CN109312012A - Actinic-radiation curable composition and the film for using it - Google Patents

Actinic-radiation curable composition and the film for using it Download PDF

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Publication number
CN109312012A
CN109312012A CN201780039287.0A CN201780039287A CN109312012A CN 109312012 A CN109312012 A CN 109312012A CN 201780039287 A CN201780039287 A CN 201780039287A CN 109312012 A CN109312012 A CN 109312012A
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methyl
acrylate
actinic
curable composition
radiation curable
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CN109312012B (en
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西泽茂年
谷冈隆浩
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DIC Corp
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Dainippon Ink and Chemicals Co Ltd
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    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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

Abstract

The present invention provides the Actinic-radiation curable composition for being capable of forming the hard conating for having taken into account high refractive index and high-antistatic and the film using it.The present invention uses a kind of Actinic-radiation curable composition, high refractive index polymerizable monomer (A), multifunctional polymerizable monomer (B), resin (C) and organic solvent (D) with alicyclic structure and quaternary ammonium salt containing refractive index for 1.55 or more.In turn, using following Actinic-radiation curable compositions, wherein above-mentioned resin (C) is the polymer for having used the polymerizable monomer with alicyclic structure of 5~40 mass % as raw material.In addition, it is 15.5~16.1MPa that above-mentioned organic solvent (D), which uses the dispersion item (δ D) in terms of Hansen Solubility Parameter,0.5Range, polarity item (δ P) be 6.3~10.4MPa0.5Range, hydrogen bond item (δ H) be 5.1~11.6MPa0.5Range organic solvent.

Description

Actinic-radiation curable composition and the film for using it
Technical field
The present invention relates to can pass through the surface coated on film and form its solidification in film surface to have high refractive index With the Actinic-radiation curable composition of the hard conating of high-antistatic and use the active energy ray-curable group Close the film of object.
Background technique
It is aobvious to be used for the plates such as liquid crystal display (LCD), organic el display (OLED), plasma scope (PDP) Show that antireflection (LR) film on the surface device (FPD) is constituted by forming multilayer made of 2 big layers of refringence on film base material (substrate/high index layer/low index layer) is realized.For above layers, antireflection film was being manufactured in order to prevent Damage in journey and require high marresistance, and in order to prevent fouling membrane, prevent adhesion, also require high-antistatic.In addition, Since antireflection film is optical film, so also requiring high transparency to each layer.
Among above-mentioned required characteristic, as the method for assigning antistatic property, proposes use and cooperated with season The scheme of the material of the resin of ammonium salt is (referring for example to Patent Documents 1 to 3.).But these materials are not high refractive index material Material.
It is therefore desirable to be able to form the active energy ray-curable of the hard conating with high refractive index and high-antistatic Composition.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2012-102166 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2008-013636 bulletin
Patent document 3: Japanese Unexamined Patent Publication 2008-255184 bulletin
Summary of the invention
The technical problems to be solved by the invention
Technical problem to be solved by the invention is to provide be capable of forming the hard painting for taking into account high refractive index and high-antistatic The Actinic-radiation curable composition of layer and the film for using the Actinic-radiation curable composition.
For solving the means of technical problem
In order to solve the above-mentioned technical problem the inventors of the present invention have made intensive studies, as a result, it has been found that, by active energy Cooperate specific high refractive index polymerizable monomer, the resin with alicyclic structure and quaternary ammonium salt in amount ray-curable composition Deng so as to form the hard conating for having taken into account high refractive index and high-antistatic, so as to complete the present invention.
That is, the present invention provides a kind of Actinic-radiation curable composition and the film using it, the active-energy are penetrated Line solidification compound is characterized in that, the high refractive index polymerizable monomer (A), multifunctional poly- for being 1.55 or more containing refractive index Conjunction property monomer (B), resin (C) and organic solvent (D) with alicyclic structure and quaternary ammonium salt.
The effect of invention
Actinic-radiation curable composition of the invention by coated on film surface and making its solidification, so as to Film surface forms the hard conating with high refractive index and high-antistatic.Therefore, active energy ray-curable group of the invention The cured coating film of object is closed as being highly useful for the material of antireflection film.
In addition, the film of the hard conating with the cured coating film comprising Actinic-radiation curable composition of the invention can Using as flat-panel monitors (FPD) such as liquid crystal display (LCD), organic el display (OLED), plasma scopes (PDP) Used in optical film and use well.In turn, also there is excellent antistatic property when for these purposes, thus, it is possible to Inhibit the attachment of dust etc..In turn, in the case where the film is used for liquid crystal display etc., additionally it is possible to prevent the electrostatic by generating The maloperation of caused display.
Specific embodiment
Actinic-radiation curable composition of the invention contains the high refractive index polymerism that refractive index is 1.55 or more Monomer (A), multifunctional polymerizable monomer (B), resin (C) and organic solvent (D) with alicyclic structure and quaternary ammonium salt.
Above-mentioned polymerizable monomer (A) as long as refractive index before curing be 1.55 or more high refractive index polymerizable monomer , preferably enumerate for example: aromatic system polymerizable monomer, fluorenes system polymerizable monomer with 2~6 aromatic rings etc..Separately Outside, the specific example as above-mentioned polymerizable monomer (A) can be enumerated: the following general formula (1) compound represented；(methyl) propylene Sour neighbour's phenyl benzyl ester, (methyl) acrylic acid have (methyl) acrylate compounds of phenylbenzyl to phenyl benzyl ester etc.；Phenyl Phenol EO acrylate etc. has (methyl) acrylate compounds of phenyl phenol；Propoxylated bisphenol two (methyl) third Olefin(e) acid ester, bisphenol-A two (methyl) acrylate with hydroxyl ethylidene, has Ethoxylated bisphenol A bis- (methyl) acrylate Bisphenol-A three (methyl) acrylate of hydroxyl ethylidene etc. has the bisphenol compound of (methyl) acryloyl group with 2~4 ranges Deng.These polymerizable monomers (A) can be used a kind, can also be used in combination two or more.Among these, controlled from refractive index Angle is set out, it is preferable to use selected from the following general formula (1) compound represented, (methyl) acrylate chemical combination with phenylbenzyl One or more of object and the bisphenol compound for having (methyl) acryloyl group with 2~4 ranges monomer are more preferably following logical Formula (1) compound represented individually, the following general formula (1) compound represented with phenylbenzyl (methyl) acroleic acid esterification Close object and use, with 2~4 ranges have (methyl) acryloyl group bisphenol compound it is independent.In addition, by the following general formula (1) compound represented and (methyl) acrylate compounds with phenylbenzyl and used time, preferably its mass ratio are 30/70 ~70/30 range.
