CN101937112A - Polarization plates and used the laminated optical component of this polarization plates - Google Patents

Abstract

The present invention provides a polarizing plate having a polyvinyl alcohol-based polarizing plate in which a dichroic dye is adsorbed and oriented, and at least one side of the polarizing plate bonded with an adhesive layer, and a laminated optical member using the polarizing plate. A protective film comprising a transparent resin, the adhesive layer is formed from a photocurable adhesive composition, and the photocurable adhesive composition contains: (A) 100 parts by weight of a cationic polymerizable compound, (B) a photocationic polymerization initiator 1 ~10 parts by weight, (C) 0.1-2 parts by weight of a photosensitizer showing maximum absorption for light with a wavelength greater than 380 nm, and (D) 0.1-10 parts by weight of a naphthalene-based photosensitizer represented by the following formula (I). (In the formula, R ¹ and R ² each independently represent an alkyl group having 1 to 6 carbon atoms.)

Description

Polarization plates and used the laminated optical component of this polarization plates

Technical field

The present invention relates to a kind of polarization plates that is fitted with the diaphragm that comprises transparent resin at the polaroid that comprises polyvinyl alcohol resin.The present invention also relates in addition and a kind of this polarization plates is layered in the laminated optical component that other optical layers forms.

Background technology

Polarization plates is useful as one of optical component that constitutes liquid crystal indicator.Polarization plates has the structure that is laminated with diaphragm on the two sides of polaroid usually, is loaded into liquid crystal indicator.Also known only have the one side at polaroid be provided with diaphragm, but what in most cases fit at another side is not simple diaphragm, but the layer that has as other function, for example optical function comes the double as diaphragm.In addition, as the manufacture method of polaroid, extensively adopt following method: the good uniaxial tension polyvinyl alcohol resin film that will utilize the dichromatism pigment dyeing carries out that boric acid is handled, after the washing, carry out drying.

Generally, after above-mentioned washing and drying, direct applying diaphragm on polaroid.There are the following problems for the result who does like this: dried polaroid physical strength is poor, when temporarily it being reeled, easily along machine direction fracture etc.Therefore, usually on dried polaroid, directly apply water system tackifier, by this tackifier diaphragm of fitting simultaneously on the two sides of polaroid as the polyvinyl alcohol resin aqueous solution.As diaphragm, the three cellulose acetate membrane of common used thickness 30～100 μ m.

The moisture permeability height of Triafol T is it as the diaphragm problem that the polarization plates form exists of fitting, damp and hot down, can take place under the condition of 70 ℃ of for example temperature, relative humidity 90% aging etc.Therefore, also known have moisture permeability is lower than Triafol T, for example is that the amorphous polyolefins of typical example is that resin is made diaphragm with the norbornene resin.

In the time of will fitting in the polyethenol series polaroid by the diaphragm that the low resin of moisture permeability constitutes; at present there are the following problems as the aqueous solution of the normally used polyvinyl alcohol resin of tackifier in the applying of polyethenol series polaroid and Triafol T: adhesive strength is insufficient, or the bad order of the polarization plates that obtains.This be since the low resin molding of moisture permeability be generally hydrophobicity or because of moisture permeability low can not be fully drying as the cause of the water of solvent etc.On the other hand; also known have different types of diaphragm of fitting on the two sides of polaroid; motion for example has: fit by amorphous polyolefins in the one side of polaroid and be the diaphragm that the low resin of moisture permeability such as resin constitutes, fit by the diaphragm that constitutes based on the high resin of the moisture permeabilitys such as cellulose-based resin of Triafol T at the another side of polaroid.

Therefore; as giving high adhesive power between diaphragm that constitutes at the resin low and the polyethenol series polaroid, simultaneously between high resin of moisture permeabilitys such as cellulose-based resin and polyethenol series polaroid, also giving the tackifier of high adhesive power, attempt using the active energy ray-curable tackifier by moisture permeability.For example, disclosing what do not contain aromatic rings in TOHKEMY 2004-245925 communique is the tackifier of principal ingredient with the epoxy compound, has proposed to make this adhesive solidification come gluing polaroid and diaphragm by the cationic polymerization that utilizes the actinic energy ray irradiation.In addition; disclosed technology is in TOHKEMY 2008-257199 communique; with combination alicyclic epoxy compound with do not have the epoxy compound of ester ring type epoxy radicals, cooperate the photo-curable tackifier of photo-induced cationic polymerization initiating agent simultaneously, be used for the gluing of polaroid and diaphragm.In this TOHKEMY 2008-257199 communique, record: by and use the photosensitizer that constitutes by anthracene compound, even contain at diaphragm under the situation of ultraviolet light absorber, also can give good adhesive power.

Promptly,, the cationically polymerizable compound that makes epoxy compound and so on cooperates the photo-induced cationic polymerization initiating agent for solidifying, but described photo-induced cationic polymerization initiating agent is generally near the light the wavelength 300nm or wavelength is shown the compound that greatly absorbs less than the light in the zone of 300nm, therefore, by cooperate to wavelength greater than the zone of 300nm, be specially wavelength and show the photosensitizer that greatly absorbs greater than the light of 380nm, near the light of this wavelength be can respond to, kation kind or lewis acidic generation promoted from the photo-induced cationic polymerization initiating agent.

In addition, expect that usually polarization plates is grey can show original color for neutrality when being applied to liquid crystal indicator.For example, in TOHKEMY 2002-169024 communique, proposed a kind of polarization plates,, and then obtained the white demonstration distinct, that contrast is high, a of the parallel form and aspect of described polarization plates of showing for white demonstration and black demonstration that can carry out more neutral ash ^*And b ^*And a of quadrature form and aspect ^*And b ^*Satisfy specific relation.

On the other hand, various improvement have also been carried out for the general Photocurable composition that uses in the field beyond the polarization plates, for example, in open No. 2006/073021 pamphlet of WO in the world, disclose the technology of anthracene compound and naphthalene compound or benzene compound combination being made photosensitizer.Also having put down in writing in open No. 2006/073021 pamphlet of WO in this world cooperates cationically polymerizable monomer and photo-induced cationic polymerization initiating agent to make Photocurable composition in above-mentioned photosensitizer, in addition, also enumerated the example of epoxy compound as the cationically polymerizable monomer.

