CN101813798B

CN101813798B - Compound polarization plate and an IPS mode Liquid crystal display device

Info

Publication number: CN101813798B
Application number: CN 201010116995
Authority: CN
Inventors: 松本寿和; 猪口雄平; 申基渊
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2009-02-23
Filing date: 2010-02-21
Publication date: 2013-08-28
Anticipated expiration: 2030-02-21
Also published as: CN101813798A

Abstract

This invention provides a polarization plate.

Description

Composite polarizing plate and the IPS mode LCD that uses it

Technical field

The present invention relates at polarizing coating a face applying transparent protective film, at the composite polarizing plate of another face applying phase retardation film and the IPS mode LCD that uses it.

Background technology

Liquid crystal indicator has little power consumption, in characteristics such as low voltage operating, light weight, slim bodies, be used to various demonstrations with in the devices.Liquid crystal indicator comprises multiple materials such as liquid crystal cells, polarizing coating, phase retardation film, light-collecting piece, diffusion barrier, light guide plate, light-reflecting sheet.Therefore, piece number by reduce constituting film or make film or the thickness attenuation of sheet, with boost productivity, the improvement of lightweight, lightness etc. is in positive the carrying out.

And then requiring liquid crystal indicator is the goods that can stand harsh durable condition.For example, for the liquid crystal indicator that Vehicular navigation system is used, be placed in the car, sometimes temperature, humidity can become very high, in addition, display of using for display, TV, the computer of mobile phone, portable terminal machine etc. etc., according to they environment for use, the place is set, sometimes also can there be the situation in the violent condition of the variation that is exposed to temperature and humidity, therefore requires also to bear the product properties of under rigor condition like this, using.

Polarization plates is generally on the two sides of polarizing coating or single face is laminated with the structure of transparent diaphragm, and described polarizing coating contains the polyvinyl alcohol resin film that the absorption orientation has the dichromatism pigment.

Polarizing coating can be made by the following method: to the polyvinyl alcohol resin film carry out that vertical single ax stretches and dyeing based on the dichromatism pigment after, carry out boric acid again and handle and cause cross-linking reaction, then wash, drying.As the dichromatism pigment, can use iodine or dichromatism organic dyestuff.At two sides or the single face stacked guard film of the polarizing coating that obtains like this, make polarizing coating, just can be assembled in the liquid crystal indicator and use.For diaphragm, use with the cellulose acetate resin film of cellulose triacetate as representative more, its thickness is generally about 30～120 μ m.In addition, stacked for diaphragm, the tackifier that use the aqueous solution by polyvinyl alcohol resin to constitute more.

By the polarization plates that such parts constitute, under the long-time situation about using, polarization property decline sometimes or diaphragm and polarizing coating become and are easy to peel off under wet heat condition.

Therefore, attempt utilizing acetate fiber prime system resin in addition to constitute at least one side's diaphragm.For example, put down in writing following technology in JPH08-43812-A: be laminated with in the polarizing coating of diaphragm on the two sides of polarizing coating, the thermoplastic norbornene that utilizes the function with phase retardation film is at least one side that resin constitutes diaphragm.In addition, in JPH09-325216-A, put down in writing following technology: utilize the film of birefringence to constitute at least one side in the protective seam of polarizing coating.

On the other hand, in the phenylethylene resin series film, owing to compare with the polarizability of the main chain of phenylethylene resin series, the polarizability of side chain big (being polarized to negative sometimes) is being studied with this as the big negative phase retardation film of the refractive index of thickness direction.But, in the phenylethylene resin series film, also there is the problem of thermotolerance, physical strength and drug resistance, do not reach practicability as yet.

Here, the negative phase retardation film that the refractive index of so-called thickness direction is big refers to the refractive index of the largest refractive index direction in the face (slow axis direction) is made as n _x, the refractive index with its orthogonal directions (leading phase shaft direction) in the face is made as n _y, the refractive index of thickness direction is made as n _zThe time, exist

Relation and (n _x-n _z)/(n _x-n _y) defined N _zCoefficient is about the film of 0 (zero).

Thermotolerance for phenylethylene resin series, known by make its with form glass transition temperature (below, sometimes slightly be called Tg) monomer of high resin, the method improved of norborene, maleic anhydride copolymerization for example, but physical strength, drug resistance are insufficient.

Also proposed a plurality of by making styrene and other monomer copolymerization, the technology of folded other resin beds on styrene mesentery upper strata.For example, in JP2002-517583-A, put down in writing, to be the technology that random copolymers in essence that the aromatic vinyl monomer of typical example and alpha-olefin form is made film with styrene, also have the enlightenment of the sandwich construction of making this film and other polymeric layer.In addition, in JP2003-50316-A, JP2003-207640-A, having put down in writing with non-cyclic olefin monomer and cyclic olefin monomers and with styrene is that the aromatic vinyl monomer of typical example carries out copolymerization and forms terpolymer, multipolymer is made the technology of phase retardation film.And then, in JP2003-90912-A, put down in writing the alignment films that will contain the alignment films of norbornene resin and contain the styrene-maleic anhydride copolymer resin by adhesive layer and carried out stackedly, make the technology of phase retardation film; In JP2004-167823-A, put down in writing the technology that is laminated with the polystyrene sheet material at the multilayer film of polyolefin.In addition, in JP2006-192637-A, also put down in writing following technology: do not containing the stacked second layer that contains the acrylic resin composition that is combined with rubber particles on the ground floor of phenylethylene resin series film across adhesive layer, making phase retardation film.

In addition, for for the IPS pattern of a kind of drive pattern of liquid crystal indicator, liquid crystal molecule and real estate almost abreast and almost same direction ground be orientated, therefore compare the angle of visibility excellent with the liquid crystal indicator of other drive patterns.But, even such with the IPS pattern be representative carrying out in the various liquid crystal indicators of angle of visibility characteristic improvement, still can produce the angle of visibility interdependence.

For the angle of visibility interdependence to the IPS mode LCD compensates, various technical schemes have been proposed.As one of them, the method for the angle of visibility by polarizer compensating polarizing plate is effective.For example, in JPH02-160204-A, the ratio of the length of delay of the length of delay when having put down in writing from vertical direction incident with from the direction incident of normal slope 40 degree the time is in the phase retardation film in certain scope, for example, and the phase retardation film that is orientated at thickness direction.In addition, in JPH07-230007-A, put down in writing to make through the thermoplastic resin film of uniaxial tension by the form with regulation and produced thermal shrinkage and the controlled phase retardation film of angle interdependence of length of delay, for example, the also phase retardation film that is orientated at thickness direction.By with such polarizer that is orientated at thickness direction, between the polarization plates and liquid crystal cell substrate of either party among 2 pieces of polarization plates that dispose so that the axis of homology of the polarization plates of the adjoining mode parallel with the slow axis of polarizer is configured in the holding liquid crystal unit, execute effectively for the compensation angle of visibility.

In addition, at T.Ishinabe etal., ' Novel Wide Viewing Angle Polarizer withHigh Achromaticity ', SID 00DIGEST, p.1094-1097 in, put down in writing the following fact, i.e. the N of preamble definition _zCoefficient is that polarizer 0.25 and 0.8, that carry out the thickness orientation has better effect.And then, in JPH11-133408-A, put down in writing following technology, for the IPS pattern, between liquid crystal cell substrate and polarization plates, be configured to positive uniaxiality mode and have the phase retardation film (layer of compensation) of optical axis in the direction vertical with real estate, namely be configured in the phase retardation film that thickness direction carries out uniaxial orientation.

But the production rate variance that these carry out the polarizer of thickness orientation needs accurate processing, so the goods costliness.

And then, compensation at the angle of visibility interdependence of IPS mode LCD, the following technology of record in JPH10-54982-A: by the polarizer (optical compensating gage) with negative uniaxiality is installed, improve the angle of visibility interdependence between liquid crystal cell substrate and at least one side's polarization plates.In this communique, show and to have the optical axis of the polarizer of negative uniaxiality, be i.e. leading phase shaft, the example that is configured in the mode parallel with the major axis of liquid crystal molecule.Therefore, hope will be supplied with the form of the one-piece type polarization plates of optical compensation films for the film-stack of above-mentioned optical compensation in polarization plates.Yet, in the mechanism of the optical compensation that proposes up to now, can't fully solve problems such as colour vision displacement (colour shift), tone reversal, expect further optimization.

In addition, in the situation with the stacked use of phase retardation film more than 2 pieces, be uniformly even the angle of orientation of each phase retardation film monomer distributes, when it is stacked, also can produce color spot in certain location sometimes, thereby existing problems.

WO2008/010562A1 is and the immediate prior art of the application.

Summary of the invention

The objective of the invention is to, the composite polarizing plate of the good angle of visibility characteristic of demonstration when possessing the polarizer that is easy to make and being applied to liquid crystal indicator is provided.Another object of the present invention is to, though stacked 2 pieces of phase retardation films are provided, be difficult to produce the composite polarizing plate of the color spot of locality.Further object of the present invention is, the liquid crystal indicator that possesses IPS mode liquid crystal unit, angle of visibility characteristic good is provided.

According to the present invention; can provide following composite polarizing plate: stacked transparent protective film on the face of first adhesive layer at polarizing coating; first phase retardation film that contains the ethylene series resin across second adhesive layer in the another side upper strata stacked package of polarizing coating; and then; across adhesive phase in the outside of above-mentioned first phase retardation film stacked second phase retardation film; described second phase retardation film has following 3-tier architecture, and described 3-tier architecture is the structure that is formed with the cortex that is formed by (methyl) acrylic resin composition that contains rubber particles on the two sides of the sandwich layer that comprises phenylethylene resin series.

And then preferred: in first phase retardation film, length of delay is 30～150nm in the face, and has following refractive index anisotropy,, the refractive index of leading phase shaft direction and thickness direction in slow axis direction, the face in the face is made as n respectively that is _x, n _yAnd n _zThe time, formula: (n _xOne n _z)/(n _x-n _y) defined N _zCoefficient satisfies greater than 1 less than 2,, satisfies following formula (1) that is,

1＜(n _x-n _z)/(n _x-n _y)＜2 (1)

In second phase retardation film, length of delay is 20～120nm in the face, and has following refractive index anisotropy, that is, and and N as defined above _zCoefficient satisfies greater than-2 less than-0.5,, satisfies following formula (2) that is.

-2＜(n _x-n _z)/(n _x-n _y)＜-0.5 (2)

Preferred so that the variation of the formed angle of the angle of orientation of first phase retardation film and second phase retardation film is that the mode below 0.4 ° is laminated with first phase retardation film and second phase retardation film in the interval of 10cm.

Constitute the ethylene series resin of first phase retardation film, be preferably the annular ethylene series resin that mainly contains the structural unit of being derived by ester ring type alkene.

In second phase retardation film, the glass transition temperature that is preferably formed the phenylethylene resin series of sandwich layer is more than 120 ℃, and the glass transition temperature that is preferably formed (methyl) acrylic resin composition of cortex is below 120 ℃.

Utilization contains the water system tackifier of the aqueous solution of water miscible polyvinyl alcohol resin can be gluing with first phase retardation film and the polarizing coating that contain the ethylene series resin, and this water system tackifier preferably contains water miscible epoxy compound.In addition, first phase retardation film and polarizing coating can be that the tackifier that the epoxy based resin composition of resin forms carries out gluing by containing epoxy that irradiation by utilizing active energy ray or heating take place to solidify also.When the epoxy based resin composition was made tackifier, this epoxy was that resin preferably has the material that is bonded to the epoxy radicals of ester ring type ring more than 1 in molecule.

And then, according to the present invention, can be provided at least one face of IPS mode liquid crystal unit, dispose the ISP mode LCD that above-mentioned arbitrary polarization plates forms.In addition; following IPS mode LCD can also be provided; namely; a face in IPS mode liquid crystal unit disposes above-mentioned arbitrary polarization plates; at another side; dispose the polarization plates that has transparent protective film in liquid crystal cell side, described transparent protective film is that length of delay is that 10nm is following, the absolute value of thickness direction retardation value is the following transparent protective film of 15nm in the face.

Length of delay Re is that the thickness of film multiply by the refringence in the face and the value that obtains in the face of film, defines by following formula (3).In addition, the thickness direction retardation value Rth of film is, the thickness of film multiply by mean refractive index in the face and thickness direction refractive index difference and the value that obtains defines by following formula (4).And then, as described in previous formula (1) and (2), N _zCoefficient defines by following formula (5).

