WO2015030000A1 - Composition permettant de former un film durci, matériau d'alignement, et matériau à différence de phase - Google Patents

Composition permettant de former un film durci, matériau d'alignement, et matériau à différence de phase Download PDF

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Publication number
WO2015030000A1
WO2015030000A1 PCT/JP2014/072305 JP2014072305W WO2015030000A1 WO 2015030000 A1 WO2015030000 A1 WO 2015030000A1 JP 2014072305 W JP2014072305 W JP 2014072305W WO 2015030000 A1 WO2015030000 A1 WO 2015030000A1
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Prior art keywords
group
acid
cured film
component
nylon
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PCT/JP2014/072305
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English (en)
Japanese (ja)
Inventor
真 畑中
昇志郎 湯川
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日産化学工業株式会社
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Priority to KR1020167005264A priority Critical patent/KR102311602B1/ko
Priority to JP2015534234A priority patent/JP6451953B2/ja
Priority to CN201480047464.6A priority patent/CN105492535B/zh
Publication of WO2015030000A1 publication Critical patent/WO2015030000A1/fr

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    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/48—Polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/48—Polymers modified by chemical after-treatment
    • C08G69/50—Polymers modified by chemical after-treatment with aldehydes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D177/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D177/06—Polyamides derived from polyamines and polycarboxylic acids
    • 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
    • G02F1/13378—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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators

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 patterned retardation material is usually arranged on a display element such as a liquid crystal panel.
  • the patterned retardation material is configured by regularly arranging a plurality of two kinds of retardation regions having different retardation characteristics.
  • 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 light (see Patent Documents 3 to 5).
  • an acrylic resin having a photodimerization site such as a cinnamoyl group or a chalcone group in the side chain has sufficient characteristics (orientation sensitivity) when applied to the formation of a retardation material. I know I can't get it.
  • a large amount of polarized UV exposure is required. . Its polarized UV exposure is sufficient polarized UV exposure to orient the liquid crystal for conventional liquid crystal panel (e.g., 100 mJ / cm 2 degrees.) Becomes significantly more than.
  • the reason why the amount of polarized UV exposure increases is that, in the case of forming a retardation material, different from the liquid crystal for a liquid crystal panel, a polymerizable liquid crystal is used in a solution state and applied onto an alignment material. ing.
  • the acrylic resin or the like when an alignment material is formed using an acrylic resin or the like having a photodimerization site such as a cinnamoyl group in the side chain, and an attempt is made to align the polymerizable liquid crystal using the alignment material, the acrylic resin or the like is first used.
  • the photocrosslinking is carried out by photodimerization reaction. And it is necessary to irradiate polarized light with a large exposure amount until resistance to the polymerizable liquid crystal solution is developed.
  • the alignment material is to be made resistant to the polymerizable liquid crystal solution (solvent resistance) using a conventional material such as the above-mentioned acrylic resin, it is necessary to advance the reaction to the inside of the alignment material, and more exposure. A quantity is required. As a result, there is a problem that the orientation sensitivity of the conventional material becomes very small.
  • a photo-alignment technique capable of improving the alignment sensitivity of the alignment material and reducing the polarized UV exposure amount, and a cured film forming composition used for forming the alignment material are required. And the technique which can provide a patterned phase difference material with high efficiency is calculated
  • the adhesion to the resin film is weak, and it is difficult to produce a highly reliable patterned retardation material on the resin film.
  • an object of the present invention is to provide a cured film forming composition for providing an alignment material having excellent photoreaction efficiency and solvent resistance, and capable of aligning a polymerizable liquid crystal with high sensitivity even on a resin film. Is to provide.
  • Another object of the present invention is obtained from the cured film-forming composition, and has excellent photoreaction efficiency and solvent resistance, and can align a polymerizable liquid crystal with high sensitivity even on a resin film.
  • An object is to provide an alignment material and a retardation material formed using the alignment material.
  • the first aspect of the present invention is: (A) a compound having a photo-alignment group and any one substituent selected from a hydroxy group, a carboxyl group, an amino group, and an alkoxysilyl group,
  • the invention relates to a cured film forming composition comprising (B) a polyamide in which at least a part of nitrogen atoms of an amide group is alkoxymethylated or alkylthiomethylated, and (C) a crosslinking catalyst.
  • the photoalignable group of the component (A) is a functional group having a structure that undergoes photodimerization or photoisomerization.
  • the photoalignable group of the component (A) is a cinnamoyl group.
  • the photoalignable group of the component (A) is a group having an azobenzene structure.
  • the polyamide of the component (B) is nylon-6, nylon-11, nylon-12, nylon-66, nylon-610, nylon-612, nylon-1010, nylon-1212, nylon A polyamide selected from the group consisting of -66/610, nylon 6/66, nylon 6/69, nylon 6-I / 6-T, and combinations of two or more thereof is N-alkoxymethylated or N-alkylthio It is preferable that it is methylated.
  • the polyamide of component (B) is N-alkoxymethylated polyamide.
  • the polyamide as the component (B) preferably has a weight average molecular weight of 1,000 to 100,000.
  • the second aspect of the present invention relates to an alignment material characterized by being obtained using the thermosetting film forming composition of the first aspect of the present invention.
  • 3rd aspect of this invention is related with the phase difference material formed using the cured film obtained from the cured film formation composition of the 1st aspect of this invention.
  • an alignment material that has excellent photoreaction efficiency and solvent resistance, can align a polymerizable liquid crystal with high sensitivity, and exhibits high adhesion to a substrate.
  • a cured film forming composition can be provided.
  • an alignment material having excellent photoreaction efficiency and solvent resistance, capable of aligning a polymerizable liquid crystal with high sensitivity, and exhibiting high adhesion to a substrate. Can do.
