WO2013133078A1 - 重合体、該重合体を含む組成物、及び単層塗布型水平配向フィルム - Google Patents

重合体、該重合体を含む組成物、及び単層塗布型水平配向フィルム Download PDF

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WO2013133078A1
WO2013133078A1 PCT/JP2013/054870 JP2013054870W WO2013133078A1 WO 2013133078 A1 WO2013133078 A1 WO 2013133078A1 JP 2013054870 W JP2013054870 W JP 2013054870W WO 2013133078 A1 WO2013133078 A1 WO 2013133078A1
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group
polymer
formula
film
mmol
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ダニエルアントニオ 櫻葉汀
昇志郎 湯川
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日産化学工業株式会社
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Priority to JP2014503773A priority patent/JP6003977B2/ja
Priority to KR1020147021693A priority patent/KR101988377B1/ko
Publication of WO2013133078A1 publication Critical patent/WO2013133078A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/58—One oxygen atom, e.g. butenolide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C08F220/301—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one oxygen in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C08F220/303—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one or more carboxylic moieties in the chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L37/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen; Compositions of derivatives of such polymers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F224/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films

Definitions

  • the present invention relates to a polymer, a composition containing the polymer, and a single-layer coating type horizontal alignment film.
  • materials having optical characteristics suitable for applications such as display devices and recording materials, particularly liquid crystalline polymers that can be suitably used for optical compensation films such as polarizing plates and retardation plates for liquid crystal displays, and the polymers And a single-layer coated horizontal alignment film obtained from the composition.
  • the polymerizable liquid crystal compound used here is generally a liquid crystal compound having a polymerizable group and a liquid crystal structure part (structure part having a spacer part and a mesogen part), and an acrylic group is widely used as the polymerizable group. ing.
  • Such a polymerizable liquid crystal compound is generally made into a polymer (film) by a method of polymerizing by irradiation with radiation such as ultraviolet rays.
  • a method of polymerizing by irradiation with radiation such as ultraviolet rays.
  • a method in which a specific polymerizable liquid crystal compound having an acrylic group is supported between supports and a polymer is obtained by irradiating radiation while maintaining the compound in a liquid crystal state Patent Document 1
  • Patent Document 2 a method of obtaining a polymer by adding a photopolymerization initiator to a mixture of two kinds of polymerizable liquid crystal compounds or a composition obtained by mixing a chiral liquid crystal with this mixture and irradiating ultraviolet rays.
  • Patent Documents 3 and 4 an alignment film using a polymerizable liquid crystal compound or polymer that does not require a liquid crystal alignment film
  • Patent Documents 5 and 6 an alignment film using a polymer containing a photocrosslinking site
  • JP-A-62-70407 JP-A-9-208957 European Patent Application No. 1093025 International Publication No. 2008/031243 JP 2008-164925 A Japanese Patent Laid-Open No. 11-189665
  • the present invention has been made in view of the above-described problems, and is obtained from a novel polymer capable of producing a single-layer coating type horizontal alignment film by a simpler process, a composition containing the polymer, and the composition.
  • An object of the present invention is to provide a single layer coating type horizontal alignment film.
  • the inventors of the present invention have included a ⁇ -butyrolactone skeleton in the main chain and a heavy chain having a cinnamate structure on the side chain extending from the ⁇ position of the lactone ring.
  • a horizontal alignment film having a high refractive index anisotropy ( ⁇ n) can be obtained without using a liquid crystal alignment film, because a stable network structure is formed after polarized ultraviolet light exposure.
  • the present inventors have found that by introducing an alkyl chain into the polymer, the solubility in an organic solvent is improved, and a horizontally oriented film having a higher ⁇ n can be produced under low temperature conditions, thereby completing the present invention.
  • a polymer comprising repeating units represented by the following formulas [1a], [1b] and [1c], [Wherein, X and Y are each independently a group represented by the following formula [2] or [3], (In the formula [3], R 1 is a hydrogen atom or a methyl group. The broken line is a bond.)
