CN103173227B - Form the compositions used by polarization film and polarization film - Google Patents

Abstract

An object of the present invention is to provide a composition for forming a thin and highly transparent polarizing film, and a polarizing film formed from the composition for forming the polarizing film. The solution of the present invention is to provide a polarizing film that contains a polymerizable liquid crystal compound, a polymerizable non-liquid crystal compound, a dichroic dye, a photopolymerization initiator, and a solvent, and satisfies the following (A) and (B) requirements. A composition and a polarizing film formed from the composition used for forming the polarizing film. (A) Both the polymerizable liquid crystal compound and the polymerizable non-liquid crystal compound contain a polymerizable group; (B) The polymerizable liquid crystal compound contained in the coating film obtained from the composition used to form a polarizing film does not appear in a phase-separated state , instead showing a nematic liquid crystal phase and a smectic liquid crystal phase.

Description

Composition for forming polarizing film and polarizing film

technical field

The present invention relates to a composition used for forming a polarizing film, a polarizing film manufactured from the composition used for forming the polarizing film, a manufacturing method thereof, and the like.

Background technique

In recent years, liquid crystal display devices are increasingly required to be thinner, and at the same time, polarizers used in the liquid crystal display devices are also required to be made of thinner materials. In order to realize a thinner polarizer, research has begun to use a film formed from a composition containing a polymerizable liquid crystal compound instead of a film formed from iodine-dyed polyvinyl alcohol as a polarizing film for use in liquid crystal display devices.

A polarizing film formed from a composition containing a polymerizable liquid crystal compound, for example, the polarizing film disclosed in Patent Document 1 that is formed only of a polymerizable smectic liquid crystal compound, a dichroic dye, a photopolymerization initiator and an inhibitor, Meanwhile, Patent Document 2 discloses a polarizing film formed only of a polymerizable liquid crystal compound, a dichroic dye, a polymerization initiator, an inhibitor, a gelling agent, and a solvent.

current technology

patent documents

Patent Document 1: Japanese Patent No. 4719156

Patent Document 2: Japanese Patent Application Publication No. 2008-547062

Contents of the invention

The problem to be solved by the invention

However, polarizing films are required to be thinner and highly transparent.

An object of the present invention is to provide a composition for producing a thin and highly transparent polarizing film, and a polarizing film formed from the composition for forming the polarizing film.

means of solving problems

The present invention includes the following inventions,

[1] A composition for forming a polarizing film, characterized in that it contains a polymerizable liquid crystal compound, a polymerizable non-liquid crystal compound, a dichroic pigment, a polymerization initiator and a solvent, and satisfies the following (A) necessary conditions and (B) Necessary conditions.

(A) Both the polymerizable liquid crystal compound and the polymerizable non-liquid crystal compound contain 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 appear in a phase-separated state, but exhibits a nematic liquid crystal phase and a smectic liquid crystal phase.

(These (A) and (B) requirements are hereinafter referred to as "(requirement A) and "(requirement B)", respectively.)

[2] The composition for forming a polarizing film according to [1], wherein the polymerizable liquid crystal compound is a compound represented by 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 1,4-phenylene that may contain a substituent or cyclohexane-1,4-diyl that may contain a substituent. However, X ^1. At least one of X ² and X ³ is a 1,4-phenylene group that may contain a substituent. The -CH ₂ - constituting the cyclohexane-1,4-diyl group can be replaced by -O-, -S- Or -NR-substituted. R represents an alkyl or phenyl group with 1 to 6 carbon atoms. Y ¹ and Y ² independently represent -CH ₂ CH ₂ -, -CH ₂ O-, -COO-, -OCOO- , single bond, -N=N-, -CR ^a =CR ^b -, -C≡C- or -CR ^a =N-. R ^a and R ^b independently represent a hydrogen atom or a carbon atom number of 1 to 4 Alkyl group. U ¹ represents a hydrogen atom or a polymerizable group. U ² represents a polymerizable group. W ¹ and W ² independently represent a single bond, -O-, -S-, -COO- or -OCOO-. V ¹ and V ² independently represent an alkylene group having 1 to 20 carbon atoms which may contain a substituent, and -CH ₂ - constituting the alkylene 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 contained in the polymerizable liquid crystal compound and the polymerizable group contained in the polymerizable non-liquid crystal compound are respectively are independently acryloyloxy (CH ₂ =CHCOO-) or methacryloyloxy (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 contained in the polymerizable liquid crystal compound and the polymerizable group contained in the polymerizable non-liquid crystal compound are identical.

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

[7] 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 based on 100 parts by mass of the polymerizable liquid crystal compound, 10 parts by mass or less.

[8] A method for producing a polarizing film including the following steps (I), (II) and (III).

(1) coating the composition used for forming a polarizing film according to any one of [1] to [7] on a substrate or an alignment film formed on a substrate, and removing the solvent to form a coating film;

(II) a step of 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 the polymerizable liquid crystal compound and the polymerizable non-liquid crystal compound in the coating film formed in (II) in which the polymerizable liquid crystal compound is in a smectic liquid crystal phase state;

[9] The method for producing a polarizing film according to [8], wherein the base material is a transparent base material subjected to orientation treatment.

[10] The method for producing a polarizing film according to [8] or [9], wherein the step (II) includes heat-treating the polymerizable liquid crystal compound contained in the coating film formed in the step (I) The step (I-1) of displaying the state of the nematic liquid crystal phase is cooling the coating film in which the polymerizable liquid crystal compound formed in the step (I-1) is in the state of the nematic liquid crystal phase until the polymerizable liquid crystal compound shows a nearly Step (I-2) of crystallizing the liquid crystal phase.

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

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

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

The effect of the invention

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

Description of drawings

FIG. 1 shows a schematic diagram of the key parts of the continuous manufacturing method (Roll to Roll) of the polarizing film of the present invention.

FIG. 2 is a schematic diagram showing a cross-sectional configuration of a liquid crystal display device using a polarizer including the polarizing film of the present invention.

FIG. 3 is a schematic diagram showing the layer sequence of a polarizer containing the polarizing film of the present invention installed in a liquid crystal display device.

Fig. 4 is a schematic diagram showing the layer sequence of a polarizer containing the polarizing film of the present invention installed in a liquid crystal display device.

FIG. 5 is a schematic diagram showing the configuration of a liquid crystal display device (in-cell type) using a polarizer including the polarizing film of the present invention.

Fig. 6 is a schematic cross-sectional view of a circular polarizing plate containing a polarizing film of the present invention.

Fig. 7 is a schematic diagram of a continuous manufacturing method of a circularly polarizing plate containing a polarizing film of the present invention.

Fig. 8 is a schematic diagram showing the configuration of an EL display device using a circularly polarizing plate including the polarizing film of the present invention.

Fig. 9 is a schematic view showing the layer sequence of a circularly polarizing plate including a polarizing film of the present invention provided in an EL display device.

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

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

Explanation of symbols

1 transparent substrate

2 Photo-alignment film

3 pieces of polarizing film

4 phase difference layer

100 polarizing film

210 1st Roller 210A Core

220 Second drum 220A Core

230 3rd drum 230A Core

240 4th drum 240A Core

211A, 211B coating device

212A, 212B drying oven

213A polarized light UV irradiation device

213B Light irradiation device

300 auxiliary roller

10 Liquid crystal display device

11 Anti-reflection layer

12a, 12b polarizing film

13a, 13b retardation film

14a, 14b Substrate

15 color filters

16 transparent electrodes

17 Liquid crystal layer

18 Interlayer insulating film

19 backlight module

20 black matrix

21 thin film transistor

22 pixel electrodes

23 Spacers

24 Liquid crystal display device

30 EL display device

31 circular polarizing plate

33 Substrate

34 Interlayer insulating film

35 pixel electrodes

36 luminous layer

37 Cathode electrode

38 desiccant

39 Package cover

40 thin film transistors

41 Ribs

42 film sealing film

110 circular polarizing plate

111 light source

112 1st lens array

112a lens

113 Second lens array

114 polarized light conversion element

115 compound lens

121, 123, 132 dichroic mirrors

122 mirrors

140R, 140G, 140B LCD panel

142, 143 Polarizer

150 cross dichroic prism

170 projection lens

180 projection screen

Specific implementation form

<Composition for Polarizing Film Formation>

The composition for forming a polarizing film of the present invention (hereinafter sometimes referred to as "the present composition") contains a polymerizable liquid crystal compound, a polymerizable non-liquid crystal compound, a dichroic dye, a polymerization initiator, and a solvent. The polarizing film (hereinafter, sometimes referred to as "this polarizing film") formed by the production method described below from this composition can be used not only for liquid crystal display devices, but also for circularly polarizing plates for organic EL display devices ( Hereinafter, it may be referred to as "the present circularly polarizing plate.") First, the present composition will be described.

<Polymerizable liquid crystal compound>

The polymerizable liquid crystal compound of the present invention contains a polymerizable group, and a coating film formed from the composition does not appear in a phase-separated state, and is a liquid crystal compound having a characteristic of exhibiting a nematic liquid crystal phase and a smectic liquid crystal phase.

Whether or not the coating film formed from this composition satisfies (requirement B) was confirmed in the following manner. The present composition is coated on a glass substrate, and the coated present composition is subjected to heat treatment and/or decompression treatment under the condition that the polymerizable liquid crystal compound and the polymerizable non-liquid crystal compound do not polymerize, and the solvent is removed. Next, 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 phase-separate and showed a nematic liquid crystal phase. Thereafter, the heated coating film was gradually cooled, and it was confirmed whether the polymerizable liquid crystal compound contained in the coating film did not phase-separate and showed a smectic liquid crystal phase. Confirmation of the nematic liquid crystal phase and the smectic liquid crystal phase is performed, for example, by texture observation with a polarizing microscope, X-ray diffraction measurement, or differential scanning calorimetry. Whether or not phase separation is formed is confirmed by, for example, surface observation with various microscopes or scattering degree measurement with a nephelometer.

The smectic liquid crystal phase exhibited by the polymerizable liquid crystal compound is preferably a higher order smectic phase. The high-order smectic phases referred to here include smectic B phase, smectic D phase, smectic E phase, smectic F phase, smectic G phase, smectic H phase, smectic I phase, smectic J phase, Among the smectic K phase and the smectic L phase, the smectic B phase, the smectic F phase, and the smectic I phase are preferable. When the smectic liquid crystal phase displayed by the polymerizable liquid crystal compound is such a higher-order smectic phase, this polarizing film with a higher degree of orientation order can be produced. At the same time, the above-mentioned polarizing film with a higher degree of orientation order can obtain Bragg peaks from hexatic phase or higher-order structures such as crystals in X-ray diffraction measurement.

As the polymerizable liquid crystal compound, a compound whose phase transition temperature from a nematic liquid crystal phase to a smectic liquid crystal phase is 40 to 200°C is preferable, and a compound is more preferably 60 to 140°C.

As a preferable polymeric liquid crystal compound, the compound represented by formula (1) (it may be called "compound (1)" below) is mentioned, for example.

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 contain a substituent or a cyclohexane-1,4-diyl group which may contain a substituent. However, at least one of X ¹ , X ² and X ³ is a 1,4-phenylene group which may contain a substituent. -CH ₂ - constituting cyclohexane-1,4-diyl may be substituted by -O-, -S- or -NR-. R represents an alkyl group or phenyl group having 1 to 6 carbon atoms.

Y ¹ and Y ² each independently represent -CH ₂ CH ₂ -, -CH ₂ O-, -COO-, -OCOO-, 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 each independently represent a single bond, -O-, -S-, -COO- or -OCOO-.

V ¹ and V ² each independently represent an alkylene group having 1 to 20 carbon atoms that may contain a substituent, and -CH ₂ - constituting the alkylene group may be substituted by -O-, -S- or -NH- .

In compound (1), at least two of X ¹ , X ² and X ³ are preferably 1,4-phenylene groups which may contain substituents.

The 1,4-phenylene which may contain a substituent is preferably unsubstituted. The cyclohexane-1,4-diyl that may contain substituents is preferably trans-cyclohexane-1,4-diyl that may contain substituents, and the trans-cyclohexane-1,4-diyl that may contain substituents The 1,4-diyl is preferably free of substituents.

