JP5291443B2 - Optically anisotropic thin film material and optically anisotropic thin film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymerizable polymer which can be subjected to development process with an aqueous alkaline solution. <P>SOLUTION: The polymer is prepared by polymerizing a monomer represented by formula (I) [wherein R<SB>1</SB>is H or CH<SB>3</SB>, A<SB>1</SB>and A<SB>2</SB>are a 1-4C alkylene group or a single bond, B<SB>1</SB>is OH or COOH, X<SB>1</SB>is a 1-18C alkylene, a 1-18C alkylene having C=O on the phenoxy side terminal, a 1-18C alkylene having a 1-6C alkylene bonded with the terminal opposite to the phenoxy side via a -COO- group, or a 1-18C alkylene having 1 to 10 -C<SB>2</SB>H<SB>4</SB>O- groups on the terminal opposite to the phenoxy side, and a and b are each an integer satisfying a+b=0 to 2] and a monomer represented by formula (II) [wherein R<SB>2</SB>is H or CH<SB>3</SB>, A<SB>3</SB>and A<SB>4</SB>are a 1-4C alkylene, -COO- or a single bond, Z<SB>1</SB>to Z<SB>3</SB>are a hydrogen, a halogen, CN, a 1-18C alkyl, or a 1-4C alkoxy, X<SB>2</SB>is a 1-18C alkylene, and c and d are each an integer satisfying c+d=0 to 2], reacting it with an epoxy group and an ethylenic double bond-containing compound, and esterifying it with a carboxylic acid anhydride. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to an optically anisotropic thin film material and an optically anisotropic thin film. More specifically, the present invention relates to a polymerizable polymer having an aromatic ring, a carbon-carbon double bond and a carboxyl group in the side chain, and a multifunctional product containing the same. The present invention relates to a liquid crystal composition, a polymerizable liquid crystal thin film, and an optically anisotropic thin film obtained by polymerizing the same.

  In recent years, optical films have been applied in various forms in the thin display field, particularly in the liquid crystal display field. For example, an optical anisotropic film (retardation film) is applied to the outside of a glass substrate of a liquid crystal display. ing. This is used to control the viewing angle, reflection, and color tone through compensation and control of birefringence by liquid crystal. However, these films are as thick as about 0.3 mm, which has begun to become a problem due to the recent preference for thinning in the thin display field.

When a polymerizable liquid crystal material having a type of optical anisotropy in which a polymerizable double bond site reacts with light or heat is polymerized using light or heat as a trigger, the optical properties before polymerization are fixed. For this reason, such a material can be made into a cured film having such orientation by giving a desired orientation in a liquid crystal state and then polymerizing it in a state in which the orientation characteristics are maintained. By using this technology, an optically anisotropic thin film layer can be provided inside the liquid crystal cell. Compared with the current technology in which a retardation film is attached to the outside of a liquid crystal glass substrate, the liquid crystal panel It is expected that merits such as reduction in thickness and cost will be obtained. Furthermore, by providing an optically anisotropic thin film layer with appropriate orientation characteristics for each predetermined pixel pixel, it is possible to improve the optical distortion and viewing angle dependent problems, contrast and brightness for each pixel pattern. become. For this reason, active research has also been conducted on so-called in-cell technology for forming an optically anisotropic thin film layer in a liquid crystal cell (for example, Patent Document 1).

Usually, a pixel pattern with a negative material is obtained by a photolithographic method in which exposure for causing a photoreaction and development processing for removing an unexposed portion that is not cured are performed. However, the photolithographic materials reported so far in the optically anisotropic thin film layer use an organic solvent as a developer, and are not materials that can meet the recent demands for workplace safety and environmental considerations. It was.

JP 2000-221506 A

  In the above background, the present invention provides a polymerizable polymer suitable for forming a pattern by development using an alkaline aqueous solution, a composition containing the polymerizable polymer, and a liquid crystal thin film obtained by polymerizing the polymerizable polymer. Objective.

The present inventor has proposed that an optical anisotropy having a property that meets the above-mentioned purpose when a specific range of a novel polymerizable polymer having an aromatic ring, a polymerizable double bond, and a carboxyl group in the side chain is polymerized. The inventors have found that a film can be provided, and have further studied to complete the present invention. That is, the present invention provides the following.
1. Formula (I):

[Wherein R ₁ is a hydrogen atom or a methyl group, A ₁ and A ₂ are each independently an alkylene group having 1 to 4 carbon atoms or a single bond, and B ₁ is a hydroxyl group or a carboxyl group. Yes, X ₁ is
(i) an alkylene group having 1 to 18 carbon atoms,
(ii) a C1-C18 alkylene group having a carbonyl group at the adjacent phenoxy side end,
(iii) a C 1-18 alkylene group having a C 1-6 alkylene group bonded to the terminal opposite to the phenoxy side via a —COO— group, or
(iv) an alkylene group having 1 to 18 carbon atoms and having 1 to 10 —C ₂ H ₄ O— groups connected in series to the terminal opposite to the phenoxy side,
a and b are 0 or a positive integer satisfying a + b = 0-2. A (meth) acrylic monomer (M1) represented by

Formula (II):

Wherein, R ₂ is a hydrogen atom or a methyl group, A ₃ and A ₄ are each independently an alkylene group having 1 to 4 carbon atoms, -COO- group, or a single bond, Z ₁ ~ Z ₃ is independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and X ₂ is an alkylene having 1 to 18 carbon atoms. C and d are 0 or a positive integer satisfying c + d = 0-2. ] A polymer (P1) obtained by polymerizing a monomer mixture containing a (meth) acrylic monomer (M2) represented by formula (1)] with an epoxy group and an ethylenic double bond-containing compound, and the hydroxyl group of the polymer (P1) Or a carboxyl group and an epoxy group are added to form a carbon-carbon double bond-containing polymerizable polymer (P2), which is converted into a monoester derivative by reaction with a carboxylic acid anhydride. Polymerizable polymer (P3).
2. The carboxyl group-containing product according to 1 above, wherein the epoxy group and the ethylenic double bond-containing compound are glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and 3,4-epoxycyclohexylmethyl (meth) acrylate. Polymerizable polymer (P3).
3. The carboxyl group-containing polymerizable polymer (P3) according to the above 1 or 2, wherein the reaction rate of the polymer (P1) with an epoxy group and an ethylenic double bond-containing compound is 60% or more.
4). A polyfunctional liquid crystal containing the carboxyl group-containing polymerizable polymer (P3) of any one of 1 to 3 above and a polyfunctional monomer having two or more ethylenically unsaturated bonds in one molecule. Polymer composition (PC).
5. The polyfunctional monomer has the formula (VI):

[Wherein, R ₁₆ is a hydrogen atom or a methyl group, R ₁₇ is an alkylene group having 1 to 18 carbon atoms, or a —COO— group and —OCO at the terminal opposite to the adjacent (meth) acryloyloxy side. -An alkylene group having 1 to 18 carbon atoms and any one of the groups, T ₁ is

(Z ₄ is a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms), Y ₁ is a single bond or —COO—, and Y ₁ ′ is a single bond or —OCO -. ] The polyfunctional liquid crystalline polymer composition (PC) described in 4 above, which is a polyfunctional liquid crystalline monomer represented by
6). 6. A photosensitive polymer composition for a liquid crystal panel, comprising the polyfunctional liquid crystalline polymer composition of 4 or 5 above.
7). A polymerizable thin film obtained by applying the polyfunctional liquid crystalline polymer composition of 4 or 5 above to a substrate surface.
8). An optically anisotropic thin film obtained by applying the 4 or 5 polyfunctional liquid crystalline polymer composition to a substrate surface and curing the composition.

