JPWO2017183682A1 - Polymerizable composition and film using the same - Google Patents

Abstract

Provided is a polymerizable liquid crystal composition that can be uniformly applied on a substrate without unevenness, and can be laminated on a film obtained by irradiating an active energy ray after coating to the substrate. An object of the present invention is to provide an optically anisotropic body and a laminate having good orientation using the polymerizable composition. The present invention provides a polymerizable liquid crystal composition containing a polymer having at least one thermally decomposable group and a polymerizable liquid crystal compound. Moreover, the optical anisotropic body and laminated body using the polymeric liquid crystal composition of this invention are also provided.

Description

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

  The polymerizable liquid crystal composition is useful as a constituent member of an optical anisotropic body, and the optical anisotropic body is applied to various liquid crystal displays as, for example, a polarizing film and a retardation film. A polarizing film or a retardation film is obtained by applying a polymerizable liquid crystal composition to a substrate, drying the solvent, and then heating or activating active energy rays in a state where the polymerizable liquid crystal composition is aligned by an alignment film or the like. It is obtained by curing the polymerizable liquid crystal composition by irradiation. Further, it is known that a circularly polarized light separating element can be obtained by using a polymerizable cholesteric liquid crystal composition obtained by adding a chiral compound to a polymerizable liquid crystal composition, and its application to a brightness enhancement film or the like is being studied.

  These polymerizable liquid crystal compositions are generally coated on a glass substrate or plastic substrate, or further on a substrate on which an alignment film is formed if necessary, and cured to produce a retardation film. It is required to apply the polymerizable liquid crystal composition uniformly and uniformly. Therefore, a fluorine-based surfactant that can significantly reduce the surface tension of the coating film is generally used as an additive. However, when a fluorine-based surfactant is used, fluorine atoms remain on the surface of the retardation film, so that the retardation film surface becomes a low surface energy layer, making it difficult to laminate the retardation film surface. In addition, when a polarizing plate is laminated on a retardation film using a non-polymerizable fluorosurfactant via an adhesive layer, the fluorosurfactant permeates the adhesive layer over time. Trouble occurred.

  As a method for improving the above-mentioned problems, a laminated film using a polymerizable fluorosurfactant has been reported. However, in this method, even if it can be applied uniformly and without unevenness, it is laminated on a retardation film. A laminate having good adhesion could not be obtained (Patent Documents 1 to 3).

JP 2003-105030 A JP 2009-41023 A Japanese Patent No. 5026060

  The problem to be solved by the present invention is a polymerizability that can be uniformly applied on a substrate and can be laminated on a film obtained by irradiating an active energy ray after coating to the substrate. An object of the present invention is to provide a liquid crystal composition and to provide an optically anisotropic body and a laminate having good alignment using the polymerizable composition.

  In order to solve the above-mentioned problems, the present invention has been conducted by intensively researching the polymerizable liquid crystal composition, and as a result, 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 kind of thermally decomposable group and a polymerizable liquid crystal compound. Moreover, the optical anisotropic body and laminated body using the polymeric liquid crystal composition of this invention are also provided.

  By using the polymerizable liquid crystal composition of the present invention, it can be uniformly applied on the substrate, and a laminate having a good adhesion can be obtained on the resulting film, Useful for optical material applications.

The best mode of the polymerizable liquid crystal composition according to the present invention will be described below. In the present invention, the “liquid crystal” of the polymerizable liquid crystal composition refers to removing the organic solvent after coating the polymerizable liquid crystal composition on a substrate. It is intended to show liquid crystal properties in the state. In the present invention, the “liquid crystal” of the polymerizable liquid crystal compound means a case where it is intended to show liquid crystal properties with only one type of polymerizable liquid crystal compound used, or a mixture with other liquid crystal compounds. It is intended to exhibit liquid crystal properties. The polymerizable liquid crystal composition can be polymerized (formed into a film) by performing a polymerization treatment by irradiation with light such as ultraviolet rays, heating, or a combination thereof.
(Thermodegradable polymer having a thermally decomposable group)
The polymerizable liquid crystal composition of the present invention is characterized by containing at least one polymer having a thermally decomposable group. A polymer having a thermally decomposable group is used by being added to the polymerizable liquid crystal composition, and the polymerizable liquid crystal composition is uniformly dispersed on a substrate composed of a substrate or an alignment film used as necessary. It can be applied without. Specific examples of the polymer having a thermally decomposable group include a polymer in which the thermally decomposable group contains a fluorine atom and / or a silicon atom.

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

(In General Formula (I-1-1) and General Formula (I-1-2), R ¹ and R ² are each independently a hydrogen atom or a linear or branched carbon atom having 1 to 18 carbon atoms. Represents an organic group, 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.

In the general formula (I-1-1) and the general formula (I-1-2), ^{R 1} is a hydrogen atom or a linear or branched 1-18 organic group carbon atoms, ^{R 1} Is preferably a hydrogen atom or a methyl group, and R ¹ is more preferably a hydrogen atom.

In the general formula (I-1-1) and the general formula (I-1-2), ^{R 2} is a hydrogen atom or a linear or branched 1-18 organic group carbon atoms, ^{R 2} Is preferably a linear alkyl group having 1 to 12 carbon atoms, 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, and Y ¹ is preferably an oxygen atom.

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

R ⁴ is preferably a group represented by the following formula (I-R4-1) to formula (I-R4-19), 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, or a phenyl group, and n5 represents an integer of 1 to 150.

  The polymer having a thermally decomposable group of the present invention has a structural unit other than the structural unit represented by the general formula (I-1-1) or general formula (I-1-2) as long as the effects of the present invention are not impaired. It may contain a structural unit. 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 are each independently a hydrogen atom or a linear or branched carbon atom having 1 to 18 carbon atoms. Represents an organic group, Y ¹¹ represents an oxygen atom or a sulfur atom, R ⁴¹ represents an organic group having 1 to 18 carbon atoms, R ²¹ and R ⁴¹ are bonded to each other, and Y ¹¹ is a hetero atom. A ring may be formed, and * represents a binding site.)
In the 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. However, the difference in polarity between the blocked carboxyl group and the restored carboxyl group is preferable. Moreover, as a side chain represented by the said general formula (I-2-1) or general formula (I-2-2), following formula (I-2-1-1) or a formula (I-2-2) The side chain represented by -1) is more preferable.

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

  Production method 1: Polymerizable monomer (α) having a hydroxyl group or a carboxyl group and the following general formula (IA)

(In the 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 polymerizing the polymerizable monomer after reacting with a vinyl ether compound represented by formula (1) to obtain a polymerizable monomer having a blocked carboxyl group.

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

  Examples of the polymerizable monomer (α) having a hydroxyl group or a carboxyl group include (meth) acrylic acid, itaconic acid, mesaconic acid, maleic acid, fumaric acid, carboxyethyl (meth) acrylate, carboxypentyl (meta ) Acrylate, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxypropylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyl Preferred examples include loxyethyl succinic acid, 2- (meth) acryloyloxyethyl maleic acid, carboxypolycaprolactone mono (meth) acrylate, 2- (meth) acryloyloxyethyl tetrahydrophthalic acid and the like. Among them, (meth) acrylic acid is preferable and methacrylic acid is more preferable because it is inexpensive and easy to handle.

  In the present invention, “(meth) acrylate” refers to one or both of methacrylate and acrylate, and “(meth) acryloyl group” refers to one or both of methacryloyl group and acryloyl group. “Acrylic acid” refers to one or both of methacrylic acid and acrylic acid.

  In the production method 1, after obtaining a polymerizable monomer having a blocked hydroxyl group or carboxyl group, when the polymerizable monomer is polymerized, or in the production method 2, it has a hydroxyl group or a carboxyl group. When obtaining a polymer obtained using the polymerizable monomer (α), a polymerizable monomer (A) other than the polymerizable monomer (α) is used in combination as long as the effects of the present invention are not impaired. Thus, a polymer can be obtained. Examples of the polymerizable monomer (A) include acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters and the like.

  Examples of the acrylic acid esters include methyl acrylate, ethyl acrylate, propyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, trimethylolpropane monoacrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydro And furfuryl acrylate.

  Examples of the methacrylic acid esters include methyl methacrylate, ethyl methacrylate, propyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, trimethylolpropane monomethacrylate, benzyl methacrylate, methoxybenzyl methacrylate, furfuryl methacrylate, tetrahydro And furfuryl methacrylate.

  Examples of the acrylamides include acrylamide, N-alkylacrylamide (alkyl groups having 1 to 3 carbon atoms, such as methyl group, ethyl group, propyl group), N, N-dialkylacrylamide (as alkyl group). Are those having 1 to 3 carbon atoms), N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N-acetylacrylamide and the like.

  Examples of the methacrylamides include methacrylamide, N-alkyl methacrylamide (alkyl groups having 1 to 3 carbon atoms, such as methyl, ethyl, propyl), N, N-dialkyl methacrylamide ( Examples of the alkyl group include those having 1 to 3 carbon atoms), N-hydroxyethyl-N-methylmethacrylamide, N-2-acetamidoethyl-N-acetylmethacrylamide and the like.

  Examples of the allyl compound include allyl esters (eg, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc.) Examples include allyloxyethanol.

  Examples of the vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl 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, tetrahydrofurfuryl vinyl ether, etc., vinyl esters: vinyl vinylate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate ,vinyl Rate, vinyl caproate, vinyl chloroacetate, vinyl di- chloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl lactate, vinyl -β- phenyl butyrate, vinyl cyclohexyl carboxylate.

  Examples of the dialkyl itaconates include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate. Examples of dialkyl esters or monoalkyl esters of fumaric acid include dibutyl fumarate and the like, and also crotonic acid, itaconic acid, acrylonitrile, methacrylonitrile, maleilonitrile, styrene, and the like.

  Moreover, the radically polymerizable monomer which has an oxyalkylene group can also be used as a polymerizable monomer (A). Examples of the radical polymerizable monomer having an oxyalkylene group include 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 Cole) 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) acrylate, polytetraethylene glycol / polybutylene glycol mono (meth) acrylate, polybutylene glycol mono (meth) acrylate, poly (ethylene glycol / trimethylene glycol) mono (meth) acrylate, polyethylene Glycol / polytrimethylene 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, and the like.

  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. The same is true for the others.

  Examples of commercially available radical polymerizable monomers having an oxyalkylene group include “NK Ester AMP-10G”, “NK Ester AMP-20G”, and “NK Ester AMP-60G” manufactured by Shin-Nakamura Chemical Co., Ltd. “Blemmer PME-100”, “Blemmer PME-200”, “Blemmer PME-400”, “Blemmer PME-4000”, “Blemmer PP-1000”, “Blemmer PP-500”, manufactured by NOF Corporation “Blemmer PP-800”, “Blemmer 70PEP-350B”, “Blemmer 55PET-800”, “Blemmer 50POEP-800B”, “Blemmer 10PPB-500B”, “Blemmer NKH-5050”, “Blemmer AP-400”, Sartomer "SR604" made by the company That. The radical polymerizable monomer (γ) can be used alone or in combination of two or more.

  Furthermore, as the polymerizable monomer (A), a radical polymerizable monomer having a fluorinated alkyl group or a poly (perfluoroalkylene ether) chain can be used as long as the effects of the present invention are not impaired. Preferred examples of the radical polymerizable monomer include those represented by the following general formula (A0).

