Method for manufacturing a patterned single-layer retardation material

Abstract

The present invention provides a method for producing a patterned single-layer retardation material, said method comprising: (I) a step for forming a coating film by applying a polymer composition onto a substrate, said polymer composition containing a liquid crystalline polymer having properties such that the alignability increases as the amount of light exposure increases if the amount of light exposure is less than the optimal amount of light exposure, while the alignability decreases as the amount of light exposure increases if the amount of light exposure is more than the optimal amount of light exposure; (II) a step for irradiating the coating film obtained in the step (I) with ultraviolet light twice, namely at least once via a mask and at least once with use of polarized ultraviolet light so that a high anisotropy region having high optical anisotropy is produced by being irradiated with polarized ultraviolet light and a low anisotropy region having relatively low optical anisotropy is produced due to deficient ultraviolet light in a region where the amount of light exposure is less than the optimal amount of light exposure and due to excessive ultraviolet light in a region where the amount of light exposure is more than the optimal amount of light exposure; and (III) a step for obtaining a retardation material by heating the coating film obtained in the step (II).

Description

[Technical Field]

[0001] The present invention relates to a method for producing a patterned single-layer retardation material and a single-layer retardation material. More specifically, the present invention relates to a material having optical properties suitable for applications such as display devices and recording materials, particularly to a patterned single-layer retardation material obtained from a composition containing a liquid crystal polymer that is suitable for use in optical compensation films such as polarizing plates and retardation plates for liquid crystal displays, and that has the property that the orientation increases with increasing exposure doses below the optimal exposure dose, and the orientation decreases with increasing exposure doses above the optimal exposure dose. [Background technology]

[0002] Due to demands for improved display quality and lighter weight of liquid crystal display devices, there is an increasing demand for polymer films with controlled internal molecular orientation structures as optical compensation films such as polarizing plates and retardation plates. To meet this demand, films utilizing the optical anisotropy of polymerizable liquid crystal compounds have been developed. The polymerizable liquid crystal compounds used here are generally liquid crystal compounds having a polymerizable group and a liquid crystal structural moiety (a structural moiety having a spacer portion and a mesogen portion), and an acrylic group is widely used as the polymerizable group.

[0003] Such polymerizable liquid crystal compounds are generally made into polymers (films) by a method of polymerizing them by irradiating them with radiation such as ultraviolet light. For example, a method is known in which a specific polymerizable liquid crystal compound having an acrylic group is supported between supports that have been subjected to an alignment treatment, and this compound is irradiated with radiation while being maintained in a liquid crystal state to obtain a polymer (Patent Document 1), and a method is known in which a photopolymerization initiator is added to a mixture of two types of polymerizable liquid crystal compounds having an acrylic group or a composition obtained by mixing this mixture with a chiral liquid crystal, and then irradiated with ultraviolet light to obtain a polymer (Patent Document 2).

[0004] In addition, various single-layer coating-type alignment films have been reported, such as alignment films using polymerizable liquid crystal compounds or polymers that do not require a liquid crystal alignment film (Patent Documents 3 and 4), and alignment films using polymers containing photocrosslinking moieties (Patent Documents 5 and 6).

[0005] On the other hand, when an oriented film using a polymer containing photo-crosslinking sites is used to produce a patterned single-layer retardation film using the same material using an exposure mask, it has become clear that haze (cloudiness) in the areas not exposed to UV light becomes a problem. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Unexamined Patent Publication No. 62-70407 [Patent Document 2] Japanese Patent Application Publication 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 Laid-Open No. 2008-164925 [Patent Document 6] Japanese Patent Application Publication No. 11-189665 Summary of the Invention [Problem to be solved by the invention]

[0007] The present invention has been made in consideration of the above problems, and aims to provide a method for manufacturing a patterned single-layer retardation material that exhibits a high retardation value in the anisotropic phase, suppresses the retardation value in the isotropic phase, and further suppresses turbidity (haze) through a simple process. [Means for solving the problem]

[0008] As a result of extensive research to solve the above problems, the inventors have discovered that by using a composition containing a specific polymer and a specific additive and applying the method for manufacturing a patterned retardation material described below, it is possible to manufacture a patterned single-layer retardation material that exhibits a high retardation value in the anisotropic phase, suppresses the retardation value in the isotropic phase, and further suppresses turbidity (haze), thereby completing the present invention.

[0009] That is, the present invention provides the following method for producing a patterned single-layer retardation material. 1. (I) A step of applying a polymer composition containing a liquid crystalline polymer, which has the property that the orientation increases with increasing exposure dose when the exposure dose is less than the optimum exposure dose, and decreases with increasing exposure dose when the exposure dose is greater than the optimum exposure dose, onto a substrate to form a coating film; (II) irradiating the coating film obtained in step (I) with polarized UV light twice, at least once through a mask and at least once with UV light, so as to produce high-anisotropy regions with high optical anisotropy by irradiation with polarized UV light, and low-anisotropy regions with relatively low optical anisotropy due to an insufficient amount of UV light in regions below the optimal exposure dose and an excess amount in regions above the optimal exposure dose; and (III) A step of heating the coating film obtained in step (II) to obtain a retardation material. A method for producing a patterned single-layer retardation material, comprising: 2. The polymer composition (A) a side chain polymer having a side chain having a photoreactive moiety represented by the following formula (a): (B) a silane coupling agent; and (C) Organic solvent The method for producing the patterned single-layer retardation material according to claim 1, which comprises: [ka] (In the formula, R 1 is an alkylene group having 1 to 30 carbon atoms, and one or more hydrogen atoms of the alkylene group may be substituted with a fluorine atom or an organic group. 1 -CH2CH2- in R may be replaced by -CH=CH-; 1In the -CH2-, -O-, -NH-C(=O)-, -C(=O)-NH-, -C(=O)-O-, -OC(=O)-, -NH-, -NH-C(=O)-NH- and -C(=O)- may be substituted with a group selected from the group consisting of -O-, -NH-C(=O)-, -C(=O)-, -OC(=O)-, -NH-, -NH-C(=O)-NH- and -C(=O)-. However, adjacent -CH2-s cannot be substituted with these groups at the same time. In addition, -CH2-s can be substituted with R 1 It may also be a terminal -CH2- in the middle. R 2 is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group, or a divalent fused ring group. R 3 is a single bond, —O—, —C(═O)—O—, —OC(═O)—, or —CH═CH—C(═O)—O—. R is 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 cyano group, or a nitro group, and when c≧2, each R may be the same or different. a is 0, 1 or 2. b is 0 or 1. c is an integer that satisfies 0≦c≦2b+4. The dashed lines represent bonds.) 3. The method for producing a patterned single-layer retardation material according to 2, wherein the side chain having the photoreactive moiety is represented by the following formula (a1): [ka] (In the formula, R 1 , R 2 and a are the same as above. R 3A is a single bond, —O—, —C(═O)—O—, or —OC(═O)—. The benzene ring in formula (a1) may be substituted with 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 cyano group, and a nitro group. The dashed lines represent bonds.) 4. (A) A method for producing a patterned single-layer retardation material, 2 or 3, in which the side chain polymer further has a side chain that only exhibits liquid crystallinity. 5. The method for producing a patterned single-layer retardation material according to 4, wherein the side chain exhibiting only liquid crystallinity is a liquid crystalline side chain represented by any one of the following formulas (1) to (13). [ka] [ka] (In the formula, A 1 , A 2 are each independently a single bond, -O-, -CH2-, -C(=O)-O-, -OC(=O)-, -C(=O)-NH-, -NH-C(=O)-, -CH=CH-C(=O)-O- or -OC(=O)-CH=CH-. R 11 is -NO2, -CN, a halogen atom, a phenyl group, a naphthyl group, a biphenylyl group, a furanyl 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 alkyloxy group having 1 to 12 carbon atoms. R 12 is a group selected from the group consisting of a phenyl group, a naphthyl group, a biphenylyl group, a furanyl group, a monovalent nitrogen-containing heterocyclic group, a monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and groups obtained by combining these, and a hydrogen atom bonded to this may be 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 13 is a hydrogen atom, -NO2, -CN, -CH=C(CN)2, -CH=CH-CN, a halogen atom, a phenyl group, a naphthyl group, a biphenylyl group, a furanyl 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- or -OC(=O)-. d is an integer from 1 to 12. k1 to k5 are each independently an integer of 0 to 2, but the sum of k1 to k5 is 2 or more. k6 and k7 each independently represent an integer of 0 to 2, but the sum of k6 and k7 is 1 or more. m1, m2 and m3 each independently represent an integer of 1 to 3. n is 0 or 1. Z 1 and Z 2 are each independently a single bond, —C(═O)—, —CH═O—, —CH═N—, or —CF═—. The dashed lines represent bonds.) 6. The method for producing a patterned single-layer retardation material according to 5, wherein the side chain exhibiting only liquid crystallinity is a liquid crystalline side chain represented by any one of formulas (1) to (11). 7. A single-layer retardation material manufactured by any of the methods 1 to 6. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a patterned retardation material having a region with a high retardation value and a region with a low retardation value, and in which whitening of the film is suppressed in the region with the low retardation value. DETAILED DESCRIPTION OF THE INVENTION

