CN104419331A - Photocurable adhesive composition, polarizer and manufacturing method thereof, optical member, and liquid crystal display device - Google Patents

Photocurable adhesive composition, polarizer and manufacturing method thereof, optical member, and liquid crystal display device Download PDF

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Publication number
CN104419331A
CN104419331A CN201410419587.XA CN201410419587A CN104419331A CN 104419331 A CN104419331 A CN 104419331A CN 201410419587 A CN201410419587 A CN 201410419587A CN 104419331 A CN104419331 A CN 104419331A
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China
Prior art keywords
composition
weight
methyl
photocurable adhesive
polaroid
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CN201410419587.XA
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Chinese (zh)
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CN104419331B (en
Inventor
浅津悠司
稻田和正
浅野洋一
佐内康之
冈崎荣一
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Toagosei Co Ltd
Sumitomo Chemical Co Ltd
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Toagosei Co Ltd
Sumitomo Chemical Co Ltd
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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
    • 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
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • 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
    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • C09J171/02—Polyalkylene oxides
    • 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
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • 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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors

Abstract

The invention provides a photocurable adhesive composition, a polarizer and a manufacturing method thereof, an optical member, and a liquid crystal display device. The photocurable adhesive can demonstrate the adhesive capability immediately after light irradiation even though a resin thin film with low moisture permeability is configured to be a protective film, after a certain period of time, the adhesive capability is good compared with other capabilities, and has no other problems after the endurance experiment. The adhesive capability is good after being subjected to the damp and hot resistance test and the adhesiveness is low. The photocurable adhesive, at a specific proportion, includes (A) polyhydric alcohol poly(methyl)acrylate having 2-15 carbon atoms, (B) polyhydric alcohol polyglycidyl ether having 2-10 carbon atoms, (C) an oxetane composition in a specified structure, (D) a (methyl) acrylic polymer, and (E) a cationic photoinitiator.

Description

Photocurable adhesive agent composition, Polarizer and manufacture method thereof, optical component and liquid crystal indicator
Technical field
The present invention relates to the Photocurable adhesive agent composition for the polaroid in Polarizer and protective membrane being fitted, using this adhesive composite that protective membrane is fitted in polaroid and the manufacture method of the Polarizer obtained and this Polarizer.The present invention also relates to the optical component and liquid crystal indicator that employ this Polarizer in addition.
Background technology
Polarizer can be used as one of optics forming liquid crystal indicator.Polarizer normally under the state on two sides protective membrane being laminated in polaroid group enter in liquid crystal indicator use.Also be known to the situation that protective membrane is only set at the one side of polaroid, but in most instances, be not only set to protective membrane on the other surface, but the layer other with optical function doubles as protective membrane and fits.In addition, as the manufacture method of polaroid, likewise known has following method: the uniaxial extension polyvinyl alcohol resin film dyeed by dichroism pigment is carried out boric acid process, washes, then dry.
Usually, after above-mentioned washing and drying, protective membrane of fitting on polaroid immediately.This is because the physical property intensity of dried polaroid is weak, once be batched, then produce in problems such as machine direction split.Therefore, for dried polaroid, be usually coated with the caking agent of water system immediately, then side by side fitted on two sides protective membrane by this caking agent.As protective membrane, usually use the triacetylcellulose film of thickness 30 ~ 120 μm.
By polaroid and protective membrane, particularly carry out bonding with the protective membrane formed by triacetylcellulose film time, mostly use the caking agent of polyvinyl alcohol, but also someone attempts replacing it and using polyurethanes caking agent.Such as; following content is described: carbamate prepolymer is set to caking agent in Japanese Unexamined Patent Publication 7-120617 publication (patent documentation 1); by polaroid high for water ratio and rhodia class protective membrane, such as triacetylcellulose film is bonding.
On the other hand, the Water Vapour Permeability of triacetyl cellulose is high, and the Polarizer thus obtained as protective membrane by this resin film of laminating has following problem: under damp and hot, such as, under the condition of temperature 70 C, relative humidity 90%, cause deterioration etc.Therefore also proposed by resin film lower than triacetylcellulose film for Water Vapour Permeability is set to protective membrane, thus solve the method for associated problem, such as known noncrystalline polyolefin resinoid is set to protective membrane.Specifically, as protective membrane at least one face thermoplasticity saturated norbornene resin sheet material being laminated in polaroid, this content is recorded in Japanese Unexamined Patent Publication 6-51117 publication (patent documentation 2).
When using device in the past to be fitted by protective membrane low for such Water Vapour Permeability; use take water as the caking agent such as polyvinyl alcohol water solution of primary solvent; protective membrane is fitted in the polaroid of polyvinyl alcohol; then by solvent seasoning; so-called wet type lamination like this has and cannot obtain sufficient bonding strength, or outward appearance becomes the problems such as bad.This be due to the low film of Water Vapour Permeability generally than the hydrophobicity of triacetylcellulose film and/or Water Vapour Permeability low, thus cannot using fully dry etc. as the water of solvent.
Therefore, in Japanese Unexamined Patent Publication 2000-321432 publication (patent documentation 3), following content is proposed: utilize polyurethanes caking agent to carry out bonding by the polaroid of polyvinyl alcohol with the protective membrane formed by thermoplasticity saturated norbornene resinoid.But polyurethanes caking agent has needs problem for a long time in solidification, and bonding force also may not be sufficient in addition.
On the other hand, also there will be a known different types of protective membrane of fitting on the two sides of polaroid, such as, following content is proposed: the protective membrane formed by noncrystalline polyolefin resinoid of fitting on a face of the polaroid formed by polyvinyl alcohol resin film in Japanese Unexamined Patent Publication 2002-174729 publication (patent documentation 4), fit by the resin different from this noncrystalline polyolefin resinoid on the other surface, the protective membrane that such as triacetyl cellulose is formed; Following content is proposed: on a face of the polarizing film formed by polyvinyl alcohol resin in Japanese Unexamined Patent Publication 2005-208456 publication (patent documentation 5), by comprising the first caking agent of the water system of specific carbamate resins and stacked ring olefine kind resin film, on the other surface by the second caking agent of the water system different from the first caking agent, the aqueous solution of such as polyvinyl alcohol resin and stacked rhodia based resin film.
In above-mentioned patent documentation 4, be called as noncrystalline polyolefin resinoid, in addition in above-mentioned patent documentation 5, be called as the resinoid material of cycloolefin and be: the unit with the monomer formed by the polycycle cycloolefin that norbornylene and/or its derivative, dimethano-octahydro naphthalene are such, and when as ring-opening polymerization polymer when residual double bond, preferably carry out hydrogenation wherein and the thermoplastic resin that obtains.
In addition; disclose a kind of with the caking agent of epoxy resin for main component not comprising aromatic nucleus in Japanese Unexamined Patent Publication 2004-245925 publication (patent documentation 6); propose following method: carry out cationoid polymerisation by irradiating active energy ray to this caking agent, thus polaroid is bonding with protective membrane.The caking agent of epoxies disclosed herein is effective especially for being fitted in by the various transparent resin films being representative with noncrystalline polyolefin resinoid and cellulosic resin for polaroid; but when particularly acrylic resin being set to protective membrane, obviously this bonding force known may not be sufficient.
Therefore; when resin film low for the Water Vapour Permeability selected from acrylic resin, vibrin, polycarbonate resin and noncrystalline polyolefin resinoid is set to the protective membrane of polaroid by the present inventor, carry out the exploitation of the low viscous Photocurable adhesive agent manifesting good bonding force in the operation of short period of time.Found that as follows: the composition comprising the glycidyl ether type epoxy resin and oxetane compound with aromatic nucleus produces good bonding force, particularly when containing 5 ~ 25 % by weight there is (methyl) acrylic ester monomer of alicyclic skeleton, show high bonding force and weather resistance (patent documentation 7).But this caking agent has following problem: although the operation of production process short period of time of utilizing rayed such itself, if without for some time after film batches, just do not manifest sufficient bonding force.Thus, the problem of carrying out film process is not easy after having the rayed in production process.
The present inventor has carried out various research to solve aforementioned problems, found that as follows: the Photocurable adhesive agent composition comprising cycloaliphatic epoxy, specific many (methyl) acrylate, Cationic photoinitiator and trimethylene oxide alcohol is effective (patent documentation 8).
This adhesive composite is the Polarizer Photocurable adhesive agent that a kind of not only bonding force and excellent in te pins of durability but also productivity are also excellent.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 7-120617 publication
Patent documentation 2: Japanese Unexamined Patent Publication 6-51117 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2000-321432 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2002-174729 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2005-208456 publication
Patent documentation 6: Japanese Unexamined Patent Publication 2004-245925 publication
Patent documentation 7: Japanese Unexamined Patent Publication 2010-209126 publication
Patent documentation 8: Japanese Unexamined Patent Publication 2012-140610 publication
Summary of the invention
The problem solved is wanted in invention
Distinguish following content: in the caking agent of aforesaid patent documentation 8; when the protective membrane of acrylic resin is bonding with polaroid; under hot and humid environment, (such as 60 DEG C 90%) implements hot resistance test; then turn back to usual environment (such as 23 DEG C 50%), the peeling adhesion force just turned back to after usual environment is quite low.
Reduce about this bonding force, place at usual environment 15 constantly little, then when the protective membrane peeling off acrylic resin, the degree that protective membrane destroys with generating material and recover peeling adhesion force.In addition, even after hot resistance test just terminates, under the effect of the power (power of shear direction or vertical direction) applied with goods form Polarizer being attached at glass, also do not cause the stripping of protective membrane.But, imagine and be exposed to hot and humid environment in Polarizer conveying, when then entering the such worst case of manufacturing procedure immediately, then expect the stripping strength improved further after hot resistance test has just terminated.
Further; when acrylic resin protective membrane is bonding with polaroid; in the stripping test that acrylic resin bends by plate polaroid being attached to glass etc. or by the T-shaped stripping test of both film bends; show good bonding force; but by stripping test bending for polaroid on plate acrylic resin being attached to glass etc., have the problem that bonding force significantly diminishes.Thus, in the manufacturing procedure etc. of Polarizer, when applying polaroid to bend such stronger power in end, then sometimes peel off.For the object preventing such problem, people require to develop acrylic resin is being fixed on plate, and by stripping test bending for polaroid, also show the caking agent of good bonding power.
The present invention wants the problem solved to be to provide a kind of Photocurable adhesive agent; even if it is when being set to protective membrane by resin film low for the Water Vapour Permeability selected in by vibrin, polycarbonate resin, acrylic resin and noncrystalline polyolefin resinoid; bonding force is manifested immediately after rayed; final bonding force after certain hour is also good; and also can not the problems such as bad order be caused after long duration test; bonding force after hot resistance test terminates is also good, and the viscosity before solidification is low.A kind of caking agent is provided further, even if it is by bonding with polaroid for acrylic resin protective membrane, acrylic resin protective membrane is pasted onboard, applies the such power bent by polaroid, also show excellent bonding force.
Another object of the present invention is to provide a kind of optical component, and it by employing the Polarizer of this caking agent, thus forms liquid crystal indicator excellent in reliability, and another object is to be applicable to liquid crystal indicator further.
For the scheme of dealing with problems
Namely; the invention provides a kind of Photocurable adhesive agent composition; it is the adhesive composite for protective membrane being adhered to polaroid; described protective membrane is formed by the transparent resin film selected in the group formed from vibrin, polycarbonate resin, acrylic resin and noncrystalline polyolefin resinoid; described polaroid, by having carried out uniaxial extension and polyvinyl alcohol resin film dichroism pigment having been carried out gas absorption quantity is formed, is characterized in that containing:
(A) have many (methyl) acrylate of the polyvalent alcohol of 2 ~ 15 carbon atoms,
(B) have many glycidyl ethers of the polyvalent alcohol (but, except the polyether glycol of the repeat number more than 3 of alkylene oxide unit) of 2 ~ 10 carbon atoms,
(C) oxetane compound shown in following formula (1),
(D) with alkyl (methyl) acrylate be required structures alone unit polymkeric substance,
(E) Cationic photoinitiator,
Described (A) ~ (E) composition in the composition containing proportional be:
(A) composition: 15 ~ 50 % by weight
(B) composition: 2 ~ 35 % by weight
(C) composition: 2 ~ 50 % by weight
(D) composition: 1 ~ 30 % by weight
(E) composition: 0.5 ~ 10 % by weight.
As (A) composition, preferably there is two (methyl) acrylate of the glycol of 2 ~ 10 carbon atoms.In addition, as (methyl) acrylate, acrylate is more preferably.
As (B) composition, preferably there is the diglycidyl ether of the glycol (but, except the polyether glycol of the repeat number more than 3 of alkylene oxide unit) of 2 ~ 10 carbon atoms.
(A) composition, (B) composition, (C) composition, (D) composition and (E) composition in the composition be preferably respectively 20 ~ 45 % by weight, 5 ~ 30 % by weight, 5 ~ 35 % by weight, 5 ~ 25 % by weight and 1 ~ 6 % by weight containing proportional.
As (D) composition, preferably comprise a kind of polymkeric substance, this polymkeric substance comprises (methyl) alkyl acrylate of the alkyl containing carbonatoms 1 ~ 10 as structures alone unit, and weight-average molecular weight is 1,000 ~ 500,000.
As this polymkeric substance, be preferably: comprise the methyl methacrylate of more than 60 % by weight as (D1) structures alone unit, and weight-average molecular weight is 1,000 ~ 200, the polymkeric substance of 000 is [following, also referred to as " (D1) composition "], and the alkyl acrylate of alkyl containing carbonatoms 1 ~ 10 comprising more than 60 % by weight is as (D2) structures alone unit, and weight-average molecular weight is 1,000 ~ 200, the polymkeric substance [hereinafter also referred to as " (D2) composition "] of 000.
As (D2) composition, more preferably a kind of polymkeric substance, its polymkeric substance for being obtained by high temperature polymerization, this polymkeric substance comprises the alkyl acrylate of the alkyl containing carbonatoms 1 ~ 10 of more than 60 % by weight as structures alone unit, weight-average molecular weight is 1,000 ~ 20,000.
As (D) composition, preferably comprise the material of (D1) composition and (D2) composition.
Further, these Photocurable adhesive agent compositions are preferably: with in the composition 1 ~ 25 % by weight containing proportional and comprise the Photocurable adhesive agent composition that (F) has the epoxy compounds of the ester ring type epoxy group(ing) shown at least two following formula (2) in the molecule.
As (F) composition, be preferably the epoxy compounds shown in following formula (3).
About free-radical polymerised compositions such as (A) compositions contained in these Photocurable adhesive agent compositions, the free radical of generation when decomposing under the effect of (E) composition at light can be utilized and be cured, but in order to obtain sufficient reactivity with few irradiation dose, preferably using less than 10 % by weight ratio and containing as the optical free radical polymerization starter of (G) composition.
