KR102345838B1 - polymer composition - Google Patents

Abstract

[PROBLEMS] This invention provides the polymer composition for liquid crystal aligning films which can orientate a polymeric crystal composition, when obtaining a polarizing element with high dichroism.
[Solutions] The present invention provides (A) a polymer composition containing a photosensitive side chain polymer having a dichroic dye in the side chain and expressing liquid crystallinity in a predetermined temperature range, and an organic solvent. A polarizing element with high dichroism can be obtained by heat-drying, after apply|coating a polymeric liquid crystal composition on the alignment film, and irradiating an ultraviolet-ray as needed for the board|substrate which has a liquid crystal aligning film formed from this polymer composition.

Description

polymer composition

The present invention relates to a polymer composition having a dichroic dye useful for forming an alignment layer for orienting a polymerizable liquid crystal composition serving as a polarizing layer in formation of a polarizing element.

As a polarizing plate used for a liquid crystal display etc., conventionally, iodine has been widely used as a dichroic dye. However, since there is a problem that the iodine-based polarizing film is inferior in heat resistance and light resistance, attempts have been made to use an organic dichroic material, that is, a dichroic dye.

Conventionally, as a dichroic dye, for the purpose of obtaining high dichroism, dyes having an azo skeleton as a basic skeleton (Patent Documents 1 and 2), dyes having an anthraquinone skeleton, and the like are used a lot.

In addition, as a method for manufacturing a polarizing plate, in addition to a method of stretching a polymer film containing iodine or a dichroic dye, as a coating-type polarizing plate, a liquid crystal composition in which a liquid crystal compound serving as a host material is mixed with a dye serving as a guest material is used as a substrate There is known a method of applying to the skin (patent document 3). Furthermore, in order to provide a more stable polarizing film, a method of using a mixture of a crosslinkable liquid crystal and a polymerizable dichroic dye (Patent Document 4); a method for producing an optically anisotropic body in which a polymerizable non-liquid crystalline solvent is added to a polymerizable liquid crystal compound and the polymerizable non-liquid crystalline solvent is left in the coating film to improve adhesion with other optical films (Patent Document 5); And the method (patent document 6) of preparing a polymerizable mesogen agent containing a polymerizable mesogen compound and a dichroic dye, and using this to prepare a polarizer effectively from the point of time and cost is also proposed.

Japanese Patent Laid-Open No. 2011-213610 Japanese Patent Publication No. 2006-525382 Japanese Patent Publication No. 2008-547062 Japanese Patent Publication No. 2004-535483 Japanese Patent Laid-Open No. 2004-198480 Japanese Patent Publication No. 2006-161051

At present, in order to improve the absorption characteristics in the visible region, it has been studied to highly blend a dichroic dye excellent in absorption characteristics into a liquid crystal composition. However, since the solubility to a solvent is generally low, there existed a problem that it was difficult to mix|blend this dichroic dye highly with a liquid crystalline composition.

Under the above background, the present invention provides a polymer composition having a dichroic dye useful for forming an alignment layer for orienting a polymerizable liquid crystal composition to be a novel polarizing layer.

MEANS TO SOLVE THE PROBLEM The present inventors discovered the following invention, as a result of earnestly examining in order to achieve the said subject.

<1> [I] (A) A polymer composition comprising a photosensitive side chain polymer having a dichroic dye in the side chain and expressing liquid crystallinity in a predetermined temperature range, and an organic solvent.

<2> The polymer composition according to <1>, wherein the component (A) has a photosensitive side chain that causes photocrosslinking, photoisomerization, or photofree transition.

<3> (A) The polymer composition as described in said <1> in which component has any 1 type of photosensitive side chain chosen from the group which consists of following formula (1)-(6).

[Formula 1]

wherein A, B and D are each independently a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO- O-, or -O-CO-CH=CH-;

S represents an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded to a carbon atom in the alkylene group may be substituted with a halogen atom;

T represents a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded to a carbon atom in the alkylene group may be substituted with a halogen atom;

Y ₁ is a monovalent substituent in which one hydrogen atom is removed from a benzene ring, a monovalent substituent in which one hydrogen atom is removed from a naphthalene ring, a monovalent substituent in which one hydrogen atom is removed from a biphenyl ring, one hydrogen from a furan ring A monovalent substituent in which an atom is removed, a monovalent substituent in which one hydrogen atom is removed from a pyrrole ring, or a monovalent substituent in which one hydrogen is removed from an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same selected from these substituents or a monovalent substituent formed by bonding 2 to 6 different substituents through a bonding group defined by B, in all of these substituents, a hydrogen atom bonding to a carbon atom is each independently -COOR ₀ (wherein R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or may be substituted with an alkyloxy group having 1 to 5 carbon atoms;

Y ₂ is a divalent substituent in which two hydrogen atoms are removed from a benzene ring, a divalent substituent in which two hydrogen atoms are removed from a naphthalene ring, a divalent substituent in which two hydrogen atoms are removed from a biphenyl ring, two hydrogens from a furan ring A divalent substituent in which atoms are removed, a divalent substituent in which two hydrogens are removed from a pyrrole ring, a divalent substituent in which two hydrogen atoms are removed from an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof. represents a divalent substituent, and in all of these substituents, a hydrogen atom bonded to a carbon atom is each independently -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen atom, and the number of carbon atoms. may be substituted with an alkyl group having 1 to 5 carbon atoms or an alkyloxy group having 1 to 5 carbon atoms;

R represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or has the same definition as _{Y 1 ;}

X is a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, ※1-CH=CH-CO-O-※2, or ※1- O-CO-CH=CH-*2, *1 represents the bonding position with P in the formulas (1) to (6), *2 represents the formulas (1) to (6) It represents a bonding position with Q, and when the number of X is 2, X may be the same or different;

Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and hydrogen atoms bonded thereto are each independently -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, may be substituted with a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;

As for q1 and q2, one is 1 and the other is 0;

q3 is 0 or 1;

P and Q are each independently a divalent substituent in which two hydrogen atoms are removed from a benzene ring, a divalent substituent in which two hydrogen atoms are removed from a naphthalene ring, a divalent substituent in which two hydrogen atoms are removed from a biphenyl ring, furan A divalent substituent in which two hydrogen atoms are removed from a ring, a divalent substituent in which two hydrogen atoms are removed from a pyrrole ring, a divalent substituent in which two hydrogen atoms are removed from an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof represents a divalent substituent selected from the group consisting of; However, when X is *1-CH=CH-CO-O-*2, or *1-O-CO-CH=CH-*2, *1 is the formula (1) to (6) above. represents a bonding position with P, *2 indicates a bonding position with Q in the formulas (1) to (6), and P or Q on the side to which -CH=CH- is bonded is two hydrogen atoms from an aromatic ring. represents a divalent substituent from which ;

l1 is 0 or 1;

l2 is an integer from 0 to 2;

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

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

H and I are each independently a divalent substituent in which two hydrogen atoms are removed from a benzene ring, a divalent substituent in which two hydrogen atoms are removed from a naphthalene ring, a divalent substituent in which two hydrogen atoms are removed from a biphenyl ring, furan A divalent substituent selected from a divalent substituent in which two hydrogen atoms are removed from a ring, a divalent substituent in which two hydrogen atoms are removed from a pyrrole ring, and a combination thereof is shown.

<4> (A) The polymer composition in any one of said <1>-<3> in which component has any 1 type of liquid crystalline side chain chosen from the group which consists of following formula (21)-(31).

[Formula 2]

wherein A, B, q1 and q2 have the same definitions as above;

Y ₃ is a monovalent substituent in which one hydrogen atom is removed from a benzene ring, a monovalent substituent in which one hydrogen atom is removed from a naphthalene ring, a monovalent substituent in which one hydrogen atom is removed from a biphenyl ring, is one hydrogen from a furan ring A monovalent substituent in which an atom is removed, a monovalent substituent in which one hydrogen atom is removed from a nitrogen-containing heterocycle, a monovalent substituent in which one hydrogen atom is removed from an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a group consisting of combinations thereof represents a monovalent substituent selected from, and among all of these substituents, a hydrogen atom bonded to a carbon atom is each independently -NO ₂ , -CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms may be substituted with an alkyloxy group;

R ₃ is a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen atom, a monovalent substituent obtained by removing one hydrogen atom from a benzene ring, and 1 from a naphthalene ring A monovalent substituent in which two hydrogen atoms are removed, a monovalent substituent in which one hydrogen atom is removed from a biphenyl ring, a monovalent substituent in which one hydrogen atom is removed from a furan ring, a monovalent substituent in which one hydrogen atom is removed from a nitrogen-containing heterocyclic ring , a monovalent substituent in which one hydrogen atom has been removed from an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;

l represents the integer of 1-12, m represents the integer of 0-2, with the proviso that in Formula (23) and Formula (24), the sum of all m is 2 or more, Formula (25) and Formula ( In 26), the sum of all m is 1 or more, and m1, m2 and m3 each independently represent an integer of 1 to 3;

R ₂ is a hydrogen atom, -NO ₂ , -CN, a halogen atom, a monovalent substituent in which one hydrogen atom is removed from a benzene ring, a monovalent substituent in which one hydrogen atom is removed from a naphthalene ring, one hydrogen from a biphenyl ring A monovalent substituent in which an atom is removed, a monovalent substituent in which one hydrogen atom is removed from a furan ring, a monovalent substituent in which one hydrogen atom is removed from a nitrogen-containing heterocycle, and one hydrogen atom from an alicyclic hydrocarbon having 5 to 8 carbon atoms represents the removed monovalent substituent, an alkyl group, or an alkyloxy group;

Z ₁ and Z ₂ represent a single bond, -CO-, -CH ₂ O-, -CH=N-, or -CF ₂ -.

<5> (B) The polymer composition in any one of said <1>-<4> characterized by containing the compound represented by following formula (c) as a component.

[Formula 3]

( ^{Wherein, any 3 to 5 of R 101} , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ and R ¹⁰⁵ are each independently a hydrogen atom, a halogen atom, a C ₁ to C ₆ alkyl group, or a C ₁ to C ₆ haloalkyl group , C ₁ to C ₆ alkoxy group, C ₁ to C ₆ haloalkoxy group, C ₃ to C ₈ cycloalkyl group, C ₃ to C ₈ halocycloalkyl group, C ₂ to C ₆ alkenyl group, C ₂ to C ₆ haloalke Nyl group, C ₃ to C ₈ cycloalkenyl group, C ₃ to C ₈ halocycloalkenyl group, C ₂ to C ₆ alkynyl group, C ₂ to C ₆ haloalkynyl group, (C ₁ to C ₆ alkyl)carbonyl group, (C ₁ to C ₆ haloalkyl)carbonyl group, (C ₁ to C ₆ alkoxy)carbonyl group, (C ₁ to C ₆ haloalkoxy)carbonyl group, (C ₁ to C ₆ alkylamino)carbonyl group, (C ₁ to C ₆ haloalkyl) represents a substituent selected from an aminocarbonyl group, a di(C ₁ to C ₆ alkyl)aminocarbonyl group, a cyano group and a nitro group, and any 3 to 4 of ^{R 101} , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ and R ^{105 are defined above} When , R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ and R ¹⁰⁵ the other one or two of the following formula (c-2)

[Formula 4]

(In formula (c-2), the broken line indicates the number of bonds, and R ¹⁰⁶ is a divalent substituent or heterocyclic group obtained by removing two hydrogen atoms from an alkylene group having 1 to 30 carbon atoms, a phenylene group, or a carbocyclic compound. A divalent substituent in which two hydrogen atoms have been removed from a cyclic compound is represented, and two hydrogen atoms are removed from an alkylene group, a phenylene group, or a divalent substituent obtained by removing two hydrogen atoms from a carbocyclic compound, or from a heterocyclic compound One or more hydrogen atoms in the divalent substituent may be substituted with a fluorine atom or an organic group, -CH ₂ CH ₂ ^{- in R 106} may be substituted with -CH=CH-, and -CH ₂ - may be substituted with a phenylene group, a divalent substituent in which two hydrogen atoms are removed from a carbocyclic compound, or a divalent substituent in which two hydrogen atoms are removed from a heterocyclic compound, and further, - in ^{R 106} CH ₂ - is, unless divalent groups selected from the group consisting of -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH-, and -CO- are adjacent to each other , may be substituted with these divalent groups.

R ¹⁰⁷ is a hydrogen atom or a methyl group.) represents the group represented by), and n represents 0 or 1.)

ADVANTAGE OF THE INVENTION According to this invention, the novel polymer composition which can obtain the polarizing plate which has high polarization performance without highly mixing|blending a dichroic dye in a liquid crystalline composition can be provided.

As a result of intensive research, the present inventors obtained the following findings and completed the present invention.

The polymer composition used in the production method of the present invention has a dichroic dye in the side chain and contains a photosensitive side chain polymer (hereinafter also simply referred to as side chain polymer) capable of expressing liquid crystallinity, the polymer The coating film obtained using the composition is a film|membrane which has photosensitive side chain type polymer|macromolecule which can express liquid crystallinity. The coating film is subjected to an orientation treatment by irradiation with polarized light without applying a rubbing treatment. Then, after polarized light irradiation, through a step of heating the side chain type polymer film, it becomes a coating film (hereinafter also referred to as an orientation layer) to which the orientation control ability is imparted. At this time, the slight anisotropy expressed by polarization irradiation becomes a driving force, and the liquid crystalline side chain polymer itself is efficiently reorientated by self-organization. As a result, as an alignment layer, highly efficient alignment treatment is realized, and an alignment layer to which high alignment control ability is imparted can be obtained. Here, by containing the dichroic dye in the side chain of the side chain polymer, an alignment layer having a high dichroism ratio can be obtained. Therefore, when forming a polarizing layer, the polymer composition of this invention is useful as a composition for orientation layer formation for orientating a liquid crystalline composition and the polarizing layer containing a dichroic dye as needed.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail.

<<(A) side chain polymer >>

(A) Component is a photosensitive side chain type polymer|macromolecule which has a dichroic dye in a side chain and expresses liquid crystallinity in a predetermined|prescribed temperature range.

(A) The side-chain polymer reacts with light in a wavelength range of 250 nm to 400 nm, and preferably exhibits liquid crystallinity in a temperature range of 60° C. to 300° C.

(A) The side chain polymer preferably has a photosensitive side chain that responds to light in a wavelength range of 250 nm to 400 nm.

(A) The side chain polymer preferably has a mesogenic group in order to exhibit liquid crystallinity in a temperature range of 60°C to 300°C.

(A) The side chain type polymer has a photosensitive side chain bonded to the main chain, and can cause a crosslinking reaction, an isomerization reaction, or a photofree dislocation in response to light. The structure of the side chain having photosensitivity is not particularly limited, but a structure in which a crosslinking reaction or a photofree dislocation is generated in response to light is preferable, and more preferably a crosslinking reaction is caused. In this case, even when exposed to external stress such as heat, the realized orientation control ability can be stably maintained for a long period of time. The structure of the photosensitive side chain type polymer film capable of expressing liquid crystallinity is not particularly limited as long as it satisfies such characteristics, but it is preferable to have a rigid mesogenic component in the side chain structure. In this case, when this side chain type polymer|macromolecule is used as a liquid crystal alignment film, stable liquid crystal alignment can be obtained.

