CN101937112B - Polarization plate and laminated optical component using the same - Google Patents

Polarization plate and laminated optical component using the same Download PDF

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Publication number
CN101937112B
CN101937112B CN201010214538.4A CN201010214538A CN101937112B CN 101937112 B CN101937112 B CN 101937112B CN 201010214538 A CN201010214538 A CN 201010214538A CN 101937112 B CN101937112 B CN 101937112B
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compound
resin
polarization plates
polaroid
photo
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CN101937112A (en
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久米悦夫
竹内智康
中川弘也
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Adeka Corp
Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
Asahi Denka Kogyo KK
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • 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
    • 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

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Organic Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Polarising Elements (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Mounting And Adjusting Of Optical Elements (AREA)
  • Laminated Bodies (AREA)

Abstract

This invention provides a polarizing plate and a laminated optical component using the same. The polarizing plate has a polyvinyl alcohol based polarizer in which a bicolored pigment is oriented by adsorption; and a protection film formed with a transparent resin laminated on at least one surface of the polarizer through an adhesive agent layer. The adhesive agent layer is formed by a photocurable adhesive agent composition containing (A) 100 parts by weight of a cation polymeric compound, (B) 1 to 10 parts by weight of a photo cationic polymerization initiator, (C) 0.1 to 2 parts by weight of a photo-sensitizer showing the maximum absorption with respect to the light having the wavelength longer than 380 nmm, and (D) 0.1 to 10 parts by weight of a naphthalene based photo-sensitizing auxiliary agent represented by the following formula (I) shown in the description; wherein R1 and R2 each independently represents an alkyl group of 1 to 6 carbon atoms). Additionally, this invention provides a laminated optical component.

Description

Polarization plates and used the laminated optical component of this polarization plates
Technical field
The present invention relates to the polarization plates that a kind of polaroid comprising polyvinyl alcohol resin is fitted with the diaphragm that comprises transparent resin.The present invention also relates in addition and a kind of this polarization plates is layered in to the laminated optical component that other optical layers forms.
Background technology
Polarization plates is useful as one of optical component that forms liquid crystal indicator.Polarization plates has the structure that is laminated with diaphragm on the two sides of polaroid conventionally, is loaded into liquid crystal indicator.Also known only have the one side at polaroid be provided with diaphragm, but in most cases another side laminating be not simple diaphragm, but the layer having as other function, for example optical function doubles as diaphragm.In addition, as the manufacture method of polaroid, extensively adopt with the following method: by utilizing dichromatism pigment dyeing, good uniaxial tension polyvinyl alcohol resin film carries out, after boric acid processing, washing, being dried.
Generally, after above-mentioned washing and being dried, the diaphragm of directly fitting on polaroid.There are the following problems for the result of doing like this: dried polaroid physical strength is poor, while temporarily being reeled, easily along machine direction fracture etc.Therefore, conventionally on dried polaroid, directly apply the water system tackifier as polyvinyl alcohol resin aqueous solution, the diaphragm of simultaneously fitting on the two sides of polaroid by this tackifier.As diaphragm, the three cellulose acetate membrane of common used thickness 30～100 μ m.
The moisture permeability of Triafol T is high, and the problem that the polarization plates that forms of laminating exists using it as diaphragm is, can occur under under damp and hot, such as the condition of temperature 70 C, relative humidity 90% aging etc.Therefore the amorphous polyolefins, also knownly have moisture permeability lower than Triafol T, the norbornene resin of for example take being typical example is that resin is made diaphragm.
When the diaphragm consisting of the low resin of moisture permeability is fitted in to polyethenol series polaroid; at present in the laminating of polyethenol series polaroid and Triafol T, as the aqueous solution of the normally used polyvinyl alcohol resin of tackifier, there are the following problems: adhesive strength is insufficient, or the bad order of the polarization plates obtaining.This is the cause that is generally hydrophobicity or can not be fully dried water as solvent etc. because moisture permeability is low due to the low resin molding of moisture permeability.On the other hand; also known have different types of diaphragm of fitting on the two sides of polaroid; motion have such as: in the one side laminating of polaroid, by amorphous polyolefins, be the diaphragm that resin that the moisture permeabilitys such as resin are low forms, in the another side laminating of polaroid by take the diaphragm that Triafol T forms as the main high resin of the moisture permeabilitys such as cellulose-based resin.
Therefore; between the diaphragm forming as the resin low by moisture permeability and polyethenol series polaroid, give high adhesive power, between the high resin of the moisture permeabilitys such as cellulose-based resin and polyethenol series polaroid, also give the tackifier of high adhesive power simultaneously, attempt using active energy ray-curable tackifier.For example, in TOHKEMY 2004-245925 communique, disclose not the tackifier that epoxy compound is principal ingredient of take containing aromatic rings, proposed by utilizing the cationic polymerization that actinic energy ray irradiates to make this adhesive solidification come gluing polaroid and diaphragm.In addition; in TOHKEMY 2008-257199 communique, disclosed technology is; by combination alicyclic epoxy compound with do not there is the epoxy compound of ester ring type epoxy radicals, coordinate the photo-curable tackifier of photo-induced cationic polymerization initiating agent simultaneously, gluing for polaroid and diaphragm.In this TOHKEMY 2008-257199 communique, record: by and use the photosensitizer being formed by anthracene compound, even in the situation that diaphragm contains ultraviolet light absorber, also can give good adhesive power.
; for being solidified, the cationically polymerizable compound of epoxy compound and so on coordinates photo-induced cationic polymerization initiating agent; but described photo-induced cationic polymerization initiating agent is generally the compound that the light display that near light wavelength 300nm or wavelength are less than to the region of 300nm is shown very big absorption; therefore; by coordinate to wavelength be greater than 300nm region, be specially the photosensitizer that light display that wavelength is greater than 380nm is shown very big absorption; near the light of this wavelength be can respond to, kation kind or lewis acidic generation from photo-induced cationic polymerization initiating agent promoted.
In addition, conventionally expect that polarization plates is that neutral ash is can show original color when being applied to liquid crystal indicator.For example, in TOHKEMY 2002-169024 communique, propose a kind of polarization plates, in order to carry out white demonstration and the black demonstration of more neutral ash, and then obtained the white demonstration distinct, contrast is high, a of the parallel form and aspect of described polarization plates of showing *and b *and a of quadrature form and aspect *and b *meet specific relation.
On the other hand, for the general Photocurable composition using in the field beyond polarization plates, various improvement have also been carried out, for example, in No. 2006/073021 pamphlet of International Publication WO, disclose the technology of anthracene compound and naphthalene compound or benzene compound combination being made to photosensitizer.In No. 2006/073021 pamphlet of this International Publication WO, also recorded and in above-mentioned photosensitizer, coordinated cationically polymerizable monomer and photo-induced cationic polymerization initiating agent to make Photocurable composition, in addition, also enumerated the example of epoxy compound as cationically polymerizable monomer.
Summary of the invention
By using the disclosed epoxy compound and photo-induced cationic polymerization initiating agent and anthracene of being combined with in above-mentioned TOHKEMY 2008-257199 communique, it is the tackifier of photosensitizer; gluing polaroid and diaphragm securely; for example; use this tackifier on polaroid, to be fitted with the polarization plates of diaphragm; can protected film or the impact of adhesive layer; according to the original degree of polarization showing of polaroid, show high degree of polarization, even after damp heat test for example, also maintain high degree of polarization like that.But in order to manifest fully described effect, needing to coordinate the anthracene of amount is to a certain degree photosensitizer.In this case, because anthracene is that the light display that photosensitizer surpasses 380nm to wavelength is shown very big absorption, therefore,, when polarization plates is disposed to Nicol crossed, there is near the blue light leakage of wavelength 400nm, the so-called blue (Japanese: Block Le one リ mono-Network) become large problem that leaks.Therefore, with Nicol crossed, observe such use be combined with in a large number anthracene be the tackifier of photosensitizer make polarization plates time, the form and aspect of known transmitted light depart to blue direction from neutral ash.Also learning in addition, is photosensitizer in the situation that coordinate the anthracene of amount to a certain degree, and the form and aspect under Nicol crossed are also because damp heat test changes sometimes.
Therefore; problem of the present invention is; a kind of polarization plates is provided; even its use in the cationically polymerizable compound of epoxy compound and so on, be combined with anthracene based compound and so at ultraviolet region, the long light of wavelength is also shown the tackifier of the photosensitizer of absorption; at polaroid, be fitted with diaphragm; when being disposed at Nicol crossed, maintain neutral ash, and humidity resistance is also excellent.Another problem of the present invention is, provides a kind of in stacked other optical layers of this polarization plates and humidity resistance excellent laminated optical component still.
The inventor etc. concentrate on studies in order to solve described problem; found that; even for being combined with photo-induced cationic polymerization initiating agent and at ultraviolet region, the long light of wavelength also being shown the photo-curable adhesive compound of the photosensitizer of absorption in cationically polymerizable compound; the specific photosensitizer additive that coordinates ormal weight; use it for the laminating of polaroid and diaphragm; thus; can obtain maintaining the neutrality ash of polaroid and also excellent polarization plates of gluing polaroid and diaphragm, humidity resistance securely, thereby complete the present invention.Also find, as cationically polymerizable compound, when the ratio with regulation coordinates alicyclic epoxy compound and aliphatic epoxy compound, such formula is effective especially simultaneously.