  The polymer composition of the present invention having the above-described structure gives an optically anisotropic thin film by applying it to a substrate in a thin film form and exposing it. Further, a predetermined pattern composed of a cured liquid crystalline thin film can be formed by performing exposure through a predetermined mask or the like and curing, followed by treatment with an alkaline aqueous solution. Therefore, according to the composition of the present invention, a polymerizable liquid crystal thin film having excellent optical characteristics can be provided not only outside the liquid crystal cell but also inside the cell, which contributes to a reduction in thickness and cost of the liquid crystal panel.

1. Production of polymer P1 The following formula (I) is a monomer forming the polymer of the present invention:

In the (meth) acrylic monomer (M1), R ₁ is a hydrogen atom or a methyl group, and A ₁ and A ₂ are each independently an alkylene group having 1 to 4 carbon atoms or a single bond. More preferably, it is a single bond. B ₁ is a hydroxyl group or a carboxyl group, and more preferably a carboxyl group. X ₁ is (i) an alkylene group having 1 to 18 carbon atoms, (ii) an alkylene group having 1 to 18 carbon atoms having a carbonyl group at the phenoxy side terminal, and (iii) —COO at the terminal opposite to the phenoxy side. An alkylene group having 1 to 6 carbon atoms bonded via a group, or an alkylene group having 1 to 18 carbon atoms, or (iv) 1 to 10 —C bonded in series to the terminal opposite to the phenoxy side _A C 1-18 alkylene group having a ₂ H ₄ O— group, a and b are 0 or a positive integer satisfying a + b = 0-2, and from the viewpoint of optical anisotropy and heat resistance, More preferably, it is 0 or a positive integer satisfying a + b = 1 to 2.
Specific examples of the (meth) acrylic monomer represented by the formula (I) are shown below. In the present specification, “(meth) acrylic” represents “acrylic” and “methacrylic” without any particular distinction.

[Wherein, n represents an integer of 1 to 18, R ₁ represents a hydrogen atom or a methyl group, and G ₁ represents a carboxyl group. ]

[Wherein, n represents an integer of 1 to 18, R ₁ represents a hydrogen atom or a methyl group, and G ₁ represents a carboxyl group. ]

[Wherein, m represents an integer of 1 to 5, n represents an integer of 1 to 18, R ₁ represents a hydrogen atom or a methyl group, and G ₁ represents a carboxyl group. ]

[Wherein, n represents an integer of 1 to 18, R ₁ represents a hydrogen atom or a methyl group, and G ₁ represents a carboxyl group. ]

[Wherein, n represents an integer of 1 to 18, R ₁ represents a hydrogen atom or a methyl group, and G ₁ represents a hydroxyl group. ]

[Wherein, n represents an integer of 1 to 18, R ₁ represents a hydrogen atom or a methyl group, and G ₁ represents a carboxyl group. ]

  The following formula (II) which is a monomer forming the polymer of the present invention:

In the (meth) acrylic monomer (M2), R ₂ is a hydrogen atom or a methyl group, and A ₃ and A ₄ are each independently an alkylene group having 1 to 4 carbon atoms or a —COO— group. Or a single bond, and a —COO— group or a single bond is more preferable. Z _{1 to} Z ₃ are each independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and a cyano group is more preferable. X ₂ is an alkylene group having 1 to 18 carbon atoms, c and d are 0 or a positive integer satisfying c + d = 0 to 2, and 0 or a positive integer satisfying c + d = 1 to 2 is more preferable. preferable.

  Preferred examples of the (meth) acrylic monomer represented by the formula (II) are shown below.

[Wherein, n is an integer of 1 to 18, R ₂ is a hydrogen atom or a methyl group, and G ₂ is a cyano group. ]

[Wherein, n is an integer of 1 to 18, R ₂ is a hydrogen atom or a methyl group, and G ₂ is a cyano group. ]

[Wherein, n is an integer of 1 to 18, and R ₂ is independently a hydrogen atom or a methyl group. ]

[Wherein, n is an integer of 1 to 18, and R ₂ is independently a hydrogen atom or a methyl group. ]

  The polymerization of the monomers (M1 and M2) for producing the polymer (P1) may be performed without a solvent or may be performed by mixing in a solvent. The method of charging materials, solvents, etc. in the polymerization process is not particularly limited, and polymerization may be started after all the materials have been charged into the reaction vessel before polymerization, or a part of (meth) acrylic monomers, solvents, etc. May be added stepwise by the method such as dropwise addition or divided addition after the start of polymerization.

  In addition, other monomers may be included in the polymerization of the monomers (M1 and M2) for the production of the polymer (P1), but such monomers may be polymerizable ethylenically unsaturated. As long as it is a compound having a bond, it is not particularly limited in other respects and may not have liquid crystallinity.

  Such monomers include, for example, methyl (meth) acrylate, t-butyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, ethoxyethyl (meth) acrylate, hydroxyethyl (meth) acrylate, phenyl (Meth) acrylate, (meth) acrylic monomers such as N, N-dimethylacrylamide, styrene, α-methylstyrene, p-styrenesulfonic acid, ethyl vinyl ether, N-vinyl imidazole, vinyl acetate, vinyl pyridine, 2-vinyl naphthalene , Vinyl chloride, vinyl fluoride, N-vinylcarbazole, vinylamine, vinylphenol, vinyl monomers such as N-vinyl-2-pyrrolidone, 4-allyl-1,2-dimethoxybenzene, 4-allylphenol , 4-allyl-based monomer such as methoxy allyl benzene, phenyl maleimide, maleimide such as cyclohexyl maleimide.

  In the polymer (P1), the ratio of the monomer (M1 and M2) constituting the polymer is preferably in the range of 10:90 to 60:40 by weight ratio (M1: M2), and 20:80 to 50: A range of 50 is more preferable.

  When polymerizing in solution, a general-purpose organic solvent can be used without any particular limitation. Specific examples of the solvent include alcohol solvents such as ethanol, propanol and butanol, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and cyclopentanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate and the like. Ester solvents, ether solvents such as diethyl ether and diglyme, hydrocarbon solvents such as hexane, cyclohexane, methylcyclohexane, toluene and xylene, nitrile solvents such as acetonitrile, amide solvents such as N-methylpyrrolidone and dimethylacetamide Etc.

