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WO2019117030A1 - 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
WO2019117030A1
WO2019117030A1 PCT/JP2018/045067 JP2018045067W WO2019117030A1 WO 2019117030 A1 WO2019117030 A1 WO 2019117030A1 JP 2018045067 W JP2018045067 W JP 2018045067W WO 2019117030 A1 WO2019117030 A1 WO 2019117030A1
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meth
acrylate
energy ray
active energy
curable resin
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Japanese (ja)
Inventor
修平 酒谷
敦子 小西
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Mitsubishi Chemical Corp
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Mitsubishi Chemical Corp
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Priority to KR1020207012070A priority Critical patent/KR102645100B1/ko
Priority to CN201880069383.4A priority patent/CN111278880A/zh
Publication of WO2019117030A1 publication Critical patent/WO2019117030A1/fr
Anticipated expiration legal-status Critical
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    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C08F2/40—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation using retarding agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • 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
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/22—Esters containing halogen
    • 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
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • 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
    • 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
    • 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
    • C08F299/08—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 polysiloxanes
    • 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
    • C08G18/675—Low-molecular-weight compounds
    • C08G18/6755—Unsaturated carboxylic acids
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic

Definitions

  • the present invention relates to an active energy ray-curable resin composition and a coating agent comprising a urethane (meth) acrylate composition, and more specifically, antifouling performance (contamination resistance and its durability) and a cured coating
  • the present invention relates to an active energy ray-curable resin composition capable of forming a coating film excellent in the properties (appearance, hardness, scratch resistance) of the above, and a coating agent containing the same.
  • a hard coating agent having high surface hardness and scratch resistance as a cured coating film as described above for example, one in which a fluorine compound is mixed with a curing component mainly composed of dipentaerythritol hexaacrylate and N-substituted acrylamide It is proposed (for example, refer patent document 1).
  • a film obtained by applying this hard coating agent on a laminated film to a film thickness of 11 ⁇ m and curing it does not get scratched even if it is reciprocated 500 times with a hardness of about 5H with a pencil hardness of about 5H It develops scratch resistance.
  • Patent Document 1 is excellent in surface hardness of a cured coating film and scratch resistance under a load of 500 g, there is no description regarding scratch resistance under a more severe 1 kg load, and further improvement is required. There is.
  • the storage stability of the coating liquid is excellent, and the antifouling performance (contamination resistance and its persistence), the characteristics of the cured coating (appearance, hardness, scratch resistance)
  • the present invention provides an active energy ray-curable resin composition capable of forming a coating film excellent in the following properties), and a coating agent using the same.
  • urethane (meth) acrylates obtained by reacting a (meth) acrylic acid adduct of polyhydric alcohol with a polyisocyanate compound as a curing component.
  • the active energy ray curable resin composition contains a larger amount of the above-mentioned polymerization inhibitor than usual. It was found that a cured coating film excellent in storage stability with the solution of (1) and when it was formed into a cured coating film was excellent in coating physical properties such as antifouling performance and scratch resistance.
  • a urethane (meth) acrylate composition [I] in which the hydroxyl group in the (meth) acrylic acid adduct of polyhydric alcohol (A) and the isocyanate group of the polyisocyanate compound (B) have reacted.
  • the coating agent formed by containing the active energy ray curable resin composition of the said 1st summary makes it a 2nd summary.
  • a polymerization inhibitor is introduced into the reaction system for the purpose of suppressing the polymerization reaction of the (meth) acryloyl group during the urethanization reaction and improving the storage stability.
  • the compounding amount should be as small as possible, since the active energy ray curability is lowered due to the presence of the polymerization inhibitor or the pigment is colored.
  • the use of the polymerization inhibitor in an amount larger than that used in the preparation of the urethane (meth) acrylate composition lowers the active energy ray curability and the coating liquid and the curing.
  • the coating liquid is excellent in storage stability, anti-soiling performance (stain resistance and its persistence), and the cured film has excellent properties (appearance, hardness, scratch resistance) It has been found that a film can be formed.
  • the active energy ray-curable resin composition of the present invention is a urethane (meth) in which the hydroxyl group in the (meth) acrylic acid adduct (A) of polyhydric alcohol and the isocyanate group of the polyisocyanate compound (B) have reacted.
  • Acrylate composition [I], fluorine-containing (meth) acrylate compound [II] and polymerization inhibitor [III], and the content of polymerization inhibitor [III] is urethane (meth) acrylate composition
  • the amount is 800 to 10,000 ppm by weight based on the total of the compound [I], the fluorine-containing (meth) acrylate compound [II] and the polymerization inhibitor [III].
  • the said polyhydric alcohol is at least one of dipentaerythritol and pentaerythritol especially among this invention, it is more excellent in the storage stability in a coating liquid, and also when it is set as a cured coating film. It becomes excellent also in antifouling performance and abrasion resistance.
  • the fluorine-containing (meth) acrylate compound [II] when the fluorine-containing (meth) acrylate compound [II] has a siloxane bond, it becomes more excellent in antifouling performance.
  • the antifouling performance is further enhanced.
  • the weight average molecular weight of the said urethane (meth) acrylate type composition [I] is 900-30,000 especially among this invention, it will become excellent by the abrasion resistance at the time of setting it as a cured coating film. .
  • the active energy ray curable resin composition of the present invention further contains a coloration inhibitor [IV], the storage stability in the coating liquid is further improved.
  • the active energy ray-curable resin composition of the present invention further contains an organic solvent having a boiling point of 80 ° C. or higher, the above urethane (meth) acrylate composition [I] and the fluorine-containing (meth) acrylate compound [ Since the compatibility with [II] is excellent, the storage stability of the coating liquid is further improved.
  • (meth) acrylic means acrylic or methacrylic
  • (meth) acryloyl means acryloyl or methacryloyl
  • (meth) acrylate means acrylate or methacrylate.
  • the active energy ray curable resin composition of the present invention comprises a urethane (meth) acrylate composition [I], a fluorine-containing (meth) acrylate compound [II] and a polymerization inhibitor [III]. The details will be described below.
  • urethane (meth) acrylate composition [I] used in the present invention reacts the hydroxyl group in the (meth) acrylic acid adduct (A) of polyhydric alcohol with the isocyanate group of the polyisocyanate compound (B) Thus, a urethane bond can be formed.
  • each component used by this invention is demonstrated.
  • the (meth) acrylic acid adduct (A) of the polyhydric alcohol used in the present invention is a compound in which (meth) acrylic acid is added to the hydroxyl group of the polyhydric alcohol, and all hydroxyl groups of the polyhydric alcohol It is a mixture including one to which (meth) acrylic acid is added, one to which (meth) acrylic acid is added to a part of hydroxyl groups of a polyhydric alcohol, and the like.
