KR20180132652A - The orientation layer forming composition - Google Patents

Abstract

[PROBLEMS] To provide a polymer composition for a liquid crystal alignment film capable of orienting a polymerizable liquid crystal composition when obtaining a polarizing element having high dichroism.
[MEANS FOR SOLVING PROBLEMS] The present invention provides a polymer composition containing (A) a photosensitive side chain type polymer exhibiting liquid crystallinity in a predetermined temperature range, (B) a dichroic dye and an organic solvent. A substrate having a liquid crystal alignment film formed from the polymer composition can be obtained by applying a polymerizable liquid crystal composition onto an alignment film, then heating and drying, and further irradiating ultraviolet light as needed to obtain a polarizing element having high dichroism.

Description

The orientation layer forming composition

The present invention relates to a polymer composition useful for forming an orientation layer for orienting a polymerizable liquid crystal composition to be a polarizing layer in the formation of a polarizing element.

As a polarizing plate used for a liquid crystal display or the like, iodine has been widely used as a dichroic dye. However, there is a problem that the iodine polarizing film is inferior in heat resistance and light resistance, and therefore attempts have been made to use an organic dichroic substance, that is, a dichroic dye.

Conventionally, dyes having an azo skeleton as a basic skeleton (Patent Documents 1 and 2) and dyes having an anthraquinone skeleton are widely used as dichroic dyes in order to obtain high dichroism.

As a method of producing a polarizing plate, a method of stretching a polymer film containing iodine or a dichroic dye or the like, a liquid crystal composition obtained by mixing a liquid crystal compound serving as a host material with a dye serving as a guest material, (Patent Document 3). Furthermore, in order to provide a more stable polarizing film, a method using a mixture of a crosslinkable liquid crystal and a polymerizable dichroic dye (Patent Document 4); A method of producing an optically anisotropic material by adding a polymerizable non-liquid crystal solvent to a polymerizable liquid crystal compound and allowing the polymerizable non-liquid crystal solvent to remain in the coating film to improve adhesion with other optical films and the like (Patent Document 5); Also, a method of preparing a polarizer by effectively preparing a polymerizable mesogen tablet containing a polymerizable mesogen compound and a dichroic dye and using the polymerizable mesogen compound in terms of time and cost (Patent Document 6) has also been proposed.

Japanese Patent Application 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 Application Laid-Open No. 2004-198480 Japanese Patent Publication No. 2006-161051

At present, in order to enhance the absorption property in the visible light region, it has been studied to highly blend a dichroic dye excellent in absorption property into the liquid crystal composition. However, such a dichroic dye generally has a low solubility in a solvent, so that there is a problem that it is difficult to formulate a liquid crystalline composition with a high degree of solubility.

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

Means for Solving the Problems The present inventors have intensively studied to achieve the above object, and as a result, found the following inventions.

≪ 1 > A polymer composition comprising (A) a photosensitive side chain polymer which exhibits liquid crystallinity in a predetermined temperature range, (B) a dichroic dye and an organic solvent.

<2> The polymer composition according to the above <1>, wherein the component (A) is a side chain type polymer having a photosensitive side chain which causes photo crosslinking, photoisomerization, or light free transition.

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

[Chemical Formula 1]

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

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

Y ₁ represents a ring selected from the group consisting of monovalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings and alicyclic hydrocarbons having 5 to 8 carbon atoms, or the same Or a group formed by bonding different 2 to 6 rings via a bonding group B, and each of the hydrogen atoms bonded to these groups independently represents -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 divalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings, alicyclic hydrocarbons having 5 to 8 carbon atoms, and combinations thereof, Each hydrogen atom is independently selected from the group consisting of -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 Lt; / RTI &gt;

R represents a hydroxyl 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 the number of X's is 2, X's may be the same or different;

Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded to these groups are each independently -NO ₂ , -CN, -CH═C (CN) ₂ , A halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;

q1 and q2 are one in one and zero in the other;

q3 is 0 or 1;

P and Q each independently represent a group selected from the group consisting of divalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings, alicyclic hydrocarbons having 5 to 8 carbon atoms, and combinations thereof ; Provided that when X is -CH = CH-CO-O- or -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 of 0 to 2;

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

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

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

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

(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 heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, May be independently substituted with -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;

R ₃ represents a hydrogen atom, -NO ₂ , -CN, -CH═C (CN) ₂ , -CH═CH-CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl 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;

(25) to (26), the sum of all m is 2 or more, and in formulas (27) to (28), m represents an integer of 1 to 12, , The sum of all m is 1 or more, m1, m2 and m3 are each independently an integer of 1 to 3;

R ₂ represents 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 heterocyclic ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, An alkyl group, or an alkyloxy group;

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

<5> The polymer composition according to any one of <1> to <4>, which comprises, as the component (C), a compound represented by the following formula (c)

(3)

Wherein any three to five of R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ and R ¹⁰⁵ are each independently a hydrogen atom, a halogen atom, C ₁ -C ₆ alkyl, C ₁ -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 ^{101, R 102, R 103,} R 104 and R if any three or four of the definition of the ^{105, R 101, R 102,} R 103, R 104 and R ¹⁰⁵ of the remaining 1 or 2 is the following formula (c-2)

[Chemical Formula 4]

(In the 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 carbon ring or a heterocyclic ring, One or plural hydrogen atoms in the carbon ring or the 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 in the case where any of the following groups is 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, and n represents 0 or 1.)

&Lt; 6 > An alignment layer-forming composition comprising the polymer composition according to any one of the above items <1> to <5>.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a novel polymer composition which can be used for obtaining a polarizing plate having a high polarization performance without highly blending a dichroic dye into the liquid crystal composition.

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

The polymer composition of the present invention has a photosensitive side chain type polymer capable of exhibiting liquid crystallinity (hereinafter simply referred to as a side chain type polymer) and a dichroic dye, and the coating film obtained by using the above polymer composition has a liquid crystalline property And is a film having a photosensitive side chain type polymer that can be expressed. This coating film can be subjected to orientation treatment by polarized irradiation without rubbing treatment. After the polarized light irradiation, the film of the orientation control ability is imparted to the film (hereinafter, also referred to as an orientation layer) through the step of heating the polymer film of the side chain type. At this time, a slight anisotropy expressed by polarized light becomes a driving force, and the liquid crystalline side chain type polymer itself is efficiently rearranged by self-organization. As a result, a highly efficient alignment treatment can be realized as the alignment layer, and an alignment layer with high alignment control capability can be obtained. Here, the polymer composition contains a dichroic dye, so that an alignment layer having a high dichroic ratio can be obtained. Therefore, the polymer composition of the present invention is useful as an orientation layer forming composition for orienting a polarizing layer containing a liquid crystal composition and, if necessary, a dichroic dye in forming a polarizing layer.

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

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

(A) is a photosensitive side chain type polymer which exhibits liquid crystallinity in a predetermined temperature range.

(A) the side chain type polymer should react with light in a wavelength range of 250 nm to 400 nm and exhibit liquid crystallinity in a temperature range of 60 ° C to 300 ° C.

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

(A) the side chain type polymer preferably has a mesogen 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 attached to the main chain, and may cause a crosslinking reaction, an isomerization reaction, or a light-free potential in response to light. The structure of the photosensitive side chain is not particularly limited, but a structure which responds to light to cause a crosslinking reaction or a light-free potential is preferable, and it is more preferable to cause a crosslinking reaction. In this case, even when exposed to external stress such as heat, the realized orientation control ability can be stably maintained for a long period of time. The structure of the photosensitive side chain type polymer membrane capable of exhibiting liquid crystallinity is not particularly limited as long as it satisfies such characteristics, but it is preferable that the structure has a mesogen component which is rigid in the side chain structure. In this case, when the side chain type polymer is used as the liquid crystal alignment film, a stable liquid crystal alignment can be obtained.

The structure of this polymer includes, for example, a polymer having a main chain and a side chain bonded to the main chain, and the side chain thereof has a mesogen component such as a biphenyl group, a terphenyl group, a phenylcyclohexyl group, a phenylbenzoate group or an azobenzene group, A structure having a photosensitive group which undergoes a crosslinking reaction or an isomerization reaction in response to light and a structure in which a side chain having a main chain and a side chain bonded to the main chain is a mesogen component and a phenyl benzoate group .

More specific examples of the structure of the photosensitive side chain type polymer membrane capable of exhibiting liquid crystallinity include hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate,? -Methylene-? -Butyrolactone, styrene, (1) to (6) and side chains composed of at least one kind of the following formulas (1) to (6), preferably at least one kind selected from the group consisting of radicals such as vinyl, maleimide and norbornene Do.

[Chemical Formula 5]

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

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

Y ₁ represents a ring selected from the group consisting of monovalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings and alicyclic hydrocarbons having 5 to 8 carbon atoms, or the same Or a group formed by bonding different 2 to 6 rings via a bonding group B, and each of the hydrogen atoms bonded to these groups independently represents -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 divalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings, alicyclic hydrocarbons having 5 to 8 carbon atoms, and combinations thereof, Each hydrogen atom is independently selected from the group consisting of -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 Lt; / RTI &gt;

R represents a hydroxyl 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 the number of X's is 2, X's may be the same or different;

Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded to these groups are each independently -NO ₂ , -CN, -CH═C (CN) ₂ , A halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;

q1 and q2 are one in one and zero in the other;

q3 is 0 or 1;

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

l1 is 0 or 1;

l2 is an integer of 0 to 2;

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

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

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

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

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

l represents an integer of 1 to 12;

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

n is an integer of 0 to 12 (provided that n is 0 and B is a single bond).

[Chemical Formula 6]

The side chain may be any one of the photosensitive side chains selected from the group consisting of the following formulas (11) to (13).

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

(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, m 1 and m 2 have the same definitions as above.

[Chemical Formula 8]

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

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

[Chemical Formula 9]

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

In the formula, A, B, Y ₁ , 1, q 1, q 2, m ₁ , and m 2 have the same definitions as above.

R ₁ represents 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 an alkyloxy group having 1 to 5 carbon atoms Lt; / RTI &gt;

[Chemical formula 10]

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

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

(11)

The side chain type polymer (A) preferably has one kind 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 heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, May be independently substituted with -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;

R ₃ represents a hydrogen atom, -NO ₂ , -CN, -CH═C (CN) ₂ , -CH═CH-CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl 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;

(25) to (26), the sum of all m is 2 or more, and in formulas (27) to (28), m represents an integer of 1 to 12, , The sum of all m is 1 or more, m1, m2 and m3 each independently represent an integer of 1 to 3;

R ₂ represents 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 heterocyclic ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, An alkyl group, or an alkyloxy group;

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

[Chemical Formula 12]

<< Preparation of photosensitive side chain type polymer >>

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

As the photoreactive group of the side chain, the following structures and derivatives thereof are preferable.

[Chemical Formula 13]

More specific examples of the photoreactive side chain monomers include radicals such as hydrocarbons, (meth) acrylates, itaconates, fumarates, maleates,? -Methylene-? -Butyrolactone, styrene, vinyl, maleimide and norbornene (7), a polymerizable group composed of at least one kind selected from the group consisting of a polymerizable group and a siloxane, and a photosensitive side chain composed of at least one of the above-mentioned formulas (1) to (6) (14) or (15), a photosensitive side chain composed of at least one kind selected from the group consisting of the compounds represented by the formulas (16) to (10), the photosensitive side chain comprising at least one of the formulas (11) (18) or (19), and the photosensitive side chain represented by the above formula (20). The photosensitive side chain represented by the formula (20) or (17)

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

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

(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.)

