TW202346380A - Polymer composition, single layer phase difference material, and liquid crystal alignment agent - Google Patents

Abstract

Provided as a polymer composition that provides a single layer phase difference material exhibiting a high phase difference value, even with low temperature firing and even as a thin film, is a polymer composition comprising: (A) a side-chain-type polymer that has a side-chain (a1) which has a photoreactive site and a side-chain (a2) which has a site represented by formula (b); and (B) an organic solvent. Also provided are a liquid crystal alignment agent and a single layer phase difference material obtained from said polymer composition. (In the formula, L, W1, W2, W3, Q1, n1, and Q are as defined in the description.).

Description

Polymer composition, single-layer phase difference material and liquid crystal alignment agent

The present invention relates to polymer compositions, single-layer retardation materials and liquid crystal alignment agents. Specifically, it relates to materials that have optical properties suitable for use in display devices, recording materials, etc., and are particularly suitable for use in optical compensation films such as polarizing plates and phase difference plates for liquid crystal displays, and optical alignment films for liquid crystal displays, Liquid crystalline polymer for organic electroluminescent (EL) circular polarizing plates, a composition containing the polymer, a single-layer retardation material and a liquid crystal alignment agent obtained from the composition.

Due to the requirements for improvement of display quality and weight reduction of liquid crystal display devices, organic EL display devices, etc., there are increasing demands for polymer films whose internal molecular alignment structures are controlled as optical compensation films such as polarizing plates and phase difference plates. In order to respond to this demand, films utilizing the optical anisotropy of polymerizable liquid crystal compounds have been developed. The polymerizable liquid crystal compound used here is generally a liquid crystal compound having a polymerizable group and a liquid crystal structure part (a structural unit having a spacer part and a mesogen part), and an acrylic group is widely used as this polymerizable group.

Such a polymerizable liquid crystal compound is generally polymerized by irradiation with radiation such as ultraviolet rays to form a polymer (film). For example, a method is known in which a specific polymerizable liquid crystal compound having an acrylic group is supported on a support that has been subjected to an alignment process and is irradiated with radiation while maintaining the compound in a liquid crystal state (Patent Document 1). A method of obtaining a polymer by adding a photopolymerization initiator to a mixture of two polymerizable liquid crystal compounds having an acrylic group or a composition in which chiral liquid crystal is mixed with the mixture and irradiating it with ultraviolet rays (Patent Document 2).

In addition, there are reports of alignment films using polymerizable liquid crystal compounds and polymers that do not require a liquid crystal alignment film (Patent Documents 3 and 4), or alignment films using polymers containing photo-crosslinked sites (Patent Documents 5 and 6). and various single-layer coating alignment films. Retardation materials are often applied to film substrates. In order to reduce damage to the film substrate, the film is required to exhibit a high phase difference value under low-temperature calcination. [Prior Technical Document] 〔Patent documents〕

[Patent Document 1] Japanese Patent Application Publication No. Sho 62-70407 [Patent Document 2] Japanese Patent Application Laid-Open No. 9-208957 [Patent Document 3] Specification of European Patent Application Publication No. 1090325 [Patent Document 4] International Publication No. 2008/031243 [Patent Document 5] Japanese Patent Application Publication No. 2008-164925 [Patent Document 6] Japanese Patent Application Publication No. 11-189665

[Problem to be solved by the invention]

The present invention was completed in view of the above problems, and aims to provide a polymer composition capable of producing a thin film and a single-layer retardation layer with a high retardation value under low-temperature calcination, and a single-layer retardation material obtained from the composition. and liquid crystal alignment agents. [Methods to solve problems]

As a result of the inventors' efforts to solve the above-mentioned problems, they found that by using a composition containing a specific polymer, it is possible to obtain high refractive index anisotropy ( Δn) phase difference material to complete the present invention.

That is, the present invention provides the following polymer composition and single-layer retardation material. ＜1＞A polymer composition containing: (A) A side chain type high-voltage side chain (a1) having a side chain (a1) having a photoreactive site, and a side chain (a2) having a site represented by the following formula (b) molecules; and (B) organic solvents. [Chemical 1] (In formula (b), W ¹ , W ² and W ³ are each independently a single bond, -O-, -C(=O)-O-, -OC(=O)-, -C(=O )-N(R')- or -N(R')-C(=O)-. When the number of W ² is 2 or more, each W ² may be the same or different from each other. R' represents the number of hydrogen atoms or carbons Alkyl group of 1 to 6. Q is an alkylene group with 1 to 10 carbon atoms. Part or all of the hydrogen atoms of the alkylene group may be substituted by halogen atoms. L represents a single bond, an alkylene group with 1 to 12 carbon atoms. , or -CH ₂ - constituting an alkylene group with 1 to 12 carbon atoms, one or more non-adjacent ones passing through -O-, -S-, -C(=O)-O-, or -OC(=O )-substituted divalent linking group, part or all of the hydrogen atoms of the alkylene group may be substituted by halogen atoms. Q ¹ is a single bond, phenyl group, naphthyl group or divalent group with 5 to 8 carbon atoms Alicyclic hydrocarbon group, part or all of the hydrogen atoms of the phenylene group and naphthylene group may be replaced by a cyano group, a halogen atom, an alkyl group with 1 to 5 carbon atoms, an alkylcarbonyl group with 2 to 6 carbon atoms, or a carbonyl group. 1 to 5 alkoxy groups are substituted. When the number of Q ¹ is 2 or more, each Q ¹ may be the same or different from each other. The hydrogen atom on the benzene ring may be selected from an alkyl group with a carbon number of 1 to 6, a carbon number 1 It is substituted with a haloalkyl group of ~6, an alkoxy group of 1 to 6 carbon atoms, a haloalkoxy group of 1 to 6 carbon atoms, a cyano group, and a nitro group. In addition, the benzene ring may be a naphthalene ring, and the benzene ring may be a naphthalene ring. The hydrogen atoms on the naphthalene ring can be selected from alkyl groups with 1 to 6 carbon atoms, haloalkyl groups with 1 to 6 carbon atoms, alkoxy groups with 1 to 6 carbon atoms, and haloalkoxy groups with 1 to 6 carbon atoms. Substituted with cyano and nitro substituents. n ₁ is 0, 1, 2 or 3. The dotted line is a bond.) <2> The polymer composition of the above <1>, wherein (A) the side chain type is high The molecule further has a side chain (a3) that only exhibits liquid crystallinity in addition to the structure represented by the aforementioned formula (b). <3> The polymer composition of the above <1>, which has a side chain (a1) of a photoreactive moiety and has a side chain represented by any one of the following formulas (a1-1) to (a1-6) . [Chemicalization 2] (In the formula, n1 and n2 are each independently 0, 1, 2 or 3. L represents a single bond, an alkylene group with 1 to 12 carbon atoms, or -CH ₂ constituting an alkylene group with 1 to 12 carbon atoms. - One or more non-adjacent divalent linking groups substituted by -O-, -S-, -C(=O)-O-, or -OC(=O)-, the hydrogen of the alkylene group Part or all of the atoms may be substituted by halogen atoms. T ¹ is a single bond or an alkylene group having 1 to 12 carbon atoms, and part or all of the hydrogen atoms of the alkylene group may be substituted by halogen atoms. A ¹ , A ² and D ¹ , each independently a single bond, -O-, -CH ₂ -, -C(=O)-O-, -OC(=O)-, -C(=O)-NH- or -NH- C(=O)-. However, when T ¹ is a single bond, A ² is also a single bond. Y ¹ and Y ² are phenyl or naphthylene groups, and the hydrogen atoms of the phenyl or naphthylene groups are Part or all of them may be substituted by a cyano group, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyl group having 2 to 6 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. P ¹ , Q ¹ and Q ² , each independently a single bond, a phenylene group, or a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms. Part or all of the hydrogen atoms of the phenylene group may be replaced by a cyano group, a halogen atom, or a cyano group, a halogen atom, or a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms. 5 alkyl group, alkylcarbonyl group having 2 to 6 carbon atoms, or alkoxy group having 1 to 5 carbon atoms. When the number of Q ¹ is 2 or more, each Q ¹ may be the same or different from each other, and the number of Q ² is When 2 or more, each Q ² may be the same or different from each other. R is a hydrogen atom, a cyano group, a halogen atom, a carboxyl group, an alkyl group with 1 to 5 carbon atoms, an alkylcarbonyl group with 2 to 6 carbon atoms, or an alkylcarbonyl group with 3 to 3 carbon atoms. 7 cycloalkyl group or alkoxy group having 1 to 5 carbon atoms. X ¹ and X ² are each independently a single bond, -O-, -C(=O)-O-, -OC(=O)- , -N=N-, -CH=CH-, -C≡C-, -CH=CH-C(=O)-O- or -OC(=O)-CH=CH-. The number of X ¹ is When the number of X 1 is 2 or more, each X ¹ may be the same or different from each other. When the number of X ² is 2 or more, each X ² may be the same or different from each other. Cou is coumarin-6-yl or coumarin-7-yl , a part of the hydrogen atoms bonded to these can be -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen atoms, alkyl groups with 1 to 5 carbon atoms or carbon numbers Alkoxy substitution of 1~5. E is -C(=O)-O-, -OC(=O)-, -C(=O)-S- or -SC(=O)-. G ¹ and G ² , each independently N or CH. The hydrogen atom of CH=CH in the above definition can be selected from cyano group, halogen atom, alkyl group with 1 to 5 carbon atoms, and alkylcarbonyl group with 2 to 6 carbon atoms. And substituted by substituents of alkoxy groups with 1 to 5 carbon atoms. The dotted lines are bonds.)

<4> The polymer composition of the above <2>, wherein the above (a3) is represented by any one of the following formulas (a3-1) to (a3 to 11). [Chemical 3] [Chemical 4] (In the formula, L represents a single bond, an alkylene group with 1 to 12 carbon atoms, or one or more -CH ₂ - constituting an alkylene group with 1 to 12 carbon atoms that are not adjacent to each other and are separated by -O-, -S -, -C(=O)-O-, or -OC(=O)-substituted divalent linking group, part or all of the hydrogen atoms of the alkylene group may be substituted by halogen atoms. A ³ and A ⁴ , each independently a single bond, -O-, -CH ₂ -, -C(=O)-O-, -OC(=O)-, -C(=O)-NH-, or -NH-C (=O)-. When the number of A ⁴ is 2 or more, each A ⁴ may be the same or different. R ¹ is -NO ₂ , -CN, halogen atom, phenyl group, naphthyl group, biphenyl group, furan group, a monovalent nitrogen-containing heterocyclic group, a monovalent alicyclic hydrocarbon group with 5 to 8 carbon atoms, an alkyl group with 1 to 12 carbon atoms, or an alkoxy group with 1 to 12 carbon atoms. R ² is phenyl, naphthyl , biphenyl, furyl, 1-valent nitrogen-containing heterocyclic group or 1-valent alicyclic hydrocarbon group with 5 to 8 carbon atoms, part or all of the hydrogen atoms of these groups can be -NO ₂ , -CN, halogen Atom, alkyl group with 1 to 5 carbon atoms or alkoxy group with 1 to 5 carbon atoms. R ³ is a hydrogen atom, -NO ₂ , -CN, halogen atom, phenyl group, naphthyl group, biphenyl group, furyl group , 1-valent nitrogen-containing heterocyclic group, 1-valent alicyclic hydrocarbon group with 5 to 8 carbon atoms, alkyl group with 1 to 12 carbon atoms, or alkoxy group with 1 to 12 carbon atoms. E is -C(=O)- O-, -OC(=O)-, -C(=O)-S- or -SC(=O)-. k1~k5 are each independently an integer from 0 to 2, but the total of k1~k5 is 2 or more. k6 and k7 are each independently an integer from 0 to 2, but the sum of k6 and k7 is more than 1. m1, m2 and m3 are each independently an integer from 1 to 3. n is 0 or 1. Z ¹ and Z ² are each independently a single bond, -C(=O)-, -CH ₂ -O-, or -CF ₂ -. Part or all of the hydrogen atoms on the benzene ring and naphthalene ring can be cyanide Substituted with a base, a halogen atom, an alkyl group with 1 to 5 carbon atoms, an alkylcarbonyl group with 2 to 6 carbon atoms, or an alkoxy group with 1 to 5 carbon atoms. The dotted line is a bond.)