  • M 1 is a group represented by the following formula [4]
  • M 2 is a group represented by the following formula [5], (In the formulas [4] and [5], s1, s2, s3 and s4 are each independently 1 or 2, and G 1 and G 2 are each independently a single bond, —COO— or —OCO—.
  • R 2 and R 3 are each independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.
  • A is a linear or branched alkyl group having 2 to 15 carbon atoms, m, n, and p are numbers satisfying 0 ⁇ m ⁇ 1, 0 ⁇ n ⁇ 1, 0 ⁇ p ⁇ 0.5, and m + n + p ⁇ 1, respectively.
  • q and r are each independently an integer of 2 to 9. ] 2. 1 polymer in which X and Y are groups represented by the above formula [3], 3.
  • a polymerizable compound represented by the following formula [7] (In the formula [7], s3 and s4 are each independently 1 or 2, G 2 is a single bond, —COO— or —OCO—, and R 3 is a hydrogen atom, a halogen atom or a cyano group. , An alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.) I will provide a.
  • the polymer of the present invention contains a ⁇ -butyrolactone skeleton in the main chain. Therefore, it is possible to produce a single-layer coated horizontal alignment film exhibiting high ⁇ n by a process of applying a composition containing this polymer, irradiating linearly polarized light at room temperature, and performing post-baking. Further, by using a polymer containing a unit having an alkyl group side chain, solubility in a solvent can be improved.
  • the polymer of the present invention contains repeating units represented by the following formulas [1a] and [1b], and further contains a repeating unit represented by the following formula [1c] as necessary.
  • X and Y are each independently a group represented by the following formula [2] or [3].
  • R 1 is a hydrogen atom or a methyl group. The broken line is a bond (the same applies hereinafter).)
  • a group represented by the formula [3] is preferable for both X and Y.
  • M 1 is a group represented by the following formula [4]
  • M 2 is a group represented by the following formula [5].
  • s1, s2, s3 and s4 are each independently 1 or 2
  • G 1 and G 2 are each independently a single bond, —COO— or —OCO—.
  • R 2 and R 3 are each independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.
  • examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • a fluorine atom is preferable.
  • the alkyl group may be linear, branched or cyclic, and the number of carbon atoms is not particularly limited, but in the present invention, a linear alkyl group having 1 to 10 carbon atoms is preferable.
  • alkyl group examples include methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, cyclobutyl group, n- Examples include a pentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decyl group. Of these, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group, an ethyl group, and the like are particularly preferable.
  • the alkoxy group may be linear, branched or cyclic, and the number of carbon atoms is not particularly limited, but in the present invention, a straight-chain alkoxy group having 1 to 10 carbon atoms is preferable.
  • Specific examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, s-butoxy group, t-butoxy group, n-pentoxy group, n-hexyl. Examples thereof include an oxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group and the like.
  • an alkoxy group having 1 to 3 carbon atoms is more preferable, and a methoxy group, an ethoxy group, and the like are particularly preferable.
  • part or all of the hydrogen atoms may be substituted with a halogen atom such as a fluorine atom.
  • R 2 or R 3 is more preferably a hydrogen atom, a fluorine atom, a cyano group, a methyl group, or a methoxy group.
  • G 1 is preferably —COO— or —OCO—, and G 2 is preferably a single bond.
  • A is a linear or branched alkyl group having 2 to 15 carbon atoms.
  • Specific examples of the alkyl group include ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group, 1-methyl group.
  • -N-butyl group 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2- Dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4- Methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group Group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propy
  • an alkyl group having 4 to 15 carbon atoms, particularly 4 to 12 carbon atoms is preferable, and an n-butyl group, 2-ethyl-n-hexyl group, n -Dodecyl group and the like are more preferable.