Summary of the invention

The disclosed epoxy compound and photo-induced cationic polymerization initiating agent and anthracene of being combined with is the tackifier of photosensitizer in the above-mentioned TOHKEMY 2008-257199 communique by using; can gluing securely polaroid and diaphragm; for example; use this tackifier on polaroid, to be fitted with the polarization plates of diaphragm; can protected film or the influence of adhesive layer; show high degree of polarization according to the original degree of polarization that shows of polaroid, even behind damp heat test for example, also keep high degree of polarization like that.But in order to manifest described effect fully, needing to cooperate the anthracene of amount to a certain degree is photosensitizer.In this case, because anthracene is a photosensitizer light that wavelength surpasses 380nm is shown greatly absorption, therefore, when polarization plates is disposed at Nicol crossed, there are near the blue light leakage of wavelength 400nm, so-called blue leakage the (Japanese: Block Le one リ one Network) become big problem.Therefore, observe with Nicol crossed such use be combined with in a large number anthracene be the tackifier of photosensitizer make polarization plates the time, as can be known the form and aspect of transmitted light from neutral ash to blue deviation in driction.Also learning in addition, is under the situation of photosensitizer at the anthracene that cooperates amount to a certain degree, and the form and aspect under the Nicol crossed also change because of damp heat test 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 on the long light of wavelength is also shown the tackifier of the photosensitizer of absorption at ultraviolet region; be fitted with diaphragm at polaroid; when being disposed at Nicol crossed, keep 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 the still excellent laminated optical component of humidity resistance.

The inventor etc. concentrate on studies in order to solve described problem; found that; even reach the photo-curable adhesive compound that the long light of wavelength is also shown the photosensitizer of absorption at ultraviolet region in the cationically polymerizable compound, being combined with the photo-induced cationic polymerization initiating agent; the specific photosensitizer additive that cooperates ormal weight; use it for the applying of polaroid and diaphragm; thus; can obtain keeping polaroid neutral ash and can gluing securely polaroid and diaphragm, the also excellent polarization plates of humidity resistance, thereby finished the present invention.Find also that simultaneously as the cationically polymerizable compound, when the ratio with regulation cooperated alicyclic epoxy compound and aliphatic epoxy compound, such prescription was effective especially.

Promptly; the invention provides a kind of polarization plates; it possesses polaroid that the polyvinyl alcohol resin film that is adsorbed and is orientated by the dichromatism pigment constitutes and the diaphragm that comprises transparent resin of fitting by adhesive layer in the one side at least of this polaroid, and this adhesive layer is formed by the photo-curable adhesive compound that contains following each composition (A)～(D).

(A) cationically polymerizable compound 100 weight portions,

(B) photo-induced cationic polymerization initiating agent 1～10 weight portion,

(C) light demonstration very big photosensitizer 0.1～2 weight portion that absorb of wavelength greater than 380nm reached

(D) naphthalene shown in the following formula (I) is photosensitizer additive 0.1～10 weight portion.

In the formula, R ¹And R ²The alkyl of representing carbon number 1～6 independently of one another.

In above-mentioned polarization plates, the cationically polymerizable compound (A) that constitutes the 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 constitutes the photo-curable adhesive compound is preferably the anthracene based compound shown in the following formula (IV).

In the formula, R ⁵And R ⁶Represent the alkyl of carbon number 1～6 or the alkoxyalkyl of carbon number 2～12 independently of one another, R ⁷The alkyl of expression hydrogen atom or carbon number 1～6.

In above-mentioned any polarization plates, consider that from the viewpoint of keeping neutral ash in the scope of the adhesive power that suitably keeps polaroid and diaphragm, the amount of the photosensitizer in the 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 to constitute the mode of the diaphragm of one side at least that is fitted in polaroid by acetate fiber prime system resin.In addition, also can take by amorphous polyolefins is that the low resin of moisture permeability of resin, polyester based resin, acrylic resin, polycarbonate-based resin, chain polyolefin-based resins and so on constitutes the mode of the diaphragm of one side at least that is fitted in polaroid.And, the one side of polaroid by described adhesive layer fit the diaphragm that comprises acetate fiber prime system resin, fit by identical described adhesive layer at the another side of polaroid that to comprise amorphous polyolefins be that the mode of the diaphragm of the low resin of the moisture permeability of resin, polyester based resin, acrylic resin, polycarbonate-based resin, chain polyolefin-based resins and so on also is one of optimal way.

These polarization plates can remain in its quadrature form and aspect the neutral 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 that is made 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; by in the photo-curable adhesive compound that reduces applying polaroid and diaphragm wavelength being shown the amount of the photosensitizer that greatly absorbs greater than the light of 380nm; cooperating the naphthalene of ormal weight is photosensitizer additive; can keep the adhesive strength between polaroid and the diaphragm, and manifest neutral ash as the form and aspect of polaroid.In addition, for polarization plates of the present invention, even place under the hygrothermal environment, degree of polarization or quadrature form and aspect also are not easy to change, and show good humidity resistance.The laminated optical component that forms in stacked other optical layers of this polarization plates also fully shows the function as polarization plates, and the humidity resistance excellence.

Embodiment

Below, the present invention is described in detail.The diaphragm that polarization plates of the present invention possesses polaroid and fits by adhesive layer in the one side at least of this polaroid.

[polaroid]

Polaroid comprises the polyvinyl alcohol resin film that the dichromatism pigment is adsorbed and is orientated.The polyvinyl alcohol resin that constitutes polaroid is by being that resin carries out saponification and obtains with polyvinyl acetate (PVA).As polyvinyl acetate (PVA) is resin, except that polyvinyl acetate (PVA) as the homopolymer of vinyl acetate, but the example vinyl acetate and can with multipolymer of other monomer of its copolymerization etc.As can with other vinyl acetate copolymerized monomer, for example can enumerate: unsaturated carboxylic acid class, olefines, vinyl ethers, unsaturated sulfonic acid class etc.The saponification degree of polyvinyl alcohol resin is generally the scope of 85～100 moles of %, preferred 98～100 moles of %.Further modification of polyvinyl alcohol resin for example can be used the polyvinyl formal that formed by the aldehydes modification or polyvinyl acetal etc.The degree of polymerization of polyvinyl alcohol resin is generally 1,000～10, and 000, preferred 1,500～5,000 scope.

Polaroid can be made through following operation: the operation of this polyvinyl alcohol resin film being carried out uniaxial tension; The polyvinyl alcohol resin film is dyeed with the dichromatism pigment, make it adsorb the operation of this dichromatism pigment; The operation that the polyvinyl alcohol resin film that is adsorbed with the dichromatism pigment is handled with boric acid aqueous solution.

Uniaxial tension both can carry out before the dyeing that utilizes the dichromatism pigment, also can carry out simultaneously with the dyeing that utilizes the dichromatism pigment, can also carry out after the dyeing that utilizes the dichromatism pigment.When carrying out uniaxial tension after the dyeing that utilizes the dichromatism pigment, this uniaxial tension both can carry out before boric acid is handled, and also can carry out in boric acid is handled.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, both can be the dry type stretching that in atmosphere, stretches, also can be for utilizing the wet type that stretches under the state of solvent swell to stretch.Draw ratio is generally about 4～8 times.

For the polyvinyl alcohol resin film is dyeed with the dichromatism pigment, for example the polyvinyl alcohol resin film immersion is got final product in the aqueous solution that contains the dichromatism pigment.As the dichromatism pigment, specifically use iodine or dichromatism organic dyestuff.

