TW201004978A - Optically anisotropic film material and optically anisotropic film - Google Patents

Abstract

The present invention provides liquid crystal polymer whose optical characteristics change less while it is at high temperature, composition containing the same, and liquid crystal film. Provided is polymer polymerized a monomer formula (I) and polymerizable polymer formed by addition reaction of epoxy having a side chain containing unsaturated bond and cyclic monomer containing oxethane between B1 and epoxy or oxethane (R1 is H or methyl; A1, A2 are C1-4 alkylene or single bond; B1 is OH or COOH; X1 is C1-18 alkylene, C1-18 alkylene with -CO- next to phenoxy, C1-18 alkylene with C1-6 alkylene bonding through the medium of -COO- at opposite side, or C1-18 alkylene with -C2H4O- of 1 to 10 at opposite side; a, b having the relation a+b=0-2 are integer number ≥ 0).

Description

201004978 VI. Description of the Invention: [Technical Field] The present invention relates to an optically anisotropic film material and an optically anisotropic film, and more particularly to an aggregation of an aromatic ring and a double bond in a side chain. A polymer, a polyfunctional liquid crystal composition containing the same, a polymerizable liquid crystal film, and an optically anisotropic film obtained by polymerizing the material. [Prior Art] In recent years, a liquid crystal material of a polymerization type in which a polymerizable double bond site is reacted by light or heat has been popularly used. The polymerizable liquid crystal material having optical anisotropy is polymerized by using light or heat as a trigger to fix the specific optical characteristics before polymerization. Therefore, the polymerizable liquid crystal material has an appropriate alignment after the liquid crystal state, and is polymerized and cured while maintaining its alignment characteristics, thereby obtaining a retardation film which maintains its optical characteristics, and has an optical anisotropy. Hardened material. Further, a technique for forming an optically anisotropic film layer in a liquid crystal cell is also popular (for example, Patent Document 1). When an optically anisotropic film layer is provided in a liquid crystal cell in comparison with a modern technique in which a phase difference film is attached to the outer side of the liquid crystal glass substrate, the liquid crystal panel is expected to be thinner and lower in cost. In this regard, the reason for the manufacturing steps of the liquid crystal panel is that the substrate or the like to which the liquid crystal material is applied is generally suitable for the inside of the liquid crystal cell because heat treatment is performed at a temperature of about 200 ° C or higher. The anisotropic material is intended to have characteristics that do not cause changes in optical anisotropy even when exposed to high temperature conditions. It is proposed to fix a polymer having a crosslinkable group under the liquid crystal polymer layer which is easily aligned in a specific direction (for example, Patent Document 2). However, the polymer containing a crosslinkable group used in the application of -4 - 201004978 has a problem that the optical characteristics are greatly lowered when exposed to the high temperature conditions as described above. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2000-257711 [Patent Document 2] The present invention provides a method for providing a change in optical characteristics even when maintained under the above-described high temperature conditions. It is intended for a liquid crystal polymer having a very small change, a composition containing the same, and a liquid crystalline film obtained by polymerizing the material. The present inventors have provided a polymerizable polymer having an aromatic ring and a polymerizable double bond in a side chain, a polyfunctional liquid crystal composition containing the same, and a polymerizable liquid crystal film using the liquid crystal composition. The present inventors have found that a novel polymerizable polymer having a specific range of an aromatic ring and a polymerizable double bond in a side chain can impart an optical anisotropic film having a property satisfying the above object when the substance is polymerized. The results of the review are thoroughly investigated and the present invention is completed. In other words, the present invention provides the following. ® 1. A polymerizable polymer which is an aromatic ring-containing polymer (AP) obtained by polymerizing a polymerizable monomer (PM) containing a (meth)acrylic monomer represented by the formula (1). And an epoxy group having a side chain (Q) having an ethylenically unsaturated bond or a cyclic monomer having an oxetane skeleton, and a hydroxyl group of the aromatic ring-containing polymer (AP) and/or Or a carboxyl group, an addition reaction with an epoxy group skeleton or an oxetane skeleton of the cyclic monomer,

201004978 (wherein 1^ is a hydrogen atom or a methyl group; A1 and A2 are each independently an alkylene group or a single bond having a carbon number of 1 to 4; 81 is a hydroxyl group or a carboxyl group; and 1 is (i) a carbon number of 1 a alkylene group of -18, (ii) an alkylene group having a carbon number of 1 to 18 at the terminal of the adjacent phenoxy group, and (iii) having a terminal via the -COO at the end opposite to the side of the phenoxy group. - a bonded alkyl group having from 1 to 6 carbon atoms having a carbon number of from 1 to 6, or

(iv) having a series of bonded 10 -C2H40-based alkyl groups having 1 to 18 carbon atoms at the end opposite to the phenoxy group side; a and b satisfying a + b = 0 to 2 2. The polymerizable polymer according to the above 1, wherein the polymerizable monomer (PM) is a monomer containing a (meth)acrylic monomer represented by the formula (Π).

(II) (wherein R2 is a hydrogen atom or a methyl group; A3 and A4 are each independently an alkylene group having a carbon number of 1 φ to 4, a -COO- group, or a single bond; and Zi to Z3 are each independently hydrogen. Atom, _ atom, an aryl group, a group having a carbon number of 1 to 18, or an alkoxy group having a carbon number of 1 to 4; X2 is an alkylene group having a carbon number of 1 to 18; C and d satisfying c + d = 0 to 2 of 0 or a positive integer). 3. The polymerizable polymer according to the above 1 or 2, wherein the cyclic monomer is an aliphatic epoxy group-containing monomer represented by the formula (III), and the aliphatic oxygen-containing heterocyclic ring represented by the formula (IV) a monomer of butane or an aliphatic (epoxy) group represented by formula (V): 201004978 r3

(wherein R3 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)

(IV) an alkyl group of 1 to 4) (wherein R4 to 116 are a hydrogen atom or a carbon number

(wherein R7 to R15 are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). 4. The polymerizable polymer according to any one of the above 1 to 3, wherein a reaction rate of the aromatic ring-containing polymer (AP) with the cyclic monomer is 5 mol% or more. A liquid crystalline polymer composition comprising the polymerizable polymer according to any one of the above 1 to 4 and a polyfunctional monomer having two ethylenically unsaturated bonds on φ in one molecule. . 6. The polyfunctional liquid crystalline polymer composition according to the above 5, wherein the polyfunctional monomer is a polyfunctional liquid crystalline monomer represented by the formula (VI). Η

Rl6 0 Rl7 ' ^ R17—0 Rt6 (VI) (wherein R! 6 is a hydrogen atom or a methyl group; an alkylene group having a carbon number of 1 to 18 or an adjacent (meth) propylene oxy group side The end of the opposite side has an alkyl group having a carbon number of 1 to 18 of any one of -C00· group and -0C0- group; 201004978 Ή is a group shown below; (Z4 is a hydrogen atom, a halogen atom, carbon Number 1~8 alkyl); Υι is a single bond or -COO-; Y!' is a single bond or -OCO-)

A polymer composition for a liquid crystal panel comprising the above-described 5 or 6 polyfunctional liquid crystalline polymer composition. A polymerizable film formed by applying the above-mentioned 5 or 6 polyfunctional liquid crystalline polymer composition onto a surface of a substrate. An optically anisotropic film obtained by applying the above-mentioned 5 or 6 polyfunctional liquid crystalline polymer composition to a surface of a substrate and hardening it. 10. The polymerizable polymer according to the above 1, Wherein the polymerizable monomer (PM) additionally contains a (meth)acrylic monomer represented by the formula (II),

(wherein R2 is a hydrogen atom or a methyl group; and A3 and A4 each independently represent an alkylene group having 1 to 4 carbon atoms, a -COO- group, or a single bond; and Z! to Z3 each independently represent 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; X2 is an alkylene group having 1 to 18 carbon atoms; c and d satisfying c + d = 0~ 2 or a positive integer) and a carboxyl group-containing monomer represented by CHfCI^-Xs-COOH [formula (C1)], wherein R! is hydrogen or methyl; X3 is a single bond or -COOR2-; R2 is a carboxyl group-containing monomer having a carbon number of 2 to 1 fluorene and/or CHfCRi-X^COOH [formula (C2)], 201004978 [wherein Ri is hydrogen or methyl·, X4 Is -coor2ocor3. Here, r2 is an alkylene group having 2 to 10 carbon atoms; R3 is an alkylene group having 2 to 10 carbon atoms or an aromatic alkyl group having 2 to 10 carbon atoms; The total amount of the carboxyl group-containing monomer does not exceed 15% by weight of the total amount of the polymerizable monomer (PM) represented by the formula (1) and the polymerizable monomer represented by the formula (II). 11. The polymerizable polymer according to 10 above, wherein the cyclic monomer is an aliphatic epoxy group-containing monomer represented by formula (111), and the aliphatic oxetane group represented by formula (IV) a monomer of an alkyl group or a monojadu body containing an alicyclic epoxy group represented by the formula (v), wherein R3 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;

❹ (wherein R4~Re is a hydrogen atom or a carbon number of 1 to 4)

(wherein R7 to R1S are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). 12. The polymerizable polymer according to 10 or 11, wherein the reaction rate of the aromatic ring-containing polymer (AP) with the cyclic monomer is 5 mol% to ±. A polyfunctional liquid crystalline polymer composition comprising the polymerizable polymer according to any one of the above-mentioned publications of the above-mentioned No. 201004978 to 12, and a polyfunctional compound having two or more ethylenically unsaturated bonds in one molecule. Formed by a monomer. 14. The polyfunctional liquid crystalline polymer composition according to the above 13, wherein the polyfunctional monomer is a polyfunctional liquid crystalline monomer represented by the formula (VI).

(VI) (wherein R16 is a hydrogen atom or a methyl group; Ri7 is an alkylene group having 1 to 18 carbon atoms or a terminal having a -COO group on the opposite side to the side of the (meth)acryloxyloxy group; - an alkyl group having 1 to 18 carbon atoms in any of the OCO groups; 1^ is Z 4

(z4 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms); ¥1 is a single bond or -COO-; Y, which is a single bond or -OCO-). A polymer composition for a liquid crystal panel comprising the polyfunctional liquid crystalline polymer composition of the above 13 or 14. ❹ 16. A polymerizable film formed by applying the above-mentioned 13 or 14 polyfunctional liquid crystalline polymer composition onto the surface of a substrate. An optically anisotropic film obtained by applying the above-mentioned 13 or 14 polyfunctional liquid crystalline polymer composition to a surface of a substrate and curing it. [Effect of the Invention] The film of the composition has excellent birefringence characteristics and has an advantageous feature that the birefringence property is not changed even at a high temperature used when it is exposed to a liquid crystal panel. Therefore, the polymerizable liquid crystal film having excellent optical properties can be provided in a liquid crystal which is better than the liquid crystal package, and the liquid crystal panel can be made thinner and lower in cost. Further, since the stable optical anisotropy can be maintained not only at room temperature but also at a high temperature, it is extremely useful as an electronic device or a hologram material in addition to the liquid crystal panel. [Embodiment] [Best Mode for Carrying Out the Invention] The polymerizable polymer of the present invention is obtained by polymerizing a polymerizable monomer (PM) containing a (meth) fluorene acrylate monomer represented by the formula (1). The aromatic ring-containing polymer (AP) and the cyclic monomer having an ethylenically unsaturated bond-containing side chain (Q) or an oxetane skeleton-containing cyclic monomer The hydroxyl group and/or carboxyl group of the ring polymer (AP) is formed by addition reaction with the epoxy group skeleton or the oxetane skeleton of the cyclic monomer.