Optional substituents of 1,4-phenylene that may contain substituents or cyclohexane-1,4-diyl that may contain substituents include, for example, methyl, ethyl, and butyl, etc. 1~4 alkyl group; cyano group; halogen atom, etc.

Y ¹ of 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, preferably a polymerizable group. Both U ¹ and U ² are preferably polymerizable groups, and at the same time, both are preferably photopolymerizable groups. The photopolymerizable group here refers to a group that participates in polymerization by absorbing light energy. A polymerizable liquid crystal compound containing a photopolymerizable group is advantageous in that it can be polymerized even at a lower temperature. As the photopolymerizable group, a radical polymerizable group is preferable. The radically polymerizable group refers to a group capable of participating in a polymerization reaction by active radicals generated by a polymerization initiator described later.

In ^compound ( ¹ ), the polymerizable groups of U1 and U2 may be different, but are preferably the same. Examples of polymerizable groups include vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, acryloyloxy, methacryloyloxy, oxiranyl and Oxetanyl, etc. Among them, acryloyloxy, methacryloyloxy and vinyloxy are preferable, and acryloyloxy and methacryloyloxy are more preferable.

Examples of the alkylene group ^of V1 and V2 include methylene, ethylene, 1,3 ^- propylene, 1,3-butylene, 1,4-butylene, and 1,5-pentylene 1,6-hexylene, 1,7-heptylene, 1,8-octylene, 1,10-decylene, 1,14-tetradecylene and 1,20-eicosylene Alkyl etc. V1 and V2 are preferably ^an alkylene group having ² to 12 carbon atoms, more preferably an alkylene group having 6 to 12 carbon atoms.

As an optional substituent group in an alkylene group having 1 to 20 carbon atoms that may contain a substituent group, for example, a cyano group and a halogen atom, etc., but the alkylene group is preferably unsubstituted, more preferably unsubstituted A radical and linear alkylene group.

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

Specific examples of the compound (1) include compounds represented by formulas (1-1) to (1-23), respectively. When a specific example of such a compound (1) contains 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 this composition individually or in mixture of 2 or more types. When two or more types are mixed, at least one type is preferably compound (1), more preferably two or more types are compound (1). The mixing ratio when mixing two types 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 this composition is usually below the temperature at which the polymerizable liquid crystal compound phase-transforms into a smectic phase. The polymerization temperature of this composition can be controlled by adjusting the component contained in this composition. Preferably, the temperature at which the polymerizable liquid crystal compound phase transitions to a smectic phase is determined in advance, and components other than the polymerizable liquid crystal compound are adjusted so that the present composition can be polymerized at a temperature lower than the phase transition temperature. When the present composition contains two or more polymerizable liquid crystal compounds, the temperature at which the mixture of the two or more polymerizable liquid crystal compounds phase transitions to the smectic phase is obtained and controlled in the same manner as above.

Among the exemplified compounds (1), formula (1-2), formula (1-3), formula (1-4), formula (1-6), formula (1-7), formula (1-8) are preferred , compounds represented by formula (1-13), formula (1-14) and formula (1-15). By interacting with other polymerizable liquid crystal compounds or polymerizable non-liquid crystal compounds, these compounds can easily maintain the liquid crystal state of the high-order smectic phase at a temperature below the phase transition temperature. Polymerize below.

The content ratio of the polymerizable liquid crystal compound in this 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, with respect to 100 parts by mass of the solid content of this composition, and further Preferably 80 to 90 parts by mass. When the content ratio of the compound (1) is within the above-mentioned range, it is preferable because the orientation tendency of the compound (2) described later is high. The solid content here is the total amount of the components except the solvent in this composition.

The polymerizable liquid crystal compound is produced by a known method described in, for example, Lub et al.

<Polymerizable non-liquid crystal compound>

The polymerizable non-liquid crystal compound of the present invention means a compound that contains a polymerizable group and does not exist in a liquid crystal state between solid and liquid even when the temperature changes.

The polymerizable non-liquid crystal compound preferably (i) does not self-color (absorb visible light), (ii) has compatibility to mix uniformly with the polymerizable liquid crystal compound, and (iii) does not hinder the polymerizable liquid crystal compound Displays the formation of liquid crystal states.

Examples of polymerizable non-liquid crystal compounds include monofunctional acrylates and polyfunctional acrylates. Monofunctional means containing one polymerizable group, and polyfunctional means containing a plurality of polymerizable groups. Since the polymerization reaction of the polymerizable liquid crystal compound and the polymerizable non-liquid crystal compound can proceed continuously, polyfunctional acrylate is preferable. The number of polymerizable groups contained in the polymerizable non-liquid crystal compound is preferably 1 to 6, more preferably 2 to 6.

Preferably, the polymerizable group contained in the polymerizable liquid crystal compound is the same as the polymerizable group contained in the polymerizable non-liquid crystal compound.

In addition, when at least one compound selected from the polymerizable liquid crystal compound and the polymerizable non-liquid crystal compound contains a plurality of polymerizable groups, it is preferable that at least one polymerizable group contained in the polymerizable liquid crystal compound is combined with the polymerizable non-liquid crystal compound. At least one polymerizable group contained is the same.

More suitable polymerizable non-liquid crystal compounds include monofunctional compounds having the characteristics of (i), (ii) and (iii) above, and containing 1 to 6, preferably 2 to 6, polymerizable groups in the molecule. Acrylates and multifunctional acrylates. In addition, since the above-mentioned monofunctional acrylate and polyfunctional acrylate are non-liquid crystalline, it is preferable not to have a mesogenic structure. At the same time, within the range that does not interfere with the nematic liquid crystal phase and smectic liquid crystal phase of the polymerizable liquid crystal compound contained in the coating film obtained from the composition, the molecule may contain a urethane structure, an amino structure, an epoxy structure, Glycol structure and polyester structure.

The polymerizable non-liquid crystal compound can be used in this composition individually or in mixture of 2 or more types.

Monofunctional acrylates are selected from the group consisting of acryloyloxy (CH ₂ =CH-COO-) and methacryloyloxy (CH ₂ =C(CH ₃ )-COO-) in its molecule Group (hereinafter, sometimes referred to as (meth)acryloyloxy group.) compound. When the polymerizable non-liquid crystal compound is a monofunctional acrylate, it is preferable that the polymerizable liquid crystal compound also contains a (meth)acryloyloxy group.

Examples of monofunctional acrylates containing one (meth)acryloyloxy group include alkyl esters of (meth)acrylic acid having 4 to 16 carbon atoms, β carboxyl groups of (meth)acrylic acid having 2 to 14 carbon atoms, Alkyl esters, alkyl-substituted phenyl esters of (meth)acrylic acid having 2 to 14 carbon atoms, methoxypolyethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate And isobornyl (meth)acrylate, etc.

Multifunctional acrylates are usually compounds containing 2 to 6 methacryloyloxy groups in their molecules. When the polymerizable non-liquid crystal compound is a polyfunctional acrylate, it is preferable that the polymerizable liquid crystal compound also contains a (meth)acryloyloxy group.

As bifunctional acrylates containing two (meth)acryloxy groups, for example, 1,3-butanediol di(meth)acrylate; 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; Bis(acryloyloxyethyl) ether of bisphenol A; Ethoxy bisphenol A di(meth)acrylate; propoxylated neopentyl glycol di(meth)acrylate; ethoxylated neopentyl glycol di(meth)acrylate and 3-methylpentanediol Alcohol di(meth)acrylate, etc.

As polyfunctional acrylates containing 3 to 6 (meth)acryloyloxy groups, there are exemplified trimethylolpropane tri(meth)acrylate; pentaerythritol tri(meth)acrylate; tris(2-hydroxyethyl) base) isocyanurate tri(meth)acrylate; ethoxylated trimethylolpropane tri(meth)acrylate; propoxylated trimethylolpropane 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;

The reactant of pentaerythritol tri(meth)acrylate and acid anhydride; the reactant of dipentaerythritol penta(meth)acrylate and acid anhydride;

The reactant of tripentaerythritol hepta(meth)acrylate and acid anhydride;

Caprolactone-modified trimethylolpropane tri(meth)acrylate; caprolactone-modified pentaerythritol tri(meth)acrylate; caprolactone-modified tris(2-hydroxyethyl)isocyanurate Tri(meth)acrylate; Caprolactone-modified pentaerythritol tetra(meth)acrylate; Caprolactone-modified dipentaerythritol penta(meth)acrylate; Caprolactone-modified dipentaerythritol hexa(meth)acrylate Esters; Caprolactone-modified tripentaerythritol tetra(meth)acrylate; Caprolactone-modified tripentaerythritol penta(meth)acrylate; Caprolactone-modified tripentaerythritol hexa(meth)acrylate; Caprolactone Modified tripentaerythritol hepta(meth)acrylate; Caprolactone modified tripentaerythritol octa(meth)acrylate; Caprolactone modified pentaerythritol tri(meth)acrylate and acid anhydride reactant; Caprolactone modified The reactant of dipentaerythritol penta(meth)acrylate and acid anhydride, and caprolactone-modified tripentaerythritol hepta(meth)acrylate and acid anhydride. In addition, in the specific example of the polyfunctional acrylate shown above, (meth)acrylate means acrylate or methacrylate. Meanwhile, caprolactone modification means that a ring-opened body or a ring-opened polymer of caprolactone is introduced between the alcohol moiety derived from the (meth)acrylate compound and the (meth)acryloyloxy group.

Such a polyfunctional acrylate can use a commercial item. Examples of such commercially available products include A-DOD-N, A-HD-N, A-NOD-N, APG-100, APG-200, APG-400, A-GLY-9E, A-GLY- 20E, 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", same as "M-325", same as "M-240", same as "M-270", same as "M-309", same as "M-310", same as "M-321", same "M-350", same as "M-360", same as "M-305", same as "M-306", same as "M-450", same as "M-451", same as "M-408", same as " M-400", Same as "M-402", Same as "M-403", Same as "M-404", Same as "M-405", Same as "M-406" (manufactured by Toagosei Co., Ltd.), "EBECRYL11" Same as "145", same "150", same "40", same "140", same "180", DPGDA, HDDA, TPGDA, HPNDA, PETIA, PETRA, TMPTA, TMPEOTA, DPHA, EBECRYL series (DAICEL CYTEC ( Daicel Sitec) Co., Ltd.), etc.

As preferable polyfunctional acrylate, the compound respectively represented by following formula (4-1)-(4-14) is mentioned, for example.

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, more preferably 3 to 7% by mass based on the total mass of the composition. More preferably, it is 0.1-19 mass parts with respect to 100 mass parts of solid content of this composition, More preferably, it is 1-15 mass parts, Especially preferably, it is 4-10 mass parts. 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 polymerizable component in the composition can be made (Polymerizable liquid crystal compound and polymerizable non-liquid crystal compound) are copolymerized, so it is preferable. Although it also varies with the types of the polymerizable liquid crystal compound and the polymerizable non-liquid crystal compound, when the content of the polymerizable non-liquid crystal compound exceeds the above range, the transparency of the polarizing film tends to decrease. Therefore, it is not preferred.

<Dichroic Pigment>

A dichroic dye is 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. If it has the above properties, the dichroic pigment can be a dye, it can also be a pigment, and it can also be a mixture of various compounds.

As the aforementioned dichroic dye, one having a maximum absorption wavelength (λMAX) in the range of 300 to 700 nm is preferable. Examples of such dichroic dyes include acridine dyes, oxazine dyes, cyanine dyes, naphthalene dyes, azo dyes, and anthraquinone dyes, among which azo dyes are preferable. Examples of the azo dyes include monoazo dyes, disazo dyes, trisazo dyes, tetrasazo dyes, and stilbene azo dyes, among which disazo dyes and trisazo dyes are preferable.

As an azo dye, the compound (it may be called "compound (2)" hereafter) represented by formula (2), for example is mentioned.