The structure of the polymer, for example, has a main chain and a side chain bonded thereto, and the side chain is a mesogenic component such as a biphenyl group, a terphenyl group, a phenylcyclohexyl group, a phenylbenzoate group, an azobenzene group, and a tip portion A structure having a photosensitive group that undergoes crosslinking or isomerization in response to light, or a main chain and a side chain bonded thereto, the side chain becomes a mesogenic component, and also a phenylbenzoate group that undergoes a photofree translocation reaction It can have a structure with

More specific examples of the structure of the photosensitive side chain polymer film capable of expressing liquid crystallinity include hydrocarbon, (meth)acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, It is preferable to have a structure having a main chain composed of at least one selected from the group consisting of a radical polymerizable group such as vinyl, maleimide, norbornene, and siloxane, and a side chain composed of at least one of the following formulas (1) to (6). do.

[Formula 5]

wherein A, B and D are each independently a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO- O-, or -O-CO-CH=CH-;

S represents an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded to a carbon atom in the alkylene group may be substituted with a halogen atom;

T represents a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded to a carbon atom in the alkylene group may be substituted with a halogen atom;

Y ₁ is a monovalent substituent in which one hydrogen atom is removed from a benzene ring, a monovalent substituent in which one hydrogen atom is removed from a naphthalene ring, a monovalent substituent in which one hydrogen atom is removed from a biphenyl ring, one hydrogen from a furan ring A monovalent substituent in which an atom is removed, a monovalent substituent in which one hydrogen atom is removed from a pyrrole ring, or a monovalent substituent in which one hydrogen atom is removed from an alicyclic hydrocarbon having 5 to 8 carbon atoms is represented, or selected from these substituents 2 to 6 identical or different substituents represent a monovalent substituent formed by bonding through a bonding group defined by B, and in all of these substituents, a hydrogen atom bonding to a carbon atom is independently -COOR ₀ (wherein R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or may be substituted with an alkyloxy group having 1 to 5 carbon atoms;

Y ₂ is a divalent substituent in which two hydrogen atoms are removed from a benzene ring, a divalent substituent in which two hydrogen atoms are removed from a naphthalene ring, a divalent substituent in which two hydrogen atoms are removed from a biphenyl ring, two hydrogens from a furan ring A divalent substituent in which an atom is removed, a divalent substituent in which two hydrogen atoms are removed from a pyrrole ring, a divalent substituent in which two hydrogen atoms are removed from an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof. represents a divalent substituent to be used, and in all of these substituents, a hydrogen atom bonded to a carbon atom is independently -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen atom, a carbon source may be substituted with an alkyl group having 1 to 5 atoms, or an alkyloxy group having 1 to 5 carbon atoms;

R represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or has the same definition as _{Y 1 ;}

X is a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, ※1-CH=CH-CO-O-※2, or ※1- O-CO-CH=CH-*2, *1 represents the bonding position with P in the formulas (1) to (6), *2 represents the formulas (1) to (6) It represents a bonding position with Q, and when the number of X is 2, X may be the same or different;

Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and hydrogen atoms bonded thereto are each independently -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, may be substituted with a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;

As for q1 and q2, one is 1 and the other is 0;

q3 is 0 or 1;

P and Q are each independently a divalent substituent in which two hydrogen atoms are removed from a benzene ring, a divalent substituent in which two hydrogen atoms are removed from a naphthalene ring, a divalent substituent in which two hydrogen atoms are removed from a biphenyl ring, furan A divalent substituent in which two hydrogen atoms are removed from a ring, a divalent substituent in which two hydrogen atoms are removed from a pyrrole ring, a divalent substituent in which two hydrogen atoms are removed from an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof represents a divalent substituent selected from the group consisting of; However, when X is *1-CH=CH-CO-O-*2, or *1-O-CO-CH=CH-*2, *1 is the formula (1) to (6) above. represents a bonding position with P, *2 indicates a bonding position with Q in the formulas (1) to (6), and P or Q on the side to which -CH=CH- is bonded is two hydrogen atoms from an aromatic ring. represents a divalent substituent from which ;

l1 is 0 or 1;

l2 is an integer from 0 to 2;

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

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

H and I are each independently a divalent substituent in which two hydrogen atoms are removed from a benzene ring, a divalent substituent in which two hydrogen atoms are removed from a naphthalene ring, a divalent substituent in which two hydrogen atoms are removed from a biphenyl ring, furan A divalent substituent selected from a divalent substituent in which two hydrogen atoms are removed from a ring, a divalent substituent in which two hydrogen atoms are removed from a pyrrole ring, and a combination thereof is shown.

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

wherein A, B, D, Y ₁ , X, Y ₂ , and R have the same definitions as above;

l represents an integer from 1 to 12;

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

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

[Formula 6]

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

In the formula, A, X, l, m, m1 and R have the same definitions as above.

[Formula 7]

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

In the formula, A, Y ₁ , X, l, m1 and m2 have the same definitions as above.

[Formula 8]

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

In the formula, A, X, l and m have the same definitions as above.

[Formula 9]

In addition, it is preferable that a side chain is a photosensitive side chain represented by following formula (18) or (19).

In the formula, A, B, Y ₁ , q1, q2, m1, and m2 have the same definitions as above.

R1 is a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms indicates.

[Formula 10]

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

In the formula, A, Y ₁ , X, l and m have the same definitions as above.

[Formula 11]

In addition, (A) side chain type polymer preferably has any one type of 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 definitions as above;

Y ₃ is a monovalent substituent in which one hydrogen atom is removed from a benzene ring, a monovalent substituent in which one hydrogen atom is removed from a naphthalene ring, a monovalent substituent in which one hydrogen atom is removed from a biphenyl ring, is one hydrogen from a furan ring A monovalent substituent in which an atom is removed, a monovalent substituent in which one hydrogen atom is removed from a nitrogen-containing heterocycle, a monovalent substituent in which one hydrogen atom is removed from an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a group consisting of combinations thereof represents a monovalent substituent selected from, and among all of these substituents, a hydrogen atom bonded to a carbon atom is each independently -NO ₂ , -CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms may be substituted with an alkyloxy group;

R ₃ is a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen atom, a monovalent substituent obtained by removing one hydrogen atom from a benzene ring, and 1 from a naphthalene ring A monovalent substituent in which two hydrogen atoms are removed, a monovalent substituent in which one hydrogen atom is removed from a biphenyl ring, a monovalent substituent in which one hydrogen atom is removed from a furan ring, a monovalent substituent in which one hydrogen atom is removed from a nitrogen-containing heterocyclic ring , a monovalent substituent in which one hydrogen atom has been removed from an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;

l represents the integer of 1-12, m represents the integer of 0-2, with the proviso that in Formula (23) and Formula (24), the sum of all m is 2 or more, Formula (25) and Formula ( In 26), the sum of all m is 1 or more, and m1, m2 and m3 each independently represent an integer of 1 to 3;

R ₂ is a hydrogen atom, -NO ₂ , -CN, a halogen atom, a monovalent substituent in which one hydrogen atom is removed from a benzene ring, a monovalent substituent in which one hydrogen atom is removed from a naphthalene ring, one hydrogen from a biphenyl ring A monovalent substituent in which an atom is removed, a monovalent substituent in which one hydrogen atom is removed from a furan ring, a monovalent substituent in which one hydrogen atom is removed from a nitrogen-containing heterocycle, and one hydrogen atom from an alicyclic hydrocarbon having 5 to 8 carbon atoms represents the removed monovalent substituent, an alkyl group, or an alkyloxy group;

Z ₁ and Z ₂ represent a single bond, -CO-, -CH ₂ O-, -CH=N-, or -CF ₂ -.

[Formula 12]

<<Method for producing a photosensitive side chain polymer having a dichroic dye in the side chain>>

The photosensitive side chain polymer capable of expressing the liquid crystallinity can be obtained by polymerizing a photoreactive side chain monomer having the photosensitive side chain, a liquid crystal side chain monomer, and a dichroic dye monomer.

[Photoreactive side chain monomer]

The photoreactive side chain monomer refers to a monomer capable of forming a polymer having a photosensitive side chain in the side chain portion of the polymer when the polymer is formed.

As a photoreactive group which a side chain has, the following structure and its derivative(s) are preferable.

[Formula 13]

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

Examples of the photoreactive side chain monomer include monomers selected from the following formulas M1-1 to M1-7 and M1-17 to M1-20.

[Formula 14]

[Formula 15]

[Formula 16]

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

[Formula 17]

(Wherein, R is OH or NH ₂ , 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-methacryloxyhexyl-1-oxy)cinnamic acid, 4-(6-acryloxyhexyl-1-oxy) R in Formula (1), such as cinnamic acid, 4-(3-methacryloxypropyl-1-oxy) cinnamic acid, and 4-(4-(6-methacryloxyhexyl-1-oxy) benzoyloxy) cinnamic acid OH, and 4-(6-methacryloxyhexyl-1-oxy)cinnamamide, 4-(6-acryloxyhexyl-1-oxy)cinnamamide, 4-(3-methacryloxypropyl- the R in the formula (M1-1), and 1-oxy) cinnamic amide and the like can be given to the NH _2.

[Liquid crystalline side chain monomer]

The liquid crystalline side chain monomer refers to a monomer in which a polymer derived from this monomer exhibits liquid crystallinity, and this polymer can form a mesogenic group in the side chain portion.

As a mesogenic group of a side chain, biphenyl or phenyl benzoate may contribute to form a mesogenic structure alone, or may contribute to form a mesogenic structure by hydrogen bonding between side chains such as benzoic acid. As a mesogenic group which a side chain has, the following structure is preferable.

[Formula 18]

More specific examples of the liquid crystalline side chain monomer include radicals such as hydrocarbon, (meth)acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene It is preferable that it is a structure which has a polymeric group comprised by at least 1 type selected from the group which consists of a polymeric group and siloxane, and has a side chain which consists of at least 1 type of said Formula (21)-(31).

Among these liquid crystalline 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 formulas M2-1 to M2-9 can also be used.

[Formula 19]

[Formula 20]

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

In addition, as a monomer having a substituent expressing liquid crystallinity, which is an example of the other monomer, a monomer represented by a formula selected from the group consisting of the following formulas M2-10 to M2-16 may be used.

[Formula 21]

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

[dichroic dye monomer]

The dichroic dye monomer refers to a monomer capable of forming a polymer having a dichroic dye in the side chain portion of the polymer when a polymer is formed, and is a compound in which a hydrogen atom of the dichroic dye is substituted with a polymerizable group. In addition, this polymeric group may be couple|bonded with the dichroic dye through a spacer.

The spacer is an alkylene group having 1 to 30 carbon atoms, a divalent substituent in which two hydrogen atoms are removed from a phenylene group or a carbocyclic compound, or a divalent substituent in which two hydrogen atoms are removed from a heterocyclic compound, and this alkylene group Among the divalent substituents in which two hydrogen atoms are removed from a phenylene group or a carbocyclic compound, or in a divalent substituent in which two hydrogen atoms have been removed from a heterocyclic compound, one or more hydrogen atoms are fluorine atoms or organic groups may be substituted. In addition, -CH ₂ CH ₂ - in the spacer may be substituted with -CH=CH-, and -CH ₂ - in the spacer is a divalent substituent obtained by removing two hydrogen atoms from a phenylene group or a carbocyclic compound, or It may be substituted with a divalent substituent in which two hydrogen atoms have been removed from the heterocyclic compound, and further, when any of the following groups are not adjacent to each other, they may be substituted with these groups; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH-, -CO-.

A dichroic dye means a dye which has the property from which the absorbance in the long-axis direction of a molecule|numerator differs from the absorbance in a short-axis direction.

It is preferable that a dichroic dye has an absorption maximum wavelength (λmax) in the range of 300-700 nm. Examples of such a dichroic dye include an acridine dye, an oxazine dye, a cyanine dye, a naphthalene dye, an azo dye, and an anthraquinone dye, and among these, an azo dye is preferable. Examples of the azo dye include a monoazo dye, a bisazo dye, a trisazo dye, a tetrakisazo dye, and a stilbenazo dye, and preferably a bisazo dye and a trisazo dye.

As an azo dye, the compound (Hereinafter, it is called "compound (b)" in some cases.) represented by Formula (b) is mentioned, for example.

A ¹ (-N=NA ² ) _p -N=NA ³ (b)

[In formula (b),

A ¹ and A ³ each independently represent an optionally substituted phenyl group, an optionally substituted naphthyl group, or an optionally substituted monovalent heterocyclic group. A ² represents an optionally substituted 1,4-phenylene group, an optionally substituted naphthalene-1,4-diyl group, or an optionally substituted divalent heterocyclic group. p represents the integer of 1-4. When p is an integer of 2 or more, a plurality of A ² may be independently the same or different from each other.]

Examples of the monovalent heterocyclic group include groups in which one hydrogen atom is removed from heterocyclic compounds such as quinoline, thiazole, benzothiazole, thienothiazole, imidazole, benzoimidazole, oxazole and benzoxazole. Examples of the divalent heterocyclic group include groups in which two hydrogen atoms have been removed from the heterocyclic compound.

Substituents optionally included in the phenyl group, naphthyl group and monovalent heterocyclic group for A ¹ and A ³ , and the 1,4-phenylene group, naphthalene-1,4- ^{diyl group and divalent heterocyclic group for A 2 include} , an alkyl group having 1 to 4 carbon atoms; an alkoxy group having 1 to 4 carbon atoms, such as a methoxy group, an ethoxy group, and a butoxy group; a fluorinated alkyl group having 1 to 4 carbon atoms, such as a trifluoromethyl group; cyano group; nitro group; halogen atom; A substituted or unsubstituted amino group such as an amino group, a diethylamino group and a pyrrolidino group (a substituted amino group is an amino group having one or two C1-C6 alkyl groups, or two substituted alkyl groups bonded to each other to have 2 carbon atoms It refers to the amino group forming the alkanediyl group of to 8. The unsubstituted amino group is -NH ₂ ).

The alkyl group having 1 to 6 carbon atoms may be either linear or branched, and may include a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 1,1-dimethylbutyl group, 1-ethylbutyl group, 1,1,2-trimethylpropyl group, etc. are mentioned.

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

[Formula 22]

[Formula 23]

[In formulas (2-1) to (2-6),

B ¹ to B ²⁰ are each independently 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 (a substituted amino group and an unsubstituted amino group) The definition is as described above), a chlorine atom or a trifluoromethyl group.

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

When n1 is 2 or more, a plurality of B ² may be the same or different independently of each other,

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

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

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

As for the said anthraquinone dye, the compound represented by Formula (2-7) is preferable.

[Formula 24]

[In formula (2-7),

R ¹ to R ⁸ each independently represent a hydrogen atom, -R ^x , -NH ₂ , -NHR ^x , -NR ^x ₂ , -SR ^x or a halogen atom.

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

As for the said oxazone dye, the compound represented by Formula (2-8) is preferable.

[Formula 25]

R ⁹ to R ¹⁵ each independently represent a hydrogen atom, -R ^x , -NH ₂ , -NHR ^x , -NR ^x ₂ , -SR ^x or a halogen atom.

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

As for the said acridine dye, the compound represented by Formula (2-9) is preferable.

[Formula 26]

[In formula (2-9),

R ¹⁶ to R ²³ each independently represent a hydrogen atom, -R ^x , -NH ₂ , -NHR ^x , -NR ^x ₂ , -SR ^x or a halogen atom.

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

^{Examples of the alkyl group having 1 to 6 carbon atoms represented by R x} in formulas (2-7), (2-8) and (2-9) include a methyl group, an ethyl group, a propyl group, a butyl group, and a pen A tyl group, a hexyl group, etc. are mentioned, A phenyl group, a toluyl group, a xylyl group, a naphthyl group, etc. are mentioned as a C6-C12 aryl group.

