CN1734321A - Method for manufacturing liquid crystal alignment film, liquid crystal alignment film, optical film and image viewing display - Google Patents

Abstract

A method for manufacturing liquid crystal alignment film of the present invention comprises the steps of: (1) aligning a transparent substrate film by rubbing; (2) laminating a surface protective sheet having a release force of 0.5 N/50 mm or less onto an aligned face of the transparent substrate; (3) coating a liquid crystal material comprising a liquid crystal monomer and/or a liquid crystal polymer onto the aligned face after releasing the surface protective sheet; and (4) fixing the liquid crystal material after aligning the liquid crystal material. The method can make satisfactorily align the liquid crystal material on the substrate.

Description

Liquid crystal aligning film and manufacture method thereof, optical thin film and image display device

Technical field

The present invention relates to a kind of manufacture method of liquid crystal aligning film.In addition, the invention still further relates to the liquid crystal aligning film that obtains by this manufacture method, use the optical thin film of 1 this liquid crystal aligning film at least.Can use liquid crystal aligning film of the present invention as optical thin films such as polarizer, viewing angle compensation film, optical compensating film, elliptic polarization optical thin films separately or with other film combinations.And then, the invention still further relates to the liquid crystal indicator, the electricity that have used above-mentioned optical thin film and cause image display devices such as EL display device, PDP.

Background technology

In recent years, in fields such as optical field and optoelectronics, the polarizer that the phase place of light is controlled becomes one of important optical element.In addition,, can obtain ellipsoidal polarizing plate, various formations be studied according to the phase difference value of polarizer, wavelength dispersion etc. by the polarizer of on polaroid, fitting.

In the past, polarizer is made by unilateral stretching or two-way stretch macromolecule membrane.As the material of macromolecule membrane, for example can enumerate the material that uses polycarbonate resin, its wavelength dispersion is big, and is high more the closer to the short wavelength side phase differential.Relative with it, at present the polarizer that uses has used the little norbornene resin of wavelength dispersion or the closer to the high more modified polycarbonate resin of long wavelength side phase differential.In addition, these polarizers are just by with the stacked use of various angles.But, to compare with polycarbonate resin, the cost of norbornene resin and modified polycarbonate is higher.Their sandwich then further makes cost improve.In addition, these sandwich need be fitted with veneer with various shaft angle degree punchings, thus also can spend process cost or time, and become reasons for quality decrease.

On the other hand, as polarizer, known have a liquid crystal aligning layer that forms on oriented substrate.This liquid crystal aligning layer is by at liquid crystal material such as coated with liquid crystal monomer or liquid crystal polymer on the oriented substrate and (with reference to patent documentation 1) that the method that is cured after its orientation unanimity is obtained.Liquid crystal material has bar-shaped nematic phase type liquid crystal or discoid liquid crystal etc., and is the same with the polarizer that has used oriented film, according to the wavelength dispersion characteristic various kinds arranged.As oriented substrate, can enumerate stretching macromolecule membrane or friction orientation film.

When on the stretching macromolecule membrane, making the liquid crystal material orientation, require the axle precision of stretching macromolecule membrane.But the axle precision of the precision more than Width ± 1 ° can not be stablized and be obtained cheaply to the stretching macromolecule membrane that the longitudinal stretching by in the past and the method for cross directional stretch are made.Thus, the stretching macromolecule membrane is sometimes as not needing the C plate of a precision (when the refractive index of establishing the plane is nx, ny, when the refractive index of thickness direction is nz, nx ny＞nz or nz＞nx ny) or the oriented substrate of cholesteric crystal, but need in the production of axle accuracy A plates (nx＞ny nz or nx＜ny nz) to be difficult to.In addition, if the surface of friction orientation film is contaminated before the coated with liquid crystal material, then the orientation of liquid crystal material reduces, and is difficult to obtain the good liquid crystal aligning layer of orientation.For example, after base film was carried out friction treatment, when the surface that made the friction orientation film before the operation of coated with liquid crystal material and roller etc. contacted, then the orientation of liquid crystal material reduced.Therefore, in the manufacture method of the liquid crystal aligning film that has used the friction orientation film, be difficult to adopt the continuous mode of production by volume to volume (roll to roll).

Patent documentation 1: specially permit instructions No. 2784680

Summary of the invention

The objective of the invention is to, a kind of manufacture method that can make the liquid crystal aligning film that liquid crystal material is orientated well on the base film that carries out orientation process by friction is provided.

In addition, the present invention also aims to, liquid crystal aligning film, the optical thin film that has used this liquid crystal aligning film that obtains by this manufacture method, the image display device that has used this optical thin film are provided.

The inventor etc. concentrate on studies in order to achieve the above object, found that the manufacture method by the liquid crystal aligning film shown in following can solve above-mentioned problem, thereby have finished the present invention.

Promptly; the present invention relates to a kind of manufacture method of liquid crystal aligning film; it is characterized in that, comprising: the operation of the transparent base film implementation orientation being handled by friction (1), be that surface protective plate below the 0.5N/50mm fits in operation (2) on the described orientation process face, peels off after the described surface protective plate operation (3) that on described orientation process face coating contains the liquid crystal material of liquid crystal monomer and/or liquid crystal polymer, makes immobilized operation (4) after the described liquid crystal material orientation peeling force.

In the manufacture method of the liquid crystal aligning film of the invention described above; arrive afterwards between the liquid crystal material working procedure of coating (3) in friction orientation treatment process (1); have surface protective plate is fitted in by the bonding process (2) of the orientation process face of friction treatment, before being about to coated liquid crystal material, can not contacted with other object by the orientation process face of friction treatment.Thereby the orientation that described orientation process face can suppress to be caused by pollution reduces, and keeps good orientation, and can make the liquid crystal material orientation in the case.Therefore, the orientation of liquid crystal material is reduced and have the liquid crystal aligning film of any slow axis by the long axis direction that volume to volume is produced relative film continuously.Thus, can make thin cheaply in addition can be with big molded dimension the corresponding and liquid crystal aligning film that can in polarizer etc., utilize.The manufacture method of liquid crystal aligning film of the present invention can be used for the manufacture method of various polarizers, but needing especially to be preferred for the manufacture method of axle accuracy A plate equiphase difference plate.

The surface protective plate that uses in operation (2) can use peeling force to be the surface protective plate below the 0.5N/50mm.Peeling force represents that relative triacetylcellulose film is by 180 ° peel off and power (N/50mm) during with the speed stripper surface screening glass of 300mm/min.Specifically, be to measure by the method for putting down in writing among the embodiment.When the peeling force of described surface protective plate surpasses 0.5N/50mm, make the orientation confusion of friction treatment face by peeling off of surface protective plate, the orientation of liquid crystal material is reduced.Described peeling force is preferably below the 0.5N/50mm, more preferably below the 0.3N/50mm.Wherein, from the functional point of view by surface protective plate protection orientation process face, peeling force is preferably more than the 0.03N/50mm, more preferably more than the 0.05N/50mm.

In the manufacture method of described liquid crystal aligning film, as surface protective plate, the preferred use has substrate layer and bonding coat and the surface protective plate by their co-extruded being gone out or making by coating bonding coat on substrate layer.Described surface protective plate preferably uses substrate layer to contain the ethylene series resin and bonding coat contains the screening glass of ethylene-vinyl acetate copolymer.

In the manufacture method of described liquid crystal aligning film, during the peeling off of the surface protective plate in carrying out operation (3), the preferably clear base film evenly has any electric charge in the plus or minus electric charge.When carrying out the peeling off of surface protective plate,, think that then the friction orientation treated side can keep orientation as long as transparent base film evenly has any electric charge.To whether evenly having the affirmation of electric charge, colored metal powder that can be by scattering band positive and negative electric charge (for example, by charged and have the toner etc. of different colours respectively) carries out.

In addition, the invention still further relates to the liquid crystal aligning film that the manufacture method by described liquid crystal aligning film obtains.

In addition, the invention still further relates to a kind of optical thin film, it is characterized in that, use 1 described liquid crystal aligning film at least.The liquid crystal aligning film is slim and has uniform phase differential, is suitable as polarizer and uses.In addition, liquid crystal aligning film (polarizer) can be suitable as ellipsoidal polarizing plate etc. with the polaroid combination.