Use the situation of iodine, adopt the method that dipping polyvinyl alcohol resin film dyes in the aqueous solution that contains iodine and potassium iodide usually as the dichromatism pigment.Usually relative water 100 weight portions of the content of the iodine in this aqueous solution are about 0.01～0.5 weight portion, and usually relative water 100 weight portions of the content of potassium iodide are about 0.5～10 weight portion.The temperature of this aqueous solution is generally about 20～40 ℃, and in addition, the time (dyeing time) that impregnated in this aqueous solution was generally about 30～300 seconds.

On the other hand, use the situation of dichromatism organic dyestuff, adopt the method that dipping polyvinyl alcohol resin film dyes in the aqueous solution that contains water miscible dichromatism organic dyestuff usually as the dichromatism pigment.Usually relative water 100 weight portions of the content of the dichromatism organic dyestuff in this aqueous solution are 1 * 10 ^-3～1 * 10 ^-2About weight portion.This aqueous solution can contain inorganic salts such as sodium sulphate.The temperature of this aqueous solution is generally about 20～80 ℃, and in addition, the time (dyeing time) that impregnated in this aqueous solution was generally about 30～300 seconds.

Utilizing boric acid after the dyeing of dichromatism pigment to handle carries out in boric acid aqueous solution by the polyvinyl alcohol resin film immersion after will dyeing.Usually relative water 100 weight portions of the content of the boric acid in the boric acid aqueous solution are about 2～15 weight portions, are preferably about 5～12 weight portions.Using under the situation of iodine as the dichromatism pigment, preferably this boric acid aqueous solution contains potassium iodide.Usually relative water 100 weight portions of the content of the potassium iodide in the boric acid aqueous solution are about 2～20 weight portions, 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 handled is washed processing usually.In water, wash processing by the polyvinyl alcohol resin film immersion that for example will carry out the boric acid processing.Dried is implemented in the washing back, can obtain polaroid.The temperature of the water during washing is handled is generally about 5～40 ℃, and dip time was generally about 2～120 seconds.Thereafter the dried of carrying out uses air drier or far infra-red heater to carry out usually.Baking temperature is generally 40～100 ℃.In addition, the time of dried was generally about 120～600 seconds.

The thickness of the polaroid that is made of the polyvinyl alcohol resin film that so obtains can be set at about 10～50 μ m.

[adhesive layer]

For the polaroid that obtains like this,, become polarization plates at its diaphragm that at least simultaneously comprises transparent resin by the adhesive layer applying.In the present invention, as the tackifier that is formed at the adhesive layer of polaroid applying diaphragm, use the photo-curable adhesive compound of each composition that contains following (A)～(D).

(A) the cationically polymerizable compound,

(B) the photo-induced cationic polymerization initiating agent,

(C) the light demonstration very big photosensitizer that absorb of wavelength greater than 380nm reached

(D) naphthalene shown in the above-mentioned formula (I) is a photosensitizer additive.

(cationically polymerizable compound)

Cationically polymerizable compound (A) is the principal ingredient of photo-curable adhesive compound, it is the composition of giving adhesive power by polymerizing curable, as long as the compound for solidifying by cationic polymerization especially preferably contains the epoxy compound that has at least 2 epoxy radicals in the molecule.Epoxy compound has: the aromatic epoxy compound that has aromatic rings in the molecule; Have at least 2 epoxy radicals, at least 1 alicyclic epoxy compound that is bonded to the ester ring type ring wherein in the molecule; Do not have aromatic rings in the molecule, contain the carbon atom bonding of ring (being generally the oxirane ring) of 2 carbon atoms of epoxy radicals and its bonding in aliphatic epoxy compound of other aliphatic carbon atom etc.Being used for photo-curable adhesive compound of the present invention is that the compound of principal ingredient is as cationically polymerizable compound (A) with epoxy resin, particularly the alicyclic epoxy compound that does not contain aromatic rings especially preferably.If use with the cationically polymerizable compound of alicyclic epoxy compound as principal ingredient; then can obtain preserving the high solidfied material of elastic modulus; in the polarization plates that forms by gluing diaphragm of this solidfied material (adhesive layer) and polaroid, polaroid is not easy to break.

As mentioned above, the alicyclic epoxy compound is to have at least 2 epoxy radicals, at least 1 compound that is bonded to the ester ring type ring wherein in the molecule.At this, what is called is bonded to the epoxy radicals of ester ring type ring, be meant as shown in the formula shown in (V), epoxy radicals (O-) 2 in conjunction with hand respectively with 2 carbon atoms (the being generally adjacent carbon atom) Direct Bonding that constitutes the 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 group bonding of form of hydrogen atom can become the alicyclic epoxy compound in the compound that other chemical constitution forms.The hydrogen that constitutes the ester ring type ring can suitably be replaced by the straight chain shape alkyl of methyl or ethyl and so on.Wherein, the compound that preferably has 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 the alicyclic epoxy compound, the effective aspect consideration that is easy to get calmly and improves the storage elastic modulus of solidfied material, the compound of any expression of further preferably following (1)～(11).

(in the formula, R ¹～R ²⁴The alkyl of representing hydrogen atom or carbon number 1～6 independently of one another, R ¹～R ²⁴During for alkyl, the position that is bonded to the ester ring type ring is any number of 1～6.The alkyl of carbon number 1～6 can be straight chain, also can have side chain, can also have the ester ring type ring.Y ⁸The alkane 2 basis of expression oxygen atom or carbon number 1～20, Y ¹～Y ⁷Expression 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 of above-mentioned (1)～(11) expression, the ester ring type di-epoxy compounds shown in the above-mentioned formula (2) obtains easily, and is therefore preferred.The ester ring type di-epoxy compounds of formula (2) is 3, the 4-epoxy radicals hexahydrobenzyl alcohol alkyl of bonding carbon number 1～6 (can on its cyclohexane ring) and 3, the carboxylate of the 4-epoxy-cyclohexane 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 3,4-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 the alicyclic epoxy compound, be effective also with the epoxy resin that does not have the ester ring type epoxy radicals basically.If will be principal ingredient, wherein and with the compound that does not have the epoxy resin of ester ring type epoxy radicals basically make the cationically polymerizable compound with the alicyclic epoxy compound; then the storage elastic modulus of solidfied material can be remained on high value, and further improve the adaptation of polaroid and diaphragm.A carbon atom bonding of ring (being generally the oxirane ring) that at this said epoxy resin that does not have the ester ring type epoxy radicals basically is 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 the preferred following formula (12).

(in the 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 substituting group in 3 kinds of substituting groups that following formula represents, this alkylidene can be replaced by halogen atom.)

(in the formula, R ²⁵And R ²⁶The naphthenic base of the carbon number 3～10 of representing 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 respectively independently or can being replaced by the alkyl of carbon number 1～10 or alkoxy, R ²⁵And R ²⁶Can link mutually and form ring, A and D be the heterocyclic radical or the halogen atom of the aryl alkyl of the aryl of the alkyl of the expression carbon number 1～10 that can be replaced by halogen atom, 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 independently respectively, methylene in this alkyl, aryl, the 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 obtains easily, and is therefore preferred.