As for the said cyanine pigment|dye, the compound represented by Formula (2-10), and the compound represented by Formula (2-11) are preferable.

[Formula 27]

[In formula (2-10),

D ¹ and D ² each independently represent a group in any one of formulas (2-10a) to (2-10d).

[Formula 28]

n5 represents an integer of 1 to 3.]

[Formula 29]

[In formula (2-11),

D ³ and D ⁴ each independently represent a group in any one of formulas (2-11a) to (2-11h).

[Formula 30]

n6 represents an integer of 1 to 3.]

More specific examples of the dichroic dye monomer include radicals such as hydrocarbon, (meth)acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene It is preferable that it is a structure which has the polymeric group comprised by at least 1 sort(s) chosen from the group which consists of a polymeric group and siloxane, and the above-mentioned dichroic dye.

Moreover, as a commercial item of a dichroic dye monomer, Disperse Red 1 acrylate, Disperse red 1 methacrylate, and Disperse yellow 7 methacrylate (made by ALDRICH) are mentioned, for example.

(A) A side chain type polymer|macromolecule can be obtained by the copolymerization reaction of the photoreactive side chain monomer which expresses the above-mentioned liquid crystal, and a dichroic dye monomer. In addition, the copolymerization of a photoreactive side chain monomer, a liquid crystalline side chain monomer, and a dichroic dye monomer that does not express liquid crystallinity, or a photoreactive side chain monomer that expresses liquid crystallinity, a liquid crystalline side chain monomer, and a dichroic dye monomer can be obtained by Furthermore, it can copolymerize with other monomers in the range which does not impair the liquid crystalline expression ability.

Examples of the other monomer include an industrially available radical polymerizable monomer.

Specific examples of the other monomer include unsaturated carboxylic acid, acrylic acid ester compound, methacrylic acid ester compound, maleimide compound, acrylonitrile, maleic anhydride, styrene compound, and vinyl compound.

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

Examples of the acrylic acid ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl 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-tricyclodecyl acrylate , and 8-ethyl-8-tricyclodecyl acrylate.

As a methacrylic acid ester compound, For example, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate Rate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methacrylate Toxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-propyl -2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate, etc. are mentioned.

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

As a styrene compound, styrene, methyl styrene, chloro styrene, bromostyrene etc. are mentioned, for example.

As a maleimide compound, maleimide, N-methyl maleimide, N-phenyl maleimide, N-cyclohexyl maleimide, etc. are mentioned, for example.

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

When the content of the photoreactive side chain in the side chain polymer is less than 10 mol% based on the total amount of side chains, the coating film formed from the polymer composition of the present invention may not sufficiently exhibit the effect as a liquid crystal aligning 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%, furthermore 10 mol% to 70 mol%, based on the total amount of side chains. desirable.

When the content of liquid crystalline side chains in the side chain polymer is higher than 90 mol% based on the total amount of side chains, the content of photoreactive side chains becomes less than 10 mol% based on the total amount of side chains, so formed from the polymer composition of the present invention A coating film may not fully exhibit the effect as a liquid crystal aligning film.

The content of the dichroic dye side chain in the side chain polymer of the present invention is preferably 0.2 mol% to 20 mol%, more preferably 0.5 mol% to 15 mol%, and 1 mol% to 10 mol% based on the total amount of side chains. More preferred is mole %.

When the content of the dichroic dye side chain in the side chain polymer is less than 0.2 mol% based on the total amount of side chains, the coating film formed from the polymer composition of the present invention may not sufficiently exhibit the effect as a liquid crystal aligning film.

The side chain polymer of the present invention may contain other side chains other than the photoreactive side chain, the liquid crystalline side chain and the dichroic dye side chain. The content is the remainder when the sum of the content of the photoreactive side chain, the liquid crystalline side chain and the dichroic dye side chain is less than 100%.

It does not specifically limit about the manufacturing method of the side chain type polymer|macromolecule of this embodiment, The general-purpose method handled industrially can be used. Specifically, it can be produced by cationic polymerization, radical polymerization, or anionic polymerization using a vinyl group of a liquid crystalline side chain monomer or a photoreactive side chain monomer. Among these, radical polymerization is particularly preferable from the viewpoint of easiness of reaction control and the like.

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

A radical thermal polymerization initiator is a compound which generates radicals by heating to a decomposition temperature or more. As such a radical thermal polymerization initiator, for example, ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), hydroperoxides ( Hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketals (dibutyl peroxide, etc.) oxycyclohexane, etc.), alkyl peresters (peroxyneodecanoic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy2-ethylcyclohexanoic acid-tert-amyl ester, etc.), persulfates compounds (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), azo compounds (such as isobisisobutyronitrile and 2,2'-di(2-hydroxyethyl)isobisisobutyronitrile) can These radical thermal polymerization initiators may be used individually by 1 type, or may be used in combination of 2 or more type.

A radical photoinitiator will not be specifically limited if it is a compound which starts radical polymerization by light irradiation. Examples of such radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexylphenylketone, isopropyl Benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methyl Thio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,4-dimethylaminoethyl benzoate, 4- Dimethylaminobenzoate isoamyl, 4,4'-di(t-butylperoxycarbonyl)benzophenone, 3,4,4'-tri(t-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 ', 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-[pN,N-di(ethoxycarbonylmethyl)]-2,6-di(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)benzthiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis(7-diethylaminocoumarin), 2-(o-chloro Phenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis (4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2 '-biimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4 ',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-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-dode Silcarbazole, 1-hydroxycyclohexylphenyl ketone, bis(5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl) )-phenyl) titanium, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(t-hexylperoxycarbonyl)benzo Phenone, 3,3'-di(methoxycarbonyl)-4,4'-di(t-butylperoxycarbonyl)benzophenone, 3,4'-di(methoxycarbonyl)-4,3' -di(t-butylperoxycarbonyl)benzophenone, 4,4'-di(methoxycarbonyl)-3,3'-di(t-butylperoxycarbonyl)benzophenone, 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 etc. are mentioned. These compounds may be used independently and may be used in mixture of 2 or more.

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

The organic solvent used for the polymerization of the photosensitive side chain polymer capable of expressing liquid crystallinity is not particularly limited as long as the resulting polymer is dissolved. The specific example is given below.

N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, Pyridine, dimethyl sulfone, hexamethyl sulfoxide, γ-butyrolactone, isopropyl alcohol, methoxymethyl pentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl Ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, 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, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol mono Acetate monomethyl ether, dipropylene glycol 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, acetic acid Ethyl, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, 3-methoxymethylpropionate, 3-ethoxymethylethylethylpropionate, 3-methoxyethylpropionate, 3-ethoxypropionic acid, 3- Methoxypropionic acid, 3-methoxypropionate propyl, 3-methoxybutylpropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N,N-dimethylpropanamide, 3- Ethoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanami de and the like.

These organic solvents may be used individually or may be used in mixture. Furthermore, even if it is a solvent which does not dissolve the polymer|macromolecule produced|generated, it can also be mixed with the organic solvent mentioned above in the range in which the produced|generated polymer does not precipitate, and can also be used.

In addition, since oxygen in the organic solvent inhibits the polymerization reaction in radical polymerization, it is preferable to use the organic solvent degassed to the extent possible.

The polymerization temperature at the time of radical polymerization can be selected from an arbitrary temperature of 30°C to 150°C, and is preferably in the range of 50°C to 100°C. In addition, the reaction can be carried out at an arbitrary concentration. If the concentration is too low, it becomes difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring becomes difficult. Therefore, the monomer concentration is preferably Preferably it is 1 mass % - 50 mass %, More preferably, it is 5 mass % - 30 mass %. In the initial stage of the reaction, it is carried out at a high concentration, and thereafter, an organic solvent can be added.

In the radical polymerization reaction described above, when the ratio of the radical polymerization initiator is large with respect to the monomer, the molecular weight of the obtained polymer becomes small, and when the ratio of the radical polymerization initiator is small, the molecular weight of the obtained polymer becomes large. It is preferable that it is from 10 mol% to 10 mol%. In addition, during polymerization, various monomer components, solvents, initiators, etc. may be added.

[Recovery of polymer]

In the case of recovering the resulting polymer from the reaction solution of the photosensitive side chain polymer capable of expressing liquid crystallinity obtained by the above-mentioned reaction, the reaction solution may be poured into a poor solvent to precipitate these polymers. Examples of the poor solvent used for precipitation include methanol, acetone, hexane, heptane, butyl cellsolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, and water. have. The polymer charged and precipitated in the poor solvent can be collected by filtration, and then dried under normal pressure or reduced pressure at room temperature or by heating. In addition, if the precipitation-recovered polymer is redissolved in an organic solvent and the operation of re-precipitating and recovering is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the poor solvent at this time include alcohols, ketones, and hydrocarbons, and it is preferable to use three or more types of poor solvents selected from these, since the efficiency of purification further increases.

The molecular weight of the (A) side chain type polymer of the present invention is the weight average obtained in terms of polystyrene measured by the GPC (Gel Permeation Chromatography) method, when the strength of the resulting coating film, workability during coating film formation, and the uniformity of the coating film are considered. As for molecular weight, 2000-1000000 are preferable, More preferably, it is 5000-100000.

<(B) component>

The polymer composition of this invention can also contain the compound represented by a following formula (c) as (B)component.

[Formula 31]

( ^{Wherein, any 3 to 5 of R 101} , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ and R ¹⁰⁵ are each independently a hydrogen atom, a halogen atom, a C ₁ to C ₆ alkyl group, or a C ₁ to C ₆ haloalkyl group , C ₁ to C ₆ alkoxy group, C ₁ to C ₆ haloalkoxy group, C ₃ to C ₈ cycloalkyl group, C ₃ to C ₈ halocycloalkyl group, C ₂ to C ₆ alkenyl group, C ₂ to C ₆ haloalke Nyl group, C ₃ to C ₈ cycloalkenyl group, C ₃ to C ₈ halocycloalkenyl group, C ₂ to C ₆ alkynyl group, C ₂ to C ₆ haloalkynyl group, (C ₁ to C ₆ alkyl)carbonyl group, (C ₁ to C ₆ haloalkyl)carbonyl group, (C ₁ to C ₆ alkoxy)carbonyl group, (C ₁ to C ₆ haloalkoxy)carbonyl group, (C ₁ to C ₆ alkylamino)carbonyl group, (C ₁ to C ₆ haloalkyl) represents a substituent selected from an aminocarbonyl group, a di(C ₁ to C ₆ alkyl)aminocarbonyl group, a cyano group and a nitro group, and any 3 to 4 of ^{R 101} , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ and R ^{105 are defined above} When , R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ and R ¹⁰⁵ the other one or two of the following formula (c-2)

[Formula 32]

(In formula (c-2), the broken line indicates the number of bonds, and R ¹⁰⁶ is an alkylene group having 1 to 30 carbon atoms, a phenylene group, or a divalent substituent in which two hydrogen atoms are removed from a carbocyclic compound or a heterocyclic compound. A divalent substituent in which two hydrogen atoms have been removed, and one of the divalent substituents in which two hydrogen atoms have been removed from an alkylene group, a phenylene group, or a carbocyclic compound, or two hydrogen atoms have been removed from a heterocyclic compound one or a plurality of hydrogen atoms, fluorine atoms, or organic groups may also be substituted, in R ¹⁰⁶ -CH ₂ CH ₂ -. -CH ₂ is in, and R ¹⁰⁶ may be substituted with -CH = CH- - may be substituted with a phenylene group, a divalent substituent in which two hydrogen atoms are removed from a carbocyclic compound, or a divalent substituent in which two hydrogen atoms are removed from a heterocyclic compound, further, -CH ₂ - in ^{R 106 is} , -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH-, and -CO-, unless a divalent group selected from the group consisting of may be substituted with a group. R ¹⁰⁷ represents a hydrogen atom or a methyl group.) represents the group represented by), and n represents 0 or 1.)

As a halogen atom in this specification, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned. In addition, the notation of "halo" in this specification also represents these halogen atoms.

The notation of the C _a to C _b alkyl group in the present specification represents a linear or branched hydrocarbon group having a to b carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group, 1 ,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 1,1-dimethylbutyl group, 1, 3-dimethylbutyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group etc. are mentioned as a specific example, Each is selected from the range of the designated number of carbon atoms.

In the present specification, _{the notation of the C a} to C _b haloalkyl group represents a linear or branched hydrocarbon group having a to b carbon atoms in which a hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom, in which case , when substituted with two or more halogen atoms, these halogen atoms may be the same as or different from each other. For example, fluoromethyl group, chloromethyl group, bromomethyl group, iodomethyl group, difluoromethyl group, chlorofluoromethyl group, dichloromethyl group, bromofluoromethyl group, trifluoromethyl group, chlorodifluoromethyl group, dichlorofluoro Methyl group, trichloromethyl group, bromodifluoromethyl group, bromochlorofluoromethyl group, dibromofluoromethyl group, 2-fluoroethyl group, 2-chloroethyl group, 2-bromoethyl group, 2,2-difluoro Ethyl group, 2-chloro-2-fluoroethyl group, 2,2-dichloroethyl group, 2-bromo-2-fluoroethyl group, 2,2,2-trifluoroethyl group, 2-chloro-2,2-di Fluoroethyl group, 2,2-dichloro-2-fluoroethyl group, 2,2,2-trichloroethyl group, 2-bromo-2,2-difluoroethyl group, 2-bromo-2-chloro-2 -Fluoroethyl group, 2-bromo-2,2-dichloroethyl group, 1,1,2,2-tetrafluoroethyl group, pentafluoroethyl group, 1-chloro-1,2,2,2-tetrafluoro Ethyl group, 2-chloro-1,1,2,2-tetrafluoroethyl group, 1,2-dichloro-1,2,2-trifluoroethyl group, 2-bromo-1,1,2,2-tetra Fluoroethyl group, 2-fluoropropyl group, 2-chloropropyl group, 2-bromopropyl group, 2-chloro-2-fluoropropyl group, 2,3-dichloropropyl group, 2-bromo-3- Fluoropropyl group, 3-bromo-2-chloropropyl group, 2,3-dibromopropyl group, 3,3,3-trifluoropropyl group, 3-bromo-3,3-difluoro Propyl group, 2,2,3,3-tetrafluoropropyl group, 2-chloro-3,3,3-trifluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 1 ,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, 2,2,3,4,4,4-hexafluorobutyl group, 2,2,3,3,4,4,4-heptafluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, nonafluorobutyl group, 4-chloro-1,1,2,2,3,3,4,4-octafluoro Robutyl group, 2-fluoro-2-methylpropyl group, 2-chloro-1,1-dimethylethyl group, 2-bromo-1,1-dimethylethyl group, 5-chloro-2,2,3,4, A 4,5,5-heptafluoropentyl group, a tridecafluorohexyl group, etc. are mentioned as a specific example, Each is selected from the range of the designated number of carbon atoms.

The notation of the C _a to C _b cycloalkyl group in the present specification represents a cyclic hydrocarbon group having a to b carbon atoms, and can form a monocyclic or complex ring structure from a 3-membered ring to a 6-membered ring. In addition, each ring may be arbitrarily substituted with an alkyl group within the range of the designated number of carbon atoms. For example, cyclopropyl group, 1-methylcyclopropyl group, 2-methylcyclopropyl group, 2,2-dimethylcyclopropyl group, 2,2,3,3-tetramethylcyclopropyl group, cyclobutyl group, cyclophene Tyl group, 2-methylcyclopentyl group, 3-methylcyclopentyl group, cyclohexyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, bicyclo[2.2.1]heptane- 2-yl group etc. are mentioned as a specific example, It is selected from the range of each designated number of carbon atoms.

