WO2011010635A1 - 光配向性を有する熱硬化膜形成組成物 - Google Patents
光配向性を有する熱硬化膜形成組成物 Download PDFInfo
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- WO2011010635A1 WO2011010635A1 PCT/JP2010/062170 JP2010062170W WO2011010635A1 WO 2011010635 A1 WO2011010635 A1 WO 2011010635A1 JP 2010062170 W JP2010062170 W JP 2010062170W WO 2011010635 A1 WO2011010635 A1 WO 2011010635A1
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- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/062—Copolymers with monomers not covered by C08L33/06
- C08L33/066—Copolymers with monomers not covered by C08L33/06 containing -OH groups
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
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- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
- B32B2457/202—LCD, i.e. liquid crystal displays
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
- C08F220/303—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one or more carboxylic moieties in the chain
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
- C09K2323/02—Alignment layer characterised by chemical composition
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
Definitions
- the present invention relates to a thermosetting film-forming composition having photo-alignment properties and a cured film formed therefrom. More specifically, the present invention relates to a thermosetting film-forming composition capable of forming a cured film having high transparency, liquid crystal alignment ability, high solvent resistance and heat resistance, and the cured film.
- the thermosetting film-forming composition having photo-alignment property of the present invention is particularly suitable for a color filter overcoat agent having a polymerizable liquid crystal alignment function for forming a built-in retardation layer in a liquid crystal display.
- a protective film is provided to prevent the element surface from being exposed to a solvent or heat during the manufacturing process.
- This protective film is required not only to have high adhesion to the substrate to be protected and high solvent resistance, but also to have excellent performance such as heat resistance.
- a protective film is used as a protective film for a color filter used in a color liquid crystal display device or a solid-state imaging device, it is highly transparent to maintain the transmittance of light transmitted through the color filter. It is required that the film has a property.
- phase difference material a phase difference material
- a polymerizable liquid crystal solution is applied and aligned, and then light is applied.
- Cured materials are commonly used.
- the lower layer film needs to be a material having orientation after rubbing treatment or polarized UV irradiation. Therefore, after forming a liquid crystal alignment layer on the overcoat of the color filter, a retardation material is formed (see FIG. 1A). If a film (see FIG. 1B) having both the liquid crystal alignment layer and the color filter overcoat can be formed, significant advantages such as cost reduction and a reduction in the number of processes can be obtained. A material that also has a coat is strongly desired.
- acrylic resin is used for the overcoat of the color filter.
- glycol solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate
- ester solvents such as ethyl lactate and butyl lactate
- ketone solvents such as cyclohexanone and methyl amyl ketone
- acrylic resins have been heat-cured or photo-cured to improve heat resistance and solvent resistance (Patent Documents 1 and 2).
- Patent Documents 1 and 2 thermosetting or photo-curing acrylic resins have appropriate transparency and solvent resistance, sufficient orientation can be obtained even when an overcoat made of this type of acrylic resin is rubbed or irradiated with polarized UV light. could not show.
- the liquid crystal alignment layer described in Patent Document 3 has a problem of low transparency when used as an overcoat material for a color filter.
- Polyimides and polyamic acids are soluble in solvents such as N-methylpyrrolidone and ⁇ -butyrolactone, but have low solubility in glycol solvents, ester solvents, and ketone solvents, so that such solvents can be used. It is difficult to apply to the coat production line.
- the liquid crystal alignment layer is irradiated with a normal polarized UV exposure amount (for example, 100 mJ / cm 2 ), the photodimerization reaction rate is low and it is not sufficiently crosslinked. The solvent resistance and heat resistance are low. Therefore, when a polymerizable liquid crystal is applied to form a phase difference material layer on the liquid crystal alignment layer, the liquid crystal alignment layer is dissolved and cannot exhibit sufficient alignment. In addition, when the exposure dose is increased to 1 J / cm 2 or more in order to increase the photodimerization reaction rate, the orientation of the polymerizable liquid crystal is improved, but the exposure time becomes very long, so it cannot be said as a practical method. .
- a normal polarized UV exposure amount for example, 100 mJ / cm 2
- the photodimerization reaction rate is low and it is not sufficiently crosslinked.
- the solvent resistance and heat resistance are low. Therefore, when a polymerizable liquid crystal is applied to form a phase difference material layer on the liquid crystal alignment layer, the liquid crystal alignment
- the material used for the conventional liquid crystal alignment layer was a material having only a photodimerization site as a cross-linking site, the number of cross-linking sites is small as a whole, and the liquid crystal alignment layer produced has sufficient heat resistance. It will not be. For this reason, there is a concern that the liquid crystal alignment layer contracts greatly during the manufacturing process of the display element performed at 200 ° C. or higher after the retardation material is formed.
- An object of the present invention is to provide a material that exhibits transparency and can be dissolved in a glycol solvent, a ketone solvent, or a lactic acid ester solvent that can be applied in the production of a color filter overcoat when a cured film is formed.
- the present inventors have found the present invention. That is, as a first aspect, the component (A) is an acrylic copolymer having a photodimerization site and a thermal crosslinking site, and the component (B) is an alkyl ester group having 2 to 5 carbon atoms and 2 to 2 carbon atoms.
- 5 is a thermosetting resin having photo-alignment properties, comprising an acrylic polymer having at least one of 5 hydroxyalkyl ester groups and at least one of a carboxyl group and a phenolic hydroxy group, and a crosslinking agent as component (C).
- the present invention relates to a film-forming composition.
- the component (A) has a photo-alignment property according to the first aspect, which is an acrylic copolymer obtained by a polymerization reaction of a monomer containing a monomer having a photodimerization site and a monomer having a thermal crosslinking site.
- the present invention relates to a thermosetting film forming composition.
- a 3rd viewpoint it is related with the thermosetting film formation composition which has the photo-alignment property as described in the 1st viewpoint or the 2nd viewpoint whose photodimerization site
- thermosetting film formation composition which has the photo-alignment property as described in any one of the 1st viewpoint thru
- the component (B) has a carboxyl group and at least one of a monomer having an alkyl ester group having 2 to 5 carbon atoms and a monomer having a hydroxyalkyl ester group having 2 to 5 carbon atoms.
- thermosetting film having a photo-alignment property which is an acrylic copolymer obtained by a polymerization reaction with at least one of a monomer and a monomer having a phenolic hydroxy group. Relates to the forming composition.
- thermosetting film-forming composition having photoalignment property according to any one of the first to fifth aspects wherein the crosslinking agent of component (C) is a crosslinking agent having a methylol group or an alkoxymethylol group.
- the present invention further relates to a thermosetting film-forming composition having a photo-alignment property according to any one of the first to sixth aspects, further containing an acid or a thermal acid generator as a component (D).
- the present invention further relates to a thermosetting film-forming composition having a photo-alignment property according to any one of the first aspect to the seventh aspect, which contains a sensitizer as the component (E).
- any one of the first aspect to the eighth aspect containing 1 to 40 parts by mass of the component (C) based on 100 parts by mass of the total amount of the component (A) and the component (B). It is related with the thermosetting film forming composition which has the photo-alignment property of one term.