[changing 1]
(in formula (1), R1、R2Hydrogen-based or methyl are respectively indicated, m, n respectively indicate 0~5 integer.)
It should be noted that in the present invention, so-called " (methyl) acrylate " refers to acrylate and methacrylic acid One or both of ester, so-called " (methyl) acryloyl group " refer to one of acryloyl group and methylacryloyl or two Person.
Above-mentioned polymerizable monomer (B) is multifunctional polymerizable monomer, is to have 2 or more polymerizable groups in 1 molecule Monomer.Above-mentioned polymerizable group is vinyl, (methyl) acryloyl group etc. as carbon-to-carbon double bond, excellent from curability Different angle is set out, preferably (methyl) acryloyl group.
As the above-mentioned polymerizable monomer (B) with (methyl) acryloyl group, it can be mentioned, for example 1,4-butanediol two (first Base) acrylate, 3- methyl-1,5- pentanediol two (methyl) acrylate, 1,6- hexylene glycol two (methyl) acrylate, new penta Glycol two (methyl) acrylate, 2- methyl-1,8- ethohexadiol two (methyl) acrylate, 2- butyl -2- ethyl -1,3- the third two Alcohol two (methyl) acrylate, Tricyclodecane Dimethanol two (methyl) acrylate, ethylene glycol two (methyl) acrylate, diethyl Glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, 3 the third two Two (methyl) acrylate of the dihydric alcohols such as alcohol two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, poly- the third two Alcohol two (methyl) acrylate, two (methyl) acrylate of three (2- hydroxyethyl) isocyanuric acid esters, at 1 mole of neopentyl glycol Two (methyl) acrylate of glycol obtained from the ethylene oxide or propylene oxide of 4 moles of upper addition or more rub in bisphenol-A 1 Two (methyl) acrylate, the trimethylolpropane of glycol obtained from 2 moles of addition of ethylene oxide or propylene oxide on that Three (methyl) acrylate, ethylene-oxide-modified trimethylolpropane tris (methyl) acrylate, three hydroxyl first of epoxy pronane modification Base propane three (methyl) acrylate, two (trihydroxy methyl) propane three (methyl) acrylate, two (trihydroxy methyl) propane, four (first Base) acrylate, three (2- (methyl) acryloyl-oxyethyl) isocyanuric acid esters, pentaerythrite three (methyl) acrylate, season Penta tetrol four (methyl) acrylate, dipentaerythritol three (methyl) acrylate, dipentaerythritol four (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate etc..These multifunctional polymerizable monomers (B) it can be used a kind, can also be used in combination two or more.In addition, in these multifunctional polymerizable monomers (B), originally from raising It sets out in terms of the marresistance of the cured coating film of the Actinic-radiation curable composition of invention, preferably dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate, pentaerythrite four (methyl) acrylate, pentaerythrite three (methyl) acrylate.
In addition, in Actinic-radiation curable composition of the invention, as above-mentioned polymerizable monomer (A) and above-mentioned Polymerizable component other than polymerizable monomer (B) can also cooperate carbamate (methyl) acrylate.Above-mentioned carbamic acid Ester (methyl) acrylate (E) is to react polyisocyanates (e1) with (methyl) acrylate (e2) with hydroxyl to obtain 's.
As above-mentioned polyisocyanates (e1), can enumerate: aliphatic polyisocyante and aromatic polyisocyanate, from energy It sets out in terms of the coloring for enough reducing the cured coating film of Actinic-radiation curable composition of the invention, preferred aliphat is more Isocyanates.
Above-mentioned aliphatic polyisocyante is the compound that the position in addition to isocyanate group is made of aliphatic hydrocarbon.Make For the specific example of the aliphatic polyisocyante, can enumerate: hexamethylene diisocyanate, relies lysine diisocyanate The aliphatic polyisocyantes such as propylhomoserin triisocyanate；Norbornene alkyl diisocyanate, isophorone diisocyanate, methylene Bis- (4- cyclohexyl isocyanates), bis- (isocyanatomethyl) hexamethylenes of 1,3-, 2- methyl-1, the cyclization of 3- diisocyanate root oneself Alkane, 2- methyl-1, ester ring types polyisocyanates such as 5- diisocyanate root trimethylcyclohexane etc..In addition, by above-mentioned aliphatic polyisocyanate cyanogen Trimer obtained from acid esters or ester ring type polyisocyanates trimerizing can also be used as above-mentioned aliphatic polyisocyante to make With.In addition, these aliphatic polyisocyantes can be used a kind, can also be used in combination two or more.
In above-mentioned aliphatic polyisocyante, in order to improve the marresistance of film, preferred aliphat polyisocyanic acid As the hexamethylene diisocyanate of the diisocyanate of straight-chain aliphatic hydrocarbon, as the drop of ester ring type diisocyanate in ester Bornylane diisocyanate, isophorone diisocyanate.
Above-mentioned (methyl) acrylate (e2) is the compound with hydroxyl He (methyl) acryloyl group.As (methyl) The specific example of acrylate (e2), can enumerate: (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid 2- hydroxybutyl, (methyl) acrylic acid 4- hydroxybutyl, 1,5-PD list (methyl) acrylate, 1,6- Hexylene glycol list (methyl) acrylate, neopentyl glycol single (methyl) acrylate, 3-hydroxypivalic acid neopentyl glycol single (methyl) third List (methyl) acrylate of the dihydric alcohols such as olefin(e) acid ester；Trimethylolpropane two (methyl) acrylate, ethylene oxide (EO) change Property trimethylolpropane (methyl) acrylate, modified trimethylolpropane two (methyl) acrylate of propylene oxide (PO), sweet The lists of trihydroxylic alcohols such as oily two (methyl) acrylate, bis- (2- (methyl) acryloyl-oxyethyl) hydroxyethyl isocyanuric acid esters or Two (methyl) acrylate or the list and two that a part of these alcohol hydroxyl groups is had obtained by modified to hydroxyl with 6-caprolactone (methyl) acrylate；Pentaerythrite three (methyl) acrylate, two (trihydroxy methyl) propane three (methyl) acrylate, two seasons Penta tetrol five (methyl) acrylate etc. have 1 function hydroxyl and (methyl) acryloyl groups more than 3 functions compound or The compound is further had obtained by modified with 6-caprolactone to the multifunctional (methyl) acrylate of hydroxyl；Dipropylene glycol list (methyl) acrylate, diethylene glycol list (methyl) acrylate, (methyl) acrylic acid 2- hydroxy methacrylates, polyethyleneglycol (methyl) acrylate etc. has (methyl) acrylate of oxyalkylene chain；Polyethylene glycol propylene glycol list (methyl) propylene Acid esters, polybutylene-polyoxypropylene list (methyl) acrylate etc. has (methyl) propylene of the oxyalkylene chain of block structure Acid esters；Poly- (ethylene glycol-tetramethylene glycol) single (methyl) acrylate, poly- (propylene glycol-tetramethylene glycol) are single (methyl) Acrylate etc. has (methyl) acrylate of oxyalkylene chain etc. of disordered structure.These (methyl) acrylate (e2) can To use a kind, can also be used in combination two or more.