© In the formula (1), the human 1 and the octa 2 are each independently an alkylene group having a carbon number of 1 to 4 or a single bond, and a single bond is preferred. Preferably, Β is a hydroxyl group or a carboxyl group is preferably a carboxyl group. Χι is (i) an alkylene group having 1 to 18 carbon atoms, (ii) an alkylene group having a carbon number of 1 to 18 at a terminal end of the adjacent phenoxy group, and (iii) a side with the phenoxy group. The opposite end has a C 1-18 alkylene group having a C 1-6 alkyl group bonded via -COO -, or (iv) has an end on the opposite side to the phenoxy side. a series of bonded 1-10-C2H40-based alkyl groups having 1-18 carbon atoms; a and b are 0 or a positive integer satisfying a + b = 0~2, in terms of optical anisotropy or heat resistance In other words, it is preferable to satisfy 0 or a positive integer of a + b = 1 to 2. -11- 201004978 Specific examples of the (meth)acrylic monomer represented by the formula (I) are as follows.

(b a) [wherein, η is an integer of from 1 to 18; R is a hydrogen atom or a methyl group; and G is a carboxyl group] Ο

0—C2H^—C—〇- 0. G (Hd) [wherein η is an integer from 1 to 18; R is a hydrogen atom or a methyl group; and G is a carboxyl group]

V-〇-f-C2H4-0-^ -CH;

(b)

R

[wherein, m is an integer of 1 to 5; η is an integer of 1 to 18; R is a hydrogen atom or a methyl group: G is a mercapto group]

(I-d) is 竣基]

[wherein, η is an integer of from 1 to 18; R is a hydrogen atom or a methyl group; G

(I~e) [wherein, η is an integer of from 1 to 18; R is a hydrogen atom or a methyl group; and G is a hydroxyl group]

[wherein η is an integer of 1 to 18; R is a hydrogen atom or a methyl group; and g is a sylylene group] In the present invention, the above-mentioned aromatic ring-containing polymer (ΑΡ) is imparted in terms of imparting an alignment property to a high temperature condition. The reaction is carried out with an epoxy group having a side chain of 12-201004978 (Q) having an ethylenically unsaturated bond or a cyclic monomer containing an oxetane skeleton. The epoxy group having a side chain (Q) having an ethylenically unsaturated bond or a cyclic monomer containing an oxetane skeleton, for example, a monomer having an aliphatic epoxy group represented by the formula (in) A monomer containing an oxetane group represented by the formula (IV) and a monomer having an alicyclic epoxy group represented by the formula (v). Specific examples of the monomer having an aliphatic epoxy group represented by the formula (III), such as glycidyl methacrylate, glycidyl acrylate, itaconic acid propylene glycol, propylene propylene Propylene, methyl propyl propyl glycopropionate and so on. Specific examples of the monomer containing the oxetane represented by the formula (IV) such as 3-methyl-3-oxetane methyl (meth)acrylate or 3-ethyl (meth)acrylate 3-oxetane methyl ester, 3-n-propylmethyl-3-oxetane methyl (meth)acrylate, 3-isopropyl-3-oxocyclo(meth)acrylate Butane methyl ester, 3-methyl-3-oxetane ethyl (meth)acrylate, 3-ethyl-3-oxetane ethyl (meth)acrylate, (meth)acrylic acid 3-n-propyl-3-oxetaneethyl ester, 3-isopropyl-3-oxetaneethyl (meth)acrylate, 2-methyl-3-(meth)acrylate Oxetane methyl ester, 2,3-dimethyl-3-oxetane methyl (meth)acrylate, 2,4-dimethyl-3-oxeidine (meth)acrylate Alkyl methyl ester, 2,3,4·trimethyl-3-oxetane methyl (meth)acrylate, 3-ethyl-2-methyl-3-oxetane (meth)acrylate Alkyl methyl ester, 3-ethyl-2,4-dimethyl-3-oxetane methyl (meth)acrylate, and the like. Specific examples of the monomer having an alicyclic epoxy group represented by the formula (V), such as 3,4-epoxycyclohexylmethyl methacrylate (trade name: CYCLOMERM-100, manufactured by DAICEL Chemical Industry Co., Ltd.), CYCLOMERM-1〇1 (trade name: manufactured by DAICEL Chemical Industry Co., Ltd.), 3,4-epoxycyclohexyl methacrylate-13- 201004978 (trade name: CYCLOMER-A-200, manufactured by DAICEL Chemical Industry Co., Ltd.), ethylene A cyclohexene monoepoxide, a limonene monoepoxide or the like. Further, the reaction rate of the aromatic ring-containing polymer (AP) and the epoxy group having a side chain (Q) having an ethylenically unsaturated bond or an oxetane skeleton is preferably 5% or more. The preferred one is 10% or more, and the more preferred one is 30% or more. In addition, the preferred one is 95% or less, and the more preferred one is 90% or less. Here, the "reaction rate" is as defined below. _ Total number of unreacted hydroxyl and carboxyl groups derived from aromatic ring-containing polymer (AP) Χ Total number of hydroxyl groups and carboxyl groups derived from aromatic ring-containing polymer (AP) before reaction Χ In addition, acid 聚合物 of polymerizable polymer It is preferably 160 or less, more preferably 100 or less. This is because when the acid mash is too high, there is a disadvantage that the alignment or the transparency of the film is lowered. Further, the polymerizable polymer preferably has a double bond equivalent of from 200 to 3,000, more preferably from 300 to 2,000. When the double bond equivalent is too high, the heat resistance is lowered, and when it is too low, the so-called misalignment is disadvantageous. In the production of the polymerizable polymer of the present invention, the above polymerizable monomer (ΡΜ) may be polymerized with a (meth)acrylic monomer represented by the following formula (II). The addition of the (meth)acrylic monomer represented by the formula (II) is useful for optimizing the softening point of the obtained polymerizable polymer. Formula (II):

In the formula, A3 and A4 each independently represent an alkylene group having 1 to 4 carbon atoms, a -COO- group or a single bond, and a _C00_ group or a single bond is preferred. Z1 to Z3 each independently represent a hydrogen atom, a _ 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 preferred. X2 is an alkyl group having 1 to 18 carbon atoms; c and d are 0 or a positive integer satisfying c + d = 0 to 2, and it is preferable to satisfy 0 or a positive integer of c + d = 1 to 2. Preferred examples of the (meth)acrylic monomer represented by the formula (?) are as follows.

("~G (II-a) [wherein η is an integer from 1 to 18. R is a hydrogen atom or a methyl group. G is a cyano group]

[wherein] η is an integer of from 1 to 18. R is a hydrogen atom or a methyl group. G is cyano]

(H-c)

[wherein, η is an integer of from 1 to 18. Each R is an independent hydrogen atom or a methyl group. ]

