CN108873137A

CN108873137A - The polarizer and its manufacturing method

Info

Publication number: CN108873137A
Application number: CN201810607630.3A
Authority: CN
Inventors: 幡中伸行
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2011-07-12
Filing date: 2012-07-10
Publication date: 2018-11-23
Also published as: JP2017107232A; KR20180120131A; JP6931023B2; TWI530733B; JP2019194728A; JP6171276B2; JP2021073537A; KR20190113717A; KR20130008466A; JP2013037353A; TW201307951A; KR102355232B1; KR101913864B1; CN102879848A; KR102028894B1; JP7170762B2; CN102879848B

Abstract

The present invention provides a kind of novel polarizer and its manufacturing method.The polarizer is formed by setting gradually oriented layer, polarization photosphere and protective layer over the transparent substrate; the polarization photosphere is fabricated by manufacturing method with the following process, the process for forming film by the composition containing polymerizable liquid crystal compound, dichroism pigment, polymerization initiator and solvent；The process of the solvent is removed from the film；Make to eliminate process of the polymerizable liquid crystal compound contained in the film of the solvent as smectic liquid crystal state；With the process for polymerizeing the polymerizable liquid crystal compound in the case where keeping the smectic liquid crystal state.

Description

The polarizer and its manufacturing method

The application is Chinese patent application《The polarizer and its manufacturing method》(the applying date：July 10, application number in 2012： 201210251074.3) divisional application.

Technical field

The present invention relates to the polarizer and its manufacturing methods etc..

Background technique

The polarization element (polarizer) that liquid crystal display device uses includes protective layer, the polarization light such as photosphere and transparent substrate Learn film.For example, describing a kind of polarizer in patent document 1, successively lamination transparent resin is protected on hyaline membrane (transparent substrate) Sheath (protective film), light absorption anisotropic band (polarization film) and hyaline membrane (transparent substrate), the light absorption anisotropic band It is the layer of the dichroism pigment containing specific structure, with nematic liquid crystal.

Existing technical literature

Patent document

Te Xu document 1：Japanese Patent Laid-Open 2010-152351 bulletin

Summary of the invention

The invention solves project

The present invention provides the novel polarizer and its manufacturing method.

The method to solve the problem

The present invention includes the invention of following [1]~[14].

[1] a kind of polarizer of is formed by setting gradually oriented layer, polarization photosphere and protective layer over the transparent substrate, described Polarization photosphere is fabricated by manufacturing method with the following process：

Film is formed by the composition containing polymerizable liquid crystal compound, dichroism pigment, polymerization initiator and solvent Process；

The process of the solvent is removed from the film；

Make to eliminate work of the polymerizable liquid crystal compound contained in the film of the solvent as smectic liquid crystal state Sequence；With

The process for polymerizeing the polymerizable liquid crystal compound in the case where keeping the smectic liquid crystal state.

[2] polarizer of the as described in above-mentioned [1], the polarization photosphere is that bragg peak is obtained in X-ray diffraction measure Polarization photosphere.

[3] polarizer of the as described in above-mentioned [1] or [2], the polarised light thickness degree is in 0.5~3 μ m.

[4] polarizer of the as described in any one of above-mentioned [1]~[3], the dichroism pigment are azopigments.

[5] polarizer of the as described in any one of above-mentioned [1]~[4], the polymerizable liquid crystal compound contain there are two types of with On polymerism smectic liquid crystal compound.

[6] polarizer of the as described in any one of above-mentioned [1]~[5], the protective layer are by containing multifunctional acrylic acid The layer that the protecting layer compositions of ester and solvent are formed, the solvent are actually made of alcoholic solvent and/or ether solvents.

[7] polarizer of the as described in any one of above-mentioned [1]~[5], the protective layer is by protective layer formation composition Formed, the protective layer formation with composition contain the polymer being polymerize by polyfunctional acrylic ester or oligomer and Water.

[8] polarizer of the as described in any one of above-mentioned [1]~[5], the protective layer, by containing water-soluble polymer Protective layer formation with water is formed with composition.

[9] a kind of liquid crystal display device of has the polarizer described in any one of above-mentioned [1]~[8].

[10] liquid crystal display device of the as described in above-mentioned [9], the polarizer are configured inside liquid crystal cell.

[11] a kind of circular polarization light board of, on the protective layer of the polarizer described in any one of above-mentioned [1]~[8] 1/4 wavelength plate is set.

[12] circular polarization light board of the as described in above-mentioned [11], 1/4 wavelength plate are that have for phase in the face of visible light Potential difference value shortens and the wavelength plate of reduced characteristic with wavelength.

[13] a kind of organic EL display device of has circular polarization light board described in above-mentioned [11] or [12] and organic EL Element.

[14] a kind of manufacturing method of the polarizer of, has：

Process (1) is arranged oriented layer over the transparent substrate and forms laminated board；

Process (2), in the oriented layer of the laminated board, coating contains polymerizable liquid crystal compound, dichroism color The composition of element and polymerization initiator, to form the 1st coated film in the oriented layer；

Process (3), it is dry under conditions of the polymerizable liquid crystal compound contained by the 1st coated film will not polymerize The 1st coated film formed in the process (2) forms the 1st dry coationg, makes the polymerism in the 1st dry coationg After liquid-crystal compounds becomes smectic liquid crystal state, in the case where keeping the smectic liquid crystal state, make the polymerizable liquid crystal chemical combination Object polymerization, to form polarization photosphere by the 1st dry coationg；With

Process (4), coating contains polyfunctional acrylic ester and molten on the polarization photosphere formed in the process (3) The protective layer of agent, which is formed, uses composition, and the 2nd coated film is formed on the polarization photosphere, makes described contained by the 2nd coated film Polyfunctional acrylic ester polymerization, to form protective layer by the 2nd coated film.

[15] manufacturing method of the polarizer of the as described in [14], it is real that the protective layer forms the solvent contained by composition It is made of on border alcoholic solvent or/and ether solvents.

[16] a kind of manufacturing method of the polarizer of, has：

Process (3) under conditions of the polymerizable liquid crystal compound contained in the 1st coated film will not polymerize, is done The 1st coated film formed in the dry process (2) forms the 1st dry coationg, makes the polymerization in the 1st dry coationg Property liquid-crystal compounds become smectic liquid crystal state after, in the case where keeping the smectic liquid crystal state, make the polymerizable liquid crystal Object polymerization is closed, to form polarization photosphere by the 1st dry coationg；With

Process (4), in the process (3) on the polarization photosphere of formation, coat protective layer, which is formed, uses composition, should Protective layer formation contains the polymer or oligomer, Yi Jishui that polyfunctional acrylic ester polymerize with composition, and inclined at this The 2nd coated film is formed on vibration photosphere, by dry 2nd coated film, protective layer is formed by the 2nd coated film.

[17] a kind of manufacturing method of the polarizer of, has：

Process (4), in the process (3) on the polarization photosphere of formation, coating contains water-soluble polymer and water Protective layer formed and use composition, and the 2nd coated film is formed on the polarization photosphere, dry 2nd coated film, thus by this 2 coated films form protective layer.

[18] a kind of polarizer of, the manufacturing method as described in any one of above-mentioned [14]~[17] are fabricated.

Invention effect

According to the present invention, it is possible to provide a kind of polarizer containing polarized light layer.

Detailed description of the invention

Fig. 1 is the schematic overview of the section constitution of the polarizer of the invention.

Fig. 2 is the schematic overview using the section constitution of the liquid crystal display device of the polarizer of the invention.

Fig. 3 is the schematic overview of the laminated order of the polarizer of the invention of liquid crystal display device setting.

Fig. 4 is the schematic overview of the laminated order of the polarizer of the invention of liquid crystal display device setting.

Fig. 5 is the signal outline using the section constitution of the liquid crystal display device (inline form) of the polarizer of the invention Figure.

Fig. 6 is the schematic overview using the section constitution of the EL display device of the polarizer of the invention.

Fig. 7 is the schematic overview using the manufacturing method of the EL display device of the polarizer of the invention.

Fig. 8 is the schematic overview of the laminated order of the polarizer of the invention of EL display device setting.

Fig. 9 is the schematic overview using the section constitution of the EL display device of the polarizer of the invention.

Figure 10 is the schematic overview using the projection type liquid crystal display apparatus of the polarizer of the invention.

Symbol description

1 polarizer (this polarizer) of the invention

2 transparent substrates

3 oriented layer

4 polarization photospheres

5 matrix

6 dichroism pigments

7 protective layers

10 liquid crystal display devices

11 antireflection films

12a, 12b polarization film

13a, 13b phase separation layer

14a, 14b substrate

15 colored filters

16 transparent electrodes

17 liquid crystal layers

18 interlayer dielectrics

19 backlight modules

20 black matrix"s

21 thin film transistor (TFT)s

22 pixel electrodes

23 gaskets

24 liquid crystal display devices

30 EL display devices

31 polarizers

32 phase separation layers

33 substrates

34 interlayer dielectrics

35 pixel electrodes

36 luminescent layers

37 cathode electrodes

38 desiccant

39 caps

40 thin film transistor (TFT)s

41 frame glues

42 thin-film package films

44 EL display devices

111 light sources

112 the 1st lens arrays

112a lens

113 the 2nd lens arrays

114 polarization light conversion elements

115 compound lenses

121,123,132 dichronic mirror

122 reflecting mirrors

140R, 140G, 140B liquid crystal display panel

142,143 polarization films

150 cross colour splitting prisms

170 projecting lens

180 projection screens

Specific embodiment

The polarizer (hereinafter, being according to circumstances referred to as " this polarizer ") of the invention is to set gradually orientation over the transparent substrate Element made of layer, polarization photosphere and protective layer,

The polarization photosphere is fabricated by following manufacturing methods, which includes：By containing polymerizable liquid crystal Close the process that the composition of object, dichroism pigment, polymerization initiator and solvent forms coated film；

The process of the solvent is removed from the coated film；

Make to eliminate the polymerizable liquid crystal compound contained in the coated film of the solvent as smectic liquid crystal state Process；With

It is illustrated when necessary referring to preferred embodiment of the figure to the manufacturing method of this polarizer.The manufacturing method it is excellent Select embodiment with the following process：

Process (2), in the oriented layer that the process (1) is formed by the laminated board, coating contains polymerism The composition of liquid-crystal compounds, dichroism pigment and polymerization initiator, to form the 1st coated film in the oriented layer；

Process (3) passes through under conditions of the polymerizable liquid crystal compound contained by the 1st coated film will not polymerize The 1st coated film formed in the dry process (2), forms the 1st dry coationg, makes the polymerism in the 1st dry coationg After liquid-crystal compounds becomes smectic liquid crystal state, in the case where keeping the smectic liquid crystal state, make the polymerizable liquid crystal chemical combination Object polymerization, to form polarization photosphere by the 1st dry coationg；

Process (4), on the polarization photosphere formed in the process (3), coating containing polyfunctional acrylic ester and The protecting layer compositions of solvent, and the 2nd coated film is formed on the polarization photosphere, make more officials contained by the 2nd coated film Energy acrylic ester polymerization, to form protective layer by the 2nd coated film.Hereinafter, each process to the manufacturing method is said It is bright.

It is to prepare transparent substrate first in the manufacturing method of this polarizer.The transparent substrate refers to the transparency Substrate, the transparency refer to the degree that light, especially visible light can penetrate.The transparency refers to for wavelength 380~ The transmitance of the light of 780nm is in 80% or more such characteristic.It specifically, can if illustrating such transparent substrate To enumerate glass baseplate, plastics translucency thin plate and light transmissive film.In addition, as the translucency piece thin plate or light transmission is constituted The plastics of property film, can enumerate, for example, the polyolefin such as polyethylene, polypropylene, norbornene-based polymer；Cycloolefin tree Rouge；Polyvinyl alcohol, polyethylene terephthalate；Polymethacrylates ester；Polyacrylate；Triacetyl cellulose, diethyl The cellulose esters such as acyl cellulose and cellulose ethanoate propionic acid；Polyethylene naphthalate；Polycarbonate；Polysulfones；Polyethers Sulfone；Polyether-ketone；Polyphenylene sulfide and polyphenylene oxide etc..In the concrete example of the above transparent substrate, plastics translucency thin plate and In translucency, preferably plastics light transmissive film, i.e. polymeric membrane.In the polymeric membrane, from be easy to be obtained from the market, the transparency From the aspect of excellent, the macromolecule (cellulose ester membrane or the ring-type that are preferably made of cellulose esters or annular ethylene series resin Olefin-based resin film).When manufacturing this polarizer using above-mentioned transparent substrate, from transport, keeping the transparent substrate when it is easy to operate From the aspect of breakage without rupture etc., supporting base material etc. can be sticked in the transparent substrate in advance.In addition, this is transparent Substrate with a thickness of the degree that can embody the above-mentioned transparency.In addition, passing through when using polymeric membrane as transparent substrate Stretch processing etc. assigns function of the polymeric membrane as phase difference film.In addition, for assigning transparent substrate as phase difference film Function the case where, be then illustrated.

More detailed narration is carried out to cellulose ester membrane and annular ethylene series resin film.In addition, being assigned in both When giving the function as phase difference film, phase difference value is easy to control on this point, and annular ethylene series resin film is also preferred.

Constitute cellulose ester membrane cellulose esters, at least part for the hydroxyl that cellulose is included be acid esterification it Object.The cellulose ester membrane being made of such cellulose esters can easily be obtained from the market.Commercially available cellulose ester membrane (three Acetylcellulose film) for example there are Off ジタッ Network Off イ Le system (Off イ Le system (strain) is drawn a portrait by Fuji), " KC8UX2M ", " KC8UY " And " KC4UY " (U ニカミノ Le タプ (strain)) etc..Such a commercially available cellulose membrane, can directly use, or Can according to need, to its surface implement non-glare treated, cure process, antistatic treatment or prevent reflection processing etc After surface treatment, it is used as transparent substrate.

As described above, assigning phase difference to the polymeric membrane by stretching polymeric membrane.By plastics, that is, thermoplastic resin The polymeric membrane that rouge is constituted can be carried out stretch processing, but in terms of easy imparting phase difference this point, preferably cyclic olefin Resin film.The annular ethylene series resin for constituting annular ethylene series resin film is by norbornene or polycyclic orbornene-based monomer The polymer of equal cyclic olefins or the object of copolymer (annular ethylene series resin) composition, the annular ethylene series resin can contain portion Separate ring structure.In addition, can also carry out adding hydrogen to the annular ethylene series resin containing open loop structure.In addition, from unobvious damage From the aspect of the transparency or the unobvious increase of hygroscopicity, which for example can be cyclic olefin and chain olefin Or the copolymer of vinylated aromatic compound (styrene etc.).In addition, for the annular ethylene series resin, it can be by polarity Base imports its intramolecular.

Annular ethylene series resin is the copolymer of cyclic olefin with aromatic compound or chain olefin with vinyl When, which is ethylene or propylene, and vinylated aromatic compound is that styrene, α-methylstyrene and alkyl take For styrene etc..In such copolymer, from cyclic olefin structural unit content ratio relative to cyclic olefin It is the entire infrastructure unit of resin, in 50 moles of % hereinafter, for example in the approximate range of 15~50 moles of %.Cycloolefin tree When rouge is the terpolymer that cyclic olefin, chain olefin and vinylated aromatic compound obtain, such as from chain Entire infrastructure unit of the content ratio of the structural unit of alkene relative to the annular ethylene series resin, substantially rubs 5~80 You are %, from the content ratio of the structural unit of vinylated aromatic compound, substantially in 5~80 moles of %.It is such The annular ethylene series resin of terpolymer has the advantage that, when manufacturing the annular ethylene series resin, the cyclic annular alkene of high price The usage amount of hydrocarbon can be fewer.

