KR102154219B1 - Polymerizable composition and film using same - Google Patents

Abstract

Provides a polymerizable liquid crystal composition that can be uniformly applied on a substrate without spotting, and can be laminated on a film formed by irradiating an active energy ray after a coating film on the substrate, and also has good orientation using the polymerizable composition. It is to provide an optically anisotropic body and a laminated body. The present invention provides a polymerizable liquid crystal composition containing a polymer having at least one or more pyrolytic groups and a polymerizable liquid crystal compound. Further, an optically anisotropic body and a laminate using the polymerizable liquid crystal composition of the present invention are also provided.

Description

Polymerizable composition and film using same

The present invention is a polymerizable liquid crystal composition useful as a constituent member of an optically anisotropic body used for optical compensation such as a liquid crystal device, a display, an optical component, a colorant, a security marking, a laser emitting member, or a liquid crystal display, and the composition thereof. It relates to an optically anisotropic body, a retardation film, a retardation patterning film, a brightness enhancement film, a viewing angle compensation film, and an antireflection film.

The polymerizable liquid crystal composition is useful as a constituent member of an optically anisotropic body, and the optically anisotropic body is applied to various liquid crystal displays as, for example, a polarizing film and a retardation film. Polarizing film or retardation film, after applying the polymerizable liquid crystal composition to a substrate and drying the solvent, in a state in which the polymerizable liquid crystal composition is oriented with an alignment film or the like, heating or irradiating an active energy ray to form a polymerizable liquid crystal composition. It is obtained by curing. Further, it is known that a circularly polarized light separation element can be obtained by using a polymerizable cholesteric liquid crystal composition in which a chiral compound is added to a polymerizable liquid crystal composition, and application to a brightness enhancing film or the like is being studied.

These polymerizable liquid crystal compositions are generally applied on a glass substrate or a plastic substrate, or on a substrate having an alignment layer formed as necessary, and cured to form a retardation film. The polymerizable liquid crystal composition is uniformly applied without stains. Is being demanded. Therefore, a fluorine-based surfactant capable of significantly lowering the surface tension of the coating film is generally used as an additive. However, when a fluorine-based surfactant is used, since fluorine atoms remain on the surface of the phase difference film, the surface of the phase difference film becomes a low surface energy layer, making it difficult to laminate on the surface of the phase difference film. In addition, when a polarizing plate is laminated through an adhesive layer on a retardation film using a non-polymerizable fluorine-based surfactant, since the fluorine-based surfactant penetrates into the adhesive layer with time, a peeling trouble of the polarizing plate may occur.

As a method of improving the above problem, a laminated film using a polymerizable fluorine-based surfactant has been reported, but in this method, even if it can be uniformly applied without stains, a laminate having good adhesion laminated to the retardation film could not be obtained. (Patent Documents 1 to 3).

Japanese Patent Publication No. 2003-105030 Japanese Patent Publication No. 2009-41023 Japanese Patent No. 5026060

The problem to be solved by the present invention is to provide a polymerizable liquid crystal composition that can be uniformly applied on a substrate without spots, and can be laminated on a film formed by irradiating an active energy ray after a coating on the substrate. It is to provide an optically anisotropic body and a laminate having good orientation using the polymerizable composition.

In order to solve the above problems, the present invention has focused on a polymerizable liquid crystal composition, and as a result of intensive research, has come to provide the present invention.

That is, the present invention provides a polymerizable liquid crystal composition containing a polymer having at least one or more pyrolytic groups and a polymerizable liquid crystal compound. Further, an optically anisotropic body and a laminate using the polymerizable liquid crystal composition of the present invention are also provided.

By using the polymerizable liquid crystal composition of the present invention, it is possible to uniformly apply on a substrate without unevenness, and a laminate having a lamination having good adhesion on the resulting film formation can be obtained, which is useful for use of an optical material.

Hereinafter, the best mode of the polymerizable liquid crystal composition according to the present invention will be described. In the present invention, the term "liquid crystal" of the polymerizable liquid crystal composition refers to a state in which the organic solvent is removed after applying the polymerizable liquid crystal composition to a substrate. It intends to show liquid crystallinity. In addition, in the present invention, the "liquid crystal" of the polymerizable liquid crystal compound means liquid crystal when it is intended to exhibit liquid crystal properties with only one kind of polymerizable liquid crystal compound to be used, or when mixed with other liquid crystal compounds to form a mixture. It is intended to indicate last name. In addition, the polymerizable liquid crystal composition can be polymerized (filmed) by performing a polymerization treatment by irradiation with light such as ultraviolet rays, heating, or a combination thereof.

(Pyrolytic polymer having a pyrolytic group)

The polymerizable liquid crystal composition of the present invention is characterized by containing at least one or more polymers having a thermally decomposable group. The polymer having a thermally decomposable group is used by adding it to the polymerizable liquid crystal composition, and the polymerizable liquid crystal composition can be uniformly applied without stains on a substrate or a substrate comprising an alignment film used as necessary. Specific examples of the polymer having the thermally decomposable group include a polymer in which the thermally decomposable group contains a fluorine atom and/or a silicon atom.

In addition, it is preferable that the polymer having a thermally decomposable group contains a structural unit represented by the following general formula (I-1-1) or (I-1-2) as a side chain.

(In general formula (I-1-1) and general formula (I-1-2), R ¹ , R ² each independently represent a hydrogen atom or a linear or branched organic group having 1 to 18 carbon atoms , Y ¹ represents an oxygen atom or a sulfur atom, R ⁴ represents an organic group having a fluorine atom and/or a silicon atom, and * represents a bonding site.) It is preferable to contain a structural unit represented by.

In general formula (I-1-1) and general formula (I-1-2), R ¹ represents a hydrogen atom or a linear or branched organic group having 1 to 18 carbon atoms, and R ¹ is a hydrogen atom or A methyl group is preferable, and R ¹ is more preferably a hydrogen atom.

In general formula (I-1-1) and general formula (I-1-2), R ² represents a hydrogen atom or a linear or branched organic group having 1 to 18 carbon atoms, and R ² is a linear An alkyl group having 1 to 12 carbon atoms is preferable, and R ² is more preferably a methyl group.

In general formula (I-1-1) and general formula (I-1-2), Y ¹ represents an oxygen atom or a sulfur atom, but Y ¹ is preferably an oxygen atom.

In the general formulas (I-1-1) and (I-1-2), R ⁴ represents an organic group having a fluorine atom and/or a silicon atom, and R ⁴ is a fluorinated alkyl group, in order to exhibit excellent smoothness, A fluorinated alkenyl group, a fluorinated aromatic group, a poly(perfluoroalkylene ether) group, a polysiloxane group in which one or two or more hydrogen atoms bonded to a silicon atom may each independently be substituted with a group selected from a methyl group and a phenylene group. , A fluorinated alkyl group having 1 to 12 carbon atoms directly bonded to a fluorine atom, a polysiloxane group in which one or two or more hydrogen atoms bonded to a silicon atom may be independently substituted with a group selected from a methyl group and a phenylene group, more preferably fluorine A fluorinated alkyl group having 1 to 8 carbon atoms to which the atom is directly bonded is particularly preferred.

As said R ⁴ , a group represented by the following formula (I-R4-1)-formula (I-R4-19) is preferable, for example.

In the above formula, * represents a bonding site to Y ¹ , R ⁵¹ to R ⁵⁶ each independently represent a hydrogen atom, a methyl group, and a phenyl group, and n5 represents an integer of 1 to 150.

The polymer having a thermally decomposable group of the present invention contains structural units other than the structural units represented by the general formula (I-1-1) or (I-1-2) within the range not impairing the effects of the present invention. You may contain it. Specifically, a side chain can be illustrated by the following general formula (I-2-1) or general formula (I-2-2).

(In General Formula (I-2-1) and General Formula (I-2-2), R ¹¹ and R ²¹ each independently represent a hydrogen atom or a linear or branched organic group having 1 to 18 carbon atoms , Y ¹¹ represents an oxygen atom or a sulfur atom, R ⁴¹ is an organic group having 1 to 18 carbon atoms, and R ²¹ and R ⁴¹ may be bonded to each other to form a heterocycle having Y ¹¹ as a hetero atom, * Represents a binding site.)

In the above, in General Formulas (I-2-1) and (I-2-2), R ¹¹ represents a hydrogen atom, R ²¹ represents a methyl group, and Y ¹¹ represents an oxygen atom or a sulfur atom. The difference in polarity between the formed carboxyl group and the reactivated carboxyl group is large, which is preferable. In addition, as a side chain represented by the said general formula (I-2-1) or general formula (I-2-2), the following formula (I-2-1-1) or a formula (I-2-2-1) The side chain represented by is more preferable.

The polymer having a thermally decomposable group of the present invention can be efficiently produced, for example, by the following method.

Preparation method 1: Polymerizable monomer (α) having a hydroxyl group or a carboxyl group and the following general formula (I-A)

(In General Formula (IA), R ¹ , R ²¹ and R ²² are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R ⁴ is an organic group having a fluorine atom and/or a silicon atom.)

A method of reacting a vinyl ether compound represented by to obtain a polymerizable monomer having a blocked carboxyl group, and then polymerizing the polymerizable monomer.

Production method 2: A method of reacting a polymer obtained by using a polymerizable monomer (?) having a hydroxyl group or a carboxyl group with a vinyl ether compound represented by the general formula (I-A).

As the polymerizable monomer (α) having a hydroxyl group or a carboxyl group, for example, (meth)acrylic acid, itaconic acid, mesaconic acid, maleic acid, fumaric acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylic Rate, 2-(meth)acryloyloxyethylhexahydrophthalic acid, 2-(meth)acryloyloxypropylhexahydrophthalic acid, 2-(meth)acryloyloxyethylphthalic acid, 2-(meth)acryloyl Oxyethyl succinic acid, 2-(meth)acryloyloxyethylmaleic acid, carboxypolycaprolactone mono(meth)acrylate, 2-(meth)acryloyloxyethyltetrahydrophthalic acid, and the like can be preferably illustrated. Among them, (meth)acrylic acid is preferred, and methacrylic acid is more preferred from the viewpoint of being inexpensive and easy to handle.

In addition, in the present invention, "(meth)acrylate" refers to one or both of methacrylate and acrylate, and "(meth)acryloyl group" refers to one of methacryloyl group and acryloyl group, or Both are said, and "(meth)acrylic acid" means one or both of methacrylic acid and acrylic acid.

In the above production method 1, after obtaining a polymerizable monomer having a blocked hydroxyl group or a carboxyl group, when the polymerizable monomer is polymerized, or in the production method 2, a polymerizable monomer having a hydroxyl group or a carboxyl group (α) When obtaining a polymer obtained by using, a polymer may be obtained by using a polymerizable monomer (A) other than the polymerizable monomer (α) together within a range that does not impair the effects of the present invention. Examples of the polymerizable monomer (A) include acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, and vinyl esters.

Examples of the acrylic acid esters include methyl acrylate, ethyl acrylate, propyl acrylate, chlorethyl acrylate, 2-hydroxyethyl acrylate, trimethylolpropane monoacrylate, benzyl acrylate, methoxybenzyl acrylate, and fur. Furyl acrylate, tetrahydrofurfuryl acrylate, etc. are mentioned.

Examples of the methacrylic acid esters include methyl methacrylate, ethyl methacrylate, propyl methacrylate, chlorethyl methacrylate, 2-hydroxyethyl methacrylate, trimethylolpropane monomethacrylate, Benzyl methacrylate, methoxybenzyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, and the like.

Examples of the acrylamides include acrylamide, N-alkylacrylamide (as an alkyl group having 1 to 3 carbon atoms, for example, methyl group, ethyl group, propyl group), N,N-dialkylacrylamide (As an alkyl group, a C1-C3 thing), N-hydroxyethyl-N-methylacrylamide, N-2-acetamide ethyl-N-acetylacrylamide, etc. are mentioned.

As the methacrylamides, for example, methacrylamide, N-alkyl methacrylamide (as an alkyl group, one having 1 to 3 carbon atoms, for example, methyl group, ethyl group, propyl group), N,N-dialkyl Methacrylamide (a C1-C3 thing as an alkyl group), N-hydroxyethyl-N-methyl methacrylamide, N-2-acetamide ethyl-N-acetyl methacrylamide, etc. are mentioned.

As the allyl compound, for example, allyl esters (e.g., allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, Allyl lactate), allyloxyethanol, etc. are mentioned.

As the vinyl ethers, for example, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chlorethyl vinyl ether, 1-methyl-2, 2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetra Vinyl esters such as hydrofurfuryl vinyl ether: vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chlor acetate, vinyl dichlor acetate, vinyl methoxy acetate, vinyl Butoxyacetate, vinyl lactate, vinyl-β-phenyl butyrate, vinylcyclohexylcarboxylate, and the like.

As said dialkyl itaconic acid, dimethyl itaconic acid, diethyl itaconic acid, dibutyl itaconic acid, etc. are mentioned. Examples of the dialkyl esters or monoalkyl esters of fumaric acid include dibutyl fumarate and the like, as well as crotonic acid, itaconic acid, acrylonitrile, methacrylonitrile, maleylonitrile, and styrene.

Further, as the polymerizable monomer (A), a radical polymerizable monomer having an oxyalkylene group can also be used. As a radical polymerizable monomer having an oxyalkylene group, for example, polypropylene glycol mono (meth) acrylate, polytetramethylene glycol (meth) acrylate, poly (ethylene glycol propylene glycol) mono (meth) acrylate, Polyethylene glycol polypropylene glycol mono (meth) acrylate, poly (ethylene glycol tetramethylene glycol) mono (meth) acrylate, polyethylene glycol polytetramethylene glycol mono (meth) acrylate, poly (propylene glycol tetramethylene) Glycol) mono (meth) acrylate, polypropylene glycol polytetramethylene glycol mono (meth) acrylate, poly (propylene glycol, butylene glycol) mono (meth) acrylate, polypropylene glycol polybutylene glycol mono ( Meth)acrylate, poly(ethylene glycol/butylene glycol) mono(meth)acrylate, polyethylene glycol/polybutylene glycol mono(meth)acrylate, poly(tetraethylene glycol/butylene glycol) mono(meth)acrylic Rate, polytetraethylene glycol polybutylene glycol mono(meth)acrylate, polybutylene glycol mono(meth)acrylate, poly(ethylene glycol trimethylene glycol) mono(meth)acrylate, polyethylene glycol polytri Methylene glycol mono(meth)acrylate, poly(propylene glycol trimethylene glycol) mono(meth)acrylate, polypropylene glycol polytrimethylene glycol mono(meth)acrylate, poly(trimethylene glycol·tetramethylene glycol) Mono(meth)acrylate, polytrimethylene glycol polytetramethylene glycol mono(meth)acrylate, poly(butylene glycol trimethylene glycol) mono(meth)acrylate, polybutylene glycol polytrimethylene glycol mono (Meth)acrylate, etc. are mentioned.

In addition, the ``poly(ethylene glycol propylene glycol)'' means a random copolymer of ethylene glycol and propylene glycol, and ``polyethylene glycol polypropylene glycol'' means a block copolymer of ethylene glycol and propylene glycol, , And so on.