[Chemical Formula 17]

(Wherein R is OH or NH ₂ , M 1 is a hydrogen atom or a methyl group , s 1 is a number of methylene groups and is a natural number of 2 to 9)

Examples of the photoreactive side chain monomer represented by the above formula (M1-1) include 4- (6-methacryloxyhexyl-1-oxy) cinnamic acid, 4- (6-acryloxyhexyl- (M1-1) such as cinnamic acid, cinnamic acid, 4- (3-methacryloxypropyl-1-oxy) cinnamic acid and 4- R represents OH and is selected from the group consisting of 4- (6-methacryloxyhexyl-1-oxy) cinnamamide, 4- (6-acryloxyhexyl- Propyl-1-oxy) cinnamamide and the like in which R in the formula (M1-1) represents NH ₂ .

[Liquid Crystalline Side-chain Monomer]

The liquid crystalline side chain monomer is a monomer in which the polymer derived from the monomer exhibits liquid crystallinity and the polymer can form a mesogen group at a side chain site.

As the mesogen group of the side chain, biphenyl or phenylbenzoate may be a single mesogen structure or may be a mesogen structure such as benzoic acid by hydrogen bonding of side chains to each other. The mesogen group of the side chain is preferably the following structure.

[Chemical Formula 18]

More specific examples of the liquid crystalline side chain monomers include radicals such as hydrocarbons, (meth) acrylates, itaconates, fumarates, maleates,? -Methylene-? -Butyrolactone, styrene, vinyl, maleimide and norbornene A polymerizable group composed of at least one kind selected from the group consisting of a polymerizable group and a siloxane, and a structure having side chains composed of at least one kind of the above-mentioned formulas (21) to (31).

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

[Chemical Formula 19]

[Chemical Formula 20]

(Wherein R represents OH or NH ₂ , M 1 represents a hydrogen atom or a methyl group, s 1 represents the number of methylene groups and is a natural number of 2 to 9)

Further, monomers represented by the formulas selected from the group consisting of the following formulas M210 to M2-16 may be used as the monomer having a substituent that exhibits liquid crystallinity, which is an example of the other monomer.

[Chemical 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.)

The side chain type polymer (A) can be obtained by a copolymerization reaction of the photoreactive side chain monomers expressing the liquid crystallinity described above. Further, it can be obtained by copolymerization of a photoreactive side chain monomer that does not exhibit liquid crystallinity and a liquid crystalline side chain monomer, or by copolymerization of a photoreactive side chain monomer that exhibits liquid crystallinity and a liquid crystalline side chain monomer. Further, it can be copolymerized with other monomers within a range that does not impair the ability of liquid crystallinity.

Other monomers include, for example, industrially available monomers capable of radical polymerization.

Specific examples of other monomers 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, methoxy triethylene glycol acrylate, 2- Methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate , And 8-ethyl-8-tricyclodecyl acrylate.

Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthrylmethyl methacrylate Methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, ethyl methacrylate, ethyl methacrylate, butyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, Methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-propyl methacrylate, 2-ethylhexyl methacrylate, Adamantyl methacrylate, 2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate.

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.

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

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 type polymer of the present invention is preferably from 10 mol% to 100 mol%, more preferably from 20 mol% to 95 mol%, still more preferably from 30 mol% to 90 mol% % Is more preferable.

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

The content of the liquid crystalline side chain in the side chain type polymer of the present invention is preferably 90 mol% or less, more preferably 5 mol% to 80 mol%, further preferably 10 mol% to 70 mol% desirable.

When the content of the liquid crystalline side chain in the side chain type polymer is higher than 90 mol% based on the total amount of side chains, the content of the photoreactive side chain is less than 10 mol% based on the entire side chain, There is a possibility that the coated film does not sufficiently exhibit the effect as the liquid crystal alignment film.

The side chain type polymer of the present invention may contain other photoreactive side chains and other side chains other than the liquid crystal side chain. The content thereof is the remaining part when the total content of the photoreactive side chain and the liquid crystalline side chain does not reach 100%.

The method of producing the side chain type polymer of the present embodiment is not particularly limited, and a general-purpose method that is handled industrially can be used. Specifically, it can be produced by cation polymerization, radical polymerization or anionic polymerization using a vinyl group of a liquid crystal side chain monomer or a photoreactive side chain monomer. Of these, radical polymerization is particularly preferable from the viewpoint of ease of reaction control and the like.

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

The radical thermal polymerization initiator is a compound which generates a radical by heating at a decomposition temperature or higher. Examples of such radical thermal polymerization initiators include ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide, diacyl peroxides such as acetyl peroxide and benzoyl peroxide and hydroperoxides such as (Di-tert-butyl peroxide, dicumyl peroxide, di-lauroyl peroxide, etc.), peroxyketal (dibutyl peroxide, (Peroxyneodecanoic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy 2-ethylcyclohexanoic acid-tert-amyl ester, etc.), persulfate Azo compounds such as azobisisobutylonitrile and 2,2'-di (2-hydroxyethyl) azobisisobutyronitrile, and the like can be used as the starting material, . These radical thermal polymerization initiators may be used singly or in combination of two or more kinds.

The radical photopolymerization initiator is not particularly limited as far as it is a compound that initiates radical polymerization by light irradiation. Examples of such radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl Benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 4-dimethylaminobenzoate, 4- Diethyl (t-butylperoxycarbonyl) benzophenone, 3,4,4'-tri (t-butylperoxycarbonyl) benzophenone, 2,4,6 - trimethylbenzoyldiphenylphosphine oxide, 2- (4'-methoxystyryl) - (Trichloromethyl) -s-triazine, 2- (3 ', 4'-dimethoxystyryl) -4,6-bis Bis (trichloromethyl) -s-triazine, 2- (2'-methoxystyryl) -4,6-bis (trichloromethyl) (trichloromethyl) -s-triazine, 4- [pN, N-di (ethoxycarbonylmethyl)] - Bis (trichloromethyl) -5- (2'-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) (P-dimethylaminostyryl) benzothiazole, 2- (p-dimethylaminostyryl) benzothiazole, 2- Mercapto benzothiazole, 3,3'-carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl- (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2, 2'-bis (2,4-dichloro Phenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2' bis (2,4-dibromophenyl) -4,4 ' -Tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl- Imidazole, 3- (2-methyl-2-dimethylaminopropionyl) carbazole, 3,6-bis Bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 3,3 ', 4,4'-tetra (t-hexylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, Di (methoxycarbonyl) -4,4'-di (t-butylperoxycarbonyl) benzophenone, 3,4'-di (methoxycarbonyl) -4,3'-di Peroxycarbonyl) benzophenone, 4,4'-di (methoxycarbonyl) -3,3'-di (t-butylperoxycarbonyl) benzophenone, 2- (3-methyl- 2-ylidene) -1-naphthalen-2-yl-ethanone, or 2- (3-methyl- Benzothiazol-2 (3H) -ylidene) -1- (2-benzoyl) ethanone. These compounds may be used alone or in admixture of two or more.

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

The organic solvent used in the polymerization reaction of the photosensitive side chain type polymer capable of exhibiting liquid crystallinity is not particularly limited as long as the resulting polymer dissolves. Specific examples thereof are given below.

N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, But are not limited to, pyridine, dimethyl sulfone, hexamethyl sulfoxide,? -Butyrolactone, isopropyl alcohol, methoxymethyl pentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, Ketones, 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 mono 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, N-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, isopropanol, n-butanol, isobutanol, Propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene acetate Glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3- Propyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy- Amide, 3-butoxy-N, N-dimethylpropanamide, and the like.

These organic solvents may be used alone or in combination. The solvent may be a solvent that does not dissolve the resulting polymer, and the solvent may be mixed with the above-described organic solvent within the range in which the resulting polymer is not precipitated.

Further, in the radical polymerization, oxygen in the organic solvent causes the polymerization reaction to be inhibited, so that it is preferable to use the organic solvent that has been degassed to the extent possible.

The polymerization temperature in the radical polymerization can be selected from any of 30 ° C to 150 ° C, preferably 50 ° C to 100 ° C. If the concentration is excessively low, it becomes difficult to obtain a polymer having a high molecular weight. If the concentration is too high, the viscosity of the reaction liquid becomes excessively high and it becomes difficult to carry out uniform stirring. Therefore, Preferably 1% by mass to 50% by mass, and more preferably 5% by mass to 30% by mass. The initial stage of the reaction may be carried out at a high concentration, and then an organic solvent may be added.

In the radical polymerization reaction described above, when the ratio of the radical polymerization initiator to the monomer is small, the molecular weight of the obtained polymer is small, and if it is small, the molecular weight of the obtained polymer is large. Therefore, the ratio of the radical initiator is preferably 0.1 mol% And more preferably 10 mol%. In addition, various monomer components, solvents, initiators and the like may be added during the polymerization.

[Recovery of Polymer]

In the case of recovering the resulting polymer from the reaction solution of the photosensitive side chain type polymer capable of exhibiting liquid crystallinity obtained by the above-mentioned reaction, the reaction solution may be put into a poor solvent to precipitate these polymers. Examples of the poor solvent used for the precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, . The polymer precipitated by charging into a poor solvent can be recovered by filtration and then dried at room temperature or under reduced pressure or at normal pressure. Further, when the polymer precipitated and recovered is redissolved in an organic solvent and the operation of re-precipitation and recovery is repeated 2 to 10 times, impurities in the polymer can be reduced. As the poor solvent at this time, for example, alcohols, ketones, hydrocarbons and the like can be exemplified, and when three or more poor solvents selected from these are used, the purification efficiency is further improved, which is preferable.

The molecular weight of the side chain type polymer (A) of the present invention is preferably in the range of from 2000 (weight average molecular weight) measured by GPC (Gel Permeation Chromatography) to 2000 To 1,000,000, and more preferably from 5,000 to 100,000.

&Lt; (B) Dichroic dye>

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

The dichroic dye preferably has an absorption maximum wavelength (λMAX) in the range of 300 to 700 nm. Such dichroic dyes include, for example, acridine dyes, oxazine dyes, cyanine dyes, naphthalene dyes, azo dyes and anthraquinone dyes, among which azo dyes are preferred. Examples of the azo dyes include monoazo dyes, bisazo dyes, trisazo dyes, tetrakisazo dyes and stilbenazo dyes, preferably bisazo dyes and trisazo dyes.

The azo dye may be, for example, a compound represented by the formula (b) (hereinafter referred to as &quot; compound (b) &quot;

A ¹ (-N = NA ² ) _p -N = NA ³ (b)

[In the formula (b)

A ¹ and A ³ independently represent a phenyl group which may have a substituent, a naphthyl group which may have a substituent or a monovalent heterocyclic group which may have a substituent. A ² represents a 1,4-phenylene group which may have a substituent, a naphthalene-1,4-diyl group which may have a substituent or a divalent heterocyclic group which may have a substituent. p represents an integer of 1 to 4; When p is an integer of 2 or more, plural A ^{2 s} may be the same or different from each other.]