  A polymerization initiator can be used for the polymerization of the aromatic ring-containing polymer (AP). The polymerization initiator may be a commonly used one. Specific examples include azobisisobutyronitrile (AIBN), diethyl-2,2′-azobisisobutyrate (V-601), 2 , 2'-azobis (2,4-dimethylvaleronitrile), azo polymerization initiators such as dimethylazobismethylpropionate, peroxides such as benzoyl peroxide, potassium persulfate, hydrogen peroxide, lauroyl peroxide Examples thereof include polymerization initiators and persulfate polymerization initiators such as potassium persulfate and ammonium persulfate. Any of these polymerization initiators may be used alone, or two or more thereof may be used in combination.

  The temperature during the polymerization varies depending on the type of polymerizable monomer (PM), the type of polymerization solvent, the type of initiator, etc., but is preferably in the range of 40 to 150 ° C., more preferably 50 to 120 ° C.

  The polymerizable polymer of the present invention comprises the above aromatic ring-containing polymer (AP) and a cyclic monomer containing an epoxy skeleton having a side chain (Q) containing an ethylenically unsaturated bond, the former hydroxyl group and / or carboxyl. It can be obtained by an addition reaction (addition reaction) between the group and the latter epoxy ring. The temperature of the addition reaction varies depending on the type of cyclic monomer, the type of reaction solvent, the type of catalyst, etc., but is preferably in the range of 30 to 140 ° C, more preferably 40 to 120 ° C.

As a catalyst in the above addition reaction, amine catalysts such as octylamine, dimethylbenzylamine, dibutylamine, triethanolamine, benzylamine, triethylamine, tetramethylammonium chloride, tetraethylammonium chloride, trimethylbenzylammonium chloride, tetraethylammonium bromide , Triethylbenzylammonium chloride, tetraethylammonium acetate, tetra-n-butylammonium bromide, tetra-n-butylammonium iodide, triethylbenzylammonium bromide, diphenyliodonium bromide, triphenylsulfonium bromide, tri-n-octylsulfonium bromide, triphenyl Sulfonium chloride, Quaternary ammonium salts such as tiger ethyl ammonium bromide, trimethyl phosphine, triphenyl phosphine, tris (4-methylphenyl) phosphine, phosphorus-based catalysts such as chloro diphenyl phosphine and the like.

  The amount of catalyst used for the addition reaction is preferably 0.0001 to 0.1 mol, and 0.003 to 0.1 mol per mol of the cyclic monomer from the viewpoint of preventing coloring and suppressing by-products. More preferably, it is 05 mol.

2. Production of polymerizable polymer (P2) containing carbon-carbon double bond Production of polymerizable polymer P2 containing carbon-carbon double bond by the reaction of polymer P1 with an epoxy group and an ethylenic double bond-containing compound This is carried out by an ordinary addition reaction between a hydroxyl group or a carboxyl group and an epoxy group and an epoxy group of an ethylenic double bond-containing compound, and at the same time, a hydroxyl group is generated by ring opening of the epoxy group.

  In the above, examples of the “epoxy group and ethylenic double bond-containing compound” include aliphatic epoxy group-containing monomers and alicyclic epoxy group-containing monomers.

  Specific examples of the aliphatic epoxy group-containing monomer include glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, glycidyl itaconate, allyl glycidyl ether, methallyl glycidyl ether, and the like.

  Specific examples of the alicyclic epoxy group-containing monomer include 3,4-epoxycyclohexylmethyl methacrylate (trade name: Cyclomer M-100, manufactured by Daicel Chemical Industries), epoxidized cyclohexyl polylactone methacrylate (trade name: Cyclomer). M-101, manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl acrylate (trade name: Cyclomer A-200, manufactured by Daicel Chemical Industries), vinylcyclohexene monoepoxide, limonene monoepoxide, and the like.

A production scheme of the polymerizable polymer (P2) is schematically shown below as an example in the case of the polymer (P1) when B ₁ is a carboxyl group in the formula (I). Here, the wavy line extending from the main chain of the polymer represents a side chain portion derived from the monomer of formula (I) or formula (II).

  In this reaction, the usage ratio of the epoxy group and the ethylenic double bond-containing compound is 0.01 to 3.0 moles with respect to 1 mole of the unit of the formula (meth) acrylic monomer M1 constituting the polymer P1. More preferably, it is in the range of 0.1 to 2.1 mol, more preferably 0.2 to 1.3 mol.

  Further, the reaction rate between the (meth) acrylic monomer M1 unit in the polymer P1, the epoxy group and the ethylenic double bond-containing compound is preferably 60% or more, and more preferably 70% or more. Here, “reaction rate” is defined as follows.

3. Production of carboxyl group-containing polymerizable polymer (P3) Next, the polymerizable polymer P2 obtained above is subjected to an esterification reaction with a carboxylic acid anhydride. Examples of carboxylic acid anhydrides for ester reaction include maleic anhydride, succinic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, hymic anhydride, Dicarboxylic acid anhydrides such as octenyl succinic anhydride and tetrapropenyl succinic anhydride, tricarboxylic acid anhydrides such as trimellitic anhydride and methylcyclohexeric carboxylic acid anhydride, butanetetracarboxylic dianhydride, bicyclo [2.2.2 ] Octa-7-ene-2,3,5,6-tetracarboxylic dianhydride, tetralin dianhydride, pyromellitic dianhydride, biphenyl tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, Ethylene glycol bistrimellitic acid Things, can be used tetracarboxylic acid anhydrides such as diphenylsulfone tetracarboxylic dianhydride. Of these, maleic anhydride, succinic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, hymic anhydride, octenyl succinic anhydride, tetrapropenyl anhydride Dicarboxylic acid anhydrides such as succinic acid are particularly preferred from the viewpoint of developability. The hydroxyl group on the polymerizable polymer P2 side that reacts with the carboxylic acid anhydride is a reaction of the hydroxyl group or carboxyl group derived from the formula (I), which is a monomer of the polymer P1, with the epoxy group and the epoxy group of the ethylenic double bond-containing compound. Thus, it can be a hydroxyl group formed by ring opening of an epoxy group. Monoesterification may be performed between the hydroxyl group and the carboxylic acid anhydride by an esterification reaction according to a conventional method. As a result, one carboxyl group is imparted to the carbon-carbon double bond-containing polymerizable polymer P2 for each ester reaction with one molecule of carboxylic acid anhydride, and a carboxy group-containing polymerizable polymer (P3) is obtained.

  The carboxyl group-containing polymerizable polymer (P3) of the present invention preferably has an acid value of 160 or less, and more preferably 100 or less. This is because if the acid value is too high, the orientation and the transparency of the film are lowered.

  The carboxyl group-containing polymerizable polymer (P3) preferably has a double bond equivalent in the range of 200 to 3000, more preferably in the range of 300 to 2000. This is because if the double bond equivalent is too high, the heat resistance is lowered, and if it is too low, the orientation is lowered.

  The carboxyl group-containing polymerizable polymer (P3) of the present invention contains components usually contained in a polymerizable composition that causes polymerization by light or heat, such as a photoinitiator, an addition reaction catalyst, a surfactant, a solvent, and the like. It may be added as appropriate and provided in the form of a polymerizable polymer composition.