As commercially available products of the radical polymerizable monomer having an oxyalkylene group, for example, ``NK ester AMP-10G'', ``NK ester AMP-20G'', ``NK ester AMP-60G'' manufactured by Shin-Nakamura Chemical Industries, Ltd. "BLEMMER PME-100", "BLEMMER PME-200", "BLEMMER PME-400", "BLEMMER PME-4000", "BLEMMER PP-1000", "BLEMMER PP-500", "BLEMMER PP-" manufactured by Chiyu Corporation. 800'', ``BLEMMER 70PEP-350B'', ``BLEMMER 55PET-800'', ``BLEMMER 50POEP-800B'', ``BLEMMER 10PPB-500B'', ``BLEMMER NKH-5050'', ``BLEMMER AP-400'', and ``Blemmer AP-400'' manufactured by Sutmar. SR604" and the like. The radical polymerizable monomer (γ) may be used alone or in combination of two or more.

Further, as the polymerizable monomer (A), a radically polymerizable monomer having a fluorinated alkyl group or a poly(perfluoroalkylene ether) chain can also be used within a range that does not impair the effects of the present invention. As said radical polymerizable monomer, what is represented by the following general formula (A0) can be illustrated preferably, for example.

[In the general formula (A0), R represents a hydrogen atom or a methyl group, L represents a group in any of the following formulas (L-1) to (L-10), and Rf is the following formula (Rf-1) It shows the group in any one of ~ (Rf-7).]

(N in the above formulas (L-1), (L-3), (L-5), (L-6) and (L-7) represents an integer of 1 to 8. The formula (L-8) , M in (L-9) and (L-10) represents an integer of 1 to 8, and n represents an integer of 0 to 8. Rf in the above formulas (L-6) and (L-7)" Represents a group in any one of the following formulas (Rf-1) to (Rf-7).)

(N in the above formulas (Rf-1) to (Rf-4) is, for example, an integer of 1 to 6, preferably an integer of 4 to 6. m in the formula (Rf-5) is an example For example, it is an integer of 1 to 18, n is an integer of 0 to 5, and the sum of m and n is 1 to 23. Preferably, m is an integer of 1 to 5, and n is an integer of 0 to 4 And the sum of m and n is 4 to 5. In the above formula (Rf-6), m is an integer of 1 to 6, n is an integer of 1 to 3, and l is an integer of 1 to 20. And p is an integer of 0 to 5, and the sum of m, p and the product of n and l is 2 to 71. Preferably, m is an integer of 1 to 3, and n is an integer of 1 to 3. And l is an integer of 1 to 6, p is an integer of 0 to 2, and the sum of m, p and the product of n and l is 2 to 23.)

As a specific example of the radical polymerizable monomer having the above fluorinated alkyl group or poly(perfluoroalkylene ether) chain, for example, the following polymerizable monomers (A-1) to (A-15), etc. will be preferably illustrated. I can.

N in Formula (A-13)-Formula (A-15) is 0-20, for example.

As the vinyl ether compound represented by the general formula (IA), for example, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1 -Vinyloxyoctane, 3,3,4,4,5,5,6,6,6-nonafluoro-1-vinyloxyhexane, etc. are mentioned. Among them, the reaction with the polymer obtained by using the polymerizable monomer (?) easily proceeds, and since the polarity difference before and after heating becomes large, it is preferable. In addition, 3,3,4,4,5,5,6,6,7,7,8,8,8 from the viewpoint of coating properties of a polymerizable liquid crystal composition containing a polymer having a pyrolytic group and ease of lamination after film formation. -Tridecafluoro-1-vinyloxyoctane is preferred.

When obtaining the polymer having a thermally decomposable group of the present invention, vinyl ether compounds other than the compound represented by the general formula (IA) are used in a range that does not impair the effects of the present invention with the vinyl ether compound represented by the general formula (IA). Can also be used in combination. As such a vinyl ether compound, for example, methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl Aliphatic vinyl ether compounds such as vinyl ether; aliphatic vinylthioether compounds corresponding to these; 2,3-dihydrofuran, 3,4-dihydrofuran, 2,3-dihydro-2H-pyran, 3,4- Dihydro-2H-pyran, 3,4-dihydro-2-methoxy-2H-pyran, 3,4-dihydro-4,4-dimethyl-2H-pyran-2-one, 3,4-dihydro Cyclic vinyl ether compounds, such as 2-ethoxy-2H-pyran and sodium 3,4-dihydro-2H-pyran-2-carboxylate; Cyclic vinyl thioether compounds corresponding to these, etc. are mentioned.

In the production method 1, a polymerizable monomer (?) having a carboxyl group and a vinyl ether compound represented by the general formula (I-A) are reacted. Thereby, a polymerizable monomer having a blocked carboxyl group can be obtained. The reaction conditions include, for example, conditions of heating to about 20 to 100°C in the presence of an acid catalyst. In addition, when polymerizing the polymerizable monomer having a blocked carboxyl group, it can be carried out under conditions of polymerizing the polymerizable monomer (α) described later.

In the above production method 2, the method of obtaining the polymer using the polymerizable monomer (α) is not particularly limited, but, for example, a polymerizable monomer (α) and, if necessary, a radical polymerizable monomer (γ) as an organic solvent. Among them, a method of polymerization using a radical polymerization initiator, etc. are mentioned. As the organic solvent used here, ketones, esters, amides, sulfoxides, ethers, and hydrocarbons are preferable, and specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, acetic acid Butyl, propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, toluene, xylene, etc. I can. These are appropriately selected in consideration of the boiling point, compatibility, and polymerizability. Examples of the radical polymerization initiator include peroxides such as benzoyl peroxide, and azo compounds such as azobisisobutyronitrile. In addition, chain transfer agents such as lauryl mercaptan, 2-mercaptoethanol, thioglycerol, ethylthioglycolic acid, and octylthioglycolic acid may be used as needed.

In the production method 2, the polymer and the vinyl ether compound represented by the general formula (I-A) can be reacted by heating at about 20 to 100°C, for example, in the presence of an acid catalyst. By this reaction, the carboxyl group of the polymer is blocked, and a polymer having a structure represented by the general formula (I-1-1) or (I-1-2) can be obtained. The blocked carboxyl group falls off the blocked vinyl ether in a high temperature environment, for example, in an environment of 150 to 300°C, and the carboxyl group is regenerated.

As the polymer having a thermally decomposable group, a polymer having a structural unit selected from the following general formulas (I-1-1-1) to (I-1-2-2) is preferable.

(In the above General Formulas (I-1-1-1) to (I-1-2-2), R ¹ represents a hydrogen atom or a linear or branched organic group having 1 to 18 carbon atoms. R ⁴¹ and R ⁵ each independently represent an alkylene group having 1 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or an alicyclic hydrocarbon group having 4 to 12 carbon atoms R ⁶ is a hydrogen atom or a methyl group R ⁴² represents an organic group having a fluorine atom and/or a silicon atom, n represents an integer of 0 to 12.)

In the general formula (I-1-1-1) to the general formula (I-1-2-2), a preferred group of R ⁴² is the general formula (I-1-1) or the general formula (I-1- It is the same as the preferable group of R ⁴ described in 2).

When the polymerizable liquid crystal composition containing the polymer having a thermally decomposable group is applied to a substrate, the polymer containing a fluorine atom and/or a silicon atom segregates on the surface of the coating film. The water repellency and oil repellency of the film-forming surface obtained by segregating on this surface and the group having a fluorine atom and/or a silicon atom are desorbed from the polymer are deteriorated. As a result of such a phenomenon, it becomes easy to laminate another film on the film formation made of the polymerizable liquid crystal composition, and a laminate can be easily obtained.

The number average molecular weight (Mn) of the polymer having a thermally decomposable group used in the present invention represented by the general formula (I-1-1-1) to the general formula (I-1-2-2) or the like is used From the viewpoint of compatibility with a liquid crystal compound and solubility in a solvent to be used, the range of 1,000 to 50,000 is preferable, the range of 1,500 to 20,000 is more preferable, and the range of 2,000 to 8,000 is still more preferable. In addition, the weight average molecular weight (Mw) is preferably in the range of 1,000 to 100,000, and more preferably in the range of 5,000 to 70,000. In addition, the number average molecular weight (Mn) and the weight average molecular weight (Mw) are values converted into polystyrene based on gel permeation chromatography (hereinafter abbreviated as "GPC").

The polymer having a thermally decomposable group used in the present invention may be used singly or in combination of two or more.

The content of the polymer having a pyrolytic group used in the present invention is 0.005 to 5 parts by mass based on 100 parts by mass of the total amount of the polymerizable liquid crystal compound, the polymerizable chiral compound, and the polymerizable discotic compound contained in the polymerizable liquid crystal composition. It is preferable, and it is more preferable to use 0.01-2 mass parts, it is still more preferable to use 0.05-1 mass parts, and it is especially preferable to use 0.1-0.5 mass parts. By setting the content of the polymer having a pyrolytic group to be contained in the polymerizable liquid crystal composition in a specific range, it can be uniformly applied on a substrate without spots, and also obtained by irradiating an active energy ray after coating on the substrate and firing. A laminate in which other layers are laminated on the film formation can be obtained.

(Polymerizable liquid crystal compound)

The polymerizable liquid crystal compound used in the present invention is not particularly limited as long as it exhibits liquid crystallinity in a composition alone or in a composition with another compound, and has at least one or more polymerizable functional groups, and known customary ones can be used.

For example, Handbook of Liquid Crystals (D.Demus, JWGoodby, GWGray, HWSpiess, V.Vill edit, published by Wiley-VCH, 1998), Quarterly Chemistry Review No.22, Liquid Crystal Chemistry (Japanese painting) Society edition, 1994), or Japanese Patent Laid-Open Hei 7-294735, Japanese Patent Laid-Open Hei 8-3111, Japanese Patent Laid-Open Hei 8-29618, Japanese Patent Laid-Open Hei 11-80090 Structures such as 1,4-phenylene group and 1,4-cyclohexylene group as described in Japanese Patent Application Laid-Open No. Hei 11-116538, Japanese Patent Application Laid-Open No. Hei 11-148079, etc. A rod-shaped polymerizable liquid crystal compound having a rigid moiety called mesogen and a polymerizable functional group such as a vinyl group, an acrylic group, or a (meth)acrylic group, or Japanese Patent Laid-Open No. 2004-2373, Japanese Patent Publication A rod-shaped polymerizable liquid crystal compound having a maleimide group as described in Publication No. 2004-99446 is mentioned. Among them, a rod-shaped liquid crystal compound having a polymerizable group is preferred because it is easy to make a thing including a low temperature before and after room temperature as a liquid crystal temperature range.

As for the polymerizable liquid crystal compound, a compound specifically represented by the following general formula (II) is preferable.

In the formula, P ² represents a polymerizable functional group,

Sp ¹ represents an alkylene group having 1 to 18 carbon atoms (the hydrogen atom in the alkylene group is substituted by at least one halogen atom, a CN group, or an alkyl group having 1 to 8 carbon atoms having a polymerizable functional group, May be present, and one CH ₂ group present in this group or two or more CH ₂ groups not adjacent to each other is each independently substituted by -O-, -COO-, -OCO-, or -OCO-O- May be present),

X ¹ is -O-, -S-, -OCH ₂ -, -CH ₂ O-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO -O-, -CO-NH-, -NH-CO-, -SCH ₂ -, -CH ₂ S-, -CF ₂ O-, -OCF ₂ -, -CF ₂ S-, -SCF ₂ -,- CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-CH ₂ CH ₂ -, -OCO-CH ₂ CH ₂ -,- CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO-CH ₂ -, -OCO-CH ₂ -, -CH ₂ -COO-, -CH ₂ -OCO-, -CH=CH- , -N=N-, -CH=NN=CH-, -CF=CF-, -C≡C- or a single bond (however, P ² -Sp ¹ and Sp ¹ -X ¹ are -OO- , -O-NH-, -SS- and -OS- groups are not included.),

q1 represents 0 or 1,

MG represents a mesogenic group,

R ² represents a hydrogen atom, a halogen atom, a cyano group, or a linear or branched alkyl group having 1 to 12 carbon atoms, and the alkyl group may be linear or branched, and the alkyl group may be one -CH ₂ -or Two or more non-adjacent -CH ₂ -are each independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O- CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-,- May be substituted by CH=CH-, -CF=CF- or -C≡C-, or R ² is a general formula (II-a)

(In the formula, P ³ represents a polymerizable functional group, Sp ² represents the same as defined in Sp ¹ , and X ² represents the same as defined in X ¹ (however, P ³ -Sp ² and Sp ² -X ² does not include -OO-, -O-NH-, -SS- and -OS- groups.), q ² represents 0 or 1),

The mesogenic group represented by the MG is the general formula (II-b)

(In the formula, B1, B2, and B3 are each independently a 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6- Diyl group, pyridin-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group, 1,2,3,4-tetra Hydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3, 4,4a,9,10a-octahydrophenanthrene-2,7-diyl group, 1,4-naphthylene group, benzo[1,2-b:4,5-b']dithiophene-2,6- Diyl group, benzo[1,2-b:4,5-b']diselenophene-2,6-diyl group, [1]benzothieno[3,2-b]thiophene-2,7-di Diary, [1] benzoselenopheno[3,2-b]selenophene-2,7-diyl group, or fluorene-2,7-diyl group, and one or more F, Cl, CF ₃ as a substituent , OCF ₃ , CN group, an alkyl group having 1 to 8 carbon atoms (the hydrogen atom in the alkyl group may be substituted with one or more phenyl groups, and one CH ₂ group present in the group or 2 not adjacent Each of the _two or more CH ₂ groups may each independently be substituted with -O-, -COO-, -OCO-, or -OCO-O-), an alkoxy group having 1 to 8 carbon atoms, and 1 carbon atom number. -8 alkanoyl group, C1-C8 alkanoyloxy group, C1-C8 alkoxycarbonyl group, C2-C8 alkenyl group, C2-C8 alkenyloxy group, Alkenoyl group having 2 to 8 carbon atoms, alkenoyloxy group having 2 to 8 carbon atoms, and/or general formula (II-c)

(In the formula, P ⁴ represents a polymerizable functional group,

Sp ³ represents the same as defined in Sp ¹ , and X ³ represents -O-, -COO-, -OCO-, -OCH ₂ -, -CH ₂ O-, -CH ₂ CH ₂ OCO-,- _{COOCH 2 CH 2 -, -OCOCH 2} CH 2 -, or represents a single bond, q ³ is 0 or 1, q ⁴ is 0 or 1. (However, P ⁴ -Sp ³ and Sp ³ -X ³ do not include -OO-, -O-NH-, -SS-, and -OS- groups.)),

Z1 and Z2 are each independently, -COO-, -OCO-, -CH ₂ CH ₂ -, -OCH ₂ -, -CH ₂ O-, -CH=CH-, -C≡C-, -CH=CHCOO -, -OCOCH=CH-, -CH ₂ CH ₂ COO-, -CH ₂ CH ₂ OCO-, -COOCH ₂ CH ₂ -, -OCOCH ₂ CH ₂ -, -C=N-, -N=C-, -CONH-, -NHCO-, -C(CF ₃ ) ₂ -, represents an alkyl group or single bond having 2 to 10 carbon atoms which may have a halogen atom, r1 represents 0, 1, 2 or 3, B1 And when a plurality of Z1s exist, each of them may be the same or different.).

It is preferable that P ² , P ³ and P ⁴ each independently represent a substituent selected from polymerizable groups represented by the following formulas (P-2-1) to (P-2-20).

Among these polymerizable functional groups, formulas (P-2-1), (P-2-2), (P-2-7), (P-2-12), (P-2) -13) is preferable, and formulas (P-2-1) and (P-2-2) are more preferable.