(3) ±0-~R (n-d) [wherein, η is an integer from 1 to 18. R is a hydrogen atom or a methyl group. G is a cyano group] The polymerizable polymer of the present invention is an aromatic ring-containing polymerization formed by polymerizing a polymerizable monomer (PM) composed of a (meth)acrylic monomer represented by the formula (I). (AP), an epoxy group having a side chain (Q) containing an ethylenically unsaturated bond, or a cyclic monomer containing an oxetane skeleton, in the polymer containing the aromatic-15-201004978 ring The addition of a hydroxyl group and/or a carboxyl group of (AP) and an epoxy group or an oxetane skeleton of the cyclic monomer to the polymerizable monomer (PM), except for the formula (I) In addition to the (meth)acrylic monomer, other monomers may be contained, but it is not necessarily necessary, and the monomer is limited to a compound having a polymerizable ethylenically unsaturated bond, and there is no particular except this point. The ratio of the (meth)acrylic monomer represented by the formula (I) constituting the object in the aromatic ring-containing polymer (AP) is not limited or may be liquid crystal. The total amount of the monomers is from 0.1 to 100.0% by weight, preferably from 5.0 to 95.0% by weight, more preferably. 20.0~80.0 wt% of the range. a monomer other than the (meth)acrylic monomer represented by the formula (I), such as methyl (meth)acrylate, tert-butyl (meth)acrylate, stearyl (meth)acrylate, (a) (cyclohexyl acrylate), ethoxyethyl (meth) acrylate, hydroxyethyl (meth) acrylate, phenyl (meth) acrylate, hydrazine, hydrazine-dimethyl decylamine, etc. Acrylic monomer, styrene, methyl styrene, ρ-styrene sulfonic acid, ethyl vinyl ether, oxime-vinylimidazole, vinyl acetate, © vinyl pyridine, 2-vinyl naphthalene, vinyl chloride, Vinyl fluoride, fluorene-vinyl carbazole, vinylamine, vinyl phenol, fluorene-vinyl-2-pyrrolidone, etc., vinyl monomer, 4-allyl-1,2-dimethoxy An allyl monomer such as benzene, 4-allylphenol or 4-methoxyallylbenzene. The above other monomer is CHfCR^X^COOH [formula (C1)] [wherein, Ri is hydrogen or methyl; X3 is a single bond or -COOR2-; R2 is an alkylene group having a carbon number of 2 to 1 Å] a carboxyl group-containing monomer, and/or CHpCRrXcCOOH [formula (C2)] [wherein, Ri is hydrogen or methyl; X4 is -COOR2OCOR3-; wherein R2 is a carbon number of 2 to 10, R3 is a carboxyl group-containing monomer represented by -16 - 201004978 alkylene group having 2 to 10 carbon atoms or aromatic alkyl group having 2 to 10 carbon atoms. The total amount of the carboxyl group-containing monomers of the formula (C1) and the formula (C2) must not exceed 15% by weight of the total amount of the polymerizable monomer of the formula (I) and the polymerizable monomer of the formula (II). When the amount is more than 15 parts by weight, the molecular alignment tends to be disordered, and the polymer obtained at the time of coating tends to cause whitening or loss of optical anisotropy. Further, the aromatic ring-containing polymer (AP) is a monomer of the formula (I), a monomer of the formula (II), and a monomer of the formula (C1) and/or a monomer of the formula (C2). In the case of φ, the amount of such monomers in the polymerization step is such that the amount of the monomer of the formula (I) is M1, the amount of the monomer of the formula (II) is M2, the formula (C1) and/or When the amount of the monomer of the formula (C2) is M3, it is preferably 10 to 60 parts by weight, M2 is 90 to 40 parts by weight, and M3 is 1 to 15 parts by weight, more preferably M1 is 20. ～60 parts by weight, M2 is 80 to 40 parts by weight, and M3 is 2 to 12 parts by weight. Specific examples of the carboxyl group-containing monomer of the formula (C1) or the formula (C2), such as (meth)acrylic acid, mono(meth)acryloxyethyl phthalate, tetrahydrophthalic acid monoacid ( Methyl) propylene methoxyethyl ester, tetrahydrogen phthalate mono(methyl) propyl decyloxypropyl methoxide, tetrahydro phthalic acid mono (meth) propylene methoxy propylene vinegar, Methyl) propylene methoxyethyl ester, (meth)acrylic acid mono ω-residue-polycaprolactone ester, acrylic acid dimer, 4-(meth) propylene methoxyethyl benzoic acid, and the like. For 1 mol of the (meth)acrylic monomer represented by the formula (I), the epoxy group having a side chain (Q) having an ethylenically unsaturated bond in the stomach or containing an oxetane skeleton The proportion of the cyclic monomer used is 0.01 to 3.0 mTorr, preferably 0.1 to 2.1 mol, more preferably 0.1 to 1.3 m, and most preferably 〇2 to 1.3 m. -17- 201004978 The polymerizable polymer of the present invention can be appropriately added to a polymerizable composition which is polymerized by light or heat, such as a photoinitiator, an addition reaction catalyst, a surfactant, a solvent, and the like. The component is provided in the form of a polymerizable polymer composition < The content of the optional components is not particularly limited, and is 0 to 30.0% by weight based on the total weight of the polymerizable polymer composition, and the addition reaction catalyst is 0 to 1.0% by weight. The surfactant is preferably 0 to 10.0% by weight, and the organic solvent is preferably 0 to 90.0% by weight. An aromatic ring-containing polymer (AP), an epoxy group having a side chain (Q) containing an ethylenically unsaturated bond, or a cyclic monomer containing an oxetane skeleton, in the aromatic ring-containing polymer The polymerizable polymer of the present invention obtained by addition reaction of a hydroxyl group and/or a carboxyl group of (AP) with an epoxy skeleton or an oxetane skeleton of the cyclic monomer, which remains in the unreacted state The aromatic ring-containing polymer (AP) or the cyclic monomer is preferably a small amount with respect to the entire polymerizable polymer, for example, preferably 0.5% by weight or less, and even if it remains to some extent, it can achieve the object of the invention within the range. There is no particular limitation on the amount of time remaining. The aromatic ring-containing polymer (AP) of the present invention can be polymerized and synthesized by polymerizing a monomer (PM) (a single type or a mixture of two or more kinds of monomers). The polymerization can be carried out without a solvent or by mixing in a solvent. The method of adding a material or a solvent to the polymerization step is not particularly limited. After all the materials are put into the reaction container before the polymerization, the polymerization may be started, or a part of the (meth)acrylic monomer or solvent may be equal to the polymerization start. Then, the segmentation is added by dropping or dividing the input. When it is polymerized in a solvent, a general organic solvent can be used without particular limitation. Specific examples of the solvent, such as water or methanol, ethanol, propanol, butanol, alcohol solvent such as -18-201004978 stearyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone An ester solvent such as a ketone solvent, butyl acetate or propylene glycol monomethyl ether acetate; an ether solvent such as diethyl ether or diglyme; hexane, cyclohexane or methylcyclohexane; A hydrocarbon solvent such as toluene or xylene; a nitrile solvent such as acetonitrile; a guanamine solvent such as N-methylpyrrolidone or dimethylacetamide; and the like. When the above aromatic group-containing polymer (AP) is polymerized, a polymerization initiator can be used. The polymerization initiator can be used by a general user, for example, azobisiso H butyronitrile (AIBN), diethyl-2,2,-azobisisobutyrate (V-601), 2,2'- An azo polymerization initiator such as azobis(2,4-dimethylvaleronitrile) or dimethylazobismethylpropionate, benzammonium peroxide, potassium persulfate, hydrogen peroxide, A peroxide-based polymerization initiator such as a perovskite or a persulfate-based polymerization initiator such as potassium persulfate or ammonium persulfate. These polymerization initiators may be used alone or in combination of two or more. The temperature at the time of the polymerization differs depending on the type of the polymerizable monomer (PM), the type of the polymerization solvent, the type of the initiator, and the like, and is preferably 40 to 150 ° C, more preferably 50 to 120 ° C. range. The polymerizable polymer of the present invention can be obtained by subjecting the above aromatic ring-containing polymer (AP) to an epoxy group skeleton having a side chain (Q) having an ethylenically unsaturated bond or containing an oxetane skeleton. The cyclic monomer is obtained by an addition reaction (addition reaction) between the former hydroxyl group and/or carboxyl group and the latter epoxy ring or oxetane. The temperature of the addition reaction may vary depending on the kind of the cyclic monomer, the kind of the reaction solvent, the type of the catalyst, and the like, and is preferably from 30 to 120 ° C, more preferably from 40 to 100 ° C. Catalyst for the above addition reaction, such as octylamine, dibutylamine, monoethanolamine, -19-201004978 triethanolamine, benzylamine, triethylamine, etc., amine-based catalyst, tetramethylammonium chloride, tetraethyl chloride Ammonium, trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tetraethylammonium acetate, tetra-n-butylammonium bromide, tetra-n-butylammonium iodide, triethylbenzylammonium bromide , tetraphenylammonium bromide, triphenylsulfonyl bromide, tri-n-octylsulfonyl bromide, triphenylsulfonyl chloride, tetraethylammonium bromide, etc. Phosphorus-based catalysts such as phosphine, triphenylphosphine, ginseng (4-methylphenyl)phosphine, and diphenylphosphine chloride. The amount of the catalyst used in the above addition reaction is preferably 0.0001 to 0.1 mol, and 0.003 to 0.05, with respect to 1 mol of the ring-shaped monomer, in terms of preventing coloration or suppressing by-products. Moore is better. The polyfunctional liquid crystalline polymer composition of the present invention is a composition comprising the above polymerizable polymer and a polyfunctional monomer having two or more ethylenically unsaturated bonds in one molecule, The two are stirred and uniformly mixed to obtain. The mixing of the polyfunctional monomer in the polymerizable polymer is useful for improving alignment stabilization or film formation stabilization. a polyfunctional monomer having two or more ethylenically unsaturated bonds in one molecule, such as a polyfunctional (meth) acrylate monomer, a polyfunctional (meth) acrylamide monomer, a polyfunctional vinyl monomer Monofunctional, polyfunctional allyl monomer. Specific examples of the polyfunctional (meth) acrylate monomer, such as ethylene glycol di(meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Fourteen ethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate , tetramethylol methane tetra(meth) acrylate, 1,4-butanediol di(meth) acrylate, 1,6-hexanediol di(meth) acrylate, neopentyl alcohol three ( Methyl), acrylate, pentaerythritol tetra(meth)acrylic acid-20-201004978 ester, dipentaerythritol hexa(meth)acrylate, and the like. Specific examples of the polyfunctional (meth) acrylamide monomer, such as polyfunctional (meth) acrylamide synthesized from N, N'. methylene bis acrylamide or ethylene diamine, phenyl diamine or the like Wait. Specific examples of the polyfunctional vinyl monomer are, for example, divinylbenzene, ethylene glycol divinyl ether, divinyl adipate, divinyl succinate or the like. Specific examples of the polyfunctional allyl monomer include, for example, diallyl phthalate, diallyl ether, diallyl malonate, p-allylstyrene, and the like. The Φ polyfunctional single system is preferably a polyfunctional (meth) acrylate monomer, and more preferably a polyfunctional liquid crystalline monomer represented by the formula (VI), which is exemplified below. These polyfunctional monomers 'may be used singly or in combination of two or more kinds.

Wherein η is an integer from 1 to 18, R is a hydrogen atom or a methyl group, and z is a hydrogen source

Sub, halogen atom or alkyl group having 1 to 8 carbon atoms]

, a halogen atom or an alkyl group having 1 to 8 carbon atoms] -21 - 201004978 The polyfunctional liquid crystalline polymer composition of the present invention may contain a generally used film to form a uniform film by light irradiation. A photopolymerization initiator is generally used. Specific examples of the photopolymerization initiator include an α-amino ketone photopolymerization initiator such as IRGACURE 907 (manufactured by Ciba Specialty Chemicals Co., Ltd.) and IRGACURE 369 (manufactured by Ciba Specialty Chemicals Co., Ltd.), and a phenoxy group. Dichloroacetophenone, 4-tert-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylindole propane - acetophenone, 1-hydroxycyclohexyl benzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butane-anthracene-ketone Photopolymerization initiator, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl acetal, etc. benzoin-based photopolymerization initiator, benzophenone , benzhydryl benzoic acid, methyl benzyl benzoate, 4-phenyl benzophenone, hydroxybenzophenone, benzoated benzophenone, 4-benzylidene-4,- a benzophenone-based photopolymerization initiator such as bisphenyl thioether, 2-oxothioxanthene, 2-methyloxythiolane, isopropyloxysulfonate, and 2, Oxygen-sulfur sulphate, such as 4-isopropanyl oxysulfonate Polymerization initiator, 2,4,6-trichloro-3-trin, 2-phenyl-4,6-bis(trichloromethyl)-3-trin, 2-(!)-methoxybenzene Base)-4,6-bis(trimethyl chloride)-s-triple trap<2-(p-tolyl)-4,6-bis(trimethyl chloride)-s_three tillage, 2 -Pepperyl-4,6-bis(methyl chloride)-s-three tillage, 2,4-bis(methyl chloride)-6-styryl-s-trisole, 2-(naphthalene -1-yl)-4,6-bis(methyl chloride)-s·three tillage, 2-(4-methoxy-naphthalen-1-yl)-4,6-bis (trichloride Base)-s-tripper, 2,4-(methyl chloride-(piperidine)-6-three tillage, 2,4-trichloromethyl (4'-methoxystyryl)_6 _Three-plowed three-well photopolymerization initiation Qi|1, oxazole photopolymerization initiator, imidazole-based photo-22- 201004978 polymerization initiator, etc.; and oxime ester, sulfhydryl phosphine oxide, glyoxylate methyl Phenyl ester, diphenylethylenedione, 9,10-phenanthrenequinone, camphole ketone, ethyl hydrazine, 4,4'-diethylisoindophenol ketone, 3,3',4,4'-tetra (first Photopolymerization initiators such as 3-butylperoxycarbonyl)benzophenone, 4,4'-diethylaminobenzophenone, oxysulfonate, and the like. The agent may be used singly or in combination of two or more kinds. The polyfunctional liquid crystalline polymer composition of the present invention may contain a general surfactant when forming a uniform film. A surfactant such as lauryl φ sulfuric acid Sodium, ammonium lauryl sulfate, triethanolamine lauryl sulfate, polyoxyethylene alkyl ether sulfate, alkyl ether phosphate, sodium squalene sodium, meat camp potassium citrate, coconut oil fatty acid potassium, lauryl amber Anionic surfactants such as sodium acetate; polyethylene glycol monolaurate, sorbitan stearate, propionate propionate, glycerol dioleate, sorbitol hard Nonionic surfactants such as fatty acid esters, sorbitan oleate, etc.; stearyl trimethylammonium chloride, behenyl trimethylamine chloride, stearyl dimethyl benzyl ammonium chloride, a cationic interfacial activity β agent such as cetyltrimethylammonium chloride; lauryl betaine, alkyl sulfobetaine, cocoguanamine propyl betaine, alkyl dimethylaminoacetate betaine, etc. Alkyl betaine, alkyl imidazoline, lauric acid An amphoteric surfactant such as sodium, yoghurt, and sodium acetate; and Β 361-361, ΒΥΚ-3 06, ΥΚ ΥΚ-3 07 ΒΥΚ Chemie Japan, FRORAID FC430 (manufactured by Sumitomo 3M), MEGAFAC F171, A surfactant such as R〇8 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.). These surfactants may be used singly or in combination of two or more. By using the polyfunctional liquid crystalline polymer composition of the present invention, a film for an electronic device excellent in thermal stability can be produced as -23-201004978, and the production method is not limited thereto. When the film is produced, for example, the polyfunctional liquid crystalline polymer composition of the present invention is diluted or applied to a substrate (such as a film) directly or with a solvent, the solvent is removed, a liquid crystal layer is formed, or light irradiation is continued. Hardening, it is preferred to fix the liquid crystal layer. A method of coating a polyfunctional liquid crystalline polymer composition 'is generally known in the art (for example, a spin coating method, a bar coating method, a screen printing method, a spray coating method, etc.) Alternatively, the resin layer may be fixed until it is fixed in a certain form. The coating film in the drying step may be subjected to a photopolymerization treatment after further heat treatment. Preferred examples of the solvent are toluene, glycerin, monoacetylene, Ethylene glycol, triethylene glycol, hexanediol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, dibutyl ether, acetone, methyl ethyl ketone, ethanol, propanol, cyclohexane, methyl ring Hexane, tetrahydrofuran, cyclohexanone, n-hexane, ethyl acetate, butyl acetate, N-methylpyrrolidone, dimethylacetamide, etc. These may be used alone or in combination of two or more kinds. Usable substrates, such as glass substrates such as alkali glass, alkali-free glass, polyimide, polyamide, acrylic, polyvinyl alcohol, triethyl cellulose, polyethylene terephthalate Diester, polyethylene, polycarbonate, polystyrene A resin substrate such as an olefin or a polytrifluoroethylene chloride, or a metal substrate such as iron, aluminum or copper is preferably a glass substrate. When the substrate is heated at a high temperature of 200 ° C or higher, the substrate has no property change. Preferably, the substrate is heat treated by a heat treatment of the coating film under a condition that a uniform orientation of the liquid crystal is obtained, for example, until the temperature is uniform until the alignment is uniform, and the film is heated by a coating of -24.201004978 and then cooled. The heat treatment is preferably in the range of 20 ° C to 120 ° C, and preferably in the range of 50 ° C to 100 ° C. In terms of production efficiency, the heat treatment is in the range of 1 〇 to 3 hours. Preferably, the range of processing time is preferably from 30 seconds to 20 minutes. The light source used in light irradiation can be used with xenon lamps, high pressure mercury lamps, excimer lasers, sodium lamps, halogen lamps, black lamps, electron beam irradiation, etc. There is no particular limitation on the wavelength of light '150 to 800 nm, preferably 180 to 600 nm. ❹

