JP2010215846A - Dichroic dye composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dye composition which exhibits high dichroism, is synthesized with a small number of steps, and comprises a dichroic pigment aligned with a high order on a rubbed alignment layer. <P>SOLUTION: The dichroic dye composition includes at least one kind of azo compound having liquid crystallinity which is expressed by general formula (1) and has a symmetric structure with respect to a linking group L. In the formula, L represents a single bond or a divalent linking group; R represents a hydrogen atom, alkyl, alkoxy or amino; Ar represents an aromatic hydrocarbon group or aromatic heterocyclic ring optionally having a substituent (when there are more than one Ar, they may be the same or different); a represents an integer of 1-3. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a dichroic dye composition. The present invention also relates to a light absorption anisotropic film, a polarizing element and a liquid crystal display device using the composition.

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 were 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 and light resistance are not sufficient. Further, the extinction color is deep blue, and it cannot be said to be an ideal achromatic polarizing element over the entire visible spectrum region.

  Therefore, a polarizing element using an organic dye as a dichroic material has been studied. However, these organic dyes have a problem that only a polarizing element having a dichroism considerably inferior to iodine can be obtained. In particular, a polarizing element is an important component in an LCD that uses the optical rotation and birefringence of light as a display principle. In recent years, a new polarizing element has been developed for the purpose of improving display performance and the like. .

  Patent Document 1 proposes a light absorption anisotropic film obtained by curing an organic dye (dichroic dye) in an oriented state. Thus, in order to arrange rod-like compounds with a high degree of orientational order, it is important that the aspect ratio (= molecular length / molecular width) of the compound is large. However, in order to obtain such a compound, it is necessary to go through many steps, and there is a problem that the synthesis is difficult.

JP 11-305036 A

  An object of the present invention is to provide a dye composition having high dichroism, which can be synthesized with a small number of steps and uses a dichroic dye that is oriented with a high degree of order on a rubbing alignment film. . Another object of the present invention is to provide a light absorption anisotropic film, a polarizing element, and a liquid crystal display device using the composition.

As a result of intensive studies, the present inventors have achieved the solution of the above problem by the following means.
<1> A dichroic dye composition containing at least one azo compound having liquid crystallinity and having a symmetric structure via a linking group L, represented by the following general formula (1).

(In the formula, L represents a single bond or a divalent linking group, R represents a hydrogen atom, an alkyl group, an alkoxy group, or an amino group, and Ar represents an aromatic hydrocarbon group which may have a substituent. Alternatively, it represents an aromatic heterocyclic ring (when there are a plurality of Ars, they may be the same or different from each other), and a represents an integer of 1 to 3.)
<2> The dichroic dye as described in <1>, wherein in the azo compound represented by the general formula (1), Ar is a phenylene group or a naphthylene group which may have a substituent. Composition.
<3> In the azo compound represented by the general formula (1), L represents a single bond, azo group, ethylene group, 1,4-cyclohexylene group, acetylene group, ester group, phenylene group, naphthylene group, piperidinyl group. The dichroic dye composition according to <1> or <2>, wherein the dichroic dye composition is a linking group composed of one or more selected from piperazinyl groups.
<4> A light absorption anisotropic film formed from the dichroic dye composition according to any one of <1> to <3>.
<5> A polarizing element having an alignment film and the light absorption anisotropic film according to <4> on a support.
<6> A liquid crystal display device having the light absorption anisotropic film according to <4> or the polarizing element according to <5>.
<7> (1) A step of rubbing the support or the alignment film formed on the support; and (2) <1> to dissolved in an organic solvent on the support or the alignment film subjected to the rubbing treatment. <5> including a step of applying the dichroic dye composition according to any one of (3) and (3) a step of orienting the dichroic dye composition by evaporating the organic solvent <5>. The manufacturing method of the polarizing element of description.

  According to the present invention, it is possible to provide a dye composition having liquid crystallinity and high dichroism by using a dichroic dye that can be synthesized with a small number of steps. Compared to the conventional case, the dichroic dye synthesis route is significantly shortened, thereby reducing the cost. Moreover, according to this invention, the light absorption anisotropic film, polarizing element, and liquid crystal display device which have the outstanding characteristic using this composition can be provided.

Hereinafter, the present invention will be described in detail.
The dichroic dye composition of the present invention contains at least one azo dye represented by the following general formula (1), which has liquid crystallinity and has a symmetrical structure via the linking group L. It is characterized by. In the present invention, the “dichroic dye” means a dye having an absorption wavelength different depending on the direction. The “dichroism” is calculated by the ratio of the absorbance of polarized light in the direction of the polarization axis to the absorbance of polarized light in the direction of the polarization axis when the dichroic dye composition is a light absorption anisotropic film.
Hereinafter, the azo compound represented by the general formula (1) will be described in detail.

(In the formula, L represents a single bond or a divalent linking group, R represents a hydrogen atom, an alkyl group, an alkoxy group, or an amino group, and Ar represents an aromatic hydrocarbon group which may have a substituent. Or it represents an aromatic heterocycle (when there are a plurality of Ars, they may be the same or different), and a represents an integer of 1 to 3.)

L represents a single bond or a divalent linking group. The linking group L itself may not have a symmetric structure, but is preferably a symmetric, linear and rigid structure.
Examples of the linking group represented by L include the following.
An azo group or an alkylene group (preferably an alkylene group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, such as a methylene group, an ethylene group, a butylene group, a hexylene group, 1,4-cyclohexylene group and the like), alkenylene group (preferably an alkenylene group having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms), an alkynylene group. (Preferably an alkynylene group having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms), an arylene group (preferably 6 to 30 carbon atoms, more preferably 6 carbon atoms). To 20 and particularly preferably an aryl group having 6 to 12 carbon atoms, such as a phenylene group and a naphthylene group), a heterocyclic divalent group (preferably Or a heterocyclic group having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, for example, a heterocyclic group having a hetero atom such as a nitrogen atom, an oxygen atom or a sulfur atom, such as a pyridyl group, a piperidinyl group, A piperazinyl group, a pyrimidinyl group, a carbazolyl group, etc.), an amide group, an ester group, a sulfoamide group, a sulfonic acid ester group, a ureido group, a sulfonyl group, a sulfinyl group, a thioether group, an ether group, a carbonyl group, and —NR ^1. - (wherein, R ¹ represents a hydrogen atom, an alkyl represents a group or an aryl group) linking group composed of 1 to 60 carbon atoms singly or in combination of two or more selected from.

