CN1885070A - Coating liquid for coating a retardation film, retardation film and composite polarizing plate using the coating liquid and method for producing retardation film, and liquid crystal display device - Google Patents

Abstract

The invention provides a coating liquid containing an organic modified clay complex, being able to reduce the haze value when formed into a coating retardation film and to maintain a high contrast ratio of the liquid crystal display device. The coating liquid is formed into a retardation film and composite polarizing plate, and the composite polarizing plate is applied to a liquid crystal device. The invention also provides a coating liquid for coating a retardation film containing an organic modified clay complex and a binder resin in an organic solvent and having a moisture content in the range from 0.15 to 0.35% by weight as measured with a Karl Fischer moisture meter.

Description

Apply polarizer with applying liquid, the polarizer that uses it and composite polarizing plate, their manufacture method and liquid crystal indicator

Technical field

The present invention relates to apply polarizer with coating liquid, the polarizer that uses it and manufacture method, the composite polarizing plate that has used this polarizer and manufacture method thereof and the liquid crystal indicator that used this composite polarizing plate.

Background technology

In recent years, consumed power few, with low voltage drive, light weight and slim LCD as portable phone, carry information terminal, computing machine is promptly popularized with display device with information such as monitor, TVs.Be accompanied by the development of liquid crystal technology, proposed the LCD of pattern miscellaneous, the problem of the LCD at response speed or contrast, narrow visual angle and so on is eliminated gradually.But, compare with cathode ray tube (CRT), it is narrow still to be considered to the visual angle, in order to enlarge the visual angle, is carrying out various trials.

Improve one of liquid crystal display mode of viewing angle characteristic as this kind, for example developed the nematic phase type liquid crystal indicator (VA-LCD) of the vertical alignment mode as announcing in speciallyying permit No. 2548979 communique (patent documentation 1).Because this vertical alignment mode is under non-driven state, liquid crystal molecule vertically is orientated with respect to substrate, thus light do not follow polarisation variation pass liquid crystal layer.Thus, dispose the linear polarization plate mutually orthogonally, under situation about seeing, can obtain black completely the demonstration basically, thereby high contrast is provided from the front by the polarizing axis that makes up and down at liquid crystal panel.

But, this kind only possessed in liquid crystal cell in the liquid crystal indicator of vertical alignment mode of Polarizer, to it under the situation of oblique observation, because the shaft angle degree of the Polarizer that is disposed departs from 90 °, bar-shaped liquid crystal molecule in the box shows birefringence in addition, therefore will produce light leak, contrast reduces significantly.

In order to eliminate this kind light leak, need between liquid crystal cell and linear polarization plate, dispose optical compensating film, adopted following mode, that is in the past, between liquid crystal cell and Polarizer up and down, respectively dispose the mode of the polarizer of 1 biaxiality respectively; With the polarizer of uniaxiality and fully biaxiality polarizer liquid crystal cell respectively dispose 1 respectively up and down, or with 2 one-sided modes that all are configured in liquid crystal cell.For example, open in the 2001-109009 communique (patent documentation 2) the spy, record following content, promptly, in the liquid crystal indicator of vertical alignment mode, up and down between Polarizer and the liquid crystal cell, dispose a-plate (being the polarizer of positive uniaxiality) and c-plate (being the polarizer of complete biaxiality) respectively.

So-called positive uniaxiality polarizer is meant, the phase difference value R in the face ₀Ratio R with the phase difference value R ' of thickness direction ₀/ R ' is about 2 film, and in addition, the so-called polarizer of biaxiality fully is meant the phase difference value R in the face ₀Be about 0 film.Here, the refractive index of slow axis direction is made as n in the face of film _x, the refractive index of leading phase shaft direction in the face of film (with the direction of slow axis direction quadrature) is made as n _y, the refractive index of the thickness direction of film is made as n _z, and when the thickness of film is made as d, the phase difference value R in the face then ₀And the phase difference value R ' of thickness direction is defined with following formula (I) and (II) respectively.

R ₀＝(n _x-n _y)×d (I)

R’＝[(n _x+n _y)/2-n _z]×d (II)

In the positive uniaxiality film, because n _z n _y, so R ₀/ R '  2.Even the film of uniaxiality, R ₀/ R ' also can change between about 1.8～2.2 because of extending the change of condition.For the film of complete biaxiality, then because n _x n _y, so R ₀ 0.Therefore the film of biaxiality has negative uniaxiality owing to be the film of the refractive index difference (little) of only thickness direction fully, also is known as the film that optic axis is in normal direction, in addition, as previously mentioned, also is known as the c-plate sometimes.The n of the film of biaxiality _x＞n _y＞n _z

As by the polarizer of the complete biaxiality of using with aforesaid purpose, the spy open flat 10-104428 communique (=USP 6,060,183; Patent documentation 3) in, announces that the useful coat that contains the organic decoration clay complex that can be scattered in the organic solvent forms the situation of polarizer.The polarizer that will be made of this coat is simplified with stacked the constituting of composite polarizing plate of given mode and Polarizer, under the situation in being applied to liquid crystal indicator, will have good viewing angle characteristic and simple property concurrently.In addition, open in the 2004-294983 communique (patent documentation 4) the spy, announcement has following polarizer plate integrated polarizing, that is, be provided with the polarizer that the layer by the composition that contains the organic decoration clay complex that can be scattered in the organic solvent and (methyl) acrylic resin constitutes at polariscope one-sided.

No. 2548979 communique of [patent documentation 1] special permission

[patent documentation 2] spy opens 2001-109009 communique (technical scheme 15 and 0036 section)

[patent documentation 3] spy opens flat 10-104428 communique (=USP 6,060,183)

[patent documentation 4] spy opens the 2004-294983 communique

But, polarizer that this kind formed by the coat that contains organic decoration clay complex and Polarizer are stacked and form composite polarizing plate, use it under the situation in the liquid crystal indicator, then, eliminates the mist degree (haze) from this polarizer because of producing polarisation, thus the situation that has contrast to reduce.In addition, at the polarizer that this kind formed by the coat that contains organic decoration clay complex, perhaps with itself and Polarizer stacked the composite polarizing plate folder under the situation of the box glass gluing of cementing agent and liquid crystal indicator, because the influence of this polarizer, have the situation of passing in time with the adhesion of liquid crystal cell glass and reducing.

The inventor furthers investigate in order to solve described problem, found that, if in organic solvent, the coating polarizer that will contain organic decoration clay complex and binder resin is adjusted into specific value with the water percentage that applies liquid, then can suppress the mist degree of the coating polarizer of gained.Also find simultaneously in addition, be reduced to below the set-point with contained chlorine dose in the employed organic decoration clay complex in the coating liquid if will apply polarizer, then the reduction of the adhesion of the coating polarizer of gained when pressing from both sides every cementing agent and liquid crystal cell glass gluing just is suppressed.The present invention is based on this kind opinion and finishes.

Summary of the invention

So one of purpose of the present invention is, following coating liquid is provided, that is, contain organic decoration clay complex, making under the situation that applies polarizer, can reduce the mist value, can keep higher contrast of LCD degree.Other purpose of the present invention is, following coating polarizer coating liquid is provided, and, in the time will applying the phase differential plate holder every cementing agent and liquid crystal cell glass gluing, can keep higher adhesion that is.Another object of the present invention is, polarizer and the manufacture method thereof of using this coating liquid to improve the mist value are provided.Another object of the present invention is, provide this polarizer and Polarizer are laminated, aspect the improvement of the viewing angle characteristic of liquid crystal indicator effective composite polarizing plate and manufacture method thereof.In addition, another object of the present invention is, following liquid crystal indicator is provided, that is, with this composite polarizing plate and liquid crystal cell combination, viewing angle characteristic is modified, and contrast is also high.

That is, according to the present invention, providing a kind of coating polarizer with coating liquid, is the coating liquid that contains organic decoration clay complex and binder resin in organic solvent, and the water percentage of measuring with Ka Er-Fei Xier Moisture Meter is 0.15～0.35 weight %.

Here, the weight ratio of organic decoration clay complex/binder resin is preferably above 0.5 and below 3.In addition, the binder resin is preferably with the urethane resin of aliphatic diisocyanate as matrix, for example with the urethane resin of isophorone diisocyanate as matrix.When machine maintenance decorations clay complex is the complex of organic compound and the clay mineral that belongs to smectite (smectite) family, the atomic ratio (Mg/Si of magnesium and 4 silicon atoms then ₄) preferably less than 2.73.In addition, organic decoration clay complex preferably has the quaternary ammonium compound and the complex that belongs to the clay mineral of smectite family that carbon number is 1～30 alkyl.

In this coating liquid, the organic decoration clay complex wherein amount of contained chlorine is made as 2, is favourable below the 000ppm.Like this, by reducing the amount of chlorine contained in the organic decoration clay complex, the reduction of in time passing the adhesion that produce of the coating phase differential plate holder of gained when cementing agent and liquid crystal cell glass gluing will tail off.

