JP2011048309A - Method of manufacturing polarizer, method of manufacturing laminated body, and display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a polarizer having a high dichroic ratio and high uniformity. <P>SOLUTION: The method of manufacturing the polarizer includes a step of applying a composition containing (A) a surfactant, (B) a solvent and (C) two or more kinds of nematic liquid crystalline azo dye expressed by general formula (1) and containing no liquid crystalline noncolorable compound by a slit coating method, where in the formula, each of R<SP>1</SP>-R<SP>4</SP>independently expresses hydrogen atom or a substituent; each of R<SP>5</SP>-R<SP>6</SP>independently expresses hydrogen atom or an alkyl which can have a substituent; L<SP>1</SP>expressed -N=N-, -N=CH-, -C(=O)O- or -OC(=O)-; A<SP>1</SP>expresses phenyl, naphthyl or aromatic heterocyclic which can have a substituent; B<SP>1</SP>expresses bivalent aromatic hydrocarbon or bivalent aromatic heterocyclic; and (n) expresses integers of 1-4. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for manufacturing a polarizer, a method for manufacturing a laminate, and a display device.

When a function to attenuate the irradiation light including laser light and natural light, a polarization function, a scattering function, a light shielding function, etc. are required, conventionally, a device that operates according to a different principle for each function has been applied. . Therefore, products corresponding to these functions are also manufactured by different manufacturing processes for each function.
For example, LCDs (liquid crystal elements) use linearly polarizing plates and circularly polarizing plates to control optical rotation and birefringence in display. A circularly polarizing plate is also used in OLED (organic electroluminescence element) to prevent reflection of external light. Conventionally, iodine has been widely used as a dichroic substance in these polarizing plates (polarizing elements). However, since iodine has a high sublimation property, when used in a polarizing element, its heat resistance is not sufficient.

Therefore, a polarizing element using an organic dye as a dichroic material has been studied. Although these organic dyes have improved heat resistance as compared with iodine, there is a problem that only a polarizing element having a considerably inferior dichroism can be obtained.
On the other hand, in recent years, application development of new polarizing elements has been promoted for the purpose of improving display performance and the like. In Patent Document 1, it is proposed to suppress the depolarization of the color filter by providing a polarizing layer (so-called in-cell polarizing layer) between the color filter layer and the liquid crystal material layer. However, the above polarizing element material does not have sufficient heat resistance to produce an in-cell polarizing layer.

  Therefore, other methods have recently attracted attention. As this method, in Patent Document 2, organic dye molecules are vapor-deposited on the alignment film from the gas phase and aligned. However, the method described in the patent has a problem that the process itself is complicated in manufacturing.

  In addition, a method of aligning a dichroic dye by utilizing an intermolecular interaction of organic dye molecules on a substrate such as glass or a transparent film by a wet film forming method has been proposed. The wet film forming method includes various coating methods such as a spin coating method, a Mayer bar coating method, a gravure coating method, a die coating method, a dip coating method, and a spray coating method, or a printing technique such as a screen printing method and an ink jet method. However, when a polarizing element is produced by such a wet film-forming method, the dye used in this polarizing element needs to be oriented with high dichroism and uniformity, so that a wet composition suitable for the dye used is used. The film method is required. In Patent Document 3, it is described that it is preferable to apply an aqueous solution containing a flat pigment by a method in which a shear stress is applied. In the examples, Mayer bar coating is performed. Moreover, in the Example described in Patent Document 4, a spin coating method is performed.

  By the way, in the manufacture of a liquid crystal display device, an increase in substrate size is inevitable, including a thin film transistor (TFT) substrate and a color filter substrate. In recent years, the substrate of the fifth generation or more in which the length of at least one side is 1000 mm or more has become mainstream. Examples of such a substrate include substrates of 960 mm × 1100 mm, 1100 mm × l250 mm, 1100 mm × 1300 mm, 1500 mm × 1800 mm, 1800 mm × 2000 mm, etc., but the substrate size is increased in this way, and the length of at least one side is 1000 mm or more. In order to form a polarizing layer on the substrate surface, application of a coating method for improving the use efficiency of the composition is strongly demanded.

JP 2008-90317 A JP-A-8-278409 JP 2002-311246 A JP 2005-189393 A

  When this inventor examined, when the polarizing layer was formed with the apply | coating method which requires a shear stress, such as the Mayer bar coat method described in patent document 3, it turned out that thickness nonuniformity tends to arise. The thickness unevenness of the polarizing layer causes the generation of scattered light and consequently the contrast. On the other hand, it has been found that the spin coating application method described in Patent Document 4 has a problem that the alignment is disturbed by a centrifugal force and alignment defects are generated. In these methods, it is difficult to form a polarizing layer having a high dichroic ratio with high uniformity and without impairing the orientation of the material. In particular, in order to form a polarizing layer on the surface of the enlarged substrate, as described above, improvement in terms of use efficiency is also necessary, and the above method is insufficient in this respect.

This invention is made | formed in view of said background art, and makes it a subject to achieve the objective shown below.
An object of the present invention is to provide a stable method for producing a polarizer having high uniformity and high dichroism, which can suppress the occurrence of alignment defects even when applied to a large area. . Moreover, this invention makes it a subject to provide the display apparatus which comprises the polarizer and laminated body which were manufactured using the said method.

As a result of intensive studies to solve the above problems, the inventors of the present invention contain (A) a surfactant, (B) a solvent, and (C) an azo dye having a specific structure having two or more nematic liquid crystal properties. It has been found that the above problems can be solved by applying the composition to be applied by the slit coating method, and the present invention has been completed.
That is, the object of the present invention is achieved by the following means.
[1] (A) Surfactant, (B) solvent, and (C) two or more kinds of azo dyes having nematic liquid crystallinity represented by the following general formula (I), and liquid crystal non-coloring property A method for producing a polarizer comprising a step of applying a composition containing no compound by a slit coating method:

式中、Ｒ¹〜Ｒ⁴はそれぞれ独立に、水素原子又は置換基を表し；Ｒ⁵及びＲ⁶はそれぞれ独立に、水素原子又は置換基を有していてもよいアルキル基を表し；Ｌ¹は、−Ｎ＝Ｎ−、−Ｎ＝ＣＨ−、−Ｃ（＝Ｏ）Ｏ−基、又は−ＯＣ（＝Ｏ）−を表し；Ａ¹は、置換基を有していてもよいフェニル基、置換基を有していてもよいナフチル基、又は置換基を有していてもよい芳香族複素環基を表し；Ｂ¹は、置換基を有していてもよい、２価の芳香族炭化水素基又は２価の芳香族複素環基を表し；ｎは１〜４の整数を表し、ｎが２以上のとき複数のＢ¹は互いに同一でも異なっていてもよい。

In the formula, R ^{1 to} R ⁴ each independently represents a hydrogen atom or a substituent; R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group which may have a substituent; L ¹ Represents —N═N—, —N═CH—, —C (═O) O— group, or —OC (═O) —; A ¹ represents an optionally substituted phenyl group; Represents a naphthyl group which may have a substituent, or an aromatic heterocyclic group which may have a substituent; B ¹ represents a divalent aromatic which may have a substituent; Represents a hydrocarbon group or a divalent aromatic heterocyclic group; n represents an integer of 1 to 4, and when n is 2 or more, a plurality of B ^{1 s} may be the same as or different from each other.

式中、Ｒ⁷及びＲ⁸はそれぞれ独立に、水素原子、メチル基、又はエチル基を表し；Ｌ^1aは、−Ｎ＝Ｎ−、−Ｎ＝ＣＨ−、−Ｏ（Ｃ＝Ｏ）−、又は−ＣＨ＝ＣＨ−を表し；Ａ^1aは、下記一般式（IIa）又は（IIIa）で表される基を表し；Ｂ^1a及びＢ^2aはそれぞれ独立に、下記式（IVa）、（Ｖａ）、又は（VIａ）で表される基を表す； [2] (C) At least one of azo dyes having nematic liquid crystal properties represented by two or more general formulas (I) is a compound represented by the following general formula (Ia) Method [1] to do:

In the formula, R ⁷ and R ⁸ each independently represents a hydrogen atom, a methyl group, or an ethyl group; L ^1a represents —N═N—, —N═CH—, —O (C═O) —, Or -CH = CH-; A ^1a represents a group represented by the following general formula (IIa) or (IIIa); B ^1a and B ^2a independently represent the following formulas (IVa), (Va) Or represents a group represented by (VIa);

式中、Ｒ⁹は、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、置換基を有していてもよいアルコキシ基、置換基を有していてもよいオキシカルボニル基、又は置換基を有していてもよいアシルオキシ基を表す；

In the formula, R ⁹ has an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent. An oxycarbonyl group which may be substituted or an acyloxy group which may have a substituent;

式中、ｍは０〜２の整数を表す。

In formula, m represents the integer of 0-2.

[3] (C) Among the azo dyes having nematic liquid crystal properties represented by two or more general formulas (I), at least one of them is an azo dye represented by the following general formula (Ib) or (Ic) [1] or [2] characterized in that:

式中、Ｒ¹⁰及びＲ¹¹はそれぞれ独立に、水素原子、メチル基、又はエチル基を表し；Ｌ^1bは、−Ｎ＝Ｎ−又は−（Ｃ＝Ｏ）Ｏ−を表し；Ｌ^2bは、−Ｎ＝ＣＨ−、−（Ｃ＝Ｏ）Ｏ−、又は−Ｏ（Ｃ＝Ｏ）−を表し；Ａ^1bは、下記式（IIb）又は（IIIb）で表される基を表し；ｍは０〜２の整数を表す；

In the formula, R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, a methyl group, or an ethyl group; L ^1b represents —N═N— or — (C═O) O—; L ^2b represents -N = CH -, - (C = O) O-, or -O (C = O) - represents; a ^1b represents a group represented by the following formula (IIb) or (IIIb); m is Represents an integer of 0 to 2;

式中、Ｒ¹⁴は、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、置換基を有していてもよいアルコキシ基、置換基を有していてもよいオキシカルボニル基、置換基を有していてもよいアシルオキシ基を表す。

In the formula, R ¹⁴ has an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent. Or an acyloxy group which may have a substituent.

式中、Ｒ¹²及びＲ¹³は、水素原子、メチル基、又はエチル基を表し、Ａ^1cは、下記式（IIc）又は（IIIc）で表される基を表す。

In the formula, R ¹² and R ¹³ represent a hydrogen atom, a methyl group, or an ethyl group, and A ^1c represents a group represented by the following formula (IIc) or (IIIc).

式中、Ｒ¹⁴は、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、置換基を有していてもよいアルコキシ基、置換基を有していてもよいオキシカルボニル基、置換基を有していてもよいアシルオキシ基を表す。

In the formula, R ¹⁴ has an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent. Or an acyloxy group which may have a substituent.

式中、Ｒ¹は、水素原子又はメチル基を表し、ｍは４〜８の整数を表す；

式中、Ｒ¹は、水素原子又はメチル基を表し、ｍは４〜８の整数を表す； [4] The surfactant (A) is
(I) a polymerization unit of a fluoroaliphatic group-containing monomer represented by the following general formula (VII) or (VIII) and (ii) a polymerization unit of an amide group-containing monomer represented by the following general formula (IX), or [1] to [3], which contain at least one fluoroaliphatic group-containing copolymer containing polymerized units derived from poly (oxyalkylene) acrylate and / or poly (oxyalkylene) methacrylate. Either way:

In the formula, R ¹ represents a hydrogen atom or a methyl group, and m represents an integer of 4 to 8;

In the formula, R ¹ represents a hydrogen atom or a methyl group, and m represents an integer of 4 to 8;

式中、Ｒ³は、水素原子又はメチル基を表し、Ｒ¹⁰、Ｒ¹¹は、炭素数１〜６のアルキル基を表す。

Wherein, R ³ represents a hydrogen atom or a methyl group, R ^10, R ¹¹ represents an alkyl group having 1 to 6 carbon atoms.

式中、Ｒ¹¹、Ｒ²²及びＲ³³は各々独立に、末端にＣＦ₃基又はＣＦ₂Ｈ基を有するアルコキシ基を表し；Ｘ¹¹、Ｘ²²及びＸ³³は各々独立に、−ＮＨ−、−Ｏ−又は−Ｓ−を表し；ｍ１１、ｍ２２及びｍ３３は各々独立に１〜３の整数を表す。 [5] Any one of [1] to [4], wherein the surfactant (A) contains at least one fluoroaliphatic group-containing compound represented by the following general formula (X): the method of.

In the formula, R ¹¹ , R ²² and R ³³ each independently represents an alkoxy group having a CF ₃ group or a CF ₂ H group at the terminal; X ¹¹ , X ²² and X ³³ each independently represent —NH—, -O- or -S-; m11, m22 and m33 each independently represents an integer of 1 to 3;

[6] The composition further comprises (D) a non-liquid crystalline polyfunctional monomer having a radical polymerizable group, and (E) a photopolymerization initiator. [1] to [5] Either way.
[7] (C) The content of two or more nematic liquid crystalline azo dyes is 20% by mass or more based on the total solid content excluding the solvent, [1] to [6] A method for producing any one of the polarizers.
[8] (C) The total content of azo dyes having two or more nematic liquid crystal properties and (D) the content of non-liquid crystalline polyfunctional monomers having radical polymerizable groups is the total solid excluding the solvent The method according to [6] or [7], wherein the content is 50% by mass or more in minutes.
[9] A polarizer produced by the method of any one of [1] to [8].
[10] Steps [1], [2] and [3] below:
[1] A step of rubbing or irradiating light with an alignment film formed on a color filter [2] A step of slit coating the composition of [1-8] on the alignment film [3] Evaporating the solvent (C) A method for producing a laminate comprising the steps of orienting azo dyes having two or more nematic liquid crystal properties to form a polarizer in this order.
[11] A laminate produced by the method of [10].
[12] A display device having the polarizer of [9] or the laminate of [11].

  ADVANTAGE OF THE INVENTION According to this invention, even if it is a case where it apply | coats to a large area, generation | occurrence | production of an orientation defect can be suppressed, and the stable manufacturing method of a polarizer with high uniformity and high dichroism can be provided. . Moreover, according to this invention, the display apparatus which comprises the polarizer and laminated body which were manufactured using the said method can be provided.

Hereinafter, the present invention will be described in detail. In the present specification, “to” is used in the present specification to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
1. Method for Producing Polarizer The method for producing a polarizer of the present invention comprises (A) a surfactant, (B) a solvent, and (C) two or more nematic liquid crystal compounds represented by the following general formula (I). A composition for a polarizer containing an azo dye is applied by a slit coating method.

