CN101995599A - Composite polarizing plate and TN mode liquid crystal panel - Google Patents

Abstract

The present invention provides a composite polarizing plate obtained by sequentially laminating a transparent protective layer, a polarizer, a biaxial retardation film made of an olefin resin, and an adhesive layer, wherein the olefin resin The biaxial retardation film constituted when the refractive index in the in-plane slow axis direction, the in-plane fast axis direction and the thickness direction measured by light with a wavelength of 590nm are set to _nx , _ny and _nz , respectively, as follows The in-plane retardation value R ₀ defined by the formula (I) is 40 to 150 nm, the retardation value R _th in the thickness direction defined by the following formula (II) is 50 to 250 nm, and the N _z coefficient defined by the following formula (III) More than 1 and less than 7, the adhesive layer exhibits a storage elastic modulus of 0.15 to 10 MPa at 23 to 80°C. The present invention can provide a composite polarizing plate capable of suppressing light leakage even after exposing a liquid crystal display device to a high temperature environment, and a TN mode liquid crystal panel using the composite polarizing plate and a TN mode liquid crystal panel using the above composite polarizing plate. R ₀ =(n _x -n _y )×d (I); R _th =[(n _x +n _y )/2-n _z ]×d (II); N _z =(n _x -n _z )/ (n _x -n _y ) (III).

Description

Composite polarizing plate and TN mode liquid crystal panel

Technical field

The present invention relates to a kind of composite polarizing plate, and use the TN mode liquid crystal panel that uses in the liquid crystal cells, liquid crystal indicator of its TN (Twisted Nematic, twisted nematic) pattern.

Background technology

The liquid crystal cells of TN pattern is to enclose nematic liquid crystal between two transparency carriers, applies this nematic liquid crystal under the state of voltage reverses 90 ° of orientations between two transparency carriers liquid crystal cells in nothing.Applied under the state of voltage between to two transparency carriers, this nematic liquid crystal is orientated in the substrate normal direction.In the liquid crystal indicator of the liquid crystal cells that possesses the TN pattern, when utilizing this nothing to apply voltage and the variation of the state of orientation of the liquid crystal when applying voltage, in 1 pair of polarization plates of the outside of two transparency carriers configuration, control optical transmission and block, thus display image.Like this, because the liquid crystal cell structure of TN pattern is fairly simple, can easily make, therefore, the TN mode liquid crystal panel and the TN mode LCD that are assembled with it are mainly used in the monitor purposes that personal computer is used.

But described TN mode LCD has for example following shortcoming: from oblique when watching picture, the viewing angle characteristic that contrast sharply reduces or gray-scale inversion that brightness and tone take place etc. is oblique is poor.

Therefore, in order to improve the shortcoming of described TN mode LCD, the optical compensation films that known use makes the discotic mesogenic orientation form under given conditions.For example, in Japanese kokai publication hei 7-191217 communique, disclose: on the transparent supporting body, be specially on the three cellulose acetate membrane, make the discoid compound orientation of discotic mesogenic and so on, make its optical axis from tilt 5～50 ° optical anisotropic device (optical compensation films) of the normal direction of film in uniaxiality mode negative on the optics thus, itself and polarizer combination are made the elliptic polarization plate.In recent years, such optical compensation films is widely used in the TN mode LCD.

But above-mentioned existing optical compensation films is owing to being base material with the three cellulose acetate membrane, and therefore, the change in size under hot environment is big, sometimes poor heat resistance.Therefore, in the liquid crystal indicator that uses this optical compensation films, exist the end be exposed to back liquid crystal display picture under the hot environment to produce the such problem of light leak, in addition, exist its brightness and contrast can not fully tackle the situation of display quality of the market demands of High Level.

Summary of the invention

The objective of the invention is to, even the composite polarizing plate of light leak also can be provided after providing a kind of liquid crystal indicator to be exposed under the hot environment and use the TN mode liquid crystal panel of this polarization plates.

In addition, the present invention also aims to, a kind of TN mode liquid crystal panel is provided, it is used to make the liquid crystal indicator of excellent heat resistance under the hot environment, horizontal contrast visual angle broadness.

Composite polarizing plate of the present invention is the phase retardation film of the biaxiality that stacks gradually protective clear layer, polaroid, be made of olefine kind resin and the composite polarizing plate that adhesive phase forms, the described biaxiality phase retardation film that constitutes by olefine kind resin in will be with the face of the light measurement of wavelength 590nm in slow-axis direction, the face refractive index of quick shaft direction and thickness direction be set at n respectively _x, n _yAnd n _zThe time, phase difference value R in the face of following formula (I) definition ₀Be 40～150nm, the phase difference value R of the thickness direction of following formula (II) definition _ThBe 50～250nm, the N of following formula (III) definition _zCoefficient is above 1 and below 7, and described adhesive phase is at 23～80 ℃ of energy storage elastic modulus that show 0.15～10MPa down.

R ₀＝(n _x-n _y)×d (I)

R _th＝[(n _x+n _y)/2-n _z]×d (II)

N _z＝(n _x-n _z)/(n _x-n _y)(III)

The present invention also provides a kind of TN mode liquid crystal panel that is fitted with above-mentioned composite polarizing plate on the two sides of TN mode liquid crystal unit by described adhesive phase.

In the composite polarizing plate of the present invention, as its optical compensation films, substitute the compensate film that the discotic mesogenic orientation is formed that uses at present, the biaxiality phase retardation film of the specific phase range that employing is made of olefine kind resin, in addition, the adhesive phase that uses when fitting with liquid crystal cells adopts the bonding agent of viscoelastic property in specific scope.Thus, this composite polarizing plate can be suppressed at the change in size under the environment of high temperature.Therefore, use the liquid crystal panel of this composite polarizing plate to have following effect in the TN mode liquid crystal unit, that is, even do not produce light leak after using its TN mode LCD to be exposed under the hot environment yet and keep good display quality.

The present invention also provides a kind of TN mode liquid crystal panel; the composite polarizing plate that biaxiality phase retardation film that stacks gradually protective clear layer, polaroid, is made of olefine kind resin and adhesive phase form is layered on the two sides of TN mode liquid crystal unit in the mode of the described phase retardation film side in the described composite polarizing plate towards described liquid crystal cell side, the described biaxiality phase retardation film that constitutes by olefine kind resin in will be with the face of the light measurement of wavelength 590nm in slow-axis direction, the face refractive index of quick shaft direction and thickness direction be set at n respectively _x, n _yAnd n _zThe time, phase difference value R in the face of following formula (I) definition ₀Be 40～150nm, the phase difference value R of the thickness direction of following formula (II) definition _ThBe 50～250nm, the N of following formula (III) definition _zCoefficient is surpassing 1 and be below 7,

R ₀＝(n _x-n _y)×d (I)

R _th＝[(n _x+n _y)/2-n _z]×d (II)

N _z＝(n _x-n _z)/(n _x-n _y)(III)

And phase difference value is set at R in the face of described liquid crystal cells when nothing applies voltage _cThe time, satisfy following formula (1) and (2).

0.13＜R ₀/R _c≤0.34(1)

0.17≤R _th/R _c＜0.54(2)

Thus, can provide a kind of excellent heat resistance, the horizontal wide TN mode liquid crystal panel in contrast visual angle under hot environment.

For TN mode liquid crystal panel of the present invention, described phase retardation film preferably is made of the cyclic olefin resinoid.

In addition; for TN mode liquid crystal panel of the present invention, the described protective clear layer of the composite polarizing plate of preferred disposition at least one face of described liquid crystal cells is made of the thickness with 20～50 μ m that is stretched, polyethylene terephthalate film with turbidity value of 0.1～40%.

The described protective clear layer of the composite polarizing plate of TN mode liquid crystal panel preferred disposition of the present invention on the one side of described liquid crystal cells has the thickness of 15～25 μ m by not stretching cyclic olefin resin film constitutes.

In addition, preferred described polaroid of TN mode liquid crystal panel of the present invention and described protective clear layer and/or described polaroid and described phase retardation film utilize the epoxies bonding agent of no-solvent type to carry out bonding.Under this situation, the epoxies bonding agent of described no-solvent type preferably solidifies by the cationic polymerization that the irradiation active energy beam carries out.

The following detailed description of understanding by being associated with accompanying drawing that the present invention relates to, above-mentioned purpose of the present invention and other purpose, feature, aspect and advantage are with more than you know.

Description of drawings

Fig. 1 is the exploded perspective view that schematically shows the TN mode liquid crystal panel of the composite polarizing plate that uses a preferred example of the present invention.

Fig. 2 is the constructed profile that is used to illustrate the liquid crystal panel at horizontal contrast visual angle.

Embodiment

Below, with reference to accompanying drawing embodiments of the present invention are elaborated as required.

[composite polarizing plate]

Fig. 1 is the exploded perspective view that schematically shows the TN mode liquid crystal panel 1 of the composite polarizing plate 2 that uses a preferred example of the present invention.Composite polarizing plate 2 of the present invention is made of protective clear layer 4, polaroid 3, phase retardation film 5 and adhesive phase 6.

[polaroid]

Polaroid 3 is made of polyvinyl alcohol resin, is the polaroid of using usually in this field.Particularly, thus can use polyvinyl alcohol resin absorption dichromatism pigment and dichromatism pigment orientation is given the rectilinearly polarized light that absorbs vibration plane and transmission to have straight line polaroid with the function of the rectilinearly polarized light of the vibration plane of its quadrature with certain direction.As the dichromatism pigment, use iodine and dichromatism organic dyestuff.Usually, the uniaxial tension by the polyvinyl alcohol resin film, utilize dyeing that the dichromatism pigment carries out and the boric acid after the dyeing to handle, can obtain such polaroid.

[protective clear layer]

For the protective clear layer on the one side that is disposed at polaroid 34; be favourable as the normally used protective seam that constitutes by the resinoid film of the cellulose acetate that is representative of the protective seam of polaroid with Triafol T (TAC), cellulose diacetate for example all the time; in addition, can also be by being that the film of cyclic olefin resinoid of representative or the film of polypropylene-based resin, the film of acrylic resin, resin molding of polyethylene terephthalate class etc. constitute with the norbornene resin.When the polyethylene terephthalate resin film is used as protective clear layer 4, the thin layerization of employed liquid crystal panel can be tackled, in addition,, purposes such as vehicle mounted can be used for aptly because permanance improves, therefore preferred.