In addition, according to the present invention, provide from described any one and apply polarizer with applying that the composition of having removed organic solvent and water the liquid is made into film like and the polarizer that forms.

The mist value of this polarizer is preferred below 0.6%.In addition, the phase difference value R in the best face of this polarizer ₀Be 0～10nm, the phase difference value R ' of thickness direction is 40～350nm.

Described polarizer can utilize following method manufacturing, promptly, to contain organic decoration clay complex, binder resin, organic solvent and water, the water percentage of measuring with Ka Er-Fei Xier Moisture Meter is that the coating liquid of 0.15～0.35 weight % is coated on the base material, then organic solvent and water is removed.

In addition, according to the present invention, also provide the composite polarizing plate that Polarizer, adhesive layer and described any one polarizer are formed with this sequential cascade.In this composite polarizing plate,, can form second adhesive layer again in the outside of polarizer.

Described composite polarizing plate can utilize following method advantageously to make, promptly, to in organic solvent, contain organic decoration clay complex and binder resin, the water percentage of measuring with Ka Er-Fei Xier Moisture Meter is that the coating liquid of 0.15～0.35 weight % is coated on the transfer substrate, from wherein removing organic solvent and water, form and apply polarizer, at the fit face that exposes of this coating polarizer of the adhesive layer side of Polarizer with adhesive layer, then, transfer substrate and described coating polarizer are peeled off.

In addition, according to the present invention, also provide the liquid crystal indicator that possesses described composite polarizing plate and liquid crystal cell.At this moment, composite polarizing plate is configured on a side the face of liquid crystal cell, makes its polarizer side face mutually with liquid crystal cell, that is, be not to make Polarizer, but make polarizer more be in the liquid crystal cell side.When the outside at polarizer is formed with second adhesive layer, then presss from both sides every this second adhesive layer and liquid crystal cell and fit.On the opposing party's of liquid crystal cell face, by with the phase difference value R in the face ₀Be about 30～300nm and the interior phase difference value R of face ₀Ratio R with the phase difference value R ' of thickness direction ₀/ R ' surpass 0 and less than 2 second polarizer, second Polarizer with this arranged in order, just can improve the viewing angle characteristic of liquid crystal cell.

Coating polarizer of the present invention can be controlled to be very little value with the mist value by the polarizer of its making with coating liquid.In addition, if minimizing as contained chlorine dose in the organic decoration clay complex of its composition use, then can suppress to be pressed from both sides at quilt by the polarizer of its making the reduction of the adhesion of the generation of passing in time under the state of cementing agent and liquid crystal cell glass gluing.With this polarizer and Polarizer stacked the composite polarizing plate wall thin, formation is simplified, and good aspect optical characteristics.On the face of a side by this composite polarizing plate being disposed at liquid crystal cell, on the opposing party's of liquid crystal cell face, dispose second Polarizer together with the polarizer with different optical characteristics (second polarizer), just can form following liquid crystal indicator, promptly, have peer-level with in the past liquid crystal indicator respectively having the vertical alignment mode of 1 biaxiality polarizer up and down or more than it optical property of level, particularly good aspect contrast.In addition, if use the coating liquid of making by the organic decoration clay complex that has reduced chlorine dose, then can keep the adhesion of the cementing agent that liquid crystal cell is bonding with applying polarizer.

Description of drawings

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

Fig. 2 is a diagrammatic cross-section of diagrammatically representing the manufacturing process of composite polarizing plate.

Fig. 3 diagrammatically is illustrated under the situation of composite polarizing plate with the drum manufacturing, until the side view of the operation that forms the coating polarizer, fit the Polarizer that has cementing agent thereon.

Fig. 4 is the side view that diagrammatically is illustrated in the operation that second adhesive layer is set on the composite polarizing plate.

Fig. 5 is a side view of diagrammatically representing the operation of situation about will carry out continuously until the formation of second adhesive layer from the formation that applies polarizer.

Fig. 6 is the diagrammatic cross-section of the configuration example of expression liquid crystal indicator of the present invention.

Wherein, 10 ... composite polarizing plate, 11 ... Polarizer, 12 ... adhesive layer, 13 ... the Polarizer that has cementing agent, 14 ... the mould release film of Polarizer, 15 ... apply polarizer, 17 ... second adhesive layer, 18 ... the mould release film of adhesive layer, 19 ... the film that has cementing agent, 20 ... transfer substrate, 21 ... transfer substrate after peeling off, 25 ... semi-manufacture, 30 ... transfer substrate is sent reel, 32 ... coating machine, 34 ... the coat dry section, 36 ... Polarizer is sent reel, and 38 ... the mould release film reel spool, 40 ... the semi-manufacture reel, 41 ... semi-manufacture rollback reel, 43 ... transfer substrate is peeled off reel, and 44 ... the transfer substrate reel spool, 45 ... the film that has cementing agent is sent reel, 46 ... the cementing agent coating machine, 47 ... the cementing agent dry section, 48 ... mould release film is sent reel, 50 ... the product reel, 60 ... liquid crystal cell, 62 ... second polarizer, 64 ... second Polarizer

Embodiment

Below with the present invention is described in detail.At first, describe with coating liquid applying polarizer.This coating polarizer is the liquid that contains organic decoration clay complex and binder resin in organic solvent with coating liquid.As the method that obtains this kind coating liquid, preferably with organic decoration clay complex and binder resin dispersion or be dissolved in method in the organic solvent.

Among the present invention, make this kind coating polarizer reach 0.15～0.35 weight % with the water percentage of coating liquid.When this water percentage surpasses 0.35 weight %, then can produce being separated in the water-insoluble organic solvent, coating liquid has the tendency that is separated into 2 layers.On the other hand, if its water percentage below 0.15 weight %, then when forming the coating polarizer, has the tendency that improves the mist value.This water percentage more preferably is made as more than the 0.18 weight %, further more than the preferred 0.2 weight %, more preferably is made as in addition below the 0.3 weight %.In the assay method of moisture, though seasoning, Ka Er-fischer's method, dielectric method etc. are arranged, among the present invention, adopt easy and can realize the Ka Er-fischer's method of the mensuration of microunit.

Though it is be not particularly limited with the method that the water percentage that applies liquid is adjusted into described scope applying polarizer, yet the method for interpolation water is very easy in coating liquid, thereby preferred.If just organic solvent, organic decoration clay complex and binder resin are mixed with usual way as used in the present invention, then can not demonstrate the above water percentage of 0.15 weight % basically.Yet, use in summer and to have taken place under the situations such as raw material of moisture absorption, also have water percentage and reach situation about 0.15 weight %.But,, also be difficult to reduce fully the mist value of the coating polarizer of gained even use the coating liquid that reaches the water percentage about 0.15 weight % because of the hygroscopic moisture of raw material.So,, and water percentage is made as described scope preferably by a spot of water of interpolation in the coating liquid that has mixed organic solvent, organic decoration clay complex and binder resin.For the method for adding water, the interpolation in whole periods at the modulating process of coating liquid is all effective, be not particularly limited, yet in the modulating process of coating liquid, through behind the certain hour, sampling and after having measured water percentage, add specified rate water method can repeatability and precision to control well aspect the water percentage be desirable.And, the also amount of the water that adds to some extent and the situation of utilizing measurement result that Ka Er-the Fei Xier Moisture Meter obtains not to be inconsistent.As its reason, a part of thinking water has produced the interaction (for example absorption) with organic decoration clay complex.But, if will remain 0.15～0.35 weight % of defined among the present invention with the moisture rate that Ka Er-Fei Xier Moisture Meter is measured, preferred 0.18～0.3 weight %, further preferred 0.2～0.3 weight % confirms that then the mist value of the coating polarizer of gained can Be Controlled get very low.

Organic decoration clay complex and binder resin preferably according to make the former/latter's weight ratio surpasses 0.5 and cooperate in the mode below 3.When both cooperation weight ratios break away from this scope, the tendency that is difficult to the mist value of the coating polarizer of gained is remained desired horizontal is arranged then.Both cooperation weight ratios more preferably are made as 1～3 scope, especially preferably are made as above 1 and below 2.

The solid formation branch concentration of this coating liquid is not as long as gelation or gonorrhoea can take place in the no problem scope in the coating liquid after the modulation in practical application, just without limits, yet as a rule, the total of organic decoration clay complex and binder resin forms branch concentration admittedly by the scope use with 3～18 weight %.Best solid formation divides concentration because according to organic decoration clay complex and binder resin kind or both ratio of componentss and different separately, so will every kind of composition be set, yet more preferably is in the scope of 8～16 weight %.In this coating liquid, also can add the viscosity modifier that is used to improve the coating when on base material, making film, the various adjuvants such as crosslinking chemical that are used for further improving hydrophobicity and/or permanance.