A ¹ (-N=NA ² ) _p -N=NA ³ (2)

[In formula (2), A ¹ and A ³ each independently represent a phenyl group that may contain a substituent, a naphthyl group that may contain a substituent, or a monovalent heterocyclic group that may contain a substituent. A2 represents an optionally substituted ^p -phenylene group, an optionally substituted naphthalene-1,4-diyl group, or an optionally substituted divalent heterocyclic group. p represents an integer of 1 to 4. When p is an integer of 2 or more, a plurality of A ² may be the same or different. ]

Examples of monovalent heterocyclic groups include groups obtained by removing one hydrogen atom from heterocyclic compounds such as quinoline, thiazole, benzothiazole, thienothiazole, imidazole, benzimidazole, oxazole, and benzoxazole. group. A group obtained by removing two hydrogen atoms from a heterocyclic compound is a divalent heterocyclic group, and specific examples of the heterocyclic compound are as described above.

Substitutions optionally contained in the phenyl, naphthyl, and monovalent heterocyclic groups in A1 and A3, and the ^{p -} phenylene, naphthalene ^- 1,4-diyl, and divalent heterocyclic groups in A2 Groups, for example, alkyl groups with 1 to 4 carbon atoms; alkoxy groups with 1 to 4 carbon atoms such as methoxy, ethoxy and butoxy; trifluoromethyl groups with 1 to 4 carbon atoms fluoroalkyl; cyano; nitro; halogen atom; substituted or unsubstituted amino such as amino, diethylamino and pyrrolidinyl (substituted amino refers to an alkane with 1 or 2 carbon atoms An amino group, or an amino group in which two substituted alkyl groups are combined to form an alkylene group with 2 to 8 carbon atoms. The unsubstituted amino group is -NH ₂ -.) In addition, specific examples of alkyl groups with 1 to 6 carbon atoms Examples of the optional substituents such as phenylene in the compound (1) are the same as the examples given.

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

[In the formulas (2-1) ~ (2-6), B ¹ ~ B ²⁰ independently represent a hydrogen atom, an alkyl group with 1 to 6 carbon atoms, an alkoxy group with 1 to 4 carbon atoms, and a cyano group , nitro group, substituted or unsubstituted amino group (the definitions of substituted amino group and unsubstituted amino group are the same as above), chlorine atom or trifluoromethyl group.

n1 to n4 each independently represent an integer of 0 to 3.

When n1 is ² or more, multiple B2s may be the same or different,

When n2 is more than 2, a plurality of B ⁶ may be the same or different,

When n3 is more than 2, a plurality of B ⁹ may be the same or different,

When n4 is 2 or more, a plurality of B ¹⁴ may be the same or different. ]

As the above-mentioned anthraquinone dye, a compound represented by the formula (2-7) is preferable.

[In 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 the above-mentioned oxazine dye, a compound represented by formula (2-8) is preferable.

[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. ]

As the above-mentioned acridine dye, a compound represented by the formula (2-9) is preferable.

[In the formula (2-9), R ¹⁶ to R ²³ 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. ]

In the formula (2-7), the formula (2-8) and the formula (2-9), the alkyl group having 1 to 4 carbon atoms represented as R ^x includes, for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc. An aryl group, a pentyl group, a hexyl group, etc. as a carbon number 6-12, for example, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, etc. are mentioned.

As the above-mentioned cyanine dye, compounds represented by formula (2-10) and compounds represented by formula (2-11) are preferable.

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

n5 represents an integer from 1 to 3. ]

[In formula (2-11), D ³ and D ⁴ each independently represent a group shown in any one of formula (2-11a) ~ formula (2-11h).

n6 represents an integer from 1 to 3. ]

The content of the dichroic dye in the composition is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, more preferably 0.1 to 20 parts by mass, relative to 100 parts by mass of the content of the polymerizable liquid crystal compound. It is not less than 10 parts by mass, particularly preferably not less than 0.1 parts by mass and not more than 5 parts by mass. If the content of the dichroic dye is within this range, the polymerizable liquid crystal compound and the polymerizable non-liquid crystal can be formed without disturbing the orientation of the polymerizable liquid crystal compound contained in the coating film obtained from the composition. The compound is polymerized, so it is preferable. Too much content of the dichroic dye may hinder the orientation of the polymerizable liquid crystal compound. Therefore, the content of the dichroic dye may also be determined within a range in which the polymerizable liquid crystal compound is kept in a liquid crystal state.

As the dichroic dye, commercially available ones can be used.

<polymerization initiator>

This composition contains a polymerization initiator. The polymerization initiator is a compound capable of initiating a polymerization reaction of a polymerizable liquid crystal compound or the like. As the polymerization initiator, a photopolymerization initiator capable of generating active radicals by the action of light is preferable.

Examples of photopolymerization initiators include benzoin compounds, benzophenone compounds, phenalkone compounds, acylphosphine oxide compounds, triazine compounds, iodonium salts, and sulfonium salts.

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

Benzophenone compounds, for example, benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl diphenyl sulfide, 3, 3',4,4'-Tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc.

Phenyl ketone compounds, such as diethoxyacetophenone, 2-methyl-2-morpholine-1-(4-methylthiophenyl)propan-1-one, 2-benzyl-2 -Dimethylamino-1-(4-morpholinephenyl)butan-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1,2-diphenyl- 2,2-Dimethoxyethane-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxyl ring Oligomers of hexylphenyl ketone and 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one, etc.

Acylphosphine oxide compounds include, for example, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide.

Triazine compounds, for example, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl) )-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1, 3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2, 4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[ 2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3, 4-dimethoxyphenyl)vinyl]-1,3,5-triazine, etc.

As a polymerization initiator, commercially available items can be used. Examples of commercially available polymerization initiators include “Irgacure 907”, “Irgacure 184”, “Irgacure 651”, “Irgacure 819”, “Irgacure 250”, and “Irgacure 369” (Chiba Japan Co., Ltd. ); "セィクォール BZ", "セィクォールZ", "セィィクォールBEE" (Seiko Chemical Co., Ltd.); "kayacure BP100" (Nippon Kayaku Co., Ltd.); UVI-6992" (manufactured by Dazu Corporation); "アデカスベルトマ-SP-152", "アデカビプトマ-SP-170" ((Co., Ltd.) ADEKA); "TAZ-A", "TAZ-PP" (Nippon シィベルヘグナナ) ; and "TAZ-104" (Sanwa Chemical Corporation), etc.

The content of the polymerization initiator in the present composition can be appropriately adjusted according to the type and amount of the polymerizable liquid crystal compound, and is usually 0.1 to 30 parts by mass relative to 100 parts by mass of the content of the polymerizable liquid crystal compound. Preferably it is 0.5-10 mass parts, More preferably, it is 0.5-8 mass parts. If the content of the polymerization initiator is within this range, the polymerizable liquid crystal compound and the polymerizable non-liquid crystal compound can be copolymerized without disturbing the orientation of the polymerizable liquid crystal compound contained in the coating film obtained from the composition. , so it is preferred.

<solvent>

This composition contains a solvent. As the solvent, a solvent capable of completely dissolving the polymerizable liquid crystal compound, the polymerizable non-liquid crystal compound, and the dichroic dye is preferable. Also, a solvent that is inert during the polymerization reaction of the present composition is preferred.

As the solvent, for example, 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 Ester, ethylene glycol methyl ether acetate, γ-butyrolactone or propylene glycol methyl ether acetate and ethyl lactate and other ester solvents; acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, Ketone solvents such as 2-heptanone and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane and n-heptane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; tetrahydrofuran and dimethoxy Ether solvents such as ethyl ethane; chlorine-containing solvents such as chloroform and chlorobenzene, etc. These solvents may be used alone or in combination.

The content of the solvent is preferably 50 to 98% by mass relative to the total amount of the composition. In other words, the solid content in the present composition is preferably 2 to 50% by mass. When the solid content is 2 mass % or more, since this polarizing film tends to be obtained more easily, it is preferable. In addition, when the solid content is 50 mass % or less, since the viscosity of the present composition is low, the thickness of the present polarizing film is substantially uniform, and unevenness tends to hardly occur in the present polarizing film, so it is preferable. Meanwhile, such a solid content is determined according to the thickness of the present polarizing film to be produced.

The present composition may contain components other than the above-mentioned components, and examples of such components include polymerization reaction assistants for controlling polymerization reactions of polymerizable liquid crystal compounds and the like.

<Polymerization Auxiliary>

This composition may further contain a sensitizer. As the sensitizer, a photosensitizer is preferable. Examples of the sensitizer include xanthone-based compounds such as xanthone and thioxanthone (for example, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, etc.), anthracene and Anthracene compounds such as alkoxy-containing anthracene (for example, dibutoxyanthracene, etc.); phenothiazine, rubrene, and the like.

When the present composition contains a sensitizer, the polymerization reaction of the polymerizable liquid crystal compound and the polymerizable non-liquid crystal compound contained in the present composition can be further accelerated. Such a sensitizer is used in an amount of preferably 0.1 to 30 parts by mass, more preferably 0.5 to 10 parts by mass, and still more preferably 0.5 to 8 parts by mass relative to 100 parts by mass of the total amount of the polymerizable liquid crystal compound.

In order to stabilize the polymerization reaction, this composition may contain a polymerization inhibitor appropriately. By containing the polymerization inhibitor, it is possible to control the progress of the polymerization reaction of the polymerizable liquid crystal compound and the polymerizable non-liquid crystal compound.

Examples of the above-mentioned polymerization inhibitor include hydroquinone and alkoxy-containing hydroquinone, alkoxy-containing catechol (such as butyl catechol, etc.), pyrogallic acid, 2, 2, 6, Radical scavengers such as 6-tetramethyl-1-piperidinyloxy radical, thiophenols, β-naphthylamines, β-naphthols, and the like.

When the composition contains a polymerization inhibitor, its content is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 10 parts by mass, and still more preferably 0.5 to 8 parts by mass, based on 100 parts by mass of the polymerizable liquid crystal compound. If the content of the polymerization inhibitor is within this range, polymerization can be carried out without disturbing the orientation of the polymerizable liquid crystal compound contained in the composition used to form the polarizing film, so the polymerizable liquid crystal compound can be more completely formed. Polymerization is carried out while maintaining the liquid crystal state.

<Leveling agent>

The present composition preferably contains a leveling agent. The leveling agent can adjust the fluidity of the present composition, and has a function of making the coating film obtained by applying the present composition more flat, and examples thereof include surfactants and the like. The leveling agent is more preferably at least one selected from the group consisting of a leveling agent mainly composed of a polyacrylate compound and a leveling agent mainly composed of a compound containing a fluorine atom. In addition, the polyacrylate compound here does not contain a polymerizable group.

Leveling agents mainly composed of polyacrylate compounds, such as "BYK-350", "BYK-352", "BYK-353", "BYK-354", "BYK-355", "BYK-358N" , "BYK-361N", "BYK-380", "BYK-381" and "BYK-392" [BYK Chemie], etc.

Examples of leveling agents mainly composed of compounds containing fluorine atoms include "Mega-fac (Megafac) R-08", "R-30", "R-90", and "F-410". , Same as "F-411", Same as "F-443", Same as "F-445", Same as "F-470", Same as "F-471", Same as "F-477", Same as "F-479", Same as "F-482" and "F-483" [DIC (Co., Ltd.)]; 393", same as "SC-101", same as "SC-105", "KH-40" and "SA-100" [AGC Seimi Chemical Co., Ltd.]; "E1830", "E5844" [(Co., Ltd.) Daikin Fine Chemical (Daikin Finchem Chemical Research Institute]; "ェフトップ EF301", the same "EF303", the same "EF351" and the same "EF352" [Mitsubishi Material Electronic Chemicals Co., Ltd.], etc.

When the composition contains a leveling agent, its content is preferably 0.3 to 5 parts by mass, more preferably 0.5 to 3 parts by mass, relative to 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 can be easily aligned in parallel, and the obtained polarizing film tends to be smoother, so it is preferable. When content of a leveling agent exceeds the said range with respect to a polymeric liquid crystal compound, since the polarizing film obtained becomes uneven easily, it is unpreferable. Moreover, this composition may contain 2 or more types of leveling agents.

