KR102307799B1 - Orientation layer forming composition - Google Patents

Abstract

PROBLEM This invention provides the polymer composition for liquid crystal aligning films which can orientate a polymeric liquid crystal composition, when obtaining a polarizing element with high dichroism.
[Solutions] The present invention provides a polymer composition containing (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range, (B) a dichroic dye 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, after the board|substrate which has a liquid crystal aligning film formed from this polymer composition.

Description

Orientation layer forming composition

The present invention relates to a polymer composition useful for forming an alignment layer for orienting a polymerizable liquid crystal composition serving as a polarizing layer in the 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 substance, that is, a dichroic dye.

Conventionally, as a dichroic dye, for the purpose of obtaining high dichroism, a dye which has an azo skeleton as a basic skeleton (patent documents 1-2), the dye which has an anthraquinone skeleton, etc. are used many.

In addition, as a method of 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 as a host material and a dye as a guest material are mixed 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 to other optical films (Patent Document 5); And the method (patent document 6) of preparing a polymerizable mesogen tablet containing a polymerizable mesogenic compound and a dichroic dye, and preparing a polarizer effectively from the point of time and cost using this 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 such a dichroic dye generally has low solubility with respect to a solvent, there existed a problem that it was difficult to mix|blend highly with a liquid crystalline composition.

Under the above background, the present invention provides a polymer composition useful for forming an alignment layer for orienting a polymerizable liquid crystal composition serving as 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> (A) a photosensitive side-chain polymer that exhibits liquid crystallinity in a predetermined temperature range, (B) a polymer composition containing a dichroic dye and an organic solvent.

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

<3> (A) The polymer composition as described in said <1> whose component is a side chain type polymer|macromolecule which has any 1 type of photosensitive side chain selected 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 thereto may be substituted with a halogen group;

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

Y ₁ represents a ring selected from the group consisting of a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same selected from their substituents Or represents a group formed by bonding 2 to 6 different rings through a bonding group B, and the hydrogen atoms bonded thereto are 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 group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms. ;

Y ₂ represents a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, Each hydrogen atom is independently -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms. may be substituted;

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-, -CH=CH-CO-O-, or -O-CO-CH= When CH- is represented and 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 group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;

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

q3 is 0 or 1;

P and Q each independently represent a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof. ; However, when X is -CH=CH-CO-O-, -O-CO-CH=CH-, P or Q on the side to which -CH=CH- is bonded is an aromatic ring;

l1 is 0 or 1;

l2 is an integer from 0 to 2;

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

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

H and I each independently represent a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and combinations thereof.

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

[Formula 2]

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

Y ₃ represents a group selected from the group consisting of a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocycle, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, Each hydrogen atom bonded to -NO ₂ , -CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms may be substituted;

R ₃ is a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen containing a heterocyclic ring, 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 an integer of 1 to 12, m is an integer of 0 to 2, with the proviso that in formulas (25) to (26), the sum of all m is 2 or more, and in formulas (27) to (28) wherein the sum of all m is 1 or more, and m1, m2 and m3 are each independently an integer of 1 to 3;

R ₂ is a hydrogen atom, -NO ₂ , -CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocycle, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, and; an alkyl group or an alkyloxy group;

Z ₁ , Z ₂ represents a single bond, -CO-, -CH ₂ O-, -CH=N-, -CF ₂ -.

<5> (C) 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, C ₁ to C ₆ alkyl, C ₁ to C ₆ haloalkyl , C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy, C ₃ -C ₈ cycloalkyl, C ₃ -C ₈ halocycloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C ₃ ~C ₈ Cycloalkenyl, C ₃ ~C ₈ Halocycloalkenyl, C ₂ ~C ₆ Alkynyl, C ₂ ~C ₆ Haloalkynyl, C ₁ ~C ₆ Alkoxy, C ₁ ~C ₆ Haloalkoxy , (C ₁ -C ₆ alkyl)carbonyl, (C ₁ -C ₆ haloalkyl)carbonyl, (C ₁ -C ₆ alkoxy)carbonyl, (C ₁ -C ₆ haloalkoxy)carbonyl, (C ₁ ~ C ₆ alkyl) carbonyl, (C ₁ ~ C ₆ haloalkyl) aminocarbonyl, di (C ₁ ~ C ₆ alkyl) aminocarbonyl, cyano, and represents a substituent selected from the group consisting of nitro, R ^When any 3 to 4 of 101 , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ and R ¹⁰⁵ are the above definitions, the other one or two of ^{R 101} , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ and R ^{105 is a formula} (c-2)

[Formula 4]

(In formula (c-2), the broken line represents the number of bonds, R ¹⁰⁶ represents an alkylene group having 1 to 30 carbon atoms, phenylene or a divalent carbocyclic or heterocyclic ring, and this alkylene group, phenylene or divalent One or more hydrogen atoms in the carbocyclic or heterocyclic ring may be substituted with a fluorine atom or an organic group, and -CH ₂ CH ₂ ^{- in R 106} may be substituted with -CH=CH-; -CH ₂ - in R ¹⁰⁶ may be substituted with phenylene or a divalent carbocyclic or heterocyclic ring, and 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-. R ¹⁰⁷ represents a hydrogen atom or a methyl group); n represents 0 or 1.)

<6> An alignment layer forming composition containing the polymer composition according to any one of <1> to <5>.

According to the present invention, it is possible to provide a novel polymer composition that can be used to obtain a polarizing plate having high polarization performance without high mixing of a dichroic dye in the liquid crystal composition.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching, this inventor came to complete this invention by obtaining the following knowledge.