In above-mentioned carbamate (methyl) acrylate (e2), in order to improve active energy beam of the invention The marresistance of the cured coating film of solidification compound, with the amino of 4 or more (methyl) acryloyl groups preferably in 1 molecule Formic acid esters (methyl) acrylate.Have 4 in 1 molecule to become above-mentioned carbamate (methyl) acrylate (E) Carbamate (methyl) acrylate of a above (methyl) acryloyl group, it is excellent as above-mentioned (methyl) acrylate (e2) Select (methyl) acrylate with 2 or more (methyl) acryloyl groups.As such (methyl) acrylate (e2), can arrange Citing such as: trimethylolpropane two (methyl) acrylate, ethylene-oxide-modified trimethylolpropane two (methyl) acrylate, Epoxy pronane modification trimethylolpropane two (methyl) acrylate, glycerol two (methyl) acrylate, bis- (2- (methyl) propylene Trimethylammonium) hydroxyethyl isocyanuric acid ester, pentaerythrite three (methyl) acrylate, two (trihydroxy methyl) propane, three (first Base) acrylate, dipentaerythritol five (methyl) acrylate etc..Relative to a kind of above-mentioned aliphatic polyisocyante, these (methyl) acrylate (e2) can be used a kind, can also be used in combination two or more.In addition, in these (methyl) acrylate (e2) in, pentaerythrite three (methyl) acrylate, dipentaerythritol five (methyl) acrylate can be improved marresistance, therefore It is preferred that.
Reacting for above-mentioned polyisocyanates (e1) and above-mentioned (methyl) acrylate (e2) can ammonia by conventional method Carbamateization reacts to carry out.In addition, preferably being urged in urethane for the progress for promoting urethane to react Urethane reaction is carried out in the presence of agent.As above-mentioned urethanation catalyst, it can be mentioned, for example: pyridine, The amine compounds such as pyrroles, triethylamine, diethylamine, dibutyl amine；The phosphorus compounds such as triphenylphosphine, triethyl phosphine；Two fourth of tin dilaurate Organo-tin compounds, the zinc octoates such as Ji Xi, trilauryl tin octylate, octyltin diacetate, dibutyltin diacetate, tin octoate etc. Organic zinc compound etc..
In addition, in Actinic-radiation curable composition of the invention, as above-mentioned polymerizable monomer (A), above-mentioned Polymerizable component other than polymerizable monomer (B) and carbamate (methyl) acrylate (E), can also use as needed Epoxy (methyl) acrylate, polyester (methyl) acrylate, polyethers (methyl) acrylate etc..As above-mentioned epoxy (methyl) Acrylate, it can be mentioned, for example: by making (methyl) acrylic acid and bisphenol-type epoxy resin, phenol aldehyde type epoxy resin, bunching water Glyceryl methacrylate etc. is reacted and is esterified obtained epoxy (methyl) acrylate.In addition, as above-mentioned poly- Ester (methyl) acrylate, it can be mentioned, for example: it is obtained and making (methyl) acrylic acid with by polybasic carboxylic acid and polyhydric alcohol Two ends be that the polyester of hydroxyl is reacted and is esterified obtained polyester (methyl) acrylate or by making (methyl) third Olefin(e) acid is reacted with substance obtained from the addition alkylene oxide on polybasic carboxylic acid and is esterified obtained polyester (methyl) propylene Acid esters.In turn, as above-mentioned polyethers (methyl) acrylate, it can be mentioned, for example: by making (methyl) acrylic acid and polyether polyols Alcohol is reacted and is esterified obtained polyethers (methyl) acrylate.
Above-mentioned resin (B) is the resin with alicyclic structure and quaternary ammonium salt.
As the manufacturing method of above-mentioned resin (C), it can be mentioned, for example following methods: with the polymerism list with alicyclic structure Body (c1) and polymerizable monomer (c2) with quaternary ammonium salt are used as essential component, and make above-mentioned polymerizable monomer (c1) and above-mentioned Polymerizable monomer (c2) is copolymerized with the polymerizable monomer (c3) that can be copolymerized.
Above-mentioned polymerizable monomer (c1) is the polymerizable monomer with alicyclic structure.As above-mentioned alicyclic structure, can enumerate Such as: cyclopropane ring, cyclobutane ring, pentamethylene ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring Etc. monocycles alicyclic structure；Bicyclic hendecane ring, decahydronaphthalene (naphthalane) ring, tricyclic [5.2.1.02,6] decane ring, bicyclic [4.3.0] The polycyclic alicyclic ring knots such as nonane ring, tricyclic [5.3.1.1] dodecane ring, tricyclic [5.3.1.1] dodecane ring, spiral shell [3.4] octane ring Structure etc..In addition, the specific example as above-mentioned polymerizable monomer (b1), can enumerate (methyl) cyclohexyl acrylate, Isosorbide-5-Nitrae-ring Hexane dimethanol list (methyl) acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid dicyclopentenyl ester, (methyl) Acrylic acid dicyclopentenyl oxygroup ethyl ester, (methyl) dicyclopentanyl acrylate etc..These polymerizable monomers (c1) can be used a kind, It can also be used in combination two or more.
As above-mentioned polymerizable monomer (c2), it can be mentioned, for example: 2- [(methyl) acryloxy] ethyl-trimethyl chlorination The counter anions such as ammonium, 3- [(methyl) acryloxy] hydroxypropyltrimonium chloride are the polymerizable monomer of chloride；2- [(methyl) acryloxy] ethyMmethylammonium bromide, 3- [(methyl) acryloxy] propyltrimethylammonium bromide etc. contend with Anion is the polymerizable monomer of bromide；2- [(methyl) acryloxy] ethyl trimethyl ammonium aminomethyl phenyl sulfonate, 2- [(methyl) acryloxy] ethyl trimethyl ammonium methyl sulfonate, 3- [(methyl) acryloxy] oxypropyl trimethyl ammonium methyl Phenylbenzimidazole sulfonic acid salt, 3- [(methyl) acryloxy] oxypropyl trimethyl ammonium methyl sulfonate, 2- [(methyl) acryloxy] second The counter anions such as base trimethylammoniumethyl sulfate, 3- [(methyl) acryloxy] oxypropyl trimethyl ammonium methyl sulphate are The polymerizable monomer etc. of non-halogen.These polymerizable monomers (c2) can be used a kind, can also be used in combination two or more.