[In the general formula (A0), R represents a hydrogen atom or a methyl group, L represents one of the following formulas (L-1) to (L-10), and Rf represents the following formula (Rf -1) to 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 above formula (L-8 ), (L-9) and (L-10), m represents an integer of 1 to 8, and n represents an integer of 0 to 8. In the above formulas (L-6) and (L-7) Rf ″ represents any one of the following formulas (Rf-1) to (Rf-7).)

(In the above formulas (Rf-1) to (Rf-4), n is, for example, an integer of 1 to 6, preferably an integer of 4 to 6. m in the above formula (Rf-5) is 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 0 to 4 And the sum of m and n is 4 to 5. In the formula (Rf-6), m is an integer of 1 to 6, for example, n is an integer of 1 to 3, and l is 1 is an integer of 1 to 20, p is an integer of 0 to 5, and m, p, and the sum of products of n and l is 2 to 71. Preferably, m is an integer of 1 to 3. N is an integer of 1 to 3, 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 .)
Specific examples of the radical polymerizable monomer having a fluorinated alkyl group or a poly (perfluoroalkylene ether) chain include, for example, the following polymerizable monomers (A-1) to (A-15). It can be illustrated preferably.

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

  Examples of the vinyl ether compound represented by the general formula (IA) include 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, and the like. Among them, it is preferable because the reaction with the polymer obtained using the polymerizable monomer (α) easily proceeds and the difference in polarity before and after heating increases. In addition, from the viewpoint of the coating property of the polymerizable liquid crystal composition containing a polymer having a thermally decomposable group and the ease of lamination after film formation, 3,3,4,4,5,5,6,6,7, 7,8,8,8-Tridecafluoro-1-vinyloxyoctane is preferred.

  When obtaining the polymer having a thermally decomposable group of the present invention, a vinyl ether compound other than the compound represented by the general formula (IA) is converted into a vinyl ether compound represented by the general formula (IA) and It can also be used in combination as long as the effects of the present invention are not impaired. Examples of such vinyl ether compounds include aliphatic vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, and cyclohexyl vinyl ether; Aliphatic vinyl thioether compound; 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-2-ethoxy-2H-pyran, 3,4-dihydro-2H-pyran-2- Cyclic vinyl such as sodium carboxylate Ether compounds, cyclic vinyl thioether compounds corresponding to these.

  In the said manufacturing method 1, the polymerizable monomer ((alpha)) which has a carboxyl group, and the vinyl ether compound represented by the said general formula (IA) are made to react. As a result, a polymerizable monomer having a blocked carboxyl group is obtained. Examples of the reaction conditions include conditions for heating to about 20 to 100 ° C. in the presence of an acid catalyst. And when polymerizing the polymerizable monomer which has the blocked carboxyl group, it can carry out on the conditions on which the polymerizable monomer ((alpha)) mentioned later is polymerized.

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

  In the said manufacturing method 2, the said polymer and the vinyl ether compound represented by the said general formula (IA) can be made to react by heating to about 20-100 degreeC in presence of an acid catalyst, for example. . 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 the general formula (I-1-2) is obtained. As for the blocked carboxyl group, the blocked vinyl ether is removed under a high temperature environment, for example, in an environment of 150 to 300 ° C., and the carboxyl group is regenerated.

  The polymer having a thermally decomposable group is preferably a polymer having a structural unit selected from the following general formula (I-1-1-1) to general formula (I-1-2-2).

(In the above general formula (I-1-1-1) to general formula (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 represents a hydrogen atom or a methyl group, R ⁴² represents an organic group having a fluorine atom and / or a silicon atom, and n represents an integer of 0 to 12.)
The general formula (I-1-1-1) ~ the general formula ^(I-1-2-2), preferred groups ^{R 42} are the above-mentioned general formula (I-1-1) or the general formula (I-1 The same as the preferable group of R ⁴ described in 2).

  When the polymerizable liquid crystal composition containing the polymer having the thermally decomposable group is applied to a substrate, the polymer containing fluorine atoms and / or silicon atoms is segregated on the coating film surface. The water repellency and oil repellency of the film-forming surface obtained by the group having fluorine atoms and / or silicon atoms being detached from the polymer in a segregated state on the surface are lowered. As a result of such a phenomenon, it becomes easier to laminate another film on the film 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) is as follows. From the viewpoint of compatibility with the polymerizable liquid crystal compound to be used and solubility in the 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 2,000 to 2,000. The range of 8,000 is more preferable. The weight average molecular weight (Mw) is preferably in the range of 1,000 to 100,000, more preferably in the range of 5,000 to 70,000. The number average molecular weight (Mn) and the weight average molecular weight (Mw) are values converted to polystyrene based on gel permeation chromatography (hereinafter abbreviated as “GPC”) measurement.

  The polymer having a thermally decomposable group used in the present invention can be used alone or in combination.

The content of the polymer having a thermally decomposable group used in the present invention is based on 100 parts by mass of the total amount of the polymerizable liquid crystal compound, polymerizable chiral compound and polymerizable discotic compound contained in the polymerizable liquid crystal composition. 0.005 to 5 parts by mass, preferably 0.01 to 2 parts by mass, more preferably 0.05 to 1 part by mass, and 0.1 to 0.5 parts by mass. It is particularly preferable to use parts. By setting the content of the polymer having a thermally decomposable group to be contained in the polymerizable liquid crystal composition within a specific range, it can be applied uniformly and evenly on the substrate, and after coating on the substrate A laminate in which other layers are laminated on a film obtained by irradiation with active energy rays and baking 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 is a compound that exhibits liquid crystallinity alone or in a composition with another compound and has at least one polymerizable functional group. Conventional ones can be used.

  For example, Handbook of Liquid Crystals (D. Demus, JW Goodby, GW Gray, H. W. Spies, V. Vill, edited by Wiley-VCH, 1998), Quarterly Chemical Review No. 22, Liquid Crystal Chemistry (edited by the Chemical Society of Japan, 1994), or JP-A-7-294735, JP-A-8-3111, JP-A-8-29618, JP-A-11-80090, A rigid part called a mesogen in which a plurality of structures such as 1,4-phenylene group and 1,4-cyclohexylene group are connected as described in Kaihei 11-116538, JP-A-11-148079, etc. And a rod-like polymerizable liquid crystal compound having a polymerizable functional group such as a vinyl group, an acrylic group or a (meth) acryl group, or a maleimide as described in JP-A Nos. 2004-2373 and 2004-99446 Examples thereof include a rod-like polymerizable liquid crystal compound having a group. Among these, a rod-like liquid crystal compound having a polymerizable group is preferable because it can easily produce a liquid crystal having a temperature range around room temperature.

  Specifically, the polymerizable liquid crystal compound is preferably a compound represented by the following 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 is one or more halogen atoms, CN group, or alkyl group having 1 to 8 carbon atoms having a polymerizable functional group) each may be substituted, two or more CH ₂ groups that are not one CH ₂ group or adjacent present in this group, independently of one another by, -O -, - COO -, - OCO- Or may be replaced by -OCO-O-).
X ¹ represents —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═N—N═CH—, —CF═CF—, —C≡C— or a single bond (wherein P ² —S p ¹ and Sp ¹ -X ¹ do not include —O—O—, —O—NH—, —S—S— and —O—S— groups.
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. In the group, 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—, —CH═CH—, —CF═CF— or —C≡C— may be substituted, or R ² may have the general formula (II-a)

(Wherein 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 do not include —O—O—, —O—NH—, —S—S— and —O—S— groups.), Q ² is 0 Or 1).
The mesogenic group represented by MG has the general formula (II-b)

(In the formula, B1, 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-octahydrofetal Nantes -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 ′] diselenophen-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 one or more F, Cl, CF ₃ , OCF ₃ , CN groups, alkyl groups having 1 to 8 carbon atoms (the alkyl group) hydrogen atom in the group may be substituted with one or more phenyl groups, each of two or more CH ₂ groups not one CH ₂ group or adjacent existing independently of one another during this group -O-, -COO-, -OCO- or -OCO-O- Or an alkoxy group having 1 to 8 carbon atoms, an alkanoyl group having 1 to 8 carbon atoms, an alkanoyloxy group having 1 to 8 carbon atoms, or an alkoxycarbonyl group having 1 to 8 carbon atoms. , An alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, an alkenoyl group having 2 to 8 carbon atoms, an alkenoyloxy group having 2 to 8 carbon atoms, and / or a general formula ( II-c)

(Wherein 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 a single bond, ^{q 3} is 0 or 1, ^{q 4} represents 0 or 1. (However, P ⁴ -Sp ³ and Sp ³ -X ³ do not include —O—O—, —O—NH—, —S—S— and —O—S— groups). You may,
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 —, an alkyl group having 2 to 10 carbon atoms which may have a halogen atom or a single bond, r1 is 0, 1, 2 or 3 In the case where a plurality of B1 and Z1 are present, they may be the same or different. ).

P ² , P ³ and P ⁴ each independently represent a substituent selected from a polymerizable group represented by the following formula (P-2-1) to formula (P-2-20). preferable.

Among these polymerizable functional groups, from the viewpoint of increasing the polymerizability, the 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) preferable.

In the formula, P ² , Sp ¹ , X ¹ , q1 and MG each represent the same definition as in the general formula (II), and R ²¹ represents a hydrogen atom, a halogen atom, a cyano group, 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. A straight chain of 1 to 12 carbon atoms which may be substituted by-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF- or -C≡C-. A chain or branched alkyl group, a linear or branched alkenyl group having 1 to 12 carbon atoms, One or two or more hydrogen atoms may be substituted by a halogen atom or a cyano group, and when a plurality of hydrogen atoms are substituted, they may be the same or different. Examples of the general formula (II-2-1) include compounds represented by the following general formulas (II-2-1-1) to (II-2-1-4). The formula is not limited.

In the formula, P ² , Sp ¹ , X ¹ , and q ¹ each represent the same definition as in the general formula (II),
B11, B12, B13, B2, and B3 represent the same definitions as B1 to B3 in the general formula (II-b), and may be the same or different,
Z11, Z12, Z13 and Z2 represent the same definitions as Z1 to Z3 in the general formula (II-b), and may be the same or different,
R ²¹ represents a hydrogen atom, a halogen atom, a cyano group, one —CH ₂ —, or two or more non-adjacent —CH ₂ —, 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 -C≡C Represents a straight-chain or branched alkyl group having 1 to 12 carbon atoms or a straight-chain or branched alkenyl group having 1 to 12 carbon atoms, which may be substituted by-, one or two of the alkyl group or alkenyl group One or more hydrogen atoms may be substituted with a halogen atom or a cyano group. May be the same or different.

  Examples of the compounds represented by the general formulas (II-2-1-1) to (II-2-1-4) include the following formulas (II-2-1-1-1) to (II-2). The compound represented by (1-1-26) is exemplified, but not limited thereto.

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, and R ²¹ represents the above general formula (II-2-1-1) to ( II-2-1-4) represents the same definition, but R ²¹ represents a hydrogen atom, a halogen atom, a cyano group, one —CH ₂ — is —O—, —CO—, —COO—, It preferably represents a linear alkyl group having 1 to 6 carbon atoms or a linear alkenyl group having 1 to 6 carbon atoms, which may be substituted by -OCO-,
The cyclic group has one or more F, Cl, CF ₃ , OCF ₃ , CN groups, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and 1 to 1 carbon atoms as a substituent. An alkanoyl group having 8 carbon atoms, an alkanoyloxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, and a carbon atom The alkenoyl group having 2 to 8 carbon atoms and the alkenoyloxy group having 2 to 8 carbon atoms may be contained.

