WO2015056741A1 - Composition pour former un film durci, matériau d'alignement et matériau de retardement - Google Patents

Composition pour former un film durci, matériau d'alignement et matériau de retardement Download PDF

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Publication number
WO2015056741A1
WO2015056741A1 PCT/JP2014/077546 JP2014077546W WO2015056741A1 WO 2015056741 A1 WO2015056741 A1 WO 2015056741A1 JP 2014077546 W JP2014077546 W JP 2014077546W WO 2015056741 A1 WO2015056741 A1 WO 2015056741A1
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group
component
cured film
carbon atoms
alignment
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PCT/JP2014/077546
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English (en)
Japanese (ja)
Inventor
伊藤　潤
昇志郎 湯川
耕平 後藤
真 畑中
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日産化学工業株式会社
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Priority to JP2015542656A priority Critical patent/JP6429030B2/ja
Priority to KR1020217012260A priority patent/KR20210049950A/ko
Priority to CN201480056944.9A priority patent/CN105659120B/zh
Priority to KR1020167009844A priority patent/KR102333902B1/ko
Publication of WO2015056741A1 publication Critical patent/WO2015056741A1/fr

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    • 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
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
    • G02F1/133788—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by light irradiation, e.g. linearly polarised light photo-polymerisation
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08F212/00—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 an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3083—Birefringent or phase retarding 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
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • 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
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine

Definitions

  • the present invention relates to a cured film forming composition, an alignment material, and a retardation material.
  • a right-eye image is visually recognized by an observer's right eye
  • a left-eye image is visually recognized by an observer's left eye, whereby a stereoscopic image can be displayed.
  • a retardation material is usually disposed on a display element such as a liquid crystal panel.
  • a retardation material a plurality of two kinds of retardation regions having different retardation characteristics are regularly arranged, and a patterned retardation material is formed.
  • a retardation material patterned so as to arrange a plurality of retardation regions having different retardation characteristics is referred to as a patterned retardation material.
  • the patterned retardation material can be produced, for example, by optically patterning a retardation material made of a polymerizable liquid crystal as disclosed in Patent Document 2.
  • Optical patterning of a retardation material made of a polymerizable liquid crystal utilizes a photo-alignment technique known for forming an alignment material for a liquid crystal panel. That is, a coating film made of a photo-alignment material is provided on a substrate, and two types of polarized light having different polarization directions are irradiated on the coating film. Then, a photo-alignment film is obtained as an alignment material in which two types of liquid crystal alignment regions having different liquid crystal alignment control directions are formed.
  • a solution-like retardation material containing a polymerizable liquid crystal is applied on the photo-alignment film to realize the alignment of the polymerizable liquid crystal. Thereafter, the aligned polymerizable liquid crystal is cured to form a patterned retardation material.
  • acrylic resins and polyimide resins having photodimerization sites such as cinnamoyl groups and chalcone groups in the side chain are known as usable photo-alignment materials.
  • These resins have been reported to exhibit the ability to control the alignment of liquid crystals (hereinafter also referred to as liquid crystal alignment) by irradiation with polarized UV (see Patent Documents 3 to 5).
  • the patterned retardation material is configured by laminating a cured polymerizable liquid crystal layer on a photo-alignment film that is an alignment material.
  • the patterned phase difference material which has such a laminated structure can be used for the structure of 3D display with the laminated state.
  • the 3D display is sometimes used as a home television, and is required to have high reliability, particularly durability over a long period of time. For this reason, durability is also required for components of 3D displays. Accordingly, the patterned phase difference agent also has long-term durability as well as being subjected to optical patterning with high accuracy and having high light transmission characteristics.
  • the conventional patterned retardation material has a problem in the adhesion between the photo-alignment film and the polymerizable liquid crystal layer.
  • the photo-alignment film and the polymerizable liquid crystal layer it is easy to peel off from the initial stage of formation, or it is excellent in adhesiveness at the initial stage of formation, but the adhesiveness is likely to deteriorate with the passage of time and easily peel off. There was something to be.
  • peeling between the photo-alignment film and the polymerizable liquid crystal layer which occurs with the passage of time, becomes a defect in a 3D display that is actually used and causes the display quality of the 3D display to deteriorate.
  • a patterned phase difference material that is capable of high-precision optical patterning, has excellent light transmission characteristics, and has excellent durability.
  • adhesion between the photo-alignment film at the initial stage of formation and the polymerizable liquid crystal layer is excellent, and the durability for maintaining the excellent adhesion for a long period of time (hereinafter referred to as adhesion durability in the present specification).
  • adhesion durability hereinafter referred to as adhesion durability in the present specification.
  • a patterned retardation material comprising:
  • an object of the present invention is to provide a cured film forming composition suitable for forming a cured film having excellent liquid crystal orientation and light transmission characteristics and excellent adhesion durability.
  • a cured film forming composition suitable for forming a cured film having excellent liquid crystal orientation and light transmission characteristics and excellent adhesion durability.
  • it when it is used as an alignment material and a polymerizable liquid crystal layer is disposed thereon, it exhibits excellent liquid crystal alignment and light transmission properties, and has a long adhesion with the polymerizable liquid crystal layer.
  • An object of the present invention is to provide an alignment material that is excellent in liquid crystal alignment and light transmission characteristics and excellent in adhesion durability.
  • An object of the present invention is to provide a retardation material capable of high-precision optical patterning and having excellent durability.
  • the first aspect of the present invention is: (A) a low orientation having a photo-alignment group and at least one substituent selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group and a group represented by the following formula (2) Polymer having molecular compound and photo-alignment group, and at least one substituent selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group and a group represented by the following formula (2) At least one selected from (Wherein R 62 represents an alkyl group, an alkoxy group or a phenyl group.) (B) a polymer having at least one substituent selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group and a group represented by the above formula (2); (C) a crosslinking agent, and (D)
  • the component (A) is a low molecular compound having a photoalignment group and a hydroxy group and / or a carboxyl group, and a polymer having a photoalignment group and a hydroxy group and / or a carboxyl group. It is preferable that it is 1 type chosen from.
  • the compound of (D) component is a compound which has a structure represented by following formula (1). (Wherein R 1 represents a hydrogen atom or a methyl group, and R 2 represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms),
  • the compound of (D) component is a compound which has a structure represented by following formula (X2).
  • R 51 represents a hydrogen atom or a methyl group.
  • R 53 is independently a linear or branched alkylene group having 2 to 20 carbon atoms, a divalent group consisting of an aliphatic ring having 5 to 6 carbon atoms, or an aliphatic ring having 5 to 6 carbon atoms. It represents a divalent aliphatic group containing, and an ether bond may be included in the structure of these groups.
  • R 54 is a divalent to nonvalent radical having a structure in which 1 to 8 hydrogen atoms are further removed from a linear or branched alkyl group having 2 to 20 carbon atoms, or an aliphatic ring having 5 to 6 carbon atoms.
  • R 52 represents a linear or branched alkyl group having 1 to 20 carbon atoms, a monovalent group consisting of an aliphatic ring having 5 to 6 carbon atoms, or an aliphatic ring having 5 to 6 carbon atoms. Represents a divalent aliphatic group, and one methylene group or a plurality of non-adjacent methylene groups in these groups may be replaced by an ether bond.
  • Z is> NCOO-, or -OCON ⁇ (where "-" indicates that there is one bond, and ">" and " ⁇ " indicate that there are two bonds. N atom Any one of the bonds represents a bond with —CH 2 OR 52 ).
  • r is a natural number of 2 or more and 9 or less. ]
  • the second aspect of the present invention relates to an alignment material characterized by being obtained using the cured film forming composition of the first aspect of the present invention.
  • the third aspect of the present invention relates to a retardation material characterized by having a cured film obtained from the cured film forming composition of the first aspect of the present invention.
  • a cured film forming composition suitable for forming a cured film having excellent liquid crystal orientation and light transmittance and excellent adhesion durability.
  • the second aspect of the present invention it is possible to provide an alignment material that is excellent in liquid crystal alignment and light transmittance and excellent in adhesion durability.
  • the third aspect of the present invention it is possible to provide a retardation material that is capable of high-precision optical patterning and excellent in durability.
  • an alignment material excellent in adhesion durability in particular, an alignment excellent in adhesion durability with a cured polymerizable liquid crystal layer, in order to produce a patterned retardation material having excellent durability.
  • the cured film formation composition suitable for formation of the orientation material of such a performance is calculated
  • a cured film obtained from a cured film-forming composition having a specific composition is excellent in light transmittance, and has a liquid crystal orientation by polarization exposure. It has been found that it can be used as an alignment material by showing liquid crystal alignment to be regulated.
  • the present inventor shows excellent adhesion durability between the cured film obtained from the cured film-forming composition having the specific composition and the polymerizable liquid crystal layer polymerized and cured thereon. I found out. That is, the cured film obtained from the cured film-forming composition having a specific composition of the present invention can constitute a photo-alignment film having excellent adhesion durability with the polymerizable liquid crystal layer.
  • the cured film forming composition of the present invention will be described in detail with specific examples of components and the like.
  • the cured film and alignment material of the present invention using the cured film forming composition of the present invention, the retardation material formed using the alignment material, the liquid crystal display element, and the like will be described.
  • the cured film forming composition of this embodiment of the present invention comprises (A) a photo-alignment group, a hydroxy group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group, and a group represented by the above formula (2).
