CN103430060A - Polarizing plate and laminated optical member - Google Patents

Polarizing plate and laminated optical member Download PDF

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Publication number
CN103430060A
CN103430060A CN2012800157488A CN201280015748A CN103430060A CN 103430060 A CN103430060 A CN 103430060A CN 2012800157488 A CN2012800157488 A CN 2012800157488A CN 201280015748 A CN201280015748 A CN 201280015748A CN 103430060 A CN103430060 A CN 103430060A
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CN
China
Prior art keywords
polarizer
resin
polaroid
diaphragm
bonding agent
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Pending
Application number
CN2012800157488A
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Chinese (zh)
Inventor
久米悅夫
竹内智康
高桥利行
本间英里
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Adeka Corp
Sumitomo Chemical Co Ltd
Original Assignee
Sumitomo Chemical Co Ltd
Asahi Denka Kogyo KK
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Publication date
Application filed by Sumitomo Chemical Co Ltd, Asahi Denka Kogyo KK filed Critical Sumitomo Chemical Co Ltd
Priority to CN201810801588.9A priority Critical patent/CN109239831B/en
Publication of CN103430060A publication Critical patent/CN103430060A/en
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers
    • 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
    • G02F2201/00—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00
    • G02F2201/50—Protective arrangements
    • 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
    • G02F2202/00—Materials and properties
    • G02F2202/28—Adhesive materials or arrangements

Abstract

Provided is a polarizing plate configured from a polyvinyl alcohol-based polarizer and a protecting film pasted to the polarizer with an adhesive therebetween, wherein the adhesive contains 100 parts by weight of a photo cation curable component (A) and 1-10 parts by weight of a photo cation polymerization initiator (B), the cured product thereof is formed from a photocurable adhesive composition exhibiting a storage elastic modulus of at least 1000 MPa at 80 DEG C, and the photo cation curable component (A) is prepared in a manner so as to contain the following (A1) and (A2) at the following quantities relative to the total quantity thereof: 50-95 wt% of an alicyclic epoxy compound (A1) having an epoxy group bonded to an alicyclic ring; and 5-50 wt% of a diglycidyl compound (A2) having no greater than 1 wt% of contained chlorine and represented by formula (I) (Z being an alkylene group or the like).

Description

Polaroid and laminated optical component
Technical field
The present invention relates to use specific photo-curable bonding agent, the polaroid obtained at the one or both sides of polarizer laminating diaphragm.The invention still further relates to the laminated optical component that other optical layers of stacked phase retardation film etc. on this polaroid forms.
Background technology
Polaroid can be used as one of optics formed liquid crystal indicator.Usually, polaroid installs to liquid crystal indicator with the state group of the two sides stacked guard film at polarizer and uses.Also known the single face at polarizer arranges diaphragm, but, under most situation, in the another side laminating, be not also singly diaphragm, but double diaphragm has the layer of other optical function.In addition, extensively the manufacture method of known polarization device is that the uniaxial tension polyvinyl alcohol resin film with dichroic dye dyeing is carried out to the boric acid processing, the method for drying after washing.
The diaphragm of normally fitting on polarizer immediately after above-mentioned washing and drying.This be due to, a little less than dried polarizer physical strength, once it is curling occur along the problem of machine direction cracking etc.Therefore, dried polarizer normally is coated with aqueous adhesive immediately, then via this bonding agent, and the diaphragm of simultaneously fitting on two sides.The tri acetyl cellulose membrane of common diaphragm used thickness 30-100 μ m.
The triacetyl cellulose moisture permeability is high, and using it as diaphragm, the polaroid that obtains of laminating exists under such condition and causes deteriorated etc. problem under damp and hot, such as temperature 70 C, relative humidity 90%.Therefore, also known will be than the moisture permeability of triacetyl cellulose low, for example to using the amorphous polyolefins that norbornene resin is representation example be that resin is as diaphragm.
When the diaphragm that resin that will be low by moisture permeability is made is fitted on the polyethenol series polarizer; if adopt the aqueous solution of the polyvinyl alcohol resin that the Chang Zuowei bonding agent was used in polyethenol series polarizer and triacetyl cellulose laminating in the past; there is the bond strength deficiency, or the problem of the bad order of gained polaroid.This be due to, the resin molding that moisture permeability is low is generally hydrophobicity, or because moisture permeability is low, can't be using the water as solvent fully dry etc.The known two sides at polarizer different types of diaphragm of fitting also.Such as the scheme that also has, propose: the diaphragm that the low resin of moisture permeability that is resin etc. by amorphous polyolefins in a face laminating of polarizer is made, in another face laminating of polarizer by take the diaphragm that the high resin of moisture permeability of cellulose-based resin that triacetyl cellulose is representative etc. makes.
Therefore; give high adhesion between the diaphragm of making as the resin to low by moisture permeability and polyethenol series polarizer, the moisture permeability of cellulose-based resin etc. also given the bonding agent of high adhesion simultaneously between high resin and polyethenol series polarizer, attempt using the active energy ray curable bonding agent.For example; disclose take in TOHKEMY 2004-245925 communique (patent documentation 1) and do not contained the bonding agent that the epoxy compound of aromatic ring is major component; propose: the cationic polymerization undertaken by the irradiation of active energy beam, this bonding agent is solidified, make polarizer and diaphragm bonding.In addition; disclose the bonding technology for polarizer and diaphragm by the photo-curable bonding agent in TOHKEMY 2008-257199 communique (patent documentation 2), this photo-curable bonding agent is that the alicyclic epoxy compound is combined, further together with the light cationic polymerization initiators, coordinates and form with the epoxy compound that does not have the ester ring type epoxy radicals.
On the other hand; TOHKEMY 2009-181046 communique (patent documentation 3), TOHKEMY 2002-365432 communique (patent documentation 4) are about using the situation of aqueous adhesive; but also record: the viscosity of the diaphragm while manufacturing due to polaroid and the wellability of bonding agent and bonding agent; polaroid generation bad order after causing manufacturing; these parameters have a significant impact productivity; also record in addition; as its countermeasure; the lowering viscousity of infiltrating raising or bonding agent self is that effectively particularly the contribution of viscosity is very large.
As patent documentation 1 and the epoxy as shown in the of 2 are that Photocurable pressure-sensitive adhesive is different from solvent type adhesive, normally mismatch in fact solvent and be prepared.In therefore a lot of situations, in order to reduce viscosity, must increase the low viscosity component ratio in composition.Change by above-mentioned proportion of composing reduces the viscosity of the bonding agent liquid before solidifying, this in situation mostly, can cause solidifying after the hardness deficiency of adhesive phase, the polaroid after bonding may be difficult to show sufficient permanance.Therefore, at present as avoiding the scheme of bad order in polaroid manufacturing process, mainly adopt membrane surface modification or by adding even paint, wellability is improved.
Patent documentation 1: TOHKEMY 2004-245925 communique
Patent documentation 2: TOHKEMY 2008-257199 communique
Patent documentation 3: TOHKEMY 2009-181046 communique
Patent documentation 4: TOHKEMY 2002-365432 communique.
Summary of the invention
The problem that invention will solve
The inventor is when using epoxy to be Photocurable pressure-sensitive adhesive laminating polarizer and diaphragm; if the bonding agent lowering viscousity before finding to make to come into force; adhesive phase after solidifying can not show enough height, in order to improve this problem, conducts in-depth research, and result has completed the present invention.Therefore; problem of the present invention is to provide a kind of polaroid; this polaroid is that the use epoxy is the polaroid that Photocurable pressure-sensitive adhesive laminating polarizer and diaphragm obtain; in the viscosity that reduces the Photocurable pressure-sensitive adhesive that wherein used, raising coating applicability; this bonding agent can obtain enough hardness after solidifying, and the bounding force of polarizer and diaphragm is improved.Another problem of the present invention is to provide: on this polaroid other optical layers such as stacked phase retardation film, be applicable to the laminated optical component of liquid crystal indicator.
Solve the mode of problem
Result of study is found: at least 2 kinds of light cation-curable epoxy compound combinations by alicyclic epoxy compound and diglycidyl compounds, do not contain in fact in the photo-curable bonding agent of solvent, by reducing the chlorine dose in diglycidyl compounds, the hardness of the adhesive phase after can making to solidify keeps in the situation of high value, and the adjusting by proportion of composing realizes lowering viscousity.The present invention comprises following content.