The total content of the monofunctional polymerizable liquid crystal compound having one polymerizable functional group in the molecule may be 0 to 90% by mass in the total amount of the polymerizable liquid crystal compound used in the polymerizable liquid crystal composition. The content is preferably 0 to 85% by mass, more preferably 0 to 80% by mass. When placing importance on the orientation of the optical anisotropic body, the lower limit value is preferably 5% by mass or more, more preferably 10% by mass or more, and when emphasizing the hardness of the coating film, the upper limit value. 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) preferable.

In the formula, P ² , Sp ¹ , X ¹ , q ¹ , MG, X ² , Sp ² , q ² , and P ³ each represent the same definition as 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). The formula is not limited.

In the formula, P ² , Sp ¹ , X ¹ , q ¹ , MG, X ² , Sp ² , q ² , and P ³ each represent the same definition as in the general formula (II),
B11, B12, B13, B2, and B3 represent the same definitions as B1 to B3 in the general formula (II-b), and may be the same or different,
Z11, Z12, Z13, and Z2 represent the same definitions as Z1 to Z3 in the general formula (II-b), and may be the same or different.

  Of 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, it is preferable because the orientation of the obtained optical anisotropic body is good and the curability is good. It is particularly preferable to use a compound represented by the general formula (II-2-2-2) having a ring structure.

  Examples of the compounds represented by the general formulas (II-2-2-1) to (II-2-2-4) include the following formulas (II-2-2-1-1) to (II-2). The compound represented by 2-1-21) is exemplified, but not limited thereto.

In the formula, R ^d and R ^e each independently represent a hydrogen atom or a methyl group,
The cyclic group has one or more F, Cl, CF ₃ , OCF ₃ , CN groups, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and 1 to 1 carbon atoms as a substituent. An alkanoyl group having 8 carbon atoms, an alkanoyloxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, and a carbon atom The alkenoyl group having 2 to 8 carbon atoms and the alkenoyloxy group having 2 to 8 carbon atoms may be contained.

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

  The liquid crystal compound having two polymerizable functional groups can be used alone or in combination of two or more, but preferably 1 to 5 types, more preferably 2 to 5 types.

The total content of the bifunctional polymerizable liquid crystal compound having two polymerizable functional groups in the molecule may be 10 to 100% by mass of the total amount of the polymerizable liquid crystal compound used in the polymerizable liquid crystal composition. The content is preferably 15 to 85% by mass, more preferably 20 to 80% by mass. When importance is attached to the hardness of the coating film, the lower limit value is preferably 30% by mass or more, more preferably 50% by mass or more, and when importance is placed on the orientation of the optical anisotropic body, the upper limit value. Is preferably 85% by mass or less, and more preferably 80% by 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 a 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 used. preferable.

^{Wherein, P 2, Sp 1, X} 1, q1, MG, X 2, Sp 2, q2, P 3, X 3, q4, Sp 3, q3, P 4 , respectively, the general formula (II) Represents the same definition. 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). The formula is not limited.

^{Wherein, P 2, Sp 1, X} 1, q1, MG, X 2, Sp 2, q2, P 3, X 3, q4, Sp 3, q3, P 4 , respectively, the general formula (II) Represents the same definition,
B11, B12, B13, B2, and B3 represent the same definitions as B1 to B3 in the general formula (II-b), and may be the same or different,
Z11, Z12, Z13, and Z2 represent the same definitions as Z1 to Z3 in the general formula (II-b), and may be the same or different.

  Examples of the compounds represented by the general formulas (II-2-3-1) to (II-2-3-8) include the following formulas (II-2-3-1-1) to (II-2). Although the compound represented by -3-1-6) is illustrated, it is not necessarily 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 are each independently a hydrogen atom, a halogen atom, or a carbon number of 1 to 6 An alkyl group, an alkoxy group having 1 to 6 carbon atoms, 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, Alternatively, the cyclic group may be substituted with one or two or more halogen atoms, and the cyclic group has one or more F, Cl, CF ₃ , OCF ₃ , CN groups, 1 to 8 carbon atoms as a substituent. An alkyl group, an alkoxy group having 1 to 8 carbon atoms, an alkanoyl group having 1 to 8 carbon atoms, an alkanoyloxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, and 2 to 2 carbon atoms. 8 alkenyl groups, carbon atoms Number 2-8 alkenyloxy group, alkenoyl group having 2 to 8 carbon atoms, which may have a alkenoyloxy group having from 2 to 8 carbon atoms.
m4 to m9 each independently represents an integer of 0 to 18, and n4 to n9 each independently represents 0 or 1.

  The polyfunctional polymerizable liquid crystal compound having three or more polymerizable functional groups can be used alone or in combination of two or more.

The total content of the polyfunctional polymerizable liquid crystal compound having three or more polymerizable functional groups in the molecule is 0 to 80% by mass of the total amount of the polymerizable liquid crystal compound used in the polymerizable liquid crystal composition. Is preferable, it is more preferable to contain 0-60 mass%, and it is especially preferable to contain 0-40 mass%. When importance is attached to the rigidity of the optical anisotropic body, the lower limit value is preferably 10% by mass or more, more preferably 20% by mass or more, and particularly preferably 30% by mass or more. When emphasizing low curing shrinkage, the upper limit is preferably 50% by mass or less, more preferably 35% by mass or less, and particularly preferably 20% by 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 use a mixture of a plurality of the polymerizable liquid crystal compounds. Curability of the optically anisotropic substance obtained when the above-mentioned at least one monofunctional polymerizable liquid crystal compound is used in combination with at least one bifunctional polymerizable liquid crystal compound and / or polyfunctional polymerizable liquid crystal compound is used. This is preferable because it improves the adhesion to the substrate and at least one monofunctional polymerizable liquid crystal compound and at least one bifunctional polymerizable liquid crystal compound are more preferably used in combination. Among them, when the polymerizable liquid crystal composition of the present invention is used as an optical anisotropic body, when the curability is to be further improved, the compound has three or more ring structures as a bifunctional polymerizable liquid crystal compound. A compound selected from (II-2-2-2) to (II-2-2-4) is preferably used as a mixture of polymerizable liquid crystal compounds, and the compound has three ring structures ( It is particularly preferable to use a mixture of the compound represented by II-2-1-2) and the compound represented by (II-2-2-2).

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 in the total amount of the polymerizable liquid crystal compound used in the polymerizable liquid crystal composition. It is especially preferable to set it as 80 mass%-100 mass%.
(Other liquid crystal compounds)
Further, the liquid crystal composition of the present invention may contain a compound containing a mesogenic group having no polymerizable group, such as a normal liquid crystal device such as STN (Super Twisted Nematic) liquid crystal, TN ( The compound used for a twisted nematic liquid crystal, TFT (thin film transistor) liquid crystal, etc. is mentioned.

  Specifically, the compound containing a mesogenic group having no polymerizable functional group is preferably a compound represented by the following general formula (5).

  The mesogenic group or mesogenic supporting group represented by MG3 has the 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 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- Octahydrof Enanthrene-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 ′] diselenophen-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 one or more F, Cl, CF ₃ , OCF ₃ , CN groups, C 1-8 alkyl groups, alkoxy groups as substituents , An alkanoyl group, an alkanoyloxy group, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group, an alkenoyl group, an alkenoyloxy 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-, an alkylene group which may have a halogen atom having 2 to 10 carbon atoms or a single bond;
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. may, independently each two or more CH ₂ groups not one CH ₂ group or adjacent present in this group to each other, in a manner that oxygen atoms are not directly bonded to each other, -O -, - S _{-, - NH -, - N} (CH 3) -, - CO -, - COO -, - OCO -, - OCOO -, - SCO -, - COS- or may be replaced by -C≡C- . ).

  Specifically, although shown below, it is not necessarily 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, or a cyano group, and these groups have 1 carbon atom. In the case of a -6 alkyl group or a C1-C6 alkoxy group, all may be unsubstituted or may be substituted by one 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. It is preferably at least mass%, preferably at least 5 mass%, more preferably at most 15 mass%, preferably at most 10 mass%.
(Other ingredients)
(Chiral compound)
The polymerizable liquid crystal composition in the present invention may contain a polymerizable chiral compound which may exhibit liquid crystallinity other than the polymerizable compound represented by the general formula (II) or may be non-liquid crystalline. it can.

  The polymerizable chiral compound used in the present invention preferably has one or more polymerizable functional groups. Examples of such compounds include JP-A-11-193287, JP-A-2001-158788, JP-T 2006-52669, JP-A-2007-269639, JP-A-2007-269640, 2009. -84178 and the like, including a chiral saccharide such as isosorbide, isomannite, glucoside, etc., and a rigid site such as a 1,4-phenylene group and a 1,4-cyclohexylene group, and a vinyl group A polymerizable chiral compound having a polymerizable functional group such as an acryloyl group, a (meth) acryloyl group or a maleimide group, a polymerizable chiral compound comprising a terpenoid derivative as described in JP-A-8-239666, NATURE VOL35 467-469 pages (November 30, 1995) Published), NATURE VOL 392, pages 476 to 479 (issued on April 2, 1998), or the like, or a polymerizable chiral compound comprising a mesogenic group and a spacer having a chiral moiety, or JP-T-2004-504285. And a polymerizable chiral compound containing a binaphthyl group as described in JP-A-2007-248945. Among these, a chiral compound having a large helical twisting power (HTP) is preferable for the polymerizable liquid crystal composition of the present invention.

  The compounding amount of the polymerizable chiral compound needs to be appropriately adjusted depending on the helical induction force of the compound, but it is preferably 0 to 25% by mass, preferably 0 to 20% by mass in the polymerizable liquid crystal composition. It is more preferable to contain, and it is especially preferable to contain 0-15 mass%.

  Examples of the general formula of the polymerizable chiral compound include general formulas (3-1) to (3-4), but are 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 is a carbon atom having one or more halogen atoms, a CN group, or a polymerizable functional group. may be substituted by an alkyl group having 1 to 8, two or more of CH ₂ groups, independently of one another each of the present in the radical is not one CH ₂ group or adjacent, each other oxygen atom in the form that does not bind directly _{to, -O -, - S -,} - NH -, - N (CH 3) -, - CO -, - COO -, - OCO -, - OCOO -, - SCO -, - COS- Or it may be replaced by -C≡C-
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, , 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-octahydro Fe Trento-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 ′] diselenophen-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 each independently represent 0 or 1, and 0 ≦ n + 1 + 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-, an alkyl group which may have a halogen atom having 2 to 10 carbon atoms or a single bond;
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. two or more CH ₂ groups not one CH ₂ group or adjacent present in the radical are each, independently of one another, in the form of 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,
Alternatively, R ^3a and R ^3b are represented by 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 ).
P ^3a preferably represents a substituent selected from a polymerizable group represented by the following formula (P-1) to formula (P-20).

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

  Specific examples of the polymerizable chiral compound include 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, R _{1 to} R ₄ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and 1 to 6 carbon atoms. An alkoxy group, a carboxy group, and a cyano group. When these groups are alkyl groups having 1 to 6 carbon atoms or alkoxy groups having 1 to 6 carbon atoms, all of them may be unsubstituted or substituted with one 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 crystallinity can also be used as the polymerizable liquid crystal compound. The polymerizable liquid crystal composition of the present invention can also contain a non-liquid crystalline polymerizable discotic compound.

