CN109154685B

CN109154685B - Alignment layer forming composition

Info

Publication number: CN109154685B
Application number: CN201780020938.1A
Authority: CN
Inventors: 伊藤潤; 菅野裕太; 稻見佳代; 畑中真
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2016-03-31
Filing date: 2017-03-30
Publication date: 2022-04-19
Anticipated expiration: 2037-03-30
Also published as: JPWO2017170951A1; WO2017170951A1; TWI734766B; JP7025702B2; TW201805367A; KR20180132652A; KR102307799B1; CN109154685A

Abstract

The present invention relates to an alignment layer forming composition. The present invention provides a polymer composition for a liquid crystal alignment film, which can align a polymerizable liquid crystal composition when obtaining a highly dichroic polarizing element. The present invention provides a polymer composition containing (A) a side chain type polymer exhibiting liquid crystal photosensitivity in a specific temperature range, (B) a dichroic dye, and an organic solvent. A substrate having a liquid crystal alignment film formed of the polymer composition can be provided with a highly dichroic polarizing element by coating a polymerizable liquid crystal composition on the alignment film, then drying the coating by heating, and if necessary, further irradiating with ultraviolet light.

Description

Alignment layer forming composition

Technical Field

The present invention relates to a polymer composition useful for forming an alignment layer for aligning a polymerizable liquid crystal composition to be a polarizing layer when forming a polarizing element.

Background

Iodine has been widely used as a dichroic dye in a polarizing plate used for a liquid crystal display or the like. However, iodine-based polarizing films have a problem of poor heat resistance, light resistance, and the like, and therefore attempts have been made to use dichroic dyes, which are organic dichroic materials.

Heretofore, as a dichroic dye, a dye having an azo skeleton as a basic skeleton (patent documents 1 to 2), a dye having an anthraquinone skeleton or the like has been often used in order to obtain high-level dichroism.

As a method for producing a polarizing plate, in addition to a method for stretching a polymer film containing iodine, a dichroic dye, or the like, a method for coating a liquid crystal composition obtained by mixing a liquid crystal compound as a host material with a dye as a guest material on a substrate is known as a coating-type polarizing plate (patent document 3). In addition, the following methods are proposed: a method of using a mixture of a crosslinkable liquid crystal and a polymerizable dichroic dye for providing a more stable polarizing film (patent document 4); a method for producing an optically anisotropic body in which a polymerizable non-liquid crystal solvent is added to a polymerizable liquid crystal compound to leave the polymerizable non-liquid crystal solvent in a coating film and adhesion to other optical films or the like is improved (patent document 5); and a method for producing a polymerizable liquid crystal base preparation containing a polymerizable liquid crystal base compound and a dichroic dye, and efficiently producing a polarizer in terms of time and cost by using the polymerizable liquid crystal base preparation (patent document 6).

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2011-213610

Patent document 2: japanese patent laid-open publication No. 2006-525382

Patent document 3: japanese patent laid-open publication No. 2008-547062

Patent document 4: japanese patent laid-open publication No. 2004-535483

Patent document 5: japanese patent laid-open No. 2004-198480

Patent document 6: japanese patent laid-open publication No. 2006-161051

Disclosure of Invention

[ problems to be solved by the invention ]

In order to improve the absorption characteristics in the visible light region, it has been studied to formulate a dichroic dye having excellent absorption characteristics at a high content in a liquid crystalline composition. However, such a dichroic dye generally has a low solubility in a solvent, and therefore, there is a problem that it is difficult to achieve a high content formulation in a liquid crystal composition.

Under the circumstances, the present invention provides a polymer composition for a liquid crystal alignment film capable of aligning a polymerizable liquid crystal composition when obtaining a highly dichroic polarizing element.

[ means for solving problems ]

The present inventors have made extensive studies to achieve the above object, and as a result, have found the following invention.

< 1 > a polymer composition comprising (A) a side chain polymer exhibiting liquid crystallinity in a specific temperature range, and (B) a dichroic dye and an organic solvent.

< 2 > the polymer composition according to < 1 >, wherein the component (A) is a side chain type polymer having a photosensitive side chain which causes photocrosslinking, photoisomerization or photofuji rearrangement.

< 3 > the polymer composition according to < 1 >, wherein the component (A) is a side chain type polymer having any one of photosensitive side chains selected from the group consisting of the following formulas (1) to (6).

[ solution 1]

Wherein A, B, D each independently represents a single bond, -O-, -CH₂-, -COO-, -OCO-, -CONH-, -NH-CO-, -CH-CO-O-or-O-CO-CH-;

s represents an alkylene group having 1 to 12 carbon atoms, and hydrogen atoms bonded to these groups may be substituted with a halogen group;

t represents a single bond or an alkylene group having 1 to 12 carbon atoms, and hydrogen atoms bonded to these groups may be substituted with a halogen group;

Y₁represents a ring selected from the group consisting of 1-valent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and C5-8 alicyclic hydrocarbon, or represents a group in which 2-6 rings, which are the same or different, selected from these substituents are bonded via a bonding group B, and hydrogen atoms bonded to these groups may be independently substituted by-COOR₀(in the formula, R₀Hydrogen atom or alkyl group having 1 to 5 carbon atoms), -NO₂、-CN、-CH＝C(CN)₂-CH ═ CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;

Y₂representing a valence selected from 2A benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination of these rings, wherein hydrogen atoms bonded to these groups may be independently substituted with-NO₂、-CN、-CH＝C(CN)₂-CH ═ CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;

r represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or Y₁The same definition;

x represents a single bond, -COO-, -OCO-, -N-, -CH-, -C.ident.C-, -CH-CO-O-or-O-CO-CH-, and when the number of X is 2, X may be the same or different from each other;

cou represents a coumarin-6-yl group or a coumarin-7-yl group, each of which is substituted independently by a hydrogen atom to which a group-NO-is bonded₂、-CN、-CH＝C(CN)₂-CH ═ CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;

q1 and q2 are one 1 and the other 0;

q3 is 0 or 1;

p and Q each independently represent a group selected from the group consisting of a 2-valent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination of these rings; wherein, when X is-CH-CO-O-, -O-CO-CH-and the side to which-CH-is bonded, P or Q is an aromatic ring;

l1 is 0 or 1;

l2 is an integer of 0 to 2;

a represents a single bond when T is a single bond, when both l1 and l2 are 0;

when l1 is 1, B represents a single bond when T is a single bond;

h and I each independently represent a group selected from the group consisting of a 2-valent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a combination of these rings.

< 4 > the polymer composition according to any one of the above < 1 > to < 3 >, wherein the component (A) is a side chain type polymer having any one liquid crystalline side chain selected from the group consisting of the following formulas (21) to (31).

[ solution 2]

Wherein A, B, q1 and q2 have the same meanings as defined above;

Y₃represents a group selected from the group consisting of 1-valent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocycle, C5-8 alicyclic hydrocarbon and a combination of these rings, and hydrogen atoms bonded to these groups may be independently substituted with-NO₂CN, -a halogen group, an alkyl group having 1 to 5 carbon atoms or an alkyloxy group having 1 to 5 carbon atoms;

R₃represents a hydrogen atom, -NO₂、-CN、-CH＝C(CN)₂-CH ═ CH — CN, halogen, 1-valent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocycle, alicyclic hydrocarbon having 5 to 8 carbon atoms, alkyl having 1 to 12 carbon atoms, or alkoxy having 1 to 12 carbon atoms;

l represents an integer of 1 to 12, m represents an integer of 0 to 2, wherein in the formulae (25) to (26), the total of all m is 2 or more, in the formulae (27) to (28), the total of all m is 1 or more, and m1, m2 and m3 are each independently an integer of 1 to 3;

R₂represents a hydrogen atom, -NO₂CN, -halogen, 1-valent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocycle, alicyclic hydrocarbon with 5-8 carbon atoms, and alkyl or alkyloxy;

Z₁、Z₂represents a single bond, -CO-, -CH₂O-、-CH＝N-、-CF₂-。

< 5 > the polymer composition according to any one of said < 1 > to < 4 >, characterized in that: contains a compound represented by the following formula (C) as the component (C).

[ solution 3]

(in the formula, R¹⁰¹、R¹⁰²、R¹⁰³、R¹⁰⁴And R¹⁰⁵Any three to five of (A) each independently represent a group selected from a hydrogen atom, a halogen atom, C₁～C₆Alkyl radical, C₁～C₆Haloalkyl, C₁～C₆Alkoxy radical, C₁～C₆Haloalkoxy, C₃～C₈Cycloalkyl radical, C₃～C₈Halocycloalkyl radical, C₂～C₆Alkenyl radical, C₂～C₆Haloalkenyl, C₃～C₈Cycloalkenyl radical, C₃～C₈Halocycloalkenyl radical, C₂～C₆Alkynyl, C₂～C₆Haloalkynyl group, C₁～C₆Alkoxy radical, C₁～C₆Haloalkoxy, (C)₁～C₆Alkyl) carbonyl (C)₁～C₆Haloalkyl) carbonyl, (C)₁～C₆Alkoxy) carbonyl (C)₁～C₆Haloalkoxy) carbonyl, (C)₁～C₆Alkylamino) carbonyl group, (C)₁～C₆Haloalkyl) aminocarbonyl, di (C)₁～C₆Alkyl) a substituent of the group consisting of aminocarbonyl, cyano and nitro, in R¹⁰¹、R¹⁰²、R¹⁰³、R¹⁰⁴And R¹⁰⁵In the case that any three to four of (A) are defined as above, R¹⁰¹、R¹⁰²、R¹⁰³、R¹⁰⁴And R¹⁰⁵One or two of the remaining(s) represent the following formula (c-2)

[ solution 4]

(in the formula (c-2), the dotted line represents a bond, R¹⁰⁶Represents an alkylene group having 1 to 30 carbon atoms, a phenylene group, or a divalent carbocyclic or heterocyclic ring, wherein 1 or more hydrogen atoms in the alkylene group, the phenylene group, or the divalent carbocyclic or heterocyclic ring may be substituted with a fluorine atom or an organic group. In addition, R¹⁰⁶In (C-CH)₂CH₂-may be substituted by-CH ═ CH-, R¹⁰⁶In (C-CH)₂May be substituted by phenylene or by a divalent carbocyclic or heterocyclic ring, and may also be substituted by any of the groups listed below without being adjacent to one another: -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH-, -CO-. R¹⁰⁷Represents a hydrogen atom or a methyl group), n represents 0 or 1)

< 6 > an alignment layer forming composition comprising the polymer composition as described in any one of said < 1 > to < 5 >.

[ Effect of the invention ]

According to the present invention, a novel polymer composition that can be used for obtaining a polarizing plate having high-level polarizing performance without blending a dichroic dye in a liquid crystal composition at a high content can be provided.

Detailed Description

The present inventors have made extensive studies and, as a result, have obtained the following findings, thereby completing the present invention.

The polymer composition of the present invention has a side chain polymer capable of exhibiting liquid-crystalline photosensitivity (hereinafter also simply referred to as a side chain polymer) and a dichroic dye, and a coating film obtained using the polymer composition is a film having a side chain polymer capable of exhibiting liquid-crystalline photosensitivity. The coating film may be subjected to alignment treatment by polarized light irradiation without being subjected to rubbing treatment. After the polarized light irradiation, the side chain polymer film is heated to form a coating film (hereinafter, also referred to as an alignment layer) to which an alignment controlling ability is imparted. At this time, the slight anisotropy exhibited by the polarized light irradiation becomes a driving force (driving force), and the liquid crystalline side chain polymer itself is efficiently realigned by self-assembly. As a result, highly efficient alignment treatment as an alignment layer is achieved, and an alignment layer imparted with high alignment controllability can be obtained. Here, by containing a dichroic dye in the polymer composition, an alignment layer having a high dichroic ratio can be obtained. Therefore, the polymer composition of the present invention is useful as an alignment layer forming composition for aligning a polarizing layer containing a liquid crystalline composition and, if necessary, a dichroic dye, when forming the polarizing layer.

Hereinafter, embodiments of the present invention will be described in detail.

< (A) a photosensitive side-chain polymer exhibiting liquid crystallinity in a specific temperature range

(A) The component (B) is a side chain type polymer which exhibits liquid crystallinity in a specific temperature range and is photosensitive.

(A) The side chain type polymer is preferably reacted under light having a wavelength in the range of 250 to 400nm and exhibits liquid crystallinity in the temperature range of 60 to 300 ℃.

(A) The side chain type polymer preferably has a photosensitive side chain which reacts with light having a wavelength in the range of 250nm to 400 nm.

(A) The side chain type polymer preferably has a mesogen group so that liquid crystallinity is exhibited in a temperature range of 60 to 300 ℃.

(A) The side chain type polymer has a photosensitive side chain bonded to a main chain, and can induce a crosslinking reaction, an isomerization reaction, or a photofuji rearrangement by light. The structure of the side chain having photosensitivity is not particularly limited, and is preferably a structure in which crosslinking reaction or photofujis rearrangement is caused by light induction, and more preferably a structure in which crosslinking reaction is caused. In this case, even if exposed to external stress such as heat, the achieved alignment controllability can be stably maintained for a long period of time. The structure of the side chain type polymer film capable of expressing liquid crystallinity and photosensitivity is not particularly limited as long as it satisfies the above characteristics, and it is preferable that the side chain structure contains a rigid mesogen component. In this case, when the side chain type polymer is formed into a liquid crystal alignment film, a stable liquid crystal alignment can be obtained.

The structure of the polymer may be, for example, the following: a side chain having a main chain and a side chain bonded to the main chain, the side chain having a liquid crystal raw component such as biphenyl, terphenyl, phenylcyclohexyl, phenylbenzoate, azophenyl, or the like, and a photosensitive group which is bonded to a terminal portion and causes a crosslinking reaction or an isomerization reaction by induced light; or a side chain having a benzoate group which is not only a liquid crystal raw component but also causes photofuji rearrangement.

As a more specific example of the structure of the side chain type polymer film capable of exhibiting liquid crystallinity, the following structure is preferred: the resin composition has a main chain composed of at least one selected from the group consisting of a radical polymerizable group such as hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, α -methylene- γ -butyrolactone, styrene, ethylene, maleimide, norbornene and siloxane, and a side chain containing at least one of the following formulas (1) to (6).