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, aliphatic diols such as 10-decanediol; Ester ring type glycol such as cyclohexanedimethanol, cyclohexane diol, hydrogenation bisphenol-A, hydrogenation Bisphenol F; The polyvalent alcohol that ternarys such as trimethylolethane, trimethylolpropane, hexose alcohols, pentose alcohols, glycerine, polyglycereol, pentaerythrite, dipentaerythritol, tetra methylol propane are above.

And with the alicyclic epoxy compound with when not having the epoxy resin of ester ring type epoxy radicals basically, both cooperation ratios are benchmark with the cationically polymerizable total amount of compound, preferably the alicyclic epoxy compound are set at 50～95 weight % and incite somebody to action the epoxy resin that will not have the ester ring type epoxy radicals basically to be set at more than the 5 weight %.By in cationically polymerizable compound integral body, cooperating the alicyclic epoxy compound more than the 50 weight %; can make the storage elastic modulus of solidfied material in the time of 80 ℃ is 1; more than the 000MPa; in the polarization plates that forms by gluing polaroid of this solidfied material (adhesive layer) and diaphragm, polaroid is not easy to break.In addition, by the epoxy resin that does not have the ester ring type epoxy radicals basically more than the relative cationically polymerizable compound overall co-ordination 5 weight %, can improve the adaptation of polaroid and diaphragm.Under the situation of cationically polymerizable compound for the binary system of the epoxy resin that do not have the ester ring type epoxy radicals basically and alicyclic epoxy compound, basically the amount that does not have the epoxy resin of ester ring type epoxy radicals is that benchmark allows to 50 weight % with the cationically polymerizable total amount of compound, it is measured when too many, the storage elastic modulus of solidfied material reduces, polaroid breaks easily, therefore, be that benchmark is set at its amount below the 45 weight % preferably with the cationically polymerizable total amount of compound.

As the cationically polymerizable compound (A) that constitutes the photo-curable adhesive compound, and with such alicyclic epoxy compound of above explanation with when not having the epoxy resin of ester ring type epoxy radicals basically, 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, but in addition epoxy compound of enumerative (1)～formula (12), oxetane compound etc.

Formula (1)～formula (12) epoxy compound in addition has: have in formula (1)～formula (11) molecule in addition in addition the aliphatic epoxy compound with the oxirane ring that is bonded to the aliphatic carbon atom of at least 1 alicyclic epoxy compound that is bonded to the epoxy radicals of ester ring type ring, formula (12), the molecule and have the aromatic epoxy compound of aromatic rings and epoxy radicals, the hydrogenation epoxy compound that the aromatic rings in the aromatic epoxy compound is hydrogenated etc.

Example as the alicyclic epoxy compound that has at least 1 epoxy radicals that is bonded to the ester ring type ring in formula (1)～formula (11) molecule in addition, 4 vinyl cyclohexene diepoxide or 1 are arranged, 2:8, the diepoxide of the vinyl cyclohexene class of 9-bicyclic oxygen citrene and so on etc.

As formula (12) aliphatic epoxy examples for compounds in addition, the triglycidyl ether of glycerine, the triglycidyl ether of trimethylolpropane, the diglycidyl ether of polyglycol etc. are arranged with the oxirane ring that is bonded to the aliphatic carbon atom.

The aromatic epoxy compound that has aromatic rings and epoxy radicals in the molecule can be the glycidol ether of the aromatic polyhydroxy compounds that has at least 2 phenol hydroxyls in the molecule, as its concrete example, the diglycidyl ether of bisphenol-A, the diglycidyl ether of Bisphenol F, the diglycidyl ether of bisphenol S, the glycidol ether of phenol phenolic varnish type resin etc. are arranged.

The hydrogenation epoxy compound that aromatic rings in the aromatic epoxy compound is hydrogenated can be for carrying out the compound that glycidyl ether forms with the hydrogenation polyol, described hydrogenation polyol is by having the aromatic polyhydroxy compounds of at least 2 phenol hydroxyls in the presence of catalyzer in the molecule as the raw material of above-mentioned aromatic epoxy compound, add to depress and optionally carry out hydrogenation and obtain, as concrete example, the diglycidyl ether of hydrogenated bisphenol A is arranged, 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, when cooperating the compound have the epoxy radicals that is bonded to the ester ring type ring, to be classified as previously defined alicyclic epoxy compound, total amount with the cationically polymerizable compound is a benchmark, and the consumption sum of the alicyclic epoxy compound shown in itself and above-mentioned formula (the 1)～formula (11) is in the scope that is no more than 95 weight %.

In addition, can become arbitrarily that the oxetane compound of cationically polymerizable compound is the compound that has 4 yuan of cyclic ethers (oxetanyl) in the molecule,, can be listed below compound as its concrete example.

3-ethyl-3-methylol oxetanes,

1, two [(3-ethyl-3-oxetanyl) methoxy] benzene of 4-,

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,

1, two [(the 3-ethyl oxetanes-3-yl) methoxyl] benzene of 3-,

The oxetanyl silsesquioxane,

Oxetanyl silicate etc.

By being benchmark with the cationically polymerizable total amount of compound, cooperating oxetane compound with the ratio below the 30 weight %, compare with the situation that only epoxy compound is used as the cationically polymerizable compound, can expect to improve the effect of curable and so on sometimes.

(photo-induced cationic polymerization initiating agent)

In the present invention, the cationic polymerization of the irradiation of aforesaid cationically polymerizable compound by utilizing actinic energy ray is solidified, thereby form adhesive layer, therefore, in the photo-curable adhesive compound, cooperate photo-induced cationic polymerization initiating agent (B).The photo-induced cationic polymerization initiating agent utilizes the irradiation of the actinic energy ray of visible light, ultraviolet ray, X ray, electron beam and so on to produce kation kind or lewis acid, causes the polyreaction of cationically polymerizable compound (A).The 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.Produce kation kind or lewis acidic compound as the irradiation that utilizes actinic energy ray, 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-aromatic hydrocarbons complex compound etc.

As the aromatic series diazo salt, can enumerate for example following compound.

Benzene diazonium hexafluoro antimonate,

Benzene diazonium hexafluorophosphate,

Benzene diazonium hexafluoro borate etc.

As the 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 the aromatic series sulfonium salt, can enumerate for example following compound.