The polymer composition of the present invention has a photosensitive side chain polymer (hereinafter simply referred to as a side chain polymer) capable of expressing liquid crystallinity and a dichroic dye, and the coating film obtained using the polymer composition has liquid crystallinity It is a film|membrane which has a photosensitive side chain type polymer|macromolecule which can express. This coating film is not subjected to a rubbing treatment, and alignment treatment can be performed by irradiation with polarized light. 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 a high alignment control ability is imparted can be obtained. Here, when a polymer composition contains a dichroic dye, the orientation layer which has a high dichroism ratio can be obtained. Accordingly, the polymer composition of the present invention is useful as an alignment layer-forming composition for orienting a polarizing layer containing a liquid crystalline composition and, if necessary, a dichroic dye when forming a polarizing layer.

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

<<(A) A photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range >>

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

(A) It is preferable that the side chain type polymer reacts with light in a wavelength range of 250 nm to 400 nm, and 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 type 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 side chain having photosensitivity bonded to the main chain, and may cause a crosslinking reaction, an isomerization reaction, or an optical Fris 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 photofrees 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 polymer film capable of expressing liquid crystallinity is not particularly limited as long as it satisfies these 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 this polymer, for example, has a main chain and a side chain bonded thereto, and the side chain is a mesogen 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 capable of crosslinking or isomerization in response to light, or having a main chain and a side chain bonded thereto, the side chain also serves as a mesogenic component, and a phenylbenzoate group that undergoes a photofreezing 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 hydrocarbons, (meth)acrylates, itaconates, fumarates, maleates, 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 radical polymerizable groups 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 thereto may be substituted with a halogen group;

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

Y ₁ represents a ring selected from the group consisting of a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same selected from their substituents Or represents a group formed by bonding 2 to 6 different rings through a bonding group B, and the hydrogen atoms bonded thereto are 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 group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms. ;

Y ₂ represents a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, Each hydrogen atom is independently -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms. may be substituted;

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-, -CH=CH-CO-O-, or -O-CO-CH= When CH- is represented and 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 group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;

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

q3 is 0 or 1;

P and Q each independently represent a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof. ; However, when X is -CH=CH-CO-O-, -O-CO-CH=CH-, P or Q on the side to which -CH=CH- is bonded represents an aromatic ring;

l1 is 0 or 1;

l2 is an integer from 0 to 2;

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

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

H and I each independently represent a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and combinations thereof.

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

In the formula, 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 from 0 to 2, m1, m2 represents an integer from 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 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 , l, q1, q2, m1, and m2 have the same definitions as above.

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

[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 represents a group selected from the group consisting of a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocycle, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, Each hydrogen atom bonded to -NO ₂ , -CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms may be substituted;

R ₃ is a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen containing a heterocyclic ring, 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 (25) to (26), the sum of all m is 2 or more, and formulas (27) to (28) In , 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 group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocycle, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, and; an alkyl group or an alkyloxy group;

Z ₁ , Z ₂ represents a single bond, -CO-, -CH ₂ O-, -CH=N-, -CF ₂ -.

[Formula 12]

<<Preparation of photosensitive side chain polymer>>

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

[Photoreactive side chain monomer]

The photoreactive side chain monomer is 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 formulas (1) to (6), preferably, for example, the formula (7) A photosensitive side chain consisting of at least one kind of to (10), a photosensitive side chain consisting of at least one kind of 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 group consisting of 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 , M1 represents a hydrogen atom or a methyl group , s1 represents the number of methylene groups, and is a natural number from 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) In formula (M1-1), such as cinnamic acid, 4-(3-methacryloxypropyl-1-oxy)cinnamic acid, and 4-(4-(6-methacryloxyhexyl-1-oxy)benzoyloxy)cinnamic acid R represents OH, and 4-(6-methacryloxyhexyl-1-oxy)cinnamamide, 4-(6-acryloxyhexyl-1-oxy)cinnamamide, 4-(3-methacryloxy) the R of the profile 1-oxy) such as cinnamic amide, formula (M1-1), and the like to represent the NH _2.

[Liquid crystalline side chain monomer]

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

As a mesogenic group of a side chain, it may be a group which becomes a mesogenic structure alone, such as biphenyl or phenylbenzoate, or it may be a group which becomes 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 from 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 side chain monomers, as the monomer having a carboxyl group or an amide group, a monomer represented by a formula selected from the group consisting of the following formulas M2-1 to M2-9 may be used.

[Formula 19]

[Formula 20]

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

Moreover, as a monomer which has a substituent which expresses liquid crystal which is an example of this other monomer, the monomer represented by the formula selected from the group which consists of following formula M2-10 - M2-16 can also be used.

[Formula 21]

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

(A) The side-chain polymer can be obtained by copolymerization of the photoreactive side-chain monomer exhibiting liquid crystallinity described above. In addition, it can be obtained by copolymerization of a photoreactive side chain monomer that does not express liquid crystallinity and a liquid crystalline side chain monomer, or copolymerization of a photoreactive side chain monomer that exhibits liquid crystallinity and a liquid crystalline side chain monomer. Moreover, it can copolymerize with other monomers in the range which does not impair liquid crystal expression ability.

Examples of the other monomer include an industrially available monomer capable of radical polymerization.

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, and the like.

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, methylstyrene, chlorostyrene, bromostyrene, etc. are mentioned, for example.

Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

The content of the photoreactive side chain in the side chain polymer of the present invention is preferably from 10 mol% to 100 mol%, more preferably from 20 mol% to 95 mol%, and from 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 based on the total amount of side chains, more preferably 5 mol% to 80 mol%, furthermore 10 mol% to 70 mol% 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 show the effect as a liquid crystal aligning film.