The notation of the C _a to C _b halocycloalkyl group in the present specification represents a cyclic hydrocarbon group having a to b carbon atoms in which a hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom, and a 3-membered ring to 6-membered ring A monocyclic or complex ring structure up to a ring can be formed. In addition, each ring may be arbitrarily substituted with an alkyl group within the range of the specified number of carbon atoms, and substitution with a halogen atom may be a ring structure moiety, a side chain moiety, or both, and further, two or more When substituted with a halogen atom, these halogen atoms may be the same as or different from each other. For example, 2,2-difluorocyclopropyl group, 2,2-dichlorocyclopropyl group, 2,2-dibromocyclopropyl group, 2,2-difluoro-1-methylcyclopropyl group, 2 ,2-dichloro-1-methylcyclopropyl group, 2,2-dibromo-1-methylcyclopropyl group, 2,2,3,3-tetrafluorocyclobutyl group, 2- (trifluoromethyl) A cyclohexyl group, 3-(trifluoromethyl)cyclohexyl group, 4-(trifluoromethyl)cyclohexyl group, etc. are mentioned as a specific example, Each is selected from the range of the designated number of carbon atoms.

In the present specification, _{the notation of the C a} to C _b alkenyl group represents an unsaturated hydrocarbon group that is a straight or branched chain having a to b carbon atoms, and has one or two or more double bonds in the molecule, e.g. For example, a vinyl group, 1-propenyl group, 2-propenyl group, 1-methylethenyl group, 2-butenyl group, 1-methyl-2-propenyl group, 2-methyl-2-propenyl group, 2-pentenyl group, 2-methyl-2-butenyl group, 3-methyl-2-butenyl group, 2-ethyl-2-propenyl group, 1,1-dimethyl-2-propenyl group, 2-hexenyl group, 2-methyl-2- A pentenyl group, a 2,4-dimethyl-2,6-heptadienyl group, a 3,7-dimethyl-2,6-octadienyl group, etc. are mentioned as a specific example, Each is selected from the range of the designated number of carbon atoms.

In the present specification, _{the notation of the C a} to C _b haloalkenyl group is a straight or branched chain having a to b carbon atoms in which a hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom, and in the molecule Represents an unsaturated hydrocarbon group having one or two or more double bonds. In this case, when substituted by two or more halogen atoms, these halogen atoms may be the same as or different from each other. For example, 2,2-dichlorovinyl group, 2-fluoro-2-propenyl group, 2-chloro-2-propenyl group, 3-chloro-2-propenyl group, 2-bromo-2-propenyl group, 3 -Bromo-2-propenyl group, 3,3-difluoro-2-propenyl group, 2,3-dichloro-2-propenyl group, 3,3-dichloro-2-propenyl group, 2,3-dibro Mo-2-propenyl group, 2,3,3-trifluoro-2-propenyl group, 2,3,3-trichloro-2-propenyl group, 1- (trifluoromethyl) ethenyl group, 3-chloro -2-butenyl group, 3-bromo-2-butenyl group, 4,4-difluoro-3-butenyl group, 3,4,4-trifluoro-3-butenyl group, 3-chloro-4, 4,4-trifluoro-2-butenyl group, 3-bromo-2-methyl-2-propenyl group, etc. are mentioned as a specific example, Each is selected from the range of the designated number of carbon atoms.

The notation of the C _a to C _b cycloalkenyl group in the present specification represents an unsaturated hydrocarbon group having a cyclic and one or two or more double bonds having a to b carbon atoms, and ranges from a 3-membered ring to a 6-membered ring. may form a monocyclic or complex ring structure. In addition, each ring may be arbitrarily substituted with an alkyl group within the range of the designated number of carbon atoms, and further, the double bond may be either endo- or exo-. For example, 2-cyclopenten-1-yl group, 3-cyclopenten-1-yl group, 2-cyclohexen-1-yl group, 3-cyclohexen-1-yl group, bicyclo[2.2.1]-5-heptene -2-yl group etc. are mentioned as a specific example, It is selected from the range of each designated number of carbon atoms.

In the present specification, _{the notation of the C a} to C _b halocycloalkenyl group is a cyclic having a to b carbon atoms in which a hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom, and 1 or 2 It represents an unsaturated hydrocarbon group having the above double bond, and can form a monocyclic or complex ring structure from a 3-membered ring to a 6-membered ring. In addition, each ring may be arbitrarily substituted with an alkyl group within the range of the designated number of carbon atoms, and further, the double bond may be either endo- or exo-. In addition, substitution by a halogen atom may be a ring structure moiety, a side chain moiety, or both thereof. When substituted with two or more halogen atoms, these halogen atoms may be the same as or different from each other. You may. For example, 2-chlorobicyclo[2.2.1]-5-hepten-2-yl group etc. are mentioned as a specific example, It is selected from the range of each designated number of carbon atoms.

In the present specification, _{the notation of the C a} to C _b alkynyl group represents an unsaturated hydrocarbon group that is linear or branched having a to b carbon atoms and has one or two or more triple bonds in the molecule, examples For example, ethynyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, 1-methyl-2-propynyl group, 2-pentynyl group, 1-methyl-2-butynyl group, 1,1-dimethyl-2 -propynyl group, 2-hexynyl group, etc. are mentioned as a specific example, Each is selected from the range of the designated number of carbon atoms.

In the present specification, _{the notation of the C a} to C _b haloalkynyl group is a straight or branched chain having a to b carbon atoms, in which a hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom, and in the molecule Represents an unsaturated hydrocarbon group having one or two or more triple bonds. In this case, when substituted by two or more halogen atoms, these halogen atoms may be the same as or different from each other. For example, 2-chloroethynyl group, 2-bromoethynyl group, 2-iodoethynyl group, 3-chloro-2-propynyl group, 3-bromo-2-propynyl group, 3-iodine-2-propy A nyl group etc. are mentioned as a specific example, It is selected from the range of each designated number of carbon atoms.

The notation of the C _a to C _b alkoxy group in the present specification represents an alkyl-O- group having the above meaning consisting of a to b carbon atoms, for example, a methoxy group, an ethoxy group, an n-propyloxy group, i -Propyloxy group, n-butyloxy group, i-butyloxy group, s-butyloxy group, t-butyloxy group, n-pentyloxy group, n-hexyloxy group etc. are mentioned as a specific example, each It is selected from the range of the specified number of carbon atoms.

The notation of the C _a to C _b haloalkoxy group in the present specification represents a haloalkyl-O- group having the above meaning consisting of a to b carbon atoms, for example, a difluoromethoxy group, a trifluoromethoxy group , chlorodifluoromethoxy group, bromodifluoromethoxy group, 2-fluoroethoxy group, 2-chloroethoxy group, 2,2,2-trifluoroethoxy group, 1,1,2,2 , -Tetrafluoroethoxy group, 2-chloro-1,1,2-trifluoroethoxy group, 2-bromo-1,1,2-trifluoroethoxy group, pentafluoroethoxy group , 2,2-dichloro-1,1,2-trifluoroethoxy group, 2,2,2-trichloro-1,1-difluoroethoxy group, 2-bromo-1,1,2 ,2-tetrafluoroethoxy group, 2,2,3,3-tetrafluoropropyloxy group, 1,1,2,3,3,3-hexafluoropropyloxy group, 2,2,2- Specific examples include trifluoro-1-(trifluoromethyl)ethoxy group, heptafluoropropyloxy group, 2-bromo-1,1,2,3,3,3-hexafluoropropyloxy group and each selected from the range of the designated number of carbon atoms.

The expression of the (C _a to C _b alkyl) carbonyl group in the present specification represents an alkyl-C(O)- group having the above meaning consisting of a to b carbon atoms, for example, an acetyl group, a propionyl group, a buty Lyl group, isobutyryl group, valeryl group, isovaleryl group, 2-methylbutanoyl group, pivaloyl group, hexanoyl group, heptanoyl group etc. are mentioned as a specific example, Each is selected from the range of the designated number of carbon atoms.

The expression of the (C _a to C _b haloalkyl) carbonyl group in the present specification represents a haloalkyl-C (O) - group with the above meaning consisting of a to b carbon atoms, for example, a fluoroacetyl group, chloro Acetyl group, difluoroacetyl group, dichloroacetyl group, trifluoroacetyl group, chlorodifluoroacetyl group, bromodifluoroacetyl group, trichloroacetyl group, pentafluoropropionyl group, heptafluorobutanoyl group , 3-chloro-2,2-dimethylpropanoyl group, etc. are given as specific examples, and each is selected from the range of the designated number of carbon atoms.

The expression of the (C _a to C _b alkoxy) carbonyl group in the present specification represents an alkyl-OC(O)- group having the above meaning consisting of a to b carbon atoms, for example, a methoxycarbonyl group, an ethoxycarbonyl group, Specific examples include n-propyloxycarbonyl group, i-propyloxycarbonyl group, n-butoxycarbonyl group, i-butoxycarbonyl group, and t-butoxycarbonyl group, each selected from the range of the designated number of carbon atoms.

The description of the (C _a to C _b haloalkoxy) carbonyl group in the present specification represents a haloalkyl-OC(O)- group having the above meaning consisting of a to b carbon atoms, for example, a 2-chloroethoxycarbonyl group , 2,2-difluoroethoxycarbonyl group, 2,2,2-trifluoroethoxycarbonyl group, 2,2,2-trichloroethoxycarbonyl group, etc. are given as specific examples, and each designated number of carbon atoms is selected from the range of

The expression of the (C _a to C _b alkylamino) carbonyl group in the present specification represents a carbamoyl group in which one of the hydrogen atoms is substituted with an alkyl group having the above meaning consisting of a to b carbon atoms, for example, Methyl carbamoyl group, ethyl carbamoyl group, n-propyl carbamoyl group, i-propyl carbamoyl group, n-butyl carbamoyl group, i-butyl carbamoyl group, s-butyl carbamoyl group, t-butyl carbamo group A diary etc. are mentioned as a specific example, Each is selected from the range of the designated number of carbon atoms.

In the present specification, _{the expression of the (C a} to C _b haloalkylamino) carbonyl group represents a carbamoyl group in which one of the hydrogen atoms is substituted with a haloalkyl group having a to b carbon atoms, for example, For example, 2-fluoroethyl carbamoyl group, 2-chloroethyl carbamoyl group, 2,2-difluoroethyl carbamoyl group, 2,2,2-trifluoroethyl carbamoyl group, etc. are mentioned as specific examples. and is selected from the range of each designated number of carbon atoms.

In the present specification, _{the notation of the di(C a} to C _b alkyl) aminocarbonyl group is substituted with an alkyl group in which both hydrogen atoms are the same or each has a to b carbon atoms, which may be different from each other. represents a carbamoyl group, for example, N,N-dimethylcarbamoyl group, N-ethyl-N-methylcarbamoyl group, N,N-diethylcarbamoyl group, N,N-di-n-propylcarbamo group A diyl group, N,N-di-n-butylcarbamoyl group, etc. are mentioned as a specific example, Each is selected from the range of the designated number of carbon atoms.

^{Substituents R 101} , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ and R ^{105 in} the cinnamic acid or benzoic acid derivative having the structure represented by formula (c) are, among them, each independently a hydrogen atom, a halogen atom, C ₁ to C ₆ It is preferably a substituent selected from an alkyl group, a C ₁ to C ₆ haloalkyl group, a C ₁ to C ₆ alkoxy group, a C ₁ to C ₆ haloalkoxy group, a cyano group and a nitro group.

In addition, R ¹⁰³ is preferably ^{a substituent other than a hydrogen atom in the definitions of R 101} , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ and R ^{105 above} , from the viewpoint of orientation sensitivity, a halogen atom, a C ₁ to C ₆₆ alkyl group , C ₁ to C ₆ A substituent selected from a haloalkyl group, a C ₁ to C ₆ alkoxy group, a C ₁ to C ₆ haloalkoxy group, a cyano group and a nitro group is more preferable.

Moreover, it ^{is also preferable that the substituent of any 1 or 2 of R 101} , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ and R ¹⁰⁵ is a group represented by the formula (c-2), and among these, R ¹⁰³ is a group represented by the formula (c-2) It is preferable that it is a group represented by ). Examples of such a monomer include a monomer selected from the above formulas M1-1 to M1-7 and M1-17 to M1-21 as a monomer having a cinnamic acid group. Moreover, as a monomer which has a benzoic acid group, the monomer chosen from said Formula M2-1 - M2-9 is mentioned.

Examples of such cinnamic acid and its derivatives include cinnamic acid derivatives such as cinnamic acid, 4-methoxycinnamic acid, 4-ethoxycinnamic acid, 4-propoxycinnamic acid, and 4-fluorocinnamic acid; 4-(6-methacryloxyhexyl-1-oxy)cinnamic acid, 4-(6-acryloxyhexyl-1-oxy)cinnamic acid, 4-(3-methacryloxypropyl-1-oxy)cinnamic acid, 4-( The monomer which has cinnamic acid groups, such as 4-(6-methacryloxyhexyl-1-oxy) benzoyloxy) cinnamic acid, etc. are mentioned.

In addition, as such benzoic acid and its derivatives, benzoic acid derivatives such as benzoic acid, 4-methoxybenzoic acid, 4-ethoxybenzoic acid, 4-propoxybenzoic acid, and 4-fluorobenzoic acid; 4-(6-methacryloxyhexyl-1-oxy)benzoic acid, 4-(6-acryloxyhexyl-1-oxy)benzoic acid, 4-(3-methacryloxypropyl-1-oxy)benzoic acid, 4-( The monomer which has benzoic acid groups, such as 4-(6-methacryloxyhexyl-1-oxy) benzoyloxy) benzoic acid, etc. are mentioned.

It is preferable that content in the case of containing (B) component in the polymer composition of this invention is 3 mass parts - 100 mass parts per 100 mass parts of side chain type polymer|macromolecule of (A) component. (B) The improvement of an irradiation dose margin is not seen as content of a component is 3 mass parts or less. Moreover, the solvent tolerance of the cured film obtained as content of (B) component exceeds 100 mass parts and is an excessive thing may fall.

<Organic solvent>

The organic solvent used for the polymer composition used for this invention will not be specifically limited if it is an organic solvent which dissolves a resin component. The specific example is given below.

N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone Don, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, γ-butyrolactone, 3-methoxy-N,N-dimethylpropanamide, 3-ethoxy-N,N-dimethylpropane Amide, 3-butoxy-N,N-dimethylpropanamide, 1,3-dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclo Hexanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy-4-methyl-2-pentanone, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl Ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol 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, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cell Losolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, 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, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol Propylene glycol monoacetate monomethyl ether, dipropylene glycol 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, tri Propylene 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, propylene glycol monoethyl ether, Methyl pyruvate, ethyl pyruvate, 3-methoxymethylpropionate, 3-ethoxymethylethylpropionate, 3-methoxyethylpropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionate propyl, 3-methyl Butyl oxypropionate, 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, methyl lactate ester, ethyl lactate ester, and lactate n-propyl ester, lactate n-butyl ester, and lactate isoamyl ester. These may be used individually or may be used in mixture.

<Polymer composition>

The polymer composition of the present invention contains (A) a photosensitive side chain polymer that has a dichroic dye in the side chain and exhibits liquid crystallinity in a predetermined temperature range, and an organic solvent. Moreover, the compound represented by the said Formula (c) is contained as (B) component as needed.