; the invention provides a kind of polarization plates; it possesses polaroid that the polyvinyl alcohol resin film that is adsorbed and is orientated by dichromatism pigment forms and at the diaphragm that comprises transparent resin that at least one side is fitted by adhesive layer of this polaroid, and this adhesive layer is formed by the photo-curable adhesive compound that contains following composition (A)～(D).
(A) cationically polymerizable compound 100 weight portions,
(B) photo-induced cationic polymerization initiating agent 1～10 weight portion,
(C) light display that wavelength is greater than to 380nm show very big absorption photosensitizer 0.1～2 weight portion and
(D) naphthalene shown in following formula (I) is photosensitizer additive 0.1～10 weight portion.
In formula, R 1and R 2the alkyl that represents independently of one another carbon number 1～6.
In above-mentioned polarization plates, the cationically polymerizable compound (A) that forms photo-curable adhesive compound preferably comprises the epoxy resin that does not contain aromatic rings.
In addition, in these polarization plates, the photosensitizer (C) that forms photo-curable adhesive compound is preferably the anthracene based compound shown in following formula (IV).
In formula, R 5and R 6represent independently of one another the alkyl of carbon number 1～6 or the alkoxyalkyl of carbon number 2～12, R 7the alkyl that represents hydrogen atom or carbon number 1～6.
In above-mentioned any polarization plates, from maintaining the viewpoint of neutral ash, consider, in the scope of adhesive power that suitably keeps polaroid and diaphragm, the amount of the photosensitizer in photo-curable adhesive compound (C) is favourable less.Therefore, relative cationically polymerizable compound (A) 100 weight portions, the amount of photosensitizer (C) is preferably set to the scope of 0.1～0.5 weight portion.
In above-mentioned any polarization plates, can take for example by acetate fiber prime system resin, to form at least mode of the diaphragm of one side that is fitted in polaroid.In addition, the low resin of moisture permeability that also can to take by amorphous polyolefins be resin, polyester based resin, acrylic resin, polycarbonate-based resin, chain polyolefin-based resins and so on forms at least mode of the diaphragm of one side that is fitted in polaroid.And the diaphragm that comprises acetate fiber prime system resin by described adhesive layer laminating in the one side of polaroid, to comprise amorphous polyolefins at the another side of polaroid by identical described adhesive layer laminating be that the mode of the diaphragm of the resin that the moisture permeability of resin, polyester based resin, acrylic resin, polycarbonate-based resin, chain polyolefin-based resins and so on is low is also one of optimal way.
These polarization plates can be held in its quadrature form and aspect the neutrality ash of polaroid, particularly, can make a value of quadrature form and aspect and b value all in-0.5～+ 0.5 scope.
In addition, the present invention also provides a kind of laminated optical component consisting of the duplexer of above-mentioned any polarization plates and other optical layers.In this laminated optical component, optical layers preferably contains polarizer.
For polarization plates of the present invention; the light display that wavelength is greater than to 380nm of fitting in the photo-curable adhesive compound of polaroid and diaphragm by minimizing is shown the amount of the photosensitizer of very big absorption; coordinating the naphthalene of ormal weight is photosensitizer additive; can keep the adhesive strength between polaroid and diaphragm, and manifest the neutrality ash as the form and aspect of polaroid.In addition, for polarization plates of the present invention, even if be placed under hygrothermal environment, degree of polarization or quadrature form and aspect are also not easy to change, and show good humidity resistance.The laminated optical component forming in stacked other optical layers of this polarization plates also fully shows the function as polarization plates, and humidity resistance is excellent.
Embodiment
Below, the present invention is described in detail.Polarization plates of the present invention possesses polaroid and at least one side diaphragm of fitting by adhesive layer of this polaroid.
[polaroid]
Polaroid comprises the polyvinyl alcohol resin film that dichromatism pigment is adsorbed and is orientated.The polyvinyl alcohol resin that forms polaroid is by being that resin carries out saponification and obtains by polyvinyl acetate (PVA).As polyvinyl acetate (PVA), be resin, except the polyvinyl acetate (PVA) of the homopolymer as vinyl acetate, can example vinyl acetate and can with multipolymer of other monomer of its copolymerization etc.As can with other vinyl acetate copolymerized monomer, can enumerate such as unsaturated carboxylic acid class, olefines, vinyl ethers, unsaturated sulfonic acid class etc.The saponification degree of polyvinyl alcohol resin is generally 85～100 % by mole, the preferred scope of 98～100 % by mole.Further modification of polyvinyl alcohol resin, can be used such as the polyvinyl formal being formed by aldehydes modification or polyvinyl acetal etc.The degree of polymerization of polyvinyl alcohol resin is generally 1,000～10, and 000, preferably 1,500～5,000 scope.
Polaroid can be manufactured through following operation: the operation of this polyvinyl alcohol resin film being carried out to uniaxial tension; Polyvinyl alcohol resin film is dyeed with dichromatism pigment, make it adsorb the operation of this dichromatism pigment; The operation that has the polyvinyl alcohol resin film of dichromatism pigment to process with boric acid aqueous solution absorption.
Uniaxial tension both can carry out before the dyeing that utilizes dichromatism pigment, also can carry out with utilizing the dyeing of dichromatism pigment simultaneously, can also after the dyeing that utilizes dichromatism pigment, carry out.While carrying out uniaxial tension after the dyeing that utilizes dichromatism pigment, this uniaxial tension both can carry out before boric acid is processed, and also can in boric acid is processed, carry out.In addition, can certainly carry out uniaxial tension in these a plurality of stages.Uniaxial tension both can carry out between the different roller of peripheral speed, also can use hot-rolling to carry out.In addition, can be both the dry type stretching stretching in atmosphere, also can be for utilizing the wet type stretching under the state of solvent swell to stretch.Draw ratio is generally 4～8 times of left and right.
For polyvinyl alcohol resin film is dyeed with dichromatism pigment, for example by polyvinyl alcohol resin film immersion in the aqueous solution that contains dichromatism pigment.As dichromatism pigment, specifically use iodine or dichromatism organic dyestuff.
Use iodine as the situation of dichromatism pigment, conventionally adopt and in the aqueous solution that contains iodine and potassium iodide, flood the method that polyvinyl alcohol resin film dyes.Conventionally relative water 100 weight portions of the content of the iodine in this aqueous solution are 0.01～0.5 weight portion left and right, and conventionally relative water 100 weight portions of the content of potassium iodide are 0.5～10 weight portion left and right.The temperature of this aqueous solution is generally 20～40 ℃ of left and right, and in addition, the time (dyeing time) that impregnated in this aqueous solution was generally about 30～300 seconds.
On the other hand, use dichromatism organic dyestuff as the situation of dichromatism pigment, conventionally adopt and in the aqueous solution that contains water miscible dichromatism organic dyestuff, flood the method that polyvinyl alcohol resin film dyes.Conventionally relative water 100 weight portions of the content of the dichromatism organic dyestuff in this aqueous solution are 1 * 10 -3～1 * 10 -2weight portion left and right.This aqueous solution can contain the inorganic salts such as sodium sulphate.The temperature of this aqueous solution is generally 20～80 ℃ of left and right, and in addition, the time (dyeing time) that impregnated in this aqueous solution was generally about 30～300 seconds.
Utilize the boric acid after the dyeing of dichromatism pigment to process by the polyvinyl alcohol resin film immersion after dyeing is carried out in boric acid aqueous solution.Conventionally relative water 100 weight portions of the content of the boric acid in boric acid aqueous solution are 2～15 weight portions left and right, are preferably 5～12 weight portions left and right.In the situation that using iodine as dichromatism pigment, preferably this boric acid aqueous solution contains potassium iodide.Conventionally relative water 100 weight portions of the content of the potassium iodide in boric acid aqueous solution are 2～20 weight portions left and right, are preferably 5～15 weight portions.The time that impregnated in boric acid aqueous solution is generally 100～1, about 200 seconds, is preferably about 150～600 seconds, more 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 after boric acid is processed is washed processing conventionally.By for example having carried out the acid-treated polyvinyl alcohol resin film immersion of boron, in water, wash processing.After washing, implement dry processing, can obtain polaroid.The temperature of the water in washing processing is generally 5～40 ℃ of left and right, and dip time was generally about 2～120 seconds.Thereafter the dry processing of carrying out is used air drier or far infra-red heater to carry out conventionally.Baking temperature is generally 40～100 ℃.In addition, the dry time of processing was generally about 120～600 seconds.
The thickness of the polaroid consisting of the polyvinyl alcohol resin film so obtaining can be set as 10～50 μ m left and right.
[adhesive layer]
For the polaroid obtaining like this, at its diaphragm that at least one side is fitted and comprised transparent resin by adhesive layer, become polarization plates.In the present invention, as the tackifier being formed at the adhesive layer of polaroid laminating diaphragm, use the photo-curable adhesive compound of each composition that contains following (A)～(D).
(A) cationically polymerizable compound,
(B) photo-induced cationic polymerization initiating agent,
(C) light display that wavelength is greater than to 380nm show very big absorption photosensitizer and
(D) naphthalene shown in above-mentioned formula (I) is photosensitizer additive.