The annular ethylene series resin of annular ethylene series resin film can be manufactured or be readily available from the market.In city For example there are " Topas " [Ticona society (Germany)] for the annular ethylene series resin that field is sold；" アート Application " [JSR (strain)]；"ゼオノア (ZEONOR) " and " ゼオネッ Network ス (ZEONEX) " [Japanese ゼオ Application (strain)]；" アペ Le " [Mitsui Chemicals (strain) Manufacture].It is filmed for example, film-forming method well known to casting or extrusion by melting etc. can be burnt by solvent, by above-mentioned ring-type Film (annular ethylene series resin film) is made in olefin-based resin.It is sold in the form of having formed a film in market in addition it is also possible to use Annular ethylene series resin film.It is above-mentioned marketed annular ethylene series resin film for example for example there are, " エスシー Na " with And " SCA40 " [ponding chemical industry (strain)]；" ゼオノア Off ィ Le system " [オプテス (strain)]；"アートンフィルム" [JSR (strain)].In addition, herein, what is recorded in " " is trade name, below similarly.

Then, the method for phase difference is given to polymeric membrane carries out simple illustration.For polymeric membrane, Phase difference can be assigned by well known drawing process.For example, preparing polymeric membrane is wrapped in the spool body on roller, from It is continuously taken out film on the spool body, the film of taking-up is transported to heating furnace.The set temperature of heating furnace is to constitute polymeric membrane Plastics glass transition temperature nearby (DEG C)~[glass transition temperature+100] (DEG C) range, preferred glass transition The range of (DEG C)~[glass transition temperature+50] (DEG C) near temperature.In the heating furnace, along film direction of advance stretch or When person stretches along the direction orthogonal with direction of advance, adjust carriage direction or tension, tilted with any angle, carry out it is uniaxial or The hot-stretch of twin shaft is handled.The multiple of stretching is usually in 1.1~6 times of approximate range, preferably in 1.1~3.5 times of substantially model It encloses.In addition, as the method that adipping stretches, as long as can continuously make the axial desired angle tilt of orientation, just It is not particularly limited, well known drawing process can be used.Above-mentioned drawing process can enumerate such as Japanese Patent Laid-Open No. Sho 50- The method that No. 83482 bulletins or Japanese Patent Laid-Open 2-113920 bulletin are recorded.

As transparent substrate in use, being to be capable of the degree of practical operation and can ensure adequately transparent from its weight From the aspect of property, the preferably thin person of high molecular thickness, if but it is excessively thin, there are strength reductions, the tendency of poor in processability.Therefore, this A little film thickness appropriate are for example at substantially 5~200 μm, and preferably 20~100 μm.This polarizer is made as aftermentioned circular polarization light board With the case where, will using the circular polarization light board display device be used for personal digital assistant device on the way when, the thickness of film is especially excellent Substantially 20~80 μm of choosing.In addition, the thickness after stretching is according to the film thickness before stretching when phase difference being given to film by stretching Or draw ratio determines.

In process (1), by the way that oriented layer is arranged in above-mentioned transparent substrate, the layer with transparent substrate and oriented layer is formed Product plate, is preferably formed as laminated board made of transparent substrate and oriented layer lamination.In addition, implementing cure process to the transparent substrate When the surface treatments such as (hard court) or anti glare anti static coatings processing, orientation is formed on the face of the opposite side in the surface treated face Layer.

The oriented layer is preferably the not significant object of modification in the forming process of aftermentioned polarization photosphere.Form oriented layer Method for example there are, using by friction can assign anchorage force orientation polymer method (hereinafter, being according to circumstances referred to as " rubbing manipulation ")；Using the method for the light orientation polymer that can assign anchorage force by irradiation polarised light (hereinafter, according to circumstances Referred to as " optical alignment method ")；By the way that silica is formed orientation and (transparent substrate surface) carries out oblique evaporation on the transparent substrate The method of layer；And it is formed by using Langmuir Blaw Ztel (langmuirBlodgett) method (LB method) with long-chain The monomolecular film of alkyl is come the method etc. that forms oriented layer.Wherein, in terms of it can obtain the excellent oriented layer of orientation uniformity, Or from the aspect of processing time for being formed of oriented layer and processing cost, preferably rubbing manipulation and optical alignment method.As oriented layer, It is preferred that composition (the aftermentioned polarization photosphere formation combination being coated in subsequent process will not be substantially dissolved in by having Object) in contain solvent solvent resistance, to the polarization photosphere formation for removing solvent etc. when the heat resistance of heat treatment, Yi Jiyu The sufficient close property of transparent substrate.In addition, when anchorage force being given to the oriented layer by rubbing manipulation, because will be to the orientation The coated film of layer formation applies friction, it is advantageous to the coated film of the oriented layer formation or constitutes the chemical combination of the oriented layer Object (such as aftermentioned orientation polymer etc.) has will not be modified by the friction etc. or oriented layer itself will not be because this rubs It wipes etc. and the property peeled off from transparent substrate.From the aspect of it can be simply forming above-mentioned oriented layer, preferably by orientation Perhaps the composition containing orientation polymer forms oriented layer or takes by light orientation polymer or containing light polymer The composition of tropism polymer forms oriented layer.

Hereinafter, the orientation polymer and light orientation polymer to oriented layer formation are illustrated.

If illustrating preferred orientation polymer, for example there are：Intramolecular has the polyamide of amido bond；Gelatin Class；Intramolecular has the polyimides and its hydrolysate polyamic acid of imine linkage；Alkyl-modified polyvinyl alcohol；Polyacrylamide； Ju oxazole；Polyethyleneimine；Polystyrene；Polyvinylpyrrolidone；The polymer such as polyacrylic acid and polyacrylate. These polymer can be individually used for the formation of oriented layer, or the two or more uses of mixing, can also will be with two or more The copolymer for constituting the structural unit of these polymer is used for the formation of oriented layer.More than, instantiate the suitable of orientation polymer Suitable example, but wherein particularly preferred polyvinyl alcohol as orientation polymer.In addition, about these orientation polymer, it can With according to its type, by the polycondensation or free radical polymerization of the progress such as dehydration polymerization, de- amine polymerization, anionic polymerisation and Polymerization well known to the chain polymerizations such as cationic polymerization, coordination polymerization or ring-opening polymerisation etc., is easily manufactured.

Light orientation polymer uses the polymer with photosensitive structure.To the polymer irradiation with photosensitive structure When polarised light, isomerization or crosslinking occur for the photosensitive structure of illuminated part, and thus light orientation polymer takes To anchorage force is as a result given to light orientation polymer, forms oriented layer.As the photosensitive structure, for example there are for example： Azobenzene structure, maleic anhydride contracting imine structure, chalcone structure, cinnamic acid structure, 1,2- ethenylidene structure, 1,2- acetylene Structure, spiro-pyrans structure, spirobenzopyran structure and fulgide structure etc..With the photosensitive of any one therefrom selected The polymer of property structure may be used alone, used in two or more when forming oriented layer.In addition, about these light Orientation polymer can choose the polycondensation or free radical polymerization, anionic polymerisation of the progress such as dehydration polymerization, de- amine polymerization And polymerization well known to the chain polymerizations such as cationic polymerization, coordination polymerization or ring-opening polymerisation etc., by with photosensitive structure Monomer (monomer) be easily manufactured.The two or more monomers with different photosensitive structures can also be used to be made Copolymer.

As the method for forming oriented layer by orientation polymer or light orientation polymer, from this point easy to operate It sees, preferably following methods, the orientation polymer or the light orientation polymer is dissolved in solvent, combination is modulated into Object uses the composition.Hereinafter, according to circumstances, the composition that will form the oriented layer is referred to as that " group is used in oriented layer formation Close object ".Such as be coated on oriented layer formation in transparent substrate with composition, by heating operation or decompression operation, from the painting Solvent is removed in cloth film, oriented layer easily can be set in the transparent substrate.Oriented layer formation is used molten with composition Agent can make appropriate choice according to the type and its dosage of orientation polymer or light orientation polymer used, specifically For example there are water；Methanol, ethyl alcohol, ethylene glycol, isopropanol, propylene glycol, methyl cellosolve, butyl cellosolve and propylene glycol list first The alcoholic solvents such as base ether；Ethyl acetate, butyl acetate, ethylene glycol, methylether acetate, gamma-butyrolacton, propylene glycol methyl ether acetic acid The ester solvents such as ester and ethyl lactate；Acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone and methyl tert-butyl The ketone solvents such as base ketone；The aliphatic hydrocarbon solvents such as pentane, hexane and heptane；The aromatic hydrocarbon solvents such as toluene and dimethylbenzene, second The nitrile solvents such as nitrile；The ether solvents such as tetrahydrofuran and dimethoxy-ethane；The chlorine such as chloroform and chlorobenzene replace hydrocarbon solvent etc..These Solvent can be used alone, and can also be used in combination.

In addition it is also possible to be used to form oriented layer using commercially available oriented layer formation composition.Commercially available oriented layer shape At with composition, for example there are " サ Application エバー " (Nissan Chemical Industries (strains)) or " オプトマー " (JSR (strain)) etc..Use this The commercially available oriented layer of sample, which is formed, uses composition, is freely orientated few oriented layer in being capable of forming or is capable of forming environmental resistance And it is advantageous in terms of the good oriented layer of mechanical resistance.

The method for forming oriented layer with composition using oriented layer formation, is to be coated with the oriented layer over the transparent substrate to be formed By heat treatment (annealing), the coated film of oriented layer formation is then formed in the transparent substrate with composition.So What the thickness of the coated film of obtained oriented layer formation was related such that, exactly make obtained oriented layer after imparting anchorage force Reach desired thickness.The thickness of the oriented layer is, for example, 10nm~10000nm, preferably 10nm~1000nm.About upper The thickness of oriented layer is stated, condition when by adjusting coating oriented layer formation composition can control.

In addition, in order to which the anchorage force of appropriateness is given to the coated film of the oriented layer formation, and oriented layer is formed, it is right The coated film of the oriented layer formation carries out friction or polarizing light irradiation.By assigning anchorage force, aftermentioned polarization can be made Polymerizable liquid crystal compound contained by the coated film (the 1st coated film) of photosphere formation is orientated in desired direction.In addition, such as It is described afterwards, when the 1st coated film includes two or more polymerizable liquid crystal compounds, that is, when including polymerizable liquid crystal mixture, Make polymerizable liquid crystal mixture orientation in desired direction.

As the method to rub to the coated film of the oriented layer formation, for example there are following methods, for example, preparing It is wound with the friction roller of the rotation of friction cloth, by the way that the coated film (painting of oriented layer formation will be formed over the transparent substrate Cloth film) obtained from laminate be placed on estrade, towards rotation friction roller convey, connect the friction roller of the coated film and rotation Touching.In addition it is also possible to by irradiating polarised light (preferably polarised light UV) to the coated film of oriented layer (light redirecting layer) formation, it will Anchorage force is given to the coated film.Carry out friction or when polarizing light irradiation, if carrying out masking, obtained this polarizer The different more than two regions (pattern) in slow axis direction can also be formed.

In process (2), the setting polarization photosphere in oriented layer as formed above.

The polarization photosphere that this polarizer has is formed with method as above.Although repeating, but this method is illustrated. Firstly, by the composition containing polymerizable liquid crystal compound, dichroism pigment, polymerization initiator and solvent (hereinafter, according to feelings Condition, referred to as " polarization photosphere forms composition ") it is coated in the oriented layer and forms the 1st coated film, pass through the dry 1st Coated film removes the solvent, to form the 1st dry coationg.Then, by making the polymerizable liquid crystal in the 1st dry coationg Compound polymerize in the case where keeping smectic liquid crystal state, forms polarization photosphere.In order to as above keep smectic liquid crystal state In the case where, it polymerize polymerizable liquid crystal compound, firstly, the phase transition temperature for the polymerizable liquid crystal compound that measurement uses, The temperature that can keep smectic phase is found out, then, under the conditions of being lower than the temperature of the temperature, polymerize the polymerizable liquid crystal compound , but the polymerization temperature for polymerizeing the polymerizable liquid crystal compound the low the more preferred.In addition, the measurement of phase transition temperature measurement Condition is illustrated in embodiments herein.

The thickness of the polarization photosphere is usually in 0.5~10 μ m, more preferably in 0.5~3 μ m.Therefore, it the 1st applies The thickness of cloth film considers the thickness of obtained polarization photosphere to determine.In addition, the thickness of the polarization photosphere is by interfering film thickness The value that the measurement of instrument or laser microscope or contact type film thickness meter acquires.

It is described polarization photosphere formation composition contained by polymerizable liquid crystal compound refer to polymerizable group, and Show the compound of liquid crystal liquid crystal property.Polymerizable group refers to the group for participating in the polymerization reaction of polymerizable liquid crystal compound.

For example there are smectic B, smectic D phase, smectic E phase, smectic F phase, smectic G phase, smectic H phases, smectic I for the smectic phase Phase, smectic J phase, smectic K phase and smectic L phase.Wherein, preferably smectic B, smectic F phase, smectic I phase, inclined smectic F phase And high dimension smectic phase as inclined smectic I phase, more preferable smectic B.If being shown using polymerizable liquid crystal compound Liquid crystalline phase be that the polarization photospheres of these liquid crystalline phases forms and uses composition, then can form the high polarised light of orientation orientation degree of order Layer.

Preferred polymerizable liquid crystal compound can enumerate, such as formula (1) compound represented is (hereinafter, be according to circumstances referred to as " compound (1) ".).

U¹-V¹-W¹-X¹-Y¹-X²-Y²-X³-W²-V²-U² (1)

[in formula (1),

X¹、X²And X³Each independently represent can have substituent group to phenylene or can have the 1,4- hexamethylene of substituent group Diyl.Wherein, X¹、X²And X³Among at least one be can have substituent group to phenylene.

Y¹And Y²Each independently represent-CH₂CH₂-、-CH₂O- ,-COO- ,-OCOO-, singly-bound ,-N=N- ,-CR^a= CR^b,-C ≡ C- or-CR^a=N-.R^aAnd R^bEach independently represent the alkyl of hydrogen atom or carbon atom number 1~4.

U¹Indicate hydrogen atom or polymerizable group.

U²Indicate polymerizable group.

W¹And W²Each independently represent singly-bound ,-O- ,-S- ,-COO- or-OCOO-.

V¹And V²The alkylidene that there can be the carbon atom number 1~20 of substituent group is each independently represented, the alkylidene is constituted - CH₂It can be replaced by-O- ,-S- or-NH-.]

In compound (1), as described above, X¹、X²And X³Among at least one be the Isosorbide-5-Nitrae-phenylene that can have substituent group, But preferably wherein at least two be can have substituent group to phenylene.

It is above-mentioned preferably unsubstituted to phenylene.Above-mentioned Isosorbide-5-Nitrae-hexamethylene diyl is preferably anti-form-1,4- hexamethylene diyl, also more It is preferably unsubstituted.

It is above-mentioned to phenylene or substituent group that above-mentioned Isosorbide-5-Nitrae-hexamethylene diyl arbitrarily has can be enumerated, methyl, ethyl and butyl Etc. carbon atom numbers 1~4 alkyl；Cyano；Halogen atom etc..In addition, constituting Isosorbide-5-Nitrae-hexamethylene diyl-CH₂Can by-O- ,-S- or- NR- replacement.R is the alkyl or phenyl of carbon atom number 1~6.

The Y of compound (1)¹Preferably-CH₂CH₂,-COO- or singly-bound, Y²It is preferred that-CH₂CH₂Or-CH₂O-。

U²For polymerizable group.U¹For hydrogen atom or polymerizable group, preferred polymeric group.That is, it is preferred that U¹And U²Simultaneously It is more preferably simultaneously polymerism group for polymerizable group.Herein, polymerism group refers to, can be poly- by aftermentioned light Close the group that living radical or the acid etc. that initiator generates participate in polymerization reaction.If using having the poly- of polymerism group Conjunction property liquid-crystal compounds then can be such that the polymerizable liquid crystal compound polymerize, be advantageous in this regard under conditions of more low temperature 's.