The amount of light is not particularly limited, and is preferably 20 to 5000 mJ/cm 2 and more preferably 100 to 1,500 mJ/cm 2 . The film thickness of the present invention is preferably in the range of 0.1 to 20.Oyrn, more preferably in the range of 1.0 to 5.0//111. The film produced by the present invention can be used as an optical film or the like, and is suitable for improving the image quality of a liquid crystal screen. In particular, the composition of the present invention can be formed entirely on the substrate of the liquid crystal panel. Alternatively, the film can be formed independently at a specific portion (pixel) of the substrate. [Examples] 1. Synthesis of aromatic ring-containing polymer (AP) [Example 1] Synthesis of aromatic ring-containing polymer (X-1) (monomer composition ratio, I-al: II-al = 40: 60)

[In the formula, η is 6, 01 is a mercapto group], the acrylic monomer shown in the formula 4.0g (〇.〇l lmol), formula (II-al)

-25- 201004978 (wherein, n is 6, G2 is a cyano group) A solution of 6.0 g (0.017 m〇l) of an acrylic monomer and 30.0 g of cyclohexanone is stirred and mixed in a nitrogen gas stream. hour. Then, the mixed solution was heated, and when the liquid temperature was 75 ° C, 0.10 g of azobisisobutyronitrile (AIBN) of a polymerization initiator was charged, and polymerization reaction was carried out for 8 hours in a temperature range of 75 to 85 °C. As a result, a polymer composition of 40. lg [containing an aromatic ring-containing polymer (χ-1) 1 0.0 g] ° <Measurement of weight average molecular weight (MW) > φ using gel filtration chromatography ( GPC) The weight average molecular weight (MW) of the aromatic ring-containing polymer (X-1) was measured. The resulting aromatic ring-containing polymer had a weight average molecular weight (MW) of 18,000. <Measurement of acid bismuth> The measurement method is as follows. In other words, about 60 ml of ethanol was added to a 100 ml Erlenmeyer flask, and phenolphthalein was used as an indicator to neutralize with an aqueous solution of 〇.im〇l/l sodium hydroxide. Approximately 1.5 g of the polymer composition was weighed, uniformly dissolved and stirred in the above solution, and titrated with 0.1 mol of a 1/1 aqueous sodium hydroxide solution, and the end point was titrated with a reddish color for about 30 seconds. The following formula is used as a benchmark to determine the acidity. Acid 値 = (0.1xfxAx56.1/B) / (C/100) A: titration (ml) f: coefficient of aqueous sodium hydroxide solution B: amount of polymer composition (g) C: polymer concentration (%) ( Amount of polymer / amount of polymer composition XI 00) -26- 201004978 The above-mentioned acid ring containing an aromatic ring polymer (χ-l) was 61 mgKOH/g. [Example 2] Synthesis of aromatic ring-containing polymer (χ-2) (monomer composition ratio, Ia-1:II-al=50:50) In addition to (meth)acrylic acid represented by formula (Ia), respectively The amount of the monomer used was changed to 5.0 g (0.014 mol), and the amount of the (meth)acrylic monomer represented by the formula (II-a) was changed to 5.0 g (0.014 mol), which was the same as in Example 1. Implementation. The obtained aromatic ring-containing polymer (X-2) had a weight average molecular weight (MW) of 14,000 and an acid hydrate of 77 mgKOH/g. 〇 [Example 3] Synthesis of aromatic ring-containing polymer (χ·3) (monomer composition ratio, I-al: II-a=100:0), except that (meth) represented by formula (Ia) The amount of the acrylic monomer used was changed to 1 〇g (〇.〇27 mol), and the amount of the (meth)acrylic monomer represented by the formula (II-a) was changed to 〇, and examples 1 is implemented in the same way. The obtained aromatic ring-containing polymer (X-3) had a weight average molecular weight (MW) of 1 8000 and an acid hydrazine of 152 mgKOH/g. [Example 4] Synthesis of aromatic ring-containing polymer (X-4) (monomer composition ratio, I-fl: β II-al = 40: 60) except for the acrylic monomer represented by the formula (I-al) The procedure was carried out in the same manner as in Example 1 except that it was changed to 4.0 g (0.014 m·l) of an acrylic monomer as shown in (I-fl).

The aromatic-containing cyclic polymer (Χ-4) obtained by the formula (wherein η is 6 and G3 is a fluorenyl group) has a weight average molecular weight (MW) of 1 8000 and an acid hydrate of 77 mgKOH/g. [Example 5] Synthesis of aromatic ring-containing polymer (X-5) (monomer composition ratio, I-fl: -27-201004978 II-al=20:80) except that the formula (I-fl) is respectively shown The amount of the acrylic monomer used was changed to 2.0 g (0.007 mol), and the amount of the (meth)acrylic monomer represented by the formula (ΙΙ-al) was changed to 8.0 g (0.022 m〇l), Example 4 was carried out in the same manner. The obtained aromatic ring-containing polymer (X-5) had a weight average molecular weight (MW) of 16,000 and a cerium acid content of 38 mgKOH/g. [Comparative Example 1] Synthesis of aromatic ring-containing polymer (X-6) (monomer composition ratio, I-al: II-al = 0: 100) In addition to the formula (I-al), the acrylic acid shown The amount of the monomer used was changed to 0, and the amount of the (meth)acrylic monomer represented by the formula (ΙΙ-al) was changed to 10.0 g (0.028 mol), and the same procedure as in Example 1 was carried out. The obtained aromatic ring-containing polymer (X-6) had a weight average molecular weight (MW) of 20,000 and an acid hydrazine of OmgKOH/g. 2. Synthesis of a polymerizable polymer (addition reaction to a cyclic monomer) [Example 6] A combination of a polymerizable polymer (Yl) (monomer composition ratio = 40: 60) was obtained in Example 1 Synthetic polymer composition (monomer composition ratio = 40:60) 40. lg [containing aromatic ring polymer (X-1) 10.0 g] - heating while stirring, at a liquid temperature of 60 ° C, injecting a Glycidyl acrylate (GMA) 1.54g (0.011mol, MW142), polymerization inhibitor, hydroquinone monomethyl ether (MEHQ) 0.006g and esterification catalyst dimethyl benzylamine 0.019g (0.000 1 43 Mol), then, heating is continued, and the reaction is carried out at a reaction temperature of 95 to 1 °C. When the acid hydrazine reaction rate is 90.0% or more, the reaction temperature is stopped until the reaction liquid temperature is cooled to 30 ° C or lower. Then, 4.43 g of cyclohexanone was added while stirring at -28 - 201004978 to obtain a polymerizable polymer composition of 46.16 g [containing a polymerizable polymer (Y-1) 11.54 g]. The obtained polymerizable polymer had a weight average molecular weight (MW) of 24,000 and an acid lanthanum of 4 mgKOH/g. The acid hydrazine reaction rate is determined based on the following calculation formula. Acid hydrazine reaction rate (%) = {1 - the number of COOH groups determined from the acid hydrazine of the poly-complex polymer} χ 1 〇〇 " Determined from the acid hydrazine containing the aromatic ring polymer before the reaction As a result of the number of COOH groups, the acid oxime reaction rate of the product was 93%. <Measurement of double bond equivalent> 双 The double bond equivalent of the polymerizable polymer (Υ-1) (the weight of the polymer per 1 mol of the ethylenically unsaturated group) was determined by the following calculation formula. The amount of the double bond equivalent polymerizable polymer (g) _ The number of the ethylenically unsaturated groups (mol) contained in the polymerizable polymer As a result, the double bond equivalent was 1134. [Example 7] Synthesis of polymerizable polymer (Y-2) (monomer composition ratio = 50:50) The polymer (γ·2) synthesized in Example 2 (monomer composition ratio = 50:50) 40.lg [Aromatic ring-containing polymer (Χ-2) 10.0g]—heated while stirring, and charged 1.93 g (0.014 mol) of glycidyl methacrylate (GMA) at a liquid temperature of 60 °C. The polymerization preventive agent was 0.006 g of hydroquinone monomethyl ether and 0.024 g (0.000181 mol) of dimethylbenzylamine of an esterification catalyst, and then heating was continued, and the reaction was carried out at a reaction temperature of 95 to 105 t. When the acid hydrazine reaction rate is 90.0% or more, the reaction liquid temperature is cooled to 30 ° C or lower, and the reaction is stopped. Then, 5.69 g of cyclohexanone was added while stirring to obtain a polymerizable polymer having a polymerizable polymer composition of 47.72 g [containing a polymerizable polymer (Y-2) -29-201004978 1 1.93 g]. The weight average molecular weight (MW) is 23,000' double bond equivalent weight is 938, and acid hydrate is 6 mg KOH/g. Moreover, the acid hydrazine reaction rate was 91%. [Example 8] Synthesis of polymerizable polymer (Y_3) (monomer composition ratio = 1 〇〇: 〇) The polymer synthesized as described above (monomer composition ratio = 1 00:0) 40.lg [containing aroma Ring polymer (X-3) 10.0 g] - heated while stirring, and charged with glycidyl methacrylate (GMA) 〇 3.86 g (〇.〇28m〇l) at a liquid temperature of 60 ° C 6 g of monomethyl ether hydrazine 〇〇 6 g and dimethyl benzylamine of esterification catalyst were used, and then heating was continued, and the reaction was carried out at a reaction temperature of 95 to 105 ° C. When the acid hydrazine reaction rate is 90.0% or more, the reaction liquid temperature is cooled to 30 ° C or lower, and the reaction is stopped. Then, 11.48 g of cyclohexanone was added while stirring to obtain 55.44 g of a polymerizable polymer composition (containing polymerizable polymer (Y_3) i 3.86 g). The obtained polymerizable polymer had a weight average molecular weight (MW) of 25,000, a double bond equivalent of 504, and an acid hydrazine of 2 mgKOH/g. Moreover, the acid hydrazine reaction rate was 98%. ® [Example 9] Synthesis of polymerizable polymer (Υ-4) (monomer composition ratio = 40:60) The aromatic ring-containing polymer synthesized as described above (monomer composition ratio = 40:60) 40_lg [including Aromatic ring polymer (χ_4) lO.Og]—heating while stirring, adding 1.93 g (0.014 mol) of glycidyl methacrylate (GMA) at a liquid temperature of 60 ° C, and a polymerization inhibitor 0.0 g (0.000181 mol) of 6 g of dimethyl benzylamine and an esterification catalyst, and then heating was continued, and the reaction was carried out at a reaction temperature of 95 to 105 °C. When the acid hydrazine reaction rate is 90.0 % or more, the temperature of the reaction liquid is cooled to 30 ° C or lower, and the reaction is stopped at -30-201004978. Then, 5.69 g of cyclohexanone was added while stirring, and the weight average molecular weight (MW) of the polymerizable polymer (γ_4) obtained by preparing the polymerizable polymer composition 47.72 g [containing polymerizable polymer 11.93 g] was 24,000. The double bond equivalent is 893' acid bismuth is 3 mgKOH/g. Moreover, the acid hydrazine reaction rate was 95%. [Example 10] Synthesis of polymerizable polymer (Υ-5) (monomer composition ratio = 20:80) The aromatic ring-containing polymer synthesized as described above (monomer composition ratio 〇 = 20: 80) 4 〇. Lg [containing aromatic ring polymer (X-5) lO.Og] - while stirring - heating, at a liquid temperature of 60 ° C, into the glycidyl methacrylate (GMA) 0.97g (0.007mol), The polymerization preventive agent was hydrogenohydromonoformate ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium hexamethyl methacrylate (0.0 00 00 00 00 00 00 00 eq. When the acid hydrazine reaction rate is 90.0% or more, the temperature of the reaction liquid is cooled to "the following, and the reaction is stopped. Then, 2.81 g of cyclohexanone is added while stirring, to obtain a polymerizable polymer composition of 4 3 · 8 8 g. [Contains polymerizable polymer (γ _ 5 ) ® 10.97 g]. The obtained polymerizable polymer has a weight average molecular weight (M w) of 18,000, a double bond equivalent of 1710, and a cerium acid content of 3 mgKOH/g ❶. The rate is 92%. 3. Synthesis of polyfunctional liquid crystalline polymer composition [Example 11] Synthesis of polyfunctional liquid crystalline polymer composition (Z-1) was carried out by introducing a polymerizable polymer composition of 46.16 g [ Containing polymerizable polymer (Yl) 11.54g], and subtype (VI-a): -31- 201004978