In addition, the invention still further relates to the image display device that has used described optical thin film.

And then, the invention still further relates in the manufacture method of described liquid crystal optics film, be used for operation (2) and peeling force be the following surface protective plate of 0.5N/50mm.

Description of drawings

Fig. 1 is the photo that is illustrated in the color distribution of the toner that adheres to that shows electriferous state among the embodiment 1.

Fig. 2 is the photo that is illustrated in the color distribution of the toner that adheres to that shows electriferous state among the embodiment 2.

Embodiment

Below, about the manufacture method of liquid crystal aligning film of the present invention, in order each operation is described.

(operation (1))

In operation (1), transparent base is carried out orientation process by friction.

＜transparent base film 〉

Transparent base film is so long as in that the material that changes liquid crystal material is taken place do not occur under the temperature of orientation, then be not particularly limited, and for example can use individual layer or stacked various plastic sheetings, glass plate, metal etc.As plastic sheeting, can be exemplified as polyester based polymers such as polyethylene terephthalate, PEN, cellulose-based polymkeric substance such as cellulose under diacetyl cellulose or three second, the polycarbonate based polymer, the film that transparent polymers such as acrylic acid series polymeric compounds such as polymethylmethacrylate constitute.In addition, can also enumerate as styrenics such as polystyrene, acrylonitritrile-styrene resins, olefin polymers such as tygon, polypropylene, polyolefin, ethylene-propylene copolymer with ring-type or norborene structure, vinyl chloride-based polymer, the film that transparent polymers such as acid amides based polymer such as nylon or aromatic polyamide constitute.And then, can also enumerate the film that constitutes as transparent polymers such as imide series polymkeric substance, sulfone based polymer, polyethersulfone based polymer, polyetheretherketone based polymer, polyphenylene sulfide based polymer, vinyl alcohol system polymer, vinylidene chloride based polymer, polyvinyl butyral based polymer, arylide based polymer, polyoxymethylene based polymer, epoxy based polymer or above-mentioned mixture of polymers etc.As transparent base film, be preferably triacetylcellulose film or norbornene resin film, ethylene series film.

In addition, transparent base film can also be used and be provided with polyvinyl alcohol film, polyimide is the material of film, polysiloxane series film, vitreous macromolecule membrane.

Material as forming vitreous macromolecule membrane tends to use alcoxide (alcoxide), particularly uses the alcoxide silicasol.The solution that alcoxide as alcohol is usually.Remove after described solution is applied on the base film and desolvate, promote sol gel reaction, on base film, form transparent vitreous macromolecule membrane thus by heating.Form the alcoxide silicon gel layer by the alcoxide silicasol.Method as the above-mentioned alcoxide silicon sol solution of coating on substrate can adopt as rolling method, photogravure coating process, excellent Tu Fa etc.As except that the method for desolvating, promoting and reacting, can utilize drying, the drying in drying oven etc. under the room temperature usually.

As friction treatment, the cloth or the cortical material that can utilize fine fibres such as rayon or cotton yarn to constitute rub to (rubbing) above the base film, carry out orientation process thus.Described cloth or skin material can adopt the method that rubs to a direction by the friction roller that they are curled.In addition, this friction roller can change the shaft angle degree to 0 °～± 45 ° directions.Use so to change the shaft angle degree and to carry out the material of friction treatment and the liquid crystal aligning film that obtains, can make polarizer (compensating plate) with various optical axises.

(operation (2))

In the operation (2) be that surface protective plate below the 0.5N/50mm fits in described orientation process face with peeling force.

As long as it is below the 0.5N/50mm, then to be not particularly limited that surface protective plate satisfies peeling force, can form by 1 layer, also can be by forming more than 2 layers.In the surface protective plate that forms by 1 layer, this 1 layer is satisfied peeling force is below the 0.5N/50mm.On the other hand, by forming more than 2 layers in the surface protective plate of surface protective plate, at least 1 layer as substrate layer, and at least 1 layer as bonding coat.The bonding coat side is fitted on the described orientation process face.

Below the surface protective plate with substrate layer and bonding coat is described.The manufacture method that formation is had the surface protective plate of substrate layer and bonding coat is not particularly limited, and preferably makes substrate layer and bonding coat film forming by the co-extruded method.As the co-extruded method, may be in accordance with in thin film fabrication etc. normally used plavini, T die head method etc. and carry out.In addition, also can adopt the manufacture method that forms the formation surface protective plates such as method of bonding coat and transfer printing by coating on substrate layer.

As the material that forms substrate layer, can enumerate as the ethylene series resin.The ethylene series resin is olefin homo system or uses multiple alkene and then use the copolymer resinses such as block polymer, atactic polymers of other monomer, be illustrated as ethylene-based polymers such as acrylic polymer, low density polyethylene, high density polyethylene, medium density polyethylene, linea low density particularly, the olefin copolymer of alkene such as olefin polymers such as ethylene-propylene copolymer, ethene-alpha-olefin copolymer, reactant TPO, ethylene-methyl methacrylate methyl terpolymer and other monomer.

For generation of preventing deterioration etc., also can add as antioxidant, ultraviolet light absorber, bulky amine in support base material be light stabilizers such as light stabilizer.In addition, also can cooperate antistatic agent, also just like the filling agent of calcium oxide, magnesium oxide, monox, zinc paste, titanium dioxide and so on, pigment is prevented the gum agent, lubricant, the adjuvant that anti blocking agent etc. are suitable.

The thickness of substrate layer is 20～300 μ m, and particularly 30～250 μ m are preferably 40～200 μ m, but are not limited to this.

As the resin that forms bonding coat, optimal ethylene-ethyl acetate multipolymer.In addition, the material as constituting bonding coat for example can use known bonding agents such as rubber system, acrylic acid series or carbamate system.Example as the rubber based polymer, can enumerate natural rubber, polyisobutylene, butyl rubber, polyisoprene, diene polymer or their hydrogenated products such as polybutadiene, ethylene-propylene rubber, ethene-alpha-olefin, ethylene series such as ethylene-propylene-alpha-olefin or propylene-alpha-olefin rubber, s-B-S (SBS) or styrene-isoprene-phenylethene (SIS), styrene-ethylene-isoprene-styrene (SEBS), the A-B-A type block polymer of styrene-ethylene-propylene-styrene (SEPS) and so on, perhaps styrene-butadiene (SB) or styrene-isoprene (SI), styrene-ethylene-butylene copolymer (SEB), the A-B type segmented copolymer of styrene-ethylene-propylene copolymer (SEP) and so on, polystyrene random copolymers of styrene butadiene rubbers (SBR) and so on or hydrogenated styrene are random copolymers (HSBR), the A-B-O type styrene of styrene-ethylene-butylene copolymer-alkene crystallization (SEBC) and so on-alkene system of crystallization segmented copolymer, the C-B-C type alkene system of crystallization segmented copolymer of alkene crystallization-ethylene-butene copolymer-alkene crystallization (CEBC) and so on etc. are as the rubber based polymer of base polymer.

When forming bonding coat, be purpose etc. with the control adhesion characteristic, as required, can cooperate as softening agent, the ethylene series resin, silicone-based polymkeric substance, aqueous acrylic acid series copolymer, the phosphate based compound, tackifier, antiaging agent, bulky amine is a light stabilizer, ultraviolet light absorber, also suitable adjuvant just like the filling agent of calcium oxide, magnesium oxide, silicon dioxide, zinc paste, titanium dioxide and so on or pigment etc.

The thickness of bonding coat can be generally 1～50 μ m according to decisions aptly such as peeling forces, is preferably 2～40 μ m, is preferably 5～20 μ m especially.Also can be as required protect for the interim separator etc. of adhering to before using at bonding coat.

Described surface protective plate is fitted to described orientation process face, but, be preferably in the back then operation (1) of operation (1) end and fit immediately in order not pollute the orientation process face.

(operation (3))

In operation (3), after above-mentioned stripper surface screening glass, contain the liquid crystal material of liquid crystal monomer and/or liquid crystal polymer in described orientation process face coating.