In compound (1), U¹And U²Polymerism group between each other can be different, but preferably similar group.Make For polymerism group, vinyl, ethyleneoxy, 1- chlorovinyl, isopropenyl, 4- ethenylphenyl, acryloyl can be enumerated Oxygroup, methacryloxy, epoxy ethyl and oxetanylmethoxy etc..Wherein, preferably acryloxy, methacryloxypropyl Base, ethyleneoxy, epoxy ethyl and oxetanylmethoxy, more preferable acryloxy.

V¹And V²Alkylidene can enumerate, methylene, 1,2- ethylidene, 1,3- propylidene, 1,3- butylidene, Isosorbide-5-Nitrae-Aden Base, 1,5- pentylidene, 1,6- hexylidene, 1,7- heptamethylene, 1,8- octamethylene, 1,10- decylene, the Asia 1,14- myristyl and 1,20- alkylene eicosyl etc..V¹And V²It is preferred that the alkylidene of carbon atom number 2~12, the alkylidene of more preferable carbon atom number 6~12.

The substituent group arbitrarily having as the alkylidene can be enumerated, and cyano and halogen atom etc., the alkylidene are preferably nothing Replace, more preferably unsubstituted and straight-chain alkylidene.

W¹And W²Preferred singly-bound or-O- each independently.

As compound (1), any compound represented of formula (1-1)~formula (1-21) etc. can be enumerated.When the chemical combination being related to When the concrete example of object (1) has Isosorbide-5-Nitrae-hexamethylene diyl, the Isosorbide-5-Nitrae-hexamethylene diyl is preferably trans- body.

The compound (1) [polymerizable liquid crystal compound] of illustration, can be used alone or be made be mixed with it is two or more Polymerizable liquid crystal mixture use.In addition, finding out the phase transition temperature of compound (1) as described above, it is being lower than the phase transition Under the conditions of the temperature of temperature, adjustment polarization photosphere forms the ingredient other than the polymerizable liquid crystal compound with composition, makes the change Closing object (1) can polymerize.As the ingredient that can control such polymerization temperature, aftermentioned Photoepolymerizationinitiater initiater can be enumerated, light increases Quick dose and polymerization inhibitor etc..By appropriate adjustment their type and amount, the polymerization temperature of controllable produced compounds (1).In addition, polarizing Photosphere is formed in composition, using two or more compounds (1) mixture, i.e. polymerizable liquid crystal compound when, equally After the phase transition temperature for acquiring the polymerizable liquid crystal compound, with polymerizable liquid crystal compound the case where is identical, to control polymerization Temperature.

As polymerizable liquid crystal compound used in polarization photosphere formation composition, among the compound (1) of illustration, Preferred formula (1-3), formula (1-6), formula (1-7), formula (1-12) or formula (1-13) compound represented.These compounds (1) are logical The interaction with the Photoepolymerizationinitiater initiater used simultaneously is crossed, it can be easily under the conditions of being lower than the temperature of phase transition temperature, i.e., The compound (1) can be made to polymerize in the case where keeping sufficient high dimension smectic liquid crystal state.More specifically, by with light The interaction of polymerization initiator, these compounds (1) can be kept under the conditions of 70 DEG C or less, preferably 60 DEG C of temperature below Sufficient high dimension smectic liquid crystal state and polymerize.

As described above, polymerizable liquid crystal compound contained in the polarization photosphere formation composition can be one Kind, be also possible to it is two or more, but preferably it is two or more, it is two or more in the compound (1) more preferably illustrated.In addition, should It polarizes photosphere and forms the polymerizable liquid crystal compound preferred polymeric smectic liquid crystal compound contained in composition, more preferably It is set to contain two or more polymerism smectic liquid crystal compounds.In addition, above-mentioned formula (1-1)~formula (1-21) compound represented (1) meet polymerism smectic liquid crystal compound.

The polarization photosphere forms the content ratio with the polymerizable liquid crystal compound in composition, relative to the polarised light Layer forms the solid component for using composition, preferably 70~99.9 mass %, more preferable 90~99.9 mass %.If the polymerism liquid The content ratio of brilliant compound within the above range, then the tendency that gets higher of orientation with polymerizable liquid crystal compound.Herein, Solid component refers to, from the polarization photosphere formation ingredient total amount eliminated after the volatile components such as solvent in composition. When polymerizable liquid crystal compound uses compound (1), compound (1) the containing relative to the polarization photosphere formation composition Ratio is in above range.When the polarization photosphere formation composition contains two or more compounds (1), always contain than Example is in above range.

Above-mentioned polarization photosphere formation preferably comprises levelling (レベリ Application グ) agent with composition.The levelling agent has following function Energy：The mobility for adjusting polymerizable liquid crystal compound, makes the described 1st obtained by being coated with as above-mentioned polarization photosphere formation with composition Coated film is more flat.The levelling agent can enumerate surfactant etc..The further preferred levelling agent is selected from polyacrylate Compound is the levelling agent of principal component and using fluorine-containing atomic compound to be at least one kind of among the levelling agent of principal component.

It can be enumerated with the levelling agent that polyacrylic acid ester compounds are main ingredient, " BYK-350 ", " BYK-352 ", " B YK- 353 ", " BYK-354 ", " BYK-355 ", " BYK-358N ", " BYK-361N ", " BYK-380 ", " B YK-381 " and " BYK- 392 " [BYK Chemie societies] etc..

It can be enumerated by the levelling agent of principal component of fluorine-containing atomic compound, " メガ Off ァッ Network R-08 ", with " R-30 ", same " R-90 ", with " F-410 ", with " F-411 ", with " F-443 ", with " F-445 ", with " F-470 ", with " F-471 ", with " F-477 ", With " F-479 ", with " F-482 " and with " F-483 " [DIC (strain)]；" サー Off ロ Application S-381 ", same " S-382 ", same " S- 383 ", with " S-393 ", with " SC-101 ", with " SC-105 ", " KH-40 " and " SA-100 " [AGC セイミケミカ Le (strain)]； " E1830 ", " E5844 " [(strain) ダイキ Application Off ァイ Application ケミカ Le research institute]；" エ Off トップ EF301 ", same " EF303 ", With " EF351 " and with " EF352 " [Mitsubishi's マテリア Le electronics is melted into (strain)] etc..

When above-mentioned polarization photosphere formation composition being made to contain levelling agent, content is relative to polymerizable liquid crystal compound 100 mass parts, more than preferably 0.3 mass parts 5 below the mass, and more than further preferred 0.5 mass parts 3 below the mass.If The content of levelling agent within the above range, then is easy to that polymerizable liquid crystal compound is made to be horizontally oriented, and has the polarised light formed Layer becomes smoother tendency.If levelling agent is more than above range relative to the content of polymerizable liquid crystal compound, has and obtain The polarization photosphere obtained is easy to generate non-uniform tendency.In addition, the polarization photosphere formation composition contains two or more stream Flat agent.Contain dichroism pigment in above-mentioned polarization photosphere formation composition.Dichroism pigment described herein refers to have Absorbance in molecular long axis direction is different from the pigment in the property of the absorbance of short-axis direction.As long as having this property Matter, dichroism pigment are not particularly limited, and can be dyestuff or pigment.The dyestuff can be used it is a variety of, pigment equally can be used it is more Kind, dyestuff and pigment combination can also be used.It is preferred that above-mentioned dichroism pigment has maximum inhale in the range of 300~700nm It receives wavelength (λ MAX).Such dichroism pigment can be enumerated, such as acridine pigment, oxazine pigment, anthocyanidin, naphthalene pigment, idol Nitrogen pigment and anthraquinone pigment etc., wherein it is preferred that azopigment.Azopigment can be enumerated, and monoazo pigment, two azopigments, three are occasionally Nitrogen pigment, four azopigments and stilbazochrome etc., preferably two azopigments and trisazo- pigment.

Azopigment can be enumerated, such as formula (2) compound represented (being also referred to as " compound (2) " below according to situation).

A¹(- N=N-A²)_p- N=N-A³ (2)

[in formula (2),

A¹And A³Each independently represent the phenyl with or without substituent group, the naphthalene with or without substituent group Or the 1 valence heterocycle with or without substituent group.A²Indicate with or without substituent group to phenylene, have or not 1,4- naphthalene-diyl with substituent group or the divalent heterocycle with or without substituent group.P indicates 1~4 integer.When p is When 2 or more integer, multiple A²It is identical or different between each other.]

1 valence heterocycle can be enumerated, from quinoline, thiazole, benzothiazole, thieno thiazole, imidazoles, benzimidazole, oxazole and The group of 1 hydrogen atom is removed in the heterocyclic compounds such as benzoxazoles.The group for removing 2 hydrogen atoms from heterocyclic compound is suitable In divalent heterocycle, the concrete example for the heterocyclic compound being related to is as described above.

As A¹And A³In phenyl, naphthalene and 1 valence heterocycle, there are also A²In to phenylene, 1,4- naphthalene-diyl and divalent The substituent group that heterocycle arbitrarily has can be enumerated：The alkyl of carbon atom number 1~4；The carbon atoms such as methoxyl group, ethyoxyl and butoxy The alkoxy of number 1~4；The fluoro-alkyl of the carbon atom numbers such as trifluoromethyl 1~4；Cyano；Nitro；Halogen atom；Amino, diethyl (substituted-amino refers to that amino has the alkane of 1 or 2 carbon atom number 1~6 to the substituted or unsubstituted amino such as base amino and pyrrole radicals 2 on base or amino replace alkyl to be in the alkylidene that key forms carbon atom number 2~8.Unsubstituted amino refers to- NH₂.).In addition, the concrete example of the alkyl of carbon atom number 1~6 can enumerate the substitution arbitrarily having with the phenylene etc. of compound (1) Identical substituent group cited by base.

In compound (2), preferred any one compound represented of following formula (2-1)~formula (2-6).

[in formula (2-1)~(2-6),

B¹~B²⁰Each independently represent hydrogen atom, the alkyl of carbon atom number 1~6, the alkoxy of carbon atom number 1~4, cyanogen Base, nitro, substituted or unsubstituted amino (substituted-amino and unsubstituted amino are defined as above), chlorine atom or trifluoromethyl.

N1~n4 each independently represents 0~3 integer.

When n1 is 2 or more, multiple B²Identical or different between each other,

When n2 is 2 or more, multiple B⁶Identical or different between each other,

When n3 is 2 or more, multiple B⁹Identical or different between each other,

When n4 is 2 or more, multiple B¹⁴It is identical or different between each other.]

The object being easy to get from city Games can be used in such azopigment.As can be used for polarizing photosphere formation group The commercially available azopigment for closing object has " NKX2029 " and " G205 " (woods protobiochemistry research is made) etc..

As above-mentioned anthraquinone pigment, preferred formula (2-7) compound represented.

[in formula (2-7),

R¹~R⁸Each independently represent hydrogen atom ,-R^x、-NH₂、-NHR^x、-NR^x ₂、-SR^xOr halogen atom.

R^xIndicate the alkyl of carbon atom number 1~4 or the aryl of carbon atom number 6~12.]

As above-mentioned acridine pigment, preferred formula (2-8) compound represented.

[in formula (2-8),

R⁹~R¹⁵Each independently represent hydrogen atom ,-R^x、-NH₂、-NHR^x、-NR^x ₂、-SR^xOr halogen atom.

As Shang Shu oxazine pigment, preferred formula (2-9) compound represented.

[in formula (2-9),

R¹⁶~R²³Each independently represent hydrogen atom ,-R^x、-NH₂、-NHR^x、-NR^x ₂、-SR^xOr halogen atom.

In above formula (2-7), formula (2-8) and formula (2-9), R^xCarbon atom number 1~4 alkyl be methyl, ethyl, propyl And butyl etc., the aryl of carbon atom number 6~12 are phenyl, tolyl, xylyl and naphthalene etc..

As above-mentioned anthocyanidin, preferred formula (2-10) compound represented and formula (2-11) compound represented.

[in formula (2-10),

D¹And D²Each independently represent formula (2-10a)~formula (2-10d) group shown in any one.

N5 indicates 1~3 integer.]

[in formula (2-11),

D³And D⁴Each independently represent formula (2-11a)~formula (2-11h) group shown in any one.

N6 indicates 1~3 integer.]

Above-mentioned polarization photosphere forms the content with the dichroism pigment in composition, can be according to the type of the dichroism pigment Deng being suitably adjusted, such as relative to 100 mass parts of total amount of polymerism smectic liquid crystal compound, preferably 0.1 mass parts Above 50 below the mass, and more than more preferable 0.1 mass parts 20 below the mass, more than further preferred 0.1 mass parts 10 matter Measure part or less.It, can be in the feelings for the orientation for not upsetting polymerizable liquid crystal compound if the content of dichroism pigment is in the range Under condition, the polymerizable liquid crystal compound is made to keep the mesomorphic state polymerization of the smectic phase of high dimension.If the content of dichroism pigment Excessively, it is likely that hinder the orientation of polymerizable liquid crystal compound.Therefore, high dimension can be able to maintain in polymerizable liquid crystal compound In the range of smectic liquid crystal state, the content of dichroism pigment is determined.

Above-mentioned polarization photosphere formation composition contains solvent.The solvent is contemplated that used polymerizable liquid crystal compound Dissolubility etc., properly select ideal solvent.Wherein, the preferably unobvious polymerization for interfering the polymerizable liquid crystal compound is anti- The atent solvent that should be carried out.For example there are methanol, ethyl alcohol, ethylene glycol, isopropanol, propylene glycol, Ethylene Glycol Methyls for such solvent The alcohols solvents such as ether, ethylene glycol butyl ether and propylene glycol monomethyl ether；Ethyl acetate, butyl acetate, Ethylene Glycol Methyl ether acetic acid The ester solvents such as ester, gamma-butyrolacton or methyl proxitol acetate and ethyl lactate；Acetone, methyl ethyl ketone, cyclopentanone, ring The ketone solvents such as ketone, 2-HEPTANONE and methyl iso-butyl ketone (MIBK)；The aliphatic hydrocarbon solvents such as pentane, hexane and heptane；Toluene and dimethylbenzene Etc. the nitrile solvents such as aromatic hydrocarbon solvents, acetonitrile；The ether solvents such as tetrahydrofuran and dimethoxy-ethane；Chloroform and chlorobenzene etc. are molten containing chlorine Agent etc..These solvents can individually a kind of use, can also multiple combinations use.

Relative to the total amount of above-mentioned polarization photosphere formation composition, the content of solvent preferably 50~98 mass %.Change speech It, polarization photosphere is formed with solid component preferably 2~50 mass % in composition.If solid component more than 2 mass %, It can get dichroism necessary to the polarization photosphere having as this polarizer.On the other hand, if the solid component is in 50 matter For amount % hereinafter, then due to the viscosity of polarization photosphere formation composition, the thickness for polarizing photosphere can become generally uniform, therefore With making the polarization photosphere be not likely to produce non-uniform trend.In addition, for the solid component being related to, it can be above-mentioned according to that can be formed The thickness of photosphere is polarized to determine.

Above-mentioned polarization photosphere formation preferably comprises polymerization initiator with composition.The polymerization initiator is can to make polymerism The compound that the polymerization reaction of liquid-crystal compounds starts, it is excellent based on it can start the polymerization reaction under conditions of more low temperature in terms of Select Photoepolymerizationinitiater initiater.Specifically, at low temperature (as described above, the low temperature refer to 70 DEG C hereinafter, it is preferred that 60 DEG C of temperature below) Under the conditions of, Photoepolymerizationinitiater initiater can be used as by the compound that the effect of light generates living radical or acid.The photopolymerization is drawn It sends out among agent, the initiator more preferably generated free radicals by the effect of light.