(Monofunctional polymerizable liquid crystal compound)

Among the compounds represented by the general formula (II), as the monofunctional polymerizable liquid crystal compound having one polymerizable functional group in the molecule, a compound represented by the following general formula (II-2-1) is preferable.

In the formula, P ² , Sp ¹ , X ¹ , q1 and MG each represent the same as defined in the general formula (II), and R ²¹ represents a hydrogen atom, a halogen atom, a cyano group, and one -CH _2- Or two or more non-adjacent -CH ₂ -are each independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O -CO-O-, -CO-NH-, -NH-CO-, -NH-, -N(CH ₃ )-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH =CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or a straight-chain or branched alkyl group having 1 to 12 carbon atoms, which may be substituted by -C≡C-, and the number of carbon atoms 1 to 12 linear or branched alkenyl groups are represented, and one or two or more hydrogen atoms of the alkyl group and the alkenyl group may be substituted with a halogen atom or a cyano group, or may be the same when multiple substitutions are made, It may be different. Examples of general formula (II-2-1) include compounds represented by the following general formulas (II-2-1-1) to (II-2-1-4), but limited to the following general formula. It does not become.

In the formula, P ² , Sp ¹ , X ¹ , and q1 each represent the same as defined in the general formula (II),

B11, B12, B13, B2, B3 represents the same as the definition of B1 to B3 in the general formula (II-b), respectively, may be the same or different,

Z11, Z12, Z13, Z2 represents the same as the definition of Z1 to Z3 in the general formula (II-b), and may be the same or different, respectively,

R ²¹ represents a hydrogen atom, a halogen atom, a cyano group, one -CH ₂ -or two or more non-adjacent -CH ₂ -s, each independently -O-, -S-, -CO-, -COO- , -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -NH-, -N(CH ₃ )-,- By CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or -C≡C- A linear or branched alkyl group having 1 to 12 carbon atoms, which may be substituted, or a linear or branched alkenyl group having 1 to 12 carbon atoms, and one or two or more hydrogen atoms of the alkyl group and the alkenyl group are halogen atoms. , May be substituted with a cyano group, or may be the same or different, respectively, in the case of a plurality of substitutions.

As a compound represented by the said general formula (II-2-1-1)-(II-2-1-4), the following formula (II-2-1-1-1)-formula (II-2-1 Although the compound represented by -1-26) is illustrated, it is not limited to these.

In the formula, R ^c represents a hydrogen atom or a methyl group, m represents an integer of 0 to 18, n represents 0 or 1, R ²¹ represents the general formula (II-2-1-1) to (II It represents the same as the definition of -2-1-4), wherein R ²¹ represents a hydrogen atom, a halogen atom, a cyano group, and one -CH ₂ -to -O-, -CO-, -COO-, -OCO- It is preferable to represent a straight-chain alkyl group having 1 to 6 carbon atoms or a straight-chain alkenyl group having 1 to 6 carbon atoms, which may be substituted by

The cyclic group is one or more F, Cl, CF ₃ , OCF ₃ , CN group as a substituent, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkano having 1 to 8 carbon atoms Diary, alkanoyloxy group having 1 to 8 carbon atoms, alkoxycarbonyl group having 1 to 8 carbon atoms, alkenyl group having 2 to 8 carbon atoms, alkenyloxy group having 2 to 8 carbon atoms, 2 to carbon atoms You may have an alkenoyl group of 8 and an alkenoyloxy group of 2 to 8 carbon atoms.

The total content of the monofunctional polymerizable liquid crystal compound having one polymerizable functional group in the molecule is preferably 0 to 90% by mass, and 0 to 85% by mass in the total amount of the polymerizable liquid crystal compound used in the polymerizable liquid crystal composition. It is more preferable to contain, and it is especially preferable to contain 0 to 80 mass %. When the orientation of the optically anisotropic body is important, the lower limit is preferably 5% by mass or more, more preferably 10% by mass or more, and when the hardness of the coating film is important, the upper limit is preferably 80% by mass or less. And more preferably 70% by mass or less.

(Bifunctional polymerizable liquid crystal compound)

Among the compounds represented by the general formula (II), as a bifunctional polymerizable liquid crystal compound having two polymerizable functional groups in the molecule, a compound represented by the following general formula (II-2-2) is preferable.

In the formula, P ² , Sp ¹ , X ¹ , q1, MG, X ² , Sp ² , q2, and P ³ each represent the same as defined in the general formula (II). Examples of the general formula (II-2-2) include compounds represented by the following general formulas (II-2-2-1) to (II-2-2-4), but limited to the following general formula. It does not become.

In the formula, P ² , Sp ¹ , X ¹ , q1, MG, X ² , Sp ² , q2, P ³ each represent the same as the definition of the general formula (II),

B11, B12, B13, B2, B3 represents the same as the definition of B1 to B3 in the general formula (II-b), respectively, may be the same or different,

Z11, Z12, Z13, and Z2 represent the same as the definition of Z1 to Z3 in the general formula (II-b), and may be the same or different, respectively.

Among the compounds represented by the general formulas (II-2-2-1) to (II-2-2-4), the general formulas (II-2-2-2) to (II-2-2-4) When a compound having three or more ring structures is used in the compound to be displayed, the orientation of the obtained optically anisotropic body is good, and since the curability is also good, it is preferable, and general formula (II-2-) having three ring structures in the compound It is particularly preferable to use the compound represented by 2-2).

As a compound represented by the said general formula (II-2-2-1)-(II-2-2-4), the following formula (II-2-2-1-1)-formula (II-2-2 Although the compound represented by -1-21) is illustrated, it is not limited to these.

In the formula, R ^d and R ^e each independently represent a hydrogen atom or a methyl group,

The cyclic group is one or more F, Cl, CF ₃ , OCF ₃ , CN group as a substituent, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkano having 1 to 8 carbon atoms Diary, alkanoyloxy group having 1 to 8 carbon atoms, alkoxycarbonyl group having 1 to 8 carbon atoms, alkenyl group having 2 to 8 carbon atoms, alkenyloxy group having 2 to 8 carbon atoms, 2 to carbon atoms You may have an alkenoyl group of 8 and an alkenoyloxy group of 2 to 8 carbon atoms.

m1 and m2 each independently represent an integer of 0 to 18, and n1, n2, n3, and n4 each independently represent 0 or 1.

Although 1 type or 2 or more types can be used for liquid crystal compounds which have two polymerizable functional groups, 1 type-5 types are preferable, and 2 types-5 types are more preferable.

The total content of the bifunctional polymerizable liquid crystal compound having two polymerizable functional groups in the molecule is preferably 10 to 100% by mass, and 15 to 85% by mass in the total amount of the polymerizable liquid crystal compound used in the polymerizable liquid crystal composition. It is more preferable to contain, and it is particularly preferable to contain 20 to 80% by mass. When the hardness of the coating film is important, the lower limit is preferably 30% by mass or more, more preferably 50% by mass or more, and when the orientation of the optically anisotropic body is important, the upper limit is preferably 85% by mass or less. And it is more preferable to set it as 80 mass% or less.

(Polyfunctional polymerizable liquid crystal compound)

As the polyfunctional polymerizable liquid crystal compound having three or more polymerizable functional groups, it is preferable to use a compound having three polymerizable functional groups. Among the compounds represented by the general formula (II), as the polyfunctional polymerizable liquid crystal compound having three polymerizable functional groups in the molecule, a compound represented by the following general formula (II-2-3) is preferable.

In the formula, P ² , Sp ¹ , X ¹ , q1, MG, X ² , Sp ² , q2, P ³ , X ³ , q4, Sp ³ , q3, P ⁴ are the definitions of the general formula (II), respectively Represents the same as Examples of the general formula (II-2-3) include compounds represented by the following general formulas (II-2-3-1) to (II-2-3-8), but limited to the following general formula. It does not become.

In the formula, P ² , Sp ¹ , X ¹ , q1, MG, X ² , Sp ² , q2, P ³ , X ³ , q4, Sp ³ , q3, P ⁴ are the definitions of the general formula (II), respectively Represents the same as

B11, B12, B13, B2, B3 represents the same as the definition of B1 to B3 in the general formula (II-b), respectively, may be the same or different,

Z11, Z12, Z13, and Z2 represent the same as the definition of Z1 to Z3 in the general formula (II-b), and may be the same or different, respectively.

As a compound represented by the said general formula (II-2-3-1)-(II-2-3-8), the following formula (II-2-3-1-1)-formula (II-2-3 Although the compound represented by -1-6) is illustrated, it is not limited to these.

In the formula, R ^f , R ^g and R ^h each independently represent a hydrogen atom or a methyl group, and R ⁱ , R ^j and R ^k each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, and 1 Represents an alkoxy group of ~ 6, a cyano group, and when these groups are an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, all are unsubstituted or substituted by one or two or more halogen atoms And, the cyclic group is one or more F, Cl, CF ₃ , OCF ₃ , CN group as a substituent, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and Alkanoyl group, alkanoyloxy group having 1 to 8 carbon atoms, alkoxycarbonyl group having 1 to 8 carbon atoms, alkenyl group having 2 to 8 carbon atoms, alkenyloxy group having 2 to 8 carbon atoms, and number of carbon atoms You may have an alkenoyl group of 2 to 8 and an alkenoyloxy group of 2 to 8 carbon atoms.

m4 to m9 each independently represent an integer of 0 to 18, and n4 to n9 each independently represent 0 or 1.

One or two or more polyfunctional polymerizable liquid crystal compounds having three or more polymerizable functional groups can be used.

The total content of the polyfunctional polymerizable liquid crystal compound having three or more polymerizable functional groups in the molecule is preferably 0 to 80% by mass, and 0 to 60% by mass in the total amount of the polymerizable liquid crystal compound used in the polymerizable liquid crystal composition. It is more preferable to contain %, and it is especially preferable to contain 0-40 mass %. When placing importance on the rigidity of the optically anisotropic body, the lower limit is preferably 10% by mass or more, more preferably 20% by mass or more, particularly preferably 30% by mass or more, while low cure shrinkage When placing importance, it is preferable to set the upper limit to 50 mass% or less, it is more preferable to set it as 35 mass% or less, and it is especially preferable to set it as 20 mass% or less.

(Combination of multiple types of polymerizable liquid crystal compounds)

In the polymerizable liquid crystal composition of the present invention, it is preferable to mix and use a plurality of the polymerizable liquid crystal compounds. When the at least one or more monofunctional polymerizable liquid crystal compounds and at least one or more bifunctional polymerizable liquid crystal compounds and/or polyfunctional polymerizable liquid crystal compounds are used in combination, the curability of the optically anisotropic body obtained is improved, and Since adhesiveness also becomes favorable, it is preferable, and it is more preferable to use at least one or more monofunctional polymerizable liquid crystal compounds and at least one or more bifunctional polymerizable liquid crystal compounds in combination. Among them, when the polymerizable liquid crystal composition of the present invention is used to form an optically anisotropic body, in the case of further improving curability, as a bifunctional polymerizable liquid crystal compound, the (II-2-) having three or more ring structures in the compound It is preferable to use a compound selected from 2-2) to (II-2-2-4) to prepare a mixture of polymerizable liquid crystal compounds, and (II-2-1-2 above having three ring structures in the compound) It is particularly preferable to use a mixture of the compound represented by) and the compound represented by (II-2-2-2) in combination.

The total amount of the monofunctional polymerizable liquid crystal compound and the bifunctional polymerizable liquid crystal compound is preferably 70% by mass to 100% by mass, and 80% by mass to 100% of the total amount of the polymerizable liquid crystal compound used in the polymerizable liquid crystal composition. It is particularly preferable to set it as mass%.

(Other liquid crystal compounds)

Further, to the liquid crystal composition of the present invention, a compound containing a mesogenic group that does not have a polymerizable group may be added, and a conventional liquid crystal device such as STN (super twisted nematic) liquid crystal or TN (twisted nema Tick) compounds used for liquid crystals, TFT (thin film transistor) liquid crystals, and the like are mentioned.

The compound containing a mesogenic group which does not have a polymerizable functional group is specifically preferably a compound represented by the following general formula (5).

Mesogenic group or mesogenic supporting group represented by MG3 is general formula (5-b)

(In the formula, A1 ^d , A2 ^d and A3 ^d are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5- Diyl group, 1,3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo(2,2,2) octylene group, decahydronaphthalene-2 ,6-diyl group, pyridin-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group, 1,2,3, 4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2 ,3,4,4a,9,10a-octahydrophenanthrene-2,7-diyl group, 1,4-naphthylene group, benzo[1,2-b:4,5-b']dithiophene-2 ,6-diyl group, benzo[1,2-b:4,5-b']diselenophene-2,6-diyl group, [1]benzothieno[3,2-b]thiophene-2, 7-diyl group, [1]benzoselenopheno[3,2-b]selenophene-2,7-diyl group, or fluorene-2,7-diyl group, and at least one F, Cl as a substituent , CF ₃ , OCF ₃ , CN group, alkyl group having 1 to 8 carbon atoms, alkoxy group, alkanoyl group, alkanoyloxy group, alkenyl group having 2 to 8 carbon atoms, alkenyloxy group, alkenoyl group, alkenoyl May have an oxy group,

Z0 ^d , Z1 ^d , Z2 ^d and Z3 ^d are each independently, -COO-, -OCO-, -CH ₂ CH ₂ -, -OCH ₂ -, -CH ₂ O-, -CH=CH-, -C ≡C-, -CH=CHCOO-, -OCOCH=CH-, -CH ₂ CH ₂ COO-, -CH ₂ CH ₂ OCO-, -COOCH ₂ CH ₂ -, -OCOCH ₂ CH ₂ -, -CONH-, -NHCO-, represents an alkylene group or a single bond which may have a halogen atom having 2 to 10 carbon atoms,

n ^e represents 0, 1 or 2,

R ⁵¹ and R ⁵² each independently represent a hydrogen atom, a halogen atom, a cyano group, or an alkyl group having 1 to 18 carbon atoms, and the alkyl group may be substituted with one or more halogen atoms or CN, and is present in this group. One CH ₂ group or two or more non-adjacent CH ₂ groups are each independently of each other, in a form in which oxygen atoms are not directly bonded to each other, -O-, -S-, -NH-, -N(CH ₃ ) Compounds represented by -, -CO-, -COO-, -OCO-, -OCOO-, -SCO-, -COS-, or -C≡C- may be substituted.).

Specifically, although shown below, it is not limited to these.

Ra and Rb each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, and a cyano group, and these groups are an alkyl group having 1 to 6 carbon atoms, or 1 In the case of the alkoxy group of ~ 6, all may be unsubstituted or substituted with one or two or more halogen atoms.

The total content of the compound having a mesogenic group is preferably 0% by mass or more and 20% by mass or less with respect to the total amount of the polymerizable liquid crystal composition, and when used, it is preferably 1% by mass or more, and preferably 2% by mass or more, It is preferable that it is 5 mass% or more, and it is preferable that it is 15 mass% or less, and it is preferable that it is 10 mass% or less.

(Other ingredients)

(Chiral compound)

The polymerizable liquid crystal composition in the present invention may contain liquid crystal properties other than the polymerizable compound represented by the general formula (II), or may contain a polymerizable chiral compound that may be non-liquid crystal.