  • Polymer having at least one selected substituent, (C) crosslinker as component, and (D) polymerizability containing C ⁇ C double bond in one molecule The at least one of a and N- alkoxymethyl group having at least one low-molecular compound curable film-forming composition of the thermosetting containing.
  • a crosslinking catalyst can be contained as the component (E).
  • other additives can be contained as long as the effects of the present invention are not impaired.
  • a solvent can be contained.
  • [(A) component] (A) component of the cured film formation composition of this embodiment is at least 1 type chosen from a low molecular photo-alignment component and a polymer photo-alignment component.
  • the component (A) is a low molecular photo-alignment component.
  • the low molecular photo-alignment component that is the component (A) is a component that imparts photo-alignment to the cured film of the present embodiment obtained from the cured film-forming composition of the present embodiment. It becomes a low molecular photo-alignment component compared with the component polymer.
  • the low molecular photoalignment component as the component (A) includes a photoalignment group, a hydroxy group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group, and the above formula ( A low molecular compound having at least one substituent selected from the group consisting of groups represented by 2) can be obtained.
  • the photo-alignment group means a functional group at a structural site that undergoes photodimerization or photoisomerization.
  • the structural part to be photodimerized that the low molecular compound of the component (A) can have as a photoalignment group is a part that forms a dimer by light irradiation.
  • Specific examples thereof include a cinnamoyl group and a chalcone group. , A coumarin group, an anthracene group and the like. Of these, a cinnamoyl group is preferred because of its high transparency in the visible light region and high photodimerization reactivity.
  • the photoisomerizable structural moiety that the low molecular compound of component (A) can have as a photoalignable group refers to a structural moiety that changes into a cis isomer and a trans isomer by light irradiation.
  • Examples include an azobenzene structure, a stilbene structure, and the like. Of these, an azobenzene structure is preferred because of its high reactivity.
  • alkoxysilyl group in the present embodiment a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, a diisopropoxymethylsilyl group, a methoxydimethylsilyl group, An ethoxydimethylsilyl group etc. are mentioned.
  • a low molecular compound having a photo-alignment group and any one of a substituent selected from a hydroxy group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group and a group represented by the above formula (2) is, for example, It is a compound represented by the following formula.
  • a 1 and A 2 each independently represent a hydrogen atom or a methyl group
  • X 11 is a single bond, an ether bond, an ester bond, an amide bond, a urea bond, a urethane bond, an amino bond, an carbonyl, or their A structure in which one to three substituents selected from an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, or a combination thereof are bonded through one or two or more bonds selected from a combination Represents.
  • X 12 represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, or a cyclohexyl group.
  • the alkyl group having 1 to 18 carbon atoms, the phenyl group, the biphenyl group, and the cyclohexyl group may be bonded through a covalent bond, an ether bond, an ester bond, an amide bond, a urethane bond, a carbonyl, or a urea bond.
  • X 13 represents a hydroxy group, a mercapto group, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, a phenoxy group, a biphenyloxy group, or a phenyl group.
  • X 14 each independently represents a single bond, an alkylene group having 1 to 20 carbon atoms, a divalent aromatic ring group, or a divalent aliphatic ring group.
  • the alkylene group having 1 to 20 carbon atoms may be branched or linear.
  • X 15 represents a hydroxy group, a carboxyl group, an amino group, an alkoxysilyl group or a group represented by the above formula (2).
  • X 14 is a single bond
  • X 15 is a hydroxy group or an amino group
  • X 0 represents a single bond, an oxygen atom or a sulfur atom.
  • X 14 is a single bond
  • X 0 is also a single bond.
  • substituents include a benzene ring
  • the benzene ring includes an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a trifluoromethyl group, and a cyano group. It may be substituted with one or a plurality of substituents which are the same or different.
  • R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or 1 carbon atom. Represents an alkoxy group, a halogen atom, a trifluoromethyl group, or a cyano group.
  • alkyl group having 1 to 18 carbon atoms defined above examples include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert- Butyl group, n-pentyl group, 1-methyl-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-di
  • examples of the alkyl group having 1 to 4 carbon atoms include groups having the corresponding number of carbon atoms among the groups listed above.
  • examples of the alkoxy group having 1 to 10 carbon atoms, the alkoxy group having 1 to 4 carbon atoms, and the alkylthio group having 1 to 10 carbon atoms include groups obtained by oxidizing or thiolating the alkyl groups listed above. Among them, groups having the corresponding number of carbon atoms are mentioned.
  • the alkylene group having 1 to 20 carbon atoms is a divalent group obtained by removing one hydrogen atom from the above alkyl group or an alkyl group having 19 to 20 carbon atoms such as n-nonadecyl group and n-eicosyl group. Is mentioned.
  • examples of the alkyl group for R 62 include an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. Group having the corresponding number of carbon atoms.
  • examples of the alkoxy group for R 62 include an alkoxy group having 1 to 10 carbon atoms.
  • the alkyl groups exemplified above such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group are oxidized.
  • Examples of the group represented by the above formula (2) include the following structures.
  • the low molecular weight compound having a photo-alignable group and a hydroxy group as the component (A) include 4- (8-hydroxyoctyloxy) cinnamic acid methyl ester, 4- (6-hydroxyhexyl), and the like.
  • the low molecular weight compound having a photo-alignable group and a carboxyl group as component (A) include cinnamic acid, ferulic acid, 4-nitrocinnamic acid, 4-methoxycinnamic acid, 3,4- Dimethoxycinnamic acid, coumarin-3-carboxylic acid, 4- (N, N-dimethylamino) cinnamic acid, 4- (6-methacryloxyhexyl-1-oxy) cinnamic acid, 4- (6-acryloxy) (Hexyl-1-oxy) cinnamic acid, 4- (3-methacryloxypropyl-1-oxy) cinnamic acid, 4- (4- (3-methacryloxypropyl-1-oxy) acryloxy) benzoic acid, 4 And-(4- (6-methacryloxyhexyl-1-oxy) benzoyloxy) cinnamic acid.
  • the low molecular weight compound having a photo-alignable group and an amide group as component (A) include cinnamic acid amide, 4-methyl cinnamic acid amide, 4-ethyl cinnamic acid amide, 4-methoxy cinnamic acid.
  • the low molecular weight compound having a photo-alignable group and an amino group as component (A) include 4-aminocinnamic acid methyl ester, 4-aminocinnamic acid ethyl ester, and 3-aminocinnamic acid methyl ester.
  • Examples include esters and 3-aminocinnamic acid ethyl ester.
  • the low molecular weight compound having a photo-alignable group and an alkoxysilyl group as the component (A) include 4- (3-trimethoxysilylpropyloxy) cinnamic acid methyl ester, 4- (3-tri Ethoxysilylpropyloxy) cinnamic acid methyl ester, 4- (3-trimethoxysilylpropyloxy) cinnamic acid ethyl ester, 4- (3-triethoxysilylpropyloxy) cinnamic acid ethyl ester, 4- (3- Trimethoxysilylhexyloxy) cinnamic acid methyl ester, 4- (3-triethoxysilylhexyloxy) cinnamic acid methyl ester, 4- (3-trimethoxysilylhexyloxy) cinnamic acid ethyl ester and 4- (3 -Triethoxysilylhexyloxy) cinn
  • the low molecular weight compound having the photoalignable group and the group represented by the above formula (2), which are the component (A) include compounds represented by the following formula (wherein, Me Represents a methyl group).
  • the component (A) is preferably a low-molecular compound in which a polymerizable group is bonded to a group in which a photo-alignment site and a thermally reactive site represented by the following formula (1a) are bonded via a spacer.
  • R 101 represents a hydroxy group, an amino group, a hydroxyphenoxy group, a carboxylphenoxy group, an aminophenoxy group, an aminocarbonylphenoxy group, a phenylamino group, a hydroxyphenylamino group, a carboxylphenylamino group, an aminophenylamino group, a hydroxy group, Represents an alkylamino group or a bis (hydroxyalkyl) amino group, X 101 represents a phenylene group which may be substituted with any substituent, and the benzene ring in the definition of these substituents is substituted with a substituent; May be.)
  • the substituent include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group; a haloalkyl group such as a trifluoromethyl group; a methoxy group, Examples thereof include alkoxy groups such as ethoxy group; halogen atoms such as iodine, bromine, chlorine and fluorine; cyano group; nitro group and the like.
  • a hydroxy group and an amino group are preferable, and a hydroxy group is particularly preferable.
  • the spacer is a divalent group selected from linear alkylene, branched alkylene, cyclic alkylene and phenylene, or a group formed by bonding a plurality of such divalent groups.
  • the bond between the divalent groups constituting the spacer, the bond between the spacer and the group represented by the above formula (1a), and the bond between the spacer and the polymerizable group include a single bond, an ester bond, and an amide bond. , Urea bond, urethane bond, carbonyl or ether bond.
  • the divalent groups may be the same or different, and when there are a plurality of the bonds, the bonds may be the same or different.
  • the monomer in which a polymerizable group is bonded to a group in which a photo-alignment site and a heat-reactive site are combined as the component (A) include 4- (6-methacryloxyhexyl-1-oxy).
  • low molecular weight photo-alignment component as component (A) can include the above-mentioned specific examples, but are not limited thereto.
  • component (A) is a polymer, that is, a high molecular weight polymer will be described below.
  • the component (A) contained in the cured film forming composition of the present invention is a polymer having a high molecular weight
  • the component (A) is a polymer having a photoalignment group, that is, as a photoalignment group.