  L is preferably a single bond, azo group, ethylene group, butylene group, hexylene group, 1,4-cyclohexylene group, vinylene group, acetylene group, ester group, ether group, phenylene group, naphthylene group, piperidinyl group, piperazinyl A linking group composed of one or more selected from a group, more preferably a single bond, an azo group, an ethylene group, a 1,4-cyclohexylene group, an acetylene group, an ester group, a phenylene group, A linking group composed of one or more selected from a naphthylene group, a piperidinyl group, and a piperazinyl group.

  R is a hydrogen atom or 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, a propyl group, A butyl group, an n-octyl group, an n-decyl group, an n-hexadecyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group and the like, an alkoxy group (preferably having 1 to 20 carbon atoms, more preferably 1 carbon atom). -12, particularly preferably 1 to 8 carbon atoms, for example, methoxy group, ethoxy group, butoxy group and the like, or substituted or unsubstituted amino group (preferably 0 to 20 carbon atoms, more preferably An amino group having 0 to 12 carbon atoms, particularly preferably 0 to 8 carbon atoms, such as an unsubstituted amino group, a methylamino group, a dimethylamino group, a diethyl group. It represents an amino group, such as an anilino group).

Ar represents an aromatic hydrocarbon group or an aromatic heterocyclic ring which may have a substituent, and when there are a plurality of Ars, they may be the same as or different from each other.
As the aromatic hydrocarbon group represented by Ar, a phenylene group and a naphthylene group are preferable, and a phenylene group is more preferable.
Examples of the substituent that the aromatic hydrocarbon group may have include an alkyl group, an alkoxy group, a hydroxy group, a halogen atom, an amino group, an acylamino group, and a cyano group, preferably an alkyl group or An alkoxy group;

As the aromatic heterocyclic group represented by Ar, 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, with a nitrogen atom and a sulfur atom being particularly preferred. 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 pyridinediyl group, a quinolinediyl group, an isoquinolinediyl group, a benzothiadiazolediyl group, and a phthalimidodiyl group. Examples of the substituent that the aromatic heterocyclic group may have include a substituent of the aromatic hydrocarbon group represented by Ar, and a preferable range thereof is also the same.

  Ar is particularly preferably a phenylene group or naphthylene group which may have a substituent, and most preferably a phenylene group which may have a substituent.

Specific examples of the azo dye represented by the general formula (1) are given below, but the present invention is not limited thereto.
“Symmetry” in the compound represented by the general formula (1) means that two residues bonded to the linking group L are the same, and symmetry is established in the spatial shape of the compound. It is not limited to the case. “Symmetry” also includes cases where the conformation of the compound is twisted or bent and there is no symmetry such as plane symmetry or point symmetry. (For example, A-5 shown below is included in the above "symmetry").

  The azo dye represented by the general formula (1) in the present invention is “Dichroic Dyes for Liquid Crystal Display” (AV Ivashchenko, CRC, 1994), “Review Synthetic Dye” (Horiguchi Hiroshi, Sankyo Publishing, 1968) and the literatures cited therein and the like.

  The azo dye represented by the general formula (1) is a rod-like compound having a large aspect ratio (= molecular length / molecular width) of the compound, and can be oriented with a high degree of orientation order. Moreover, it has a symmetric molecular structure via the linking group L, and can be synthesized by simultaneously extending both ends using the core portion at the center of the molecule as a starting material, so that the synthesis route can be greatly reduced.

  In the dichroic dye composition containing the azo dye represented by the general formula (1) according to the present invention, the composition containing this dye has nematic liquid crystal properties. A higher-order molecular orientation state can be realized through a lamination process such as coating. Therefore, if the dichroic dye composition containing the azo dye represented by the general formula (1) according to the present invention is used as a light absorption anisotropic film, a polarizing element having high polarization characteristics can be produced. it can.

  In the present invention, the azo dye represented by the general formula (1) may be used alone or in combination of two or more. Alternatively, the azo dye according to the present invention may be used in combination with a dye compound other than these. Examples of these include azo dyes other than those used in the present invention, cyanine dyes, azo metal complexes, phthalocyanine dyes, pyrylium dyes, thiopyrylium dyes, azurenium dyes, squarylium dyes, naphthoquinone dyes, Examples thereof include triphenylmethane dyes and triallylmethane dyes.

The light absorption anisotropic film of the present invention is formed with a dichroic dye as a main component, and the content of the dichroic dye in the dichroic dye composition of the present invention is 70% by mass or more, 80 mass% or more is especially preferable, and 90 mass% or more is the most preferable.
Further, the content of the azo dye represented by the general formula (1) is preferably 50% by mass or more, and particularly preferably 70% by mass or more of the dichroic dye.
Further, the content of the azo dye represented by the general formula (1) in the dichroic dye composition of the present invention is not particularly limited, but is preferably 70% by mass or more, and particularly preferably 80% by mass or more.

[Additive of light absorption anisotropic film]
In the dichroic dye composition of the present invention, in addition to the dichroic dye, any additive can be used in combination. Examples of the additive include wind unevenness inhibitor, repellency inhibitor, additive for controlling the tilt angle of the alignment film (tilt angle of the dichroic dye at the light absorption anisotropic film / alignment film interface), Additives for controlling the tilt angle of the air interface (light absorption anisotropic film / tilt angle of the dichroic dye at the air interface), polymerization initiator, additive (plasticizer) for lowering the orientation temperature, polymerization Chemical monomers, sugars, antifungal agents, antibacterial agents, and agents having at least one function of sterilization. Hereinafter, each additive will be described.

[Wind unevenness prevention agent]
In general, a fluorine-based polymer can be suitably used as a material for use in combination with a dichroic dye to prevent wind unevenness during coating. There is no restriction | limiting in particular as a fluorine-type polymer to be used, unless the tilt angle change and orientation of a dichroic dye are inhibited significantly. Examples of fluoropolymers that can be used as wind unevenness inhibitors are described in JP-A No. 2004-198511, JP-A No. 2004-333852, JP-A No. 2005-179636, and JP-A No. 2005-206638. . By using the dichroic dye and the fluorine-based polymer in combination, an image with high display quality can be displayed without causing unevenness. Furthermore, applicability such as repelling is improved. In order not to inhibit the orientation of the dichroic dye, the amount of the fluorine-based polymer used for the purpose of preventing wind unevenness is preferably in the range of 0.1 to 2% by mass with respect to the dichroic dye. The content is more preferably in the range of 0.1 to 1% by mass, and still more preferably in the range of 0.4 to 1% by mass.

