CN103597049A - Active-energy-ray-curable adhesive composition for plastic film or sheet - Google Patents
Active-energy-ray-curable adhesive composition for plastic film or sheet Download PDFInfo
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- CN103597049A CN103597049A CN201280028664.8A CN201280028664A CN103597049A CN 103597049 A CN103597049 A CN 103597049A CN 201280028664 A CN201280028664 A CN 201280028664A CN 103597049 A CN103597049 A CN 103597049A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/35—Heat-activated
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/05—Polymer mixtures characterised by other features containing polymer components which can react with one another
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Laminated Bodies (AREA)
Abstract
The invention provides an active-energy-ray-curable adhesive composition having low viscosity, excellent curability, excellent adherability to various plastic films or sheets and particularly to hydrophilic plastic films or sheets, and excellent durability. The active-energy-ray-curable adhesive composition for plastic films or sheets comprises at least a curable component and a polymerization initiator, wherein the curable component comprises at least components (A) and (B), and the polymerization initiator comprises at least component (C). Component (A) is an aromatic epoxy compound including two or more epoxy groups in the molecule thereof. Component (B) is an ethylenically unsaturated compound comprising at least: (B1) at least one compound selected from the group consisting of 4-hydroxybutyl acrylate and 2-hydroxybutyl acrylate; and (B2) a compound including two or more ethylenically unsaturated groups in the molecule thereof. Component (C) is a photo-cationic polymerization initiator.
Description
Technical field
The present invention relates to a kind ofly can carry out by irradiating electron beam or ultraviolet isoreactivity energy-ray the active energy ray curable binder composition of bonding various plastics maskings or sheet, composition of the present invention is preferred for bonding by convered structure of the thin layers such as plastics masking or sheet, further be preferred for the various bloomings that use in liquid crystal display device etc. or the manufacture of sheet, it is favored in these technical fields.
Be explained; in this manual; acrylate and/or methacrylic ester are expressed as (methyl) acrylate, and acryl and/or methacryloyl are expressed as (methyl) acryl, and vinylformic acid and/or methacrylic acid are expressed as (methyl) vinylformic acid.
In addition, below, in the situation that there is no specified otherwise, by plastics masking or sheet unified representation, be " plastic film etc. ", by film or sheet unified representation, be " film etc. ".
Background technology
All the time, for the thin layers such as the plastic film of fitting by convered structure each other or thin layer such as laminating plastic film etc. by convered structure with the thin layer being formed by other material by the laminating of convered structure, mainly carry out following dry lamination method: the Solvent Adhesive composition that contains vinyl-vinyl acetate copolymer or polyurethane series polymkeric substance is coated on to the first thin layer by convered structure and make it dry, then uses second thin layers of crimping thereon such as nip rolls by convered structure.
The binder composition using in the method is generally in order to make the glue spread of composition evenly contain a large amount of solvents, and a large amount of solvent vapour volatilization when dry, therefore exists the problems such as toxicity, operational security and environmental pollution.In addition, the heat-sealing for bonding gained laminated film of this binder composition after just laminating thin layer is by convered structure, the post-treatment operation of carving the crossed process etc. of establishing groove, thin layer is peeled off each other by convered structure, and this is the problem existing.
As the binder composition addressing these problems, studied solvent-free binder composition.
As solvent-free binder composition, be widely used binary liquid shape binder composition and by ultraviolet ray or the curing binder composition of electron beam isoreactivity energy-ray.
As binary liquid shape binder composition, main use be take polymkeric substance that end has a hydroxyl and had the so-called polyurethane series binder composition that the polyisocyanate compound of isocyanate group is solidifying agent as host and the end of take.Yet said composition exists solidifies the long shortcoming of required time, therefore, deposits the problem of following isoproductivity aspect: after the thin layer of just fitting is by convered structure, cannot enter in the post-treatment operations such as crossed process.
In contrast to this, the curing speed of active energy ray curable binder composition is fast, so productivity is excellent, receives much concern in recent years.
On the other hand, liquid crystal indicator, due to features such as slim, light weight and low power consumptions, spreads to screen and the television indicator of word processor and computer from miniaturized electronicss such as Vehicular guidance system, mobile phone and PDA.
In recent years, in this liquid crystal display device, active energy ray curable tackiness agent is also brought into use in the laminating of various bloomings used etc.
As blooming etc., can enumerate: polaroid, phase retardation film, compensation film for angular field of view, brightness enhancement film, antireflection film, antiglare film, lens and diffusion sheet etc. can be used various plastics in these bloomings.
In these plastics, as plastics conventional especially in polaroid, can enumerate: polyvinyl alcohol and tri acetyl cellulose.These plastics contain hydroxyl, compare with common plastics, have the advantages that wetting ability is very high.
The active energy ray curable binder composition of using as polaroid, the known favourable optical free radical polymerizable composition with light radical polymerization, utilizes the light cationic polymerization type composition of light cationoid polymerisation and and with the mixed composition of light radical polymerization and light cationoid polymerisation.
As optical free radical polymerizable composition, known have with specified proportion comprise the free-radical polymerised compound that contains hydroxyl or carboxyl isopolarity group and composition of the free-radical polymerised compound of polar functionalities (patent documentation 1) etc. not.
Yet contraction when said composition is solidified is larger, according to by the kind of convered structure, in interface, produces stress and be difficult to obtain sufficient stripping strength.
In addition, in order to address this problem, studied the composition (for example, patent documentation 2 etc.) that contains the urethane that molecular weight is larger (methyl) acrylate.
Yet said composition, due to viscosity rise, has and cannot utilize applying device to carry out the problems such as thin film cladding.In addition, also can relax by the flexibility of raising binder composition the string stress while solidifying, but such method can reduce thermotolerance and the water tolerance of tackiness agent, therefore, in requiring the purposes of strict weather resistance, there is the such problem of undesirable condition of peeling off, foam, ftractureing and so on that produces.
As light cationic polymerization type composition, known have the composition (patent documentation 3) that the epoxy resin of take not containing aromatic ring is principal constituent or contain aliphatic epoxide and the composition of alicyclic epoxy thing and/or trimethylene oxide (patent documentation 4) etc.
Compare with optical free radical polymerizable composition, contraction when said composition is solidified is less, therefore, has advantages of that the stress that can suppress to produce on interface is such.
Yet well-known, in general, light cationoid polymerisation can cause polymerization to be obstructed because of moisture or alkaline matter, under the high environment of humidity or the base material, surface that contain in a large number moisture for being difficult to obtain sufficient stripping strength in alkaline base material.In addition, by employing, contain polyfunctional epoxy resin as the composition of main component, can reduce the polymerization retardation impact that solidified nature is reduced, but such composition exists viscosity rise and cannot utilize applying device to carry out the problems such as thin film cladding.
As mixed composition, known have comprise (methyl) acrylate with tricarbimide ring skeleton, alicyclic epoxy compound, the compound of hydroxyl and the composition of photo-acid generator (patent documentation 5), comprising at least 1 of having in 2 above epoxy group(ing) and these groups is the epoxy resin of ester ring type epoxy group(ing), there are 2 above epoxy group(ing) and do not there is the epoxy resin of ester ring type epoxy group(ing), the composition of light cationic polymerization initiators and polymerizable monomer (patent documentation 6), comprise the compound with 2 above (methyl) acrylics, the compound with hydroxyl and 1 (methyl) acrylic, the cationically polymerizable compound with (methyl) acrylic, the composition of optical free radical polymerization starter and light cationic polymerization initiators (patent documentation 7) etc.
The problem such as it is polymerization retardation that these compositions have solved by hybridization that contraction when curing and moisture causes, but the inventor distinguishes by research the problem shown below that exists.
In patent documentation 5 disclosed composition contain there is tricarbimide ring skeleton (methyl) acrylic compound as essential component; but distinguish according to the inventor's research; in composition, contain described (methyl) acrylate in a large number with more than 2 (methyl) acryl; contraction while solidifying is so not little; the stress that therefore can not suppress on interface produces; therefore, according to the difference of base material, be difficult to obtain sufficient stripping strength.
Although disclosed composition is conceptive in patent documentation 6, contain the composition that hybridization forms, the disclosed composition composition for being formed separately by cationically photopolymerizable monomer only in embodiment, the composition forming about hybridization is specifically open.
In patent documentation 7 disclosed composition using specified proportion contain there is (methyl) acrylic cationically polymerizable compound as essential component, but distinguish according to the inventor's research, if contain a large amount of these compounds in composition, contraction while solidifying is so not little, therefore can not be suppressed at and on interface, produce stress, therefore, according to the difference of base material, be difficult to obtain sufficient stripping strength.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2008-009329 communique (claims)
Patent documentation 2: TOHKEMY 2007-177169 communique (claims)
Patent documentation 3: TOHKEMY 2004-245925 communique (claims)
Patent documentation 4: TOHKEMY 2008-134384 communique (claims)
Patent documentation 5: TOHKEMY 2008-233279 communique (claims)
Patent documentation 6: TOHKEMY 2008-257199 communique (claims)
Patent documentation 7: TOHKEMY 2008-260879 communique (claims)
Summary of the invention
The problem that invention will solve
According to contriver's etc. research, in the situation that the light cationic polymerization type composition that use contains epoxy resin etc. is as tackiness agent, except the problems referred to above, because reaction after finishing in active energy beam irradiation is still carried out and curing what is called " dark reaction " phenomenon generation, therefore, sometimes according to the difference of purposes, produce unfavorable condition.For example, in the situation that composition of the present invention is manufactured to duplexer for the bonding of membranaceous base material, if reel film laminated body after irradiating active energy beam, the shape that exists dark reaction to carry out and make to reel is directly residual, or easily with such problems of vestige such as the fluctuating of film or flat traces.