<Formation method of this polarizing film>

Next, the method of forming this polarizing film from this composition is demonstrated. First, the present composition is coated on a substrate or an alignment film formed on the substrate. It is preferably applied on an alignment film formed on a substrate. A transparent substrate is preferred as the substrate.

<Transparent substrate>

A transparent substrate refers to a substrate having transparency to such an extent that light, especially visible light, can be transmitted. This transparency is a property of having a transmittance of 80% or more with respect to light in the wavelength range of 380 to 780nm. Specifically, as the transparent substrate, for example, a glass substrate or a plastic substrate is exemplified. In addition, examples of plastics constituting the plastic substrate include polyolefins such as polyethylene, polypropylene, and norbornene-based polymers; cyclic olefin-based resins; polyvinyl alcohol; polyethylene terephthalate; Acrylates; polyacrylates; cellulose esters such as cellulose triacetate, cellulose diacetate, and cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polysulfone; polyethersulfone; Polyether ketone; plastics such as polyphenylene sulfide and polyphenylene ether. Among them, cellulose esters, cyclic olefin resins, polycarbonate, polyethylene terephthalate, or polymethacrylate are particularly preferable because of ease of commercial availability and remarkable transparency. Such a transparent substrate is used in the production of the present polarizing film, and a support substrate or the like may be attached to the transparent substrate from the viewpoint of being less likely to be damaged during transportation and storage and easy to handle. At the same time, as described later, when a circularly polarizing plate is produced from this polarizing film, retardation may be imparted to the plastic substrate. At this time, retardation can be imparted to the plastic substrate by stretching. In addition, a method of imparting phase difference to a transparent substrate will be described later.

Cellulose ester is obtained by esterifying at least a part of hydroxyl groups contained in cellulose with acetic acid. A cellulose ester film made of such a cellulose ester is easily available on the market. Commercially available cellulose triacetate films include, for example, "Fujitack Film" (Fuji Photo Film Co., Ltd.); "KC8UX2M", "KC8UY" and "KC4UY" (Konika Minolta Opto Co., Ltd.). Such a commercially available cellulose triacetate film can be used as a transparent substrate as it is or after imparting retardation properties as needed. At the same time, the surface of the formed transparent substrate can be used as a transparent substrate after surface treatment such as anti-glare treatment, hard coating treatment, anti-static treatment or anti-reflection treatment.

Cyclic olefin-based resins refer to polymers or copolymers (cyclic olefin-based resins) of cyclic olefins such as norbornene or polycyclic norbornene-based monomers. The cyclic olefin-based resins may be partially Contains an open ring structure. Meanwhile, a cyclic olefin-based resin containing a ring-opening portion may be hydrogenated. Furthermore, the cyclic olefin-based resin may be a copolymer of cyclic olefins and chain olefins or vinylated aromatic compounds (styrene, etc.) in view of not significantly affecting transparency and not significantly increasing hygroscopicity. At the same time, polar groups can be introduced into the molecule of the cyclic olefin resin.

When the cyclic olefin-based resin is a copolymer of cyclic olefins and chain olefins or aromatic compounds containing vinyl, the chain olefins are ethylene or propylene, etc., while vinylated aromatic compounds are styrene, α-form Alkyl styrene and alkyl substituted styrene, etc. In such a copolymer, the content ratio of the structural unit derived from the cyclic olefin is not more than 50 mol %, for example, in the range of about 15 to 50 mol % with respect to the total structural units of the cyclic olefin-based resin. When the cyclic olefin-based resin is a terpolymer of cyclic olefin, chain olefin, and vinylated aromatic compound, for example, the content ratio of the structural unit derived from the chain olefin relative to the total amount of the cyclic olefin-based resin The structural unit is about 5 to 80 mol%, and the content ratio 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 high-valent cyclic olefin used is relatively small when the cyclic olefin-based resin is produced.

Cyclic olefin-based resins are readily available on the market. As a commercially available cyclic olefin-based resin, for example, "Topas" [Ticona Corporation (Germany)]; Japan ゼォン (Co., Ltd.)]; "アペル" [Mitsui Chemicals (Co., Ltd.)] and so on. Such a cyclic olefin-based resin is produced into a film (cyclic olefin-based resin film) by, for example, a known film-forming method such as a solvent casting method or a melt-extrusion method. Meanwhile, a commercially available cyclic olefin-based resin film in a film-formed state can also be used. Examples of such commercially available cyclic olefin-based resin films include "エスシナナ" and "SCA40" [Sekisui Chemical Industry Co., Ltd.]; JSR (strain)] and so on.

Next, a method for imparting retardation to a plastic substrate will be briefly described. Plastic substrates can be given retardation properties by known stretching methods. For example, a roll (roll body) in which a plastic base material is wound is prepared, the plastic base material is continuously unwound from the roll body, and the unrolled plastic base material is transported to a heating furnace. The set temperature of the heating furnace is within the range of the glass transition temperature of the plastic substrate (°C) ~ [glass transition temperature + 100] (°C), preferably near the glass transition temperature (°C) ~ [glass transition temperature +50] (°C) range. In this heating furnace, when the plastic substrate is stretched in the forward direction or in a direction perpendicular to the forward direction, the conveying direction or tension is adjusted to incline at an arbitrary angle, and uniaxial or biaxial thermal stretching is performed. The stretching ratio is usually in the range of about 1.1 to 6 times, preferably in the range of about 1.1 to 3.5 times. Meanwhile, the method of stretching in the oblique direction is not particularly limited as long as it continuously inclines the orientation axis at a desired angle, and a known stretching method can be used. Such stretching methods include, for example, the methods described in JP-A-50-83482 or JP-A-2-113920.

The thickness of the transparent substrate is preferably thin in order to have a practical weight and ensure sufficient transparency, but excessively thin tends to lower strength and lower workability. 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 this polarizing film is used as a circular polarizing plate described later, especially when used as a circular polarizing plate for mobile equipment, the thickness of the transparent substrate is preferably thinner. When using a glass substrate, the thickness is preferably about 100 to 500 μm. In the case of a plastic base material, the thickness is preferably about 20 to 100 μm. In addition, when imparting phase difference to a plastic substrate by stretching, the thickness after stretching is determined by the thickness before stretching and the stretching ratio.

<Orientation film>

It is preferable to form an alignment film on the base material used when manufacturing this polarizing film. At this time, the present composition is coated on the alignment film. Therefore, the alignment film preferably has solvent resistance such that the present composition does not dissolve when applied. At the same time, it is preferable to have heat resistance in the heat treatment for removing the solvent and aligning the liquid crystal. Such an alignment film can be formed using an alignment polymer.

As the above-mentioned alignment polymer, for example, polyamide or gelatin having an amide bond in the molecule, polyimide having an imide bond in the molecule and polyamic acid, polyvinyl alcohol, alkyl Polymers such as modified polyvinyl alcohol, polyacrylamide, polyoxazole, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid or polyacrylates. Among them, polyvinyl alcohol is preferable. These alignment polymers which form an alignment film may be used individually or in mixture of 2 or more types.

The alignment polymer can be applied on a substrate as an alignment polymer composition (orientation polymer-containing solution) dissolved in a solvent to form an alignment film on the substrate. As the solvent, for example, water; alcohol solvents such as methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ethyl acetate, butyl acetate , ethylene glycol, methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate and ethyl lactate and other ester solvents; acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, Ketone solvents such as methyl amyl ketone and 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; tetrahydrofuran and dimethoxy Ether solvents such as ethyl ethane; chlorine-substituted hydrocarbon solvents such as chloroform and chlorobenzene, etc. These organic solvents may be used alone or in combination.

Meanwhile, in order to form an alignment film, a commercially available alignment film material can be used as the alignment polymer composition. Examples of commercially available alignment film materials include Suneba (registered trademark, manufactured by Nissan Chemical Industry Co., Ltd.), Optoma (registered trademark, JSR Corporation), and the like.

As a method of forming an alignment film on the above-mentioned substrate, for example, coating the above-mentioned alignment polymer composition or a commercially available alignment film material on the above-mentioned substrate, and then annealing can form an alignment film on the above-mentioned substrate. . 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 anchor force to the alignment film, rubbing (rubbing method) is preferably performed as necessary. The polymerizable liquid crystal compound can be aligned in a desired direction by imparting an alignment anchoring force.

As a method of imparting alignment anchoring force by a rubbing method, for example, there is a rotating rubbing roll with a rubbing cloth wound around it, and a laminate in which a coating film for alignment film formation is formed on a substrate is placed on a table and transported to A rotating rubbing roll, a method of bringing the coating film for forming an alignment film into contact with a rotating rubbing roll.

Meanwhile, a so-called photo-alignment film may also be used. The photo-alignment film refers to coating a composition containing a polymer having a photoreactive group or a monomer and a solvent (hereinafter sometimes referred to as a "composition for forming a photo-alignment layer") on a substrate. A photo-alignment-inducing layer is formed on the base material, and an alignment anchoring force is given to the photo-alignment-inducing layer by irradiation with polarized light (preferably polarized light UV), thereby forming an alignment film with a photo-alignment layer. A photoreactive group is a group which produces liquid-crystal orientation ability by irradiation with light (photoirradiation). Specifically, it is a photoreactive group that induces orientation or isomerization reaction, dimerization reaction, photocrosslinking reaction, or photodecomposition reaction of product molecules by light irradiation, which induces liquid crystal orientation ability. Among the photoreactive groups, those that undergo a dimerization reaction or a photocrosslinking reaction are preferred because they have excellent orientation and maintain a smectic liquid crystal state when forming a polarizing film. As the photoreactive group for the above reaction, it is preferred to contain an unsaturated bond, especially a double bond, especially preferably containing a carbon-carbon double bond (C=C bond), a carbon-nitrogen double bond (C=N bond), At least one group selected from the group consisting of nitrogen-nitrogen double bond (N=N bond) and carbon-oxygen double bond (C=O bond).

Examples of the photoreactive group containing a C=C bond include a vinyl group, a polyalkenyl group, a stilbene group, a styrylpyridyl group, a heterostilbene group, a chalcone group, and a cinnamoyl group. Examples of photoreactive groups containing a C=N bond include groups containing structures such as aromatic Schiff bases and aromatic hydrazones. As a photoreactive group containing an N=N bond, for example, there are azophenyl, azonaphthyl, aromatic heterocyclic azo, disazo, formazan, etc., or azobenzene oxide, etc. group for the basic structure. As a photoreactive group containing C=O, a benzophenone group, a coumarin group, an anthraquinone group, a maleimide group etc. are mentioned, for example. These groups may contain substituents such as alkyl, alkoxy, aryl, allyloxy, cyano, alkoxycarbonyl, hydroxyl, sulfonic acid, and alkyl halides.

Among them, photoreactive groups that can undergo photodimerization reactions are preferred, preferably cinnamoyl groups and chalcone groups, because the necessary amount of polarized light irradiation is relatively small during its photoalignment, and it is easy to obtain thermal stability and time stability. Excellent photo-alignment layer. Furthermore, as a photoreactive group-containing polymer, it is particularly preferable that the terminal portion of the side chain of the polymer has a cinnamoyl group constituting a cinnamic acid structure.

As a solvent of the composition used for forming a photo-alignment layer, the solvent which dissolves the polymer which has a photoreactive group, and a monomer is preferable, As this solvent, the solvent used for the said alignment polymer composition is mentioned, for example.

With respect to the composition used for forming the photo-alignment layer, the polymer containing the photoreactive group or the concentration of the monomer can be based on the type of the polymer or the monomer containing the photo-reactive group and the photo-alignment film to be manufactured. The thickness is appropriately adjusted, but when expressed as a solid content concentration, it is preferably at least 0.2% by mass, particularly preferably in the range of 0.3 to 10% by mass. Meanwhile, the composition may contain a polymer material such as polyvinyl alcohol or polyimide, or a photosensitizer within a range that does not significantly impair the properties of the photo-alignment film.