[In the formula, Π is 6] The polyfunctional liquid crystalline monomer I7.31 g [1.5 times the weight of the polymerizable polymer (Y-1)] and 1.44 g of the photopolymerization initiator IRGACURE 907 The solution of 86.54 g of cyclohexanone was mixed and mixed for 1 hour to prepare a functionally functional liquid crystalline polymer composition of 151.55 g. The solid component 'double bond equivalent contained in the composition of the obtained polyfunctional liquid crystalline polymer (Z1) was 468, and the acid hydrazine was 2 mgKOH/g. [Example 12] Synthesis of polyfunctional liquid crystalline polymer composition (Z-2): The polymerizable polymer composition was changed to the polymerizable polymer composition of Example 7 47.72 g [containing a polymerizable polymer] (Y_2) u 93g], and the polyfunctional liquid crystalline monomer of the above formula (VI-a) [wherein η is 6] is changed to 17.90 g [1.5 times with respect to the polymerizable polymer (γ 2 )] The operation was carried out in the same manner as in the example i. The solid content contained in the composition of the obtained polyfunctional liquid crystalline polymer (Z-2) was 4 52 in terms of double bond and 2 mg KOH/g in acid. [Example 13] Synthesis of polyfunctional liquid crystalline polymer composition (z_3): The polymerizable polymer composition was changed to the polymerizable polymer composition of Example 8 and 55.44 g [containing a polymerizable polymer (Y- 3) 13.86g], and the polyfunctional liquid crystalline monomer of the above formula (VI-a) [wherein η is 6] is changed to 2〇.79g [1.5 times relative to the polymerizable polymer (γ_3)] The operation was carried out in the same manner as in Example 11 except for the above. The solid content contained in the composition of the obtained polyfunctional liquid crystalline polymer (Z-3) had a double bond equivalent of 388 and an acid hydrazine of 1 mgKOH/g. -32-201004978 [Example 14] Synthesis of polyfunctional liquid crystalline polymer composition (Z-4): 46.16 g [containing polymerizable polymer (Y-1) 11.54 g] was added to the polymerizable polymer composition. Further, the polyfunctional liquid crystalline monomer of the above formula (VI-a) [wherein η is 6] 17_31 g, the photopolymerization initiator IRGACURE 907 1.44 g, cyclohexanone 86.54 g and BYK-323 (surfactant) The solution of 29 g of yttrium was stirred and mixed for 1 hour to prepare 151.48 g of a polyfunctional liquid crystalline polymer. The solid component contained in the composition of the obtained polyfunctional liquid crystalline polymer (Z-4) had a double bond equivalent of 468 and an acid hydrazine of 2 mgKOH/g.实施 [Example 15] Synthesis of polyfunctional liquid crystalline polymer composition (2-5) In addition to changing the polymerizable polymer composition to the polymerizable polymer composition of Example 9, 47.72 g [Polymerizable polymer (γ_4) Ii.93g], and the polyfunctional liquid crystalline monomer of the above formula (VI-a) is changed to iy.Mg [1.5 times with respect to the polymerizable polymer (Y-4)] Implement the operation. The solid content contained in the composition of the obtained polyfunctional liquid crystalline polymer (Z-5) had a double bond equivalent of 448 and an acid hydrazone of 1 mg K 〇 H / g. [Example 1 6] Synthesis of polyfunctional liquid crystalline polymer composition (z-6) In addition to changing the polymerizable polymer composition to the polymerizable polymer composition of Example 10, 43.8 8 g [Polymerizable polymer] (Y_5) i〇97g], and the polyfunctional liquid crystalline monomer of the above formula (VI-a) was changed to 16 46 g [1.5 times with respect to the polymerizable polymer (Y-5)], and examples 14 performs the same operation. The solid component 'double bond equivalent contained in the composition of the obtained polyfunctional liquid crystalline polymer (Z-6) was 495, and the acid hydrate was img K 〇 H / g. [Example 17] Synthesis of polyfunctional liquid crystalline polymer composition (z_7): The polymerizable polymer composition was changed to the polymerizable polymer composition of Example 8 and 55.44 g [polymerizable polymer (γ_3) η In the same manner as in Example 14, except that the polyfunctional liquid crystalline monomer of the formula (VI-a) of the above-mentioned -33-201004978 was changed to 20.79 g [1.5 times with respect to the polymerizable polymer (Y_3)]. Implement the operation. The solid content contained in the composition of the obtained polyfunctional liquid crystalline polymer (Ζ-7) was 388 in terms of double bond and imgKOH/g in acid. [Comparative Example 2] Synthesis of polyfunctional liquid crystalline polymer composition (Z-9): The polymerizable polymer composition was changed to the aromatic ring-containing polymer composition of Example 1 (monomer composition ratio = 40: 60) The operation was carried out in the same manner as in Example 11 except that 40.g [containing an aromatic ring polymer (Xl) lO.Og]. The solid content contained in the composition of the obtained polymer (z-9) was 560 in terms of double bond and 24 mg KOH/g in acid. [Comparative Example 3] Synthesis of polyfunctional liquid crystalline polymer composition (Z-10) The polymerizable polymer composition was changed to the aromatic ring-containing polymer composition of Comparative Example 1 (monomer composition ratio = 0: 100) The operation was carried out in the same manner as in Example 11 except that 40. lg [containing an aromatic ring polymer (X-6) 10 O.Og]. Regarding the solid content contained in the composition of the obtained polymer (Z-10), the double bond equivalent was 560 « acid hydrazine was OmgKOH/g. The composition and ratio of the polymer of the examples and the comparative examples, the acid enthalpy of the polymer, the double bond equivalent weight, and the weight average molecular weight are shown in Tables 1 to 3 below. -34- 201004978 [Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Composition containing aromatic ring polymer (X-1) Aromatic ring-containing polymer (X-2) Aromatic ring-containing polymer (X-3) Aromatic ring-containing polymer (X-4) Aromatic ring-containing polymer (X-5) Polymerizable polymer (Y-1) Polymerizable polymer (Y-2) Single Body (I-al) ratio 4 5 10 - - 4 5 Monomer (I-fl) ratio - - - 4 2 - - Monomer (Π-al) ratio 6 5 0 6 8 6 5 Is there a GMA addition GMA? GMA-free, GMA-free, GMA-free, GMA-free, GMA-free, GMA, polymer-based monomer (VI-a), wt%, solids, surfactant, weight%, acid 値61 77 152 77 38 4 6 Double bond equivalent - - - - - 1134 938 Weight average molecular weight 18000 14000 18000 18000 16000 24000 23000

-35-201004978 [Table 2] Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Composition Polymerizable Polymer (Y-3) Polymerizable Polymer (Y-4) Polymerizable Polymer (Y-5) Polyfunctional liquid crystalline polymer composition (Z-1) Polyfunctional liquid crystalline polymer composition (Z-2) Polyfunctional liquid crystalline polymer composition (Z-3) Monomer ( I-al) ratio 10 - - 4 5 10 monomer (I-fl) ratio - 4 2 - - - monomer (Π-al) ratio 0 6 % 6 5 0 Whether there is GMA addition GMA has GMA with GMA GMA has GMA and GMA has a weight percentage of monomer (VI-a) for the polymer 150% 150% 150% % by weight of surfactant for solid content Acid 値 2 3 3 2 2 1 Double bond Equivalent 504 893 1710 468 452 388 Weight average molecular weight 25000 24000 18000 - - Ο -36- 201004978 [Table 3]