The present invention completes just in view of the above problems, its object is to provide a kind of active energy ray curable binder composition for plastic film or sheet, the viscosity of said composition is low and solidified nature is excellent, excellent to the bonding force of various plastic films etc., particularly wetting ability plastic film etc., under hot and humid such rigor condition, also require can bring into play sufficient performance in the purposes of weather resistance, and then the problems such as film fluctuating that do not have dark reaction to cause.
Solve the means of problem
The inventor etc. have carried out various research, found that, comprise that " molecule contains the aromatic ring oxygen compounds of 2 above epoxy group(ing), any one or two kinds of in vinylformic acid 4-hydroxyl butyl ester and vinylformic acid 2-hydroxyl butyl ester, and the compound in molecule with 2 above ethylenically unsaturated groups " as solidified nature composition, and comprise light cationic polymerization initiators as the active energy ray curable binder composition of polymerization starter to various plastic films etc., particularly bounding force excellence and the viscosity of wetting ability plastic film etc. are low, in the purposes that requires strict weather resistance, also there is sufficient performance, so far completed the present invention.
Be explained, by binder composition of the present invention, can obtain stacking gradually the cured article layer of composition described in base material, claim 1～5 any one and the duplexer of plastics masking or sheet and, stack gradually the cured article layer of composition described in polyethenol series polarization element film or sheet, claim 1～5 any one and polaroid of plastics masking or sheet etc.
Below, describe the present invention in detail.
Invention effect
Composition of the present invention is used specific epoxy compounds and specific alefinically unsaturated compounds as solidified nature composition and at least can be solidified with light cationic polymerization initiators, therefore, composition of the present invention is that low viscosity and screening characteristics are excellent, to various plastic films etc., even if particularly wetting ability plastic film etc. also can maintain high reliability under high temperature and super-humid conditions, and then the problems such as film fluctuating that do not exist dark reaction to cause, to the thin layers such as various plastic films by convered structure bonding effectively, be particularly preferred for the manufacture of the blooming that uses in liquid crystal indicator etc.
Embodiment
The present invention relates to a kind of plastics masking or sheet active energy ray curable binder composition, it at least consists of solidified nature composition and polymerization starter, solidified nature composition at least consists of following (A) composition and following (B) composition, and polymerization starter at least consists of following (C) composition.
(A) composition: molecule contains the aromatic ring oxygen compound (preferably containing 10～80 % by weight in solidified nature composition total amount 100 % by weight) of 2 above epoxy group(ing).
(B) composition: at least there are by being selected from the alefinically unsaturated compounds that the compound (B2) of 2 above ethylenically unsaturated groups forms at least a kind of compound (B1) of vinylformic acid 4-hydroxyl butyl ester and vinylformic acid 2-hydroxyl butyl ester and molecule.
(C) composition: light cationic polymerization initiators (preferably containing 0.1～20 weight part with respect to solidified nature composition total amount 100 weight parts).
Below, to (A) of the essential component as composition～(C) composition describes.
1.(A) composition
(A) composition is the aromatic ring oxygen compound that molecule contains 2 above epoxy group(ing).At this, aromatic ring oxygen compound is the compound having containing the aromatic ring frame of epoxy group(ing).
As the example of (A) composition, can enumerate: the bisphenol-type epoxy resins such as two or polyglycidyl ether of bisphenol A diglycidyl ether, Bisphenol F diglycidylether, bisphenol-S diglycidyl ether, brominated bisphenol A diglycidylether, brominated bisphenol F diglycidylether, brominated bisphenol S diglycidylether, modified rubber bisphenol A diglycidyl ether, bisphenol fluorene or its epoxide affixture; The novolac epoxys such as novolac epoxy, cresol-novolak epoxy resin, brominated phenols formaldehyde epoxy resin, bromination cresol-novolak epoxy resin, dicyclopentadiene-novolac epoxy; Naphthalene type epoxy resin; Alkyl diphenyl phenol-type epoxy resin; Naphthol type epoxy resin; Biphenyl type epoxy resin; Quinhydrones diglycidylether; Resorcinol diglycidyl ether; Terephthalic acid diglycidylether; Phthalic acid diglycidylether; The epoxide of styrene-butadiene copolymer; The epoxide of styrene-isoprene copolymer; The addition reaction of end carboxylic acid polyhutadiene and bisphenol A type epoxy resin; N, N, N ', N '-four glycidyl group-m-xylene diamine etc.
In addition, except these compounds, also can enumerate: document " epoxy resin-latest developments-" (clear rolling hall, nineteen ninety distribution) the 2nd chapter and document " Process Technology of Polymer " supplementary issue 9 the 22nd volume increase the various compounds of record in 4～6 pages, 9～16 pages, 29～55 pages of number of the edition epoxy resin (meeting of polymer publication, clear and issue for 48 years).
At this, epoxy resin refers to that per molecule on average has 2 above epoxy group(ing) and curing compound or the polymkeric substance by reacting.According to the convention of this area, in this manual, so long as in molecule, there is the solidified nature compound of 2 above epoxy group(ing), even monomer is sometimes also referred to as epoxy resin.
As the aromatic ring oxygen compound outside them, can enumerate: EPICOAT5050,5051,1031S, 1032H60,604,630,871,872,191P, YX310,545, YL6810, YX8800, YL980[are japan epoxy resin (strain) system above] etc.
As (A) composition, in above-claimed cpd, preferred bisphenol-type epoxy resin, more preferably bisphenol A diglycidyl ether.
As (A) composition, can use separately a kind of in above-claimed cpd, also can be used together two or more.
Ratio for (A) composition in solidified nature composition and aftermentioned (B) composition, in solidified nature composition total amount 100 % by weight, (A) composition is that 10～80 % by weight, (B) composition are 20～90 % by weight, more preferably (A) composition is that 20～70 % by weight, (B) composition are 30～80 % by weight, and further preferably (A) composition is that 30～60 % by weight, (B) composition are 40～70 % by weight.By making the ratio of (A) composition, be more than 10 % by weight, it is excellent that the thermotolerance of cured article and water tolerance become, and by making the ratio of (A) composition, is below 80 % by weight, and the viscosity of composition and screening characteristics are excellent, and the bounding force of cured article is excellent.
2.(B) composition
(B) composition is alefinically unsaturated compounds, at least by (B1) composition and (B2) composition form.
By (B1) of the present invention composition, can make the reduced viscosity of composition and cementability, water tolerance and solidified nature excellent.(B1) ratio of composition, in solidified nature composition total amount 100 % by weight, is preferably 10～50 % by weight, more preferably 20～40 % by weight.
By making the ratio of (B1) composition, being more than 10 % by weight, can improving bounding force and solidified nature, is below 50 % by weight by making the ratio of (B1) composition, can reduce the water tolerance of composition.
As mentioned above, (B1) any or both of composition in vinylformic acid 4-hydroxyl butyl ester and vinylformic acid 2-hydroxyl butyl ester form.
By (B2) of the present invention composition, can solve active energy beam irradiate finish after (A) composition still continue reaction and above-mentioned unfavorable condition that the so-called dark reaction of solidifying causes, particularly, can solve: in the situation that manufacturing duplexer for bonding membranaceous base material, while reeling film laminated body after irradiating active energy beam, dark reaction is carried out and the shape that makes to reel is directly residual or easily with film, rise and fall or the problem of the vestige such as scratch.In addition, by cross-linking density, uprise, thermotolerance also improves.
As (B2) composition, can enumerate:
1, 4-butyleneglycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 1, 6-hexylene glycol two (methyl) acrylate, 3-methyl isophthalic acid, 5-pentanediol two (methyl) acrylate, 2-butyl-2-ethyl-1, 3-nonanediol diacrylate, 2-methyl isophthalic acid, 8-ethohexadiol two (methyl) acrylate, 2-hydroxyl-1, 3-bis-(methyl) acryloxy propane, 2-hydroxyl-3-(methyl) acryloxy propyl group (methyl) acrylate, glycerine two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, the polyvalent alcohols such as ditrimethylolpropane four (methyl) acrylate gather (methyl) acrylate,
Neopentyl glycol oxyalkylene affixture two (methyl) acrylate, 1, poly-(methyl) acrylate of the oxyalkylene affixture of the polyvalent alcohols such as oxyalkylene affixture three (methyl) acrylate of 6-hexylene glycol oxyalkylene affixture two (methyl) acrylate, glycerine, TriMethylolPropane(TMP) oxyalkylene affixture three (methyl) acrylate, tetramethylolmethane oxyalkylene affixture three (methyl) acrylate;
Poly-(methyl) acrylate of polyvalent alcohol of the glycol modification such as TriMethylolPropane(TMP) two (methyl) acrylate of neopentyl glycol modification;
Poly-(methyl) acrylate of polyvalent alcohol of the caprolactone modification such as Dipentaerythritol six (methyl) acrylate of caprolactone modification;
Aklylene glycol two (methyl) acrylate such as ethylene glycol bisthioglycolate (methyl) acrylate and propylene glycol two (methyl) acrylate and tetramethylene glycol two (methyl) acrylate;
Glycol ether two (methyl) acrylate, triglycol two (methyl) acrylate, polyalkylene glycol two (methyl) acrylate;
Ester ring type glycol two (methyl) acrylate such as tristane dihydroxymethyl two (methyl) acrylate and two (methyl) vinylformic acid, two cyclopentyl esters;
Bis-phenol based compound oxyalkylene affixture two (methyl) acrylate such as dihydroxyphenyl propane oxyalkylene affixture two (methyl) acrylate, Bisphenol F oxyalkylene affixture two (methyl) acrylate and bisphenol S oxyalkylene affixture two (methyl) acrylate;
A Hydrogenated Bisphenol A based compound two (methyl) acrylate such as Hydrogenated Bisphenol A oxyalkylene affixture two (methyl) acrylate and A Hydrogenated Bisphenol A F oxyalkylene affixture two (methyl) acrylate;
The tricarbimides such as tricarbimide oxyalkylene affixture two (methyl) acrylate, tricarbimide oxyalkylene affixture three (methyl) acrylate, tricarbimide caprolactone affixture three (methyl) acrylate gather (methyl) acrylate;
Two (methyl) acrylate of the esterdiols such as neopentyl glycol hydroxy new pentane acid two (methyl) acrylate and hydroxy new pentane acid neopentyl glycol two (methyl) acrylate;
Esterdiol two (methyl) acrylate of the caprolactone modification such as neopentyl glycol hydroxy new pentane acid two (methyl) acrylate of caprolactone modification;
Fatty acid modified Dipentaerythritol five (methyl) acrylate and fatty acid modified Dipentaerythritol four (methyl) acrylate that the fatty acid response of polyvalent alcohol and (methyl) vinylformic acid and carbon number 2～4 is obtained;
Three propylene formaldehyde (triacrylformal); And
TriMethylolPropane(TMP) phenylformic acid (methyl) acrylate, オ グ ソ ー Le EA-0200,0500,1000(fluorenes are acrylate, Osaka combustion gas chemical company system) etc. aromatics multifunctional (methyl) acrylate.