The side chain polymer of the present invention may include other side chains other than the photoreactive side chain and the liquid crystal side chain. The content is the remainder when the sum of the content of the photoreactive side chain and the liquid crystalline side chain does not reach 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 prepared 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 (azobisisobutyronitrile, 2,2'-di(2-hydroxyethyl) azobisisobutyronitrile, etc.) 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 the radical photopolymerization initiator include benzophenone, Michler 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-dodecylcarba Sol, 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)benzophenone, 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-Benzothiazole-2-ylidene)-1-naphthalen-2-yl-ethanone, or 2-(3-methyl-1,3-benzothiazole-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 reaction of the photosensitive side chain polymer capable of expressing liquid crystallinity is not particularly limited as long as the resulting polymer dissolves. 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, methoxymethylpentanol, 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 mono Butyl 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 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, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diiso Butyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, acetic acid Methyl, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid , 3-methoxypropionic acid, 3-methoxypropionic acid propyl, 3-methoxybutyl propionate, 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 independently or may be mixed and used. Moreover, even if it is a solvent which does not dissolve the polymer|macromolecule produced|generated, you may use it in the range in which the produced|generated polymer does not precipitate, mixing with the above-mentioned organic solvent.

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 during radical polymerization may be any temperature of 30°C to 150°C, but is preferably in the range of 50°C to 100°C. In addition, the reaction can be carried out at any concentration, but 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, so that the monomer concentration is, Preferably they are 1 mass % - 50 mass %, More preferably, they are 5 mass % - 30 mass %. The initial reaction may be carried out at a high concentration, and thereafter, an organic solvent may be added.

In the above-mentioned radical polymerization reaction, 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 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 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 cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, and water. can The polymer precipitated by pouring into 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 polymer of the present invention is the weight average molecular weight measured by the GPC (Gel Permeation Chromatography) method, in consideration of the strength of the obtained coating film, workability during coating film formation, and the uniformity of the coating film, 2000 ~1000000 is preferable, More preferably, it is 5000-100000.

<(B) Dichroic dye>

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. The dichroic dye may include, for example, an acridine dye, an oxazine dye, a cyanine dye, a naphthalene dye, an azo dye, and an anthraquinone dye, but among them, an azo dye is preferable. Examples of the azo dye include mono-azo dye, bi-azo dye, tris azo dye, tetrakis azo dye, and stilbenazo dye, and preferably a bi-azo dye and tris azo 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 a group in which one hydrogen atom has been removed from a heterocyclic compound such as quinoline, thiazole, benzothiazole, thienothiazole, imidazole, benzoimidazole, oxazole and benzoxazole. Examples of the divalent heterocyclic group include a group 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 p-phenylene group, naphthalene-1,4- ^{diyl group and divalent heterocyclic group for A 2 include a carbon source} an alkyl group of 1-4 embroidery; an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group and a butoxy group; a C1-C4 fluorinated alkyl group, 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 means an amino group forming the alkanediyl group of ~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, independently of each other, 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 the same as above), a chlorine atom or a trifluoromethyl group.

n1-n4 represent the integer of 0-3 mutually independently.

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 independently the same or different from 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 pigment|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 6 carbon atoms or an aryl group having 6 to 12 carbon atoms.]

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

[Formula 25]

[In formula (2-8),

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

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

Equation (2-7) and (2-8) and, with an alkyl group carbon atom number 1-6 indicating the R ^x in the formula (2-9) is a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group, and examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a toluyl group, a xylyl group, and a naphthyl group.

The cyanine pigment is preferably a compound represented by the formula (2-10) and a compound represented by the formula (2-11).

[Formula 27]

[In formula (2-10),

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

[Formula 28]

n5 represents an integer from 1 to 3.]

[Formula 29]

[In formula (2-11),

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

[Formula 30]

n6 represents an integer from 1 to 3.]

Moreover, as a commercial item of the above dichroic dyes, For example, G-207, G-241, G-470 (made by Hayashibara), Yellow-8, KRD-901, KRD-902 (Showa Chemical Industry Co., Ltd.) Co., Ltd.) and SI-486 (made by Mitsui Chemicals Co., Ltd.) are mentioned.

Content of the dichroic dye which is (B) component in an orientation layer formation composition is 0.1 mass part or more with respect to 100 mass parts of side chain type polymer|macromolecule which is (A) component from a viewpoint of making the orientation of a dichroic dye favorable. 30 parts by mass or less is preferable, 0.1 parts by mass or more and 20 parts by mass or less are more preferable, and 0.1 parts by mass or more and 10 parts by mass or less are still more preferable.

<(C)component>

The polymer composition of this invention can also contain the compound represented by a following formula (c) as (C)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, C ₁ to C ₆ alkyl, C ₁ to C ₆ haloalkyl , C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy, C ₃ -C ₈ cycloalkyl, C ₃ -C ₈ halocycloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C ₃ -C ₈ Cycloalkenyl, C ₃ -C ₈ Halocycloalkenyl, C ₂ -C ₆ Alkynyl, C ₂ -C ₆ Haloalkynyl, (C ₁ -C ₆ Alkyl)carbonyl, (C ₁ ~C ₆ Haloalkyl)carbonyl, (C ₁ ~C ₆ Alkoxy)carbonyl, (C ₁ ~C ₆ Haloalkoxy)carbonyl, (C ₁ ~C ₆ Alkylamino)carbonyl, (C ₁ ~C ₆ haloalkyl)aminocarbonyl, di(C ₁ -C ₆ alkyl)aminocarbonyl, cyano and nitro, any of R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ and R ¹⁰⁵ . When 3 to 4 are the above definitions, the ^{other one or two of R 101} , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ and R ¹⁰⁵ is the following formula (c-2)

[Formula 32]

(In formula (c-2), the broken line represents the number of bonds, R ¹⁰⁶ represents an alkylene group having 1 to 30 carbon atoms, phenylene or a divalent carbocyclic or heterocyclic ring, and this alkylene group, phenylene or divalent One or more hydrogen atoms in the carbocyclic or heterocyclic ring may be substituted with a fluorine atom or an organic group, and -CH ₂ CH ₂ ^{- in R 106} may be substituted with -CH=CH-; -CH ₂ - in R ¹⁰⁶ may be substituted with phenylene or a divalent carbocyclic or heterocyclic ring, and 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-. R ¹⁰⁷ represents a hydrogen atom or a methyl group); 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 C _a to C _b alkyl 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 C a} to C _b haloalkyl 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, and this When substituted by 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 group 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 C a} to C _b cycloalkyl 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 by 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 C a} to C _b halocycloalkyl 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 the substitution by a halogen atom may be a ring structure moiety, a side chain moiety, or both, or two When substituted with the above halogen atoms, 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 C a} to C _b alkenyl 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 carbon atom number.