  • m, n, and p are numbers satisfying 0 ⁇ m ⁇ 1, 0 ⁇ n ⁇ 1, 0 ⁇ p ⁇ 0.5, and m + n + p ⁇ 1, respectively.
  • m, n, and p are 0.2 ⁇ m ⁇ 0.9, 0.1 ⁇ n ⁇ 0.8, and 0 ⁇ p ⁇ 0. Is preferably a number satisfying 0.2 ⁇ m ⁇ 0.8, 0.1 ⁇ n ⁇ 0.5, and 0.1 ⁇ p ⁇ 0.3.
  • q and r are each independently an integer of 2 to 9, preferably 3 to 6, and more preferably 5 or 6 as q.
  • the polymerizable compound that is a raw material of the polymer of the present invention is represented by the following formula [6], [7], or [8]. [Wherein, R 2 , R 3 , G 1 , G 2 , A, q, r, and s1 to s4 are the same as above.
  • X ′ and Y ′ are each independently a polymerizable group represented by the following formula [9] or [10]. (Wherein R 1 is the same as above)]
  • G 1 is —COO—, as shown in the following scheme, it is produced by condensing a benzoic acid derivative represented by the formula [12] and a phenol derivative in a solvent in the presence of a condensing agent.
  • the (In the formula, R 2 , X ′, q, s1 and s2 are the same as above.
  • DCC represents N, N′-dicyclohexylcarbodiimide and DMAP represents 4-dimethylaminopyridine.
  • G 1 is —OCO—, it is produced by condensing a phenol derivative represented by the formula [13] and a benzoic acid derivative in a solvent in the presence of a condensing agent, as represented by the following scheme.
  • a condensing agent as represented by the following scheme. The (Wherein R 2 , X ′, q, s1 and s2 are the same as above)
  • the compounds represented by the above formulas [12] and [13] are commercially available from SYNTHON Chemicals or Midori Chemical Co. when X ′ is a group represented by the formula [9]. Further, in the compounds represented by the above formulas [12] and [13], when X ′ is a group represented by the formula [10], for example, Talaga et al. (P. Talaga, M. Schaeffer, C. Benezra and JL Stampf, Synthesis, 530 (1990)). As shown in the following synthesis scheme (A1), this technique is a method of reacting 2- (bromomethyl) propenoic acid with aldehyde or ketone using SnCl 2. .
  • 2- (Bromomethyl) acrylic acid can be obtained by a method proposed by Ramarajan et al. (K. Ramarajan, K. Kamalingam, DJ O'Donnell and KD Berlin, Organic Synthesis, vol. 61, pp. 56- 59 (1983)).
  • R ′ represents a monovalent organic group
  • Amberlyst (registered trademark) 15 is an ion exchange resin manufactured by Rohm and Haas
  • THF represents tetrahydrofuran
  • Et represents an ethyl group.
  • an ⁇ -methylene- ⁇ -butyrolactone structure can also be obtained by reaction with a corresponding acetal or ketal instead of an aldehyde or a ketone.
  • the acetal or ketal include compounds having a dimethyl acetal group, a diethyl acetal group, a 1,3-dioxane group, a 1,3-dioxolane group, and the like.
  • a synthesis method and a protecting group when acetal or ketal is used are shown in the following synthesis scheme (A2).
  • a compound represented by the formula [12] or [13] can be synthesized by the method of the following synthesis scheme (B) or (C) to which the method of the synthesis scheme (A1) or (A2) is applied.
  • q and s1 are the same as above.
  • Me represents a methyl group.
  • PCC represents pyridinium chlorochromate.
  • the compound represented by the formula [7] is, for example, condensed with a compound represented by the formula [14] and a cinnamic acid compound in a solvent in the presence of a condensing agent, as represented by the following scheme. It is manufactured by. (In the formula, R 3 , G 2 , r, s3 and s4 are the same as above.)
  • the compound represented by the formula [14] can be obtained, for example, by the method shown in the following synthesis scheme (D). (In the formula, G 2 , r, s3 and s4 are the same as above.)