It as above-mentioned Photoepolymerizationinitiater initiater, can enumerate, such as benzoin compound, benzophenone cpd, benzene alkyl ketone Compound, acylphosphine oxide compound, triaizine compounds, salt compounded of iodine and sulfonium salt etc..

Hereinafter, enumerating the concrete example of the Photoepolymerizationinitiater initiater.

Benzoin compound can be enumerated, such as styrax, styrax methyl ether, styrax ethylether, benzoin isobutyl propyl Ether and benzoin isobutyl butyl ether etc..

As benzophenone cpd, it can be mentioned, for example benzophenone, o-benzoyl yl benzoic acid methyl esters, 4- phenyl hexichol Ketone, 4- benzoyl -4 '-methyldiphenyl sulfide, 3,3 ', 4,4 '-four (t-butylperoxycarbonyl) benzophenone and 2,4,6- tri-methyl benzophenone etc..

Benzene alkyl ketone compound can be enumerated, such as diethoxy acetophenone, 2- methyl -2- morpholino -1- (4- methyl sulphur benzene Base) -1- acetone, 2- benzyl -2- dimethylamino -1- (4- morpholinyl phenyl) -1- butanone, 2- hydroxy-2-methyl -1- phenyl -1- Acetone, 1,2- diphenyl -2,2- dimethoxy -1- ethyl ketone, 2- hydroxy-2-methyl -1- (4- (2- hydroxyl-oxethyl) phenyl) -1- Acetone, 1- hydroxycyclohexylphenylketone and 2- hydroxy-2-methyl -1- (4- (1- methyl ethylene) phenyl) -1- acetone it is oligomeric Object etc..

Acylphosphine oxide compound can be enumerated, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and two (2,4,6- tri- Methyl benzoyl) phenyl phosphine oxide etc..

Triaizine compounds can be enumerated, such as 2,4- bis- (trichloromethyl) -6- (4- methoxyphenyl) -1,3,5-triazines, 2, 4- bis- (trichloromethyl) -6- (4- methoxyl group naphthalene) -1,3,5- triazine, 2,4- bis- (trichloromethyl) -6- (4- methoxy styrene Base) -1,3,5- triazine, 2,4- bis- (trichloromethyl) -6- (2- (5- methylfuran -2- base) vinyl) -1,3,5- triazine, 2,4- Two (trichloromethyl) -6- (2- (furans -2- base) vinyl) -1,3,5- triazine, 2,4- bis- (trichloromethyl) -6- (2- (4- diethyl Base amino-2-methyl phenyl) vinyl) -1,3,5- triazine and 2,4- bis- (trichloromethyl) -6- (2- (3,4- dimethoxy benzene Base) vinyl) -1,3,5- triazine etc..

The product for being easy to obtain from market can be used in Photoepolymerizationinitiater initiater.Commercially available Photoepolymerizationinitiater initiater can be enumerated, " イ Le ガキュア(Irgacure)907”、“イルガキュア184”、“イルガキュア651”、“イルガキュア819”、 " イ Le ガキュア 250 ", " イ Le ガキュア 369 " (チバジャパ Application (strain))；"セイクオールBZ","セイクオー Le Z ", " セイクオー Le BEE " (Seiko chemistry (strain))；" カヤキュアー (kayacure) BP100 " (day This chemical drug (strain))；" カヤキュアー UVI-6992 " (ダウ society system)；"アデカオプトマーSP-152","アデカオプトマー SP-170 " ((strain) ADEKA)；" TAZ-A ", " TAZ-PP " (Japanese シイベ Le ヘグナー society)；And " TAZ- 104 " (three and ケミカ Le societies) etc..

Above-mentioned polarization photosphere forms the content with the polymerization initiator in composition, can be according to the polarization photosphere formation group The type and its amount for closing the polymerizable liquid crystal compound contained by object are suitably regulated, for example, relative to polymerizable liquid crystal 100 mass parts of total amount of compound, the content of polymerization initiator preferably 0.1~30 mass parts, more preferable 0.5~10 mass parts, Further preferred 0.5~8 mass parts.If the content of polymerizing initiator is in the range, since polymerism liquid can not be upset The orientation of brilliant compound and be allowed to polymerize, therefore the polymerism smectic liquid crystal compound can keep high dimension smectic liquid crystal state In the case of polymerize.

When above-mentioned polarization photosphere formation composition contains Photoepolymerizationinitiater initiater, the composition can also contain light enhanced sensitivity Agent.The photosensitizing agent can be enumerated, such as the xanthones such as xanthone and thioxanthones compound (such as 2,4- diethyl thioxanthene Ketone, 2-isopropylthioxanthone etc.)；The anthracene compounds such as anthracene and anthracene (such as dibutoxy anthracene etc.) containing alkoxy；Phenothiazine and Rubrene etc..

When polarization photosphere formation composition contains Photoepolymerizationinitiater initiater and photosensitizing agent, it can further promote the polarization Photosphere forms the polymerization reaction of the polymerizable liquid crystal compound contained in composition.Though the usage amount of relevant photosensitizing agent Can according to Photoepolymerizationinitiater initiater and the type and its amount of polymerizable liquid crystal compound be suitably regulated, but preference It is 0.1~30 mass parts such as relative to 100 mass parts of the total amount of polymerizable liquid crystal compound, more preferable 0.5~10 mass parts, Further preferred 0.5~8 mass parts.

Though being illustrated by making above-mentioned polarization photosphere formation composition contain photosensitizing agent, polymerizable liquid crystal can be promoted The polymerization reaction of object is closed, but in order to carry out the polymerization reaction steadily, in the polarization photosphere formation composition, can also be fitted Contain polymerization inhibitor in locality.By containing polymerization inhibitor, the progress of polymerizable liquid crystal compound polymerization reaction can control.

Above-mentioned polymerization inhibitor can be enumerated, for example, hydroquinone, hydroquinone containing alkoxy, catechol containing alkoxy (such as Butyl-catechol etc.), pyrogallol, the free radical scavengers such as 2,2,6,6- tetramethyl -1- piperidines oxygroup free radical；Benzenethiol Class；Betanaphthyl amine and betanaphthol class etc..

When above-mentioned polarization photosphere formation composition contains polymerization inhibitor, content can be according to the polymerizable liquid crystal used The type and its amount and the usage amount of photosensitizing agent etc. for closing object are suitably regulated, but preferably for example relative to polymerism 100 mass parts of total amount of liquid-crystal compounds, the content of polymerization inhibitor are 0.1~30 mass parts, more preferable 0.5~10 mass parts, into One step preferably 0.5~8 mass parts.When the content of polymerization inhibitor in the range when, then formed since the polarization photosphere can not be upset It is allowed to polymerize with the orientation of the polymerizable liquid crystal compound or polymerizable liquid crystal compound that contain in composition, therefore the polymerization Property liquid-crystal compounds or polymerizable liquid crystal compound can keep being gathered in the case where high dimension smectic liquid crystal state well It closes.

By polarization photosphere formation composition described above, it is coated on the laminated board for having transparent substrate and oriented layer In oriented layer, the 1st coated film is obtained, is not assembled by the polymerizable liquid crystal compound contained in the 1st coated film It is dried under conditions of conjunction, forms the 1st dry coationg.

As the method (coating method) for being coated with the polarization photosphere formation composition on stating laminated board, for example there are examples Such as, extrusion coating methods, direct intaglio plate coating, reversed intaglio plate coating, CAP rubbing method, die coating method, Dipcoat method, Rod coating method and spin-coating method etc..In addition, these coating methods be also applied for for oriented layer formation being coated on composition it is transparent On substrate.In addition, setting application conditions, so that the thickness of the polarization photosphere obtained is in above-mentioned preferred scope.

Then, by drying the 1st coated film, solvent is removed from the 1st coated film, forms the 1st dry coationg. When removing solvent, the volatile component other than solvent contained by the 1st coated film is also eliminated together.The removing method of solvent, Usually using drying means (seasoning), can carry out natural seasoning, aeration-drying method perhaps hypobaric drying method or they Combined method.In addition, any one can be used in seasoning, but the drying condition preferably set will not make the 1st coated film Contained polymerizable liquid crystal compound polymerization.

In process (3), the mesomorphic state of the polymerizable liquid crystal compound contained by the 1st dry coationg is maintained at smectic In the case where mesomorphic state, it polymerize the polymerizable liquid crystal compound, to form polarization photosphere by the 1st dry coationg.

In order to make polymerizable liquid crystal compound contained by the 1st dry coationg mesomorphic state become smectic phase (hereinafter, According to circumstances, referred to as " smectic phase " or " mesomorphic state of smectic phase "), the 1st dry coationg is heated to temperature appropriate , in other words, the element being made of the laminated board with the 1st dry coationg is heated to be found out by phase transition temperature suitable When temperature.In addition, when forming smectic phase, once the liquid of polymerizable liquid crystal compound contained by the 1st dry coationg It is preferably smectic phase by the nematic Phase after crystalline state becomes nematic phase (nematic liquid crystal state).In order to like this via Nematic phase and form smectic phase, for example, by using following methods, polymerizable liquid crystal compound contained by the 1st dry coationg is heated to Phase transition is the temperature of nematic mesomorphic state or more, then, which is cooled to display smectic liquid The temperature of crystalline state.

Smectic liquid crystal state aspect is being formed via nematic phase, the polarization photosphere formation composition particularly preferably contains Above-mentioned levelling agent.When forming mesomorphic state, if the 1st dry coationg contains levelling agent, have the advantage that, it is dry the 1st In dry envelope, levelling agent is easy flowing, and polymerizable liquid crystal compound or polymerizable liquid crystal compound are easy horizontal alignment.It is formed More than temperature when nematic phase and smectic phase, preferably nematic Phase point and below 100 DEG C of temperature higher than nematic Phase point Range, more than more preferable nematic Phase point, 50 DEG C of temperature range below higher than nematic Phase point.It can also be simultaneously It carries out for being orientated to the heat treatment of desired liquid crystalline phase and the drying process of above-mentioned solvent.

When polymerizeing the polymerizable liquid crystal compound, in order to keep smectic liquid crystal state well, as the polymerism Liquid-crystal compounds is, it is preferable to use (more containing the polymerizable liquid crystal mixture being made of two or more polymerizable liquid crystal compounds It is preferred that the polymerizable liquid crystal mixture being made of two or more polymerism smectic liquid crystal compounds) polarization photosphere form use Composition.If using the content to each polymerizable liquid crystal compound in the polymerizable liquid crystal compound than carrying out the inclined of adjustment The photosphere that shakes, which is formed, uses composition, then has the advantage that, after forming smectic liquid crystal state via nematic phase, can be temporarily forming supercooling But state is easy to keep the smectic liquid crystal state of high dimension.

So that the polarization photosphere formation composition is contained Photoepolymerizationinitiater initiater, makes the polymerism liquid in the 1st dry coationg After the mesomorphic state of brilliant compound becomes smectic phase, in the case where keeping the smectic liquid crystal state, make the polymerizable liquid crystal Compound carries out photopolymerization and is described in detail herein to the light polymerization process.In photopolymerization, as to the 1st dry coationg into The light of row irradiation, according to the type of Photoepolymerizationinitiater initiater contained by the 1st dry coationg or polymerizable liquid crystal compound Type (in particular, the type for the photopolymerizable group that the polymerizable liquid crystal compound has) and its amount can be used suitably and be selected from Visible light, the light of ultraviolet light and laser or active electrons ray carry out.Wherein, from the progress for being easy to control polymerization reaction, or The device for the object that is widely used in this field is able to use as photopolymerization being related to from the aspect of, preferred ultraviolet light.It is therefore preferable that Pre-select the type of polymerizable liquid crystal compound contained by the polarization photosphere formation composition or Photoepolymerizationinitiater initiater, choosing Selecting being capable of photopolymerization by ultraviolet light.In addition, cooling hand appropriate can also be used while ultraviolet light when polymerization Section, to cool down the 1st dry coationg, controls polymerization temperature with this.It, can be at lower temperatures by using such cooling way If the polymerization for implementing polymerizable liquid crystal compound, then also have the advantage that, even if above-mentioned transparent substrate or oriented layer are using resistance to Hot relatively low substance, can also be properly formed polarization photosphere.In addition, when photopolymerization, can also it is hidden by photoetching or Development, obtains patterned polarization photosphere.

By carrying out photopolymerization as above, the polymerizable liquid crystal compound gathers in the case where keeping smectic liquid crystal state It closes, preferably polymerize in the case where keeping the smectic liquid crystal state of high dimension, form polarization photosphere.Polymerizable liquid crystal compound or Person's polymerizable liquid crystal compound polymerize in the case where keeping smectic liquid crystal state, and obtains polarization photosphere, polarization photosphere tool There is the advantages of its polarised light performance is significantly larger than previous polarization photosphere, previous polarization photosphere is to keep nematic liquid Photosphere is polarized obtained from polymerizeing polymerizable liquid crystal compound etc. in the case where crystalline state.

In addition, the polarization photosphere being thusly-formed is particularly preferred, bragg peak can be obtained in X-ray diffraction measure The polarization photosphere of (bragg peak).As such polarization photosphere that can obtain bragg peak, there can be exemplified for example, aobvious Show the polarization photosphere of the diffraction maximum from hexagonal phase or crystal phase.In addition, the determination condition for the X-ray diffraction measure being related to is lifted Example has such as the condition that embodiments herein is recorded.

In process (3), oriented layer and polarization photosphere are set gradually over the transparent substrate, and obtain laminated board, process (4) It is the process that protective layer is formed on the polarization photosphere of the laminated board.Polarization photosphere in this polarizer is, for example, in smectic B Etc relatively high dimension smectic liquid crystal state under make polymerizable liquid crystal compound polymerize and formed polarization photosphere when, the polarization Photosphere observable deterioration due to external environmental factor sometimes.By forming protective layer on polarization photosphere, can extremely efficient prevent Only the polarization photosphere is rotten.

As process (4), for example there are following processes etc.,

Process (4-1), by the way that on the polarization photosphere that the process (3) is formed, coating contains multifunctional acrylic acid The protective layer of ester and solvent, which is formed, uses composition 1, and the 2nd coated film is formed on the polarization photosphere, makes contained by the 2nd coated film The polyfunctional acrylic ester polymerization, to form protective layer by the 2nd coated film；

Process (4-2), by the way that on the polarization photosphere that the process (3) is formed, coat protective layer is formed with combination Object 2, the protective layer formation with composition 2 contain polymerize polyfunctional acrylic ester polymer or oligomer and Water, and the 2nd coated film is formed on the polarization photosphere, keep the 2nd coated film dry, to form protection by the 2nd coated film Layer；And

Process (4-3), by the way that on the polarization photosphere that the process (3) is formed, coating contains water-soluble polymer With the protective layer formation composition 3 of water, and the 2nd coated film is formed on the polarization photosphere, keep the 2nd coated film dry, from And protective layer is formed by the 2nd coated film.

