Polymer composition and single-layer phase difference material

Abstract

The present invention provides a polymer composition capable of producing a phase difference film with little turbidity by a simpler process, the polymer composition comprising (A) a block copolymer and (B) an organic solvent, the block copolymer has a photosensitive side-chain polymer block (A1) capable of exhibiting liquid crystalline properties, and a polymer block (A2) containing a repeating unit that does not contain a photo-alignment side chain or a liquid crystalline side chain.

Description

Technical Field

[0001] The present invention relates to a composition comprising a polymer and a single-layer phase difference material. Background Art

[0002] From the requirements of improving the display quality and lightening of liquid crystal display devices, the requirements for polymer films with controlled internal molecular orientation structures as optical compensation films such as polarizing plates and phase difference plates have increased. In order to meet this requirement, films using the optical anisotropy of polymerizable liquid crystal compounds have been developed. The polymerizable liquid crystal compounds used herein are generally liquid crystal compounds having a polymerizable group and a liquid crystal structural part (a structural part having a spacer part and a liquid crystal unit (mesogen) part), and as the polymerizable group, an acrylic group is widely used.

[0003] Such polymerizable liquid crystal compounds are usually polymerized by irradiation with radiation such as ultraviolet rays to form polymers (films). For example, it is known that a specific polymerizable liquid crystal compound having an acrylic group is loaded between supports, and the compound is irradiated with radiation while being kept in a liquid crystal state to obtain a polymer (Patent Document 1); a photopolymerization initiator is added to a mixture of two polymerizable liquid crystal compounds having acrylic groups or a composition in which a chiral liquid crystal is mixed in the mixture, and ultraviolet rays are irradiated to obtain a polymer (Patent Document 2).

[0004] In addition, various single-layer coating type alignment films such as alignment films obtained by using polymerizable liquid crystal compounds and polymers without the need for liquid crystal alignment films (Patent Documents 3 and 4), and alignment films obtained by using polymers containing photocrosslinking sites (Patent Documents 5 and 6) have been reported. Polymers showing high orientation have low solubility, and as phase difference materials, they will cause problems such as haze (Haze, turbidity) and insufficient phase difference. No material has been found to solve such problems so far.

[0005] Prior art literature Patent Literature Patent Document 1: Japanese Patent Application Laid-Open No. 62-70407 Patent Document 2: Japanese Patent Application Laid-Open No. 9-208957 Patent Document 3: 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 Laid-Open No. 11-189665 Summary of the invention

[0006] Technical problem to be solved by the invention

[0007] The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a polymer composition capable of producing a single-layer retardation material with less turbidity by a simpler process, and a single-layer retardation material obtained from the polymer composition.

[0008] Technical solutions for solving technical problems

[0009] The inventors of the present invention have repeatedly conducted in-depth studies to solve the above-mentioned technical problems, and as a result, have found that by using a composition containing a specific polymer and a specific additive, a single-layer phase difference material with less turbidity and anisotropy (Δn) can be produced at low temperature without using a liquid crystal alignment film, thereby completing the present invention.

[0010] That is, the present invention provides the following polymer composition and single-layer phase difference material.

[0011] 1. A polymer composition comprising (A) a block copolymer and (B) an organic solvent, wherein the block copolymer comprises: a photosensitive side chain polymer block (A1) capable of exhibiting liquid crystal properties, and a polymer block (A2) comprising a repeating unit containing no photo-alignment side chain and no liquid crystal side chain.

[0012] 2. The polymer composition according to 1, wherein the side chain type polymer block (A1) has a side chain represented by any one of the following formulae (a1) to (a6).

[0013] [Chemistry 1]

[0014] (Wherein, n1 and n2 are each independently 0, 1, 2 or 3.

[0015] L is a single bond or an alkylene group having 1 to 12 carbon atoms, and a part or all of the hydrogen atoms of the alkylene group may be substituted with halogen atoms.

[0016] T 1 It is a single bond or an alkylene group having 1 to 12 carbon atoms, and a part or all of the hydrogen atoms of the alkylene group may be substituted with halogen atoms.

[0017] A 1 , A 2 and D 1 Each is independently a single bond, -O-, -CH2-, -C(=O)-O-, -OC(=O)-, -C(=O)-NH- or -NH-C(=O)-. 1 When A is a single bond, 2 Also a single bond.

[0018] Y 1and Y 2 It is a phenylene group or a naphthylene group, and a part or all of the hydrogen atoms of the phenylene group and the naphthylene group may be replaced by a cyano group, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.

[0019] 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, wherein a part or all of the hydrogen atoms of the phenylene group may be replaced by a cyano group, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms. 1 When the number is 2 or more, each Q 1 They can be the same or different; when Q 2 When the number is 2 or more, each Q 2 They can be the same or different.

[0020] R is a hydrogen atom, a cyano group, a halogen atom, a carboxyl group, an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.

[0021] X 1 and X 2 Each is 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-. 1 When the number is 2 or more, each X 1 They can be the same or different; when X 2 When the number is 2 or more, each X 2 They can be the same or different.

[0022] Z 1a and Z 2a Each independently represents a hydrogen atom, a halogen atom, a cyano group or an alkyl group having 1 to 3 carbon atoms, wherein a part or all of the hydrogen atoms of the alkyl group may be replaced by fluorine atoms.

[0023] Cou is a coumarin-6-yl group or a coumarin-7-yl group, and a part of the hydrogen atoms bonded thereto may be replaced by -NO2, -CN, -CH=C(CN)2, -CH=CH-CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.

[0024] E is -C(=O)-O-, -OC(=O)-, -C(=O)-S- or -SC(=O)-.

[0025] G 1 and G 2 are each independently N or CH.

[0026] The dotted line is a bond.)

[0027] 3. The polymer composition according to 1 or 2, wherein the side chain type polymer block (A1) further has a side chain that undergoes neither photodimerization nor photoisomerization.

[0028] 4. The polymer composition according to 3, wherein the side chain that undergoes neither photodimerization nor photoisomerization is a side chain represented by any one of the following formulae (b1) to (b13).

[0029] [Chemistry 2]

[0030] [Chemistry 3]

[0031] [Chemistry 4]

[0032] (In the formula, A 3 and A 4 Each is independently a single bond, -O-, -CH2-, -C(=O)-O-, -OC(=O)-, -C(=O)-NH-, or -NH-C(=O)-. 4 When the number is 2 or more, each A 4 They can be the same or different.

[0033] R 1 It is -NO2, -CN, a halogen atom, a phenyl group, a naphthyl group, a biphenyl group, a furyl group, a monovalent nitrogen-containing heterocyclic group, a monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.

[0034] R 2 It is a phenyl group, a naphthyl group, a biphenyl group, a furyl group, a monovalent nitrogen-containing heterocyclic group or a monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and a part or all of the hydrogen atoms in these groups may be replaced by -NO2, -CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms.

[0035] R 3It is a hydrogen atom, -NO2, -CN, -CH=C(CN)2, -CH=CH-CN, a halogen atom, a phenyl group, a naphthyl group, a biphenyl group, a furyl group, a monovalent nitrogen-containing heterocyclic group, a monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.

[0036] E is -C(=O)-O-, -OC(=O)-, -C(=O)-S- or -SC(=O)-.

[0037] a is an integer from 1 to 12.

[0038] k1 to k5 are each independently an integer of 0 to 2, and the total of k1 to k5 is 2 or more.

[0039] k6 and k7 are each independently an integer of 0 to 2, and the total of k6 and k7 is 1 or more.

[0040] m1, m2 and m3 are each independently an integer of 1-3.

[0041] n is 0 or 1.

[0042] Z 1 and Z 2 Each is independently a single bond, -C(=O)-, -CH2-O-, or -CF2-.

[0043] W 1 , W 2 and W 3 Each is independently a single bond, -O-, -C(=O)-O-, -OC(=O)-, -C(=O)-N(R')- or -N(R')-C(=O)-. 2 When the number is 2 or more, each W 2 They may be the same as or different from each other. R' represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0044] Q is an alkylene group having 1 to 10 carbon atoms. A part or all of the hydrogen atoms in the alkylene group may be substituted with halogen atoms.

[0045] L represents a single bond or an alkylene group having 1 to 12 carbon atoms, or a divalent linking group in which one or more -CH2- constituting the alkylene group having 1 to 12 carbon atoms is replaced by -O-, -S-, -C(=O)-O-, or -OC(=O)-, and a part or all of the hydrogen atoms of the alkylene group may be replaced by halogen atoms.

[0046] Q 1is a single bond, a phenylene group, a naphthylene group or a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and part or all of the hydrogen atoms of the phenylene group and the naphthylene group may be replaced by a cyano group, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms. 1 When the number is 2 or more, each Q 1 They can be the same or different.

[0047] n1 is 0, 1, 2 or 3.

[0048] The hydrogen atoms on the benzene ring and the naphthalene ring may be replaced by a substituent selected from an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, a halogen atom, a cyano group and a nitro group.

[0049] The dotted line is a bond.)

[0050] 5. The polymer composition according to 1, wherein the polymer block (A2) comprising a repeating unit having no photo-alignment side chain and no liquid crystal side chain is a polymer block derived from a polymeric polymerization initiator.

[0051] 6. The polymer composition according to 5, wherein the polymeric polymerization initiator has a repeating unit represented by the following formula (1).

[0052] [Chemistry 5]

[0053] (Where R a1 ~R a4 Each R is independently a linear or branched alkyl group having 1 to 6 carbon atoms, or a cyano group. L1 and R L2 Each independently represents an alkylene group having 1 to 10 carbon atoms. 1 and L 2 Each independently represents -C(=O)-O-, -OC(=O)-, -C(=O)-NH- or -NH-C(=O)-. X represents a divalent group represented by the following formula (2) or (3).

[0054] [Chemistry 6]

[0055] (Where R a5 ~R a8 It is a linear or branched alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms. L3 , R L4 , R L5 and R L6Each is independently an alkylene group having 1 to 10 carbon atoms. x and y are each independently a positive integer.)

[0056] 7. The polymer composition according to 6, wherein the polymeric polymerization initiator is represented by any one of the following formulas (In-1) to (In-2).

[0057] [Chemistry 7]

[0058] (Wherein, x and y are the same as above. n is a positive integer.)

[0059] 8. The polymer composition according to 1, wherein the polymer block (A2) comprising a repeating unit having no photo-alignment side chain and no liquid crystal side chain is a polymer block derived from a polymeric chain transfer agent.