  The epoxy group-containing ethylenic double bond-containing compound that can remain unreacted in the carboxyl group-containing polymerizable polymer (P3) of the present invention is a small amount, for example, 30% by weight, based on the total carboxyl group-containing polymerizable polymer (P3). Less than, preferably less than 15% by weight, more preferably less than 10% by weight, the object of the present invention can be achieved even if it remains to some extent, and the remaining amount is not particularly limited as long as it remains.

  The content of these optional components is not particularly limited, but the photoinitiator is 0.01 to 30.0% by weight and the addition reaction catalyst is 0 to 1.0% by weight based on the total weight of the polymerizable polymer composition. The surfactant is preferably contained in the range of 0 to 10.0% by weight and the organic solvent in the range of 0 to 90.0% by weight.

4). Production of polyfunctional liquid crystalline polymer composition (PC) The polyfunctional liquid crystalline polymer composition (PC) has the above carboxyl group-containing polymerizable polymer and two or more ethylenically unsaturated bonds in one molecule. It is a composition comprising a polyfunctional monomer, and can be obtained by stirring and mixing them uniformly. Mixing such a polyfunctional monomer with a polymerizable polymer is useful for improving alignment stabilization and film formation stabilization.

  Examples of polyfunctional monomers having two or more ethylenically unsaturated bonds in one molecule include polyfunctional (meth) acrylate monomers, polyfunctional (meth) acrylamide monomers, polyfunctional vinyl monomers, and polyfunctional allyl monomers. Can be mentioned.

  Specific examples of polyfunctional (meth) acrylate monomers include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetradecaethylene glycol di (meth) acrylate, dipropylene glycol Di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. It is below.

  Specific examples of the polyfunctional (meth) acrylamide monomer include polyfunctional (meth) acrylamide synthesized from N, N′-methylenebisacrylamide, ethylenediamine, phenylenediamine, and the like.

  Specific examples of the polyfunctional vinyl monomer include divinylbenzene, ethylene glycol divinyl ether, divinyl adipate, divinyl succinate and the like.

  Specific examples of the polyfunctional allyl monomer include diallyl phthalate, diallyl ether, diallyl malonate, p-allyl styrene, and the like.

  As the polyfunctional monomer, a polyfunctional (meth) acrylate monomer is more preferable, and among them, a polyfunctional liquid crystal monomer represented by the formula (VI) is particularly preferable, and examples thereof include the following. Any of these polyfunctional monomers may be used alone, or two or more thereof may be used in combination.

[Wherein, n is an integer of 1 to 18, and R is a hydrogen atom or a methyl group. ]

[Wherein, n is an integer of 1 to 18, R is a hydrogen atom or a methyl group, Z is a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms. ]

[Wherein, n is an integer of 1 to 18, R is a hydrogen atom or a methyl group, Z is a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms. ]

  The polyfunctional liquid crystalline polymer composition (PC) of the present invention may contain a general-purpose photopolymerization initiator generally known for forming a uniform film by irradiation with a small amount of light.

Specific examples of the photopolymerization initiator include α-aminoketone photopolymerization initiators such as Irgacure 907 (Ciba Specialty Chemicals), Irgacure 369 (Ciba Specialty Chemicals), 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino- Acetophenone-based photopolymerization initiators such as 1- (4-morpholinophenyl) -butan-1-one, benzoin-based light such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyldimethyl ketal Benzophenone photopolymerization initiators such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 2-chlorothio Thioxanthone photopolymerization initiators such as xanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6 -Bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) ) -S-triazine, 2-piperonyl-4,6-bi S (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s- Triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloro Triazine-based photopolymerization initiators such as methyl (4′-methoxystyryl) -6-triazine, carbazole-based photopolymerization initiators, imidazole-based photopolymerization initiators, and the like; and α-acyloxyesters, acylphosphine oxides, Methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4 ' Diethyl isophthalophenone phenone, 3,3 ', 4,4'-tetra (t- butylperoxycarbonyl) benzophenone, 4,4'-diethylamino benzophenone photopolymerization initiators such as thioxanthone and the like. Any of the photopolymerization initiators may be used alone, or two or more of them may be used in combination.

  The polyfunctional liquid crystalline polymer composition (PC) of the present invention may contain a general-purpose surfactant in order to form a uniform film. Surfactants include, for example, sodium lauryl sulfate, ammonium lauryl sulfate, triethanolamine lauryl sulfate, polyoxyethylene alkyl ether sulfate, alkyl ether phosphate, sodium oleyl succinate, potassium myristate, potassium coconut oil, sodium lauroyl Anionic surfactants such as sarcosinate; Nonionic surfactants such as polyethylene glycol monolaurate, sorbitan stearate, glyceryl myristate, glyceryl dioleate, sorbitan stearate, sorbitan oleate; stearyl trimethylammonium chloride, chloride Chatin such as behenyltrimethylammonium, stearyldimethylbenzylammonium chloride, cetyltrimethylammonium chloride Surfactants; amphoteric surfactants such as alkylbetaines such as laurylbetaine, alkylsulfobetaine, cocamidopropylbetaine, alkyldimethylaminoacetic acid betaine, alkylimidazolines, sodium lauroyl sarcosine, sodium cocoamphoacetate; and BYK-361, Surfactants such as BYK-306, BYK-307 (manufactured by Big Chemie Japan Co., Ltd.), Florard FC430 (manufactured by Sumitomo 3M Co., Ltd.), Megafac F171, R08 (manufactured by Dainippon Ink & Chemicals, Inc.) and the like can be mentioned. Any of these surfactants may be used alone, or two or more thereof may be used in combination.

  By using the polyfunctional liquid crystalline polymer composition (PC) of the present invention, a thin film for electronic devices having excellent thermal stability can be produced. Although it illustrates below, the manufacturing method is not limited to these.

  In order to produce a thin film, for example, the polyfunctional liquid crystalline polymer composition of the present invention is applied directly to a substrate such as a film or diluted by adding a solvent, and the solvent is removed to form a liquid crystal layer. Alternatively, the liquid crystal layer may be fixed by curing by light irradiation. As a coating method of the polyfunctional liquid crystalline polymer composition, any method generally known in the art may be used, for example, spin coating method, bar coating method, die coater method, screen printing method, spray coater. There are laws. After application of the composition, the solvent is removed to form a liquid crystal layer that is a layer of the composition. Any method may be used for solvent removal until the resin layer is fixed in a fixed form. The coating film that has undergone the drying step may be further photopolymerized after further heat treatment.

  Preferred examples of the solvent include toluene, ethylbenzene, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, propylene glycol methyl ether, dibutyl ether, acetone, methyl ethyl ketone, ethanol, propanol, cyclohexane, cyclopentanone, methylcyclohexane, tetrahydrofuran, cyclohexanone, n- Examples include hexane, ethyl acetate, butyl acetate, propylene glycol methyl ether acetate, methoxybutyl acetate, N-methylpyrrolidone, and dimethylacetamide. Any of these may be used alone or in combination of two or more.