In the present specification, _{the notation of C a} to C _b haloalkenyl is a linear or branched chain consisting of 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 An unsaturated hydrocarbon group having one or two or more double bonds. In this case, when substituted with 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.

In the present specification, _{the notation of C a} to C _b cycloalkenyl 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 of In addition, each ring may be optionally substituted with an alkyl group within the range of the designated number of carbon atoms, and the double bond may be in any form of 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 carbon atom number.

In the present specification, _{the notation of C a} to C _b halocycloalkenyl 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 optionally substituted with an alkyl group within the range of the designated number of carbon atoms, and the double bond may be in any form of 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 or mutually may be different. 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 C a} to C _b alkynyl 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 triple bonds in the molecule, e.g. 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 C a} to C _b haloalkynyl is a linear or branched chain consisting of 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 An unsaturated hydrocarbon group having one or two or more triple bonds. In this case, when substituted with 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 C _a to C _b alkoxy 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.

In the present specification, _{the notation of C a} to C _b haloalkoxy represents a haloalkyl-O- group having the above meaning consisting of a to b carbon atoms, for example, a difluoromethoxy group or 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 are selected from the range of each designated number of carbon atoms.

In the present specification, _{the expression of (C a} -C _b alkyl) carbonyl represents an alkyl-C (O) - group having the above meaning consisting of a to b carbon atoms, for example, an acetyl group or a propionyl group. , butyryl group, isobutyryl group, valeryl group, isovaleryl group, 2-methylbutanoyl group, pivaloyl group, hexanoyl group, heptanoyl group, etc. are given as specific examples, and each is selected from the range of the designated number of carbon atoms.

The notation of (C _a -C _b haloalkyl) carbonyl in the present specification represents a haloalkyl-C (O) - group having the above meaning consisting of a to b carbon atoms, for example, a fluoroacetyl group , chloroacetyl group, difluoroacetyl group, dichloroacetyl group, trifluoroacetyl group, chlorodifluoroacetyl group, bromodifluoroacetyl group, trichloroacetyl group, pentafluoropropionyl group, heptafluoro A butanoyl group, 3-chloro-2,2-dimethylpropanoyl group, etc. are mentioned as a specific example, Each is selected from the range of the designated number of carbon atoms.

The notation of (C _a ~ C _b alkoxy) carbonyl 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, ethoxy Specific examples include a carbonyl group, n-propyloxycarbonyl group, i-propyloxycarbonyl group, n-butoxycarbonyl group, i-butoxycarbonyl group, t-butoxycarbonyl group, and the like, each selected from the range of the designated number of carbon atoms. .

The notation of (C _a ~ C _b haloalkoxy) carbonyl in the present specification represents a haloalkyl-OC(O)- group having the above meaning consisting of a to b carbon atoms, for example, in 2-chloro Specific examples include oxycarbonyl group, 2,2-difluoroethoxycarbonyl group, 2,2,2-trifluoroethoxycarbonyl group, 2,2,2-trichloroethoxycarbonyl group, and each designation It is selected from the range of the number of carbon atoms.

The notation of (C _a to C _b alkylamino) carbonyl 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, 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 carbamoyl group A parent 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 (C a} to C _b haloalkyl) aminocarbonyl represents a carbamoyl group in which one of the hydrogen atoms is substituted with a haloalkyl group having the above meaning consisting of a to b carbon atoms, examples 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.

_{The notation of di(C a} -C _b alkyl) aminocarbonyl in the present specification is an alkyl group having the above meaning consisting of a to b number of carbon atoms, which may have both hydrogen atoms, may be the same, or may be different from each other. represents a carbamoyl group substituted by, for example, N,N-dimethylcarbamoyl group, N-ethyl-N-methylcarbamoyl group, N,N-diethylcarbamoyl group, N,N-di-n -Propylcarbamoyl 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 others, each independently a hydrogen atom, a halogen atom, C ₁ to C ₆ It is preferably a substituent selected from the group consisting of alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C _{6 haloalkoxy, cyano and nitro.}

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 described above} in terms of orientation sensitivity, and a halogen atom, C ₁ to C ₆ alkyl A substituent selected from the group consisting of , C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy, cyano and nitro is more preferred.

Moreover, it ^{is also preferable that any 1 or 2 substituent of R 101} , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ and R ¹⁰⁵ is a group represented by the formula (c-2), and among them, R ¹⁰³ is a group represented by the formula (c-2). It is preferable that it is a group represented by ). As such a monomer, 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 is exemplified. 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-( Monomers which have 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.

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

<Organic solvent>

The organic solvent used for the polymer composition of 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-methoxymethyl propionate, 3-ethoxy methyl ethyl propionate, 3-methoxy ethyl propionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionate propyl, 3- Butyl methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate , Propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate ester, ethyl lactate ester , lactate n-propyl ester, lactate n-butyl ester, lactate isoamyl ester, and the like. 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 exhibits liquid crystallinity in a predetermined temperature range, (B) a dichroic dye and an organic solvent. Moreover, (C) The compound represented by the said Formula (c) is contained 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 the photosensitive side chain type polymer capable of expressing the liquid crystallinity described above. At this time, as for content of a resin component, 1 mass % - 20 mass % are preferable, More preferably, they are 3 mass % - 15 mass %, Especially preferably, they are 3 mass % - 10 mass %.

