WO2013146469A1 - Composition for forming cured film, orientation material, and phase difference material - Google Patents
Composition for forming cured film, orientation material, and phase difference material Download PDFInfo
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- WO2013146469A1 WO2013146469A1 PCT/JP2013/057824 JP2013057824W WO2013146469A1 WO 2013146469 A1 WO2013146469 A1 WO 2013146469A1 JP 2013057824 W JP2013057824 W JP 2013057824W WO 2013146469 A1 WO2013146469 A1 WO 2013146469A1
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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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
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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
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
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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
- C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
- C09D101/08—Cellulose derivatives
- C09D101/26—Cellulose ethers
- C09D101/28—Alkyl ethers
- C09D101/284—Alkyl ethers with hydroxylated hydrocarbon radicals
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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
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
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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
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
- C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3016—Polarising elements involving passive liquid crystal elements
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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
- C08L2312/00—Crosslinking
Definitions
- the present invention relates to a cured film forming composition, an alignment material, and a retardation material.
- a right-eye image is visually recognized by an observer's right eye
- a left-eye image is visually recognized by an observer's left eye, whereby a stereoscopic image can be displayed.
- a retardation material is usually disposed on a display element such as a liquid crystal panel.
- a retardation material a plurality of two kinds of retardation regions having different retardation characteristics are regularly arranged, and a patterned retardation material is formed.
- a retardation material patterned so as to arrange a plurality of retardation regions having different retardation characteristics is referred to as a patterned retardation material.
- the patterned retardation material can be produced, for example, by optically patterning a retardation material made of a polymerizable liquid crystal as disclosed in Patent Document 2.
- Optical patterning of a retardation material made of a polymerizable liquid crystal utilizes a photo-alignment technique known for forming an alignment material for a liquid crystal panel. That is, a coating film made of a photo-alignment material is provided on a substrate, and two types of polarized light having different polarization directions are irradiated on the coating film. Then, a photo-alignment film is obtained as an alignment material in which two types of liquid crystal alignment regions having different liquid crystal alignment control directions are formed.
- a solution-like retardation material containing a polymerizable liquid crystal is applied on the photo-alignment film to realize the alignment of the polymerizable liquid crystal. Thereafter, the aligned polymerizable liquid crystal is cured to form a patterned retardation material.
- acrylic resins and polyimide resins having photodimerization sites such as cinnamoyl groups and chalcone groups in the side chain are known as usable photo-alignment materials.
- These resins have been reported to exhibit the ability to control the alignment of liquid crystals (hereinafter also referred to as liquid crystal alignment) by irradiation with polarized UV (see Patent Documents 3 to 5).
- such an acrylic resin having a photodimerization site such as a cinnamoyl group or a chalcone group in the side chain may not have sufficient characteristics when applied to the formation of a retardation material.
- a large amount of polarized UV exposure is required. .
- the polarized UV exposure amount is much larger than the polarized UV exposure amount (for example, about 100 mJ / cm 2 ) sufficient to align the liquid crystal for a normal liquid crystal panel.
- the reason for increasing the amount of polarized UV exposure is that, in the case of retardation material formation, unlike liquid crystals for liquid crystal panels, polymerizable liquid crystals are used in the state of solution and applied onto the alignment material. Yes.
- an alignment material is formed using an acrylic resin having a photodimerization site such as a cinnamoyl group in the side chain, and the polymerizable liquid crystal is to be aligned, the acrylic resin is subjected to photocrosslinking by a 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. In order to align the liquid crystal of the liquid crystal panel, it is usually only necessary to dimerize only the surface of the photo-alignment alignment material.
- 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 photo-alignment film formed from the conventional materials as described above cannot be aligned well due to the influence of Na content in the alkali glass.
- 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 an alkali glass. Is to provide.
- Another object of the present invention is obtained from the cured film-forming composition, has excellent photoreaction efficiency, has solvent resistance, and can orient the polymerizable liquid crystal with high sensitivity even on alkali glass.
- 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 photoalignment group and any one substituent selected from a hydroxy group, a carboxyl group and an amino group, (B) A cured film containing a hydrophilic polymer having one or more substituents selected from a hydroxy group, a carboxyl group and an amino group, and (C) an alkoxysilane compound having an amino group Relates to forming compositions.
- 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 component (B) is preferably at least one polymer selected from the group consisting of polyether polyol, polyester polyol, polycarbonate polyol and polycaprolactone polyol.
- the component (B) is preferably cellulose or a derivative thereof.
- the component (B) is at least one of a polyethylene glycol ester group 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 preferable that it is an acrylic polymer which has.
- the component (B) includes at least one of a monomer having a polyethylene glycol ester group and a monomer having a hydroxyalkyl ester group having 2 to 5 carbon atoms, a monomer having a carboxyl group, and An acrylic copolymer obtained by a polymerization reaction of a monomer containing at least one of monomers having a phenolic hydroxy group is preferable.
- the component (B) is preferably cyclodextrin or a derivative thereof.
- the ratio of the component (A) to the component (B) is preferably 5:95 to 60:40 by mass ratio.
- component (C) it is preferable to contain 10 parts by mass to 100 parts by mass of component (C) based on 100 parts by mass of the total amount of component (A) and component (B).
- 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.
- 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 an alkali glass. Things can be provided.
- the second aspect of the present invention it is possible to provide an alignment material having excellent photoreaction efficiency and solvent resistance and capable of aligning a polymerizable liquid crystal with high sensitivity even on an alkali glass.
- the third aspect of the present invention it is possible to provide a retardation material that can be formed on an alkali glass with high efficiency and can be subjected to optical patterning.
- the cured film forming composition of the present embodiment includes a low molecular photo-alignment component as component (A), a hydrophilic polymer as component (B), and an alkoxysilane compound having an amino group as component (C). Containing.
- the cured film forming composition of the present embodiment contains other additives in addition to the component (A), the component (B), and the component (C), as long as the effects of the present invention are not impaired. Can do.
- the component (A) contained in the cured film forming composition of the present embodiment is the above-described low molecular photoalignment component.
- the low molecular photo-alignment component which is (A) component can be made into the compound which has a photo-alignment group and any one substituent chosen from a hydroxyl group, a carboxyl group, and an amino group.
- the photoreactive group is a hydrophobic photoreactive moiety in the photoreaction component.
- the hydroxy group or the like constitutes a hydrophilic thermal reaction part.
- the photo-alignment group means a functional group at a structural site that undergoes photodimerization or photoisomerization.
- the structural site to be photodimerized is a site that forms a dimer by light irradiation, and specific examples thereof include a cinnamoyl group, a chalcone group, a coumarin group, and an anthracene group. Among these, a cinnamoyl group having high transparency in the visible light region and photodimerization reactivity is preferable.
- the structural site that undergoes photoisomerization refers to a structural site that changes into a cis form and a trans form upon irradiation with light, and specific examples thereof include a site comprising an azobenzene structure, a stilbene structure, or the like. Of these, an azobenzene structure is preferred because of its high reactivity.
- the compound having a photo-alignment group and a hydroxy group is represented by the following formula, for example.
- X 1 represents a single bond or an alkylene, phenylene, biphenylene or cyclohexylene having 1 to 18 carbon atoms bonded via a covalent bond, an ether bond, an ester bond, an amide bond, an amino bond or a urea bond.
