TWI585472B - A polarizing film forming composition, and a polarizing film - Google Patents

Description

Polarizing film forming composition and polarizing film

The present invention relates to a composition for forming a polarizing film, a polarizing film produced by the composition for forming a polarizing film, a method for producing the same, and the like.

In recent years, liquid crystal display devices have been strongly required to be thinned, and as a result, the polarizers used in the liquid crystal display devices are also required to be thinner. In order to realize a thinner type of photo-polarizer, it has been studied to replace a film comprising iodine-dyed polyvinyl alcohol so far by a composition formed of a composition containing a polymerizable liquid crystal compound.

As a polarizing film formed of a composition containing a polymerizable liquid crystal compound, for example, Patent Document 1 discloses a polarized light composed only of a polymerizable smectic liquid crystal compound, a dichroic dye, a photopolymerization initiator, and an inhibitor. Further, Patent Document 2 discloses a polarizing film comprising only a polymerizable liquid crystal compound, a dichroic dye, a polymerization initiator, an inhibitor, a gelling agent, and a solvent.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 4719156

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2008-547062

However, it is further required to reduce the thickness and transparency of the polarizing film.

It is an object of the present invention to provide a thin and highly transparent fabric The polarizing film forming composition of the polarizing film and the polarizing film formed from the polarizing film forming composition.

The present invention provides the following invention.

[1] A composition for forming a polarizing film comprising a polymerizable liquid crystal compound, a polymerizable non-liquid crystal compound, a dichroic dye, a polymerization initiator, and a solvent, and satisfying the following requirements (A) and (B): (A) The polymerizable liquid crystal compound and the polymerizable non-liquid crystal compound all have a polymerizable group; (B) the polymerizable liquid crystal compound contained in the coating film obtained from the composition for forming a polarizing film does not form a phase separation state, and is displayed. The nematic liquid crystal phase and the smectic liquid crystal phase; (hereinafter, the necessary conditions of (A) and (B) are respectively referred to as "(required condition A)" and "(required condition B)").

[2] The composition for forming a polarizing film according to [1], wherein the polymerizable liquid crystal compound is a compound represented by the formula (1): U ¹ -V ¹ -W ¹ -X ¹ -Y ¹ -X ² -Y ² -X ³ -W ² -V ² -U ² (1)

(wherein X ¹ , X ² and X ³ each independently represent a 1,4-phenylene group which may have a substituent or a cyclohexane-1,4-diyl group which may have a substituent; wherein X ¹ , At least one of X ² and X ³ is a 1,4-phenylene group which may have a substituent; -CH ₂ - which constitutes a cyclohexane-1,4-diyl group may be -O-, -S- or -NR-substituted; R represents an alkyl group having 1 to 6 carbon atoms or a phenyl group; Y ¹ and Y ² independently of each other represent -CH ₂ CH ₂ -, -CH ₂ O-, -COO-, -OCOO-, single a bond, -N=N-, -CR ^a =CR ^b -, -C≡C- or -CR ^a =N-; R ^a and R ^b independently of each other represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; U ¹ represents a hydrogen atom or a polymerizable group; U ² represents a polymerizable group; and W ¹ and W ² each independently represent a single bond, -O-, -S-, -COO- or -OCOO-; V ¹ and V ² The alkanediyl group having 1 to 20 carbon atoms which may have a substituent is independently represented by each other, and -CH ₂ - constituting the alkanediyl group may be substituted by -O-, -S- or -NH-).

[3] The composition for forming a polarizing film according to [1] or [2] wherein the polymerizable non-liquid crystal compound is a monofunctional acrylate or a polyfunctional acrylate.

[4] The composition for forming a polarizing film according to any one of [1] to [3] wherein the polymerizable group of the polymerizable liquid crystal compound and the polymerizable group of the polymerizable non-liquid crystal compound are each independently Acryloxy (CH ₂ =CHCOO-) or methacryloxyl (CH ₂ =C(CH ₃ )COO-).

[5] The composition for forming a polarizing film according to any one of [1] to [4] wherein the polymerizable group of the polymerizable liquid crystal compound is the same as the polymerizable group of the polymerizable non-liquid crystal compound.

[6] The composition for forming a polarizing film according to any one of [1] to [5] wherein the polymerizable liquid crystal compound has 1 to 2 polymerizable groups in the molecule, and the polymerizable non-liquid crystal compound has 2 in the molecule. ~6 polymerizable groups.

The composition for forming a polarizing film according to any one of [1] to [6], wherein the content of the polymerizable non-liquid crystal compound is 3 parts by mass or more and 10 parts by mass based on 100 parts by mass of the polymerizable liquid crystal compound. the following.

[8] A method for producing a polarizing film, comprising the following steps (I), (II), and (III): (I) The composition for forming a polarizing film according to any one of [1] to [7] a step of coating a substrate or forming an alignment film on a substrate, removing the solvent to form a coating film; (II) a step of bringing the polymerizable liquid crystal compound contained in the coating film formed in (I) into a smectic liquid crystal phase; (III) the polymerizable liquid crystal compound formed in (II) is a smectic liquid crystal In the coating film of the phase state, a step of copolymerizing the polymerizable liquid crystal compound and the polymerizable non-liquid crystal compound.

[9] The method for producing a polarizing film according to [8], wherein the substrate is a transparent substrate on which an alignment treatment is performed.

[10] The method for producing a polarizing film according to [8] or [9], wherein the step (II) comprises the steps of the step (I-1) and the step (I-2), wherein the step (I-1) is carried out The heat treatment is carried out until the polymerizable liquid crystal compound contained in the coating film formed in the step (I) exhibits a nematic liquid crystal phase, and the above step (I-2) is the polymerizability formed in the step (I-1). The liquid crystal compound is cooled in a coating film in a nematic liquid crystal phase until the polymerizable liquid crystal compound exhibits a smectic liquid crystal phase.

[11] A polarizing film produced by the production method according to any one of [8] to [10].

[12] The polarizing film according to [11], which exhibits a Bragg peak in a diffraction measurement of X-rays.

[13] A display device comprising the polarizing film of [11] or [12].

According to the polarizing film-forming composition of the present invention, a thin and highly transparent polarizing film can be produced.

<Polarizing film forming composition>

The composition for forming a polarizing film of the present invention (hereinafter sometimes referred to as "the present combination" The material ") contains a polymerizable liquid crystal compound, a polymerizable non-liquid crystal compound, a dichroic dye, a polymerization initiator, and a solvent. A polarizing film (hereinafter sometimes referred to as "the present polarizing film") formed of the present composition by the following production method can produce a circular polarizing plate which is suitable not only for a liquid crystal display device but also for an organic EL display device (hereinafter, It is called "the circular polarizer". First, the present composition will be described.

<Polymeric liquid crystal compound>

The polymerizable liquid crystal compound of the present invention refers to a liquid crystal compound having a polymerizable group and having the following characteristics: a phase separation state is not formed in the coating film formed of the composition, and a nematic liquid crystal phase and a smectic liquid crystal are exhibited. phase.

Whether or not the coating film formed of the present composition is satisfied (Requirement B) can be confirmed, for example, in the following manner. The present composition is applied onto a glass substrate, and the applied composition is subjected to heat treatment and/or reduced pressure treatment under conditions in which the polymerizable liquid crystal compound and the polymerizable non-liquid crystal compound are not polymerized, thereby removing the solvent. Then, the coating film formed on the glass substrate was heated, and it was confirmed whether the polymerizable liquid crystal compound contained in the coating film did not form phase separation and exhibited a nematic liquid crystal phase. Then, the heated coating film was slowly cooled, and it was confirmed whether or not the polymerizable liquid crystal compound contained in the coating film showed no phase separation and showed a smectic liquid crystal phase. The confirmation of the nematic liquid crystal phase and the smectic liquid crystal phase can be performed, for example, by texture observation using a polarizing microscope, X-ray diffraction measurement, or differential scanning calorimetry. The confirmation of the formation of phase separation can be carried out, for example, by surface observation using various microscopes or by scattering measurement using a haze meter.

The stratified liquid crystal phase exhibited by the polymerizable liquid crystal compound is more preferably a high-order layer phase. Here, the high-order layer phase refers to the layer B phase, the smectic D phase, the smectic phase E phase, the smectic F phase, the smectic G phase, the smectic H phase, the smectic phase I phase, and the smectic phase J phase The smectic K phase and the smectic L phase, and more preferably the smectic B phase, the smectic F phase, and the smectic phase I phase. When the stratified liquid crystal phase exhibited by the polymerizable liquid crystal compound is the high-order smectic phase, the present polarizing film having a higher alignment degree can be produced. Further, in the X-ray diffraction measurement, the present polarizing film having a higher degree of alignment can be obtained from a hexagonal liquid phase (hexagonal liquid phase) or a Bragg peak having a crystal-equivalent higher order structure.

The polymerizable liquid crystal compound is preferably a compound having a phase transition from a nematic liquid crystal phase to a smectic liquid crystal phase of 40 to 200 ° C, more preferably a compound having a phase transition temperature of 60 to 140 ° C.

The compound represented by the formula (1) (hereinafter sometimes referred to as "compound (1)")) is exemplified as a preferred polymerizable liquid crystal compound.

U ¹ -V ¹ -W ¹ -X ¹ -Y ¹ -X ² -Y ² -X ³ -W ² -V ² -U ² (1)

[In the formula (1), X ¹ , X ² and X ³ each independently represent a 1,4-phenylene group which may have a substituent or a cyclohexane-1,4-diyl group which may have a substituent. Wherein at least one of X ¹ , X ² and X ³ is a 1,4-phenylene group which may have a substituent. The -CH ₂ - constituting the cyclohexane-1,4-diyl group may be substituted by -O-, -S- or -NR-. R represents an alkyl group having 1 to 6 carbon atoms or a phenyl group.

Y ¹ and Y ² independently of each other represent -CH ₂ CH ₂ -, -CH ₂ O-, -COO-, -OCOO-, a single bond, -N=N-, -CR ^a =CR ^b -, -C≡ C- or -CR ^a =N-. R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

U ¹ represents a hydrogen atom or a polymerizable group.

U ² represents a polymerizable group.

W ¹ and W ² independently of each other represent a single bond, -O-, -S-, -COO- or -OCOO-.

V ¹ and V ² independently of each other represent an alkanediyl group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - constituting the alkanediyl group may be substituted by -O-, -S- or -NH-].

In the compound (1), at least two of X ¹ , X ² and X ³ are preferably a 1,4-phenylene group which may have a substituent.

The 1,4-phenylene group which may have a substituent is preferably unsubstituted. The cyclohexane-1,4-diyl group which may have a substituent is preferably a trans-cyclohexane-1,4-diyl group which may have a substituent, and a trans-cyclohexane-1 which may have a substituent The 4-diyl group is preferably unsubstituted.

Examples of the substituent which the 1,4-phenylene group which may have a substituent or the cyclohexane-1,4-diyl which may have a substituent may have a carbon number such as a methyl group, an ethyl group or a butyl group. 1 to 4 alkyl groups, cyano groups, halogen atoms, and the like.

Y ^{1 of the} compound (1) is preferably -CH ₂ CH ₂ -, -COO- or a single bond, and Y ^{2 is} preferably -CH ₂ CH ₂ - or -CH ₂ O-.

U ² is a polymerizable group. U ¹ is a hydrogen atom or a polymerizable group, and is preferably a polymerizable group. U ¹ and U ^{2 are} preferably all polymerizable groups, and are preferably all photopolymerizable groups. Here, the photopolymerizable group refers to a group that receives energy of light and participates in polymerization. The polymerizable liquid crystal compound having a photopolymerizable group is advantageous in that it can be polymerized under lower temperature conditions. The photopolymerizable group is preferably a radical polymerizable group. The radical polymerizable group means a group which can participate in a polymerization reaction by an active radical generated from a polymerization initiator described below.

In the compound (1), the polymerizable groups of U ¹ and U ² may be different from each other, and are preferably the same. Examples of the polymerizable group include a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, an acryloxy group, a methacryloxy group, and an oxirane group. An oxypropylene group or the like. Among them, an acryloxy group, a methacryloxy group, and a vinyloxy group are preferred, and an acryloxy group and a methacryloxy group are more preferred.

Examples of the alkanediyl group of V ¹ and V ² include a methylene group, an ethylidene group, a propane-1,3-diyl group, a butane-1,3-diyl group, and a butane-1,4-diyl group. Pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, decane-1,10-diyl , tetradecane-1,14-diyl and eicosane-1,20-diyl and the like. V ¹ and V ^{2 are} preferably an alkanediyl group having 2 to 12 carbon atoms, more preferably an alkanediyl group having 6 to 12 carbon atoms.

Examples of the substituent which the alkanediyl group having 1 to 20 carbon atoms which may have a substituent has may be a cyano group or a halogen atom, and the alkanediyl group is preferably unsubstituted, more preferably unsubstituted and straight. Chain-like alkanediyl.

W ¹ and W ^{2 are} preferably each independently a single bond or -O-.