[0011] The method for producing a patterned single-layer retardation material of the present invention is a method including the following steps [I] to [III]. (I) a step of applying a polymer composition containing a liquid crystalline polymer, which has a property that the orientation increases with increasing exposure dose when the exposure dose is less than the optimum exposure dose, and decreases with increasing exposure dose when the exposure dose is greater than the optimum exposure dose, to form a coating film; (II) irradiating the coating film obtained in step (I) with polarized UV light twice, at least once through a mask and at least once with UV light, so as to produce high-anisotropy regions with high optical anisotropy by irradiation with polarized UV light, and low-anisotropy regions with relatively low optical anisotropy due to an insufficient amount of UV light in regions below the optimal exposure dose and an excess amount in regions above the optimal exposure dose; and (III) A step of heating the coating film obtained in step (II) to obtain a retardation material.

[0012] The polymer composition contains a liquid-crystalline polymer (hereinafter simply referred to as a side-chain polymer) that exhibits a property that the orientation increases with increasing exposure doses below the optimal exposure dose and decreases with increasing exposure doses above the optimal exposure dose. The coating film obtained using the polymer composition contains a photosensitive side-chain polymer capable of exhibiting liquid crystallinity. This coating film is subjected to an orientation treatment by polarized light irradiation without a rubbing treatment. After polarized light irradiation, the coating film is heated to form a film (hereinafter also referred to as a single-layer retardation film) imparted with optical anisotropy. The slight anisotropy exhibited by polarized light irradiation serves as a driving force, and the liquid-crystalline side-chain polymer itself efficiently realigns by self-organization. As a result, a highly efficient orientation treatment is achieved, resulting in a single-layer retardation film imparted with high optical anisotropy.

[0013] In addition, the method for manufacturing the patterned single-layer retardation material of the present invention comprises the steps of irradiating polarized ultraviolet light twice, at least once through a mask and at least once using polarized ultraviolet light, so that the highly anisotropic region with high optical anisotropy is produced by irradiating polarized ultraviolet light, and the amount of ultraviolet light is insufficient in the region below the optimal exposure dose, and excessive in the region above the optimal exposure dose, resulting in the low anisotropy region with relatively low optical anisotropy.By having such a step, ultraviolet light is irradiated both in the region with anisotropy and in the region with less anisotropy, and the hardness of the film is increased, so that the film in the patterned retardation material can be prevented from becoming cloudy, that is, the so-called whitening phenomenon, in the region with low anisotropy.Therefore, it is possible to obtain a patterned retardation material with reduced haze.

[0014] Hereinafter, embodiments of the present invention will be described in detail.

[0015] [Polymer composition] The polymer composition used in the production method of the present invention contains (A) a side chain polymer having a side chain with a photoreactive site, (B) a silane coupling agent, and (C) an organic solvent.

[0016] [(A) Side chain polymer] Component (A) is a photosensitive side chain polymer that exhibits liquid crystallinity within a predetermined temperature range, and has a side chain (hereinafter also referred to as side chain a) having a photoreactive moiety represented by the following formula (a): [ka]

[0017] In formula (a), R 1 is an alkylene group having 1 to 30 carbon atoms, and one or more hydrogen atoms of the alkylene group may be substituted with a fluorine atom or an organic group. 1 -CH2CH2- in R may be replaced by -CH=CH-; 1 In the -CH2-, -O-, -NH-C(=O)-, -C(=O)-NH-, -C(=O)-O-, -OC(=O)-, -NH-, -NH-C(=O)-NH- and -C(=O)- may be substituted with a group selected from the group consisting of -O-, -NH-C(=O)-, -C(=O)-, -OC(=O)-, -NH-, -NH-C(=O)-NH- and -C(=O)-. However, adjacent -CH2-s cannot be substituted with these groups at the same time. In addition, -CH2-s can be substituted with R 1 It may be a terminal -CH2- in the middle. 2 R is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group, or a divalent fused ring group. 3 is a single bond, -O-, -C(=O)-O-, -OC(=O)-, or -CH=CH-C(=O)-O-. R is 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 cyano group, or a nitro group, and when c≧2, each R may be the same or different. a is 0, 1, or 2. b is 0 or 1. c is an integer that satisfies 0≦c≦2b+4. The dashed lines represent bonds.

[0018] R 1The alkylene group having 1 to 30 carbon atoms represented by the formula (I) may be linear, branched, or cyclic, and specific examples thereof include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, and a decane-1,10-diyl group.

[0019] R 2 Examples of the divalent aromatic group represented by R include a phenylene group and a biphenylylene group. 2 Examples of the divalent alicyclic group represented by R include a cyclohexanediyl group. 2 Examples of the divalent heterocyclic group represented by R include a furandiyl group. 2 Examples of the divalent fused ring group represented by the formula: include a naphthylene group.

[0020] The side chain a is preferably one represented by the following formula (a1) (hereinafter also referred to as side chain a1). [ka]

[0021] In formula (a1), R 1 , R 2 and a are the same as above. R 3A is a single bond, -O-, -C(=O)-O-, or -OC(=O)-. The benzene ring in formula (a1) may be substituted with 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 cyano group, and a nitro group. The dashed lines represent bonds.

[0022] The side chain a1 is preferably, for example, one represented by the following formula (a1-1). [ka]

[0023] In formula (a1-1), L is a linear or branched alkylene group having 1 to 16 carbon atoms, and X is a single bond, -O-, -C(=O)-O-, or -OC(=O)-.

[0024] The (A) side chain polymer preferably reacts with light in the wavelength range of 250 to 400 nm and exhibits liquid crystallinity in the temperature range of 100 to 300° C. The (A) side chain polymer preferably has a photosensitive side chain that reacts with light in the wavelength range of 250 to 400 nm.

[0025] (A) Side-chain polymers have photosensitive side chains attached to their main chains, and can undergo crosslinking or isomerization in response to light. The structure of the photosensitive side-chain polymers capable of exhibiting liquid crystallinity is not particularly limited as long as they satisfy these properties, but it is preferable that the side-chain structure has a rigid mesogen component. When the side-chain polymers are used as a single-layer retardation material, stable optical anisotropy can be obtained.

[0026] A more specific example of the structure of the photosensitive side chain polymer capable of exhibiting liquid crystallinity is preferably a structure having a main chain composed of at least one selected from the group consisting of radical polymerizable groups such as (meth)acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene, and siloxane, and a side chain a.

[0027] Furthermore, since the (A) side chain polymer exhibits liquid crystallinity in the temperature range of 100 to 300° C., it is preferable that it further has a side chain that exhibits only liquid crystallinity (hereinafter also referred to as side chain b). Note that "exhibiting only liquid crystallinity" here means that a polymer having only side chain b does not exhibit photosensitivity and exhibits only liquid crystallinity during the production process of the retardation material of the present invention (i.e., steps (I) to (III) described below).