Length of delay Re=(n in the face _x-n _y) * d (3)

Thickness direction retardation value Rth={ (n _x+ n _y)/2-n _z) * d (4)

N _zCoefficient=(n _x-n _z)/(n _x-n _y) (5)

(in the formula, n _x, n _yAnd n _zBe the film three axial refractive indexes of previous definition, d is the thickness of film).

Re, Rth and N _zCoefficient can utilize commercially available various phasometers to measure.

For these values, as usual with near the value measured of wavelength the central authorities of visible light as typical value, said length of delay and N in this instructions _zCoefficient is the value of measuring at wavelength 590nm.

Description of drawings

Fig. 1 is the diagrammatic cross-section of an example of the layer formation of expression composite polarizing plate of the present invention.

The distribution plan of the contrast of LCD degree ratio that Fig. 2 makes for the composite polarizing plate that uses embodiment 1.

The distribution plan of the contrast of LCD degree ratio that Fig. 3 makes for the composite polarizing plate that uses embodiment 2.

The distribution plan of the contrast of LCD degree ratio that Fig. 4 makes for the composite polarizing plate that uses embodiment 3.

The distribution plan of the contrast of LCD degree ratio that Fig. 5 makes for the composite polarizing plate that uses embodiment 4.

The distribution plan of the contrast of LCD degree ratio that Fig. 6 makes for the composite polarizing plate that uses comparative example 1.

The distribution plan of the contrast of LCD degree ratio that Fig. 7 makes for the composite polarizing plate that uses embodiment 5.

Fig. 8 is at embodiment 5 employed 2 kinds of composite polarizing plates, with constitute each composite polarizing plate 2 pieces of phase retardation films the formed angle of the angle of orientation Width chart and curve map.

Symbol description

100 composite polarizing plates

101 polarizing coatings

102 transparent protective films

103 first phase retardation films

104 adhesive phases

105 second phase retardation films

106 first tackifier (then drug) layer

107 second adhesive layers

108 adhesive phases (adhesion drug)

109 separators

31 sandwich layers

32 cortexes

Embodiment

[composite polarizing plate]

Fig. 1 is the diagrammatic cross-section of an example of the layer formation of expression composite polarizing plate of the present invention.Composite polarizing plate 100 shown in Figure 1 possesses: according to transparent protective film 102, polarizing coating 101, contain the polarization plates that first phase retardation film, 103 such orders of ethylene series resin are laminated; On first phase retardation film 103 of this polarization plates across adhesive phase 104 and the second stacked phase retardation film 105.On a face of polarizing coating 101, be laminated with transparent protective film 102 across first adhesive layer 106, be laminated with first phase retardation film 103 that contains the ethylene series resin across second adhesive layer 107 at the another side of polarizing coating 101.

Second phase retardation film 105 has following 3-tier architecture, namely is formed with the cortex 32 that is made of (methyl) acrylic resin composition that contains rubber particles, 32 3-tier architecture on the two sides of the sandwich layer 31 that contains phenylethylene resin series.Second phase retardation film 105, with the face of face opposition side that fits in first phase retardation film 103 on; be typically provided with the adhesive phase 108 for miscellaneous parts such as applying liquid crystal cells; in its outside; before fitting in miscellaneous part, all be provided with the separator 109 that the surface of adhesive phase 108 is glued in advance protection.In addition, in Fig. 1, for the ease of understanding, the layer of a part separated represent, but each in fact adjacent layer fits tightly.Below, each parts that constitutes composite polarizing plate are described in detail.

[polarizing coating]

Employed polarizing coating 101 among the present invention is generally the polarizing coating of making through following operation, and described operation is: utilize known method the polyvinyl alcohol resin film to be carried out the operation of uniaxial tension; Utilize the dichromatism pigment polyvinyl alcohol resin film to be dyeed, makes the operation of dichromatism pigment absorption; The operation of utilizing boric acid aqueous solution that the polyvinyl alcohol resin film that is adsorbed with the dichromatism pigment is handled; And the operation of after boric acid aqueous solution is handled, washing.

As polyvinyl alcohol resin, can use with polyvinyl acetate be resin carry out saponification and resin.Be resin as polyvinyl acetate, except the polyvinyl acetate of the homopolymer of vinyl acetate, can enumerate can with other monomers of vinyl acetate copolymerization and the multipolymer of vinyl acetate etc.As can with other monomers of vinyl acetate base copolymerization, for example, can enumerate unsaturated carboxylic acid class, olefines, vinyl ethers, unsaturated sulfonic acid class and have acrylic amide of ammonium etc.

The saponification degree of polyvinyl alcohol resin is generally about 85～100mo1%, more than the preferred 98mol%.Also this polyvinyl alcohol resin can be carried out modification, for example, also can use and utilize aldehydes to carry out modified polyethylene alcohol formal, polyvinyl acetal etc.In addition, the degree of polymerization of polyvinyl alcohol resin is generally about 1000～10000, and preferred about 1500～5000.

With such polyvinyl alcohol resin film processed and film, can be used as the reel film (Japanese: former anti-Off イ Le system) use of polarizing coating.The method of film polyvinyl alcohol resin processed has no particular limits, and can use known method film processed.The thickness of polyethenol series reel film has no particular limits, and for example, is about 10 μ m～150 μ m.

The uniaxial tension of polyvinyl alcohol resin film can carry out before the dyeing of dichromatism pigment, also can carry out in dyeing, or carry out after dyeing.When carrying out uniaxial tension after dyeing, this uniaxial tension also can carry out before boric acid is handled or among the boric acid processing.In addition, can in these a plurality of stages, carry out uniaxial tension.

For uniaxial tension, can between the different roller of rotating speed, stretch with single shaft, also can use hot-rolling to stretch with single shaft.In addition, uniaxial tension can be the dry type stretching that stretches in atmosphere, also can be to use the water equal solvent, and the wet type that stretches under the state that makes polyvinyl alcohol resin film swelling stretches.Stretching ratio is generally about 3～8 times.

As the method for utilizing the dichromatism pigment that the polyvinyl alcohol resin film is dyeed, for example can adopt the method for polyvinyl alcohol resin film immersion in the aqueous solution that contains the dichromatism pigment.As the dichromatism pigment, specifically, can use iodine, dichroic dye.In addition, preferably before dyeing is handled, the polyvinyl alcohol resin film is implemented water retting in advance handle.

When using iodine as the dichromatism pigment, adopt the method that the polyvinyl alcohol resin film immersion is dyeed in containing iodine and potassium iodide aqueous solution usually.Usually the content of the iodine in this aqueous solution is about 0.01～1 weight portion with respect to water 100 weight portions.In addition, the content of potassium iodide is about 0.5～20 weight portion with respect to water 100 weight portions usually.The temperature of the aqueous solution of using in the dyeing is generally about 20～40 ℃.

In addition, the dip time in this aqueous solution (dyeing time) was generally about 20～1800 seconds.

On the other hand, when using dichroic dye as the dichromatism pigment, adopt the method for dipping polyvinyl alcohol resin film in containing the aqueous dye solutions of water-soluble dichroic dye usually.The content of the dichroic dye in this aqueous dye solutions is 1 * 10 with respect to water 100 weight portions usually ^-4About～10 weight portions, preferred 1 * 10 ^-3About～1 weight portion.This aqueous solution can also contain inorganic salts such as sodium sulphate as dyeing assistant.Normally 20～80 ℃ of the temperature of the dichroic dye aqueous solution of using in the dyeing, in addition, the dip time in aqueous dye solutions (dyeing time) is normally about 10～1800 seconds.

Boric acid after the dyeing of dichromatism pigment is handled, usually by dyed polyvinyl alcohol resin film immersion is carried out in the aqueous solution that contains boric acid.

Usually contain boric acid content in the aqueous solution of boric acid with respect to water 100 weight portions normally about 2～15 weight portions, about preferred 5～12 weight portions.When using iodine as the dichromatism pigment in the above-mentioned dyeing treatment process, the aqueous solution of using in this boric acid treatment process that contains boric acid preferably contains potassium iodide.At this moment, the amount that contains the potassium iodide in the aqueous solution of boric acid is generally about 0.1～15 weight portion with respect to water 100 weight portions usually, about preferred 5～12 weight portions.Dip time in containing the aqueous solution of boric acid is normally about 60～1200 seconds, and preferred about 150～600 seconds, and then preferred about 200～400 seconds.Contain the temperature of aqueous solution of boric acid normally more than 50 ℃, preferred 50～85 ℃, more preferably 60～80 ℃.

Polyvinyl alcohol resin film after boric acid is handled is washed processing usually.Washing is handled, for example, and by the polyvinyl alcohol resin film immersion after boric acid is handled is carried out in water.The temperature of the water during washing is handled is generally about 5～40 ℃.In addition, dip time was generally about 1～120 second.

The dry processing implemented in the washing back, can obtain polarizing coating.Dry processing can use air drier, far infra-red heater to wait to carry out.Baking temperature is normally about 30～100 ℃, preferred 50～80 ℃.Dry normally 60～600 seconds time of handling, preferred 120～600 seconds.

Handle by drying, the moisture rate of polarizing coating can be reduced to practical level.This moisture rate is generally 5～20 weight %, preferred 8～15 weight %.If moisture rate is less than 5 weight %, then the pliability of polarizing coating is lost, and polarizing coating damages in its dry back sometimes, or fracture.In addition, if moisture rate is greater than 20 weight %, the thermal stability variation of polarizing coating sometimes then.

Operate the thickness that the dichromatism pigment is adsorbed the polarizing coating that is orientated and obtains like this, can make usually about 5～40 μ m.

[first phase retardation film that contains the ethylene series resin]

In composite polarizing plate of the present invention, first phase retardation film 103 that disposes in liquid crystal cell side is the film that contains the ethylene series resin.So-called ethylene series resin refers to, contain chain aliphatics alkene such as ethene and propylene or norborene and the resin of the structural unit of being derived by ester ring type alkene such as substituent (below, these are generically and collectively referred to as the norborneol alkene monomer).The multipolymer that the ethylene series resin also can be to use the monomer more than 2 kinds to form.

Wherein, as the ethylene series resin, preferred use mainly contains the annular ethylene series resin of the resin of the structural unit of being derived by ester ring type alkene.As the typical example of the ester ring type alkene that constitutes annular ethylene series resin, can enumerate norborneol alkene monomer etc.So-called norborene refers to that 1 carbon-carbon bond of norcamphane becomes the compound of two keys, according to the IUPAC nomenclature, and the compound of called after dicyclo [2,2,1] seven-2-alkene (bicyclo[2,2,1] hept-2-ene).Example as the substituent of norborene, the position of double bond of norborene is located at 1, the 2-position, can enumerate 3-substituent, 4-substituent, 4,5-is di-substituted etc., and then, also with bicyclopentadiene, dimethano octahydro naphthalene (Dimethanooctahydronaphthalene) etc. as the monomer that constitutes annular ethylene series resin.

Annular ethylene series resin can have the norcamphane ring in its structural unit, also can not have.As forming the norborneol alkene monomer that does not have the annular ethylene series resin of norcamphane ring in the structural unit, for example can enumerate the compound that becomes 5 yuan of rings by open loop, representational have norborene, bicyclopentadiene, 1-or 4-methyl norborene, a 4-phenyl norborene etc.When annular ethylene series resin was multipolymer, the ordered state of its molecule was not particularly limited, and can be random copolymers, also can be segmented copolymer, can also be graft copolymer.

Example more specifically as annular ethylene series resin, for example can enumerate the ring opening copolymer thing of ring-opening polymerization polymer, norborneol alkene monomer and other monomers of norborneol alkene monomer, with addition such as they and maleic acid, cyclopentadiene and the polymer modification thing and with the addition copolymer of addition polymer, norborneol alkene monomer and other monomers of the polymkeric substance of their hydrogenation or multipolymer, norborneol alkene monomer etc.Other monomers when making multipolymer can be enumerated alpha-olefines, cyclenes class, non-conjugated diene class etc.In addition, annular ethylene series resin also can be to use the multipolymer of norborneol alkene monomer and other ester ring type alkene more than a kind or 2 kinds.