As the polymerizable chiral compound used in the present invention, it is preferable to have one or more polymerizable functional groups. As such a compound, for example, Japanese Patent Laid-Open No. 11-193287, Japanese Patent Laid-Open No. 2001-158788, Japanese Patent Laid-Open No. 2006-52669, Japanese Patent Laid-Open No. 2007-269639, Japanese Including chiral saccharides such as isosorbide, isomannite, and glucoside, as described in Japanese Patent Application Laid-Open No. 2007-269640 and 2009-84178, and 1,4-phenylene group, 1 A polymerizable chiral compound having a rigid moiety such as a ,4-cyclohexylene group, a vinyl group, an acryloyl group, a (meth)acryloyl group, and a polymerizable functional group such as a maleimide group, Japanese Patent Laid-Open No. 8 Polymeric chiral compounds composed of terpenoid derivatives, as described in Publication No. 239666, NATURE VOL35 pages 467 to 469 (issued on November 30, 1995), NATURE VOL392 pages 476 to 479 (April 2, 1998) As described in Japan), a polymerizable chiral compound composed of a spacer having a mesogenic group and a chiral moiety, or as described in Japanese Patent Publication No. 2004-504285 and Japanese Patent Publication No. 2007-248945. The same polymerizable chiral compound containing a binaphthyl group is mentioned. Among them, a chiral compound having a large helical torsional force (HTP) is preferable for the polymerizable liquid crystal composition of the present invention.

The blending amount of the polymerizable chiral compound is required to be appropriately adjusted according to the helical organic force of the compound, but it is preferable to contain 0 to 25% by mass, more preferably 0 to 20% by mass, in the polymerizable liquid crystal composition. , It is particularly preferable to contain 0 to 15% by mass.

As an example of the general formula of the polymerizable chiral compound, general formulas (3-1) to (3-4) can be mentioned, but it is not limited to the following general formula.

In the formula, Sp ^3a and Sp ^3b each independently represent an alkylene group having 0 to 18 carbon atoms, and the alkylene group has one or more halogen atoms, CN groups, or 1 to 8 carbon atoms having a polymerizable functional group. May be substituted by an alkyl group, one CH ₂ group present in this group or two or more non-adjacent CH ₂ groups are each independently of each other, in a form in which oxygen atoms are not directly bonded to each other, -O-, -S -, -NH-, -N(CH ₃ )-, -CO-, -COO-, -OCO-, -OCOO-, -SCO-, -COS- or -C≡C- may be substituted,

A1, A2, A3, A4, and A5 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group , 1,3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6 -Diyl group, pyridin-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group, 1,2,3,4- Tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3 ,4,4a,9,10a-octahydrophenanthrene-2,7-diyl group, 1,4-naphthylene group, benzo[1,2-b:4,5-b']dithiophene-2,6 -Diyl group, benzo[1,2-b:4,5-b']diselenophene-2,6-diyl group, [1]benzothieno[3,2-b]thiophene-2,7- Diyl group, [1]benzoselenopheno[3,2-b]selenophene-2,7-diyl group, or fluorene-2,7-diyl group, n, l and k are each independently, Represents 0 or 1, and 0≤n+l+k≤3,

Z0, Z1, Z2, Z3, Z4, Z5, and Z6 are each independently, -COO-, -OCO-, -CH ₂ CH ₂ -, -OCH ₂ -, -CH ₂ O-, -CH=CH- , -C≡C-, -CH=CHCOO-, -OCOCH=CH-, -CH ₂ CH ₂ COO-, -CH ₂ CH ₂ OCO-, -COOCH ₂ CH ₂ -, -OCOCH ₂ CH ₂ -,- CONH-, -NHCO-, represents an alkyl group or a single bond which may have a halogen atom having 2 to 10 carbon atoms,

n5 and m5 each independently represent 0 or 1,

R ^3a and R ^3b represent a hydrogen atom, a halogen atom, a cyano group, or an alkyl group having 1 to 18 carbon atoms, and the alkyl group may be substituted with one or more halogen atoms or CN, and 1 Two CH ₂ groups or two or more non-adjacent CH ₂ groups are each independently of each other, in a form in which oxygen atoms are not directly bonded to each other, -O-, -S-, -NH-, -N(CH ₃ )-, -CO-, -COO-, -OCO-, -OCOO-, -SCO-, -COS- or -C≡C- may be substituted,

Or R ^3a and R ^3b are the general formula (3-a)

(In the formula, P ^3a represents a polymerizable functional group, and Sp ^3a represents the same meaning as Sp ¹ .)

It is preferable that P ^3a represents a substituent selected from polymerizable groups represented by the following formulas (P-1) to (P-20).

Among these polymerizable functional groups, formula (P-1) or formula (P-2), (P-7), (P-12), (P-13) is preferable from the viewpoint of enhancing polymerization and storage stability. , Formulas (P-1), (P-7), and (P-12) are more preferable.

Specific examples of the polymerizable chiral compound include compounds of compounds (3-5) to (3-25), but are not limited to the following compounds.

In the formula, m, n, k, and l each independently represent an integer of 1 to 18, and R ₁ to R ₄ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a carboxyl group And a cyano group. When these groups are a C1-C6 alkyl group or a C1-C6 alkoxy group, all may be unsubstituted or may be substituted by 1 or 2 or more halogen atoms.

(Polymerizable discotic compound)

In the polymerizable liquid crystal composition of the present invention, a polymerizable discotic liquid crystal compound exhibiting liquid crystal properties may be used as the polymerizable liquid crystal compound. Further, the polymerizable liquid crystal composition of the present invention may contain a non-liquid crystal polymerizable discotic compound.

As the polymerizable discotic compound used in the present invention, it is preferable to have one or more polymerizable functional groups. As such a compound, for example, Japanese Patent Laid-Open No. Hei 7-281028, Japanese Patent Laid-Open No. Hei 7-287120, Japanese Patent Laid-Open No. Hei 7-333431, and Japanese Patent Laid-Open No. Hei 8-27284 Polymerizable compounds as described in the publication are mentioned.

As the polymerizable discotic liquid crystal compound exhibiting liquid crystallinity, which is the polymerizable liquid crystal compound, a compound represented by the following general formula (III) can be mentioned.

(In the formula, R ⁷ each independently represents a substituent represented by the general formula (III-a).

(In the formula, R ⁹ and R ¹⁰ each independently represent a hydrogen atom, a halogen atom or a methyl group, and R ⁸ represents an alkoxy group having 1 to 20 carbon atoms, and the hydrogen atom in the alkoxy group is the general formula (III-b ), may be substituted by a substituent represented by the general formula (III-c), or the general formula (III-d), and at least one of R ⁸ present in the general formula (III) is a general formula (III-b ), a substituent represented by the general formula (III-c), or the general formula (III-d).)

(In the formula, R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ , R ⁸⁵ , R ⁸⁶ , R ⁸⁷ , R ⁸⁸ and R ⁸⁹ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms, , n represents 0 or 1.))

At least one of R ⁸ present in the general formula (III) is substituted by a substituent represented by the general formula (III-b), the general formula (III-c), or the general formula (III-d), All R ⁸ present in the general formula (III) are each independently substituted by a substituent represented by the general formula (III-b), the general formula (III-c), or the general formula (III-d). It is desirable.

Further, the substituent represented by the general formula (III-a) is specifically preferably a substituent represented by the general formula (III-e).

(In the formula, n2 represents the integer of 1-18.)

As the compound represented by the general formula (III), a compound represented by the following general formula (III-1) or (III-2) can be mentioned as a suitable compound.

(In General Formula (III-1) and General Formula (III-2), n represents the integer of 1-18.)

As the polymerizable liquid crystal compound, one or two or more polymerizable discotic liquid crystal compounds exhibiting liquid crystal properties can be used.

As the polymerizable liquid crystal compound, only a polymerizable discotic liquid crystal compound may be used, or a polymerizable rod-shaped liquid crystal compound and a polymerizable discotic liquid crystal compound may be used in combination.

When a polymerizable rod-shaped liquid crystal compound and a polymerizable discotic liquid crystal compound are used in combination as the polymerizable liquid crystal compound, the total content of the polymerizable discotic liquid crystal compound exhibiting liquid crystal is the total amount of the polymerizable liquid crystal compound used in the polymerizable liquid crystal composition Among them, it is preferable to contain from 5 to 95% by mass, more preferably from 10 to 90% by mass, and particularly preferably from 20 to 80% by mass.

As an example of the general formula of other polymerizable discotic compounds, general formulas (4-1) to (4-3) can be exemplified, but it is not limited to the following general formula.

In the formula, Sp ⁴ represents an alkylene group having 0 to 18 carbon atoms, and the alkylene group is substituted with at least one halogen atom, a CN group, or an alkyl group having 1 to 8 carbon atoms having a polymerizable functional group. And, one CH ₂ group present in this group or two or more CH ₂ groups not adjacent to each other independently of each other, in a form in which oxygen atoms are not directly bonded to each other, -O-, -S-, -NH-, -N(CH ₃ )-, -CO-, -COO-, -OCO-, -OCOO-, -SCO-, -COS- or -C≡C- may be substituted,

Z ^4a is -CO-, -CH ₂ CH ₂ -, -CH ₂ O-, -CH=CH-, -CH=CHCOO-, -CH ₂ CH ₂ COO-, -CH ₂ CH ₂ OCO-,- COCH ₂ CH ₂ -, represents an alkyl group or a single bond which may have a halogen atom having 2 to 10 carbon atoms,

R ⁴ represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group having 1 to 18 carbon atoms, and the alkyl group may be substituted with one or more halogen atoms or CN, and one CH ₂ present in the group A group or two or more CH ₂ groups not adjacent to each other independently of each other, in a form in which oxygen atoms are not directly bonded to each other, -O-, -S-, -NH-, -N(CH ₃ )-, -CO- , -COO-, -OCO-, -OCOO-, -SCO-, -COS- or -C≡C- may be substituted,

Or R ⁴ is the general formula (4-a)

(In the formula, P ^4a represents a polymerizable functional group, and Sp ^3a represents the same meaning as Sp ¹ .)

It is preferable that P ^4a represents a substituent selected from polymerizable groups represented by the following formulas (P-1) to (P-20).

Among these polymerizable functional groups, formula (P-1) or formula (P-2), (P-7), (P-12), (P-13) is preferable from the viewpoint of enhancing polymerization and storage stability. , Formulas (P-1), (P-7), and (P-12) are more preferable.

Specific examples of the polymerizable discotic compound include compounds of compounds (4-4) to (4-6), but are not limited to the following compounds.

In General Formula (4-4)-General Formula (4-6), n represents the integer of 1-18.

(Organic solvent)

You may add an organic solvent to the polymerizable liquid crystal composition in this invention. The organic solvent to be used is not particularly limited, but an organic solvent in which the polymerizable liquid crystal compound exhibits good solubility is preferable, and it is preferably an organic solvent that can be dried at a temperature of 100°C or less. Examples of such solvents include aromatic hydrocarbons such as toluene, xylene, cumene and mesitylene, ester solvents such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexa Ketone solvents such as rice paddy and cyclopentanone, ether solvents such as tetrahydrofuran, 1,2-dimethoxyethane, and anisole, N,N-dimethylformamide, and N-methyl-2-pyrrolidone Amide solvents, propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, γ-butyrolactone, chlorobenzene, and the like. These may be used alone or in combination of two or more, but it is preferable from the viewpoint of solution stability to use any one or more of a ketone-based solvent, an ether-based solvent, an ester-based solvent, and an aromatic hydrocarbon-based solvent.

The composition used in the present invention can be applied to a substrate as long as it is a solution of an organic solvent, and the ratio of the organic solvent used in the polymerizable liquid crystal composition is not particularly limited as long as the applied state is not significantly impaired. It is preferable that the total amount of the organic solvent contained in a liquid crystal composition is 10 to 95 mass %, it is more preferable that it is 12 to 90 mass %, and it is especially preferable that it is 15 to 85 mass %.

When dissolving the polymerizable liquid crystal composition in an organic solvent, in order to dissolve it uniformly, it is preferable to heat and stir. The heating temperature at the time of heating and stirring may be appropriately adjusted in consideration of the solubility of the composition to be used in the organic solvent, but from the viewpoint of productivity, 15°C to 110°C is preferable, 15°C to 105°C is more preferable, and 15°C to 100°C is more preferable, and it is particularly preferable to set it to 20°C to 90°C.

Moreover, when adding a solvent, it is preferable to stir and mix with a dispersion stirrer. Specifically, as the dispersion agitator, a disperser, a propeller, a disperser having stirring blades such as a turbine blade, a paint shaker, a planetary stirring device, a shaker, a shaker, or a rotary evaporator can be used. Other than that, an ultrasonic irradiation apparatus can be used.

The number of rotations for stirring when adding the solvent is preferably appropriately adjusted according to the stirring device to be used.In order to obtain a uniform polymerizable liquid crystal composition solution, the number of stirring rotations is preferably 10 rpm to 1000 rpm, and 50 rpm to 800 rpm. It is more preferable to set it, and it is especially preferable to set it as 150 rpm-600 rpm.

(Polymerization inhibitor)

It is preferable to add a polymerization inhibitor to the polymerizable liquid crystal composition in the present invention. As a polymerization inhibitor, a phenol compound, a quinone compound, an amine compound, a thioether compound, a nitroso compound, etc. are mentioned.

As a phenolic compound, p-methoxyphenol, cresol, t-butylcatechol, 3,5-di-t-butyl-4-hydroxytoluene, 2,2'-methylenebis(4-methyl-6-t -Butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), 4-methoxy- 1-naphthol, 4,4'-dialkoxy-2,2'-bi-1-naphthol, etc. are mentioned.

Examples of the quinone-based compound include hydroquinone, methylhydroquinone (MEHQ), tert-butylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, tert-butyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2- Hydroxy-1,4-naphthoquinone, 1,4-naphthoquinone, 2,3-dichloro-1,4-naphthoquinone, anthraquinone, diphenoquinone, etc. are mentioned.

As an amine compound, p-phenylenediamine, 4-aminodiphenylamine, N,N'-diphenyl-p-phenylenediamine, Ni-propyl-N'-phenyl-p-phenylenediamine, N-( 1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N,N'-di-2-naphthyl-p-phenylenediamine, diphenylamine, N-phenyl-β-naphthylamine , 4,4'-dicumyl-diphenylamine, 4,4'-dioctyl-diphenylamine, and the like.

As a thioether compound, phenothiazine, distearyl thiodipropionate, etc. are mentioned.

As a nitroso compound, N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, N-nitrosodinaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso -β-naphthol, etc., N,N-dimethylp-nitrosoaniline, p-nitrosodiphenylamine, p-nitrosodiphenylamine, p-nitrosone-N,N-diethylamine, N-nitrosoethanolamine , N-nitrosodi-n-butylamine, N-nitroso-Nn-butyl-4-butanolamine, N-nitroso-diisopropanolamine, N-nitroso-N-ethyl-4-butanolamine, 5- Nitroso-8-hydroxyquinoline, N-nitrosomorpholine, N-nitroso-N-phenylhydroxylamine ammonium salt, nitrosobenzene, 2,4,6-tri-tert-butylnitrobenzene, N- Nitroso-N-methyl-p-toluenesulfonamide, N-nitroso-N-ethyl urethane, N-nitroso-Nn-propyl urethane, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol , 1-nitroso-2-naphthol-3,6-sodium sulfonate, 2-nitroso-1-naphthol-4-sodium sulfonate, 2-nitroso-5-methylaminophenol hydrochloride, 2-nitroso-5- Methylaminophenol hydrochloride, etc. are mentioned.

It is preferable that it is 0.01-1.0 mass% with respect to the polymerizable liquid crystal composition, and, as for the addition amount of a polymerization inhibitor, it is more preferable that it is 0.05-0.5 mass %.