- alkylene, phenylene and biphenylene may be substituted with one or more substituents selected from the same or different groups selected from a halogen atom and a cyano group.
- X 2 represents a hydrogen atom, a cyano group, a nitro 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, an amino bond, or a urea bond.
- the group and the biphenyl group may be substituted with either a halogen atom or a cyano group.
- 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 to 4 carbon atoms. Represents an alkoxy group, a halogen atom, a trifluoromethyl group or a cyano group.
- the (A) component compound having a photoalignable group and a hydroxy group include, for example, 4- (8-hydroxyoctyloxy) cinnamic acid methyl ester, 4- (6-hydroxyhexyloxy) silicic acid.
- 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-hydroxymethyloxycinnamic 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-hydroxy (Ropyloxy) cinnamic acid ethyl ester, 4- (2-hydroxyethyloxy) cinnamic acid ethyl ester, 4-hydroxymethyloxy cinnamic acid ethyl ester, 4-hydroxycinnamic
- the compound having a photo-alignment group and a carboxyl group include cinnamic acid, ferulic acid, 4-nitrocinnamic acid, 4-methoxy cinnamic acid, 3,4-dimethoxy cinnamic acid, coumarin-3- Carboxylic acid, 4- (N, N-dimethylamino) cinnamic acid and the like can be mentioned.
- Specific examples of the compound having a photo-alignment group and an amino group include methyl-4-aminocinnamic acid, ethyl-4-aminocinnamic acid, methyl-3-aminocinnamic acid, and ethyl-3-aminocinnamic acid. An acid etc. are mentioned.
- Specific examples of the low molecular photo-alignment component as the component (A) are not limited to these.
- the photo-alignment component as the component (A) is a compound having a photo-alignment group and a hydroxy group
- the component (A) two or more photo-alignment 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.
- a compound represented by the following formula can be shown as an example of a compound having two or more photoalignable groups and hydroxy groups in the molecule.
- the photo-alignment component (A) it is possible to control to increase the molecular weight of the photo-alignment component as the component (A).
- the photo-alignment component (A) and the polymer (B) component and the cross-linking agent (C) are thermally reacted, the photo-alignment component (A) It can suppress that a component sublimates.
- the cured film formation composition of this Embodiment can form alignment material with high photoreaction efficiency as a cured film.
- a compound of (A) component in the cured film formation composition of this Embodiment it has multiple types which have a photo-alignment group and any one substituent chosen from a hydroxyl group, a carboxyl group, and an amino group. A mixture of these compounds may also be used.
- the component (B) contained in the cured film forming composition of the present embodiment is a hydrophilic polymer.
- the polymer which is (B) component can be made into the polymer (henceforth a specific polymer) which has 1 type, or 2 or more types of substituents chosen from a hydroxy group, a carboxyl group, and an amino group.
- a specific polymer As the specific polymer as the component (B), it is preferable to select a highly hydrophilic polymer having high hydrophilicity so as to be more hydrophilic than the component (A). .
- a specific polymer is a polymer which has hydrophilic groups, such as a hydroxyl group, a carboxyl group, and an amino group, Specifically, 1 type or 2 types chosen from a hydroxy group, a carboxyl group, and an amino group A polymer having the above substituents is preferred.
- Examples of the polymer as the component (B) include acrylic polymer, polyamic acid, polyimide, polyvinyl alcohol, polyester, polyester polycarboxylic acid, polyether polyol, polyester polyol, polycarbonate polyol, polycaprolactone polyol, polyalkyleneimine, poly Examples include allylamines, celluloses (cellulose or derivatives thereof), polymers having a linear or branched structure such as phenol novolac resins and melamine formaldehyde resins, and cyclic polymers such as cyclodextrins.
- acrylic polymer a polymer obtained by polymerizing a monomer having an unsaturated double bond such as acrylic ester, methacrylic ester or styrene can be applied.
- the specific polymer as the component (B) is preferably Hydroxyalkyl cyclodextrins, ⁇ Cellulose, An acrylic polymer having at least one of a polyethylene glycol ester group and a hydroxyalkyl ester group having 2 to 5 carbon atoms, and at least one of a carboxyl group and a phenolic hydroxy group, An acrylic polymer having an aminoalkyl group in the side chain, ⁇ Polyether polyol, ⁇ Polyester polyol, Polycarbonate polyol and polycaprolactone polyol.
- (B) It is a preferred example of the specific polymer of the component, and has at least one of a polyethylene glycol ester group and a hydroxyalkyl ester group having 2 to 5 carbon atoms, and at least one of a carboxyl group and a phenolic hydroxy group.
- the acrylic polymer may be an 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 As a structural unit having at least one of a polyethylene glycol ester group and a hydroxyalkyl ester group having 2 to 5 carbon atoms, a preferred structural unit is represented by the following formula [B1]. 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].
- X 3 and X 4 each independently represent a hydrogen atom or a methyl group
- Y 1 represents an H— (OCH 2 CH 2 ) n — group (where n The value is 2 to 50, preferably 2 to 10.) or a hydroxyalkyl group having 2 to 5 carbon atoms
- Y 2 represents a carboxyl group or a phenolic hydroxy group.
- the acrylic polymer as an example of 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. More preferably, it is 000. 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, When cured, it may become insufficiently cured and solvent resistance and heat resistance may decrease.
- the weight average molecular weight is a value obtained by using gel as a standard material by gel permeation chromatography (GPC).
- GPC gel permeation chromatography
- a monomer having at least one of a polyethylene glycol ester group and a hydroxyalkyl ester group having 1 to 4 carbon atoms (hereinafter also referred to as b1 monomer) is used.
- a method of copolymerizing a monomer having at least one of a carboxyl group and a phenolic hydroxy group (hereinafter also referred to as b2 monomer) is simple.
- Examples of the monomer having a polyethylene glycol ester group described above include monoacrylate or monomethacrylate of H— (OCH 2 CH 2 ) n —OH.
- the value of n is 2 to 50, preferably 2 to 10.
- Examples of the monomer having a hydroxyalkyl ester group having 2 to 5 carbon atoms include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, and 4-hydroxybutyl acrylate. 4-hydroxybutyl methacrylate.
- Examples of the monomer having a carboxyl group described above include acrylic acid, methacrylic acid, and vinyl benzoic acid.
- Examples of the monomer having a phenolic hydroxy group described above include p-hydroxystyrene, m-hydroxystyrene, and o-hydroxystyrene.
- a monomer other than the b1 monomer and the b2 monomer, specifically a hydroxy group when synthesizing an acrylic polymer as an example of the component (B), a monomer other than the b1 monomer and the b2 monomer, specifically a hydroxy group, unless the effects of the present invention are impaired. And a monomer having neither of the carboxyl groups can be used in combination.
- Examples of such a monomer include acrylic acid ester compounds such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl methacrylate, butyl acrylate, isobutyl acrylate, and t-butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, Methacrylic acid ester compounds such as isopropyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, maleimide compounds such as maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide, acrylamide compounds, acrylonitrile, maleic anhydride, styrene Examples thereof include compounds and vinyl compounds.
- acrylic acid ester compounds such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl
- the amount of the b1 monomer and b2 monomer used to obtain the acrylic polymer which is an example of the component (B) is based on the total amount of all monomers used to obtain the acrylic polymer which is the component (B). It is preferable that the monomer is 2 mol% to 95 mol% and the b2 monomer is 5 mol% to 98 mol%.