<5>A manufacturing method of single-layer phase difference material, which has: [I] The step of applying the composition according to any one of the above <1> to <4> on a substrate to form a coating film; [II] The step of irradiating polarized ultraviolet rays on the coating film obtained in [I]; and [III] The step of heating the coating film obtained in [II] to obtain a phase difference material. <6> A single-layer retardation material obtained from the polymer composition according to any one of the above <1> to <4>. <7> A liquid crystal alignment agent obtained from the polymer composition according to any one of the above <1> to <4>. [Effects of the invention]

According to the present invention, it is possible to provide a single-layer retardation material and a liquid crystal alignment agent that are thin films and have a high retardation value even in a low-temperature calcination process.

As a result of diligent research, the inventors of the present invention obtained the following insights and completed the present invention. The polymer composition of the present invention has a photosensitive side-chain polymer (hereinafter, also simply referred to as a side-chain polymer) that can exhibit liquid crystallinity. The coating film obtained by using the aforementioned polymer composition has a photosensitivity that can A side-chain polymer film that exhibits liquid crystalline photosensitivity. This coating film is not subjected to rubbing treatment, but is subjected to alignment treatment by polarized light irradiation. Then, after irradiation with polarized light, the side chain type polymer film is heated to form a film provided with optical anisotropy (hereinafter also referred to as a single-layer retardation material). At this time, the slight anisotropy developed by polarized light irradiation becomes a driving force, and the liquid crystalline side chain polymer itself is self-organized and rearranged efficiently. As a result, a highly efficient alignment process is achieved as a single-layer coating-type horizontal alignment film, and a single-layer coating-type horizontal alignment film imparted with high optical anisotropy can be obtained.

Furthermore, in the polymer composition of the present invention, the side chain type polymer which is the component (A) contains the side chain (a1) having a photoalignment moiety, and the side chain (a1) represented by the above formula (b). a2), polymer aggregation is inhibited. As a result, the phase difference material obtained from the polymer composition of the present invention still exhibits high retardation even in a thin film under low-temperature calcination conditions of 100°C to 120°C. Furthermore, these include the inventor's insights regarding the mechanism of the invention and do not limit the invention. Hereinafter, embodiments of the present invention will be described in detail.

＜Polymer composition＞ The polymer composition of the present invention is characterized by containing (A) a side chain type polymer, which is a photosensitive side chain type polymer that exhibits liquid crystallinity within a predetermined temperature range, and which has a side chain type polymer having a photoreactive site. Chain (a1) and side chain (a2) having the site represented by the above formula (b); and (B) organic solvent.

＜＜(A) Side chain polymer＞＞ Component (A) is a side chain type polymer, which is a side chain type polymer that exhibits liquid crystalline photosensitivity within a specified temperature range. It has a side chain (a1) with a photoreactive site and has the above formula ( b) The side chain (a2) of the indicated part. (A) The side chain type polymer preferably reacts under light in the wavelength range of 250 nm to 400 nm and exhibits liquid crystallinity in the temperature range of 80°C to 300°C. (A) The side chain type polymer preferably has a photosensitive side chain that reacts with light in the wavelength range of 250 nm to 400 nm. (A) The side chain type polymer exhibits liquid crystallinity in the temperature range of 80° C. to 300° C., so it is preferable that it has a side chain (a3) that only exhibits liquid crystallinity in addition to the structure represented by the above formula (b).

(A) Side chain type polymers have photosensitive side chains bonded to the main chain, which can sense light and cause cross-linking reactions or isomerization reactions. The structure of the side chain-type polymer that can exhibit liquid crystallinity and photosensitivity is not particularly limited as long as it satisfies such characteristics. Preferably, it is a mesogen component that has rigidity in the side chain structure. In this case, when the side chain type polymer is used as a single-layer retardation material, stable optical anisotropy can be obtained.

As a more specific example of the structure of the side chain type polymer that can exhibit liquid crystalline photosensitivity, it is preferable to have a structure selected from the group consisting of (meth)acrylate, itonate, fumarate, and maleate. At least one of the group consisting of acid ester, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene and other radically polymerizable groups, and siloxane. The structure of the main chain and the side chain (a1) of the photoreactive site.

The side chain (a1) is preferably represented by any one of the following formulas (a1-1) to (a1-6). In addition, from the viewpoint of solubility in a solvent, the number of benzene rings per side chain (a1) is preferably within 3. [Chemistry 5]

In formulas (a1-1) to (a1-6), n1 and n2 are each independently 0, 1, 2 or 3. L represents a single bond, an alkylene group with 1 to 12 carbon atoms, or one or more -CH ₂ - constituting an alkylene group with 1 to 12 carbon atoms that are not adjacent to each other and are separated by -O-, -S-, -C (=O)-O- or -OC(=O)-substituted divalent linking group, and part or all of the hydrogen atoms of the alkylene group may be substituted by halogen atoms. T ¹ is a single bond or an alkylene group having 1 to 12 carbon atoms, and part or all of the hydrogen atoms in the alkylene group may be substituted by halogen atoms. A ¹ , A ² and D ¹ are each independently a single bond, -O-, -CH ₂ -, -C(=O)-O-, -OC(=O)-, -C(=O)- NH- or -NH-C(=O)-. However, when T ¹ is a single bond, A ² is also a single bond. Y ¹ and Y ² are phenylene groups or naphthylene groups. Part or all of the hydrogen atoms of the phenylene groups and naphthylene groups may be replaced by cyano groups, halogen atoms, alkyl groups having 1 to 5 carbon atoms, or alkyl groups having 1 to 5 carbon atoms. Substituted by an alkylcarbonyl group with 2 to 6 carbon atoms or an alkoxy group with 1 to 5 carbon atoms. P ¹ , Q ¹ and Q ² are each independently a single bond, a phenylene group or a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms. Some or all of the hydrogen atoms of the phenylene group may be replaced by a cyano group. , halogen atom, alkyl group with 1 to 5 carbon atoms, alkylcarbonyl group with 2 to 6 carbon atoms, or alkoxy group with 1 to 5 carbon atoms. When the number of Q ¹ is 2 or more, each Q ¹ may be the same or different from each other. When the number of Q ² is 2 or more, each Q ² may be the same or different from each other. R is a hydrogen atom, a cyano group, a halogen atom, a carboxyl group, an alkyl group with 1 to 5 carbon atoms, an alkylcarbonyl group with 2 to 6 carbon atoms, a cycloalkyl group with 3 to 7 carbon atoms, or an alkoxy group with 1 to 5 carbon atoms. base. X ¹ and X ² are each independently a single bond, -O-, -C(=O)-O-, -OC(=O)-, -N=N-, -CH=CH-, -C≡ C-, -CH=CH-C(=O)-O- or -OC(=O)-CH=CH-. When the number of X ¹ is 2 or more, each X ¹ may be the same or different from each other. When the number of X ² is 2 or more, each X ² may be the same or different from each other. Cou is coumarin-6-yl or coumarin-7-yl, and part of the hydrogen atoms bonded to these can be -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH -CN, halogen atom, alkyl group with 1 to 5 carbon atoms or alkoxy group with 1 to 5 carbon atoms substituted. E is -C(=O)-O-, -OC(=O)-, -C(=O)-S- or -SC(=O)-. G ¹ and G ² are each independently N or CH. The hydrogen atom of CH=CH in the above definition can be selected from a cyano group, a halogen atom, an alkyl group with 1 to 5 carbon atoms, an alkylcarbonyl group with 2 to 6 carbon atoms, and an alkoxy group with 1 to 5 carbon atoms. Substituent substitution. The dotted lines are bonds.

The aforementioned alkylene group having 1 to 12 carbon atoms may be linear, branched, or cyclic. Specific examples thereof include methylene, ethylidene, and propane-1, 3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1, 8-diyl, nonane-1,9-diyl, decane-1,10-diyl, etc.

Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom, iodine atom, etc.

The alkyl group having 1 to 5 carbon atoms may be linear or branched. Specific examples thereof include: methyl, ethyl, n-propyl, isopropyl, and n-butyl. base, tertiary butyl, n-pentyl, etc.

Specific examples of the alkylcarbonyl group having 2 to 6 carbon atoms include methylcarbonyl (ethylcarbonyl), ethylcarbonyl, n-propylcarbonyl, n-butylcarbonyl, n-pentylcarbonyl, and the like.

Specific examples of the alkoxy group having 1 to 5 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, n-pentyloxy group, and the like.

Specific examples of the divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms include cyclopentanediyl, cyclohexanediyl, cycloheptanediyl, and cyclooctanediyl.

Specific examples of the aforementioned cycloalkyl group having 3 to 7 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.

The side chain (a1) is more preferably the following formula (a1-1-1), (a1-1-2), (a1-2-1), (a1-3-1), (a1- 4-1), (a1-5-1) or (a1-6-1). [Chemical 6] (In the formula, L ^, A ¹ , A ^{2 ,} Y ¹ , Y ² , Q ¹ , ^{T 1} , R ^, It is a phenylene group or a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms. Part or all of the phenylene group and the hydrogen atoms of CH=CH may be replaced by a cyano group, a halogen atom, or an alkane having 1 to 5 carbon atoms. Substituted with alkylcarbonyl group, alkylcarbonyl group with 2 to 6 carbon atoms, or alkoxy group with 1 to 5 carbon atoms.)

The side chain represented by the formula (a1-1-1) is preferably a side chain represented by the following formula (a1-1-1-1), and the side chain represented by the formula (a1-1-2) is preferably In other words, side chains represented by formulas (a1-1-2-1), (a1-1-2-2) and (a1-1-2-3) are preferred. [Chemical 7] (In the formula, Me means base, L, R and dotted lines are the same as above.)

The side chain represented by formula (a1-2-1) is preferably a side chain represented by the following formula (a1-2-1-1). [Chemical 8] (In the formula, L, A ² , Q ¹ , T ¹ , R and the dotted line are the same as before.)

The side chain represented by formula (a1-3-1) is preferably the following formula (a1-3-1-1), (a1-3-1-2) or (a1-3-1-3 ) represents the side chain. [Chemical 9] (In the formula, L, Cou and dotted lines are the same as before.)

The side chain represented by formula (a1-4-1) is preferably the following formula (a1-4-1-1), (a1-4-1-2), (a1-4-1-3) ) or the side chain represented by (a1-4-1-4). [Chemical 10] (In the formula, L, R and dotted lines are the same as before.)

The side chain represented by formula (a1-5-1) is preferably a side chain represented by the following formula (a1-5-1-1) or (a1-5-1-2). [Chemical 11] (In the formula, L, R and dotted lines are the same as before.)

The side chain represented by formula (a1-6-1) is preferably the following formula (a1-6-1-1), (a1-6-1-2) or (a1-6-1-3) ) represents the side chain. [Chemical 12] (In the formula, L, R and dotted lines are the same as before.)

Moreover, (A) a side chain type polymer contains the side chain (a2) of the photoreactive moiety represented by the said formula (b).

Furthermore, (A) the side chain type polymer exhibits liquid crystallinity in the temperature range of 80 to 300°C, and therefore is preferably selected from the group consisting of the above formulas (a3-1) to (a3-11) Either one exhibits only liquid crystalline side chain (a3). In addition, the so-called "only exhibiting liquid crystallinity" here means a polymer having only a side chain (a3). In the production process of the retardation material of the present invention (ie, steps [I] to [III] described below) , does not show photosensitivity, but only shows liquid crystallinity.

＜＜How to prepare photosensitive side chain polymer＞＞ The above-mentioned photosensitive side chain type polymer which can exhibit liquid crystallinity can be obtained by combining a monomer (MA) containing a side chain (a1) having a photoreactive moiety and a monomer (MA) having a moiety represented by the formula (b). It is obtained by polymerizing MB) and a monomer (MC) that has a portion that exhibits liquid crystallinity.