  The polymerizable discotic compound used in the present invention preferably has one or more polymerizable functional groups. Examples of such compounds include polymerizable compounds described in, for example, JP-A-7-281028, JP-A-7-287120, JP-A-7-333431, and JP-A-8-27284. Is mentioned.

  Examples of the polymerizable discotic liquid crystal compound exhibiting liquid crystallinity as the polymerizable liquid crystal compound include compounds represented by the following general formula (III).

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

(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 generally May be substituted by a substituent represented by formula (III-b), general formula (III-c), or general formula (III-d), and at least R ⁸ present in general formula (III) One is substituted by a substituent represented by general formula (III-b), general formula (III-c), or general formula (III-d).

Wherein R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ , R ⁸⁵ , R ⁸⁶ , R ⁸⁷ , R ⁸⁸ and R ⁸⁹ are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 5 carbon atoms. N1 represents 0 or 1))
At least one of R ⁸ present in the general formula (III) is substituted with a substituent represented by the general formula (III-b), the general formula (III-c), or the general formula (III-d). However, all R ⁸ present in the general formula (III) is independently represented by the general formula (III-b), the general formula (III-c), or the general formula (III-d). It is preferably substituted by the substituent represented.

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

(In the formula, n2 represents an integer of 1 to 18.)
Preferred examples of the compound represented by the general formula (III) include compounds represented by the following general formula (III-1) and general formula (III-2).

(In General Formula (III-1) and General Formula (III-2), n represents an integer of 1 to 18)
As the polymerizable liquid crystal compound, one or more polymerizable discotic liquid crystal compounds exhibiting liquid crystallinity can be used.

  Only a polymerizable discotic liquid crystal compound can be used as the polymerizable liquid crystal compound, or a polymerizable rod-like liquid crystal compound and a polymerizable discotic liquid crystal compound can 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 crystallinity is determined based on the polymerizable liquid crystal compound used in the polymerizable liquid crystal composition. The total amount is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, and particularly preferably 20 to 80% by mass.

  Examples of general formulas of other polymerizable discotic compounds include general formulas (4-1) to (4-3), but are not limited to the following general formulas.

In the formula, Sp ⁴ represents an alkylene group having 0 to 18 carbon atoms, and the alkylene group is substituted with one or more halogen atoms, CN group, or an alkyl group having 1 to 8 carbon atoms having a polymerizable functional group. may be, independently each two or more CH ₂ groups not one CH ₂ group or adjacent present in this group to each other, in a manner that oxygen atoms are not directly bonded to each other, -O Replaced by —, —S—, —NH—, —N (CH ₃ ) —, —CO—, —COO—, —OCO—, —OCOO—, —SCO—, —COS— or —C≡C—. You may,
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 which may have a halogen atom having 2 to 10 carbon atoms or a single bond,
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 two or more CH ₂ groups not one CH ₂ group or adjacent to existing independently of one another each in the form of oxygen atoms are not directly bonded to each other, -O -, - S -, - NH-, _{-N (CH 3) -, -} CO -, - COO -, - OCO -, - OCOO -, - SCO -, - COS- or may be replaced by -C≡C-,
Or R ⁴ represents 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 ).
P ^4a preferably represents a substituent selected from a polymerizable group represented by the following formula (P-1) to formula (P-20).

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

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

In General Formula (4-4) to General Formula (4-6), n represents an integer of 1 to 18.
(Organic solvent)
An organic solvent may be added to the polymerizable liquid crystal composition in the present invention. Although there is no limitation in particular as an organic solvent to be used, the organic solvent in which a polymeric liquid crystal compound shows favorable solubility is preferable, and it is preferable that it is an organic solvent which can be dried at the temperature of 100 degrees 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, cyclohexanone, cyclohexane, and the like. Ketone solvents such as pentanone, ether solvents such as tetrahydrofuran, 1,2-dimethoxyethane and anisole, amide solvents such as N, N-dimethylformamide and N-methyl-2-pyrrolidone, propylene glycol monomethyl ether acetate , Diethylene glycol monomethyl ether acetate, γ-butyrolactone, chlorobenzene and the like. These can be used alone or in combination of two or more, but any one of ketone solvents, ether solvents, ester solvents and aromatic hydrocarbon solvents It is preferable to use the above from the viewpoint of solution stability.

  The composition used in the present invention can be applied to a substrate as an organic solvent solution, 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. However, the total amount of organic solvents contained in the polymerizable liquid crystal composition is preferably 10 to 95% by mass, more preferably 12 to 90% by mass, and particularly preferably 15 to 85% by mass. preferable.

  When the polymerizable liquid crystal composition is dissolved in the organic solvent, it is preferably heated and stirred in order to uniformly dissolve the polymerizable liquid crystal composition. 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 is preferably 15 ° C to 110 ° C, more preferably 15 ° C to 105 ° C from the viewpoint of productivity, 15 to 100 degreeC is further more preferable, and it is especially preferable to set it as 20 to 90 degreeC.

  Moreover, when adding a solvent, it is preferable to stir and mix with a dispersion stirrer. Specific examples of the dispersion stirrer include a disperser having a stirring blade such as a disper, a propeller, and a turbine blade, a paint shaker, a planetary stirring device, a shaker, a shaker, or a rotary evaporator. In addition, an ultrasonic irradiation apparatus can be used.

The stirring rotation speed when adding the solvent is preferably adjusted appropriately depending on the stirring device used, but in order to obtain a uniform polymerizable liquid crystal composition solution, the stirring rotation speed is preferably 10 rpm to 1000 rpm, preferably 50 rpm to 800 rpm is more preferable, and 150 rpm to 600 rpm is particularly preferable.
(Polymerization inhibitor)
It is preferable to add a polymerization inhibitor to the polymerizable liquid crystal composition in the present invention. Examples of the polymerization inhibitor include phenol compounds, quinone compounds, amine compounds, thioether compounds, nitroso compounds, and the like.

  Examples of phenolic compounds include 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-tert-butylphenol), 4.4′-thiobis (3-methyl-6-tert-butylphenol), 4-methoxy-1-naphthol, 4,4′- Dialkoxy-2,2′-bi-1-naphthol, and the like.

  As quinone compounds, hydroquinone, methylhydroquinone (MEHQ), tert-butylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, tert-butyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy-1, Examples include 4-naphthoquinone, 1,4-naphthoquinone, 2,3-dichloro-1,4-naphthoquinone, anthraquinone, and diphenoquinone.

  Examples of amine compounds include p-phenylenediamine, 4-aminodiphenylamine, N.I. N'-diphenyl-p-phenylenediamine, Ni-propyl-N'-phenyl-p-phenylenediamine, N- (1.3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N.I. N′-di-2-naphthyl-p-phenylenediamine, diphenylamine, N-phenyl-β-naphthylamine, 4.4′-dicumyl-diphenylamine, 4.4′-dioctyl-diphenylamine and the like.

  Examples of thioether compounds include phenothiazine and distearyl thiodipropionate.

  Examples of nitroso compounds include N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, N-nitrosodinaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol, and N, N-dimethyl. p-nitrosoaniline, p-nitrosodiphenylamine, p-nitronedimethylamine, p-nitrone-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, ditrosobenzene, 2,4.6-tri-tert-butylnitronebenzene, N-nitroso-N-methyl-p-toluenesulfonamide, N-nitroso-N-ethylurethane, N-nitroso-N- n-propyl urethane, 1-nitroso-2-naphthol, 2-nitroso 1-naphthol, sodium 1-nitroso-2-naphthol-3,6-sulfonate, sodium 2-nitroso-1-naphthol-4-sulfonate, Examples include 2-nitroso-5-methylaminophenol hydrochloride and 2-nitroso-5-methylaminophenol hydrochloride.

The addition amount of the polymerization inhibitor is preferably 0.01 to 1.0% by mass and more preferably 0.05 to 0.5% by mass with respect to the polymerizable liquid crystal composition.
(Antioxidant)
In order to improve 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, nitrosamine polymerization inhibitors, hindered phenol antioxidants, and more specifically, tert-butyl hydroquinone, methyl hydroquinone, manufactured by Wako Pure Chemical Industries, Ltd. “IRGANOX1010”, “IRGANOX1035”, “IRGANOX1076”, “IRGANOX1098”, “IRGANOX1135”, “IRGANOX1330”, “IRGANOX1425”, “IRGANOX1520”, “IRGANOX1726”, BASF Corporation “IRGANOX245”, “IRGANOX259”, “IRGANOX3114”, “IRGANOX3790”, “IRGANOX5057”, “IRGANOX565” And so on.

The addition amount of the antioxidant is preferably 0.01 to 2.0% by mass and more preferably 0.05 to 1.0% by mass with respect to the polymerizable liquid crystal composition.
(Photopolymerization initiator)
The polymerizable liquid crystal composition in the present invention preferably contains a photopolymerization initiator. It is preferable to contain at least one photopolymerization initiator. Specifically, “Irgacure 651”, “Irgacure 184”, “Irgacure 907”, “Irgacure 127”, “Irgacure 369”, “Irgacure 379”, “Irgacure 819”, “Irgacure 2959” manufactured by BASF Japan Ltd. , “Irgacure 1800”, “Irgacure 250”, “Irgacure 754”, “Irgacure 784”, “Irgacure OXE01”, “Irgacure OXE02”, “Lucirin TPO”, “Darocur 1173”, “Darocur MBF” and LAMBSON “Esacure 1001M”, “Esacure KIP150”, “Speed Cure BEM”, “Speed Cure BMS”, “Speed Cure MBP”, “Speed Cure PBZ”, “Speed Cure ITX”, “Speed” "Cure DETX", "Speed Cure EBD", "Speed Cure MBB", "Speed Cure BP", "Kaya Cure DMBI" manufactured by Nippon Kayaku Co., Ltd., "TAZ-" manufactured by Nippon Shibel Hegner Co., Ltd. (currently DKSH Japan Co., Ltd.) “A”, “Adekaoptomer SP-152”, “Adekaoptomer SP-170”, “Adekaoptomer N-1414”, “Adekaoptomer N-1606”, “Adekaoptomer N-” manufactured by ADEKA Corporation 1717 "," Adekaoptomer N-1919 "and the like.

The amount of the photopolymerization initiator used is preferably from 0.1 to 10% by weight, particularly preferably from 0.5 to 7% by weight, based on the polymerizable liquid crystal composition. These can be used alone or in combination of two or more, and a sensitizer or the like may be added.
(Thermal polymerization initiator)
In the polymerizable liquid crystal composition of the present invention, a thermal polymerization initiator may be used in combination with a photopolymerization initiator. Specifically, “V-40”, “VF-096” manufactured by Wako Pure Chemical Industries, Ltd., “Perhexyl D”, “Perhexyl I” of Nippon Oil & Fats Co., Ltd. (currently Nippon Oil Co., Ltd.) Etc.

The amount of the thermal polymerization initiator used is preferably from 0.1 to 10% by weight, particularly preferably from 0.5 to 5% by weight, based on the polymerizable liquid crystal composition. These can be used alone or in combination of two or more.
(Surfactant)
The polymerizable liquid crystal composition of the present invention may further contain at least one surfactant in a range that does not impair the effects of the present invention in order to reduce film thickness unevenness when an optically anisotropic substance is used. . Surfactants that can be included include alkyl carboxylates, alkyl phosphates, alkyl sulfonates, fluoroalkyl carboxylates, fluoroalkyl phosphates, fluoroalkyl sulfonates, polyoxyethylene derivatives, fluoro Examples thereof include alkylethylene oxide derivatives, polyethylene glycol derivatives, alkylammonium salts, fluoroalkylammonium salts and the like, and fluorine-containing surfactants are particularly preferable.