In the polymer composition of the present embodiment, the above-mentioned resin component may be a photosensitive side-chain type polymer capable of expressing the liquid crystallinity all described above, but other than these in the range not impairing the liquid crystal expression ability and the photosensitive performance. Other polymers may be mixed. 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 expressing liquid crystallinity are exemplified.

The polymer composition used for this invention may contain components other than said (A) and (B) and an organic solvent. Examples thereof include, but are not limited to, a compound for improving film thickness uniformity and surface smoothness when applying a polymer composition, a compound for improving adhesion between an alignment layer and a substrate, and the like.

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.), Asahi Guard (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 [ the usage ratio of these surfactant / 100 mass parts of resin components contained in a polymer composition ], Preferably it is 0.01 mass part - 2 mass parts, More preferably, they are 0.01 mass part - 1 mass part.

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

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, you may contain the additive of the following phenoplast type|system|group and an epoxy group containing compound in a polymer composition for the purpose of providing heat resistance. 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, 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.

In addition, the present invention relates to a method for manufacturing a substrate and a change device 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 photosensitive side chain polymer that exhibits liquid crystallinity in a predetermined temperature range, (B) a step of coating a polymer composition containing a dichroic dye and an organic solvent on a substrate to form a coating film;

[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 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, (B) a polarizing layer-forming composition containing a dichroic dye and (D) a polymerizable liquid crystal is applied, and a coating film is formed by drying by heating, a process of irradiating the coating film with ultraviolet rays;

[V-2] A step of forming a coating film by applying (E) a polarizing layer-forming composition 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 process of [I]-[III] and [IV] which the manufacturing method of this invention has is demonstrated.

<Process[I]>

In step [I], (A) a photosensitive branched-chain polymer that exhibits liquid crystallinity in a predetermined temperature range, (B) a polymer composition containing a dichroic dye and an organic solvent is applied on a substrate to form a coating film .

<substrate>

The substrate is usually a transparent substrate. On the other hand, when the substrate of the polarizing plate of the present invention (hereinafter also referred to as the present polarizing plate) is not installed on the display surface of the display element, for example, when the polarizing film in which the substrate is removed from the present polarizing plate is installed on the display surface of the display element , the substrate does not have to be transparent. The transparent substrate means a substrate having transparency that can transmit 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. From the viewpoints of availability and transparency, polyethylene terephthalate, polymethacrylic acid ester, cellulose ester, cyclic olefin resin, or polycarbonate is 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 in the market. Moreover, a cellulose ester base material can also be obtained easily in the 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 in a market. As commercially available cyclic olefin resin, "Topas" [Ticona Corporation (Germany)], "Aton" [JSR Corporation], "ZEONOR" [Nippon Zeon Corporation], "ZEONEX (ZEONEX)" )"Nippon Zeon Co., Ltd.] and "Apel" [made by 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 “Scina” [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 an expensive cyclic olefin can be comparatively reduced in the manufacture.

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

The surface of the substrate on which the polarizing layer is not formed may be subjected to a hard coat treatment, an antireflection treatment, an antistatic treatment, or the like. 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 for applying the above-described polymer composition on the substrate is not particularly limited.

As for the coating method, industrially, a method of performing screen printing, offset printing, flexographic printing, inkjet method, or the like 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 ~ 230 ℃, preferably at 50 ~ 200 ℃ 0.4 minutes ~ 60 minutes, Preferably, the coating film can be obtained by evaporating the solvent for 0.5 minutes to 10 minutes. The drying temperature at this time 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 anisotropy expression, 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 was 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 by 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 ray to be used, an ultraviolet ray 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, an ultraviolet ray 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 a 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 which 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 a thin film surface 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. For this reason, it is more preferable that the heating temperature is in the temperature range of the liquid-crystal expression temperature on the surface of a 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 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 When the heating temperature is lower than the above temperature range, the effect of amplifying the anisotropy by heat in the coating film tends to be insufficient, and when 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 and forming 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 the ability to control the alignment of the liquid crystal is prepared.

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 photo-crosslinkable 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 is performed. After performing, a polarizing element is created.

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

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 and anisotropic introduction|transduction to a coating film can be implement|achieved.

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 groups in the coating film for photocrosslinking reaction, photoisomerization reaction, or photofree potential reaction. corresponding to the amount of irradiation. As a result of irradiating polarized ultraviolet light to the coating film used in the present invention, if there are few photosensitive groups in the side chain that undergo photocrosslinking reaction, photoisomerization reaction, or photofreeze potential reaction, a sufficient amount of photoreaction is not obtained. In that case, even after heating, sufficient self-organization does not proceed. On the other hand, in the coating film used in the present invention, when polarized ultraviolet light is irradiated with respect to a structure having a photocrosslinkable group, when the photosensitive group of the side chain to be crosslinked becomes excessive, the crosslinking reaction between the side chains proceeds excessively. In that case, the obtained film|membrane 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 rays are irradiated with respect to a structure having an optical fleece potential, if the photosensitive groups of the side chain reacting with the optical fleece potential are excessive, the liquid crystallinity of the coating film is excessively lowered. In that case, the liquid crystallinity of the obtained film|membrane also falls, and it may interfere with the progress of self-organization by subsequent heating. In addition, when polarized ultraviolet light is irradiated with respect to a structure having a photofree potential, if the irradiation amount of ultraviolet light is too large, the side chain type polymer is photodegraded, which may interfere with 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 mol of the photosensitive group of the side chain type polymer film It is preferable to set it as % - 40 mol%, 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 such a range, self-organization in the subsequent heat treatment proceeds efficiently, and highly anisotropic 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 photofreezing dislocation 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 polarized-ultraviolet rays.

That is, with respect to the coating film used in the present invention, the ultraviolet absorption in the direction parallel to the polarization direction of the polarized ultraviolet rays and the ultraviolet absorption in the 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 the direction parallel to the polarization direction of the polarized ultraviolet rays and the ultraviolet absorbance in the perpendicular direction, in 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 polarized 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 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 UV light to undergo photocrosslinking.

