CN102344763A - Photocurable adhesive composition, polarizing plate and a process of producing the same, optical member, and liquid crystal display device - Google Patents
Photocurable adhesive composition, polarizing plate and a process of producing the same, optical member, and liquid crystal display device Download PDFInfo
- Publication number
- CN102344763A CN102344763A CN2011101685727A CN201110168572A CN102344763A CN 102344763 A CN102344763 A CN 102344763A CN 2011101685727 A CN2011101685727 A CN 2011101685727A CN 201110168572 A CN201110168572 A CN 201110168572A CN 102344763 A CN102344763 A CN 102344763A
- Authority
- CN
- China
- Prior art keywords
- composition
- methyl
- protective membrane
- resin
- polarization element
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
- C09J163/10—Epoxy resins modified by unsaturated compounds
-
- 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
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
-
- 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
Abstract
To provide a photocurable adhesive with which a protective film is bonded to a polarizer with sufficient adhesive strength in a short-time process even when a resin film with low moisture vapor transmission is used as the protective film, and which has low viscosity, and with which no problem such as poor appearance is caused after an endurance test, and to provide a polarizing plate including a polarizer with the protective film bonded thereto by using the adhesive. The photocurable adhesive composition is an adhesive composition used for the purpose of bonding the protective film which is composed of a transparent resin film selected from predetermined four kinds of transparent resin films to the polarizer composed of a polyvinyl alcohol-based resin film, and includes: (A) an epoxy compound having two or more epoxy groups and one or more aromatic rings; (B) a di(meth)acrylate of a 5-10C diol (except an ether compound) optionally having an ester skeleton; and (C) a cationic photopolymerization initiator, and 20-60 wt.% of the component (A), 5-45 wt.% of the component (B), and 0.5-10 wt.% of the component (C) are included in the composition.
Description
Technical field
The present invention relates to be used in the applying of polaroid polarization element and protective membrane the light solidified binder composition, use this binder composition to be fitted with the method for manufacture of polaroid and this polaroid of protective membrane at polarization element.The invention still further relates to the optics and the liquid crystal indicator that use this polaroid.
Background technology
Polaroid is as a kind of optics that constitutes liquid crystal indicator.Polaroid is usually so that the range upon range of state that protective membrane arranged is assembled in the liquid crystal indicator and uses on the two sides of polarization element.Though it is known only in the one side of polarization element protective membrane being set, as a rule, not as simple protective membrane but have the layer double as protective membrane of other optical function and be fitted in another side.In addition, as the method for manufacture of polarization element, have as everyone knows the uniaxial extension polyvinyl alcohol resin film that utilizes the dichroism pigment dyeing is carried out the method that boric acid is handled, washed after drying.
Usually, after above-mentioned washing and drying, immediately to polarization element applying protective membrane.This be because, a little less than the physical strength of dried polarization element, in case when it is reeled, then can produce problems of crack on the machine direction.Thereby, usually on dried polarization element, be coated with the tackiness agent of water system immediately, then through this tackiness agent protective membrane of fitting simultaneously on the two sides of polarization element.Usually, as protective membrane, used thickness is the tri acetyl cellulose film of 30～120 μ m.
At polarization element and protective membrane, particularly with the protective membrane that constitutes by the tri acetyl cellulose film bonding in, use the tackiness agent of polyethenol series mostly, also have the tackiness agent of attempting using polyurethane series to replace the tackiness agent of this polyethenol series.For example, in japanese kokai publication hei 7-120617 communique (patent documentation 1), put down in writing the use polyurethane prepolymer as tackiness agent, for example the tri acetyl cellulose film is bonding for polarization element that water ratio is high and cellulose acetate prime system protective membrane.
On the other hand,, therefore be fitted with the polaroid of this resin molding, down for example under the such condition of 70 ℃ of temperature, relative humidity 90%, have problems such as causing deterioration damp and hot as protective membrane because the Water Vapour Permeability of tri acetyl cellulose is high.Therefore, also proposed resin molding through Water Vapour Permeability is lower than the tri acetyl cellulose film as protective membrane, solved the method for this problem, for example, known to have noncrystalline polyolefin be that resin is as protective membrane.Particularly, at least one surface layer of in japanese kokai publication hei 6-51117 communique (patent documentation 2), having put down in writing at polarization element closes thermoplasticity saturated norbornene series resin sheet material as protective membrane.
Situation at the low protective membrane of such Water Vapour Permeability of fitting with device in the past; Use with water as the tackiness agent of primary solvent for example polyvinyl alcohol water solution, protective membrane fitted to the so-called wet type lamination that makes solvent seasoning after the polarization element of polyethenol series; Have and can not get enough bond strengths, or problem such as bad order.This be because, the film that Water Vapour Permeability is low is compared with the tri acetyl cellulose film, is generally hydrophobic, and owing to Water Vapour Permeability is low, thus can not thorough drying as the water of solvent.
Therefore, in TOHKEMY 2000-321432 communique (patent documentation 3), having proposed through the polyurethane series tackiness agent is that the protective membrane of resin carries out the adherent scheme with the polarization element of polyethenol series with comprising the thermoplasticity saturated norbornene.But the polyurethane series tackiness agent has curing needs long problem, and its bounding force is also not necessarily abundant.
On the other hand; The also known scheme that different types of diaphragm of fitting on the two sides of polarization element is arranged; For example in TOHKEMY 2002-174729 communique (patent documentation 4), proposed; One side applying at the polarization element that is made of the polyvinyl alcohol resin film comprises the diaphragm that amorphous polyolefins is a resin; Comprising with this amorphous polyolefins in the another side applying is the for example diaphragm of tri acetyl cellulose of the different resin of resin; And in TOHKEMY 2005-208456 communique (patent documentation 5), proposed; Water system first adhesive by containing the particular polyurethane resin is at a surface layer cyclization olefin-based resin molding of the light polarizing film that comprises polyvinyl alcohol resin, by water system second adhesive different with first adhesive for example the aqueous solution of polyvinyl alcohol resin close the cellulose acetate resin film at another surface layer.
In above-mentioned patent documentation 4, being called as noncrystalline polyolefin is resin or the resin that in above-mentioned patent documentation 5, is called as the cyclic olefine resin; Be to have the monomeric unit that is constituted by norbornylene or derivatives thereof, the such polycycle cycloolefin of dimethano-octahydro naphthalene; And residual when two key is arranged as ring-opening polymerization polymer, the thermoplastic resin that is hydrogenated in preferred two keys.
In addition; In TOHKEMY 2004-245925 communique (patent documentation 6), disclosing with the Resins, epoxy that does not contain aromatic nucleus is the tackiness agent of principal constituent; And proposed to make it carry out cationoid polymerisation, thereby the method for bonding polarization element and protective membrane to this tackiness agent irradiation active energy beam.Though wherein disclosed epoxy is a tackiness agent in that will to be that resin and cellulose-based resin are that the various transparent resin films of representative fit in polarization element with noncrystalline polyolefin effective especially; But find gradually; When being protective membrane with the acrylic resin, its bounding force is not necessarily abundant especially.
The prior art document
Patent documentation
Patent documentation 1: japanese kokai publication hei 7-120617 communique
Patent documentation 2: japanese kokai publication hei 6-51117 communique
Patent documentation 3: TOHKEMY 2000-321432 communique
Patent documentation 4: TOHKEMY 2002-174729 communique
Patent documentation 5: TOHKEMY 2005-208456 communique
Patent documentation 6: TOHKEMY 2004-245925 communique
Summary of the invention
The problem that invention will solve
Problem when through the wet type lamination polarization element of polyethenol series and the low protective membrane of Water Vapour Permeability being fitted in order to solve; Dry furnace superintendent lengthening after having considered to fit is to obtain more time of drying; But when increasing dry furnace superintendent merely, produce the problem that causes variable color because of the thermal degradation when of polarization element easily.Therefore, considered the reduction drying temperature, but in this case,, needed further to increase dry furnace superintendent, had the excessive problem of facility investment for thorough drying so that can not cause the polarization element thermal degradation when.In addition; When different types of protective membrane is fitted on the two sides of polarization element; Because the shrinking percentage that these protective membranes are heated is different; Therefore be bonding with polarization element under the shrinkage different state of two surface protective films; Have when after drying, being back to normal temperature, curling problem takes place in polaroid easily.
In order to improve this problem, can consider to adopt applying method through dry lamination.But; Owing to the viscosity of the tackiness agent with dry lamination suitability is high; Problem a little less than the physical strength of polarization element, the adhesive bonding method of polarization element and protective membrane is subject at the protective membrane coating adhesive, and then it is conformed to the method for polarization element.In the method, before fitting when the coated face of tackiness agent is attached with foreign matter, can't hidden foreign matter, and, therefore become the reason of fleck defect being that starting point produces bubble between tack coat and polarization element with the foreign matter after the applying.
The inventor is being that the low resin molding of the Water Vapour Permeability of resin is during as the polarization element protective membrane in order to develop to be selected from vibrin, polycarbonate resin, acrylic resin and noncrystalline polyolefin; The light solidified tackiness agent that can reveal good adhesion with the activity list of short period of time; And carried out positive research; The result finds to pass through to use specific light solidified tackiness agent, can be with these protective membranes of operation applying of short period of time.So find, though this tackiness agent with the acrylic resin film during as protective membrane, also can be at the high bounding force of performance between itself and the polarization element.
In addition, the adhesive thickness of polaroid from viewpoints such as slimming and weather resistance, is preferably below the 5 μ m, but in order to be coated with solvent-free light solidified tackiness agent, and to obtain thickness be the following level and smooth coated faces of 5 μ m, need carry out the lowering viscousity of tackiness agent., make solvent-freely when being the tackiness agent lowering viscousity, bounding force usually can descend.Yet; The inventor finds; Through using specific light solidified tackiness agent, it is the low viscous while, can and be selected between the protective membrane that vibrin, polycarbonate resin, acrylic resin and noncrystalline polyolefin are resin at polarization element and give play to high adhesion.
Therefore; The objective of the invention is to; The light solidified tackiness agent is provided and uses this tackiness agent to be fitted with the polaroid of protective membrane at polarization element; Even wherein this light solidified tackiness agent is being that the low resin molding of the Water Vapour Permeability of resin is during as protective membrane to be selected from vibrin, polycarbonate resin, acrylic resin and noncrystalline polyolefin; Also can be with sufficient bond strength that protective membrane and polarization element is bonding with the operation of short period of time; And viscosity is low, and after long duration test, also can not cause problems such as bad order.Another object of the present invention is to, the optics that uses this polaroid can form the excellent liquid crystal indicator of reliability is provided, and is applied to liquid crystal indicator.
The method that is used to deal with problems
Promptly; According to the present invention; The light solidified binder composition is provided; It is to be used for protective membrane is bonded in the binder composition that the absorption that comprises uniaxial extension is orientated the polarization element of the polyvinyl alcohol resin film that the dichroism pigment is arranged; This protective membrane comprises and is selected from the transparent resin film that vibrin, polycarbonate resin, acrylic resin and noncrystalline polyolefin are resin, and said composition is characterised in that and contains
(A) intramolecularly have at least 2 epoxy group(ing) and at least 1 aromatic nucleus epoxy compounds,
(B) can have the ester skeleton have carbon number be 5～10 glycol (wherein, except the ether compound) two (methyl) acrylate and
(C) light cationic polymerization initiators,
Containing of said (A)～(C) composition proportionally in composition does
(A) composition: 20～60 weight %
(B) composition: 5～45 weight %
(C) composition: 0.5～10 weight %.
In this light solidified binder composition,, be preferably bisphenol A type epoxy resin as (A) composition.Perhaps, as (B) composition, be preferably neopentyl glycol, hydroxy new pentane acid and acrylic acid esterification reaction product.
In addition, with regard to the light solidified binder composition, in order to make the composition lowering viscousity, and obtain good solidified nature and binding property, in composition, preferably contain 5～45 weight % and be the oxetane compound shown in the following formula (1) of (D) composition.
[Chemical formula 1]
In addition, with regard to the light solidified binder composition,, in composition, preferably contain 1～20 weight % as the oxetane compound shown in the following formula (2) of (E) composition in order to obtain better binding property to dry polarization element.
[Chemical formula 2]
Contained (B) the free-radical polymerised composition that becomes to grade in these light solidified binder compositions; Can solidify through the free radical that (C) composition is produced when being subjected to photolysis; But, preferably contain optical free radical polymerization starter as (F) composition with the ratio below the 10 weight % in order to obtain sufficient reactivity with few irradiation dose.
With regard to these light solidified binder compositions,, preferably in composition, also contain the flow agent of 0.01～0.5 weight % as (G) composition in order to obtain the excellent coated face of smoothness.