On the polarization photosphere that the process (3) are formed, it is coated with the protection containing polyfunctional acrylic ester and solvent Layer, which is formed, uses composition 1, and the 2nd coated film is formed on the polarization photosphere, makes described multifunctional third contained by the 2nd coated film Olefin(e) acid polyisocyanate polyaddition is illustrated this method to form protective layer by the 2nd coated film.Use is formed by such protective layer It is extremely simple that the method that composition 1 forms protective layer also has the advantages that it is operated.<Protective layer, which is formed, uses composition 1>

The protective layer, which is formed, contains polyfunctional acrylic ester and solvent with composition 1.The protective layer, which is formed, uses composition 1 Contained polyfunctional acrylic ester refers to such compound, i.e., its intramolecular is with 2 or more selected from by acrylate-based (CH₂=CH-CO-) and methacrylate (CH₂=C (CH₃)-CO-) and constitute group group, do not have liquid crystal liquid crystal property such as The compound (1).Preferred polyfunctional acrylic ester is that there are intramolecular 2~6 to be selected from by acrylate-based and methyl The compound of the group of the group of acrylate-based composition.In addition, according to the number of group, hereinafter, will have 2 above-mentioned groups Polyfunctional acrylic ester etc. be referred to as " 2 functional acrylate " etc., will be with the polyfunctional acrylic ester of 3 or more above-mentioned groups Referred to as " above polyfunctional acrylic ester " etc. of 3 functions.

Further, for protective layer formation polyfunctional acrylic ester contained by composition 1, make the multifunctional propylene When acid esters hardens reaction and is made protective layer, such protective layer selection has the substance of the transparency, which refers to The degree that light, especially visible light can penetrate.In addition, " degree that the transparency can be penetrated in visible light " described here, Its meaning is identical as the meaning illustrated in the transparency of the transparent substrate.

Here, illustrating preferred polyfunctional acrylic ester.

As in the molecule with 2 groups selected from the group being made of acrylate-based and methacrylate 2 functional acrylates, for example there are：1,3 butylene glycol two (methyl) acrylate；1,3 butylene glycol (methyl) acrylate；1, 6- hexylene glycol two (methyl) acrylate；Ethylene glycol two (methyl) acrylate；Diethylene glycol two (methyl) acrylate；New penta Glycol two (methyl) acrylate；Triethylene glycol two (methyl) acrylate；Tetraethylene glycol two (methyl) acrylate；Poly- second two Alcohol diacrylate；Bis- (acryloyl-oxyethyl) ethers of bisphenol-A；Ethoxylated bisphenol A bis- (methyl) acrylate；Propoxyl group Change neopentyl glycol two (methyl) acrylate；Ethoxylation neopentyl glycol two (methyl) acrylate and 3- methyl pentanediol two (methyl) acrylate etc..

As intramolecular there are 3~6 to be selected from the group being made of acrylate-based and methacrylate More than 3 functions of group 6 functions polyfunctional acrylic esters below,

Trimethylolpropane tris (methyl) acrylate；Pentaerythrite three (methyl) acrylate；Three (2- ethoxys) are different Cyanurate three (methyl) acrylate；Ethoxylated trimethylolpropane three (methyl) acrylate；Three hydroxyl first of propoxylation Base propane three (methyl) acrylate；Pentaerythrite four (methyl) acrylate；Dipentaerythritol five (methyl) acrylate；Two Pentaerythrite six (methyl) acrylate；Tripentaerythritol four (methyl) acrylate；Tripentaerythritol five (methyl) acrylic acid Ester；Tripentaerythritol six (methyl) acrylate；Tripentaerythritol seven (methyl) acrylate；Tripentaerythritol eight (methyl) third Olefin(e) acid ester；

The reactant of pentaerythrite three (methyl) acrylate and acid anhydrides；Dipentaerythritol five (methyl) acrylate and acid The reactant of acid anhydride；

The reactant of tripentaerythritol seven (methyl) acrylate and acid anhydrides；

Caprolactone modification trimethylolpropane tris (methyl) acrylate；Caprolactone modification pentaerythrite three (methyl) propylene Acid esters；Caprolactone modification triisopropyl second sulphonyl (2- ethoxy) isocyanuric acid ester three (methyl) acrylate；Caprolactone modification Pentaerythrite four (methyl) acrylate；Caprolactone modification dipentaerythritol five (methyl) acrylate；Two season of caprolactone modification Penta tetrol six (methyl) acrylate；Caprolactone modification tripentaerythritol four (methyl) acrylate；Three season penta of caprolactone modification Tetrol five (methyl) acrylate；Caprolactone modification tripentaerythritol six (methyl) acrylate；Three season penta 4 of caprolactone modification Alcohol seven (methyl) acrylate；Caprolactone modification tripentaerythritol eight (methyl) acrylate；Caprolactone modification pentaerythrite three The reactant of (methyl) acrylate and acid anhydrides；Caprolactone modification dipentaerythritol five (methyl) acrylate is reacted with acid anhydrides Object and (methyl) acrylate of caprolactone modification tripentaerythritol seven and the reactant of acid anhydrides etc..In addition, what is illustrated herein is more In the concrete example of functional acrylate, (methyl) acrylate refers to acrylate or methacrylate.In addition, caprolactone Modification, which refers to, imports oneself between the position and (methyl) acryloxy from ethyl alcohol of (methyl) acrylate compounds The open loop body or ring-opening polymerization polymer of lactone.

The big protective layer of surface hardness in order to obtain, it is preferable to use 3 officials in the concrete example of above-mentioned polyfunctional acrylic ester Polyfunctional acrylic ester more than energy particularly preferably uses 6 functional acrylates.In addition, the protective layer, which is formed, uses composition 1 A kind of polyfunctional acrylic ester can be contained, more than two polyfunctional acrylic esters can also be contained.

In addition, from the aspect of the gauffer of the printing of protective layer formation composition 1 or obtained protective layer, in the guarantor Adhesive resin can also be contained in sheath formation composition 1.

Adhesive resin citing preferably is selected from least the one of the group being made of unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides The copolymer of the monomer of kind and the other monomers that can be copolymerized with the monomer.

For example there are the unsaturated monocarboxylics such as acrylic acid, methacrylate and butenoic acid for the concrete example of unsaturated carboxylic acid Class；The unsaturated dicarboxylic acids class such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid；Mono succinate 2 yuan or more of (2- (methyl) acryloyl-oxyethyl), phthalic acid list (2- (methyl) acryloyl-oxyethyl) etc. it is polynary Single ((methyl) acryloxyalkyl) esters of the unsaturation of carboxylic acid；Containing in hydroxyl in the same molecules such as α-(methylol) acrylic acid Base and the unsaturated esters of acrylic acid of carboxyl etc..Unsaturated carboxylic acid anhydrides are the acid anhydrides of unsaturated carboxylic acid shown here.Wherein, Described adhesive resin manufacture monomer, preferably acrylic acid, methacrylic acid and maleic anhydride etc..These acrylic acid, Methacrylate and maleic anhydride, it is good from polymerisation reactivity when being copolymerized with other various monomers, obtain adhesive The glass transition temperature (Tg) and mechanical property of resin be high, it is non-wrinkled see, and be preferably used.In addition, manufacture adhesive When resin, about the monomer selected from the group being made of unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides, one kind can be used, it can also It is two or more to use.

As other lists that can be copolymerized with the monomer selected from the group being made of unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides Body, for example there are,

(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) acrylic acid Zhong Ding Ester and (methyl) tert-butyl acrylate etc. (methyl) alkyl-acrylates；

(methyl) cyclohexyl acrylate, (methyl) acrylic acid -2- methyl cyclohexyl, (methyl) acrylic acid tricyclic [5.2.1.02,6] decyl- 8- base ester (in this field, usual entitled (methyl) dicyclopentyl acrylate), acrylate Ester, acrylic acid -2- methyl cyclohexyl, acrylic acid tricyclic [5.2.1.02,6] decyl- 8- base ester (in this field, usual entitled third Olefin(e) acid bicyclopentyl ester), (methyl) acrylic acid bicyclopentyl 2-ethoxyethyl acetate, (methyl) acrylic acid such as (methyl) isobornyl acrylate Cyclic alkyl esters；

Cyclohexyl acrylate, acrylic acid -2- methyl cyclohexyl, acrylic acid tricyclic [5.2.1.02,6] decyl- 8- base ester (ability In domain, usual entitled dicyclopentyl acrylate), acrylic acid bicyclopentyl 2-ethoxyethyl acetate, the acrylic acid such as isobornyl acrylate Cyclic alkyl esters；

(methyl) phenyl acrylate and (methyl) benzyl acrylate etc. (methyl) benzyl acrylate class；

The dicarboxylic diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate；

The hydroxy alkyls esters such as (methyl) 2-Hydroxy ethyl acrylate and (methyl) 2-hydroxypropyl acrylate；

Two rings [2.2.1] -2- heptene, 5- methyl bicyclic [2.2.1] -2- heptene, 5- ethyl two rings [2.2.1] -2- heptene, 5- hydroxyl two rings [2.2.1] -2- heptene, 5- carboxyl two rings [2.2.1] -2- heptene, 5- hydroxyl two rings [2.2.1] -2- heptene, 5- (2'- ethoxy) two rings [2.2.1] -2- heptene, 5- methoxyl group two rings [2.2.1] -2- heptene, two ring of 5- ethyoxyl [2.2.1] - 2- heptene, 5,6- dihydroxy two rings [2.2.1] -2- heptene, 5,6- dicarboxyl two rings [2.2.1] -2- heptene, (the hydroxyl first of 5,6- bis- Base) two rings [2.2.1] -2- heptene, 5,6- bis- (2'- ethoxy) two rings [2.2.1] -2- heptene, two ring of 5,6- dimethoxy [2.2.1] -2- heptene, 5,6- diethoxy two rings [2.2.1] -2- heptene, 5- hydroxy-5-methyl base two ring [2.2.1] -2- heptan Alkene, 5- hydroxyl -5- ethyl two ring [2.2.1] -2- heptene, 5- carboxyl -5- methyl bicyclic [2.2.1] -2- heptene, 5- carboxyl -5- Two ring of ethyl [2.2.1] -2- heptene, 5- methylol -5- methyl bicyclic [2.2.1] -2- heptene, 5- carboxyl -6- methyl bicyclic [2.2.1] -2- heptene, 5- carboxyl -6- ethyl two ring [2.2.1] -2- heptene, 5,6- dicarboxyl, two ring [2.2.1] -2- heptenoic acid Acid anhydride (carbic acid), two ring of 5- tert-butoxycarbonyl [2.2.1] -2- heptene, two ring [2.2.1] of 5- cyclohexyl carbonyloxy group - 2- heptene, two ring of 5- phenyloxycarbonyl [2.2.1] -2- heptene, 5,6- bis- (tert-butoxycarbonyl) two ring [2.2.1] -2- heptene And 5, the two ring unsaturated compound classes such as 6- bis- (cyclohexyl carbonyloxy group) two rings [2.2.1] -2- heptene；

N- phenylmaleimide, N- cyclohexylmaleimide, N- benzyl maleimide, N- Succinimide -3- maleimide benzoic ether, N- succinimide -4- maleimide butyl ester, N- amber Acid imide -6- maleimide capronate, N- succinimide -3- maleimide propionic ester, N- (9- acridine Base) the dicarbonyl imides derivative species such as maleimide；

Styrene, α-methylstyrene, m-methyl styrene, p-methylstyrene, vinyltoluene, to methoxybenzene Ethylene, acrylonitrile, methacrylonitrile, vinyl chloride, dichloroethylene, acrylamide, Methacrylamide, vinylacetate, 1,3- Butadiene, isoprene and 2,3- dimethyl -1,3-butadiene etc..

Protective layer formation solvent contained by composition 1 for example there are, such as with the polarizing layer formation composition The identical solvent of the object that contained solvent enumerates.Wherein, solvent contained by the protective layer formation composition 1 preferably contains By the substance for the solvent selected from the group being made of alcoholic solvent and ether solvents, more preferably actually by alcoholic solvent and/or Person's ether solvents composition.Herein, following any objects are actually referred to by the solvent that alcoholic solvent and/or ether solvents form Matter is practically free of the substance of the solvent except the alcoholic solvent, is practically free of the substance of the solvent except the ether solvents, is practically free of The substance of solvent except the alcoholic solvent and the ether solvents.Only, it is actually made of alcoholic solvent and/or ether solvents Solvent in, can be containing not being deliberately containing it moisture etc., as long as micro in the degree for being capable of forming protective layer.The alcohol is molten Agent is as described above, for example there are methanol, ethyl alcohol, butanol, ethylene glycol, isopropanol, propylene glycol, Ethylene glycol methyl ether, ethylene glycol butyl Ether and propylene glycol monomethyl ether etc..For example there are ethylene glycol single methyl ether acetic acid esters and propylene glycol monomethyl ether second for the ether solvents Acid esters etc..Among these, which forms the solvent contained by composition it is further preferred that ethyl alcohol, isopropanol, propylene glycol monomethyl ether And propylene glycol monomethyl ether, and the two or more mixed solvents selected from these.

What protective layer formation solvent contained by composition 1 was actually made of alcoholic solvent and/or ether solvents Words will not significantly damage the state of orientation of polarization photosphere when being coated with the protective layer formation composition 1 on polarizing photosphere, can To form protective layer in the case where keeping the state of orientation.At this point, if the protective layer is formed contained by composition 1 Solvent is actually made of alcoholic solvent and/or ether solvents, then can steadily manufacture this polarizer.In addition, making like this It is also advantageous on this point its is easy to operate with protective layer formation with the method that composition 1 forms protective layer.In addition, about Protective layer forms the content of the solvent contained by composition 1, considers the protective layer formation composition 1 being coated on polarization photosphere Coating when upper is determined, for example, 100 mass parts of total amount relative to protective layer formation composition 1, preferably molten The content of agent is 10~80 mass parts, more preferably 20~60 mass parts.

When forming protective layer with composition 1 by protective layer formation, need to make contained by the protective layer formation composition 1 much Functional acrylic polyisocyanate polyaddition and harden.The polymerization of the polyfunctional acrylic ester it is also preferred that, formed in the polarization photosphere with combination Photopolymerization described in the polymerization of polymerizable liquid crystal compound contained by object.The photopolymerization of the polyfunctional acrylic ester can pass through For the 2nd dry coationg being formed on the polarization photosphere by the protective layer formation composition 1, visible light or ultraviolet is irradiated Line is implemented.In addition, the preferably described protective layer, which is formed, to be used in order to more effectively implement the photopolymerization of polyfunctional acrylic ester Composition 1 contains Photoepolymerizationinitiater initiater.For example there are and contained by the polarization photosphere formation composition for the Photoepolymerizationinitiater initiater Identical Photoepolymerizationinitiater initiater illustrated by Photoepolymerizationinitiater initiater.

Hereinafter, carrying out simple illustration to the operation for forming protective layer.

Formation for protective layer, firstly, the protective layer formation composition 1 is coated on the polarization photosphere, And form the 2nd coated film.Such protective layer forms the coating method for using composition 1, for example, with as being coated with the polarised light The method that the method for layer formation composition is illustrated is identical.

Then, removed in the 2nd coated film obtained from being coated on polarization photosphere solvent (preferably alcoholic solvent and/or Person's ether solvents), obtain the 2nd dry coationg.Related drying can also form the described 1st using with by the 1st coated film The identical method of the method enumerated in the drying means of dry coationg.It is dry during keeping the 2nd dry coationg dry Middle needs accomplish that unpolymerized polymerizable liquid crystal compound will not be mixed into the 2nd dry coationg from the polarization photosphere.Cause This, the range that preferably 0~60 DEG C or so of temperature condition, more preferable 20~50 DEG C or so of range.

When protective layer formation solvent contained by composition 1 is the solvent that example more preferably is illustrated, By above-mentioned suitable temperature condition, the 2nd coated film can be dried.In addition, in order to implement drying in such temperature range, According to the type of protective layer formation solvent contained by composition 1, under reduced pressure appropriate, the 2nd coated film is kept ?.

The inventors discovered that its solvent is actually formed use by the protective layer that alcoholic solvent and/or ether solvents form Composition 1 will not damage the property of the polarization photosphere when being coated on the polarization photosphere.Therefore, if using above-mentioned protective layer It is formed and uses composition 1, formed protective layer on polarization photosphere, then by protective layer, can not only prevent this polarizer well The polarization photosphere having changes over time matter, and in protective layer formation, can prevent the property of damage polarization photosphere well The generation of matter.Said effect never directly embodies in the manufacture of the previous polarizer, is seeing based on the present inventor individual What solution was made.