[Monomer (MA) containing side chain (a1) having a photoreactive moiety] Regarding the monomer (hereinafter, also referred to as monomer MA) containing a side chain (a1) having a photoreactive moiety, Examples include compounds represented by the following formula (M1), (M2), (M3), (M4), (M5) or (M6). [Chemical 13] (In the formula, PG is a polymerizable group, A ¹ , A ² , D ¹ , L, T ¹ , Y ¹ , Y ² , P ¹ , Q ¹ , Q ² , R, Cou, E, X ¹ , X ² , G ¹ , G ² , n1 and n2 are the same as above. The hydrogen atom of CH=CH in the above definition can be selected from cyano group, halogen atom, alkyl group with carbon number 1~5, carbon number 2~6 Substituted with substituents of alkylcarbonyl and alkoxy having 1 to 5 carbon atoms.)

In the formulas (M1) to (M6), PG is a polymerizable group, preferably a group represented by any one of the following formulas (PG1) to (PG7). Among them, from the viewpoint of easy control of the polymerization reaction and the stability of the polymer, an acrylic group or a methacrylic group represented by formula (PG1) is preferred. [Chemical 14] (In the formula, R ^A and R ^B are each independently a hydrogen atom or a methyl group, and the dotted line is the bond with L.)

The compound represented by formula (M1) is preferably represented by the following formula (M1-1), (M1-2), (M1-3) or (M1-4). [Chemical 15] (In the formula, Me means methyl, and PG, L, Y ¹ , P ^1' , and R are the same as above.)

The compound represented by formula (M2) is preferably represented by the following formula (M2-1). [Chemical 16] (In the formula, PG, A ² , L, T ¹ , Y ¹ , P ¹ , Q ¹ and R are the same as above.)

The compound represented by formula (M3) is preferably represented by the following formula (M3-1). [Chemical 17] (In the formula, PG, A ¹ , L, X ¹ , Q ¹ , Cou and n1 are the same as above.)

The compound represented by formula (M4) is preferably represented by the following formula (M4-1). [Chemical 18] (In the formula, PG, A ¹ , L, X ¹ , Y ¹ , Y ² , Q ¹ , E, R and n1 are the same as above.)

The compound represented by formula (M5) is preferably represented by the following formula (M5-1). [Chemical 19] (In the formula, PG, A ¹ , L, X ¹ , Y ¹ , Y ² , Q ¹ , R and n1 are the same as above.)

The compound represented by formula (M6) is preferably represented by the following formula (M6-1). [Chemistry 20] (In the formula, PG, A ¹ , L, X ¹ , Y ¹ , Y ² , Q ¹ , G ¹ , G ² , R and n1 are the same as above.)

The compound represented by the formula (M1-1) is preferably represented by the following formula (M1-1-1), and the compound represented by the formula (M1-2) is preferably represented by the following formula (M1 -2-1), for the compound represented by the formula (M1-3), the compound represented by the following formula (M1-3-1) is preferred, and for the compound represented by the formula (M1-4) , preferably a compound represented by the following formula (M1-4-1). [Chemistry 21] (In the formula, Me means base, PG, L and R are the same as above.)

The compound represented by formula (M2-1) is preferably represented by the following formula (M2-2). [Chemistry 22] (In the formula, PG, A ² , L, T ¹ , Q ¹ and R are the same as above.)

The compound represented by formula (M3-1) is preferably represented by the following formula (M3-2), (M3-3) or (M3-4). [Chemistry 23] (In the formula, PG, L and Cou are the same as before.)

The compound represented by formula (M4-1) is preferably represented by the following formula (M4-2), (M4-3), (M4-4) or (M4-5). [Chemistry 24] (In the formula, PG, L and R are the same as before.)

The compound represented by formula (M5-1) is preferably represented by the following formula (M5-2) or (M5-3). [Chemical 25] (In the formula, PG, L and R are the same as before.)

The compound represented by formula (M6-1) is preferably represented by the following formula (M6-2), (M6-3), or (M6-4). [Chemical 26] (In the formula, PG, L and R are the same as before.)

Examples of the compound represented by the formula (M1) include those represented by any one of the following formulas (A-1-1-1) to (A-1-1-12). In the following formulas (A-1-1-1) to (A-1-1-12), PG is a polymerizable group, and s1 represents the number of methylene groups, which is an integer of 2 to 9. R ¹¹ is -H, -CH ₃ , -OCH ₃ , -C(CH ₃ ) ₃ , -C(=O)-CH ₃ or -CN, R ¹² is -H, -CH ₃ , -CN or -F . [Chemical 27]

[Chemical 28]

[Chemical 29]

[Chemical 30]

In addition, examples of the compound represented by the formula (M1) include those represented by any one of the following formulas (A-1-2-1) to (A-1-2-6). In the following formula, PG is a polymerizable group, and s1 is the same as mentioned above. [Chemical 31] (In the formula, Me means nail.)

Specific examples of the compound represented by formula (M1) include: 4-(6-methacrylooxyhexyl-1-oxy)cinnamic acid, 4-(6-acrylooxyhexyl-1) -Oxy)cinnamic acid, 4-(3-methacrylooxypropyl-1-oxy)cinnamic acid, 4-[4-(6-methacrylooxyhexyl-1-oxy) Benzyloxy]cinnamic acid, etc.

Examples of the compound represented by the formula (M2) include those represented by any one of the following formulas (A-2-1) to (A-2-9). In the following formulas (A-2-1) to (A-2-9), PG is a polymerizable group, s1 and s1 represent the number of methylene groups, and are each independently an integer of 2 to 9. R ²¹ is -CH ₃ , -OCH ₃ , -C(CH ₃ ) ₃ , -C(=O)-CH ₃ , -CN or -F. [Chemical 32]

[Chemical 33]

[Chemical 34]

Examples of the compound represented by the formula (M3) include those represented by any one of the following formulas (A-3-1) to (A-3-5). In the following formula, PG is a polymerizable group, and s1 is the same as mentioned above. [Chemical 35]

Examples of the compound represented by the formula (M4) include those represented by any one of the following formulas (A-4-1) to (A-4-4). In the following formula, PG is a polymerizable group, and s1 is the same as mentioned above. [Chemical 36]

Examples of the compound represented by formula (M5) include those represented by any one of the following formulas (A-5-1) to (A-5-3). In the following formula, PG is a polymerizable group, and s1 is the same as mentioned above. [Chemical 37]

Examples of the compound represented by formula (M6) include those represented by any one of the following formulas (A-6-1) to (A-6-3). In the following formula, PG is a polymerizable group, and s1 is the same as mentioned above. [Chemical 38]

Some of the aforementioned monomers are commercially available, and some can be produced by the method described in International Publication No. 2015/002292, for example.

[Monomer (MB) having a moiety represented by formula (b)] Examples of monomers having a moiety represented by formula (b) (hereinafter also referred to as monomer MB.) include the following formula (bm1- 1) represents the compound. [Chemical 39] In the formula (bm1-1), the definition of each substituent is the same as the definition in the above-mentioned formula (b), and the definition of PG is the same as the above-mentioned PG. Some of these monomers are commercially available, and some can be produced from well-known substances using well-known production methods.

Preferred examples of the monomer MB of the moiety represented by formula (b) include the following formulas MB-1 to MB-10. [Chemical 40] (In the formula, s1 represents the number of methylene groups, which is an integer from 2 to 9.)

[Monomer (MC) having a structure that exhibits only liquid crystallinity] An example of a monomer (hereinafter also referred to as monomer MC) having a structure that only exhibits liquid crystallinity other than the structure represented by the above formula (b) is a monomer that can form a mesogen group in a side chain. .

The mesogen group may be a group such as biphenyl or phenyl benzate that alone forms a mesogen structure, or a group such as benzoic acid or the like in which side chains form hydrogen bonds with each other to form a mesogen structure. The mesogen group having a side chain is preferably a structure represented by any one of the following formulas (b1) to (b11). [Chemical 41]

Specific examples of the monomer MC are preferably those derived from a hydrocarbon, (meth)acrylate, itaconate, fumarate, maleate, α-methylene-γ- At least one polymerizable group from the group consisting of a radically polymerizable group such as butyrolactone, styrene, vinyl, maleimide, norbornene, and siloxane, and the formula (b1) above The structure of at least one structure of ~(b11). In particular, it is preferable that monomer MC has a polymerizable group derived from (meth)acrylate.

Preferable examples of monomer MC include those represented by the following formulas (MC-1) to (MC-10). In addition, in the following formula, PG is a polymerizable group, and p represents the number of methylene groups, which is an integer of 2 to 9. [Chemical 42]

Moreover, it can be copolymerized with other monomers within the range which does not impair the photoreactivity and/or the ability to express liquid crystallinity. Examples of other monomers include industrially available monomers capable of radical polymerization.

Specific examples of other monomers include unsaturated carboxylic acids, acrylate compounds, methacrylate compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds, vinyl compounds, etc. .

Specific examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and the like.

Examples of the acrylate compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthracene acrylate, anthracenyl methyl acrylate, phenyl acrylate, and 2,2 acrylate. , 2-trifluoroethyl ester, tertiary butyl acrylate, cyclohexyl acrylate, isocamphenyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate Ester, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-triacrylate Cyclodecyl ester, and 8-ethyl-8-tricyclodecyl acrylate, etc.

Examples of the methacrylate compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthracene methacrylate, Anthracenyl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tertiary butyl methacrylate, cyclohexyl methacrylate, isocamphenyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxy methacrylate Butyl ester, 2-methyl-2-adamantyl methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and methacrylic acid 8-ethyl-8-tricyclodecyl ester, etc.

Examples of the vinyl compound include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, propyl vinyl ether, and the like. Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, bromostyrene, and the like. Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide. wait.

The content of the side chain (a1) in the side chain type polymer of the present invention is preferably 5 to 99.9 mol%, considering photoreactivity, and more preferably 5 to 50 mol%, considering light stability. From this point of view, a further preferred range is 5 to 20 mol%.

The content of the side chain (a2) in the side chain type polymer of the present invention is preferably 5 to 95 mol%, more preferably 5 to 80 mol%, and further preferably 5 from the perspective of phase difference. ~50 mol%.

The side chain type polymer used in the present invention preferably has a side chain (a3) that exhibits only liquid crystallinity. In addition, other side chains may be included. The content of the side chain (a3) and other side chains is the remainder when the total content of the side chain (a1) and the side chain (a2) is less than 100 mol%.

The method for producing the polymer that is the component (A) is not particularly limited, and a general method used industrially can be used. Specifically, it can be produced by cationic polymerization, radical polymerization, or anionic polymerization of a vinyl group using the above-described monomer MA, monomer MB, monomer MC used as desired, and other monomers used as desired. Among these, radical polymerization is particularly preferred from the viewpoint of ease of reaction control.

As the polymerization initiator for radical polymerization, well-known compounds such as radical polymerization initiators and reversible addition fragment transfer (RAFT) polymerization reagents can be used.

A free radical thermal polymerization initiator is a compound that generates free radicals by heating to a temperature above the decomposition temperature. Examples of such radical thermal polymerization initiators include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide , benzyl peroxide, etc.), hydroperoxides (hydrogen peroxide, tertiary butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (dihydroperoxide Tertiary butyl), dicumyl peroxide, dilauryl peroxide, etc.), peroxyketals (dibutylperoxycyclohexane, etc.), alkyl peroxyesters (peroxynedecyl Tertiary butyl acid, tertiary butyl peroxytrimethylacetate, tertiary amyl peroxy 2-ethylcyclohexanoate, etc.), persulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc. ), azo compounds (azobisisobutyronitrile, 2,2'-bis(2-hydroxyethyl)azobisisobutyronitrile, etc.). One type of such radical thermal polymerization initiator can be used alone, or two or more types can be used in combination.