In addition; According to the present invention; Polaroid is provided; It is to comprise through tackiness agent that to be selected from vibrin, polycarbonate resin, acrylic resin and noncrystalline polyolefin be that the protective membrane of the transparent resin film of resin fits in the absorption orientation that comprises uniaxial extension and has the polarization element of the polyvinyl alcohol resin film of dichroism pigment to form, and this tackiness agent is formed by above-mentioned any light solidified binder composition.
This polaroid can be through following method manufacturing; This method comprises: be coated with the adhesive coated operation of aforementioned any light solidified binder composition, binder layer through gained in the one side at least of the binding face of polarization element and protective membrane; The bonding process that polarization element and protective membrane are fitted and under the state of polarization element and protective membrane being fitted through this binder layer makes light solidified binder composition solidified curing process.Particularly, can adopt: after uncured above-mentioned light solidified binder composition is coated polarization element, protective membrane is fitted in this binder composition coated face, this binder composition is solidified to form the method for binder layer; After uncured above-mentioned light solidified binder composition coated protective membrane, polarization element is fitted in this binder composition coated face, this binder composition is solidified to form the method for binder layer; The uncured above-mentioned light solidified binder composition of curtain coating between polarization element and protective membrane; Applying thing with clamping polarization elements such as roller and protective membrane; And roll binder composition wide equably; Make its pressing simultaneously, make this binder composition solidify with the method that forms binder layer etc. then.
Further, according to the present invention, provide layer to close above-mentioned polaroid and the optics that shows the optical layers of other optical function.Other optical layers under this situation preferably comprises phase difference film.The liquid crystal indicator that this optics is configured in the one or both sides of liquid crystal cell and forms also is provided.
The invention effect
Light solidified binder composition of the present invention easily solidifies through irradiation ultraviolet radiation isoreactivity energy-ray, with bonding securely polarization element of the operation of short period of time and protective membrane.This binder composition is particularly useful under the situation that protective membrane is made up of acrylic resin.Because this binder composition solidifies with the operation of short period of time, therefore, can productivity make the polaroid that obtains through this binder composition applying polarization element and protective membrane well.Further, the optics with this polaroid and the combination of other optical layers can form the excellent liquid crystal indicator of reliability.
Embodiment
Below, describe the present invention in detail.The present invention will be bonded in by the protective membrane that transparent resin film constitutes when by the absorption of uniaxial extension orientation the polarization element that the polyvinyl alcohol resin film of dichroism pigment constitutes being arranged, and use the light solidified binder composition of specific composition.Like this, polarization element and protective membrane are fitted, obtain polaroid thus through using the light solidified binder composition.This polaroid can be formed optics with having the optics laminated of other optical function.In addition, this optics can be configured at least one side of liquid crystal cell and form liquid crystal indicator.Below, describe according to the order of the method for manufacture of light solidified binder composition, polaroid, polaroid, optics, liquid crystal indicator.
[light solidified binder composition]
The present invention uses the light solidified binder composition of specific composition for polarization element and protective membrane are fitted.Below, abbreviate this light solidified binder composition as " light solidified tackiness agent " or " composition " sometimes.Light solidified tackiness agent of the present invention must contain following (A), (B) and (C) three kinds of compositions.
(A) intramolecularly have at least 2 epoxy group(ing) and at least 1 aromatic nucleus epoxy compounds,
(B) can have the ester skeleton have carbon number be 5～10 glycol (wherein, except the ether compound) two (methyl) acrylate and
(C) light cationic polymerization initiators.
This specification sheets also is called above-mentioned (A) epoxy compounds " (A) composition " or " epoxy compounds (A) "; Also (B) two (methyl) acrylate is called " (B) composition " or " two (methyl) acrylate (B) ", also (C) light cationic polymerization initiators is called " (C) composition " or " light cationic polymerization initiators (C) ".
Make the ratio of (A)～(C) composition in composition do, (A) composition is 20～60 weight %, and (B) composition is 5～45 weight %, and (C) composition is 0.5～10 weight %.
This light solidified tackiness agent; Can contain arbitrarily as the oxetane compound shown in the following formula (1) of (D) composition; As the oxetane compound shown in the following formula (2) of (E) composition; As the optical free radical polymerization starter of (F) composition, and the flow agent of conduct (G) composition.
[chemical formula 3]
[chemical formula 4]
This specification sheets also is called above-mentioned (E) oxetane compound " (E) composition " or " oxetane compound (E) "; Also (F) optical free radical polymerization starter is called " (F) composition " or " optical free radical polymerization starter (F) ", also (G) flow agent is called " (G) composition " or " flow agent (G) ".
< epoxy compounds (A) >
In light solidified tackiness agent of the present invention, form the epoxy compounds of (A) composition, be the compound that has at least 2 epoxy group(ing) and at least 1 aromatic nucleus at intramolecularly, it can use known various solidified nature epoxy compoundss usually.
As the object lesson of (A) composition, can enumerate the bisphenol-type epoxy resin the diglycidylether of diglycidylether and brominated bisphenol A of diglycidylether like dihydroxyphenyl propane, Bisphenol F; Phenolic resin varnish type epoxy resin as phenol novolak type epoxy resin and cresols phenolic resin varnish type epoxy resin; And biphenyl type epoxy resin, quinhydrones diglycidylether, resorcinol diglycidyl ether, terephthalic acid diglycidyl ester, o-phthalic acid diglycidyl ester, end are the polyhutadiene of carboxylic acid and the addition reaction of bisphenol A type epoxy resin etc.
Here, Resins, epoxy is meant the epoxy group(ing) that on average has in the molecule more than 2, solidified compound or polymkeric substance through reaction.According to the convention of this area, in this specification sheets, so long as have the solidified nature compound of 2 above epoxy group(ing) in the molecule, even monomer also is called as Resins, epoxy.
As (A) composition; According to excellent viewpoint such as the solidified nature of composition and binding property; The glycidyl ether of preferred fragrance compounds of group, the more preferably diglycidylether of the diglycidylether of dihydroxyphenyl propane, Bisphenol F and phenol novolak type epoxy resin, especially preferably bisphenol A type epoxy resin.
As bisphenol A type epoxy resin,, can select few goods of cl content or the few goods of number of repeat unit from aspects such as solidified nature.
(A) epoxy compounds of composition can use a kind separately, also can use mixing more than 2 kinds.
With whole compositions is benchmark, and (A) the cooperation ratio of the epoxy compounds of composition is the scope of 20～60 weight %.Through being this ratio, can make composition have the low viscosity that can obtain level and smooth coated face, can access good binding property and solidified nature.
< two (methyl) acrylate (B) >
In light solidified tackiness agent of the present invention, form (B) composition two (methyl) acrylate, be two (methyl) acrylate that carbon number is 5～10 a glycol (wherein, except the ether compound) that has that (B) can have the ester skeleton.
As (B) composition, when using intramolecular (methyl) acryloyl radix to be two more than 3 (methyl) acrylate, the binding property of polarization element is become bad easily.In addition, intramolecular (methyl) acryloyl radix is 1 o'clock, at ultraviolet irradiation amount after a little while, often have remaining monomer residue or cause binding property and weather resistance bad.In addition, even for having the glycol of carbon number 5～10, also not enough to the binding property of polarization element as the glycol of ether compound.
Through using (B) composition, not only reduced the viscosity of composition, even and the high polarization element of ridity is being carried out when bonding, binding property and weather resistance be excellence also.
In (B) composition; Object lesson as two (methyl) acrylate of the glycol with 5～10 carbon numbers; Can enumerate two (methyl) vinylformic acid DOPCP, two (methyl) vinylformic acid 1; 6-hexylene glycol ester, two (methyl) vinylformic acid 3-methyl isophthalic acid; 5-pentadiol ester, two (methyl) vinylformic acid 2-butyl-2-ethyl-1; Ammediol ester and two (methyl) vinylformic acid 1,9-nonanediol ester etc.
(B) composition can have the ester skeleton, as object lesson, can enumerate neopentyl glycol, hydroxy new pentane acid and (methyl) acrylic acid esterification reaction product etc.
Wherein, according to lowering viscousity, binding property, weather resistance, low odor, the excellent viewpoint of low skin irritability, preferred especially neopentyl glycol, hydroxy new pentane acid and (methyl) acrylic acid esterification reaction product.
With whole compositions is benchmark, and (B) the cooperation ratio of composition is the scope of 5～45 weight %.Through being this ratio, can access excellent coating that viscosityization brings and good binding property.(B) the more preferably cooperation ratio of composition is 10～40 weight %, and further is preferably 15～40 weight %.
< light cationic polymerization initiators (C) >
Light solidified tackiness agent of the present invention; Contain above the epoxy compounds (A) of explanation and as required after the oxetane compound stated as cure component; In them any all solidifies through cationoid polymerisation, therefore cooperates the light cationic polymerization initiators as (C) composition.This light cationic polymerization initiators through irradiation visible light, ultraviolet ray, X ray, electron beam isoreactivity energy-ray, and produces positively charged ion kind or Lewis acid, thereby causes the polyreaction of epoxy group(ing) or oxetanyl.
Through cooperating light cationic polymerization initiators as (C) composition, can solidify at normal temperatures, can reduce the thermotolerance of considering polarization element and because of expanding or shrink the necessity that causes distortion, and bonding well protective membrane.In addition, owing to the light cationic polymerization initiators is brought into play catalyst action under the irradiation of active energy beam, therefore, even mix with epoxy compounds (A) and oxetane compound (B), its storage stability, operation property are also excellent.As producing positively charged ion kind or lewis acidic compound, can enumerate salt as aromatic series diazonium salt, aromatic series salt compounded of iodine and aromatic series sulfonium salt, iron-propadiene complex compound etc. through the irradiation active energy beam.
As the aromatic series diazonium salt, for example can enumerate following compound.
Benzene diazonium hexafluoro antimonate,
Benzene diazonium hexafluorophosphate,
Benzene diazonium hexafluoro borate etc.
As the aromatic series salt compounded of iodine, for example can enumerate following compound.
Phenylbenzene iodine four (pentafluorophenyl group) borate,
Diphenyl iodine hexafluorophosphate,
Phenylbenzene iodine hexafluoro antimonate,
Two (4-nonyl phenyl) iodine hexafluorophosphate etc.
As the aromatic series sulfonium salt, for example can enumerate following compound.
The triphenylsulfonium hexafluorophosphate,
The triphenylsulfonium hexafluoro antimonate,
Triphenylsulfonium four (pentafluorophenyl group) borate,
The two hexafluorophosphates of 4,4 '-two (phenylbenzene sulfonium base) diphenyl sulfide,
The two hexafluoro antimonates of 4,4 '-two [two (beta-hydroxy oxyethyl group) phenyl sulfonium base] diphenyl sulfide,
The two hexafluorophosphates of 4,4 '-two [two (beta-hydroxy oxyethyl group) phenyl sulfonium base] diphenyl sulfide,
7-[two (to toluyl) sulfonium base)-2-isopropyl thioxanthone hexafluoro antimonate,
7-[two (to toluyl) sulfonium base)-2-isopropyl thioxanthone four (pentafluorophenyl group) borate,
4-phenylcarbonyl group-4 '-phenylbenzene blunderbuss base-diphenyl sulfide hexafluorophosphate,
4-(to the tert-butyl-phenyl carbonyl)-4 '-phenylbenzene blunderbuss base-diphenyl sulfide hexafluoro antimonate,
4-(to the tert-butyl-phenyl carbonyl)-4 '-two (to toluyl) sulfonium base-diphenyl sulfide four (pentafluorophenyl group) borate etc.
As iron-propadiene complex compound, can enumerate following compound.
Xylenes-cyclopentadienyl iron (II) hexafluoro antimonate,
Cumene-cyclopentadienyl iron (II) hexafluorophosphate,
Xylenes-cyclopentadienyl iron (II)-three (trifluoromethyl sulfonyl) methide etc.
These light cationic polymerization initiators can use a kind separately separately, also can use mixing more than 2 kinds.Wherein, even owing to particularly also have the ultraviolet radiation absorption characteristic in the wavelength region may of aromatic series blunderbuss salt more than 300nm, thereby the cured article that solidified nature is excellent, have good mechanical strength and bond strength can be provided, therefore preferred use.