As the method of applying the composition for forming the photo-alignment layer on the base material, spin coating method, extrusion method, gravure coating method, die coating method, rod coating method, applicator method, etc. can be used. Well-known methods, such as a coating method, printing methods, such as a flexo printing method, etc. are used. In addition, when producing the present polarizing film, when a continuous production method is carried out in a roll-to-roll system as described later, printing methods such as gravure coating, die coating, or flexo printing are generally used as the coating method.

In addition, when rubbing or polarized light irradiation is performed, a plurality of regions (patterns) having different orientation directions can be formed by shielding.

<Manufacturing method of this polarizing film>

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

Next, the solvent is removed under conditions where the polymerizable liquid crystal compound and the polymerizable non-liquid crystal compound contained in the coating film do not polymerize, thereby forming a coating film. As a removal method, a natural drying method, a ventilation drying method, a heat drying method, and a reduced-pressure drying method etc. are mentioned, for example. Thereafter, the polymerizable liquid crystal composition contained in the coating film is made to exhibit a smectic liquid crystal phase. In this case, it is preferable to make use of the properties of the polymerizable liquid crystal compound to first display a nematic liquid crystal phase in its liquid crystal state, and then transform the nematic liquid crystal phase into a smectic liquid crystal phase. The transition of the liquid crystal phase as described above is carried out by first heating the polymerizable liquid crystal compound contained in the coating film to a temperature above the temperature showing a nematic liquid crystal phase, and then cooling the polymerizable liquid crystal compound to a temperature showing a smectic liquid crystal phase, etc. method.

The temperature at which the polymerizable liquid crystal compound in the coating film exhibits a smectic liquid crystal phase or a nematic liquid crystal phase is obtained by observing the texture of the composition in advance as described above.

When the polymerizable liquid crystal compound and the polymerizable non-liquid crystal compound are polymerized, in order to keep the polymerizable liquid crystal compound in the smectic liquid crystal phase intact, it is preferable to use this composition containing two or more polymerizable liquid crystal compounds as the polymerizable liquid crystal compound. . The use of this composition in which the content ratio of the two or more polymerizable liquid crystal compounds is adjusted has the advantage that after forming a smectic liquid crystal phase via a nematic liquid crystal phase, even at a temperature at which a crystal phase is originally displayed, it may temporarily It will be in a supercooled state, so it is easy to maintain the liquid crystal state of the high-order smectic phase. When two kinds of polymerizable liquid crystal compounds are contained, the content ratio of the two kinds of polymerizable liquid crystal compounds is usually 1:99-50:50, preferably 5:95-50:50, more preferably 10:90-50:50.

Next, the polymerization process 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 becomes a smectic liquid crystal phase, the polymerizable liquid crystal compound and the polymerizable non-liquid crystal compound are polymerized by irradiating energy on the coating film while maintaining the smectic liquid crystal phase. Since this composition contains a polymerization initiator, it is preferable to irradiate the energy which activates a polymerization initiator, For example, light is preferable as an example of energy. As the irradiation light, depending on the kind of the polymerization initiator contained in the coating film, or the kind of the polymerizable liquid crystal compound and the polymerizable non-liquid crystal compound (in particular, the kind of the polymer group containing the polymerizable liquid crystal compound) and the amount thereof, Light is suitably selected among the group of visible light, ultraviolet light, and laser light or by active electron beams. Among them, ultraviolet light is preferable because it is easy to control the progress of the polymerization reaction or the devices involved in the polymerization are widely used in the art. Therefore, it is preferable to select in advance the types of the polymerizable liquid crystal compound, the polymerizable non-liquid crystal compound and the polymerization initiator contained in the present composition so that they can be polymerized by ultraviolet light. At the same time, during polymerization, ultraviolet radiation can also pass through an appropriate cooling device to cool the coating film to control the polymerization temperature. If by adopting such a cooling means, the polymerization of the polymerizable liquid crystal compound and the polymerizable non-liquid crystal compound can be carried out at a lower temperature, then there is a possibility that the polarizing film can be properly formed even if the above-mentioned base material is made of a material with low heat resistance. advantage. In addition, during polymerization, this polarizing film with a pattern can also be obtained by shielding or developing.

Through the above-mentioned polymerization, the above-mentioned polymerizable liquid crystal compound is polymerized while maintaining the liquid crystal state of the smectic phase, preferably the exemplified higher-order smectic phase, to form the present polarizing film. The polarizing film obtained by polymerizing the polymerizable liquid crystal compound in the liquid crystal state of the smectic phase, along with the effect of the above-mentioned dichroic pigment, is polymerized with the conventional host-guest type polarizing film, that is, maintaining the liquid crystal state in the nematic phase. Compared with the polarizing film obtained by polymerizing polar liquid crystal compounds, it has the advantage of higher polarization performance. Further, compared with the polarizing film coated only with dichroic pigment or lyotropic liquid crystal, it has the advantage of higher strength.

The thickness of the present polarizing film thus formed is preferably in the range of 0.5 μm to 10 μm, more preferably 1 μm to 5 μm. Therefore, the thickness of the coating film used to form the present polarizing film is determined in consideration of the thickness of the obtained present polarizing film. In addition, the thickness of the polarizing film is measured by an interference film thickness meter, a laser microscope or a stylus film thickness meter.

Transparency can be assessed by the Haze value. Preferably the turbidity value is below 5%, more preferably below 2%.

Meanwhile, the present polarizing film formed in this manner is particularly preferably one in which Bragg peaks are obtained in X-ray diffraction measurement as described above. As this polarizing film which acquires such a Bragg peak, the present polarizing film which shows the diffraction peak derived from a hexagonal phase or a crystal phase is mentioned, for example.

<Continuous production method of this polarizing film>

The manufacturing method of the polarizing film has been briefly described above. When the polarizing film is manufactured commercially, a method that can continuously manufacture the polarizing film is required. Such a continuous manufacturing method is a method using a roll-to-roll format, and is sometimes referred to as "this manufacturing method". In addition, this manufacturing method is demonstrated centering on the case where a base material is a transparent base material.

This manufacturing method includes, for example,

The process of preparing the first roll obtained by winding the transparent base material on the first core,

The process of continuously sending out the transparent substrate from the first roller,

The process of continuously coating the composition used to form the above-mentioned photo-alignment layer on a transparent substrate,

The process of removing the solvent in the composition used for forming the photo-alignment layer and continuously forming the first coating film on the transparent substrate,

By irradiating the coating film with polarized light UV, continuously forming a photo-alignment layer and forming a photo-alignment film,

On this photo-alignment film, the process of continuously coating this composition,

The process of continuously forming a second coating film on the photo-alignment film by drying the coated composition under conditions where the polymerizable liquid crystal compound and the polymerizable non-liquid crystal compound do not polymerize,

After making the liquid crystal state of the polymerizable liquid crystal compound contained in the coating film into a smectic liquid crystal phase, the process of continuously obtaining a polarizing film by polymerizing the polymerizable liquid crystal compound while maintaining the smectic liquid crystal phase,

A step of winding the continuously obtained laminate containing the transparent substrate, photo-alignment film, and polarizing film around a second core to obtain a second roll.

Here, the present manufacturing method will be described with reference to FIG. 1 .

The first roll 210 in which the transparent base material is wound around the first core 210A is easily available in the market, for example. As such a transparent substrate commercially available in the form of a roll, for example, cellulose ester, cyclic olefin-based resin, polycarbonate, polyethylene terephthalate, etc. among the transparent substrates already exemplified Or polymethacrylate film, etc. Simultaneously, when this polarizing film is used as circularly polarizing plate, the transparent base material that endowed retardation property also is easy to buy in the market in advance, for example has the one made of cellulose ester, polycarbonate or cyclic olefin resin. Retardation film, etc.

Next, the transparent substrate is sent out from the above-mentioned first roller 210 . The method of sending out the transparent base material is to install an appropriate rotating device in the winding core 210A of the first roll 210, and rotate the first roll 210 by the rotating device. In addition, an appropriate auxiliary roller 300 may be provided in the direction in which the first roller 210 sends out the transparent substrate, and the transparent substrate may be sent out by a rotating device of the auxiliary roller 300 . Furthermore, a rotating device may be provided to the first winding core 210A and the auxiliary roller 300 at the same time, and an appropriate tension may be applied to the transparent substrate while feeding it out.

When the transparent substrate sent out from the first roller 210 passes through the coating device 211A, the surface of the transparent substrate is coated with a composition for forming a photo-alignment layer by the coating device 211A. The coating device 211A, which continuously coats the composition for forming the photo-alignment layer as described above, is usually a printing device that can perform coating such as gravure coating, die coating, and flexo printing.

The film passing through the coating device 211A is conveyed to the drying furnace 212A, and heated by the drying furnace 212A to remove the solvent from the coated composition and continuously form the first coating film on the transparent substrate. As the drying furnace 212A, for example, a hot-air drying furnace or the like can be used. The set temperature of the drying oven 212A is determined according to the type of solvent contained in the photo-alignment layer-forming composition applied by the coating device 211A, and the like. At the same time, the drying furnace 212A can be divided into a plurality of regions, each of which can be set to a different temperature, and a plurality of drying furnaces connected in series can also be arranged, and the respective setting temperatures can be different.

The first coating film formed continuously through the heating furnace 212A continuously passes through the polarized light UV irradiation device 213A, and can be irradiated with polarized light UV on the surface of the first coating film or the surface on the transparent substrate side to form photo-alignment. layer to form a photo-alignment film.

The laminate of the base material and the photo-alignment film thus formed continuously passes through the coating device 211B. After coating the composition on the photo-alignment film, it passes through the drying oven 212B to form the polymer contained in the composition. The second coating film in which the neutral liquid crystal compound exhibits a smectic liquid crystal phase. The drying oven 212B is used to remove the solvent in the composition coated on the photo-alignment film, and also to give the composition heat energy, so that the polymerizable liquid crystal compound contained in the composition changes from a nematic liquid crystal phase to a near-nematic liquid crystal phase. Crystalline phase. In order to transform the polymerizable liquid crystal compound from a nematic liquid crystal phase to a smectic liquid crystal phase, the drying oven 212B may perform multi-stage heat treatment. That is, the drying furnace 212B may be divided into a plurality of zones similarly to the drying furnace 212A, and each of the divided multiple zones may be set to a different temperature, or a plurality of drying furnaces may be arranged in series, and each set temperature may be different.

The solvent contained in this composition is fully removed through the film of the drying oven 212B, and the polymerizable liquid crystal compound in the second coating film is kept in a smectic liquid crystal phase, and is transported to the light irradiation device 213B. The polymerizable liquid crystal compound is kept in the smectic liquid crystal phase by the light irradiation of the light irradiation device 213B, and the present polarizing film is continuously formed on the photo-alignment film by photopolymerization together with the polymerizable non-liquid crystal compound.

The present polarizing film formed continuously in this way is wound around the second winding core 220A as a laminate including a transparent base material and a photo-alignment film to obtain a form of the second roll 220 . When obtaining the formed 2nd roll wound with this polarizing film, it can wind together using a spacer suitably.

As mentioned above, the transparent substrate sequentially passes through the first roller/coating device 211A/drying furnace 212A/polarized light UV irradiation device 213A/coating device 211B/drying furnace 212B/light irradiation device 213B, and the light on the transparent substrate The polarizing film is continuously produced on the alignment film.

Simultaneously, this manufacturing method of Fig. 1 shows the continuous manufacturing method from transparent substrate to this polarizing film, but also can for example, make transparent substrate successively pass through the 1st roller/coating device 211A/drying furnace 212A/polarized light UV Irradiation device 213A, the continuously formed laminated body of the substrate and the photo-alignment film is wound around the core, and the laminated body is manufactured in the form of a drum, and the laminated body is sent out from the roller, and the sent out laminated body, This polarizing film is produced by passing through the coating device 211B/drying furnace 212B/light irradiation device 213B in this order.

The present polarizing film obtained by this production method has a film-like and elongated shape. When this polarizing film is used in a liquid crystal display device described later, it can be cut into a desired size according to the scale of the liquid crystal display device and the like.