The radical photopolymerization initiator is not particularly limited as long as it is a compound that starts radical polymerization by light irradiation. Examples of such radical photopolymerization initiators include benzophenone, Michelone, 4,4'-bis(diethylamino)diphenylketone, triacetone, and thioxanthone. , isopropylthioxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4 '-Isopropylbenzophenone, 1-hydroxycyclohexylphenylketone, isopropylbenzoin ether, isobutylbenzoin ether, 2,2-diethoxyacetophenone, 2,2-di Methoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1-[4-(methylthio)phenyl]-2-𠰌linylpropan-1-one, 2-Benzyl-2-dimethylamino-1-(4-𠰌linylphenyl)-butanone-1,4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzene Isoamyl formate, 4,4'-bis(tertiary butylperoxycarbonyl)diphenyl ketone, 3,4,4'-bis(tertiary butylperoxycarbonyl)diphenyl ketone, 2,4 ,6-trimethylbenzyldiphenylphosphine oxide, 2-(4'-methoxystyryl)-4,6-bis(trichloromethyl)-s-tris-triphenidate, 2- (3',4'-dimethoxystyrene)-4,6-bis(trichloromethyl)-s-trimethoxy, 2-(2',4'-dimethoxystyrene) -4,6-bis(trichloromethyl)-s-trifluoroethylene, 2-(2'-methoxystyryl)-4,6-bis(trichloromethyl)-s-trifluoroethylene, 2 -(4'-pentyloxystyryl)-4,6-bis(trichloromethyl)-s-trimethyl, 4-[p-N,N-bis(ethoxycarbonylmethyl)]-2 , 6-bis(trichloromethyl)-s-triphosphate, 1,3-bis(trichloromethyl)-5-(2'chlorophenyl)-s-triphosphate, 1,3-bis(trichloromethane) Chloromethyl)-5-(4'-methoxyphenyl)-s-trimethyl, 2-(p-dimethylaminostyryl)benzozoazole, 2-(p-dimethylaminostyryl) Styryl)benzothiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis(7-diethylaminocoumarin), 2-(o-chlorophenyl)-4,4',5 ,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-four(4-ethoxycarbonylphenyl) )-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4'-5,5'-tetraphenyl-1,2'-biimidazole, 2 ,2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6 -Trichlorophenyl)-4,4'-5,5'-tetraphenyl-1,2'-biimidazole, 3-(2-methyl-2-dimethylaminopropyl)carbazole , 3,6-bis(2-methyl-2-𠰌linylpropionyl)-9-n-dodecylcarbazole, 1-hydroxycyclohexylphenyl ketone, bis(5-2,4-cyclopentyl Dien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, 3,3',4,4'-quaternary butyl Peroxycarbonyl) diphenyl ketone, 3,3',4,4'-(tertiary hexylperoxycarbonyl) diphenyl ketone, 3,3'-bis(methoxycarbonyl)-4,4' -Bis(tertiary butylperoxycarbonyl)diphenylketone, 3,4'-bis(methoxycarbonyl)-4,3'-bis(tertiary butylperoxycarbonyl)diphenylketone, 4 ,4'-bis(methoxycarbonyl)-3,3'-bis(tertiary butylperoxycarbonyl)diphenylketone, 2-(3-methyl-3H-benzothiazole-2-ylidene) )-1-naphthalen-2-yl-ethanone, or 2-(3-methyl-1,3-benzothiazole-2(3H)-ylidene)-1-(2-benzoyl)ethane Ketones etc. These compounds can be used individually or in mixture of 2 or more types.

The radical polymerization method is not particularly limited, and emulsion polymerization, suspension polymerization, dispersion polymerization, precipitation polymerization, block polymerization, solution polymerization, etc. can be used.

The organic solvent used in the polymerization reaction is not particularly limited as long as it can dissolve the produced polymer. Specific examples are listed below.

N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylhexanolide Amide, dimethyltrisoxide, tetramethylurea, pyridine, dimethyltrisine, hexamethyltrisoxide, γ-butyrolactone, isopropyl alcohol, cyclohexanol, cyclopentanol, methoxymethylpentanol, bis Pentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isopentyl ketone, methyl isopropyl ketone, methyl serosulo, ethyl serosulo, methyl serosulo Lusu acetate, ethyl selusu acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol Alcohol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol tertiary butyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, Dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate mono Propyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, Diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dihexane, n-hexane, n-pentane, n-octane , diethyl ether, cyclohexanone, cyclopentanone, ethyl carbonate, propyl carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether Acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methylethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxy propionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diethylene glycol dimethyl ether, 4-hydroxy-4-methyl- 2-Pentanone, 3-methoxy-N,N-dimethylpropamide, 3-ethoxy-N,N-dimethylpropamide, 3-butoxy-N,N-di Methylpropamide, tetrahydrofuran, etc.

These organic solvents can be used alone or in mixture. Furthermore, even if it is a solvent that does not dissolve the produced polymer, it can be mixed with the above-mentioned organic solvent within the range that the produced polymer does not precipitate. In addition, in radical polymerization, oxygen in the organic solvent hinders the polymerization reaction. Therefore, it is preferable to use an organic solvent that has been degassed as much as possible.

The polymerization temperature during radical polymerization can be selected from any temperature range of 30 to 150°C, but is preferably in the range of 50 to 100°C. In addition, the reaction can be carried out at any concentration. However, if the concentration is too low, it becomes difficult to obtain a high molecular weight polymer. If the concentration is too high, the viscosity of the reaction liquid becomes excessively high and uniform stirring becomes difficult. Therefore, the monomer The concentration is preferably 1 to 50 mass%, more preferably 5 to 30 mass%. The reaction can be carried out at a high concentration in the initial stage, and an organic solvent can be added later.

In the above-mentioned free radical polymerization reaction, if the ratio of the free radical polymerization initiator is more than that of the monomer, the molecular weight of the polymer obtained will become smaller. If it is less, the molecular weight of the polymer obtained will become larger. Therefore, the free radical initiator The ratio of the polymerized monomer is preferably 0.1 to 15 mol%. In addition, various monomer components, solvents, initiators, etc. can also be added during polymerization.

[Polymer recycling] When recovering the polymer produced from the reaction solution obtained by the above reaction, the reaction solution may be put into a poor solvent to precipitate the polymer. Examples of poor solvents used for precipitation include: methanol, acetone, hexane, heptane, butylthiol, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, Diethyl ether, methyl ethyl ether, water, etc. The precipitated polymer is put into a poor solvent, filtered and recovered, and then dried under normal pressure or reduced pressure, at normal temperature or by heating. In addition, if the operation of redissolving the polymer recovered by precipitation in an organic solvent and reprecipitating the polymer is repeated 2 to 10 times, the impurities in the polymer can be reduced. Examples of poor solvents in this case include alcohols, ketones, hydrocarbons, etc. It is preferable to use three or more poor solvents selected from these because the purification efficiency will be further improved.

The molecular weight of (A) the side chain type polymer of the present invention is the weight average measured by the GPC (Gel Permeation Chromatography) method, taking into account the strength of the coating film obtained, the workability during coating film formation, and the uniformity of the coating film. The molecular weight is preferably 2,000 to 2,000,000, more preferably 5,000 to 150,000. Alternatively, the aforementioned weight average molecular weight is preferably 2,000 to 1,000,000, more preferably 5,000 to 200,000.

＜＜(B) Organic solvent＞＞ The organic solvent used in the polymer composition used in the present invention is not particularly limited as long as it can dissolve the resin component. Specific examples are listed below. N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methyl-ε-caprolactam, 2-pyrrolidone , N-ethyl-pyrrolidone, N-vinyl-2-pyrrolidone, dimethyltrisoxide, tetramethylurea, pyridine, dimethyltrisine, hexamethylphosphatamide, γ-butyrolactone, 3-Methoxy-N,N-dimethylpropylamide, 3-ethoxy-N,N-dimethylpropylamide, 3-butoxy-N,N-dimethylpropylamide , 1,3-dimethyl-imidazolinone, cyclohexanone, cyclopentanone, ethyl carbonate, propyl carbonate, diethylene glycol dimethyl ether, 4-hydroxy-4-methyl-2 -Pentanone, propylene glycol monomethyl ether, propylene glycol tertiary butyl ether, diethylene glycol, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono Propyl ether, tripropylene glycol methyl ether, tetrahydrofuran, etc., can be used alone or mixed.

The polymer composition used in the present invention may also contain components other than the above-mentioned components (A) and (B). Examples thereof include, but are not limited to, solvents and compounds that improve film thickness uniformity and surface smoothness when coating a polymer composition, compounds that improve the adhesion between a retardation material and a substrate, and the like.

Specific examples of solvents (poor solvents) that improve film thickness uniformity and surface smoothness are as follows. Examples include isopropyl alcohol, methoxymethylpentanol, cyclohexanol, cyclopentanol, methylsiluso, ethylsiluso, butylsiluso, and methylsiluso acetate. , ethyl carbitol acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl Ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol tertiary butyl ether, diethylene glycol, propylene glycol monomethyl ether acetate, diethylene glycol monoacetate, diethyl Glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, Dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, Ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, 1-hexanol, n-hexane , n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, acetone Ethyl acid ester, methyl 3-methoxypropionate, methylethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropane Acid, 3-methoxypropylpropionate, 3-methoxybutylpropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy- 2-Propanol, 1-phenoxy-2-propanol, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetic acid Ester, dipropylene glycol, 2-(2-ethoxypropoxy) propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isopentyl lactate, ethyl amyl ketone, methyl lactate Nonyl ketone, methyl ethyl ketone, methyl isopentyl ketone, methyl isopropyl ketone, propylene glycol monoacetate, diethylene glycol monoacetate, 3-methyl-3-methoxy acetate Butyl ester, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monoacetate monopropyl ether and other solvents with low surface tension.

These poor solvents may be used alone or in combination of multiple types. When the above solvent is used, in order not to significantly reduce the solubility of the entire solvent contained in the polymer composition, it is preferably 1 to 60 mass % of the entire solvent, and more preferably 1 to 40 mass %.

Examples of compounds that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, polysiloxane-based surfactants, and nonionic surfactants. More specifically, examples include: EFTOP (registered trademark) 301, EF303, EF352 (manufactured by Top Chemical Products Co., Ltd.), Megaface (registered trademark) F171, F173, F560, F563, R-30, R-40, R- 41 (manufactured by DIC Corporation), Florado FC430, FC431 (manufactured by Japan 3M Corporation), Asahi Guard (registered trademark) AG710 (manufactured by AGC Corporation), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106, (manufactured by AGC Seimei Chemical Co., Ltd.), etc. The usage ratio of these surfactants is preferably 0.01 to 2 parts by mass, and more preferably 0.01 to 1 part by mass relative to 100 parts by mass of the resin composition contained in the polymer composition.

Specific examples of the compound that improves the adhesion between the retardation material and the substrate include the functional silane-containing compounds shown below. Examples include: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-urea Propyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyl Triethoxysilane, N-(3-triethoxysilylpropyl)triethylenetetramine, N-(3-trimethoxysilylpropyl)triethylenetetramine, 10-trimethoxy Silyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-di Azanonylacetate, 9-triethoxysilyl-3,6-diazanonylacetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl -3-Aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, etc.

Furthermore, in addition to improving the adhesion between the substrate and the retardation material, for the purpose of preventing the degradation of characteristics due to backlight when constituting the polarizing plate, the following phenolic plastics may also be included in the polymer composition. (phenoplast)-based, epoxy-containing compound additives. Specific phenolic plastic additives are shown below, but are not limited to this structure. [Chemical 43]

Specific examples of the epoxy group-containing compound include: ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and tripropylene glycol diglycidyl ether. ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-diglycidyl ether Bromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraepoxypropyl-2,4-hexanediol, N,N,N',N'-tetraepoxypropyl meta Xylylenediamine, 1,3-bis(N,N-diepoxypropylaminomethyl)cyclohexane, N,N,N',N'-tetraepoxypropyl-4,4'- Diaminodiphenylmethane, etc.