In above-mentioned concrete example, as annular ethylene series resin, the preferred resin that the ring-opening polymerization polymer that has utilized the norborneol alkene monomer is carried out hydrogenation that uses.Such annular ethylene series resin, except implementing stretch processing and make the phase retardation film it, beyond stretching, the shrinkage factor shrinkability film that has a regulation by applying is implemented heat shrink and is handled, and can make the homogeneity height, have the phase retardation film of bigger length of delay.

As the commercially available product of the annular ethylene series resin of using such norborneol alkene monomer, can enumerate " ZEONEX " that Japanese ZEON (strain) sells and " ZEONOR ", " ARTON " that JSR (strain) sells etc. with trade name.The film of these annular ethylene series resin and stretched film also can buy commercially available product, for example, can enumerate " the ZEONOR film " that Japanese ZEON (strain) sells with trade name, " エスシ one Na " that " the ARTON film " that JSR (strain) sells, ponding chemical industry (strain) are sold etc.

In addition, in the present invention in first phase retardation film of Shi Yonging, the film that can use the film that constituted by the hybrid resin that contains ethylene series resin more than 2 kinds, be constituted by the hybrid resin of ethylene series resin and other thermoplastic resins.For example, as the hybrid resin that contains 2 kinds of ethylene series resins, can enumerate the potpourri of above-mentioned annular ethylene series resin and chain aliphatic olefin hydrocarbon system resin.When using the hybrid resin of ethylene series resin and other thermoplastic resins, other thermoplastic resins can carry out suitable selection according to purpose.As concrete example, can enumerate the polyvinyl chloride resin, cellulose-based resin, polystyrene resin, the acrylonitrile/butadiene/styrene copolymer resins, vinyl cyanide/styrene copolymerized resin, (methyl) acrylic resin, polyvinyl acetate is resin, Vingon is resin, polyamide-based resin, polyacetal is resin, polycarbonate-based resin, the modification polyphenylene ether is resin, polybutylene terephthalate is resin, ethylene glycol terephthalate is resin, polyphenylene sulfide is resin, polysulfones is resin, polyethersulfone is resin, polyetheretherketone is resin, polyarylate is resin, the liquid crystal liquid crystal property resin, polyamidoimide is resin, polyimide is resin, teflon is resin etc.These thermoplastic resins can be distinguished use separately, or use with more than one other resin combination.In addition, above-mentioned thermoplastic resin can carry out re-using after the suitable arbitrarily polymer modification.As the example of polymer modification, can enumerate copolymerization, crosslinked, molecular end modification, give three-dimensional regularity etc.

When using the hybrid resin of ethylene series resin and other thermoplastic resins, the content of other thermoplastic resin usually with respect to resin integral body be about 50 weight % below, about preferred 40 weight % below.Be set in this scope the wavelength dispersion characteristic that the absolute value that can obtain photoelastic constant is little, demonstration is good, and permanance, physical strength and the excellent phase retardation film of the transparency by the content with other thermoplastic resins.

Such ethylene series resin by from the The tape casting of solution, extrusion by melting etc., can film processed be film.During by the hybrid resin film processed more than 2 kinds, this film-forming method is had no particular limits, for example can adopt following method: resinous principle ratio and solvent according to the rules together mixed and obtain homogeneous solution, use this solution by the method for The tape casting molding; Resinous principle ratio is according to the rules carried out melting mixing, utilize the method for extrusion by melting making film etc.

In the above-mentioned film that contains the ethylene series resin, in not damaging purpose scope of the present invention, can contain other compositions such as remaining solvent, stabilizing agent, plastifier, anti aging dope, antistatic agent and ultraviolet light absorber as required.In addition, in order to reduce surface roughness, can also contain levelling agent.

In first phase retardation film of the above-mentioned ethylene series resin molding that uses in containing the present invention, length of delay Re is 30～150nm and has the defined N of above-mentioned formula (5) in the preferred face _zCoefficient greater than 1 less than 2 refractive index anisotropy.

Has the anisotropic ethylene series resin molding of above-mentioned refractive index, can be by known vertical single ax stretching, the horizontal uniaxial tension of stenter, Biaxially stretched, Biaxially stretched etc. obtaining in turn simultaneously, in the mode that obtains desirable length of delay stretching ratio and draw speed are suitably adjusted, the selection that all temps such as preheat temperature that in addition, can be when stretching, draft temperature, heating setpoint temperature, chilling temperature and pattern thereof suit.

Employed stretched annular ethylene series resin film among the present invention, preferably its thickness is in the scope of 20～80 μ m, more preferably in the scope of 40～80 μ m.During the thickness less than 20 μ m of annular ethylene series resin film, the difficult treatment of film has the trend of the length of delay that is difficult to embody regulation in addition, on the other hand, if thickness surpasses 80 μ m, then become the film of poor in processability, the transparency descends in addition, perhaps makes the weight of the polarization plates that obtains become big sometimes.

[transparent protective film]

Stacked transparent protective film 102 on the face of polarizing coating, preferably the material by the excellences such as stability of the transparency, physical strength, thermal stability, covering property of moisture, length of delay constitutes.Material as such formation transparent protective film; have no particular limits, for example can enumerate with methyl methacrylate is that resin is (methyl) acrylic resin of typical example; be the polyolefin-based resins of typical example with the propylene resin; annular ethylene series resin; the polyvinyl chloride resin; cellulose-based resin; phenylethylene resin series; the acronitrile-butadiene-styrene based copolymerized resin; vinyl cyanide polystyrene copolymer resins; polyvinyl acetate is resin; Vingon is resin; polyamide-based resin; polyacetal is resin; polycarbonate-based resin; the modification polyphenylene ether is resin; polybutylene terephthalate is resin; polyethylene terephthalate is resin; polysulfones is resin; polyethersulfone is resin; polyarylate is resin; polyamidoimide is resin; polyimide is resin etc.

These resins can be distinguished use separately or use with the above resin combination of other 1 kinds.In addition, these resins, can carry out re-using after the suitable arbitrarily polymer modification, as this polymer modification, for example can enumerate copolymerization, crosslinked, molecular end modification, three-dimensional regularity control, comprise and follow the not modifications such as mixing of the situation of the reaction between the similar polymers.

Among these, as the material of above-mentioned transparent protective film, preferably to use with methyl methacrylate be resin as (methyl) acrylic resin, the ethylene glycol terephthalate of typical example is resin, propylene resin or cellulose-based resin.

So-called methyl methacrylate is resin, refers to contain the polymkeric substance of the above methyl methacrylate units of 50 weight %.The content of methyl methacrylate units is preferably more than the 70 weight %, can be 100 weight %.Methyl methacrylate units is the polymkeric substance of 100 weight %, be methyl methacrylate is carried out independent polymerization and imperplex.

This methyl methacrylate is resin, usually under the coexistence of radical polymerization initiator and chain-transferring agent, obtains by carrying out polymerization as the monofunctional monomer of major component with methyl methacrylate.In the polymerization, also make a small amount of polyfunctional monomer and its copolymerization sometimes.

As can with the monofunctional monomer of methyl methacrylate copolymer, for example can enumerate the methyl acrylic ester beyond the methyl methacrylates such as Jia Jibingxisuanyizhi, butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, methacrylic acid 2-Octyl Nitrite and 2-hydroxyethyl methacrylate; Esters of acrylic acids such as methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-EHA and acrylic acid 2-hydroxy methacrylate; Hydroxy alkyl acrylate classes such as 2-(hydroxymethyl) methyl acrylate, 2-(1-hydroxyethyl) methyl acrylate, 2-(hydroxymethyl) ethyl acrylate and 2-(hydroxymethyl) acrylic acid butyl; Unsaturated acids such as methacrylic acid and acrylic acid; Halogenated styrenes such as chlorostyrene and bromstyrol class; Substituted phenylethylene such as vinyltoluene and α-Jia Jibenyixi class; Unsaturated nitrile such as vinyl cyanide and methacrylonitrile; Unsaturated acid anhydride such as maleic anhydride and citraconic anhydride class; Unsaturated acid imides such as phenyl maleimide and cyclohexyl maleimide etc.These co-polymerized monomers can be distinguished separately and to use, also can with other more than a kind combination of monomers use.

As can with the polyfunctional monomer of methyl methacrylate copolymer, for example can enumerate two terminal hydroxyls of ethylene glycol such as ethylene glycol bisthioglycolate (methyl) acrylate, diglycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, nine ethylene glycol bisthioglycolates (methyl) acrylate and ten TEG two (methyl) acrylate or its oligomer and the compound that esterification takes place in acrylic or methacrylic acid; The compound of esterification takes place in two terminal hydroxyls of propylene glycol or its oligomer and acrylic or methacrylic acid; The compound of esterification takes place in the hydroxyl of divalent alcohol such as dimethyltrimethylene glycol two (methyl) acrylate, hexanediol two (methyl) acrylate and butylene glycol two (methyl) acrylate and acrylic or methacrylic acid; The sour compound that esterification takes place and get of two terminal hydroxyls of the alkylene oxide addition product of bisphenol-A, bisphenol-A or their halogen substituent and acrylic or methacrylic; The compound that esterification forms takes place and makes glycidyl acrylate or the epoxy radicals generation open loop of glycidyl methacrylate adds the compound of the terminal hydroxyl that is formed in them in the acid of polyvalent alcohol such as trimethylolpropane and pentaerythrite and acrylic or methacrylic; The epoxy ring-opening of glycidyl acrylate or glycidyl methacrylate is added be formed in succinic acid, hexane diacid, terephthalic acid (TPA), phthalic acid, they dibasic acid such as halogen substituent and they alkylene oxide addition product etc. on the compound that forms; Allyl (methyl) acrylate; Divinyl aromatic compounds such as divinylbenzene etc.Wherein, preferably use ethylene glycol dimethacrylate, TEG dimethylacrylate and neopentylglycol dimethacrylate.

Methyl methacrylate is that resin can be the resin that further reacts between can the functional group of copolymerization and be modified.As this reaction, for example can enumerate separating methanol condensation reaction in the macromolecular chain that the hydroxyl of the methyl ester group of methyl acrylate and 2-(hydroxymethyl) methyl acrylate takes place, the interior dehydration condensation of the macromolecular chain that the hydroxyl of acrylic acid carboxyl and 2-(hydroxymethyl) methyl acrylate takes place etc.

Such methyl methacrylate is that resin can easily obtain commercially available product, for example, can enumerate Sumipex (sumitomo chemical company system), ACRYPET (the beautiful positive corporate system of Mitsubishi), Delpet (Asahi Chemical Industry's corporate system), Parapet (Kuraray corporate system), Acryviewa (Japanese catalyst corporate system) etc. according to trade name separately.

So-called ethylene glycol terephthalate is that resin refers to, the above resin that is made of ethylene glycol terephthalate of the 80mol% of repetitive can contain other dicarboxylic acid composition and diol components.As other dicarboxylic acid compositions, for example, can enumerate m-phthalic acid, 4,4 '-dicarboxyl diphenyl, 4,4 '-benzophenonedicarboxylic acid, two (4-carboxyl phenyl) ethane, hexane diacid, decanedioic acid, 1,4-dicarboxyl cyclohexane etc.

As other diol components, can enumerate oxirene addition product, polyglycol, polypropylene glycol, polytetramethylene glycol of propylene glycol, butanediol, neopentyl glycol, diglycol, cyclohexane diol, bisphenol-A etc.

These dicarboxylic acid composition or diol components can be used in combination more than 2 kinds as required.In addition, also can and with P-hydroxybenzoic acid, to hydroxycarboxylic acids such as beta-hydroxy ethoxybenzoic acids.In addition, as other copolymer compositions, also can use dicarboxylic acid composition or the diol component that contains a spot of amido link, amino-formate bond, ehter bond, carbonic acid ester bond etc.

Be the manufacture method of resin as ethylene glycol terephthalate, can adopt following method: make the directly method of polycondensation of terephthalic acid (TPA) and ethylene glycol (and other dicarboxylic acid as required or other glycol), make dialkyl and the ethylene glycol (and the dialkyl of other dicarboxylic acid as required or other glycol) of terephthalic acid (TPA) that ester exchange reaction take place, make the method for its polycondensation then; Make the terephthalic acid (TPA) glycol ester of (with other dicarboxylic acid as required) (with other diol esters as required) that method of polycondensation etc. take place in the presence of catalyzer.And then, can carry out solid phase as required, molecular weight is improved, or low molecular weight compositions is descended.