Further, about these Photocurable adhesive agent compositions, in order to obtain the coated face of smoothness excellence, preferably contain the flow agent as (I) composition of 0.01 ~ 0.5 % by weight in the composition.
The invention provides a kind of Polarizer in addition; it is for fitting in the Polarizer of polaroid by protective membrane by caking agent; described protective membrane is formed by the transparent resin film selected from vibrin, polycarbonate resin, acrylic resin and noncrystalline polyolefin resinoid; described polaroid is by having carried out uniaxial extension and polyvinyl alcohol resin film dichroism pigment having been carried out gas absorption quantity is formed; wherein, this caking agent is formed by any one Photocurable adhesive agent composition above-mentioned.
This Polarizer manufactures by following method, and the method comprises following operation: at least one party among the binding face of polaroid and protective membrane is coated with the caking agent painting process of any one Photocurable adhesive agent composition aforementioned; Pass through the bonding process that polaroid and protective membrane are fitted by obtained bond layer; Under the state of polaroid and protective membrane being fitted by this bond layer, by the curing process that Photocurable adhesive agent composition is cured.Specifically, can adopt with the following method: on polaroid, be coated with uncured above-mentioned Photocurable adhesive agent composition, then at this adhesive composite coated face laminating protective membrane, then this adhesive composite be cured and form the method for bond layer; Be coated with uncured above-mentioned Photocurable adhesive agent composition at protective membrane, then at this adhesive composite coated face laminating polaroid, then this adhesive composite be cured and form the method for bond layer; The above-mentioned Photocurable adhesive agent composition that curtain coating is uncured between polaroid and protective membrane; with roller etc., the laminating thing of polaroid and protective membrane is clamped and adhesive composite is extruded expansion on one side equably; while crimping, then this adhesive composite be cured and form the method etc. of bond layer.
The present invention further provides a kind of optical component being laminated with the optical layers of above-mentioned Polarizer and other display optical function.Other optical layers in the case preferably comprises polarizer.A kind of liquid crystal indicator this optical component being configured at the one-sided of liquid crystal cells or both sides is also provided.
The effect of invention
About Photocurable adhesive agent composition of the present invention; even if when resin film low for the Water Vapour Permeability selected from vibrin, polycarbonate resin, acrylic resin and noncrystalline polyolefin resinoid is set to protective membrane; bonding force is manifested immediately after rayed; final bonding force after certain hour is also good; and also can not cause the problems such as bad order after long duration test; further, hot resistance test terminate after bonding force excellent.This adhesive composite is particularly useful when protective membrane is made up of acrylic resin.About this adhesive composite, when by bonding with polaroid for acrylic resin, in the stripping test that stripping strength dies down, namely, acrylic resin is being fixed on level and smooth plate, and in stripping test when having been bent by polaroid, is also showing good bonding force.Thus, also excellent in not easily peeling off in manufacturing procedure.
In addition, the viscosity of adhesive composite of the present invention is very low, is thus easily coated with thinly and does not fit defectively.The Polarizer of polaroid and protective membrane being fitted and obtaining about utilizing this adhesive composite; this adhesive composite not only solidifies in the operation of rayed such short period of time; and after rayed just terminates, also can obtain the bonding force of some strength, thus can productivity and manufacturing well.
Further, the optical component obtained about this Polarizer and other optical layers being carried out combining, can form liquid crystal indicator excellent in reliability.
Embodiment
Below, the present invention is described in detail.In the present invention; the protective membrane formed by transparent resin film is being adhered to by having carried out uniaxial extension and when the polaroid that formed of the polyvinyl alcohol resin film that dichroism pigment has been carried out gas absorption quantity, having used the Photocurable adhesive agent composition of specific composition.By so polaroid and protective membrane being fitted via Photocurable adhesive agent composition, thus Polarizer can be obtained.This Polarizer by stacked with other optical layers with optical function, thus can be made into optical component.In addition, this optical component is configured at least one party side of liquid crystal cells, thus can be made into liquid crystal indicator.Below, according to the manufacture method of Photocurable adhesive agent composition, Polarizer, Polarizer, optical component, liquid crystal indicator order and be described.
[Photocurable adhesive agent composition]
In the present invention, in order to polaroid and protective membrane be fitted, the Photocurable adhesive agent composition of specific composition is thus used.Below, sometimes also can by this Photocurable adhesive agent composition referred to as " Photocurable adhesive agent " or " composition ".Photocurable adhesive agent of the present invention is the Photocurable adhesive agent that must contain following (A), (B), (C), (D) and (E) these five kinds of compositions.
(A) have many (methyl) acrylate of the polyvalent alcohol of 2 ~ 15 carbon atoms,
(B) have many glycidyl ethers of the polyvalent alcohol (but, except the polyether glycol of the repeat number more than 3 of alkylene oxide unit) of 2 ~ 10 carbon atoms,
(C) oxetane compound shown in following formula (1),
(D) with alkyl (methyl) acrylate be required structures alone unit polymkeric substance,
(E) Cationic photoinitiator
In this manual, (methyl) acrylate represents acrylate or (methyl) acrylate, and (methyl) acryl refers to acryl or methacryloyl.
In this manual, also many (methyl) acrylate of above-mentioned (A) is called " (A) composition " or " many (methyl) acrylate (A) ", also the epoxy compounds of above-mentioned (B) is called " (B) composition " or " epoxy compounds (B) ", also the oxetane compound of above-mentioned (C) is called " (C) composition " or " oxetane compound (C) ", also is the polymkeric substance of structures alone unit to be called " (D) composition " by above-mentioned (D) with alkyl (methyl) acrylate, also the Cationic photoinitiator of above-mentioned (E) is called " (E) composition " or " Cationic photoinitiator (E) ".
About in the composition of (A) ~ (E) composition containing proportional, all for benchmark with composition, (A) is become to be divided into 15 ~ 50 % by weight, (B) become to be divided into 2 ~ 35 % by weight, (C) become to be divided into 2 ~ 50 % by weight, (D) become to be divided into 1 ~ 30 % by weight, (E) becomes to be divided into 0.5 ~ 10 % by weight.
This Photocurable adhesive agent optionally containing there is the epoxy compounds of the ester ring type epoxy group(ing) shown at least two aftermentioned formulas (2) as (F) composition in the molecule, be preferably set in the composition 1 ~ 25 % by weight containing proportional.As (F) composition, be preferably the epoxy compounds shown in aftermentioned formula (3).
In addition, can containing optical free radical polymerization starter as (G) composition, be preferably set to less than 10 % by weight containing proportional.In addition, when compounding (F) composition, preferably contain the oxetane compound shown in aftermentioned formula (4) of 1 ~ 10 % by weight as (H) composition.Further, can containing flow agent as (I) composition.
In this manual, also the epoxy compounds of above-mentioned (F) is called " (F) composition " or " epoxy compounds (F) ", also the optical free radical polymerization starter of (G) is called " (G) composition " or " optical free radical polymerization starter (G) ", also the oxetane compound of (H) is called " (H) composition " or " oxetane compound (H) ", also the flow agent of (I) is called " (I) composition " or " flow agent (I) ".
< many (methyl) acrylate (A) >
In Photocurable adhesive agent of the present invention, many (methyl) acrylate becoming (A) composition is many (methyl) acrylate of the polyvalent alcohol with 2 ~ 15 carbon atoms.
The number of intramolecular (methyl) acryl is that the weather resistance such as the cold cycling tolerance of (methyl) acrylate of 1 easily become not enough.
By using (A) composition, thus reduce the viscosity of composition, and make to become excellence to the bonding force of protective membrane and weather resistance.Herein, as (A) composition, be more preferably two (methyl) acrylate of the glycol with 2 ~ 10 carbon atoms from the viewpoint of low viscosity, bonding force, weather resistance.In addition, as (methyl) acrylate, be preferably acrylate from the viewpoint of solidified nature.
As the object lesson of (A) composition, list neopentyl glycol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, 3-methyl isophthalic acid, 5-pentanediol two (methyl) acrylate, cyclohexane dimethylol two (methyl) acrylate, 2-butyl-2-ethyl-1,3-PD two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, propylene glycol two (methyl) acrylate, tetramethylene glycol two (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, tristane dihydroxymethyl two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, two (TriMethylolPropane(TMP)) four (methyl) acrylate, tetramethylolmethane three or four (methyl) acrylate, Dipentaerythritol five or six (methyl) acrylate, and two of Hydrogenated Bisphenol A (methyl) acrylate etc.
(A) composition also can have ester skeleton and/or isocyanuric acid ester skeleton.As the object lesson of compound with ester skeleton, list neopentyl glycol and hydroxypivalic acid and (methyl) acrylic acid esterification reaction product etc., as the example of compound with isocyanuric acid ester skeleton, list two or three (methyl) acrylate etc. of tricarbimide oxirane affixture.
Among them, 1,6-hexylene glycol two (methyl) acrylate and neopentyl glycol and hydroxypivalic acid and (methyl) acrylic acid esterification reaction product are from the viewpoint of lowering viscousity, cementability and excellent in te pins of durability and smell is particularly preferably few.
About (A) composition containing proportional, with composition all for benchmark and be set to 15 ~ 50 % by weight scope.By being set to this ratio, thus the bonding force after rayed just terminates, final bonding force and weather resistance can be made good.In addition, by make (A) composition containing proportional be 20 ~ 45 % by weight scope, thus bonding force can be made better.
< epoxy compounds (B) >
In Photocurable adhesive agent of the present invention, the epoxy compounds becoming (B) composition is many glycidyl ethers of the polyvalent alcohol (but, except the polyether glycol of the repeat number more than 3 of alkylene oxide unit) with 2 ~ 10 carbon atoms.
The number of intramolecular glycidyl ether is that the weather resistance such as the bonding force of the epoxy compounds of 1 and/or cold cycling tolerance easily becomes not enough.In addition, even have the polyvalent alcohol of 2 ~ 10 carbon atoms, the weather resistance such as the bonding force of the how glycidyl etherified compound obtained by the polyether glycol of the repeat number more than 3 of alkylene oxide unit and/or cold cycling tolerance also easily become not enough.
By using (B) composition, thus reduce the viscosity of composition, and make the bonding force of polaroid as excellent.Herein, as (B) composition, from the viewpoint of composition can being set to low viscosity and can be made into the material of bonding force excellence, be more preferably the diglycidyl ether of the glycol (but, except the polyether glycol of the repeat number more than 3 of alkylene oxide unit) with 2 ~ 10 carbon atoms.
As the object lesson of (B) composition, list ethylene glycol diglycidyl base ether, propylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexylene glycol diglycidyl ether, hydroxymethyl-cyclohexane diglycidyl ether, 1, 9-nonanediol diglycidyl ether, diethylene glycol diglycidyl glyceryl ether, dipropylene glycol diglycidyl ether, quinhydrones diglycidyl ether, Resorcinol diglycidyl ether, trimethylolpropane tris glycidyl ether, tetramethylolmethane three or four glycidyl group ether, and two of tricarbimide ethylene oxide adduct or triglycidyl group ether etc.
Among them, from the viewpoint of low viscosity and bonding force, be particularly preferably the alkane glycol diglycidyl ether of carbonatoms 2 ~ 10.
Proportional about containing of (B) composition, all for benchmark with composition, be set to the scope of 2 ~ 35 % by weight.By being set to this ratio, thus the bonding force after the bonding force after rayed just terminates, final bonding force and hot resistance test can be made good.Consider from this viewpoint, about (B) composition containing proportional, be preferably 5 ~ 30 % by weight, be more preferably 10 ~ 30 % by weight, more preferably 15 ~ 30 % by weight.
< oxetane compound (C) >
In Photocurable adhesive agent of the present invention, the oxetane compound becoming (C) composition is the oxetane compound shown in following formula (1).
Proportional about containing of (C) composition, all for benchmark with composition, be set to the scope of 2 ~ 50 % by weight.By being set to this ratio, thus can make the bonding force after rayed just terminates and final bonding force good.By compounding (C) composition in right amount, thus contribute to improving the bonding force to various base material, but particularly improve the bonding force to acrylic resin protective membrane widely.
(C) composition containing proportional less than 2 % by weight time, the bonding force after rayed just terminates and final bonding force are not enough.In addition, during more than 50 % by weight, then the bonding force of polaroid is reduced.
Proportional as containing of (C) composition, more excellent from the viewpoint of bonding force, be preferably 5 ~ 35 % by weight, be more preferably 10 ~ 30 % by weight.
< is polymkeric substance (D) > of required structures alone unit with (methyl) alkyl acrylate
In Photocurable adhesive agent of the present invention, by comprising (D) composition, thus the bonding force after final bonding force and hot resistance test can be made good.
As (D) composition, if be the polymkeric substance of structures alone unit then must can use various polymkeric substance with (methyl) alkyl acrylate.As (D) composition, preferably (methyl) alkyl acrylate is set to structures alone unit, and comprise the polymkeric substance of more than 50 % by mole relative to the entire infrastructure monomeric unit in polymkeric substance, be more preferably the polymkeric substance comprising more than 80 % by mole.
As (methyl) alkyl acrylate, list (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) isobutyl acrylate, (methyl) Ethyl acrylate, (methyl) cyclohexyl acrylate, (methyl) 2-EHA, (methyl) n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) vinylformic acid ester in the positive ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the positive last of the ten Heavenly stems, (methyl) isodecyl acrylate, (methyl) vinylformic acid dodecyl ester, (methyl) vinylformic acid n-tridecane base ester and (methyl) n-myristyl base ester etc.
Among them, be preferably (methyl) propylene alkyl acid esters of the alkyl containing carbonatoms 1 ~ 10, be more preferably (methyl) alkyl acrylate of the low alkyl group with carbonatoms 1 ~ 4.
As (D) composition, also can be (methyl) alkyl acrylate and the multipolymer that can carry out the ethylenically unsaturated monomer (hereinafter referred to as " other monomer ") of copolymerization with (methyl) acrylate.
As the object lesson of other monomer, list the carboxylic monomers such as (methyl) vinylformic acid; Acrylamide 2-methyl propane sulfonic acid and styrene sulfonic acid etc. are containing sulfonic monomer; The monomer of phosphorous acidic group; Monomer, the vinyl ester of the cyano-containings such as (methyl) vinyl cyanide; The aromatic ethenyl compound such as vinylbenzene and alpha-methyl styrene; Containing the monomer of anhydride group; The monomer of the hydroxyls such as (methyl) hydroxyalkyl acrylates such as (methyl) Hydroxyethyl acrylate, (methyl) Hydroxyethyl acrylate and (methyl) hy-droxybutyl; The monomer of the amide-containings such as acrylamide, DMAA, acrylamide; Containing amino monomer; Containing the monomer of imide; (methyl) glycidyl acrylates etc. are containing the monomer of epoxy group(ing); (methyl) acryloyl morpholine; And vinyl ether etc.
