WO2019124190A1 - (meth)acrylic composition manufacturing method, (meth)acrylic composition-containing coating, and hardened product - Google Patents

(meth)acrylic composition manufacturing method, (meth)acrylic composition-containing coating, and hardened product Download PDF

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Publication number
WO2019124190A1
WO2019124190A1 PCT/JP2018/045688 JP2018045688W WO2019124190A1 WO 2019124190 A1 WO2019124190 A1 WO 2019124190A1 JP 2018045688 W JP2018045688 W JP 2018045688W WO 2019124190 A1 WO2019124190 A1 WO 2019124190A1
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carbon atoms
group
meth
acrylate
general formula
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PCT/JP2018/045688
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French (fr)
Japanese (ja)
Inventor
和起 河野
竜也 宇多村
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三菱瓦斯化学株式会社
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Application filed by 三菱瓦斯化学株式会社 filed Critical 三菱瓦斯化学株式会社
Priority to KR1020207015454A priority Critical patent/KR20200090791A/en
Priority to JP2019561007A priority patent/JP7351222B2/en
Priority to CN201880081273.XA priority patent/CN111491963B/en
Publication of WO2019124190A1 publication Critical patent/WO2019124190A1/en

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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
    • 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
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • 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
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • 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
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C08J2333/00—Characterised by the use 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; Derivatives of such polymers
    • C08J2333/04—Characterised by the use 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; Derivatives of such polymers esters
    • C08J2333/14—Characterised by the use 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; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen

Definitions

  • the present invention relates to a method for producing a (meth) acrylic composition, and a paint comprising the (meth) acrylic composition.
  • the present invention also relates to a cured product of this composition.
  • Patent Document 1 a specific ratio of o-phenylbenzyl acrylate (OPBA; or 2-phenylbenzyl acrylate), which is an isomer of phenylbenzyl acrylate, and p-phenylbenzyl acrylate (PPBA; or 4-phenylbenzyl acrylate) is used.
  • OPBA o-phenylbenzyl acrylate
  • PPBA p-phenylbenzyl acrylate
  • Patent Document 2 describes that a composition having a high refractive index and a low viscosity can be obtained by mixing phenylbenzyl acrylate and a difunctional (meth) acrylate or a diphenyl derivative.
  • Patent Documents 3 to 7 disclose that a resin composition for an optical material is obtained by mixing phenoxybenzyl (meth) acrylate and a polyfunctional (meth) acrylate (fluorene-based bisphenol derivative or bisphenol A derivative) having a high refractive index. It is done.
  • the present invention is directed to such problems, wherein the viscosity of the composition is low, the refractive index is high when cured, and the (meth) acrylic composition less yellowing in environmental tests under high temperature and high humidity conditions. It is an object of the present invention to provide a method of production and a paint comprising such (meth) acrylic composition. Another object of the present invention is to provide a cured product of the above composition.
  • R 13 and R 14 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent,
  • the substituents are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms;
  • c represents an integer of 1 to 20.
  • R 15 and R 16 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or 1 carbon atom which may have a substituent] Alkoxy group of ⁇ 5, aryl group having 6 to 12 carbon atoms which may have a substituent, alkenyl group having 2 to 5 carbon atoms which may have a substituent, and carbon number which may have a substituent Or any one of the group consisting of 7 to 17 aralkyl groups, or R 15 and R 16 respectively bond to each other to form a carbocyclic ring or heterocyclic ring having 1 to 20 carbon atoms;
  • the substituents are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
  • R 17 to R 20 each independently represent a hydrogen atom, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a carbon number which may have a substituent 1 to 5 alkoxy group, optionally substituted aryl group having 6 to 12 carbon atoms, optionally substituted alkenyl group having 2 to 5 carbon atoms and carbon optionally having substituent group
  • R 17 and R 18 and R 19 and R 20 are each bonded to each other to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms.
  • R 21 to R 30 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • a method of producing a liquid composition comprising Including mixing the (meth) acrylate represented by the said General formula (1) with the polyvalent (meth) acrylic-type monomer represented by the said General formula (2) at the temperature of 35 degreeC or more and 120 degrees C or less ,Method. [2] The method according to [1], wherein in the formula (1), p and q are both 0.
  • a method for producing a (meth) acrylic composition having a low viscosity of the composition, a high refractive index upon curing, and less yellowing in environmental tests under high temperature and humidity is possible to provide a paint comprising a (meth) acrylic composition.
  • a cured product of the above composition can be provided.
  • a method of producing a liquid composition comprising Mixing the (meth) acrylate represented by the general formula (1) with the polyvalent (meth) acrylic monomer represented by the general formula (2) at a temperature of 35 ° C. or more and 120 ° C. or less .
  • Patent Document 1 discloses that p-phenylbenzyl (meth) acrylate which is a kind of (meth) acrylate having a structure of the general formula (1) is solid at normal temperature (mp: 32 ° C.). It is considered that it can not be used.
  • a liquid composition is obtained by mixing o-phenylbenzyl (meth) acrylate which is liquid at normal temperature and p-phenylbenzyl (meth) acrylate in a specific ratio.
  • the present inventors liquefy the (meth) acrylate having the structure of the general formula (1) by heating the (meth) acrylate having the structure of the general formula (1) to a predetermined temperature range.
  • a liquid composition can be obtained by mixing with the polyvalent (meth) acrylic monomer having the structure of the general formula (2) in that state.
  • the (meth) acrylate having the structure of the general formula (1) is liquefied and then mixed with the polyvalent (meth) acrylic monomer having the structure of the general formula (2).
  • the liquid composition thus obtained had a low viscosity, had a high refractive index upon curing, and exhibited little yellowing in environmental tests under high temperature and high humidity.
  • the present invention is based on such findings.
  • the temperature at which the (meth) acrylate having the structure of the general formula (1) in the production method of the present invention is mixed with the polyvalent (meth) acrylic monomer having the structure of the general formula (2) is 35 ° C. or higher It is 120 ° C. or less, preferably 40 ° C. or more and 100 ° C. or less, and more preferably 45 ° C. or more and 80 ° C. or less. If the temperature at the time of mixing is 35 ° C. or more, the (meth) acrylate having the structure of the general formula (1) can be sufficiently liquefied, and if it is 120 ° C. or less, the polymerization of the monomer can be prevented.
  • the temperature of the (meth) acrylate having at least the structure of the general formula (1) may be adjusted to the above temperature range, and a polyvalent (meth) acrylic monomer having the structure of the general formula (2) May be mixed at normal temperature.
  • the viscosity of the liquid composition of the present invention is less than 10,000 mPa ⁇ s when measured at a measurement temperature of 25 ° C. using an E-type viscometer (TV-22 type), preferably 5,000 mPa ⁇ s. s or less, more preferably 5 to 2,000 mPa ⁇ s.
  • (Meth) Acrylate The (meth) acrylate used in the composition obtained by the production method of the present invention has a structure represented by the following general formula (1).
  • R 2 and R 3 each independently represent a hydrogen atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms, It is a linear alkoxy group having 1 to 10 carbon atoms, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon carbon atom
  • Y is an alkylene group having 2 to 6 carbon atoms which may be branched, a cycloalkylene group having 6 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms.
  • R 1 is a hydrogen atom or a methyl group, preferably a hydrogen atom.
  • R 4 and R 5 each independently represent a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, or 1 to 10 carbon atoms And a linear alkoxy group, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a halogen atom, a phenyl group or a phenylphenyl group.
  • n is an integer of 1 to 2, preferably 1. More preferably, n is 1 and m is 0.
  • p is an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0.
  • q is an integer of 0 to 5, preferably an integer of 0 to 2, and more preferably 0. More preferably, p and q are both 0. When p and q are 0, it means that the hydrogen of the benzene ring is not substituted by the functional group of R 4 or R 5 .
  • Examples of the (meth) acrylate represented by the above general formula (1) include 4-phenylbenzyl (meth) acrylate, 3-phenylbenzyl (meth) acrylate, 2-phenylbenzyl (meth) acrylate, 4-biphenylbenzyl (Meth) acrylate, 3-biphenyl benzyl (meth) acrylate, 2-biphenyl benzyl (meth) acrylate, 4-benzyl benzyl (meth) acrylate, 3-benzyl benzyl (meth) acrylate, 2-benzyl benzyl (meth) acrylate, 4-phenethyl benzyl (meth) acrylate, 3-phenethyl benzyl (meth) acrylate, 2-phenethyl benzyl (meth) acrylate, 4-phenethyl phenethyl (meth) acrylate, 3-phenethyl benzyl (meth) acryl
  • the (meth) acrylate may be a blend of two or more types of compounds, in which case at least one type of methacrylate may be a (meth) acrylate represented by the above general formula (1).
  • the above (meth) acrylates preferred are 2-phenylbenzyl (meth) acrylate, 4-phenylbenzyl (meth) acrylate, 4-phenoxybenzyl (meth) acrylate and 4-benzylbenzyl (meth) acrylate, More preferably, 2-phenylbenzyl acrylate, 4-phenylbenzyl acrylate, 4-phenoxybenzyl acrylate and 4-benzyl benzyl acrylate.
  • the compounding quantity of (meth) acrylate contained in the composition obtained by the manufacturing method of this invention is not specifically limited if it is a range which does not deviate from the main point of this invention, (meth) acrylate and General formula (2)
  • the content of the polyvalent (meth) acrylic monomer to be added is preferably 1: 9 to 9: 1 by mass ratio, more preferably 2: 8 to 8: 2, and 3: 7 It is further preferable that the ratio is -7: 3, and particularly preferably 4: 6 to 6: 4.
  • the higher the ratio of monofunctional (meth) acrylates the more preferable in that peeling at high temperature and high humidity can be prevented. Without being bound by theory, it is presumed that the decrease in adhesion between the substrate and the cured product is caused by a large water absorption.
  • Multivalent (Meth) Acrylic-Based Monomer The composition obtained by the production method of the present invention can be copolymerized with the (meth) acrylate represented by the above general formula (1), which is represented by the following general formula (2) It further contains a multivalent (meth) acrylic monomer represented by
  • R 10 and R 11 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or the like It is selected from a cycloalkoxyl group of 5 to 20, an aryl group of 6 to 20 carbon atoms, an aryloxy group of 6 to 20 carbon atoms, and a halogen atom, preferably a hydrogen atom.
  • R 12 is a hydrogen atom or a methyl group.
  • X represents a structure of any of the group consisting of a single bond, -O-, -S-, -SO-, -SO 2- , -CO- and the following general formulas (3) to (6).
  • Y and Z each independently represent an alkylene group having 2 to 6 carbon atoms which may be branched, a cycloalkylene group having 6 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms.
  • p and q are each independently an integer of 0 to 4, and preferably both p and q are 0.
  • R 13 and R 14 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, The aryl group having 6 to 12 carbon atoms which may have a group, the alkenyl group having 2 to 5 carbon atoms which may have a substituent, and the aralkyl group having 7 to 17 carbon atoms which may have a substituent And the substituents each independently represent a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
  • both R 13 and R 14 are hydrogen atoms.
  • c represents an integer of 1 to 20, preferably an integer of 1 to 10, more preferably an integer of 1 to 5.
  • R 15 and R 16 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, An aryl group having 6 to 12 carbon atoms which may have a group, an alkenyl group having 2 to 5 carbon atoms which may have a substituent, and an aralkyl group having 7 to 17 carbon atoms which may have a substituent R 15 and R 16 are each bonded to each other to form a carbocyclic ring or a heterocyclic ring having 1 to 20 carbon atoms, and the substituents each independently represent a halogen atom or a carbon atom. It is an alkyl group of 1 to 20 or an aryl group of 6 to 12 carbon atoms.
  • R 15 and R 16 are both hydrogen atoms.
  • R 17 to R 20 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, The aryl group having 6 to 12 carbon atoms which may have a substituent, the alkenyl group having 2 to 5 carbon atoms which may have a substituent, and the aralkyl group having 7 to 17 carbon atoms which may have a substituent Or R 17 and R 18 and R 19 and R 20 respectively bind to each other to form a carbocyclic ring or heterocyclic ring having 1 to 20 carbon atoms, and the substituents are Each of them is independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
  • R 17 to R 20 are both hydrogen atoms.
  • R 21 to R 30 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • R 21 to R 30 are both hydrogen atoms.
  • X has a structure shown by General formula (4).
  • Examples of the polyvalent (meth) acrylic monomers represented by the above general formula (2) include 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 4,4 '-Isopropylidenediphenol di (meth) acrylate, 2,2'-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] propane, bis [4- (2- (meth) acryloyloxyethoxy) phenyl Methane, 1,1′-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] methane, bis [4- (2- (meth) acryloyloxyethoxy) phenyl] ether, bis [4- (2) -(Meth) acryloyloxyethoxy) phenyl] sulfoxide, bis [4- (2- (meth) acryloyloxyethoxy) phenyl]
  • composition obtained by the production method of the present invention may contain various optional additives in addition to the above-mentioned components according to the application without departing from the scope of the present invention.
  • additives include at least one additive selected from the group consisting of heat stabilizers, antioxidants, flame retardants, flame retardant aids, UV absorbers, mold release agents and colorants.
  • Ru The compounding amount of the additive is 100 parts by mass in total of the (meth) acrylate represented by the general formula (1) and the polyvalent (meth) acrylic monomer represented by the general formula (2). The amount is preferably 0.005 parts by mass to 0.1 parts by mass, and more preferably 0.01 parts by mass to 0.05 parts by mass.
  • composition obtained by the method of the present invention can be cured by various methods. Although the details will be described later, the composition obtained by the method of the present invention is preferably an active energy ray curable composition.
  • the paint of the present invention comprises the composition obtained by the method of the present invention.
  • the paint of the present invention can be mainly used for applications such as a coating agent for an optical member and a hard coating agent.
  • a wetting agent such as a silicone or an acrylic compound may be added to the paint in order to assist the surface of various substrates to be wetted.
  • Suitable humectants include BYK 331, BYK 333, BYK 340, BYK 347, BYK 348, BYK 378, BYK 380, BYK 381 and the like available from Bick Chemie. When these are added, the range of 0.01 to 2.0% by mass is preferable based on the total mass of the paint.
  • tackifiers such as a xylene resin, a terpene resin, a phenol resin, rosin resin, in a coating material as needed.
  • tackifiers such as a xylene resin, a terpene resin, a phenol resin, rosin resin
  • a coupling agent such as a silane coupling agent or a titanium coupling agent may be added to the paint.
  • a coupling agent such as a silane coupling agent or a titanium coupling agent may be added to the paint.
  • the range of 0.01 to 5.0% by mass is preferable based on the total mass of the paint.
  • inorganic fillers such as silica, alumina, mica, talc, aluminum flakes and glass flakes may be added to the paint. When these are added, the range of 0.01 to 10.0% by mass is preferable based on the total mass of the paint.
  • silicone or acrylic compound is added to the paint in order to aid the disappearance of bubbles generated during stirring and mixing. May be added.
  • Suitable antifoam agents include BYK019, BYK052, BYK065, BYK066N, BYK067N, BYK070, BYK080, etc., which are available from Bick Chemie, with BYK065 being particularly preferred. When these are added, the range of 0.01 to 3.0% by mass is preferable based on the total mass of the paint.
  • rust-preventive additives such as zinc phosphate, iron phosphate, calcium molybdate, vanadium oxide, water-dispersed silica, fumed silica, phthalocyanine-based organic pigments, condensed polycyclic organic compounds
  • rust-preventive additives such as zinc phosphate, iron phosphate, calcium molybdate, vanadium oxide, water-dispersed silica, fumed silica, phthalocyanine-based organic pigments, condensed polycyclic organic compounds
  • a necessary amount of each component such as an organic pigment such as pigment, an inorganic pigment such as titanium oxide, zinc oxide, calcium carbonate, barium sulfate, alumina, carbon black may be added.
  • coating methods for applying the paint of the present invention on various substrates include bar coater coating, mayer bar coating, air knife coating, gravure coating, reverse gravure coating, microgravure coating, and micro Commonly used coating methods such as reverse gravure coater coating, die coater coating, slot die coater coating, vacuum die coater coating, dip coating, spin coating coating, spray coating, and brush coating Both may be used. Roll application or spray application is preferred.
  • the cured product of the present invention is a cured product obtained by curing the composition obtained by the method of the present invention.
  • the cured product of the present invention has a high refractive index of 1.580 or more, and less yellowing in environmental tests under high temperature and high humidity.
  • the cured product of the present invention preferably has a high refractive index of 1.585 or more, and more preferably a high refractive index of 1.590 or more.
  • the cured product of the present invention preferably has a yellowness (YI) of 4.0 or less when stored in an atmosphere at 85 ° C./85% RH for 350 hours, and 1 in an atmosphere at 85 ° C./85% RH It is preferable that the yellowness (YI) at the time of storing for 2,000 hours is 6.5 or less.
  • the cured product of the present invention is (A) Structural units derived from (meth) acrylates represented by the general formula (1) and Structural units derived from multivalent (meth) acrylic monomers represented by the general formula (2) including.
  • X, Y, R 1 , R 4 , R 5 , m, n, p and q in the general formula (1) are respectively the same as those of the composition obtained by the method of the present invention.
  • R 10 , R 11 , R 12 , X, Y, Z, p and q in the general formula (2) are respectively the same as those of the composition obtained by the method of the present invention.
  • led-out from the (meth) acrylate represented by General formula (1) shows the structural unit which has a structure of following formula (1a)
  • the structural unit derived from the multivalent (meth) acrylic monomer represented by the general formula (2) indicates a structural unit having a structure of the following formula (2a).
  • X, Y, R 1 , R 4 , R 5 , m, n, p and q in the general formula (1a) correspond to those in the general formula (1), respectively, and R in the general formula (2a) 10 , R 11 , R 12 , X, Y, Z, p and q correspond to those of the general formula (2).
  • the method for producing a cured product of the present invention includes the steps of obtaining a composition by the method of the present invention and curing the composition.
  • the method of curing is not particularly limited, and may be performed by various known methods.
  • the composition of the present invention may be cured by photopolymerization by irradiating active energy rays.
  • active energy ray means ultraviolet light, electron beam, ion beam, X-ray and the like.
  • a photopolymerization initiator is not necessarily required.
  • a photoinitiator for example, Irgacure® 2959 (1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-l available from Ciba Propan-1-one, Irgacure® 184 (1-hydroxycyclohexyl phenyl ketone), Irgacure® 500 (1-hydroxycyclohexyl phenyl ketone, benzophenone), Irgacure® 651 (2, 2-dimethoxyamine) -1,2-Diphenylethan-1-one), Irgacure 369 (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1), Irgacure 907 ( 2-Methyl-1 [4-methylthiophen [Nyl] -2-morpholinoprop
  • MP-triazine (2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine) manufactured by Sanwa Chemical Co., Ltd., manufactured by Midori Chemical AZ-113 (2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine), Midori Kagaku TAZ-108 (2- (3 , 4-Dimethoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine), benzophenone, 4,4'-bisdiethylaminobenzophenone, methyl-2-benzophenone, 4-benzoyl-4'- Methyl diphenyl sulfide, 4-phenyl benzophenone, ethyl Michler's ketone, 2-chlorothioxanthone, 2-methyl thioxanthone, 2-is
  • Part and “%” in an Example represent “mass part” and “mass%”, respectively.
  • composition Viscosity The viscosity of the composition obtained by the method described below was measured at a measurement temperature of 25 ° C. using an E-type viscometer (TV-22 type).
  • the refractive index of the composition The composition obtained by the method described below was measured at a measurement wavelength of 589 nm at a measurement temperature of 23 ° C. using a multi-wavelength Abbe refractometer DR-M2 (manufactured by Atago Co., Ltd.). It was measured.
  • Refractive Index of Cured Product A cured product of the composition obtained by the method described below is measured using a multi-wavelength Abbe refractometer DR-M2 (manufactured by Atago Co., Ltd.) at a measurement wavelength of 589 nm and a measurement temperature of 23 It measured at ° C.
  • Yellowness (YI) The yellowness (YI) was measured according to JIS K 7373 using a haze meter NDH4000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.).
  • Example 1 Preparation of composition and its cured product>
  • the liquid composition with the composition of Table 1 Examples 1 to 13 were prepared. Blend the monofunctional (meth) acrylate with the polyvalent (meth) acrylic monomer represented by the general formula (2) whose viscosity is lowered by heating at 60 ° C. for 1 hour, and stir well The solution was uniformly dissolved to obtain a liquid composition. Next, the temperature of the composition was brought to 23 ° C. by storing for 12 hours under an atmosphere of 23 ° C. Thereafter, the viscosity and the refractive index were measured.
  • the following compounds were used as the compounds of chemical formulas (A) to (D).
  • the compound of the formula (D) was synthesized by a known method using POB-A manufactured by the company. Specifically, the synthesis method of the compound of the chemical formula (D) is as follows.
  • Example 2 Physical Properties of Each Liquid Composition and Its Cured Body> Liquid composition examples 14 to 16 comprising a monofunctional (meth) acrylate and a polyvalent (meth) acrylic monomer represented by the general formula (2) in a ratio of 50:50 are prepared, the composition and Various physical properties of the cured product were measured. 20 parts by mass of the polyvalent (meth) acrylic monomer represented by the general formula (2) whose viscosity is lowered by heating at 60 ° C.
  • a pencil is pressed on the surface of the dried coated film in order from the lowest hardness at an angle of 45 degrees and a load of 750 g against the surface of the polyester film on which the cured product of the liquid composition is formed.
  • the hardness of the hardest pencil was evaluated as pencil hardness.
  • the pencil hardness is shown by 2B, B, HB, F, H, 2H, 3H, 4H, 5H, 6H and 7H in ascending order of rank.
  • [Elongation] 20 parts by mass of the polyvalent (meth) acrylic monomer represented by the general formula (2) whose viscosity is lowered by heating at 60 ° C.
  • a liquid composition was obtained by blending 1.2 parts by mass of Irugacure 184 (manufactured by Ciba Specialty Chemicals), which is a photopolymerization initiator, and thoroughly stirring to dissolve uniformly. Next, a liquid composition was applied to the non-corona treated surface of a 50 ⁇ m thick polyester film (Toyobo Co., Ltd .; Toyobo Ester Film E5100), which is a substrate, as a bar coater No.
  • the haze was measured according to JIS K 7136 using a haze meter NDH4000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.).
  • Total light transmittance The total light transmittance (TT) was measured according to JIS K 7375 using a haze meter NDH4000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.).
  • saturated water absorption rate A cured product of the liquid composition was made as described above, and a 5 cm ⁇ 5 cm sample piece was made and dried at 50 ° C. for 24 hours.
  • Example 3 Coloring evaluation under high temperature and high humidity of each liquid composition and its cured product> Liquid composition examples 17 to 25 containing monofunctional (meth) acrylate and the polyvalent (meth) acrylic monomer represented by the general formula (2) in the proportions described in Table 3 are prepared, and respective high temperature The coloration under high humidity was evaluated. At the time of preparation, the polyvalent (meth) acrylic monomer represented by the general formula (2) whose viscosity is lowered by heating at 60 ° C. for 1 hour is monofunctional in the ratio described in Table 3 Mixed with methacrylate. At the same time, the occurrence of peeling under high temperature and high humidity was also confirmed. The polyester film on which the cured product of the liquid composition is formed is stored in a constant temperature and humidity chamber set at 85 ° C./85% RH atmosphere, and yellowness is measured by the above measuring method at 350 hours and 1000 hours. (YI) was measured.
  • Example 4 Evaluation of Crystallization Liquid composition examples 26 to 49 containing monofunctional (meth) acrylate and polyvalent (meth) acrylic monomer represented by the general formula (2) in the proportions described in Tables 4 to 6 are prepared, It was evaluated whether changing the blending temperature affects the generation of crystals. The results are shown in Tables 4 to 7.
  • Chemical formula (D) / (C) means a mixture of the compound of chemical formula (D) and the compound of chemical formula (C) in a weight ratio of 1: 1.
  • Example 5 Solubility of Multivalent (Meth) Acrylic-Based Monomer Represented by Crystallized General Formula (2)>
  • the polyvalent (meth) acrylic monomer represented by the general formula (2) is already crystallized before blending with the monofunctional (meth) acrylate, it is blended with the heated monofunctional (meth) acrylate It was evaluated whether the crystals dissolved.
  • a monofunctional (meth) acrylate and a polyvalent (meth) acrylic monomer are mixed at each blending temperature, and then the polyvalent (meth) acrylic monomer crystallized by maintaining at 60 ° C. It was evaluated whether it was dissolved.
  • the results are shown in Table 8.
  • surface means the grade of melt