[ solution 5]

Y₂represents a group selected from the group consisting of a 2-valent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination of these ringsThe hydrogen atoms bonded to these groups may each independently be substituted by-NO₂、-CN、-CH＝C(CN)₂-CH ═ CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;

q1 and q2 are one 1 and the other 0;

q3 is 0 or 1;

p and Q each independently represent a group selected from the group consisting of a 2-valent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination of these rings; wherein, when X is-CH-CO-O-, -O-CO-CH-, P or Q on the side to which-CH-is bonded represents an aromatic ring;

l1 is 0 or 1;

l2 is an integer of 0 to 2;

a represents a single bond when T is a single bond, when both l1 and l2 are 0;

when l1 is 1, B represents a single bond when T is a single bond;

The side chain is preferably any one of photosensitive side chains selected from the group consisting of the following formulae (7) to (10).

In the formula, A, B, D, Y₁、X、Y₂And R has the same meaning as defined above;

l represents an integer of 1 to 12;

m represents an integer of 0 to 2, m1 and m2 represent an integer of 1 to 3;

n represents an integer of 0 to 12 (wherein, when n is 0, B is a single bond).

[ solution 6]

The side chain is preferably any one of photosensitive side chains selected from the group consisting of the following formulae (11) to (13).

Wherein A, X, l, m and R have the same meanings as defined above.

[ solution 7]

The side chain is preferably a photosensitive side chain represented by the following formula (14) or (15).

In the formula, A, Y₁X, l, m1 and m2 have the same definitions as described.

[ solution 8]

The side chain is preferably a photosensitive side chain represented by the following formula (16) or (17).

Wherein A, X, l and m have the same meanings as defined above.

[ solution 9]

The side chain is preferably a photosensitive side chain represented by the following formula (18) or (19).

In the formula, A, B, Y₁L, q1, q2, m1 and m2 have the same definitions as described.

R₁Represents a hydrogen atom, -NO₂、-CN、-CH＝C(CN)₂a-CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms or an alkyloxy group having 1 to 5 carbon atoms.

[ solution 10]

The side chain is preferably a photosensitive side chain represented by the following formula (20).

In the formula, A, Y₁X, l and m have the same definitions as stated.

[ solution 11]

The side chain polymer (a) preferably has any liquid crystalline side chain selected from the group consisting of the following formulas (21) to (31).

Wherein A, B, q1 and q2 have the same meanings as defined above;

l represents an integer of 1 to 12, m represents an integer of 0 to 2, wherein in the formulae (25) to (26), the total of all m is 2 or more, in the formulae (27) to (28), the total of all m is 1 or more, and m1, m2 and m3 each independently represents an integer of 1 to 3;

R₂represents a hydrogen atom, -NO₂CN, -halogen radical, 1-valent benzene ringA naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocycle, an alicyclic hydrocarbon with 5-8 carbon atoms, and an alkyl group or an alkyloxy group;

Z₁、Z₂represents a single bond, -CO-, -CH₂O-、-CH＝N-、-CF₂-。

[ solution 12]

Method for producing photosensitive side chain type polymer

The side chain type polymer capable of exhibiting photosensitivity of liquid crystallinity can be obtained by polymerizing a photoreactive side chain monomer having the photosensitive side chain and a liquid crystalline side chain monomer.

[ photoreactive side chain monomer ]

The photoreactive side chain monomer is a monomer that can form a polymer having a photosensitive side chain at a side chain site of the polymer when the polymer is formed.

The photoreactive group in the side chain is preferably represented by the following structure or a derivative thereof.

[ solution 13]

More specific examples of the photoreactive side chain monomer are preferably a structure having a polymerizable group comprising at least one member selected from the group consisting of a radical polymerizable group such as hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, α -methylene- γ -butyrolactone, styrene, ethylene, maleimide, norbornene and a siloxane, and a photosensitive side chain comprising at least one member selected from the group consisting of the photosensitive side chains represented by the formulae (1) to (6), and preferably, for example, a photosensitive side chain comprising at least one member selected from the formulae (7) to (10), a photosensitive side chain comprising at least one member selected from the formulae (11) to (13), a photosensitive side chain represented by the formula (14) or (15), a photosensitive side chain represented by the formula (16) or (17), a photosensitive side chain, A photosensitive side chain represented by the formula (18) or (19) or a photosensitive side chain represented by the formula (20).

Examples of such photoreactive side chain monomers include monomers selected from the group consisting of the following formulae M1-1 to M1-7 and M1-17 to M1-20.

[ solution 14]

[ solution 15]

[ solution 16]

(wherein M1 represents a hydrogen atom or a methyl group, and s1 represents the number of methylene groups and is a natural number of 2 to 9.)

[ solution 17]

(wherein R is OH or NH)₂M1 represents a hydrogen atom or a methyl group, s1 represents the number of methylene groups and is a natural number of 2 to 9)

Examples of the photoreactive side chain monomer represented by the formula (M1-1) include: 4- (6-methacryloyloxyhexyl-1-oxy) cinnamic acid, 4- (6-acryloyloxyhexyl-1-oxy) cinnamic acid, 4- (3-methacryloyloxypropyl-1-oxy) cinnamic acid, 4- (4- (6-methacryloyloxyhexyl-1-oxy) benzoyloxy) cinnamic acid wherein R in the equation (M1-1) represents OH, and 4- (6-methacryloyloxyhexyl-1-oxy) cinnamamide, 4- (6-acryloyloxyhexyl-1-oxy) cinnamamide, 4- (3-R in methacryloxypropyl-1-oxy) cinnamamide equation (M1-1) represents NH₂And the like.

[ liquid Crystal side chain monomer ]

The liquid crystalline side chain monomer is a monomer derived from a polymer having liquid crystallinity and capable of forming a mesogen group at a side chain position.

The mesogen group of the side chain may be a group having a mesogen structure alone, such as a biphenyl group or a benzoate group, or may be a group having a mesogen structure in which side chains are hydrogen-bonded to each other, such as benzoic acid. The following structure is preferred as the mesogen group of the side chain.

[ solution 18]

More specific examples of the liquid crystalline side chain monomer preferably have the following structure: the resin composition has a polymerizable group comprising at least one member selected from the group consisting of a radical polymerizable group such as hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, α -methylene- γ -butyrolactone, styrene, ethylene, maleimide, norbornene and a siloxane, and a side chain comprising at least one member selected from the group consisting of the above-mentioned formulas (21) to (31).

Among such liquid crystalline side chain monomers, as the monomer having a carboxyl group or an amide group, a monomer represented by a formula selected from the group consisting of the following formulae M2-1 to M2-9 may be used.

[ solution 19]

[ solution 20]

(wherein R is as defined in the formulaRepresents OH or NH₂M1 represents a hydrogen atom or a methyl group, s1 represents the number of methylene groups and is a natural number of 2 to 9)

As an example of the other monomer, a monomer having a substituent group which exhibits liquid crystallinity may be used, and a monomer represented by a formula selected from the group consisting of the following formulae M2-10 to M2-16 may be used.

[ solution 21]

(wherein M1 represents a hydrogen atom or a methyl group, s1 represents the number of methylene groups and is a natural number of 2 to 9.)

(A) The side chain type polymer can be obtained by copolymerization of the photoreactive side chain monomer exhibiting liquid crystallinity. The side chain monomer is obtained by copolymerization of a photoreactive side chain monomer that does not exhibit liquid crystallinity and a liquid crystalline side chain monomer, or copolymerization of a photoreactive side chain monomer that exhibits liquid crystallinity and a liquid crystalline side chain monomer. In addition, copolymerization with other monomers can be carried out within a range not impairing the performance of liquid crystal properties.

Examples of the other monomer include monomers capable of radical polymerization, which can be obtained by industrial means.

Specific examples of the other monomers include: unsaturated carboxylic acid, acrylate compound, methacrylate compound, maleimide compound, acrylonitrile, maleic anhydride, styrene compound, vinyl compound, and the like.

Specific examples of the unsaturated carboxylic acid include: acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and the like.

Examples of the acrylate compound include: methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2, 2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecanyl acrylate, and 8-ethyl-8-tricyclodecanyl acrylate.

Examples of the methacrylate ester compound include: methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2, 2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecanyl methacrylate, and 8-ethyl-8-tricyclodecanyl methacrylate.

Examples of the vinyl compound include: vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, propyl vinyl ether, and the like.

Examples of the styrene compound include: styrene, methylstyrene, chlorostyrene, bromostyrene, and the like.

Examples of the maleimide compound include: maleimide, N-methyl maleimide, N-phenyl maleimide, and N-cyclohexyl maleimide.

The content of the photoreactive side chain in the side chain polymer of the present invention is preferably 10 to 100 mol%, more preferably 20 to 95 mol%, and still more preferably 30 to 90 mol%, based on the total amount of the side chains.

When the content of the photoreactive side chain in the side chain type polymer is less than 10 mol% based on the total amount of the side chain, the coating film formed from the polymer composition of the present invention may not sufficiently exhibit the effect as a liquid crystal alignment film.

The content of the liquid crystalline side chain in the side chain polymer of the present invention is preferably 90 mol% or less, more preferably 5 mol% to 80 mol%, and still more preferably 10 mol% to 70 mol%, based on the total amount of the side chain.

When the content of the liquid crystalline side chain in the side chain type polymer is more than 90 mol% based on the total amount of the side chain, the content of the photoreactive side chain is less than 10 mol% based on the total amount of the side chain, and therefore, the coating film formed from the polymer composition of the present invention may not sufficiently exhibit the effect as a liquid crystal alignment film.

The side chain polymer of the present invention may further contain a side chain other than the photoreactive side chain and the liquid crystalline side chain. When the total content of the photoreactive side chain and the liquid crystalline side chain is less than 100%, the content of the other side chain is the remaining part.

The method for producing the side chain polymer of the present embodiment is not particularly limited, and a method generally used in industrial operations can be used. Specifically, the polymer can be produced by cationic polymerization, radical polymerization, or anionic polymerization of a vinyl group using a liquid crystalline side chain monomer or a photoreactive side chain monomer. Among these, radical polymerization is particularly preferable from the viewpoint of ease of reaction control.

As the polymerization initiator for radical polymerization, a known compound such as a radical polymerization initiator or a reversible addition-fragmentation chain transfer (RAFT) polymerization reagent can be used.

The radical thermal polymerization initiator is a compound that generates radicals by heating to a temperature above the decomposition temperature. Examples of such a radical thermal polymerization initiator include: ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), hydrogen peroxides (hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-t-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketals (dibutyl peroxycyclohexane, etc.), alkyl peroxides (t-butyl peroxyneodecanoate, t-butyl peroxypivalate, t-amyl 2-ethylcyclohexane peroxide, etc.), persulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), azo compounds (azobisisobutyronitrile, 2' -bis (2-hydroxyethyl) azobisisobutyronitrile, etc.). Such radical thermal polymerization initiators may be used in 1 kind alone, or 2 or more kinds may be used in combination.

The radical photopolymerization initiator is not particularly limited as long as it is a compound that initiates radical polymerization by irradiation with light. Examples of such a radical photopolymerization initiator include: benzophenone, milrinone, 4 '-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropyl xanthone, 2, 4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4' -isopropylphenylacetone, 1-hydroxycyclohexylphenylketone, isopropyl benzoin ether, isobutyl benzoin ether, 2-diethoxyacetophenone, 2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1-one Ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4 '-bis (tert-butylperoxycarbonyl) benzophenone, 3,4,4' -tris (tert-butylperoxycarbonyl) benzophenone, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, 2- (4 '-methoxystyryl) -4, 6-bis (trichloromethyl) s-triazine, 2- (3',4 '-dimethoxystyryl) -4, 6-bis (trichloromethyl) s-triazine, 2- (2' -methoxystyryl) -4, 6-bis (trichloromethyl) s-triazine, 2- (4 '-pentyloxystyryl) -4, 6-bis (trichloromethyl) s-triazine, 4- [ p-N, N-bis (ethoxycarbonylmethyl) ] -2, 6-bis (trichloromethyl) s-triazine, 1, 3-bis (trichloromethyl) -5- (2' -chlorophenyl) s-triazine, 1, 3-bis (trichloromethyl) -5- (4 '-methoxyphenyl) s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzothiazole, 2-mercaptobenzothiazole, 3' -carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4',5,5' -tetraphenyl-1, 2' -biimidazole, 2' -bis (2-chlorophenyl) -4,4',5,5' -tetrakis (4-ethoxycarbonylphenyl) -1,2' -biimidazole, 2' -bis (2, 4-dichlorophenyl) -4,4',5,5' -tetraphenyl-1, 2' -biimidazole, 2' -bis (2, 4-dibromophenyl) -4,4',5,5' -tetraphenyl-1, 2' -biimidazole, 2' -bis (2,4, 6-trichlorophenyl) -4,4',5,5' -tetraphenyl-1, 2' -biimidazole, 3- (2-methyl-2-dimethylaminopropionyl) carbazole, 3, 6-bis (2-methyl-2-morpholinopropionyl) -9- N-dodecylcarbazole, 1-hydroxycyclohexylphenylketone, bis (5-2, 4-cyclopentadien-1-yl) -bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 3',4,4' -tetrakis (tert-butylperoxycarbonyl) benzophenone, 3',4,4' -tetrakis (tert-hexylperoxycarbonyl) benzophenone, 3 '-bis (methoxycarbonyl) -4,4' -bis (tert-butylperoxycarbonyl) benzophenone, 3,4 '-bis (methoxycarbonyl) -4,3' -bis (tert-butylperoxycarbonyl) benzophenone, 4,4 '-bis (methoxycarbonyl) -3,3' -bis (tert-butylperoxycarbonyl) benzophenone, bis (5-2, 4-cyclopentadien-1-yl) -bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 2- (3-methyl-3H-benzothiazol-2-ylidene) -1-naphthalen-2-yl-ethanone or 2- (3-methyl-1, 3-benzothiazol-2 (3H) -ylidene) -1- (2-benzoyl) ethanone, and the like. These compounds may be used alone, or 2 or more of them may be used in combination.

The radical polymerization method is not particularly limited, and emulsion polymerization, suspension polymerization, dispersion polymerization, precipitation polymerization, bulk polymerization, solution polymerization, and the like can be used.

The organic solvent used for the polymerization reaction of the side chain type polymer capable of exhibiting liquid crystallinity is not particularly limited as long as it can dissolve the polymer to be produced. Specific examples of the organic solvent are shown below.

Examples thereof include: n, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethylsulfoxide, gamma-butyrolactone, isopropanol, methoxymethylpentanol, dipentene, ethylpentyl ketone, methylnonyl ketone, methylethyl ketone, methylisoamyl ketone, methylisopropyl ketone, methylcellosolve, ethylcellosolve, methylcellosolve acetate, ethylcellosolve acetate, butylcarbitol, ethylcarbitol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol, Diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, methyl propionate, ethyl propionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionate, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diethylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N, N-dimethylpropionamide, 3-ethoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, and the like.