Specifically, "Megafuck F-251", "Megafuck F-444", "Megafuck F-477", "Megafuck F-510", "Megafuck F-552", "Megafuck F-""553","MegafuckF-554","MegafuckF-555","MegafuckF-556","MegafuckF-557","MegafuckF-558","MegafuckF-559" , “Megafuck F-560”, “Megafuck F-561”, “Megafuck F-562”, “Megafuck F-563”, “Megafuck F-565”, “Megafuck F-567”, “ “Megafuck F-568”, “Megafuck F-569”, “Megafuck F-570”, “Megafuck F-571”, “Megafuck R-40” , “Megafuck R-41”, “Megafuck R-43”, “Megafuck R-94”, “Megafuck RS-72-K”, “Megafuck RS-75”, “Megafuck RS-76-” E "," Megafuck RS-90 "(above, manufactured by DIC Corporation),
“Furgent 100”, “Furgent 100C”, “Furgent 110”, “Furgent 150”, “Furgent 150CH”, “Furgent A”, “Furgent 100A-K”, “Furgent 501”, "Factent 300", "Factent 310", "Factent 320", "Factent 400SW", "FTX-400P", "Factent 251", "Factent 215M", "Factent 212MH", "Footer Gent 250, Fategent 222F, Fategent 212D, FTX-218, FTX-209F, FTX-213F, FTX-233F, Fate 245F, FTX-208G ”,“ FTX-240G ”,“ FT -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 Corporation),
“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 "(manufactured by BYK Japan KK),
“TEGO Rad2100”, “TEGO Rad2200N”, “TEGO Rad2250”, “TEGO Rad2300”, “TEGO Rad2500”, “TEGO Rad2600”, “TEGO Rad2700” (above, manufactured by TEGO)
Examples include “N215”, “N535”, “N605K”, “N935” (above, manufactured by Solvay Solexis).

  The addition amount of the surfactant is preferably 0.01 to 2% by mass and more preferably 0.05 to 0.5% by mass with respect to the polymerizable composition.

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

  The polymerizable liquid crystal composition in the present invention is represented by the following general formula (7), which has an effect of effectively reducing the tilt angle of the air interface when the optical anisotropic body is used within a range not impairing the effects of the present invention. And a compound having a repeating unit having a weight average molecular weight of 100 or more.

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 one or more hydrogen atoms in the hydrocarbon group It may be substituted with a halogen atom.

  Suitable examples of the compound represented by the general formula (7) include polyethylene, polypropylene, polyisobutylene, paraffin, liquid paraffin, chlorinated polypropylene, chlorinated paraffin, and chlorinated liquid paraffin.

The amount of the compound represented by the general formula (7) is preferably 0.01 to 1% by mass and more preferably 0.05 to 0.5% by mass with respect to the polymerizable liquid crystal composition. preferable.
(Other additives)
Furthermore, in order to adjust the physical properties, additives such as polymerizable compounds that do not have liquid crystallinity, thixotropic agents, ultraviolet absorbers, infrared absorbers, antioxidants, surface treatment agents, etc., do not significantly reduce the alignment ability of liquid crystals. To the extent that can be added.
(Optical anisotropic body manufacturing method)
(Optical anisotropic)
The optical anisotropic body produced using the polymerizable liquid crystal composition of the present invention is obtained by sequentially laminating a base material, if necessary, an alignment film, and a polymer of the polymerizable liquid crystal composition.
(Base material)
The substrate used for the optical anisotropic body of the present invention is a substrate that is usually used for liquid crystal devices, displays, optical components and optical films, and is heated during drying after the application of the polymerizable liquid crystal composition of the present invention. If it is the material which has heat resistance which can endure, there will be no restriction | limiting in particular. Examples of such a substrate include organic materials such as a glass substrate, a metal substrate, a ceramic substrate, and a plastic substrate. In particular, when the substrate is an organic material, examples thereof include cellulose derivatives, polyolefins, polyesters, polycarbonates, polyacrylates (acrylic resins), polyarylate, polyether sulfone, polyimide, polyphenylene sulfide, polyphenylene ether, nylon, and polystyrene. Among them, plastic base materials such as polyester, polystyrene, polyacrylate, polyolefin, cellulose derivative, polyarylate, and polycarbonate are preferable, and base materials such as polyacrylate, polyolefin, and cellulose derivative are more preferable, and COP (cycloolefin polymer) is used as the polyolefin. It is particularly preferable to use TAC (triacetyl cellulose) as the cellulose derivative and PMMA (polymethyl methacrylate) as the polyacrylate. As a shape of a base material, you may have a curved surface other than a flat plate. These base materials may have an electrode layer, an antireflection function, and a reflection function as needed.

In order to improve the applicability and adhesiveness 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, silane coupling treatment, and the like. In addition, in order to adjust the light transmittance and reflectance, an organic thin film, an inorganic oxide thin film, a metal thin film, etc. are provided on the surface of the substrate by a method such as vapor deposition, or in order to add optical added value. The material may be a pickup lens, a rod lens, an optical disk, a retardation film, a light diffusion film, a color filter, or the like. Among these, a pickup lens, a retardation film, a light diffusion film, and a color filter that have higher added value are preferable.
(Orientation treatment)
In addition, the substrate is usually subjected to an alignment treatment or provided with an alignment film so that the polymerizable liquid crystal composition is aligned when the polymerizable liquid crystal composition of the present invention is applied and dried. Also good. Examples of the alignment treatment include stretching treatment, rubbing treatment, polarized ultraviolet visible light irradiation treatment, ion beam treatment, and the like. When the alignment film is used, a known and conventional alignment film is used. Such alignment films include polyimide, polysiloxane, polyamide, polyvinyl alcohol, polycarbonate, polystyrene, polyphenylene ether, polyarylate, polyethylene terephthalate, polyether sulfone, epoxy resin, epoxy acrylate resin, acrylic resin, coumarin compound, chalcone. Examples of the compound include compounds, cinnamate compounds, fulgide compounds, anthraquinone compounds, azo compounds, and arylethene compounds. The compound subjected to the alignment treatment by rubbing is preferably an alignment treatment or a compound in which crystallization of the material is promoted by inserting a heating step after the alignment treatment. Among the compounds that perform alignment treatment other than rubbing, it is preferable to use a photo-alignment material.

In the present invention, the substrate and the alignment-treated film using an alignment film may be collectively referred to as a substrate.
(Application)
Application methods for obtaining the optical anisotropic body of the present invention include applicator method, bar coating method, spin coating method, roll coating method, direct gravure coating method, reverse gravure coating method, flexo coating method, ink jet method, and die coating. A publicly known method such as a method, a cap coating method, a dip coating method, or a slit coating method can be used. The polymerizable liquid crystal composition is applied to a substrate and then dried as necessary.
(Polymerization process)
Regarding the polymerization operation of the polymerizable liquid crystal composition of the present invention, the liquid crystal compound in the polymerizable liquid crystal composition is generally ultraviolet rays in a state where the liquid crystal compound is horizontally aligned, vertically aligned, hybrid aligned, or cholesteric aligned (planar aligned) with respect to the substrate. Or the like, or by heating. When the polymerization is performed by light irradiation, specifically, it is preferable to irradiate ultraviolet light having a wavelength of 390 nm or less, and it is most preferable to irradiate light having a wavelength of 250 to 370 nm. However, when the polymerizable liquid crystal composition causes decomposition or the like due to ultraviolet light of 390 nm or less, it may be preferable to perform polymerization treatment with ultraviolet light of 390 nm or more. This light is preferably diffused light and unpolarized light.
(Polymerization method)
Examples of the method for polymerizing the polymerizable liquid crystal composition of the present invention include a method of irradiating active energy rays and a thermal polymerization method. However, since the reaction proceeds at room temperature without requiring heating, active energy rays are used. A method of irradiating is preferable, and among them, a method of irradiating light such as ultraviolet rays is preferable because the operation is simple.

The temperature at the time of irradiation is preferably set to 40 ° C. or less as much as possible in order to avoid the induction of thermal polymerization of the polymerizable liquid crystal composition so that the polymerizable liquid crystal composition of the present invention can maintain the liquid crystal phase. The liquid crystal composition usually has a liquid crystal phase in the range from the C (solid phase) -N (nematic) transition temperature (hereinafter abbreviated as C-N transition temperature) to the NI transition temperature in the temperature rising process. Indicates. On the other hand, in the temperature lowering process, a non-equilibrium state is taken thermodynamically, so that the liquid crystal state may be maintained without being solidified even at a temperature lower than 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 the state in which the liquid crystal phase is retained. Specifically, it is preferable to irradiate ultraviolet light of 390 nm or less, and it is most preferable to irradiate light having a wavelength of 250 to 370 nm. However, when the polymerizable composition causes decomposition or the like due to ultraviolet light of 390 nm or less, it may be preferable to perform the polymerization treatment with ultraviolet light of 390 nm or more. This light is preferably diffused light and unpolarized light. The ultraviolet irradiation intensity is preferably in the range of 0.05 kW / m ^{2 to} 10 kW / m ² . In particular, a 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 lot of time to complete the polymerization. On the other hand, when the strength exceeds ² kW / m ² , liquid crystal molecules in the polymerizable liquid crystal composition tend to be photodegraded, or a large amount of polymerization heat is generated to increase the temperature during polymerization. The parameter may change, and the retardation of the film after polymerization may be distorted.

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

  Further, when only a specific portion was polymerized by ultraviolet irradiation using a mask, the alignment was regulated in advance by applying an electric field, magnetic field or temperature to the unpolymerized polymerizable liquid crystal composition, and the state was maintained. An optical anisotropic body having a plurality of regions having different orientation directions can also be obtained by irradiating light from above the mask and polymerizing it.

The optical anisotropic body obtained by polymerizing the polymerizable liquid crystal composition of the present invention can be peeled off from the substrate and used alone as an optical anisotropic body, or it can be used as an optical anisotropic body as it is without peeling off from the substrate. You can also In particular, since it is difficult to contaminate other members, it is useful when used as a laminated substrate or by being attached to another substrate.
(Baking treatment of a polymer having a thermally decomposable group)
The optically anisotropic body produced through the coating step and the polymerization step using the polymerizable liquid crystal composition of the present invention requires a step (baking treatment) for heating in an environment of 180 to 300 ° C. When a polymer having a thermally decomposable group containing a fluorine atom and / or silicon atom is segregated on the surface of the optical anisotropic body, the optical anisotropic body contains a fluorine atom and / or silicon atom when heated. The thermally decomposable group part is detached from the polymer contained in the optical anisotropic body, and the water repellency and oil repellency of the film formation surface are lowered. As a result of such a phenomenon, it becomes easier to laminate another film on the film made of the polymerizable liquid crystal composition, and a laminate can be easily obtained. In order to remove the thermally decomposable group portion bonded to the polymer having a thermally decomposable group, it is preferable to perform a calcination treatment at 180 to 300 ° C. for 30 minutes, and a calcination treatment at 200 to 250 ° C. for 30 minutes. More preferred.
(Retardation film)
The retardation film of the present invention is prepared in the same manner as the optical anisotropic body of the present invention. The obtained retardation film can be used as a homogeneous liquid crystal film or the like. The liquid crystal device, the display, the optical element, the optical component, the colorant, the marking for security, the member for laser emission, the optical film, and the compensation film are formed in a form suitable for the application.