(Antioxidant)

In order to increase the stability of the polymerizable liquid crystal composition in the present invention, it is preferable to add an antioxidant or the like. Examples of such compounds include hydroquinone derivatives, nitrosoamine-based polymerization inhibitors, hindered phenol-based antioxidants, and the like. More specifically, tert-butylhydroquinone, methylhydroquinone, Wako Pure Chemical Industries Ltd. ``Q-1300 '', ``Q-1301'', BASF's ``IRGANOX 1010'', ``IRGANOX 1035'', ``IRGANOX 1076'', ``IRGANOX 1098'', ``IRGANOX 1135'', ``IRGANOX 1330'', ``IRGANOX 1425'', ``IRGANOX 1520'', "IRGANOX 1726", "IRGANOX 245", "IRGANOX 259", "IRGANOX 3114", "IRGANOX 3790", "IRGANOX 5057", "IRGANOX 565", and the like.

It is preferable that it is 0.01 to 2.0 mass% with respect to the polymerizable liquid crystal composition, and, as for the addition amount of an antioxidant, it is more preferable that it is 0.05 to 1.0 mass %.

(Photopolymerization initiator)

It is preferable that the polymerizable liquid crystal composition in this invention contains a photoinitiator. It is preferable to contain at least one or more types of photoinitiators. Specifically, "Irgacure 651", "Irgacure 184", "Irgacure 907", "Irgacure 127", "Irgacure 369" and "Irgacure 379" manufactured by BASF Japan Co., Ltd. , ``Irgacure 819'', ``Irgacure 2959'', ``Irgacure 1800'', ``Irgacure 250'', ``Irgacure 754'', ``Irgacure 784'', ``Irgacure OXE01'', "Irgacure OXE02", "Lucyrin TPO", "Darocure 1173", "Darocure MBF" or LAMBSON's "Esacure 1001M", "Esacure KIP150", "SpeedCure BEM", "SpeedCure." BMS", "SpeedCure MBP", "SpeedCure PBZ", "SpeedCure ITX", "SpeedCure DETX", "SpeedCure EBD", "SpeedCure MBB", "SpeedCure BP" or manufactured by Nihon Kayaku Co., Ltd. ``Kayacure DMBI'', ``TAZ-A'' manufactured by Nippon Sibel Hegner Co., Ltd. (currently DKSH Japan Co., Ltd.), ``Adeka Optomer SP-152'', ``Adeka Optomer SP-170'' manufactured by ADEKA Inc., "Adeka Optomer N-1414", "Adeka Optomer N-1606", "Adeka Optomer N-1717", and "Adeka Optomer N-1919".

The amount of the photoinitiator used is preferably 0.1 to 10% by mass, particularly preferably 0.5 to 7% by mass, based on the polymerizable liquid crystal composition. These may be used alone, or two or more types may be mixed and used, and a sensitizer or the like may be added.

(Thermal polymerization initiator)

In the polymerizable liquid crystal composition in the present invention, a thermal polymerization initiator may be used in combination with a photoinitiator. Specifically, "V-40" and "VF-096" manufactured by Wako Junyaku Industries, Ltd., "Perhexyl D" and "Perhexyl I" manufactured by Nippon Yushi Co., Ltd.

The amount of the thermal polymerization initiator to be used is preferably 0.1 to 10% by mass, particularly preferably 0.5 to 5% by mass, based on the polymerizable liquid crystal composition. These may be used alone or in combination of two or more.

(Surfactants)

The polymerizable liquid crystal composition in the present invention may further contain at least one or more surfactants within a range that does not impair the effects of the present invention in order to reduce the film thickness unevenness in the case of an optically anisotropic body. As surfactants that may be contained, alkyl carboxylates, alkyl phosphates, alkyl sulfonates, fluoroalkyl carboxylates, fluoroalkyl phosphates, fluoroalkyl sulfonates, polyoxyethylene derivatives, fluoroalkylethylene oxide derivatives , Polyethylene glycol derivatives, alkyl ammonium salts, fluoroalkyl ammonium salts, and the like, and a fluorinated surfactant is particularly preferable.

Specifically, "Megapack F-251", "Megapack F-444", "Megapack F-477", "Megapack F-510", "Megapack F-552", "Megapack F-553" '', ``Megapack F-554'', ``Megapack F-555'', ``Megapack F-556'', ``Megapack F-557'', ``Megapack F-558'', ``Megapack F-559'', ``Megapack F-560'', ``Megapack F-561'', ``Megapack F-562'', ``Megapack F-563'', ``Megapack F-565'', ``Megapack F-567'', ``Mega Pack F-568'', ``Megapack F-569'', ``Megapack F-570'', ``Megapack F-571'', ``Megapack R-40'', ``Megapack R-41'', ``Megapack R -43'', ``Megapack R-94'', ``Megapack RS-72-K'', ``Megapack RS-75'', ``Megapack RS-76-E'', ``Megapack RS-90'' (or higher, DIC Corporation),

``Ptergent 100'', ``Ptergent 100C'', ``Ptergent 110'', ``Ptergent 150'', ``Ptergent 150CH'', ``Ptergent A'', ``Ptergent 100A-K'', ``Ptergent 501'', ``Ptergent 300'', ``Ptergent 310'', ``Ptergent 320'', ``Ptergent 400SW'', ``FTX-400P'', ``Ptergent 251'', ``Ptergent 215M'', ``Ptergent 212MH'', ``Peter Gent 250", "Ftergent 222F", "Ftergent 212D", "FTX-218", "FTX-209F", "FTX-213F", "FTX-233F", "Ftergent 245F", "FTX-208G 」, 「FTX-240G」, 「FTX-206D」, 「FTX-220D」, 「FTX-230D」, 「FTX-240D」, 「FTX-207S」, 「FTX-211S」, 「FTX-220S」, 「FTX-230S」, 「FTX-750FM」, 「FTX-730FM」, 「FTX-730FL」, 「FTX-710FS」, 「FTX-710FM」, 「FTX-710FL」, 「FTX-750LL」, 「FTX -730LS", "FTX-730LM", "FTX-730LL", "FTX-710LL" (above, manufactured by Neos Co., Ltd.),

「BYK-300」, 「BYK-302」, 「BYK-306」, 「BYK-307」, 「BYK-310」, 「BYK-315」, 「BYK-320」, 「BYK-322」, 「BYK -323", "BYK-325", "BYK-330", "BYK-331", "BYK-333", "BYK-337", "BYK-340", "BYK-344", "BYK-3440" '', ``BYK-370'', ``BYK-375'', ``BYK-377'', ``BYK-350'', ``BYK-352'', ``BYK-354'', ``BYK-355'', ``BYK-356'', 「BYK-358N」, 「BYK-361N」, 「BYK-357」, 「BYK-390」, 「BYK-392」, 「BYK-UV3500」, 「BYK-UV3510」, 「BYK-UV3570」, 「BYK -Silclean3700'' (above, manufactured by Big Chemie Japan),

「TEGO Rad2100」, 「TEGO Rad2200N」, 「TEGO Rad2250」, 「TEGO Rad2300」, 「TEGO Rad2500」, 「TEGO Rad2600」, 「TEGO Rad2700」(above, manufactured by Tego)

Examples such as "N215", "N535", "N605K", and "N935" (above, manufactured by Solvay Solexis) may be mentioned.

It is preferable that it is 0.01-2 mass% with respect to the polymerizable composition, and, as for the addition amount of surfactant, it is more preferable that it is 0.05-0.5 mass %.

In addition, by using the surfactant, when the polymerizable liquid crystal composition of the present invention is an optically anisotropic body, the tilt angle of the air interface can be effectively reduced.

The polymerizable liquid crystal composition in the present invention is a repeating unit represented by the following general formula (7) having an effect of effectively reducing the tilt angle of the air interface in the case of an optically anisotropic body within a range that does not impair the effect of the present invention. The compounds having a weight average molecular weight of 100 or more are mentioned.

In the formula, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and even if the hydrogen atom in the hydrocarbon group is substituted with one or more halogen atoms do.

As a suitable compound represented by general formula (7), polyethylene, polypropylene, polyisobutylene, paraffin, liquid paraffin, chlorinated polypropylene, chlorinated paraffin, chlorinated liquid paraffin, etc. are mentioned, for example.

It is preferable that it is 0.01-1 mass% with respect to a polymerizable liquid crystal composition, and, as for the addition amount of the compound represented by general formula (7), it is more preferable that it is 0.05-0.5 mass %.

(Other additives)

In addition, in order to adjust the physical properties, depending on the purpose, additives such as a polymerizable compound having no liquid crystal property, a thixotropic agent, an ultraviolet absorber, an infrared absorber, an antioxidant, and a surface treatment agent may be added to an extent that does not significantly reduce the alignment ability of the liquid crystal. have.

(Manufacturing method of optically anisotropic body)

(Optical anisotropic)

The optically anisotropic body produced by using the polymerizable liquid crystal composition of the present invention is obtained by sequentially laminating a base material, an alignment film, and a polymer of the polymerizable liquid crystal composition as necessary.

(materials)

The substrate used for the optically anisotropic body of the present invention is a substrate commonly used for liquid crystal devices, displays, optical components and optical films, and has heat resistance that can withstand heating during drying after application of the polymerizable liquid crystal composition of the present invention. As long as it is a material to have, there is no restriction|limiting in particular. Examples of such substrates include organic materials such as glass substrates, metal substrates, ceramics substrates and plastic substrates. In particular, when the substrate is an organic material, cellulose derivative, polyolefin, polyester, polycarbonate, polyacrylate (acrylic resin), polyarylate, polyethersulfone, polyimide, polyphenylene sulfide, polyphenylene ether, nylon or Polystyrene, etc. are mentioned. Among them, plastic substrates such as polyester, polystyrene, polyacrylate, polyolefin, cellulose derivative, polyarylate, and polycarbonate are preferable, and substrates such as polyacrylate, polyolefin, and cellulose derivative are more preferable, and the polyolefin is COP ( It is particularly preferable to use a cycloolefin polymer), to use TAC (triacetyl cellulose) as the cellulose derivative, and to use PMMA (polymethyl methacrylate) as the polyacrylate. The shape of the base material may have a curved surface in addition to a flat plate. These substrates may have an electrode layer, an antireflection function, and a reflection function, if necessary.

In order to improve the coatability and adhesion of the polymerizable liquid crystal composition of the present invention, these substrates may be subjected to surface treatment. Examples of the surface treatment include ozone treatment, plasma treatment, corona treatment, and silane coupling treatment. In addition, in order to adjust the transmittance or reflectance of light, an organic thin film, an inorganic oxide thin film, or a metal thin film is installed on the surface of the substrate by a method such as vapor deposition, or to add optical added value, the substrate is a pickup lens or a rod lens. , An optical disk, a retardation film, a light diffusion film, a color filter, or the like. Among them, a pickup lens, a retardation film, a light diffusion film, and a color filter whose added value is higher are preferable.

(Orientation treatment)

In addition, alignment treatment may be usually performed or an alignment film may be provided on the substrate so that the polymerizable liquid crystal composition is aligned when the polymerizable liquid crystal composition of the present invention is applied and dried. Examples of the orientation treatment include stretching treatment, rubbing treatment, polarized ultraviolet visible light irradiation treatment, and ion beam treatment. In the case of using an alignment film, a well-known and commonly used alignment film is used. As such an alignment film, polyimide, polysiloxane, polyamide, polyvinyl alcohol, polycarbonate, polystyrene, polyphenylene ether, polyarylate, polyethylene terephthalate, polyethersulfone, epoxy resin, epoxy acrylate resin, acrylic resin, coumarin Compounds, such as a compound, a chalcone compound, a cinnamate compound, a fulgide compound, an anthraquinone compound, an azo compound, and an arylethene compound, are mentioned. In the compound subjected to orientation treatment by rubbing, it is preferable that the crystallization of the material is accelerated by giving a heating step after orientation treatment or orientation treatment. It is preferable to use a photo-alignment material among the compounds which perform alignment treatment other than rubbing.

In the present invention, the substrate and the film subjected to alignment treatment using an alignment film or the like may be collectively referred to as a substrate.

(apply)

As a coating method for obtaining the optically anisotropic body of the present invention, the applicator method, bar coating method, spin coating method, roll coating method, direct gravure coating method, reverse gravure coating method, flexo coating method, inkjet method, die coating method , A cap coating method, a dip coating method, a slit coating method, or other known and common methods can be performed. After applying the polymerizable liquid crystal composition to a substrate, it is dried as necessary.

(Polymerization process)

Regarding the polymerization operation of the polymerizable liquid crystal composition of the present invention, in a state in which the liquid crystal compound in the polymerizable liquid crystal composition is horizontally oriented, vertically oriented, or hybrid oriented, or cholesteric oriented (planar alignment) with respect to the substrate, generally ultraviolet rays, etc. It is performed by light irradiation or heating. When polymerization is carried out by light irradiation, it is specifically preferable to irradiate ultraviolet light of 390 nm or less, and most preferably, irradiation of light with a wavelength of 250 to 370 nm. However, when the polymerizable liquid crystal composition causes decomposition or the like by ultraviolet light of 390 nm or less, it may be preferable to perform polymerization treatment with ultraviolet light of 390 nm or more. It is preferable that this light is diffused light and is light which is not polarized.

(Polymerization method)

As a method of polymerizing the polymerizable liquid crystal composition of the present invention, there may be mentioned a method of irradiating an active energy ray or a thermal polymerization method, but it does not require heating, and since the reaction proceeds at room temperature, irradiating an active energy ray The method is preferable, and among them, the method of irradiating light such as ultraviolet rays is preferable from the viewpoint of easy operation.

The temperature at the time of irradiation is preferably a temperature at which the polymerizable liquid crystal composition of the present invention can maintain a liquid crystal phase, and to avoid organic thermal polymerization of the polymerizable liquid crystal composition, and is preferably 40°C or less as much as possible. In addition, a liquid crystal composition usually exhibits a liquid crystal phase within an NI transition temperature range from a C (solid phase) -N (nematic) transition temperature (hereinafter, abbreviated as CN transition temperature) in a temperature raising process. On the other hand, in the temperature-falling process, since the thermodynamically non-equilibrium state is taken, there is a case where the liquid crystal state is maintained without solidifying even below the CN transition temperature. This state is called a supercooled state. In the present invention, the liquid crystal composition in a supercooled state is also included in a state in which the liquid crystal phase is maintained. Specifically, it is preferable to irradiate ultraviolet light of 390 nm or less, and it is most preferable to irradiate light with a wavelength of 250 to 370 nm. However, when the polymerizable composition causes decomposition or the like by ultraviolet light of 390 nm or less, it may be preferable to perform polymerization treatment with ultraviolet light of 390 nm or more. It is preferable that this light is diffused light and is light which is not polarized. The ultraviolet ray irradiation intensity is, the range of ^{0.05kW / m 2 ~ 10kW / m} 2 is preferred. In particular, the range of 0.2 kW/m ² to 2 kW/m ² is preferable. When the ultraviolet intensity is less than 0.05 kW/m ² , it takes a long time to complete polymerization. On the other hand, at an intensity exceeding ² kW/m ² , the liquid crystal molecules in the polymerizable liquid crystal composition tend to be photo-decomposed, or a large amount of polymerization heat is generated, the temperature during polymerization increases, and the order parameter of the polymerizable liquid crystal changes, and polymerization. There is a possibility that an abnormality may occur in the retardation of the later film.