[0028] The side chain b is preferably any one liquid crystalline side chain selected from the group consisting of the following formulae (1) to (13). [ka]

[0029] [ka]

[0030] In formulas (1) to (13), A 1 , A 2 are each independently a single bond, -O-, -CH2-, -C(=O)-O-, -OC(=O)-, -C(=O)-NH-, -NH-C(=O)-, -CH=CH-C(=O)-O- or -OC(=O)-CH=CH-. R 11 R is -NO2, -CN, a halogen atom, a phenyl group, a naphthyl group, a biphenylyl group, a furanyl 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 alkyloxy group having 1 to 12 carbon atoms. 12 R is a group selected from the group consisting of a phenyl group, a naphthyl group, a biphenylyl group, a furanyl group, a monovalent nitrogen-containing heterocyclic group, a monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and a group obtained by combining these, and a hydrogen atom bonded to the group may be 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. 13 represents a hydrogen atom, -NO2, -CN, -CH=C(CN)2, -CH=CH-CN, a halogen atom, a phenyl group, a naphthyl group, a biphenylyl group, a furanyl 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 represents -C(=O)-O- or -OC(=O)-. d represents an integer of 1 to 12. k1 to k5 are each independently an integer of 0 to 2, provided that the sum of k1 to k5 is 2 or greater. k6 and k7 are each independently an integer of 0 to 2, provided that the sum of k6 and k7 is 1 or greater. 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)-, -CHO-, -CH=N-, or -CF-. The dashed lines represent bonds.

[0031] Among these, the side chain b is preferably one represented by any one of formulas (1) to (11).

[0032] The side chain polymer of component (A) can be obtained by polymerizing a monomer having a structure represented by formula (a) and, if desired, a monomer having a structure that only exhibits liquid crystallinity.

[0033] Examples of the monomer having a structure represented by formula (a) (hereinafter also referred to as monomer M1) include compounds represented by the following formula (M1). [ka] (In the formula, R 1 , R 2 , R 3 , R, a, m and n are the same as above.)

[0034] The monomer M1 is preferably one represented by the following formula (M1A). [ka] (In the formula, R 1 , R 2 , R 3A , R and a are the same as above.)

[0035] Of the monomers M1A, those represented by the following formula (M1B) are more preferred. [ka] (wherein L and X are the same as above.)

[0036] In the formulae (M1), (M1A) and (M1B), PL is a polymerizable group represented by any one of the following formulae (PL-1) to (PL-5). [ka]

[0037] In formulas (PL-1) to (PL-5), Q 1 , Q 2 and Q 3 is a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or a linear or branched alkyl group having 1 to 10 carbon atoms substituted with a halogen atom. 1 or a bond to L. Some of these monomers are commercially available, and others can be produced from known materials by known production methods.

[0038] Preferred examples of the monomer M1 include those represented by the following formulae (M1-1) to (M1-5). [ka] (In the formula, PL is the same as above, and p is an integer of 2 to 9.)

[0039] A monomer having a structure that only exhibits liquid crystallinity (hereinafter also referred to as monomer M2) is a monomer that allows a polymer derived from the monomer to exhibit liquid crystallinity and that can form a mesogenic group in the side chain portion.

[0040] The mesogenic group in the side chain may be a group that forms a mesogenic structure by itself, such as biphenyl or phenylbenzoate, or a group that forms a mesogenic structure by hydrogen bonding between side chains, such as benzoic acid. The mesogenic group in the side chain preferably has the following structure: [ka]

[0041] More specific examples of the monomer M2 include a structure having a polymerizable group derived from at least one selected from the group consisting of radically polymerizable groups such as hydrocarbons, (meth)acrylates, itaconates, fumarates, maleates, α-methylene-γ-butyrolactone, styrenes, vinyls, maleimides, and norbornenes, and siloxanes, and at least one structure represented by formulas (1) to (13). In particular, the monomer M2 is preferably one having a (meth)acrylate as the polymerizable group, and one having a side chain terminal of -COOH.

[0042] Preferred examples of the monomer M2 include those represented by the following formulas (M2-1) to (M2-11). [ka]

[0043] [ka] (In the formula, PL and p are the same as above.)

[0044] In addition, other monomers can be copolymerized within a range that does not impair the photoreactivity and / or liquid crystallinity. Examples of other monomers include industrially available radically polymerizable monomers. Specific examples of other monomers include unsaturated carboxylic acids, acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds, and vinyl compounds.

[0045] Specific examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid.

[0046] Examples of acrylic acid ester compounds include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthrylmethyl 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-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate.

[0047] Examples of methacrylic acid ester compounds include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthrylmethyl 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-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate.

[0048] Examples of vinyl compounds include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether. Examples of styrene compounds include styrene, 4-methylstyrene, 4-chlorostyrene, and 4-bromostyrene. Examples of maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

[0049] The content of the side chain a in the side chain type polymer of the present invention is preferably from 20 to 99.9 mol %, more preferably from 30 to 95 mol %, and even more preferably from 40 to 90 mol %, from the viewpoint of photoreactivity.

[0050] The content of the side chain b in the side chain type polymer of the present invention is preferably from 0.1 to 80 mol %, more preferably from 5 to 70 mol %, and even more preferably from 10 to 60 mol %, from the viewpoint of retardation value.

[0051] As described above, the side chain polymer of the present invention may contain other side chains. When the total content of side chain a and side chain b is less than 100 mol %, the content of the other side chains is the remaining portion.

[0052] The method for producing the side chain polymer of component (A) is not particularly limited, and a general-purpose method used industrially can be used. Specifically, it can be produced by radical polymerization, cationic polymerization, or anionic polymerization using the vinyl groups of the above-mentioned monomers M1 and M2, and optionally other monomers. Among these, radical polymerization is particularly preferred from the viewpoint of ease of reaction control, etc.

[0053] As the polymerization initiator for radical polymerization, known compounds such as radical polymerization initiators (radical thermal polymerization initiators, radical photopolymerization initiators) and reversible addition-fragmentation chain transfer (RAFT) polymerization reagents can be used.

[0054] The radical thermal polymerization initiator is a compound that generates radicals when heated to a temperature equal to or higher than its decomposition temperature. Examples of such 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 (dibutylperoxycyclohexane, etc.), alkyl peresters (peroxyneodecanoic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy-2-ethylcyclohexanoic acid-tert-amyl ester, etc.), persulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), and azo compounds (azobisisobutyronitrile, 2,2′-di(2-hydroxyethyl)azobisisobutyronitrile, etc.). The radical thermal polymerization initiators may be used alone or in combination of two or more.

[0055] The radical photopolymerization initiator is not particularly limited as long as it is a compound that initiates radical polymerization by light irradiation. Examples of such radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexylphenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone ... ,2-Diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid isoamyl ester, 4,4'-di(tert-butylperoxycarbonyl)benzophenone, 3,4,4'-tri(tert-butylperoxycarbonyl)benzophenone Carbonyl)benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-(4'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-pentyloxy) Styryl)-4,6-bis(trichloromethyl)-s-triazine, 4-[pN,N-di(ethoxycarbonylmethyl)]-2,6-di(trichloromethyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(2'-chlorophenyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(4'-methoxyphenyl)-s-triazine, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 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'-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(t-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(t-hexylperoxycarbonyl)benzophenone, 3,3'-di(methoxycarbonyl)-4,4'-di(t-butylperoxycarbonyl)benzophenone, 3,4'- Examples of the radical photopolymerization initiator include di(methoxycarbonyl)-4,3'-di(t-butylperoxycarbonyl)benzophenone, 4,4'-di(methoxycarbonyl)-3,3'-di(t-butylperoxycarbonyl)benzophenone, 2-(3-methyl-3H-benzothiazol-2-ylidene)-1-naphthalen-2-yl-ethanone, and 2-(3-methyl-1,3-benzothiazol-2(3H)-ylidene)-1-(2-benzoyl)ethanone. The radical photopolymerization initiator may be used alone or in combination of two or more.

[0056] The radical polymerization method is not particularly limited, and may be an emulsion polymerization method, a suspension polymerization method, a dispersion polymerization method, a precipitation polymerization method, a bulk polymerization method, a solution polymerization method, or the like.