  As such a retardation film, for example, a positive A plate in which a rod-like liquid crystalline compound is substantially horizontally aligned with respect to a substrate, and a negative A plate in which a disk-like liquid crystalline compound is uniaxially aligned with respect to a substrate. A positive C plate in which rod-like liquid crystalline compounds are aligned substantially vertically with respect to the substrate, a rod-like liquid crystalline compound is cholesteric aligned with respect to the substrate, or a negative C in which disc-like liquid crystalline compounds are horizontally aligned uniaxially. An orientation mode of a plate, a biaxial plate, a positive O plate in which a rod-like liquid crystalline compound is hybrid-aligned with respect to a substrate, and a negative O plate in which a disc-like liquid crystalline compound is hybrid-aligned with respect to a substrate can be applied. When used in a liquid crystal display element, various orientation modes can be applied without particular limitation as long as the viewing angle dependency is improved.

  For example, orientation modes 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. Further, it is more preferable to stack a positive A plate and a negative C plate.

  Here, the positive A plate means an optical anisotropic body in which the polymerizable liquid crystal composition is homogeneously aligned. Moreover, a negative C plate means the optically anisotropic body which made the polymerizable liquid crystal composition the cholesteric orientation.

  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 compensate the viewing angle dependence of polarization axis orthogonality and widen the viewing angle. Here, when the positive A plate has a refractive index in the in-plane slow axis direction of the film as nx, a refractive index in the in-plane fast axis direction of the film as ny, and a refractive index in the thickness direction of the film as nz, The relationship is “nx> ny = nz”. The positive A plate preferably has an in-plane retardation value in the range of 30 to 500 nm at a wavelength of 550 nm. Moreover, the thickness direction retardation value is not particularly limited. The Nz coefficient is preferably in the range of 0.9 to 1.1.

  In order to cancel the birefringence of the liquid crystal molecules themselves, a so-called negative C plate having negative refractive index anisotropy is preferably used as the second retardation layer. Further, a negative C plate may be laminated on a positive A plate.

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

The refractive index anisotropy in the thickness direction is represented by a thickness direction retardation value Rth defined by the following formula (2). As the thickness direction retardation value Rth, an in-plane retardation value R ₀ , a retardation value R ₅₀ measured with a slow axis as an inclination axis and an inclination of 50 °, a film thickness d, and an average refractive index n ₀ of the film are used. Thus, nx, ny, and nz can be obtained by numerical calculation from the formula (1) and the following formulas (4) to (7), and these can be substituted into the formula (2). The Nz coefficient = can be calculated from the equation (3). The same applies to other descriptions in the present 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 the commercially available phase difference measuring device, the numerical calculation shown here is automatically performed in the device, and the in-plane retardation value _R0 , the thickness direction retardation value Rth, etc. are automatically displayed. There are many. An example of such a measuring apparatus is RETS-100 (manufactured by Otsuka Chemical Co., Ltd.).
(Phase difference patterning film)
The retardation patterning film of the present invention is obtained by sequentially laminating a substrate, an alignment film, and a polymer of a polymerizable liquid crystal composition in the same manner as the optical anisotropic body of the present invention. Are patterned so as to obtain different phase differences. The patterning may be in different directions, such as linear patterning, lattice patterning, circular patterning, polygonal patterning, and the like. The liquid crystal device, display, optical element, optical component, colorant, security marking, laser emission member, optical film, compensation film, and the like are used.

As a method of obtaining a partially different phase difference, an alignment film is provided on the substrate, and the polymerizable liquid crystal composition is patterned and aligned when the polymerizable liquid crystal composition of the present invention is applied and dried during the alignment treatment. To process. Examples of such an alignment treatment include a fine rubbing treatment, a polarized ultraviolet visible light irradiation treatment through a photomask, and a fine shape processing treatment. As the alignment film, known and conventional ones are used. Such alignment films include polyimide, polysiloxane, polyamide, polyvinyl alcohol, polycarbonate, polystyrene, polyphenylene ether, polyarylate, polyethylene terephthalate, polyether sulfone, epoxy resin, epoxy acrylate resin, acrylic resin, coumarin compound, chalcone. Examples of the compound include compounds, cinnamate compounds, fulgide compounds, anthraquinone compounds, azo compounds, and arylethene compounds. The compound subjected to the alignment treatment by fine rubbing is preferably an alignment treatment or a compound in which crystallization of the material is promoted by adding a heating step after the alignment treatment. Among the compounds that perform alignment treatment other than rubbing, it is preferable to use a photo-alignment material.
(Brightness enhancement film)
The brightness enhancement film of the present invention is a brightness enhancement film having a λ / 4 plate and a reflective polarizer, and the reflective polarizer has a first light reflection layer and a second light reflection layer from the λ / 4 plate side. And a third light reflecting layer in this order, and the first light reflecting layer, the second light reflecting layer and the third light reflecting layer are all light reflecting layers in which a cholesteric liquid crystal phase is fixed, A blue light reflection layer having a reflectance peak in which any one of the first light reflection layer, the second light reflection layer, and the third light reflection layer has a reflection center wavelength of 380 to 499 nm and a half width of 100 nm or less. Any one is a green light reflecting layer having a reflectance peak having a reflection center wavelength of 500 to 599 nm and a half-value width of 200 nm or less, and any one of them has a reflection center wavelength of 600 to 750 nm and a half-value width of 150 nm or less. Has a reflectance peak The red light reflecting layer is characterized in that the sign of Rth (550) of the first light reflecting layer is opposite to that of Rth (550) of the second light reflecting layer. With such a configuration, the brightness enhancement film of the present invention has high brightness and can suppress oblique color change when incorporated in a liquid crystal display device.
(Cholesteric reflective film)
The cholesteric reflective film of the present invention is a discarded lick reflective film composed of a cured product of a planar aligned polymerizable liquid crystal composition, and the polymerizable liquid crystal composition has only one polymerizable functional group. A chiral compound containing one or more liquid crystal compounds having a tolan skeleton, one or more liquid crystal compounds having two or more polymerizable functional groups, and one or more polymerizable functional groups 1 type or 2 types or more are contained and 1 or 2 types or more of polymerization initiators are contained. (Antireflection 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. A phase difference plate or the like is used when changing linearly polarized light into circularly polarized light, changing circularly polarized light into linearly polarized light, or changing the polarization direction of linearly polarized light. In particular, a so-called quarter-wave plate (also referred to as a λ / 4 plate) is used as a retardation plate that changes linearly polarized light into circularly polarized light or changes circularly polarized light into linearly polarized light. A half-wave plate (also referred to as a 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 of a reflective liquid crystal display device in which an image is displayed in color, and also has an antireflection function. Examples of the retardation plate include a liquid crystal polymer alignment film, a liquid crystal polymer alignment layer supported by a film, and the like. The retardation plate may have an appropriate retardation according to the purpose of use, such as those for the purpose of compensating for various wavelength plates or birefringence of the liquid crystal layer, viewing angle, and the like. What laminated | stacked the phase difference plate and controlled optical characteristics, such as phase difference, etc. may be used.
(Viewing angle compensation film)
The viewing angle compensation film of the present invention is a film for widening the viewing angle so that the image can be seen relatively clearly even when the screen of the liquid crystal display device is viewed from a slightly oblique direction rather than perpendicular to the screen. Examples of such a viewing angle compensation film include an alignment film such as a retardation film and a liquid crystal polymer, and a film in which an alignment layer such as a liquid crystal polymer is supported on a transparent substrate. A normal retardation film uses a birefringent polymer film or a uniaxially oriented liquid crystal polymer film that is uniaxially stretched in the plane direction, whereas a retardation film used as a viewing angle compensation film has a surface. A birefringent polymer film stretched biaxially in the direction, a polymer having a birefringence with a controlled refractive index in the thickness direction and uniaxially stretched in the plane direction and stretched in the thickness direction, and a tilted orientation film Such a bi-directionally stretched film is used. Examples of the tilted alignment film include a film obtained by obliquely aligning a liquid crystal polymer and a polymer film polymerized by active energy rays such as ultraviolet rays in a state where a polymerizable liquid crystal is obliquely aligned. An appropriate material is used for the purpose of preventing coloring or the like due to a change in the viewing angle based on the phase difference due to the liquid crystal cell and increasing the viewing angle for good viewing.

In addition, an optical compensation retardation plate in which an optically anisotropic layer made of a liquid crystal polymer tilted alignment film is supported by an optical film is preferably used from the viewpoint of achieving a wide viewing angle with good visibility.
(Reflective polarizing plate)
The reflective polarizing plate of the present invention is a reflective polarizing plate in which a cholesteric reflective film, an adhesive layer, and a linear polarizing film are sequentially laminated, and the cholesteric reflective film uses the cholesteric reflective film of the present invention. Further, one or more retardation films may be included in the reflective polarizing plate, and retardation films having different retardations may be used. Lamination of the retardation film is performed by bonding an adhesive or an adhesive film to the obtained retardation film, and then attaching the cholesteric reflective film of the present invention and the retardation film via an adhesive or an adhesive film. Obtained by pasting. In the case of using an adhesive or an adhesive film, known adhesives and adhesive films for optical film use are used.

Hereinafter, the present invention will be described with reference to synthesis examples, examples, and comparative examples, but the present invention is not limited to these examples. Unless otherwise specified, “part” and “%” are based on mass.
(Synthesis of fluorine-containing thermally decomposable polymer (D-1))
Into a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, 26.8 g of acrylic acid and 3,3,4,4,5,5,6,6,7,7,8,8,8- Tridecafluoro-1-vinyloxyoctane (30.0 g) was charged and stirred at room temperature for 21 hours in a dry air stream. Next, 0.003 g of methoquinone and 107.6 g of diisopropyl ether were added, and 161.4 g of a saturated aqueous sodium carbonate solution and 161.4 g of ion-exchanged water were added to separate the layers. Next, after taking out the upper layer, 161.4 g of ion-exchanged water was added for liquid separation. Furthermore, after taking out the upper layer, the solvent was removed to obtain a polymerizable monomer having a blocked carboxyl group.

A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 50 g of propylene glycol monomethyl ether acetate as a solvent, and the temperature was raised to 80 ° C. while stirring in 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 as a radical polymerization initiator are used. , 2'-azobis (methyl isobutyrate) 0.5g and a polymerization initiator solution in which 17g of propylene glycol monomethyl ether acetate was dissolved were set in separate dropping devices, and the flask was heated to 80 ° C. While maintaining, dropping was started simultaneously, and the monomer solution was dropped over 3 hours and the initiator solution was dropped over 4 hours. After completion of the dropwise addition, the mixture was stirred at 80 ° C. for 10 hours, and then propylene glycol monomethyl ether acetate was further added to obtain a propylene glycol monomethyl ether acetate solution containing 20% by mass of the fluorine-containing thermally decomposable resin (D-1) of the present invention. It was. As a result of measuring the molecular weight of the obtained fluorine-containing thermally decomposable resin by GPC (polystyrene equivalent molecular weight), the number average molecular weight was 2,900, the weight average molecular weight was 28,000, and the maximum molecular weight was 300,000.
(Synthesis of siloxane-containing thermally decomposable polymer (D-2))
In the following examples, a polymerizable monomer represented by the formula (D-2a) is synthesized by the same production method as the above (D-1) compound, and is represented by the (D-2a). A polymer (D-2) of a polymerizable monomer and propylene glycol polybutylene glycol monomethacrylate (number average molecular weight 2,500, weight average molecular weight 15,000, maximum molecular weight 160,000) was used.