Specific examples of the compound (1) include compounds represented by the formulae (1-1) to (1-23), and the like. In the case where the specific example of the compound (1) has a cyclohexane-1,4-diyl group, the cyclohexane-1,4-diyl group is preferably a trans form.

The polymerizable liquid crystal compound can be used in the present composition alone or in combination of two or more. When two or more kinds are mixed, at least one of the compounds (1) is preferred, and two or more of the compounds (1) are more preferred. The mixing ratio in the case of mixing two kinds of polymerizable liquid crystal compounds is usually 1:99 to 50:50, preferably 5:95 to 50:50, more preferably 10:90 to 50:50.

The polymerization temperature of the present composition is usually not more than the smectic phase transition temperature of the polymerizable liquid crystal compound. The polymerization temperature of the present composition can be controlled by adjusting the components contained in the composition. It is preferred to determine the smectic phase transition temperature of the polymerizable liquid crystal compound in advance, and adjust the components other than the polymerizable liquid crystal compound to polymerize the composition at a temperature lower than the phase transition temperature. In the case where the composition contains two or more kinds of polymerizable liquid crystal compounds, the smectic phase transition temperature of the mixture of the two or more polymerizable liquid crystal compounds is determined and controlled in the same manner.

Among the compound (1) exemplified, preferred are the formula (1-2), the formula (1-3), the formula (1-4), the formula (1-6), the formula (1-7), and the formula (1). 1-8), a compound represented by the formula (1-13), the formula (1-14), and the formula (1-15). These compounds by other polymerizability The interaction between the liquid crystal compound or the polymerizable non-liquid crystal compound can be easily carried out under the temperature conditions of the smectic phase transition temperature or lower, that is, the liquid crystal state of the high-order layer phase is sufficiently maintained.

The content ratio of the polymerizable liquid crystal compound in the composition is usually 70 to 99.5 parts by mass, preferably 80 to 99 parts by mass, more preferably 80 to 94 parts by mass, per 100 parts by mass of the solid content component of the composition. Further, it is preferably 80 to 90 parts by mass. When the content ratio of the compound (1) is in the above range, the alignment of the following compound (2) tends to be high, and it is preferred. Here, the solid content component is a total amount of components obtained by removing the solvent from the composition.

The polymerizable liquid crystal compound can be produced, for example, by a known method described in Lub et al. Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996), or Japanese Patent No. 4719156.

<Polymeric non-liquid crystal compound>

The polymerizable non-liquid crystal compound of the present invention means a compound having a polymerizable group and having no liquid crystal state between a solid and a liquid even if the temperature changes.

The polymerizable non-liquid crystal compound preferably has (i) no coloration (absorption of visible light) by itself, (ii) compatibility with a degree of uniform mixing with the polymerizable liquid crystal compound, and (iii) does not interfere with the polymerizable liquid crystal. The formation of the liquid crystal state exhibited by the compound.

The polymerizable non-liquid crystal compound is exemplified by a monofunctional acrylate and a polyfunctional acrylate. The term "monofunctional" means having one polymerizable group, and the term "multifunctional" means having a plurality of polymerizable groups. Polymeric liquid crystal compound The polyfunctional acrylate is preferred from the viewpoint that the polymerization reaction of the polymerizable non-liquid crystal compound is continuously performed. The number of the polymerizable groups of the polymerizable non-liquid crystal compound is preferably from 1 to 6, more preferably from two to six.

The polymerizable group of the polymerizable non-liquid crystal compound is preferably the same as the polymerizable group of the polymerizable liquid crystal compound.

In addition, when at least one compound selected from the group consisting of a polymerizable liquid crystal compound and a polymerizable non-liquid crystal compound has a plurality of polymerizable groups, at least one polymerizable group and polymerization of the polymerizable liquid crystal compound are preferred. The at least one polymerizable group of the non-liquid crystal compound is the same.

The more preferable polymerizable non-liquid crystal compound is a single one having the characteristics of the above (i), (ii) and (iii) and having one to six, preferably two to six, polymerizable groups in the molecule. Functional acrylates and multifunctional acrylates. Further, since the monofunctional acrylate and the polyfunctional acrylate are non-liquid crystalline, they are preferably not provided with a liquid crystal original structure. Further, the urethane structure and the amine group may be contained in the molecule in a range that does not disturb the nematic liquid crystal phase and the smectic liquid crystal phase of the polymerizable liquid crystal compound contained in the coating film obtained from the composition. Structure, epoxy structure, ethylene glycol structure and polyester structure.

The polymerizable non-liquid crystal compound can be used in the present composition alone or in combination of two or more.

By monofunctional acrylate, it is meant that one molecule selected from the group consisting of acryloxy (CH ₂ =CH-COO-) and methacryloxy (CH ₂ =C(CH ₃ )-COO-) A compound in the group (hereinafter sometimes referred to as (meth) acryloxy). In the case where the polymerizable non-liquid crystal compound is a monofunctional acrylate, the polymerizable liquid crystal compound preferably has a (meth) acryloxy group.

Examples of the monofunctional acrylate having one (meth) propylene fluorenyloxy group include a (meth)acrylic acid alkyl ester having 4 to 16 carbon atoms and a (meth)acrylic acid-β-carbon having 2 to 14 carbon atoms. a carboxyalkyl ester, an alkylated phenyl (meth)acrylate having 2 to 14 carbon atoms, a methoxypolyethylene glycol (meth) acrylate, a phenoxy polyethylene glycol (meth) acrylate, and (meth)acrylic acid Ester and the like.

The polyfunctional acrylate generally means a compound having two to six (meth)acryloxy groups in the molecule. When the polymerizable non-liquid crystal compound is a polyfunctional acrylate, the polymerizable liquid crystal compound preferably further has a (meth) acryloxy group.

Examples of the bifunctional acrylate having two (meth)acryloxycarbonyl groups include 1,3-butanediol di(meth)acrylate and 1,3-butanediol (meth)acrylate. 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, Triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol diacrylate, bisphenol A bis(acryloxyethyl)ether, ethoxylate Bisphenol A di(meth)acrylate, propoxylated neopentyl glycol di(meth)acrylate, ethoxylated neopentyl glycol di(meth)acrylate and 3-methylpentane Alcohol di(meth)acrylate and the like.

Examples of the polyfunctional acrylate having 3 to 6 (meth)acryloxycarbonyl groups include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and tris(2- Hydroxyethyl)isocyanurate tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trihydroxyl Methylpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (meth) acrylate, Tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate; pentaerythritol tri (meth) acrylate and anhydride a reactant, a reaction of dipentaerythritol penta (meth) acrylate with an acid anhydride; a reaction of tripentaerythritol hepta (meth) acrylate with an acid anhydride; caprolactone modified trimethylolpropane tri(meth)acrylic acid Ester, caprolactone modified pentaerythritol tri(meth)acrylate, caprolactone modified tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, caprolactone modified pentaerythritol IV Methyl) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, caprolactone modified tripentaerythritol tetra (meth) acrylate , caprolactone modified tripentaerythritol penta (methyl) propyl Acid ester, caprolactone modified tripentaerythritol hexa(meth) acrylate, caprolactone modified tripentaerythritol hepta (meth) acrylate, caprolactone modified tripentaerythritol octa (meth) acrylate, Reaction of ester-modified pentaerythritol tri(meth) acrylate with an acid anhydride, reaction of caprolactone-modified dipentaerythritol penta (meth) acrylate with an acid anhydride, and caprolactone-modified tripellitate (yield) a reactant of an acrylate and an acid anhydride, and the like. Further, in the specific example of the polyfunctional acrylate shown here, the term "(meth)acrylate" means acrylate or methacrylate. Further, the term "caprolactone modification" means a ring-opening or a ring-opening polymerization in which a caprolactone is introduced between a portion derived from an alcohol of a (meth) acrylate compound and a (meth) acryloxy group. Things.

Commercially available products can also be used as the polyfunctional acrylate.

As such a commercial item, A-DOD-N, A-HD-N, A-NOD-N, APG-100, APG-200, APG-400, A-GLY-9E, A-GLY-20E are mentioned. , A-TMM-3, A-TMPT, AD-TMP, ATM-35E, A-TMMT, A-9550, A-DPH, HD-N, NOD-N, NPG, TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.) ), "ARONIX M-220", "ARONIX M-325", "ARONIX M-240", "ARONIX M-270", "ARONIX M-309", "ARONIX M-310", "ARONIX M-321", " ARONIX M-350, ARONIX M-360, ARONIX M-305, ARONIX M-306, ARONIX M-450, ARONIX M-451, ARONIX M-408, ARONIX M-400", "ARONIX M-402", "ARONIX M-403", "ARONIX M-404", "ARONIX M-405", "ARONIX M-406" (manufactured by Toagosei Co., Ltd.), "EBECRYL 11", "EBECRYL 145", "EBECRYL 150", "EBECRYL 40", "EBECRYL 140", "EBECRYL 180", DPGDA, HDDA, TPGDA, HPNDA, PETIA, PETRA, TMPTA, TMPOTOA, DPHA, EBECRYL series (Daicel - manufactured by Cytec Co., Ltd.).

Preferred examples of the polyfunctional acrylate include compounds represented by the following formulas (4-1) to (4-14).

The content of the polymerizable non-liquid crystal compound in the composition is usually 0.1 to 20% by mass, preferably 1 to 10% by mass, and more preferably 3 to 7% by mass based on the total mass of the composition. It is more preferably 0.1 to 19 parts by mass, still more preferably 1 to 15 parts by mass, even more preferably 4 to 10 parts by mass, per 100 parts by mass of the solid content of the composition. Furthermore, it is especially preferably 3 parts by mass or more and 10 parts by mass or less with respect to 100 parts by weight of the polymerizable liquid crystal compound. If the content of the polymerizable non-liquid crystal compound is within the above range, the composition can be disturbed without disturbing In the case of the alignment property of the polymerizable liquid crystal compound contained in the coating film obtained by the object, the polymerizable component (polymerizable liquid crystal compound and polymerizable non-liquid crystal compound) in the composition is copolymerized, which is preferable. The content is also determined by the type of each of the polymerizable liquid crystal compound and the polymerizable non-liquid crystal compound. When the content of the polymerizable non-liquid crystal compound is more than the above range, the transparency of the polarizing film tends to be lowered, which is not preferable.

<dichroic pigment>

The dichroic dye refers to a dye having a property in which the absorbance in the long axis direction of the molecule is different from the absorbance in the short axis direction. The dichroic dye may be a dye or a pigment as long as it has such a property, or may be a mixture of a plurality of compounds.

The dichroic dye preferably has a maximum absorption wavelength (λMAX) in the range of 300 to 700 nm. Examples of such a dichroic dye include acridine dyes. A dye, a cyanine dye, a naphthalene dye, an azo dye, an anthraquinone dye, etc., among them, an azo dye is preferable. Examples of the azo dye include a monoazo dye, a disazo dye, a trisazo dye, a tetrazo pigment, and a stilbene azo dye, and a disazo dye and a trisazo dye are preferable.

The azo dye is, for example, a compound represented by the formula (2) (hereinafter sometimes referred to as "compound (2)").

A ¹ (-N=NA ² ) _p -N=NA ³ (2)

In the formula (2), A ¹ and A ³ each independently represent a phenyl group which may have a substituent, a naphthyl group which may have a substituent, or a monovalent heterocyclic group which may have a substituent. A ² represents a para-phenyl group which may have a substituent, a naphthalene-1,4-diyl group which may have a substituent or a divalent heterocyclic group which may have a substituent. P represents an integer from 1 to 4. In the case where p is an integer of 2 or more, the plurality of A ^{2 's} may be the same or different from each other].

Examples of the monovalent heterocyclic group include quinoline, thiazole, benzothiazole, thienothiazole, imidazole, and benzimidazole. Oxazole and benzo A group obtained by removing one hydrogen atom from a heterocyclic compound such as azole. The group obtained by removing two hydrogen atoms from the heterocyclic compound corresponds to a divalent heterocyclic group, and the specificity of the heterocyclic compound is as described above.

Examples of the phenyl group, the naphthyl group and the monovalent heterocyclic group in A ¹ and A ³ , and the substituents optionally substituted for the phenyl, naphthalene-1,4-diyl and divalent heterocyclic groups in A ² Examples thereof include an alkyl group having 1 to 4 carbon atoms; an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, and a butoxy group; and a fluoroalkyl group having 1 to 4 carbon atoms such as a trifluoromethyl group; a substituted or unsubstituted amine group such as a cyano group; a nitro group; a halogen atom; an amine group, a diethylamino group, and a pyrrolidinyl group (the so-called substituted amino group means 1 or 2 carbon atoms 1~) The amine group of the alkyl group of 6 or the two substituted alkyl groups bonded to each other to form an amine group having a C 2-8 alkanediyl group; the unsubstituted amine group is -NH ₂ ). Further, specific examples of the alkyl group having 1 to 6 carbon atoms are the same as those exemplified as the substituent which the phenyl group of the compound (1) has.

Among the compounds (2), preferred are the compounds represented by the following formulas (2-1) to (2-6).