Examples of the monovalent heterocyclic group include groups 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 groups obtained by removing two hydrogen atoms from the heterocyclic compound.

As the substituent optionally having a phenyl group, a naphthyl group and a monovalent heterocyclic group in A ¹ and A ³ and a p-phenylene group, a naphthalene-1,4-diyl group and a divalent heterocyclic group in A ² , An alkyl group of 1 to 4 in embroidery; An alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group and a butoxy group; A fluorinated alkyl group having 1 to 4 carbon atoms such as a trifluoromethyl group; Cyano; A nitro group; A halogen atom; A substituted or unsubstituted amino group such as an amino group, a diethylamino group and a pyrrolidino group (the substituted amino group means an amino group having one or two alkyl groups having 1 to 6 carbon atoms or two substituted alkyl groups bonded together to form a carbon atom number 2 Quot; means an amino group forming an alkanediyl group of 1 to 8, and an unsubstituted amino group is -NH ₂ ).

The alkyl group having 1 to 6 carbon atoms may be either linear or branched and may be a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, methylbutyl group, 1-methylpropyl 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 and the like.

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

[Chemical Formula 22]

(23)

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

B ¹ to B ²⁰ independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, a nitro group, a substituted or unsubstituted amino group (substituted amino group and unsubstituted amino group Is as defined above, a chlorine atom or a trifluoromethyl group.

n1 to n4 independently represent an integer of 0 to 3;

If more than n1 is 2, a plurality of B ² may be different may be the same independently of one another,

When n2 is 2 or more, a plurality of B &lt; ⁶ &gt; may be the same or different from each other,

When n3 is 2 or more, a plurality of B &lt; ⁹ &gt; may be the same or different from each other,

When n4 is 2 or more, plural B &lt; ¹⁴ &gt; may be the same or different from each other independently.]

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

&Lt; EMI ID =

[In the formula (2-7)

R ¹ to R ⁸ 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.

The oxazone dye is preferably a compound represented by the formula (2-8).

(25)

[In the formula (2-8)

R ⁹ to R ¹⁵ 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.

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

(26)

[In the formula (2-9)

R ¹⁶ to R ²³ 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.

Examples of the alkyl group having 1 to 6 carbon atoms representing R ^x in the formulas (2-7), (2-8) and (2-9) include a methyl group, an ethyl group, a propyl group, And a hexyl group. 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 dye is preferably a compound represented by the formula (2-10) and a compound represented by the formula (2-11).

(27)

[In the formula (2-10)

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

(28)

and n5 represents an integer of 1 to 3.]

[Chemical Formula 29]

[In the formula (2-11)

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

(30)

and n6 represents an integer of 1 to 3.]

Examples of commercially available dichroic dyes include G-207, G-241 and G-470 (Hayashibara Co.), Yellow-8, KRD-901 and KRD-902 Ltd.) and SI-486 (manufactured by Mitsui Chemicals, Inc.).

The content of the dichroic dye as the component (B) in the alignment layer-forming composition is preferably 0.1 part by mass or more based on 100 parts by mass of the side chain polymer as the component (A) from the viewpoint of improving the alignment of the dichroic dye More preferably 0.1 parts by mass or more and 20 parts by mass or less, and still more preferably 0.1 parts by mass or more and 10 parts by mass or less.

&Lt; Component (C) >

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

(31)

Wherein any three to five of R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ and R ¹⁰⁵ are each independently a hydrogen atom, a halogen atom, C ₁ -C ₆ alkyl, C ₁ -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 halocycloalkyl alkenyl, 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 alkyl) carbonyl, (C ₁ ~ C ₆ haloalkyl) aminocarbonyl, any of the di (C ₁ ~ C ₆ alkyl) aminocarbonyl, cyano, and represents a substituent selected from the group consisting of nitro, R ^101, R ^102, R ^103, R ¹⁰⁴ and R ¹⁰⁵ three or four, if the definition of ^{the, R 101, R 102, R} 103, R 104 and R ¹⁰⁵ of the remaining one or two of the following formula (c-2)

(32)

(In the 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 carbon ring or a heterocyclic ring, One or plural hydrogen atoms in the carbon ring or the 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 in the case where any of the following groups is 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, and n represents 0 or 1.)

Examples of the halogen atom in the present specification include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. In the present specification, the notation of &quot; halo &quot;

The notation of C _a to C _b alkyl in the present specification represents a linear or branched chain hydrocarbon group having a number of carbon atoms ranging from a to b and includes, for example, a methyl group, ethyl group, n-propyl group, butyl group, a 1-methylbutyl group, a 3-methylbutyl group, a 1-ethylpropyl group, a 1-ethylbutyl group, a 1-methylbutyl group, , 1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-dimethylbutyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, and the like, and they are selected within the respective specified number of carbon atoms.

In the present specification, the notation of C _a to C _b haloalkyl means a straight or branched chain hydrocarbon group of a to b carbon atoms in which a hydrogen atom bonded to a carbon atom is optionally substituted by a halogen atom, , When they are substituted by two or more halogen atoms, these halogen atoms may be the same or different from each other. For example, fluoromethyl, chloromethyl, bromomethyl, iodomethyl, difluoromethyl, chlorofluoromethyl, dichloromethyl, bromofluoromethyl, trifluoromethyl, chlorodifluoromethyl, dichlorofluoro A methyl group, a trichloromethyl group, a bromodifluoromethyl group, a bromochlorfluoromethyl group, a dibromofluoromethyl group, a 2-fluoroethyl group, a 2-chloroethyl group, a 2-bromoethyl group, Bromo-2-fluoroethyl group, 2,2,2-trifluoroethyl group, 2-chloro-2,2-di 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-1,1,2,2-tetrafluoroethyl group, 1,2-dichloro-1,2,2-trifluoroethyl group, 2-chloro-1,1,2,2-tetrafluoroethyl group, Fluoropropyl group, 2-chloropropyl group, 2-bromopropyl group, 2-chloro-2-fluoropropyl group, 2-chloropropyl group, 3-dichloropropyl group, 2-bromo-3-fluoropropyl group, 3-bromo-2-chloropropyl group, 2,3-dibromopropyl group, , 3-bromo-3,3-difluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2-chloro-3,3,3-trifluoropropyl group, 3,3,3-pentafluoropropyl group, 1,1,2,3,3,3-hexafluoropropyl group, heptafluoropropyl group, 2,3-dichloro-1,1,2,3, 1-methylethyl group, 2-bromo-1-methylethyl group, 2,2,2-trifluoro-1- ( Trifluoromethyl) ethyl group, 1,2,2,2-tetrafluoro (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 , A 1,2,2,3,3,4,4-octafluorobutyl group, a 2-fluoro-2-methylpropyl group, a 2-chloro-1,1-dimethylethyl group, 1-dimethylethyl group, 5-chloro-2,2,3,4,4,5,5-heptafluoropentyl group, tridecafluorohexyl group, and the like. Specific examples of the Lt; / RTI &gt;

In the present specification, the notation of C _a to C _b cycloalkyl represents a cyclic hydrocarbon group having a number of carbon atoms ranging from a to b, and may form a monocyclic or bicyclic ring structure from a 3-membered ring to a 6-membered ring. In addition, each ring may be optionally substituted with an alkyl group in the range of the specified number of carbon atoms. For example, a cyclopropyl group, a 1-methylcyclopropyl group, a 2-methylcyclopropyl group, a 2,2-dimethylcyclopropyl group, a 2,2,3,3-tetramethylcyclopropyl group, a cyclobutyl group, Cyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, bicyclo [2.2.1] heptane-2-methylcyclopentyl group, 2-yl group, and the like, and is selected in the range of the respective designated carbon number.

In the present specification, the notation of C _a to C _b halocycloalkyl represents a cyclic hydrocarbon group having a carbon atom number of a to b in which a hydrogen atom bonded to a carbon atom is optionally substituted by a halogen atom, To form a monocyclic ring or a complex ring structure up to the ring. Each ring may be optionally substituted with an alkyl group in the range of a specified number of carbon atoms, and the substitution by a halogen atom may be a ring structure part, a side chain part, or both of them, Halogen atoms, these halogen atoms may be the same 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) Cyclohexyl group, 3- (trifluoromethyl) cyclohexyl group, 4- (trifluoromethyl) cyclohexyl group, and the like, and they are selected within the range of the respective specified number of carbon atoms.

In the present specification, the notation of C _a to C _b alkenyl represents a linear or branched chain of a to b number of carbon atoms and an unsaturated hydrocarbon group having one or two or more double bonds in the molecule, Propenyl group, a 2-propenyl group, a 1-methylethenyl group, a 2-butenyl group, a 1-methyl- Methyl-2-butenyl group, a 2-ethyl-2-propenyl group, a 1,1-dimethyl-2-propenyl group, Pentenyl group, 2,4-dimethyl-2,6-heptadienyl group, 3,7-dimethyl-2,6-octadienyl group and the like, and they are selected within the respective specified number of carbon atoms.

The notation of C _a to C _b haloalkenyl in the present specification is a straight chain or branched chain in which a hydrogen atom bonded to a carbon atom is optionally substituted by a halogen atom and the number of carbon atoms is a to b, Or an unsaturated hydrocarbon group having one or more double bonds. In this case, when they are substituted by two or more halogen atoms, these halogen atoms may be the same or different from each other. 2-propenyl group, 3-chloro-2-propenyl group, 2-bromo-2-propenyl group, 3-chloro-2-propenyl group, 2-propenyl group, 3,3-dichloro-2-propenyl group, 2,3-dibromo-2-propenyl group, Propyl group, a 2,3-trichloro-2-propenyl group, a 1- (trifluoromethyl) ethenyl group, a 3- 2-butenyl, 3-bromo-2-butenyl, 4,4-difluoro-3-butenyl, 3,4,4-trifluoro-3-butenyl, 4-trifluoro-2-butenyl group, 3-bromo-2-methyl-2-propenyl group and the like are exemplified and are selected within the respective specified number of carbon atoms.

In the present specification, the notation of C _a to C _b cycloalkenyl refers to an unsaturated hydrocarbon group having a carbon number of a to b and having one or two or more double bonds, Lt; RTI ID = 0.0 &gt; of-C &lt; / RTI &gt; In addition, each ring may be optionally substituted with an alkyl group in the range of the specified number of carbon atoms, and the double bond may be in any form of endo- or exo-. Cyclohexene-1-yl group, bicyclo [2.2.1] -5-heptene, 2-cyclopentene-1-yl group, 3- 2-yl group, and the like, and is selected in the range of the respective specified carbon atom number.

In the present specification, the notation of C _a to C _b halocycloalkenyl means that the hydrogen atom bonded to the carbon atom is a cyclic group having a carbon atom number of a to b, which is optionally substituted by a halogen atom, Or an unsaturated hydrocarbon group having a double bond or more and can form a monocyclic or a mixed ring structure from a 3-membered ring to a 6-membered ring. In addition, each ring may be optionally substituted with an alkyl group in the range of the specified number of carbon atoms, and the double bond may be in any form of endo- or exo-. The substitution by a halogen atom may be a cyclic moiety, a side chain moiety, or both of them, and when they are substituted by two or more halogen atoms, these halogen atoms may be the same as each other, May be different. For example, 2-chlorobicyclos [2.2.1] -5-hepten-2-yl group, and the like, and they are selected within the range of the respective specified number of carbon atoms.