- the b1 monomer is 60 mol% to 95 mol% and the b2 monomer is based on the total amount of all monomers used to obtain the acrylic polymer as the component (B). 5 mol% to 40 mol% is preferable.
- the b1 monomer is 2 mol% to 80 mol% and the b2 monomer is 20 mol% to 98 mol%.
- the method to obtain the acrylic polymer which is an example of a component is not specifically limited,
- the solvent which coexisted the monomer other than b1 monomer and b2 monomer with the monomer other than b1 monomer and the polymerization initiator etc. if desired In the polymerization reaction at a temperature of 50 to 110 ° C.
- 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 the ⁇ Solvent> section below.
- the acrylic polymer having an aminoalkyl group in the side chain which is a preferred example of the specific polymer of component (B), includes aminoalkyl ester monomers such as aminoethyl acrylate, aminoethyl methacrylate, aminopropyl acrylate and aminopropyl methacrylate. What polymerized or what copolymerized the said aminoalkyl ester monomer and 1 type, or 2 or more types of monomers chosen from said acrylic monomer are mentioned.
- the acrylic polymer as an example of the component (B) obtained by the above method is usually in a solution state dissolved in a solvent.
- the acrylic polymer solution which is an example of the component (B) obtained by the above method, is poured into diethyl ether or water under stirring to cause reprecipitation, and the generated precipitate is filtered and washed. Under normal pressure or reduced pressure, it can be dried at room temperature or dried to obtain an acrylic polymer powder as an example of the component (B).
- the polymerization initiator and unreacted monomer coexisting with the acrylic polymer as an example of the component (B) can be removed.
- the purified acrylic polymer as an example of the component (B) A powder is obtained. If sufficient purification cannot be achieved by a single operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.
- polyether polyol which is a preferred example of the specific polymer of component (B), polyethylene glycol, polypropylene glycol, propylene glycol, bisphenol A, triethylene glycol, sorbitol and other polyhydric alcohols, propylene oxide, polyethylene glycol, polypropylene glycol, etc. Is added.
- polyether polyols include ADEKA Adeka Polyether P Series, G Series, EDP Series, BPX Series, FC Series, CM Series, NOF UNIOX (registered trademark) HC-40, HC-60, ST- 30E, ST-40E, G-450, G-750, Uniol (registered trademark) TG-330, TG-1000, TG-3000, TG-4000, HS-1600D, DA-400, DA-700, DB-400 Nonion (registered trademark) LT-221, ST-221, OT-221 and the like.
- polyester polyol which is a preferable example of the specific polymer of component
- diols such as ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol and polypropylene glycol are added to polyvalent carboxylic acids such as adipic acid, sebacic acid and isophthalic acid. Can be mentioned.
- polyester polyols include DIC polylite (registered trademark) OD-X-286, OD-X-102, OD-X-355, OD-X-2330, OD-X-240, OD-X-668, OD-X-2108, OD-X-2376, OD-X-2044, OD-X-688, OD-X-2068, OD-X-2547, OD-X-2420, OD-X-2523, OD- X-2555, OD-X-2560, Kuraray polyols P-510, P-1010, P-2010, P-3010, P-4010, P-5010, P-6010, F-510, F-1010, F -2010, F-3010, P-1011, P-2011, P-2013, P-2030, N-2010, PNNA-2016, C-590, C-1050, C-2050, C-2090, C-3090 Etc.
- DIC polylite registered trademark
- polycaprolactone polyol examples include those obtained by reacting polycaprolactone with a polyhydric alcohol such as trimethylolpropane or ethylene glycol.
- polyhydric alcohol such as trimethylolpropane or ethylene glycol.
- Specific examples of the polycaprolactone polyol include DIC polylite (registered trademark) OD-X-2155, OD-X-640, OD-X-2568, Daicel Chemical's Plaxel (registered trademark) 205, L205AL, 205U, 208, 210 212, L212AL, 220, 230, 240, 303, 305, 308, 312, 320, and the like.
- polycarbonate polyol which is a preferable example of the specific polymer of a component, what made polycarbonate react with polyhydric alcohols, such as a trimethylol propane and ethylene glycol, is mentioned.
- polyhydric alcohols such as a trimethylol propane and ethylene glycol
- Specific examples of the polycarbonate polyol include Plaxel (registered trademark) CD205, CD205PL, CD210, and CD220 manufactured by Daicel Chemical.
- cellulose examples include hydroxyalkylcelluloses such as hydroxyethylcellulose and hydroxypropylcellulose, hydroxyalkylalkylcelluloses such as hydroxyethylmethylcellulose, hydroxypropylmethylcellulose and hydroxyethylethylcellulose, and cellulose.
- hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose are preferable.
- the cyclodextrin which is a preferred example of the specific polymer of the component (B) includes cyclodextrins such as ⁇ -cyclodextrin, ⁇ -cyclodextrin and ⁇ -cyclodextrin, methyl- ⁇ -cyclodextrin, methyl- ⁇ -cyclodextrin And methylated cyclodextrins such as methyl- ⁇ -cyclodextrin, hydroxymethyl- ⁇ -cyclodextrin, hydroxymethyl- ⁇ -cyclodextrin, hydroxymethyl- ⁇ -cyclodextrin, hydroxymethyl- ⁇ -cyclodextrin, 2-hydroxyethyl- ⁇ -cyclodextrin, 2- Hydroxyethyl- ⁇ -cyclodextrin, 2-hydroxyethyl- ⁇ -cyclodextrin, 2-hydroxypropyl- ⁇ -cyclodextrin, 2-hydroxypropyl- ⁇ -cyclodextrin, 2-hydroxypro Pill- ⁇ -cycl
- the melamine formaldehyde resin which is a preferable example of the specific polymer of the component (B) is a resin obtained by polycondensation of melamine and formaldehyde, and is represented by the following formula.
- R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
- the methylol group generated during the polycondensation of melamine and formaldehyde is alkylated from the viewpoint of storage stability.
- the method for obtaining the melamine formaldehyde resin as the component (B) is not particularly limited. Generally, melamine and formaldehyde are mixed, made weakly alkaline using sodium carbonate, ammonia, etc., and then heated at 60 to 100 ° C. Is synthesized. Further, the methylol group can be alkoxylated by reacting with alcohol.
- the component (B) melamine formaldehyde resin preferably has a weight average molecular weight of 250 to 5,000, more preferably 300 to 4,000, and still more preferably 350 to 3,500. If the weight average molecular weight is over 5,000, the solubility in the solvent may be lowered and the handling property may be lowered. If the weight average molecular weight is less than 250 and the weight is too small, Insufficient curing may reduce solvent resistance and heat resistance.
- the melamine formaldehyde resin as the component (B) may be used in a liquid form or a solution form in which a purified liquid is redissolved in a solvent described later.
- the (B) component melamine formaldehyde resin may be a mixture of a plurality of types of (B) component melamine formaldehyde resins.
- phenol novolak resin which is a preferred example of the specific polymer of the component (B) include phenol-formaldehyde polycondensate.
- the polymer of the component (B) may be used in a powder form or a solution form in which the purified powder is redissolved in a solvent described later.
- the polymer of component (B) may be a mixture of a plurality of types of polymer of component (B).