Coat protective layer, which is formed, on the polarization photosphere that the process (3) are formed uses composition 2, which forms Contain polymer or oligomer and water obtained from polymerizeing polyfunctional acrylic ester with composition 2, and in the polarization photosphere The 2nd coated film of upper formation keeps the 2nd coated film dry, to form protective layer by the 2nd coated film, says to this method It is bright.It is extremely simple with the method that composition 2 forms protective layer also to have the advantages that it is operated by such protective layer formation.

The protective layer formation composition 2 contains polymer or oligomeric obtained from making polyfunctional acrylic ester polymerization Object and water.For example there are such as aliphatic amines formic acid second for polymer obtained from polymerizeing polyfunctional acrylic ester or oligomer Ester acrylate etc..

For the content of protective layer formation water contained by composition 2, which is coated with by consideration Coating when polarizing on photosphere determines, for example, 100 mass parts of total amount relative to protective layer formation composition 2, The content of water preferably 50~99 mass parts, more preferable 60~95 mass parts.

Hereinafter, carrying out simple illustration to the operation that protective layer is formed.

Protective layer is formed, firstly, the protective layer formation composition 2 is coated on the polarization photosphere, is formed 2nd coated film.Related protective layer forms the coating method for using composition 2, for example, with as being coated with the polarization photosphere shape It is identical at method illustrated by the method with composition.

Then, water is removed from the 2nd coated film, obtains protective layer.The method and conduct that related drying can use The method of the drying means citing of 1st coated film is identical.As temperature condition, preferably 0~100 DEG C of approximate range, more It is preferred that 20~80 DEG C of approximate range.

On the polarization photosphere that the process (3) are formed, it is coated with the protective layer shape containing water-soluble polymer and water At with composition 3, and the 2nd coated film is formed on the polarization photosphere, keep the 2nd coated film dry, thus by the 2nd coated film Protective layer is formed, this method is illustrated.Also had by the method that such protective layer formation composition 1 forms protective layer It operates extremely simple advantage.

The protective layer, which is formed, contains water-soluble polymer and water with composition 3.For example there are such as poly- for water-soluble polymer Vinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinylpyrrolidone, starch, methylcellulose, carboxy methyl cellulose, alginic acid Sodium etc., preferable examples have polyvinyl alcohol.

For the content of protective layer formation water contained by composition 3, which is coated with by consideration Coating when polarizing on photosphere determines, for example, 100 mass parts of total amount relative to protective layer formation composition 3, The content of water preferably 50~99 mass parts, more preferable 60~95 mass parts.

Protective layer is formed, firstly, the protective layer formation composition 3 is coated on the polarization photosphere, is formed 2nd coated film.Related protective layer forms the coating method for using composition 3, for example, with as being coated with the polarization photosphere shape It is identical at method illustrated by the method with composition.

Then, water is removed from the 2nd coated film, obtains protective layer.The method and conduct that related drying can use The method of the drying means citing of 1st coated film is identical.As temperature condition, preferably 0~100 DEG C or so of range, more It is preferred that 20~80 DEG C or so of range.

The thickness of protective layer can carry out adjustment appropriate, example according to the type etc. for the polarization photosphere protected by protective layer Such as, preferably 0.1~30 μm of range, more preferable 1~5 μm of range.Method used by the measurement of related thickness also with The method that the measuring method of thickness as the polarization photosphere illustrates is identical.

By this polarizer obtained with process (1)~process (4) manufacturing method, by being provided with protective layer, not only The marresistance or excellent solvent resistance of its polarised light layer surface, and in the heat resistance and humidity resistance of this polarizer itself It is on this point excellent, also more advantageous than the previous polarizer.In addition, the manufacturer of this polarizer with process (1)~process (4) The embodiment of method, can carry out various modifications in the range of not changing following manner, and which refers at 25 ± 10 DEG C Under the conditions of temperature, make the polymerizable liquid crystal compound or polymerism liquid contained in the 1st dry coationg of process (3) Brilliant composition polymerize in the case where keeping smectic liquid crystal state.For example, formed or preparatory process (1) transparent substrate with take To layer laminated board when, the transparent substrate itself, which can be used, has orientation characteristic, it is also possible that composition, in addition to taking To layer, lamination phase difference film is gone back, is configured with oriented layer, polarization photosphere, phase separation layer and guarantor in order over the transparent substrate Sheath.In addition, it is different to be mixed into ultraviolet absorbing agent, antistatic agent or refractive index in the protective layer that process (4) is formed In the resin of the ball shape of protection composition of layer.Only, it is formed as forming the protective layer used in protective layer with combination It is the solvent being actually made of alcoholic solvent and/or ether solvents as solvent in object, or to be advantageous when water, institute It is advisable with using the protective layer formation of related solvents that can implement process (4) with composition.

More than, this polarizer is illustrated, the explanation is with transparent substrate/oriented layer/polarization photosphere/protective layer layer Centered on the mode of product body, but this polarizer can be with the layer other than these layers of lamination.As described above, this polarizer can be into one Step has phase difference film, can also be further equipped with anti-reflection layer or brightness enhancement film.In addition it is also possible to 1/4 wavelength plate Combination is made circular polarization light board.1/4 wavelength plate used when manufacturing circular polarization light board is preferably the face for having it for visible light Interior phase difference value shortens and the wavelength plate of reduced characteristic with wavelength.

The purposes > of this polarizer of <

This polarizer can be used for various display devices.Display device refers to the device with display element, and it includes shine Element or light emitting device are as light emitting source.Display device can be enumerated, such as the display of liquid crystal display device, organic electroluminescent (EL) Device, inorganic EL (EL) display device, electron emission display (such as field-emission display device (FED), surface Conduct electron emission display (SED)), Electronic Paper is (using electronic ink or electrophoresis element display device, plasma display dress It sets, projection display device (such as grating light valve (GLV) display device, the display dress with digital microlens device (DMD) Set) and piezoelectric ceramics display etc..Liquid crystal display device equally includes that transmissive liquid crystal display device, semi-transparent liquid crystal are shown Device, reflection-type liquid-crystal display device, direct view liquid crystal display device and projection type liquid crystal display apparatus etc. it is any.These are aobvious Showing device can be the display device of display two dimensional image, can also be the 3 d display device of display 3-D image.

This polarizer is also effectively used for especially organic electroluminescent (EL) display device or inorganic EL (EL) display device of display device.

Fig. 1 is the schematic overview of the simplest section constitution of this polarizer.From the successively lamination oriented layer of transparent substrate 2 3, photosphere 4 and protective layer 7 are polarized, about polarization photosphere 4, is dispersed in the matrix 5 that polymerizable liquid crystal compound is polymerized There is dichroism pigment 6.

Fig. 2 and Fig. 5 is that the liquid crystal display device of this polarizer has been used (to be also referred to as " this liquid crystal display below according to situation Device ") 10 section constitution schematic overview.Liquid crystal layer 17 is held between two pieces of substrate 14a and substrate 14b.

Fig. 4 and Fig. 7 is that the EL display device of this polarizer has been used (to be also referred to as " this EL display dress below according to situation Set ") section constitution schematic overview.

Fig. 8 is the schematic overview for having used the composition of projection type liquid crystal display apparatus of this polarizer.

Firstly, being illustrated to shown in Fig. 2 liquid crystal display device.

This polarizer is configured at its light incident side preferably with respect to liquid crystal layer.It is configured in 17 side of liquid crystal layer of substrate 14a Colored filter 15.Colored filter 15 is configured at the position opposite with the pixel electrode 22 of clamping liquid crystal layer 17, black matrix" 20 are configured at the opposite position in region between pixel electrode.Transparent electrode 16 is configured at 17 side of liquid crystal layer, covers colorized optical filtering Piece 15 and black matrix" 20.In addition, can have protective film layer (not shown) between colored filter 15 and transparent electrode 16.

In 17 side of liquid crystal layer of substrate 14b, thin film transistor (TFT) 21 and pixel electrode 22 are by rule configuration.Pixel electrode 22 is matched It is placed in the position opposite with the colored filter 15 of clamping liquid crystal layer 17.Between thin film transistor (TFT) 21 and pixel electrode 22, match It is equipped with the interlayer dielectric 18 with connecting hole (not shown).

As substrate 14a and substrate 14b, glass substrate and plastic base are used.The glass substrate and plastic base being related to, Substrate identical with material cited by the transparent substrate as this polarizer can be used.In the colour that manufacture is formed on substrate When optical filter 15 or thin film transistor (TFT) 21, in the case where the process for needing to heat under high temperature, preferably glass substrate or quartz Substrate.

Thin film transistor (TFT) can be according to the material of substrate 14b, using best mode.Thin film transistor (TFT) 21 can be enumerated, and be formed in The poly- silicon transistor of high temperature on quartz base plate, the low-temperature poly-silicon transistor being formed on glass substrate, be formed in glass substrate or Amorphous silicon transistor on plastic base.In order to make this liquid crystal display device smallerization, drive can also be formed on substrate 14b Dynamic IC.

Liquid crystal layer 17 is configured between transparent electrode 16 and pixel electrode 22.In liquid crystal layer 17, in order to make substrate 14a And certain distance is kept between substrate 14b, it is configured with gasket 23.It in addition, column gasket is shown in Fig. 2, but is not by the pad Piece is limited to column, as long as can make to maintain a certain distance between substrate 14a and substrate 14b, shape is arbitrary shape.

, can be on the face contacted with liquid crystal layer 17 among the layer formed on substrate 14a and substrate 14b, being respectively configured makes The oriented layer that liquid crystal is orientated to desired orientation.In addition, this polarizer is configured inside liquid crystal cell, that is, can with 17 phase of liquid crystal layer The side in the face connect configures this polarizer.Such form hereinafter is referred to as " embedded ".This is embedded be detailed in it is aftermentioned.

Each component is by substrate 14a, colored filter 15 and black matrix" 20, transparent electrode 16, liquid crystal layer 17, pixel electrode 22, interlayer dielectric 18 and thin film transistor (TFT) 21, there are also substrate 14b, lamination is formed in order.

The polarizer is provided on the outside of substrate 14b in such substrate 14a and substrate 14b for being clamped with liquid crystal layer 17 12a and 12b, at least one in them are this polarizers.

Further, preferably it is laminated with phase separation layer (such as 1/4 wavelength plate or optical compensation films) 13a and 13b.Two are risen In inclined device, by configuring polarizer 12b, the function that this liquid crystal display device 10 converts incident light into rectilinearly polarized light can be assigned Energy.In addition, phase can not also be configured according to the type of the liquid-crystal compounds contained in the structure of liquid crystal display device or liquid crystal layer 17 Also polarization film can be further arranged in the light emitting side (outside) of this polarizer 1 in potential difference film 13a and 13b.

It can also match in the outside (when this polarizer 1 is further configured with polarization film, on the outside) of this polarizer 1 Set the antireflection film 11 for preventing ambient light from reflecting.

As described above, this polarizer 1 can be used in the polarizer 12a or 12b of this liquid crystal display device 10 of Fig. 2.It is logical It crosses and this polarizer 1 is set to the polarizer 12a and/or 12b, there is the effect for the slimming that can reach this liquid crystal display device 10 Fruit.

When this polarizer 1 is used for polarizer 12a or 12b, laminated order is not particularly limited.It is empty referring to being used in Fig. 2 The enlarged drawing of A and part B that coil goes out are described.

Fig. 3 is the section enlarged diagram of the part A in Fig. 2.In (A1) of Fig. 3, use this polarizer 1 as being polarized When device 12a, it is shown that configuring in order transparent substrate 2, oriented layer 3, polarization photosphere 4 and protective layer 7 from the side phase separation layer 13a This polarizer 1 is set.In addition, (A2) of Fig. 3 is shown from the side phase separation layer 13a, protective layer 7, polarization photosphere are configured in order 4, this polarizer 1 is arranged in oriented layer 3, transparent substrate 2.

Fig. 4 is the enlarged diagram of the part B of Fig. 2.(B2) of Fig. 4 is shown, use this polarizer as being polarized When device 12b, this polarizer 1 is taken from the side phase difference film 13b, configures in order protective layer 7, polarization photosphere 4, oriented layer 3 and transparent It is arranged made of substrate 2.

In the outside of polarizer 12b, configured with the backlight module 19 as light emitting source.Backlight module 19 includes light source, leads Body of light, reflecting plate, diffusion sheet and visual angle trimmer.Light source can be enumerated, electroluminescent, cold-cathode tube, thermionic-cathode tube, light-emitting diodes Pipe (LED), laser light source and mercury lamp etc..In addition, the type of this polarizer can be selected according to the characteristic of these light sources.

When this liquid crystal display device 10 is transmissive liquid crystal display device, issued from the light source in backlight module 19 white Coloured light injects light guide, after changing incident light walking route by reflecting plate, is diffused by diffusion sheet.Diffusion light passes through visual angle Trimmer is adjusted to after having desired directive property, injects polarizer 12b by backlight module 19.

Among the incident light of no polarization, only a certain rectilinearly polarized light penetrates the polarizer 12b of liquid crystal display panel.The straight line Polarised light is converted to circularly polarized light or Elliptical circularly polarized light, successively penetrates substrate 14b, pixel electrode 22 by phase separation layer 13b Deng arrival liquid crystal layer 17.

Herein, according to the liquid whether there is or not potential difference, contained in liquid crystal layer 17 between pixel electrode 22 and opposite transparent electrode 16 The state of orientation of brilliant molecule starts to change, and then controls the brightness of the light projected from this liquid crystal display device 10.When liquid crystal layer 17 For directly make polarised light penetrate state of orientation when, the polarised light penetrate liquid crystal layer 17, transparent electrode 16, certain particular range of wavelengths Light reach polarizer 12a through colored filter 15, further by antireflection film 11, liquid crystal display device is shown most The bright color determined by colored filter.

On the contrary, when liquid crystal layer 17 is that switchable polarisation light is allowed to the state of orientation penetrated again, through liquid crystal layer 17, transparent electricity The light of pole 16 and colored filter 15 is polarized device 12a absorption.The pixel is shown as black as a result,.If this 2 states Intermediate orientation state, then the brightness of the light projected from this liquid crystal display device 10 is also among the two, therefore the pixel It is shown as Neutral colour.

When this liquid crystal display device 10 be transflective liquid crystal display device when, it is preferable to use this polarizer polarised light Layer is further laminated with this polarizer obtained from 1/4 wavelength plate on side.At this point, pixel electrode 22 has by transparent material shape At through portion, and the reflecting part formed by the material of reflected light, through portion is the same as above-mentioned transmissive liquid crystal display device, display figure Picture.On the other hand, in reflecting part, ambient light injects liquid crystal display device from the direction of antireflection film 11, by this polarizer into The effect for 1/4 wavelength plate that one step has passes through liquid crystal layer 17 through the circularly polarized light of this polarizer, anti-via pixel electrode 22 It penetrates, to be utilized in display.

Then, referring to Fig. 5, to embedded suitable liquid crystal display device (this liquid crystal display dress for using this polarizer 1 It sets and 24) is illustrated.