In the formulae (2-1) to (2-6), B ¹ to B ²⁰ independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, and a nitrate. A group, a substituted or unsubstituted amine group (substituted amino group and unsubstituted amine group are as defined above), a chlorine atom or a trifluoromethyl group.

N1 to n4 independently represent an integer of 0 to 3.

When n1 is 2 or more, the plurality of B ² may be the same or different from each other. When n2 is 2 or more, the plurality of B ⁶ may be the same or different from each other, and when n3 is 2 or more, the plural The B ⁹ groups may be the same or different from each other, and in the case where n4 is 2 or more, the plurality of B ¹⁴ may be the same or different from each other].

The above-mentioned anthraquinone dye is preferably a compound represented by the formula (2-7).

In the formula (2-7), R ¹ to R ⁸ each independently represent a hydrogen atom, -R ^x , -NH ₂ , -NHR ^x , -NR ^x ₂ , -SR ^x or a halogen atom.

R ^x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms.

As above The pigment is preferably a compound represented by the formula (2-8).

In the formula (2-8), R ⁹ to R ¹⁵ each independently represent a hydrogen atom, -R ^x , -NH ₂ , -NHR ^x , -NR ^x ₂ , -SR ^x or a halogen atom.

R ^x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms.

The acridine dye is preferably a compound represented by the formula (2-9).

In the formula (2-9), R ¹⁶ to R ²³ independently of each other represent a hydrogen atom, -R ^x , -NH ₂ , -NHR ^x , -NR ^x ₂ , -SR ^x or a halogen atom.

R ^x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ^x in the formula (2-7), the formula (2-8) and the formula (2-9) include a methyl group, an ethyl group, a propyl group and a butyl group. Examples of the aryl group having a carbon number of 6 to 12 and a pentyl group and a hexyl group include a phenyl group, a tolylmethyl group, a xylyl group, and a naphthyl group.

The cyanine dye is preferably a compound represented by the formula (2-10) and a compound represented by the formula (2-11).

In the formula (2-10), D ¹ and D ² each independently represent a group represented by any one of the formulae (2-10a) to (2-10d).

N5 represents an integer from 1 to 3].

In the formula (2-11), D ³ and D ⁴ each independently represent a group represented by any one of the formulae (2-11a) to (2-11h).

N6 represents an integer from 1 to 3].

The content of the dichroic dye in the composition is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 0.1 parts by mass or more and 20 parts by mass or less, based on 100 parts by mass of the content of the polymerizable liquid crystal compound. It is preferably 0.1 parts by mass or more and 10 parts by mass or less, and particularly preferably 0.1 parts by mass or more and 5 parts by mass or less. When the content of the dichroic dye is within this range, the polymerizable liquid crystal compound and the polymerizable non-liquid crystal can be obtained without disturbing the alignment of the polymerizable liquid crystal compound contained in the coating film obtained from the composition. It is preferred that the compound is polymerized. When the content of the dichroic dye is too large, there is a possibility that the alignment of the polymerizable liquid crystal compound is hindered. Therefore, the content of the dichroic dye can also be determined within a range in which the polymerizable liquid crystal compound can maintain the liquid crystal state.

A dichroic dye can be used by a commercial one.

<Polymerization initiator>

The present composition contains a polymerization initiator. The polymerization initiator is a compound which can initiate polymerization of a polymerizable liquid crystal compound or the like. As the polymerization initiator, a photopolymerization initiator which can generate living radicals by the action of light is preferred.

Examples of the polymerization initiator include a benzoin compound, a diphenyl ketone compound, an alkyl phenone compound, a decyl phosphine oxide compound, and the like. Compounds, strontium salts and strontium salts.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Examples of the diphenyl ketone compound include diphenyl ketone, methyl phthalyl benzoate, 4-phenyl diphenyl ketone, and 4-benzylidene-4'-methyl diphenyl sulphide. Ether, 3,3',4,4'-tetrakis(t-butylperoxycarbonyl)diphenyl ketone and 2,4,6-trimethyldiphenyl ketone.

Examples of the alkylphenone compound include diethoxyacetophenone and 2-methyl-2- Lolinyl-1-(4-methylthienyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4- Polinylphenyl)butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1,2-diphenyl-2,2-dimethoxyethane- 1-ketone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2- An oligomer of methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one or the like.

Examples of the fluorenylphosphine oxide compound include 2,4,6-trimethylbenzimidyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide. .

As three The compound may, for example, be 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-three 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-three And 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-tri Wait.

A polymerization initiator can be used by a commercial one. Examples of commercially available polymerization initiators include "Irgacure 907", "Irgacure 184", "Irgacure 651", "Irgacure 819", "Irgacure 250", and "Irgacure 369" (Ciba-Japan). "Seikuol BZ", "Seikuol Z", "Seikuol BEE" (Seiko Chemicals Co., Ltd.); "Kayacure BP100" (Nippon Chemicals Co., Ltd.); "Kayacure UVI-6992" (manufactured by DOW); "Adeka Optomer SP-152", "Adeka Optomer SP-170" (ADEKA (share)); "TAZ-A", "TAZ-PP" (Nihon Siber Hegner); and "TAZ-104" (SANWA CHEMICAL).

The content of the polymerization initiator in the composition is appropriately adjusted depending on the type and amount of the polymerizable liquid crystal compound, and is usually 0.1 to 30 parts by mass based on 100 parts by mass of the content of the polymerizable liquid crystal compound. It is preferably 0.5 to 10 parts by mass, more preferably 0.5 to 8 parts by mass. When the content of the polymerization initiator is in this range, the polymerizable liquid crystal compound and the polymerizable non-liquid crystal compound can be obtained without disturbing the alignment of the polymerizable liquid crystal compound contained in the coating film obtained from the composition. Copolymerization is therefore preferred.

<solvent>

The composition contains a solvent. The solvent is preferably a solvent which can completely dissolve the polymerizable liquid crystal compound, the polymerizable non-liquid crystal compound, and the dichroic dye. Further, a solvent which exhibits inactivity to the polymerization reaction in the present composition is preferred.

Examples of the solvent include alcohol solvents such as methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, and propylene glycol monomethyl ether; ethyl acetate, butyl acetate, and ethylene Ester solvent such as alcohol methyl ether acetate, γ-butyrolactone, or propylene glycol methyl ether acetate and ethyl lactate; acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone and Ketone solvents such as isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane and heptane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran and dimethoxyethane; And chlorine-containing solvents such as chloroform and chlorobenzene. These solvents may be used singly or in combination of plural kinds.

The content of the solvent is preferably from 50 to 98% by mass based on the total amount of the composition. In other words, the solid content in the composition is preferably from 2 to 50% by mass. When the solid content component is 2% by mass or more, it tends to be easy to obtain the polarizing film. In addition, when the solid content is 50% by mass or less, it is preferable that the viscosity of the present composition is low, so that the thickness of the polarizing film becomes substantially uniform, whereby the polarizing film is less likely to be uneven. Further, the solid content can be determined in consideration of the thickness of the present polarizing film to be produced.

The composition may contain a component other than the above components, and as the component, a polymerization reaction for controlling polymerization of a polymerizable liquid crystal compound or the like may be mentioned. Should be an auxiliary.

<Polymerization Aid>

The composition may further comprise a sensitizer. As the sensitizer, a photosensitizer is preferred. As the sensitizer, for example, Ketone and 9-oxosulfur Wait Ketone compounds (eg 2,4-diethyl-9-oxosulfur 2-isopropyl-9-oxosulfur And other compounds such as anthracene and alkoxy-containing anthracene (e.g., dibutoxyanthracene); And red fluorene and the like.

When the composition contains a sensitizer, the polymerization reaction of the polymerizable liquid crystal compound and the polymerizable non-liquid crystal compound contained in the composition can be further promoted. The amount of the sensitizer used is preferably from 0.1 to 30 parts by mass, more preferably from 0.5 to 10 parts by mass, even more preferably from 0.5 to 8 parts by mass, per 100 parts by mass of the total of the polymerizable liquid crystal compound.

In order to allow the polymerization reaction to proceed stably, the polymerization inhibitor may be appropriately contained in the present composition. By containing a polymerization inhibitor, the degree of progress of the polymerization reaction of the polymerizable liquid crystal compound and the polymerization reaction of the polymerizable non-liquid crystal compound can be controlled.

Examples of the polymerization inhibitor include hydroquinone, alkoxy-containing hydroquinone, alkoxy-containing catechol (for example, butyl catechol), and pyrogallol. A radical scavenger such as 2,2,6,6-tetramethyl-1-piperidinyloxy radical; thiophenols; β-naphthylamines and β-naphthols.

In the case where the polymerization inhibitor is contained in the composition, the content of the polymerization inhibitor is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the polymerizable liquid crystal compound. Further, it is preferably 0.5 to 8 parts by mass. If the content of the polymerization inhibitor is within the range, When the polymerization is carried out without disturbing the alignment of the polymerizable liquid crystal compound contained in the composition for forming a polarizing film, the polymerizable liquid crystal compound can be polymerized while maintaining the liquid crystal state more satisfactorily.

<leveling agent>

The present composition preferably contains a leveling agent. The leveling agent refers to a function of adjusting the fluidity of the composition and making the coating film obtained by applying the composition flatter, and examples thereof include a surfactant. The leveling agent is more preferably at least one selected from the group consisting of a leveling agent containing a polyacrylate compound as a main component and a leveling agent containing a fluorine atom-containing compound as a main component. Further, the polyacrylate compound herein does not have a polymerizable group.

Examples of the leveling agent containing a polyacrylate compound as a main component include "BYK-350", "BYK-352", "BYK-353", "BYK-354", "BYK-355", and "BYK-" 358N", "BYK-361N", "BYK-380", "BYK-381" and "BYK-392" [BYK Chemie].

Examples of the leveling agent containing a fluorine atom-containing compound as a main component include "MEGAFAC R-08", "MEGAFAC R-30", "MEGAFAC R-90", "MEGAFAC F-410", and "MEGAFAC F-" 411", "MEGAFAC F-443", "MEGAFAC F-445", "MEGAFAC F-470", "MEGAFAC F-471", "MEGAFAC F-477", "MEGAFAC F-479", "MEGAFAC F-482" And "MEGAFAC F-483" [DIC (share)]; "Surflon S-381", "Surflon S-382", "Surflon S-383", "Surflon S-" 393", "Surflon SC-101", "Surflon SC-105", "KH-40" and "SA-100" [AGC Seimi Chemical (share)]; "E1830", "E5844" [Daikin Fine Chemical Institute (shares)]; "Eftop EF301", "Eftop EF303", "Eftop EF351" and "Eftop EF352" [Mitsubishi Materials Electronic Chemicals (share)].

In the case where the composition contains a leveling agent, the content thereof is preferably 0.3 parts by mass or more and 5 parts by mass or less, more preferably 0.5 parts by mass or more and 3 parts by mass or less based on 100 parts by mass of the polymerizable liquid crystal compound. When the content of the leveling agent is within the above range, the polymerizable liquid crystal compound tends to be horizontally aligned, and the obtained polarizing film tends to be smoother, which is preferable. When the content of the leveling agent relative to the polymerizable liquid crystal compound exceeds the above range, the obtained polarizing film tends to be uneven and tends to be unsatisfactory. Further, the present composition may contain two or more kinds of leveling agents.

<Method of Forming the Polarizing Film>

Next, a method of forming the present polarizing film from the present composition will be described. First, the present composition is applied to a substrate or formed on an alignment film on a substrate. It is preferably applied to an alignment film formed on a substrate. As the substrate, a transparent substrate is preferred.

<Transparent substrate>

The transparent substrate is a substrate having transparency to the extent that light, particularly visible light, is transmitted. The term "transparency" refers to a property of having a transmittance of light having a wavelength of 380 to 780 nm of 80% or more. Specifically, examples of the transparent substrate include a glass substrate or a plastic substrate. Further, as the plastic constituting the plastic substrate, for example, polyethylene, polypropylene, and lower are mentioned. Polyolefin such as olefinic polymer; cyclic olefin resin; polyvinyl alcohol; polyethylene terephthalate; polymethacrylate; polyacrylate; cellulose triacetate, cellulose diacetate and acetic acid propionate Cellulose esters such as cellulose; polyethylene naphthalate; polycarbonate; polyfluorene; polyether oxime; polyether ketone; polyphenylene sulfide and polyphenylene ether. Among them, cellulose ester, cyclic olefin resin, polycarbonate, polyethylene terephthalate or polymethacrylic acid can be easily obtained from the market or excellent in transparency. ester. In the case where the polarizing film is produced by using the transparent substrate, the support substrate can be attached to the transparent substrate in advance in terms of easy handling when the transparent substrate is transported or stored without causing breakage such as breakage. Materials and so on. Further, the case where the phase difference is imparted to the plastic substrate when the circular polarizing plate is produced from the polarizing film will be described below. In this case, it is only necessary to impart phase difference to the plastic substrate by stretching treatment or the like. Further, a method of imparting phase difference to a transparent substrate will be described below.

