WO2018003293A1 - 活性エネルギー線硬化性組成物及びそれを用いたフィルム - Google Patents

活性エネルギー線硬化性組成物及びそれを用いたフィルム Download PDF

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WO2018003293A1
WO2018003293A1 PCT/JP2017/017495 JP2017017495W WO2018003293A1 WO 2018003293 A1 WO2018003293 A1 WO 2018003293A1 JP 2017017495 W JP2017017495 W JP 2017017495W WO 2018003293 A1 WO2018003293 A1 WO 2018003293A1
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meth
acrylate
mass
curable composition
active energy
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PCT/JP2017/017495
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English (en)
French (fr)
Japanese (ja)
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茂年 西澤
谷岡　隆浩
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Dic株式会社
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Priority to KR1020187035874A priority Critical patent/KR102148790B1/ko
Priority to JP2017542206A priority patent/JP6288538B1/ja
Priority to CN201780039287.0A priority patent/CN109312012B/zh
Publication of WO2018003293A1 publication Critical patent/WO2018003293A1/ja

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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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/025—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing nitrogen atoms
    • 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09D201/025—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16

Definitions

  • the present invention relates to an active energy ray-curable composition capable of forming a hard coat layer having a high refractive index and high antistatic properties on a film surface by coating and curing the film surface, and a film using the same.
  • Antireflective (LR) films used on the surface of flat panel displays (FPD) such as liquid crystal displays (LCDs), organic EL displays (OLEDs), plasma displays (PDPs), etc. have a large refractive index difference on the film substrate
  • FPD flat panel displays
  • LCDs liquid crystal displays
  • OLEDs organic EL displays
  • PDPs plasma displays
  • LR refractive index difference
  • This is realized by a multilayer structure in which two layers are formed (base material / high refractive index layer / low refractive index layer).
  • base material high refractive index layer / low refractive index layer
  • Each of these layers is required to have high scratch resistance in order to prevent scratches in the production process of the antireflection film, and also to have high antistatic properties in order to prevent contamination and blocking of the film.
  • an antireflection film is an optical film, each layer is also required to have high transparency.
  • the problem to be solved by the present invention is to provide an active energy ray-curable composition capable of forming a hard coat layer having both a high refractive index and a high antistatic property, and a film using the same.
  • the active energy ray-curable composition contains a resin having a specific high refractive index polymerizable monomer, an alicyclic structure, and a quaternary ammonium salt. It was found that a hard coat layer having both a high refractive index and a high antistatic property can be formed by blending, and the present invention was completed.
  • the present invention has a high refractive index polymerizable monomer (A) having a refractive index of 1.55 or more, a polyfunctional polymerizable monomer (B), an alicyclic structure and a quaternary ammonium salt.
  • the present invention provides an active energy ray-curable composition containing a resin (C) and an organic solvent (D), and a film using the same.
  • the active energy ray-curable composition of the present invention can form a hard coat layer having a high refractive index and a high antistatic property on the film surface by coating and curing on the film surface. Therefore, the cured coating film of the active energy ray-curable composition of the present invention is very useful as a material for an antireflection film.
  • the film which has a hard-coat layer which consists of a cured coating film of the active energy ray curable composition of this invention is flat panel displays, such as a liquid crystal display (LCD), an organic electroluminescent display (OLED), and a plasma display (PDP) ( It can be suitably used as an optical film used for FPD). Furthermore, since it has excellent antistatic properties when used in these applications, adhesion of dust and the like can be suppressed. Furthermore, when this film is used for a liquid crystal display or the like, malfunction of the display due to generated static electricity can be prevented.
  • LCD liquid crystal display
  • OLED organic electroluminescent display
  • PDP plasma display
  • the active energy ray-curable composition of the present invention comprises a high refractive index polymerizable monomer (A) having a refractive index of 1.55 or more, a polyfunctional polymerizable monomer (B), an alicyclic structure, and It contains a resin (C) having a quaternary ammonium salt and an organic solvent (D).
  • the polymerizable monomer (A) is not particularly limited as long as it has a high refractive index of 1.55 or more before curing.
  • an aromatic polymerizable monomer having 2 to 6 aromatic rings Preferred examples include fluorene polymerizable monomers.