These organic solvents may be used alone or in combination. In addition, a solvent that does not dissolve the produced polymer may be used in combination with the organic solvent in a range where the produced polymer does not precipitate.

In addition, in radical polymerization, oxygen in an organic solvent causes polymerization reaction to be hindered, and therefore, the organic solvent is preferably a solvent that is degassed as much as possible.

The polymerization temperature in the radical polymerization may be any temperature of 30 to 150 ℃, and preferably 50 to 100 ℃. The reaction may be carried out at any concentration, but if the concentration is too low, it is difficult to obtain a polymer having a high molecular weight, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult, so the monomer concentration is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The reaction may be carried out at a high concentration in the initial stage, and then an organic solvent may be added.

In the radical polymerization reaction, if the ratio of the radical polymerization initiator to the monomer is too large, the molecular weight of the obtained polymer becomes small, and if it is too small, the molecular weight of the obtained polymer becomes large, so the ratio of the radical polymerization initiator to the monomer to be polymerized is preferably 0.1 to 10 mol%. In addition, various monomer components, solvents, initiators, and the like may be added during the polymerization.

[ recovery of Polymer ]

When the polymer produced is recovered from the reaction solution of the side chain type polymer capable of exhibiting liquid-crystalline photosensitivity obtained by the above reaction, the reaction solution may be charged into a poor solvent to precipitate the polymer. As the poor solvent for precipitation, there can be mentioned: methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, water, etc. The polymer precipitated after the addition of the poor solvent is filtered and recovered, and then dried at normal temperature or under reduced pressure or dried by heating. Further, if the polymer recovered by precipitation is dissolved again in the organic solvent, and precipitation recovery is performed again, and this operation is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the poor solvent in this case include alcohols, ketones, hydrocarbons, and the like, and it is preferable to use 3 or more kinds of poor solvents selected from these solvents, whereby the purification efficiency can be further improved.

The molecular weight of the side chain polymer (a) of the present invention is preferably 2000 to 1000000, more preferably 5000 to 100000, in weight average molecular weight measured by GPC (Gel Permeation Chromatography) method in consideration of the strength of the obtained coating film, workability at the time of forming the coating film, and uniformity of the coating film.

(B) dichroic dye

The dichroic dye is a dye having a property that the absorbance of a molecule in the major axis direction and the absorbance of the molecule in the minor axis direction are different from each other.

The dichroic dye preferably has an absorption maximum wavelength (λ MAX) within a range of 300 to 700 nm. Examples of such dichroic pigments include: acridine pigment, oxazine pigment, cyanine pigment, naphthalene pigment, azo pigment, anthraquinone pigment, and the like, and among them, azo pigment is preferable. Examples of the azo dye include: monoazo pigments, disazo pigments, trisazo pigments, tetraazo pigments, stilbene-azo pigments and the like, and disazo pigments and trisazo pigments are preferred.

Examples of the azo dye include a compound represented by the formula (b) (hereinafter, referred to as "compound (b)" in some cases).

A¹(-N＝N-A²)_p-N＝N-A³(b)

[ in the formula (b),

A¹and A³Independently represent an optionally substituted phenyl group, an optionally substituted naphthyl group or an optionally substituted 1-valent heterocyclic group. A. the²Represents an optionally substituted 1, 4-phenylene group, an optionally substituted naphthalene-1, 4-diyl group or an optionally substituted 2-valent heterocyclic group. p represents an integer of 1 to 4. When p is an integer of 2 or more, a plurality of A²Are independent of each other, can be the same or different]

Examples of the heterocyclic group having a valence of 1 include groups obtained by removing 1 hydrogen atom from a heterocyclic compound such as quinoline, thiazole, benzothiazole, thienothiazole, imidazole, benzimidazole, oxazole and benzoxazole. As the heterocyclic group having a valence of 2, a group obtained by removing 2 hydrogen atoms from the heterocyclic compound is exemplified.

As A¹And A³Phenyl, naphthyl and heterocyclic group having 1 valence in (A)²The substituent optionally having the p-phenylene group, naphthalene-1, 4-diyl group and 2-valent heterocyclic group in (1) includes: an alkyl group having 1 to 4 carbon atoms; alkoxy groups having 1 to 4 carbon atoms such as methoxy, ethoxy and butoxy groups; a fluorinated alkyl group having 1 to 4 carbon atoms such as a trifluoromethyl group; a cyano group; a nitro group; a halogen atom; substituted or unsubstituted amino groups such as amino, diethylamino and pyrrolidinyl (so-called substituted amino groups)The amino group is an amino group having 1 or 2 alkyl groups having 1 to 6 carbon atoms, or an amino group in which 2 substituted alkyl groups are bonded to each other to form an alkanediyl group having 2 to 8 carbon atoms. Unsubstituted amino is-NH₂)。

The alkyl group having 1 to 6 carbon atoms may be optionally straight-chain or branched, and includes: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-dimethylpropyl, 2-dimethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 1-dimethylbutyl, 1-ethylbutyl, 1, 2-trimethylpropyl, and the like.

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

[ solution 22]

[ solution 23]

[ formulae (2-1) to (2-6),

B¹～B²⁰independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, a nitro group, a substituted or unsubstituted amino group (the substituted amino group and the unsubstituted amino group are as defined above), a chlorine atom or a trifluoromethyl group.

n1 to n4 are independent of each other and represent an integer of 0 to 3.

When n1 is 2 or more, a plurality of B²Are independent of each other, can be the same or different,

when n2 is 2 or more, a plurality of B⁶Are independent of each other, can be the same or different,

when n3 is 2 or more, a plurality of B⁹Are independent of each other, can be the same or different,

when n4 is 2 or more, a plurality of B¹⁴Are independent of each other, can be the same or different]

The anthraquinone pigment is preferably a compound represented by formula (2-7).

[ solution 24]

[ in the formula (2-7),

R¹～R⁸independently of each other, represents a hydrogen atom, -R^x、-NH₂、-NHR^x、-NR^x ₂、-SR^xOr a halogen atom.

R^xRepresents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms]

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

[ solution 25]

[ in the formula (2-8),

R⁹～R¹⁵independently of each other, represents a hydrogen atom, -R^x、-NH₂、-NHR^x、-NR^x ₂、-SR^xOr a halogen atom.

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

[ solution 26]

[ in the formula (2-9),

R¹⁶～R²³independently of each other, represents a hydrogen atom, -R^x、-NH₂、-NHR^x、-NR^x ₂、-SR^xOr a halogen atom.

R in the formulae (2-7), (2-8) and (2-9)^xExamples of the alkyl group having 1 to 6 carbon atoms include: methyl, ethyl, propyl, butyl, pentyl, hexyl, and the like, and examples of the aryl group having 6 to 12 carbon atoms include: phenyl, toluyl, xylyl, naphthyl, and the like.

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

[ solution 27]

[ in the formula (2-10),

D¹and D²Each independently represents a group represented by any one of formulae (2-10a) to (2-10 d).

[ solution 28]

n5 represents an integer of 1 to 3

[ solution 29]

[ in the formula (2-11),

D³and D⁴Each represents a group represented by any one of the formulae (2-11a) to (2-11h) independently of the other.

[ solution 30]

n6 represents an integer of 1 to 3

Further, as a commercially available product of the above-mentioned dichroic dye, for example, there can be mentioned: g-207, G-241, G-470 (manufactured by Yunyuan Co., Ltd.), Yellow-8, KRD-901, KRD-902 (manufactured by Showa chemical industries, Ltd.), SI-486 (manufactured by Mitsui chemical Co., Ltd.).

The content of the dichroic dye as the component (B) in the alignment layer forming composition is preferably 0.1 part by mass or more and 30 parts by mass or less, more preferably 0.1 part by mass or more and 20 parts by mass or less, and still more preferably 0.1 part by mass or more and 10 parts by mass or less, with respect to 100 parts by mass of the side chain polymer as the component (a), from the viewpoint of improving the alignment of the dichroic dye.

< ingredient (C) >

The polymer composition of the present invention may further contain a compound represented by the following formula (C) as the component (C).

[ solution 31]

(in the formula, R¹⁰¹、R¹⁰²、R¹⁰³、R¹⁰⁴And R¹⁰⁵Any three to five of (A) each independently represent a group selected from a hydrogen atom, a halogen atom, C₁～C₆Alkyl radical, C₁～C₆Haloalkyl, C₁～C₆Alkoxy radical, C₁～C₆Haloalkoxy, C₃～C₈Cycloalkyl radical, C₃～C₈Halocycloalkyl radical, C₂～C₆Alkenyl radical, C₂～C₆Haloalkenyl, C₃～C₈Cycloalkenyl radical, C₃～C₈Halocycloalkenyl radical, C₂～C₆Alkynyl, C₂～C₆Haloalkynyl, (C)₁～C₆Alkyl) carbonyl (C)₁～C₆Haloalkyl) carbonyl, (C)₁～C₆Alkoxy) carbonyl (C)₁～C₆Haloalkoxy) carbonyl, (C)₁～C₆Alkylamino) carbonyl group, (C)₁～C₆Haloalkyl) aminocarbonyl, di (C)₁～C₆Alkyl) a substituent of the group consisting of aminocarbonyl, cyano and nitro, in R¹⁰¹、R¹⁰²、R¹⁰³、R¹⁰⁴And R¹⁰⁵In the case that any three to four of (A) are defined as above, R¹⁰¹、R¹⁰²、R¹⁰³、R¹⁰⁴And R¹⁰⁵One or two of the remaining(s) represent the following formula (c-2)

[ solution 32]

Examples of the halogen atom in the present specification include: fluorine atom, chlorine atom, bromine atom and iodine atom. In the present specification, the term "halogen" also means these halogen atoms.

In this specification C_a～C_bThe notation of alkyl represents a linear or branched hydrocarbon group having a to b carbon atoms, and specific examples thereof include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butylButyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group, 1-dimethylpropyl group, 1, 2-dimethylpropyl group, 2-dimethylpropyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 1-dimethylbutyl group, 1, 3-dimethylbutyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, and the like, and they may be selected depending on the range of the number of carbon atoms specified for each group.

In this specification C_a～C_bThe notation "haloalkyl" denotes a linear or branched hydrocarbon group having a carbon number of a to b, wherein the hydrogen atom bonded to the carbon atom is optionally substituted with a halogen atom, and in this case, when the hydrogen atom is substituted with 2 or more halogen atoms, these halogen atoms may be the same as each other or different from each other. Specific examples thereof include: fluoromethyl, chloromethyl, bromomethyl, iodomethyl, difluoromethyl, chlorofluoromethyl, dichloromethyl, bromofluoromethyl, trifluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trichloromethyl, bromodifluoromethyl, bromochlorofluoromethyl, dibromofluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2, 2-difluoroethyl, 2-chloro-2-fluoroethyl, 2, 2-dichloroethyl, 2-bromo-2-fluoroethyl, 2,2, 2-trifluoroethyl, 2-chloro-2, 2-difluoroethyl, 2, 2-dichloro-2-fluoroethyl, 2,2, 2-trichloroethyl, 2-bromo-2, 2-difluoroethyl, 2-bromo-2-chloro-2-fluoroethyl, 2-bromo-2, 2-dichloroethyl, 1,2, 2-tetrafluoroethyl, pentafluoroethyl, 1-chloro-1, 2,2, 2-tetrafluoroethyl, 2-chloro-1, 1,2, 2-tetrafluoroethyl, 1, 2-dichloro-1, 2, 2-trifluoroethyl, 2-bromo-1, 1,2, 2-tetrafluoroethyl, 2-fluoropropyl, 2-chloropropyl, 2-bromopropyl, 2-chloro-2-fluoropropyl, 2, 3-dichloropropyl, 2-bromo-3-fluoropropyl, 3-bromo-2-chloropropyl, 2, 3-dibromopropyl, 3,3, 3-trifluoropropyl, 3-bromo-3, 3-difluoropropyl, perfluoropropyl, and perfluoropropyl, 2-2, 2-bromo-2, 2-2, 2,2, 2-3, 3, 3-3, 3-3, 3, 3-difluoro-3, 3-3, 3, 3-3, 3-3, 3, 3-3, 3, 3-difluoropropyl, 3-3, 3-difluoropropyl, 3,3, 3-difluoropropyl, 3-3, 3, 3-difluoropropyl, 3,3, and 2-difluoropropyl, 3,3,3-, 2,2,3, 3-tetrafluoropropyl group, 2-chloro-3, 3, 3-trifluoropropyl group, 2,2,3,3, 3-pentafluoropropyl group, 1,2,3,3, 3-hexafluoropropyl group, heptafluoropropyl group, 2, 3-dichloro-1, 1,2,3, 3-pentafluoropropyl group, 2-fluoro-1-methylethyl group, 2-chloro-1-methylethyl group, 2-bromo-1-methylethyl group, 2,2, 2-trifluoro-1- (trifluoromethyl) ethyl group, 1,2,2, 2-tetrafluoro-1- (trifluoromethyl) ethyl group, 2,2,3,3,4, 4-hexafluorobutyl group, 2,2,3,3,4,4, 4-heptafluorobutyl, 1,2,2,3,3,4, 4-octafluorobutyl,Nonafluorobutyl, 4-chloro-1, 1,2,2,3,3,4, 4-octafluorobutyl, 2-fluoro-2-methylpropyl, 2-chloro-1, 1-dimethylethyl, 2-bromo-1, 1-dimethylethyl, 5-chloro-2, 2,3,4,4,5, 5-heptafluoropentyl, tridecafluorohexyl and the like, and they may be selected in accordance with the range of the number of carbon atoms specified for each.

In this specification C_a～C_bThe notation of cycloalkyl represents a cyclic hydrocarbon group having a to b carbon atoms, and can form a single ring or a complex ring structure of 3-to 6-membered rings. Each ring may be optionally substituted with an alkyl group within a specified carbon number range. Specific examples thereof include: cyclopropyl, 1-methylcyclopropyl, 2-dimethylcyclopropyl, 2,3, 3-tetramethylcyclopropyl, cyclobutyl, cyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, bicyclo [2.2.1 ] g]Heptane-2-yl group, etc., can be selected depending on the respective specified ranges of the number of carbon atoms.