- Component (C) contained in the cured film forming composition of the present embodiment is an alkoxysilane compound having an amino group.
- alkoxysilane compound having an amino group examples include N, N′-bis [3- (trimethoxysilyl) propyl] -1,2-ethanediamine, N, N′-bis [3- (triethoxysilyl) Propyl] -1,2-ethanediamine, N- [3- (trimethoxysilyl) propyl] -1,2-ethanediamine, N- [3- (triethoxysilyl) propyl] -1,2-ethanediamine, Bis- ⁇ 3- (trimethoxysilyl) propyl ⁇ amine, bis- ⁇ 3- (triethoxysilyl) propyl ⁇ amine, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, trimethoxy ⁇ 3- (methyl) Amino) propylsilane, 3- (N-allylamino) propyltrimethoxysilane, 3- (N-allylamino)
- alkoxysilane compounds having an amino group can be used alone or in combination of two or more.
- the content of the alkoxysilane compound having an amino group as the component (C) in the cured film forming composition of the present embodiment is 100 parts by mass of the total amount of the compound as the component (A) and the polymer as the component (B). Is preferably 10 parts by mass to 100 parts by mass, and more preferably 15 parts by mass to 80 parts by mass.
- the content of the alkoxysilane compound having an amino group as component (C) is too small, the solvent resistance and heat resistance of the cured film obtained from the cured film forming composition are lowered, and the sensitivity during photo-alignment is lowered. To do.
- the content is excessive, the photo-alignment property and the storage stability may be lowered.
- the cured film forming composition of the present embodiment is mainly used in a solution state dissolved in a solvent.
- the solvent used in that case should just be able to melt
- 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 alone or in combination of two or more.
- 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.
- the ratio of the sensitizer used in the cured film forming composition of the present embodiment is 0.000 with respect to 100 parts by mass of the total mass of the specific copolymer (A) and the acrylic polymer (B). It is preferably 1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass. If this ratio is too small, the effect as a sensitizer may not be sufficiently obtained. If it is too large, the transmittance may be lowered and the coating film may be roughened.
- the cured film forming composition of the present embodiment is a (A) component low molecular photo-alignment component, and (B) component (A) a polymer that is more hydrophilic than the photo-alignment component; (C) the alkoxysilane compound which has an amino group which is a component. And as long as the effect of this invention is not impaired, another additive can be contained.
- the mixing ratio of the component (A) and the component (B) is preferably 5:95 to 60:40 by mass ratio.
- the content of the component (B) is excessive, the liquid crystal orientation is liable to be lowered, and when it is too small, the solvent resistance is lowered and the orientation is liable to be lowered.
- Preferred examples of the cured film forming composition of the present embodiment are as follows. [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 component (A) and the component (B). A cured film forming composition containing 10 parts by mass to 100 parts by mass of component (C).
- a cured film forming composition containing 10 parts by mass to 100 parts by mass of component (C) and a solvent based on 100 parts by mass of the total amount of component (A) and component (B).
- 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% by mass to 60% by mass, more preferably 5% by mass to 40% by mass.
- solid content means what remove
- the method for preparing the cured film forming composition of the present embodiment is not particularly limited.
- 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 solution of a specific copolymer obtained by a polymerization reaction in a solvent can be used as it is.
- a monomer having a polyethylene glycol ester group and a monomer having a hydroxyalkyl ester group having 2 to 5 carbon atoms at least one of a monomer having a carboxyl group and a monomer having a phenolic hydroxy group
- the components (A) and (C) are added to the solution of the component (B) obtained by copolymerizing the 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 heating and drying conditions may be such that the cross-linking reaction with the cross-linking agent proceeds to such an extent that the components of the alignment material formed from the cured film do not elute into the polymerizable liquid crystal solution applied thereon.
- a heating temperature and a heating time appropriately selected from the range of 0 ° C. to 200 ° C. and a time of 0.4 minutes to 60 minutes are employed.
- the heating temperature and heating time are preferably 70 ° C. to 160 ° C., 0.5 minutes to 10 minutes.
- the film thickness of the cured film formed using the curable composition of the present embodiment is, for example, 0.05 ⁇ m to 5 ⁇ m, and is appropriately selected in consideration of the level difference of the substrate to be used and the optical and electrical properties. be able to.
- the cured film thus formed can function as an alignment material, that is, a member for aligning a liquid crystal compound such as liquid crystal by performing polarized UV irradiation.
- ultraviolet light or visible light having a wavelength of 150 nm to 450 nm is usually used, and irradiation is performed by irradiating linearly polarized light from a vertical or oblique direction at room temperature or in a heated state.
- the alignment material formed from the cured film composition of the present embodiment has solvent resistance and heat resistance, after applying a retardation material composed of a polymerizable liquid crystal solution on the alignment material, By heating to the phase transition temperature, the phase difference material is brought into a liquid crystal state and is aligned on the alignment material. Then, the retardation material in an oriented state can be cured as it is to form a retardation material as 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.
- 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.
- the phase difference material that forms such a phase difference material is in a liquid crystal state and has an alignment state such as horizontal alignment, cholesteric alignment, vertical alignment, hybrid alignment, etc. on the alignment material. It can be used properly according to the phase difference.
- the patterned phase difference material used for 3D display it is predetermined
- polarized UV exposure is performed in the +45 degree direction from the reference, and then the polarized
- 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. Therefore, the cured film forming composition of this Embodiment can be used suitably for manufacture of various retardation materials (retardation film), a liquid crystal display element, etc.
- MAA methacrylic acid MMA: methyl methacrylate
- HEMA 2-hydroxyethyl methacrylate
- AIBN ⁇ , ⁇ '-azobisisobutyronitrile
- HPCEL hydroxypropyl cellulose
- AADEG polyester (adipic acid / diethylene glycol)
- BTESA bis- ⁇ 3- (triethoxysilyl) propyl ⁇ amine
- BTMSA bis- ⁇ 3- (trimethoxysilyl) propyl ⁇ amine
- BTESE Bistriethoxysilylethane
- BTESAC N, N′-bis [(3-triethoxysilylpropyl) aminocarbonyl] polyethylene oxide
- 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 5 Comparative Examples 1 and 2> Each cured film forming composition of Examples 1 to 5 was prepared with the composition shown in Table 1, and adhesion, orientation sensitivity, pattern formability, and transmittance were evaluated for each.
- a coating film having a thickness of 1.0 ⁇ m was formed. This film was exposed at 1000 mJ / cm 2 to prepare a retardation material. A crosscut (1 mm ⁇ 1 mm ⁇ 100 square) is put into the retardation material on the obtained substrate using a cutter knife, and then a cellophane tape is applied, and then the film on the substrate is peeled off when the cellophane tape is peeled off. The number of squares remaining without peeling was counted. A film in which 90 or more cells remained without peeling off the film was judged to have good adhesion.
- a 1.0 ⁇ m coating film was formed.
- the coating film on this substrate was exposed at 1000 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.
- 313 nm linearly polarized light is irradiated vertically by 15 mJ / cm 2 to obtain an alignment material in which two types of liquid crystal alignment regions having different liquid crystal alignment control directions are formed by 90 degrees. It was.
- a polymerizable liquid crystal solution RMS03-013C for horizontal alignment manufactured by Merck Co., Ltd. was applied using a spin coater, and then pre-baked on a hot plate at 60 ° C. for 60 seconds to form a film.