This liquid crystal display device 24, by antireflection film 11, substrate 14a, polarizer 12a, phase difference film 13a, colorized optical filtering Piece 15 and black matrix" 20, transparent electrode 16, liquid crystal layer 17, pixel electrode 22, interlayer dielectric 18 and thin film transistor (TFT) 21, phase Lamination forms in sequence for potential difference film 13b, polarizer b, substrate 14b and backlight module 19, it is preferable to use this rises in this composition Inclined device 1 is used as polarizer 12a.In this composition, this polarizer take from 11 side of antireflection film by transparent substrate 2, oriented layer 3, partially Setting made of vibration photosphere 4 and protective layer 7 configure in order.The composition being related to by this, has this liquid crystal of this polarizer Showing device 24 imparts the function that incident light is changed into rectilinearly polarized light.In addition, it is identical as this liquid crystal display device 10, according to The type of the liquid-crystal compounds contained in liquid crystal layer 17 can not also configure phase separation layer 13a and 13b.

Then, referring to Fig. 6 and Fig. 7, this EL display device for using this polarizer is illustrated.

EL display device 30 is organic function layer of the lamination as light emitting source on the substrate 33 for being formed with pixel electrode 35 36 and cathode electrode 37 and be made.Phase plate 32 and polarization plate 31 are configured to, and hold substrate with organic function layer 36 33, this polarizer 1 is used as the polarization plate 31 being related to positioned at the side opposite with organic function layer 36.By in pixel Electrode 35 applies positive voltage, and cathode electrode 37 applies negative voltage, the applying direct current between pixel electrode 35 and cathode electrode 37 Stream, organic function layer 36 shine.As the organic function layer 36 of light emitting source, by electron supplying layer, luminescent layer and hole transporting layer Deng composition.From organic function layer 36 project light, by pixel electrode 35, interlayer dielectric 34, substrate 33, phase plate 32 with And the polarizer 31 (this polarizer 1).Though the organic EL display device with organic function layer 36 is illustrated, but it is also suitable for Inorganic EL display device with inorganic functional layer.

When manufacturing this EL display device 30, firstly, forming the thin film transistor (TFT) 40 of intended shape on substrate 33.Then Interlayer dielectric 34 is formed, film, that is, pixel electrode 35 is then formed with sputtering method, forms pattern.Later, lamination organic function layer 36。

Then, in the opposing face in the face of the setting thin film transistor (TFT) 40 of substrate 33, it is arranged the polarizer 31 (this polarizer 1). It is preferred that phase separation layer 32 is arranged between the polarizer 31 and substrate 33, the more preferable phase separation layer 32 is made of 1/4 wavelength plate.It wants Phase separation layer 32 is set, prepares the laminate 45 as made of the polarizer 31 (this polarizer 1) and 32 lamination of phase separation layer in advance, it will The laminate 45 fits on substrate 33.It is schematically shown in Fig. 5 using the manufacturing method of the laminate 45.

When this polarizer 1 is used for the polarizer 31, its laminated order is not particularly limited.With virtual coil in reference Fig. 4 The enlarged drawing of C portion out is described.Fig. 8 is the section enlarged diagram of the C portion in Fig. 6.In (C1) of Fig. 8, When using this polarizer 1 as the polarizer 31, it is shown that configuring in order transparent substrate 2, oriented layer from 32 side of phase separation layer 3, photosphere 4 and protective layer 7 are polarized this polarizer 1 is arranged.In addition, (A2) of Fig. 8 is shown from 32 side of phase separation layer, successively Configuration protective layer 7 polarizes photosphere 4, oriented layer 3 and transparent substrate 2 this polarizer 1 is arranged.

Then, the component other than this polarizer of this EL display device is briefly described.

Substrate 33 can be enumerated, sapphire glass substrate, quartz glass substrate, sodium (ソーダ) glass substrate and aluminium oxide etc. Ceramic substrate；The metal substrates such as copper；Plastic base etc..

Though figure is not shown, heat conductivity film can be formed on substrate 33.Heat conductivity film can be enumerated, DLC film (DLC etc.) etc..When pixel electrode 35 is reflection-type, light is projected from the direction opposite with substrate 33.Therefore, it is not only transparent material Material, it is possible to use the non-transparent materials such as stainless steel.Substrate can take single form, can also take and be bonded multiple substrates with cement It is made the form of laminated substrate.In addition, these substrates are not limited to plate, it can also be film.

As thin film transistor (TFT) 40, such as use polysilicon transistors etc..Thin film transistor (TFT) 40 is set to pixel electricity The end of pole 35, substantially 10~30 μm of size.In addition, the size of pixel electrode 35 20 μm~300 μ m of substantially 20 μ m 300μm。

On substrate 33, it is provided with the link electrode of thin film transistor (TFT) 40.The resistance of link electrode is low, has and pixel electricity Pole 35 is electrically connected, and resistance value is inhibited the function in low value, and generally, which, which uses, contains Al, Al and transition metal Any one kind or two or more object in (but not including Ti), Ti or titanium nitride (TiN).

Interlayer dielectric 34 is provided between thin film transistor (TFT) 40 and pixel electrode 35.Interlayer dielectric 34 can be down Any one for stating film, by SiO₂The film that the inorganic based materials such as equal silica, silicon nitride are formed by sputtering or vacuum evaporation；With SOG(スピン·オン·グラス：Spin-on-glass) formed silicon oxide layer, photoresist, polyimides and acrylic acid Resins based material film such as resin etc. has the film of insulating properties.

On interlayer dielectric 34, frame glue 41 is formed.Frame glue 41 is configured at the edge (adjacent pixels of pixel electrode 35 Between).The material of frame glue 41 can be enumerated, acrylic resin and polyimide resin etc..Preferably 1.0 μm or more of the thickness of frame glue 41 3.5 μm hereinafter, more preferable 1.5 μm or more 2.5 μm or less.

Then, to by the pixel electrode 35 as transparent electrode, the organic function layer 36 as light emitting source, cathode electrode 37 The EL element of composition is illustrated.Organic function layer 36 is at least each 1 layer in hole transporting layer and luminescent layer, for example, pressing Sequence has electron injection transfer layer, luminescent layer, hole transporting layer and hole injection layer.

Pixel electrode 35 can be enumerated, such as ITO (tin-doped indium oxide), IZO (mixing zinc indium oxide), IGZO, ZnO, SnO₂And In₂O₃Deng particularly preferred ITO or IZO.As long as the thickness of pixel electrode 35 have can sufficiently carry out hole injection it is certain with On thickness, preferably approximately 10~500nm.

Pixel electrode 35 can be formed by vapor deposition (preferably sputtering method).Sputter gas is not particularly limited, using Ar, He, Ne, The inert gases such as Kr and Xe or their mixed gas.

As the constituent material of cathode electrode 37, can be used such as K, Li, Na, Mg, La, Ce, Ca, Sr, Ba, Al, Ag, The metallic elements such as In, Sn, Zn and Zr, but the job stability in view of improving electrode is, it is preferable to use selected from metallic element is illustrated 2 kinds of ingredients or 3 kinds of ingredients alloy body.Alloy body preferably such as AgMg (Ag：1~20at%), AlLi (Li：0.3~ 14at%), InMg (Mg：50~80at%) and AlCa (Ca：5~20at%) etc..

Cathode electrode 37 can be formed by vapor deposition and sputtering method etc..It is preferred that the thickness of cathode electrode 37 is in 0.1nm or more, it is excellent Select 1~500nm or more.

Hole injection layer has and makes to inject easy function from the hole of pixel electrode 35, and hole transporting layer has conveying empty Cave and the function of interfering electronics, also referred to as electric charge injection layer and charge transport layer.

The thickness of the thickness of luminescent layer, the overall thickness of hole injection layer and hole transporting layer and electron injection transfer layer without It is particularly limited to, it is different because of forming method difference, it is preferably made the thickness of substantially 5~100nm.Hole injection layer or hole transporting layer In, it is possible to use various organic compounds.When forming hole injection transfer layer, luminescent layer and electron injection transfer layer, it is based on Homogeneous film this point can be formed, vacuum vapour deposition can be used.

It as the organic function layer 36 of light emitting source, can be used, utilize the material from singlet exciton luminous (fluorescence) Material, using from Triplet exciton (phosphorescence) material, containing shining (fluorescence) using from singlet exciton Material and using from Triplet exciton (phosphorescence) material material, formed by organic matter material, containing by having The material of material and the material formed by inorganic matter that machine object is formed, low molecule material, contains high molecular material at high molecular material With the material of low molecule material etc..Wherein, without being limited thereto, use organic function of the well known a variety of materials as EL element Ergosphere 36 can be applied to this EL display device 30.

Desiccant 38 is configured between cathode electrode 37 and the space of cap 39.This is because organic function layer 36 intolerant to Humidity.Moisture is absorbed by desiccant 38, prevents the deterioration of organic function layer 36.

Fig. 9 is the skeleton diagram for indicating the section constitution of another way of this EL display device 30.This EL display device 30 With the encapsulating structure for using thin-film package film 42, emergent light can also be obtained from the opposing face of array substrate.

As thin-film package film 42, it is preferable to use being vapor-deposited with the DLC of DLC (diamond-like-carbon) on electrolytic capacitor film Film.The characteristic that DLC film has moisture permeable excessively poor, moisture-proof characteristic are high.In addition, DLC film etc. can also be directly deposited in 37 surface of cathode electrode and formed.In addition, can also multilayer lamination resin film and metallic film, formed thin-film package film 42.

As described above, providing one kind novel polarizer (this polarizer) of the present invention and having the novel of this polarizer Display device (this liquid crystal display device and this EL display device).

Finally the projection type liquid crystal display apparatus for using this polarizer 1 is illustrated.

Figure 10 is the skeleton diagram for showing the projection type liquid crystal display apparatus using this polarizer 1.

As the polarization film 142 and/or polarization film 143 of the projection type liquid crystal display apparatus, this polarizer 1 is used.

The light shafts projected from the light source (such as high-pressure sodium lamp) 111 as light emitting source, pass through the 1st lens array first 112, the 2nd lens array 113, polarization light conversion element 114, compound lens 115, it is thus that the brightness of reflective strand cross-sectional is uniform Change, polarize photochemical.

Specifically, the light shafts projected from light source 111, are formed as the 1st rectangular lens array via micro lens 112a Column 112 are divided into the small light shafts of multi beam.The 2nd lens array 113 and compound lens 115 are configured, so that divided light Beam can the entirety respectively to 3 liquid crystal display panels 140R, 140G, 140B as lighting object be irradiated, each liquid crystal surface as a result, The surface of plate incident side can integrally obtain uniform illumination.

Polarization light conversion element 114 is made of polarization beam apparatus array, is configured at the 2nd lens array 113 and compound lens Between 115.The random polarised light in light source can be converted to the polarised light with specific polarization light direction as a result, in advance, had The effect for reducing the light loss in the aftermentioned incident side polarizer, improving picture brightness.

As described above, brightness is homogenized and is polarized photochemical light, via reflecting mirror 122, pass sequentially through for dividing From for the trichromatic dichronic mirror 121,123,132 of RGB, it is separated into red channel, green channel, blue channel, injects liquid crystal surface respectively Plate 140R, 140G, 140B.

In liquid crystal display panel 140R, 140G, 140B, the polarizer 142 of the invention, exiting side are configured in its incident side respectively Configured with the polarizer 143 of the invention.

It is configured at the polarizer 142 and the polarizer 143 of each optical path of RGB, makes respective absorption axiss are orthogonal to be configured.Configuration In each liquid crystal display panel 140R, 140G, 140B of each optical path, has and turn the polarized light state for controlling each pixel according to picture signal It is changed to the function of light quantity.

This polarizer 1 is suitable for the type of the dichroism pigment in corresponding channel by selection, can be usefully as blue logical The excellent polarization film of durability in road, green channel and each optical path in red channel.

According to the image data of liquid crystal display panel 140R, 140G, 140B, incident light is made with different transmitances for each pixel Through the optical imagery being thus made is synthesized via cross colour splitting prism 150, passes through projecting lens 170, enlarging projection to projection On screen 180.

Electronic Paper can be enumerated, and be orientated the device that such molecule is shown by optical anisotropy and dye molecule； Pass through electrophoresis, the device shown by particle that particle is mobile, crystal grain rotates (particle returns translocation), phase change etc；Pass through The device that one end of film is moved to be shown；The device shown by color development/phase change of molecule；Pass through molecule The device that is shown of light absorption；The device etc. for generating self-luminous in conjunction with hole by electronics to be indicated.More specifically Ground can enumerate microcapsule-type electrophoresis, horizontal motion electrophoresis, vertically-moving electrophoresis, spherical twist ball type, magnetic twisting ball Type, cylinder twist ball type, charged toner, electronics powder fluid, magnetic flowing type, magnetic heat seeking, electrowetting, light scattering (it is transparent/ Gonorrhoea variation), cholesteric liquid crystal/optical conductive layer, cholesteric liquid crystal, bistability nematic liquid crystal, lure electrical liquid crystal, dichroism color by force Plain dispersed liquid crystal type, movable film, according to the colour changing of leuco dye, photochromic, electrochromism, electro-deposition, flexible organic EL Deng.Electronic Paper can be applied not only to the personal use of text or image, applies also for advertisement and shows (label) etc..According to this hair Bright optical film can reduce the thickness of Electronic Paper.

As 3 d display device, it is thus proposed that for example microelectrode (マイ Network ロポー Le) style is poor by out of phase The alternately arranged method of film (Japanese Patent Laid-Open 2002-185983 bulletin), but using optical film of the invention as polarised light Film in use, be readily formed pattern since printing, ink-jet, photoetching etc. can be passed through, therefore the manufacturing process of display device can be shortened, And phase difference film is not needed.

Embodiment

Hereinafter, by embodiment, the present invention will be described in more detail." % " and " portion " in example is as long as no special Illustrate, is exactly quality % and mass parts.

In the present embodiment, using following polymerizable liquid crystal compounds.

Compound (1-6) (following formula (1-6) compound represented)

Compound (1-6) uses Lub et al.Recl.Trav.Chim.Pays-Bas, 115,321-328 (1996) note The method of load is synthesized.

(measurement of phase transition temperature)

For the phase transition temperature of compound (1-6), by the phase transition temperature for finding out the film being made of compound (1-6) Confirmed.Its operation is as follows.

The film being made of compound (1-6) is formed on the glass substrate for be formed with alignment films, side heating, side uses polarization Light microscope confirms phase transition temperature by observation structure (テ Network スチャー).The film heating being made of compound (1-6) To after 120 DEG C, in temperature-fall period, confirming at 112 DEG C phase transition is nematic phase, and phase transition is smectic C at 110 DEG C, 94 Phase transition is carried out to smectic B at DEG C.

Compound (1-7) (following formula (1-7) compound represented)

Above compound (1-6) synthesis of the synthesized reference of compound (1-7).

(phase transition Wen Du Measuring is fixed)

In the same manner as the measurement of the phase transition temperature of compound (1-6), the phase transition temperature of compound (1-7) is confirmed.Chemical combination After object (1-7) is warming up to 140 DEG C, in temperature-fall period, confirming phase transfer at 133 DEG C is nematic phase, and phase transition is at 118 DEG C Smectic C carries out phase transition to smectic B at 78 DEG C.

Embodiment 1

(polarization photosphere forms the modulation for using composition)

Following compositions are mixed, by being stirred 1 hour at 80 DEG C, polarization photosphere formation is obtained and uses composition.

Polymerizable liquid crystal compound：50 parts of compound (1-6)

50 parts of compound (1-7)

Dichroism pigment：Azopigment (NKX2029；Woods protobiochemistry research is made) 2.5 parts

Polymerization initiator：

2- methylamino -2- benzyl -1- (4- morpholino base phenyl) 1- butanone

(イルガキュア369；チバスペシャ Le ティケミカ Le ズ society system) 6 parts

Levelling agent：Polyacrylic acid ester compounds (BYK-361N；BYK-Chemie society system) 1.2 parts

Solvent：250 parts of ring valeric acid

(measurement of phase transition temperature)

In the same manner as compound (1-6) and compound (1-7), finds out polarization photosphere made of as above modulation and formed with combination The phase transition temperature of polymerizable liquid crystal compound contained by object.After the polymerizable liquid crystal compound is warming up to 120 DEG C, cooling down Cheng Zhong, confirming at 112 DEG C phase transfer is nematic phase, and phase transition is smectic C at 104 DEG C, carries out phase to smectic B at 78 DEG C Transformation.