At least a part of the hydroxyl group contained in the cellulose ester cellulose is acetated. Cellulose ester films comprising such cellulose esters are readily available on the market. As a commercially available cellulose triacetate film, for example, "Fujitac Film" (Fuji Film Co., Ltd.); "KC8UX2M", "KC8UY", and "KC4UY" (Konica Minolta Opto) are available. Such a commercially available cellulose triacetate film can be used as a transparent substrate directly or as needed to impart phase difference. Moreover, the surface of the prepared transparent substrate may be subjected to surface treatment such as anti-glare treatment, hard coating treatment, antistatic treatment or anti-reflection treatment. Bright substrate.

The term "cyclic olefin resin" means, for example, Alkene or polycyclic drop A polymer or a copolymer (cyclic olefin resin) of a cyclic olefin such as an olefinic monomer, and the cyclic olefin resin may partially contain a ring-opening portion. Further, it may be a hydrogenated cyclic olefin resin containing an open ring portion. Further, the cyclic olefin resin may be, for example, a cyclic olefin and a chain olefin or a vinylated aromatic compound in terms of not significantly impairing the transparency or not significantly increasing the hygroscopicity ( Copolymer of styrene, etc.). Further, the cyclic olefin resin may be introduced into a polar group in its molecule.

When the cyclic olefin resin is a copolymer of a cyclic olefin and a chain olefin or an aromatic compound having a vinyl group, the chain olefin is ethylene or propylene, and is also a vinylated aromatic compound. It is styrene, α-methylstyrene, and alkyl-substituted styrene. In such a copolymer, the content ratio of the structural unit derived from the cyclic olefin is 50 mol% or less, and is, for example, about 15 to 50 mol%, based on all the structural units of the cyclic olefin resin. When the cyclic olefin resin is a terpolymer obtained from a cyclic olefin, a chain olefin, or a vinylated aromatic compound, for example, the chain is derived from the total structural unit of the cyclic olefin resin. The content ratio of the structural unit of the olefin is about 5 to 80 mol%, and the content of the structural unit derived from the vinylated aromatic compound is about 5 to 80 mol%. The cyclic olefin-based resin of such a terpolymer has an advantage that the amount of the expensive cyclic olefin can be relatively reduced when the cyclic olefin-based resin is produced.

The cyclic olefin resin can be easily obtained from the market. As a market ring Examples of the olefin-based resin include "Topas" [Ticona (Germany)]; "ARTON" [JSR (share)]; "ZEONOR" and "ZEONEX" [Japan ZEON (share)]; "APEL" [Mitsui Chemical (share) manufacturing] and so on. The cyclic olefin-based resin can be formed into a film (cyclic olefin-based resin film) by a known film forming method such as a solvent casting method or a melt extrusion method. Further, a cyclic olefin resin film which has been commercially available in the form of a film can also be used. Examples of the commercially available cyclic olefin resin film include "S-SINA" and "SCA40" [Sekisui Chemical Industry Co., Ltd.]; "ZEONOR film" [Optronics]; "ARTON film" [ JSR (shares) and so on.

Next, a method of imparting phase difference to a plastic substrate will be briefly described. The plastic substrate can impart phase difference by a known stretching method. For example, a roll (wound body) obtained by winding a plastic substrate onto a roll is prepared, and a plastic substrate is continuously wound out from the take-up body, and the rolled plastic substrate is transferred to a heating furnace. The set temperature of the heating furnace is set to the range of the glass transition temperature (°C) to [glass transition temperature +100] (°C) of the plastic substrate, preferably set to the vicinity of the glass transition temperature (°C)~[glass transition temperature +50] (°C) range. In the heating furnace, when extending in the direction perpendicular to the progress direction of the plastic substrate or in the direction orthogonal to the progress direction, the conveyance direction or the tension is adjusted, and the uniaxial or biaxial heat extension treatment is performed by inclining at an arbitrary angle. The magnification of the stretching is usually in the range of about 1.1 to 6 times, preferably in the range of about 1.1 to 3.5 times. Further, the method of extending in the oblique direction is not particularly limited as long as the alignment axis can be continuously inclined at a desired angle, and a known extension method can be employed. The method of the above-described stretching method is exemplified by the method described in Japanese Laid-Open Patent Publication No. Hei. No. Hei.

The thickness of the transparent substrate is preferably thin in terms of the practical degree of the weight and the sufficient transparency, but if it is too thin, the strength is lowered and the workability is poor. . The appropriate thickness of the glass substrate is, for example, about 100 to 3000 μm, preferably 100 to 1000 μm. The appropriate thickness of the plastic substrate is, for example, about 5 to 300 μm, preferably 20 to 200 μm. When the polarizing film is used as the circular polarizing plate described below, the thickness of the transparent substrate is preferably thinner in the case of a circular polarizing plate for use in a mobile machine, and the thickness in the case of a glass substrate. Preferably, it is about 100 to 500 μm, and the thickness of the plastic substrate is preferably about 20 to 100 μm. Further, in the case where phase difference is imparted to the plastic substrate by stretching, the thickness after stretching is determined according to the thickness or the stretching ratio before stretching.

<Alignment film>

It is preferred to form an alignment film on the substrate used for the production of the polarizing film. In this case, the present composition is applied to the alignment film. Therefore, the alignment film preferably has solvent resistance to such an extent that it is not dissolved by coating or the like of the composition. Further, it is preferable to have heat resistance in a heat treatment for removing a solvent or aligning a liquid crystal. As the alignment film, an alignment polymer can be used.

Examples of the above-mentioned alignment polymer include polyamine or gelatin having a guanamine bond in the molecule, polyimine having a quinone bond in the molecule, and polyglycolic acid or polyethylene as a hydrolyzate thereof. Alcohol, alkyl modified polyvinyl alcohol, polypropylene decylamine, poly A polymer such as azole, polyethylenimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid or polyacrylate. Among these, polyvinyl alcohol is preferred. These alignment polymers which form an alignment film may be used singly or in combination of two or more.

The alignment polymer is applied to the substrate in the form of an alignment polymer composition (solution containing the alignment polymer) dissolved in a solvent, whereby an alignment film can be formed on the substrate. Examples of the solvent include water; alcohol solvents such as methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, methyl stilbene, butyl racelu and propylene glycol monomethyl ether; ethyl acetate and butyl acetate; Ester solvent such as ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate and ethyl lactate; acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl pentanone And ketone solvents such as methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane and heptane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; ethers such as tetrahydrofuran and dimethoxyethane Solvent; chlorine-substituted hydrocarbon solvent such as chloroform or chlorobenzene. These organic solvents may be used singly or in combination of plural kinds.

Further, as the alignment polymer composition for forming the alignment film, a commercially available alignment film material can be used as it is. The commercially available alignment film material may, for example, be Sunever (registered trademark, manufactured by Nissan Chemical Industries Co., Ltd.) or Optomer (registered trademark, manufactured by JSR Co., Ltd.).

As a method of forming an alignment film on the substrate, for example, the alignment polymer composition or a commercially available alignment film material may be applied onto the substrate, and then annealed to form an alignment on the substrate. membrane. The thickness of the alignment film thus obtained is, for example, in the range of 10 nm to 10000 nm, preferably in the range of 10 nm to 1000 nm.

In order to impart an alignment restriction force to the alignment film, it is preferably carried out as needed Friction (friction method). The polymerizable liquid crystal compound can be aligned in a desired direction by imparting an alignment regulating force.

As a method of imparting the alignment regulating force by the rubbing method, for example, a rubbing roll in which a rubbing cloth is wound and rotated is prepared, and a laminated body on which a coating film for forming an alignment film is formed on a substrate is placed on a stage. The film is conveyed to the rotating rubbing roller, whereby the coating film for forming an alignment film is brought into contact with the rotating rubbing roll.

Further, a so-called photoalignment film can also be used. The photo-alignment film is generally applied to a substrate by a polymer containing a photoreactive group or a composition of a monomer and a solvent (hereinafter sometimes referred to as a "photo-alignment layer-forming composition"). The photo-alignment-inducing layer is formed on the substrate, and the alignment control force is applied to the photo-alignment-inducing layer by irradiation of polarized light (preferably, polarized UV) to form an alignment film of the photo-alignment layer. The photoreactive group refers to a group which generates a liquid crystal alignment ability by irradiation of light (light irradiation). Specifically, it refers to a photoreactor that becomes the origin of liquid crystal alignment ability, such as alignment induction or isomerization reaction, dimerization reaction, photocrosslinking reaction or photodecomposition reaction of a molecule caused by irradiation of light. . Among the photoreactive groups, a dimerization reaction or a photocrosslinking reaction is preferred because it has excellent alignment properties and maintains a smectic liquid crystal state at the time of forming a polarizing film. As the photoreactive group capable of causing the reaction as described above, it is preferred to have an unsaturated bond, especially a double bond, and it is particularly preferred to have a carbon-carbon double bond (C=C bond) and a carbon-nitrogen double bond. A group of at least one of a group consisting of a bond (C=N bond), a nitrogen-nitrogen double bond (N=N bond), and a carbon-oxygen double bond (C=O bond).

Examples of the photoreactive group having a C=C bond include a vinyl group. Polyalkenyl, distyryl, distyrylzolyl, distyrazolylhydrazyl, chalcone, and cinnamyl. Examples of the photoreactive group having a C=N bond include a group having a structure such as an aromatic Schiff base and an aromatic fluorene. Examples of the photoreactive group having a N=N bond include an azophenyl group, an azonaphthyl group, an aromatic heterocyclic azo group, a bisazo group, and a fluorenyl group, or an azobenzene group. For the basic structure. Examples of the photoreactive group having a C=O bond include a diphenylketone group, a coumarin group, an anthracenyl group, and a maleimide group. These groups may have a substituent such as an alkyl group, an alkoxy group, an aryl group, an allyloxy group, a cyano group, an alkoxycarbonyl group, a hydroxyl group, a sulfonic acid group or a halogenated alkyl group.

Among them, a photoreactive group which can cause a photodimerization reaction is preferred, and a cinnabarinyl group and a chalcone group are required to have a relatively small amount of polarized light irradiation and excellent thermal stability or stability over time. The light alignment layer is preferred. Further, as the polymer having a photoreactive group, it is particularly preferred that the terminal portion of the side chain of the polymer has a cassia base which forms a cinnamic acid structure.

The solvent of the photo-alignment layer-forming composition is preferably a polymer or a monomer in which a photoreactive group is dissolved. Examples of the solvent include a solvent used in the above-mentioned alignment polymer composition.

The concentration of the polymer or monomer having a photoreactive group may be based on the type of the polymer or monomer having the photoreactive group or the thickness of the photoalignment film to be produced, relative to the composition for forming the photoalignment layer. The amount of the solid content component is preferably adjusted to at least 0.2% by mass, and more preferably 0.3 to 10% by mass. Further, the composition may contain a polymer material such as polyvinyl alcohol or polyimine or a photosensitizer in a range that does not significantly impair the characteristics of the photoalignment film.

As a method of coating the composition for forming a photoalignment layer on a substrate, a coating method such as a spin coating method, an extrusion coating method, a gravure coating method, a die coating method, a bar coating method, or an applicator method can be employed. Or a known method such as a printing method such as a flexographic printing method. Further, in the case where the polarizing film is produced by the following roll-to-roll continuous manufacturing method, the coating method is usually a printing method such as a gravure coating method, a die coating method or a flexographic printing method.

Further, if shielding is performed during rubbing or polarized light irradiation, a plurality of regions (patterns) having different alignment directions may be formed.

<Method of Manufacturing the Polarizing Film>

The present composition is applied onto the above-mentioned substrate or an alignment film formed on a substrate, and the solvent is removed to obtain a coated film. The coating method (coating method) is, for example, the same as the method exemplified as a method of applying an alignment polymer or a composition for forming an optical alignment layer on a substrate.

Then, the solvent is removed under the condition that the polymerizable liquid crystal compound and the polymerizable non-liquid crystal compound contained in the coating film are not polymerized, thereby forming a coating film. Examples of the removal method include a natural drying method, a ventilation drying method, a heat drying method, and a vacuum drying method. Then, the polymerizable liquid crystal composition contained in the coating film is in a state in which a smectic liquid crystal phase is exhibited. In this case, it is preferred to exhibit the characteristics of the polymerizable liquid crystal compound so that the liquid crystal state becomes a nematic liquid crystal phase, and the nematic liquid crystal phase is converted into a smectic liquid crystal phase. In order to change the liquid crystal phase in this manner, the method is as follows: first, heating until the polymerizable liquid crystal compound contained in the coating film exhibits a temperature higher than the temperature of the nematic liquid crystal phase, and then cooling until the polymerizable liquid crystal compound exhibits a temperature of the smectic liquid crystal phase until.

The polymerizable liquid crystal compound in the coating film as described above may exhibit the temperature of the smectic liquid crystal phase or the nematic liquid crystal phase as long as described above by using the texture observation or the like of the composition.