- any of the seventh to ninth aspects containing 0.01 to 5 parts by mass of component (D) based on 100 parts by mass of the total amount of component (A) and component (B) as the tenth aspect It relates to a thermosetting film-forming composition having a photo-alignment property according to claim 1.
- any one of the eighth to tenth aspects containing 0.1 to 20 parts by mass of the (E) component based on 100 parts by mass of the total amount of the component (A) and the component (C). It relates to a thermosetting film-forming composition having a photo-alignment property according to claim 1.
- thermosetting film formation composition which has the photo-alignment property as described in any one of a 1st viewpoint thru
- an optical device comprising a liquid crystal alignment layer formed from the thermosetting film-forming composition having the photoalignment property according to any one of the first to eleventh aspects together with a retardation layer thereon About.
- thermosetting film forming composition having photo-alignment property of the present invention can form a cured film having liquid crystal alignment ability (photo-alignment property) by light irradiation in addition to high transparency, high solvent resistance, and high heat resistance. It can be used as a material for forming a photo-alignment liquid crystal alignment film and an overcoat.
- a “polymerizable liquid crystal alignment layer” that combines the characteristics of both the layer that aligns the polymerizable liquid crystal and the overcoat layer of the color filter in order to form a retardation material in the display cell. Therefore, the manufacturing process can be simplified and the cost can be reduced by reducing the number of processes.
- thermosetting film-forming composition having photo-alignment property of the present invention is soluble in glycol solvents, ketone solvents, and lactic acid ester solvents, an overcoat production line for color filters that mainly uses these solvents. Can be suitably used.
- a liquid crystal cell in which a color filter (CF) overcoat having an orientation is formed using the liquid crystal cell (a) having a liquid crystal orientation film formed by a conventional technique and the thermosetting film-forming composition having a photo-alignment property of the present invention. It is a model figure shown by contrasting with (b).
- the present invention is characterized in that in addition to the above-described transparency, solvent resistance, and heat resistance, the performance of liquid crystal alignment ability (photo-alignment) by light irradiation is improved. That is, the present invention relates to an acrylic copolymer having a photodimerization site and a thermal crosslinking site as the component (A), an alkyl ester group having 2 to 5 carbon atoms and a hydroxy group having 2 to 5 carbon atoms as the component (B).
- thermosetting film having photo-alignment properties comprising an acrylic polymer having at least one of an alkyl ester group and at least one of a carboxyl group and a phenolic hydroxy group, and a crosslinking agent as component (C) Relates to the forming composition.
- photo-alignment that can also contain an acid or thermal acid generator as the component (D) and a sensitizer as the component (E).
- the present invention relates to a thermosetting film-forming composition having properties.
- the thermosetting film having photo-alignment refers to a film cured by heating in which optical anisotropy is induced by irradiating linearly polarized light.
- the component (A) is an acrylic copolymer having a photodimerization site and a thermal crosslinking site.
- the acrylic copolymer a copolymer obtained by polymerizing a monomer having an unsaturated double bond such as acrylic acid ester, methacrylic acid ester or styrene can be applied.
- the acrylic copolymer (A) having a photodimerization site and a thermal crosslinking site (hereinafter also referred to as a specific copolymer) may be an acrylic copolymer having such a structure, and constitutes an acrylic copolymer. There are no particular restrictions on the main chain skeleton and side chain type of the polymer.
- the photodimerization site is a site that forms a dimer by light irradiation, and specific examples thereof include a structure having a cinnamoyl group, a chalcone group, a coumarin group, an anthracene group, and the like. Of these, a structure having a cinnamoyl group exhibiting high transparency in the visible light region and photodimerization reactivity is preferable.
- a particularly preferred partial structure of the cinnamoyl group is represented by the following formula [A1] or [A2]. (In the formula [A1], X 1 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group or a biphenyl group.
- X 2 represents a hydrogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, or a cyclohexyl group.
- the alkyl group having 1 to 18 carbon atoms, the phenyl group, the biphenyl group, and the cyclohexyl group may be bonded via a covalent bond, an ether bond, an ester bond, an amide bond, or a urea bond.
- R 1 , R 2 , R 3 , and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a trifluoromethyl group, or a cyano group. Represents. )
- the thermal crosslinking site is a site that is bonded to the crosslinking agent by heating, and specific examples thereof include a hydroxy group, a carboxyl group, and a glycidyl group.
- the specific copolymer of component (A) 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 preferably it is. If the weight average molecular weight is over 200,000, the solubility in the solvent may be reduced and the handling property may be lowered. 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 weight average molecular weight is a value obtained by using gel as a standard sample by gel permeation chromatography (GPC).
- Examples of the monomer having a photodimerization site include monomers having a cinnamoyl group, a chalcone group, a coumarin group, or an anthracene group.
- a monomer having a cinnamoyl group having good transparency in the visible light region and good photodimerization reactivity is particularly preferable.
- a monomer having a partial structure of a cinnamoyl group represented by the above formula [A1] or [A2] is more preferable. Specific examples of such a monomer are shown in the following formula [A3] or [A4].
- X 1 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group or a biphenyl group.
- the phenyl group and the biphenyl group are each a halogen atom or a cyano group.
- X 2 represents a hydrogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, or a cyclohexyl group, wherein 1 to 18 carbon atoms are substituted.
- the alkyl group, phenyl group, biphenyl group and cyclohexyl group may be bonded via a covalent bond, an ether bond, an ester bond, an amide bond or a urea bond, and X 3 and X 5 are each independently a single bond or a carbon atom.
- X 4 and X 6 each represent an alkylene group, an aromatic ring group, or an aliphatic ring group represented by Formula 1 to 20.
- R 1 , R 2 , R 3 , and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a trifluoromethyl group, or a cyano group. Represents. )
- the alkylene group having 1 to 20 carbon atoms may be branched or linear.
- Specific examples of the polymerizable group include acryloyl group, methacryloyl group, styrene group, maleimide group, acrylamide group, and methacrylamide group.
- Examples of the monomer having a thermal crosslinking site include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2,3 -Dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, caprolactone 2- (acryloyloxy) ethyl ester, caprolactone 2- (methacryloyloxy) ethyl ester, poly (ethylene glycol) ethyl ether acrylate, Poly (ethylene glycol) ethyl ether methacrylate, 5-acryloyl Monomers having a hydroxy group such as cis-6-hydroxynorbornene-2-carboxyl-6-lactone, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxy
- a specific functional group copolymerizable with the monomer is added.
- Monomers that do not have can be used in combination.
- Such 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, glycidyl acrylate, 2,2,2-trifluoroethyl acrylate.
- methacrylic acid ester compound examples include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate.
- maleimide compound examples include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.
- styrene compound examples include styrene, methyl styrene, chlorostyrene, and bromostyrene.
- vinyl compound examples include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl carbazole, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo [4.1.0] heptane, 1,2-epoxy-5-hexene. And 1,7-octadiene monoepoxide.
- the amount of each monomer used to obtain the specific copolymer is a monomer having a photodimerization site of 25 to 90 mol%, a monomer having a thermal crosslinking site of 10 to 75 mol%, based on the total amount of all monomers. 0 to 65 mol% of a monomer having no specific functional group is preferable.