Moreover, the following compounds were used as the compounds of (D-3) to (D-7).
BYK-352 (Bic Chemie Japan Co., Ltd.) (D-3)
TEGOFLOW ZFS-460 (Evonik Japan Co., Ltd.) (D-4)
Mega Fuck F-554 (manufactured by DIC Corporation) (D-5)
Megafuck F-447 (manufactured by DIC Corporation) (D-6)
Mega Fuck RS-75 (manufactured by DIC Corporation) (D-7)
(Preparation of polymerizable liquid crystal composition (1))
As shown in Table 1, 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) 0.1 part by mass of the compound (D-1), 5 parts by mass of the polymerization initiator (E-1), and paramethoxyphenol (MEHQ) (F-1) 0. Using 1 part by mass, using a stirrer having a stirring propeller using cyclopentanone (H-1) as an organic solvent so that the total amount of these compounds is 20% by mass, the stirring speed is 300 rpm. After stirring for 1 hour under the condition of a solution temperature of 80 ° C., the solution 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))
Similarly to the preparation of the polymerizable liquid crystal composition (1) of the present invention, (A-1) to (A-14), (B-1) to (B-11), and ( (C-1) to (C-5), (D-1) to (D-7), a compound represented by (E-1), a compound represented by (E-2), (F -1), the compound represented by (F-2), and the compound represented by the formula (G-1) are changed to the ratios shown in Tables 1 to 4, respectively, and the organic solvent Each of the polymerizable liquid crystal compositions is the same as the preparation of the polymerizable liquid crystal composition (1) except that the blending ratio of cyclopentanone (H-1) is changed to the ratios shown in Tables 1 to 4, respectively. (2) to (29) and comparative polymerizable liquid crystal compositions (C1) to (C3) were obtained.

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

Irgacure 907 (manufactured by BASF Japan Ltd.) (E-1)
Lucilin TPO (BASF Japan Ltd.) (E-2)
MEHQ (Wako Pure Chemical Industries, Ltd.) (F-1)
IRGANOX-1076 (BASF Japan Ltd.) (F-2)

(Manufacture of optical anisotropic body using polymerizable liquid crystal composition)
Example 1
The polyimide film for alignment film was applied to a glass substrate having a thickness of 0.7 mm using a spin coating method, dried at 100 ° C. for 10 minutes, and then baked 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 apparatus.

The polymerizable liquid crystal composition (1) of the present invention was applied to a rubbed substrate by spin coating at room temperature, dried at 80 ° C. for 2 minutes, and allowed to stand at room temperature for 2 minutes. Then, using a conveyor-type high-pressure mercury lamp, the coating film is polymerized by irradiating with UV light for 10 seconds under the condition of 50 mW / cm ² , and leveling properties and wettability of the obtained coating film surface are improved. Measurement was performed under the following conditions.

Thereafter, the coating film 0 obtained by the polymerization was baked at 230 ° C. for 30 minutes to obtain a coating film 1 (retardation film) of Example 1. Moreover, the retardation (Re) of the obtained coating film 1 was measured under the following conditions. Moreover, the wettability of the surface of the obtained coating film 1 was measured again.
<Evaluation of leveling properties>
The leveling property of the surface of the obtained coating film 0 was visually observed and evaluated as follows.
○: There is no repellency on the entire surface of the coating film by visual observation, and the surface is uniform and smooth.
Δ: The surface of the coating film is not repelled by visual observation, but has a partially unsmoothed surface state.
X: The surface of the coating film is repelled 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 coating film 1 was evaluated under the following conditions based on the contact angle of water. In the said evaluation, it represents that wettability is so good that the contact angle of water becomes low.
(Measurement conditions for contact angle) 3 μL of ultrapure water was dropped on the coating film 0 and the coating film 1. After the dropping, a photograph after 3000 ms was taken, and the contact angle was determined from the photographed droplet image using the θ / 2 method. As a measuring apparatus, “DropMaster 500” manufactured by Kyowa Interface Science Co., Ltd. was used.
<Measurement of phase difference (Re (θr))>
The phase difference in the θr = 0 ° direction of the obtained coating film 1 was measured with RETS-100. θr is the angle of incident light with respect to the coating surface, θr = 0 ° represents a direction perpendicular to the coating film, and θr = ± 50 ° represents a direction inclined by 50 ° from the vertical direction with respect to the coating film.

  The results are shown in the table below.

(Examples 2-18, Comparative Examples 1-2)
A coating film 1 (retardation film) was produced using the polymerizable liquid crystal compositions (2) to (18) and (C1) to (C3) under the same conditions as in Example 1. Further, Re (θr), leveling property, and wettability (before firing and after firing) were measured under the same conditions as in Example 1, and the results were taken as Examples 2 to 18 and Comparative Examples 1 and 2, and the above table. Shown in 5-7.
(Example 19)
The polymerizable liquid crystal composition (19) of the present invention was applied by spin coating at room temperature to a glass substrate on which a rubbed polyimide coating film formed in the same manner as in Example 1 was formed, and dried at 80 ° C. for 2 minutes. And left at room temperature for 2 minutes. Then, using a conveyor type high pressure mercury lamp, the coating film was polymerized by irradiating with UV light for 10 seconds under the condition of 50 mW / cm ² , and the coating film obtained by the polymerization was further heated to 230 ° C. Was baked for 30 minutes to obtain a coating film 1 which is a cholesteric reflective film having a thickness of 5.0 microns.

  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. Moreover, when the selective reflection wavelength of the obtained coating film 1 was measured using a spectrophotometer U-4100 (manufactured by Hitachi, Ltd.), the polarization reflection band was 265 nm.

  The results obtained are shown in the table below.

(Example 20 and Comparative Example 3)
A coating film 1 which is a cholesteric reflective film was produced using the polymerizable liquid crystal composition (20) of the present invention and the comparative polymerizable liquid crystal composition (C3) under the same conditions as in Example 19. Further, Re (θr), leveling property, wettability (before firing, after firing), and selective reflection wavelength were measured under the same conditions as in Example 19, and the results were taken as Example 20 and Comparative Example 3, and the results 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 thermally decomposable group has improved wettability after firing. This is because the polymer having a thermally decomposable group segregates on the surface of the coating film in the coating drying process, and the thermally decomposable group portion of the polymer imparting water repellency and oil repellency is removed in the subsequent baking process. It is considered that the surface energy of the coating film surface increased due to the separation. On the other hand, in Comparative Examples 1 to 3 using a surfactant that has been conventionally used as an additive, there is no significant difference in wettability before and after baking of the coating film. It is considered that there was no increase in the surface energy of the coating surface.
(Manufacture of laminates)
(Example 21)
The polyimide film for alignment film was applied to a glass substrate having a thickness of 0.7 mm using a spin coating method, dried at 100 ° C. for 10 minutes, and then baked 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 apparatus.

The polymerizable liquid crystal composition (1) of the present invention was applied to a glass substrate (substrate: glass with rubbing PI) on which a rubbed polyimide coating was formed by spin coating at room temperature, and dried at 80 ° C. for 2 minutes. Left at room temperature for 2 minutes. Then, using a conveyor type high pressure mercury lamp, the coating film was polymerized by irradiating with UV light for 10 seconds under the condition of 50 mW / cm ² , and the coating film obtained by the polymerization was further heated to 230 ° C. Were baked for 30 minutes to obtain a coating film 1 (retardation film) which is a positive A plate having a thickness of 0.6 microns.

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 left at room temperature for 2 minutes. . Then, using a conveyor type high-pressure mercury lamp, the coating film was polymerized by irradiating with UV light for 10 seconds under the condition of 50 mW / cm ² , and a 0.6 micron positive A plate and a thickness of 4. A coating film 2 (retardation film laminate) in which 0-micron negative C plates were laminated in this order was obtained. The repellency on the surface of the obtained coating film 2 was evaluated under the following conditions.
<Evaluation of repelling>
The repellency of the obtained coating film 2 was visually observed and evaluated as follows.
○: No repelling is observed on the entire surface of the coating film by visual observation.
Δ: Repelling is observed in part of the coating film by visual observation.
X: Repelling is observed 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)
Under the same conditions as in Example 21, the coating film 1 as a positive A plate was produced using the polymerizable liquid crystal compositions (2) to (10) and (C1) to (C2). Furthermore, the positive A plate and the negative C plate were used in this order on the coating film 1 which was the positive A plate using the polymerizable liquid crystal compositions (21) to (24) under the same conditions as in Example 21. A laminated coating film 2 was produced. The polymerizable liquid crystal composition used for coating film 1 and coating film 2 and the obtained results are shown in Table 9 above as Examples 22 to 32, Comparative Example 5 and Comparative Example 6.
(Example 33)
A coating film 1 which is a positive A plate having a thickness of 0.9 μm was produced using the polymerizable liquid crystal composition (1) under the same conditions as in Example 21, except that the spin coating conditions were changed. Next, a silane coupling material (manufactured by JNC: DMOAP) for a vertical alignment film is applied onto the coating film 1 which is a positive A plate by a spin coating method and baked at 100 ° C. for 1 hour. A vertical alignment film was formed thereon. A polymerizable liquid crystal composition (27) was applied onto the obtained vertical alignment film by a spin coating method and dried at 80 ° C. for 2 minutes. The obtained coating film was cooled to room temperature, and then irradiated with ultraviolet rays at an intensity of 50 mW / cm ² for 10 seconds using a high-pressure mercury lamp, a 0.9 micron thick positive A plate and a 1.0 micron thickness. A coating film 2 in which positive C plates were laminated in this order was prepared. When repelling of the surface of the obtained coating film 2 was confirmed in the same manner as in Example 21, no repelling was found on the entire surface of the coating film by visual observation.

  The results are shown in the table below.

(Examples 34 to 42)
The coating film 1 which is a positive A plate was produced using the polymerizable liquid crystal compositions (1) to (5) and (7) to (10) under the same conditions as in Example 33. Furthermore, the positive A plate and the positive C plate were used in this order on the coating film 1 as the positive A plate, using the polymerizable liquid crystal compositions (27) and (28) under the same conditions as in Example 33. The coating film 2 laminated | stacked by this was produced. The polymerizable liquid crystal composition used for coating film 1 and 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, coating film 1, which was a positive A plate having a thickness of 0.9 μm, was produced using polymerizable liquid crystal composition (2). Next, the prepared polymerizable liquid crystal composition (29) was applied on the coating film 1 as a positive A plate by spin coating at room temperature, dried at 80 ° C. for 2 minutes, and left at room temperature for 2 minutes. . Then, using a conveyor-type high-pressure mercury lamp, the coating film was polymerized by irradiating with UV light under the condition of 50 mW / cm ² for 10 seconds, and a positive A plate having a thickness of 0.9 microns and a thickness of A coating film 2 in which 1.0 micron positive O plates were laminated in this order was obtained. When repelling of the surface of the obtained coating film 2 was confirmed in the same manner as in Example 33, no repelling was found on the entire surface of the coating film by visual observation.
(Example 44)
5 parts of a 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 with a 0.45 μm membrane filter to obtain a photo-alignment solution (30).

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

  The results are shown in the table below.