  • the method for synthesizing the polymer of the present invention is not particularly limited, and radical polymerization, anionic polymerization, cationic polymerization and the like can be employed. Of these, radical polymerization is particularly preferred.
  • the polymerizable compound may be heated and polymerized in a solvent in the presence of a polymerization initiator.
  • the polymerization initiator can be appropriately selected from conventionally known ones.
  • peroxides such as benzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide; persulfates such as sodium persulfate, potassium persulfate, ammonium persulfate; azobisisobutyronitrile (AIBN), azo
  • AIBN azobisisobutyronitrile
  • azo compounds such as bismethylbutyronitrile and azobisisovaleronitrile. These can be used individually by 1 type or in combination of 2 or more types.
  • the amount of the polymerization initiator used is preferably about 0.01 to 0.05 mol with respect to 1 mol of the polymerizable compound.
  • the reaction temperature may be appropriately set from 0 ° C. to the boiling point of the solvent used, but is preferably about 20 to 100 ° C.
  • the reaction time is preferably about 0.1 to 30 hours.
  • the solvent used in the polymerization reaction is not particularly limited, and may be appropriately selected from various solvents generally used in the polymerization reaction. Specifically, water; methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, i-butanol, t-butanol, 1-pentanol, 2-pentanol, 3-pentanol, alcohols such as i-pentanol, t-pentanol, 1-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 2-octanol, 2-ethyl-1-hexanol, benzyl alcohol, cyclohexanol; diethyl ether , Ethers such as diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, tetrahydrofuran and 1,4-dioxane; halogenated
  • the polymer of the present invention preferably has a weight average molecular weight of 3,000 to 200,000, more preferably 4,000 to 150,000, and further preferably 5,000 to 100,000. preferable. If the weight average molecular weight exceeds 200,000, the solubility in a solvent may be reduced and handling properties may be reduced. If the weight average molecular weight is less than 3,000, curing is insufficient at the time of thermosetting, and solvent resistance and heat resistance are reduced. May decrease.
  • a weight average molecular weight is a polystyrene conversion measured value by gel permeation chromatography (GPC).
  • the polymer of the present invention may contain other repeating units other than the above formulas [1a] to [1c] as long as the effects of the present invention are not impaired.
  • the polymerizable compound that gives other repeating units include acrylic ester compounds, methacrylic ester compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, and styrene compounds.
  • the content of the other repeating units is preferably 0 to 10 mol% in 100 mol% of all repeating units. If the content of the other repeating unit is too large, the properties of the polymer of the present invention, for example, properties such as liquid crystallinity may be deteriorated.
  • the polymer of the present invention contains the other repeating unit, as a synthesis method thereof, the polymerization may be carried out in the presence of a polymerizable compound that gives the other repeating unit.
  • the polymer of the present invention may be any of a random copolymer, an alternating copolymer, and a block copolymer.
  • composition of the present invention can be obtained by mixing at least one of the above polymers and an organic solvent.
  • organic solvent examples include ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbons such as benzene, toluene and xylene; polar solvents such as N, N-dimethylformamide and N-methyl-2-pyrrolidone; , Esters such as butyl acetate and ethyl lactate; methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate, 2-ethoxypropion Alkoxy esters such as ethyl acetate; Glycol dialkyl ethers such as ethylene glycol dimethyl ether and propylene glycol dimethyl ether; Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Diglycol dialkyl ethers such as methyl ethyl ether and dipropy
  • propylene glycol monomethyl ether propylene glycol monomethyl ether acetate, ethyl lactate, cyclohexanone and the like are preferable.
  • the amount of the organic solvent used is preferably about 60 to 95% by mass in the composition.
  • a surfactant may be added to the composition of the present invention for the purpose of improving the affinity with the substrate.
  • the surfactant is not particularly limited, and examples thereof include fluorine-based surfactants, silicone-based surfactants, nonionic surfactants, etc., but fluorine-based surfactants having a high effect of improving affinity with the substrate. Agents are preferred.