The triphenylsulfonium hexafluorophosphate,

The triphenylsulfonium hexafluoro antimonate,

Triphenylsulfonium four (pentafluorophenyl group) borate,

The two hexafluorophosphates of 4,4 '-two [diphenyl sulfonium base] diphenyl sulphur,

The two hexafluoro antimonates of 4,4 '-two [two (beta-hydroxy ethoxy) phenyl sulfonium base] diphenyl sulphur,

The two hexafluorophosphates of 4,4 '-two [two (beta-hydroxy ethoxy) phenyl sulfonium base] diphenyl sulphur,

7-[two (p-methylphenyl) sulfonium base]-2-isopropyl thioxanthone hexafluoro antimonate,

7-[two (p-methylphenyl) sulfonium]-2-isopropyl thioxanthone four (pentafluorophenyl group) borate,

4-phenylcarbonyl group-4 '-diphenyl sulfonium base-diphenyl sulphur hexafluorophosphate,

4-(to the tert-butyl-phenyl carbonyl)-4 '-diphenyl sulfonium base-diphenyl sulphur hexafluoro antimonate,

4-(to the tert-butyl-phenyl carbonyl)-4 '-two (p-methylphenyl) sulfonium base-diphenyl sulphur four (pentafluorophenyl group) borate etc.

As iron-aromatic hydrocarbons complex compound, 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 (the 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, perhaps also can mix use more than 2 kinds.Wherein, even especially near the wavelength region may of aromatic series sulfonium salt 300nm also has the UVA characteristic, so, the curable excellence, therefore the solidfied material that can obtain having excellent mechanical intensity or adhesive strength, especially preferably uses.

Relative whole 100 weight portions of cationically polymerizable compound (A), the use level of photo-induced cationic polymerization initiating agent (B) is set at 1～10 weight portion.Cooperate the above photo-induced cationic polymerization initiating agent of 1 weight portion by relative cationically polymerizable compound (A) 100 weight portions, cationically polymerizable compound (A) is solidified fully, give the physical strength and the adhesive strength of the polarization plate hight that obtains.On the other hand, when its amount increases, because of increasing the hydroscopicity that causes solidfied material, the ionic substance in the solidfied material raises, the endurance quality of polarization plates is descended, therefore, the relative cationically polymerizable compound of the amount of photo-induced cationic polymerization initiating agent (B) (A) 100 weight portions are set at below 10 weight portions.The relative cationically polymerizable compound of the use level of preferred photic cationic polymerization initiators (B) (A) 100 weight portions are set at more than 2 weight portions, in addition, are preferably set to below 6 weight portions.

(photosensitizer)

For being used for photo-curable adhesive compound of the present invention, except the aforesaid cationically polymerizable compound (A) and photo-induced cationic polymerization initiating agent (B) that contains epoxy compound, also contain wavelength is shown the photosensitizer (C) that greatly absorbs greater than the light of 380nm.Above-mentioned photo-induced cationic polymerization initiating agent (B) near the 300nm or its short light of wavelength ratio show greatly and absorb, 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 induction, can cooperate the photosensitizer (C) that this wavelength is shown very big absorption greater than the light of 380nm.As described photosensitizer (C), can advantageously use the anthracene based compound shown in the above-mentioned formula (IV).Concrete example as the anthracene based compound shown in the 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-two amoxy anthracenes,

9,10-two own oxygen base anthracenes,

9, two (2-methoxy ethoxy) anthracenes of 10-,

9, two (2-ethoxy ethoxy) anthracenes of 10-,

9, two (the 2-butoxy ethoxy) anthracenes of 10-,

9, two (the 3-butoxy propoxyl group) anthracenes of 10-,

2-methyl or 2-ethyl-9,10-dimethoxy anthracene,

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-two amoxy anthracenes,

2-methyl or 2-ethyl-9,10-two own oxygen base anthracenes etc.

By in the photo-curable adhesive compound, cooperating aforesaid photosensitizer (C), to compare with the situation of mismatching it, the curable of adhesive compound improves.By being set at more than 0.1 weight portion, can manifest such effect with respect to the use level of the photosensitizer (C) of cationically polymerizable compound (A) 100 weight portions that constitute the photo-curable adhesive compound.On the other hand, when the use level of photosensitizer (C) increases, can occur in the low temperature keeping and problem such as the time separate out, therefore, cationically polymerizable compound (A) 100 weight portions relatively, its amount is set at below 2 weight portions.Consider from the neutral grey viewpoint of keeping polarization plates; in the scope of the 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 preferably are set at the amount of photosensitizer (C) 0.1～0.5 weight portion, further are the scope of 0.1～0.3 weight portion.

(photosensitizer additive)

For being used 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 the photosensitizer (C) of above explanation, also containing the naphthalene shown in the 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 is the concrete example of photosensitizer additive (D), can be listed below compound.

1, the 4-dimethoxy-naphthalene,

1-ethoxy-4-methoxynaphthalene,

1,4-diethoxy naphthalene,

1,4-dipropoxy naphthalene,

1,4-dibutoxy naphthalene etc.

By cooperate naphthalene in the photo-curable adhesive compound is photosensitizer additive (D), compares with the situation of mismatching it, and the curable of adhesive compound improves.By being that the use level of photosensitizer additive (D) is set at more than 0.1 weight portion, can manifest such effect with respect to the naphthalene of cationically polymerizable compound (A) 100 weight portions that constitute the photo-curable adhesive compound.On the other hand, when naphthalene is the use level of photosensitizer additive (D) when increasing, problem such as separate out in the time of can occurring in the low temperature keeping, therefore, cationically polymerizable compound (A) 100 weight portions relatively, its amount is set at 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,, can make it contain additive component as other composition of any composition.As additive component, except that above-mentioned photo-induced cationic polymerization initiating agent and photosensitizer (C), can cooperate in addition photosensitizer 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, above-mentioned relatively 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 that is made of the polyvinyl alcohol resin film of explanation by photo-curable adhesive compound stacked guard film described above, solidifies the photo-curable adhesive compound in front, makes polarization plates.Diaphragm can be by constituting as the most widely used resin molding that is lower than Triafol T based on the cellulose acetate resin film or the moisture permeability of Triafol T of the diaphragm of polarization plates at present.The moisture permeability of Triafol T probably is 400g/m ²About/24hr.

In an optimal way, the diaphragm of fitting in the one side at least of polaroid comprises acetate fiber prime system resin.In another optimal way, the diaphragm of fitting in the one side at least of polaroid comprises resin molding, for example moisture permeability 300g/m that moisture permeability is lower than Triafol T ²The resin molding that/24hr is following.As the resin that constitutes the low resin molding of this moisture permeability, 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; fitting by above-mentioned adhesive layer in the one side of polaroid comprises the diaphragm of acetate fiber prime system resin, and fitting by identical above-mentioned adhesive layer at the another side of polaroid comprises the diaphragm of the low transparent resin of aforesaid moisture permeability.

Acetate fiber prime system resin be at least a portion hydroxyl in the cellulose by the resin of acetic acid esterification, can be for a part by acetic acid esterification, a part by the mixed ester of other acid estersization.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 the polymkeric substance of the such polymerized unit with cyclic olefin of substituent compound is arranged, can be the multipolymer that cyclic olefin and chain alkene and/or aromatic ethenyl compound copolymerization are formed.Under the situation of the multipolymer of the homopolymer of cyclic olefin or the cyclic olefin more than 2 kinds, residual pair of key by ring-opening polymerization, therefore, the material that generally uses hydrogenation there to form is a resin as amorphous polyolefins.Wherein, representative substances is that thermoplastic norbornene is a resin.