(1) Preparation of Composition for Forming Polarizer First, the composition for forming a polarizer used in the production method of the present invention will be described in detail.
The composition for forming a polarizer used in the production method of the present invention includes (A) a surfactant, (B) a solvent, and (C) two or more nematic liquid crystals represented by the general formula (I). Containing an azo dye having properties. However, the composition does not contain a liquid crystal non-coloring compound. That is, in the present invention, the azo dye molecule is aligned by its own alignment ability, and functions as a polarizer by fixing its state. For example, using a composition containing a liquid crystal compound together with a dichroic dye, the molecules of the dichroic dye are aligned along the alignment of the molecules of the liquid crystal compound, and a predetermined dichroic ratio is achieved. A so-called guest-host (GH) type polarizer is distinguished from a polarizer manufactured by the manufacturing method of the present invention.

(C) Two or more kinds of azo dyes having nematic liquid crystal properties represented by the general formula (I):

In the formula, R ^{1 to} R ⁴ each independently represents a hydrogen atom or a substituent; R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group which may have a substituent; L ¹ Represents —N═N—, —N═CH—, —C (═O) O— group, or —OC (═O) —; A ¹ represents an optionally substituted phenyl group; Represents a naphthyl group which may have a substituent, or an aromatic heterocyclic group which may have a substituent; B ¹ represents a divalent aromatic which may have a substituent; Represents a hydrocarbon group or a divalent aromatic heterocyclic group; n represents an integer of 1 to 4, and when n is 2 or more, a plurality of B ^{1 s} may be the same as or different from each other.

In the general formula (I), examples of the substituent represented by R ^{1 to} R ⁴ include the following groups.
An alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, such as a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group and the like, alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, Particularly preferred are alkenyl groups having 2 to 8 carbon atoms, such as vinyl group, aryl group, 2-butenyl group and 3-pentenyl group), alkynyl groups (preferably having 2 to 20 carbon atoms, more preferred). Is an alkynyl group having 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, such as propargyl group and 3-pentynyl group. An aryl group (preferably an aryl group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as a phenyl group, a 2,6-diethylphenyl group, 3,5-ditrifluoromethylphenyl group, naphthyl group, biphenyl group and the like), substituted or unsubstituted amino group (preferably having 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, particularly preferably carbon An amino group of 0 to 6, and examples thereof include an unsubstituted amino group, a methylamino group, a dimethylamino group, a diethylamino group, and an anilino group).

  An alkoxy group (preferably having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 6 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, and a butoxy group), an oxycarbonyl group (Preferably having 2 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, particularly preferably 2 to 10 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group, and phenoxycarbonyl group), acyloxy group (preferably Has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, particularly preferably 2 to 6 carbon atoms, and examples thereof include an acetoxy group and a benzoyloxy group), an acylamino group (preferably 2 to 20 carbon atoms, More preferably, it has 2 to 10 carbon atoms, particularly preferably 2 to 6 carbon atoms. For example, acetylamino group, benzoyl Mino group and the like), alkoxycarbonylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, particularly preferably 2 to 6 carbon atoms, and examples thereof include methoxycarbonylamino group). Aryloxycarbonylamino group (preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 12 carbon atoms, and examples thereof include a phenyloxycarbonylamino group). A sulfonylamino group (preferably having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, such as a methanesulfonylamino group and a benzenesulfonylamino group), sulfamoyl Group (preferably having 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, particularly preferably A prime number of 0 to 6, for example, a sulfamoyl group, a methylsulfamoyl group, a dimethylsulfamoyl group, a phenylsulfamoyl group, etc.), a carbamoyl group (preferably having a carbon number of 1 to 20, more preferably carbon 1 to 10 and particularly preferably 1 to 6 carbon atoms, and examples thereof include an unsubstituted carbamoyl group, a methylcarbamoyl group, a diethylcarbamoyl group, and a phenylcarbamoyl group).

An alkylthio group (preferably having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, such as a methylthio group and an ethylthio group), an arylthio group (preferably a carbon atom) 6 to 20, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as a phenylthio group, and a sulfonyl group (preferably 1 to 20 carbon atoms, more preferably carbon 1 to 10, particularly preferably 1 to 6 carbon atoms, for example, mesyl group, tosyl group and the like, sulfinyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, especially Preferably it is C1-C6, for example, a methanesulfinyl group, a benzenesulfinyl group etc. are mentioned), a ureido group (preferably carbon number). To 20, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, and examples thereof include an unsubstituted ureido group, a methylureido group, and a phenylureido group), a phosphoric acid amide group (preferably Has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, and examples thereof include a diethylphosphoric acid amide group and a phenylphosphoric acid amide group), a hydroxy group, a mercapto Group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group (—CH═N— or —N═CH—) , An azo group, a heterocyclic group (preferably a heterocyclic group having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms such as a nitrogen atom, an oxygen atom, a sulfur atom A heterocyclic group having a hetero atom such as imidazolyl group, pyridyl group, quinolyl group, furyl group, piperidyl group, morpholino group, benzoxazolyl group, benzimidazolyl group, benzthiazolyl group, etc.) Silyl group (preferably a silyl group having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, and examples thereof include a trimethylsilyl group and a triphenylsilyl group) Is included.
These substituents may be further substituted with these substituents. Further, when two or more substituents are present, they may be the same or different. If possible, they may be bonded to each other to form a ring.

The group represented by R ^{1 to} R ⁴ is preferably a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, more preferably a hydrogen atom, an alkyl group or an alkoxy group, still more preferably a hydrogen atom or methyl. It is a group.

The alkyl group which may have a substituent represented by R ⁵ and R ⁶ is preferably an alkyl having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms. Group, and examples thereof include a methyl group, an ethyl group, and an n-octyl group. Examples of the substituent of the alkyl group represented by R ⁵ and R ^6, the same meaning as the substituents represented by R ¹ to R ^4. When R ⁵ or R ⁶ represents an alkyl group, it may be linked to R ² or R ⁴ to form a ring structure. R ⁵ and R ⁶ are preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom, a methyl group, or an ethyl group.

A ¹ represents a phenyl group which may have a substituent, a naphthyl group which may have a substituent, or an aromatic heterocyclic group which may have a substituent.
Examples of the substituent that the phenyl group or the naphthyl group may have include a group that is introduced to improve the solubility and nematic liquid crystal properties of the azo compound, and an electron that is introduced to adjust the color tone as a dye. A group having a donating property or an electron-withdrawing property, or a group having a polymerizable group introduced to fix the orientation is preferable, and specifically, the same as the substituent represented by R ^{1 to} R ^4. is there. Preferably, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an aryl group which may have a substituent An alkoxy group that may have a substituent, an oxycarbonyl group that may have a substituent, an acyloxy group that may have a substituent, an acylamino group that may have a substituent, Amino group optionally having substituent, alkoxycarbonylamino group optionally having substituent, sulfonylamino group optionally having substituent, sulfamoyl group optionally having substituent A carbamoyl group which may have a substituent, an alkylthio group which may have a substituent, a sulfonyl group which may have a substituent, a ureido group which may have a substituent, nitro Group, hydro Si group, cyano group, imino group, azo group, halogen atom, particularly preferably, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, and a substituent. An aryl group which may have a substituent, an alkoxy group which may have a substituent, an oxycarbonyl group which may have a substituent, an acyloxy group which may have a substituent, a nitro group, an imino group, An azo group. Among these substituents, those having carbon atoms are preferably in the same range as the number of carbon atoms for the substituents represented by R ^{1 to} R ⁴ .

The phenyl group or the naphthyl group may have 1 to 5 of these substituents, and preferably 1 of them. More preferably, the phenyl group has one substituent at the para position with respect to L ¹ .

  As the aromatic heterocyclic group, a group derived from a monocyclic or bicyclic heterocyclic ring is preferable. Examples of atoms other than carbon constituting the aromatic heterocyclic group include a nitrogen atom, a sulfur atom, and an oxygen atom. When the aromatic heterocyclic group has a plurality of atoms constituting a ring other than carbon, these may be the same or different. Specific examples of the aromatic heterocyclic group include a pyridyl group, a quinolyl group, a thiophenyl group, a thiazolyl group, a benzothiazolyl group, a thiadiazolyl group, a quinolonyl group, a naphthalimidoyl group, and a thienothiazolyl group.

  The aromatic heterocyclic group is preferably a pyridyl group, a quinolyl group, a thiazolyl group, a benzothiazoly group, a thiadiazolyl group, or a thienothiazolyl group, more preferably a pyridyl group, a benzothiazolyl group, a thiadiazolyl group, or a thienothiazolyl group, and a pyridyl group, a benzothiazolyl group. Or a thienothiazolyl group is more preferable.

A ¹ is particularly preferably an optionally substituted phenyl group, pyridyl group, benzothiazolyl group, or thienothiazolyl group.

B ¹ represents a divalent aromatic hydrocarbon group or a divalent aromatic heterocyclic group which may have a substituent. n represents 1 to 4, and when n is 2 or more, the plurality of B ¹ may be the same or different from each other.

  As the aromatic hydrocarbon group, a phenyl group and a naphthyl group are preferable. Examples of the substituent that the aromatic hydrocarbon group may have include an alkyl group that may have a substituent, an alkoxy group that may have a substituent, a hydroxy group, a nitro group, and a halogen atom. , An amino group which may have a substituent, an acylamino group which may have a substituent, and a cyano group. The substituent that the aromatic hydrocarbon group may have is preferably an alkyl group that may have a substituent, an alkoxy group that may have a substituent, a hydroxy group, or a halogen atom, An alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a halogen atom are more preferable, and a methyl group or a halogen atom is more preferable.

As the aromatic heterocyclic group, a group derived from a monocyclic or bicyclic heterocyclic ring is preferable. Examples of atoms other than carbon constituting the aromatic heterocyclic group include a nitrogen atom, a sulfur atom, and an oxygen atom. When the aromatic heterocyclic group has a plurality of atoms constituting a ring other than carbon, these may be the same or different. Specific examples of the aromatic heterocyclic group include a pyridyl group, a quinolyl group, an isoquinolyl group, a benzothiadiazole group, a phthalimide group, and a thienothiazole group. Of these, a thienothiazole group is particularly preferable.
Examples of the substituent that the aromatic heterocyclic group may have include an alkyl group such as a methyl group and an ethyl group; an alkoxy group such as a methoxy group and an ethoxy group; an amino group such as an unsubstituted or methylamino group; Examples thereof include an acetylamino group, an acylamino group, a nitro group, a hydroxy group, a cyano group, and a halogen atom. Among these substituents, those having carbon atoms are preferably in the same range as the number of carbon atoms for the substituents represented by R ^{1 to} R ⁴ .

  Preferable examples of the azo dye represented by the general formula (I) include azo dyes represented by any one of the following general formulas (Ia) to (Ic).

In the formula, R ⁷ and R ⁸ each independently represents a hydrogen atom, a methyl group, or an ethyl group; L ^1a represents —N═N—, —N═CH—, —O (C═O) —, Or -CH = CH-; A ^1a represents a group represented by the following general formula (IIa) or (IIIa); B ^1a and B ^2a independently represent the following formulas (IVa), (Va) Or represents a group represented by (VIa);

In the formula, R ⁹ has an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent. Represents an oxycarbonyl group which may be substituted or an acyloxy group which may have a substituent.

  In formula, m represents the integer of 0-2.

In the formula, R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, a methyl group, or an ethyl group; L ^1b represents —N═N— or — (C═O) O—; L ^2b represents -N = CH -, - (C = O) O-, or -O (C = O) - represents; a ^1b represents a group represented by the following formula (IIb) or (IIIb); m is Represents an integer of 0 to 2;

In the formula, R ¹⁴ has an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent. Or an acyloxy group which may have a substituent.

In the formula, R ¹² and R ¹³ represent a hydrogen atom, a methyl group, or an ethyl group, and A ^1c represents a group represented by the following formula (IIc) or (IIIc).

In the formula, R ¹⁴ has an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent. Or an acyloxy group which may have a substituent.

In the general formulas (Ia), (Ib) and (Ic), examples of the substituents which each group has are the same as the examples of the substituents represented by R ^{1 to} R ⁴ in the general formula (I). is there. As for the group having a carbon atom such as an alkyl group, preferable range of the number of carbon atoms is the same as the preferred range of number of carbon atoms of the substituent represented by R ¹ to R ^4.

The compounds represented by the general formulas (I), (Ia), (Ib) and (Ic) may have a polymerizable group as a substituent. It is preferable to have a polymerizable group because the hardening property is improved. Examples of the polymerizable group include an unsaturated polymerizable group, an epoxy group, and an aziridinyl group, preferably an unsaturated polymerizable group, and particularly preferably an ethylenically unsaturated polymerizable group. Examples of the ethylenically unsaturated polymerizable group include acryloyl group and methacryloyl group.
The polymerizable group is preferably located at the molecular end, that is, in the formula (I), preferably present as a substituent for R ⁵ and / or R ^{6 and as} a substituent for Ar ¹ .

Although the specific example of a compound represented by general formula (I) below is given, it is not limited to the following specific examples.

  The azo dye represented by the general formula (I) according to the present invention can be easily synthesized according to the method described in Journal of Materials Chemistry (1999), 9 (11), 2755-2763.

  About the liquid crystal property of the azo dye represented by the said general formula (I), Preferably it is 10-300 degreeC, More preferably, a nematic liquid crystal phase is shown at 100-250 degreeC.

The composition for forming a polarizer contains (C) an azo dye represented by two or more general formulas (I). Although there is no restriction | limiting in particular about the combination of an azo pigment | dye, In order for the polarizer to manufacture to achieve high polarization degree, it is preferable to mix with the combination used as black.
The azo dye represented by the general formula (Ia) of the present invention is a magenta azo dye, and the azo dye represented by the general formula (Ib) is a yellow or magenta azo dye represented by the general formula (Ic). The azo dye is a cyan azo dye.
Of the two or more azo dyes represented by the general formula (I) contained in the polarizer-forming composition, at least one azo dye is preferably an azo dye represented by the general formula (Ia).
Of the two or more azo dyes represented by the general formula (I) contained in the composition for forming a polarizer, at least one azo dye represented by the general formula (Ib) or (Ic) is used. It is preferable that
The polarizer-forming composition contains at least one azo dye represented by the general formula (Ia) and at least one azo dye represented by the general formula (Ib) or (Ic). It is preferable.
The polarizer-forming composition includes at least one azo dye represented by the general formula (Ia), at least one compound represented by the general formula (Ib), and at least one (Ic). More preferably, it contains an azo dye represented by:
In addition, the said composition for polarizer formation may further contain the coloring material which is pigment | dyes other than the azo pigment | dye represented by general formula (I) in the range which does not impair the effect of this invention. The dye other than the azo dye represented by the general formula (I) is also preferably selected from compounds exhibiting liquid crystallinity.