Used organic solvent is not particularly limited in the coating liquid, yet, can also enumerate the high polar solvent etc. of halogenated hydrocarbons etc. of the lower alcohols, phenixin, chloroform, methylene chloride, ethylene dichloride and so on of the ketone that comprises acetone, methyl ethyl ketone, methyl isobutyl ketone and so on, methyl alcohol, ethanol, propyl alcohol and so on for example except the low polarity that can enumerate benzene,toluene,xylene and so on aromatic hydrocarbon based.Wherein, from can disperseing organic decoration clay complex, dissolving binder resin can suppress to apply the viewpoint of the gelation of liquid and consider preferred toluene, dimethylbenzene, acetone, methyl isobutyl ketone or their potpourri.

The binder resin just is not particularly limited, yet in order to obtain good thermotolerance or the property handled, preferably has hydrophobic resin so long as be dissolved in resin in the described organic solvent.As preferred binder resin, for example can enumerate the such acrylic resin of polyvinylbutyral, polyvinylformal such polyvinyl acetal resin, cellulose acetate-butyrate such cellulosic resin, butylacrylic acid ester, methacrylic resin, urethane resin, epoxy resin, vibrin etc.Wherein, as preferred resin, can enumerate with the aliphatic diisocyanate is the urethane resin of matrix.

The urethane resin that with the aliphatic diisocyanate is matrix is by the fatty compound that has a plurality of isocyanate group in molecule, the compound generation addition reaction that has a plurality of hydroxyl isoreactivity hydrogen in molecule are generated.As the fatty compound that in molecule, has a plurality of isocyanate group, can enumerate hexamethylene diisocyanate, dicyclohexyl methyl hydride diisocyanate, cyclohexane diisocyanate, hydrogenated xylene diisocyanate, isophorone diisocyanate, norborene diisocyanate etc.In the middle of them, preferred especially is the compound of matrix with the isophorone diisocyanate.

In addition, as the compound that in molecule, has a plurality of hydroxyls, can enumerate polyether polyol, polyester polyol, polycarbonate polyol, polycaprolactone type polyvalent alcohol etc.In the middle of them, preferably use polyether polyol or polyester polyol, yet be not limited thereto, also can use their potpourri in addition.

Polyether polyol for example is utilized oxirane, epoxypropane, oxetanes, epoxy butane, Alpha-Methyl oxetanes, 3, the ring-opening polymerization or the copolymerization of cyclic ethers such as 3-dimethyl oxetanes, tetrahydrofuran, dioxane prepare, and are the materials that also is known as PTMEG, polyoxy oxyalkylene glycol.

Polyester polyol is to utilize polycondensation to make by polybase organic acid, particularly dicarboxylic acid and polyvalent alcohol.As dicarboxylic acid, for example can enumerate the aromatic carboxylic acid etc. of the unsaturated fatty acid, phthalic acid, isophthalic acid and so on of the saturated fatty acid, maleic acid, fumaric acid and so on of oxalic acid, succinic acid, glutaric acid, hexane diacid, heptandioic acid, suberic acid, azelaic acid, decanedioic acid, isosebacic acid and so on.As polyvalent alcohol, for example can enumerate six alcohol etc. of the triol, sorbierite and so on of the glycol, trimethylolpropane, trimethylolethane, hexanetriol, glycerine and so on of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butylene glycol and so on, yet be not limited to these, also can mix in addition and use more than 2 kinds.

The glass transition temperature of binder resin is preferred below 20 ℃, and preferred glass transition temperature is below-20 ℃.When the glass transition temperature of binder resin was high, caoutchouc elasticity deficiency then in the stacked composite polarizing plate, had the tendency of connecting airtight property or flexible variation at polarizer or with itself and Polarizer.

Organic decoration clay complex is the complex of organic compound and clay mineral, specifically, is to have the compound material of having changed of the clay mineral of layered struture and organic compound.As clay mineral with layered struture, can enumerate smectite family or swelling mica etc., utilize its cation exchange can be able to realize compoundization with organic compound.Wherein, smectite family is because good aspect transparent, therefore preferred the use.As the mineral that belong to smectite family, can hectorite, porcelain earth, bentonitic clay etc. or their replacement, derivant and potpourri etc. be shown example.In the middle of them,, transparency aspect such as good few from impurity by the mineral of chemosynthesis considered more preferred.Particularly, the synthetic li-montmorillonite of controlling particle diameter very little is owing to can suppress the scattering of luminous ray, therefore preferred the use.

As the organic compound of quilt with compoundization of clay mineral, can enumerate can with the compound of the oxygen atom of clay mineral or hydroxyl reaction, can be with the ionic compound of exchangeable cation exchange etc., so long as can make organic decoration clay complex can be in organic solvent swelling or dispersion, just be not particularly limited, yet specifically, can enumerate nitrogen-containing compound etc.As nitrogen-containing compound, for example can enumerate 1 grade (primary), 2 grades (second month in a season) or 3 grades of (uncle) ammonia, quaternary ammonium compound, urea, hydrazine etc.Wherein, owing to reasons such as cation exchange are easy to, the therefore preferred quaternary ammonium compound that uses.

As quaternary ammonium compound, for example can enumerate the compound with chain alkyl, compound etc. with alkyl ether chain.Wherein, preferably have carbon number be 1～30 alkyl, n=1～50-(CH ₂CH (CH ₃) O) _nH base or (CH ₂CH ₂CH ₂O) _nThe quaternary ammonium compound of H base.More preferably has carbon number and is the compound of 6～10 alkyl.

When organic decoration clay complex is constituted with the clay mineral that belongs to smectite family with organic compound, this belong to smectite family clay mineral so long as can be under the state that forms with the complex of organic compound the mineral of swelling or dispersion in organic solvent, just be not particularly limited, yet exchangeable cation is difficult to the clay mineral that exchanged by ionic organic compound, is difficult to disperse in organic solvent.In the composite of the clay mineral that belongs to smectite family, through its surface attachment of being everlasting magnesium compounds such as magnesium hydroxide are arranged, when the amount of this kind magnesium compound is a lot, then can hinder the exchangeable cation position.So, wait the material of removing the existence ratio minimizing that makes magnesium by being present in surperficial magnesium compound utilization acid cleaning, specifically, magnesium is with respect to the atomic ratio (Mg/Si of 4 silicon atoms ₄) material less than 2.73, owing in organic solvent, disperse easily, therefore preferred.For example, the hectorite such as the chemical voluminous dictionary editorial board that belong to smectite family compile shown in " chemical voluminous dictionary " (the upright altogether Co., Ltd. that publishes, clear and first edition distribution on February 28th, 37), typically under the situation by with Na _0.66(Mg _5.34Li _0.66) Si ₈O ₂₀(OH) ₄NH ₂O or Na _1/3(Mg _8/3Li _1/3) Si ₄O ₁₀(OH) ₂MH ₂The composition formula of O is represented, the Mg/Si under this state ₄Atomic ratio is 2.67, and in synthetic li-montmorillonite, since the aforesaid magnesium compound that is present in the surface, Mg/Si ₄Atomic ratio will be slightly larger than 2.67.

This kind is present in surperficial magnesium compound utilization acid cleaning etc. removes, and make Mg/Si ₄Atomic ratio is preferably used near 2.67 material as far as possible.In containing the smectite family clay mineral of hectorite or synthetic li-montmorillonite, sodium becomes exchangeable cation, because it and organic compound, and for example quaternary ammonium group exchange, and become organic decoration clay complex, therefore Mg/Si before and after modifying ₄Atomic ratio can not change.So, for Mg/Si with organic decoration clay complex ₄Atomic ratio is made as less than 2.73, and the way that the clay mineral before will modifying with organism cleans with acid is effective.

Organic decoration clay complex also can will be used in combination more than 2 kinds.In the commercially available product of suitable organic decoration clay complex, the synthetic li-montmorillonite sold with the trade name of " Le-セ Application イ ト STN " or " Le-セ Application イ ト SPN " by Co-op CHEMICAL (strain) and the complex of quaternary ammonium compound etc. are arranged respectively.

In organic decoration clay complex, because the influence of employed various auxiliary materials in it is made, the situation that often has the compound that contains chlorine to sneak into as impurity.When the amount of this kind chlorine compound for a long time, then might from film, ooze out after applying polarizer forming.Under this situation, when cementing agent should apply polarizer and liquid crystal cell glass gluing, then adhesion can be passed in time and reduce significantly at folder.So, preferably from organic decoration clay complex, utilize to clean in advance chlorine compound is removed, if wherein the amount of contained chlorine is made as 2, below the 000ppm, then can suppress the reduction of this kind adhesion.The method that can utilize the washing of organic decoration clay complex of removing of chlorine compound is carried out.