Above, the structure and production method of this polarizing film have been described centering on the form of the laminated body of transparent substrate/photo-alignment film/this polarizing film, but as a laminated body containing this polarizing film, it can be obtained from the following The laminated body may be a form in which layers or films other than the transparent substrate/photo-alignment film/this polarizing film are laminated after the photo-alignment film or the transparent substrate is removed. As these layers and films, as mentioned above, this polarizing film may further contain a retardation film, and may further contain an antireflection layer or a brightness enhancement film.

At the same time, a circular polarizing plate or an elliptically polarizing plate in the form of a retardation film/photo-alignment film/this polarizing film can be obtained by using the transparent substrate itself as a retardation film. For example, when using a 1/4 wavelength plate obtained by uniaxial stretching as a retardation film, by setting the irradiation direction of polarized light UV to approximately 45° with respect to the transport direction of the transparent substrate, circular polarization can be produced by a roll-to-roll method. Light board. As the 1/4 wavelength plate used in the production of the above-mentioned circularly polarizing plate, it is preferable that the in-plane retardation value with respect to visible light becomes smaller as the wavelength becomes shorter.

Simultaneously, by using the 1/2 wavelength plate as retardation film, make the linear polarizing plate cylinder that sets its slow axis and the angle of the absorption axis of polarizing film to stagger, on the opposite side with the face that forms this polarizing film By forming a 1/4 wavelength plate, a broadband circularly polarized light plate can be obtained.

<Applications of this polarizing film>

The polarizing film can be used in various display devices. A display device is a device including a display element, and includes a light-emitting element or a light-emitting device as a light-emitting source. As the display device, for example, a liquid crystal display device, an organic electroluminescence (EL) display device, an inorganic electroluminescence (EL) display device, an electron emission display device (such as a field emission display device (FED), a surface field emission display device, etc.) device (SED)), electronic paper (display devices using electronic ink or electrophoretic elements, plasma display devices, projection display devices (such as grid light valve (GLV) display devices, display devices containing digital microlens devices (DMD) devices) and piezoelectric ceramic displays, etc. The liquid crystal display device includes any one of a transmissive liquid crystal display device, a semi-transmissive liquid crystal display device, a reflective liquid crystal display device, a direct-view liquid crystal display device, and a projection type liquid crystal display device. These display devices may be display devices that display 2D images, or may be stereoscopic display devices that display 3D images.

The present polarizing film can be effectively used in a display device, particularly an organic electroluminescence (EL) display device or an inorganic electroluminescence (EL) display device.

2 and 5 are schematic diagrams showing a cross-sectional configuration of a liquid crystal display device (hereinafter referred to as "this liquid crystal display device" depending on the occasion) using this polarizing film. The liquid crystal layer 17 is sandwiched between the two substrates 14a and 14b.

FIG. 10 is a schematic diagram showing a cross-sectional structure of an EL display device using the present polarizing film (hereinafter referred to as "the present EL display device" depending on the occasion).

FIG. 11 is a schematic diagram showing the configuration of a projection-type liquid crystal display device using the present polarizing film.

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

The 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 facing the pixel electrodes 22 sandwiching the liquid crystal layer 17 , and the black matrix 20 is disposed at a position facing a boundary between the pixel electrodes. The transparent electrode 16 is disposed on the side of the liquid crystal layer 17 to cover the color filter 15 and the black matrix 20 . In addition, a protective film layer (not shown in the figure) may be included between the color filter 15 and the transparent electrode 16 .

Thin film transistors 21 and pixel electrodes 22 are regularly arranged on the side of the liquid crystal layer 17 of the substrate 14 b. The pixel electrodes 22 are disposed at positions facing the color filters 15 with the liquid crystal layer 17 interposed therebetween. An interlayer insulating film 18 including a connection hole (not shown in the figure) 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 are used. As such a glass substrate or a plastic substrate, the same material as the exemplified material of the transparent substrate used in the production of this polarizing film is used. Meanwhile, the transparent base material of the present polarizing film can also serve as the base material 14a and the base material 14b. When manufacturing the color filter 15 and the thin film transistor 21 formed on the base material, a glass base material or a quartz base material is preferable when a high-temperature heating process is required.

The most suitable material is used for the thin film transistor according to the material of the base material 14b. The thin film transistor 21 includes, for example, a high-temperature polysilicon transistor formed on a quartz substrate, a low-temperature polysilicon transistor formed on a glass substrate, and an amorphous silicon transistor formed on a glass substrate or a plastic substrate. In order to make the present liquid crystal display device more compact, a dry driver IC may be formed on the substrate 14b.

A liquid crystal layer 17 is arranged between the transparent electrode 16 and the pixel electrode 22 . In order to maintain a constant distance between the base material 14 a and the base material 14 b , a spacer 23 is arranged in the liquid crystal layer 17 . In addition, although a columnar spacer is shown in FIG. 2 , the spacer is not limited to a columnar shape, and may have any shape as long as a certain distance can be maintained between the base material 14 a and the base material 14 b.

Alignment layers capable of aligning liquid crystals in desired directions may be disposed on the surfaces of the layers formed by the base material 14 a and the base material 14 b that are in contact with the liquid crystal layer 17 . In addition, the polarizing film can be placed inside the liquid crystal cell, that is, the polarizing film is arranged on the side of the contact surface with the liquid crystal layer 17 . Such a form is called "embedded (in cell) type".

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

Among the substrates 14a and 14b sandwiching the liquid crystal layer 17, polarizers 12a and 12b are provided outside the substrates 14a and 14b, and at least one of the polarizers includes this polarizing film.

Furthermore, it is preferable to laminate retardation layers (for example, 1/4 wavelength plate or optical compensation film) 13a and 13b. Among the polarizers 12a and 12b, the function of converting incident light into linearly polarized light can be given to the liquid crystal display device 10 by incorporating the present polarizing film in the polarizer 12b. In addition, according to the structure of the liquid crystal display device or the type of liquid crystal compound contained in the liquid crystal layer 17, the phase difference films 13a and 13b may not be arranged. In the case of a polarizing plate, since the retardation film can be used as a retardation layer, the retardation layers 13a and/or 13b in FIG. 2 can also be omitted. A polarizing film may be further provided on the light exit side (outer side) of the polarizer including this polarizing film.

Simultaneously, the outer side (when this polarizing film is further provided with polarizing film, on its outside) of the polarizer that contains this polarizing film, can be provided with anti-reflection film for preventing the reflection of external light.

As described above, this polarizing film can be used for the polarizer 12a or 12b of the liquid crystal display device 10 of FIG. 2 .

By arranging the polarizing film in the polarizers 12a and/or 12b, there is an effect of further thinning the liquid crystal display device 10 finally.

When this polarizing film is used in the polarizer 12a or 12b, there is no particular limitation on the lamination sequence thereof. This will be described with reference to the enlarged views of parts A and B surrounded by dotted lines in FIG. 2 .

FIG. 3 is an enlarged cross-sectional schematic view of part A of FIG. 2 . (A1) of FIG. 3 shows that when the polarizer 100 is used as the polarizer 12a, the polarizing film 3, the photo-alignment film 2, and the transparent substrate 1 are arranged in this order on the retardation layer 13a side. Meanwhile, (A2) of FIG. 3 shows that the transparent substrate 1, the photo-alignment film 2, and the present polarizing film 3 are arranged in order on the phase difference layer 13a side.

FIG. 4 is an enlarged schematic view of part B of FIG. 2 . (B1) of FIG. 4 shows that when the polarizer 100 is used as the polarizer 12b, the transparent substrate 1, the photo-alignment film 2, and the polarizing film 3 are arranged in order on the retardation film 13b side. Meanwhile, when (B2) of FIG. 4 shows that the polarizer 100 is used as the polarizer 12b, the polarizing film 3, the photo-alignment film 2, and the transparent substrate 1 are arranged in order on the retardation layer 13b side.

A backlight module 19 as a light source is disposed outside the polarizer 12b. The backlight module 19 includes a light source, a light guide, a reflector, a diffusion sheet, and a viewing angle adjustment sheet. Examples of light sources include electroluminescence, cold cathode tubes, hot cathode tubes, light emitting diodes (LEDs), laser light sources, and mercury lamps. At the same time, the type of the polarizing film can be selected according to the characteristics of the light source.

When the liquid crystal display device 10 is a transmissive liquid crystal display device, the white light generated by the light source in the backlight module 19 is used to enter the light guide body, and the light path is changed by the reflector and diffused in the diffusion sheet. The diffused light is adjusted to a desired directivity through the viewing angle adjustment sheet, and enters the polarizer 12 b from the backlight module 19 .

As unpolarized incident light, only one kind of linearly polarized light passes through the polarizer 12b of the liquid crystal panel. The linearly polarized light is converted into circularly polarized light or elliptically polarized light by the phase difference layer 13b, and then passes through the substrate 14b, the pixel electrode 22, etc. to reach the liquid crystal layer 17 in sequence.

Depending on the presence or absence of a potential difference between the transparent electrodes 16 facing the pixel electrodes 22 here, the alignment state of liquid crystal molecules contained in the liquid crystal layer 17 changes, and the brightness of light emitted from the liquid crystal display device 10 is controlled. When the liquid crystal layer 17 is in the orientation state where polarized light directly passes through it, the polarized light passes through the liquid crystal layer 17 and the transparent electrode 16, and light in a certain wavelength range passes through the color filter 15 to reach the polarizer 12a, and the liquid crystal display device will Displays the maximum brightness of the color determined by the color filter.

Conversely, when the liquid crystal layer 17 is in an alignment state where the polarized light is changed to transmit it, the light transmitted through the liquid crystal layer 17, the transparent electrode 16, and the color filter 15 is absorbed in the polarizer 12a. Through this, the pixel displays black. In the intermediate alignment state between these two states, the luminance of the light emitted from the liquid crystal display device 10 is also intermediate between the above two states, and the pixels at this time display an intermediate color.

When the liquid crystal display device 10 is a transflective liquid crystal display device, it is preferable to use a product obtained by laminating a 1/4 wavelength plate on the polarizing layer side of the polarizing film (circular polarizing plate). In this case, the pixel electrode 22 includes a transmissive portion formed of a transparent material and a reflective portion formed of a light reflective material, and the same image as that of the above-mentioned transmissive liquid crystal display device is displayed in the transmissive portion. On the other hand, in the reflector, external light enters the liquid crystal display device, and through the function of the 1/4 wavelength plate further provided by the polarizing film, the circularly polarized light passing through the polarizing film passes through the liquid crystal layer 17 and passes through the liquid crystal layer 17. The pixel electrode 22 is reflective and thus used for display.

Next, the present EL display device 30 using the present polarizing film will be described with reference to FIG. 8 . When using this polarizing film in this EL display device, it is preferable to use this polarizing film as a circularly polarizing plate (hereinafter sometimes referred to as "this circularly polarizing plate"). This circular polarizing plate usually has two embodiments. Therefore, before describing the configuration and the like of the EL display device 30, two embodiments of the circularly polarizing plate will be described with reference to FIG. 6 .

(A) of FIG. 6 shows a schematic cross-sectional view of the first embodiment of the circular polarizing plate 110 . This first embodiment is a polarizer 100 in which a retardation layer (retardation film) 4 is further provided on a polarizing film 3 and a circular polarizing plate 110 . (B) of Fig. 6 shows a schematic cross-sectional view of the second embodiment of the circularly polarizing plate 110. In this second embodiment, as the transparent base material used in the manufacture of the polarizer 100, the transparent base material 1 (retardation film 4) to which the retardation property has been provided in advance is used, so the transparent base material 1 itself has a function as a retardation layer. 4 functions of the present circular polarizing plate 110.

Here, a method of manufacturing the circularly polarizing plate 110 will be described. Second Embodiment of the Circularly Polarizing Plate 110 As described above, in this manufacturing method of manufacturing the polarizing film 100, it is possible to use the transparent substrate 1 to which retardation has been given in advance, that is, the retardation film, as the transparent substrate. to manufacture. In the first embodiment of the circularly polarizing plate 110 , a retardation film may be bonded on the present polarizing film 3 manufactured by the present manufacturing method B to form the retardation layer 4 . In addition, when the polarizing film 100 is manufactured in the form of the second roller 220 by the manufacturing method B, the polarizing film 100 can be unwound and output from the second roller 220, and can be cut into a predetermined size. A retardation film is pasted on the polarizing film 100; however, it is also possible to prepare a third roll on which the retardation film is wound around a core, and continuously manufacture the circular polarizing plate 110 which is film-shaped and strip-shaped.