Be explained, as above-mentioned oxyalkylene affixture, can enumerate: ethylene oxide adduct and propylene oxide adduct etc.
In addition, as the oligopolymer that can be used as (B2) composition, can enumerate: polyester (methyl) acrylate, epoxy (methyl) acrylate and polyethers (methyl) acrylate etc.In addition, these oligopolymer are for having the compound of 2 (methyl) acryls, and according to routine, unless otherwise specified, brief note is (methyl) acrylate.
As polyester (methyl) acrylate, can enumerate polyester polyol and (methyl) acrylic acid dehydration condensation etc.
At this, as polyester polyol, can enumerate the reactant of polyvalent alcohol and carboxylic acid or its acid anhydrides etc.
As polyvalent alcohol, can enumerate: ethylene glycol, glycol ether, triglycol, Tetraglycol 99, polyoxyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butyleneglycol, polytetramethylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, cyclohexanedimethanol, 3-methyl isophthalic acid, 5-pentanediol, 1, the low molecular weight polyols such as 6-hexylene glycol, TriMethylolPropane(TMP), glycerine, tetramethylolmethane and Dipentaerythritol and their oxyalkylene affixture etc.
As carboxylic acid or its acid anhydrides, can enumerate: the diprotic acid such as phthalic acid, m-phthalic acid, terephthalic acid, hexanodioic acid, succsinic acid, fumaric acid, toxilic acid, hexahydrophthalic acid, tetrahydrophthalic acid and trimellitic acid or its acid anhydrides etc.
As poly-(methyl) acrylate of polyester in addition, can enumerate: those compounds described in 74th～76 pages, above-mentioned document " UVEB solidify material " etc.
(methyl) acrylic acid epoxy ester, for making (methyl) vinylformic acid and epoxy resin carry out the compound that addition reaction obtains, can be enumerated: those compounds described in 74th～75 pages, above-mentioned document " UVEB solidify material " etc.
As epoxy resin, can enumerate aromatic epoxy resin and aliphatic epoxy resin etc.
As aromatic epoxy resin, specifically can enumerate: resorcinol diglycidyl ether; Two or polyglycidyl ether of dihydroxyphenyl propane, Bisphenol F, bisphenol S, bisphenol fluorene or its oxyalkylene affixture; The novolac epoxys such as novolac epoxy and cresol-novolak epoxy resin; Glycidyl phthalic imidine; Phthalic acid diglycidyl ester etc.
In addition, also can enumerate: document " epoxy resin-latest developments-" (clear rolling hall, nineteen ninety distribution) the 2nd chapter and document " Process Technology of Polymer " supplementary issue 9 the 22nd volume increase the various compounds of record in 4～6 pages, 9～16 pages, 29～55 pages of number of the edition epoxy resin (meeting of polymer publication, clear and issue for 48 years).
As aliphatic epoxy resin, specifically can enumerate: the aklylene glycol diglycidylethers such as ethylene glycol, propylene glycol, BDO and 1,6-hexylene glycol; The polyalkylene glycol such as polyoxyethylene glycol and polypropylene glycol diglycidyl ether diglycidylether; Neopentyl glycol, dibromoneopentyl glycol and oxyalkylene affixture diglycidylether thereof; The polyglycidyl ether of the polyvalent alcohols such as two, three or four glycidyl ethers of two or triglycidyl ether of trimethylolethane, TriMethylolPropane(TMP), glycerine and oxyalkylene affixture thereof and tetramethylolmethane and oxyalkylene affixture thereof; Two or polyglycidyl ether of Hydrogenated Bisphenol A and oxyalkylene affixture thereof; Tetrahydrophthalic acid diglycidylether; Quinhydrones diglycidylether etc.
In addition, also can enumerate: those compounds described in 3～6 pages of above-mentioned document " Process Technology of Polymer " supplementary issue epoxy resin.
Except these aromatic epoxy resins and aliphatic epoxy resin, also can enumerate: on skeleton, there is the epoxy compounds of triazine core, such as TEPIC[daily output chemistry (strain)], long rapids the changing into (strain) of Denacol EX-310[] etc.; Or those compounds described in 289～296 pages of above-mentioned document " Process Technology of Polymer " supplementary issue epoxy resin etc.
In above-mentioned, as the oxyalkylene of oxyalkylene affixture, optimization ethylene oxide and propylene oxide etc.
As polyethers (methyl) origoester acrylate, there is polyalkylene glycol two (methyl) acrylate, can enumerate: polyoxyethylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate and polytetramethylene glycol two (methyl) acrylate etc.
As the polymkeric substance that can be used as (B2) composition; have have (methyl) acryloxy (methyl) acrylic acid polymer, to having in (methyl) acrylic acid polymer of functional group, import the polymkeric substance as (methyl) acryl of side chain, can enumerate those compounds described in 78th～79 pages of above-mentioned document " UVEB solidify material " etc.
From preventing the unfavorable condition that dark reaction causes and improving stable on heating viewpoint and consider, as (B2) composition, preferred polyalkylene glycol two (methyl) acrylate, tristane dihydroxymethyl two (methyl) acrylate, oxyalkylene modifier two (methyl) acrylate of dihydroxyphenyl propane, oxyalkylene modifier two (methyl) acrylate of Bisphenol F, the oxyalkylene modifier triacrylate of tricarbimide.From maintaining with the viewpoint of the bounding force of wetting ability plastics, consider, particularly preferably the oxyalkylene modifier triacrylate of polyalkylene glycol two (methyl) acrylate, tricarbimide.
(B2) ratio of composition, in solidified nature composition total amount 100 % by weight, is preferably 0.5～40 % by weight, more preferably 1～30 % by weight.
By making the ratio of (B2) composition, be more than 0.5 % by weight, can prevent the unfavorable condition that dark reaction causes and improve thermotolerance, by making the ratio of (B2) composition, be below 40 % by weight, cure shrinkage that can composite inhibiting, thus make the composition of bounding force excellence.
As (B1) composition and (B2) (B) composition beyond composition, can enumerate the compound in (B1) composition molecule in addition with 1 ethylenically unsaturated group, for example, in molecule, there is compound, vinyl compound and the allylic cpd in the compound, molecule of 1 ethylenically unsaturated group and hydroxyl with the aromatic ring frame that contains 1 ethylenically unsaturated group or ester ring type skeleton, (methyl) acrylamide compound, aliphatic series (methyl) acrylate, containing (methyl) acrylate of carboxylic acid, phosphoric acid (methyl) acrylate etc.
As thering is the compound of 1 ethylenically unsaturated group and hydroxyl in the molecule beyond (B1) composition, preferably there is (methyl) acrylate of 1 hydroxyl.Specifically can enumerate: (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, cyclohexanedimethanol mono acrylic ester, (methyl) vinylformic acid affixture of cyclohexene oxide, polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, polytetramethylene glycol list (methyl) acrylate, polyethylene glycol-propylene glycol list (methyl) acrylate, polyethylene glycol-tetramethylene glycol list (methyl) acrylate, polypropylene glycol-polytetramethylene glycol list (methyl) acrylate, (methyl) vinylformic acid 2-hydroxyl-3-phenoxy group propyl ester, (methyl) vinylformic acid 2-hydroxyl-3-butoxy propyl ester, 2-(methyl) acryloxy ethyl-2-hydroxyethyl phthalic ester, 2-(methyl) acryloxy ethyl-2-hydroxypropyl phthalic ester etc.
Wherein, in order to make composition, be low viscosity and excellent in adhesion, preferred molecular weight is lower than 300 compound.As the compound that meets this molecular weight, such as enumerating (methyl) vinylformic acid affixture, (methyl) vinylformic acid 2-hydroxyl-3-phenoxy group propyl ester of (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 3-hydroxypropyl acrylate, cyclohexanedimethanol mono acrylic ester, cyclohexene oxide etc.
In order to make composition, be low viscosity and thermotolerance and bounding force excellence, preferably there is molecule and contain the aromatic ring frame of 1 ethylenically unsaturated group or the compound of ester ring type skeleton.Specifically can enumerate: ester ring type (methyl) acrylate, aromatics (methyl) acrylate, imide (methyl) acrylate.
As ester ring type (methyl) acrylate, can enumerate: (methyl) isobornyl acrylate, (methyl) vinylformic acid norbornene ester, (methyl) vinylformic acid three ring esters in the last of the ten Heavenly stems, (methyl) vinylformic acid two ring pentyl esters, (methyl) vinylformic acid 4-butyl cyclohexyl, (methyl) vinylformic acid tetrahydro furfuryl ester, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid two cyclopentenes esters, (methyl) vinylformic acid adamantane esters, tristane (methyl) acrylate, (methyl) vinylformic acid dicyclopentenyl oxygen base ethyl ester etc.