  Examples of usable base materials include glass base materials such as alkali glass and non-alkali glass, polyimide, polyamide, acrylic resin, polyvinyl alcohol, triacetyl cellulose, polyethylene terephthalate, polyethylene, polycarbonate, polystyrene, and poly (trifluorotrifluoroethylene). Resin base materials such as iron, aluminum, copper and the like, and glass substrates are more preferable. The substrate is preferably a substrate that does not change in properties even when heated to a high temperature of 200 ° C. or higher.

  The heat treatment of the coating film is preferably performed under the condition that the uniform orientation of the liquid crystal is obtained. As a heat treatment method, for example, there is a method in which the coating film is heated to a temperature at which the orientation becomes uniform and then cooled. In the heat treatment, a temperature range of 20 ° C. to 120 ° C. is more preferable, and a temperature range of 50 ° C. to 100 ° C. is more preferable. From the viewpoint of production efficiency, the heat treatment is more preferably in the range of 10 seconds to 3 hours, and more preferably in the range of 30 seconds to 20 minutes.

As a light source used for light irradiation, a xenon lamp, a high-pressure mercury lamp, an excimer laser, a sodium lamp, a halogen lamp, black light, electron beam irradiation, and the like can be used.
Although the wavelength of light is not limited, 150-800 nm is more preferable and 180-600 nm is still more preferable.
The amount of light is not limited by the photopolymerization initiator, and is preferably 20 to 5000 mJ / cm 2, and more preferably 100 to 1500 mJ / cm 2.

  The thickness of the thin film of the present invention is more preferably in the range of 0.1 to 20.0 μm, and further preferably in the range of 1.0 to 5.0 μm.

  The thin film produced by the method of the present invention can be suitably used for improving the image quality of a liquid crystal screen as an optical film or the like. In particular, the composition of the present invention can be formed on the entire surface of the substrate of the liquid crystal display panel, or a thin film can be independently formed at a specific location (pixel) on the substrate.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, it is not intended that the present invention be limited to the examples.

1. Synthesis of polymer (P1) [Example 1] Synthesis of polymer (W-1) (monomer composition ratio, I-a1: II-a1 = 40: 60) Formula (I-a1):

[Wherein n is 6 and G ₁ is a carboxyl group. ] 4.0 g (0.011 mol) of an acrylic monomer represented by the formula (II-a1):

[Wherein n is 6 and G ₂ is a cyano group. ] A solution obtained by mixing 6.0 g (0.017 mol) of the acrylic monomer represented by the above and 30.0 g of cyclohexanone was stirred and mixed in a nitrogen stream for 1 hour. Thereafter, when the mixed solution was heated and the liquid temperature reached 75 ° C., 0.10 g of a polymerization initiator azobisisobutyronitrile (AIBN) was added and the polymerization reaction was carried out at a temperature range of 75 to 85 ° C. for 8 hours. I was allowed to do. As a result, 40.1 g of the polymer composition [containing 10.0 g of the aromatic ring-containing polymer (W-1)] is contained. 〕was gotten.

<Measurement of weight average molecular weight (MW)>
The weight average molecular weight (MW) of the polymer (W-1) was measured using gel filtration chromatography (GPC). The weight average molecular weight (MW) of the obtained aromatic ring-containing polymer was 18000.

<Measurement of acid value>
The measuring method is as follows. That is, about 60 ml of ethanol was taken in a 100 ml Erlenmeyer flask and neutralized with a 0.1 mol / l sodium hydroxide aqueous solution using phenolphthalein as an indicator. About 1.5 g of the polymer composition is precisely weighed, uniformly dissolved in the above solution, stirred, titrated with a 0.1 mol / l aqueous sodium hydroxide solution, and the titration end point is the point where the faint red color does not disappear for about 30 seconds. .
The acid value was calculated according to the following formula.
Acid value = (0.1 × f × A × 56.1 / B) / (C / 100)
A: Titration volume (ml)
f: Factor B of sodium hydroxide aqueous solution: Polymer composition amount (g)
C: Polymer concentration (%)
(Amount of polymer / Amount of polymer composition × 100)
The acid value of the polymer (W-1) was 61 mgKOH / g.

Example 2 Synthesis of Polymer (W-2) (Monomer Composition Ratio, I-a1: II-a1 = 20: 80) The amount of the (meth) acrylic monomer represented by the formula (Ia) used was 2.0 g. The same procedure as in Example 1 was performed except that the amount of the (meth) acrylic monomer represented by the formula (II-a) was changed to 8.0 g (0.023 mol) at (0.005 mol).
The obtained polymer (W-2) had a weight average molecular weight (MW) of 14,000 and an acid value of 28 mgKOH / g.

Example 3 Synthesis of Polymer (W-3) (Monomer Composition Ratio, I-a1: II-a1 = 30: 70) The amount of the (meth) acrylic monomer represented by the formula (Ia) used was 3.0 g ( 0.008 mol) was carried out in the same manner as in Example 1 except that the amount of the (meth) acrylic monomer represented by the formula (II-a) was changed to 7.0 g (0.020 mol).
The obtained polymer (W-3) had a weight average molecular weight (MW) of 14,000 and an acid value of 45 mgKOH / g.

2. Synthesis of polymerizable polymer (P2) [Addition reaction of epoxy group and ethylenic double bond-containing compound to epoxy group]
[Example 4] Synthesis of polymerizable polymer (X-1) (monomer composition ratio = 40:60) 40.1 g of polymer composition (monomer composition ratio = 40:60) synthesized in Example 1 [fragrance Ring-containing polymer (W-1) 10.0 g] is heated with stirring, and at a liquid temperature of 60 ° C., glycidyl methacrylate (GMA) 1.54 g (0.011 mol: MW 142), polymerization inhibitor hydroquinone monomethyl ether ( MEHQ) (0.006 g) and esterification catalyst dimethylbenzylamine (0.019 g, 0.000143 mol) were added, and heating was continued thereafter to react in a reaction temperature range of 95 to 105 ° C. When the acid value reaction rate reached 90.0% or more, the reaction solution temperature was cooled to 30 ° C. or less, and the reaction was completed. Thereafter, 4.43 g of cyclohexanone was added with stirring to obtain 46.16 g of a polymerizable polymer composition (including 11.43 g of polymerizable polymer (X-1)). The weight average molecular weight (MW) of the obtained polymerizable polymer was 24000, and the acid value was 4 mgKOH / g.

The acid value reaction rate was calculated according to the following formula.

  As a result, the acid value reaction rate of the product was 93%.

<Measurement of double bond equivalent>
The double bond equivalent (polymer weight per 1 mol of ethylenically unsaturated groups) of the polymerizable polymer (X-1) was calculated according to the following formula.

  As a result, the double bond equivalent was 1134.