In order not pollute the orientation process face, peeling off preferably of described surface protective plate soon carried out before the coated with liquid crystal material.Stripping means to surface protective plate is not particularly limited, and preferably peels off with certain speed so that do not damage the orientation of orientation process face.For example preferably carry out with 180 ° peel off.In the present invention, owing to use peeling force to be the surface protective plate below the 0.5N/50mm, the orientation process face of the transparent base film after the stripper surface screening glass can have any electric charge in the plus or minus electric charge equally.

Liquid crystal material contains liquid crystal monomer or liquid crystal polymer or their potpourri.

Liquid crystal monomer is to have demonstration to the various skeletons of the liquid crystal aligning of row, cholesterol or smectic and have the liquid crystal compounds of polymerism functional groups such as unsaturated double-bonds such as at least a kind of acryloyl group, methacryl, vinyl or epoxy radicals endways.In these liquid crystal monomers, what tend to use is to have liquid-crystal compoundss unsaturated double-bond, nematic crystal such as at least a kind of acryloyl group or methacryl.As liquid crystal monomer,, preferably has the monomer of 2 above optical polymerism functional groups in order to improve permanance.As such liquid crystal monomer, can specifically enumerate monomer with following formula (1) expression.These liquid crystal monomers can be a kind, and also two or more kinds may be used.

[changing 1]

In above-mentioned formula (1), A ¹And A ²Represent polymerizable group respectively, can be identical, also can be different.In addition, A ¹And A ²In any one party can be hydrogen.X represent respectively singly-bound ,-O-,-S-,-C=N-,-O-CO-,-CO-O-,-O-CO-O-,-CO-NR-,-N-R-CO-,-NR-,-O-CO-NR-,-NR-CO-O-,-CH ₂-O-or-NR-CO-NR, in described X, R represents H or C ₁～C ₄Alkyl, M are represented linearity atomic group (mesogene) base.

In above-mentioned formula (1), X can be identical, also can be different, but be preferably identical.Even in the monomer of above-mentioned formula (1), preferred A ²Relative A ¹Be configured in contraposition.

In addition, preferred A ¹And A ²Independent respectively also with following formula Z-X-(Sp) _n(2) expression, A ¹And A ²Be preferably identical group.

In above-mentioned formula (2), Z represents crosslinkable groups, and X is identical with above-mentioned formula (1), and Sp represents the isolation group that is made of the straight or branched alkyl with 1～30 C atom, and n represents 0 or 1.Carbochain among the above-mentioned Sp also can be by sulphur, non-adjacent imino group or the C in the oxygen in the ether functional group, the thioether functional group ₁～C ₄Calkings such as alkyl imino.

In above-mentioned formula (2), Z is preferably any one in the atomic group of representing with following formula.In following formula,, can be exemplified as groups such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, the tert-butyl group as R.

[changing 2] H ₂C=CH-, HC ≡ C-,

-N＝C＝O，-N＝C＝S，-O-C≡N，

In addition, in above-mentioned formula (2), Sp is preferably any one in the atomic group of representing with following formula, and in following formula, preferred m is 1～3, and p is 1～12.

[changing 3]

-(CH ₂) _p-，-(CH ₂CH ₂O) _nCH ₂CH ₂-，-CH ₂CH ₂SCH ₂CH ₂-，

-CH ₂CH ₂NHCH ₂CH ₂-，

In above-mentioned formula (1), M preferably uses following formula (3) expression, and in following formula (3), X is identical with X in the above-mentioned formula (1).Q for example represents to replace or unsubstituted alkylidene or aromatic hydrocarbon atomic group, in addition, for example also can be to replace or unsubstituted straight chain or side chain C ₁～C ₁₂Alkylidene etc.

[changing 4]

At above-mentioned Q is under the situation of above-mentioned aromatic hydrocarbon atomic group, for example preferably as represented atomic group of following formula or their replacement analog.

[changing 5]

As the replacement analog of the aromatic hydrocarbon atomic group of in above-mentioned formula, representing, for example can on each aromatic ring, have 1～4 substituting group, in addition, also can on each aromatic ring or group, have 1 or 2 substituting group.Above-mentioned substituting group can be identical or different respectively.As described substituting group, can enumerate for example C ₁～C ₄Alkyl, nitro, halogens such as F, Cl, Br, I, phenyl, C ₁～C ₄Alkoxy etc.

As the concrete example of described liquid crystal polymer, for example can enumerate monomer with following formula (4)～(19) expression.

[changing 6]

The temperature range that above-mentioned liquid crystal monomer demonstrates liquid crystal liquid crystal property is according to its kind and difference for example is preferably 40～120 ℃ of scopes, and more preferably 50～100 ℃ of scopes are preferably 60～90 ℃ of scopes especially.

In containing the liquid crystal material of liquid crystal monomer, contain polymerization initiator usually.Can suitably select and the corresponding polymerization initiator of the polymerization of liquid crystal monomer.As the polymerization of polymerizable liquid crystal monomer, can enumerate for example ultraviolet polymerization, use Photoepolymerizationinitiater initiater in this case.Can use various Photoepolymerizationinitiater initiaters with being not particularly limited.As Photoepolymerizationinitiater initiater, can illustration such as Irgacure 907, Irgacure 184, Irgacure 651, the Irgacure 369 etc. of チ ノ ミ ス ベ シ ヤ リ テ イ ケ ミ カ Le ズ corporate system.Consider the kind of liquid crystal monomer, the addition of Photoepolymerizationinitiater initiater can be added to the degree that does not upset orientation.Usually, relative 100 weight portion liquid crystal monomers are preferably about 0.5～30 weight portion.More preferably 2～7 weight portions, more preferably 3～6 weight portions.

Liquid crystal polymer can be used the polymkeric substance of demonstration to backbone chain type, side chain type or their the compound various skeletons of the liquid crystal aligning of row, cholesterol or smectic with being not particularly limited.

Liquid crystal polymer as backbone chain type, can enumerate condensation based polymer, for example polymkeric substance such as polyethers system, polyamide-based, polycarbonate-based, polyester-imide system with the structure that combines linearity atomic group (mesogene) base that constitutes by aromatic series unit etc.As the above-mentioned aromatic series unit that becomes linearity atomic group (mesogene) base, can enumerate phenyl system, biphenyl base system, naphthyl system, these aromatic series unit also can have substituting groups such as cyano group, alkyl, alkoxy, halogen.

As the liquid crystal polymer of side chain type, can enumerate main chain with polyacrylate system, polymethacrylate system, polysiloxane series, poly-malonic acid system and be skeleton and on side chain, have the polymkeric substance of linearity atomic group (mesogene) base that constitutes by annular unit etc.Above-mentioned annular unit as becoming linearity atomic group (mesogene) base can be exemplified as biphenyl base system, phenylbenzoate system, cyclohexylbenzene system, azoxy benzene series, azomethine system, azo benzene series, phenyl pyrimidine system, tolane system, diphenyl benzene formic ether system, bis cyclohexane system, cyclohexyl benzene series, terphenyl system etc.Wherein, the end at these annular units also can have for example substituting groups such as cyano group, alkyl, alkoxy, halogen.

In addition, linearity atomic group (mesogene) base of liquid crystal polymer can be by the isolation group portion combination of giving flexibility arbitrarily.As isolating group portion, can enumerate polymethylene chain, polyoxymethylene chain etc.The repeat number that forms the structural unit of isolating group portion is suitable decision of chemical constitution by linearity atomic group (mesogene) portion, but the repetitive of polymethylene chain is 0～20, be preferably 2～12, the repetitive of polyoxymethylene chain is 0～10, is preferably 1～3.

Wherein, the nematic phase type is that liquid crystal polymer can to become cholesterol be liquid crystal polymer by containing low molecular chiral agent or import the chirality composition in component of polymer.

Molecular weight to liquid crystal polymer is not particularly limited, but preferable weight-average molecular weight is about 2,000～100,000.If it is big that the weight-average molecular weight of liquid crystal polymer becomes, then from the orientation as liquid crystal, the weight-average molecular weight of liquid crystal polymer is more preferably below 50,000.In addition, if the weight-average molecular weight of liquid crystal polymer diminishes, the tendency of shortage as the film forming of non-current layer arranged, so the weight-average molecular weight of liquid crystal polymer is more preferably more than 2.5 thousand.