(cationically polymerizable compound)
Cationically polymerizable compound (A) is the principal ingredient of photo-curable adhesive compound, by polymerizing curable, to give the composition of adhesive power, as long as for by the curing compound of cationic polymerization, particularly preferably contain the epoxy compound in molecule with at least 2 epoxy radicals.Epoxy compound has: the aromatic epoxy compound in molecule with aromatic rings; In molecule, there is at least 2 epoxy radicals, at least 1 alicyclic epoxy compound that is bonded to ester ring type ring wherein; A carbon atom bonding of the ring of 2 carbon atoms that do not have aromatic rings in molecule, contain epoxy radicals and its bonding (being generally oxirane ring) is in aliphatic epoxy compound of other aliphatic carbon atom etc.For photo-curable adhesive compound of the present invention, particularly preferably using not containing the epoxy resin of aromatic rings, compound that particularly alicyclic epoxy compound is principal ingredient as cationically polymerizable compound (A).If used, take the cationically polymerizable compound that alicyclic epoxy compound is principal ingredient; can obtain preserving the solidfied material that elastic modulus is high; in the polarization plates forming by the gluing diaphragm of this solidfied material (adhesive layer) and polaroid, polaroid is not easy to break.
As mentioned above, alicyclic epoxy compound is in molecule, to have at least 2 epoxy radicals, at least 1 compound that is bonded to ester ring type ring wherein.At this, what is called is bonded to the epoxy radicals of ester ring type ring, refer to as shown in the formula shown in (V), 2 of epoxy radicals (O-) in conjunction with hand respectively with 2 carbon atoms (the be generally adjacent carbon atom) Direct Bonding that forms ester ring type ring.In following formula (V), m represents 2～5 integer.
Removed (the CH in one or more formulas (V) 2) min the compound that forms in other chemical constitution of the group bonding of form of hydrogen atom can become alicyclic epoxy compound.The hydrogen that forms ester ring type ring can suitably be replaced by the straight chain-like alkyl of methyl or ethyl and so on.The compound wherein, preferably with epoxy radicals cyclopentane ring [ring of m=3 in above-mentioned formula (V)] or epoxy-cyclohexane ring [ring of m=4 in above-mentioned formula (V)].
In alicyclic epoxy compound, be easy to get calmly and the effective aspect that improves the storage elastic modulus of solidfied material is considered, further the preferred compound of any expression of following (1)～(11).
(in formula, R 1～R 24the alkyl that represents independently of one another hydrogen atom or carbon number 1～6, R 1～R 24during for alkyl, the position that is bonded to ester ring type ring is the Arbitrary Digit of 1～6.The alkyl of carbon number 1～6 can be straight chain, also can have side chain, can also have ester ring type ring.Y 8the alkane 2 basis that represents oxygen atom or carbon number 1～20, Y 1～Y 7representing independently of one another can be for straight chain, also can have side chain, can also have the alkane 2 basis of the carbon number 1～20 of ester ring type ring, and n, p, q and r represent 0～20 number independently of one another.)
In the compound representing in above-mentioned (1)～(11), the ester ring type di-epoxy compounds shown in above-mentioned formula (2) easily obtains, therefore preferably.The ester ring type di-epoxy compounds of formula (2) is 3, the carboxylate of the 4-epoxy radicals hexahydrobenzyl alcohol alkyl of bonding carbon number 1～6 (can on its cyclohexane ring) and 3,4-epoxy-cyclohexane the carboxylic acid alkyl of bonding carbon number 1～6 (can on its cyclohexane ring).As its concrete example, can be listed below compound.
3,4-epoxy radicals cyclohexyl methyl 3, and 4-epoxy-cyclohexane carboxylate [in formula (2), R 5=R 6the compound of=H, n=0], 3,4-epoxy radicals-6-methyl cyclohexane ylmethyl 3,4-epoxy radicals-6-methylcyclohexanecarboxylic acid ester [in formula (2), R 5=6-methyl, R 6the compound of=6-methyl, n=0] etc.
In addition, in alicyclic epoxy compound, with the epoxy resin substantially without ester ring type epoxy radicals, be also effective.If will take alicyclic epoxy compound as principal ingredient, wherein and with the compound substantially without the epoxy resin of ester ring type epoxy radicals make cationically polymerizable compound; the storage elastic modulus of solidfied material can be remained on to high value, and further improve the adaptation of polaroid and diaphragm.At this said epoxy resin substantially without ester ring type epoxy radicals, be that the carbon atom bonding of ring (being generally oxirane ring) of molecule 2 carbon atoms containing epoxy radicals and its bonding is in the compound of other aliphatic carbon atom.As the example, can enumerate the polyglycidyl ether of polyvalent alcohol (phenol).Wherein, the effective aspect consideration that is easy to get calmly and improves the adaptation of polaroid and diaphragm, the 2-glycidyl ether compound shown in preferred following formula (12).
(in formula, X represents alkylidene, ester ring type alkyl, O, S, the SO of Direct Bonding, methylene, carbon number 1～4 2, SS, SO, CO, OCO or be selected from the substituting group in 3 kinds of substituting groups that following formula represents, this alkylidene can be replaced by halogen atom.)
(in formula, R 25and R 26the naphthenic base of the carbon number 3～10 that represents independently respectively the alkyl of hydrogen atom, carbon number 1～3, the phenyl that can be replaced by the alkyl of carbon number 1～10 or alkoxy or can be replaced by the alkyl of carbon number 1～10 or alkoxy, R 25and R 26can mutually link and form ring, heterocyclic radical or the halogen atom of the aryl alkyl of the aryl of the alkyl of A and the D carbon number 1～10 that expression can be replaced by halogen atom independently respectively, the carbon number 6～20 that can be replaced by halogen atom, the carbon number 7～20 that can be replaced by halogen atom, the carbon number 2～20 that can be replaced by halogen atom, methylene in this alkyl, aryl, aryl alkyl can by unsaturated link ,-O-or-S-interrupts, a represents 0～4 number, and d represents 0～4 number.)
As the 2-glycidyl ether compound of formula (12), for example can enumerate: the such bisphenol-type epoxy resin of diglycidyl ether of the diglycidyl ether of bisphenol-A, the diglycidyl ether of Bisphenol F, bisphenol S; The epoxy resin of the multifunctional type of the glycidol ether of tetrahydroxy benzene methylmethane, the glycidol ether of tetrahydroxybenzophenone, epoxidation polyvinylphenol and so on; The polyglycidyl ether of aliphatic polyol; The polyglycidyl ether of the alkylene oxide adducts of aliphatic polyol; The diglycidyl ethers of aklylene glycol etc., wherein, the polyglycidyl ether of aliphatic polyol easily obtains, therefore preferably.
As above-mentioned aliphatic polyol, can example the aliphatic polyol in the scope of carbon number 2～20 for example.More specifically, for example can enumerate: ethylene glycol, 1, 2-propylene glycol, 1, ammediol, 2-methyl isophthalic acid, ammediol, 2-butyl-2-ethyl-1, ammediol, 1, 4-butylene glycol, neopentyl glycol, 3-methyl-2, 4-pentanediol, 2, 4-pentanediol, 1, 5-pentanediol, 3-methyl isophthalic acid, 5-pentanediol, 2-methyl-2, 4-pentanediol, 2, 4-diethyl-1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptandiol, 3, 5-heptandiol, 1, 8-ethohexadiol, 2-methyl isophthalic acid, 8-ethohexadiol, 1, 9-nonanediol, 1, the aliphatic diols such as 10-decanediol, the ester ring type glycol such as cyclohexanedimethanol, cyclohexane diol, hydrogenation bisphenol-A, hydrogenation Bisphenol F, the polyvalent alcohol more than ternary such as trimethylolethane, trimethylolpropane, hexose alcohols, pentose alcohols, glycerine, polyglycereol, pentaerythrite, dipentaerythritol, tetra methylol propane.
And with alicyclic epoxy compound with while substantially not thering is the epoxy resin of ester ring type epoxy radicals, both mixing ratios be take cationically polymerizable total amount of compound as benchmark, more than preferably alicyclic epoxy compound being set as to 50～95 % by weight and the epoxy resin substantially without ester ring type epoxy radicals being set as to 5 % by weight.By coordinate alicyclic epoxy compounds more than 50 % by weight in cationically polymerizable compound integral body; can make the storage elastic modulus of solidfied material in the time of 80 ℃ is 1; more than 000MPa; in the polarization plates forming by the gluing polaroid of this solidfied material (adhesive layer) and diaphragm, polaroid is not easy to break.In addition, by more than relative cationically polymerizable compound overall co-ordination 5 % by weight substantially not thering is the epoxy resin of ester ring type epoxy radicals, can improve the adaptation of polaroid and diaphragm.In the situation that cationically polymerizable compound is not for substantially having the binary system of epoxy resin and the alicyclic epoxy compound of ester ring type epoxy radicals, the amount substantially without the epoxy resin of ester ring type epoxy radicals be take cationically polymerizable total amount of compound as benchmark permission is to 50 % by weight, it is measured when too many, the storage elastic modulus of solidfied material reduces, polaroid easily breaks, therefore, preferably take cationically polymerizable total amount of compound is set as its amount below 45 % by weight as benchmark.
As the cationically polymerizable compound (A) that forms photo-curable adhesive compound, and with such alicyclic epoxy compound described above with while substantially not thering is the epoxy resin of ester ring type epoxy radicals, in its amount is respectively the scope of amount described above, on their basis, can also contain other cationically polymerizable compound.As other cationically polymerizable compound, can enumerative (1)～formula (12) epoxy compound in addition, oxetane compound etc.