  • fluorosurfactants hereinafter referred to as trade names
  • EFTOP EF301, EF303, EF352 manufactured by Tochem Products
  • MegaFuck F171, F173, R-30 manufactured by DIC Corporation
  • FLORARD FC430, FC431 Suditomo 3M Co., Ltd.
  • Asahi Guard AG710 Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.), etc. Is not to be done.
  • surfactant can also be used individually or in combination of multiple types, The addition amount is 5 mass parts or less with respect to 100 mass parts of polymers.
  • Adhesion promoters include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane; trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, phenyltri Alkoxysilanes such as ethoxysilane; silazanes such as hexamethyldisilazane, N, N′-bis (trimethylsilyl) urea, dimethyltrimethylsilylamine, trimethylsilylimidazole; vinyltrichlorosilane, ⁇ -chloropropyltrimethoxysilane, ⁇ -amino Propy
  • the adhesion promoter can be used alone or in combination of two or more kinds, and the addition amount is preferably 1 part by mass or less with respect to 100 parts by mass of the polymer.
  • the composition of the present invention described above is a substrate (for example, a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, chromium, etc., a glass substrate, a quartz substrate, an ITO substrate, etc.
  • a substrate for example, a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, chromium, etc., a glass substrate, a quartz substrate, an ITO substrate, etc.
  • films for example, triacetyl cellulose (TAC) film, cycloolefin polymer film, polyethylene terephthalate film, resin film such as acrylic film), etc., bar coat, spin coat, flow coat, roll coat, slit coat,
  • TAC triacetyl cellulose
  • a film can be formed by applying a slit coat followed by spin coating, an ink jet method, a printing method, or the like to form a coating film, followed by heat drying with a hot plate or an oven.
  • a heating temperature and a heating time appropriately selected from the range of a temperature of 50 to 100 ° C. and a time of 0.1 to 60 minutes are employed.
  • the heating temperature and heating time are preferably 50 to 80 ° C. and 0.1 to 2 minutes.
  • the film thus formed is irradiated with linearly polarized light and post-baked to obtain a single-layer coating type horizontal alignment film.
  • a method of irradiating linearly polarized light ultraviolet light to visible light having a wavelength of 150 to 450 nm is usually used, and it is performed by irradiating the linearly polarized light at room temperature or in a heated state.
  • the post-bake may be heated with a hot plate or an oven, and the temperature and time are preferably 90 to 150 ° C. and 2 to 20 minutes, more preferably 95 to 120 ° C. and 5 to 20 minutes. is there.
  • the film thickness of the single-layer coating type horizontal alignment film of the present invention can be appropriately selected in consideration of the level difference of the substrate to be used and the optical and electrical properties, and is preferably 0.1 to 3 ⁇ m, for example.
  • the thus obtained single-layer coating type horizontal alignment film of the present invention is a material having optical characteristics suitable for applications such as display devices and recording materials, and in particular, polarizing plates and retardation plates for liquid crystal displays. It is suitable as an optical compensation film.
  • the precipitated DCC urea was filtered off, and the filtrate was washed with 0.5 mol / L hydrochloric acid 150 mL, saturated aqueous sodium hydrogen carbonate solution 150 mL and saturated brine 150 mL successively, dried over magnesium sulfate, and the solvent was removed. Distilled off and purified by recrystallization with ethanol to obtain 39.6 g of the target polymerizable compound (M1) (yield 89%). The measurement results of NMR are shown below.
  • the precipitated DCC urea was filtered off, and the filtrate was washed twice with 50 mol of 0.5 mol / L hydrochloric acid, 50 mL of saturated aqueous sodium hydrogen carbonate solution and 50 mL of saturated brine successively, dried over magnesium sulfate, and the solvent was removed. Distilled off and purified by recrystallization with ethanol to obtain 3.4 g of the target polymerizable compound (M3) (yield 72%).