Polyethylene terephthalate is meant the above resin that is made of ethylene glycol terephthalate of 80 moles of % of repetitive.As other copolymer composition, for example can enumerate: m-phthalic acid, 4,4 '-dicarboxyl diphenyl, 4,4 '-benzophenonedicarboxylic acid, two (4-carboxyl phenyl) ethane, hexane diacid, decanedioic acid, 5-sodium sulfo isophthalate, 1, dicarboxylic acid compositions such as 4-dicarboxyl cyclohexane; Diol components such as the ethylene oxide adduct of propylene glycol, butylene glycol, neopentyl glycol, diglycol, cyclohexanediol, bisphenol-A, polyglycol, polypropylene glycol and polytetramethylene glycol.These dicarboxylic acid compositions, diol component can be used in combination as required.In addition, also can and with P-hydroxybenzoic acid, to hydroxycarboxylic acids such as '-hydroxyethoxy yl benzoic acids.The copolymer composition of like this other can also contain the compound that has amido link, ammonia ester bond, ehter bond, carbonic acid ester bond etc. on a small quantity.

As the manufacture method of polyethylene terephthalate, can adopt so-called direct polymerization, the dimethyl esters that makes terephthalic acid (TPA) and ethylene glycol that terephthalic acid (TPA) and ethylene glycol are directly reacted to carry out the whole bag of tricks well known in the art such as so-called ester exchange reaction method of ester exchange reaction.In addition, as required, can contain known adjuvant.For example can contain lubricant, anticaking agent, thermal stabilizer, antioxidant, antistatic agent, photostabilizer, resistance to impact modifying agent etc.But owing to require the transparency in optical applications, therefore, the use level of adjuvant is preferably limited to Min..

The polyethylene terephthalate film when the protective clear layer 4, is preferably implemented uniaxial tension, stretching such as biaxial stretch-formed.

By being membranaceous with the above-mentioned raw materials ester moulding and implementing stretch processing, can make the polyethylene terephthalate film that stretched.Stretching can utilize along the uniaxial tension of MD direction (flow direction) or TD direction (with the direction of flow direction quadrature) stretching, not carry out along the arbitrary method such as oblique extension biaxial stretch-formed, that neither also do not stretch along the TD direction along the stretching of MD direction of MD direction and the stretching of TD direction both direction.By implementing such stretched operation, can obtain the high polyethylene terephthalate film of physical strength.The polyethylene terephthalate film that has carried out such stretching is being preferred aspect throughput rate and the intensity through biaxial stretch-formed polyethylene terephthalate film particularly, in addition, use the liquid crystal indicator of liquid crystal panel of the present invention that the trend that is difficult to produce the interference inequality is arranged, therefore preferred.

The method for making of the polyethylene terephthalate film of drawn is arbitrarily, for example, during for uniaxial tension, can enumerate following method: with the fusion of above-mentioned raw materials resin, the no alignment films that with extrusion molding is sheet is implemented the method that heat fixation is handled after carrying out cross directional stretch (stretching along the TD direction) with stenter under the temperature more than the glass temperature.Draft temperature is preferably 80～130 ℃, and more preferably 90～120 ℃, stretching ratio is preferably 2.5～6 times, more preferably 3～5.5 times.If stretching ratio is low, then the polyethylene terephthalate film has the trend that can not show the sufficient transparency.When biaxial stretch-formed, for example can enumerate following method: with extrusion molding is the no alignment films of sheet under the temperature more than the glass temperature longitudinally (MD) stretch the then method that stretches along laterally (TD), the perhaps method that stretches simultaneously along transverse and longitudinal etc.

The viewpoint of the deflection of the orientation main shaft from reduce the polyethylene terephthalate film is considered, preferably implement relaxation processes after stretching.For example when making monadic stretching membrane, can enumerate the method for behind cross directional stretch, carrying out implementing before heat fixation is handled relaxation processes by above-mentioned cross directional stretch.The temperature of relaxation processes is 90～200 ℃, is preferably 120～180 ℃.Slack is according to stretching condition and difference, and is preferred so that the percent thermal shrinkage of the film after the relaxation processes under 150 ℃ set slack and temperature in the mode below 2%.

The temperature that heat fixation is handled is generally 180～250 ℃, is preferably 200～245 ℃.Heat fixation is handled and preferably at first to be carried out processing under the said temperature condition with fixed length, and then is that the mode of 1～10% (preferred 2～5%) is handled with the lax ratio of the Width of film.It is below 10 degree that the polyethylene terephthalate film that the deflection of the orientation main shaft that obtains has thus reduced can make maximal value of the deflection of its orientation main shaft, and the maximal value of the deflection of this orientation main shaft is more preferably below 8 degree, more preferably below 5 degree.When the maximal value of the deflection of use orientation main shaft surpasses the polyethylene terephthalate film of 10 degree, when polarization plates therefrom is used for the liquid crystal panel of liquid crystal indicator, the big trend of painted bad change is arranged.The maximal value of the deflection of the orientation main shaft of above-mentioned polyethylene terephthalate film for example can use phase retardation film testing fixture " RETS system " (big tomb electronics (strain) system) to measure.

When the protective clear layer 4, its thickness is preferably in the scope of 20～50 μ m with the polyethylene terephthalate film.When the polyethylene terephthalate film of used thickness less than 20 μ m, the processing of film has the trend that becomes difficult, and on the other hand, when used thickness surpassed the polyethylene terephthalate film of 50 μ m, the advantage of thin-walled property weakened.

The polyethylene terephthalate film can be given turbidity and use in 0.1～40% scope, preferred turbidity value is 0.1～10%, more preferably 0.1～5% scope.Turbidity value is defined as the ratio of diffused transmission rate and total light transmittance as JIS K 7136 defineds, can measure with commercially available nephelometer.

As the method for giving polyethylene terephthalate film turbidity, for example can adopt following method: the method for in material resin polyethylene terephthalate film, mixing inorganic particles or organic fine particles; In resin binder (binder), be mixed with the method for the coating fluid of inorganic particles or organic fine particles in the surface coated of above-mentioned film.At this,, can enumerate typically: silicon dioxide, silica gel, aluminium oxide, alumina sol, alumina silicate, alumina silica composite oxides, porcelain earth, talcum, mica, lime carbonate, calcium phosphate etc. as inorganic particles.In addition, as organic fine particles, for example can enumerate: heat-resistant resin particles such as crosslinked polypropylene acid particles, crosslinked polystyrene particle, crosslinked polymethylmethacrylaparticles particle, silicone resin particle, polyimide particle.

Phase difference value R in the preferred face of polyethylene terephthalate film ₀More than 1000nm, more preferably more than the 3000nm.Phase difference value R in use face ₀During the polyethylene terephthalate film of not enough 1000nm, positive painted showy trend is arranged.Phase difference value R in the face of polyethylene terephthalate film ₀The upper limit be sufficient about 10000nm.

The polyethylene terephthalate film that possesses above-mentioned characteristic is in comprehensive excellences in aspect such as engineering properties, solvent resistance, scratch-resistant, costs.

Can on the polyethylene terephthalate film, give easy adhesive linkage.Easily adhesive linkage is meant the layer that is provided with for the cementability that improves polaroid and polyethylene terephthalate.This formation method of having given the polyethylene terephthalate film of easy adhesive linkage is not particularly limited, and for example can adopt following method: the method that forms easy adhesive linkage on the film of having finished whole stretching process; In the operation of stretching polyethylene terephthalate film, promptly between longitudinal stretching operation and cross directional stretch operation, form the method for easy adhesive linkage; Before bonding with polaroid or bonding back form the method etc. of easy adhesive linkage.When making biaxially-stretched film, consider, preferably adopt behind the longitudinal stretching polyethylene terephthalate, to form easy adhesive linkage, then carry out the method for cross directional stretch from the viewpoint of throughput rate.Can on the two sides of polyethylene terephthalate film or by bonding agent with the bonding one side of the polaroid that constitutes by polyvinyl alcohol resin on give easy adhesive linkage.

The composition that constitutes easy adhesive linkage for example can for: have polar group and molecular weight are lower, glass temperature is also lower polyester resin, polyurethanes resin, acrylic resin etc. in the skeleton.In addition, as required, also can contain crosslinking chemical, organic or inorganic filler, surfactant, lubricant etc.

For in the protective clear layer 4 and the opposite face bonding face of polaroid 3, can implement non-glare treated, be coated with and handle and surface treatments such as electrostatic prevention processing firmly.In addition, also can form the coating that constitutes by liquid crystal compounds or its high-molecular weight compounds etc.In addition, even replace the polyethylene terephthalate film to use poly (ethylene naphthalate) film, also can obtain effect much at one.

Such polyethylene terephthalate film can easily obtain commercially available product, for example can enumerate the following respectively commercially available product of trade name: Diafoil (Mitsubishi Plastics Inc's system), Hostaphan (Mitsubishi Plastics Inc's system), Fusion (Mitsubishi Plastics Inc's system), Supreme Being people Te Duolong film (film Co., Ltd. of Supreme Being people Du Pont system), Melinex (film Co., Ltd. of Supreme Being people Du Pont system), Mylar (film Co., Ltd. of Supreme Being people Du Pont system), teflex (film Co., Ltd. of Supreme Being people Du Pont system), ester film (Toyo Boseki K.K's system) spins in Japan, Espet film (Toyo Boseki K.K's system) spins in Japan, Cosmoshine (Toyo Boseki K.K's system), Crisper (Toyo Boseki K.K's system), RUMIRER (eastern beautiful film is processed Co., Ltd.'s system), EMBLON (Unitika Co., Ltd. system), Emblett (Unitika Co., Ltd. system), SkyRoll (SKC corporate system), コ one Off イ Le (Co., Ltd.'s high system of closing), Easthome's polyester film (STC Corp.'s system), pavilion polyester film (Futamura KCC system) etc. too.

In the present invention, the also preferred cyclic olefin resin film that does not stretch that uses of protective clear layer 4.So-called cyclic olefin resinoid is also referred to as amorphous polyolefins resinoid, ester ring type polyolefin resin, norbornene resin etc. usually.The unified in this manual cyclic olefin resin that is called.

When using the cyclic olefin resin film as protective clear layer 4, can help the thin layerization of liquid crystal panel, the permanance of this liquid crystal panel raises, and can be preferred for purposes such as vehicle mounted.When the cyclic olefin resin film was used as protective clear layer 4, its thickness was preferably in the scope of 15～25 μ m.During its thickness less than 15 μ m, it is difficult that the processing of film sometimes becomes.In addition, by making its thickness below 25 μ m, help thin layerization.

The protective clear layer 4 that is made of the cyclic olefin resinoid is that the transparency is excellent and to be orientated little be the little sheet material of phase differential.Particularly, for its transparency, total turbidity value of measuring according to JIS K 7136 is below 1%, to be preferably below 0.5%.Phase difference value is generally below the 5nm in the face, is preferably below the 3nm, and in addition, the phase difference value of thickness direction is generally below the 10nm, is preferably below the 5nm.

