrease or the viscosity increases.
  • the content ratio of dipentaerythritol tetra (meth) acrylate (b4) to the total of the (meth) acrylates (b1) to (b5) is preferably 2 to 40% by weight, particularly preferably 3 to It is 35% by weight, more preferably 4 to 30% by weight. If the content is too small, the flexibility tends to decrease, and if it is too large, the hardness tends to decrease or the viscosity increases.
  • dipentaerythritol is reacted with (meth) acrylic acid to prepare a (meth) acrylic acid adduct of dipentaerythritol, but the reaction between dipentaerythritol and (meth) acrylic acid is generally known. It can be done by the method.
  • the mixture (B) may contain a side reaction product such as a Michael adduct of acrylic acid.
  • the hydroxyl value can be adjusted, for example, by adjusting the content ratio of (meth) acrylates (b1) to (b6).
  • the polyvalent isocyanate (CB) reacts with the (meth) acrylates (b1) to (b5), specifically, the same polyvalent isocyanate (CA) as described above. Can be illustrated.
  • the polyvalent isocyanate (CB) may be the same as or different from the polyvalent isocyanate (CA).
  • the polyisocyanate (CB) may be a reaction product of the polyisocyanate and a polyol.
  • polyols include low molecular weight polyols and high molecular weight polyols, specifically polyether polyols, polyester polyols, polycarbonate polyols, polybutadiene polyols, ethylene / isoprene / butadiene, etc.
  • CB polyisocyanates
  • alicyclic polyisocyanates and aromatic polyisocyanates are preferable in terms of weather resistance and strength, and particularly preferable are isophorone diisocyanate, hydrogenated xylylene diisocyanate, and xylylene. Range isocyanate and tolylene diisocyanate.
  • the urethane (meth) acrylate composition [II] comprises the hydroxyl groups of (meth) acrylates (b1) to (b5) in the mixture (B) of the above (meth) acrylates (b1) to (b6) and It can be obtained by reacting with the isocyanate group of the polyvalent isocyanate (CB).
  • the urethane (meth) acrylate-based composition [II] is obtained by reacting (meth) acrylate (b1) and polyvalent isocyanate (CB), (meth) acrylate (b2) and polyvalent isocyanate (CB).
  • the reaction molar ratio of the charge of the polyvalent isocyanate (CB) and the mixture (B) of (meth) acrylates (b1) to (b6) is, for example, when the polyisocyanate (CB) has two isocyanate groups.
  • the polyisocyanate (CB) :( meth) acrylate mixture (B) is preferably 1: 1 to 1: 5, particularly preferably 1: 1 to 1: 4, and more preferably 1: 1 to 1. : 3.
  • reaction between (meth) acrylates (b1) to (b5) and the polyvalent isocyanate (CB) in the (meth) acrylate mixture (B) is usually performed by reacting the above mixture (B) and the polyvalent isocyanate (CB). What is necessary is just to make it react to the vessel collectively or separately.
  • a catalyst for the purpose of accelerating the reaction, and examples of the catalyst include those described in the urethane (meth) acrylate composition [I].
  • the preparation of the urethane (meth) acrylate composition [II] can be carried out according to the preparation of the urethane (meth) acrylate composition [I].
  • the urethane (meth) acrylate composition [II] preferably has a weight average molecular weight of 1,000 to 20,000, more preferably 1,500 to 18,000, particularly preferably 2,000 to 16. , 000. If the weight average molecular weight is too small, the cured coating film tends to be brittle, and if it is too large, the viscosity tends to be high and difficult to handle. In addition, the measuring method of said weight average molecular weight is the same as the said measuring method.
  • the viscosity of the urethane (meth) acrylate composition [II] at 60 ° C. is preferably 1,000 to 300,000 mPa ⁇ s, particularly preferably 1,500 to 200,000 mPa ⁇ s, and still more preferably. 2,000 to 100,000 mPa ⁇ s.
  • the measuring method of the viscosity in 60 degreeC uses an E-type viscosity meter.
  • the urethane (meth) acrylate content in the urethane (meth) acrylate composition [II] is preferably 35% by weight or more, particularly preferably 40% by weight or more, more preferably 45% by weight or more, and particularly preferably. It is 50% by weight or more, particularly preferably 60% by weight or more.
  • the upper limit is usually 95% by weight.
  • the mixture (A) is a mixture of the (meth) acrylates (a1) to (a4) obtained by reacting the pentaerythritol and (meth) acrylic acid, and has a hydroxyl value of 200 mgKOH / g or more. Preferably from 210 to 380 mg KOH / g, particularly preferably from 230 to 320 mg KOH / g.
  • Examples of the mixture (A) are the same as those described in the urethane (meth) acrylate composition [I].
  • the (meth) acrylates (a1) to (a3) having a hydroxyl group react with the later-described polyvalent isocyanate (CC).
  • the mixture (B) is a mixture of the above (meth) acrylates (b1) to (b6) obtained by reacting the dipentaerythritol and (meth) acrylic acid, and has a hydroxyl value of 40 mgKOH / g or more. It is necessary that it is preferably 43 to 130 mgKOH / g, particularly preferably 45 to 125 mgKOH / g, and further preferably 70 to 120 mgKOH / g.
  • Examples of the mixture (B) are the same as those described in the urethane (meth) acrylate composition [II].
  • the (meth) acrylates (b1) to (b5) having a hydroxyl group react with the following polyvalent isocyanate (CC).
  • CC Polyvalent isocyanate
  • the polyvalent isocyanate (CC) which is a constituent material of the urethane (meth) acrylate composition [III] will be described.
  • the polyvalent isocyanate (CC) reacts with a hydroxyl group-containing (meth) acrylate, that is, the (meth) acrylates (a1) to (a3) and the (meth) acrylates (b1) to (b5).