  In the composition for forming a polarizer, the content of (C) the azo dye represented by two or more general formulas (I) is 80% by mass or more based on the total content of all the dyes contained. It is preferable that it is 90 mass% or more. The upper limit is 100% by mass, that is, all the dyes contained may of course be azo dyes represented by the general formula (I).

In the total solid content excluding the solvent (B) contained in the composition for forming a polarizer, the content of the azo dye represented by (C) two or more general formulas (I) is 20% by mass or more. It is preferable that it is 30 mass% or more. Although the upper limit is not particularly limited, in order that the effect of the surfactant (A) is sufficient, and in the embodiment containing the components (D) and (E) described later, the effect of addition thereof is sufficiently obtained. It is necessary to add a certain amount of each, and in these viewpoints, (C) two or more general formulas (C) in the total solid content excluding the solvent (B) contained in the polarizer-forming composition ( The content of the azo dye represented by I) is preferably 98% by mass or less, and more preferably 50% by mass or less.
In the GH type polarizer described above, the composition used for formation usually contains 90% by mass or more of the liquid crystal compound serving as the host in the total solid content, and the content of the guest dye is 1 to 5% by mass. Degree.

(A) Surfactant:
The polarizer-forming composition used in the present invention contains (A) a surfactant together with (C) two or more nematic liquid crystalline azo dyes. The surfactant is added for the purpose of preventing wind unevenness during slit coating. The surfactant may also contribute to (C) two or more types of nematic liquid crystalline azo dye molecules in a more stable horizontal alignment state. More specifically, it acts as a horizontal alignment agent at the air interface, and the occurrence of reverse tilt domains on the air interface side can be suppressed.

  Examples of surfactants added from the viewpoint of preventing wind unevenness include general fluoropolymer interfacial agents, and the fluoropolymer used is not particularly limited as long as the change in the tilt angle and orientation of the dye are not significantly inhibited. There is no. Examples of the fluoropolymer that can be used as the surfactant include JP-A No. 2004-198511, JP-A No. 4190275, JP-A No. 2004-333852, JP-A No. 2005-206638, and Japanese Patent Application No. 2008-193565. There is description in the gazette.

An example of the surfactant is
(i) Polymerized units of fluoroaliphatic group-containing monomers represented by the following general formula (VII) or (VIII) and (ii) polymerized units derived from poly (oxyalkylene) acrylate and / or poly (oxyalkylene) methacrylate Is a first fluoroaliphatic group-containing copolymer. The first fluoroaliphatic group-containing copolymer contributes to the reduction of wind unevenness.

In the formula, R ¹ represents a hydrogen atom or a methyl group, and m represents an integer of 4 to 8. m is preferably 4 or 6. Mixtures of these may be used.

Next, poly (oxyalkylene) acrylate and / or poly (oxyalkylene) methacrylate will be described (hereinafter, when referring to both acrylate and methacrylate, both may be collectively referred to as (meth) acrylate).
Polyoxyalkylene group can be represented by (OR) x, R is an alkylene group having 2 to 4 carbon atoms, such as _{-CH 2 CH 2 -, - CH} 2 CH 2 CH 2 -, - CH (CH ₃ ) It is preferably CH ₂ — or —CH (CH ₃ ) CH (CH ₃ ) —.

The oxyalkylene units in the poly (oxyalkylene) group may be the same as in poly (oxypropylene), or two or more different oxyalkylenes may be randomly distributed. It may be a linear or branched oxypropylene or oxyethylene unit, or a linear or branched oxypropylene unit block and an oxyethylene unit block.
In the poly (oxyalkylene) chain, a plurality of poly (oxyalkylene) units are one or more chain bonds (for example, —CONH—Ph—NHCO—, —S—, etc., where Ph represents a phenylene group. ) Can be included. If the chain bond has a valence of 3 or more, this provides a means for obtaining branched oxyalkylene units. When this copolymer is used in the present invention, the molecular weight of the poly (oxyalkylene) group is suitably from 250 to 3,000.

Poly (oxyalkylene) acrylates and methacrylates are commercially available hydroxypoly (oxyalkylene) materials such as “Pluronic” [Pluronic (Asahi Denka Kogyo Co., Ltd.), “Adeka Polyether” (Asahi Denka Kogyo Co., Ltd.). "Carbowax" (Carbowax (Glico Product)), "Triton" (Toriton (Rohm and Haas) and "PEG" (Daiichi Kogyo Seiyaku Co., Ltd.) Can be produced by reacting the product with acrylic acid, methacrylic acid, acrylic chloride, methacrylic chloride or acrylic acid anhydride in a known manner.
Poly (oxyalkylene) diacrylate produced by a known method can also be used.

  Preferred examples of the polyoxyalkylene (meth) acrylate are polyoxyethylene (meth) acrylate and polyoxypropylene (meth) acrylate.

  The preferred copolymerization ratio of the fluoroaliphatic group-containing monomer in the first fluoroaliphatic group-containing copolymer is an embodiment in which the fluoroaliphatic group-containing monomer is a compound represented by the general formula (VII) Then, the amount of the monomer is preferably 50% by mass or more and 99% by mass or less, more preferably 70% by mass or more and 98% by mass or less, and particularly preferably 80% by mass or more and 98% by mass or less. In the embodiment in which the fluoroaliphatic group-containing monomer is a compound represented by the general formula (VIII), the monomer is preferably 20% by mass or more and 60% by mass or less, more preferably 30% by mass based on the total monomers. It is 35 mass% or more and 50 mass% or less especially preferably 35 mass% or more.

  The preferred weight average molecular weight of the first fluoroaliphatic group-containing copolymer is preferably 3000 to 100,000, more preferably 6,000 to 80,000.

  Hereinafter, examples of specific structures of the first fluoroaliphatic group-containing copolymer are shown, but the present invention is not limited thereto. In addition, the number in a formula shows the mass ratio of each monomer component, and Mw represents a weight average molecular weight.

  Using a fluoropolymer such as the fluoroaliphatic group-containing copolymer as a surfactant in combination with (C) two or more nematic liquid crystalline azo dyes, forming a film by the slit coating method produces unevenness. Therefore, a polarizer having a high degree of polarization can be stably formed. Furthermore, applicability such as repelling is improved. The addition amount of the fluorine-based polymer used for the purpose of preventing wind unevenness so as not to hinder the orientation of the dye is generally 0.1 to 10% by mass relative to the total amount of (C) two or more azo dyes. It is preferable that it is the range of 0.5-10 mass%, and it is more preferable that it exists in the range of 0.5-5 mass%.

Other examples of the surfactant (A) used in the present invention are as follows:
(1) a fluoroaliphatic group-containing compound represented by the following general formula (III); or
(2) selected from the group consisting of polymerized units of a fluoroaliphatic group-containing monomer represented by the general formula (VII) or (VIII) and polymerized units of an amide group-containing monomer represented by the general formula (IX) A second fluoroaliphatic group-containing copolymer comprising at least one polymerized unit;
It is. These surfactants are surfactants that contribute to the horizontal alignment of azo dye molecules at the air interface of the coating film. In particular, these surfactants act as a horizontal alignment agent at the air interface and reverse on the air interface side. It has the effect of suppressing the occurrence of tilt domains. Each will be described below. First, (1) the fluoroaliphatic group-containing compound represented by the general formula (III) will be described.

In the formula, R ¹¹ , R ²² and R ³³ each independently represents an alkoxy group having a CF ₃ group or a CF ₂ H group at the terminal, and X ¹¹ , X ²² and X ³³ each independently represent —NH—, -O- or -S- is represented, and m11, m22 and m33 each independently represent an integer of 1 to 3.

The substituent represented by each of R ¹¹ , R ²² and R ³³ is an alkoxy group having a CF ₃ group or a CF ₂ H group at the terminal, and may be linear or branched. Preferably it is C4-C20, More preferably, it is C4-C16, Most preferably, it is 6-16. The alkoxy group having a CF ₃ group or a CF ₂ H group at the terminal is an alkoxy group in which part or all of the hydrogen atoms contained in the alkoxy group are substituted with fluorine atoms. 50% or more of hydrogen atoms in the alkoxy group are preferably substituted with fluorine atoms, more preferably 60% or more are substituted, and particularly preferably 70% or more are substituted. Examples of alkoxy groups having a CF ₃ group or a CF ₂ H group at the ends represented by R ¹¹ , R ²² and R ³³ are shown below.

R1: n-C ₈ F ₁₇ —O—
_{R2: n-C 6 F 13} -O-
_{R3: n-C 4 F 9} -O-
_{R4: n-C 8 F 17} - (CH 2) 2 -O- (CH 2) 2 -O-
_{R5: n-C 6 F 13} - (CH 2) 2 -O- (CH 2) 2 -O-
_{R6: n-C 4 F 9} - (CH 2) 2 -O- (CH 2) 2 -O-
_{R7: n-C 8 F 17} - (CH 2) 3 -O-
_{R8: n-C 6 F 13} - (CH 2) 3 -O-
_{R9: n-C 4 F 9} - (CH 2) 3 -O-
_{R10: H- (CF 2) 8} -O-
R11: H— (CF ₂ ) ₆ —O—
R12: H— (CF ₂ ) ₄ —O—
_{R13: H- (CF 2) 8} - (CH 2) -O-
_{R14: H- (CF 2) 6} - (CH 2) -O-
_{R15: H- (CF 2) 4} - (CH 2) -O-
_{R16: H- (CF 2) 8} - (CH 2) -O- (CH 2) 2 -O-
_{R17: H- (CF 2) 6} - (CH 2) -O- (CH 2) 2 -O-
_{R18: H- (CF 2) 4} - (CH 2) -O- (CH 2) 2 -O-

In the general formula (III), X ¹¹ , X ²² and X ³³ each preferably represent —NH— or —O—, and most preferably represents —NH—. m ¹¹ , m ²² and m ³³ are each preferably 2.

  Specific examples of the compound represented by the general formula (III) are shown below, but are not limited thereto.

Next, (2) a group consisting of polymerized units of a fluoroaliphatic group-containing monomer represented by the general formula (VII) or (VIII) and polymerized units of an amide group-containing monomer represented by the general formula (IX) The second fluoroaliphatic group-containing copolymer containing at least one polymer unit selected from is described.
For the fluoroaliphatic group-containing monomer represented by the general formula (VII) or the general formula (VIII), the general formula (VII) or the general formula (VIII) described in the first fluoroaliphatic group-containing copolymer is used. And the preferred examples are also the same.

In the formula, R ³ represents a hydrogen atom, a halogen atom or a methyl group, and more preferably a hydrogen atom or a methyl group.
R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aromatic group having 6 to 20 carbon atoms or a heterocyclic group having 1 to 20 carbon atoms, and these substituents are further substituted It may have a group. In addition, an alkyl group having 1 to 12 carbon atoms and an aromatic group having 6 to 15 carbon atoms are more preferable, and an alkyl group having 1 to 6 carbon atoms and an aromatic group having 6 to 12 carbon atoms are further included. preferable. R ¹⁰ and R ¹¹ may be linked to each other to form a heterocyclic ring. Examples of the formed heterocyclic ring include a pyrrolidine ring, a piperidine ring, and a morpholine ring.

  The second fluoroaliphatic group-containing copolymer may contain a fluoroaliphatic group-containing monomer and an amide group-containing monomer as polymerized units. The polymer may contain two or more kinds of each monomer as polymerized units, or may be a copolymer containing one or more other copolymerizable monomers as polymerized units. Other types of such copolymerizable monomers include Polymer Handbook 2nd ed. , J .; Brandrup, Wiley lnterscience (1975) Chapter 2 Pages 1-483 can be used. Examples thereof include compounds having one addition polymerizable unsaturated bond selected from acrylic esters, methacrylic esters, methacrylamides, allyl compounds, vinyl ethers, vinyl esters and the like.

  The preferred mass average molecular weight of the second fluoroaliphatic group-containing copolymer is 2000 to 100,000, more preferably 3000 to 80,000, and even more preferably 4,000 to 60,000. Here, the mass average molecular weight and the molecular weight were converted into polystyrene by GTH analyzer using columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (both trade names manufactured by Tosoh Corp.) by detection of solvent THF and differential refractometer. Is the molecular weight.

  Examples of the second fluoroaliphatic group-containing copolymer that can be used in the present invention are shown below, but are not limited to the following specific examples. In addition, the number in a formula shows the mass ratio of each monomer component. Mw represents a mass average molecular weight.

  In addition, horizontal alignment agents described in JP-A-2005-99248, JP-A-2005-134484, JP-A-2006-126768, and JP-A-2006-267183 can also be used.

  (A) The fluoroaliphatic group-containing compound or (2) the second fluoroaliphatic group-containing copolymer used as the surfactant may be used alone or in combination of two or more. May be used. The addition amount of the (1) fluoroaliphatic group-containing compound or (2) the second fluoroaliphatic group-containing copolymer is (0.002% relative to the total content of C92 or more nematic liquid crystalline azo dyes. It is preferably 1% by mass to 10% by mass, more preferably 0.5% by mass to 10% by mass, and particularly preferably 0.5% by mass to 5% by mass.

The composition for a polarizer used in the present invention may further contain one or more of the following additives.
(D) Non-liquid crystalline polyfunctional monomer having a radical polymerizable group:
It is preferable that the said composition for polarizers contains (D) 1 or more types of the non-liquid crystalline polyfunctional monomer which has a radically polymerizable group.
In the present invention, the “non-liquid crystalline polyfunctional monomer having a radical polymerizable group” refers to a non-liquid crystalline monomer which is a polyfunctional monomer in which a growth active species undergoes a radical polymerization reaction. The polyfunctional monomer is preferably a polyfunctional monomer having two or more double bonds in the molecule, particularly preferably an ethylenic (aliphatic) unsaturated double bond, specifically, Multifunctional monomers having functional groups such as alkenes, dienes, acrylates, methacrylates, diesters of unsaturated polycarboxylic acids, amides of α, β-unsaturated carboxylic acids, unsaturated nitriles, styrene and derivatives thereof, vinyl esters, vinyl ethers, etc. Can be mentioned. The number of double bonds in the molecule is preferably 2-20, more preferably 2-15, and even more preferably 2-6. The polyfunctional monomer is preferably an ester of a polyol having two or more hydroxyl groups in the molecule and an unsaturated fatty acid. Examples of unsaturated fatty acids include acrylic acid, methacrylic acid, maleic acid and itaconic acid, with acrylic acid and methacrylic acid being preferred. The polyol having 4 or more hydroxyl groups in the molecule is preferably a tetrahydric or higher alcohol or a trihydric or higher alcohol oligomer. The oligomer has a molecular structure in which polyhydric alcohols are linked by an ether bond, an ester bond or a urethane bond. Oligomers having a molecular structure in which polyhydric alcohols are linked by ether bonds are preferred.