When the polymerizable liquid crystal compound and the polymerizable non-liquid crystal compound are polymerized, in order to maintain the stratified liquid crystal phase favorably in the polymerizable liquid crystal compound, it is preferred to use two or more kinds of polymerizable liquid crystal compounds as the polymerizable liquid crystal compound. combination. When the content ratio of the two or more kinds of polymerizable liquid crystal compounds is adjusted, the composition has the following advantages: after the smectic liquid crystal phase is formed via the nematic liquid crystal phase, it is convenient to simultaneously display the temperature of the crystal phase. It is also possible to temporarily form a supercooled state, and it is easy to maintain the liquid crystal state of the high-order layer phase. The content ratio of the two kinds of polymerizable liquid crystal compounds in the case of containing two kinds of polymerizable liquid crystal compounds is usually from 1:99 to 50:50, preferably from 5:95 to 50:50, more preferably from 10:90 to 50: 50.

Next, the polymerization step of the polymerizable liquid crystal compound and the polymerizable non-liquid crystal compound will be described.

After the polymerizable liquid crystal compound in the coating film is a smectic liquid crystal phase, the coating film is irradiated with energy while maintaining the smectic liquid crystal phase, whereby the polymerizable liquid crystal compound and the polymerizable non-liquid crystal compound are polymerized. Since the composition contains a polymerization initiator, it is preferred to irradiate energy for activating the polymerization initiator. Preferred energy is light. The type of the polymerization initiator contained in the coating film or the type of the polymerizable liquid crystal compound and the polymerizable non-liquid crystal compound (especially the type of the polymerizable group of the polymerizable liquid crystal compound) And its amount, suitably by light or living selected from the group consisting of visible light, ultraviolet light and laser light Conducted by a beam of electrons. Among these, ultraviolet light is preferred in terms of easy control of the progress of the polymerization reaction, or as a means for polymerization, which can be widely used in the field. Therefore, it is preferred to preliminarily select the type of the polymerizable liquid crystal compound, the polymerizable non-liquid crystal compound, and the polymerization initiator contained in the composition to be polymerizable by ultraviolet light. Further, at the time of polymerization, the coating film may be cooled by an appropriate cooling method while irradiating ultraviolet light, thereby controlling the polymerization temperature. When the polymerization of the polymerizable liquid crystal compound and the polymerizable non-liquid crystal compound is carried out at a lower temperature by such a cooling method, there is also an advantage that even if the substrate is used in a relatively low heat resistance, it may be appropriately formed. The polarizing film. Further, at the time of polymerization, the patterned local polarizing film can also be obtained by masking or developing.

By carrying out the polymerization as described above, the polymerizable liquid crystal compound is polymerized while maintaining the liquid crystal state of the smectic phase, preferably the high-order smectic phase as exemplified above, to form the present polarizing film. The present polarizing film obtained by polymerizing the polymerizable liquid crystal compound while maintaining the liquid crystal state of the smectic phase also has the following advantages along with the action of the above-mentioned dichroic dye: the same as the prior guest-type polarizing film, that is, maintaining the nematic In the case of a liquid crystal state, the polarizing film obtained by polymerization of a polymerizable liquid crystal compound or the like has an advantage of having high polarizing performance. Further, there is an advantage that the strength is excellent as compared with a case where only a dichroic dye is applied or a liquid crystal liquid is applied.

The thickness of the present polarizing film thus formed is preferably in the range of 0.5 μm or more and 10 μm or less, more preferably 1 μm or more and 5 μm or less. Therefore, the thickness of the coating film for forming the polarizing film is determined in consideration of the thickness of the obtained polarizing film. Furthermore, the thickness of the polarizing film utilizes an interference film thickness The measurement is performed by a meter, a laser microscope, or a stylus type film thickness meter.

The transparency can be evaluated using a haze value. The haze value is preferably 5% or less, more preferably 2% or less.

Further, as described above, the present polarizing film formed as described above is particularly preferably a Bragg peak obtained by X-ray diffraction measurement. As the present polarizing film which can obtain the Bragg peak, for example, the present polarizing film which exhibits a diffraction peak derived from a hexagonal liquid phase or a crystal phase can be cited.

<Continuous manufacturing method of the polarizing film>

The outline of the method for producing the polarizing film has been described above, and when the polarizing film is commercially produced, a method of continuously producing the polarizing film is required. Such a continuous manufacturing method is based on a roll-to-roll format, and is sometimes referred to as "this manufacturing method." In the present manufacturing method, the case where the substrate is a transparent substrate will be mainly described.

The manufacturing method includes, for example, a step of preparing a first roll of a transparent substrate wound on a first core, continuously feeding a transparent substrate from the first roll, and continuously coating the composition for forming an optical alignment layer. Dissolving on a transparent substrate; removing a solvent from the applied composition for forming a light alignment layer, continuously forming a first coating film on the transparent substrate; and irradiating the coating film with polarized UV, thereby continuously Forming a photo-alignment layer to form a photo-alignment film; continuously applying the composition on the photo-alignment film; and dispersing the polymerizable liquid crystal compound and the polymerizable non-liquid crystal compound The coated composition is dried to form a second coating film continuously on the photo-alignment film; and the liquid crystal state of the polymerizable liquid crystal compound contained in the coating film becomes a smectic liquid crystal phase The polymerizable liquid crystal compound is polymerized while maintaining the smectic liquid crystal phase, thereby continuously obtaining a polarizing film; and the continuously obtained laminated body including the transparent substrate, the photoalignment film, and the polarizing film is taken up in the second volume On the core, get the second volume. The present manufacturing method will be described here with reference to FIG. 1.

The first roll 210 in which the transparent substrate is wound up on the first core 210A can be easily obtained, for example, from the market. As such a transparent substrate which can be obtained from the market in the form of a roll, the transparent substrate exemplified above includes a cellulose ester, a cyclic olefin resin, polycarbonate, and polyethylene terephthalate. A film of a diester or a polymethacrylate or the like. Further, when the polarizing film is used as a circularly polarizing plate, a transparent substrate having phase difference imparted in advance can be easily obtained from the market, and examples thereof include cellulose ester, polycarbonate, or cyclic olefin resin. A retardation film or the like.

Then, the transparent substrate is sent from the first roll 210 described above. The method of feeding out the transparent substrate is performed by providing an appropriate rotating mechanism on the winding core 210A of the first roll 210, and rotating the first roll 210 by the rotating mechanism. Further, a suitable auxiliary roll 300 may be provided in the direction in which the transparent substrate is fed from the first roll 210, and the transparent substrate may be fed by the rotating mechanism of the auxiliary roll 300. Further, a rotation mechanism may be provided on both the first core 210A and the auxiliary roll 300 to feed the transparent substrate while applying appropriate tension to the transparent substrate.

When the transparent substrate fed from the first roll 210 is passed through the coating device 211A, the composition for forming a light alignment layer is applied onto the surface of the coating device 211A. The coating device 211A for applying the composition for forming an optical alignment layer in such a manner as described above is usually a printing device which can be applied by a gravure coating method, a die coating method, a flexographic printing method or the like.

The film which has passed through the coating device 211A is transferred to the drying furnace 212A, heated by the drying furnace 212A, and the solvent is removed from the applied composition to continuously form the first coating film on the transparent substrate. . As the drying furnace 212A, for example, a hot air drying oven or the like can be used. The set temperature of the drying furnace 212A is determined according to the type of the solvent contained in the composition for forming an optical alignment layer to be applied by the coating device 211A. Further, the drying furnace 212A may be a drying furnace in a form in which a plurality of divided regions are divided into a plurality of regions, and a plurality of drying furnaces may be arranged in series, and the drying furnaces may each have different set temperatures. The drying oven in the form of.

The surface of the first coating film or the surface of the transparent substrate side is irradiated with polarized light UV by the polarizing UV irradiation device 213A by the first coating film continuously formed by the heating furnace 212A to form a photoalignment layer. Light alignment film.

The laminate of the substrate and the photo-alignment film which are continuously formed in this manner is coated on the photo-alignment film by the coating device 211B, and then passed through the drying furnace 212B to form the composition. The polymerizable liquid crystal compound exhibits a second coating film of a smectic liquid crystal phase. The drying oven 212B functions to remove the solvent from the composition coated on the photo-alignment film, and at the same time, also functions to: polymerize the liquid crystalline compound contained in the composition. Thermal energy is imparted to the composition in such a manner that a smectic liquid crystal phase is exhibited by the nematic liquid crystal phase. In order to change the polymerizable liquid crystal compound into a nematic liquid crystal phase and then to form a smectic liquid crystal phase, the drying furnace 212B may be a multi-stage heat treatment. In other words, in the same manner as the drying furnace 212A, the drying furnace 212B may be a drying furnace in a form in which a plurality of divided regions are divided into a plurality of regions, and a plurality of drying furnaces may be arranged in series. Each of the drying furnaces has a drying furnace of a different temperature.

The film which has passed through the drying furnace 212B is conveyed to the light irradiation device 213B in a state where the solvent contained in the composition is sufficiently removed and the polymerizable liquid crystal compound in the second coating film holds the liquid crystal phase of the layer. By the light irradiation of the light irradiation device 213B, the polymerizable liquid crystal compound is photopolymerized together with the polymerizable non-liquid crystal compound while maintaining the liquid crystal phase of the smectic layer, and the polarizing film is continuously formed on the photoalignment film.

The present polarizing film thus continuously formed is wound up onto the second core 220A in the form of a laminate including a transparent substrate and a photo-alignment film, and the second roll 220 is obtained. When the second polarizing film is obtained by winding up the formed polarizing film, an appropriate spacer can be used for the winding.

In this manner, the transparent substrate is sequentially passed through the first roll/coating device 211A/drying furnace 212A/polarized UV irradiation device 213A/coating device 211B/drying furnace 212B/light irradiation device 213B, thereby being formed on the transparent substrate. The present polarizing film is continuously produced on the photoalignment film.

Further, in the present production method shown in Fig. 1, a method of continuously producing a transparent substrate from the transparent substrate to the present polarizing film is shown. For example, the transparent substrate may be sequentially passed through the first roll/coating device 211A/ Drying furnace 212A / polarized UV irradiation device 213A, the laminated body of the substrate and the optical alignment film which are continuously formed by this is taken up on the winding core, and the laminated body is produced in the form of a roll, and the laminated body is sent out from the roll, and the laminated body is sent out The present polarizing film is produced by sequentially passing through the coating device 211B/drying furnace 212B/light irradiation device 213B.

The present polarizing film obtained by the present production method has a shape of a film and a strip shape. When the present polarizing film is used in a liquid crystal display device or the like described below, it is used in accordance with the scale of the liquid crystal display device or the like to be cut into a desired size.

In the above, the configuration and manufacturing method of the polarizing film are described mainly on the case of the laminated body of the transparent substrate/photoalignment film/the present polarizing film. However, the laminated body including the polarizing film can be peeled off from the laminated body. The light alignment film or the transparent substrate may be in the form of a layer or a film in which a layer other than the transparent substrate/photoalignment film/the polarizing film is laminated. As described above, the polarizing film may further include a retardation film as described above, and may further include an antireflection layer or a brightness enhancement film.

Further, a transparent polarizing substrate itself may be used as a retardation film to form a circularly polarizing plate or a circularly polarizing plate in the form of a retardation film/optical alignment film/the present polarizing film. For example, when a uniaxially extending quarter-wave plate is used as the retardation film, the irradiation direction of the polarized light UV is set to be substantially 45° with respect to the conveyance direction of the transparent substrate, whereby the pair can be wound A circular polarizing plate is produced by means of a roll. As a quarter-wavelength plate used for manufacturing a circularly polarizing plate in this manner, it is preferable to have a characteristic that the in-plane retardation value with respect to visible light becomes shorter as the wavelength becomes shorter.

Alternatively, a 1⁄2 wavelength plate can be used as a retardation film to make it a late phase A linear polarizing plate roll whose axis is offset from the absorption axis of the polarizing film and formed on the side opposite to the surface on which the polarizing film is formed is formed to form a quarter-wavelength plate, thereby producing a wide-band circularly polarizing plate.

<Use of the polarizing film>

The polarizing film can be used in various display devices. A display device is a device having a display element, and includes a light-emitting element or a light-emitting device as a light-emitting source. Examples of the display device include a liquid crystal display device, an organic electroluminescence (EL) display device, an inorganic electroluminescence (EL) display device, and an electron emission display device (for example, a field emission display device (FED), Surface Conduction Electron Emitter Display (SED), electronic paper (display device using electronic ink or electrophoretic element), plasma display device, projection display device (eg, grating light valve (GLV, Grating) Light Valve) display device, display device having a digital micro-mirror device (DMD), piezoelectric ceramic display, and the like. The liquid crystal display device also includes any of a transmissive liquid crystal display device, a transflective liquid crystal display device, a reflective liquid crystal display device, a direct-view liquid crystal display device, and a projection liquid crystal display device. The display device may be a display device that displays a two-dimensional image or a stereoscopic display device that displays a three-dimensional image.

The present polarizing film is particularly useful for a display device of an organic electroluminescence (EL) display device or an inorganic electroluminescence (EL) display device.

FIG. 2 and FIG. 5 are schematic diagrams showing a cross-sectional configuration of a liquid crystal display device (hereinafter sometimes referred to as "the present liquid crystal display device") 10 using the polarizing film. The liquid crystal layer 17 is sandwiched between two base materials 14a and 14b.