So-called propylene resin refers to utilize that 80 weight % of repetitive are above be the chain olefinic monomer of propylene monomer, the resin that the use catalyst for polymerization carries out polymerization.Wherein, the homopolymer of preferred propylene.In the homopolymer of propylene, more preferably solvable composition (CXS composition) is polymkeric substance below the 1 weight % in 20 ℃ dimethylbenzene, and further preferred CXS composition is the following polymkeric substance of 0.5 weight %.In addition, also preferred following multipolymer, that is, and with propylene as main body, make can with the comonomer of its copolymerization, with the ratio of 1～20 weight %, the ratio of preferred 3～10 weight % carry out with it and must multipolymer.

When using propylene copolymer, as with propylene can copolymerization comonomer, optimal ethylene, 1-butylene and 1-hexene.Wherein, from the transparency than more excellent viewpoint, preferably make ethene with the ratio copolymerization of 3～10 weight % multipolymer.Be made as more than the 1 weight % by the copolymerization ratio with ethene, can embody the effect that improves the transparency.On the other hand, if its ratio surpasses 20 weight %, then the fusing point of resin descends, and sometimes the required thermotolerance of diaphragm is caused damage.

So-called cellulose-based resin; refer to utilize acetyl group, propiono and/or bytyry to replace part or all cellulose organic ester that forms or the cellulose mixed organic acid ester of the hydrogen atom in the cellulosic hydroxyl that is obtained by cotton linter, wood pulp raw celluloses such as (broad leaf tree paper pulp, conifer paper pulp).For example can enumerate the resin that contains cellulosic acetic acid esters, propionic ester, butyric ester and their mixed ester etc.Wherein, preferred tri acetyl cellulose membrane, diacetyl cellulose film, cellulose acetate propionic ester film, cellulose acetate butyric ester film etc.

Be that resin, ethylene glycol terephthalate are the method that resin, propylene resin, cellulose-based resin wait to make gluing transparent protective film in polarizing coating as utilizing above methyl methacrylate; method that can be suitable according to this Choice of Resin is not particularly limited.For example can adopt following method: will be dissolved in the resin of solvent to metal band processed or cylinder curtain coating, dry desolventizing obtains the solvent cast method of film; With resin be heated to its more than melt temperature, carry out mixingly, from die head, extrude again, cooling, thereby obtain the extrusion by melting etc. of film.

In extrusion by melting, can extrude monofilm, also multilayer film can be extruded simultaneously.

Can be used as the film that diaphragm uses; can easily obtain commercially available product; for the methyl methacrylate resin film; for example according to trade name separately can enumerate Technoloy (sumitomo chemical company system), Acrylite and Acryplen (more than; the beautiful positive corporate system of Mitsubishi), Delaglas (Asahi Chemical Industry's corporate system), Paraglas and Comoglas (more than, Kuraray corporate system), Acryviewa (Japanese catalyst corporate system) etc.

As the ethylene glycol terephthalate resin film, for example, can enumerate Novaclear (Mitsubishi Chemical Ind's system) and Supreme Being people A-PET sheet (Supreme Being people changes into corporate system) etc. by trade name separately.

As the propylene resin film, for example, FILMAXCPP film (FILMAX corporate system), Suntox (SunTox corporate system), Tocello (Tocello corporate system), Japan be can enumerate by trade name separately and Pylen film (Japan's paj is knitted corporate system), Torayfan (eastern beautiful film processing corporate system), Japanese Port リエ one ス (Japanese Port リエ one ス corporate system), pavilion FC (Futamura chemical company system) etc. too spun.

In addition, as cellulose-based resin molding, for example, can enumerate FUJITAC TD (Fuji Photo Film Co., Ltd.'s system), Konicaminolta TAC film KC (Konica Minolta Optical Co., Ltd system) etc. by trade name separately.

Can give anti-dazzle property (turbidity) to employed transparent protective film among the present invention.As the method for giving anti-dazzle property, for example can adopt following method: in material resin, mix the method that inorganic particles or organic fine particles carry out membranization; Utilize multilayer to extrude, utilize to mix fine-grained resin and constitute a side, utilize unmixed fine-grained resin to constitute the opposing party and make the method for two tunics, make the method for trilamellar membrane outside the resin that maybe will be mixed with particle places; The coating fluid that inorganic particles or organic fine particles is mixed in curing property base-material (バイ Application ダ one) resin and forms is coated the one-sided of film with this coating fluid, binder resin is solidified and the method etc. of antiglare layer is set.

Give the inorganic particles of anti-dazzle property as being used for, for example, can enumerate silicon dioxide, cataloid, aluminium oxide, alumina sol, aluminosilicate, alumina silica composite oxides, porcelain earth, talcum, mica, calcium carbonate, calcium phosphate etc.In addition, as organic fine particles, for example can enumerate crosslinked polypropylene acid particles, methyl methacrylate/styrene copolymer resin particle, crosslinked polystyrene particle, cross-linked poly methyl methacrylate particle, silicone resin particle, polyimide particle etc.

Given the turbidity value of the transparent protective film of anti-dazzle property, preferably in 6～45% scope.If the turbidity value of anti-dazzle property diaphragm then can not show sufficient antiglare effect sometimes less than 6%.In addition, if its turbidity value surpasses 45%, the picture of then using the liquid crystal indicator of this film sometimes turns white, and causes the decline of image quality.

Turbidity value can use commercially available turbidimeter according to JISK7136, and for example turbidity transmitance meter HM-150 (color technical institute corporate system in the village) measures.When carrying out the mensuration of turbidity value, in order to prevent the warpage of film, for example, the preferred use utilizes optical transparent adhesives that face is fitted in glass substrate so that anti-dazzle property is given the mensuration sample that face becomes the surface.

On above-mentioned transparent protective film, functional layers such as conductive layer, hard coat, low reflection layer can also be set.When forming above-mentioned antiglare layer, as its coating fluid, also can be selected from the resin combination with these functions.

In addition, for transparent protective film, before fitting with polarizing coating, preferably implement saponification processing, corona treatment, plasma treatment etc.

From viewpoints such as intensity, operability, the thickness of transparent protective film is generally about 1～500 μ m, preferred 10～200 μ m, further preferred 20～100 μ m.So long as the thickness in this scope just can mechanically be protected polarizing coating, hot and humidly down polarizing coating is not shunk and keep stable optical characteristics even be exposed to.

[first adhesive layer and second adhesive layer]

As transparent protective film 102 and first phase retardation film 103 that contains the ethylene series resin are laminated in the method for polarizing coating 101, first and second adhesive layers 106,107 are set respectively make its integrated method thereby can adopt.At this moment, preferred 0.1～35 μ m of the thickness of adhesive layer, more preferably 0.1～15 μ m.As long as in this scope, stacked transparent protective film and contain first phase retardation film of ethylene series resin and polarizing coating between just can not break away from, peel off, can obtain the practical adhesive power that goes up no problem.

Adhesive layer can suitably use suitable adhesive layer according to by the kind of adherent and purpose.

For example, solvent adhesive, emulsion adhesive, pressure-sensitive adhesive, remoistening adhesive, bunching mould assembly tackifier, solventless adhesive, membranaceous tackifier, hot-melt adhesive etc. are arranged.

A preferred adhesives of second adhesive layer that formation is gluing with polarizing coating and first phase retardation film is the water system tackifier.As this water system tackifier, for example have the tackifier of polyvinyl alcohol resin as major component.The water system tackifier can use commercially available, also can be mixed with the material of solvent, adjuvant in commercially available tackifier.Commercially available polyvinyl alcohol resin as becoming the water system tackifier for example has the KL-318 of Kuraray corporate system etc.

This water system tackifier can contain crosslinking chemical.As crosslinking chemical, preferred amines compound, aldehyde compound, methylol compound, epoxy compound, isocyanate compound, multivalent metal salt etc., preferred especially epoxy compound.As the commercially available product of crosslinking chemical, for example, have glyoxal, firmly change the スミレ one ズレジ Application 650 (30) etc. of the aqueous solution of the soluble epoxide compound that Chemtex (strain) sells.

In addition, as another preferred tackifier, can enumerate by containing the tackifier that the epoxy based resin composition constitutes, described epoxy based resin composition contains the epoxy resin that curing takes place by the irradiation of active energy ray or heating.

During tackifier that use is made of such epoxy based resin composition; for transparent protective film with contain first phase retardation film of ethylene series resin and polarizing coating gluing; can carry out by the following method; namely; to being present in the coating layer irradiation active energy ray of the tackifier between these films; or heat, thereby the epoxy resin of the curing that contains in tackifier is solidified.Based on the curing of the epoxy resin of the irradiation of active energy ray or heating, preferably the cationic polymerization by epoxy resin carries out.In addition, in this manual, so-called epoxy resin refers to have in the molecule compound of the epoxy radicals more than 2.

From viewpoints such as weatherability, refractive index, cationically polymerizables, the epoxy resin that contains in the curable epoxy resin composition as tackifier does not contain the epoxy resin of aromatic rings in the preferred molecule.As such epoxy resin, can hydrogenated epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin etc. be shown example.

Hydrogenated epoxy resin, can obtain by the method for the nuclear hydrogenation polyol being carried out the glycidyl etherificate, described nuclear hydrogenation polyol is optionally to carry out the nuclear hydrogenation reaction and obtain in the presence of catalyzer, adding to depress as the polyol of the raw material of aromatic epoxy resin.Be resin as aromatic epoxies, can enumerate the diglycidyl ether of bisphenol-A for example, the diglycidyl ether of Bisphenol F, the such bisphenol-type epoxy resin of diglycidyl ether of bisphenol S; The epoxy resin of the phenol aldehyde type that phenol novolac epoxy resins, cresol novolak epoxy, hydroxy benzaldehyde phenol novolac epoxy resins are such; Epoxy resin of the multifunctional type that the glycidol ether of tetrahydroxy diphenyl methane, the glycidol ether of tetrahydroxybenzophenone, epoxidation polyvinyl phenol are such etc.In hydrogenated epoxy resin, the glycidol ether of preferred bisphenol-A hydride.

So-called ester ring type epoxy is resin, and referring to have in the molecule epoxy that is bonded in the epoxy radicals on the ester ring type ring more than is resin.So-called " being bonded in the epoxy radicals on the ester ring type ring " refers to oxygen atom-O-of putting up a bridge in the structure shown in the following formula, and in the formula, m is 2～5 integer.

[changing 1]

With (the CH in the above-mentioned formula ₂) _mIn one or more hydrogen remove and the group that obtains and other chemical constitution bondings and compound, can become ester ring type epoxy based compound.(CH ₂) _mIn one or more hydrogen, can also suitably replace with straight chain shape alkyl such as methyl, ethyls.In ester ring type epoxy based compound, have the epoxy based compound of oxabicyclo hexane ring (material of m=3 in the above-mentioned formula (1)), oxabicyclo heptane (material of m=4 in the above-mentioned formula), preferred owing to show good tackiness.Below, particular instantiation the structure of the preferred ester ring type epoxy based compound that uses in the present invention, but be not limited to these compounds.

(a) the epoxycyclohexyl methyl epoxycyclohexane carboxylate class shown in the following formula (I):

[changing 2]

(in the formula, R ¹And R ²The straight chain shape alkyl of representing hydrogen atom or carbon number 1～5 independently of each other.)

(b) the epoxycyclohexane carboxylate class of the alkanediol shown in the following formula (II):

[changing 3]

(in the formula, R ³And R ⁴Represent the straight chain shape alkyl of hydrogen atom or carbon number 1～5 independently of each other, n represents 2～20 integer.)

(c) the epoxycyclohexyl methyl ester class of the dicarboxylic acid shown in the following formula (III):

[changing 4]

(in the formula, R ⁵And R ⁶Represent the straight chain shape alkyl of hydrogen atom or carbon number 1～5 independently of each other, p represents 2～20 integer.)