[0057] The organic solvent used in the polymerization reaction is not particularly limited as long as it dissolves the produced 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, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl 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 ... 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, methylcyclohexene, propyl ether, dihexyl ether, 1,4-Dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N,N-dimethylpropanamide, 3-ethoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, etc.

[0058] The organic solvents may be used alone or in combination of two or more. Furthermore, even if the solvent does not dissolve the polymer to be produced, it may be mixed with the organic solvents described above to the extent that the polymer does not precipitate. Furthermore, since oxygen in the organic solvent inhibits the polymerization reaction in radical polymerization, it is preferable to use an organic solvent that has been degassed to the greatest extent possible.

[0059] The polymerization temperature during radical polymerization can be selected from any temperature between 30 and 150°C, but is preferably in the range of 50 to 100°C. The reaction can be carried out at any concentration, but if the concentration is too low, it becomes difficult to obtain a polymer with a high molecular weight, and if the concentration is too high, the reaction solution becomes too viscous, making uniform stirring difficult. Therefore, the monomer concentration is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The reaction can be carried out at a high concentration initially, and then an organic solvent can be added.

[0060] In the above-mentioned radical polymerization reaction, if the ratio of the radical polymerization initiator to the monomer is high, the molecular weight of the obtained polymer will be small, and if it is low, the molecular weight of the obtained polymer will be large, so the ratio of the radical initiator to the monomer to be polymerized is preferably 0.1 to 10 mol %. Furthermore, various monomer components, solvents, initiators, etc. can also be added during polymerization.

[0061] To recover the polymer produced from the reaction solution obtained by the above reaction, the reaction solution may be poured into a poor solvent to precipitate the polymer. Examples of poor solvents used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, and water. The polymer precipitated by pouring into the poor solvent can be recovered by filtration and then dried at room temperature or by heating under atmospheric or reduced pressure. Furthermore, the recovered polymer can be redissolved in an organic solvent and reprecipitated and recovered 2 to 10 times to reduce the amount of impurities in the polymer. Examples of poor solvents include alcohols, ketones, and hydrocarbons. Using three or more poor solvents selected from these solvents is preferred because it further increases the efficiency of purification.

[0062] In consideration of the strength of the resulting coating film, the workability during coating film formation, and the uniformity of the coating film, the side chain polymer (A) of the present invention preferably has a weight average molecular weight, measured by GPC (Gel Permeation Chromatography), of 2,000 to 2,000,000, more preferably 2,000 to 1,000,000, and even more preferably 5,000 to 200,000.

[0063] [(B) Silane coupling agent] The polymer composition of the present invention contains (B) a silane coupling agent. The silane coupling agent is preferably a silane compound represented by the following formula (B). [ka]

[0064] In formula (B), R 21 is a reactive functional group. 22 is a hydrolyzable group. 23 is a methyl group or an ethyl group. x is an integer of 0 to 3. y is an integer of 1 to 3.

[0065] R 21 Examples of the reactive functional group represented by the formula (I) include an amino group, a ureido group, a (meth)acryloxy group, a vinyl group, an epoxy group, a mercapto group, and a group having an oxetane structure, among which an amino group, a ureido group, a (meth)acryloyloxy group, and a group having an oxetane structure are preferred, and a group having an oxetane structure is particularly preferred.

[0066] R 22 Examples of the hydrolyzable group represented by the formula (I) include a halogen atom, an alkoxy group having 1 to 3 carbon atoms, and an alkoxyalkoxy group having 2 to 4 carbon atoms. Examples of the halogen atom include a chlorine atom and a bromine atom. The alkoxy group having 1 to 3 carbon atoms is preferably a linear or branched group, and specific examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group. Specific examples of the alkoxyalkoxy group having 2 to 4 carbon atoms include a methoxymethoxy group, a 2-methoxyethoxy group, an ethoxymethoxy group, and a 2-ethoxyethoxy group.

[0067] Specific examples of (B) silane coupling agents include 3-aminopropyltrichlorosilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrichlorosilane, allyltrimethoxysilane, and allyltriethoxysilane. Examples thereof include 3-(3-ethyloxetan-3-ylmethyloxy)propyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-(3-ethyloxetan-3-ylmethyloxy)propyltrimethoxysilane, 3-(3-ethyloxetan-3-ylmethyloxy)propyltriethoxysilane, 3-(3-ethyloxetan-3-ylmethyloxy)propylmethyldimethoxysilane, and 3-(3-ethyloxetan-3-ylmethyloxy)propylmethyldiethoxysilane.

[0068] Among these, 3-(3-ethyloxetan-3-ylmethyloxy)propyltrimethoxysilane, 3-(3-ethyloxetan-3-ylmethyloxy)propyltriethoxysilane, 3-(3-ethyloxetan-3-ylmethyloxy)propylmethyldimethoxysilane, 3-(3-ethyloxetan-3-ylmethyloxy)propylmethyldiethoxysilane, etc. are particularly preferred. Commercially available products can be used as the silane coupling agent.

[0069] In the polymer composition of the present invention, the content of the silane coupling agent (B) is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, and even more preferably 0.05 to 1 part by mass, per 100 parts by mass of the polymer.

[0070] [(C) Organic solvent] The organic solvent of component (C) is not particularly limited as long as it is an organic solvent that can dissolve 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, tetramethylurea, pyridine, dimethyl sulfone, hexamethylphosphoric triamide, γ-butyrolactone, 3-methoxy-N,N-dimethylpropanamide, 3-ethoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, 1,3-dimethyl-2-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme, and 4-hydroxy-4-methyl-2-pentanone. These may be used alone or in combination of two or more.

[0071] [Other ingredients] The polymer composition of the present invention may contain components other than the components (A) to (C), such as, but not limited to, solvents and compounds that improve the film thickness uniformity and surface smoothness when the polymer composition is applied, and compounds that improve the adhesion between the retardation material and the substrate.

[0072] Specific examples of solvents (poor solvents) that improve the uniformity of the film thickness and the surface smoothness include isopropyl alcohol, methoxymethyl pentanol, methyl cellosolve, ethyl cellosolve, butyl 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, 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, and dipropylene glycol monoacetate. Monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, 1-hexanol, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, acetic acid Methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 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 diacetate,Examples of solvents having low surface tension include propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, and 2-(2-ethoxypropoxy)propanol.

[0073] These poor solvents may be used alone or in combination of two or more. When the poor solvent is used, its content in the solvent is preferably 5 to 80% by mass, more preferably 20 to 60% by mass, so as not to significantly reduce the solubility of all the solvents contained in the polymer composition.

[0074] Compounds that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. Specific examples include EFTOP (registered trademark) 301, EF303, and EF352 (manufactured by Tochem Products Co., Ltd.), MEGAFACE (registered trademark) F171, F173, R-30, and R-40 (manufactured by DIC Corporation), Fluorad FC430 and FC431 (manufactured by 3M Limited), Asahiguard (registered trademark) AG710 (manufactured by AGC Corporation), and Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (manufactured by AGC Seimi Chemical Co., Ltd.). The content of these surfactants is preferably 0.01 to 2 parts by mass, and more preferably 0.01 to 1 part by mass, per 100 parts by mass of component (A).

[0075] Furthermore, in order to improve the adhesion between the substrate and the retardation material and to prevent deterioration of properties due to light such as a backlight, a phenoplast compound or an epoxy group-containing compound may be added to the polymer composition.

[0076] Specific examples of phenoplast additives are shown below, but are not limited to these. [ka]

[0077] Specific examples of epoxy group-containing compounds 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, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, and N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane.

[0078] When a compound that improves adhesion to the substrate is used, the content thereof is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass, per 100 parts by mass of the polymer component contained in the polymer composition. If the content is less than 0.1 part by mass, the effect of improving adhesion cannot be expected, and if it is more than 30 parts by mass, the alignment of the liquid crystal may be deteriorated.

[0079] A photosensitizer can also be used as an additive, and as the photosensitizer, a colorless sensitizer and a triplet sensitizer are preferred.