  • the third aspect of the present invention it is possible to provide a retardation material that can be formed with high efficiency even on a resin film and that can be subjected to optical patterning.
  • the low molecular photo-alignment component as component (A) and the nitrogen atom of the amide group as component (B) are alkoxymethylated or alkylthiomethylated.
  • the cured film forming composition of the present embodiment further includes a hydroxyalkyl ester group having 2 to 5 carbon atoms as the component (D), alkoxy
  • An acrylic polymer having at least one of a silyl group, an N-alkoxymethyl group, a carboxyl group, and a phenolic hydroxy group can be contained. And as long as the effect of this invention is not impaired, another additive can be contained.
  • details of each component will be described.
  • the component (A) of the composition of the present invention is a low molecular orientation component.
  • the component (A) is a component that imparts photo-alignment to the cured film of the present embodiment obtained from the composition of the present invention, and has a low molecular photo-alignment compared to the polymer of the later-described component (B) serving as a base. Become an ingredient.
  • the low molecular alignment component as the component (A) is a compound having a photoalignable group and one group selected from the group consisting of a hydroxy group, a carboxyl group, an amino group, and an alkoxysilyl group It is.
  • the photoalignable group means a functional group having a photodimerization structure or a functional group having a photoisomerization structure.
  • photo-alignment group a functional group that causes a photofleece rearrangement reaction (example compound: benzoate ester compound, etc.), a group that causes a photodecomposition reaction (example compound: cyclobutane ring, etc.), and the like can also be used.
  • the photo-dimerizing structure part that the compound (A) can have as a photo-alignment group is a part that forms a dimer by light irradiation, and 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 site that the compound of component (A) can have as a photoalignable group refers to a structural site that changes into a cis form and a trans form by light irradiation, and specific examples thereof include an azobenzene structure. And a site comprising a stilbene structure and the like. Of these, an azobenzene structure is preferred because of its high reactivity.
  • the compound having a photo-alignment group and one selected from the group consisting of a hydroxy group, a carboxyl group, an amino group, and an alkoxysilyl group are shown in the following formulas [A1] to [A5].
  • the compound of A component is not limited to the following specific example.
  • a 1 and A 2 each independently represent a hydrogen atom or a methyl group.
  • X 1 is a single bond, an ether bond, an ester bond, a carbonyl, an amide bond, a urethane bond, a urea bond, an amino bond, or a combination thereof, or a combination of the one or two kinds 1 to 3 substituents selected from an alkylene group having 1 to 18 carbon atoms, a phenylene group, a biferene group, and a combination thereof are bonded to each other, and the substituent is bonded via the bond.
  • a structure in which a plurality of them are connected may be used.
  • X 2 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, or a urea bond.
  • X 3 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 phenyl group, a phenoxy group, a biphenyl group, or a biphenyloxy group.
  • X 4 each independently represents a single bond, an alkylene group having 1 to 20 carbon atoms, an aromatic ring group, or an aliphatic ring group.
  • the alkylene group having 20 to 20 carbon atoms may be branched or linear.
  • X 5 represents a hydroxy group, a carboxyl group, an amino group or an alkoxysilyl group.
  • X represents a single bond, an oxygen atom or a sulfur atom.
  • the phenyl group and the biphenyl group are the same or selected from 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 more different substituents.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 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.
  • the compound having a photo-alignable group and a hydroxy group as the component (A) include compounds represented by the above formulas [A1] to [A5] and compounds other than the above formulas such as 4- ( 8-hydroxyoctyloxy) cinnamic acid methyl ester, 4- (6-hydroxyhexyloxy) cinnamic acid methyl ester, 4- (4-hydroxybutyloxy) cinnamic acid methyl ester, 4- (3-hydroxypropyloxy) ) Cinnamic acid methyl ester, 4- (2-hydroxyethyloxy) cinnamic acid methyl ester, 4-hydroxymethyloxy cinnamic acid methyl ester, 4-hydroxycinnamic acid methyl ester, 4- (8-hydroxyoctyloxy) ) Cinnamic acid ethyl ester, 4- (6-hydroxyhexyloxy) cinnamic acid ethyl ester, 4- 4-hydroxybutyloxy) cinnna
  • the compound (A) having a photo-alignment group and a carboxyl group include cinnamic acid, ferulic acid, 4-nitrocinnamic acid, 4-methoxycinnamic acid, and 3,4-dimethoxycinnamic acid. Cinnamic acid, coumarin-3-carboxylic acid, 4- (N, N-dimethylamino) cinnamic acid and the like.
  • Specific examples of the compound having a photo-alignable group and an amino group as component (A) include 4-aminocinnamic acid methyl ester, 4-amino cinnamic acid ethyl ester, 3-amino cinnamic acid methyl ester, Examples thereof include 3-aminocinnamic acid ethyl ester.
  • Specific examples of the compound (A) having a photo-alignment group and an alkoxysilyl group include 4- (3-trimethoxysilylpropyloxy) cinnamic acid methyl ester, 4- (3-triethoxysilyl) Propyloxy) cinnamic acid methyl ester, 4- (3-trimethoxysilylpropyloxy) cinnamic acid ethyl ester, 4- (3-triethoxysilylpropyloxy) cinnamic acid ethyl ester, 4- (6-trimethoxy Silylhexyloxy) cinnamic acid methyl ester, 4- (6-triethoxysilylhexyloxy) cinnamic acid methyl ester, 4- (6-trimethoxysilylhexyloxy) cinnamic acid methyl ester, 4- (6-trimethoxysilylhexyloxy) cinnamic acid ethyl
  • the low molecular orientation component which is the component (A) is a compound having a photoalignment group and a hydroxy group
  • the component (A) two or more photoalignment groups and / or hydroxy are present in the molecule. It is possible to use compounds having two or more groups.