[1] polaroid, this polaroid consists of polarizer and diaphragm, the polyvinyl alcohol resin film that described polarizer is adsorbed and is being orientated by dichroic dye is made, described diaphragm is fitted via bonding agent at least one face of this polarizer, by transparent resin, made, this bonding agent is formed by Photocurable adhesive composition, described Photocurable adhesive composition contains 100 weight portion light cation-curable compositions (A) and 1-10 weight portion light cationic polymerization initiators (B), its solidfied material shows the storage modulus more than 1000MPa under 80 ℃, above-mentioned smooth cation-curable composition (A) be take its total amount as benchmark, following (A1) that contains following amount and (A2) prepare:
There is 2 above epoxy radicals, at least 1 alicyclic epoxy compound (A1) closed with the ester ring type loops wherein in 50-95 % by weight molecule, and
5-50 % by weight chlorinity is that 1 % by weight is following, the diglycidyl compounds (A2) shown in following formula (I):
In formula, Z means the alkylene base, carbon number 3 of carbon number 1-9 or 4 alkylidene radical, divalent ester ring type alkyl or formula-C mH 2m-Z 1-C nH 2n-shown in the divalent group, here ,-Z 1-expression-SO 2-,-S-O-or-CO-, m and n are independent separately, mean the integer more than 1, both add up to below 9.
[2] polaroid of [1], wherein, the diaphragm be fitted at least one face of polarizer is become by acetyl fibre prime system resin.
[3] polaroid of [1], wherein, fitting in diaphragm at least one face of polarizer is that the transparent resin of resin, polyester based resin, polycarbonate-based resin and chain polyolefin-based resins is made by being selected from amorphous polyolefins.
[4] polaroid of [1]; wherein; the diaphragm become by acetyl fibre prime system resin fits on a face of polarizer via above-mentioned bonding agent; on the another side of polarizer, by being selected from amorphous polyolefins, be that the diaphragm of the film made of the transparent resin of resin, polyester based resin, polycarbonate-based resin and chain polyolefin-based resins is fitted via above-mentioned bonding agent.
[5] laminated optical component, this laminated optical component comprises the polaroid of any one in [1]-[4] and the duplexer of other optical layers.
[6] laminated optical component of [5], wherein, above-mentioned optical layers comprises phase retardation film.
The invention effect
For polaroid of the present invention, its photo-curable bonding agent used in manufacturing shows low viscosity before solidifying, and the coating applicability improves, and after solidifying, shows high storage modulus, polarizer and diaphragm excellent bonds simultaneously.Even this polaroid is when for example repeatedly being placed under hot environment and being placed in the cold shock testing (thermal shock test) under low temperature environment, the possibility that polarizer breaks is also little, the reliability excellence.In addition, similarly, even be placed under harsh condition, the polarizer possibility of breaking is also little for the laminated optical component that stacked other optical layers such as phase retardation film obtain on this polarizer, adopts the reliability of liquid crystal indicator of this polaroid also excellent.
Embodiment
Below describe embodiment of the present invention in detail.In the present invention, via the photo-curable bonding agent, the diaphragm that at least one face of the polarizer of making at the polyvinyl alcohol resin film by having adsorbed dichroic dye orientation, laminating is made by transparent resin, make polaroid.This photo-curable bonding agent is formed by Photocurable adhesive composition, described Photocurable adhesive composition contains 100 weight portion light cation-curable compositions (A) and 1-10 weight portion light cationic polymerization initiators (B), and its solidfied material shows the storage modulus more than 1000MPa under 80 ℃.Further stacked other optical layers on this polaroid, can be made into the laminated optical component that is applicable to liquid crystal indicator.Therefore, successively to the Photocurable adhesive composition for the polaroid manufacture, use the polaroid of said composition and use the laminated optical component of this polaroid to describe.
[Photocurable adhesive composition]
As mentioned above, the Photocurable adhesive composition used in the present invention contains 100 weight portion light cation-curable compositions (A) and 1-10 weight portion light cationic polymerization initiators (B), and this light cation-curable composition (A) be take its total amount as benchmark, following (A1) that contains following amount and (A2):
There is 2 above epoxy radicals, at least 1 alicyclic epoxy compound (A1) closed with the ester ring type loops wherein in 50-95 % by weight molecule: and
5-50 % by weight chlorinity is below 1%, the diglycidyl ether compound (A2) shown in above formula (I).
(light cation-curable composition)
Alicyclic epoxy compound (A1) as the major component of light cation-curable composition (A) can be general known epoxy compound, from weatherability, refractive index and photo-curable, considers, preferably in its molecular structure, does not contain aromatic ring.Alicyclic epoxy compound (A1) for example can be enumerated the compound shown in following general formula (1)-(23).
Figure 636632DEST_PATH_IMAGE002
Figure 953213DEST_PATH_IMAGE003
Figure 767585DEST_PATH_IMAGE004
Figure 793310DEST_PATH_IMAGE005
In above-mentioned each general formula, R 1-R 46Independent separately, the alkyl of expression hydrogen atom or carbon number 1-6.R 1-R 46During for alkyl, the position of being combined with alicyclic structure is the position arbitrarily of 1-6.The alkyl of carbon number 1-6 can be that straight chain can be also side chain, can also have alicyclic structure.Y 1Mean oxygen atom or alkane two bases, Y 2-Y 21Independent separately, expression can be straight chain, also can have side chain, also can have alkane two bases of alicyclic structure.As the carbon number of alkane two bases, Y 2, Y 4, Y 9, Y 10, Y 11, Y 12, Y 13, Y 14, Y 15, Y 18, Y 19, Y 20, Y 21For 1-20, Y 1, Y 3, Y 5, Y 6, Y 7, Y 8, Y 17, Y 18For 2-20.Z 1-Z 2Independent separately, expression can be straight chain, also can have side chain, also can have alkane three bases of alicyclic structure.As the carbon number of alkane three bases, Z 1For 2-20, Z 2For 1-20.T 1Expression can be straight chain, also can have side chain, also can have alkane four bases of the carbon number 1-20 of alicyclic structure.A-r means the integer of 0-20.
Above-mentioned alicyclic epoxy compound (A1) can be used separately a kind, or two or more is mixed and uses.
The another kind of composition diglycidyl compounds (A2) of light cation-curable composition (A) is meaned by above formula (I).In formula (I), the alkylene base that Z is carbon number 1-9, carbon number 3 or 4 alkylidene radical, divalent ester ring type alkyl or formula-C mH 2m-Z 1-C nH 2n-shown in the divalent group, here ,-Z 1-be-SO 2-,-SO-or-CO-, m and n are independent separately, are the integer more than 1, both add up to below 9.The exemplary of divalent ester ring type alkyl is cyclopentylene or cyclohexylidene.
In formula (I), the compound that Z is alkylene base is the diglycidyl ether of alkylene base glycol.Provide its object lesson, ethylene glycol bisthioglycolate glycidyl ether, propylene glycol diglycidyl ether, 1,3-propane diol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexane diol diglycidyl ether, neopentyl glycol diglycidyl ether, 3-methyl isophthalic acid, 5-pentane diol diglycidyl ether, 2-methyl isophthalic acid, 8-octane glycol diglycidyl ether, 1,4-CHDM etc.
In formula (I), Z is formula-C mH 2m-Z 1-C nH 2n-shown in the compound of divalent group be equivalent to: Z is the alkylene base of carbon number more than 2, the C-C key quilt-SO of this alkylene base 2-,-SO-or-CO-cuts off.
The reason of diglycidyl compounds based on manufacturing process shown in formula (I), usually to contain in a large number the state circulation of chlorine., when the manufacture of this compound, if employing two-step approach, , at sulfuric acid, boron trifluoride, under the existence of the acidic catalysts such as butter of tin, make chloropropylene oxide and take that the alkylene base glycols is representative, the diol reaction that is equivalent to formula HO-Z-OH, manufacture the chloroethene alcohol ether, then, method by the chloroethene alcohol ether by alkali closed loop in molecule, in the addition reaction of the chloropropylene oxide of the 1st operation, can't avoid generating 2 moles of addition compound products of chloropropylene oxide, the contained organochlorine of these 2 moles of addition compound products does not decompose in the intramolecular ring-closing reaction of the 2nd operation, in addition, usually the glycidyl ethers can't distillation purifying, therefore as chlorine component, the organochlorine compound that contains 1-3 % by weight left and right in gained glycidyl ethers.
The chlorinity of the diglycidyl compounds of using in the present invention (A2) is necessary for below 1%, for example can make by the following method its chlorinity reduce: (1) is under the existence of alkali metal hydroxide, limit by the water in reaction system and azeotropic solvent (for example, as the hydro carbons of normal hexane, cyclohexane, normal heptane, benzene or toluene, ethers as ether or isopropyl ether, as 1,2-ethylene dichloride, 1, the halogenated hydrocarbon of 2-propylene dichloride, triclene or chloroform, the solvent that the azeotropic temperature of sulfoxide compound etc. is 30-90 ℃) azeotropic makes the method for 2 yuan of alcohol and chloropropylene oxide reaction except trimming; (2) equivalent of alkali metal hydroxide is adjusted to 0.5-1.5, makes its reaction under the existence of chloropropylene oxide, by washing and/or alkali sorbent treatment, the method for then heating up in a steamer chloropropylene oxide; (3), under the existence of alkali, make hydroxyl compound and chloropropylene oxide condensation, while irradiate method that ultrasound wave reacted etc.