Example 14 Example 15 Example 16 Example 17 Comparative Example 1 Comparative Example 2 Comparative Example 3 Composition Polyfunctional Liquid Crystal Polymer Composition (Z-4) Polyfunctional Liquid Crystal Polymer Composition (Z-5) Polyfunctional liquid crystalline polymer composition (Z-6) Polyfunctional liquid crystalline polymer composition (Z-7) Polymer containing aromatic ring (X-6) Polyfunctional liquid crystalline polymer composition ( Z-9) Polyfunctional liquid crystalline polymer composition (Z-10) Monomer (I-al) ratio 4 - 10 0 4 0 Monomer (I-fl) ratio - 4 2 0 - - - Monomer ( Il-al) Proportion 6 6 8 0 10 6 10 Is there a GMA addition GMA with GMA with GMA with GMA with GMA without GMA without GMA without polymer for monomer (VI-a) by weight % 150% 150 % 150% 150% 150% 150% % by weight of surfactant for solid components 0.1 0.1 0.1 0.1 Acid bismuth 2 1 1 1 0 24 0 Double bond equivalent 468 448 495 388 - 560 560 Weight average molecular weight - - - - 20000 - -37- 201004978 4. Evaluation of performance of polyfunctional liquid crystalline polymer Each of the polyfunctional liquid crystalline polymer groups of the above respective examples and comparative examples The film is formed in the following order, and the film coating property, transparency, retardation in the thickness direction per unit thickness (Rth/d), and retardation in the in-plane direction per unit thickness (Re) /d), evaluated by the following method. <Film formation method> (1) Treatment film at 90 ° C: About 2 ml of a polyfluorene-functional liquid crystalline polymer composition was cast on a substrate (glass and polyimide, 10 x 10 cm 2 ), and a film was formed by spin coating. Thereafter, it was dried (90 ° C / 10 minutes) to prepare an alignment film having a thickness of about 2 / / m, and was cooled to 30 ° C. (2) 23 ° C treatment film: After cooling the alignment film prepared as described above to 30 ° C, the film was irradiated with ultraviolet light having an exposure amount of 900 mJ/cm 2 and cured to a high temperature treatment (230 ° C / 1 〜 After 3 hours), it was cooled to 30 °C. <Evaluation of the applicability and the transparency of the film> The film prepared by the above was visually observed and evaluated, and the coating property and transparency were evaluated based on the following criteria. Coating property: A: The film surface was uniform and good B: A small amount of streaks or discharge marks were observed. C: A large number of streaks or discharge marks were observed to cause transparency of the film: Evaluation was made regarding the film produced by the above. 〇:Transparent-38-201004978 χ: Whitening situation <Evaluation of optical characteristics> With respect to the film obtained above, the polarizing analyzer OPTIPRO (manufactured by SHINTEC) was measured under the following conditions to obtain Rth/d and Re/d. . Measurement wavelength; I: 550 [nm] • Thickness of film d: 2 [# m] < evaluation result> The evaluation results described above are shown in Tables 4 to 8 below. As can be seen from the table, the polyfunctional liquid crystalline polymer composition of the Φ embodiment can provide a film having good birefringence characteristics, coatability, film transparency, and birefringence which does not change even when exposed to a high temperature. . E-39-201004978 [Table 4] 90 ° C treated film on glass substrate Evaluation Example 1 Evaluation Example 2 Evaluation Example 3 Evaluation Comparative Example 1 Evaluation Comparative Example 2 Composition Example 11 Example 12 Example 13 Comparison of Comparative Example 2 Example 3 polyfunctional polyfunctional polyfunctional liquid polyfunctional liquid liquid crystalline polymerized liquid crystalline polymerizable liquid crystalline polymerizable crystalline polymer crystalline polymer composition composition composition composition Composition (Z-1) (Z-2) (Z-3) (Z-9) (Z-10) Rth/d -0.13 -0.13 -0.10 -0.11 0.13 Re/d 0.00 0.00 0.00 0.00 0.00 Coating AAAAA film transparency 〇〇〇〇X substrate glass glass glass glass reference [Table 5] 90 ° C treatment film evaluation on the polyimide substrate 4 Evaluation Example 5 Evaluation Comparative Example 3 Evaluation Comparative Example 4 Composition Example 11 The polyfunctional energy-possible liquid crystalline polymerizable liquid crystalline polymerizable polymerizable liquid crystalline polymerizable liquid crystalline polymer composition of the compound of Comparative Example 2 Composition (Z-1) (Z-2) (Z-9) (Z-10) Re/ d 0.09 0.09 0.07 0.17 Coating B B A B Film 〇 〇 X Transparency Substrate Polyimine Polyimine Polyimine Polyimine Polyamine -40- 201004978 [Table 6] 230 ° C treatment on glass substrate

Evaluation Example 6 - Example 7 - Example 8 Evaluation Comparative Example 5 Evaluation Comparative Example 6 Composition Example Π Polyfunctional liquid crystalline polymer composition (Z-1) The polyfunctional liquid crystalline polymer composition of Example 12 (Z-2) Polyfunctional liquid crystalline polymer composition (Z-3) of Example 13 Polyfunctional liquid crystalline polymer composition of Comparative Example 2 (Z-9) Polyfunctional liquid crystallinity of Comparative Example 3 Polymer composition (Ζ-10) Rth/d (1 hour) -0.08 -0.05 -0.08 Unable to measure Rth/d (2 hours) -0.07 -0.05 -0.08 Rth/d (3 hours) -0.06 •0.03 -0.07 Re/d (1 hour) 0.00 0.00 0.00 Re/d (2 hours) 0.00 0.00 0.00 Re/d (3 hours) 0.00 0.00 0.00 Coating AAACC film transparency 〇〇〇 XX substrate glass glass glass glass - 41 - 201004978 [Table 7] 230 ° C treatment film on polyimide substrate

Evaluation Example 9 Evaluation Example 10 Evaluation Comparative Example 7 Evaluation Comparative Example 8 Composition Example 1 1 Multiple Example 12 Multiple Comparative Example 2 Multifunctional Liquid Crystal Functional Liquid Crystal Functional Functional Liquid Crystal Functional Liquid crystalline polymer composition Polymer composition Polymer composition Polymer composition (Z-1) (Z-2) (Z-9) (Z-10) Rth/d 0.01 0.03 Unmeasurable measurement impossible (1 H) Rth/d 0.02 0.02 (2 hours) Rth/d 0.02 0.02 (3 hours) Re/d 0.08 0.08 (1 hour) Re/d 0.08 0.08 (2 hours) Re/d 0.07 0.08 (3 hours) Coating BBCC Film transparency XX substrate polyimide polyimide polyimide polyimide polyimide polyimide 42-201004978 [Table 8] 230 ° C treatment on polyimide substrate evaluation Example 11 Evaluation Example 12 Evaluation Example 13 Evaluation Example 14 Composition type for evaluation Example 1 Multifunctional liquid crystalline polymer composition (Z-4) Example 1 5 polyfunctional liquid crystalline polymer composition (Z-5) Example 1 6 polyfunctional liquid crystalline polymer composition (Z- 6) The polyfunctional liquid crystalline polymer composition of Example 17 (Z-7) Re/d (1 hour) 0.11 0.10 0.10 0.08 Re/d (2 hours) 0.10 0.09 0.09 0.08 Re/d (3 hours) 0.10 0.08 0.09 0.07 Coating AAAA Film Transparency 〇〇〇〇 Substrate Polyimine Polyimine Polyimine Polyimine 5. Synthesis of Aromatic Ring Polymer (AP)-2 [Example 18] Acrylic monomer represented by a synthetic formula (Ι-al) containing an aromatic ring polymer (W-1) (monomer composition ratio, I-al: II-al: methacrylic acid = 40:5 0: 1 0) 4.0g (0.011mol), ginseng

(Bu a1) (wherein η is 6, 01 is a carboxyl group.) An acrylic monomer represented by the formula (Ibal) 5.0 g (0.017 mol),