As (D) composition, the various polymkeric substance selected from aforementioned polymer can be used.
For the deliquescent object improving cementability and improvement and composition, be preferably the multipolymer of (methyl) alkyl acrylate and the monomer containing acidic groups.
As the monomer containing acidic groups, list the monomer etc. of carboxylic monomer, the monomer containing sulfo group, the monomer containing anhydride group and phosphorous acidic group, preferred carboxylic monomer.
As this multipolymer, for the reason making the storage stability of composition well such, preferred acid number is the multipolymer of below 20mgKOH/g, is more preferably below 15mgKOH/g.
As the molecular weight of (D) composition, be preferably 1,000 ~ 500,000 according to weight-average molecular weight (hereinafter referred to as " Mw "), be more preferably 1,000 ~ 200,000.
In addition, in the present invention, Mw represents the value obtained by the molecular weight determined by gel permeation chromatography (hereinafter referred to as " GPC ") is carried out polystyrene conversion.
As (D) composition, the various polymkeric substance selected from aforementioned polymer can be used, but be preferably: (methyl) alkyl acrylate comprising the alkyl containing carbonatoms 1 ~ 10 is 1 as structures alone unit, weight-average molecular weight, the polymkeric substance of 000 ~ 500,000.
As the preferred example of this polymkeric substance, include, for example following two kinds of polymkeric substance.
(D1) composition: the methyl methacrylate comprising more than 60 % by weight is 1,000 ~ 200 as structures alone unit, Mw, the polymkeric substance of 000
(D2) composition: the alkyl acrylate comprising the alkyl containing carbonatoms 1 ~ 10 of more than 60 % by weight is 1,000 ~ 200 as structures alone unit, Mw, the polymkeric substance of 000
(D1) composition be methyl methacrylate is set to structures alone unit and comprise more than 60 % by weight, Mw is 1,000 ~ 200, the polymkeric substance of 000, for the reason of the bonding force excellence to acrylic resin preferably.
(D1) composition also can be the multipolymer with the monomer containing acidic groups, as the monomer containing acidic groups, lists and aforementioned same monomer, is preferably carboxylic monomer.
As this multipolymer, for aforementioned same reason, be preferably acid number be the multipolymer of below 20mgKOH/g, be more preferably the multipolymer of below 15mgKOH/g.
Commercially available have (D1) composition, (methyl methacrylate containing more than 60 % by weight is as structures alone unit such as to list the DIANALBR-80 that Mitsubishi's beautiful sun (strain) makes, Mw95, 000, polymethylmethacrylate (PMMA) base polymer of acid number 0mgKOH/g), (methyl methacrylate containing more than 60 % by weight is as structures alone unit for DIANAL BR-83, Mw40, 000, the PMMA base polymer of acid number 2mgKOH/g) and DIANALBR-87 (methyl methacrylate containing more than 60 % by weight is as structures alone unit, Mw25, 000, the PMMA base polymer of acid number 10.5mgKOH/g) etc.
As (D1) composition, also can by high temperature polymerization described later, manufacture preferably by high temperature successive polymerization.
(D2) composition comprises the alkyl acrylate of the alkyl containing carbonatoms 1 ~ 10 of more than 60 % by weight as structures alone unit, and Mw is 1,000 ~ 200, and 000, for the reason of the final bonding force excellence to polaroid preferably.
As the alkyl acrylate of the alkyl containing carbonatoms 1 ~ 10, list and aforementioned same compound.
About (D2) composition, if the alkyl acrylate of the alkyl containing carbonatoms 1 ~ 10 is set to structures alone unit and comprises more than 60 % by weight, it so also can be the multipolymer with alkyl methacrylate and/or other monomer.
(D2) composition also can be: the segmented copolymer [hereinafter referred to as " (D2-1) composition "] of the alkyl acrylate of the alkyl containing carbonatoms 1 ~ 10 and, alkyl methacrylate and/or other monomer.
As the preferably combination of the monomer in (D2-1) composition, can enumerate: the block polymer etc. of the block unit of the block polymer with polyacrylic ester block unit and polymethacrylate block unit and the polymkeric substance with polyacrylic ester block unit and other monomer.
Among them, preferably there is the block polymer of polyacrylate(s) block unit and polymethacrylate block unit, more preferably comprise poly-butyl propyleneglycol acid esters and the polymethylmethacrylate block polymer as block unit.
As (D2-1) composition, can using by using aforementioned monomer and polymerization conventionally and the composition that manufactures, such as, listing radical polymerization, active anionic polymerization method, living radical polymerization etc.In addition, as the form of polymerization, such as, solution polymerization process, emulsion polymerization, suspension polymerization and mass polymerization etc. are listed.
Commercially available have (D2-1) composition, lists the Clarity (LA1114, LA2140e, LA2330, LA2250) etc. of Kuraray Co., Ltd..
(D2) composition is Mw is 1,000 ~ 200, the polymkeric substance of 000, but being preferably Mw is 1,000 ~ 100, and the polymkeric substance of 000, is more preferably 1,000 ~ 20,000.About the polymkeric substance with this Mw, be low viscosity for it, the composition obtained also easy with the reason of low viscosity coating preferably, even if and/or for the restriction of lowering viscousity having composition, also can increase compounding number, can improve as a result bonding force reason and preferably.
When wanting to manufacture this low-molecular weight polymer by common polymerization process, then usually need to increase chain-transfer agent and/or polymerization starter.When using the polymkeric substance employing chain-transfer agent in a large number, then the cation-curable of composition and/or bonding force easily reduce, and in addition, when using the polymkeric substance employing polymerization starter in a large number, then the storage stability of composition easily reduces.
Thus, be preferably a kind of polymkeric substance [hereinafter referred to as " (D2-2) composition "], it is the polymkeric substance that manufactures by not needing the high temperature polymerization of a large amount of chain-transfer agents and/or polymerization starter, this polymkeric substance comprises the alkyl acrylate of the alkyl containing carbonatoms 1 ~ 10 of more than 60 % by weight as structures alone unit, Mw is 1,000 ~ 20,000.
In addition, in the present invention, Mw represents and the molecular weight determined by GPC is carried out polystyrene conversion and the value obtained.
The temperature of high temperature polymerization is preferably 160 ~ 350 DEG C, is more preferably 180 ~ 300 DEG C.
Among high temperature polymerization, high temperature successive polymerization not only productivity is excellent, and has following strong point: owing to not easily there is the composition distribution in copolymer artcle, thus excellent compatibility etc.
High temperature successive polymerization can utilize known method and implement (such as, the clear 57-502171 publication of Japanese Unexamined Patent Application Publication, Japanese Laid-Open Patent Publication 59-6207 publication and Japanese Laid-Open Patent Publication 60-215007 publication etc.).
Specifically list following method: fill the reactor that can pressurize with solvent, be set as specified temperature under elevated pressure, then with certain feed speed, the compositing monomer mixture by monomer or polymer solvent as required, polymerization starter is supplied to reactor, extract the reaction solution of the amount matched with the feed rate of monomer mixture.
About the second-order transition temperature of (D2-2) composition, be preferably less than 20 DEG C, be more preferably-90 ~ 0 DEG C.
In addition, in the present invention, second-order transition temperature represents the value by using differential scanning calorimeter (DSC) to determine with the heat-up rate of 2 DEG C/min.
(D) composition in the present invention also can be: in polymkeric substance, import the composition that the free-radical polymerised functional group such as (methyl) acryl and/or the cationically polymerizable such as epoxy group(ing) and/or oxetanylmethoxy functional group obtain.As the introduction method of these functional groups, such as, list: be directed in the method for the end of active anionic polymerization and/or active free radical polymerization, the compound with polymerizable functional group added the method etc. of the functional group be formed in polymkeric substance.In addition, when importing the cationically polymerizable functional group such as epoxy group(ing) and/or oxetanylmethoxy, (methyl) acrylate with these functional group's bases also can be made to carry out copolymerization.
As (D) composition, only can use the one in aforesaid compound, also can and with two or more.
As the preferably combination of (D) composition; excellence is become from the viewpoint of making the bonding force to polaroid and the bonding force to protective membrane; preferably (D1) composition and the combination of (D2) composition are used, more preferably (D1) composition and the combination of (D2-2) composition are used.
As the also use ratio of (D1) composition with (D2) composition, be preferably 1/9 ~ 7/3.
Proportional as containing of (D) composition, need to be set to 1 ~ 30 % by weight for benchmark so that composition is all, be preferably 5 ~ 25 % by weight.Contain (D) composition by the ratio with 1 ~ 30 % by weight, thus the bonding force after the bonding force after rayed just completes, final bonding force and hot resistance test can be made good.
< Cationic photoinitiator (E) >
In Photocurable adhesive agent of the present invention, as cation-curable composition, containing the epoxy compounds be explained above (B), oxetane compound (C) and epoxy compounds described later as required and/or oxetane compound, thus compounding Cationic photoinitiator is as (E) composition.This Cationic photoinitiator by irradiating visible rays, ultraviolet, x-ray, electric wire isoreactivity energy line, thus produces positively charged ion kind or Lewis acid, causes the polyreaction of epoxy group(ing) and/or oxetanylmethoxy.
By compounding Cationic photoinitiator as (E) composition, thus the solidification under normal temperature can be carried out, consider polaroid thermotolerance and/or by expanding or shrinking the necessity minimizing of the deformation caused, can bonding protective membrane well.In addition, Cationic photoinitiator is worked by the irradiation of active energy ray catalytic, even if be thus mixed in epoxy compounds (B), oxetane compound (C) and epoxy compounds described later and/or oxetane compound, storage stability and/or workability are also excellent.Generating positively charged ion kind and/or lewis acidic compound as by irradiating active energy ray, include, for example the such salt of aromatic diazonium salt, aromatic iodonium salts and/or aromatic series sulfonium salt, iron-allene complex thing etc.
As aromatic diazonium salt, such as, list following such compound.
Benzene diazonium hexafluoro antimonate,
Benzene diazonium hexafluorophosphate,
Benzene diazonium hexafluoro borate etc.
As aromatic iodonium salts, such as, list following such compound.
Phenylbenzene iodine four (pentafluorophenyl group) boric acid ester,
Diphenyl iodine hexafluorophosphate,
Phenylbenzene iodine hexafluoro antimonate,
Two (4-nonyl phenyl) iodine hexafluorophosphate etc.
As aromatic series sulfonium salt, such as, list following such compound.
Triphenylsulfonium hexafluorophosphate,
Triphenylsulfonium hexafluoro antimonate,
Triphenylsulfonium four (pentafluorophenyl group) boric acid ester,
The two hexafluorophosphate of 4,4 '-bis-(phenylbenzene sulphur) diphenyl sulfide,
The two hexafluoro antimonate of 4,4 '-bis-[two (beta-hydroxy oxyethyl group) phenyl sulphur] diphenyl sulfide,
The two hexafluorophosphate of 4,4 '-bis-[two (beta-hydroxy oxyethyl group) phenyl sulphur] diphenyl sulfide,
7-[two (to toluyl) sulphur]-ITX hexafluoro antimonate,
7-[two (to toluyl) sulphur]-ITX four (pentafluorophenyl group) boric acid ester,
4-phenylcarbonyl group-4 '-phenylbenzene sulphur-diphenyl sulfide hexafluorophosphate,
4-(to tert-butyl-phenyl carbonyl)-4 '-phenylbenzene sulphur-diphenyl sulfide hexafluoro antimonate,
4-(to tert-butyl-phenyl carbonyl)-4 '-two (to toluyl) sulphur-diphenyl sulfide four (pentafluorophenyl group) boric acid ester etc.
As iron-allene complex thing, such as, list following compound.
Dimethylbenzene-cyclopentadienyl iron (II) hexafluoro antimonate,
Isopropyl benzene-cyclopentadienyl iron (II) hexafluorophosphate,
Dimethylbenzene-cyclopentadienyl iron (II)-three (trifluoromethyl sulfonyl) methide (メ タ Na イ De) etc.
These Cationic photoinitiators individually can use one, also two or more mixing can be used.Even if particularly aromatic series sulfonium salt also has Ultraviolet Light in the wavelength region of more than 300nm among them, thus can produce solidified nature excellence and there is good physical strength and/or the cured article of bonding strength, therefore preferably using.
(E) composition easily can obtain commercially available product, such as, respectively according to trade(brand)name, can list: " Kayarad PCI-220 ", " Kayarad PCI-620 " (more than, Japanese chemical drug (strain) is made), " UVI-6992 " (The Dow Chemical Company system), " AdekaoptomerSP-150 ", " Adekaoptomer SP-160 " (more than, (strain) ADEKA system), " CI-5102 ", " CIT-1370 ", " CIT-1682 ", " CIP-1866S ", " CIP-2048S ", " CIP-2064S " (more than, Japanese Cao Da (strain) makes), " DPI-101 ", " DPI-102 ", " DPI-103 ", " DPI-105 ", " MPI-103 ", " MPI-105 ", " BBI-101 ", " BBI-102 ", " BBI-103 ", " BBI-105 ", " TPS-101 ", " TPS-102 ", " TPS-103 ", " TPS-105 ", " MDS-103 ", " MDS-105 ", " DTS-102 ", " DTS-103 " (more than, Midori KagakuCo., Ltd. system), " PI-2074 " (Rhodia Inc.), " Irgacure 250 ", " IrgacurePAG103 ", " Irgacure PAG108 ", " Irgacure PAG121 ", " IrgacurePAG203 " (more than, BASF AG's system), " CPI-100P ", " CPI-101A ", " CPI-210S ", " CPI-110P " (more than, San-Apro Ltd. system) etc.Particularly, " CPI-100P " and " CPI-110P " of San-Apro Ltd. from the viewpoint of solidified nature and cementability, particularly preferably.
Proportional about containing of (E) composition, all for benchmark with composition, be set to the scope of 0.5 ~ 10 % by weight.Its ratio lower than 0.5 % by weight time, then the solidification of caking agent becomes insufficient, physical strength and/or bonding strength reduce, when its ratio is more than 10 % by weight on the other hand, then the water absorbability of cured article is caused to uprise because the ionic substance in cured article increases sometimes, endurance quality reduces, thus not preferred.In addition, as (E) composition containing proportional, be preferably 1 ~ 6 % by weight, by being set to this scope, thus can make the optical characteristics such as the transparency and/or endurance quality better.
< epoxy compounds (F) >
In Photocurable adhesive agent of the present invention, the preferably compounding as described above epoxy compounds becoming (F) composition.