As aromatics (methyl) acrylate, can enumerate: (methyl) phenyl acrylate, (methyl) acrylate of phenol derivatives, (methyl) benzyl acrylate, (methyl) vinylformic acid phenoxy ethyl, (methyl) acrylate of the oxyalkylene modifier of phenol, (methyl) acrylate of the oxyalkylene modifier of cresols, (methyl) acrylate to the oxyalkylene modifier of cumyl phenol, (methyl) acrylate of the oxyalkylene modifier of nonylphenol, (methyl) acrylate of the oxyalkylene modifier of orthoxenol, (methyl) acrylate of the oxyalkylene modifier of p-phenyl phenol, (methyl) acrylate of the oxyalkylene modifier of tribromophenol, neopentyl glycol (methyl) vinylformic acid benzoic ether etc.
As imide (methyl) acrylate, can enumerate: N-(methyl) acryloxy ethyl hexahydrophthalic phthalimide, 2-(1,2-hexamethylene-1-alkene dicarboximide) ethyl (methyl) acrylate, FANCRYL FA-502A(Hitachi change into industry system) etc.
Wherein, from improving the reason of thermotolerance and bounding force, consider, preferably (methyl) acrylate of the oxyalkylene modifier of (methyl) isobornyl acrylate, (methyl) vinylformic acid two cyclopentyl esters, (methyl) vinylformic acid tetrahydro furfuryl ester, (methyl) vinylformic acid two cyclopentenes esters, (methyl) vinylformic acid dicyclopentenyl oxygen base ethyl ester, (methyl) benzyl acrylate, (methyl) vinylformic acid phenoxy ethyl, phenol, N-(methyl) acryloxy ethyl hexahydrophthalic phthalimide, 2-(1,2-hexamethylene-1-alkene dicarboximide) ethyl (methyl) acrylate etc.
As vinyl compound, can enumerate: the polyfunctional vinyl compounds such as monofunctional vinyl compound, Vinylstyrene such as vinylbenzene, Vinyl toluene, NVP, N-caprolactam, vinyl imidazole, vinyl pyridine.
As allylic cpd, can enumerate: the multifunctional allylic cpds such as simple function allylic cpd, Phthalic acid, diallyl ester, triallyl isocyanurate, triallyl cyanurate such as vinyl carbinol.
As (methyl) acrylamide compound; can enumerate: two acetone (methyl) acrylamide, isobutoxy methyl (methyl) acrylamide, N; N-dimethyl (methyl) acrylamide, tertiary octyl group (methyl) acrylamide, N; N-diethyl (methyl) acrylamide, N, N-dimethylamino-propyl (methyl) acrylamide, (methyl) acryloyl morpholine, acrylamide-2-methyl propane sulfonic, N-sec.-propyl (methyl) acrylamide etc.
As the concrete example of aliphatic series (methyl) acrylate, can enumerate: (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) vinylformic acid isopentyl ester, (methyl) Ethyl acrylate, (methyl) vinylformic acid heptyl ester, (methyl) Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) 2-EHA, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) vinylformic acid undecyl ester, (methyl) dodecylacrylate, (methyl) lauryl acrylate, (methyl) alkyl acrylate of carbon number 12～13, (methyl) aliphatic acrylate, (methyl) vinylformic acid stearyl, (methyl) vinylformic acid isooctadecane base ester, the different tetradecyl ester of (methyl) vinylformic acid, (methyl) vinylformic acid methoxyl group ethyl ester, (methyl) vinylformic acid 3-methoxyl group butyl ester, ethyl carbitol (methyl) acrylate, 2-ethylhexyl Trivalin SF (methyl) acrylate, (methyl) vinylformic acid ethoxy ethoxy ethyl ester, (methyl) vinylformic acid butoxyethyl, methoxyl group ethylene glycol (methyl) acrylate, ethoxydiglycol (methyl) acrylate, (methyl) vinylformic acid ethoxy ethyl ester, methoxyl group triglycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, methoxyl group polypropylene glycol (methyl) acrylate, (methyl) dimethylaminoethyl acrylate, (methyl) vinylformic acid lignocaine ethyl ester, 7-amino-3,7-dimethyl octyl group (methyl) acrylate etc.
As (methyl) acrylate containing carboxylic acid, can enumerate: (methyl) vinylformic acid, (methyl) acrylic acid dimer, 2-(methyl) acryloxy ethyl succsinic acid, 2-(methyl) acryloxy ethyl phthalic acid, 2-(methyl) acryloxy ethyl hexahydrophthalic acid, ω-carboxyl polycaprolactone (methyl) acrylate etc. are containing (methyl) acrylate of carboxylic acid.
As phosphoric acid (methyl) acrylate, can enumerate: 2-(methyl) acryloxy ethyl phosphate ester acid etc.
In addition, as (B1) composition and (B2) (B) composition beyond composition, can enumerate: those compounds described in 53rd～56 pages of document " up-to-date UV curing technology " [(strain) printing information association, distribution in 1991] etc.
(B1) composition and (B2) ratio of composition (B) composition in addition, in solidified nature composition total amount 100 % by weight, be preferably 0～40 % by weight, more preferably 0～30 % by weight.In this ratio, higher than 40 % by weight in the situation that, sometimes cannot give full play to effect of the present invention.
3.(C) composition
(C) composition is light cationic polymerization initiators.That is, by irradiating active energy beam, produce positively charged ion or Lewis acid and free radical, thereby cause the compound of the polymerization of cationically photopolymerizable compound (A) composition, optical free radical polymerizable compound (B) composition.
As the concrete example of (C) composition, can enumerate: sulfonium salt, iodine
salt and diazonium salt etc.
As the example of sulfonium salt, for example, can enumerate:
Triphenylsulfonium hexafluorophosphate,
Triphenylsulfonium hexafluoro antimonate,
Triphenylsulfonium four (pentafluorophenyl group) borate,
Phenylbenzene-4-(thiophenyl) phenyl sulfonium hexafluorophosphate,
Phenylbenzene-4-(thiophenyl) phenyl sulfonium hexafluoro antimonate,
The two hexafluorophosphates of 4,4 '-bis-[phenylbenzene sulfydryl] diphenyl sulfide,
The two hexafluoro antimonates of 4,4 '-bis-[two (beta-hydroxy oxyethyl group) phenyl sulfydryl] diphenyl sulfide,
The two hexafluorophosphates of 4,4 '-bis-[two (beta-hydroxy oxyethyl group) phenyl sulfydryl] diphenyl sulfide,
7-[bis-(toluoyl base) sulfydryl]-ITX hexafluoro antimonate,
7-[bis-(toluoyl base) sulfydryl]-ITX four (pentafluorophenyl group) borate,
4-phenylcarbonyl group-4 '-phenylbenzene sulfydryl-diphenyl sulfide hexafluorophosphate,
4-(to tert-butyl-phenyl carbonyl)-4 '-phenylbenzene sulfydryl-diphenyl sulfide hexafluoro antimonate,
The triarylsulfonium salts such as 4-(to tert-butyl-phenyl carbonyl)-4 '-bis-(toluoyl base) sulfydryl-diphenyl sulfide four (pentafluorophenyl group) borates.
As iodine
the example of salt, for example can enumerate:
Phenylbenzene iodine
four (pentafluorophenyl group) borate,
Phenylbenzene iodine
hexafluorophosphate,
Phenylbenzene iodine
hexafluoro antimonate,
Two (4-tert-butyl-phenyl) iodine
hexafluorophosphate,
Two (4-tert-butyl-phenyl) iodine
hexafluoro antimonate,
Tolyl cumyl iodine
four (pentafluorophenyl group) borate,
Iodine
(4-aminomethyl phenyl) [4-(2-methyl-propyl) phenyl]-hexafluorophosphate,
Two (4-nonyl phenyl) iodine
hexafluorophosphate,
Two (4-alkyl phenyl) iodine
hexafluorophosphate
Deng diaryl iodine
salt.
As the example of diazonium salt, for example, can enumerate:
Phenyl diazonium hexafluoro antimonate,
Phenyl diazonium hexafluorophosphate etc.
As the commercially available product of (C) composition, can enumerate: ADEKA OPTOMERSP-100,150,152,170,172[(strain) ADEKA system], light trigger 2074(Rhodia company system), KAYARAD PCI-220,620[Japan's chemical drug (strain) system], Irgacure250(Ciba Japan company system], CPI-100P, 101A, 200K, 210S[San-Apro (strain) system), WPI-113,116(and the pure pharmaceutical worker of light industry system), BBI-102, BBI-103, TPS-102, TPS-103, DTS-102, DTS-103[body ど り chemistry (strain) system] etc.
Wherein, from reasons such as active energy ray-curable excellence, cured film water tolerance excellence and non-colorings, consider, preferably triarylsulfonium salt and diaryl iodine
salt, particularly considers from the viewpoint of solidified nature excellence, preferably diaryl iodine
salt.
As triarylsulfonium salt, in above-claimed cpd, preferred triphenylsulfonium hexafluorophosphate and phenylbenzene-4-(thiophenyl) phenyl sulfonium hexafluorophosphate.As diaryl iodine
salt, in above-claimed cpd, preferred tolyl cumyl iodine
four (pentafluorophenyl group) borate (light trigger 2074; Rhodia Japan (strain) system), phenylbenzene iodine
hexafluorophosphate, iodine
(4-aminomethyl phenyl) [4-(2-methyl-propyl) phenyl]-hexafluorophosphate (Irgacure250; BASF Japan (strain) system), two (4-tert-butyl-phenyl) iodine
hexafluorophosphate and WPI-113(and the pure pharmaceutical worker of light industry system).
As (C) composition, can use separately above-claimed cpd, or also can use two or more.