  • a polymer having a functional group at a structural site to be quantified or photoisomerized, particularly an acrylic copolymer having at least a photodimerization site is preferable.
  • At least one substituent selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group and a group represented by the above formula (2) (hereinafter referred to as these An acrylic copolymer having a group including a group) is also desirable.
  • the acrylic copolymer refers to a copolymer obtained by polymerizing a monomer having an unsaturated double bond such as an acrylic ester, a methacrylic ester or styrene.
  • the acrylic copolymer having a photodimerization site and a thermal crosslinking site (A) as the component may be an acrylic copolymer having such a structure.
  • A thermal crosslinking site
  • Examples of the photodimerization site include a cinnamoyl group, a chalcone group, a coumarin group, and an anthracene group. Of these, a cinnamoyl group is preferred because of its high transparency in the visible light region and high photodimerization reactivity. More preferred examples of the cinnamoyl group and the substituent containing a cinnamoyl structure include structures represented by the following formula [1] or [2].
  • a group in which the benzene ring in the cinnamoyl group is a naphthalene ring is also included in the “cinnamoyl group” and the “substituent containing a cinnamoyl structure”.
  • X 1 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group or a biphenyl group.
  • the phenyl group and the biphenyl group may be substituted by either a halogen atom or a cyano group.
  • X 2 represents a hydrogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, or a cyclohexyl group.
  • the alkyl group having 1 to 18 carbon atoms, the phenyl group, the biphenyl group, and the cyclohexyl group may be formed from a covalent bond, an ether bond, an ester bond, an amide bond, a urea bond, a urethane bond, an amino bond, a carbonyl, or a combination thereof.
  • Plural types may be bonded through one or two or more selected bonds.
  • A represents one of formula [A1], formula [A2], formula [A3], formula [A4], formula [A5] and formula [A6].
  • R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 and R 38 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a trifluoromethyl group, or a cyano group.
  • the thermal crosslinking site is a site that is bonded to the component (B) by heating.
  • Specific examples thereof include a hydroxy group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group, and a group represented by the formula (2). Can be mentioned.
  • the component (A) acrylic copolymer preferably has a weight average molecular weight of 3,000 to 200,000. If the weight average molecular weight is over 200,000, the solubility in the solvent may be lowered and the handling property may be lowered. On the other hand, the weight average molecular weight is less than 3,000 and is too small. In some cases, the heat resistance may cause insufficient curing, resulting in a decrease in solvent resistance or a decrease in heat resistance.
  • the method for synthesizing the acrylic copolymer having a photodimerization site and a thermal crosslinking site as the component (A) is a simple method of copolymerizing a monomer having a photodimerization site and a monomer having a thermal crosslinking site.
  • Examples of the monomer having a photodimerization site include monomers having a cinnamoyl group, a chalcone group, a coumarin group, an anthracene group, and the like.
  • a monomer having a cinnamoyl group is particularly preferable because of its high transparency in the visible light region and high photodimerization reactivity.
  • a cinnamoyl group having a structure represented by the above formula [1] or [2] and a monomer having a substituent containing a cinnamoyl structure are more preferable.
  • a monomer having a substituent containing a cinnamoyl structure are more preferable.
  • it is a monomer represented by the following formula [3] or formula [4].
  • X 1 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group or a biphenyl group.
  • the phenyl group and the biphenyl group may be substituted by either a halogen atom or a cyano group.
  • L 1 and L 2 each independently represent a covalent bond, an ether bond, an ester bond, an amide bond, a urea bond or a urethane bond.
  • X 2 represents a hydrogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, or a cyclohexyl group.
  • the alkyl group having 1 to 18 carbon atoms, the phenyl group, the biphenyl group, and the cyclohexyl group may be bonded via a covalent bond, an ether bond, an ester bond, an amide bond, or a urea bond.
  • X 3 and X 5 are each independently a single bond, an alkylene group having 1 to 20 carbon atoms, a divalent aromatic ring group, or a divalent aliphatic ring group. Show. Here, the alkylene group having 1 to 20 carbon atoms may be branched or linear.
  • X 4 and X 6 represent a polymerizable group.
  • the polymerizable group include an acryloyl group, a methacryloyl group, a styrene group, a maleimide group, an acrylamide group, and a methacrylamide group.
  • A is the same as formula [A1], formula [A2], formula [A3], formula [A4], formula [A5] as in formula [1] and formula [2]. ] And formula [A6].
  • alkyl group and alkylene group are given as the alkyl group having 1 to 18 carbon atoms and the alkylene group having 1 to 20 carbon atoms in the definitions of the groups in the formulas [1] to [4]. Can do.
  • Examples of the monomer having a thermal crosslinking site include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2,3 -Dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, caprolactone 2- (acryloyloxy) ethyl ester, caprolactone 2- (methacryloyloxy) ethyl ester, poly (ethylene glycol) ethyl ether acrylate, Poly (ethylene glycol) ethyl ether methacrylate, 5-acryloyl Monomers having a hydroxy group such as cis-6-hydroxynorbornene-2-carboxyl-6-lactone, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxy
  • the amount of the monomer having a photodimerization site and the monomer having a thermal crosslinking site used for obtaining the specific copolymer is determined based on the total amount of all monomers used for obtaining the specific copolymer. It is preferable that the monomer having 40 mass% to 95 mass% and the monomer having a thermal crosslinking site is 5 mass% to 60 mass%.
  • a monomer copolymerizable with a monomer having a photodimerization site and a thermal crosslinking site (hereinafter also referred to as a specific functional group) when obtaining a specific copolymer ( (Hereinafter also referred to as a monomer having a non-reactive functional group) can be used in combination.
  • Such monomers include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds and vinyl compounds.
  • acrylic acid ester compounds methacrylic acid ester compounds
  • maleimide compounds maleimide compounds
  • acrylamide compounds acrylonitrile
  • maleic anhydride maleic anhydride
  • styrene compounds vinyl compounds.
  • acrylic ester compound described above examples include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, glycidyl acrylate, 2,2,2-trifluoroethyl.
  • methacrylic acid ester compounds described above include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl.
  • Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl carbazole, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo [4.1.0] heptane, and 1,2-epoxy-5. Examples include hexene and 1,7-octadiene monoepoxide.
  • styrene compound described above examples include styrene, methylstyrene, chlorostyrene, and bromostyrene.
  • maleimide compound described above examples include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.
  • the method for obtaining the specific copolymer used in the cured film-forming composition of the present invention is not particularly limited.
  • a monomer having a specific functional group a monomer having a photodimerization site and a monomer having a thermal cross-linking site
  • non-specific if desired. It is obtained by carrying out a polymerization reaction at a temperature of 50 ° C. to 110 ° C. in a solvent in which a monomer having a reactive functional group and a polymerization initiator coexist.
  • the solvent used will not be specifically limited if it dissolves the monomer which has a specific functional group, the monomer which has a non-reactive functional group used depending on necessity, a polymerization initiator, etc. Specific examples include solvents described in Solvents described below.
  • the specific copolymer thus obtained is usually in the form of a solution dissolved in a solvent and can be used as it is as the solution of component (A) in the present invention.
  • the solution of the specific copolymer obtained as described above is re-precipitated by stirring with stirring such as diethyl ether or water, and the generated precipitate is filtered and washed, and then under normal pressure or reduced pressure.
  • the powder of the specific copolymer can be obtained by drying at room temperature or by heating. By such an operation, the polymerization initiator and unreacted monomer coexisting with the specific copolymer can be removed, and as a result, a purified powder of the specific copolymer can be obtained. If sufficient purification cannot be achieved by one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.
  • the powder of the specific copolymer may be used as it is as the component (A), or the powder is re-dissolved in, for example, a solvent described later to form a solution. It may be used.
  • the acrylic copolymer as the component (A) may be a mixture of a plurality of types of specific copolymers.
  • a low molecular weight compound or a high molecular weight specific copolymer can be used as the component (A).
  • the component (A) may be a mixture of one or more low molecular weight compounds and a high molecular weight specific copolymer.
  • Component (B) The component (B) contained in the cured film forming composition of this embodiment is at least one selected from a hydroxy group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group, and a group represented by the above formula (2).
  • a polymer having two substituents hereinafter also referred to as specific functional groups).
  • a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, a diisopropoxymethylsilyl group, a methoxydimethylsilyl group, An ethoxydimethylsilyl group etc. are mentioned.
  • polymer as the component (B) examples include acrylic polymer, polyamic acid, polyimide, polyvinyl alcohol, polyester, polyester polycarboxylic acid, polyether polyol, polyester polyol, polycarbonate polyol, polycaprolactone polyol, polyalkyleneimine, poly Examples include allylamine, celluloses (cellulose or derivatives thereof), polymers having a linear or branched structure such as phenol novolac resin and melamine formaldehyde resin, and cyclic polymers such as cyclodextrins.
  • Preferred examples of the specific polymer (B) include acrylic polymers, hydroxyalkylcyclodextrins, celluloses, polyether polyols, polyester polyols, polycarbonate polyols, and polycaprolactone polyols.
  • the acrylic polymer which is a preferred example of the specific polymer of the component (B) is a polymer obtained by polymerizing a monomer having an unsaturated double bond such as acrylic acid, methacrylic acid, styrene, and a vinyl compound. Any polymer may be used as long as it is a polymer obtained by polymerizing a monomer containing a monomer having a specific functional group or a mixture thereof, and the type of the main chain skeleton and side chain of the polymer constituting the acrylic polymer is not particularly limited. .