As above-mentioned polymerizable monomer (c3), it can be mentioned, for example: (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) acrylic acid n-pentyl ester, (methyl) the just own ester of acrylic acid, the positive heptyl ester of (methyl) acrylic acid, (methyl) n-octyl, (methyl) acrylic acid 2- ethyl hexyl (methyl) acrylic acid alkyls such as ester, (methyl) nonyl acrylate, (methyl) decyl acrylate, (methyl) dodecylacrylate Ester；Methoxy poly (ethylene glycol) list (methyl) acrylate, octyloxy polyethylene glycol (methyl) acrylic acid 2- hydroxy methacrylates, the moon Osmanthus oxygroup polyethyleneglycol (methyl) acrylate, stearic oxygroup polyethyleneglycol (methyl) acrylate, the poly- second two of phenoxy group Alcohol list (methyl) acrylate, phenoxy group polyethylene glycol (methyl) acrylic acid 2- hydroxy methacrylates, Nonylphenoxy poly- the third two The polyalkylene glycol such as single (methyl) acrylate of alcohol list (methyl) acrylate, Nonylphenoxy poly- (ethylene glycol propylene glycol) List (methyl) acrylate；(methyl) acrylic acid 2- perfluoro hexyl ethyl ester etc. has (methyl) acrylate of fluoro-alkyl Deng.These polymerizable monomers (c3) can be used a kind, can also be used in combination two or more.
In above-mentioned polymerizable monomer (c3), combined from active energy ray-curable of the invention can be further increased It sets out in terms of the antistatic property of the cured coating film of object, preferably list (methyl) acrylate of polyalkylene glycol, more preferable first Oxygroup polyethyleneglycol (methyl) acrylate.In addition, (methyl) acrylate with fluoro-alkyl from have can be into one It sets out in terms of the effect of the antistatic property of the cured coating film of step raising Actinic-radiation curable composition of the invention It is preferred that.
In list (methyl) acrylate of above-mentioned polyalkylene glycol, from active energy of the invention can be further increased It sets out in terms of the antistatic property for measuring the cured coating film of ray-curable composition, becomes the list (first of above-mentioned polyalkylene glycol Base) acrylate raw material polyalkylene glycol number-average molecular weight be preferably 200~8,000 range, more preferably 300 ~6,000 range, further preferably 400~4,000 range, particularly preferably 400~2,000 range.
From the antistatic property for the cured coating film that can further increase Actinic-radiation curable composition of the invention Aspect set out, the ratio of the above-mentioned polymerizable monomer (c1) in the raw material total amount of above-mentioned resin (C) is preferably 5~55 mass % Range, the more preferably range of 10~50 mass %, the further preferably range of 12~45 mass %.
In addition, quiet from resisting for the cured coating film that can further increase Actinic-radiation curable composition of the invention Electrical aspect is set out, and the ratio of the above-mentioned polymerizable monomer (c2) in the raw material total amount of above-mentioned resin (C) is preferably 30~90 The range of quality %, the more preferably range of 40~80 mass %, the more preferably range of 45~70 mass %.
In turn, list (methyl) acrylate of polyalkylene glycol is stated in use as above-mentioned polymerizable monomer (c3) In the case of, from the antistatic property of the cured coating film that can further increase Actinic-radiation curable composition of the invention Aspect is set out, and the ratio of list (methyl) acrylate of the polyalkylene glycol in the raw material total amount of above-mentioned resin (C) is preferably 5 The range of~60 mass %, the more preferably range of 10~50 mass %, the further preferably range of 20~40 mass %.
In addition, using feelings of (methyl) acrylate with above-mentioned fluoro-alkyl as above-mentioned polymerizable monomer (c3) Under condition, from the side of the antistatic property for the cured coating film that can further increase Actinic-radiation curable composition of the invention Face is set out, and the ratio of (methyl) acrylate with fluoro-alkyl in the raw material total amount of above-mentioned resin (C) is preferably 0.1~ The range of 20 mass %, the more preferably range of 0.5~10 mass %, the further preferably range of 1~5 mass %.
From the antistatic property for the cured coating film that can further increase Actinic-radiation curable composition of the invention Aspect set out, the weight average molecular weight of above-mentioned resin (C) is preferably 1,000~100,000 range, more preferably 2,000~ 50,000 range, further preferably 3,000~30,000 range.It should be noted that the Weight-average molecular in the present invention Amount is the value in terms of polystyrene conversion measured by gel permeation chromatography (GPC) method.
From the antistatic property for the cured coating film that can further increase Actinic-radiation curable composition of the invention Aspect set out, conjunction of the use level of above-mentioned resin (C) relative to above-mentioned polymerizable monomer (A) and above-mentioned polymerizable monomer (B) The range that 100 mass parts are preferably 0.1~30 mass parts, the more preferably range of 0.5~20 mass parts are counted, further preferably The range of 1~10 mass parts, the particularly preferably range of 1.5~7 mass parts.
Above-mentioned organic solvent (D) as long as other in Actinic-radiation curable composition of the invention can be dissolved The organic solvent of ingredient, so that it may use without particular limitation.In addition, from active-energy of the invention can be further increased It sets out in terms of the antistatic property of the cured coating film of ray-curable composition, the dispersion preferably in terms of Hansen Solubility Parameter Item (δ D) is 15.5~16.1MPa0.5Range, polarity item (δ P) be 6.3~10.4MPa0.5Range, hydrogen bond item (δ H) be 5.1~11.6MPa0.5Range organic solvent.
It should be noted that the definition and calculating of Hansen Solubility Parameter write " Hansen in Charles M.Hansen Solubility Parameters；It is on the books in A Users Handbook (CRC Press, 2007) ".In addition, by using Computer software " Hansen Solubility Parameters in Practice (HSPiP) ", thus about not having in document The organic solvent of the record of parameter value also can extrapolate Hansen Solubility Parameter by its chemical structure.In the present invention, for There is the organic solvent of the record of parameter value in document, using the value, for there is no the organic solvent of the record of parameter value in document, Using the parameter value calculated using HSPiP edition 4 .1.06.
1 kind of organic solvent can be used in above-mentioned organic solvent (D), two or more organic solvent and use can also be made For mixed solvent use.It, can be with by the Hansen Solubility Parameter of various organic solvents by two or more be used in combination 3 parameter weightings it is average obtained from value used as the combination in above-mentioned range.