(d) the epoxycyclohexyl methyl ethers of the polyglycol shown in the following formula (IV):

[changing 5]

(in the formula, R ⁷And R ⁸Represent the straight chain shape alkyl of hydrogen atom or carbon number 1～5 independently of each other, q represents 2～10 integer.)。

(e) the epoxycyclohexyl methyl ethers of the alkane diol shown in the following formula (V):

[changing 6]

(in the formula, R ⁹And R ¹⁰Represent the straight chain shape alkyl of hydrogen atom or carbon number 1～5 independently of each other, r represents 2～20 integer.)

(f) bicyclic oxygen three spiro-compounds shown in the following formula (VI):

[changing 7]

(in the formula, R ¹¹And R ¹²The straight chain shape alkyl of representing hydrogen atom or carbon number 1～5 independently of each other.)

(g) the bicyclic oxygen list spiro-compound shown in the following formula (VII):

[changing 8]

(in the formula, R ¹³And R ¹⁴The straight chain shape alkyl of representing hydrogen atom or carbon number 1～5 independently of each other.)

(h) the vinyl cyclohexene diepoxide class shown in the following formula (VIII):

[changing 9]

(in the formula, R ¹⁵The straight chain shape alkyl of expression hydrogen atom or carbon number 1～5.)

(i) the epoxide ring amyl group ethers shown in the following formula (IX):

[changing 10]

(in the formula, R ¹⁶And R ¹⁷The straight chain shape alkyl of representing hydrogen atom or carbon number 1～5 independently of each other.)

(j) the bicyclic oxygen tristane shown in the following formula (X) (diepoxy tricyclodecane) class:

[changing 11]

(in the formula, R ¹⁸The straight chain shape alkyl of expression hydrogen atom or carbon number 1～5.)

Being in the resin at above-mentioned illustrative ester ring type epoxy, is resin for following ester ring type epoxy, from having commercially available or its analog ratio is easier to reasons such as acquisition, the preferred use.

(A) carboxylate of 7-oxabicyclo [4.1.0] heptane-3-carboxylic acid and (7-oxa--two ring [4.1.0] heptan-3-yl) methyl alcohol [in above-mentioned formula (I), R ¹=R ²The compound of=H]

(B) carboxylate of 4-methyl-7-oxabicyclo [4.1.0] heptane-3-carboxylic acid and (4-methyl-7-oxa--two ring [4.1.0] heptan-3-yl) methyl alcohol [in above-mentioned formula (I), R ¹=4-CH ₃, R ²=4-CH ₃Compound]

(C) carboxylate of 7-oxabicyclo [4.1.0] heptane-3-carboxylic acid and 1,2-ethylene glycol [in above-mentioned formula (II), R ³=R ⁴The compound of=H, n=2]

(D) carboxylate of (7-oxabicyclo [4.1.0] heptan-3-yl) methyl alcohol and hexane diacid [in above-mentioned formula (III), R ⁵=R ⁶The compound of=H, p=4]

(E) carboxylate of (4-methyl-7-oxabicyclo [4.1.0] heptan-3-yl) methyl alcohol and hexane diacid [in above-mentioned formula (III), R ⁵=4-CH ₃, R ⁶=4-CH ₃, p=4 compound]

(F) etherate of (7-oxabicyclo [4.1.0] heptan-3-yl) methyl alcohol and 1,2-ethylene glycol [in above-mentioned formula (V), R ⁹=R ¹⁰The compound of=H, r=2]

In addition, as aliphatic epoxy resin, can enumerate the polyglycidyl ether of aliphatic polyol or its alkylene oxide addition product.More specifically, can enumerate 1, the diglycidyl ether of 4-butylene glycol, the diglycidyl ether of 1,6-hexanediol, the triglycidyl ether of glycerine, the triglycidyl ether of trimethylolpropane, the diglycidyl ether of polyglycol, the diglycidyl ether of propylene glycol, on the such aliphatic polyol of ethylene glycol, propylene glycol, glycerine addition more than a kind or 2 kinds alkylene oxide (oxirane, epoxypropane) and polyglycidyl ether of the polyether glycol that obtains etc.

Constitute the epoxy resin of the tackifier that contains the epoxy based resin composition, can only use a kind, also two or more kinds may be used.The epoxide equivalent of the epoxy resin that uses in said composition is usually at 30～3000g/ equivalent, in the scope of preferred 50～1500g/ equivalent.If epoxide equivalent less than the 30g/ equivalent, then exists the pliability of the composite polarizing plate after solidifying to descend, or the possibility of adhesive strength decline.On the other hand, if surpass the 3000g/ equivalent, then exist with tackifier in the possibility that descends of the intermiscibility of other compositions of containing.

In this tackifier, from reactive viewpoint, preferably use cationic polymerization as the curing reaction of epoxy resin.Therefore, in the curable epoxy resin composition as tackifier, preferably cooperate cationic polymerization initiators.By luminous ray, ultraviolet ray, the X line, irradiation or the heating of electronics line isoreactivity energy line, cationic polymerization initiators produces kation kind or lewis acid, thereby causes the polyreaction of epoxy radicals.The cationic polymerization initiators of any type is all given potentiality, from the viewpoint of operability and preferred.Below, to produce kation kind or lewis acid by the irradiation of active energy ray, the cationic polymerization initiators that causes the polyreaction of epoxy radicals is called " light cationic polymerization initiators ", produce kation kind or lewis acid by heat, the cationic polymerization initiators that causes the polyreaction of epoxy radicals is called " hot cationic polymerization initiators ".

Utilize the light cationic polymerization initiators; carry out the method for the curing of tackifier by the irradiation of active energy ray; can be in normal temperature cure; can reduce the thermotolerance of polarizing coating or the consideration of swollen deformation of rising, from can with transparent protective film and polarizing coating well gluing viewpoint be preferred.In addition, because the light cationic polymerization initiators utilizes light performance catalytic activity, even therefore mix in epoxy resin, its storage stability, operability are also excellent.

As the light cationic polymerization initiators, have no particular limits, for example, can enumerate for example aromatic series diazo salt; Aromatic series salt compounded of iodine, the such salt of aromatic series sulfonium salt; The luxuriant iron complex of virtue etc.

As the aromatic series diazo salt, can enumerate for example benzene diazonium hexafluoro antimonate, benzene diazonium hexafluorophosphate, benzene diazonium hexafluoro borate etc.In addition, as the aromatic series salt compounded of iodine, can enumerate for example diphenyl iodonium four (pentafluorophenyl group) borate, diphenyl iodonium hexafluorophosphate, diphenyl iodonium hexafluoro antimonate, two (4-nonyl phenyl) iodine hexafluorophosphate etc.

As the aromatic series sulfonium salt, can enumerate for example triphenylsulfonium hexafluorophosphate, the triphenylsulfonium hexafluoro antimonate, triphenylsulfonium four (pentafluorophenyl group) borate, 4, the two hexafluorophosphates of 4 '-two (diphenyl sulfonium) diphenyl sulfide, 4, the two hexafluoro antimonates of 4 '-two [two (beta-hydroxy ethoxy) phenyl sulfonium] diphenyl sulfide, the two hexafluorophosphates of 4,4 '-two [two (beta-hydroxy ethoxy) phenyl sulfonium] diphenyl sulfide, 7-[two (p-methylphenyl) sulfonium]-2-isopropyl thioxanthone hexafluoro antimonate, 7-[two (p-methylphenyl) sulfonium]-2-isopropyl thioxanthone four (pentafluorophenyl group) borate, 4-phenylcarbonyl group-4 '-diphenyl sulfonium-diphenyl sulfide hexafluorophosphate, 4-(to the tert-butyl-phenyl carbonyl)-4 '-diphenyl sulfonium-diphenyl sulfide hexafluoro antimonate, 4-(to the tert-butyl-phenyl carbonyl)-4 '-(p-methylphenyl) sulfonium-diphenyl sulfide four (pentafluorophenyl group) borate etc.

In addition, as the luxuriant iron complex of virtue, can enumerate for example dimethylbenzene-cyclopentadienyl group iron (II) hexafluoro antimonate, isopropyl benzene-cyclopentadienyl group iron (II) hexafluorophosphoric acid ester, dimethylbenzene-cyclopentadienyl group iron (II)-three (trifluoromethyl sulphonyl) methanides etc.

These light cationic polymerization initiators, can easily obtain commercially available product, for example, if name with trade name respectively, then can enumerate " Kayarad PCI-220 ", " Kayarad PCI-620 " (above by Nippon Kayaku K. K's system), " UVI-6990 " (associating carbonide (Union Carbide) corporate system), " Adeka Optomer SP-150 ", " Adeka Optomer SP-170 " (above by (strain) ADEKA system), " CI-5102 ", " CIT-1370 ", " CIT-1682 ", " CIP-1866S ", " CIP-2048S ", " CIP-2064S " (above by Tso Tat Co., Ltd., Japan's system), " DPI-101 ", " DPI-102 ", " DPI-103 ", " DPI-105 ", " MPI-103 ", " MPI-105 ", " BBI-101 ", " BBI-102 ", " BBI-103 ", " BBI-105 ", " TPS-101 ", " TPS-102 ", " TPS-103 ", " TPS-105 ", " MDS-103 ", " MDS-105 ", " DTS-102 ", " DTS-103 " (above by greening Co., Ltd. system), " PI-2074 " (Luo Diya (Rhodia) corporate system), Deng.

These light cationic polymerization initiators can be distinguished separately and use, and also can mix more than 2 kinds and use.Wherein, aromatic series sulfonium salt especially, even if the wavelength region may more than 300nm also has the UVA characteristic, therefore curing property excellence can provide the solidfied material with good mechanical strength and adhesive strength, therefore preferred the use.

The use level of light cationic polymerization initiators, with respect to epoxy resin 100 weight portions, 0.5～20 weight portion normally, more than preferred 1 weight portion, and below preferred 15 weight portions.

In the use level of light cationic polymerization initiators with respect to epoxy resin 100 weight portions during less than 0.5 weight portion, solidify insufficient, the trend that exists physical strength, adhesive strength to reduce.On the other hand, if the use level of light cationic polymerization initiators with respect to epoxy resin 100 weight portions greater than 20 weight portions, then the ionic substance in the solidfied material increases, so the hydroscopicity of solidfied material improves the possibility that exists endurance quality to reduce.

When making with the light cationic polymerization initiators, in the curable epoxy resin composition as tackifier, as required, can also contain light sensitizer.By using light sensitizer, the reactivity of cationic polymerization improves, and the physical strength of solidfied material, adhesive strength are improved.As light sensitizer, for example can enumerate carbonyls, organosulfur compound, persulfide, redox based compound, azo and diazo-compounds, halogenide, photo-reduction pigment etc.

As concrete light sensitizer, for example can enumerate benzoin methylether, benzoin iso-propylether, α, the alpha, alpha-dimethyl oxygen base-α-such benzoin derivatives of phenyl acetophenone; Benzophenone, 2,4-dichloro benzophenone, o-benzoyl yl benzoic acid methyl esters, 4,4 '-two (dimethylamino) benzophenone, 4, the 4 '-such benzophenone derivates of two (lignocaine) benzophenone; 2-clopenthixal ketone, the such thioxanthone derivates of 2-isopropyl thioxanthone; 2-chloroanthraquinone, the such anthraquinone derivative of 2-tectoquinone; N-methylacridine ketone, the such acridone derivatives of N-butyl acridone; In addition, α, α-diethoxy acetophenone, benzil, Fluorenone, xanthene ketone, uranyl compound, halogenide etc.These can be used alone, but also also mix together respectively.Preferably with respect to curable epoxy resin composition 100 weight portions, contain photosensitizer with the scope of 0.1～20 weight portion.

On the other hand, as hot cationic polymerization initiators, can enumerate benzyl sulfonium salt, thiophene salt, thiophene salt (チオラニウム salt), benzyl ammonium salt, pyridiniujm, hydrazonium salt, carboxylate, sulphonic acid ester, amine acid imide etc.These initiating agents can easily obtain commercially available product, if name with trade name respectively, then can enumerate " ADEKA OPTON CP77 " and " ADEKA OPTON CP66 " (above by Asahi Denka Kogyo K. K's system), " CI-2639 " and " CI-2624 " (above by Tso Tat Co., Ltd., Japan's system), " San-Aid SI-60L ", " San-Aid SI-80L " and " San-Aid SI-100L " (above by three new chemical industry Co., Ltd. systems) etc.