  • polyvalent isocyanate (CA) described in the urethane (meth) acrylate-based composition [I] and the polyvalent isocyanate described in the urethane (meth) acrylate-based composition [II] The same thing as (CB) can be illustrated.
  • the polyvalent isocyanate (CC) may be the same as or different from the polyvalent isocyanate (CA) or polyvalent isocyanate (CB).
  • the polyvalent isocyanate (CC), the polyvalent isocyanate (CA), and the polyvalent isocyanate (CB) may be collectively referred to as “polyvalent isocyanate (C)”.
  • the hydroxyl groups of (meth) acrylates (a1) to (a3) in the mixture (A) of the (meth) acrylates (a1) to (a4) and the (meth) acrylates (b1) to (b6) ) By reacting the hydroxyl groups of (meth) acrylates (b1) to (b5) in the mixture (B) with the isocyanate groups of the polyvalent isocyanate (CC), to obtain a urethane (meth) acrylate composition [III] Can be obtained.
  • the urethane (meth) acrylate composition [III] is a reaction of (meth) acrylate (a1) and polyvalent isocyanate (CC), (meth) acrylate (a2) and polyvalent isocyanate (CC).
  • the (meth) acrylate mixture (A) :( meth) acrylate mixture (B) is preferably 90:10 to 10:90 by weight, particularly preferably 70:30 to 15:85, Preferably it is 50:50 to 20:80.
  • the ratio of the mixture (B) to the mixture (A) is too large, the amount of low molecular weight monomers increases, and curling tends to increase due to an increase in curing shrinkage. If the ratio of the mixture (B) is too small, hardness and There is a tendency for the scratch resistance to decrease.
  • reaction may be performed by charging the above mixture (A), mixture (B), and polyvalent isocyanate (CC) into a reactor all at once or separately.
  • a catalyst for the purpose of accelerating the reaction, and examples of the catalyst include those described in the urethane (meth) acrylate composition [I].
  • the preparation of the urethane (meth) acrylate composition [III] can be carried out according to the preparation of the urethane (meth) acrylate composition [I].
  • urethane obtained by reacting the above [ ⁇ ] (meth) acrylates (a1) to (a3), the above [ ⁇ ] (meth) acrylates (b1) to (b5), and the polyvalent isocyanate (CC).
  • a (meth) acrylate composition [III] is obtained.
  • a polyol is also contained and reacted with a polyvalent isocyanate (CC) to produce ( ⁇ ) (meth) acrylates (a1) to (a3), [ ⁇ ] (meth) acrylate (b1). It is also possible to obtain a urethane (meth) acrylate composition [III] composed of (b5), a polyvalent isocyanate (CC) and a polyol.
  • CC polyvalent isocyanate
  • polyol examples include low molecular weight polyols and high molecular weight polyols, specifically, polyols obtained by reacting polyether polyols, polyester polyols, polycarbonate polyols, ethylene / isoprene / butadiene, and the like. Or the hydrogenated thing, polyolefin polyols other than the above, polyols, such as (meth) acrylic-type polyol, etc. are mentioned.
  • the urethane (meth) acrylate composition [III] preferably has a weight average molecular weight of 1,000 to 20,000, more preferably 2,000 to 15,000, particularly preferably 3,000 to 12. 1,000, particularly preferably 4,000 to 10,000. If the weight average molecular weight is too small, the cured coating film tends to be brittle, and if it is too large, the viscosity tends to be high and difficult to handle.
  • the said weight average molecular weight is a weight average molecular weight by standard polystyrene molecular weight conversion, a column: ACQUITY APC XT 450, ACQUITY APC XT 200, on a high-speed liquid chromatograph (Waters, "ACQUITY APC system”). 1 and ACQUITY APC XT 45, 2 in total, and 4 in total.
  • the urethane (meth) acrylate content in the urethane (meth) acrylate composition [III] is preferably 50% by weight or more, particularly preferably 60% by weight or more, more preferably 70% by weight or more, and particularly preferably. 80% by weight or more.
  • the upper limit is usually 95% by weight.
  • the active energy ray-curable resin composition of the present invention includes a first aspect (invention according to the first aspect) containing the urethane (meth) acrylate composition [I] and the urethane (meth) acrylate system.
  • 2nd aspect invention which concerns on 2nd summary
  • composition [I] and urethane (meth) acrylate type composition [II] containing composition [I] and urethane (meth) acrylate type composition [II]
  • the said urethane (meth) acrylate type composition [III] are contained. It has a 3rd aspect (invention based on a 3rd summary).
  • the active energy ray-curable resin composition according to the second aspect includes the urethane (meth) acrylate composition [I] and the urethane (meth) acrylate composition [II] as described above.
  • the content ratio ([I] / [II]) of the urethane (meth) acrylate composition [I] and the urethane (meth) acrylate composition [II] is 90/10 to 10/90 by weight ratio. It is preferably, particularly preferably 87/13 to 20/80, more preferably 85/15 to 30/70, particularly preferably 80/20 to 55/45, and even more preferably 80/20 to 65/35. It is. If the content is too small, the flexibility tends to decrease, and if it is too large, the hardness tends to be insufficient.
  • the active energy ray-curable resin composition of the present invention of the first to third aspects preferably further contains a photopolymerization initiator (D).
  • a photopolymerization initiator D
  • other urethane (meth) acrylates, ethylenically unsaturated monomers other than urethane (meth) acrylate, acrylic resins, surface conditioners, leveling agents, polymerization inhibitors, etc. are added within a range not impairing the effects of the present invention.