The continuous manufacturing method of the first embodiment of the circularly polarizing plate 110 will be described with reference to FIG. 7 . Such a manufacturing method consists of the following steps:

While continuously unwinding and outputting the polarizing film 100 from the above-mentioned second roller 220, the process of continuously unwinding and outputting the above-mentioned retardation film by the third roller 230 wound with the retardation film,

The polarizing layer provided on the polarizing film 100 that is unwound from the second roll 220 and the above-mentioned retardation film that is unwound from the third roll are continuously attached to form the circular polarizing plate 110,

The process of winding the formed circularly polarizing plate 110 into the fourth winding core 240A to obtain the fourth roll 240 .

The manufacturing method of the first embodiment of the circular polarizing plate 110 has been described above. When the polarizing film 3 in the polarizer 100 is bonded with the retardation film, an appropriate adhesive can be used. The formed adhesive layer bonds the polarizing film 3 and the phase difference film together.

Next, the present EL display device including the present 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 arranged on the side opposite to the organic functional layer 36 sandwiching the substrate 33 , and this circular polarizing plate 110 is used for such a circular polarizing plate 31 . By applying a positive voltage to the pixel electrode 35 and a negative voltage to the cathode electrode 37 , a direct current flows 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 emitting source is composed of an electron transport layer, a light emitting layer and a hole transport layer. 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 circular polarizing plate 31 (this circular polarizing plate 110 ). Although an organic EL display device including the organic functional layer 36 has been described, it is also applicable to an inorganic EL display device including an inorganic functional layer.

To manufacture this EL display device 30 , first, a thin film transistor 40 of a desired shape is formed on a substrate 33 . After that, the interlayer insulating film 34 is formed, and then the pixel electrode 35 is formed by sputtering to form a pattern, and then the organic functional layer 36 is laminated.

Next, the circular polarizing plate 31 (this circular polarizing plate 110 ) is provided on the reverse side of the substrate 33 on which the thin film transistor 40 is provided.

When the circularly polarizing plate 110 is used as the circularly polarizing plate 31 , the lamination sequence thereof will be described with reference to the enlarged view of the part C enclosed by the dotted line in FIG. 8 . When this circularly polarizing plate 110 is used as the circularly polarizing plate 31 , the retardation layer 4 is arranged on the substrate 33 side in this circularly polarizing plate 110 . (C1) of FIG. 9 is an enlarged view of the first embodiment of the circular polarizing plate 110 used as the circular polarizing plate 31, and (C2) of FIG. 9 is the second embodiment of the circular polarizing plate 110 used as the circular polarizing plate 31. enlarged view of .

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

As the base material 33 , for example, a sapphire glass base material, a quartz glass base material, a soda glass base material, and a ceramic base material such as alumina; a metal base material such as copper; a plastic base material; and the like. Although not shown in the drawings, a thermally conductive film may be formed on the base material 33 . As a heat conductive film, a diamond thin film (DLC etc.) etc. are mentioned, for example. When the pixel electrode 35 is reflective, light is emitted in a direction opposite to that of the substrate 33 . Therefore, not only transparent materials but also impermeable materials such as stainless steel can be used. The base material may be formed alone, or may be a laminated base material in which a plurality of base materials are bonded together with an adhesive. Meanwhile, these substrates are not limited to a plate shape, but may be a film.

As the thin film transistor 40, for example, a polysilicon transistor or the like can be used. The thin film transistor 40 is disposed at the end of the pixel electrode 35 and has a size of about 10-30 μm. In addition, the size of the pixel electrode 35 is about 20 μm×20 μm to 300 μm×300 μm.

The wiring electrodes of the thin film transistor 40 are provided on the substrate 33 . The resistance of the wiring electrode is low, and it has the function of suppressing the resistance value after it is electrically connected with the pixel electrode 35. Generally, this wiring electrode uses Al, Al and transition metal (excluding Ti), Ti or titanium nitride (TiN) Any one or two or more of them.

An interlayer insulating film 34 is provided between the thin film transistor 40 and the pixel electrode 35 . The interlayer insulating film 34 may be silicon oxide such as SiO ₂ , inorganic materials such as silicon nitride formed by sputtering or vacuum evaporation, or silicon oxide formed by SOG (spin on glass; spin-on-glass method). layer, photoresist, coating film of resin-based materials such as polyimide and acrylic resin, and other insulating materials.

Ribs 41 are formed on the interlayer insulating film 34 . The ribs 41 are arranged around the pixel electrodes 35 (between adjacent pixels). As a material of the rib 41, acrylic resin, polyimide resin, etc. are mentioned, for example. The thickness of the ribs 41 is preferably not less than 1.0 μm and not more than 3.5 μm, more preferably not less than 1.5 μm and not more than 2.5 μm.

Next, an EL element formed of the pixel electrode 35 as a transparent electrode, the organic functional layer 36 as a light-emitting source, and the cathode electrode 37 will be described. Each of the organic functional layers 36 includes at least one hole transport layer and a light-emitting layer, for example, an electron injection and transport layer, a light-emitting layer, a hole transport layer, and a hole injection layer in this order.

The pixel electrode 35 includes, for example, ITO (tin-doped indium oxide), IZO (zinc-doped indium oxide), IGZO, ZnO, SnO ₂ , and In ₂ O ₃ , and is particularly preferably ITO or IZO. The thickness of the pixel electrode 35 is sufficient as long as it sufficiently injects holes, and is preferably 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 inert gases such as Ar, He, Ne, Kr, and Xe, or a mixed gas of these gases can be used.

Metal elements such as K, Li, Na, Mg, La, Ce, Ca, Sr, Ba, Al, Ag, In, Sn, Zn and Zr can be used as the constituent material of the cathode electrode 37. In order to improve the working stability of the electrode, An alloy body having two or three components selected from the exemplified metal elements is preferably used. As the alloy body, for example, Ag·Mg (Ag: 1~20 at%), Al·Li (Li: 0.3~14 at%), In·Mg (Mg: 50~80 at%) and Al·Ca (Ca: 5~ 20at%) etc.

Cathode electrode 37 is formed by vapor deposition and sputtering. The thickness of the cathode electrode 37 is 0.1 nm or more, preferably 1 to 500 nm or more.

The hole injection layer has a function of facilitating hole injection from the pixel electrode 35, and the hole transport layer has a function of transporting holes and blocking electrons, and is 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 and transport layer are not particularly limited, and may vary depending on the formation method, but are preferably about 5 to 100 nm. Various organic compounds can be used for the hole injection layer or the hole transport layer. When forming the hole injecting and transporting layer, the light emitting layer, and the electron injecting and transporting layer, a vacuum vapor deposition method can be used because a homogeneous thin film can be formed.

As the organic functional layer 36 of the light emitting source, a material that emits light (fluorescence) by singlet excitons, a material that emits light (phosphorescence) by triplet excitons, or a material that contains light (fluorescence) by singlet excitons can be used. Materials with materials that emit light (phosphorescence) using triplet excitons, materials formed by organic substances, materials containing materials formed by organic substances and materials formed by inorganic substances, polymer materials, low molecular materials, and materials containing polymers Materials with low molecular weight materials, etc. However, it is not limited thereto, and the organic functional layer 36 using various materials known as EL elements can be used in the EL display device 30 .

A desiccant 38 is arranged in the space between the cathode electrode 37 and the encapsulation cover 39 because the organic functional layer 36 is not resistant to moisture. Moisture absorption by the desiccant 38 can prevent deterioration of the organic functional layer 36 .

FIG. 10 is a schematic diagram showing a cross-sectional configuration of another embodiment of the present EL display device 30 . This EL display device 30 has a sealing structure using a thin film sealing film 41, and can also obtain emitted light from the back surface of the array substrate.

As the thin-film sealing film 41 , it is preferable to use a DLC film obtained by vapor-depositing DLC (diamond-like carbon) on a film of an electrolytic capacitor. DLC film is very difficult to be penetrated by moisture, and has high moisture resistance. At the same time, a DLC film or the like may be directly vapor-deposited on the surface of the electrode 37 . At the same time, the thin film sealing film 41 may also be formed by laminating multiple layers of a resin thin film and a metal thin film.

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

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

FIG. 11 is a schematic diagram showing a projection-type liquid crystal display device using the present polarizing film.

This polarizing film is used for the polarizer 142 and/or the polarizer 143 of the projection type liquid crystal display device.

The light beam emitted by 111 as a light source (such as a high-pressure mercury lamp) as a light source first passes through the first lens array 112, the second lens array 113, the polarized light conversion element 114, and the compound lens 115 to realize the improvement of the brightness of the reflective beam section. Homogenization and polarization.

Specifically, the light beams emitted from the light source 111 are divided into a plurality of tiny light beams by the first lens array 112 formed in a matrix by the microlenses 112 a. The second lens array 113 and compound lens 115 are arranged so that the divided beams of light irradiate the entirety of the three liquid crystal panels 140R, 140G, and 140B to be illuminated, so that the incident-side surfaces of the respective liquid crystal panels form a substantially uniform illuminance as a whole. .

The polarization conversion element 114 is composed of a polarization beam splitting array, and is arranged between the second lens array 113 and the composite lens 115 . In this way, the random polarized light from the light source can be converted into polarized light with a specific polarized direction in advance, reducing the light loss of the polarizer on the incident side described later, and achieving the effect of improving the brightness of the screen.

The above-mentioned uniform brightness and polarized light, through the reflector 122, sequentially pass through the dichroic mirrors 121, 123, 132 to separate the three primary colors of RGB, separate them into the red channel, green channel, and blue channel, respectively incident to the liquid crystal panels 140R, 140G, and 140B.

In the liquid crystal panels 140R, 140G, and 140B, the polarizer 142 is arranged on the incident side, and the polarizer 143 is arranged on the output side. This polarizing film can be used for the polarizer 142 and the polarizer 143 .

The polarizer 142 and the polarizer 143 arranged in each RGB optical path are arranged so that their respective absorption axes are perpendicular to each other. Each of the liquid crystal panels 140R, 140G, and 140B disposed in each optical path has a function of converting the polarization state of each pixel controlled by an image signal into a light quantity.

The present polarizing film 100 is useful as a polarizing film excellent in durability in any optical path of the blue channel, green channel, and red channel by selecting the type of dichroic dye suitable for the corresponding channel.

Based on the image data of the liquid crystal panels 140R, 140G, and 140B, an optical image formed by transmitting incident light with a different transmittance for each pixel is synthesized in the cross dichroic prism 150 and enlarged on the projection screen 180 through the projection lens 170 projection.

Examples of electronic paper include devices that display molecules such as optical anisotropy and dye molecule orientation; devices that display particles such as electrophoresis, particle movement, crystal grain rotation, and phase change; devices that display particles through one end of the film Devices for displaying; devices for displaying by molecular color/phase change; devices for displaying by molecular light absorption; devices for displaying by combining electrons and holes to generate self-luminescence, etc. More specifically, microcapsule type electrophoresis, horizontal movement type electrophoresis, vertical movement type electrophoresis, spherical torsion sphere type, magnetic torsion sphere type, cylindrical torsion sphere type, charged carbon powder, electronic powder fluid, magnetophoresis type, magnetothermal Inductive, electrowetting, light scattering (transparency/turbidity change), cholesteric liquid crystal/photoconductive layer, cholesteric liquid crystal, bistable nematic liquid crystal, ferroelectric liquid crystal, dichroic dye liquid crystal dispersion type, Movable film, color change by leuco dye, photochromic, electrochromic, electrodeposition, flexible organic EL, etc. Electronic paper can be applied not only for personal use of text or images, but also for advertising display (signage), etc. According to the polarizing film, the thickness of electronic paper can be reduced.