[0060] 9. The polymer composition according to 8, wherein the polymeric chain transfer agent is represented by the following formula (4).

[0061] [Chemistry 8]

[0062] (wherein, Y is a linear or branched alkyl group having 1 to 3 carbon atoms, a hydroxyl group, a carboxyl group, or a sulfanyl group.) L7 and R L8 Each is independently a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms. x is a positive integer.)

[0063] 10. The polymer composition according to 1, wherein the number average molecular weight of the photosensitivity side chain polymer block (A1) capable of expressing liquid crystallinity is 5,000 to 300,000.

[0064] 11. The polymer composition according to 1, wherein the polymer block (A2) comprising a repeating unit having no photo-alignment side chain and no liquid crystal side chain has a number average molecular weight of 200 to 10,000.

[0065] 12. A method for producing a single-layer phase difference material, comprising the following steps: (I) coating the polymer composition of any one of 1 to 11 on a substrate to form a coating film;

[0066] (II) irradiating the coating film with polarized ultraviolet rays; and

[0067] (III) A step of heating the coating film irradiated with ultraviolet rays to obtain a phase difference material.

[0068] 13. A single-layer phase difference material obtained from the polymer composition according to any one of 1 to 11.

[0069] Effects of the Invention According to the present invention, it is possible to provide a single-layer retardation material which has little turbidity even in a thin film and exhibits a retardation even when fired at a low temperature, and a polymer composition for providing the single-layer retardation material. DETAILED DESCRIPTION

[0070] The present inventors have conducted intensive studies and, as a result, have obtained the following findings and have completed the present invention.

[0071] The polymer composition of the present invention contains a block copolymer (hereinafter, also referred to as a side chain type block copolymer), and the block copolymer has: a side chain type polymer block (A1) (hereinafter, also referred to as a side chain type polymer block) that can show liquid crystal sensitivity and a polymer block (A2) containing repeating units that do not contain a light-oriented side chain and a liquid crystal side chain, and the coating obtained using the polymer composition becomes a film with a side chain that can show liquid crystal sensitivity. The coating is not subjected to friction treatment, and an orientation treatment is performed by polarized light irradiation. Then, after polarized light irradiation, through the process of heating the polymer film, it becomes a film (hereinafter, also referred to as a single-layer phase difference material) endowed with optical anisotropy. At this time, the tiny anisotropy shown by polarized light irradiation becomes a driving force, and the side chain type block copolymer itself is effectively reoriented by self-organization. As a result, it is possible to achieve efficient orientation treatment, and a single-layer phase difference material endowed with high optical anisotropy is obtained.

[0072] In addition, the polymer composition of the present invention is characterized in that the polymer of (A) component is a block copolymer of a polymer block (A2) having a photosensitivity that can show liquid crystallinity and a repeating unit that does not contain a light-oriented side chain and a liquid crystal side chain. Thus, the molecular mobility of the side chain block copolymer of (A) component in a solvent is improved, and as a result, the molecular crystallinity in the film of the phase difference material obtained by the polymer composition of the present invention is suppressed, and visual recognition haze (visual recognition haze) is suppressed. It should be noted that these include the insights of the inventors on the mechanism of the present invention, and do not limit the present invention.

[0073] Hereinafter, embodiments of the present invention will be described in detail.

[0074] The polymer composition of the present invention is characterized in that it comprises: (A) a block copolymer and (B) an organic solvent, wherein the block copolymer has a side chain type polymer block (A1) and a polymer block (A2), wherein the side chain type polymer block (A1) has a side chain having a photoreactive portion, and the polymer block (A2) comprises a repeating unit that does not contain a photo-alignable side chain and a liquid crystal side chain.

[0075] [(A) Side chain type block copolymer]

[0076] (A) component is a side chain type block copolymer that exhibits liquid crystallinity within a specified temperature range, which comprises: a side chain type polymer block (A1) having a side chain with a photoreactive site, and a polymer block (A2) comprising a repeating unit that does not contain a photo-oriented side chain and a liquid crystal side chain. The side chain type polymer block (A1) has a photoreactive site that reacts by ultraviolet light in the side chain, specifically, a photosensitive side chain that can exhibit liquid crystallinity and a liquid crystal side chain as required. The polymer block (A2) comprising a repeating unit that does not contain a photo-oriented side chain and a liquid crystal side chain may also have a main chain from a specified polymerization initiator described later. The coating film obtained by the polymer composition comprising such a side chain type block copolymer becomes a film having liquid crystallinity and photosensitivity caused by the side chain type polymer block (A1), and high solvent solubility and film softness (low glass transition temperature capability) caused by the polymer block (A2) comprising a repeating unit that does not contain a photo-oriented side chain and a liquid crystal side chain. The coating film is not subjected to friction treatment, and an orientation treatment is performed by polarized light irradiation. Then, after polarized light irradiation, through the process of heating the side chain polymer film, a film (single-layer phase difference film) endowed with optical anisotropy is formed. At this time, the slight anisotropy exhibited by polarized light irradiation becomes a driving force, and the side chain block copolymer itself is effectively reoriented by self-organization. As a result, as a single-layer phase difference film, an efficient orientation treatment can be achieved, and a single-layer phase difference film endowed with high optical anisotropy can be obtained.

[0077] In the present invention, photoreactivity refers to the property of causing any one of (A-1) photocrosslinking (photodimerization) reaction, (A-2) photoisomerization, or (A-3) photoFries rearrangement, or a plurality of reactions.

[0078] The side chain block copolymer is (i) a polymer that exhibits liquid crystallinity within a specified temperature range and has a photoreactive side chain. The side chain block copolymer (ii) can react under light in a wavelength range of 200 to 400 nm, preferably 240 to 400 nm, and exhibits liquid crystallinity within a temperature range of 50 to 300° C. The side chain block copolymer (iii) preferably has a photoreactive side chain that reacts to light in a wavelength range of 200 to 400 nm, preferably 240 to 400 nm, particularly polarized ultraviolet light. In order to exhibit liquid crystallinity within a temperature range of 50 to 300° C., the side chain block copolymer (iv) preferably has a liquid crystal base group.

[0079] As described above, the side chain type block copolymer has a photoreactive side chain with photoreactivity. The structure of the side chain is not particularly limited, preferably having a structure in which the above-mentioned (A-1), (A-2) and / or (A-3) reactions occur, and particularly preferably having a structure in which (A-1) photocrosslinking reaction and / or (A-2) photoisomerization reaction occur. It should be noted that the structure in which (A-1) photocrosslinking reaction occurs is preferably from the aspect that the orientation of the side chain type polymer block can be stably maintained for a long time even if the structure after the reaction is exposed to external stresses such as heat. In addition, the structure in which (A-2) photoisomerization reaction occurs, compared with photocrosslinking and photoFries rearrangement, can be oriented under low exposure, which is preferably from the aspect of improving the production efficiency during the manufacture of the phase difference film.

[0080] It is preferred that the side chain structure of the side chain polymer block has a rigid liquid crystal unit component because the liquid crystal orientation is stable. Examples of the liquid crystal unit component include, but are not limited to, biphenyl, terphenyl, phenylcyclohexyl, and phenyl benzoate.

[0081] As the side chain having a photoreactive site that undergoes photoreaction by ultraviolet light contained in the side chain type polymer block (hereinafter also referred to as side chain a), a side chain represented by any one of the following formulae (a1) to (a6) is preferred. It should be noted that the number of benzene rings possessed by one side chain a is preferably within 3 from the viewpoint of solubility in a solvent.

[0082] [Chemistry 9]

[0083] In formulae (a1) to (a6), n1 and n2 are each independently 0, 1, 2 or 3. L is a single bond or an alkylene group having 1 to 12 carbon atoms, and a part or all of the hydrogen atoms of the alkylene group may be substituted by halogen atoms. 1 A is a single bond or an alkylene group having 1 to 12 carbon atoms, and a part or all of the hydrogen atoms of the alkylene group may be substituted by halogen atoms. 1 , A 2 and D 1 Each is independently a single bond, -O-, -CH2-, -C(=O)-O-, -OC(=O)-, -C(=O)-NH- or -NH-C(=O)-. 1 When A is a single bond, 2 It is also a single bond. 1 and Y 2 is a phenylene group or a naphthylene group, and part or all of the hydrogen atoms of the phenylene group and the naphthylene group may be replaced by a cyano group, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. 1 , Q1 and Q 2 Each independently represents a single bond, a phenylene group or a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, wherein a part or all of the hydrogen atoms of the phenylene group may be replaced by a cyano group, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms. 1 When the number is 2 or more, each Q 1 They can be the same or different; when Q 2 When the number is 2 or more, each Q 2 They may be the same or different. R is a hydrogen atom, a cyano group, a halogen atom, a carboxyl group, an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. 1 and X 2 Each is 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-. 1 When the number is 2 or more, each X 1 They can be the same or different; when X 2 When the number is 2 or more, each X 2 They can be the same or different. 1a and Z 2a Each is independently a hydrogen atom, a halogen atom, a cyano group or an alkyl group having 1 to 3 carbon atoms, and a part or all of the hydrogen atoms of the alkyl group may be replaced by fluorine atoms. Cou is a coumarin-6-yl group or a coumarin-7-yl group, and a part of the hydrogen atoms bonded thereto may be replaced by -NO2, -CN, -CH=C(CN)2, -CH=CH-CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms. E is -C(=O)-O-, -OC(=O)-, -C(=O)-S- or -SC(=O)-. G 1 and G 2 Each is independently N or CH. The dotted line is a bond.

[0084] The alkylene group having 1 to 12 carbon atoms may be any of a linear, branched or cyclic group, and specific examples thereof include methylene, ethylene, 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 and decane-1,10-diyl.

[0085] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0086] The alkyl group having 1 to 5 carbon atoms may be linear or branched, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and n-pentyl.

[0087] Specific examples of the alkylcarbonyl group having 1 to 5 carbon atoms include methylcarbonyl (acetyl) group, ethylcarbonyl group, n-propylcarbonyl group, n-butylcarbonyl group, n-pentylcarbonyl group and the like.

[0088] Specific examples of the alkoxy group having 1 to 5 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and an n-pentoxy group.

[0089] Specific examples of the divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms include a cyclopentanediyl group, a cyclohexanediyl group, a cycloheptanediyl group, and a cyclooctanediyl group.

[0090] Specific examples of the cycloalkyl group having 3 to 7 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0091] The alkyl group having 1 to 3 carbon atoms may be linear or branched, and specific examples thereof include a methyl group, an ethyl group, a n-propyl group, and an isopropyl group.