With regard to (C) composition; Can easily obtain commercially available article; For example, can enumerate " the カ ヤ ラ Star De PCI-220 " that representes with trade(brand)name respectively; " カ ヤ ラ Star De PCI-620 " (above is Japanese chemical drug (strain) system); " UVI-6992 " (De ウ ケ ミ カ Le society system); " ア デ カ オ プ ト マ one SP-150 "; " ア デ カ オ プ ト マ one SP-160 " (above is (strain) ADEKA system); " CI-5102 "; " CIT-1370 "; " CIT-1682 "; " CIP-1866S "; " CIP-2048S "; " CIP-2064S " (above is Japanese Cao Da (strain) system); " 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 " (above is body ど り chemistry (strain) system); " PI-2074 " (ロ one デ イ ア society system); " IRGACURE 250 "; " IRGACURE PAG103 "; IRGACURE PAG108 "; IRGACURE PAG121 "; IRGACURE PAG203 " (above is vapour corporate system in the sixth of the twelve Earthly Branches); " CPI-100P "; " CPI-101A "; " CPI-210S " (above is サ Application ア プ ロ (strain) system) etc.Particularly, according to solidified nature and fusible viewpoint, the CPI-100P that preferred especially サ Application ア プ ロ (strain) makes.
With whole compositions is benchmark, and (C) the cooperation ratio of composition is the scope of 0.5～10 weight %.When this ratio during less than 0.5 weight %, the curing of tackiness agent is insufficient, and physical strength and bond strength descend; On the other hand, when this ratio surpassed 10 weight %, the ionic substance in the cured article increased; Therefore the water absorbability of cured article increases, and endurance quality reduces, and is therefore not preferred.
< oxetane compound (D) >
In light solidified tackiness agent of the present invention; For the lowering viscousity that obtains composition and good solidified nature and binding property; The preferred compound that cooperates as structure shown in the aforementioned formula (1) of (D) composition, i.e. 3-ethyl-3-[(3-ethyl trimethylene oxide-3-yl) methoxymethyl] trimethylene oxide.
As the cooperation ratio of (D) composition, be benchmark with whole compositions, be the scope of 5～45 weight %.Through being this ratio, can make composition have the low viscosity that can obtain level and smooth coated face, can access good binding property and solidified nature.
< oxetane compound (E) >
In light solidified tackiness agent of the present invention; Even at polarization element when more composition also need be brought into play excellent adhesiveness under the dry situation; The preferred compound that cooperates as structure shown in the aforementioned formula (2) of (E) composition, i.e. 3-ethyl-3-hydroxymethyl trimethylene oxide.
To the binding property of exsiccant polarization element more when good, the cooperation ratio that forms the oxetane compound of (E) composition is a benchmark with whole compositions, preferably contains 1～20 weight %.If it is less than 1 weight %, then often additive effect is little, when its during more than 20 weight %, often solidified nature variation, binding property descend.
< optical free radical polymerization starter (F) >
Contained (B) the radically curing property composition that becomes to grade can solidify through the free radical that (C) composition is produced when being subjected to photolysis in the light solidified tackiness agent of the present invention; But in order to obtain sufficient reactivity with few irradiation dose, the preferred optical free radical polymerization starter that cooperates as (F) composition.With whole compositions is benchmark, and (F) the cooperation ratio of composition is preferably following, 0.1～3 weight % more preferably of 10 weight %.When use level is 10 weight % when above, often cause the decline of weather resistance, therefore not preferred.
As the object lesson of (F) composition, for example, can enumerate following compound.
Like 4 '-phenoxy group-2; The 2-Er Lvyixianben; 4 '-tertiary butyl-2; The 2-Er Lvyixianben; 2; 2-dimethoxy-2-phenyl acetophenone; 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholinyl third-1-ketone; The 1-hydroxycyclohexylphenylketone; α, α-diethoxy phenyl methyl ketone; 2-hydroxy-2-methyl-1-phenyl third-1-ketone; 1-(4-isopropyl phenyl)-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 such acetyl benzene series Photoepolymerizationinitiater initiater of 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) fourth-1-ketone;
Benzoin ether as bitter almond oil camphor, benzoin methyl ether, bitter almond oil camphor ethyl ether, bitter almond oil camphor isopropyl ether and bitter almond oil camphor isobutyl ether is a Photoepolymerizationinitiater initiater;
Like UVNUL MS-40, o-benzoyl yl benzoic acid methyl esters, 4-phenyl benzophenone, 4-benzoyl-4 '-methyldiphenyl base sulfide and 2,4, the benzophenone series Photoepolymerizationinitiater initiater that the 6-tri-methyl benzophenone is such;
Like 2-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-two clopenthixal ketones and the such thioxanthone of 1-chloro-4-propoxy-thioxanthone are Photoepolymerizationinitiater initiater;
As 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, two (2,6-dimethoxy benzoyl)-2,4,4-tri-methyl-amyl phosphine oxide is a Photoepolymerizationinitiater initiater with two (2,4, the 6-trimethylbenzoyl) such acylphosphine oxide of phenylphosphine oxide;
1,2-acetyl caproyl, 1-[4-(thiophenyl phenyl)]-, the such oxime ester of 2-(O-benzoyl oxime) is a Photoepolymerizationinitiater initiater;
Camphorquinone etc.
With regard to (F) composition, can use a kind separately, also can cooperate more than 2 kinds and use according to the performance of hope.When cooperating the optical free radical polymerization starter of (F) composition, its cooperation ratio is a benchmark with whole compositions, is preferably below the 10 weight %, more preferably 0.1～3 weight %.When the amount of optical free radical polymerization starter (F) is too much, often can't obtain enough intensity, in addition, during its quantity not sufficient, often tackiness agent can't fully solidify.
< flow agent (G) >
In light solidified tackiness agent of the present invention,, preferably contain (G) composition flow agent in order to obtain the excellent coated face of smoothness.
As (G) composition, can enumerate silicon-type flow agent and fluorine is flow agent etc., can use commercially available various flow agents.
(G) the preferred cooperation ratio of composition is a benchmark with whole compositions, is 0.01～0.5 weight %.When adding umber and be less than 0.01 part, the additive effect of flow agent is little, on the contrary, when its during more than 0.5 part, binding property descends.
< other solidified nature composition >
Light solidified tackiness agent of the present invention except above-mentioned (A)～(G) composition, can also contain other cation-curable composition or radically curing property composition.
As (A) composition, (D) composition and (E) the cation-curable composition beyond the composition, can enumerate various epoxy compoundss or oxetane compound and vinyl ether compound.
Object lesson as the epoxy compounds beyond (A) composition; Can enumerate the Dicyclopentadiene (DCPD) dioxide; The limonene dioxide; The 4 vinyl cyclohexene dioxide; 3; 4-epoxy group(ing) cyclohexyl methyl-3; 4-epoxy-cyclohexane carboxylicesters; Two (3; 4-epoxy group(ing) cyclohexyl methyl) adipic acid ester; 1; The 6-hexanediol diglycidyl ether; Trihydroxymethylpropanyltri diglycidyl ether; Tetramethylolmethane four glycidyl ethers; Gather 1; The 4-butanediol diglycidyl ether; The Hydrogenated Bisphenol A diglycidylether; Epoxidized vegetable oil; 2-(3; 4-epoxy group(ing) cyclohexyl) ethyl trimethoxy silane; 2-(3; 4-epoxy group(ing) cyclohexyl) ethyl triethoxysilane; The 3-glycidoxypropyltrimewasxysilane; 3-glycidoxypropyl methyl dimethoxysilane; Two ends are the polyhutadiene diglycidylether of hydroxyl; The inner loop oxide compound of polyhutadiene; Two keys of styrene-butadiene copolymer by the epoxidised compound of part (for example; " the エ Port Off レ Application De " that ダ イ セ Le chemical industry (strain) is made); And the isoprene unit of the segmented copolymer of ethylene-butene copolymer and polyisoprene is by epoxidised compound of part (for example, " L-207 " of KRATON manufactured) etc.
Object lesson as (D) composition and oxetane compound beyond (E) composition; Can enumerate the such simple function trimethylene oxide that contains alkoxyalkyl of 3-ethyl-3-(2-ethyl hexyl oxy methyl) trimethylene oxide; The simple function trimethylene oxide that contains the aromatic series base that 3-ethyl-3-phenoxymethyl trimethylene oxide is such; 1; Two [(the 3-ethyl trimethylene oxide-3-yl) methoxymethyl] benzene of 4-; 1; Two [(the 3-ethyl trimethylene oxide-3-yl) methoxyl group] benzene of 4-; 1; Two [(the 3-ethyl trimethylene oxide-3-yl) methoxyl group] benzene of 3-; 1; Two [(the 3-ethyl trimethylene oxide-3-yl) methoxyl group] benzene of 2-; 4; 4 '-two [(3-ethyl trimethylene oxide-3-yl) methoxyl group] biphenyl; 2; 2 '-two [(3-ethyl trimethylene oxide-3-yl) methoxyl group] biphenyl; 3; 3 '; 5; 5 '-tetramethyl--4; 4 '-two [(3-ethyl trimethylene oxide-3-yl) methoxyl group] biphenyl; 2; Two [(the 3-ethyl trimethylene oxide-3-yl) methoxyl group] naphthalenes of 7-; Two [4-{ (3-ethyl trimethylene oxide-3-yl) methoxyl group } phenyl] methane; Two [2-{ (3-ethyl trimethylene oxide-3-yl) methoxyl group } phenyl] methane; 2; 2-pair [4-{ (3-ethyl trimethylene oxide-3-yl) methoxyl group } phenyl] propane; The etherification modified thing that utilizes 3-chloromethyl-3-ethyl trimethylene oxide of phenolic varnish type resol; 3 (4), 8 (9)-two [(3-ethyl trimethylene oxide-3-yl) methoxymethyl]-three ring [5.2.1.0
2.6] decane; 2; Two [(the 3-ethyl trimethylene oxide-3-yl) methoxymethyl] norbornanes of 3-; 1; 1; 1-three [(3-ethyl trimethylene oxide-3-yl) methoxymethyl] propane; 1-butoxy-2; Two [(the 3-ethyl trimethylene oxide-3-yl) methoxymethyl] butane of 2-; 1; Two [{ 2-(the 3-ethyl trimethylene oxide-3-yl) methoxyl group } ethyl sulfenyl] ethane of 2-; Two [{ 4-(3-ethyl trimethylene oxide-3-yl) methyl sulfenyl } phenyl] sulfide; 1; Two [(the 3-ethyl trimethylene oxide-3-yl) methoxyl groups]-2 of 6-; 2; 3; 3; 4; 4; 5,5-octafluoro hexane; 3-[(3-ethyl trimethylene oxide-3-yl) methoxyl group] propyl trimethoxy silicane; 3-[(3-ethyl trimethylene oxide-3-yl) methoxyl group] propyl-triethoxysilicane; 3-[(3-ethyl trimethylene oxide-3-yl) methoxyl group] hydrolytic condensate of propyl trialkoxy silane; The condenses of four [(3-ethyl trimethylene oxide-3-yl) methyl] silicon ester etc.
As the object lesson of vinyl ether compound, can enumerate cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, dodecyl vinyl, 4-hydroxybutyl vinyl ether, Diethylene Glycol mono vinyl ether, triethylene glycol divinyl ether, cyclohexanedimethanol divinyl ether etc.
(A) composition, (D) composition and (E) the cooperation ratio of the cation-curable composition beyond the composition are benchmark with whole compositions, are preferably less than 20 weight %, more preferably less than 10 weight %, especially preferably less than 5 weight %.
As the radically curing property composition beyond (B) composition; Can enumerate all cpds; For example, can enumerate (methyl) esters of acrylic acid, (methyl) acrylic amide, maleimide, (methyl) vinylformic acid, toxilic acid, methylene-succinic acid, (methyl) propenal, (methyl) acryloyl morpholine, N-vinyl-2-Pyrrolidone, cyanacrylate, hexanodioic acid divinyl ester, vinyltrimethoxy silane etc.