  • the monomer having a specific functional group includes a monomer having a polyethylene glycol ester group, a monomer having a hydroxyalkyl ester group having 2 to 5 carbon atoms, a monomer having a phenolic hydroxy group, a monomer having a carboxyl group, and an amide group.
  • Examples of the monomer having a polyethylene glycol ester group described above include monoacrylate or monomethacrylate of H— (OCH 2 CH 2 ) n—OH.
  • the value of n is 2 to 50, preferably 2 to 10.
  • Examples of the monomer having a hydroxyalkyl ester group having 2 to 5 carbon atoms include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, and 4-hydroxybutyl acrylate. 4-hydroxybutyl methacrylate.
  • Examples of the above-mentioned monomer having a phenolic hydroxy group include p-hydroxystyrene, m-hydroxystyrene, and o-hydroxystyrene.
  • Examples of the above-mentioned monomer having a carboxyl group include acrylic acid, methacrylic acid, and vinyl benzoic acid.
  • Examples of the monomer having an amino group in the side chain described above include 2-aminoethyl acrylate, 2-aminoethyl methacrylate, aminopropyl acrylate, and aminopropyl methacrylate.
  • Examples of the monomer having an alkoxysilyl group in the side chain include 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropyltrimethoxy. Examples thereof include silane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, and allyltriethoxysilane.
  • Examples of the monomer having a group represented by the above formula (2) in the side chain include 2-acetoacetoxyethyl acrylate, 2-acetoacetoxyethyl methacrylate, and the like.
  • Such monomers include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds and vinyl compounds.
  • acrylic ester compound examples include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl.
  • methacrylic acid ester compound examples include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl.
  • maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.
  • styrene compound examples include styrene, methyl styrene, chlorostyrene, bromostyrene, and the like.
  • vinyl compound examples include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.
  • the usage-amount of the monomer which has a specific functional group used in order to obtain the acrylic polymer which is an example of a component is based on the total amount of all the monomers used in order to obtain the acrylic polymer which is (B) component, It is preferably 2 mol% to 98 mol%.
  • the monomer having the specific functional group is too small, the liquid crystal orientation of the resulting cured film tends to be insufficient, and when it is too large, the compatibility with the component (A) tends to decrease.
  • the method to obtain the acrylic polymer which is an example of a component is not specifically limited,
  • the monomer containing the monomer which has a specific functional group, the monomer which does not have a specific functional group depending on necessity, a polymerization initiator, etc. Is obtained by a polymerization reaction at a temperature of 50 ° C. to 110 ° C. in a solvent coexisting with.
  • the solvent used will not be specifically limited if it dissolves the monomer which has a specific functional group, the monomer which does not have the specific functional group used depending on necessity, a polymerization initiator, etc. Specific examples are described in the section of [Solvent] described later.
  • the acrylic polymer which is an example of the component (B) obtained by the above method is usually in a solution state dissolved in a solvent.
  • the acrylic polymer solution which is an example of the component (B) obtained by the above method, is poured into diethyl ether or water under stirring to cause reprecipitation, and the generated precipitate is filtered and washed. Under normal pressure or reduced pressure, it can be dried at room temperature or dried to obtain an acrylic polymer powder as an example of the component (B).
  • the polymerization initiator and unreacted monomer coexisting with the acrylic polymer which is an example of the component (B) can be removed, and as a result, the acrylic polymer which is an example of the purified component (B) Of powder is obtained. If sufficient purification cannot be achieved by a single operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.
  • the acrylic polymer which is a preferred example of the component (B) has a weight average molecular weight of preferably 3000 to 200000, more preferably 4000 to 150,000, and still more preferably 5000 to 100,000. If the weight average molecular weight exceeds 200,000, the solvent solubility may decrease and handling may decrease. If the weight average molecular weight is less than 3,000, the curing may be insufficient during thermal curing. The solvent resistance and heat resistance may be reduced.
  • the weight average molecular weight is a value obtained by using gel as a standard material by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • polyether polyol which is a preferable example of the specific polymer of the component (B)
  • polyether polyols include ADEKA Adeka Polyether P Series, G Series, EDP Series, BPX Series, FC Series, CM Series, NOF UNIOX (registered trademark) HC-40, HC-60, ST- 30E, ST-40E, G-450, G-750, Uniol (registered trademark) TG-330, TG-1000, TG-3000, TG-4000, HS-1600D, DA-400, DA-700, DB-400 Nonion (registered trademark) LT-221, ST-221, OT-221 and the like.
  • polyester polyol which is a preferable example of the specific polymer of component
  • diols such as ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol and polypropylene glycol are added to polyvalent carboxylic acids such as adipic acid, sebacic acid and isophthalic acid. Can be mentioned.
  • polyester polyol examples include DIC polylite (registered trademark) OD-X-286, OD-X-102, OD-X-355, OD-X-2330, OD-X-240, OD-X-668, OD-X-2108, OD-X-2376, OD-X-2044, OD-X-688, OD-X-2068, OD-X-2547, OD-X-2420, OD-X-2523, OD- X-2555, OD-X-2560, Kuraray polyols P-510, P-1010, P-2010, P-3010, P-4010, P-5010, P-6010, F-510, F-1010, F -2010, F-3010, P-1011, P-2011, P-2013, P-2030, N-2010, PNNA-2016 and the like.
  • DIC polylite registered trademark
  • polycaprolactone polyol which is a preferred example of the specific polymer of the component (B) include those obtained by ring-opening polymerization of ⁇ -caprolactone using a polyhydric alcohol such as trimethylolpropane or ethylene glycol as an initiator.
  • polyhydric alcohol such as trimethylolpropane or ethylene glycol as an initiator.
  • Specific examples of the polycaprolactone polyol include DIC's Polylite (registered trademark) OD-X-2155, OD-X-640, OD-X-2568, Daicel Chemical's Plaxel (registered trademark) 205, L205AL, 205U, 208, 210 212, L212AL, 220, 230, 240, 303, 305, 308, 312, 320, and the like.
  • polycarbonate polyol which is a preferable example of the specific polymer of the component (B) include those obtained by reacting a polyhydric alcohol such as trimethylolpropane or ethylene glycol with diethyl carbonate, diphenyl carbonate, ethylene carbonate, or the like.
  • a polyhydric alcohol such as trimethylolpropane or ethylene glycol
  • diethyl carbonate diethyl carbonate
  • diphenyl carbonate ethylene carbonate
  • ethylene carbonate or the like.
  • Specific examples of the polycarbonate polyol include Placel (registered trademark) CD205, CD205PL, CD210, CD220 manufactured by Daicel Chemical Industries, and C-590, C-1050, C-2050, C-2090, C-3090 manufactured by Kuraray, and the like.
  • cellulose examples include hydroxyalkylcelluloses such as hydroxyethylcellulose and hydroxypropylcellulose, hydroxyalkylalkylcelluloses such as hydroxyethylmethylcellulose, hydroxypropylmethylcellulose and hydroxyethylethylcellulose, and cellulose.
  • hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose are preferable.
  • cyclodextrins such as ⁇ -cyclodextrin, ⁇ -cyclodextrin and ⁇ cyclodextrin, methyl- ⁇ -cyclodextrin, methyl- ⁇ -cyclodextrin and Methylated cyclodextrins such as methyl- ⁇ -cyclodextrin, hydroxymethyl- ⁇ -cyclodextrin, hydroxymethyl- ⁇ -cyclodextrin, hydroxymethyl- ⁇ -cyclodextrin, 2-hydroxyethyl- ⁇ -cyclodextrin, 2-hydroxy Ethyl- ⁇ -cyclodextrin, 2-hydroxyethyl- ⁇ -cyclodextrin, 2-hydroxypropyl- ⁇ -cyclodextrin, 2-hydroxypropyl- ⁇ -cyclodextrin, 2-hydroxypropyl- ⁇ -cyclodextrin, 2-hydroxypropyl Lopyl- ⁇ -cyclodextrin,
  • the melamine formaldehyde resin which is a preferable example of the specific polymer of the component (B) is a resin obtained by polycondensation of melamine and formaldehyde, and is represented by the following formula.
  • R 21 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • n is a natural number representing the number of repeating units.
  • alkyl group having 1 to 4 carbon atoms include groups having the corresponding number of carbon atoms among the alkyl groups exemplified above or below.
  • the methylol group generated during the polycondensation of melamine and formaldehyde is alkylated from the viewpoint of storage stability.
  • the method for obtaining the melamine formaldehyde resin as the component (B) is not particularly limited, but in general, melamine and formaldehyde are mixed, made weakly alkaline using sodium carbonate, ammonia, etc., and then heated at 60 ° C. to 100 ° C. Is synthesized. Further, the methylol group can be alkoxylated by reacting with alcohol.
  • the (B) component melamine formaldehyde resin preferably has a weight average molecular weight of 250 to 5000, more preferably 300 to 4000, and even more preferably 350 to 3500. If the weight average molecular weight exceeds 5,000, the solubility in the solvent may decrease and handling may decrease. If the weight average molecular weight is less than 250, the curing may be insufficient during thermal curing. Therefore, the effect of improving solvent resistance and heat resistance may not be sufficiently exhibited.
  • the melamine formaldehyde resin as the component (B) may be used in a liquid form or a solution form in which a purified liquid is redissolved in a solvent described later.