Formula (1)～formula (12) epoxy compound in addition has: in formula (1)～formula (11) molecule in addition, have in the aliphatic epoxy compound with the oxirane ring that is bonded to aliphatic carbon atom in addition of at least 1 alicyclic epoxy compound that is bonded to the epoxy radicals of ester ring type ring, formula (12), molecule and have the aromatic epoxy compound of aromatic rings and epoxy radicals, the hydrogenation epoxy compound that the aromatic rings in aromatic epoxy compound is hydrogenated etc.
As the example in formula (1)～formula (11) molecule in addition with the alicyclic epoxy compound of at least 1 epoxy radicals that is bonded to ester ring type ring, there are 4 vinyl cyclohexene diepoxide or 1,2:8, the diepoxide of the vinyl cyclohexene class of 9-bicyclic oxygen citrene and so on etc.
Example as formula (12) the aliphatic epoxy compound with the oxirane ring that is bonded to aliphatic carbon atom in addition, has the triglycidyl ether of glycerine, the diglycidyl ether of the triglycidyl ether of trimethylolpropane, polyglycol etc.
The aromatic epoxy compound in molecule with aromatic rings and epoxy radicals can be for having the glycidol ether of the aromatic polyhydroxy compounds of at least 2 phenol hydroxyls in molecule, as its concrete example, there is the diglycidyl ether of bisphenol-A, the glycidol ether of the diglycidyl ether of the diglycidyl ether of Bisphenol F, bisphenol S, phenol phenolic varnish type resin etc.
The hydrogenation epoxy compound that aromatic rings in aromatic epoxy compound is hydrogenated can be for carrying out by hydrogenation polyol the compound that glycidyl ether forms, described hydrogenation polyol is that aromatic polyhydroxy compounds by have at least 2 phenol hydroxyls in the molecule of the raw material as above-mentioned aromatic epoxy compound is under the existence of catalyzer, add to depress and optionally carry out hydrogenation and obtain, as concrete example, the diglycidyl ether that has hydrogenated bisphenol A, the diglycidyl ether of A Hydrogenated Bisphenol A F, the diglycidyl ether of A Hydrogenated Bisphenol A S etc.
In these formulas (1)～formula (12) epoxy compound in addition, coordinate have be bonded to the epoxy radicals of ester ring type ring, while being classified as the compound of previously defined alicyclic epoxy compound, the total amount of cationically polymerizable compound of take is benchmark, and the consumption sum of the alicyclic epoxy compound shown in itself and above-mentioned formula (1)～formula (11) is in being no more than the scope of 95 % by weight.
In addition, can become the oxetane compound of cationically polymerizable compound is arbitrarily the compound in molecule with 4 yuan of cyclic ethers (oxetanyl), as its concrete example, can be listed below compound.
3-ethyl-3-methylol oxetanes,
Isosorbide-5-Nitrae-bis-[(3-ethyl-3-oxetanyl) methoxy] benzene,
3-ethyl-3-(phenoxymethyl) oxetanes,
Two [(3-ethyl-3-oxetanyl) methyl] ether,
3-ethyl-3-(2-ethylhexyl oxygen ylmethyl) oxetanes,
3-ethyl-3-(cyclohexyl oxygen ylmethyl) oxetanes,
Phenol phenolic varnish type oxetanes,
Two [(3-Ethyloxetane-3-yl) methoxyl] benzene of 1,3-,
Oxetanyl silsesquioxane,
Oxetanyl silicate etc.
By take cationically polymerizable total amount of compound as benchmark, with the ratio cooperation oxetane compound below 30 % by weight, compare with the situation that only epoxy compound is used as to cationically polymerizable compound, sometimes can expect to improve the effect of curability and so on.
(photo-induced cationic polymerization initiating agent)
In the present invention, make cationically polymerizable compound as above by utilizing the cationic polymerization of the irradiation of actinic energy ray to solidify, thereby formation adhesive layer therefore, coordinates photo-induced cationic polymerization initiating agent (B) in photo-curable adhesive compound.Photo-induced cationic polymerization initiating agent utilizes the irradiation of the actinic energy ray of visible ray, ultraviolet ray, X ray, electron beam and so on to produce kation kind or lewis acid, causes the polyreaction of cationically polymerizable compound (A).Photo-induced cationic polymerization initiating agent is to bring into play catalytic action by light, and therefore, even mix with cationically polymerizable compound (A), its storage stability or operability are also excellent.As utilizing the irradiation of actinic energy ray to produce kation kind or lewis acidic compound, can enumerate for example aromatic series diazo salt; The salt of aromatic series salt compounded of iodine or aromatic series sulfonium salt and so on; Iron-arene complex etc.
As aromatic series diazo salt, can enumerate for example following compound.
Benzene diazonium hexafluoro antimonate,
Benzene diazonium hexafluorophosphate,
Benzene diazonium hexafluoro borate etc.
As aromatic series salt compounded of iodine, can enumerate for example following compound.
Diphenyl iodine four (pentafluorophenyl group) borate,
Diphenyl iodine hexafluorophosphate,
Diphenyl iodine hexafluoro antimonate,
Two (4-nonyl phenyl) iodine hexafluorophosphate etc.
As aromatic series sulfonium salt, can enumerate for example following compound.
Triphenylsulfonium hexafluorophosphate,
Triphenylsulfonium hexafluoro antimonate,
Triphenylsulfonium four (pentafluorophenyl group) borate,
The two hexafluorophosphates of 4,4 '-bis-[diphenyl sulfonium base] diphenyl sulphur,
The two hexafluoro antimonates of 4,4 '-bis-[two (beta-hydroxy ethoxy) phenyl sulfonium base] diphenyl sulphur,
The two hexafluorophosphates of 4,4 '-bis-[two (beta-hydroxy ethoxy) phenyl sulfonium base] diphenyl sulphur,
7-[bis-(p-methylphenyl) sulfonium base]-ITX hexafluoro antimonate,
7-[bis-(p-methylphenyl) sulfonium]-ITX four (pentafluorophenyl group) borate,
4-phenylcarbonyl group-4 '-diphenyl sulfonium base-diphenyl sulphur hexafluorophosphate,
4-(to tert-butyl-phenyl carbonyl)-4 '-diphenyl sulfonium base-diphenyl sulphur hexafluoro antimonate,
4-(to tert-butyl-phenyl carbonyl)-4 '-bis-(p-methylphenyl) sulfonium base-diphenyl sulphur four (pentafluorophenyl group) borate etc.
As iron-arene complex, can enumerate for example following compound.
Dimethylbenzene-cyclopentadienyl group iron (II) hexafluoro antimonate,
Isopropyl benzene-cyclopentadienyl group iron (II) hexafluorophosphate,
Dimethylbenzene-cyclopentadienyl group iron (II) three (trifluoromethyl sulfonyl) fibric acid salt (corresponding Japanese of fibric acid salt: メ タ Na イ De) etc.
These photo-induced cationic polymerization initiating agents both can have been distinguished use separately, or also can two or more mix use.Wherein, even if especially near the wavelength region may of aromatic series sulfonium salt 300nm also has UVA characteristic, so curability is excellent, can obtain having the solidfied material of good physical strength or adhesive strength, therefore, particularly preferably use.
Relative whole 100 weight portions of cationically polymerizable compound (A), the use level of photo-induced cationic polymerization initiating agent (B) is set as 1～10 weight portion.By relative cationically polymerizable compound (A) 100 weight portions, coordinate photo-induced cationic polymerization initiating agent more than 1 weight portion, can make cationically polymerizable compound (A) solidify fully, physical strength and the adhesive strength of giving the polarization plate hight obtaining.On the other hand, when its amount increases, because increasing, the ionic substance in solidfied material cause the hydroscopicity of solidfied material to raise, may make the endurance quality of polarization plates decline, therefore, the relative cationically polymerizable compound of the amount of photo-induced cationic polymerization initiating agent (B) (A) 100 weight portions are set as below 10 weight portions.The relative cationically polymerizable compound of use level (A) 100 weight portions of preferred photic cationic polymerization initiators (B) in addition, are preferably set to below 6 weight portions more than being set as 2 weight portions.
(photosensitizer)
For for photo-curable adhesive compound of the present invention, except the cationically polymerizable compound (A) and photo-induced cationic polymerization initiating agent (B) that contains epoxy compound as above, also contain the photosensitizer (C) that the light display that wavelength is greater than to 380nm is shown very big absorption.Above-mentioned photo-induced cationic polymerization initiating agent (B) near 300nm or its short light display of wavelength ratio show very big absorption, photoinduction near the wavelength it, produce kation kind or lewis acid, cause the cationic polymerization of cationically polymerizable compound (A), for its long light of wavelength ratio is also had to induction, can coordinate the light display that this wavelength is greater than to 380nm to show the photosensitizer (C) of very big absorption.As described photosensitizer (C), can advantageously use the anthracene based compound shown in above-mentioned formula (IV).Concrete example as the anthracene based compound shown in formula (IV), can be listed below compound.
9,10-dimethoxy anthracene,
9,10-diethoxy anthracene,
9,10-dipropoxy anthracene,
9,10-diisopropoxy anthracene,
9,10-dibutoxy anthracene,
9,10-, bis-amoxy anthracenes,
The own oxygen base of 9,10-bis-anthracene,
Two (2-methoxy ethoxy) anthracenes of 9,10-,
Two (2-ethoxy ethoxy) anthracenes of 9,10-,
Two (the 2-butoxy ethoxy) anthracenes of 9,10-,
Two (the 3-butoxy propoxyl group) anthracenes of 9,10-,
2-methyl or EDMO,
2-methyl or 2-ethyl-9,10-diethoxy anthracene,
2-methyl or 2-ethyl-9,10-dipropoxy anthracene,
2-methyl or 2-ethyl-9,10-diisopropoxy anthracene,
2-methyl or 2-ethyl-9,10-dibutoxy anthracene,
2-methyl or 2-ethyl-9,10-bis-amoxy anthracenes,
2-methyl or 2-ethyl-9, the own oxygen base of 10-bis-anthracene etc.