(C) ratio of composition, with respect to solidified nature composition total amount 100 weight parts, is preferably 0.1～20 weight part, more preferably 1～10 weight part, more preferably 2～7 weight parts.By making the ratio of (C) composition, be more than 0.1 weight part, can make the active energy ray-curable of composition abundant and excellent in adhesion, on the other hand, by making the ratio of (C) composition, be below 20 weight parts, can make the inside solidification of adhesive linkage good and make excellent in adhesion.
In addition, while using (C) composition, in order to improve the photolysis efficiency of (C) composition, also can be used together sensitizing agent, these also can be used as (C) composition and contain.
As sensitizing agent, can enumerate: anthracene compound, 4-methoxyl group-1-naphthols, fluorenes, pyrene and stilbene etc.
As anthracene compound, for example can enumerate anthracene, 9,10-dimethoxy anthracene, 9,10-diethoxy anthracene, 9,10-dipropoxy anthracene, 2-ethyl-9,10-dimethoxy anthracene, 2-ethyl-9,10-diethoxy anthracene, 2-ethyl-9,10-dipropoxy anthracene, 4 '-nitrobenzyl-9,10-dimethoxy anthracene-2-sulphonate, 4 '-nitrobenzyl-9,10-diethoxy anthracene-2-sulphonate and 4 '-nitrobenzyl-9,10-dipropoxy anthracene-2-sulphonate etc.
Wherein, the high viewpoint of sensibilized excellent from solvability composition, (C) composition considers, preferably 9, and 10-dimethoxy anthracene, 9,10-diethoxy anthracene and 9,10-dipropoxy anthracene.
As the commercially available product of these sensitizing agents, can enumerate: Anthracure UVS-1331,1221,1101, ET-2111[Kawasaki change into industry (strain) system].
The ratio of sensitizing agent, with respect to solidified nature composition total amount 100 weight parts, is preferably 0.1～10 weight part, more preferably 0.1～5 weight part.
In the situation that as large by the ultraviolet radiation absorption of the plastics of convered structure and use sulfonium salt as (C) composition, preferably and with anthracene compound as sensitizing agent.
4.(D) composition
(D) composition is optical free radical polymerization starter.Polymerization starter of the present invention, except above-mentioned (C) composition, also can contain this (D) composition as required.
(D) composition is for producing free radical by irradiating active energy beam, thereby causes as the compound of polymerization of (B) composition with the compound of ethylenically unsaturated group.In addition, different according to the kind of (D) composition, the sensitizing agent that also can be used as the photolysis of promotion (C) composition plays a role.
As the concrete example of (D) composition, can enumerate:
Benzyl dimethyl ketal, benzil, bitter almond oil camphor, bitter almond oil camphor ethyl ether, bitter almond oil camphor isopropyl ether, bitter almond oil camphor isobutyl ether, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-[4-(2-hydroxyl-oxethyl)-phenyl]-2-hydroxy-2-methyl-1-propane-1-ketone, oligomeric [2-hydroxy-2-methyl-1-[4-1-(methyl ethylene) phenyl] acetone, 2-hydroxyl-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl }-2-methylpropane-1-ketone, 2-methyl isophthalic acid-[4-(methylthio group)] phenyl]-2-morpholino propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butane-1-ketone, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholine-4-base-phenyl)-butane-1-ketone, Adeka Optomer N-1414(rising sun electrification system), phenyl dihydroxy acetic acid methyl esters, the aromatic ketone such as EAQ and phenanthrenequione compound,
Benzophenone, 2 methyl benzophenone, 3-methyldiphenyl ketone, 4-methyldiphenyl ketone, 2, 4, 6-tri-methyl benzophenone, 4-phenyl benzophenone, 4-(methylbenzene sulfenyl) phenyl methane, methyl-2-benzophenone, 1-[4-(4-benzoylphenyl alkylsulfonyl) phenyl]-2-methyl-2-(4-aminomethyl phenyl alkylsulfonyl) propane-1-ketone, 4, 4 '-bis-(dimethylamino) benzophenone, 4, 4 '-bis-(diethylin) benzophenone, N, N '-tetramethyl--4, 4 '-diaminobenzophenone, N, N '-tetraethyl--4, 4 '-diaminobenzophenone and 4-methoxyl group-4 '-benzophenone based compounds such as dimethylamino benzophenone,
Two (2,4,6-trimethylbenzoyl)-phenyl phosphine oxide, 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, ethyl-(2,4,6-trimethylbenzoyl) phenyl phosphonic acid esters and two (2,6-dimethoxy benzoyl)-2,4, the acylphosphine oxide compounds such as 4-tri-methyl-amyl phosphine oxide;
Thioxanthone, CTX, 2,4-diethyl thioxanthone, isopropyl thioxanthone, the chloro-4-propyl group of 1-thioxanthone, 3-[3,4-dimethyl-9-oxo-9H-thioxanthone-2-yl] oxygen base]-2-hydroxypropyl-N, N, the thioxanthone based compounds such as N-trimethyl ammonium chloride and fluorine thioxanthone;
The dihydroketoacridine based compounds such as dihydroketoacridine and 10-butyl-2-chloro-acridine ketone;
1, 2-acetyl caproyl 1-[4-(thiophenyl)-2-(o-benzoyl oxime)], ethyl ketone 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl] the oxime ester class such as-1-(O-ethanoyl oxime), 2-(Chloro-O-Phenyl)-4, 5-diphenyl-imidazole dipolymer, 2-(Chloro-O-Phenyl)-4, 5-bis-(m-methoxyphenyl) imidazole dimer, 2-(adjacent fluorophenyl)-4, 5-phenylimidazole dipolymer, 2-(o-methoxyphenyl)-4, 5-diphenyl-imidazole dipolymer, 2-(p-methoxyphenyl)-4, 5-diphenyl-imidazole dipolymer, 2, 4-bis-(p-methoxyphenyl)-5-phenylimidazole dipolymer and 2-(2, 4-Dimethoxyphenyl)-4, 5-diphenyl-imidazole dipolymer etc. 2, 4, 5-triarylimidazoles dipolymer, and
The acridine derivatives such as two (9, the 9 '-acridyl) heptane of 9-phenylacridine and 1,7-etc.
Wherein, the sensitization effect of (C) composition of thioxanthone based compound is high, therefore preferably.In thioxanthone based compound,, cured film painted few viewpoint excellent from active energy ray-curable consider, more preferably 2, and 4-diethyl thioxanthone and isopropyl thioxanthone.
As (D) composition, can use separately above-claimed cpd, or also can use two or more.
(D) ratio of composition, with respect to solidified nature composition total amount 100 weight parts, is preferably 0.1～10 weight part, more preferably 0.5～5 weight part.By making the ratio of (D) composition more than 0.1 weight part, the active energy ray-curable that can make composition fully and make excellent in adhesion, on the other hand, by making the ratio of (D) composition, be below 10 weight parts, can make the inside solidification of adhesive linkage good and excellent in adhesion.
5. other composition
And then, as the preferred component that can use in the present invention, can enumerate: the compound more than thering is 1 in molecule beyond (A) composition of cationically polymerizable group.As this compound, can enumerate: in molecule, have 1 above epoxy group(ing) and wherein at least 1 for ester ring type epoxy group(ing) is (at this, ester ring type epoxy group(ing) is illustrated in the ester ring type group that forms epoxide between 2 the adjacent carbon atoms that form ring) epoxy compounds (below, be called " alicyclic epoxy compound "), there are 2 above epoxy group(ing) in molecule and not containing above-mentioned " the alicyclic epoxy compound " of aromatic ring compound (being called " aliphatic epoxy compounds " below), oxetane compound, vinyl ether compound in addition.
Example as alicyclic epoxy compound, can enumerate: bicyclopentadiene dioxide, limonene dioxide, dioxidized 4-vinyl cyclohexene, 3,4-epoxycyclohexyl methyl (3,4-epoxy group(ing)) cyclohexane carboxylate, two (3,4-epoxycyclohexyl methyl) adipic acid ester, 3,4-epoxycyclohexyl methyl (methyl) acrylate etc.
In addition, in addition, also can enumerate: as document " epoxy resin-latest developments-" (clear rolling hall, nineteen ninety distribution) those compounds described in 7 pages, 18～20 pages of the 2nd chapter and document " Process Technology of Polymer " supplementary issue 9 the 22nd volume increasing number of the edition epoxy resin (meeting of polymer publication, clear and distribution in 48 years).
As the concrete example of aliphatic epoxy compounds, can enumerate: the aklylene glycol diglycidylethers such as ethylene glycol, propylene glycol, BDO and 1,6-hexylene glycol; The polyalkylene glycol such as polyoxyethylene glycol and polypropylene glycol diglycidyl ether diglycidylether; Neopentyl glycol, dibromoneopentyl glycol and oxyalkylene affixture diglycidylether thereof; The polyglycidyl ether of the polyvalent alcohols such as two, three or four glycidyl ethers of two or triglycidyl ether of trimethylolethane, TriMethylolPropane(TMP), glycerine and oxyalkylene affixture thereof and tetramethylolmethane and oxyalkylene affixture thereof; Two or polyglycidyl ether of Hydrogenated Bisphenol A and oxyalkylene affixture thereof; Tetrahydrophthalic acid diglycidylether; Quinhydrones diglycidylether etc.
In addition, also can enumerate: those compounds described in 3～6 pages of above-mentioned document " Process Technology of Polymer " supplementary issue epoxy resin.
As aliphatic epoxy compounds in addition, can enumerate: Denalex R-45EPT[Nagase ChemteX (strain) system], Epofriend AT501, CT310, more than Epolead PB3600[, Daicel chemical industry (strain) system], KL-630[Kuraray (strain) system], Tetrad C[Mitsubishi aerification length of schooling), TEPIC[daily output chemical industry (strain) system] etc.