  • the melamine formaldehyde resin as the component (B) may be a mixture of plural types of melamine formaldehyde resins as the component (B).
  • phenol novolak resin which is a preferred example of the specific polymer of the component (B) include phenol-formaldehyde polycondensate.
  • the polymer of the component (B) may be used in a powder form or in a solution form in which a purified powder is redissolved in a solvent described later.
  • the component (B) may be a mixture of a plurality of types of polymers exemplified as the component (B).
  • the cured film forming composition of this embodiment contains a crosslinking agent as (C) component. More specifically, the component (C) reacts with the component (A), the component (B) and the component (D) described later, and the component (A) is a low molecular photo-alignment component. A) A crosslinking agent that reacts at a temperature lower than the sublimation temperature of the component.
  • the component (C) is at a temperature lower than the sublimation temperature of the component (A), and the hydroxy group, carboxyl group, amide group, amino group, alkoxysilyl group and the above formula (A) Substituents selected from the groups represented by 2), hydroxy groups, carboxyl groups, amide groups, amino groups, alkoxysilyl groups contained in the component (B) and substitutions selected from the groups represented by the above formula (2) Bonds to the group (D) component compound.
  • the (A) component, the (B) component, the (D) component, and the crosslinking agent as the (C) component are thermally reacted, the (A) component is prevented from sublimating. can do.
  • the cured film formation composition of this Embodiment can form alignment material with high photoreaction efficiency as a cured film.
  • crosslinking agent (C) examples include compounds such as epoxy compounds, methylol compounds and isocyanate compounds, with methylol compounds being preferred.
  • methylol compound described above examples include compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine.
  • alkoxymethylated glycoluril examples include, for example, 1,3,4,6-tetrakis (methoxymethyl) glycoluril, 1,3,4,6-tetrakis (butoxymethyl) glycoluril, 1,3,4 , 6-tetrakis (hydroxymethyl) glycoluril, 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea, 1,1,3,3-tetrakis (methoxymethyl) Examples include urea, 1,3-bis (hydroxymethyl) -4,5-dihydroxy-2-imidazolinone, and 1,3-bis (methoxymethyl) -4,5-dimethoxy-2-imidazolinone.
  • glycoluril compounds (trade names: Cymel (registered trademark) 1170, Powderlink (registered trademark) 1174) manufactured by Mitsui Cytec Co., Ltd., methylated urea resins (trade name: UFR (registered trademark) 65) ), Butylated urea resin (trade names: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), urea / formaldehyde resin (high condensation type, commercial product) manufactured by Dainippon Ink & Chemicals, Inc. Name: Beccamine (registered trademark) J-300S, P-955, N) and the like.
  • alkoxymethylated benzoguanamine examples include, for example, tetramethoxymethylbenzoguanamine.
  • Commercially available products manufactured by Mitsui Cytec Co., Ltd. (trade name: Cymel (registered trademark) 1123), manufactured by Sanwa Chemical Co., Ltd. (trade names: Nicalac (registered trademark) BX-4000, BX-37, BL- 60, BX-55H) and the like.
  • alkoxymethylated melamine examples include, for example, hexamethoxymethylmelamine.
  • methoxymethyl type melamine compounds (trade names: Cymel (registered trademark) 300, 301, 303, 350) manufactured by Mitsui Cytec Co., Ltd., butoxymethyl type melamine compounds (trade name: My Coat (registered trademark)) 506, 508), Sanwa Chemical's methoxymethyl-type melamine compound (trade names: Nicalak (registered trademark) MW-30, MW-22, MW-11, MS-001, MX-002, MX-730, MX-750, MX-035), butoxymethyl type melamine compounds (trade names: Nicalac (registered trademark) MX-45, MX-410, MX-302) and the like.
  • it may be a compound obtained by condensing a melamine compound, urea compound, glycoluril compound and benzoguanamine compound in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group.
  • a melamine compound urea compound, glycoluril compound and benzoguanamine compound in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group.
  • the high molecular weight compound manufactured from the melamine compound and the benzoguanamine compound which are described in US Patent 6,323,310 is mentioned.
  • Examples of commercially available products of the melamine compound include trade name: Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.).
  • Examples of commercially available products of the benzoguanamine compound include product name: Cymel (registered trademark) 1123 ( Mitsui Cytec Co., Ltd.).
  • an acrylamide compound substituted with a hydroxymethyl group or an alkoxymethyl group such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, N-butoxymethylmethacrylamide, or the like Polymers produced using methacrylamide compounds can also be used.
  • Examples of such a polymer include poly (N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methylmethacrylate, and N-ethoxymethyl.
  • Examples thereof include a copolymer of methacrylamide and benzyl methacrylate, and a copolymer of N-butoxymethylacrylamide, benzyl methacrylate and 2-hydroxypropyl methacrylate.
  • the weight average molecular weight of such a polymer is 1000 to 500000, preferably 2000 to 200000, more preferably 3000 to 150,000, and still more preferably 3000 to 50000.
  • cross-linking agents can be used alone or in combination of two or more.
  • the content of the crosslinking agent of component (C) in the cured film forming composition of the present embodiment is the total amount of at least one selected from the low molecular compound and polymer as component (A) and the polymer of component (B). It is preferably 10 to 100 parts by mass, more preferably 15 to 80 parts by mass based on 100 parts by mass.
  • content of a crosslinking agent is too small, the solvent tolerance and heat resistance of the cured film obtained from a cured film formation composition will fall, and the orientation sensitivity at the time of photo-alignment will fall.
  • the content is excessive, the photo-alignment property and the storage stability may be lowered.
  • the component (D) contained in the cured film forming composition of this embodiment has at least one polymerizable group containing a C ⁇ C double bond in one molecule and at least one N-alkoxymethyl group. Low molecular weight compound.
  • the polymerizable liquid crystal of the polymerizable liquid crystal is improved so that the adhesion between the alignment material and the polymerizable liquid crystal layer is improved.
  • the polymerizable functional group and the crosslinking reaction site of the alignment material can be linked by a covalent bond.
  • the retardation material of this embodiment formed by laminating a cured polymerizable liquid crystal on the alignment material of this embodiment can maintain strong adhesion even under high temperature and high quality conditions, such as peeling. High durability can be exhibited.
  • Examples of the polymerizable group containing a C ⁇ C double bond include an acryl group, a methacryl group, a vinyl group, an allyl group, and a maleimide group.
  • N of N-alkoxymethyl group that is, nitrogen atom is adjacent to amide nitrogen atom, thioamide nitrogen atom, urea nitrogen atom, thiourea nitrogen atom, urethane nitrogen atom, nitrogen atom of nitrogen-containing heterocycle And a nitrogen atom bonded to. Therefore, the N-alkoxymethyl group includes an amide nitrogen atom, a thioamide nitrogen atom, a urea nitrogen atom, a thiourea nitrogen atom, a urethane nitrogen atom, and a nitrogen bonded to the adjacent position of the nitrogen atom of the nitrogen-containing heterocyclic ring. Examples include a structure in which an alkoxymethyl group is bonded to a nitrogen atom selected from atoms and the like.
  • any compound having the above-mentioned group may be used, and preferably, for example, a compound represented by the following formula (1) is exemplified.
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms
  • alkyl group examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, and 1-methyl-n.
  • Specific examples of the compound represented by the above formula (1) include N-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-methylolacrylamide and the like. .
  • a compound represented by the following formula (X2) is preferable.
  • R 51 represents a hydrogen atom or a methyl group.
  • R 53 is a linear or branched alkylene group having 2 to 20 carbon atoms, a divalent group composed of an aliphatic ring having 5 to 6 carbon atoms, or a divalent group containing an aliphatic ring having 5 to 6 carbon atoms. Represents a valent aliphatic group and may contain an ether bond in the structure.
  • R 54 is a divalent to nonvalent group having a structure in which 1 to 8 hydrogen atoms are removed from a linear or branched alkyl group having 2 to 20 carbon atoms, or an aliphatic cyclic group having 5 to 6 carbon atoms.
  • R 52 represents a linear or branched alkyl group having 1 to 20 carbon atoms, a monovalent group consisting of an aliphatic ring having 5 to 6 carbon atoms, or an aliphatic ring having 5 to 6 carbon atoms. Represents a divalent aliphatic group, and one methylene group or a plurality of non-adjacent methylene groups in these groups may be replaced by an ether bond.
  • Z is> NCOO-, or -OCON ⁇ (where "-" indicates that there is one bond, and ">" and " ⁇ " indicate that there are two bonds. N atom Any one of the bonds represents a bond with —CH 2 OR 52 ).
  • r is a natural number of 2 or more and 9 or less. ]
  • Specific examples of the thruvalent group include divalent to ninevalent groups in which 1 to 8 hydrogen atoms are further removed from the alkyl group having 2 to 20 carbon atoms shown below.
  • alkyl group having 2 to 20 carbon atoms include ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n -Pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, n-hexyl group, 1-methyl -N-pentyl, 2-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, n- Heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecy
  • R 53 is an ethylene group
  • R 54 is a hexylene group, from the viewpoint of availability of raw materials.
  • alkyl group having 1 to 20 carbon atoms in the definition of R 52 include a specific example of an alkyl group having 2 to 20 carbon atoms and a methyl group in the description of the definitions of R 53 and R 54 above. Of these, an alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group, an ethyl group, an n-propyl group, or an n-butyl group is particularly preferable.