Abstract

The present invention provides: a method for manufacturing a (meth)acrylic composition which has low viscosity, exhibits high refractive index when hardened, and is less susceptible to yellowing after undergoing an environmental test at high temperature and high humidity; and a coating containing such a (meth)acrylic composition. The method according to one embodiment of the present invention comprises mixing, within a prescribed temperature range, a (meth)acrylate represented by general formula (1) with a multivalent (meth)acrylic monomer represented by general formula (2).

Description

（メタ）アクリル系組成物の製造方法、（メタ）アクリル系組成物を含む塗料および硬化体Method for producing (meth) acrylic composition, paint containing (meth) acrylic composition and cured product
　本発明は、（メタ）アクリル系組成物の製造方法、および（メタ）アクリル系組成物を含む塗料に関する。また、本発明は、この組成物の硬化体にも関する。 The present invention relates to a method for producing a (meth) acrylic composition, and a paint comprising the (meth) acrylic composition. The present invention also relates to a cured product of this composition.
　近年、光学用オーバーコート剤、ハードコート剤、反射防止膜、眼鏡レンズ、光ファイバー、光導波路、ホログラム等の光学部品には、加工・生産性に優れる点から樹脂材料が広く用いられている。さらに光学部品の分野では小型化や薄型化の傾向が高まっており、それに伴い、屈折率の高い材料が求められている。そして、そのような要求に対しては、硬化時に高屈折率を有する樹脂組成物を含む塗料が広く用いられている。一方、そのような塗料は一般的に比較的粘度が高いという特徴があるため、薄く塗布することが困難である場合があった。そこでこの点を改良した粘度の低い組成物が提案されている。 In recent years, resin materials are widely used in optical components such as optical overcoating agents, hard coating agents, antireflective films, spectacle lenses, optical fibers, optical waveguides, holograms and the like in terms of excellent processing and productivity. Furthermore, in the field of optical components, the trend of downsizing and thinning is increasing, and accordingly, materials having a high refractive index are required. And to such a request | requirement, the coating material containing the resin composition which has high refractive index at the time of hardening is used widely. On the other hand, since such a paint is generally characterized by having a relatively high viscosity, it may have been difficult to apply thinly. Therefore, low viscosity compositions have been proposed which improve this point.
　例えば、特許文献１では、フェニルベンジルアクリレートの異性体であるｏ－フェニルベンジルアクリレート（ＯＰＢＡ；あるいは２－フェニルベンジルアクリレート）とｐ－フェニルベンジルアクリレート（ＰＰＢＡ；あるいは４－フェニルベンジルアクリレート）を特定の比率で混合することによって、高屈折率かつ低粘度の組成物が提案されている。また、特許文献２では、フェニルベンジルアクリレートと二官能（メタ）アクリレートまたはジフェニル誘導体を混合することによって、高屈折率かつ低粘度の組成物が得られると記載されている。 For example, in Patent Document 1, a specific ratio of o-phenylbenzyl acrylate (OPBA; or 2-phenylbenzyl acrylate), which is an isomer of phenylbenzyl acrylate, and p-phenylbenzyl acrylate (PPBA; or 4-phenylbenzyl acrylate) is used. A composition with high refractive index and low viscosity has been proposed by mixing at Further, Patent Document 2 describes that a composition having a high refractive index and a low viscosity can be obtained by mixing phenylbenzyl acrylate and a difunctional (meth) acrylate or a diphenyl derivative.
　特許文献３～７では、フェノキシベンジル（メタ）アクリレートと高屈折率を有する多官能（メタ）アクリレート(フルオレン系ビスフェノール誘導体やビスフェノールＡ誘導体)を混合し、光学材料用樹脂組成物を得ることが記載されている。 Patent Documents 3 to 7 disclose that a resin composition for an optical material is obtained by mixing phenoxybenzyl (meth) acrylate and a polyfunctional (meth) acrylate (fluorene-based bisphenol derivative or bisphenol A derivative) having a high refractive index. It is done.
特開２０１２－８２３８７号公報JP 2012-82387 A 特開２０１２－８２３８６号公報JP 2012-82386 A 特開２０１０－２４８３５８号公報JP, 2010-248358, A 特開２０１１－１２６９９１号公報JP, 2011-126991, A 特開２０１２－２１９２０５号公報JP 2012-219205 A 特開２０１３－５３３１０号公報JP, 2013-53310, A 特開２０１４－１８５３３７号公報JP, 2014-185337, A
　以上のように、これまで高屈折率かつ低粘度の種々の組成物が提案されている。しかし、粘度の低い単官能（メタ）アクリレートは屈折率が低いことが多く、他方、屈折率が高い単官能（メタ）アクリレートでは、高屈折率を有する多官能（メタ）アクリレートの粘度を下げる効果が十分に得られない場合がある。このような状況から、高屈折率かつ低粘度の単官能（メタ）アクリレートの開発が行われている。その一例として化学式（Ｃ）で表されるフェノキシベンジル（メタ）アクリレートが新たに見い出され、研究が進められている（例えば、特許文献４、（Ｂ）成分１など）。
Figure JPOXMLDOC01-appb-C000007
 As described above, various compositions having high refractive index and low viscosity have been proposed. However, monofunctional (meth) acrylates with low viscosity often have low refractive index, while monofunctional (meth) acrylates with high refractive index have the effect of lowering the viscosity of multifunctional (meth) acrylates with high refractive index May not be obtained enough. Under these circumstances, development of monofunctional (meth) acrylates with high refractive index and low viscosity has been conducted. As an example thereof, phenoxybenzyl (meth) acrylate represented by the chemical formula (C) is newly found and studied (for example, Patent Document 4, (B) component 1, etc.).
Figure JPOXMLDOC01-appb-C000007
　しかし、化学式（Ｃ）で表されるフェノキシベンジル（メタ）アクリレートを使用すると、高温高湿度（具体的には85℃/85%RH）下での環境試験において、塗膜の黄変が激しいことが判明している。このことから、組成物の粘度が低く、硬化時に高い屈折率を有し、さらに高温高湿度下での環境試験において黄変の小さな（メタ）アクリル系組成物が求められている。 However, when phenoxybenzyl (meth) acrylate represented by the chemical formula (C) is used, yellowing of the coating is severe in environmental tests under high temperature and high humidity (specifically, 85 ° C./85% RH) Is known. From this, a (meth) acrylic composition having a low viscosity, a high refractive index upon curing, and a small yellowing in an environmental test under high temperature and high humidity is required.
　本発明はこのような課題に対するものであり、組成物の粘度が低く、硬化時に高い屈折率を有し、さらに高温高湿度下での環境試験において黄変の少ない（メタ）アクリル系組成物の製造方法、およびそのような（メタ）アクリル系組成物を含む塗料を提供することを目的とする。また、本発明は上記組成物の硬化体を提供することも目的とする。 The present invention is directed to such problems, wherein the viscosity of the composition is low, the refractive index is high when cured, and the (meth) acrylic composition less yellowing in environmental tests under high temperature and high humidity conditions. It is an object of the present invention to provide a method of production and a paint comprising such (meth) acrylic composition. Another object of the present invention is to provide a cured product of the above composition.
　本発明者らは、上記課題を解決するために鋭意検討を行った結果、後述の一般式（１）の（メタ）アクリレートを所定の温度範囲で後述の一般式（２）の多価（メタ）アクリル系単量体と混合することで上記課題を解決し得ることを見出し、本発明に至った。 As a result of intensive studies to solve the above problems, the inventors of the present invention have found that (meth) acrylates of the general formula (1) described later are polyvalent (meta) of the general formula (2) described below in a predetermined temperature range. The present invention has been found out that the above problems can be solved by mixing with an acrylic monomer.
　すなわち本発明は、以下に記載する特徴を有するものである。
［１］
　（Ａ）下記一般式（１）で表される（メタ）アクリレートと、
Figure JPOXMLDOC01-appb-C000008
 [式（１）中、
　Ｘは、単結合、－Ｃ（Ｒ２）（Ｒ３）－、－Ｃ（＝Ｏ）－、－Ｏ－、－ＯＣ（＝Ｏ）－、－ＯＣ（＝Ｏ）Ｏ－、－Ｓ－、－ＳＯ－、－ＳＯ２－およびこれらの任意の組み合わせからなる群から選択される二価の基であり（ここで、Ｒ２およびＲ３は、各々独立に、水素原子、炭素数１～１０の直鎖状アルキル基、炭素数３～１０の分岐状アルキル基、炭素数３～１０の環状アルキル基、炭素数１～１０の直鎖状アルコキシ基、炭素数３～１０の分岐状アルコキシ基、炭素数３～１０の環状アルコキシ基、フェニル基またはフェニルフェニル基であり；あるいは、Ｒ２およびＲ３は、相互に連結して、これらが結合する炭素原子と一緒になって炭素数３～１０の環状アルキル基を形成していてもよい）；
　Ｙは、分岐していてもよい炭素数２～６のアルキレン基、炭素数６～１０のシクロアルキレン基、または炭素数６～１０のアリーレン基であり；
　Ｒ１は、水素原子またはメチル基であり；
　Ｒ４およびＲ５は、各々独立に、炭素数１～１０の直鎖状アルキル基、炭素数３～１０の分岐状アルキル基、炭素数３～１０の環状アルキル基、炭素数１～１０の直鎖状アルコキシ基、炭素数３～１０の分岐状アルコキシ基、炭素数３～１０の環状アルコキシ基、ハロゲン原子、フェニル基またはフェニルフェニル基であり；
　ｍは、０～１０の整数であり；
　ｎは、１～２の整数であり；
　ｐは、０～４の整数であり；
　ｑは、０～５の整数である]
　（Ｂ）下記一般式（２）で表される多価（メタ）アクリル系単量体と
Figure JPOXMLDOC01-appb-C000009
 [式（２）中、
　Ｒ１０およびＲ１１は、それぞれ独立に、水素原子、炭素数１～２０のアルキル基、炭素数１～２０のアルコキシル基、炭素数３～２０のシクロアルキル基、炭素数５～２０のシクロアルコキシル基、炭素数６～２０のアリール基、炭素数６～２０のアリールオキシ基、およびハロゲン原子から選択され、
　Ｒ１２は、水素原子またはメチル基であり；
　Ｘは、単結合、－Ｏ－、－Ｓ－、－ＳＯ－、－ＳＯ２－、－ＣＯ－および下記一般式（３）～（６）からなる群のうち、いずれかの構造を表し；
　ＹおよびＺは、それぞれ独立に、分岐していてもよい炭素数２～６のアルキレン基、炭素数６～１０のシクロアルキレン基、または炭素数６～１０のアリーレン基であり；
　ｐおよびｑは、それぞれ独立に、０～４の整数である。］
Figure JPOXMLDOC01-appb-C000010
 ［式（３）中、
　Ｒ１３およびＲ１４はそれぞれ独立に水素原子、ハロゲン原子、置換基を有してもよい炭素数１～２０のアルキル基、置換基を有してもよい炭素数１～５のアルコキシ基、置換基を有してもよい炭素数６～１２のアリール基、置換基を有してもよい炭素数２～５のアルケニル基、および置換基を有してもよい炭素数７～１７のアラルキル基からなる群のうちいずれかを表し；
　前記置換基はそれぞれ独立に、ハロゲン原子、炭素数１～２０のアルキル基、または炭素数６～１２のアリール基であり；
　ｃは１～２０の整数を表す。］
Figure JPOXMLDOC01-appb-C000011
 ［式（４）中、Ｒ１５およびＲ１６はそれぞれ独立に水素原子、ハロゲン原子、置換基を有してもよい炭素数１～２０のアルキル基、置換基を有してもよい炭素数１～５のアルコキシ基、置換基を有してもよい炭素数６～１２のアリール基、置換基を有してもよい炭素数２～５のアルケニル基および置換基を有してもよい炭素数７～１７のアラルキル基からなる群のうちいずれかを表すか、または、Ｒ１５およびＲ１６はそれぞれ互いに結合して、炭素数１～２０の炭素環若しくは複素環を形成し；
　前記置換基はそれぞれ独立に、ハロゲン原子、炭素数１～２０のアルキル基、または炭素数６～１２のアリール基である。］
Figure JPOXMLDOC01-appb-C000012
 ［式（５）中、Ｒ１７～Ｒ２０はそれぞれ独立に水素原子、ハ口ゲン、置換基を有してもよい炭素数１～２０のアルキル基、置換基を有してもよい炭素数１～５のアルコキシ基、置換基を有してもよい炭素数６～１２のアリール基、置換基を有してもよい炭素数２～５のアルケニル基および置換基を有してもよい炭素数７～１７のアラルキル基からなる群のうちいずれかを表すか、または、Ｒ１７およびＲ１８並びにＲ１９およびＲ２０は、それぞれ互いに結合して、炭素数１～２０の炭素環若しくは複素環を形成し；
　前記置換基はそれぞれ独立に、ハロゲン原子、炭素数１～２０のアルキル基、または炭素数６～１２のアリール基である。］
Figure JPOXMLDOC01-appb-C000013
 ［式（６）中、Ｒ２１～Ｒ３０はそれぞれ独立に水素原子または炭素数１～３のアルキル基である。］
　を含む液体組成物の製造方法であって、
　前記一般式（１）で表される（メタ）アクリレートを３５℃以上１２０℃以下の温度で前記一般式（２）で表される多価（メタ）アクリル系単量体と混合することを含む、方法。
［２］
　前記式（１）中、ｐおよびｑが共に０である、［１］に記載の方法。
［３］
　前記式（１）中、ｎが１であり、ｍが０である、［１］または［２］に記載の方法。
［４］
　前記一般式（１）で表される（メタ）アクリレートと前記一般式（２）で表される多価（メタ）アクリル系単量体の含有量が、質量比で１：１０～１０：１である、［１］～［３］のいずれかに記載の方法。
［５］
　前記一般式（１）で表される（メタ）アクリレートが２種類以上の化合物のブレンド体である、［１］～［４］のいずれかに記載の方法。
［６］
　前記式（２）中、Ｘが一般式（４）で示される構造を有する、［１］～［５］のいずれかに記載の方法。
［７］
　前記液体組成物が活性エネルギー線硬化性組成物である、［１］～［６］のいずれかに記載の方法。
［８］
　［１］～［７］のいずれかに記載の方法で得られた組成物を含む塗料。
［９］
　［１］～［７］のいずれかに記載の方法で得られた組成物が硬化されてなる硬化体。
［１０］
　硬化体の製造方法であって、
　［１］～［７］のいずれかに記載の方法で組成物を得る工程と、
　前記組成物を硬化させる工程と
を含む、方法。 That is, the present invention has the features described below.
[1]
(A) (meth) acrylate represented by the following general formula (1),
Figure JPOXMLDOC01-appb-C000008
 [In the formula (1),
X represents a single bond, -C (R 2 ) (R 3 )-, -C (= O)-, -O-, -OC (= O)-, -OC (= O) O-, -S- A divalent group selected from the group consisting of -SO-, -SO 2 -and any combination thereof (wherein R 2 and R 3 each independently represent a hydrogen atom or C 1 -C 2 10 linear alkyl group, branched alkyl group having 3 to 10 carbon atoms, cyclic alkyl group having 3 to 10 carbon atoms, linear alkoxy group having 1 to 10 carbon atoms, branched alkoxy having 3 to 10 carbon atoms Group, a cyclic alkoxy group having 3 to 10 carbon atoms, a phenyl group or a phenylphenyl group; or alternatively, R 2 and R 3 are linked to each other, and together with the carbon atom to which they are bonded, have 3 carbon atoms To 10 cyclic alkyl groups may be formed);
Y represents an alkylene group having 2 to 6 carbon atoms which may be branched, a cycloalkylene group having 6 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms;
R 1 is a hydrogen atom or a methyl group;
R 4 and R 5 each independently represent a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, or 1 to 10 carbon atoms A linear alkoxy group, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a halogen atom, a phenyl group or a phenylphenyl group;
m is an integer of 0 to 10;
n is an integer of 1 to 2;
p is an integer of 0 to 4;
q is an integer of 0 to 5]
(B) a multivalent (meth) acrylic monomer represented by the following general formula (2)
Figure JPOXMLDOC01-appb-C000009
 [In the formula (2),
R 10 and R 11 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a cycloalkoxyl group having 5 to 20 carbon atoms A group, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and a halogen atom,
R 12 is a hydrogen atom or a methyl group;
X represents a structure of any one of the group consisting of a single bond, -O-, -S-, -SO-, -SO 2- , -CO- and the following general formulas (3) to (6);
Y and Z each independently represent an alkylene group having 2 to 6 carbon atoms which may be branched, a cycloalkylene group having 6 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms;
p and q are each independently an integer of 0 to 4. ]
Figure JPOXMLDOC01-appb-C000010
 [In the formula (3),
R 13 and R 14 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, The aryl group having 6 to 12 carbon atoms which may have a group, the alkenyl group having 2 to 5 carbon atoms which may have a substituent, and the aralkyl group having 7 to 17 carbon atoms which may have a substituent Represents any one of the group consisting of
The substituents are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms;
c represents an integer of 1 to 20. ]
Figure JPOXMLDOC01-appb-C000011