As the cyclic olefin resinoid, for example can enumerate: carry out ring-opening metathesis polymerization, and then carry out the resin that hydrogenation obtains as monomer with the norborene or derivatives thereof; (popular name: dimethylene octahydro naphthalene) or derivatives thereof carries out ring-opening metathesis polymerization, and then carries out the resin that hydrogenation obtains as monomer with tetracyclododecen; Use more than 2 kinds the cyclic olefin monomers that constitutes by norborene, tetracyclododecen, their derivant etc. to carry out ring-opening metathesis polymerization equally, and then carry out the copolymer resins that hydrogenation obtains; Make aforesaid cyclic olefin monomers and have the aliphatics of vinyl or aromatics carries out resin that copolymerization obtains etc. by addition polymerization.

Such cyclic olefin resinoid can easily obtain commercially available product, for example can enumerate the respectively following commercially available product of trade name: Topas (Topas Advanced Polymers GmbH system), Arton (JSR Corp.'s system), Zeonor (Japanese Zeon Co., Ltd. system), Zeonex (Japanese Zeon Co., Ltd. system), Apel (Mitsui Chemicals, Inc's system) etc.

The cyclic olefin resin film can be by being membranaceous obtaining with above-mentioned cyclic olefin ester moulding.With ester moulding is that membranaceous method is not particularly limited, the manufacturing process that can adopt any known is heating and melting forming process, solution casting method for example, but the viewpoint of residual volatile ingredient is considered from reduce film, the preferred heating and melting forming process that adopts, wherein special preferred molten extrusion molding method.

The condition that melt extrudes shaping is suitably selected according to the proterties and the manufacturing installation of employed resin, is not particularly limited, and for example preferably bowl temperature is set at about 100～600 ℃, more preferably is set at 150～350 ℃.

When making the cyclic olefin resin film, can in the scope that does not hinder purpose of the present invention, add adjuvant.As the adjuvant that can cooperate, for example can enumerate plastifier and anti aging dope etc.Plastifier adds for mechanical properties or the raising rate of drying that improves film.The example of concrete plastifier has phosphate and carboxylate.

As the phosphate that becomes plastifier, for example can enumerate triphenyl phosphate, tricresyl phosphate etc.In addition, as the carboxylate that becomes plastifier, for example can enumerate: repefral, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, and the phthalic ester of diphenyl phthalate and so on; The citrate of o-acetyl-triethyl citrate and adjacent tributyl 2-acetylcitrate and so on; The high-grade aliphatic ester of butyl oleate, castor oil acid methyl acetonyl ester and dibutyl sebacate and so on; Trimellitate etc.

As anti aging dope, for example can enumerate: antioxidant, peroxide decomposer, radical polymerization inhibitor, metal passivator, oxygen agent for capturing, amine etc.Concrete anti aging dope has the anti aging dope of record in Japanese kokai publication hei 3-199201 communique, Japanese kokai publication hei 5-197073 communique, Japanese kokai publication hei 5-194789 communique, Japanese kokai publication hei 5-271471 communique, Japanese kokai publication hei 6-107854 communique etc.

The use level of these adjuvants is generally below the 20 weight % with respect to the cyclic olefin resinoid, is preferably below the 10 weight %, more preferably below the 5 weight %.

The cyclic olefin resin film can be by selecting suitable known film formation device, uses the technique known selection suitable with the film forming condition of cyclic olefin resinoid as raw material, make in the mode that shows above-mentioned thickness, turbidity value and phase difference value.

[phase retardation film]

Another side at polaroid 3 is provided with the biaxiality phase retardation film 5 that is made of olefine kind resin.This phase retardation film 5 can obtain by stretching olefine kind resin film.So-called olefine kind resin film, be meant by use catalyst for polymerization make chain such as ethene and propylene olefinic monomer for example or with above-mentioned protective clear layer in dimethylene octahydro naphthalene) and cyclic olefin monomers polymerization such as their derivant and film that the resin that obtains constitutes identical norborene, the tetracyclododecen (popular name: that illustrates.The present invention especially preferably uses the cyclic olefin resinoid.When using the cyclic olefin resinoid, by using the cyclic olefin mixture of polymers of the cyclic olefin base polymer of positive wavelength dispersing characteristic and the long dispersing characteristic of head sea is carried out film that membranization and stretching make etc., the wavelength dispersion characteristic can be easily regulated, the phase retardation film of biaxiality can be easily obtained.

When the cyclic olefin resinoid is made phase retardation film 5, can use with above-mentioned transparent protective film in the same resin that illustrates.The cyclic olefin thickness of resin film that becomes the coiled strip of phase retardation film can be according to the suitably decisions such as application target of the stretched film that obtains, be not particularly limited, for example consider from the viewpoint that obtains uniform stretched film by stable stretch processing, be preferably more than the 10 μ m, more preferably more than the 20 μ m, be preferably especially more than the 30 μ m.In addition, the cyclic olefin thickness of resin film is preferably below the 300 μ m, more preferably below the 200 μ m, more preferably below the 100 μ m, is preferably especially below the 80 μ m.

The unstretching film that uses the olefine kind resin making is by carrying out can making the phase retardation film of biaxiality along its vertically (MD) and the laterally stretching of (TD) successively or simultaneously.This moment the stretching main shaft, be that the big direction of stretching ratio both can be also can be Width vertically, when the stretching main shaft is set at Width, can obtain rectangular and wide phase retardation film.

Temperature during the stretching unstretching film is when being made as Tg with the glass temperature of olefine kind resin, preferably in the scope of Tg-30 ℃～Tg+60 ℃, more preferably in the scope of Tg-10 ℃～Tg+50 ℃.In addition, stretching ratio preference such as following setting: for the stretching ratio separately that vertically reaches Width, from 1.01～30 times, preferred 1.01～10 times, more preferably select 1.01～5 times the scope, and the stretching ratio of stretching main shaft (preferred aforesaid Width) is than big with the stretching ratio of the direction of its quadrature.

The phase retardation film that is made of the olefine kind resin film can easily obtain commercially available product, during the example of illustration cyclic olefin resin film, can enumerate the following respectively commercially available product of trade name: Zeonor film (Japanese Zeon Co., Ltd. system), Arton film (JSR Corp.'s system), エ ス シ one Na phase retardation film (ponding chemical industry (strain) system) etc.

Phase difference value to phase retardation film 5 describes.The refractive index of slow-axis direction in the face of film is set at n _x, the refractive index of quick shaft direction (with the direction of slow axis quadrature in face) is set at n in the face _y, thickness direction refractive index be set at n _z, when thickness setting is d, phase difference value R in the face ₀, thickness direction phase difference value R _Th, and N _zCoefficient is used following formula (I), (II) and (III) definition respectively

R ₀＝(n _x-n _y)×d (I)

R _th＝[(n _x+n _y)/2-n _z]×d (II)

N _z＝(n _x-n _z)/(n _x-n _y)(III)

In addition, from these formulas (I), (II) and (III) can draw N _zPhase difference value R in coefficient and the face ₀And the phase difference value R of thickness direction _ThRelation can represent with following formula (IV).

N _z＝R _th/R ₀+0.5?(IV)

Among the present invention, from the phase differential of compensation TN mode liquid crystal unit, particularly enlarge the viewpoint at the horizontal visual angle of picture, use the phase retardation film of biaxialities as phase retardation film 5.At this, so-called biaxiality is meant three axial refractive index ns of above-mentioned definition _x, n _yAnd n _zSatisfy n _x＞n _y＞n _zRelation.Phase difference value R in the face of phase retardation film 5 ₀Be 40～150nm, be preferably 60～130nm.In addition, the phase difference value R of the thickness direction of phase retardation film 5 _ThBe 50～250nm, be preferably 100～200nm.In addition, N _zCoefficient surpasses 1 and be below 7, and more preferably 1.5～4.

The thickness of the phase retardation film that is made of olefine kind resin is generally 10～100 μ m, is preferably 20～80 μ m.During thickness less than 10 μ m, there are situations such as the property handled reduction.

In addition, this phase retardation film preferably is controlled at its residual volatile ingredient below 1000 ppm by weight, more preferably is controlled at below 500 ppm by weight, further preferably is controlled at below 200 ppm by weight.When residual volatile ingredient surpassed 1000 ppm by weight, described volatile ingredient was discharged into the outside during use, and the size of phase retardation film can change, and produced internal stress.Therefore, when being made composite polarizing plate and being applied in the liquid crystal indicator by the many phase retardation films of so residual volatile ingredient, the black display part attenuation (can see and turning white) of generation sometimes etc. shows inhomogeneous.If use the phase retardation film of volatile component content in above-mentioned scope, even then use liquid crystal indicator for a long time, do not show yet inhomogeneous etc., the excellent in stability of optical characteristics.

Also preferred its saturated water absorption of this phase retardation film is below the 0.01 weight %.If saturated water absorption surpasses 0.01 weight %, then according to the difference of environment for use sometimes the size of phase retardation film change, produce internal stress.Therefore, when being made composite polarizing plate and being applied in the liquid crystal indicator by the high phase retardation film of such saturated water absorption, the black display part attenuation (can see and turning white) of generation sometimes etc. shows inhomogeneous.If use the phase retardation film of saturated water absorption in above-mentioned scope, even then use liquid crystal indicator for a long time, do not show yet inhomogeneous etc., the excellent in stability of optical characteristics.

[polaroid and protective clear layer and phase retardation film bonding]

In the time of will being adhered to polaroid 3 by the phase retardation film 5 that the olefine kind resin film constitutes, both axles close on the basis tie up to the viewing angle characteristic considered in the target liquid crystal indicator, change color characteristic suitably to be selected to get final product.With in the panel use, the absorption axes of the slow axis of phase retardation film 5 and polaroid 3 is many to be configured in mode parallel or the almost relation of quadrature almost at TN.At this, so-called almost parallel or " almost " of quadrature almost is meant with the relation (being parallel or quadrature at this moment) in this record to be to allow about misalignment ± 10 °.Departing from preferably in ± 5 °, more preferably in ± 2 ° of this angle.

In the purposes that TN mode liquid crystal panel is used, when the axis of homology of polarization plates and the frictional direction of liquid crystal cells overlap, be defined as the E pattern; When the axis of homology of polarization plates is vertical with the frictional direction of liquid crystal cells, be defined as the O pattern.In the present invention, in order to make the viewing angle characteristic excellence, the O pattern of the frictional direction quadrature of the E pattern that the frictional direction of the axis of homology of composite polarizing plate 10 and liquid crystal cells 50 overlaps, the axis of homology of composite polarizing plate 10 and liquid crystal cells 50 all can be used.In order to obtain more excellent viewing angle characteristic, preferably use the O pattern.