  • polymerizable monomer (A) examples include compounds represented by the following general formula (1): phenylbenzyl such as o-phenylbenzyl (meth) acrylate and p-phenylbenzyl (meth) acrylate (Meth) acrylate compound having a group; (meth) acrylate compound having a phenylphenol group such as phenylphenol EO acrylate; propoxylated bisphenol A di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, oxyethylene group Examples thereof include bisphenol compounds having 2 to 4 (meth) acryloyl groups such as bisphenol A di (meth) acrylate having an oxyethylene group and bisphenol A tri (meth) acrylate having an oxyethylene group.
  • phenylbenzyl such as o-phenylbenzyl (meth) acrylate and p-phenylbenzyl (meth) acrylate (Meth) acrylate compound having
  • These polymerizable monomers (A) can be used alone or in combination of two or more.
  • the compound represented by the following general formula (1), a (meth) acrylate compound having a phenylbenzyl group, and a (meth) acryloyl group in a range of 2 to 4 It is preferable to use one or more monomers selected from the group consisting of bisphenol compounds, a compound represented by the following general formula (1) alone, a compound represented by the following general formula (1), and a phenylbenzyl group More preferred is a combined use of a (meth) acrylate compound having a bisphenol compound alone having 2 to 4 (meth) acryloyl groups.
  • the mass ratio thereof may be in the range of 30/70 to 70/30. preferable.
  • R 1 and R 2 each represent a hydrogen group or a methyl group, and m and n each represent an integer of 0 to 5.
  • (meth) acrylate refers to one or both of acrylate and methacrylate
  • (meth) acryloyl refers to one or both of acryloyl and methacryloyl.
  • the polymerizable monomer (B) is a polyfunctional polymerizable monomer and has two or more polymerizable groups in one molecule.
  • the polymerizable group may be any vinyl group that is a carbon-carbon double bond, a (meth) acryloyl group, or the like, but a (meth) acryloyl group is preferred because of excellent curability.
  • Examples of the polymerizable monomer (B) having a (meth) acryloyl group include 1,4-butanediol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, 1 , 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol Di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, Tripropylene glycol di (meta Di (meth) acrylate of dihydric
  • polyfunctional polymerizable monomers (B) can be used alone or in combination of two or more.
  • these polyfunctional polymerizable monomers (B) since the scratch resistance of the cured coating film of the active energy ray-curable composition of the present invention is improved, dipentaerythritol hexa (meth) acrylate, Dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, and pentaerythritol tri (meth) acrylate are preferred.
  • the active energy ray-curable composition of the present invention contains urethane (meth) acrylate as a polymerizable component other than the polymerizable monomer (A) and the polymerizable monomer (B). Also good.
  • the urethane (meth) acrylate (E) is obtained by reacting a polyisocyanate (e1) with a (meth) acrylate (e2) having a hydroxyl group.
  • polyisocyanate (e1) examples include aliphatic polyisocyanates and aromatic polyisocyanates. Since the coloring of the cured coating film of the active energy ray-curable composition of the present invention can be reduced, the aliphatic polyisocyanate is preferable.
  • the aliphatic polyisocyanate is a compound in which a portion excluding an isocyanate group is composed of an aliphatic hydrocarbon.
  • Specific examples of the aliphatic polyisocyanate include aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, and lysine triisocyanate; norbornane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 1,3-bis (isocyanato).
  • cycloaliphatic polyisocyanates such as methyl) cyclohexane, 2-methyl-1,3-diisocyanatocyclohexane and 2-methyl-1,5-diisocyanatocyclohexane.
  • a trimerized product obtained by trimming the aliphatic polyisocyanate or the alicyclic polyisocyanate can also be used as the aliphatic polyisocyanate.
  • these aliphatic polyisocyanates can be used alone or in combination of two or more.
  • aliphatic polyisocyanates in order to improve the scratch resistance of the coating film, among the aliphatic polyisocyanates, hexamethylene diisocyanate, which is a linear aliphatic hydrocarbon diisocyanate, norbornane diisocyanate, which is an alicyclic diisocyanate, isophorone Diisocyanate is preferred.
  • the (meth) acrylate (e2) is a compound having a hydroxyl group and a (meth) acryloyl group.
  • Specific examples of the (meth) acrylate (e2) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, Dihydric alcohols such as 1,5-pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, hydroxypivalate neopentyl glycol mono (meth) acrylate, etc.
  • Mono- or di (meth) acrylate of trivalent alcohols such as relate, glycerin di (meth) acrylate, bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, or a part of these alcoholic hydroxyl groups
  • the urethane (meth) acrylate (e2) since it can improve the scratch resistance of the cured coating film of the active energy ray-curable composition of the present invention, it has four or more (meth) acryloyl groups in one molecule. Those are preferred. Since the urethane (meth) acrylate (E) has four or more (meth) acryloyl groups in one molecule, the (meth) acrylate (e2) has two or more (meth) acryloyl groups. What has is preferable.