As a three-dimensional display device, for example, a method of alternately arranging different retardation films such as the micro polarizing film (μPol) proposed (Japanese Patent Laid-Open No. 2002-185983), when the optical film of the present invention is used as a polarizing film , can be easily patterned by printing, inkjet, photolithography, etc., and therefore, the manufacturing process of the display device can be shortened, and the retardation film is no longer required.

Example

Hereinafter, the present invention will be further described in detail through examples. Unless otherwise specified, "%" and "part" in the following examples represent mass % and a mass part.

In this example, the following polymerizable liquid crystal compounds were used.

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

Compound (1-6) was synthesized by the method described in Lub et al. Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996).

[Measurement of Phase Transition Temperature]

The phase transition temperature of the compound (1-6) is determined by obtaining the phase transition temperature of the film formed from the compound (1-6), and the operation is as follows.

A film made of compound (1-6) was formed on an alignment film formed on a glass substrate, and the phase transition was confirmed by observing the texture with a polarizing microscope (BX-51, manufactured by Olympus Corporation) while heating. temperature. The film formed by compound (1-6) can be confirmed that after the temperature rises to 120°C, when the temperature is lowered, the phase changes to the nematic phase at 112°C, and the phase changes to the smectic A phase at 110°C, and at 94°C Phase transition to smectic B phase.

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

Compound (1-7) was synthesized referring to the synthesis of compound (1-6) above.

[Measurement of Phase Transition Temperature]

The phase transition temperature of compound (1-7) was determined in the same manner as the phase transition temperature of compound (1-6). After the compound (1-7) was heated up to 140°C, when the temperature was lowered, the phase changed to a nematic phase at 133°C, to a smectic A phase at 118°C, and to a smectic B phase at 78°C.

Example 1

[Preparation of this composition etc.]

Mix the following ingredients and stir at 80°C for 1 hour to obtain this composition (composition for forming a polarizing film)

Polymeric 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-Hydroxycyclohexyl phenyl ketone

((イルガキュァ184: manufactured by Ciba Specialty Chemical Co., Ltd.)

6 servings

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

Polymeric non-liquid crystal compound; multifunctional acrylate (4-5) 5.0 parts

Solvent: 250 parts of cyclopentanone

[Measurement of Phase Transition Temperature]

In the same manner as compound (1-6) and compound (1-7), the phase transition temperature of the polymerizable liquid crystal compound contained in the present composition prepared as described above was determined. When the temperature is raised to 140°C, when the temperature is lowered, the phase transitions to a nematic phase at 109°C without forming a phase separation state, and the phase transitions to a smectic A phase at 98°C, without forming a phase separation state, the phase transition occurs at 74°C It is a smectic B phase without forming a phase separation state.

<Manufacture and evaluation of this polarizing film>

1. Formation of Alignment Film

A glass substrate is used as the transparent substrate.

On this glass substrate, a 2% by mass aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 complete saponification type, manufactured by Wako Pure Chemical Industries, Ltd.) (composition for forming an alignment layer) was applied by spin coating, and dried to form A film with a thickness of 100 nm. Next, rubbing treatment was applied to the surface of the obtained film to form an alignment layer, thereby producing a polarizing film. The rubbing process uses a semi-automatic rubbing device (trade name: LQ-008 type, manufactured by Changyang Engineering Co., Ltd.), through a cloth (trade name: YA-20-RW, manufactured by Yoshikawa Chemical Co., Ltd.), at a pressure distance of 0.15mm, and a rotation speed of 500rpm , under the condition of 16.7mm/s. Through such a rubbing treatment, a laminate 1 in which an alignment film was formed on a glass substrate was obtained.

2. Formation of polarizing film

On the alignment film of laminate 1, apply the composition used to form the above-mentioned polarizing film by spin coating, heat and dry on a hot plate at 120°C for 1 minute, and quickly cool to room temperature to form a coating on the above-mentioned alignment film. membrane. The liquid crystal state of the polymerizable liquid crystal compound contained in such a coating film is a smectic B phase. Next, the coating film was irradiated with ultraviolet light at an exposure dose of 2000 mJ/cm ² (based on 313 nm) using a UV irradiation device (SPOT CURE SP-7; manufactured by Usio Electric Co., Ltd.), and the polymerizable liquid crystal contained in the coating film The compound is polymerized while maintaining the above-mentioned liquid crystal state, and a polarizing film is produced from the coating film. At this time, when the thickness of the polarizing film was measured with a laser microscope (OLS3000 manufactured by Olympus Corporation), it was 1.6 μm.

3. X-ray diffraction measurement

The obtained polarizing film was subjected to X-ray diffraction measurement using an X-ray diffractometer X'Pert PRO MPD (manufactured by Spectris Corporation). Using Cu as the target, X-rays generated under the conditions of X-ray tube current 40mA and X-ray tube voltage 45kV pass through the fixed divergence slit 1/2° from the orientation direction, within the scanning range 2θ=4.0~40.0° As a result of scanning measurement with a step width of 2θ=0.01671°, a sharp Bragg peak with half maximum width (FWHM)=about 0.1718° was obtained around 2θ=20.24°. At the same time, the same result can be obtained from the incident direction parallel to the surface of the polarizing film and perpendicular to the alignment direction. The lattice period (order period) (d) obtained from the peak positions is approximately From this, it can be seen that a structure reflecting a higher-order smectic phase is formed.

4. Determination of dichromatic ratio (DR)

The dichroic ratio was measured as follows.

The absorbance (A ¹ ) and Absorbance in the direction of the absorption axis (A ² ). The folding device is equipped with a mesh screen that cuts off 50% of the light quantity on the reference side. The ratio (A ² /A ¹ ) was calculated from the measured values of the absorbance (A ^{1 ) in the transmission axis and the absorbance (A 2 )} in the absorption axis, and it was defined as a dichromatic ratio. The higher the dichroic ratio, the more excellent the properties of the polarizing film. Table 1 shows the maximum absorption wavelength of the absorbance (A ² ) in the absorption axis and the measurement results of the dichromatic ratio at this wavelength.

5. Determination of turbidity value

In order to confirm the transparency of the polarizer, the turbidity value was measured with a turbidity meter (HZ-2; manufactured by Suga Testing Instrument Co., Ltd.). The measurement results are shown in Table 1.

Examples 2 to 8, Reference Example 1, and Comparative Examples 1 to 2 were prepared in the same manner as the present composition except for changing the type and content of the polymerizable non-liquid crystal compound. Meanwhile, in Comparative Example 3, a composition was prepared without adding a polymerizable non-liquid crystal compound, coated and dried at 120° C., and quickly moved to a hot plate at 70° C., and then a polarizing film was made under UV exposure. Table 1 shows the results of the respective measurements.

In Examples 9 to 15, the dichroic pigment was changed to the following structural formula (2-3-1), except that the type and content of the polymerizable non-liquid crystal compound were changed, and other polarizing films were produced in the same manner as in Example 1. Table 1 shows the results of the respective measurements.

Table 1

Examples 1-15 did not appear phase separation state, showing good parallel orientation and high dichroism. Good parallel alignment is because the polymerizable liquid crystal compound shows a nematic liquid crystal phase, and high dichroism is because the polymerizable liquid crystal compound shows a smectic liquid crystal phase.

Industrial availability

The polarizing film is suitable as a display device (display). Therefore, this composition which can manufacture such this polarizing film is industrially highly useful.

Claims (13)

1. a polarization film, is formed by the compositions formed used by polarization film, it is characterised in that described compositions contains poly- Conjunction property liquid-crystal compounds, polymerism non-liquid crystal compound, dichroism pigment, polymerization initiator and solvent, and below meeting (A) essential condition and (B) essential condition, described polymerizable liquid crystal compound is maintained at smectic phase,

(A) polymerizable liquid crystal compound and polymerism non-liquid crystal compound all contain polymerizable group；

(B) polymerizable liquid crystal compound contained in the coated film obtained by the compositions formed used by polarization film does not haves Phase-separated state, and be as cooling and transferred to smectic liquid crystal phase mutually mutually by nematic liquid crystal.

Polarization film the most according to claim 1, it is characterised in that polymerizable liquid crystal compound is the change shown in formula (1) Compound,

U¹-V¹-W¹-X¹-Y¹-X²-Y²-X³-W²-V²-U²(1)

In formula, X¹、X²And X³It is to represent independently of each other containing substituent group or the Isosorbide-5-Nitrae-phenylene without substituent group or contain Substituent group or the hexamethylene-Isosorbide-5-Nitrae-diyl without substituent group, but, X¹、X²And X³Among at least 1 be containing substituent group or Isosorbide-5-Nitrae-phenylene without substituent group；Constitute-the CH of hexamethylene-Isosorbide-5-Nitrae-diyl₂-replaced by-O-,-S-or-NR-or not by Replace；R represents alkyl or the phenyl of carbon number 1～6；Y¹And Y²Expression-CH independently of each other₂CH₂-、-CH₂O-、- COO-,-OCOO-, singly-bound ,-N=N-,-CR^a=CR^b-,-C ≡ C-or-CR^a=N-；R^aAnd R^bRepresent hydrogen independently of each other Atom or the alkyl of carbon number 1～4；U¹Represent hydrogen atom or polymerism base；U²Represent polymerism base, W¹And W²Phase Represent singly-bound ,-O-,-S-,-COO-or-OCOO-independently mutually；V¹And V²Represent independently of each other containing substituent group or not The alkylidene of the carbon number 1～20 containing substituent group, constitutes-the CH of this alkylidene₂-replaced by-O-,-S-or-NH-or not It is replaced.

Polarization film the most according to claim 1 and 2, it is characterised in that polymerism non-liquid crystal compound is simple function third Olefin(e) acid ester or polyfunctional acrylic ester.

Polarization film the most according to claim 1, it is characterised in that the polymerizable group that polymerizable liquid crystal compound contains The polymerizable group contained with polymerism non-liquid crystal compound is independently of one another acryloxy (CH₂=CHCOO-) or first Base acryloxy (CH₂=C (CH₃)COO-)。

Polarization film the most according to claim 1, it is characterised in that the polymerizable group that polymerizable liquid crystal compound contains The polymerizable group contained with polymerism non-liquid crystal compound is identical group.

Polarization film the most according to claim 1, it is characterised in that polymerizable liquid crystal compound intramolecular contains 1～2 Polymerizable group, polymerism non-liquid crystal compound molecule is contained within 2～6 polymerizable groups.

Polarization film the most according to claim 1, it is characterised in that the content of polymerism non-liquid crystal compound is relative to poly- Conjunction property liquid-crystal compounds 100 mass parts, is more than 3 mass parts, below 10 mass parts.

8. the manufacture method of a polarization film, it is characterised in that containing following (I), (II) and (III) operation:

(I) compositions used by polarization film that formed described in any one of claim 1～7 is coated on base material or base material In the alignment films of upper formation, remove solvent and form the operation of coated film；

(II) polymerizable liquid crystal compound contained in the coated film formed in (I) operation is made to become the work of smectic liquid crystal phase state Sequence；

(III), in coated film that formed in (II) operation, that polymerizable liquid crystal compound is smectic liquid crystal phase state, polymerization is made Property liquid-crystal compounds and polymerism non-liquid crystal compound copolymerization operation.

The manufacture method of polarization film the most according to claim 8, it is characterised in that base material implements orientation process Transparent base.

The manufacture method of the polarization film the most according to Claim 8 or described in 9, it is characterised in that (II) operation comprises, and adds Heat treatment is until polymerizable liquid crystal compound contained in the coated film of formation in (I) operation shows the operation of nematic liquid crystal phase (I-1), cool down, directly with by middle for operation (I-1) coated film that this polymerizable liquid crystal compound is nematic liquid crystal phase state formed Operation (I-2) to this polymerizable liquid crystal compound display smectic liquid crystal phase.

11. 1 kinds of polarization films, it is characterised in that by the manufacture method manufacture described in any one of claim 8～10.

12. polarization films according to claim 11, its X-ray diffraction shows bragg peak in measuring.

13. 1 kinds of display devices, it includes the polarization film described in claim 11 or 12.