After polymerization of only a specific part by UV irradiation using a mask, the orientation state of the unpolymerized part is changed by applying an electric field, magnetic field, or temperature, and then the unpolymerized part is polymerized. An optically anisotropic body having a plurality of regions can also be obtained.

In addition, when using a mask to polymerize only a specific part by UV irradiation, an electric field, magnetic field, or temperature is applied to the polymerizable liquid crystal composition in an unpolymerized state to regulate orientation, and light from the mask while maintaining the state Also by irradiating and polymerizing, an optically anisotropic body having a plurality of regions having different orientation directions can be obtained.

The optically anisotropic body obtained by polymerizing the polymerizable liquid crystal composition of the present invention may be peeled off from the substrate and used as an optically anisotropic body alone, or may be used as an optically anisotropic body as it is without being peeled off from the substrate. In particular, since it is difficult to contaminate other members, it is useful when used as a laminated substrate or bonded to another substrate.

(Firing treatment of polymer having pyrolytic group)

The optically anisotropic body produced through a coating step and a polymerization step using the polymerizable liquid crystal composition of the present invention requires a step of heating (baking treatment) in an environment of 180 to 300°C. When a polymer having a pyrolytic group containing a fluorine atom and/or a silicon atom is heated in a state segregated on the surface of the optical anisotropic body, a portion of the pyrolytic group containing a fluorine atom and/or a silicon atom is transferred to the optical anisotropic body. It detaches from the contained polymer, and the water repellency and oil repellency of a film formation surface fall. As a result of such a phenomenon, it becomes easy to laminate another film on the film formation made of the polymerizable liquid crystal composition, and a laminate can be easily obtained. In order to desorb the part of the pyrolyzing group bonded to the polymer having a pyrolytic group, it is preferable to perform a baking treatment at 180 to 300°C for 30 minutes, and more preferably at 200 to 250°C for 30 minutes.

(Phase difference)

The retardation film of the present invention is prepared in the same manner as the optically anisotropic body of the present invention. The obtained retardation film can be used as a homogeneous liquid crystal film or the like. It is formed in a form suitable for use in accordance with the use of a liquid crystal device, a display, an optical element, an optical component, a colorant, a security marking, a member for laser light emission, an optical film, and a compensation film.

As such a retardation film, for example, a positive A plate in which a rod-like liquid crystal compound is substantially horizontally oriented with respect to the substrate, a negative A plate in which a disk-shaped liquid crystal compound is uniaxially oriented vertically with respect to the substrate, and a rod-shaped substrate. Positive C plate in which the liquid crystal compound is substantially vertically aligned, the rod-shaped liquid crystal compound is cholesteric aligned with respect to the substrate, or the negative C plate in which the disk-shaped liquid crystal compound is horizontally uniaxially aligned, the biaxial plate, and the substrate On the other hand, an alignment mode of a positive O plate in which a rod-like liquid crystal compound is hybridly aligned and a negative O plate in which a disk-like liquid crystal compound is hybridly aligned with respect to the base material can be applied. In the case of using for a liquid crystal display device, various alignment modes can be applied without particular limitation as long as the viewing angle dependence is improved.

For example, the orientation mode of positive A plate, negative A plate, positive C plate, negative C plate, biaxial plate, positive O plate, and negative O plate can be applied. Among them, it is preferable to use a positive A plate and a negative C plate. In addition, it is more preferable to laminate the positive A plate and the negative C plate.

Here, the positive A plate means an optically anisotropic body obtained by homogeneous alignment of a polymerizable liquid crystal composition. In addition, the negative C plate means an optically anisotropic body in which a polymerizable liquid crystal composition was cholesterically aligned.

In a liquid crystal cell using a retardation film, it is preferable to use a positive A plate as the first retardation layer in order to widen the viewing angle by compensating for the viewing angle dependence of polarization axis orthogonality. Here, in the positive A plate, when the refractive index in the in-plane slow axis direction of the film is nx, the refractive index in the in-plane fast axis direction of the film is ny, and the refractive index in the thickness direction of the film is nz. And "nx>ny=nz". As the positive A plate, it is preferable that the in-plane retardation value at a wavelength of 550 nm is in the range of 30 to 500 nm. In addition, the retardation value in the thickness direction is not particularly limited. The Nz coefficient is preferably in the range of 0.9 to 1.1.

Further, in order to eliminate the birefringence of the liquid crystal molecules themselves, it is preferable to use a so-called negative C plate having negative refractive index anisotropy as the second retardation layer. In addition, a negative C plate may be laminated on the positive A plate.

Here, in the negative C plate, when the refractive index in the in-plane slow axis direction of the retardation layer is nx, the refractive index in the in-plane fast axis direction of the retardation layer is ny, and the refractive index in the thickness direction of the retardation layer is nz, ``nx=ny>nz It is the phase difference layer which becomes the relationship of ". The thickness direction retardation value of the negative C plate is preferably in the range of 20 to 400 nm.

In addition, the refractive index anisotropy in the thickness direction is expressed by the thickness direction retardation value Rth defined by the following formula (2). The thickness direction retardation value (Rth) is the in-plane retardation value (R ₀ ), the retardation value measured by inclining by 50° with the slow axis as the inclined axis (R ₅₀ ), the thickness of the film (d), and the average refractive index of the film (n ₀ ), nx, ny, and nz can be obtained by numerical calculation from equations (1) and equations (4) to (7), and can be calculated by substituting them into equation (2). In addition, the Nz coefficient can be calculated from Formula (3). Hereinafter, it is the same in other description of this specification.

R ₀ =(nx-ny)×d (1)

Rth=[(nx+ny)/2-nz]×d (2)

Nz coefficient=(nx-nz)/(nx-ny) (3)

R ₅₀ =(nx-ny')×d/cos(φ) (4)

(nx+ny+nz)/3=n0 (5)

here,

φ=sin ^-1 [sin(50°)/n ₀ ] (6)

ny'=ny×nz/[ny ² ×sin ² (φ)+nz ² ×cos ² (φ)] ^1/2 (7)

In many commercially available phase difference measuring devices, the numerical calculation shown here is automatically performed in the device, and the in-plane retardation value R ₀ , the thickness direction retardation value Rth, and the like are displayed automatically. As such a measuring apparatus, RETS-100 (made by Otsuka Chemical Co., Ltd.) is mentioned, for example.

(Phase difference patterning film)

Similar to the optically anisotropic body of the present invention, the phase difference patterning film of the present invention is obtained by sequentially laminating a base material, an alignment film, and a polymer of a polymerizable liquid crystal composition, but is patterned so as to partially obtain a different phase difference in the polymerization step. Patterning may be in different directions such as linear patterning, lattice patterning, circular patterning, polygonal patterning, or the like. It is applied depending on applications such as a liquid crystal device, a display, an optical element, an optical component, a colorant, a security marking, a member for laser light emission, an optical film, and a compensation film.

As a method of obtaining a partially different phase difference, an alignment film is provided on a substrate, and the polymerizable liquid crystal composition of the present invention is applied and dried during alignment treatment so that the polymerizable liquid crystal composition is patterned and aligned. Examples of such orientation treatment include fine rubbing treatment, polarized ultraviolet visible light irradiation treatment through a photomask, and fine shape processing treatment. As for the alignment film, a well-known and common one is used. As such an alignment film, polyimide, polysiloxane, polyamide, polyvinyl alcohol, polycarbonate, polystyrene, polyphenylene ether, polyarylate, polyethylene terephthalate, polyethersulfone, epoxy resin, epoxy acrylate resin, acrylic resin, coumarin Compounds, such as a compound, a chalcone compound, a cinnamate compound, a fulgide compound, an anthraquinone compound, an azo compound, and an arylethene compound, are mentioned. In the compound subjected to orientation treatment by fine rubbing, it is preferable that the crystallization of the material is accelerated by putting in a heating step after orientation treatment or orientation treatment. It is preferable to use a photo-alignment material among the compounds which perform alignment treatment other than rubbing.

(Brightness Enhancement Film)

The brightness improving film of the present invention is a brightness enhancing film having a λ/4 plate and a reflective polarizer, and the reflective polarizer includes a first light reflection layer, a second light reflection layer, and a third light reflection layer in this order from the λ/4 plate side. And, the first light reflection layer, the second light reflection layer, and the third light reflection layer are all light reflection layers formed by fixing the cholesteric liquid crystal phase, and any one of the first light reflection layer, the second light reflection layer, and the third light reflection layer is The reflection center wavelength is 380 to 499 nm and is a blue light reflecting layer having a reflectance peak with a half width of 100 nm or less, one of which is a green light reflecting layer having a reflection center wavelength of 500 to 599 nm and a reflectance peak of 200 nm or less, and either is a reflection center wavelength of 600 It is a red light reflecting layer having a reflectance peak of ~750 nm and a half width of 150 nm or less, and the sign of Rth 550 of the first light reflecting layer and Rth 550 of the second light reflecting layer are opposite. With such a configuration, when the luminance improving film of the present invention is attached to a liquid crystal display device, the luminance is high and the oblique color tone change can be suppressed.

(Cholesteric reflective film)

The cholesteric reflective film of the present invention is a cholesteric reflective film composed of a cured product of a planar-oriented polymerizable liquid crystal composition, and the polymerizable liquid crystal composition has only one polymerizable functional group, and has a tolan skeleton. Contains one or two or more compounds, contains one or two or more liquid crystal compounds having two or more polymerizable functional groups, contains one or two or more chiral compounds having one or more polymerizable functional groups, It is characterized by containing one or two or more polymerization initiators.

(Anti-reflective film)

The antireflection film of the present invention is a circularly polarizing plate in which a retardation plate is further laminated on a polarizing plate. When the linearly polarized light is changed to circularly polarized light, the circularly polarized light is linearly polarized, or the polarization direction of linearly polarized light is changed, a retardation plate or the like is used. In particular, as a retardation plate that converts linearly polarized light into circularly polarized light or converts circularly polarized light into linearly polarized light, a so-called quarter wave plate (also referred to as a λ/4 plate) is used. The 1/2 wave plate (also referred to as λ/2 plate) is usually used when changing the polarization direction of linearly polarized light.

The circularly polarizing plate is effectively used, for example, when adjusting the color tone of an image in a reflective liquid crystal display device in which an image is displayed in color, and has a function of preventing reflection. Examples of the retardation plate described above include an alignment film of a liquid crystal polymer and a film supporting the alignment layer of a liquid crystal polymer. The retardation plate may have an appropriate retardation according to the purpose of use, such as coloration by birefringence of various wavelength plates or liquid crystal layers or for compensation of vision, etc., and two or more retardation plates are laminated to It may be one in which optical properties such as phase difference are controlled.

(View angle compensation film)

The viewing angle compensation film of the present invention is a film for widening the viewing angle so that an image can be seen relatively clearly even when the screen of the liquid crystal display device is viewed from a slightly inclined direction rather than perpendicular to the screen. As such a viewing angle compensation film, for example, an alignment film such as a retardation film or a liquid crystal polymer, or an alignment layer such as a liquid crystal polymer is supported on a transparent substrate. A typical retardation plate is a polymer film having birefringence uniaxially stretched in the plane direction or a liquid crystal polymer film uniaxially oriented, whereas a retardation plate used as a viewing angle compensation film has birefringence biaxially stretched in the plane direction. A polymer film, a polymer having a birefringence in which the refractive index in the thickness direction is controlled uniaxially stretched in the plane direction and also stretched in the thickness direction, or a two-way stretched film such as an oblique oriented film is used. Examples of the obliquely oriented film include those in which a liquid crystal polymer is obliquely oriented or a polymer film superimposed with an active energy ray such as ultraviolet rays in a state in which a polymerizable liquid crystal is obliquely oriented. A suitable one is used for the purpose of preventing coloring or the like due to a change in the viewing angle based on the phase difference caused by the liquid crystal cell, or expanding the viewing angle of both visually.

In addition, since both viewers achieve a wide viewing angle, an optical compensation retardation plate in which an optically anisotropic layer made of an inclined alignment film of a liquid crystal polymer is supported by an optical film is preferably used.

(Reflective polarizer)

The reflective polarizing plate of the present invention is a reflective polarizing plate in which a cholesteric reflective film, an adhesive layer, and a linearly polarizing film are sequentially stacked, and the cholesteric reflective film uses the cholesteric reflective film of the present invention. Further, one or more retardation films may be provided in the reflective polarizing plate, and a retardation film having a different phase difference may be used for the retardation film. Lamination of a retardation film is obtained by bonding an adhesive or an adhesive film to the obtained retardation film, and then bonding the cholesteric reflective film and the retardation film of the present invention through an adhesive or an adhesive film. In the case of using an adhesive or an adhesive film, as the adhesive and an adhesive film, a conventionally known adhesive for optical film applications is used.

Example

Hereinafter, the present invention will be described with reference to Synthesis Examples, Examples, and Comparative Examples, but of course the present invention is not limited thereto. In addition, unless otherwise specified, "parts" and "%" are based on mass.

(Synthesis of Fluorinated Pyrolytic Polymer (D-1))

In a glass flask equipped with a stirring device, thermometer, cooling tube, and dropping device, 26.8 g of acrylic acid and 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro 30.0 g of ro-1-vinyloxyoctane was put, and it stirred at room temperature under a dry air stream for 21 hours. Next, 0.003 g of metoquinone and 107.6 g of diisopropyl ether were added, 161.4 g of a saturated sodium carbonate aqueous solution and 161.4 g of ion-exchanged water were added, followed by liquid separation. Subsequently, after taking out the upper layer, 161.4 g of ion-exchanged water was added and liquid-separated. Moreover, after taking out the upper layer, it solvent-removed, and the polymerizable monomer which has a blocked carboxyl group was obtained.

50 g of propylene glycol monomethyl ether acetate was put as a solvent in a glass flask equipped with a stirring device, a thermometer, a cooling tube, and a dropping device, and the temperature was raised to 80° C. while stirring under a nitrogen stream. Next, a monomer solution in which 17.5 g of the polymerizable monomer having a blocked carboxyl group and 32.5 g of propylene glycol polybutylene glycol monomethacrylate are dissolved in 40 g of propylene glycol monomethyl ether acetate, and 2,2'-azo as a radical polymerization initiator Two dropping solutions of the polymerization initiator solution in which 0.5 g of bis(methyl isobutyrate) was dissolved in 17 g of propylene glycol monomethyl ether acetate were set in separate dropping devices, respectively, and the dropping was started while maintaining the inside of the flask at 80°C. , The monomer solution was added dropwise over 3 hours and the initiator solution was added dropwise over 4 hours. After completion of the dropwise addition, after stirring at 80°C for 10 hours, propylene glycol monomethyl ether acetate is further added, and a propylene glycol monomethyl ether acetate solution containing 20% by mass of the fluorinated pyrolytic resin (D-1) of the present invention Got it. As a result of measuring the molecular weight of the obtained fluorinated thermally decomposable resin by GPC (polystyrene conversion molecular weight), it was a number average molecular weight of 2,900, a weight average molecular weight of 28,000, and a maximum molecular weight of 300,000.

(Synthesis of siloxane-containing pyrolytic polymer (D-2))

In the following examples by the same production method as the compound (D-1), a polymerizable monomer represented by the formula (D-2a) was synthesized, and the polymerizable monomer represented by the (D-2a) and propylene A polymer (D-2) of glycol polybutylene glycol monomethacrylate (number average molecular weight 2,500, weight average molecular weight 15,000, maximum molecular weight 160,000) was used.