 [In Formula (4), R 15 and R 16 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or 1 carbon atom which may have a substituent] Alkoxy group of ̃5, aryl group having 6 to 12 carbon atoms which may have a substituent, alkenyl group having 2 to 5 carbon atoms which may have a substituent, and carbon number which may have a substituent Or any one of the group consisting of 7 to 17 aralkyl groups, or R 15 and R 16 respectively bond to each other to form a carbocyclic ring or heterocyclic ring having 1 to 20 carbon atoms;
The substituents are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms. ]
Figure JPOXMLDOC01-appb-C000012
 [In formula (5), R 17 to R 20 each independently represent a hydrogen atom, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a carbon number which may have a substituent 1 to 5 alkoxy group, optionally substituted aryl group having 6 to 12 carbon atoms, optionally substituted alkenyl group having 2 to 5 carbon atoms and carbon optionally having substituent group R 17 and R 18 and R 19 and R 20 are each bonded to each other to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms. Form;
The substituents are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms. ]
Figure JPOXMLDOC01-appb-C000013
 In the formula (6), R 21 to R 30 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ]
A method of producing a liquid composition comprising
Including mixing the (meth) acrylate represented by the said General formula (1) with the polyvalent (meth) acrylic-type monomer represented by the said General formula (2) at the temperature of 35 degreeC or more and 120 degrees C or less ,Method.
[2]
The method according to [1], wherein in the formula (1), p and q are both 0.
[3]
The method according to [1] or [2], wherein in the formula (1), n is 1 and m is 0.
[4]
The content of the (meth) acrylate represented by the general formula (1) and the polyvalent (meth) acrylic monomer represented by the general formula (2) is 1:10 to 10: 1 in mass ratio The method according to any one of [1] to [3], which is
[5]
The method according to any one of [1] to [4], wherein the (meth) acrylate represented by the general formula (1) is a blend of two or more types of compounds.
[6]
The method according to any one of [1] to [5], wherein in the formula (2), X has a structure represented by the general formula (4).
[7]
The method according to any one of [1] to [6], wherein the liquid composition is an active energy ray curable composition.
[8]
A paint comprising the composition obtained by the method according to any one of [1] to [7].
[9]
A cured product obtained by curing the composition obtained by the method according to any one of [1] to [7].
[10]
A method of producing a cured product,
Obtaining a composition by the method according to any one of [1] to [7];
Curing the composition.
　本発明によると、組成物の粘度が低く、硬化時に高い屈折率を有し、さらに高温高湿度下での環境試験において黄変の少ない（メタ）アクリル系組成物の製造方法、およびそのような（メタ）アクリル系組成物を含む塗料を提供することができる。また、本発明によると上記組成物の硬化体を提供することもできる。 According to the present invention, a method for producing a (meth) acrylic composition having a low viscosity of the composition, a high refractive index upon curing, and less yellowing in environmental tests under high temperature and humidity, and such It is possible to provide a paint comprising a (meth) acrylic composition. Also, according to the present invention, a cured product of the above composition can be provided.
　以下、本発明の実施の形態について、詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
＜製造方法＞
　本発明の液体組成物の製造方法は、
（Ａ）下記一般式（１）で表される（メタ）アクリレートと、
Figure JPOXMLDOC01-appb-C000014
 [式（１）中、
　Ｘは、単結合、－Ｃ（Ｒ２）（Ｒ３）－、－Ｃ（＝Ｏ）－、－Ｏ－、－ＯＣ（＝Ｏ）－、－ＯＣ（＝Ｏ）Ｏ－、－Ｓ－、－ＳＯ－、－ＳＯ２－およびこれらの任意の組み合わせからなる群から選択される二価の基であり（ここで、Ｒ２およびＲ３は、各々独立に、水素原子、炭素数１～１０の直鎖状アルキル基、炭素数３～１０の分岐状アルキル基、炭素数３～１０の環状アルキル基、炭素数１～１０の直鎖状アルコキシ基、炭素数３～１０の分岐状アルコキシ基、炭素数３～１０の環状アルコキシ基、フェニル基またはフェニルフェニル基であり；あるいは、Ｒ２およびＲ３は、相互に連結して、これらが結合する炭素原子と一緒になって炭素数３～１０の環状アルキル基を形成していてもよい）；
　Ｙは、分岐していてもよい炭素数２～６のアルキレン基、炭素数６～１０のシクロアルキレン基、または炭素数６～１０のアリーレン基であり；
　Ｒ１は、水素原子またはメチル基であり；
　Ｒ４およびＲ５は、各々独立に、炭素数１～１０の直鎖状アルキル基、炭素数３～１０の分岐状アルキル基、炭素数３～１０の環状アルキル基、炭素数１～１０の直鎖状アルコキシ基、炭素数３～１０の分岐状アルコキシ基、炭素数３～１０の環状アルコキシ基、ハロゲン原子、フェニル基またはフェニルフェニル基であり；
　ｍは、０～１０の整数であり；
　ｎは、１～２の整数であり；
　ｐは、０～４の整数であり；
　ｑは、０～５の整数である]
　（Ｂ）下記一般式（２）で表される多価（メタ）アクリル系単量体と
Figure JPOXMLDOC01-appb-C000015
 [式（２）中、
　Ｒ１０およびＲ１１は、それぞれ独立に、水素原子、炭素数１～２０のアルキル基、炭素数１～２０のアルコキシル基、炭素数３～２０のシクロアルキル基、炭素数５～２０のシクロアルコキシル基、炭素数６～２０のアリール基、炭素数６～２０のアリールオキシ基、およびハロゲン原子から選択され、
　Ｒ１２は、水素原子またはメチル基であり；
　Ｘは、単結合、－Ｏ－、－Ｓ－、－ＳＯ－、－ＳＯ２－、－ＣＯ－および後述の一般式（３）～（６）からなる群のうち、いずれかの構造を表し；
　ＹおよびＺは、それぞれ独立に、分岐していてもよい炭素数２～６のアルキレン基、炭素数６～１０のシクロアルキレン基、または炭素数６～１０のアリーレン基であり；
　ｐおよびｑは、それぞれ独立に、０～４の整数である。］
　を含む液体組成物の製造方法であって、
　一般式（１）で表される（メタ）アクリレートを３５℃以上１２０℃以下の温度で一般式（２）で表される多価（メタ）アクリル系単量体と混合することを含んでなる。 <Manufacturing method>
The method for producing a liquid composition of the present invention is
(A) (meth) acrylate represented by the following general formula (1),
Figure JPOXMLDOC01-appb-C000014
 [In the formula (1),
X represents a single bond, -C (R 2 ) (R 3 )-, -C (= O)-, -O-, -OC (= O)-, -OC (= O) O-, -S- A divalent group selected from the group consisting of -SO-, -SO 2 -and any combination thereof (wherein R 2 and R 3 each independently represent a hydrogen atom or C 1 -C 2 10 linear alkyl group, branched alkyl group having 3 to 10 carbon atoms, cyclic alkyl group having 3 to 10 carbon atoms, linear alkoxy group having 1 to 10 carbon atoms, branched alkoxy having 3 to 10 carbon atoms Group, a cyclic alkoxy group having 3 to 10 carbon atoms, a phenyl group or a phenylphenyl group; or alternatively, R 2 and R 3 are linked to each other, and together with the carbon atom to which they are bonded, have 3 carbon atoms To 10 cyclic alkyl groups may be formed);
Y represents an alkylene group having 2 to 6 carbon atoms which may be branched, a cycloalkylene group having 6 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms;
R 1 is a hydrogen atom or a methyl group;
R 4 and R 5 each independently represent a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, or 1 to 10 carbon atoms A linear alkoxy group, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a halogen atom, a phenyl group or a phenylphenyl group;
m is an integer of 0 to 10;
n is an integer of 1 to 2;
p is an integer of 0 to 4;
q is an integer of 0 to 5]
(B) a multivalent (meth) acrylic monomer represented by the following general formula (2)
Figure JPOXMLDOC01-appb-C000015
 [In the formula (2),
R 10 and R 11 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a cycloalkoxyl group having 5 to 20 carbon atoms A group, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and a halogen atom,
R 12 is a hydrogen atom or a methyl group;
X represents a structure of any one of the group consisting of a single bond, -O-, -S-, -SO-, -SO 2- , -CO- and general formulas (3) to (6) described later ;
Y and Z each independently represent an alkylene group having 2 to 6 carbon atoms which may be branched, a cycloalkylene group having 6 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms;
p and q are each independently an integer of 0 to 4. ]
A method of producing a liquid composition comprising
Mixing the (meth) acrylate represented by the general formula (1) with the polyvalent (meth) acrylic monomer represented by the general formula (2) at a temperature of 35 ° C. or more and 120 ° C. or less .
　上記のように、一般式（１）の構造を有する（メタ）アクリレートを所定の温度範囲で一般式（２）の構造を有する多価（メタ）アクリル系単量体と混合することで得られる液体組成物は、粘度が低く、硬化時に高い屈折率を有し、さらに高温高湿度下での環境試験において黄変が小さい。理論に拘束されるものではないが、黄変の発生は、ガラス転移温度の低さが原因と推定される。また、一般式（１）の構造を有する（メタ）アクリレートは常温では常に固体である物が多く、高屈折率かつ高粘度の一般式（２）多価（メタ）アクリル系単量体の粘度を低下させる目的で用いることができないと考えられていた。例えば、特許文献１には、一般式（１）の構造を有する（メタ）アクリレートの一種であるp-フェニルベンジル（メタ）アクリレートが常温で固体（mp：32℃）であるため、本用途では使用できないとされている。そして、特許文献１では、常温で液体であるｏ－フェニルベンジル（メタ）アクリレートと、p-フェニルベンジル（メタ）アクリレートとを特定の割合で混合することで液体組成物を得ている。 As mentioned above, it is obtained by mixing the (meth) acrylate which has a structure of General formula (1) with the polyvalent (meth) acrylic-type monomer which has a structure of General formula (2) in a predetermined | prescribed temperature range The liquid composition has a low viscosity, a high refractive index upon curing, and less yellowing in environmental tests under high temperature and humidity. Without being bound by theory, the occurrence of yellowing is presumed to be due to the low glass transition temperature. In addition, many of (meth) acrylates having the structure of the general formula (1) are always solid at normal temperature, and the viscosity of the general formula (2) polyvalent (meth) acrylic monomer having high refractive index and high viscosity It was thought that it could not be used for the purpose of lowering the For example, Patent Document 1 discloses that p-phenylbenzyl (meth) acrylate which is a kind of (meth) acrylate having a structure of the general formula (1) is solid at normal temperature (mp: 32 ° C.). It is considered that it can not be used. In Patent Document 1, a liquid composition is obtained by mixing o-phenylbenzyl (meth) acrylate which is liquid at normal temperature and p-phenylbenzyl (meth) acrylate in a specific ratio.
　そのような状況下、本発明者らは一般式（１）の構造を有する（メタ）アクリレートを所定の温度範囲に加熱することで、一般式（１）の構造を有する（メタ）アクリレートが液化し、その状態で一般式（２）の構造を有する多価（メタ）アクリル系単量体と混合することで、液体組成物が得られることを知得した。そして驚くべきことに、一般式（１）の構造を有する（メタ）アクリレートを液化した後で一般式（２）の構造を有する多価（メタ）アクリル系単量体と混合した場合、得られた液体組成物をその後冷却しても結晶等は析出せず、安定な液体組成物となることを知得した。さらにこのようにして得られた液体組成物は粘度が低く、硬化時に高い屈折率を有し、さらに高温高湿度下での環境試験において黄変が小さいものであった。本発明はこのような知見に基づくものである。 Under such circumstances, the present inventors liquefy the (meth) acrylate having the structure of the general formula (1) by heating the (meth) acrylate having the structure of the general formula (1) to a predetermined temperature range Then, it was known that a liquid composition can be obtained by mixing with the polyvalent (meth) acrylic monomer having the structure of the general formula (2) in that state. And, surprisingly, it is obtained when the (meth) acrylate having the structure of the general formula (1) is liquefied and then mixed with the polyvalent (meth) acrylic monomer having the structure of the general formula (2). Even if the liquid composition was cooled thereafter, crystals and the like did not precipitate, and it was found that a stable liquid composition was obtained. Furthermore, the liquid composition thus obtained had a low viscosity, had a high refractive index upon curing, and exhibited little yellowing in environmental tests under high temperature and high humidity. The present invention is based on such findings.
　本発明の製造方法における一般式（１）の構造を有する（メタ）アクリレートを一般式（２）の構造を有する多価（メタ）アクリル系単量体と混合する際の温度は、３５℃以上１２０℃以下であり、好ましくは４０℃以上１００℃以下であり、より好ましくは４５℃以上８０℃以下である。混合する際の温度が３５℃以上であれば一般式（１）の構造を有する（メタ）アクリレートが十分に液化し、１２０℃以下であればモノマーの重合を防止することができる。混合をする際、少なくとも一般式（１）の構造を有する（メタ）アクリレートの温度を上記温度範囲に調整すればよく、一般式（２）の構造を有する多価（メタ）アクリル系単量体は常温のまま混合してもよい。 The temperature at which the (meth) acrylate having the structure of the general formula (1) in the production method of the present invention is mixed with the polyvalent (meth) acrylic monomer having the structure of the general formula (2) is 35 ° C. or higher It is 120 ° C. or less, preferably 40 ° C. or more and 100 ° C. or less, and more preferably 45 ° C. or more and 80 ° C. or less. If the temperature at the time of mixing is 35 ° C. or more, the (meth) acrylate having the structure of the general formula (1) can be sufficiently liquefied, and if it is 120 ° C. or less, the polymerization of the monomer can be prevented. When mixing, the temperature of the (meth) acrylate having at least the structure of the general formula (1) may be adjusted to the above temperature range, and a polyvalent (meth) acrylic monomer having the structure of the general formula (2) May be mixed at normal temperature.
　本発明の液体組成物の粘度は、Ｅ型粘度計（ＴＶ－２２型）を用いて、測定温度：２５℃で測定した場合に１０，０００ｍＰａ・ｓ未満であり、好ましくは、５，０００ｍＰａ・ｓ以下であり、より好ましくは、５～２，０００ｍＰａ・ｓである。 The viscosity of the liquid composition of the present invention is less than 10,000 mPa · s when measured at a measurement temperature of 25 ° C. using an E-type viscometer (TV-22 type), preferably 5,000 mPa · s. s or less, more preferably 5 to 2,000 mPa · s.