In the present specification, the notation of C _a to C _b alkynyl represents an unsaturated hydrocarbon group having 1 to b carbon atoms in a straight chain or a branched chain and having one or two or more triple bonds in the molecule, Propyl group, a 2-propynyl group, a 1-methyl-2-propynyl group, a 2-pentynyl group, a 1-methyl- -Propinyl group, 2-hexynyl group, and the like, and they are selected within the range of the respective specified number of carbon atoms.

The notation of C _a to C _b haloalkynyl in the present specification is a straight chain or branched chain in which a hydrogen atom bonded to a carbon atom is optionally substituted by a halogen atom and the number of carbon atoms is a to b, Or an unsaturated hydrocarbon group having one or more triple bonds. In this case, when they are substituted by two or more halogen atoms, these halogen atoms may be the same or different from each other. For example, a 2-chloroethynyl group, a 2-bromoethynyl group, a 2-iodoethynyl group, a 3-chloro-2-propynyl group, Nyl group, and the like, and is selected in the range of the respective specified number of carbon atoms.

In the present specification, the notation of C _a to C _b alkoxy represents an alkyl-O- group having the above-mentioned meaning consisting of a to b carbon atoms and includes, for example, a methoxy group, an ethoxy group, Specific examples thereof include a propyloxy group, a n-butyloxy group, an i-butyloxy group, a s-butyloxy group, a t-butyloxy group, a n- pentyloxy group and a n- 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-mentioned meaning consisting of a to b carbon atoms and includes, for example, a difluoromethoxy group, a trifluoromethoxy group , Chlorodifluoromethoxy group, bromodifluoromethoxy group, 2-fluoroethoxy group, 2-chloroethoxy group, 2,2,2-trifluoroethoxy group, 1,1,2,2 , A tetrafluoroethoxy group, a 2-chloro-1,1,2-trifluoroethoxy group, a 2-bromo-1,1,2-trifluoroethoxy group, a 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- Trifluoro-1- (trifluoromethyl) ethoxy group, heptafluoropropyloxy group, 2-bromo-1,1,2,3,3,3-hexafluorov There may be mentioned pilok time such as a specific example, it is selected in the range of each of the specified number of carbon atoms.

In the present specification, the notation of (C _a to C _b alkyl) carbonyl represents an alkyl-C (O) - group having the above-mentioned meaning consisting of a to b carbon atoms and includes, for example, acetyl group, propionyl group , Butyryl group, isobutyryl group, valeryl group, isovaleryl group, 2-methylbutanoyl group, pivaloyl group, hexanoyl group, heptanoyl group and the like, and they are selected within the respective specified number of carbon atoms.

The notation of (C _a to C _b haloalkyl) carbonyl in the present specification represents a haloalkyl-C (O) - group having the above-mentioned meaning consisting of a to b carbon atoms and includes, for example, a fluoroacetyl group , A chloroacetyl group, a difluoroacetyl group, a dichloroacetyl group, a trifluoroacetyl group, a chlorodifluoroacetyl group, a bromodifluoroacetyl group, a trichloroacetyl group, a pentafluoropropionyl group, a heptafluoro Butanoyl group, 3-chloro-2,2-dimethylpropanoyl group, and the like, and they are selected within the range of the respective specified number of carbon atoms.

The notation of (C _a to C _b alkoxy) carbonyl in the present specification represents an alkyl-OC (O) - group having the above-mentioned meaning having a carbon number of a to b and includes, for example, a methoxycarbonyl group, ethoxy Specific examples thereof include a carbonyl group, an n-propyloxycarbonyl group, an i-propyloxycarbonyl group, an n-butoxycarbonyl group, an i-butoxycarbonyl group and a t-butoxycarbonyl group, .

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

The notation of (C _a to C _b alkylamino) carbonyl in the present specification indicates a carbamoyl group in which one of the hydrogen atoms is substituted by an alkyl group having the above-mentioned meaning of a to b number of carbon atoms, For example, methylcarbamoyl, ethylcarbamoyl, n-propylcarbamoyl, i-propylcarbamoyl, n-butylcarbamoyl, i-butylcarbamoyl, s- A phenoxy group, a phenoxy group, a phenoxy group, a phenoxy group, a phenoxy group, a phenoxy group, a phenoxy group, and a phenoxy group.

The notation of (C _a to C _b haloalkyl) aminocarbonyl in the present specification indicates a carbamoyl group in which one of the hydrogen atoms is substituted by a haloalkyl group having the above-mentioned meaning of a to b number of carbon atoms, For example, a 2-fluoroethylcarbamoyl group, a 2-chloroethylcarbamoyl group, a 2,2-difluoroethylcarbamoyl group, a 2,2,2-trifluoroethylcarbamoyl group, And is selected in the range of the respective specified number of carbon atoms.

In the present specification, the notation of di (C _a to C _b alkyl) aminocarbonyl may be either a hydrogen atom, an alkyl group of the above meaning having the number of carbon atoms of a to b, which may be the same or different from each other, For example, an N, N-dimethylcarbamoyl group, an N-ethyl-N-methylcarbamoyl group, an N, N-diethylcarbamoyl group, an N, -Propylcarbamoyl group, an N, N-di-n-butylcarbamoyl group and the like, and they are selected in the range of the respective specified number of carbon atoms.

The 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 the formula (c) are each independently a hydrogen atom, a halogen atom, a C ₁ -C ₆ 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.

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} from the viewpoint of orientation sensitivity and is preferably a halogen atom, a C ₁ -C ₆ alkyl , C ₁ ~ C ₆ haloalkyl, C ₁ ~ C ₆ alkoxy, C ₁ ~ C ₆ haloalkoxy, cyano, and more preferably substituents selected from the group consisting of a nitro group.

Also, R ^101, R ^102, R ^103, R ¹⁰⁴ and R group is a substituent of any one or two of the ¹⁰⁵ represented by the formula (c-2) is also preferred, and among them, R ¹⁰³ is formula (c-2 ) Is preferable. Examples of such a monomer include monomers selected from the above formulas M1-1 to M1-7 and M1-17 to M1-21 as cinnamic acid group-containing monomers. Examples of the monomer having a benzoic acid group include monomers selected from the above formulas M2-1 to M2-9.

Examples of such cinnamic acid and its derivatives include cinnamic acid derivatives such as cinnamic acid, 4-methoxy cinnamic acid, 4-ethoxy cinnamic acid, 4-propoxy cinnamic acid, and 4-fluoro cinnamic acid; 4- (3-methacryloxypropyl-1-oxy) cinnamic acid, 4- (3-methacryloxypropyl-1-oxy) And cinnamic acid group-containing monomers such as 4- (6-methacryloxyhexyl-1-oxy) benzoyloxy) cinnamic acid.

Examples of the benzoic acid and its derivatives include benzoic acid derivatives such as benzoic acid, 4-methoxybenzoic acid, 4-ethoxybenzoic acid, 4-propoxybenzoic acid and 4-fluorobenzoic acid; 4- (3-methacryloxypropyl) -benzoic acid, 4- (3-methacryloxypropyl) -benzoic acid, 4- And monomers having a benzoic acid group such as 4- (6-methacryloxyhexyl-1-oxy) benzoyloxy) benzoic acid.

The content of the component (C) in the polymer composition of the present invention is preferably 3 parts by mass to 100 parts by mass per 100 parts by mass of the polymer (A). When the content of the component (C) is less than 3 parts by mass, the irradiation dose margin is not improved. If the content of the component (C) exceeds 100 parts by mass, the solvent resistance of the resulting cured film may be deteriorated.

<Organic solvent>

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

N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N- N, N-dimethylpropaneamide, 3-ethoxy-N, N-dimethylpropane, N, N-dimethylacetamide, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, Amide, 3-butoxy-N, N-dimethylpropanamide, 1,3-dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isobutyl ketone, methyl isopropyl ketone, Propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, 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, methoxymethyl pentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve Propylene glycol monoacetate, propylene glycol monomethyl ether, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, 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, di Butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, 1-hexanol, n-hexane, n-butyl acetate, - pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n- Butyl propionate, propyleneglycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methylethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3 Methoxypropionate, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene Propylene glycol monoacetate, glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2-ethoxypropoxy) , Lactic acid methyl ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester, and lactic acid bisulphate ester. These may be used alone or in combination.

&Lt; Polymer composition >

The polymer composition of the present invention comprises (A) a photosensitive side chain type polymer which exhibits liquid crystallinity in a predetermined temperature range, (B) a dichroic dye and an organic solvent. (C) a compound represented by the above formula (c), if necessary.

[Preparation of polymer composition]

The polymer composition used in the present invention is preferably prepared as a coating liquid so as to be suitable for the formation of an orientation layer. That is, it is preferable that the polymer composition used in the present invention is 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 exhibiting the liquid crystallinity described above. In this case, the content of the resin component is preferably 1% by mass to 20% by mass, more preferably 3% by mass to 15% by mass, and particularly preferably 3% by mass to 10% by mass.

In the polymer composition of the present embodiment, the above-mentioned resin component may be a photosensitive side chain type polymer capable of exerting all of the liquid crystallinity described above. However, in the range of not deteriorating the liquid crystal- Other polymers may be mixed. At this time, the content of the other polymer in the resin component is 0.5% by mass to 80% by mass, preferably 1% by mass to 50% by mass.

Such another polymer includes, for example, a polymer which is composed of poly (meth) acrylate, polyamic acid, polyimide or the like and is not a photosensitive side chain type polymer capable of exhibiting liquid crystallinity.

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

Examples of the compound that improves film thickness uniformity and surface smoothness include fluorinated surfactants, silicone surfactants, and nonionic surfactants.

More specifically, it is possible to use, for example, EFTAX (registered trademark) 301, EF303, EF352 (manufactured by Tohchem Products), Megapack (registered trademark) F171, F173, R-30 (manufactured by DIC), Fluorad FC430, FC431 SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seiyaku Chemical Co., Ltd.), and the like can be given as examples of commercially available products such as those available from Asahi Glass Co., have. The use ratio of these surfactants is preferably 0.01 parts by mass to 2 parts by mass, more preferably 0.01 parts by mass to 1 part by mass based on 100 parts by mass of the resin component contained in the polymer composition.

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

For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3 3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxy (2-aminoethyl) Aminopropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, Amine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl Acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N- Bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- Aminopropyltriethoxysilane, and the like.

Furthermore, in addition to the improvement of the adhesion between the substrate and the orientation layer, additives such as the following phenoplast series or epoxy group-containing compounds may be contained in the polymer composition for the purpose of imparting heat resistance. Specific phenoplast additives are shown below, but the structure is not limited thereto.

(33)

Specific epoxy group-containing compounds 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-xylylenediamine, 1,3-bis (N, N-diglycidylamino Methyl) cyclohexane, N, N, N ', N', -tetraglycidyl-4, 4'-diaminodiphenylmethane and the like.

In the case of using a compound improving the adhesiveness with the substrate, the amount of the compound used is preferably from 0.1 part by mass to 30 parts by mass, more preferably from 1 part by mass to 20 parts by mass with respect to 100 parts by mass of the resin component contained in the polymer composition Mass part. If the amount is less than 0.1 part by mass, the effect of improving the adhesion can not be expected. If the amount is more than 30 parts by mass, the alignment property of the liquid crystal may be deteriorated.