[0092] As the side chain a, a side chain represented by the following formula (a1-1), (a1-2), (a2-1), (a3-1), (a4-1), (a5-1) or (a6-1) is more preferable.

[0093] [Chemistry 10]

[0094] (In the formula, L, A 1 , A 2 , Y 1 , Y 2 , P 1 , Q 1 , T 1 , R, X 1 , Z 1a , Z 2a , Cou, E, G 1 , G 2 , n1 and the dotted line are the same as above. 2 It is a phenylene group or a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and a part or all of the hydrogen atoms of the phenylene group may be replaced by a cyano group, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.

[0095] The side chain represented by the formula (a1-1) is preferably a side chain represented by the following formula (a1-1-1), and the side chain represented by the formula (a1-2) is preferably O or a side chain represented by the formula (a1-2-1).

[0096] [Chemistry 11]

[0097] (In the formula, n1, L, Q 1 , X 1 , R and dotted line are the same as above. )

[0098] As the side chain represented by the formula (a2-1), a side chain represented by the following formula (a2-1-1) is preferred.

[0099] [Chemistry 12]

[0100] (In the formula, L, A 2 , Q 1 , T 1 , R and dotted line are the same as above. )

[0101] The side chain represented by the formula (a3-1) is preferably a side chain represented by the following formula (a3-1-1), (a3-1-2) or (a3-1-3).

[0102] [Chemistry 13]

[0103] (Wherein, L, Cou and the dotted line are the same as above.)

[0104] The side chain represented by the formula (a4-1) is preferably a side chain represented by the following formula (a4-1-1), (a4-1-2), (a4-1-3) or (a4-1-4).

[0105] [Chemistry 14]

[0106] (Where L, R and the dotted line are the same as above.)

[0107] As the side chain represented by the formula (a5-1), a side chain represented by the following formula (a5-1-1) or (a5-1-2) is preferred.

[0108] [Chemistry 15]

[0109] (Where L, R and the dotted line are the same as above.)

[0110] The side chain represented by the formula (a6-1) is preferably a side chain represented by the following formula (a6-1-1), (a6-1-2) or (a6-1-3).

[0111] [Chemistry 16]

[0112] (Where L, R and the dotted line are the same as above.)

[0113] (A) The side chain type block copolymer has a photosensitive side chain bonded to the main chain of the side chain type polymer block, which can sense the best light selected from the wavelength of 200 to 400 nm, especially the light of 254 nm, 313 nm or 365 nm, to cause a crosslinking reaction, an isomerization reaction or a Fries rearrangement. The structure of the photosensitive side chain type polymer block is not particularly limited as long as it satisfies such characteristics, and preferably has a rigid liquid crystal unit component in the side chain structure. When the side chain type block copolymer is made into a single-layer phase difference film, a stable optical anisotropy can be obtained.

[0114] As a more specific example of the structure of the side chain type polymer block, it is preferably a structure having a main chain and a side chain a composed of at least one free radical polymerizable group selected from (meth)acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene and the like and siloxane.

[0115] The side chain polymer block may further include a side chain that undergoes neither photodimerization nor photoisomerization (hereinafter referred to as side chain b). Such side chain b is preferably a side chain represented by any one of the following formulae (b1) to (b13), but is not limited thereto.

[0116] [Chemistry 17]

[0117] [Chemistry 18]

[0118] [Chemistry 19]

[0119] (In formulas (b1) to (b3), A 3 and A 4 Each is independently a single bond, -O-, -CH2-, -C(=O)-O-, -OC(=O)-, -C(=O)-NH-, or -NH-C(=O)-. 4 When the number is 2 or more, each A 4 They can be the same or different.

[0120] R 1 It is -NO2, -CN, a halogen atom, a phenyl group, a naphthyl group, a biphenyl group, a furyl group, a monovalent nitrogen-containing heterocyclic group, a monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.

[0121] R 2 It is a phenyl group, a naphthyl group, a biphenyl group, a furyl group, a monovalent nitrogen-containing heterocyclic group or a monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and a part or all of the hydrogen atoms in these groups may be replaced by -NO2, -CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms.

[0122] R 3 It is a hydrogen atom, -NO2, -CN, -CH=C(CN)2, -CH=CH-CN, a halogen atom, a phenyl group, a naphthyl group, a biphenyl group, a furyl group, a monovalent nitrogen-containing heterocyclic group, a monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.

[0123] E is -C(=O)-O-, -OC(=O)-, -C(=O)-S- or -SC(=O)-.

[0124] a is an integer from 1 to 12.

[0125] k1 to k5 are each independently an integer of 0 to 2, and the total of k1 to k5 is 2 or more.

[0126] k6 and k7 are each independently an integer of 0 to 2, and the total of k6 and k7 is 1 or more.

[0127] m1, m2 and m3 are each independently an integer of 1-3.

[0128] n is 0 or 1.

[0129] Z 1 and Z 2 Each is independently a single bond, -C(=O)-, -CH2-O-, or -CF2-.

[0130] W 1 , W 2 and W 3 Each is independently a single bond, -O-, -C(=O)-O-, -OC(=O)-, -C(=O)-N(R')- or -N(R')-C(=O)-. 2 When the number is 2 or more, each W 2 They may be the same as or different from each other. R' represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0131] Q is an alkylene group having 1 to 10 carbon atoms. A part or all of the hydrogen atoms in the alkylene group may be substituted with halogen atoms.

[0132] L represents a single bond or an alkylene group having 1 to 12 carbon atoms, or a divalent linking group in which one or more -CH2- constituting the alkylene group having 1 to 12 carbon atoms is replaced by -O-, -S-, -C(=O)-O-, or -OC(=O)-, and a part or all of the hydrogen atoms of the alkylene group may be replaced by halogen atoms.

[0133] Q 1 is a single bond, a phenylene group, a naphthylene group or a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and part or all of the hydrogen atoms of the phenylene group and the naphthylene group may be replaced by a cyano group, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms. 1 When the number is 2 or more, each Q 1 They can be the same or different.

[0134] n1 is 0, 1, 2 or 3.

[0135] The hydrogen atoms on the benzene ring and the naphthalene ring may be replaced by a substituent selected from an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, a halogen atom, a cyano group and a nitro group.

[0136] The dotted lines are bonding bonds.

[0137] Specific examples of the monovalent nitrogen-containing heterocyclic group include pyrrolidinyl, piperidinyl, piperazinyl, pyrrolyl, pyridyl, etc. Specific examples of the monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms include cyclopentyl, cyclohexyl, etc. In addition, the alkyl group and alkoxy group include the same groups as those exemplified in the description of formulas (a1) to (a6).

[0138] The side chain type polymer block can be obtained by polymerizing a monomer that provides a side chain a and, if necessary, a monomer that provides a side chain b.

[0139] Examples of the monomer that supplies the side chain a (hereinafter also referred to as monomer MA) include compounds represented by the following formula (M1), (M2), (M3), (M4), (M5) or (M6).

[0140] [Chemistry 20]

[0141] (wherein, PG is a polymerizable group, A 1 , A 2 , D 1 , L, T1 , Y 1 , Y 2 , P 1 , Q 1 , Q 2 , R, Cou, E, X 1 , X 2 , Z 1a , Z 2a , G 1 , G 2 , n1 and n2 are the same as above. )

[0142] In formulae (M1) to (M6), PG is a polymerizable group, preferably a group represented by any one of the following formulae (PG1) to (PG7). Among them, from the viewpoint of easy control of the polymerization reaction and the stability of the polymer, an acrylic acid group or a methacrylic acid group represented by formula (PG1) is preferred.

[0143] [Chemistry 21]

[0144] (Where R A is a hydrogen atom or a methyl group, and the dotted line is a bond to L. )

[0145] The compound represented by the formula (M1) is preferably a compound represented by the following formula (M1-1-1) or (M1-2-1).

[0146] [Chemistry 22]

[0147] (In the formula, PG, L, Q 1 , X 1 , Y 1 , Z 1a , Z 2a , P 2 and R are the same as above. )

[0148] The compound represented by the formula (M2) is preferably a compound represented by the following formula (M2-1).

[0149] [Chemistry 23]

[0150] (In the formula, PG, A 2 , L, T 1 , Y 1 , Z 1a , Z 2a , P 1 , Q 1 and R are the same as above. )

[0151] The compound represented by the formula (M3) is preferably a compound represented by the following formula (M3-1).

[0152] [Chemistry 24]

[0153] (In the formula, PG, A 1 , L, X 1 , Q 1 , Cou and n1 are the same as above. )

[0154] The compound represented by the formula (M4) is preferably a compound represented by the following formula (M4-1).

[0155] [Chemistry 25]

[0156] (In the formula, PG, A 1 , L, X 1 , Y 1 , Y 2 , Q 1 , E, R and n1 are the same as above. )

[0157] The compound represented by the formula (M5) is preferably a compound represented by the following formula (M5-1).

[0158] [Chemistry 26]

[0159] (In the formula, PG, A 1 , L, X 1 , Y 1 , Y 2 , Q 1 , R and n1 are the same as above. )

[0160] The compound represented by the formula (M6) is preferably a compound represented by the following formula (M6-1).

[0161] [Chemistry 27]

[0162] (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. )

[0163] The compound represented by the formula (M1-1-1) is preferably a compound represented by the following formula (M1-1-2), and the compound represented by the formula (M1-2-1) is preferably a compound represented by the following formula (M1-2-2).

[0164] [Chemistry 28]

[0165] (In the formula, PG, n1, L, Q 1 , X 1 and R are the same as above. )

[0166] The compound represented by the formula (M2-1) is preferably a compound represented by the following formula (M2-2).

[0167] [Chemistry 29]

[0168] (In the formula, PG, A 2 , L, T 1 , Q 1 and R are the same as above. )

[0169] The compound represented by the formula (M3-1) is preferably a compound represented by the following formula (M3-2), (M3-3) or (M3-4).

[0170] [Chemistry 30]

[0171] (Wherein, PG, L and Cou are the same as above.)

[0172] The compound represented by the formula (M4-1) is preferably a compound represented by the following formula (M4-2), (M4-3), (M4-4) or (M4-5).

[0173] [Chemistry 31]

[0174] (In the formula, PG, L and R are the same as above.)

[0175] The compound represented by the formula (M5-1) is preferably a compound represented by the following formula (M5-2) or (M5-3).

[0176] [Chemistry 32]

[0177] (In the formula, PG, L and R are the same as above.)

[0178] The compound represented by the formula (M6-1) is preferably a compound represented by the following formula (M6-2), (M6-3), or (M6-4).