　以下、本発明の製造方法によって得られる組成物に含まれる各成分について、順に説明する。
１．（メタ）アクリレート
　本発明の製造方法によって得られる組成物に用いられる（メタ）アクリレートは下記一般式(１)で表される構造を有する。
Figure JPOXMLDOC01-appb-C000016
 Hereinafter, each component contained in the composition obtained by the manufacturing method of this invention is demonstrated in order.
1. (Meth) Acrylate The (meth) acrylate used in the composition obtained by the production method of the present invention has a structure represented by the following general formula (1).
Figure JPOXMLDOC01-appb-C000016
　式（１）中、Ｘは、単結合、－Ｃ（Ｒ２）（Ｒ３）－、－Ｃ（＝Ｏ）－、－Ｏ－、－ＯＣ（＝Ｏ）－、－ＯＣ（＝Ｏ）Ｏ－、－Ｓ－、－ＳＯ－、－ＳＯ２－およびこれらの任意の組み合わせからなる群から選択される二価の基であり、好ましくは、単結合、－Ｃ（Ｒ２）（Ｒ３）－、－Ｏ－、およびこれらの任意の組み合わせからなる群から選択される二価の基である。ここで、Ｒ２およびＲ３は、各々独立に、水素原子、炭素数１～１０の直鎖状アルキル基、炭素数３～１０の分岐状アルキル基、炭素数３～１０の環状アルキル基、炭素数１～１０の直鎖状アルコキシ基、炭素数３～１０の分岐状アルコキシ基、炭素数３～１０の環状アルコキシ基、フェニル基またはフェニルフェニル基である。あるいは、Ｒ２およびＲ３は、相互に連結して、これらが結合する炭素原子と一緒になって炭素数３～１０の環状アルキル基を形成していてもよい。好ましくは、Ｒ２およびＲ３は、共に水素原子である。 In formula (1), X is a single bond, -C (R 2 ) (R 3 )-, -C (= O)-, -O-, -OC (= O)-, -OC (= O) A divalent group selected from the group consisting of O-, -S-, -SO-, -SO 2 -and any combination thereof, preferably a single bond, -C (R 2 ) (R 3 And -O-, and any combination thereof, which is a divalent group selected from the group consisting of Here, R 2 and R 3 each independently represent a hydrogen atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms, It is a linear alkoxy group having 1 to 10 carbon atoms, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a phenyl group or a phenylphenyl group. Alternatively, R 2 and R 3 may be linked together to form a C 3-10 cyclic alkyl group together with the carbon atom to which they are attached. Preferably, R 2 and R 3 are both hydrogen atoms.
　Ｙは、分岐していてもよい炭素数２～６のアルキレン基、炭素数６～１０のシクロアルキレン基、または炭素数６～１０のアリーレン基である。 Y is an alkylene group having 2 to 6 carbon atoms which may be branched, a cycloalkylene group having 6 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms.
　Ｒ１は、水素原子またはメチル基であり、好ましくは水素原子である。
　Ｒ４およびＲ５は、各々独立に、炭素数１～１０の直鎖状アルキル基、炭素数３～１０の分岐状アルキル基、炭素数３～１０の環状アルキル基、炭素数１～１０の直鎖状アルコキシ基、炭素数３～１０の分岐状アルコキシ基、炭素数３～１０の環状アルコキシ基、ハロゲン原子、フェニル基またはフェニルフェニル基である。 R 1 is a hydrogen atom or a methyl group, preferably a hydrogen atom.
R 4 and R 5 each independently represent a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, or 1 to 10 carbon atoms And a linear alkoxy group, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a halogen atom, a phenyl group or a phenylphenyl group.
　ｍは、０～１０の整数であり、好ましくは０～５の整数であり、より好ましくは０である。
　ｎは、１～２の整数であり、好ましくは１である。
　さらに好ましくは、ｎが１であり、ｍが０である。
　ｐは、０～４の整数であり、好ましくは０～２の整数であり、より好ましくは０である。
　ｑは、０～５の整数であり、好ましくは０～２の整数であり、より好ましくは０である。
　さらに好ましくは、ｐおよびｑが共に０である。ｐおよびｑが０の場合は、ベンゼン環の水素がＲ４やＲ５の官能基で置換されていないことを意味する。 m is an integer of 0 to 10, preferably an integer of 0 to 5, and more preferably 0.
n is an integer of 1 to 2, preferably 1.
More preferably, n is 1 and m is 0.
p is an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0.
q is an integer of 0 to 5, preferably an integer of 0 to 2, and more preferably 0.
More preferably, p and q are both 0. When p and q are 0, it means that the hydrogen of the benzene ring is not substituted by the functional group of R 4 or R 5 .
　上記一般式（１）で表される（メタ）アクリレートとしては、例えば、４－フェニルベンジル（メタ）アクリレート、３－フェニルベンジル（メタ）アクリレート、２－フェニルベンジル（メタ）アクリレート、４－ビフェニルベンジル（メタ）アクリレート、３－ビフェニルベンジル（メタ）アクリレート、２－ビフェニルベンジル（メタ）アクリレート、４－ベンジルベンジル（メタ）アクリレート、３－ベンジルベンジル（メタ）アクリレート、２－ベンジルベンジル（メタ）アクリレート、４－フェネチルベンジル（メタ）アクリレート、３－フェネチルベンジル（メタ）アクリレート、２－フェネチルベンジル（メタ）アクリレート、４－フェネチルフェネチル（メタ）アクリレート、３－フェネチルフェネチル（メタ）アクリレート、２－フェネチルフェネチル（メタ）アクリレート、４－（４－メチルフェニル）ベンジル（メタ）アクリレート、３－（４－メチルフェニル）ベンジル（メタ）アクリレート、２－（４－メチルフェニル）ベンジル（メタ）アクリレート、４－（４－メトキシフェニル）ベンジル（メタ）アクリレート、３－（４－メトキシフェニル）ベンジル（メタ）アクリレート、２－（４－メトキシフェニル）ベンジル（メタ）アクリレート、４－（４－ブロモフェニル）ベンジル（メタ）アクリレート、３－（４－ブロモフェニル）ベンジル（メタ）アクリレート、２－（４－ブロモフェニル）ベンジル（メタ）アクリレート、４－ベンゾイルベンジル（メタ）アクリレート、３－ベンゾイルベンジル（メタ）アクリレート、２－ベンゾイルベンジル（メタ）アクリレート、４－（フェニルスルフィニル）ベンジル（メタ）アクリレート、３－（フェニルスルフィニル）ベンジル（メタ）アクリレート、２－（フェニルスルフィニル）ベンジル（メタ）アクリレート、４－（フェニルスルフォニル）ベンジル（メタ）アクリレート、３－（フェニルスルフォニル）ベンジル（メタ）アクリレート、２－（フェニルスルフォニル）ベンジル（メタ）アクリレート、４－（（フェノキシカルボニル）オキシ）ベンジル（メタ）アクリレート、３－（（フェノキシカルボニル）オキシ）ベンジル（メタ）アクリレート、２－（（フェノキシカルボニル）オキシ）ベンジル（メタ）アクリレート、４－（（（メタ）アクリロキシ）メチル）フェニルベンゾエート、３－（（（メタ）アクリロキシ）メチル）フェニルベンゾエート、２－（（（メタ）アクリロキシ）メチル）フェニルベンゾエート、フェニル４－（（（メタ）アクリロキシ）メチル）ベンゾエート、フェニル３－（（（メタ）アクリロキシ）メチル）ベンゾエート、フェニル２－（（（メタ）アクリロキシ）メチル）ベンゾエート、４－（１－フェニルシクロヘキシル）ベンジル（メタ）アクリレート、３－（１－フェニルシクロヘキシル）ベンジル（メタ）アクリレート、２－（１－フェニルシクロヘキシル）ベンジル（メタ）アクリレート、４－フェノキシベンジル（メタ）アクリレート、３－フェノキシベンジル（メタ）アクリレート、２－フェノキシベンジル（メタ）アクリレート、４－（フェニルチオ）ベンジル（メタ）アクリレート、３－（フェニルチオ）ベンジル（メタ）アクリレート、２－（フェニルチオ）ベンジル（メタ）アクリレートおよび３－メチル－４－（２－メチルフェニル）ベンジルメタクリレートを挙げることができる。これらは、１種単独で、または２種以上を組み合わせて用いることができる。例えば、（メタ）アクリレートが２種類以上の化合物のブレンド体であってもよく、その場合、少なくとも１種のメタアクリレートが上記一般式（１）で表される（メタ）アクリレートであればよい。上記の（メタ）アクリレートのうち、好ましくは、２－フェニルベンジル（メタ）アクリレート、４－フェニルベンジル(メタ)アクリレート、４－フェノキシベンジル(メタ)アクリレートおよび４－ベンジルベンジル(メタ)アクリレートであり、より好ましくは、２－フェニルベンジルアクリレート、４－フェニルベンジルアクリレート、４－フェノキシベンジルアクリレートおよび４－ベンジルベンジルアクリレートである。 Examples of the (meth) acrylate represented by the above general formula (1) include 4-phenylbenzyl (meth) acrylate, 3-phenylbenzyl (meth) acrylate, 2-phenylbenzyl (meth) acrylate, 4-biphenylbenzyl (Meth) acrylate, 3-biphenyl benzyl (meth) acrylate, 2-biphenyl benzyl (meth) acrylate, 4-benzyl benzyl (meth) acrylate, 3-benzyl benzyl (meth) acrylate, 2-benzyl benzyl (meth) acrylate, 4-phenethyl benzyl (meth) acrylate, 3-phenethyl benzyl (meth) acrylate, 2-phenethyl benzyl (meth) acrylate, 4-phenethyl phenethyl (meth) acrylate, 3-phenethyl phenethyl (meth) acrylic And 2-phenethylphenethyl (meth) acrylate, 4- (4-methylphenyl) benzyl (meth) acrylate, 3- (4-methylphenyl) benzyl (meth) acrylate, 2- (4-methylphenyl) benzyl (meth) acrylate Meta) acrylate, 4- (4-methoxyphenyl) benzyl (meth) acrylate, 3- (4-methoxyphenyl) benzyl (meth) acrylate, 2- (4-methoxyphenyl) benzyl (meth) acrylate, 4- (4) -Bromophenyl) benzyl (meth) acrylate, 3- (4-bromophenyl) benzyl (meth) acrylate, 2- (4-bromophenyl) benzyl (meth) acrylate, 4-benzoylbenzyl (meth) acrylate, 3-benzoyl Benzyl (meth) acrylate, 2-benzoyl Nidyl (meth) acrylate, 4- (phenylsulfinyl) benzyl (meth) acrylate, 3- (phenylsulfinyl) benzyl (meth) acrylate, 2- (phenylsulfinyl) benzyl (meth) acrylate, 4- (phenylsulfonyl) benzyl Meta) acrylate, 3- (phenylsulfonyl) benzyl (meth) acrylate, 2- (phenylsulfonyl) benzyl (meth) acrylate, 4-((phenoxycarbonyl) oxy) benzyl (meth) acrylate, 3- (phenoxycarbonyl) Oxy) benzyl (meth) acrylate, 2- ((phenoxycarbonyl) oxy) benzyl (meth) acrylate, 4- (((meth) acryloxy) methyl) phenyl benzoate, 3- (((meth) acrylonitrile Di) methyl) phenylbenzoate, 2-(((meth) acryloxy) methyl) phenylbenzoate, phenyl 4-((meth) acryloxy) methyl) benzoate, phenyl 3-(((meth) acryloxy) methyl) benzoate, phenyl 2-(((Meth) acryloxy) methyl) benzoate, 4- (1-phenylcyclohexyl) benzyl (meth) acrylate, 3- (1-phenylcyclohexyl) benzyl (meth) acrylate, 2- (1-phenylcyclohexyl) benzyl (Meth) acrylate, 4-phenoxybenzyl (meth) acrylate, 3-phenoxybenzyl (meth) acrylate, 2-phenoxybenzyl (meth) acrylate, 4- (phenylthio) benzyl (meth) acrylate, 3- (phenylthio) And benzyl (meth) acrylate, 2- (phenylthio) benzyl (meth) acrylate and 3-methyl-4- (2-methylphenyl) benzyl methacrylate. These can be used singly or in combination of two or more. For example, the (meth) acrylate may be a blend of two or more types of compounds, in which case at least one type of methacrylate may be a (meth) acrylate represented by the above general formula (1). Among the above (meth) acrylates, preferred are 2-phenylbenzyl (meth) acrylate, 4-phenylbenzyl (meth) acrylate, 4-phenoxybenzyl (meth) acrylate and 4-benzylbenzyl (meth) acrylate, More preferably, 2-phenylbenzyl acrylate, 4-phenylbenzyl acrylate, 4-phenoxybenzyl acrylate and 4-benzyl benzyl acrylate.
　本発明の製造方法によって得られる組成物に含まれる（メタ）アクリレートの配合量は、本発明の主旨を逸脱しない範囲であれば特に限定されないが、（メタ）アクリレートと一般式（２）で表される多価（メタ）アクリル系単量体の含有量が、質量比で１：９～９：１であることが好ましく、２：８～８：２であることがより好ましく、３：７～７：３であることがさらに好ましく、４：６～６：４であることが特に好ましい。また、単官能性（メタ）アクリレートの比率が高いほど、高温・高湿環境下での剥離が防止できる点で好ましい。理論に拘束されるものではないが、基材と硬化体との間の密着性低下は、吸水率が大きいことが原因と推定される。 Although the compounding quantity of (meth) acrylate contained in the composition obtained by the manufacturing method of this invention is not specifically limited if it is a range which does not deviate from the main point of this invention, (meth) acrylate and General formula (2) The content of the polyvalent (meth) acrylic monomer to be added is preferably 1: 9 to 9: 1 by mass ratio, more preferably 2: 8 to 8: 2, and 3: 7 It is further preferable that the ratio is -7: 3, and particularly preferably 4: 6 to 6: 4. Moreover, the higher the ratio of monofunctional (meth) acrylates, the more preferable in that peeling at high temperature and high humidity can be prevented. Without being bound by theory, it is presumed that the decrease in adhesion between the substrate and the cured product is caused by a large water absorption.
３．多価（メタ）アクリル系単量体
　本発明の製造方法によって得られる組成物は、上記一般式（１）で表される（メタ）アクリレートとの共重合が可能な、下記一般式（２）で表される多価（メタ）アクリル系単量体をさらに含む。
Figure JPOXMLDOC01-appb-C000017
 3. Multivalent (Meth) Acrylic-Based Monomer The composition obtained by the production method of the present invention can be copolymerized with the (meth) acrylate represented by the above general formula (1), which is represented by the following general formula (2) It further contains a multivalent (meth) acrylic monomer represented by
Figure JPOXMLDOC01-appb-C000017
　式（２）中、Ｒ１０およびＲ１１は、それぞれ独立に、水素原子、炭素数１～２０のアルキル基、炭素数１～２０のアルコキシル基、炭素数３～２０のシクロアルキル基、炭素数５～２０のシクロアルコキシル基、炭素数６～２０のアリール基、炭素数６～２０のアリールオキシ基、およびハロゲン原子から選択され、好ましくは水素原子である。
　Ｒ１２は、水素原子またはメチル基である。
　Ｘは、単結合、－Ｏ－、－Ｓ－、－ＳＯ－、－ＳＯ２－、－ＣＯ－および下記一般式（３）～（６）からなる群のうち、いずれかの構造を表す。
　ＹおよびＺは、それぞれ独立に、分岐していてもよい炭素数２～６のアルキレン基、炭素数６～１０のシクロアルキレン基、または炭素数６～１０のアリーレン基である。
　ｐおよびｑは、それぞれ独立に、０～４の整数であり、好ましくはｐおよびｑは共に０である。 In formula (2), R 10 and R 11 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or the like It is selected from a cycloalkoxyl group of 5 to 20, an aryl group of 6 to 20 carbon atoms, an aryloxy group of 6 to 20 carbon atoms, and a halogen atom, preferably a hydrogen atom.
R 12 is a hydrogen atom or a methyl group.
X represents a structure of any of the group consisting of a single bond, -O-, -S-, -SO-, -SO 2- , -CO- and the following general formulas (3) to (6).
Y and Z each independently represent an alkylene group having 2 to 6 carbon atoms which may be branched, a cycloalkylene group having 6 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms.
p and q are each independently an integer of 0 to 4, and preferably both p and q are 0.
　下記式（３）中、
Figure JPOXMLDOC01-appb-C000018
 　Ｒ１３およびＲ１４はそれぞれ独立に水素原子、ハロゲン原子、置換基を有してもよい炭素数１～２０のアルキル基、置換基を有してもよい炭素数１～５のアルコキシ基、置換基を有してもよい炭素数６～１２のアリール基、置換基を有してもよい炭素数２～５のアルケニル基、および置換基を有してもよい炭素数７～１７のアラルキル基からなる群のうちいずれかを表し、ここで、置換基はそれぞれ独立に、ハロゲン原子、炭素数１～２０のアルキル基、または炭素数６～１２のアリール基である。好ましくはＲ１３およびＲ１４は共に水素原子である。
　ｃは１～２０の整数を表し、好ましくは１～１０の整数、より好ましくは１～５の整数を表す。 In the following formula (3),
Figure JPOXMLDOC01-appb-C000018
 R 13 and R 14 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, The aryl group having 6 to 12 carbon atoms which may have a group, the alkenyl group having 2 to 5 carbon atoms which may have a substituent, and the aralkyl group having 7 to 17 carbon atoms which may have a substituent And the substituents each independently represent a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms. Preferably, both R 13 and R 14 are hydrogen atoms.
c represents an integer of 1 to 20, preferably an integer of 1 to 10, more preferably an integer of 1 to 5.
　下記式（４）中、
Figure JPOXMLDOC01-appb-C000019
 　Ｒ１５およびＲ１６はそれぞれ独立に水素原子、ハロゲン原子、置換基を有してもよい炭素数１～２０のアルキル基、置換基を有してもよい炭素数１～５のアルコキシ基、置換基を有してもよい炭素数６～１２のアリール基、置換基を有してもよい炭素数２～５のアルケニル基および置換基を有してもよい炭素数７～１７のアラルキル基からなる群のうちいずれかを表すか、または、Ｒ１５およびＲ１６はそれぞれ互いに結合して、炭素数１～２０の炭素環若しくは複素環を形成し、置換基はそれぞれ独立に、ハロゲン原子、炭素数１～２０のアルキル基、または炭素数６～１２のアリール基である。好ましくは、Ｒ１５およびＲ１６は共に水素原子であることが好ましい。 In the following formula (4),
Figure JPOXMLDOC01-appb-C000019