Object lesson as (methyl) esters of acrylic acid that has 1 (methyl) acryl at intramolecularly; Can enumerate (methyl) methyl acrylate; (methyl) ethyl propenoate; (methyl) propyl acrylate; (methyl) isopropyl acrylate; (methyl) Bing Xisuandingzhi; (methyl) isobutyl acrylate; (methyl) 2-EHA; (methyl) Octyl acrylate; (methyl) Isooctyl acrylate monomer; (methyl) lauryl acrylate; (methyl) vinylformic acid stearyl; (methyl) vinylformic acid 2-hydroxy methacrylate; (methyl) vinylformic acid 2-hydroxy propyl ester; (methyl) vinylformic acid 4-hydroxyl butyl ester; (methyl) cyclohexyl acrylate; (methyl) IBOA; 1; 4-hexanaphthene dihydroxymethyl list (methyl) acrylate; Two cyclopentyl (methyl) acrylate; Dicyclopentenyl (methyl) acrylate; Dicyclopentenyl oxygen base ethyl (methyl) acrylate; (methyl) vinylformic acid benzyl ester; (methyl) acrylate of oxidation of phenol alkene affixture; (methyl) acrylate to cumyl phenol oxyalkylene affixture; (methyl) acrylate of orthoxenol oxyalkylene affixture; (methyl) acrylate of nonylphenol oxyalkylene affixture; 2-methoxy ethyl (methyl) acrylate; Ethoxy ethoxy ethyl (methyl) acrylate; (methyl) acrylate of the oxyalkylene affixture of 2-ethylhexyl alcohol; Glycol monomethyl (methyl) acrylate; Ucar 35 list (methyl) acrylate; Pentanediol list (methyl) acrylate; Hexylene glycol list (methyl) acrylate; The list of Diethylene Glycol (methyl) acrylate; The list of triethylene glycol (methyl) acrylate; The list of TEG (methyl) acrylate; The list of polyoxyethylene glycol (methyl) acrylate; The list of dipropylene glycol (methyl) acrylate; The list of tripropylene glycol (methyl) acrylate; The list of polypropylene glycol (methyl) acrylate; 2-hydroxyl-3-phenoxy propyl (methyl) acrylate; 2-hydroxyl-3-butoxy propyl group (methyl) acrylate; (methyl) tetrahydrofurfuryl acrylate; Caprolactone modification (methyl) tetrahydrofurfuryl acrylate; (2-ethyl-2-methyl isophthalic acid; 3-dioxolane-4-yl) methyl (methyl) acrylate; (2-isobutyl--2-methyl isophthalic acid; 3-dioxolane-4-yl) methyl (methyl) acrylate; (1; 4-dioxy spiral shell [4; 5] methyl (methyl) acrylate decane-2-yl); (methyl) glycidyl acrylate; 3,4-epoxy group(ing) cyclohexyl methyl (methyl) acrylate; (3-ethyl trimethylene oxide-3-yl) methyl (methyl) acrylate; 2-(methyl) acryloxy ethyl isocyanate; (methyl) allyl acrylate; N-(methyl) acryloxy ethyl hexahydrophthalic phthalimide; N-(methyl) acryloxy ethyl tetrahydric phthalimide; 2-(methyl) acryloxy ethyl hexahydrophthalic acid; 2-(methyl) acryloxy ethyl succsinic acid; ω-carboxyl-polycaprolactone list (methyl) acrylate; 2-(methyl) acryloxy ethyl acid phosphoric acid ester; 3-(methyl) acryloxy propyl trimethoxy silicane; 3-(methyl) acryloxy propyl group dimethoxy-methyl silane; 3-(methyl) acryloxy propyl-triethoxysilicane etc.
In addition; As the object lesson of (methyl) esters of acrylic acid beyond (B) composition that has (methyl) acryl more than 2 at intramolecularly, can enumerate tristane dihydroxymethyl two (methyl) acrylate; Two (methyl) acrylate of dihydroxyphenyl propane oxyalkylene affixture; Two (methyl) acrylate of Hydrogenated Bisphenol A; Two (methyl) acrylate of bisphenol A diglycidyl ether; Ethylene glycol bisthioglycolate (methyl) acrylate; Diethylene Glycol two (methyl) acrylate; Triethylene glycol two (methyl) acrylate; Ucar 35 two (methyl) acrylate; Dipropylene glycol two (methyl) acrylate; Tripropylene glycol two (methyl) acrylate; Trimethylolpropane tris (methyl) acrylate; Three (methyl) acrylate of the oxyalkylene affixture of TriMethylolPropane(TMP); Two-TriMethylolPropane(TMP) four (methyl) acrylate; Tetramethylolmethane three (methyl) acrylate; Tetramethylolmethane four (methyl) acrylate; Dipentaerythritol five (methyl) acrylate; Dipentaerythritol six (methyl) acrylate; Two or three (methyl) acrylate of isocyanuric acid oxyalkylene affixture; Urethane (methyl) acrylate; Polyester (methyl) acrylate and epoxy group(ing) (methyl) acrylate etc.
Object lesson as (methyl) acrylic amide; Can enumerate (methyl) acrylamide, N; N-dimethyl (methyl) acrylamide, N; N-diethyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-(3-N; The N-dimethylaminopropyl) (methyl) acrylamide, methylene-bis (methyl) acrylamide, ethylenebis (methyl) acrylamide, N, N-diallyl (methyl) acrylamide etc.
As the object lesson of maleimide, can enumerate the urethane acrylate of N-methyl maleimide, N-hydroxyethyl maleimide, N-hydroxyethyl citraconimide, N-hydroxyethyl citraconimide and isophorone diisocyanate etc.
With whole compositions is benchmark, and (B) the cooperation ratio of the radically curing property composition beyond the composition is preferably less than 20 weight %, more preferably less than 10 weight %, and especially preferably less than 5 weight %.
< other composition that does not have solidified nature >
Photocurable pressure-sensitive adhesive of the present invention also can be in the scope of not damaging effect of the present invention further cooperation other composition of not having solidified nature arbitrarily, particularly, can enumerate photosensitizers, hot cationic polymerization initiators, polyol compound, water etc.
As the object lesson of photosensitizers, can enumerate UVNUL MS-40, o-benzoyl yl benzoic acid methyl esters, 2-isopropyl thioxanthone, 9,10-dibutoxy anthracene etc.Wherein, though the compound that is equivalent to aforementioned (F) composition optical free radical polymerization starter is also arranged, so-called here photosensitizers is to become the material of beam split cationic polymerization initiators as sensitizer with respect to (C).They can use separately separately, also can use mixing more than 2 kinds.
With whole compositions is benchmark, and the cooperation ratio of photosensitizers is preferably less than 3 weight %.
As the object lesson of hot cationic polymerization initiators, can enumerate benzyl sulfonium salt, thiophene salt, tetrahydro-thiophene salt (チ ォ ラ ニ ゥ system salt), benzyl ammonium salt, pyridinium salt, hydrazonium salt, carboxylicesters, sulphonate, amine imide etc.These initiators can obtain commercially available article at an easy rate; For example, can enumerate " the ァ デ カ ォ プ ト Application CP77 " and " ァ デ カ ォ プ ト Application CP66 " that represent with trade(brand)name respectively (above be (strain) ADEKA system), " CI-2639 " and " CI-2624 " (above be that Japanese Cao Da (strain) makes), " サ Application ェ ィ De SI-60L ", " サ Application ェ ィ De SI-80L " and " サ Application ェ ィ De SI-100L " (more than be that three new chemical industry (strain) are made) etc.
With whole compositions is benchmark, and the cooperation ratio of hot cationic polymerization initiators is preferably less than 3 weight %.
As the object lesson of polyol compound, can enumerate polyether polyols, polyester polyols alkylol cpd, polycaprolactone polyol compound, polycarbonate polyol compound etc.
With whole compositions is benchmark, and the cooperation ratio of polyol compound is preferably less than 5 weight %.
With regard to the viscosity of Photocurable pressure-sensitive adhesive of the present invention; For the coating that obtains in the manufacturing process of polaroid, can using; Even promptly for film also obtains the excellent coated face of smoothness, preferably the viscosity under 25 ℃ is below the 200mPas, more preferably below the 150mPas.
With regard to Photocurable pressure-sensitive adhesive of the present invention,, also can add a spot of water in order to obtain good adhesion to the high polarization element of ridity.Under this situation, be benchmark with whole compositions, the addition of water is preferably less than 3 weight %, more preferably less than 1 weight %.
In addition, only otherwise damage effect of the present invention, can also cooperate ion capturing agent, oxidation inhibitor, photostabilizer, chain-transfer agent, tackifier, thermoplastic resin, metal oxide microparticle, defoamer, pigment, organic solvent etc.
[polaroid]
Above Shuo Ming light solidified tackiness agent is used for protective membrane is bonded in the polarization element that the absorption orientation by uniaxial extension has the polyvinyl alcohol resin film of dichroism pigment to be constituted, and thus protective membrane is fitted in polarization element to form polaroid.That is the polaroid that, the present invention relates to is the polaroid that is fitted with protective membrane at the polarization element that the absorption orientation by uniaxial extension has the polyvinyl alcohol resin film of dichroism pigment to be constituted.Protective membrane can only be fitted in the one side of polarisation optical element, also can be fitted in the two sides of polarization element.When at the two sides of polarization element applying protective membrane, each protective membrane can be by the resin formation of identical type, also can be by different types of resin formation.
< polarization element >
The polyvinyl alcohol resin that constitutes polarization element is through being that the resin saponification obtains with polyvinyl acetate.As polyvinyl acetate is resin, except polyvinyl acetate as leifa, can also give an example vinyl-acetic ester with can be with other monomeric multipolymer of its copolymerization etc.As can with other monomer of vinyl acetate copolymerization, for example, can enumerate unsaturated carboxylic acid class, olefines, vinyl ethers, unsaturated sulfonic acid class etc.The saponification deg of polyvinyl alcohol resin is generally the scope of 85～100 moles of %, preferred 98～100 moles of %.This polyvinyl alcohol resin, further modification for example, can be used by aldehydes modified polyethylene alcohol formal or polyvinylacetal etc.The polymerization degree of polyvinyl alcohol resin is generally 1000～10000, is preferably 1500～10000 scope.
Polaroid is through following operation manufacturing, with such polyvinyl alcohol resin film carry out uniaxial extension operation, with the dichroism pigment to the polyvinyl alcohol resin film dye operation of making its this dichroism pigment of absorption, with boric acid aqueous solution handle the operation of the polyvinyl alcohol resin film that has adsorbed the dichroism pigment, the operation of washing after using boric acid aqueous solution to handle and protective membrane fitted in implemented the operation that these operations and absorption have been orientated the uniaxial extension polyvinyl alcohol resin film of dichroism pigment.
Uniaxial extension can carry out before utilizing the dichroism pigment dyeing, also can when utilizing the dichroism pigment dyeing, carry out, and can also after utilizing the dichroism pigment dyeing, carry out.When after utilizing the dichroism pigment dyeing, carrying out uniaxial extension, this uniaxial extension can carry out before boric acid is handled, and also can in boric acid is handled, carry out.In addition, can certainly in this several stages, carry out uniaxial extension.Uniaxial extension can also can use hot-rolling along uniaxial extension along uniaxial extension between the different roller of circumferential speed.In addition, can be tensile dry type stretching in atmosphere, also can be to carry out the tensile wet type under the state of solvent-swollen and stretch utilizing.Stretching ratio is generally about 4～8 times.
When using the dichroism pigment that the polyvinyl alcohol resin film is dyeed, for example, need only the polyvinyl alcohol resin film immersion in the aqueous solution that contains the dichroism pigment.As the dichroism pigment, specifically, can use iodine or dichroic dye.
When using iodine, be employed in usually and flood the polyvinyl alcohol resin film in the aqueous solution that contains iodine and potassiumiodide and carry out painted method as the dichroism pigment.Normally per 100 weight parts waters of the content of the iodine in this aqueous solution are about 0.01～0.5 weight part, and normally per 100 weight parts waters of the content of potassiumiodide are about 0.5～10 weight part.The temperature of this aqueous solution is generally about 20～40 ℃, and in addition, the dipping time in this aqueous solution was generally about 30～300 seconds.
On the other hand, when using dichroic dye, be employed in the next painted method of dipping polyvinyl alcohol resin film in the aqueous solution that comprises water-soluble dichroic dye usually as the dichroism pigment.The content of the dichroic dye in this aqueous solution, normally per 100 weight parts waters are 1 * 10
-3～1 * 10
-2About weight part.This aqueous solution also can contain inorganic salt such as sodium sulfate.The temperature of this aqueous solution is generally about 20～80 ℃, and in addition, the dipping time in this aqueous solution was generally about 30～300 seconds.
Utilize the boric acid after the dichroism pigment dyes to handle, can be through painted polyvinyl alcohol resin film immersion be carried out in boric acid aqueous solution.Normally per 100 weight parts waters of the content of the boric acid in the boric acid aqueous solution are about 2～15 weight parts, are preferably about 5～12 weight parts.When using iodine as the dichroism pigment, this boric acid aqueous solution preferably contains potassiumiodide.The content of the potassiumiodide in the boric acid aqueous solution, normally per 100 weight parts waters is about 2～20 weight parts, be preferably 5～15 weight parts.Dipping time in boric acid aqueous solution was generally about 100～1200 seconds, was preferably about 150～600 seconds, further was preferably about 200～400 seconds.The temperature of boric acid aqueous solution is generally more than 50 ℃, is preferably 50～85 ℃.
Polyvinyl alcohol resin film to after the boric acid processing is washed processing usually.Washing is handled for example through borated polyvinyl alcohol resin film immersion is carried out in water.Drying treatment is implemented in the washing back, obtains polarization element.The temperature of the water during washing is handled is generally about 5～40 ℃, and dipping time was generally about 2～120 seconds.Thereafter the drying treatment of carrying out uses hot air dryer or far infra-red heater to carry out usually.Drying temperature is generally 40～100 ℃.Treatment time in the drying treatment was generally about 120～600 seconds.