Oxetane compound for having the compound of more than 1 trimethylene oxide ring in molecule.Specifically can enumerate: the various oxetane compounds of recording in Japanese kokai publication hei 8-85775 communique and Japanese kokai publication hei 8-134405 communique etc., wherein, preferably have the compound of one or more oxetanyls.As the example of simple function trimethylene oxide, can enumerate: 3-ethyl-3-(methylol) trimethylene oxide, 3-ethyl-3-[(phenoxy group) methyl] trimethylene oxide, 3-ethyl-3-(hexyloxy methyl) trimethylene oxide, 3-ethyl-3-(2-ethyl hexyl oxy methyl) trimethylene oxide, 3-ethyl-3-(chloromethyl) trimethylene oxide etc.As the example of two sense trimethylene oxide, can enumerate: Isosorbide-5-Nitrae-bis-[(3-ethyl-3-trimethylene oxide ylmethoxy) methyl] benzene, two { [1-ethyl (3-oxetanyl)] methyl } ether etc.
Vinyl ether compound is the compound in molecule with 1 above vinyl ether group.Specifically can enumerate: n-propyl vinyl ether, isopropyl-ethylene base ether, n-butyl vinyl ether, 2-hydroxyethyl vinyl ether, cyclohexanedimethanol mono vinyl ether, diglycol monotertiary vinyl ether, 4-hydroxy butyl vinyl ether, cyclohexyl vinyl ether, dodecyl vinyl, octadecyl vinyl ether, lauryl vinyl ether, cetyl vinylether, 2-ethylhexyl vinyl ether, the monofunctional vinyl ethers such as (methyl) vinylformic acid 2-(2-vinyloxy group oxyethyl group) ethyl ester, 1, 4-butyleneglycol divinyl ether, cyclohexanedimethanol divinyl ether, diethylene glycol divinyl ether, the polyfunctional vinyl ethers such as triethylene glycol divinyl ether.
As the compound beyond (A) composition of cationically polymerizable group more than thering is 1 in molecule, from improving cementability and fall low viscous viewpoint and consider, preferred low-molecular-weight compound, particularly, the compound of preferred molecular weight below 2,000.As more preferred example, can enumerate: limonene dioxide, 3,4-epoxycyclohexyl methyl (3,4-epoxy) cyclohexane carboxylate, 3-ethyl-3-(methylol) trimethylene oxide, 3-ethyl-3-[(phenoxy group) methyl] trimethylene oxide, two (3-ethyl-3-trimethylene oxide ylmethyl) ether.
In composition of the present invention, except above-mentioned, also can coordinate normally used other composition in binder composition.
Particularly, can coordinate: as inert fractions such as silane coupling agent, inorganic filler, tenderizer, antioxidant, antiaging agent, stablizer, tackifying resin, flow agent, defoamer, softening agent, organic solvent, dyestuff, pigment, treatment agent and UV blockers.As tackifying resin, such as enumerating: the rosin based such as sylvic acid, polymerized rosin acid and rosin ester, terpine resin, terpene phenolic resin, aromatic hydrocarbon resin, aliphatic saturated hydrocarbon resin and petroleum resin etc.
As silane coupling agent, can enumerate: 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyldiethoxysilane, 3-glycidoxy propyl-triethoxysilicane, 3-(methyl) acryloxy propyl group methyl dimethoxysilane, 3-methacryloxypropyl trimethoxy silane, 3-(methyl) acryloxy propyl group methyldiethoxysilane, 3-(methyl) acryloxy propyl-triethoxysilicane, N-2-(amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-2-(amino-ethyl)-3-TSL 8330, N-2-(amino-ethyl)-APTES, 3-TSL 8330, APTES, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene) propylamine, N-phenyl-3-TSL 8330, 3-sulfydryl propyl group methyl dimethoxysilane, 3-sulfydryl propyl trimethoxy silicane etc.Silane coupling agent can only be used a kind of above-claimed cpd, and also two or more kinds may be used.
6. plastics masking or sheet active energy ray curable binder composition
The present invention is for containing above-mentioned (A)～(C) plastics masking or sheet active energy ray curable binder composition of composition.
As the manufacture method of composition, can be by stirring according to conventional methods and mixing above-mentioned (A)～(C) composition and other one-tenth as required assigns to manufacture.
Now, also can heat as required.As Heating temperature, according to the suitable settings such as used composition, base material and object, preferably 30～80 ℃.
As the viscosity of composition, from the viewpoint of the screening characteristics excellence to base material, consider, preferably 10～1000mPas.
Composition of the present invention can be used for the bonding of bonding, the plastic film each other such as plastic film etc. and various base materials (following, to be called other base material) in addition.
Be explained, in the present invention, in the situation that being only expressed as " base material ", refer to the general name of plastic film etc. and other base material.
As other base material, can enumerate: paper and metal etc.
The using method of the present composition adopts ordinary method, as concrete example, can enumerate: be coated on base material afterwards and method etc. that another base material is fitted and irradiated active energy beam.
As the material of plastic film etc., such as enumerating polyvinyl chloride (PVC) RESINS, polyvinylidene dichloride, cellulose-based resin, polyethylene, polypropylene, polystyrene, ABS resin, polymeric amide, polyester, polycarbonate, urethane, polyvinyl alcohol, tri acetyl cellulose, cyclic olefin polymer, polymethylmethacrylate, vinylformic acid/styrene resin, vinyl-vinyl acetate copolymer and Chlorinated Polypropylene III etc.
As paper, can enumerate: wood-free writing paper, good quality paper, kraft paper, enamelled paper, cast-coated paper, glazed paper, parchment, wet-strong paper, glassine paper and fluting board etc.
As tinsel, such as enumerating aluminium foil etc.
The coating of base material is needed only according in the past known method, can enumerate: natural style coating machine (natural coater), cutter band coating machine (knife belt coater), floating cutter, roll-type knife coater, knife on blanket coater, spraying, dipping, roller are licked the methods such as formula coating machine, squeeze roll coater, reverse roll coater, air-blade type coating machine, curtain application device, comma roll coater, intaglio plate coating machine, miniature intaglio plate coating machine, mould painting machine and curtain coater.
In addition, the coating thickness of the present composition can be selected according to used base material and purposes, is preferably 0.1～100 μ m, more preferably 1～25 μ m.
As active energy beam, can enumerate: visible rays, ultraviolet ray, X ray and electron beam etc., in order to use cheap device, preferably ultraviolet ray.
Light source when by ultraviolet curing, can be used various light sources, such as enumerating pressurization or high voltage mercury lamp, metal halide lamp, xenon lamp, electrodeless discharge lamp, carbon arc lamp and LED etc.
By electrocuring in the situation that, as operable EB irradiating unit, can use various devices, such as enumerating Cockcroft-Walton accelerator type, model De Graff type and resonant transformer type device etc., as electron beam, the energy preferably with 50～1000eV, more preferably has the energy of 100～300eV.
Composition of the present invention is applicable to the bonding thin layer as base material by the situation of convered structure.
At bonding thin layer by convered structure in the situation that, the method that its using method adopts when manufacturing layered product conventionally.
For example can enumerate: composition is coated in to the first thin layer by convered structure and be dried as required, and second thin layer of then fitting is thereon by convered structure the method etc. of irradiating active energy beam.
As thin layer, by convered structure, can enumerate: the paper such as plastic film or tinsel etc.
Plastic films etc. need to see through the film of active energy beam, as thickness, according to used thin layer, by convered structure and purposes, are selected, and preferred thickness is below 0.2mm.
Composition of the present invention these thin layers by convered structure in, be preferred for each other bonding such as plastic film, can further be preferred for wetting ability plastics, be specifically used for polyvinyl alcohol or tri acetyl cellulose system by convered structure.
In addition, bonding by convered structure before, in order to increase interlayer adhesion, can carry out activation treatment to the surface of one or both.As surface activation process, can enumerate: Cement Composite Treated by Plasma, Corona discharge Treatment, liquid processing, roughened processing and etch processes, flame treating etc., also can and use them.
To thin layer by the coating of convered structure according to known method in the past, can enumerate and above-mentioned same method.
In addition, the coating thickness of the present composition is selected by convered structure and purposes according to used thin layer, preferably coating thickness same as described above.
In addition, in this case, be not limited to flat state, also can under curved surface state, carry out bonding.
That is, can enumerate: base material is bent into concavity or convex, under this state after coating composition, the method for fitting another base material and irradiating active energy beam.
As other method, can enumerate: on base material is under flat state, apply composition of the present invention, another base material of fitting, is bent into concavity or convex and irradiates active energy beam and carry out bonding method again.
In this case, as the method for coating composition under flat state, according to aforesaid method.As the method for coating composition under curved surface state, can enumerate: the method for using spraying, dipping, curtain application device, silk screen printing and slit coater etc.
By above method, manufacture duplexer that the cured article/plastic film by plastic film/present composition forms, by the duplexer that cured article/other base material forms of plastic film/present composition.
The bounding force of the duplexers such as the laminated film being obtained by the present composition under high temperature and super-humid conditions is excellent, therefore, can be preferred for the bloomings such as the middle polaroids that use such as liquid crystal indicator and protective membrane, phase retardation film.
Composition of the present invention can be particularly preferred for polaroid and with the manufacture of the polaroid of phase retardation film.Below, the manufacture method of polaroid is described.
Be explained, in this manual, polaroid represents to have film or the film of polarisation function described later, polaroid refer to film or film protection polarization element one-sided or both sides, with the polarization element of protective layer.In addition, with the polaroid of phase retardation film, refer to and on polarization element or polaroid, fit phase retardation film or by coating, form the film with phase difference function.
As mentioned above, composition of the present invention can be preferred for the bonding of wetting ability plastics, and in the manufacture of polaroid, the polyvinyl alcohol using as polarization element, the tri acetyl cellulose using as the protective membrane of polarization element are equivalent to wetting ability plastics.