 R 15 and R 16 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, An aryl group having 6 to 12 carbon atoms which may have a group, an alkenyl group having 2 to 5 carbon atoms which may have a substituent, and an aralkyl group having 7 to 17 carbon atoms which may have a substituent R 15 and R 16 are each bonded to each other to form a carbocyclic ring or a heterocyclic ring having 1 to 20 carbon atoms, and the substituents each independently represent a halogen atom or a carbon atom. It is an alkyl group of 1 to 20 or an aryl group of 6 to 12 carbon atoms. Preferably, R 15 and R 16 are both hydrogen atoms.
　下記式（５）中、
Figure JPOXMLDOC01-appb-C000020
 　Ｒ１７～Ｒ２０はそれぞれ独立に水素原子、ハ口ゲン、置換基を有してもよい炭素数１～２０のアルキル基、置換基を有してもよい炭素数１～５のアルコキシ基、置換基を有してもよい炭素数６～１２のアリール基、置換基を有してもよい炭素数２～５のアルケニル基および置換基を有してもよい炭素数７～１７のアラルキル基からなる群のうちいずれかを表すか、または、Ｒ１７およびＲ１８並びにＲ１９およびＲ２０は、それぞれ互いに結合して、炭素数１～２０の炭素環若しくは複素環を形成し、置換基はそれぞれ独立に、ハロゲン原子、炭素数１～２０のアルキル基、または炭素数６～１２のアリール基である。好ましくは、Ｒ１７～Ｒ２０は共に水素原子である。 In the following formula (5),
Figure JPOXMLDOC01-appb-C000020
 R 17 to R 20 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, The aryl group having 6 to 12 carbon atoms which may have a substituent, the alkenyl group having 2 to 5 carbon atoms which may have a substituent, and the aralkyl group having 7 to 17 carbon atoms which may have a substituent Or R 17 and R 18 and R 19 and R 20 respectively bind to each other to form a carbocyclic ring or heterocyclic ring having 1 to 20 carbon atoms, and the substituents are Each of them is independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms. Preferably, R 17 to R 20 are both hydrogen atoms.
　下記式（６）中、
Figure JPOXMLDOC01-appb-C000021
 　Ｒ２１～Ｒ３０はそれぞれ独立に水素原子または炭素数１～３のアルキル基である。好ましくは、Ｒ２１～Ｒ３０は共に水素原子である。 In the following formula (6),
Figure JPOXMLDOC01-appb-C000021
 R 21 to R 30 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Preferably, R 21 to R 30 are both hydrogen atoms.
　上記式（２）中、Ｘが一般式（４）で示される構造を有することが好ましい。 In said Formula (2), it is preferable that X has a structure shown by General formula (4).
　上記一般式（２）で表される多価（メタ）アクリル系単量体としては、例えば、９，９－ビス[４－（２－（メタ）アクリロイルオキシエトキシ）フェニル]フルオレン、４，４’－イソプロピリデンジフェノールジ（メタ）アクリレート、２，２’－ビス[４－（２－(メタ)アクリロイルオキシエトキシ）フェニル]プロパン、ビス[４－（２－(メタ)アクリロイルオキシエトキシ）フェニル]メタン、１，１’－ビス[４－（２－(メタ)アクリロイルオキシエトキシ）フェニル]メタン、ビス[４－（２－(メタ)アクリロイルオキシエトキシ）フェニル]エーテル、ビス[４－（２－(メタ)アクリロイルオキシエトキシ）フェニル]スルフォキシド、ビス[４－（２－(メタ)アクリロイルオキシエトキシ）フェニル]スルファイド、ビス（４－（２－(メタ) (メタ)アクリロイルオキシエトキシ）フェニル]スルホン、ビス（４－（２－(メタ)アクリロイルオキシエトキシ）フェニル]ケトン、エトキシ化ビスフェノールＡジアクリレートおよび４，４’－ジ（メタ）アクリロイルオキシビフェニル、等が挙げられる。中でも、９，９－ビス[４－（２－（メタ）アクリロイルオキシエトキシ）フェニル]フルオレン、４，４’－イソプロピリデンジフェノールジ（メタ）アクリレート、エトキシ化ビスフェノールＡジアクリレートおよび２，２’－ビス[４－（２－(メタ)アクリロイルオキシエトキシ）フェニル]プロパンが好ましく、エトキシ化ビスフェノールＡジアクリレートおよび９，９－ビス[４－（２－（メタ）アクリロイルオキシエトキシ）フェニル]フルオレンがより好ましい。また、上記一般式（２）で表される多価（メタ）アクリル系単量体のうち市販されているものとしては、例えば、新中村化学工業株式会社製のＡＢＥ-３００やＡ－ＢＰＥ－４、Ａ－ＢＰＥＦ、共栄社化学株式会社製のライトアクリレートＢＰ－４ＥＡＬ、新中村化学工業株式会社製のビスコート＃７００ＨＶ、日立化成株式会社製のＦＡ－３２４Ａ等が挙げられるが、これらに限定されるものではない。 Examples of the polyvalent (meth) acrylic monomers represented by the above general formula (2) include 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 4,4 '-Isopropylidenediphenol di (meth) acrylate, 2,2'-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] propane, bis [4- (2- (meth) acryloyloxyethoxy) phenyl Methane, 1,1′-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] methane, bis [4- (2- (meth) acryloyloxyethoxy) phenyl] ether, bis [4- (2) -(Meth) acryloyloxyethoxy) phenyl] sulfoxide, bis [4- (2- (meth) acryloyloxyethoxy) phenyl] sulfide, bis (4- (2- (meth) TA) Acryloyloxyethoxy) phenyl] sulfone, bis (4- (2- (meth) acryloyloxyethoxy) phenyl] ketone, ethoxylated bisphenol A diacrylate and 4,4'-di (meth) acryloyloxybiphenyl etc. Among them, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, 4,4'-isopropylidenediphenol di (meth) acrylate, ethoxylated bisphenol A diacrylate and , 2′-Bis [4- (2- (meth) acryloyloxyethoxy) phenyl] propane, preferably ethoxylated bisphenol A diacrylate and 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl More preferred is fluorene, and the compound represented by the above general formula ( Among the polyvalent (meth) acrylic monomers represented by 2), commercially available ones are, for example, ABE-300, A-BPE-4, A-BPEF manufactured by Shin-Nakamura Chemical Co., Ltd., Examples thereof include light acrylate BP-4EAL manufactured by Kyoeisha Chemical Co., Ltd., biscoat # 700 HV manufactured by Shin-Nakamura Chemical Co., Ltd., FA-324A manufactured by Hitachi Chemical Co., Ltd., and the like, but the invention is not limited thereto.
３．任意の添加剤
　本発明の製造方法によって得られる組成物は、上記の構成成分以外に、本発明の主旨を逸脱しない範囲で用途に応じて種々の任意の添加剤を含むことができる。そのような添加剤としては、熱安定剤、酸化防止剤、難燃剤、難燃助剤、紫外線吸収剤、離型剤および着色剤から成る群から選択される少なくとも１種類の添加剤が例示される。添加剤の配合量は、上記一般式（１）で表される（メタ）アクリレートと上記一般式（２）で表される多価（メタ）アクリル系単量体の合計１００質量部に対して、０．００５質量部～０．１質量部であることが好ましく、０．０１質量部～０．０５質量部であることがより好ましい。 3. Optional Additives The composition obtained by the production method of the present invention may contain various optional additives in addition to the above-mentioned components according to the application without departing from the scope of the present invention. Examples of such additives include at least one additive selected from the group consisting of heat stabilizers, antioxidants, flame retardants, flame retardant aids, UV absorbers, mold release agents and colorants. Ru. The compounding amount of the additive is 100 parts by mass in total of the (meth) acrylate represented by the general formula (1) and the polyvalent (meth) acrylic monomer represented by the general formula (2). The amount is preferably 0.005 parts by mass to 0.1 parts by mass, and more preferably 0.01 parts by mass to 0.05 parts by mass.
　本発明の方法で得られた組成物は、種々の方法によって硬化することができる。詳細については後述するが、本発明の方法で得られた組成物は、好ましくは、活性エネルギー線硬化性組成物である。 The composition obtained by the method of the present invention can be cured by various methods. Although the details will be described later, the composition obtained by the method of the present invention is preferably an active energy ray curable composition.
＜塗料＞
　本発明の塗料は、本発明の方法で得られた組成物を含んでなる。本発明の塗料は主に、光学部材用のコート剤やハードコート剤等の用途に用いることができる。 <Paint>
The paint of the present invention comprises the composition obtained by the method of the present invention. The paint of the present invention can be mainly used for applications such as a coating agent for an optical member and a hard coating agent.
　本発明の塗料をプラスチックなど一般的な基材に塗布する場合においては、各種基材の表面の湿潤を助けるために、塗料中に、シリコーンあるいはアクリル系化合物といった湿潤剤を添加してもよい。適切な湿潤剤としては、ビックケミー社から入手し得るＢＹＫ３３１、ＢＹＫ３３３、ＢＹＫ３４０、ＢＹＫ３４７、ＢＹＫ３４８、ＢＹＫ３７８、ＢＹＫ３８０、ＢＹＫ３８１などがある。これらを添加する場合には、塗料の全質量を基準として０．０１～２．０質量％の範囲が好ましい。 When the paint of the present invention is applied to a general substrate such as a plastic, a wetting agent such as a silicone or an acrylic compound may be added to the paint in order to assist the surface of various substrates to be wetted. Suitable humectants include BYK 331, BYK 333, BYK 340, BYK 347, BYK 348, BYK 378, BYK 380, BYK 381 and the like available from Bick Chemie. When these are added, the range of 0.01 to 2.0% by mass is preferable based on the total mass of the paint.
　また、各種材料に対する粘着性を向上させるために、塗料中に、必要に応じてキシレン樹脂、テルペン樹脂、フェノール樹脂、ロジン樹脂などの粘着付与剤を添加してもよい。これらを添加する場合には、塗料の全質量を基準として０．０１～２．０質量％の範囲が好ましい。 Moreover, in order to improve the adhesiveness with respect to various materials, you may add tackifiers, such as a xylene resin, a terpene resin, a phenol resin, rosin resin, in a coating material as needed. When these are added, the range of 0.01 to 2.0% by mass is preferable based on the total mass of the paint.
　各種材料に対する接着性を向上させるために、塗料中にシランカップリング剤、チタンカップリング剤などのカップリング剤を添加してもよい。これらを添加する場合には、塗料の全質量を基準として０．０１～５．０質量％の範囲が好ましい。 In order to improve adhesion to various materials, a coupling agent such as a silane coupling agent or a titanium coupling agent may be added to the paint. When these are added, the range of 0.01 to 5.0% by mass is preferable based on the total mass of the paint.
　また、耐衝撃性などの諸性能を向上させるために、塗料中にシリカ、アルミナ、マイカ、タルク、アルミニウムフレーク、ガラスフレークなどの無機フィラーを添加してもよい。これらを添加する場合には、塗料の全質量を基準として０．０１～１０．０質量％の範囲が好ましい。 In order to improve various performances such as impact resistance, inorganic fillers such as silica, alumina, mica, talc, aluminum flakes and glass flakes may be added to the paint. When these are added, the range of 0.01 to 10.0% by mass is preferable based on the total mass of the paint.
　さらに、本発明の塗料を金属やコンクリート、プラスチックなど一般的な基材に塗布する場合においては、撹拌混合や塗布時に発生する泡の消失を助けるため、塗料中に、シリコーン系あるいはアクリル系化合物からなる消泡剤を添加してもよい。適切な消泡剤としては、ビックケミー社から入手し得るＢＹＫ０１９、ＢＹＫ０５２、ＢＹＫ０６５、ＢＹＫ０６６Ｎ、ＢＹＫ０６７Ｎ、ＢＹＫ０７０、ＢＹＫ０８０などが挙げられるが、特にＢＹＫ０６５が好ましい。これらを添加する場合には、塗料の全質量を基準として０．０１～３．０質量％の範囲が好ましい。 Furthermore, when the paint of the present invention is applied to a general substrate such as metal, concrete, plastic, etc., silicone or acrylic compound is added to the paint in order to aid the disappearance of bubbles generated during stirring and mixing. May be added. Suitable antifoam agents include BYK019, BYK052, BYK065, BYK066N, BYK067N, BYK070, BYK080, etc., which are available from Bick Chemie, with BYK065 being particularly preferred. When these are added, the range of 0.01 to 3.0% by mass is preferable based on the total mass of the paint.
　本発明の塗料には、必要に応じてリン酸亜鉛、リン酸鉄、モリブデン酸カルシウム、酸化バナジウム、水分散シリカ、ヒュームドシリカなどの防錆添加剤、フタロシアニン系有機顔料、縮合多環系有機顔料などの有機顔料、酸化チタン、酸化亜鉛、炭酸カルシウム、硫酸バリウム、アルミナ、カーボンブラックなどの無機顔料などの各成分を必要量添加してもよい。 In the paint of the present invention, if necessary, rust-preventive additives such as zinc phosphate, iron phosphate, calcium molybdate, vanadium oxide, water-dispersed silica, fumed silica, phthalocyanine-based organic pigments, condensed polycyclic organic compounds A necessary amount of each component such as an organic pigment such as pigment, an inorganic pigment such as titanium oxide, zinc oxide, calcium carbonate, barium sulfate, alumina, carbon black may be added.
　本発明の塗料を各種基材上に塗布する際の塗装形式としては、例えば、バーコーター塗工、メイヤーバー塗工、エアナイフ塗工、グラビア塗工、リバースグラビア塗工、マイクログラビア塗工、マイクロリバースグラビアコーター塗工、ダイコーター塗工、スロットダイコーター塗工、バキュームダイコーター塗工、ディップ塗工、スピンコート塗工、スプレー塗工、はけ塗りなどの一般的に使用される塗装形式のいずれも使用され得る。ロール塗布又はスプレー塗布が好ましい。 Examples of coating methods for applying the paint of the present invention on various substrates include bar coater coating, mayer bar coating, air knife coating, gravure coating, reverse gravure coating, microgravure coating, and micro Commonly used coating methods such as reverse gravure coater coating, die coater coating, slot die coater coating, vacuum die coater coating, dip coating, spin coating coating, spray coating, and brush coating Both may be used. Roll application or spray application is preferred.
＜硬化体＞
　本発明の硬化体は、本発明の方法で得られた組成物を硬化させてなる硬化体である。本発明の硬化体は、１．５８０以上の高い屈折率を有し、かつ、高温高湿度下での環境試験において黄変が少ない。また、本発明の硬化体は、１．５８５以上の高い屈折率を有するのが好ましく、１．５９０以上の高い屈折率を有するのがより好ましい。また、本発明の硬化体は、８５℃／８５％ＲＨ雰囲気中に３５０時間保管した際の黄色度（ＹＩ）が４．０以下であることが好ましく、８５℃／８５％ＲＨ雰囲気中に１,０００時間保管した際の黄色度（ＹＩ）が６．５以下であることが好ましい。 <Cured body>
The cured product of the present invention is a cured product obtained by curing the composition obtained by the method of the present invention. The cured product of the present invention has a high refractive index of 1.580 or more, and less yellowing in environmental tests under high temperature and high humidity. The cured product of the present invention preferably has a high refractive index of 1.585 or more, and more preferably a high refractive index of 1.590 or more. In addition, the cured product of the present invention preferably has a yellowness (YI) of 4.0 or less when stored in an atmosphere at 85 ° C./85% RH for 350 hours, and 1 in an atmosphere at 85 ° C./85% RH It is preferable that the yellowness (YI) at the time of storing for 2,000 hours is 6.5 or less.
　本発明の硬化体は、
（Ａ）一般式（１）で表される（メタ）アクリレートから誘導される構成単位と
Figure JPOXMLDOC01-appb-C000022
 　一般式（２）で表される多価（メタ）アクリル系単量体から誘導される構成単位と
Figure JPOXMLDOC01-appb-C000023
 を含む。 The cured product of the present invention is
(A) Structural units derived from (meth) acrylates represented by the general formula (1) and
Figure JPOXMLDOC01-appb-C000022
 Structural units derived from multivalent (meth) acrylic monomers represented by the general formula (2)
Figure JPOXMLDOC01-appb-C000023
 including.