FIG. 12 is a schematic view showing a cross-sectional configuration of an EL display device (hereinafter sometimes referred to as "the present EL display device") using the polarizing film.

Fig. 13 is a schematic view showing the configuration of a projection type liquid crystal display device using the present polarizing film.

First, the liquid crystal display device 10 shown in Fig. 2 will be described.

A color filter 15 is disposed on the liquid crystal layer 17 side of the substrate 14a. The color filter 15 is disposed at a position sandwiching the liquid crystal layer 17 and facing the pixel electrode 22, and the black matrix 20 is disposed at a position facing the boundary between the pixel electrodes. The transparent electrode 16 is disposed on the liquid crystal layer 17 side so as to cover the color filter 15 and the black matrix 20. Further, a protective layer (not shown) may be provided between the color filter 15 and the transparent electrode 16.

The thin film transistor 21 and the pixel electrode 22 are regularly arranged on the liquid crystal layer 17 side of the substrate 14b. The pixel electrode 22 is disposed at a position opposed to the color filter 15 by sandwiching the liquid crystal layer 17. An interlayer insulating film 18 having a connection hole (not shown) is disposed between the thin film transistor 21 and the pixel electrode 22.

As the base material 14a and the base material 14b, a glass base material and a plastic base material can be used. The glass substrate or the plastic substrate may be made of the same material as that exemplified as the transparent substrate used in the production of the polarizing film. Further, the transparent substrate of the polarizing film may also serve as the substrate 14a and the substrate 14b. In the case where a step of heating to a high temperature is required for producing the color filter 15 or the thin film transistor 21 formed on the substrate, a glass substrate or a quartz substrate is preferable.

The thin film transistor can be preferably used depending on the material of the substrate 14b. Examples of the thin film transistor 21 include a high-temperature polycrystalline germanium transistor formed on a quartz substrate, and a low-temperature polycrystalline germanium transistor formed on a glass substrate. An amorphous germanium transistor on a glass substrate or a plastic substrate. In order to further reduce the size of the liquid crystal display device, a driving IC (integrated circuit) may be formed on the substrate 14b.

A liquid crystal layer 17 is disposed between the transparent electrode 16 and the pixel electrode 22. A spacer 23 is disposed on the liquid crystal layer 17 to maintain a constant distance between the substrate 14a and the substrate 14b. Further, although the columnar spacer is illustrated in FIG. 2, the spacer is not limited to the columnar shape, and the shape is such that the substrate 14a and the substrate 14b can be held at a certain distance therebetween. Any.

An alignment layer for aligning the liquid crystal in a desired direction may be disposed on the surface of the layer formed on the substrate 14a and the substrate 14b in contact with the liquid crystal layer 17. Further, the present polarizing film may be disposed inside the liquid crystal cell, that is, the polarizing film may be disposed on the surface side contacting the liquid crystal layer 17. This form is hereinafter referred to as "inline form".

Each member is laminated in the order of the substrate 14a, the color filter 15, the black matrix 20, the transparent electrode 16, the liquid crystal layer 17, the pixel electrode 22, the interlayer insulating film 18, the thin film transistor 21, and the substrate 14b.

Among the base material 14a and the base material 14b that sandwich the liquid crystal layer 17, polarizers 12a and 12b are provided on the outer side of 14a and the base material 14b, and at least one of the polarizers includes the present polarizing film.

Further, a laminated retardation layer (for example, a quarter-wave plate or an optical compensation film) 13a and 13b is preferable. By arranging the polarizing film on the polarizer 12b in the polarizers 12a and 12b, the liquid crystal display device 10 can be provided with a function of converting incident light into linearly polarized light. Further, depending on the structure of the liquid crystal display device or the type of the liquid crystal compound contained in the liquid crystal layer 17, the retardation films 13a and 13b are also When the transparent substrate is a retardation film or a (polar) polarizing plate containing the polarizing film, the retardation film can be set as a retardation layer, and thus the phase difference layer of FIG. 2 can be omitted. 13a and / or 13b. Further, a polarizing film may be further provided on the light exit side (outer side) of the polarizer including the polarizing film.

Further, an anti-reflection film for preventing reflection of external light may be disposed on the outer side of the polarizer including the polarizing film (in the case where the polarizing film is further provided on the polarizing film).

As described above, the present polarizing film can be used in the polarizer 12a or 12b of the liquid crystal display device 10 of Fig. 2. By providing the polarizing film on the polarizers 12a and/or 12b, it is possible to achieve a further reduction in thickness of the liquid crystal display device 10.

In the case where the polarizing film is used in the polarizer 12a or 12b, the order of lamination is not particularly limited. The order of lamination will be described with reference to an enlarged view of portions A and B surrounded by a broken line in Fig. 2 .

Figure 3 is an enlarged schematic cross-sectional view of a portion A of Figure 2. In the case where the polarizer 100 is used as the polarizer 12a, the polarizing film 3, the photoalignment film 2, and the transparent substrate 1 are arranged in this order from the retardation layer 13a side. . Moreover, (A2) of FIG. 3 is provided so that the transparent base material 1, the optical alignment film 2, and the present polarizing film 3 are arranged in order from the phase difference layer 13a side.

Figure 4 is an enlarged schematic view of a portion of B of Figure 2. (B1) of FIG. 4 is a case where the polarizing substrate 100 is used as the polarizer 12b, and the transparent substrate 1, the optical alignment film 2, and the present polarizing film 3 are arranged in this order from the retardation film 13b side. . Figure 4 (B2) is based on the use of polarizer 100 as a polarizer In the case of 12b, the polarizing film 3, the optical alignment film 2, and the transparent substrate 1 are disposed in this order from the side of the retardation film 13b.

A backlight unit 19 as a light source is disposed on the outer side of the polarizer 12b. The backlight unit 19 includes a light source, a light guide, a reflector, a diffusion sheet, and a viewing angle adjustment sheet. Examples of the light source include electroluminescence, a cold cathode tube, a hot cathode tube, a light-emitting diode (LED), a laser light source, and a mercury lamp. Further, the type of the polarizing film can be selected in accordance with the characteristics of the light source.

When the liquid crystal display device 10 is a transmissive liquid crystal display device, white light emitted from a light source in the backlight unit 19 is incident into the light guide body, and the path is changed by the reflector to be diffused through the diffusion sheet. The diffused light is incident from the backlight unit 19 into the polarizer 12b by adjusting the viewing angle adjusting sheet so as to have a desired directivity.

Among the incident light without polarization, only a certain linearly polarized light passes through the polarizer 12b of the liquid crystal panel. The linearly polarized light is converted into circularly polarized light or circularly polarized light by the retardation layer 13b, and sequentially passes through the substrate 14b, the pixel electrode 22, and the like to reach the liquid crystal layer 17.

Here, depending on the potential difference between the pixel electrode 22 and the opposite transparent electrode 16, the alignment state of the liquid crystal molecules contained in the liquid crystal layer 17 changes, and the brightness of the light emitted from the liquid crystal display device 10 is controlled. When the liquid crystal layer 17 is in an alignment state in which the polarized light is directly transmitted, the polarized light passes through the liquid crystal layer 17 and the transparent electrode 16, and light of a specific wavelength range passes through the color filter 15 to reach the polarizer 12a, and the liquid crystal display device The brightest level shows the color determined by the color filter.

On the other hand, when the liquid crystal layer 17 is in an alignment state in which the polarized light is converted and transmitted, the light transmitted through the liquid crystal layer 17, the transparent electrode 16, and the color filter 15 is absorbed by the polarizer 12a. Thereby, the pixel is black. In the intermediate alignment state of the two states, the brightness of the light emitted from the liquid crystal display device 10 is also in the middle of the above two, so that the pixel displays the intermediate color.

When the liquid crystal display device 10 is a transflective liquid crystal display device, it is preferable to use a quarter-wave plate (circular polarizing plate) on the polarizing layer side of the polarizing film. At this time, the pixel electrode 22 has a transmissive portion formed of a transparent material and a reflecting portion formed of a material that reflects light, and an image is displayed in the transmissive portion in the same manner as the transmissive liquid crystal display device. On the other hand, in the reflection portion, external light is incident on the liquid crystal display device, and the circularly polarized light that has passed through the polarizing film passes through the liquid crystal layer 17 through the pixel electrode 22 by the action of the quarter-wave plate further provided on the polarizing film. Reflected and used for display.

Next, the present EL display device 30 using the present polarizing film will be described with reference to FIG. In the case where the present polarizing film is used in the present EL display device, it is preferable to use the polarizing film as a circular polarizing plate (hereinafter sometimes referred to as "the present polarizing plate"). The circular polarizing plate generally has two embodiments. Therefore, before describing the configuration of the EL display device 30 and the like, two embodiments of the circular polarizing plate will be described with reference to FIG.

Fig. 6(A) is a cross-sectional view schematically showing the first embodiment of the circular polarizing plate 110. In the first embodiment, the present polarizing film 3 in the polarizer 100 is further provided with a circular polarizing plate 110 of a retardation layer (retardation film) 4. Fig. 6(B) schematically shows a cross section of the second embodiment of the circular polarizing plate 110. Figure. In the second embodiment, the transparent substrate 1 (retardation film 4) to which retardation is applied in advance is used as the transparent substrate 1 used for the production of the polarizer 100, whereby the transparent substrate 1 itself has a phase difference. The present circular polarizing plate 110 functions as the layer 4.

Here, a method of manufacturing the circular polarizing plate 110 will be described in advance. In the second embodiment of the circularly polarizing plate 110, as described above, in the present manufacturing method for producing the polarizing film 100, a transparent substrate 1 having a phase difference imparted in advance, that is, a retardation film can be used as a transparent substrate. Manufactured from material 1. In the first embodiment of the circularly polarizing plate 110, the retardation film 4 may be formed by laminating the retardation film on the polarizing film 3 produced by the present manufacturing method B. In the case where the polarizing film 100 is produced in the form of the second roll 220 by the manufacturing method B, the polarizing film 100 may be taken up from the second roll 220 and cut into a specific size, and then cut. In the form of a phase difference film bonded to the polarizing film 100, a phase difference film may be wound up on the third roll of the core, thereby continuously producing a film-shaped and elongated circular polarizing plate. 110.

A method of continuously manufacturing the circular polarizing plate 110 will be described with reference to Fig. 7 . The manufacturing method includes the steps of continuously winding up the polarizing film 100 from the second roll 220, and continuously winding the retardation film from the third roll 230 in which the retardation film is wound; The polarizing layer provided on the polarizing film 100, which is wound up in the second roll 220, is continuously bonded to the retardation film wound from the third roll to form the circular polarizing plate 110; The circular polarizing plate 110 is taken up on the fourth core 240A to obtain the fourth volume 240.

In the above, the manufacturing method of the first embodiment of the circular polarizing plate 110 has been described. However, when the polarizing film 3 and the retardation film in the polarizer 100 are bonded, an appropriate adhesive can be used, and the adhesive can be passed through the adhesive. The formed adhesive layer is bonded to the polarizing film 3 and the retardation film.

Next, the present EL display device including the circular polarizing plate 110 will be described with reference to Fig. 8 .

The EL display device 30 is formed by laminating an organic functional layer 36 as a light-emitting source and a cathode electrode 37 on a substrate 33 on which a pixel electrode 35 is formed. The circular polarizing plate 31 is disposed on the side opposite to the organic functional layer 36, and the circular polarizing plate 110 is used as the circular polarizing plate 31. By applying a positive voltage to the pixel electrode 35, a negative voltage is applied to the cathode electrode 37, and a direct current is applied between the pixel electrode 35 and the cathode electrode 37, and the organic functional layer 36 emits light. The organic functional layer 36 as a light source includes an electron transport layer, a light emitting layer, a hole transport layer, and the like. The light emitted from the organic functional layer 36 passes through the pixel electrode 35, the interlayer insulating film 34, the substrate 33, and the circularly polarizing plate 31 (the present circular polarizing plate 110). The organic EL display device including the organic functional layer 36 has been described, and can also be applied to an inorganic EL display device including an inorganic functional layer.

When the EL display device 30 is manufactured, the thin film transistor 40 is first formed on the substrate 33 in a desired shape. Then, the interlayer insulating film 34 is formed into a film, and then the pixel electrode 35 is formed into a film by sputtering to be patterned. Thereafter, an organic functional layer 36 is laminated.

Then, a circular polarizing plate 31 (the present circular polarizing plate 110) is provided on the opposite surface of the substrate 33 on which the surface of the thin film transistor 40 is provided.

When the circular polarizing plate 110 is used as the circular polarizing plate 31, reference is made to An enlarged view of a portion C surrounded by a broken line in Fig. 8 illustrates the order of lamination. When the circular polarizing plate 110 is used as the circular polarizing plate 31, the phase difference layer 4 on the circular polarizing plate 110 is disposed on the substrate 33 side. 9(C1) is an enlarged view of the circular polarizing plate 31 using the first embodiment of the circular polarizing plate 110, and (C2) is a circular polarizing plate 31 using the second embodiment of the circular polarizing plate 110. Enlarged image.