  • fillers dyes, pigments, oils, plasticizers, waxes, desiccants, dispersants, wetting agents, gelling agents, stabilizers, antifoaming agents, surfactants, leveling agents, thixotropic properties
  • Additives, antioxidants, flame retardants, antistatic agents, fillers, reinforcing agents, matting agents, crosslinking agents, silica, water-dispersed or solvent-dispersed silica, zirconium compounds, preservatives, etc. is there.
  • 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-hydroxycyclohexyl phenyl ketone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy -1- ⁇ 4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl ⁇ -2-methyl-propane, 2-methyl-2-morpholino (4-thiomethylphenyl) propane-1 -One, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 2-hydroxy- Acetophenones such as methyl-1- [4- (1-methylvinyl) phenyl] propanone
  • benzyl dimethyl ketal 1-hydroxycyclohexyl phenyl ketone, benzoyl isopropyl ether, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 2-hydroxy-2-methyl-1- It is preferable to use phenylpropan-1-one.
  • auxiliaries include triethanolamine, triisopropanolamine, 4,4′-dimethylaminobenzophenone (Michler ketone), 4,4′-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, 4-dimethylamino.
  • the content of the photopolymerization initiator (D) is preferably 0.1 to 20 parts by weight, particularly preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the curing component contained in the resin composition. Part by weight, more preferably 1 to 10 parts by weight. If the content of the photopolymerization initiator (D) is too small, curing tends to be poor and film formation tends to be difficult, and if too large, yellowing of the cured coating film tends to occur, and coloring problems tend to occur.
  • ethylenically unsaturated monomers other than urethane (meth) acrylates include monofunctional monomers, bifunctional monomers, and trifunctional or higher polyfunctional monomers. These may be used alone or in combination of two or more.
  • Examples of such monofunctional monomers include styrene monomers such as styrene, vinyl toluene, chlorostyrene, ⁇ -methylstyrene, methyl (meth) acrylate, ethyl (meth) acrylate, acrylonitrile, 2-methoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2-hydroxy -3-phenoxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, glycidyl (meth) acrylate, lauryl (meth) acrylate Lilate, cyclohexyl (meth)
  • bifunctional monomers examples include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and di Propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide modified bisphenol A type di (meth) acrylate, propylene oxide modified bisphenol A Type di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, ethoxylated cyclohexanedimethanol di ( Acrylate), dimethylol dicyclopentane di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, 1,6-
  • tri- or higher functional monomer examples include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( (Meth) acrylate, tri (meth) acryloyloxyethoxytrimethylolpropane, glycerin polyglycidyl ether poly (meth) acrylate, isocyanuric acid ethylene oxide modified triacrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol hexa (Meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate, cap Lactone modified pentaerythritol
  • a Michael adduct of acrylic acid or 2-acryloyloxyethyl dicarboxylic acid monoester can be used in combination.
  • examples of the Michael adduct of acrylic acid include (meth) acrylic acid dimer, (meth) acrylic acid trimer, ) Acrylic acid tetramer and the like.
  • the above-mentioned 2-acryloyloxyethyl dicarboxylic acid monoester is a carboxylic acid having a specific substituent, such as 2-acryloyloxyethyl succinic acid monoester, 2-methacryloyloxyethyl succinic acid monoester, 2-acryloyloxy Examples include ethyl phthalic acid monoester, 2-methacryloyloxyethyl phthalic acid monoester, 2-acryloyloxyethyl hexahydrophthalic acid monoester, 2-methacryloyloxyethyl hexahydrophthalic acid monoester, and the like. Furthermore, other oligoester acrylates can be mentioned.
  • the hardening components contained in an active energy ray-curable resin composition is preferably 60% by weight or less, particularly preferably 55% by weight or less, and still more preferably 50% by weight or less.
  • the lower limit is usually 5% by weight.
  • the content of the ethylenically unsaturated monomer other than urethane (meth) acrylate is 50% in all the curing components contained in the active energy ray-curable resin composition.
  • the content is preferably not more than wt%, particularly preferably not more than 40 wt%, further preferably not more than 30 wt%, particularly preferably not more than 20 wt%.
  • the lower limit is usually 5% by weight.
  • Examples of the surface conditioner include cellulose resin and alkyd resin.
  • cellulose resin has an action of improving the surface smoothness of the coating film
  • alkyd resin has an action of imparting a film-forming property at the time of coating.
  • leveling agent a known general leveling agent can be used as long as it has an effect of imparting wettability to the base material of the coating liquid and a function of reducing the surface tension.
  • An alkyl-modified resin or the like can be used. These may be used alone or in combination of two or more.
  • the same ones used during the reaction can be used.
  • These may be used alone or in combination of two or more.
  • the active energy ray-curable resin composition of the present invention preferably uses an organic solvent for dilution, if necessary, in order to make the viscosity at the time of coating appropriate.
  • organic solvents 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, toluene, xylene And the like, 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.
  • glycol ethers such as propylene glycol monomethyl ether and ketones such as methyl ethyl ketone and alcohols such as methanol, or ketones such as methyl ethyl ketone and alcohols such as methanol It is preferable from the viewpoint of the coating film appearance that a combination and two or more kinds selected from alcohols such as methanol are used in combination.
  • the active energy ray-curable resin composition of the present invention is effectively used as a curable composition for forming a coating film, such as a top coat agent and an anchor coat agent for various substrates. Then, after applying the active energy ray-curable resin composition to the base material (when the resin composition diluted with an organic solvent is applied, after further drying), the active energy ray is irradiated. Cured.
  • Examples of the base material to which the active energy ray-curable resin composition of the present invention is applied include, for example, polyolefin resins, polyester resins, polycarbonate resins, acrylonitrile butadiene styrene copolymers (ABS), and polystyrene resins.