　ここで、一般式（１）におけるＸ、Ｙ、Ｒ１、Ｒ４、Ｒ５、ｍ、ｎ、ｐおよびｑは、それぞれ本発明の方法で得られた組成物のものと同様である。また、一般式（２）におけるＲ１０、Ｒ１１、Ｒ１２、Ｘ、Ｙ、Ｚ、ｐおよびｑも、それぞれ本発明の方法で得られた組成物のものと同様である。 Here, X, Y, R 1 , R 4 , R 5 , m, n, p and q in the general formula (1) are respectively the same as those of the composition obtained by the method of the present invention. In addition, R 10 , R 11 , R 12 , X, Y, Z, p and q in the general formula (2) are respectively the same as those of the composition obtained by the method of the present invention.
　なお、一般式（１）で表される（メタ）アクリレートから誘導される構成単位とは、下記式（１ａ）の構造を有する構成単位を示し、
Figure JPOXMLDOC01-appb-C000024
 　一般式（２）で表される多価（メタ）アクリル系単量体から誘導される構成単位とは、下記式（２ａ）の構造を有する構成単位を示す。
Figure JPOXMLDOC01-appb-C000025
 In addition, the structural unit derived | led-out from the (meth) acrylate represented by General formula (1) shows the structural unit which has a structure of following formula (1a),
Figure JPOXMLDOC01-appb-C000024
 The structural unit derived from the multivalent (meth) acrylic monomer represented by the general formula (2) indicates a structural unit having a structure of the following formula (2a).
Figure JPOXMLDOC01-appb-C000025
　ここで、一般式（１ａ）におけるＸ、Ｙ、Ｒ１、Ｒ４、Ｒ５、ｍ、ｎ、ｐおよびｑは、それぞれ一般式（１）のものと対応し、一般式（２ａ）におけるＲ１０、Ｒ１１、Ｒ１２、Ｘ、Ｙ、Ｚ、ｐおよびｑは、一般式（２）のものと対応する。 Here, X, Y, R 1 , R 4 , R 5 , m, n, p and q in the general formula (1a) correspond to those in the general formula (1), respectively, and R in the general formula (2a) 10 , R 11 , R 12 , X, Y, Z, p and q correspond to those of the general formula (2).
　本発明の硬化体の製造方法は、本発明の方法で組成物を得る工程と、その組成物を硬化させる工程とを含む。ここで、硬化を行う方法は特に限定されず、種々の公知の方法によって行ってもよい。例えば、本発明の組成物は、活性エネルギー線を照射することによる光重合によって硬化させてもよい。本明細書において、「活性エネルギー線」とは、紫外線、電子線、イオンビーム、およびＸ線等を意味する。 The method for producing a cured product of the present invention includes the steps of obtaining a composition by the method of the present invention and curing the composition. Here, the method of curing is not particularly limited, and may be performed by various known methods. For example, the composition of the present invention may be cured by photopolymerization by irradiating active energy rays. In the present specification, “active energy ray” means ultraviolet light, electron beam, ion beam, X-ray and the like.
　本発明の方法で得られた組成物を活性エネルギー線により硬化させる場合、光重合開始剤は必ずしも必要でない。しかし、光重合開始剤を添加する場合、例えば、Ｃｉｂａ社から入手可能なＩｒｇａｃｕｒｅ（登録商標）２９５９(１－［４－（２－ヒドロキシエトキシ）フェニル］－２－ヒドロキシ－２－メチル－１－プロパン－１－オン、Ｉｒｇａｃｕｒｅ（登録商標）１８４（１－ヒドロキシシクロヘキシルフェニルケトン）、Ｉｒｇａｃｕｒｅ（登録商標）５００（１－ヒドロキシシクロヘキシルフェニルケトン、ベンゾフェノン）、Ｉｒｇａｃｕｒｅ（登録商標）６５１（２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン）、Ｉｒｇａｃｕｒｅ（登録商標）３６９（２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）ブタノン－１）、Ｉｒｇａｃｕｒｅ（登録商標）９０７（２－メチル－１［４－メチルチオフェニル］－２－モルフォリノプロパン－１－オン、Ｉｒｇａｃｕｒｅ（登録商標）８１９（ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド、Ｉｒｇａｃｕｒｅ（登録商標）１８００（ビス（２，６－ジメトキシベンゾイル）－２，４，４－トリメチル－ペンチルフォスフィンオキサイド，１－ヒドロキシ－シクロヘキシル－フェニル－ケトン）、Ｉｒｇａｃｕｒｅ（登録商標）１８００（ビス（２，６－ジメトキシベンゾイル）－２，４，４－トリメチル－ペンチルフォスフィンオキサイド，２－ヒドロキシ－２－メチル－１－フェニル－１－プロパン－１－オン）、Ｉｒｇａｃｕｒｅ（登録商標）ＯＸＥ０１（１，２－オクタンジオン，１－［４－（フェニルチオ）フェニル］－２－（Ｏ－ベンゾイルオキシム）、Ｄａｒｏｃｕｒ（登録商標）１１７３（２－ヒドロキシ－２－メチル－１－フェニル－１－プロパン－１－オン）、Ｄａｒｏｃｕｒ（登録商標）１１１６、１３９８、１１７４及び１０２０、ＣＧＩ２４２（エタノン，１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］－１－（Ｏ－アセチルオキシム）、ＢＡＳＦ社から入手可能なＬｕｃｉｒｉｎＴＰＯ（２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイド）、Ｌｕｃｉｒｉｎ ＴＰＯ－Ｌ（２，４，６－トリメチルベンゾイルエトキシフェニルホスフィンオキサイド）、日本シイベルヘグナー社から入手可能なＥＳＡＣＵＲＥ１００１Ｍ（１－［４－ベンゾイルフェニルスルファニル］フェニル］－２－メチル－２－（４－メチルフェニルスルホニル）プロパン－１－オン、旭電化社から入手可能なアデカオプトマー（登録商標）Ｎ－１４１４（カルバゾール・フェノン系）、アデカオプトマー（登録商標）Ｎ－１７１７（アクリジン系）、アデカオプトマー（登録商標）Ｎ－１６０６（トリアジン系）、三和ケミカル製のＴＦＥ－トリアジン（２－［２－（フラン－２－イル）ビニル］－４，６－ビス（トリクロロメチル）－１，３，５－トリアジン）、三和ケミカル製のＴＭＥ－トリアジン（２－［２－（５－メチルフラン－２－イル）ビニル］－４，６－ビス（トリクロロメチル）－１，３，５－トリアジン）、三和ケミカル製のＭＰ－トリアジン（２－（４－メトキシフェニル）－４，６－ビス（トリクロロメチル）－１，３，５－トリアジン）、ミドリ化学製ＴＡＺ－１１３（２－［２－（３，４－ジメトキシフェニル）エテニル］－４，６－ビス（トリクロロメチル）－１，３，５－トリアジン）、ミドリ化学製ＴＡＺ－１０８（２－（３，４－ジメトキシフェニル）－４，６－ビス（トリクロロメチル）－１，３，５－トリアジン）、ベンゾフェノン、４，４’－ビスジエチルアミノベンゾフェノン、メチル－２－ベンゾフェノン、４－ベンゾイル－４’－メチルジフェニルスルフィド、４－フェニルベンゾフェノン、エチルミヒラーズケトン、２－クロロチオキサントン、２－メチルチオキサントン、２－イソプロピルチオキサントン、４－イソプロピルチオキサントン、２，４－ジエチルチオキサントン、１－クロロ－４－プロポキシチオキサントン、２－メチルチオキサントン、チオキサントンアンモニウム塩、ベンゾイン、４，４’－ジメトキシベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル、ベンジルジメチルケタール、１，１，１－トリクロロアセトフェノン、ジエトキシアセトフェノンおよびジベンゾスベロン、ｏ－ベンゾイル安息香酸メチル、２－ベンゾイルナフタレン、４－ベンゾイルビフェニル、４－ベンゾイル ジフェニルエーテル、１，４－ベンゾイルベンゼン、ベンジル、１０－ブチル－２－クロロアクリドン、［４－（メチルフェニルチオ）フェニル］フェニルメタン）、２－エチルアントラキノン、２，２－ビス（２－クロロフェニル）４，５，４’，５’－テトラキス（３，４，５－トリメトキシフェニル）１，２’－ビイミダゾール、２，２－ビス（ｏ－クロロフェニル）４，５，４’，５’－テトラフェニル－１，２’－ビイミダゾール、トリス（４－ジメチルアミノフェニル）メタン、エチル－４－（ジメチルアミノ）ベンゾエート、２－（ジメチルアミノ）エチルベンゾエート、ブトキシエチル－４－（ジメチルアミノ）ベンゾエート、等が挙げられる。これらの光重合開始剤は単独で使用してもよいし、２種以上組み合せて用いてもよい。また、これらの光重合開始剤の添加量は、組成物中、０．０１質量％～１５質量％、好ましくは０．１質量％～１０質量％の範囲である。 When the composition obtained by the method of the present invention is cured by active energy radiation, a photopolymerization initiator is not necessarily required. However, when a photoinitiator is added, for example, Irgacure® 2959 (1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-l available from Ciba Propan-1-one, Irgacure® 184 (1-hydroxycyclohexyl phenyl ketone), Irgacure® 500 (1-hydroxycyclohexyl phenyl ketone, benzophenone), Irgacure® 651 (2, 2-dimethoxyamine) -1,2-Diphenylethan-1-one), Irgacure 369 (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1), Irgacure 907 ( 2-Methyl-1 [4-methylthiophen [Nyl] -2-morpholinopropan-1-one, Irgacure® 819 (Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, Irgacure® 1800 (Bis (2,6- Dimethoxybenzoyl) -2,4,4-trimethyl-pentyl phosphine oxide, 1-hydroxy-cyclohexyl-phenyl-ketone), Irgacure® 1800 (bis (2,6-dimethoxybenzoyl) -2,4,4 -Trimethyl-pentylphosphine oxide, 2-hydroxy-2-methyl-1-phenyl-1-propan-1-one), Irgacure® OXE01 (1,2-octanedione, 1- [4- (phenylthio) ) Phenyl] -2- (O-benzoyloxy ), Darocur® 1173 (2-hydroxy-2-methyl-1-phenyl-1-propan-1-one), Darocur® 1116, 1398, 1174 and 1020, CGI 242 (ethanone, 1- [1 9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), LucirinTPO (2,4,6-trimethylbenzoyl diphenyl phosphine oxide available from BASF) Lucirin TPO-L (2,4,6-trimethyl benzoyl ethoxy phenyl phosphine oxide), ESACURE 1001 M (1- [4-benzoylphenylsulfanyl] phenyl] -2-methyl-2- (4 available from Nippon Shiver Hegner) -Methyl Phenylsulfonyl) propan-1-one, Adekaoptomer (registered trademark) N-1414 (carbazole / phenone type) available from Asahi Denka Co., Adeka optomer (registered trademark) N-1717 (acridine type), adecaopter MER (registered trademark) N-1606 (triazine series), TFE-triazine (2- [2- (furan-2-yl) vinyl] -4,6-bis (trichloromethyl) -1,3 manufactured by Sanwa Chemical Co., Ltd. , 5-triazine), TME-triazine (2- [2- (5-methylfuran-2-yl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, manufactured by Sanwa Chemical Co., Ltd. ), MP-triazine (2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine) manufactured by Sanwa Chemical Co., Ltd., manufactured by Midori Chemical AZ-113 (2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine), Midori Kagaku TAZ-108 (2- (3 , 4-Dimethoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine), benzophenone, 4,4'-bisdiethylaminobenzophenone, methyl-2-benzophenone, 4-benzoyl-4'- Methyl diphenyl sulfide, 4-phenyl benzophenone, ethyl Michler's ketone, 2-chlorothioxanthone, 2-methyl thioxanthone, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 1-chloro-4-propoxy thioxanthone, 2-Methylthioxanthone, Thioxa Ton ammonium salts, benzoin, 4,4'-dimethoxybenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, 1,1,1-trichloroacetophenone, diethoxyacetophenone and dibenzosuberone Methyl, o-benzoylbenzoate, 2-benzoylnaphthalene, 4-benzoylbiphenyl, 4-benzoyldiphenylether, 1,4-benzoylbenzene, benzyl, 10-butyl-2-chloroacridone, [4- (methylphenylthio)] Phenyl] phenylmethane), 2-ethylanthraquinone, 2,2-bis (2-chlorophenyl) 4,5,4 ', 5'-tetrakis (3,4,5-trimethoxyphenyl) 1 2'-biimidazole, 2,2-bis (o-chlorophenyl) 4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole, tris (4-dimethylaminophenyl) methane, ethyl-4 And-(dimethylamino) benzoate, 2- (dimethylamino) ethyl benzoate, butoxyethyl 4- (dimethylamino) benzoate and the like. These photopolymerization initiators may be used alone or in combination of two or more. The addition amount of these photopolymerization initiators is in the range of 0.01% by mass to 15% by mass, preferably 0.1% by mass to 10% by mass in the composition.
　以下、本発明について実施例を参照して詳述するが、本発明の技術的範囲はこれに限定されるものではない。実施例中の「部」および「％」は、それぞれ「質量部」および「質量％」を表す。 Hereinafter, the present invention will be described in detail with reference to Examples, but the technical scope of the present invention is not limited thereto. "Part" and "%" in an Example represent "mass part" and "mass%", respectively.
　また、実施例および比較例における各物性の測定は、以下の方法により行った。 Moreover, the measurement of each physical property in an Example and a comparative example was performed with the following method.
１．組成物粘度
　下記に記載の方法で得られる組成物の粘度を、Ｅ型粘度計（ＴＶ－２２型）を用いて、測定温度：２５℃で測定した。 1. Composition Viscosity The viscosity of the composition obtained by the method described below was measured at a measurement temperature of 25 ° C. using an E-type viscometer (TV-22 type).
２．組成物の屈折率
　下記に記載の方法で得られる組成物を、多波長アッべ屈折率計ＤＲ－Ｍ２（株式会社アタゴ社製）を用いて、測定波長：５８９ｎｍ、測定温度：２３℃にて測定した。 2. The refractive index of the composition: The composition obtained by the method described below was measured at a measurement wavelength of 589 nm at a measurement temperature of 23 ° C. using a multi-wavelength Abbe refractometer DR-M2 (manufactured by Atago Co., Ltd.). It was measured.
３．硬化物の屈折率
　下記に記載の方法で得られる組成物の硬化物を、多波長アッべ屈折率計ＤＲ－Ｍ２（株式会社アタゴ社製）を用いて、測定波長：５８９ｎｍ、測定温度：２３℃にて測定した。 3. Refractive Index of Cured Product A cured product of the composition obtained by the method described below is measured using a multi-wavelength Abbe refractometer DR-M2 (manufactured by Atago Co., Ltd.) at a measurement wavelength of 589 nm and a measurement temperature of 23 It measured at ° C.
４．黄色度（ＹＩ）
　ヘーズメーターＮＤＨ４０００（日本電色工業株式会社製）を用いて、ＪＩＳ Ｋ ７３７３に準じて黄色度（ＹＩ）の測定を行った。 4. Yellowness (YI)
The yellowness (YI) was measured according to JIS K 7373 using a haze meter NDH4000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.).
５．剥離性
　下記に記載の方法で得られた組成物の硬化体を、８５℃・８５％ＲＨ環境下で保管を行った。所定の時間が経過した際に、基材フィルムであるＰＥＴフィルムから、組成物の硬化体が剥離しているかを目視で確認した。 5. Peelability The cured product of the composition obtained by the method described below was stored under an environment of 85 ° C. and 85% RH. When a predetermined time passed, it was visually confirmed whether the cured product of the composition had peeled off from the PET film which is the base film.
＜実施例１：組成物およびその硬化体の調製＞
　単官能（メタ）アクリレートと一般式（２）で表される多価（メタ）アクリル系単量体とを含む液体組成物の粘度と屈折率を調べるために、表１の組成で液体組成物例１～例１３を調製した。６０℃で１時間加温することで粘度を低下させた一般式（２）で表される多価（メタ）アクリル系単量体と、単官能（メタ）アクリレートとをブレンドし、よく撹拌することで、均一に溶解させて液体組成物を得た。次に、２３℃の雰囲気下で１２時間保管することで、組成物の温度を２３℃とした。その後、粘度と屈折率を測定した。
Figure JPOXMLDOC01-appb-T000026
 <Example 1: Preparation of composition and its cured product>
In order to investigate the viscosity and refractive index of a liquid composition containing a monofunctional (meth) acrylate and a polyvalent (meth) acrylic monomer represented by the general formula (2), the liquid composition with the composition of Table 1 Examples 1 to 13 were prepared. Blend the monofunctional (meth) acrylate with the polyvalent (meth) acrylic monomer represented by the general formula (2) whose viscosity is lowered by heating at 60 ° C. for 1 hour, and stir well The solution was uniformly dissolved to obtain a liquid composition. Next, the temperature of the composition was brought to 23 ° C. by storing for 12 hours under an atmosphere of 23 ° C. Thereafter, the viscosity and the refractive index were measured.
Figure JPOXMLDOC01-appb-T000026
　化学式（Ａ）～（Ｄ）の化合物としては、下記の化合物を使用した。化学式（Ａ）の化合物として大阪ガスケミカル株式会社製のOGSOL EA0200を用い、化学式（Ｂ）の化合物として新中村化学工業株式会社製のALEN-10を用い、化学式（Ｃ）の化合物として共栄社化学株式会社製のPOB-Aを用い、化学式（Ｄ）の化合物は公知の方法によって合成した。
　化学式（Ｄ）の化合物の合成方法は、具体的には、次のとおりである。まず、ビフェニルメタノール ９０重量部、アクリル酸メチル１５６重量部、４－メトキシフェノール０．４ 重量部を丸底フラスコに仕込み、空気流通下で加熱して系内の水分を除去した後、チタンテトライソプロポキシド ０．８２重量部を添加して反応を開始した。反応液を９０℃に加熱して、反応により生じたメタノールを除去し、適宜アクリル酸メチルを追加しながら６時間反応させた。反応終了後、純水１０重量部を添加することで触媒を加水分解した。さらに蒸留、濾過により精製し、化学式（Ｄ）の化合物を得た。
 