(F) composition is the epoxy compounds in molecule with the ester ring type epoxy group(ing) shown at least two following formula (2), generally speaking can use known various solidified nature epoxy compoundss.
As the object lesson of (F) composition, list 3,4-epoxycyclohexyl-methyl-3,4-epoxycyclohexane carboxylate, two (3,4-epoxycyclohexyl-methyl) adipic acid ester, 3,4-epoxycyclohexyl-methyl-3, the carboxylate of the caprolactone modification thing of 4-epoxycyclohexane carboxylate, polycarboxylic acid and 3,4-epoxycyclohexyl methyl alcohol or caprolactone modification thing, there is at end (gathering) siloxane compound etc. of the ester ring type epoxy group(ing) shown in above-mentioned formula (2).
As (F) composition, from the viewpoint of low viscosity, solidified nature, based on the bonding force of cutting machine interpolation and excellent in te pins of durability, be preferably the epoxy compounds shown in following formula (3).
(F) epoxy compounds of composition can be used alone one, also two or more mixing can be used.
About the epoxy compounds of (F) composition, from the viewpoint of productivity, improving the bonding force after rayed just completes, or when improving the bonding force based on cutting machine interpolation, all for benchmark with composition, preferably containing 1 ~ 25 % by weight.
< optical free radical polymerization starter (G) >
About radically curing compositions such as (A) compositions contained in Photocurable adhesive agent of the present invention, when (E) composition can be utilized to decompose under the effect of light produce free radical and be cured, but in order to obtain sufficient reactivity with few irradiation dose, preferred compounding optical free radical polymerization starter is as (G) composition.About the compounding ratio of (G) composition, be more preferably 0.1 ~ 10 % by weight so that composition is all for benchmark and be preferably less than 10 % by weight, more preferably 0.1 ~ 3 % by weight.When compounding amount is below 10 % by weight, then excellent in te pins of durability, therefore preferably.
As the object lesson of (G) composition, include, for example following compound.
4 '-phenoxy group-2, 2-dichloroacetophenone, 4 '-tertiary butyl-2, 2-dichloroacetophenone, 2, 2-dimethoxy-2-phenyl acetophenone, 2-methyl isophthalic acid-(4-methylphenyl-sulfanyl)-2-morpholino third-1-ketone, 1-hydroxycyclohexylphenylketone, α, α-diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenyl third-1-ketone, 1-(4-cumyl)-2-hydroxy-2-methyl third-1-ketone, 1-(4-dodecylphenyl)-2-hydroxy-2-methyl third-1-ketone, 1-[4-(2-hydroxyl-oxethyl) phenyl]-2-hydroxy-2-methyl third-1-ketone, and the acetophenones Photoepolymerizationinitiater initiater that 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl) fourth-1-ketone is such,
The benzoin ethers Photoepolymerizationinitiater initiater that bitter almond oil camphor, benzoin methylether, ethoxybenzoin, benzoin isopropyl ether and benzoin isobutyl ether are such;
Benzophenone, o-benzoyl yl benzoic acid methyl esters, 4-phenyl benzophenone, 4-benzoyl-4 '-methyldiphenyl sulfide and the such benzophenone Photoepolymerizationinitiater initiater of 2,4,6-tri-methyl benzophenone;
The thioxanthene ketone Photoepolymerizationinitiater initiater that ITX, 2,4-diethyl thioxanthones, 2,4-bis-clopenthixal ketones and 1-chloro-4-propoxythioxanthone are such;
TMDPO, two (2,6-Dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide and two (2,4,6-trimethylbenzoyl) the such acylphosphine oxide class Photoepolymerizationinitiater initiater of phenyl phosphine oxide;
Oxime, ester class Photoepolymerizationinitiater initiater that 1-[4-(phenyl sulfur phenenyl)]-1,2-octadione-2-(O-benzoyl oxime) is such;
Camphorquinone etc.
(G) composition can be used alone one, or can be compounding two or more and use according to desired performance.
When the optical free radical polymerization starter of compounding (G) composition, about it containing proportional, all for benchmark with composition, be preferably less than 10 % by weight, be more preferably 0.1 ~ 3 % by weight.Optical free radical polymerization starter (G) containing proportional be below 10 % by weight time, then obtain sufficient intensity, when being more than 0.1 % by weight in addition, then the solidified nature of caking agent is excellent.
< oxetane compound (H) >
In Photocurable adhesive agent of the present invention, also can the oxetane compound shown in compounding following formula (4) as (H) composition.About (H) composition, when containing (F) composition, have and improve in the bonding force after rayed just terminates or the effect improving the bonding force when sword of cutting machine being inserted in acrylic resin protective membrane.Consider from this viewpoint, proportional about containing of (H) composition, be preferably set to 1 ~ 10 % by weight.
< flow agent (I) >
In Photocurable adhesive agent of the present invention, for the object of the coated face of acquisition smoothness excellence, the flow agent preferably containing (I) composition.
As (I) composition, list (gathering) type siloxane flow agent and fluorine class flow agent etc., commercially available various flow agents can be used.
All for benchmark with composition, (I) composition preferred containing proportional be 0.01 ~ 0.5 % by weight.When adding proportion is more than 0.01 % by weight, then fully can obtain the additive effect of flow agent, on the contrary, time below 0.5 % by weight, then excellent in adhesion.
Other solidified nature composition of < >
In Photocurable adhesive agent of the present invention, except above-mentioned (A) ~ (I) composition, also other cation-curable composition and/or radically curing composition can be contained.
As the cation-curable composition except (B) composition, (C) composition, (F) composition and (H) composition, list various epoxy compounds and/or oxetane compound and vinyl ether compound.
As the object lesson of the epoxy compounds except (B) composition and (F) composition, list: the diglycidyl ether of dihydroxyphenyl propane, the diglycidyl ether of Bisphenol F, the diglycidyl ether of brominated bisphenol-A, phenol novolak type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, terephthalic acid diglycidyl ester, o-phthalic acid diglycidyl ester, the addition reaction of terminal carboxylic's polyhutadiene and bisphenol A type epoxy resin, dicyclopentadiene dioxide, limonene dioxide, 4 vinyl cyclohexene dioxide, polyoxyethylene glycol (repeat number more than 3) diglycidyl ether, polypropylene glycol (repeat number more than 3) diglycidyl ether, polytetramethylene glycol (repeat number more than 3) diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, epoxidized vegetable oil, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3,4-epoxycyclohexyl) ethyl triethoxysilane, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxypropyl dimethoxysilane, the polyhutadiene diglycidyl ether of two terminal hydroxyls, the inner loop oxide compound of polyhutadiene, a part of initial ring oxidation of the double bond of styrene-butadiene copolymer and the compound " Epoflend " of Daicel Chemical Industries, Ltd [such as ,] that obtains, and the compound that a part of initial ring of the isoprene unit of the segmented copolymer of ethylene-butene copolymer and polyisoprene is oxidized and obtains " L-207 " of KRATON Inc. (such as) etc.
As the object lesson of the oxetane compound except (C) composition and (H) composition, list: the simple function trimethylene oxide containing alkoxyalkyl that 3-ethyl-3-(2-Ethylhexoxymethyl) trimethylene oxide is such, the simple function trimethylene oxide containing aromatic group that 3-ethyl-3-phenoxymethyloxetane is such, 1, two [(3-Ethyloxetane-3-base) methoxymethyl] benzene of 4-, 1, two [(3-Ethyloxetane-3-base) methoxyl group] benzene of 4-, 1, two [(3-Ethyloxetane-3-base) methoxyl group] benzene of 3-, 1, two [(3-Ethyloxetane-3-base) methoxyl group] benzene of 2-, 4, 4 '-bis-[(3-Ethyloxetane-3-base) methoxyl group] biphenyl, 2, 2 '-bis-[(3-Ethyloxetane-3-base) methoxyl group] biphenyl, 3, 3 ', 5, 5 '-tetramethyl--4, 4 '-bis-[(3-Ethyloxetane-3-base) methoxyl group] biphenyl, 2, two [(3-Ethyloxetane-3-base) methoxyl group] naphthalene of 7-, two [4-{ (3-Ethyloxetane-3-base) methoxyl group } phenyl] methane, two [2-{ (3-Ethyloxetane-3-base) methoxyl group } phenyl] methane, 2, 2-pair [4-{ (3-Ethyloxetane-3-base) methoxyl group } phenyl] propane, the etherification modified thing obtained based on 3-chloromethyl-3-Ethyloxetane of novolak phenolics (novolaktype phenol formaldehyde resin), 3 (4), 8 (9)-bis-[(3-Ethyloxetane-3-base) methoxymethyl]-three ring [5.2.1.0 2,6] decane, two [(3-Ethyloxetane-3-base) methoxymethyl] norcamphane of 2,3-, 1,1,1-tri-[(3-Ethyloxetane-3-base) methoxymethyl] propane, two [(3-Ethyloxetane-3-base) methoxymethyl] butane of 1-butoxy-2,2-, two [{ 2-(3-Ethyloxetane-3-base) methoxyl group } ethylmercapto group] ethane of 1,2-, two [{ 4-(3-Ethyloxetane-3-base) methylthio group } phenyl] thioether, two [(3-Ethyloxetane-3-base) methoxyl group]-2,2,3,3,4,4,5, the 5-octafluoro hexanes of 1,6-, 3-[(3-Ethyloxetane-3-base) methoxyl group] propyl trimethoxy silicane, 3-[(3-Ethyloxetane-3-base) methoxyl group] propyl-triethoxysilicane, the hydrolytic condensate of 3-[(3-Ethyloxetane-3-base) methoxyl group] propyl trialkoxy silane, four [(3-Ethyloxetane-3-base) methyl] silicon ester, the condensation reaction products etc. of 3-Ethyloxetane-3-base methyl alcohol and silane tetrol polycondensate.
As the object lesson of vinyl ether compound, list cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, dodecyl vinyl, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl base ether, triethyleneglycol divinylether, cyclohexanedimethanol divinyl base ether etc.
Proportional about containing of the cation-curable composition except (B) composition, (C) composition, (F) composition and (H) composition, all for benchmark with composition, be preferably less than 30 % by weight, more preferably less than 20 % by weight, particularly preferably less than 10 % by weight.
As the radically curing composition except (A) composition; list various compound; such as list (methyl) esters of acrylic acid; (methyl) acrylic amide; maleimide, (methyl) vinylformic acid, toxilic acid, methylene-succinic acid, (methyl) propenal, (methyl) acryloyl morpholine, NVP, cyanacrylate, hexanodioic acid divinyl ester, vinyltrimethoxy silane etc.
As the object lesson of (methyl) esters of acrylic acid in molecule with (methyl) acryl, list: (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) 2-EHA, (methyl) Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) lauryl acrylate, (methyl) stearyl acrylate ester, (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 4-hydroxy butyl ester, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, Isosorbide-5-Nitrae-cyclohexane dimethylol list (methyl) acrylate, dicyclo pentyl (methyl) acrylate, double cyclopentenyl (methyl) acrylate, dicyclo amylene oxygen base ethyl (methyl) acrylate, (methyl) benzyl acrylate, (methyl) acrylate of phenol oxirane affixture, (methyl) acrylate of p-cumylphenol oxirane affixture, (methyl) acrylate of orthoxenol oxirane affixture, (methyl) acrylate of nonylphenol oxirane affixture, (methyl) vinylformic acid 2-methoxy acrylate, (methyl) ethoxyethoxy ethyl acrylate, (methyl) acrylate of the oxirane affixture of 2-Ethylhexyl Alcohol, pentanediol list (methyl) acrylate, hexylene glycol list (methyl) acrylate, list (methyl) acrylate of Diethylene Glycol, list (methyl) acrylate of triethylene glycol, list (methyl) acrylate of TEG, list (methyl) acrylate of polyoxyethylene glycol, list (methyl) acrylate of dipropylene glycol, list (methyl) acrylate of tripropylene glycol, list (methyl) acrylate of polypropylene glycol, 2-hydroxyl-3-phenoxy propyl (methyl) acrylate, 2-hydroxyl-3-butoxypropyl (methyl) acrylate, (methyl) tetrahydrofurfuryl acrylate, caprolactone modification tetrahydrofurfuryl (methyl) acrylate, (2-Ethyl-2-Methyl-DOX-4-base) methyl (methyl) acrylate, (2-isobutyl--2-methyl isophthalic acid, 3-dioxolane-4-base) methyl (methyl) acrylate, (Isosorbide-5-Nitrae-dioxo spiro [4,5] decane-2-base) methyl (methyl) acrylate, glycidyl (methyl) acrylate, 3,4-epoxycyclohexyl-methyl (methyl) acrylate, (3-Ethyloxetane-3-base) methyl (methyl) acrylate, 2-(methyl) acryloyloxyethyl isocyanate, allyl group (methyl) acrylate, N-(methyl) acryloyl-oxyethyl hexahydrobenzene dicarboximide, N-(methyl) acryloyl-oxyethyl tetrahydrochysene Phthalimide, 2-(methyl) acryloyl-oxyethyl hexahydrophthalic acid, 2-(methyl) acryloyl-oxyethyl succsinic acid, ω-carboxyl-polycaprolactone list (methyl) acrylate, 2-(methyl) acryloyl-oxyethyl phosphate ester acid, 3-(methyl) acryloxypropyl Trimethoxy silane, 3-(methyl) acryloxypropyl dimethoxymethylsilane, 3-(methyl) acryloxypropyl triethoxyl silane etc.
In addition; as having the object lesson of (methyl) esters of acrylic acid [hereinafter referred to as " multifunctional (methyl) acrylate "] except (A) composition of plural (methyl) acryl in molecule, list polyoxyethylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, two (methyl) acrylate of bisphenol-A epoxy alkane affixture, carbamate (methyl) acrylate, polyester (methyl) acrylate and epoxy group(ing) (methyl) acrylate etc.As polyester (methyl) acrylate of (methyl) acryl with more than three, list (methyl) acrylate etc. of dendritic macromole type.
As the compounding ratio of multifunctional (methyl) acrylate, be preferably 2 ~ 20 % by weight in the composition.
As the object lesson of (methyl) acrylic amide, list (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N, N-diethyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-(3-N, N-dimethylaminopropyl) (methyl) acrylamide, methylene-bis (methyl) acrylamide, ethylene two (methyl) acrylamide, N, N-diallyl (methyl) acrylamide etc.
As the object lesson of maleimide, list the polyurethane-reinforcement reactant etc. of N-methylmaleimido, N-hydroxyethylmaleimide, N-hydroxyethyl citraconimide, N-hydroxyethyl citraconimide and isophorone diisocyanate.
Proportional about containing of the radically curing composition except (A) composition, all for benchmark with composition, be preferably less than 20 % by weight.