- the content of the monomer having a photodimerization site is less than 25 mol%, it is difficult to impart high-sensitivity and good liquid crystal alignment.
- the content of the monomer having a thermal crosslinking site is less than 10 mol%, it is difficult to impart sufficient heat resistance, and it is difficult to maintain high sensitivity and good liquid crystal alignment.
- the method for obtaining the specific copolymer used in the present invention is not particularly limited.
- a solvent in which a monomer having a specific functional group, a monomer not having the specific functional group if desired, and a polymerization initiator coexist It can be obtained by a polymerization reaction at a temperature of 50 to 110 ° C.
- the solvent used will not be specifically limited if it dissolves the monomer which has a specific functional group, the monomer which does not have the specific functional group used depending on necessity, a polymerization initiator, etc. Specific examples are described in ⁇ Solvent> described later.
- the specific copolymer obtained by the above method is usually in a solution state dissolved in a solvent.
- the solution of the specific copolymer obtained by the above method is poured into diethyl ether or water being stirred for reprecipitation, and after filtering and washing the generated precipitate, under normal pressure or reduced pressure, It can be dried at room temperature or heat to obtain a powder of the specific copolymer.
- the polymerization initiator and unreacted monomer coexisting with the specific copolymer can be removed, and as a result, a purified powder of the specific copolymer 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 specific copolymer 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 specific copolymer of component (A) may be a mixture of a plurality of types of specific copolymers.
- Component (B) is an acrylic having at least one of an alkyl ester group having 2 to 5 carbon atoms and a hydroxyalkyl ester group having 2 to 5 carbon atoms, and at least one of a carboxyl group and a phenolic hydroxy group. It is a polymer.
- the acrylic polymer a polymer obtained by polymerizing a monomer having an unsaturated double bond such as acrylic acid ester, methacrylic acid ester or styrene can be applied.
- Acrylic polymer having at least one of an alkyl ester group having 2 to 5 carbon atoms and a hydroxyalkyl ester group having 2 to 5 carbon atoms and at least one of a carboxyl group and a phenolic hydroxy group. May be any acrylic polymer having such a structure, and is not particularly limited with respect to the main chain skeleton and side chain type of the polymer constituting the acrylic polymer.
- a preferred structural unit is represented by the following formula [B1].
- a structural unit having at least one of a carboxyl group and a phenolic hydroxy group As a structural unit having at least one of a carboxyl group and a phenolic hydroxy group, a preferred structural unit is represented by the following formula [B2]. (In the formulas [B1] and [B2], R 5 and R 6 each independently represent a hydrogen atom or a methyl group, and Y 1 represents an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl having 1 to 3 carbon atoms. And Y 2 represents a carboxyl group or a phenolic hydroxy group.)
- the acrylic polymer as the component (B) 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 weight average molecular weight is a value obtained by using gel as a standard sample by gel permeation chromatography (GPC).
- the method for synthesizing the acrylic polymer of the component (B) includes a monomer having at least one of an alkyl ester group having 2 to 5 carbon atoms and a hydroxyalkyl ester group having 1 to 4 carbon atoms (hereinafter referred to as “a”).
- B1 monomer and a monomer having at least one of a carboxyl group and a phenolic hydroxy group (hereinafter referred to as b2 monomer) are convenient.
- Examples of the monomer having an alkyl ester group having 2 to 5 carbon atoms include methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, propyl methacrylate, propyl acrylate, isopropyl methacrylate, isopropyl acrylate, butyl methacrylate, butyl acrylate, and isobutyl methacrylate. , Isobutyl acrylate, t-butyl methacrylate, and t-butyl acrylate.
- 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, and 2-hydroxypropyl 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 such monomers include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds and vinyl compounds.
- the specific example of the said monomer is not limited, it is monomers other than b1 monomer and b2 monomer which can be used for a specific copolymer.
- the amount of b1 monomer and b2 monomer used to obtain the acrylic polymer of component (B) is 2 to 2 based on the total amount of all monomers used to obtain the acrylic polymer of component (B). It is preferably 95 mol% and the b2 monomer content is 5 to 98 mol%.
- the b1 monomer is preferably 60 to 95 mol% and the b2 monomer is preferably 5 to 40 mol%.
- the b1 monomer is preferably 2 to 80 mol% and the b2 monomer is preferably 20 to 98 mol%. If the b2 monomer is too small, the liquid crystal orientation tends to be insufficient, and if it is too large, the compatibility with the acrylic copolymer of the component (A) tends to decrease.
- the method for obtaining the acrylic polymer of component (B) used in the present invention is not particularly limited.
- the solvent used is not particularly limited as long as it dissolves the b1 monomer and the b2 monomer, the monomer other than the b1 monomer and the b2 monomer used as desired, a polymerization initiator, and the like. Specific examples are described in ⁇ Solvent> described later.
- the (B) 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 (B) obtained by the above method is poured into diethyl ether or water being stirred for reprecipitation, and after 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 (B).
- the polymerization initiator and unreacted monomer coexisting with the acrylic polymer of component (B) can be removed, and as a result, a purified acrylic polymer powder of component (B) 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 (B) 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 (B) component acrylic polymer may be a mixture of a plurality of types of (B) component acrylic polymers.
- (C) component of this invention is a crosslinking agent couple
- the crosslinking agent include compounds such as an epoxy compound, a methylol compound, and an isocyanate compound, and a methylol compound is preferable.
- methylol compound examples include compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine.
- alkoxymethylated glycoluril include, for example, 1,3,4,6-tetrakis (methoxymethyl) glycoluril, 1,3,4,6-tetrakis (butoxymethyl) glycoluril, 1,3,4 , 6-tetrakis (hydroxymethyl) glycoluril, 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea, 1,1,3,3-tetrakis (methoxymethyl) Examples include urea, 1,3-bis (hydroxymethyl) -4,5-dihydroxy-2-imidazolinone, and 1,3-bis (methoxymethyl) -4,5-dimethoxy-2-imidazolinone.
- glycoluril compounds (trade names: Cymel [registered trademark] 1170, Powderlink [registered trademark] 1174) manufactured by Nippon Cytec Industries Co., Ltd. (former Mitsui Cytec Co., Ltd.), methylated urea resins ( Trade name: UFR [registered trademark] 65), butylated urea resin (trade names: UFR [registered trademark] 300, U-VAN10S60, U-VAN10R, U-VAN11HV), DIC Corporation (former Dainippon Ink and Chemicals) And Urea / formaldehyde resin (high condensation type, trade name: Beccamin [registered trademark] J-300S, P-955, N).
- alkoxymethylated benzoguanamine examples include tetramethoxymethyl benzoguanamine.
- Commercially available products are made by Nippon Cytec Industries Co., Ltd. (former Mitsui Cytec Co., Ltd.) (trade name: Cymel [registered trademark] 1123), manufactured by Sanwa Chemical Co., Ltd. (trade name: Nicalak [registered trademark] BX-4000). BX-37, BL-60, BX-55H) and the like.
- Specific examples of alkoxymethylated melamine include, for example, hexamethoxymethylmelamine.