(light cationic polymerization initiators)
The light cationic polymerization initiators (B) be matched with in Photocurable adhesive composition is to discharge the compound of the material that causes cationic polymerization by irradiation, particularly preferably is by irradiation and discharges the lewis acidic or derivatives thereof of the double salt as salt.The representational example of described compound can be enumerated: general formula [A] Y+[B] Y-Shown kation and the salt of negative ion.
Here, cation A Y+Be preferably, its structure example is as can be by [(R 41) xQ] Y+Mean.
And, R 45For carbon number 1-60, can contain the organic group of the atom beyond several carbon atoms, the integer that x is 1-5.X R 45Independent separately, can be the same or different.Also preferably at least one is aromatic group.Q is atom or the atomic group that is selected from S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, N=N.In addition, cation A Y+In the atomicity of Q while being z, must have the relation of y=x-z to set up.
Negative ion B Y-Be preferably halide complex, its structure example is as can be with [LX s] Y-Mean.
Here, the metal of the central atom that L is halide complex or semimetal (metalloid), be B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co etc.X is halogen.The integer that s is 3-7.In addition, negative ion B Y-In the atomicity of L while being t, must have the relation of y=s-t to set up.
Negative ion in above-mentioned general formula [LXs] Y-Object lesson can enumerate: tetrafluoroborate (BF 4) -, hexafluorophosphate (PF 6) -, hexafluoro antimonate (SbF 6) -, hexafluoro arsenate (AsF 6) -, chlordene antimonic salt (SbCl 6) -Deng.
In addition, negative ion B Y-Can preferably use [LXs -1(OH)] Y-Shown structure.L, X, s and above-mentioned same.Other operable negative ion also can be enumerated: high chloro acid ion (ClO 4) -, trifluoromethyl sulfurous acid ion (CF 3SO 3) -, fluosulfonic acid ion (FSO 3) -, toluenesulfonic acid negative ion, trinitro-benzene-sulfonic acid negative ion etc.
Negative ion B Y-Also can preferably use four (pentafluorophenyl group) borate.
In the present invention, in described salt, use aromatics salt effective especially.Wherein No. 50-151997, preferred Japanese kokai publication sho, the aromatic halonium salts of putting down in writing in Japanese kokai publication sho 50-158680 communique, No. 50-151997, Japanese kokai publication sho, No. 52-30899, Japanese kokai publication sho, No. 56-55420, Japanese kokai publication sho, the VIA family aromatics salt of record in Japanese kokai publication sho 55-125105 communique etc., the VA family aromatics salt of Japanese kokai publication sho 50-158698 communique record, No. 56-8428, Japanese kokai publication sho, No. 56-149402, Japanese kokai publication sho, oxa-sulfur oxide (oxo-sulfoxonium) salt of record in Japanese kokai publication sho 57-192429 communique etc., the aryl diazonium salt of No. 49-17040 record of Japanese kokai publication sho, the sulfo-pyralium salt of No. 4139655 instructions record of United States Patent (USP).
Particularly preferred as follows in these aromatics salt.
The cationic compound of sulfoxonium with following structure
Figure 919398DEST_PATH_IMAGE006
In formula, R 46-R 59For hydrogen atom, halogen atom that separately can be identical or different or can contain oxygen atom or halogen atom alkyl or can be with substituent alkoxy, Ar is that the hydrogen atom more than 1 can substituted phenyl.
There is cationic compound as described below:
(tolyl cumyl) iodine, two (tert-butyl-phenyl) iodine, triphenylsulfonium etc.
Providing concrete compound name, is for example 4-(4-benzoyl-thiophenyl) phenyl-bis--(4-fluorophenyl) sulfonium hexafluorophosphate, 4,4 '-bis-[two ((beta-hydroxy ethoxy) phenyl) sulfonium base] diphenyl sulfide-bis--hexafluorophosphate, 4,4 '-bis-[two ((beta-hydroxy ethoxy) phenyl) sulfonium base] diphenyl sulfide-bis--hexafluoro antimonate, 4,4 '-bis-(difluorophenyl sulfonium base) diphenyl sulfide-bis--hexafluorophosphate, 4,4 '-bis-(difluorophenyl sulfonium base) diphenyl sulfide-bis--hexafluoro antimonate, 4,4 '-bis-(phenyl sulfonium base) diphenyl sulfide-bis--hexafluorophosphate, 4,4 '-bis-(phenyl sulfonium base) diphenyl sulfide-bis--hexafluoro antimonate, 4-(4-benzophenone sulfenyl) phenyl-bis--(4-(beta-hydroxy ethoxy) phenyl) sulfonium hexafluorophosphate, 4-(4-benzophenone sulfenyl) phenyl-bis--(4-(beta-hydroxy ethoxy) phenyl) sulfonium hexafluoro antimonate, 4-(4-benzophenone sulfenyl) phenyl-bis--(4-fluorophenyl) sulfonium hexafluorophosphate, 4-(4-benzophenone sulfenyl) phenyl-bis--(4-fluorophenyl) sulfonium hexafluoro antimonate, 4-(4-benzophenone sulfenyl) phenyl-diphenyl sulfonium hexafluorophosphate, 4-(4-benzophenone sulfenyl) phenyl-diphenyl sulfonium hexafluoro antimonate, 4-(thiophenyl) phenyl-bis--(4-(beta-hydroxy ethoxy) phenyl) sulfonium hexafluorophosphate, 4-(thiophenyl) phenyl-bis--(4-(beta-hydroxy ethoxy) phenyl) sulfonium hexafluoro antimonate, 4-(thiophenyl) phenyl-bis--(4-fluorophenyl) sulfonium hexafluorophosphate, 4-(thiophenyl) phenyl-bis--(4-fluorophenyl) sulfonium hexafluoro antimonate, 4-(thiophenyl) phenyl-diphenyl sulfonium hexafluorophosphate, 4-(thiophenyl) phenyl-diphenyl sulfonium hexafluoro antimonate, two (4-fluorophenyl) the sulfonium hexafluorophosphates of 4-(the chloro-4-benzophenone of 2-sulfenyl) phenyl, two (4-fluorophenyl) the sulfonium hexafluoro antimonates of 4-(the chloro-4-benzophenone of 2-sulfenyl) phenyl, 4-(the chloro-4-benzophenone of 2-sulfenyl) phenyl diphenyl sulfonium hexafluorophosphate, 4-(the chloro-4-benzophenone of 2-sulfenyl) phenyl diphenyl sulfonium hexafluoro antimonate, two (4-hydroxy phenyl) the sulfonium hexafluorophosphates of 4-(the chloro-4-benzophenone of 2-sulfenyl) phenyl, two (4-hydroxy phenyl) the sulfonium hexafluoro antimonates of 4-(the chloro-4-benzophenone of 2-sulfenyl) phenyl, the triphenylsulfonium hexafluorophosphate, the triphenylsulfonium hexafluoro antimonate, (tolyl cumyl) iodine hexafluorophosphate, (tolyl cumyl) iodine hexafluoro antimonate, (tolyl cumyl) iodine four (pentafluorophenyl group) borate, two (tert-butyl-phenyl) iodine hexafluorophosphate, two (tert-butyl-phenyl) iodine hexafluoro antimonate, two (tert-butyl-phenyl) iodine four (pentafluorophenyl group) borate, benzyl-4-hydroxy phenyl methyl sulfonium hexafluorophosphate, benzyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate, benzyl dimethyl sulfonium hexafluorophosphate, benzyl dimethyl sulfonium hexafluoro antimonate, p-chlorobenzyl-4-hydroxy phenyl methyl sulfonium hexafluorophosphate, p-chlorobenzyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate, 4-acetoxyl group phenyl dimethyl sulfonium hexafluorophosphate, 4-acetoxyl group phenyl dimethyl sulfonium hexafluoro antimonate, 4-methoxycarbonyl oxygen base phenyl dimethyl sulfonium hexafluorophosphate, 4-methoxycarbonyl oxygen base phenyl dimethyl sulfonium hexafluoro antimonate, 4-ethoxy carbonyl oxygen base phenyl dimethyl sulfonium hexafluorophosphate, 4-ethoxy carbonyl oxygen base phenyl dimethyl sulfonium hexafluoro antimonate, Alpha-Naphthyl methyl dimethoxy base sulfonium hexafluorophosphate, Alpha-Naphthyl methyl dimethoxy base sulfonium hexafluoro antimonate, Alpha-Naphthyl methyl butylidene sulfonium hexafluorophosphate, Alpha-Naphthyl methyl butylidene sulfonium hexafluoro antimonate, cinnamyl dimethyl sulfonium hexafluorophosphate, cinnamyl dimethyl sulfonium hexafluoro antimonate, cinnamyl butylidene sulfonium hexafluorophosphate, cinnamyl butylidene sulfonium hexafluoro antimonate, N-(α-phenylbenzyl) cyanopyridine hexafluorophosphate, N-(α-phenylbenzyl)-2-cyanopyridine hexafluoro antimonate, N-cinnamyl-2-cyanopyridine hexafluorophosphate, N-cinnamyl-2-cyanopyridine hexafluoro antimonate, N-(Alpha-Naphthyl methyl)-2-cyanopyridine hexafluorophosphate, N-(Alpha-Naphthyl methyl)-2-cyanopyridine hexafluoro antimonate, N-benzyl-2-cyanopyridine hexafluorophosphate, N-benzyl-2-cyanopyridine hexafluoro antimonate etc.