< does not have other composition > of solidified nature
Further, in Photocurable adhesive agent of the present invention, do not damaging the scope of effect of the present invention, can compounding other composition without solidified nature arbitrarily, specifically list photosensitizers, hot cationic polymerization initiators, polyol compound, water etc.
As the object lesson of photosensitizers, list benzophenone, o-benzoyl yl benzoic acid methyl esters, ITX, 9,10-dibutoxy anthracenes etc.Among them, also have the compound of the optical free radical polymerization starter being equivalent to aforementioned (G) composition, but said photosensitizers is as the sensitizing agent for the Cationic photoinitiator relative to (E) composition and the reagent worked herein.They individually can be used, also two or more mixing can be used.
Proportional about containing of photosensitizers, all for benchmark with composition, be preferably less than 3 % by weight.
As the object lesson of hot cationic polymerization initiators, can enumerate: benzylsulfonium, thiophene salt, tetramethylene sulfide salt, benzyl ammonium salt, pyridinium salt, hydrazonium salt, carboxylicesters, sulphonate, amine imide etc.About these initiators, easily can obtain commercially available product, such as, any one is all represented by trade(brand)name, list: " Adekaoputon CP77 " and " AdekaoputonCP66 " (more than, (strain) ADEKA system), " CI-2639 " and " CI-2624 " (more than, Japan Cao Da (strain) system), " San-Aid SI-60L ", " San-Aid SI-80L " and " San-AidSI-100L " (more than, three new chemical industry Co., Ltd. systems) etc.
Proportional about containing of hot cationic polymerization initiators, all for benchmark with composition, be preferably less than 3 % by weight.
As the object lesson of polyol compound, ethylene glycol, propylene glycol, polyether polyols, polyester polyol compound, polycaprolactone polyol compound, polycarbonate polyol compound etc. can be enumerated.
About the compounding ratio of polyol compound, all for benchmark with composition, be preferably less than 10 % by weight.
About the viscosity of Photocurable adhesive agent of the present invention, in order to obtain spendable coating in the manufacturing process of Polarizer, even that is, in order to obtain the also excellent coated face of film, smoothness, viscosity at 25 DEG C is preferably below 150mPas, is more preferably below 100mPas.More preferably below 50mPas.
In Photocurable adhesive agent of the present invention, being good to make the bonding force of the high polaroid of ridity, also can adding a small amount of water.In the case, the addition of water is preferably less than 3 % by weight for benchmark with composition entirety, is more preferably less than 1 % by weight.
Outside them, only otherwise damage effect of the present invention, just also can compounding ion trap agent, antioxidant, photostabilizer, chain-transfer agent, tackifiers, thermoplastic resin, metal oxide microparticle, defoamer, pigment, organic solvent etc.
[Polarizer]
Protective membrane, in order to be adhered to by protective membrane by having carried out uniaxial extension and the polaroid that the polyvinyl alcohol resin film that dichroism pigment has been carried out gas absorption quantity is formed uses, so be fitted in polaroid thus making Polarizer by the Photocurable adhesive agent be explained above.Namely Polarizer of the present invention is Polarizer protective membrane being fitted in polaroid and obtains, and this polaroid is by having carried out uniaxial extension and polyvinyl alcohol resin film dichroism pigment having been carried out gas absorption quantity is formed.Protective membrane only can fit in the one side of polaroid, also can fit in the two sides of polaroid.When protective membrane being fitted in the two sides of polaroid, respective protective membrane can be by the protective membrane of the resin formation of identical type, also can be by the protective membrane of different types of resin formation.
< polaroid >
The polyvinyl alcohol resin of composition polaroid is by obtaining the saponification of polyvinyl acetate esters resin.As polyvinyl acetate esters resin, except exemplifying the polyvinyl acetate as the homopolymer of vinyl-acetic ester, also exemplify vinyl-acetic ester and the multipolymer etc. that can carry out other monomer of copolymerization with it.As copolymerization other monomer in vinyl-acetic ester, such as, list unsaturated carboxylic acid class, olefines, vinyl ethers, unsaturated sulfonic acid class etc.The saponification deg of polyvinyl alcohol resin is generally 85 ~ 100 % by mole, is preferably the scope of 98 ~ 100 % by mole.This polyvinyl alcohol resin also can modification further, such as, also can use the polyvinyl formal obtained by carrying out modification with aldehydes and/or polyvinyl acetal etc.The polymerization degree of polyvinyl alcohol resin is generally 1, and 000 ~ 10,000, be preferably 1,500 ~ 10, the scope of 000.
Polarizer is through following operation manufacture: the operation of such polyvinyl alcohol resin film being carried out uniaxial extension; With dichroism pigment, polyvinyl alcohol resin film is dyeed, thus adsorb the operation of this dichroism pigment; With boric acid aqueous solution, the polyvinyl alcohol resin film having adsorbed dichroism pigment is carried out the operation processed; Carry out the operation of washing after based on the process of boric acid aqueous solution; And protective membrane is fitted in the operation of by implementing these operations, dichroism pigment having been carried out the uniaxial extension polyvinyl alcohol resin film of gas absorption quantity.
About uniaxial extension, can carry out before the dyeing based on dichroism pigment, also can carry out with the dyeing based on dichroism pigment simultaneously, also can carry out after the dyeing based on dichroism pigment.When carrying out uniaxial extension after the dyeing based on dichroism pigment, this uniaxial extension can carry out before boric acid process, also can carry out in boric acid process.Certain in addition, also can carry out uniaxial extension in these multiple stages.In order to carry out uniaxial extension, can stretch between the roller that circumferential speed is different single shaft, also can use hot-rolling and single shaft stretch.In addition, can for carrying out the dry type stretching that stretches in an atmosphere, also can stretch for the wet type of carrying out stretching under the state by solvent-swollen.Stretching ratio is generally about 4 ~ 8 times.
In order to polyvinyl alcohol resin film being dyeed with dichroism pigment, such as, by polyvinyl alcohol resin membranes submerged in the aqueous solution containing dichroism pigment.As dichroism pigment, specifically iodine or dichroic dye can be used.
When using iodine as dichroism pigment, enter method under usually adopting: by polyvinyl alcohol resin membranes submerged in the aqueous solution containing iodine and potassiumiodide, thus dyeing.About the content of the iodine in this aqueous solution is 0.01 ~ 0.5 weight part relative to water 100 weight part usually, about the content of potassiumiodide is 0.5 ~ 10 weight part relative to water 100 weight part usually.The temperature of this aqueous solution is generally about 20 ~ 40 DEG C, in addition, is generally about 30 ~ 300 seconds to the Immersion time in this aqueous solution.
On the other hand, when using dichroic dye as dichroism pigment, usually adopt with the following method: by polyvinyl alcohol resin membranes submerged in the aqueous solution comprising water-soluble dichroic dye, thus dyeing.The content of the dichroic dye in this aqueous solution is 1 × 10 relative to water 100 weight part usually -3~ 1 × 10 -2about weight part.This aqueous solution also can containing inorganic salt such as sodium sulfate.The temperature of this aqueous solution is generally about 20 ~ 80 DEG C, in addition, is generally about 30 ~ 300 seconds to the Immersion time in this aqueous solution.
About the boric acid process after the dyeing based on dichroism pigment, carried out in boric acid aqueous solution by the polyvinyl alcohol resin membranes submerged that will have dyeed.About the content of the boric acid in boric acid aqueous solution is 2 ~ 15 weight parts relative to water 100 weight part usually, about being preferably 5 ~ 12 weight parts.When using iodine as dichroism pigment, preferably this boric acid aqueous solution contains potassiumiodide.The content of the potassiumiodide in boric acid aqueous solution is preferably 5 ~ 15 weight parts about being usually 2 ~ 20 weight parts relative to water 100 weight part.Be generally 100 ~ 1 to the Immersion time in boric acid aqueous solution, about 200 seconds, be preferably about 150 ~ 600 seconds, more preferably about 200 ~ 400 seconds.The temperature of boric acid aqueous solution is generally more than 50 DEG C, is preferably 50 ~ 85 DEG C.
Polyvinyl alcohol resin film after boric acid process carries out washing process usually.About washing process, such as, to be carried out in water by the polyvinyl alcohol resin membranes submerged by boric acid process.By implementing drying treatment after washing, thus obtain polaroid.The temperature of the water in washing process is generally about 5 ~ 40 DEG C, and Immersion time is generally about 2 ~ 120 seconds.Usually undertaken by use hot air dryer and/or far infra-red heater in the drying treatment of carrying out thereafter.Drying temperature is generally 40 ~ 100 DEG C.Treatment time in drying treatment is generally about 120 ~ 600 seconds.
So can obtain by the polaroid that the polyvinyl alcohol resin film having carried out gas absorption quantity as iodine or the dichroic dye of dichroism pigment is formed.
< protective membrane >
Then, for this polaroid, use the Photocurable adhesive agent previously described, thus protective membrane is fitted in its one or two sides.The triacetylcellulose film as the protective membrane of polaroid is always adopted to have roughly 400g/m widely 2the Water Vapour Permeability of about/24hr; but in the present invention, as the protective membrane at least one face fitting in polaroid, adopt the resin that display is lower than the Water Vapour Permeability of this triacetyl cellulose; that is, vibrin, polycarbonate resin, acrylic resin or noncrystalline polyolefin resinoid.
Kind for the protection of the vibrin of film is not particularly limited, but from the viewpoint of mechanical properties, solvent resistance, scratch-resistant, cost etc., is particularly preferably polyethylene terephthalate.Polyethylene terephthalate refers to more than the 80 % by mole resins be made up of ethylene glycol terephthalate of repeating unit, also can comprise the structural unit being derived from other copolymer composition.As other copolymer composition, list m-phthalic acid, to beta-hydroxy ethoxybenzoic acid, 4,4 '-dicarboxyl hexichol, 4, the dicarboxylic acid component that 4 '-benzophenonedicarboxylic acid, two (4-carboxyl phenyl) ethane, hexanodioic acid, sebacic acid, 5-sodiosulfoisophthalic acid and Isosorbide-5-Nitrae-dicarboxyl hexanaphthene are such; The diol component that the ethylene oxide adduct of propylene glycol, butyleneglycol, neopentyl glycol, Diethylene Glycol, cyclohexanediol, dihydroxyphenyl propane, polyoxyethylene glycol, polypropylene glycol and polytetramethylene glycol are such.These dicarboxylic acid component and/or diol component also can combine two or more as required and respectively and use.In addition, also can together with above-mentioned dicarboxylic acid component and/or diol component, and with the such hydroxycarboxylic acid of P-hydroxybenzoic acid.As other copolymer composition, the dicarboxylic acid component and/or diol component with amido linkage, ammonia ester bond, ehter bond, carbonic acid ester bond etc. also can be used on a small quantity.
As the manufacture method of vibrin, following arbitrary method can be adopted: make terephthalic acid and ethylene glycol (using other dicarboxylic acid and/or other glycol as required further) carry out the so-called direct polymerization method of direct reaction, the dimethyl ester of terephthalic acid and ethylene glycol (using the dimethyl ester of other dicarboxylic acid and/or other glycol as required further) be carried out the so-called transesterification reaction method etc. of transesterification reaction.In addition, vibrin also can contain known additive as required.As the additive that can contain, include, for example slip(ping)agent, anti-hard caking agent (Block ロ ッ キ Application グ prevents drug), thermo-stabilizer, antioxidant, static inhibitor, photostabilizer, shock-resistance modifying agent etc.But need the transparency as the protective membrane being laminated in polarizing film, therefore preferably the prior amount of these additives control is inferior limit.
Be film like by above-mentioned raw materials resin forming, implement uniaxial extension or biaxial stretch-formed process, thus the protective membrane formed by the vibrin stretched can be made.By implementing stretch processing, thus the high film of physical strength can be obtained.The making method of the polyester resin film stretched is any, be not particularly limited, following method can be enumerated: by by by above-mentioned raw materials resin melting and the No yield point film carrying out extrusion moulding with sheet and obtain, temperature more than second-order transition temperature utilizes tenter machine and carries out horizontal stretching, then implements heat fixation process.
When using vibrin as protective membrane, in order to obtain good cementability, preferably before coating adhesive, implement corona treatment, or use the polyester resin film with the easy bonding processing layer in surface.
Polycarbonate resin for the protection of film is the polyester formed by carbonic acid and glycol or bis-phenol.Wherein, the aromatic copolycarbonate in molecular chain with phenylbenzene alkane, due to thermotolerance, weathering resistance and acid resistance excellence, thus can preferably use.As such polycarbonate, exemplify: by 2, two (4-hydroxy phenyl) propane (another name dihydroxyphenyl propane), 2 of 2-, two (4-hydroxy phenyl) butane, 1 of 2-, 1-bis(4-hydroxyphenyl) cyclohexane, 1, two (4-hydroxy phenyl) Trimethylmethane of 1-or the derivative polycarbonate of the such bisphenols of two (4-hydroxy phenyl) ethane of 1,1-.
As the manufacture method of polycarbonate resin film, any one method such as casting film method, extrusion by melting can be used.As the example of concrete manufacture method, method can be listed below: polycarbonate resin is dissolved in suitable organic solvent and makes polycarbonate resin solution, its curtain coating is formed net in metal support, this net is stripped from aforementioned metal support, then the net stripped is carried out warm air drying thus obtain film.
Acrylic resin for the protection of film is also not particularly limited, but is generally the polymkeric substance of the monomer based on methacrylic ester, preferably makes the multipolymer of other a small amount of comonomer components and its copolymerization.About the methacrylic ester of main component becoming acrylic resin, usually preferably use alkylmethacrylate, particularly preferably use methyl methacrylate.In addition, as comonomer components, generally use methyl acrylate, ethyl propenoate, butyl acrylate, 2-EHA etc.Further, sometimes also aromatic ethenyl compound such for vinylbenzene and/or the such vinyl cyanide compound etc. of vinyl cyanide can be set to comonomer components.
As the manufacture method of acrylic resin, the arbitrary method such as common mass polymerization, suspension polymerization, letex polymerization can be adopted.The mass polymerization that there is not water soluble component in polymer class is particularly preferably used among them.In addition, in order to obtain applicable second-order transition temperature, or be shaped to the viscosity of the formability of applicable film to obtain display, preferably the usage chain transfer agent when being polymerized.About the amount of chain-transfer agent, suitably determine according to the kind of monomer and composition.In addition, acrylic resin also can contain known additive as required.As known additive, include, for example slip(ping)agent, anti-hard caking agent, thermo-stabilizer, antioxidant, static inhibitor, photostabilizer, shock-resistance modifying agent, tensio-active agent etc.But need the transparency as the protective membrane being laminated in polarizing film, therefore preferably the prior amount of these additives control is inferior limit.