  • Examples of the aliphatic ring group having 5 to 6 carbon atoms in the definition of R 52 , R 53 and R 54 include a group based on a cyclopentyl group and a cyclohexyl group, and a monovalent group such as a cyclopentyl group and a cyclohexyl group.
  • R may be a natural number of 2 or more and 9 or less, preferably 2 to 6.
  • Compound (X2) is obtained by the production method represented by the following reaction scheme. That is, a carbamate compound having an acryl or methacryl group represented by the following formula (X2-1) (hereinafter also referred to as compound (X2-1)) is reacted in a solvent to which trimethylsilyl chloride and paraformaldehyde are added. It is produced by synthesizing an intermediate represented by the following formula (X2-2), and adding and reacting an alcohol represented by R 52 —OH to the reaction solution.
  • R 51 , R 52 , R 53 , R 54 , Z and r represent the above-mentioned meanings, and X represents —NHCOO— or —OCONH—.
  • trimethylsilyl chloride and paraformaldehyde to be used with respect to compound (X2-1) is not particularly limited. However, in order to complete the reaction, trimethylsilyl chloride is 1.0 to 6.0 equivalent times the amount of one carbamate bond in the molecule, Paraformaldehyde is preferably used in an amount of 1.0 to 3.0 equivalents, and more preferably the equivalent of trimethylsilyl chloride is greater than the equivalent of paraformaldehyde.
  • the reaction solvent is not particularly limited as long as it is inert to the reaction.
  • hydrocarbons such as hexane, cyclohexane, benzene and toluene; methylene chloride, carbon tetrachloride, chloroform, 1,2-dichloroethane and the like Halogenated hydrocarbons; ethers such as diethyl ether, diisopropyl ether, 1,4-dioxane and tetrahydrofuran; nitriles such as acetonitrile and propionitrile; N, N-dimethylformamide, N, N-dimethylacetamide, N -Nitrogen-containing aprotic polar solvents such as methyl-2-pyrrolidone and 1,3-dimethyl-2-imidazolidinone; pyridines such as pyridine and picoline. These solvents may be used alone, or two or more of these may be mixed and used.
  • Preferred are m
  • reaction concentration is not particularly limited, but the reaction may be carried out without using a solvent.
  • a solvent 0.1 to 100 mass relative to compound (X2-1) is used. Double the solvent may be used. Preferably it is 1 thru
  • the reaction temperature is not particularly limited but is, for example, ⁇ 90 to 200 ° C., preferably ⁇ 20 to 100 ° C., and more preferably ⁇ 10 to 50 ° C.
  • the reaction time is usually 0.05 to 200 hours, preferably 0.5 to 100 hours.
  • the reaction can be carried out at normal pressure or under pressure, and can be batch or continuous.
  • a polymerization inhibitor may be added during the reaction.
  • BHT 2,6-di-tert-butyl-para-cresol
  • hydroquinone para-methoxyphenol, etc.
  • para-methoxyphenol para-methoxyphenol
  • the addition amount in the case of adding a polymerization inhibitor is not particularly limited, but is 0.0001 to 10 wt%, preferably 0.01 to 1 wt% with respect to the total amount (mass) of compound (X2-1). is there. In the present specification, wt% means mass%.
  • a base may be added to suppress hydrolysis under acidic conditions.
  • the base include pyridines such as pyridine and picoline, and tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine and tributylamine. Triethylamine and diisopropylethylamine are preferable, and triethylamine is more preferable.
  • the addition amount in the case of adding a base is not particularly limited, but it may be used 0.01 to 2.0 equivalents, more preferably 0.5 to 1 with respect to the addition amount of trimethylsilyl chloride used in the reaction. 0.0 equivalents.
  • the synthesis method of compound (X2-1) is not particularly limited, but it can be produced by reacting (meth) acryloyloxyalkyl isocyanate with a polyol compound or reacting a hydroxyalkyl (meth) acrylate compound with a polyisocyanate compound. I can do it.
  • (meth) acryloyloxyalkyl isocyanate examples include, for example, 2-methacryloyloxyethyl isocyanate (manufactured by Showa Denko KK, trade name: Karenz MOI [registered trademark]), 2-acryloyloxyethyl isocyanate (Showa). Denko Co., Ltd., trade name: Karenz AOI [registered trademark]) and the like.
  • polyol compound examples include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, Examples include diol compounds such as 1,6-hexanediol and 1,4-cyclohexanedimethanol, triol compounds such as glycerin and trimethylolpropane, pentaerythritol, dipentaerythritol, and diglycerin.
  • hydroxyalkyl (meth) acrylate compounds include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, and diethylene glycol.
  • monomers having a hydroxy group such as monoacrylate, diethylene glycol monomethacrylate, poly (ethylene glycol) ethyl ether acrylate, poly (ethylene glycol) ethyl ether methacrylate, and the like.
  • polyisocyanate compound examples include aliphatic diisocyanates such as hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate and dimer diisocyanate, isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), ⁇ , ⁇ Alicyclic diisocyanates such as' -diisocyanate dimethylcyclohexane, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 1,3,6-hexamethylene triisocyanate, And triisocyanates such as bicycloheptane triisocyanate.
  • aliphatic diisocyanates such as hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate and dimer diisocyanate
  • the content of the component (D) in the cured film-forming composition of the embodiment of the present invention is at least one selected from the low molecular compound and polymer as the component (A), the polymer as the component (B), and the component (C). Preferably it is 0.1 mass part thru
  • the content of the component (D) is 0.1 parts by mass or more, sufficient adhesion can be imparted to the formed cured film. However, when it is more than 40 parts by mass, the storage stability of the cured film forming composition may be lowered.
  • the component (D) may be a mixture of a plurality of compounds of the component (D).
  • the cured film forming composition of the present embodiment may contain a crosslinking catalyst as the component (E) in addition to the component (A), the component (B), the component (C) and the component (D) described above. it can.
  • (E) As a crosslinking catalyst which is a component, it can be set as an acid or a thermal acid generator, for example. This component (E) is effective in promoting a thermosetting reaction in the formation of a cured film using the cured film forming composition of the present embodiment.
  • the component (E) is a sulfonic acid group-containing compound, hydrochloric acid or a salt thereof, a compound that generates an acid by thermal decomposition during pre-baking or post-baking, that is, a temperature of 80
  • the compound is not particularly limited as long as it is a compound capable of generating an acid by thermal decomposition at from 250C to 250C.
  • Examples of such compounds include hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid, trifluoro.
  • L-methanesulfonic acid p-phenolsulfonic acid, 2-naphthalenesulfonic acid, mesitylenesulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, 1H, 1H, 2H, 2H-perfluorooctanesulfonic acid, perfluoro (2-ethoxyethane) sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid, sulfonic acid such as dodecylbenzenesulfonic acid, or a hydrate or salt thereof Is mentioned.
  • Examples of the compound that generates an acid by heat include bis (tosyloxy) ethane, bis (tosyloxy) propane, bis (tosyloxy) butane, p-nitrobenzyl tosylate, o-nitrobenzyl tosylate, 1,2, 3-phenylene tris (methyl sulfonate), p-toluenesulfonic acid pyridinium salt, p-toluenesulfonic acid morphonium salt, p-toluenesulfonic acid ethyl ester, p-toluenesulfonic acid propyl ester, p-toluenesulfonic acid butyl ester, p-toluenesulfonic acid isobutyl ester, p-toluenesulfonic acid methyl ester, p-toluenesulfonic acid phenethyl ester, cyanomethyl p-
  • the content of the component (E) in the cured film forming composition according to the embodiment of the present invention is at least one selected from the low molecular compound and polymer as the component (A), the polymer as the component (B), and the component (C). Preferably it is 0.01 mass part thru
  • the content of the component (E) can be made favorable by setting it as 10 mass parts or less.
  • the cured film forming composition of the embodiment of the present invention can contain other additives as long as the effects of the present invention are not impaired.
  • a sensitizer can be contained.
  • the sensitizer is effective in promoting the photoreaction when the cured film of the embodiment of the present invention is formed from the cured film forming composition of the present embodiment.
  • sensitizer examples include benzophenone, anthracene, anthraquinone and thioxanthone derivatives and nitrophenyl compounds.
  • N, N-diethylaminobenzophenone which is a derivative of benzophenone and 2-nitrofluorene, 2-nitrofluorenone, 5-nitroacenaphthene, 4-nitrobiphenyl, 4-nitrocinnamic acid, which are nitrophenyl compounds, 4- Nitrostilbene, 4-nitrobenzophenone and 5-nitroindole are particularly preferred.
  • These sensitizers are not particularly limited to those described above. These can be used alone or in combination of two or more compounds.
  • the use ratio of the sensitizer is 0.1 parts by mass to 100 parts by mass of the total amount of the component (A), the component (B), the component (C), and the component (D). It is preferably 20 parts by mass, more preferably 0.2 parts by mass to 10 parts by mass. If this ratio is too small, the effect as a sensitizer may not be sufficiently obtained. If it is too large, the transmittance of the formed cured film may be reduced or the coating film may be roughened. There are things to do.
  • the cured film forming composition according to the embodiment of the present invention includes, as other additives, silane coupling agents, surfactants, rheology modifiers, pigments, dyes, storage stability, as long as the effects of the present invention are not impaired. Agents, antifoaming agents, antioxidants, and the like.
  • the cured film forming composition of the embodiment of the present invention is often used in a solution state dissolved in a solvent.