  • the polyhydric alcohol is preferably a trihydric or higher polyol, but a dihydric alcohol may be used.
  • a dihydric alcohol may be used as a kind of alcohol, aliphatic alcohol, alicyclic alcohol, aromatic alcohol etc. are mentioned, for example, Especially, aliphatic alcohol is preferable.
  • trivalent or higher aliphatic polyols examples include pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, trimethylolpropane, trimethylolethane, 1,3,6-hexanetriol, adamantantriol and the like. These can be used alone or in combination of two or more. Among them, pentaerythritol and dipentaerythritol are preferable.
  • (meth) acrylic acid adducts of pentaerythritol and dipentaerythritol which are suitable polyhydric alcohols [(meth) acrylic acid adduct of pentaerythritol (A1) and (meth) acrylic acid adduct of dipentaerythritol ((meth) acrylic acid adduct A2)] will be described.
  • the (meth) acrylic acid adduct of pentaerythritol means, in its component, pentaerythritol tetra (4) having (meth) acrylic acid added to all four of the four hydroxyl groups possessed by pentaerythritol.
  • the (meth) acrylic acid adduct (A1) of pentaerythritol may be one obtained by reacting pentaerythritol and (meth) acrylic acid according to a generally known method.
  • the hydroxyl value of the (meth) acrylic acid adduct (A1) of pentaerythritol is preferably 50 to 300 mg KOH / g, more preferably 70 to 200 mg KOH / g, and particularly preferably 100 to 160 mg KOH / g. . If the hydroxyl value is too small, the content of pentaerythritol tetra (meth) acrylate which is low in molecular weight and has a large number of ethylenic unsaturated groups and does not react with isocyanate groups increases, so that curing shrinkage during curing becomes large and curls It tends to be easier.
  • the content of the polyol component such as pentaerythritol di (meth) acrylate diol or pentaerythritol mono (meth) acrylate triol increases, so that the molecular weight of the resulting urethane acrylate becomes large, The viscosity increases and tends to be difficult to handle.
  • the hydroxyl value of the (meth) acrylic acid adduct (A1) of pentaerythritol mentioned above means the hydroxyl value of the mixture of (meth) acrylic acid adducts of pentaerythritol as a whole. Further, in the present invention, the hydroxyl value is a value obtained by a method according to JIS K 1557-1.
  • the adjustment of the hydroxyl value of the (meth) acrylic acid adduct (A1) of pentaerythritol can be performed, for example, by adjusting the ratio of (meth) acrylic acid to be added to pentaerythritol.
  • the (meth) acrylic acid adduct of dipentaerythritol refers to dipentaerythritol in which (meth) acrylic acid is added to all six of the six hydroxyl groups possessed by dipentaerythritol in the component.
  • dipentaerythritol hexa (meth) acrylate dipentaerythritol penta (meth) acrylate monool having 5 (meth) acrylic acid added thereto, and dipentaerythritol tetra (meth) acrylate having 4 (meth) acrylic acid added Diol, dipentaerythritol tri (meth) acrylate triol to which (meth) acrylic acid is added to three, dipentaerythritol di (meth) acrylate tetraol to which (meth) acrylic acid is added to two, only one (Meth) acrylic acid added to dipentaerythritol (meth) It is a mixture containing chestnut rate pentaols.
  • the (meth) acrylic acid adduct (A2) of dipentaerythritol may be any one obtained by reacting dipentaerythritol and (meth) acrylic acid according to a generally known method.
  • the hydroxyl value of the (meth) acrylic acid adduct (A2) of dipentaerythritol is preferably 10 to 120 mg KOH / g, more preferably 20 to 80 mg KOH / g, particularly preferably 30 to 70 mg KOH / g, Particularly preferably, it is 40 to 60 mg KOH / g. If the hydroxyl value is too small, the content of dipentaerythritol hexa (meth) acrylate which has a low molecular weight and a large number of ethylenic unsaturated groups and does not react with the isocyanate group increases, so the curing shrinkage upon curing becomes large, and curling occurs. It tends to be easy to do.
  • the content of the polyol component such as dipentaerythritol tetra (meth) acrylate diol or dipentaerythritol tri (meth) acrylate triol increases, so the molecular weight of the resulting urethane acrylate becomes large. Since the viscosity is increased, it tends to be difficult to handle.
  • the hydroxyl value of the (meth) acrylic acid adduct (A2) of dipentaerythritol mentioned above means the hydroxyl value of the whole mixture of (meth) acrylic acid adducts of dipentaerythritol.
  • the adjustment of the hydroxyl value of the (meth) acrylic acid adduct (A2) of dipentaerythritol can be performed, for example, by adjusting the ratio of (meth) acrylic acid to be added to dipentaerythritol.
  • Polyisocyanate Compound (B) As the polyisocyanate compound (B) which reacts with the hydroxyl group of the (meth) acrylic acid adduct (A) of the polyhydric alcohol, known general compounds generally used for the production of urethane (meth) acrylate compositions These polyisocyanate compounds can be used.
  • polyisocyanate compound (B) examples include aromatic compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, phenylene diisocyanate and naphthalene diisocyanate.
  • aromatic compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, phenylene diisocyanate and naphthalene diisocyanate.
  • polyisocyanate pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, aliphatic diisocyanates such as lysine diisocyanate and lysine triisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, etc. Alicyclic polyisocyanates or trimeric compound or multimeric compounds of these polyisocyanates, allophanate type polyisocyanate, buret type polyisocyanate, water dispersible polyisocyanate, and the like. These polyisocyanate compounds (B) can be used alone or in combination of two or more.
  • the polyisocyanate compound (B) may be selected from various polyols, for example, low molecular weight polyols and high molecular weight polyols, particularly polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, polybutadiene polyols ( It may be a reaction product of a polyol such as a meth) acrylic polyol and a polyisocyanate compound.
  • aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate and lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene, in terms of excellent yellowing resistance and versatility.
  • Alicyclic diisocyanates such as diisocyanates are preferred, and isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate and hexamethylene diisocyanate are more preferred, and isophorone diisocyanate and hexamethylene diisocyanate are more preferred.
  • the urethane (meth) acrylate composition [I] used in the present invention is the hydroxyl group in the (meth) acrylic acid adduct of polyhydric alcohol (A) and the isocyanate of the polyisocyanate compound (B) It is obtained by reacting a group.