  • M3 target polymerizable compound
  • the precipitated DCC urea was filtered off, and the filtrate was washed with 0.5 mol / L hydrochloric acid 150 mL, saturated aqueous sodium hydrogen carbonate solution 150 mL and saturated brine 150 mL successively, dried over magnesium sulfate, and the solvent was removed. Distilled off and purified by recrystallization with ethanol to obtain 21.5 g of the target polymerizable compound (M4) (yield 54%).
  • the measurement results of NMR are shown below.
  • the precipitated DCC urea was filtered off, and the filtrate was washed twice with 100 mol of 0.5 mol / L hydrochloric acid, 100 mL of saturated aqueous sodium hydrogen carbonate solution and 100 mL of saturated brine successively, dried over magnesium sulfate, and the solvent was removed. Distilled off and purified by recrystallization with ethanol to obtain 14.5 g of the target polymerizable compound (M5) (yield 74%). The measurement results of NMR are shown below.
  • compositions were prepared using the polymers obtained in the above Examples and Comparative Examples, films were prepared according to the following conditions, and the characteristics were examined.
  • Film production conditions Spin coating: 300 rpm / 5 seconds, 800-2,000 rpm / 20 seconds
  • Pre-baking 50 ° C./20 seconds (hot plate)
  • Exposure linearly polarized ultraviolet light, wavelength 313 nm, vertical irradiation, irradiation dose 500 mJ / cm 2
  • Post-bake 100 ° C / 10 minutes (hot plate)
  • Example 11 150 mg of polymer (1) and 0.3 mg of surfactant R-30 (manufactured by DIC Corporation) were dissolved in 850 mg of cyclohexanone to obtain a solution of polymer (1). This solution was applied to a glass substrate by spin coating, pre-baked, and then allowed to cool to room temperature. At this time, the obtained film on the substrate was transparent. Next, after the coating film formed on the glass substrate was exposed, it was post-baked. The obtained film had a thickness of 0.8 ⁇ m, and when observed with a polarizing microscope, it was confirmed that the film was horizontally oriented with respect to the substrate surface. And the retardation value ((DELTA) nd) was 62.3 nm and haze value was 2.1%.
  • Example 12 150 mg of the polymer (3) and 0.3 mg of surfactant R-30 (manufactured by DIC Corporation) were dissolved in 850 mg of cyclohexanone to obtain a solution of the polymer (3). This solution was applied to a glass substrate by spin coating, pre-baked, and then allowed to cool to room temperature. At this time, the obtained film on the substrate was transparent. Next, after the coating film formed on the glass substrate was exposed, it was post-baked. The obtained film had a thickness of 0.8 ⁇ m, and when observed with a polarizing microscope, it was confirmed that the film was horizontally oriented with respect to the substrate surface. And the (DELTA) nd was 96.7 nm and haze value was 1.3%.
  • Example 13 150 mg of the polymer (4) and 0.3 mg of the surfactant R-30 (manufactured by DIC Corporation) were dissolved in 850 mg of cyclohexanone to obtain a solution of the polymer (4). This solution was applied to a glass substrate by spin coating, pre-baked, and then allowed to cool to room temperature. At this time, the obtained film on the substrate was transparent. Next, after the coating film formed on the glass substrate was exposed, it was post-baked. The obtained film had a thickness of 0.9 ⁇ m, and when observed with a polarizing microscope, it was confirmed that the film was horizontally oriented with respect to the substrate surface. The ⁇ nd was 118.8 nm and the haze value was 0.9%.
  • Example 14 150 mg of the polymer (5) and 0.3 mg of the surfactant R-30 (manufactured by DIC Corporation) were dissolved in 850 mg of cyclohexanone to obtain a solution of the polymer (5). This solution was applied to a glass substrate by spin coating, pre-baked, and then allowed to cool to room temperature. At this time, the obtained film on the substrate was transparent. Next, after the coating film formed on the glass substrate was exposed, it was post-baked. The obtained film had a thickness of 0.9 ⁇ m, and when observed with a polarizing microscope, it was confirmed that the film was horizontally oriented with respect to the substrate surface. The ⁇ nd was 99.1 nm and the haze value was 0.4%.