Polyester based resin is the polymkeric substance that the polycondensation by dibasic acid and dibasic alcohol obtains, and representative substances is a polyethylene terephthalate.Acrylic resin is to be the polymkeric substance of principal monomer with the methyl methacrylate, 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 to have carbonic acid ester bond (polymkeric substance O-CO-O-), the material that representative substances obtains for the polycondensation by bisphenol-A and phosgene on the main chain.The chain polyolefin-based resins is that the chain alkene with ethene or propylene and so on is the polymkeric substance of principal monomer, can be homopolymer or multipolymer.Wherein, representative substances is the multipolymer that copolymerization has small amount of ethylene in the homopolymer of propylene or the propylene.

For this diaphragm, on the face opposite, can have the various surface-treated layers of hard conating, anti-reflecting layer, antiglare layer, antistatic layer and so on the face that fits in polaroid.Diaphragm comprises under the situation that is formed with this surface-treated layer, can be about 5～150 μ m with its thickness setting.Its thickness is preferably more than the 10 μ m, in addition, is preferably below the 120 μ m, more preferably below the 100 μ m.

[polaroid and diaphragm gluing]

When gluing polaroid and diaphragm; form the overlay of photo-curable adhesive compound described above at the one or both sides of the gluing surface of polaroid and diaphragm; by this overlay applying polaroid and diaphragm; by the irradiation actinic energy ray overlay of the uncured photo-curable adhesive compound of such formation is solidified, diaphragm is anchored on the 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 for example scraper coating, metal thread bar coating, die head coating, funny point type coating, gravure coating.In addition, Yi Bian also can to adopt on one side binding face with polaroid and diaphragm be that the mode of inboard is supplied with polaroid and diaphragm continuously, made the mode of adhesive compound curtain coating betwixt.Each application pattern has optimum viscosity scope separately, and therefore, using the viscosity of solvent adjustment photo-curable adhesive compound also is useful technology.The solvent that is used for this can use the solvent that dissolves the photo-curable adhesive compound under the condition that the optical characteristics that can not make polaroid descends well, and its kind is not particularly limited.For example can use with toluene as the hydro carbons of representative, with the organic solvents such as ester class of ethyl acetate as representative.The thickness of adhesive layer is generally below the 20 μ m, is preferably below the 10 μ m, more preferably below the 5 μ m.During the adhesive layer thickening, the reaction rate decline of adhesive compound, the humidity resistance of polarization plates are worsened.

When gluing polaroid and diaphragm; for both one or both sides of binding face; before the overlay that forms 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 that uses for the overlay to the photo-curable adhesive compound shines actinic energy ray gets final product so long as produce the light source of ultraviolet ray, electron beam, X ray etc.Especially preferably use and below wavelength 400nm, have for example Cooper-Hewitt lamp of luminescence distribution, 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.Actinic energy ray exposure intensity to the 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 0.1～100mW/cm ²When to the rayed intensity of photo-curable adhesive compound less than 0.1mW/cm ²The time, the reaction time is long, when its greater than 100mW/cm ²The time, because the heat release during from the heat of lamp radiation and the polymerization of photo-curable adhesive compound, it is aging that photo-curable adhesive compound generation xanthochromia or polaroid are taken place.The rayed time to the photo-curable adhesive compound is controlled by each cured compositions, still is not particularly limited, and preferably the accumulative total light quantity of representing with the long-pending form of exposure intensity and irradiation time is 10～5,000mJ/cm ²Mode set.When the photo-curable adhesive compound being carried out light-struck accumulative total light quantity less than 10mJ/cm ²The time, might make the generation of the spike that comes from initiating agent insufficient, the curing of the adhesive layer that obtains is insufficient, on the other hand, when its accumulative total light quantity surpasses 5,000mJ/cm ²The time, irradiation time is very long, is unfavorable for boosting productivity.

When the two sides of polaroid applying diaphragm; the irradiation which diaphragm side to carry out actinic energy ray from can; for example; contain ultraviolet light absorber at a diaphragm, another diaphragm does not contain under the situation of ultraviolet light absorber; aspect effectively utilizing the actinic energy ray that shone, improving curing rate, preferably never contain the diaphragm side irradiation actinic energy ray of ultraviolet light absorber.

[optical characteristics of polarization plates]

For polarization plates of the present invention; by what cooperated in the minimizing photo-curable adhesive compound wavelength is shown that greater than the light of 380nm the amount of the photosensitizer (C) that greatly absorbs, the naphthalene of cooperation ormal weight are photosensitizer additive (D); the adhesive strength between polaroid and the diaphragm can be kept, and the form and aspect that polaroid had originally can be directly manifested.Therefore,, just can remain untouched and keep its neutral ash, for example, can make a value of quadrature form and aspect and b value be-0.5～+ 0.5 scope as long as polaroid shows the neutral ash of expectation.

So-called quadrature form and aspect are meant when 2 polarization plates are under with the overlapping state of the mode of separately absorption axes quadrature, from an irradiates light from the form and aspect of the light of another side transmission.A and b, use standard light C that the form and aspect are here represented by the Lab color specification system measure.The Lab color specification system is represented with the brightness index L of Hunter and form and aspect a and b as JIS K 5981:2006 " 5.5 promote atmospheric exposure test " are put down in writing.The value of L, a and b by tristimulus values X, Y and the Z of defined among the 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 being exposed to, polarization plates of the present invention also is not easy deterioration, humidity resistance excellence under the hot and humid condition.For example, behind 240 hours damp heat test of placement under the hygrothermal environment of 60 ℃ of temperature, relative humidity 90%, also a value and the b value of quadrature form and aspect can be remained on above-mentioned scope even carry out.

[laminated optical component]

For polarization plates of the present invention, the optical layers with optical function beyond the laminated polarizing plate can be made laminated optical component.Typical way is; pass through tackifier or the stacked applying optical layers of bonding agent by diaphragm in polarization plates; 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 applying diaphragm, at the another side of polaroid by tackifier (Japanese: then cut open) or the stacked applying optical layers of bonding agent (Japanese: adhesion is cutd open).The latter's situation, as being used to the tackifier of polaroid and optical layers of fitting, as long as use the photo-curable adhesive compound of stipulating among the present invention, then its optical layers also can become the diaphragm of stipulating among the present invention simultaneously.

Enumerate the example of the optical layers that is laminated in polarization plates, about the polarization plates of the rear side that is disposed at liquid crystal cells, there are reflection horizon, Transflective layer, light diffusion layer, solar panel, the brightness that are laminated in this polarization plates to improve film etc. with towards the liquid crystal cell side opposition side.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, all have be laminated in this polarization plates towards the polarizer of liquid crystal cell side etc.