In this specification C_a～C_bThe term "halocycloalkyl" refers to a cyclic hydrocarbon group having a carbon number of a to b, in which a hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom, and can form a 3-to 6-membered ring having a single ring or a complex ring structure. Each ring may be optionally substituted with an alkyl group within a predetermined range of the number of carbon atoms, and the substitution with a halogen atom may be performed in the ring structure portion, the side chain portion, or both portions, or when substituted with 2 or more halogen atoms, these halogen atoms may be the same or different from each other. Specific examples thereof include: 2, 2-difluorocyclopropyl group, 2-dichlorocyclopropyl group, 2-dibromocyclopropyl group, 2-difluoro-1-methylcyclopropyl group, 2-dichloro-1-methylcyclopropyl group, 2-dibromo-1-methylcyclopropyl group, 2,3, 3-tetrafluorocyclobutyl group, 2- (trifluoromethyl) cyclohexyl group, 3- (trifluoromethyl) cyclohexyl group, 4- (trifluoromethyl) cyclohexyl group and the like, and they can be selected depending on the range of the number of carbon atoms specified in each group.

In this specification C_a～C_bThe notation of alkenyl denotes a straight chain having a to b carbon atoms orExamples of the branched unsaturated hydrocarbon group having 1 or 2 or more double bonds in the molecule include: vinyl group, 1-propenyl group, 2-propenyl group, 1-methylvinyl group, 2-butenyl group, 1-methyl-2-propenyl group, 2-pentenyl group, 2-methyl-2-butenyl group, 3-methyl-2-butenyl group, 2-ethyl-2-propenyl group, 1-dimethyl-2-propenyl group, 2-hexenyl group, 2-methyl-2-pentenyl group, 2, 4-dimethyl-2, 6-heptadienyl group, 3, 7-dimethyl-2, 6-octadienyl group and the like, and they may be selected depending on the range of the number of carbon atoms specified for each.

In this specification C_a～C_bThe term "haloalkenyl" denotes a linear or branched unsaturated hydrocarbon group having 1 or 2 or more double bonds in the molecule, wherein the hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom, and the carbon atom number is a to b. In this case, when the halogen atoms are substituted by 2 or more halogen atoms, these halogen atoms may be the same or different from each other. Specific examples thereof include: 2, 2-dichlorovinyl, 2-fluoro-2-propenyl, 2-chloro-2-propenyl, 3-chloro-2-propenyl, 2-bromo-2-propenyl, 3, 3-difluoro-2-propenyl, 2, 3-dichloro-2-propenyl, 3, 3-dichloro-2-propenyl, 2, 3-dibromo-2-propenyl, 2,3, 3-trifluoro-2-propenyl, 2,3, 3-trichloro-2-propenyl, 1- (trifluoromethyl) vinyl, 3-chloro-2-butenyl, 3-bromo-2-butenyl, 4, 4-two fluorine-3-butene radical, 3,4, 4-three fluoro-3-butene radical, 3-chlorine-4, 4, 4-three fluoro-2-butene radical, 3-bromine-2-methyl-2-allyl, etc., according to the number of carbon atoms in the range to choose.

In this specification C_a～C_bThe notation of cycloalkenyl denotes an unsaturated hydrocarbon group having 1 or 2 or more double bonds and having a cyclic structure with a to b carbon atoms, and can form a monocyclic or complex ring structure of a 3-to 6-membered ring. The rings may be optionally substituted with an alkyl group within the specified carbon number range, and the double bond may be in the form of endo- (inner) or exo- (outer). Specific examples thereof include: 2-cyclopenten-1-yl, 3-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, bicyclo [2.2.1 ]]-5-hepten-2-yl and the like,and may be selected according to the range of the number of carbon atoms specified for each.

In this specification C_a～C_bThe notation of halocycloalkenyl denotes a cyclic unsaturated hydrocarbon group having 1 or 2 or more double bonds, wherein the hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom, and the unsaturated hydrocarbon group has a carbon atom number of a to b, and can form a single ring or a complex ring structure of a 3-to 6-membered ring. Further, each ring may be optionally substituted with an alkyl group within the specified carbon number range, and the double bond may be in the form of endo-or exo-. The substitution with a halogen atom may be performed in the ring structure part, the side chain part, or both, and when 2 or more halogen atoms are substituted, these halogen atoms may be the same or different from each other. Specific examples thereof include 2-chlorobicyclo [ 2.2.1%]-5-hepten-2-yl and the like, which can be selected in accordance with the respective specified ranges of the number of carbon atoms.

In this specification C_a～C_bThe term "alkynyl" denotes a linear or branched unsaturated hydrocarbon group having a carbon number of a to b and having 1 or 2 or more triple bonds in the molecule, and specific examples thereof include: ethynyl, 1-propynyl, 2-butynyl, 1-methyl-2-propynyl, 2-pentynyl, 1-methyl-2-butynyl, 1-dimethyl-2-propynyl, 2-hexynyl and the like, and they may be selected depending on the range of the number of carbon atoms specified for each.

In this specification C_a～C_bThe expression "haloalkynyl group" denotes a linear or branched unsaturated hydrocarbon group having 1 or 2 or more triple bonds in the molecule, wherein the hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom, and the carbon number is a to b. In this case, when the halogen atoms are substituted by 2 or more halogen atoms, these halogen atoms may be the same or different from each other. Specific examples thereof include: 2-chloroethynyl group, 2-bromoethynyl group, 2-iodoethynyl group, 3-chloro-2-propynyl group, 3-bromo-2-propynyl group, 3-iodo-2-propynyl group and the like can be selected depending on the range of the number of carbon atoms specified for each group.

In this specification C_a～C_bThe expression "alkoxy" denotes an alkyl-O-group as defined above having a to b carbon atoms, and specific examples thereof include: methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n-pentyloxy group, n-hexyloxy group, etc., and they may be selected in accordance with the range of the number of carbon atoms specified for each group.

In this specification C_a～C_bThe notation of haloalkoxy denotes a haloalkyl-O-group as defined above having a to b carbon atoms, and specific examples include: difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, bromodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2,2, 2-trifluoroethoxy, 1,2, 2-tetrafluoroethoxy, 2-chloro-1, 1, 2-trifluoroethoxy, 2-bromo-1, 1, 2-trifluoroethoxy, pentafluoroethoxy, 2, 2-dichloro-1, 1, 2-trifluoroethoxy, 2,2, 2-trichloro-1, 1-difluoroethoxy, 2-bromo-1, 1,2, 2-tetrafluoroethoxy, 2,2,3, 3-tetrafluoropropyloxy, 1,2,3,3, 3-hexafluoropropyloxy, 2,2, 2-trifluoro-1- (trifluoromethyl) ethoxy, 2-chloroethoxy, 2,2, 2-chloroethoxy, pentafluoroethoxy, 2-dichloro-1, 1,2,3, 3-hexafluoropropyloxy, 2-dichloro-1, 2,3, 3-difluoroethoxy, 2-trifluoro-1- (trifluoromethyl) ethoxy, 2, 2-fluoroethoxy, 2, 2-chloro-1, 2-trifluoro-1- (trifluoromethyl) ethoxy, 2-1, 2-trifluoroethoxy, 2, 2-chloro-1, 2-trifluoroethoxy, 2, 2-1, 2-trifluoroethoxy, 2-1, 2-hexafluoroethoxy, 2,2,2, 3,3, 2,2,2, 3,3,3, or a-hexafluoroethoxy, 2,3,3, or a, Heptafluoropropyloxy group, 2-bromo-1, 1,2,3,3, 3-hexafluoropropyloxy group and the like, and they can be selected in accordance with the respective specified ranges of the number of carbon atoms.

(C) in the present specification_a～C_bThe notation of alkyl) carbonyl represents the alkyl-C (O) -group of the above definition having a to b carbon atoms, and specific examples thereof include: acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, 2-methylbutyryl, pivaloyl, hexanoyl, heptanoyl, and the like, and can be selected in accordance with the range of the number of carbon atoms specified for each.

(C) in the present specification_a～C_bThe notation of haloalkyl) carbonyl represents a haloalkyl-C (O) -group of the above definition having a to b carbon atoms, and specific examples thereof include: fluoroacetyl, chloroacetyl, difluoroacetyl, dichloroacetyl, trifluoroacetyl, chlorodifluoroacetyl, bromodifluoroacetyl, trichloroacetyl, pentafluoropropionyl, heptafluorobutyryl, 3-chloro-2, 2-dimethylpropionyl, etc., optionallySelected according to the range of the number of carbon atoms specified for each.

(C) in the present specification_a～C_bThe notation of alkoxy) carbonyl represents the above-defined alkyl-O-C (O) -group having a to b carbon atoms, and specific examples thereof include: methoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, isobutyloxycarbonyl, tert-butyloxycarbonyl and the like can be selected depending on the range of the number of carbon atoms specified for each.

(C) in the present specification_a～C_bThe notation of haloalkoxy) carbonyl represents the above-defined haloalkyl-O-C (O) -group having a to b carbon atoms, and specific examples thereof include: 2-chloroethoxycarbonyl group, 2, 2-difluoroethoxycarbonyl group, 2,2, 2-trifluoroethoxycarbonyl group, 2,2, 2-trichloroethoxycarbonyl group and the like, and they can be selected in accordance with the respective specified ranges of the number of carbon atoms.

(C) in the present specification_a～C_bAlkylamino) carbonyl represents a carbamoyl group in which one hydrogen atom is substituted by the above-defined alkyl group having a to b carbon atoms, and specific examples thereof include: methylcarbamoyl, ethylcarbamoyl, n-propylcarbamoyl, isopropylcarbamoyl, n-butylcarbamoyl, isobutylcarbamoyl, sec-butylcarbamoyl, tert-butylcarbamoyl and the like, and they can be selected depending on the range of the number of carbon atoms specified for each.

(C) in the present specification_a～C_bHaloalkyl) aminocarbonyl represents a carbamoyl group in which one hydrogen atom is substituted by a haloalkyl group having a to b carbon atoms as defined above, and specific examples thereof include: 2-fluoroethylcarbamoyl, 2-chloroethylcarbamoyl, 2, 2-difluoroethylcarbamoyl, 2,2, 2-trifluoroethylcarbamoyl and the like, and they may be selected depending on the range of the number of carbon atoms specified for each.

Two (C) in this specification_a～C_bAlkyl) aminocarbonyl means that both hydrogen atoms are taken by an alkyl group of the above definition having a to b carbon atoms which are the same or different from each otherSpecific examples of the substituted carbamoyl group include: n, N-dimethylcarbamoyl group, N-ethyl-N-methylcarbamoyl group, N-diethylcarbamoyl group, N-di-N-propylcarbamoyl group, N-di-N-butylcarbamoyl group, etc., and they may be selected depending on the range of the number of carbon atoms specified for each group.

A substituent R in cinnamic acid or benzoic acid derivatives having a structure represented by the formula (c)¹⁰¹、R¹⁰²、R¹⁰³、R¹⁰⁴And R¹⁰⁵Wherein, each is preferably independently selected from the group consisting of a hydrogen atom, a halogen atom, and C₁～C₆Alkyl radical, C₁～C₆Haloalkyl, C₁～C₆Alkoxy radical, C₁～C₆A substituent of the group consisting of a haloalkoxy group, a cyano group and a nitro group.

In addition, as R¹⁰³The suitable R is preferable in terms of alignment sensitivity¹⁰¹、R¹⁰²、R¹⁰³、R¹⁰⁴And R¹⁰⁵The substituent other than hydrogen atom in the definition of (1) is more preferably selected from the group consisting of halogen atom and C₁～C₆Alkyl radical, C₁～C₆Haloalkyl, C₁～C₆Alkoxy radical, C₁～C₆A substituent of the group consisting of a haloalkoxy group, a cyano group and a nitro group.

In addition, R is also preferable¹⁰¹、R¹⁰²、R¹⁰³、R¹⁰⁴And R¹⁰⁵Wherein R is preferably R, any one or two substituents of the above-mentioned group are a group represented by the formula (c-2)¹⁰³Is a group represented by the formula (c-2). As such a monomer, a monomer having a cinnamic acid group may be mentioned one selected from the above-mentioned formulae M1-1 to M1-7 and M1-17 to M1-21. Further, examples of the monomer having a benzoic acid group include monomers selected from the group consisting of the above-mentioned formulae M2-1 to M2-9.

Examples of such cinnamic acids and derivatives thereof include: cinnamic acid derivatives such as cinnamic acid, 4-methoxy cinnamic acid, 4-ethoxy cinnamic acid, 4-propoxy cinnamic acid, and 4-fluoro cinnamic acid; monomers having a cinnamic acid group such as 4- (6-methacryloyloxyhexyl-1-oxy) cinnamic acid, 4- (6-acryloyloxyhexyl-1-oxy) cinnamic acid, 4- (3-methacryloyloxypropyl-1-oxy) cinnamic acid, and 4- (4- (6-methacryloyloxyhexyl-1-oxy) benzoyloxy) cinnamic acid.

Further, examples of the benzoic acid and its derivative include: benzoic acid derivatives such as benzoic acid, 4-methoxybenzoic acid, 4-ethoxybenzoic acid, 4-propoxybenzoic acid, 4-fluorobenzoic acid and the like; and a monomer having a benzoic acid group such as 4- (6-methacryloyloxyhexyl-1-oxy) benzoic acid, 4- (6-acryloyloxyhexyl-1-oxy) benzoic acid, 4- (3-methacryloyloxypropyl-1-oxy) benzoic acid, and 4- (4- (6-methacryloyloxyhexyl-1-oxy) benzoyloxy) benzoic acid.

The content of the component (C) in the polymer composition of the present invention is preferably 3 to 100 parts by mass relative to 100 parts by mass of the side chain polymer of the component (a). If the content of the component (C) is less than 3 parts by mass, the irradiation dose range is not widened. If the content of the component (C) exceeds 100 parts by mass and is too large, the solvent resistance of the cured film obtained may be lowered.

< organic solvent >

The organic solvent used in the polymer composition of the present invention is not particularly limited as long as it is an organic solvent capable of dissolving the resin component. Specific examples of the organic solvent are shown below.

Examples thereof include: n, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethyl sulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, gamma-butyrolactone, 3-methoxy-N, N-dimethylpropionamide, 3-ethoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, 1, 3-dimethyl-imidazolidinone, ethylpentyl ketone, methylnonyl ketone, methylethylketone, methylisoamylketone, methylisopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diethylene glycol dimethyl ether, dimethyl sulfoxide, and methyl amyl ketone, 4-hydroxy-4-methyl-2-pentanone, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol t-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, isopropanol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol acetate, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, Propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, 1-hexanol, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, or n-butyl acetate, or n-butyl acetate, Propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, propylene glycol acetate, 2- (2-ethoxypropoxy) and propylene glycol acetate, propylene glycol acetate, and propylene glycol acetate, propylene glycol acetate, and propylene glycol acetate, propylene glycol acetate, Methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, and the like. These may be used alone or in combination.