When a compound that improves adhesion to the substrate is used, the usage amount is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass relative to 100 parts by mass of the resin component contained in the polymer composition. parts by mass. If the usage amount is less than 0.1 parts by mass, the effect of improving adhesion cannot be expected, and if it is more than 30 parts by mass, the alignment of liquid crystal may deteriorate.

Photosensitizers can also be used as additives. Preferred are colorless sensitizers and triplet sensitizers. As for photosensitizers, there are aromatic nitro compounds, coumarins (7-diethylamino-4-methylcoumarin, 7-hydroxy-4-methylcoumarin), and ketocoumarins. , carbonyl dicoumarin, aromatic 2-hydroxyketones, and aromatic 2-hydroxyketones substituted with amine groups (2-hydroxydiphenylketone, mono or two pairs of (dimethylamino)-2-hydroxy Diphenyl ketone), acetophenone, anthraquinone, thioxanthone, benzanthrone, thiazoline (2-benzylmethylene-3-methyl-β-naphthothiazoline, 2-(β-naphthylmethylene)-3-methylbenzothiazoline, 2-(α-naphthylmethylene)-3-methylbenzothiazoline, 2-(4 -Biphenylcarboxylmethylene)-3-methylbenzothiazoline, 2-(β-naphthylcarboxylmethylene)-3-methyl-β-naphthothiazoline, 2-(4 -biphenylmethylmethylene)-3-methyl-β-naphthothiazoline, 2-(p-fluorobenzoylmethylene)-3-methyl-β-naphthothiazoline), Thazoline (2-benzoethazoline-3-methyl-β-naphthoethazoline, 2-(β-naphthylmethylene)-3-methylbenzoethazoline , 2-(α-naphthylmethylmethylene)-3-methylbenzoethazoline, 2-(4-biphenylmethylmethylene)-3-methylbenzoethazoline, 2-(β-naphthylmethylmethylene)-3-methyl-β-naphthoethazoline, 2-(4-biphenylmethylmethylene)-3-methyl-β-naphthalene Tetrazoline, 2-(p-fluorobenzoylmethylene)-3-methyl-β-naphthoxazoline), benzothiazole, nitroaniline (m- or p-nitroaniline, 2, 4,6-trinitrobenzene) or nitrobenzene (5-nitrobenzene), (2-[(m-hydroxy-p-methoxy)styryl]benzothiazole, benzoin alkyl ether, N- Alkylated phthalone, acetophenone ketal (2,2-dimethoxyphenylethanone), naphthalene, anthracene (2-naphthylmethanol, 2-naphthoic acid, 9-anthracenemethanol, and 9-anthracenecarboxylic acid ), benzopyran, azoindamide, merlotcoumarin, etc. Preferred are aromatic 2-hydroxyketone (diphenylketone), coumarin, ketocoumarin, carbonyl dicoumarin, acetophenone, anthraquinone, thioxanthone, and acetophenone ketal ketone.

In addition to the above, in the polymer composition, as long as the effects of the present invention are not impaired, a dielectric, A conductive substance and a cross-linking compound may also be added for the purpose of improving the hardness and density of the film when forming the retardation material.

[Preparation of polymer composition] The polymer composition used in the present invention is preferably prepared in the form of a coating liquid in a manner suitable for the formation of a retardation film. That is, the polymer composition used in the present invention is preferably composed of the above-mentioned component (A) and the above-mentioned solvents and compounds that improve film thickness uniformity and surface smoothness, compounds that improve the adhesion between the liquid crystal alignment film and the substrate, etc. It is prepared in the form of a solution dissolved in an organic solution. Here, the content of component (A) is preferably 1 to 30 mass%, more preferably 3 to 25 mass%, and particularly preferably 3 to 20 mass%.

In the polymer composition of this embodiment, in addition to component (A), other polymers may be mixed within a range that does not impair the liquid crystal display ability and photosensitive performance. At this time, the content of other polymers in the resin component is 0.5 to 80 mass%, preferably 1 to 50 mass%. Examples of such other polymers include polymers composed of poly(meth)acrylate, polyamide, polyimide, etc., and are not photosensitive side chain polymers that can exhibit liquid crystallinity.

[Single layer phase difference material] The phase difference material of the present invention can be produced by a method including the following [I] to [III]. [I] The step of applying the composition of the present invention on a substrate to form a coating film; [II] The step of irradiating polarized ultraviolet rays on the coating film obtained in [I]; and [III] The step of heating the coating film obtained in [II] to obtain a phase difference material.

＜Step [I]＞ Step [I] is a process of coating the composition of the present invention on a substrate. More specifically, the composition of the present invention is coated on the base material ( For example: silicon/silicon dioxide coated substrates, silicon nitride substrates, substrates coated with metals such as aluminum, molybdenum, chromium, etc., glass substrates, quartz substrates, ITO substrates, etc.), films (such as triacetyl cellulose (TAC) ) film, cyclic olefin polymer film, polyethylene terephthalate film, acrylic film and other resin films), etc. After coating, the solvent can be evaporated at 30 to 200°C, preferably at 30 to 150°C, using heating means such as a hot plate, a thermal cycle oven, or an IR (infrared) oven, to obtain a coating film.

＜Step [II]＞ In step [II], the coating film obtained in step [I] is irradiated with polarized ultraviolet light. When polarized ultraviolet rays are irradiated on the surface of the coating film, the polarized ultraviolet rays are irradiated from a certain direction to the substrate through the polarizing plate. As for the ultraviolet rays used, ultraviolet rays with a wavelength in the range of 100 to 400 nm can be used. It is better to select the most suitable wavelength through a filter according to the type of coating used. Furthermore, for example, ultraviolet rays with a wavelength in the range of 290 to 400 nm can be selected and used so as to selectively cause a photocrosslinking reaction. As for ultraviolet rays, for example, light emitted from a high-pressure mercury lamp can be used.

The amount of polarized UV irradiation depends on the coating used. The irradiation dose is preferably the maximum value of ΔA (hereinafter also referred to as ΔA _max ) that achieves the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet rays and the ultraviolet absorbance in the direction perpendicular to the polarized ultraviolet rays in the coating film. The amount of polarized ultraviolet rays is in the range of 1 to 70%, and more preferably in the range of 1 to 50%.

＜Step [III]＞ In step [III], the coating film irradiated with polarized ultraviolet rays in step [II] is heated. By heating, the coating film can be given alignment control capabilities.

For heating, heating means such as a hot plate, a heat cycle oven, or an IR (ultraviolet) oven can be used. The heating temperature can be determined by considering the temperature at which the liquid crystallinity of the coating film used is developed.

The heating temperature is preferably within the temperature range at which the specific polymer contained in the composition of the present invention exhibits liquid crystallinity (hereinafter, referred to as the liquid crystal display temperature). In the case of a thin film surface such as a coating film, the liquid crystal display temperature on the coating film surface is expected to be lower than the liquid crystal display temperature when the specific polymer is observed as a whole. Therefore, the heating temperature is preferably within the temperature range of the liquid crystal display temperature on the surface of the coating film. That is, the temperature range of the heating temperature after polarized ultraviolet irradiation is preferably 10°C lower than the lower limit of the liquid crystal display temperature range of the specific polymer used and 10°C lower than the upper limit of the liquid crystal temperature. The temperature is used as the upper limit of the range. If the heating temperature is lower than the above temperature range, the effect of amplifying the anisotropy caused by heat in the coating film tends to become insufficient. On the other hand, if the heating temperature is excessively higher than the above temperature range, the coating film may deteriorate. It tends to become close to an isotropic liquid state (homogeneous phase). At this time, it may become difficult to realign in one direction due to self-organization.

In addition, the liquid crystal display temperature is above the liquid crystal transition temperature at which the polymer or coating surface transitions from the solid phase to the liquid crystal phase. It refers to the isotropic phase where the phase transition from the liquid crystal phase occurs to the isotropic phase (homogeneous phase). The temperature below the transfer temperature (Tiso). For example, "displaying liquid crystallinity at 130°C or lower" means that the liquid crystal transition temperature at which phase transition from a solid phase to a liquid crystal phase occurs is 130°C or lower.

The thickness of the coating film formed after heating can be appropriately selected taking into account the height difference, optical and electrical properties of the substrate used, and is preferably 0.5 to 10 μm, for example.

The single-layer retardation material of the present invention obtained in this way has optical properties suitable for use in display devices, recording materials, etc., and is particularly suitable as optical compensation films such as polarizing plates and retardation plates for liquid crystal displays, organic Retardation film for EL circular polarizing plates.

＜Liquid crystal alignment agent＞ The present invention provides a liquid crystal alignment agent having the above-mentioned polymer composition, or essentially consisting of the above-mentioned polymer composition, or consisting only of the above-mentioned polymer composition, and in particular, provides a liquid crystal alignment agent for liquid crystal display elements, and more particularly It provides liquid crystal alignment agents for lateral electric field driven liquid crystal display elements.

<Liquid crystal alignment film> or <Substrate with liquid crystal alignment film> The present invention provides a liquid crystal alignment film formed from the above-mentioned liquid crystal alignment agent, particularly a liquid crystal alignment film for a liquid crystal display element, and more particularly, a liquid crystal alignment film for a lateral electric field driven liquid crystal display element. Furthermore, the present invention provides a liquid crystal alignment film formed from the above-mentioned liquid crystal alignment agent, particularly a substrate having a liquid crystal alignment film for a liquid crystal display element, and more particularly, a liquid crystal alignment film for a lateral electric field driven liquid crystal display element. A substrate is provided, in particular, a substrate for a liquid crystal display element is provided, and more particularly, a substrate for a transverse electric field driven liquid crystal display element is provided.

<Method for manufacturing liquid crystal alignment film> or <Method for manufacturing substrate with liquid crystal alignment film> The above-mentioned liquid crystal alignment film can obtain a liquid crystal alignment film endowed with alignment control capability or a substrate having the liquid crystal alignment film by having the above-mentioned steps [I] to [III]. In particular, a liquid crystal alignment film for a liquid crystal display element can be obtained. A film or a substrate having the liquid crystal alignment film, more particularly, a liquid crystal alignment film for a lateral electric field driven liquid crystal display element or a substrate having the liquid crystal alignment film can be obtained.

＜＜Substrate>> The substrate is not particularly limited, but when the liquid crystal display element to be manufactured is a transmission type, it is preferable to use a substrate with high transparency. In this case, it is not particularly limited, and a glass substrate or a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used. Furthermore, considering application to reflective liquid crystal display elements, opaque substrates such as silicon wafers can also be used.

＜＜Conductive film for transverse electric field driving＞＞ When used in a transverse electric field drive type liquid crystal display element, the substrate has a conductive film for transverse electric field drive. Examples of the conductive film include, but are not limited to, ITO (Indium Tin Oxide: indium tin oxide), IZO (Indium Zinc Oxide: indium zinc oxide), and the like when the liquid crystal display element is a transmission type. In the case of a reflective liquid crystal display element, examples of the conductive film include materials that reflect light such as aluminum, but are not limited thereto. As a method of forming the conductive film on the substrate, conventionally known techniques can be used.

Steps [I]~[III] are the same as above. However, if the thickness of the coating film in step [I] when forming the liquid crystal alignment film is too thick, it will be disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be reduced. Therefore, Preferably, it is 5~300nm, and more preferably, it is 10~150nm.

<Liquid crystal display element> and <Manufacturing method of liquid crystal display element> The present invention provides a liquid crystal display element having a substrate having the liquid crystal alignment film obtained above, and in particular, provides a lateral electric field driven liquid crystal display element.

Specifically, by preparing a second substrate in addition to the substrate having the liquid crystal alignment film obtained above (the first substrate), a lateral electric field driven liquid crystal display element can be obtained. When a second substrate without a conductive film for transverse electric field driving is used instead of a substrate with a conductive film for transverse electric field driving, a substrate with a conductive film for transverse electric field driving may be used in the same manner as the first substrate. . Moreover, it is preferable that the 2nd substrate has a liquid crystal alignment film similarly to the 1st substrate.