Reflection horizon, Transflective layer or light diffusion layer are respectively to be provided with for the polarization plates (optical component) of the polarization plates (optical component) of the polarization plates (optical component) of making reflection-type, Transflective or diffused.The polarization plates of reflection-type can be used for making the liquid crystal indicator that reflects the type that shows from the incident light of identification side, can omit light sources such as back of the body irradiation, therefore, and easily with the liquid crystal indicator slimming.In addition, the polarization plates of Semitransmissive is used in the where there is light as reflection-type, in the dark by the liquid crystal indicator from the type that shows of light of back of the body irradiation.Optical component as reflection type polarizer can form as the reflection horizon by for example set up the paper tinsel or the vapor-deposited film that are made of metals such as aluminium on the diaphragm on the polaroid.Can be as the optical component of Semitransmissive polarization plates by above-mentioned reflection horizon being made half-mirror, maybe will containing pearl pigment etc. and the radioparent reflecting plate of display light and polarization plates is gluing forms.On the other hand, the optical component as the diffused polarization plates can form the micro concavo-convex structure and form by using the method for for example the diaphragm enforcement delustring of polarization plates being handled, the method that coating contains the resin of particulate, the gluing the whole bag of tricks such as method that contain the film of particulate on the surface.

And laminated optical component also can be the dual-purpose polarization plates of reflection diffusion.The dual-purpose polarization plates of reflection diffusion can utilize the methods such as reflection horizon that its concaveconvex structure of mapping for example is set on the micro concavo-convex structural plane of diffused polarization plates to form.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.In addition, containing the resin bed of particulate or film also has and can spread, suppress the unequal advantage of light and shade when incident light and reflected light transmission thereof contain the particulate layer.For the reflection horizon that makes surperficial micro concavo-convex structure mapping, can utilize methods such as the evaporation of for example vacuum evaporation, ion plating, sputter and so on or plating, the surface that metal directly is attached to the micro concavo-convex structure forms.The particulate that cooperates in order to form surperficial micro concavo-convex structure can be that the silicon dioxide of 0.1～30 μ m, aluminium oxide, titanium dioxide, zirconia, tin oxide, indium oxide, cadmium oxide, antimony oxide and so on inorganic is organic system particulate of particulate, crosslinked or noncrosslinking polymkeric substance and so on etc. for for example mean grain size.

Solar panel is in order to carry out light path control etc. and 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 that improves in the 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, the alignment films of cholesteric liquid crystal polymers or the circularly polarizing separation sheet of its aligned liquid-crystal layer etc. arranged in the film base material upper support.

On the other hand, be to use as the polarizer of above-mentioned optical layers in order to compensate the phase differential that causes by liquid crystal cells etc.As the example, can enumerate: the birefringent film, the orientation that are made of the stretched film of various plastics etc. are fixed with the film of discoid liquid crystal or nematic liquid crystal, are formed with the film of above-mentioned liquid crystal layer etc. on film base materials.On film base material, form the situation of liquid crystal layer,, preferably use cellulose-based resin moldings such as Triafol T as film base material.

As the plastics of form dielectric grid film, for example can enumerate: 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 handling in suitable modes such as single shaft or twin shafts.Need to prove that in order to control optical characteristics such as wide bandization, polarizer can be used in combination more than 2.

In laminated optical component, contain polarizer and when being applied to liquid crystal indicator, can carry out optical compensation effectively as the laminated optical component of the optical layers beyond the polarization plates, therefore, the preferred use.The phase difference value of polarizer (reaching thickness direction in the face) selects best phase difference value to get final product according to the liquid crystal cells of using.

Laminated optical component can make up polarization plates and by in the above-mentioned various optical layers according to application target select more than 1 layer or 2 layers, make the duplexer more than 2 layers or 3 layers.At this moment, the various optical layers that form laminated optical component use tackifier or bonding agent to carry out integration with polarization plates, as long as for this reason and the tackifier or the bonding agent of use can form adhesive layer or adhesive phase well, just are not particularly limited.Consider from the simplicity of gluing operation or the viewpoint that prevents optical skew, preferably use bonding agent (being also referred to as the pressure-sensing glue stick).Bonding agent can use with the bonding agent as base polymer such as acrylic acid series polymeric compounds or silicone-based polymkeric substance, polyester, polyurethane, polyethers.Wherein, preferably select to use as acrylic adhesive optical transparence excellence, keep suitable wetting quality or cohesiveness, with the tackiness of base material also excellent and have weatherability or thermotolerance etc., heat or the condition of humidification under do not arch upward or the bonding agent of the problem of peeling off such as peel off.In acrylic adhesive, cooperate and to have (methyl) acrylic acid Arrcostab that carbon numbers such as methyl or ethyl or butyl are the alkyl below 20 and to contain functional group's acrylic monomer by formations such as (methyl) acrylic acid or (methyl) Hydroxyethyl Acrylate, so that its glass transition temperature is preferably below 25 ℃, more preferably below 0 ℃, the weight-average molecular weight of Xing Chenging is that the acrylic acid series copolymer more than 100,000 is useful as base polymer thus.

Can utilize following mode on polarization plates, to form adhesive layer, for example: make adhesive compound be dissolved or dispersed in organic solvents such as toluene or ethyl acetate and prepare the solution of 10～40 weight %, it is applied directly to mode on the polarization plates; On diaphragm, form adhesive phase in advance, it is transferred to mode on the polarization plates etc.The thickness of adhesive phase is determined according to its adhesive power etc., is suitably the scope about 1～50 μ m.

In addition, can be as required in adhesive phase, cooperate the filling agent, pigment or the colorant that constitute 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 of use is for arbitrarily, and can use is various liquid crystal cells formation liquid crystal indicators such as the driving liquid crystal cells of the simple matrix of representative with film transistor type as the liquid crystal cells of the active matrix drive-type of representative, with super-twist nematic for example.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 the example, the % of expression content or consumption and part are weight standard unless otherwise specified.In addition, the cationically polymerizable compound that uses 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, the 4-epoxycyclohexane carboxylate [in above-mentioned formula (2), R ⁵=R ⁶The compound of=H, n=0]

(a2) CELLOXIDE 2081 (Daicel chemical company system alicyclic epoxy resin) [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 system alicyclic epoxy resin) [in above-mentioned formula (3), R ⁷=R ⁸=R ⁹=H, Y ³=Y ⁴=(CH ₂) ₅, p=q=1 compound]

(a4) 1, and the 4-butanediol diglycidyl ether [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 of formula (13) expression

(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, show greatly at wavelength 382nm absorb]

(D) photosensitizer additive (in table, being abbreviated as " sensitization auxiliary agent ")

(d1) 1, and 4-diethoxy naphthalene [in above-mentioned formula (I), R ¹=R ²The compound of=ethyl]

(d2) 1-naphthols

[reference example] (making) with polyethylene terephthalate film of antiglare layer

Prepare will following each composition to be dissolved in the ultra-violet solidified resin composition that can obtain 1.53 refractive index after ethyl acetate, the curing 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; the solid constituent of this ultra-violet solidified resin composition is 100 parts relatively; add 2 parts on 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) are made coating liquid.