By coordinate photosensitizer as above (C) in photo-curable adhesive compound, to compare with the situation of mismatching it, the curability of adhesive compound improves.More than the use level of the photosensitizer (C) of cationically polymerizable compound (A) 100 weight portions with respect to formation photo-curable adhesive compound is set as to 0.1 weight portion, can manifest such effect.On the other hand, when the use level of photosensitizer (C) increases, can occur in low temperature when keeping the problem such as to separate out, therefore, cationically polymerizable compound (A) 100 weight portions relatively, its amount is set as below 2 weight portions.From maintaining the viewpoint of the neutrality ash of polarization plates, consider; in the scope of adhesive power that suitably keeps polaroid and diaphragm; the use level of photosensitizer (C) is favourable less; for example; relative cationically polymerizable compound (A) 100 weight portions, are preferably set as the amount of photosensitizer (C) 0.1～0.5 weight portion, are further the scope of 0.1～0.3 weight portion.
(photosensitizer additive)
For for photo-curable adhesive compound of the present invention, except such the cationically polymerizable compound (A) that contains epoxy compound, photo-induced cationic polymerization initiating agent (B) and photosensitizer (C) described above, also containing the naphthalene shown in above-mentioned formula (I) is photosensitizer additive (D).In above-mentioned formula (I), R 1and R 2be the alkyl of carbon number 1～6 independently respectively.As naphthalene, be the concrete example of photosensitizer additive (D), can be listed below compound.
Isosorbide-5-Nitrae-dimethoxy-naphthalene,
1-ethoxy-4-methoxynaphthalene,
Isosorbide-5-Nitrae-diethoxy naphthalene,
Isosorbide-5-Nitrae-dipropoxy naphthalene,
Isosorbide-5-Nitrae-dibutoxy naphthalene etc.
By coordinate naphthalene in photo-curable adhesive compound, be photosensitizer additive (D), compare with the situation of mismatching it, the curability of adhesive compound improves.More than being set as 0.1 weight portion by the use level that is photosensitizer additive (D) by the naphthalene with respect to forming cationically polymerizable compound (A) 100 weight portions of photo-curable adhesive compound, can manifest such effect.On the other hand, when the naphthalene use level that is photosensitizer additive (D) increases, the problem such as in the time of can occurring in low temperature keeping, separate out, therefore, cationically polymerizable compound (A) 100 weight portions relatively, its amount is set as below 10 weight portions.Naphthalene is that the relative cationically polymerizable compound of the use level of photosensitizer additive (D) (A) 100 weight portions are preferably below 5 weight portions.
And then, in photo-curable adhesive compound of the present invention, only otherwise damage effect of the present invention, as other composition of any composition, can make it contain additive component.As additive component, except above-mentioned photo-induced cationic polymerization initiating agent and photosensitizer (C), can coordinate photosensitizer in addition of photosensitizer (C), hot cationic polymerization initiators, polyalcohols, ion-trapping agent, antioxidant, light stabilizer, chain-transferring agent, bonding imparting agent, thermoplastic resin, filling agent, flow modifier, plastifier, defoamer, levelling agent, pigment, organic solvent etc.
Make its situation that contains additive component, relatively above-mentioned cationically polymerizable compound (A) 100 weight portions, the consumption of additive component is preferably below 1000 weight portions.When this consumption is that 1000 weight portions are when following, utilization is as the combination of cationically polymerizable compound (A), photo-induced cationic polymerization initiating agent (B), photosensitizer (C) and the photosensitizer additive (D) of the essential composition of photo-curable adhesive compound of the present invention, can bring into play well to improve storage stability, prevent variable color, improve curing rate, guarantee the effect of good tackiness.
[diaphragm]
In the present invention, the polaroid consisting of polyvinyl alcohol resin film illustrating above, by photo-curable adhesive compound stacked guard film described above, solidifies photo-curable adhesive compound, makes polarization plates.Diaphragm can be by present take Triafol T to be main cellulose acetate resin film or moisture permeability form lower than the resin molding of Triafol T as the diaphragm of polarization plates is the most widely used.The moisture permeability of Triafol T is probably 400g/m 2/ 24hr left and right.
In an optimal way, at the diaphragm of at least one side laminating of polaroid, comprise acetate fiber prime system resin.In another optimal way, at the diaphragm of at least one side laminating of polaroid, comprise moisture permeability lower than resin molding, for example moisture permeability 300g/m of Triafol T 2resin molding below/24hr.As the resin that forms the resin molding that this moisture permeability is low, can enumerate: amorphous polyolefins is resin, polyester based resin, acrylic resin, polycarbonate-based resin, chain polyolefin-based resins etc.And then; in another optimal way; the diaphragm of fitting and comprising acetate fiber prime system resin by above-mentioned adhesive layer in the one side of polaroid, the diaphragm of fitting and comprising the transparent resin that moisture permeability as above is low by identical above-mentioned adhesive layer at the another side of polaroid.
Acetate fiber prime system resin be at least a portion hydroxyl in cellulose by the resin of acetic acid esterified, can be for a part by acetic acid esterified, a part by the mixed ester of other acid esters.As the concrete example of acetate fiber prime system resin, can enumerate: Triafol T, cellulose diacetate, cellulose acetate propionate, acetylbutyrylcellulose etc.
Amorphous polyolefins be resin be norborene or tetracyclododecane (another name dimethylene octahydro naphthalene) or wherein bonding have the polymkeric substance of the such polymerized unit with cyclic olefin of substituent compound, can be the multipolymer that cyclic olefin and chain alkene and/or aromatic ethenyl compound copolymerization are formed.In the situation that the homopolymer of cyclic olefin or the multipolymer of cyclic olefin of more than two kinds, the residual pair of key by ring-opening polymerization, therefore, generally using the material that hydrogenation forms is there resin as amorphous polyolefins.Wherein, representative substances is that thermoplastic norbornene is resin.
Polyester based resin is the polymkeric substance that the polycondensation by dibasic acid and dibasic alcohol obtains, and representative substances is polyethylene terephthalate.Acrylic resin is to take the polymkeric substance that methyl methacrylate is principal monomer, except the homopolymer of methyl methacrylate, can be the multipolymer of the acrylate of methyl methacrylate and methyl acrylate and so on or aromatic ethenyl compound etc.Polycarbonate-based resin is the polymkeric substance on main chain with carbonic acid ester bond (O-CO-O-), the material that representative substances obtains for the polycondensation by bisphenol-A and phosgene.Chain polyolefin-based resins is to take the polymkeric substance that the chain alkene of ethene or propylene and so on is principal monomer, can be homopolymer or multipolymer.Wherein, in the homopolymer that representative substances is propylene or propylene, copolymerization has the multipolymer of a small amount of ethene.
For this diaphragm, on the contrary face of the face with fitting in polaroid, can there are the various surface-treated layers of hard conating, anti-reflecting layer, antiglare layer, antistatic layer and so on.Diaphragm comprises in the situation that is formed with this surface-treated layer, its thickness can be set as to 5～150 μ m left and right.More than its thickness is preferably 10 μ m, in addition, be preferably below 120 μ m, more preferably below 100 μ m.
[polaroid and diaphragm gluing]
When gluing polaroid and diaphragm; at the one or both sides of the gluing surface of polaroid and diaphragm, form the overlay of photo-curable adhesive compound described above; by this overlay laminating polaroid and diaphragm; by irradiating actinic energy ray, the overlay of the uncured photo-curable adhesive compound of formation is like this solidified, diaphragm is anchored on polaroid.The overlay of photo-curable adhesive compound both can be formed at the binding face of polaroid, also can be formed at the binding face of diaphragm.The formation of overlay can utilize various application pattern such as scraper coating, metal thread bar coating, die head coating, funny point type coating, gravure coating.In addition, Yi Bian Yi Bian also can adopt and take the binding face of polaroid and diaphragm and supply with continuously polaroid and diaphragm, make betwixt the mode of adhesive compound curtain coating as the mode of inner side.Each application pattern has optimum viscosity scope separately, and therefore, using the viscosity of solvent adjustment photo-curable adhesive compound is also useful technology.Solvent for this can be used the solvent that dissolves well photo-curable adhesive compound under the condition declining in the optical characteristics that can not make polaroid, and its kind is not particularly limited.Can use such as take the hydro carbons that toluene is representative, the organic solvents such as ester class that the ethyl acetate of take is representative.The thickness of adhesive layer is generally below 20 μ m, is preferably below 10 μ m, more preferably below 5 μ m.During adhesive layer thickening, likely can make the reaction rate decline of adhesive compound, the humidity resistance of polarization plates worsen.
When gluing polaroid and diaphragm; for both one or both sides of binding face; before forming the overlay of adhesive compound, can implement easy the to be gluing processing of Corona discharge Treatment, Cement Composite Treated by Plasma, flame treatment, primary coat processing, the processing of cementation coating and so on.