A method for manufacturing a liquid crystal display element, particularly a lateral electric field drive type liquid crystal display element, includes [IV] placing the first and second substrates obtained above, with the liquid crystal alignment films of the first and second substrates facing each other across the liquid crystal. Steps for obtaining liquid crystal display elements by arranging them in opposite directions. Thereby, a liquid crystal display element can be obtained, in particular, a lateral electric field driven liquid crystal display element can be obtained.

＜Step [IV]＞ [IV] The step [IV] is to obtain the substrate (first substrate) having a liquid crystal alignment film on a conductive film for lateral electric field driving obtained in step [III], and obtain it in the same manner as in the above [I'] to [III']. The substrate with the liquid crystal alignment film (the second substrate) is arranged to face each other with the liquid crystal alignment films on both sides across the liquid crystal, and a liquid crystal cell is produced using a well-known method to produce a lateral electric field driven liquid crystal display element. In addition, steps [I'] to [III'] can be performed in the same manner as steps [I] to [III], except for the presence or absence of a conductive film for transverse electric field driving in step [I]. The only difference between steps [I]~[III] and steps [I’]~[III’] is the presence or absence of the above-mentioned conductive film, so the description of steps [I’]~[III’] is omitted.

An example of manufacturing a liquid crystal cell or a liquid crystal display element is as follows: preparing the above-mentioned first and second substrates, spreading spacers on the liquid crystal alignment film of one substrate so that the liquid crystal alignment film surface is inside, and laminating the other substrate. , a method of injecting liquid crystal under reduced pressure and sealing it, or a method of dropping liquid crystal on the surface of a liquid crystal alignment film with spacers spread, and then laminating the substrate and sealing it, etc. At this time, when manufacturing a transverse electric field drive type liquid crystal display element, it is preferable to use a substrate having an electrode having a comb-like structure for transverse electric field drive on one side of the substrate. The diameter of the spacer is preferably 1 μm to 30 μm, more preferably 2 μm to 10 μm. The diameter of the spacer determines the distance between a pair of substrates sandwiching the liquid crystal layer, that is, determines the thickness of the liquid crystal layer.

As mentioned above, the polymer composition or liquid crystal alignment agent of the present invention, the liquid crystal alignment film formed using the composition or liquid crystal alignment agent or the substrate with the alignment film, and the liquid crystal display element formed with the liquid crystal alignment film or substrate, It can be suitably used in large-screen, high-resolution LCD TVs, etc. [Example]

Hereinafter, synthesis examples, preparation examples, examples and comparative examples will be given to explain the present invention in more detail, but the present invention is not limited to the following examples.

The monomers MA1 to MA2 having photoreactive groups and the monomers MB1 to MB4 and MC1 to MC3 having liquid crystallinity used in the examples are shown below. MA1 was synthesized according to the synthesis method described in International Publication No. 2011/084546. MA2 was synthesized according to the synthesis method described in Japanese Patent Application Laid-Open No. 2012-27354. MC1 was synthesized according to the synthesis method described in Japanese Patent Application Laid-Open No. 9-118717. MB1 was synthesized according to the synthesis method described in Japanese Patent Application Laid-Open No. 2016-128403. MB2~MB4 are new compounds, and the synthesis method is shown below. MC2 and MC3 were synthesized according to the synthesis method described in International Publication No. 2017/135130. In addition, the side chain derived from MA1 corresponds to the side chain (a1), the side chain derived from MB1 to MB4 corresponds to the side chain (a2), and the side chain derived from MC1 to MC3 corresponds to the side chain (a3). [Chemical 44]

The abbreviations of other reagents used in this example are shown below. (organic solvent) DMF: N,N-dimethylformamide THF: Tetrahydrofuran MeCN: Acetonitrile NMP: N-methyl-2-pyrrolidone BCS: Dinky Selousu PGME: propylene glycol monomethyl ether PGMEA: propylene glycol monomethyl ether acetate CPN: cyclopentanone (polymerization initiator) AIBN: 2,2’-azobisisobutyronitrile (surfactant) F560: Megaface F-560 (made by DIC Corporation)

<Measurement of ¹ H-NMR> Equipment: Fourier transform superconducting nuclear magnetic resonance device (FR-NMR) "AVANCE III" (manufactured by Bruker Corporation) 500 MHz. Solvent: Deuterated dimethyl sulfoxide (DMSO-d ₆ ). Standard material: tetramethylsilane (TMS).

＜Measurement of molecular weight of polymer＞ The conditions for measuring the molecular weight of the polymer are as follows. Device: Nexera GPC system (Shimadzu SCL-40) manufactured by Shimadzu Corporation Pipe column: Pipe column manufactured by Shodex Company (LF-804, KF-801) Tube string temperature: 40℃ Eluate: Tetrahydrofuran (HPLC grade) Flow rate: 1.0mL/minute Standard sample for calibration curve preparation: polystyrene (PStQuick E/PStQuick F) (manufactured by Tosoh Corporation)

[1]Synthesis of monomers ＜＜Synthesis of MB2＞＞In a 200mL four-necked flask, add MC1 (10.0g, 32.6mmol), DMF (50mg), and THF (50g), add oxalate chloride (4.56g, 35.9mmol) dropwise, and place in the chamber Stir while warm. After the reaction was completed, the reaction solution was concentrated using a rotary evaporator to obtain chloride (light yellow liquid). Add THF (50g) and 3-(4-hydroxyphenyl)methoxymethylpropionate (7.19g, 34.2mmol) to the obtained chloride, cool it with ice in a nitrogen atmosphere, and add triethylamine (Et) dropwise. ₃ N, 3.96g, 39.1mmol) and stir at room temperature. After the reaction was completed, the reaction solution was concentrated using a rotary evaporator. Ethyl acetate (100g) was added, and extraction was performed using pure water (200g). The organic layer was concentrated using a rotary evaporator and the solvent was distilled off to obtain MB2-1 (light brown liquid). In a 500 mL single-neck flask, MB2-1, MeCN (150 g), and 1N hydrochloric acid (50 g) obtained above were added, and the mixture was stirred at room temperature. After the reaction was completed, the reaction liquid was poured into pure water (200 g), and the precipitate was filtered. The obtained crude product was recrystallized from ethanol (50 g), whereby 11.2 g of MB2 (white solid) was obtained (yield 75.7%). The results of ¹ H-NMR of the target substance are shown below. From this result, it was confirmed that the obtained solid was the target MB2. ¹ H-NMR (400MHz, DMSO-d ₆ ): δ (ppm) = 12.2 (s, 1H), 8.03-8.07 (d, 2H), 7.28-7.32 (d, 2H), 7.13-7.17 (d, 2H) ), 7.08-7.12(d, 2H), 6.02(s, 1H), 5.66(s, 1H), 4.06-4.13(m, 4H), 2.82-2.88(m, 2H), 2.54-2.59(t, 2H ), 1.88(s, 3H), 1.72-1.80(m, 2H), 1,61-1,69(m, 2H), 1,38-1.50(m, 4H).

[Chemical 46] ＜＜Synthesis of MB3>> In a 200mL four-necked flask, add MC2 (15g, 35.2mmol), 3-(4-hydroxyphenyl)propionic acid methoxymethyl ester (7.78g, 37.0mmol), and THF (75g ), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC.HCl, 8.09g, 42.2mmol), and 4-dimethylaminopyridine (DMAP , 0.43g, 3.52mmol), stirred at room temperature. After the reaction was completed, pure water (450 g) was poured into the mixture, and the precipitate was filtered to obtain MB3-1 (white solid). In a 500 mL single-neck flask, MB3-1 obtained above, MeCN (225 g), and 1N hydrochloric acid (75 g) were added, and the mixture was stirred at room temperature. After the reaction was completed, the precipitated precipitate was filtered and repulped and washed with MeCN (45g). The obtained crude product was recrystallized from a mixed solvent of THF (150 g) and MeCN (150 g), thereby obtaining 12.7 g of MB3 (white solid) (yield 62.9%). The results of ¹ H-NMR of the target substance are shown below. From this result, it was confirmed that the obtained solid was the target MB3. ¹ H-NMR (400MHz, DMSO-d ₆ ): δ (ppm) = 12.2 (s, 1H), 8.20-8.24 (d, 2H), 8.08-8.12 (d, 2H), 7.50-7.54 (d, 2H) ), 7.31-7.35(d, 2H), 7.19-7.23(d, 2H), 7.11-7.16(d,2H), 6.02(s, 1H), 5.67(s, 1H), 4.08-4.14(m, 4H ), 2.84-2.89(t, 2H), 2.54-2.60(t, 2H), 1.88(s, 3H), 1.73-1.81(m, 2H), 1,62-1,69(m, 2H), 1 ,38-1.51(m, 4H).

[Chemical 47] ＜＜Synthesis of MB4＞＞In a 200mL four-necked flask, add MC3 (10.0g, 26.1mmol), DMF (50mg), and THF (50g), add oxalate chloride (3.64g, 28.7mmol) dropwise, and place in the chamber Stir while warm. After the reaction was completed, the reaction solution was concentrated using a rotary evaporator to obtain chloride (white solid). Add THF (50g) and 3-(4-hydroxyphenyl) methoxymethyl propionate (5.76g, 27.4mmol) to the obtained chloride, cool it with ice in a nitrogen atmosphere, and add triethylamine (3.17 g, 31.3 mmol) and stirred at room temperature. After the reaction was completed, the reaction solution was poured into pure water (200g), and the obtained precipitate was filtered to obtain MB4-1 (white solid). In a 1,000 mL single-neck flask, MB4-1 obtained above, MeCN (300 g), and 1N hydrochloric acid (100 g) were added, and the mixture was stirred at room temperature. After the reaction was completed, the precipitated precipitate was filtered and repulped and washed with MeCN (30 g). The obtained crude product was recrystallized from a mixed solvent of THF (10 g) and MeCN (100 g), thereby obtaining 11.3 g of MB4 (white solid) (yield 81.9%). The results of ¹ H-NMR of the target substance are shown below. From this result, it was confirmed that the obtained solid was the target MB4. ¹ H-NMR (400MHz, DMSO-d ₆ ): δ (ppm) = 12.2 (s, 1H), 8.13-8.17 (d, 2H), 7.84-7.88 (d, 2H), 7.71-7.75 (d, 2H) ), 7.30-7.34(d, 2H), 7.18-7.21(d, 2H), 7.04-7.08(d,2H), 6.02(s, 1H), 5.66(s, 1H), 4.09-4.13(t, 2H ), 4.01-4.06(t, 2H), 2.83-2.89(t, 2H), 2.55-2.60(t, 2H), 1.88(s, 3H), 1.71-1.79(m, 2H), 1,61-1 ,69(m, 2H), 1,38-1.51(m, 4H).

[2] Synthesis of polymers ＜Synthesis example 1＞ In NMP (21.4g), MA1 (2.24g, 6.74mmol), MC1 (10.3g, 33.6mmol), MB1 (1.98g, 4.49mmol) and AIBN (0.740g, 4.51mmol) were dissolved to prepare a monomer mixture. solution. In a nitrogen atmosphere, the monomer mixed solution was added dropwise to NMP (14.3 g) at 60° C. over 2 hours. After completion of the dropwise addition, the reaction was carried out at 60° C. for 12 hours. After the reaction was completed, the reaction solution was poured into a methanol/pure water mixed solvent to precipitate the polymer, which was filtered and washed with methanol to obtain polymer powder P-1 (13.0 g). P-1 has a number average molecular weight of 22,000 and a weight average molecular weight of 74,000.

＜Synthesis example 2＞ In NMP (28.6g), MA1 (2.24g, 6.74mmol), MC1 (8.96g, 29.3mmol), MB1 (3.96g, 8.99mmol) and AIBN (0.740g, 4.51mmol) were dissolved to prepare a monomer mixture solution. In a nitrogen atmosphere, the monomer mixed solution was added dropwise to NMP (19.1 g) at 60° C. over 2 hours. After completion of the dropwise addition, the reaction was carried out at 60° C. for 12 hours. After the reaction was completed, the reaction solution was poured into a methanol/pure water mixed solvent to precipitate the polymer, and was filtered and washed with methanol to obtain polymer powder P-2 (13.6 g). P-2 has a number average molecular weight of 23,000 and a weight average molecular weight of 84,000.