  • the solvent used in that case is one that dissolves the component (A), the component (B), the component (C) and the component (D), and if necessary, the component (E) and / or other additives.
  • the solvent include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether Acetate, propylene glycol propyl ether acetate, cyclopentyl methyl ether, isopropyl alcohol, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, ⁇ -butyrolactone , Ethyl 2-hydroxypropionate, 2- Ethyl droxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate
  • solvents can be used alone or in combination of two or more.
  • the cured film forming composition of the embodiment of the present invention is a thermosetting cured film forming composition having photo-alignment properties.
  • the cured film forming composition of the present embodiment is at least one selected from the low molecular compound and polymer as the component (A), and the hydroxy group, carboxyl group, amide group, amino group as the component (B).
  • a polymer having at least one substituent selected from an alkoxysilyl group and a group represented by the above formula (2), (C) a crosslinking agent as component, and (D) component It contains a low molecular compound having at least one polymerizable group containing a C double bond and having at least one N-alkoxymethyl group.
  • a crosslinking catalyst can be contained as (E) component.
  • another additive can be contained and a solvent can be contained further.
  • the mixing ratio of the component (A) and the component (B) is preferably 5:95 to 80:20 by mass ratio.
  • the content of the component (B) is excessive, the liquid crystal orientation is liable to be lowered, and when it is too small, the solvent resistance is lowered and the orientation is liable to be lowered.
  • Preferred examples of the cured film forming composition of the present embodiment are as follows.
  • the blending ratio with the polymer having at least one substituent selected is 5:95 to 80:20 by mass ratio, and the low molecular weight compound as the component (A) and at least one selected from the polymer and the component (B) Based on 100 parts by mass of the total amount with the polymer, 10 to 100 parts by mass of the (C) component crosslinking agent, and the (A) component low molecular compound and polymer In 100 molecules of the total amount of at least one kind selected from the polymer of the component (B) and the crosslink
  • the blending ratio of the component (A) and the component (B) is 5:95 to 80:20 by mass ratio, and the component (A) is at least one selected from low molecular compounds and polymers, and (B) 10 parts by mass to 100 parts by mass of component (C) based on 100 parts by mass of the total amount of the components with the polymer, and at least one selected from low molecular compounds and polymers as component (A), component (B)
  • the blending ratio of the component (A) and the component (B) is 5:95 to 80:20 by mass ratio, and the component (A) is at least one selected from low molecular compounds and polymers, and (B) 10 parts by weight to 100 parts by weight of component (C) based on 100 parts by weight of the total amount of the component polymer, component (A), low molecular weight compound, and polymer selected from polymer (B) And 100 parts by mass of the total amount of the crosslinking agent of component (C), selected from 0.1 part by mass to 40 parts by mass of component (D), and (A) component low molecular weight compound and polymer.
  • the blending ratio, preparation method, and the like when the cured film forming composition of the present embodiment is used as a solution will be described in detail below.
  • the ratio of the solid content in the cured film forming composition of the present embodiment is not particularly limited as long as each component is uniformly dissolved in the solvent, but is 1% by mass to 80% by mass, preferably It is 3% by mass to 60% by mass, and more preferably 5% by mass to 40% by mass.
  • solid content means what remove
  • the method for preparing the cured film forming composition of the present embodiment is not particularly limited.
  • a preparation method for example, the (A) component, the (C) component, the (D) component, and the (E) component are mixed in a predetermined ratio to the solution of the (B) component dissolved in the solvent to obtain a uniform solution. Or a method in which other additives are further added and mixed as necessary at an appropriate stage of the preparation method.
  • a solution of a specific copolymer obtained by a polymerization reaction in a solvent can be used as it is.
  • the (A) component, the (C) component, the (D) component, and the (E) component are added to the solution prepared from the (B) component acrylic polymer to obtain a uniform solution.
  • a solvent may be further added for the purpose of adjusting the concentration.
  • the solvent used in the preparation process of the component (B) and the solvent used for adjusting the concentration of the cured film forming composition may be the same or different.
  • the prepared cured film-forming composition solution is preferably used after being filtered using a filter having a pore size of about 0.2 ⁇ m.
  • the cured film forming composition of this embodiment of the present invention is represented by (A) a photo-alignment group and a hydroxy group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group, and the above formula (2).
  • a low molecular compound having at least one substituent selected from the group to be selected and at least one selected from polymers (B) a hydroxy group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group, and the above formula (2) And a polymer having at least one substituent selected from the above groups.
  • the photoalignment group constitutes a hydrophobic photoreactive portion, and includes a hydroxy group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group, and the above At least one substituent selected from the group represented by the formula (2) constitutes a hydrophilic thermal reaction part.
  • the hydroxyl group, carboxyl group, amide group, amino group, alkoxysilyl group and at least one substituent selected from the group represented by the above formula (2) are also hydrophilic.
  • the cured film formed from the cured film forming composition of the present embodiment is formed with hydrophilic inside due to the nature of the component (B) so that the film structure is stabilized.
  • at least 1 type chosen from the low molecular compound and polymer of (A) component in a cured film comes to be unevenly distributed in the surface vicinity of a cured film.
  • at least one selected from the low molecular compound and polymer of the component (A) has a structure in which the hydrophilic thermal reaction part faces the inner side of the cured film and the hydrophobic photoreaction part faces the surface side. While being removed, it is unevenly distributed near the surface of the cured film.
  • the cured film of the present embodiment realizes a structure in which the ratio of the photoreactive group of the component (A) existing near the surface is increased. And when the cured film of this embodiment is used as an alignment material, the efficiency of the photoreaction for photo-alignment can be improved and it can have the outstanding orientation sensitivity. Furthermore, it becomes an orientation material suitable for formation of a patterned phase difference material, and the patterned phase difference material manufactured using this can have the outstanding pattern formation property.
  • the cured film forming composition of this embodiment contains a crosslinking agent as (C) component as mentioned above. Therefore, in the cured film obtained from the cured film-forming composition of the present embodiment, before the photoreaction with at least one photoalignable group selected from the low molecular compound and polymer of the component (A) (C ) A crosslinking reaction by a thermal reaction with a crosslinking agent can be performed. As a result, when used as an alignment material, it is possible to improve the resistance to the polymerizable liquid crystal applied thereon and its solvent.
  • the compound as component (D) is between the cured polymerizable liquid crystal layer formed thereon. It functions to reinforce the adhesion.
  • a solution of the cured film forming composition according to the present embodiment is applied to a substrate (for example, a silicon / silicon dioxide-coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, or chromium, a glass substrate, or a quartz substrate.
  • a substrate for example, a silicon / silicon dioxide-coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, or chromium, a glass substrate, or a quartz substrate.
  • a cured film can be formed by coating by slit coating, spin coating following the slit, inkjet coating, printing, or the like to form a coating film, followed by heat drying with a hot plate or oven.
  • TAC triacetyl cellulose
  • cycloolefin polymer film polyethylene terephthalate film
  • resin film such as acrylic film
  • bar coating spin coating
  • flow coating roll coating
  • a cured film can be formed by coating by slit coating, spin coating following the slit, inkjet coating, printing, or the like to form a coating film, followed by heat drying with a hot plate or oven.
  • the heating and drying conditions may be such that the curing reaction proceeds to such an extent that the alignment material component formed from the cured film does not elute into the polymerizable liquid crystal solution applied thereon, for example, a temperature of 60 ° C. to 200 ° C.
  • the heating temperature and the heating time appropriately selected from the range of time 0.4 minutes to 60 minutes are employed.
  • the heating temperature and heating time are preferably 70 ° C. to 160 ° C., 0.5 minutes to 10 minutes.
  • the film thickness of the cured film formed using the curable composition of the present embodiment is, for example, 0.05 ⁇ m to 5 ⁇ m, and is appropriately selected in consideration of the level difference of the substrate to be used and the optical and electrical properties. be able to.
  • the cured film thus formed can function as an alignment material, that is, a member for aligning a liquid crystalline compound including a polymerizable liquid crystal by performing polarized UV irradiation.
  • ultraviolet light or visible light having a wavelength of 150 nm to 450 nm is usually used, and irradiation is performed by irradiating linearly polarized light from a vertical or oblique direction at room temperature or in a heated state.
  • the alignment material formed from the cured film composition of the present embodiment has solvent resistance and heat resistance, after applying a retardation material comprising a polymerizable liquid crystal solution on the alignment material, the liquid crystal The phase difference material is brought into a liquid crystal state by heating up to the phase transition temperature, and aligned on the alignment material. Then, the retardation material in a desired orientation state is cured as it is, and a retardation material having a layer having optical anisotropy can be formed.
  • the retardation material for example, a liquid crystal monomer having a polymerizable group and a composition containing the same are used. And when the board
  • the phase difference material that forms such a phase difference material is in a liquid crystal state and has an alignment state such as horizontal alignment, cholesteric alignment, vertical alignment, hybrid alignment, etc. on the alignment material. It can be used properly according to the phase difference characteristic.
  • the patterned phase difference material used for 3D display it is predetermined
  • the polymerizable liquid crystal in a liquid crystal state is aligned on an alignment material on which two types of liquid crystal alignment regions are formed, and forms an alignment state corresponding to each liquid crystal alignment region. Then, the retardation material in which such an orientation state is realized is cured as it is, the above-described orientation state is fixed, and a plurality of two kinds of retardation regions having different retardation characteristics are regularly arranged. A phase difference material can be obtained.