In the coating liquid that gets when mixed organic decoration clay complex and binder resin and a spot of water in organic solvent, when having the big solid of particle diameter, then in coating polarizer, will produce polarisation elimination effect, cause using the reduction of optical property of its liquid crystal indicator by its making.In addition, though organic decoration clay complex attenuates particle diameter because of the stirring dispergation of coating liquid, yet when there being not dispergation fully, the complex that particle diameter is still bigger when for example having the complex of particle diameter more than 1 μ m, then still can cause applying the reduction of the optical property of polarizer.So this coating liquid preferably utilizes filtrator to filter earlier, this kind solid that will have the possibility of existence is removed.But, in this filtration treatment, must make the dispergation of coating in the liquid organic decoration clay complex be not removed.As long as filtrator is owing to can remove the solid of most of particle diameter more than 1 μ m, therefore when the variation of also considering to cause that can filter particle diameter etc. by the obstruction of filtrator etc., from the aperture be about 0.5～10 μ m among, the filtrator that preferred use can be removed the solid major part more than the particle diameter 1 μ m.In addition, dispergation the particle diameter of organic decoration clay complex be about about 10～200nm.

Below, polarizer and manufacture method thereof are described.With as described above, contain organic decoration clay complex, binder resin, organic solvent and water and water percentage is adjusted to the coating liquid of particular range is coated on the smooth base material, by organic solvent and water are removed, just can obtain polarizer.At this moment, as previously mentioned, organic decoration clay complex preferably is made as Mg/Si in advance ₄Atomic ratio is less than 2.73, and in addition, wherein contained chlorine dose preferably is made as in advance 2, below the 000ppm.The removing of organic solvent after the coating and water as a rule is utilized drying and carries out.So polarizer of the present invention is a plate of the composition of having removed organic solvent and water from described coating liquid being made film like.This polarizer is provided with independent film like that is made of described composition or the state that has applied the film like of said composition on support base material.

Utilize aforesaid coating, drying, the layered struture of the unit crystallizing layer of organic decoration clay complex will be orientated abreast with smooth substrate surface, and face in towards randomly the orientation.So, do not need to carry out special orientation process, just can demonstrate the refractive index structure of the interior refractive index of pellicular front greater than the refractive index of film thickness direction.

Be not particularly limited though be used to be coated with the base material of coating liquid, for example can enumerate and be implemented pet film that the demoulding handles etc.In addition, it is enough that the temperature and time that applies film drying is needed only for removing used organic solvent and water, just be not particularly limited, for example suitably select the scope of temperature from about 50 ℃～150 ℃ to get final product, suitably select the scope of time from about 30 seconds～30 minutes in addition to get final product.

The mist value of polarizer of the present invention is preferred below 0.6%, in addition more preferably below 0.5%.When the mist value surpasses 0.6%, then eliminate, thereby used the contrast of LCD degree reduction of this polarizer because of the scattering of the linear polarization that sees through produces polarisation.The mist value also is known as the cloud valency, is the numerical value with (diffusion transmitance/whole light penetrations) * 100 (%) expression, by JIS K 7105 regulations.Utilize to use that the foregoing coating liquid that water percentage is adjusted into particular range applies, dry method, just can reduce this mist value.

Phase difference value R in the best face of this polarizer ₀Be in the scope of 0～10nm, preferably the phase difference value R ' of thickness direction is in the scope of 40～350nm.Here, the phase difference value R in face to face ₀When 10nm is above, then can't ignore this value, the negative uniaxiality of thickness direction is compromised.In addition, the phase difference value R ' of thickness direction is the purposes with this polarizer, particularly fits composite polarizing plate and value that the characteristic coupling ground of the liquid crystal cell that uses is suitably selected, about preferred especially 50～300nm.Though according to the kind of liquid crystal cell and difference, yet the phase difference value R ' of thickness direction often is set to the scope about about 50～200nm.Thickness when the phase difference value R ' of this thickness direction can utilize the described coating liquid of coating is controlled.So the film thickness that is used to form polarizer that has been dried is not particularly limited, so long as necessary thickness gets final product in realizing the desired phase differential of polarizer.

The refractive index anisotropy of thickness direction is by with the phase difference value R ' expression by the thickness direction of described formula (II) definition, this value can according to the slow axis in the face as sloping shaft tilt phase difference value R40 that 40 degree measure and the phase difference value R in the face ₀Calculate.

Utilize the phase difference value R ' of the thickness direction that formula (II) obtains followingly to calculate, that is, and the phase difference value R in the use face ₀, slow axis tilted 40 degree as sloping shaft and the phase difference value R that measures ₄₀, the thickness d of film and the mean refractive index n of film ₀,, utilize numerical evaluation to try to achieve n according to following formula (III)～(V) _x, n _yAnd n _z, the described formula of their substitutions (II) is calculated.

R ₀＝(n _x-n _y)×d (III)

R ₄₀＝(n _x-n _y’)×d/cos(φ) (IV)

(n _x+n _y+n _z)/3＝n ₀ (V)

Here, φ=sin ^-1[sin (40 °)/n ₀]

n _y’＝n _y×n _z/[n _y ²×sin ²(φ)+n _z ²×cos ²(φ)] ^1/2

Below, composite polarizing plate is described.Composite polarizing plate of the present invention shown in Fig. 1 (A), be Polarizer 11, adhesive layer 12 and above illustrated polarizer 15 by with this sequential cascade member.Polarizer 11 and adhesive layer 12 are prepared by the form with the Polarizer 13 that has cementing agent usually.Polarizer 15 constitutes by having the anisotropic described coat of refractive index, and this coat both can also can be constituted with the multilayer more than 2 layers by with 1 layer of formation.

This composite polarizing plate 10 is usually by according to making its polarizer 15 be in the mode of liquid crystal cell side, in other words, by so that Polarizer 11 is in the state in the outside, is fitted on the liquid crystal cell and uses.So, for the applying on liquid crystal cell, can be shown in Fig. 1 (B), at arranged outside second adhesive layer 17 of polarizer 15.Under this situation, at the arranged outside mould release film 18 of second adhesive layer 17, this mould release film 18 is stripped from before applying and is removed, thereby is fitted on the liquid crystal cell with the surface of second adhesive layer 17.That also can prepare to be provided with adhesive layer 17 on mould release film 18 has an adhesive film 19, is laminated in these adhesive layer 17 sides to apply on the polarizer 15.

When forming composite polarizing plate of the present invention, for example can adopt following method, that is, and after having formed coating polarizer 15 on the transfer substrate, to the surface transfer of the adhesive layer 12 that has cementing agent Polarizer 13.Based on Fig. 2 this example is described.

At first, shown in Fig. 2 (A), for preparing to have formed on the surface of Polarizer 11 adhesive layer 12 has a cementing agent Polarizer 13.In addition, shown in Fig. 2 (B), form coating polarizer 15 on the surface of transfer substrate 20.Then, (A) the coating polarizer 15 on the transfer substrate 20 shown in the adhesive layer that has cementing agent Polarizer 13 12 shown in, (B) is fitted mutually bondingly, forms the semi-manufacture 25 that applied the state of polarizer 15/ transfer substrate 20 formations by 11/ adhesive layer 12/ of the Polarizer shown in Fig. 2 (C).If as Fig. 2 (D) shown in transfer substrate 20 peeled off, then can obtain the composite polarizing plate 10 of state Fig. 1 (A) shown in thereafter.In addition,, second adhesive layer 17 and mould release film 18 are set, then can obtain the composite polarizing plate that has adhesive layer 17 10 of the state shown in Fig. 1 (B) on the surface of having peeled off the coating polarizer 15 after the transfer substrate if shown in Fig. 2 (E).Second adhesive layer 17 both can be provided with applying direct adhesive stripe-coating on the polarizer 15, also can prepare on mould release film 18 adhesive stripe-coating in advance and carry out drying and have an adhesive film 19, with its adhesive layer 17 sides with apply polarizer 15 and fit and be provided with.

In addition, in order to improve adhesive layer 12 and the adhesion that applies polarizer 15, coating polarizer 15 and second adhesive layer 17, also can be to the corona treatment of surface enforcement arbitrarily.

Used Polarizer 11 in the composite polarizing plate just is not particularly limited so long as have the material that sees through ability of selection for the linear polarization of certain vibration direction.Specifically, have resin films such as polyvinyl alcohols as matrix, absorption therein has been orientated the material of dichromatism pigment.As dichromatism pigment, can use iodine or dichromatism organic dyestuff under the typical situation.For example, can enumerate in the uniaxial extension polyvinyl alcohol (PVA) material etc. that absorption has been orientated the material of iodine molecule, absorption has been orientated the dichroic dye of azo class in the uniaxial extension polyvinyl alcohol (PVA) as the example of Polarizer.The polyvinyl alcohol polariscope that these absorption have been orientated dichromatism pigment has following function, that is, the linear polarization that will have vibration plane on the direction of orientation of dichromatism pigment absorbs, will with the direction of its quadrature on have a vibration plane linear polarization see through.

In general these Polarizers are used with following form, that is, the single or double at the polariscope of being made by the polyvinyl alcohol film has formed the protective seam of being made by macromolecule membranes such as cellulose triacetate films.When only when the single face of polariscope has protective seam, then following configuration, that is, the outside when this protective seam is in and fits with liquid crystal cell in addition, does not have the face of protective seam to be in adhesive linkage 12 sides.