[Preparation of polymer composition]

It is preferable that the polymer composition used for this invention is prepared as a coating liquid so that it may become suitable for formation of an orientation layer. That is, the polymer composition used in the present invention is preferably prepared as a solution in which a resin component for forming a resin film is dissolved in an organic solvent. Here, the resin component is a resin component containing a photosensitive side chain polymer that has a dichroic dye in the side chain described above and can express liquid crystallinity. At this time, the content of the resin component is preferably 1% by mass to 20% by mass, more preferably 3% by mass to 15% by mass, and particularly preferably 3% by mass to 10% by mass.

In the polymer composition of the present invention, the above-mentioned resin component may be a photosensitive side-chain type polymer capable of expressing liquid crystallinity, all of which have a dichroic dye in the above-mentioned side chain, liquid crystal expression ability and photosensitivity performance Polymers other than these may be mixed in a range that does not damage the polymer. At this time, content of the other polymer in a resin component is 0.5 mass % - 80 mass %, Preferably they are 1 mass % - 50 mass %.

Such other polymers include, for example, poly(meth)acrylates, polyamic acids, polyimides, and the like, and polymers other than the photosensitive side chain polymers capable of exhibiting liquid crystallinity are exemplified.

The polymer composition used for this invention may contain components other than said (A) and an organic solvent. Examples thereof include, but are not limited to, compounds that improve film thickness uniformity and surface smoothness when a polymer composition is applied, and compounds that improve adhesion between an alignment layer and a substrate.

As a compound which improves the uniformity of a film thickness and surface smoothness, a fluorine-type surfactant, a silicone type surfactant, a nonionic surfactant, etc. are mentioned.

More specifically, for example, FTOP (registered trademark) 301, EF303, EF352 (manufactured by Tochem Products), Megapac (registered trademark) F171, F173, R-30 (manufactured by DIC), Fluorad FC430, FC431 ( Sumitomo 3M Co., Ltd.), AsahiGuard (registered trademark) AG710 (manufactured by Asahi Glass Co., Ltd.), Sufflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical), etc. have. To 100 parts by mass of the resin component contained in the polymer composition, the amount of the surfactant used is preferably 0.01 parts by mass to 2 parts by mass, more preferably 0.01 parts by mass to 1 part by mass.

As a specific example of the compound which improves the adhesiveness of an orientation layer and a board|substrate, the functional silane containing compound etc. which are shown below are mentioned.

For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3 -Aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxy Carbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetri Amine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl Acetate, 9-triethoxysilyl-3,6-diazanonylacetate, 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-aminopropyltri Ethoxysilane etc. are mentioned.

Furthermore, in addition to the improvement of the adhesiveness of a board|substrate and an orientation layer, in order to provide heat resistance, the additive of the following phenoplast type|system|group or an epoxy group containing compound can also be contained in a polymer composition. Although a specific phenoplast type additive is shown below, it is not limited to this structure.

[Formula 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, neo Pentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6 -Tetraglycidyl-2,4-hexanediol, N,N,N',N',-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidylamino methyl)cyclohexane, N,N,N',N',-tetraglycidyl-4, 4'-diaminodiphenylmethane and the like are exemplified.

When using the compound which improves adhesiveness with a board|substrate, it is preferable that the usage-amount is 0.1 mass part - 30 mass parts with respect to 100 mass parts of resin components contained in a polymer composition, More preferably, it is 1 mass part - 20 mass parts. is the mass part. When the usage-amount is less than 0.1 mass part, the effect of an adhesive improvement cannot be anticipated, and when it increases more than 30 mass parts, the orientation of a liquid crystal may worsen.

As an additive, a photosensitizer can also be used. Achromatic sensitizers and triplet sensitizers are preferred.

Examples of the photosensitizer include aromatic nitro compounds, coumarin (7-diethylamino-4-methylcoumarin, 7-hydroxy4-methylcoumarin), ketocoumarin, carbonylbiscoumarin, aromatic 2-hydroxyketone, 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-(β-naphthoylmethylene)-3-methylbenzothiazoline, 2-(α-naphthoylmethylene)-3 -Methylbenzothiazoline, 2-(4-biphenoylmethylene)-3-methylbenzothiazoline, 2-(β-naphthoylmethylene)-3-methyl-β-naphthothiazoline, 2-(4-biphenoyl) Methylene)-3-methyl-β-naphthothiazoline, 2-(p-fluorobenzoylmethylene)-3-methyl-β-naphthothiazoline), oxazoline (2-benzoylmethylene-3-methyl-β-naph Tooxazoline, 2-(β-naphthoylmethylene)-3-methylbenzoxazoline, 2-(α-naphthoylmethylene)-3-methylbenzoxazoline, 2-(4-biphenoylmethylene)-3- Methylbenzoxazoline, 2-(β-naphthoylmethylene)-3-methyl-β-naphthooxazoline, 2-(4-biphenoylmethylene)-3-methyl-β-naphthooxazoline, 2-( p-fluorobenzoylmethylene)-3-methyl-β-naphthooxazoline), benzothiazole, nitroaniline (m- or p-nitroaniline, 2,4,6-trinitroaniline) or nitroacenaphthene (5- nitroacenaphthene), (2-[(m-hydroxy-p-methoxy) styryl] benzothiazole, benzoin alkyl ether, N-alkylated phthalone, acetophenone ketal (2,2-dimethoxyphenyl ethanone) ), naphthalene, anthracene (2-naphthalenemethanol, 2-naphthalenecarboxylic acid, 9-anthracenemethanol, and 9-anthracenecarboxylic acid), benzopyran, azoindolizine, merocumarin, and the like.

Preferred are aromatic 2-hydroxyketone (benzophenone), coumarin, ketocoumarin, carbonylbiscoumarin, acetophenone, anthraquinone, xanthone, thioxanthone, and acetophenoneketal.

Further, the present invention relates to a method for manufacturing a substrate and a polarizing element having a liquid crystal alignment film using the polymer composition.

A method for producing a substrate having a liquid crystal alignment film formed from the polymer composition of the present invention,

[I] (A) A step of forming a coating film by coating a polymer composition containing a photosensitive side chain polymer that has a dichroic dye in the side chain and expresses liquid crystallinity in a predetermined temperature range, and an organic solvent on a substrate ;

[II] The process of irradiating the polarized ultraviolet-ray to the coating film obtained in [I]; and

[III] A step of heating the coating film obtained in [II];

has

According to the said process, the liquid crystal aligning film to which the orientation control ability was provided can be obtained, and the board|substrate which has this liquid crystal aligning film can be obtained.

The manufacturing method of the polarizing element,

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

[V-1] On the alignment layer of the substrate having the alignment layer, a composition for forming a polarizing layer containing a dichroic dye and (C) a polymerizable liquid crystal is applied, and a coating film is formed by heating and drying, , process of irradiating ultraviolet rays to the obtained coating film;

[V-2] A step of forming a coating film by applying (D) a composition for forming a polarizing layer containing a dye having lyotropic liquid crystallinity on the alignment layer of the substrate having the alignment layer and drying by heating.

Thereby, a polarizing element can be obtained.

Hereinafter, each step of [I] to [III] and [IV] of the production method of the present invention will be described.

<Process[I]>

In step [I], (A) a photosensitive side chain polymer that has a dichroic dye in the side chain and expresses liquid crystallinity in a predetermined temperature range, and a polymer composition containing an organic solvent are applied on the substrate to apply a coating film to form

<substrate>

The substrate is usually a transparent substrate. On the other hand, when the substrate of the polarizing plate of the present invention (hereinafter, sometimes referred to as the present polarizing plate) is not installed on the display surface of the display element, for example, a polarizing film in which the substrate is removed from the present polarizing plate is applied to the display surface of the display element. In the case of installation, the board|substrate does not need to be transparent. The transparent substrate means a substrate having transparency capable of transmitting light, particularly visible light, and the transparency refers to a characteristic in which the transmittance of light over a wavelength of 380 to 780 nm is 80% or more. Specific examples of the transparent substrate include a translucent resin substrate. Examples of the resin constituting the translucent resin substrate include polyolefins such as polyethylene and polypropylene; Cyclic olefin-type resin, such as a norbornene-type polymer; polyvinyl alcohol; polyethylene terephthalate; polymethacrylic acid ester; polyacrylic acid ester; cellulose esters such as triacetyl cellulose, diacetyl cellulose, and cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polysulfone; polyethersulfone; polyether ketone; Polyphenylene sulfide and polyphenylene oxide are mentioned. A polyethylene terephthalate, polymethacrylic acid ester, a cellulose ester, cyclic olefin resin, or a polycarbonate from a viewpoint of the easiness of acquisition and transparency are preferable.

As for a cellulose ester, a part or all of the hydroxyl groups contained in a cellulose are esterified, and can obtain it easily from a market. Moreover, a cellulose ester base material can also be obtained easily from a market. As a commercially available cellulose ester board|substrate, For example, "Fujitac Film" (Fuji Photo Film Co., Ltd.); “KC8UX2M”, “KC8UY” and “KC4UY” (Konica Minolta Opto Co., Ltd.) and the like.

Cyclic olefin resin can be obtained easily from a market. As a commercially available cyclic olefin resin, "Topas" [Ticona Corporation (Germany)], "Aton" [JSR Corporation], "ZEONOR" [Nippon Zeon Corporation], "ZEONEX (ZEONEX)" )” [Nippon Zeon Co., Ltd.] and “Appel” [Mitsui Chemicals Co., Ltd.]. Such a cyclic olefin resin can be formed into a film by well-known means, such as a solvent casting method and a melt extrusion method, for example, and it can be set as a board|substrate. Moreover, a commercially available cyclic olefin resin substrate can also be used. Commercially available cyclic olefin resin substrates include “S Thinner” [Sekisui Chemical Industry Co., Ltd.], “SCA40” [Sekisui Chemical Industry Co., Ltd.], “Zeonoa Film” [Optes Co., Ltd.] and “Aton Film” [JSR Co., Ltd.] is mentioned.

When the cyclic olefin resin is a copolymer of a cyclic olefin and an aromatic compound having a chain olefin or a vinyl group, the content ratio of the structural unit derived from the cyclic olefin is usually 50 mol% or less with respect to the total structural units of the copolymer. , preferably in the range of 15 to 50 mol%. Examples of the chain olefin include ethylene and propylene, and examples of the aromatic compound having a vinyl group include styrene, α-methylstyrene and alkyl-substituted styrene. 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 It is 80 mol%, and the content rate of the structural unit derived from the aromatic compound which has a vinyl group is 5-80 mol% normally with respect to the total structural unit of a copolymer. Such a terpolymer has the advantage that the usage-amount of expensive cyclic olefin can be comparatively small in the manufacture.

Although the characteristic required for a board|substrate differs with the structure of a polarizing plate, normally, the board|substrate with retardation property as small as possible is preferable. As a board|substrate with retardation as small as possible, a cellulose ester film which does not have retardation, such as Zero-tack (Konica Minolta Opto Co., Ltd.) and Z-tack (Fujifilm Corporation), is mentioned. Moreover, an unstretched cyclic olefin resin base material is also preferable.

In the case of a polarizing plate in which a polarizing layer is formed on a substrate via an alignment film, a hard coat treatment, antireflection treatment, antistatic treatment, or the like may be applied to the surface of the substrate on which the polarization layer is not formed. Moreover, the hard-coat layer may contain additives, such as a ultraviolet absorber, in the range which does not affect performance.

When the thickness of the substrate is too thin, the strength decreases and the workability tends to be inferior. Therefore, it is usually 5 to 300 µm, and preferably 20 to 200 µm.

The method of apply|coating the above-mentioned polymer composition on a board|substrate is not specifically limited.

As for the coating method, industrially, a method of performing screen printing, offset printing, flexographic printing, or inkjet method is common. Other coating methods include a dip method, a roll coater method, a slit coater method, a spinner method (rotary coating method) or a spray method, and these may be used depending on the purpose.

After applying the polymer composition on the substrate, by a heating means such as a hot plate, heat circulation type oven or IR (infrared) type oven at 50 to 230 ℃, preferably 50 to 200 ℃ 0.4 minutes to 60 minutes, Preferably, the coating film can be obtained by evaporating the solvent for 0.5 to 10 minutes. At this time, the drying temperature is preferably lower than the liquid crystal phase expression temperature of the side chain type polymer.

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

On the other hand, it is also possible to provide a process of cooling the substrate on which the coating film is formed to room temperature after the [I] process and before the subsequent [II] process.

<Process [II]>

In process [II], the polarized ultraviolet-ray is irradiated to the coating film obtained in process [I]. When irradiating the polarized ultraviolet-ray to the film surface of a coating film, the polarized ultraviolet-ray is irradiated through a polarizing plate from a fixed direction with respect to a board|substrate. As the ultraviolet rays to be used, ultraviolet rays having a wavelength of 100 nm to 400 nm can be used. Preferably, an optimal wavelength is selected through a filter or the like according to the type of coating film to be used. And, for example, in order to selectively induce a photocrosslinking reaction, ultraviolet rays having a wavelength of 290 nm to 400 nm may be selected and used. As the ultraviolet light, for example, light emitted from a high-pressure mercury lamp can be used.

The irradiation amount of the polarized ultraviolet rays depends on the coating film to be used. The amount of irradiation is the amount of polarized ultraviolet rays that realizes the maximum value of ΔA (hereinafter also referred to as ΔAmax), which is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet rays and the ultraviolet absorbance in the perpendicular direction in this coating film It is preferable to set it as within the range of 1 % - 70%, and it is more preferable to set it as within the range of 1 % - 50%.

<Process[III]>

In process [III], the coating film irradiated with the ultraviolet-ray polarized in process [II] is heated. By heating, orientation control ability can be provided to a coating film.

Heating may use a heating means such as a hot plate, heat circulation type oven or IR (infrared) type oven. The heating temperature can be determined in consideration of the temperature at which the liquid crystallinity of the coating film to be used is expressed.

The heating temperature is preferably within a temperature range of the temperature at which the side chain polymer exhibits liquid crystallinity (hereinafter referred to as liquid crystal expression temperature). In the case of the surface of a thin film such as a coating film, the liquid crystal expression temperature of the surface of the coating film is expected to be lower than the liquid crystal expression temperature when the photosensitive side chain polymer capable of expressing liquid crystallinity is observed in bulk. Therefore, the heating temperature is more preferably within the temperature range of the liquid crystal expression temperature on the surface of the coating film. That is, the temperature range of the heating temperature after irradiation with polarized UV light is a temperature 10 ° C lower than the lower limit of the temperature range of the liquid crystal expression temperature of the side chain type polymer to be used, and the upper limit is a temperature 10 ° C lower than the upper limit of the liquid crystal temperature range. It is preferable that it is a temperature in the range made into If the heating temperature is lower than the above temperature range, the effect of amplifying anisotropy by heat in the coating film tends to be insufficient, and if the heating temperature is too high than the above temperature range, the state of the coating film is in an isotropic liquid state (isotropic top), and in this case, it may be difficult to reorient in one direction due to self-organization.

On the other hand, the liquid crystal expression temperature is above the glass transition temperature (Tg) at which the side chain polymer or the surface of the coating film undergoes a phase transition from the solid phase to the liquid crystal phase, and the isotropic phase transition temperature ( Tiso) or less.

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

By having the above process, in the manufacturing method of this invention, highly efficient and anisotropic introduction to a coating film can be implement|achieved. And it is possible to manufacture a substrate with an alignment layer with high efficiency.