Liquid crystal material can contain liquid crystal monomer or liquid crystal polymer or their potpourri.Described liquid crystal material is coated on the method for described orientation process face, can enumerates use liquid crystal material is dissolved in the method for fusion coating after the solution coating method of the solution in the solvent or the fusion, wherein preferred solution coating method.

As the solvent that when modulating described solution, uses, according to the kind of liquid crystal material or transparent base film and difference, therefore cannot treat different things as the same, but can use chloroform usually, methylene chloride, ethylene dichloride, tetrachloroethane, triclene, zellon, halogenated hydrocarbons such as chlorobenzene, phenol, phenols such as parachlorophenol, benzene, toluene, dimethylbenzene, methoxybenzene, 1,2-dimethoxy benzenes etc. are aromatic hydrocarbon based, acetone, ethyl acetate, the tert-butyl alcohol, glycerine, ethylene glycol, triethylene glycol, glycol monoethyl ether, diethylene glycol dimethyl ether, ethyl cellosolve, butyl cellosolve, 2-Pyrrolidone, the N-N-methyl-2-2-pyrrolidone N-, pyridine, triethylamine, tetrahydrofuran, the diformazan formamide, dimethyl acetamide, dimethyl sulfoxide (DMSO), acetonitrile, butyronitrile, carbon disulphide etc.The concentration of solution depend on use liquid crystal material dissolubility or as the thickness of the liquid crystal liquid crystal property film of final purpose, so cannot treat different things as the same, but, be preferably the scope of 7～30 weight % usually at 3～50 weight %.

In addition, also can suitably contain adjuvant in the liquid crystal material.In addition, also can become cholesteric liquid crystal material by adding the chirality agent.

The thickness of the liquid crystal aligning layer that obtains from the described liquid crystal material of coating is preferably about 1～10 μ m.Wherein, under the situation that needs accurate control liquid crystal layer thickness especially,, pay particular attention to the concentration of control solution, the thickness of coated film etc. owing to roughly determine thickness in the stage that is coated to transparent base film.

Be coated in coating method on the orientation process face of implementing friction treatment as the described solution that will use above-mentioned solvent and be adjusted into desired concn, can adopt as rolling method, photogravure coating process, excellent Tu Fa etc.After the coating, remove and desolvate, on base film, form liquid crystal layer.The condition of removing to solvent is not particularly limited, and desolvate as long as can be substantially remove, and liquid crystal layer can not occur flowing, flow down and get final product.Usually utilizing at room temperature drying, the drying in drying oven, the heating on heating plate etc. to remove desolvates.

(operation (4))

In operation (4), make above-mentioned liquid crystal material orientation after, liquid crystal aligning layer is carried out immobilization.Thus, fixing liquid crystal aligning layer and obtain the liquid crystal aligning film.

The orientation of liquid crystal material is orientated by making liquid crystal monomer and/or liquid crystal polymer become mesomorphic state.For example, heat-treat so that liquid crystal material in liquid crystal temperature range, is orientated under mesomorphic state.As heat treatment method, can carry out with the method identical with above-mentioned drying means.Heat treatment temperature is according to the kind of liquid crystal material that uses and base film and different, so cannot treat different things as the same, but usually at 60～300 ℃, is preferably in 70～200 ℃ the scope and carries out.In addition, heat treatment time is according to the kind of the liquid crystal material of heat treatment temperature and use, base film and different, thus cannot treat different things as the same, but usually between 10 seconds～30 minutes, be preferably 30 seconds～scope between 15 minutes selects.When than 10 seconds in short-term, might fully be orientated formation; When longer than 30 minutes, producing efficient in batches might variation.

Process for fixation as the liquid crystal material of described orientation when liquid crystal material contains liquid crystal monomer, makes its polymerizing curable.Polymerizing curable can adopt various means according to the kind of liquid crystal monomer, for example, can adopt by light-struck optical polymerism method.The preferred employing by light-struck polymerizing curable.By polymerizing curable, liquid crystal monomer carries out polymerization or crosslinked immobilization then, thereby obtains the high film of permanance.Rayed is for example undertaken by the ultraviolet ray irradiation.The ultraviolet ray illuminate condition is fully carrying out with the promotion reaction in inert gas environment preferably.Normally used representative be to have about 80～300mW/cm ²The high-pressure mercury uviol lamp of illumination.Also can use the lamp of other kinds such as metal halide UV lamp or incandescent lamp.Also have, the liquid crystal layer surface temperature when making the ultraviolet ray irradiation in liquid crystal temperature range, can carry out up to film apart from cold mirror, water-cooled, other cooling processing or accelerate linear velocity etc. and suitably adjusting.

When liquid crystal material does not contain liquid crystal cells and when only containing liquid crystal polymer, can liquid crystal aligning layer is cooled to below the liquid crystal temperature by cooling, thus fixing.

Liquid crystal aligning film by described liquid crystal aligning layer constitutes can use with described base film, in addition, it can also be peeled off and uses as optical thin film from base film.And then, also it can be transferred on other optical thin film and use.Above-mentioned liquid crystal aligning film can be separately or with other film combinations, thereby as optical thin films such as polarizer, viewing angle compensation film, optical compensating film, elliptic polarization optical thin films.Below they are described.

In the optical thin film that is used for image display devices such as liquid crystal indicator, use polaroid.Polaroid normally has protective film in polariscopic one or both sides.Polariscope is not particularly limited, can uses various polariscopes.As polariscope, can be exemplified as on the hydrophilic macromolecule films such as dividing the saponification film at polyvinyl alcohol film, part dimethoxym ethane polyvinyl alcohol film, ethylene-vinyl acetate copolymer pastern the material of unilateral stretching after the dichroic substance such as absorption iodine or dichroic dye; Polyenes such as the desalination acid treatment thing of the processed thing of polyvinyl alcohol (PVA) or Polyvinylchloride are oriented film etc.Wherein, preferably using stretching polyethylene alcohol is to adsorb dichroic material (iodine, dyestuff) behind the film and be orientated the polariscope that forms.There is no particular limitation to polariscopic thickness, but be generally about about 5～80 μ m.

With polyvinyl alcohol film with iodine staining after the polariscope that unilateral stretching forms for example, after can dyeing by the aqueous solution that polyvinyl alcohol (PVA) be impregnated in iodine, make for 3 to 7 times that are stretched to raw footage.As required, also can impregnated in the aqueous solution of boronic acid containing or potassium iodide etc.In addition, as required, also can be before dyeing polyvinyl alcohol film be impregnated in the water and wash.By the washing polyvinyl alcohol film, except can the lip-deep dirt of flush away polyvinyl alcohol film and anti blocking agent, can also prevent non-uniform phenomenons such as stain by making the polyvinyl alcohol film swelling.Stretch and both can after with iodine staining, carry out,, can also after stretching, dye with iodine on one side also can stretch by an Edge Coloring.Also can or stretch in the water-bath in the aqueous solution of boric acid or potassium iodide etc.

In being arranged at the protective film of above-mentioned polariscopic one or both sides, the preferred material that has good character at aspects such as the transparency, physical strength, thermal stability, moisture shielding, isotropy.As the material of above-mentioned protective film, for example, can be exemplified as polyester based polymers such as polyethylene terephthalate or PEN; Cellulose-based polymkeric substance such as diacetyl cellulose or triacetyl cellulose; Acrylic acid series polymeric compounds such as polymethylmethacrylate; Polystyrene or acrylonitritrile-styrene resin styrenics such as (AS resins); Polycarbonate based polymer etc.In addition, as the example of the polymkeric substance that forms protective film, the polyolefin that can also be exemplified as tygon, polypropylene, have ring system or norborene structure, the polyolefin polymkeric substance of ethylene-propylene copolymer and so on; Vinyl chloride-based polymer; Acid amides such as nylon or aromatic polyamide based polymer; The imide series polymkeric substance; The sulfone based polymer; The polyethersulfone based polymer; The polyetheretherketone based polymer; The polyphenylene sulfide based polymer; The vinyl alcohol based polymer, the vinylidene chloride based polymer; The polyvinyl butyral based polymer; The arylide based polymer; The polyoxymethylene based polymer; The epoxy based polymer; Perhaps described mixture of polymers etc.In addition, can also enumerate material of Thermocurable, uv curing resins etc. such as acrylic acid series, carbamate system, propenoic methyl carbamate system, epoxy system, silicone-based being carried out filming etc.