As an additive, a photosensitizer may be used. Colorless sensitizer and triplet sensitizer are preferable.

Examples of the photosensitizer include an aromatic nitro compound, coumarin (7-diethylamino-4-methylcoumarin, 7-hydroxy4-methylcoumarin), ketocoumarin, carbonylbiscumarin, aromatic 2- (2-hydroxybenzophenone, mono- or di-p- (dimethylamino) -2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, (2-benzoylmethylene-3-methyl- beta -naphthothiazoline, 2- (beta -naphthoylmethylene) -3-methylbenzothiazoline, 2- (alpha -naphthoylmethylene) -3 -Methyl-β-naphthothiazoline, 2- (4-biphenoylmethylene) -3-methylbenzothiazoline, 2- Methyl-β-naphthothiazoline, 2- (p-fluorobenzoylmethylene) -3-methyl-β-naphthothiazoline), oxazoline (2-benzoylmethylene- Oxazoline, 2- (p-naphthoylmethylene) -3- Methylbenzooxazoline, 2- (? -Naphthoylmethylene) -3-methylbenzooxazoline, 2- (4-biphenoylmethylene) Methyl-β-naphthooxazoline, 2- (p-fluorobenzoylmethylene) -3-methyl-β-naphtho Nitro- aniline, 2,4,6-trinitroaniline) or nitroascenaphthene (5-nitroceaphthene), (2 - [(m-hydroxy-p- Benzoin alkyl ether, N-alkylated phthalone, acetophenone ketal (2,2-dimethoxyphenyl ethane), naphthalene, anthracene (2-naphthalene methanol, 2-naphthalenecarboxylic acid , 9-anthracene methanol, and 9-anthracene carboxylic acid), benzopyran, azoindolizine, merocoumarin, and the like.

Preferred are aromatic 2-hydroxy ketone (benzophenone), coumarin, ketocoumarin, carbonylbiscumarin, acetophenone, anthraquinone, xanthone, thioxanthone, and acetophenone ketal.

The present invention also relates to a substrate using the polymer composition and a manufacturing method of the modification device.

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

[I] A process for forming a coating film by applying a polymeric composition containing (A) a photosensitive side-chain type polymer exhibiting liquid crystallinity in a predetermined temperature range, (B) a dichroic dye and an organic solvent on a substrate;

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

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

Respectively.

By this process, it is possible to obtain a liquid crystal alignment film imparted with orientation control ability, and a substrate having this liquid crystal alignment film can be obtained.

A method of manufacturing a polarizing element,

[IV] preparing a substrate having the orientation layer obtained as described above; And [V-1] and [V-2] shown below.

[V-1] A polarizing layer-forming composition containing (B) a dichroic dye and (D) a polymerizable liquid crystal is introduced onto an orientation layer of the substrate having the orientation layer and heated and dried to form a coating film, A step of irradiating the coating film with ultraviolet rays;

[V-2] A step of forming a coating film by applying a polarizing layer-forming composition containing (E) a dye having lyotropic liquid crystallinity on an orientation layer of a substrate having the above-mentioned alignment layer, .

Thus, a polarizing element can be obtained.

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

&Lt; Process [I] >

In the step (I), a coating film is formed on a substrate by applying a polymer composition containing (A) a photosensitive side chain type polymer exhibiting liquid crystallinity in a predetermined temperature range, (B) a dichroic dye and an organic solvent .

<Substrate>

The substrate is usually a transparent substrate. On the other hand, when the substrate of the polarizing plate (hereinafter also referred to as the present polarizing plate) of the present invention is not provided on the display surface of the display element, for example, when the polarizing film from which the substrate is removed from the polarizing plate is provided on the display surface of the display element The substrate may not be transparent. The transparent substrate means a substrate having transparency that can transmit light, in particular, visible light, and transparency means a property that a transmittance to a light ray having a wavelength of 380 to 780 nm is 80% or more. As a specific transparent substrate, a translucent resin substrate can be mentioned. Resins constituting the light transmitting resin substrate include polyolefins such as polyethylene and polypropylene; Cyclic olefin-based resins such as norbornene-based polymers; Polyvinyl alcohol; Polyethylene terephthalate; Polymethacrylic acid esters; Polyacrylic acid esters; Cellulose esters such as triacetylcellulose, diacetylcellulose, and cellulose acetate propionate; Polyethylene naphthalate; Polycarbonate; Polysulfone; Polyethersulfone; Polyether ketones; Polyphenylene sulfide, and polyphenylene oxide. Polyethylene terephthalate, polymethacrylic acid ester, cellulose ester, cyclic olefin resin or polycarbonate are preferable from the viewpoints of easiness of obtaining and transparency.

As the cellulose ester, some or all of the hydroxyl groups contained in the cellulose are esterified, and are readily available on the market. In addition, cellulose ester bases are also readily available on the market. Examples of commercially available cellulose ester substrates include "Fujifilm Film" (Fuji Photo Film Co., Ltd.); , "KC8UX2M", "KC8UY" and "KC4UY" (Konica Minolta Opto).

The cyclic olefin-based resin is easily available on the market. Commercially available cycloolefin resins include "Topas" (Ticona), "Aton" (JSR), "Zeonor" (Japan), "Zeonex ) &Quot; Japan Xeon Co., Ltd. &quot; and &quot; Arpel &quot; [manufactured by Mitsui Chemicals Co., Ltd.]. The cycloolefin resin may be formed into a substrate by a known means such as a solvent casting method or a melt extrusion method. A commercially available cycloolefin resin substrate may also be used. Commercially available cycloolefin resin substrates include "Essen" (manufactured by Sekisui Chemical Co., Ltd.), "SCA40" (manufactured by Sekisui Chemical Co., Ltd.), "Zeonoafilm" &Quot; Aton film &quot; [JSR Co., Ltd.].

When the cyclic olefin resin is a copolymer of a cyclic olefin and an aromatic compound having a chain olefin or vinyl group, the content ratio of the structural unit derived from the cyclic olefin is usually 50 mol% or less based on the total structural units of the copolymer , Preferably from 15 to 50 mol%. Examples of the chain olefin include ethylene and propylene. Examples of the aromatic compound having a vinyl group include styrene,? -Methylstyrene and alkyl-substituted styrene. In the case where the cyclic olefin resin is a ternary copolymer 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 generally from 5% 80 mol%, and the content ratio of the structural unit derived from an aromatic compound having a vinyl group is usually 5 to 80 mol% based on the total structural units of the copolymer. Such a terpolymer has an advantage in that it can relatively reduce the amount of expensive cyclic olefin used in the production thereof.

The properties required for the substrate are different depending on the constitution of the polarizing plate, but are usually as small as possible as long as the retardation is possible. Examples of the substrate as small as possible of retardation include a cellulose ester film having no retardation such as Zero tack (Konica Minolta Opto Co., Ltd.), Zack (Fuji Film Co., Ltd.) and the like. Further, an unoriented cycloolefin resin base material is also preferable.

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

The thickness of the substrate is usually from 5 to 300 탆, preferably from 20 to 200 탆, since the thickness of the substrate tends to be lowered and the workability tends to deteriorate when it is too thin.

The method of applying the above-mentioned polymer composition onto a substrate is not particularly limited.

As a coating method, a method generally employed is screen printing, offset printing, flexographic printing, or inkjet printing. Examples of other application methods include a dip method, a roll coater method, a slit coater method, a spinner method (spin coating method), a spray method, and the like, depending on the purpose.

After the polymer composition is applied onto the substrate, it is heated at 50 to 230 DEG C, preferably 50 to 200 DEG C for 0.4 to 60 minutes by a heating means such as a hot plate, a heat circulation type oven or an IR (infrared) And the solvent is evaporated for preferably 0.5 minute to 10 minutes to obtain a coating film. The drying temperature at this time is preferably lower than the liquid crystal phase temperature of the side chain type polymer.

When the thickness of the coating film is excessively large, it becomes disadvantageous in terms of anisotropy. When the thickness of the coating film is too thin, there is a problem in the polarization characteristic, and therefore it is usually in the range of 10 nm to 10,000 nm, preferably in the range of 10 nm to 1000 nm, And more preferably in the range of 10 nm to 300 nm.

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

&Lt; Process [II] >

In the step [II], the coated film obtained in the step [I] is irradiated with polarized ultraviolet rays. When polarized ultraviolet rays are irradiated to the film surface of the coating film, polarized ultraviolet rays are irradiated to the substrate through a polarizer from a predetermined direction. As ultraviolet rays to be used, ultraviolet rays having a wavelength in the range of 100 nm to 400 nm can be used. Preferably, an optimum wavelength is selected through a filter or the like depending on the kind of the coating film to be used. For example, ultraviolet rays having a wavelength in the range of 290 nm to 400 nm can be selectively used so that the photo-crosslinking reaction can be induced (induced). As ultraviolet rays, for example, light emitted from a high-pressure mercury lamp can be used.

The irradiation amount of the polarized ultraviolet ray depends on the coating film to be used. The irradiation dose is the amount of the polarized ultraviolet light that realizes the maximum value of? A (hereinafter also referred to as? Amma) which is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet ray and the ultraviolet absorbance in the perpendicular direction Is preferably within a range of 1% to 70%, and more preferably within a range of 1% to 50%.

&Lt; Process [III] >

In the step [III], the coated film irradiated with polarized ultraviolet rays in the step [II] is heated. By heating, orientation control ability can be imparted to the coating film.

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

The heating temperature is preferably within the temperature range at which the side chain type polymer exhibits liquid crystallinity (hereinafter referred to as liquid crystal forming temperature). In the case of a thin film surface such as a coating film, it is expected that the liquid crystal display temperature at the surface of the coating film is lower than the liquid crystal temperature when the photosensitive side chain polymer capable of exhibiting liquid crystallinity is observed in bulk. Therefore, it is more preferable that the heating temperature is within the temperature range of the liquid crystal forming temperature on the surface of the coating film. That is, the temperature range of the heating temperature after irradiation with the polarized ultraviolet rays is set to a temperature lower by 10 占 폚 than the lower limit of the temperature range of the liquid crystal display temperature of the side chain type polymer to be used as the lower limit and a temperature 10 占 폚 lower than the upper limit of the liquid crystal temperature range, The temperature is preferably in the range of &lt; RTI ID = 0.0 &gt; If the heating temperature is lower than the above temperature range, the effect of amplifying the anisotropy due to heat in the coating film tends to become insufficient. If the heating temperature is too high than the above temperature range, the coating film is in an isotropic liquid state Phase), and in this case, it may become difficult to reorient in one direction by self-organization.

On the other hand, the liquid crystal display temperature is not lower than the glass transition temperature (Tg) at which the side chain type polymer or the surface of the coating film undergoes phase transition from the solid phase to the liquid crystal phase, and the isotropic phase transition temperature (isotropic phase transition temperature Tiso).

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 the step [I].

By the above process, the production method of the present invention can realize introduction of anisotropy to the coating film with high efficiency. Then, a substrate with an alignment layer can be manufactured with high efficiency.

In the method for producing a coated film-attached substrate of the present invention, the polymer composition is coated on a substrate to form a coated film, and then irradiated with polarized ultraviolet rays. Subsequently, by heating, introduction of high-efficiency anisotropy into the side chain-type polymer membrane is realized, and a liquid crystal alignment film-attached substrate having the liquid crystal orientation control ability is produced.