- methoxymethyl type melamine compound (trade name: Cymel [registered trademark] 300, 301, 303, 350) manufactured by Nippon Cytec Industries Co., Ltd. (former Mitsui Cytec Co., Ltd.), butoxymethyl type melamine compound (Product names: My Coat [registered trademark] 506, 508), Sanwa Chemical Co., Ltd.
- methoxymethyl type melamine compound (Product names: Nicalac [registered trademark] MW-30, MW-22, MW-11) MS-001, MX-002, MX-730, MX-750, MX-035), butoxymethyl type melamine compound (trade name: Nicalac [registered trademark] MX-45, MX-410, MX-302).
- a compound obtained by condensing a melamine compound, urea compound, glycoluril compound and benzoguanamine compound in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group may be used.
- examples thereof include high molecular weight compounds produced from melamine compounds and benzoguanamine compounds described in US Pat. No. 6,323,310.
- Commercially available products of the melamine compounds include trade name Cymel [registered trademark] 303 (manufactured by Nippon Cytec Industries Co., Ltd.
- an acrylamide compound substituted with a hydroxymethyl group or an alkoxymethyl group such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, N-butoxymethylmethacrylamide, or the like Polymers produced using methacrylamide compounds can also be used.
- Examples of such a polymer include poly (N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methylmethacrylate, and N-ethoxymethyl. Examples thereof include a copolymer of methacrylamide and benzyl methacrylate, and a copolymer of N-butoxymethylacrylamide, benzyl methacrylate and 2-hydroxypropyl methacrylate.
- the weight average molecular weight of such a polymer is 1,000 to 500,000, preferably 2,000 to 200,000, more preferably 3,000 to 150,000, and even more preferably 3 , 50,000 to 50,000.
- the weight average molecular weight is a value obtained by using gel as a standard sample by gel permeation chromatography (GPC).
- cross-linking agents can be used alone or in combination of two or more.
- the content of the crosslinking agent of component (C) in the thermosetting film-forming composition having photo-alignment property of the present invention is the total amount of the specific copolymer of component (A) and the acrylic polymer of component (B).
- the amount is preferably 1 to 40 parts by weight, more preferably 5 to 30 parts by weight based on 100 parts by weight.
- the content of the crosslinking agent is too small, the solvent resistance and heat resistance of the cured film obtained from the thermosetting film-forming composition having photo-alignment properties are lowered, and the sensitivity during photo-orientation is lowered.
- the content of the crosslinking agent is excessive, the photo-alignment property and the storage stability may be lowered.
- an acid or thermal acid generator may be contained as the component (D).
- This component (D) is effective in promoting the thermosetting reaction of the thermosetting film-forming composition having the photo-alignment property of the present invention.
- component (D) a sulfonic acid group-containing compound, hydrochloric acid or a salt thereof, and a compound that generates heat by acid decomposition during pre-bake or post-bake, that is, heat decomposes at a temperature of 80 to 250 ° C. to generate an acid. If it is a compound, it will not specifically limit.
- Examples of such compounds include hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid, trifluoro.
- L-methanesulfonic acid p-phenolsulfonic acid, 2-naphthalenesulfonic acid, mesitylenesulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, 1H, 1H, 2H, 2H-perfluorooctanesulfonic acid, perfluoro (2-ethoxyethane) sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid, sulfonic acid such as dodecylbenzenesulfonic acid, or a hydrate or salt thereof Is mentioned.
- Examples of the compound that generates an acid by heat include bis (tosyloxy) ethane, bis (tosyloxy) propane, bis (tosyloxy) butane, p-nitrobenzyl tosylate, o-nitrobenzyl tosylate, 1,2,3- 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
- Content of (D) component in the thermosetting film formation composition which has the photo-alignment property of this invention is 100 mass parts of the total amount of the specific copolymer of (A) component, and the acrylic polymer of (B) component. Is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, and still more preferably 0.1 to 1 part by mass.
- a sensitizer may be contained as the component (E).
- This component (E) is effective in promoting the photodimerization reaction after the thermosetting film of the present invention is formed.
- benzophenone, anthracene, anthraquinone, thioxanthone, etc. and their derivatives, or nitrophenyl compounds can be mentioned.
- benzophenone derivatives and nitrophenyl compounds are preferred.
- Specific examples of preferred compounds include N, N-diethylaminobenzophenone, 2-nitrofluorene, 2-nitrofluorenone, 5-nitroacenaphthene, 4-nitrobiphenyl 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.
- the content of the sensitizer of component (E) in the thermosetting film-forming composition having photo-alignment property of the present invention is the total amount of the specific copolymer of component (A) and the acrylic polymer of component (B).
- the amount is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass with respect to 100 parts by mass. If this ratio is too small, the effect as a sensitizer may not be sufficiently obtained. If it is too large, the transmittance may be lowered and the coating film may be roughened.
- thermosetting film-forming composition having photo-alignment property of the present invention is mainly used in a solution state dissolved in a solvent.
- the solvent used in that case is only required to be able to dissolve the component (A), the component (B) and the component (C), and if necessary, the component (D), the component (E) and / or other additives described below.
- the kind and structure are not particularly limited.
- the solvent include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate.
- solvents can be used singly or in combination of two or more.
- thermosetting film-forming composition having the photo-alignment property of the present invention is a silane coupling agent, a surfactant, a rheology adjusting agent, a pigment, a dye, as long as the effects of the present invention are not impaired.
- Storage stabilizers, antifoaming agents, antioxidants and the like can be contained.
- thermosetting film-forming composition having photo-alignment property of the present invention contains a specific copolymer of component (A), an acrylic polymer of component (B), and a crosslinking agent of component (C), and is desired.
- the composition can contain one or more of (D) component acid or thermal acid generator, (E) component sensitizer, and other additives. Usually, they are used as a solution in which they are dissolved in a solvent.
- the mixing ratio of the component (A) and the component (B) is preferably 5:95 to 60:40.
- the content of the component (B) is excessive, the liquid crystal orientation is liable to be lowered, and when it is too small, the compatibility with the component (A) is lowered and the formed coating film is likely to be whitened.
- thermosetting film-forming composition having photo-alignment properties [3]: Based on 100 parts by mass of the total amount of component (A) and component (B), 1 to 40 parts by mass of component (C), 0.01 to 5 parts by mass of component (D), solvent A thermosetting film-forming composition having photo-alignment properties. [4]: Based on 100 parts by mass of the total amount of component (A) and component (B), 1 to 40 parts by mass of component (C), 0.01 to 5 parts by mass of component (D), 0 A thermosetting film-forming composition having a photo-alignment property, which contains 1 to 20 parts by mass of component (E) and a solvent.
- thermosetting film-forming composition having photo-alignment property of the present invention is used as a solution.
- the ratio of the solid content in the thermosetting film-forming composition having photo-alignment property of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, but is 1 to 80% by mass. , Preferably 3 to 60% by mass, more preferably 5 to 40% by mass.
- solid content means what remove
- the method for preparing the thermosetting film-forming composition having photo-alignment property of the present invention is not particularly limited.