In addition, open in the 2001-343529 communique (WO 01/37007) thin polymer film of record the spy, can be exemplified as comprise (A) side chain have replace and/or not substituted imido thermoplastic resin and (B) have the resin combination of the thermoplastic resin of replacement and/or unsubstituted phenyl and itrile group at side chain.As concrete example, can be exemplified as and contain by the contract film of resin combination of alternating copolymer that imines forms and acrylonitritrile-styrene resin of isobutylene and N-methyl maleic anhydride.As film, the film that can use mixing extruded product by resin combination etc. to constitute.

From viewpoints such as polarized light characteristic and permanance, the protective film that can especially preferably use is with alkali etc. the triacetylcellulose film that saponification is handled to be carried out on the surface.Protective clear layer can be any thickness, but is purpose with slimming of polaroid etc., generally is preferably below the 500 μ m, and then is preferably 1～300 μ m, is preferably 5～300 μ m especially.Wherein, when being provided with protective film in polariscopic both sides, the transparent protective film that can use the outside in it to constitute by different polymkeric substance etc.

In addition, transparent protective film had better not be painted.Therefore; the preferred use (wherein with Rth=(nx-nz) d; nx is the refractive index of the slow axis direction in the thin film planar, and nz is the refractive index of film thickness direction, and d is a film thickness) phase difference value of the film thickness direction of expression for-90nm～+ protective film of 75nm.Phase difference value (Rth) by using this thickness direction for-90nm～+ protective film of 75nm, can roughly eliminate painted (optical clouration) of the polaroid that causes by protective film.Thickness direction phase difference value (Rth) more preferably-80nm～+ 60nm, be preferably especially-70nm～+ 45nm.

Between described polariscope and protective film, normally adhere to by aqueous adhesive.As aqueous adhesive, can be illustrated as the polyethenol series tackifier, gelatin is tackifier, ethene base system latex system, aqueous polyurethane, water system polyester etc.

As above-mentioned protective film, can also use and implement hard conating or antireflection processing, anti (sticking), with the protective film of diffusion or anti-dazzle processing as purpose.

The purpose of implementing to be coated with firmly processing is the surface distress etc. that prevents polaroid, and mode that for example can be by the curing tunicle that the additional hardness that is made of suitable uv curing resin such as acrylic acid series and silicone-based, sliding properties etc. are good on the surface of protective film etc. forms.Implementing the purpose that antireflection handles is the outer reflection of light that prevents on the polaroid surface, can finish by forming to wait based in the past antireflection film.In addition, implementing purpose that anti handles is the adhesion that prevents with adjacent layer.

In addition; the purpose of implementing non-glare treated is to prevent that outer light from disturbing the identification of polaroid transmitted light etc. in the polaroid surface reflection; for example; can give the micro concavo-convex structure to the protective film surface and form by mode of slightly coming to the surface that adopts sandblast mode or embossing processing mode or the suitable modes such as mode that cooperate transparent particulate.As the particulate that in the formation of described surperficial micro concavo-convex structure, contains, for example, can use mean grain size is the inorganic transparent particulates of being made up of silicon dioxide, aluminium oxide, titanium dioxide, zirconia, tin oxide, indium oxide, cadmium oxide, antimony oxide etc. such as organic system particulate that are particulate, are made up of crosslinked or uncrosslinked polymkeric substance etc. that often have electric conductivity of 0.5～50 μ m.When forming surperficial micro concavo-convex structure, the use amount of particulate is typically about 2～50 weight portions, preferred 5～25 weight portions with respect to transparent resin 100 weight portions that form surperficial micro concavo-convex structure.Antiglare layer also can be held concurrently to work as and be used for the polaroid transmitted light is spread and the diffusion layer (visual angle expanded functionality etc.) at expansion visual angle etc.

Also have, described anti-reflection layer, antiblocking layers, diffusion layer or antiglare layer etc. can also be as other optical layers, with the transparent protective film separate configuration except being arranged on protective film from one's body.

The ellipsoidal polarizing plate or the circular polarizing disk that above-mentioned polaroid can be constituted as stacked polarizer.Above-mentioned ellipsoidal polarizing plate or circular polarizing disk are described.They can change into rectilinearly polarized light elliptically polarized light or circularly polarized light by polarizer, perhaps elliptically polarized light or circularly polarized light are changed into rectilinearly polarized light, perhaps change the polarization direction of rectilinearly polarized light.Particularly, as rectilinearly polarized light being changed into circularly polarized light or circularly polarized light being changed into the polarizer of rectilinearly polarized light, can use so-called 1/4 wavelength sheet (be also referred to as λ/4 slice).1/2 wavelength sheet (be also referred to as λ/2 slice) is generally used for changing the situation of the polarization direction of rectilinearly polarized light.

Ellipsoidal polarizing plate can be used for following situation etc. effectively, i.e. compensation (preventing) supertwist nematic phase (STN) type liquid crystal indicator painted (blue or yellow) that produce because of the birefringence of liquid crystal layer, thus carry out the above-mentioned painted white black situation that shows that do not have.In addition, it is painted that the polaroid of control three-dimensional refractive index produces in the time of can also compensating (preventing) from the picture of oblique observation liquid crystal indicator, thereby preferred.Circular polarizing disk can be used for the situation adjusted as the tone of the image of the reflection-type liquid-crystal display device that coloured image is shown etc. effectively, but also has the function of reflecting of preventing.

In polarizer, can use for example various wavelength sheets or be used to compensate the member at painted or visual angle that the birefringence by liquid crystal layer causes etc. etc., can also stackedly have the polarizer of the proper phase difference that adapts with application target more than 2 kinds and optical characteristics such as control phase difference.As polarizer, can enumerate that the film that the suitable polymer blend by polycarbonate, norbornene resin, polyvinyl alcohol (PVA), polystyrene, polymethylmethacrylate, polypropylene or other polyolefin, polyarylate, polyamide and so on is constituted carries out stretch processing and the birefringent film that forms, by the oriented film that liquid crystal materials such as liquid crystal polymer are formed, the member of the oriented layer of usefulness film support liquid crystal material etc.

In addition, as the viewing angle compensation film, it can be laminated on the polaroid and use as wide visual angle polaroid.Compensation film for angular field of view is also to make image seem more clearly, be used to enlarge the film at visual angle under the situation of the direction that tilts a little observation liquid crystal display picture that is not orthogonal to picture.

As this kind viewing angle compensation polarizer, can use to be implemented in addition that two-way stretch is handled or on the both direction of quadrature, to implement stretch processing etc. and have birefringent film or the biaxially oriented film as the tilted alignment film etc.As the tilted alignment film, for example can enumerate behind the bonding heat-shrinkable film on the thin polymer film under effect because of the convergent force that adds thermosetting, thin polymer film is carried out stretch processing or/and the material of shrink process, make the material of liquid crystal polymer tilted alignment etc.The viewing angle compensation film can or enlarge the good visual angle of identification etc. with the painted grade that variation caused at the identification angle of the phase differential that prevents to cause based on liquid crystal cells and suit to make up as purpose.

In addition, from realizing the viewpoint at the wide visual angle that identification is good, can preferably use with triacetylcellulose film and support the optical compensation polarizer that optical anisotropic layer that the tilted alignment layer by the oriented layer of liquid crystal polymer, particularly discoid liquid crystal polymer constitutes forms.