When protective clear layer 4 and polaroid 3 bonding or the phase retardation film 5 that is made of olefine kind resin and polaroid 3 are bonding; for example can use with epikote, polyurethanes resin, cyanoacrylate resin, acrylamide resinoid etc. be as the bonding agent of composition, uses in these any can obtain good bonding force.As preferred bonding agent can be enumerated the no-solvent type bonding agent from making the thin viewpoint of bond layer, be specially by heating or irradiation energy ray to make monomer or oligomer reaction be solidified to form the bonding agent of bond layer.

Bonding agent to no-solvent type describes.The bonding agent of so-called no-solvent type does not contain the solvent of significant quantity, comprises usually based on the curable compound of heating or irradiation energy ray polymerization and polymerization initiator to constitute.From reactive viewpoint, the preferred bonding agent that is cured by cationic polymerization especially preferably uses the bonding agent of epoxies.

As preferred example, can enumerate protective clear layer 4 and polaroid 3 or come bonding mode by the epoxies bonding agent of no-solvent type respectively by phase retardation film 5 and polaroid 3 that olefine kind resin constitutes.This bonding agent more preferably solidifies based on heating or the cationic polymerization of irradiation energy ray.Particularly from viewpoints such as weatherability and refractive indexes, the epoxy compound that does not contain aromatic rings in the molecule is preferably used as the curable compound.Use the bonding agent that does not contain the epoxy compound of aromatic rings in the molecule for example to be recorded in the TOHKEMY 2004-245925 communique.As such epoxy compound that does not contain aromatic rings, hydride that can the illustration aromatic epoxy compound, alicyclic epoxy compound, aliphatic epoxy compound etc.The epoxy compound of the curable of using in the bonding agent contains 2 above epoxy radicals usually in molecule.

The hydride of aromatic epoxy compound can be by carrying out selective hydrogenation with the aromatic polyhydroxy compounds of the raw material of aromatic epoxy compound on aromatic rings under the existence of catalyzer, pressurized conditions, and the nuclear hydrogenation polyol that will obtain thus carries out glycidyl ether and obtains.As the raw material aromatic polyhydroxy compounds of aromatic epoxy compound, for example can enumerate: the bisphenols of bisphenol-A, Bisphenol F and bisphenol S and so on; The novolac resin of phenol novolac resin, cresols novolac resin and hydroxy benzaldehyde phenol novolac resin and so on; Tetrahydroxy diphenyl methane, tetrahydroxybenzophenone, and the compound of the multifunctional type of polyvinylphenol and so on etc.By hydride and the epichlorohydrin reaction that makes such aromatic polyhydroxy compounds, can glycidyl ether.As preferred hydride in the hydride of aromatic epoxy compound, can enumerate the diglycidyl ether of the bisphenol-A of hydrogenation.

The alicyclic epoxy compound is shown below, for have in the molecule at least 1 directly be combined on the ester ring type ring (compound O-), here, m represents 2～5 integer.

Removed (the CH in one or more these formulas ₂) _mIn the group of hydrogen atom and the compound of other chemical constitution bonding can form the alicyclic epoxy compound.In addition, the hydrogen of formation ester ring type ring can suitably be replaced by straight chained alkyls such as methyl and ethyls.Wherein, the preferred compound that uses with cyclopentane epoxide ring (m=3 in the following formula) and 7-oxa-bicyclo[4.1.0 ring (m=4 in the following formula).As the concrete example of alicyclic epoxy compound, can enumerate following compound.

3,4-epoxycyclohexyl methyl 3,4-epoxycyclohexane carboxylate

3,4-epoxy-6-methyl cyclohexane ylmethyl 3,4-epoxy-6-methylcyclohexanecarboxylic acid ester

Ethene two (3, the 4-epoxycyclohexane carboxylate)

Two (3,4-epoxycyclohexyl methyl) adipate

Two (3,4-epoxy-6-methyl cyclohexane ylmethyl) adipate

Diethylene glycol bis-(3,4-epoxycyclohexyl methyl ether)

Ethylene glycol bis (3,4-epoxycyclohexyl methyl ether)

2,3,14,15-diepoxy-7,11,18,21-four oxa-s three spiral shells-[5.2.2.5.2.2] heneicosane (also can called after 3,4-7-oxa-bicyclo[4.1.0 volution-2 ', 6 '-dioxo spiro-3 ", 5 "-dioxo spiro-3 " compound of ', 4 " '-7-oxa-bicyclo[4.1.0)

4-(3, the 4-epoxycyclohexyl)-2,6-two oxa-s-8,9-epoxy volution [5.5] undecane

The 4 vinyl cyclohexene dioxide

1,2:8,9-diepoxy citrene

Two-2,3-epoxide ring amyl ether

The bicyclopentadiene dioxide

The aliphatic epoxy compound can be the polyglycidyl ether of aliphatic polyol or its epoxy alkylidene addition product.For example can enumerate: by 1, the diglycidyl ether of 4-butylene glycol, 1, diglycidyl ether, ethylene glycol or the polypropylene glycol of the triglycidyl ether of the diglycidyl ether of 6-hexanediol, the triglycidyl ether of glycerine, trihydroxy methyl propyl ester, the diglycidyl ether of polyglycol, polypropylene glycol, and aliphatic polyol such as glycerine in the polyglycidyl ether etc. of one or more epoxyalkane of addition (oxirane, epoxypropane) and the polyether glycol that obtains.

Here illustrative epoxy compound both can have been distinguished use separately, also can be also with different multiple compounds.

The epoxide equivalent of the epoxy compound that uses in the bonding agent of no-solvent type is generally 30～3000g/ equivalent, is preferably 50～1500g/ equivalent.If epoxide equivalent is not enough 30g/ equivalent, the flexible reduction of the diaphragm after then existence is solidified or the situation that bonding strength reduces.On the other hand, if the situation that epoxide equivalent above the 3000g/ equivalent, then exists and the intermiscibility of other composition reduces.

For epoxy compound is solidified, cooperate cationic polymerization initiators.Cationic polymerization initiators produces kation kind or lewis acid by irradiation luminous ray, ultraviolet ray, X ray and electron beam isoreactivity energy-ray or heating, causes the polyreaction of epoxy radicals.From the viewpoint of operation, preferably give potentiality to the cationic polymerization initiators of any kind.

Below, the light cationic polymerization initiators is described.When making with the light cationic polymerization initiators, just can solidify at normal temperatures, necessity of the thermotolerance of consideration polaroid or the distortion that caused by expansion can reduce, can phase retardation film and polaroid is bonding well.In addition, because the light cationic polymerization initiators carries out catalytic action by light, therefore, even be blended in the epoxy compound, storage stability and operation are also excellent.As producing kation kind or lewis acidic compound, for example can enumerate: the aromatic series diazo salt by the irradiation active energy beam; Salt such as aromatic series salt compounded of iodine and aromatic series sulfonium salt; Iron-propadiene complex compound etc.Wherein,, the curable excellence can be provided and have excellent mechanical intensity and the solidfied material of bonding strength because near the wavelength region may of aromatic series sulfonium salt 300nm shows the UVA characteristic, therefore preferred especially.

The light cationic polymerization initiators can easily obtain commercially available product, for example can enumerate the following respectively commercially available product of trade name: KAYARAD PCI-220 (Japanese chemical drug (strain) system), KAYARAD PCI-620 (Japanese chemical drug (strain) system), UVI-6990 (Union Carbide Corporation's system), Adeka optomer SP-150 ((strain) ADEKA system), Adeka optomer SP-170 ((strain) ADEKA system), CI-5102 (Japanese Cao Da (strain) system), CIT-1370 (Japanese Cao Da (strain) system), CIT-1682 (Japanese Cao Da (strain) system), CIP-1866S (Japanese Cao Da (strain) system), CIP-2048S (Japanese Cao Da (strain) system), CIP-2064S (Japanese Cao Da (strain) system), DPI-101 ((strain) system is learned in greening), DPI-102 ((strain) system is learned in greening), DPI-103 ((strain) system is learned in greening), DPI-105 ((strain) system is learned in greening), MPI-103 ((strain) system is learned in greening), MPI-105 ((strain) system is learned in greening), BBI-101 ((strain) system is learned in greening), BBI-102 ((strain) system is learned in greening), BBI-103 ((strain) system is learned in greening), BBI-105 ((strain) system is learned in greening), TPS-101 ((strain) system is learned in greening), TPS-102 ((strain) system is learned in greening), TPS-103 ((strain) system is learned in greening), TPS-105 ((strain) system is learned in greening), MDS-103 ((strain) system is learned in greening), MDS-105 ((strain) system is learned in greening), DTS-102 ((strain) system is learned in greening), DTS-103 ((strain) system is learned in greening), PI-2074 (Rhodia corporate system) etc.

The use level of light cationic polymerization initiators is generally 0.5～20 weight portion with respect to epoxy compound 100 weight portions, is preferably 1～15 weight portion.

And then, as required, can and use photosensitizer.By using photosensitizer, the reactive raising can be improved the physical strength and the bonding strength of solidfied material.As photosensitizer, for example can enumerate: carbonyls, organosulfur compound, persulfide, redox compounds, azo and diazo-compounds, halogenide and photo-reduction pigment etc.When cooperating photosensitizer, its amount is generally about 0.1～20 weight portion when being 100 weight portions with the cationically photopolymerizable composition epoxy resin.

Next, hot cationic polymerization initiators is described.As producing kation kind or lewis acidic compound, can enumerate: benzyl sulfonium salt, thiophene salt, thiophane salt, hexadecyldimethyl benzyl ammonium, pyridiniujm, hydrazonium salt, carboxylate, sulphonic acid ester and amine acid imide etc. by heating.Hot cationic polymerization initiators also can easily obtain commercially available product, for example can enumerate trade name following commercially available product: Adeka opton CP77 ((strain) ADEKA system), Adeka opton CP66 ((strain) ADEKA system), CI-2639 (Japanese Cao Da (strain) system), CI-2624 (Japanese Cao Da (strain) system), San-Aid SI-60L (three new chemical industry (strain)), San-Aid SI-80L (three new chemical industry (strain)), San-AidSI-100L (three new chemical industry (strain)) etc. respectively.

Can and use light cationic polymerization and hot cationic polymerization.The epoxies bonding agent can further contain the compound that oxetanes class and polyalcohols etc. promote cationic polymerization.