  • Plastic substrates such as resins and their molded products (films, sheets, cups, etc.), optical films such as polyethylene terephthalate films, triacetyl cellulose films, cycloolefin films, composite substrates thereof, glass fibers, Composite base materials of the above materials mixed with inorganic materials, metals (aluminum, copper, iron, SUS, zinc, magnesium, alloys thereof, etc.) and glass, or base materials provided with a primer layer on these base materials, etc. Is mentioned.
  • Examples of the coating method of the active energy ray-curable resin composition of the present invention include wet coating methods such as spray, shower, gravure, dipping, roll, spin, and screen printing. What is necessary is just to apply to a base material.
  • the active energy ray-curable resin composition of the present invention may be applied as it is, or may be applied after diluting with an organic solvent.
  • the organic solvent is used so that the solid content is usually 3 to 70% by weight, preferably 5 to 60% by weight.
  • the drying conditions for the dilution with the organic solvent include a temperature of usually 40 to 120 ° C., preferably 50 to 100 ° C., and a drying time of usually 1 to 20 minutes, preferably 2 to 10 minutes. That's fine.
  • the viscosity of the resin composition at 20 ° C. is preferably 5 to 50,000 mPa ⁇ s, particularly preferably 10 to 10,000 mPa ⁇ s. s, more preferably 50 to 5,000 mPa ⁇ s.
  • the method for measuring the viscosity at 20 ° C. is based on a B-type viscometer. However, if the B-type viscometer at 20 ° C. cannot be measured due to high viscosity without solvent dilution, the measurement is performed using an E-type viscometer at 60 ° C.
  • Examples of the active energy ray used when the active energy ray-curable resin composition coated on the substrate is cured include, for example, deep ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, X-rays, ⁇ rays, etc.
  • ultraviolet irradiation is advantageous from the viewpoint of curing speed, availability of an irradiation device, price, and the like.
  • it can harden
  • ultraviolet irradiation When curing by ultraviolet irradiation, using a high-pressure mercury lamp, ultra-high pressure mercury lamp, carbon arc lamp, metal halide lamp, xenon lamp, chemical lamp, electrodeless discharge lamp, LED lamp, etc.
  • a high-pressure mercury lamp ultra-high pressure mercury lamp, carbon arc lamp, metal halide lamp, xenon lamp, chemical lamp, electrodeless discharge lamp, LED lamp, etc.
  • ultraviolet rays 30 to 3,000 mJ / cm 2 , preferably 100 to 1,500 mJ / cm 2 may be irradiated. After the ultraviolet irradiation, heating can be performed as necessary to complete the curing.
  • the coating film thickness (film thickness after curing) is usually 1 to 1,000 ⁇ m in view of light transmission so that the photopolymerization initiator (D) can react uniformly as an active energy ray-curable coating film.
  • the thickness is preferably 2 to 500 ⁇ m, particularly preferably 3 to 200 ⁇ m.
  • the active energy ray-curable resin composition of the present invention is preferably used as a coating agent, and particularly preferably used as a hard coat coating agent or an optical film coating agent.
  • the active energy ray-curable resin composition is applied to a polyethylene terephthalate (PET) film having a size of 15 cm ⁇ 15 cm and a thickness of 100 ⁇ m so that the cured coating film has a thickness of 10 ⁇ m.
  • PET polyethylene terephthalate
  • an 80 W high-pressure mercury lamp is prepared at a height of 18 cm from the surface of the PET film so that the integrated irradiation amount becomes 500 mJ / cm 2 at a speed of 5.1 m / min.
  • a cured coating film is obtained by irradiating with ultraviolet rays.
  • the cured coating film is cut out to be 10 cm ⁇ 10 cm, and the average value of the height of the four corners of the cut-out cured coating film is 40 mm or less, particularly 30 mm or less, and further, a coating that becomes a cured coating film of 25 mm or less. It is preferable to use an agent.
  • the active energy ray-curable resin composition is applied to an easy-adhesion PET film having a size of 15 cm ⁇ 15 cm and a thickness of 125 ⁇ m so that the cured coating film has a thickness of 10 ⁇ m, and a temperature of 60
  • an 80 W high-pressure mercury lamp is prepared at a height of 18 cm from the surface of the easy-adhesive PET film so that the integrated irradiation amount becomes 500 mJ / cm 2 at a speed of 5.1 m / min.
  • a cured coating film is obtained by irradiating with ultraviolet rays.
  • the cured coating film is evaluated for flexibility using a cylindrical mandrel bending tester in accordance with JIS K 5600-5-1.
  • a coating agent having a maximum diameter (integer value, mm) of 20 mm or less, particularly 15 mm or less, more preferably 10 mm or less, and particularly 8 mm or less.
  • the active energy ray-curable resin composition is applied to an easy-adhesion PET film having a size of 15 cm ⁇ 15 cm and a thickness of 125 ⁇ m so that the cured coating film has a thickness of 10 ⁇ m.
  • an 80 W high-pressure mercury lamp is prepared at a height of 18 cm from the surface of the easy-adhesive PET film so that the integrated irradiation amount becomes 500 mJ / cm 2 at a speed of 5.1 m / min.
  • a cured coating film is obtained by irradiating with ultraviolet rays.
  • the surface of the cured coating film was reciprocated 10 times while applying a load of 500 g. Also, the surface of the coating film having no scratch is preferable.
  • the invention according to the first aspect of the present invention is a (meth) acrylate (A) in a mixture (A) of the above (meth) acrylates (a1) to (a4), which is a reaction product of pentaerythritol and (meth) acrylic acid ( a urethane (meth) acrylate composition [I] obtained by reacting a1) to (a3) with a polyvalent isocyanate (CA), and the mixture (A) has a hydroxyl value of 200 mgKOH / g or more. It is an active energy ray-curable resin composition.