Like this, can obtain being orientated the polarization element that the polyvinyl alcohol resin film as the iodine of dichroism pigment or dichroic dye is constituted by absorption.
< protective membrane >
Then, this polarization element uses the illustrated light solidified tackiness agent in front, at its one or both sides applying protective membrane.All the time, as the protective membrane of polarization element and the tri acetyl cellulose film that extensively adopts has the 400g/m of being roughly
2Water Vapour Permeability about/24hr; And among the present invention; As the protective membrane of being fitted in the one side at least of polarization element, adopting vibrin, polycarbonate resin, acrylic resin or noncrystalline polyolefin as the resin that demonstrates lower Water Vapour Permeability than said tri acetyl cellulose is resin.
The kind that can be used for the vibrin of protective membrane does not have special qualification, considers from aspects such as mechanical properties, solvent resistance, scratch resistance, costs, preferred especially polyethylene terephthalate.Polyethylene terephthalate is meant the above resin that is made up of ethylene glycol terephthalate of 80 moles of % of repeating unit, and can contain the formation unit from other copolymer composition.As other copolymer composition; Can enumerate like m-phthalic acid, right-beta-hydroxy ethoxybenzoic acid, 4; 4 '-dicarboxylate biphenyl, 4; 4 '-benzophenonedicarboxylic acid, two (4-carboxyl phenyl) ethane, hexanodioic acid, sebacic acid, 5-sodiosulfoisophthalic acid and 1, the dicarboxylic acid composition that 4-dicarboxylic acid basic ring hexane is such; Like ethylene oxide adduct, polyoxyethylene glycol, the polypropylene glycol of Ucar 35, butyleneglycol, neopentyl glycol, Diethylene Glycol, cyclohexanediol, dihydroxyphenyl propane with gather 1, the diol component that the 4-butyleneglycol is such etc.For these dicarboxylic acid composition or diol component, can respectively it be made up use more than 2 kinds as required.In addition, can also and use the hydroxycarboxylic acid as P-hydroxybenzoic acid and above-mentioned dicarboxylic acid composition or glycol component.As other copolymer composition, also can use on a small quantity have amido linkage, the dicarboxylic acid composition and/or the glycol component of amino-formate bond, ehter bond, carbonic acid ester bond etc.
Method of manufacture as vibrin; Can adopt make terephthalic acid and terepthaloyl moietie (and; Other dicarboxylic acid as required and/or other dibasic alcohol) the so-called direct polymerization method of direct reaction, the dimethyl ester that makes terephthalic acid and terepthaloyl moietie (and, the dimethyl esters of other dicarboxylic acid as required and/or other dibasic alcohol) carries out any means such as so-called transesterification reaction method of transesterification reaction.In addition, vibrin also can contain known additive as required.As the additive that can contain, for example, can enumerate lubricant, anti, thermo-stabilizer, antioxidant, static inhibitor, photostabilizer, shock resistance improving agent etc.But, needing the transparency owing to be laminated in the protective membrane of light polarizing film, therefore preferred amount with these additives is limited in inferior limit.
Through being membranaceous with the above-mentioned raw materials ester moulding, implement uniaxial extension or biaxial stretch-formed processing, can make the protective membrane that constitutes by the tensile vibrin.Through implementing stretch processing, can obtain the high film of physical strength.The method of manufacture of tensile polyester resin film is arbitrarily, and not special the qualification can be enumerated following method; With the fusion of above-mentioned raw materials resin; With tenter machine under the temperature more than the second-order transition temperature, extrusion moulding is flaky non-oriented film cross directional stretch after, implement heat setting type and handle.
When using vibrin as protective membrane, in order to obtain good binding property, preferably before coating adhesive, implement corona treatment, perhaps use to have the polyester resin film that the surface is prone to the adhesion process layer.
The polycarbonate resin that is used for protective membrane is by carbonic acid and dibasic alcohol or the formed polyester of bis-phenol.Wherein, in molecular chain, have the aromatic copolycarbonate of hydrocarbon with two phenyls alkane, because thermotolerance, weathering resistance and acid resistance are excellent, therefore preferred the use.As such polycarbonate; Can enumerate as 2; Two (4-hydroxy phenyl) propane (having another name called dihydroxyphenyl propane), 2 of 2-; Two (4-hydroxy phenyl) butane, 1 of 2-; 1-bis(4-hydroxyphenyl) cyclohexane, 1; Two (4-hydroxy phenyl) Trimethylmethanes or 1 of 1-, two (4-hydroxy phenyl) ethane of 1-such by bisphenols institute deutero-polycarbonate.
As the method for manufacture of polycarbonate resin adipose membrane, can use any one methods such as casting film method, extrusion by melting.Example as concrete method of manufacture; Can enumerate polycarbonate resin is dissolved in the suitable organic solvent; Form polycarbonate resin solution; With its curtain coating on the metal support; Form reticulation; And this reticulation peeled off from the aforementioned metal support, the reticulation after will peeling off is then carried out warm air drying and is obtained the method for film.
The acrylic resin that is used for protective membrane, not special limit is the polymkeric substance of principal monomer with the methacrylic ester normally, and is preferably the multipolymer that makes a small amount of other comonomer composition and its copolymerization.Methacrylic ester as the acrylic resin principal constituent is generally alkyl methacrylate, and especially preferably uses methyl methacrylate.In addition, as the comonomer composition, use methyl acrylate, ethyl propenoate, Bing Xisuandingzhi, 2-EHA etc. usually.Also can be further with like aromatic ethenyl compound the vinylbenzene or the thiazolinyl nitrile compound as vinyl cyanide etc. as the comonomer composition.
As the method for manufacture of acrylic resin, can adopt any means such as common mass polymerization, suspension polymerization, letex polymerization.Wherein, especially preferably be employed in the mass polymerization that does not have water soluble component in the polymerization system.In addition, in order to obtain suitable second-order transition temperature,, preferably when polymerization, use chain-transfer agent perhaps in order to obtain demonstrating the suitable viscosity of film forming plasticity.The amount of chain-transfer agent, decision gets final product with forming suitably according to monomeric kind.In addition, for acrylic resin, can contain known additive as required.As known additive, for example can enumerate lubricant, anti, thermo-stabilizer, antioxidant, static inhibitor, photostabilizer, shock resistance improving agent, tensio-active agent etc.But, need the transparency owing to be laminated in the protective membrane of light polarizing film, so the amount of these additives is preferably limited to inferior limit.
As the method for manufacture of acrylic resin film, also can use any methods such as extrusion by melting as fusion casting method, T modulus method or blow moulding, rolling process.Wherein,, preferably material resin is for example melt extruded by the T mould according to the viewpoint that can obtain the good film of surface texture, make the gained membranoid substance at least-face and roller or band contact and make the method for film.
From the viewpoints such as shock resistance of film forming system film property and film, acrylic resin can contain the acrylic rubber particle as the impact improving agent.So-called here acrylic rubber particle; Be to be the particle of the elastomeric polymer of main body as neccessary composition with the acrylate, its particle that in fact only can enumerate the single layer structure that is formed by this elastomeric polymer is maybe with the particle of this elastomeric polymer as 1 layer multilayered structure.As the example of said elastomeric polymer, can enumerate with the alkyl acrylate and be principal constituent and make the cross-linking elasticity multipolymer that can get with other vinyl monomer and cross-linkable monomer copolymerization of its copolymerization.As the alkyl acrylate that constitutes the elastomeric polymer principal constituent; For example; The carbon number that can enumerate alkyl such as methyl acrylate, ethyl propenoate, Bing Xisuandingzhi, 2-EHA is about 1～8 alkyl acrylate, and preferred especially the use has the acrylate that carbon number is the alkyl more than 4.As can with other vinyl monomer of this alkyl acrylate copolymer; Can enumerate the compound that has 1 polymerizability carbon-carbon double bond at intramolecularly; More particularly, can enumerate like the methacrylic ester the methyl methacrylate, like the aromatic ethenyl compound the vinylbenzene, thiazolinyl nitrile compound etc. as vinyl cyanide.In addition; As cross-linkable monomer; Can enumerate the cross-linked compound that has at least 2 polymerizability carbon-carbon double bonds at intramolecularly; More particularly, can enumerate (methyl) esters of acrylic acid of the polyvalent alcohol as ethylene glycol bisthioglycolate (methyl) acrylate and butyleneglycol two (methyl) acrylate, (methyl) the acrylic acid alkenyl esters as (methyl) vinylformic acid allyl ester, Vinylstyrene etc.
In addition, also can be with the layer compound of the film that constitutes by the acrylic resin that does not contain rubber particles and the film that constitutes by the acrylic resin that comprises rubber particles as protective membrane.
When using acrylic resin as protective membrane; When using composition of the present invention, can not obtain good binding property even do not carry out corona treatment yet, but in order to obtain good fusible coating; Perhaps make binding property better, also can before coating adhesive, implement corona treatment.
The noncrystalline polyolefin that is used for protective membrane is a resin; Normally have by norbornylene or derivatives thereof, the such polycycle cycloolefin institute deutero-polymerized unit of dimethano-octahydro naphthalene; And residual when two key is arranged as ring-opening polymerization polymer, the thermoplastic resin that preferred two keys are hydrogenated.Noncrystalline polyolefin is that resin also can be the multipolymer of cyclic olefin and chain alkene, also can import polar group in addition.Wherein, the thermoplasticity saturated norbornene is that resin is representational.Enumerate the example that commercially available noncrystalline polyolefin is a resin, " ア one ト Application ", " ZEONEX " and " ZEONOR " of Japanese ゼ オ Application (strain) of JSR (strain), " APO " and " ア ペ Le " of Mitsui Chemicals (strain) etc. are arranged.When with noncrystalline polyolefin being resin system film formation film, the system film can suitably use known methods such as solvent cast method, extrusion by melting.
Using noncrystalline polyolefin is resin during as protective membrane, in order to obtain good binding property, preferably before coating adhesive, implements corona treatment.
Recognize the polaroid of side being used for looking of liquid crystal indicator, can look and recognize side and promptly give anti-dazzle photosensitiveness being configured in this with the protective membrane of liquid crystal cell opposition side.Under this situation, form protective membrane look the surface of recognizing side, promptly with the face of the face opposition side that is fitted in polarization element, be provided with usually and have the antiglare layer of concave-convex surface.Antiglare layer generally forms through following method; Promptly; It is concavo-convex to use embossing on the active energy ray-curable resin, to give, and perhaps in the active energy ray-curable resin, cooperates the particulate that has with its different refractivity, and makes it to solidify and give concavo-convex method.In addition; When constituting protective membrane by acrylic resin, use in as the acrylic resin of binding agent, cooperate have with the particulate of its different refractivity optical diffusion layer to constitute protective membrane with laminate film by the transparent layer that acrylic resin constituted that does not cooperate said particulate also be effective.Under this situation; Can adopt the form that will be fitted with its optical diffusion layer side and polarization element by above-mentioned optical diffusion layer and these 2 layers of formed laminate films of above-mentioned transparent layer, the laminate film of 3-tier architecture that maybe will use the above-mentioned optical diffusion layer of above-mentioned transparent layer clamping two sides is with the form of its transparent layer and polarization element applying etc.And will be when containing acrylic resin laminate film that such optical diffusion layer gives anti-dazzle photosensitiveness as protective membrane; Form this look recognize side the surface promptly with the face of the face opposition side that is fitted in polarization element; Aforesaid anti-dazzle photosphere is set, and also is effective for further raising anti-dazzle performance.
As previously mentioned; Particularly with the acrylic resin film during as protective membrane; The binding property of the epoxy monomer that does not contain aromatic nucleus shown in the patent documentation 6 in the past (TOHKEMY 2004-245925 communique) is not necessarily abundant; And composition of the present invention; Even during as protective membrane, also giving good bounding force with said acrylic resin film.Therefore, the present invention is particularly useful during as protective membrane with the acrylic resin film.
The present invention is through the light solidified tackiness agent of preamble explanation, the one side at least of polarization element fit above explanation by being selected from the protective membrane that transparent resin film constituted that vibrin, polycarbonate resin, acrylic resin and noncrystalline polyolefin are resin.Only when the one side applying protective membrane of polarization element, for example, also can take on the another side of polarization element the form of the binder layer that directly is provided for fitting with other parts such as liquid crystal cell.