The bonding agent that uses the above-mentioned curing type that comprises epoxies is with polaroid and protective clear layer or polaroid and phase retardation film when bonding; usually adopt be coated with this bonding agent, and fit by two bonding films and method that bonding agent is solidified by this bonding agent coating layer by the one side at least of bonding plane.Also can fit simultaneously protective clear layer and phase retardation film and it is solidified simultaneously from the two sides of polaroid.On by bonding plane during coating adhesive, for example can adopt to comprise the various coating methods that scraper, line rod, mould are coated with machine, comma coating machine and intaglio plate coating machine etc.In addition, because each coating method has optimal separately range of viscosities, therefore, can use a spot of solvent to carry out the viscosity adjustment.The solvent of Shi Yonging gets final product for the optical property that does not make polaroid reduces the solvent that can be dissolved in the epoxies bonding agent well for this reason, for example can use with toluene as the hydro carbons of representative, with the organic solvents such as ester class of ethyl acetate as representative.When using the epoxies bonding agent of no-solvent type, the thickness of bond layer is generally below the 50 μ m, more preferably below the 20 μ m, more preferably below the 10 μ m, is generally in addition more than the 1 μ m.

By uncured bond layer behind applying protective clear layer and/or phase retardation film on the polaroid, irradiation active energy beam or heating are solidified the epoxies bond layer, and protective clear layer and/or phase retardation film are fixed on the polaroid.When carrying out on polaroid bonding protective clear layer and bonding phase retardation film respectively, repeat these operations.When being cured by the irradiation active energy beam, preferred use ultraviolet ray.As concrete ultraviolet light source, for example can enumerate low pressure mercury lamp, medium pressure mercury lamp, high-pressure sodium lamp, black lamp, metal halide lamp etc.Active energy beam, particularly ultraviolet irradiation intensity and exposure are so that polymerization initiator fully activates and the mode that the bond layer after solidifying or polaroid, phase retardation film and protective clear layer do not produce bad influence is suitably selected to get final product.In addition; when being cured by heating; generally can adopt known method to heat, the temperature and time of this moment is also so that polymerization initiator fully activates and the mode that the bond layer after solidifying and polaroid, phase retardation film and protective clear layer do not produce bad influence is suitably selected to get final product.

In addition, as operable other preferred bonding agent among the present invention, can enumerate the water system bonding agent, promptly the be dissolved in the water bonding agent that forms or its of bonding agent composition is dispersed in the bonding agent that forms in the water.If use the water system bonding agent, then can make the thickness of bond layer littler.As the bonding agent composition of water system bonding agent, for example can enumerate the bonding agent that contains water-soluble cross-linked epoxy resin or soluble polyurethane resinoid etc.

As water-soluble cross-linked epoxy resin, for example can enumerate: the daiamid epoxy resin that polyamide polyamine that the dicarboxylic acid reaction of the polyalkylene polyamine of diethylenetriamine and triethylene tetramine and so on and hexane diacid and so on obtains and epichlorohydrin reaction are obtained.As the commercially available product of such daiamid epoxy resin, Sumirez Resin 650 (firmly changing CHEMTEX (strain) sells), Sumirez Resin675 (firmly changing CHEMTEX (strain) sells) etc. are arranged.

When using water-soluble cross-linked epoxy resin as the bonding agent composition, in order further to improve coating and cementability, other water soluble resin such as preferred mixing pva resinoid.Polyvinyl alcohol resin can also be the modified polyvinylalcohol resinoid of carboxy-modified polyvinyl alcohol (PVA), acetoacetyl modified polyvinylalcohol, methylol modified polyvinylalcohol, amino modified polyvinyl alcohol (PVA) and so on except that partly-hydrolysed polyvinyl alcohol (PVA) and fully saponified polyvinyl alcohol (PVA).Wherein, preferably using the saponified of multipolymer of vinyl acetate and unsaturated carboxylic acid or its salt is carboxy-modified polyvinyl alcohol (PVA).In addition, said here " carboxyl " comprises-notion of COOH and salt thereof.

As commercially available preferred carboxy-modified polyvinyl alcohol (PVA), for example can enumerate: Kuraray Poval KL-506 (sale of (strain) Kuraray), Kuraray Poval KL-318 (strain) Kuraray sell), Kuraray Poval KL-118 (sale of (strain) Kuraray), Gohsenol T-330 (Japanese synthetic chemical industry (strain) sale), Gohsenol T-350 (Japanese synthetic chemical industry (strain) sale), DR-0415 (electrochemical industry (strain) sale), AF-17 (Japan Vam﹠amp; Poval (strain) sale), AP-17 (Japan Vam﹠amp; Poval (strain) sells) etc.

In containing the bonding agent of water-soluble cross-linked epoxy resin, can be with above-mentioned epoxy resin and other water soluble resin such as the polyvinyl alcohol resin that adds as required be dissolved in the water, prepare with the adhesive solution form.At this moment, water-soluble cross-linked epoxy resin preferably is set in the concentration of the scope about 0.2～2 weight portion with respect to 100 weight parts waters.In addition, when cooperating polyvinyl alcohol resin, its amount preferably with respect to 100 weight parts waters about 1～10 weight portion, preferably about 1～5 weight portion.

On the other hand, when use contains the resinoid water system bonding agent of polyurethane, as the example of suitable urethane resin, can enumerate the urethane resin of ionomer type, particularly polyesters ionomer type polyurethane resin.At this, so-called ionomer type is to import the material that a spot of ionic composition (hydrophilic component) is arranged in the urethane resin that constitutes skeleton.In addition, so-called polyesters ionomer type polyurethane resin is to have the urethane resin of polyester backbone and import the urethane resin that a spot of ionic composition (hydrophilic component) is arranged therein.This ionomer type polyurethane resin do not use emulsifying agent and directly in water emulsification form emulsion, therefore, be preferred as the bonding agent of water system.As the commercially available product of polyesters ionomer type polyurethane resin, Hydran AP-20 (DIC (strain) sale), Hydran APX-101H (DIC (strain) sale) etc. are for example arranged, any can both obtain with the form of emulsion.

With the urethane resin of ionomer type during as the bonding agent composition, the further preferred crosslinking chemical such as isocyanates that cooperates.The isocyanates crosslinking chemical is to have at least two isocyanos (compound NCO) in molecule, as its example, remove 2, the 4-toluene diisocyanate, phenylene vulcabond, 4, the 4-methyl diphenylene diisocyanate, 1, the 6-hexamethylene diisocyanate, beyond the polyisocyanate monomer of isophorone diisocyanate and so on, also have above-mentioned a plurality of molecular compound to add on the polyvalent alcohol that is formed in trimethylolpropane and so on and the adduct that obtains, 3 molecule diisocyanate partly form the isocyanuric acid ester body of 3 functional groups of isocyanurate ring with a terminal isocyano separately, 3 molecule diisocyanate partly carry out hydration with a terminal isocyano separately, ester modified body of polyisocyanate of decarboxylation and biuret body of forming and so on etc.As the commercially available isocyanates crosslinking chemical that can preferably use, for example can enumerate Ha イ De ラ Application ァ シ ス タ one C-1 (DIC sale) etc.

When use contains the aqueous adhesive of ionomer type polyurethane resin, from the viewpoint of viscosity and cementability, preferably make its dissolving or be dispersed in the water in the mode of 10～70 weight % and then preferred 20 weight %～50 weight % with the concentration of described urethane resin.When cooperating the isocyanates crosslinking chemical, be that mode about 5～100 weight portions is suitably selected with use level with respect to polyurethanes resin 100 weight portion isocyanates crosslinking chemicals.

When stating aqueous adhesive in the use, the bonding of the bonding or polaroid of polaroid and protective clear layer and phase retardation film can be fitted the two to carry out on the one side at least by the bonding plane of sticky object by this bonding agent is coated on.More specifically, can adopt be coated with the water system bonding agent on the bonding plane that coating methods such as machine, comma coating machine and intaglio plate coating machine are uniformly coated at least one film by scraper, line rod, mould after, on coated face, overlap another film and utilize roller etc. to fit, carry out again dry method.Drying for example can be carried out under the temperature about 60～100 ℃.In order further to improve cementability, after drying, preferably in for example slaking 1～10 day under the temperature about 30～50 ℃ of the temperature higher slightly than room temperature.

The epoxies bonding agent of above-mentioned water system bonding agent and above-mentioned no-solvent type is same, can be preferred for the applying of protective clear layer and polaroid or biaxiality phase retardation film and the applying of polaroid or the two the applying that is made of the olefine kind resin film.Can use with the two sides that is layered in polaroid on the bonding identical bonding agent of film, also can use different bonding agents, oversimplify and reduce the member of polarization plates in order to make manufacturing process, preferably use identical bonding agent.

[adhesive phase]

Composite polarizing plate of the present invention is laminated with adhesive phase 6 in the outside of the face that disposes phase retardation film.This adhesive phase is used for TN mode liquid crystal unit bonding.

Preventing under the situation of light leak that the bonding agent that constitutes this adhesive phase 6 preferably shows the energy storage elastic modulus of 0.15～10MPa under 23～80 ℃.Said in this instructions " showing the energy storage elastic modulus of 0.15～10MPa under 23～80 ℃ " is meant that the energy storage elastic modulus all is the value of above-mentioned scope under any temperature of this scope.The energy storage elastic modulus rises along with temperature usually and reduces gradually, therefore, when the energy storage elastic modulus under 23 ℃ and 80 ℃ is all in above-mentioned scope, can think the energy storage elastic modulus that shows above-mentioned scope under the temperature of this scope.

At this, so-called energy storage elastic modulus is the value that obtains by general Measurement of Dynamic Viscoelasticity.Promptly, be by sample being applied in time vibration distortion or stress, measure its stress that causes or thereby the value that the Measurement of Dynamic Viscoelasticity method of the mechanical property of this sample is obtained is determined in distortion, particularly, be that the stress (or distortion) that will produce is divided into and is in synchronous composition with the distortion (or stress) that applies and during with 2 ripples of the composition of 90 ° of phase deviations, by being in the elastic modulus that synchronous composition is obtained with the distortion that applies (or stress).This energy storage elastic modulus can use commercially available determination of viscoelasticity device for example to measure at the Measurement of Dynamic Viscoelasticity device shown in the aftermentioned embodiment (DVA-220IT instrumentation control (strain) system).In this Measurement of Dynamic Viscoelasticity device, circulation thermostat, electric heater, and various known temperature control equipments such as Peltier element can be suitably used in the temperature of sample control.In addition, for sample, usually apply 0.01～10% distortion or the stress of 0.001～10N with the vibration of 0.01～10Hz.And then usually, the stress of generation or distortion are measured in the linear areas of its stress-distortion.The energy storage elastic modulus of stipulating among the present invention applies 0.1% distortion with the vibration of 1Hz and records under design temperature.