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000030
   The following compounds were used as the compounds of chemical formulas (A) to (D). Kyo Oisha Chemical Co., Ltd. as a compound of chemical formula (C) using OGSOL EA0200 manufactured by Osaka Gas Chemical Co., Ltd. as the compound of chemical formula (A) and ALEN-10 manufactured by Shin-Nakamura Chemical Co., Ltd. as the compound of chemical formula (B) The compound of the formula (D) was synthesized by a known method using POB-A manufactured by the company.
Specifically, the synthesis method of the compound of the chemical formula (D) is as follows. First, 90 parts by weight of biphenyl methanol, 156 parts by weight of methyl acrylate and 0.4 parts by weight of 4-methoxyphenol are charged in a round bottom flask and heated under air flow to remove water in the system, and then titanium tetraiso is removed. The reaction was initiated by the addition of 0.82 parts by weight of propoxide. The reaction solution was heated to 90 ° C. to remove methanol produced by the reaction, and the reaction was allowed to proceed for 6 hours while adding methyl acrylate as appropriate. After completion of the reaction, 10 parts by weight of pure water was added to hydrolyze the catalyst. Further purification by distillation and filtration gave a compound of the formula (D).

Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000030
　上記の結果から、化学式（Ｄ）の化合物を用いると、低粘度であり、かつ、硬化時に高い屈折率を有する液体組成物が得られることが分かる。 From the above results, it can be seen that when the compound of the formula (D) is used, a liquid composition having a low viscosity and a high refractive index upon curing can be obtained.
＜実施例２：各液体組成物組成物およびその硬化体の物性＞
　単官能（メタ）アクリレートと一般式（２）で表される多価（メタ）アクリル系単量体とを５０：５０の割合で含む液体組成物例１４～１６を調製し、その組成物および硬化体の諸物性を測定した。６０℃で１時間加温することで粘度を低下させた一般式（２）で表される多価（メタ）アクリル系単量体を２０質量部と、単官能（メタ）アクリレートを２０質量部と、光重合開始剤であるＩｒｕｇａｃｕｒｅ１８４（チバ・スペシャリティ・ケミカルズ製）を１．２質量部とをブレンドし、よく撹拌することで、均一に溶解させて液体組成物を得た。次に、基材である厚み５０μｍのポリエステルフィルム（東洋紡株式会社製；東洋紡エステルフィルムＥ５１００）のコロナ処理面に、液体組成物をバーコーターＮｏ．６０を用いて塗布し、すぐさま、３００ｍＪ／ｃｍ２の紫外線照射量となるように設定したコンベアタイプの紫外線照射装置Ｕ－０３０３（株式会社ＧＳユアサ製、高圧水銀ランプ使用、ランプ出力：８０Ｗ／ｃｍ、コンベアスピード：４．８ｍ／ｍｉｎ）を用いて紫外線を照射し、ポリエステルフィルム上に液体組成物の硬化体が形成されたフィルムを得た。結果を表２に示す。
Figure JPOXMLDOC01-appb-T000031
 　表２に記載の各物性は、下記の方法で測定した。
［鉛筆硬度］
　鉛筆硬度はＪＩＳ Ｋ５６００－５－４に準じて測定した。具体的には、液体組成物の硬化体が形成されたポリエステルフィルムの表面に対して、角度４５度、荷重７５０ｇで乾燥塗膜表面に硬度の低い方から順番に鉛筆を押し付け、傷跡を生じなかった最も硬い鉛筆の硬度を鉛筆硬度として評価した。鉛筆硬度は、ランクが低い順に、２Ｂ、Ｂ、ＨＢ、Ｆ、Ｈ、２Ｈ、３Ｈ、４Ｈ、５Ｈ、６Ｈおよび７Ｈで示される。
［伸び］
　６０℃で１時間加温することで粘度を低下させた一般式（２）で表される多価（メタ）アクリル系単量体を２０質量部と単官能（メタ）アクリレートを２０質量部、光重合開始剤であるＩｒｕｇａｃｕｒｅ１８４（チバ・スペシャリティ・ケミカルズ製）を１．２質量部ブレンドし、よく撹拌することで、均一に溶解させることで液体組成物を得た。次に、基材である厚み５０μｍのポリエステルフィルム（東洋紡株式会社製；東洋紡エステルフィルムＥ５１００）の非コロナ処理面に、液体組成物をバーコーターＮｏ．６０を用いて塗布し、すぐさま、３００ｍＪ／ｃｍ２の紫外線照射量となるように設定したコンベアタイプの紫外線照射装置Ｕ－０３０３（株式会社ＧＳユアサ製、高圧水銀ランプ使用、ランプ出力：８０Ｗ／ｃｍ、コンベアスピード：４．８ｍ／ｍｉｎ）を用いて紫外線を照射し、ポリエステルフィルム上に液体組成物の硬化体が形成されたフィルムを得た。ポリエステルフィルム面から液体組成物の硬化体を剥し、ＪＩＳＫ７１６１－１に準じて引張試験を行った。
［ＨＡＺＥ］
ヘーズメーターＮＤＨ４０００（日本電色工業株式会社製）を用いて、ＪＩＳ Ｋ ７１３６に準じてＨＡＺＥの測定を行った。
［全光線透過率］
ヘーズメーターＮＤＨ４０００（日本電色工業株式会社製）を用いて、ＪＩＳ Ｋ ７３７５に準じて全光線透過率（Ｔ．Ｔ．）の測定を行った。
［飽和吸水率］
上記のように液体組成物の硬化体を作成し、５ｃｍ×５ｃｍのサンプル片を作成し、５０℃で２４時間乾燥させた。次に、乾燥させたサンプルの重量を測定し、その後、２３℃の水に浸漬後、所定時間経過後、試験片を水から取り出し、水分を拭き取りその質量を測定した。吸水率が飽和するまで、この作業を続け、飽和した時の試験片の重量を飽和した時の重量として、下記の計算式で飽和吸水率を測定した。
飽和吸水率（％）＝飽和した時の試験片の重量／乾燥させたサンプルの重量×１００
［ガラス転移温度］
　ＤＳＣ６２００（セイコーインスツル株式会社製）を用いて、ＪＩＳ－Ｋ－７１２１に準じてガラス転移温度の測定を行った。 <Example 2: Physical Properties of Each Liquid Composition and Its Cured Body>
Liquid composition examples 14 to 16 comprising a monofunctional (meth) acrylate and a polyvalent (meth) acrylic monomer represented by the general formula (2) in a ratio of 50:50 are prepared, the composition and Various physical properties of the cured product were measured. 20 parts by mass of the polyvalent (meth) acrylic monomer represented by the general formula (2) whose viscosity is lowered by heating at 60 ° C. for 1 hour, and 20 parts by mass of monofunctional (meth) acrylate And 1.2 parts by mass of Irugacure 184 (manufactured by Ciba Specialty Chemicals), which is a photopolymerization initiator, were blended and stirred well to be uniformly dissolved to obtain a liquid composition. Next, on the corona-treated surface of a 50 μm thick polyester film (Toyobo Co., Ltd .; Toyobo Ester Film E5100) as a substrate, the liquid composition was treated with a bar coater No. Apply using 60 and immediately set a UV irradiation dose of 300 mJ / cm 2 Conveyer type UV irradiation device U-0303 (GS Yuasa Co., Ltd., using high pressure mercury lamp, lamp output: 80 W / cm The film was irradiated with ultraviolet light using a conveyor speed of 4.8 m / min) to obtain a film in which a cured product of the liquid composition was formed on a polyester film. The results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000031
 Each physical property described in Table 2 was measured by the following method.
[Pencil hardness]
The pencil hardness was measured according to JIS K5600-5-4. Specifically, a pencil is pressed on the surface of the dried coated film in order from the lowest hardness at an angle of 45 degrees and a load of 750 g against the surface of the polyester film on which the cured product of the liquid composition is formed. The hardness of the hardest pencil was evaluated as pencil hardness. The pencil hardness is shown by 2B, B, HB, F, H, 2H, 3H, 4H, 5H, 6H and 7H in ascending order of rank.
[Elongation]
20 parts by mass of the polyvalent (meth) acrylic monomer represented by the general formula (2) whose viscosity is lowered by heating at 60 ° C. for 1 hour, and 20 parts by mass of monofunctional (meth) acrylate, A liquid composition was obtained by blending 1.2 parts by mass of Irugacure 184 (manufactured by Ciba Specialty Chemicals), which is a photopolymerization initiator, and thoroughly stirring to dissolve uniformly. Next, a liquid composition was applied to the non-corona treated surface of a 50 μm thick polyester film (Toyobo Co., Ltd .; Toyobo Ester Film E5100), which is a substrate, as a bar coater No. Apply using 60 and immediately set a UV irradiation dose of 300 mJ / cm 2 Conveyer type UV irradiation device U-0303 (GS Yuasa Co., Ltd., using high pressure mercury lamp, lamp output: 80 W / cm The film was irradiated with ultraviolet light using a conveyor speed of 4.8 m / min) to obtain a film in which a cured product of the liquid composition was formed on a polyester film. The cured product of the liquid composition was peeled off from the polyester film surface, and a tensile test was performed according to JIS K7161-1.
[HAZE]
The haze was measured according to JIS K 7136 using a haze meter NDH4000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.).
[Total light transmittance]
The total light transmittance (TT) was measured according to JIS K 7375 using a haze meter NDH4000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.).
[Saturated water absorption rate]
A cured product of the liquid composition was made as described above, and a 5 cm × 5 cm sample piece was made and dried at 50 ° C. for 24 hours. Next, the weight of the dried sample was measured, and after immersion in water at 23 ° C., after a predetermined time elapsed, the test piece was taken out of the water, the water was wiped off, and the mass was measured. This work was continued until the water absorption was saturated, and the saturated water absorption was measured by the following formula as the weight when the weight of the test piece when saturated was saturated.
Saturated water absorption (%) = weight of test piece when saturated / weight of dried sample × 100
[Glass-transition temperature]
The glass transition temperature was measured according to JIS-K-7121 using DSC 6200 (manufactured by Seiko Instruments Inc.).
　上記の結果から、化学式（Ｄ）の単官能（メタ）アクリレートを用いると、高屈折率、低吸水率、かつ高Ｔｇの硬化体が得られることが分かる。 From the above results, it is understood that when using the monofunctional (meth) acrylate of the chemical formula (D), a cured product having a high refractive index, a low water absorption, and a high Tg can be obtained.
＜実施例３：各液体組成物およびその硬化体の高温高湿度下での着色評価＞
　単官能（メタ）アクリレートと一般式（２）で表される多価（メタ）アクリル系単量体とを表３に記載の割合で含む液体組成物例１７～２５を調製し、それぞれの高温・高湿下での着色を評価した。調製の際には、６０℃で１時間加温することで粘度を低下させた一般式（２）で表される多価（メタ）アクリル系単量体を表３に記載の比率で単官能メタアクリレートと混合した。併せて、高温・高湿下での剥離の発生についても確認した。液体組成物の硬化体が形成されたポリエステルフィルムを、８５℃／８５％ＲＨ雰囲気に設定した恒温恒湿機中に保管し、３５０時間経過時と１０００時間経過時に、上記の測定方法で黄色度（ＹＩ）を測定した。
Figure JPOXMLDOC01-appb-T000032
 <Example 3: Coloring evaluation under high temperature and high humidity of each liquid composition and its cured product>
Liquid composition examples 17 to 25 containing monofunctional (meth) acrylate and the polyvalent (meth) acrylic monomer represented by the general formula (2) in the proportions described in Table 3 are prepared, and respective high temperature The coloration under high humidity was evaluated. At the time of preparation, the polyvalent (meth) acrylic monomer represented by the general formula (2) whose viscosity is lowered by heating at 60 ° C. for 1 hour is monofunctional in the ratio described in Table 3 Mixed with methacrylate. At the same time, the occurrence of peeling under high temperature and high humidity was also confirmed. The polyester film on which the cured product of the liquid composition is formed is stored in a constant temperature and humidity chamber set at 85 ° C./85% RH atmosphere, and yellowness is measured by the above measuring method at 350 hours and 1000 hours. (YI) was measured.
Figure JPOXMLDOC01-appb-T000032
　上記の結果から、化学式（Ｄ）の単官能（メタ）アクリレートを用いると、高温・高湿下でも着色が抑えられ、単官能メタクリレートの添加量を７５ｗｔ％とすることで、剥離も効果的に抑えられることが分かった。 From the above results, when the monofunctional (meth) acrylate of the chemical formula (D) is used, coloring is suppressed even under high temperature and high humidity, and peeling is also effectively performed by setting the amount of monofunctional methacrylate to 75 wt%. It turned out that it can be suppressed.
＜実施例４：結晶化の評価＞
　単官能（メタ）アクリレートと一般式（２）で表される多価（メタ）アクリル系単量体とを表４～６に記載の割合で含む液体組成物例２６～４９を調製し、その際ブレンド温度を変えることで結晶の発生に影響するかを評価した。結果を表４～表７に示す。表に示す温度に調温した化学式（Ａ）、（Ｃ）、（Ｄ）の化合物を用いて、表に示す配合および方法でブレンドし、よく撹拌し、均一に溶解させることで液体組成物を得た。なお、化学式（Ｄ）／（Ｃ）は、化学式（Ｄ）の化合物と化学式（Ｃ）の化合物の重量比１：１の混合物を意味する。次に、表に示す保管条件で保管を実施し、所定の時間が経過したところで、目視で結晶の析出の有無を確認した。なお、「２３℃／１ｄａｙ→５℃保管」は、２３℃で１日保管した後に５℃で保管することを意味し、「結晶化（５℃／５ｄａｙ）」は５℃で５日間保管することを意味する。
Figure JPOXMLDOC01-appb-T000033
 　例２６および例２７の結果から、ブレンド温度を４０℃とすることで、２３℃でブレンドした場合よりも結晶化を抑制する効果があることがわかる。
Figure JPOXMLDOC01-appb-T000034
Figure JPOXMLDOC01-appb-T000035
Figure JPOXMLDOC01-appb-T000036
 Example 4 Evaluation of Crystallization
Liquid composition examples 26 to 49 containing monofunctional (meth) acrylate and polyvalent (meth) acrylic monomer represented by the general formula (2) in the proportions described in Tables 4 to 6 are prepared, It was evaluated whether changing the blending temperature affects the generation of crystals. The results are shown in Tables 4 to 7. Using the compounds of the chemical formulas (A), (C) and (D), which have been temperature-controlled to the temperatures shown in the table, they are blended by the formulation and method shown in the table, well stirred and uniformly dissolved to make the liquid composition Obtained. Chemical formula (D) / (C) means a mixture of the compound of chemical formula (D) and the compound of chemical formula (C) in a weight ratio of 1: 1. Next, storage was carried out under the storage conditions shown in the table, and when a predetermined time passed, the presence or absence of precipitation of crystals was visually confirmed. “Storage at 23 ° C./1 day → 5 ° C.” means storage at 23 ° C. for 1 day and then storage at 5 ° C. “Crystallization (5 ° C./5 day)” is storage at 5 ° C. for 5 days It means that.
Figure JPOXMLDOC01-appb-T000033
 From the results of Example 26 and Example 27, it can be seen that setting the blending temperature to 40 ° C. has the effect of suppressing crystallization more than the case of blending at 23 ° C.
Figure JPOXMLDOC01-appb-T000034
Figure JPOXMLDOC01-appb-T000035
Figure JPOXMLDOC01-appb-T000036
　上記の結果から、ブレンド温度を60℃以上とすることで、更に結晶化が抑制され、5℃/30日間以上保管後も液体組成物中に結晶が発生しないことがわかる。また、単官能（メタ）アクリレートのみを60℃に加温した場合であっても、得られた液体組成物を5℃/30日間以上保管しても結晶は発生しなかった。また、化学式（Ａ）の化合物として、新中村化学株式会社製のA-BPEFを用いた場合にも、同様の結果が得られた。なお、１２０℃を超える温度でブレンドした場合、モノマーの（メタ）アクリレートが重合する可能性があるため、試験は１２０℃までとした。 From the above results, it can be seen that crystallization is further suppressed by setting the blending temperature to 60 ° C. or higher, and no crystals are generated in the liquid composition even after storage at 5 ° C. for 30 days or more. Further, even when only monofunctional (meth) acrylate was heated to 60 ° C., no crystals were generated even when the obtained liquid composition was stored at 5 ° C./30 days or more. In addition, similar results were obtained when A-BPEF manufactured by Shin-Nakamura Chemical Co., Ltd. was used as the compound of the chemical formula (A). In addition, when it blended at temperature over 120 degreeC, since the (meth) acrylate of a monomer may superpose | polymerize, the test was made to 120 degreeC.
＜実施例５：結晶化した一般式（２）で表される多価（メタ）アクリル系単量体の溶解性＞
　単官能（メタ）アクリレートとブレンドする前に既に一般式（２）で表される多価（メタ）アクリル系単量体が結晶化している場合に、加熱した単官能（メタ）アクリレートとブレンドすることで結晶が溶解するかを評価した。その際、各ブレンド温度で単官能（メタ）アクリレートと多価（メタ）アクリル系単量体とを混合し、その後６０℃に保持して結晶化した多価（メタ）アクリル系単量体が溶解するかを評価した。結果を表８に示す。なお、表中の「溶解性（６０℃／Ｎｄａｙ）」は、６０℃でＮ日間保管した際の溶解の程度を意味する。
Figure JPOXMLDOC01-appb-T000037
 Example 5 Solubility of Multivalent (Meth) Acrylic-Based Monomer Represented by Crystallized General Formula (2)>
When the polyvalent (meth) acrylic monomer represented by the general formula (2) is already crystallized before blending with the monofunctional (meth) acrylate, it is blended with the heated monofunctional (meth) acrylate It was evaluated whether the crystals dissolved. At that time, a monofunctional (meth) acrylate and a polyvalent (meth) acrylic monomer are mixed at each blending temperature, and then the polyvalent (meth) acrylic monomer crystallized by maintaining at 60 ° C. It was evaluated whether it was dissolved. The results are shown in Table 8. In addition, "solubility (60 degreeC / Nday)" in a table | surface means the grade of melt | dissolution at the time of N day storage at 60 degreeC.
Figure JPOXMLDOC01-appb-T000037
　上記の結果から、化学式（Ｄ）の単官能（メタ）アクリレートを用いることで、一般式（２）で表される多価（メタ）アクリル系単量体が結晶化していたとしても、良好に溶解されることが分かる。 From the above results, by using the monofunctional (meth) acrylate of the chemical formula (D), even if the multivalent (meth) acrylic monomer represented by the general formula (2) is crystallized, It turns out that it is dissolved.