[Anti-repellent agent]
As a material for preventing repelling at the time of application of a dichroic dye, generally a polymer compound can be suitably used. The polymer to be used is not particularly limited as long as it is compatible with the dichroic dye and does not significantly inhibit the tilt angle change or orientation of the dichroic 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 dichroic dye, the amount of the polymer used for the purpose of preventing repellency is preferably in the range of generally 0.1 to 10% by mass relative to the dichroic dye composition, It is more preferably in the range of 0.1 to 8% by mass, and still more preferably in the range of 0.1 to 5% by mass.

[Alignment film tilt angle control agent]
As an additive for controlling the tilt angle of the alignment film, a compound having both a polar group and a nonpolar group in the molecule can be added. 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 - NO ₂ and P ^O —CN and their organic salts are preferred examples. Here, as the organic salt, in addition to the organic salt of the above compound (for example, ammonium salt, carboxylate, sulfonate, etc.), pyridinium salt and the like can be preferably employed. Among the compounds having both a polar group and a non-polar 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 of P ^O represents a non-polar group, if P ^O is more, each of P ^O 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 alkynyl groups having 1 to 30 carbon atoms), aryl groups (preferably 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 the present invention, by adding an alignment film tilt control agent to the dichroic dye composition coating liquid and the like, and orienting the dichroic dye in the presence of the alignment film tilt control agent, the dichroism at the alignment film side interface is achieved. The tilt angle of the dye can be adjusted. In general, the addition amount of the alignment film tilt angle control agent is preferably 0.0001% by mass to 30% by mass with respect to the mass of the dichroic dye, and is 0.001% by mass to 20% by mass. More preferably, it is 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.

[Polymerization initiator]
It is preferable to form a light absorption anisotropic film by fixing the orientation state of the dichroic dye, and it is preferable to fix the dichroic dye 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 order to prevent deformation of the support and the like due to heat, the photopolymerization reaction is performed. preferable. Examples of the photopolymerization initiator, the amount of photopolymerization initiator used, and the value of light irradiation energy for polymerization are described in paragraphs [0050] to [0051] of JP-A No. 2001-91741 in the present invention. Applicable.

[Polymerizable monomer]
A polymerizable monomer may be used together with the dichroic dye. The polymerizable monomer that can be used in the present invention is not particularly limited as long as it is compatible with the dichroic dye and does not cause a significant change in tilt angle or inhibition of orientation of the dichroic dye. Among these, compounds having a polymerization active ethylenically unsaturated group such as a vinyl group, a vinyloxy group, an acryloyl group, and a methacryloyl group are preferably used. The addition amount of the polymerizable monomer is generally in the range of 1 to 50% by mass and preferably in the range of 5 to 30% by mass with respect to the dichroic dye. In addition, it is particularly preferable to use a monomer having two or more reactive functional groups because an effect of improving the adhesion between the alignment film and the optically anisotropic layer can be expected.

[Sugar]
Saccharides may be added to the composition of 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 the saccharide include sugar derivatives such as monosaccharides, disaccharides, polysaccharides, and 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 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 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 dye, which may undesirably deteriorate 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, soratriose, melezitose, planteose, gentianose, umbelliferose, raffinose, 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 of them may be used alone or in the composition of the present invention. Moreover, saccharides may be used individually by 1 type in the composition of this invention, and 2 or more types may be used in combination.

  The saccharide content relative to the pigment in the composition of the present invention is preferably in the range of 0.1 or more and 1 or less by weight. 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. If the saccharide content exceeds this upper limit, the degree of orientation of the aggregate is likely to decrease, and if it is less than the lower limit, it may be insufficient to increase the degree of association of the dye aggregate.

[Antidepressants, antibacterial agents and bactericides]
You may add the chemical | medical agent which has at least any function of antifungal, antibacterial, and disinfection to the composition of this invention. By adding these additives, the storage stability of the composition can be improved.

  The agent having at least one of antifungal, antibacterial, and sterilizing functions as referred to in the present invention is an antifungal ability that suppresses the generation / growth / growth of mold, the bactericidal ability that kills microorganisms, the generation / growth of microorganisms Any agent may be used as long as it has at least one function of antibacterial ability to suppress proliferation, and known antifungal agents, bactericides, and antibacterial agents can be used. However, it is preferable that the optical properties of the anisotropic film prepared using the composition of the present invention are not deteriorated. Examples of the agent having at least one of antifungal, antibacterial, and bactericidal functions used in the present invention include, for example, conventional phenols such as 2,4,4′-trichloro-2′-hydroxydiphenyl, chlorine dioxide, and the like. Examples thereof include iodine, such as chlorine and iodine, and quaternary ammonium salt, such as benzalkonium chloride.

In addition, as an active ingredient, 1,2-benzisothiazole-3-one, Proxel BDN, Proxel BD20, Proxel GXL, Proxel LV, Proxel XL, Proxel XL2, Proxel Ultra 10 (above, trade name, manufactured by Avecia) Polyhexylene biguanide hydrochloride as an active ingredient, Proxel IB (Avecia, product name), Dithio-2,2'-bis (benzmethylamide) as an active ingredient, Densil P (Aveci product, Aveci product) ) And the like.
In addition, a compound represented by the following formula (11) is also effective, and is particularly preferable because it exhibits an antibacterial effect particularly in a very small amount.