  • the functional group molar ratio of the isocyanate group of the above-mentioned polyisocyanate compound (B) and the hydroxyl group of the (meth) acrylic acid adduct of polyhydric alcohol (A) is adjusted, and, if necessary, dibutyltin A urethane (meth) acrylate composition [I] is obtained by reacting a polyisocyanate compound (B) and a (meth) acrylic acid adduct of a polyhydric alcohol (A) using a catalyst such as dilaurate. Can.
  • an acrylic acid adduct of dipentaerythritol (A2) having a hydroxyl value of 60 mg KOH / g or more as an acrylic acid adduct of polyhydric alcohol (A), and xylylene It excludes the urethane (meth) acrylate type composition which the at least 1 sort (s) of polyisocyanate system compound selected from the group which consists of an isocyanate, hydrogenated xylylene diisocyanate, and these derivatives reacted.
  • reaction molar ratio [(B) :( A)] of the preparation of the polyisocyanate compound (B) and the (meth) acrylic acid adduct (A) of polyhydric alcohol is about 1: 2 to 1: 5. is there.
  • the reaction of the (meth) acrylic acid adduct (A) of the polyhydric alcohol with the polyisocyanate compound (B) is generally carried out by the (meth) acrylic acid adduct of the above polyhydric alcohol (A), a polyisocyanate compound B) may be charged to the reactor all at once or separately and reacted.
  • a catalyst for the purpose of promoting the reaction, and examples of such a catalyst include dibutyltin dilaurate, dibutyltin diacetate, trimethyltin hydroxide, tetra-n-butyltin and zinc bisacetylacetonate.
  • Organometallic compounds such as zirconium tris (acetylacetonate) ethylacetoacetate, zirconium tetraacetylacetonate, tin octylate, tin octenate, zinc hexanoate, zinc octenate, zinc stearate, zirconium 2-ethylhexanoate, Metal salts such as cobalt naphthenate, stannous chloride, stannous chloride, potassium acetate, etc., triethylamine, triethylenediamine, benzyldiethylamine, 1,4-diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [5 , 4 0] Amine based catalysts such as undecene, N, N, N ', N'-tetramethyl-1,3-butanediamine, N-methylmorpholine, N-ethylmorpholine, bismut
  • polymerization inhibitor [III '] publicly known general agents used as a polymerization inhibitor can be used, and examples thereof include p-benzoquinone, naphthoquinone, toluquinone, 2,5-diphenyl-p-benzoquinone and the like.
  • Quinones hydroquinone, 2,5-di-t-butylhydroquinone, methylhydroquinone, mono-t-butylhydroquinone, 4-methoxyphenol, 2,6-di-t-butylcresol, p-t-butylcatechol, etc.
  • phenols are preferable, and 4-methoxyphenol and 2,6-di-t-butylcresol are particularly preferable. These can be used alone or in combination of two or more.
  • the content of the polymerization inhibitor [III '] in the above reaction is 0.005 to about the total 100 parts by weight of the (meth) acrylic acid adduct of polyhydric alcohol (A) and the polyisocyanate compound (B). It is 0.095 parts by weight, preferably 0.01 to 0.08 parts by weight. If the content of the polymerization inhibitor [III '] is too small, polymerization of acryloyl group may occur during the reaction. Furthermore, the liquid stability of the urethane (meth) acrylate composition [I] tends to decrease, and the composition tends to gel during storage. On the other hand, when the content of the polymerization inhibitor [III '] is too large, coloring tends to occur, and curing tends to be difficult even when irradiated with active energy rays.
  • an organic solvent having no functional group reactive to an isocyanate group for example, esters such as ethyl acetate, butyl acetate, 2-methoxy-1-methylethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, etc.
  • organic solvents such as aromatics such as toluene and xylene.
  • the reaction temperature of the above reaction is usually 30 to 90 ° C., preferably 40 to 80 ° C., and the reaction time is usually 2 to 30 hours, preferably 3 to 20 hours.
  • the urethane (meth) acrylate composition [I] used in the present invention contains plural kinds of urethane (meth) acrylates, and (meth) acrylic acid adduct of polyisocyanate compound (B) and unreacted polyhydric alcohol
  • the polymer (A) may further contain, for example, a polymer of a (meth) acrylic acid adduct of a polyhydric alcohol (A).
  • the weight average molecular weight of the above urethane (meth) acrylate composition [I] is preferably 900 to 30,000, more preferably 1,000 to 20,000, and particularly preferably 1,100 to 10,000. Particularly preferably, it is 1,200 to 5,000.
  • the weight-average molecular weight is too small, the cured coating tends to be brittle, and when it is too large, the viscosity becomes high and it becomes difficult to handle.
  • the weight average molecular weight in the present invention is a weight average molecular weight based on standard polystyrene molecular weight conversion, and in a high performance liquid chromatograph (manufactured by Waters, “ACQUITY APC system”), columns: ACQUITY APC XT 450 ⁇ 1, ACQUITY APC It is measured by using four XT 200 ⁇ 1 and ACQUITY APC XT 45 ⁇ 2 in series.
  • the viscosity of the urethane (meth) acrylate composition [I] at 60 ° C. is preferably 500 to 300,000 mPa ⁇ s, in particular 750 to 100,000 mPa ⁇ s, and further preferably 1,000 to 30.
  • the viscosity is preferably 1,000 mPa ⁇ s. If the viscosity is outside the above range, the coatability tends to decrease.
  • the measuring method of a viscosity is based on E-type viscosity meter.
  • the content of urethane (meth) acrylate in the urethane (meth) acrylate composition [I] used in the present invention is preferably 10% by weight or more, particularly preferably 20% by weight or more, and further preferably 30% by weight or more. Particularly preferably, it is 50% by weight or more.
  • the upper limit is usually 80% by weight.
  • the fluorine-containing (meth) acrylate compound [II] used in the present invention is a compound having a (meth) acryloyl group and a fluorine atom.
  • the structure other than the (meth) acryloyl group and the fluorine atom is not particularly limited, and may further have a heteroatom such as oxygen, nitrogen, silicon, sulfur and the like.
  • the fluorine-containing (meth) acrylate compound [II] is preferably a compound in which a fluorine atom is bonded to an alkyl group of a (meth) acrylic acid alkyl ester, for example, “Optool DAC” manufactured by Daikin Industries, Ltd.
  • fluorine-containing (meth) acrylate compounds [II] fluorine-containing (meth) acrylate compounds having a siloxane bond in the structure are preferable in that they are more excellent in antifouling performance, and “KY-1203” is particularly preferable preferable.
  • the weight average molecular weight of the fluorine-containing (meth) acrylate compound [II] is preferably 1,000 to 100,000, more preferably 5,000 to 70,000, and particularly preferably 10,000 to 1,000. It is preferably 50,000, more preferably 15,000 to 40,000.