In the coating film used in the present invention, the introduction of high efficiency anisotropy into the coating film is realized by utilizing the principle of molecular reorientation induced by the light reaction of side chains and the self-organization based on liquid crystallinity. In the production method of the present invention, in the case of a structure having a photocrosslinking group as a photoreactive group on the side chain-type polymer, a coating film is formed on the substrate using the side chain-type polymer, then polarized ultraviolet light is irradiated, After that, a polarizing element is formed.

Therefore, the coating film used in the method of the present invention can be an orientation layer which introduces anisotropy with high efficiency and has excellent orientation control ability, by sequentially irradiating the coating film with polarized ultraviolet light and performing heat treatment.

In the coating film used in the method of the present invention, the irradiation amount of the polarized ultraviolet ray to the coating film and the heating temperature in the heating treatment are optimized. Thus, introduction of anisotropy into the coating film with high efficiency can be realized.

The irradiation amount of the polarized ultraviolet ray most suitable for introducing the high efficiency anisotropy into the coating film used in the present invention is preferably such that the amount of the polarized ultraviolet ray which optimizes the amount of the photosensitive group to react with the light crosslinking reaction or the optical isomerization reaction, Corresponds to dose. As a result of irradiating the coating film used in the present invention with polarized ultraviolet rays, a sufficient photoreaction amount can not be obtained when a photo-crosslinking reaction, a photo-isomerization reaction, or a photosensitive group of a side chain which reacts with light- In that case, sufficient self-organization does not proceed even after heating. On the other hand, in the coating film used in the present invention, the structure having a photocrosslinkable group is irradiated with polarized ultraviolet rays. As a result, when the photosensitive group of the side chain to be crosslinked is excessive, the cross-linking reaction in the side chain is excessively advanced. In this case, the resulting film becomes rigid and may interfere with the progress of self-organization by subsequent heating. In addition, in the coating film used in the present invention, polarized ultraviolet rays are irradiated to a structure having a light-free stress period, and as a result, when the photosensitive group of the side chain which reacts to the light-free potential is excessive, the liquid crystallinity of the coating film is excessively lowered. In such a case, the liquid crystallinity of the resulting film is also lowered, which may interfere with the progress of self-organization by the subsequent heating. In the case of irradiating polarized ultraviolet rays to a structure having a light-free stress period, if the irradiation dose of ultraviolet light is too high, the side chain type polymer is photolyzed and 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 photo-crosslinking reaction, photoisomerization reaction, or photo-free potential reaction of the photosensitive group of the side chain by irradiation with polarized ultraviolet light is 0.1 mol of the photosensitive group of the side chain- % To 40 mol%, and more preferably 0.1 mol% to 20 mol%. By setting the amount of the photosensitive group of the photoreactive side chain within this range, the self-organization in the subsequent heat treatment proceeds efficiently, and high anisotropy can be formed in the film.

In the coating film used in the method of the present invention, the amount of photo-crosslinking reaction, optical isomerization reaction, or light-free potential reaction of the photosensitive group in the side chain of the side chain-type polymer membrane is optimized by optimizing the irradiation amount of polarized ultraviolet rays. In addition to the subsequent heat treatment, introduction of anisotropy into the coating film used in the present invention with high efficiency is realized. In this case, the amount of the polarized ultraviolet ray can be determined based on the evaluation of the ultraviolet absorption of the coating film used in the present invention.

That is, for the coating film used in the present invention, ultraviolet absorption in a direction parallel to the polarization direction of polarized ultraviolet rays after irradiation with polarized ultraviolet light and ultraviolet absorption in a perpendicular direction are respectively measured. From the measurement results of ultraviolet absorption, ΔA which is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet ray and the ultraviolet absorbance in the perpendicular direction in the coating film is evaluated. Then, the maximum value DELTA Amax realized in the coating film used in the present invention and the irradiation amount of the polarized ultraviolet ray for realizing the maximum value DELTA Amax are obtained. In the production method of the present invention, the amount of polarized ultraviolet ray to be irradiated in the production of the liquid crystal alignment film can be determined on the basis of the amount of irradiated polarized ultraviolet light realizing the DELTA Amma.

In the production method of the present invention, the amount of irradiated polarized ultraviolet rays to the coating film used in the present invention is preferably in the range of 1% to 70% of the amount of the polarized ultraviolet ray realizing DELTA Amma, and 1% to 50% And more preferably within the range. In the coating film used in the present invention, the irradiation amount of the polarized ultraviolet ray within the range of 1% to 50% of the amount of the polarized ultraviolet ray realizing DELTA Amma is 0.1 to 20 mol% of the whole photosensitive group of the side chain- And corresponds to the amount of polarized ultraviolet ray to be subjected to photo-crosslinking reaction.

From the above, in the production method of the present invention, in order to realize introduction of high efficiency anisotropy into the coating film, it is preferable to set the above-mentioned favorable heating temperature on the basis of the liquid crystal temperature range of the side chain type polymer. Therefore, for example, when the liquid crystal temperature range of the side chain type polymer used in the present invention is 60 ° C to 200 ° C, it is preferable to set the heating temperature after the polarized ultraviolet irradiation to 50 ° C to 190 ° C. By doing so, a greater anisotropy is imparted to the coating film used in the present invention.

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

&Lt; Polarizing layer forming composition >

The polarizing layer-forming composition used for forming the polarizing element of the present invention is a composition containing (B) a dichroic dye and (D) a polymerizable liquid crystal, or (E) a dye containing a lyotropic liquid crystalline property. The composition for forming a polarizing layer containing a dichroic dye (B) and a polymerizable liquid crystal (D) usually includes a solvent. Examples of the solvent include the same solvents as those contained in the above-mentioned oriented polymer composition, ) Can be appropriately selected depending on the solubility of the polymerizable liquid crystal.

(E) The composition containing the dye having lyotropic liquid crystalline property usually includes a solvent, and the solvent is not particularly limited and conventionally known solvents may be used, but aqueous solvents are preferred. Examples of the aqueous solvent include water, a hydrophilic solvent, a mixed solvent of water and a hydrophilic solvent, and the like. The hydrophilic solvent is a solvent which dissolves substantially uniformly in water. Examples of the hydrophilic solvent include alcohols such as methanol and isopropyl alcohol; Glycols such as ethylene glycol; Cellosolve such as methylcellosolve, ethylcellosolve; Ketones such as acetone and methyl ethyl ketone; Esters such as ethyl acetate; And the like. The water-based solvent is preferably water or a mixed solvent of water and a hydrophilic solvent.

As the dichroic dye (B), the above-mentioned component (B) is used.

<(D) Polymerizable liquid crystal>

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

The polymerizable group means a group participating in the polymerization reaction and is preferably a photopolymerizable group. Here, the photopolymerizable group means a group capable of undergoing a polymerization reaction with an active radical or an acid generated from a photopolymerization initiator described later. Examples of the polymerizable group include vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloyloxy group, methacryloyloxy group, oxiranyl group and 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. The compound exhibiting liquid crystallinity may be either a thermotropic liquid crystal or a lyotropic liquid crystal, or may be a nematic liquid crystal or a smectic liquid crystal in a thermotropic liquid crystal.

The polymerizable liquid crystal is preferably a smectic liquid crystal compound in that higher polarization characteristics can be obtained, and a higher order smectic liquid crystal compound is more preferable. Among them, a Smectic B phase, a Smectic D phase, a Smectic E phase, a Smectic F phase, a Smectic G phase, a Smectic H phase, a Smectic I phase, a Smectic J phase, A higher order smectic liquid crystal compound forming an L phase is more preferable, and a higher order smectic liquid crystal compound forming a 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 in a high-order smectic phase, a polarizing film having a higher degree of alignment can be produced. Further, in the elongated polarizing film having such a high degree of alignment as described above, a black peak derived from a higher order structure such as a hexaic phase or a crystal phase can be obtained by X-ray diffraction measurement. The black peak is a peak derived from the periodic structure of the molecular orientation. When the liquid crystal phase formed by the polymerizable liquid crystal compound is in the high-order smectic phase, a film having a periodic interval of 3.0 to 6.0 Å can be obtained.

Such a compound specifically includes a compound represented by the following formula (d) (hereinafter sometimes referred to as a compound (d)). 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 the formula (d)

X ¹ , X ² and X ³ independently represent a 1,4-phenylene group which may have a substituent or a cyclohexane-1,4-diyl group which may have a substituent. Provided that at least one of X ¹ , X ² and X ³ is a 1,4-phenylene group which may have a substituent. The -CH ₂ - constituting the cyclohexane-1,4-diyl group may be substituted with -O-, -S- or -NR-. R represents an alkyl group having 1 to 6 carbon atoms or a phenyl group.

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

V ¹ and V ² independently represent an alkanediyl group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - which constitutes the alkanediyl group may be replaced by -O-, -S- or - NH-. &Lt; / RTI &gt;

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.

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

The substituent optionally having a 1,4-phenylene group which may have a substituent or a cyclohexane-1,4-diyl group which may have a substituent includes an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group and a butyl group, And halogen atoms.

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. It is preferable that U ¹ and U ² are all polymerizable groups, and it is preferable that all of them are a photopolymerizable group. The polymerizable liquid crystal compound having a photopolymerizable group is advantageous in that it can be polymerized at a lower temperature.

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 vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloyloxy group, methacryloyloxy group, oxiranyl group and 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- Diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, decane-1,10-diyl group, tetradecane- Diyl group and icosane-1, 20-diyl group. V ¹ and V ² are preferably an alkanediyl group having 2 to 12 carbon atoms, more preferably an alkanediyl group having 6 to 12 carbon atoms.

Examples of the substituent optionally having an alkanediyl group having 1 to 20 carbon atoms which may have a substituent include a cyano group and a halogen atom. The alkanediyl group is preferably unsubstituted, and the unsubstituted or substituted More preferably an alkanediyl group.

W ¹ and W ² are, independently of each other, preferably a single bond or -O-.

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

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(35)

(36)

(37)

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

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

When two or more polymerizable liquid crystal compounds are combined, at least one compound (c) is preferable, and two or more compounds (d) are more preferable. It may be possible to temporarily maintain liquid crystallinity even at a temperature lower than the liquid crystal-crystal phase transition temperature. The mixing ratio in the case of combining two kinds of polymerizable liquid crystal compounds is usually 1:99 to 50:50, preferably 5:95 to 50:50, and more preferably 10:90 to 50:50 .

Compound (d) can be prepared, for example, by Lub et al. Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996), or Japanese Patent No. 4719156 and the like.

&Lt; (E) Lyotropic liquid crystal coloring matter >

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

Examples of such pigments having lyotropic liquid crystallinity include azo-based compounds, anthraquinone-based compounds, perylene-based compounds, quinophthalone-based compounds, naphthoquinone-based compounds and merocyanine-based compounds. In view of good lyotropic liquid crystallinity, it is preferable to use an azo-based compound.

Among the azo compounds, an azo compound having an aromatic ring in the molecule is preferable, and a disazo compound having a naphthalene ring is more preferable. By applying and drying a coating solution containing such an azo-based compound, a polarizing layer having excellent polarization characteristics can be obtained.

The azo-based compound is preferably an azo-based compound having a polar group in its molecule. The azo compound having a polar group is soluble in an aqueous solvent and dissolved in an aqueous solvent to form a supramolecular complex. For this reason, a coating liquid containing an azo compound having a polar group exhibits particularly good lyotropic liquid crystallinity.