[0080] Photosensitizers include aromatic nitro compounds, coumarins (7-diethylamino-4-methylcoumarin, 7-hydroxy-4-methylcoumarin), ketocoumarins, carbonylbiscoumarins, aromatic 2-hydroxyketones (2-hydroxybenzophenone, mono- or di-p-(dimethylamino)-2-hydroxybenzophenone, etc.), acetophenone, anthraquinone, xanthone, thioxanthone, benzanthrone, thiazoline (2-benzoylmethylene-3-methyl-β-naphthothiazoline, 2-(β-naphthoyl)-2-methyl ... methylene)-3-methylbenzothiazoline, 2-(α-naphthoylmethylene)-3-methylbenzothiazoline, 2-(4-biphenoylmethylene)-3-methylbenzothiazoline, 2-(β-naphthoylmethylene)-3-methyl-β-naphthothiazoline, 2-(4-biphenoylmethylene)-3-methyl-β-naphthothiazoline, 2-(p-fluorobenzoylmethylene)-3-methyl-β-naphthothiazoline, etc.), oxazoline (2-benzoylmethylene-3-methyl-β-naphthoxazoline, 2-(β-naphthoylmethylene)-3-methyl-β-naphthoxazoline, etc.), 2-(α-naphthoylmethylene)-3-methylbenzoxazoline, 2-(4-biphenoylmethylene)-3-methylbenzoxazoline, 2-(β-naphthoylmethylene)-3-methyl-β-naphthoxazoline, 2-(4-biphenoylmethylene)-3-methyl-β-naphthoxazoline, 2-(p-fluorobenzoylmethylene)-3-methyl-β-naphthoxazoline, etc.), benzothiazole, nitroaniline (m- or p-nitroaniline, 2, 4,6-trinitroaniline, etc.), nitroacenaphthene (5-nitroacenaphthene, etc.), 2-[(m-hydroxy-p-methoxy)styryl]benzothiazole, benzoin alkyl ether, N-alkylated phthalone, acetophenone ketal (2,2-dimethoxyphenylethanone, etc.), naphthalene, anthracene (2-naphthalenemethanol, 2-naphthalenecarboxylic acid, 9-anthracenemethanol, 9-anthracenecarboxylic acid, etc.), benzopyran, azoindolizine, merocoumarin, etc.Of these, aromatic 2-hydroxyketones (benzophenones), coumarins, ketocoumarins, carbonylbiscoumarins, acetophenones, anthraquinones, xanthones, thioxanthones, and acetophenone ketals are preferred.

[0081] In addition to the above, the polymer composition of the present invention may contain a dielectric or conductive substance for the purpose of changing the electrical properties such as the dielectric constant or conductivity of the retardation material, and further may contain a crosslinkable compound for the purpose of increasing the hardness or density of the film when made into a retardation material, as long as the effects of the present invention are not impaired.

[0082] [Preparation of polymer composition] The polymer composition of the present invention is preferably prepared as a coating solution suitable for forming a single-layer retardation material. That is, the polymer composition used in the present invention is preferably prepared as a solution in which the components (A) and (B), as well as the solvents and compounds that improve the film thickness uniformity and surface smoothness described above, and the compounds that improve the adhesion between the liquid crystal alignment film and the substrate, are dissolved in the organic solvent of the component (C). Here, the content of the component (A) in the composition of the present invention is preferably 1 to 30% by mass.

[0083] The polymer composition of the present invention may contain other polymers in addition to the polymer of component (A) to the extent that the liquid crystallinity and photosensitivity are not impaired. In this case, the content of the other polymers in the polymer component is preferably 0.5 to 80 mass %, more preferably 1 to 50 mass %. Examples of the other polymers include polymers that are not photosensitive side-chain polymers capable of exhibiting liquid crystallinity, such as poly(meth)acrylate, polyamic acid, and polyimide.

[0084] [Manufacturing method of single-layer retardation material] As described above, the method for producing the patterned single-layer retardation material of the present invention includes the following steps (I) to (III). (I) a step of applying a polymer composition containing a liquid crystalline polymer, which has a property that the orientation increases with increasing exposure dose when the exposure dose is less than the optimum exposure dose, and decreases with increasing exposure dose when the exposure dose is greater than the optimum exposure dose, to form a coating film; (II) irradiating the coating film obtained in step (I) with polarized UV light twice, at least once through a mask and at least once with UV light, so as to produce high-anisotropy regions with high optical anisotropy by irradiation with polarized UV light, and low-anisotropy regions with relatively low optical anisotropy due to an insufficient amount of UV light in regions below the optimal exposure dose and an excess amount in regions above the optimal exposure dose; and (III) A step of heating the coating film obtained in step (II) to obtain a retardation material.

[0085] [Process (I)] Step (I) is a process of forming a coating film by applying a polymer composition containing a liquid crystalline polymer, which has the property that the orientation increases with increasing exposure doses below the optimal exposure dose, and decreases with increasing exposure doses above the optimal exposure dose. More specifically, the composition is applied to a substrate (e.g., a silicon / silicon dioxide-coated substrate, a silicon nitride substrate, a metal-coated substrate such as aluminum, molybdenum, or chromium, a glass substrate, a quartz substrate, an ITO substrate, etc.) or a film (e.g., a triacetyl cellulose (TAC) film, a cycloolefin polymer film, a polyethylene terephthalate film, an acrylic film, or other resin film) by a method such as bar coating, spin coating, flow coating, roll coating, slit coating, slit coating followed by spin coating, inkjet printing, or printing. After application, the solvent is evaporated by heating means such as a hot plate, a heat circulation oven, or an IR (infrared) oven, preferably at 50 to 200°C, more preferably at 50 to 150°C, to obtain a coating film.

[0086] [Process (II)] In step (II), the coating film obtained in step (I) is irradiated with polarized UV light twice, at least once through a mask and at least once using polarized UV light, so that high-anisotropy regions with high optical anisotropy are produced by irradiating the coating film with polarized UV light, and low-anisotropy regions with relatively low optical anisotropy due to insufficient UV light in regions below the optimal exposure dose and excessive UV light in regions above the optimal exposure dose. More specific embodiments of this process include the following steps (II-1) to (II-3).

[0087] [Process (II-1)] In step (II-1), a first UV irradiation is performed through a mask so that only the region to be anisotropic is covered. The UV light used here may be either full-spectrum UV light or polarized UV light. Next, the mask is removed and the film is irradiated with polarized UV light. As a result, the region covered by the mask during the first irradiation is irradiated with polarized UV light only once, thereby imparting anisotropy, and the region that was irradiated with UV light the first time is irradiated with UV light the second time, thereby reducing the anisotropy.

[0088] [Process (II-2)] In step (II-2), after a first UV irradiation using polarized UV, a second UV irradiation is performed through a mask so that only the region to be anisotropic is covered. The UV light used for the second irradiation may be either full-spectrum UV or polarized UV. As a result, the region covered by the mask during the second irradiation is irradiated with polarized UV only once, thereby imparting anisotropy, and the anisotropy is reduced in the region irradiated with the second UV.

[0089] [Process (II-3)] In step (II-3), the film is irradiated with total UV light for the first time, followed by polarized UV light for the second time through a mask so that only the areas where anisotropy is not desired are covered. The total UV light used for the first irradiation is preferably used in a smaller dose than the polarized UV light used for the second irradiation. This allows the areas not covered by the mask during the second irradiation to be irradiated with polarized UV light, thereby imparting anisotropy, while suppressing the anisotropy in the areas that have only been irradiated with UV light for the first time.

[0090] When irradiating with polarized ultraviolet light, the substrate is irradiated with polarized ultraviolet light from a specific direction via a polarizing plate. The ultraviolet light used can have a wavelength in the range of 100 to 400 nm. Preferably, an optimal wavelength is selected through a filter or the like depending on the type of coating film used. For example, ultraviolet light having a wavelength in the range of 290 to 400 nm can be selected and used so as to selectively induce a photocrosslinking reaction. For example, light emitted from a high-pressure mercury lamp can be used as the ultraviolet light.