The light source using for the overlay to photo-curable adhesive compound irradiates actinic energy ray, so long as produce the light source of ultraviolet ray, electron beam, X ray etc.Particularly preferably use to have below wavelength 400nm and send out such as Cooper-Hewitt lamp, middle medium pressure mercury lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, chemical lamp, black lamp, microwave-excitation mercury vapor lamp, metal halide lamp etc. photodistributed.Actinic energy ray exposure intensity to photo-curable adhesive compound is determined by each objective composition, is not particularly limited, and the exposure intensity of the effective wavelength region may of activation of initiating agent is preferably to 0.1～100mW/cm 2.When the irradiation intensity to photo-curable adhesive compound is less than 0.1mW/cm 2time, the reaction time is long, when it is greater than 100mW/cm 2time, the heat release during due to the heat from lamp radiation and the polymerization of photo-curable adhesive compound, likely can make photo-curable adhesive compound generation xanthochromia or polaroid occur aging.The irradiation time of photo-curable adhesive compound is controlled by each curing composition, be still not particularly limited, the accumulative total light quantity that the long-pending form of exposure intensity and irradiation time of preferably take represents is 10～5,000mJ/cm 2mode set.When photo-curable adhesive compound being carried out to light-struck accumulative total light quantity, be less than 10mJ/cm 2time, the generation of spike that likely can make to come from initiating agent is insufficient, the adhesive layer obtaining curing insufficient, on the other hand, when its accumulative total light quantity surpasses 5,000mJ/cm 2time, irradiation time is very long, is unfavorable for boosting productivity.
When the two sides of polaroid laminating diaphragm; the irradiation which diaphragm side to carry out actinic energy ray from can; for example; in the situation that a diaphragm contains ultraviolet light absorber, another diaphragm and does not contain ultraviolet light absorber; aspect the actinic energy ray irradiating in effective utilization, raising curing rate, the diaphragm side that preferably never contains ultraviolet light absorber is irradiated actinic energy ray.
[optical characteristics of polarization plates]
For polarization plates of the present invention; by reducing, the light display that wavelength is greater than to 380nm coordinating in photo-curable adhesive compound is shown the amount of the photosensitizer (C) of very big absorption, to coordinate the naphthalene of ormal weight be photosensitizer additive (D); the adhesive strength between polaroid and diaphragm can be kept, and the form and aspect that polaroid had originally can be directly manifested.Therefore, as long as polaroid shows the neutrality ash of expectation, just can remain untouched and maintain its neutral ash, for example, can make a value of quadrature form and aspect and b value be-0.5～+ 0.5 scope.
So-called quadrature form and aspect, refer to that 2 polarization plates are under the overlapping state of the mode of the absorption axes quadrature with separately, from simultaneously irradiating the light time from the form and aspect of the light of another side transmission.The a that the form and aspect are here represented by Lab color specification system and b, use standard light C measure.Lab color specification system, as recorded in JIS K 5981:2006 " 5.5 promote atmospheric exposure test ", represents with the brightness index L of Hunter and form and aspect a and b.Tristimulus values X, Y and the Z of the value of L, a and b defined in JIS Z 8722:2009, utilize following formula to calculate.
L＝10Y 1/2
a＝17.5(10.2X-Y)/Y 1/2
b＝7.0(Y-0.847Z)/Y 1/2
In addition, even if polarization plates of the present invention is exposed to and is also not easy deterioratedly under hot and humid condition, humidity resistance is excellent.For example, even if carry out placing after the damp heat test of 240 hours, also a value of quadrature form and aspect and b value can be remained on to above-mentioned scope under the hygrothermal environment of temperature 60 C, relative humidity 90%.
[laminated optical component]
For polarization plates of the present invention, the optical layers with optical function beyond laminated polarizing plate, can make laminated optical component.Typical way is; by the diaphragm in polarization plates, pass through tackifier or the stacked laminating optical layers of bonding agent; make laminated optical component; in addition, for example also can the one side of polaroid according to the present invention by photo-curable adhesive compound laminating diaphragm, at the another side of polaroid by tackifier (Japanese: then cut open) or the stacked laminating optical layers of bonding agent (Japanese: adhere and cut open).The latter's situation, as the tackifier for fit polaroid and optical layers, as long as use the photo-curable adhesive compound of stipulating in the present invention, its optical layers also can become the diaphragm of stipulating in the present invention simultaneously.
Enumerate the example of the optical layers that is laminated in polarization plates, about being disposed at the polarization plates of the rear side of liquid crystal cells, having, be laminated in this polarization plates and reflection horizon towards liquid crystal cell side opposition side, Transflective layer, light diffusion layer, solar panel, brightness improves film etc.In addition, no matter be disposed at liquid crystal cells front face side polarization plates and be disposed at which of polarization plates of the rear side of liquid crystal cells, have the polarizer towards liquid crystal cell side etc. that is laminated in this polarization plates.
Reflection horizon, Transflective layer or light diffusion layer are respectively polarization plates (optical component), the polarization plates (optical component) of Transflective or the polarization plates (optical component) of diffused in order to make reflection-type and arrange.The liquid crystal indicator that the polarization plates of reflection-type can be used for making the type that the incident light from identification side reflects to show, can omit the light sources such as backlight, therefore, and easily by liquid crystal indicator slimming.In addition, the polarization plates of Semitransmissive is used in daylight as the liquid crystal indicator of reflection-type, the type that in the dark shown by the light from backlight.Optical component as reflection type polarizer can form as reflection horizon by setting up the paper tinsel or the vapor-deposited film that consist of metals such as aluminium on the diaphragm such as on polaroid.Can be by above-mentioned reflection horizon being made to half-mirror, maybe containing pearl pigment etc. and the radioparent reflecting plate of display light and polarization plates is gluing forms as the optical component of Semitransmissive polarization plates.On the other hand, the optical component as diffused polarization plates can be by being used the method for processing such as the diaphragm enforcement delustring to polarization plates, the method that applies the resin that contains particulate, the whole bag of tricks such as method of the gluing film containing particulate to form in surface formation micro concavo-convex structure.
And laminated optical component can be also the dual-purpose polarization plates of reflection diffusion.The dual-purpose polarization plates of reflection diffusion can be utilized such as the methods such as reflection horizon that its concaveconvex structure of mapping is set on the micro concavo-convex structural plane in diffused polarization plates and form.The reflection horizon with micro concavo-convex structure has and can utilize diffuse reflection to make incident light diffusion, prevents directionality or dazzle, suppress the unequal advantage of light and shade.While in addition, also having incident light and reflected light transmission thereof containing particulate layer containing fine-grained resin bed or film, can spread, suppress the unequal advantage of light and shade.For the reflection horizon that makes surperficial micro concavo-convex structure mapping, can utilize the methods such as evaporation such as vacuum evaporation, ion plating, sputter or plating, the surface of metal straight attachment being located to micro concavo-convex structure forms.The particulate coordinating in order to form surperficial micro concavo-convex structure can be for being that silicon dioxide, aluminium oxide, titanium dioxide, zirconia, tin oxide, indium oxide, cadmium oxide, antimony oxide and so on inorganic of 0.1～30 μ m is the organic system particulate of particulate, crosslinked or noncrosslinking polymkeric substance and so on etc. such as mean grain size.
Solar panel is in order to carry out light path control etc. and to use, and can set up sheet etc. for prism array sheet or lens array sheet or point.
Brightness improves film and uses for the brightness improving in liquid crystal indicator, as the example, can enumerate: the anisotropy of stacked a plurality of refractive indexes mutually different films so that reflectivity produce reflective polarizing light separating sheet that anisotropic mode is designed to, in film base material upper support, have the alignment films of cholesteric liquid crystal polymers or the circularly polarizing separation sheet of its aligned liquid-crystal layer etc.
On the other hand, as the polarizer of above-mentioned optical layers, be to use in order to compensate the phase differential that caused by liquid crystal cells etc.As the example, can enumerate: the birefringent film, the orientation that the stretched film of various plastics etc., consist of are fixed with the film of discoid liquid crystal or nematic liquid crystal, on film base material, are formed with the film of above-mentioned liquid crystal layer etc.On film base material, form the situation of liquid crystal layer, as film base material, preferably use the cellulose-based resin moldings such as Triafol T.
As the plastics of form dielectric grid film, can enumerate such as: amorphous polyolefins is chain polyolefin-based resins, polyvinyl alcohol (PVA), polystyrene, polyarylate, polyamide of resin, polycarbonate-based resin, acrylic resin, polypropylene and so on etc.Stretched film can be the film of processing in suitable modes such as single shaft or twin shafts.It should be noted that, in order to control the optical characteristics such as wide band, polarizer can 2 be used in combination above.
In laminated optical component, contain polarizer and when being applied to liquid crystal indicator, can effectively carry out optical compensation as the laminated optical component of the optical layers beyond polarization plates, therefore, preferably use.The phase difference value of polarizer (face in and thickness direction) is selected best phase difference value according to the liquid crystal cells of application.