In addition, as the compound of (D-3) to (D-7), the following compounds were used.

BYK-352 (manufactured by Big Chemistry Japan Co., Ltd.) (D-3)

TEGOFLOW ZFS-460 (manufactured by Evonik Japan) (D-4)

Megapack F-554 (manufactured by DIC Corporation) (D-5)

Megapack F-447 (manufactured by DIC Corporation) (D-6)

Megapack RS-75 (manufactured by DIC Corporation) (D-7)

(Preparation of polymerizable liquid crystal composition (1))

As shown in Table 1, the total value of 40 parts by mass of the compound represented by formula (A-1), 40 parts by mass of the compound represented by formula (A-2), and 20 parts by mass of the compound represented by formula (A-3) Based on 100 parts by mass, 0.1 parts by mass of the compound of (D-1), 5 parts by mass of the polymerization initiator (E-1), and 0.1 parts by mass of paramethoxyphenol (MEHQ) (F-1) are used, and Using the organic solvent cyclopentanone (H-1) so that the total amount is 20% by mass, and using a stirring device having a stirring propeller, stirring for 1 hour under conditions of a stirring speed of 300 rpm and a solution temperature of 80°C Thereafter, it was filtered through a 0.2 μm membrane filter to obtain a polymerizable liquid crystal composition (1).

(Preparation of polymerizable liquid crystal compositions (2) to (29) and comparative polymerizable liquid crystal compositions (C1) to (C3))

Similar to the preparation of the polymerizable liquid crystal composition (1) of the present invention, the formulas (A-1) to (A-14), formulas (B-1) to (B-11), and (C) shown in Table 1 -1) to formula (C-5), (D-1) to (D-7) compound, (E-1) compound, (E-2) compound, (F-1) Each compound of the compound represented by, the compound represented by (F-2), and the compound represented by formula (G-1) was changed to the ratio shown in Tables 1 to 4, respectively, and the organic solvent, cyclopentanone (H Except that the mixing ratio of -1) was changed to the ratio shown in Tables 1 to 4, respectively, under the same conditions as the preparation of the polymerizable liquid crystal composition (1), the polymerizable liquid crystal compositions (2) to (29) and Comparative polymerizable liquid crystal compositions (C1) to (C3) were obtained.

In Tables 1 to 4, specific compositions of the polymerizable liquid crystal compositions (1) to (29) and comparative polymerizable liquid crystal compositions (C1) to (C3) of the present invention are shown.

Irgacure 907 (manufactured by BASF Japan Co., Ltd.) (E-1)

Lucilin TPO (manufactured by BASF Japan Co., Ltd.) (E-2)

MEHQ (manufactured by Wako Junyaku Industry Co., Ltd.) (F-1)

IRGANOX-1076 (manufactured by BASF Japan Co., Ltd.) (F-2)

(Production of optically anisotropic body using polymerizable liquid crystal composition)

(Example 1)

A polyimide solution for an alignment film was applied to a glass substrate having a thickness of 0.7 mm by spin coating, dried at 100°C for 10 minutes, and fired at 200°C for 60 minutes to obtain a polyimide coating film. The obtained polyimide coating film was rubbed. The rubbing treatment was performed using a commercially available rubbing device.

The polymerizable liquid crystal composition (1) of the present invention was applied to the rubbed substrate by spin coating at room temperature, dried at 80°C for 2 minutes, and left at room temperature for 2 minutes. Thereafter, using a conveyor-type high-pressure mercury lamp, UV light was irradiated for 10 seconds under the condition of 50 mW/cm ² to perform polymerization of the coating film, and the leveling property and wettability of the obtained coating film surface were measured under the following conditions.

Thereafter, the coating film 0 obtained by polymerization was fired at 230° C. for 30 minutes to obtain a coating film 1 (phase difference film) of Example 1. In addition, the measurement of the phase difference (Re) of the obtained coating film 1 was performed under the following conditions. Moreover, the wettability of the surface of the obtained coating film 1 was measured again.

<Evaluation of leveling property>

The leveling property of the obtained coating film 0 surface was observed visually, and evaluated as follows.

○: By visual observation, there is no lump on the entire surface of the coating film, and it has a uniform and smooth surface state.

(Triangle|delta): There is no lump on the entire surface of the coating film by visual observation, but it has a surface state that is not partially smooth.

×: There is agglomeration on the entire surface of the coating film by visual observation, and has a non-uniform surface state.

<Evaluation of wettability>

The wettability of the surface of the obtained coating film 0 and the coating film 1 was evaluated by the contact angle of water under the following conditions. In this evaluation, the lower the contact angle of water, the better the wettability.

(Measurement conditions of contact angle) 3 µL of ultrapure water was dripped onto the coating film 0 and the coating film 1. After dropping, a photograph after 3000 ms was taken, and a contact angle was obtained from the image of the captured droplet using the θ/2 method. In addition, as a measuring device, "DropMaster500" manufactured by Kyowa Kaimen Chemical Co., Ltd. was used.

<Measurement of phase difference (Re(θr))>

The retardation of the obtained coating film 1 in the θr = 0° direction was measured by RETS-100. θr is the angle of incident light with respect to the coating film, θr=0° indicates a direction perpendicular to the coating film, and θr=±50° indicates a direction inclined by 50° from the vertical direction with respect to the coating film.

The results are shown in the table below.

(Examples 2 to 18, Comparative Examples 1 to 2)

Under the same conditions as in Example 1, the polymerizable liquid crystal compositions (2) to (18) and (C1) to (C3) were used to prepare a coating film 1 (phase difference film). In addition, under the same conditions as in Example 1, Re(θr), leveling property, and wettability (before firing and after firing) were measured, and the results were taken as Examples 2 to 18 and Comparative Examples 1 to 2, and Table 5 above. It is shown in ~7.

(Example 19)

The polymerizable liquid crystal composition (19) of the present invention was applied to the glass substrate on which the rubbed polyimide coating film was formed in the same manner as in Example 1 by spin coating at room temperature, dried at 80°C for 2 minutes, and then at room temperature for 2 minutes. Neglected. Thereafter, using a conveyor-type high-pressure mercury lamp, UV light was irradiated for 10 seconds under the condition of 50 mW/cm ² to perform polymerization of the coating film, and the coating film obtained by polymerization was fired at 230° C. for 30 minutes, and the thickness Coating 1, which is a 5.0 micron cholesteric reflective film, was obtained.

Re(θr), leveling property, and wettability (before firing and after firing) of the obtained coating film 1 were measured under the same conditions as in Example 1. Further, as a result of measuring the selective reflection wavelength of the obtained coating film 1 using a spectrophotometer U-4100 (manufactured by Hitachi Corporation), the polarization reflection band was 265 nm.

The obtained results are shown in the table below.

(Example 20 and Comparative Example 3)

Under the same conditions as in Example 19, the polymerizable liquid crystal composition (20) of the present invention and the comparative polymerizable liquid crystal composition (C3) were used to prepare a coating film 1 which is a cholesteric reflective film. In addition, under the same conditions as in Example 19, Re(θr), leveling property, wettability (before firing, after firing), and selective reflection wavelength were measured, and the results were taken as Example 20 and Comparative Example 3, and are shown in Table 8 above. Show.

As described above, the coating film using the polymerizable liquid crystal composition of the present invention containing a polymer having a pyrolytic group has improved wettability after firing. This is because the polymer having a pyrolytic group segregates on the surface of the coating film in the drying process of the coating film, and the thermally decomposable group portion of the polymer imparting water repellency and oil repellency is desorbed in the subsequent firing process, thereby increasing the surface energy of the coating film surface. It is considered that it was because it did. On the other hand, in Comparative Examples 1 to 3 using a surfactant conventionally used as an additive, there is no significant difference in the wettability of the coating film before and after firing, and the desorption of a specific portion by firing and the accompanying surface energy of the coating film It is considered that there was no rise.

(Production of laminate)

(Example 21)

A polyimide solution for an alignment film was applied to a glass substrate having a thickness of 0.7 mm by spin coating, dried at 100°C for 10 minutes, and fired at 200°C for 60 minutes to obtain a polyimide coating film. The obtained polyimide coating film was rubbed. The rubbing treatment was performed using a commercially available rubbing device.

The polymerizable liquid crystal composition (1) of the present invention was applied to a glass substrate (substrate: glass with rubbing PI) on which the rubbed polyimide coating was formed by spin coating at room temperature, dried at 80°C for 2 minutes, and left at room temperature for 2 minutes. did. Thereafter, using a conveyor-type high-pressure mercury lamp, UV light was irradiated for 10 seconds under the condition of 50 mW/cm ² to perform polymerization of the coating film, and the coating film obtained by polymerization was fired at 230° C. for 30 minutes, and the thickness Coating film 1 (phase difference film) which is a 0.6 micron positive A plate was obtained.

Next, the prepared polymerizable liquid crystal composition (21) was applied onto the coating film 1 as a positive A plate by spin coating at room temperature, dried at 80°C for 2 minutes, and allowed to stand at room temperature for 2 minutes. Thereafter, using a conveyor-type high-pressure mercury lamp, UV light was irradiated for 10 seconds under the condition of 50 mW/cm ² to perform polymerization of the coating film, and a 0.6 micron positive A plate and a 4.0 micron thick negative C plate were formed. The coating film 2 (layered body of phase difference films) laminated in this order was obtained. Aggregation of the surface of the obtained coating film 2 was evaluated under the following conditions.

<Evaluation of aggregation>

The aggregation of the obtained coating film 2 was observed visually, and evaluated as follows.

○: Visual observation shows no lumps on the entire surface of the coating.

△: A lump is seen in part of the coating film by visual observation.

×: A lump is seen on the entire surface of the coating film by visual observation.

The results are shown in the table below.

(Examples 22 to 32, Comparative Example 5 and Comparative Example 6)

On the same conditions as in Example 21, the polymerizable liquid crystal compositions (2) to (10) and (C1) to (C2) were used to prepare a coating film 1 which is a positive A plate. Further, on the obtained positive A plate, coating film 1, under the same conditions as in Example 21, using polymerizable liquid crystal compositions (21) to (24), coating film 2 in which a positive A plate and a negative C plate were laminated in this order. Produced. The polymerizable liquid crystal composition used for the coating film 1 and the coating film 2, and the obtained results are shown in Table 9 above as Examples 22 to 32, Comparative Examples 5 and 6.

(Example 33)

Except for changing the spin-coating conditions as in Example 21, the polymerizable liquid crystal composition (1) was used to prepare a coating film 1 as a positive A plate having a thickness of 0.9 microns under the same conditions. Next, a silane coupling-based material for a vertical alignment film (manufactured by JNC: DMOAP) was applied on the coating film 1 which is a positive A plate by a spin coating method, and fired at 100°C for 1 hour to form a vertical alignment film on the coating film 1. The polymerizable liquid crystal composition (27) was applied onto the obtained vertical alignment film by spin coating, and dried at 80°C for 2 minutes. After cooling the obtained coating film to room temperature, using a high-pressure mercury lamp, UV rays were irradiated for 10 seconds at an intensity of 50 mW/cm ² , and a 0.9 micron thick positive A plate and a 1.0 micron thick positive C plate were laminated in this order. Painted film 2 was produced. As a result of confirming the aggregation of the surface of the obtained coating film 2 in the same manner as in Example 21, no aggregation was observed on the entire surface of the coating film by visual observation.

The results are shown in the table below.

(Examples 34 to 42)

On the same conditions as in Example 33, the polymerizable liquid crystal compositions (1) to (5) and (7) to (10) were used to prepare a coating film 1 which is a positive A plate. Further, on the obtained positive A plate, coating film 1, under the same conditions as in Example 33, using the polymerizable liquid crystal compositions (27) and (28), coating film 2 in which a positive A plate and a positive C plate were laminated in this order. Produced. The polymerizable liquid crystal composition used for the coating film 1 and the coating film 2, and the obtained results are shown in Table 10 above as Examples 34 to 42.

(Example 43)

Under the same conditions as in Example 21, using the polymerizable liquid crystal composition (2), a coating film 1 as a positive A plate having a thickness of 0.9 microns was produced. Next, the prepared polymerizable liquid crystal composition 29 was applied onto the coating film 1 which is a positive A plate by spin coating at room temperature, dried at 80°C for 2 minutes, and allowed to stand at room temperature for 2 minutes. Thereafter, using a conveyor-type high-pressure mercury lamp, UV light was irradiated for 10 seconds under the condition of 50 mW/cm ² to perform polymerization of the coating film, and a positive A plate having a thickness of 0.9 microns and a positive O plate having a thickness of 1.0 micron were obtained. The coating film 2 laminated|stacked in this order was obtained. As a result of confirming the aggregation of the surface of the obtained coating film 2 in the same manner as in Example 33, no aggregation was observed on the entire surface of the coating film by visual observation.

(Example 44)

5 parts of the photo-alignment material (Mw: 100,000 to 300,000) represented by the following formula (30-1) was dissolved in 47.5 parts of toluene and 47.5 parts of propylene glycol monomethyl ether acetate to obtain a solution. The obtained solution was filtered through a 0.45 μm membrane filter to obtain a photo-alignment solution (30).

Next, under the same conditions as in Example 33, using the polymerizable liquid crystal composition (1), a coating film 1 as a positive A plate having a thickness of 0.9 microns was produced. The photo-alignment solution 30 was applied on the positive A plate, coating film 1, using a spin coating method, dried at 80° C. for 2 minutes, and immediately irradiated with linearly polarized light of 313 nm at an intensity of 10 mW/cm ² for 20 seconds. , A photo-alignment film 1 was formed on the coating film 1 which is a positive A plate. The polymerizable liquid crystal composition (25) was applied onto the obtained photo-alignment film (1) by spin coating, and dried at 80°C for 2 minutes. After cooling the obtained coating film to room temperature, using a high-pressure mercury lamp, irradiation with ultraviolet rays for 10 seconds at an intensity of 50 mW/cm ² , a positive A plate having a thickness of 0.9 microns and a positive A plate having a thickness of 1.8 microns in this order The coating film 2 laminated with was obtained. This coating film 2 functioned as a circularly polarizing plate. As a result of confirming the aggregation of the surface of the coating film 2 in the same manner as in Example 33, no aggregation was observed on the entire surface of the coating film by visual observation.

The results are shown in the table below.

(Examples 45 to 48)

On the same conditions as in Example 44, the polymerizable liquid crystal compositions (2) to (3) and (7) were used to prepare a coating film 1 which is a 1.0 micron-thick positive C plate. On the obtained coating film 1, under the same conditions as in Example 44, a photo-alignment film (1) was formed, and by using the polymerizable liquid crystal compositions (25) and (26), a positive A plate having a thickness of 0.9 microns and a thickness A coating film 2 was prepared in which a 1.8 micron positive A plate was laminated in this order. This coating film 2 functioned as a circularly polarizing plate. The polymerizable liquid crystal composition used for the coating film 1 and the coating film 2, and the obtained results are shown in Table 11 as Examples 45 to 48.

(Example 49)

A silane coupling material (manufactured by JNC: DMOAP) for a vertical alignment film was applied on a glass substrate by a spin coating method, and fired at 100° C. for 1 hour to form a vertical alignment film on the glass substrate. The polymerizable liquid crystal composition (11) was applied on the obtained vertical alignment film by spin coating, and dried at 80°C for 2 minutes. After cooling the obtained coating film to room temperature, using a conveyor-type high-pressure mercury lamp, UV light was irradiated with UV light at an intensity of 50 mW/cm ² for 10 seconds to perform polymerization of the coating film, and further, the coating film obtained by polymerization was 230°C. It fired at for 30 minutes, and obtained the coating film 1 which is a 1.0 micron-thick positive C plate.