From the above, in the production 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 polarized UV irradiation to 50 ° C. to 190 ° C. By doing in this way, the coating film used for this invention WHEREIN: A larger anisotropy comes to be provided.

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

<Polarizing layer forming composition>

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

(E) The composition containing the pigment|dye which has lyotropic liquid crystal 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, and a mixed solvent of water and a hydrophilic solvent. 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.

(B) The component (B) mentioned above is used as a dichroic dye.

<(D) Polymerizable liquid crystal>

(D) 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 them, 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. A thermotropic liquid crystal or a lyotropic liquid crystal may be sufficient as the compound which shows liquid crystal, and a nematic liquid crystal or a smectic liquid crystal in a thermotropic liquid crystal may be sufficient as it.

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 them, 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 L phase is more preferable, and a higher-order smectic liquid crystal compound that forms smectic B phase, smectic F phase or smectic I phase is more preferable. If the liquid crystal phase formed by the polymerizable liquid crystal compound is a higher-order smectic phase, a polarizing film having a higher degree of alignment order can be manufactured. In addition, a black peak derived from a higher-order structure such as a hexatic phase or a crystal phase is obtained in the X-ray diffraction measurement of a long polarizing film having such a high degree of alignment order. The black peak is a peak derived from the periodic structure of molecular alignment, and if the liquid crystal phase formed by the polymerizable liquid crystal compound is their higher order smectic phase, a film having a periodic interval of 3.0 to 6.0 Å can be obtained.

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

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 optionally substituted alkanediyl group having 1 to 20 carbon atoms, 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 trans-cyclohexane-1,4 optionally substituted. - It is preferable that the diyl group is unsubstituted.

The substituents optionally included in the optionally substituted 1,4-phenylene group or the optionally substituted cyclohexane-1,4-diyl group include an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group and a butyl group, and a cyano group. and a halogen atom.

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. A polymerizable liquid crystal compound having a photopolymerizable group is advantageous in that it can be polymerized under lower temperature conditions.

The ^{polymerizable groups represented by U 1} and U ² may be independently different from each other, but 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 them, 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 optionally substituted 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, unsubstituted and linear It is more preferable that it is an alkanediyl group.

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 each represented by formulas (1-13), (1-14) and (1-15) is preferable.

Exemplary 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 compound (c), and it is more preferable that 2 or more types are 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.

<(E) Dye having lyotropic liquid crystal properties>

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

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

Among azo-type 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 a coating solution containing such an azo compound, a polarizing layer having excellent polarization characteristics 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. For this reason, the coating liquid containing the azo compound which has a polar group shows especially favorable lyotropic liquid crystal property.

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 (E-1) is preferable.

[Formula 38]

In the general formula (E-1), Q ¹ represents a substituted or unsubstituted aryl group, Q ² represents a substituted or unsubstituted arylene group, and R ^E 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 , represents an integer from 0 to 6. However, at least either one of m7 and n7 is not 0 and 1≤m7+n7≤6. When m7 is 2, each R ^E is the same or different.

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

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 (E-1) is not particularly limited. The said naphthyl group points out the naphthyl group shown on the right side in Formula (E-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 E} of the general formula (E-1) has a substituent, the substituent includes the substituents exemplified in the following aryl group or arylene group. .

R ¹ is preferably a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted acetyl group, and more preferably a hydrogen atom.

As said substituted or unsubstituted alkyl group, a substituted or unsubstituted C1-C6 alkyl group is mentioned.

M (counterion) of the said general formula (E-1), Preferably, it is 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; an ammonium ion optionally substituted with an alkyl group or a hydroxyalkyl group; and salts of organic amines. As the metal ion, 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 above general formula (E-1), when SO ₃ M is two or more, each M may be the same or different. In addition, in the general formula (E-1), when _{M of SO 3 M is a cation having a divalent or higher cation, it bonds with SO 3} ⁻ of an azo compound of the other general formula (E-1) adjacent to it to form a supramolecular association. can form.

m7 of the said general formula (E-1) becomes like this. Preferably it is 1. Moreover, n7 of general formula (E-1) becomes like this. Preferably it is 1 or 2.

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

[Formula 39]

In the general formula (E-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 in addition to 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. In any case in which the aryl group or the arylene group is substituted or unsubstituted, the aromatic disazo compound of the general formula (E-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 the group consisting of an alkoxy group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, a carboxyl group, a sulfonic acid group, and a nitro group. The aromatic disazo compound having such a substituent is particularly 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 (E-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 (E-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 (E-2), R ^E , M , m7 and n7 are the same as those in the general formula (E-1).

In general formula (E-2), A ^E and B ^E represent a substituent, and a and b represent the substitution number. A ^E and B ^E 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 a is an integer of 0-5, said b represents the integer of 0-4. However, at least either one of a and b is not 0. When a is 2 or more, the substituents A ^E may be the same or different. When b is 2 or more, the substituent B ^E may be the same or different.

It is preferable to use the aromatic disazo compound represented by the following general formula (E-3) among the aromatic disazo compounds contained in general formula (E-2). In the aromatic disazo compound of the general formula (E-3), the substituent A ^E is bonded to the para position with respect to the azo group (-N=N-). Moreover, in the aromatic disazo compound of general formula (E-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 (E-3) is used, a polarizing plate with a high degree of polarization can be obtained.

[Formula 41]

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

In general formula (E-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 (E-1) to (E-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 a symbol map (pages 135 to 152).

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

The content ratio of the (D) polymerizable liquid crystal compound or (E) a dye having lyotropic liquid crystal properties in the polarizing layer-forming composition is usually based on the solid content of the polarizing layer-forming composition from the viewpoint of enhancing the orientation of the liquid crystal compound. It is 70-99.9 mass parts, Preferably it is 80-99.9 mass parts, More preferably, it is 85-99 mass parts, More preferably, it is 90-99 mass parts.