  • Example 15 150 mg of polymer (6) and 0.3 mg of surfactant R-30 (manufactured by DIC Corporation) were dissolved in 850 mg of cyclohexanone to obtain a solution of polymer (6). This solution was applied to a glass substrate by spin coating, pre-baked, and then allowed to cool to room temperature. At this time, the obtained film on the substrate was transparent. Next, after the coating film formed on the glass substrate was exposed, it was post-baked. The obtained film had a thickness of 0.8 ⁇ m, and when observed with a polarizing microscope, it was confirmed that the film was horizontally oriented with respect to the substrate surface. And the (DELTA) nd was 113.3 nm and haze value was 0.9%.
  • Example 16 150 mg of polymer (7) and 0.3 mg of surfactant R-30 (manufactured by DIC Corporation) were dissolved in 850 mg of cyclohexanone to obtain a solution of polymer (7). This solution was applied to a glass substrate by spin coating, pre-baked, and then allowed to cool to room temperature. At this time, the obtained film on the substrate was transparent. Next, after the coating film formed on the glass substrate was exposed, it was post-baked. The obtained film had a thickness of 0.9 ⁇ m, and when observed with a polarizing microscope, it was confirmed that the film was horizontally oriented with respect to the substrate surface. The ⁇ nd was 118.3 nm and the haze value was 1.8%.
  • Example 17 150 mg of polymer (9) and 0.3 mg of surfactant R-30 (manufactured by DIC Corporation) were dissolved in 850 mg of cyclohexanone to obtain a solution of polymer (9). This solution was applied to a glass substrate by spin coating, pre-baked, and then allowed to cool to room temperature. At this time, the obtained film on the substrate was transparent. Next, after the coating film formed on the glass substrate was exposed, it was post-baked. The obtained film had a thickness of 0.8 ⁇ m, and when observed with a polarizing microscope, it was confirmed that the film was horizontally oriented with respect to the substrate surface. The ⁇ nd was 86.0 nm and the haze value was 2.2%.
  • Example 18 150 mg of the polymer (10) and 0.3 mg of the surfactant R-30 (manufactured by DIC Corporation) were dissolved in 850 mg of cyclohexanone / toluene (25/75, mass ratio), and the solution of the polymer (10) was dissolved. Obtained. This solution was applied to a glass substrate by spin coating, pre-baked, and then allowed to cool to room temperature. At this time, the obtained film on the substrate was transparent. Next, after the coating film formed on the glass substrate was exposed, it was post-baked. The obtained film had a thickness of 1.0 ⁇ m, and when observed with a polarizing microscope, it was confirmed that the film was horizontally oriented with respect to the substrate surface. And the (DELTA) nd was 77.3 nm and haze value was 0.5%.
  • Example 19 150 mg of the polymer (11) and 0.3 mg of the surfactant R-30 (DIC Corporation) were dissolved in 850 mg of cyclohexanone / toluene (25/75, mass ratio), and the solution of the polymer (11) was dissolved. Obtained. This solution was applied to a glass substrate by spin coating, pre-baked, and then allowed to cool to room temperature. At this time, the obtained film on the substrate was transparent. Next, after the coating film formed on the glass substrate was exposed, it was post-baked. The obtained film had a thickness of 0.9 ⁇ m, and when observed with a polarizing microscope, it was confirmed that the film was horizontally oriented with respect to the substrate surface. And the (DELTA) nd was 76.2 nm and haze value was 0.5%.
  • FIG. 1 and 2 show the angle dependency of the retardation value ( ⁇ nd) of the films produced in Examples 11 to 16 and Comparative Examples 3 and 4.

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