Composition of the present invention can be used for the bonding of the bonding or polaroid of polarization element and protective membrane and phase retardation film.
Polarization element refers to have optionally the element seeing through from the function of the linear polarisation of a direction of natural light.
As the concrete example of polarization element, can enumerate: the iodine polarizing element that adsorbs iodine and be orientated on polyvinyl alcohol mesentery, on polyvinyl alcohol mesentery, adsorb dichroic dye and the dyestuff that is orientated be polarization element, on polyvinyl alcohol mesentery coating (lyotropic) mesomorphic state pigment and be orientated, immobilized application type polarization element etc.
These iodine polarizing elements, dyestuff are that polarization element, application type polarization element have optionally and to see through from the linear polarisation of a direction of natural light and to absorb the element of function of the linear polarisation of other direction, are called as absorption-type polarization element.
At above-mentioned iodine polarizing element and dyestuff, be in polarization element, conventionally at its single or double, protective layer be set, composition of the present invention can be used for the bonding of polarization element and protective membrane.
As the protective membrane using in protective layer, such as enumerating: the cyclic polyolefin resin film that the cellulose acetate resin molding as tri acetyl cellulose or diacetyl cellulose, acrylic resin film, polyester resin film, polyarylate resin film, polyethersulfone resin membrane, the such cyclic olefin of the norbornylene of take are monomer etc.
What in addition, composition of the present invention also can be for polaroid and phase retardation film is bonding.
In this case, as polaroid, can use the polaroid at its single or double with protective layer.
In this case, as protective layer, can, for being fitted with the protective layer of said protection film, can be also the protective membrane forming by coating.
At one side, only arrange protective layer polaroid with the mutually bonding face of phase retardation film can be for thering is the face of protective layer, also can be for not thering is the face of protective layer.
As phase retardation film, can use various phase retardation films, can enumerate: implemented the optical film of single shaft or the processing such as biaxial stretch-formed or on base material coating fluid crystallinity compound etc. the optical film etc. that carried out orientation, immobilized processing, it controls the magnitude relationship (index ellipsoid) of three-dimensional refractive index according to working conditions.Be mainly used in the variation of the phase differential that the painted compensation causing by the liquid crystal layer by liquid-crystal display and compensation cause by visual angle.
If enumerate the concrete example of phase retardation film, as the starting material that implement to stretch wait the blooming of processing, can illustration: the polyolefine as polyethylene, polypropylene, cyclic polyolefin or polycarbonate, polyvinyl alcohol, polystyrene, polymethylmethacrylate, polyarylester compound and polymeric amide etc.
The general general designation that above-mentioned cyclic polyolefin is the resin that obtained by norbornylene, tetracyclododecane or their cyclic olefins such as derivative, such as enumerating: the cyclic polyolefin of recording in Japanese kokai publication hei 3-14882 communique, Japanese kokai publication hei 3-122137 communique etc.
Particularly, can illustration: the random copolymers of the alpha-olefins such as the ring-opening polymerization polymer of cyclic olefin, the addition polymer of cyclic olefin, cyclic olefin and ethene, propylene and the graft modification thing that they are formed with modifications such as unsaturated carboxylic acid or derivatives thereofs etc.And then, can enumerate their hydride.As commodity, can enumerate: Arton, the Topas of Ticona company system etc. of Zeonex, the Zeonor of Japanese auspicious father-in-law (strain) system, JSR (strain) system.
In addition, as coating fluid crystallinity compound on base material etc. the optical film that carried out orientation, immobilized processing, can enumerate: " WV film " [Fujiphoto (strain) system], " LC film ", " NH film " [being the JX day ore deposit day stone energy (strain) system] etc.
Below, illustrate and use the present composition to manufacture polaroid or with the method for the polaroid of phase retardation film.
As this manufacture method, can enumerate the method that comprises following operation [1]～[3].
Operation [1], is coated in the present composition as by any one in the polarization element of convered structure, polaroid, protective film, protective membrane, phase-contrast film, phase retardation film;
Operation [2], on the film that has applied above-mentioned composition laminating as another by any one in the polarization element of convered structure, polaroid, protective film, protective membrane, phase-contrast film, phase retardation film;
Operation [3], after laminating film, irradiates active energy beam across the base material that is coated with the present composition.
The in the situation that of one-sided laminating protective membrane only or phase retardation film; can manufacture polaroid or with the polaroid of phase retardation film by said sequence; the in the situation that of laminating in both sides; can after repeating 2 operations [1] and [2], implement operation [3], also can repeat 2 operations [1], [2] and [3].
Active energy beam illuminating method in coating method in above-mentioned operation [1], above-mentioned operation [3] by with above-mentioned same method.
In addition, also can under curved surface state, carry out as described above bonding.
In the situation that use with the polaroid of phase retardation film as rotatory polarization sheet, in order to realize circularly polarized light state in broad band region, also can be at the phase retardation film side of the polaroid with the phase retardation film different phase retardation film of phase differential of further fitting.
Particularly, there is following method: laminating has the phase retardation film of 1/2 wavelength with respect to each wavelength on polarization element film, then fits and with respect to each wavelength, have the phase retardation film of 1/4 wavelength.In this case, can after repeating 3 operations [1] and [2], implement operation [3], also can repeat 3 operations [1], [2] and [3].
Embodiment
Below, enumerate embodiment and comparative example is described more specifically the present invention.Be explained, below " part " in each example refer to weight part.
(Production Example 1 of polarization element)
Iodine 0.05 mass parts, potassiumiodide 0.5 mass parts are dissolved in the water of 100 mass parts, prepare staining fluid.This staining fluid is heated to 55 ℃, PVA film ((strain) Kuraray polyvinyl film processed VF-PS, 75 μ m) was flooded after 1 minute, film is stretched to 6 times along 1 direction.And then, make boric acid 4 mass parts, potassiumiodide 6 mass parts be dissolved in the water of 90 mass parts in and then cleaning after dyeing in the aqueous solution that obtains, makes it dry, make the polarization element of thickness 30 μ m.
(Production Example 1 of polaroid)
In adding of thickness 80 μ m, there is the tri acetyl cellulose of UV absorption agent film [trade(brand)name FUJITAC; Fujiphoto (strain) system; hereinafter referred to as " UVA-TAC "] upper corona treatment (the Navitas Port リ processed ダ イ Application 1 of implementing as easy bonding processing; output rating 0.1kW, 1 second/cm of processing speed).
Then on the polarizer that, uses excellent painting machine to obtain, be coated with the active energy ray curable binder composition that 5 μ m are thick in Production Example 1.Lamination has been implemented the UVA-TAC of corona treatment thereon, then turns over, and similarly carries out the coating of active energy ray curable binder composition and has implemented the lamination of the UVA-TAC of corona treatment.Then, using the metal halide lamp his-and-hers watches back side of 80W/cm light-focusing type respectively to irradiate once ultraviolet ray solidifies it.Then, at room temperature maintain 12 hours, the TAC manufacturing as test body is polaroid.Uitraviolet intensity is 250mW/cm
2, accumulative total light quantity is 300mJ/cm
2(being the value at 365nm place).
(Production Example 2 of polaroid)
The tri acetyl cellulose film that does not add UV absorption agent of used thickness 100 μ m [LOFO system, hereinafter referred to as " TAC "] replaces UVA-TAC, in addition, similarly makes polaroid with the Production Example 1 of polaroid.
Zero embodiment 1～embodiment 7, comparative example 1～comparative example 7
Within 1 hour, make it dissolve (A) shown in following table 1～(D) composition and other composition heated and stirred at 60 ℃, manufacture active energy ray curable binder composition.
Numeral umber in table 1.In addition, the abbreviation in table 1 is as described below.
1) (A) composition
JER828: bisphenol A diglycidyl ether, japan epoxy resin (strain) jER-828(trade(brand)name processed)
2) (B1) composition
4HBA: vinylformic acid 4-hydroxyl butyl ester, Osaka organic chemistry industry (strain) Viscoat4-HBA(trade(brand)name processed)
2HBA: vinylformic acid 2-hydroxyl butyl ester, chemistry (strain) the Light Acrylate processed HOB-A(of common prosperity society trade(brand)name)
3) (B2) composition
M270: polypropylene glycol (n 12) diacrylate, (strain) Aronix M-270(processed trade(brand)name is synthesized in East Asia)
M313: tricarbimide EO modification two/triacrylate, (strain) Aronix M-313(processed trade(brand)name is synthesized in East Asia)
4) other (B) composition
PEA: vinylformic acid phenoxy ethyl, chemistry (strain) the Light Acrylate processed PO-A(of common prosperity society trade(brand)name)
THFA: vinylformic acid tetrahydro furfuryl ester, Osaka organic chemistry industry (strain) Viscoat#150(trade(brand)name processed)
HEA: vinylformic acid 2-hydroxy methacrylate, (strain) ア Network processed リ ッ Network ス HEA(trade(brand)name is synthesized in East Asia)
HPA: vinylformic acid 2-hydroxy propyl ester, chemistry (strain) the Light Ester processed HOP-A(of common prosperity society trade(brand)name)
M5700: vinylformic acid 2-hydroxyl-3-phenoxy group propyl ester, (strain) Aronix M-5700(processed trade(brand)name is synthesized in East Asia)
5) (C) composition
Irg: iodine
salt is light cationic initiator, BASF JAPAN Irgacure250(trade(brand)name processed)
CPI: sulfonium salt is the polypropylene carbonate ester solution of 50 % by weight of light cationic initiator, San-Apro CPI-100P(trade(brand)name processed)
DBA:9,10-dibutoxy anthracene, Kawasaki changes into Anthracure UVS-1331(trade(brand)name processed)
6) (D) composition
DETX:2,4-diethyl thioxanthone, Japanese chemical drug (strain) DETX-S(trade(brand)name processed)
7) other composition
CEL2021:3,4-oxirane ring hexenyl methyl-3 ', 4 '-oxirane ring hexene carboxylicesters, Daicel chemical industry (strain) Celloxide2021P(trade(brand)name processed)
YX: Hydrogenated Bisphenol A diglycidylether, japan epoxy resin (strain) YX-8000(trade(brand)name processed)
evaluate
According to following test method, evaluate resulting composition.These be the results are shown in to table 2.