  • the weight average molecular weight of the fluorine-containing (meth) acrylate compound [II] is too small, the scratch resistance and the antifouling performance tend to decrease, and when the weight average molecular weight is too large, the urethane (meth) acrylate composition [I The compatibility with the solvent and the solvent tends to be reduced.
  • the content of the fluorine-containing (meth) acrylate compound [II] in the active energy ray curable resin composition of the present invention is usually 0. 0 parts by weight based on 100 parts by weight of the urethane (meth) acrylate composition [I].
  • the content is from 01 to 5 parts by weight, preferably from 0.05 to 3 parts by weight, and particularly preferably from 0.1 to 1 parts by weight.
  • the active energy ray curable resin composition of the present invention contains the polymerization inhibitor [III] more than a general active energy ray curable resin composition.
  • the addition of a large amount of the polymerization inhibitor [III] causes reduction in active energy ray curability, coloring, etc.
  • the content of the polymerization inhibitor [III] is an amount such that the content of the polymerization inhibitor [III] is generally used in the production of the above-mentioned urethane (meth) acrylate composition [I].
  • the active energy ray curing is carried out
  • the content of the polymerization inhibitor [III] is larger than the amount used for the water-soluble resin composition, the liquid energy stability of the active energy ray-curable resin composition is free from the problem of decrease in the active energy ray curability and coloring problems The effect is to improve and to suppress gelation during storage.
  • polymerization inhibitor [III] used in the present invention known general ones can be used, and specifically, the same compounds as the compounds listed in the above-mentioned polymerization inhibitor [III '] can be used . Further, as the polymerization inhibitor [III] to be added to the active energy ray curable resin composition, the same compound as the polymerization inhibitor [III '] used in the production of the urethane (meth) acrylate composition [I] is used although it is preferred, different compounds may be used.
  • the content of the polymerization inhibitor [III] is relative to the total of the urethane (meth) acrylate composition [I], the fluorine-containing (meth) acrylate compound [II] and the polymerization inhibitor [III]. It is important that it is 800 to 10,000 ppm by weight, preferably 1,000 to 8,000 ppm, more preferably 1,500 to 7,000 ppm, still more preferably 2,000 to 6,000 ppm, in particular Preferably, it is 3,100 to 5,000 ppm.
  • the content of the polymerization inhibitor [III] is too small, the liquid stability of the active energy ray-curable resin composition before curing is reduced, and the composition becomes easy to gel during storage.
  • a coloring inhibitor is further added. It is preferable to contain [IV].
  • the above coloring inhibitors [IV] include aryl phosphine compounds such as triphenyl phosphine, 1,1,3,3-tetramethyldisilazane, 1,1,3,3,3-hexamethyldisilazane and the like.
  • Examples thereof include silazane compounds, and hydrazine compounds such as phenylhydrazine, benzophenylhydrolazine, and diacetylhydrazine.
  • hydrazine compounds such as phenylhydrazine, benzophenylhydrolazine, and diacetylhydrazine.
  • One of these coloring inhibitors may be used alone, or two or more thereof may be used in combination.
  • aryl phosphine compounds are preferable, and triphenyl phosphine is particularly preferable, in that the coloring of the urethane (meth) acrylate composition [I] can be further prevented.
  • the content of the above-mentioned coloring inhibitor [IV] is the total of urethane (meth) acrylate composition [I], fluorine-containing (meth) acrylate compound [II] and polymerization inhibitor [III],
  • the concentration is usually 10 to 10,000 ppm, preferably 100 to 5,000 ppm, and more preferably 250 to 2,000 ppm by weight.
  • the active energy ray curable resin composition of the present invention further contains a photopolymerization initiator.
  • an ethylenically unsaturated monomer other than urethane (meth) acrylate, an acrylic resin, a surface control agent, a leveling agent, and the like can be blended within a range that does not impair the effects of the present invention.
  • Fillers, reinforcing agents, matting agents, crosslinking agents, silica, water-dispersed or solvent-dispersed silica, zirconium compounds, preservatives and the like can also be blended. These may be used alone or in combination of two or more.
  • photopolymerization initiator examples include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl 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-one ⁇ 4- [4- (2-Hydroxy-2-methyl-propionyl) -benzyl] -phenyl ⁇ -2-methyl-propane, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 2-hydroxy Acetophenones such as 2-methyl-1- [4- (1-methylvinyl) phenyl]
  • acetophenones more preferably benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoin isopropyl ether, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, particularly preferably 1-hydroxycyclohexyl phenyl ketone.
  • the content thereof is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the curing component contained in the active energy ray curable resin composition, and in particular The amount is preferably 0.5 to 10 parts by weight, more preferably 1 to 10 parts by weight. If the content of the photopolymerization initiator is too small, curing tends to be poor and film formation tends to be difficult, and if too large, it causes yellowing of the cured coating film and tends to cause coloring problems.
  • auxiliary agent of the said photoinitiator for example, triethanolamine, triisopropanolamine, 4,4'-dimethylamino benzophenone (Michler's ketone), 4,4'- diethylamino benzophenone, 2-dimethylaminoethyl benzoic acid, Ethyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate (n-butoxy), isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2, It is also possible to use 4-diisopropylthioxanthone and the like in combination.
  • ethylenic unsaturated monomers other than the said urethane (meth) acrylate a monofunctional monomer, a bifunctional monomer, the trifunctional or more than trifunctional polyfunctional monomer etc. are mentioned, for example. These ethylenically unsaturated monomers can be used alone or in combination of two or more.
  • Examples of such monofunctional monomers include styrene-based 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) a Lilate, cyclohexyl (meth
  • ethylene glycol di (meth) acrylate for example, 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, 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, cyclohexane dimethanol di (meth) acrylate, ethoxylated cyclohexane dimethanol di ( Ta) acrylate, dimethylol dicyclopentadi (meth) acrylate, tricyclodecane dimethanol di (meth)
  • trifunctional or higher functional monomers examples include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa ( Meta) acrylate, tri (meth) acryloyloxy ethoxy trimethylol propane, glycerin polyglycidyl ether poly (meth) acrylate, isocyanurate ethylene oxide modified triacrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol hexamer (Meth) acrylate, caprolactone modified pentaerythritol tri (meth) acrylate, cap Lactone modified pentaerythritol tetra (
  • a Michael adduct of (meth) acrylic acid or 2-acryloyloxyethyl dicarboxylic acid monoester can also be used in combination.
  • Michael adducts of (meth) acrylic acid include (meth) acrylic acid dimers, (meth) acrylic acid trimers, and (meth) acrylic acid tetramers.
  • the 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-acryloyloxyethyl.