[Example 5] Synthesis of polymerizable polymer (X-2) (monomer composition ratio = 20:80) 40.1 g of aromatic ring-containing polymer (monomer composition ratio = 20:80) synthesized in Example 2 [Aroma The ring-containing polymer (W-2) 10.0 g] is heated with stirring, and at a liquid temperature of 60 ° C., glycidyl methacrylate (GMA) 0.77 g (0.0054 mol: MW 142), polymerization inhibitor hydroquinone monomethyl ether 006 g and 0.0093 g (0.000070 mol) of the esterification catalyst dimethylbenzylamine were added, and then the heating was continued to react at a reaction temperature of 95 to 105 ° C. When the acid value reaction rate reached 90.0% or more, the reaction solution temperature was cooled to 30 ° C. or less, and the reaction was completed. Thereafter, 2.19 g of cyclohexanone was added while stirring to obtain 43.08 g of a polymerizable polymer composition (including 10.69 g of polymerizable polymer (X-2)). The obtained polymerizable polymer had a weight average molecular weight (MW) of 23000. The acid value reaction rate was 90%.

[Example 6] Synthesis of polymerizable polymer (X-3) (when monomer composition ratio = 30:70) 40.1 g of polymerizable polymer (monomer composition ratio = 30:70) synthesized in Example 3 [polymerizability Polymer (W-3) 10.0 g] was heated with stirring and at a liquid temperature of 60 ° C., glycidyl methacrylate (GMA) 1.16 g (0.0082 mol: MW 142), polymerization inhibitor hydroquinone monomethyl ether 0.006 g, Then, 0.0142 g (0.000107 mol) of the esterification catalyst dimethylbenzylamine was added, and the heating was continued after that to react at a reaction temperature of 95 to 105 ° C. When the acid value reaction rate reached 70.0% or more, the reaction solution temperature was cooled to 30 ° C. or less, and the reaction was completed. Thereafter, 3.38 g of cyclohexanone was added while stirring to obtain 44.64 g of a polymerizable polymer composition (including 10.81 g of polymerizable polymer (X-3)). The obtained polymerizable polymer had a weight average molecular weight (MW) of 23000. The acid value reaction rate was 70%.

[Example 7] Synthesis of polymerizable polymer (X-4) (monomer composition ratio = 40:60) 40.1 g of polymerizable polymer (monomer composition ratio = 40:60) synthesized in Example 1 [polymerizability Polymer (W-1) 10.0 g] is heated with stirring, and at a liquid temperature of 60 ° C., 4-hydroxybutyl acrylate glycidyl ether (4HBAGE) 1.85 g (0.0093 mol: MW200), polymerization inhibitor hydroquinone monomethyl 0.006 g of ether and 0.0161 g (0.000121 mol) of an esterification catalyst dimethylbenzylamine were added, and then the heating was continued to react in a reaction temperature range of 95 to 105 ° C. When the acid value reaction rate reached 90.0% or more, the reaction solution temperature was cooled to 30 ° C. or less, and the reaction was completed. Thereafter, 5.45 g of cyclohexanone was added while stirring to obtain 47.40 g of a polymerizable polymer composition (including 11.18 g of polymerizable polymer (X-4)). The obtained polymerizable polymer had a weight average molecular weight (MW) of 23000. The acid value reaction rate was 90%.

  3. Synthesis (monoesterification) of carboxyl group-containing polymerizable polymer (P3)

[Example 8] Synthesis of carboxyl group-containing polymerizable polymer (Y-1) (monomer composition ratio = 40:60)
46.16 g of the polymerizable polymer composition (monomer composition ratio = 40: 60) synthesized in Example 4 (11.43 g of polymerizable polymer (X-1)) was heated with stirring to a liquid temperature of 80 ° C. Then, 1.49 g (0.0098 mol: MW 152) of tetrahydrophthalic anhydride was added and reacted at a reaction temperature of 80 ° C. When absorption of an acid anhydride group in the vicinity of 1780 cm ⁻¹ disappeared in the product by infrared spectroscopic analysis, the reaction solution was cooled to 30 ° C. or lower and the reaction was completed. Thereafter, 4.47 g of cyclohexanone was added while stirring to obtain 52.12 g of a carboxyl group-containing polymerizable polymer composition (including 12.92 g of a carboxyl group-containing polymerizable polymer (Y-1)). The obtained carboxyl group-containing polymerizable polymer had a weight average molecular weight (MW) of 25000, a double bond equivalent of 1281, and an acid value of 56 mgKOH / g.

Example 9 Synthesis of carboxyl group-containing polymerizable polymer (Y-2) (monomer composition ratio = 20: 80)
The polymerizable polymer composition synthesized in Example 5 (monomer composition ratio = 20: 80) 43.08 g [polymerizable polymer (X-2) 10.69 g] was heated with stirring to a liquid temperature of 80 ° C. Then, 0.74 g (0.0049 mol: MW152) of tetrahydrophthalic anhydride was added and reacted at a reaction temperature of 80 ° C. When absorption of an acid anhydride group in the vicinity of 1780 cm ⁻¹ disappeared in the product by infrared spectroscopic analysis, the reaction solution was cooled to 30 ° C. or lower and the reaction was completed. Thereafter, 2.22 g of cyclohexanone was added while stirring to obtain 46.04 g of a carboxyl group-containing polymerizable polymer composition (including 11.43 g of a carboxyl group-containing polymerizable polymer (Y-2)). The obtained carboxyl group-containing polymerizable polymer had a weight average molecular weight (MW) of 25000, a double bond equivalent of 2343, and an acid value of 30 mgKOH / g.

[Example 10] Synthesis of carboxyl group-containing polymerizable polymer (Y-3) (monomer composition ratio = 30:70)
The polymerizable polymer composition (monomer composition ratio = 30: 70) 44.64 g [polymerizable polymer (X-3) 10.81 g] synthesized in Example 6 was heated with stirring to a liquid temperature of 80 ° C. Then, 1.12 g (0.0074 mol: MW 152) of tetrahydrophthalic anhydride was added, and the reaction was performed at a reaction temperature of 80 ° C. When absorption of an acid anhydride group in the vicinity of 1780 cm ⁻¹ disappeared in the product by infrared spectroscopic analysis, the reaction solution was cooled to 30 ° C. or lower and the reaction was completed. Thereafter, 3.36 g of cyclohexanone was added while stirring to obtain 49.12 g of a carboxyl group-containing polymerizable polymer (including 11.93 g of a carboxyl group-containing polymerizable polymer (Y-3)). The obtained carboxyl group-containing polymerizable polymer had a weight average molecular weight (MW) of 25000, a double bond equivalent of 2087, and an acid value of 46 mgKOH / g.

[Example 11] Synthesis of carboxyl group-containing polymerizable polymer (Y-4) (monomer composition ratio = 40:60)
The polymerizable polymer composition (monomer composition ratio = 40: 60) 47.40 g [polymerizable polymer (X-4) 11.18 g] synthesized in Example 7 was heated with stirring to a liquid temperature of 80 ° C. Then, 1.49 g (0.0098 mol: MW 152) of tetrahydrophthalic anhydride was added and reacted at a reaction temperature of 80 ° C. When absorption of an acid anhydride group in the vicinity of 1780 cm ⁻¹ disappeared in the product by infrared spectroscopic analysis, the reaction solution was cooled to 30 ° C. or lower and the reaction was completed. Thereafter, 4.47 g of cyclohexanone was added while stirring to obtain 53.36 g of a carboxyl group-containing polymerizable polymer composition (including 12.67 g of a carboxyl group-containing polymerizable polymer (Y-4)). The obtained carboxyl group-containing polymerizable polymer had a weight average molecular weight (MW) of 25000, a double bond equivalent of 1522, and an acid value of 53 mgKOH / g.