The epoxy resin that contains in the tackifier can be cured by any method of light cationic polymerization or hot cationic polymerization, also can solidify by light cationic polymerization and two kinds of methods of hot cationic polymerization.Under the latter's the situation, preferred also with light cationic polymerization initiators and hot cationic polymerization initiators.

In addition, can also contain oxetanes class, polyalcohols etc. in the curable epoxy resin composition, promote the compound of cationic polymerization.

Oxygen heterocycle butane is the compound that has the four-membered ring ether structure in molecule at least, can enumerate for example 3-ethyl-3-hydroxymethyl 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-ethyl hexyl oxy methyl) oxetanes, phenol phenolic aldehyde oxetanes etc.These oxetanes based compounds, can easily obtain commercially available product, for example, all give an example with trade name, can enumerate " ARON OXETANE OXT-101 ", " ARON OXETANE OXT-121 ", " ARON OXETANE OXT-211 ", " ARON OXETANE OXT-221 ", " ARON OXETANE OXT-212 " (above is that make in East Asia synthetic (strain)) etc.In curable epoxy resin composition, the ratio with 5～95 weight %, preferred 30～70 weight % contains these oxetanes based compounds usually.

As polyalcohols, the polyalcohols that preferably has the acidic-group beyond the phenol hydroxyl can be enumerated the polyol compound that for example do not have the functional group beyond the hydroxyl, polyester polyols alcoholic compound, polycaprolactone polyol compound, the polyol compound with phenol hydroxyl, polycarbonate polyol compound etc.The molecular weight of these polyalcohols is generally more than 48, is preferably more than 62, more preferably more than 100, and is preferably below 1000.The use level of these polyvalent alcohols is generally in curable epoxy resin composition below the 50 weight %, below the preferred 30 weight %.

And then, only otherwise damage effect of the present invention, in curable epoxy resin composition, can cooperate other adjuvants, for example ion-trapping agent, antioxidant, chain-transferring agent, sensitizer, tackifier, thermoplastic resin, filling agent, flow modifier, plastifier, defoamer etc.As ion-trapping agent, for example can enumerate the mineral compound of pulverous bismuth system, antimony system, magnesium system, aluminium system, calcium system, titanium system and their mixed stocker etc., as antioxidant, for example can enumerate hindered phenol is antioxidant etc.

The tackifier that will comprise the above curable epoxy resin composition that contains epoxy resin; a side or both sides at the gluing surface of polarizing coating and transparent protective film; after perhaps applying on a side of the gluing surface of polarizing coating and first phase retardation film or the both sides; the face that is coated with tackifier is fitted; by irradiation active energy ray or heating this uncured adhesive layer is solidified; thereby the adhesive layer of solidfied material layer that can be by comprising curable epoxy resin composition fits in polarizing coating with transparent protective film, perhaps first phase retardation film is fitted in polarizing coating.As the coating method of tackifier, rod is coated with, mould is coated with, various coating methods such as comma is coated with, intaglio plate coating for example can to utilize scraper to be coated with, to wind the line.

Gluing in polarizing coating 101 and the tackifier that contains epoxy resin that uses in order to make transparent protective film 102 and to contain first phase retardation film 103 of ethylene series resin; basically can use the solventless adhesive that does not contain solvent composition in fact; but owing in each application pattern, there are the suitableeest various range of viscosities, therefore can contain solvent for the viscosity adjustment.Preferably after being coated on film, make before the adhesive solidification, carry out heat treated etc., remove the solvent of adjusting for viscosity.

As solvent, the solvent that preferred use does not make the optical property of polarizing coating descend, composition epoxy resin is dissolved well, for example, can to enumerate with toluene be the representative hydro carbons, be the organic solvents such as ester class of representative with ethyl acetate.

When carrying out the curing of tackifier by the irradiation active energy beam, the light source that uses is not particularly limited, and can use for example low pressure mercury lamp that has luminous distribution below wavelength 400nm, medium pressure mercury lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, chemical lamp, black lamp, microwave-excitation mercury lamp, metal halide lamp etc.Curable epoxy resin composition is carried out light-struck illumination penetrate intensity and determine as composition of object according to each, preferably the exposure intensity to the effective wavelength coverage of activation of light cationic polymerization initiators is 0.1～100mW/cm ²Undercapacity 0.1mW/cm is penetrated in the illumination of curable epoxy resin composition ²The time, the reaction time is long, is surpassing 100mW/cm ²The time, because the heat release during from the heat of lamp radiation and curable epoxy resin composition polymerization exists the xanthochromia that produces solidification compound, the possibility of polarizing coating variation.The illumination of the curable epoxy resin composition time of penetrating is treated that according to each cured compositions controls, still is not particularly limited that preferably setting into the represented accumulative total light quantity of the product of exposure intensity and irradiation time is 10～5000mJ/cm ²

At the accumulative total deficiency in light quantity 10mJ/cm to the solidification compound irradiation ²The time, insufficient from the generation of the spike of light cationic polymerization initiators, the curing of adhesive layer is insufficient sometimes.On the other hand, surpass 5000mJ/cm in the accumulative total light quantity ²The time, it is very long that irradiation time becomes, and improves in throughput rate to become unfavorable.

When carrying out polymerization by heat, can using usually, known method heats, its condition etc. also is not particularly limited, produce the kation kind, heat more than the lewis acidic temperature, usually about 50～200 ℃ by the cationic polymerization thermal initiator that in curable epoxy resin composition, cooperates.

When irradiation active energy beam or add is cured under arbitrary condition of pining for, also preferably at degree of polarization, transmissivity and form and aspect, the transparent protective film of polarizing coating with contain the transparency of first phase retardation film of ethylene series resin and scope that all functions of phase difference characteristics and polarization plates can not reduce is cured.

[second phase retardation film]

In second phase retardation film 105, its sandwich layer 31 contains phenylethylene resin series, forms the cortex 32 that is made of (methyl) acrylic resin composition that contains rubber particles on the two sides of sandwich layer.

Constituting the phenylethylene resin series of sandwich layer 31, can be the homopolymer of styrene or derivatives thereof, also can be binary or the above multipolymer of binary that styrene or derivatives thereof and other co-polymerized monomers form in addition.Here, so-called styrene derivative, refer to the compound that other group bondings form in styrene, can enumerate for example o-methyl styrene, a methyl styrene, p-methylstyrene, 2,4-dimethyl styrene, adjacent ethyl styrene, to the ring-alkylated styrenes of ethyl styrene and so on, hydroxy styrenes, tert-butoxy styrene, vinyl benzoic acid, chloro styrene, the ring at cinnamic benzene of chlorostyrene and so on is imported substituted phenylethylene of hydroxyl, alkoxy, carboxyl, halogen etc. etc.Also can use disclosed terpolymer among TOHKEMY JP2003-50316-A, the JP2003-207640-A.Optimization styrene is that resin is styrene or styrene derivative, with the multipolymer that is selected from least a kind monomer in vinyl cyanide, maleic anhydride, methyl acrylate and the butadiene.The phenylethylene resin series of sandwich layer preferably is made of heat-resistant resin, and generally its Tg is more than 100 ℃.The more preferably Tg of phenylethylene resin series is more than 120 ℃.

The sandwich layer 31 that contains phenylethylene resin series, preferably its thickness setting is 10～100 μ m.During its thickness less than 10 μ m, be difficult to show enough length of delays by stretching sometimes.On the other hand, if its thickness surpasses 100 μ m, then the impact strength of film is easy to die down, and has the trend that causes retardation variation to increase by external stress, when being applied to liquid crystal indicator, is easy to produce hickie etc., and display performance descends easily.

The cortex 32 that disposes on the two sides of the sandwich layer 31 that contains above-mentioned phenylethylene resin series is made of (methyl) acrylic resin composition that is combined with rubber particles in (methyl) acrylic resin.

Here, as (methyl) acrylic resin, for example, can enumerate the multipolymer etc. of homopolymer, alkyl methacrylate and the alkyl acrylate of alkyl methacrylate or alkyl acrylate.As alkyl methacrylate, specifically, can enumerate methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate etc., in addition as alkyl acrylate, specifically, can enumerate methyl acrylate, ethyl acrylate, propyl acrylate etc.In such (methyl) acrylic resin, can use the commercially available product as general (methyl) acrylic resin.In addition, in (methyl) acrylic resin, contain the compound that is called shock-resistant (methyl) acrylic resin, in addition, also contain have the glutaric anhydride structure in the main chain, the compound that is called as high heat-resisting (methyl) acrylic resin of lactonic ring structure.

The rubber particles that in (methyl) acrylic resin, cooperates, the rubber particles of preferred acrylic acid series.So-called acrylic rubber particle, be alkyl acrylate with butyl acrylate, 2-EHA and so on as major component, in the presence of polyfunctional monomer, make their polymerizations and the particle with caoutchouc elasticity.The particle with caoutchouc elasticity like this can form individual layer, also can be the multilayer structure making with at least 1 layer of rubber elastic layer.As the acrylic rubber particle of sandwich construction, can enumerate following example: as nuclear, utilize the alkyl methacrylate based polymer of hard that the particle that forms will be covered around it on above-mentioned particle with caoutchouc elasticity; As nuclear, utilize above-mentioned acrylic acid series polymeric compounds with caoutchouc elasticity to cover the particle that forms around it alkyl methacrylate based polymer of hard; Utilize acrylic acid series polymeric compounds with caoutchouc elasticity to cover around the nuclear of hard in addition, so around it alkyl methacrylate based polymer of recycling hard cover and particle etc.

These rubber particles, the mean diameter of the particle that forms in elastic layer is generally about 50～400nm.

The content of the above-mentioned rubber particles in (methyl) acrylic resin composition of formation cortex 32 with respect to (methyl) acrylic resin 100 weight portions, is generally about 5～50 weight portions.For (methyl) acrylic resin and acrylic rubber particle, owing to be the state of its mixing is sold, therefore can be used its commercially available product.As the example of the commercially available product of (methyl) acrylic resin that is combined with the acrylic rubber particle, can enumerate " HT55X " that sumitomo chemical company sells, " Technoloy (registered trademark) S001 " etc.(methyl) acrylic resin composition so generally has the Tg below 160 ℃, but preferred Tg is below 120 ℃, and is further preferred below 110 ℃.

By the cortex 32 that (methyl) acrylic resin composition that is combined with rubber particles, preferred acrylic rubber particle constitutes, its thickness preferably is controlled to be 10～100 μ m.Its thickness is during less than 10 μ m, has the become trend of difficulty of film processed.On the other hand, if greater than 100 μ m, then there is the trend of the length of delay that can not ignore this (methyl) acrylic resin layer in thickness.

As mentioned above, in the present invention in second phase retardation film 105 of Shi Yonging, sandwich layer 31 preferred its Tg that contain phenylethylene resin series are more than 120 ℃, on the other hand, cortex 32 by (methyl) acrylic resin composition formation that is combined with rubber particles, preferred its Tg is below 120 ℃, and is further preferred below 110 ℃.Preferably both Tg are not overlapping, contain the sandwich layer 31 of phenylethylene resin series, have the Tg higher than the cortex that is made of (methyl) acrylic resin composition that is combined with rubber particles 32.

Second phase retardation film 105 used in the present invention can be made by the following method: for example, phenylethylene resin series, (methyl) acrylic resin composition of being combined with rubber particles are together extruded, stretched then.In addition, make its heat fusion by heat lamination after also can utilizing the film of making individual layer respectively, again with the method for its stretching.

In this second phase retardation film 105, make following 3-tier architecture, that is, be formed with the cortex 32 that is constituted by (methyl) acrylic resin composition that is combined with rubber particles at two faces that contain phenylethylene resin series sandwich layer 31.In this 3-tier architecture, make roughly the same thickness usually at the cortex 32 that two faces dispose.Like this by forming 3-tier architecture, the cortex 32 that is made of (methyl) acrylic resin composition that is combined with rubber particles can play the effect of protective seam, and physical strength, drug resistance become good.

By stretching, can give phase differential in the face to second phase retardation film 105 by the above formation.Stretching can be by known vertical single ax stretching, the horizontal uniaxial tension of stenter, the while is Biaxially stretched, the Biaxially stretched grade carried out one by one, and stretching according to the mode that obtains required length of delay gets final product.