(manufacture and evaluation of this polarizer)

1. the formation of oriented layer

Transparent substrate uses glass substrate.

By spin-coating method, pva coating (the fully saponified type of polyvinyl alcohol 1000 and the pure medicine of light on the glass substrate Industrial Co., Ltd System) 2 mass % aqueous solutions (oriented layer formed use composition), after dry, formed with a thickness of 100nm's Film.Then, friction treatment is implemented by the surface to obtained film, forms oriented layer.About friction treatment, rubbed using semi-automatic Wipe device (trade name：LQ-008 type, Joyo Engineering Co., Ltd.'s system), with cloth (trade name：YA-20-RW, lucky river chemical industry strain formula Commercial firm's system), it is carried out under conditions of intrusion 0.15mm, revolving speed 500rpm, 16.7mm/s.By related friction treatment, Obtain the laminate 1 for forming oriented layer on the glass substrate.

2. polarizing the formation of photosphere

By spin-coating method, the polarization photosphere formation is coated in the oriented layer of laminate 1 with composition, at 120 DEG C Electric furnace on after heat drying 3 minutes, be cooled to 70 DEG C (temperature of shown smectic phase when cooling) immediately hereinafter, in institute State the 1st dry coationg of formation in oriented layer.In related 1st dry coationg, contained by polymerizable liquid crystal compound Mesomorphic state is smectic B.Then, using UV irradiation unit (SPOT CURE SP-7；ウシオ Electric Co., Ltd system), Light exposure 2400mJ/cm²Under conditions of (365nm benchmark), ultraviolet light irradiation is carried out to the 1st dry coationg, is keeping described poly- In the case where the mesomorphic state of conjunction property liquid-crystal composition, it polymerize polymerizable liquid crystal compound contained by the 1st dry coationg, by 1st dry coationg forms polarization photosphere, obtains laminate 2.With laser microscope (society of オリ Application パス Co., Ltd. system OLS3000 polarization photosphere at this time) is measured, result is 1.8 μm.

3.X ray diffraction determination

X-ray diffraction device X ' Pert PRO MPD (スペ Network トリス Co. Ltd. system) is used to the laminate 2 of acquisition Carry out X-ray diffraction measure.Cu will be used to produce as target, under conditions of x-ray tube current 40mA, x-ray tube voltage 45kV Raw x-ray passes through 1/2 ° of fixed divergent slit and (finds out the friction for the oriented layer being present under polarization photosphere in advance along frictional direction Direction) it is incident, it is scanned with the range of 2 θ=4.0~40.0 ° of scanning range, 2 θ=0.01671 ° of step width, the result of measurement It is that the sharp diffraction maximum (bragg peak) of half-peak breadth (FWHM)=about 0.187 ° is nearby obtained in 2 θ=20.22 °.In addition, Identical result has also been obtained from perpendicular to frictional direction incidence.It is asked to obtain lattice period (order period) (d) by the position at peak AboutIt knows to form the structure for reflecting high dimension smectic phase.

4. manufacturing this polarizer by forming protective layer

By dipentaerythritol hexaacrylate (アロニッ Network ス M-403 Toagosei Co., Ltd system, multifunctional propylene Acid esters) 50 parts, 50 parts of acrylate (4858 ダイセルユーシービー Co. Ltd. system of エベ Network リ Le), 2- first [4- (methyl mercapto) the phenyl] -2- morpholino base -1- of base -1 acetone (イ Le ガキュア 907；チバスペシャルティケミカ Le ズ She System) 3 parts be dissolved in 250 parts of isopropanol and obtain solution (protective layer is formed with composition), by spin-coating method, by the solution It is coated on the polarization photosphere of laminate 2, on 50 DEG C of electric furnace after heat drying 1 minute, uses UV irradiation unit (SPOT CURE SP-7；ウシオ Electric Co., Ltd system), in light exposure 400mJ/cm²Under conditions of (365nm benchmark), it is carried out Irradiation, by forming protective layer on the polarization photosphere, manufactures this polarizer (hereinafter referred to as this polarizer A.).It is aobvious with laser Micro mirror (オリ Application パス Co., Ltd. society OLS3000) is measured protective layer at this time, and result is 2.8 μm.

5. the measurement of dichroic ratio

Use the bracket that the subsidiary polarizer is provided on spectrophotometer (Shimadzu Corporation UV-3150) Device, by dijection collimation method measure maximum absorption wavelength in the absorbance (A for penetrating axis direction¹) and absorb axis direction extinction Spend (A²).The reference side of the bracket is provided with the mesh screen (メッシュ) of light quantity reduction 50%.From the axis direction of penetrating of measurement Absorbance (A¹) and absorb axis direction absorbance (A²) value, calculate ratio (A²/A¹), as dichroic ratio.It the results are shown in Table.Two Color ratio is higher, more useful as polarization photosphere.The measurement result of dichroic ratio is shown in Table 1.

Embodiment 2

By dichroism pigment from azopigment (NKX2029：Woods protobiochemistry research is made) it is changed to azopigment (G205：Woods protobiochemistry research is made), in addition to this, tested in the same manner as in Example 1, manufacture this polarizer (with Under, referred to as " this polarizer B ".For the phase transition course of polymerizable liquid crystal compound at this time, confirmation is to be warming up to 120 DEG C Afterwards, in temperature-fall period, phase transfer is nematic phase at 112 DEG C, and phase transition is smectic C at 105 DEG C, to smectic B at 77 DEG C Carry out phase transition.The dichroic ratio measurement result of this obtained polarizer is shown in Table 1.

Embodiment 3

Solvent contained by protective layer formation composition is changed to ethyl alcohol from isopropanol, in addition to this, in the same manner as in Example 1 Ground is tested, this polarizer (hereinafter referred to as " this polarizer C ") is manufactured.The dichroic ratio measurement result of the polarizer of production is shown in In table 1.

Embodiment 4

Solvent contained by protective layer formation composition is changed to propylene glycol monomethyl ether from isopropanol, except this it Outside, it is tested in the same manner as in Example 1, manufactures this polarizer (hereinafter referred to as " this polarizer D ").The two of the polarizer of production Color ratio measurement result is shown in Table 1.

Embodiment 5

Solvent contained by protective layer formation composition is changed to propylene glycol monomethyl ether from isopropanol, in addition to this, with Embodiment 1 is equally tested, this polarizer (hereinafter referred to as " this polarizer E ") is manufactured.The dichroic ratio of the polarizer of production Measurement result is shown in Table 1.

Embodiment 6

Via the adhesive layer that pressure sensitive adhesive (PSA) is formed, TAC (triacetyl cellulose) film is bonded in embodiment 1 On the protective layer of obtained this polarizer A.By the dichroic ratio of the obtained structural body (hereinafter referred to as " this polarizer A+TAC ") Measurement result is shown in Table 1.

Embodiment 7

Via the adhesive layer that pressure sensitive adhesive (PSA) is formed, TAC (triacetyl cellulose) film is bonded in embodiment 2 On the protective layer of obtained this polarizer B.By the dichroic ratio of the obtained structural body (hereinafter referred to as " this polarizer B+TAC ") Measurement result is shown in Table 1.

Embodiment 8

By implementing sided corona treatment on the polarization photosphere made in the same manner as in Example 1, makes its surface activation, use spin coating 10 mass % of method pva coating (the fully saponified type of polyvinyl alcohol 1000 and Guang Chun medicine Industrial Co., Ltd system) on it Aqueous solution forms protective layer on the polarization photosphere in heat drying 1 minute on 80 DEG C of electric furnace, and it is (following to manufacture this polarizer Referred to as " this polarizer F ").The dichroic ratio measurement result of the polarizer of production is shown in Table 1.

Embodiment 9

By implementing sided corona treatment on the polarization photosphere made in the same manner as in Example 1, makes its surface activation, use spin coating Method is coated with solution (UCECOAT7655, ダイセ Le for being dispersed with aliphatic urethane acrylate on it サイテックZhu Shihui society System), in heat drying 1 minute on 60 DEG C of electric furnace, protective layer is formed on the polarization photosphere, is made Make this polarizer (hereinafter referred to as " this polarizer G ").The dichroic ratio measurement result of the polarizer of production is shown in Table 1.

Embodiment 10

Via the adhesive layer that pressure sensitive adhesive (PSA) is formed, TAC (triacetyl cellulose) film is bonded in embodiment 8 On the protective layer of obtained this polarizer F.By the dichroic ratio of the obtained structural body (hereinafter referred to as " this polarizer F+TAC ") Measurement result is shown in Table 1.

Embodiment 11

Via the adhesive layer that pressure sensitive adhesive (PSA) is formed, TAC (triacetyl cellulose) film is bonded in embodiment 9 On the protective layer of obtained this polarizer G.By the dichroic ratio of the obtained structural body (hereinafter referred to as " this polarizer G+TAC ") Measurement result is shown in Table 1.

Table 1

(※)

IPA：Isopropanol

ETA：Ethyl alcohol

PGMEA：Propylene glycol monomethyl ether

PGME：Propylene glycol monomethyl ether

Evaluate example

1. durability test

As the durability test of this polarizer, ongoing change test below is carried out.

Structural body (this polarizer A+ that this polarizer and embodiment 6~7,10 that Examples 1 to 2 is obtained obtain TAC, this polarizer B+TAC or this polarizer F+TAC) investment Hitachi's thermostat (trade name：EC-15HHP, Co., Ltd. day Li Kong Tone システ system system) [condition：60 DEG C of humidity 90%RH of dry-bulb temperature or 85 DEG C of humidity 0%], measurement is passed through 100 hours Absorbance afterwards, finds out dichroic ratio.So using dichroic ratio after 100 hours, is measured again, judgement is divided into two ranks, will be first The case where dichroic ratio of phase is determined as " g " (good, good) with the substantially unconverted situation of dichroic ratio after lasting, deterioration determines For " b " (bad, bad).As a result it is shown in table 2.

Table 2

2. solvent-resistance test

This polarizer is used in liquid crystal cell, that is, when being used in the liquid crystal display device of inline mode, needs originally be polarized PI (polyimides) alignment films are set on the protective layer of device.NMP (N- methyl-is used most of when forming PI alignment films formation 2-Pyrrolidone) solution.It is, requiring this polarizer that there is solvent resistance for NMP.Therefore, by NMP drop in these protections It in layer surface, is kept for 5 minutes, is then wiped, whether evaluation protective layer dissolves.Evaluation result is divided into two ranks and is determined, The case where being dissolved without discovery by NMP, is determined as " g " (good), finds to be determined as " b " (bad) the case where dissolution by NMP.Knot Fruit is shown in table 3.

【Table 3】

	Measure object	Determine
			Evaluate example 6	This polarizer A	g
Evaluate example 7	This polarizer B	g
			Evaluate example 8	This polarizer F	g

Industrial availability

The polarizer of the invention is in manufacture liquid crystal display device, (organic) EL display device and projection type liquid crystal display apparatus Aspect is exceedingly useful.

Claims

1. a kind of polarizer is formed by setting gradually oriented layer, polarization photosphere and protective layer over the transparent substrate,

The polarization photosphere is fabricated by manufacturing method with the following process：

The process that film is formed by the composition containing polymerizable liquid crystal compound, dichroism pigment, polymerization initiator and solvent；

The process of the solvent is removed from the film；

Make to eliminate process of the polymerizable liquid crystal compound contained in the film of the solvent as smectic liquid crystal state；With

2. the polarizer as described in claim 1, the polarization photosphere is to obtain the inclined of bragg peak in X-ray diffraction measure Shake photosphere.

3. the polarizer as described in claim 1 or 2, range of the thickness of the polarization photosphere at 0.5~3 μm.

4. the polarizer according to any one of claims 1 to 3, the dichroism pigment is azopigment.

5. the polarizer as described in any one of claims 1 to 4, the polymerizable liquid crystal compound contains two or more gather Conjunction property smectic liquid crystal compound.

6. such as the polarizer according to any one of claims 1 to 5, the protective layer is by containing polyfunctional acrylic ester and molten The layer that the protecting layer compositions of agent are formed, the solvent are actually made of alcoholic solvent and/or ether solvents.

7. such as the polarizer according to any one of claims 1 to 5, the protective layer is formed by protective layer formation with composition, The protective layer formation contains the polymer or oligomer and water that polyfunctional acrylic ester polymerize with composition.

8. the protective layer is by the guarantor containing water-soluble polymer and water such as the polarizer according to any one of claims 1 to 5 Sheath formation is formed with composition.

9. a kind of liquid crystal display device has the polarizer according to any one of claims 1 to 8.

10. liquid crystal display device as claimed in claim 9, the polarizer is configured inside liquid crystal cell.

11. a kind of circular polarization light board is arranged 1/4 on the protective layer of the polarizer according to any one of claims 1 to 8 Wavelength plate.

12. circular polarization light board as claimed in claim 11,1/4 wavelength plate is that have for phase difference in the face of visible light Value shortens and the wavelength plate of reduced characteristic with wavelength.

13. a kind of organic EL display device has circular polarization light board described in claim 11 or 12 and organic EL element.

14. a kind of manufacturing method of the polarizer, has：

Process (2), in the oriented layer of the laminated board coating containing polymerizable liquid crystal compound, dichroism pigment and The composition of polymerization initiator, to form the 1st coated film in the oriented layer；

Process (3) under conditions of the polymerizable liquid crystal compound contained by the 1st coated film will not polymerize, makes the work The 1st coated film formed in sequence (2) is dry, forms the 1st dry coationg, makes the polymerism liquid in the 1st dry coationg After brilliant compound becomes smectic liquid crystal state, in the case where keeping the smectic liquid crystal state, make the polymerizable liquid crystal compound Polymerization, to form polarization photosphere by the 1st dry coationg；With

Process (4), coating contains polyfunctional acrylic ester and solvent on the polarization photosphere formed in the process (3) Protective layer, which is formed, uses composition, forms the 2nd coated film on the polarization photosphere, makes described multifunctional contained by the 2nd coated film Acrylic ester polymerization, to form protective layer by the 2nd coated film.

15. the manufacturing method of the polarizer as claimed in claim 14, it is real that the protective layer forms the solvent contained by composition It is made of in matter alcoholic solvent or/and ether solvents.

16. a kind of manufacturing method of the polarizer, has：

Process (3) under conditions of the polymerizable liquid crystal compound contained in the 1st coated film will not polymerize, makes described The 1st coated film formed in process (2) is dry, forms the 1st dry coationg, makes the polymerism in the 1st dry coationg After liquid-crystal compounds becomes smectic liquid crystal state, in the case where keeping the smectic liquid crystal state, make the polymerizable liquid crystal chemical combination Object polymerization, to form polarization photosphere by the 1st dry coationg；With

Process (4), coat protective layer forms and uses composition on the polarization photosphere of formation in the process (3), and at this It polarizes and forms the 2nd coated film on photosphere, it is dry by making the 2nd coated film, so that protective layer is formed by the 2nd coated film, it should Protective layer formation contains the polymer or oligomer and water that polyfunctional acrylic ester polymerize with composition.

17. a kind of manufacturing method of the polarizer, has：

Process (4) is coated with the protection containing water-soluble polymer and water in the process (3) on the polarization photosphere of formation Layer, which is formed, uses composition, and the 2nd coated film is formed on the polarization photosphere, keeps the 2nd coated film dry, to be applied by the 2nd Cloth film forms protective layer.

18. a kind of polarizer, the manufacturing method as described in any one of claim 14~17 is fabricated.