(In formula, X represents the alkyl group which may have a substituent, the cycloalkyl group which may have a substituent, or the aromatic hydrocarbon ring group which may have a substituent. R ²¹ and R ²² each independently represents a hydrogen atom, a halogen atom or an alkyl group.)
Examples of the alkyl group represented by X include an alkyl group having 1 to 6 carbon atoms, and the alkyl group is preferably an alkyl group having a substituent. Examples of the substituent for the alkyl group include a hydroxyl group, a halogen atom, a cyano group, a phenylamino group, a halophenylamino group, a carboxy group, an alkoxycarbonyl group, an alkoxy group, an aryloxy group, a morpholino group, a piperidino group, a pyrrolidino group, and a carbamoyl group. An oxy group or an isothiazolonyl group is mentioned. The halogen atom in the halogen atom and the halophenyl group is a chlorine atom or a bromine atom, and the alkoxy group in the alkoxy group or the alkoxycarbonyl group is a linear or branched chain having 1 to 6 carbon atoms. As the aryl group of the aryloxy group, an alkoxy group is preferably a phenyl group or a phenyl group substituted with a lower alkyl group such as a methyl group or an ethyl group.
Examples of the cycloalkyl group represented by X include cycloalkyl groups having 5 to 7 carbon atoms, and among them, a cyclohexyl group is preferable. Moreover, as a substituent of a cycloalkyl group, a C1-C6 alkyl group is preferable.
The aromatic hydrocarbon ring group represented by X is preferably a phenyl group, and the aromatic hydrocarbon ring group preferably has a substituent. As the substituent of the aromatic hydrocarbon ring group, a nitro group, an alkyl group or an alkoxycarbonyl group is preferable. As the alkyl group, a lower alkyl group is preferable, and a methyl group and an ethyl group are particularly preferable. The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 7 carbon atoms.

  Among the above, the group represented by X is a C 1-6 alkyl group substituted with a halogen atom, a hydroxyl group, a cyano group or a morpholino group; a C 1-6 alkyl group which may be substituted with a C 1-6 alkyl group. An alkyl group; or an aromatic hydrocarbon ring group substituted with a halogen atom, a nitro group, or an alkyl group having 1 to 6 carbon atoms is preferable.

R ²¹ and R ²² each independently represents a hydrogen atom, a halogen atom or an alkyl group, and the halogen atom is preferably a chlorine atom or a bromine atom, and the alkyl group is preferably an alkyl group having 1 to 6 carbon atoms. . Among these, R ²¹ is more preferably a hydrogen atom or a halogen atom, and particularly preferably a hydrogen atom. R ²² is preferably a halogen atom.

In the present invention, “may have a substituent” means that it may have one or more substituents. Further, when the number of carbon atoms in the alkyl group and the portion corresponding to the alkyl group of the substituent is 3 or more, it may be either linear or branched.
Typical specific examples of the compound represented by the formula (11) are shown below.

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 of this invention can also be used individually or in combination of 2 or more types.
The content of the drug having at least one of antifungal, antibacterial and bactericidal functions in the dichroic dye 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. If the content of the drug having at least one of antifungal, antibacterial and sterilizing functions is too small, the dichroic dye composition does not have sufficient antifungal, antibacterial or sterilizing effects, and if the content is too large There is a risk of causing optical defects such as point defects and light scattering because phase separation may occur when a dichroic dye composition is deposited in the dichroic dye composition or an anisotropic dye film is formed. .

  Since the light absorption anisotropic film of the present invention has a high dichroic ratio, the dichroic dye composition of the present invention has an electron-deficient discotic compound and an electron-rich (Electron-Rich). ) It is preferable to contain a compound. In the present invention, for example, those described in JP-A-2006-323377 can be used as the electron-deficient discotic compound and the electron-rich compound.

  The ratio of the electron-deficient discotic compound in the composition of the present invention 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. In addition, the range is usually 50 parts by mass or less, preferably 40 parts by mass or less. If the proportion of the compound is too small, there is a possibility that the effect due to the use of an electron-deficient discotic compound may not be obtained, and if it is too large, the viscosity of the composition as a solution becomes high, Since it may become difficult to handle, it is not preferable.

  The ratio of the electron-rich compound in the composition of the present invention is usually 50 parts by mass or less, preferably 40 parts by mass or less, based on 100 parts by mass of the entire composition. If the amount is too large, the viscosity of the resulting solution of the composition is increased, which may be difficult to handle.

  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.

[Coating solvent]
The light absorption anisotropic film of the present invention is preferably formed using a coating solution of the dichroic dye composition of the present invention. As a solvent used for preparation of a coating liquid, an organic solvent is preferable. Examples of organic solvents include amides (eg, N, N-dimethylformamide), sulfoxides (eg, dimethyl sulfoxide), heterocyclic compounds (eg, pyridine), hydrocarbons (eg, benzene, hexane), alkyl halides (eg, , Chloroform, dichloromethane), esters (eg, methyl acetate, butyl acetate), ketones (eg, acetone, methyl ethyl ketone), ethers (eg, tetrahydrofuran, 1,2-dimethoxyethane). Alkyl halides and ketones are preferred. Two or more organic solvents may be used in combination.

[Application method]
Application of the dichroic dye composition coating liquid to the alignment film surface is performed by a usual method (for example, wire bar coating method, extrusion coating method, direct gravure coating method, reverse gravure coating method, die coating method, ink jet method). Can be implemented. Moreover, 1-20 mass% is preferable, as for content of the dichroic dye composition in a dichroic dye composition coating liquid, 1-10 mass% is more preferable, and 1-5 mass% is further more preferable.

The light absorption anisotropic film of the present invention is preferably formed by a wet film formation method. For the production of the light absorption anisotropic film in the present invention, after preparing the dichroic dye composition of the present invention, it is applied to various substrates such as a glass plate, etc. The method is adopted.
Specifically, as a wet film formation method, Yuji Harasaki, “Coating Engineering”, Asakura Shoten Co., Ltd., published on March 20, 1971, pages 253-277 and Kunihiro Ichimura, “Creation and Application of Molecular Cooperative Materials” CMC Publishing Co., Ltd., published on March 3, 1998, pages 118 to 149, etc., such as spin coating, spray coating, bar Examples of the method include coating by a coating method, a roll coating method, a blade coating method, a free span coating method, a die coating method, and an ink jet method.

  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.

  Since the light absorption anisotropic film manufactured by such a method may have low mechanical strength, a protective layer is provided if necessary. This protective layer is formed by lamination with a transparent polymer film such as triacetate, acrylic, polyester, polyimide, triacetylcellulose, or urethane film, and is practically used.

  Further, when the light absorption anisotropic film of the present invention is used as a polarizing filter or the like for various display elements such as LCDs and OLEDs, a dye film is directly formed on an electrode substrate or the like constituting these display elements, A substrate on which a dye film is formed can be used as a constituent member of these display elements.