(Examples 45 to 48)
Under the same conditions as in Example 44, coating film 1 as a positive C plate having a thickness of 1.0 μm was produced using polymerizable liquid crystal compositions (2) to (3) and (7). A photo-alignment film (1) is formed on the obtained coating film 1 under the same conditions as in Example 44. Further, using the polymerizable liquid crystal compositions (25) and (26), the thickness is 0.9 microns. A coating film 2 was prepared by laminating a positive A plate having a thickness of 1.8 microns and a positive A plate having a thickness of 1.8 microns in this order. This coating film 2 functioned as a circularly polarizing plate. The polymerizable liquid crystal composition used for coating film 1 and coating film 2 and the obtained results are shown in Table 11 above as Examples 45 to 48.
(Example 49)
A silane coupling material (manufactured by JNC: DMOAP) for a vertical alignment film was applied onto a glass substrate by a spin coating method and baked at 100 ° C. for 1 hour to form a vertical alignment film on the glass substrate. A polymerizable liquid crystal composition (11) was applied on the obtained vertical alignment film by a spin coating method and dried at 80 ° C. for 2 minutes. After the obtained coating film was cooled to room temperature, the coating film was polymerized by irradiating UV light with an intensity of 50 mW / cm ² for 10 seconds using a conveyor type high-pressure mercury lamp, and The coating film obtained by polymerization was baked at 230 ° C. for 30 minutes to obtain a coating film 1 which is a positive C plate having a thickness of 1.0 μm.

Next, the photo-alignment solution (30) was applied onto the coating film 1 using a spin coating method, dried at 80 ° C. for 2 minutes, and immediately irradiated with 313 nm linearly polarized light at an intensity of 10 mW / cm ² for 20 seconds. The photo-alignment film (1) was formed on the coating film 1. A polymerizable liquid crystal composition (25) was applied on the obtained photo-alignment film (1) by a spin coating method and dried at 80 ° C. for 2 minutes. The obtained coating film was cooled to room temperature, and then irradiated with ultraviolet light at an intensity of 50 mW / cm ² for 10 seconds using a high-pressure mercury lamp and a positive C plate having a thickness of 1.0 micron and a positive having a thickness of 0.9 micron. The coating film 2 which laminated | stacked C plate in this order was obtained. The repellency on 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 to 56)
Under the same conditions as in Example 49, the coating film 1 as a positive C plate having a thickness of 1.0 μm was produced using the polymerizable liquid crystal compositions (11) to (15). A photo-alignment film (1) is formed on the obtained coating film 1 under the same conditions as in Example 44. Further, the polymerizable liquid crystal compositions (25) and (26) are used, and the thickness is 1.0 micron. A coating film 2 was prepared by laminating a positive C plate and a positive A plate having a thickness of 0.9 microns in this order. The polymerizable liquid crystal composition used for coating film 1 and coating film 2 and the obtained results are shown in Table 12 above as Examples 50 to 56.
(Manufacture of transfer-type polarizing plate laminate)
(Example 57)
A silane coupling material (manufactured by JNC: DMOAP) for a vertical alignment film was applied onto a glass substrate by a spin coating method and baked at 100 ° C. for 1 hour to form a vertical alignment film on the glass substrate. A polymerizable liquid crystal composition (16) was applied onto the obtained vertical alignment film by a spin coating method and dried at 80 ° C. for 2 minutes. After the obtained coating film was cooled to room temperature, the coating film was polymerized by irradiating UV light with an intensity of 50 mW / cm ² for 10 seconds using a conveyor type high-pressure mercury lamp, and The coating film obtained by polymerization was baked at 230 ° C. for 30 minutes to obtain a coating film 1 as a positive O plate having a thickness of 0.5 μm.

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. Thereafter, the glass substrate was peeled off to obtain a transfer type viewing angle compensation polarizing plate on which the coating film 1 was laminated. 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 conducting a heat resistance test at 85 ° C. for 500 hours.
○: There is no peeled portion between the coating film 1 and the polarizing plate.
(Triangle | delta): There exists a part which peeled slightly between the coating film 1 and a polarizing plate.
X: There exists the part which peeled partially between the coating film 1 and a polarizing plate.

  The results are shown in the table below.

(Examples 58 to 60)
In the same manner as in Example 57, a transfer type viewing angle compensation polarizing plate which is a laminate of a hybrid alignment layer having a thickness of 0.5 microns and a polarizing plate is obtained using the polymerizable liquid crystal compositions (16) to (18). It was.

The results obtained are shown in Table 13 above.
(Reflective polarizing plate)
(Example 61)
The polymerizable liquid crystal composition (19) of the present invention was applied by spin coating at room temperature to a glass substrate on which a rubbed polyimide coating film formed in the same manner as in Example 21 was formed, and dried at 80 ° C. for 2 minutes. And left at room temperature for 2 minutes. Then, using a conveyor type high pressure mercury lamp, the coating film was polymerized by irradiating with UV light for 10 seconds under the condition of 50 mW / cm ² , and the coating film obtained by the polymerization was further heated to 230 ° C. Was baked for 30 minutes to obtain a coating film 1 which is a cholesteric reflective film having a thickness of 5.0 microns.

  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. Thereafter, the glass substrate was peeled off to obtain a reflective polarizing plate (laminate) on which a cholesteric reflective film was laminated. The heat-resistant peelability of the obtained reflective polarizing plate was measured in the same manner as in Example 57.

  The results obtained 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 cholesteric reflective film having a thickness of 5.0 microns was laminated using the polymerizable liquid crystal composition (20) of the present invention and the comparative polymerizable liquid crystal composition (C3). Got. The heat-resistant peelability of the obtained reflective polarizing plate was measured in the same manner as in Example 57.

  The results obtained 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 thermally decomposable group can be a laminate in which a further coating film is laminated on the coating film. Thus, it was clarified that the surface of the obtained laminate was excellent in leveling property and had excellent heat-resistant peelability.

Claims (17)

  A polymerizable liquid crystal composition comprising a polymer having at least one kind of thermally decomposable group and a polymerizable liquid crystal compound.   The polymerizable liquid crystal composition according to claim 1, wherein the thermally decomposable group contains a fluorine atom and / or a silicon atom. The thermally decomposable group is represented by 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 and R ² are each independently a hydrogen atom or a linear or branched carbon atom having 1 to 18 carbon atoms. Represents an organic group, 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. The polymerizable liquid crystal composition according to claim 1 or 2. The polymerizable liquid crystal compound has the general formula (II)

(Wherein 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 by one or more halogen atoms or CN, and one CH ₂ present in the group). Or two or more non-adjacent CH ₂ groups may each be independently replaced by —O—, —COO—, —OCO— or —OCO—O—).
X ¹ represents —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═N—N═CH—, —CF═CF—, —C≡C— or a single bond (wherein P ² —S p ¹ and Sp ¹ -X ¹ do not include —O—O—, —O—NH—, —S—S— and —O—S— groups.
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. In the group, 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—, —CH═CH—, —CF═CF— or —C≡C— may be substituted, or R ² may have the general formula (II-a)

(Wherein P ³ represents a polymerizable functional group,
Sp ² represents the same as defined in Sp ¹ ,
X ² represents the same as defined for X ¹ (where P ³ -Sp ² and Sp ² -X ² are -O-O-, -O-NH-, -S-S, respectively). -And -O-S- groups are not included).
q ² represents 0 or 1. ) Represents a group represented by )
The polymerizable liquid crystal composition according to any one of claims 1 to 3, which is a compound represented by the formula: In the general formula (II), MG represents the general formula (II-b).

(In the formula, B1, 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-octahydrofetal Nantes -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 ′] diselenophen-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 one or more F, Cl, CF ₃ , OCF ₃ , CN groups, alkyl groups having 1 to 8 carbon atoms (the alkyl group) hydrogen atom in the group may be substituted with one or more phenyl groups, each of two or more CH ₂ groups not one CH ₂ group or adjacent existing independently of one another during this group -O-, -COO-, -OCO- or -OCO-O- An alkoxy group, an alkanoyl group, an alkanoyloxy group, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group, an alkenoyl group, an alkenoyloxy group, and / or a compound represented by the general formula (II-c). )

(Wherein 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- represents, ^{q 3} is 0 or 1, ^{q 4} represents 0 or 1. (However, P ⁴ -Sp ³ and Sp ³ -X ³ do not include —O—O—, —O—NH—, —S—S— and —O—S— groups). You may,
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-, a halogen atom Represents an alkyl group having 2 to 10 carbon atoms or a single bond which may have,
r1 represents 0, 1 or 2, and when a plurality of B1 and Z1 are present, they may be the same or different. The polymerizable liquid crystal composition according to claim 4, which is a compound represented by The general formula (II) is the 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 (a hydrogen atom in the alkylene group). May be substituted by one or more halogen atoms, CN groups, or alkyl groups having 1 to 8 carbon atoms having a polymerizable functional group, and one CH ₂ group present in the group or adjacent thereto. Or two or more CH ₂ groups that are not, independently of one another, may be replaced 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 It represents ^(wherein, P 2 -S ^1, and ^S 1 ^-X 1 is, -O-O -, - O -NH -, -. Containing no S-S- and -O-S- group), q1 and q2 independently represents 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- , 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 '] Diselenophen-2,6-diyl group, [1] benzothieno [3,2-b] thiophene-2,7-diyl group, [1] benzoselenopheno [3,2-b] selenophene-2,7- Represents a diyl group or a fluorene-2,7-diyl group. As a substituent, one or more F, Cl, CF ₃ , OCF ₃ , CN group, an alkyl group having 1 to 8 carbon atoms, 1 to 1 carbon atom 8 alkoxy groups, alkanoyl groups having 1 to 8 carbon atoms, alkanoyloxy groups having 1 to 8 carbon atoms, alkoxycarbonyl groups having 1 to 8 carbon atoms, alkenyl groups having 2 to 8 carbon atoms, carbon atoms 2-8 alkenyloxy groups, 2-8 carbon atoms The alkenoyl group may have an alkenoyloxy group having 2 to 8 carbon atoms, and 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 —, a carbon atom optionally having a halogen atom An alkyl group having a number of 2 to 10 or a single bond is represented. The polymerizable liquid crystal composition according to claim 5, which is at least one compound selected from the group consisting of compounds represented by: The polymerizable liquid crystal compound has the general formula (III)

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

(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 generally May be substituted by a substituent represented by formula (III-b), general formula (III-c), or general formula (III-d), and at least R ⁸ present in general formula (III) One is substituted by a substituent represented by general formula (III-b), general formula (III-c), or general formula (III-d).

Wherein R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ , R ⁸⁵ , R ⁸⁶ , R ⁸⁷ , R ⁸⁸ and R ⁸⁹ are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 5 carbon atoms. And n represents 0 or 1.) The polymerizable liquid crystal composition according to any one of claims 1 to 3, which is a compound represented by the following formula:   A polymer obtained by polymerizing the polymerizable liquid crystal composition according to any one of claims 1 to 7.   An optically anisotropic body using the polymerizable liquid crystal composition according to any one of claims 1 to 7.   A retardation film formed using the polymerizable liquid crystal composition according to claim 1.   A retardation patterning film comprising the polymerizable liquid crystal composition according to claim 1.   The brightness improvement film which uses the polymeric liquid crystal composition as described in any one of Claims 1-7.   An antireflection film comprising the polymerizable liquid crystal composition according to any one of claims 1 to 7.   A viewing angle compensation film using the polymerizable liquid crystal composition according to any one of claims 1 to 7.   A retardation film obtained by laminating a negative C plate on the retardation film according to claim 10.   A retardation film obtained by laminating a positive C plate on the retardation film according to claim 10.   A retardation film obtained by laminating a positive A plate on the retardation film according to claim 10.