Next, members other than the present polarizing film 31 (circular polarizing plate 110) of the present EL display device 30 will be briefly described.

Examples of the substrate 33 include a sapphire glass substrate, a quartz glass substrate, a soda glass substrate, and a ceramic substrate such as alumina; a metal substrate such as copper; and a plastic substrate. Although not shown, a thermally conductive film may be formed on the substrate 33. Examples of the thermally conductive film include a diamond film (such as DLC (Diamond-Like Carbon)). When the pixel electrode 35 is in a reflective mode, light is emitted in a direction opposite to the substrate 33. Therefore, not only a transparent material but also a non-transmissive material such as stainless steel can be used. The substrate may be formed singly or in the form of a laminated substrate by bonding a plurality of substrates with an adhesive. Moreover, these base materials are not limited to a plate shape, and may be a film.

As the thin film transistor 40, for example, a polycrystalline germanium transistor or the like may be used. The thin film transistor 40 is provided at the end of the pixel electrode 35 and has a size of about 10 to 30 μm. Furthermore, the size of the pixel electrode 35 is about 20 μm × 20 μm to 300 μm × 300 μm.

A wiring electrode of the thin film transistor 40 is provided on the substrate 33. The wiring electrode has a low resistance, and has a function of electrically connecting to the pixel electrode 35 and suppressing the resistance value to be low. The wiring electrode is usually made of Al, Al, and transition. Any one or two or more of a metal (excluding Ti), Ti, or titanium nitride (TiN).

An interlayer insulating film 34 is provided between the thin film transistor 40 and the pixel electrode 35. The interlayer insulating film 34 is formed by sputtering an inorganic material such as cerium oxide or tantalum nitride such as SiO ₂ by sputtering or vacuum deposition, and is formed by SOG (Spin-On-Glass). Any one of the enamel layer, the coating film of a resin material such as a photoresist, a polyimide, or an acrylic resin may be insulating.

A barrier wall 41 is formed on the interlayer insulating film 34. The barrier 41 is disposed on the peripheral portion of the pixel electrode 35 (between adjacent pixels). Examples of the material of the barrier rib 41 include an acrylic resin and a polyimide resin. The thickness of the barrier rib 41 is preferably 1.0 μm or more and 3.5 μm or less, and more preferably 1.5 μm or more and 2.5 μm or less.

Next, an EL element including a pixel electrode 35 as a transparent electrode, an organic functional layer 36 as a light source, and a cathode electrode 37 will be described. The organic functional layer 36 has at least one layer of a hole transport layer and a light-emitting layer, for example, an electron injection transport layer, a light-emitting layer, a hole transport layer, and a hole injection layer.

Examples of the pixel electrode 35 include ITO (Indium Tin Oxides), IZO (Indium Zinc Oxide), IGZO (Indium Gallium Zinc Oxide), ZnO, and SnO _{2 .} And In ₂ O ₃ and the like, and particularly preferably ITO or IZO. The thickness of the pixel electrode 35 may be a thickness of a certain thickness or more sufficient for hole injection, and is preferably set to about 10 to 500 nm.

The pixel electrode 35 can be formed by a vapor deposition method (preferably, a sputtering method). The sputtering gas is not particularly limited, and any inert gas such as Ar, He, Ne, Kr or Xe or a mixed gas thereof may be used.

As a constituent material of the cathode electrode 37, for example, a metal element such as K, Li, Na, Mg, La, Ce, Ca, Sr, Ba, Al, Ag, In, Sn, Zn, or Zr may be used, but in order to improve the electrode The stability of the action is preferably an alloy system selected from the group consisting of two or three of the metal elements exemplified. As the alloy system, for example, Ag-Mg (Ag: 1 to 20 at%), Al-Li (Li: 0.3 to 14 at%), In-Mg (Mg: 50 to 80 at%), and Al-Ca are preferable. (Ca: 5~20 at%), etc.

The cathode electrode 37 is formed by a vapor deposition method, a sputtering method, or the like. Preferably, the cathode electrode 37 has a thickness of 0.1 nm or more, preferably 1 to 500 nm or more.

The hole injection layer has a function of facilitating the injection of holes from the pixel electrode 35, and the hole transport layer has a function of transmitting holes and a function of blocking electrons, and is also called a charge injection layer or a charge transport layer.

The thickness of the light-emitting layer, the combined thickness of the hole injection layer and the hole transport layer, and the thickness of the electron injection transport layer are not particularly limited, and are different depending on the formation method, but are preferably set to about 5 to 100 nm. . Various organic compounds can be used for the hole injection layer or the hole transport layer. When a hole injection transport layer, a light-emitting layer, and an electron injecting and transporting layer are formed, a vacuum thin film method can be used in terms of forming a homogeneous thin film.

As the light-emitting source, the organic functional layer 36 can be used by those who emit light (fluorescence) derived from singlet excitons, those that emit light from a triplet exciton (phosphorescence), and those that utilize singlet excitons. Luminous (fluorescent) and utilization a layer derived from a triplet exciton luminescence (phosphorescence), a layer formed of an organic substance, a layer formed of an organic substance and a layer formed of an inorganic substance, a polymer material, a low molecular material, a polymer material, and a low Molecular materials, etc. However, the present invention is not limited thereto, and the organic functional layer 36 using various materials known as EL elements can be used in the present EL display device 30.

A desiccant 38 is disposed in the space between the cathode electrode 37 and the sealing cover 39. The reason for this is that the organic functional layer 36 is not resistant to moisture. The deterioration of the organic functional layer 36 is prevented by the moisture absorbed by the desiccant 38.

FIG. 10 is a schematic view showing a cross-sectional configuration of another aspect of the EL display device 30. The EL display device 30 has a sealing structure using a film sealing film 41, and light can be emitted from the opposite surface of the array substrate.

As the film sealing film 41, a DLC film in which DLC (Diamond-Like Carbon) is vapor-deposited on a film of an electrolytic capacitor is preferably used. The DLC film has a characteristic of poor moisture permeability and high moisture resistance. Further, DLC may be directly deposited on the surface of the cathode electrode 37 to form a DLC film or the like. Further, the resin film and the metal thin film may be laminated in a plurality of layers to form the film sealing film 41.

As described above, the novel polarizing film (the present polarizing film) of the present invention and the novel display device (the present liquid crystal display device and the present EL display device) including the polarizing film are provided.

Finally, a projection type liquid crystal display device using the present polarizing film will be described.

Fig. 11 is a schematic view showing a projection type liquid crystal display device using the present polarizing film.

As a polarizer 142 and/or a polarizer of the projection type liquid crystal display device 143, the use of this polarizing film.

The light beam emitted from the light source (for example, the high-pressure mercury lamp) 111 as the light-emitting source first passes through the first lens array 112, the second lens array 113, the polarization conversion element 114, and the superimposing lens 115, thereby performing luminance on the cross-beam beam profile. Homogenization and polarization.

Specifically, the light beam emitted from the light source 111 is divided into a plurality of minute light beams by the first lens array 112 in which the minute lenses 112a are formed in a matrix. Since the divided light beams are irradiated with the entire three liquid crystal panels 140R, 140G, and 140B as the illumination target, the second lens array 113 and the superimposing lens 115 are provided. Therefore, the overall illumination on the incident side surface of each liquid crystal panel is substantially uniform.

The polarization conversion element 114 is composed of a polarization beam splitter array and is disposed between the second lens array 113 and the superimposing lens 115. Thereby, the following effects are achieved: the random polarization from the light source is converted into a polarized light having a specific polarization direction in advance, and the amount of light loss in the incident side polarizer is reduced to improve the brightness of the screen.

The light uniformized and polarized by the brightness as described above is sequentially passed through the mirror 122, and is sequentially passed through the red channel, the green channel, and the blue channel by the dichroic mirrors 121, 123, and 132 which are separated into three primary colors of RGB. The separation is incident on the liquid crystal panels 140R, 140G, and 140B, respectively.

The liquid crystal panels 140R, 140G, and 140B are each provided with a polarizer 142 on the incident side thereof, and a polarizer 143 is disposed on the exit side. The polarizing film can be used for the polarizer 142 and the polarizer 143.

The polarizer 142 and the polarizer 143 disposed on each of the RGB optical paths are each The absorption axes are arranged in an orthogonal manner. Each of the liquid crystal panels 140R, 140G, and 140B disposed on each optical path has a function of converting a polarization state controlled for each pixel in accordance with an image signal into a light amount.

The polarizing film 100 can be used as a polarizing film excellent in durability in any of the blue channel, the green channel, and the red channel by selecting a type suitable for the corresponding channel dichroic dye.

According to the image data of the liquid crystal panels 140R, 140G, and 140B, the incident light is transmitted at different transmittances of the respective pixels, whereby the optical image produced is synthesized by the combining aperture 150, and enlarged by the projection lens 170. Projected on screen 180.

Examples of the electronic paper include those in which a molecule such as an optical anisotropy and a dye molecule is aligned, and a particle is displayed by electrophoresis, particle movement, particle rotation, or phase change, and the film is moved by one end of the film. When the display is performed, the display is performed by the color development/phase change of the molecule, and the display is performed by light absorption of the molecules, and the electrons are combined with the holes to display the person by self-luminescence. More specifically, microcapsule electrophoresis, horizontal mobile electrophoresis, vertical mobile electrophoresis, spherical torsion sphere, magnetic torsion sphere, cylindrical torsion sphere method, charged toner, electronic powder fluid, magnetic migration type, magnetic Thermal sensing, electrowetting, light scattering (transparent/white turbidity change), cholesteric liquid crystal/photoconductive layer, cholesteric liquid crystal, bistable nematic liquid crystal, ferroelectric liquid crystal, 2-color pigment-liquid crystal dispersion type, movable film The use of leuco dyes for color reduction, photochromism, electron coloration, electrodeposition, soft organic EL, and the like. Electronic paper can be used not only for individuals who use text or images, but also for advertisement display (signage). Electronic paper can be made by the polarizing film The thickness is thin.

As a stereoscopic display device, for example, a method of arranging retardation films different from each other as in the case of a microsphere is proposed (Japanese Patent Laid-Open Publication No. 2002-185983), and the optical film of the present invention is used as a polarizing film, which is easy to use. Printing, inkjet, photolithography, and the like are performed, so that the manufacturing steps of the display device can be shortened, and a retardation film is not required.

[Examples]

Hereinafter, the present invention will be described in further detail by way of examples. In the examples, "%" and "parts" are % by mass and parts by mass unless otherwise specified.

In the present embodiment, the following polymerizable liquid crystal compound was used.

Compound (1-6) (a compound represented by the following formula (1-6))

The compound (1-6) was synthesized by the method described in Lubetal. Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996).

[Measurement of phase transition temperature]

The phase transition temperature of the compound (1-6) was confirmed by determining the phase transition temperature of the film containing the compound (1-6). Its operation is as follows.

A film containing the compound (1-6) was formed on the alignment film formed on the glass substrate, and the phase transition temperature was confirmed by the texture observation using a polarizing microscope (BX-51, manufactured by Olympus Co., Ltd.) while heating. It was confirmed that the film containing the compound (1-6) was phase-transformed into a nematic phase at 112 ° C when the temperature was raised to 120 ° C, and the phase was converted into a smectic phase A at 110 ° C, and the phase was converted to a phase at 94 ° C. Layer B phase.

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

The compound (1-7) is synthesized by using the synthesis of the above compound (1-6) as a reference.

[Measurement of phase transition temperature]

The phase transition temperature of the compound (1-7) was confirmed in the same manner as the phase transition temperature measurement of the compound (1-6). It was confirmed that the compound (1-7) was phase-transformed into a nematic phase at 133 ° C when the temperature was raised to 140 ° C, and the phase was converted into a smectic phase A at 118 ° C, and the phase was converted into a smectic phase B at 78 ° C. .

Example 1 [Preparation of the present composition, etc.]

The following components were mixed and stirred at 8 ° C for 1 hour to obtain the present composition (a composition for forming a polarizing film).

Polymerizable liquid crystal compound: Compound (1-6) 75 parts

Compound (1-7) 25 parts

Dichroic pigment: compound (2-1-1) 2.5 parts

D10 pigment described in Japanese Patent No. 3687130

Polymerization initiator: 1-hydroxy-cyclohexyl-phenyl ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) 6 parts

Leveling agent: BYK-361N (manufactured by BYK-Chemie) 1.5 parts

Polymerizable non-liquid crystal compound: polyfunctional acrylate (4-5) 5.0 parts

Solvent: cyclopentanone 250 parts

[Measurement of phase transition temperature]

The phase transition temperature of the polymerizable liquid crystal compound contained in the present composition prepared as described above was determined in the same manner as in the case of the compound (1-6) and the compound (1-7). It was confirmed that when the temperature was raised to 140 ° C and then the temperature was lowered, the phase separation state was not formed at 109 ° C and the phase was converted into a nematic phase. The phase separation state was not formed at 98 ° C and the phase was converted into the smectic phase A phase at 74 ° C. The phase separation state is not formed and the phase is converted into the smectic B phase.