In the present invention, the dichroic dye composition of the present invention is applied on a substrate that has been aligned in one direction at an angle that is not parallel to the alignment processing direction on the substrate, and the light absorbing anisotropic A functional film can be formed. Furthermore, it is more preferable to apply the dichroic dye composition of the present invention in a direction substantially coinciding with the vertical or horizontal direction of the substrate. Thereby, it is possible to provide a light-absorbing anisotropic film having no optical defect and having a high dichroic ratio. In addition, after applying the dichroic dye composition, it is not necessary to cut out the base material in order to give the necessary polarization angle, and the productivity is high.
The preferable application method of the dichroic dye composition of the present invention is described in, for example, JP-A-2007-127897.

  In the present invention, a dichroic dye composition coating solution is applied to the alignment film surface to form a light-absorbing anisotropic film, and then the anisotropic film is subjected to reduced pressure to evaporate the organic solvent and dry. Can do. Thereby, a light absorption anisotropic film having a high dichroic ratio can be provided.

The decompression treatment here refers to placing the light absorption anisotropic film under a decompression condition. At this time, the base material having the light absorption anisotropic film is preferably 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 light absorption anisotropic film, the better. The time is preferably from 1 second to 30 seconds.
Examples of the decompression method include the following methods. The light absorption anisotropic film obtained by applying the coating solution on the substrate is put 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 dye 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. Moreover, Preferably it is 1 Pa or more, More preferably, it is 1 * 10 < ¹ > Pa or more. Usually, the pressure finally reached in the system is preferably as described above. If it is too high, drying may not be possible and the orientation may be disturbed. If it is too low, drying may be too rapid and defects may occur.
The decompression time is preferably 5 seconds or more and 180 seconds or less. If it is too long, the dye film cannot be dried rapidly before the orientation relaxation, and the orientation may be disturbed. If it is too short, it may not be dried and 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 it is too high, convection may occur at the time of drying, which may cause non-uniformity in the coating film, and if it is too low, it may not be possible to dry and the orientation may be disturbed.
Moreover, when apply | coating a pigment | dye film | membrane by the wet film forming method, you may heat a base material and may cool it. The temperature of the base material at this time is preferably 10 ° C. or higher and 60 ° C. or lower. If it is too high, the orientation may be disturbed before drying under reduced pressure, and if it is too low, water droplets may form on the surface of the substrate, which may impede coating. The substrate may be heated when the dye film applied by the wet film forming method is dried under reduced pressure. The temperature of the base material at this time is preferably 60 ° C. or lower. If it is too high, the orientation may be disturbed before drying under reduced pressure.

[Characteristics of light absorption anisotropic film]
The thickness of the light absorption anisotropic film is preferably 0.01 to 2 μm, more preferably 0.05 to 1 μm, and most preferably 0.05 to 0.5 μm.

When the dichroic dye composition coating liquid of the present invention is applied on the alignment film, the dichroic dye is aligned at the tilt angle of the alignment film at the interface with the alignment film, and at the tilt angle of the air interface at the interface with air. Orient. Horizontal orientation can be realized by applying the dichroic dye composition coating liquid of the present invention to the surface of the alignment film and then orienting the dichroic dye uniformly (monodomain orientation).
A light absorption anisotropic film formed by horizontally aligning a dichroic dye and fixing the dichroic dye in the aligned state can be used as a polarizing element.

Generally, the tilt angle of the dichroic dye on the air interface side is determined by other compounds added as desired (for example, JP-A-2005-99248, JP-A-2005-134484, JP-A-2006-126768). Can be adjusted by selecting a horizontal aligning agent described in JP-A-2006-267183, etc., and is preferable as a polarizing element of a liquid crystal display device to which the light absorption anisotropic film of the present invention is applied. An alignment state can be realized.
Further, the tilt angle of the dichroic dye on the alignment film side can be controlled by the above-described method (alignment film tilt angle control agent or the like).

[Tilt angle]
In the present invention, the tilt angle refers to an angle formed between the long axis direction of the molecule of the dichroic dye and the interface (alignment film interface or air interface). Optical performance preferable as a polarizing element can be more effectively obtained by reducing the tilt angle on the alignment film side to some extent and performing horizontal alignment. Therefore, from the viewpoint of polarization performance, the preferred tilt angle on the alignment film side is 0 ° to 10 °, more preferably 0 ° to 5 °, particularly preferably 0 ° to 2 °, and most preferably 0 ° to 1 °. is there. The preferred tilt angle on the air interface side is 0 ° to 10 °, more preferably 0 to 5 °, and particularly preferably 0 to 2 °.

[Alignment film]
The alignment film is an organic compound (eg, ω-tricosanoic acid) formed by rubbing treatment of an organic compound (preferably polymer), oblique deposition of an inorganic compound, formation of a layer having a 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. As long as the desired orientation can be imparted to the dichroic dye of the light absorption anisotropic film provided on the alignment film, any layer may be used as the alignment film. From the viewpoint of ease of control, an alignment film formed by a rubbing treatment of a polymer is particularly preferable. The rubbing treatment can be generally carried out by rubbing the surface of the polymer layer several times in a certain direction with paper or cloth. In particular, in the present invention, it is described in “Liquid Crystal Handbook” (Maruzen Co., Ltd.). It is preferable to carry out by a method.
The thickness of the alignment film is preferably 0.01 to 10 μm, and more preferably 0.05 to 1 μm.
The polymer used for the alignment film is described in many documents, and many commercially available products can be obtained. In the alignment film in the present invention, polyvinyl alcohol and its derivatives are preferably used. Particularly preferred is a modified polyvinyl alcohol having a hydrophobic group bonded thereto. Regarding the alignment film, reference can be made to the description of page 43, line 24 to page 49, line 8 of WO01 / 88574A1.
In the present invention, the alignment film may be the same as the support.

[Rubbing density of alignment film]
As a method for changing the rubbing density of the alignment film, a method described in “Liquid Crystal Handbook” (Maruzen Co., Ltd.) 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 reverse this.
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.

[Support]
The support used in the present invention may be transparent or a support made opaque by coloring or the like, but is preferably a transparent support (transparent support) and has a light transmittance of 80%. The above is preferable. It is preferable to use an optically isotropic polymer film. As the specific examples and preferred embodiments of the polymer, the description in paragraph [0013] of JP-A-2002-22294 can be applied. 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

  As the polymer film, it is preferable to use cellulose acetate having an acetylation degree of 55.0 to 62.5%. In particular, the acetylation degree is preferably 57.0 to 62.0%. The description of paragraph number [0021] of JP-A No. 2002-196146 can be applied to the degree of acetylation, the range thereof, and the chemical structure of cellulose acetate. The production of a cellulose acylate film using a non-chlorine solvent is described in detail in JIII Journal of Technical Disclosure No. 2001-1745, and the cellulose acylate film described therein is also preferably used in the present invention. Can do.