- a preparation method for example, the component (A) dissolved in the solvent and the component (B) dissolved in the solvent are mixed, and the component (C), the component (D), and the component (E) are added to the solution. And a method of further mixing other additives as required at an appropriate stage of the preparation method.
- thermosetting film-forming composition having photo-alignment property of the present invention a solution of a specific copolymer obtained by a polymerization reaction in a solvent can be used as it is.
- a solution of component (A) obtained by copolymerizing a monomer having a photodimerization site and a monomer having a thermal crosslinkable site, a monomer having 2 to 5 carbon atoms and a hydroxyalkyl ester At least one of the monomers having a group and a solution of component (B) obtained by copolymerizing at least one of a monomer having a carboxyl group and a monomer having a phenolic hydroxy group, Similarly, the (C) component, (D) component, (E) component and the like are added to obtain a uniform solution.
- an additional solvent may be added for the purpose of adjusting the concentration.
- the solvent used in the production process of the component (A), the solvent used in the production process of the component (B), and the solvent used to adjust the concentration of the thermosetting film-forming composition having photo-alignment are the same. It may be different or different.
- the prepared solution of the thermosetting film-forming composition having photo-alignment property is preferably used after being filtered using a filter having a pore diameter of about 0.2 ⁇ m.
- thermosetting film-forming composition having photo-alignment properties is coated with a substrate (for example, a silicon / silicon dioxide-coated substrate, a silicon nitride substrate, a metal such as aluminum, molybdenum, or chromium).
- a substrate for example, a silicon / silicon dioxide-coated substrate, a silicon nitride substrate, a metal such as aluminum, molybdenum, or chromium.
- Substrate, glass substrate, quartz substrate, ITO substrate, etc.) and film for example, resin film such as triacetyl cellulose film, polyester film, acrylic film), etc., spin coating, flow coating, roll coating, slit coating,
- a coating film can be formed by coating by spin coating following the slit, ink jet coating, printing, etc., and then pre-drying (pre-baking) with a hot plate or oven. Then, a cured film is formed by heat-treating (post-baking) this coating film.
- a heating temperature and a heating time appropriately selected from the range of a temperature of 70 ° C. to 160 ° C. and a time of 0.3 to 60 minutes are adopted.
- the heating temperature and heating time are preferably 80 to 140 ° C. and 0.5 to 10 minutes.
- the treatment is performed at a heating temperature selected from the range of 140 ° C. to 250 ° C. for 5 to 30 minutes when on a hot plate, and for 30 to 90 minutes when in an oven. The method is taken.
- the film thickness of the cured film formed using the thermosetting composition having the photo-alignment property of the present invention is, for example, 0.1 to 30 ⁇ m, taking into account the step difference of the substrate to be used and optical and electrical properties. It can be selected appropriately.
- thermosetting film-forming composition having the photo-alignment property of the present invention it is possible to sufficiently cover the step of the substrate by curing the coating film formed using the thermosetting film-forming composition having the photo-alignment property of the present invention. Yes, a cured film having high transparency can be formed.
- thermosetting film having photoalignment formed in this manner can function as a liquid crystal material alignment layer, that is, a layer for aligning a compound having liquid crystallinity, by performing polarized UV irradiation.
- a method for irradiating polarized UV ultraviolet light having a wavelength of 150 to 450 nm is usually used, and irradiation is performed by irradiating linearly polarized light from a vertical or oblique direction at room temperature or in a heated state.
- the liquid crystal alignment layer formed from the thermosetting film composition having photo-alignment property of the present invention has solvent resistance and heat resistance, after applying a retardation material on the liquid crystal alignment layer, the liquid crystal alignment layer By heating to the phase transition temperature, the phase difference material can be brought into a liquid crystal state and photocured to form a layer having optical anisotropy.
- the retardation material for example, a liquid crystal monomer having a polymerizable group and a composition containing the same are used. And when the base material which forms a liquid crystal aligning layer is a film, it is useful as an optically anisotropic film.
- Such retardation materials include those having alignment properties such as horizontal alignment, cholesteric alignment, vertical alignment, hybrid alignment, and the like, and can be selectively used depending on the required phase difference.
- liquid crystal is injected between the substrates, and the liquid crystal A liquid crystal display element in which is aligned can also be obtained.
- thermosetting film-forming composition having photo-alignment property of the present invention can be suitably used for various optical anisotropic films and liquid crystal display elements.
- thermosetting film-forming composition having photo-alignment property of the present invention is also useful as a material for forming a cured film such as a protective 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.
- TFT thin film transistor
- it is also suitable as a material for forming an overcoat material for a color filter, an interlayer insulating film for a TFT type liquid crystal element, an insulating film for an organic EL element, and the like.
- the number average molecular weight and the 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 was flowed at 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
- the obtained specific copolymer had Mn of 7,240 and Mw of 15,350.
- Examples 1 to 7 and Comparative Examples 1 to 4 The compositions of Examples 1 to 7 and Comparative Examples 1 to 4 were prepared with the compositions shown in Table 1, and the solvent resistance, orientation, heat resistance, and transmittance were evaluated for each of the compositions.
- Example 1 to Example 7 and Comparative Example 1 to Comparative Example 4 were applied to a silicon wafer using a spin coater and then pre-baked on a hot plate at a temperature of 110 ° C. for 120 seconds.
- a 1 ⁇ m coating film was formed.
- the film thickness was measured using F20 manufactured by FILMETRICS.
- This coating film was post-baked in a hot air circulating oven at a temperature of 230 ° C. for 30 minutes to form a cured film having a thickness of 1.0 ⁇ m.
- the cured film was immersed in CHN or NMP for 60 seconds, and then dried at a temperature of 100 ° C. for 60 seconds, and the film thickness was measured.
- the case where there was no change in film thickness after immersion in CHN or NMP was marked with ⁇ , and the case where the film thickness decreased after immersion was marked with x.
- the substrate was exposed at 1000 mJ / cm 2 under a nitrogen atmosphere.
- the produced substrate was sandwiched between deflection plates, and the exposure amount of polarized UV necessary for showing the orientation was defined as the orientation sensitivity. Those which were not oriented at 200 mJ / cm 2 or more were designated as “not oriented”.
- Example 1 to Example 7 and Comparative Example 1 to Comparative Example 4 were applied to a silicon wafer using a spin coater and then pre-baked on a hot plate at a temperature of 110 ° C. for 120 seconds.
- a 1 ⁇ m coating film was formed.
- the film thickness was measured using F20 manufactured by FILMETRICS.
- This coating film was post-baked in a hot air circulating oven at a temperature of 230 ° C. for 30 minutes to form a cured film having a thickness of 1.0 ⁇ m.
- This cured film was irradiated vertically with 313 nm linearly polarized light 50 mJ / cm 2 .
- This cured film was further baked in a hot air circulating oven at 230 ° C. for 3 hours, and the remaining film ratio with respect to the film pressure after post-baking was measured.
- Examples 1 to 7 had high heat resistance and transparency, and were resistant to both CHN and NMP. In addition, orientation was exhibited with a small exposure amount.