The polyfunctional monomer is particularly preferably soluble in an organic solvent.
An example of such a monomer is a compound having a boiling point of 100 ° C. or higher at normal pressure.

  Among the polyfunctional monomers described above, as the bifunctional (meth) acrylate, for example, ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, Polypropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, bisphenoxyethanol full orange acrylate, and the like are listed. Examples of commercially available products include Aronix M-210, M-240, and M-6200 (Toa). Synthetic Chemical Industry Co., Ltd.), KAYARAD HDDA, HX-220, R-604 (Nippon Kayaku Co., Ltd.), Biscoat 260, 312 and 335HP (Osaka Organic Chemical Co., Ltd.), etc. Is mentioned.

  Examples of the trifunctional or higher functional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol tetra (meth) acrylate, Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like can be mentioned, and examples of commercially available products thereof include Aronix M-309, M-400, M-405, M-450, and the like. M-7100, M-8030, M-8060 (both trade names, manufactured by Toa Gosei Chemical Co., Ltd.), KAYARAD TMPTA, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120 (both quotient Name, manufactured by Nippon Kayaku Co., Ltd.), BISCOAT 295, the 300, the 360, the same GPT, the same 3PA, the 400 (trade name, manufactured by Osaka Organic Chemical Industry Co., Ltd.), and the like.

  As examples of further monomers and oligomers, bifunctional or trifunctional or higher (meth) acrylates include, for example, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane diacrylate. , Neopentyl glycol di (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyl) Oxyethyl) cyanurate, glycerin tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, dipenta Lithitol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate; polyfunctional acrylates such as those obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as trimethylolpropane and glycerin and then (meth) acrylated Functional methacrylate; Poly (meth) acrylate of polyether polyol, poly (meth) acrylate of polyester polyol and poly (meth) acrylate of polyurethane polyol are included.

  Monomers composed of an ester of polyol and acrylic acid are commercially available from Mitsubishi Rayon Co., Ltd. (trade name: Diabeam UK-4154) and Nippon Kayaku Co., Ltd. (trade name: KYARAD / DPHA, SR355).

  These bifunctional or trifunctional or higher functional (meth) acrylates may be used alone or in combination, and may be used in combination with monofunctional (meth) acrylate.

  Examples of monofunctional (meth) acrylates include 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, and 2- (meth) acryloyloxyethyl. 2-hydroxypropyl phthalate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate, ethylene glycol (meth) acrylate, and the like. -101, M-111, M-114 (manufactured by Toa Gosei Chemical Industry Co., Ltd.), KAYARAD TC-110S, TC-120S (manufactured by Nippon Kayaku Co., Ltd.), Biscote 158, 2311 (Osaka) Machine Chemical Industries Co., Ltd.) and the like.

  As will be described later, when preparing the polarizer, it is preferable to fix the alignment state of the nematic liquid crystalline dye, and as a means for fixing, the alignment of the dye is fixed using a polymerization reaction. The polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator and a photopolymerization reaction using a photopolymerization initiator.

  In the composition for forming a polarizer, the total content of (C) two or more azo dyes and (D) a non-liquid crystalline polymerizable polyfunctional monomer in the total solid content excluding the solvent (B) is 50. It is preferably at least 70% by mass, particularly preferably at least 70% by mass.

(E) Polymerization initiator:
(D) In a composition containing a non-liquid crystalline polyfunctional monomer having a radical polymerizable group, it is preferable to contain a polymerization initiator in order to cause the monomer to undergo a curing reaction.
As the polymerization initiator, known compounds can be suitably used according to photopolymerization and thermal polymerization. For example, α-carbonyl compounds (US Pat. Nos. 2,367,661 and 2,367,670) can be used as examples of the photopolymerization initiator. ), Acyloin ether (described in U.S. Pat. No. 2,448,828), α-hydrocarbon-substituted aromatic acyloin compound (described in U.S. Pat. No. 2,722,512), polynuclear quinone compound (U.S. Pat. Nos. 3,046,127 and 2,951,758). No. 3), a combination of triarylimidazole dimer and p-aminophenyl ketone (described in U.S. Pat. No. 3,549,367), acridine and phenazine compound (Japanese Patent Laid-Open No. 60-105667, U.S. Pat. No. 4,239,850) Oxadiazole compounds (US Pat. No. 42129) No. 70).

The amount of the photopolymerization initiator used is preferably 0.01 to 20% by mass, more preferably 1 to 10% by mass, based on the total solid content excluding the solvent.
Regarding the examples of the photopolymerization initiator, the amount of the photopolymerization initiator used, and the value of the light irradiation energy for polymerization, the descriptions in paragraphs [0050] to [0051] of JP-A-2001-91741 are also included in this book. Applicable to the invention.

Other additives:
(A) a surfactant, (B) a solvent, and (C) two or more nematic liquid crystalline azo dyes, and (D) radicals optionally added to the composition for forming a polarizer used in the present invention. In addition to the non-liquid crystalline polyfunctional monomer having a polymerizable group and (E) the polymerization initiator, any additive can be blended and used in combination. Examples of additives include non-liquid crystalline binder polymers, anti-repellent agents, additives for controlling the tilt angle of the alignment film (tilt angle of the liquid crystalline azo dye at the polarizer film / alignment film interface), air An additive for controlling the tilt angle of the interface (tilt angle of the liquid crystalline azo dye at the polarizer film / air interface), a saccharide, a drug having at least one function of antifungal, antibacterial and sterilization. Hereinafter, each additive will be described.

Non-liquid crystalline binder polymer:
A non-liquid crystalline binder polymer may be added to the composition for forming a polarizer used in the present invention. Examples of non-liquid crystalline polymers include acrylic resins such as polyacrylonitrile, polyacrylic acid esters and polyacrylamide, polyvinyl acetal resins such as polystyrene resin, polyvinyl acetoacetal and polyvinyl butyral, ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxy cellulose, hydroxy Modified cellulose resins such as propyl cellulose, ethyl hydroxyethyl cellulose, methyl cellulose, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, cellulose nitrate, etc., cellulose resins such as ethyl hydroxyethyl cellulose and ethyl cellulose, polyurethane resins, polyamide resins, Polyester resin, polycarbonate resin, phenoxy resin, phenol resin , Epoxy resins, various elastomers, and the like. These may be used alone or in combination of two or more or a copolymer.
As the non-liquid crystalline binder polymer, an acrylic polymer (a resin having an acrylic copolymer or a styrene copolymer as a main chain) is particularly preferable, and it is particularly preferable that it is soluble in an organic solvent.

  For example, a known radical polymerization method can be applied to the production of the acrylic polymer. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. in the production by the radical polymerization method can be easily set by those skilled in the art, and the conditions should be determined experimentally. You can also.

  As for specific copolymerization components of the above acrylic polymer, unsaturated carboxylic acid (eg, (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid), aromatic vinyl compound (eg, styrene, α-methylstyrene, vinyltoluene, 2-vinylpyridine, 4-vinylpyridine, N-vinylimidazole, etc.), (meth) acrylic acid alkyl esters (eg, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl) (Meth) acrylate, i-butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, dodecyl (meth) acrylate, etc.), (meth) acrylic acid alkyl aryl ester (eg, benzyl (meth) acrylate, etc.) ), (Meth) acrylic acid substituted alkyl ester Tellurium (eg, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate), carboxylic acid vinyl esters (eg, vinyl acetate and vinyl propionate), vinyl cyanide (eg, (meth) acrylonitrile and α-chloro) Acrylonitrile) and aliphatic conjugated dienes (eg, 1,3-butadiene and isoprene). Among these, unsaturated carboxylic acids, aromatic vinyl compounds, (meth) acrylic acid alkyl esters, (meth) acrylic acid alkyl aryl esters and carboxylic acid vinyl esters are preferred. Here, (meth) acrylic acid is a general term that combines acrylic acid and methacrylic acid, and (meth) acrylate is also a general term for acrylate and methacrylate.

Furthermore, an acrylic polymer having a (meth) acryloyl group in the side chain or a macromonomer (for example, a polystyrene macromonomer, a polymethyl methacrylate macromonomer, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene as a copolymerization component) An acrylic graft polymer containing glycol polypropylene glycol mono (meth) acrylate and the like is also preferable.
These can be used alone or in combination of two or more.

Anti-repellent agent:
In the composition for forming a polarizer used in the present invention, as a material for preventing repelling during coating, in addition to the surfactant (A), other polymer compounds can be added. The polymer compound used for this purpose is not particularly limited as long as it is compatible with the liquid crystalline azo dye and does not significantly inhibit the tilt angle change or orientation of the dye. Examples of polymers that can be used as repellency inhibitors are described in JP-A-8-95030, and particularly preferred specific polymer examples include cellulose esters. Examples of cellulose esters include cellulose acetate, cellulose acetate propionate, hydroxypropyl cellulose, and cellulose acetate butyrate. In order not to inhibit the orientation of the azo dye, the amount of the polymer used for the purpose of preventing repellency is generally in the range of 0.1 to 10% by mass with respect to (C) two or more liquid crystalline azo dyes. Is more preferable, being in the range of 0.1 to 8% by mass, and more preferably in the range of 0.1 to 5% by mass.

Alignment film tilt angle control agent:
An additive for controlling the tilt angle of the (C) two or more kinds of liquid crystalline azo dye molecules on the alignment film side may be added to the composition for forming a polarizer. Examples of the additive having such an action include compounds having both a polar group and a nonpolar group in the molecule. Examples of the compound having both a polar group and a nonpolar group in the molecule include P ^O —OH, P ^O —COOH, P ^O —O—P ^O , P ^O —NH ₂ , P ^O —NH—P ^O , P ^{O -SH, P O -S-P} O, P O -CO-P O, P O -COO-P O, P O -CONH-P O, P O -CONHCO-P O, P O -SO 3 H , P ^O —SO ₃ —P ^O , P ^O —SO ₂ NH—P ^O , P ^O —SO ₂ NHSO ₂ —P ^O , P ^O —C═N—P ^O , HO—P (—OP ^O ) _{2 , (HO-) 2 PO-OP} O, P (-OP O) 3, HO-PO (-OP O) 2, (HO-) 2 PO-OP O, PO (-OP O) 3, P O - Preferred examples include NO ₂ and P ^O —CN and organic salts thereof. Here, as the organic salt, in addition to the organic salt of the above compound (for example, ammonium salt, carboxylate, sulfonate, etc.), a pyridinium salt or the like can be preferably employed. Among the compounds having both a polar group and a nonpolar group in the molecule, P ^O —OH, P ^O —COOH, P ^O —O—P ^O , P ^O —NH ₂ , P ^O —SO ₃ H, HO _{^{-PO (-OP O) 2, (}} HO-) 2 PO-OP O, PO (-OP O) 3 or their organic salts. Here, each P ^O represents a nonpolar group, and when there are a plurality of P ^O , they may be the same or different.

As P 2 ^O , for example, an alkyl group (preferably a linear, branched or cyclic substituted or unsubstituted alkyl group having 1 to 30 carbon atoms), an alkenyl group (preferably a linear or branched chain having 1 to 30 carbon atoms, Cyclic substituted or unsubstituted alkenyl groups), alkynyl groups (preferably linear, branched, cyclic substituted or unsubstituted alkenyl groups having 1 to 30 carbon atoms), aryl groups (preferably having 6 to 30 carbon atoms). Examples thereof include substituted or unsubstituted aryl groups) and silyl groups (preferably substituted or unsubstituted silyl groups having 3 to 30 carbon atoms). These nonpolar groups may further have a substituent. Examples of the substituent include a halogen atom, an alkyl group (including a cycloalkyl group and a bicycloalkyl group), an alkenyl group (a cycloalkenyl group and a bicycloalkenyl group). Alkynyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy Group, aryloxycarbonyloxy group, amino group (including anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkylsulfonylamino group, arylsulfonyl Mino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group Preferred examples include carbamoyl group, arylazo group, heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, silyl group and the like.

In general, the addition amount of the alignment film tilt angle control agent is preferably about 0.0001% by mass to 30% by mass with respect to the total mass of (C) two or more liquid crystalline azo dyes, It is more preferably about 0.001% by mass to 20% by mass, and further preferably about 0.005% by mass to 10% by mass.
In the present invention, the alignment film tilt control agent described in JP-A-2006-58801 can be used.

Sugars:
Saccharides may be added to the composition for forming a polarizer used in the present invention. By adding saccharides, the degree of association of the dye aggregate can be improved, and as a result, the molecular orientation of the dye can be increased.
Examples of saccharides that can be used include monosaccharides, disaccharides, polysaccharides, and sugar derivatives such as sugar alcohols. Among the saccharides, in order to achieve the effects of the present invention, those having a hydroxyl group of usually 2 or more, preferably 3 or more, preferably 18 or less, and more preferably 12 or less are preferable from the viewpoint of molecular association. If there are too many hydroxyl groups, the interaction with the dye will be too strong and will precipitate, which will impair the orientation of the dye film, and if too little, the interaction with the dye will be insufficient and the orientation will be improved. It is not preferable because it cannot be done.

  The molecular weight of the saccharide used is preferably 1,000 or less, more preferably 700 or less. If the molecular weight of the saccharide is too large, it is not preferred because it may cause phase separation from the dye and impair the orientation of the dye film.

  The carbon number of the saccharide used is usually 36 or less, preferably 24 or less. If the saccharide has too many carbon atoms, the molecular weight of the saccharide increases, which causes phase separation from the azo dye, which may impair the orientation of the dye film.