By two or more organic solvents and in the case where use and carry out use as above-mentioned organic solvent (D), as tune The method of the whole range for the Hansen Solubility Parameter, it can be mentioned, for example: ethyl alcohol (δ D=15.8MPa0.5, δ P=8.8MPa0.5、δ H=19.4MPa0.5) etc. alcoholic solvents and methyl ethyl ketone (δ D=16.0MPa0.5, δ P=9.0MPa0.5, δ H=5.1MPa0.5) etc. ketone it is molten The combination of agent can also enumerate above-mentioned ketone series solvent and methyl acetate (δ D=15.5MPa0.5, δ P=7.2MPa0.5, δ H= 7.6MPa0.5) etc. ester solvents combination.In addition, other than the combination of the alcoholic solvent and ketone solvent, it is above-mentioned organic molten by making Also diacetone alcohol (the δ D=15.8MPa containing 3~40 mass % in agent (D)0.5, δ P=8.2MPa0.5, δ H=10.8MPa0.5)、 Acetylacetone,2,4-pentanedione (δ D=16.1MPa0.5, δ P=10.0MPa0.5, δ H=6.2MPa0.5), dimethyl carbitol (δ D= 15.7MPa0.5, δ P=6.1MPa0.5, δ H=6.5MPa0.5), propylene glycol monomethyl ether (δ D=15.6MPa0.5, δ P= 5.6MPa0.5, δ H=9.8MPa0.5) etc. boiling points be 100~180 DEG C of high boiling solvent, so as to improve coating stability, From that can prevent from cracking in cured coating film, so that appearance of film is become excellent aspect and set out, be preferred.
The use level of above-mentioned organic solvent (D) in Actinic-radiation curable composition of the invention is preferably set to reach To the amount for the viscosity for being suitable for aftermentioned coating method.
In addition, Actinic-radiation curable composition of the invention can be by coated on the active energy of irradiation after substrate It measures ray and cured coating film is made.The active energy beam refers to the electricity such as ultraviolet light, electron ray, alpha ray, β ray, gamma-rays From radioactive ray.In the case where cured coating film is made as active energy beam in irradiation ultraviolet light, preferably in work of the invention Property energy ray-curable composition in addition Photoepolymerizationinitiater initiater (F) improve curability.In addition, if desired, then Photosensitizer (G) can be added further to improve curability.On the other hand, due to using electron ray, alpha ray, β ray, In the case where the ionizing radiations such as gamma-rays, even if not using Photoepolymerizationinitiater initiater (F), photosensitizer (G), also can rapidly it consolidate Change, so It is not necessary to being especially added with Photoepolymerizationinitiater initiater (F), photosensitizer (G).
As above-mentioned Photoepolymerizationinitiater initiater (F), it can be mentioned, for example: diethoxy acetophenone, 2- hydroxy-2-methyl -1- benzene Base propane -1- ketone, oligomeric { 2- hydroxy-2-methyl -1- [4- (1- methyl ethylene) phenyl] acetone }, benzil dimethyl contracting Ketone, 1- (4- isopropyl phenyl) -2- hydroxy-2-methyl propane -1- ketone, 4- (2- hydroxyl-oxethyl) phenyl-(2- hydroxyl -2- third Base) ketone, 1- hydroxycyclohexylphenylketone, 2- methyl -2- morpholino (4- sulfidomethyl phenyl) propane -1- ketone, 2- benzyl -2- diformazan The acetophenones based compounds such as base amino -1- (4- morphlinophenyl)-butanone；Benzoin, benzoin methyl ether, benzoin isopropyl The benzoins based compound such as ether；2,4,6- trimethylbenzene acyloin diphenyl phosphine oxides, bis- (2,4,6- trimethylbenzoyl)-benzene The acylphosphine oxide compounds such as base phosphine oxide；Benzil (dibenzoyl), methyl phenyl glyoxylate ester, hydroxyphenyl acetic acid 2- The benzils systems such as (2- hydroxyl-oxethyl) ethyl ester, hydroxyphenyl acetic acid 2- (2- oxo -2- phenylacetyl oxygroup ethyoxyl) ethyl ester Compound；Benzophenone, o-benzoyl yl benzoic acid methyl esters -4- phenyl benzophenone, 4,4 '-dichloro benzophenones, hydroxyl two Benzophenone, 4- benzoyl -4 '-methyl-diphenylsulfide, acrylated benzophenone, 3,3 ', 4,4 '-four (t-butyl peroxies Change carbonyl) benzophenone, 3,3 '-dimethyl -4- methoxy benzophenones, 2,4,6- tri-methyl benzophenones, 4- methyldiphenyl The benzophenone based compounds such as ketone；2-isopropylthioxanthone, 2,4- dimethyl thioxanthone, 2,4- diethyl thioxanthone, 2,4- The thioxanthones based compound such as two clopenthixal ketones；Michler's keton, 4, the aminobenzophenones system such as 4 '-diethylamino benzophenone chemical combination Object；10- butyl -2- chloro-acridine ketone, 2- ethyl hydrazine, 9,10- phenanthrenequione, camphorquinone, 1- [4- (4- benzoylphenylsulfanyl) benzene Base] -2- methyl -2- (4- methylphenylsulfonyl) propane -1- ketone etc..These Photoepolymerizationinitiater initiaters (F) can be used a kind, It can be used in combination two or more.
In addition, as above-mentioned photosensitizer (G), it can be mentioned, for example: the uncles such as diethanol amine, N methyldiethanol amine, tri-n-butylamine The carbamide compounds such as amine compounds, o-tolyl thiocarbamide, diethyldithioposphoric acid sodium, s- benzylisothiourea tosilate etc. Sulphur compound etc..
The usage amount of above-mentioned Photoepolymerizationinitiater initiater (F) and photosensitizer (G) is solid relative to active energy beam of the invention Include the polymerizable component total 100 including above-mentioned polymerizable monomer (A) and above-mentioned polymerizable monomer (B) in the property changed composition Mass parts are respectively preferably 0.05~20 mass parts, more preferably 0.5~10 mass %.
In Actinic-radiation curable composition of the invention, as other other than above-mentioned ingredient (A)~(G) Complex, can depending on the application, require characteristic cooperate polymerization inhibitor, surface conditioner, antistatic agent, defoaming agent, viscosity adjustment Agent, resistance to light stabilizer, weathering stabilizers, heat-resisting stabilizing agent, ultraviolet absorbing agent, antioxidant, levelling agent, organic pigment, nothing The additives such as machine pigment, pigment dispersing agent, silica bead, organic bead；Silica, aluminium oxide, titanium oxide, zirconium oxide, Inorganic fillers such as antimony pentaoxide etc..These other complexs can be used a kind, can also be used in combination two or more.