  • Examples of such (meth) acrylate (e2) include trimethylolpropane di (meth) acrylate, ethylene oxide modified trimethylolpropane di (meth) acrylate, propylene oxide modified trimethylolpropane di (meth) acrylate, glycerin di (Meth) acrylate, bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. .
  • (meth) acrylates (e2) can be used singly or in combination of two or more with respect to one of the aliphatic polyisocyanates.
  • pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate are preferable because they can improve scratch resistance.
  • the reaction between the polyisocyanate (e1) and the (meth) acrylate (e2) can be carried out by a conventional urethanization reaction. Moreover, in order to accelerate
  • urethanization catalyst examples include amine compounds such as pyridine, pyrrole, triethylamine, diethylamine and dibutylamine; phosphorus compounds such as triphenylphosphine and triethylphosphine; dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dibutyltin Examples thereof include organic tin compounds such as diacetate and tin octylate, and organic zinc compounds such as zinc octylate.
  • the active energy ray-curable composition of the present invention includes a polymerizable component other than the polymerizable monomer (A), the polymerizable monomer (B), and the urethane (meth) acrylate (E).
  • epoxy (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, or the like can be used.
  • the epoxy (meth) acrylate include those obtained by reacting (meth) acrylic acid with bisphenol-type epoxy resin, novolac-type epoxy resin, polyglycidyl methacrylate and the like and esterifying it.
  • polyester (meth) acrylate (meth) acrylic acid is made to react and esterify with the polyester which the both terminal obtained by polycondensation of polyhydric carboxylic acid and polyhydric alcohol is a hydroxyl group, for example. Or a product obtained by reacting (meth) acrylic acid with ester obtained by adding an alkylene oxide to a polyvalent carboxylic acid.
  • polyether (meth) acrylate what was obtained by reacting (meth) acrylic acid with polyether polyol and esterifying is mentioned, for example.
  • the resin (B) has an alicyclic structure and a quaternary ammonium salt.
  • Examples of the method for producing the resin (C) include the polymerizable monomer (c1) having an alicyclic structure and the polymerizable monomer (c2) having a quaternary ammonium salt as essential components. Examples thereof include a method of copolymerizing the monomer (c1) and the polymerizable monomer (c2) with a copolymerizable polymerizable monomer (c3).
  • the polymerizable monomer (c1) is a polymerizable monomer having an alicyclic structure.
  • the alicyclic structure include a monocyclic alicyclic structure such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, and a cyclodecane ring; a bicycloundecane ring, a decahydro ring Naphthalene (decalin) ring, tricyclo [5.2.1.0 2,6 ] decane ring, bicyclo [4.3.0] nonane ring, tricyclo [5.3.1.1] dodecane ring, tricyclo [5.
  • polymerizable monomer (c1) examples include cyclohexyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, Examples include dicyclopentenyloxyethyl (meth) acrylate and dicyclopentanyl (meth) acrylate.
  • polymerizable monomers (c1) can be used alone or in combination of two or more.
  • Examples of the polymerizable monomer (c2) include those in which the counter anion such as 2-[(meth) acryloyloxy] ethyltrimethylammonium chloride and 3-[(meth) acryloyloxy] propyltrimethylammonium chloride is chloride; Counter anions such as 2-[(meth) acryloyloxy] ethyltrimethylammonium bromide, 3-[(meth) acryloyloxy] propyltrimethylammonium bromide and the like, wherein 2-[(meth) acryloyloxy] ethyltrimethylammonium methylphenyl Sulfonate, 2-[(meth) acryloyloxy] ethyltrimethylammonium methylsulfonate, 3-[(meth) acryloyloxy] propyltrimethylammonium methyl Phenylsulfonate, 3-[(meth) acryloyloxy] propyltrimethylam
  • Examples of the polymerizable monomer (c3) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n- Pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, Alkyl (meth) acrylates such as dodecyl (meth) acrylate; methoxypolyethylene glycol mono (meth) acrylate, octoxypolyethyleneglycol / polypropyleneglycol mono (meth) acrylate, lauroxypoly
  • the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention can be further improved, mono (meth) acrylate of polyalkylene glycol is preferable, and methoxypolyethylene Glycol mono (meth) acrylate is more preferred.