On the other hand, when the two sides of polarization element applying protective membrane, each protective membrane can be identical type, also can be different sorts.Particularly; For example can adopt following form: in the form of applying polyester resin film in the two sides of polarization element as protective membrane; In the form of applying polycarbonate resin in the two sides of polarization element as protective membrane; In the form of applying acrylic resin in the two sides of polarization element as protective membrane; At the two sides of polarization element applying noncrystalline polyolefin is the form of resin as protective membrane, and fitting in the one side of polarization element is selected from vibrin; Polycarbonate resin; Acrylic resin and noncrystalline polyolefin are that any transparent resin film of resin is as protective membrane; And fit at the another side of polarization element and to be selected from vibrin; Polycarbonate resin; The different transparent resin film of above-mentioned protective membrane of any of acrylic resin and amorphism polyolefin-based resins is as form of protective membrane etc.Further; Also can adopt following form: on the one side of polarization element, fit be selected from vibrin, polycarbonate resin, acrylic resin and noncrystalline polyolefin be any transparent resin film of resin as protective membrane, applying is the form of any different transparent resin film of resin as protective membrane with vibrin, polycarbonate resin, acrylic resin and noncrystalline polyolefin on the another side of polarization element.When the two sides of polarization element applying protective membrane, can divide to relate to simultaneously 2 protective membranes of applying of one side, also can be with a step applying two sides.
When the two sides of polarization element applying protective membrane; When making it simultaneously when being different other resin molding of resin with vibrin, polycarbonate resin, acrylic resin and noncrystalline polyolefin; As the preferred example of this other resin, can enumerate cellulose-based resin.In addition; What be fitted in the polarization element one side is the protective membrane that resin constitutes by vibrin, polycarbonate resin, acrylic resin and noncrystalline polyolefin; According to the present invention; Though it is bonding that the light solidified tackiness agent through preamble explanation carries out, the protective membrane that is fitted in the polarization element another side also can carry out bonding through other tackiness agent.For example; In the one side setting of polarization element by the such Water Vapour Permeability of cellulose-based resin molding during than the higher protective membrane that resin molding constituted; At the binding face of the high resin molding of said Water Vapour Permeability, also can use the tackiness agents beyond the epoxy system such as polyethenol series tackiness agent.But, therefore, use the method operation of same binder simpler on the two sides of polarization element because even light solidified tackiness agent of the present invention also can give high adhesion for the cellulose-based resin molding of giving an example here, be favourable therefore.
As the cellulose-based resin of the protective membrane of another side, be cellulosic partially or completely carboxylate, for example, can enumerate cellulosic acetic ester, propionic ester, butyric ester, their mixed ester etc.Specifically can enumerate tri acetyl cellulose, diacetyl cellulose, cellulose acetate propionate, cellulose acetate butyrate etc.Enumerate when being the example of commercially available article of the film that constitutes of resin, can enumerate " Off ジ タ Star Network TD80 ", " the Off ジ タ Star Network TD80UF " and " Off ジ タ Star Network TD80UZ " that the Off イ of Fuji Le system (strain) makes, " KC8UX2M " and " KC8UY " of コ ニ カ ミ ノ Le タ オ プ ト (strain) manufacturing etc. by such cellulose ester.In addition, also can use the cellulose-based resin molding of giving optical compensation function.As said optical compensation films; For example, can enumerate and make the film that contains compound in the cellulose-based resin, have the film of the compound of phase differential adjustment function, cellulose-based resin molding carried out the film of single shaft or biaxial stretch-formed gained etc. in the surface coated of cellulose-based resin molding with phase differential adjustment function.When enumerating the example of commercially available cellulose-based optical compensation films; Can enumerate " ワ イ De PVC ユ one Off イ Le system WV BZ 438 " and " ワ イ De PVC ユ one Off イ Le system WV EA " that the Off イ of Fuji Le system (strain) is made, " KC4FR-1 " and " KC4HR-1 " of コ ニ カ ミ ノ Le タ オ プ ト (strain) manufactured etc.
As being the example of the low transparent resin of the Water Vapour Permeability of other different resin of resin and the protective membrane that can be used as another side, can enumerate polysulfone resin, ester ring type polyimide resin etc. with vibrin, polycarbonate resin, acrylic resin and noncrystalline polyolefin.
Protective membrane can be implemented easy adhesion process such as saponification processing, corona treatment, Cement Composite Treated by Plasma, bottoming coated to binding face before fitting with polarization element.In addition, on surface protective membrane and the opposition side polarization element binding face, also can have various processing layers such as hard coat, anti-reflection layer, anti-dazzle photosphere.The thickness of protective membrane is generally the scope about 5～200 μ m, is preferably 10～120 μ m, and further is preferably 10～85 μ m.
[method of manufacture of polaroid]
Polaroid of the present invention can be through following method manufacturing; This method comprises: the polarization element of preamble explanation with by being selected from the one side at least of binding face that vibrin, polycarbonate resin, acrylic resin and noncrystalline polyolefin are the protective membrane that transparent resin film constituted of resin, the adhesive coated operation of the light solidified tackiness agent of coating preamble explanation; The bonding process that binder layer through gained is fitted polarization element and protective membrane; And passing through to make light solidified binder composition solidified curing process under the state of this binder layer with polarization element and protective membrane applying.
< adhesive coated operation >
In the adhesive coated operation, the one side at least in the binding face of polarization element and protective membrane is coated with the light solidified tackiness agent of preamble explanation.When the surface of polarization element or protective membrane directly was coated with the light solidified tackiness agent, its coating process did not have special qualification.For example, can adopt scraper, coiling rod, mould to be coated with various coating methods such as machine, comma formula coating machine, intaglio printing coating machine.In addition, also can be employed in the light solidified tackiness agent of the explanation of curtain coating preamble between polarization element and the protective membrane after, thereby the method for using roller etc. to pressurize it is evenly spread out.
<bonding process >
After so being coated with the light solidified tackiness agent, it is provided to bonding process.In this bonding process, for example, before painting process in during surface coated light solidified tackiness agent at polarization element, protective membrane is superimposed with it; Before painting process in during surface coated light solidified tackiness agent at protective membrane, polarization element is superimposed with it.In addition, during curtain coating light solidified tackiness agent, polarization element and protective membrane is superimposed between polarization element and protective membrane with this state.When the two sides of polarization element applying protective membrane and on the two sides, all using light solidified tackiness agent of the present invention, through the light solidified tackiness agent superimposed protective membrane on the two sides of polarization element respectively.Then, using roller etc. (during the superimposed protective membrane of one side, to be polarization element side and protective membrane side under this state usually at polarization element from the two sides; In addition, during superimposed protective membrane, be the protective membrane side on this two sides on the two sides of polarization element) clamping, pressurize thus.Here, the material of roller can be used metal or rubber etc.The roller that is configured in the two sides can be identical material, also can be different materials.
< curing process >
As stated, will the material under the state of polarization element and protective membrane applying be provided to ensuing curing process through uncured light solidified tackiness agent.In this curing process, to light solidified tackiness agent irradiation active energy beam, the binder layer that contains epoxy compounds or oxetane compound etc. is solidified, make polarization element and protective membrane bonding.When the one side applying protective membrane of polarization element, active energy beam can be from any side irradiation of polarization element side, protective membrane side.In addition; When the two sides of polarization element applying protective membrane; Protective membrane is being fitted under the state on polarization element two sides through the light solidified tackiness agent respectively, from arbitrary protective membrane side irradiation active energy beam, it is favourable that the light solidified tackiness agent on two sides is solidified simultaneously.But; (for example be combined with UV light absorber in the protective membrane of one side in office; Will be combined with the cellulose-based resin molding of UV light absorber as the situation of the protective membrane of one side) time and active energy beam during for ultraviolet ray, do not cooperate the protective membrane side irradiation ultraviolet radiation of UV light absorber usually from another side.
As active energy beam, can use visible light, ultraviolet ray, X ray, electron beam etc., but consider preferred usually use ultraviolet ray from easy processing and the also enough viewpoints of curing speed.The light source of active energy beam does not have special qualification, can use the for example low pressure mercury lamp that below wavelength 400nm, has luminescence distribution, medium pressure mercury lamp, high voltage mercury lamp, ultrahigh pressure mercury lamp, chemical lamp, black lamp, microwave-excitation mercury lamp, metal halide lamp, LED lamp etc.
Rayed intensity to the light solidified tackiness agent is decided according to each objective composition; Its equally not special qualification, but preferably the exposure intensity of the effective wavelength region may of activation of polymerization starter is made that (the medium wavelength zone ultraviolet ray of 280～320nm) is 1～3000mW/cm as UV-B
2Exposure intensity is less than 1mW/cm
2The time, the reaction times is long, and on the other hand, this exposure intensity surpasses 3000mW/cm
2The time, because the heating when lamp institute radiating heat and the polymerization of light solidified tackiness agent, might produce the deterioration of the xanthochromia or the polarization element of light solidified tackiness agent.
Rayed time basis to the light solidified tackiness agent respectively wants cured compositions to regulate, its not special equally qualification, and the long-pending represented accumulation light quantity that still preferably sets with exposure intensity and irradiation time is 10～5000mJ/cm
2The accumulation light quantity is less than 10mJ/cm
2The time, the generation of spike that comes from polymerization starter is insufficient, and the curing of binder layer maybe be not enough, and on the other hand, this accumulation light quantity surpasses 5000mJ/cm
2The time, irradiation time is very long, and is unfavorable for boosting productivity.
When the irradiation active energy beam solidifies the light solidified tackiness agent, preferably, each function of polaroids such as the transparency of degree of polarization, transmissivity and the color and luster of polarization element and protective membrane do not make its curing under have the condition of decline.
In the polaroid of gained like this, the thickness of binder layer is generally below the 50 μ m, is preferably below the 20 μ m, further is preferably below the 10 μ m.
[optics]
When using polaroid, also can be formed on the optics that one of which side layer has closed the optical layers that shows the optical function beyond the polarisation function.Being laminated in the optical layers of polaroid in order to form optics, for example is employed various optical layers in the formation of liquid crystal indicator etc. such as reflecting layer, Semitransmissive reflecting layer, optical diffusion layer, phase difference film, light-collecting piece, brightness improving film.Aforementioned reflecting layer, Semitransmissive reflecting layer and optical diffusion layer are the materials that when formation comprises the formed optics of dual-purpose type polaroid of reflection-type or Semitransmissive or diffusion type, uses.
The polaroid of reflection-type is used to make the liquid crystal indicator of considering oneself as the incident light reflection of recognizing side and carrying out display type, owing to can omit the light source backlight of Denging, so easily with the liquid crystal indicator slimming.In addition, the polaroid of Semitransmissive is used at bright place showing, in the dark to use light source such as backlight to carry out the liquid crystal indicator of display type as reflection-type.As the optics of reflective polaroid, for example can the protective membrane on polarization element set up the paper tinsel that constitutes by metals such as aluminium or vapor-deposited film and form the reflecting layer.As the optics of the polaroid of Semitransmissive, can through with aforesaid reflecting layer as semi-permeable mirror, maybe will contain pearly pigment etc. and to demonstrate reflector plate and the polaroid of transmitance bonding and form.On the other hand; Optics as diffusion type polaroid; For example use the protective membrane on the polaroid is implemented the method for delustring processing, method, the bonding the whole bag of tricks such as method that contain the film of particulate that coating contains the resin of particulate, form the micro concavo-convex structure on the surface.
Further, as the formation of the optics that reflects the dual-purpose polaroid of diffusion, the methods such as reflecting layer that this concaveconvex structure of reflection for example can be set through the micro concavo-convex structural plane at diffusion type polaroid are carried out.The reflecting layer of micro concavo-convex structure has the diffuse-reflectance of utilizing makes the incident light diffusion, prevents directional property or dazzle, the inhibition light and shade is uneven advantage etc.In addition, contain the resin layer or the film of particulate, also have when incident light and reflected light thereof see through the layer that contains particulate and further suppressed the unequal advantage of light and shade by diffusion.The reflecting layer of reflecting surperficial micro concavo-convex structure for example can be through with methods such as vapor deposition such as vacuum evaporation, ion plating, sputter or plating, directly sets up metal on the surface of micro concavo-convex structure and forms.The particulate that cooperates as being used to form surperficial micro concavo-convex structure; For example; Can use median size be 0.1～30 μ m by silicon-dioxide, aluminum oxide, titanium oxide, zirconium white, stannic oxide, Indium sesquioxide etc. formed inorganic be particulate, or by formed organic system particulates such as crosslinked or uncrosslinked polymkeric substance etc.
On the other hand, as the phase difference film of above-mentioned optical layers, be to use in order to compensate the phase differential that causes because of liquid crystal cell.As its example, can enumerate by the film of the formed birefringence films such as stretched film of various plastics, dish-type liquid crystal or the setting of nematic liquid crystal orientation, on film base material, form the material of above-mentioned liquid crystal layer etc.Under this situation, the film base material as supporting the aligned liquid-crystal layer preferably uses Mierocrystalline cellulose mesenterys such as tri acetyl cellulose.