[0091] The amount of polarized UV light to be applied depends on the coating film used. The amount of application is preferably within a range of 1 to 70%, and more preferably within a range of 1 to 50%, of the amount of polarized UV light that achieves the maximum value of ΔA (hereinafter also referred to as ΔAmax), which is the difference between the UV absorbance in the direction parallel to the polarization direction of the polarized UV light and the UV absorbance in the direction perpendicular to the polarization direction of the polarized UV light.

[0092] The pattern shape and pattern size of the exposure mask to be used are not particularly limited. Examples of the pattern shape include a line pattern, a line / space (L / S) pattern, and a dot pattern. A micrometer-sized pattern can be formed. For example, by using an exposure mask having a fine L / S pattern, a fine L / S pattern of about 0.5 to 500 μm can be formed.

[0093] [Process (III)] In step (III), the coating film irradiated with polarized ultraviolet light in step (II) is heated, which can impart orientation controllability to the coating film.

[0094] Heating can be performed using a heating means such as a hot plate, a heat circulation oven, an IR (infrared) oven, etc. The heating temperature can be determined taking into consideration the temperature at which the coating film to be used will exhibit liquid crystallinity.

[0095] The heating temperature is preferably within the range of the temperature at which the polymer contained in the polymer composition exhibits liquid crystallinity (hereinafter referred to as the liquid crystal onset temperature). In the case of a thin film surface such as a coating film, the liquid crystal onset temperature at the coating film surface is expected to be lower than the liquid crystal onset temperature when the polymer is observed in bulk. Therefore, the heating temperature is more preferably within the range of the liquid crystal onset temperature at the coating film surface. That is, the heating temperature range after irradiation with polarized UV light is preferably within a range having a lower limit 10°C lower than the lower limit of the liquid crystal onset temperature range of the polymer used and an upper limit 10°C lower than the upper limit of the liquid crystal temperature range. If the heating temperature is lower than the above temperature range, the effect of thermally amplifying the anisotropy in the coating film tends to be insufficient. If the heating temperature is too higher than the above temperature range, the state of the coating film tends to approach an isotropic liquid state (isotropic phase), in which case it may be difficult to achieve unidirectional reorientation by self-organization.

[0096] The liquid crystal development temperature refers to a temperature that is equal to or higher than the liquid crystal transition temperature at which the polymer or coating surface undergoes a phase transition from a solid phase to a liquid crystal phase and equal to or lower than the isotropic phase transition temperature (Tiso) at which the liquid crystal phase undergoes a phase transition from an isotropic phase. For example, developing liquid crystallinity at 130°C or lower means that the liquid crystal transition temperature at which the phase transition from a solid phase to a liquid crystal phase occurs is 130°C or lower.

[0097] The thickness of the coating film formed after heating can be appropriately selected taking into consideration the unevenness of the substrate used and the optical and electrical properties, and is preferably, for example, 0.5 to 10 μm.

[0098] The single-layer retardation material of the present invention obtained in this manner is a material having optical properties suitable for applications such as display devices and recording materials, and is particularly suitable as an optical compensation film such as a polarizing plate and a retardation plate for liquid crystal displays. [Example]

[0099] The present invention will be described in more detail below with reference to synthesis examples, preparation examples, working examples and comparative examples, but the present invention is not limited to the following examples.

[0100] The monomer M1 having a photoreactive group and the monomer M2 having a liquid crystalline group used in the examples are shown below. M1 and M2 were each synthesized as follows. M1 was synthesized according to the synthesis method described in WO 2011 / 084546. M2 was synthesized according to the synthesis method described in JP-A-9-118717. The side chain derived from M1 exhibits photoreactivity and liquid crystallinity, while the side chain derived from M2 only possesses liquid crystallinity. [ka]

[0101] The abbreviations for the other reagents used in this example are shown below. (organic solvent) THF: tetrahydrofuran NMP: N-ethyl-2-pyrrolidone BCS: butyl cellosolve PGME: propylene glycol monomethyl ether

[0102] (Polymerization initiator) AIBN: 2,2'-azobisisobutyronitrile

[0103] (Polymerization initiator) (additives) TESOX-D: 3-ethyl-3-[3-(triethoxysilyl)propoxymethyl]oxetane [ka]

[0104] [Synthesis Example] Synthesis of methacrylate polymer powder P1 M1 (49.9 g, 150 mmol) and M2 (68.9 g, 225 mmol) were dissolved in THF (482.2 g) and degassed using a diaphragm pump. Then, AIBN (1.23 g, 7.5 mmol) was added and degassed again. The mixture was then allowed to react at 60°C for 8 hours to obtain a methacrylate polymer solution. This polymer solution was added dropwise to a mixture of methanol (3,020 g) and pure water (1,200 g), and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure to obtain 101.1 g of methacrylate polymer powder P1.

[0105] [Preparation Example] Preparation of polymer solution The methacrylate polymer powder P1 (20.0 g) obtained in Polymer Synthesis Example P1 was added to NMP (50.0 g) and dissolved by stirring at room temperature for 3 hours. To this solution, PGME (10.0 g), BCS (20.0 g), TESOX-D (1.00 g), and Megafac R-40 (0.01 g) were added and stirred to obtain polymer solution Q1.

[0106] [Fabrication of phase difference evaluation substrate] [Example 1] The polymer solution Q1 was filtered through a filter with a pore size of 5.0 μm, spin-coated on a glass substrate equipped with a transparent electrode, and dried on a hot plate at 70°C for 240 seconds to form a retardation film with a thickness of 3.0 μm. Next, polarized ultraviolet light was irradiated on the coated film surface at 20 mJ / cm. 2 After irradiation (313 nm equivalent), a total ultraviolet ray of 100 mJ / cm was applied through an exposure mask with L / S = 30 μm. 2 After the second exposure to ultraviolet light, the substrate was heated on a hot plate at 140° C. for 20 minutes to obtain a substrate R1 with a retardation film.

[0107] [Example 2] The polymer solution Q1 was filtered through a filter with a pore size of 5.0 μm, then spin-coated onto a glass substrate with a transparent electrode, and dried on a hot plate at 70°C for 240 seconds to form a retardation film with a thickness of 3.0 μm. Next, the coating surface was exposed to a total ultraviolet ray of 100 mJ / cm2 through an exposure mask with an L / S=30 μm. 2 After irradiation (313 nm equivalent), the exposure mask was removed and polarized UV light was applied at 20 mJ / cm 2 After the second exposure to ultraviolet light, the substrate was heated on a hot plate at 140° C. for 20 minutes to obtain a substrate R2 with a retardation film.

[0108] [Example 3] The polymer solution Q1 was filtered through a filter with a pore size of 5.0 μm, spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at 70°C for 240 seconds to form a retardation film with a thickness of 3.0 μm. Then, the coated film was irradiated with total ultraviolet light at 10 mJ / cm2. 2 After irradiation (313 nm equivalent), polarized ultraviolet light was applied at 20 mJ / cm through an exposure mask with L / S = 30 μm. 2 After the second exposure to ultraviolet light, the substrate was heated on a hot plate at 140° C. for 20 minutes to obtain a substrate R3 with a retardation film.

[0109] [Example 4] The polymer solution Q1 was filtered through a filter with a pore size of 5.0 μm, spin-coated on a glass substrate equipped with a transparent electrode, and dried on a hot plate at 70°C for 240 seconds to form a retardation film with a thickness of 3.0 μm. Polarized ultraviolet light was irradiated on the coated film surface at 20 mJ / cm. 2 Subsequently, polarized ultraviolet light was irradiated at 20 mJ / cm 2 through an exposure mask having an L / S of 30 μm, so as to be perpendicular to the polarization axis of the first polarized ultraviolet light. 2 After the second exposure to ultraviolet light, the substrate was heated on a hot plate at 140° C. for 20 minutes to obtain a substrate R4 with a retardation film.

[0110] [Example 5] The polymer solution Q1 was filtered through a filter with a pore size of 5.0 μm, spin-coated onto a glass substrate equipped with a transparent electrode, and dried on a hot plate at 70°C for 240 seconds to form a retardation film with a thickness of 3.0 μm. Polarized ultraviolet light was irradiated at 20 mJ / cm2 through an exposure mask with an L / S=30 μm on the coated surface. 2 Next, the exposure mask was removed, and polarized UV light was irradiated at 20 mJ / cm 2 so as to be perpendicular to the polarization axis of the first polarized UV light. 2 After the second exposure to ultraviolet light, the substrate was heated on a hot plate at 140° C. for 20 minutes to obtain a substrate R5 with a retardation film.