Film of the invention is that active energy ray-curable combination of the invention is applied by least 1 face in film base material Object irradiates active energy beam later film obtained from cured coating film is made.
As the material of above-mentioned film base material used in film of the invention, the high resin of preferably clear, it can be mentioned, for example: The polyester based resins such as polyethylene terephthalate, polybutylene terephthalate (PBT), polyethylene naphthalate；Poly- third The polyolefin-based resins such as alkene, polyethylene, polymethylpentene -1；Cellulose acetate (diacetyl cellulose, tri acetyl cellulose Deng), cellulose-acetate propionate, cellulose acetate-butyrate, acetate propionate cellulose butyrate, Cellacefate, nitre The cellulose-based resins such as acid cellulose；The acrylic resins such as polymethyl methacrylate；The chlorine such as polyvinyl chloride, Vingon Vinylite；Polyvinyl alcohol；Vinyl-vinyl acetate copolymer；Polystyrene；Polyamide；Polycarbonate；Polysulfones；Polyethers Sulfone；Polyether-ether-ketone；The polyimides system resins such as polyimides, polyetherimide；Norbornene resin is (for example, Zeon Corporation system " ZEONOR "), modified norbornene resin (for example, JSR Corp.'s system " ARTON "), cyclic olefin Copolymer (for example, Mitsui Chemicals, Inc's system " APEL ") etc..In turn, it also can be used two or more comprising these resins Substrate fitting obtained from substrate.
In addition, above-mentioned film base material can be membranaceous, or sheet, thickness are preferably 20~500 μm of range.Separately Outside, using membranaceous base material film, thickness is preferably 20~200 μm of range, and more preferably 30~150 μm Range, further preferably 40~130 μm of range.By the way that the thickness of film base material is set as the range, thus in the list of film In the case that hard conating is arranged using Actinic-radiation curable composition of the invention in face, inhibition volume is also become easy It is bent.
As the method for applying Actinic-radiation curable composition of the invention on above-mentioned film base material, example can be enumerated Such as: die coating, intaglio plate coating, roller coating, comma coating, airblade coating, licks painting, spraying coating, dip coated, rotation at micro- intaglio plate coating It applies, brushes, utilizes full version coating, bar coating, flow coat of silk screen etc..
In addition, will live in the case where including organic solvent in Actinic-radiation curable composition of the invention Property energy ray-curable composition be coated on base material film after and before irradiating active energy beam, it is organic molten in order to make Agent volatilization, in addition, it is segregated above-mentioned resin (B) in film coated surface, and it is preferred that carrying out heating or drying at room temperature.As heat drying Condition, as long as the condition for making organic solvent volatilize, there is no particular limitation, be generally preferably 50~100 DEG C in temperature Range is interior, the time is to be thermally dried in the range of 0.5~10 minute.
As the cured active energy beam of Actinic-radiation curable composition of the invention is made, as described above, being The ionizing radiations such as ultraviolet light, electron ray, alpha ray, β ray, gamma-rays.Here, use ultraviolet light as active-energy In the case where ray, as the device for irradiating the ultraviolet light, it can be mentioned, for example: low pressure mercury lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, Metal halide lamp, electrodeless lamp (fusion lamp), chemical lamp, black light lamp, mercury-xenon lamp, short-arc lamp, He-Cd laser, argon laser, Sunlight, LED light etc..
When about the cured coating film for forming Actinic-radiation curable composition of the invention on above-mentioned film base material The film thickness of cured coating film from becoming the hardness of cured coating film sufficiently, and is able to suppress as caused by the cure shrinkage of film Film curling in terms of set out, preferably 1~30 μm of range, more preferably 3~15 μm of range, further preferably 4 ~10 μm of range.
Embodiment
Hereinafter, being more specifically illustrated by embodiment to the present invention.
(Production Example 1: the manufacture of the resin (C-1) with alicyclic structure and quaternary ammonium salt)
Nitrogen is imported in the flask for having agitating device, reflux condensing tube and nitrogen ingress pipe, by the air in flask It is replaced with nitrogen.Later, in flask add 53.7 mass parts of 2- (methacryloxy) ethyl-trimethyl salmiac, 29.3 mass parts of cyclohexyl methacrylate, methoxy polyethylene glycol methacrylate-styrene polymer (Japan Oil Co system " BLEMMER PME-1000"；Number of repeat unit n ≈ 23, molecular weight 1,000) 14.6 mass parts, 1.9 mass of acrylic acid 2- perfluoro hexyl ethyl ester Part, 0.5 mass parts of methacrylic acid, 50 mass parts of methanol and propylene glycol monomethyl ether (hereinafter referred to as " PGME ") 10 mass Part.Then, with 30 minutes be added dropwise by 0.1 mass parts PGME2.4 mass parts of polymerization initiator (azobis isobutyronitrile) dissolution and Then obtained solution reacts 3 hours at 65 DEG C.Then, methanol dilution is added, obtains having alicyclic structure and quaternary ammonium salt 45 mass % solution of resin (C-1).The weight average molecular weight of obtained resin (C-1) is 10,000.
(Production Example 2: the manufacture of the resin (C-2) with alicyclic structure and quaternary ammonium salt)
Nitrogen is imported in the flask for having agitating device, reflux condensing tube and nitrogen ingress pipe, by the air in flask It is replaced with nitrogen.Later, in flask add 53.7 mass parts of 2- (methacryloxy) ethyl-trimethyl salmiac, 14.6 mass parts of cyclohexyl methacrylate, methoxy polyethylene glycol methacrylate-styrene polymer (Japan Oil Co system " BLEMMER PME-1000"；Number of repeat unit n ≈ 23, molecular weight 1,000) 29.3 mass parts, methacrylic acid 2- perfluoro hexyl ethyl ester 1.9 Mass parts, 0.5 mass parts of methacrylic acid, 50 mass parts of methanol and PGME10 mass parts.Then, being added dropwise with 30 minutes will polymerization Solution obtained from 0.1 mass parts of initiator (azobis isobutyronitrile) are dissolved with PGME2.4 mass parts, then reacts at 65 DEG C 3 hours.Then, methanol dilution is added, the 45 mass % solution with the resin (C-2) of alicyclic structure and quaternary ammonium salt are obtained.Institute The weight average molecular weight of obtained resin (C-2) is 10,000.