  • the (meth) acrylate which has a fluorinated alkyl group is also preferable from the effect that the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention can be further improved.
  • the number average molecular weight of the polyalkylene glycol is preferably in the range of 200 to 8,000, more preferably in the range of 300 to 6,000, still more preferably in the range of 400 to 4,000, and 400 to 2 Those in the range of 1,000 are particularly preferred.
  • the ratio of the polymerizable monomer (c1) in the total amount of the raw material of the resin (C) can further improve the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention.
  • the range of mass% is preferable, the range of 10 to 50 mass% is more preferable, and the range of 12 to 45 mass% is more preferable.
  • the ratio of the polymerizable monomer (c2) in the total amount of the raw material of the resin (C) can further improve the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention.
  • the range of ⁇ 90% by mass is preferred, the range of 40 ⁇ 80% by mass is more preferred, and the range of 45 ⁇ 70% by mass is more preferred.
  • the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention can be further improved.
  • the proportion of the poly (alkylene glycol) mono (meth) acrylate in the total amount of the raw material of the resin (C) is preferably in the range of 5 to 60% by mass, more preferably in the range of 10 to 50% by mass, and 20 to 40% by mass. The range of is more preferable.
  • the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention can be further improved.
  • the ratio of the (meth) acrylate having a fluorinated alkyl group in the total amount of the raw material of the resin (C) is preferably in the range of 0.1 to 20% by mass, more preferably in the range of 0.5 to 10% by mass. The range of 1 to 5% by mass is more preferable.
  • the weight average molecular weight of the resin (C) is preferably in the range of 1,000 to 100,000 because the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention can be further improved.
  • the range of ⁇ 50,000 is more preferred, and the range of 3,000 ⁇ 30,000 is more preferred.
  • the weight average molecular weight in this invention is the value in polystyrene conversion measured by the gel permeation chromatography (GPC) method.
  • the polymerizable monomer (A) and the polymerizable monomer The range of 0.1 to 30 parts by mass is preferable, the range of 0.5 to 20 parts by mass is more preferable, and the range of 1 to 10 parts by mass is more preferable with respect to the total of 100 parts by mass of (B). A range of 5 to 7 parts by mass is particularly preferred.
  • the organic solvent (D) can be used without particular limitation as long as it can dissolve other components in the active energy ray-curable composition of the present invention. Further, since the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention can be further improved, the dispersion term ( ⁇ D) in the Hansen solubility parameter is in the range of 15.5 to 16.1 MPa 0.5 . It is preferable that the polarization term ( ⁇ P) is in the range of 6.3 to 10.4 MPa 0.5 and the hydrogen bond term ( ⁇ H) is in the range of 5.1 to 11.6 MPa 0.5 .
  • Hansen solubility parameters For the definition and calculation of Hansen solubility parameters, please refer to Charles M. Hansen, “Hansen Solubility Parameters: A Users Handbook (CRC Press, 2007)”. Further, by using the computer software “Hansen Solubility Parameters in Practice (HSPiP)”, the Hansen solubility parameter can be estimated from the chemical structure of an organic solvent whose parameter value is not described in the literature. In the present invention, the value is used for an organic solvent whose parameter value is described in the literature, and the parameter value estimated using HSPiP version 4.1.06 is used for the organic solvent whose parameter value is not described in the literature. Use.
  • the organic solvent (D) can be used as a single organic solvent or as a mixed solvent using two or more organic solvents in combination. When using 2 or more types together, the value which carried out the weighted average of three parameters of the Hansen solubility parameter of each organic solvent can be used in the said range.
  • the compounding amount of the organic solvent (D) in the active energy ray-curable composition of the present invention is preferably an amount that provides a viscosity suitable for the coating method described later.
  • the active energy ray-curable composition of the present invention can be formed into a cured coating film by irradiating active energy rays after coating on a substrate.
  • the active energy rays refer to ionizing radiation such as ultraviolet rays, electron beams, ⁇ rays, ⁇ rays, and ⁇ rays.
  • a photopolymerization initiator (F) to the active energy ray curable composition of the present invention.
  • a photosensitizer (G) can be further added to improve curability.