[Manufacture and evaluation of this polarizing film] 1. Formation of alignment film

A glass substrate was used as the transparent substrate.

A 2% by mass aqueous solution (composition for forming an alignment layer) of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified, manufactured by Wako Pure Chemical Industries Co., Ltd.) was applied to the glass substrate by a spin coating method, and dried. Thereafter, a film having a thickness of 100 nm was formed. Then, an alignment layer was formed by subjecting the surface of the obtained film to a rubbing treatment to prepare a polarizing film. The friction treatment system uses a semi-automatic friction device (trade name: LQ-008 type, manufactured by Changyang Engineering Co., Ltd.), and uses a cloth (trade name: YA-20-RW, manufactured by Yoshikawa Chemical Co., Ltd.) at a press-in amount of 0.15 mm. The speed was 500 rpm and 16.7 mm/s. By this rubbing treatment, the laminated body 1 in which the alignment film was formed on the glass substrate was obtained.

2. Formation of polarizing film

The polarizing film-forming composition is applied onto the alignment film of the laminate 1 by a spin coating method, and dried by heating on a hot plate at 120 ° C for 1 minute, and then rapidly cooled to room temperature to form on the alignment film. Coating film. In the coating film, the liquid crystal state of the polymerizable liquid crystal compound contained is a smectic B phase. Then, a UV irradiation device (SPOTCURE SP-7, manufactured by Ushio Electric Co., Ltd.) was used, and the coating film was irradiated with ultraviolet rays at an exposure amount of 2000 mJ/cm ² (313 nm) to thereby polymerize the coating film. The liquid crystal compound is polymerized while maintaining the liquid crystal state, and a polarizing film is formed from the coating film. The thickness of the polarizing film at this time was measured by a laser microscope (OLS3000 manufactured by Olympus Co., Ltd.), and it was 1.6 μm.

3. X-ray diffraction measurement

X-ray diffraction measurement was performed on the obtained polarizing film using an X-ray diffraction apparatus X'Pert PRO MPD (manufactured by Spectris Co., Ltd.). X-rays were generated using Cu as a target at an X-ray tube current of 40 mA and an X-ray tube voltage of 45 kV, and the generated X-rays were incident from the alignment direction by a fixed divergence slit of 1/2° in the scanning range 2θ. The measurement was performed in a step of 2θ=0.01671° in the range of 4.0 to 40.0°, and as a result, a steep Bragg peak of FWHM (Full Width Half Maximum)=about 0.1718° was obtained in the vicinity of 2θ=20.24°. It was also found that the same result was obtained even if it was incident from the surface parallel to the surface of the polarizing film and perpendicular to the direction of the alignment. The order period (d) obtained from the peak position is about 4.4 Å, forming a structure reflecting the high-order stratigraphic phase.

4. Measurement of dichroic ratio (DR, Dichroic Ratio) = Determination of dichroic ratio in the following manner

The absorbance in the direction of the transmission axis at the maximum absorption wavelength was measured by a two-beam method using a device in which a folder with a polarizing photon was mounted on a spectrophotometer (UV-3150 manufactured by Shimadzu Corporation) (A ^{1 )} And absorbance (A ² ) in the direction of the absorption axis. The folder is placed on the reference side with a web that cuts off 50% of the light. Ratio (A ² / A ^1), as the dichroic ratio of the transmission from the measured absorbance (A ¹⁾ and (A ²⁾ of the absorbance value of the absorption axis direction of the axis of calculating. The higher the dichroic ratio, the more excellent the characteristics as a polarizing film. The measurement results of the maximum absorption wavelength of the absorbance (A ² ) in the absorption axis direction and the dichroic ratio at the wavelength are shown in Table 1.

5. Determination of haze value

In order to confirm the transparency of the polarizer, a haze value was measured using a haze meter (HZ-2, manufactured by Suga Test Instruments Co., Ltd.). The measurement results are shown in Table 1.

In Examples 2 to 8, Reference Example 1, and Comparative Examples 1 and 2, the present composition was produced in the same manner except that the type and content of the polymerizable non-liquid crystal compound were changed. Further, in Comparative Example 3, the composition was prepared without adding a polymerizable non-liquid crystal compound, and after drying at 120 ° C after application, it was rapidly moved on a hot plate at 70 ° C, and then UV exposure was carried out. This makes a polarizing film. The results of the respective measurements are shown in Table 1.

In the same manner as in Example 1, except that the dichroic dye was changed to the following structural formula (2-3-1), and the type and content of the polymerizable non-liquid crystal compound were changed, polarized light was produced in the same manner as in Example 1. membrane. The results of the respective measurements are shown in Table 1.

Examples 1 to 15 did not form a phase separation state and exhibited good horizontal alignment and higher dichroism. The good horizontal alignment is due to the fact that the polymerizable liquid crystal compound exhibits a nematic liquid crystal phase, and the higher dichroism is due to the polymerizable liquid crystal compound exhibiting a smectic liquid crystal phase.

[Industrial availability]

The present polarizing film can be preferably used as a display device (display). Therefore, the present composition which can produce the present polarizing film has a high industrial value.

1‧‧‧Transparent substrate

2‧‧‧Light alignment film

3‧‧‧This polarizing film

4‧‧‧ phase difference layer

10‧‧‧Liquid crystal display device

11‧‧‧Anti-reflective layer

12a, 12b‧‧‧ polarizing film

13a, 13b‧‧‧ phase difference film

14a, 14b‧‧‧Substrate

15‧‧‧Color filters

16‧‧‧Transparent electrode

17‧‧‧Liquid layer

18‧‧‧Interlayer insulating film

19‧‧‧Backlight unit

20‧‧‧Black matrix

21‧‧‧film transistor

22‧‧‧pixel electrode

23‧‧‧ spacers

24‧‧‧Liquid crystal display device

30‧‧‧EL display device

31‧‧‧Polar polarizer

33‧‧‧Substrate

34‧‧‧Interlayer insulating film

35‧‧‧pixel electrode

36‧‧‧Lighting layer

37‧‧‧Cathode electrode

38‧‧‧Drying agent

39‧‧‧ Sealing cover

40‧‧‧film transistor

41‧‧‧ blocking wall

42‧‧‧film sealing film

100‧‧‧ polarizing film

110‧‧‧round polarizing plate

111‧‧‧Light source

112‧‧‧1st lens array

112a‧‧ lens

113‧‧‧2nd lens array

114‧‧‧Polarized light conversion element

115‧‧‧Overlapping lens

121, 123, 132‧ ‧ dichroic mirror

122‧‧‧Mirror

140R, 140G, 140B‧‧‧ LCD panel

142, 143‧‧‧ polarized photons

150‧‧‧合光稜鏡

170‧‧‧Projection lens

180‧‧‧ screen

210‧‧‧ Volume 1

210A‧‧‧core

211A, 211B‧‧‧ coating device

212A, 212B‧‧‧ drying oven

213A‧‧‧Polarized UV irradiation device

213B‧‧‧Lighting device

220‧‧‧ Volume 2

220A‧‧‧core

230‧‧‧ Volume 3

230A‧‧‧core

240‧‧‧Volume 4

240A‧‧‧core

300‧‧‧Auxiliary volume

Fig. 1 is a schematic view showing essential parts of a continuous manufacturing method (Roll to Roll form) of a polarizing film of the present invention.

Fig. 2 is a schematic view showing a cross-sectional configuration of a liquid crystal display device using a polarizer containing the polarizing film of the present invention.

3(A1) and (A2) show the contents of the present invention installed on the liquid crystal display device. A schematic diagram of the stacking order of the polarizers of the polarizing film of the invention.

4(B1) and (B2) are schematic views showing the order of lamination of the polarizers including the polarizing film of the present invention provided on the liquid crystal display device.

Fig. 5 is a schematic view showing the configuration of a liquid crystal display device (embedded form) using a polarizer containing the polarizing film of the present invention.

6(A) and 6(B) are schematic cross-sectional views showing a circularly polarizing plate containing the polarizing film of the present invention.

Fig. 7 is a schematic view showing a continuous production method of a circularly polarizing plate containing the polarizing film of the present invention.

Fig. 8 is a schematic view showing the configuration of an EL (Electro Luminescence) display device using a circularly polarizing plate containing the polarizing film of the present invention.

9(C1) and (C2) are schematic views showing the order of lamination of the circularly polarizing plates including the polarizing film of the present invention provided on the EL display device.

Fig. 10 is a schematic view showing the configuration of an EL display device using a circularly polarizing plate containing the polarizing film of the present invention.

Fig. 11 is a schematic view showing the configuration of a projection type liquid crystal display device using a polarizer containing the polarizing film of the present invention.

Claims (12)

A composition for forming a polarizing film, comprising a polymerizable liquid crystal compound, a polymerizable non-liquid crystal compound, a dichroic dye, a polymerization initiator, and a solvent, wherein the polymerizable liquid crystal compound is a compound represented by the formula (1), and the compound The composition for forming a polarizing film satisfies the following requirements (A) and (B): (A) both the polymerizable liquid crystal compound and the polymerizable non-liquid crystal compound have a polymerizable group; and (B) the composition for forming a polarizing film is obtained. The polymerizable liquid crystal compound contained in the coating film does not form a phase separation state, and exhibits a nematic liquid crystal phase and a smectic liquid crystal phase; U ¹ -V ¹ -W ¹ -X ¹ -Y ¹ -X ² -Y ² -X ³ -W ² -V ² -U ² (1) (wherein X ¹ , X ² and X ³ independently of each other represent a 1,4-phenylene group which may have a substituent or a ring which may have a substituent Hexane-1,4-diyl; wherein at least one of X ¹ , X ² and X ³ is a 1,4-phenylene group which may have a substituent; and constitutes a cyclohexane-1,4-diyl group -CH ₂ - may be substituted by -O-, -S- or -NR-; R represents an alkyl group having 1 to 6 carbon atoms or a phenyl group; and Y ¹ and Y ² each independently represent -CH ₂ CH ₂ -, _{-CH 2 O -, - COO -} , - OCOO-, a single bond, -N = N -, - CR a = CR b - -C≡C- or -CR ^a = N-; R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms of; the ^U-1 represents a hydrogen atom or a polymerizable group; U ² represents a polymerizable group ; W ¹ and W ² independently of each other represent a single bond, -O-, -S-, -COO- or -OCOO-; and V ¹ and V ² independently of each other represent an alkyl group having 1 to 20 carbon atoms which may have a substituent; The diradical, -CH ₂ - constituting the alkanediyl group may be substituted by -O-, -S- or -NH-). The composition for forming a polarizing film according to claim 1, wherein the polymerizable non-liquid crystal The compound is a monofunctional acrylate or a multifunctional acrylate. The composition for forming a polarizing film according to claim 1 or 2, wherein the polymerizable group of the polymerizable liquid crystal compound and the polymerizable group of the polymerizable non-liquid crystal compound are each independently a propylene oxime group (CH ₂ =CHCOO). -) or methacryloxycarbonyl (CH ₂ = C(CH ₃ )COO-). The composition for forming a polarizing film according to claim 1 or 2, wherein the polymerizable group of the polymerizable liquid crystal compound is the same as the polymerizable group of the polymerizable non-liquid crystal compound. The composition for forming a polarizing film according to claim 1 or 2, wherein the polymerizable liquid crystal compound has 1 to 2 polymerizable groups in the molecule, and the polymerizable non-liquid crystal compound has 2 to 6 polymerizable groups in the molecule. The composition for forming a polarizing film according to claim 1 or 2, wherein the content of the polymerizable non-liquid crystal compound is 3 parts by mass or more and 10 parts by mass or less based on 100 parts by mass of the polymerizable liquid crystal compound. A method for producing a polarizing film, comprising the steps of (I), (II), and (III): (I) applying the composition for forming a polarizing film according to any one of claims 1 to 6 to a substrate a step of forming a coating film by removing the solvent on the alignment film formed on the substrate; (II) making the polymerizable liquid crystal compound contained in the coating film formed in (I) into a smectic liquid crystal phase state (III) A step of copolymerizing a polymerizable liquid crystal compound and a polymerizable non-liquid crystal compound in a coating film in a state of a smectic liquid crystal phase in the polymerizable liquid crystal compound formed in (II). The method for producing a polarizing film according to claim 7, wherein the substrate is a transparent substrate on which alignment treatment is carried out. The method for producing a polarizing film according to claim 7 or 8, wherein the step (II) comprises the steps of the step (I-1) and the step (I-2), and the step (I-1) is subjected to heat treatment until (I) The polymerizable liquid crystal compound contained in the coating film formed in the step exhibits a nematic liquid crystal phase, and the step (I-2) is such that the polymerizable liquid crystal compound formed in the step (I-1) is a nematic The coating film in a liquid crystal phase state is cooled until the polymerizable liquid crystal compound exhibits a smectic liquid crystal phase. A polarizing film manufactured by the manufacturing method according to any one of claims 7 to 9. The polarizing film of claim 10, wherein the Bragg peak is displayed in the diffraction measurement of the X-ray. A display device comprising a polarizing film as claimed in claim 10 or 11.