In the present invention in second phase retardation film 105 of Shi Yonging, length of delay Re is 20～120nm in the preferred face, and have above-mentioned formula (5) N _zCoefficient is less than-0.5 refractive index anisotropy greater than-2.

When first phase retardation film 103 and second phase retardation film 105 is stacked, the variation of the angulation of the angle of orientation of preferred first phase retardation film 103 and second phase retardation film 105 was made as below 0.4 ° in the interval of 10cm.If the variation of the angulation of the angle of orientation is greater than 0.4 °, then polarization state can change sharp in the part, can observe color spot when therefore being installed on liquid crystal indicator.Here, the so-called angle of orientation refers to the maximum orientation of refractive index in each position of each film.

In stretched film, generally will in face, be called slow axis by the axle of refractive index maximum, if examine, there is small variation in this at each position, therefore, such angle of orientation also is defined simultaneously.The angle of orientation can be utilized commercially available phasometer or pick-up unit, and for example the phase retardation film optical material pick-up unit RETS of the system of the big tomb electronics (strain) shown in the embodiment described later measures.For the variation (deviation) with the angulation of the angle of orientation of first phase retardation film 103 and second phase retardation film 105 is decreased to above-mentioned scope, for example, preferably for first phase retardation film 103 and second phase retardation film 105, use the little film of deviation of the angle of orientation respectively.

[bonding agent]

Across bonding agent 104 stacked first phase retardation film 103 and second phase retardation films 105 that contain the ethylene series resin, this phase retardation film 105 has the structure with the two sides of the cortex 32 that contains acrylic resin, sandwich layer 31 that 32 clampings contain phenylethylene resin series.The thickness of adhesive phase 104 is generally about 5～100 μ m, preferred 5～40 μ m.If adhesive phase is thin excessively, then cohesive descends, if blocked up, then is easy to produce unfavorable conditions such as bonding agent is forced out.Be used to form the bonding agent of adhesive phase 104, can use known adhesive, usually constituted by following composition, described composition is with acrylic resin, phenylethylene resin series, silicone-based resins etc. are as base resin, add crosslinking chemicals such as isocyanate compound, epoxy compound, aziridine cpd therein, can also add silane coupling agent etc. as required and the composition that forms.

[liquid crystal indicator]

By at the outside of second phase retardation film 105 configuration adhesive phase 108, the composite polarizing plate 100 of the above formation can be fitted in liquid crystal cells.And then in the outside of adhesive phase 108, applying separator 109, before using adhesive phase 108 being glued protection in advance is common way.This composite polarizing plate 100 is laminated at least one side of liquid crystal cells, can constitutes liquid crystal indicator.When being applied to liquid crystal indicator, peel off separator 109 earlier, utilizing adhesive phase 108 just can fit in liquid crystal cells.

Can dispose this composite polarizing plate at two faces of liquid crystal cells, also can dispose this composite polarizing plate at the single face of liquid crystal cells, and dispose other polarizing coatings at another face.To the applying of liquid crystal cells the time, be configured in the mode of phase retardation film side to liquid crystal cells.

Liquid crystal indicator of the present invention can be the formation that disposes composite polarizing plate of the present invention on the two sides of liquid crystal cells, also can be the formation that disposes composite polarizing plate of the present invention at the single face of liquid crystal cells.Under the latter's the situation, do not dispose a side of composite polarizing plate of the present invention, can dispose other polarization plates.The liquid crystal indicator of such formation, effective especially when liquid crystal cells is transverse electric field mode.

In liquid crystal indicator of the present invention; when a face of liquid crystal cells disposes composite polarizing plate of the present invention; preferably be configured in the polarization plates that liquid crystal cell side has transparent protective film at another side, described transparent protective film is that length of delay Re is that 10nm absolute value following and thickness direction retardation value Rth is the following diaphragm of 15nm in the face.The liquid crystal cell side diaphragm of this polarization plates, further preferred Re is below the 5nm, the absolute value of Rth is below the 10nm in addition.

Employed material in the transparent protective film that length of delay Re in the face is below the 10nm as satisfying, the absolute value of thickness direction retardation value Rth is these main points below the 15nm, for example can enumerate cellulose-based resin, annular ethylene series resin, (methyl) acrylic resin, ethylene glycol terephthalate is resin, propylene resin etc.

[embodiment]

Below, enumerate the present invention of embodiment and further specifically describe, the invention is not restricted to these examples.In the example, " part " and " % " of expression use amount or content there not being when special instruction, refers to weight basis.In addition, in the thickness of film, face and thickness direction retardation value and N _zThe following method of coefficients by using is measured.

[Determination of thickness method]

Use the digital mircrometer gauge MH-15M of NIKON's system, measure the thickness of film.

[length of delay, thickness direction retardation value and N in the face _zThe assay method of coefficient]

Use prince's instrumentation machine (strain) system with the phasometer KOBRA-21ADH of parallel Nikkor rotary process as principle, at 23 ℃ of light that utilize wavelength 590nm, length of delay Re, thickness direction retardation value Rth and N in the opposite _zCoefficient is measured.

At first, the example of making the tackifier, bonding agent and second phase retardation film that use in embodiment and the comparative example is shown, and the two sides that described second phase retardation film is included in the sandwich layer that contains phenylethylene resin series is formed with the 3-tier architecture of the cortex that is made of (methyl) acrylic resin composition that contains rubber particles.

[preparation of water system tackifier]

With respect to 100 parts in water, 3 parts of carboxy-modified polyvinyl alcohol (PVA) [KL-318 of Kuraray corporate system] are dissolved, in its aqueous solution, adding 1.5 parts of daiamid epoxies as the soluble epoxide compound is that adjuvant [is firmly changed the スミレ one ズレジ Application 650 (30) of Chemtex (strain) system, Gu form the aqueous solution of dividing concentration 30%], make the water system tackifier.

[preparation of the tackifier that is constituted by curable epoxy resin composition]

With two (3,4-epoxycyclohexyl methyl) hexane diacid is 100 parts, 25 parts of diglycidyl ether of hydrogenated bisphenol A and as 4 of light cationic polymerization initiators, two (hexafluorophosphate) the 2.2 parts of mixing of 4 '-two (diphenyl sulfonium) diphenylsulfide, carry out deaeration then, obtain the tackifier that is constituted by curable epoxy resin composition.

In addition, for the light cationic polymerization initiators, make 50% carbonic allyl ester solution and cooperate again.

[preparation of acrylic adhesive]

In butyl acrylate and acrylic acid multipolymer, be combined with urethane acrylate oligomer and isocyanate-based crosslinking chemical, and make organic solvent solution, utilize mould to be coated with machine this organic solvent solution so that dried thickness reaches the mode of 25 μ m is coated in and has implemented on the demoulding treated side of polyethylene terephthalate film (separator) that thickness that the demoulding handles is 38 μ m, and make its drying, make acrylic adhesive.

[making of second phase retardation film that is constituted by 3-tier architecture]

(phase retardation film A)

With phenylethylene-maleic anhydride based copolymerized resin (" DYLARK (registered trademark) D332 " of Novachemical corporate system, Tg=131 ℃) as sandwich layer, with have an appointment metha crylic resin (" Technoloy (registered trademark) S001 " of Sumitomo Chemical (strain) system of acrylic rubber particle of 20% mean grain size 200nm of cooperation, Tg=105 ℃) as cortex, carry out 3 layers of coextrusion, obtain forming on the two sides of sandwich layer corticated resin 3 tunics.These resin 3 tunics are stretched, make Re=47.3nm, N _zThe phase retardation film of coefficient=-1.06.With it as phase retardation film A.

(phase retardation film B)

Resin 3 tunics that will be identical with the film that uses in the making of above-mentioned phase retardation film A stretch, and make Re=47.3nm, N _zThe phase retardation film of coefficient=-0.98.With it as phase retardation film B.

(phase retardation film C)

Resin 3 tunics that will be identical with the film that uses in the making of above-mentioned phase retardation film A stretch, and make Re=55.0nm, N _zThe phase retardation film of coefficient=-1.1.With it as phase retardation film C.

[embodiment 1]

(A) making of composite polarizing plate

Will be about 2400 by average degree of polymerization, the polyvinyl alcohol film of thick 75 μ m that 99.9 moles of polyvinyl alcohol (PVA) more than the % of saponification degree constitute with dry type stretching mode uniaxial tension to about 5 times, and then kept the constant pure water dipping at 60 ℃ of tensioning state 1 minute, be 60 seconds of dipping in 0.05/5/100 the aqueous solution in the weight ratio of iodine/potassium iodide/water of 28 ℃ then.In the weight ratio of 72 ℃ potassium iodide/boric acid/water it is in the aqueous solution of 8.5/8.5/100 dipping 300 seconds thereafter.Then, utilize 26 ℃ pure water to wash for 20 seconds, carry out drying with 65 ℃ then, thereby obtain having in polyvinyl alcohol (PVA) absorption orientation the polarizing coating of iodine.

On a face of this polarizing coating; the tri cellulose acetate membrane of the thick 80 μ m of saponification processing was implemented in applying as the surface of transparent protective film; on another face; fit following film as first phase retardation film; and make the absorption axes of polarizing coating parallel with the leading phase shaft of first phase retardation film; thereby the making polarization plates, described film be the film of purchasing in the thick 38.6 μ rn of Japanese ZEON (strain) that contains annular ethylene series resin, and Re=74.2nm, N _zCoefficient=1.41.In order to fit, the water system tackifier that uses preamble to illustrate respectively, 5 minutes dryings are carried out with 80 ℃ in the back of fitting, thereby make transparent protective film and first phase retardation film gluing in polarizing coating.Then, with 40 ℃ condition, the polarization plates that obtains carried out 168 hours maintenance.

Utilize acrylic adhesive in the absorption axes of the polarizing coating mode parallel with the leading phase shaft of second phase retardation film, at the phase retardation film A shown in the first phase retardation film side applying preamble of the above polarization plates that obtains as second phase retardation film, thereby make composite polarizing plate.

(B) making of liquid crystal indicator and evaluation

Take off backlight from the liquid crystal indicator of the liquid crystal cells that contains the IPS pattern [VIERA of Panasonic's (strain) system (model: TH-37LZ85)], and then take off the polarization plates in the backlight side configuration of liquid crystal cells, its glass face is cleaned.Then, backlight side at this liquid crystal cells, the composite polarizing plate of in acrylic adhesive bonding above-mentioned (A), making, so that the absorption axes of its absorption axes and the polarization plates of original configuration is identical and second phase retardation film is in liquid crystal cell side, thus the making liquid crystal panel.At last, the backlight of temporarily taking off is re-assemblied, thereby be assembled into liquid crystal indicator.

For this liquid crystal indicator, lighting backlight after 30 minutes, use the liquid crystal angle of visibility determinator " EZ Contrast 88XL " of ELDIM corporate system to measure the distribution plan of contrast ratio, and be shown in Fig. 2.Among the figure, the numeral polar angle of transverse axis, the numeral position angle of circumference, the contrast of the distribution of contrast ratio by scale shown in the right side is than corresponding white black deep or light performance the (Fig. 3～7 are also identical).The position (circle among the figure) of 60 ° of 135 °, polar angle shows 192 contrast ratio at the position angle.Here, so-called contrast ratio refers to the ratio of the brightness of the brightness of white show state/black show state.In addition, the position angle be in the picture right as 0 ° and with the inverse time rotation as positive value, polar angle is the pitch angle from the picture normal direction.

[embodiment 2]

(A) making of composite polarizing plate

Relative (A) of embodiment 1, with first phase retardation film of embodiment 1 change to purchase in the thick 29.8 μ m of Japanese ZEON (strain) contain annular ethylene series resin, Re=79.2nm, N _zThe film of coefficient=1.21, second phase retardation film is changed to the phase retardation film B shown in the preamble, composite polarizing plate is made in other same operations, this phase retardation film B has the 3-tier architecture that is formed with the cortex that is made of (methyl) acrylic resin composition that contains rubber particles on the two sides of the sandwich layer that contains phenylethylene resin series

(B) making of liquid crystal indicator and evaluation

Here except the composite polarizing plate that use obtains, similarly operate with (B) of embodiment 1, make liquid crystal indicator.Adopt with embodiment 1 (B) same method and measure for this liquid crystal indicator, the distribution plan of contrast ratio is shown in Fig. 3.The position (circle among the figure) of 60 ° of 135 °, polar angle shows 195 contrast ratio at the position angle.