Next, the photo-alignment solution 30 was applied on the coating film 1 using a spin coating method, dried at 80° C. for 2 minutes, and immediately irradiated with linearly polarized light of 313 nm at an intensity of 10 mW/cm ² for 20 seconds, A photo-alignment film 1 was formed on the coating film 1. The polymerizable liquid crystal composition (25) was applied onto the obtained photo-alignment film (1) by spin coating, and dried at 80°C for 2 minutes. After cooling the obtained coating film to room temperature, using a high-pressure mercury lamp, irradiated with ultraviolet rays for 10 seconds at an intensity of 50 mW/cm ² , a 1.0 micron-thick positive C plate and a 0.9-micron-thick positive C plate were laminated in this order. Coating 2 was obtained. Aggregation of the surface of the obtained coating film 2 was evaluated in the same manner as in Example 21.

The results are shown in the table below.

(Examples 50-56)

Under the same conditions as in Example 49, using the polymerizable liquid crystal compositions (11) to (15), coating film 1 as a positive C plate having a thickness of 1.0 microns was produced. On the obtained coating film 1, under the same conditions as in Example 44, a photo-alignment film (1) was formed, and a positive C plate having a thickness of 1.0 micron and a thickness was obtained by using the polymerizable liquid crystal compositions (25) and (26). A coating film 2 was prepared in which 0.9 micron positive A plates were stacked in this order. The polymerizable liquid crystal composition used for the coating film 1 and the coating film 2, and the obtained results are shown in Table 12 above as Examples 50 to 56.

(Manufacture of a transfer type polarizing plate laminate)

(Example 57)

A silane coupling material (manufactured by JNC: DMOAP) for a vertical alignment film was applied on a glass substrate by a spin coating method, and fired at 100° C. for 1 hour to form a vertical alignment film on the glass substrate. The polymerizable liquid crystal composition (16) was applied onto the obtained vertical alignment film by spin coating, and dried at 80°C for 2 minutes. After cooling the obtained coating film to room temperature, using a conveyor-type high-pressure mercury lamp, UV light was irradiated with UV light at an intensity of 50 mW/cm ² for 10 seconds to perform polymerization of the coating film, and further, the coating film obtained by polymerization was 230°C. It fired at for 30 minutes, and obtained the coating film 1 which is a 0.5 micron-thick positive O plate.

Next, a polarizing plate was laminated on the surface of the coating film 1 using DAITAC ZB7010W-15 (manufactured by DIC Corporation) as an adhesive material. Then, the glass substrate was peeled off, and the transfer type viewing angle compensation polarizing plate on which the coating film 1 was laminated was obtained. The heat-resistant peelability of the obtained transfer type viewing angle compensation polarizing plate (laminate) was evaluated under the following conditions.

<Evaluation of heat-resistant peelability>

The peelability of the obtained laminate was evaluated as follows by performing a heat resistance test at 85°C for 500 hours.

○: There is no part peeled between the coating film 1 and the polarizing plate.

(Triangle|delta): There is a part which peeled slightly between coating film 1 and a polarizing plate.

X: There is a part peeled off between the coating film 1 and a polarizing plate.

The results are shown in the table below.

(Examples 58-60)

In the same manner as in Example 57, a transfer type viewing angle compensation polarizing plate as a laminate of a 0.5 micron-thick hybrid alignment layer and a polarizing plate was obtained using the polymerizable liquid crystal compositions (16) to (18).

The obtained results are shown in Table 13 above.

(Reflective polarizer)

(Example 61)

The polymerizable liquid crystal composition (19) of the present invention was applied to a glass substrate with a rubbed polyimide coating film prepared in the same manner as in Example 21 by spin coating at room temperature, dried at 80°C for 2 minutes, and then at room temperature for 2 minutes. Neglected. Thereafter, using a conveyor-type high-pressure mercury lamp, UV light was irradiated for 10 seconds under the condition of 50 mW/cm ² to perform polymerization of the coating film, and the coating film obtained by polymerization was fired at 230° C. for 30 minutes, and the thickness Coating 1, which is a 5.0 micron cholesteric reflective film, was obtained.

Next, a polarizing plate was laminated on the surface of the coating film 1 using DAITAC ZB7010W-15 (manufactured by DIC Corporation) as an adhesive material. Then, the glass substrate was peeled off, and the reflective polarizing plate (laminated body) which laminated|stacked the cholesteric reflective film was obtained. The heat-resistant peelability of the obtained reflective polarizing plate was performed in the same manner as in Example 57.

The obtained results are shown in the table below.

(Example 62, Comparative Example 6)

In the same manner as in Example 61, a reflective polarizing plate in which a 5.0 micron-thick cholesteric reflective film was laminated was obtained using the polymerizable liquid crystal composition (20) of the present invention and the comparative polymerizable liquid crystal composition (C3). The heat-resistant peelability of the obtained reflective polarizing plate was performed in the same manner as in Example 57.

The obtained results are shown in Table 14 above.

As described above, the coating film 1 using the polymerizable liquid crystal composition of the present invention containing a polymer having a pyrolytic group can be formed as a laminate in which an additional coating film is laminated on the coating film, and the resulting laminate surface has excellent leveling properties. Moreover, it became clear that the heat-resistant peelability was also very high.

Claims (17)

In the polymerizable liquid crystal composition containing a polymer having at least one or more pyrolytic groups and a polymerizable liquid crystal compound,
The thermally decomposable group is the following general formula (I-1-1) or general formula (I-1-2)

(In general formula (I-1-1) and general formula (I-1-2), R ¹ , R ² each independently represent a hydrogen atom or a linear or branched organic group having 1 to 18 carbon atoms , Y ¹ represents an oxygen atom or a sulfur atom, R ⁴ represents an organic group having a fluorine atom and/or a silicon atom, and * represents a bonding site.), a polymerizable liquid crystal composition containing a structural unit represented by. The method according to claim 1,
The polymerizable liquid crystal compound is the general formula (II)

(In the formula, P ² represents a polymerizable functional group,
Sp ¹ represents an alkylene group having 1 to 18 carbon atoms (the hydrogen atom in the alkylene group may be substituted with one or more halogen atoms or CN, and one CH ₂ group present in this group or not adjacent Two or more CH ₂ groups which are not each independently of each other may be substituted by -O-, -COO-, -OCO-, or -OCO-O-.),
X ¹ is -O-, -S-, -OCH ₂ -, -CH ₂ O-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO -O-, -CO-NH-, -NH-CO-, -SCH ₂ -, -CH ₂ S-, -CF ₂ O-, -OCF ₂ -, -CF ₂ S-, -SCF ₂ -,- CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-CH ₂ CH ₂ -, -OCO-CH ₂ CH ₂ -,- CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO-CH ₂ -, -OCO-CH ₂ -, -CH ₂ -COO-, -CH ₂ -OCO-, -CH=CH- , -N=N-, -CH=NN=CH-, -CF=CF-, -C≡C- or a single bond (however, P ² -Sp ¹ and Sp ¹ -X ¹ are -OO- , -O-NH-, -SS- and -OS- groups are not included.),
q1 represents 0 or 1,
MG represents a mesogenic group,
R ² represents a hydrogen atom, a halogen atom, a cyano group, or a linear or branched alkyl group having 1 to 12 carbon atoms, and the alkyl group may be linear or branched, and the alkyl group may be one -CH ₂ -or Two or more non-adjacent -CH ₂ -are each independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O- CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-,- It may be substituted by CH=CH-, -CF=CF-, or -C≡C-, or R ² is general formula (II-a)

(In the formula, P ³ represents a polymerizable functional group,
Sp ² represents the same as defined in Sp ¹ ,
X ² represents the same as defined in X ¹ (however, P ³ -Sp ² and Sp ² -X ² do not include -OO-, -O-NH-, -SS- and -OS- groups. .),
q ² represents 0 or 1.) represents a group represented by.)
The polymerizable liquid crystal composition which is a compound represented by. The method according to claim 2,
In the general formula (II), MG is the general formula (II-b)

(In the formula, B1, B2, and B3 are each independently a 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6- Diyl group, pyridin-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group, 1,2,3,4-tetra Hydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3, 4,4a,9,10a-octahydrophenanthrene-2,7-diyl group, 1,4-naphthylene group, benzo[1,2-b:4,5-b']dithiophene-2,6- Diyl group, benzo[1,2-b:4,5-b']diselenophene-2,6-diyl group, [1]benzothieno[3,2-b]thiophene-2,7-di Diary, [1] benzoselenopheno[3,2-b]selenophene-2,7-diyl group, or fluorene-2,7-diyl group, and one or more F, Cl, CF ₃ as a substituent , OCF ₃ , CN group, an alkyl group having 1 to 8 carbon atoms (the hydrogen atom in the alkyl group may be substituted with one or more phenyl groups, and one CH ₂ group present in the group or 2 not adjacent Each of the _two or more CH ₂ groups may each independently be substituted with -O-, -COO-, -OCO-, or -OCO-O-.), alkoxy group, alkanoyl group, alkanoyloxy group, carbon atom Number 2-8 alkenyl group, alkenyloxy group, alkenoyl group, alkenoyloxy group, and/or general formula (II-c)

(In the formula, P ⁴ represents a polymerizable functional group,
Sp ³ represents an alkylene group having 1 to 18 carbon atoms, and X ³ represents -O-, -COO-, -OCO-, -OCH ₂ -, -CH ₂ O-, -CH ₂ CH ₂ OCO- , Or -CH ₂ CH ₂ COO-, q ³ represents 0 or 1, and q ⁴ represents 0 or 1. (However, P ⁴ -Sp ³ and Sp ³ -X ³ do not include -OO-, -O-NH-, -SS-, and -OS- groups.)),
Z1 and Z2 are each independently, -COO-, -OCO-, -CH ₂ CH ₂ -, -OCH ₂ -, -CH ₂ O-, -CH=CH-, -C≡C-, -CH=CHCOO -, -OCOCH=CH-, -CH ₂ CH ₂ COO-, -CH ₂ CH ₂ OCO-, -COOCH ₂ CH ₂ -, -OCOCH ₂ CH ₂ -, -CONH-, -NHCO-, have a halogen atom Also represents an alkyl group or a single bond having 2 to 10 carbon atoms,
r1 represents 0, 1, or 2, and when a plurality of B1 and Z1 are present, they may be the same or different, respectively.). The method of claim 3,
General formula (II) is general formula (II-2-2-2)

(In the formula, P ² and P ³ each independently represent a polymerizable functional group, and Sp ¹ and Sp ² each independently represent an alkylene group having 1 to 18 carbon atoms (the hydrogen atom in the alkylene group is one It may be substituted by the above halogen atom, CN group, or an alkyl group having 1 to 8 carbon atoms having a polymerizable functional group, and one CH ₂ group present in the group or two or more CH ₂ groups not adjacent to each other Independently of each other, they may be substituted by -O-, -COO-, -OCO-, or -OCO-O-.),
X ¹ and X ² are each independently -O-, -S-, -OCH ₂ -, -CH ₂ O-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO -, -O-CO-O-, -CO-NH-, -NH-CO-, -SCH ₂ -, -CH ₂ S-, -CF ₂ O-, -OCF ₂ -, -CF ₂ S-, -SCF ₂ -, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-CH ₂ CH ₂ -, -OCO-CH ₂ CH ₂ -, -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO-CH ₂ -, -OCO-CH ₂ -, -CH ₂ -COO-, -CH ₂ -OCO- , -CH=CH-, -N=N-, -CH=NN=CH-, -CF=CF-, -C≡C- or a single bond (however, P ² -S ¹ and S ¹ -X ¹ does not include -OO-, -O-NH-, -SS- and -OS- groups.), q1 and q2 each independently represent 0 or 1,
B11, B2 and B3 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1,3- Dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo(2,2,2) octylene group, decahydronaphthalene-2,6-diyl group, pyridine -2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group, 1,2,3,4-tetrahydronaphthalene-2 ,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9,10a-octahydrophenanthrene-2,7-diyl group, 1,4-naphthylene group, benzo[1,2-b:4,5-b']dithiophene-2,6-diyl group, benzo [1,2-b:4,5-b']diselenophene-2,6-diyl group, [1]benzothieno[3,2-b]thiophene-2,7-diyl group, [1 ]Benzoselenopheno[3,2-b]selenophen-2,7-diyl group, or fluorene-2,7-diyl group, and as a substituent at least one F, Cl, CF ₃ , OCF ₃ , CN group, a C1-C8 alkyl group, a C1-C8 alkoxy group, a C1-C8 alkanoyl group, a C1-C8 alkanoyloxy group, a C1-C8 alkoxy group It may have an alkoxycarbonyl group of 8, an alkenyl group of 2 to 8 carbon atoms, an alkenyloxy group of 2 to 8 carbon atoms, an alkenoyl group of 2 to 8 carbon atoms, an alkenoyloxy group of 2 to 8 carbon atoms ,
Z11 and Z2 are each independently, -COO-, -OCO-, -CH ₂ CH ₂ -, -OCH ₂ -, -CH ₂ O-, -CH=CH-, -C≡C-, -CH=CHCOO -, -OCOCH=CH-, -CH ₂ CH ₂ COO-, -CH ₂ CH ₂ OCO-, -COOCH ₂ CH ₂ -, -OCOCH ₂ CH ₂ -, -C=N-, -N=C-, -CONH-, -NHCO-, -C(CF ₃ ) ₂ -, represents an alkyl group having 2 to 10 carbon atoms or a single bond which may have a halogen atom.) At least 1 selected from the group consisting of compounds represented by The polymerizable liquid crystal composition which is a compound of species. The method according to claim 1,
The polymerizable liquid crystal compound is the general formula (III)

(In the formula, R ⁷ each independently represents a substituent represented by the general formula (III-a).

(In the formula, R ⁹ and R ¹⁰ each independently represent a hydrogen atom, a halogen atom or a methyl group, and R ⁸ represents an alkoxy group having 1 to 20 carbon atoms, and the hydrogen atom in the alkoxy group is the general formula (III-b ), may be substituted by a substituent represented by the general formula (III-c), or the general formula (III-d), and at least one of R ⁸ present in the general formula (III) is a general formula (III-b ), a substituent represented by the general formula (III-c), or the general formula (III-d).)

(In the formula, R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ , R ⁸⁵ , R ⁸⁶ , R ⁸⁷ , R ⁸⁸ and R ⁸⁹ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms, , n represents 0 or 1. The polymerizable liquid crystal composition which is a compound represented by)). A polymer obtained by polymerizing the polymerizable liquid crystal composition according to claim 1 or 5. An optically anisotropic body formed using the polymerizable liquid crystal composition according to claim 1 or 5. A retardation film made of the polymerizable liquid crystal composition according to claim 1 or 5. A retardation patterning film formed by using the polymerizable liquid crystal composition according to claim 1 or 5. A brightness improving film obtained by using the polymerizable liquid crystal composition according to claim 1 or 5. An antireflection film formed using the polymerizable liquid crystal composition according to claim 1 or 5. A viewing angle compensation film formed by using the polymerizable liquid crystal composition according to claim 1 or 5. A retardation film formed by laminating a negative C plate on the retardation film according to claim 8. A retardation film formed by laminating a positive C plate on the retardation film according to claim 8. A retardation film formed by laminating a positive A plate on the retardation film according to claim 8. delete delete