Except above-mentioned, stacked optical layers when reality is used is had no particular limits, for example can use the film that becomes optical layers that reflecting plate or half transmitting plate etc. use in the formation of liquid crystal indicator etc. more than 1 layer or 2 layers.Particularly preferred polaroid is reflection type polarizer or the semi-transmission type polaroid that further stacked reflecting plate or semi-penetration plate form on ellipsoidal polarizing plate or circular polarizing disk; Perhaps further stacked brightness improving film and the polaroid that forms on polaroid.

Reflection type polarizer is provided with the reflection horizon and forms on polaroid, can be used for forming the liquid crystal indicator of the type that reflection shows from the incident light of identification side (demonstration side) incident etc., and can omit built-in light sources such as backlight, thereby have advantages such as being easy to make the liquid crystal indicator slimming.When forming reflection type polarizer, can be by being undertaken as required and by the suitable modes such as mode that protective clear layer etc. is set up the reflection horizon that is made of metal etc. in the one side of polaroid.

As the object lesson of reflection type polarizer, can be exemplified as required on the one side of the protective film of handling through delustring, set up the paper tinsel that constitutes by reflective metal such as aluminium or vapor-deposited film and form the polaroid etc. in reflection horizon.In addition, can also enumerate and make described protective film contain particulate and form surperficial micro concavo-convex structure, and have the reflection type polarizer etc. in the reflection horizon of micro concavo-convex structure thereon.The reflection horizon of described micro concavo-convex structure makes incident light diffusion by diffuse reflection, prevents that thus directionality or outward appearance are shinny, has the advantage that can suppress the light and shade inequality etc.In addition, the transparent protective film that contains particulate also has when incident light and reflected light thereof see through it the advantage etc. that can further suppress the light and shade inequality by diffusion.The formation in reflection horizon of the micro concavo-convex structure of the surperficial micro concavo-convex structure of reflection protective film, method that for example can be by directly setting up metal on the surface of protective clear layer with suitable modes such as evaporation mode such as vacuum evaporation mode, ion plating mode and sputter mode or plating modes etc. is carried out.

Instead reflecting plate directly is attached to the mode on the protective film of described polaroid, the reflection horizon can also be set on the suitable film that with this transparent membrane is benchmark forms reflector plate etc. and then use.Also have; because the reflection horizon is made up of metal usually; so from the decline of the reflectivity that prevents to cause, and then keep the viewpoint of initial reflectance for a long time and the viewpoint avoiding establishing protective seam in addition waits, preferably cover the type of service of its reflecting surface with protective film or polaroid etc. owing to oxidation.

Also have, in above-mentioned, the semi-transmission type polaroid can come reflected light that the reflection horizon of the semi-transmission types such as semi-transparent semi-reflecting lens of light transmission is obtained by making with the reflection horizon.The semi-transmission type polaroid is located at the rear side of liquid crystal cells usually, can form the liquid crystal indicator of following type etc., promptly, in brighter environment, use under the situation of liquid crystal indicator etc., reflection comes from the incident light of identification side (demonstration side) and display image, in darker environment, use the built-in light sources such as backlight at the back side that is built in the semi-transmission type polaroid to come display image.Promptly, the semi-transmission type polaroid is useful in the formation of liquid crystal indicator of following type etc., that is, under bright environment, can save the energy that uses light sources such as backlight, under darker environment, also can use in the formation of liquid crystal indicator etc. of type of built-in light source very useful.

The back side one side that polaroid and the film adhered polaroid that together forms of brightness improving is set at usually liquid crystal cells is then used.The brightness improving film is the film that shows below characteristic, promptly, when natural light incident being arranged because of the backlight of liquid crystal indicator etc. or from the reflection of rear side etc., the rectilinearly polarized light of reflection regulation polarizing axis or the circularly polarized light of prescribed direction, and make other light transmissions.Therefore brightness improving film and the stacked polaroid that forms of polaroid can be made the light incident from light sources such as backlights, and obtain the light that sees through of regulation polarized light state, simultaneously, the light beyond the described regulation polarized light state can not see through and quilt is reflected.By reflection horizon that is arranged at its rear side etc. the light that reflects on this brightness improving pellicular front is reversed once more, and make it to incide once more on the brightness improving film, make its part or all light transmission as the regulation polarized light state, thereby increase the light that sees through the brightness improving film, simultaneously provide the polarized light that is difficult to absorb to polariscope, can be thereby increase in the light quantity of utilization in the demonstration of liquid crystal display image etc., and can improve brightness thus.Promptly, pass polariscope and make under the situation of light incident from the rear side of liquid crystal cells with backlight etc. not using the brightness improving film, have light with the inconsistent polarization direction of polariscopic polarizing axis and be polarized mirror basically and absorb, thereby can't see through polariscope.That is, though can be different because of employed polariscopic characteristic, about 50% light can be polarized mirror and sponge, and therefore, the light quantity that can utilize in liquid crystal image demonstration etc. will reduce, and cause the image deepening.Because the brightness improving film carries out following operation repeatedly, promptly, making the light with the polarization direction that can be polarized the mirror absorption is not to incide on the polariscope, but such light is reflected on the brightness improving film, and then finish counter-rotating by reflection horizon of being located at its rear side etc., light is incided on the brightness improving film once more, like this, the brightness improving film only makes in the light of the two reflection and counter-rotating, its polarization direction becomes and can see through by the polarized light of polariscopic polarization direction, provide it to polariscope simultaneously, therefore can in the demonstration of the image of liquid crystal indicator, use the light of backlight etc. effectively, thereby can make picture bright.

Also can between brightness improving film and described reflection horizon etc., diffuser plate be set.Towards described reflection horizon etc., set diffuser plate can spread the light that passes through equably by the light of the polarized light state of brightness improving film reflection, eliminates polarized light state simultaneously and becomes the nonpolarized light state.That is, diffuser plate makes polarized light return to original natural light state.Carry out following process repeatedly, that is, and with this nonpolarized light state light directive reflection horizon that is the natural light state etc., after reflections such as reflection horizon, once more by diffuser plate and incide on the brightness improving film.Make polarized light return to the diffuser plate of original natural light state by between brightness improving film and above-mentioned reflection horizon etc., being provided with, can be in the brightness of keeping display frame, reduce the brightness disproportionation of display frame, thereby even and bright picture can be provided.By this diffuser plate is set, can suitably increase the repeated reflection number of times of first incident light, and utilize the diffusion function of diffuser plate, the display frame of homogeneous and bright can be provided.

As above-mentioned brightness improving film, for example can use: the demonstration of thin-film multilayer duplexer that dielectric multilayer film or refractive index anisotropy are different and so on send as an envoy to the rectilinearly polarized light of regulation polarizing axis see through and reflect the characteristic of other light film, cholesteric liquid crystal polymer alignment films or in the film substrate upper support the demonstrating any circularly polarized light reflection that will be in left-handed or the dextrorotation of film and so on of this aligned liquid-crystal layer and film that the film etc. of the characteristic of other light transmissions is suited.

Therefore, in the brightness improving film of the type that the above-mentioned rectilinearly polarized light that makes the regulation polarizing axis sees through, directly incide on the polaroid by making this see through light, can when suppressing the absorption loss that causes by polaroid, light be seen through effectively along the direction consistent with polarizing axis.On the other hand, in the brightness improving film that makes the type that circularly polarized light sees through of cholesteric and so on, though light is incided on the polariscope, but consider from suppressing the absorption loss this point, preferably this circularly polarized light carry out rectilinearly polarized lightization, reenter afterwards and be mapped on the polaroid by polarizer.And, by using 1/4 wavelength sheet, circularly polarized light can be transformed to rectilinearly polarized light as this polarizer.

About in the wide wavelength coverage in visible region, playing the polarizer of 1/4 wavelength sheet effect, for example can utilize following mode to obtain, that is, the phase separation layer that will play 1/4 wavelength sheet effect with respect to the light luminous energy of wavelength 550nm carries out overlapping mode etc. with the phase separation layer that the phase separation layer that shows other phase difference characteristics for example can play 1/2 wavelength sheet effect.So the polarizer that is disposed between polaroid and the brightness improving film can be made of the phase separation layer more than 1 layer or 2 layers.