(wherein, η was 6, G2 was a cyano group) and a solution of methacrylic acid 1.0 g and cyclohexanone 3 〇.〇g was stirred and mixed for 1 hour in a nitrogen gas stream. Then, the mixed solution is heated to form an azobisisobutyronitrile (AIBN) O.lg which is charged with a polymerization initiator at a liquid temperature of 75 ° C, and is carried out at a temperature of from 75 to 85 ° C in the range of -43 to 201004978. The polymerization was carried out for 8 hours. As a result, a polymer composition of 4 〇.lg [containing an aromatic ring-containing polymer (W-l) lO.Og] was obtained. <Measurement of Weight Average Molecular Weight (MW)> The weight average molecular weight (MW) of the aromatic ring-containing polymer (W-1) was measured by gel filtration chromatography (GPC). The weight average molecular weight (MW) of the obtained aromatic ring-containing polymer was 1 800 00. <Measurement of acid bismuth> The measurement method is as follows. In other words, about 60 ml of ethanol was added to a 1000 ml Erlenmeyer flask, and phenolphthalein was used as an indicator to neutralize with a 〇.lm〇l/aqueous sodium hydroxide solution. About 1.5 g of the polymer composition was weighed, uniformly dissolved and stirred in the above solution, and titrated with a 0.1 mol of a 1/1 sodium hydroxide aqueous solution, and the reddish color disappeared for about 30 seconds as the end point of the titration. The following formula is used as a benchmark to determine the acidity. Acid 値 = (0.1xfxAx56.1 / B) / (C / 100) A: titration (ml) pf: coefficient of aqueous sodium hydroxide solution B: amount of polymer composition (g) C: polymer concentration (%) ( Amount of polymer / amount of polymer composition X100) The above-mentioned acid ring of the aromatic ring-containing polymer (W-1) was 34 mgKOH/g. [Example 19] Synthesis of aromatic ring-containing polymer (W-2) (monomer composition ratio, Ia-1: II-al: acrylic acid = 20:70:10), except that the formula (Ia) was respectively The amount of the (meth)acrylic monomer used was changed to 2. 〇g (〇.〇〇5 mol), and the amount of the (meth)acrylic monomer-44 - 201004978 represented by the formula (ΙΙ-a) was changed to The same procedure as in Example 18 was carried out except that 7.0 g (0.023 mol) was used instead of methacrylic acid using 1.0 g of acrylic acid. The obtained aromatic ring-containing polymer (W-2) had a weight average molecular weight (MW) of 14,000 and a strontium acid of 27 mgKOH/g. [Example 20] Synthesis of aromatic ring-containing polymer (W-3) (monomer composition ratio, I-al: II-al: ARONIXM-5300 = 30:57:13), except that the formula (Ia) is respectively shown The amount of the (meth)acrylic monomer used was changed to 3.0 g (0.008 mol), and the amount of the (meth)acrylic monomer m ¥ represented by the formula (ΙΙ-a) was changed to 5.7 g (0.019 mol). And using ARONIXM-5300 [〇>-carboxypolycaprolactone (η* 2) monoacrylate: (:112 = (:11(:〇〇-(<:51110(:〇〇)11- 11. East Asia Synthetic Co., Ltd. was carried out in the same manner as in Example 1 except that methacrylic acid was used. The obtained aromatic ring-containing polymer (W-3) had a weight average molecular weight (MW) of 14,000 and a strontium acid of 18 mgKOH/ g. [Comparative Example 4] Synthesis of aromatic ring-containing polymer (W-4) (monomer composition ratio, I-al: @II-al=40:60), except for the formula (Ia) The amount of the acrylic monomer used was changed to 4.0 g (0.005 mol), and the amount of the (meth)acrylic monomer represented by the formula (ΙΙ-a) was changed to 6.0 g (0.023 mol), and was carried out. Example 1 was carried out in the same manner. The obtained aromatic ring-containing polymer (W-2), weight average score The amount (MW) was 22,000, and the acid hydrazine was i5 mgKOH/g. [Comparative Example 5] Aromatic ring-containing polymer (W-5) (monomer composition ratio, l-ai: Π-al: acrylic acid = 20:60:20 The synthesis of the (meth)acrylic monomer represented by the formula (Ia) is changed from -45 to 201004978 to 2.0 g (0.005 mol), and the (meth) group represented by the formula (ΙΙ-a) The amount of the acrylic monomer used was changed to 6.0 g (0-023 mol) and 2.0 g of acrylic acid, and the same procedure as in Example 1 was carried out. The obtained aromatic ring-containing polymer (W-2) had a weight average molecular weight (MW) of 14,000. The acid hydrazine is 46 mgKOH/g. 6. Synthesis of a polymerizable polymer (addition reaction to a cyclic monomer)-2 [Example 21] Polymerizable polymer (XX-1) (monomer composition ratio, la Synthesis of -1 : II-al : methacrylic acid = 4 0: 50: 10) The polymer composition synthesized in Example 18 was 40. lg [containing an aromatic ring polymer (W_l) lO.Og]. Heating while stirring, adding 1.5 g (0.011 mol, MW142) of glycidyl methacrylate (GMA), hydroquinone monomethyl ether (MEHQ) 0.006 g of polymerization inhibitor, and esterification touch at a liquid temperature of 60 ° C Medium dimethyl benzylamine 0.02g (0.000 1 43m Ol), then, heating is continued, and the reaction is carried out at a reaction temperature of 95 to 105 °C. The following formula: Acid hydrazine reaction rate (%) = {1_ __ The number of COOH oximes determined from the acid hydrazide of the polymerizable polymer _ } xl 〇〇 by the acid ring containing the aromatic ring polymer before the reaction When the acid hydrazine reaction rate defined by the number of C00H groups determined is 90.0% or more, the reaction liquid temperature is cooled to 30 ° C or lower, and the reaction is stopped. Then, 4.4 g of cyclohexanone was added thereto with stirring to obtain 46.0 g of a polymerizable polymer composition [containing a polymerizable polymer (XX-1) 11.4 g]. The obtained polymerizable polymer had a weight average molecular weight (MW) of 24,000 and a strontium acid of 18 mgKOH/g. <Measurement of double bond equivalent> The double bond equivalent of the polymerizable polymer (XX-1) (the weight of the polymer of the unsaturated group per 1 mol of the ethyl group - 46 - 201004978) was determined by the following calculation formula. Double bond equivalent = amount of polymerizable polymer (g)_ Number of ethylenically unsaturated groups (mol) contained in the polymerizable polymer As a result, the double bond equivalent was 1150. [Example 22] Synthesis of polymerizable polymer (XX-2) (monomer composition ratio, Ia-1: II-al: acrylic acid = 20:70:10) The polymer composition synthesized in Example 19 was used. .lg [Aromatic ring containing polymer (W-2) 10.0g] - heated while stirring, and charged with 4-hydroxybutyl acrylate glycidyl ether (4HBAGE) at a liquid temperature of 6 ° C. (0.008 mol, MW200), 0.006 g of hydroquinone monomethyl ether of a polymerization preventive agent and 0.002 g (0.000163 mol) of an esterification catalyst of dimethyl benzylamine, and then heating was continued at a reaction temperature of 95 to 105 ° C. The range is reacted. When the acid hydrazine reaction rate is 90.0% or more, the reaction liquid temperature is cooled to 30 ° C or lower, and the reaction is stopped. Then, 3.7 g of cyclohexanone was added while stirring to obtain 45.4 g of a polymerizable polymer composition [containing a polymerizable polymer (XX-2) ❹ 1 1.4 g]. The obtained polymerizable polymer had a weight average molecular weight (MW) of 23,000. Further, the acid hydrate was 15 mgKOH/g. The above polymerizable polymer (XX-2) has a double bond equivalent of 1 590. [Example 23] Synthesis of polymerizable polymer (XX-3) (monomer composition ratio, Ia-l··II-al: ARONIXM_5300 = 30:57:13) The polymer composition synthesized in Example 20 was used. 40.1 g [Polymerizable polymer (W-3) l〇.〇g] - heated while stirring, and charged with glycidyl methacrylate (GMA) 1.5 g (0.0070) at a liquid temperature of 60 °C M〇l, -47- 201004978 MW142), a polymerization inhibitor of hydroquinone monomethyl ether 0.006 g and an esterification catalyst of dimethylbenzylamine 0.014 g (0.000107 mol) 'then, continue heating at a reaction temperature of 95 The reaction was carried out in the range of ~105 t. When the acid hydrazine reaction rate is 70.0% or more, the reaction liquid temperature is cooled to 30 ° C or lower, and the reaction is stopped. Then, 3.3 g of cyclohexanone was added while stirring to obtain 44.4 g of a polymerizable polymer composition [containing polymerizable polymer (XX-3) 10.7 g]. The obtained polymerizable polymer had a weight average molecular weight (MW) of 23,000. The acid bismuth is 10 mgKOH/g. The above polymerizable polymer (X-3) double bond equivalent (weight of polymer per 1 mol of the non-saturated group of 1 mol) was 2,180. [Comparative Example 6] Synthesis of polymerizable polymer (XX-4) 40.1 g [polymerizable polymer (W-4) 10 · Og] of the polymer composition synthesized in Comparative Example 4 was heated while stirring. At a liquid temperature of 60 〇c, 0.77 g of glycidyl methacrylate (GMA) (0.005 m〇l, MW142), a hydroquinone monomethyl ether 聚合.〇〇6g of a polymerization inhibitor, and an esterification catalyst were introduced. Dimethylbenzylamine 0-015 g (0.000114 mol), and then heating was continued, and the reaction was carried out at a reaction temperature of 95 to 105 °C. When the acid hydrazine reaction rate is 90.0% ® or more, the reaction is stopped until the temperature of the reaction liquid is cooled to 30 ° C or lower. Then, 2.6 g of cyclohexanone was added while stirring to obtain 43.4 g of a polymerizable polymer composition (containing 10.7 g of a polymerizable polymer (x_4)). The obtained polymerizable polymer had a weight average molecular weight (MW) of 23,000. Further, the acid strontium was 8 mgKOH/g. The double bond equivalent of the polymerizable polymer (X·' (the weight of the polymer per 1 mol of the ethylenically unsaturated group) was 2,380. [Comparative Example 7] Synthesis of a polymerizable polymer (χχ_5) was synthesized in Comparative Example 5. Polymer composition 40.1 g [polymerizable polymer (W-5) 10.0 g] - while stirring - heating, at a liquid temperature of 6 〇〇 c -48 - 201004978, 4-hydroxybutyl acrylate epoxy Propyl ether (4HBAGE) l-60g (0.008mol, MW: 200), polymerization inhibitor, hydroquinone monomethyl ether 0.0055g and esterification catalyst dimethyl benzylamine oxime. 〇 2g (〇. 〇〇〇 1 5 mol), then 'continue heating, and the reaction is carried out at a reaction temperature of 95 to 105 ° C. When the acid hydrazine reaction rate is 90% or more, the reaction liquid temperature is cooled to 30 ° C or less until the reaction is stopped. Then, 3.4 g of cyclohexanone was added while stirring to obtain a polymerizable polymer composition of 45.1 g [containing polymerizable polymer (XX-5) 1 1.4 g]. The weight average molecular weight of the obtained polymerizable polymer ( MW) is ❹ 23000. Further, the acid bismuth is 32 mgKOH/g. The double bond equivalent of the above polymerizable polymer (XX-5) (per ethylenicity is not The weight of the polymer of the saturated group of 1 mol is 1580. 7. Production of a polyfunctional liquid crystalline polymer composition-2 [Example 24] Production of a polyfunctional liquid crystalline polymer composition (ZZ-1) - 2 The polymerizable polymer composition of Example 21 was 46. Og [containing polymerizable polymer (XX-1) 11.4 g], and the following formula (VI-a):

[In the formula, η is 6], the polyfunctional liquid crystalline monomer l7. lg [1.5 times the weight of the polymerizable polymer (XX-1)] photopolymerization initiator IRGACURE 907 of 1 · 4 g [ The total weight of the polyfunctional liquid crystalline monomer relative to the polymerizable polymer (XX-1) and the formula (VI-a) is 5%], cyclohexanone 97.2 g, and BYK_323 (surfactant) 〇.〇3g [The total weight of the polyfunctional liquid crystalline polymer with respect to the polymerizable polymer (XX-1) and the formula (VI-a) is 0.1 ° /. The solution was stirred and mixed for 1 hour to prepare a polyfunctional liquid crystal. -49 - 201004978 Polymer composition 160.3 g. The solid content contained in the composition of the obtained polyfunctional liquid crystalline polymer (Z-1) was 545 in terms of double bond and 27 mg KOH/g in acid strontium. [Example 25] Synthesis of polyfunctional liquid crystalline polymer composition (zz_2): The polymerizable polymer composition was changed to the user of Example 23, 44.4 g [containing polymerizable polymer (χχ·3) l〇 _7g] was carried out in the same manner as in Example 24 except that the polyfunctional liquid crystalline monomer of the formula (vi-a) was changed to 16.lg [1.5 times with respect to the polymerizable polymer (χχ_3)]. The solid content contained in the composition of the obtained polyfunctional liquid crystalline polymer (ZZ-2) had a double bond equivalent of 599 and an acid lanthanum of 15 mgKOH/g. [Example 26] Synthesis of polyfunctional liquid crystalline polymer composition (ZZ_3) except that the photopolymerization initiator was changed to 111 〇8 (:1; 11 £ 907 [relative to polymerizable polymer and polyfunctional liquid crystallinity The total weight of the monomers was 3%] and OXE-02 [the total weight of the polymerizable polymer and the polyfunctional liquid crystalline monomer was 2%], and the operation was carried out in the same manner as in Example 24. The obtained polyfunctionality The solid content contained in the composition of the liquid crystalline polymer (ZZ-3) was 545 by double bond and 27 mgKOH/g of acid strontium. [Comparative Example 8] Polyfunctional liquid crystalline polymer composition (ZZ- 5) Synthesis except that the polymerizable polymer composition was changed to the polymerizable polymer composition of Comparative Example 6 43.4 § [Polymerizable polymer (also -4) 10.78], and the formula (¥1-&amp;) The polyfunctional liquid crystalline polymer obtained in the same manner as in Example 24 except that the polyfunctional liquid crystalline monomer was changed to 16.1 g [1.5 times with respect to the polymerizable polymer (XX-4)] The solid content contained in the composition of ZZ-5) was 603 and the acid bond was 12 mgKOH/g. [Comparative Example 9] Polyfunctional liquid crystalline polymer group Synthesis of the substance (ZZ-6) - 50 - 201004978 The polymerizable polymer composition was changed to the polymerizable polymer composition of Comparative Example 7 by 45.1 g [polymerizable polymer (XX-5) 1 1.4 g], and The polyfunctional liquid crystal monomer of the formula (Vl_a) was changed to 17. lg [1.5 times with respect to the polymerizable polymer (XX-5)], and the operation was carried out in the same manner as in Example 24. The solid component contained in the composition of the liquid crystalline polymer (ZZ-6) had a double bond equivalent of 574 and an acid lanthanum of 49 mgKOH/g. When the polymers of Examples 24 to 26 and Comparative Examples 8, 9 were produced. The composition and ratio, the acid enthalpy of the polymer, and the double bond equivalent are shown in the following Table 9. 〇❿ -51 - 201004978 [Table 9] 实施 Example 24 Example 25 Example 26 Comparative Example 8 Comparative Example 9 Composition Polyfunctional liquid crystalline polymer composition (ZZ-1) Polyfunctional liquid crystalline polymer composition (ΖΖ-2) Polyfunctional liquid crystalline polymer composition (ΖΖ-3) Polyfunctional liquid crystalline polymer composition (ΖΖ-5) Polyfunctional liquid crystalline polymer composition (ΖΖ-6) Monomer (I-al) ratio 40 30 40 40 20 Monomer (Π-al) ratio Example 50 57 50 60 60 Proportion of methacrylic acid 10 10 - - Proportion of acrylic acid - - - - 20 ARONIXM-5300 Proportion 13 ~ - - Is there any GMA addition? There is Jtrrt. Is there any 4HBAGE addition? ΑττΤ No weight (%) of the monomer (VI-a) for the polymer 150% 150% 150% 15 0% 150% % by weight of the surfactant for the solid component 0.1 0.1 0.1 0.1 0.1 27 15 27 12 49 Double bond equivalent 545 599 545 603 574 Φ 8. Evaluation of properties of each polyfunctional liquid crystalline polymer composition - Each of the polyfunctional liquid crystals of Examples 24 to 27 and Comparative Examples 8, 9 The composition was formed into a film in the following order, and the coating properties, transparency, and retardation Re (Re/d) in the in-plane direction per unit thickness of each film were evaluated by the following methods. &lt;Film formation method&gt; (1) Treatment film at 230 ° C: Approximately 2 ml of a functional liquid crystalline polymer composition was cast on a substrate (glass and polyimine, l〇xl〇cm 2 ), After the film was formed by a spin coating method, it was dried (90 ° C / 10 minutes) to form an alignment film having a thickness of about 2 ° C, and cooled to 30 ° C. Then, the ultraviolet light having an exposure amount of 900 mJ/cm 2 was irradiated. The alkali aqueous solution (0.1% sodium carbonate aqueous solution) was treated to remove only the non-exposure range, and the produced film was subjected to high temperature treatment (23 0 ° C / 1 hour), and then cooled to 3 Torr. (:.) The film obtained by the above was evaluated by visual observation and the transparency was recorded. 〇: Transparent X: whitening condition &lt;developability&gt; The time required for the non-exposure range of the aqueous solution (0.1% sodium carbonate aqueous solution) of the membrane method. &lt;Evaluation of optical characteristics&gt; ® The film obtained as described above was subjected to the following conditions, polarizing analyzer OPTIPRO (SHINTEC ( (Measurement) and determination of Re/d. • Measurement wavelength: 550 [nm] • Thickness of film d: 2 [μm] &lt; alignment uniformity&gt; The film obtained above was evaluated using a polarizing microscope The alignment uniformity was observed under a direct polarized light, and it was confirmed that there was no light leakage phenomenon from the alignment defect of the liquid crystal, and X was not the case. <Evaluation of heat resistance> -53- 201004978 The above film was added. After heating at 23 ° C for 3 hours, 'Re/d was obtained again, and the change of Re/d before heating was determined. <Evaluation Results> The evaluation results described above are shown in Table 10 below. As can be seen from the table, the number of examples 24 to 26 The functional liquid crystalline polymer composition can provide a film having good birefringence characteristics, film transparency, and which does not change even when exposed to the temperature of the birefringence.