< Polymer composition >

The polymer composition of the present invention contains (A) a side chain polymer exhibiting liquid crystallinity in a specific temperature range, and (B) a dichroic dye and an organic solvent. Further, the compound represented by the formula (C) is contained as required.

[ preparation of Polymer composition ]

The polymer composition used in the present invention is preferably prepared in the form of a coating liquid in order to be suitable for forming an alignment layer. That is, the polymer composition used in the present invention is preferably prepared in the form of a solution obtained by dissolving a resin component for forming a resin coating film in an organic solvent. Here, the resin component is a resin component containing the side chain type polymer capable of exhibiting liquid-crystalline photosensitivity described above. In this case, the content of the resin component is preferably 1 to 20% by mass, more preferably 3 to 15% by mass, and particularly preferably 3 to 10% by mass.

In the polymer composition of the present embodiment, the resin component may be all the side chain type polymers capable of expressing liquid crystal photosensitivity, or other polymers than these may be mixed in a range where liquid crystal expression ability and photosensitivity are not impaired. In this case, the content of the other polymer in the resin component is 0.5 to 80% by mass, preferably 1 to 50% by mass.

Examples of such other polymers include polymers of side chain type polymers that do not exhibit liquid crystal photosensitivity, such as poly (meth) acrylate, polyamic acid, and polyimide.

The polymer composition used in the present invention may further contain components other than the components (A) and (B) and the organic solvent. Examples thereof include a compound that improves film thickness uniformity and surface smoothness when the polymer composition is applied, and a compound that improves adhesion between the alignment layer and the substrate, but the invention is not limited thereto.

Examples of the compound for improving the film thickness uniformity or surface smoothness include: fluorine-based surfactants, silicone-based surfactants, nonionic surfactants, and the like.

More specifically, for example, there may be mentioned: eftop (registered trademark) 301, EF303, EF352 (manufactured by Tochem Products), MEGAFAC (registered trademark) F171, F173, R-30 (manufactured by DIC), Fluorad FC430, FC431 (manufactured by Sumitomo 3M), Asahiguard (registered trademark) AG710 (manufactured by Asahi glass Co., Ltd.), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC beauty chemical Co., Ltd.), and the like. The use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, based on 100 parts by mass of the resin component contained in the polymer composition.

Specific examples of the compound for improving the adhesion between the alignment layer and the substrate include the following functional silane-containing compounds.

Examples thereof include: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1, 4, 7-triazacyclodecane, 10-triethoxysilyl-1, 4, 7-triazacyclodecane, 9-trimethoxysilyl-3, 6-diazanone acetate, 9-triethoxysilyl-3, 6-diazanone acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane and the like.

In addition, in order to improve the adhesion between the substrate and the alignment layer and to impart heat resistance, an additive such as a phenol resin (phenoplast) type or an epoxy group-containing compound described below may be added to the polymer composition. Specific phenolic resin additives are disclosed below, but the present invention is not limited to these structures.

[ solution 33]

Specific examples of the epoxy group-containing compound include: ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2-dibromoneopentyl glycol diglycidyl ether, 1,3,5, 6-tetraglycidyl-2, 4-hexanediol, N ' -tetraglycidyl m-xylylenediamine, 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, N ' -tetraglycidyl-4, 4' -diaminodiphenylmethane, and the like.

When a compound that improves adhesion to a substrate is used, the amount of the compound used is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the resin component contained in the polymer composition. If the amount is less than 0.1 part by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the alignment of the liquid crystal may be deteriorated.

As additives, photosensitizers may also be used. Preferred are leuco sensitizers and triplet sensitizers.

As photosensitizers, there are aromatic nitro compounds, coumarins (7-diethylamino-4-methylcoumarin, 7-hydroxy-4-methylcoumarin), ketocoumarins, carbonylbiscoumarin, aromatic 2-hydroxyketones and amino-substituted aromatic 2-hydroxyketones (2-hydroxybenzophenone, mono-or di-p- (dimethylamino) -2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, benzanthrone, thiazoline (2-benzoylmethylene-3-methyl- β -naphthothiazoline, 2- (. beta. -naphthoylmethylene) -3-methylbenzothiazoline, 2- (. alpha. -naphthoylmethylene) -3-methylbenzothiazoline, and, 2- (4-Bibenzoylmethylene) -3-methylbenzothiazoline, 2- (. beta. -naphthoylmethylene) -3-methyl-. beta. -naphthothiazoline, 2- (4-Bibenzoylmethylene) -3-methyl-. beta. -naphthothiazoline, 2- (p-fluorobenzoylmethylene) -3-methyl-. beta. -naphthothiazoline), oxazoline (2-benzoylmethylene-3-methyl-. beta. -naphthooxazoline, 2- (. beta. -naphthoylmethylene) -3-methylbenzoxazoline, 2- (. alpha. -naphthoylmethylene) -3-methylbenzoxazoline, 2- (4-Bibenzoylmethylene) -3-methylbenzothiazoline, 2- (. beta. -naphthoylmethylene) -3-methyl-. beta. -naphthooxazoline, 2- (. beta. -dibenzoylmethylene) -3-methyl-. beta. -naphthooxazoline, 2- (. p-fluorobenzoylmethylene) -3-methyl-. beta. -naphthooxazoline), benzothiazole, nitroaniline (m-or p-nitroaniline, 2,4, 6-trinitroaniline) or nitroacenaphthylene (5-nitroacenaphthylene), (2- [ (m-hydroxy-p-methoxy) styryl ] benzothiazole, benzoin alkyl ether, N-alkylated phthalide, acetophenone ketal (2, 2-dimethoxyacetophenone), naphthalene, anthracene (2-naphthalenemethanol, 2-naphthalenecarboxylic acid, 9-anthracenemthanol and 9-anthracenecarboxylic acid), Benzopyran, azoindolizine, merocumarin and the like.

Aromatic 2-hydroxyketones (benzophenone), coumarins, ketocoumarins, carbonyldicoumarins, acetophenones, anthraquinones, xanthones, thioxanthones and acetophenone ketals are preferred.

The present invention also relates to a method for producing a substrate and a modification element using the polymer composition.

The method for manufacturing a substrate having a liquid crystal alignment film formed of the polymer composition of the present invention comprises:

a step (I) of coating a polymer composition containing (A) a side chain polymer exhibiting photosensitivity in a specific temperature range, (B) a dichroic dye, and an organic solvent on a substrate to form a coating film;

a step [ II ] of irradiating the coating film obtained in [ I ] with polarized ultraviolet rays; and

and step [ III ] of heating the coating film obtained in [ II ].

Through the steps, a liquid crystal alignment film to which an alignment control capability is imparted can be obtained, and a substrate having the liquid crystal alignment film can be obtained.

The method for manufacturing the polarizing element includes:

[ IV ] a step of preparing the obtained substrate having an alignment layer; and a step selected from the following [ V-1] and [ V-2 ].

A step [ V-1] of applying a polarizing layer-forming composition containing (B) a dichroic dye and (D) a polymerizable liquid crystal on the alignment layer of the substrate having the alignment layer, heating and drying the composition to form a coating film, and irradiating the obtained coating film with ultraviolet rays;

and a step [ V-2] of applying a polarizing layer-forming composition containing (E) a dye having lyotropic liquid crystal properties onto the alignment layer of the substrate having an alignment layer, and heating and drying the composition to form a coating film.

Thereby, a polarizing element can be obtained.

The steps of [ I ] to [ III ] and [ IV ] of the production method of the present invention will be described below.

< step [ I ] >

In the step [ I ], a polymer composition containing (A) a side chain polymer exhibiting photosensitivity in a specific temperature range, (B) a dichroic dye and an organic solvent is applied to a substrate to form a coating film.

< substrate >

The substrate is typically a transparent substrate. When a substrate of the polarizing plate of the present invention (hereinafter, sometimes referred to as the present polarizing plate) is not provided on the display surface of the display element, for example, when a polarizing film obtained by removing the substrate from the present polarizing plate is provided on the display surface of the display element, the substrate may not be transparent. The transparent substrate is a substrate having transparency which allows light, particularly visible light, to pass therethrough, and the transparency is a characteristic that the transmittance of light having a wavelength of 380 to 780nm is 80% or more. Specific examples of the transparent substrate include a light-transmitting resin substrate. Examples of the resin constituting the light-transmitting resin substrate include: polyolefins such as polyethylene and polypropylene; cyclic olefin resins such as norbornene polymers; polyvinyl alcohol; polyethylene terephthalate; polymethacrylates; a polyacrylate; cellulose esters such as triacetyl cellulose, diacetyl cellulose, and cellulose acetate propionate; polyethylene naphthalate; a polycarbonate; polysulfones; polyether sulfone; a polyether ketone; polyphenylene sulfide and polyphenylene oxide. From the viewpoint of easy availability or transparency, polyethylene terephthalate, polymethacrylate, cellulose ester, cycloolefin resin, or polycarbonate is preferable.

Cellulose esters are those obtained by esterifying a part or all of the hydroxyl groups contained in cellulose, and are readily commercially available. In addition, cellulose ester substrates are also readily commercially available. Examples of commercially available cellulose ester substrates include: "Fujitac film" (Fuji film Co., Ltd.); "KC 8UX 2M", "KC 8 UY", and "KC 4 UY" (Konica Minolta Opto Co., Ltd.), etc.

The cycloolefin-based resin is conveniently commercially available. Examples of commercially available cycloolefin resins include: "Topas" [ Ticona (Germany) ], "ARTON" [ JSR Co., Ltd ], "ZEONOR" [ Japanese Ruyan Co., Ltd ], "ZEONEX" [ Japanese Ruyan Co., Ltd ] and "APEL" [ manufactured by Mitsui Chemicals Co., Ltd ]. The substrate can be produced by forming a film of such a cyclic olefin resin by a known method such as a solvent casting method or a melt extrusion method. In addition, a commercially available cycloolefin resin substrate may be used. Examples of the commercially available cycloolefin resin base material include: "S-SINA" [ Water chemistry industry Co., Ltd ], "SCA 40" [ Water chemistry industry Co., Ltd ], "Zeonor Film" [ Optronics Co., Ltd ], and "ARTON Film" [ JSR Co., Ltd ].

When the cyclic olefin resin is a copolymer of a cyclic olefin and a linear olefin or an aromatic compound having a vinyl group, the content ratio of the structural unit derived from the cyclic olefin is usually 50 mol% or less, preferably in the range of 15 to 50 mol% relative to the total structural units of the copolymer. Examples of the chain olefin include ethylene and propylene, and examples of the aromatic compound having a vinyl group include: styrene, alpha-methylstyrene and alkyl-substituted styrenes. When the cyclic olefin resin is a terpolymer of a cyclic olefin, a chain olefin and an aromatic compound having a vinyl group, the content ratio of the structural unit derived from the chain olefin is usually 5 to 80 mol% based on the total structural units of the copolymer, and the content ratio of the structural unit derived from the aromatic compound having a vinyl group is usually 5 to 80 mol% based on the total structural units of the copolymer. This terpolymer has the advantage that the amount of expensive cyclic olefin used can be relatively reduced in the production of the copolymer.

The required characteristics of the substrate vary depending on the constitution of the polarizing plate, and a substrate having as small a retardation as possible is generally preferred. As the substrate having the smallest retardation property, there can be mentioned: and cellulose ester films having no phase difference, such as ZEROTAC (Konica Minolta Opto Co., Ltd.), Z-TAC (Fuji film Co., Ltd.). Further, an unstretched cycloolefin resin substrate is also preferable.

The surface of the substrate on which the polarizing layer is not formed may be subjected to a hard coating treatment, an antireflection treatment, an antistatic treatment, or the like. In addition, the hard coat layer may contain an additive such as an ultraviolet absorber within a range that does not affect the performance.

The thickness of the substrate is usually 5 to 300 μm, preferably 20 to 200 μm, because the strength tends to be lowered and the workability tends to be deteriorated if the thickness is too thin.

The method for coating the polymer composition on a substrate is not particularly limited.

Coating is generally carried out industrially by a coating method such as screen printing, offset printing, flexographic printing or ink jet method. As other coating methods, there are a dipping method, a roll coating method, a slit coating method, a spin coating method (spinner method), a spraying method, and the like, and these methods can be selected according to the purpose.

After coating the polymer composition on the substrate, the solvent can be evaporated at 50 to 230 ℃, preferably 50 to 200 ℃ for 0.4 to 60 minutes, preferably 0.5 to 10 minutes by using a heating device such as a hot plate, a thermal cycle oven or an IR (infrared) oven to obtain a coating film. The drying temperature in this case is preferably lower than the liquid crystal phase appearance temperature of the side chain type polymer.

The thickness of the coating film is usually in the range of 10nm to 10000nm, preferably 10nm to 1000nm, more preferably 500nm or less, and further preferably 10nm to 300nm because it is disadvantageous in the expression of anisotropy if it is too thick, and has a problem in polarization characteristics if it is too thin.

Further, a step of cooling the substrate having the coating film formed thereon to room temperature may be provided after the step [ I ] and before the next step [ II ].

< step [ II ] >

In step [ II ], the coating film obtained in step [ I ] is irradiated with polarized ultraviolet rays. When polarized ultraviolet light is irradiated to the film surface of the coating film, ultraviolet light polarized by a polarizing plate is irradiated from a certain direction to the substrate. As the ultraviolet ray to be used, ultraviolet rays having a wavelength in the range of 100nm to 400nm can be used. The optimum wavelength is preferably selected via a filter or the like according to the type of the coating film used. For example, ultraviolet rays having a wavelength of 290 to 400nm may be selectively used so as to selectively induce the photocrosslinking reaction. As the ultraviolet rays, for example, light emitted from a high-pressure mercury lamp can be used.

The irradiation amount of polarized ultraviolet light depends on the coating film used. The irradiation amount is preferably in the range of 1% to 70%, more preferably in the range of 1% to 50%, of the amount of polarized ultraviolet light that achieves the maximum value of Δ a (hereinafter also referred to as Δ Amax), which is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet light and the ultraviolet absorbance in the direction perpendicular to the polarization direction in the coating film.

< step [ III ] >

In the step [ III ], the coating film irradiated with the polarized ultraviolet ray in the step [ II ] is heated. By heating, the alignment controllability can be imparted to the coating film.