[0179] [Chemistry 33]

[0180] (In the formula, PG, L and R are the same as above.)

[0181] Examples of the compound represented by formula (M1) include compounds 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. 11 is -H, -CH3, -OCH3, -C(CH3)3, -C(=O)-CH3 or -CN, R 12 It is -H, -CH3, -CN or -F.

[0182] [Chemistry 34]

[0183] [Chemistry 35]

[0184] [Chemistry 36]

[0185] [Chemistry 37]

[0186] Examples of the compound represented by formula (M1) include compounds represented by any one of the following formulae (A-1-2-1) to (A-1-2-4). In the following formulae, PG is a polymerizable group, and s1 is the same as described above.

[0187] [Chemistry 38]

[0188] Specific examples of the compound represented by formula (M1) include 4-(6-methacryloyloxyhexyl-1-oxy)cinnamic acid, 4-(6-acryloyloxyhexyl-1-oxy)cinnamic acid, 4-(3-methacryloyloxypropyl-1-oxy)cinnamic acid, and 4-[4-(6-methacryloyloxyhexyl-1-oxy)benzoyloxy]cinnamic acid.

[0189] Examples of the compound represented by formula (M2) include compounds 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, and s1 and s2 represent the number of methylene groups, each independently being an integer of 2 to 9. 21 It is -CH3, -OCH3, -C(CH3)3, -C(=O)-CH3, -CN or -F.

[0190] [Chemistry 39]

[0191] [Chemistry 40]

[0192] [Chemistry 41]

[0193] Examples of the compound represented by formula (M3) include compounds represented by any one of the following formulae (A-3-1) to (A-3-5). In the following formulae, PG is a polymerizable group, and s1 is the same as described above.

[0194] [Chemistry 42]

[0195] Examples of the compound represented by formula (M4) include compounds represented by any one of the following formulae (A-4-1) to (A-4-4). In the following formulae, PG is a polymerizable group, and s1 is the same as described above.

[0196] [Chemistry 43]

[0197] Examples of the compound represented by formula (M5) include compounds represented by any one of the following formulae (A-5-1) to (A-5-3). In the following formulae, PG is a polymerizable group, and s1 is the same as described above.

[0198] [Chemistry 44]

[0199] Examples of the compound represented by formula (M6) include compounds represented by any one of the following formulae (A-6-1) to (A-6-3). In the following formulae, PG is a polymerizable group, and s1 is the same as described above.

[0200] [Chemistry 45]

[0201] Some of the monomers are commercially available, and some can be produced by the method described in, for example, International Publication No. 2015 / 002292.

[0202] An example of a monomer that provides a side chain b that undergoes neither photodimerization nor photoisomerization (hereinafter, also referred to as a monomer MB) is a monomer that can form a mesogen group on a side chain.

[0203] The liquid crystal unit group may be a group that forms a liquid crystal unit structure independently, such as biphenyl or phenyl benzoate, or a group that forms a liquid crystal unit structure by hydrogen bonding such as benzoic acid. The liquid crystal unit group having a side chain preferably has the following structure.

[0204] [Chemistry 46]

[0205] As a specific example of the monomer MB, the following structure is preferred, wherein the structure has a polymerizable group derived from at least one of free radical polymerizable groups selected from hydrocarbons, (meth)acrylates, itaconates, fumarates, maleates, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene, and siloxane, and at least one of the structures of formulae (b1) to (b13). It is particularly preferred that the monomer MB has a polymerizable group derived from a (meth)acrylate.

[0206] Preferred examples of the monomer MB include monomers represented by the following formulae (MB-1) to (MB-18). In the following formulae, PG is a polymerizable group, and p represents the number of methylene groups, which is an integer of 2 to 9.

[0207] [Chemistry 47]

[0208] [Chemistry 48]

[0209] In addition, other monomers can be copolymerized within the range that does not impair the performance of photoreactivity and / or liquid crystal properties. Examples of the other monomers include monomers that are industrially available and capable of free radical polymerization. Specific examples of the other monomers include unsaturated carboxylic acids, acrylate compounds, methacrylate compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds, vinyl compounds, and the like.

[0210] Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid.

[0211] Specific examples of the acrylate compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthracene acrylate, anthracene methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclo[5.2.1.0(2,6)]decyl acrylate, and 8-ethyl-8-tricyclo[5.2.1.0(2,6)]decyl acrylate.

[0212] Specific examples of the methacrylate compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthracene methacrylate, anthracene methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclo[5.2.1.0(2,6)]decyl methacrylate, and 8-ethyl-8-tricyclo[5.2.1.0(2,6)]decyl methacrylate.

[0213] Specific 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.

[0214] Specific examples of the styrene compound include styrene, 4-methylstyrene, 4-chlorostyrene, 4-bromostyrene, and the like.

[0215] Specific examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

[0216] In the side chain polymer block, the content of side chain a and side chain b is not particularly limited. Side chain a can be a homopolymer of 100 mol%, or two or more side chains a can be used. In the case of a copolymer of side chain a and side chain b, from the perspective of photoreactivity, side chain a is preferably 5 to 99.9 mol%, more preferably 5 to 95 mol%, and from the perspective of photostability, it is further preferably 5 to 50 mol%. In addition, from the perspective of photoreactivity, side chain b is preferably 95 mol% or less, more preferably 5 to 95 mol%, and from the perspective of photostability, it is further preferably 50 mol% or more. In the case of a copolymer, two or more side chains a and side chains b can also be used.

[0217] The side chain type polymer block may contain other side chains. When the total content of the side chain a and the side chain b is less than 100 mol %, the content of the other side chains is the remainder.

[0218] The polymer block (A2) containing repeating units not containing photo-oriented side chains and liquid crystal side chains is a block that imparts flexibility to the polymer as (A) component. As such a polymer block (A2) containing repeating units not containing photo-oriented side chains and liquid crystal side chains, it is preferably a block with flexibility, for example, polyethers and polysiloxanes can be cited. It is simple to introduce the polymer block (A2) containing repeating units not containing photo-oriented side chains and liquid crystal side chains through a polymer-type polymerization initiator. In the present invention, a polymer-type polymerization initiator refers to a polymerization initiator having a polymer segment and a polymerization initiation active group. It should be noted that the polymer segment is a part of a polymer segment containing repeating units not containing photo-oriented side chains and liquid crystal side chains in a side chain block copolymer.

[0219] The polymeric polymerization initiator preferably has a repeating unit represented by the following formula (1).

[0220] [Chemistry 49]

[0221] In formula (1), R a1 ~R a4 Each R is independently a linear or branched alkyl group having 1 to 6 carbon atoms, or a cyano group. L1 and R L2 Each independently represents an alkylene group having 1 to 10 carbon atoms. 1 and L 2 Each independently represents -C(=O)-O-, -OC(=O)-, -C(=O)-NH- or -NH-C(=O)-. X represents a divalent group represented by the following formula (2) or (3).

[0222] [Chemistry 50]

[0223] In formulas (2) and (3), R a5 ~R a8 It is a linear or branched alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms. L3 , R L4 , R L5 and R L6 Each independently represents an alkylene group having 1 to 10 carbon atoms. x and y each independently represent a positive integer, and are usually 5 to 2000, preferably 5 to 1000, more preferably 10 to 300, and further preferably 10 to 200.

[0224] Examples of the linear or branched alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, cyclopentyl and cyclohexyl.

[0225] The alkylene group having 1 to 10 carbon atoms may be any of a linear, branched or cyclic group, and specific examples include a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a pentamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, a 2-methylpropylene group, a 1-methylethylene group, and a cyclohexylene group.

[0226] Examples of the aryl group having 6 to 12 carbon atoms include phenyl, 1-naphthyl, 2-naphthyl, 1-biphenylyl, and 2-biphenylyl.

[0227] R a1 ~R a4 It is preferably an alkyl group having 1 to 3 carbon atoms or a cyano group, and more preferably a methyl group or a cyano group.

[0228] R L1 and R L2 An alkylene group having 1 to 5 carbon atoms is preferred, and an alkylene group having 1 to 3 carbon atoms is more preferred.

[0229] L 1 Preferably it is -C(=O)-O- or -C(=O)-NH-. 2 It is preferably -OC(=O)- or -NH-C(=O)-. In particular, L is more preferably 1 -C(=O)-O-, L 2 is a combination of -OC(=O)-, and L 1 -C(=O)-NH-, L 2 It is a combination of -NH-C(=O)-.

[0230] About X, R a5 ~Ra8 An alkyl group having 1 to 3 carbon atoms is preferred, and a methyl group or an ethyl group is more preferred.

[0231] R L3 , R L4 , R L5 and R L6 An alkylene group having 1 to 5 carbon atoms is preferred, and an alkylene group having 1 to 3 carbon atoms is more preferred.

[0232] Specific examples of the polymeric polymerization initiator include a polymer azo polymerization initiator containing a polyethylene glycol unit represented by the following formula (In-1) and a polymer azo polymerization initiator containing a polydimethylsiloxane unit represented by the following formula (In-2).

[0233] [Chemistry 51]

[0234] In formula (In-1) and formula (In-2), x and y are the same as described above. n is a positive integer and is usually 1 to 100, preferably 3 to 50, and more preferably 5 to 30.

[0235] As the polymer-type polymerization initiator, commercially available products can be used, for example, VPE-0201 as the polymerization initiator represented by the above formula (In-1) and VPS-1001N as the polymerization initiator represented by the above formula (In-2) ​​(both manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).

[0236] In addition, the polymer block (A2) containing repeating units not containing photo-oriented side chains and liquid crystal side chains can also be introduced by a polymeric chain transfer agent. In the present invention, a polymeric chain transfer agent refers to a chain transfer agent having a site and a polymer segment that generates new free radicals by accepting free radicals from a growing polymer chain. It should be noted that the polymer segment is a portion of a polymer block containing repeating units not containing photo-oriented side chains and liquid crystal side chains in a side chain block copolymer.

[0237] As the polymeric chain transfer agent, a polymeric chain transfer agent represented by the following formula (4) is preferred.

[0238] [Chemistry 52]

[0239] In formula (4), Y is a linear or branched alkyl group having 1 to 3 carbon atoms, a hydroxyl group, a carboxyl group, or a mercapto group. L7 and R L8 Each is independently a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms. x is a positive integer.