  • this active energy ray-curable resin composition has a small curing shrinkage, it is difficult to curl, and can form a cured coating film having excellent hardness and flexibility, and further, an uncured coating film before curing.
  • the coating surface is not sticky and has the effect of being able to form a tack-free coating surface, especially as a coating agent (and hard coating agent and optical film coating agent). It is also useful as a paint or ink.
  • the invention according to the second aspect of the present invention is the (meth) acrylate (A) in the mixture (A) of the above (meth) acrylates (a1) to (a4) which is a reaction product of pentaerythritol and (meth) acrylic acid ( a urethane (meth) acrylate composition [I] obtained by reacting a1) to (a3) with a polyvalent isocyanate (CA), and a reaction product of dipentaerythritol and (meth) acrylic acid shown below (meta ) Urethane (meth) acrylate composition [II] obtained by reacting (meth) acrylates (b1) to (b5) in the mixture (B) of acrylates (b1) to (b6) with the polyvalent isocyanate (CB) And the mixture (A) has a hydroxyl value of 200 mgKOH / g or more, and the mixture (B) has a hydroxyl value of 40 mgKOH / g or more.
  • This active energy ray-curable resin composition has an effect that it is difficult to curl because of its small curing shrinkage and can form a cured coating film having excellent hardness and flexibility.
  • the invention according to the third aspect of the present invention includes the (meth) acrylates (a1) to (a3) of [ ⁇ ], the (meth) acrylates (b1) to (b5) of [ ⁇ ], and a polyvalent
  • This is an active energy ray-curable resin composition comprising a urethane (meth) acrylate-based composition [III] reacted with isocyanate (CC).
  • This active energy ray-curable resin composition has an effect that it is difficult to curl due to small curing shrinkage and can form a cured coating film having excellent hardness, flexibility and scratch resistance. It is useful as a coating agent (further, a hard coat coating agent or an optical film coating agent). It is also useful as a paint or ink.
  • Example using urethane (meth) acrylate-based composition [I] >> The urethane acrylate composition [I] ([I-1] to [I-4]) and the urethane acrylate composition [I ′] ([I′-1] to [I′-1] I′-4]) was prepared.
  • the reaction was terminated to obtain a urethane acrylate composition [I-1] (resin concentration 50%).
  • the obtained urethane acrylate composition [I-1] had a weight average molecular weight of 4,700 and a viscosity at 20 ° C. of 80 mPa ⁇ s.
  • the viscosity at 20 ° C. was measured using a B-type viscometer. The viscosity measurement at 20 ° C. is the same in the following.
  • the content ratio of each component to the total of the following components (a1) to (a4) in the acrylate mixture (A-1) is as follows.
  • the content ratio of each component in the mixture is measured by using a column (Imtakt, Cadenza CD-C18 100 ⁇ 3 mm, 3 ⁇ m) in a liquid chromatograph (Agilent, “Technology HP 1100”).
  • urethane acrylate composition [I′-1] (resin concentration 100%).
  • the resulting urethane acrylate composition [I′-1] had a weight average molecular weight of 1,400 and a viscosity at 60 ° C. of 3,000 mPa ⁇ s. However, since it was high viscosity, it measured using the E-type viscosity meter.
  • the content ratio of each component with respect to the total of the following components (a1) to (a4) in the acrylate mixture (A′-1) is as follows.
  • the content ratio of the components (a2) to (a4) is shown.
  • Adduct 14 g, polyester polyol consisting of adipic acid and neopentyl glycol (DIC, “ODX-2044”, number average molecular weight: about 2,000) 114 g, 4-methoxyphenol 0.08 g as a polymerization inhibitor, reaction As a catalyst, 0.05 g of dibutyltin dilaurate was added and reacted at 60 ° C. When the residual isocyanate group reached 3.9%, an acrylate mixture (A-1) having a hydroxyl value of 288 mgKOH / g (addition of acrylic acid of pentaerythritol) ) Add 35g, anti-react at 60 °C It was.
  • A-1 having a hydroxyl value of 288 mgKOH / g (addition of acrylic acid of pentaerythritol)
  • the reaction was terminated to obtain a urethane acrylate composition [I′-2] (resin content concentration 100%).
  • the urethane acrylate composition [I′-2] to be obtained does not have a reaction product of only (A-1) and (C-1).
  • the obtained urethane acrylate composition [I′-2] had a weight average molecular weight of 18,000 and a viscosity at 60 ° C. of 700,000 mPa ⁇ s. However, since it was high viscosity, it measured using the E-type viscosity meter.
  • the reaction was terminated when the group reached 0.1%, and a urethane acrylate composition [I′-3] was obtained (resin concentration 50%).
  • the obtained urethane acrylate composition [I′-3] had a weight average molecular weight of 2,100 and a viscosity at 20 ° C. of 73 mPa ⁇ s.
  • the content ratio of each component with respect to the total of the following components (a1) to (a4) in the acrylate mixture (A′-2) is as follows.
  • the reaction was terminated when the residual isocyanate group reached 0.1%, and a urethane acrylate composition [I′-4] was obtained (resin concentration 50%).
  • the obtained urethane acrylate composition [I′-4] had a weight average molecular weight of 2,200 and a viscosity at 20 ° C. of 85 mPa ⁇ s.
  • Examples 1 to 4 and Comparative Examples 1 to 4 [Production of active energy ray-curable resin composition]
  • the urethane acrylate composition obtained above ([I], [I ′]) is cured with 1-hydroxycyclohexyl phenyl ketone (“Omnirad 184” manufactured by IGM) as a photopolymerization initiator (D).