  The description of paragraph numbers [0018] to [0019] of JP-A No. 2002-139621 can be applied to the retardation value in the thickness direction of the cellulose ester film used as the transparent support and the range of the birefringence.

  In order to adjust the retardation of a polymer film used as a transparent support, particularly a cellulose acylate film, an aromatic compound having at least two aromatic rings can also be used as a retardation increasing agent. The description of paragraph numbers [0021] to [0023] of JP-A No. 2002-139621 can be applied to the preferred range and usage amount of the aromatic compound. Such retardation increasing agents are described in International Publication No. WO01 / 88574A1, International Publication No. WO00 / 2619A1, Japanese Unexamined Patent Publication No. 2000-1111914, No. 2000-275434, No. 2002-363343, and the like. ing.

  The cellulose acylate film is preferably produced by a solvent cast method from the prepared cellulose acylate solution (dope). It is preferable to add the above-mentioned retardation increasing agent to the dope. Using the prepared cellulose acylate solution (dope), a film can be formed by casting two or more layers of the dope. The description of paragraph numbers [0038] to [0040] of JP-A No. 2002-139621 can be applied to the formation of the film.

  The retardation of the cellulose acylate film can be further adjusted by a stretching treatment. The draw ratio is preferably in the range of 3 to 100%. When stretching the cellulose acylate film, tenter stretching is preferably used, and in order to control the slow axis with high accuracy, it is preferable to make the difference between the left and right tenter clip speeds, the separation timing, etc. as small as possible. .

  A plasticizer can be added to the cellulose ester film in order to improve mechanical properties or increase the drying speed. As a plasticizer, the aspect of paragraph number [0043] of JP, 2002-139621, A and a desirable range are applicable to the present invention.

  Degradation inhibitors (eg, antioxidants, peroxide decomposers, radical inhibitors, metal deactivators, acid scavengers, amines) and UV inhibitors may be added to the cellulose ester film. Regarding the deterioration preventing agent, the description in paragraph number [0044] of JP-A No. 2002-139621 can be applied. As a particularly preferred example of the deterioration preventing agent, butylated hydroxytoluene (BHT) can be mentioned. The ultraviolet ray preventing agent is described in JP-A-7-11056.

  Regarding the surface treatment of the cellulose acylate film and the surface energy of the solid, the description in paragraph numbers [0051] to [0052] of JP-A No. 2002-196146 can be applied.

  The thickness of the cellulose acylate film varies depending on the purpose of use, but is usually in the range of 5 to 500 μm, more preferably in the range of 20 to 250 μm, and most preferably in the range of 30 to 180 μm. In addition, as an optical use, the range of 30-110 micrometers is especially preferable.

[Use of light absorption anisotropic film]
The light-absorbing anisotropic film of the present invention functions as a polarizing film for obtaining linearly polarized light, circularly-polarized light, elliptically-polarized light, etc. by utilizing the anisotropy of light absorption, as well as a film forming process and a composition containing a substrate and a dye. By selecting an object, it can be functionalized as various anisotropic films such as refractive anisotropy and conduction anisotropy, and a polarizing element that can be used in various types and various applications can be obtained.
The polarizing element of the present invention includes (1) a step of rubbing the support or the alignment film formed on the support, and (2) the present invention dissolved in an organic solvent on the rubbed support or alignment film. And (3) a step of orienting the dichroic dye composition by evaporating the organic solvent. The details of the steps (1) to (3) are as described above.

When the light absorption anisotropic film of the present invention is formed on a substrate and used as a polarizing element, the formed light absorption anisotropic film itself may be used. Besides the protective layer as described above, Function as adhesive layer or antireflection layer, alignment film, retardation film, function as brightness enhancement film, function as reflection film, function as transflective film, function as diffusion film, function as optical compensation film A layer having various functions, such as a layer having an optical function, may be laminated by a wet film formation method or the like, and used as a laminate.
These layers having optical functions can be formed, for example, by the following method.

  The layer having a function as a retardation film is subjected to, for example, a stretching process described in Japanese Patent No. 2841377, Japanese Patent No. 3094113, or a process described in Japanese Patent No. 3168850. Can be formed.

  In addition, the layer having a function as a brightness enhancement film is formed by forming fine holes by a method described in, for example, Japanese Patent Application Laid-Open No. 2002-169025 or Japanese Patent Application Laid-Open No. 2003-29030, or selective reflection. It can be formed by superposing two or more cholesteric liquid crystal layers having different center wavelengths.

The layer having a function as a reflective film or a transflective film can be formed using a metal thin film obtained by vapor deposition or sputtering.
The layer having a function as a diffusion film can be formed by coating the protective layer with a resin solution containing fine particles.
The layer having a function as a retardation film or an optical compensation film can be formed by coating and aligning a liquid crystal compound such as a discotic liquid crystal compound.

  An in-cell polarizer can be produced by applying and forming the dichroic dye composition of the present invention. In this case, by controlling the electric conductivity and / or sodium ion concentration of the dichroic dye composition to a certain value or less, an in-cell type having a high voltage holding ratio (charge holding characteristics) suitable for active driving. A polarizer can be obtained, and as a result, a liquid crystal element using the In-Cell polarizer excellent in driving performance and display performance can be obtained.

  In the present invention, the electric conductivity of the dichroic dye composition is preferably 25 mS / cm or less, more preferably 10 mS / cm or less, and still more preferably 1 mS / cm or less. By setting it as such a range, it becomes possible to obtain an in-cell type polarizer having a high voltage holding ratio. In addition, it is 0.2 mS / cm or more normally. Exceeding the upper limit is undesirable because the solubility of polar impurities increases.

  The electrical conductivity of the composition for in-cell polarizers is determined by a conductivity meter using a two-electrode method (cell) or a four-electrode method (cell). Specifically, it can be measured by various methods in accordance with the method of measuring electrical conductivity defined in K0101: 1998 “Industrial Water Test Method” of Japanese Industrial Standard (JIS), but it can be measured by a guard electrode. From the viewpoint of improving measurement accuracy, the four-electrode method (cell) is more likely to be unevenly distributed by the applied voltage (potential difference generated between the electrodes) than the two-electrode method (cell). From the viewpoint of eliminating the phenomenon, measurement by applying alternating current (AC) is preferable to applying direct current (DC).