As the manufacture method of acrylic resin films, any one method such as extrusion by melting, rolling process that melting casting method, T-shaped modulus method and/or inflation method are such can be used.Wherein, such as melt extrude from T-shaped mould about by material resin, at least one side of obtained tympan is contacted with the method for roller or belt and masking, from the viewpoint of obtaining the good film of surface texture preferably.
In acrylic resin, consider from viewpoints such as the shock-resistance to the masking of film and/or film, also can containing the acrylic rubber particle as impact modifying agent.Said acrylic rubber particle refers to the particle elastomeric polymer based on acrylate being set to required composition herein, lists the particle of single layer structure substance only comprising this elastomeric polymer, this elastomeric polymer is set to the particle of the multilayered structure of one deck.As the example of relevant elastomeric polymer, list: take alkyl acrylate as main component, can carry out with other vinyl monomer of its copolymerization and cross-linkable monomer the cross-linking elasticity multipolymer that copolymerization obtains.As the alkyl acrylate of main component becoming elastomeric polymer, the carbonatoms such as listing the alkyl such as methyl acrylate, ethyl propenoate, butyl acrylate, 2-EHA is the alkyl acrylate of about 1 ~ 8, particularly preferably uses the acrylate with the alkyl of carbonatoms more than four.As can with other vinyl monomer of this alkyl acrylate copolymer, the compound in molecule with a polymerizability carbon-to-carbon double bond can be listed, more specifically list the vinyl cyanide compound etc. that the such aromatic ethenyl compound of the such methacrylic ester of methyl methacrylate, vinylbenzene, vinyl cyanide are such.In addition, as cross-linkable monomer, the compound of the bridging property with at least two polymerizability carbon-to-carbon double bonds can be set forth in molecule, more specifically list (methyl) esters of acrylic acid of ethylene glycol bisthioglycolate (methyl) acrylate and the such polyvalent alcohol of butyleneglycol two (methyl) acrylate, (methyl) acrylic acid alkenyl esters, Vinylstyrene etc. that allyl group (methyl) acrylate is such.
Further, also the film formed by the acrylic resin not comprising rubber grain and the sandwich of the film formed by the acrylic resin comprising rubber grain can be made protective membrane.
When using acrylic resin as protective membrane; when using composition of the present invention; even if then do not carry out corona treatment can obtain good cementability yet; but be good for making the coating of caking agent; or make cementability be better object, also can implement corona treatment before coating adhesive.
Noncrystalline polyolefin resinoid for the protection of film normally has the resin of the polymerized unit of being derived by the cyclic olefin of the such polycycle of norbornylene and/or its derivative, dimethano-octahydro naphthalene; when remaining double bond as ring-opening polymerization polymer, preferably carry out hydrogenation wherein and the thermoplastic resin obtained.Noncrystalline polyolefin resinoid also can be the multipolymer of cyclic olefin and chain olefin, also can import polar group in addition.Wherein, thermoplasticity saturated norbornene resinoid is representational.When enumerating the resinoid example of commercially available noncrystalline polyolefin, then have " ARTON " of JSR Corporation, " ZEONEX " of ZEON Corporation and " ZEONOR ", Mitsui Chemicals, Inc " APO " and " APEL (ア ペ Le) " etc.When being filmed by noncrystalline polyolefin resinoid and making film, in masking, suitably use the known methods such as solvent streams casting, extrusion by melting.
When using noncrystalline polyolefin resinoid as protective membrane, in order to obtain good cementability, preferably before coating adhesive, implement corona treatment.
On the Polarizer that the visible side of liquid crystal indicator uses, for be configured at its visible side, namely, the protective membrane of contrary with liquid crystal cells side, can anti-glare be given.In the case, the structure of protective membrane be visible side surface, namely, fit on the face of opposition side in the face of polaroid, general the antiglare layer with concave-convex surface is set.Antiglare layer is generally formed by the following method: give in active energy ray-curable resin by embossing (emboss method) by concavo-convex, or there is the particulate of the specific refractory power different from it by compounding in active energy ray-curable resin and solidify, thus giving concavo-convex.In addition when protective membrane is made up of acrylic resin, it is also effective for forming protective membrane by following layers laminate film: by structure be tackiness agent acrylic resin in the light scattering layer that obtains of the compounding particulate with the specific refractory power different from it and the laminate film by the transparent layer not having the acrylic resin of this particulate compounding to be formed.Can adopt following form in the case: the form two-layer laminate film formed by above-mentioned light scattering layer and above-mentioned transparent layer being fitted on its light scattering layer side polaroid, and/or the laminate film of the three-decker obtained being clamped on the two sides of above-mentioned light scattering layer by above-mentioned transparent layer fits in the form etc. of polaroid on an one transparent layer.Further; even if when the acrylic resin laminate film imparting anti-glare by comprising such light scattering layer is set to protective membrane; also its become visible side surface, namely, fit in the face of polaroid opposition side face on arrange as antiglare layer as described above; thus further improving anti-dazzle performance, this is also effective.
As the aforementioned; particularly when acrylic resin films is set to protective membrane; the cementability not comprising the epoxy resin single component of aromatic nucleus shown in aforesaid patent documentation 6 (Japanese Unexamined Patent Publication 2004-245925 publication) may not be sufficient; but; about composition of the present invention; even if when this acrylic resin films is set to protective membrane, also produce good bonding force.Therefore the present invention is particularly useful when acrylic resin films being set to protective membrane.
In the present invention; by previously described Photocurable adhesive agent, the protective membrane formed by the transparent resin film selected from vibrin described above, polycarbonate resin, acrylic resin and noncrystalline polyolefin resinoid of fitting at least one face of polaroid.Only when the single-sided lamination protective membrane of polaroid, such as, also can adopt and the forms such as the adhering agent layer for fitting in other components such as liquid crystal cells are directly set at the another side of polaroid.
On the other hand, when protective membrane being fitted in the two sides of polaroid, respective protective membrane can be the protective membrane of identical type, also can be different types of protective membrane.Specifically such as can adopt following form: in the form of laminating polyester resin film in the two sides of polaroid as protective membrane; In the form of laminating polycarbonate resin in the two sides of polaroid as protective membrane; In the form of laminating acrylic resin in the two sides of polaroid as protective membrane; In the form of the two sides of polaroid laminating noncrystalline polyolefin resinoid as protective membrane; Fit the transparent resin film of any one selected from vibrin, polycarbonate resin, acrylic resin and noncrystalline polyolefin resinoid as protective membrane in the one side of polaroid; fit from any one vibrin, polycarbonate resin, acrylic resin and noncrystalline polyolefin resinoid at the another side of polaroid, and the transparent resin film different from the protective membrane of above-mentioned one side is as the form etc. of protective membrane.Also can adopt following form further: fit the transparent resin film of any one selected from vibrin, polycarbonate resin, acrylic resin and noncrystalline polyolefin resinoid as protective membrane in the one side of polaroid, in the another side laminating of polaroid from any one all different transparent resin film selected in vibrin, polycarbonate resin, acrylic resin and noncrystalline polyolefin resinoid as protective membrane.When protective membrane being fitted in the two sides of polaroid, two protective membranes periodically can be fitted in each face one by one, also can be fitted at one-phase in two sides.
When protective membrane being fitted in the two sides of polaroid; and when the side in them is set to other resin film different from vibrin, polycarbonate resin, acrylic resin and noncrystalline polyolefin resinoid; as the preference of this other resin, cellulosic resin can be enumerated.In addition; according to the present invention; bonding by previously described Photocurable adhesive agent at the protective membrane formed by vibrin, polycarbonate resin, acrylic resin and noncrystalline polyolefin resinoid of a face laminating of polaroid, but the protective membrane of fitting in another face of polaroid is also bonding by other caking agent.Such as; when a face of polaroid arranges the protective membrane formed by the resin film that the Water Vapour Permeability that cellulosic resin film is such is higher; on the binding face of the high resin film of this Water Vapour Permeability, also can use the caking agent except epoxies such as polyvinyl alcohol caking agent.But Photocurable adhesive agent of the present invention also produces high bonding force for illustrative cellulosic resin film herein, thus uses identical caking agent that operation can be made to become simple on the two sides of polaroid, thus favourable.
About the cellulosic resin of protective membrane that can be used as the opposing party, cellulosic partial esterification thing or full carboxylate can be enumerated, include, for example cellulosic acetic ester, propionic ester, butyric ester, their mixed ester etc.Specifically list triacetyl cellulose, diacetyl cellulose, cellulose acetate propionate, cellulose acetate butyrate etc.When enumerating the example by the commercially available product of the film of such cellulose esters resin formation, then there are " the Fujitac TD80 ", " Fujitac TD80UF " and " Fujitac TD80UZ " of Fujifilm Corporation, " KC8UX2M " and " KC8UY " of KonicaMinolta Opto Co., Ltd. etc.In addition, the cellulosic resin film imparting optical compensation function can also be used.As relevant optical compensating film, such as, list: in cellulosic resin containing have adjusting offset function compound and obtain film, the surface coated of cellulosic resin film have adjusting offset function compound and obtain film, cellulosic resin film single shaft or twin shaft are stretched and the film etc. that obtains.When enumerating the example of the optical compensating film of commercially available cellulose family, then have " the Wide View Film WV BZ 438 " and " Wide View Film WV EA " of Fujifilm Corporation, " KC4FR-1 " and " KC4HR-1 " of Konica Minolta Opto Co., Ltd. etc.
Can be used as the example of the low transparent resin of the Water Vapour Permeability of the protective membrane of the opposing party as other resin different from vibrin, polycarbonate resin, acrylic resin and noncrystalline polyolefin resinoid, list polysulfone resin, ester ring type polyimide resin etc.
About protective membrane, before polaroid laminating, also the easy bonding process such as saponification process, corona treatment, prime treatment, anchor coating process can be implemented to binding face.In addition, on the surface of the opposition side of the binding face side to polaroid laminating of protective membrane, also can have the various processing layers such as hard coat, anti-reflection layer, antiglare layer.The thickness of protective membrane is generally the scope of about 5 ~ 200 μm, is preferably 10 ~ 120 μm, more preferably 10 ~ 85 μm.
[manufacture method of Polarizer]
Polarizer of the present invention manufactures by following method, the method comprises following operation operation: at least one party among previously described polaroid with the binding face of the protective membrane formed by the transparent resin film selected from vibrin, polycarbonate resin, acrylic resin and noncrystalline polyolefin resinoid, is coated with the caking agent painting process of the Photocurable adhesive agent previously described; Pass through the bonding process that polaroid and protective membrane are fitted by obtained bond layer; Under the state of polaroid and protective membrane having been fitted by this bond layer, the curing process that Photocurable adhesive agent is cured.
< caking agent painting process >
In caking agent painting process, at least one party among the binding face of polaroid and protective membrane, is coated with previously described Photocurable adhesive agent.When the surface of polaroid or protective membrane is directly coated with Photocurable adhesive agent, there is no particular limitation for its coating process.Such as can utilize the various coating method such as scraper, line rod, mould painting machine, comma coater, gravure coater.In addition, also can utilize following method: between polaroid and protective membrane, previously described Photocurable adhesive agent is carried out curtain coating, then carry out pressurizeing with roller etc. and extrude expansion equably.
The envrionment temperature of caking agent painting process is preferably 15 ~ 30 DEG C, is particularly preferably 20 ~ 25 DEG C.In addition, the relative humidity of coating environment is preferably less than 80%, is more preferably less than 70%, and more preferably 30 ~ 70%, be particularly preferably 40 ~ 60%.By being above-mentioned scope by the envrionment temperature of caking agent painting process and moisture control, thus bonding force can be made to manifest speed and/or final bonding force is stably good.
In addition, different from envrionment temperature, about the temperature of the caking agent when coating, for the object that the coating caused by lowering viscousity improves and/or bonding force described later improves, also can carry out heating or heating.Now heat or Heating temperature is preferably less than 80 DEG C, be more preferably the scope of 20 ~ 60 DEG C.But between after coating film to entering bonding process, manifest speed and/or final bonding force is good from the viewpoint of making bonding force, preferred caking agent film is exposed to 15 ~ 30 DEG C, the environment of humidity less than 80%.
< bonding process >
After being so coated with Photocurable adhesive agent, be supplied in bonding process.In this bonding process; such as, when the Photocurable adhesive agent that utilized painting process above in the surface coated of polaroid, at the superimposed protective membrane in this place; when the Photocurable adhesive agent that utilized painting process above in the surface coated of protective membrane, at the superimposed polaroid in this place.In addition, between polaroid and protective membrane when curtain coating Photocurable adhesive agent, superimposed polaroid and protective membrane in this condition.When protective membrane being fitted in the two sides of polaroid, and when two sides all uses Photocurable adhesive agent of the present invention, on the two sides of polaroid respectively by Photocurable adhesive agent superimposed protective membrane.And; typically, in this condition, with roller etc. from two sides (when the superimposed protective membrane of the one side of polaroid; in polaroid side and protective membrane side or on the two sides of polaroid when superimposed protective membrane, the protective membrane side from this two sides) clamping and pressurizeing.The material of roller can use metal and/or rubber etc. herein.The roller being configured at two sides can, for identical material, also can be different materials.
< curing process >
As described above, by the laminating thing of state of polaroid and protective membrane being fitted by uncured Photocurable adhesive agent, then curing process is supplied in.In this curing process, by irradiating active energy ray to Photocurable adhesive agent, thus by comprising epoxy compounds, the bond layer of (methyl) acrylate and oxetane compound etc. is cured, and polaroid is bonding with protective membrane.When protective membrane being fitted in the one side of polaroid, also can irradiate active energy ray from the either side polaroid side, protective membrane side.In addition; when protective membrane being fitted in the two sides of polaroid; on the two sides of polaroid by Photocurable adhesive agent respectively under the state of protective membrane of fitting, irradiate active energy ray from the protective membrane side of either party, it is favourable for being solidified by the Photocurable adhesive agent on two sides simultaneously.But; in the protective membrane of either party when compounding UV light absorber (such as; when the cellulosic resin film of compounding UV light absorber is set to the protective membrane of a side); under active energy ray is ultraviolet situation, usually from the protective membrane side irradiation ultraviolet radiation not having compounding UV light absorber of the opposing party.
As active energy ray, visible rays, ultraviolet, x-ray, electric wire etc. can be used, but process easily and curing speed is also abundant, thus general preferred use ultraviolet.The light source of active energy ray is not particularly limited, but at below wavelength 400nm, there is luminescence distribution, such as, can use Cooper-Hewitt lamp, middle medium pressure mercury lamp, high pressure mercury vapour lamp, extra-high-pressure mercury vapour lamp, chemical lamp, black lamp, microwave-excitation mercuryvapour lamp, metal halide lamp, LED etc.