  • An active energy ray-curable resin composition was obtained by adding 4 parts to 100 parts.
  • the obtained urethane acrylate compositions ([I], [I ′]) were diluted with ethyl acetate so as to have a resin content of 50%. In the same manner as above, an active energy ray-curable resin composition was obtained.
  • the coating film before hardening (dry coating film) was formed as follows, and the stickiness of the coating film was evaluated. Furthermore, a cured coating film was formed as described below, and the hardness and flexibility of the cured coating film were evaluated. The evaluation results are as shown in Table 1 below.
  • the active energy ray-curable resin composition obtained above is coated with an adhesive PET film (Toyobo Co., Ltd., “A4300”, size 15 cm ⁇ 15 cm, thickness 125 ⁇ m) using a bar coater.
  • An adhesive PET film Toyobo Co., Ltd., “A4300”, size 15 cm ⁇ 15 cm, thickness 125 ⁇ m
  • the obtained uncured coating film was pushed in using a tacking tester (“TAC-II”, manufactured by Reska Co., Ltd.) at 120 mm / min, lifting speed 600 mm / min, pressure 20.4 gf, and pressurizing time 1.0.
  • the probe tack test was conducted under the condition of seconds.
  • the active energy ray-curable resin composition obtained above is coated with an adhesive PET film (Toyobo Co., Ltd., “A4300”, size 15 cm ⁇ 15 cm, thickness 125 ⁇ m) using a bar coater. Is applied to a thickness of 10 ⁇ m, dried at 60 ° C. for 3 minutes, and then irradiated with two passes of UV light at a conveyor speed of 5.1 m / min from a height of 18 cm using a high pressure mercury lamp 80 W and one lamp. (Integrated irradiation amount 500 mJ / cm 2 ) was performed to form a cured coating film. The above cured coating film coated on the easy-adhesion PET film was tested according to JIS K-5600, and the pencil hardness was measured.
  • a cured coating film was formed in the same manner as the above hardness evaluation, and the cured coating film coated on the easy-adhesion PET film was bent using a cylindrical mandrel bending tester according to JIS K 5600-5-1. Sexuality was evaluated. The maximum diameter (integer value, mm) at which cracking or peeling occurred was measured when the evaluation cured coating film was wound around a test bar such that the coating film surface was on the outside. It means that it is a coating film with high flexibility, so that a value is small.
  • the cured coating films obtained from the active energy ray-curable resin compositions containing the urethane acrylate compositions [I] of Examples 1 to 4 are excellent in hardness and flexibility, and before being cured. It can be seen that even an uncured coating film is not sticky.
  • Comparative Example 1 is inferior in the flexibility of the cured coating film. The film was sticky.
  • the comparative example 2 was inferior to the hardness of a cured coating film, and also the coating film before hardening had a stickiness.
  • the cured coating film was inferior in flexibility. From these, the active energy ray-curable resin compositions of Examples 1 to 4 are tack-free, have good hardness and flexibility, and are used as coating agents, particularly hard coat coating agents and optical film coating agents. Is useful.
  • urethane (meth) acrylate-based compositions [I] and [II] Examples using urethane (meth) acrylate-based compositions [I] and [II] >> As described below, urethane acrylate composition [I] ([I-5] to [I-7]), [II] ([II-1] to [II-2]), and urethane for comparison An acrylate composition [I ′] ([I′-5] to [I′-7]) was prepared.
  • the reaction was terminated to obtain a urethane acrylate composition [I-5] (resin concentration 50%).
  • the obtained urethane acrylate composition [I-5] had a weight average molecular weight of 4,700 and a viscosity at 20 ° C. of 80 mPa ⁇ s.
  • the viscosity at 20 ° C. was measured using a B-type viscometer. The viscosity measurement at 20 ° C. is the same in the following.
  • the content ratio of each component to the total of the following components (a1) to (a4) in the acrylate mixture (A-1) is as follows.
  • urethane acrylate composition [II-1] (resin concentration 100%).
  • the obtained urethane acrylate composition [II-1] had a weight average molecular weight of 5,500 and a viscosity at 60 ° C. of 39,400 mPa ⁇ s.
  • the viscosity at 60 ° C. was measured using an E-type viscometer. The viscosity measurement at 60 ° C. is the same in the following.
  • the content ratio of each component with respect to the total of the following components (b1) to (b6) in the acrylate mixture (B-1) is as follows.
  • (B4) Dipentaerythritol tetraacrylate 18%
  • (B5) Dipentaerythritol pentaacrylate 51%
  • (B6) Dipentaerythritol hexaacrylate 31%
  • the inclusion of components (b4) to (b6) was below the measurement limit value, the inclusion of components (b4) to (b6) The percentage is shown.
  • the urethane acrylate composition [II-2] was obtained (resin concentration 100%).
  • the resulting urethane acrylate composition [II-2] had a weight average molecular weight of 67,000 and a viscosity at 60 ° C. of 65,000 mPa ⁇ s.
  • the urethane acrylate composition [II-3] was obtained (resin concentration 100%).
  • the obtained urethane acrylate composition [II-3] had a weight average molecular weight of 2,000 and a viscosity at 60 ° C. of 1,700 mPa ⁇ s.
  • the content ratio of each component with respect to the total of the following components (b1) to (b6) in the acrylate mixture (B-2) is as follows.
  • (B4) Dipentaerythritol tetraacrylate 6%
  • (B5) Dipentaerythritol pentaacrylate 54%
  • (B6) Dipentaerythritol hexaacrylate 40%
  • the content of (b1) dipentaerythritol monoacrylate, (b2) dipentaerythritol diacrylate, and (b3) dipentaerythritol triacrylate was below the measurement limit value, the inclusion of components (b4) to (b6) The percentage is shown.