As described above, the dichroic dye composition of the present invention is a mixture (solution) comprising a dye, a solvent, and various additives such as a surfactant used as necessary. It is thought that the chemical species of each component constituting this mixture and impurities derived from each component, particularly polar components and ionic components, contribute to the electrical conductivity of the composition. By reducing these contents, electricity It is considered that the conductivity can be reduced.
A technique for reducing the electrical conductivity of the dichroic dye composition of the present invention is described in, for example, JP-A-2006-309185, and can be applied to the present invention.

  In the present invention, the sodium ion concentration of the dichroic dye composition is preferably 2500 ppm or less, more preferably 1000 ppm or less, and even more preferably 100 ppm or less. The lower limit is usually 10 ppm or more. If it is too high, elution into the liquid crystal element (liquid crystal layer) and further adverse effects on electrical characteristics are not preferable. As a method for bringing the sodium ion concentration within the above range, for example, various methods exemplified above as a method for reducing impurities can be used.

  The sodium ion concentration of the dichroic dye composition can be determined by using an ion-selective electrode whose electrode potential changes in response to the concentration of specific ions present in the composition and a comparative electrode. Specifically, various methods such as flame photometry, flame atomic absorption, ion chromatography and the like according to the measurement method of sodium (ion) specified in K0101: 1998 “Test method for industrial water” of Japanese Industrial Standard (JIS) Although it is possible to measure by the method, it is specified in K0122: 1998 “General Rules for Ion Electrode Measurement Method” of Japanese Industrial Standard (JIS) because it can directly measure the amount of sodium ions at a relatively high concentration. An ion electrode measuring method according to the measuring method is preferred. Furthermore, it is preferable to use an ion meter that uses an ion-selective electrode that does not require pH adjustment with a buffer solution because the change in the dissociated state due to pH can be suppressed.

  The optically anisotropic film may be directly formed on the surface of a protective film for a polarizing plate, for example, by a coating method. Alternatively, the transfer material described below may be used for transfer. That is, as an example of the manufacturing method of the liquid crystal display device of the present invention, there is a method including forming an optically anisotropic layer made of the optically anisotropic film by transferring it from a transfer material. By forming an optically anisotropic layer using a transfer material, the number of steps can be reduced, and a liquid crystal display device with good display characteristics can be manufactured by a simple method.

Hereinafter, a transfer material useful for forming the optically anisotropic layer in a liquid crystal display device will be described.
[Transfer material]
The transfer material that can be used in the present invention has at least a support and an optically anisotropic layer as shown in FIG. 3A of JP-A-2007-279705, for example. As shown in FIG. 3B of the above publication, it is preferable to further have at least one photosensitive resin layer. The photosensitive resin layer is useful because it facilitates the transfer of the optically anisotropic layer even when it is not subjected to a process such as patterning. Also, for example, as shown in FIG. 3C of the above publication, a mechanical property such as cushioning for absorbing irregularities on the counterpart substrate side during transfer between the support and the optically anisotropic layer. It may have a layer for imparting control or uneven tracking, and as shown in FIG. 3 (d) of the above publication, the orientation of the dichroic dye in the optically anisotropic layer is controlled. For this purpose, a layer functioning as an alignment layer may be disposed, or both layers may be provided as shown in FIG. Further, as shown in FIG. 3F of the above publication, a peelable protective layer may be provided on the outermost surface for the purpose of protecting the surface of the photosensitive resin layer.

[Support]
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 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 (trade name, manufactured by JSR Corporation), Zeonex, Zeonore (all of which are trade names, manufactured by Nippon Zeon Co., Ltd.) and the like can be used. Inexpensive polycarbonate, polyethylene terephthalate, and the like are also preferably used.

[Optically anisotropic layer]
The optically anisotropic layer 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 an exposure process performed in the transfer process, Finally, the polarizing film required for the polarizing film may be exhibited.

[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 oligomer, and (3) a photopolymerization initiator or photopolymerization start. It is preferable to form from the resin composition containing an agent 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 optically anisotropic layer 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 optically anisotropic layer and the photosensitive resin layer, and the orientation layer, the thermoplastic resin layer, and the intermediate layer, which are formed as required, are dip coat method, air knife coat method, curtain coat method, roller coat method, wire bar. It can be formed by coating by a coating method, a gravure coating method or an extrusion coating method (US Pat. No. 2,681,294). Two or more layers may be applied simultaneously. The method of simultaneous application is 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).

[Method of forming optically anisotropic layer 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 optically anisotropic layer 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 optically anisotropic layer 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 solid optically anisotropic layer is provided on a transparent support. 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 optically anisotropic layer, an adhesive layer may be provided on the material to be transferred.

EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these.
In the following examples, the measurement of optical characteristics of the light absorption anisotropic film was performed as follows.

<Dichroic ratio>
The dichroic ratio was calculated by the following equation after measuring the absorbance of the light-absorbing anisotropic film with a spectrophotometer in which an iodine-type polarizing element was arranged in the incident optical system.
Dichroic ratio (D) = Az / Ay
Az: Absorbance with respect to polarized light in the absorption axis direction of the light absorption anisotropic film Ay: Absorbance with respect to polarization in the polarization axis direction of the light absorption anisotropic film

(Synthesis Example 1)
The azo compound (B-1) was synthesized as follows.
P-ethynylaniline (1) synthesized by the method described in J. Org. Chem., 2004, 69 (5), 1752-1755 is dissolved in pyridine, and excess copper (II) acetate is added at room temperature. Then, a homocoupling reaction was performed to obtain a diacetylene compound (2). This compound was suspended in hydrochloric acid and diazotized by gradually adding an aqueous sodium nitrite solution while keeping the liquid temperature at 5 ° C. or lower. This reaction solution was added to a methanolic phenol solution made basic with potassium hydroxide to obtain an azo compound (3). This compound was dissolved in a butanol / toluene mixed solvent to which a catalytic amount of sulfuric acid was added, and heated to reflux in a flask equipped with a Dean-Stark distillation apparatus to obtain an azo compound (B-1).
_{^{1 H-NMR (CDCl 3)}} : δ = 0.98 (t, 6H), 1.51 (m, 4H), 1.80 (m, 4H), 4.06 (t, 4H), 7.0 (m, 4H), 7.6-8.0 ( m, 12H)

  As described above, the azo compound (B-1) can be efficiently synthesized through a short synthesis route.