As the plastics of form dielectric grid property film, for example can enumerate polycarbonate, polyvinyl alcohol, polystyrene, polymethylmethacrylate, the polyolefine as polypropylene, polyarylester, polymeric amide, noncrystalline polyolefin is resin etc.Stretched film can be to handle the film of gained through single shaft or suitable mode such as biaxial stretch-formed.In addition, thus also can be through with heat-shrinkable film adherent state under apply the birefringence film of specific refractory power of the thickness direction of convergent force and/or drawing force controlling diaphragm.In addition, in order to control optical characteristics such as broadband, also can make up 2 with on use phase difference film.
Light-collecting piece uses in order to control light path etc., and it can be used as prism array sheet, lens array sheet or point and sets up sheet etc. and form.
The brightness improving film uses for the brightness that improves liquid crystal indicator etc.; As its example, can enumerate layer and close the mutually different film of anisotropy of multi-disc specific refractory power and be designed to and producing anisotropic reflection-type rectilinearly polarized light separate sheet on the reflectivity, on film base material, supporting the alignment films of cholesteric liquid crystal polymers or the circularly polarizing separation sheet of its aligned liquid-crystal layer etc.
Optics can be with polaroid and the laminate more than 2 layers or 3 layers that is made up by the optical layers of selecting in aforesaid reflecting layer or Semitransmissive reflecting layer, optical diffusion layer, phase difference film, light-collecting piece or the brightness improving film etc. more than 1 layer or 2 layers according to application target.Under this situation, optical layers such as optical diffusion layer or phase difference film, light-collecting piece or brightness improving film also can dispose respectively more than 2 layers.In addition, the configuration of each optical layers is not special limits.
The various optical layers and the polaroid that will form optics through using tackiness agent are integrated, as long as used for this reason tackiness agent can form bonding coat well, and just not special the qualification.From the simplicity of bonding operation with prevent viewpoint such as optical skew, preferably use pressure sensitive adhesive (also being called as the pressure-sensitive tackiness agent).Pressure sensitive adhesive can use the pressure sensitive adhesive as base polymer such as acrylic acid polymer, silicon-type polymkeric substance, polyester, urethane or polyethers.Wherein, Preferred select to use the such optical transparence of acrylic pressure-sensitive adhesive excellent, maintain suitable wettability and cohesive force, also excellent with the binding property of base material, and further have weathering resistance and thermotolerance etc., and under the condition of heating or humidification perk can not take place or the pressure sensitive adhesive of the problem of peeling off such as strip off.In acrylic pressure-sensitive adhesive; Cooperation is (methyl) acrylic acid alkyl ester of the alkyl below 20 and the formed functional groups' of containing such as (methyl) vinylformic acid, (methyl) Hydroxyethyl Acrylate acrylic monomer by the carbon number that has as methyl, ethyl or butyl; Second-order transition temperature is preferably below 25 ℃; And further be preferably below 0 ℃; And to make its polymerization and obtain weight-average molecular weight be the acrylic copolymer more than 100,000, and this acrylic copolymer is useful as base polymer.
Pressure sensitive adhesive layer is in the formation of polaroid; Can be through contact adhesive composition being dissolved or being dispersed in the organic solvent as toluene or ethyl acetate; Be modulated into the liquid that solid component concentration is 10～40 weight %; And it directly is coated on the polaroid mode that forms pressure sensitive adhesive layer; Perhaps, through in advance form pressure sensitive adhesive layer on the barrier film, again with its transfer and be bonded in mode of forming pressure sensitive adhesive layer on the polaroid etc. and carry out.The thickness of pressure sensitive adhesive layer waits to confirm according to its bounding force, and the scope about 1～50 μ m is suitable.
In addition, pressure-sensitive adhesive layer can be combined with by formed weighting agent, pigment or tinting material, antioxidant, UV light absorber etc. such as glass fibre, granulated glass sphere, resin bead, metal powder or other inorganic powders as required.As UV light absorber, can be salicylate based compound, UVNUL MS-40 based compound, benzotriazole based compound, cyanoacrylate based compound or nickel complexing salt based compound etc.
[liquid crystal indicator]
Aforesaid optics can be disposed on the one or both sides of liquid crystal cell, form liquid crystal indicator.The liquid crystal cell that uses is arbitrarily, for example can use with film transistor type as the liquid crystal cell of the active matrix drive-type of representative, with super-twist nematic as the driving various liquid crystal cells such as liquid crystal cell of the simple matrix of representative to form liquid crystal indicator.The optics that is arranged on the liquid crystal cell both sides can be identical, also can be different.
[embodiment]
Below, enumerate embodiment and comparative example, the present invention more specifically is described, but the present invention is not limited to these examples.In example, the % of expression usage quantity or content, short of special instruction is weight basis.
In embodiment and comparative example, the various compositions that are used for the light modulated curing adhesive composition are as described below, below with compound name or separately symbol (trade(brand)name itself or its a part of) represent.
(A) composition: epoxy compounds
JER-828: bisphenol A type epoxy resin, " jER-828 " that japan epoxy resin (strain) is made.
(B) composition: two (methyl) acrylic compound
FM-400: neopentyl glycol, hydroxy new pentane acid and acrylic acid esterification reaction product, " the カ ヤ ラ Star De FM-400 " that Japanese chemical drug (strain) is made.
HDDA:1,6-hexanediyl ester, " ラ イ ト ア Network リ レ one ト 1, the 6HX-A " that common prosperity society chemistry (strain) is made.
(B) ' composition: (B) (methyl) acrylic compound beyond the composition
M-309: Viscoat 295, " the ア ロ ニ Star Network ス M-309 " that East Asia synthetic (strain) makes.
M-203: tristane dihydroxymethyl diacrylate, " the ア ロ ニ Star Network ス M-203 " that East Asia synthetic (strain) makes.Carbon number is the diacrylate of 12 dibasic alcohol.
M-220: polypropylene glycol (average number of repeat unit is about 3) diacrylate, " the ア ロ ニ Star Network ス M-220 " that East Asia synthetic (strain) makes.Average carbon number with ether structure is the diacrylate of 9 dibasic alcohol.
M-240: polyoxyethylene glycol (average number of repeat unit is about 4) diacrylate, " the ア ロ ニ Star Network ス M-240 " that East Asia synthetic (strain) makes.Average carbon number with ether structure is the diacrylate of 8 dibasic alcohol.
(C) composition: light cationic polymerization initiators
CPI-100P: with the triaryl matte hexafluorophosphate is that the effective constituent of main component is 50% carbonic allyl ester solution, " CPI-100P " that サ Application ア プ ロ (strain) makes.Put down in writing the umber of effective constituent in the table.
(D) composition: the oxetane compound of expression in the aforementioned formula (1)
OXT-221:3-ethyl-3-[(3-ethyl trimethylene oxide-3-yl) methoxymethyl] trimethylene oxide, " the ア ロ Application オ キ セ タ Application OXT-221 " that East Asia synthetic (strain) makes.
(E) composition: the oxetane compound of expression in the aforementioned formula (2)
OXT-101:3-ethyl-3-hydroxymethyl trimethylene oxide, " the ア ロ Application オ キ セ タ Application OXT-101 " that East Asia synthetic (strain) makes.
(F) composition: optical free radical polymerization starter
The Irg184:1-hydroxycyclohexylphenylketone, " IRGACURE 184 " of vapour manufactured in the sixth of the twelve Earthly Branches.
(G) composition: flow agent
8019 Additive: the polysiloxane series flow agent " 8019Additive " that eastern beautiful DOW CORNING (strain) is made.
Other composition
Propylene carbonate
[modulation of Photocurable pressure-sensitive adhesive composition]
Each composition shown in table 1 and the table 2 is cooperated with separately ratio, and mix the light modulated curing adhesive composition according to usual method.In addition, as previously mentioned,, therefore, in table, (C) composition and propylene carbonate are separately represented because " CPI-100P " that uses as (C) composition is the carbonic allyl ester solution that contains 50% effective constituent.That is, the use level of " CPI-100P " in the table, the ratio of expression effective constituent, the use level that " CPI-100P " is own is that (C) becomes amount shown in the subfield and the amount sum shown in the propylene carbonate hurdle.
The viscosity of resulting composition under 25 ℃ is 100 ± 20mPas, and coating is all good.
[making of polaroid]
Use 2 kinds of following films as protective membrane here.
Stretching norbornene resin film: thickness is 70 μ m, and commodity are called " ZEONOR film ", Japanese ゼ オ Application (strain) system.This film is implemented Corona discharge Treatment, use it for applying then with polarization element.
The acrylic resin film: thickness is 80 μ m, trade(brand)name " テ Network ノ ロ イ S001 ", Sumitomo Chemical (strain) system.This film is also implemented Corona discharge Treatment, use it for applying then with polarization element.
Use rod to be coated with machine, be coated with above-mentioned synthetic composition with the thickness of 3 μ m at the Corona discharge Treatment face of the Corona discharge Treatment face of above-mentioned stretching norbornene resin film and acrylic resin film.Then, the mode of the polarization element of iodine is arranged, use roller 3 films of fitting simultaneously between these 2 films, to be clamped in the polyvinyl alcohol absorption orientation.Through the subsidiary UV irradiation equipment (lamp uses " the Fusion H bulb " of Fusion manufactured) that belt conveyer is arranged, the two sides of gained like this has been fitted with the accumulation light quantity on since stretch norbornene resin film surface is 300mJ/cm since the polarization element of protective membrane
2(UV-B) come irradiation ultraviolet radiation,, be produced on fitted on the one side protective membrane that is constituted by the acrylic resin film and the polaroid of on another side, having fitted stretching norbornene resin film then 23 ℃, the environment held of 50%R.H. 1 day.
23 ℃, the standard conditions of 50～60%R.H., and under 23 ℃, the drying conditions both of these case of 20～30%R.H., implementing should test.
[evaluation test]
To the polaroid of gained, estimate binding property and weather resistance by following method, the result is summarized in table 1 and table 2.
<binding property >
Zero shear knife inserts test
With the blade of shear knife when the top of acrylic resin film tilts to insert; The average evaluation that blade can't be inserted between the polarization element is zero; Blade inserted a little but have certain intensity and during the course protective membrane disruptive average evaluation be △, and the average evaluation that will insert easily for *.
The polaroid under standard conditions, made and the polaroid under drying conditions, made are implemented this evaluation, and as described belowly carry out fusible comprehensive evaluation.
◎: all be zero under two kinds of conditions
Zero: being zero under a kind of condition, is △ under another kind of condition
△: all be △ under two kinds of conditions
*: under a kind of condition be *
* *: under two kinds of conditions all be *
< weather resistance >
For in table 1 and table 2, be the sample more than the △ for binding property, be implemented in-35 ℃ of held 60 minutes, again+70 ℃ of held 60 minutes, and circulation 300 times thermal shock round-robin test repeatedly, result's bad order unconfirmed can know that its weather resistance is good.
[table 1]
[table 2]
As shown in table 1, all compositions of the embodiment 1 of composition of appropriate amount (A)～(E) that comprise of the present invention all demonstrate excellent binding property under two kinds of conditions.
The composition that does not comprise the embodiment 2～embodiment 4 of (E) composition demonstrates excellent binding property under standard conditions, poorer than embodiment 1 under drying conditions, but demonstrates the binding property of the degree that in practicality, do not have problems.
Do not comprise embodiment 5 of (D) composition and the composition of embodiment 6, under standard conditions with drying conditions under all poor than embodiment 1, but demonstrate the binding property of the degree that in practicality, do not have problems.
On the other hand, do not comprise the composition of the comparative example 1 of (B) composition, though under standard conditions, demonstrate excellent binding property, bonding bad under drying conditions.In addition, (B) the cooperation ratio of composition surpasses the composition of the comparative example 2 of the present invention (B) components matching ratio upper limit 45%, under standard conditions with drying conditions under all bonding bad.Further; At the M-309, the carbon number that contain 37% 3 functional acrylates is the M-203 of the diacrylate of 12 dibasic alcohol, M-220 and the M-240 of diacrylate during as the acrylate beyond (B) composition with ether structure; Shown in comparative example 3～comparative example 6, under standard conditions with drying conditions under all bonding bad.
Utilizability in the industry
Photocurable pressure-sensitive adhesive composition of the present invention solidifies easily through irradiation ultraviolet radiation isoreactivity energy-ray, for being effective with the short period of time with polarization element and protective membrane good bond.
Claims (12)
1. light solidified binder composition; It is to be used for protective membrane is bonded in the binder composition that the absorption that comprises uniaxial extension is orientated the polarization element of the polyvinyl alcohol resin film that the dichroism pigment is arranged; This protective membrane comprises and is selected from the transparent resin film that vibrin, polycarbonate resin, acrylic resin and noncrystalline polyolefin are resin, and said composition is characterised in that and contains
(A) have the epoxy compounds of at least 2 epoxy group(ing) and at least 1 aromatic nucleus at intramolecularly,
(B) can have the ester skeleton have carbon number be 5～10 glycol (wherein, except the ether compound) two (methyl) acrylate and
(C) light cationic polymerization initiators,
Containing of said (A)～(C) composition proportionally in composition does
(A) composition: 20～60 weight %
(B) composition: 5～45 weight %
(C) composition: 0.5～10 weight %.