  • the residual isocyanate group was 0.3% or less.
  • the reaction was terminated to obtain a urethane acrylate composition [I′-5] (resin content concentration 100%).
  • the obtained urethane acrylate composition [I′-5] had a weight average molecular weight of 1,400 and a viscosity at 60 ° C. of 3,000 mPa ⁇ s.
  • the content ratio of each component with respect to the total of the following components (a1) to (a4) in the acrylate mixture (A′-1) is as follows.
  • the content ratio of the components (a2) to (a4) was shown.
  • the reaction was terminated when the residual isocyanate group reached 0.1%, and a urethane acrylate composition [I′-6] was obtained (resin content concentration 50%).
  • the obtained urethane acrylate composition [I′-6] had a weight average molecular weight of 2,200 and a viscosity at 20 ° C. of 85 mPa ⁇ s.
  • the content ratio of each component with respect to the total of the following components (a1) to (a4) in the acrylate mixture (A′-2) is as follows.
  • the reaction was terminated to obtain a urethane acrylate composition [I′-7] (resin concentration 50%).
  • the obtained urethane acrylate composition [I′-7] had a weight average molecular weight of 2,100 and a viscosity at 20 ° C. of 73 mPa ⁇ s.
  • a cured coating film was formed as follows, and the hardness and flexibility of the cured coating film were evaluated. The evaluation results are as shown in Table 2 below.
  • the active energy ray-curable resin composition obtained above is coated with an adhesive PET film (Toyobo Co., Ltd., “A4300”, size 15 cm ⁇ 15 cm, thickness 125 ⁇ m) using a bar coater. Is applied to a thickness of 10 ⁇ m, dried at 60 ° C. for 3 minutes, and then irradiated with two passes of UV light at a conveyor speed of 5.1 m / min from a height of 18 cm using a high pressure mercury lamp 80 W and one lamp. (Integrated irradiation amount 500 mJ / cm 2 ) was performed to form a cured coating film. The above cured coating film coated on the easy-adhesion PET film was tested according to JIS K-5600, and the pencil hardness was measured.
  • a cured coating film was formed in the same manner as the above hardness evaluation, and the cured coating film coated on the easy-adhesion PET film was bent using a cylindrical mandrel bending tester according to JIS K 5600-5-1. Sexuality was evaluated. The maximum diameter (integer value, mm) at which cracking or peeling occurred was measured when the evaluation cured coating film was wound around a test bar such that the coating film surface was on the outside. It means that it is a coating film with high flexibility, so that a value is small.
  • the cured coating films obtained from the active energy ray-curable resin compositions containing the urethane acrylate compositions [I] and [II] of Examples 5 to 12 are excellent in both hardness and flexibility. I understand that. On the other hand, in Comparative Example 5 which did not contain the urethane acrylate composition [I] and used only the urethane acrylate composition [II], the flexibility of the cured coating film was inferior. Furthermore, in Comparative Examples 6 and 7 containing a urethane acrylate composition prepared using an acrylate mixture having a low hydroxyl value, the flexibility of the cured coating film was inferior.
  • A-1 Acrylic acid adduct of pentaerythritol having a hydroxyl value of 288 mgKOH / g, and the content ratio of each component to the total of the following components (a1) to (a4) is as follows.
  • A′-1 Acrylic acid adduct of pentaerythritol having a hydroxyl value of 118 mgKOH / g, and the content ratio of each component to the total of the following components (a1) to (a4) is as follows.
  • the content ratio of the components (a2) to (a4) was shown.
  • A′-2 Acrylic acid adduct of pentaerythritol having a hydroxyl value of 184.2 mgKOH / g, and the content ratio of each component to the total of the following components (a1) to (a4) is as follows.
  • A4 Pentaerythritol tetraacrylate 34.2%
  • B4 Dipentaerythritol tetraacrylate 18%
  • B5 Dipentaerythritol pentaacrylate 51%
  • B6 Dipentaerythritol hexaacrylate 31%
  • the content of (b1) dipentaerythritol monoacrylate, (b2) dipentaerythritol diacrylate, and (b3) dipentaerythritol triacrylate was below the measurement limit value, the inclusion of components (b4) to (b6) The percentage is shown.
  • B-2 An acrylic acid adduct of dipentaerythritol having a hydroxyl value of 54 mgKOH / g, and the content ratio of each component to the total of the following components (b1) to (b6) is as follows.
  • B4 Dipentaerythritol tetraacrylate 6%
  • B5 Dipentaerythritol pentaacrylate 54%
  • B6 Dipentaerythritol hexaacrylate 40%
  • the content of (b1) dipentaerythritol monoacrylate, (b2) dipentaerythritol diacrylate, and (b3) dipentaerythritol triacrylate was below the measurement limit value, the inclusion of components (b4) to (b6) The percentage is shown.
  • D-1 1-hydroxycyclohexyl phenyl ketone (manufactured by IGM, “Omnilad 184”)
  • urethane acrylate composition (III-1) had a weight average molecular weight of 4,900 and a viscosity at 20 ° C. of 40 mPa ⁇ s.
  • the viscosity at 20 ° C. was measured using a B-type viscometer. The viscosity measurement at 20 ° C. is the same in the following.
  • the reaction was terminated to obtain a urethane acrylate composition (III-3).
  • (Resin concentration 70%) The resulting urethane acrylate composition (III-3) had a weight average molecular weight of 3,300 and a viscosity at 20 ° C. of 460 mPa ⁇ s.