On the other hand, the polar group means a functional group having polarity. Examples of the polar group include a functional group containing oxygen and / or nitrogen having relatively high electronegativity such as an OH group, a COOH group, an NH ₂ group, a NO ₂ group, and a CN group.

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

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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 independently represents a hydrogen atom, A substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group; M represents a bivalent ion; m7 represents an integer of 0 to 2; and n7 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted acetyl group, , And an integer of 0 to 6. However, at least 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 be bonded to any one of 7 substitution sites of the naphthyl ring.

In the present specification, the term "substituted or unsubstituted" means "substituted with a substituent or not substituted with a substituent".

The bonding position of the naphthyl group of the above general formula (E-1) and the azo group (-N═N-) is not particularly limited. The naphthyl group refers to a naphthyl group shown on the right side of the formula (E-1). Preferably, the naphthyl group and the azo group are bonded at one or two positions of the naphthyl group.

When the alkyl group, acetyl group, benzoyl group or phenyl group of R ^E in the general formula (E-1) has a substituent, examples of the substituent include the following 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, more preferably a hydrogen atom.

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

The M (bionate) of the above general formula (E-1) is preferably a hydrogen ion; Alkali metal ions such as Li, Na, K, and Cs; Alkaline earth metal ions such as Ca, Sr and Ba; Other metal ions; An ammonium ion which may be substituted with an alkyl group or a hydroxyalkyl group; Salts of organic amines and the like. The metal ions include, 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 alkyl amines having 1 to 6 carbon atoms, alkyl amines having 1 to 6 carbon atoms having a hydroxyl group, and alkyl amines having 1 to 6 carbon atoms having a carboxyl group. In the general formula (E-1), when SO ₃ M is 2 or more, each M may be the same or different. When the M of SO ₃ M in the general formula (E-1) is a cation having a valence of at least 2, it is bonded to the SO ₃ ^- of the adjacent azo compound of the general formula (E-1) Can be formed.

The m7 in the general formula (E-1) is preferably 1. Furthermore, n7 in the general formula (E-1) is preferably 1 or 2.

Specific examples of the naphthyl group of the formula (E-1) include, for example, the following formulas (Ea) to (El). R ^E and M in formulas (Ea) to (El) are the same as in formula (E-1).

[Chemical Formula 39]

In the general formula (E-1), the aryl group represented by Q ¹ includes a condensed ring group in which two or more benzene rings such as a naphthyl group are condensed in addition to a phenyl group.

The arylene group represented by Q &lt; ² &gt; includes, in addition to the phenylene group, a condensed ring group in which two or more benzene rings are condensed such as a naphthylene 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 where 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 has excellent solubility in an aqueous solvent.

When the aryl group or the 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 sulfonic acid group such as a carboxyl group such as a COOM group and a SO ₃ M group, a hydroxyl group, a cyano group, a nitro group, an amino group, a nitro group, a nitro 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 one or more than two. The substituent may be substituted at an arbitrary ratio.

Q ¹ in the general formula (E-1) is preferably a substituted or unsubstituted phenyl group, 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 represented by the general formula (E-1) wherein Q ¹ is a substituted or unsubstituted phenyl group and Q ² is a substituted or unsubstituted 1,4-naphthylene group, ).

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

In the general formula (E-2), A ^E and B ^E represent a substituent, and a and b represent the number of substitution. A ^E and B ^E each independently represent 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 hydroxyl group, a cyano group, a nitro group, an amino group and a halogeno group such as a carboxyl group such as a COOM group and a SO ₃ M group such as a hydroxyalkyl group having 1 to 6 carbon atoms such as a dihydroxypropyl group. Wherein a is an integer of 0 to 5, and b is an integer of 0 to 4. However, at least one of a and b is not zero. When a is 2 or more, the substituent A ^E may be the same or different. When b is 2 or more, the substituents B ^E may be the same or different.

Among the aromatic disazo compounds contained in the general formula (E-2), it is preferable to use an aromatic disazo compound represented by the following general formula (E-3). In the aromatic disazo compound of the formula (E-3), the substituent A ^E is bonded to the para position on the basis of the azo group (-N = N-). The aromatic disazo compound of the formula (E-3) is bonded to the position (ortho position) adjacent to the azo group of the OH group of the naphthyl group. By using the aromatic disazo compound of the formula (E-3), a polarizing plate having a high degree of polarization can be obtained.

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

In the general formula (E-3), p7 represents an integer of 0 to 4. P7 is preferably 1 or 2, and more preferably 1.

The aromatic disazo compounds represented by the above general formulas (E-1) to (E-3) can be obtained, for example, by the method described in Hosoda Yutaka, &quot; Theoretical Preparation Dye Chemistry (5th edition) &quot; (July 15, , Journal of the Institute of Electronics, Information and Communication Engineers, pp. 135 to 152).

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

The proportion of the (D) polymerizable liquid crystal compound or (E) the dye having lyotropic liquid crystallinity in the composition for forming a polarizing layer is preferably in a range of usually from Preferably 70 to 99.9 parts by mass, more preferably 80 to 99.9 parts by mass, still more preferably 85 to 99 parts by mass, and further preferably 90 to 99 parts by mass.

&Lt; Process [IV] and Process [V]

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

[V-1] A polarizing layer-forming composition containing (B) a dichroic dye and (D) a polymerizable liquid crystal is introduced onto an orientation layer of the substrate having the orientation layer and heated and dried to form a coating film, A step of irradiating the coating film with ultraviolet rays;

[V-2] A step of forming a coating film by applying a polarizing layer-forming composition containing (E) a dye having lyotropic liquid crystallinity on an orientation layer of a substrate having the above-mentioned alignment layer, followed by heating and drying.

The application of the composition for forming a polarizing layer is usually carried out by a known method such as a coating 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, Lt; / RTI &gt; When the composition for forming the polarizing layer (D) contains a polymerizable liquid crystal, the solvent is removed under the condition that the polymerizable liquid crystal (D) contained in the obtained coating film is not polymerized after application. Examples of the drying method include a natural drying method, a ventilation drying method, a heat drying method and a reduced pressure drying method.

(D) the polymerizable liquid crystal in the step of irradiating ultraviolet light onto the coating film containing the dichroic dye (B) and the polymerizable liquid crystal (D) is carried out by a known method of polymerizing a compound having a polymerizable functional group . Specifically, thermal polymerization and photopolymerization can be mentioned, and from the viewpoint of easy polymerization, photopolymerization is preferable. In the case of polymerizing a polymerizable liquid crystal by photopolymerization, a composition containing a photopolymerization initiator is further applied to a polarizing layer forming composition containing (D) a dichroic dye and (D) a polymerizable liquid crystal, followed by drying, It is preferable to perform the photopolymerization while keeping the liquid crystal state in the liquid crystal state.

Photopolymerization is usually carried out by irradiating a dry film with light. The light to be irradiated is appropriately selected according to the type of the photopolymerization initiator contained in the dried film, (D) the type of the polymerizable liquid crystal (in particular, the type of the photopolymerizable group of the polymerizable liquid crystal (D)), Specifically, light and active electron rays selected from the group consisting of visible light, ultraviolet light and laser light can be cited. Of these, ultraviolet light is preferable, and (D) is preferably used in order to be able to be photopolymerized by ultraviolet light, from the viewpoint that the progress of the polymerization reaction can be easily controlled and the photopolymerization apparatus widely used in the field can be used, It is preferable to select the kind of the polymerizable liquid crystal or the photopolymerization initiator. Further, at the time of polymerization, the polymerization temperature may be controlled by irradiating light while cooling the dried film by an appropriate cooling means. By employing such a cooling means, polymerization of the polymerizable liquid crystal (D) at a lower temperature allows the polarizing layer to be suitably formed even if the substrate has a relatively low heat resistance.

The application in the step of forming a coating film by applying a polarizing layer-forming composition containing a dye having (E) lyotropic liquid crystallinity onto an orientation layer of the substrate having the above-mentioned orientation layer is usually carried out by a spin Coating method, extrusion method, gravure coating method, die coating method, bar coating method, applicator method, etc., printing method such as flexo printing method and the like. The drying method is not particularly limited, and natural drying or forced drying can be carried out. Examples of the forced drying include, for example, reduced pressure drying, heat drying, and reduced pressure heat drying. Preferably, natural drying is used.

The drying time can be appropriately selected depending on the drying temperature and the type of the 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.

The drying temperature is not particularly limited, but is preferably lower than the glass transition temperature (Tg) of the substrate. If the drying temperature exceeds the glass transition temperature of the substrate, the properties of the substrate (such as mechanical strength and optical characteristics) may be deteriorated. Concretely, the drying temperature is preferably 10 ° C to 100 ° C, more preferably 10 ° C to 90 ° C, and particularly preferably 10 ° C to 80 ° C.

On the other hand, the drying temperature means the temperature of the atmosphere in which the coating film is dried, not the temperature of the surface or inside of the coating film containing (E) the dye having lyotropic liquid crystallinity.

The sum of the thicknesses of the alignment layer and the polarizing layer in this polarizing element is 10 mu m or less. The thickness of the orientation layer is preferably 0.5 μm or more and 9.5 μm or less, more preferably 1 μm or more and 5 μm or less. The thickness of the polarizing layer is preferably 0.5 m or more and 9.5 m or less, and more preferably 1 m or more and 5 m or less. The thicknesses of the orientation layer and the polarizing layer can be generally determined by measurement with an interference fringe system, a laser microscope or a stylus film fringe system.

As described above, the obtained polarizing element can be widely applied to various display devices requiring polarized light by using a known technique. For example, an antireflection film (circular polarizing plate) such as a liquid crystal display element or an organic EL, , Optical switches and optical filters, and various optical measuring instruments using these as components.

Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited to these Examples.

Example

Hereinafter, the present invention will be described in detail with reference to 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 propylene glycol monomethyl ether (PM), cyclohexanone (CYH), and methyl isobutyl ketone (MIBK) were used as the solvent.

&Lt; Measurement of molecular weight of polymer &

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

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

Column temperature: 50 ° C

(30 mmol / L of lithium bromide-hydrate (LiBr.H ₂ O), 30 mmol / L of phosphoric acid-anhydrous crystal (o-phosphoric acid), and tetrahydrofuran (THF) 10 mL / L)

Flow rate: 1.0 mL / min

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

&Lt; Synthesis Example 1 &

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

&Lt; Synthesis Example 2 &

Hydroxybenzoic acid and 1-bromo-6-hexanol were heated under alkaline conditions to synthesize 4- (6-hydroxyhexyloxy) benzoic acid. This product was reacted with methacrylic acid chloride under a basic condition to obtain a compound represented by the formula (Ex-A) (hereinafter also referred to as a 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).

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&Lt; Synthesis Example 4 &

16.0 g of methacrylic acid ester represented by the above formula (Ex-1) and 0.4 g of?,? '- azobisisobutyronitrile as a polymerization catalyst were dissolved in 180.0 g of 1,4-dioxane, Hour reaction to obtain an acrylic copolymer solution. Acrylic copolymer solution was slowly added dropwise to 1000.0 g of diethyl ether to precipitate a solid, which was filtered and dried under reduced pressure to remove the remaining monomer to obtain an acrylic polymer (P1). The obtained acrylic copolymer had Mn of 9,300 and Mw of 16,000.