- Comparative Example 1 In Comparative Example 1, sufficient solvent resistance was not obtained, and the alignment sensitivity was greatly reduced. In Comparative Examples 2 and 3, sufficient solvent resistance, transparency and heat resistance were obtained, but no orientation was exhibited even at an exposure amount of 200 mJ / cm 2 . In Comparative Example 4, sufficient solvent resistance, heat resistance and transmittance were not obtained, and the orientation sensitivity was greatly reduced.
- thermosetting film-forming composition having photo-alignment property is very useful as a material for an optically anisotropic film or a liquid crystal alignment layer of a liquid crystal display element.
- a thin film transistor (TFT) type liquid crystal display element organic Materials for forming cured films such as protective films and insulating films in various displays such as EL elements, especially as materials for forming interlayer insulating films for TFT liquid crystal elements, overcoats for color filters, insulating films for organic EL elements, etc. Is also suitable.
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Abstract
Description
加えて、この様な保護膜を、カラー液晶表示装置や固体撮像素子に用いられるカラーフィルタの保護膜として使用する場合には、カラーフィルタを透過する光の透過率を維持するために、高い透明性を有する膜であることが必要とされる。
すなわち、第1観点として、(A)成分である光二量化部位及び熱架橋部位を有するアクリル共重合体と、(B)成分である炭素原子数2乃至5のアルキルエステル基及び炭素原子数2乃至5のヒドロキシアルキルエステル基のうち少なくとも一方と、カルボキシル基及びフェノール性ヒドロキシ基のうち少なくとも一方とを有するアクリル重合体と、(C)成分である架橋剤とを含有する光配向性を有する熱硬化膜形成組成物に関する。
第2観点として、(A)成分が、光二量化部位を有するモノマー及び熱架橋部位を有するモノマーを含むモノマーの重合反応により得られるアクリル共重合体である第1観点に記載の光配向性を有する熱硬化膜形成組成物に関する。
第3観点として、(A)成分の光二量化部位がシンナモイル基である第1観点又は第2観点に記載の光配向性を有する熱硬化膜形成組成物に関する。
第4観点として、(A)成分の熱架橋部位がヒドロキシ基である第1観点乃至第3観点のいずれか一項に記載の光配向性を有する熱硬化膜形成組成物に関する。
第5観点として、(B)成分が、炭素原子数2乃至5のアルキルエステル基を有するモノマー及び炭素原子数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のうちの少なくとも一方と、カルボキシル基を有するモノマー及びフェノール性ヒドロキシ基を有するモノマーのうちの少なくとも一方との重合反応により得られるアクリル共重合体である第1観点乃至第4観点のいずれか一項に記載の光配向性を有する熱硬化膜形成組成物に関する。
第6観点として、(C)成分の架橋剤がメチロール基またはアルコキシメチロール基を有する架橋剤である第1観点乃至第5観点のいずれか一項に記載の光配向性を有する熱硬化膜形成組成物に関する。
第7観点として、更に、(D)成分として酸または熱酸発生剤を含有する、第1観点乃至第6観点のいずれか一項に記載の光配向性を有する熱硬化膜形成組成物に関する。
第8観点として、更に、(E)成分として増感剤を含有する、第1観点乃至第7観点のいずれか一項に記載の光配向性を有する熱硬化膜形成組成物に関する。
第9観点として、(A)成分と(B)成分との合計量の100質量部に基づいて、1乃至40質量部の(C)成分を含有する、第1観点乃至第8観点のいずれか一項に記載の光配向性を有する熱硬化膜形成組成物に関する。
第10観点として(A)成分と(B)成分との合計量の100質量部に基づいて、0.01乃至5質量部の(D)成分を含有する、第7観点乃至第9観点のいずれか一項に記載の光配向性を有する熱硬化膜形成組成物に関する。
第11観点として(A)成分と(C)成分との合計量の100質量部に基づいて、0.1乃至20質量部の(E)成分を含有する、第8観点乃至第10観点のいずれか一項に記載の光配向性を有する熱硬化膜形成組成物に関する。
第12観点として、第1観点乃至第11観点のいずれか一項に記載の光配向性を有する熱硬化膜形成組成物から形成される液晶配向層に関する。
第13観点として、第1観点乃至第11観点のいずれか一項に記載の光配向性を有する熱硬化膜形成組成物から形成される液晶配向層をその上の位相差層とともに備えた光デバイスに関する。
<(A)成分>
(A)成分は光二量化部位及び熱架橋部位を有するアクリル共重合体である。
本発明において、アクリル共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共重合体が適用されうる。
(A)成分の光二量化部位及び熱架橋部位を有するアクリル共重合体(以下、特定共重合体ともいう)は、斯かる構造を有するアクリル共重合体であればよく、アクリル共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。
式[A2]中、X2は水素原子、シアノ基、炭素原子数1乃至18のアルキル基、フェニル基、ビフェニル基また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、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、尿素結合を介して結合してもよい。
R1、R2、R3、及びR4はそれぞれ独立に水素原子、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、又はシアノ基を表す。)
特に、上記式[A1]又は式[A2]で表される、シンナモイル基の部分構造を有するモノマーがより好ましい。そのようなモノマーの具体例を、下記式[A3]又は式[A4]に示す。
R1、R2、R3、及びR4はそれぞれ独立に水素原子、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、又はシアノ基を表す。)
前記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、グリシジルアクリレート、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、2-アミノ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、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、及び、8-エチル-8-トリシクロデシルアクリレート等が挙げられる。
前記方法により得られる特定共重合体は、通常、溶剤に溶解した溶液の状態である。
(B)成分は炭素原子数2乃至5のアルキルエステル基及び炭素原子数2乃至5のヒドロキシアルキルエステル基のうちの少なくとも一方と、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方とを有するアクリル重合体である。
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。
(B)成分の炭素原子数2乃至5のアルキルエステル基及び炭素原子数2乃至5のヒドロキシアルキルエステル基のうち少なくとも一方と、カルボキシル基及びフェノール性ヒドロキシ基のうち少なくとも一方と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。
カルボキシル基及び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[B2]で表される。