Other preferred light cationic polymerization initiators also can be enumerated: the iron/arene Complex of imines etc., aluminium complex/light analysing silicon series of compounds initiating agent etc. between dimethylbenzene-cyclopentadienyl group iron (II) hexafluoro antimonate, cumene-cyclopentadienyl group iron (II) hexafluorophosphate, dimethylbenzene-cyclopentadienyl group iron (II)-tri-(trifluoromethyl sulfonyl).
The light cationic polymerization initiators (B) of above-mentioned explanation can be used separately respectively a kind, also two or more can be mixed and uses, and its use amount is all with respect to 100 weight portion light cation-curable compositions (A), is the 1-10 % by weight.If the use level of light cationic polymerization initiators (B) is very few, bonding agent is curing insufficient, and bond strength reduces.On the other hand, if its amount too much, the ionic substance in solidfied material increases, and the hydroscopicity of solidfied material improves as a result, and the endurance quality of polaroid reduces.
(can be matched with other composition in Photocurable adhesive composition)
In order to improve the coating applicability, in this Photocurable adhesive composition, can coordinate on a small quantity organic solvent.Organic solvent is not so long as make the optical property of polarizer reduce, but the excellent dissolution Photocurable adhesive composition get final product, its kind is not particularly limited.Take the hydro carbons that toluene is representative, the organic solvents such as ester class that the ethyl acetate of take is representative such as using.
This Photocurable adhesive composition can further contain alicyclic epoxy compound (A1) and diglycidyl compounds (A2) polymerizable monomer in addition.Polymerizable monomer can exemplify: cationically polymerizable monomer, free radical polymerization monomer etc.
The cationically polymerizable monomer for example can be enumerated the oxetanes class.The oxetanes class is the compound that has 4 yuan of cyclic ethers in molecule, for example can enumerate: 3-ethyl-3-hydroxymethyl oxetanes, Isosorbide-5-Nitrae-bis-[(3-ethyl-3-oxa-cyclobutyl) methoxy] benzene, 3-ethyl-3-(phenoxymethyl) oxetanes, two [(3-ethyl-3-oxa-cyclobutyl) methyl] ether, 3-ethyl-3-(2-ethyl hexyl oxy methyl) oxetanes, linear novolaks oxetanes.These oxetane compounds can easily obtain commercial goods, such as these trade names, can enumerate: " ア ロ Application オ キ セ タ Application OXT-101 ", " ア ロ Application オ キ セ タ Application OXT-121 ", " ア ロ Application オ キ セ タ Application OXT-211 ", " ア ロ Application オ キ セ タ Application OXT-221 ", " ア ロ Application オ キ セ タ Application OXT-212 " (above East Asia synthetic (strain) manufactures) etc.
Above-mentioned cationically polymerizable monomer has the effect that the adaptation after bonding agent solidifies is improved, and can as required, weatherability, photo-curable not had in influential scope and use.
Free radical polymerization monomer for example can be enumerated: acrylate compounds, methacrylate compound (below, on the meaning that comprises acrylate and methacrylate, also be recited as (methyl) acrylate), allyl amino formic acid ester compound, unsaturated polyester compound, polystyrene compound.During for photo-curable bonding agent of the present invention, from easy acquisition, easily application consideration, preferably (methyl) acrylate.(methyl) acrylate can be enumerated: (methyl) acrylate of carbamate (methyl) acrylate, (gathering) ester (methyl) acrylate, (gathering) ether (methyl) acrylate, alcohols, other (methyl) acrylate.
Here, carbamate (methyl) acrylate exemplified as (methyl) acrylate compounds is the ester compounds with amino-formate bond, can be to make (methyl) acrylate of hydroxyl react with one kind or two or more (gathering) isocyanate compound (methyl) acrylate obtained, wherein, (methyl) acrylate of described hydroxyl is the polyvalent alcohol and (methyl) acrylic acid ester compounds of one kind or two or more (gathering) ester type polyvalent alcohol, (gathering) ether type polyvalent alcohol, polyvalent alcohol etc.; Make the polyvalent alcohol of one kind or two or more (gathering) ester type polyvalent alcohol, (gathering) ether type polyvalent alcohol, polyvalent alcohol etc. react (methyl) acrylate obtained etc. with (methyl) acrylate and the isocyanates of hydroxyl.
The polyvalent alcohol that can derive (gathering) ester type polyvalent alcohol for example can be enumerated: 1,3-butanediol, 1,4-butanediol, 1,6-hexane diol, diglycol, triethylene glycol, neopentyl glycol, polyglycol, polypropylene glycol, polytetramethylene glycol, trimethylolpropane, glycerine, pentaerythrite, dipentaerythritol etc.Can derive the polybasic carboxylic acid of (gathering) ester type polyvalent alcohol such as enumerating: hexane diacid, terephthalic acid (TPA), phthalic anhydride, trimellitic acid, trimesic acid etc.
(gathering) ether type polyvalent alcohol can be enumerated: in above-mentioned polyvalent alcohol addition the product of the alkylene oxides such as oxirane, epoxypropane, epoxy butane.(gathering) isocyanate compound can be enumerated the isocyanates more than 1 yuan or 2 yuan, preferably the isocyanates more than 2 yuan.
Isocyanates more than 2 yuan can be enumerated: 2, 4-and/or 2, the 6-toluene diisocyanate, diphenyl methane-4, 4 '-diisocyanate, PPDI, the xylylene diisocyanate, 1, the 5-naphthalene diisocyanate, 3, 3 '-dimethyl diphenyl-4, 4 '-diisocyanate, two anisidine diisocyanate, tetramethylbenzene dimethyl diisocyanate, isophorone diisocyanate, dicyclohexyl methyl hydride-4, 4 '-diisocyanate, trans and/or cis-1, the 4-cyclohexane diisocyanate, the norborene diisocyanate, 1, the 6-hexylidene diisocyanate, 2, 2, 4 and/or (2, 4, 4)-trimethyl hexylidene diisocyanate, lysinediisocyanate, triphenylmethane triisocyanate, 1-methylbenzene-2, 4, the 6-triisocyanate, dimethyl triphenyl methane tetraisocyanate.
Polyester (methyl) acrylate is to have 1 or 2 above hydroxyls (gathering) ester and (methyl) acrylic acid ester compounds in molecule.(gathering) ester that has 1 or 2 above hydroxyl in molecule can be enumerated: the ester compounds of one kind or two or more polyvalent alcohol and one kind or two or more monocarboxylic acid or polybasic carboxylic acid.
The polyvalent alcohol that can derive in molecule (gathering) ester with 1 or 2 above hydroxyl can be enumerated the compound same with above-claimed cpd, and monocarboxylic acid is such as enumerating: formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, sad, 2 ethyl hexanoic acid, benzoic acid etc.Polybasic carboxylic acid can be enumerated the compound same with above-claimed cpd.
(gathering) ether (methyl) acrylate is to have 1 or 2 above hydroxyls (gathering) ether and (methyl) acrylic acid ester compounds in molecule.(gathering) ether that has 1 or 2 above hydroxyl in molecule can be enumerated: the compound that the one kind or two or more alkylene oxide of addition obtains in 2-methyl cellosolve, cellosolvo, butoxy ethanol, polyvalent alcohol.Polyvalent alcohol and alkylene oxide can be enumerated the compound same with above-claimed cpd.Can enumerate specifically: trimethylolpropane tris (methyl) acrylate of two (methyl) acrylic acid diglycol ester, two (methyl) acrylic acid triethyleneglycol ester, two (methyl) polyalkylene glycol acrylate ester, two (methyl) acrylic acid polypropylene glycol ester, oxirane modification, trimethylolpropane tris (methyl) acrylate of epoxy pronane modification, six (methyl) acrylic acid dipentaerythritol ester etc.