In the manufacturing method of the board|substrate with a coating film of this invention, after apply|coating a polymer composition on a board|substrate to form a coating film, polarized ultraviolet-ray is irradiated. Then, by heating, a high-efficiency anisotropy introduction into the side chain type polymer film is realized, and a substrate with a liquid crystal alignment film having a liquid crystal orientation control ability is manufactured.

In the coating film used in the present invention, the principle of molecular reorientation induced by the photoreaction of side chains and self-organization based on liquid crystallinity is utilized to realize highly efficient anisotropy introduction into the coating film. In the production method of the present invention, in the case of a structure having a photocrosslinkable group as a photoreactive group in the side chain polymer, a coating film is formed on the substrate using the side chain polymer, then irradiated with polarized ultraviolet light, and then heating After performing, a polarizing element is created.

Therefore, in the coating film used in the method of the present invention, by sequentially performing irradiation of polarized ultraviolet rays and heat treatment to the coating film, anisotropy can be introduced with high efficiency and an alignment layer having excellent orientation control ability can be obtained.

And in the coating film used for the method of this invention, the irradiation amount of the ultraviolet-ray polarized to the coating film, and the heating temperature in heat processing are optimized. Thereby, highly efficient introduction of anisotropy to the coating film can be realized.

The optimal dose of polarized UV light for the introduction of highly efficient anisotropy to the coating film used in the present invention is that of polarized UV that optimizes the amount of photosensitive group photocrosslinking reaction, photoisomerization reaction, or photofree translocation reaction in the coating film. corresponding to the amount of irradiation. When the coating film used in the present invention is irradiated with polarized ultraviolet rays, if there are few photosensitive groups in the side chain that undergo photocrosslinking reaction, photoisomerization reaction, or photofree translocation reaction, a sufficient amount of photoreaction is not obtained. In this case, sufficient self-organization does not proceed even after heating. On the other hand, in the coating film used in the present invention, as a result of irradiating polarized ultraviolet light to a structure having a photocrosslinkable group, if the photosensitive group of the side chain to be crosslinked is excessive, the crosslinking reaction between the side chains will proceed excessively. In this case, the obtained film becomes rigid, and it may interfere with the progress of self-organization by subsequent heating. In addition, in the coating film used in the present invention, when polarized ultraviolet light is irradiated with respect to a structure having an optical fleece potential group, if the photosensitive group of the side chain reacting with the optical fleece potential is excessive, the liquid crystallinity of the coating film is excessively reduced. In this case, the liquid crystallinity of the obtained film also falls, and it may interfere with advancing of self-assembly by subsequent heating. Furthermore, when polarized ultraviolet light is irradiated to a structure having an optical fleece potential group, if the irradiation amount of ultraviolet light is too large, the side chain polymer is photodegraded, which may hinder the progress of self-organization by subsequent heating.

Therefore, in the coating film used in the present invention, the optimal amount of the photosensitive group of the side chain to photocrosslinking reaction, photoisomerization reaction, or photofree potential reaction by irradiation with polarized ultraviolet light is 0.1 mole of the photosensitive group of the side chain type polymer film % - 40 mol% is preferable, and it is more preferable to set it as 0.1 mol% - 20 mol%. By setting the amount of the photosensitive group of the photoreactive side chain within this range, self-organization in the subsequent heat treatment proceeds efficiently, and highly efficient anisotropy formation in the film becomes possible.

In the coating film used in the method of the present invention, the amount of photocrosslinking reaction, photoisomerization reaction, or photofree translocation reaction of the photosensitive group in the side chain of the side chain type polymer film is optimized by optimizing the irradiation amount of polarized ultraviolet light. Then, together with the subsequent heat treatment, high-efficiency, anisotropic introduction to the coating film used in the present invention is realized. In that case, it is possible to carry out based on evaluation of the ultraviolet absorption of the coating film used for this invention about the quantity of suitable polarization|polarized-light ultraviolet rays.

That is, with respect to the coating film used in the present invention, the ultraviolet absorption in a direction parallel to the polarization direction of the polarized ultraviolet rays and ultraviolet absorption in a perpendicular direction after irradiation with polarized ultraviolet rays are respectively measured. From the measurement result of the ultraviolet absorption, ΔA, which is the difference between the ultraviolet absorbance in a direction parallel to the polarization direction of the polarized ultraviolet rays and the ultraviolet absorbance in a direction perpendicular to the coating film, is evaluated. And the maximum value (ΔAmax) of ΔA realized in the coating film used in the present invention and the amount of irradiation of polarized ultraviolet rays that realize it are calculated. In the manufacturing method of this invention, on the basis of the polarized-ultraviolet irradiation amount which implement|achieves this (DELTA)Amax, the amount of the polarized-light ultraviolet-ray of a preferable amount to irradiate in manufacture of a liquid crystal aligning film can be determined.

In the manufacturing method of the present invention, the irradiation amount of polarized ultraviolet light to the coating film used in the present invention is preferably within the range of 1% to 70% of the amount of polarized ultraviolet light that realizes ΔAmax, and 1% to 50% It is more preferable to set it as within the range. In the coating film used in the present invention, the irradiation amount of polarized ultraviolet rays within the range of 1% to 50% of the amount of polarized ultraviolet rays to realize ΔAmax is 0.1 mol% to 20 mol% of the total photosensitive groups of the side chain type polymer film It corresponds to the amount of polarized ultraviolet light to be photocrosslinked.

From the above, in the manufacturing method of the present invention, in order to realize highly efficient anisotropy introduction to the coating film, it is preferable to determine the suitable heating temperature as described above based on the liquid crystal temperature range of the side chain type polymer. Therefore, for example, when the liquid crystal temperature range of the side chain polymer used in the present invention is 60° C. to 200° C., it is preferable to set the heating temperature after irradiation with polarized UV light to 50° C. to 190° C. By doing in this way, larger anisotropy is provided in the coating film used for this invention.

By doing so, the polarizing element provided by the present invention exhibits high reliability against external stress such as light or heat.

<Composition for forming a polarizing layer>

The composition for forming a polarizing layer used for formation of the polarizing element of this invention is a composition containing a dichroic dye and (C) a polymeric liquid crystal, or (D) a dye which has lyotropic liquid crystallinity. The composition for polarizing layer formation containing a dichroic dye and (C) polymeric liquid crystal contains a solvent normally, As a solvent, the thing similar to the solvent contained in the above-mentioned orientation polymer composition is mentioned, (C) It can select suitably according to the solubility of a polymerizable liquid crystal.

(D) The composition containing the pigment|dye which has lyotropic liquid crystalline property contains a solvent normally, The said solvent is not specifically limited, Although a conventionally well-known solvent can be used, an aqueous solvent is preferable. Examples of the aqueous solvent include water, a hydrophilic solvent, a mixed solvent of water and a hydrophilic solvent, and the like. The said hydrophilic solvent is a solvent which melt|dissolves substantially uniformly in water. As a hydrophilic solvent, For example, alcohol, such as methanol and isopropyl alcohol; glycols such as ethylene glycol; cellosolves such as methyl cellosolve and ethyl cellosolve; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate; and the like. The aqueous solvent is preferably water, or a mixed solvent of water and a hydrophilic solvent is used.

Although the compound shown to (A) component mentioned above is used as a dichroic dye, the dichroic dye which does not have a polymeric group may be sufficient.

As a commercial item of the dichroic dye which does not have a polymeric group, For example, G-207, G-241, G-470 (made by Hayashibara), Yellow-8, KRD-901, KRD-902 (Showa Chemical Industry Co., Ltd.) ) and SI-486 (manufactured by Mitsui Chemicals Co., Ltd.).

<(C) Polymerizable liquid crystal>

(C) A polymerizable liquid crystal is a compound which has a polymeric group and shows liquid crystallinity.

The polymerizable group means a group involved in the polymerization reaction, and is preferably a photopolymerizable group. Here, the photopolymerizable group refers to a group capable of polymerization reaction with an active radical or acid generated from a photopolymerization initiator described later. Examples of the polymerizable group include a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, an acryloyloxy group, a methacryloyloxy group, an oxiranyl group, and an oxetanyl group. . Among these, an acryloyloxy group, a methacryloyloxy group, a vinyloxy group, an oxiranyl group, and an oxetanyl group are preferable, and an acryloyloxy group is more preferable. The compound showing liquid crystallinity may be a thermotropic liquid crystal or a lyotropic liquid crystal, or may be a nematic liquid crystal or a smectic liquid crystal in a thermotropic liquid crystal.

The polymerizable liquid crystal is preferably a smectic liquid crystal compound, and more preferably a higher order smectic liquid crystal compound, from the viewpoint of obtaining higher polarization properties. Among these, 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 phase A higher-order smectic liquid crystal compound that forms an L phase is more preferable, and a higher-order smectic liquid crystal compound that forms a smectic B phase, a smectic F phase, or a smectic I phase is more preferable. If the liquid crystal phases formed by the polymerizable liquid crystal compound are these higher-order smectic phases, a polarizing film having a higher degree of alignment order can be produced. In addition, such a long polarizing film with a high degree of alignment order obtained Bragg peaks derived from higher-order structures such as hexatic phase and crystal phase in X-ray diffraction measurement. The Bragg peak is a peak derived from the periodic structure of molecular orientation, and if the liquid crystal phase formed by the polymerizable liquid crystal compound is these higher-order smectic phases, a film having a periodic interval of 3.0 to 6.0 angstroms can be obtained.

Specific examples of such a compound include a compound represented by the following formula (d) (hereinafter sometimes referred to as compound (d).) and the like. This polymerizable liquid crystal compound may be used independently and may be combined.

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

[In formula (d),

X ¹ , X ² and X ³ each independently represent an optionally substituted 1,4-phenylene group or an optionally substituted cyclohexane-1,4-diyl group. However, ^{at least one of X 1} , X ² and X ³ is a 1,4-phenylene group which may have a substituent. _{-CH 2} - constituting the cyclohexane-1,4-diyl group may be substituted with -O-, -S- or -NR-. R represents a C1-C6 alkyl group or a phenyl group.

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

U ¹ represents a hydrogen atom or a polymerizable group.

U ² represents a polymerizable group.

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

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

In the compound (d), ^{at least one of X 1} , X ² and X ³ is preferably a 1,4-phenylene group which may have a substituent.

It is preferable that the 1, 4- phenylene group which may have a substituent is unsubstituted. The optionally substituted cyclohexane-1,4-diyl group is preferably an optionally substituted trans-cyclohexane-1,4-diyl group, and optionally optionally substituted trans-cyclohexane- The 1,4-diyl group is preferably unsubstituted.

The 1,4-phenylene group which may have a substituent or the optionally substituted cyclohexane-1,4-diyl group which may have a substituent is an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group and a butyl group; A cyano group, a halogen atom, etc. are mentioned.

Y ¹ is _{preferably -CH 2} CH ₂ -, -COO- or a single bond, and Y ² is _{preferably -CH 2} CH ₂ - or -CH ₂ O-.

U ² is a polymerizable group. U ¹ is a hydrogen atom or a polymerizable group, preferably a polymerizable group. Both U ¹ and U ² are preferably a polymerizable group, and both are preferably a photopolymerizable group. The polymerizable liquid crystal compound having a photopolymerizable group is advantageous in that it can be polymerized under lower temperature conditions.

Although ^{the polymerizable groups represented by U 1} and U ² may independently differ from each other, they are preferably the same. Examples of the polymerizable group include a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, an acryloyloxy group, a methacryloyloxy group, an oxiranyl group, and an oxetanyl group. . Among these, an acryloyloxy group, a methacryloyloxy group, a vinyloxy group, an oxiranyl group, and an oxetanyl group are preferable, and an acryloyloxy group is more preferable.

Examples of the alkanediyl group represented by V ¹ and V ² include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,3-diyl group, a butane-1,4-diyl group, and a pentane-1 group. ,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, decane-1,10-diyl group, tetradecane-1,14-di diyl and icosan-1,20-diyl group; and the like. V ¹ and V ² are preferably 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 included in the alkanediyl group having 1 to 20 carbon atoms which may have a substituent include a cyano group and a halogen atom. The alkanediyl group is preferably unsubstituted, and is unsubstituted and linear. It is more preferable that it is an alkanediyl group of

W ¹ and W ² each independently represent a single bond or —O—.

Specific examples of the compound (d) include compounds represented by formulas (1-1) to (1-23). When the compound (d) has a cyclohexane-1,4-diyl group, it is preferable that the cyclohexane-1,4-diyl group is a trans body.

[Formula 34]

[Formula 35]

[Formula 36]

[Formula 37]

Among the illustrated compounds (d), formula (1-2), formula (1-3), formula (1-4), formula (1-6), formula (1-7), formula (1-8), At least one selected from the group consisting of compounds represented by formulas (1-13), (1-14) and (1-15) is preferable.

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

Moreover, when combining 2 or more types of polymerizable liquid crystal compounds, it is preferable that at least 1 type is a compound (c), and it is more preferable if 2 or more types are a compound (d). By combining, liquid crystallinity can be temporarily maintained even at a temperature below the liquid crystal-crystal phase transition temperature in some cases. The mixing ratio in the case of combining two types of polymeric liquid crystal compounds is 1:99-50:50 normally, Preferably it is 5:95-50:50, More preferably, it is 10:90-50:50 .

Compound (d) is described, for example, in Lub et al. Recl.Trav.Chim.Pays-Bas, 115, 321-328 (1996), or manufactured by a known method described in Japanese Patent No. 4719156.

<(D) Dye having lyotropic liquid crystallinity>

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

Examples of the dye having such lyotropic liquid crystallinity include azo compounds, anthraquinone compounds, perylene compounds, quinophthalone compounds, naphthoquinone compounds, and melocyanine compounds. From the viewpoint of showing good lyotropic liquid crystallinity, it is preferable to use an azo compound.

Among azo compounds, the azo compound which has an aromatic ring in a molecule|numerator is preferable, and the disazo compound which has a naphthalene ring is more preferable. By applying and drying the coating solution containing the azo compound, a polarizing layer having excellent polarization properties can be obtained.

Moreover, as for an azo compound, the azo compound which has a polar group in the molecule|numerator is preferable. The azo compound having a polar group is soluble in an aqueous solvent, and is easily dissolved in the aqueous solvent to form a supramolecular association. Therefore, the coating liquid containing the azo compound having a polar group exhibits particularly good lyotropic liquid crystallinity.

In addition, a polar group means the functional group which has polarity. Examples of the polar group include a functional group containing oxygen and/or nitrogen having a relatively high electronegativity such as OH group, COOH group, NH ₂ group, NO _{2 group, and CN group.}

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

[Formula 38]

In the general formula (D-1), Q ¹ represents a substituted or unsubstituted aryl group, Q ² represents a substituted or unsubstituted arylene group, and R ^D is, independently, a hydrogen atom, a substituted or unsubstituted represents a substituted alkyl group, a substituted or unsubstituted acetyl group, a substituted or unsubstituted benzoyl group, a substituted or unsubstituted phenyl group, M represents a counterion, m7 represents an integer of 0 to 2, n7 represents , an integer of 0 to 6 is represented. However, at least one of m7 and n7 is not 0 and 1≤m7+n7≤6. When m7 is 2, each R ^D is the same or different.

^{In each of OH, (NHR D} ) _m7 , and (SO ₃ M) _n7 represented by the general formula (D-1), a naphthyl ring may be bonded to any of the seven substitution sites.

In addition, in this specification, "substituted or unsubstituted" means "substituted with a substituent or not substituted with a substituent".