Heating may be performed using a heating device such as a hot plate, a thermal cycle type oven, or an IR (infrared ray) type oven. The heating temperature may be determined in consideration of the temperature at which the coating film used exhibits liquid crystallinity.

The heating temperature is preferably within a temperature range at which the side chain polymer exhibits liquid crystallinity (hereinafter referred to as a liquid crystal display temperature). In the case of a film surface such as a coating film, it is predicted that the liquid crystal display temperature on the coating film surface is lower than the liquid crystal display temperature when a side chain type polymer capable of displaying photosensitivity of liquid crystallinity is observed in a bulk state. Therefore, the heating temperature is more preferably within the temperature range of the liquid crystal display temperature of the coating film surface. That is, the temperature range of the heating temperature after irradiation with the polarized ultraviolet ray is preferably a temperature in a range having a lower limit of 10 ℃ lower than the lower limit of the temperature range of the liquid crystal display temperature of the side chain polymer to be used and an upper limit of 10 ℃ lower than the upper limit of the liquid crystal temperature range. If the heating temperature is lower than the above temperature range, the effect of increasing anisotropy by heat in the coating film tends to be insufficient, and if the heating temperature is too high as compared with the above temperature range, the state of the coating film tends to be close to an isotropic liquid state (isotropic phase), and in this case, it may be difficult to perform realignment in one direction by self-assembly.

The liquid crystal display temperature is a temperature not lower than the glass transition temperature (Tg) at which the side chain polymer or the coating film surface undergoes phase transition from a solid phase to a liquid crystal phase, and not higher than the isotropic phase transition temperature (Tiso) at which the liquid crystal phase undergoes phase transition to an isotropic phase.

The thickness of the coating film formed after heating is preferably 5nm to 500nm, more preferably 50nm to 300nm, for the same reason as described in the step [ I ].

By having the above steps, the production method of the present invention can realize highly efficient introduction of anisotropy into a coating film. In addition, the substrate with the alignment layer can be efficiently manufactured.

The method for producing a substrate with a coating film of the present invention comprises coating a polymer composition on a substrate to form a coating film, and then irradiating the coating film with polarized ultraviolet light. Then, the substrate is heated to efficiently introduce anisotropy into the side chain polymer film, thereby producing a substrate with a liquid crystal alignment film having liquid crystal alignment controllability.

The coating film used in the present invention utilizes the principle of photoreaction of side chains and molecular realignment induced by self-assembly based on liquid crystallinity, thereby realizing efficient introduction of anisotropy into the coating film. In the case where the side chain type polymer has a structure in which a photocrosslinkable group is a photoreactive group, the production method of the present invention forms a coating film on a substrate using the side chain type polymer, irradiates the coating film with polarized ultraviolet rays, and then heats the coating film to produce a polarizing element.

Therefore, the coating film used in the method of the present invention can be subjected to irradiation with polarized ultraviolet rays and heat treatment in order to efficiently introduce anisotropy into the coating film, and thus can be an alignment layer having excellent alignment controllability.

In addition, the coating film used in the method of the present invention is optimized in the irradiation amount of polarized ultraviolet rays to be irradiated to the coating film and the heating temperature in the heating treatment. This enables efficient introduction of anisotropy into the coating film.

The irradiation amount of the polarized ultraviolet ray which is optimal for efficiently introducing anisotropy into the coating film used in the present invention corresponds to the irradiation amount of the polarized ultraviolet ray which is optimal for the amount of the photosensitive group which is subjected to the photocrosslinking reaction, the photoisomerization reaction, or the photofuji rearrangement reaction in the coating film. When the coating film used in the present invention is irradiated with polarized ultraviolet light, if the side chain photosensitive group which undergoes the photocrosslinking reaction, the photoisomerization reaction, or the photofuji rearrangement reaction is too small, the photoreaction amount is insufficient. In this case, even after the heating, the self-assembly does not proceed sufficiently. On the other hand, in the coating film used in the present invention, when the structure having a photocrosslinkable group is irradiated with polarized ultraviolet light, if the photosensitive group of the side chain to be subjected to the crosslinking reaction is too large, the crosslinking reaction between the side chains excessively proceeds. In this case, the obtained film becomes rigid, and the progress of self-assembly due to heating thereafter may be hindered. In addition, in the coating film used in the present invention, when polarized ultraviolet light is irradiated to the structure having the photovoltine rearrangement group, if the number of the photosensitive groups of the side chain in which the photovoltine rearrangement reaction occurs is too large, the liquid crystallinity of the coating film is excessively lowered. In this case, the liquid crystallinity of the obtained film may be reduced, which may hinder the progress of self-assembly due to subsequent heating. In addition, when polarized ultraviolet light is irradiated to a structure having a photofrizzled rearrangement group, if the irradiation amount of ultraviolet light is too large, the side chain polymer is photolyzed, and the self-assembly due to heating may be inhibited.

Therefore, in the coating film used in the present invention, the optimum amount of the photosensitive group of the side chain which undergoes the photocrosslinking reaction, the photoisomerization reaction, or the photofuji rearrangement reaction by irradiation with polarized ultraviolet rays is preferably 0.1 to 40 mol%, more preferably 0.1 to 20 mol%, of the photosensitive group of the side chain type polymer film. By setting the amount of the photosensitive group of the side chain which is photoreactive in such a range, the progress efficiency of self-assembly by the heat treatment thereafter becomes excellent, and anisotropy can be efficiently formed in the film.

In the coating film used in the method of the present invention, the amount of the photosensitive group in the side chain of the side chain type polymer film, which undergoes the photocrosslinking reaction, the photoisomerization reaction or the photofuji rearrangement reaction, is optimized by optimizing the irradiation amount of polarized ultraviolet light. Further, the coating film used in the present invention can be efficiently provided with anisotropy by the synergistic effect with the subsequent heat treatment. In this case, the amount of suitable polarized ultraviolet rays can be evaluated based on the ultraviolet absorption of the coating film used in the present invention.

That is, after the coating film used in the present invention is irradiated with polarized ultraviolet light, ultraviolet absorption in a direction parallel to the polarization direction of the polarized ultraviolet light and ultraviolet absorption in a direction perpendicular to the polarization direction are measured. From the measurement results of the ultraviolet absorption, the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet light and the ultraviolet absorbance in the direction perpendicular to the polarization direction, i.e., Δ a, in the coating film was evaluated. In addition, the maximum value (Δ Amax) of Δ a that can be achieved by the coating film used in the present invention and the irradiation amount of polarized ultraviolet light that achieves the maximum value are determined. In the production method of the present invention, a preferable irradiation amount of polarized ultraviolet rays to be irradiated in producing the liquid crystal alignment film can be determined with reference to the irradiation amount of polarized ultraviolet rays to realize Δ Amax.

In the production method of the present invention, the irradiation amount of polarized ultraviolet light to the coating film used in the present invention is preferably in the range of 1% to 70%, more preferably in the range of 1% to 50%, of the amount of polarized ultraviolet light that achieves Δ Amax. In the coating film used in the present invention, the irradiation amount of the polarized ultraviolet ray in the range of 1% to 50% of the amount of the polarized ultraviolet ray that realizes Δ Amax corresponds to the amount of the polarized ultraviolet ray that causes the photocrosslinking reaction to proceed in 0.1 mol% to 20 mol% of all the photosensitive groups of the side chain type polymer film.

Accordingly, in the production method of the present invention, in order to efficiently introduce anisotropy into a coating film, it is preferable to determine an appropriate heating temperature as described above with reference to the liquid crystal temperature range of the side chain polymer. Therefore, for example, when the liquid crystal temperature of the side chain polymer used in the present invention is in the range of 60 to 200 ℃, it is preferable that the temperature for heating after irradiation with polarized ultraviolet rays is 50 to 190 ℃. Thereby, the coating film used in the present invention is imparted with greater anisotropy.

Thus, the polarizing element provided by the invention has high reliability to external stress such as light or heat.

< polarizing-layer-forming composition >

The polarizing layer forming composition used for forming the polarizing element of the present invention is a composition containing (B) a dichroic dye and (D) a polymerizable liquid crystal, or a composition containing (E) a dye having lyotropic liquid crystal properties. The polarizing layer forming composition containing (B) the dichroic dye and (D) the polymerizable liquid crystal generally contains a solvent, and the solvent may be the same as the solvent contained in the above-mentioned alignment polymer composition, and may be appropriately selected depending on the solubility of the polymerizable liquid crystal (D).

The composition containing (E) a dye having lyotropic liquid crystallinity generally contains a solvent, and the solvent is not particularly limited, and a solvent known heretofore can be used, and an aqueous solvent is preferred. Examples of the aqueous solvent include: water, a hydrophilic solvent, a mixed solvent of water and a hydrophilic solvent, and the like. The hydrophilic solvent is a solvent that is substantially uniformly dissolved in water. Examples of the hydrophilic solvent include: alcohols such as methanol and isopropanol; glycols such as ethylene glycol; cellosolves such as methyl cellosolve and ethyl cellosolve; ketones such as acetone and methyl ethyl ketone; and esters such as ethyl acetate. The aqueous solvent is preferably water or a mixed solvent of water and a hydrophilic solvent.

The component (B) is used as the dichroic dye (B).

(D) polymerizable liquid Crystal

The polymerizable liquid crystal (D) is a compound having a polymerizable group and exhibiting liquid crystallinity.

The polymerizable group means a group involved in polymerization reaction, and is preferably a photopolymerizable group. Here, the photopolymerizable group means a group capable of undergoing a polymerization reaction by an active radical generated from a photopolymerization initiator described below, an acid, or the like. Examples of the polymerizable group include: vinyl, vinyloxy, 1-chloroethenyl, isopropenyl, 4-vinylphenyl, acryloxy, methacryloxy, oxirane, oxetanyl and the like. Among them, acryloyloxy, methacryloyloxy, vinyloxy, oxirane and oxetanyl groups are preferable, and acryloyloxy group is more preferable. The compound exhibiting liquid crystallinity may be a thermotropic liquid crystal, or a lyotropic liquid crystal, and may be a nematic liquid crystal or a smectic liquid crystal among thermotropic liquid crystals.

The polymerizable liquid crystal is preferably a smectic liquid crystal compound, and more preferably a higher order smectic liquid crystal compound, in view of obtaining higher polarization characteristics. Among these, higher order smectic liquid crystal compounds which form a smectic B phase, smectic D phase, smectic E phase, smectic F phase, smectic G phase, smectic H phase, smectic I phase, smectic J phase, smectic K phase or smectic L phase are more preferable, and higher order smectic liquid crystal compounds which form a smectic B phase, smectic F phase or smectic I phase are more preferable. If the liquid crystal phase formed by the polymerizable liquid crystal compound is such a higher smectic phase, the polymerizable liquid crystal compound can be usedA polarizing film having a higher alignment order is produced. In addition, the long polarizing film having such a high alignment order degree obtains a bragg peak derived from a high-order structure such as a hexagonal phase or a crystal phase in an X-ray diffraction measurement. The Breger peak is a peak of a periodic structure derived from molecular alignment, and if the liquid crystal phase formed by the polymerizable liquid crystal compound is such a higher order smectic phase, a period interval of

The film of (1).

Specific examples of such a compound include a compound represented by the following formula (d) (hereinafter, may be referred to as a compound (d)). The polymerizable liquid crystal compounds may be used alone or in combination.

U¹-V¹-W¹-X¹-Y¹-X²-Y²-X³-W²-V²-U² (d)

[ in the formula (d),

X¹、X²and X³Independently of each other, a1, 4-phenylene group which may have a substituent or a cyclohexane-1, 4-diyl group which may have a substituent. Wherein, X¹、X²And X³At least one of them is a1, 4-phenylene group which may have a substituent. -CH constituting cyclohexane-1, 4-diyl₂-may be substituted by-O-, -S-or-NR-. R represents an alkyl group having 1 to 6 carbon atoms or a phenyl group.

Y¹And Y²Independently of one another represent-CH₂CH₂-、-CH₂O-, -COO-, -OCOO-, single bond, -N ═ N-, -CR^a＝CR^b-, -C.ident.C-or-CR^a＝N-。

R^aAnd R^bIndependently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

U¹Represents a hydrogen atom or a polymerizable group.

U²Represents a polymerizable group.

W¹And W²Independently of one another, represents a single bond, -O-, -S-, -COO-or-OCOO-.

V¹And V²Independently represents an alkanediyl group having 1 to 20 carbon atoms which may have a substituent, and-CH constituting the alkanediyl group₂May be substituted by-O-, -S-or-NH-]

In the compound (d), X¹、X²And X³At least one of them is preferably a1, 4-phenylene group which may have a substituent.

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

Examples of the substituent optionally having a1, 4-phenylene group which may have a substituent or a cyclohexane-1, 4-diyl which may have a substituent include: alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl and butyl, cyano groups, halogen atoms and the like.

Y¹preferably-CH₂CH₂-, -COO-or a single bond, Y²preferably-CH₂CH₂-or-CH₂O-。

U²Is a polymerizable group. U shape¹Is a hydrogen atom or a polymerizable group, and a polymerizable group is preferred. U shape¹And U²Preferably, all of them are polymerizable groups, and preferably all of them are photopolymerizable groups. The polymerizable liquid crystal compound having a photopolymerizable group is advantageous for polymerization under lower temperature conditions.

U¹And U²The polymerizable groups represented may be different from each other, but are preferably the same. Examples of the polymerizable group include: vinyl, vinyloxy, 1-chloroethenyl, isopropenyl, 4-vinylphenyl, acryloxy, methacryloxy, oxirane, oxetanyl and the like. Among them, acryloyloxy, methacryloyloxy, vinyloxy, oxirane and oxetanyl groups are preferable, and acryloyloxy group is more preferable.

As V¹And V²Examples of the alkanediyl group include: methylene, ethylene, propane-1, 3-diyl, butane-1, 4-diyl, pentane-1, 5-diyl, hexane1, 6-diyl, heptane-1, 7-diyl, octane-1, 8-diyl, decane-1, 10-diyl, tetradecane-1, 14-diyl, eicosane-1, 20-diyl, and the like. V¹And V²Preferably an alkanediyl group having 2 to 12 carbon atoms, and more preferably an alkanediyl group having 6 to 12 carbon atoms.

Examples of the substituent optionally having an alkanediyl group having 1 to 20 carbon atoms which may have a substituent include a cyano group, a halogen atom and the like, but the alkanediyl group is preferably unsubstituted, and more preferably unsubstituted and linear alkanediyl group.

W¹And W²Preferably independently of one another, a single bond or-O-.