(methyl) acrylate of alcohols is alcohol (particularly aliphatic alcohol or the aromatic alcohol) class that has 1 or 2 above hydroxyl in molecule and the ester compounds of (methyl) acrylate.For example can enumerate: (methyl) 2-EHA, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid isopentyl ester, (methyl) acrylic acid Lauryl Ester, (methyl) stearyl acrylate base ester, (methyl) isooctyl acrylate ester, (methyl) acrylic acid tetrahydrofuran base ester, (methyl) isobornyl acrylate, (methyl) acrylic acid benzyl ester, (methyl) acrylic acid 1, 3-butanediol ester, (methyl) acrylic acid 1, 4-butanediol ester, (methyl) acrylic acid DOPCP, (methyl) acrylic acid 1, 6-hexane diol ester, trimethylolpropane tris (methyl) acrylate, four (methyl) acrylic acid, five pentaerythritol esters etc.
Other acrylate can be enumerated: six (methyl) acrylic acid dipentaerythritol ester of 6-caprolactone modification, fluorene derivative two (methyl) acrylate, carbazole derivates two (methyl) acrylate etc.
Above-mentioned free radical polymerization monomer is for regulating curing rate.
When polymerizable monomer is used free radical polymerization monomer, also coordinate the optical free radical polymerization initiator.The optical free radical polymerization initiator can be enumerated: the ketone based compounds such as acetophenone based compound, benzil based compound, benzophenone based compound, thioxanthones based compound.
The acetophenone based compound for example can be enumerated: diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 4 '-isopropyl-2-hydroxy-2-methyl propiophenone, 2-hydroxymethyl-2-methyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-ketone, to the dimethylamino benzoylformaldoxime, to tert-butyl group dichloroacetophenone, to tert-butyl group trichloroacetophenone, to the azido benzalacetophenone, the 1-hydroxycyclohexylphenylketone, 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino acetone-1, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-1, benzoin, benzoin methyl ether, benzoin ethyl ether, the benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether etc., the benzil based compound can be enumerated: benzil, anisil etc., the benzophenone based compound for example can be enumerated: benzophenone, methyl o-benzoylbenzoate, michaelis ketone, 4,4 '-bis-diethylamino benzophenone, 4,4 '-dichloro benzophenone, 4-benzoyl-4 '-methyldiphenyl thioether etc., the thioxanthones based compound can be enumerated: thioxanthones, 2-methyl thioxanthones, 2-ethyl thioxanthones, CTX, ITX, 2,4-diethyl thioxanthone etc.
These optical free radical polymerization initiators can coordinate one kind or two or more use according to desired properties, with respect to free radical polymerization monomer, preferably coordinate 0.05-10 quality %, more preferably 0.1-10 quality %.The optical free radical polymerization initiator is that 0.05 quality % is when above with respect to the use level of free radical polymerization monomer, can carry out more well solidifying of photo-curable bonding agent, be 10 quality % when following, the physical strength of the adhesive phase that photo-curable bonding agent of the present invention is solidified to form is good.
It can be also potpourri of more than two kinds that the compound used as polymerizable monomer can be a kind.When the photo-curable bonding agent contains the polymerizable monomer except ester ring type epoxy compound (A1) and diglycidyl compounds (A2), the use amount of these polymerizable monomers is with respect to the 100 above-mentioned alicyclic epoxy compounds of weight portion (A1), is preferably below 100 weight portions.The use amount of polymerizable monomer is 100 weight portions when following, when using the photo-curable bonding agent to make polaroid, can make the bond strength of polarizer and diaphragm keep well.More preferably polymerizable monomer is more than 5 weight portions with respect to the use amount of 100 weight portion alicyclic epoxy compounds (A1), can well obtain the modified effect that polymerizable monomer brings in this case.Also more preferably the use amount of polymerizable monomer is below 50 weight portions.
In the scope of not damaging effect of the present invention, in this photo-curable bonding agent, can contain various additive components.Additive component, except above-mentioned optical free radical polymerization initiator, can also coordinate photosensitizer, hot cationic polymerization initiators, polyalcohols, ion trap agent, antioxidant, light stabilizer, chain-transferring agent, sensitizer, gluing agent, thermoplastic resin, filling agent, flowing regulator, plastifier, defoamer, even paint, dyestuff, the organic solvent etc. of providing.
While containing additive component, preferably its use amount is below 1000 weight portions with respect to the 100 above-mentioned alicyclic epoxy compounds of weight portion (A1).This use amount is 1000 weight portions when following, can bring into play well that combination as at least alicyclic epoxy compound (A1), diglycidyl compounds (A2) and the light cationic polymerization initiators (B) of the essential composition of photo-curable bonding agent is that bring, raising that guarantee storage stability, anti-variable color, the raising of curing rate, good fusible effect.
[polaroid]
Use above-mentioned Photocurable adhesive composition by polarizer and diaphragm laminating, manufacture polaroid.Between polarizer and diaphragm, the method for coating photo-curable bonding agent is not particularly limited, such as adopting paint chipping chisel, scraper blade coating device, mould to be coated with the various coating methods such as machine, unfilled corner wheel coating machine, intaglio plate coating machine.Also can utilize and drip above-mentioned photo-curable bonding agent between polarizer and diaphragm, then with pressurizations such as rollers, the method evenly pressed off.Here, the material of roller can be used metal or rubber etc., and the material after dripping above-mentioned photo-curable bonding agent between polarizer and diaphragm is pressurizeed between by roller and roller, and when it is extended, these rollers can be identical materials, can be also different materials.The thickness of adhesive phase is generally below 50 μ m, preferably below 20 μ m, further preferably below 10 μ m.
Like this, on the adhesive phase formed by the photo-curable bonding agent, laminating has transparent diaphragm.Here the diaphragm that used is not particularly limited, specifically can use at present as the diaphragm of the polaroid acetylcellulose mesentery such as widely used triacetyl cellulose, or than triacetyl cellulose moisture permeability the film of low transparent resin.The moisture permeability of triacetyl cellulose is approximately 400g/m 2About/24 hours.When the two sides of polarizer laminating diaphragm, can, by the simultaneously laminating of one side stage by stage of 2 diaphragms, also two sides one step can be fitted.
The acetylcellulose mesentery used in the present invention, except above-mentioned tri acetyl cellulose membrane, also can be enumerated: diacetyl cellulose film, acetyl tributyl cellulose membrane etc.
The example of the transparent resin film that the moisture permeability of using in the present invention is low can be enumerated: amorphous polyolefins resin film, polyester based resin film, acrylic resin film, polycarbonate resin film, polysulfones resin film, ester ring type polyimide resin film etc.Wherein particularly preferably using by amorphous polyolefins is the film that resin is made.Amorphous polyolefins is that resin usually has as norborene or encircles the polymerized unit of the cyclic olefin the norborneol alkene monomer more, can be also the multipolymer of cyclic olefin and chain alkene.Wherein, the thermoplasticity saturated norbornene is that resin is representational.In addition, the resin of introducing polar group is also effective.Commercially available amorphous polyolefins is that resin has: the “ ア ー ト Application that ジ ェ イ エ ス ア ー Le (strain) is manufactured ", " ZEONEX " and " ZEONOR " that manufacture of Japanese ゼ オ Application (strain), " APO " and " ア ペ Le " of Mitsui Chemicals (strain) manufacture etc.Be the resin film forming by amorphous polyolefins, make film, during film forming, can suitably adopt the known methods such as solvent cast method, extrusion by melting.
In the present invention, one of preferred scheme is that diaphragm is that 300g/m is made, had to resin by amorphous polyolefins 2Moisture permeability below/24 hours.
When the two sides of polarizer laminating diaphragm, both can be identical type, can be also different kinds.When different types of diaphragm is fitted on the two sides of polarizer; one side diaphragm can be used the low resin molding of moisture permeability of above-mentioned amorphous polyolefins resin film, polyester based resin film, acrylic resin film, polycarbonate resin film, polysulfones resin film, ester ring type polyimide resin film etc., and the diaphragm of opposite side also can be used the cellulose ethanoate mesenterys such as above-mentioned tri acetyl cellulose membrane, diacetyl cellulose film or acetyl tributyl cellulose membrane except these.In addition; as above on a face of polarizer, arrange by as cellulose ethanoate mesentery etc. the higher resin molding of moisture permeability make diaphragm the time, the binding face of the resin molding that described moisture permeability is high can be used the epoxy system bonding agent in addition of polyethenol series bonding agent etc.