[0240] In addition, the polymer block (A2) comprising the repeating unit not containing light-oriented side chain and liquid crystal side chain can also be introduced by a monomer without light-oriented side chain and liquid crystal side chain. After synthesizing the side chain polymer block (A1), the monomer without light-oriented side chain and liquid crystal side chain is added for polymerization, so that the side chain block copolymer comprising each block can be obtained. The polymerization method is not particularly limited, and the active radical polymerization (NMP) using nitroxide as dormant species, the reversible addition-fragmentation chain transfer (RAFT) polymerization using sulfur compounds as dormant species, the active radical polymerization such as reversible transfer catalysis polymerization (RTCP) using alkyl iodide compounds as dormant species, phosphorus compounds, alcohols, etc. as catalysts can be cited.

[0241] The method for producing the side chain type block copolymer is not particularly limited, and a general method for industrial processing can be used. Specifically, for example, the side chain type block copolymer can be produced by a method including the following steps (1) to (2), but the present invention is not limited thereto.

[0242] Step (1): a step of mixing monomer MA, monomer MB as required, other monomers, and a non-polymeric polymerization initiator, and performing free radical polymerization in a solvent to form a side chain polymer block (A1);

[0243] Step (2): A step of adding a polymeric polymerization initiator to the reaction solution obtained in the above step (1) and performing radical polymerization in a solvent to introduce a polymer block (A2) including a repeating unit having no photo-alignment side chain and no liquid crystal side chain.

[0244] As the non-polymer type polymerization initiator for the radical polymerization in the step (1), known compounds such as the following free radical thermal polymerization initiator, free radical photopolymerization initiator, and reversible addition-fragmentation chain transfer (RAFT) polymerization agent can be used.

[0245] The free radical thermal polymerization initiator is a compound that generates free radicals by heating to a decomposition temperature or higher. Examples of such free radical thermal polymerization initiators include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), hydroperoxides (hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketals (dibutyl cyclohexane peroxide, etc.), alkyl peresters (tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate, tert-amyl peroxy-2-ethylcyclohexane acid, etc.), persulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), and azo compounds (2,2′-azobisisobutyronitrile and 2,2′-bis(2-hydroxyethyl)azobisisobutyronitrile, etc.). Such radical thermal polymerization initiators may be used alone or in combination of two or more.

[0246] The free radical photopolymerization initiator is not particularly limited as long as it is a compound that initiates free radical polymerization by light irradiation. Examples of such free radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, isopropyl xanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-one, and 1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one. 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid isopentyl ester, 4,4'-bis(tert-butylperoxycarbonyl)benzophenone, 3,4,4'-tris(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-(4'-methoxyphenylvinyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxyphenylvinyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2',4'-dimethoxyphenylvinyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2'-methoxyphenylvinyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'- 1,3-bis(trichloromethyl)-5-(2′-chlorophenyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(4′-methoxyphenyl)-s-triazine, 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)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′-tetraphenyl-1,2′-biimidazole, 5,5′-Tetrakis(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-dimethylaminopropionyl)carbazole, 3,6-bis(2-methyl-2-morpholinopropionyl)-9-n-dodecylcarbazole, 1-hydroxycyclohexyl phenyl ketone, bis(5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, 3,3′,4,4′-tetra(tert-butylperoxycarbonyl)benzophenone, 3,3′,4,4′-tetra(tert-hexylperoxycarbonyl)benzophenone, 3,3′-bis(methoxycarbonyl)-4,4′-bis(tert-butylperoxycarbonyl)benzophenone, 3,4′-bis(methoxycarbonyl)-4,3′-bis(tert-butylperoxycarbonyl)benzophenone, 4,4′-bis(methoxycarbonyl)-3,3′-bis(tert-butylperoxycarbonyl)benzophenone, 2-(3-methyl-3H-benzothiazol-2-ylidene)-1-naphth-2-yl-ethanone, or 2-(3-methyl-1,3-benzothiazol-2(3H)-ylidene)-1-(2-benzoyl)ethanone, etc. These compounds may be used alone or in combination of two or more.

[0247] The radical polymerization method is not particularly limited, and emulsion polymerization, suspension polymerization, dispersion polymerization, precipitation polymerization, bulk polymerization, solution polymerization, and the like can be used.

[0248] The organic solvent used in the polymerization reaction is not particularly limited as long as it is an organic solvent that dissolves the generated polymer. Specific examples thereof include: N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methyl-ε-caprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethylphosphoric triamide, γ-butyrolactone, γ-valerolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl solvent, and the like. Cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol tert-butyl ether, dipropylene glycol monomethyl 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 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, methyl cyclohexene, propyl ether, dihexyl ether, 1,4-dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, cyclopentanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, ethyl acetate 3-methoxypropionic acid propyl ester, 3-methoxypropionic acid butyl ester, diethylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N,N-dimethylpropionamide, 3-ethoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, etc. These organic solvents may be used alone or in combination of two or more.

[0249] Furthermore, even a solvent that does not dissolve the produced polymer may be used by mixing with the above-mentioned organic solvent as long as the produced polymer does not precipitate.

[0250] In addition, in radical polymerization, oxygen in the organic solvent becomes a cause of inhibiting the polymerization reaction, and therefore, it is preferable to use an organic solvent that is degassed as much as possible.

[0251] The polymerization temperature during free radical polymerization can be selected from any temperature in the range of 20 to 150° C., preferably in the range of 30 to 100° C. In addition, the reaction can be carried out at any concentration. If the concentration is too low, it is difficult to obtain a high molecular weight polymer. If the concentration is too high, the viscosity of the reaction solution becomes too high, and uniform stirring becomes difficult. Therefore, the monomer concentration is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass. The reaction can be carried out at a high concentration at the beginning, and then an organic solvent can be added.

[0252] In the free radical polymerization reaction in the step (1), if the ratio of the free radical polymerization initiator is large relative to the monomer, the molecular weight of the obtained polymer becomes small, and if the ratio of the free radical polymerization initiator is small relative to the monomer, the molecular weight of the obtained polymer becomes large, so the ratio of the free radical initiator is preferably 0.1 to 15 mol% relative to the monomer to be polymerized. In addition, various monomer components, solvents, initiators, etc. can also be added during polymerization.

[0253] In the free radical polymerization reaction in the step (2), the amount of the polymeric polymerization initiator used is preferably 0.01 to 0.2 in terms of molar ratio relative to the total amount of monomers supplied to the side chain polymer block, taking into account the half-life of the polymeric polymerization initiator, in order to facilitate the free radical polymerization. In addition, various monomer components, solvents, initiators, etc. may also be added during the polymerization.

[0254] The side chain block copolymer generated by the reaction solution obtained by the reaction can be put into a poor solvent to precipitate and recover, but the reprecipitation treatment is not necessary. As the poor solvent used in the precipitation, there can be mentioned: methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, water, etc. The polymer put into the poor solvent and precipitated can be filtered and recovered, and then dried at room temperature or heated under normal pressure or reduced pressure. In addition, if the operation of redissolving the recovered polymer in an organic solvent and reprecipitating and recovering is repeated 2 to 10 times, the impurities in the polymer can be reduced. As the poor solvent at this time, for example, alcohols, ketones, hydrocarbons, etc. can be mentioned. If more than 3 poor solvents selected from them are used, the efficiency of purification is further improved, so it is preferred.

[0255] The ratio (molar ratio) of the side chain type polymer block to the polymer block derived from the initiator in the side chain type block copolymer is generally determined by the total amount of monomers supplied to the side chain type polymer block and the amount of the polymer type polymerization initiator used.

[0256] The weight average molecular weight (Mw) of the photosensitivity side chain polymer block (A1) capable of expressing liquid crystallinity is preferably 5000 to 300000. The number average molecular weight (Mn) of the polymer block (A2) including repeating units having no photo-alignment side chain and liquid crystal side chain is preferably 200 to 10000.

[0257] Considering the strength of the obtained coating film, the workability during coating film formation, and the uniformity of the coating film, the weight average molecular weight (Mw) of the side chain type block copolymer used in the present invention is preferably 5200 to 310000, more preferably 5500 to 250000, and further preferably 6000 to 200000. It should be noted that in the present invention, Mn and Mw are polystyrene conversion measurement values ​​based on gel permeation chromatography (GPC) method.

[0258] [(B) Organic solvent]

[0259] The polymer composition of the present invention contains an organic solvent (good solvent). The organic solvent (good solvent) is not particularly limited as long as it is an organic solvent that dissolves the polymer component. Specific examples thereof include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methyl-ε-caprolactam, 2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethylphosphoramide, γ-butyrolactone, 3-methoxy-N,N-dimethylpropionamide, 3-ethoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, 1,3-dimethyl-2-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, cyclopentanone, ethylene carbonate, propylene carbonate, diethylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, tetrahydrofuran, and tetrahydrofurfuryl alcohol. These organic solvents may be used alone or in combination of two or more.

[0260] In addition, the polymer composition may include components other than the side chain block copolymer and the organic solvent (good solvent). As examples thereof, solvents (poor solvents), compounds that improve the uniformity of film thickness and surface smoothness when the polymer composition is applied, compounds that improve the adhesion of the phase difference film to the substrate, etc., can be cited, but are not limited to these.

[0261] Specific examples of the solvent (poor solvent) for improving the uniformity of the film thickness and the surface smoothness include isopropyl alcohol, methoxymethylpentyl alcohol, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether (butyl cellosolve), propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether ...ethylene glycol monoacetate, ethylene glycol monomethyl ether, ethylene glycol monoacetate, ethylene glycol monomethyl ether, ethylene glycol monoacetate, ethylene glycol monomethyl ether, ethylene glycol monoacetate, ethylene glycol monomethyl ether, ethylene glycol monoacetate, ethylene glycol monomethyl ether, ethylene glycol monoacetate, ethylene glycol monoacetate, ethylene glycol monomethyl ether, ethylene glycol monoacetate, ethylene glycol monoacetate, ethylene glycol monoacetate, ethylene glycol monoacetate, ethylene glycol monoacetate, ethylene glycol monoacetate, ethylene glycol monoacetate, ethylene glycol monoacetate, ethylene glycol monoacetate, ethylene glycol monoacetate, ethylene glycol monoacetate, ethylene glycol monoacetate, ethylene glycol monoace Ether, propylene glycol tert-butyl ether, dipropylene glycol monomethyl 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 monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutyl olefins, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methyl cyclohexene, propyl ether, dihexyl ether, 1-hexanol, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isopentyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-methoxypropionic acid Solvents having low surface tension include ethyl ester, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol, and 2-(2-ethoxypropoxy)propanol.