Photo-irradiation intensity to Photocurable adhesive agent is the photo-irradiation intensity determined for each objective composition, although be not particularly limited, but for the activation of polymerization starter, the exposure intensity of effective wavelength region is preferably set to UV-B (the medium wavelength region ultraviolet of 280 ~ 320nm), and according to becoming 1 ~ 3,000mW/cm 2mode set.Exposure intensity is 1mW/cm 2time above, then the reaction times is the length of appropriateness, and this exposure intensity is 3,000mW/cm on the other hand 2time following, then under the effect from the heating when heat of lamp radiation and Photocurable adhesive agent polymerization, thus the generation of the yellow of Photocurable adhesive agent and/or the deterioration of polaroid can be suppressed.
The rayed time to Photocurable adhesive agent is rayed time of the composition controlling each solidification, although be not particularly limited, by the integrating light quantity of the product representation of exposure intensity and irradiation time, preferably with UV-B according to becoming 10 ~ 5,000mJ/cm 2mode set.Integrating light quantity is 10mJ/cm 2time above, then the generation being derived from the active centre of polymerization starter is abundant, and the solidification of bond layer is fully carried out, and this integrating light quantity is 5,000mJ/cm on the other hand 2time following, then irradiation time appropriateness, productivity is excellent.
When irradiating active energy ray and Photocurable adhesive agent being cured, solidify under the condition preferably do not reduced in each function of the such Polarizer of the transparency of the degree of polarization of polaroid, transmissivity and form and aspect, protective membrane.
In thus obtained Polarizer, the thickness of bond layer is generally less than 50 μm, is preferably less than 20 μm, more preferably less than 10 μm, is particularly preferably less than 5 μm.
As making the preferred method that the bonding force of caking agent of the present invention and protective membrane is larger; also can after polaroid and protective membrane be fitted by use caking agent; before irradiation active energy ray, in the scope of optical characteristics not damaging polaroid, add heating process.As heating condition now, be preferably set to do not produce the contraction of polaroid and/or the deterioration of optical characteristics scope in.About preferred heating condition, change according to molecular weight of acrylic resin etc., but such as list 60 DEG C 1 ~ 10 second, 40 DEG C 5 ~ 30 seconds etc.After heating, between having irradiated to active energy ray, even if the temperature of caking agent is cooled to less than 40 DEG C, do not damage the effect that bonding force improves yet.
In addition; as other the preferred method of bonding force improving caking agent of the present invention and protective membrane; also following method can be listed: even if do not heat; namely; even if at 20 ~ 25 DEG C; by making the length of the manufacture line irradiated to active energy ray from laminating polaroid and protective membrane, thus it is about 60 seconds by the time lengthening after caking agent and acrylic contact.
But caking agent of the present invention has following strong point: though caking agent contact with acrylic resin protective membrane after at 20 ~ 25 DEG C about 20 ~ 30 seconds time, also manifest good bonding force.
[optical component]
When use Polarizer, also can be made into the optical layers at the optical function of the stacked display in its side except polarisation function and the optical component that obtains.For formed optical component object and be laminated in Polarizer optical layers in, such as have reflecting layer, Semitransmissive reflecting layer, light scattering layer, polarizer, solar panel, luminance brightness-improving film etc. for the formation of the various parts of liquid crystal indicator etc.Aforementioned reflecting layer, Semitransmissive reflecting layer and light scattering layer are following parts: the parts used when forming the optical component be made up of reflection-type and even Semitransmissive and/or scatter-type, their Polarizer of dual-purpose type.
About the Polarizer of reflection-type, use in the liquid crystal indicator of the type shown will the reflected incident light of visible side be derived from, the light sources such as backlight can be omitted, thus easy liquid crystal indicator is carried out slimming.In addition, about the Polarizer of Semitransmissive, the form display sentencing reflection-type bright, in the dark use the light sources such as backlight and use in the liquid crystal indicator of type that shows.About the optical component as reflection-type Polarizer, such as, set up the paper tinsel and/or vapor-deposited film that are formed by metals such as aluminium by the protective membrane on polaroid, thus can reflecting layer be formed.About the optical component of the Polarizer as Semitransmissive, by aforementioned reflecting layer is set to one-way vision mirror, or will the radioparent reflector of display light is adhered to Polarizer containing pearl pigment etc., thus formed.On the other hand; about the optical component as scatter-type Polarizer; such as; by using the method to the protective membrane enforcement delustring process on Polarizer, being coated with containing various methods such as the method for fine-grained resin, the bonding methods containing fine-grained film, thus form minute concave-convex structure on surface.
Further, about the formation of the optical component as the dual-purpose Polarizer of specular scattering, such as, reflect the methods such as the reflecting layer of this concaveconvex structure by arranging in the minute concave-convex structure face of scatter-type Polarizer, thus carry out.The reflecting layer of minute concave-convex structure has following advantage: by incident light being carried out diffuse-reflectance and scattering, preventing directive property and/or flicker, light and shade can be suppressed uneven.In addition, containing fine-grained resin layer and/or film, also there is following advantage: incident light and reflected light thereof, when particulate being contained layer transmission, scattering occurs, thus can more suppress light and shade uneven.Such as, about the reflecting layer reflecting surperficial minute concave-convex structure, by methods such as evaporation and/or plating such as vacuum evaporation, ion plating, sputterings, metal straight attachment is located at the surface of minute concave-convex structure, thus is formed.As in order to form surperficial minute concave-convex structure and compounding particulate, such as, can utilize the mineral-type particulate be made up of the silicon-dioxide, aluminum oxide, titanium oxide, zirconium white, stannic oxide, Indium sesquioxide etc. of median size 0.1 ~ 30 μm, the organic particulate etc. be made up of be cross-linked or uncrosslinked polymkeric substance etc.
On the other hand, about the polarizer as above-mentioned optical layers, use for the purpose of compensation of the phase differential based on liquid crystal cells etc.As its example, list: the birefringent film be made up of the oriented film etc. of various plastics, discotic mesogenic and/or nematic liquid crystal carried out orientation and fix and the film obtained, on film substrate, form above-mentioned liquid crystal layer and the material etc. obtained.In the case, as the film substrate supporting aligned liquid-crystal layer, preferably use the cellulose family films such as triacetyl cellulose.
As the plastics of form dielectric grid film, such as, list polyolefine, polyarylester, polymeric amide, noncrystalline polyolefin resinoid etc. that polycarbonate, polyvinyl alcohol, polystyrene, polymethylmethacrylate, polypropylene are such.Oriented film can be the oriented film carrying out processing in the mode that single shaft and/or twin shaft etc. are suitable and obtain.In addition, also can be by controlling the birefringent film of film in the specific refractory power of thickness direction at the bonding lower applying convergent force and/or drawing force with heat-schrinkable film.In addition, polarizer also can combine more than two and uses for the purpose of the control of the wide optical characteristics such as frequency band.
Solar panel is the parts used for objects such as light path control, with prism array sheet material and/or lens arra sheet material or can put the form formation of setting up sheet material etc.
Luminance brightness-improving film is the parts used for the object of the brightness improved in liquid crystal indicator etc., as its example, list: the oriented film of the reflection-type linear polarization separator sheet producing anisotropic patten's design according to being carried out by films mutually different for the anisotropy of specific refractory power multiple stacked and obtain on reflectivity, cholesteric liquid crystal polymer and/or its aligned liquid-crystal layer are supported in the rotatory polarization separator sheet etc. that film substrate obtains.
About optical component, by by Polarizer and one deck of selecting according to application target from aforementioned reflecting layer and even Semitransmissive reflecting layer, light scattering layer, polarizer, solar panel, luminance brightness-improving film etc. or two-layer more than optical layers combine, thus make two-layer or more than three layers duplexer.In this case, the optical layers such as light scattering layer and/or polarizer, solar panel and/or luminance brightness-improving film also can configure respectively two-layer more than.In addition, the configuration of each optical layers is not limited to.
The various optical layers forming optical component are carried out integrated by using caking agent with Polarizer, and therefore used caking agent is if the caking agent forming adhesive linkage well is then not particularly limited.From the simplicity of bonding process and/or prevent the viewpoints such as the generation of warp from considering, preferably use tackiness agent (also referred to as pressure adhesive).In tackiness agent, can use and acrylic polymers and/or (gathering) siloxane type polymers, polyester, urethane, polyethers etc. are set to matrix polymer and the tackiness agent obtained.Wherein, use preferably by the following tackiness agent of selection, this tackiness agent is as acrylic acid or the like tackiness agent, the transparency of optics is excellent, keep wettability and/or the cohesive force of appropriateness, also excellent with the cementability of base material, further there is weathering resistance and/or thermotolerance etc., heating and/or humidification condition under do not produce stripping problems such as floating and/or peel off.In acrylic acid or the like tackiness agent, be (methyl) acrylic acid alkyl ester of the alkyl of less than 20 and, the acrylic monomer containing functional group that be made up of (methyl) vinylformic acid and/or hydroxyethyl (methyl) acrylate etc. by the carbonatoms had as methyl and/or ethyl, butyl, according to second-order transition temperature preferably less than 25 DEG C, preferably the mode of less than 0 DEG C is compounding further, thus be polymerized, the weight-average molecular weight obtained be more than 100,000 acrylic copolymer can be used as matrix polymer.
Adhering agent layer is formed about to Polarizer, such as by carrying out as under type etc.: dissolve in the organic solvent as toluene, ethyl acetate or dispersion adhesion agent composition and prepare the liquid of solid concentration 10 ~ 40 % by weight, it is directly coated Polarizer and forms the mode of adhering agent layer, and/or on isolated film, form adhering agent layer in advance, moved and be connected on Polarizer thus form the mode of adhering agent layer.The thickness of adhering agent layer is determined according to its bonding force etc., but the scope of about 1 ~ 50 μm is suitable.
In addition, in adhesive coating, also can be compounding as required: weighting agent, pigment and/or the tinting material, antioxidant, UV light absorber etc. that comprise glass fibre, granulated glass sphere, resin bead, metal powder and/or other inorganic powder etc.In UV light absorber, have salicylate compounds and/or benzophenone compound, benzotriazole compound, cyanoacrylate compound, nickel complexing salt compounds etc.
[liquid crystal indicator]
Optical component such is above configured at the one-sided of liquid crystal cells or both sides, thus can be made into liquid crystal indicator.The liquid crystal cells used is any, such as, liquid crystal indicator is formed by using the various liquid crystal cells such as the driving liquid crystal cells of the single matrix (simple matrix) representated by the liquid crystal cells of the active matrix drive-type representated by film transistor type, super-twist nematic.The optical component being arranged at the both sides of liquid crystal cells can, for identical optical component, also can be different optical components.
Embodiment
Below, embodiment and comparative example are shown, illustrate the present invention further, but the present invention is not limited to these examples.In example, representing usage quantity and even contain proportional % so long as not special record, is exactly weight basis.In addition, the % of humidity represents the relative humidity at 23 DEG C.In addition, number represents weight part.
In embodiment and comparative example, each composition used in the preparation of Photocurable adhesive agent composition is as follows, is represented below by compound name or respective mark (trade(brand)name self or its part).
(A) composition: many (methyl) acrylic compound
" LIGHTACRYLATE 1,6HX-A " that HDDA:1,6-hexanediyl ester, common prosperity society chemistry (strain) make.
(B) composition: how glycidyl etherified compound
" Denacol EX-212L " (total chlorine 0.4%) of HD-DGE:1,6-hexylene glycol diglycidyl ether, Nagase chemtexCorporation.
(C) composition: the oxetane compound shown in previously described formula (1)
" Aron Oxetane OXT-221 " that OXT-221:3-ethyl-3-[(3-Ethyloxetane-3-base) methoxymethyl] trimethylene oxide, East Asia synthesis (strain) are made.
(D) composition: (methyl) acrylic polymers
BR-87: the methyl methacrylate containing more than 60 % by weight as structures alone unit, Mw25,000, the PMMA base polymer of acid number 10.5mgKOH/g, Mitsubishi's beautiful sun (strain) " the DIANAL BR-87 " that make.
Polymer A: the polymkeric substance obtained in aftermentioned Production Example 1.
(E) composition: Cationic photoinitiator
CPI-110P: " CPI-110P " of triaryl matte hexafluorophosphate (effective constituent 100%), San-Apro Ltd..
(F) composition: cycloaliphatic epoxy
CEL-2021: the cycloaliphatic epoxy shown in previously described formula (3), Daicel ChemicalIndustries, Ltd " Celloxide 2021P ".
(G) composition: optical free radical polymerization starter
Irg-184:1-hydroxy-cyclohexyl-phenyl-one, BASF AG " Irgacure 184 ".
(H) composition: the oxetane compound shown in previously described formula (4)
" Aron Oxetane OXT-101 " that OXT-101:3-ethyl-3-hydroxymethyl oxetane, East Asia synthesis (strain) are made.
(I) composition: flow agent
(gathering) type siloxane flow agent " DOW CORNING TORAY SH 28 PAINT ADDITIVE " of SH-28:Dow Corning Toray Co., Ltd..
[Production Example 1]
The jacket temperature that the adding pressure type having the capacity 1000mL of oil jacket stirs tank reactor is remained 181 DEG C.Then, while the pressure of reactor is remained necessarily, while start by butyl acrylate (45 parts), 2-EHA (45 parts), methyl methacrylate (10 parts), as the Virahol (9 parts) of polymer solvent, methylethylketone (9 parts), as the monomer mixture that the ditertiary butyl peroxide (0.25 part) of polymerization starter forms, with certain feed speed (48g/ minute, residence time: 12 minutes) be supplied in reactor continuously from head tank, the reaction solution suitable with the feed rate of monomer mixture is extracted continuously from exporting.After reaction has just started, after temporarily reducing temperature of reaction, find that the temperature caused because of heat of polymerization raises, but by controlling oil jacket temperature, thus temperature in reactor is held in 183 ~ 185 DEG C.What the time point after after stable for temperature in reactor 36 minutes is set to reaction solution takes starting point, and after this continue reaction in 25 minutes, result, for the monomer mixed solution giving 1.2kg, has reclaimed the reaction solution of 1.2kg.Thereafter by reaction solution is directed in thin-film evaporator, the volatile components such as unreacted monomer are separated, thus remove the volatile components such as unreacted monomer, obtain polymkeric substance " polymer A ".Carried out GPC mensuration, result is the number-average molecular weight (Mn) of polystyrene conversion is 2,500, and weight-average molecular weight (Mw) is 7,500, and the viscosity at 25 DEG C is 20,000mPas.
zero embodiment 1 ~ embodiment 4, comparative example 1 ~ comparative example 8
[preparation of Photocurable adhesive agent composition]
With respective ratio by compounding for each composition shown in table 1 ~ table 3, be conventionally uniformly mixed, thus prepared Photocurable adhesive agent composition.