  • Examples thereof include phthalic acid monoester, 2-methacryloyloxyethyl phthalic acid monoester, 2-acryloyloxyethyl hexahydrophthalic acid monoester, and 2-methacryloyloxyethyl hexahydrophthalic acid monoester.
  • other oligoester acrylates and the like can be mentioned.
  • the content of the ethylenically unsaturated monomer other than urethane (meth) acrylate is preferably 70% by weight or less, particularly preferably 50% by weight, based on all the curing components contained in the active energy ray curable resin composition. % Or less, more preferably 30% by weight or less.
  • cellulose resin an alkyd resin, etc.
  • the cellulose resin has the effect of improving the surface smoothness of the coating film
  • the alkyd resin has the effect of improving the film forming property at the time of coating.
  • any generally known leveling agent can be used as long as it has the action of imparting wettability to the substrate of the coating liquid and the action of lowering surface tension.
  • silicone modified resin, fluorine modified resin And alkyl-modified resins can be used.
  • the active energy ray curable resin composition of the present invention comprises a mixture of a urethane (meth) acrylate composition [I], a fluorine-containing (meth) acrylate compound [II], a polymerization inhibitor [III] and other optional components. It can be obtained by The mixing method is not particularly limited, and various methods such as a method of mixing each component at once, a method of mixing optional components, and a method of collectively or sequentially mixing the remaining components are adopted. can do.
  • the active energy ray-curable resin composition of the present invention thus obtained is excellent in storage stability in a coating liquid, and further excellent in abrasion resistance when formed into a cured coating film and antifouling property after abrasion. It is a thing.
  • the active energy ray curable resin composition of the present invention may be coated as it is, or may be diluted with an organic solvent and coated.
  • the solid concentration may be usually 3 to 90% by weight (preferably 5 to 60% by weight) using an organic solvent.
  • organic solvent examples include alcohols such as methanol, ethanol, propanol, n-butanol and i-butanol, ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone and cyclohexanone, and aromatics such as toluene and xylene.
  • Glycol ethers such as -methoxy-2-propanol (alias: propylene glycol monomethyl ether), propylene glycol monomethyl ether acetate, ethyl cellosolve, acetates such as methyl acetate, ethyl acetate, butyl acetate, diacetone alcohol, etc. .
  • These organic solvents may be used alone or in combination of two or more.
  • Solvents having a boiling point of 80.degree. C. or higher, particularly 100.degree. C. or higher, more preferably 120 to 170.degree. C. are preferable, glycol ethers are more preferable, and 1-methoxy-2-propanol is particularly preferable.
  • Propylene glycol monomethyl ether acetate is particularly preferable.
  • a combination of a glycol ether such as propylene glycol monomethyl ether and a ketone such as methyl ethyl ketone or an alcohol such as methanol or a glycol ether such as propylene glycol monomethyl ether A combination of esters such as butyl acetate and a combination of ketones such as methyl ethyl ketone and alcohols such as methanol can be used.
  • the viscosity at 20 ° C. of the active energy ray-curable resin composition of the present invention is preferably 5 to 50,000 mPa ⁇ s, particularly preferably 10 to 10,000 mPa ⁇ s, still more preferably 15 to 5, It is 000 mPa ⁇ s. If the viscosity is outside the above range, the coatability tends to decrease. In addition, the measuring method of a viscosity is based on E-type viscosity meter.
  • 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 top coat agent and anchor coat agent for various substrates, and such active energy ray cure After the base resin composition is applied to the substrate (in the case where the active energy ray-curable resin composition diluted with an organic solvent is applied, after further drying), the active energy ray is cured to cure it. Be done.
  • Examples of the substrate 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 copolymer (ABS), and polystyrene.
  • Base materials such as acrylic resins, acrylic resins etc.
  • the coating method of the active energy ray-curable resin composition of the present invention includes, for example, wet coating methods such as spray, shower, gravure, dipping, roll, spin, screen printing, etc. It may be coated on the substrate under the condition of temperature range without heating.
  • temperature is usually 40-120 degreeC (preferably 50-100 degreeC), and drying time is And usually 1 to 20 minutes (preferably 2 to 10 minutes).
  • an active energy ray used when hardening the active energy ray curable resin composition coated on the base material for example, light rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, X rays, ⁇ rays and the like
  • light rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, X rays, ⁇ rays and the like
  • electron beams, proton beams, neutron beams and the like can be used, but ultraviolet rays or electron beams, particularly ultraviolet rays are preferable in view of curing speed, availability of an irradiation apparatus, cost and the like.
  • hardening by irradiation of an electron beam even if it does not use a photoinitiator, it can harden
  • UV irradiation When curing by ultraviolet irradiation, use a high pressure mercury lamp, an ultra high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrode discharge lamp, an LED lamp, etc. that emit light in the 150 to 450 nm wavelength range.
  • ultraviolet rays of 30 to 3,000 mJ / cm 2 (preferably 100 to 1,500 mJ / cm 2 ) may be applied. After irradiation with ultraviolet light, heating may be performed as necessary to complete curing.
  • the coating film thickness (film thickness after curing) is usually 1 to 1,000 ⁇ m from the viewpoint of transmitting light so that the photopolymerization initiator reacts 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 particularly preferably used as a coating agent, and particularly preferably used as a coating agent for hard coat or a coating agent for optical film.
  • the active energy ray-curable resin composition of the present invention is excellent in the storage stability of the solution, and further excellent in the scratch resistance when formed into a cured coating film and the antifouling property after scratching.
  • it is useful as a coating agent (further, a coating agent for a hard coat or a coating agent for an optical film), and is also useful as a paint, an ink or the like.
  • the reaction was terminated, and the reaction was terminated when the residual isocyanate group reached 0.1%, to obtain a urethane acrylate composition [I-1] (resin concentration: 100%).
  • the weight average molecular weight of the resulting urethane acrylate composition [I-1] was 1,400, and the viscosity at 60 ° C. was 3,000 mPa ⁇ s.
  • the reaction was terminated when the residual isocyanate group reached 0.3%, to obtain a urethane acrylate composition [I-3] (resin concentration: 100%).
  • the weight average molecular weight of the resulting urethane acrylate composition [I-3] was 1,700, and the viscosity at 60 ° C. was 1,500 mPa ⁇ s.
  • the urethane acrylate composition [I-4] was obtained (resin concentration 100%).
  • the weight average molecular weight of the resulting urethane acrylate composition [I-4] was 3,700, and the viscosity at 60 ° C. was 3,000 mPa ⁇ s.
  • an active energy ray-curable resin composition was produced using the above-mentioned urethane acrylate compositions [I-1] to [I-4].