The energy storage elastic modulus height of the common TN mode LCD or the employed bonding agent of blooming of its use is to the 0.1MPa, because the TN mode liquid crystal panel with horizontal contrast visual angle broadness is a purpose, therefore, can use the bonding agent of general energy storage elastic modulus, but the bonding agent that uses in the present invention is when preventing to produce light leak as purpose, and preferably its energy storage elastic modulus is aforesaid high value.By using the high energy storage elastic modulus of such demonstration is hard bonding agent, can remedy and place following time of hot environment or be placed on hot environment repeatedly and the deficiency of the cohesive force in low temperature environment following time, can suppress to follow the change in size of the contraction of the polaroid that produces this moment.Utilize this effect, the TN mode LCD that possesses the TN mode liquid crystal panel that uses composite polarizing plate of the present invention can keep good display quality.This energy storage elastic modulus for example can be for below the 5MPa or below the 2MPa.

As long as the bonding agent of the formation adhesive phase that uses among the present invention has desired each the characteristic (transparency of the bonding agent of blooming, permanance and re-workability etc.), and satisfy above-mentioned viscoelastic property, just there is no particular limitation for its constituent, the for example preferred acrylic adhesives that contains acrylic resin and crosslinking chemical that uses, described acryl resin are major component with (methyl) acrylate and also contain the acrylic monomer potpourri with a spot of functional group (methyl) acrylic monomers and carry out free radical polymerization form in the presence of polymerization initiator, glass temperature (Tg) is at the acrylic resin below 0 ℃.

At this, can use following formula as (methyl) acrylate of the major component of acrylic resin:

CH ₂=C (R ₁) COOR ₂Expression, in the formula, R ₁Expression hydrogen atom or methyl, R ₂The alkyl or the aralkyl of expression carbon number 1～14 constitute R ₂The hydrogen atom of alkyl or the hydrogen atom that constitutes aralkyl can be replaced by the alkoxy of carbon number 1～10.

In addition, (methyl) acrylic monomers with functional group contains hydroxyl, carboxyl, amino, epoxy radicals isopolarity functional group and an olefinic double bond (being generally (methyl) acryloyl group) at molecule.

Need to prove, in this manual, so-called " (methyl) acrylic acid ... ", be meant " acrylic acid ... " or " methacrylic acid ... "

When enumerating (methyl) acrylate as the major component of acrylic resin, R is for example arranged ₁Be H, R ₂Butyl acrylate and R for normal-butyl ₁Be H, R ₂Be 2-EHA of 2-ethylhexyl etc.In addition, when enumerating the concrete example of (methyl) acrylic monomers, for example,, (methyl) acrylic acid 2-hydroxyethyl ester is arranged as (methyl) acrylic monomers with hydroxyl with functional group; (methyl) acrylic monomers as having carboxyl has acrylic acid etc.And then, when making this acrylic resin, also can make the monomer minor amounts of copolymerized that has a plurality of (methyl) acryloyl group in the molecule, as its example, can enumerate 1,4-butylene glycol two (methyl) acrylate.

When making acrylic resin, above-mentioned (methyl) acrylate and (methyl) acrylic monomers with functional group both can only use each a kind of, also can and with multiple.In addition, also can be the acrylic resin combination with multiple (methyl) acrylate and the multipolymer with (methyl) acrylic monomers of functional group or cooperate in as the acrylic resin of multipolymer (methyl) acrylic monomers that other acryl resin for example contains functional group separately or the acrylic resin of multipolymer at this, thereby with the acrylic resin composition the made resinous principle as bonding agent.

The crosslinking chemical that is engaged in the acrylic adhesives can be isocyanate ester compound, epoxy compounds, metal complex compounds, aziridine compounds etc.Isocyanate ester compound is except that can (the form of compound NCO) self uses, using with forms such as the adduct that makes it to form with polyol reaction, its dimer, tripolymers to have at least two isocyanos in the molecule.When enumerating the concrete example of crosslinking chemical, as diisocyanate compound, the trimethylolpropane adduct of hexamethylene diisocyanate, the trimethylolpropane adduct of toluene diisocyanate etc. are arranged, how use in the mode that is dissolved in the solution in the organic solution such as ethyl acetate respectively.

The aforesaid propylene acid resin is dissolved in the organic solution such as ethyl acetate, further adds crosslinking chemical, form acrylic adhesives solution.In addition, in this acrylic adhesives solution, as required, can contain silane coupling agent, weather-proof stabilizing agent, tackifier, plastifier, softening agent, pigment, inorganic filler or the light diffusing particulate that constitutes by organic microballon etc.

The acrylic adhesives solution that obtains like this is coated on the stripping film usually, heats distillation in about 0.5～10 minute down at 60～120 ℃ and removes organic solvent, forms adhesive phase.After being fitted in this adhesive phase on the phase retardation film that constitutes above-mentioned composite polarizing plate, for example slaking 5～20 days under the atmosphere of 23 ℃ of temperature, humidity 65% is fully reacted crosslinking chemical and is got final product.

In addition, after obtaining adhesive phase on the stripping film, the stripping film of further fitting also can be supported on the independent sheet material of adhesive phase on the base materials such as diaphragm.At this moment, same, behind the applying stripping film, for example, crosslinking chemical is fully reacted in 23 ℃ of temperature, 65% time slaking of humidity 5～20 days.The independent sheet material of such bonding agent is fitted on the phase retardation film behind the stripping film that can peel off a side period in necessity when making composite polarizing plate and uses.

There is no particular limitation to give the method for the above-mentioned high energy storage elastic modulus of adhesive phase, for example can enumerate: cooperating with the oligomer of ammonia ester esters of acrylic acid, the monomer of polyfunctional acrylic ester class in the adhesive ingredients of above-mentioned explanation is the active energy ray-curable compound of typical example, the method that the irradiation energy ray makes it to solidify.When adopting this method, in the acrylic adhesives solution of above-mentioned explanation, further cooperate the active energy ray-curable compound in advance, it be coated on the stripping film, remove organic solvent after, the irradiation active energy beam makes it to solidify and gets final product.At this moment, the slaking that is used to crosslinking chemical is fully reacted of above-mentioned explanation both can be carried out before the irradiation active energy beam, also can carry out after irradiation, according to circumstances also can omit.

It is known giving the adhesive composition of high energy storage elastic modulus thus or it is coated on the sheet bonding agent that makes it on the stripping film to solidify and give high energy storage elastic modulus, can obtain from bonding agent manufacturer.In addition, for example in the open WO2009/069799 number open text in the world, show the example of several bonding agents of giving high energy storage elastic modulus like this.

The thickness of the adhesive phase that composite polarizing plate of the present invention uses is about 5～50 μ m.In addition, on phase retardation film, during the applying adhesive phase, can implement surface treatments such as corona treatment to the adhesive surface of phase retardation film or adhesive phase.

[TN mode liquid crystal unit and TN mode liquid crystal panel]

The TN mode liquid crystal unit 11 that uses among the present invention is the liquid crystal cells that use in the TN mode LCD, it is characterized in that, in inside, unit, to have twisted 90 ° state configuration nematic liquid crystal, it utilizes the optical activity of the rectilinearly polarized light of this liquid crystal phase of transmission to realize white the demonstration along thickness direction.

Phase difference value (R in the face of the TN mode liquid crystal unit 11 that uses among the present invention _c) preferably in the scope of 300～600nm, more preferably at 400～500nm, particularly preferably in 400～470nm.Here phase difference value is the value of not having when applying voltage in the face of said liquid crystal cells.

Composite polarizing plate of the present invention is applied to TN mode liquid crystal unit makes TN mode liquid crystal panel, and then when making liquid crystal indicator, constitute the biaxiality phase retardation film of composite polarizing plate and the phase difference value of TN mode liquid crystal unit and preferably satisfy following formula (1) and formula (2).

0.13＜R ₀/R _c≤0.34(1)

0.17≤R _th/R _c＜0.54(2)

At this, in the formula, R ₀, R _Th, R _cAs follows respectively.

R ₀(nm): phase difference value in the face of the biaxiality phase retardation film that constitutes by olefine kind resin

R _Th(nm): the phase difference value of the thickness direction of the biaxiality phase retardation film that constitutes by olefine kind resin

R _c(nm): phase difference value in the face the when nothing of liquid crystal cells applies voltage

Formula (1) is meant R ₀/ R _cGreater than 0.13 and be below 0.34, this value is preferably in 0.2～0.27 scope.In addition, formula (2) is meant R _Th/ R _cBe more than 0.17 and less than 0.54, this value is more preferably in 0.27～0.3 scope.These formulas are tried to achieve by experiment, and the viewpoint from horizontal visual angle enlarges preferably satisfies formula (1) and formula (2) simultaneously.When the relation of the phase difference value of biaxiality phase retardation film and TN mode liquid crystal unit did not satisfy above-mentioned formula, horizontal sometimes visual angle narrowed down.

With respect to TN mode liquid crystal unit 11, the form that disposes (absorption axes of polarization plates is parallel with the frictional direction of liquid crystal cell substrate) in the mode of the frictional direction quadrature of the axis of homology of polarization plates and liquid crystal cell substrate is defined as O pattern (Ordinary Mode), in addition, the mode that overlaps with the frictional direction of the axis of homology of polarization plates and the liquid crystal cell substrate form that disposes (the frictional direction quadrature of the absorption axes of polarization plates and liquid crystal cell substrate) is defined as E pattern (Extra Ordinary Mode).Here the frictional direction of said liquid crystal cell substrate is meant from visual side and observes liquid crystal cells, is 0 ° with the long side direction right side, is rotated counterclockwise the angle of 45 ° or 135 °.In TN mode liquid crystal unit, because nematic liquid crystal distortion is orientated for 90 °, therefore, the frictional direction of 2 liquid crystal cell substrates is staggered 90 °.

[liquid crystal indicator]

The side that Fig. 1 is illustrated in the TN mode liquid crystal panel 1 that possesses 2 composite polarizing plates 2 and TN mode liquid crystal unit 11 further disposes the example of back light unit 12.In this embodiment, be state separately though show each layer, in fact adjacent each layer connected airtight.In example shown in Figure 1, from the below with the arranged in order of back light unit 12/ composite polarizing plate 2/TN mode liquid crystal unit 11/ composite polarizing plate 2.

In liquid crystal indicator of the present invention, adopt O pattern that the axis of homology make the polaroid that constitutes composite polarizing plate disposes with the frictional direction quadrature of the substrate that is fitted with described composite polarizing plate of TN mode liquid crystal unit or the axis of homology that makes the polaroid of formation composite polarizing plate to overlap and the E pattern that disposes can obtain high display quality with the frictional direction of TN mode liquid crystal unit.In order to obtain more excellent viewing angle characteristic, preferably use the O pattern.