Among the saccharides used in the present invention, monosaccharides, oligosaccharides, and monosaccharide alcohols are preferable because they satisfy the above-described optimum hydroxyl group number and molecular weight range.
Examples of monosaccharides include xylose, ribose, glucose, fructose, mannose, sorbose, and galactose.
Examples of the oligosaccharide include trehalose, kojibiose, nigerose, maltose, maltotriose, isomaltotriose, maltotetraose, isomaltose, sophorose, laminaribiose, cellobiose, gentiobiose, lactose, sucrose, melibiose, lutinose, primiverose, Examples include turanose, panose, isopanose, cellotriose, manninotriose, solatriose, melezitose, planteose, gentianose, umbelliferose, raffinose, and stachyose.
Examples of the sugar alcohol include compounds obtained by reducing the above monosaccharides and oligosaccharides such as threitol, xylitol, ribitol, arabitol, sorbitol, and mannitol.

  As the saccharide, xylose, mannose, maltose, maltotriose and arabitol are particularly preferable.

  These saccharides and sugar alcohols each have optical isomers, but each may be used alone or both in the composition used in the present invention. Moreover, 1 type of saccharides may be used independently in the said composition, and 2 or more types may be used in combination.

  In the composition used in the present invention, the saccharide content relative to (C) two or more liquid crystalline azo dyes is preferably in the range of 0.1 to 1 in terms of mass ratio. More preferably, it is 0.2 or more, particularly preferably 0.3 or more, further preferably 0.7 or less, and particularly preferably 0.6 or less. When the saccharide content is in the above range, the association degree of the dye aggregate can be increased without decreasing the degree of orientation of the aggregate.

Antifungal, antibacterial and fungicides:
You may add the chemical | medical agent which has at least any function of antifungal, antibacterial, and disinfection to the said composition for polarizer forming used by this invention. By adding these additives, the storage stability of the composition can be improved.
In the present specification, “a drug having at least one of antifungal, antibacterial, and sterilization functions” refers to an antifungal ability that suppresses the generation / growth / growth of mold, a sterilizing ability that kills microorganisms, and a microorganism It means a drug having at least one function of antibacterial activity that suppresses the generation, growth and proliferation of sucrose. Known antifungal agents, bactericides, and antibacterial agents can be used. However, it is preferable that the optical property of the polarizer formed from the composition is not deteriorated. Examples of the drug having at least one of antifungal, antibacterial and bactericidal functions that can be used in the present invention include conventional phenols such as 2,4,4′-trichloro-2′-hydroxydiphenyl, chlorine dioxide and the like. And quaternary ammonium salts such as benzalkonium chloride and the like.

  In addition, as an active ingredient 1,2-benzisothiazoline-3-one, Proxel BDN, Proxel BD20, Proxel GXL, Proxel LV, Proxel XL, Proxel XL2, Proxel Ultra10 (above, manufactured by Avecia, trade name), Polyhexametylene biguanide hydrochloride as an active ingredient, Proxel IB (Avecia, trade name), Dithio-2,2'-bis (benzmethylamide) as an active ingredient, Densil P (Avecia, trade name) ) And the like.

Further, the following compounds are particularly preferable because they exhibit an antibacterial effect particularly in a very small amount.
No. Compound name 2-chloromethyl-5-chloro-3-isothiazolone 2. 2-cyanomethyl-5-chloro-3-isothiazolone 2-hydroxymethyl-5-chloro-3-isothiazolone4. 2- (3-Methylcyclohexyl) -3-isothiazolone 2- (4-Chlorophenyl) -4,5-dichloro-3-isothiazolone6. 6. 2- (4-Ethylphenyl) -3-isothiazolone 2- (4-Nitrophenyl) -5-chloro-3-isothiazolone8. 2-chloromethyl-3-isothiazolone9. 2-methoxyphenyl-4-methyl-5-chloro-3-isothiazolone 2-morpholinomethyl-5-chloro-3-isothiazolone These compounds can be synthesized with reference to, for example, Japanese Patent Application Laid-Open No. Hei 2-278, but trade name: Tribactrane (manufactured by Hoechst), etc. Commercial products can also be used.

Moreover, the chemical | medical agent which has at least any one function of antifungal, antibacterial, and disinfection which can be used by this invention can also be used individually or in combination of 2 or more types.
The content of the agent having at least one of antifungal, antibacterial and bactericidal functions in the composition is not particularly limited, but is usually 0.01% by mass or more, preferably 0.001% by mass or more. On the other hand, it is usually 0.5% by mass or less, preferably 0.3% by mass or less. When the content of the drug having at least one of antifungal, antibacterial and sterilizing functions is within the above range, sufficient antifungal and antibacterial can be achieved without causing the precipitation of the drug or phase separation during film formation. Or the bactericidal effect is acquired.

Electron-Deficient lamellar compounds and Electron-Rich compounds:
Since the polarizer obtained by the method of the present invention has a high degree of polarization, the composition contains an electron-deficient discotic compound and an electron-rich compound. Is preferred. As the electron-deficient discotic compound and the electron-rich compound, for example, those described in JP-A-2006-323377 can be used.

The ratio of the electron-deficient discotic compound in the composition is usually 0.1 parts by mass or more, preferably 0.2 parts by mass or more, when the total composition is 100 parts by mass. Moreover, it is 50 mass parts or less normally, Preferably it is the range of 40 mass parts or less. When the ratio of the compound is within this range, the effect of addition can be obtained without excessively increasing the viscosity of the composition as a solution.
Moreover, the ratio of the electron-rich compound in the composition is usually 50 parts by mass or less, preferably 40 parts by mass or less when the entire composition is 100 parts by mass. When the ratio of the compound is within this range, the effect of addition can be obtained without excessively increasing the viscosity of the composition as a solution.
The mass fraction of the electron-deficient discotic compound and the electron-rich compound is usually preferably in the range of 10/90 to 90/10. Outside this range, it is not preferable because the effect of using an electron-deficient discotic compound or an electron-rich compound may not be obtained.

(B) Solvent:
The composition for forming a polarizer contains (B) a solvent. That is, the composition for a polarizer is prepared as a coating solution. The solvent is preferably an organic solvent. Examples of usable organic solvents include amides (eg, N, N-dimethylformamide), sulfoxides (eg, dimethyl sulfoxide), heterocyclic compounds (eg, pyridine), hydrocarbons (eg, benzene, toluene, hexane). , Alkyl halides (eg, chloroform, dichloromethane), esters (eg, methyl acetate, butyl acetate), ketones (eg, acetone, methyl ethyl ketone), ethers (eg, tetrahydrofuran, 1,2-dimethoxyethane). Hydrocarbons, alkyl halides and ketones are preferred. Two or more organic solvents may be used in combination.

  There is no restriction | limiting in particular about the preparation method of the coating liquid of the said composition for polarizer formation. It is prepared by dissolving (A) a surfactant, (C) two or more nematic liquid crystalline azo dyes, and one or more of the above-mentioned additives that are optionally added in a solvent (B). The coating liquid may not be completely dissolved but may be dispersed.

  The composition is preferably prepared as a coating solution having a total solid content of about 0.1 to 10% by mass, more preferably about 0.5 to 5% by mass. When prepared as a coating solution in this concentration range, slit coating can be stably performed.

(2) Application by slit coating method In the method of the present invention, the above-mentioned composition for forming a polarizer is applied to the surface of a substrate or the like by a slit coating method to produce a polarizer. In the slit coating method, no shear stress is applied to the coating solution during coating, and a highly uniform film can be stably formed. In addition, in the slit coating method, the direction in which the coating liquid is extruded from the slit can be matched with the rubbing treatment direction or the light irradiation direction of the alignment film, so that the spreading direction of the coating liquid does not match the orientation treatment direction. (For example, in the spin coating method, since the coating liquid is spread on the surface by centrifugal force, it is difficult to make the spreading direction and the orientation treatment direction coincide on the entire surface). In this invention, the composition containing said (A)-(C) is apply | coated to the surface by the slit coating method, (C) The molecule | numerator of a predetermined liquid crystalline azo pigment | dye is the presence of (A) surfactant. (C) The molecules of the predetermined liquid crystalline azo dye can be aligned in the horizontal direction almost completely without being inclined with respect to the layer surface in a high order in the alignment treatment direction. As a result, a polarizer with high uniformity and dichroism (specifically, a dichroic ratio of 20 or more) can be formed. The polarizer produced by the production method of the present invention is suitable not only as a polarizer installed on the outer surface side of a normal substrate but also as a polarizer (so-called in-cell polarizer) installed on the inner surface side of the substrate. Can be applied.

Slit coating method:
An example of the slit coating method is as follows.
The substrate composition is coated with the polarizer composition from a slit die of a casting coating machine having a relative movement speed of 50 to 150 mm / sec with respect to a substrate having a side length of 800 mm or more. to form a wet film having a thickness of L ¹ in. Thereafter, if necessary, a step of pre-baking the wet coating film to remove the solvent and forming a pre-baked coating film having a film thickness L ² is performed. At this time, the film thickness L ^{1 of the} wet coating film is preferably 0.1 to 20 μm, and the film thickness L ² of the dry coating film is preferably 0.01 to ² μm. The gap between the discharge port of the slit die and the substrate surface is preferably in the range of 50 μm to 200 μm.

  By using the above-mentioned composition for a polarizer and utilizing a slit coating method, for example, when a fifth generation glass substrate (1100 mm × 1250 mm) is applied, a highly uniform polarizer film can be produced. Can be manufactured well.

  The temperature during application is preferably 0 ° C. or higher and 80 ° C. or lower, and the humidity is preferably about 10% RH or higher and 80% RH or lower.

Moreover, when applying the composition for polarizers by the slit coating method, the substrate may be heated or cooled. The temperature of the substrate at this time is preferably 10 ° C. or higher and 60 ° C. or lower. If the upper limit is exceeded, the orientation may be disturbed before drying under reduced pressure, which will be described in detail below, and if it is lower than the lower limit, water droplets may adhere to the substrate surface, which may hinder coating.
Further, the applied polarizer may be dried under reduced pressure, and the substrate may be heated at that time. The temperature of the substrate at this time is preferably 60 ° C. or lower. If the upper limit is exceeded, the orientation may be disturbed before drying under reduced pressure.

  In the method of the present invention, a composition for a polarizer is applied on a substrate, color filter or alignment film that has been subjected to alignment treatment in one direction at an angle that is not parallel to the alignment treatment direction on the substrate, color filter or alignment film. Thus, a polarizer can be formed. Furthermore, it is more preferable to apply the composition for a polarizer in a direction substantially coinciding with the vertical or horizontal direction of the substrate. Thereby, a polarizer having no alignment defect and a high degree of polarization can be formed. Further, after applying the composition for a polarizer, it is not necessary to cut out the substrate in order to have a necessary polarization angle, and the productivity is increased.

(3) Drying and orientation step A coating film of the composition is formed by the coating step, and a solute such as an organic solvent is evaporated from the coating layer to orient the composition for a polarizer. Preferably, it is naturally dried at room temperature. It is preferable not to disturb the orientation state of the azo dye molecules formed by coating (avoid thermal relaxation or the like). In the pressure reduction treatment, it is also preferable to evaporate the solvent and dry at a lower temperature.

The term “depressurization” as used herein refers to removing a solvent by evaporating a substrate having a coating film (polarizer film) under reduced pressure. At this time, it is preferable that the substrate having the polarizer film be kept horizontal so that it does not flow from the high part to the bottom part.
The shorter the time from the start of application to the pressure reduction treatment of the polarizer film, the better. The time is preferably from 1 second to 30 seconds.
Examples of the decompression method include the following methods. The polarizer film obtained by applying the coating solution is put together with the substrate into a reduced pressure processing apparatus and subjected to reduced pressure processing. For example, a decompression processing apparatus as shown in FIGS. 9 and 10 of JP-A-2006-201759 can be used. Details of the decompression processing apparatus are described in JP-A No. 2004-169975.

As the conditions for the decompression treatment, the pressure in the system where the polarizer film is present is preferably 2 × 10 ⁴ Pa or less, more preferably 1 × 10 ⁴ Pa or less, and particularly preferably 1 × 10 ³ Pa or less. Further, it is preferably ¹ Pa or more, more preferably 1 × 10 ¹ Pa or more. Usually, the pressure finally reached in the system is preferably as described above. If the upper limit is exceeded, drying may fail and orientation may be disturbed. If the lower limit is exceeded, drying may be too rapid and defects may occur.
The decompression time is preferably 5 seconds or more and 180 seconds or less. If the upper limit is exceeded, the polarizer film cannot be dried rapidly before the orientation relaxation, and the orientation may be disturbed. If the lower limit is not reached, the orientation may be disturbed.

  Further, the temperature in the system during the decompression treatment is preferably 10 ° C. or more and 60 ° C. or less. If the upper limit is exceeded, convection may occur during drying, and non-uniformity may occur in the polarizer film. If the lower limit is not reached, drying may not be possible and orientation may be disturbed.

  When the coating film is dried and the composition for a polarizer is oriented, the substrate may be heated to promote the orientation. The temperature of the substrate at this time is preferably 50 ° C. or higher and 200 ° C. or lower, and particularly preferably 70 ° C. or higher and 180 ° C. or lower. In order to lower the orientation temperature, an additive such as a plasticizer may be used in combination with the polarizer composition.

For example, when the polarizer-forming composition is applied to the alignment film surface, (C) two or more kinds of liquid crystalline azo dye molecules are aligned at the tilt angle of the alignment film at the interface with the alignment film, and Orientation is performed at the tilt angle of the air interface. In order to produce a polarizer having a high degree of polarization, it is preferable to horizontally align the azo dye at any interface and fix the alignment state.
In the present specification, “tilt angle” means an angle formed between the major axis direction of an azo dye molecule and an interface (alignment film interface or air interface). From the viewpoint of polarization performance, the tilt angle on the alignment film side is preferably 0 ° to 10 °, more preferably 0 ° to 5 °, particularly preferably 0 ° to 2 °, and still more preferably 0 ° to 1 °. . Further, the tilt angle on the air interface side is preferably 0 ° to 10 °, more preferably 0 to 5 °, and particularly preferably 0 to 2 °.

In order to reduce the tilt angle on the air interface side of the molecule of the azo dye to the above range, the above composition is used as (A) a surfactant as described above, (1) a fluoro fat represented by the general formula (III) Or (2) a polymerized unit of a fluoroaliphatic group-containing monomer represented by general formula (VII) or (VIII) and a polymerized unit of an amide group-containing monomer represented by general formula (IX) It is preferable that the second fluoroaliphatic group-containing copolymer containing at least one polymer unit selected from the group consisting of: By orienting the azo dye molecules in the presence of at least one of these, the tilt angle on the air interface side can be reduced to the above range.
Incidentally, the alignment film side tilt angle tends to be reduced by the action of the alignment film as compared with the air interface side tilt angle, but by adding the above-described alignment film tilt control agent to the composition, By further reducing the tilt angle on the alignment film side, the azo dye molecules can be stably in a horizontal alignment state.