Also have, with regard to cholesteric, also can make up the material of different reflection wavelengths, constitute overlapping arrangement more than 2 layers or 3 layers, obtain the member of wide wavelength coverage internal reflection circularly polarized light thus, thereby can obtain the circularly polarized light that sees through of broad wavelength coverage based on this in the visible region.

In addition, polaroid is as described polarized light divergence type polaroid, can be made of the member of stacked polaroid and the optical layers more than 2 layers or 3 layers.So, also can be to have made up the reflection-type ellipsoidal polarizing plate of above-mentioned reflection type polarizer or semi-transmission type polaroid and polarizer or semi-transmission type ellipsoidal polarizing plate etc.

Above-mentioned ellipsoidal polarizing plate or reflection-type ellipsoidal polarizing plate are by suitably combination and laminated polarizing sheet or reflection type polarizer and polarizer form.These class ellipsoidal polarizing plates etc. also can form by independent successively stacked (reflection-type) polaroid and polarizer in the manufacture process of liquid crystal indicator, to constitute the combination of (reflection-type) polaroid and polarizer, and stacked in advance be under the situation of optical thin films such as ellipsoidal polarizing plate, because outstanding, therefore has the advantage of the manufacturing efficient that can improve liquid crystal indicator etc. at aspects such as quality of stability or lamination operation.

On optical thin film of the present invention, also can be provided with bonding coat.Adhesive phase can also be used for the stacked of optical layers except being used for adhering on the liquid crystal cells.When bonding above-mentioned optical thin film, can their optic axis be adjusted into suitable arrangement angles according to purpose phase difference characteristics etc.

The bonding agent that forms bonding coat is not particularly limited, for example can selects aptly to use with bonding agent such as the polymkeric substance of acrylic acid series polymeric compounds, silicone-based polymkeric substance, polyester, polyurethane, polyamide, polyethers, fluorine system or rubber system etc. as base polymer.The preferred especially optical transparence that uses similar acrylic adhesive is good and demonstrate the adhesion characteristic and the good bonding agents such as against weather or thermotolerance of wetting state, coherency and the cementability of appropriateness.

And, except above-mentioned, from prevent the foamed phenomenon that causes because of moisture absorption or peel off phenomenon, the warpage of the decline of the optical characteristics that causes because of thermal expansion difference etc. or liquid crystal cells and then from the viewpoints such as formation of the good liquid crystal indicator of high-quality and permanance, the bonding coat of the low and excellent heat resistance of preferred hydroscopicity.

For example natural or synthetic resin, particularly tackifying resin or the filling agent that constitutes by glass fibre, beaded glass, metal powder, other inorganic powder etc., pigment, colorant, antioxidant etc. can be contained in the bonding coat and adjuvant in the bonding coat can be made an addition to.Also can be to contain particulate and the diffusible bonding coat of display light etc. in addition.

Can utilize suitable mode to carry out when on the one or both sides of optical thin film, setting up bonding coat.As its example, for example can enumerate following mode, promptly be modulated at the binder solution of about 10～40 weight % that dissolving in the solvent that pure material or potpourri by suitable solvent such as toluene or ethyl acetate constitute or dispersion base polymer or its composition form, directly it be attached to mode on the polaroid or on the optical thin film by suitable expansion mode such as curtain coating mode or application pattern then; Perhaps based on above-mentioned and after forming bonding coat on the separator with its handover and stick on mode on the polaroid or on the optical thin film etc.

Bonding coat also can be formed or the overlapping layer of each layer of kind etc. and being arranged on the one or both sides of polaroid or optical thin film as difference.In addition, in the time of on being arranged at the two sides, the inside and outside of polaroid or optical thin film also can be the bonding coat of different compositions, kind or thickness etc.The thickness of bonding coat can suitably be determined according to application target or bonding force etc., be generally 1～500 μ m, preferred 5～200 μ m, preferred especially 10～100 μ m.

For the face that exposes of bonding coat, for before using in order to prevent its pollution etc., can paste separator to cover temporarily.Can prevent the phenomenon that under common mode of operation, contacts thus with bonding coat.As separator, on the basis of satisfying above-mentioned thickness condition, for example can use as required with suitable removers such as silicone-based or chain alkyl system, fluorine system or molybdenum sulfides plastic sheeting, sheet rubber, paper, cloth, nonwoven fabrics, net, foam sheet or metal forming, their suitable thin slice bodies such as duplexer are applied suitable separators commonly used in the past such as material after the processing.

Also have; in the present invention; also can be on each layers such as the polariscope that forms above-mentioned polaroid, transparent protective film, optical thin film etc. and bonding coat; utilize the modes such as mode of for example using salicylate based compound or benzo phenol (benzophenol) based compound, benzotriazole based compound or ultraviolet light absorbers such as cyanoacrylate based compound, nickel coordination compound based compound to handle, make it to have ultraviolet absorption ability etc.

Optical thin film of the present invention can be preferred for the formation of various devices such as liquid crystal indicator etc.Liquid crystal indicator can form according to method in the past.Promptly, in general, liquid crystal indicator can form by the component parts such as combination of liquid crystals unit and optical thin film aptly and the illuminator that adds as required and the driving circuit of packing into, in the present invention, except using optical thin film of the present invention, be not particularly limited, can form according to method in the past.For liquid crystal cells, also can use for example liquid crystal cells of any type such as TN type or STN type, π type.

The one or both sides that can be formed in liquid crystal cells have disposed the liquid crystal indicator of above-mentioned optical thin film, used the suitable liquid crystal indicators such as device of backlight or reflecting plate in illuminators.At this moment, optical thin film of the present invention can be arranged on the one or both sides of liquid crystal cells.When optical thin film was arranged on both sides, they both can be identical, also can be different.In addition, when forming liquid crystal indicator, can be on suitable position suitable parts such as for example diffuser plate of configuration more than 1 layer or 2 layers, antiglare layer, antireflection film, fender, prism array, lens arra thin slice, light diffusing sheet, backlight.

Then, Organnic electroluminescent device (organic EL display) is described.Usually, organic EL display is to stack gradually transparency electrode, organic luminous layer and metal electrode and form luminophor (organic electroluminescent body) on transparency carrier.Here, organic luminous layer is the duplexer of various organic films, and known have: for example duplexer of the duplexer of hole injection layer that is made of triphenylamine derivant etc. and the luminescent layer that is made of fluorescence organic solids such as anthracenes or this kind luminescent layer and the electron injecting layer that is made of perylene derivant etc. or the various combinations such as duplexer of these hole injection layers, luminescent layer and electron injecting layer.

Organic EL display carries out luminous according to following principle, promptly, by on transparency electrode and metal electrode, applying voltage, injected hole and electronics in organic luminous layer, the energy excitation fluorescent material that produces by the compound of these holes and electronics, when the fluorescent material that is excited is got back to ground state, will radiate bright dipping.Middle multiple mechanism is identical with general diode, also can infer thus, and electric current and luminous intensity demonstrate with respect to impressed voltage and follow the stronger non-linear of rectification.

In organic EL display, in order to take out the light that produces in the organic luminous layer, at least one side's electrode must be transparent, will be used as anode by the transparency electrode that tin indium oxide transparent conductive bodies such as (ITO) is made usually.On the other hand, improve luminescence efficiency in order to carry out electronics to inject easily, it is crucial using the less material of work function on negative electrode, uses metal electrodes such as Mg-Ag, Al-Li usually.

In having the organic EL display of this formation, organic luminous layer is that film as thin as a wafer about 10nm constitutes by thickness.Therefore, organic luminous layer is also the same with transparency electrode, and light is almost completely seen through.Consequently, when not luminous from the incident of transparency carrier surface and see through transparency electrode and organic luminous layer and can be once more penetrating to the face side of transparency carrier at the light of metal electrode reflection, therefore, when carrying out identification from the outside, the display surface of organic El device is as minute surface.

In the organic EL display that comprises organic electroluminescent body as described below, can polaroid be set in the face side of transparency electrode, simultaneously between these transparency electrodes and polaroid, polarizer is set, above-mentioned organic electroluminescent body is to be provided with transparency electrode by applying the face side that voltage carries out luminous organic luminous layer, is provided with metal electrode and forms in the rear side of organic luminous layer simultaneously.