Before fitting on polarizer, the binding face of diaphragm can be implemented the easily adhesion process such as saponification processing, corona treatment, Cement Composite Treated by Plasma, anchoring coating processing.Can there are the various processing layers such as hard coat, anti-reflection layer, antiglare layer on a contrary side surface of the face of fitting with polarizer of diaphragm.The thickness of diaphragm is generally the scope of 5-200 μ m left and right, preferred 10-120 μ m, further preferred 10-85 μ m.
The polarizer obtained for the diaphragm of fitting on polarizer via uncured adhesive phase as mentioned above, then irradiate active energy beam, makes thus the adhesive phase of being made by composition epoxy resin solidify, and diaphragm is bonded on polarizer.
The light source of active energy beam is not particularly limited, can use below wavelength 400nm, have send out photodistributed, such as low pressure mercury lamp, medium pressure mercury lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, chemical lamp, black lamp, microwave-excitation mercury lamp, metal halid lamp etc.The irradiation intensity of composition epoxy resin according to every kind of objective composition and definite, also is not particularly limited, and is preferably 0.1-100mW/cm to the exposure intensity of the effective wavelength region may of activation of initiating agent 2.If to the irradiation intensity of resin combination lower than 0.1mW/cm 2, the reaction time long, and if surpass 100mW/cm 2, by the heat of lamp radiation and composition, the heating when the polymerization may produce the deteriorated of the xanthochromia of composition epoxy resin or polarizer.To irradiation time of composition be subject to every kind will be curing the control of composition, also be not particularly limited, be preferably set to: the accumulated light of product representation of exposure intensity and irradiation time of take is 10-5,000mJ/cm 2.If to the accumulated light of above-mentioned composition epoxy resin lower than 10mJ/cm 2,, from the generation deficiency of the activation kind of initiating agent, the curing of gained diaphragm may be insufficient, and this accumulated light surpasses 5,000mJ/cm 2, irradiation time is very long, and productivity raising aspect is unfavorable.
When the irradiation by active energy beam is solidified the photo-curable bonding agent, preferably in the scope that each function of the polaroid of polarization luminosity, transmissivity and the form and aspect of polarizer or the transparency of diaphragm etc. does not reduce, it is solidified.
[laminated optical component]
During the polaroid application, also can, via protective film of the present invention, make the optical component that is provided with the optical layers that shows polarisation function optical function in addition.On the target polaroid in the optical layers of stacked formation optical component, such as the member of the formation for liquid crystal indicator etc. that reflection horizon, Transflective layer, light diffusion layer, phase difference film, light-collecting piece, raising brightness film etc. are arranged.Above-mentioned reflection horizon, Transflective layer, light diffusion layer are used to form the situation of the optical component of being made by reflection-type and Semitransmissive or diffused, their polaroid of dual-purpose type.
The liquid crystal indicator of the type that the incident light that the polaroid of reflection-type is recognized side for considering oneself as by reflection is shown, can omit the light source backlight of Denging, therefore easily makes the liquid crystal indicator slimming.And the polaroid of Semitransmissive at bright place as the liquid crystal indicator of reflection-type, the type that in the dark shown via light source backlight etc.Such as being to set up paper tinsel or the vapor-deposited film formed by metals such as aluminium on the diaphragm of polarizer, form reflection horizon as the optical component of reflection type polarizer.As the optical component of Semitransmissive polaroid, be that half-mirror is made in above-mentioned reflection horizon, or will contain pearlescent pigment, show that reflecting plate and the polaroid-bindnig of half transmitting form.On the other hand, as the optical component of diffused polaroid, be for example to adopt the diaphragm on polaroid is implemented to the method that delustring is processed; Coating is containing the method for the resin of particulate; The whole bag of tricks such as method of the bonding film containing particulate, form the micro concavo-convex structure on surface.
The formation of the optical component of the dual-purpose polaroid form of reflection diffusion, such as adopting the method that the reflection horizon of having reflected this concaveconvex structure etc. is set on the micro concavo-convex structural plane of diffused polaroid to carry out.The reflection horizon of micro concavo-convex structure has by scattering to be made the incident light diffusion, prevent directivity or dazzle, can suppress the advantage of light and shade inequality etc.In addition, containing fine-grained resin bed or film, when incident light and reflected light thereof see through the layer containing particulate, spread, also have advantages of that can to suppress light and shade unequal.Methods such as evaporation that can be by vacuum evaporation, ion plating, sputter etc. or coating of the reflection horizon of reflecting surperficial micro concavo-convex structure, the surface that directly metal is attached to the micro concavo-convex structure forms.The particulate coordinated in order to form surperficial micro concavo-convex structure is such as can be to comprise that the inorganic of silicon dioxide that mean grain size is 0.1-30 μ m, aluminium oxide, titanium dioxide, zirconia, tin oxide, indium oxide, cadmium oxide, antimony oxide etc. is particulate, the organic system particulate of being made by crosslinked or noncrosslinking polymkeric substance etc. etc.
On the other hand, the purpose of the phase difference film of above-mentioned optical layers form is phase difference compensation for liquid crystal cell etc.Its example can be enumerated: the birefringence film of being made by stretched film of various plastics etc., be orientated and be fixed with the film of discotic mesogenic or nematic liquid crystal, formed the material of above-mentioned liquid crystal layer etc. on film base material.In this case, the film base material as supporting the aligned liquid-crystal layer, preferably used the cellulose-based resin moldings such as triacetyl cellulose.
The plastics of form dielectric grid film for example can be enumerated: the polyolefin of polycarbonate, polyvinyl alcohol (PVA), polystyrene, polymethacrylate, polypropylene and so on, polyarylate, polyamide etc.Stretched film can be processed and obtain by suitable modes such as single shaft or twin shafts.Under bonding with heat-shrinkable film, by applying convergent force and/or tensile force, can obtain the controlled birefringence film of refractive index of the thickness direction of film.Should illustrate, the purpose of phase difference film is to carry out the control of the optical characteristics such as broadband, can will more than 2, be used in combination.
Light collecting plate be take light path control etc. and is used as purpose, therefore can make the form of the plate etc. of prism array sheet or lens array plate or attachment point.
The purpose that improves the brightness film is the raising for the brightness of liquid crystal indicator etc., so its example can be enumerated: be designed to the anisotropy of refractive index stacked, the anisotropic reflective polarizing light separating sheet that produces reflectivity of different film multi-disc mutually; Circularly polarizing separation sheet formed at alignment films or this aligned liquid-crystal layer of film base material upper support cholesteric liquid crystal polymkeric substance etc.
Optical component can be by polaroid, combine with the optical layers more than 1 layer or 2 layers of selecting from above-mentioned reflection horizon and Transflective layer, light diffusion layer, phase difference film, light-collecting piece, raising brightness film etc. according to application target, makes the duplexer more than 2 layers or 3 layers.In this case, the optical layers of light diffusion layer or phase difference film, light-collecting piece or raising brightness film etc. can configure respectively more than 2 layers.Should illustrate, the configuration of each optical layers is not particularly limited.
The various optical layers that form laminated optical component are used bonding agents to make one, as long as for this reason and the bonding agent used can well form adhesive phase, are not particularly limited.From the simplicity of bonding operation or prevent the considerations such as generation of optical aberration, preferably use tackifier (also referred to as contact adhesive).Tackifier can be used usings the material as raw polymer such as acrylic acid series polymeric compounds or silicon-type polymkeric substance, polyester, polyurethane, polyethers.Wherein, as acrylic pressure-sensitive adhesive, preferably select optical transparence excellent, keep appropriate wellability or aggregation force, also excellent and there are weatherability or thermotolerance etc., under the condition of heating or humidification, perk occur or peel off etc. to peel off problem and use with the cohesive of base material.In acrylic pressure-sensitive adhesive, acrylic acid series copolymer can be used as raw polymer, this acrylic acid series copolymer has coordinated the acrylic monomer containing functional group that has (methyl) acrylic acid Arrcostab that methyl or the carbon numbers such as ethyl or butyl are the alkyl below 20 and made by (methyl) acrylic acid or (methyl) Hydroxyethyl Acrylate etc., its glass transition temperature is preferably below 25 ℃, further preferably below 0 ℃, weight-average molecular weight is more than 100,000.
Form adhesive phase on polaroid, such as carrying out in the following manner: dissolve or the dispersion agent adhesive composition in the organic solvents such as toluene or ethyl acetate, the solution of preparation 10-40 % by weight, directly coat by it mode that forms adhesive layer on polaroid; Perhaps form in advance adhesive layer on diaphragm, its transfer lamination is formed thus to mode of adhesive layer etc. to polaroid.The thickness of adhesive layer is according to decisions such as its bounding forces, and the scope of 1-50 μ m left and right is comparatively suitable.