(4) Curing Step In an embodiment in which the polarizer-forming composition contains curable components such as (D) a non-liquid crystalline radical polymerizable polyfunctional monomer and (E) a polymerization initiator, an azo dye molecule It is preferable that polymerization curing proceeds by light irradiation (preferably ultraviolet irradiation), heating, or a combination thereof after making the desired orientation state.
In addition, the description of paragraphs [0050] to [0051] of JP-A-2001-91741 can be referred to for the value of light irradiation energy for polymerization.

  A polarizing element can be formed as described above.

(5) Substrate The polarizer can be formed on a substrate. The substrate to be used will be selected depending on the application of the polarizer. For example, alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass used for liquid crystal display elements, OLED elements, etc .; photoelectric conversion element substrate used for solid-state imaging elements, etc .; silicon substrate; plastic substrate; And a substrate on which a functional layer such as a transparent conductive film, a color filter film, an electrode and a TFT is formed. On these substrates, a black matrix for isolating each pixel may be formed, or a transparent resin layer may be provided for promoting adhesion. It is also preferable that the plastic substrate has a gas barrier layer and / or a solvent resistant layer on the surface thereof.

  The light transmittance of the substrate used in the present invention is preferably 80% or more. The plastic substrate is preferably an optically isotropic polymer film. The description of paragraph number [0013] of JP-A No. 2002-22294 can be applied to specific examples and preferred embodiments of the polymer. Further, even a conventionally known polymer such as polycarbonate or polysulfone that easily develops birefringence is used by reducing the expression by modifying the molecule described in International Publication WO00 / 26705. You can also.

  An example of the production method of the present invention is a so-called in-cell polarizer production method. In this example, examples of the substrate include non-alkali glass, soda glass, Pyrex (registered trademark) glass, quartz glass, and a plastic substrate used as a liquid crystal cell substrate. In order to suppress the occurrence of scattered light due to depolarization by the color filter layer, in an aspect using the in-cell polarizer, the polarizer is preferably disposed between the color filter layer and the liquid crystal layer. Therefore, it is preferable that a color filter is formed on a substrate and a polarizer is formed thereon by the above method.

(6) Alignment film It is preferable to use an alignment film in the method of the present invention. The alignment film used in the present invention may be any layer as long as (C) two or more liquid crystalline azo dye molecules can be brought into a desired alignment state on the alignment film. Organic compound (eg, ω-tricosanoic acid) by rubbing treatment of organic compound (preferably polymer) on film surface, oblique deposition of inorganic compound, formation of layer having microgroove, or Langmuir-Blodgett method (LB film) , Dioctadecylmethylammonium chloride, methyl stearylate). Furthermore, an alignment film in which an alignment function is generated by application of an electric field, application of a magnetic field or light irradiation is also known. Among them, in the present invention, an alignment film formed by rubbing treatment is preferable from the viewpoint of easy control of the pretilt angle of the alignment film, and a photo alignment film formed by light irradiation is preferable from the viewpoint of uniformity of alignment.

-Rubbing treatment alignment film The polymer material used for the alignment film formed by the rubbing treatment is described in a large number of documents, and a large number of commercially available products can be obtained. In the alignment film of the present invention, polyvinyl alcohol or polyimide and derivatives thereof are preferably used. For the alignment film, reference can be made to the description on page 43, line 24 to page 49, line 8 of WO01 / 88574A1.
The thickness of the alignment film is preferably 0.01 to 10 μm, and more preferably 0.01 to 1 μm.

The rubbing treatment can be generally carried out by rubbing the surface of the polymer layer several times with paper or cloth in a certain direction. In particular, in the present invention, “Liquid Crystal Handbook” (published by Maruzensha, October 30, 2000). It is preferable to carry out by the method described in (1).
As a method for changing the rubbing density, a method described in “Liquid Crystal Handbook” (published by Maruzen) can be used. The rubbing density (L) is quantified by the following formula (A).
Formula (A) L = Nl (1 + 2πrn / 60v)
In the formula (A), N is the number of rubbing, l is the contact length of the rubbing roller, r is the radius of the roller, n is the number of rotations (rpm) of the roller, and v is the stage moving speed (second speed).

In order to increase the rubbing density, the rubbing frequency should be increased, the contact length of the rubbing roller should be increased, the radius of the roller should be increased, the rotation speed of the roller should be increased, and the stage moving speed should be decreased, while the rubbing density should be decreased. To do this, you can do the reverse.
Between the rubbing density and the pretilt angle of the alignment film, there is a relationship in which the pretilt angle decreases as the rubbing density increases and the pretilt angle increases as the rubbing density decreases.

-Photo-alignment film The photo-alignment material used for the alignment film formed by light irradiation has description in many literatures. In the alignment film of the present invention, for example, JP 2006-285197 A, JP 2007-76839 A, JP 2007-138138 A, JP 2007-94071 A, JP 2007-121721 A, The azo compounds described in JP 2007-140465 A, JP 2007-156439 A, JP 2007-133184 A, JP 2009-109831 A, Patent No. 3888848, and Japanese Patent No. 4151746, No. 229039, a maleimide and / or alkenyl-substituted nadiimide compound having a photo-alignment unit described in JP-A No. 2002-265541 and JP-A No. 2002-317013, Japanese Patent No. 4205195, Patent Photocrosslinking property described in No. 4205198 Run derivatives, Kohyo 2003-520878, JP-T-2004-529220 and JP-mentioned as examples photocrosslinkable polyimide, polyamide, or an ester are preferred according to Patent No. 4,162,850. Particularly preferred are azo compounds, photocrosslinkable polyimides, polyamides, or esters.

The photo-alignment film formed from the above material is irradiated with linearly polarized light or non-polarized light to produce a photo-alignment film.
In this specification, “linearly polarized light irradiation” is an operation for causing a photoreaction in the photo-alignment material. The wavelength of light used varies depending on the photo-alignment material used, and is not particularly limited as long as it is a wavelength necessary for the photoreaction. Preferably, the peak wavelength of light used for light irradiation is 200 nm to 700 nm, and more preferably ultraviolet light having a peak wavelength of light of 400 nm or less.

  The light source used for light irradiation is a commonly used light source such as a tungsten lamp, a halogen lamp, a xenon lamp, a xenon flash lamp, a mercury lamp, a mercury xenon lamp, a carbon arc lamp, or various lasers (eg, semiconductor laser, helium). Neon laser, argon ion laser, helium cadmium laser, YAG laser), light emitting diode, cathode ray tube, and the like.

  As means for obtaining linearly polarized light, a method using a polarizing plate (eg, an iodine polarizing plate, a dichroic dye polarizing plate, a wire grid polarizing plate), a reflection using a prism system element (eg, Glan-Thompson prism) or a Brewster angle. A method using a type polarizer or a method using light emitted from a laser light source having polarization can be employed. Moreover, you may selectively irradiate only the light of the required wavelength using a filter, a wavelength conversion element, etc.

In the case of linearly polarized light, a method of irradiating light from the top surface or the back surface to the alignment film surface perpendicularly or obliquely to the alignment film is employed. The incident angle of the light varies depending on the photo-alignment material, but is, for example, 0 to 90 ° (vertical), preferably 40 to 90.
When non-polarized light is used, the non-polarized light is irradiated obliquely. The incident angle is 10 to 80 °, preferably 20 to 60, and particularly preferably 30 to 50 °.
The irradiation time is preferably 1 minute to 60 minutes, more preferably 1 minute to 10 minutes.

  When patterning is required, a method of performing light irradiation using a photomask as many times as necessary for pattern formation or a method of writing a pattern by laser beam scanning can be employed.

(7) Transparent resin cured layer In order to impart physical strength, durability, or optical properties to the polarizer produced by the method of the present invention, it is also preferable to provide a transparent resin cured layer on the surface of the polarizer. The layer thickness of the transparent resin cured layer is preferably in the range of 1 to 30 μm, and particularly preferably 1 to 10 μm.
The transparent resin cured layer is preferably formed by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound. The transparent resin cured layer in the present invention is obtained by applying a coating composition containing an ionizing radiation curable polyfunctional monomer or polyfunctional oligomer on the surface of the polarizer, and crosslinking reaction or polymerization reaction of the polyfunctional monomer or polyfunctional oligomer. Can be formed.
The functional group of the ionizing radiation curable polyfunctional monomer or polyfunctional oligomer is preferably a light, electron beam, or radiation polymerizable group, and among them, a photopolymerizable functional group is preferable.
Examples of the photopolymerizable functional group include unsaturated polymerizable functional groups such as a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group. Among them, a (meth) acryloyl group is preferable. Moreover, inorganic fine particles can also be contained.

As a specific example of a photopolymerizable polyfunctional monomer having a photopolymerizable functional group,
(Meth) acrylic acid diesters of alkylene glycol such as neopentyl glycol acrylate, 1,6-hexanediol (meth) acrylate, propylene glycol di (meth) acrylate;
(Meth) acrylic acid diesters of polyoxyalkylene glycols such as triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate;
(Meth) acrylic acid diesters of polyhydric alcohols such as pentaerythritol di (meth) acrylate;
(Meth) acrylic acid diesters of ethylene oxide or propylene oxide adducts such as 2,2-bis {4- (acryloxy · diethoxy) phenyl} propane and 2-bis {4- (acryloxy · polypropoxy) phenyl} propane ;
Etc.

  Furthermore, epoxy (meth) acrylates, urethane (meth) acrylates, and polyester (meth) acrylates are also preferably used as the photopolymerizable polyfunctional monomer.

  Among these, esters of polyhydric alcohol and (meth) acrylic acid are preferable. More preferably, a polyfunctional monomer having 3 or more (meth) acryloyl groups in one molecule is preferable. Specifically, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, 1,2,4-cyclohexanetetra (meth) acrylate, pentaglycerol triacrylate, pentaerythritol tetra (meth) acrylate, penta Erythritol tri (meth) acrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol triacrylate, tripentaerythritol hexatriacrylate, etc. Is mentioned. Two or more polyfunctional monomers may be used in combination.

As a polymerization initiator used for forming the transparent resin cured layer, it is preferable to use a photopolymerization initiator. As the photopolymerization initiator, a photoradical polymerization initiator and a photocationic polymerization initiator are preferable, and a photoradical polymerization initiator is particularly preferable.
Examples of the radical photopolymerization initiator include acetophenones, benzophenones, Michler's benzoylbenzoate, α-amyloxime ester, tetramethylthiuram monosulfide, and thioxanthones.

  As a commercially available photo radical polymerization initiator, Kayacure (DETX-S, BP-100, BDDK, CTX, BMS, 2-EAQ, ABQ, CPTX, EPD, ITX, QTX, BTC, manufactured by Nippon Kayaku Co., Ltd. MCA, etc., all trade names), Irgacure (651, 184, 127, 500, 907, 369, 1173, 2959, 4265, 4263 etc., all trade names) manufactured by Ciba Specialty Chemicals Co., Ltd., Sartomer Examples include Esacure (KIP100F, KB1, EB3, BP, X33, KT046, KT37, KIP150, TZT, all of which are trade names).

In particular, photocleavable photoradical polymerization initiators are preferred. The photocleavable photoradical polymerization initiator is described in the latest UV curing technology (P.159, issuer; Kazuhiro Takasawa, publisher; Technical Information Association, published in 1991).
Examples of commercially available photocleavable photoradical polymerization initiators include Irgacure (651, 184, 127, 907, trade names) manufactured by Ciba Specialty Chemicals.

It is preferable to use a photoinitiator in the range of 0.1-15 mass parts with respect to 100 mass parts of curable resin, More preferably, it is the range of 1-10 mass parts.
In addition to the photopolymerization initiator, a photosensitizer may be used. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone.
Examples of commercially available photosensitizers include KAYACURE (DMBI, EPA, both trade names) manufactured by Nippon Kayaku Co., Ltd.
The photopolymerization reaction is preferably carried out by UV irradiation after application and drying of the high refractive index layer.

In order to impart brittleness, the transparent resin cured layer may be added with an oligomer or polymer having a mass average molecular weight of 500 or more, or both.
Examples of the oligomer and polymer include (meth) acrylate-based, cellulose-based, and styrene-based polymers, urethane acrylate, and polyester acrylate. Preferable examples include poly (glycidyl (meth) acrylate) and poly (allyl (meth) acrylate) having a functional group in the side chain.

  The total amount of oligomer and polymer in the transparent resin cured layer is preferably 5 to 80% by mass, more preferably 25 to 70% by mass, and particularly preferably 35 to 65% by mass with respect to the total mass of the resin layer. is there.

The strength of the transparent resin cured layer is preferably H or more, more preferably 2H or more, and even more preferably 3H or more in a pencil hardness test according to JIS K5400.
Further, in the Taber test according to JIS K5400, the smaller the wear amount of the test piece before and after the test, the better.
In the formation of the transparent resin cured layer, when the ionizing radiation curable compound is formed by a crosslinking reaction or a polymerization reaction, the crosslinking reaction or the polymerization reaction is preferably performed in an atmosphere having an oxygen concentration of 10% by volume or less. . By forming in an atmosphere having an oxygen concentration of 10% by volume or less, a transparent resin cured layer excellent in physical strength and durability can be formed, which is preferable.
Preferably, it is formed by a crosslinking reaction or polymerization reaction of an ionizing radiation curable compound in an atmosphere having an oxygen concentration of 6% by volume or less, more preferably an oxygen concentration of 4% by volume or less, particularly preferably an oxygen concentration of 2 It is not more than volume%, more preferably not more than 1 volume%.

As a method of reducing the oxygen concentration to 10% by volume or less, it is preferable to replace the atmosphere (nitrogen concentration of about 79% by volume, oxygen concentration of about 21% by volume) with another gas, particularly preferably replacement with nitrogen (nitrogen purge). It is to be.
The transparent resin cured layer may further have a function of optical anisotropy.

The transparent resin cured layer can be produced by the following method.
First, a curable transparent resin composition containing the above materials is prepared. As a solvent used for preparing the composition, it is preferable to use a liquid having a boiling point of 60 to 170 ° C. Specifically, water, alcohol (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketone (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ester (eg, methyl acetate, ethyl acetate, propyl acetate) , Butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene chloride, chloroform, carbon tetrachloride), aromatic hydrocarbons (Eg, benzene, toluene, xylene), amide (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran), ether alcohol (eg, 1-methoxy) 2-propanol) and the like. Of these, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethanol and butanol are preferred, and particularly preferred dispersion media are methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and ethanol.
The amount of the solvent used is preferably such that the solid content concentration of the curable transparent resin composition is 2 to 50% by mass, and more preferably 3 to 40% by mass.