Example 12 Synthesis of carboxyl group-containing polymerizable polymer (Y-5) (monomer composition ratio = 40: 60)
46.16 g of the polymerizable polymer composition (monomer composition ratio = 40: 60) synthesized in Example 4 (11.43 g of polymerizable polymer (X-1)) was heated with stirring to a liquid temperature of 80 ° C. Then, 1.45 g (0.0098 mol: MW 148) of phthalic anhydride was added and reacted at a reaction temperature of 80 ° C. When absorption of an acid anhydride group in the vicinity of 1780 cm ⁻¹ disappeared in the product by infrared spectroscopic analysis, the reaction solution was cooled to 30 ° C. or lower and the reaction was completed. Thereafter, 4.35 g of cyclohexanone was added while stirring to obtain 51.96 g of a carboxyl group-containing polymerizable polymer composition (including 12.88 g of a carboxyl group-containing polymerizable polymer (Y-5)). The obtained carboxyl group-containing polymerizable polymer had a weight average molecular weight (MW) of 25000, a double bond equivalent of 1277, and an acid value of 57 mgKOH / g.

4). Production of polyfunctional liquid crystalline polymer composition [Example 13] Production of polyfunctional liquid crystalline polymer composition (Z-1) 52.12 g of carboxyl group-containing polymerizable polymer composition of Example 8 (carboxyl group-containing polymerization) Polymer (Y-1) 12.92 g) and the following formula (VI-a):

[Wherein n is 6. ] 19.38 g [1.5 times the weight of carboxyl group-containing polymerizable polymer (Y-1)] and 1.62 g of photopolymerization initiator Irgacure 907 [acid anhydride] Product addition polymer (Y-1) and polyfunctional liquid crystalline monomer of the above formula (VI-a) (wherein n is 6), 5% of the total weight, and cyclohexanone 97.16 g, , BYK-323 (surfactant) of 0.032 g [carboxyl group-containing polymerizable polymer (Y-1) and a polyfunctional liquid crystalline monomer of the above formula (VI-a) wherein n is 6] The solution containing 0.1% of the total weight] was stirred and mixed for 1 hour to obtain 170.31 g of a polyfunctional liquid crystalline polymer composition. With respect to the solid content contained in the composition of the obtained polyfunctional liquid crystalline polymer (Z-1), the double bond equivalent was 502, and the acid value was 22 mgKOH / g.

Example 14 Synthesis of Polymerized Liquid Crystalline Polymer Composition (Z-2) 46.04 g of the carboxyl group-containing polymerizable polymer composition of Example 9 [11.43 g of carboxyl group-containing polymerizable polymer (Y-2) And a polyfunctional liquid crystalline monomer of the above formula (VI-a) wherein n is 6. ] Was changed to 17.15 g [1.5 times the weight of carboxyl group-containing polymerizable polymer polymer (Y-2)], and then the same operation as in Example 13 was performed. With respect to the solid content in the composition of the obtained polyfunctional liquid crystalline polymer (Z-2), the double bond equivalent was 538, and the acid value was 12 mgKOH / g.

[Example 15] Synthesis of polyfunctional liquid crystalline polymer composition (Z-3) 49.12 g of the carboxyl group-containing polymerizable polymer composition of Example 10 [carboxyl group-containing polymerizable polymer (Y-3) 11] The polyfunctional liquid crystalline monomer (VI-a) (wherein n is 6). ] Was changed to 17.90 g (1.5 times the weight of carboxyl group-containing polymerizable polymer (Y-3)), and the same operation as in Example 13 was performed. With respect to the solid content contained in the composition of the obtained polyfunctional liquid crystalline polymer (Z-3), the double bond equivalent was 532, and the acid value was 18 mgKOH / g.

Example 16 Synthesis of Polyfunctional Liquid Crystalline Polymer Composition (Z-4) 53.36 g of the carboxyl group-containing polymerizable polymer composition of Example 11 [carboxyl group-containing polymerizable polymer (Y-4) 12 The polyfunctional liquid crystalline monomer (VI-a) (wherein n is 6). ] Was changed to 19.01 g (1.5 times the weight of the carboxyl group-containing polymerizable polymer (Y-4)), and the same operation as in Example 13 was performed. With respect to the solid content contained in the composition of the obtained polyfunctional liquid crystalline polymer (Z-4), the double bond equivalent was 514, and the acid value was 21 mgKOH / g.

[Example 17] Synthesis of polyfunctional liquid crystalline polymer composition (Z-5) 51.96 g of the carboxyl group-containing polymerizable polymer composition of Example 12 [carboxyl group-containing polymerizable polymer (Y-5) 12] .88 g are included], and the polyfunctional liquid crystalline monomer (VI-a) above (wherein n is 6). ] Was changed to 19.32 g (1.5 times the weight of carboxyl group-containing polymerizable polymer (Y-5)), and the same operation as in Example 13 was performed. With respect to the solid content contained in the composition of the obtained polyfunctional liquid crystal polymer (Z-5), the double bond equivalent was 501 and the acid value was 23 mgKOH / g.

[Example 18] Synthesis of polyfunctional liquid crystalline polymer composition (Z-6) 46.16 g of the polymerizable polymer composition of Example 4 was used as the carboxyl group-containing polymerizable polymer [carboxyl group-containing polymerizable polymer (X-1). ) 11.43 g], except that the polyfunctional liquid crystalline monomer of the above formula (VI-a) was changed to 17.15 g [1.5 times the weight of the polymerizable polymer (X-1)]. Were carried out in the same manner as in Example 13. With respect to the solid content in the composition of the obtained polyfunctional liquid crystalline polymer (Z-6), the double bond equivalent was 492, and the acid value was 2 mgKOH / g.

[Example 19] Synthesis of polyfunctional liquid crystalline polymer composition (Z-7)
Photopolymerization initiator Irgacure 907 [5% with respect to the total weight of the acid anhydride addition polymer and polyfunctional liquid crystalline monomer] as the photopolymerization initiator of Example 12 Irgacure 907 [carboxyl group-containing polymerization] Photopolymerization initiator OXE-01 [2% based on the total weight of the carboxyl group-containing polymerizable polymer and polyfunctional liquid crystalline monomer] The operation was performed in the same manner as in Example 13 except that the change was made. With respect to the solid content contained in the composition of the obtained polyfunctional liquid crystal polymer (Z-7), the double bond equivalent was 502, and the acid value was 22 mgKOH / g.