＜Synthesis Example 3＞ In NMP (29.7g), MA1 (2.24g, 6.74mmol), MC1 (7.59g, 24.8mmol), MB1 (5.95g, 13.5mmol) and AIBN (0.740g, 4.51mmol) were dissolved to prepare a monomer mixture. solution. In a nitrogen atmosphere, the monomer mixed solution was added dropwise to NMP (19.8 g) at 60° C. over 2 hours. After completion of the dropwise addition, the reaction was carried out at 60° C. for 12 hours. After the reaction was completed, the reaction solution was poured into a methanol/pure water mixed solvent to precipitate the polymer, which was filtered and washed with methanol to obtain polymer powder P-3 (13.8 g). P-3 has a number average molecular weight of 30,000 and a weight average molecular weight of 95,000.

＜Synthesis example 4＞ In NMP (22.4g), MA1 (1.75g, 5.26mmol), MC1 (6.97g, 22.8mmol), MB2 (3.18g, 7.00mmol) and AIBN (0.570g, 3.47mmol) were dissolved to prepare a monomer mixture. solution. In a nitrogen atmosphere, the monomer mixed solution was added dropwise to NMP (15.0 g) at 60° C. over 2 hours. After completion of the dropwise addition, the reaction was carried out at 60° C. for 12 hours. After the reaction was completed, the reaction solution was poured into a methanol/pure water mixed solvent to precipitate the polymer, and was filtered and washed with methanol to obtain polymer powder P-4 (9.98 g). P-4 has a number average molecular weight of 19,000 and a weight average molecular weight of 54,000.

＜Synthesis Example 5＞ MA1 (2.49g, 7.49mmol), MC1 (13.0g, 42.4mmol) and AIBN (0.820g, 5.00mmol) were dissolved in NMP (22.9g) to prepare a monomer mixed solution. In a nitrogen atmosphere, the monomer mixed solution was added dropwise to NMP (15.2 g) at 60° C. over 2 hours. After completion of the dropwise addition, the reaction was carried out at 60° C. for 12 hours. After the reaction was completed, the reaction solution was poured into a methanol/pure water mixed solvent to precipitate the polymer, which was filtered and washed with methanol to obtain polymer powder P-5 (12.4 g). P-5 has a number average molecular weight of 34,000 and a weight average molecular weight of 98,000.

＜Synthesis example 6＞ In NMP (22.7g), MA1 (1.79g, 5.39mmol), MC1 (7.17g, 23.4mmol), MC2 (3.07g, 7.20mmol) and AIBN (0.59g, 3.59mmol) were dissolved to prepare a monomer mixture solution. In a nitrogen atmosphere, the monomer mixed solution was added dropwise to NMP (15.2 g) at 60° C. over 2 hours. After completion of the dropwise addition, the reaction was carried out at 60° C. for 12 hours. After the reaction was completed, the reaction solution was poured into a methanol/pure water mixed solvent to precipitate the polymer, which was filtered and washed with methanol to obtain polymer powder P-6 (10.1 g).

＜Synthesis Example 7＞ In NMP (21.3g), MA1 (1.99g, 6.00mmol), MC1 (7.97g, 26.0mmol), MB3 (4.58g, 8.00mmol) and AIBN (0.66g, 4.00mmol) were dissolved to prepare a monomer mixture solution. In a nitrogen atmosphere, the monomer mixed solution was added dropwise to NMP (14.2 g) at 60° C. over 2 hours. After completion of the dropwise addition, the reaction was carried out at 60° C. for 12 hours. After the reaction was completed, the reaction solution was poured into a methanol/pure water mixed solvent to precipitate the polymer, which was filtered and washed with methanol to obtain polymer powder P-7 (12.1 g). P-7 has a number average molecular weight of 23,000 and a weight average molecular weight of 45,000.

＜Synthesis example 8＞ In NMP (20.8g), MA1 (1.99g, 6.00mmol), MC1 (7.97g, 26.0mmol), MB4 (4.25g, 8.00mmol) and AIBN (0.66g, 4.00mmol) were dissolved to prepare a monomer mixture solution. In a nitrogen atmosphere, the monomer mixed solution was added dropwise to NMP (13.9 g) at 60° C. over 2 hours. After completion of the dropwise addition, the reaction was carried out at 60° C. for 12 hours. After the reaction was completed, the reaction solution was poured into a methanol/pure water mixed solvent to precipitate the polymer, which was filtered and washed with methanol to obtain polymer powder P-8 (12.6 g). P-8 has a number average molecular weight of 24,000 and a weight average molecular weight of 52,000.

＜Synthesis Example 9＞ In NMP (15.8g), MA2 (1.75g, 4.00mmol), MB1 (1.76g, 4.00mmol), MC1 (3.68g, 12.0mmol) and AIBN (0.33g, 2.00mmol) were dissolved to prepare a monomer mixture. solution. In a nitrogen atmosphere, the monomer mixed solution was added dropwise to NMP (6.76 g) at 60° C. over 2 hours. After completion of the dropwise addition, the reaction was carried out at 60° C. for 12 hours. After the reaction was completed, the reaction solution was poured into a methanol/pure water mixed solvent to precipitate the polymer, and was filtered and washed with methanol to obtain polymer powder P-9 (6.01 g). P-9 has a number average molecular weight of 21,000 and a weight average molecular weight of 99,000.

＜Synthesis Example 10＞ In NMP (15.7g), MA2 (1.75g, 4.00mmol), MC1 (3.68g, 12.0mmol), MC2 (1.71g, 4.00mmol) and AIBN (0.33g, 2.00mmol) were dissolved to prepare a monomer mixture solution. In a nitrogen atmosphere, the monomer mixed solution was added dropwise to NMP (6.72 g) at 60° C. over 2 hours. After completion of the dropwise addition, the reaction was carried out at 60° C. for 12 hours. After the reaction was completed, the reaction solution was poured into a methanol/pure water mixed solvent to precipitate the polymer, which was filtered and washed with methanol to obtain polymer powder P-10 (6.12 g). P-10 has a number average molecular weight of 20,000 and a weight average molecular weight of 50,000.

[3] Preparation of retardation film forming materials <Preparation Example 1> To the polymer powder P-1 (3.60g) obtained in Synthesis Example 1, NMP (2.00g), PGME (7.00g), BCS (2.00g), PGMEA (5.38g), and F560 (18.0mg) were added and stirring, thereby obtaining polymer solution T-1. This polymer solution T-1 is directly used as a material for forming a retardation film.

＜Preparation Examples 2~8＞ The polymer solutions T-2 to T-8 were obtained in the same manner as in Preparation Example 1 except that the polymer powder used was replaced from P-1 to P-2 to P-8. This polymer solution T-2~T-8 is directly used as a material for forming a retardation film. Hereinafter, the retardation film forming materials are summarized in Table 1. In Table 1, the numerical values in parentheses of the composition ratio indicate the blending amount (mol parts) of each monomer relative to a total of 100 mol parts of the monomers used.

<Preparation Example 9> To the polymer powder P-2 (3.60 g) obtained in Synthesis Example 2, CPN (16.38 g) and F560 (18.0 mg) were added and stirred to obtain a polymer solution T-9. This polymer solution T-9 is directly used as a material for forming a retardation film.

<Preparation Examples 10, 11> The polymer solutions T-10 and T-11 were obtained in the same manner as in Preparation Example 9 except that the polymer powder used was replaced from P-2 to P-9 and P-10. The polymer solutions T-10 and T-11 are directly used as materials for forming the retardation film. Hereinafter, the retardation film forming materials are summarized in Table 1. In Table 1, the numerical values in parentheses of the composition ratio indicate the blending amount (mol parts) of each monomer relative to a total of 100 mol parts of the monomers used.

[Table 1]

[4] Production of single-layer retardation film <Example 1> After filtering the polymer solution T-1 with a filter with a pore size of 5.0 μm, the polymer solution T-1 was coated on an alkali-free glass substrate using a bar coater. The substrate was dried in a thermal cycle oven at 80° C. for 3 minutes, and then irradiated with 365 nm polarized ultraviolet light of 1200 mJ/cm ² from a high-pressure mercury lamp through a 365 nm bandpass filter and a polarizing plate. Heating in an IR oven at 100° C. for 20 minutes produced a glass substrate S-1 with a retardation film. In addition, the film thickness of the retardation layer of S-1 is 2.5 μm.

<Examples 2~16> Except having changed the polymer solution, the exposure amount, and the main calcination temperature as shown in Table 2 to Table 3, it was carried out in the same manner as in Example 1, thereby producing glass substrates S-2 to S-16 with retardation films.

<Example 17> After filtering the polymer solution T-9 with a filter with a pore size of 5.0 μm, the polymer solution T-9 was coated on a COP membrane (ZF16-100, manufactured by Nippon Zeon) using a bar coater. The substrate was dried in a thermal cycle oven at 50° C. for 3 minutes, and then the substrate was irradiated with polarized ultraviolet light of 1200 mJ/cm ² at 365 nm from a high-pressure mercury lamp through a 365 nm bandpass filter and a polarizing plate. Heat in an IR oven at 120°C for 10 minutes to produce COP film S-17 with a retardation film. In addition, the film thickness of the retardation layer of S-17 is 2.0 μm.

<Example 18> After filtering the polymer solution T-10 using a filter with a pore size of 5.0 μm, the polymer solution T-10 was coated on a COP membrane (ZF16-100 manufactured by Japan Zeon) using a bar coater. The substrate was dried in a thermal cycle oven at 50° C. for 3 minutes, and then irradiated with 313 nm polarized ultraviolet light of 200 mJ/cm ² from a high-pressure mercury lamp through a 313 nm bandpass filter and a polarizing plate. Heat in an IR oven at 120°C for 10 minutes to produce COP film S-18 with a retardation film. In addition, the film thickness of the retardation layer of S-18 is 2.0 μm.

<Comparative Example 1> After filtering the polymer solution T-5 through a filter with a pore size of 5.0 μm, the polymer solution T-5 was coated on an alkali-free glass substrate using a bar coater. The substrate was dried in a thermal cycle oven at 80° C. for 3 minutes, and then irradiated with 365 nm polarized ultraviolet light of 1200 mJ/cm ² from a high-pressure mercury lamp through a 365 nm bandpass filter and a polarizing plate. Heating in an IR oven at 100° C. for 20 minutes produced a glass substrate R-1 with a retardation film. In addition, the film thickness of the retardation layer of R-1 is 2.3 μm.

＜Comparative Examples 2~4＞ Glass substrates R-2 to R-4 with retardation films were produced in the same manner as Comparative Example 1, except that the polymer solution, exposure amount, and main calcination temperature were changed as shown in Tables 2 and 3.

<Comparative Example 5> After filtering the polymer solution T-8 with a filter with a pore size of 5.0 μm, the polymer solution T-8 was coated on a COP membrane (ZF16-100 manufactured by Nippon Zeon) using a bar coater. The substrate was dried in a thermal cycle oven at 50° C. for 3 minutes, and then irradiated with 313 nm polarized ultraviolet light of 200 mJ/cm ² from a high-pressure mercury lamp through a 313 nm bandpass filter and a polarizing plate. Heating in an IR oven at 120°C for 10 minutes produced a COP film R-5 with a retardation film. In addition, the film thickness of the retardation layer of R-5 is 2.0 μm.

For each of the substrates S-1 to S-18 and R-1 to R-5 with a retardation film, the film thickness, retardation value and Δn were evaluated by the following method.

[Film thickness evaluation] The film thickness of the retardation layer of the glass substrate with the retardation film was measured using a high-precision fine shape measuring machine (ET4000M) manufactured by Kosaka Laboratory Co., Ltd. The film thickness of the retardation layer of the COP film with a retardation film was measured using an F20 film thickness meter manufactured by Fila Corporation.