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が挙げられる。
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。
b2モノマーとしてカルボキシル基のみを有するモノマーを用いる場合、b1モノマーが60乃至95モル%、b2モノマーが5乃至40モル%であることが好ましい。
他方、b2モノマーとしてフェノール性ヒドロキシ基のみを有するモノマーを用いる場合、b1モノマーが2乃至80モル%、b2モノマーが20乃至98モル%であることが好ましい。b2モノマーが過小の場合は液晶配向性が不充分となり易く、過大の場合は(A)成分のアクリル共重合体との相溶性が低下し易い。
前記方法により得られる(B)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。
本発明の(C)成分は、(A)成分である特定共重合体の熱架橋部位及び(B)成分に含まれるカルボキシル基及び/又はフェノール性ヒドロキシ基部位と結合する架橋剤である。架橋剤としては、エポキシ化合物、メチロール化合物、及びイソシアナート化合物等の化合物が挙げられるが、好ましくはメチロール化合物である。
アルコキシメチル化グリコールウリルの具体例としては、例えば、1,3,4,6-テトラキス(メトキシメチル)グリコールウリル、1,3,4,6-テトラキス(ブトキシメチル)グリコールウリル、1,3,4,6-テトラキス(ヒドロキシメチル)グリコールウリル、1,3-ビス(ヒドロキシメチル)尿素、1,1,3,3-テトラキス(ブトキシメチル)尿素、1,1,3,3-テトラキス(メトキシメチル)尿素、1,3-ビス(ヒドロキシメチル)-4,5-ジヒドロキシ-2-イミダゾリノン、及び1,3-ビス(メトキシメチル)-4,5-ジメトキシ-2-イミダゾリノン等が挙げられる。市販品として、日本サイテックインダストリーズ(株)(旧三井サイテック(株))製グリコールウリル化合物(商品名:サイメル[登録商標]1170、パウダーリンク[登録商標]1174)等の化合物、メチル化尿素樹脂(商品名:UFR[登録商標]65)、ブチル化尿素樹脂(商品名:UFR[登録商標]300、U-VAN10S60、U-VAN10R、U-VAN11HV)、DIC(株)(旧大日本インキ化学工業(株))製尿素/ホルムアルデヒド系樹脂(高縮合型、商品名:ベッカミン[登録商標]J-300S、同P-955、同N)等が挙げられる。
アルコキシメチル化ベンゾグアナミンの具体例としてはテトラメトキシメチルベンゾグアナミン等が挙げられる。市販品として、日本サイテックインダストリーズ(株)(旧三井サイテック(株))製(商品名:サイメル[登録商標]1123)、(株)三和ケミカル製(商品名:ニカラック[登録商標]BX-4000、同BX-37、同BL-60、同BX-55H)等が挙げられる。
アルコキシメチル化メラミンの具体例としては、例えば、ヘキサメトキシメチルメラミン等が挙げられる。市販品として、日本サイテックインダストリーズ(株)(旧三井サイテック(株))製メトキシメチルタイプメラミン化合物(商品名:サイメル[登録商標]300、同301、同303、同350)、ブトキシメチルタイプメラミン化合物(商品名:マイコート[登録商標]506、同508)、(株)三和ケミカル製メトキシメチルタイプメラミン化合物(商品名:ニカラック[登録商標]MW-30、同MW-22、同MW-11、同MS-001、同MX-002、同MX-730、同MX-750、同MX-035)、ブトキシメチルタイプメラミン化合物(商品名:ニカラック[登録商標]MX-45、同MX-410、同MX-302)等が挙げられる。
本発明においては(D)成分として酸または熱酸発生剤を含有しても良い。この(D)成分は、本発明の光配向性を有する熱硬化膜形成組成物の熱硬化反応を促進させることにおいて有効である。
本発明においては(E)成分として増感剤を含有しても良い。この(E)成分は、本発明の熱硬化膜形成後の光二量化反応を促進させることにおいて有効である。
本発明の光配向性を有する熱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、(B)成分及び(C)成分、必要に応じて(D)成分、(E)成分及び/又は、後述するその他添加剤を溶解できればよく、その種類及び構造などは特に限定されるものでない。
更に、本発明の光配向性を有する熱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、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。
本発明の光配向性を有する熱硬化膜形成組成物は、(A)成分の特定共重合体と、(B)成分のアクリル重合体と、(C)成分の架橋剤とを含有し、所望により(D)成分の酸または熱酸発生剤、(E)成分の増感剤、更にその他添加剤のうち一種以上を含有することができる組成物である。そして、通常は、それらが溶剤に溶解した溶液として用いられる。
[1]:(A)成分と(B)成分の配合比が5:95乃至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、1乃至40質量部の(C)成分を含有する光配向性を有する熱硬化膜形成組成物。
[2]:(A)成分と(B)成分との合計量の100質量部に基づいて、1乃至40質量部の(C)成分、溶剤を含有する光配向性を有する熱硬化膜形成組成物。
[3]:(A)成分と(B)成分との合計量の100質量部に基づいて、1乃至40質量部の(C)成分、0.01乃至5質量部の(D)成分、溶剤を含有する光配向性を有する熱硬化膜形成組成物。
[4]:(A)成分と(B)成分との合計量の100質量部に基づいて、1乃至40質量部の(C)成分、0.01乃至5質量部の(D)成分、0.1乃至20質量部の(E)成分、溶剤を含有する光配向性を有する熱硬化膜形成組成物。
本発明の光配向性を有する熱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乃至80質量%であり、好ましくは3乃至60質量%であり、より好ましくは5乃至40質量%である。ここで、固形分とは、光配向性を有する熱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。
本発明の一態様として、光配向性を有する熱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フィルム、ポリエステルフィルム、アクリルフィルム等の樹脂フィルム)等の上に、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、その後、ホットプレート又はオーブン等で予備乾燥(プリベーク)することにより、塗膜を形成することができる。その後、この塗膜を加熱処理(ポストベーク)することにより、硬化膜が形成される。
偏光UVの照射方法としては、通常150乃至450nmの波長の紫外光が用いられ、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。
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。
<アクリル重合体原料>
HEMA:2-ヒドロキシエチルメタクリレート
MMA:メチルメタクリレート
MAA:メタクリル酸
CHMI:N-シクロヘキシルマレイミド
CIN:4-(6-メタクリルオキシヘキシル-1-オキシ)ケイ皮酸メチルエステル
AIBN:α、α’-アゾビスイソブチロニトリル
<架橋剤>
HMM:ヘキサメトキシメチルメラミン
TMGU:1,3,4,6-テトラキス(メトキシメチル)グリコールウリル
<酸または熱酸発生剤>
PTSA:p-トルエンスルホン酸一水和物
<増感剤>
DEAB:N,N’-ジエチルアミノベンゾフェノン
NF:4-ニトロフルオレン
<溶剤>
CHN:シクロヘキサノン
PM:プロピレングリコールモノメチルエーテル
PMA:プロピレングリコールモノメチルエーテルアセテート
CIN 40.0g、HEMA 10.0g、重合触媒としてAIBN 1.2gをCHN 133.5gに溶解し85℃にて20時間反応させることにより特定共重合体溶液(固形分濃度27質量%)を得た(P1)。得られた特定共重合体のMnは7,080、Mwは14,030であった。
CIN 48.0g、MMA 12.0g、重合触媒としてAIBN 1.3gをCHN 166.8gに溶解し80℃にて20時間反応させることにより特定共重合体溶液(固形分濃度27質量%)を得た(P2)。得られた特定共重合体のMnは8,700、Mwは18,000であった。
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%)を得た(P3)。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。
MAA 3.5g、MMA 7.0g、HEMA 7.0g、重合触媒としてAIBN 0.5gをPM 53.9gに溶解し75℃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%)を得た(P4)。得られたのMnは10,300、Mwは24,600であった。