- a coating film having a thickness of 1.0 ⁇ m was formed.
- the coating film on this substrate was exposed at 1000 mJ / cm 2 to prepare a patterned retardation material.
- the patterned phase difference material on the produced substrate was observed using a polarizing microscope, and evaluation was made with ⁇ indicating that the phase difference pattern was formed without alignment defects, and ⁇ indicating that the alignment defects were observed.
- Table 2 shows the results of the above evaluation.
- Examples 1 to 5 all showed liquid crystal alignment with a small exposure amount, showed high alignment sensitivity, and were able to perform optical patterning. Furthermore, it showed high transparency.
- Comparative Examples 1 and 2 had low alignment sensitivity and were difficult to perform optical patterning.
- the cured film forming composition according to the present invention is very useful as an alignment material for forming a liquid crystal alignment film of a liquid crystal display element and an optically anisotropic film provided inside or outside the liquid crystal display element, It is suitable as a material for forming a patterned retardation material for a 3D display. Further, a material for forming a cured film such as a protective film, a planarizing film and an insulating film in various displays such as a thin film transistor (TFT) type liquid crystal display element and an organic EL element, in particular, an interlayer insulating film and a color filter of the TFT type liquid crystal element It is also suitable as a material for forming a protective film or an insulating film of an organic EL element.
- TFT thin film transistor
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Abstract
Description
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).
(A)光配向性基とヒドロキシ基、カルボキシル基およびアミノ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)ヒドロキシ基、カルボキシル基およびアミノ基から選ばれる1種または2種以上の置換基を有する親水性ポリマー、並びに
(C)アミノ基を有するアルコキシシラン化合物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 photoalignment group and any one substituent selected from a hydroxy group, a carboxyl group and an amino group,
(B) A cured film containing a hydrophilic polymer having one or more substituents selected from a hydroxy group, a carboxyl group and an amino group, and (C) an alkoxysilane compound having an amino group Relates to forming compositions.
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)成分である親水性ポリマーと、(C)成分であるアミノ基を有するアルコキシシラン化合物とを含有する。本実施の形態の硬化膜形成組成物は、(A)成分、(B)成分、(C)成分に加えて、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。 <Curing film forming composition>
The cured film forming composition of the present embodiment includes a low molecular photo-alignment component as component (A), a hydrophilic polymer as component (B), and an alkoxysilane compound having an amino group as component (C). Containing. The cured film forming composition of the present embodiment contains other additives in addition to the component (A), the component (B), and the component (C), as long as the effects of the present invention are not impaired. Can do.
<(A)成分>
本実施の形態の硬化膜形成組成物に含有される(A)成分は、上述した、低分子の光配向成分である。 Hereinafter, details of each component will be described.
<(A) component>
The component (A) contained in the cured film forming composition of the present embodiment is the above-described low molecular photoalignment component.
尚、本発明において、光配向性基としては光二量化または光異性化する構造部位の官能基を言う。 And the low molecular photo-alignment component which is (A) component can be made into the compound which has a photo-alignment group and any one substituent chosen from a hydroxyl group, a carboxyl group, and an amino group. In a compound having a photo-alignment group and any one substituent selected from a hydroxy group, a carboxyl group and an amino group, as described above, the photoreactive group is a hydrophobic photoreactive moiety in the photoreaction component. And the hydroxy group or the like constitutes a hydrophilic thermal reaction part.
In the present invention, the photo-alignment group means a functional group at a structural site that undergoes photodimerization or photoisomerization.
光配向性基とアミノ基とを有する化合物の具体例としてはメチル-4-アミノけい皮酸、エチル-4-アミノけい皮酸、メチル-3-アミノけい皮酸、エチル-3-アミノけい皮酸等が挙げられる。
(A)成分である低分子の光配向成分は、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 having a photo-alignment group and a carboxyl group include cinnamic acid, ferulic acid, 4-nitrocinnamic acid, 4-methoxy cinnamic acid, 3,4-dimethoxy cinnamic acid, coumarin-3- Carboxylic acid, 4- (N, N-dimethylamino) cinnamic acid and the like can be mentioned.
Specific examples of the compound having a photo-alignment group and an amino group include methyl-4-aminocinnamic acid, ethyl-4-aminocinnamic acid, methyl-3-aminocinnamic acid, and ethyl-3-aminocinnamic acid. An acid etc. are mentioned.
Specific examples of the low molecular photo-alignment component as the component (A) are not limited to these.
本実施の形態の硬化膜形成組成物に含有される(B)成分は、親水性のポリマーである。
そして、(B)成分であるポリマーは、ヒドロキシ基、カルボキシル基およびアミノ基から選ばれる1種または2種以上の置換基を有するポリマー(以下、特定重合体とも言う。)とすることができる。 <(B) component>
The component (B) contained in the cured film forming composition of the present embodiment is a hydrophilic polymer.
And the polymer which is (B) component can be made into the polymer (henceforth a specific polymer) which has 1 type, or 2 or more types of substituents chosen from a hydroxy group, a carboxyl group, and an amino group.
このうち、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。 Examples of the polymer as the component (B) include acrylic polymer, polyamic acid, polyimide, polyvinyl alcohol, polyester, polyester polycarboxylic acid, polyether polyol, polyester polyol, polycarbonate polyol, polycaprolactone polyol, polyalkyleneimine, poly Examples include allylamines, celluloses (cellulose or derivatives thereof), polymers having a linear or branched structure such as phenol novolac resins and melamine formaldehyde resins, and cyclic polymers such as cyclodextrins.
Among these, as the acrylic polymer, a polymer obtained by polymerizing a monomer having an unsaturated double bond such as acrylic ester, methacrylic ester or styrene can be applied.
・ヒドロキシアルキルシクロデキストリン類、
・セルロース類、
・ポリエチレングリコールエステル基および炭素原子数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、カルボキシル基およ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、
・アミノアルキル基を側鎖に有するアクリル重合体、
・ポリエーテルポリオール、
・ポリエステルポリオール、
・ポリカーボネートポリオールおよび
・ポリカプロラクトンポリオールである。 The specific polymer as the component (B) is preferably
Hydroxyalkyl cyclodextrins,
・ Cellulose,
An acrylic polymer having at least one of a polyethylene glycol ester group and a hydroxyalkyl ester group having 2 to 5 carbon atoms, and at least one of a carboxyl group and a phenolic hydroxy group,
An acrylic polymer having an aminoalkyl group in the side chain,
・ Polyether polyol,
・ Polyester polyol,
Polycarbonate polyol and polycaprolactone polyol.
カルボキシル基およ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。 As a structural unit having at least one of a polyethylene glycol ester group and a hydroxyalkyl ester group having 2 to 5 carbon atoms, a preferred structural unit is represented by the following formula [B1].
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].
上述した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 carboxyl group described above include acrylic acid, methacrylic acid, and vinyl benzoic acid.
Examples of the monomer having a phenolic hydroxy group described above include p-hydroxystyrene, m-hydroxystyrene, and o-hydroxystyrene.
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モル%乃至80モル%、b2モノマーが20モル%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)成分との相溶性が低下し易い。 When a monomer having only a carboxyl group is used as the b2 monomer, the b1 monomer is 60 mol% to 95 mol% and the b2 monomer is based on the total amount of all monomers used to obtain the acrylic polymer as the component (B). 5 mol% to 40 mol% is preferable.