  • Adduct 49 g, hydroxyl group value 54 mg KOH / g acrylate mixture (B-2) (dipentaerythritol acrylic acid adduct) 112 g, polymerization inhibitor 0.08 g 4-methoxyphenol, dibutyltin dilaurate 0. 05 g was charged and reacted at 60 ° C. When the residual isocyanate group reached 0.1%, the reaction was terminated to obtain a urethane acrylate composition (III-3) (resin concentration 100%). The weight average molecular weight of the obtained urethane acrylate composition (III-4) was 3,800. Since the viscosity was very high, the viscosity could not be measured.
  • the urethane acrylate composition (III′-1) (Resin concentration 70%) was obtained.
  • the resulting urethane acrylate composition (III′-1) had a weight average molecular weight of 1,700 and a viscosity at 20 ° C. of 140 mPa ⁇ s.
  • composition (III′-2) was obtained (resin concentration: 50%).
  • the resulting urethane acrylate composition (III′-2) had a weight average molecular weight of 2,300 and a viscosity at 20 ° C. of 65 mPa ⁇ s.
  • the urethane acrylate composition (III′-4) was obtained (resin content concentration 100%).
  • the resulting urethane acrylate composition (III′-4) had a weight average molecular weight of 5,500 and a viscosity at 60 ° C. of 39,400 mPa ⁇ s.
  • the viscosity at 60 ° C. was measured using an E-type viscometer.
  • the active energy ray-curable resin composition obtained above is coated with an adhesive PET film (Toyobo Co., Ltd., “A4300”, size 15 cm ⁇ 15 cm, thickness 125 ⁇ m) using a bar coater. Is applied to a thickness of 10 ⁇ m, dried at 60 ° C. for 3 minutes, and then irradiated with two passes of UV light at a conveyor speed of 5.1 m / min from a height of 18 cm using a high pressure mercury lamp 80 W and one lamp. (Integrated irradiation amount 500 mJ / cm 2 ) was performed to form a cured coating film. The above cured coating film coated on the easy-adhesion PET film was tested according to JIS K-5600, and the pencil hardness was measured.
  • a cured coating film was formed in the same manner as the above hardness evaluation, and the cured coating film coated on the easy-adhesion PET film was bent using a cylindrical mandrel bending tester according to JIS K 5600-5-1. Sexuality was evaluated. The maximum diameter (integer value, mm) at which cracking or peeling occurred was measured when the evaluation cured coating film was wound around a test bar such that the coating film surface was on the outside. It means that it is a coating film with high flexibility so that a value is small.
  • a cured coating film was formed in the same manner as in the above hardness evaluation, and a 500 g load was applied to the cured coating film coated on the easy-adhesive PET film using steel wool (Nihon Steel Wool Co., Ltd., Bonster # 0000). Then, after the surface of the cured coating was reciprocated 10 times, the degree of scratching on the surface was visually observed. (Evaluation) ⁇ ⁇ ⁇ ⁇ Scratches can not be confirmed ⁇ ⁇ ⁇ ⁇ Scratches can be confirmed
  • the cured coating film obtained from the active energy ray-curable resin composition containing the urethane acrylate composition [III] of Examples 13 to 16 has not only hardness and flexibility but also scratch resistance. Can also be seen as excellent.
  • Comparative Example 10 using a low hydroxyl value pentaerythritol acrylic acid adduct (A′-1) having a hydroxyl value of less than 200 mgKOH / g, among the mixtures (A) and (B) dipentaerythritol
  • Comparative Example 13 using only the acrylic acid adduct (B-1) the flexibility of the cured coating film was inferior.
  • Comparative Example 11 using the pentaerythritol acrylic acid adduct (A′-2) having a slightly lower hydroxyl value, the hardness was slightly inferior and the scratch resistance was inferior. Furthermore, in the case of Comparative Example 12 using only the acrylic acid adduct (A-1) of pentaerythritol having a high hydroxyl value among the mixtures (A) and (B), the cured coating film was inferior in scratch resistance. there were. From these, the active energy ray-curable resin compositions of Examples 13 to 16 are excellent in hardness and flexibility, as well as scratch resistance, and coating agents such as hard coat coating agents and optical film coating agents. It turns out to be useful in the application.
  • the active energy ray-curable resin composition of the present invention is capable of forming a coating film that is hard to curl and has excellent hardness and flexibility due to small curing shrinkage when a cured coating film is formed. It is useful as a coating agent, especially as a coating agent for hard coats and a coating agent for optical films. It is also useful as a paint or ink. Furthermore, after affixing the resin composition side of the uncured laminated film in which the active energy ray-curable resin composition layer is formed on the film to the molded product, various active energy ray curings are performed. A cured film can be easily formed on the molded product.

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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • General Physics & Mathematics (AREA)
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Abstract

L'invention concerne une composition de résine durcissable par rayonnement d'énergie active contenant une composition à base de (méth)acrylate d'uréthane, présentant un faible retrait au durcissement et étant ainsi capable de former un film de revêtement durci, le film de revêtement durci ne se recourbant pas facilement et présentant une dureté et une flexibilité remarquables. La composition de résine durcissable par rayonnement d'énergie active contient une composition à base de (méth)acrylate d'uréthane [I] obtenue par réaction d'un groupe isocyanate d'un isocyanate polyvalent (CA) avec un groupe hydroxy d'un (méth)acrylate contenu dans un mélange de (méth)acrylate (A) qui est un produit de réaction du pentaérythritol et de l'acide (méth)acrylique, l'indice d'hydroxyle du mélange (A) étant au moins égal à 200 mgKOH/g.
PCT/JP2018/013806 2017-03-31 2018-03-30 Composition de résine durcissable par rayonnement d'énergie active et agent de revêtement WO2018181972A1 (fr)

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JP2012229412A (ja) * 2011-04-13 2012-11-22 Nippon Synthetic Chem Ind Co Ltd:The 樹脂組成物、コーティング剤
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