Composite polarizing plate 2 is made of adhesive phase 6/ phase retardation film 5/ polaroid 3/ protective clear layer 4.In composite polarizing plate, the slow axis 5a of phase retardation film 5 and the absorption axes 3a of polaroid 3 are orthogonality relations, the polaroid 3 of downside is that 45 ° mode disposes with the long side direction 11A of the relative TN mode liquid crystal of its absorption axes 3A unit 11, and the polaroid 3 of upside is that 135 ° mode disposes with its absorption axes 3A with respect to the long side direction 11A of TN mode liquid crystal unit 11.When being fitted on the TN liquid crystal cells, dispose to the mode of liquid crystal cells with phase retardation film 5 sides.

Below, embodiment is shown the present invention is carried out more specific description, but the present invention is not limited to these examples.In the example, part of expression use amount and content and % are weight standard just unless otherwise specified.Physical property measurement method in the following example is as follows.

[energy storage Determination of Modulus]

The energy storage elastic modulus of bonding agent is to measure according to the order of following (i)～(iii).

(i) from bonding agent, take by weighing 2 parts of respectively samples of 25 ± 1mg, be formed separately to slightly spherical.

(ii) the sample that obtains in above-mentioned (i) is bonded on the top and bottom of I type anchor clamps, top and bottom is all sandwiched in the L type anchor clamps make the mensuration sample.The formation of this mensuration sample is L type anchor clamps-bonding agent-I type anchor clamps-bonding agent-L type anchor clamps.

(iii) use Measurement of Dynamic Viscoelasticity device (DVA-220, IT instrumentation Heat ﹠ Control Pty Ltd. system), be warming up to 200 ℃ from-70 ℃, at the energy storage elastic modulus of measuring under the condition of frequency 1Hz under 23 ℃ and 80 ℃ of the mensuration sample made with the programming rate of 4 ℃/min.

[mensuration of the phase difference value of phase retardation film]

Use measuring difference of phases device KOBRA-WR (prince's instrumentation machine (strain) system), measure at wavelength 590nm place.

[mensuration of the phase difference value of liquid crystal cells]

Use transmission-absorption spectromtry device MCPD-1000 (Da mound electronics (strain) system), phase difference value in wavelength 400nm～1000nm place measures the face that does not have the liquid crystal cells that applies voltage status.

[mensuration of light leak amount]

Utilize cutting device Super cutter rpN16001 ((strain) reed wild smart mechanism do made) to block into 2 of big or small 237mm * 421nm the polarization plates of composite polarizing plate or comparative example.Utilize other method, decompose TN mode liquid crystal monitor (TN mode LCD) (CMV937A, CMO corporate system), from the TN mode liquid crystal panel that takes out, peel off the polarization plates of configuration, prepare TN mode liquid crystal unit.Measure this TN mode liquid crystal unit phase difference value R in nothing applies face under the voltage status _c, the result is 407nm.

In this TN mode liquid crystal unit outer, with the polaroid the fit polarization plates of composite polarizing plate described later or comparative example of the parallel mode of absorption axes of the frictional direction of substrate of orthogonal polarization microscope (Cross Nicol) state and TN mode liquid crystal unit and polaroid.Then, with autoclave (the former making of pressurized deairing device, (strain) chestnut is made), pressurization is 20 minutes under 0.5MPa, 50 ℃ condition, makes the evaluation of light leak amount with TN mode liquid crystal panel.

This TN mode liquid crystal panel left standstill 250 hours in 80 ℃ heated-air circulation oven after, the assembling LCD monitor also makes it work, be under 50% the environment at 23 ℃, relative humidity, use look measure of spread device Eye Scale 3W (Eye Scale corporate system) to measure the brightness of the periphery of the black display surface that shows of conduct from normal direction, deduct the brightness of central authorities by the high-high brightness on four limits, with the value that obtains as the light leak amount.

In addition, in following example, as bonding agent, the form to clamp with stripping film from the adhesive phase two sides that used thickness is 25 μ m forms sheet and sale and bonding agent that give energy storage elastic modulus shown below, after peeling off stripping film of its one side, applying phase retardation film or replace its film.

Acrylic adhesives A: give at 23 ℃ of following 0.30MPa, at the energy storage elastic modulus of 80 ℃ of following 0.18MPa.

Acrylic adhesives B: give at 23 ℃ of following 0.04MPa, at the energy storage elastic modulus of 80 ℃ of following 0.03MPa.

Acrylic adhesives C: give at 23 ℃ of following 0.11MPa, at the energy storage elastic modulus of 80 ℃ of following 0.06MPa.

＜embodiment 1 〉

The one side configuration three cellulose acetate membrane of the polaroid that absorption orientation iodine forms on polyvinyl alcohol (PVA) (KC8UX2MW, Konica Minolta (strain) system, thickness: 80 μ m), the phase retardation film that configuration is made of the cyclic olefin resinoid on its opposite face (Zeonor film, Japanese Zeon (strain) system, R ₀: 80nm, R _Th: 110nm, thickness: 40 μ m) make the absorption axes of polaroid and the slow axis quadrature of phase retardation film, use adhesive bonds separately.At this moment, after implementing Corona discharge Treatment under the condition of accumulative total exposure 1680J, coating epoxies ultraviolet hardening bonding agent is fitted with polaroid on phase retardation film and three cellulose acetate membrane bonding plane separately to the bonding plane side of phase retardation film.Then, use ultraviolet irradiation system (Fusion UV systems corporate system), under the condition of output power 300mW, exposure 300mJ,, bonding agent is solidified, obtain composite polarizing plate from cyclic olefin resin film side irradiation ultraviolet radiation.To the cyclic olefin resin film side of this composite polarizing plate after implementing Corona discharge Treatment under the condition of accumulative total exposure 1680J, applying acrylic adhesives A.

Use the composite polarizing plate of making like this, measure the light leak amount by said method, the result is 0.8cd/m ²In addition, phase difference value R in the face of phase retardation film ₀And thickness direction phase difference value R _ThPhase difference value R with liquid crystal cells _cRelation and N _zCoefficient is as follows.

R ₀/R _c＝0.20

R _th/R _c＝0.27

N _z＝1.9

＜embodiment 2 〉

Except that three cellulose acetate membrane is replaced with biaxial stretch-formed polyethylene terephthalate film (thickness: 38 μ m, turbidity: 2.3%) and embodiment 1 operate equally, make composite polarizing plate.Use is estimated the light leak amount by the TN mode liquid crystal monitor that the TN mode liquid crystal panel that is fitted with this composite polarizing plate constitutes, and the result is 1.0cd/m ²

＜comparative example 1 〉

Except that replacing with by the phase retardation film that the cyclic olefin resinoid constitutes orientation on the three cellulose acetate membrane is fixed with the compensation film for angular field of view (EA-WV film, Fujiphoto (strain) system) of discotic mesogenic and embodiment 1 operate the making composite polarizing plate equally.Use is estimated the light leak amount by the TN mode liquid crystal monitor that the TN mode liquid crystal panel that is fitted with this composite polarizing plate constitutes, and the result is 8.2cd/m ²

＜comparative example 2 〉

Except that will replace with by the phase retardation film that the cyclic olefin resinoid constitutes three cellulose acetate membrane (KC8UX2MW, Konica Minolta (strain) system, thickness: 80 μ m) and embodiment 1 operate the making polarization plates equally.Use is estimated the light leak amount by the TN mode liquid crystal monitor that the TN mode liquid crystal panel that is fitted with this polarization plates constitutes, and the result is 1.3cd/m ²

＜comparative example 3 〉

Remove will replace with by the phase retardation film that the cyclic olefin resinoid constitutes three cellulose acetate membrane (with use in the comparative example 2 identical, thickness is 80 μ m), acrylic adhesives A is replaced with beyond the acrylic adhesives B, operate equally with embodiment 1, make polarization plates.Use is estimated the light leak amount by the TN mode liquid crystal monitor that the TN mode liquid crystal panel that is fitted with this polarization plates constitutes, and the result is 3.7cd/m ²

＜comparative example 4 〉

Except that acrylic adhesives A being replaced with acrylic adhesives C and embodiment 1 operate equally, make composite polarizing plate.Use is estimated the light leak amount by the TN mode liquid crystal monitor that the TN mode liquid crystal panel that is fitted with this composite polarizing plate constitutes, and the result is 7.1cd/m ²

Main formation in above embodiment and the comparative example and result together are shown in table 1.

Table 1

In table 1, " TAC " in " protective clear layer " hurdle reaches " PET " and represents following resin respectively.

TAC: Triafol T

PET: polyethylene terephthalate

＜embodiment 3 〉

(a) making of composite polarizing plate

The one side configuration of the polaroid that absorption orientation iodine forms on polyvinyl alcohol (PVA) is as the Triafol T (KC8UX2MW, Konica Minolta (strain) system) of the thickness 80 μ m of protective clear layer, and the phase retardation film of the about 40 μ m of thickness that are made of the cyclic olefin resinoid in the opposite face configuration of polaroid (obtains from Japanese Zeon (strain); R ₀=80nm, R _Th=110nm), make composite polarizing plate.At this moment; at first the bonding plane side of phase retardation film is implemented Corona discharge Treatment under the condition of accumulative total exposure 1680J; then on the bonding plane of the bonding plane of this phase retardation film and the diaphragm that constitutes by Triafol T, be coated with epoxies ultraviolet hardening bonding agent respectively, fit with polaroid.Then, use the ultraviolet irradiation system of Fusion UV systems corporate system, under the condition of output power 300mW, exposure 300mJ,, bonding agent is solidified from phase retardation film side irradiation ultraviolet radiation.The adhesive phase by acrylic adhesives C (energy storage elastic modulus: at 23 ℃ of following 0.11MPa, at 80 ℃ of following 0.06MPa) formation of the about 15 μ m of thickness further is set in described phase retardation film side, obtains composite polarizing plate with bonding agent.The outside that is produced on adhesive phase is fitted with the composite polarizing plate of the band bonding agent of stripping film, and the thickness of the composite polarizing plate of the band bonding agent except that stripping film is 170.6 μ m.

(b) making of liquid crystal panel

The LCD TV " CMV937A " of decomposing the CMO system of the liquid crystal cells that possesses the TN pattern, unload liquid crystal panel, peel off the polarization plates on the two sides that is bonded in liquid crystal cells in this liquid crystal panel, instead, the polarization plates that the composite polarizing plate of the band bonding agent that will make from above-mentioned (a) has been peeled off stripping film all is fitted in (this configuration is called the O pattern) on the adhesive phase side with the mode of the frictional direction quadrature of liquid crystal cells with its axis of homology on the two sides, makes liquid crystal panel.The layer of this moment constitutes and axle concerns as shown in Figure 1.

Phase difference value is 410nm in the face of TN mode liquid crystal used herein unit.Therefore, phase difference value R in the face of the phase retardation film that constitutes by the cyclic olefin resinoid ₀And phase difference value R in the thickness direction face _ThWith phase difference value R in the face of TN mode liquid crystal unit _cThe pass be R ₀/ R _c=80/410=0.20, R _Th/ R _c=110/410=0.27.