  • Examples of the photopolymerization initiator (F) include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, oligo ⁇ 2-hydroxy-2-methyl-1- [4- ( 1-methylvinyl) phenyl] propanone ⁇ , benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy -2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) -Acetophenone compounds such as butanone; benzoin, benzoin methyl ether, benzo Benzoin compounds such as isopropyl ether; acylphosphine oxide compounds such as 2,4,6-
  • Examples of the photosensitizer (G) include tertiary amine compounds such as diethanolamine, N-methyldiethanolamine and tributylamine, urea compounds such as o-tolylthiourea, sodium diethyldithiophosphate, and s-benzylisothiuro. And sulfur compounds such as nitro-p-toluenesulfonate.
  • tertiary amine compounds such as diethanolamine, N-methyldiethanolamine and tributylamine
  • urea compounds such as o-tolylthiourea, sodium diethyldithiophosphate, and s-benzylisothiuro.
  • sulfur compounds such as nitro-p-toluenesulfonate.
  • the photopolymerization initiator (F) and the photosensitizer (G) are used in the amounts of the polymerizable monomer (A) and the polymerizable monomer in the active energy ray-curable composition of the present invention.
  • the total amount of polymerizable components including (B) is preferably 0.05 to 20 parts by mass, and more preferably 0.5 to 10% by mass, based on 100 parts by mass in total.
  • a polymerization inhibitor As a compound other than the above components (A) to (G), a polymerization inhibitor, a surface conditioner, and an antistatic agent are used depending on applications and required characteristics. Addition of antifoaming agent, viscosity modifier, light stabilizer, weathering stabilizer, heat stabilizer, UV absorber, antioxidant, leveling agent, organic pigment, inorganic pigment, pigment dispersant, silica beads, organic beads, etc. Agents: Inorganic fillers such as silicon oxide, aluminum oxide, titanium oxide, zirconia, and antimony pentoxide can be blended. These other blends can be used alone or in combination of two or more.
  • the film of the present invention is obtained by applying the active energy ray-curable composition of the present invention to at least one surface of a film substrate, and then irradiating the active energy ray to form a cured coating film. is there.
  • the material of the film base used in the film of the present invention is preferably a highly transparent resin, for example, a polyester resin such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate; polypropylene, polyethylene, polymethylpentene-1 Polyolefin resins such as cellulose acetate (diacetyl cellulose, triacetyl cellulose, etc.), cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate propionate butyrate, cellulose acetate phthalate, cellulose nitrate and other cellulose resins; poly Acrylic resins such as methyl methacrylate; polyvinyl chloride resins such as polyvinyl chloride and polyvinylidene chloride; polyvinyl alcohol; ethylene-acetic acid Nyl copolymer; polystyrene; polyamide; polycarbonate; polysulfone; polyethersulfone; polyetheretherketone; polyimide resin
  • the film substrate may be in the form of a film or a sheet, and the thickness is preferably in the range of 20 to 500 ⁇ m.
  • the thickness is preferably in the range of 20 to 200 ⁇ m, more preferably in the range of 30 to 150 ⁇ m, and still more preferably in the range of 40 to 130 ⁇ m.
  • Examples of the method for applying the active energy ray-curable composition of the present invention to the film substrate include die coating, microgravure coating, gravure coating, roll coating, comma coating, air knife coating, kiss coating, spray coating, and dip coating. , Spinner coating, brush coating, solid coating by silk screen, wire bar coating, flow coating and the like.
  • the active energy ray-curable composition of the present invention contains an organic solvent
  • the organic solvent In order to volatilize and to segregate the resin (B) on the coating film surface, it is preferable to heat or dry at room temperature.
  • the conditions for heat drying are not particularly limited as long as the organic solvent volatilizes. Usually, the heat drying is performed at a temperature in the range of 50 to 100 ° C. and for a time in the range of 0.5 to 10 minutes. preferable.
  • the active energy rays for curing the active energy ray-curable composition of the present invention are ionizing radiations such as ultraviolet rays, electron beams, ⁇ rays, ⁇ rays, and ⁇ rays.
  • ultraviolet rays examples of devices that emit ultraviolet rays include low-pressure mercury lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, metal halide lamps, electrodeless lamps (fusion lamps), chemical lamps, Examples thereof include a black light lamp, a mercury-xenon lamp, a short arc lamp, a helium / cadmium laser, an argon laser, sunlight, and an LED lamp.
  • the film thickness of the cured coating film when forming the cured coating film of the active energy ray-curable composition of the present invention on the film substrate is sufficient for the hardness of the cured coating film and curing of the coating film. Since the curling of the film due to shrinkage can be suppressed, the range of 1 to 30 ⁇ m is preferable, the range of 3 to 15 ⁇ m is more preferable, and the range of 4 to 10 ⁇ m is more preferable.