Laminated optical component can combine polarization plates and in above-mentioned various optical layers, according to application target, select more than 1 layer or 2 layers, make 2 layers or 3 layers of above duplexer.Now, the various optical layers that form laminated optical component are used tackifier or bonding agent to carry out integration with polarization plates, as long as for this reason and tackifier or the bonding agent of use can form adhesive layer or adhesive phase well, are just not particularly limited.From the simplicity of gluing operation or the viewpoint that prevents optical skew, consider, preferably use bonding agent (also referred to as pressure-sensing glue stick).Bonding agent can be used take the bonding agent that acrylic acid series polymeric compounds or silicone-based polymkeric substance, polyester, polyurethane, polyethers etc. be base polymer.Wherein, preferably choice for use optical transparence as acrylic adhesive excellent, keep suitable wetting quality or cohesiveness, also excellent and the bonding agent of the problem of peeling off such as there are weatherability or thermotolerance etc., under the condition of heating or humidification, do not arch upward or peel off with the tackiness of base material.In acrylic adhesive, coordinate have (methyl) acrylic acid Arrcostab that the carbon numbers such as methyl or ethyl or butyl are the alkyl below 20 and by (methyl) acrylic acid or (methyl) Hydroxyethyl Acrylate etc., formed containing functional group's acrylic monomer, so that its glass transition temperature be preferably 25 ℃ following, more preferably below 0 ℃, the weight-average molecular weight forming is thus that more than 100,000 acrylic acid series copolymers is useful as base polymer.
Can utilize following mode in polarization plates, to form adhesive layer, such as: make adhesive compound be dissolved or dispersed in the organic solvents such as toluene or ethyl acetate and prepare the solution of 10～40 % by weight, being applied directly to the mode in polarization plates; On diaphragm, form in advance adhesive phase, transferred to mode in polarization plates etc.The thickness of adhesive phase is determined according to its adhesive power etc., is suitably the scope of 1～50 μ m left and right.
In addition, can be as required in adhesive phase, coordinate the filling agent, pigment or the colorant that are formed by glass fibre or beaded glass, resin bead, metal powder or other inorganic powder etc., antioxidant, ultraviolet light absorber etc.Ultraviolet light absorber has salicylate based compound or benzophenone based compound, benzotriazole based compound, cyanoacrylate based compound, nickel complex salt based compound etc.
Laminated optical component can be configured in the one or both sides of liquid crystal cells.The liquid crystal cells using is for arbitrarily, can use such as take the liquid crystal cells of the active matrix drive-type that film transistor type is representative, the driving various liquid crystal cells formation liquid crystal indicators such as liquid crystal cells of simple matrix that the super-twist nematic of take is representative.The gluing common adhesive of using of laminated optical component and liquid crystal cells.
Embodiment
Below, illustrative embodiments, further specifically describes the present invention, but the present invention is not limited by these embodiment.In example, represent % and part of content or consumption, be unless otherwise specified weight standard.In addition, the cationically polymerizable compound using in following example, photo-induced cationic polymerization initiating agent, photosensitizer and photosensitizer additive are as described below, below symbolically respectively.
(A) cationically polymerizable compound (in table, being abbreviated as " epoxy compound ")
(a1) 3,4-epoxycyclohexyl methyl 3,4-epoxycyclohexane carboxylate [in above-mentioned formula (2), R 5=R 6the compound of=H, n=0]
(a2) CELLOXIDE 2081 (Daicel chemical company alicyclic epoxy resin processed) [in above-mentioned formula (2), R 5=R 6=H, Y 2=(CH 2) 5, n=1 compound]
(a3) EPOLEAD GT-301 (Daicel chemical company alicyclic epoxy resin processed) [in above-mentioned formula (3), R 7=R 8=R 9=H, Y 3=Y 4=(CH 2) 5, p=q=1 compound]
(a4) BDDE [in above-mentioned formula (12), X=(CH 2) 4compound]
(a5) Adeka Resin EP-4080E[is in above-mentioned formula (12), X=2, the compound of 2-isobutylene-dicyclohexyl]
(a6) compound that formula (13) represents
(B) photo-induced cationic polymerization initiating agent (in table, being abbreviated as " initiating agent ")
(b1) triaryl matte hexafluorophosphoric acid ester
(C) photosensitizer
(c1) 9, and 10-dibutoxy anthracene [in above-mentioned formula (IV), R 5=R 6=butyl, R 7the compound of=H, at wavelength 382nm, show greatly and absorb]
(D) photosensitizer additive (in table, being abbreviated as " sensitization auxiliary agent ")
(d1) Isosorbide-5-Nitrae-diethoxy naphthalene [in above-mentioned formula (I), R 1=R 2the compound of=ethyl]
(d2) 1-naphthols
[reference example] (thering is the making of the polyethylene terephthalate film of antiglare layer)
Preparation is dissolved in following composition ethyl acetate, can obtains the ultra-violet solidified resin composition of 1.53 refractive index after solidifying with solid component concentration 60%.
60 parts of pentaerythritol triacrylates
40 parts of polyfunctional carbamate acrylate (reaction product of hexamethylene diisocyanate and pentaerythritol triacrylate)
Then; 100 parts of the solid constituents of relative this ultra-violet solidified resin composition; add 2 parts, porous silica particle [trade name " サ イ リ シ ア ", シ リシ ア Co., Ltd. of Fuji system], as 2 of Photoepolymerizationinitiater initiater; 4; 5 parts of 6-trimethylbenzoyl diphenyl phosphine oxides (trade name " Le シ リ Application TPO ", BASF AG's system), make coating liquid.
This coating liquid is coated in to biaxial stretch-formed polyethylene terephthalate film (thickness 38 μ m) upper, forms ultra-violet solidified resin composition layer, in being set as the dryer of 80 ℃, make its dry 3 minutes.From the ultra-violet solidified resin composition layer side of dried film, with h ray conversion light quantity, count 300mJ/cm 2mode irradiate from intensity 20mW/cm 2the light of high-pressure mercury-vapor lamp, ultra-violet solidified resin composition layer is solidified, obtain duplexer antiglare film formation, that turbidity value is 10% by the irregular antiglare layer of surperficial tool (cured resin) and biaxial stretch-formed polyethylene terephthalate film.It should be noted that, turbidity value is used turbidity transmissivity instrument " HM-150 " [Murakami K. K.'s dye technology institute system] to measure.
[embodiment 1～26 and comparative example 1～13]
(1) preparation of photo-curable adhesive compound
The mixing ratio shown in table 1 (unit is part) of take is mixed after each composition, carries out deaeration, makes photo-curable tackifier liquid.It should be noted that, photo-induced cationic polymerization initiating agent (b1) coordinates with the form of 50% polypropylene carbonate ester solution, in table 1, with its solid constituent scale, shows.
[table 1]
(2) making of polarization plates
Corona discharge Treatment is implemented in the surface of the three cellulose acetate membrane of the thickness 80 μ m that contain ultraviolet light absorber [trade name " Off ジ タ Star Network ", Fuji Photo Film Co., Ltd.'s system], on this Corona discharge Treatment face, the mode of using excellent painting machine to be about 3 μ m with the thickness after solidifying applies the tackifier liquid separately of making above.Polyvinyl alcohol (PVA)-the iodine of fitting on its adhesive layer is polaroid.In addition, the binding face (with the surface of antiglare layer side opposition side) of the biaxial stretch-formed polyethylene terephthalate film with antiglare layer (thickness 43 μ m) that reference example is made is implemented Corona discharge Treatment, and the mode that is about 3 μ m with the thickness after solidifying on its Corona discharge Treatment face applies with excellent painting machine and identical above tackifier liquid.The one side of making above adhesive layer laminating at it is fitted with the polaroid side of the polaroid of three cellulose acetate membrane, makes sandwich.From the biaxial stretch-formed polyethylene terephthalate film side with antiglare layer of this sandwich, use the ultraviolet lamp (lamp is used " D light valve (the バ Le Block) " of U.S. spoke deep UV system house system) being attached with conveyor take adding up light quantity is 750mJ/cm 2mode irradiation ultraviolet radiation, make adhesive solidification.The two sides that is produced on thus polaroid is fitted with the polarization plates of diaphragm.
(3) the optical characteristics evaluation of polarization plates
The polarization plates that above-mentioned (2) are made is cut into the size of 30mm * 30mm, measures a value and the b value (in table, being abbreviated as respectively " quadrature a " and " quadrature b ") of quadrature transmissivity separately, degree of polarization, quadrature form and aspect.In mensuration, in the ultraviolet-visible pectrophotometer " UV-2450 " of use Shimadzu Scisakusho Ltd system, be fixed with the equipment as " with the membrane support of polaroid " of free accessory, obtain the axis of homology direction of the polarization plates in the scope of wavelength 380nm～780nm and absorb axial transmitted spectrum, utilizing the subsidiary software of this spectrophotometer " UV-Probe " to calculate a value and the b value of quadrature transmissivity, degree of polarization and quadrature form and aspect in wavelength 410nm, 550nm and 650nm.Together with the variable (amount of photosensitizer and photosensitizer additive) that result is formed with tackifier in table 1, be shown in table 2.
(4) durability evaluation of the polarization plates under damp and hot
The polarization plates that above-mentioned (2) are made is cut into the size of 30mm * 30mm, carries out placing the damp heat test of 240 hours under the hygrothermal environment of temperature 60 C, relative humidity 90% a value of the degree of polarization of the polarization plates after determination test, quadrature form and aspect and b value.With measuring with above-mentioned (3) same method.Result is shown in to table 2 simultaneously.In table 2, " before test " hurdle is the value of the polarization plates gained for before carrying out damp heat test, i.e. after making shown in above-mentioned (3), and " after test " hurdle is for for carrying out the value of the polarization plates gained after damp heat test.