(c) assembling of liquid crystal indicator and evaluation

Liquid crystal panel is transformed to panel of making in above-mentioned (b), all the other with decompose before the same state of LCD TV under assemble liquid crystal indicator.Make this liquid crystal indicator work, use the liquid crystal visual angle determinator " EZ Contrast 88XL " of ELDIM corporate system, measure the horizontal contrast of picture and be 100 angles when above.At this, the ratio of the brightness when brightness when contrast is white demonstration the and black the demonstration.In addition, the horizontal contrast of so-called picture is 100 angles when above, be meant in the diagrammatic cross-section of liquid crystal panel shown in Figure 2, with the normal direction 62 with respect to the display surface 61 of liquid crystal panel 60 is the center, with the determinator of contrast when the tilting of picture, in picture right side contrast is 100 o'clock direction and the direction angulation 63 that is at 100 o'clock in picture left side contrast, at this, the contrast the when position about picture two is divided into (vertically central portion) measured from the direction observation that picture tilts.The results are shown in table 2.In table 2, be that 100 angles when above are expressed as " visual angle that CR100 is above " with above-mentioned contrast.

＜embodiment 4 〉

As the phase retardation film that constitutes by the cyclic olefin resinoid, use R ₀Be 60nm, R _ThBe the film of 70nm, in addition and embodiment 3 operate equally, make liquid crystal panel, and then the assembling liquid crystal indicator is estimated.The results are shown in table 2.

＜embodiment 5 〉

As the phase retardation film that constitutes by the cyclic olefin resinoid, use R ₀Be 60nm, R _ThBe the film of 90nm, in addition and embodiment 3 operate equally, make liquid crystal panel, and then the assembling liquid crystal indicator is estimated.The results are shown in table 2.

＜embodiment 6 〉

As the phase retardation film that constitutes by the cyclic olefin resinoid, use R ₀Be 60nm, R _ThBe the film of 110nm, in addition and embodiment 3 operate equally, make liquid crystal panel, and then the assembling liquid crystal indicator is estimated.The results are shown in table 2.

＜embodiment 7 〉

As the phase retardation film that constitutes by the cyclic olefin resinoid, use R ₀Be 110nm, R _ThBe the film of 150nm, in addition and embodiment 3 operate equally, make liquid crystal panel, and then the assembling liquid crystal indicator is estimated.The results are shown in table 2.

＜embodiment 8 〉

As the phase retardation film that constitutes by the cyclic olefin resinoid, use R ₀Be 140nm, R _ThBe the film of 125nm, in addition and embodiment 3 operate equally, make liquid crystal panel, and then the assembling liquid crystal indicator is estimated.The results are shown in table 2.

＜embodiment 9 〉

As the phase retardation film that constitutes by the cyclic olefin resinoid, use R ₀Be 90nm, R _ThFilm for 130nm, and use the LCD TV " REGZA19A3500 " (phase difference value is 460nm in the face of the liquid crystal cells when nothing applies voltage) of (strain) Toshiba system of the liquid crystal cells that possesses the TN pattern, in addition, operate equally with embodiment 3, make liquid crystal panel, and then the assembling liquid crystal indicator is estimated.The results are shown in table 2.

＜embodiment 10 〉

Replace three cellulose acetate membrane, (maximal value of the distortion of orientation main shaft is 4.5 degree to the biaxial stretch-formed polyethylene terephthalate film of the about 38 μ m of used thickness, turbidity 2.3%, phase difference value R in the face ₀Be 2245nm), to this film with the bonding face side of polaroid after implementing Corona discharge Treatment under the condition of accumulative total exposure 1680J, coating adhesive in addition and embodiment 3 (a) same operation, is made the composite polarizing plate of band bonding agent.The thickness of the composite polarizing plate of this band bonding agent except that stripping film (containing adhesive phase) is 129.1 μ m.Except that using this composite polarizing plate and embodiment 3 (b) same operation, make liquid crystal panel, and then with embodiment 3 (c) same operation, the assembling liquid crystal indicator is estimated.The results are shown in table 2.

＜embodiment 11 〉

Replace three cellulose acetate membrane, the nothing orientation ring-type olefine kind resin film of the about 23 μ m of used thickness, turbidity 0% (obtains from Japanese Zeon (strain); Phase difference value R in the face ₀=1.3nm, thickness direction phase difference value R _Th=2.6nm), in addition and embodiment 3 (a) same operation, make the composite polarizing plate of band bonding agent.The thickness of the composite polarizing plate of this band bonding agent except that stripping film (containing adhesive phase) is 114.1 μ m.This composite polarizing plate is fitted in the dorsal part (backlight side) of liquid crystal cells, the composite polarizing plate of making among the embodiment 11 is fitted in the front side (look and recognize side) of liquid crystal cells, in addition, with embodiment 3 (b) same operation, make liquid crystal panel, and then with embodiment 3 (c) same operation, the assembling liquid crystal indicator is estimated.The results are shown in table 2.

＜comparative example 5 〉

The phase retardation film that replacement is made of the cyclic olefin resinoid, use is orientated the optical compensation films (" EA-WV " of Fujiphoto (strain) system) that is fixed with discotic mesogenic on three cellulose acetate membrane, in addition, operate equally with embodiment 3, make composite polarizing plate, and then the assembling liquid crystal indicator is estimated.The results are shown in table 2.

＜comparative example 6 〉

The phase retardation film that replacement is made of the cyclic olefin resinoid, used thickness is the three cellulose acetate membrane (Konica Minolta (strain) system " KC8UX2MW ") of 80 μ m, in addition and embodiment 3 operate equally, make liquid crystal panel, and then the assembling liquid crystal indicator is estimated.The results are shown in table 2.

＜comparative example 7 〉

As the phase retardation film that constitutes by the cyclic olefin resinoid, use R ₀Be 55nm, R _ThBe the film of 124nm, in addition and embodiment 3 operate equally, make liquid crystal panel, and make liquid crystal indicator evaluation.The results are shown in table 2.

＜comparative example 8 〉

As the phase retardation film that constitutes by the cyclic olefin resinoid, use R ₀Be 60nm, R _ThBe the film of 220nm, in addition and embodiment 3 operate equally, make liquid crystal panel, and then the assembling liquid crystal indicator is estimated.The results are shown in table 2.

Main formation in above embodiment 3～11 and the comparative example 5～8 and result together are shown in table 2.

Table 2

In table 2, " TAC " in " protective clear layer " hurdle, " PET " reach " COP " respectively

The resin that expression is following.

TAC: Triafol T

PET: polyethylene terephthalate

COP: cyclic olefin resinoid

＜embodiment 12 〉

The liquid crystal panel of making among the embodiment 3 is arranged in the heated-air circulation oven that temperature is set at 80 ℃ with standing.After 300 hours, take out this liquid crystal panel, be cooled to room temperature, be assembled into liquid crystal indicator and make it work.Making image is black the demonstration, observe, the result, on the picture all not discovery the place of light leak is arranged.

＜comparative example 9 〉

The liquid crystal panel and the embodiment 12 that make in the comparative example 5 are arranged in the heated-air circulation oven equally, take out, be cooled to room temperature, then be assembled into liquid crystal indicator and make it work through after the same time.Making image is black the demonstration, observes, and the result finds to have the place of light leak along 4 limits of picture.

Claims (8)

1. composite polarizing plate, biaxiality phase retardation film and adhesive phase that it stacks gradually protective clear layer, polaroid, be made of olefine kind resin obtain, wherein,

The described biaxiality phase retardation film that constitutes by olefine kind resin in will be with the face of the light measurement of wavelength 590nm in slow-axis direction, the face refractive index of quick shaft direction and thickness direction be set at n respectively _x, n _yAnd n _zThe time, phase difference value R in the face of following formula (I) definition ₀Be 40～150nm, the phase difference value R of the thickness direction of following formula (II) definition _ThBe 50～250nm, the N of following formula (III) definition _zCoefficient surpasses 1 and below 7,

Described adhesive phase shows the energy storage elastic modulus of 0.15～10MPa under 23～80 ℃,

R ₀＝(n _x-n _y)×d (I)

R _th＝[(n _x+n _y)/2-n _z]×d (II)

N _z＝(n _x-n _z)/(n _x-n _y)(III)。

2. TN mode liquid crystal panel, its on the two sides of TN mode liquid crystal unit by the described composite polarizing plate of described adhesive phase applying claim 1.

3. TN mode liquid crystal panel; wherein; the composite polarizing plate that biaxiality phase retardation film that stacks gradually protective clear layer, polaroid, is made of olefine kind resin and adhesive phase form is layered on the two sides of TN mode liquid crystal unit in the mode of the described phase retardation film side in the described composite polarizing plate towards liquid crystal cell side

The described biaxiality phase retardation film that constitutes by olefine kind resin in will be with the face of the light measurement of wavelength 590nm in slow-axis direction, the face refractive index of quick shaft direction and thickness direction be set at n respectively _x, n _yAnd n _zThe time, phase difference value R in the face of following formula (I) definition ₀Be 40～150nm, the phase difference value R of the thickness direction of following formula (II) definition _ThBe 50～250nm, the N of following formula (III) definition _zCoefficient surpasses 1 and be below 7,

R ₀＝(n _x-n _y)×d (I)

R _th＝[(n _x+n _y)/2-n _z]×d (II)

N _z＝(n _x-n _z)/(n _x-n _y)(III)

And phase difference value is set at R in the face of described liquid crystal cells when nothing applies voltage _cThe time, satisfy following formula (1) and (2),

0.13＜R ₀/R _c≤0.34(1)

0.17≤R _th/R _c＜0.54(2)。

4. TN mode liquid crystal panel as claimed in claim 3, wherein, described phase retardation film is made of the cyclic olefin resinoid.

5. TN mode liquid crystal panel as claimed in claim 3; wherein, the described protective clear layer that is configured in the composite polarizing plate at least one face of described liquid crystal cells is made of the thickness that is stretched and have 20～50 μ m, polyethylene terephthalate film with turbidity value of 0.1～40%.

6. TN mode liquid crystal panel as claimed in claim 3, wherein, the described protective clear layer that is configured in the composite polarizing plate on the one side of described liquid crystal cells has the thickness of 15～25 μ m by not stretching cyclic olefin resin film constitutes.

7. TN mode liquid crystal panel as claimed in claim 3, wherein, described polaroid and described protective clear layer and/or described polaroid and described phase retardation film utilize the epoxies bonding agent of no-solvent type to carry out bonding.

8. TN mode liquid crystal panel as claimed in claim 7, wherein, the epoxies bonding agent of described no-solvent type solidifies by the cationic polymerization based on the irradiation active energy beam.

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