Used cementing agent in the formation as composite polarizing plate, can enumerate with acrylic polymer zoarium, silicone polymkeric substance, polyester, polyurethane, polyethers etc. is the material of matrix polymer.Wherein, preferably use optics transparent good as acrylic adhesive, the wellability or the cohesiveness that keep appropriateness, also good with the cementability of base material, have against weather or thermotolerance etc. in addition, under the condition of heating or humidification, can not produce the material of problems such as floating or peel off.In acrylic adhesive, as the usefully following material of matrix polymer, promptly, to have carbon numbers such as methyl, ethyl, butyl and be (methyl) alkyl acrylate of the alkyl below 20, contain functional group's acrylic monomer by formations such as (methyl) acrylic acid or (methyl) hydroxy-ethyl acrylates, according to making glass transition temperature preferred below 25 ℃, more preferably the mode below 0 ℃ cooperate and the weight-average molecular weight of polymerization at the acrylic compounds interpolymer more than 100,000.The thickness of adhesive layer 12,17 is generally respectively about 15～30 μ m.

Below, the manufacture method of composite polarizing plate of the present invention is described.As the front with reference to Fig. 2 illustrated, among the present invention, preferably adopt following method, that is, be pre-formed on the transfer substrate 20 have the anisotropic coating polarizer 15 of refractive index after, with its transfer printing on the adhesive layer on the Polarizer 11 12.By adopting this kind method, just need be in the operation of the enterprising enforcement coat of Polarizer drying, therefore the problem of the coat that causes with regard to the deterioration that can not produce the polariscope that is caused by heat, by dry deficiency can advantageously be made composite polarizing plate.

Transfer substrate 20 is the films that have been implemented the processing that the layer that is formed at its surface easily can be peeled off, in general, sale has following film, that is, at release agents such as the surface coated silicone resin of resin films such as polyethylene terephthalate or fluororesin and be carried out demoulding processing.In addition, apply polarizer 15 in order to form on transfer substrate 20, the water contact angle of transfer substrate 20 preferably is in 90～130 ° scope, more preferably more than 100 °, in addition at the water contact angle below 120 °.If water contact angle is less than 90 °, then the fissility of transfer substrate 20 is poor, is easy to generate the unequal defective of phase differential in applying polarizer 15.In addition, when water contact angle during, then on transfer substrate 20, be easy to generate depression in the coating liquid before dry, thereby the situation of the mottled phase differential inequality of generation in face is arranged greater than 130 °.Here, the contact angle when so-called water contact angle is meant and has used water as liquid, its value is big more, and then expression is difficult to and water infiltration more.And, be limited to 180 ° on the water contact angle.

Similarly with reference to Fig. 2, its (E) particularly, as explanation in front like that, the outside at coating polarizer 15 can be provided with second adhesive layer 17.When second adhesive layer 17 is set like this, order with the first following operation and second operation is favourable, promptly, first operation is after having formed coating polarizer 15 on the transfer substrate 20, the operation that the adhesive layer that exposes face and Polarizer 11 12 of this coating polarizer 15 is stacked, second operation is when on the coating polarizer 15 on being laminated in Polarizer transfer substrate 20 being peeled off, and forms the operation of second adhesive layer 17 on this applies the transfer substrate release surface of polarizer 15.For the situation of producing composite polarizing plate with drum, with the summary of described first operation in Fig. 3 with the side view illustration, in addition with the summary of second operation in Fig. 4 with the side view illustration.

In first operation, on transfer substrate, form and have the anisotropic coating polarizer of refractive index, reeling of this coating polarizer to the bonding plane that exposes applying Polarizer on the face of air.If further describe in detail with reference to Fig. 3, then on the surface of sending the transfer substrate 20 of pulling out the reel 30 from transfer substrate, 32 coatings apply polarizer with applying liquid by coating machine,, be used to and the applying that has cementing agent Polarizer 13 after being dried continuing across dry section 34.Have cementing agent Polarizer 13 owing to as a rule supplied with by the form of the mould release film that can peel off to have fitted on its adhesive layer surface, therefore from send having on the cementing agent Polarizer 13 that reel 36 pulls out by Polarizer, at first mould release film 14 is stripped from, and is wound onto on the mould release film reel spool 38.In addition, have exposing of cementing agent Polarizer 13 face of adhesive layer be fitted in the surface of the coating polarizer that is formed on the described transfer substrate, become layer semi-manufacture of forming by Polarizer/adhesive layer/coating polarizer/transfer substrate 25 that constitutes, be wound onto on the semi-manufacture reel 40.

This first operation and reeling at the coating polarizer to the exposing applying protective film on the face of air; then pull it; when protective film is peeled off; compare with the usual way that Polarizer is fitted; process number reduces; not only favourable on cost, and because be difficult to produce defective that adhesion when being peeled off by protective film etc. causes, from the foreign matter defective of protective film etc., therefore can obtain the semi-manufacture 25 of excellent quality.In addition, when reeling these semi-manufacture, for the release agent that prevents transfer substrate 20 shifts to applying polarizer because of winding pressure, using side band (side tape) also is useful technology according to making the way that discontiguous mode is reeled between half-finished surface.

Employed application pattern is not particularly limited when forming the coating polarizer in first operation, can use known various cladding processes such as direct intaglio printing (direct gravure) method, reverse gravure (reverse gravure) method, mould cladding process, intermittent application (comma coat) method, excellent cladding process.Wherein, the intermittent application method, do not use backing roll mould cladding process etc. because good aspect thickness and precision, therefore preferred the employing.

Next, second operation is when the semi-manufacture of gained from first operation are peeled off transfer substrate, and the coating polarizer surface after peeling off forms the operation of adhesive layer, that is, be the operation of implementing bonding processing.If be further elaborated with reference to Fig. 4, then the semi-manufacture 25 that temporarily are wound in first operation shown in Figure 3 on the semi-manufacture reel 40 are pulled out from identical reel 40, after peeling off reel 43 with transfer substrate transfer substrate 21 peeled off, from send reel 45, pull out have adhesive film 19 by with its adhesive layer side snugly to supplying with because of the surface of peeling off the coating polarizer that exposes, both are fitted, and are wound onto on the product reel 50.21 of the transfer substrate of having peeled off with semi-manufacture 25 are wound onto on the transfer substrate reel spool 44.Here, though in the formation of second adhesive layer, represented to use the mode that has adhesive film 19, as previously mentioned, also cementing agent directly can be coated on the coating polarizer.Through these operations, can obtain by composite polarizing plate with the arranged in order of Polarizer/adhesive layer/coating polarizer/adhesive layer.

Also can be with first operation shown in Figure 3 and the second operation serialization shown in Figure 4.The side view of example under this situation with summary is shown among Fig. 5.Among Fig. 5, Fig. 3 and the identical part of Fig. 4 are used identical symbol, will omit about their detailed description.In this example, on the surface of sending the transfer substrate 20 of pulling out the reel 30 from transfer substrate, use coating machine 32 coatings to apply polarizer with applying liquid, continuing across dry section 34 after being dried, send the cementing agent Polarizer 13 that has of pulling out the reel 36 and having peeled off behind the mould release film 14 from Polarizer and be fitted in this coating polarizer side with its adhesive layer side, thereby obtain the semi-manufacture 25 that constitutes of layer be made up of Polarizer/adhesive layer/coating polarizer/transfer substrate, first operation with shown in Figure 3 till here is identical.

Thereafter, semi-manufacture 25 are not wound into reel, and after passing semi-manufacture rollback reel 41, peel off reel 43 by transfer substrate transfer substrate is peeled off, and the transfer substrate 21 after peeling off is wound onto on the reel spool 44.On the other hand, coating polarizer surface after having peeled off transfer substrate 21, by cementing agent coating machine 46 coating cementing agents, passing cementing agent dry section 47 after being dried, on its applicator surface, the mould release film 18 that applying is pulled out from mould release film reel 48 is wound on the product reel 50.In this example, represented in the formation of second adhesive layer, used the direct coating drying mode of cementing agent coating machine 46 and dry section 47, yet also can adopt as shown in Figure 4 use to have the mode of adhesive film.

If make placement for a long time under coating polarizer 15 and transfer substrate 20 state of contact, then the release agent on the transfer substrate 20 just shifts to applying polarizer 15, and the water contact angle on the surface of the coating polarizer 15 after the transfer substrate 20 (being 21 after peeling off) has been peeled off in raising.Consider from the viewpoint of the connecting airtight property of the surface of having peeled off the coating polarizer 15 after the transfer substrate 21 and second adhesive layer 17, the contact angle that exposes face to air of the water contact angle on coating polarizer 15 surfaces after transfer substrate is peeled off coating polarizer 15 of [with reference to Fig. 2 (B)] when having formed coating polarizer 15 on transfer substrate 20 is compared, reaching in 15 °, under preferred 10 ° of conditions, preferably carry out the transfer substrate of second operation and peel off and bonding processing with interior recruitment.For this reason, first operation preferably turns to second operation after finishing as quickly as possible.In addition, the coating polarizer of having peeled off after the transfer substrate 21 15 is carried out the bonding man-hour that adds, to implement the way of corona treatment all be useful technology to applying the surface of any one in the middle of the polarizer 15 and second adhesive layer 17.