  • the alignment material formed from the cured film composition of this embodiment can also be used as a liquid crystal alignment film of a liquid crystal display element.
  • the alignment materials on both the substrates are bonded to each other via a spacer, and then between the substrates.
  • a liquid crystal display element in which liquid crystal is aligned can be manufactured by injecting liquid crystal into the liquid crystal. Therefore, the cured film forming composition of this Embodiment can be used suitably for manufacture of various retardation materials (retardation film), a liquid crystal display element, etc.
  • compositional components used in Examples and their abbreviations Each composition component used in the following examples and comparative examples is as follows.
  • Me represents a methyl group
  • t-Bu represents a tert-butyl group.
  • CIN 4 4- (6-Methacryloxyhexyl-1-oxy) cinnamic acid
  • Polyester polyol polymer (Adipic acid / diethylene glycol copolymer having the following structural units. Molecular weight 4,800) (In the above formula, R represents alkylene.)
  • Each of the cured film forming compositions of Examples and Comparative Examples contained a solvent, and propylene glycol monomethyl ether (PM), butyl acetate (BA), and methyl ethyl ketone (MEK) were used as the solvent.
  • PM propylene glycol monomethyl ether
  • BA butyl acetate
  • MEK methyl ethyl ketone
  • Example 1 3.5 g of MAA, 7.0 g of MMA, 7.0 g of HEMA, and 0.5 g of AIBN as a polymerization catalyst were dissolved in 53.9 g of PM and reacted at 70 ° C. for 20 hours to obtain an acrylic copolymer solution (solid content concentration). 25% by mass) (P1) was obtained. Mn of the obtained acrylic copolymer was 10,300 and Mw was 24,600.
  • BMAA Nn-butoxymethylacrylamide
  • AIBN AIBN as a polymerization catalyst
  • the mixed solution of the two organic layers was further washed with 170 g of brine, and the obtained organic layer was dried over magnesium sulfate. Magnesium sulfate was removed by filtration, and the resulting dichloromethane solution was concentrated and dried to obtain the desired [D-6] (16.2 g, 33.1 mmol, yield 91.0%).
  • the structure of the compound [D-6] was confirmed by obtaining the following spectral data by 1 H-NMR analysis.
  • the acrylic film used as the substrate can be prepared, for example, by the following method. That is, raw material pellets made of a copolymer containing methyl methacrylate as a main component are melted by an extruder at 250 ° C., passed through a T-die, and an acrylic film having a thickness of 40 ⁇ m is formed through a casting roll and a drying roll. can do.
  • a TAC film can be similarly produced.
  • Examples 1 to 18 and Comparative Examples 1 and 2 Each cured film formation composition of an Example and a comparative example was prepared with the composition shown in Table 1, and orientation, pattern formation property, and adhesiveness were evaluated about each.
  • the coating film on this substrate was exposed at 300 mJ / cm 2 to produce a retardation material.
  • the phase difference material on the prepared substrate is sandwiched between a pair of polarizing plates, the state of the phase difference characteristic in the phase difference material is observed, ⁇ if the phase difference is expressed without defects, and no phase difference is expressed This was described as x in the column of “Orientation” in Table 2.
  • the alignment material obtained by using the cured film forming compositions of Examples 1 to 18 showed good alignment properties, similar to the alignment material obtained by using the cured film forming composition of the comparative example.
  • the alignment material obtained using the cured film forming compositions of Examples 1 to 18 showed good pattern formability similarly to the alignment material obtained using the cured film forming composition of the comparative example. It was.
  • the cured films obtained using the cured film forming compositions of Examples 1 to 18 maintained high adhesion even after high temperature and high humidity treatment, and exhibited excellent adhesion durability. On the other hand, it was difficult for the cured film obtained using the cured film forming composition of the comparative example to maintain the initial adhesion after the high temperature and high humidity treatment.
  • the cured film forming composition according to the present invention is very useful as an alignment material for forming a liquid crystal alignment film of a liquid crystal display element and an optically anisotropic film provided inside or outside the liquid crystal display element, It is suitable as a material for forming a patterned retardation material for a 3D display. Further, a material for forming a cured film such as a protective film, a planarizing film and an insulating film in various displays such as a thin film transistor (TFT) type liquid crystal display element and an organic EL element, in particular, an interlayer insulating film and a color filter of the TFT type liquid crystal element It is also suitable as a material for forming a protective film or an insulating film of an organic EL element.
  • TFT thin film transistor

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  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

L'invention a pour objet de réaliser une composition pour former un film durci qui convient pour former un film durci possédant d'excellentes propriétés d'alignement de cristaux liquides et de stabilité d'adhérence, de réaliser un matériau d'alignement et d'utiliser le matériau d'alignement pour produire un matériau de retardement. L'invention réalise à cet effet une composition pour former un film durci qui contient : (A) au moins une substance choisie parmi des composés à faible masse moléculaire qui comprennent un groupe photo-alignable et au moins un groupe choisi au sein du groupe composé d'un groupe d'hydroxydes, un groupe de carboxyles, un groupe d'aminés, un groupe d'alkoxysilyles et le groupe qui est représenté par la formule (2) (formule chimique (1)) et des polymères qui comprennent un groupe photo-alignable et un substitut qui est choisi dans le groupe composé d'un groupe d'hydroxydes, un groupe de carboxyles, un groupe d'amides, un groupe d'aminés, un groupe d'alkoxysilyles et le groupe qui est représenté par la formule (2) ; (B) un polymère qui comprend au moins un substitut choisi parmi un groupe d'hydroxydes, un groupe de carboxyles, un groupe d'aminés, un groupe d'alkoxysilyles et le groupe qui est représenté par la formule (2) ; (C) un agent de réticulation ; et (D) un composé à faible masse moléculaire qui comprend au moins un groupe polymérisable ayant une double liaison C=C par molécule de celui-ci et au moins un groupe de N-alkoxyméthyle. La composition pour former un film durci est utilisée pour former un film durci et une technologie de photo-alignement est utilisée pour former le matériau d'alignement. Un cristal liquide polymérisable est appliqué sur le matériau d'alignement et durci afin d'obtenir le matériau de retardement.
PCT/JP2014/077546 2013-10-17 2014-10-16 Composition pour former un film durci, matériau d'alignement et matériau de retardement WO2015056741A1 (fr)

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JP2015542656A JP6429030B2 (ja) 2013-10-17 2014-10-16 硬化膜形成組成物、配向材および位相差材
KR1020217012260A KR20210049950A (ko) 2013-10-17 2014-10-16 경화막 형성 조성물, 배향재 및 위상차재
CN201480056944.9A CN105659120B (zh) 2013-10-17 2014-10-16 固化膜形成用组合物、取向材料及相位差材料
KR1020167009844A KR102333902B1 (ko) 2013-10-17 2014-10-16 경화막 형성 조성물, 배향재 및 위상차재

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JP2013216571 2013-10-17
JP2013-216571 2013-10-17
JP2014061914 2014-03-25
JP2014-061914 2014-03-25
JP2014-140802 2014-07-08
JP2014140802 2014-07-08

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WO2015146905A1 (fr) * 2014-03-25 2015-10-01 日産化学工業株式会社 Composé possédant un groupe polymérisable et un groupe réticulable et son procédé de production
WO2016031917A1 (fr) * 2014-08-28 2016-03-03 日産化学工業株式会社 Composition permettant la formation d'un film durci, matériau d'alignement et matériau de retard optique
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CN107615148A (zh) * 2015-06-02 2018-01-19 日产化学工业株式会社 光取向用液晶取向剂、取向材料及相位差材料
WO2017155023A1 (fr) * 2016-03-09 2017-09-14 シャープ株式会社 Composition, panneau à cristaux liquides, dispositif d'affichage à cristaux liquides et dispositif électronique
CN110366698A (zh) * 2016-12-28 2019-10-22 日产化学株式会社 液晶取向剂、液晶取向膜、以及液晶表示元件
JPWO2018174102A1 (ja) * 2017-03-23 2019-11-07 富士フイルム株式会社 シート用硬化性組成物、硬化物及びその製造方法、立体成型用シート、光学部材、レンチキュラーシート、並びに３次元構造物
WO2018174102A1 (fr) * 2017-03-23 2018-09-27 富士フイルム株式会社 Composition durcissable pour feuilles, produit durci et son procédé de production, feuille pour mise en forme tridimensionnelle, élément optique, feuille lenticulaire et structure tridimensionnelle
JPWO2018181364A1 (ja) * 2017-03-27 2020-02-06 日産化学株式会社 硬化膜形成組成物、配向材および位相差材
WO2018181364A1 (fr) * 2017-03-27 2018-10-04 日産化学株式会社 Composition formant film durci, matériau d'alignement, et matériau à différence de phase
JP7260853B2 (ja) 2017-03-27 2023-04-19 日産化学株式会社 硬化膜形成組成物、配向材および位相差材
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JP7401855B2 (ja) 2018-07-10 2023-12-20 日産化学株式会社 硬化膜、配向材および位相差材
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JPWO2015056741A1 (ja) 2017-03-09
TWI650356B (zh) 2019-02-11
CN105659120A (zh) 2016-06-08
JP6429030B2 (ja) 2018-11-28
KR20160075515A (ko) 2016-06-29
KR20210049950A (ko) 2021-05-06
TW201529669A (zh) 2015-08-01

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