The bonding position between the naphthyl group and the azo group (-N=N-) of the general formula (D-1) is not particularly limited. The said naphthyl group points out the naphthyl group shown on the right in Formula (D-1). Preferably, the naphthyl group and the azo group are bonded at the 1st or 2nd position of the naphthyl group.

^{When the alkyl group, acetyl group, benzoyl group, or phenyl group of R D} in the general formula (D-1) has a substituent, the substituent includes each of the substituents exemplified in the following aryl group or arylene group. .

R ^D is preferably a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted acetyl group, and more preferably a hydrogen atom.

Examples of the substituted or unsubstituted alkyl group include a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms.

M (counter ion) in the general formula (D-1) is preferably a hydrogen ion; alkali metal ions such as Li, Na, K, and Cs; alkaline earth metal ions such as Ca, Sr, and Ba; other metal ions; ammonium ion optionally substituted with an alkyl group or a hydroxyalkyl group; and salts of organic amines. The metal ions may be, for example, Ni ^+, Fe ^{3 +,} Cu ^{2 +,} Ag ^+, Zn ^{2 +,} Al ^3+, Pd ^{+ 2,} Cd ^{+ 2,} Sn ^{+ 2,} Co ^{+ 2,} Mn ^{2 +} , Ce ^{3 +} , and the like. Examples of the organic amine include an alkylamine having 1 to 6 carbon atoms, an alkylamine having 1 to 6 carbon atoms having a hydroxyl group, and an alkylamine having 1 to 6 carbon atoms having a carboxyl group. In the general formula (D-1), when SO ₃ M is two or more, each M may be the same or different. In addition, in the general formula (D-1), when _{M of SO 3 M is a divalent or higher cation, it bonds with SO 3} ⁻ of the azo compound of the other general formula (D-1) adjacent to it to form a supramolecular association. can form.

m7 of the said General formula (D-1) becomes like this. Preferably it is 1. In addition, n7 of general formula (D-1) becomes like this. Preferably it is 1 or 2.

As a specific example of the naphthyl group of general formula (D-1), following formula (Da) - a formula (Dl) etc. are mentioned, for example. ^{R D} and M in formulas (Da) to (Dl) are the same as in formula (D-1).

[Formula 39]

In the general formula (D-1), examples of ^{the aryl group represented by Q 1} include condensed cyclic groups in which two or more benzene rings such as a naphthyl group are condensed other than a phenyl group.

Examples of the ^{arylene group represented by Q 2} include condensed cyclic groups in which two or more benzene rings such as a naphthylene group are condensed other than a phenylene group.

The aryl group of Q ¹ or the arylene group of Q ² may each have a substituent, or may not have a substituent. Even when the aryl group or the arylene group is substituted or unsubstituted, the aromatic disazo compound of the general formula (D-1) having a polar group is excellent in solubility in an aqueous solvent.

When the aryl group or arylene group has a substituent, the substituent includes, for example, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylamino group having 1 to 6 carbon atoms, a phenylamino group, An acylamino group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms such as a dihydroxypropyl group, a carboxyl group such as a COOM _{group, a sulfonic acid group such as an SO 3} M group, a hydroxyl group, a cyano group, a nitro group, an amino group , halogeno group, and the like. Preferably, the substituent is one selected from an alkoxy group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, a carboxyl group, a sulfonic acid group, and a nitro group. The aromatic disazo compound which has such a substituent is especially excellent in water solubility. These substituents may be substituted by 1 type(s) or 2 or more types. In addition, the said substituent may be substituted by arbitrary ratios.

^{Q 1} in the general formula (D-1) is preferably a substituted or unsubstituted phenyl group, and more preferably a phenyl group having the above substituent.

Q ² is preferably a substituted or unsubstituted naphthylene group, more preferably a naphthylene group having the above substituent, and particularly preferably a 1,4-naphthylene group having the above substituent.

^{The aromatic disazo compound in which Q 1} of the general formula (D-1) is a substituted or unsubstituted phenyl group and Q ² is a substituted or unsubstituted 1,4-naphthylene group is, ) is indicated.

[Formula 40]

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

In general formula (D-2), A ^D and B ^D represent a substituent, and a7 and b7 represent the substitution number. A ^D and B ^D are each independently an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylamino group having 1 to 6 carbon atoms, a phenylamino group, an acylamino group having 1 to 6 carbon atoms, A hydroxyalkyl group having 1 to 6 carbon atoms such as a dihydroxypropyl group, a carboxyl group such as a COOM _{group, a sulfonic acid group such as an SO 3} M group, a hydroxyl group, a cyano group, a nitro group, an amino group, and a halogeno group are represented. Said a7 is an integer of 0-5, said b7 represents the integer of 0-4. However, at least either one of a7 and b7 is not 0. When a7 is 2 or more, the substituents A ^D may be the same or different. When b7 is 2 or more, the substituent B ^D may be the same or different.

It is preferable to use the aromatic disazo compound represented by the following general formula (D-3) among the aromatic disazo compounds contained in General formula (D-2). In the aromatic disazo compound of the general formula (D-3), the substituent A ^D is bonded to the para position with respect to the azo group (-N=N-). Furthermore, in the aromatic disazo compound of general formula (D-3), the OH group of the naphthyl group is couple|bonded with the position (ortho position) adjacent to the azo group. When the aromatic disazo compound of such general formula (D-3) is used, a polarizing plate with a high degree of polarization can be obtained.

[Formula 41]

In the general formula (D-3), R ^D , M , m7 and n7 are the same as those in the general formula (D-1), and A ^D is the same as in the general formula (D-2).

In general formula (D-3), p7 represents the integer of 0-4. Said p7 becomes like this. Preferably it is 1 or 2, More preferably, it is 1.

The aromatic disazo compounds represented by the general formulas (D-1) to (D-3) are, for example, “Theoretical Manufacturing Dye Chemistry (5th Edition)” by Yutaka Hosoda (July 15, Showa 43) It can be synthesized according to the issuance of symbol maps, pages 135 to 152).

For example, the aromatic disazo compound of general formula (D-3) is obtained by diazotizing and coupling an aniline derivative and a naphthalenesulfonic acid derivative to obtain a monoazo compound, then diazotizing the monoazo compound, Again, it can be synthesized by coupling reaction with a 1-amino-8-naphtholsulfonic acid derivative.

The content ratio of the (C) polymerizable liquid crystal compound or (D) the dye having lyotropic liquid crystallinity in the composition for forming a polarizing layer is determined from the viewpoint of enhancing the alignment property of the liquid crystal compound to the solid content of the composition for forming a polarizing layer. To that, it 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, still more preferably 90 to 99 parts by mass.

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

[V-1] On the alignment layer of the substrate having the alignment layer, a composition for forming a polarizing layer containing a dichroic dye and (C) a polymerizable liquid crystal is applied, and a coating film is formed by heating and drying, and to the obtained coating film The process of irradiating ultraviolet rays;

[V-2] A step of forming a coating film by applying (D) a composition for forming a polarizing layer containing a dye having lyotropic liquid crystallinity on the alignment layer of the substrate having the alignment layer and drying by heating.

The application of the composition for forming a polarizing layer is usually a spin coating method, an extrusion method, a gravure coating method, a die coating method, a bar coating method, a coating method such as an applicator method, or a printing method such as a flexographic method. done by the method When the composition for forming a polarizing layer contains (C) polymerizable liquid crystal, a dry film is usually formed after application by removing the solvent under conditions in which the (C) polymerizable liquid crystal contained in the obtained coating film does not polymerize. . As a drying method, a natural drying method, a ventilation drying method, heat drying, and a reduced pressure drying method are mentioned.

In the step of irradiating an ultraviolet ray to a coating film containing a dichroic dye and (C) polymerizable liquid crystal, polymerization of (C) polymerizable liquid crystal can be performed by a known method for polymerizing a compound having a polymerizable functional group. . Specific examples thereof include thermal polymerization and photopolymerization, and from the viewpoint of easiness of polymerization, photopolymerization is preferable. When polymerizable liquid crystal is polymerized by photopolymerization, polymerizable liquid crystal in a dry film obtained by coating and drying a composition containing a photoinitiator in addition to a composition for forming a polarizing layer containing a dichroic dye and (C) polymerizable liquid crystal After making the liquid crystal state, it is preferable to photopolymerize while maintaining this liquid crystal state.

Photopolymerization is normally performed by irradiating light to a dry film. The light to be irradiated is appropriately selected according to the type of the photoinitiator contained in the dry film, the type of (C) the polymerizable liquid crystal (in particular, the type of photopolymerization group possessed by the (C) polymerizable liquid crystal) and the amount thereof, Specifically, light selected from the group consisting of visible light, ultraviolet light, and laser light, and an active electron beam. Among these, ultraviolet light is preferable from the viewpoint of being easy to control the progress of the polymerization reaction, and that one widely used in the art can be used as a photopolymerization apparatus, so that photopolymerization by ultraviolet light is possible (C) It is preferable to select the kind of a polymerizable liquid crystal or a photoinitiator. Further, during polymerization, the polymerization temperature can be controlled by irradiating with light while cooling the dried film by an appropriate cooling means. By employing such a cooling means, if polymerization of the (C) polymerizable liquid crystal is carried out at a lower temperature, even if a substrate having relatively low heat resistance is used, the polarizing layer can be appropriately formed.

On the alignment layer of the substrate having the alignment layer, (D) a composition for forming a polarizing layer containing a dye having lyotropic liquid crystallinity is applied, and the application in the step of forming a coating film by heating and drying is usually, It is carried out by a known method including a coating method such as a spin coating method, an extrusion method, a gravure coating method, a die coating method, a bar coating method, and an applicator method, and a printing method such as a flexographic method. The drying method is not particularly limited, and natural drying or forced drying can be performed. Examples of forced drying include drying under reduced pressure, drying by heating, drying by heating under reduced pressure, and the like. Preferably, natural drying is used.

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

In addition, the drying temperature is not particularly limited, but is preferably lower than the glass transition temperature (Tg) of the substrate. When the drying temperature exceeds the glass transition temperature of the substrate, there is a risk that the properties (mechanical strength, optical properties, etc.) of the substrate may be altered. Specifically, the drying temperature is preferably 10°C to 100°C, more preferably 10°C to 90°C, and particularly preferably 10°C to 80°C.

On the other hand, the drying temperature means (D) the temperature of the atmosphere for drying the coating film, not the surface or internal temperature of the coating film containing the dye having lyotropic liquid crystallinity.

The sum total of the thickness of an orientation layer and a polarizing layer in this polarizing element is 10 micrometers or less. 0.5 micrometer or more and 9.5 micrometers or less are preferable, and, as for the thickness of an orientation layer, 1 micrometer or more and 5 micrometers or less are more preferable. 0.5 micrometer or more and 9.5 micrometers or less are preferable, and, as for the thickness of a polarizing layer, 1 micrometer or more and 5 micrometers or less are more preferable. The thickness of an orientation layer and a polarizing layer can be calculated|required by the measurement by an interference film thickness meter, a laser microscope, or a stylus type film thickness meter normally.

The polarizing element obtained as described above can be widely applied to various display elements requiring polarization by using a known method, for example, an antireflection film (circularly polarizing plate) such as a liquid crystal display element and organic EL , optical switches and optical filters, and various optical measuring instruments comprising them as components.

Example

Hereinafter, the present invention will be specifically described by way of examples of the present invention, but the present invention should not be construed as being limited thereto.

<solvent>

Each of the compositions for forming an alignment layer in Examples and Comparative Examples contained a solvent, and as the solvents, propylene glycol monomethyl ether (PM), cyclohexanone (CYH), and methyl isobutyl ketone (MIBK) were used.

<Measurement of molecular weight of polymer>

The molecular weight of the acrylic copolymer in the polymerization example was as follows using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) manufactured by Shodex Corporation, and a column (KD-803, KD-805) manufactured by Shodex Corporation. and measured.

On the other hand, the following number average molecular weight (hereinafter referred to as Mn.) and weight average molecular weight (hereinafter referred to as Mw.) are expressed in terms of polystyrene.

Column temperature: 50℃

Eluent: N,N-dimethylformamide (as an additive, lithium bromide-hydrate (LiBr H ₂ O) is 30 mmol/L, phosphoric acid/anhydrous crystal (o-phosphoric acid) is 30 mmol/L, tetrahydrofuran (THF) is 10mL/L)

Flow rate: 1.0 mL/min

Standard samples for calibration curve preparation: TSK standard polyethylene oxide (molecular weights about 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation, and polyethylene glycol manufactured by Polymer Laboratories (molecular weights of about 12,000, 4,000, 1,000).

<Synthesis Example 1>

4-(6-hydroxyhexyloxy)cinnamic acid was synthesized by heating 4-hydroxycinnamic acid and 1-bromo-6-hexanol under alkaline conditions. This product was reacted with methacrylic acid 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 4-hydroxybenzoic acid and 1-bromo-6-hexanol under alkaline conditions. This product was reacted with methacrylic acid chloride under basic conditions to obtain a compound represented by compound (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).

[Formula 42]

<Synthesis Example 4>

18.0 g of the methacrylic acid ester represented by the formula (EX-1), 1.0 g of dichroic dye Disperse 1 methacrylate, and 0.3 g of α,α'-isobisisobutyronitrile as a polymerization catalyst 1,4 - Dissolved in 170.0g of dioxane, and made to react at 80 degreeC for 20 hours, the acrylic copolymer solution was obtained. The acrylic copolymer solution was gradually added dropwise to 1000.0 g of diethyl ether to precipitate a solid, filtered and dried under reduced pressure to remove residual monomers to obtain an acrylic polymer (P1). Mn of the obtained acrylic copolymer was 10,000, and Mw was 22,000.

<Synthesis Example 5>

9.6 g of the methacrylic acid ester represented by the above formula (EX-1), 8.0 g of the methacrylic acid ester represented by the above formula (EX-A), 1.0 g of dichroic dye Disperse 1 methacrylate, as a polymerization catalyst An acrylic copolymer solution was obtained by dissolving 0.3 g of α,α′-isobisisobutyronitrile in 170.0 g of 1,4-dioxane, and reacting it at 80° C. for 20 hours. The acrylic copolymer solution was gradually added dropwise to 1000.0 g of diethyl ether to precipitate a solid, filtered and dried under reduced pressure to remove residual monomers to obtain an acrylic copolymer (P2). Mn of the obtained acrylic copolymer was 12,000 and Mw was 28,000.

<Synthesis Example 6>

9.5 g of the methacrylic acid ester represented by the formula (EX-1), 10.6 g of the methacrylic acid ester represented by the formula (EX-2), 1.0 g of dichroic dye Disperse 1 methacrylate, as a polymerization catalyst An acrylic copolymer solution was obtained by dissolving 0.3 g of α,α′-isobisisobutyronitrile in 190.0 g of 1,4-dioxane, and reacting it at 80° C. for 20 hours. The acrylic copolymer solution was gradually added dropwise to 1000.0 g of diethyl ether to precipitate a solid, filtered and dried under reduced pressure to remove residual monomers to obtain an acrylic copolymer (P3). Mn of the obtained acrylic copolymer was 11,000, and Mw was 21,000.

<Synthesis Example 7>

16.0 g of the methacrylic acid ester represented by the formula (EX-1) and 0.4 g of α,α'-isobisisobutyronitrile as a polymerization catalyst were dissolved in 180.0 g of 1,4-dioxane, and 20 An acrylic copolymer solution was obtained by making it time-react. The acrylic copolymer solution was gradually added dropwise to 1000.0 g of diethyl ether to precipitate a solid, filtered and dried under reduced pressure to remove residual monomers to obtain an acrylic polymer (P4). Mn of the obtained acrylic copolymer was 9,300, and Mw was 16,000.