Should apply liquid and be coated on the biaxial stretch-formed polyethylene terephthalate film (thickness 38 μ m), form the ultra-violet solidified resin composition layer, in being set at 80 ℃ dryer, make its dry 3 minutes.Count 300mJ/cm from the ultra-violet solidified resin composition layer side of dried film with h ray conversion light quantity ²Mode shine from intensity 20mW/cm ²The light of high-pressure mercury-vapor lamp, the ultra-violet solidified resin composition layer is solidified, obtain by the surface have concavo-convex antiglare layer (cured resin) and biaxial stretch-formed polyethylene terephthalate film the duplexer formation, turbidity value is 10% antiglare film.Need to prove that turbidity value uses 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

After mixing each composition with the cooperation ratio shown in the table 1 (unit is part), carry out deaeration, make photo-curable tackifier liquid.Need to prove that photo-induced cationic polymerization initiating agent (b1) cooperates with the form of 50% polypropylene carbonate ester solution, shows with its solid constituent scale in table 1.

[table 1]

(2) making of polarization plates

Corona discharge Treatment is implemented on surface to the three cellulose acetate membrane [trade name " Off ジ タ Star Network ", Fuji Photo Film Co., Ltd.'s system] of the thickness 80 μ m that contain ultraviolet light absorber, on this Corona discharge Treatment face, use rod to be coated with machine and apply the tackifier liquid of making above separately in the mode that the thickness after solidifying is about 3 μ m.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, is coated with machine in the mode that is about 3 μ m with the thickness after solidifying on its Corona discharge Treatment face with rod and applies and top identical tackifier liquid.The one side of making on its adhesive layer is fitted 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, using to add has the ultraviolet lamp (lamp uses U.S. spoke deep UV system house system " D light valve (バ Le Block) ") of being with conveyor to be 750mJ/cm with the accumulative total light quantity ²The mode irradiation ultraviolet radiation, make adhesive solidification.The two sides that is produced on polaroid thus 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, be abbreviated as " quadrature a " respectively and reach " quadrature b ") of separately quadrature transmissivity, degree of polarization, quadrature form and aspect.In mensuration, be fixed with equipment in the ultraviolet-visible pectrophotometer " UV-2450 " of use Shimadzu Scisakusho Ltd system as " membrane support of band 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, utilize the subsidiary software " UV-Probe " of this spectrophotometer to calculate a value and the b value of quadrature transmissivity, degree of polarization and quadrature form and aspect among wavelength 410nm, 550nm and the 650nm.The variable (amount of photosensitizer and photosensitizer additive) that the result is formed with the tackifier in the table 1 is shown in table 2.

The durability evaluation of the polarization plates under (4) damp and hot

The polarization plates that above-mentioned (2) are made is cut into the size of 30mm * 30mm, carries out placing under the hygrothermal environment of 60 ℃ of temperature, relative humidity 90% 240 hours damp heat test, a value of the degree of polarization of the polarization plates behind the determination test, quadrature form and aspect and b value.With measuring with above-mentioned (3) same method.The result is shown in table 2 simultaneously.In the table 2, " test before " hurdle for for carry out before the damp heat test, i.e. the value of polarization plates gained after the making shown in above-mentioned (3), " test back " hurdle is for for carrying out the value of the polarization plates gained behind the damp heat test.

[table 2]

As shown in Table 2, for be combined with anthracene in large quantities in tackifier is the polarization plates that the comparative example 1～3,6 and 11 of photosensitizer (c1) obtains, quadrature transmissivity height under the wavelength 410nm, leak blue light, and the absolute value of a value of quadrature form and aspect and b value is all high, from neutral grey to blue deviation in driction.In addition, great changes will take place by damp heat test quadrature form and aspect.On the other hand, for do not cooperate anthracene in tackifier is the polarization plates that the comparative example 4,8,9 and 13 of photosensitizer (c1) obtains, though after making, demonstrate good degree of polarization, there is not the light of blue light to leak yet, can obtain the form and aspect of neutral ash, but humidity resistance is poor, degree of polarization is less than 99% behind damp heat test, in addition, the quadrature form and aspect also depart from from neutral ash.

Relative therewith, can confirm, for having used a small amount of cooperation anthracene is 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 that a value and b value approach 0 in high degree of polarization and the quadrature form and aspect, and these values are almost constant before and after damp heat test, have good humidity resistance.

Claims (10)

1. A polarizing plate, wherein, have: a polarizing plate composed of a polyvinyl alcohol-based resin film in which a dichroic dye is adsorbed and oriented; and A protective film comprising a transparent resin bonded to at least one side of the polarizer through an adhesive layer, Wherein, the adhesive layer is formed by a photocurable adhesive composition, and the photocurable adhesive composition comprises: (A) 100 parts by weight of cationic polymerizable compound; (B) 1 to 10 parts by weight of a photocationic polymerization initiator; (C) 0.1 to 2 parts by weight of a photosensitizer that exhibits maximum absorption for light with a wavelength greater than 380 nm; and (D) 0.1 to 10 parts by weight of a naphthalene-based photosensitizer represented by the following formula (I),

In the formula, R ¹ and R ² each independently represent an alkyl group having 1 to 6 carbon atoms. 2. The polarizing plate according to claim 1, wherein, The cationically polymerizable compound (A) is an epoxy resin not containing an aromatic ring. 3. The polarizing plate according to claim 1, wherein, The photosensitizer (C) is an anthracene compound represented by the following formula (IV),

In the formula, R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 6 carbons or an alkoxyalkyl group having 2 to 12 carbons, and R ⁷ represents a hydrogen atom or an alkyl group having 1 to 6 carbons. 4. The polarizing plate according to claim 1, wherein, In the said photocurable adhesive composition, 0.1-0.5 weight part of said photosensitizers (C) are contained with respect to 100 weight part of said cationically polymerizable compounds (A). 5. The polarizing plate according to claim 1, wherein, The protective film bonded to at least one surface of the polarizing plate contains cellulose acetate resin. 6. The polarizing plate according to claim 1, wherein, The protective film bonded to at least one surface of the polarizer contains a transparent resin selected from amorphous polyolefin resins, polyester resins, acrylic resins, polycarbonate resins, and chain polyolefin resins. 7. The polarizing plate according to claim 1, wherein, have: A protective film comprising cellulose acetate-based resin bonded on one side of the polarizer through the adhesive layer; and A transparent resin selected from amorphous polyolefin resins, polyester resins, acrylic resins, polycarbonate resins, and chain polyolefin resins is bonded to the other side of the polarizer through the adhesive layer. protective film. 8. The polarizing plate according to claim 1, wherein, Both the a value and the b value of the orthogonal hue are in the range of -0.5 to +0.5. 9. A laminated optical member comprising a laminate of the polarizing plate according to claim 1 and other optical layers. 10. The laminated optical member according to claim 9, wherein, The optical layer contains a phase difference plate.