(25 ℃ of viscosity)
Use the viscosity of the active energy ray curable binder composition at 25 ℃ of E type viscometer determinings.When using coating machine to carry out thin film cladding, more low better the viscosity of 25 ℃, therefore by following standard, judge.
Zero: lower than 100mPas, △: 100～200mPas, *: surpass 200mPas
(stripping strength)
Test consideration Production Example by above-mentioned polaroid 1 or 2 being obtained via double sticky tape is attached on glass, measures under the following conditions the stripping strength of UVA-TAC or TAC and polaroid.
Tensile testing machine: InstronJapan Co., ltd Instron5564 processed
Test film: 25mm * 100mm
Test method: peel off for 90 °
Peeling rate: 200mm/min
(humidity resistance)
The test body that Production Example by above-mentioned polaroid 1 or 2 is obtained is placed 500～1000 hours in the controlled thermohygrostat of 60 ℃/90%RH, observes appearance change.
Zero: without decolouring
△: find part decolouring
*: decolouring substantially completely
(film warpage)
The test body obtaining in the Production Example 1 or 2 of above-mentioned polaroid is cut into width 50mm * length 100mm, uses Cellotape(registered trademark) be attached on the test tube of 3 inches.Then, at room temperature place after 24 hours, take off film, be placed in the outward appearance of observing film in horizontal table top.With scale, measure the depth of camber of 4 jiaos of ends of film, measure its mean value.The smaller the better.
Zero: the fluctuating height of film end is lower than 1cm
*: the fluctuating of film end is highly more than 1cm
[table 2]
As shown in Table 2, the outward appearance after the viscosity of the present composition low and stripping strength and high wet test is excellent, and the film warpage that the dark reaction after UV solidifies causes is also suppressed.
In contrast to this, not containing the composition (comparative example 1～4) of (B1) of the present invention composition, all not insufficient containing outward appearance, film warpage after the composition (comparative example 5) of (B2) of the present invention composition, the viscosity that does not contain the composition (comparative example 6～7) of (A) of the present invention composition, stripping strength, high wet test.
Industrial applicability
Composition of the present invention can be used as the tackiness agent of tackiness agent, particularly the wetting ability plastics etc. of various plastic films etc., can be particularly preferred for the manufacture of manufacture, particularly polaroid of the blooming of liquid crystal indicator etc.
Claims (12)
1. a plastics masking or sheet active energy ray curable binder composition, it at least consists of solidified nature composition and polymerization starter, described solidified nature composition at least consists of following (A) composition and following (B) composition, and described polymerization starter at least consists of following (C) composition
(A) composition: molecule contains the aromatic ring oxygen compound of 2 above epoxy group(ing);
(B) composition: at least there are by being selected from the alefinically unsaturated compounds that the compound (B2) of 2 above ethylenically unsaturated groups forms at least a kind of compound (B1) of vinylformic acid 4-hydroxyl butyl ester and vinylformic acid 2-hydroxyl butyl ester and molecule;
(C) composition: light cationic polymerization initiators.
2. plastics masking claimed in claim 1 or sheet active energy ray curable binder composition, wherein, described (A) composition is bisphenol-type epoxy resin.
3. the plastics masking described in claim 1 or 2 or sheet active energy ray curable binder composition, wherein, in solidified nature composition total amount 100 % by weight, with the ratio of 10～80 % by weight, contain (A) composition and contain (B) composition with the ratio of 20～90 % by weight
With respect to solidified nature composition total amount 100 weight parts, with the ratio of 0.1～20 weight part, contain (C) composition.
4. the plastics masking described in claim 1～3 any one or sheet active energy ray curable binder composition, wherein, in solidified nature composition total amount 100 % by weight, with the ratio of 10～50 % by weight, contain (B1) composition and contain (B2) composition with the ratio of 0.5～40 % by weight.
5. the plastics masking described in claim 1～4 any one or sheet active energy ray curable binder composition, wherein, described polymerization starter also contains (D) optical free radical polymerization starter.
6. plastics masking claimed in claim 5 or sheet active energy ray curable binder composition, wherein, with respect to solidified nature composition total amount 100 weight parts, contain (D) composition with the ratio of 0.1～10 weight part.
7. the plastics masking described in claim 1～6 any one or sheet active energy ray curable binder composition, wherein, described (B) composition also comprises the compound with aromatic ring frame or ester ring type skeleton, and described aromatic ring frame or ester ring type skeleton contain 1 ethylenically unsaturated group at molecule.
8. the polaroid manufacture binder composition described in claim 1～7 any one, wherein, plastics masking or sheet are wetting ability plastics masking or sheet.
9. polaroid manufacture binder composition claimed in claim 8, wherein, wetting ability plastics masking or sheet are polyethenol series polarization element film.
10. a duplexer, it is to stack gradually the cured article layer of the composition described in base material, claim 1～7 any one and plastics masking or sheet to form.
11. duplexers claimed in claim 10, wherein, described base material is plastics masking or sheet.
12. 1 kinds of polaroids, it is to stack gradually the cured article layer of the composition described in polyethenol series polarization element film or sheet, claim 1～7 any one and plastics masking or sheet to form.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP2011-130756 | 2011-06-11 | ||
| JP2011130756 | 2011-06-11 | ||
| PCT/JP2012/064787 WO2012173055A1 (en) | 2011-06-11 | 2012-06-08 | Active-energy-ray-curable adhesive composition for plastic film or sheet |
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| Country | Link |
|---|---|
| JP (1) | JP5978505B2 (en) |
| KR (1) | KR101989420B1 (en) |
| CN (1) | CN103597049A (en) |
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| WO (1) | WO2012173055A1 (en) |
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| CN107849420A (en) * | 2015-07-29 | 2018-03-27 | 东亚合成株式会社 | Plastics are film-made or piece active energy ray curable adhesive compound |
| CN108884363A (en) * | 2016-04-04 | 2018-11-23 | 德莎欧洲股份公司 | The pressure sensitive adhesive tape of radiation activatable and application thereof with dark reaction |
| CN111073522A (en) * | 2019-12-04 | 2020-04-28 | 络合高新材料(上海)有限公司 | Special epoxy adhesive for bonding UV (ultraviolet) photocuring PVC (polyvinyl chloride) base materials |
| CN112574649A (en) * | 2019-09-29 | 2021-03-30 | 常州格林感光新材料有限公司 | Cationically curable compositions for plastic substrates, coatings, plastic articles and applications |
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| JPWO2014178239A1 (en) * | 2013-05-02 | 2017-02-23 | Dic株式会社 | Adhesive composition and polarizing plate |
| JP6260143B2 (en) * | 2013-08-23 | 2018-01-17 | 東洋インキＳｃホールディングス株式会社 | Active energy ray polymerizable resin composition and laminate |
| JP6493900B2 (en) * | 2013-08-09 | 2019-04-03 | デクセリアルズ株式会社 | Transparent laminate and protective equipment using the same |
| TW201602285A (en) * | 2014-06-20 | 2016-01-16 | Toagosei Co Ltd | Activation energy beam-curable adhesive composition for plastic film or sheet |
| KR101724616B1 (en) | 2014-09-18 | 2017-04-07 | 주식회사 엘지화학 | Curable composition used instead of glass |
| JP6097815B1 (en) * | 2015-12-18 | 2017-03-15 | 古河電気工業株式会社 | Adhesive composition, adherend bonding method using the same, and laminate manufacturing method |
| US20190168493A1 (en) * | 2016-06-27 | 2019-06-06 | Kuraray Co., Ltd. | Molded body comprising acrylic resin composition |
| DE102017001696A1 (en) | 2017-02-22 | 2018-08-23 | Lohmann Gmbh & Co. Kg | UV-activated structural pressure-sensitive adhesive tape |
| WO2019177134A1 (en) * | 2018-03-15 | 2019-09-19 | 東亞合成株式会社 | Active energy ray-curable adhesive composition for plastic films and sheets, laminate, and polarizing plate |
| JP7373303B2 (en) * | 2018-09-28 | 2023-11-02 | 住友化学株式会社 | Optical laminates, polarizing plate composites, and image display devices |
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| CN107849420A (en) * | 2015-07-29 | 2018-03-27 | 东亚合成株式会社 | Plastics are film-made or piece active energy ray curable adhesive compound |
| CN108884363A (en) * | 2016-04-04 | 2018-11-23 | 德莎欧洲股份公司 | The pressure sensitive adhesive tape of radiation activatable and application thereof with dark reaction |
| CN112574649A (en) * | 2019-09-29 | 2021-03-30 | 常州格林感光新材料有限公司 | Cationically curable compositions for plastic substrates, coatings, plastic articles and applications |
| CN112574649B (en) * | 2019-09-29 | 2022-06-17 | 常州格林感光新材料有限公司 | Cationically curable compositions for plastic substrates, coatings, plastic articles and applications |
| CN111073522A (en) * | 2019-12-04 | 2020-04-28 | 络合高新材料(上海)有限公司 | Special epoxy adhesive for bonding UV (ultraviolet) photocuring PVC (polyvinyl chloride) base materials |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201249949A (en) | 2012-12-16 |
| WO2012173055A1 (en) | 2012-12-20 |
| JP5978505B2 (en) | 2016-08-24 |
| TWI537357B (en) | 2016-06-11 |
| KR20140031244A (en) | 2014-03-12 |
| KR101989420B1 (en) | 2019-06-14 |
| JPWO2012173055A1 (en) | 2015-02-23 |
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Application publication date: 20140219 |