Become the effect of polarized light because polarizer and polaroid have to make from outside incident and at the light of metal electrode reflection, therefore, have the effect that can't pick out the minute surface of metal electrode by this polarized light effect from the outside.Particularly, when adopting 1/4 wavelength sheet to constitute polarizer and the angle of the polarization direction of polaroid and polarizer is adjusted into π/4, can cover the minute surface of metal electrode fully.

That is, the exterior light that is incident to this organic EL display has only the rectilinearly polarized light composition because of the existence of polaroid and sees through.This rectilinearly polarized light generally can be converted to elliptically polarized light by polarizer, and when polarizer be the angle of the polarization direction of 1/4 wavelength sheet and polaroid and polarizer when being π/4, become circularly polarized light.

This circularly polarized light sees through transparency carrier, transparency electrode, organic film, reflects on metal electrode, sees through organic film, transparency electrode, transparency carrier afterwards once more, converts rectilinearly polarized light once more to by polarizer.Then, because this rectilinearly polarized light is vertical with the polarization direction of polaroid, so can't see through polaroid.Its result can be covered the minute surface of metal electrode fully.

Embodiment

Below, by embodiment the present invention is specifically described, but the present invention is not limited by these embodiment.

The modulation of the coating liquid of＜liquid crystal material 〉

Modulation shows 10g liquid crystal monomer (BASF AG's system of nematic crystal phase, PaliocolorLC242) and the 3g Photoepolymerizationinitiater initiater (Chiba specialty chemicals corporate system, Irgacure907) (to polymerizable liquid crystal compound) is dissolved in the solution that forms in the 40g toluene.

＜peeling force 〉

With surface protective plate (150mm * 50mm) fit on the triacetic acid acyl cellophane; after 23 ℃ are placed 20 minutes down; power (N/50mm) when measuring speed stripper surface screening glass with 180 ° peel off, 300mm/min with cupping machine (オ リ エ Application テ Star Network (strain) system, テ Application シ ロ Application).

The affirmation of＜electriferous state 〉

The liquid crystal aligning film is different with obtaining, and confirms electriferous state immediately after transparent base film stripper surface screening glass.After transparent base film stripper surface screening glass, carrying out following affirmation immediately: promptly; on the face of this transparent base film, spill after the blue toner and electronegative red color tone toner of following positively charged; remove and enclose the toner that adheres to, the color distribution of the toner that Visual Confirmation adheres to.Under the situation of having only blue toner to adhere to, it is electronegative equably to be judged as the surface; Under the situation of having only the red color tone toner to adhere to, can be judged as surperficial homogeneous band positive electricity.Mix under the situation about existing at red color tone toner and blue toner, can judge that the electriferous state on surface is inhomogeneous.In embodiment 1, the photo of the color distribution of the toner that will adhere to as the demonstration of judging object is shown in Fig. 1, will be shown in Fig. 2 about the photo of comparative example 2.

Embodiment 1

The triacetylcellulose film surface is carried out after the orientation process by friction with rayon cloth, the peeling force of fitting immediately is the surface protective plate of 0.05N/50mm.The 6221F of surface protective plate Shi Yong Plot water chemistry (strain) system.Be to go out the substrate layer (thickness 50 μ m, tygon) of surface protective plate and bonding coat (ethylene-ethyl acetate copolymer) and make by co-extruded.Then, stripper surface screening glass (180 ° peel off) before the coating liquid that is about to the coated with liquid crystal material applies described coating liquid with wire bar #10 on described orientation process face.90 ℃ dry 5 minutes down, make the liquid crystal material orientation after, with metal halide light irradiation 1mJ/cm ²Light, make curable liquid crystal layer, obtain the liquid crystal aligning film of thick 2 μ m.

Embodiment 2

In embodiment 1, except using the surface protective plate of peeling force, with the embodiment 1 the same liquid crystal aligning film that obtains as 0.1N/50mm.Surface protective plate uses the サ Application テ Network ト PAC3 of (strain) サ Application エ-change development.Be to go out the substrate layer (thickness 60 μ m, tygon) of surface protective plate and bonding coat (ethylene-ethyl acetate copolymer) and make by co-extruded.

Embodiment 3

In embodiment 1, except using the surface protective plate of peeling force, with the embodiment 1 the same liquid crystal aligning film that obtains as 0.3N/50mm.

Comparative example 1

In embodiment 1, except not using surface protective plate, advance the 1 the same liquid crystal aligning film that obtains with embodiment.In comparative example 1, can see contacting between triacetylcellulose film and the roller.

Comparative example 2

In embodiment 1, except using the surface protective plate of peeling force, with the embodiment 1 the same liquid crystal aligning film that obtains as 1.5N/50mm.Surface protective plate uses the Y-16F of (strain) サ Application エ-change development.

Comparative example 3

In embodiment 1, except using the surface protective plate of peeling force, with the embodiment 1 the same liquid crystal aligning film that obtains as 1.0N/50mm.Surface protective plate uses day E-MASK of eastern electrician (strain) system.

The liquid crystal aligning film that obtains in embodiment and comparative example is carried out following evaluation.To the results are shown in the table 1.

(orientation)

Prepare the polaroid (SEG1425DU) of 2 day east electrician's system, be quadrature, between it, be configured in the liquid crystal aligning film (polarizer) that makes in above-mentioned and make an absorption axes (or see through spool) of frictional direction and a polaroid consistent.To this, measure its transmitance Y (%) with the DOT-3 of color corporate system in the village.When the friction orientation angle is disorderly, can confirm that transmitance rises, orientation reduces.If transmitance, can be judged liquid crystal below 0.1% and be in the state that evenly is orientated on the frictional direction, it is decided to be well.Be bad in addition.

Table 1

	Surface protective plate		Electriferous state	Orientation
						Have or not	Peeling force (N/50mm)	Transmitance (%)	Judge
	Embodiment 1	Have		0.05	Have only blue toner adhere to/electronegative					0.05	Well
Embodiment 2			Have			0.1	Have only blue toner adhere to/electronegative	0.07	Well
	Embodiment 3	Have		0.3	Have only blue toner adhere to/electronegative					0.06	Well
Comparative example 1			Do not have			-	Red color tone toner and blue toner mixing existence/charged inhomogeneous	0.25	Bad
	Comparative example 2	Have		1.5	Red color tone toner and blue toner mixing existence/charged inhomogeneous					1.24	Bad
Comparative example 3			Have			1.0	Red color tone toner and blue toner mixing existence/charged inhomogeneous	1.86	Bad

Claims (8)

1. the manufacture method of a liquid crystal aligning film is characterized in that, comprising:

By the operation (1) of friction to the processing of transparent base film implementation orientation,

With peeling force is the operation (2) that surface protective plate below the 0.5N/50mm fits in described orientation process face,

Peel off described surface protective plate applies the liquid crystal material that contains liquid crystal monomer and/or liquid crystal polymer afterwards on described orientation process face operation (3),

Carry out immobilized operation (4) after making described liquid crystal material orientation.

2. the manufacture method of liquid crystal aligning film according to claim 1 is characterized in that,

Surface protective plate has substrate layer and bonding coat, is by their co-extruded being gone out or by the surface protective plate made of coating bonding coat on substrate layer.

3. the manufacture method of liquid crystal aligning film according to claim 2 is characterized in that,

Substrate layer contains the ethylene series resin, and bonding coat contains ethene-vinyl acetate co-polymer.

4. according to the manufacture method of any described liquid crystal aligning film in the claim 1～3, it is characterized in that,

During the peeling off of the surface protective plate in carrying out operation (3), transparent base film evenly has any electric charge in the plus or minus electric charge.

5. a liquid crystal aligning film is characterized in that,

Be that manufacture method by any described liquid crystal aligning film in the claim 1～4 obtains.

6. an optical thin film is characterized in that,

At least use 1 described liquid crystal aligning film of claim 5.

7. an image display device is characterized in that,

Use the described optical thin film of claim 6.

8. a surface protective plate is characterized in that,

Be in the manufacture method of the described liquid crystal aligning film of claim 1～4, be used for operation (2) and peeling force be surface protective plate below the 0.5N/50mm.

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