On the other hand, when a monomer having only a phenolic hydroxy group is used as the b2 monomer, it is preferable that the b1 monomer is 2 mol% to 80 mol% and the b2 monomer is 20 mol% to 98 mol%. When the b2 monomer is too small, the liquid crystal orientation tends to be insufficient, and when it is too large, the compatibility with the component (A) tends to decrease.
(B)成分のメラミンホルムアルデヒド樹脂は、保存安定性の観点からメラミンとホルムアルデヒドの重縮合の際に生成したメチロール基がアルキル化されていることが好ましい。 The melamine formaldehyde resin which is a preferable example of the specific polymer of the component (B) is a resin obtained by polycondensation of melamine and formaldehyde, and is represented by the following formula.
In the melamine formaldehyde resin as the component (B), it is preferable that the methylol group generated during the polycondensation of melamine and formaldehyde is alkylated from the viewpoint of storage stability.
本実施の形態の硬化膜形成組成物に含有される(C)成分は、アミノ基を有するアルコキシシラン化合物である。 <(C) component>
Component (C) contained in the cured film forming composition of the present embodiment is an alkoxysilane compound having an amino group.
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、(B)成分および(C)成分、および/または、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 in that case should just be able to melt | dissolve (A) component, (B) component and (C) component, and / or the other additive mentioned later, and the kind, structure, etc. are not specifically limited.
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.
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、(A)成分の光配向性成分より親水性であるポリマーと、(C)成分であるアミノ基を有するアルコキシシラン化合物とを含有する。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>
The cured film forming composition of the present embodiment is a (A) component low molecular photo-alignment component, and (B) component (A) a polymer that is more hydrophilic than the photo-alignment component; (C) the alkoxysilane compound which has an amino group which is a component. And as long as the effect of this invention is not impaired, another additive can be contained.
[1]:(A)成分と(B)成分の配合比が質量比で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、10質量部乃至100質量部の(C)成分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 component (A) and the component (B). A cured film forming composition containing 10 parts by mass to 100 parts by mass of component (C).
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%乃至80質量%であり、好ましくは3質量%乃至60質量%であり、より好ましくは5質量%乃至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% by mass to 60% by mass, more preferably 5% by mass to 40% by mass. 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.
そのため、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.
Therefore, the cured film forming composition of this Embodiment can be used suitably for manufacture of various retardation materials (retardation film), a liquid crystal display element, etc.
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。
<光配向性基とヒドロキシ基とを有する化合物>
CIN1:4-ヒドロキシヘキシルオキシけい皮酸メチルエステル
CIN2:3-メトキシ-4-ヒドロキシヘキシルオキシけい皮酸メチルエステル [Abbreviations used in Examples]
The meanings of the abbreviations used in the following examples are as follows.
<Compound having photoalignable group and hydroxy group>
CIN1: 4-hydroxyhexyloxycinnamic acid methyl ester CIN2: 3-methoxy-4-hydroxyhexyloxy cinnamic acid methyl ester
MAA:メタクリル酸
MMA:メタクリル酸メチル
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
HPCEL:ヒドロキシプロピルセルロース
AADEG:ポリエステル(アジピン酸/ジエチレングリコール) <Specific polymer raw material>
MAA: methacrylic acid MMA: methyl methacrylate HEMA: 2-hydroxyethyl methacrylate AIBN: α, α'-azobisisobutyronitrile HPCEL: hydroxypropyl cellulose AADEG: polyester (adipic acid / diethylene glycol)
BTESA:ビス-{3-(トリエトキシシリル)プロピル}アミン
BTMSA:ビス-{3-(トリメトキシシリル)プロピル}アミン <Alkoxysilane compound having an amino group>
BTESA: bis- {3- (triethoxysilyl) propyl} amine BTMSA: bis- {3- (trimethoxysilyl) propyl} amine
BTESE:ビストリエトキシシリルエタン
BTESAC:N,N‘-ビス[(3-トリエトキシシリルプロピル)アミノカルボニル]ポリエチレンオキシド <Alkoxysilane compound having no amino group>
BTESE: Bistriethoxysilylethane BTESAC: N, N′-bis [(3-triethoxysilylpropyl) aminocarbonyl] polyethylene oxide
PM:プロピレングリコールモノメチルエーテル <Solvent>
PM: Propylene glycol monomethyl ether
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 1>
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.
表1に示す組成にて実施例1乃至5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 5, Comparative Examples 1 and 2>
Each cured film forming composition of Examples 1 to 5 was prepared with the composition shown in Table 1, and adhesion, orientation sensitivity, pattern formability, and transmittance were evaluated for each.
実施例および比較例の各硬化膜形成組成物をアルカリガラス上にスピンコータを用いて2000rpmで30秒間回転塗布した後、温度110℃で120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50mJ/cm2照射した。露光後の基板上の配向材の上にメルク株式会社製の水平配向用重合性液晶溶液RMS03-013Cを、スピンコータを用いて塗布し、次いで、60℃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1000mJ/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、セロハンテープを貼り付け、次いで、そのセロハン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]
Each of the cured film forming compositions of Examples and Comparative Examples was spin-coated on an alkali glass at 2000 rpm for 30 seconds using a spin coater, and then heated and dried in a thermal circulation oven at 110 ° C. for 120 seconds to form a cured film. Formed. This cured film was irradiated with 50 mJ / cm 2 of 313 nm linearly polarized light vertically. On the alignment material on the substrate after the exposure, a polymerizable liquid crystal solution RMS03-013C for horizontal alignment manufactured by Merck Co., Ltd. was applied using a spin coater, and then pre-baked on a hot plate at 60 ° C. for 60 seconds, A coating film having a thickness of 1.0 μm was formed. This film was exposed at 1000 mJ / cm 2 to prepare a retardation material. A crosscut (1 mm × 1 mm × 100 square) is put into the retardation material on the obtained substrate using a cutter knife, and then a cellophane tape is applied, and then the film on the substrate is peeled off when the cellophane tape is peeled off. The number of squares remaining without peeling was counted. A film in which 90 or more cells remained without peeling off the film was judged to have good adhesion.
実施例および比較例の各硬化膜形成組成物をアルカリガラス上にスピンコータを用いて2000rpmで30秒間回転塗布した後、温度110℃で120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、メルク株式会社製の水平配向用重合性液晶溶液RMS03-013Cを、スピンコータを用いて塗布し、次いで、60℃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1000mJ/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]
Each of the cured film forming compositions of Examples and Comparative Examples was spin-coated on an alkali glass at 2000 rpm for 30 seconds using a spin coater, and then heated and dried in a thermal circulation oven at a temperature of 110 ° C. for 120 seconds to obtain a cured film. Formed. This cured film was irradiated vertically with 313 nm linearly polarized light to form an alignment material. On the alignment material on the substrate, a polymerizable liquid crystal solution RMS03-013C for horizontal alignment manufactured by Merck Co., Ltd. was applied using a spin coater, and then pre-baked on a hot plate at 60 ° C. for 60 seconds to obtain a film thickness. A 1.0 μm coating film was formed. The coating film on this substrate was exposed at 1000 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.