[0262] The poor solvent may be used alone or in combination of two or more. When a poor solvent is used, its content is preferably 5 to 80% by mass, more preferably 10 to 60% by mass in the solvent so as not to significantly reduce the solubility of the polymer.

[0263] As compounds for improving the uniformity of the film thickness and the surface smoothness, fluorine-based surfactants, silicone-based surfactants, nonionic surfactants, etc. can be cited. As specific examples thereof, EFTOP (registered trademark) 301, EF303, EF352 (manufactured by Tohkem Products Co., Ltd.), MEGAFACE (registered trademark) F-171, F-173, F-563, R-30, R-40 (manufactured by DIC Co., Ltd.), Fluorad FC430, FC431 (manufactured by 3M Co., Ltd.), AsahiGuard (registered trademark) AG710 (manufactured by AGC Co., Ltd.), SURFLON (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimei Chemical Co., Ltd.), etc. can be cited. The content of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, based on 100 parts by mass of the side chain type block copolymer.

[0264] Specific examples of compounds that improve the adhesion between the phase difference film and the substrate include compounds containing functional silanes, and specific examples thereof include: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilane Propyl triethylenetriamine, N-trimethoxysilylpropyl triethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyl trimethoxysilane, N-benzyl-3-aminopropyl triethoxysilane, N-phenyl-3-aminopropyl trimethoxysilane, N-phenyl-3-aminopropyl triethoxysilane, N-di(ethylene oxide)-3-aminopropyl trimethoxysilane, N-di(ethylene oxide)-3-aminopropyl triethoxysilane, and the like.

[0265] The polymer composition may contain a phenoplast compound or an epoxy group-containing compound in order to improve the adhesion between the substrate and the retardation film and prevent the degradation of the characteristics due to the backlight when constituting a polarizing plate.

[0266] Specific examples of the phenolic plastic compound include the following compounds, but are not limited to these.

[0267] [Chemistry 53]

[0268] Specific examples of the epoxy group-containing compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N′,N′-tetraglycidyl-m-xylene diamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, and N,N,N′,N′-tetraglycidyl-4,4′-diaminodiphenylmethane.

[0269] When using a compound that improves adhesion to a substrate, the content is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the side chain type block copolymer contained in the polymer composition. If the content 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, there is a situation where the orientation of the liquid crystal deteriorates.

[0270] As an additive, a photosensitizer can also be used. As the photosensitizer, a colorless sensitizer and a triplet sensitizer are preferred.

[0271] Examples of the photosensitizer include aromatic nitro compounds, coumarins (7-diethylamino-4-methylcoumarin, 7-hydroxy-4-methylcoumarin), ketocoumarins, carbonyl dicoumarins, aromatic 2-hydroxyketones, aromatic 2-hydroxyketones (2-hydroxybenzophenone, mono-p-(dimethylamino)-2-hydroxybenzophenone or di-p-(dimethylamino)-2-hydroxybenzophenone, etc.), acetophenones, anthraquinones, xanthone, thioxanthone, benzanthrone, thiazolines (2-benzoylmethylene- 3-methyl-β-naphthothiazoline, 2-(β-naphthoylmethylene)-3-methylbenzothiazoline, 2-(α-naphthoylmethylene)-3-methylbenzothiazoline, 2-(4-biphenylylmethylene)-3-methylbenzothiazoline, 2-(β-naphthoylmethylene)-3-methyl-β-naphthothiazoline, 2-(4-biphenylylmethylene)-3-methyl-β-naphthothiazoline, 2-(p-fluorobenzoylmethylene)-3-methyl-β-naphthothiazoline, etc.), oxadiazole oxazoline (2-benzoylmethylene-3-methyl-β-naphthooxazoline, 2-(β-naphthoylmethylene)-3-methylbenzoxazoline, 2-(α-naphthoylmethylene)-3-methylbenzoxazoline, 2-(4-biphenylmethylene)-3-methylbenzoxazoline, 2-(β-naphthoylmethylene)-3-methyl-β-naphthooxazoline, 2-(4-biphenylmethylene)-3-methyl-β-naphthooxazoline, 2-(p-fluorobenzoylmethylene)-3-methyl

[0043] The present invention relates to an alkyl benzoate, ...

[0272] In addition to the above-mentioned substances, the polymer composition may contain dielectrics and conductive substances in order to change the electrical properties such as the dielectric constant and conductivity of the phase difference film, as long as the effects of the present invention are not impaired. In addition, a cross-linking compound may be added to increase the hardness and density of the film when the phase difference film is made.

[0273] The polymer composition is preferably prepared as a coating liquid in a manner suitable for forming a monolayer phase difference film. That is, the polymer composition used in the present invention is preferably prepared in the form of a solution, wherein the solution is a solution in which the side chain block copolymer and the above-mentioned compound for improving film thickness uniformity and surface smoothness, and the compound for improving adhesion to the substrate are dissolved in an organic solvent (good solvent).

[0274] In the polymer composition, the content of the side chain type block copolymer is preferably 1 to 30% by mass, and more preferably 3 to 25% by mass.

[0275] It should be noted that the polymer composition may also include other polymers in addition to the side chain block copolymer without damaging the liquid crystal performance and photosensitivity. As the other polymers, for example, there can be mentioned: polymers such as poly (meth) acrylates, polyamic acids, polyimides, etc. that do not contain side chains that can show liquid crystal sensitivity. In the case of including the other polymers, the content thereof is preferably 0.5 to 80% by mass, and more preferably 1 to 50% by mass in all polymer components.

[0276] In the polymer composition of the present invention, in addition to the above-mentioned substances, dielectrics and conductive substances may be added to change the electrical properties such as the dielectric constant and conductivity of the phase difference material within the range that does not impair the effects of the present invention. In addition, cross-linking compounds may be added to increase the hardness and density of the film when the phase difference material is made.

[0277] [Preparation of polymer composition]

[0278] The polymer composition of the present invention is preferably prepared as a coating liquid in a manner suitable for the formation of a monolayer phase difference material. That is, the polymer composition used in the present invention is preferably prepared as a solution in which the component (A) and the above-mentioned solvent or compound for improving film thickness uniformity and surface smoothness, and the compound for improving the adhesion between the liquid crystal alignment film and the substrate are dissolved in the organic solvent of the component (B). Here, the content of the component (A) is preferably 1 to 30% by mass, more preferably 3 to 25% by mass in the polymer composition of the present invention.

[0279] [Single-layer phase difference material]

[0280] The single-layer retardation material of the present invention can be produced by a method including the following steps (I) to (III).

[0281] (I) a step of applying the polymer composition of the present invention onto a substrate to form a coating film;

[0282] (II) irradiating the coating film with polarized ultraviolet rays; and

[0283] (III) A step of heating the coating film irradiated with ultraviolet rays to obtain a phase difference material.

[0284] [Step (I)]

[0285] Step (I) is a step of applying the polymer composition of the present invention on a substrate to form a coating film. More specifically, the polymer composition of the present invention is applied on a substrate (e.g., a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a glass substrate coated with a metal (e.g., aluminum, molybdenum, chromium, etc.), a glass substrate, a quartz substrate, an ITO substrate, etc.), a film (e.g., a resin film such as a triacetylcellulose (TAC) film, a cycloolefin polymer film, a polyethylene terephthalate film, an acrylic film, etc.) by a method such as rod coating, spin coating, flow coating, roller coating, slit coating, slit coating followed by spin coating, inkjet method, printing method, etc. After coating, the solvent can be evaporated at 50 to 200° C., preferably 50 to 150° C. by heating means such as a hot plate, a hot air circulation oven, an IR (infrared) oven, etc. to obtain a coating film.

[0286] [Step (II)]

[0287] In step (II), the coating obtained in step (I) is irradiated with polarized ultraviolet rays. When the film surface of the coating is irradiated with polarized ultraviolet rays, the substrate is irradiated with polarized ultraviolet rays from a specific direction through a polarizing plate. As the above-mentioned ultraviolet rays, ultraviolet rays with a wavelength range of 100 to 400 nm can be used. It is preferred to select the optimal wavelength through a filter or the like according to the type of coating used. Then, for example, in order to selectively induce a photocrosslinking reaction, ultraviolet rays with a wavelength range of 290 to 400 nm can be selected. As ultraviolet rays, for example, light radiated from a high-pressure mercury lamp can be used.

[0288] The irradiation amount of polarized ultraviolet rays depends on the coating film used. The irradiation amount is preferably set to be within the range of 1 to 70% of the amount of polarized ultraviolet rays that achieves the maximum value of ΔA, which is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet rays in the coating film and the ultraviolet absorbance in the direction perpendicular to the polarization direction of the polarized ultraviolet rays, and more preferably within the range of 1 to 50%.

[0289] [Step (III)]

[0290] In step (III), the coating film irradiated with polarized ultraviolet rays in step (II) is heated. Heating can impart orientation control capability to the coating film.

[0291] The heating can be performed by using a heating means such as a hot plate, a hot air circulation type oven, an IR (infrared) type oven, etc. The heating temperature can be determined in consideration of the temperature at which the coating film to be used exhibits liquid crystallinity.

[0292] The heating temperature is preferably within the temperature range at which the polymer of the component (A) contained in the polymer composition of the present invention exhibits liquid crystallinity (hereinafter referred to as the liquid crystal manifestation temperature). In the case of a thin film surface such as a coating, it is expected that the liquid crystal manifestation temperature of the coating surface is lower than the liquid crystal manifestation temperature when the polymer of the component (A) is observed as a body. Therefore, the heating temperature is more preferably within the temperature range of the liquid crystal manifestation temperature of the coating surface. That is, the temperature range of the heating temperature after polarized ultraviolet irradiation is preferably a temperature range with a lower limit of 10°C lower than the lower limit of the temperature range of the liquid crystal manifestation temperature of the polymer of the component (A) as the lower limit and a temperature range with an upper limit of 10°C lower than the upper limit of the liquid crystal temperature range. If the heating temperature is lower than the temperature range, there is a tendency that the anisotropic enhancement effect generated by heat in the coating becomes insufficient. In addition, if the heating temperature is too high compared to the temperature range, there is a tendency that the state of the coating is close to an isotropic liquid state (isotropic phase), in which case it is sometimes difficult to reorient in one direction by self-organization.

[0293] It should be noted that the liquid crystal display temperature refers to a temperature above the liquid crystal transition temperature at which a phase transition occurs from a solid phase to a liquid crystal phase on the surface of a polymer or coating film, and below the isotropic phase transition temperature (Tiso) at which a phase transition occurs from a liquid crystal phase to an isotropic phase. For example, the liquid crystal property is displayed below 130°C, which means that the liquid crystal transition temperature at which a phase transition occurs from a solid phase to a liquid crystal phase is below 130°C.