<Synthesis Example 8>

8.0 g of the methacrylic acid ester represented by the formula (EX-1), 9.8 g of the methacrylic acid ester represented by the formula (EX-2), and 0.2 g of α,α'-isobisisobutyronitrile as a polymerization catalyst was dissolved in 180.0 g of 1,4-dioxane, and reacted at 80° C. for 20 hours to obtain an acrylic copolymer solution. The acrylic copolymer solution was gradually added dropwise to 1000.0 g of diethyl ether to precipitate a solid, followed by filtration and drying under reduced pressure to remove residual monomers to obtain an acrylic copolymer (P5). Mn of the obtained acrylic copolymer was 14,000, and Mw was 24,000.

<Production Example 1>

14.6 g of a polymerizable liquid crystal (RMM141C, manufactured by Merck Corporation) and 0.44 g of a dichroic dye (Disperse Red 1 methacrylate, manufactured by ALDRICH) were dissolved in 35.0 g of MIBK to prepare a composition for forming a polarizing layer having a solid content concentration of 30% by mass did

<Examples 1 to 4> and <Comparative Examples 1 to 2>

With the composition shown in Table 1, each composition for forming an alignment layer of Examples 1 to 4 and Comparative Examples 1 to 2 was prepared. An orientation layer was formed using each composition for orientation layer formation, and the dichroism ratio measurement was performed about each orientation layer. Next, a polarizing element was formed using the composition for forming a polarizing layer. About each obtained polarizing element, evaluation of orientation, a polarization degree measurement, and a dichroic ratio measurement were performed.

<Example 1>

[Formation of alignment layer]

The composition for forming an alignment layer shown in Table 1 was spin-coated on a quartz substrate, dried on a hot plate at 55°C for 60 seconds, and then a coating film having a thickness of 200 nm was formed. Next, linearly polarized light of 313 nm was vertically irradiated with an exposure amount of ² mJ/cm 2 through a polarizing plate on the coating film surface. Then, it heated at 170 degreeC for 5 minutes with a hotplate, and formed the orientation layer.

[Measurement of dichroism ratio of alignment layer]

The dichroism ratio of the obtained orientation layer was measured as follows. The absorbance (A1) in the transmission axis direction and the absorbance (A2) in the absorption axis direction were measured using a spectrophotometer (UV-3600 manufactured by Shimadzu Corporation) in which a folder with a polarizer was set. From the measured values of the absorbance (A1) in the transmission axis direction and the absorbance (A2) in the absorption axis direction, the dichroic ratio was calculated using the following formula. Table 2 shows the measurement results.

Dichroic ratio = (A2)/(A1)

[Formation of Polarizing Layer]

On the obtained orientation layer, the composition for polarizing layer formation was spin-coated at 2000 rpm*30 sec, and it dried for 60 second on a 65 degreeC hotplate, and formed the coating film. Next, the polarizing element was obtained by exposing this coating film at 500 mJ/cm<^2>.

[Evaluation of orientation]

The orientation of the obtained polarizing element was confirmed by observation with a polarizing microscope. The sample was inserted in the direction of 0° and 45° between cross nicol under a polarizing microscope, and the light leakage state was observed. In the case of orientation, light leakage does not occur at 0° and a dark field state is observed, and at 45° light leakage occurs and a bright field state is observed. The case where a dark field was obtained at 0° and a bright field was obtained at 45° was set to "○", and when it was not obtained, it was set as "x". Table 2 shows the results of these measurements.

[Polarization measurement]

The polarization degree of the obtained polarizing element was measured as follows. The transmittance (T1) in the transmission axis direction and transmittance (T2) in the absorption axis direction were measured using a spectrophotometer (UV-3600 manufactured by Shimadzu Corporation) in which a folder with a polarizer was set. From the values of the measured transmittance (T1) in the transmission axis direction and transmittance (T2) in the absorption axis direction, the degree of polarization was calculated using the following formula. Table 2 shows the measurement results.

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

[Measurement of dichroism ratio of polarizing element]

The dichroism ratio of the obtained polarizing element was measured as follows. The absorbance (A1) in the transmission axis direction and the absorbance (A2) in the absorption axis direction were measured using a spectrophotometer (UV-3600 manufactured by Shimadzu Corporation) in which a folder with a polarizer was set. From the measured values of the absorbance (A1) in the transmission axis direction and the absorbance (A2) in the absorption axis direction, the dichroic ratio was calculated using the following formula. Table 2 shows the measurement results.

Dichroic ratio = (A2)/(A1)

<Example 2>

A polarizing element was created in the same manner as in Example 1 except that the heating temperature after polarization exposure at the time of orientation layer formation was 150 degreeC. Table 2 summarizes the results.

<Example 3>

A polarizing element was created in the same manner as in Example 1, except that the heating temperature after polarization exposure at the time of formation of the alignment layer was 110°C. Table 2 summarizes the results.

<Example 4>

A polarizing element was created in the same manner as in Example 1, except that the heating temperature after polarization exposure at the time of orientation layer formation was 150 degreeC. Table 2 summarizes the results.

<Comparative Example 1>

It carried out similarly to Example 1, and created the polarizing element. Table 2 summarizes the results.

<Comparative Example 2>

A polarizing element was created in the same manner as in Example 1 except that the heating temperature after polarization exposure at the time of orientation layer formation was 110 degreeC. Table 2 summarizes the results.

In Comparative Examples 1 and 2 using the acrylic copolymer not containing the dichroic dye in the alignment layer, the dichroism ratio of the alignment layer was 0. On the other hand, in Examples 1 to 4 in which the acrylic copolymer containing the dichroic dye was used in the orientation layer, a dichroic ratio was obtained, and it was possible to orient the dichroic dye in the orientation layer.

The polarizers obtained in Examples 1-4 were able to express a high polarization degree and a dichroism ratio compared with Comparative Examples 1-2.

Claims (5)

(A) containing a photosensitive side chain type polymer that has a dichroic dye in the side chain and expresses liquid crystallinity in a predetermined temperature range, and an organic solvent,
(A) The polymer composition which has any 1 type of photosensitive side chains which a component is chosen from the group which consists of following formula (1)-(6).

wherein A, B and D are each independently a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO- O-, or -O-CO-CH=CH-;
S represents an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded to a carbon atom in the alkylene group may be substituted with a halogen atom;
T represents a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded to a carbon atom in the alkylene group may be substituted with a halogen atom;
Y ₁ is a monovalent substituent in which one hydrogen atom is removed from a benzene ring, a monovalent substituent in which one hydrogen atom is removed from a naphthalene ring, a monovalent substituent in which one hydrogen atom is removed from a biphenyl ring, one hydrogen from a furan ring A monovalent substituent in which an atom is removed, a monovalent substituent in which one hydrogen atom is removed from a pyrrole ring, or a monovalent substituent in which one hydrogen atom is removed from an alicyclic hydrocarbon having 5 to 8 carbon atoms is represented, or selected from these substituents 2 to 6 identical or different substituents represent a monovalent substituent formed by bonding through a bonding group defined by B, and in all of these substituents, a hydrogen atom bonding to a carbon atom is independently -COOR ₀ (wherein R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or may be substituted with an alkyloxy group having 1 to 5 carbon atoms;
Y ₂ is a divalent substituent in which two hydrogen atoms are removed from a benzene ring, a divalent substituent in which two hydrogen atoms are removed from a naphthalene ring, a divalent substituent in which two hydrogen atoms are removed from a biphenyl ring, two hydrogens from a furan ring A divalent substituent in which an atom is removed, a divalent substituent in which two hydrogen atoms are removed from a pyrrole ring, a divalent substituent in which two hydrogen atoms are removed from an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof. represents a divalent substituent to be used, and in all of these substituents, a hydrogen atom bonded to a carbon atom is independently -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen atom, a carbon source may be substituted with an alkyl group having 1 to 5 atoms, or an alkyloxy group having 1 to 5 carbon atoms;
R represents a hydroxy group or an alkoxy group having 1 to 6 carbon atoms, or has the same definition as _{Y 1 ;}
X is a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, ※1-CH=CH-CO-O-※2, or ※1- O-CO-CH=CH-*2, *1 represents the bonding position with P in the formulas (1) to (6), *2 represents the formulas (1) to (6) It represents a bonding position with Q, and when the number of X is 2, X may be the same or different;
Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and hydrogen atoms bonded thereto are each independently -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, may be substituted with a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
As for q1 and q2, one is 1 and the other is 0;
q3 is 0 or 1;
P and Q are each independently a divalent substituent in which two hydrogen atoms are removed from a benzene ring, a divalent substituent in which two hydrogen atoms are removed from a naphthalene ring, a divalent substituent in which two hydrogen atoms are removed from a biphenyl ring, furan A divalent substituent in which two hydrogen atoms are removed from a ring, a divalent substituent in which two hydrogen atoms are removed from a pyrrole ring, a divalent substituent in which two hydrogen atoms are removed from an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof represents a divalent substituent selected from the group consisting of; However, when X is *1-CH=CH-CO-O-*2, or *1-O-CO-CH=CH-*2, *1 is the formula (1) to (6) above. represents a bonding position with P, *2 indicates a bonding position with Q in the formulas (1) to (6), and P or Q on the side to which -CH=CH- is bonded is two hydrogen atoms from an aromatic ring. represents a divalent substituent from which ;
l1 is 0 or 1;
l2 is an integer from 0 to 2;
When both l1 and l2 are 0, and when T is a single bond, A also represents a single bond;
When l1 is 1, and when T is a single bond, B also represents a single bond;
H is a divalent substituent in which two hydrogen atoms are removed from a naphthalene ring, a divalent substituent in which two hydrogen atoms are removed from a biphenyl ring, a divalent substituent in which two hydrogen atoms are removed from a furan ring, two hydrogen atoms from a pyrrole ring A divalent substituent selected from a divalent substituent from which is removed, and a combination thereof is shown.
I is a divalent substituent in which two hydrogen atoms are removed from a benzene ring, a divalent substituent in which two hydrogen atoms are removed from a naphthalene ring, a divalent substituent in which two hydrogen atoms are removed from a biphenyl ring, two hydrogen atoms from a furan ring A divalent substituent selected from a divalent substituent in which is removed, a divalent substituent in which two hydrogen atoms are removed from a pyrrole ring, and a combination thereof is shown. delete delete According to claim 1,
(A) The polymer composition in which a component has any 1 type of liquid crystalline side chain chosen from the group which consists of following formula (21)-(31).

wherein A, B, q1 and q2 have the same definitions as above;
Y ₃ is a monovalent substituent in which one hydrogen atom is removed from a benzene ring, a monovalent substituent in which one hydrogen atom is removed from a naphthalene ring, a monovalent substituent in which one hydrogen atom is removed from a biphenyl ring, is one hydrogen from a furan ring A monovalent substituent in which an atom is removed, a monovalent substituent in which one hydrogen atom is removed from a nitrogen-containing heterocycle, a monovalent substituent in which one hydrogen atom is removed from an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a group consisting of combinations thereof represents a monovalent substituent selected from, and among all of these substituents, a hydrogen atom bonded to a carbon atom is each independently -NO ₂ , -CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms may be substituted with an alkyloxy group;
R ₃ is a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen atom, a monovalent substituent obtained by removing one hydrogen atom from a benzene ring, and 1 from a naphthalene ring A monovalent substituent in which two hydrogen atoms are removed, a monovalent substituent in which one hydrogen atom is removed from a biphenyl ring, a monovalent substituent in which one hydrogen atom is removed from a furan ring, a monovalent substituent in which one hydrogen atom is removed from a nitrogen-containing heterocyclic ring , a monovalent substituent in which one hydrogen atom has been removed from an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;
l represents the integer of 1-12, m represents the integer of 0-2, with the proviso that in formulas (23) and (24), the sum of all m is 2 or more, and formulas (25) and formulas ( In 26), the sum of all m is 1 or more, and m1, m2 and m3 each independently represent an integer of 1 to 3;
R ₂ is a hydrogen atom, -NO ₂ , -CN, a halogen atom, a monovalent substituent in which one hydrogen atom is removed from a benzene ring, a monovalent substituent in which one hydrogen atom is removed from a naphthalene ring, one hydrogen from a biphenyl ring A monovalent substituent in which an atom is removed, a monovalent substituent in which one hydrogen atom is removed from a furan ring, a monovalent substituent in which one hydrogen atom is removed from a nitrogen-containing heterocycle, and one hydrogen atom from an alicyclic hydrocarbon having 5 to 8 carbon atoms represents the removed monovalent substituent, an alkyl group, or an alkyloxy group;
Z ₁ and Z ₂ represent a single bond, -CO-, -CH ₂ O-, -CH=N-, or -CF ₂ -. 5. The method of claim 1 or 4,
(B) As a component, the compound represented by following formula (c) is contained, The polymer composition characterized by the above-mentioned.

( ^{Wherein, any 3 to 5 of R 101} , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ and R ¹⁰⁵ are each independently a hydrogen atom, a halogen atom, a C ₁ to C ₆ alkyl group, or a C ₁ to C ₆ haloalkyl group , C ₁ to C ₆ alkoxy group, C ₁ to C ₆ haloalkoxy group, C ₃ to C ₈ cycloalkyl group, C ₃ to C ₈ halocycloalkyl group, C ₂ to C ₆ alkenyl group, C ₂ to C ₆ haloalke Nyl group, C ₃ to C ₈ cycloalkenyl group, C ₃ to C ₈ halocycloalkenyl group, C ₂ to C ₆ alkynyl group, C ₂ to C ₆ haloalkynyl group, (C ₁ to C ₆ alkyl)carbonyl group, (C ₁ to C ₆ haloalkyl)carbonyl group, (C ₁ to C ₆ alkoxy)carbonyl group, (C ₁ to C ₆ haloalkoxy)carbonyl group, (C ₁ to C ₆ alkylamino)carbonyl group, (C ₁ to C ₆ haloalkyl) represents a substituent selected from an aminocarbonyl group, a di(C ₁ to C ₆ alkyl)aminocarbonyl group, a cyano group and a nitro group, and any 3 to 4 of ^{R 101} , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ and R ^{105 are defined above} When , R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ and R ¹⁰⁵ the other one or two of the following formula (c-2)

(In formula (c-2), the broken line indicates the number of bonds, and R ¹⁰⁶ is an alkylene group having 1 to 30 carbon atoms, a phenylene group, or a divalent substituent in which two hydrogen atoms are removed from a carbocyclic compound or a heterocyclic compound. A divalent substituent in which two hydrogen atoms have been removed is represented, and two hydrogen atoms have been removed from an alkylene group, a phenylene group, or a divalent substituent obtained by removing two hydrogen atoms from a carbocyclic compound, or a divalent substituent obtained by removing two hydrogen atoms from a heterocyclic compound one or a plurality of hydrogen atoms, the group is a fluorine atom or an organic addition, may be substituted, R ¹⁰⁶ of the -CH ₂ CH ₂ -. may be substituted by -CH = CH-, R ¹⁰⁶ of the -CH ₂ - may be substituted with a phenylene group or a divalent substituent in which two hydrogen atoms are removed from a carbocyclic compound or a divalent substituent in which two hydrogen atoms are removed from a heterocyclic compound, and further, -CH ₂ ^{in R 106} - is, unless divalent groups selected from the group consisting of -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH-, and -CO- are not adjacent to each other, these It may be substituted with a divalent group. R ¹⁰⁷ represents a hydrogen atom or a methyl group.) represents the group represented by), and n represents 0 or 1.)