[table 2]
As shown in Table 2, for be combined with in large quantities anthracene in tackifier, it is the polarization plates that the comparative example 1～3,6 and 11 of photosensitizer (c1) obtains, quadrature transmissivity under wavelength 410nm is high, leak blue light, and a value of quadrature form and aspect and the absolute value of b value all high, from neutral ash, to blue direction, depart from.In addition, by damp heat test quadrature form and aspect, great changes will take place.On the other hand, for do not coordinate anthracene in tackifier, it is the polarization plates that the comparative example 4,8,9 and 13 of photosensitizer (c1) obtains, although demonstrate good degree of polarization after manufacturing, do not have the light of blue light to leak yet, can obtain the form and aspect of neutral ash, but humidity resistance is poor, after damp heat test, degree of polarization is less than 99%, in addition, quadrature form and aspect also depart from from neutral ash.
On the other hand, can confirm, for having used a small amount of cooperation anthracene, be that photosensitizer (c1) and the naphthalene that is combined with ormal weight are the polarization plates that the embodiment 1～26 of the tackifier of photosensitizer additive (d1) obtains, can obtain in high degree of polarization and quadrature form and aspect a value and b value close to 0, and these values are almost constant before and after damp heat test, have good humidity resistance.

Claims (9)

1. a polarization plates, wherein,
Have:
The polaroid that the polyvinyl alcohol resin film that is adsorbed and is orientated by dichromatism pigment forms; With
At the diaphragm that comprises transparent resin that at least one side is fitted by adhesive layer of described polaroid,
Wherein, described adhesive layer is formed by photo-curable adhesive compound, and this photo-curable adhesive compound comprises:
(A) cationically polymerizable compound 100 weight portions;
(B) photo-induced cationic polymerization initiating agent 1～10 weight portion;
(C) light display that wavelength is greater than to 380nm is shown photosensitizer 0.1～2 weight portion of very big absorption; And
(D) naphthalene shown in following formula (I) is photosensitizer additive 0.1～10 weight portion,
In formula, R 1and R 2the alkyl that represents independently of one another carbon number 1～6,
The a value of the quadrature form and aspect of this polarization plates and b value are all in-0.5～+ 0.5 scope.
2. polarization plates according to claim 1, wherein,
Described cationically polymerizable compound (A) is not for containing the epoxy resin of aromatic rings.
3. polarization plates according to claim 1, wherein,
Described photosensitizer (C) is the anthracene based compound shown in following formula (IV),
In formula, R 5and R 6represent independently of one another the alkyl of carbon number 1～6 or the alkoxyalkyl of carbon number 2～12, R 7the alkyl that represents hydrogen atom or carbon number 1～6.
4. polarization plates according to claim 1, wherein,
In described photo-curable adhesive compound, cationically polymerizable compound (A) described in relative 100 weight portions, contains photosensitizer (C) described in 0.1～0.5 weight portion.
5. polarization plates according to claim 1, wherein,
The diaphragm that at least one side is fitted at polaroid comprises acetate fiber prime system resin.
6. polarization plates according to claim 1, wherein,
At the diaphragm of at least one side laminating of polaroid, comprise that to be selected from amorphous polyolefins be the transparent resin in resin, polyester based resin, acrylic resin, polycarbonate-based resin and chain polyolefin-based resins.
7. polarization plates according to claim 1, wherein,
Have:
The diaphragm that comprises acetate fiber prime system resin of fitting by described adhesive layer in the one side of polaroid; With
Comprising of fitting by described adhesive layer at the another side of polaroid is selected from the diaphragm that amorphous polyolefins is the transparent resin in resin, polyester based resin, acrylic resin, polycarbonate-based resin and chain polyolefin-based resins.
8. a laminated optical component, its duplexer by polarization plates claimed in claim 1 and other optical layers forms.
9. laminated optical component according to claim 8, wherein,
Described optical layers contains polarizer.
CN201010214538.4A 2009-06-26 2010-06-25 Polarization plate and laminated optical component using the same Active CN101937112B (en)

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Families Citing this family (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5827483B2 (en) * 2011-03-29 2015-12-02 住友化学株式会社 Polarizing plate and laminated optical member using photocurable adhesive
JP5945098B2 (en) * 2011-03-29 2016-07-05 住友化学株式会社 Polarizing plate and laminated optical member
JP5677883B2 (en) * 2011-03-29 2015-02-25 住友化学株式会社 Photo-curable adhesive, polarizing plate and laminated optical member
WO2012144261A1 (en) * 2011-04-19 2012-10-26 Dic株式会社 Cationic polymerizable adhesive and polarizing plate obtained using same
JP5966310B2 (en) * 2011-10-24 2016-08-10 住友化学株式会社 Polarizing plate and laminated optical member using the same
JP5855947B2 (en) * 2012-01-12 2016-02-09 住友化学株式会社 Photocurable adhesive, polarizing plate and laminated optical member using the same
JP5831249B2 (en) * 2012-01-23 2015-12-09 住友化学株式会社 Polarizing film, method for producing the same, and polarizing plate
KR102073987B1 (en) * 2012-02-28 2020-02-05 스미또모 가가꾸 가부시키가이샤 Compound and dichroic dye, and polarizing film
KR102129135B1 (en) * 2012-02-28 2020-07-01 스미또모 가가꾸 가부시키가이샤 Polarizing film, circular polarizing plate and method of producing the same
JP2013186397A (en) * 2012-03-09 2013-09-19 Sumitomo Bakelite Co Ltd Polarizable resin laminate, spectacles article and protection product
JP5953875B2 (en) * 2012-03-29 2016-07-20 住友化学株式会社 Polarizing plate and laminated optical member using the same
JP6047905B2 (en) * 2012-03-29 2016-12-21 住友化学株式会社 Polarizing plate and laminated optical member using the same
CN102660300B (en) * 2012-04-28 2014-02-12 深圳市华星光电技术有限公司 Liquid crystal medium composite as well as liquid crystal display using same and manufacturing method of liquid crystal medium composite
CN102746855B (en) * 2012-07-20 2015-02-25 深圳市华星光电技术有限公司 Liquid crystal medium mixture for liquid crystal display
CN102876336A (en) * 2012-09-21 2013-01-16 深圳市华星光电技术有限公司 Liquid crystal medium mixture and liquid crystal display employing liquid crystal medium mixture
JP2014133408A (en) * 2012-12-10 2014-07-24 Sumitomo Chemical Co Ltd Surface-treated laminate film and polarizing plate using the same
KR101628428B1 (en) * 2012-12-17 2016-06-08 제일모직주식회사 Polarizing plate, method for preparing the same and optical display apparatus comprising the same
TWI572600B (en) 2013-01-10 2017-03-01 Konica Minolta Inc Resin composition, triazole compound, optical film, polarizing plate, optical lens, circular polarizing plate, and image display device
JP2014137477A (en) * 2013-01-17 2014-07-28 Sumitomo Chemical Co Ltd Polarizing plate
JP2014191005A (en) * 2013-03-26 2014-10-06 Sumitomo Chemical Co Ltd Polarizing plate
JP6348291B2 (en) * 2014-02-04 2018-06-27 住友化学株式会社 Polarizing plate and display device
KR101542714B1 (en) 2014-04-04 2015-08-12 주식회사 엘지화학 Hetero-cyclic compound and organic light emitting device comprising the same
KR102096980B1 (en) * 2015-01-26 2020-04-03 동우 화인켐 주식회사 Polarizing plate
JP2016145286A (en) * 2015-02-06 2016-08-12 デクセリアルズ株式会社 Adhesive composition and method for production of connection structure
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JP2017122882A (en) * 2016-01-08 2017-07-13 住友化学株式会社 Photo-curable adhesive, and polarizing plate and laminate optical member using the same
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KR101941650B1 (en) * 2017-11-24 2019-01-23 주식회사 엘지화학 Polarizing plate and image display apparatus comprising the same
TWI843713B (en) * 2018-02-09 2024-06-01 日商住友化學股份有限公司 Circularly polarizing plate and optical display device
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KR102225902B1 (en) * 2018-05-21 2021-03-10 주식회사 엘지화학 Polarizing plate, image display apparatus comprising same and adhesive composition for plarizing plate
TWI819142B (en) * 2018-11-30 2023-10-21 日商住友化學股份有限公司 Photocurable adhesive, polarizing plate and laminated optical member
CN110441853B (en) * 2019-08-14 2021-07-13 佛山纬达光电材料股份有限公司 Xenon-lamp-resistant test polarizer and preparation method thereof

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6949297B2 (en) * 2001-11-02 2005-09-27 3M Innovative Properties Company Hybrid adhesives, articles, and methods
WO2006073021A1 (en) * 2005-01-06 2006-07-13 Kawasaki Kasei Chemicals Ltd. Photosensitizer, photosensitive acid generating agent, and photocurable composition
JP2007126612A (en) * 2005-11-07 2007-05-24 Kawasaki Kasei Chem Ltd Photosensitizer, photosensitive acid generator and photocurable composition
JP2007292944A (en) * 2006-04-24 2007-11-08 Fujifilm Corp Liquid crystal display device
JP4919403B2 (en) * 2006-09-14 2012-04-18 日本化薬株式会社 High durability polarizing plate
JP5448024B2 (en) * 2007-03-15 2014-03-19 住友化学株式会社 Photocurable adhesive, polarizing plate using the photocurable adhesive, method for producing the same, optical member, and liquid crystal display device
JP2009069375A (en) * 2007-09-12 2009-04-02 Sumitomo Chemical Co Ltd Method of manufacturing polarizing plate
FR2925908A1 (en) * 2007-12-27 2009-07-03 Bmuestar Silicones France Sas CATIONICALLY POLYMERIZABLE / CROSS-LINKABLE COMPOSITION COMPRISING IODONIUM BORATE AND FREEZING ACCEPTABLE ODOR

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