[0294] The thickness of the coating film formed after heating can be appropriately selected in consideration of the height difference, optical properties, and electrical properties of the substrate to be used, and is preferably 0.5 to 10 μm, for example.

[0295] The single-layer retardation material of the present invention thus obtained has optical properties suitable for use in display devices, recording materials, and the like, and is particularly suitable as an optical compensation film such as a polarizing plate and a retardation plate for a liquid crystal display.

[0296] Example

[0297] Hereinafter, the present invention will be described in more detail with reference to synthesis examples, preparation examples, examples and comparative examples, but the present invention is not limited to the following examples.

[0298] The monomers MA-1 and MA-8 having photoreactive groups and the monomers MA-2 to MA-7 having non-photosensitive groups used in the examples are shown below. It should be noted that the side chains derived from MA-1 and MA-8 exhibit photoreactivity and liquid crystallinity, while the side chains derived from MA-2 to MA-7 exhibit only liquid crystallinity.

[0299] [Chemistry 54]

[0300] In addition, the abbreviations of the reagents used in this example are shown below.

[0301] (Organic Solvent)

[0302] NMP: N-methyl-2-pyrrolidone

[0303] BCS: Butyl Cellosolve

[0304] PGME: 1-methoxy-2-propanol

[0305] PGMEA: Propylene glycol monomethyl ether acetate

[0306] CPN: Cyclopentanone

[0307] (Polymerization initiator)

[0308] AIBN: 2,2′-azobisisobutyronitrile

[0309] VPE: A high molecular weight azo polymerization initiator represented by the above formula (In-1) and containing a polyethylene glycol unit (VPE-0201 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., molecular weight of the polyethylene glycol unit: about 2000)

[0310] (Surfactant)

[0311] F563: Megaface F-563 (manufactured by DIC Corporation)

[0312] R40: Megaface R-40 (manufactured by DIC Corporation)

[0313] (Determination of Molecular Weight)

[0314] The molecular weight of the polymer was measured as follows using a room temperature gel permeation chromatography (GPC) apparatus (CBM-20A) (manufactured by Shimadzu Corporation) and a column (Shodex (registered trademark) KF-804L and KF-803L connected in series) (manufactured by Showa Denko K.K.).

[0315] Column temperature: 40°C

[0316] Eluent: Tetrahydrofuran

[0317] Flow rate: 1.0mL / min

[0318] Standard sample for preparing calibration curve: Standard polystyrene (molecular weight: 197000, 55100, 12800, 3950, 1260) (manufactured by Tosoh Corporation)

[0319] [1] Synthesis of polymers

[0320] <Synthesis example 1>

[0321] M-1 (3.79 g, 11.4 mmol), M-2 (2.33 g, 7.60 mmol), M-3 (4.23 g, 15.2 mmol), M-4 (1.45 g, 3.80 mmol) and AIBN (0.62 g, 3.80 mmol) were dissolved in NMP (22.4 g) to prepare a monomer mixed solution. In addition, VPE (0.62 g) was dissolved in NMP (1.86 g) to prepare an additional addition solution. Under a nitrogen atmosphere, the monomer mixed solution was added dropwise to NMP (14.9 g) heated to 70°C for 2 hours. After the addition was completed, the mixture was reacted at 70°C for 3 hours to obtain a solution of a polymer (weight average molecular weight Mw: 45700) corresponding to the side chain polymer block (A1). Furthermore, the additional addition solution was added dropwise to the above solution at 80°C for 60 minutes under a nitrogen atmosphere. After the dropwise addition, the mixture was reacted at 80°C for 12 hours. After the reaction, the reaction solution was added to methanol (300 g), and the generated precipitate was separated by filtration. The filtrate was washed with methanol and dried under reduced pressure at 40°C to obtain polymer powder P-1.

[0322] <Synthesis Examples 2 to 8>

[0323] As shown in Table 1 below, polymer powders P-2 to P-8 were obtained by carrying out the same operation as in Synthesis Example 1 except that the types and amounts of the monomers used and the amount of the polymerization initiator VPE were changed.

[0324] <Synthesis Example 9>

[0325] M-1 (3.79 g, 11.4 mmol), M-2 (2.33 g, 7.60 mmol), M-3 (4.23 g, 15.2 mmol), M-4 (1.45 g, 3.80 mmol) and AIBN (0.62 g, 3.80 mmol) were dissolved in NMP (22.4 g) to prepare a monomer mixed solution. Under a nitrogen atmosphere, the monomer mixed solution was added dropwise to NMP (14.9 g) heated to 70°C for 2 hours. After the addition was completed, the reaction was carried out at 70°C for 12 hours. After the reaction was completed, the reaction solution was added to a mixed solution of methanol (250 g) and pure water (50 g), and the generated precipitate was separated by filtration. The filtrate was washed with methanol and dried under reduced pressure at 40°C to obtain polymer powder P-9.

[0326] <Synthesis Example 10>

[0327] As shown in Table 1 below, the same operation as in Synthesis Example 9 was carried out except that the types and amounts of the monomers used were changed, thereby obtaining a polymer powder P-10.

[0328] <Synthesis Example 11>

[0329] M-1 (1.99 g, 6.00 mmol), M-2 (10.4 g, 34.0 mmol) and AIBN (0.66 g, 4.00 mmol) were dissolved in NMP (18.3 g) to prepare a monomer mixed solution. Under a nitrogen atmosphere, the monomer mixed solution was added dropwise to NMP (9.5 g) heated to 70°C for 2 hours. After the addition was completed, the mixture was reacted at 70°C for 12 hours. After the reaction was completed, the solution was returned to room temperature to obtain a polymer solution P-11.

[0330] <Synthesis Example 12>

[0331] M-1 (1.99 g, 6.00 mmol), M-2 (10.4 g, 34.0 mmol) and VPE (8.0 g) were dissolved in NMP (38.1 g) to prepare a monomer mixed solution. Under a nitrogen atmosphere, the monomer mixed solution was added dropwise to NMP (9.5 g) heated to 80°C over a period of 1.5 hours. After the addition was completed, the mixture was reacted at 80°C for 20 hours. After the reaction was completed, the solution was returned to room temperature to obtain a polymer solution P-12.

[0332] [Table 1]

[0333] [2] Preparation of materials for forming phase difference films

[0334] <Preparation Example 1>

[0335] NMP (1.0 g), BCS (1.0 g), PGME (3.5 g), PGMEA (2.7 g) and F563 (9.0 mg) were added to the polymer powder P-1 (1.8 g) obtained in Synthesis Example 1 and stirred. The mixture was filtered using a filter with a pore size of 5.0 μm to obtain a polymer preparation liquid T-1. The polymer preparation liquid T-1 was directly used as a material for forming a phase difference film.

[0336] <Preparation Examples 2 to 10>

[0337] As shown in Table 2 below, the same operation as in Preparation Example 1 was carried out except that the type and amount of the polymer powder and the amount of the solvent and additives introduced were changed to obtain polymer preparation solutions T-2 to T-10.

[0338] <Preparation Example 11>

[0339] BCS (2.0 g), CPN (1.3 g) and R40 (10.0 mg) were added to the polymer solution P-11 (6.7 g) obtained in Synthesis Example 11 and stirred. The solution was filtered using a filter with a pore size of 5.0 μm to obtain a polymer preparation solution T-11. The polymer preparation solution T-11 was used as a material for forming a phase difference film.

[0340] <Preparation Example 12>

[0341] As shown in Table 2 below, the same operation as in Preparation Example 11 was carried out except that the type of the polymer solution was changed to obtain a polymer preparation solution T-12.

[0342] [Table 2]

[0343] [3]Manufacturing of single-layer retardation film

[0344] <Example 1>

[0345] The polymer preparation liquid T-1 was applied to an alkali-free glass substrate using a bar coater to a film thickness of about 3.8 μm. The substrate was dried in a hot air circulation oven at 80°C for 3.5 minutes, and then irradiated with ultraviolet light (100 to 1200 mJ / cm2) at a wavelength of 365 nm from a high-pressure mercury lamp through a cutoff filter (365 nm bandpass filter) and a polarizing plate. 2 ). The substrate was heated in an IR oven at 160° C. for 20 minutes to prepare a glass substrate S-1 with a retardation film.

[0346] <Examples 2 to 8, Comparative Examples 1 and 2>

[0347] As shown in Table 3 below, the same operation as in Example 1 was carried out except that the type and film thickness of the polymer preparation solution and the firing conditions were changed to obtain glass substrates S-2 to S-8 and R-1 to R-2 with retardation films.

[0348] <Comparative Example 3>

[0349] The polymer preparation liquid T-11 was applied to an alkali-free glass substrate by a spin coater in a film thickness of about 2.0 μm. The substrate was dried on a hot plate at 60°C for 4 minutes, and then irradiated with ultraviolet light (50 to 800 mJ / cm2) at a wavelength of 365 nm from a high-pressure mercury lamp through a cutoff filter (365 nm bandpass filter) and a polarizing plate. 2 ). The substrate was heated in an IR oven at 120° C. for 20 minutes to prepare a glass substrate R-3 with a retardation film.

[0350] <Comparative Example 4>

[0351] As shown in Table 3 below, the same operation as in Comparative Example 3 was carried out except that the type of the polymer preparation liquid was changed, thereby obtaining a glass substrate R-4 with a retardation film.

[0352] [Table 3]

[0353] The retardation film-attached substrates S-1 to S-8 and R-1 to R-4 were evaluated for retardation, haze, NZ coefficient, and exposure margin by the following methods.

[0354] [Phase difference evaluation]

[0355] The linear retardation at a wavelength of 550 nm was measured using AxoScan manufactured by Axometrics, and Δn was calculated using the following formula. Table 4 summarizes the optimum exposure amount at which Δn becomes maximum and the value of Δn at that time.

[0356] Δn=phase difference value [nm] / film thickness [nm]

[0357] Phase difference value: Linear phase difference measured by Axo Scan

[0358] Film thickness: The measured film thickness of the retardation film

[0359] [Haze evaluation]

[0360] The substrate was set so that the light source was perpendicular to the substrate using a HAZE METER HZ-V3 manufactured by Suga Test Instruments, and the haze was measured at room temperature. The data are summarized in Table 4.