実施例および比較例の各硬化膜形成組成物をアルカリガラス上にスピンコータを用いて2000rpmで30秒間回転塗布した後、温度110℃で120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100μmのラインアンドスペースマスクを介し313nmの直線偏光を30mJ/cm2垂直に照射した。マスクを取り外し、基板を90度回転させた後、313nmの直線偏光を15mJ/cm2垂直に照射し、液晶の配向制御方向が90度異なる2種類の液晶配向領域が形成された配向材を得た。この基板上の配向材の上に、メルク株式会社製の水平配向用重合性液晶溶液RMS03-013Cを、スピンコータを用いて塗布し、次いで、60℃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1000mJ/cm2で露光し、パターン化位相差材を作製した。作製した基板上のパターン化位相差材を、偏光顕微鏡を用いて観察し、配向欠陥なく位相差パターンが形成されているものを○、配向欠陥が見られるものを×として評価した。 [Evaluation of pattern formability]
Each of the cured film forming compositions of Examples and Comparative Examples was spin-coated on an alkali glass at 2000 rpm for 30 seconds using a spin coater, and then heated and dried in a thermal circulation oven at 110 ° C. for 120 seconds to form a cured film. Formed. This cured film was irradiated with 313 nm linearly polarized light vertically by 30 mJ / cm 2 through a 100 μm line and space mask. After removing the mask and rotating the substrate by 90 degrees, 313 nm linearly polarized light is irradiated vertically by 15 mJ / cm 2 to obtain an alignment material in which two types of liquid crystal alignment regions having different liquid crystal alignment control directions are formed by 90 degrees. It was. On the alignment material on the substrate, a polymerizable liquid crystal solution RMS03-013C for horizontal alignment manufactured by Merck Co., Ltd. was applied using a spin coater, and then pre-baked on a hot plate at 60 ° C. for 60 seconds to form a film. A coating film having a thickness of 1.0 μm was formed. The coating film on this substrate was exposed at 1000 mJ / cm 2 to prepare a patterned retardation material. The patterned phase difference material on the produced substrate was observed using a polarizing microscope, and evaluation was made with ◯ indicating that the phase difference pattern was formed without alignment defects, and × indicating that the alignment defects were observed.
実施例および比較例の各硬化膜形成組成物を石英基板上にスピンコータを用いて2000rpmで30秒間回塗布した後、温度110℃で120秒間ホットプレート上において加熱乾燥ベークを行い膜厚300nmの硬化膜を形成した。膜厚はFILMETRICS社製 F20を用いて測定した。この硬化膜を紫外線可視分光光度計((株)島津製作所製SHIMADZU 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。 [Evaluation of light transmittance (transparency)]
Each of the cured film forming compositions of Examples and Comparative Examples was applied on a quartz substrate for 30 seconds at 2000 rpm using a spin coater, and then heat-dried and baked on a hot plate at 110 ° C. for 120 seconds to cure to a thickness of 300 nm. A film was formed. The film thickness was measured using F20 manufactured by FILMETRICS. The cured film was measured for transmittance with respect to light having a wavelength of 400 nm using an ultraviolet-visible spectrophotometer (SHIMADZU UV-2550 model number, manufactured by Shimadzu Corporation).
以上の評価を行った結果を表2に示す。 [Evaluation results]
Table 2 shows the results of the above evaluation.
Claims (13)
- (A)光配向性基とヒドロキシ基、カルボキシル基およびアミノ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)ヒドロキシ基、カルボキシル基およびアミノ基から選ばれる1種または2種以上の置換基を有する親水性ポリマー、並びに
(C)アミノ基を有するアルコキシシラン化合物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 photoalignment group and any one substituent selected from a hydroxy group, a carboxyl group and an amino group,
(B) A cured film containing a hydrophilic polymer having one or more substituents selected from a hydroxy group, a carboxyl group and an amino group, and (C) an alkoxysilane compound having an amino group Forming composition. - (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.
- (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 cinnamoyl group.
- (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乃至3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 3, wherein the photoalignable group of the component (A) is a group having an azobenzene structure.
- (A)成分が2個以上のヒドロキシ基を有することを特徴とする請求項1乃至4のいずれか1項に記載の硬化膜形成組成物。 The (A) component has two or more hydroxy groups, The cured film forming composition of any one of Claims 1 thru | or 4 characterized by the above-mentioned.
- (B)成分が、ポリエーテルポリオール、ポリエステルポリオール、ポリカーボネートポリオールおよびポリカプロラクトンポリオールよりなる群から選ばれた少なくとも1種のポリマーであることを特徴とする請求項1乃至5のいずれか1項に記載の硬化膜形成組成物。 The component (B) is at least one polymer selected from the group consisting of polyether polyols, polyester polyols, polycarbonate polyols, and polycaprolactone polyols, according to any one of claims 1 to 5. Cured film forming composition.
- (B)成分がセルロースまたはその誘導体であることを特徴とする請求項1乃至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 component (B) is cellulose or a derivative thereof.
- (B)成分が、ポリエチレングリコールエステル基および炭素原子数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、カルボキシル基およ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ことを特徴とする請求項1乃至5のいずれか1項に記載の硬化膜形成組成物。 The component (B) is an acrylic polymer having at least one of a polyethylene glycol ester group and a hydroxyalkyl ester group having 2 to 5 carbon atoms, and at least one of a carboxyl group and a phenolic hydroxy group. The cured film forming composition according to any one of claims 1 to 5, wherein:
- (B)成分がシクロデキストリンまたはその誘導体であることを特徴とする請求項1乃至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 component (B) is cyclodextrin or a derivative thereof.
- (A)成分と(B)成分の比率が質量比で5:95乃至60:40であることを特徴とする請求項1乃至9のいずれか1項に記載の硬化膜形成組成物。 The ratio of the (A) component and the (B) component is 5:95 thru | or 60:40 by mass ratio, The cured film formation composition of any one of the Claims 1 thru | or 9 characterized by the above-mentioned.
- (A)成分および(B)成分の合計量100質量部に基づいて、10質量部乃至100質量部の(C)成分を含有することを特徴とする請求項1乃至10のいずれか1項に記載の硬化膜形成組成物。 The component (A) and the component (B) based on a total amount of 100 parts by mass, containing 10 parts by mass to 100 parts by mass of the component (C), according to any one of claims 1 to 10. The cured film forming composition as described.
- 請求項1乃至11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 11.
- 請求項1乃至11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 any one of claims 1 to 11.