The application method of the polarizer is preferably used for applying the coating solution, but the following application method may be used.
Specific wet deposition methods include Yuji Harasaki, “Coating Engineering”, Asakura Shoten Co., Ltd., published March 20, 1971, pages 253-277 and “Creation and Application of Molecularly Cooperative Materials” supervised by Kunihiro Ichimura. Company CMC Publishing, published on March 3, 1998, pages 118 to 149, etc., such as spin coating method, spray coating method, slit and spin method, wire bar coating method, roll coating method , Blade coating method, free span coating method, extrusion coating method, direct gravure coating method, reverse gravure coating method, die coating method, and inkjet method.

  When forming a transparent resin cured layer, curing is preferably performed by ultraviolet irradiation.

2. Polarizer The polarizer produced by the production method of the present invention is formed by orienting the molecules of (C) two or more nematic liquid crystalline azo dyes in the presence of (A) a surfactant. Have a high dichroic ratio. Therefore, even a thin film can achieve a high degree of polarization. Further, since it is formed by using a slit coating method, it can be formed as a highly uniform thin film without any alignment defects. The preferred range of the degree of polarization varies depending on the application. For example, in an embodiment used as a so-called in-cell type polarizer, the degree of polarization is preferably 0.4 or more, more preferably 0.5 or more, and 0.6 or more. Further preferred. The upper limit is better as the theoretical limit is 1 and closer to 1, but there is no problem at 0.99 or less, no problem at 0.95 or less, and no problem at 0.90 or less.
Moreover, it is preferable that the thickness of the polarizer manufactured by the manufacturing method of this invention is 0.01-2 micrometers, and it is more preferable that it is 0.05-2 micrometers.

3. Laminated body and method for producing the same The present invention includes the following steps [1], [2] and [3]:
[1] Step of rubbing or irradiating light with an alignment film formed on a color filter [2] On the alignment film, (A) a surfactant, (B) a solvent, and (C) two or more nematics Step of slit coating a polarizer-forming composition containing an azo dye having liquid crystallinity [3] By evaporating the solvent, (C) two or more kinds of nematic liquid crystal azo dyes are aligned. The present invention also relates to a method for manufacturing a laminate including the steps of forming a polarizer in this order, and a laminate manufactured by the method.

  The details of the steps [1] to [3], the alignment film used in each step, the composition for forming a polarizer, and the like are as described in each step described in the production method of the present invention, and a preferred embodiment. Is the same. Moreover, as a color filter utilized for the manufacturing method of the said laminated body, what is generally used as a color filter board | substrate in a display apparatus can be used. For example, a color filter substrate in which a color filter layer is formed on the surface of an alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass, a plastic substrate, or the like can be used. The color filter substrate may have other functional layers such as a transparent conductive film, a color filter film, an electrode, and a TFT in addition to the color filter layer. Further, a black matrix for isolating each pixel may be formed.

  The laminate produced by the production method of the present invention can be used as a color filter substrate of a display device.

The laminate produced by the method of the present invention may be a transfer material. A polarizer may be transferred onto a liquid crystal cell substrate using the transfer material.
Hereinafter, a transfer material useful for forming the polarizer in a liquid crystal display device, particularly in a liquid crystal cell will be described.
3. -1 Transfer Material The transfer material usable in the present invention has at least a support and a film functioning as a polarizer (hereinafter referred to as “polarizing film”). Furthermore, it is preferable to have at least one photosensitive resin layer on the polarizing film. The photosensitive resin layer is useful because it facilitates the transfer of the polarizing film even when the process such as patterning is not performed. Further, for example, there may be a layer between the support and the polarizing film for controlling mechanical properties such as cushioning for absorbing irregularities on the counterpart substrate side during transfer, or for imparting irregularity followability. Alternatively, a layer functioning as an alignment layer for controlling the alignment of the dye of the polarizing film may be disposed, or both layers may be provided. Moreover, you may provide the protective layer which can peel on the outermost surface for the objectives, such as surface protection of the photosensitive resin layer.

  The support used for the above transfer material may be transparent or opaque and is not particularly limited. Examples of the polymer constituting the support include cellulose ester (eg, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose acetate butyrate), polyolefin (eg, norbornene-based polymer), poly (Meth) acrylic acid esters (eg, polymethyl methacrylate), polycarbonate, polyester and polysulfone are included. For the purpose of inspecting optical properties in the production process, the transparent support is preferably a transparent and low birefringent material, and cellulose ester and norbornene are preferred from the viewpoint of low birefringence. As a commercially available norbornene-based polymer, Arton (manufactured by JSR Co., Ltd.), Zeonex, Zeonore (manufactured by Nippon Zeon Co., Ltd.), or the like can be used. Inexpensive polycarbonate, polyethylene terephthalate, and the like are also preferably used.

  The polarizing film is formed on the support using the slit coating method. Alternatively, an alignment film may be formed on the support, and a polarizing film may be formed thereon by a slit coating method. Note that the polarizing film included in the transfer material does not need to satisfy the optical characteristics sufficient for the polarization performance. For example, the polarization performance is expressed or changed through the exposure process performed in the transfer process, and the final film is obtained. In particular, the polarizing film may exhibit a polarizing performance necessary for the polarizing film.

Photosensitive resin layer:
The transfer material preferably has a photosensitive resin layer. The photosensitive resin layer is made of a photosensitive resin composition, and the photosensitive resin layer includes at least (1) an alkali-soluble resin, (2) a monomer or an oligomer, and (3) a photopolymerization initiator or photopolymerization. It is preferable to form from the resin composition containing an initiator system.

(1) Alkali-soluble resin The alkali-soluble resin (hereinafter sometimes simply referred to as “binder”) is preferably a polymer having a polar group such as a carboxylic acid group or a carboxylic acid group in the side chain. Examples thereof include JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and JP-A-57-36. A methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer as described in JP-A-59-71048 Etc. Moreover, the cellulose derivative which has a carboxylic acid group in a side chain can also be mentioned, In addition to this, what added the cyclic acid anhydride to the polymer which has a hydroxyl group can also be used preferably. Further, as particularly preferred examples, copolymers of benzyl (meth) acrylate and (meth) acrylic acid described in US Pat. No. 4,139,391, benzyl (meth) acrylate, (meth) acrylic acid and other monomers And a multi-component copolymer. The binder polymer having these polar groups may be used alone or in the state of a composition used in combination with a normal film-forming polymer, and contained in the total solid content of the photosensitive resin composition. The amount is generally 20 to 50% by mass, and preferably 25 to 45% by mass.

(2) Monomer or oligomer The monomer or oligomer used in the photosensitive resin layer is preferably a monomer or oligomer that has two or more ethylenically unsaturated double bonds and undergoes addition polymerization by light irradiation. . Examples of such monomers and oligomers include compounds having at least one addition-polymerizable ethylenically unsaturated group in the molecule and having a boiling point of 100 ° C. or higher at normal pressure. Examples include monofunctional acrylates and monofunctional methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) ) Acrylate, trimethylolethane triacrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexane All di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate; multifunctional such as trimethylolpropane and glycerin Polyfunctional acrylates and polyfunctional methacrylates such as those obtained by adding ethylene oxide or propylene oxide to alcohol and then (meth) acrylated can be mentioned.

Further, urethane acrylates described in JP-B-48-41708, JP-B-50-6034 and JP-A-51-37193; JP-A-48-64183, JP-B-49-43191 And polyester acrylates described in Japanese Patent Publication No. 52-30490; polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid.
Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferable.
In addition, “polymerizable compound B” described in JP-A-11-133600 can also be mentioned as a preferable example.
These monomers or oligomers may be used alone or in admixture of two or more. The content of the photosensitive resin composition with respect to the total solid content is generally 5 to 50% by mass, and 10 to 40% by mass. % Is preferred.

(3) Photopolymerization initiator or photopolymerization initiator system As the photopolymerization initiator or photopolymerization initiator system used in the photosensitive resin layer, a vicinal poly disclosed in US Pat. No. 2,367,660 is used. Ketaldonyl compounds, acyloin ether compounds described in US Pat. No. 2,448,828, aromatic acyloin compounds substituted with α-hydrocarbons described in US Pat. No. 2,722,512, US Pat. No. 3,046,127 And a polynuclear quinone compound described in U.S. Pat. No. 2,951,758, a combination of a triarylimidazole dimer described in U.S. Pat. No. 3,549,367 and a p-aminoketone, and a benzoin described in JP-B 51-48516. Thiazole compounds and trihalomethyl-s-triazine compounds, US Pat. No. 4,239,850 The listed trihalomethyl - triazine compound include a trihalomethyl oxadiazole compounds described in U.S. Pat. No. 4,212,976. In particular, trihalomethyl-s-triazine, trihalomethyloxadiazole, and triarylimidazole dimer are preferable.
In addition, “polymerization initiator C” described in JP-A-11-133600 can also be mentioned as a preferable example.
These photopolymerization initiators or photopolymerization initiator systems may be used singly or as a mixture of two or more, but it is particularly preferable to use two or more. When at least two kinds of photopolymerization initiators are used, display characteristics, particularly display unevenness, can be reduced.
The content of the photopolymerization initiator or photopolymerization initiator system with respect to the total solid content of the photosensitive resin composition is generally 0.5 to 20% by mass, and preferably 1 to 15% by mass.

Other layers:
It is preferable to form a thermoplastic resin layer between the support and the polarizing film of the transfer material in order to control the mechanical properties and the unevenness followability. As the component used for the thermoplastic resin layer, organic polymer substances described in JP-A-5-72724 are preferable, and the polymer softening point according to the Viker Vicat method (specifically, the American Material Testing Method ASTM D1 ASTM D1235). It is particularly preferable that the softening point by the measurement method is selected from organic polymer substances having a temperature of about 80 ° C. or less. Specifically, polyolefins such as polyethylene and polypropylene, ethylene copolymers such as ethylene and vinyl acetate or saponified products thereof, ethylene and acrylic acid esters or saponified products thereof, polyvinyl chloride, vinyl chloride and vinyl acetate and saponified products thereof. Vinyl chloride copolymer such as fluoride, polyvinylidene chloride, vinylidene chloride copolymer, polystyrene, styrene copolymer such as styrene and (meth) acrylic acid ester or saponified product thereof, polyvinyl toluene, vinyl toluene and (meta ) Vinyl toluene copolymer such as acrylic ester or saponified product thereof, poly (meth) acrylic ester, (meth) acrylic ester copolymer such as butyl (meth) acrylate and vinyl acetate, vinyl acetate copolymer Combined nylon, copolymer nylon, N-alkoxyme Le nylon, and organic polymeric polyamide resins such as N- dimethylamino nylon.

  In the transfer material, it is preferable to provide an intermediate layer for the purpose of preventing mixing of components during application of a plurality of application layers and during storage after application. As the intermediate layer, it is preferable to use an oxygen-blocking film having an oxygen-blocking function, which is described as “separation layer” in JP-A-5-72724. This reduces the time load and improves productivity. The oxygen barrier film is preferably one that exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkali solution, and can be appropriately selected from known ones. Among these, a combination of polyvinyl alcohol and polyvinyl pyrrolidone is particularly preferable.

  The thermoplastic resin layer and the intermediate layer can also be used as the alignment layer. In particular, polyvinyl alcohol and polyvinyl pyrrolidone preferably used for the intermediate layer are also effective as an alignment layer, and it is preferable that the intermediate layer and the alignment layer are made into one layer.

  A thin protective film is preferably provided on the resin layer in order to protect it from contamination and damage during storage. The protective film may be made of the same or similar material as the temporary support, but must be easily separated from the resin layer. As the protective film material, for example, silicon paper, polyolefin or polytetrafluoroethylene sheet is suitable.

  The polarizing film and the photosensitive resin layer, and the alignment layer, the thermoplastic resin layer, and the intermediate layer, which are formed as desired, can be formed by a method similar to the method for forming the polarizing film. Two or more layers may be applied simultaneously. The methods of simultaneous application are described in US Pat. Nos. 2,761,791, 2,941,898, 3,508,947, and 3,526,528 and Yuji Harasaki, Coating Engineering, page 253, Asakura Shoten (1973).

3. -2 Forming method of polarizing film using transfer material:
The method for transferring the transfer material on the substrate in the present invention is not particularly limited, and the method is not particularly limited as long as the polarizing film and the photosensitive resin layer can be simultaneously transferred onto the substrate. For example, the transfer material referred to in the present invention formed in a film shape is attached by pressing or thermocompression bonding with a roller or flat plate heated and / or pressurized using a laminator with the photosensitive resin layer side facing the substrate surface side. be able to. Specific examples include laminators and laminating methods described in JP-A-7-110575, JP-A-11-77942, JP-A-2000-334836, and JP-A-2002-148794. From this point of view, it is preferable to use the method described in JP-A-7-110575. Thereafter, the support may be peeled off, and another layer such as an electrode layer may be formed on the surface of the polarizing film exposed by peeling.

There is no particular limitation on the substrate that is a transfer material to which the transfer material is transferred. For example, a soda glass plate having a silicon oxide film on the surface, a known glass plate such as a low expansion glass, a non-alkali glass, a quartz glass plate, or a plastic film can be used. The material to be transferred may be one in which a layer such as a color filter is provided on a transparent substrate. Moreover, the material to be transferred can be well adhered to the photosensitive resin layer by performing a coupling treatment in advance. As the coupling treatment, a method described in JP 2000-39033 A is preferably used. In addition, although it does not necessarily limit, as a film thickness of a board | substrate, 700-1200 micrometers is generally preferable.
Instead of providing an adhesive layer on the polarizing film, an adhesive layer may be provided on the transfer material.

4). Display Device The display device of the present invention includes at least one polarizer manufactured by the manufacturing method of the present invention or a laminate manufactured by the manufacturing method of the present invention. There is no particular limitation on the configuration and the like. Specifically, transmissive, reflective, or transflective liquid crystal display devices of various modes such as TN, STN, VA, ECB, IPS, and OCB, OLED, and the like can be given. Particularly preferred is a display device in which the polarizer of the present invention is installed on the inner surface side of the substrate (so-called in-cell polarizer), and more preferred is a display device laminated on a color filter substrate. With such a configuration, it is possible to reduce a decrease in contrast due to scattered light caused by depolarization by the color filter layer.