Example 1
Two parts of an azo compound (B-1) having nematic liquid crystal properties was added to 98 parts of chloroform, dissolved by stirring, and filtered to obtain a dichroic dye composition coating solution. Next, the coating solution was applied onto the alignment film formed and rubbed on the glass substrate, and then naturally dried in chloroform at room temperature. Polyvinyl alcohol was used as the alignment film.
Absorbance (Az) for polarized light having a vibration plane in the direction of the absorption axis in the dye film plane and absorbance (Ay) for polarized light having a vibration plane in the direction of the polarization axis in the plane of the dye film in the obtained light absorption anisotropic film Table 1 shows the dichroic ratio (D), the maximum absorption wavelength (λmax), and the phase transition temperature obtained from the above. The obtained light absorption anisotropic film had a high dichroic ratio (light absorption anisotropy) capable of functioning sufficiently as a polarizing film.

(Examples 2-9)
In Example 1, the azo compound (B-1) was converted into an azo compound (B-3), (C-1), (C-3), (C-5), (C-6), ( A light absorption anisotropic film was obtained in the same manner except that it was changed to C-7), (D-2), and (D-3). Table 1 shows the dichroic ratio (D), the maximum absorption wavelength (λmax), and the phase transition temperature. The obtained light absorption anisotropic film had a high dichroic ratio (light absorption anisotropy) capable of functioning sufficiently as a polarizing film.

(Comparative Example 1)
The same procedure as in Example 1 was carried out except that the azo compound (B-1) was changed to the following azo compound (E-1) having nematic liquid crystallinity, but crystallization occurred on the alignment film, resulting in a light absorption anisotropic film. Was not obtained. The azo compound (E-1) is a compound that can be synthesized with the same number of synthesis steps as the azo compound (B-1) shown in Synthesis Example 1. As is apparent from the following structural formula, the azo compound (B- The molecular length is shorter than 1). Table 1 shows the dichroic ratio (D), the maximum absorption wavelength (λmax), and the phase transition temperature.

(Synthesis Example 2)
The following azo compound (E-2) was synthesized as follows.
p-Butylaniline (4) was suspended in hydrochloric acid, and a sodium nitrite aqueous solution was gradually added while maintaining the liquid temperature at 5 ° C. or lower for diazotization. This reaction solution was added to a methanolic solution of sodium phenylaminomethanesulfonate to obtain an azo compound (5). This compound was hydrolyzed under basic conditions to obtain an azo compound (6). This compound was suspended in hydrochloric acid and diazotized by gradually adding an aqueous sodium nitrite solution while keeping the liquid temperature at 5 ° C. or lower. This reaction solution was added to a methanol solution of 1-aminonaphthalene to obtain an azo compound (7). This compound was suspended in hydrochloric acid and diazotized by gradually adding an aqueous sodium nitrite solution while keeping the liquid temperature at 5 ° C. or lower. This reaction solution was added to a methanol solution of phenol basified with potassium hydroxide to obtain an azo compound (8). This compound was dissolved in a mixed solvent of hexanol / toluene to which a catalytic amount of sulfuric acid was added, and heated to reflux in a flask equipped with a Dean-Stark distillation apparatus to obtain an azo compound (E-2).
¹ H-NMR (CDCl ₃ ): δ = 0.92 (t, 3H), 0.95 (t, 3H), 1.14-1.67 (m, 10H), 1.82 (m, 2H), 2.71 (t, 2H), 4.04 ( t, 2H), 6.77 (d, 2H), 7.33 (d, 2H), 7.6-8.3 (m, 12H), 9.04 (m, 2H)

  As described above, the synthesis of the azo compound (E-2) requires a long synthetic route.

(Comparative Example 2)
A light absorption anisotropic film was obtained in the same manner as in Example 1 except that the azo compound (B-1) was changed to the following azo compound (E-2) having nematic liquid crystallinity. Table 1 shows the dichroic ratio (D), the maximum absorption wavelength (λmax), and the phase transition temperature. As described above, the synthesis of the azo compound (E-2) requires more steps than the azo compound (B-1) shown in Synthesis Example 1, but the light absorption anisotropic property obtained from the composition of this compound The dichroic ratio (light absorption anisotropy) of the conductive film and the dichroic ratio of the light absorption anisotropic film obtained in Example 1 were approximately the same.

Ｋ：結晶相
Ｎ：ネマチック相

K: Crystal phase N: Nematic phase

Claims (7)

A dichroic dye composition containing at least one azo compound having liquid crystallinity, which is a symmetric structure via a linking group L, represented by the following general formula (1).

(In the formula, L represents a single bond or a divalent linking group, R represents a hydrogen atom, an alkyl group, an alkoxy group, or an amino group, and Ar represents an aromatic hydrocarbon group which may have a substituent. Alternatively, it represents an aromatic heterocyclic ring (when there are a plurality of Ars, they may be the same or different from each other), and a represents an integer of 1 to 3.)   2. The dichroic dye composition according to claim 1, wherein Ar is an optionally substituted phenylene group or naphthylene group in the azo compound represented by the general formula (1).   In the azo compound represented by the general formula (1), L is a single bond, azo group, ethylene group, 1,4-cyclohexylene group, acetylene group, ester group, phenylene group, naphthylene group, piperidinyl group, piperazinyl group. The dichroic dye composition according to claim 1, wherein the dichroic dye composition is a linking group configured by combining one or more selected from the group consisting of:   The light absorption anisotropic film formed from the dichroic dye composition of any one of Claims 1-3.   A polarizing element having an alignment film and the light absorption anisotropic film according to claim 4 on a support.   A liquid crystal display device comprising the light absorption anisotropic film according to claim 4 or the polarizing element according to claim 5.   (1) A step of rubbing the support or the alignment film formed on the support; and (2) any one of claims 1 to 3 dissolved in an organic solvent on the support or alignment film subjected to the rubbing treatment. The polarizing element according to claim 5, comprising: a step of applying the dichroic dye composition according to claim 1; and a step of orienting the dichroic dye composition by evaporating the organic solvent. Manufacturing method.