  • Example 1 While stirring a solution of 100 parts of the urethane acrylate composition [I-1] obtained above in 100 parts of 1-methoxy-2-propanol (boiling point 120 ° C.), the fluorine-containing acrylate compound [II- 1) “KY-1203” (20% active ingredient, weight-average molecular weight (measured value) 27,000 manufactured by Shin-Etsu Chemical Co., Ltd.) 0.2 part (1 part including solvent ingredient) active ingredient, polymerization prohibited 0.3 part of 2,6-di-t-butylcresol as agent [III-1] (urethane acrylate composition [I-1], fluorine-containing acrylate compound [II-1] and polymerization inhibitor [III
  • the active energy ray curable resin composition was obtained by blending 2,990 ppm with respect to the total of 1), and 0.05 parts of "CSP" (manufactured by SEIKO CHEMICAL CO., LTD.) As a coloring
  • the content of the polymerization inhibitor [III] (including the polymerization inhibitor [III ′] used in the production of the urethane acrylate composition) is the urethane acrylate composition [I], the fluorine-containing acrylate compound [I] It was 3,780 ppm with respect to the sum total of II] and polymerization inhibitor [III].
  • Example 2 An active energy ray-curable resin composition was prepared in the same manner as in Example 1 except that the urethane acrylate composition [I-2] was used instead of the urethane acrylate composition [I-1] in Example 1. And an active energy ray-curable resin composition containing a photopolymerization initiator.
  • the content of the polymerization inhibitor [III] (including the polymerization inhibitor [III ′] used in the production of the urethane acrylate composition [I]) is a urethane acrylate composition [I], a fluorine-containing acrylate
  • the amount was 3,380 ppm based on the total of the compound [II] and the polymerization inhibitor [III].
  • Example 3 The same procedure as in Example 1 was repeated except that the content of the fluorine-containing acrylate compound [II-1] was changed to 0.05 parts (0.25 parts in terms of solvent) in the active ingredient in Example 1.
  • the content of the polymerization inhibitor [III] (including the polymerization inhibitor [III ′] used in the production of the urethane acrylate composition [I]) is a urethane acrylate composition [I], a fluorine-containing acrylate
  • the total amount was 3,790 ppm based on the total of the compound [II] and the polymerization inhibitor [III].
  • Example 4 The active energy ray curing is carried out in the same manner as in Example 1 except that the compounding amount of the fluorine-containing acrylate compound [II-1] is changed to 1 part (5 parts in terms of solvent component included) in Example 1 Energy ray curable resin composition containing the water soluble resin composition and the photopolymerization initiator is obtained.
  • the content of the polymerization inhibitor [III] (including the polymerization inhibitor [III ′] used in the production of the urethane acrylate composition [I]) is a urethane acrylate composition [I], a fluorine-containing acrylate It was 3,750 ppm relative to the total of the compound [II] and the polymerization inhibitor [III].
  • Example 5 In Example 1, in place of the fluorine-containing acrylate compound [II-1], “Optool DAC-HP” (20% of active ingredient, manufactured by Daikin Industries, weight average molecular weight An active energy ray-curable resin composition and a photopolymerization initiator in the same manner as in Example 1 except that 0.2 part (1 part in terms of solvent component) was used as the active component (measured value) 2,300) as the active component.
  • the content of the polymerization inhibitor [III] (including the polymerization inhibitor [III ′] used in the production of the urethane acrylate composition [I]) is a urethane acrylate composition [I], a fluorine-containing acrylate
  • the amount was 3,780 ppm based on the total of the compound [II] and the polymerization inhibitor [III].
  • Example 6 In Example 1, in place of the fluorine-containing acrylate compound [II-1], “IRX-380” (active ingredient 10%, manufactured by AGC, weight average molecular weight (measured value) as the fluorine-containing acrylate compound [II-3]
  • the active energy ray-curable resin composition and the photopolymerization initiator are contained in the same manner as in Example 1 except that 0.2 parts (2 parts by solvent included) of 1,300) is used as an active ingredient. An active energy ray curable resin composition was obtained.
  • the content of the polymerization inhibitor [III] (including the polymerization inhibitor [III ′] used in the production of the urethane acrylate composition [I]) is a urethane acrylate composition [I], a fluorine-containing acrylate
  • the amount was 3,780 ppm based on the total of the compound [II] and the polymerization inhibitor [III].
  • Example 7 An active energy ray curable resin composition and a photopolymerization initiator are contained in the same manner as in Example 1 except that the blending amount of the polymerization inhibitor [III-1] is changed to 0.9 part in Example 1. An active energy ray curable resin composition was obtained.
  • the content of the polymerization inhibitor [III] (including the polymerization inhibitor [III ′] used in the production of the urethane acrylate composition [I]) is a urethane acrylate composition [I], a fluorine-containing acrylate It was 9,690 ppm based on the total of the compound [II] and the polymerization inhibitor [III].
  • Example 8 Example 1 is the same as example 1 except that 4-methoxyphenol is used as polymerization inhibitor [III-2] in place of polymerization inhibitor [III-1] 2,6-di-t-butylcresol.
  • an active energy ray curable resin composition containing an active energy ray curable resin composition and a photopolymerization initiator was obtained.
  • the content of the polymerization inhibitor [III] (including the polymerization inhibitor [III ′] used in the production of the urethane acrylate composition [I]) is a urethane acrylate composition [I], a fluorine-containing acrylate
  • the amount was 3,780 ppm based on the total of the compound [II] and the polymerization inhibitor [III].
  • Example 9 In Example 1, instead of the urethane acrylate composition [I-1], 100 parts of the urethane acrylate composition [I-3] and 0.1 parts of “CSP” as the coloring inhibitor [IV-1] An active energy ray curable resin composition containing an active energy ray curable resin composition and a photopolymerization initiator was obtained in the same manner as in Example 1 except for the above.
  • the content of the polymerization inhibitor [III] (including the polymerization inhibitor [III ′] used in the production of the urethane acrylate composition [I]) is a urethane acrylate composition [I], a fluorine-containing acrylate It was 3,580 ppm with respect to the total of the compound [II] and the polymerization inhibitor [III].
  • Example 10 An active energy ray-curable resin composition in the same manner as in Example 9 except that a urethane acrylate composition [I-4] was used in place of the urethane acrylate composition [I-3] in Example 9, and An active energy ray-curable resin composition containing a photopolymerization initiator was obtained.
  • the content of the polymerization inhibitor [III] (including the polymerization inhibitor [III ′] used in the production of the urethane acrylate composition [I]) is a urethane acrylate composition [I], a fluorine-containing acrylate
  • the amount was 3,780 ppm based on the total of the compound [II] and the polymerization inhibitor [III].