&Lt; Synthesis Example 5 &

8.0 g of the methacrylic acid ester represented by the above formula (Ex-1), 7.4 g of the methacrylic acid ester represented by the above formula (Ex-A), 0.8 g of the α, α'-azobisisobutyronitrile Was dissolved in 145.0 g of 1,4-dioxane and reacted at 80 DEG C for 20 hours to obtain an acrylic copolymer solution. The acrylic copolymer solution was slowly added dropwise to 1000.0 g of diethyl ether to precipitate a solid, which was filtered and dried under reduced pressure to remove the remaining monomer to obtain an acrylic copolymer (P2). The obtained acrylic copolymer had Mn of 8,000 and Mw of 20,000.

&Lt; Synthesis Example 6 &

10.0 g of the methacrylic acid ester represented by the above-mentioned formula (Ex-1), 5.3 g of the methacrylic acid ester represented by the above formula (Ex-2), 0.2 g of?,? '- azobisisobutyronitrile Was dissolved in 165.0 g of 1,4-dioxane and reacted at 80 DEG C for 20 hours to obtain an acrylic copolymer solution. The acrylic copolymer solution was slowly added dropwise to 1000.0 g of diethyl ether to precipitate a solid, which was filtered and dried under reduced pressure to remove the remaining monomer to obtain an acrylic copolymer (P3). The acrylic copolymer thus obtained had an Mn of 11,000 and an Mw of 21,000.

&Lt; Synthesis Example 7 &

8.0 g of the methacrylic acid ester represented by the above formula (Ex-1), 9.8 g of the methacrylic acid ester represented by the above formula (Ex-2), 0.2 g of the?,? '- azobisisobutyronitrile Was dissolved in 180.0 g of 1,4-dioxane and reacted at 80 DEG C for 20 hours to obtain an acrylic copolymer solution. The acrylic copolymer solution was slowly added dropwise to 1000.0 g of diethyl ether to precipitate a solid, which was filtered and dried under reduced pressure to remove the remaining monomers to obtain an acrylic copolymer (P4). The obtained acrylic copolymer had Mn of 14,000 and Mw of 24,000.

&Lt; Preparation Example 1 &

[Preparation of polarizing layer forming composition RM1]

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

&Lt; Preparation Example 2 &

[Preparation of polarizing layer forming composition RM2]

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

&Lt; Examples 1 to 6 > and < Comparative Examples 1 and 2 &

Each of the alignment layer forming compositions of Examples 1 to 6 and Comparative Examples 1 and 2 was prepared with the composition shown in Table 1. An alignment layer was formed using each orientation layer forming composition, and the dichroism ratio was measured for each alignment layer. Next, a polarizing element was formed using the composition for forming a polarizing layer. The obtained polarizing elements were each evaluated for orientation, polarization degree and dichroism ratio.

[Table 1]

&Lt; Example 1 >

[Formation of orientation layer]

The alignment layer forming composition shown in Table 1 was spin-coated on a quartz substrate and dried on a hot plate at 55 占 폚 for 60 seconds to form a coating film having a film thickness of 200 nm. Next, linearly polarized light having a wavelength of 313 nm was vertically irradiated with a light exposure of ² mJ / cm ² through a polarizer on the coated film surface. Subsequently, the substrate was heated on a hot plate at 170 DEG C for 5 minutes to form an alignment layer.

[Measurement of dichroism ratio of orientation layer]

The dichroic ratio of the obtained alignment layer was measured as follows. Absorbance (A1) in the transmission axis direction and absorbance (A2) in the absorption axis direction were measured using a spectrophotometer (UV-3600 manufactured by Shimadzu Corporation) equipped with a polarizer attached folder. The dichroism ratio was calculated from the values of the absorbance (A1) in the transmission axis direction and the absorbance (A2) in the absorption axis direction using the following formula. The measurement results are shown in Table 2.

Dichroic ratio = (A2) / (A1)

[Formation of polarizing layer]

On the obtained alignment layer, the composition for forming a polarizing layer RM1 was spin-coated at 2000 rpm for 30 seconds and dried on a hot plate at 65 DEG C for 60 seconds to form a coating film. Subsequently, this coating film was exposed at 500 mJ / cm ² to obtain a polarizing element.

[Evaluation of orientation]

The orientation property of the obtained polarizing element was confirmed by observation with a polarizing microscope. A sample was inserted between the polarizing microscope Cross-Nicol in the directions of 0 DEG and 45 DEG, and the light leakage state was observed. In the case of being oriented, the light leakage does not occur at 0 °, and the dark field is observed. At 45 °, the light leakage occurs and the bright field is observed. &Quot; &amp; cir &amp; &quot; was obtained when the bright field was obtained at 45 deg., And &quot; x &quot; The results of these measurements are shown in Table 2.

[Measurement of polarization degree]

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

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 in the following manner. Absorbance (A1) in the transmission axis direction and absorbance (A2) in the absorption axis direction were measured using a spectrophotometer (UV-3600 manufactured by Shimadzu Corporation) equipped with a polarizer attached folder. The dichroism ratio was calculated from the values of the absorbance (A1) in the transmission axis direction and the absorbance (A2) in the absorption axis direction using the following formula. The measurement results are shown in Table 2.

Dichroic ratio = (A2) / (A1)

&Lt; Example 2 >

A polarizing element was prepared in the same manner as in Example 1 except that the linear polarization at the time of forming the alignment layer was 5 mJ / cm ² and the heating temperature after the polarization exposure was 150 ° C. The results are summarized in Table 2.

&Lt; Example 3 >

A polarizing element was prepared in the same manner as in Example 1 except that the heating temperature after the polarizing exposure at the time of formation of the orientation layer was 120 캜. The results are summarized in Table 2.

<Example 4>

A polarizing element was prepared in the same manner as in Example 1 except that the heating temperature after the polarizing exposure at the time of formation of the orientation layer was 100 캜. The results are summarized in Table 2.

&Lt; Example 5 >

A polarizing element was prepared in the same manner as in Example 1 except that the heating temperature after polarizing exposure at the time of formation of the alignment layer was 140 캜. The results are summarized in Table 2.

&Lt; Example 6 >

A polarizing element was prepared in the same manner as in Example 1 except that the heating temperature after the polarizing exposure at the orientation layer formation was set to 100 캜 and that RM2 was used for the composition for forming a polarizing layer. The results are summarized in Table 2.

&Lt; Comparative Example 1 &

A polarizing element was prepared in the same manner as in Example 1 except that the heating temperature after the polarizing exposure at the time of formation of the orientation layer was 100 캜. The results are summarized in Table 2.

&Lt; Comparative Example 2 &

A polarizing element was prepared in the same manner as in Example 1 except that the heating temperature after the polarizing exposure at the orientation layer formation was set to 100 캜 and that RM2 was used for the composition for forming a polarizing layer. The results are summarized in Table 2.

[Table 2]

In Comparative Examples 1 and 2 in which no dichroic dye was added to the alignment layer, the dichroic ratio of the alignment layer was 0. On the other hand, in Examples 1 to 6 in which a dichroic dye was added to the orientation layer, a high dichroic ratio was obtained, and it was possible to orient the dichroic dye in the orientation layer.

The polarizers obtained in Examples 1 to 5 were able to exhibit high polarization and dichroism ratios as compared with Comparative Example 1. [

The polarizer obtained in Example 6 was able to exhibit high polarization and dichroism ratios as compared with Comparative Example 2.

Claims (6)

(A) a polymeric composition containing a photosensitive side-chain type polymer exhibiting liquid crystallinity at a predetermined temperature range, (B) a dichroic dye and an organic solvent. The method according to claim 1,
Wherein the component (A) is a side chain type polymer having a photosensitive side chain which causes photo-crosslinking, photoisomerization, or light-free transition. The method according to claim 1,
Wherein the component (A) is a side chain type polymer having any one photosensitive side chain selected from the group consisting of the following formulas (1) to (6).
[Chemical Formula 1]

Wherein A, B and D each independently represent a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH- O-, or -O-CO-CH = CH-;
S represents an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded to them 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 to them may be substituted with a halogen group;
Y ₁ represents a ring selected from the group consisting of monovalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings and alicyclic hydrocarbons having 5 to 8 carbon atoms, or the same Or a group formed by bonding different 2 to 6 rings via a bonding group B, and each of the hydrogen atoms bonded to these groups independently represents -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 divalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings, alicyclic hydrocarbons having 5 to 8 carbon atoms, and combinations thereof, Each hydrogen atom is independently selected from the group consisting of -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 Lt; / RTI &gt;
R represents a hydroxyl 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 the number of X's is 2, X's may be the same or different;
Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded to these groups are each independently -NO ₂ , -CN, -CH═C (CN) ₂ , A halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
q1 and q2 are one in one and zero in the other;
q3 is 0 or 1;
P and Q each independently represent a group selected from the group consisting of divalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings, alicyclic hydrocarbons having 5 to 8 carbon atoms, and combinations thereof ; Provided that when X is -CH = CH-CO-O- or -O-CO-CH = CH-, P or Q on the side bonded with -CH = CH- represents an aromatic ring;
l1 is 0 or 1;
l2 is an integer of 0 to 2;
When l1 and l2 are both 0, when T is a single bond, A also represents a single bond;
When l1 is 1, B is also a single bond when T is a single bond;
H and I each independently represent a group selected from the group consisting of divalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings, and combinations thereof. 4. The method according to any one of claims 1 to 3,
(A) has any one kind of liquid crystalline side chain selected from the group consisting of the following formulas (21) to (31).
(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 heterocyclic ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, May be independently substituted with -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;
R ₃ represents a hydrogen atom, -NO ₂ , -CN, -CH═C (CN) ₂ , -CH═CH-CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl 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;
(25) to (26), the sum of all m is 2 or more, and in formulas (27) to (28), m represents an integer of 1 to 12, , The sum of all m is 1 or more, m1, m2 and m3 each independently represent an integer of 1 to 3;
R ₂ represents 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 heterocyclic ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, An alkyl group, or an alkyloxy group;
Z ₁ and Z ₂ represent a single bond, -CO-, -CH ₂ O-, -CH═N-, or -CF ₂ -. The method according to any one of claims 1 to 4,
(C) a compound represented by the following formula (c).
(3)

Wherein any three to five of R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ and R ¹⁰⁵ are each independently a hydrogen atom, a halogen atom, C ₁ -C ₆ alkyl, C ₁ -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 halocycloalkyl alkenyl, 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 alkyl) carbonyl, (C ₁ ~ C ₆ haloalkyl) aminocarbonyl, any of the di (C ₁ ~ C ₆ alkyl) aminocarbonyl, cyano, and represents a substituent selected from the group consisting of nitro, R ^101, R ^102, R ^103, R ¹⁰⁴ and R ¹⁰⁵ three or four, if the definition of ^{the, R 101, R 102, R} 103, R 104 and R ¹⁰⁵ of the remaining one or two of the following formula (c-2)
[Chemical Formula 4]

(In the 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 carbon ring or a heterocyclic ring, One or plural hydrogen atoms in the carbon ring or the 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 in the case where any of the following groups is 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, and n represents 0 or 1.) A composition for forming an orientation layer containing the polymer composition according to any one of claims 1 to 5.