  The present invention will be described more specifically with reference to the following examples. The materials, reagents, amounts and ratios of substances, operations, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples. In the following, all parts and% are based on mass unless otherwise specified.

[Example 1]
(Preparation of composition for alignment film)
Components of the following composition were prepared as a composition for rubbing alignment film.
-Alignment film material: 0.40 mass part of the following polyvinyl alcohol-Solvent: Water 74.70 mass parts Methanol 24.90 mass parts

(Preparation of glass substrate with rubbing alignment film)
The obtained alignment film composition is applied onto a glass substrate with a # 14 wire bar, dried at 80 ° C. for 5 minutes, and then rubbed to provide a 0.7 μm-thick rubbed alignment film. A glass substrate was produced. The glass substrate had a thickness of 0.7 mm and a size of 150 mm × 150 mm.

(Preparation of polarizer composition)
As the composition for a polarizer of the present invention, components having the following composition were prepared.
(A) Surfactant: Megafac F780, manufactured by Dainippon Ink Co., Ltd. (compound described in Example 1 of Japanese Patent No. 4190275) 0.01 parts by mass (B) Solvent: 99.99 parts by mass of chloroform (C) Azo Dye: 0.50 part by mass of the following compound (A-16)
The following compound (D-1) 0.50 mass part

(Preparation of polarizer film)
The obtained composition for a polarizer was fed into a slit die having a coating width of 150 mm, applied to the glass substrate with a rubbing alignment film disposed on the stage from the die discharge port, and wet having a film thickness L ^{1 of} 6 μm. A coating film was formed. The moving speed (relative moving speed) of the substrate with respect to the fixed die was 100 mm / sec, and the gap between the die discharge port and the surface of the substrate was 150 μm.
After forming the wet coating film, drying was performed at 70 ° C. for 60 seconds to form a dry coating film having a film thickness L ^{2 of} 0.06 μm.

(Evaluation of polarizer film)
The formed polarizer film was evaluated by the following method.
(1) Evaluation of dichroism The dichroic ratio was calculated by the following formula after measuring the absorbance of the polarizer film with a spectrophotometer in which an iodine-type polarizing element was arranged in the incident optical system. Absorbance (Az) at 500 nm for polarized light having a vibration plane in the direction of the absorption axis in the plane of the polarizer film and absorbance at 500 nm for polarized light having a plane of vibration in the direction of the polarization axis in the plane of the polarizer film. Table 1 shows the dichroic ratio and the phase transition temperature obtained from (Ay). Dichroic ratio (D) = Az / Ay
Az: Absorbance with respect to the polarized light in the absorption axis direction of the polarizer film Ay: Absorbance with respect to the polarized light in the polarization axis direction of the polarizer film (2) Evaluation of alignment defects The presence or absence of alignment defects was visually inspected with an optical microscope. Evaluated by criteria. The results are shown in Table 1. As shown in Example 1, almost no alignment defects were visually observed, and the level was “◯”.
A: Not visible at all.
○: Slightly visible.
Δ: Occurrence is observed in the outer peripheral portion.
X: An alignment defect can be confirmed in most of the whole part.

  As shown in the following table, all of the azo dyes represented by the formula (I) used in Example 1 have nematic liquid crystal properties, and the film produced in Example 1 is sufficient as a polarizing film. It had a high dichroic ratio that could function. Furthermore, the alignment defects were hardly observed and were good.

[Examples 2 to 4]
A polarizer film was produced in the same manner as in Example 1 except that the azo dye was changed as shown in Table 1 below.
Table 1 shows the dichroic ratio and phase transition temperature of the obtained polarizer film.
All of the azo dyes represented by the formula (I) used in Examples 2 to 4 have nematic liquid crystal properties, and the films produced in each Example can sufficiently function as a polarizing film. It had a dichroic ratio. Furthermore, almost no alignment defects were observed, and all were at the “◯” level.

[Example 5]
(Preparation of polarizer composition)
As the composition for a polarizer, components having the following composition were prepared.
(A) Surfactant: 0.02 parts by mass of the following compound (I-6) (B) Solvent: 93.89 parts by mass of chloroform (C) Azo dye: 1.00 parts by mass of the following compound C-22
Compound D-1 1.00 parts by mass (D) Non-liquid crystalline polyfunctional monomer:
Ethylene oxide modified trimethylolpropane triacrylate (V # 360, manufactured by Osaka Organic Chemical Co., Ltd.) 2.00 parts by mass Dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) 2.00 parts by mass (E ) Polymerization initiator: Irgacure 907
(Ciba Specialty Chemicals Co., Ltd.) 0.06 parts by mass (F) sensitizer: Kayacure DETX
(Nippon Kayaku Co., Ltd.) 0.03 parts by mass

(Preparation of polarizer film)
The obtained composition for a polarizer was fed into a slit die having a coating width of 150 mm, applied to the glass substrate with a rubbing alignment film disposed on the stage from the die discharge port, and wet having a film thickness L ^{1 of} 6 μm. A coating film was formed. The moving speed of the substrate relative to the fixed die and the gap between the die outlet and the surface of the substrate were the same as in Example 1.
After forming the wet coating film, drying was performed at 50 ° C. for 60 seconds to form a dry coating film having a film thickness L ^{2 of} 0.36 μm. Then, after irradiating 5 J ultraviolet rays under a nitrogen atmosphere (oxygen concentration of 100 ppm or less) to photopolymerize the coating film, it is further heated at 180 ° C. for 1 hour to obtain a polarizer film in which the alignment state is fixed. It was.

(Evaluation of polarizer film)
Table 1 shows the dichroic ratio and phase transition temperature of the obtained polarizer film.
The azo dyes represented by formula (I) used in Example 5 all have nematic liquid crystal properties, and the film produced in Example 5 has a high dichroic ratio that can sufficiently function as a polarizing film. Had. Furthermore, almost no alignment defects were observed, and the level was “◯”.

[Example 6]
(Preparation of composition for photo-alignment film)
The composition for the photo-alignment film was prepared by making components of the following composition into a uniform solution and then pressure-filtering with a 0.45 μm membrane filter.
-Alignment film material: 1.00 parts by mass of the following azo compound-Solvent: 49.50 parts by mass of N-methyl-2-pyrrolidone
49-50 parts by mass of 2-butoxyethanol

(Preparation of glass substrate with photo-alignment film)
The obtained composition for photo-alignment film is coated on a glass substrate with a wire bar, dried at 100 ° C. for 1 minute, and then linearly polarized light having a wavelength of around 365 nm through a band-pass filter through an ultra-high pressure mercury lamp. The substrate was irradiated with the ultraviolet rays from the vertical direction to produce a glass substrate with a photo-alignment film having a thickness of 0.07 μm. The integrated light quantity was 5 J / cm ² .

(Preparation of polarizer composition)
As the composition for a polarizer of the present invention, components having the following composition were prepared.
(A) Surfactant: Compound (I-6) 0.01 parts by mass (B) Solvent: Chloroform 99.99 parts by mass (C) Azo dye: 0.50 parts by mass of the following compound (A-46)
The following compound (B-18) 0.50 mass part

(Preparation of polarizer film)
The obtained composition for a polarizer was fed into a slit die having a coating width of 150 mm, and applied to the glass substrate with a photo-alignment film disposed on the stage from the discharge port of the die, and a wet thickness of L ¹ : 6 μm. A coating film was formed. The moving speed (relative moving speed) of the substrate with respect to the fixed die was 100 mm / sec, and the gap between the die discharge port and the surface of the substrate was 150 μm.
After the wet coating film was formed, drying was performed at 70 ° C. for 60 seconds to form a dry coating film having a film thickness L ^{2 of} 0.06 μm.

(Evaluation of polarizer film)
Table 1 shows the dichroic ratio and phase transition temperature of the obtained polarizer film. The azo dyes represented by formula (I) used in Example 6 all have nematic liquid crystal properties, and the film produced in Example 6 has a high dichroic ratio that can sufficiently function as a polarizing film. Had. Furthermore, no alignment defects were observed, and the level was “レ ベ ル”.

[Comparative Example 1]
(Preparation of polarizer film)
The composition for polarizer of Example 1 was applied to the glass substrate with a rubbing alignment film of Example 1 with a spin coater, and then dried at 70 ° C. for 60 seconds to obtain a film thickness L ^{2 of} 0.06 μm. A dry coating was formed.

(Evaluation of polarizer film)
Table 1 shows the dichroic ratio and phase transition temperature of the obtained polarizer film. Although the dichroic ratio was lowered, it was a level capable of functioning as a polarizing film, but schlieren-like alignment defects were observed around the outer peripheral portion, and the alignment defects were at the “Δ” level.

[Comparative Example 2]
(Preparation of polarizer film)
The composition for polarizer of Example 6 was applied to the glass substrate with a photo-alignment film of Example 6 using a spin coater, and then dried at 70 ° C. for 60 seconds to obtain a film thickness L ^{2 of} 0.06 μm. A dry coating was formed.

(Evaluation of polarizer film)
Table 1 shows the dichroic ratio and phase transition temperature of the obtained polarizer film. The dichroic ratio decreased, and further, schlieren-like alignment defects were observed on the entire surface, and the alignment defects were at the “x” level.

[Comparative Example 3]
(Preparation of polarizer film)
A polarizer film was prepared by the method of Example 6 except that (A) surfactant: Compound (I-6) was not added to the polarizer composition of Example 6.

(Evaluation of polarizer film)
The dichroic ratio of the obtained polarizer film was 20 and almost the same level as the result of Example 6, and no schlieren-like alignment defect was observed, but the reverse tilt domain was observed on the entire surface, and the alignment defect was “ “△” level.

Claims (12)

(A) Surfactant, (B) solvent, and (C) two or more kinds of azo dyes having nematic liquid crystallinity represented by the following general formula (I), including liquid crystalline non-coloring compounds The manufacturing method of a polarizer including the process of apply | coating the composition which does not have a slit coating method:

In the formula, R ^{1 to} R ⁴ each independently represents a hydrogen atom or a substituent; R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group which may have a substituent; L ¹ Represents —N═N—, —N═CH—, —C (═O) O— group, or —OC (═O) —; A ¹ represents an optionally substituted phenyl group; Represents a naphthyl group which may have a substituent, or an aromatic heterocyclic group which may have a substituent; B ¹ represents a divalent aromatic which may have a substituent; Represents a hydrocarbon group or a divalent aromatic heterocyclic group; n represents an integer of 1 to 4, and when n is 2 or more, a plurality of B ^{1 s} may be the same as or different from each other. (C) At least one of azo dyes having a nematic liquid crystal property represented by two or more general formulas (I) is a compound represented by the following general formula (Ia): Method according to 1:

In the formula, R ⁷ and R ⁸ each independently represents a hydrogen atom, a methyl group, or an ethyl group; L ^1a represents —N═N—, —N═CH—, —O (C═O) —, Or -CH = CH-; A ^1a represents a group represented by the following general formula (IIa) or (IIIa); B ^1a and B ^2a independently represent the following formulas (IVa), (Va) Or represents a group represented by (VIa);

In the formula, R ⁹ has an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent. An oxycarbonyl group which may be substituted or an acyloxy group which may have a substituent;

In formula, m represents the integer of 0-2. (C) At least one of the azo dyes having nematic liquid crystal properties represented by two or more general formulas (I) is an azo dye represented by the following general formula (Ib) or (Ic). Method according to claim 1 or 2, characterized in that:

In the formula, R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, a methyl group, or an ethyl group; L ^1b represents —N═N— or — (C═O) O—; L ^2b represents -N = CH -, - (C = O) O-, or -O (C = O) - represents; a ^1b represents a group represented by the following formula (IIb) or (IIIb); m is Represents an integer of 0 to 2;

In the formula, R ¹⁴ has an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent. Or an acyloxy group which may have a substituent.

In the formula, R ¹² and R ¹³ represent a hydrogen atom, a methyl group, or an ethyl group, and A ^1c represents a group represented by the following formula (IIc) or (IIIc).

In the formula, R ¹⁴ has an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent. Or an acyloxy group which may have a substituent. The (A) surfactant is
(I) a polymerization unit of a fluoroaliphatic group-containing monomer represented by the following general formula (VII) or (VIII) and (ii) a polymerization unit of an amide group-containing monomer represented by the following general formula (IX), or 4. The composition according to claim 1, comprising at least one fluoroaliphatic group-containing copolymer containing a polymer unit derived from poly (oxyalkylene) acrylate and / or poly (oxyalkylene) methacrylate. Method according to item 1:

In the formula, R ¹ represents a hydrogen atom or a methyl group, and m represents an integer of 4 to 8;

In the formula, R ¹ represents a hydrogen atom or a methyl group, and m represents an integer of 4 to 8;

Wherein, R ³ represents a hydrogen atom or a methyl group, R ^10, R ¹¹ represents an alkyl group having 1 to 6 carbon atoms. The said (A) surfactant contains at least 1 sort (s) of the fluoro aliphatic group containing compound represented by the following general formula (X), The any one of Claims 1-4 characterized by the above-mentioned. Method.

In the formula, R ¹¹ , R ²² and R ³³ each independently represents an alkoxy group having a CF ₃ group or a CF ₂ H group at the terminal; X ¹¹ , X ²² and X ³³ each independently represent —NH—, -O- or -S-; m11, m22 and m33 each independently represents an integer of 1 to 3;   6. The composition according to any one of claims 1 to 5, wherein the composition further comprises (D) a non-liquid crystalline polyfunctional monomer having a radical polymerizable group, and (E) a photopolymerization initiator. The method described. (C) Content of 2 or more types of azo pigment | dye which has nematic liquid crystallinity is 20 mass% or more in the total solid content except a solvent, The any one of Claims 1-6 characterized by the above-mentioned. A method for producing a polarizer. (C) The total content of azo dyes having two or more nematic liquid crystal properties and (D) a non-liquid crystalline polyfunctional monomer having a radical polymerizable group is 50 in the total solid content excluding the solvent. The method according to claim 6 or 7, characterized in that the content is not less than mass%. The polarizer manufactured by the method of any one of Claims 1-8. The following steps [1], [2] and [3]:
[1] Step of rubbing or irradiating the alignment film formed on the color filter [2] Step of slit coating the composition according to any one of claims 1 to 8 on the alignment film [3] Evaporating the solvent (C) The manufacturing method of the laminated body which orientates the azo pigment | dye which has 2 or more types of nematic liquid crystallinity, and makes it a polarizer in this order. The laminated body manufactured by the method of Claim 10. A display device comprising the polarizer according to claim 9 or the laminate according to claim 11.