And in Fig. 3～Fig. 5, curve arrow is represented the sense of rotation of reel.

Below, liquid crystal indicator is described.Liquid crystal indicator of the present invention is as representing its configuration example among Fig. 6 with diagrammatic cross-section, on a side's of liquid crystal cell 60 face, above illustrated composite polarizing plate 10 in its polarizer 15 sides, generally disposed every second adhesive layer 17 by folder, on the opposing party's of liquid crystal cell 60 face, second polarizer 62 and second Polarizer 64 are by with this arranged in order.

Be disposed at the interior phase difference value R of face of second polarizer 62 between the liquid crystal cell 60 and second Polarizer 64 ₀Be 30～300nm, the phase difference value R in the face ₀Ratio R with the phase difference value R ' of thickness direction ₀/ R ' is above 0 and less than 2, promptly with 0＜R ₀The condition of/R '＜2 constitutes.By the polarizer and the described composite polarizing plate combination of the present invention that will have this kind phase difference characteristics, just can improve the viewing angle characteristic of liquid crystal indicator.The polarizer of giving this kind phase difference characteristics for example can utilize following method manufacturing,, macromolecule reel film is used stenter etc. that is, carries out the stiff end uniaxial extension, carries out the horizontal uniaxial extension of stiff end specifically.Based on can easily making of the stiff end uniaxial extension, or reason, the R of second polarizer 62 such as the optical characteristics when being applied in the liquid crystal indicator is good ₀/ R ' preferably is in 0.8～1.4 scope.R ₀/ R ' also can be below 1.3.

The material of second polarizer 62 is not particularly limited, for example can be polycarbonate, polyurethane, with the polycyclic olefin as the norborene as cyclic olefin resinoid, cellulose family, the polyolefins of monomer, used the interpolymer etc. of the monomer of these macromolecular compounds of formation more than 2 kinds.Under high temperature and super-humid conditions, the viewpoint that has perhaps applied the stability of the optical characteristics under the state of tension force is considered preferred light elasticity coefficient circlet shape olefine kind resin.In addition, in this second polarizer 62, the wavelength dependency of phase difference value also is not particularly limited, yet considers from the painted viewpoint that suppresses appearance, preferably has along with the wavelength polarizer that phase differential that phase difference value diminishes distributes that shortens.

Second Polarizer 64 is with previous identical with reference to the illustrated Polarizer 11 of Fig. 1, can be the Polarizer that has formed the protective seam of being made by macromolecule membrane at the single or double that absorption has been orientated the polyvinyl alcohol polariscope of dichromatism pigment.

Second Polarizer 64 expose face (among Fig. 6 for downside) at least, preferably be configured to exist protective seam.In addition, second polarizer 62 also can not be the one-sided protective seam with second Polarizer 64, but the polariscope that is used tackifier or the cementing agent and second Polarizer 64 directly connects airtight.Under this situation, second Polarizer 64 only has protective seam at the single face of linear polarization mirror, does not have stacked second polarizer 62 of a side of protective seam at it.

Though second Polarizer 64 and second polarizer 62 are arranged to the former absorption axes and slow axis crossing getting final product between 80～100 ° of the latter, yet consider that from the viewpoint of the minimizing of higher contrast or irregular colour both shaft angle degree preferably are between 85～95 °.More preferably both shaft angle degree are set between 89～91 °.

And, though the diagram omission, in the applying of the liquid crystal cell 60 and second polarizer 62, can use cementing agents such as acrylic compounds.In addition, the applying of second polarizer 62 and second Polarizer 64, the applying when particularly second Polarizer 64 has protective seam on the two sides also can be used cementing agents such as acrylic compounds.For acrylic adhesive, we can say identical with previous explanation.

When liquid crystal indicator shown in Figure 6 is used with infiltration type, in the outside of its composite polarizing plate 10 or any side in the outside of second Polarizer 64, the configuration backlight.Which side no matter backlight be disposed at can.So, the mode one of liquid crystal indicator is following mode, that is, composite polarizing plate 10 of the present invention is disposed at the front side (side is recognized in knowledge) of liquid crystal cell 60, second polarizer 62 and second Polarizer 64 are disposed at rear side (situation for infiltration type is the backlight side).In addition, the mode two of liquid crystal indicator is following mode,, composite polarizing plate 10 is disposed at the rear side of liquid crystal cell 60 that is, and second polarizer 62 and second Polarizer 64 are disposed at the front side.In these configurations, the shaft angle degree of each layer etc. all is set to and makes viewing angle characteristic reach best.

The box glass of liquid crystal cell 60 is being pressed from both sides under the state that second adhesive layer 17 is fitted with applying polarizer 15, and the adhesion to liquid crystal cell glass of this second adhesive layer 17 preferably is difficult to passing in time and changes.Adhesion is the bonding plane and the power that is produced by contacting of the face of convered structure because of adhesive sheet, and its test method is by JIS Z 0237 regulation.Be woven in the polarizer that the coating liquid in the organic solvent makes with the binder resin by the organic decoration clay complex that chlorinity is high, behind cementing agent and liquid crystal cell glass gluing, compare soon, pass adhesion in time and reduce significantly with folder.So, if used the material of after making organic decoration clay complex, implementing washing etc. and having reduced chlorinity, then just diminished by the reduction of passing the adhesion that produces in time of coating polarizer when pressing from both sides that the coating liquid that has cooperated it obtains every cementing agent and liquid crystal cell glass gluing.Specifically, to apply under the state that polarizer and liquid crystal cell fitted every cementing agent at folder, or will apply polarizer side folder under the state of cementing agent and liquid crystal cell glass gluing with it at the stacked composite polarizing plate that applies polarizer on the Polarizer, can be maintained at more than 60% with respect to soon adhesion after fitting at 23 ℃ of adhesions after having taken care of 1 month, even can be maintained at more than 80%.

[embodiment]

Below, will utilize embodiment that the present invention is further elaborated, yet the present invention is not limited by these examples.In the example, the % of expression content or use amount and part short of particularly pointing out then all are weight basis.In the following example in the modulation of coating liquid used material as follows.

(A) organic decoration clay complex

Trade name " Le-セ Application イ ト STN ": Co-op Chemical (strain) system, the complex of synthetic li-montmorillonite and tricaprylmethylammonium ion.

(B) binder resin

Trade name " SBU ラ Star カ-0866 ": firmly change Bayer polyurethane (strain) system, the solid formation branch concentration of isophorone diisocyanate matrix is 30% urethane resin varnish.

In addition, the physics value of sample is measured and is estimated and is based on that following method carries out.

(1) water percentage

For applying polarizer, use the Ka Er-Fei Xier Moisture Meter " KFT テ イ ト リ-ノ 795 types " of メ ト ロ-system corporate system to measure with coating liquid.And, in the mensuration, used the mixed solvent of chloroform 55% with ethylene chlorhydrin 45%.

(2) the phase difference value R in the face ₀

The coating phase differential plate holder that is formed on the transfer substrate is transferred on the square glass plate of 4cm every cementing agent.For the polarizer that is fitted in the state on the glass plate like this, use the mensuration machine " KOBRA-21ADH " of prince's instrumentation machine (strain) system, with the monochromatic light utilization rotation analyzer method of wavelength 559nm, the phase difference value R in the mensuration face ₀And, the phase difference value R in the face of the polarizer of making by the extension film of resin ₀Directly use described " KOBRA-21ADH " to measure.

(3) the phase difference value R ' of thickness direction

Phase difference value R in the use face ₀, slow axis tilted 40 degree as sloping shaft and the phase difference value R that measures ₄₀, the thickness d of polarizer and the mean refractive index n of polarizer ₀, try to achieve n with the method shown in previous _x, n _y, n _z, then, utilize the phase difference value R ' of described formula (II) calculated thickness direction.

(4) mist value

To being formed at the coating polarizer on the glass plate, use the mist value instrument " HGM-2DP " of ス ガ testing machine (strain) system to measure.

(5) contrast

The liquid crystal indicator that has disposed the Polarizer of regulation is controlled according to realizing black mode that shows and show in vain and backlight combination, utilize brightness measuring device " EZ-Contrast " under the different visual angles of ELDIM corporate system, measure the contrast (positive contrast) of the normal direction of display surface.The ratio of the brightness when here, the brightness of contrast by with white show the time is with black the demonstration is represented.