-54-201004978 [Table 10] Example 24 Example 25 Example 26 Comparative Example 8 Comparative Example 9 Developability 50 seconds 70 seconds 50 seconds Undevelopable peeling transparency 〇〇〇〇 Unable to measure alignment uniformity 〇〇〇〇 The Re/d of the treated film at 23 °C was measured. 0.085 0.065 0.085 0.085 Cannot measure 230 °C 'The rate of change of Re/d after additional heating for 3 hours (%) 9 14 8 11 Cannot be measured ❹ [Industrial price] The film using the composition of the present invention has good birefringence characteristics and has an advantageous feature that the birefringence does not change even when exposed to a high temperature used in manufacturing a liquid crystal panel, and therefore, according to the composition of the present invention, The polymerizable liquid crystal film having excellent optical properties is provided in the liquid crystal cell, which is more preferable than the outside of the liquid crystal cell, and is extremely advantageous in terms of thinning and cost reduction of the liquid crystal panel. Further, since the optical anisotropy can be maintained stably not only at room temperature but also at a high temperature, it can be used for various electronic devices or hologram materials outside the liquid crystal panel. [Simple description of the diagram]. None. [Main component symbol description] None. -55-

Claims (1)

201004978 VII. Patent Application Range: 1. A polymerizable polymer which is an aromatic ring containing a polymerizable monomer (PM) formed by a (meth)acrylic monomer represented by the formula (1). a polymer (AP), an epoxy group having a side chain (Q) containing an ethylenically unsaturated bond, or a cyclic monomer having an oxetane skeleton, in the aromatic ring-containing polymer (AP) a hydroxyl group and/or a carboxyl group, and an addition reaction with an epoxy group or an oxetane skeleton of the cyclic monomer, (wherein, L is a hydrogen atom or a methyl group; and eight, and A2 are each independently an alkylene group or a single bond having a carbon number of 1 to 4; a hydroxyl group or a carboxyl group; and X is (i) a carbon number of 1-18. An alkyl group having an alkyl group having a carbonyl group of 1 to 18 at a terminal end of the adjacent phenoxy group, (iii) having a C 1-18 alkylene group having a carbon number of 1-6 alkyl group bonded via -COO-bonding at the end opposite to the phenoxy group side, or (iv) The end opposite to the phenoxy side has a series of bonded 1-10-C2H40-based alkyl groups having 1-18 carbon atoms; a and b are 0 or positive satisfying a + b = 0~2 Integer). 2. The polymerizable polymer according to claim 1, wherein the polymerizable monomer (PM) is a monomer containing a (meth)acrylic monomer represented by the formula (II). -56- 201004978 (wherein, r2 is a hydrogen atom or a methyl group; A3 and A4 are each independently an alkylene group having a carbon number of 1 to 4, a -COO- group, or a single bond; and Z! to Z3 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; X2 is an alkylene group having 1 to 18 carbon atoms; c and d satisfying c + d = 0 to 2 of 0 or a positive integer). 3. The polymerizable polymer according to claim 1 or 2, wherein the cyclic monomer is an aliphatic epoxy group-containing monomer represented by formula (III), and the fat represented by formula (IV) a monomer of a oxetane or a monomer containing a alicyclic aliphatic epoxy group represented by the formula (V), r3^^q (10) (wherein R3 is a hydrogen atom or a carbon number of 1 to 4) alkyl) (wherein R4 to R6 are a hydrogen atom or a courtyard having a carbon number of 1 to 4) Rn Rn (In the formula, R7 to R15 are a hydrogen atom or a polymer group having a carbon number of 1 to 4, and a polymerizable polymer according to any one of claims 1 to 3, wherein the aromatic ring-containing polymer (AP) The reaction rate with the cyclic monomer is 5 mol% or more. -57 - 201004978 5 - a polyfunctional liquid crystalline polymer composition - which contains any of the first to fourth aspects of the patent application scope The polymerizable polymer of the present invention is formed of a polyfunctional monomer having two or more ethylenically unsaturated bonds in one molecule. 6 · The polyfunctional liquid crystalline polymer composition of claim 5 Wherein the polyfunctional monomer is a polyfunctional liquid crystalline monomer represented by the formula (VI), Y. -Yr^yji-0_Ti_〇_iL^^_Y 〇R16 0-Rn R, 7-〇Rl6 (VI) (wherein R16 is a hydrogen atom or a methyl group; Ri7 is an alkylene group having 1 to 18 carbon atoms or a terminal of the opposite side of the (meth)acryloxyloxy group having a -C00-group and - 0C0 - any one of the groups having an alkyl group having 1 to 18 carbon atoms; Ti is a group shown below; Z4 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms; and 丫1 is a single bond or -coo- ; Yi' is a single bond or -0C0-) Z4 ❿ 7. A polymer composition for a liquid crystal panel comprising a polyfunctional liquid crystalline polymer composition as disclosed in claim 5 or 6. A polymerizable film formed by applying a polyfunctional liquid crystalline polymer composition of claim 5 or 6 to a surface of a substrate. An optically anisotropic film formed by applying a polyfunctional liquid crystalline polymer composition according to claim 5 or 6 to a surface of a substrate and hardening it. The polymerizable polymer according to the first aspect of the invention, wherein the polymerizable monomer (PM) additionally contains a (meth)acrylic monomer represented by the formula (II), And r2 (wherein r2 is a hydrogen atom or a methyl group; 八3 and a4 each independently represent an alkylene group having a carbon number of 1 to 4, a -COO. group or a single bond; and the Zi to Z3 systems are each independently represented. a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, φ or an alkoxy group having 1 to 4 carbon atoms; X2 is an alkylene group having 1 to 18 carbon atoms; c and d are satisfying c + d = 0 or 2 of 0 or a positive integer) and a carboxyl group-containing monomer represented by CHfd-Xs-COOH [formula (C1)], wherein R! is hydrogen or methyl; X3 is a single bond or -COOR2 - R2 is a carboxyl group-containing monomer having a carbon number of 2 to 10 carbon atoms and/or CHeCRi-X^COOH [formula (C2)], wherein 111 is hydrogen or methyl; 4 is -(:001120(:0113-; here, 112 is an alkylene group having a carbon number of 2 to 10; R3 is an alkylene group having a carbon number of 2 to 10 or an aromatic group having a carbon number of 2 to 10; The alkyl group is formed, and the total amount of the carboxyl group-containing monomer is not more than 1 5 wt of the total amount of the polymerizable monomer (PM) represented by the formula (1) and the polymerizable monomer represented by the formula (II). 11. The polymerizable polymer according to claim 10, wherein the cyclic monomer is an aliphatic epoxy group represented by formula (III) Containing body, of formula (IV) shown in the aliphatic-containing oxetanyl monomer, or of formula (V) shown in the monomeric cyclic aliphatic epoxy groups, -59- (III) 201004978 1 to 4 alkyl) (wherein r3 is a hydrogen atom or a carbon number (wherein R4 to R6 are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) Rq Ra ❷ (wherein R7 to R1S are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). 12. The polymerizable polymer according to claim 1 or 11, wherein the reaction rate of the aromatic ring-containing polymer (AP) with the cyclic monomer is 5 mol% or more. The functional liquid crystalline polymer composition, which contains a polymerizable polymer according to any one of claims 10 to 12, and a polyfunctional compound having two or more ethylenically unsaturated bonds in one molecule. Formed by a monomer. 14. The polyfunctional liquid crystalline polymer composition according to claim 13, wherein the polyfunctional monomer is a polyfunctional liquid crystal represented by the formula (VI) -60- 201004978 (wherein, Rl6 is a hydrogen atom or a methyl group; Rl7 is an alkylene group having a carbon number of 1 to 18 or a -COO- group at the opposite end of the side adjacent to the (meth)acryloxy group; -OCO-based any of the alkyl groups having a carbon number of 1 to 18; T! is Ζ 4 (Ζ4 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms); Υι is a single bond or -COO-; Υ!, a single bond or -oco-). A polymer composition for a liquid crystal panel comprising a polyfunctional liquid crystalline polymer composition as disclosed in claim 13 or 14. A polymerizable film formed by coating a polyfunctional liquid crystalline polymer composition of claim 13 or 14 on a surface of a substrate. An optically anisotropic film which is formed by applying a polyfunctional liquid crystalline polymer composition as disclosed in claim 13 or 14 to a surface of a substrate and hardening it. 61 - 201004978 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the component symbols of this representative figure: 4E. ^ 5. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: ❹