(Production Example 3: the manufacture of the resin (C-3) with alicyclic structure and quaternary ammonium salt)
Nitrogen is imported in the flask for having agitating device, reflux condensing tube and nitrogen ingress pipe, by the air in flask It is replaced with nitrogen.Later, in flask add 53.7 mass parts of 2- (methacryloxy) ethyl-trimethyl salmiac, 14.6 mass parts of cyclohexyl methacrylate, methoxy polyethylene glycol methacrylate-styrene polymer (Japan Oil Co system " BLEMMER PME-1000"；Number of repeat unit n ≈ 23, molecular weight 1,000) 29.3 mass parts, 1.9 mass of acrylic acid 2- perfluoro hexyl ethyl ester Part, 0.5 mass parts of methacrylic acid, 50 mass parts of methanol and PGME10 mass parts.Then, it was added dropwise with 30 minutes and causes polymerization Solution obtained from 0.1 mass parts of agent (azobis isobutyronitrile) are dissolved with PGME2.4 mass parts, then reaction 3 is small at 65 DEG C When.Then, methanol dilution is added, the 45 mass % solution with the resin (C-3) of alicyclic structure and quaternary ammonium salt are obtained.It is acquired Resin (C-3) weight average molecular weight be 10,000.
(Production Example 4: the manufacture of the resin (C-4) with alicyclic structure and quaternary ammonium salt)
Nitrogen is imported in the flask for having agitating device, reflux condensing tube and nitrogen ingress pipe, by the air in flask It is replaced with nitrogen.Later, in flask add 53.7 mass parts of 2- (methacryloxy) ethyl-trimethyl salmiac, 43.9 mass parts of cyclohexyl methacrylate, 1.9 mass parts of acrylic acid 2- perfluoro hexyl ethyl ester, 0.5 mass parts of methacrylic acid, 50 mass parts of methanol and PGME10 mass parts.Then, it was added dropwise with 30 minutes by 0.1 mass of polymerization initiator (azobis isobutyronitrile) Part solution obtained from the dissolution of PGME2.4 mass parts, then reacts 3 hours at 65 DEG C.Then, methanol dilution is added, is obtained To 45 mass % solution of the resin (C-4) with alicyclic structure and quaternary ammonium salt.The weight average molecular weight of obtained resin (C-4) It is 10,000.
(Production Example 5: the manufacture of the resin (C-5) with alicyclic structure and quaternary ammonium salt)
Nitrogen is imported in the flask for having agitating device, reflux condensing tube and nitrogen ingress pipe, by the air in flask It is replaced with nitrogen.Later, in flask add 54.7 mass parts of 2- (methacryloxy) ethyl-trimethyl salmiac, 19.9 mass parts of cyclohexyl methacrylate, methoxy polyethylene glycol methacrylate-styrene polymer (Japan Oil Co system " BLEMMER PME-1000"；Number of repeat unit n ≈ 23, molecular weight 1,000) 24.9 mass parts, 0.5 mass parts of methacrylic acid, 50 matter of methanol Measure part and PGME10 mass parts.Then, it was added dropwise with 30 minutes and uses 0.1 mass parts of polymerization initiator (azobis isobutyronitrile) Solution obtained from the dissolution of PGME2.4 mass parts, then reacts 3 hours at 65 DEG C.Then, methanol dilution is added, is had There are 45 mass % solution of the resin (C-5) of alicyclic structure and quaternary ammonium salt.The weight average molecular weight of obtained resin (C-5) is 1 Ten thousand.
(Production Example 6: the manufacture of the resin (C ' -1) with alicyclic structure and quaternary ammonium salt)
Nitrogen is imported in the flask for having agitating device, reflux condensing tube and nitrogen ingress pipe, by the air in flask It is replaced with nitrogen.Later, in flask add 54.0 mass parts of 2- (methacryloxy) ethyl-trimethyl salmiac, Methoxy polyethylene glycol methacrylate-styrene polymer (Japan Oil Co's system " BLEMMER PME-1000 "；Number of repeat unit n ≈ 23, Molecular weight 1,000) 44.1 mass parts, 1.9 mass parts of acrylic acid 2- perfluoro hexyl ethyl ester, 50 mass parts of methanol and PGME10 mass Part.Then, with 30 minutes be added dropwise by 0.1 mass parts PGME2.4 mass parts of polymerization initiator (azobis isobutyronitrile) dissolution and Then obtained solution reacts 3 hours at 65 DEG C.Then, methanol dilution is added, obtains having alicyclic structure and quaternary ammonium salt 45 mass % solution of resin (C ' -1).The weight average molecular weight of obtained resin (C ' -1) is 10,000.
(Production Example 7: the manufacture of the resin (C ' -2) with alicyclic structure and quaternary ammonium salt)
Nitrogen is imported in the flask for having agitating device, reflux condensing tube and nitrogen ingress pipe, by the air in flask It is replaced with nitrogen.Later, in flask add 54.7 mass parts of 2- (methacryloxy) ethyl-trimethyl salmiac, Methoxy polyethylene glycol methacrylate-styrene polymer (Japan Oil Co's system " BLEMMER PME-1000 "；Number of repeat unit n ≈ 23, Molecular weight 1,000) 44.8 mass parts, 0.5 mass parts of methacrylic acid, 50 mass parts of methanol and PGME10 mass parts.Then, it uses Solution obtained from dissolving 0.1 mass parts of polymerization initiator (azobis isobutyronitrile) with PGME2.4 mass parts is added dropwise within 30 minutes, Then it is reacted 3 hours at 65 DEG C.Then, methanol dilution is added, the resin (C ' -2) with alicyclic structure and quaternary ammonium salt is obtained 45 mass % solution.The weight average molecular weight of obtained resin (C ' -2) is 10,000.
Resin (C-1) obtained above~(C-5), (C ' -1) and (C ' -2) weight average molecular weight passes through gel permeation chromatography (GPC) method measures under conditions of following.
Measurement device: high speed GPC device (TOSOH Co., Ltd's system " HLC-8220GPC ")
Column: following columns of TOSOH Co., Ltd are connected in series to use.
" TSKgel G5000 " (7.8mmI.D. × 30cm) × 1 piece
" TSKgel G4000 " (7.8mmI.D. × 30cm) × 1 piece
" TSKgel G3000 " (7.8mmI.D. × 30cm) × 1 piece
" TSKgel G2000 " (7.8mmI.D. × 30cm) × 1 piece
Detector: RI (differential refractometer)
Column temperature: 40 DEG C
Eluent: tetrahydrofuran (THF)
Flow velocity: 1.0mL/ minutes
Injection rate: 100 μ L (tetrahydrofuran solution of 0.4 mass % of sample solution concentration)
Standard sample: standard curve is made using following standard polystyrens.