[Example 20] Synthesis of polymerizable liquid crystalline polymer composition (Z-8)
The photopolymerization initiator Irgacure 907 [5% based on the total weight of the carboxyl group-containing polymerizable polymer and the polyfunctional liquid crystalline monomer] of the photopolymerization initiator Irgacure 907 [carboxyl group-containing] 3% based on the total weight of the polymerizable polymer and the polyfunctional liquid crystalline monomer], photopolymerization initiator OXE-02 [2 based on the total weight of the carboxyl group-containing polymerizable polymer and the polyfunctional liquid crystalline monomer %] Was performed in the same manner as in Example 13. With respect to the solid content contained in the composition of the obtained polyfunctional liquid crystalline polymer (Z-8), the double bond equivalent was 502, and the acid value was 22 mgKOH / g.

4). Performance Evaluation for Each Polyfunctional Liquid Crystalline Polymer Composition For each polyfunctional liquid crystalline polymer composition produced in each of the above Examples and Comparative Examples, a film was formed according to the following procedure. The retardation in the in-plane direction per unit thickness (Re / d) was evaluated as follows.

<Film formation method>
(1) 230 ° C. treated film:
About 2 ml of the polyfunctional liquid crystalline polymer composition is cast on a substrate (glass and polyimide, 10 × 10 cm ² ), a thin film is formed by spin coating, and then dried (90 ° C./10 minutes) to a thickness of 2 μm. An oriented film was prepared and cooled to 30 ° C.
Thereafter, ultraviolet light with an exposure amount of 900 mJ / cm ² is irradiated, the film is processed with an alkaline aqueous solution (0.1% aqueous sodium carbonate solution), and only the non-exposed areas are removed. 1 hour) and then cooled to 30 ° C.

<Transparency>
The film produced as described above was visually observed, and the transparency was evaluated and recorded based on the following criteria.
○: Transparent
×: Whitening

<Developability>
The time required to remove only the non-exposed areas during the treatment with the alkaline aqueous solution (0.1% sodium carbonate aqueous solution) in the above film forming method was measured.

<Evaluation of optical properties>
About the film | membrane obtained above, it measured with the ellipsometer OPTIPRO (made by Shintec Co., Ltd.) on the following conditions, and calculated | required Re / d.
Measurement wavelength λ: 550 [nm]
Film thickness d: 2 [μm]

<Uniformity uniformity>
About the film | membrane obtained above, the orientation uniformity was evaluated using the polarizing microscope. The prepared film was observed under crossed Nicols, and recorded as O where no light leakage due to alignment defects of the liquid crystal was confirmed and X as not.

<Evaluation of heat resistance>
The film was additionally heated to 230 ° C. for 3 hours, and then Re / d was obtained again, and the change from Re / d before heating was obtained.
<Evaluation results>
The results of the evaluation are summarized in Tables 1 and 2 below. As can be seen from the table, the polyfunctional liquid crystalline polymer compositions of the examples have good birefringence characteristics and film transparency, and the birefringence characteristics do not change even when exposed to high temperatures. It can be seen that a membrane can be provided.

  Films using the composition of the present invention have good birefringence characteristics and thermal stability that can maintain sufficient birefringence characteristics even when exposed to high temperatures used in the production of liquid crystal panels. Furthermore, since it has an advantageous feature that it can be developed in an alkaline aqueous solution that is environmentally friendly, according to the composition of the present invention, a polymerizable liquid crystal thin film having excellent optical properties can be obtained not only from the outside of the liquid crystal cell but also from the cell. The liquid crystal panel can be provided in a predetermined shape at a required position, which is advantageous in reducing the thickness and cost of the liquid crystal panel. In addition, since the optical anisotropy can be stably maintained not only at room temperature but also at high temperatures, it can be used as various electronic devices other than liquid crystal panels, organic EL displays, and holographic materials.

Claims (8)

Formula (I):

[Wherein R ₁ is a hydrogen atom or a methyl group, A ₁ and A ₂ are each independently an alkylene group having 1 to 4 carbon atoms or a single bond, and B ₁ is a hydroxyl group or a carboxyl group. Yes, X ₁ is
(i) an alkylene group having 1 to 18 carbon atoms,
(ii) a C1-C18 alkylene group having a carbonyl group at the adjacent phenoxy side end,
(iii) a C 1-18 alkylene group having a C 1-6 alkylene group bonded to the terminal opposite to the phenoxy side via a —COO— group, or
(iv) an alkylene group having 1 to 18 carbon atoms and having 1 to 10 —C ₂ H ₄ O— groups connected in series to the terminal opposite to the phenoxy side,
a and b are 0 or a positive integer satisfying a + b = 0-2. A (meth) acrylic monomer (M1) represented by
Formula (II):

Wherein, R ₂ is a hydrogen atom or a methyl group, A ₃ and A ₄ are each independently an alkylene group having 1 to 4 carbon atoms, -COO- group, or a single bond, Z ₁ ~ Z ₃ is independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and X ₂ is an alkylene having 1 to 18 carbon atoms. C and d are 0 or a positive integer satisfying c + d = 0-2. ] A polymer (P1) obtained by polymerizing a monomer mixture containing a (meth) acrylic monomer (M2) represented by formula (1)] with an epoxy group and an ethylenic double bond-containing compound, and the hydroxyl group of the polymer (P1) Or a carboxyl group and an epoxy group are added to form a carbon-carbon double bond-containing polymerizable polymer (P2), which is converted into a monoester derivative by reaction with a carboxylic acid anhydride. Polymerizable polymer (P3). The carboxyl group according to claim 1 , wherein the epoxy group and the ethylenic double bond-containing compound are glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and 3,4-epoxycyclohexylmethyl (meth) acrylate. Containing polymerizable polymer (P3).   The carboxyl group-containing polymerizable polymer (P3) according to claim 1 or 2, wherein a reaction rate of the polymer (P1) with an epoxy group and an ethylenic double bond-containing compound is 60% or more.   A polyfunctional liquid crystal comprising the carboxyl group-containing polymerizable polymer (P3) according to any one of claims 1 to 3 and a polyfunctional monomer having two or more ethylenically unsaturated bonds in one molecule. Polymer composition (PC). The polyfunctional monomer has the formula (VI):

[Wherein, R ₁₆ is a hydrogen atom or a methyl group, R ₁₇ is an alkylene group having 1 to 18 carbon atoms, or a —COO— group and —OCO at the terminal opposite to the adjacent (meth) acryloyloxy side. -An alkylene group having 1 to 18 carbon atoms and any one of the groups, T ₁ is

(Z ₄ is a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms), Y ₁ is a single bond or —COO—, and Y ₁ ′ is a single bond or —OCO -. ] The polyfunctional liquid crystalline polymer composition (PC) of Claim 4 which is a polyfunctional liquid crystalline monomer shown by these.   A polymer composition for a liquid crystal panel, comprising the polyfunctional liquid crystalline polymer composition according to claim 4 or 5.   A polymerizable thin film obtained by applying the polyfunctional liquid crystalline polymer composition of claim 4 or 5 to a substrate surface.   An optically anisotropic thin film obtained by applying the polyfunctional liquid crystalline polymer composition of claim 4 or 5 to a substrate surface and curing the composition.