(6) adhesion

Light transmission shaft with polariscope is cut into wide 25mm as long limit with composite polarizing plate, is about 250mm, behind the liquid crystal cell glass gluing, uses autoclave, at pressure 5kgf/cm ², carry out 20 minutes pressurized treatments under 50 ℃ of the temperature.Then, use the mensuration machine " AUTOGRAPH AG-1 " of (strain) Shimadzu Seisakusho Ltd. system, under 180 ℃, peel off, with draw speed 300mm/ minute mensuration adhesion.

Embodiment 1

(a) making of coating polarizer

Modulated coating liquid with following composition.

7.5 parts in urethane resin varnish " SBU ラ Star カ-0866 "

6.8 parts of organic decoration clay complexs " Le-セ Application イ ト STN "

85.7 parts of toluene

0.2 part in water

Here used organic decoration clay complex is to clean by carrying out acid after the synthetic li-montmorillonite manufacturing of producer before organic decoration, with its organic decoration the material that obtains of state, its Mg/Si ₄Atomic ratio is 2.68 (producer's measured values).This coating liquid is after mixing with described composition, having stirred 360 minutes, with the membrane filter filtration of aperture 6 μ m.In this coating liquid, the solid formation branch weight ratio of organic decoration clay complex/urethane resin is 3/1, is 9% Gu form branch concentration.The water percentage of measuring with Ka Er-Fei Xier Moisture Meter of coating liquid that has added the state of 0.2 part of water is 0.27%.This coating liquid use applicator is coated on the pet film (water contact angle of demoulding treated side is 110 °) of the thickness 38 μ m that have been implemented demoulding processing, thereafter, drying is 1 minute under 50 ℃, descended dry 3 minutes at 90 ℃ then, obtained being applied to the polarizer on the film.Behind the phase difference value of having measured this coating polarizer, R ₀=0.1nm, R '=127nm.In addition, the mist value that similarly is coated in the polarizer on the glass plate is 0.5%.

(b) making of composite polarizing plate

Exposing on the face of the coat of the polarizer that in described (a), obtains; to have protective seam on the two sides of polyvinyl alcohol (PVA)-iodine class polariscope and fit with its adhesive side, make semi-manufacture by Polarizer/adhesive layer/coating polarizer/mould release film constitutes at the Polarizer (Sumitomo Chemical (strain) system trade name " ス ミ カ ラ Application SRW842A ") that single face has been endowed adhesive layer.Then, peeling off on the coating polarizer surface behind the mould release film, the pet film that additionally will apply cementing agent on demoulding treated side is fitted with its adhesive side, has made the composite polarizing plate by Polarizer/adhesive layer/coating polarizer/adhesive layer/mould release film constitutes.

(c) making of liquid crystal indicator and evaluation

The mould release film by Polarizer/adhesive layer/composite polarizing plate that coating polarizer/adhesive layer/mould release film constitutes that will obtain in described (b) is peeled off, folder is every this adhesive layer, be laminated in VA type liquid crystal cell (commercially available product) above, below liquid crystal cell, folder every the stacked extension film of cementing agent by cyclic polyolefin make, phase difference value R in the face ₀Second polarizer of phase difference value the R '=130nm of=100nm, thickness direction; then under it; folder has second Polarizer of the protective seam (trade name " ス ミ カ ラ Application SQ0642A " of Sumitomo Chemical (strain) system every the single face that adhesive layer is stacked in polyvinyl alcohol (PVA)-iodine class polariscope; orlop below making becomes the protective seam of second Polarizer, has made liquid crystal indicator.Here, the absorption axes angulation of the composite polarizing plate and second Polarizer is configured to 90 °, the absorption axes of second Polarizer and the slow axis angulation of second polarizer are configured to 90 °.Having measured this contrast of LCD degree, is 631.

Comparative example 1

(a) making of coating polarizer

Made coating liquid with following composition.

7.5 parts in urethane resin varnish " SBU ラ Star カ-0866 "

6.8 parts of organic decoration clay complexs " Le-セ Application イ ト STN "

85.7 parts of toluene

Here used organic decoration clay complex cleans by carrying out acid after the synthetic li-montmorillonite manufacturing of producer before organic decoration, be with its organic decoration the material that obtains of state, its Mg/Si ₄Atomic ratio is 2.73 (producer's measured values).This coating liquid filters with the membrane filter of aperture 6 μ m after mixing with described composition, having stirred 360 minutes.In this coating liquid, the solid formation branch weight ratio of organic decoration clay complex/urethane resin is 3/1, is 9% Gu form branch concentration.The water percentage that the Yi Kaer of this coating liquid-Fei Xier Moisture Meter is measured is 0.14%.This coating liquid has been used the condition identical with embodiment 1 to be coated in to be implemented on the pet film of the thickness 38 μ m that the demoulding handles, drying has obtained being coated on the polarizer on the film.Measured the phase difference value of this coating polarizer, R ₀=0.1nm, R '=126nm.In addition, the mist value that similarly is coated on the polarizer on the glass plate is 2.8%.

(b) making of composite polarizing plate

The polarizer that use obtains in described (a), made in the same manner by the semi-manufacture that Polarizer/adhesive layer/coating polarizer/mould release film constitutes with embodiment 1 (b), made composite polarizing plate then by Polarizer/adhesive layer/coating polarizer/adhesive layer/mould release film constitutes.

(c) making of liquid crystal indicator and evaluation

Use in described (b), obtain by the composite polarizing plate that Polarizer/adhesive layer/coating polarizer/adhesive layer/mould release film constitutes, made liquid crystal indicator in the same manner with (c) of embodiment 1.Having measured this contrast of LCD degree, is 604.

Embodiment 2

(a) making of coating polarizer

Modulated coating liquid with following composition.

16.0 parts in urethane resin varnish " SBU ラ Star カ-0866 "

7.2 parts of organic decoration clay complexs " Le-セ Application イ ト STN "

76.8 parts of toluene

0.3 part in water

Here used organic decoration clay complex is by having carried out sour cleaning after the synthetic li-montmorillonite manufacturing of producer before organic decoration, the material that obtains with the state that its organic decoration has been carried out then washing.Wherein contained chlorine dose is 1,257ppm, Mg/Si in addition ₄Atomic ratio is 2.68 (producer's measured values).This coating liquid filters with the membrane filter of aperture 6 μ m after mixing with described composition, having stirred 360 minutes.In this coating liquid, the solid formation branch weight ratio of organic decoration clay complex/urethane resin is 1.5/1, is 12% Gu form branch concentration.Having added the water percentage that the Yi Kaer-Fei Xier Moisture Meter of the coating liquid under the state of 0.3 part of water measures is 0.27%.This coating liquid use applicator is coated on the pet film (water contact angle of demoulding treated side is 110 °) of the thickness 38 μ m that have been implemented demoulding processing, thereafter following dry 1 minute at 50 ℃, descended dry 3 minutes at 90 ℃ then, obtained being coated on the polarizer on the film.Measured the phase difference value of this coating polarizer, R ₀=0nm, R '=151nm.In addition, the mist value that similarly is coated on the polarizer on the glass plate is 0.3%.

(b) making of composite polarizing plate

Exposing on the face of the coat of the polarizer that in described (a), obtains; to have protective seam on the two sides of polyvinyl alcohol (PVA)-iodine class polariscope and fit with its adhesive side, make semi-manufacture by Polarizer/adhesive layer/coating polarizer/mould release film constitutes at the Polarizer (Sumitomo Chemical (strain) system trade name " ス ミ カ ラ Application SRW842A ") that single face has been endowed adhesive layer.Then, peeling off on the coating polarizer surface behind the mould release film, the pet film that additionally will apply cementing agent on demoulding treated side is fitted with its adhesive side, has made the composite polarizing plate by Polarizer/adhesive layer/coating polarizer/adhesive layer/mould release film constitutes.

(c) making of liquid crystal indicator and evaluation

The mould release film by Polarizer/adhesive layer/composite polarizing plate that coating polarizer/adhesive layer/mould release film constitutes that will obtain in described (b) is peeled off, folder is every this adhesive layer, be laminated in VA type liquid crystal cell (commercially available product) above, below liquid crystal cell, folder every the stacked extension film of cementing agent by cyclic polyolefin make, phase difference value R in the face ₀Second polarizer of phase difference value the R '=130nm of=100nm, thickness direction; then under it; folder has second Polarizer of the protective seam (trade name " ス ミ カ ラ Application SQ0642A " of Sumitomo Chemical (strain) system every the single face that adhesive layer is stacked in polyvinyl alcohol (PVA)-iodine class polariscope; orlop below making becomes the protective seam of second Polarizer, has made liquid crystal indicator.Here, the absorption axes angulation of the composite polarizing plate and second Polarizer is configured to 90 °, the absorption axes of second Polarizer and the slow axis angulation of second polarizer are configured to 90 °.Having measured this contrast of LCD degree, is 641.Soon adhesion was 6.34N/25mm after the top composite polarizing plate of this liquid crystal indicator was fitted, and in addition, the adhesion of having taken care of under 23 ℃ after 1 week is 7.13N/25mm, and the adhesion of having taken care of under the uniform temp after 1 month is 8.05N/25mm.With compare soon after composite polarizing plate is fitted, 1 week of keeping and keeping are after 1 month down at 23 ℃, adhesion increases on the contrary.