<Process[IV] and Process[V]>

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

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

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

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

(B) In the step of irradiating an ultraviolet ray to a coating film containing a dichroic dye and (D) a polymerizable liquid crystal, (D) polymerization of the polymerizable liquid crystal is carried out by a known method of polymerizing a compound having a polymerizable functional group. can be done 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, polymerization in a dry film obtained by coating and drying a composition containing a photopolymerization initiator in addition to a polarizing layer-forming composition containing (B) a dichroic dye and (D) a polymerizable liquid crystal After making the liquid crystal into a 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 photopolymerization initiator contained in the dry film, the type of (D) the polymerizable liquid crystal (in particular, the type of the photopolymerization group possessed by the (D) 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 them, ultraviolet light is preferable from the viewpoint of being able to easily control the progress of the polymerization reaction and being widely used in the art as a photopolymerization apparatus, so that photopolymerization by ultraviolet light is possible (D) 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, when polymerization of the (D) polymerizable liquid crystal is carried out at a lower temperature, even if a substrate having relatively low heat resistance is used, a polarizing layer can be appropriately formed.

On the alignment layer of the substrate having the alignment layer, (E) a polarizing layer-forming composition containing a dye having lyotropic liquid crystal properties is applied, and the coating in the step of forming a coating film by heating and drying is usually performed by spin. It is carried out by a known method such as a coating method, such as a coating method, an extrusion method, a gravure coating method, a die coating method, a bar coating method, an applicator method, or 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.

In addition, the drying temperature means the temperature of the atmosphere which dries a coating film, not the temperature inside or the surface of the coating film containing the pigment|dye which has (E) 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 the alignment layer and the polarizing layer can be determined by measurement with an interference film thickness meter, a laser microscope, or a stylus film thickness meter.

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.

Hereinafter, although this invention is demonstrated using an Example, this invention is not limited to this Example.

Example

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

<solvent>

Each of the resin compositions of 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 determined 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.

In addition, the following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) were expressed in terms of polystyrene.

Column temperature: 50℃

Eluent: N,N-dimethylformamide (as an additive example, lithium bromide-hydrate (LiBr·H ₂ O) is 30 mmol/L, phosphoric acid/anhydrous crystal (o-phosphoric acid) is 30 mmol/L, tetrahydrofuran (THF) 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 1-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 1-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 the formula (Ex-A) (hereinafter also referred to as compound (Ex-A)). This compound (Ex-A) was reacted with methoxyphenol in the presence of DCC and DMAP to obtain a compound represented by the following formula (Ex-2).

[Formula 42]

<Synthesis Example 4>

16.0 g of the methacrylic acid ester represented by the formula (Ex-1) and 0.4 g of α,α'-azobisisobutyronitrile 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, followed by filtration and drying under reduced pressure to remove residual monomers to obtain an acrylic polymer (P1). Mn of the obtained acrylic copolymer was 9,300, and Mw was 16,000.

<Synthesis Example 5>

8.0 g of the methacrylic acid ester represented by the formula (Ex-1), 7.4 g of the methacrylic acid ester represented by the formula (Ex-A), 0.8 g of α,α′-azobisisobutyronitrile as a polymerization catalyst was dissolved in 145.0 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, filtered and dried under reduced pressure to remove residual monomers to obtain an acrylic copolymer (P2). Mn of the obtained acrylic copolymer was 8,000, and Mw was 20,000.

<Synthesis Example 6>

10.0 g of the methacrylic acid ester represented by the formula (Ex-1), 5.3 g of the methacrylic acid ester represented by the formula (Ex-2), 0.2 g of α,α'-azobisisobutyronitrile as a polymerization catalyst was dissolved in 165.0 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 (P3). Mn of the obtained acrylic copolymer was 11,000, and Mw was 21,000.

<Synthesis Example 7>

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), 0.2 g of α,α'-azobisisobutyronitrile 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, filtered and dried under reduced pressure to remove residual monomers to obtain an acrylic copolymer (P4). Mn of the obtained acrylic copolymer was 14,000, and Mw was 24,000.

<Production Example 1>

[Preparation of polarizing layer forming composition RM1]

14.6 g of a polymerizable liquid crystal (RMM141C, manufactured by Merck Corporation) and 0.44 g of a dichroic dye (G-241, manufactured by Hayashibara) were dissolved in 35.0 g of MIBK to prepare a polarizing layer-forming composition (RM1) having a solid content concentration of 30% by mass.

<Production Example 2>

[Preparation of polarizing layer-forming composition RM2]

14.4 g of a polymerizable liquid crystal (RMM141C, manufactured by Merck Corporation) and 0.58 g of a dichroic dye (G-470, manufactured by Hayashibara) were dissolved in 35.0 g of MIBK to prepare a polarizing layer-forming composition (RM2) having a solid content concentration of 30% by mass.

<Examples 1 to 6> and <Comparative Examples 1 to 2>

Each alignment layer forming composition of Examples 1 to 6 and Comparative Examples 1 to 2 was prepared with the composition shown in Table 1. An alignment layer was formed using each alignment layer-forming composition, and the dichroic ratio was measured for each alignment layer. Next, a polarizing element was formed using the polarizing layer-forming composition. About each of the obtained polarizing elements, evaluation of orientation, a polarization degree measurement, and a dichroic ratio measurement were performed.

[Table 1]

<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 DEG 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 to the coating film surface through a polarizing plate.} Then, it was heated at 170° C. for 5 minutes on a hot plate to form an alignment layer.

[Measurement of dichroic ratio of alignment layer]

The dichroic 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 polarizing layer forming composition RM1 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 degree and 45 degree between cross nicol of a polarizing microscope, and the light leakage state was observed. In the case of orientation, no light leakage occurs at 0° and a dark field state is observed, and at 45° light leakage occurs and a bright field state is observed. A 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". These measurement results are shown in Table 2.