Claims (10)

  1. 　（Ａ）下記一般式（１）で表される（メタ）アクリレートと、
    Figure JPOXMLDOC01-appb-C000001
     [式（１）中、
    　Ｘは、単結合、－Ｃ（Ｒ２）（Ｒ３）－、－Ｃ（＝Ｏ）－、－Ｏ－、－ＯＣ（＝Ｏ）－、－ＯＣ（＝Ｏ）Ｏ－、－Ｓ－、－ＳＯ－、－ＳＯ２－およびこれらの任意の組み合わせからなる群から選択される二価の基であり（ここで、Ｒ２およびＲ３は、各々独立に、水素原子、炭素数１～１０の直鎖状アルキル基、炭素数３～１０の分岐状アルキル基、炭素数３～１０の環状アルキル基、炭素数１～１０の直鎖状アルコキシ基、炭素数３～１０の分岐状アルコキシ基、炭素数３～１０の環状アルコキシ基、フェニル基またはフェニルフェニル基であり；あるいは、Ｒ２およびＲ３は、相互に連結して、これらが結合する炭素原子と一緒になって炭素数３～１０の環状アルキル基を形成していてもよい）；
    　Ｙは、分岐していてもよい炭素数２～６のアルキレン基、炭素数６～１０のシクロアルキレン基、または炭素数６～１０のアリーレン基であり；
    　Ｒ１は、水素原子またはメチル基であり；
    　Ｒ４およびＲ５は、各々独立に、炭素数１～１０の直鎖状アルキル基、炭素数３～１０の分岐状アルキル基、炭素数３～１０の環状アルキル基、炭素数１～１０の直鎖状アルコキシ基、炭素数３～１０の分岐状アルコキシ基、炭素数３～１０の環状アルコキシ基、ハロゲン原子、フェニル基またはフェニルフェニル基であり；
    　ｍは、０～１０の整数であり；
    　ｎは、１～２の整数であり；
    　ｐは、０～４の整数であり；
    　ｑは、０～５の整数である]
    　（Ｂ）下記一般式（２）で表される多価（メタ）アクリル系単量体と
    Figure JPOXMLDOC01-appb-C000002
     [式（２）中、
    　Ｒ１０およびＲ１１は、それぞれ独立に、水素原子、炭素数１～２０のアルキル基、炭素数１～２０のアルコキシル基、炭素数３～２０のシクロアルキル基、炭素数５～２０のシクロアルコキシル基、炭素数６～２０のアリール基、炭素数６～２０のアリールオキシ基、およびハロゲン原子から選択され、
    　Ｒ１２は、水素原子またはメチル基であり；
    　Ｘは、単結合、－Ｏ－、－Ｓ－、－ＳＯ－、－ＳＯ２－、－ＣＯ－および下記一般式（３）～（６）からなる群のうち、いずれかの構造を表し；
    　ＹおよびＺは、それぞれ独立に、分岐していてもよい炭素数２～６のアルキレン基、炭素数６～１０のシクロアルキレン基、または炭素数６～１０のアリーレン基であり；
    　ｐおよびｑは、それぞれ独立に、０～４の整数である。］
    Figure JPOXMLDOC01-appb-C000003
     ［式（３）中、
    　Ｒ１３およびＲ１４はそれぞれ独立に水素原子、ハロゲン原子、置換基を有してもよい炭素数１～２０のアルキル基、置換基を有してもよい炭素数１～５のアルコキシ基、置換基を有してもよい炭素数６～１２のアリール基、置換基を有してもよい炭素数２～５のアルケニル基、および置換基を有してもよい炭素数７～１７のアラルキル基からなる群のうちいずれかを表し；
    　前記置換基はそれぞれ独立に、ハロゲン原子、炭素数１～２０のアルキル基、または炭素数６～１２のアリール基であり；
    　ｃは１～２０の整数を表す。］
    Figure JPOXMLDOC01-appb-C000004
     ［式（４）中、Ｒ１５およびＲ１６はそれぞれ独立に水素原子、ハロゲン原子、置換基を有してもよい炭素数１～２０のアルキル基、置換基を有してもよい炭素数１～５のアルコキシ基、置換基を有してもよい炭素数６～１２のアリール基、置換基を有してもよい炭素数２～５のアルケニル基および置換基を有してもよい炭素数７～１７のアラルキル基からなる群のうちいずれかを表すか、または、Ｒ１５およびＲ１６はそれぞれ互いに結合して、炭素数１～２０の炭素環若しくは複素環を形成し；
    　前記置換基はそれぞれ独立に、ハロゲン原子、炭素数１～２０のアルキル基、または炭素数６～１２のアリール基である。］
    Figure JPOXMLDOC01-appb-C000005
     ［式（５）中、Ｒ１７～Ｒ２０はそれぞれ独立に水素原子、ハ口ゲン、置換基を有してもよい炭素数１～２０のアルキル基、置換基を有してもよい炭素数１～５のアルコキシ基、置換基を有してもよい炭素数６～１２のアリール基、置換基を有してもよい炭素数２～５のアルケニル基および置換基を有してもよい炭素数７～１７のアラルキル基からなる群のうちいずれかを表すか、または、Ｒ１７およびＲ１８並びにＲ１９およびＲ２０は、それぞれ互いに結合して、炭素数１～２０の炭素環若しくは複素環を形成し；
    　前記置換基はそれぞれ独立に、ハロゲン原子、炭素数１～２０のアルキル基、または炭素数６～１２のアリール基である。］
    Figure JPOXMLDOC01-appb-C000006
     ［式（６）中、Ｒ２１～Ｒ３０はそれぞれ独立に水素原子または炭素数１～３のアルキル基である。］
    　を含む液体組成物の製造方法であって、
    　前記一般式（１）で表される（メタ）アクリレートを３５℃以上１２０℃以下の温度で前記一般式（２）で表される多価（メタ）アクリル系単量体と混合することを含む、方法。     (A) (meth) acrylate represented by the following general formula (1),
    Figure JPOXMLDOC01-appb-C000001
     [In the formula (1),
    X represents a single bond, -C (R 2 ) (R 3 )-, -C (= O)-, -O-, -OC (= O)-, -OC (= O) O-, -S- A divalent group selected from the group consisting of -SO-, -SO 2 -and any combination thereof (wherein R 2 and R 3 each independently represent a hydrogen atom or C 1 -C 2 10 linear alkyl group, branched alkyl group having 3 to 10 carbon atoms, cyclic alkyl group having 3 to 10 carbon atoms, linear alkoxy group having 1 to 10 carbon atoms, branched alkoxy having 3 to 10 carbon atoms Group, a cyclic alkoxy group having 3 to 10 carbon atoms, a phenyl group or a phenylphenyl group; or alternatively, R 2 and R 3 are linked to each other, and together with the carbon atom to which they are bonded, have 3 carbon atoms To 10 cyclic alkyl groups may be formed);
    Y represents an alkylene group having 2 to 6 carbon atoms which may be branched, a cycloalkylene group having 6 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms;
    R 1 is a hydrogen atom or a methyl group;
    R 4 and R 5 each independently represent a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, or 1 to 10 carbon atoms A linear alkoxy group, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, a halogen atom, a phenyl group or a phenylphenyl group;
    m is an integer of 0 to 10;
    n is an integer of 1 to 2;
    p is an integer of 0 to 4;
    q is an integer of 0 to 5]
    (B) a multivalent (meth) acrylic monomer represented by the following general formula (2)
    Figure JPOXMLDOC01-appb-C000002
     [In the formula (2),
    R 10 and R 11 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a cycloalkoxyl group having 5 to 20 carbon atoms A group, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and a halogen atom,
    R 12 is a hydrogen atom or a methyl group;
    X represents a structure of any one of the group consisting of a single bond, -O-, -S-, -SO-, -SO 2- , -CO- and the following general formulas (3) to (6);
    Y and Z each independently represent an alkylene group having 2 to 6 carbon atoms which may be branched, a cycloalkylene group having 6 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms;
    p and q are each independently an integer of 0 to 4. ]
    Figure JPOXMLDOC01-appb-C000003
     [In the formula (3),
    R 13 and R 14 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, The aryl group having 6 to 12 carbon atoms which may have a group, the alkenyl group having 2 to 5 carbon atoms which may have a substituent, and the aralkyl group having 7 to 17 carbon atoms which may have a substituent Represents any one of the group consisting of
    The substituents are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms;
    c represents an integer of 1 to 20. ]
    Figure JPOXMLDOC01-appb-C000004
     [In Formula (4), R 15 and R 16 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or 1 carbon atom which may have a substituent] Alkoxy group of ̃5, aryl group having 6 to 12 carbon atoms which may have a substituent, alkenyl group having 2 to 5 carbon atoms which may have a substituent, and carbon number which may have a substituent Or any one of the group consisting of 7 to 17 aralkyl groups, or R 15 and R 16 respectively bond to each other to form a carbocyclic ring or heterocyclic ring having 1 to 20 carbon atoms;
    The substituents are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms. ]
    Figure JPOXMLDOC01-appb-C000005
     [In formula (5), R 17 to R 20 each independently represent a hydrogen atom, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a carbon number which may have a substituent 1 to 5 alkoxy group, optionally substituted aryl group having 6 to 12 carbon atoms, optionally substituted alkenyl group having 2 to 5 carbon atoms and carbon optionally having substituent group R 17 and R 18 and R 19 and R 20 are each bonded to each other to form a carbocyclic or heterocyclic ring having 1 to 20 carbon atoms. Form;
    The substituents are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms. ]
    Figure JPOXMLDOC01-appb-C000006
     In the formula (6), R 21 to R 30 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ]
    A method of producing a liquid composition comprising
    Including mixing the (meth) acrylate represented by the said General formula (1) with the polyvalent (meth) acrylic-type monomer represented by the said General formula (2) at the temperature of 35 degreeC or more and 120 degrees C or less ,Method.
  2. 　前記式（１）中、ｐおよびｑが共に０である、請求項１に記載の方法。 The method according to claim 1, wherein p and q are both 0 in the formula (1).
  3. 　前記式（１）中、ｎが１であり、ｍが０である、請求項１または２に記載の方法。 The method according to claim 1 or 2, wherein in the formula (1), n is 1 and m is 0.
  4. 　前記一般式（１）で表される（メタ）アクリレートと前記一般式（２）で表される多価（メタ）アクリル系単量体の含有量が、質量比で１：１０～１０：１である、請求項１～３のいずれか１項に記載の方法。 The content of the (meth) acrylate represented by the general formula (1) and the polyvalent (meth) acrylic monomer represented by the general formula (2) is 1:10 to 10: 1 in mass ratio The method according to any one of claims 1 to 3, which is
  5. 　前記一般式（１）で表される（メタ）アクリレートが２種類以上の化合物のブレンド体である、請求項１～４のいずれか１項に記載の方法。 The method according to any one of claims 1 to 4, wherein the (meth) acrylate represented by the general formula (1) is a blend of two or more kinds of compounds.
  6. 　前記式（２）中、Ｘが一般式（４）で示される構造を有する、請求項１～５のいずれか１項に記載の方法。 The method according to any one of claims 1 to 5, wherein in the formula (2), X has a structure represented by the general formula (4).
  7. 　前記液体組成物が活性エネルギー線硬化性組成物である、請求項１～６のいずれか１項に記載の方法。 The method according to any one of claims 1 to 6, wherein the liquid composition is an active energy ray curable composition.
  8. 　請求項１～７のいずれか１項に記載の方法で得られた組成物を含む塗料。 A paint comprising the composition obtained by the method according to any one of claims 1 to 7.
  9. 　請求項１～７のいずれか１項に記載の方法で得られた組成物が硬化されてなる硬化体。 A cured product obtained by curing the composition obtained by the method according to any one of claims 1 to 7.
  10. 　硬化体の製造方法であって、
    　請求項１～７のいずれか１項に記載の方法で組成物を得る工程と、
    　前記組成物を硬化させる工程と
    を含む、方法。
     
          A method of producing a cured product,
    Obtaining a composition by the method according to any one of claims 1 to 7;
    Curing the composition.

PCT/JP2018/045688 2017-12-19 2018-12-12 (meth)acrylic composition manufacturing method, (meth)acrylic composition-containing coating, and hardened product WO2019124190A1 (en)

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JP2010106046A (en) * 2007-02-28 2010-05-13 Nippon Kayaku Co Ltd Energy ray-curable type resin composition for optical lens sheet, and its cured product
JP2012082387A (en) * 2010-09-14 2012-04-26 Dic Corp High refractive index composition for optical material, and cured product thereof
JP2013112744A (en) * 2011-11-29 2013-06-10 Dic Corp (meth)acrylic acid derivative, composition and cured product of the same
JP2014185337A (en) * 2013-02-25 2014-10-02 Osaka Gas Chem Kk Curable composition and cured product of the same
JP6327408B1 (en) * 2016-08-03 2018-05-23 三菱瓦斯化学株式会社 (Meth) acrylic composition, paint and cured product containing the same

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