  • Example 9 is the same as Example 9 except that the compounding amount of the fluorine-containing acrylate compound [II-1] is changed to 0.05 parts (0.25 parts in terms of the solvent component) in terms of the active ingredient.
  • An active energy ray curable resin composition containing an active energy ray curable resin composition and a photopolymerization initiator was obtained.
  • the content of the polymerization inhibitor [III] (including the polymerization inhibitor [III ′] used in the production of the urethane acrylate composition [I]) is a urethane acrylate composition [I], a fluorine-containing acrylate It was 3,590 ppm with respect to the total of the compound [II] and the polymerization inhibitor [III].
  • Example 12 The active energy ray curability is the same as in Example 9, except that in Example 9, the compounding amount of the fluorine-containing acrylate compound [II-1] is changed to 1 part (5 parts in terms of solvent) including the active ingredient.
  • An active energy ray curable resin composition containing a resin composition and a photopolymerization initiator was obtained.
  • the content of the polymerization inhibitor [III] (including the polymerization inhibitor [III ′] used in the production of the urethane acrylate composition [I]) is a urethane acrylate composition [I], a fluorine-containing acrylate It was 3,550 ppm relative to the total of the compound [II] and the polymerization inhibitor [III].
  • Example 13 In Example 9, in place of the fluorine-containing acrylate compound [II-1], “Optool DAC-HP” (20% of active ingredient, manufactured by Daikin Industries, weight average molecular weight Measured value: 2,300) The active energy ray-curable resin composition and the photopolymerization initiator were prepared in the same manner as in Example 9, except that 0.2 part (1 part in the solvent component included) was used as the active component. The active energy ray curable resin composition to be contained was obtained.
  • the content of the polymerization inhibitor [III] (including the polymerization inhibitor [III ′] used in the production of the urethane acrylate composition [I]) is a urethane acrylate composition [I], a fluorine-containing acrylate It was 3,580 ppm with respect to the total of the compound [II] and the polymerization inhibitor [III].
  • Example 14 In Example 9, in place of the fluorine-containing acrylate compound [II-1], “IRX-380” (active ingredient 10%, product of AGC, weight average molecular weight (measured value) as the fluorine-containing acrylate compound [II-3]
  • the active energy ray curable resin composition and the photopolymerization initiator are contained in the same manner as in Example 9 except that 0.2 part (2 parts in terms of solvent) is used as the active ingredient). An active energy ray-curable resin composition was obtained.
  • the content of the polymerization inhibitor [III] (including the polymerization inhibitor [III ′] used in the production of the urethane acrylate composition [I]) is a urethane acrylate composition [I], a fluorine-containing acrylate It was 3,580 ppm with respect to the total of the compound [II] and the polymerization inhibitor [III].
  • Example 15 An active energy ray curable resin composition and a photopolymerization initiator are contained in the same manner as in Example 9 except that the blending amount of the polymerization inhibitor [III-1] is changed to 0.9 part in Example 9. An active energy ray curable resin composition was obtained.
  • the content of the polymerization inhibitor [III] (including the polymerization inhibitor [III ′] used in the production of the urethane acrylate composition [I]) is a urethane acrylate composition [I], a fluorine-containing acrylate It was 9,500 ppm based on the total of the compound [II] and the polymerization inhibitor [III].
  • Example 9 is the same as Example 9 except that in place of the polymerization inhibitor [III-1] 2,6-di-t-butylcresol, 4-methoxyphenol is used as the polymerization inhibitor [III-2]. Similarly, an active energy ray curable resin composition containing an active energy ray curable resin composition and a photopolymerization initiator was obtained.
  • the content of the polymerization inhibitor [III] (including the polymerization inhibitor [III ′] used in the production of the urethane acrylate composition [I]) is a urethane acrylate composition [I], a fluorine-containing acrylate It was 3,580 ppm with respect to the total of the compound [II] and the polymerization inhibitor [III].
  • Example 17 An active energy ray curable resin composition containing an active energy ray curable resin composition and a photopolymerization initiator in the same manner as in Example 9 except that the coloring inhibitor [IV-1] is not used in Example 9. I got a thing.
  • the content of the polymerization inhibitor [III] (including the polymerization inhibitor [III ′] used in the production of the urethane acrylate composition [I]) is a urethane acrylate composition [I], a fluorine-containing acrylate It was 3,580 ppm with respect to the total of the compound [II] and the polymerization inhibitor [III].
  • Comparative Example 1 An active energy ray-curable composition containing an active energy ray-curable resin composition and a photopolymerization initiator in the same manner as in Example 1 except that the fluorine-containing acrylate compound [II-1] is not used in Example 1. A resin composition was obtained.
  • the content of the polymerization inhibitor [III] (including the polymerization inhibitor [III ′] used in the production of the urethane acrylate composition) is the urethane acrylate composition [I], the fluorine-containing acrylate compound [I] It was 3,790 ppm with respect to the sum total of II] and polymerization inhibitor [III].
  • Comparative Example 2 An active energy ray curable resin composition containing an active energy ray curable resin composition and a photopolymerization initiator in the same manner as in Example 1 except that the polymerization inhibitor [III-1] is not used in Example 1. I got a thing.
  • the content of the polymerization inhibitor [III] (including the polymerization inhibitor [III ′] used in the production of the urethane acrylate composition) is the urethane acrylate composition [I], the fluorine-containing acrylate compound [I] It was 800 ppm with respect to the sum total of II] and polymerization inhibitor [III].
  • Example 9 an active energy ray-curable composition containing an active energy ray-curable resin composition and a photopolymerization initiator in the same manner as in Example 9 except that the fluorine-containing acrylate compound [II-1] is not used.
  • a resin composition was obtained.
  • the content of the polymerization inhibitor [III] (including the polymerization inhibitor [III ′] used in the production of the urethane acrylate composition) is the urethane acrylate composition [I], the fluorine-containing acrylate compound [I] It was 3,590 ppm with respect to the sum total of II] and polymerization inhibitor [III].
  • Comparative Example 4 An active energy ray curable resin composition containing an active energy ray curable resin composition and a photopolymerization initiator in the same manner as in Example 9 except that the polymerization inhibitor [III-1] is not used in Example 9. I got a thing.
  • the content of the polymerization inhibitor [III] (including the polymerization inhibitor [III ′] used in the production of the urethane acrylate composition) is the urethane acrylate composition [I], the fluorine-containing acrylate compound [I] It was 600 ppm with respect to the sum total of II] and polymerization inhibitor [III].
  • Example 9 Comparative Example 5 In Example 9, except that trimethylolpropane triacrylate (manufactured by Toagosei Co., Ltd., “Alonix M-309”, containing 100 ppm of a polymerization inhibitor) was used in place of the urethane acrylate composition [I-3]. In the same manner as in Example 9, an active energy ray-curable resin composition containing an active energy ray-curable resin composition and a photopolymerization initiator was obtained.