  • a compound having two or more photo-alignable groups and two hydroxyl groups in the molecule can be used.
  • compounds having two or more photoalignable groups and hydroxy groups in the molecule can be exemplified by compounds represented by the following formulae.
  • the molecular weight of the low molecular orientation component (A) component is controlled to a value within a desired range.
  • heat curing is required, but when the heating is performed, the low molecular orientation component (A) component sublimes. Can be suppressed.
  • the compound of component (A) in the composition of the present invention is a mixture of a plurality of types of compounds having a photoalignment group and any one of a hydroxy group, a carboxyl group, an amino group, and an alkoxysilyl group. May be.
  • composition of this invention can contain the compound which has a photo-alignment group represented by following formula [1] as (A) component.
  • each A 1 and A 2 independently represent a hydrogen atom or a methyl group
  • a 3 is a hydroxy group, a mercapto group, an alkoxy group having 1 to 10 carbon atoms, hydroxyalkoxy group having 1 to 10 carbon atoms
  • * represents a bonding end.
  • the hydrogen atoms of the benzene ring and the phenyl group are each independently a substituent selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, a cyano group, and a nitro group. May be substituted.
  • a 1 is preferably a hydrogen atom or a methyl group
  • a 2 is preferably a hydrogen atom
  • a 3 is preferably an alkoxy group having 1 to 10 carbon atoms, a phenyl group, or the like.
  • Specific examples of the compound having a photoalignable group and a hydroxy group represented by the above formula [1] include 4- [4- (8-hydroxyoctyloxy) benzoyl] cinnamic acid methyl ester, 4- [ 4- (6-hydroxyhexyloxy) benzoyl] cinnamic acid methyl ester, 4- [4- (4-hydroxybutyloxy) benzoyl] cinnamic acid methyl ester, 4- [4- (3-hydroxypropyloxy) benzoyl ] Cinnamic acid methyl ester, 4- [4- (2-hydroxyethyloxy) benzoyl] cinnamic acid methyl ester, 4- [4-hydroxymethyloxybenzoyl] cinnamic acid methyl ester, 4- [4-hydroxybenzoyl] ] Cinnamic acid methyl ester, 4- [4- (8-hydroxyoctyloxy) benzoyl] cinnamic acid Ester, 4- [4-
  • Specific examples of the compound having a photoalignable group and a carboxyl group represented by the above formula [1] include 4-benzoylcinnamic acid, 4- (4-nitrobenzoyl) cinnamic acid, 4- (4-methoxy Benzoyl) cinnamic acid, 4- (3,4-dimethoxybenzoyl) cinnamic acid and the like.
  • Specific examples of the compound having a photoalignable group and an amino group represented by the above formula [1] include 4- (4-aminobenzoyl) cinnamic acid methyl ester, 4- (4-aminobenzoyl) cinnamic acid Ethyl ester, 4- (4-aminobenzoyl) cinnamic acid tertiary butyl ester, 4- (3-aminobenzoyl) cinnamic acid methyl ester, 4- (3-aminobenzoyl) cinnamic acid ethyl ester, 4- ( And 3-aminobenzoyl) cinnamic acid tertiary butyl ester.
  • the compound having a photoalignable group represented by the above formula [1] and an alkoxysilyl group include 4- [4- (3-trimethoxysilylpropyloxy) benzoyl] cinnamic acid methyl ester, 4 -[4- (3-triethoxysilylpropyloxy) benzoyl] cinnamic acid methyl ester, 4- [4- (3-trimethoxysilylpropyloxy) benzoyl] cinnamic acid ethyl ester, 4- [4- (3 -Triethoxysilylpropyloxy) benzoyl] cinnamic acid ethyl ester, 4- [4- (3-trimethoxysilylpropyloxy) benzoyl] cinnamic acid tertiary butyl ester, 4- [4- (3-triethoxysilyl) Propyloxy) benzoyl] cinnamic acid tertiary
  • a 1 and A 2 each independently represent a hydrogen atom or a methyl group
  • a 3 represents a hydroxy group, a mercapto group, an alkoxy group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms.
  • This compound is a novel compound not described in any document, and can be produced, for example, by the method shown in the following scheme.
  • a 1 , A 2 , A 3 and n are as defined in the above formula [2], and Hal represents a halogen atom.
  • the cured film forming composition of this Embodiment contains the polyamide by which at least one part of the nitrogen atom of the amide group was alkoxymethylated or alkylthiomethylated as (B) component.
  • the polyamide of component (B) in the present invention is a polyamide synthesized by polycondensation of ⁇ -aminocarboxylic acid, ring-opening polymerization of the lactam, a polyamide synthesized by polycondensation of dicarboxylic acid and diamine, or the like. Two or more copolymers or blends can be used.
  • Polyamides synthesized by polycondensation of ⁇ -aminocarboxylic acids or ring-opening polymerization of the lactams are disclosed in, for example, Nylon Plastics (Melvin L. Kohan, 1973, John Wiley and Sons, Inc.). Examples thereof include nylon-6, nylon-11, nylon-12, or combinations of two or more thereof. Examples of polyamides prepared from more than one type of lactam or aminocarboxylic acid include nylon-6,12. Examples of frequently used polyamides include nylon-6, nylon-11, nylon-12, and nylon-6,12, or combinations of two or more thereof.
  • diamines having no aromatic ring such as aliphatic diamine and alicyclic diamine are preferable.
  • aliphatic diamines examples include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,3-diamino-2,2-dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1,7 -Diamino-2,5-dimethylheptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane, 1,9-diamino-5-methylheptane, 1,12-diamino Examples include dodecane, 1,18-diaminoocta
  • alicyclic diamines examples include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4′-diaminodicyclohexylmethane, 4,4′-diamino-3,3′-dimethyldicyclohexylamine, isophorone diamine Etc.
  • aromatic diamine, aromatic-aliphatic diamine, heterocyclic diamine, etc. may be used as long as the effects of the present invention are not impaired.
  • the total amount of these aromatic diamines, aromatic-aliphatic diamines, heterocyclic diamines and the like is preferably 10 mol or less per 100 mol of the total amount of all diamines. If the content of aromatic diamine, aromatic-aliphatic diamine, heterocyclic diamine, etc. is excessive, formaldehyde reacts with the aromatic ring during N-alkoxymethyl modification, and the resulting resin is handled. Properties and physical properties may deteriorate.
  • aromatic diamines examples include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 3,5-diaminotoluene, 1,4-diamino -2-methoxybenzene, 2,5-diamino-p-xylene, 1,3-diamino-4-chlorobenzene, 3,5-diaminobenzoic acid, 1,4-diamino-2,5-dichlorobenzene, 4,4 '-Diamino-1,2-diphenylethane, 4,4'-diamino-2,2'-dimethylbibenzyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane 4,4′-diamin
  • aromatic-aliphatic diamines include 3-aminobenzylamine, 4-aminobenzylamine, 3-amino-N-methylbenzylamine, 4-amino-N-methylbenzylamine, 3-aminophenethylamine, 4-aminobenzylamine, Aminophenethylamine, 3-amino-N-methylphenethylamine, 4-amino-N-methylphenethylamine, 3- (3-aminopropyl) aniline, 4- (3-aminopropyl) aniline, 3- (3-methylaminopropyl) Aniline, 4- (3-methylaminopropyl) aniline, 3- (4-aminobutyl) aniline, 4- (4-aminobutyl) aniline, 3- (4-methylaminobutyl) aniline, 4- (4-methyl Aminobutyl) aniline, 3- (5-aminopentyl) aniline, 4- (5-aminopentyl) Aniline, 3- (5-methyl)
  • heterocyclic diamines examples include 2,6-diaminopyridine, 2,4-diaminopyridine, 2,4-diamino-1,3,5-triazine, 2,7-diaminodibenzofuran, 3,6-diaminocarbazole 2,4-diamino-6-isopropyl-1,3,5-triazine, 2,5-bis (4-aminophenyl) -1,3,4-oxadiazole and the like.
  • the dicarboxylic acid to be reacted with the diamine component in order to obtain the polyamide of the present invention is preferably a dicarboxylic acid having no aromatic ring, such as an aliphatic dicarboxylic acid or an alicyclic dicarboxylic acid.
  • dicarboxylic acids or their aliphatic dicarboxylic acids include malonic acid, succinic acid, dimethylmalonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, muconic acid, 2-methyladipic acid, trimethyladipine And dicarboxylic acids such as acid, pimelic acid, 2,2-dimethylglutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid and suberic acid.
  • Examples of the alicyclic dicarboxylic acid include 1,1-cyclopropanedicarboxylic acid, 1,2-cyclopropanedicarboxylic acid, 1,1-cyclobutanedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, and 1,3-cyclobutanedicarboxylic acid.
  • aromatic dicarboxylic acid, dicarboxylic acid containing a heterocyclic ring, or the like may be used as long as the effects of the present invention are not impaired.
  • the total amount of the aromatic dicarboxylic acid and the dicarboxylic acid containing a heterocyclic ring is preferably 10 mol or less per 100 mol of the total amount of all dicarboxylic acids. If the content of aromatic dicarboxylic acid or dicarboxylic acid containing a heterocyclic ring is excessive, formaldehyde reacts with the aromatic ring during N-alkoxymethyl modification, and the handling properties and physical properties of the resulting resin are reduced. May decrease.
  • aromatic dicarboxylic acids o-phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butylisophthalic acid, 5-aminoisophthalic acid, 5-hydroxyisophthalic acid, 2,5-dimethylterephthalic acid Acid, tetramethylterephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-anthracenedicarboxylic acid, 1,4 Anthraquinone dicarboxylic acid, 2,5-biphenyl dicarboxylic acid, 4,4′-biphenyl dicarboxylic acid, 1,5-biphenylene dicarboxylic acid, 4,4 ′′ -terphenyl dicarboxylic acid, 4,4′-diphenylmethane dicarboxylic acid
  • dicarboxylic acid containing a heterocyclic ring examples include 1,5- (9-oxofluorene) dicarboxylic acid, 3,4-furandicarboxylic acid, 4,5-thiazole dicarboxylic acid, 2-phenyl-4,5-thiazole dicarboxylic acid, 1,2,5-thiadiazole-3,4-dicarboxylic acid, 1,2,5-oxadiazole-3,4-dicarboxylic acid, 2,3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, 2, Examples include 5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid, and 3,5-pyridinedicarboxylic acid.
  • the above various dicarboxylic acids may be acid dihalides or anhydrous structures. Some of the above dicarboxylic acid compounds have isomers, but a mixture containing them may also be used. Two or more compounds may be used in combination.
  • the dicarboxylic acids used in the present invention are not limited to the above exemplary compounds.
  • Methods for producing polyamide by polycondensation of dicarboxylic acid and diamine include reaction of dicarboxylic acid dichloride and diamine component, and reaction of dicarboxylic acid and diamine component in the presence of a suitable condensing agent and base. Can be mentioned.
  • dicarboxylic acid dichloride and diamine are reacted in the presence of a base and an organic solvent at ⁇ 20 ° C. to 150 ° C., preferably 0 ° C. to 50 ° C., for 30 minutes to 24 hours, preferably 1 to 4 hours.
  • a base and an organic solvent at ⁇ 20 ° C. to 150 ° C., preferably 0 ° C. to 50 ° C., for 30 minutes to 24 hours, preferably 1 to 4 hours.
  • pyridine triethylamine, 4-dimethylaminopyridine can be used, but pyridine is preferable because the reaction proceeds gently.
  • the addition amount of the base is preferably 2 to 4 moles relative to the dicarboxylic acid dichloride from the viewpoint that it can be easily removed and a high molecular weight product can be easily obtained.
  • condensation polymerization is carried out in the presence of a condensing agent, triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N′-carbonyldiimidazole, Dimethoxy-1,3,5-triazinylmethylmorpholinium, O- (benzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium tetrafluoroborate, O- (benzo Triazol-1-yl) -N, N, N ′, N′-tetramethyluronium hexafluorophosphate, (2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonate diphenyl, 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) 4-methoxymorpholium chloride
  • the reaction proceeds efficiently by adding Lewis acid as an additive.
  • Lewis acid lithium halides such as lithium chloride and lithium bromide are preferable.
  • the amount of Lewis acid added is preferably 0.1 to 1.0 times the molar amount of the dicarboxylic acid.
  • the organic solvent used for the reaction between the dicarboxylic acid and the diamine component is not particularly limited as long as the produced polyamide is soluble. Specific examples are given below.
  • N-methyl-2-pyrrolidone and ⁇ -butyrolactone are preferred in view of the solubility of the monomer and polymer, and these may be used alone or in combination.
  • the total monomer concentration during the synthesis is preferably 1 to 30% by mass and more preferably 5 to 20% by mass from the viewpoint that polymer precipitation is unlikely to occur and a high molecular weight product is easily obtained.
  • the polyamide used in the present invention has a viscosity (viscosity number: VN) measured at 0.5% in 96% H 2 SO 4 according to ISO 307 every about 140 to about 270 cubic centimeters. an aliphatic polyamide in the range of grams (cm 3 / g).
  • preferred polyamides are nylon-6, nylon-11, nylon-12, nylon-66, nylon-610, nylon-612, nylon-1010, nylon-1212, nylon-66 / 610, nylon-6. / 66, nylon 6/69, or polyamide selected from the group consisting of combinations of two or more thereof.
  • Nylon 6/66 (polyamide 6/66) is a product name of “Ultramid C4” and “Ultramid C35” from BASF or a product name of “Ube5033 FXD27” from Ube Industries Ltd. (Ube Industries Ltd.). It is commercially available.
  • Nylon 6 (polyamide 6) is, for example, E.I. I. It is commercially available from du Pont de Nemours.
  • More preferable polyamides include poly- ⁇ -capramide (nylon-6), polyhexamethylene adipamide (nylon 66), polyhexamethylene sebacamide (nylon 610), and other aliphatic polyamides, fats
  • polyamide containing a ring or a hetero ring in the main chain may be used.
  • aliphatic polyamide can refer to aliphatic polyamides, aliphatic copolyamides, and blends or mixtures thereof.
  • Polyamides thus obtained and commercially available polyamides can be synthesized by, for example, a method such as proposed by TLCairns et al. (J. Am. Chem. Soc., 71, P651 (1949)) to the nitrogen atom N of the amide bond with alkoxymethyl. Groups or alkylthiomethyl groups can be introduced.
  • a modified polyamide can be produced by allowing formalin and alcohol or mercaptan to act directly on the polyamide using a phosphoric acid catalyst at high temperature and high pressure.
  • the degree of substitution can be selected in a wide range depending on the reaction conditions.
  • the degree of substitution is 10 to 50 mol%, preferably 20 to 40 mol%. Those in this substitution region are most soluble in alcohol and have good stability in solution. If the content is lower than 10 mol%, the solvent solubility, adhesion, and volume resistivity cannot satisfy the characteristics. On the other hand, when the degree of substitution is higher than 50 mol%, it is difficult to set reaction conditions.
  • the type of the substituent of the nitrogen atom of the amide bond can be selected depending on the solvent used for the modification reaction. When an alcohol is used, for example, one having a methoxymethyl group, an ethoxymethyl group, an isobutoxymethyl group or the like is obtained.
  • mercaptan for example, those having an ethylthiomethyl group, an isobutylthiomethyl group or the like can be obtained.
  • the solubility of the resulting resin can be improved by the function of the polar group in which the nitrogen atom of the amide bond of the modified polyamide resin is substituted.
  • N-alkoxymethylated or N-alkylthiomethylated polyamide commercially available products can be used.
  • commercially available products include, for example, Toresin (registered trademark) flake type F-30K, MF-30, EF-30T, and water-soluble resin type FS-350E5AS from Nagase ChemteX Corporation.
  • the weight average molecular weight is a value obtained by using gel as a standard sample by gel permeation chromatography (GPC).
  • the cured film forming composition of this Embodiment contains a crosslinking catalyst as (C) component in addition to (A) component and (B) mentioned above.
  • the crosslinking catalyst for the component can be, for example, an acid or a thermal acid generator. This crosslinking catalyst is effective in promoting the thermosetting reaction in the formation of a cured film using the cured film forming composition of the present embodiment.
  • the component (C) is a sulfonic acid group-containing compound, hydrochloric acid or a salt thereof, a compound that generates heat by pre-baking or post-baking to generate an acid, that is, a temperature of 80
  • the compound is not particularly limited as long as it is a compound which generates an acid by thermal decomposition at a temperature of from 250 to 250 ° C.
  • 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, Trifluoromethanesulfonic 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
  • 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-phenylenetris (methylsulfonate), 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 (C) in the cured film forming composition of the embodiment of the present invention is such that at least a part of the compound (A) and the nitrogen atom of the amide group of the component (B) is alkoxymethylated or
  • the total amount with respect to 100 parts by mass of the alkylthiomethylated polyamide is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 8 parts by mass, and still more preferably 0.1 parts by mass. Parts to 6 parts by mass.
  • the content of the crosslinking catalyst By setting the content of the crosslinking catalyst to 0.01 parts by mass or more with respect to the total amount, sufficient thermosetting and solvent resistance can be imparted, and high sensitivity to exposure can also be imparted.
  • the storage stability of a cured film forming composition can be made favorable by making content of a crosslinking catalyst into 10 mass parts or less with respect to the said total amount.
  • the present invention may contain a component (D) in addition to the components (A) to (C).
  • Component (D) is an acrylic polymer having at least one of a hydroxyalkyl ester group having 2 to 5 carbon atoms, an alkoxysilyl group, an N-alkoxymethyl group, a carboxyl group and a phenolic hydroxy group.
  • a preferred addition amount of the component (D) is 5 to 100 parts by weight, more preferably 10 to 80 parts by weight based on 100 parts by weight of the total amount of the components (A) and (B). is there.
  • acrylic polymer a polymer obtained by polymerizing a monomer having an unsaturated double bond such as acrylic ester, methacrylic ester, styrene, acrylamide, or methacrylamide may be applied.
  • the acrylic polymer having at least one of a hydroxyalkyl ester group having 2 to 5 carbon atoms, an alkoxysilyl group, an N-alkoxymethyl group, a carboxyl group and a phenolic hydroxy group as the component (D) has such a structure.
  • a preferred structural unit is represented by the following formula [D1].
  • a structural unit having at least one of a carboxyl group or a phenolic hydroxy group is represented by the following formula [D2].
  • a structural unit having an N-alkoxymethyl group is represented by the following formula [D3].
  • X 11 , X 12 and X 13 each independently represent a hydrogen atom or a methyl group
  • Y 1 represents a hydroxyalkyl group having 1 to 3 carbon atoms or an alkoxysilylalkyl group having 1 to 4 carbon atoms. It represents, Y 2 is a carboxyl group or a phenolic hydroxy group, Y 3 represents a (carbon atom number of 1 to 6 alkoxy) methyl group.
  • the acrylic polymer as component (D) preferably has a weight average molecular weight of 3,000 to 200,000, more preferably 4,000 to 150,000, and 5,000 to 100,000. Even more preferred. If the weight average molecular weight is over 200,000, the solubility in the solvent may be reduced and the handling property may be reduced. If the weight average molecular weight is less than 3,000, There may be insufficient curing during curing and solvent resistance and heat resistance may decrease.
  • the method for synthesizing the acrylic polymer of component (D) includes a C2-C5 hydroxyalkyl ester group, an alkoxysilyl group, an N-alkoxymethyl group, a carboxyl group, and a phenolic hydroxy group.
  • a method of copolymerizing a monomer having at least one of the above is convenient.
  • 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, 4-hydroxybutyl methacrylate, 4- Examples include hydroxybutyl acrylate.
  • Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, and vinyl benzoic acid.
  • Examples of the monomer having a phenolic hydroxy group include p-hydroxystyrene, m-hydroxystyrene, and o-hydroxystyrene.
  • Examples of the monomer having an alkoxysilyl group include methacryloyloxypropyltrimethoxysilane, methacryloyloxypropyltriethoxysilane, acryloyloxypropyltrimethoxysilane, and acryloyloxypropyltriethoxysilane.
  • Examples of monomers having an N-alkoxymethyl group include N-methoxymethyl acrylamide, N-methoxymethyl methacrylamide, N-butoxymethyl acrylamide, N-butoxymethyl methacrylamide, N- (isobutoxymethyl) acrylamide, N- (Isobutoxymethyl) methacrylamide.
  • Examples of the other monomers include acrylic ester compounds, methacrylic ester compounds, maleimide compounds, acrylamide 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 compounds such as styrene, methylstyrene, chlorostyrene, bromostyrene, and 4-tert-butylstyrene.
  • vinyl compound examples include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl anthracene, vinyl biphenyl, vinyl carbazole, 2-hydroxyethyl vinyl ether, phenyl vinyl ether and propyl vinyl ether.
  • acrylic ester compounds and methacrylic ester compounds are preferable, and methyl methacrylate (methyl methacrylate) is particularly preferable in terms of availability and solubility.
  • the usage-amount of this other monomer is based on the total amount of all the monomers used in order to obtain the acrylic polymer of (D) component, 5 to 100 mol% is preferable.
  • the amount of the other monomer used is too small, the desired resistance to the liquid crystal solvent cannot be obtained, that is, the resistance may be lowered.
  • the method for obtaining the acrylic polymer of component (D) used in the present invention is not particularly limited.
  • a solvent in which the above-mentioned monomer, and optionally other monomers other than the above and a polymerization initiator coexist 50 to 110 It is obtained by a polymerization reaction at a temperature of ° C.
  • the solvent used will not be specifically limited if a monomer, a polymerization initiator, etc. are dissolved. Specific examples are described in ⁇ Solvent> described later.
  • the (D) component acrylic polymer obtained by the above method is usually in the form of a solution dissolved in a solvent.
  • the solution of the acrylic polymer of component (D) 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 reduced pressure, it can be dried at room temperature or by heating to obtain an acrylic polymer powder of component (D).
  • the polymerization initiator and unreacted monomer coexisting with the acrylic polymer of component (D) can be removed, and as a result, purified acrylic polymer powder of component (D) 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 of component (D) may be used in the form of a powder or in the form of a solution obtained by re-dissolving the purified powder in a solvent described later.
  • the (D) component acrylic polymer may be a mixture of a plurality of types of (D) component acrylic polymers.
  • the cured film forming composition of the present embodiment is mainly used in a solution state dissolved in a solvent.
  • the solvent used at that time is only required to be able to dissolve the component (A), the component (B), the component (C), and the component (D) and other additives as described below, if necessary. It is not limited.
  • the solvent include, for example, methanol, ethanol, 2-propanol, 1-butanol, 2-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-pentanone , 2-heptanone, ⁇ -butyrolactone, 2-hydroxypro Ethyl onate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethoxya
  • solvents can be used singly or in combination of two or more, and can also be used by mixing with water.
  • the cured film-forming composition of the present embodiment is a sensitizer, a silane coupling agent, a surfactant, a rheology modifier, a pigment, a dye, Storage stabilizers, antifoaming agents, antioxidants and the like can be contained.
  • a sensitizer is effective in promoting a photoreaction after forming a thermosetting film using the cured film forming composition of the present embodiment.
  • sensitizers examples include benzophenone, anthracene, anthraquinone, thioxanthone, and derivatives thereof, and nitrophenyl compounds.
  • benzophenone derivatives and nitrophenyl compounds are preferred.
  • Specific examples of preferred compounds include N, N-diethylaminobenzophenone, 2-nitrofluorene, 2-nitrofluorenone, 5-nitroacenaphthene, 4-nitrobiphenyl, 4-nitrocinnamic acid, 4-nitrostilbene, 4-nitrobenzophenone. , 5-nitroindole and the like.
  • N, N-diethylaminobenzophenone which is a derivative of benzophenone is preferable.
  • sensitizers are not limited to those described above.
  • the sensitizers can be used alone or in combination of two or more compounds.
  • a preferred use ratio of the sensitizer in the cured film forming composition of the present embodiment is that at least a part of the nitrogen atom of the compound (A) and the amide group (B) is alkoxymethylated or alkylthiomethyl.
  • the amount is 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass with respect to 100 parts by mass of the total mass with the modified polyamide. If this ratio is too small, the effect as a sensitizer may not be sufficiently obtained. If it is too large, the transmittance may be lowered and the coating film may be roughened.
  • the low molecular photo-alignment component as component (A) and the nitrogen atom of the amide group as component (B) are at least partially alkoxymethylated or alkylthiomethylated.
  • the obtained polyamide and the crosslinking catalyst (C) are dissolved in a solvent.
  • the cured film-forming composition of the present embodiment includes a component (D) of a hydroxyalkyl ester group having 2 to 5 carbon atoms, an alkoxysilyl group, an N-alkoxymethyl group, a carboxyl group, and a phenolic hydroxy group.
  • An acrylic polymer having at least one of the following can be contained. And as long as the effect of this invention is not impaired, another additive can be contained.
  • the content of the component (B) is excessively larger than the above numerical range, the liquid crystal orientation is likely to be lowered, and when it is too small, the solvent resistance is lowered and the orientation is likely to be lowered.
  • Preferred examples of the cured film forming composition of the present embodiment are as follows. [1]: The mixing ratio of the component (A) and the component (B) is 5:95 to 60:40 by mass ratio, and is based on 100 parts by mass of the total amount of the components (A) and (B). A cured film forming composition containing 0.01 to 10 parts by mass of component (C) and a solvent. [2]: The mixing ratio of the component (A) and the component (B) is 5:95 to 60:40 by mass ratio, and is based on 100 parts by mass of the total amount of the components (A) and (B). 0.01 parts by weight to 10 parts by weight of component (C), based on 100 parts by weight of the total amount of components (A) and (B), 5 parts by weight to 100 parts by weight of component (D), A cured film-forming composition containing a solvent.
  • 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 preferably 1% by mass to 80% by mass, preferably Is 3% to 60% by weight, more preferably 5% to 40% by weight.
  • solid content means what remove
  • the method for preparing the cured film forming composition of the present embodiment is not particularly limited.
  • the preparation method for example, a method of mixing the component (A) and the component (C) in a predetermined ratio with the solution of the component (B) dissolved in a solvent to obtain a uniform solution, or an appropriate method of this preparation method In the stage, there may be mentioned a method in which other additives are further added and mixed as necessary.
  • a polymer or copolymer solution obtained by a polymerization reaction in a solvent can be used as it is.
  • the (A) component and the (C) component are put into the solution of the (B) component in the same manner as described above to obtain a uniform solution.
  • a solvent may be further added for the purpose of adjusting the concentration.
  • the solvent used in the production 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 solution of the cured film forming composition according to the present embodiment is a substrate (for example, a silicon / silicon dioxide-coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, 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 crosslinking reaction heat curing
  • a heating temperature and a heating time appropriately selected from the range of a temperature of 60 ° C. to 200 ° C. and a time of 0.4 minutes to 60 minutes are employed.
  • the heating temperature and the heating time are preferably 70 to 160 ° C. and 0.5 to 10 minutes.
  • the film thickness of the cured film formed using the cured film forming 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 optical and electrical properties. can do.
  • the cured film thus formed can function as an alignment material, that is, a member for aligning a liquid crystal compound such as liquid crystal by performing polarized UV irradiation.
  • ultraviolet light to visible light having a wavelength of 150 nm to 450 nm is usually used, and it 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. Therefore, after applying a retardation material composed of a polymerizable liquid crystal solution, which will be described later, on this alignment material, the retardation material is changed to a liquid crystal state by heating to the phase transition temperature of the liquid crystal, and then aligned on the alignment material.
  • a retardation material can be formed as a layer having optical anisotropy by curing the retardation material in an oriented state as it is.
  • the retardation material for example, a liquid crystal monomer having a polymerizable group and a composition containing the same (that is, a polymerizable liquid crystal solution) are used.
  • substrate which forms an orientation material is a film
  • the film which has the phase difference material of this Embodiment is useful as a phase difference film.
  • Some of the retardation materials that form such a retardation material take an alignment state such as a horizontal alignment, a cholesteric alignment, a vertical alignment, and a hybrid alignment on the alignment material when in a liquid crystal state. It can be used properly according to the phase difference.
  • the patterned phase difference material used for 3D display it is predetermined
  • the alignment materials on both the substrates are bonded to each other through a spacer, and then the substrates A liquid crystal display element in which the liquid crystal is aligned can also be obtained by injecting liquid crystal therebetween.
  • 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.
  • FR-101 A product of 30% methoxymethylated low-polymerization degree 6 nylon produced by Lead City Co., Ltd. prepared in a 20 wt% ethanol solution
  • FR-103 20% of 6 nylon copolymer polyamide produced by Lead City Co., Ltd.
  • HMM Cymel 303 (Hexamethoxymethylmelamine) manufactured by Nihon Cytec Industries, Ltd.
  • EM-220 Made by Lead City Co., Ltd.
  • ⁇ (D) component> MAA: methacrylic acid MMA: methyl methacrylate HEMA: 2-hydroxyethyl methacrylate AIBN: ⁇ , ⁇ '-azobisisobutyronitrile
  • the number average molecular weight and weight average molecular weight of the acrylic copolymer obtained in accordance with the following synthesis examples were measured using a GPC apparatus (Shodex (registered trademark) columns KF803L and KF804L) manufactured by JASCO Corporation, and the elution solvent tetrahydrofuran at a flow rate of 1 mL. It was measured under the condition that the column was eluted at a rate of 40 minutes per minute (column temperature: 40 ° C.).
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • Examples 1 to 6 Comparative Examples 1 and 2> Prepare the cured film forming compositions of Examples 1 to 6 and Comparative Examples 1 to 4 with the compositions shown in Tables 1 and 2, and evaluate the adhesion, orientation sensitivity, pattern formability, and transmittance for each. went.
  • a film was formed. This film was exposed at 300 mJ / cm 2 to prepare a retardation material. Put a crosscut (1 mm ⁇ 1 mm ⁇ 100 mass) using a cutter knife to the retardation material on the obtained substrate, and then stick an adhesive tape (Cello Tape (registered trademark) manufactured by Nichiban Co., Ltd.), then When the adhesive tape was peeled off, the number of cells remaining without peeling off the film on the substrate was counted and evaluated as [number of remaining cells / 100]. A film in which 90 or more cells remained without peeling off the film was judged to have good adhesion.
  • Examples 1 to 6 regardless of the type of substrate used, all show liquid crystal alignment with a small exposure amount, and a cured film (alignment material) having excellent photoreaction efficiency and solvent resistance is obtained. I was able to. Furthermore, the obtained cured film showed high adhesion to the substrate regardless of the type of the substrate.
  • Comparative Examples 1 to 4 were not aligned even when irradiated with 100 mJ / cm 2 of linearly polarized light, and the adhesion was not evaluated.
  • 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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Abstract

Le problème décrit par la présente invention est de fournir une composition permettant de former un film durci qui forme un film durci présentant d'excellentes propriétés d'efficacité de photoréaction et de résistance aux solvants, et de fournir un matériau d'alignement pour l'alignement optique et un matériau à différence de phase formé à l'aide dudit matériau d'orientation. La solution selon l'invention porte sur une composition permettant de former un film durci contenant (A) un composé portant un groupe de photoalignement et au moins un groupe substituant choisi parmi un groupe hydroxyle, un groupe carboxyle, et un groupe aminé, (B) un polyamide dans lequel au moins une partie des atomes d'azote dans les groupes amide sont alcoxyméthylés ou alkylthiométhylés, et (C) un catalyseur de la réticulation. Un film durci est formé à l'aide de ladite composition permettant de former un film durci, et un matériau d'alignement est formé en faisant appel à une technique de photoalignement. Un matériau à différence de phase est obtenu en appliquant un revêtement de cristaux liquides polymérisables sur le matériau d'alignement et en durcissant ensuite les cristaux liquides polymérisables.
PCT/JP2014/072305 2013-08-27 2014-08-26 Composition permettant de former un film durci, matériau d'alignement, et matériau à différence de phase WO2015030000A1 (fr)

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KR1020167005264A KR102311602B1 (ko) 2013-08-27 2014-08-26 경화막 형성조성물, 배향재 및 위상차재
JP2015534234A JP6451953B2 (ja) 2013-08-27 2014-08-26 硬化膜形成組成物、配向材および位相差材
CN201480047464.6A CN105492535B (zh) 2013-08-27 2014-08-26 固化膜形成用组合物、取向材料及相位差材料

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JPWO2016194846A1 (ja) * 2015-06-02 2018-04-05 日産化学工業株式会社 光配向用液晶配向剤、配向材および位相差材
WO2019221137A1 (fr) * 2018-05-14 2019-11-21 コニカミノルタ株式会社 Film optique, film de retard, plaque de polarisation, et dispositif d'affichage à cristaux liquides
JPWO2021221100A1 (fr) * 2020-04-30 2021-11-04

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WO2019066225A1 (fr) * 2017-09-27 2019-04-04 주식회사 제이에이치씨 Film adhésif conducteur présentant une remarquable résistance à la chaleur et une remarquable résistance à l'humidité
KR102230885B1 (ko) * 2019-01-18 2021-03-23 주식회사 제이에이치씨 전도성 접착제 조성물 및 이를 이용한 전도성 접착 필름.

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JP6451953B2 (ja) 2019-01-16
TW201523130A (zh) 2015-06-16
KR102311602B1 (ko) 2021-10-13
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JPWO2015030000A1 (ja) 2017-03-02

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