[Polarization measurement]

The polarization degree of the obtained polarizing element was measured as follows. The transmittance (T1) in the direction of the transmission axis and the transmittance (T2) in the direction of the absorption axis 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 polarization degree was calculated using the following formula. Table 2 shows the measurement results.

Polarization degree (%)={(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 prepared in the same manner as in Example 1, except that the linearly polarized light at the time of forming the alignment layer was 5 mJ/cm ^{2 , and the heating temperature after the polarized light exposure was 150°C.} 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 orientation layer formation was 120 degreeC. 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 100 degreeC. Table 2 summarizes the results.

<Example 5>

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 140 degreeC. Table 2 summarizes the results.

<Example 6>

A polarizing element was prepared in the same manner as in Example 1 except that the heating temperature after polarization exposure at the time of forming the alignment layer was 100°C, and RM2 was used for the polarizing layer forming composition. Table 2 summarizes the results.

<Comparative Example 1>

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 100 degreeC. Table 2 summarizes the results.

<Comparative Example 2>

A polarizing element was prepared in the same manner as in Example 1 except that the heating temperature after polarization exposure at the time of forming the alignment layer was 100°C, and RM2 was used for the polarizing layer forming composition. Table 2 summarizes the results.

[Table 2]

In Comparative Examples 1 and 2 in which the dichroic dye was not added to the alignment layer, the dichroic ratio of the alignment layer was 0. On the other hand, in Examples 1-6 which mix|blended the dichroic dye with the orientation layer, high dichroism ratio was obtained and it was possible to orientate the dichroic dye in the orientation layer.

The polarizer obtained in Examples 1-5 was able to express a high polarization degree and dichroism ratio, when compared with the comparative example 1.

The polarizer obtained in Example 6 was able to express a high polarization degree and dichroism ratio, when compared with the comparative example 2.

Claims (6)

A polymer composition comprising (A) a photosensitive side-chain polymer that exhibits liquid crystallinity in a predetermined temperature range, (B) a dichroic dye and an organic solvent,
(A) The polymer composition whose component is a side chain type polymer|macromolecule which has any 1 type of photosensitive side chains 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 thereto may be substituted with a halogen group;
T represents a single bond or an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded thereto may be substituted with a halogen group;
Y ₁ represents a ring selected from the group consisting of a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same selected from their substituents Or represents a group formed by bonding 2 to 6 different rings through a bonding group B, and the hydrogen atoms bonded thereto are 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 group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms. ;
Y ₂ represents a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, Each hydrogen atom is independently -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms. may be substituted;
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-, -CH=CH-CO-O-, or -O-CO-CH= When CH- is represented and 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 group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
q1 and q2, one is 1 and the other is 0;
q3 is 0 or 1;
P and Q each independently represent a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof ; However, when X is -CH=CH-CO-O- or -O-CO-CH=CH-, P or Q on the side to which -CH=CH- is bonded represents an aromatic ring;
l1 is 0 or 1;
l2 is an integer from 0 to 2;
When both l1 and l2 are 0 and T is a single bond, A also represents a single bond;
When l1 is 1 and T is a single bond, B also represents a single bond;
H represents a group selected from the group consisting of a divalent naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and combinations thereof;
I represents a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and combinations thereof. 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 represents a group selected from the group consisting of a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocycle, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and combinations thereof, Each hydrogen atom bonded to -NO ₂ , -CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms may be substituted;
R ₃ is a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen containing a heterocyclic ring, 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 (25) to (26), the sum of all m is 2 or more, and formulas (27) to (28) In , 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 group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocycle, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, and; an alkyl group or an alkyloxy group;
Z ₁ , Z ₂ represents a single bond, -CO-, -CH ₂ O-, -CH=N-, -CF ₂ -. According to claim 1,
(C) The polymer composition characterized by containing the compound represented by following formula (c) as a component.

( ^{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, C ₁ to C ₆ alkyl, C ₁ to C ₆ haloalkyl , C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy, C ₃ -C ₈ cycloalkyl, C ₃ -C ₈ halocycloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ haloalkenyl, C ₃ -C ₈ Cycloalkenyl, C ₃ -C ₈ Halocycloalkenyl, C ₂ -C ₆ Alkynyl, C ₂ -C ₆ Haloalkynyl, (C ₁ -C ₆ Alkyl)carbonyl, (C ₁ ~C ₆ Haloalkyl)carbonyl, (C ₁ ~C ₆ Alkoxy)carbonyl, (C ₁ ~C ₆ Haloalkoxy)carbonyl, (C ₁ ~C ₆ Alkylamino)carbonyl, (C ₁ ~C ₆ haloalkyl)aminocarbonyl, di(C ₁ -C ₆ alkyl)aminocarbonyl, cyano and nitro, any of R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ and R ¹⁰⁵ . When 3 to 4 are the above definitions, the ^{other one or two of R 101} , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ and R ¹⁰⁵ is the following formula (c-2)

(In formula (c-2), the broken line represents the number of bonds, R ¹⁰⁶ represents an alkylene group having 1 to 30 carbon atoms, phenylene or a divalent carbocyclic or heterocyclic ring, and this alkylene group, phenylene or divalent One or more hydrogen atoms in the carbocyclic or heterocyclic ring may be substituted with a fluorine atom or an organic group, and -CH ₂ CH ₂ ^{- in R 106} may be substituted with -CH=CH-; -CH ₂ - in R ¹⁰⁶ may be substituted with phenylene or a divalent carbocyclic or heterocyclic ring, and 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-. R ¹⁰⁷ represents a hydrogen atom or a methyl group); n represents 0 or 1.) An alignment layer forming composition comprising the polymer composition according to any one of claims 1, 4 and 5.