  • trimethylolpropane triacrylate manufactured by Toagosei Co., Ltd., “Alonix M-309”, containing 100 ppm of a polymerization inhibitor
  • the content of the polymerization inhibitor [III] (including the polymerization inhibitor contained in trimethylolpropane triacrylate) is the total of trimethylolpropane, fluorine-containing acrylate compound [II] and polymerization inhibitor [III] against 3,090 ppm.
  • the liquid storage stability of the active energy ray curable resin composition obtained above was evaluated by the following method.
  • the Hazen color number (APHA) of the above-mentioned active energy ray-curable resin composition was measured using a spectrocolorimeter "SE6000: manufactured by Nippon Denshoku Kogyo Co., Ltd.”.
  • the active energy ray-curable resin composition was placed in a closed glass test container, and subjected to a heat resistance test under heat resistance conditions (stored for 4 weeks in a 60 ° C. environment) to measure the value of APHA after the heat resistance test.
  • the results are shown in Tables 1 to 3 below.
  • the active energy ray-curable resin composition containing the photopolymerization initiator obtained above is applied onto an easily-adhered PET film (Toyobo Co., Ltd., “Cosmo Shine A4300, thickness 125 ⁇ m) substrate, The coating is applied so that the film thickness after drying is 5 ⁇ m, and after drying at 90 ° C. for 3 minutes, using a 80 W high-pressure mercury lamp, 1 lamp, from a height of 18 cm to a conveyor speed of 5.1 m / min 2 The pass was irradiated with ultraviolet light (accumulated irradiation amount: 450 mJ / cm 2 ) to form a cured coating film.
  • ultraviolet light accumulated irradiation amount: 450 mJ / cm 2
  • the composition containing the urethane (meth) acrylate composition [I] and the fluorine-containing (meth) acrylate compound [II] further contains a predetermined amount of the polymerization inhibitor [III]
  • the storage stability in the coating liquid was excellent.
  • the example contains the polymerization inhibitor [III] more than Comparative Examples 2 and 4, it is also excellent in antifouling performance and scratch resistance when made into a cured coating film. there were.
  • Comparative Examples 1 and 3 which do not contain the fluorine-containing (meth) acrylate compound [II], they are inferior in antifouling performance and scratch resistance and other than the production of the urethane (meth) acrylate composition [I]
  • Comparative Examples 2 and 4 in which the blending of the polymerization inhibitor [III] was not performed, the storage stability of the solution was inferior.
  • Comparative Example 5 in which the urethane (meth) acrylate composition [I] was not used, the curability was insufficient, and the object of the present invention was not satisfied.
  • the active energy ray-curable resin composition of the present invention is excellent in the storage stability of the coating solution, and has antifouling performance (contamination resistance and its persistence), properties of the cured coating (appearance, hardness, scratch resistance) (6) can be formed, and is useful as a coating agent, in particular, a coating agent for a hard coat or a coating agent for an optical film. It is also useful as a paint, an ink and the like.

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

Abstract

À titre de composition de résine durcissable par rayonnement d'énergie active ayant une excellente stabilité au stockage d'une solution de revêtement et capable de former un film de revêtement ayant d'excellentes performances antisalissures (résistance à la contamination et durabilité de celle-ci) et autres propriétés (aspect, dureté, résistance à l'abrasion), la présente invention propose une composition de résine durcissable par rayonnement d'énergie active qui contient : une composition de (méth)acrylate d'uréthane [I] obtenue par réaction d'un groupe hydroxyle contenu dans un additif (A) de type acide (méth)acrylique de polyalcool et d'un groupe isocyanate contenu dans un composé de polyisocyanate (B) l'un avec l'autre ; un composé de (méth)acrylate contenant du fluor [II] ; et un inhibiteur de polymérisation [III]. La teneur en inhibiteur de polymérisation [III] représente de 800 à 10 000 ppm sur une base en poids total combiné de la composition de (méth)acrylate d'uréthane [I], du composé de (méth)acrylate contenant du fluor [II], et de l'inhibiteur de polymérisation [III].
PCT/JP2018/045067 2017-12-14 2018-12-07 Composition de résine durcissable par rayonnement d'énergie active et agent de revêtement Ceased WO2019117030A1 (fr)

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CN201880069383.4A CN111278880A (zh) 2017-12-14 2018-12-07 活性能量射线固化性树脂组合物及涂布剂

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JP2013023548A (ja) * 2011-07-19 2013-02-04 Bridgestone Corp 光硬化性樹脂組成物、並びに、それを用いた水周り部材及び機能性パネル
WO2013151119A1 (fr) * 2012-04-06 2013-10-10 東亞合成株式会社 Composition durcissable sous énergie active pour formation de couche optique
WO2014034030A1 (fr) * 2012-08-28 2014-03-06 株式会社ブリヂストン Élément ayant une couche durcie formé par durcissement d'une composition de résine durcissable sur au moins une surface de celui-ci
JP2014091776A (ja) * 2012-11-02 2014-05-19 Dic Corp 活性エネルギー線硬化性組成物、その硬化物及びその硬化塗膜を有する物品

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JP5162306B2 (ja) * 2008-04-03 2013-03-13 精工化学株式会社 着色防止剤
JP6217208B2 (ja) * 2013-07-22 2017-10-25 東亞合成株式会社 活性エネルギー線硬化型組成物
WO2016043263A1 (fr) * 2014-09-19 2016-03-24 横浜ゴム株式会社 Composition de résine durcissable à la lumière ultraviolette et stratifié l'utilisant
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JP2005283849A (ja) * 2004-03-29 2005-10-13 Fuji Photo Film Co Ltd 硬化性樹脂組成物、それを用いた反射防止フィルムの製造方法、反射防止フィルム、偏光板、および画像表示装置
JP2013023548A (ja) * 2011-07-19 2013-02-04 Bridgestone Corp 光硬化性樹脂組成物、並びに、それを用いた水周り部材及び機能性パネル
WO2013151119A1 (fr) * 2012-04-06 2013-10-10 東亞合成株式会社 Composition durcissable sous énergie active pour formation de couche optique
WO2014034030A1 (fr) * 2012-08-28 2014-03-06 株式会社ブリヂストン Élément ayant une couche durcie formé par durcissement d'une composition de résine durcissable sur au moins une surface de celui-ci
JP2014091776A (ja) * 2012-11-02 2014-05-19 Dic Corp 活性エネルギー線硬化性組成物、その硬化物及びその硬化塗膜を有する物品

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