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

[ chemical 34]

[ solution 35]

[ solution 36]

[ solution 37]

Among the compounds (d) mentioned above, at least one compound selected from the group consisting of compounds represented by the formulae (1-2), (1-3), (1-4), (1-6), (1-7), (1-8), (1-13), (1-14) and (1-15) is preferred.

The exemplified compound (d) may be used alone or in combination for a long polarizing film.

When 2 or more polymerizable liquid crystal compounds are combined, at least one is preferably the compound (c), and more preferably 2 or more are the compound (d). By combining these, liquid crystallinity may be temporarily maintained even at a temperature not higher than the liquid crystal-crystalline phase transition temperature. The mixing ratio in the case of combining 2 kinds of polymerizable liquid crystal compounds is usually 1: 99-50: 50, preferably 5: 95-50: 50, more preferably 10: 90-50: 50.

the compound (d) can be produced by a known method described in Lub et al, Recl. Travv. Chim. Pays-Bas,115,321-328(1996), Japanese patent No. 4719156, or the like.

< (E) a dye having lyotropic liquid crystallinity

When the polarizing layer contains (E) a dye having lyotropic liquid crystal properties, the dye is not particularly limited as long as it has lyotropic liquid crystal properties and can form a supramolecular aggregate.

Examples of such a dye having lyotropic liquid crystallinity include: azo compounds, anthraquinone compounds, perylene compounds, quinophthalone compounds, naphthoquinone compounds, merocyanine compounds, and the like. From the viewpoint of exhibiting good lyotropic liquid crystallinity, azo compounds are preferably used.

Among azo compounds, azo compounds having an aromatic ring in the molecule are preferable, and disazo compounds having a naphthalene ring are more preferable. By applying a coating liquid containing such an azo compound and drying it, a polarizing layer having excellent polarizing properties can be obtained.

The azo compound is preferably an azo compound having a polar group in the molecule. Azo compounds having a polar group are soluble in an aqueous solvent and easily dissolved in an aqueous solvent to form a supramolecular aggregate. Therefore, the coating liquid containing the azo-based compound having a polar group exhibits particularly good lyotropic liquid crystallinity.

The polar group means a functional group having polarity. As the polar group, there can be mentioned: OH group, COOH group, NH₂Radical, NO₂Relatively electronegative, oxygen and/or nitrogen containing functional groups such as radicals, CN radicals and the like.

As the azo-based compound having a polar group, for example, an aromatic disazo compound represented by the following general formula (E-1) is preferable.

[ solution 38]

In the general formula (E-1), Q¹Represents a substituted or unsubstituted aryl group, Q²Represents a substituted or unsubstituted arylene radical, R^EIndependently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted acetyl group, a substituted or unsubstituted benzoyl group, a substituted or unsubstituted phenyl group, M represents a counter ion, M7 represents an integer of 0 to 2, and n7 represents an integer of 0 to 6. Wherein at least one of m7 and n7 is not 0, 1 ≦ m7+ n7 ≦ 6. When m7 is 2, each R^EThe same or different.

OH, (NHR) shown in the general formula (E-1)^E)_m7And (SO)₃M)_n7Each of the 7 substituents may be bonded to the naphthalene ring.

In the present specification, the term "substituted or unsubstituted" means "substituted or unsubstituted with a substituent".

The bonding position between the naphthyl group and the azo group (-N ═ N-) of the general formula (E-1) is not particularly limited. The naphthyl group means a naphthyl group shown on the right side in the formula (E-1). Preferably, the naphthyl group and the azo group are bonded at the 1-or 2-position of the naphthyl group.

In the general formula (E-1) R^EWhen the alkyl group, acetyl group, benzoyl group or phenyl group in (a) has a substituent, examples of the substituent include the substituents exemplified for the aryl group and the arylene group described below.

The R is¹Preferred are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted acetyl group, and more preferred is a hydrogen atom.

The substituted or unsubstituted alkyl group includes a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms.

M (counter ion) of the general formula (E-1) may be preferably exemplified by: hydrogen ions; alkali metal ions such as Li, Na, K, Cs and the like; ca. Alkaline earth metal ions such as Sr and Ba; other metal ions; ammonium ions which may be substituted by alkyl or hydroxyalkyl; salts of organic amines, and the like. Examples of the metal ion include: ni⁺、Fe³⁺、Cu²⁺、Ag⁺、Zn²⁺、Al³⁺、Pd²⁺、Cd²⁺、Sn²⁺、Co²⁺、Mn²⁺、Ce³⁺And the like. As the organic amine, there can be exemplified: alkylamine having 1 to 6 carbon atoms, alkylamine having 1 to 6 carbon atoms and hydroxyl, alkylamine having 1 to 6 carbon atoms and carboxyl, and the like. In the general formula (E-1), in SO₃When M is 2 or more, M may be the same or different. In addition, in the general formula (E-1), in SO₃When M is a cation having a valence of 2 or more, it may be bonded to SO of another adjacent azo-based compound of the general formula (E-1)₃ ^-Bonding to form supramolecular aggregates.

M7 of the general formula (E-1) is preferably 1. Further, n7 in the general formula (E-1) is preferably 1 or 2.

Specific examples of the naphthyl group of the general formula (E-1) include the following formulae (E-a) to (E-l). R of formulae (E-a) to (E-l)^EAnd M is the same as the general formula (E-1).

[ solution 39]

In the general formula (E-1), as the Q¹Examples of the aryl group include a condensed ring group obtained by condensing 2 or more benzene rings such as a naphthyl group, in addition to a phenyl group.

As said Q²Examples of the arylene group include a condensation ring group obtained by condensation of 2 or more benzene rings such as naphthylene group and the like, in addition to phenylene group.

Q¹Aryl or Q of²The arylene group of (a) may have a substituent or may have no substituent. In the aryl or arylene substituted or unsubstituted cases, having polar groups of the general formula (E-1) aromatic double azo compounds in the water system solvent solubility is excellent.

In the case where the aryl group or the arylene group has a substituent, examples of the substituent include: c1-6 hydroxyalkyl such as C1-6 alkyl, C1-6 alkoxy, C1-6 alkylamino, phenylamino, C1-6 acylamino, dihydroxypropyl, or the like, or carboxyl such as COOM group, SO₃Sulfonic acid groups such as M group, hydroxyl group, cyano group, nitro group, amino group, and halogen group. The substituent is preferably one selected from the group consisting of an alkoxy group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, a carboxyl group, a sulfonic group and a nitro group. The aromatic disazo compound having such a substituent is particularly excellent in water solubility. These substituents to be substituted may be 1 or 2 or more. The substitution ratio of the substituent may be arbitrary.

Q of the general formula (E-1)¹Substituted or unsubstituted phenyl is preferred, and phenyl having the substituent is more preferred.

Said Q²Preferred is a substituted or unsubstituted naphthylene, more preferred is a naphthylene having the substituent, and particularly preferred is a1, 4-naphthylene having the substituent.

Q of the formula (E-1)¹Is substituted or unsubstituted phenyl, and Q²The aromatic disazo compound which is a substituted or unsubstituted 1, 4-naphthylene is represented by the following general formula (E-2)。

[ solution 40]

In the general formula (E-2), R^EM, m7 and n7 are the same as those in the general formula (E-1).

In the general formula (E-2), A^EAnd B^ERepresents a substituent, and a and b represent the number of substitution of the substituent. A is described^EAnd B^EIndependently represent alkyl with 1-6 carbon atoms, alkoxy with 1-6 carbon atoms, alkylamino with 1-6 carbon atoms, phenylamino, acylamino with 1-6 carbon atoms, hydroxy alkyl with 1-6 carbon atoms such as dihydroxypropyl, carboxyl such as COOM group, SO, etc₃And a sulfonic acid group such as an M group, a hydroxyl group, a cyano group, a nitro group, an amino group, or a halogen group. The a is an integer of 0-5, and the b represents an integer of 0-4. Wherein at least one of a and b is not 0. When a is 2 or more, the substituent A^EMay be the same or different. When B is 2 or more, the substituent B^EMay be the same or different.

Among the aromatic disazo compounds contained in the general formula (E-2), an aromatic disazo compound represented by the following general formula (E-3) is preferably used. In the aromatic disazo compound of the general formula (E-3), the substituent A^EAnd bonded in the para position based on an azo group (-N-). In the aromatic disazo compound of the general formula (E-3), the OH group of the naphthyl group is bonded to a position adjacent to the azo group (ortho position). When the aromatic disazo compound of the general formula (E-3) is used, a polarizing plate having a high degree of polarization can be obtained.

[ solution 41]

In the general formula (E-3), R^EM, m7 and n7 are the same as those in the general formula (E-1), A^EThe same as that in the general formula (E-2).

In the general formula (E-3), p7 represents an integer of 0 to 4. The p7 is preferably 1 or 2, more preferably 1.

The aromatic disazo compounds represented by the general formulae (E-1) to (E-3) can be synthesized, for example, according to "theoretical dyestuff chemistry (5 th edition)" manufactured by Sedi, published by Nippon Tech, 7 and 15, 1968, pages 135 to 152.

For example, the aromatic disazo compound of the general formula (E-3) can be synthesized by subjecting an aniline derivative and a naphthalenesulfonic acid derivative to diazotization and coupling reaction to obtain a monoazo compound, then diazotizing the monoazo compound, and thereafter further subjecting the monoazo compound to coupling reaction with a 1-amino-8-naphtholsulfonic acid derivative.

The content ratio of the polymerizable liquid crystal compound (D) or the dye having lyotropic liquid crystallinity (E) in the polarizing layer-forming composition is usually 70 to 99.9 parts by mass, preferably 80 to 99.9 parts by mass, more preferably 85 to 99 parts by mass, and still more preferably 90 to 99 parts by mass, relative to the solid content of the polarizing layer-forming composition, from the viewpoint of improving the alignment property of the liquid crystal compound.

< step [ IV ] and step [ V ] >

Step [ IV ] is a step of preparing the substrate having an alignment layer; and step [ V ] is a step selected from the following [ V-1] and [ V-2 ].

The polarizing layer forming composition is usually applied by a known method such as a spin coating method, an extrusion coating method, a gravure coating method, a die coating method, a bar coating method, a coating method or the like, or a printing method such as a flexographic method. In the case where the polarizing layer forming composition contains (D) a polymerizable liquid crystal, the solvent is usually removed after coating under conditions such that the polymerizable liquid crystal (D) contained in the obtained coating film does not polymerize, thereby forming a dried coating film. Examples of the drying method include: natural drying, air drying, heat drying and reduced pressure drying.

In the step of irradiating the coating film containing the dichroic dye (B) and the polymerizable liquid crystal (D) with ultraviolet rays, the polymerization of the polymerizable liquid crystal (D) can be carried out by a known method of polymerizing a compound having a polymerizable functional group. Specifically, thermal polymerization and photopolymerization are mentioned, and photopolymerization is preferred in terms of easy polymerizability. When polymerizing the polymerizable liquid crystal by photopolymerization, it is preferable to apply a composition obtained by further including a photopolymerization initiator to the polarizing layer forming composition containing the dichroic dye (B) and the polymerizable liquid crystal (D), dry the composition so that the polymerizable liquid crystal in the obtained dry film is in a liquid crystal phase state, and then perform photopolymerization while maintaining the liquid crystal state.

Photopolymerization is generally performed by irradiating a dry film with light. The light to be irradiated is appropriately selected depending on the kind of photopolymerization initiator contained in the dried film, the kind of (D) polymerizable liquid crystal (particularly, the kind of photopolymerizable group contained in (D) polymerizable liquid crystal) and the content, and specifically, light selected from the group consisting of visible light, ultraviolet light, and laser light, and an active electron beam are exemplified. Among them, in terms of easy control of the progress of the polymerization reaction and in terms of availability of a photopolymerization device which is generally used in this field, ultraviolet light is preferable, and (D) the type of the polymerizable liquid crystal or the photopolymerization initiator is preferably selected so that photopolymerization can be performed by ultraviolet light. In addition, the polymerization temperature may be controlled by irradiating the dried film with light while cooling the film by a suitable cooling method. By carrying out the polymerization of the polymerizable liquid crystal (D) at a lower temperature by using such a cooling method, the polarizing layer can be formed well even if a base material having relatively low heat resistance is used.

The polarizing layer-forming composition containing (E) a dye having lyotropic liquid crystal property is applied onto the alignment layer of the substrate having an alignment layer, and the composition is heated and dried to form a coating film, and the coating in this step is usually performed by a known method such as a coating method such as a spin coating method, an extrusion coating method, a gravure coating method, a die coating method, a bar coating method, or a dressing method, or a printing method such as a flexographic method. The drying method is not particularly limited, and natural drying or forced drying may be performed. Examples of forced drying include: drying under reduced pressure, drying by heating under reduced pressure, and the like. Natural drying is preferably employed.

The drying time may be appropriately selected depending on the drying temperature or the kind of the solvent. For example, in the case of natural drying, the drying time is preferably 1 second to 120 minutes, more preferably 10 seconds to 5 minutes.

The drying temperature is not particularly limited, but is preferably lower than the glass transition temperature (Tg) of the substrate. If the drying temperature exceeds the glass transition temperature of the substrate, the properties (mechanical strength, optical characteristics, etc.) of the substrate may change. Specifically, the drying temperature is preferably 10 to 100 ℃, more preferably 10 to 90 ℃, and particularly preferably 10 to 80 ℃.

The drying temperature is the temperature of the environment in which the coating film is dried, and is not the temperature of the surface or the interior of the coating film containing (E) the dye having lyotropic liquid crystal properties.

The total thickness of the alignment layer and the polarizing layer in the polarizing element is 10 [ mu ] m or less. The thickness of the alignment layer is preferably 0.5 μm or more and 9.5 μm or less, and more preferably 1 μm or more and 5 μm or less. The thickness of the polarizing layer is preferably 0.5 μm or more and 9.5 μm or less, and more preferably 1 μm or more and 5 μm or less. The thicknesses of the alignment layer and the polarizing layer are generally determined by measurement using an interferometric film thickness meter, a laser microscope, or a stylus film thickness meter.

The polarizing element obtained by the above-described method can be widely used in various display elements requiring polarization by a known method, and can be used in, for example, a liquid crystal display element, an antireflection film (circular polarizing plate) such as an organic EL (Electroluminescence) element, an optical switch, an optical filter, and various optical measurement devices using these as components.

The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[ examples ]

The present invention will be described in more detail with reference to examples of the present invention, but the present invention is not to be construed as being limited thereto.