Also can as required, coordinate the filling agent of being made by glass fibre or beaded glass, resin bead, metal powder or other inorganic powder etc., pigment or colorant, antioxidant, ultraviolet light absorber etc. in adhesive layer.Ultraviolet light absorber has: salicylate based compound or benzophenone based compound, benzotriazole based compound, cyanoacrylate based compound, nickel complex salt based compound etc.
The configurable one or both sides at liquid crystal cell of optical component.The liquid crystal cell used is arbitrarily, such as for take that film transistor type is representative active matrix drive-type, simple matrix that the super-twist nematic of take is representative is driving etc., can use various liquid crystal cells to form liquid crystal indicators.The optical component that is arranged at the liquid crystal cell both sides can be the same or different.
Embodiment
Below provide embodiment, further illustrate the present invention, but the present invention is not subject to the restriction of these embodiment.In example, as long as no special instructions, mean that the % of content and use amount and part are weight basis.Given first is made the reference example as the film of the polyethylene terephthalate with antiglare layer of the diaphragm use of polarizer one side.
[reference example] (making with polyethylene terephthalate film of antiglare layer)
Below each composition with solid content composition 60%, be dissolved in ethyl acetate, obtain the ultra-violet solidified resin composition of 1.53 refractive indexes after prepare solidifying.
60 parts of pentaerythritol triacrylates
40 parts of polyfunctional carbamate, acrylate.
Polyfunctional carbamate, acrylate: the reaction product of hexylidene diisocyanate and pentaerythritol triacrylate.
Then, solid composition with respect to 100 parts of these ultra-violet solidified resin compositions, add 2 parts of porous silica particles [trade name " サ イ リ シ ア ", the シ リ シ ア of Fuji chemistry (strain) is manufactured], 5 parts as 2 of Photoepolymerizationinitiater initiater, 4,6-trimethylbenzene formyl hexichol phosphorous oxides (trade name " Le シ リ Application TPO ", BASF manufactures), preparation antiglare layer coating fluid.
This coating fluid is coated to the face that easy bonding coat is not set (face of being made by polyethylene terephthalate itself) of the biaxial stretch-formed polyethylene terephthalate film of the easy bonding coat of single face, thickness 38 μ m, form the ultra-violet solidified resin composition layer, in being set as the dryer of 80 ℃ dry 3 minutes.With UVA (315-400nm) wavelength, illumination 250mW/cm 2, accumulated light 300mJ/cm 2Irradiated the light of high-pressure sodium lamp by ultra-violet solidified resin composition layer one side of dried film, the ultra-violet solidified resin composition layer is solidified, obtain the antiglare film of being made by the duplexer of the antiglare layer (cured resin) of the irregular thickness 5 μ m of surperficial tool and biaxial stretch-formed polyethylene terephthalate film.Use mist degree transmissivity instrument " HM-150 " [in (strain) village, color technical institute manufactures] to measure the haze value of this antiglare film, obtain 10% haze value.
Then prepare Photocurable adhesive composition, provide and be applicable to embodiment and the comparative example that polaroid is made.The light cation-curable composition and the light cationic polymerization initiators that in following example, use are as follows, with following symbol, mean respectively.
(A) light cation-curable composition
(A1) alicyclic epoxy compound
A1:3,4-epoxy-cyclohexane formic acid 3,4-epoxy radicals cyclohexyl methyl esters
(A2) diglycidyl compounds
A21:1,4-butanediol diglycidyl ether [chlorinity 0.5%]
A21c:1,4-butanediol diglycidyl ether [chlorinity 8.0%]
A22: neopentyl glycol diglycidyl ether [chlorinity 0.5%]
A22c: neopentyl glycol diglycidyl ether [chlorinity 8.1%]
A23: cyclohexanedimethanol diglycidyl ether [chlorinity 0.4%]
A23c: cyclohexanedimethanol diglycidyl ether [chlorinity 7.7%].
(B) light cationic polymerization initiators (in table referred to as " initiating agent ")
(b1) triaryl matte hexafluorophosphate
[embodiment 1 and 2 and comparative example 1-9]
(1) preparation of Photocurable adhesive composition
According to proportioning shown in table 1, light cation-curable composition and light cationic polymerization initiators are mixed, then deaeration, prepare photo-curable bonding agent liquid.Should illustrate, light cationic polymerization initiators (b1) is the form cooperation with 50% polypropylene carbonate ester solution, and table 1 is with its solid matter quantity representation.
(2) solidify the mensuration of the cl concn of front bonding agent
Contained cl concn in each bonding agent liquid of the above-mentioned preparation of following mensuration.; at first each bonding agent liquid is decomposed in burner " TOX-100 " [manufacture of (strain) ダ イ ア イ Application ス Star Le メ Application Star]; by gas entrapment in absorption liquid; then obtain chlorine dose by chromatography of ions device " ICS-2000 " (ダ イ オ ネ Network ス), the amount of the bonding agent liquid used in this amount and initial decomposition is calculated cl concn.Each cl concn measurement result is illustrated in table 1.
(3) mensuration of the storage modulus of solidfied material under 80 ℃
Use coating machine [metering bar coater, the first physics and chemistry (strain) is manufactured], polyethylene terephthalate film [the trade name " エ ス テ Le Off ィ Le system E7002 spins in Japan " that does not there is easy bonding coat on surface, Japan weaving (strain) is manufactured] a face on each bonding agent liquid of preparation in coating above-mentioned (1), the thickness after making to solidify is about 25 μ m.Then, " D バ Le Block " irradiation ultraviolet radiation of manufacturing with フ ュ ー ジ ョ Application UV シ ス テ system ズ society, accumulated light is 3,000mJ/cm 2, bonding agent is solidified.Its cutting is become to 5mm * 30mm size, peel off the polyethylene terephthalate film, obtain the cured film of bonding agent.Use ア イ テ ィ ー instrumentation to control the Measurement of Dynamic Viscoelasticity device " DVA-220 " that (strain) manufactures, clamp cured film obtained above with grip separation 2cm, making its long limit is draw direction, the frequency of draw and shrink is 1Hz, programming rate is set as to 3 ℃/minute, obtains the storage modulus at 80 ℃ of temperature.Result is as shown in table 1.
(4) manufacture of polaroid
Tri acetyl cellulose membrane [trade name " Off ジ タ ッ Network " to the thickness 80 μ m that contain ultraviolet light absorber, the Off イ of Fuji Le system (strain) is manufactured] surface implement Corona discharge Treatment, use metering bar coater, each bonding agent liquid of preparation in coating above-mentioned (1) on this Corona discharge Treatment face, the thickness after solidifying is 3 μ m approximately.Polyvinyl alcohol (PVA)-the iodine of fitting on this adhesive phase is polarizer.Also Corona discharge Treatment is implemented in the surface (easy bonding aspect) of the side relative with antiglare layer of the biaxial stretch-formed polyethylene terephthalate film made in reference example, have antiglare layer, thickness 43 μ m, use metering bar coater, coating and above-mentioned same bonding agent liquid on this Corona discharge Treatment face, the thickness after solidifying is 3 μ m approximately.Polarizer one side of the polarizer of the tri acetyl cellulose membrane of the above-mentioned preparation of having fitted on a face is fitted on this adhesive phase, makes sandwich.Use is with the ultraviolet lamp of travelling belt, " the D バ Le Block " manufactured by フ ュ ー ジ ョ Application UV シ ス テ system ズ company, by the biaxial stretch-formed polyethylene terephthalate film one side irradiation ultraviolet radiation with antiglare layer of this sandwich, accumulated light is 750mJ/cm 2, bonding agent is solidified.Like this, made the polaroid of the diaphragm of having fitted on the polarizer two sides.
(5) estimate the permanance of polaroid by cold shock testing
The polaroid cutting of making in above-mentioned (4) is become to the size of 170mm * 110mm, the adhesive layer of the acrylic acid series of thickness 25 μ m is set in tri acetyl cellulose membrane one side, this adhesive layer is pasted on glass plate, carries out cold shock testing (thermal shock test).Cold shock testing is that the polaroid sample fitted on above-mentioned glass plate is kept 1 hour under-35 ℃, then is warming up to 70 ℃, keeps 1 hour, using this operation as 1 cycle, it is added up to 30 cycles repeatedly.Each 6 polaroid samples are carried out to this test, after test, to observe polarizer, have the number broken to be estimated with respect to the ratio of all sample numbers (6).Result is as shown in table 1.
[table 1]
Figure 118298DEST_PATH_IMAGE007
As shown in table 1, alicyclic epoxy compound (A1) in light cation-curable composition (A) is 50-60%, in the Photocurable adhesive composition that diglycidyl compounds (A2) is 50-40%, use be chlorinity many 1, 4-butanediol diglycidyl ether (a21c), neopentyl glycol diglycidyl ether (a22c), or cyclohexanedimethanol diglycidyl ether (a23c) is as the comparative example 2-5 of diglycidyl compounds (A2), the solidfied material of bonding agent only shows low storage modulus, while making polaroid, its state is that cold shock testing causes polarizer easily to break.