2. light solidified binder composition as claimed in claim 1 is characterized in that (A) composition is a bisphenol A type epoxy resin.
3. like claim 1 or the described light solidified binder composition of claim 2, it is characterized in that (B) composition is neopentyl glycol, hydroxy new pentane acid and (methyl) acrylic acid esterification reaction product or two (methyl) vinylformic acid hexylene glycol ester.
4. like each described light solidified binder composition in claim 1～claim 3, it is characterized in that in composition, also containing the oxetane compound shown in 5～45 following formulas of weight % (D) (1),
5. like each described light solidified binder composition in claim 1～claim 4, it is characterized in that in composition, also containing the oxetane compound shown in 1～20 following formula of weight % (E) (2),
6. like each described light solidified binder composition in claim 1～claim 5, it is characterized in that in composition, also containing (F) optical free radical polymerization starter of the following ratio of 10 weight %.
7. like each described light solidified binder composition in claim 1～claim 6, it is characterized in that in composition, also containing 0.01～0.5 weight % (G) flow agent.
8. polaroid; It is to comprise through tackiness agent that to be selected from vibrin, polycarbonate resin, acrylic resin and noncrystalline polyolefin be that the protective membrane of the transparent resin film of resin is fitted in polarization element and forms; The absorption orientation that this polarization element comprises uniaxial extension has the polyvinyl alcohol resin film structure of dichroism pigment, and it is characterized in that said tackiness agent is formed by each described light solidified binder composition in claim 1～claim 7.
9. the method for manufacture of polaroid; It is will comprise through tackiness agent to be selected from vibrin; Polycarbonate resin; Acrylic resin and noncrystalline polyolefin are that the protective membrane of the transparent resin film of resin is fitted in polarization element; Thereby make the method for polaroid; The absorption that this polarization element comprises uniaxial extension is orientated the polyvinyl alcohol resin film that the dichroism pigment is arranged; The method is characterized in that and comprise: in the one side at least of the binding face of said polarization element and said protective membrane, the adhesive coated operation of each described light solidified binder composition in coating claim 1～claim 7;
Through the binder layer of gained, with the bonding process of said polarization element and the applying of said protective membrane;
And passing through to make said light solidified binder composition solidified curing process under the state of said binder layer with polarization element and protective membrane applying.
10. optics is characterized in that closing other optical layers in the described layer of polarizer of claim 8.
11. optics as claimed in claim 10, said other optical layers comprises phase difference film.
12. liquid crystal indicator is characterized in that claim 10 or the described optics of claim 11 are configured in the one or both sides of liquid crystal cell.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010087628A JP5495906B2 (en) | 2010-04-06 | 2010-04-06 | Photocurable adhesive composition, polarizing plate and method for producing the same, optical member and liquid crystal display device |
| JP2010-087628 | 2010-04-06 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102344763A true CN102344763A (en) | 2012-02-08 |
| CN102344763B CN102344763B (en) | 2015-06-24 |
Family
ID=45028082
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110168572.7A Active CN102344763B (en) | 2010-04-06 | 2011-04-02 | Photocurable adhesive composition, polarizing plate and a process of producing the same, optical member, and liquid crystal display device |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5495906B2 (en) |
| KR (1) | KR101806875B1 (en) |
| CN (1) | CN102344763B (en) |
| TW (1) | TWI504711B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105683787A (en) * | 2013-09-30 | 2016-06-15 | Lg化学株式会社 | Polarizing plate and image display apparatus comprising same |
| CN106133080A (en) * | 2014-05-27 | 2016-11-16 | 日本合成化学工业株式会社 | Adhesive composite, polarization plates adhesive composite, polarization plates bonding agent and use its polarization plates |
| CN107340560A (en) * | 2012-07-02 | 2017-11-10 | 住友化学株式会社 | The manufacture method and manufacture device of polarization plates |
| CN112512800A (en) * | 2018-08-08 | 2021-03-16 | 三菱瓦斯化学株式会社 | Laminate for molding |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI537356B (en) * | 2010-12-17 | 2016-06-11 | Toagosei Co Ltd | Photo-curable adhesive composition, polarizing adhesive and manufacturing method thereof, optical member and liquid crystal display device (1) |
| KR101378817B1 (en) | 2011-10-14 | 2014-04-03 | 주식회사 엘지화학 | Adhesive for polarizing plate and polarizing plate comprising the same |
| US9523792B2 (en) | 2011-10-14 | 2016-12-20 | Lg Chem, Ltd. | Polarizer having protection films in two sides and optical device comprising the same |
| KR101560033B1 (en) * | 2011-10-14 | 2015-10-16 | 주식회사 엘지화학 | Polarizer having protection films in two sides and optical device comprising the same |
| JP5530470B2 (en) * | 2012-03-09 | 2014-06-25 | チェイル インダストリーズ インコーポレイテッド | Adhesive for polarizing plate |
| KR101291441B1 (en) * | 2012-05-01 | 2013-07-30 | 코니카 미놀타 어드밴스드 레이어즈 인코포레이티드 | Retardation film, method of manufacturing polarizing plate, and liquid crystal display device |
| JP5788841B2 (en) * | 2012-08-15 | 2015-10-07 | チェイル インダストリーズ インコーポレイテッド | Adhesive for polarizing plate |
| KR102215376B1 (en) * | 2012-10-11 | 2021-02-10 | 스미또모 가가꾸 가부시끼가이샤 | Photocurable adhesive composition, polarizer and process for producing same, optical member, and liquid-crystal display device |
| KR101640631B1 (en) * | 2012-12-12 | 2016-07-18 | 제일모직주식회사 | Adhesive film for polarizing plate, adhesive composition for the same, polarizing plate comprising the same and optical display apparatus comprising the same |
| JP6098938B2 (en) * | 2013-04-02 | 2017-03-22 | ナガセケムテックス株式会社 | Adhesive for electronic component sealing |
| JP5971198B2 (en) * | 2013-06-12 | 2016-08-17 | コニカミノルタ株式会社 | Polarizing plate, method for manufacturing the same, and organic electroluminescence display device including the same |
| JP6075237B2 (en) * | 2013-07-12 | 2017-02-08 | 東亞合成株式会社 | Active energy ray-curable adhesive composition for plastic film or sheet |
| KR20150016877A (en) * | 2013-08-05 | 2015-02-13 | 주식회사 엘지화학 | Pressure sensitive adhesive compositions, pressure sensitive adhesive film and encapsulation method of organic electronic device using the same |
| KR101611005B1 (en) * | 2013-08-09 | 2016-04-08 | 제일모직주식회사 | Adhesive composition for polarizing plate, polarizing plate using the same and optical member comprising the same |
| KR101617016B1 (en) * | 2013-12-31 | 2016-04-29 | 에스케이씨 주식회사 | Protective film, polarizer and display device having the same |
| KR102253510B1 (en) * | 2014-05-07 | 2021-05-18 | 에스케이씨 주식회사 | A protective film for polarizer and polarizer using it |
| KR101748409B1 (en) * | 2014-07-30 | 2017-06-16 | 주식회사 엘지화학 | Resin composition for polarizer protecting film, polarizer protecting film and polarizer plate comprising the same |
| TWI681028B (en) * | 2015-03-04 | 2020-01-01 | 日商東亞合成股份有限公司 | Active energy ray hardening type adhesive composition for plastic film or sheet |
| WO2017090637A1 (en) * | 2015-11-24 | 2017-06-01 | 日本合成化学工業株式会社 | Adhesive composition, adhesive composition for polarizing plate, and polarizing plate obtained using same |
| JP6909270B2 (en) * | 2018-04-06 | 2021-07-28 | 住友化学株式会社 | Polarizing plate manufacturing method and manufacturing equipment |
| JP7088765B2 (en) * | 2018-07-20 | 2022-06-21 | ナガセケムテックス株式会社 | Photo-curing adhesive |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1646593A (en) * | 2002-04-15 | 2005-07-27 | 东亚合成株式会社 | Actinic radiation hardenable resin composition and hardening product thereof |
| KR20080060258A (en) * | 2005-10-26 | 2008-07-01 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | Concurrently curable hybrid adhesive composition |
| JP2008257199A (en) * | 2007-03-15 | 2008-10-23 | Sumitomo Chemical Co Ltd | Photocurable adhesive agent, polarizing plate using the photocurable adhesive agent, method for production of the polarizing plate, optical member, and liquid crystal display device |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001131518A (en) * | 1999-11-08 | 2001-05-15 | Dainippon Ink & Chem Inc | Ultraviolet-curing adhesive composition for laminated optical disk and optical disk using the composition |
| JP2008134396A (en) * | 2006-11-28 | 2008-06-12 | Kyoritsu Kagaku Sangyo Kk | Polarizing plate and liquid crystal display apparatus |
-
2010
- 2010-04-06 JP JP2010087628A patent/JP5495906B2/en active Active
-
2011
- 2011-03-09 TW TW100107985A patent/TWI504711B/en active
- 2011-04-02 CN CN201110168572.7A patent/CN102344763B/en active Active
- 2011-04-04 KR KR1020110030767A patent/KR101806875B1/en active IP Right Grant
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1646593A (en) * | 2002-04-15 | 2005-07-27 | 东亚合成株式会社 | Actinic radiation hardenable resin composition and hardening product thereof |
| KR20080060258A (en) * | 2005-10-26 | 2008-07-01 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | Concurrently curable hybrid adhesive composition |
| JP2008257199A (en) * | 2007-03-15 | 2008-10-23 | Sumitomo Chemical Co Ltd | Photocurable adhesive agent, polarizing plate using the photocurable adhesive agent, method for production of the polarizing plate, optical member, and liquid crystal display device |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107340560A (en) * | 2012-07-02 | 2017-11-10 | 住友化学株式会社 | The manufacture method and manufacture device of polarization plates |
| CN105683787A (en) * | 2013-09-30 | 2016-06-15 | Lg化学株式会社 | Polarizing plate and image display apparatus comprising same |
| CN105683787B (en) * | 2013-09-30 | 2018-01-26 | Lg化学株式会社 | Polarizer and the image display including the Polarizer |
| CN106133080A (en) * | 2014-05-27 | 2016-11-16 | 日本合成化学工业株式会社 | Adhesive composite, polarization plates adhesive composite, polarization plates bonding agent and use its polarization plates |
| CN106133080B (en) * | 2014-05-27 | 2019-06-11 | 三菱化学株式会社 | Adhesive composite, polarization plates adhesive composite, polarization plates bonding agent and the polarization plates using it |
| CN112512800A (en) * | 2018-08-08 | 2021-03-16 | 三菱瓦斯化学株式会社 | Laminate for molding |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI504711B (en) | 2015-10-21 |
| KR20110112217A (en) | 2011-10-12 |
| CN102344763B (en) | 2015-06-24 |
| JP2011219548A (en) | 2011-11-04 |
| TW201139585A (en) | 2011-11-16 |
| KR101806875B1 (en) | 2017-12-08 |
| JP5495906B2 (en) | 2014-05-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102344763B (en) | Photocurable adhesive composition, polarizing plate and a process of producing the same, optical member, and liquid crystal display device | |
| CN101845286B (en) | Photocurable adhesive composition, polarizing plate and a process for producing the same, optical member and liquid crystal display device | |
| CN102533135A (en) | Photo-curing adhesive composition, polaroid and manufacturing method thereof, optical component and LED device | |
| CN104745104B (en) | Photocurable adhesive agent composition, polarizer and its manufacturing method, optical component and liquid crystal display device | |
| CN104823087B (en) | Photocurable adhesive agent composition, polarization plates and its manufacture method, optical component and liquid crystal display device | |
| CN101636672B (en) | Photocurable adhesive agent, polarizing plate using the photocurable adhesive agent, method for production of the polarizing plate, optical member, and liquid crystal display device | |
| CN104419331A (en) | Photocurable adhesive composition, polarizer and manufacturing method thereof, optical member, and liquid crystal display device | |
| CN105008971B (en) | Photo-curable adhesive and polarization plates, laminated optical component and the liquid crystal display device using the adhesive | |
| KR20120015780A (en) | Polarizing plate and liquid crystal display comprising the same | |
| CN107076907A (en) | Photo-curable adhesive and polarization plates, laminated optical component and the liquid crystal display device using the photo-curable adhesive | |
| JP2014013283A (en) | Polarizing plate and liquid crystal display device | |
| CN107090259A (en) | Photo-curable adhesive and the polarization plates and laminated optical component using it |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |