WO2015030000A1 - Cured film-forming composition, alignment material, and phase difference material - Google Patents

Cured film-forming composition, alignment material, and phase difference material 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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French (fr)
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 JP2015534234A priority Critical patent/JP6451953B2/en
Priority to CN201480047464.6A priority patent/CN105492535B/en
Priority to KR1020167005264A priority patent/KR102311602B1/en
Publication of WO2015030000A1 publication Critical patent/WO2015030000A1/en

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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

Abstract

[Problem] To provide a cured film-forming composition that forms a cured film having excellent photoreaction efficiency and solvent resistance, and to provide an alignment material for optical alignment and a phase difference material formed using this alignment material. [Solution] Provided is a cured film-forming composition containing (A) a compound having a photo-aligning group and at least one substituent group selected from among a hydroxyl group, a carboxyl group, and an amino group, (B) a polyamide in which at least some of the nitrogen atoms in the amide groups are alkoxymethylated or alkylthiomethylated, and (C) a crosslinking catalyst. A cured film is formed using this cured film-forming composition, and an alignment material is formed by using a photo-alignment technique. A phase difference material is obtained by coating polymerizable liquid crystals on the alignment material and then curing the polymerizable liquid crystals.

Description

硬化膜形成組成物、配向材および位相差材Cured film forming composition, alignment material and retardation material
　本発明は、硬化膜形成組成物、配向材および位相差材に関する。 The present invention relates to a cured film forming composition, an alignment material, and a retardation material.
　近年、液晶パネルを用いたテレビ等のディスプレイの分野においては、高性能化に向けた取り組みとして、３Ｄ画像を楽しむことができる３Ｄディスプレイの開発が進められている。３Ｄディスプレイでは、例えば、観察者の右目に右目用画像を視認させ、観察者の左目に左目用画像を視認させることにより、立体感のある画像を表示させることができる。 In recent years, in the field of displays such as televisions using liquid crystal panels, development of 3D displays that can enjoy 3D images is being promoted as an effort to improve performance. In the 3D display, for example, a right-eye image is visually recognized by an observer's right eye, and a left-eye image is visually recognized by an observer's left eye, whereby a stereoscopic image can be displayed.
　３Ｄ画像を表示する３Ｄディスプレイの方式には多様なものがあり、専用のメガネを必要としない方式としては、レンチキュラレンズ方式およびパララックスバリア方式等が知られている。
　そして、観察者がメガネを着用して３Ｄ画像を観察するディスプレイの方式の１つとしては、円偏光メガネ方式等が知られている（例えば、特許文献１を参照。）。 There are various 3D display methods for displaying 3D images, and lenticular lens methods, parallax barrier methods, and the like are known as methods that do not require dedicated glasses.
And as one of the display systems in which an observer wears glasses and observes a 3D image, a circularly polarized glasses system or the like is known (see, for example, Patent Document 1).
　円偏光メガネ方式の３Ｄディスプレイの場合、液晶パネル等の画像を形成する表示素子の上にパターニングされた位相差材が配置されるのが通常である。このパターニングされた位相差材は、位相差特性の異なる２種類の位相差領域がそれぞれ複数、規則的に配置されることにより構成される。尚、以下、本明細書においては、このような位相差特性の異なる複数の位相差領域を配置するようにパターニングされた位相差材をパターン化位相差材と称する。 In the case of a circular polarized glasses type 3D display, 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. Hereinafter, in the present specification, 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.
　パターン化位相差材は、例えば、特許文献２に開示されるように、重合性液晶からなる位相差材料を光学パターニングすることで作製することができる。重合性液晶からなる位相差材料の光学パターニングは、液晶パネルの配向材形成で知られた光配向技術を利用する。すなわち、基板上に光配向性の材料からなる塗膜を設け、これに偏光方向が異なる２種類の偏光を照射する。そして、液晶の配向制御方向の異なる２種類の液晶配向領域が形成された配向材として光配向膜を得る。この光配向膜の上に重合性液晶を含む溶液状の位相差材料を塗布し、重合性液晶の配向を実現する。その後、配向された重合性液晶を硬化してパターン化位相差材を形成する。 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.
　液晶パネルの光配向技術を用いた配向材形成では、利用可能な光配向性の材料として、側鎖にシンナモイル基およびカルコン基等の光二量化部位を有するアクリル樹脂やポリイミド樹脂等が知られている。これらの樹脂は、偏光ＵＶ照射することにより、液晶の配向を制御する性能（以下、液晶配向性とも言う。）を示すことが報告されている（特許文献３～特許文献５を参照。）。 In the formation of alignment materials using the photo-alignment technology of liquid crystal panels, 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).
特開平１０－２３２３６５号公報Japanese Patent Laid-Open No. 10-232365 特開２００５－４９８６５号公報JP 2005-49865 A 特許第３６１１３４２号公報Japanese Patent No. 3611342 特開２００９－０５８５８４号公報JP 2009-058584 A 特表２００１－５１７７１９号公報JP-T-2001-517719
　しかしながら、本発明者らの検討によれば、こうした側鎖にシンナモイル基やカルコン基等の光二量化部位を有するアクリル樹脂は、位相差材の形成に適用した場合に充分な特性（配向感度）が得られないことが分かっている。特に、これらの樹脂に偏光ＵＶを照射して配向材を形成し、その配向材を用いて重合性液晶からなる位相差材料の光学パターニングをするためには、大きな偏光ＵＶ露光量が必要となる。その偏光ＵＶ露光量は、通常の液晶パネル用の液晶を配向させるのに十分な偏光ＵＶ露光量（例えば、１００ｍＪ／ｃｍ２程度。）より格段に多くなる。 However, according to the study by the present inventors, 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. In particular, in order to form an alignment material by irradiating these resins with polarized UV and to perform optical patterning of a retardation material composed of a polymerizable liquid crystal using the alignment material, 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.
　偏光ＵＶ露光量が多くなる理由としては、位相差材形成の場合には液晶パネル用の液晶と異なり、重合性液晶が溶液の状態で用いられ、配向材の上に塗布されることが挙げられている。 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.
　具体的には、側鎖にシンナモイル基等の光二量化部位を有するアクリル樹脂等を用いて配向材を形成し、該配向材を用いて重合性液晶を配向させようとする場合、まずアクリル樹脂等において光二量化反応による光架橋が行われる。そして、重合性液晶溶液に対する耐性が発現するまで、大きな露光量の偏光照射を行う必要がある。
　一方、液晶パネルの液晶を配向させるためには、通常、光配向性の配向材の表面のみを二量化反応させればよい。
　しかし、上述のアクリル樹脂等の従来材料を用いて配向材に重合性液晶溶液に対する耐性（溶剤耐性）を発現させようとすると、配向材の内部まで反応を進行させる必要があり、より多くの露光量が必要となる。その結果、従来材料の配向感度は非常に小さくなってしまうという問題があった。 Specifically, 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.
On the other hand, in order to align the liquid crystal of the liquid crystal panel, it is usually sufficient to dimerize only the surface of the photo-alignment alignment material.
However, if 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.
　また、上述の従来材料である樹脂にこのような溶剤耐性を発現させるため、架橋剤を添加する技術が知られている。しかし、架橋剤による熱硬化反応を行った後、形成される塗膜の内部には３次元構造が形成され、光反応性が低下することがわかっている。すなわち従来材料に架橋剤を添加して使用しても、結果として配向感度が大きく低下してしまい、所望とする効果は得られていない。 In addition, a technique of adding a crosslinking agent in order to develop such solvent resistance in the above-described conventional resin is known. However, it has been found that after a thermosetting reaction with a crosslinking agent, a three-dimensional structure is formed inside the formed coating film and the photoreactivity is lowered. That is, even when a crosslinking agent is added to a conventional material, the orientation sensitivity is greatly reduced as a result, and a desired effect is not obtained.
　以上より、配向材の配向感度を向上させ、偏光ＵＶ露光量を低減できる光配向技術と、その配向材の形成に用いられる硬化膜形成組成物が求められている。そして、高効率にパターン化位相差材を提供することができる技術が求められている。 From the above, 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 | required.
　また、光配向技術を用いて３Ｄディスプレイのパターン化位相差材を製造する場合、従来はガラス基板上での形成がなされてきた。しかし、近年は製造コスト低減の要求に応じ、ＴＡＣ（トリアセチルセルロース）フィルム、ＣＯＰ（シクロオレフィンポリマー）フィルムなどの安価な樹脂フィルム上で、所謂ロールツーロールにより生産されることが求められている。 Also, in the case of producing a patterned retardation material for a 3D display using a photo-alignment technique, it has been conventionally formed on a glass substrate. However, in recent years, in response to demands for manufacturing cost reduction, it has been demanded to be produced by so-called roll-to-roll on inexpensive resin films such as TAC (triacetyl cellulose) film and COP (cycloolefin polymer) film. .
　しかしながら、上述したような従来材料から形成された光配向膜では、樹脂フィルムへの密着性が弱く、樹脂フィルムの上で高信頼のパターン化位相差材を製造することは困難であった。 However, in the photo-alignment film formed from the conventional material as described above, the adhesion to the resin film is weak, and it is difficult to produce a highly reliable patterned retardation material on the resin film.
　したがって、樹脂フィルムへの密着性に優れ、ＴＡＣフィルム等の樹脂フィルム上でも高信頼の位相差材を形成することができ、光配向技術に適用可能な配向材と、そうした配向材を形成するための硬化膜形成組成物が求められている。 Therefore, it has excellent adhesion to a resin film, can form a highly reliable phase difference material on a resin film such as a TAC film, and the like, and an alignment material that can be applied to a photo-alignment technique and such an alignment material. There is a need for a cured film forming composition.
　本発明は、以上の知見や検討結果に基づいてなされたものである。すなわち、本発明の目的は、優れた光反応効率を有するとともに耐溶剤性を備え、樹脂フィルム上でも高感度で重合性液晶を配向させることができる配向材を提供するための硬化膜形成組成物を提供することである。 The present invention has been made based on the above knowledge and examination results. That is, 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.
　そして、本発明の別の目的は、その硬化膜形成組成物から得られ、優れた光反応効率を有するとともに耐溶剤性を備え、樹脂フィルム上でも高感度で重合性液晶を配向させることができる配向材とその配向材を用いて形成された位相差材を提供することにある。 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.
　本発明の他の目的および利点は、以下の記載から明らかとなるであろう。 Other objects and advantages of the present invention will become apparent from the following description.
　本発明の第１の態様は、
　（Ａ）光配向性基と、ヒドロキシ基、カルボキシル基、アミノ基およびアルコキシシリル基から選ばれるいずれか１つの置換基とを有する化合物、
　（Ｂ）アミド基の窒素原子のうちの少なくとも一部がアルコキシメチル化またはアルキルチオメチル化されたポリアミド、及び
　（Ｃ）架橋触媒、を含有することを特徴とする硬化膜形成組成物に関する。 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.
　本発明の第１の態様において、（Ａ）成分の光配向性基が光二量化または光異性化する構造の官能基であることが好ましい。 In the first aspect of the present invention, it is preferable that the photoalignable group of the component (A) is a functional group having a structure that undergoes photodimerization or photoisomerization.
　本発明の第１の態様において、（Ａ）成分の光配向性基がシンナモイル基であることが好ましい。 In the first aspect of the present invention, it is preferable that the photoalignable group of the component (A) is a cinnamoyl group.
　本発明の第１の態様において、（Ａ）成分の光配向性基がアゾベンゼン構造の基であることが好ましい。 In the first aspect of the present invention, it is preferable that the photoalignable group of the component (A) is a group having an azobenzene structure.
　本発明の第１の態様において、（Ｂ）成分のポリアミドが、ナイロン－６、ナイロン－１１、ナイロン－１２、ナイロン－６６、ナイロン－６１０、ナイロン－６１２、ナイロン－１０１０、ナイロン－１２１２、ナイロン－６６／６１０、ナイロン６／６６、ナイロン６／６９、ナイロン６－Ｉ／６－Ｔ、およびこれらの２種以上の組合せからなる群から選択されるポリアミドをＮ－アルコキシメチル化またはＮ－アルキルチオメチル化したものであることが好ましい。 In the first embodiment of the present invention, 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.
　本発明の第１の態様において、（Ｂ）成分のポリアミドが、ポリアミドをＮ－アルコキシメチル化したものであることが好ましい。 In the first embodiment of the present invention, it is preferable that the polyamide of component (B) is N-alkoxymethylated polyamide.
　本発明の第１の態様において、（Ａ）成分、（Ｂ）成分及び（Ｃ）成分のほかに（Ｄ）炭素原子数２乃至５のヒドロキシアルキルエステル基、アルコキシシリル基、Ｎ－アルコキシメチル基、カルボキシル基及びフェノール性ヒドロキシ基のうちの少なくとも一つを有するアクリル重合体をさらに含有することが好ましい。
　本発明の第１の態様において、（Ｂ）成分のポリアミドが１，０００～１００，０００の重量平均分子量を有することが好ましい。 In the first embodiment of the present invention, in addition to the components (A), (B) and (C), (D) a hydroxyalkyl ester group having 2 to 5 carbon atoms, an alkoxysilyl group, an N-alkoxymethyl group It is preferable to further contain an acrylic polymer having at least one of a carboxyl group and a phenolic hydroxy group.
In the first embodiment of the present invention, the polyamide as the component (B) preferably has a weight average molecular weight of 1,000 to 100,000.
　本発明の第２の態様は、本発明の第１の態様の熱硬化膜形成組成物を用いて得られることを特徴とする配向材に関する。 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.
　本発明の第３の態様は、本発明の第１の態様の硬化膜形成組成物から得られる硬化膜を使用して形成されることを特徴とする位相差材に関する。 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.
　本発明の第１の態様によれば、優れた光反応効率と耐溶剤性を備え、高感度で重合性液晶を配向させることができ、基板との高い密着性を示す配向材を提供するための硬化膜形成組成物を提供することができる。 According to the first aspect of the present invention, there is provided 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.
　本発明の第２の態様によれば、優れた光反応効率と耐溶剤性を備え、高感度で重合性液晶を配向させることができ、基板との高い密着性を示す配向材を提供することができる。 According to the second aspect of the present invention, there is 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.
　本発明の第３の態様によれば、樹脂フィルム上であっても高い効率で形成でき、且つ光学パターニングの可能な位相差材を提供することができる。 According to 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.
＜硬化膜形成組成物＞
　本実施の形態の硬化膜形成組成物は、（Ａ）成分である低分子の光配向成分と、（Ｂ）成分であるアミド基の窒素原子のうちの少なくとも一部がアルコキシメチル化またはアルキルチオメチル化されたポリアミド及び（Ｃ）成分である架橋触媒とを含有する。本実施の形態の硬化膜形成組成物は、（Ａ）成分、（Ｂ）成分及び（Ｃ）成分に加えて、さらに、（Ｄ）成分として炭素原子数２乃至５のヒドロキシアルキルエステル基、アルコキシシリル基、Ｎ－アルコキシメチル基、カルボキシル基及びフェノール性ヒドロキシ基のうちの少なくとも一つを有するアクリル重合体を含有することができる。そして、本発明の効果を損なわない限りにおいて、その他の添加剤を含有することができる。
　以下、各成分の詳細を説明する。 <Curing film forming composition>
In the cured film forming composition of the present embodiment, the low molecular photo-alignment component as component (A) and the nitrogen atom of the amide group as component (B) are alkoxymethylated or alkylthiomethylated. And a cross-linking catalyst as component (C). In addition to the component (A), the component (B), and the component (C), 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.
Hereinafter, details of each component will be described.
＜（Ａ）成分＞
　本発明の組成物の（Ａ）成分は、低分子配向成分である。（Ａ）成分は、本発明の組成物から得られる本実施形態の硬化膜に光配向性を付与する成分であり、ベースとなる後述の（Ｂ）成分のポリマーに比べて低分子の光配向成分となる。 <(A) component>
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.
　本発明の組成物において、（Ａ）成分である低分子配向成分は、光配向性基、並びに、ヒドロキシ基、カルボキシル基、アミノ基およびアルコキシシリル基からなる群から選ばれる一つの基を有する化合物である。
　尚、本発明において、光配向性基とは、光二量化する構造を有する官能基または光異性化する構造を有する官能基を言う。また光配向性基としては、光フリース転位反応を起こす官能基（例示化合物：安息香酸エステル化合物など）、光分解反応を起こす基（例示化合物；シクロブタン環など）などを使用することもできる。 In the composition of the present invention, 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.
In the present invention, the photoalignable group means a functional group having a photodimerization structure or a functional group having a photoisomerization structure. Further, as the 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.
　また、（Ａ）成分の化合物が光配向性基として有することのできる光二量化する構造部位とは、光照射により二量体を形成する部位であり、その具体例としては、シンナモイル基、カルコン基、クマリン基、アントラセン基等が挙げられる。これらのうち可視光領域での透明性の高さ、並びに光二量化反応性の高さからシンナモイル基が好ましい。 In addition, 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.
　また、（Ａ）成分の化合物が光配向性基として有することのできる光異性化する構造部位とは、光照射によりシス体とトランス体とに変わる構造部位を指し、その具体例としてはアゾベンゼン構造、スチルベン構造等からなる部位が挙げられる。これらのうち反応性の高さからアゾベンゼン構造が好ましい。 In addition, 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.
　光配向性基と、ヒドロキシ基、カルボキシル基、アミノ基およびアルコキシシリル基からなる群から選ばれる一つとを有する化合物の具体例を、下記式［Ａ１］～式［Ａ５］に示す。なおＡ成分の化合物は下記具体例に限定されるものではない。 Specific examples of 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]. In addition, the compound of A component is not limited to the following specific example.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　前記式中、Ａ１とＡ２はそれぞれ独立に、水素原子またはメチル基を表す。
　Ｘ１は単結合、エーテル結合、エステル結合、カルボニル、アミド結合、ウレタン結合、ウレア結合、アミノ結合及びそれらの組み合わせから選ばれる１種又は２種以上の結合、或いは該１種または２種の結合を介して、炭素原子数１乃至１８のアルキレン基、フェニレン基、ビフェレン基及びそれらの組み合わせから選ばれる１乃至３の置換基が結合してなる構造であって、前記置換基は前記結合を介してそれぞれ複数個が連結してなる構造であってもよい。
　Ｘ２は水素原子、ハロゲン原子、シアノ基、炭素原子数１乃至１８のアルキル基、フェニル基、ビフェニル基又はシクロヘキシル基を表す。その際、炭素原子数１乃至１８のアルキル基、フェニル基、ビフェニル基及びシクロヘキシル基は、共有結合、エーテル結合、エステル結合、アミド結合又は尿素結合を介して結合してもよい。
　Ｘ３はヒドロキシ基、メルカプト基、炭素原子数１乃至１０のアルコキシ基、炭素原子数１乃至１０のアルキルチオ基、フェニル基、フェノキシ基、ビフェニル基、ビフェニルオキシ基を表す。
　Ｘ４はそれぞれ独立に単結合、炭素原子数１乃至２０のアルキレン基、芳香族環基、又は、脂肪族環基を表す。ここで炭素原子数乃至２０のアルキレン基は分岐状でも直鎖状でもよい。
　Ｘ５はヒドロキシ基、カルボキシル基、アミノ基またはアルコキシシリル基を表す。
　Ｘは単結合、酸素原子又は硫黄原子を表す。
　なお、これらの置換基において、フェニル基とビフェニル基は、炭素原子数１乃至４のアルキル基、炭素原子数１乃至４のアルコキシ基、ハロゲン原子、トリフルオロメチル基およびシアノ基から選ばれる同一又は相異なる１または複数の置換基によって置換されていてもよい。 In the formula, 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. In this case, 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. Here, 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.
In these substituents, 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.
　上記式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７およびＲ８は、それぞれ独立して水素原子、炭素原子数１乃至４のアルキル基、炭素原子数１乃至４のアルコキシ基、ハロゲン原子、トリフルオロメチル基またはシアノ基を表す。 In the above formula, 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.
　（Ａ）成分である、光配向性基およびヒドロキシ基を有する化合物の具体例として、上記式［Ａ１］～［Ａ５］で表される化合物並びに該式以外の化合物としては、例えば、４－（８－ヒドロキシオクチルオキシ）けい皮酸メチルエステル、４－（６－ヒドロキシヘキシルオキシ）けい皮酸メチルエステル、４－（４－ヒドロキシブチルオキシ）けい皮酸メチルエステル、４－（３－ヒドロキシプロピルオキシ）けい皮酸メチルエステル、４－（２－ヒドロキシエチルオキシ）けい皮酸メチルエステル、４－ヒドロキシメチルオキシけい皮酸メチルエステル、４－ヒドロキシけい皮酸メチルエステル、４－（８－ヒドロキシオクチルオキシ）けい皮酸エチルエステル、４－（６－ヒドロキシヘキシルオキシ）けい皮酸エチルエステル、４－（４－ヒドロキシブチルオキシ）けい皮酸エチルエステル、４－（３－ヒドロキシプロピルオキシ）けい皮酸エチルエステル、４－（２－ヒドロキシエチルオキシ）けい皮酸エチルエステル、４－ヒドロキシメチルオキシけい皮酸エチルエステル、４－ヒドロキシけい皮酸エチルエステル、４－（８－ヒドロキシオクチルオキシ）けい皮酸フェニルエステル、４－（６－ヒドロキシヘキシルオキシ）けい皮酸フェニルエステル、４－（４－ヒドロキシブチルオキシ）けい皮酸フェニルエステル、４－（３－ヒドロキシプロピルオキシ）けい皮酸フェニルエステル、４－（２－ヒドロキシエチルオキシ）けい皮酸フェニルエステル、４－ヒドロキシメチルオキシけい皮酸フェニルエステル、４－ヒドロキシけい皮酸フェニルエステル、４－（８－ヒドロキシオクチルオキシ）けい皮酸ビフェニルエステル、４－（６－ヒドロキシヘキシルオキシ）けい皮酸ビフェニルエステル、４－（４－ヒドロキシブチルオキシ）けい皮酸ビフェニルエステル、４－（３－ヒドロキシプロピルオキシ）けい皮酸ビフェニルエステル、４－（２－ヒドロキシエチルオキシ）けい皮酸ビフェニルエステル、４－ヒドロキシメチルオキシけい皮酸ビフェニルエステル、４－ヒドロキシけい皮酸ビフェニルエステル、けい皮酸８－ヒドロキシオクチルエステル、けい皮酸６－ヒドロキシヘキシルエステル、けい皮酸４－ヒドロキシブチルエステル、けい皮酸３－ヒドロキシプロピルエステル、けい皮酸２－ヒドロキシエチルエステル、けい皮酸ヒドロキシメチルエステル、４－（８－ヒドロキシオクチルオキシ）アゾベンゼン、４－（６－ヒドロキシヘキシルオキシ）アゾベンゼン、４－（４－ヒドロキシブチルオキシ）アゾベンゼン、４－（３－ヒドロキシプロピルオキシ）アゾベンゼン、４－（２－ヒドロキシエチルオキシ）アゾベンゼン、４－ヒドロキシメチルオキシアゾベンゼン、４－ヒドロキシアゾベンゼン、４－（８－ヒドロキシオクチルオキシ）カルコン、４－（６－ヒドロキシヘキシルオキシ）カルコン、４－（４－ヒドロキシブチルオキシ）カルコン、４－（３－ヒドロキシプロピルオキシ）カルコン、４－（２－ヒドロキシエチルオキシ）カルコン、４－ヒドロキシメチルオキシカルコン、４－ヒドロキシカルコン、４’－（８－ヒドロキシオクチルオキシ）カルコン、４’－（６－ヒドロキシヘキシルオキシ）カルコン、４’－（４－ヒドロキシブチルオキシ）カルコン、４’－（３－ヒドロキシプロピルオキシ）カルコン、４’－（２－ヒドロキシエチルオキシ）カルコン、４’－ヒドロキシメチルオキシカルコン、４’－ヒドロキシカルコン、７－（８－ヒドロキシオクチルオキシ）クマリン、７－（６－ヒドロキシヘキシルオキシ）クマリン、７－（４－ヒドロキシブチルオキシ）クマリン、７－（３－ヒドロキシプロピルオキシ）クマリン、７－（２－ヒドロキシエチルオキシ）クマリン、７－ヒドロキシメチルオキシクマリン、７－ヒドロキシクマリン、６－ヒドロキシオクチルオキシクマリン、６－ヒドロキシヘキシルオキシクマリン、６－（４－ヒドロキシブチルオキシ）クマリン、６－（３－ヒドロキシプロピルオキシ）クマリン、６－（２－ヒドロキシエチルオキシ）クマリン、６－ヒドロキシメチルオキシクマリン、６－ヒドロキシクマリンが挙げられる。 Specific examples of 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) cinnamic acid ethyl ester, 4- (3-hydroxypropyloxy) cinnamic acid ethyl ester, 4- (2-hydroxyethyloxy) cinnamic acid ethyl ester, 4-hydroxymethyloxy cinnamic acid Ethyl ester, 4-hydroxycinnamic acid ethyl ester, 4- (8-hydroxyoctyloxy) cinnamic acid phenyl ester, 4- (6-hydroxyhexyloxy) cinnamic acid phenyl ester, 4- (4-hydroxybutyloxy) ) Cinnamic acid phenyl ester, 4- (3-hydroxypropyloxy) cinnamic acid phenyl ester, 4- (2-hydroxyethyloxy) cinnamic acid phenyl ester, 4-hydroxymethyloxy cinnamic acid phenyl ester, 4- Hydroxycinnamic acid phenyl ester, 4- (8 Hydroxyoctyloxy) cinnamic acid biphenyl ester, 4- (6-hydroxyhexyloxy) cinnamic acid biphenyl ester, 4- (4-hydroxybutyloxy) cinnamic acid biphenyl ester, 4- (3-hydroxypropyloxy) cinnamic Cinnamic acid biphenyl ester, 4- (2-hydroxyethyloxy) cinnamic acid biphenyl ester, 4-hydroxymethyloxycinnamic acid biphenyl ester, 4-hydroxycinnamic acid biphenyl ester, cinnamic acid 8-hydroxyoctyl ester, silicic acid Cinnamic acid 6-hydroxyhexyl ester, cinnamic acid 4-hydroxybutyl ester, cinnamic acid 3-hydroxypropyl ester, cinnamic acid 2-hydroxyethyl ester, cinnamic acid hydroxymethyl ester, 4- (8-hydroxyoctyloxy) ) Azobenzene, 4- (6-hydroxyhexyloxy) azobenzene, 4- (4-hydroxybutyloxy) azobenzene, 4- (3-hydroxypropyloxy) azobenzene, 4- (2-hydroxyethyloxy) azobenzene, 4-hydroxy Methyloxyazobenzene, 4-hydroxyazobenzene, 4- (8-hydroxyoctyloxy) chalcone, 4- (6-hydroxyhexyloxy) chalcone, 4- (4-hydroxybutyloxy) chalcone, 4- (3-hydroxypropyloxy) ) Chalcone, 4- (2-hydroxyethyloxy) chalcone, 4-hydroxymethyloxychalcone, 4-hydroxychalcone, 4 ′-(8-hydroxyoctyloxy) chalcone, 4 ′-(6-hydroxyhexyloxy) chalcone, 4 ' (4-hydroxybutyloxy) chalcone, 4 ′-(3-hydroxypropyloxy) chalcone, 4 ′-(2-hydroxyethyloxy) chalcone, 4′-hydroxymethyloxychalcone, 4′-hydroxychalcone, 7- ( 8-hydroxyoctyloxy) coumarin, 7- (6-hydroxyhexyloxy) coumarin, 7- (4-hydroxybutyloxy) coumarin, 7- (3-hydroxypropyloxy) coumarin, 7- (2-hydroxyethyloxy) Coumarin, 7-hydroxymethyloxycoumarin, 7-hydroxycoumarin, 6-hydroxyoctyloxycoumarin, 6-hydroxyhexyloxycoumarin, 6- (4-hydroxybutyloxy) coumarin, 6- (3-hydroxypropyloxy) coumarin, 6- (2-Hide Carboxyethyl oxy) coumarin, 6-hydroxy methyloxy coumarin include 6-hydroxy coumarin.
　（Ａ）成分である、光配向性基およびカルボキシル基を有する化合物の具体例としては、けい皮酸、フェルラ酸、４－ニトロけい皮酸、４－メトキシけい皮酸、３，４－ジメトキシけい皮酸、クマリン－３－カルボン酸、４－（Ｎ，Ｎ－ジメチルアミノ）けい皮酸等が挙げられる。 Specific examples of 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.
　（Ａ）成分である、光配向性基およびアミノ基を有する化合物の具体例としては、４－アミノけい皮酸メチルエステル、４－アミノけい皮酸エチルエステル、３－アミノけい皮酸メチルエステル、３－アミノけい皮酸エチルエステル等が挙げられる。 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.
　（Ａ）成分である、光配向性基とアルコキシシリル基とを有する化合物の具体例としては、４－（３－トリメトキシシリルプロピルオキシ）けい皮酸メチルエステル、４－（３－トリエトキシシリルプロピルオキシ）けい皮酸メチルエステル、４－（３－トリメトキシシリルプロピルオキシ）けい皮酸エチルエステル、４－（３－トリエトキシシリルプロピルオキシ）けい皮酸エチルエステル、４－（６－トリメトキシシリルヘキシルオキシ）けい皮酸メチルエステル、４－（６－トリエトキシシリルヘキシルオキシ）けい皮酸メチルエステル、４－（６－トリメトキシシリルヘキシルオキシ）けい皮酸エチルエステルおよび４－（６－トリエトキシシリルヘキシルオキシ）けい皮酸エチルエステル等が挙げられる。
　（Ａ）成分である低分子配向成分は、以上の具体例を挙げることができるが、これらに限定されるものではない。 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 ethyl ester and 4- (6-tri Ethoxysilylhexyloxy) cinnamic acid ethyl ester and the like.
Specific examples of the low molecular orientation component as the component (A) can include the above specific examples, but are not limited thereto.
　また、（Ａ）成分である低分子配向成分が、光配向性基およびヒドロキシ基を有する化合物である場合、（Ａ）成分として、分子内に、光配向性基を２個以上および／またはヒドロキシ基を２個以上有する化合物を用いることが可能である。具体的には、（Ａ）成分として、分子内に１個のヒドロキシ基とともに２個以上の光配向性基を有する化合物や、分子内に１個の光配向性基とともに２個以上のヒドロキシ基を有する化合物や、分子内に光配向性基とヒドロキシ基をそれぞれ２個以上有する化合物を用いることが可能である。例えば、分子内に光配向性基とヒドロキシ基をそれぞれ２個以上有する化合物については、下記式で表される化合物を例示することができる。 Moreover, when the low molecular orientation component which is the component (A) is a compound having a photoalignment group and a hydroxy group, as 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. Specifically, as the component (A), a compound having two or more photoalignable groups with one hydroxy group in the molecule, or two or more hydroxy groups with one photoalignable group in the molecule Or a compound having two or more photo-alignable groups and two hydroxyl groups in the molecule can be used. For example, compounds having two or more photoalignable groups and hydroxy groups in the molecule can be exemplified by compounds represented by the following formulae.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　このような化合物を適宜選択することにより、（Ａ）成分である低分子配向成分の分子量を所望範囲の値に制御することが可能となる。本発明の組成物を用い、本実施形態の硬化膜を形成するためには、加熱硬化が必要となるが、その加熱を行う際に、（Ａ）成分である低分子配向成分が昇華するのを抑制することができる。 By appropriately selecting such a compound, it is possible to control the molecular weight of the low molecular orientation component (A) component to a value within a desired range. In order to form the cured film of the present embodiment using the composition of the present invention, heat curing is required, but when the heating is performed, the low molecular orientation component (A) component sublimes. Can be suppressed.
　尚、本発明の組成物における（Ａ）成分の化合物としては、光配向性基とヒドロキシ基、カルボキシル基、アミノ基およびアルコキシシリル基のいずれか一つとを有する、複数種の化合物の混合物であってもよい。 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.
　また本発明の組成物は（Ａ）成分として、下記式［１］で表される光配向性基を有する化合物を含有することができる。
Figure JPOXMLDOC01-appb-C000003
 Moreover, the composition of this invention can contain the compound which has a photo-alignment group represented by following formula [1] as (A) component.
Figure JPOXMLDOC01-appb-C000003
　式中、Ａ１とＡ２はそれぞれ独立に、水素原子またはメチル基を表し、Ａ３はヒドロキシ基、メルカプト基、炭素原子数１乃至１０のアルコキシ基、炭素原子数１乃至１０のヒドロキシアルコキシ基、炭素原子数１乃至１０のアルキルチオ基、フェニル基、フェノキシ基、ビフェニル基またはビフェニルオキシ基を表し、＊は結合端を表す。
　ここで上記ベンゼン環とフェニル基の水素原子は、それぞれ独立に、炭素原子数１乃至１０のアルキル基、炭素原子数１乃至１０のアルコキシ基、ハロゲン原子、シアノ基およびニトロ基から選ばれる置換基で置換されていてもよい。 Wherein 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 an alkylthio group having 1 to 10 carbon atoms, a phenyl group, a phenoxy group, a biphenyl group or a biphenyloxy group, and * represents a bonding end.
Here, 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.
　中でも、上記Ａ１としては、水素原子またはメチル基が好ましく、Ａ２としては水素原子が好ましく、Ａ３としては炭素原子数１～１０のアルコキシ基、フェニル基等が好ましい。 Among these, A 1 is preferably a hydrogen atom or a methyl group, A 2 is preferably a hydrogen atom, and A 3 is preferably an alkoxy group having 1 to 10 carbon atoms, a phenyl group, or the like.
　上記式［１］で表される光配向性基およびヒドロキシ基を有する化合物の具体例としては、例えば、４－［４－（８－ヒドロキシオクチルオキシ）ベンゾイル］けい皮酸メチルエステル、４－［４－（６－ヒドロキシヘキシルオキシ）ベンゾイル］けい皮酸メチルエステル、４－［４－（４－ヒドロキシブチルオキシ）ベンゾイル］けい皮酸メチルエステル、４－［４－（３－ヒドロキシプロピルオキシ）ベンゾイル］けい皮酸メチルエステル、４－［４－（２－ヒドロキシエチルオキシ）ベンゾイル］けい皮酸メチルエステル、４－［４－ヒドロキシメチルオキシベンゾイル］けい皮酸メチルエステル、４－［４－ヒドロキシベンゾイル］けい皮酸メチルエステル、４－［４－（８－ヒドロキシオクチルオキシ）ベンゾイル］けい皮酸エチルエステル、４－［４－（６－ヒドロキシヘキシルオキシ）ベンゾイル］けい皮酸エチルエステル、４－［４－（４－ヒドロキシブチルオキシ）ベンゾイル］けい皮酸エチルエステル、４－［４－（３－ヒドロキシプロピルオキシ）ベンゾイル］けい皮酸エチルエステル、４－［４－（２－ヒドロキシエチルオキシ）ベンゾイル］けい皮酸エチルエステル、４－［４－ヒドロキシメチルオキシベンゾイル］けい皮酸エチルエステル、４－［４－ヒドロキシベンゾイル］けい皮酸エチルエステル、４－［４－（８－ヒドロキシオクチルオキシ）ベンゾイル］けい皮酸ターシャリーブチルエステル、４－［４－（６－ヒドロキシヘキシルオキシ）ベンゾイル］けい皮酸ターシャリーブチルエステル、４－［４－（４－ヒドロキシブチルオキシ）ベンゾイル］けい皮酸ターシャリーブチルエステル、４－［４－（３－ヒドロキシプロピルオキシ）ベンゾイル］けい皮酸ターシャリーブチルエステル、４－［４－（２－ヒドロキシエチルオキシ）ベンゾイル］けい皮酸ターシャリーブチルエステル、４－［４－ヒドロキシメチルオキシベンゾイル］けい皮酸ターシャリーブチルエステル、４－［４－（８－ヒドロキシオクチルオキシ）ベンゾイル］けい皮酸フェニルエステル、４－［４－（６－ヒドロキシヘキシルオキシ）ベンゾイル］けい皮酸フェニルエステル、４－［４－（４－ヒドロキシブチルオキシ）ベンゾイル］けい皮酸フェニルエステル、４－［４－（３－ヒドロキシプロピルオキシ）ベンゾイル］けい皮酸フェニルエステル、４－［４－（２－ヒドロキシエチルオキシ）ベンゾイル］けい皮酸フェニルエステル、４－［４－ヒドロキシメチルオキシベンゾイル］けい皮酸フェニルエステル、４－［４－ヒドロキシベンゾイル］けい皮酸フェニルエステル、４－［４－（８－ヒドロキシオクチルオキシ）ベンゾイル］けい皮酸ビフェニルエステル、４－［４－（６－ヒドロキシヘキシルオキシ）ベンゾイル］けい皮酸ビフェニルエステル、４－［４－（４－ヒドロキシブチルオキシ）ベンゾイル］けい皮酸ビフェニルエステル、４－［４－（３－ヒドロキシプロピルオキシ）ベンゾイル］けい皮酸ビフェニルエステル、４－［４－（２－ヒドロキシエチルオキシ）ベンゾイル］けい皮酸ビフェニルエステル、４－［４－ヒドロキシメチルオキシベンゾイル］けい皮酸ビフェニルエステル、４－［４－ヒドロキシベンゾイル］けい皮酸ビフェニルエステル、４－ベンゾイルけい皮酸８－ヒドロキシオクチルエステル、４－ベンゾイルけい皮酸６－ヒドロキシヘキシルエステル、４－ベンゾイルけい皮酸４－ヒドロキシブチルエステル、４－ベンゾイルけい皮酸３－ヒドロキシプロピルエステル、４－ベンゾイルけい皮酸２－ヒドロキシエチルエステル、４－ベンゾイルけい皮酸ヒドロキシメチルエステル、４－［４－（８－ヒドロキシオクチルオキシ）ベンゾイル］カルコン、４－［４－（６－ヒドロキシヘキシルオキシ）ベンゾイル］カルコン、４－［４－（４－ヒドロキシブチルオキシ）ベンゾイル］カルコン、４－［４－（３－ヒドロキシプロピルオキシ）ベンゾイル］カルコン、４－［４－（２－ヒドロキシエチルオキシ）ベンゾイル］カルコン、４－（４－ヒドロキシメチルオキシベンゾイル）カルコン、４－（４－ヒドロキシベンゾイル）カルコン等が挙げられる。 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- (6-hydroxyhexyloxy) benzoyl] cinnamic acid ethyl ester, 4- [4- (4-hydroxybutyloxy) benzoyl] cinnamic acid ethyl ester, 4- [4- (3- Hydroxypropyloxy) benzoyl] cinnamic acid ethyl ester, 4- [4- (2-hydroxyethyloxy) benzoyl] cinnamic acid ethyl ester, 4- [4-hydroxymethyloxybenzoyl] cinnamic acid ethyl ester, 4- [4-hydroxybenzoyl] cinnamic acid ethyl ester, 4- [4- (8-hydroxyoctyloxy) benzoyl] cinnamic acid tertiary butyl ester, 4- [4- (6-hydroxyhexyloxy) benzoyl] cinnamic Acid tertiary butyl ester, 4- [4- (4-hydroxybutyloxy) Nzoyl] cinnamic acid tertiary butyl ester, 4- [4- (3-hydroxypropyloxy) benzoyl] cinnamic acid tertiary butyl ester, 4- [4- (2-hydroxyethyloxy) benzoyl] cinnamic acid tarsha Libutyl ester, 4- [4-hydroxymethyloxybenzoyl] cinnamic acid tertiary butyl ester, 4- [4- (8-hydroxyoctyloxy) benzoyl] cinnamic acid phenyl ester, 4- [4- (6- Hydroxyhexyloxy) benzoyl] cinnamic acid phenyl ester, 4- [4- (4-hydroxybutyloxy) benzoyl] cinnamic acid phenyl ester, 4- [4- (3-hydroxypropyloxy) benzoyl] cinnamic acid phenyl Ester, 4- [4- (2-hydroxyethyloxy) ben Zoyl] cinnamic acid phenyl ester, 4- [4-hydroxymethyloxybenzoyl] cinnamic acid phenyl ester, 4- [4-hydroxybenzoyl] cinnamic acid phenyl ester, 4- [4- (8-hydroxyoctyloxy) Benzoyl] cinnamic acid biphenyl ester, 4- [4- (6-hydroxyhexyloxy) benzoyl] cinnamic acid biphenyl ester, 4- [4- (4-hydroxybutyloxy) benzoyl] cinnamic acid biphenyl ester, 4- [4- (3-hydroxypropyloxy) benzoyl] cinnamic acid biphenyl ester, 4- [4- (2-hydroxyethyloxy) benzoyl] cinnamic acid biphenyl ester, 4- [4-hydroxymethyloxybenzoyl] cinnamic Acid biphenyl ester, 4- [4-hydroxybenzo L] cinnamic acid biphenyl ester, 4-benzoylcinnamic acid 8-hydroxyoctyl ester, 4-benzoyl cinnamic acid 6-hydroxyhexyl ester, 4-benzoyl cinnamic acid 4-hydroxybutyl ester, 4-benzoyl cinnamic acid 3-hydroxypropyl ester, 4-benzoylcinnamic acid 2-hydroxyethyl ester, 4-benzoylcinnamic acid hydroxymethyl ester, 4- [4- (8-hydroxyoctyloxy) benzoyl] chalcone, 4- [4- ( 6-hydroxyhexyloxy) benzoyl] chalcone, 4- [4- (4-hydroxybutyloxy) benzoyl] chalcone, 4- [4- (3-hydroxypropyloxy) benzoyl] chalcone, 4- [4- (2- Hydroxyethyloxy) benzoyl] chalcone, 4 (4-hydroxymethyl-oxybenzoyl) chalcone, 4- (4-hydroxybenzoyl) chalcone and the like.
　上記式［１］で表される光配向性基およびカルボキシル基を有する化合物の具体例としては、４－ベンゾイルけい皮酸、４－（４－ニトロベンゾイル）けい皮酸、４－（４－メトキシベンゾイル）けい皮酸、４－（３，４－ジメトキシベンゾイル）けい皮酸等が挙げられる。
　上記式［１］で表される光配向性基およびアミノ基を有する化合物の具体例としては、４－（４－アミノベンゾイル）けい皮酸メチルエステル、４－（４－アミノベンゾイル）けい皮酸エチルエステル、４－（４－アミノベンゾイル）けい皮酸ターシャリーブチルエステル、４－（３－アミノベンゾイル）けい皮酸メチルエステル、４－（３－アミノベンゾイル）けい皮酸エチルエステル、４－（３－アミノベンゾイル）けい皮酸ターシャリーブチルエステル等が挙げられる。 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.
　上記式［１］で表される光配向性基とアルコキシシリル基とを有する化合物の具体例としては、４－［４－（３－トリメトキシシリルプロピルオキシ）ベンゾイル］けい皮酸メチルエステル、４－［４－（３－トリエトキシシリルプロピルオキシ）ベンゾイル］けい皮酸メチルエステル、４－［４－（３－トリメトキシシリルプロピルオキシ）ベンゾイル］けい皮酸エチルエステル、４－［４－（３－トリエトキシシリルプロピルオキシ）ベンゾイル］けい皮酸エチルエステル、４－［４－（３－トリメトキシシリルプロピルオキシ）ベンゾイル］けい皮酸ターシャリーブチルエステル、４－［４－（３－トリエトキシシリルプロピルオキシ）ベンゾイル］けい皮酸ターシャリーブチルエステル、４－［４－（６－トリメトキシシリルヘキシルオキシ）ベンゾイル］けい皮酸メチルエステル、４－［４－（６－トリエトキシシリルヘキシルオキシ）ベンゾイル］けい皮酸メチルエステル、４－［４－（６－トリメトキシシリルヘキシルオキシ）ベンゾイル］けい皮酸エチルエステル、４－［４－（６－トリエトキシシリルヘキシルオキシ）ベンゾイル］けい皮酸エチルエステル、４－［４－（６－トリメトキシシリルヘキシルオキシ）ベンゾイル］けい皮酸ターシャリーブチルエステルおよび４－［４－（６－トリエトキシシリルヘキシルオキシ）ベンゾイル］けい皮酸ターシャリーブチルエステル等が挙げられる。 Specific examples of 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 butyl ester, 4- [4- (6-trimethoxysilylhexyl) Ruoxy) benzoyl] cinnamic acid methyl ester, 4- [4- (6-triethoxysilylhexyloxy) benzoyl] cinnamic acid methyl ester, 4- [4- (6-trimethoxysilylhexyloxy) benzoyl] cinnamic Acid ethyl ester, 4- [4- (6-triethoxysilylhexyloxy) benzoyl] cinnamic acid ethyl ester, 4- [4- (6-trimethoxysilylhexyloxy) benzoyl] cinnamic acid tertiary butyl ester and 4- [4- (6-Triethoxysilylhexyloxy) benzoyl] cinnamic acid tertiary butyl ester and the like.
　なお、光配向性基として上記式［１］で表される基を有する化合物としては、例えば、下記式［２］で表される化合物があげられる。
Figure JPOXMLDOC01-appb-C000004
 In addition, as a compound which has group represented by said Formula [1] as a photoalignment group, the compound represented by following formula [2] is mention | raise | lifted, for example.
Figure JPOXMLDOC01-appb-C000004
　上記式［２］中、Ａ１とＡ２はそれぞれ独立に、水素原子またはメチル基を表し、Ａ３はヒドロキシ基、メルカプト基、炭素原子数１乃至１０のアルコキシ基、炭素原子数１乃至１０のヒドロキシアルコキシ基、炭素原子数１乃至１０のアルキルチオ基、フェニル基、フェノキシ基、ビフェニル基またはビフェニル基オキシを表し、ここでベンゼン環とフェニル基の水素原子は、それぞれ独立に、炭素原子数１乃至１０のアルキル基、炭素原子数１乃至１０のアルコキシ基、ハロゲン原子、シアノ基およびニトロ基から選ばれる置換基で置換されていてもよく、ｎは２～２０の整数である。
　この化合物は、文献未記載の新規化合物であり、例えば、下記のスキームで示される方法で製造することができる。 In the above formula [2], 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. A hydroxyalkoxy group, an alkylthio group having 1 to 10 carbon atoms, a phenyl group, a phenoxy group, a biphenyl group or a biphenyl group oxy, wherein the hydrogen atoms of the benzene ring and the phenyl group are each independently 1 It may be substituted with 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, and n is an integer of 2 to 20.
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.
Figure JPOXMLDOC01-appb-C000005
 　上記式中、Ａ１、Ａ２、Ａ３及びｎは前記式［２］で定義されたものと同義であり、Ｈａｌはハロゲン原子を表す。
Figure JPOXMLDOC01-appb-C000005
 In the above formula, A 1 , A 2 , A 3 and n are as defined in the above formula [2], and Hal represents a halogen atom.
＜（Ｂ）成分＞
　本実施の形態の硬化膜形成組成物は、（Ｂ）成分として、アミド基の窒素原子のうちの少なくとも一部がアルコキシメチル化またはアルキルチオメチル化されたポリアミドを含有する。
　本発明における（Ｂ）成分のポリアミドは、ω－アミノカルボン酸の重縮合、そのラクタムの開環重合によって合成されたポリアミド、またはジカルボン酸とジアミンとの重縮合等によって合成されたポリアミド、あるいはこれらの２以上の共重合あるいはブレンド物を使用できる。 <(B) component>
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 ω-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.
　ω－アミノカルボン酸の重縮合、またはそのラクタムの開環重合によって合成されたポリアミドは例えばＮｙｌｏｎ　Ｐｌａｓｔｉｃｓ（Ｍｅｌｖｉｎ　Ｌ．Ｋｏｈａｎ編，１９７３，Ｊｏｈｎ　Ｗｉｌｅｙ　ａｎｄ　Ｓｏｎｓ，Ｉｎｃ．）に開示されており、そのようなものとして、ナイロン－６、ナイロン－１１、ナイロン－１２、またはこれらの２種以上の組合せが挙げられる。１種類を超える上記ラクタムまたは上記アミノカルボン酸から調製されたポリアミドとしては、ナイロン－６，１２が挙げられる。使用頻度の高いポリアミドとしては、ナイロン－６、ナイロン－１１、ナイロン－１２、およびナイロン－６，１２、またはこれらの２種以上の組合せが挙げられる。 Polyamides synthesized by polycondensation of ω-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.
　ジカルボン酸とジアミンとの重縮合等によってポリアミドを製造する際のジアミン成分としては、脂肪族ジアミンや脂環式ジアミン等の、芳香族環を有しないジアミンが好ましい。 As the diamine component when producing polyamide by polycondensation of dicarboxylic acid and diamine, diamines having no aromatic ring such as aliphatic diamine and alicyclic diamine are preferable.
　脂肪族ジアミン類の例としては、１，２－ジアミノエタン、１，３－ジアミノプロパン、１，４－ジアミノブタン、１，５－ジアミノペンタン、１，６－ジアミノヘキサン、１，７－ジアミノヘプタン、１，８－ジアミノオクタン、１，９－ジアミノノナン、１，１０－ジアミノデカン、１，３－ジアミノ－２，２－ジメチルプロパン、１，６－ジアミノ－２，５－ジメチルヘキサン、１，７－ジアミノ－２，５－ジメチルヘプタン、１，７－ジアミノ－４，４－ジメチルヘプタン、１，７－ジアミノ－３－メチルヘプタン、１，９－ジアミノ－５－メチルヘプタン、１，１２－ジアミノドデカン、１，１８－ジアミノオクタデカン、１，２－ビス（３－アミノプロポキシ）エタンなどが挙げられる。 Examples of aliphatic diamines 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-diaminooctadecane, and 1,2-bis (3-aminopropoxy) ethane.
　脂環式ジアミンの例としては、１，４－ジアミノシクロヘキサン、１，３－ジアミノシクロヘキサン、４，４’－ジアミノジシクロヘキシルメタン、４，４’－ジアミノ－３，３’－ジメチルジシクロヘキシルアミン、イソホロンジアミン等が挙げられる。 Examples of alicyclic diamines include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4′-diaminodicyclohexylmethane, 4,4′-diamino-3,3′-dimethyldicyclohexylamine, isophorone diamine Etc.
　なお、本発明に用いるポリアミドを製造する際に、本発明の効果を損なわない限り、芳香族ジアミン、芳香族－脂肪族ジアミン、複素環式ジアミン等を用いてもよい。その際、これら芳香族ジアミン、芳香族－脂肪族ジアミン、複素環式ジアミン等の合計量は、全ジアミンの合計量１００モルあたり１０モル以下にすることが好ましい。芳香族ジアミン、芳香族－脂肪族ジアミン、複素環式ジアミン等の含有量が過大であると、Ｎ－アルコキシメチル変性の際にホルムアルデヒドと芳香族環とが反応してしまい、得られる樹脂の取り扱い性、物性等が低下する場合がある。 In producing the polyamide used in the present invention, aromatic diamine, aromatic-aliphatic diamine, heterocyclic diamine, etc. may be used as long as the effects of the present invention are not impaired. In that case, 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.
　芳香族ジアミン類の例としては、ｏ－フェニレンジアミン、ｍ－フェニレンジアミン、ｐ－フェニレンジアミン、２，４－ジアミノトルエン、２，５－ジアミノトルエン、３，５－ジアミノトルエン、１，４－ジアミノ－２－メトキシベンゼン、２，５－ジアミノ－ｐ－キシレン、１，３－ジアミノ－４－クロロベンゼン、３，５－ジアミノ安息香酸、１，４－ジアミノ－２，５－ジクロロベンゼン、４，４’－ジアミノ－１，２－ジフェニルエタン、４，４’－ジアミノ－２，２’－ジメチルビベンジル、４，４’－ジアミノジフェニルメタン、３，３’－ジアミノジフェニルメタン、３，４’－ジアミノジフェニルメタン、４，４’－ジアミノ－３，３’－ジメチルジフェニルメタン、２，２’－ジアミノスチルベン、４，４’－ジアミノスチルベン、４，４’－ジアミノジフェニルエーテル、３，４’－ジアミノジフェニルエーテル、４，４’－ジアミノジフェニルスルフィド、４，４’－ジアミノジフェニルスルホン、３，３’－ジアミノジフェニルスルホン、４，４’－ジアミノベンゾフェノン、１，３－ビス（３－アミノフェノキシ）ベンゼン、１，３－ビス（４－アミノフェノキシ）ベンゼン、１，４－ビス（４－アミノフェノキシ）ベンゼン、３，５－ビス（４－アミノフェノキシ）安息香酸、４，４’－ビス（４－アミノフェノキシ）ビベンジル、２，２－ビス［（４－アミノフェノキシ）メチル］プロパン、２，２－ビス［４－（４－アミノフェノキシ）フェニル］ヘキサフルオロプロパン、２，２－ビス［４－（４－アミノフェノキシ）フェニル］プロパン、ビス［４－（３－アミノフェノキシ）フェニル］スルホン、ビス［４－（４－アミノフェノキシ）フェニル］スルホン、１，１－ビス（４－アミノフェニル）シクロヘキサン、α，α’－ビス（４－アミノフェニル）－１，４－ジイソプロピルベンゼン、９，９－ビス（４－アミノフェニル）フルオレン、２，２－ビス（３－アミノフェニル）ヘキサフルオロプロパン、２，２－ビス（４－アミノフェニル）ヘキサフルオロプロパン、４，４’－ジアミノジフェニルアミン、２，４－ジアミノジフェニルアミン、１，８－ジアミノナフタレン、１，５－ジアミノナフタレン、１，５－ジアミノアントラキノン、１，３－ジアミノピレン、１，６－ジアミノピレン、１，８－ジアミノピレン、２，７－ジアミノフルオレン、１，３－ビス（４－アミノフェニル）テトラメチルジシロキサン、ベンジジン、２，２’－ジメチルベンジジン、１，２－ビス（４－アミノフェニル）エタン、１，３－ビス（４－アミノフェニル）プロパン、１，４－ビス（４－アミノフェニル）ブタン、１，５－ビス（４－アミノフェニル）ペンタン、１，６－ビス（４－アミノフェニル）ヘキサン、１，７－ビス（４－アミノフェニル）ヘプタン、１，８－ビス（４－アミノフェニル）オクタン、１，９－ビス（４－アミノフェニル）ノナン、１，１０－ビス（４－アミノフェニル）デカン、１，３－ビス（４－アミノフェノキシ）プロパン、１，４－ビス（４－アミノフェノキシ）ブタン、１，５－ビス（４－アミノフェノキシ）ペンタン、１，６－ビス（４－アミノフェノキシ）ヘキサン、１，７－ビス（４－アミノフェノキシ）ヘプタン、１，８－ビス（４－アミノフェノキシ）オクタン、１，９－ビス（４－アミノフェノキシ）ノナン、１，１０－ビス（４－アミノフェノキシ）デカン、ジ（４－アミノフェニル）プロパン－１，３－ジオエート、ジ（４－アミノフェニル）ブタン－１，４－ジオエート、ジ（４－アミノフェニル）ペンタン－１，５－ジオエート、ジ（４－アミノフェニル）ヘキサン－１，６－ジオエート、ジ（４－アミノフェニル）ヘプタン－１，７－ジオエート、ジ（４－アミノフェニル）オクタン－１，８－ジオエート、ジ（４－アミノフェニル）ノナン－１，９－ジオエート、ジ（４－アミノフェニル）デカン－１，１０－ジオエート、１，３－ビス〔４－（４－アミノフェノキシ）フェノキシ〕プロパン、１，４－ビス〔４－（４－アミノフェノキシ）フェノキシ〕ブタン、１，５－ビス〔４－（４－アミノフェノキシ）フェノキシ〕ペンタン、１，６－ビス〔４－（４－アミノフェノキシ）フェノキシ〕ヘキサン、１，７－ビス〔４－（４－アミノフェノキシ）フェノキシ〕ヘプタン、１，８－ビス〔４－（４－アミノフェノキシ）フェノキシ〕オクタン、１，９－ビス〔４－（４－アミノフェノキシ）フェノキシ〕ノナン、１，１０－ビス〔４－（４－アミノフェノキシ）フェノキシ〕デカンなどが挙げられる。 Examples of aromatic diamines 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′-diamino-3,3′-dimethyldiphenylmethane, 2,2′-diaminostilbene, 4,4′-dia Nostilbene, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'- Diaminobenzophenone, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,5-bis (4- Aminophenoxy) benzoic acid, 4,4'-bis (4-aminophenoxy) bibenzyl, 2,2-bis [(4-aminophenoxy) methyl] propane, 2,2-bis [4- (4-aminophenoxy) Phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] propa Bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, 1,1-bis (4-aminophenyl) cyclohexane, α, α′-bis (4 -Aminophenyl) -1,4-diisopropylbenzene, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) ) Hexafluoropropane, 4,4'-diaminodiphenylamine, 2,4-diaminodiphenylamine, 1,8-diaminonaphthalene, 1,5-diaminonaphthalene, 1,5-diaminoanthraquinone, 1,3-diaminopyrene, 1, 6-diaminopyrene, 1,8-diaminopyrene, 2,7-diaminofluorene, 1,3-bis (4 Aminophenyl) tetramethyldisiloxane, benzidine, 2,2′-dimethylbenzidine, 1,2-bis (4-aminophenyl) ethane, 1,3-bis (4-aminophenyl) propane, 1,4-bis ( 4-aminophenyl) butane, 1,5-bis (4-aminophenyl) pentane, 1,6-bis (4-aminophenyl) hexane, 1,7-bis (4-aminophenyl) heptane, 1,8- Bis (4-aminophenyl) octane, 1,9-bis (4-aminophenyl) nonane, 1,10-bis (4-aminophenyl) decane, 1,3-bis (4-aminophenoxy) propane, 1, 4-bis (4-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) hexane, 1,7-bi (4-aminophenoxy) heptane, 1,8-bis (4-aminophenoxy) octane, 1,9-bis (4-aminophenoxy) nonane, 1,10-bis (4-aminophenoxy) decane, di ( 4-aminophenyl) propane-1,3-dioate, di (4-aminophenyl) butane-1,4-dioate, di (4-aminophenyl) pentane-1,5-dioate, di (4-aminophenyl) Hexane-1,6-dioate, di (4-aminophenyl) heptane-1,7-dioate, di (4-aminophenyl) octane-1,8-dioate, di (4-aminophenyl) nonane-1,9 -Dioate, di (4-aminophenyl) decane-1,10-dioate, 1,3-bis [4- (4-aminophenoxy) phenoxy] propane, 4-bis [4- (4-aminophenoxy) phenoxy] butane, 1,5-bis [4- (4-aminophenoxy) phenoxy] pentane, 1,6-bis [4- (4-aminophenoxy) phenoxy] Hexane, 1,7-bis [4- (4-aminophenoxy) phenoxy] heptane, 1,8-bis [4- (4-aminophenoxy) phenoxy] octane, 1,9-bis [4- (4-amino Phenoxy) phenoxy] nonane, 1,10-bis [4- (4-aminophenoxy) phenoxy] decane, and the like.
　芳香族－脂肪族ジアミンの例としては、３－アミノベンジルアミン、４－アミノベンジルアミン、３－アミノ－Ｎ－メチルベンジルアミン、４－アミノ－Ｎ－メチルベンジルアミン、３－アミノフェネチルアミン、４－アミノフェネチルアミン、３－アミノ－Ｎ－メチルフェネチルアミン、４－アミノ－Ｎ－メチルフェネチルアミン、３－（３－アミノプロピル）アニリン、４－（３－アミノプロピル）アニリン、３－（３－メチルアミノプロピル）アニリン、４－（３－メチルアミノプロピル）アニリン、３－（４－アミノブチル）アニリン、４－（４－アミノブチル）アニリン、３－（４－メチルアミノブチル）アニリン、４－（４－メチルアミノブチル）アニリン、３－（５－アミノペンチル）アニリン、４－（５－アミノペンチル）アニリン、３－（５－メチルアミノペンチル）アニリン、４－（５－メチルアミノペンチル）アニリン、２－（６－アミノナフチル）メチルアミン、３－（６－アミノナフチル）メチルアミン、２－（６－アミノナフチル）エチルアミン、３－（６－アミノナフチル）エチルアミンなどが挙げられる。 Examples of 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-methylaminopentyl) aniline, 4- (5-methylaminopentyl) aniline, 2- (6-aminonaphthyl) methylamine, 3- (6-aminonaphthyl) methylamine, 2- (6 -Aminonaphthyl) ethylamine, 3- (6-aminonaphthyl) ethylamine and the like.
　複素環式ジアミンの例としては、２，６－ジアミノピリジン、２，４－ジアミノピリジン、２，４－ジアミノ－１，３，５－トリアジン、２，７－ジアミノジベンゾフラン、３，６－ジアミノカルバゾール、２，４－ジアミノ－６－イソプロピル－１，３，５－トリアジン、２，５－ビス（４－アミノフェニル）－１，３，４－オキサジアゾールなどが挙げられる。 Examples of heterocyclic diamines 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.
　本発明のポリアミドを得るためにジアミン成分と反応させるジカルボン酸としては、芳香族環を有しないジカルボン酸、例えば脂肪族ジカルボン酸や脂環式系のジカルボン酸が好ましい。そのようなジカルボン酸またはその誘導体の脂肪族ジカルボン酸の具体例として、マロン酸、蓚酸、ジメチルマロン酸、コハク酸、フマル酸、グルタル酸、アジピン酸、ムコン酸、２－メチルアジピン酸、トリメチルアジピン酸、ピメリン酸、２，２－ジメチルグルタル酸、３，３－ジエチルコハク酸、アゼライイン酸、セバシン酸およびスベリン酸等のジカルボン酸を挙げることができる。 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. Specific examples of such 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.
　脂環式系のジカルボン酸としては、１，１－シクロプロパンジカルボン酸、１，２－シクロプロパンジカルボン酸、１，１－シクロブタンジカルボン酸、１，２－シクロブタンジカルボン酸、１，３－シクロブタンジカルボン酸、３，４－ジフェニル－１，２－シクロブタンジカルボン酸、２，４－ジフェニル－１，３－シクロブタンジカルボン酸、１－シクロブテン－１，２－ジカルボン酸、１－シクロブテン－３，４－ジカルボン酸、１，１－シクロペンタンジカルボン酸、１，２－シクロペンタンジカルボン酸、１，３－シクロペンタンジカルボン酸、１，１－シクロヘキサンジカルボン酸、１，２－シクロヘキサンジカルボン酸、１，３－シクロヘキサンジカルボン酸、１，４－シクロヘキサンジカルボン酸、１，４－（２－ノルボルネン）ジカルボン酸、ノルボルネン－２，３－ジカルボン酸、ビシクロ［２．２．２］オクタン－１，４－ジカルボン酸、ビシクロ［２．２．２］オクタン－２，３－ジカルボン酸、２，５－ジオキソ－１，４－ビシクロ［２．２．２］オクタンジカルボン酸、１，３－アダマンタンジカルボン酸、４，８－ジオキソ－１，３－アダマンタンジカルボン酸、２，６－スピロ［３．３］ヘプタンジカルボン酸、１，３－アダマンタン二酢酸、カンファ－酸等を挙げることができる。 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. Acid, 3,4-diphenyl-1,2-cyclobutanedicarboxylic acid, 2,4-diphenyl-1,3-cyclobutanedicarboxylic acid, 1-cyclobutene-1,2-dicarboxylic acid, 1-cyclobutene-3,4-dicarboxylic acid Acid, 1,1-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,1-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexane Dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,4- (2-nor Lunene) dicarboxylic acid, norbornene-2,3-dicarboxylic acid, bicyclo [2.2.2] octane-1,4-dicarboxylic acid, bicyclo [2.2.2] octane-2,3-dicarboxylic acid, 2, 5-dioxo-1,4-bicyclo [2.2.2] octanedicarboxylic acid, 1,3-adamantane dicarboxylic acid, 4,8-dioxo-1,3-adamantane dicarboxylic acid, 2,6-spiro [3. 3] Heptanedicarboxylic acid, 1,3-adamantanediacetic acid, camphoric acid and the like.
　なお、本発明に用いるポリアミドを製造する際に、本発明の効果を損なわない限り、芳香族ジカルボン酸や複素環を含むジカルボン酸等を用いてもよい。その際、芳香族ジカルボン酸や複素環を含むジカルボン酸の合計量は、全ジカルボン酸の合計量１００モルあたり１０モル以下にすることが好ましい。芳香族ジカルボン酸や複素環を含むジカルボン酸の含有量が過大であると、Ｎ－アルコキシメチル変性の際にホルムアルデヒドと芳香族環とが反応してしまい、得られる樹脂の取り扱い性、物性等が低下する場合がある。 In producing the polyamide used in the present invention, 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. At that time, 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.
　芳香族ジカルボン酸としては、ｏ－フタル酸、イソフタル酸、テレフタル酸、５－メチルイソフタル酸、５－ｔｅｒｔ－ブチルイソフタル酸、５－アミノイソフタル酸、５－ヒドロキシイソフタル酸、２，５－ジメチルテレフタル酸、テトラメチルテレフタル酸、１，４－ナフタレンジカルボン酸、２，５－ナフタレンジカルボン酸、２，６－ナフタレンジカルボン酸、２，７－ナフタレンジカルボン酸、１，４－アントラセンジカルボン酸、１，４－アントラキノンジカルボン酸、２，５－ビフェニルジカルボン酸、４，４’－ビフェニルジカルボン酸、１，５－ビフェニレンジカルボン酸、４，４’’－ターフェニルジカルボン酸、４，４’－ジフェニルメタンジカルボン酸、４，４’－ジフェニルエタンジカルボン酸、４，４’－ジフェニルプロパンジカルボン酸、２，２－ビス（フェニル）プロパンジカルボン酸、４，４’－ジフェニルヘキサフルオロプロパンジカルボン酸、２，２－ジフェニルヘキサフルオロプロパン－４，４’－ジカルボン酸、４，４’－ジフェニルエーテルジカルボン酸、４，４’－ビベンジルジカルボン酸、４，４’－スチルベンジカルボン酸、４，４’－トランジカルボン酸、４，４’－カルボニル二安息香酸、４，４’－ジフェニルスルホンジカルボン酸、４，４’－ジフェニルスルフィドジカルボン酸、ｐ－フェニレン二酢酸、３，３’－ｐ－フェニレンジプロピオン酸、４－カルボキシ桂皮酸、ｐ－フェニレンジアクリル酸、３，３’－［４，４’－（メチレンジ－ｐ－フェニレン）］ジプロピオン酸、４，４’－［４，４’－（オキシジ－ｐ－フェニレン）］ジプロピオン酸、４，４’－［４，４’－（オキシジ－ｐ－フェニレン）］二酪酸、（イソプロピリデンジ－ｐ－フェニレンジオキシ）二酪酸、ビス（ｐ－カルボキシフェニル）ジメチルシラン等のジカルボン酸を挙げることができる。 As 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, 4,4'-diphenylethanedicarboxylic acid, 4,4'-di Phenylpropanedicarboxylic acid, 2,2-bis (phenyl) propanedicarboxylic acid, 4,4′-diphenylhexafluoropropanedicarboxylic acid, 2,2-diphenylhexafluoropropane-4,4′-dicarboxylic acid, 4,4 ′ -Diphenyl ether dicarboxylic acid, 4,4'-bibenzyldicarboxylic acid, 4,4'-stilbene dicarboxylic acid, 4,4'-transidicarboxylic acid, 4,4'-carbonyldibenzoic acid, 4,4'-diphenylsulfone Dicarboxylic acid, 4,4′-diphenylsulfide dicarboxylic acid, p-phenylenediacetic acid, 3,3′-p-phenylenedipropionic acid, 4-carboxycinnamic acid, p-phenylenediacrylic acid, 3,3 ′-[ 4,4 ′-(methylenedi-p-phenylene)] dipropionic acid, 4,4 ′-[4,4 ′-(oxy) Di-p-phenylene)] dipropionic acid, 4,4 '-[4,4'-(oxydi-p-phenylene)] butyric acid, (isopropylidenedi-p-phenylenedioxy) dibutyric acid, bis (p Mention may be made of dicarboxylic acids such as -carboxyphenyl) dimethylsilane.
　複素環を含むジカルボン酸としては、１，５－（９－オキソフルオレン）ジカルボン酸、３，４－フランジカルボン酸、４，５－チアゾールジカルボン酸、２－フェニル－４，５－チアゾールジカルボン酸、１，２，５－チアジアゾール－３，４－ジカルボン酸、１，２，５－オキサジアゾール－３，４－ジカルボン酸、２，３－ピリジンジカルボン酸、２，４－ピリジンジカルボン酸、２，５－ピリジンジカルボン酸、２，６－ピリジンジカルボン酸、３，４－ピリジンジカルボン酸、３，５－ピリジンジカルボン酸等を挙げることができる。 Examples of the dicarboxylic acid containing a heterocyclic ring 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.
　上記の各種ジカルボン酸は、酸ジハライドあるいは無水の構造のものであってもよい。上記各種ジカルボン酸の化合物には異性体が存在するものもあるが、それらを含む混合物であってもよい。また、２種以上の化合物を併用してもよい。なお、本発明に使用するジカルボン酸類は、上記の例示化合物に限定されるものではない。 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.
　ジカルボン酸とジアミンとの重縮合等によってポリアミドを製造する方法としては、ジカルボン酸ジクロリドとジアミン成分との反応や、ジカルボン酸とジアミン成分を適当な縮合剤、塩基の存在下にて反応させる方法が挙げられる。 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.
　具体的には、ジカルボン酸ジクロリドとジアミンとを塩基と有機溶剤の存在下で－２０℃～１５０℃、好ましくは０℃～５０℃において、３０分～２４時間、好ましくは１～４時間反応させることによって合成することができる。 Specifically, 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. Can be synthesized.
　前記塩基には、ピリジン、トリエチルアミン、４－ジメチルアミノピリジンが使用できるが、反応が穏和に進行するためにピリジンが好ましい。塩基の添加量は、除去が容易な量で、かつ高分子量体が得やすいという観点から、ジカルボン酸ジクロリドに対して、２～４倍モルであることが好ましい。 As the base, 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.
　縮合剤存在下にて縮合重合を行なう場合、該縮合剤としてトリフェニルホスファイト、ジシクロヘキシルカルボジイミド、１－エチル－３－（３－ジメチルアミノプロピル）カルボジイミド塩酸塩、Ｎ，Ｎ’－カルボニルジイミダゾール、ジメトキシ－１，３，５－トリアジニルメチルモルホリニウム、Ｏ－（ベンゾトリアゾール－１－イル）－Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチルウロニウム　テトラフルオロボラート、Ｏ－（ベンゾトリアゾール－１－イル）－Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチルウロニウムヘキサフルオロホスファート、（２，３－ジヒドロ－２－チオキソ－３－ベンゾオキサゾリル）ホスホン酸ジフェニル、４－（４，６－ジメトキシ－１，３，５－トリアジンー２－イル）４－メトキシモルホリウムクロリド　ｎ－水和物などが使用できる。 When 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 n- And the like can be used hydrate.
　また、上記縮合剤を用いる方法において、ルイス酸を添加剤として加えることで反応が効率的に進行する。ルイス酸としては、塩化リチウム、臭化リチウムなどのハロゲン化リチウムが好ましい。ルイス酸の添加量はジカルボン酸に対して０．１～１．０倍モル量であることが好ましい。 In the method using the condensing agent, the reaction proceeds efficiently by adding Lewis acid as an additive. As the 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.
　ジカルボン酸類とジアミン成分との反応に用いる有機溶媒としては、生成したポリアミドが溶解するものであれば特に限定されない。その具体例を以下に挙げる。 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，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチル－２－ピロリドン、Ｎ－エチル－２－ピロリドン、Ｎ－メチルカプロラクタム、ジメチルスルホキシド、テトラメチル尿素、ピリジン、ジメチルスルホン、γ－ブチロラクトン、イソプロピルアルコール、メトキシメチルペンタノール、ジペンテン、エチルアミルケトン、メチルノニルケトン、メチルエチルケトン、メチルイソアミルケトン、メチルイソプロピルケトン、メチルセルソルブ、エチルセルソルブ、メチルセロソルブアセテート、エチルセロソルブアセテート、ブチルカルビトール、エチルカルビトール、エチレングリコール、エチレングリコールモノアセテート、エチレングリコールモノイソプロピルエーテル、エチレングリコールモノブチルエーテル、プロピレングリコール、プロピレングリコールモノアセテート、プロピレングリコールモノメチルエーテル、プロピレングリコール－ｔｅｒｔ－ブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジエチレングリコール、ジエチレングリコールモノアセテート、ジエチレングリコールジメチルエーテル、ジプロピレングリコールモノアセテートモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノアセテートモノエチルエーテル、ジプロピレングリコールモノプロピルエーテル、ジプロピレングリコールモノアセテートモノプロピルエーテル、３－メチル－３－メトキシブチルアセテート、トリプロピレングリコールメチルエーテル、３－メチル－３－メトキシブタノール、ジイソプロピルエーテル、エチルイソブチルエーテル、ジイソブチレン、アミルアセテート、ブチルブチレート、ブチルエーテル、ジイソブチルケトン、メチルシクロへキセン、プロピルエーテル、ジヘキシルエーテル、ジオキサン、ｎ－へキサン、ｎ－ペンタン、ｎ－オクタン、ジエチルエーテル、シクロヘキサノン、エチレンカーボネート、プロピレンカーボネート、乳酸メチル、乳酸エチル、酢酸メチル、酢酸エチル、酢酸ｎ－ブチル、酢酸プロピレングリコールモノエチルエーテル、ピルビン酸メチル、ピルビン酸エチル、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、３－エトキシプロピオン酸、３－メトキシプロピオン酸、３－メトキシプロピオン酸プロピル、３－メトキシプロピオン酸ブチル、ジグライム、４－ヒドロキシ－４－メチル－２－ペンタノン、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド、３－エトキシ－Ｎ，Ｎ－ジメチルプロパンアミド、３－ブトキシ－Ｎ，Ｎ－ジメチルプロパンアミドなどが挙げられる。これらは単独で使用しても、混合して使用してもよい。さらに、ポリアミック酸を溶解させない溶媒であっても、生成したポリアミドが析出しない範囲で、上記溶媒に混合して使用してもよい。 N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, γ-butyrolactone , Isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl Carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether Ter, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monoethyl Ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxy Butanol, di Isopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, Cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, 3-methoxy Ethyl propionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxy Propyl propionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy-N, N-dimethylpropanamide, 3 -Butoxy-N, N-dimethylpropanamide and the like. These may be used alone or in combination. Further, even a solvent that does not dissolve polyamic acid may be used by mixing with the above solvent as long as the produced polyamide does not precipitate.
　モノマーおよびポリマーの溶解性からＮ－メチル－２－ピロリドン、γ－ブチロラクトンが好ましく、これらは１種又は２種以上を混合して用いてもよい。合成時のモノマーの合計濃度は、ポリマーの析出が起こりにくく、かつ高分子量体が得やすいという観点から、１～３０質量％が好ましく、５～２０質量％がより好ましい。 N-methyl-2-pyrrolidone and γ-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.
　好ましい実施形態においては、本発明で使用するポリアミドは、ＩＳＯ３０７に準拠して９６％Ｈ２ＳＯ４中０．５％で測定された粘度（粘度数：ＶＮ）が、約１４０～約２７０立方センチメートル毎グラム（ｃｍ３／ｇ）の範囲にある脂肪族ポリアミドである。 In a preferred embodiment, 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).
　上記ポリアミドのうち、好ましいポリアミドとしては、ナイロン－６、ナイロン－１１、ナイロン－１２、ナイロン－６６、ナイロン－６１０、ナイロン－６１２、ナイロン－１０１０、ナイロン－１２１２、ナイロン－６６／６１０、ナイロン６／６６、ナイロン６／６９、またはこれらの２種以上の組合せからなる群から選択されるポリアミドが挙げられる。さらに好ましくは、Ｈ－（ＮＨ－（ＣＨ２）５－ＣＯ）ｎ－ＯＨ（ナイロン－６）単独重合体または共重合体、Ｈ－（ＮＨ－（ＣＨ２）６－ＨＮ－ＣＯ－（ＣＨ２）４－ＣＯ）ｎ－ＯＨ（ナイロン６６）、Ｈ－（ＮＨ－（ＣＨ２）６－ＨＮ－ＣＯ－（ＣＨ２）８－ＣＯ）ｎ－ＯＨ（ナイロン６１０）、Ｈ－（ＮＨ－（ＣＨ２）６－ＨＮ－ＣＯ－（ＣＨ２）１０－ＣＯ）ｎ－ＯＨ（ナイロン６１２）、Ｈ－（ＮＨ－（ＣＨ２）５－ＣＯ）－ＯＨ＋Ｈ－（ＮＨ－（ＣＨ２）６－ＨＮ－ＣＯ－（ＣＨ２）４－ＣＯ）－ＯＨ（不規則配列）（ナイロン６／６６）、Ｈ－ＮＨ－（ＣＨ２）５－ＣＯ）－ＯＨ＋Ｈ－（ＮＨ－（ＣＨ２）１１－ＣＯ）－ＯＨ（不規則配列）（ナイロン６／１２）、およびＨ－（ＮＨ－（ＣＨ２）５－ＣＯ）－ＯＨ＋Ｈ－（ＮＨ－（ＣＨ２）６－ＨＮ－ＣＯ－（ＣＨ２）７－ＣＯ）－ＯＨ（不規則配列）（ナイロン６／６９）、ならびに上述のポリアミドの混合物を含むポリアミドが挙げられる。 Among the above polyamides, 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. More preferably, H— (NH— (CH 2 ) 5 —CO) n —OH (nylon-6) homopolymer or copolymer, H— (NH— (CH 2 ) 6 —HN—CO— (CH 2 ) 4 —CO) n —OH (nylon 66), H— (NH— (CH 2 ) 6 —HN—CO— (CH 2 ) 8 —CO) n —OH (nylon 610), H— (NH— (CH 2 ) 6 —HN—CO— (CH 2 ) 10 —CO) n —OH (nylon 612), H— (NH— (CH 2 ) 5 —CO) —OH + H— (NH— (CH 2 ) 6 —HN—CO— (CH 2 ) 4 —CO) —OH (irregular arrangement) (nylon 6/66), H—NH— (CH 2 ) 5 —CO) —OH + H— (NH— (CH 2 ) 11 -CO) -OH (irregular arrangement) (nylon 6/12), and H- (NH (CH 2) 5 -CO) -OH + H- (NH- (CH 2) 6 -HN-CO- (CH 2) 7 -CO) -OH ( irregularly arranged) (nylon 6/69), and the above-mentioned polyamide And polyamides containing a mixture of
　なおナイロン６／６６（ポリアミド６／６６）は、ＢＡＳＦ社から「Ｕｌｔｒａｍｉｄ　Ｃ４」および「Ｕｌｔｒａｍｉｄ　Ｃ３５」の商品名で、または宇部興産（株）（Ｕｂｅ　Ｉｎｄｕｓｔｒｉｅｓ　Ｌｔｄ．）から「Ｕｂｅ５０３３ＦＸＤ２７」の商品名で市販されている。ナイロン６（ポリアミド６）は、例えば、Ｅ．Ｉ．ｄｕ　Ｐｏｎｔ　ｄｅ　Ｎｅｍｏｕｒｓ社から市販されている。 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.
　より好ましいポリアミドとしては、ポリ－ε－カプラミド（ナイロン－６）、ポリヘキサメチレンアジパミド（ナイロン６６）、ポリヘキサメチレンセバカミド（ナイロン６１０）等があるが、その他の脂肪族ポリアミド、脂環あるいは異節環を主鎖に含むポリアミドでも差し支えない。
　本明細書において使用される「脂肪族ポリアミド」という用語は、脂肪族ポリアミド、脂肪族コポリアミド、およびこれらのブレンドまたは混合物を指すことができる。 More preferable polyamides include poly-ε-capramide (nylon-6), polyhexamethylene adipamide (nylon 66), polyhexamethylene sebacamide (nylon 610), and other aliphatic polyamides, fats A polyamide containing a ring or a hetero ring in the main chain may be used.
As used herein, the term “aliphatic polyamide” can refer to aliphatic polyamides, aliphatic copolyamides, and blends or mixtures thereof.
　こうして得られるポリアミドや、市販のポリアミドを、例えば、T.L.Cairnsら（J.Am.Chem.Soc.，71,P651(1949)）が提案するような方法で、アミド結合の窒素原子Ｎにアルコキシメチル基またはアルキルチオメチル基を導入することができる。 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.
　例えば、ポリアミドのギ酸溶液に、ホルマリンのアルコールまたはメルカプタン溶液を作用させた後、水／アセトン混合液などの貧溶媒中に注ぎ、アンモニアで中和することによって変性ポリアミドの沈澱物が生じる。また、工業的には、上記ポリアミドに、高温、高圧下でりん酸触媒を用いて、直接にホルマリンとアルコールまたはメルカプタンを作用させることにより、変性ポリアミドを作製することができる。ポリアミドの窒素原子Ｎの置換度が進むにつれて、樹脂の結晶性、融点、弾性率は低下し、溶解性、柔軟性は増大する。置換度は、反応条件によって広範囲で選択することができるが、本発明においては、置換度が１０～５０モル％、好ましくは２０～４０モル％のものが用いられる。この置換領域のものが、最もアルコールに可溶で、溶液状態での安定性がよい。１０モル％より低いものは、溶剤溶解性や密着性、および体積抵抗率において特性を満足することができない。他方、置換度が５０モル％より高くなると、反応条件設定が困難になる。アミド結合の窒素原子の置換基の種類は、変性反応に用いる溶剤によって選択することができ、アルコールを用いる場合は、例えば、メトキシメチル基、エトキシメチル基、イソブトキシメチル基等を有するものが得られ、メルカプタンを用いる場合は、例えば、エチルチオメチル基、イソブチルチオメチル基等を有するものが得られる。この上記変性ポリアミド樹脂のアミド結合の窒素原子を置換した極性基の機能により、得られる樹脂の溶解度を向上させることができる。 For example, after a formalin alcohol or mercaptan solution is allowed to act on a polyamide formic acid solution, it is poured into a poor solvent such as a water / acetone mixture, and neutralized with ammonia to produce a precipitate of a modified polyamide. Further, industrially, 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. As the degree of substitution of the nitrogen atom N in the polyamide proceeds, the crystallinity, melting point and elastic modulus of the resin decrease, and the solubility and flexibility increase. The degree of substitution can be selected in a wide range depending on the reaction conditions. In the present invention, 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. In the case of using 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.
　なお、Ｎ－アルコキシメチル化またはＮ－アルキルチオメチル化されたポリアミドとしては、市販されているものを用いることができる。そのような市販されているものとしては、例えば、ナガセケムテックス（株）のトレジン（登録商標）フレークタイプ　Ｆ－３０Ｋ、ＭＦ－３０、ＥＦ－３０Ｔ、トレジン水溶性タイプＦＳ－３５０Ｅ５ＡＳ、（株）鉛市のファインレジン（登録商標）ＦＲ－１０１、ＦＲ－１０１Ｋ、ＦＲ－１０４、ＦＲ－１０５、ＦＲ－３０１、ＥＭ－１２０、ＥＭ－２２０、ＥＭ－３２５、ＮＫ－１００１、ファインレックス（登録商標）ＳＮ－８０２、ＳＮ－８０３、ＦＲ－７００Ｅ、ＦＲ－７５０Ｅ、ＳＧ－２０００等が挙げられる。 As the N-alkoxymethylated or N-alkylthiomethylated polyamide, commercially available products can be used. Examples of such 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. Fine Resin (registered trademark) FR-101, FR-101K, FR-104, FR-105, FR-301, EM-120, EM-220, EM-325, NK-1001, Finelex (registered trademark) ) SN-802, SN-803, FR-700E, FR-750E, SG-2000 and the like.
　なお本発明において（Ｂ）成分として、１，０００～１００，０００の重量平均分子量を有するポリアミドを用いることが好ましい。なお本明細書において、重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により、標準試料としてポリスチレンを用いて得られる値である。 In the present invention, it is preferable to use a polyamide having a weight average molecular weight of 1,000 to 100,000 as the component (B). In this specification, the weight average molecular weight is a value obtained by using gel as a standard sample by gel permeation chromatography (GPC).
＜（Ｃ）成分＞
　本実施の形態の硬化膜形成組成物は、上述した（Ａ）成分および（Ｂ）に加え、（Ｃ）成分として架橋触媒を含有する。 <(C) component>
The cured film forming composition of this Embodiment contains a crosslinking catalyst as (C) component in addition to (A) component and (B) mentioned above.
　（Ｃ）成分の架橋触媒としては、例えば、酸または熱酸発生剤とすることができる。この架橋触媒は、本実施の形態の硬化膜形成組成物を用いた硬化膜の形成において、熱硬化反応の促進に有効となる。 (C) 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.
　（Ｃ）成分として酸または熱酸発生剤を用いる場合、（Ｃ）成分は、スルホン酸基含有化合物、塩酸またはその塩、プリベークまたはポストベーク時に熱分解して酸を発生する化合物、すなわち温度８０℃～２５０℃で熱分解して酸を発生する化合物であれば特に限定されるものではない。 When an acid or thermal acid generator is used as the component (C), 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.
　そのような化合物としては、例えば、塩酸、並びにメタンスルホン酸、エタンスルホン酸、プロパンスルホン酸、ブタンスルホン酸、ペンタンスルホン酸、オクタンスルホン酸、ベンゼンスルホン酸、ｐ－トルエンスルホン酸、カンファスルホン酸、トリフルオロメタンスルホン酸、ｐ－フェノールスルホン酸、２－ナフタレンスルホン酸、メシチレンスルホン酸、ｐ－キシレン－２－スルホン酸、ｍ－キシレン－２－スルホン酸、４－エチルベンゼンスルホン酸、１Ｈ，１Ｈ，２Ｈ，２Ｈ－パーフルオロオクタンスルホン酸、パーフルオロ（２－エトキシエタン）スルホン酸、ペンタフルオロエタンスルホン酸、ノナフルオロブタン－１－スルホン酸、ドデシルベンゼンスルホン酸等のスルホン酸またはその水和物や塩等が挙げられる。 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-sulfonic acid, dodecylbenzenesulfonic acid and other sulfonic acids or hydrates and salts thereof Etc.
　また、熱により酸を発生する化合物としては、例えば、ビス（トシルオキシ）エタン、ビス（トシルオキシ）プロパン、ビス（トシルオキシ）ブタン、ｐ－ニトロベンジルトシレート、ｏ－ニトロベンジルトシレート、１，２，３－フェニレントリス（メチルスルホネート）、ｐ－トルエンスルホン酸ピリジニウム塩、ｐ－トルエンスルホン酸モルホニウム塩、ｐ－トルエンスルホン酸エチルエステル、ｐ－トルエンスルホン酸プロピルエステル、ｐ－トルエンスルホン酸ブチルエステル、ｐ－トルエンスルホン酸イソブチルエステル、ｐ－トルエンスルホン酸メチルエステル、ｐ－トルエンスルホン酸フェネチルエステル、シアノメチルｐ－トルエンスルホネート、２，２，２－トリフルオロエチルｐ－トルエンスルホネート、２－ヒドロキシブチルｐ－トシレート、Ｎ－エチル－４－トルエンスルホンアミド、および下記式［ＴＡＧ－１］～式［ＴＡＧ－４１］で表される化合物等を挙げることができる。 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-toluenesulfonate, 2,2,2-trifluoroethyl p-toluenesulfonate, 2-hydride Kishibuchiru p- tosylate, N- ethyl-4-toluenesulfonamide, and the following formula [TAG-1] can be exemplified ~ compound represented by [TAG-41], and the like.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
　本発明の実施形態の硬化膜形成組成物における（Ｃ）成分の含有量は、（Ａ）成分である化合物と（Ｂ）成分のアミド基の窒素原子のうちの少なくとも一部がアルコキシメチル化またはアルキルチオメチル化されたポリアミドとの合計量の１００質量部に対して、好ましくは０．０１質量部～１０質量部、より好ましくは０．０５質量部～８質量部、さらに好ましくは０．１質量部～６質量部である。架橋触媒の含有量を上記合計量に対して０．０１質量部以上とすることで、充分な熱硬化性と溶剤耐性を付与することができ、露光に対する高い感度をも付与することができる。また、架橋触媒の含有量を上記合計量に対して１０質量部以下とすることで、硬化膜形成組成物の保存安定性を良好にすることができる。 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. 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. Moreover, 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.
＜（Ｄ）成分＞
　本発明は上記（Ａ）乃至（Ｃ）成分に加えて、（Ｄ）成分を含有してもよい。（Ｄ）成分は炭素原子数２乃至５のヒドロキシアルキルエステル基、アルコキシシリル基、Ｎ－アルコキシメチル基、カルボキシル基及びフェノール性ヒドロキシ基のうちの少なくとも一つを有するアクリル重合体である。（Ｄ）成分を添加することにより、溶剤に対する溶解性が向上する。（Ｄ）成分の好ましい添加量は、（Ａ）成分と（Ｂ）成分との合計量の１００質量部に基づいて、５質量部～１００質量部、さらに好ましくは１０質量部～８０質量部である。 <(D) component>
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. By adding the component (D), solubility in a solvent is improved. 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.
　本発明において、アクリル重合体としてはアクリル酸エステル、メタクリル酸エステル、スチレン、アクリルアミド、メタクリルアミド等の不飽和二重結合を有するモノマーを重合して得られる重合体が適用されうる。 In the present invention, as the 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.
　（Ｄ）成分の炭素原子数２乃至５のヒドロキシアルキルエステル基、アルコキシシリル基、Ｎ－アルコキシメチル基、カルボキシル基及びフェノール性ヒドロキシ基のうちの少なくとも一つを有するアクリル重合体は、斯かる構造を有するアクリル重合体であればよく、アクリル重合体を構成する高分子の主鎖の骨格及び側鎖の種類などについて特に限定されない。 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. There is no particular limitation on the type of the main chain skeleton and side chain of the polymer constituting the acrylic polymer.
　例えば、炭素原子数２乃至５のヒドロキシアルキルエステル基またはアルコキシシリル基を有する構造単位として、好ましい構造単位は下記式［Ｄ１］で表される。
　またカルボキシル基またはフェノール性ヒドロキシ基のうち少なくとも一方を有する構造単位として、好ましい構造単位は下記式［Ｄ２］で表される。
　さらにＮ－アルコキシメチル基を有する構造単位として、好ましい構造単位は下記式［Ｄ３］で表される。 For example, as a structural unit having a hydroxyalkyl ester group having 2 to 5 carbon atoms or an alkoxysilyl group, a preferred structural unit is represented by the following formula [D1].
As a structural unit having at least one of a carboxyl group or a phenolic hydroxy group, a preferred structural unit is represented by the following formula [D2].
Further, as a structural unit having an N-alkoxymethyl group, a preferred structural unit is represented by the following formula [D3].
Figure JPOXMLDOC01-appb-C000013
 　上記式中、Ｘ１１、Ｘ１２及びＸ１３はそれぞれ独立に水素原子又はメチル基を表し、Ｙ１は炭素原子数１乃至３のヒドロキシアルキル基又は炭素原子数１乃至４のアルコキシシリルアルキル基を表し、Ｙ２はカルボキシル基又はフェノール性ヒドロキシ基を表し、Ｙ３は（炭素原子数１乃至６のアルコキシ）メチル基を表す。
Figure JPOXMLDOC01-appb-C000013
 In the above formula, X 11 , X 12 and X 13 each independently represent a hydrogen atom or a methyl group, and 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.
（Ｄ）成分のアクリル重合体は、重量平均分子量が３，０００乃至２００，０００であることが好ましく、４，０００乃至１５０，０００であることがより好ましく、５，０００乃至１００，０００であることがさらになお好ましい。重量平均分子量が２００，０００を超えて過大なものであると、溶剤に対する溶解性が低下しハンドリング性が低下する場合があり、重量平均分子量が３，０００未満で過小なものであると、熱硬化時に硬化不足になり溶剤耐性及び耐熱性が低下する場合がある。 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.
　上述のように、（Ｄ）成分のアクリル重合体の合成方法としては、炭素原子数２乃至５のヒドロキシアルキルエステル基、アルコキシシリル基、Ｎ－アルコキシメチル基、カルボキシル基及びフェノール性ヒドロキシ基のうちの少なくとも一つを有するモノマーを共重合する方法が簡便である。 As described above, 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.
　炭素原子数２乃至５のヒドロキシアルキルエステル基を有するモノマーとしては、例えば２－ヒドロキシエチルメタクリレート、２－ヒドロキシエチルアクリレート、２－ヒドロキシプロピルメタクリレート、２－ヒドロキシプロピルアクリレート、４－ヒドロキシブチルメタクリレート、４－ヒドロキシブチルアクリレートが挙げられる。 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.
　カルボキシル基を有するモノマーとしては、例えばアクリル酸、メタクリル酸、ビニル安息香酸が挙げられる。 Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, and vinyl benzoic acid.
　フェノール性ヒドロキシ基を有するモノマーとしては、例えばｐ－ヒドロキシスチレン、ｍ－ヒドロキシスチレン、ｏ－ヒドロキシスチレンが挙げられる。 Examples of the monomer having a phenolic hydroxy group include p-hydroxystyrene, m-hydroxystyrene, and o-hydroxystyrene.
　アルコキシシリル基を有するモノマーとしては、例えばメタクリロイルオキシプロピルトリメトキシシラン、メタクリロイルオキシプロピルトリエトキシシラン、アクリロイルオキシプロピルトリメトキシシラン、アクリロイルオキシプロピルトリエトキシシランが挙げられる。 Examples of the monomer having an alkoxysilyl group include methacryloyloxypropyltrimethoxysilane, methacryloyloxypropyltriethoxysilane, acryloyloxypropyltrimethoxysilane, and acryloyloxypropyltriethoxysilane.
　Ｎ－アルキコキシメチル基を有するモノマーとしては、Ｎ－メトキシメチルアクリルアミド、Ｎ－メトキシメチルメタクリルアミド、Ｎ－ブトキシメチルアクリルアミド、Ｎ－ブトキシメチルメタクリルアミド、Ｎ－（イソブトキシメチル）アクリルアミド、Ｎ－（イソブトキシメチル）メタクリルアミドが挙げられる。 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.
　また、本発明においては、（Ｄ）成分のアクリル重合体を得る際に、本発明の効果を損なわない限り、上記モノマーの他に、該モノマーと共重合可能なモノマー（以下、その他モノマーとも称する）を併用することができる。 In addition, in the present invention, when obtaining the acrylic polymer of component (D), a monomer copolymerizable with the monomer (hereinafter also referred to as other monomer) in addition to the above monomer, unless the effects of the present invention are impaired. ) Can be used in combination.
　当該その他モノマーとしては、アクリル酸エステル化合物、メタクリル酸エステル化合物、マレイミド化合物、アクリルアミド化合物、アクリロニトリル、マレイン酸無水物、スチレン化合物及びビニル化合物等が挙げられる。 Examples of the other monomers include acrylic ester compounds, methacrylic ester compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds, and vinyl compounds.
　その他モノマーの具体例は、限定されるものではないが、そのようなモノマーの具体例をあえて挙げるとすれば、以下の通りである。 Specific examples of other monomers are not limited, but specific examples of such monomers are as follows.
　アクリル酸エステル化合物としては、例えば、メチルアクリレート、エチルアクリレート、イソプロピルアクリレート、ベンジルアクリレート、ナフチルアクリレート、アントリルアクリレート、アントリルメチルアクリレート、フェニルアクリレート、２，２，２－トリフルオロエチルアクリレート、ｔｅｒｔ－ブチルアクリレート、シクロヘキシルアクリレート、イソボルニルアクリレート、２－メトキシエチルアクリレート、メトキシトリエチレングリコールアクリレート、２－エトキシエチルアクリレート、テトラヒドロフルフリルアクリレート、３－メトキシブチルアクリレート、２－メチル－２－アダマンチルアクリレート、γ－ブチロラクトンアクリレート、２－プロピル－２－アダマンチルアクリレート、８－メチル－８－トリシクロデシルアクリレート、８－エチル－８－トリシクロデシルアクリレート、２，３－ジヒドロキシプロピルアクリレート、ジエチレングリコールモノアクリレート、カプロラクトン２－（アクリロイルオキシ）エチルエステル、ポリ（エチレングリコール）エチルエーテルアクリレートおよび５－アクリロイルオキシ－６－ヒドロキシノルボルネン－２－カルボキシリック－６－ラクトンなどが挙げられる。 Examples of the acrylic ester compound 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. Acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, γ- Butyrolactone acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8 Tricyclodecyl acrylate, 8-ethyl-8-tricyclodecyl acrylate, 2,3-dihydroxypropyl acrylate, diethylene glycol monoacrylate, caprolactone 2- (acryloyloxy) ethyl ester, poly (ethylene glycol) ethyl ether acrylate and 5-acryloyl And oxy-6-hydroxynorbornene-2-carboxyl-6-lactone.
　メタクリル酸エステル化合物としては、例えば、メチルメタクリレート、エチルメタクリレート、イソプロピルメタクリレート、ベンジルメタクリレート、ナフチルメタクリレート、アントリルメタクリレート、アントリルメチルメタクリレート、フェニルメタクリレート、２，２，２－トリフルオロエチルメタクリレート、ｔｅｒｔ－ブチルメタクリレート、シクロヘキシルメタクリレート、イソボルニルメタクリレート、２－メトキシエチルメタクリレート、メトキシトリエチレングリコールメタクリレート、２－エトキシエチルメタクリレート、テトラヒドロフルフリルメタクリレート、３－メトキシブチルメタクリレート、２－メチル－２－アダマンチルメタクリレート、γ－ブチロラクトンメタクリレート、２－プロピル－２－アダマンチルメタクリレート、８－メチル－８－トリシクロデシルメタクリレート、８－エチル－８－トリシクロデシルメタクリレート、２，３－ジヒドロキシプロピルメタクリレート、ジエチレングリコールモノメタクリレート、カプロラクトン２－（メタクリロイルオキシ）エチルエステル、ポリ（エチレングリコール）エチルエーテルメタクリレートおよび５－メタクリロイルオキシ－６－ヒドロキシノルボルネン－２－カルボキシリック－６－ラクトンなどが挙げられる。 Examples of the methacrylic acid ester compound 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. Methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, γ- Butyrolactone methacrylate, 2-propyl-2- Damantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl methacrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monomethacrylate, caprolactone 2- (methacryloyloxy) ethyl ester, poly ( And ethylene glycol) ethyl ether methacrylate and 5-methacryloyloxy-6-hydroxynorbornene-2-carboxyl-6-lactone.
　マレイミド化合物としては、例えば、マレイミド、Ｎ－メチルマレイミド、Ｎ－フェニルマレイミドおよびＮ－シクロヘキシルマレイミドなどが挙げられる。 Examples of maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.
　スチレン化合物としては、例えば、スチレン、メチルスチレン、クロロスチレン、ブロモスチレン、４－ｔｅｒｔ－ブチルスチレン等のスチレン化合物が挙げられる。 Examples of the styrene compound include styrene compounds such as styrene, methylstyrene, chlorostyrene, bromostyrene, and 4-tert-butylstyrene.
　ビニル化合物としては、例えば、メチルビニルエーテル、ベンジルビニルエーテル、ビニルナフタレン、ビニルアントラセン、ビニルビフェニル、ビニルカルバゾール、２－ヒドロキシエチルビニルエーテル、フェニルビニルエーテルおよびプロピルビニルエーテルなどが挙げられる。 Examples of the vinyl compound 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.
　その他モノマーとしては、上記化合物の中でも、アクリル酸エステル化合物、メタクリル酸エステル化合物が好ましく、特に、メチルメタクリレート（メタクリル酸メチル）が入手性及び溶解性等の点で好ましい。 As other monomers, among the above compounds, acrylic ester compounds and methacrylic ester compounds are preferable, and methyl methacrylate (methyl methacrylate) is particularly preferable in terms of availability and solubility.
　（Ｄ）成分のアクリル重合体を得るために上記その他モノマーを使用する場合、該その他モノマーの使用量は、（Ｄ）成分のアクリル重合体を得るために用いる全モノマーの合計量に基づいて、５乃至１００モル％であることが好ましい。上記その他モノマーの使用量が過小である場合、液晶溶剤に対する所望の耐性が得られず、すなわち耐性が低下する場合がある。 (D) When using the said other monomer in order to obtain the acrylic polymer of a component, 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. When 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.
　本発明に用いる（Ｄ）成分のアクリル重合体を得る方法は特に限定されないが、例えば、上記モノマーと所望により上記以外のその他モノマーと重合開始剤等とを共存させた溶剤中において、５０乃至１１０℃の温度下で重合反応により得られる。その際、用いられる溶剤は、モノマー及び重合開始剤等を溶解するものであれば特に限定されない。具体例としては、後述する＜溶剤＞に記載する。 The method for obtaining the acrylic polymer of component (D) used in the present invention is not particularly limited. For example, in 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. In that case, 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.
　前記方法により得られる（Ｄ）成分のアクリル重合体は、通常、溶剤に溶解した溶液の状態である。 The (D) component acrylic polymer obtained by the above method is usually in the form of a solution dissolved in a solvent.
　また、上記方法で得られた（Ｄ）成分のアクリル重合体の溶液を、撹拌下のジエチルエーテルや水等に投入して再沈殿させ、生成した沈殿物を濾過・洗浄した後に、常圧又は減圧下で、常温乾燥又は加熱乾燥し、（Ｄ）成分のアクリル重合体の粉体とすることができる。前記操作により、（Ｄ）成分のアクリル重合体と共存する重合開始剤及び未反応のモノマーを除去することができ、その結果、精製した（Ｄ）成分のアクリル重合体の粉体が得られる。一度の操作で充分に精製できない場合は、得られた粉体を溶剤に再溶解させ、上記の操作を繰り返し行えばよい。 In addition, 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). By the above operation, 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.
　本発明においては、（Ｄ）成分のアクリル重合体は粉体形態で、あるいは精製した粉末を後述する溶剤に再溶解した溶液形態で用いてもよい。 In the present invention, 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.
　また、本発明においては、（Ｄ）成分のアクリル重合体は、複数種の（Ｄ）成分のアクリル重合体の混合物であってもよい。 In the present invention, the (D) component acrylic polymer may be a mixture of a plurality of types of (D) component acrylic polymers.
＜溶剤＞
　本実施の形態の硬化膜形成組成物は、主として溶剤に溶解した溶液状態で用いられる。その際に使用する溶剤は、（Ａ）成分および（Ｂ）成分、（Ｃ）成分、そのほか必要に応じて（Ｄ）成分および後述するその他添加剤を溶解できればよく、その種類および構造などは特に限定されるものでない。 <Solvent>
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.
　溶剤の具体例としては、例えば、メタノール、エタノール、２－プロパノール、１－ブタノール、２－ブタノール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、メチルセロソルブアセテート、エチルセロソルブアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、プロピレングリコール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールプロピルエーテルアセテート、トルエン、キシレン、メチルエチルケトン、シクロペンタノン、シクロヘキサノン、２－ブタノン、３－メチル－２－ペンタノン、２－ペンタノン、２－ヘプタノン、γ－ブチロラクトン、２－ヒドロキシプロピオン酸エチル、２－ヒドロキシ－２－メチルプロピオン酸エチル、エトキシ酢酸エチル、ヒドロキシ酢酸エチル、２－ヒドロキシ－３－メチルブタン酸メチル、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－エトキシプロピオン酸エチル、３－エトキシプロピオン酸メチル、ピルビン酸メチル、ピルビン酸エチル、酢酸エチル、酢酸ブチル、乳酸エチル、乳酸ブチル、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、およびＮ－メチルピロリドン等が挙げられる。これらのうち（Ｂ）成分の溶解性が高いことから、メタノール、エタノール、２－プロパノール、プロピレングリコールモノメチルエーテル等の溶媒が好ましい。 Specific examples of 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, γ-butyrolactone, 2-hydroxypro Ethyl onate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxy Ethyl propionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone Etc. Of these, solvents such as methanol, ethanol, 2-propanol, propylene glycol monomethyl ether are preferred because of the high solubility of component (B).
　これらの溶剤は、１種単独でまたは２種以上の組合せで使用することができ、更に水と混合して使用することができる。 These solvents can be used singly or in combination of two or more, and can also be used by mixing with water.
＜その他添加剤＞
　さらに、本実施の形態の硬化膜形成組成物は、本発明の効果を損なわない限りにおいて、必要に応じて、増感剤、シランカップリング剤、界面活性剤、レオロジー調整剤、顔料、染料、保存安定剤、消泡剤、酸化防止剤等を含有することができる。 <Other additives>
Furthermore, as long as the effect of the present invention is not impaired, 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.
　例えば、増感剤は、本実施の形態の硬化膜形成組成物を用いて熱硬化膜を形成した後、光反応を促進することにおいて有効である。 For example, a sensitizer is effective in promoting a photoreaction after forming a thermosetting film using the cured film forming composition of the present embodiment.
　その他添加剤の一例であるの増感剤としては、ベンゾフェノン、アントラセン、アントラキノン、チオキサントン等およびその誘導体、並びにニトロフェニル化合物等が挙げられる。これらのうち、ベンゾフェノン誘導体およびニトロフェニル化合物が好ましい。好ましい化合物の具体例としてＮ，Ｎ－ジエチルアミノベンゾフェノン、２－ニトロフルオレン、２－ニトロフルオレノン、５－ニトロアセナフテン、４－ニトロビフェニル、４－ニトロけい皮酸、４－ニトロスチルベン、４－ニトロベンゾフェノン、５－ニトロインドール等が挙げられる。特に、ベンゾフェノンの誘導体であるＮ，Ｎ－ジエチルアミノベンゾフェノンが好ましい。 Examples of other sensitizers that are additives include benzophenone, anthracene, anthraquinone, thioxanthone, and derivatives thereof, and nitrophenyl compounds. Of these, 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. In particular, N, N-diethylaminobenzophenone which is a derivative of benzophenone is preferable.
　これらの増感剤は上記のものに限定されるものではない。また、増感剤は単独でまたは２種以上の化合物を組み合わせて併用することが可能である。 These sensitizers are not limited to those described above. The sensitizers can be used alone or in combination of two or more compounds.
　本実施の形態の硬化膜形成組成物における増感剤の好ましい使用割合は、（Ａ）成分の化合物と（Ｂ）成分のアミド基の窒素原子のうちの少なくとも一部がアルコキシメチル化またはアルキルチオメチル化されたポリアミドとの合計質量の１００質量部に対して０．１質量部～２０質量部であり、より好ましくは０．２質量部～１０質量部である。この割合が過小である場合には、増感剤としての効果を充分に得られない場合があり、過大である場合には透過率の低下および塗膜の荒れが生じることがある。 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.
＜硬化膜形成組成物の調製＞
　本実施の形態の硬化膜形成組成物は、（Ａ）成分である低分子の光配向成分、（Ｂ）成分であるアミド基の窒素原子のうちの少なくとも一部がアルコキシメチル化またはアルキルチオメチル化されたポリアミド及び（Ｃ）成分である架橋触媒が溶媒に溶解したものである。さらに、本実施の形態の硬化膜形成組成物は、（Ｄ）成分として炭素原子数２乃至５のヒドロキシアルキルエステル基、アルコキシシリル基、Ｎ－アルコキシメチル基、カルボキシル基及びフェノール性ヒドロキシ基のうちの少なくとも一つを有するアクリル重合体を含有することができる。そして、本発明の効果を損なわない限りにおいて、その他の添加剤を含有することができる。 <Preparation of cured film forming composition>
In the cured film forming composition of the present embodiment, 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. Furthermore, 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.
　（Ａ）成分と（Ｂ）成分の配合比は、質量比で（Ａ）成分：（Ｂ）成分＝５：９５～６０：４０が好ましい。（Ｂ）成分の含有量が上記数値範囲より過大の場合は液晶配向性が低下し易く、過小の場合は溶剤耐性が低下することにより配向性が低下し易い。 The compounding ratio of the (A) component and the (B) component is preferably (A) component: (B) component = 5: 95 to 60:40 by mass ratio. When 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.
　本実施の形態の硬化膜形成組成物の好ましい例は、以下のとおりである。
［１］：（Ａ）成分と（Ｂ）成分の配合比が質量比で５：９５～６０：４０であり、（Ａ）成分と（Ｂ）成分との合計量の１００質量部に基づいて、０．０１質量部～１０質量部の（Ｃ）成分、溶剤を含有する硬化膜形成組成物。
［２］：（Ａ）成分と（Ｂ）成分の配合比が質量比で５：９５～６０：４０であり、（Ａ）成分と（Ｂ）成分との合計量の１００質量部に基づいて、０．０１質量部～１０質量部の（Ｃ）成分、（Ａ）成分と（Ｂ）成分との合計量の１００質量部に基づいて、５質量部～１００質量部の（Ｄ）成分、溶剤を含有する硬化膜形成組成物。 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.
　本実施の形態の硬化膜形成組成物を溶液として用いる場合の配合割合、調製方法等を以下に詳述する。
　本実施の形態の硬化膜形成組成物における固形分の割合は、各成分が均一に溶剤に溶解している限り、特に限定されるものではないが、１質量％～８０質量％であり、好ましくは３質量％～６０質量％であり、より好ましくは５質量％～４０質量％である。ここで、固形分とは、硬化膜形成組成物の全成分から溶剤を除いたものをいう。 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. Here, solid content means what remove | excluded the solvent from all the components of the cured film formation composition.
　本実施の形態の硬化膜形成組成物の調製方法は、特に限定されない。調製法としては、例えば、溶剤に溶解した（Ｂ）成分の溶液に（Ａ）成分および（Ｃ）成分を所定の割合で混合し、均一な溶液とする方法、或いは、この調製法の適当な段階において、必要に応じてその他添加剤をさらに添加して混合する方法が挙げられる。 The method for preparing the cured film forming composition of the present embodiment is not particularly limited. As 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.
　本実施の形態の硬化膜形成組成物の調製においては、溶剤中の重合反応によって得られる重合体または共重合体の溶液をそのまま使用することができる。この場合、例えば、（Ｂ）成分の溶液に前記と同様に（Ａ）成分および（Ｃ）成分を入れて均一な溶液とする。この際に、濃度調整を目的としてさらに溶剤を追加投入してもよい。このとき、（Ｂ）成分の生成過程で用いられる溶剤と、硬化膜形成組成物の濃度調整に用いられる溶剤とは同一であってもよく、また異なってもよい。 In preparing the cured film forming composition of the present embodiment, a polymer or copolymer solution obtained by a polymerization reaction in a solvent can be used as it is. In this case, for example, 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. At this time, a solvent may be further added for the purpose of adjusting the concentration. At this time, 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.
　また、調製された硬化膜形成組成物の溶液は、孔径が０．２μｍ程度のフィルタなどを用いて濾過した後、使用することが好ましい。 The prepared cured film-forming composition solution is preferably used after being filtered using a filter having a pore size of about 0.2 μm.
＜硬化膜、配向材および位相差材＞
　本実施の形態の硬化膜形成組成物の溶液を基板（例えば、シリコン／二酸化シリコン被覆基板、シリコンナイトライド基板、金属、例えば、アルミニウム、モリブデン、クロムなどが被覆された基板、ガラス基板、石英基板、ＩＴＯ基板等）やフィルム（例えば、トリアセチルセルロース（ＴＡＣ）フィルム、シクロオレフィンポリマーフィルム、ポリエチレンテレフタレートフィルム、アクリルフィルム等の樹脂フィルム）等の上に、バーコート、回転塗布、流し塗布、ロール塗布、スリット塗布、スリットに続いた回転塗布、インクジェット塗布、印刷などによって塗布して塗膜を形成し、その後、ホットプレートまたはオーブン等で加熱乾燥することにより、硬化膜を形成することができる。 <Hardened film, alignment material and retardation material>
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. , ITO substrate, etc.) and films (for example, triacetyl cellulose (TAC) film, cycloolefin polymer film, polyethylene terephthalate film, resin film such as acrylic film), etc., 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.
　加熱乾燥の条件としては、硬化膜から形成される配向材を構成する成分が、その上に塗布される重合性液晶溶液に溶出しない程度に、架橋反応（加熱硬化）が進行すればよく、例えば、温度６０℃～２００℃、時間０．４分間～６０分間の範囲の中から適宜選択された加熱温度および加熱時間が採用される。加熱温度および加熱時間は、好ましくは７０℃～１６０℃、０．５分間～１０分間である。 As the conditions for the heat drying, it is sufficient that the crosslinking reaction (heat curing) proceeds to such an extent that the component constituting the alignment material formed from the cured film does not elute into the polymerizable liquid crystal solution applied thereon. 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.
　本実施の形態の硬化膜形成組成物を用いて形成される硬化膜の膜厚は、例えば、０．０５μｍ～５μｍであり、使用する基板の段差や光学的、電気的性質を考慮し適宜選択することができる。 The film thickness of the cured film formed using the cured film forming composition of the present embodiment is, for example, 0.05 μm to 5 μm, and is appropriately selected in consideration of the level difference of the substrate to be used and optical and electrical properties. can do.
　このようにして形成された硬化膜は、偏光ＵＶ照射を行うことで配向材、すなわち、液晶等の液晶性を有する化合物を配向させる部材として機能させることができる。 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.
　偏光ＵＶの照射方法としては、通常１５０ｎｍ～４５０ｎｍの波長の紫外光～可視光が用いられ、室温または加熱した状態で、垂直または斜め方向から直線偏光を照射することによって行われる。 As the irradiation method of polarized UV, 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.
　本実施形態の硬化膜組成物から形成された配向材は耐溶剤性および耐熱性を有している。従って、この配向材上に、後述する重合性液晶溶液からなる位相差材料を塗布した後、液晶の相転移温度まで加熱することで位相差材料を液晶状態とし、配向材上で配向させ、その後配向状態となった位相差材料をそのまま硬化させることにより、光学異方性を有する層として位相差材を形成することができる。 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.
　位相差材料としては、例えば、重合性基を有する液晶モノマーおよびそれを含有する組成物（即ち重合性液晶溶液）等が用いられる。そして、配向材を形成する基板がフィルムである場合には、本実施の形態の位相差材を有するフィルムは、位相差フィルムとして有用である。このような位相差材を形成する位相差材料には、液晶状態とした際に配向材上で水平配向、コレステリック配向、垂直配向、ハイブリッド配向等の配向状態をとるものがあり、それぞれ必要とされる位相差に応じて使い分けることが出来る。 As 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. And when the board | 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.
　また、３Ｄディスプレイに用いられるパターン化位相差材を製造する場合には、本実施形態の硬化膜組成物から上記した方法で形成された硬化膜に、ラインアンドスペースパターンのマスクを介して所定の基準から、例えば、＋４５度の向きで偏光ＵＶ露光し、次いで、マスクを外してから－４５度の向きで偏光ＵＶを露光し、液晶の配向制御方向の異なる２種類の液晶配向領域が形成された配向材を得る。その後、重合性液晶溶液からなる上述の位相差材料を塗布した後、液晶の相転移温度まで加熱することで位相差材料を液晶状態とし、配向材上で配向させる。そして、配向状態となった位相差材料をそのまま硬化させ、位相差特性の異なる２種類の位相差領域がそれぞれ複数、規則的に配置された、パターン化位相差材を得ることができる。 Moreover, when manufacturing the patterned phase difference material used for 3D display, it is predetermined | prescribed via the mask of a line and space pattern to the cured film formed by the above-mentioned method from the cured film composition of this embodiment. For example, polarized UV exposure is performed in the +45 degree direction from the reference, and then the polarized UV light is exposed in the -45 degree direction after removing the mask, and two types of liquid crystal alignment regions having different liquid crystal alignment control directions are formed. To obtain an alignment material. Then, after apply | coating the above-mentioned phase difference material which consists of a polymeric liquid crystal solution, it heats to the phase transition temperature of a liquid crystal, makes a phase difference material a liquid crystal state, and aligns it on an orientation material. Then, the retardation material in an oriented state is cured as it is, and a patterned retardation material in which a plurality of two types of retardation regions having different retardation characteristics are regularly arranged can be obtained.
　また、上記のようにして形成された、本実施の形態の配向材を有する２枚の基板を用い、スペーサを介して両基板上の配向材が互いに向かい合うように張り合わせた後、それらの基板の間に液晶を注入して、液晶が配向した液晶表示素子とすることもできる。
　このように、本実施の形態の硬化膜形成組成物は、各種位相差材（位相差フィルム）や液晶表示素子等の製造に好適に用いることができる。 Further, after using the two substrates having the alignment material of the present embodiment formed as described above, 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.
Thus, 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.
　以下、実施例を挙げて、本実施の形態をさらに詳しく説明するが、本実施の形態は、これら実施例に限定されるものでない。 Hereinafter, the present embodiment will be described in more detail with reference to examples. However, the present embodiment is not limited to these examples.
［実施例で用いる略記号］
　以下の実施例で用いる略記号の意味は、次のとおりである。
＜（Ａ）成分：光配向性基およびヒドロキシ基を有する化合物＞
ＣＩＮ１：４－（６－ヒドロキシヘキシルオキシ）けい皮酸メチルエステル
ＣＩＮ２：４－［４－（６－ヒドロキシヘキシルオキシ）ベンゾイル］けい皮酸ターシャリーブチルエステル [Abbreviations used in Examples]
The meanings of the abbreviations used in the following examples are as follows.
<(A) component: Compound having photo-alignable group and hydroxy group>
CIN1: 4- (6-hydroxyhexyloxy) cinnamic acid methyl ester CIN2: 4- [4- (6-hydroxyhexyloxy) benzoyl] cinnamic acid tertiary butyl ester
＜（Ｂ）成分＞
ＦＲ－１０１：（株）鉛市製　低重合度６ナイロンの３０％メトキシメチル化した樹脂を２０ｗｔ％エタノール溶液に調製したもの
ＦＲ－１０３：（株）鉛市製　６ナイロン共重合ポリアミドの２０％メトキシメチル化した樹脂を２０ｗｔ％エタノール溶液に調製したもの
ＨＭＭ：日本サイテックインダストリーズ（株）製　サイメル３０３（ヘキサメトキシメチルメラミン）
ＥＭ－２２０：（株）鉛市製　低重合度６ナイロンの３０％メトキシメチル化した樹脂を２０ｗｔ％エタノール溶液に調製したもの <(B) component>
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. A methoxymethylated resin prepared in a 20 wt% ethanol solution HMM: Cymel 303 (Hexamethoxymethylmelamine) manufactured by Nihon Cytec Industries, Ltd.
EM-220: Made by Lead City Co., Ltd. Low polymerization degree 6 nylon 30% methoxymethylated resin prepared in 20 wt% ethanol solution
＜（Ｃ）成分：架橋触媒＞
ＰＴＳＡ：ｐ－トルエンスルホン酸・一水和物 <Component (C): Cross-linking catalyst>
PTSA: p-toluenesulfonic acid monohydrate
＜（Ｄ）成分＞
ＭＡＡ：メタクリル酸
ＭＭＡ：メチルメタクリレート
ＨＥＭＡ：２－ヒドロキシエチルメタクリレート
ＡＩＢＮ：α，α’－アゾビスイソブチロニトリル <(D) component>
MAA: methacrylic acid MMA: methyl methacrylate HEMA: 2-hydroxyethyl methacrylate AIBN: α, α'-azobisisobutyronitrile
＜溶剤＞
ＰＭ：プロピレングリコールモノメチルエーテル
ＥｔＯＨ：エタノール <Solvent>
PM: Propylene glycol monomethyl ether EtOH: Ethanol
　以下の合成例に従い得られたアクリル共重合体の数平均分子量及び重量平均分子量は、日本分光（株）製ＧＰＣ装置（Ｓｈｏｄｅｘ（登録商標）カラムＫＦ８０３ＬおよびＫＦ８０４Ｌ）を用い、溶出溶媒テトラヒドロフランを流量１ｍＬ／分でカラム中に（カラム温度４０℃）流して溶離させるという条件で測定した。尚、下記の数平均分子量（以下、Ｍｎと称す。）および重量平均分子量（以下、Ｍｗと称す。）は、ポリスチレン換算値にて表した。 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.). The following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) were expressed in terms of polystyrene.
（合成例１）ＣＩＮ２の合成
（合成例１－１）ＣＩＮ２の前駆体ＣＩＮ２－１の合成 Synthesis Example 1 Synthesis of CIN2 (Synthesis Example 1-1) Synthesis of CIN2 Precursor CIN2-1
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　１Ｌ四口フラスコに、４－ブロモ－４'－ヒドロキシベンゾフェノンを８０.０ｇ、Ｎ，Ｎ－ジメチルアセトアミド（ＤＭＡｃ）を５００ｍＬ、アクリル酸ｔｅｒｔ－ブチルを５５．４ｇ、トリブチルアミン（Ｂｕ３Ｎ）を１６０．２ｇ、酢酸パラジウム（Ｐｄ（ＯＡｃ）２）を１．２９ｇ、トリ（ｏ－トリル）ホスフィン（Ｐ－（ｏ－Ｔｏｌ）３）を３．５０ｇ加えて、１００℃に加熱しながら撹拌した。反応終了後、２Ｌの酢酸エチルに反応系を注ぎ、１Ｎ－塩酸水溶液、飽和食塩水を用いて抽出を行った。抽出した有機層に無水硫酸マグネシウムを加えて脱水乾燥し、無水硫酸マグネシウムを濾過した。得られた濾液をロータリーエバポレーターを用いて溶媒留去し、１０９．４ｇの目的物ＣＩＮ２－１（赤褐色粘体）を得た。得られたＣＩＮ２－１は精製せずに次の反応に用いた。 In a 1 L four-necked flask, 80.0 g of 4-bromo-4′-hydroxybenzophenone, 500 mL of N, N-dimethylacetamide (DMAc), 55.4 g of tert-butyl acrylate, tributylamine (Bu 3 N) 160.2 g, 1.29 g palladium acetate (Pd (OAc) 2), tri (o-tolyl) phosphine (P- (o-Tol) 3 ) was added 3.50g was stirred while heating to 100 ° C. . After completion of the reaction, the reaction system was poured into 2 L of ethyl acetate and extracted with 1N-hydrochloric acid aqueous solution and saturated brine. To the extracted organic layer, anhydrous magnesium sulfate was added, dehydrated and dried, and anhydrous magnesium sulfate was filtered. The obtained filtrate was evaporated using a rotary evaporator to obtain 109.4 g of the desired product CIN2-1 (red brown viscous body). The obtained CIN2-1 was used in the next reaction without purification.
（合成例１－２）ＣＩＮ２の合成
Figure JPOXMLDOC01-appb-C000015
 (Synthesis Example 1-2) Synthesis of CIN2
Figure JPOXMLDOC01-appb-C000015
　２Ｌ四口フラスコに、ＣＩＮ２－１を９３．４ｇ、Ｎ，Ｎ－ジメチルホルムアミド（ＤＭＦ）を１Ｌ、６－クロロ－１－ヘキサノールを３９．３ｇ、炭酸カリウム（Ｋ２ＣＯ３）を１１９．４ｇ、ヨウ化カリウム（ＫＩ）を４．８ｇ加えて、１００℃に加熱しながら撹拌した。反応終了後、５Ｌの水に反応系を注ぎ、１Ｎ－塩酸水溶液で中和を行い、酢酸エチルを用いて抽出を行った。抽出した有機層に無水硫酸マグネシウムを加えて脱水乾燥し、無水硫酸マグネシウムを濾過した。得られた濾液をロータリーエバポレーターを用いて溶媒留去を行った。残渣をイソプロパノール／ヘキサン＝１／１０を用いて再結晶を行い、ＣＩＮ２（黄土色固体）を１１３．８ｇ得た。目的物の１Ｈ－ＮＭＲで測定した結果を以下に示す。この結果から、得られた固体が、目的のＣＩＮ２であることを確認した。
1H NMR (400 MHz,［D6］-DMSO):δ7.86-7.88 (d,2H), 7.73-7.75 (d,2H), 7.69-7.71 (d,2H), 7.62-7.66 (d,1H), 7.08-7.10 (d,2H), 6.65-6.69 (d,1H), 4.35-4.37 (t,1H), 4.06-4.09 (t,2H), 3.37-3.42 (q,2H), 1.73-1.77 (m,2H), 1.50 (s,9H), 1.37-1.46 (m,6H) In a 2 L four-necked flask, 93.4 g of CIN2-1, 1 L of N, N-dimethylformamide (DMF), 39.3 g of 6-chloro-1-hexanol, and 119.4 g of potassium carbonate (K 2 CO 3 ) Then, 4.8 g of potassium iodide (KI) was added and stirred while heating to 100 ° C. After completion of the reaction, the reaction system was poured into 5 L of water, neutralized with 1N hydrochloric acid aqueous solution, and extracted with ethyl acetate. To the extracted organic layer, anhydrous magnesium sulfate was added, dehydrated and dried, and anhydrous magnesium sulfate was filtered. The obtained filtrate was evaporated using a rotary evaporator. The residue was recrystallized using isopropanol / hexane = 1/10 to obtain 113.8 g of CIN2 (ocher solid). The results measured by 1 H-NMR of desired product are shown below. From this result, it was confirmed that the obtained solid was the target CIN2.
1 H NMR (400 MHz, [ D 6] -DMSO): δ7.86-7.88 (d, 2H), 7.73-7.75 (d, 2H), 7.69-7.71 (d, 2H), 7.62-7.66 (d, 1H), 7.08-7.10 (d, 2H), 6.65-6.69 (d, 1H), 4.35-4.37 (t, 1H), 4.06-4.09 (t, 2H), 3.37-3.42 (q, 2H), 1.73- 1.77 (m, 2H), 1.50 (s, 9H), 1.37-1.46 (m, 6H)
＜合成例２＞
　ＭＡＡ　２．５ｇ、ＭＭＡ　９．２ｇ、ＨＥＭＡ　５．０ｇ、重合触媒としてＡＩＢＮ　０．２ｇをＰＭ　５０．７ｇに溶解し、７０℃にて２０時間反応させることによりアクリル共重合体溶液（固形分濃度２５質量％）（Ｐ１）を得た。得られたアクリル共重合体のＭｎは１９，６００、Ｍｗは４５，２００であった。 <Synthesis Example 2>
MAA 2.5 g, MMA 9.2 g, HEMA 5.0 g, 0.2 g of AIBN as a polymerization catalyst were dissolved in 50.7 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 19,600 and Mw was 45,200.
＜実施例１～６、比較例１、２＞
　表１、２に示す組成にて実施例１～６、および比較例１～４の各硬化膜形成組成物を調製し、それぞれについて、密着性、配向感度、パターン形成性、透過率の評価を行った。 <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.
Figure JPOXMLDOC01-appb-T000016
Figure JPOXMLDOC01-appb-T000016
［配向感度の評価］
　実施例および比較例の各硬化膜形成組成物を、無アルカリガラス、ＴＡＣフィルム、アクリルフィルム上に、バーコーターを用いてＷｅｔ膜厚４μｍにて塗布した後、温度１００℃で６０秒間、熱循環式オーブン中で加熱乾燥を行い、硬化膜を形成した。この硬化膜に３１３ｎｍの直線偏光を種々の露光量（最大１００ｍＪ／ｃｍ２）で垂直に照射し、配向材を形成した。基板上の配向材の上に、メルク（株）製の水平配向用重合性液晶溶液を、バーコーターを用いてＷｅｔ膜厚６μｍにて塗布し、次いで、６５℃で６０秒間ホットプレート上においてプリベークを行い、膜厚１．０μｍの塗膜を形成した。この基板上の塗膜を３００ｍＪ／ｃｍ２で露光し、位相差材を作製した。作製した基板上の位相差材を一対の偏光板で挟み込み、位相差材における位相差特性の発現状況を観察し、配向材が液晶配向性を示すのに必要な偏光ＵＶの露光量を配向感度とした。 [Evaluation of orientation sensitivity]
The cured film forming compositions of Examples and Comparative Examples were coated on a non-alkali glass, a TAC film, and an acrylic film with a wet film thickness of 4 μm using a bar coater, and then thermally circulated at a temperature of 100 ° C. for 60 seconds. Heat drying was carried out in a type oven to form a cured film. This cured film was irradiated vertically with 313 nm linearly polarized light at various exposure doses (maximum 100 mJ / cm 2 ) to form an alignment material. On the alignment material on the substrate, a polymerizable liquid crystal solution for horizontal alignment manufactured by Merck Co., Ltd. was applied at a wet film thickness of 6 μm using a bar coater, and then pre-baked on a hot plate at 65 ° C. for 60 seconds. And a coating film having a thickness of 1.0 μm was formed. The coating film on this substrate was exposed at 300 mJ / cm 2 to produce a retardation material. The retardation material on the prepared substrate is sandwiched between a pair of polarizing plates, the state of retardation property development in the retardation material is observed, and the exposure amount of polarized UV necessary for the alignment material to exhibit liquid crystal alignment is determined. It was.
［密着性の評価］
　実施例および比較例の各硬化膜形成組成物を、無アルカリガラス、ＴＡＣフィルム、アクリルフィルム上に、バーコーターを用いてＷｅｔ膜厚４μｍにて塗布した後、温度１００℃で６０秒間、熱循環式オーブン中で加熱乾燥を行い、硬化膜を形成した。この硬化膜に３１３ｎｍの直線偏光を垂直に２０ｍＪ／ｃｍ２照射した。露光後の基板上にメルク（株）製の水平配向用重合性液晶溶液を、スピンコータを用いて塗布し、次いで、６５℃で６０秒間ホットプレート上においてプリベークを行い、膜厚１．０μｍの塗膜を形成した。このフィルムを３００ｍＪ／ｃｍ２で露光し、位相差材を作製した。得られた基板上の位相差材にカッターナイフを用いてクロスカット（１ｍｍ×１ｍｍ×１００マス）を入れ、その後、粘着テープ（ニチバン（株）製　セロテープ（登録商標））を貼り付け、次いで、その粘着テープを剥がした時に基板上の膜が剥がれず残っているマス目の個数をカウントし、［残っているマス目数／１００］として評価した。膜が剥がれず残っているマス目が９０個以上残っているものを密着性が良好と判断した。 [Evaluation of adhesion]
The cured film forming compositions of Examples and Comparative Examples were coated on a non-alkali glass, a TAC film, and an acrylic film with a wet film thickness of 4 μm using a bar coater, and then thermally circulated at a temperature of 100 ° C. for 60 seconds. Heat drying was carried out in a type oven to form a cured film. This cured film was irradiated with 20 mJ / cm 2 of 313 nm linearly polarized light vertically. On the exposed substrate, a polymerizable liquid crystal solution for horizontal alignment manufactured by Merck Co., Ltd. was applied using a spin coater, and then pre-baked on a hot plate at 65 ° C. for 60 seconds. 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.
［評価の結果］
　以上の評価を行った結果を、次の表２に示す。 [Evaluation results]
The results of the above evaluation are shown in Table 2 below.
Figure JPOXMLDOC01-appb-T000017
Figure JPOXMLDOC01-appb-T000017
　実施例１～６は、使用した基板の種類によらず、いずれも少ない露光量で液晶配向性を示し、優れた光反応効率と耐溶剤性とを備えた硬化膜（配向材）を得ることができた。
さらに得られた硬化膜は、基板の種類によらず、基板に対する高い密着性を示した。 In 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.
　一方、比較例１～４は、１００ｍＪ／ｃｍ２の直線偏光を照射しても配向せず、密着性の評価に至らなかった。 On the other hand, 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.
　本発明による硬化膜形成組成物は、液晶表示素子の液晶配向膜や、液晶表示素子に内部や外部に設けられる光学異方性フィルムを形成するための配向材として非常に有用であり、特に、３Ｄディスプレイのパターン化位相差材の形成材料として好適である。さらに、薄膜トランジスタ（ＴＦＴ）型液晶表示素子や有機ＥＬ素子などの各種ディスプレイにおける保護膜、平坦化膜および絶縁膜などの硬化膜を形成する材料、特に、ＴＦＴ型液晶素子の層間絶縁膜、カラーフィルタの保護膜または有機ＥＬ素子の絶縁膜などを形成する材料としても好適である。 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.

Claims (10)

  1. （Ａ）光配向性基と、ヒドロキシ基、カルボキシル基、アミノ基およびアルコキシシリル基から選ばれるいずれか１つの置換基とを有する化合物、
    （Ｂ）アミド基の窒素原子のうちの少なくとも一部がアルコキシメチル化またはアルキルチオメチル化されたポリアミド、及び
    （Ｃ）架橋触媒、を含有することを特徴とする硬化膜形成組成物。     (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,
    (B) A cured film-forming composition comprising a polyamide in which at least a part of nitrogen atoms of an amide group is alkoxymethylated or alkylthiomethylated, and (C) a crosslinking catalyst.
  2. （Ａ）成分の光配向性基が、光二量化または光異性化する構造の官能基であることを特徴とする、請求項１に記載の硬化膜形成組成物。 The cured film forming composition according to claim 1, wherein the photo-alignment group of the component (A) is a functional group having a structure that undergoes photodimerization or photoisomerization.
  3. （Ａ）成分の光配向性基が、シンナモイル基であることを特徴とする、請求項１または請求項２に記載の硬化膜形成組成物。 The cured film forming composition according to claim 1 or 2, wherein the photo-alignable group of the component (A) is a cinnamoyl group.
  4. （Ａ）成分の光配向性基が、アゾベンゼン構造の基であることを特徴とする、請求項１または請求項２に記載の硬化膜形成組成物。 The cured film forming composition according to claim 1 or 2, wherein the photo-alignment group of the component (A) is a group having an azobenzene structure.
  5. （Ｂ）成分のポリアミドが、ナイロン－６、ナイロン－１１、ナイロン－１２、ナイロン－６６、ナイロン－６１０、ナイロン－６１２、ナイロン－１０１０、ナイロン－１２１２、ナイロン－６６／６１０、ナイロン６／６６、ナイロン６／６９、ナイロン６－Ｉ／６－Ｔ、及びこれらの２種以上の組合せからなる群から選択されるポリアミドをＮ－アルコキシメチル化またはＮ－アルキルチオメチル化したものである、請求項１乃至請求項４のいずれか１項に記載の硬化膜形成組成物。 The polyamide of component (B) is nylon-6, nylon-11, nylon-12, nylon-66, nylon-610, nylon-612, nylon-1010, nylon-1212, nylon-66 / 610, nylon 6/66. N-alkoxymethylated or N-alkylthiomethylated polyamide selected from the group consisting of nylon 6/69, nylon 6-I / 6-T, and combinations of two or more thereof. The cured film forming composition according to any one of claims 1 to 4.
  6. （Ｂ）成分のポリアミドが、ポリアミドをＮ－アルコキシメチル化したものである、求項１乃至請求項５のいずれか１項に記載の硬化膜形成組成物。 The cured film forming composition according to any one of claims 1 to 5, wherein the polyamide as component (B) is N-alkoxymethylated polyamide.
  7. （Ｄ）炭素原子数２乃至５のヒドロキシアルキルエステル基、アルコキシシリル基、Ｎ－アルコキシメチル基、カルボキシル基及びフェノール性ヒドロキシ基のうちの少なくとも一つを有するアクリル重合体をさらに含有する、請求項１乃至請求項６のいずれか１項に記載の硬化膜形成組成物。 (D) It further contains 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. The cured film forming composition according to any one of claims 1 to 6.
  8. （Ｂ）成分のポリアミドが、１，０００～１００，０００の重量平均分子量を有することを特徴とする、請求項１乃至請求項７のいずれか１項に記載の硬化膜形成組成物。 The cured film forming composition according to any one of claims 1 to 7, wherein the polyamide as component (B) has a weight average molecular weight of 1,000 to 100,000.
  9. 請求項１乃至請求項８のいずれか１項に記載の硬化膜形成組成物を用いて得られることを特徴とする配向材。 An alignment material obtained by using the cured film-forming composition according to any one of claims 1 to 8.
  10. 請求項１乃至請求項８のいずれか１項に記載の硬化膜形成組成物から得られる硬化膜を使用して形成されることを特徴とする位相差材。 A phase difference material formed using a cured film obtained from the cured film forming composition according to claim 1.
PCT/JP2014/072305 2013-08-27 2014-08-26 Cured film-forming composition, alignment material, and phase difference material WO2015030000A1 (en)

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