< solvent >

Each of the resin compositions of examples and comparative examples contains a solvent, and propylene glycol monomethyl ether (PM), Cyclohexanone (CYH), and methyl isobutyl ketone (MIBK) are used as the solvent.

< determination of the molecular weight of the Polymer >

The molecular weight of the acrylic copolymer in the polymerization example was measured by using a Gel Permeation Chromatography (GPC) apparatus (GPC-101) manufactured by Shodex Ltd., and columns (KD-803, KD-805) manufactured by Shodex Ltd., as follows.

The number average molecular weight (hereinafter referred to as Mn) and the weight average molecular weight (hereinafter referred to as Mw) are expressed in terms of polystyrene.

Temperature of the pipe column: 50 deg.C

Eluent: n, N-dimethylformamide (as additive, lithium bromide hydrate (LiBr. H)₂O) is 30mmol/L, anhydrous phosphoric acid crystals (O-phosphoric acid) is 30mmol/L, Tetrahydrofuran (THF) is 10mL/L)

Flow rate: 1.0mL/min

Standard samples for calibration curves were made: TSK standard polyethylene oxides (molecular weight of about 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh corporation and polyethylene glycols (molecular weight of about 12,000, 4,000, 1,000) manufactured by Polymer Laboratories, Inc.

< Synthesis example 1 >

4- (6-hydroxyhexyloxy) cinnamic acid is synthesized by heating 1-hydroxycinnamic acid and 1-bromo-6-hexanol under alkaline conditions. This product was reacted with methacryloyl chloride under basic conditions to obtain a compound (M1) represented by the following formula (Ex-1).

< Synthesis example 2 >

4- (6-hydroxyhexyloxy) benzoic acid was synthesized by heating 1-hydroxybenzoic acid and 1-bromo-6-hexanol under basic conditions. This product and methacryloyl chloride are reacted under basic conditions to obtain a compound represented by the formula (Ex-a) (hereinafter also referred to as compound (Ex-a)). This compound (Ex-A) was reacted with methoxyphenol in the presence of DCC and DMAP to obtain a compound represented by the following formula (Ex-2).

[ solution 42]

< Synthesis example 4 >

16.0g of the methacrylic acid ester represented by the above formula (Ex-1) and 0.4g of α, α' -azobisisobutyronitrile as a polymerization catalyst were dissolved in 180.0g of 1, 4-dioxane, and reacted at 80 ℃ for 20 hours to obtain an acrylic copolymer solution. The acrylic copolymer solution was slowly dropped into 1000.0g of diethyl ether to precipitate a solid, and the residue was removed by filtration and drying under reduced pressure to obtain an acrylic polymer (P1). The obtained acrylic copolymer had Mn of 9,300 and Mw of 16,000.

< Synthesis example 5 >

8.0g of the methacrylate represented by the formula (Ex-1), 7.4g of the methacrylate represented by the formula (Ex-A), and 0.8g of α, α' -azobisisobutyronitrile as a polymerization catalyst were dissolved in 145.0g of 1, 4-dioxane, and reacted at 80 ℃ for 20 hours to obtain an acrylic copolymer solution. The acrylic copolymer solution was slowly dropped into 1000.0g of diethyl ether to precipitate a solid, and the residue was removed by filtration and drying under reduced pressure to obtain an acrylic copolymer (P2). The obtained acrylic copolymer had Mn of 8,000 and Mw of 20,000.

< Synthesis example 6 >

10.0g of the methacrylate represented by the formula (Ex-1), 5.3g of the methacrylate represented by the formula (Ex-2) and 0.2g of α, α' -azobisisobutyronitrile as a polymerization catalyst were dissolved in 165.0g of 1, 4-dioxane, and reacted at 80 ℃ for 20 hours to obtain an acrylic copolymer solution. The acrylic copolymer solution was slowly dropped into 1000.0g of diethyl ether to precipitate a solid, and the residue was removed by filtration and drying under reduced pressure to obtain an acrylic copolymer (P3). The obtained acrylic copolymer had Mn of 11,000 and Mw of 21,000.

< Synthesis example 7 >

8.0g of the methacrylate represented by the formula (Ex-1), 9.8g of the methacrylate represented by the formula (Ex-2) and 0.2g of α, α' -azobisisobutyronitrile as a polymerization catalyst were dissolved in 180.0g of 1, 4-dioxane, and reacted at 80 ℃ for 20 hours to obtain an acrylic copolymer solution. The acrylic copolymer solution was slowly dropped into 1000.0g of diethyl ether to precipitate a solid, and the residue was removed by filtration and drying under reduced pressure to obtain an acrylic copolymer (P4). The obtained acrylic copolymer had Mn of 14,000 and Mw of 24,000.

< production example 1 >

[ preparation of polarizing layer Forming composition RM 1]

A polarizing layer forming composition (RM1) having a solid content of 30 mass% was prepared by dissolving 14.6G of a polymerizable liquid crystal (RMM141C, Merck) and 0.44G of a dichroic dye (G-241, Yunyuan) in 35.0G of MIBK.

< production example 2 >

[ preparation of polarizing layer Forming composition RM 2]

A polarizing layer forming composition (RM2) having a solid content of 30 mass% was prepared by dissolving 14.4G of a polymerizable liquid crystal (RMM141C, Merck) and 0.58G of a dichroic dye (G-470, Lingyuan) in 35.0G of MIBK.

< examples 1 to 6 > and < comparative examples 1 to 2 >

Each alignment layer forming composition of examples 1 to 6 and comparative examples 1 to 2 was prepared according to the composition shown in table 1. Alignment layers were formed using the alignment layer-forming compositions, and dichroic ratio measurements were performed for the alignment layers. Then, a polarizing element is formed using the polarizing layer forming composition. For each of the obtained polarizing elements, evaluation of alignment, measurement of polarization degree, and measurement of dichroic ratio were performed.

[ Table 1]

< example 1 >

[ formation of alignment layer ]

The alignment layer-forming composition shown in Table 1 was spin-coated on a quartz substrate, and dried on a hot plate at 55 ℃ for 60 seconds to form a coating film having a thickness of 200 nm. Then, the film surface was coated at a thickness of 2mJ/cm through a polarizing plate²The exposure amount of (A) was perpendicular to the linear polarization of 313 nm. Then, the alignment layer was formed by heating at 170 ℃ for 5 minutes using a hot plate.

[ measurement of dichroic ratio of alignment layer ]

The dichroic ratio of the obtained alignment layer was determined as follows. The absorbance in the transmission axis direction (A1) and the absorbance in the absorption axis direction (A2) were measured using a device obtained by attaching a jig (holder) with a polarizer to a spectrophotometer (UV-3600 manufactured by Shimadzu corporation). From the measured values of the absorbance in the transmission axis direction (a1) and the absorbance in the absorption axis direction (a2), the dichroic ratio was calculated by using the following formula. The measurement results are shown in table 2.

Dichroic ratio (a2)/(a1)

[ formation of polarizing layer ]

The polarizing layer-forming composition RM1 was spin-coated on the obtained alignment layer at 2000rpm 30sec, and dried on a hot plate at 65 ℃ for 60 seconds to form a coating film. Then, at 500mJ/cm²The coating film was exposed to light, thereby obtaining a polarizing element.

[ evaluation of alignment Properties ]

The alignment of the obtained polarizing element was confirmed by observation with a polarizing microscope. The sample was inserted between crossed nicols of a polarizing microscope in the directions of 0 ° and 45 °, and the light leakage state was observed. When the alignment was achieved, light leakage did not occur at 0 ° and a dark field was observed, and light leakage occurred at 45 ° and a bright field was observed. The case where a dark field was obtained at 0 °, a bright field was obtained at 45 ° was marked as "o", and the case where no dark field was obtained was marked as "x". The measurement results are shown in table 2.

[ measurement of degree of polarization ]

The degree of polarization of the obtained polarizing element was measured as follows. The transmittance in the transmission axis direction (T1) and the transmittance in the absorption axis direction (T2) were measured using a device obtained by mounting a jig with a polarizer on a spectrophotometer (UV-3600 manufactured by shimadzu corporation). From the measured values of the transmittance in the transmission axis direction (T1) and the transmittance in the absorption axis direction (T2), the degree of polarization was calculated using the following equation. The measurement results are shown in table 2.

Degree of polarization (%) { (T1-T2)/(T1 + T2) }^1/2×100

[ measurement of dichroic ratio of polarizing element ]

The dichroic ratio of the obtained polarizing element was measured as follows. The absorbance in the transmission axis direction (A1) and the absorbance in the absorption axis direction (A2) were measured using a device obtained by mounting a jig with a polarizer on a spectrophotometer (UV-3600 manufactured by Shimadzu corporation). From the measured values of the absorbance in the transmission axis direction (a1) and the absorbance in the absorption axis direction (a2), the dichroic ratio was calculated by using the following formula. The measurement results are shown in table 2.

Dichroic ratio (a2)/(a1)

< example 2 >

The linear polarization at the time of formation of the alignment layer was set to 5mJ/cm²A polarizing element was produced in the same manner as in example 1, except that the heating temperature after the polarizing exposure was 150 ℃. The results are shown in Table 2.

< example 3 >

A polarizing element was produced in the same manner as in example 1, except that the heating temperature after the polarized light exposure in the formation of the alignment layer was set to 120 ℃. The results are shown in Table 2.

< example 4 >

A polarizing element was produced in the same manner as in example 1, except that the heating temperature after the polarized light exposure in the formation of the alignment layer was set to 100 ℃. The results are shown in Table 2.

< example 5 >

A polarizing element was produced in the same manner as in example 1, except that the heating temperature after the polarized light exposure in the formation of the alignment layer was set to 140 ℃. The results are shown in Table 2.

< example 6 >

A polarizing element was produced in the same manner as in example 1, except that the heating temperature after the polarized light exposure at the time of forming the alignment layer was set to 100 ℃, and RM2 was used as the polarizing layer forming composition. The results are shown in Table 2.

< comparative example 1 >

< comparative example 2 >

[ Table 2]

In comparative examples 1 to 2 in which no dichroic dye was added to the alignment layer, the dichroic ratio of the alignment layer was 0. On the other hand, in examples 1 to 6 in which dichroic dyes were blended in the alignment layer, a high dichroic ratio was obtained, and the dichroic dyes could be aligned in the alignment layer.

The polarizers obtained in examples 1 to 5 can exhibit a high level of polarization degree and dichroic ratio, compared to comparative example 1.

The polarizer obtained in example 6 can exhibit a high level of polarization degree and dichroic ratio, compared to comparative example 2.

Claims

1. A polymer composition comprising (A) a side chain polymer exhibiting photosensitivity in a specific temperature range, (B) a dichroic dye and an organic solvent,

wherein the component (A) is a side chain type polymer having any one photosensitive side chain selected from the group consisting of the following formulas (1) to (6),

[ solution 1]

Y₂represents a group selected from the group consisting of a 2-valent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination of these rings, and hydrogen atoms bonded to these groups may be independently substituted with-NO₂、-CN、-CH＝C(CN)₂-CH ═ CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;

r represents a hydroxyl group or an alkane having 1 to 6 carbon atomsOxy, or represents and Y₁The same definition;

q1 and q2 are one 1 and the other 0;

q3 is 0 or 1;

l1 is 0 or 1;

l2 is an integer of 0 to 2;

a represents a single bond when T is a single bond, when both l1 and l2 are 0;

when l1 is 1, B represents a single bond when T is a single bond;

h and I each independently represent a group selected from the group consisting of a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a combination of these rings.

2. The polymer composition according to claim 1, wherein the component (A) is a side chain type polymer having a photosensitive side chain which causes photocrosslinking, photoisomerization or photofuji rearrangement.

3. The polymer composition according to claim 1 or 2, wherein the component (A) has any one liquid crystalline side chain selected from the group consisting of the following formulas (21) to (31),

[ solution 2]

Wherein A, B, q1 and q2 have the same meanings as defined above;

Z₁、Z₂represents a single bond, -CO-, -CH₂O-、-CH＝N-、-CF₂-。

4. The polymer composition according to any one of claims 1 to 3, which contains a compound represented by the following formula (C) as the (C) component,

[ solution 3]

In the formula, R¹⁰¹、R¹⁰²、R¹⁰³、R¹⁰⁴And R¹⁰⁵Any three to five of (A) each independently represent a group selected from a hydrogen atom, a halogen atom, C₁～C₆Alkyl radical, C₁～C₆Haloalkyl, C₁～C₆Alkoxy radical, C₁～C₆Haloalkoxy, C₃～C₈Cycloalkyl radical, C₃～C₈Halocycloalkyl radical, C₂～C₆Alkenyl radical, C₂～C₆Haloalkenyl, C₃～C₈Cycloalkenyl radical, C₃～C₈Halocycloalkenyl radical, C₂～C₆Alkynyl, C₂～C₆Haloalkynyl, (C)₁～C₆Alkyl) carbonyl (C)₁～C₆Haloalkyl) carbonyl, (C)₁～C₆Alkoxy) carbonyl (C)₁～C₆Haloalkoxy) carbonyl, (C)₁～C₆Alkylamino) carbonyl group, (C)₁～C₆Haloalkyl) aminocarbonyl, di (C)₁～C₆Alkyl) a substituent of the group consisting of aminocarbonyl, cyano and nitro, in R¹⁰¹、R¹⁰²、R¹⁰³、R¹⁰⁴And R¹⁰⁵In the case that any three to four of (A) are defined as above, R¹⁰¹、R¹⁰²、R¹⁰³、R¹⁰⁴And R¹⁰⁵One or two of the remaining(s) represent the following formula (c-2)

[ solution 4]

(in the formula (c-2), the dotted line represents a bond, R¹⁰⁶Represents an alkylene group having 1 to 30 carbon atoms, a phenylene group, or a divalent carbocyclic or heterocyclic ring, wherein 1 or more hydrogen atoms in the alkylene group, the phenylene group, or the divalent carbocyclic or heterocyclic ring may be substituted with a fluorine atom or an organic group; in addition, R¹⁰⁶In (C-CH)₂CH₂-may be substituted by-CH ═ CH-, R¹⁰⁶In (C-CH)₂May be substituted by phenylene or by a divalent carbocyclic or heterocyclic ring, and may also be substituted by any of the radicals listed below without being adjacent to one anotherAnd in the case of alkyl radicals, are substituted by these radicals: -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH-, -CO-; r¹⁰⁷Represents a hydrogen atom or a methyl group), and n represents 0 or 1.

5. An alignment layer forming composition containing the polymer composition according to any one of claims 1 to 4.