[0111] [Example 6] The polymer solution Q1 was filtered through a filter with a pore size of 5.0 μm, spin-coated on a glass substrate equipped with a transparent electrode, and dried on a hot plate at 70°C for 240 seconds to form a retardation film with a thickness of 3.0 μm. Polarized ultraviolet light was irradiated on the coated film surface at 20 mJ / cm. 2 Subsequently, polarized ultraviolet light was irradiated at 100 mJ / cm 2 through an exposure mask having an L / S of 30 μm so as to be parallel to the polarization axis of the first polarized ultraviolet light. 2 After the second exposure to ultraviolet light, the substrate was heated on a hot plate at 140° C. for 20 minutes to obtain a substrate R6 with a retardation film.

[0112] [Example 7] The polymer solution Q1 was filtered through a filter with a pore size of 5.0 μm, spin-coated on a glass substrate equipped with a transparent electrode, and dried on a hot plate at 70°C for 240 seconds to form a retardation film with a thickness of 3.0 μm. Polarized ultraviolet light was irradiated on the coated film surface at 20 mJ / cm. 2 Subsequently, polarized ultraviolet light was irradiated at 200 mJ / cm 2 through an exposure mask having an L / S of 30 μm so as to be parallel to the polarization axis of the first polarized ultraviolet light. 2 After the second exposure to ultraviolet light, the substrate was heated on a hot plate at 140° C. for 20 minutes to obtain a substrate R7 with a retardation film.

[0113] [Example 8] The polymer solution Q1 was filtered through a filter with a pore size of 5.0 μm, spin-coated on a glass substrate equipped with a transparent electrode, and dried on a hot plate at 70°C for 240 seconds to form a retardation film with a thickness of 3.0 μm. Polarized ultraviolet light was irradiated on the coated film surface at 20 mJ / cm. 2 Subsequently, polarized UV light was irradiated at 400 mJ / cm 2 through an exposure mask having an L / S of 30 μm so as to be parallel to the polarization axis of the first polarized UV light. 2 After the second exposure to ultraviolet light, the substrate was heated on a hot plate at 140° C. for 20 minutes to obtain a substrate R8 with a retardation film.

[0114] [Comparative Example 1] The polymer solution Q1 was filtered through a filter with a pore size of 5.0 μm, spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at 70°C for 240 seconds to form a retardation film with a thickness of 3.0 μm. Next, polarized ultraviolet light was irradiated on the coated film surface at 20 mJ / cm through an exposure mask with an L / S=20 μm. 2 After the polarized UV exposure, the film was heated on a hot plate at 140° C. for 20 minutes to obtain a substrate S1 with a retardation film.

[0115] The exposure steps of Examples 1 to 8 and Comparative Example 1 are summarized in Table 1. In Examples 1, 2, and 4 to 8, the areas covered by the exposure mask became high anisotropy regions (hereinafter also referred to as anisotropic phase regions), and the areas not covered by the exposure mask became low anisotropy regions (hereinafter also referred to as isotropic phase regions). In Example 3, the areas covered by the exposure mask became isotropic phase.

[0116] [Table 1]

[0117] [Creating a haze evaluation board] [Preparation of substrate T1] The polymer solution Q1 was filtered through a filter with a pore size of 5.0 μm, spin-coated on a glass substrate equipped with a transparent electrode, and dried on a hot plate at 70°C for 240 seconds to form a retardation film with a thickness of 3.0 μm. Next, polarized ultraviolet light was irradiated on the coated film surface at 20 mJ / cm. 2 After the ultraviolet exposure, the substrate was heated on a hot plate at 140°C for 20 minutes to obtain a substrate T1 with a retardation film. The substrate T1 is a substrate that imitates the haze of the anisotropic phase regions of Examples 1 and 2, Examples 4 to 8, and Comparative Example 1.

[0118] [Preparation of substrate T2] The polymer solution Q1 was filtered through a filter with a pore size of 5.0 μm, spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at 70°C for 240 seconds to form a retardation film with a thickness of 3.0 μm. Then, the coated film was irradiated with total ultraviolet light at 10 mJ / cm2. 2 (313 nm equivalent) After irradiation with polarized UV light at 20 mJ / cm 2 After the second exposure to ultraviolet light, the substrate was heated on a hot plate at 140°C for 20 minutes to obtain a substrate T2 with a retardation film. The substrate T2 is a substrate that imitates the haze of the anisotropic phase region of Example 3.

[0119] [Preparation of substrate T3] The polymer solution Q1 was filtered through a filter with a pore size of 5.0 μm, spin-coated on a glass substrate equipped with a transparent electrode, and dried on a hot plate at 70°C for 240 seconds to form a retardation film with a thickness of 3.0 μm. Next, polarized ultraviolet light was irradiated on the coated film surface at 20 mJ / cm. 2 After irradiation (313 nm equivalent), the total UV light is 100 mJ / cm 2 After the second UV exposure, the substrate was heated on a hot plate at 140°C for 20 minutes to obtain a substrate S3 with a retardation film. The substrate T3 is a substrate simulating the haze in the isotropic phase region of Example 1.

[0120] [Preparation of substrate T4] The polymer solution Q1 was filtered through a filter with a pore size of 5.0 μm, spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at 70°C for 240 seconds to form a retardation film with a thickness of 3.0 μm. Then, the coated film was irradiated with total ultraviolet light at 100 mJ / cm2. 2 (313 nm equivalent) After irradiation with polarized UV light at 20 mJ / cm 2 After the second UV exposure, the substrate was heated on a hot plate at 140°C for 20 minutes to obtain a substrate T4 with a retardation film. The substrate T4 is a substrate that mimics the haze in the isotropic phase region of Example 2.

[0121] [Preparation of substrate T5] The polymer solution Q1 was filtered through a filter with a pore size of 5.0 μm, spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at 70°C for 240 seconds to form a retardation film with a thickness of 3.0 μm. Then, the coated film was irradiated with total ultraviolet light at 10 mJ / cm2. 2 After the ultraviolet exposure, the substrate was heated on a hot plate at 140° C. for 20 minutes to obtain a substrate T5 with a retardation film. The substrate T5 is a substrate simulating the haze in the isotropic phase region of Example 3.

[0122] [Preparation of substrate T6] The polymer solution Q1 was filtered through a filter with a pore size of 5.0 μm, spin-coated on a glass substrate equipped with a transparent electrode, and dried on a hot plate at 70°C for 240 seconds to form a retardation film with a thickness of 3.0 μm. Polarized ultraviolet light was irradiated on the coated film surface at 20 mJ / cm. 2 (313 nm equivalent). Then, polarized UV light was irradiated at 20 mJ / cm 2 so that the polarization axis was perpendicular to the first polarized UV light. 2 After the second UV exposure, the substrate was heated on a hot plate at 140°C for 20 minutes to obtain a substrate T6 with a retardation film. Substrate T6 is a substrate that mimics the haze in the isotropic phase region of Examples 4 and 5.

[0123] [Preparation of substrate T7] The polymer solution Q1 was filtered through a filter with a pore size of 5.0 μm, spin-coated on a glass substrate equipped with a transparent electrode, and dried on a hot plate at 70°C for 240 seconds to form a retardation film with a thickness of 3.0 μm. Polarized ultraviolet light was irradiated on the coated film surface at 20 mJ / cm. 2 (313 nm equivalent). Then, polarized UV light was irradiated at 100 mJ / cm 2 so that the polarization axis was parallel to the first polarized UV light. 2 After the second UV exposure, the substrate was heated on a hot plate at 140°C for 20 minutes to obtain substrate T7 with a retardation film. Substrate T7 is a substrate that mimics the haze in the isotropic phase region of Example 6.