  • a solution prepared by dissolving 0.1 parts by mass of a polymerization initiator (azobisisobutyronitrile) with 2.4 parts by mass of PGME was added dropwise over 30 minutes, and then reacted at 65 ° C. for 3 hours.
  • methanol was added for dilution to obtain a 45% by mass solution of a resin (C-3) having an alicyclic structure and a quaternary ammonium salt.
  • the weight average molecular weight of the obtained resin (C-3) was 10,000.
  • a solution prepared by dissolving 0.1 parts by mass of a polymerization initiator (azobisisobutyronitrile) with 2.4 parts by mass of PGME was added dropwise over 30 minutes, and then reacted at 65 ° C. for 3 hours.
  • methanol was added for dilution to obtain a 45% by mass solution of a resin (C-4) having an alicyclic structure and a quaternary ammonium salt.
  • the weight average molecular weight of the obtained resin (C-4) was 10,000.
  • the obtained resin (C-5) had a weight average molecular weight of 10,000.
  • the obtained resin (C′-1) had a weight average molecular weight of 10,000.
  • the obtained resin (C′-2) had a weight average molecular weight of 10,000.
  • the weight average molecular weights of the resins (C-1) to (C-5), (C′-1) and (C′-2) obtained above were determined by gel permeation chromatography (GPC) method. The measurement was performed under the following conditions.
  • Measuring device High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were connected in series. "TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000” (7.8 mm ID x 30 cm) x 1 "TSKgel G3000” (7.8 mm ID x 30 cm) x 1 “TSKgel G2000” (7.8 mm ID ⁇ 30 cm) ⁇ 1 detector: RI (differential refractometer) Column temperature: 40 ° C Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 mL / min Injection amount: 100 ⁇ L (tetrahydrofuran solution with a sample concentration of 0.4 mass%) Standard sample: A calibration curve was prepared using the following standard polystyrene.
  • Example 1 High refractive index polymerizable monomer (9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, refractive index 1.616) (hereinafter abbreviated as “monomer (A-1)”) .) 17 parts by mass, high refractive index polymerizable monomer (equivalent mixture of o-phenylbenzyl acrylate and p-phenylbenzyl acrylate, refractive index 1.591, phenyl) (hereinafter “monomer (A-2 ) ”)) 17 parts by mass, polyfunctional acrylate mixture (mixture of 64% by mass of dipentaerythritol hexaacrylate, 17% by mass of dipentaerythritol pentaacrylate, 19% by mass of dipentaerythritol tetraacrylate) (hereinafter referred to as” single (Abbreviated as “mer (B-1)”) 66 parts by mass,
  • Irgacure 184 1-hydroxycyclohexyl phenyl ketone 5 parts by mass, methyl ethyl ketone (hereinafter abbreviated as “MEK”) 40 parts by mass and PGME 60 Mass parts were mixed uniformly to obtain an active energy ray-curable composition (1) having a nonvolatile content of 50% by mass.
  • MEK methyl ethyl ketone
  • Examples 2 to 7 Active energy ray-curable compositions (2) to (7) were obtained in the same manner as in Example 1 except that the compositions shown in Tables 1 to 3 were changed.
  • the active energy ray-curable composition was applied to a 60 ⁇ m-thick triacetylcellulose (TAC) film (manufactured by Fuji Film Co., Ltd.) with a bar coater so as to have a film thickness of 5 ⁇ m, and then at 60 ° C. for 1.5 minutes. After drying, irradiation was performed at an irradiation light amount of 3 kJ / m 2 using an ultraviolet irradiation device (manufactured by Eye Graphics Co., Ltd., high-pressure mercury lamp) in an air atmosphere, and a TAC film having a cured coating film was obtained as an evaluation sample. .
  • TAC triacetylcellulose
  • the cured coating films of the active energy ray-curable compositions of the present invention of Examples 1 to 7 have a high refractive index and a surface resistance value of 10 on the order of 9 to the 10th power. It was confirmed that the antistatic property was also high.
  • Comparative Examples 1 and 2 are examples using a resin having no alicyclic structure and having a quaternary ammonium salt. In both cases, the refractive index was high, but the surface resistance value exceeded 10 13, confirming that the antistatic property was poor.

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  • Chemical & Material Sciences (AREA)
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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Laminated Bodies (AREA)
  • Polymerisation Methods In General (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
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