On the other hand, use be chlorinity few 1, in the embodiment 1-6 of 4-butanediol diglycidyl ether (a21), neopentyl glycol diglycidyl ether (a22) or cyclohexanedimethanol diglycidyl ether (a23), the solidfied material of the bonding agent combined with alicyclic epoxy compound (A1) shows high storage modulus, and confirms can effectively prevent breaking of polarizer when making polaroid.
Use chlorinity few 1, during 4-butanediol diglycidyl ether (a21), the bonding agent of the comparative example 1 that is 50% in light cation-curable composition (A) for its use level, the storage modulus of its solidfied material is low, and the state while making polaroid is: cold shock testing causes polarizer easily to break.Like this, kind difference due to diglycidyl compounds (A2), even minimizing chlorinity, if the use level of this diglycidyl compounds (A2) in light cation-curable composition (A) is near 50%, can not make solidfied material there is enough storage moduluss, but can recognize: as defined in the present invention, in order to make solidfied material show the storage modulus more than 1000MPa under 80 ℃, can be by alicyclic epoxy compound (A1) and diglycidyl compounds (A2) combination.
In embodiment 1-6, if the amount of the alicyclic epoxy compound (A1=a1) in light cation-curable composition (A) is increased to 70% or 80%, change remaining into the diglycidyl compounds that chlorinity is few (a21, a22 or a23), although the corresponding rising of the viscosity of bonding agent liquid, but still can be controlled in the viscosity of the degree that can be coated with under room temperature, and solidfied material has high storage modulus, while making polaroid, still can effectively prevent breaking of polarizer.

Claims (6)

1. polaroid, this polaroid consists of polarizer and diaphragm, the polyvinyl alcohol resin film that described polarizer is adsorbed and is being orientated by dichroic dye is made, described diaphragm is fitted at least one face of this polarizer via bonding agent, by transparent resin, made, above-mentioned bonding agent is formed by Photocurable adhesive composition, described Photocurable adhesive composition contains 100 weight portion light cation-curable compositions (A) and 1-10 weight portion light cationic polymerization initiators (B), above-mentioned smooth cation-curable composition (A) is to take its total amount as benchmark, contain in 50-95 % by weight molecule and there is the epoxy radicals more than 2, at least 1 alicyclic epoxy compound (A1) closed with the ester ring type loops wherein, and 5-50 % by weight chlorinity is below 1 % by weight, diglycidyl compounds (A2) shown in following formula (I):
Figure 323101DEST_PATH_IMAGE001
In formula, Z means the alkylene base, carbon number 3 of carbon number 1-9 or 4 alkylidene radical, divalent ester ring type alkyl or formula-C mH 2m-Z 1-C nH 2n-shown in the divalent group, here ,-Z 1-expression-SO 2-,-SO-or-CO-, m and n are independent separately, mean the integer more than 1, both add up to below 9;
Its solidfied material shows the storage modulus more than 1000MPa under 80 ℃.
2. the polaroid of claim 1, wherein, the diaphragm be fitted at least one face of polarizer is become by acetyl fibre prime system resin.
3. the polaroid of claim 1, wherein, fitting in diaphragm at least one face of polarizer is that the transparent resin of resin, polyester based resin, polycarbonate-based resin and chain polyolefin-based resins is made by being selected from amorphous polyolefins.
4. the polaroid of claim 1; wherein; the diaphragm become by acetyl fibre prime system resin fits on a face of polarizer via above-mentioned bonding agent; on the another side of polarizer, as being that the diaphragm of the film made of the transparent resin of resin, polyester based resin, polycarbonate-based resin and chain polyolefin-based resins is fitted via above-mentioned bonding agent by being selected from amorphous polyolefins.
5. laminated optical component, this laminated optical component comprises the polaroid of claim 1 and the duplexer of other optical layers.
6. the laminated optical component of claim 5, wherein, above-mentioned optical layers contains phase retardation film.
CN2012800157488A 2011-03-29 2012-03-23 Polarizing plate and laminated optical member Pending CN103430060A (en)

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* Cited by examiner, † Cited by third party
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CN112789530A (en) * 2018-09-28 2021-05-11 住友化学株式会社 Optical laminate, polarizing plate composite, and image display device

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US9487685B2 (en) 2011-10-14 2016-11-08 Lg Chem, Ltd. Adhesive for polarizing plate and polarizing plate including the same
KR102155921B1 (en) * 2013-02-20 2020-09-14 스미또모 가가꾸 가부시키가이샤 Photocurable adhesive, polarizing plate using same, multilayer optical member and liquid crystal display device
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JP6620180B2 (en) * 2017-04-07 2019-12-11 住友化学株式会社 Polarizer
JP7348719B2 (en) * 2017-11-10 2023-09-21 住友化学株式会社 Composite retardation plate, optical laminate, and image display device

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1521523A (en) * 2003-02-12 2004-08-18 ס�ѻ�ѧ��ҵ��ʽ���� Polarizer and its manufacturing method ,optical element and liquid crystal display device
CN101236269A (en) * 2007-02-02 2008-08-06 Jsr株式会社 Polarizing filter and manufacturing method thereof
CN101636672A (en) * 2007-03-15 2010-01-27 住友化学株式会社 Photocurable adhesive agent, the polarization plates of using this Photocurable adhesive agent and manufacture method, optical component and liquid crystal indicator
JP2010091603A (en) * 2008-10-03 2010-04-22 Sumitomo Chemical Co Ltd Polarizing plate and liquid crystal display
CN101824296A (en) * 2009-03-05 2010-09-08 Dic株式会社 Cation-polymerizable adhesive and polarizing plate using the same
JP2011017820A (en) * 2009-07-08 2011-01-27 Sumitomo Chemical Co Ltd Polarizing plate and layered optical member including the same

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11315132A (en) * 1998-05-07 1999-11-16 Dainippon Ink & Chem Inc Ultraviolet-hardenable composition for optical disk, and optical disk by using the same
JP2002365432A (en) 2001-06-07 2002-12-18 Nitto Denko Corp Method for manufacturing polarizing plate and display device using the same
JP5000053B2 (en) * 2001-09-05 2012-08-15 三菱化学株式会社 Liquid epoxy resin composition and cured epoxy resin
JP4306270B2 (en) 2003-02-12 2009-07-29 住友化学株式会社 Polarizing plate, manufacturing method thereof, optical member, and liquid crystal display device
KR100784991B1 (en) * 2005-06-10 2007-12-11 주식회사 엘지화학 Acrylic pressure-sensitive adhesive compositions
JP5348580B2 (en) 2008-01-31 2013-11-20 住友化学株式会社 Manufacturing method of polarizing plate
JP5644064B2 (en) * 2009-06-09 2014-12-24 住友化学株式会社 Liquid crystal display device and polarizing plate used therefor
JP5557281B2 (en) * 2009-06-26 2014-07-23 住友化学株式会社 Polarizing plate and laminated optical member using the same
TWI493005B (en) * 2009-07-28 2015-07-21 Toagosei Co Ltd An active energy ray hardening agent composition for a plastic film or sheet
CN102471660B (en) * 2009-08-21 2014-04-09 Dic株式会社 Cationically polymerizable adhesive and polarizing plate obtained using same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1521523A (en) * 2003-02-12 2004-08-18 ס�ѻ�ѧ��ҵ��ʽ���� Polarizer and its manufacturing method ,optical element and liquid crystal display device
CN101236269A (en) * 2007-02-02 2008-08-06 Jsr株式会社 Polarizing filter and manufacturing method thereof
CN101636672A (en) * 2007-03-15 2010-01-27 住友化学株式会社 Photocurable adhesive agent, the polarization plates of using this Photocurable adhesive agent and manufacture method, optical component and liquid crystal indicator
JP2010091603A (en) * 2008-10-03 2010-04-22 Sumitomo Chemical Co Ltd Polarizing plate and liquid crystal display
CN101824296A (en) * 2009-03-05 2010-09-08 Dic株式会社 Cation-polymerizable adhesive and polarizing plate using the same
JP2011017820A (en) * 2009-07-08 2011-01-27 Sumitomo Chemical Co Ltd Polarizing plate and layered optical member including the same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107850719A (en) * 2015-09-15 2018-03-27 株式会社Lg化学 Polarization element diaphragm including its Polarizer and the liquid crystal display device including Polarizer
CN112789530A (en) * 2018-09-28 2021-05-11 住友化学株式会社 Optical laminate, polarizing plate composite, and image display device

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