[Evaluation of phase difference value and Δn] The linear phase difference at a wavelength of 550 nm was evaluated using Axo Scan manufactured by Axometrics. The linear phase difference was divided by the film thickness to calculate Δn (birefringence) and summarized in Tables 2, 3, and 4.

[Table 2]

[table 3]

[Table 4]

The single-layer retardation material obtained from the polymer composition using the monomer MB shows a higher Δn than the single-layer retardation material obtained from the polymer composition not using the monomer MB. It shows good Δn in low-temperature calcination at 100~120℃, so it can form a retardation layer of the film base material.

[5] Manufacturing of liquid crystal alignment film <Preparation Example 12> NMP (7.6 g) was added to 0.4 g of the obtained polymer powder (P-2), and the mixture was stirred at room temperature for 1 hour to dissolve. BCS (2.0g) was added to this solution and stirred, thereby obtaining a liquid crystal alignment agent (U-1).

[Preparation of substrate for order parameter measurement] <Example 19> A substrate for order parameter measurement was produced using the procedure shown below using the liquid crystal alignment agent (U-1). A quartz substrate with a size of 40 mm×40 mm and a thickness of 1.0 mm was used as the substrate. The liquid crystal alignment agent (U-1) was filtered with a 1.0 μm filter, spin-coated on a quartz substrate, and dried on a hot plate at 60° C. for 90 seconds to form a thin film with a thickness of 100 nm. Next, 313nm polarized ultraviolet light of 5 to 50mJ/cm ² was irradiated from a high-pressure mercury lamp through a 313nm bandpass filter and a polarizing plate, and then heated with a 120°C hot plate for 10 minutes to obtain a substrate with a liquid crystal alignment film.

[Measurement of Ordering Parameter] In order to measure the optical anisotropy of the liquid crystal alignment film using the substrate with the liquid crystal alignment film produced above, S, which is the ordering parameter, was calculated from the absorbance of polarized light using the following formula. [Number 1] Here, A _para represents the absorbance in a direction parallel to the direction of the irradiated polarized ultraviolet light, and A _per represents the absorbance in a direction perpendicular to the direction of the irradiated polarized ultraviolet light. The closer the absolute value of the in-plane alignment degree is to 1, the more uniform the alignment state is. The closer the order parameter is to 1 or -1, the more uniform the alignment state is. The calculated absolute values of the order parameter (S) are shown in Table 5. In addition, the absolute values of the ordered parameters are expressed using the following evaluation criteria. ＜＜Evaluation criteria＞＞ ○: 0.5 or more ○△: 0.4 or more and less than 0.5 △: 0.3 or more and less than 0.4 ×: less than 0.3 In addition, for the measurement of absorbance, ultraviolet-visible light-made by Shimadzu Corporation was used. Near infrared spectrophotometer U-3100PC.

[table 5]

As shown in Table 5, the liquid crystal alignment agent obtained from the polymer composition using the monomer MB showed an order parameter value of approximately 0.4 to 0.5 under low-temperature calcination conditions of 120°C, confirming that it can function as a liquid crystal alignment film. Function.

Claims (7)

A polymer composition containing: (A) a side chain type polymer having a side chain (a1) having a photoreactive site and a side chain (a2) having a site represented by the following formula (b); and (B) Organic solvent; [Chemical 1] In formula (b), W ¹ , W ² and W ³ are each independently a single bond, -O-, -C(=O)-O-, -OC(=O)-, -C(=O) -N(R')- or -N(R')-C(=O)-; when the number of W ² is 2 or more, each W ² can be the same or different; R' represents a hydrogen atom or a carbon number of 1 ~6 alkyl group; Q is an alkylene group with 1 to 10 carbon atoms; part or all of the hydrogen atoms of the alkylene group may be replaced by halogen atoms; L represents a single bond, an alkylene group with 1 to 12 carbon atoms, Or -CH ₂ - constituting an alkylene group with 1 to 12 carbon atoms, one or more non-adjacent ones passing through -O-, -S-, -C(=O)-O-, or -OC(=O) - Substituted divalent linking group, part or all of the hydrogen atoms of the alkylene group may be substituted by halogen atoms; Q ¹ is a single bond, phenylene group, naphthylene group or divalent lipid with 5 to 8 carbon atoms Cyclic hydrocarbon group, part or all of the hydrogen atoms of the phenyl and naphthylene groups may be replaced by a cyano group, a halogen atom, an alkyl group with 1 to 5 carbon atoms, an alkylcarbonyl group with 2 to 6 carbon atoms, or a cyano group with 1 carbon atoms. ~5 alkoxy groups are substituted; when the number of Q ¹ is 2 or more, each Q ¹ can be the same or different from each other; the hydrogen atom on the benzene ring can be selected from an alkyl group with a carbon number of 1 to 6, a carbon number of 1 ~ 6 haloalkyl groups, alkoxy groups having 1 to 6 carbon atoms, haloalkoxy groups having 1 to 6 carbon atoms, cyano groups, and nitro group substituents; in addition, the benzene ring can be a naphthalene ring, and the naphthalene ring can be The hydrogen atoms on the ring can be selected from alkyl groups with 1 to 6 carbon atoms, haloalkyl groups with 1 to 6 carbon atoms, alkoxy groups with 1 to 6 carbon atoms, haloalkoxy groups with 1 to 6 carbon atoms, and cyanide. Substituted by substituents of base and nitro; n ₁ is 0, 1, 2 or 3; the dotted line is the bond. The polymer composition of claim 1, wherein (A) the side chain type polymer further has a side chain (a3) that only exhibits liquid crystallinity other than the structure represented by formula (b). The polymer composition of claim 1, wherein the side chain (a1) of the photoreactive moiety has a side chain represented by any one of the following formulas (a1-1) to (a1-6); [Chemical 2 ] In the formula, n1 and n2 are each independently 0, 1, 2 or 3; L represents a single bond, an alkylene group with 1 to 12 carbon atoms, or -CH ₂ - constituting an alkylene group with 1 to 12 carbon atoms. One or more non-adjacent divalent linking groups substituted by -O-, -S-, -C(=O)-O-, or -OC(=O)-, the hydrogen atom of the alkylene group Part or all of the hydrogen atoms in the alkylene group may be substituted by halogen atoms; T ¹ is a single bond or an alkylene group with 1 to 12 carbon atoms, and part or all of the hydrogen atoms in the alkylene group may be substituted by halogen atoms; A ¹ , A ² and D ¹ , each independently a single bond, -O-, -CH ₂ -, -C(=O)-O-, -OC(=O)-, -C(=O)-NH- or -NH-C (=O)-; However, when T ¹ is a single bond, A ² is also a single bond; Y ¹ and Y ² are phenyl or naphthylene groups, and part of the hydrogen atoms of the phenyl or naphthylene groups or all, may be substituted by a cyano group, a halogen atom, an alkyl group with 1 to 5 carbon atoms, an alkylcarbonyl group with 2 to 6 carbon atoms, or an alkoxy group with 1 to 5 carbon atoms; P ¹ , Q ¹ and Q ² , Each independently represents a single bond, a phenylene group, or a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms. Part or all of the hydrogen atoms of the phenylene group may be replaced by a cyano group, a halogen atom, or a carbon number of 1 to 5. Substituted with an alkyl group, an alkylcarbonyl group with 2 to 6 carbon atoms, or an alkoxy group with 1 to 5 carbon atoms; when the number of Q ¹ is 2 or more, each Q ¹ can be the same or different from each other, and the number of Q ² is 2 In the above, each Q ² may be the same or different from each other; R is a hydrogen atom, a cyano group, a halogen atom, a carboxyl group, an alkyl group with 1 to 5 carbon atoms, an alkylcarbonyl group with 2 to 6 carbon atoms, or an alkylcarbonyl group with 3 to 7 carbon atoms. cycloalkyl or alkoxy group with 1 to 5 carbon atoms; X ¹ and X ² are each independently a single bond, -O-, -C(=O)-O-, -OC(=O)-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-C(=O)-O- or -OC(=O)-CH=CH-; the number of X ¹ is 2 In the above case, each X ¹ may be the same or different from each other. When the number of X ² is 2 or more, each X ² may be the same or different from each other; Cou is a coumarin-6-yl group or a coumarin-7-yl group, Part of the hydrogen atoms bonded to these can be -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen atoms, alkyl groups with 1 to 5 carbon atoms, or 1 carbon group ~5 alkoxy substitution; E is -C(=O)-O-, -OC(=O)-, -C(=O)-S- or -SC(=O)-; G ¹ and G ² , each independently N or CH; The hydrogen atom of CH=CH in the above definition can be selected from cyano group, halogen atom, alkyl group with 1 to 5 carbon atoms, alkylcarbonyl group with 2 to 6 carbon atoms and The substituent of the alkoxy group with 1 to 5 carbon atoms is substituted; the dotted line is the bond. The polymer composition of claim 2, wherein the above (a3) is represented by any one of the following formulas (a3-1) to (a3 to 11); [Chemical 3] [Chemical 4] In the formula, L represents a single bond, an alkylene group with 1 to 12 carbon atoms, or one or more -CH ₂ - constituting an alkylene group with 1 to 12 carbon atoms that are not adjacent to each other and are separated by -O-, -S- , -C(=O)-O-, or -OC(=O)-substituted divalent linking group, part or all of the hydrogen atoms of the alkylene group may be substituted by halogen atoms; A ³ and A ⁴ , Each independently is a single bond, -O-, -CH ₂ -, -C(=O)-O-, -OC(=O)-, -C(=O)-NH-, or -NH-C( =O)-; when the number of A ⁴ is 2 or more, each A ⁴ may be the same or different; R ¹ is -NO ₂ , -CN, halogen atom, phenyl group, naphthyl group, biphenyl group, furyl group , 1-valent nitrogen-containing heterocyclic group, 1-valent alicyclic hydrocarbon group with 5 to 8 carbon atoms, alkyl group with 1 to 12 carbon atoms, or alkoxy group with 1 to 12 carbon atoms; R ² is phenyl, naphthyl, Biphenyl group, furyl group, monovalent nitrogen-containing heterocyclic group or monovalent alicyclic hydrocarbon group with 5 to 8 carbon atoms. Part or all of the hydrogen atoms of these groups can be -NO ₂ , -CN, halogen atoms , substituted by an alkyl group with 1 to 5 carbon atoms or an alkoxy group with 1 to 5 carbon atoms; R ³ is a hydrogen atom, -NO ₂ , -CN, halogen atom, phenyl, naphthyl, biphenyl, furyl, 1-valent nitrogen-containing heterocyclic group, 1-valent alicyclic hydrocarbon group with 5 to 8 carbon atoms, alkyl group with 1 to 12 carbon atoms, or alkoxy group with 1 to 12 carbon atoms; E is -C(=O)-O -, -OC(=O)-, -C(=O)-S- or -SC(=O)-; k1~k5 are each independently an integer from 0 to 2, but the total of k1~k5 is 2 Above; k6 and k7 are each independently an integer from 0 to 2, but the sum of k6 and k7 is more than 1; m1, m2 and m3 are each independently an integer from 1 to 3; n is 0 or 1; Z ¹ and Z ² , each independently a single bond, -C(=O)-, -CH ₂ -O-, or -CF ₂ -; part or all of the hydrogen atoms on the benzene ring and naphthalene ring may be replaced by cyano groups , halogen atom, alkyl group with 1 to 5 carbon atoms, alkylcarbonyl group with 2 to 6 carbon atoms, or alkoxy group with 1 to 5 carbon atoms; the dotted line is a bond. A manufacturing method of single-layer phase difference material, which has: [I] The step of applying the polymer composition according to any one of claims 1 to 4 on a substrate to form a coating film; [II] The step of irradiating polarized ultraviolet rays on the coating film obtained in [I]; and [III] The step of heating the coating film obtained in [II] to obtain a phase difference material. A single-layer retardation material obtained from the polymer composition according to any one of claims 1 to 4. A liquid crystal alignment agent obtained from the polymer composition of any one of claims 1 to 4.