(standard polystyren)
TOSOH Co., Ltd's system " TSKgel standard polystyren A-500 "
TOSOH Co., Ltd's system " TSKgel standard polystyren A-1000 "
TOSOH Co., Ltd's system " TSKgel standard polystyren A-2500 "
TOSOH Co., Ltd's system " TSKgel standard polystyren A-5000 "
TOSOH Co., Ltd's system " TSKgel standard polystyren F-1 "
TOSOH Co., Ltd's system " TSKgel standard polystyren F-2 "
TOSOH Co., Ltd's system " TSKgel standard polystyren F-4 "
TOSOH Co., Ltd's system " TSKgel standard polystyren F-10 "
TOSOH Co., Ltd's system " TSKgel standard polystyren F-20 "
TOSOH Co., Ltd's system " TSKgel standard polystyren F-40 "
TOSOH Co., Ltd's system " TSKgel standard polystyren F-80 "
TOSOH Co., Ltd's system " TSKgel standard polystyren F-128 "
TOSOH Co., Ltd's system " TSKgel standard polystyren F-288 "
TOSOH Co., Ltd's system " TSKgel standard polystyren F-550 "
(embodiment 1)
By high refractive index polymerizable monomer (9,9- bis- [4- (2- acryloyloxyethoxy) phenyl] fluorenes, refractive index 1.616) (hereinafter referred to as " monomer (A-1) ".) 17 mass parts, high refractive index polymerizable monomer (acrylic acid neighbour's phenyl benzyl ester with Equal amount of mixture of the acrylic acid to phenyl benzyl ester, refractive index 1.591, phenyl) (hereinafter referred to as " monomer (A-2) ".) 17 mass Part, polyfunctional acrylic ester mixture (64 mass % of dipentaerythritol hexaacrylate, 17 matter of Dipentaerythritol Pentaacrylate Measure the mixture of %, 19 mass % of dipentaerythritol tetraacrylate) (hereinafter referred to as " monomer (B-1) ".) 66 mass parts, system Make 45 mass % solution, 6.7 mass parts (3 mass parts are calculated as with resin (C-1)), the photopolymerization of resin obtained in example 1 (C-1) Initiator (BASF Japan Co., Ltd. " Irgacure 184 "；1- hydroxycyclohexylphenylketone) 5 mass parts, methyl ethyl ketone (hereinafter referred to as " MEK ".) 40 mass parts and PGME60 mass parts equably mix, obtain the work of 50 mass % of nonvolatile component Property energy ray-curable composition (1).
(embodiment 2~7)
Other than being changed to form shown in table 1~3, carries out similarly to Example 1, obtain active energy beam Solidification compound (2)~(7).
(comparative example 1~2)
It other than being changed to form shown in table 3, carries out similarly to Example 1, it is solid to obtain active energy beam The property changed composition (R1) and (R2).
It should be noted that the abbreviation recorded in table 1~3 indicates following substances.
Monomer (A-3): Dainippon Ink Chemicals's system " UNIDIC EQS-1179 " (bisphenol A-type polyfunctional acrylic ester, refractive index 1.555)
DMC: dimethyl carbonate
Using Actinic-radiation curable composition (1) obtained in the above embodiments 1~7 and comparative example 1~2~ (7), (R1) and (R2) carries out following tests, measurement.
[production of sample for evaluation]
By Actinic-radiation curable composition bar coater coated on a thickness of 60 in such a way that film thickness becomes 5 μm μm tri acetyl cellulose (TAC) film (Fuji Photo Film Co., Ltd.'s system) on, at 60 DEG C after dry 1.5 minutes, in air Using ultraviolet lamp (Eye Graphics Co., Ltd. system, high-pressure sodium lamp) with irradiate light quantity 3kJ/m under atmosphere2Into Row irradiation, the TAC film for obtaining having cured coating film is as sample for evaluation.
[measurement of pencil hardness]
For the surface of the cured coating film of sample for evaluation obtained above, according to JIS test method K5600-5-4: 1999, measure pencil hardness.
[measurement (transparent evaluation) of mist degree]
Haze meter (Japan's electricity is used according to JIS test method K7136:2000 for sample for evaluation obtained above Color Industrial Co., Ltd system " NDH2000 ") measure haze value.
[measurement of refractive index]
Sample for evaluation obtained above is reflected according to the A method of JIS test method K7142:2014 using Abbe Rate meter (Atago Co., Ltd. system " DR-M2 ") measures refractive index.
[measurement (evaluation of antistatic property) of sheet resistance value]
The surface of the cured coating film of sample for evaluation obtained above is made according to JIS test method K6911-1995 With high resistivity meter (Mitsubishi Chemical Analytech Co., Ltd. system " HIRESTA-UP MCP-HT450 "), Sheet resistance value is measured to apply voltage 500V, minute 10 seconds.
By the result of said determination it is shown in table 1~3 in.
[table 1]
[table 2]
[table 3]
The evaluation result as shown in table 1~3 is able to confirm that out: the active-energy of the invention of Examples 1 to 7 is penetrated For the cured coating film of line solidification compound, refractive index is high, and sheet resistance value is also 10 9~10 power orders of magnitude, resists Static behaviour is also high.
On the other hand, comparative example 1 and 2 is to have used without alicyclic structure and the example of the resin with quaternary ammonium salt.Energy Enough confirm: their refractive index is also all high, but sheet resistance value is more than 10 13 powers, and antistatic property is poor.

Claims (6)

1. a kind of Actinic-radiation curable composition, which is characterized in that it contains the high refraction that refractive index is 1.55 or more Rate polymerizable monomer (A), multifunctional polymerizable monomer (B), resin (C) and organic solvent with alicyclic structure and quaternary ammonium salt (D)。
2. Actinic-radiation curable composition according to claim 1, wherein the resin (C) is to have used 5 matter Measure polymer of the polymerizable monomer with alicyclic structure of the mass of %~40 % as raw material.
3. Actinic-radiation curable composition according to claim 1 or 2, wherein the organic solvent (D) be with The dispersion item δ D of Hansen Solubility Parameter meter is 15.5MPa0.5~16.1MPa0.5Range, polarity item δ P be 6.3MPa0.5~ 10.4MPa0.5Range, hydrogen bond item δ H be 5.1MPa0.5~11.6MPa0.5Range solvent.
4. Actinic-radiation curable composition described in any one of claim 1 to 3, wherein the resin (C) Use level relative to total 100 mass parts of the polymerizable monomer (A) and the polymerizable monomer (B) be 0.1 mass parts The range of~30 mass parts.
5. a kind of solidfied material is the solidification of Actinic-radiation curable composition according to any one of claims 1 to 4 Object.
6. a kind of film, which is characterized in that it is with active energy ray-curable group according to any one of claims 1 to 4 Close the cured coating film of object.
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