MMA 9.0g、HEMA 6.0g、重合触媒としてAIBN 0.2gをPM 45.5g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%)を得た(P5)。得られたアクリル共重合体のMnは18,100、Mwは47,100であった。
CHMI 17.8g、MAA 9.8g、MMA 12.8g、HEMA 9.8g、重合触媒としてAIBN 2.8gをPMA 116gに溶解し85℃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30質量%)を得た(P6)。得られたアクリル共重合体のMnは7,200、Mwは15,200であった。
CIN 40.0g、MAA 10.0g、重合触媒としてAIBN 1.2gをCHN 133.5gに溶解し80℃にて20時間反応させることにより特定共重合体溶液(固形分濃度27質量%)を得た(P7)。得られた特定共重合体のMnは7,240、Mwは15,350であった。
実施例1乃至実施例7並びに比較例1乃至比較例4の各組成物をシリコンウエハーにスピンコーターを用いて塗布した後、温度110℃で120秒間ホットプレート上においてプリベークを行い、膜厚1.1μmの塗膜を形成した。膜厚はFILMETRICS社製 F20を用いて測定した。この塗膜を温度230℃で30分間熱風循環式オーブン中でポストベークを行い、膜厚1.0μmの硬化膜を形成した。
この硬化膜をCHN又はNMP中に60秒間浸漬させた後、それぞれ温度100℃にて60秒間乾燥し、膜厚を測定した。CHN又はNMP浸漬後の膜厚変化がないものを○、浸漬後に膜厚の減少が見られたものを×とした。
実施例1乃至実施例7並びに比較例1乃至比較例4の各組成物をITO基板上にスピンコーターを用いて塗布した後、温度110℃で120秒間ホットプレート上においてプリベークを行い膜厚1.1μmの塗膜を形成した。膜厚はFILMETRICS社製 F20を用いて測定した。この塗膜を温度230℃で30分間熱風循環式オーブン中でポストベーク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照射した。この基板上に液晶モノマーからなる位相差材料溶液をスピンコーターを用いて塗布した後、80℃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1.4μmの塗膜を形成した。この基板を窒素雰囲気下1000mJ/cm2で露光した。作製した基板を偏向板に挟み、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。200mJ/cm2以上で配向しないものは「配向せず」とした。
実施例1乃至実施例7並びに比較例1乃至比較例4の各組成物をシリコンウエハーにスピンコーターを用いて塗布した後、温度110℃で120秒間ホットプレート上においてプリベークを行い、膜厚1.1μmの塗膜を形成した。膜厚はFILMETRICS社製 F20を用いて測定した。この塗膜を温度230℃で30分熱風循環式オーブン中でポストベークを行い膜厚1.0μmの硬化膜を形成した。この硬化膜に313nmの直線偏光50mJ/cm2を垂直に照射した。この硬化膜をさらに温度230℃で3時間熱風循環式オーブン中で焼成し、ポストベーク後の膜圧に対する残膜率を測定した。
実施例1乃至実施例7並びに比較例1乃至比較例4の各組成物を石英基板上にスピンコーターを用いて塗布した後、温度110℃で120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。膜厚はFILMETRICS社製 F20を用いて測定した。この塗膜を温度230℃で30分間熱風循環式オーブン中でポストベークを行い硬化膜を形成した。
この硬化膜を紫外線可視分光光度計((株)島津製作所製SHIMADSU UV-2550型番)を用いて波長400nmの光に対する透過率を測定した。
Claims (13)
- (A)成分である光二量化部位及び熱架橋部位を有するアクリル共重合体と、(B)成分である炭素原子数2乃至5のアルキルエステル基及び炭素原子数2乃至5のヒドロキシアルキルエステル基のうちの少なくとも一方と、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方とを有するアクリル重合体と、(C)成分である架橋剤とを含有する光配向性を有する熱硬化膜形成組成物。
- (A)成分が、光二量化部位を有するモノマー及び熱架橋部位を有するモノマーを含むモノマーの重合反応により得られるアクリル共重合体である請求項1に記載の光配向性を有する熱硬化膜形成組成物。
- (A)成分の光二量化部位がシンナモイル基である請求項1又は請求項2に記載の光配向性を有する熱硬化膜形成組成物。
- (A)成分の熱架橋部位がヒドロキシ基である請求項1乃至請求項3のいずれか一項に記載の光配向性を有する熱硬化膜形成組成物。
- (B)成分が、炭素原子数2乃至5のアルキルエステル基を有するモノマー及び炭素原子数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のうちの少なくとも一方と、カルボキシル基を有するモノマー及びフェノール性ヒドロキシ基を有するモノマーのうちの少なくとも一方との重合反応により得られるアクリル共重合体である請求項1乃至請求項4のいずれか一項に記載の光配向性を有する熱硬化膜形成組成物。
- (C)成分の架橋剤がメチロール基またはアルコキシメチロール基を有する架橋剤である請求項1乃至請求項5のいずれか一項に記載の光配向性を有する熱硬化膜形成組成物。
- 更に、(D)成分として酸または熱酸発生剤を含有する、請求項1乃至請求項6のいずれか一項に記載の光配向性を有する熱硬化膜形成組成物。
- 更に、(E)成分として増感剤を含有する、請求項1乃至請求項7のいずれか一項に記載の光配向性を有する熱硬化膜形成組成物。
- (A)成分と(B)成分の合計量の100質量部に基づいて、1乃至40質量部の(C)成分を含有する、請求項1乃至請求項8のいずれか一項に記載の光配向性を有する熱硬化膜形成組成物。
- (A)成分と(B)成分との合計量の100質量部に基づいて、0.01乃至5質量部の(D)成分を含有する、請求項7乃至請求項9のいずれか一項に記載の光配向性を有する熱硬化膜形成組成物。
- (A)成分と(B)成分との合計量の100質量部に基づいて、0.1乃至20質量部の(E)成分を含有する、請求項8乃至請求項10に記載の光配向性を有する熱硬化膜形成組成物。
- 請求項1乃至請求項11のいずれか一項に記載の光配向性を有する熱硬化膜形成組成物から形成される液晶配向層。
- 請求項1乃至請求項11のいずれか一項に記載の光配向性を有する熱硬化膜形成組成物から形成される液晶配向層をその上の位相差層とともに備えた光デバイス。
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US13/381,836 US9796843B2 (en) | 2009-07-21 | 2010-07-20 | Composition for forming thermoset film having photo alignment properties |
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KR1020127002345A KR101791446B1 (ko) | 2009-07-21 | 2010-07-20 | 광배향성을 갖는 열경화막 형성 조성물 |
CN201080032575.1A CN102471629B (zh) | 2009-07-21 | 2010-07-20 | 形成具有光取向性的热固化膜的组合物 |
JP2011523655A JP5748061B2 (ja) | 2009-07-21 | 2010-07-20 | 光配向性を有する熱硬化膜形成組成物 |
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CN102471629A (zh) | 2012-05-23 |
US20120114879A1 (en) | 2012-05-10 |
TWI541284B (zh) | 2016-07-11 |
TW201116570A (en) | 2011-05-16 |
US9796843B2 (en) | 2017-10-24 |
JP5748061B2 (ja) | 2015-07-15 |
JPWO2011010635A1 (ja) | 2012-12-27 |
EP2457964B1 (en) | 2015-09-09 |
CN102471629B (zh) | 2015-09-09 |
KR101791446B1 (ko) | 2017-10-30 |
EP2457964A1 (en) | 2012-05-30 |
KR20120050981A (ko) | 2012-05-21 |
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