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014065324A1 (en) * | 2012-10-24 | 2014-05-01 | 日産化学工業株式会社 | Cured-film-forming composition, alignment material, and phase-difference material |
WO2014104320A1 (en) * | 2012-12-27 | 2014-07-03 | 日産化学工業株式会社 | Composition for forming cured film, orientation material, and phase difference material |
WO2014136889A1 (en) * | 2013-03-08 | 2014-09-12 | 日産化学工業株式会社 | Cured-film forming composition, alignment material, and retardation material |
TWI757687B (en) * | 2014-02-28 | 2022-03-11 | 日商日產化學工業股份有限公司 | Resin composition for forming retardation material, alignment material and retardation material |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016143860A1 (en) * | 2015-03-11 | 2016-09-15 | 日産化学工業株式会社 | Cured film-forming composition, alignment material and the phase difference material |
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11131013A (en) * | 1997-10-31 | 1999-05-18 | Hitachi Chem Co Ltd | Resin composition for color filter protecting film, and color filter protecting film and color filter using the same |
JP2003160711A (en) * | 2001-11-27 | 2003-06-06 | Dainippon Ink & Chem Inc | Thermosetting resin composition, protective film material for optical device, resin cured product and color filter |
JP2007009048A (en) * | 2005-06-30 | 2007-01-18 | Sumitomo Chemical Co Ltd | Composition for forming insulating film and method for producing insulating film |
JP2007092070A (en) * | 2005-09-05 | 2007-04-12 | Jts Kk | Thermoset type aqueous ultra-violet ray protection paint, and ultra-violet light protection cut-glass bottle and plate glass |
JP2011001421A (en) * | 2009-06-17 | 2011-01-06 | Asahi Kasei Chemicals Corp | Photosensitive resin composition, and photosensitive inkjet ink, photosensitive adhesive, photosensitive coating agent and semiconductor sealing material using the same |
WO2011010635A1 (en) * | 2009-07-21 | 2011-01-27 | 日産化学工業株式会社 | Composition forming heat cured film having photo alignment property |
WO2011126022A1 (en) * | 2010-04-08 | 2011-10-13 | 日産化学工業株式会社 | Composition forming heat-cured film having photo-alignment properties |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6097324A (en) * | 1983-10-31 | 1985-05-31 | Sharp Corp | Manufacture of liquid crystal display element |
JPS611342A (en) | 1984-06-14 | 1986-01-07 | Noboru Yamada | Smoking process |
JPS61277921A (en) * | 1985-05-31 | 1986-12-08 | Nitto Electric Ind Co Ltd | Production of liquid crystal sandwiching substrate |
JP3767962B2 (en) | 1997-02-19 | 2006-04-19 | シャープ株式会社 | Video display system |
CN1211418C (en) | 1997-09-25 | 2005-07-20 | 罗列克股份公司 | Photocrosslinkable polyimides |
JP2000302792A (en) * | 1999-04-19 | 2000-10-31 | Ck Witco Corp | Bis-silyl tertiary amines |
JP2002241722A (en) * | 2001-02-19 | 2002-08-28 | Sumitomo Bakelite Co Ltd | Anisotropic conductive adhesive |
US7074344B2 (en) * | 2001-10-03 | 2006-07-11 | Jsr Corporation | Liquid crystal aligning agent and liquid crystal display element |
JP2005049865A (en) | 2003-07-17 | 2005-02-24 | Arisawa Mfg Co Ltd | Manufacturing method of optical phase difference element |
JP4128116B2 (en) * | 2003-07-29 | 2008-07-30 | 旭化成エレクトロニクス株式会社 | Positive photosensitive resin composition |
JP2009040984A (en) * | 2007-08-13 | 2009-02-26 | Dainippon Printing Co Ltd | Liquid crystal composition, retardation-controlling members using the same, and liquid crystal display |
JP5316740B2 (en) | 2007-08-30 | 2013-10-16 | Jsr株式会社 | Method for forming liquid crystal alignment film |
JP2009104065A (en) * | 2007-10-25 | 2009-05-14 | Nippon Zeon Co Ltd | Luminance enhancing film and liquid crystal display device |
JP5413610B2 (en) * | 2008-04-28 | 2014-02-12 | Jsr株式会社 | Liquid crystal aligning agent and method for forming liquid crystal aligning film |
JP2010235786A (en) * | 2009-03-31 | 2010-10-21 | Aica Kogyo Co Ltd | Modified silicone resin composition |
WO2010117223A2 (en) * | 2009-04-09 | 2010-10-14 | 주식회사 엘지화학 | Alignment layer composition, alignment layer prepared with the same, preparation method of alignment layer, optical film containing the same, and display device including the optical film |
KR20130045856A (en) * | 2010-04-08 | 2013-05-06 | 닛산 가가쿠 고교 가부시키 가이샤 | Composition forming heat-cured film having photo-alignment properties |
-
2013
- 2013-03-19 WO PCT/JP2013/057824 patent/WO2013146469A1/en active Application Filing
- 2013-03-19 CN CN201380016279.6A patent/CN104204120B/en active Active
- 2013-03-19 JP JP2014507754A patent/JP6086115B2/en active Active
- 2013-03-19 KR KR1020147026994A patent/KR102097067B1/en active IP Right Grant
- 2013-03-27 TW TW106109788A patent/TWI627214B/en active
- 2013-03-27 TW TW102110902A patent/TWI627210B/en active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11131013A (en) * | 1997-10-31 | 1999-05-18 | Hitachi Chem Co Ltd | Resin composition for color filter protecting film, and color filter protecting film and color filter using the same |
JP2003160711A (en) * | 2001-11-27 | 2003-06-06 | Dainippon Ink & Chem Inc | Thermosetting resin composition, protective film material for optical device, resin cured product and color filter |
JP2007009048A (en) * | 2005-06-30 | 2007-01-18 | Sumitomo Chemical Co Ltd | Composition for forming insulating film and method for producing insulating film |
JP2007092070A (en) * | 2005-09-05 | 2007-04-12 | Jts Kk | Thermoset type aqueous ultra-violet ray protection paint, and ultra-violet light protection cut-glass bottle and plate glass |
JP2011001421A (en) * | 2009-06-17 | 2011-01-06 | Asahi Kasei Chemicals Corp | Photosensitive resin composition, and photosensitive inkjet ink, photosensitive adhesive, photosensitive coating agent and semiconductor sealing material using the same |
WO2011010635A1 (en) * | 2009-07-21 | 2011-01-27 | 日産化学工業株式会社 | Composition forming heat cured film having photo alignment property |
WO2011126022A1 (en) * | 2010-04-08 | 2011-10-13 | 日産化学工業株式会社 | Composition forming heat-cured film having photo-alignment properties |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014065324A1 (en) * | 2012-10-24 | 2014-05-01 | 日産化学工業株式会社 | Cured-film-forming composition, alignment material, and phase-difference material |
WO2014104320A1 (en) * | 2012-12-27 | 2014-07-03 | 日産化学工業株式会社 | Composition for forming cured film, orientation material, and phase difference material |
WO2014136889A1 (en) * | 2013-03-08 | 2014-09-12 | 日産化学工業株式会社 | Cured-film forming composition, alignment material, and retardation material |
US9529132B2 (en) | 2013-03-08 | 2016-12-27 | Nissan Chemical Industries, Ltd. | Cured film formation composition, orientation material, and retardation material |
US9823401B2 (en) | 2013-03-08 | 2017-11-21 | Nissan Chemical Industries, Ltd. | Cured film formation composition, orientation material, and retardation material |
TWI757687B (en) * | 2014-02-28 | 2022-03-11 | 日商日產化學工業股份有限公司 | Resin composition for forming retardation material, alignment material and retardation material |
Also Published As
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CN104204120B (en) | 2017-03-08 |
JPWO2013146469A1 (en) | 2015-12-10 |
TWI627210B (en) | 2018-06-21 |
TW201404816A (en) | 2014-02-01 |
JP6086115B2 (en) | 2017-03-01 |
TW201726798A (en) | 2017-08-01 |
TWI627214B (en) | 2018-06-21 |
KR102097067B1 (en) | 2020-04-03 |
KR20140142257A (en) | 2014-12-11 |
CN104204120A (en) | 2014-12-10 |
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