[0361] [NZ coefficient evaluation]

[0362] The refractive index in the three-dimensional direction of the retardation film at a wavelength of 550 nm was measured using AxoScan manufactured by Axometrics, and the NZ coefficient was calculated. The NZ coefficient is an index of the magnitude relationship of the three-dimensional refractive index and is represented by the following formula.

[0363] NZ coefficient = (nx-nz) / (nx-ny)

[0364] nx: Refractive index in the x-axis direction (slow axis direction)

[0365] ny: Refractive index in the y-axis direction (direction perpendicular to the slow axis)

[0366] nz: refractive index in the z-axis direction (thickness direction)

[0367] Table 4 summarizes the results of calculations of the glass substrates S-1 to S-8 and R-1 to R-4 with retardation films, assuming that the average refractive index of the retardation films was 1.55.

[0368] [Exposure margin evaluation]

[0369] From the optimum exposure with the maximum Δn, increase or decrease the exposure by 200 mJ / cm 2 When the change in NZ coefficient was 0.05 or less, it was evaluated as "◎", when it was greater than 0.05 and less than 0.15, it was evaluated as "○", and when it was greater than 0.15, it was evaluated as "×". The evaluation results are summarized in Table 4.

[0370] [Table 4]

[0371] According to the results of Comparative Examples 3 and 4 in Table 4, if all the polymerization initiators are replaced with polymeric polymerization initiators (from the low molecular weight polymerization initiator used in Comparative Example 3 to the one used in Comparative Example 4), the haze is suppressed, but Δn is greatly reduced. On the other hand, in the case where a polymeric polymerization initiator is added as in Examples 1 to 8, Δn maintains a high value and the haze is suppressed. In order to show sufficient phase difference, the side chain components need to form continuous blocks, and it is believed that Examples 1 to 8, in which polymerization reactions are also carried out before the introduction of the polymeric polymerization initiator, maintain high Δn. In addition, it is believed that by introducing a polymer block containing repeating units that do not contain photo-aligning side chains and liquid crystal side chains into the side chain polymer block, the formation of polydomains is hindered, the scattering of light in the transparent film is reduced, and the haze is suppressed.

[0372] Furthermore, the value of the NZ coefficient is shifted to the positive side in the embodiment compared with the comparative example in which the polymer block containing repeating units not containing photo-oriented side chains and liquid crystal side chains is not introduced. In addition, a wide exposure margin relative to the NZ coefficient is confirmed in the embodiment. In Examples 1 to 8, the block copolymer composed of the side chain polymer block and the polymer block containing repeating units not containing photo-oriented side chains and liquid crystal side chains forms microphase separation, so it is believed that the orientation is stable and a wide exposure margin is obtained.

Claims

1. A polymer composition, characterized in that The method comprises (A) a block copolymer and (B) an organic solvent, wherein the block copolymer has: A photosensitivity side chain polymer block (A1) capable of exhibiting liquid crystallinity, and The polymer block (A2) comprises a repeating unit having no photo-alignment side chain and no liquid crystal side chain.

2. The polymer composition according to claim 1, wherein The side chain type polymer block (A1) has a side chain represented by any one of the following formulae (a1) to (a6), In formulas (a1) to (a6), n1 and n2 are each independently 0, 1, 2 or 3, L is a single bond or an alkylene group having 1 to 12 carbon atoms, wherein some or all of the hydrogen atoms of the alkylene group are replaced by halogen atoms or not, T 1 is a single bond or an alkylene group having 1 to 12 carbon atoms, wherein some or all of the hydrogen atoms of the alkylene group are replaced by halogen atoms or not, A 1 , A 2 and D 1 Each independently represents a single bond, -O-, -CH2-, -C(=O)-O-, -OC(=O)-, -C(=O)-NH- or -NH-C(=O)-, wherein when T 1 When A is a single bond, 2 Also a single bond, Y 1 and Y 2 is a phenylene group or a naphthylene group, wherein a part or all of the hydrogen atoms of the phenylene group and the naphthylene group are substituted with a cyano group, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyl group having 1 to 5 carbon atoms, or an alkoxy group having 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, wherein a part or all of the hydrogen atoms of the phenylene group are replaced by a cyano group, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms; when Q 1 When the number is 2 or more, each Q 1 The same or different from each other; when Q 2 When the number is 2 or more, each Q 2 Same or different from each other, R is a hydrogen atom, a cyano group, a halogen atom, a carboxyl group, an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, X 1 and X 2 Each independently represents 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 X 1 When the number is 2 or more, each X 1 The same or different from each other; when X 2 When the number is 2 or more, each X 2 Same or different from each other, Z 1a and Z 2a are each independently a hydrogen atom, a halogen atom, a cyano group, or an alkyl group having 1 to 3 carbon atoms, wherein a part or all of the hydrogen atoms of the alkyl group are replaced by fluorine atoms, Cou is coumarin-6-yl or coumarin-7-yl, and a part of the hydrogen atoms bonded thereto is or is not replaced by -NO2, -CN, -CH=C(CN)2, -CH=CH-CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, 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 dotted lines are bonding bonds.

3. The polymer composition according to claim 1, wherein The side chain type polymer block (A1) further has a side chain that undergoes neither photodimerization nor photoisomerization.

4. The polymer composition according to claim 3, wherein The side chain that undergoes neither photodimerization nor photoisomerization is a side chain represented by any one of the following formulae (b1) to (b13), In formulas (b1) to (b13), A 3 and A 4 Each independently represents a single bond, -O-, -CH2-, -C(=O)-O-, -OC(=O)-, -C(=O)-NH-, or -NH-C(=O)-. 4 When the number is 2 or more, each A 4 Same or different from each other, R 1 is -NO2, -CN, a halogen atom, a phenyl group, a naphthyl group, a biphenyl group, a furyl group, a monovalent nitrogen-containing heterocyclic group, a monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms, R 2 is phenyl, naphthyl, biphenyl, furyl, a monovalent nitrogen-containing heterocyclic group, or a monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, wherein a part or all of the hydrogen atoms of these groups are substituted with -NO2, -CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, R 3 is a hydrogen atom, -NO2, -CN, -CH=C(CN)2, -CH=CH-CN, a halogen atom, a phenyl group, a naphthyl group, a biphenyl group, a furyl group, a monovalent nitrogen-containing heterocyclic group, a monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms, E is -C(=O)-O-, -OC(=O)-, -C(=O)-S- or -SC(=O)-, a is an integer from 1 to 12, k1 to k5 are each independently an integer of 0 to 2, and the total of k1 to k5 is 2 or more, k6 and k7 are each independently an integer of 0 to 2, and the total of k6 and k7 is 1 or more, m1, m2 and m3 are each independently an integer of 1 to 3, n is 0 or 1, Z 1 and Z 2 are each independently a single bond, -C(=O)-, -CH2-O-, or -CF2-, W 1 , W 2 and W 3 Each independently represents a single bond, -O-, -C(=O)-O-, -OC(=O)-, -C(=O)-N(R')- or -N(R')-C(=O)-, when W 2 When the number is 2 or more, each W 2 are the same or different from each other; R′ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Q is an alkylene group having 1 to 10 carbon atoms, wherein some or all of the hydrogen atoms of the alkylene group are substituted with halogen atoms, or none of them are substituted with halogen atoms. L represents a single bond or an alkylene group having 1 to 12 carbon atoms; or represents a divalent linking group in which one or more of -CH2- constituting the alkylene group having 1 to 12 carbon atoms is replaced by -O-, -S-, -C(=O)-O-, or -OC(=O)-, and a part or all of the hydrogen atoms of the alkylene group are or are not replaced by halogen atoms, Q 1 is a single bond, a phenylene group, a naphthylene group, or a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, wherein a part or all of the hydrogen atoms of the phenylene group and the naphthylene group are replaced by a cyano group, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, and when Q 1 When the number is 2 or more, each Q 1 Same or different from each other, n1 is 0, 1, 2, or 3, The hydrogen atoms on the benzene ring and the naphthalene ring are or are not replaced by a substituent selected from an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, a halogen atom, a cyano group and a nitro group, The dotted lines are bonding bonds.

5. The polymer composition according to claim 1, wherein The polymer block (A2) including a repeating unit having no photo-alignment side chain and no liquid crystal side chain is a polymer block derived from a polymeric polymerization initiator.

6. The polymer composition according to claim 5, wherein The polymeric polymerization initiator has a repeating unit represented by the following formula (1): In formula (1), R a1 ~R a4 are each independently a linear or branched alkyl group having 1 to 6 carbon atoms, or a cyano group, and R L1 and R L2 are each independently an alkylene group having 1 to 10 carbon atoms, L 1 and L 2 are each independently -C(=O)-O-, -OC(=O)-, -C(=O)-NH- or -NH-C(=O)-, X is a divalent group represented by the following formula (2) or (3), In formula (2) and formula (3), R a5 ~R a8 is a linear or branched alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, R L3 , R L4 , R L5 and R L6 Each is independently an alkylene group having 1 to 10 carbon atoms, and x and y are each independently a positive integer.

7. The polymer composition according to claim 6, wherein The polymeric polymerization initiator is represented by any one of the following formulas (In-1) to (In-2), In formula (In-1) and formula (In-2), x and y are the same as described above, and n is a positive integer.

8. The polymer composition according to claim 1, wherein The polymer block (A2) including a repeating unit having no photo-alignment side chain and no liquid crystal side chain is a polymer block derived from a polymeric chain transfer agent.

9. The polymer composition according to claim 8, wherein The polymeric chain transfer agent is represented by the following formula (4): In formula (4), Y is a linear or branched alkyl group having 1 to 3 carbon atoms, a hydroxyl group, a carboxyl group, or a mercapto group, and R L7 and R L8 Each is independently a single bond, or a linear or branched alkylene group having 1 to 6 carbon atoms, and x is a positive integer.

10. The polymer composition according to claim 1, wherein The number average molecular weight of the photosensitivity side chain polymer block (A1) capable of expressing liquid crystallinity is 5,000 to 300,000.

11. The polymer composition according to claim 1, wherein The number average molecular weight of the polymer block (A2) including a repeating unit having no photo-alignment side chain and no liquid crystal side chain is 200 to 10,000.

12. A method for manufacturing a single-layer phase difference material, characterized in that: The process includes the following steps: (I) a step of applying the polymer composition according to any one of claims 1 to 11 onto a substrate to form a coating film; (II) irradiating the coating film with polarized ultraviolet rays; and (III) A step of heating the coating film irradiated with ultraviolet rays to obtain a phase difference material.

13. A single-layer phase difference material, characterized in that: The polymer composition is obtained from any one of claims 1 to 11.

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