The E type viscometer that viscosity at 25 DEG C of the composition obtained is made by eastern machine industry (strain) measures.
[making of Polarizer]
Herein, as protective membrane, use two kinds of films below.
Stretching norbornene resin film: thickness 70 μm, trade(brand)name " ZEONOR film ", ZEON Corporation system.Corona discharge Treatment is implemented to this film, is then supplied in the laminating with polaroid.
Acrylic resin films: thickness 80 μm, trade(brand)name " Technolloy S001 ", Sumitomo Chemical (strain) are made.For this film, also implement Corona discharge Treatment, be then supplied in the laminating with polaroid.
On the Corona discharge Treatment face of above-mentioned stretching norbornene resin film, with metering bar coater by the composition prepared above coating be 3 μm thick.This coated face is fitted in the polaroid by being obtained in polyvinyl alcohol by iodine gas absorption quantity by use hand roller.
Then, on the Corona discharge Treatment face of acrylic resin films, with metering bar coater by the composition prepared above coating be 3 μm thick.Thereafter, use hand roller, the polaroid integrated with norbornene resin film with aqueous composition is fitted in the coated face on acrylic resin films.
Utilize UV irradiation equipment (the lamp use EYE Graphics with conveying belt; Co., Ltd.'s high pressure mercury vapour lamp), protective membrane is fitted in two sides and the polaroid obtained for like this; from the face side of norbornene resin film, with integrating light quantity 250mJ/cm 2(UV-B) irradiation ultraviolet radiation, is cured adhesive composite.
23 DEG C, implement this experiment under the condition of relative humidity 50%.
In addition, in the experiment of table 1 ~ table 3, after adhesive composite is coated acrylic resin films, by until the time unification of irradiation ultraviolet radiation is the scope of 20 ~ 25 seconds.
[evaluation test]
About the Polarizer after uviolizing, evaluated by following method the bonding force after uviolizing just terminates, cutting machine insert bonding force, normal temperature article in custody (before hot resistance test) polaroid bend peeling adhesion force, hot resistance test, hot resistance test after polaroid bend peeling adhesion force and thermal cycling test, result is come together in table 1 ~ table 3.
The bonding force > of < after uviolizing just terminates
After irradiation ultraviolet radiation after 15 seconds, peel off between acrylic resin films and polaroid with hand, according to degree and the bonding force of solidification now, judge according to following three levels.
Zero: have cured fully, in addition, the film had in the mill transports the sufficient bonding force can not peeled off in operation.
△: although have cured, bonding force is slightly weak.
×: solidify insufficient and easily produce bubble in film transport operation, although or have cured, bonding force is quite weak, transports in operation easily peel off at film.
< cutting machine inserts bonding force >
For the Polarizer that have passed through more than two days after irradiation ultraviolet radiation, the sword of cutter is inserted from the inclined upward of acrylic resin films, according to appearance now and power, judges according to following four levels.
◎: sword does not enter, even if or when sword enters resistance also quite strong, acrylic resin films breaks immediately.
Zero: sword enters but resistance is strong, and when wanting stripping to expand, then acrylic resin films breaks.
△: sword enters, also feels resistance, but can expand stripping.
×: sword enters, and in interface, sword more carries out then with a little power that resistance is more weak.
The polaroid of < normal temperature article in custody (before hot resistance test) bends peeling adhesion force >
The Polarizer that have passed through more than 2 days after irradiation ultraviolet radiation is cut out the short strip shape into width 1 inch, length 15cm, utilize adhesive tape that acrylic resin films side is attached at sheet glass.Then, the polaroid film being adhered to norbornene resin film of upside is peeled off, and 180 ° of stripping tests are implemented in the mode of draw speed 300mm/ minute, bonding force (N/ inch) is recorded in table.
< hot resistance test >
The Polarizer that have passed through more than 2 days after irradiation ultraviolet radiation is cut out into width 4cm, length 6cm, 60 DEG C, placed 500 hours under the hot and humid environment of relative humidity 90%.For the Polarizer after hot resistance test, by visual observation stripping, variable color, judge according to following three levels.
Zero: can't see stripping, variable color.
△: slightly found stripping, variable color.
×: find stripping, variable color.
Polaroid after < hot resistance test bends peeling adhesion force >
The Polarizer that have passed through more than 2 days after irradiation ultraviolet radiation is cut out the short strip shape into width 1 inch, length 15cm, by adhesive tape, acrylic resin films side is attached at sheet glass.By its 60 DEG C, placed 500 hours under the hot and humid environment of relative humidity 90%, then take out in 23 DEG C, the environment of relative humidity 50%, the bonding force after determining taking-up after 5 minutes.About mensuration, by being peeled off by the polaroid film being adhered to norbornene resin film of upside, carried out 180 ° of methods peeled off with draw speed 300mm/ minute and implement, (N/ inch) is recorded in table by result.
< thermal cycling test >
For the Polarizer that have passed through more than 2 days after irradiation ultraviolet radiation, repeatedly carry out 300 times-35 DEG C place 60 minutes, then place the circulation of 60 minutes at+70 DEG C, thus implement thermal shock round-robin test.By the Polarizer after visual observation thermal cycling test, judge according to following three levels.
Zero: do not find bad order.
△: slightly found bad order.
×: find bad order.
Table 1
Table 2
Table 3
The composition of embodiment 1 is low viscosity and coating is excellent, and bonding force after uviolizing just terminates, cutting machine insert bonding force, the polaroid of normal temperature article in custody bend peeling adhesion force, hot resistance test, hot resistance test after polaroid any one result bent in the result of peeling adhesion force and thermal cycling test be all good.Particularly, the polaroid before and after hot resistance test bends peeling adhesion force excellence.
The composition of embodiment 2 and embodiment 3 is by reducing (B) composition and (C) composition in the composition of embodiment 1, and appropriate add (F) composition and (H) composition and the composition that obtains, it is excellent especially that cutting machine inserts bonding force.Bend peeling adhesion force about polaroid, the embodiment 3 being 11% with the content of (B) composition is compared, and the embodiment 2 comprising (B) composition of 19% has more powerful bonding force.
About and used the composition of the embodiment 2 of (D1) composition and (D2) composition, with do not comprise (D1) composition as (D) composition and correspondingly only comprise as the polymer A of (D2) composition embodiment 4 comparatively speaking, it is more excellent that the cutting machine polaroid inserted before and after bonding force and hot resistance test bends peeling adhesion force.And used (D1) composition and (D2) composition excellent as the bonding force of (D) composition that is.But the composition of embodiment 4 is provided with the feature lower with the composition phase specific viscosity of embodiment 2.
On the other hand, about the composition of comparative example 1 ~ comparative example 3 not comprising (D) composition, the bonding force after uviolizing just terminates, cutting machine insert at least one among bonding force and thermal cycling test for bad.
In addition, about the composition of comparative example 4 not comprising (B) composition, it is bad that polaroid before and after hot resistance test bends peeling adhesion force, exceed the composition of the comparative example 5 of the upper limit 35 % by weight about (B) composition, the bonding force after uviolizing just terminates is bad.About the composition of comparative example 5, the result that cutting machine inserts bonding force and thermal cycling test is also insufficient.
Exceed the composition of the comparative example 6 of the upper limit 50 % by weight about (A) composition, it is bad that cutting machine inserts bonding force, and it is insufficient that the bonding force after uviolizing just terminates and polaroid bend peeling adhesion force.About the composition of the comparative example 7 of the not enough lower limit 15 % by weight of (A) composition, although comprise (F) composition of a lot of solidified nature excellence, the bonding force after uviolizing just terminates or insufficient.Further, it is bad that the polaroid after hot resistance test bends peeling adhesion force.
About the composition of comparative example 8 not comprising (C) composition, it is bad that the polaroid of normal temperature article in custody bends peeling adhesion force, and it is insufficient that the bonding force after uviolizing just terminates and cutting machine insert bonding force.
Zero embodiment 5
In embodiment 5, acrylic resin films will be coated from adhesive composite until the time of irradiation ultraviolet radiation is set as 60 seconds longlyer, in addition, all test similarly to Example 3.
Its result is: before and after hot resistance test, all by strong to polaroid and acrylic resin films bonding, both cannot be peeled off, cannot measure peeling adhesion force.So, elongated by the time making caking agent be corroded by acrylic resin films, thus significantly can improve bonding force.
In addition, the result that the bonding force after uviolizing just terminates, cutting machine insert bonding force, hot resistance test and thermal cycling test is excellent similarly to Example 3.
Utilizability in industry
Photocurable adhesive agent composition of the present invention is low viscosity and is easily coated with in a thin film, bonding force after rayed just terminates and final bonding force excellence, and the bonding force after hot resistance test terminates is also excellent, the weather resistance of the Polarizer obtained is also excellent, thus can preferably be used in manufacture Polarizer.

Claims (19)

1. a Photocurable adhesive agent composition; it is the adhesive composite for protective membrane being adhered to polaroid; described protective membrane is formed by the transparent resin film selected in the group formed from vibrin, polycarbonate resin, acrylic resin and noncrystalline polyolefin resinoid; described polaroid, by having carried out uniaxial extension and polyvinyl alcohol resin film dichroism pigment having been carried out gas absorption quantity is formed, is characterized in that said composition contains:
(A) have many (methyl) acrylate of the polyvalent alcohol of 2 ~ 15 carbon atoms,
(B) have many glycidyl ethers of the polyvalent alcohol (but, except the polyether glycol of the repeat number more than 3 of alkylene oxide unit) of 2 ~ 10 carbon atoms,
(C) oxetane compound shown in following formula (1),
(D) with (methyl) alkyl acrylate be required structures alone unit polymkeric substance,
(E) Cationic photoinitiator,
Described (A) ~ (E) composition in the composition containing proportional be:
(A) composition: 15 ~ 50 % by weight
(B) composition: 2 ~ 35 % by weight
(C) composition: 2 ~ 50 % by weight
(D) composition: 1 ~ 30 % by weight
(E) composition: 0.5 ~ 10 % by weight.
2. Photocurable adhesive agent composition according to claim 1, wherein, (A) composition is two (methyl) acrylate of the glycol with 2 ~ 10 carbon atoms.
3. Photocurable adhesive agent composition according to claim 1, wherein, (B) composition is the diglycidyl ether of the glycol (but, except the polyether glycol of the repeat number more than 3 of alkylene oxide unit) with 2 ~ 10 carbon atoms.
4. Photocurable adhesive agent composition according to claim 1, wherein, (A) composition, (B) composition, (C) composition, (D) composition and (E) composition in the composition be respectively 20 ~ 45 % by weight, 5 ~ 30 % by weight, 5 ~ 35 % by weight, 5 ~ 25 % by weight and 1 ~ 6 % by weight containing proportional.
5. Photocurable adhesive agent composition according to claim 1, wherein, (D) composition comprises a kind of polymkeric substance, this polymkeric substance comprises (methyl) alkyl acrylate of the alkyl containing carbonatoms 1 ~ 10 as structures alone unit, weight-average molecular weight is 1,000 ~ 500,000.
6. Photocurable adhesive agent composition according to claim 5, wherein, (D) composition comprises a kind of polymkeric substance, this polymkeric substance comprises the methyl methacrylate of more than 60 % by weight as (D1) structures alone unit, weight-average molecular weight is 1,000 ~ 200,000.
7. Photocurable adhesive agent composition according to claim 5, wherein, (D) composition comprises a kind of polymkeric substance, this polymkeric substance comprises the alkyl acrylate of the alkyl containing carbonatoms 1 ~ 10 of more than 60 % by weight as (D2) structures alone unit, weight-average molecular weight is 1,000 ~ 200,000.
8. Photocurable adhesive agent composition according to claim 7, wherein, (D2) composition comprises a kind of polymkeric substance, its polymkeric substance for being obtained by high temperature polymerization, this polymkeric substance comprises the alkyl acrylate of the alkyl containing carbonatoms 1 ~ 10 of more than 60 % by weight as structures alone unit, weight-average molecular weight is 1,000 ~ 20,000.
9. Photocurable adhesive agent composition according to claim 6, wherein, (D) composition has also used (D1) composition and (D2) composition.
10. Photocurable adhesive agent composition according to claim 1, its further using in the composition 1 ~ 25 % by weight containing proportional and be included in molecule there is the ester ring type epoxy group(ing) shown at least two following formula (2) epoxy compounds as (F) composition
11. Photocurable adhesive agent compositions according to claim 10, wherein, (F) composition is the epoxy compounds shown in following formula (3)
12. Photocurable adhesive agent compositions according to claim 1, its further with in the composition less than 10 % by weight ratio and contain (G) optical free radical polymerization starter.
13. Photocurable adhesive agent compositions according to claim 1, its further using in the composition 1 ~ 10 % by weight containing proportional and comprise the oxetane compound shown in following formula (4) as (H) composition
14. Photocurable adhesive agent compositions according to claim 1, it contains the flow agent of in the composition 0.01 ~ 0.5 % by weight further as (I) composition.
15. 1 kinds of Polarizers; it is for fitting in the Polarizer of polaroid by protective membrane by caking agent; described protective membrane is formed by the transparent resin film selected in the group formed from vibrin, polycarbonate resin, acrylic resin and noncrystalline polyolefin resinoid; described polaroid is by having carried out uniaxial extension and polyvinyl alcohol resin film dichroism pigment having been carried out gas absorption quantity is formed; it is characterized in that, the Photocurable adhesive agent composition of described caking agent according to any one of claim 1 ~ 14 is formed.
The manufacture method of 16. 1 kinds of Polarizers; it is for fitting in polaroid by caking agent by protective membrane; thus manufacture the method for Polarizer; described protective membrane is formed by the transparent resin film selected in the group formed from vibrin, polycarbonate resin, acrylic resin and noncrystalline polyolefin resinoid; described polaroid, by having carried out uniaxial extension and polyvinyl alcohol resin film dichroism pigment having been carried out gas absorption quantity is formed, is characterized in that comprising following operation:
At least one party among the binding face of described polaroid and described protective membrane is coated with the caking agent painting process of the Photocurable adhesive agent composition according to any one of claim 1 ~ 14,
Pass through the bonding process that described polaroid and described protective membrane are fitted by obtained bond layer,
By curing process that described Photocurable adhesive agent composition is cured under the state of polaroid and protective membrane having been fitted by described bond layer.
17. 1 kinds of optical components, is characterized in that, Polarizer according to claim 15 is laminated with other optical layers.
18. optical components according to claim 17, wherein, other optical layers comprises polarizer.
19. 1 kinds of liquid crystal indicators, is characterized in that, by optical component according to claim 17 being configured at the one-sided of liquid crystal cells or both sides form.
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