[embodiment 3]

(A) making of composite polarizing plate and polarization plates

With operation similarly among (A) of embodiment 2, fit at a face of polarizing coating and to contain the transparent protective film of cellulose triacetate, at another surface layer folded Re=79.2nm, N _zFirst phase retardation film that contains annular ethylene series resin and the phase retardation film B of coefficient=1.21, thereby making composite polarizing plate, described phase retardation film B have the 3-tier architecture that is formed with the cortex that is made of (methyl) acrylic resin composition that contains rubber particles on the two sides of the sandwich layer that contains phenylethylene resin series.

On the other hand; coating surface on the face of the polarizing coating made according to method shown in (A) first half of embodiment 1 was implemented the tri cellulose acetate membrane of the thick 80 μ m that saponification handles; at another side; containing of thick 40 μ m transparent protective film cellulose triacetate, Re=0.7nm, Rth=-0.1nm [Konica Minolta optics (strain) system KC4UEW] of fitting, thus the polarization plates that the two sides all is laminated with the transparent protective film that constitutes with cellulose triacetate made.In order to fit, the water system tackifier that uses preamble to illustrate respectively, the back of fitting is with 80 ℃ of dryings 5 minutes, from but the transparent protective film on two sides is gluing in polarizing coating respectively.

(B) making of liquid crystal indicator and evaluation

Take off backlight in the liquid crystal indicator of the liquid crystal cells of the same IPS pattern of from (B) that contain embodiment 1, using, take off the polarization plates on liquid crystal cells two sides again, wash its glass face.Then, backlight side at this liquid crystal cells, across acrylic adhesive that the composite polarizing plate shown in the first half of above-mentioned (A) is bonding, so that second phase retardation film is in liquid crystal cell side, recognize side looking of liquid crystal cells, across the polarization plates shown in acrylic adhesive bonding above-mentioned (A) latter half of, so that the tri cellulose acetate membrane of thick 40 μ m is in liquid crystal cell side and each absorption axes is identical with the absorption axes of the polarization plates of original configuration, thereby make liquid crystal panel.At last, the backlight of temporarily taking off is re-assemblied, thereby be assembled into liquid crystal indicator.

Adopt with embodiment 1 (B) same method and measure for this liquid crystal indicator, the distribution plan of contrast ratio is shown in Fig. 4.The position (circle among the figure) of 60 ° of 135 °, polar angle shows 195 contrast ratio at the position angle.

[embodiment 4]

(A) making of composite polarizing plate and polarization plates

Similarly operate with embodiment 2 (A), fit at a face of polarizing coating and contain the transparent protective film of cellulose triacetate, at the folded Re=79.2nm of another surface layer, N _zFirst phase retardation film that contains annular ethylene series resin and the phase retardation film B of coefficient=1.21, thereby making composite polarizing plate, described phase retardation film B have the 3-tier architecture that is formed with the cortex that is made of (methyl) acrylic resin composition that contains rubber particles on the two sides of the sandwich layer that contains phenylethylene resin series.

On the other hand; on a face of the polarizing coating of making according to method shown in (A) first half of embodiment 1; coating surface was implemented the tri cellulose acetate membrane of the thick 80 μ m of saponification processing; on another face; applying contains transparent protective film annular ethylene series resin, Re=2.1nm, Rth=2.8nm [purchasing in Japanese ZEON (strain)] of thick 40 μ m, thereby is produced on the polarization plates that the two sides is laminated with transparent protective film.In order to fit, the water system tackifier that uses preamble to illustrate respectively, 5 minutes dryings are carried out with 80 ℃ in the back of fitting, thereby make transparent protective film and first phase retardation film gluing in polarizing coating.Then, with 40 ℃ condition, the polarization plates that obtains carried out 168 hours maintenance.

(B) making of liquid crystal indicator and evaluation

Take off backlight in the liquid crystal indicator of the liquid crystal cells of the same IPS pattern of from (B) that contain embodiment 1, using, take off the polarization plates on liquid crystal cells two sides again, wash its glass face.Then; backlight side at this liquid crystal cells; across the composite polarizing plate shown in the first half of acrylic adhesive bonding above-mentioned (A); so that second phase retardation film is in liquid crystal cell side; recognize side looking of liquid crystal cells; across the polarization plates shown in acrylic adhesive bonding above-mentioned (A) latter half of, so that the protective film that contains annular ethylene series resin of thick 40 μ m is in liquid crystal cell side and each absorption axes is identical with the absorption axes of the polarization plates of original configuration, thereby make liquid crystal panel.At last, the backlight of temporarily taking off is re-assemblied, thereby be assembled into liquid crystal indicator.

Adopt with embodiment 1 (B) same method and measure for this liquid crystal indicator, the distribution plan of contrast ratio is shown in Fig. 5.The position (circle among the figure) of 60 ° of 135 °, polar angle shows 195 contrast ratio at the position angle.

[comparative example 1]

(A) coating surface was implemented the tri cellulose acetate membrane of the thick 80 μ m that saponification handles on a face of the polarizing coating of making according to method shown in (A) first half of the making embodiment 1 of polarization plates; at another side; containing of thick 40 μ m transparent protective film cellulose triacetate, Re=0.7nm, Rth=-0.1nm [Konica Minolta optics (strain) system KC4UEW] of fitting, thus the polarization plates that the two sides all is laminated with the transparent protective film that constitutes with cellulose triacetate made.In order to fit, the water system tackifier that uses preamble to illustrate respectively, the back of fitting is with 80 ℃ of dryings 5 minutes, thereby makes the transparent protective film on two sides gluing in polarizing coating respectively.

(B) making of liquid crystal indicator and evaluation

Except using the polarization plates of making here, with embodiment 1 (B) same operation, make liquid crystal indicator.This polarization plates, gluing in liquid crystal cells with the tri cellulose acetate membrane side of thick 40 μ m.Adopt with embodiment 1 (B) same method and measure for this liquid crystal indicator, the distribution plan of contrast ratio is shown in Fig. 6.The position (circle among the figure) of 60 ° of 135 °, polar angle shows 26 contrast ratio at the position angle.

[embodiment 5]

(A) making of composite polarizing plate

For embodiment 1 (A), with first phase retardation film change to purchase in the thick 35.8 μ m of Japanese ZEON (strain) contain annular ethylene series resin, Re=76.2nm, N _zThe film of coefficient=1.37, second phase retardation film is changed to the phase retardation film C shown in the preamble, other make composite polarizing plate for same operation, and described phase retardation film C has the 3-tier architecture that is formed with the cortex that is made of (methyl) acrylic resin composition that contains rubber particles on the two sides of the sandwich layer that contains phenylethylene resin series.

(B) making of liquid crystal indicator and evaluation

Except using the polarization plates of making here, with embodiment 1 (B) same operation, make liquid crystal indicator.Adopt with embodiment 1 (B) same method and measure for this liquid crystal indicator, the distribution plan of contrast ratio is shown in Fig. 7.The position of 60 ° of 135 °, polar angle shows 326 contrast ratio at the position angle.

In this liquid crystal indicator, see the color spot of locality in the demonstration.Therefore, the composite polarizing plate that uses is peeled off from liquid crystal panel, centered by the part of the color spot of seeing locality, cut out along the picture width direction, second phase retardation film that will contain 3-tier architecture is peeled off with first phase retardation film that contains annular ethylene series resin, the state of fitting with quilt separately, measure the angle of orientation of corresponding position, mensuration is to utilize the phase retardation film optical material pick-up unit RETS of big tomb electronics (strain) system, and carry out along the Width span 80cm of picture, calculate the angle that constitutes (side the angle of orientation and the opposing party's the angle of orientation poor) of the angle of orientation at each position.It is the results are shown in Fig. 8 (a).The variation of the angle that the angle of orientation of phase retardation film used herein 2 pieces constitutes on the interval of 10cm is 0.43 ° to the maximum.

(C) making of other composite polarizing plates and liquid crystal indicator and evaluation

On the one hand, use with above-mentioned (A) in the film that uses as first phase retardation film as same levels, but be other batch film [purchase in the thick 35.8 μ m of Japanese ZEON (strain) contain annular ethylene series resin, Re=76.2nm, N _zThe film of coefficient=1.37], other and above-mentioned (A) identical operations are made composite polarizing plate, use this plate and above-mentioned (B) similarly to assemble liquid crystal indicator.The distribution of this contrast of LCD degree ratio is identical with Fig. 7, and the position that 135 ° at the position angle, polar angle are 60 ° shows 326 contrast ratio, does not see the color spot of locality in the demonstration.Composite polarizing plate used herein is peeled off from liquid crystal panel, cut out part identical when measuring the angle of orientation along the picture width direction in the above, second phase retardation film that will comprise 3-tier architecture is peeled off with first phase retardation film that contains annular ethylene series resin, the state of fitting with quilt separately, measure the angle of orientation of corresponding position, mensuration is to utilize the phase retardation film optical material pick-up unit RETS of big tomb electronics (strain) system, and carry out along the Width span 80cm of picture, calculate the angle that constitutes (side the angle of orientation and the opposing party's the angle of orientation poor) of the angle of orientation at each position.It is the results are shown in Fig. 8 (b).The variation of the angle that the angle of orientation of phase retardation film used herein 2 pieces constitutes in the interval of 10cm is 0.27 ° to the maximum.

Claims

1. composite polarizing plate, wherein,

Be laminated with transparent protective film across first adhesive layer at a face of polarizing coating, be laminated with first phase retardation film that contains the ethylene series resin across second adhesive layer at the another side of polarizing coating,

And then, be laminated with second phase retardation film across adhesive phase in the outside of first phase retardation film,

It is characterized in that described second phase retardation film has 3-tier architecture, described 3-tier architecture is the 3-tier architecture that is formed with the cortex that is formed by (methyl) acrylic resin composition that contains rubber particles on the two sides of the sandwich layer that contains phenylethylene resin series.

2. composite polarizing plate according to claim 1,

In first phase retardation film, length of delay is 30～150nm in the face, and has following refractive index anisotropy,, the refractive index of leading phase shaft direction and thickness direction in slow axis direction, the face in its face is made as n respectively that is _x, n _yAnd n _zThe time, formula: (n _x-n _z)/(n _x-n _y) defined Nz coefficient greater than 1 less than 2,

In second phase retardation film, length of delay is 20～120nm in the face, and has following refractive index anisotropy, that is, and and Ding Yi N as mentioned above _zCoefficient greater than-2 less than-0.5.

3. composite polarizing plate according to claim 1 and 2, wherein, so that being mode below 0.4 °, the variation of the formed angle of the angle of orientation of first phase retardation film and second phase retardation film is laminated with first phase retardation film and second phase retardation film in the interval of 10cm.

4. composite polarizing plate according to claim 1 and 2, wherein, the ethylene series resin is the annular ethylene series resin that contains the structural unit of being derived by ester ring type alkene.

5. composite polarizing plate according to claim 1 and 2, second phase retardation film comprises sandwich layer and cortex, it is phenylethylene resin series more than 120 ℃ that described sandwich layer contains glass transition temperature, and described cortex is that (methyl) acrylic resin composition below 120 ℃ forms by glass transition temperature.

6. composite polarizing plate according to claim 1 and 2, wherein, second adhesive layer comprises the water system tackifier that contains polyvinyl alcohol resin and epoxy compound.

7. composite polarizing plate according to claim 1 and 2, wherein, second adhesive layer is formed by the solidfied material layer of epoxy based resin composition, and described epoxy based resin composition contains the irradiation that utilizes active energy ray or heating and the epoxy that solidifies is resin.

8. composite polarizing plate according to claim 7, wherein, epoxy is that resin contains and has the compound that is bonded to the epoxy radicals of ester ring type ring more than 1 in the molecule.

9. IPS mode LCD, wherein, at least one face in IPS mode liquid crystal unit disposes each described composite polarizing plate in the claim 1～8.

10. IPS mode LCD according to claim 9; wherein a face in IPS mode liquid crystal unit disposes each described composite polarizing plate of claim 1～8; dispose the polarization plates that has transparent protective film in liquid crystal cell side at another side, described transparent protective film is that length of delay is that 10nm is following, the absolute value of thickness direction retardation value is the following transparent protective film of 15nm in the face.