[0124] [Preparation of substrate T8] The polymer solution Q1 was filtered through a filter with a pore size of 5.0 μm, spin-coated on a glass substrate equipped with a transparent electrode, and dried on a hot plate at 70°C for 240 seconds to form a retardation film with a thickness of 3.0 μm. Polarized ultraviolet light was irradiated on the coated film surface at 20 mJ / cm. 2 (313 nm equivalent). Then, polarized UV light was irradiated at 200 mJ / cm 2 so that the polarization axis was parallel to the first polarized UV light. 2 After the second UV exposure, the substrate was heated on a hot plate at 140°C for 20 minutes to obtain a substrate T8 with a retardation film. Substrate T8 is a substrate that mimics the haze in the isotropic phase region of Example 7.

[0125] [Preparation of substrate T9] The polymer solution Q1 was filtered through a filter with a pore size of 5.0 μm, spin-coated on a glass substrate equipped with a transparent electrode, and dried on a hot plate at 70°C for 240 seconds to form a retardation film with a thickness of 3.0 μm. Polarized ultraviolet light was irradiated on the coated film surface at 20 mJ / cm. 2 (313 nm equivalent). Then, polarized UV light was irradiated at 400 mJ / cm 2 so that the polarization axis was parallel to the first polarized UV light. 2 After the second exposure to ultraviolet light, the substrate was heated on a hot plate at 140°C for 20 minutes to obtain a substrate T9 with a retardation film. Substrate T9 is a substrate that mimics the haze in the isotropic phase region of Example 8.

[0126] [Preparation of substrate T10] Polymer solution Q1 was filtered through a 5.0 μm pore size filter, then spin-coated onto a glass substrate with a transparent electrode and dried on a hot plate at 70°C for 240 seconds to form a 3.0 μm thick retardation film. It was then heated on a hot plate at 140°C for 20 minutes to obtain substrate T10 with a retardation film. Substrate T10 is a substrate that mimics the haze in the isotropic phase region of Comparative Example 1.

[0127] [Phase difference evaluation] The retardation values ​​at 550 nm of the retardation film-coated substrates R1 to R8 and the retardation film-coated substrate S1 were evaluated using Axo Step manufactured by Axo Metrix. The results are shown in Table 2.

[0128] [HAZE rating] The haze of the retardation film-attached substrates T1 to T10 was evaluated using a haze meter HZ-V3 manufactured by Suga Test Instruments Co., Ltd. The results are shown in Table 2.

[0129] [Table 2]

[0130] From the results in Table 2, comparing Examples 1 to 8 with Comparative Example 1, it was found that the haze value of the isotropic phase region was suppressed by irradiating the isotropic phase region with ultraviolet light. However, differences in the irradiation process resulted in differences in the retardation values ​​of the anisotropic and isotropic phases in Examples 1 to 8. Among them, Examples 4 and 5 not only suppressed the haze value, but also showed a large difference in the retardation values ​​between the anisotropic and isotropic phases, resulting in a high retardation value in the anisotropic phase and a suppressed retardation value in the isotropic phase, resulting in very good results. Furthermore, Examples 6 to 8 showed that the retardation value of the isotropic phase was suppressed as the second polarized light exposure dose increased. This is because the methacrylate polymer powder P1 has the property of reducing orientation at exposure doses exceeding the optimal exposure dose. [Industrial Applicability]

[0131] The method of the present invention is useful as a method for producing a patterned single-layer retardation material in which the haze value of the isotropic phase region is suppressed.

Claims

1. (I) a step of applying a polymer composition containing a liquid crystalline polymer, the polymer having a property that the orientation increases with increasing exposure amount when the exposure amount is less than the optimum exposure amount, and decreases with increasing exposure amount when the exposure amount is more than the optimum exposure amount, to a substrate to form a coating film; (II) irradiating the coating film obtained in step (I) with polarized UV light twice, at least once through a mask and at least once with UV light, so as to produce high-anisotropy regions with high optical anisotropy by irradiation with polarized UV light, and low-anisotropy regions with relatively low optical anisotropy due to an insufficient amount of UV light in regions below the optimal exposure dose and an excess amount in regions above the optimal exposure dose; and (III) A step of heating the coating film obtained in step (II) to obtain a retardation material. A method for manufacturing a patterned single-layer retardation material, comprising: A method for producing a patterned single-layer retardation material, wherein in step (II), ultraviolet light is irradiated to both the region having anisotropy and the region having less anisotropy than that.

2. The polymer composition (A) a side chain polymer having a side chain having a photoreactive moiety represented by the following formula (a): (B) a silane coupling agent; and (C) Organic Solvent The method for producing a patterned single-layer retardation material according to claim 1, comprising: 【Chemistry 1】 (In the formula, R 1 is an alkylene group having 1 to 30 carbon atoms, and one or more hydrogen atoms of the alkylene group may be substituted with a fluorine atom or an organic group. 1 -CH in 2 CH 2 - may be replaced by -CH=CH-, and R 1 -CH in 2 - may be substituted with a group selected from the group consisting of -O-, -NH-C(=O)-, -C(=O)-NH-, -C(=O)-O-, -O-C(=O)-, -NH-, -NH-C(=O)-NH- and -C(=O)-, provided that adjacent -CH 2 - cannot be substituted with these groups at the same time. 2 - is R 1 -CH at the end of the middle 2 - may also be the case. R 2 is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group, or a divalent fused ring group. R 3 represents a single bond, —O—, —C(═O)—O—, —O—C(═O)—, or —CH═CH—C(═O)—O—. R is 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 cyano group, or a nitro group, and when c≧2, each R may be the same or different. a is 0, 1 or 2. b is 0 or 1. c is an integer that satisfies 0≦c≦2b+4. The dashed lines represent bonds.)

3. 3. The method for producing a patterned single-layer retardation material according to claim 2, wherein the side chain having the photoreactive site is represented by the following formula (a1): 【Chemistry 2】 (In the formula, R 1 , R 2 and a are the same as above. R 3A is a single bond, —O—, —C(═O)—O— or —O—C(═O)—. The benzene ring in formula (a1) may be substituted with 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 cyano group, and a nitro group. The dashed lines represent bonds.)

4. 4. The method for producing a patterned single-layer retardation material according to claim 2, wherein the side chain type polymer (A) further has a side chain that exhibits only liquid crystallinity.

5. 5. The method for producing a patterned single-layer retardation material according to claim 4, wherein the side chain exhibiting only liquid crystallinity is a liquid crystalline side chain represented by any one of the following formulas (1) to (13): 【Transformation 3】 【Chemistry 4】 (In the formula, A 1 , A 2 are each independently a single bond, —O—, or —CH 2 -, -C(=O)-O-, -O-C(=O)-, -C(=O)-NH-, -NH-C(=O)-, -CH=CH-C(=O)-O- or -O-C(=O)-CH=CH-. R 11 Ha-NO 2 , —CN, a halogen atom, a phenyl group, a naphthyl group, a biphenylyl group, a furanyl 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 alkyloxy group having 1 to 12 carbon atoms. R 12 is a group selected from the group consisting of a phenyl group, a naphthyl group, a biphenylyl group, a furanyl group, a monovalent nitrogen-containing heterocyclic group, a monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and groups obtained by combining these groups, and the hydrogen atom bonded to the group is -NO 2 , —CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. R 13 is a hydrogen atom, -NO 2 , -CN, -CH=C(CN) 2 , -CH=CH-CN, a halogen atom, a phenyl group, a naphthyl group, a biphenylyl group, a furanyl 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— or —O—C(═O)—. d is an integer from 1 to 12. k1 to k5 are each independently an integer of 0 to 2, provided that the sum of k1 to k5 is 2 or more. k6 and k7 each independently represent an integer of 0 to 2, provided that the sum of k6 and k7 is 1 or greater. m1, m2, and m3 each independently represent an integer of 1 to 3. n is 0 or 1. Z 1 and Z 2 are each independently a single bond, —C(═O)—, or —CH 2 O—, —CH═N—, or —CF 2 - is. The dashed lines represent bonds.)

6. 6. The method for producing a patterned single-layer retardation material according to claim 5, wherein the side chain exhibiting only liquid crystallinity is a liquid crystalline side chain represented by any one of formulas (1) to (11).

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