Embodiment 3

(a) making of coating polarizer

Modulated coating liquid with following composition.

16.0 parts in urethane resin varnish " SBU ラ Star カ-0866 "

7.2 parts of organic decoration clay complexs " Le-セ Application イ ト STN "

76.8 parts of toluene

0.3 part in water

Here used organic decoration clay complex also is by having carried out sour cleaning after the synthetic li-montmorillonite manufacturing of producer before organic decoration, the material that obtains with the state that its organic decoration has been carried out then washing.Wherein contained chlorine dose is 1,659ppm, Mg/Si in addition ₄Atomic ratio is 2.68 (producer's measured values).This coating liquid also is after mixing with described composition, having stirred 360 minutes, filters with the membrane filter of aperture 6 μ m.In this coating liquid, the solid formation branch weight ratio of organic decoration clay complex/urethane resin is 1.5/1, is 12% Gu form branch concentration.Having added the water percentage that the Yi Kaer-Fei Xier Moisture Meter of the coating liquid under the state of 0.3 part of water measures is 0.27%.This coating liquid is being coated under the condition identical with embodiment 2 on the pet film that has been implemented the thickness 38 μ m that the demoulding handles, and drying has obtained being coated on the polarizer on the film.Measured the phase difference value of this coating polarizer, R ₀=0nm, R '=133nm.In addition, the mist value that similarly is coated on the polarizer on the glass plate is 0.3%.

(b) making of composite polarizing plate

The polarizer that use obtains in described (a), semi-manufacture have been made in the same manner with (b) of embodiment 2 by Polarizer/adhesive layer/coating polarizer/mould release film constitutes, then, made composite polarizing plate by Polarizer/adhesive layer/coating polarizer/adhesive layer/mould release film constitutes.

(c) making of liquid crystal indicator and evaluation

Use in described (b), obtain by the composite polarizing plate that Polarizer/adhesive layer/coating polarizer/adhesive layer/mould release film constitutes, made liquid crystal indicator in the same manner with (c) of embodiment 2.Having measured this contrast of LCD degree, is 652.Soon adhesion was 8.10N/25mm after the top composite polarizing plate of this liquid crystal indicator was fitted, and in addition, the adhesion of having taken care of under 23 ℃ after 1 week is 7.76N/25mm, and the adhesion of having taken care of under the uniform temp after 1 month is 7.46N/25mm.With compare soon after composite polarizing plate is fitted, keeping 96% adhesion after 1 week of keeping down at 23 ℃, after keeping 1 month, kept 92% adhesion in addition.

Comparative example 2

(a) making of coating polarizer

Made coating liquid with following composition.

16.0 parts in urethane resin varnish " SBU ラ Star カ-0866 "

7.2 parts of organic decoration clay complexs " Le-セ Application イ ト STN "

76.8 parts of toluene

Here used identical among used organic decoration clay complex and the embodiment 2, wherein contained chlorine dose is 1,257ppm, Mg/Si in addition ₄Atomic ratio is 2.68 (producer's measured values).This coating liquid also is after mixing with described composition, having stirred 360 minutes, filters with the membrane filter of aperture 6 μ m.In this coating liquid, the solid formation branch weight ratio of organic decoration clay complex/urethane resin is 1.5/1, is 12% Gu form branch concentration.The water percentage that the Yi Kaer of this coating liquid-Fei Xier Moisture Meter is measured is 0.11%.This coating liquid is being coated under the condition identical with embodiment 2 on the pet film that has been implemented the thickness 38 μ m that the demoulding handles, and drying has obtained being coated on the polarizer on the film.Measured the phase difference value of this coating polarizer, R ₀=0nm, R '=111nm.In addition, the mist value that similarly is coated on the polarizer on the glass plate is 3.7%.

(b) making of composite polarizing plate

The polarizer that use obtains in described (a), made in the same manner by the semi-manufacture that Polarizer/adhesive layer/coating polarizer/mould release film constitutes with embodiment 2 (b), made composite polarizing plate then by Polarizer/adhesive layer/coating polarizer/adhesive layer/mould release film constitutes.

(c) making of liquid crystal indicator and evaluation

Use in described (b), obtain by the composite polarizing plate that Polarizer/adhesive layer/coating polarizer/adhesive layer/mould release film constitutes, made liquid crystal indicator in the same manner with (c) of embodiment 2.Having measured this contrast of LCD degree, is 592.Soon adhesion was 12.43N/25mm after the top composite polarizing plate of this liquid crystal indicator was fitted, and in addition, the adhesion of having taken care of under 23 ℃ after 1 week is 11.12N/25mm, and the adhesion of having taken care of under the uniform temp after 1 month is 10.24N/25mm.In this example,, therefore apply the mist value height of polarizer, used its contrast of LCD degree low owing to apply the water percentage adjustment of liquid.On the other hand, owing to used the low organic decoration clay complex of chlorinity, therefore compare soon after fitting on the liquid crystal cell with composite polarizing plate, keeping 1 Zhou Houji keeping is after 1 month down at 23 ℃, and adhesion all is maintained very high value.

Of the present invention with polarizer and Polarizer stacked composite polarizing plate for vertical orientated (VA), for the liquid crystal indicator of twisted nematic phase (TN), optical compensation curved various patterns such as (OCB), can effectively utilize aspect the improvement of viewing angle characteristic in addition.

Claims (14)

1. one kind applies polarizer with coating liquid, is the coating liquid that contains organic decoration clay complex and binder resin in organic solvent, it is characterized in that the water percentage of measuring with Ka Er-Fei Xier Moisture Meter is 0.15～0.35 weight %.

2. coating polarizer according to claim 1 is with coating liquid, wherein, the weight ratio of organic decoration clay complex/binder resin greater than 0.5 below 3.

3. coating polarizer according to claim 1 and 2 is with applying liquid, and wherein, the binder resin is with the urethane resin of isophorone diisocyanate as matrix.

According to any described coating polarizer in the claim 1～3 with coating liquid, wherein, organic decoration clay complex is to have the quaternary ammonium compound and the complex that belongs to the clay mineral of smectite family that carbon number is 1～30 alkyl.

5. according to any described coating polarizer coating liquid in the claim 1～3, wherein, organic decoration clay complex is organic compound and the complex that belongs to the clay mineral of smectite family, the atomic ratio Mg/Si of magnesium and 4 silicon atoms ₄Less than 2.73.

6. according to any described coating polarizer is with applying liquid in the claim 1～5, wherein, the amount of contained chlorine is 2, below the 000ppm in the organic decoration clay complex.

7. a polarizer is characterized in that, requires any described coating polarizer in 1～6 to make film like and form with applying the composition of having removed in the liquid behind organic solvent and the water by accessory rights.

8. polarizer according to claim 7, wherein, the mist value is below 0.6%.

9. according to claim 7 or 8 described polarizers, wherein, the phase difference value in the face is 0～10nm, and the phase difference value of thickness direction is 40～350nm.

10. the manufacture method of a polarizer, it is characterized in that, to contain organic decoration clay complex, binder resin, organic solvent and water and be that the coating liquid of 0.15～0.35 weight % is coated on the base material, then organic solvent and water be removed with the water percentage that Ka Er-Fei Xier Moisture Meter measures.

11. a composite polarizing plate is characterized in that, has stacked gradually any described polarizer in Polarizer, adhesive layer and the claim 7～9.

12. composite polarizing plate according to claim 11 wherein, in the outside of polarizer, also is formed with second adhesive layer.

13. the manufacture method of a composite polarizing plate, be to have stacked gradually Polarizer, the manufacture method of the composite polarizing plate of adhesive layer and polarizer, it is characterized in that, to in organic solvent, contain organic decoration clay complex and binder resin and be that the coating liquid of 0.15～0.35 weight % is coated on the transfer substrate with the water percentage that Ka Er-Fei Xier Moisture Meter measures, remove organic solvent and water then, form and apply polarizer, at the fit face that exposes of this coating polarizer of this adhesive layer side of the Polarizer with adhesive layer, then, peel off transfer substrate from described coating polarizer.

14. a liquid crystal indicator is characterized in that possessing:

Liquid crystal cell;

On the one side of liquid crystal cell according to making polarizer more be in claim 11 or the 12 described composite polarizing plates that the mode of liquid crystal cell side disposes than Polarizer;

Be disposed on the another side of this liquid crystal cell and the phase difference value R in the face ₀Be the phase difference value R in 30～300nm, the face ₀Ratio R with the phase difference value R ' of thickness direction ₀/ R ' is greater than 0 and less than 2 second polarizer;

What be disposed at this second polarizer is second Polarizer of an opposite side with liquid crystal cell.

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