WO2012018121A1 - 樹脂組成物、液晶配向材および位相差材 - Google Patents
樹脂組成物、液晶配向材および位相差材 Download PDFInfo
- Publication number
- WO2012018121A1 WO2012018121A1 PCT/JP2011/067969 JP2011067969W WO2012018121A1 WO 2012018121 A1 WO2012018121 A1 WO 2012018121A1 JP 2011067969 W JP2011067969 W JP 2011067969W WO 2012018121 A1 WO2012018121 A1 WO 2012018121A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- component
- resin composition
- group
- composition according
- liquid crystal
- Prior art date
Links
Images
Classifications
-
- 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
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
- C08G73/1053—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the tetracarboxylic moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
- C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- 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
-
- 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
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/13363—Birefringent elements, e.g. for optical compensation
Definitions
- the present invention relates to a resin composition, a liquid crystal alignment material, and a retardation material.
- a retardation film has been arranged outside the liquid crystal cell for the purpose of compensating the viewing angle of the liquid crystal display.
- the type of the retardation film varies depending on the liquid crystal display mode in the liquid crystal display.
- a biaxial plate having different in-plane x and y directions and three refractive indexes in the thickness direction is used as a retardation film alone, or it is produced by uniaxial stretching.
- the viewing angle is compensated by combining the positive A plate and the negative C plate into a retardation film.
- the former is produced by biaxial stretching, and the latter is produced by uniaxial stretching.
- phase difference material is formed by applying a polymerizable liquid crystal solution to an appropriate portion in a liquid crystal cell, and performing photo-curing after a desired orientation.
- a polymerizable liquid crystal exhibiting horizontal alignment is used in the case of a positive A plate.
- a polymerizable liquid crystal exhibiting cholesteric alignment or discotic alignment is used in the case of a negative C plate.
- a polymerizable liquid crystal exhibiting biaxial orientation is used in the case of a biaxial plate. Therefore, in order to introduce a retardation material having a biaxial retardation into the liquid crystal cell, a polymerizable liquid crystal exhibiting biaxial alignment is used, or a polymerizable liquid crystal exhibiting cholesteric alignment and horizontal alignment are used. It was necessary to laminate and use the polymerizable liquid crystal shown.
- FIG. 2 is a schematic configuration diagram of a liquid crystal cell in which a liquid crystal alignment film is formed by a conventional technique.
- the liquid crystal layer 208 is sandwiched between two substrates 201 and 211.
- an ITO 210 and an alignment film 209 are formed on the substrate 211.
- a color filter 202, a color filter (CF) overcoat (hereinafter referred to as a CF overcoat) 203, an alignment film 204, a phase difference material 205, an ITO 206, an alignment A film 207 is formed in this order.
- CF color filter
- the alignment film is formed through processes such as rubbing treatment and polarized light irradiation. That is, as shown in FIG. 2, conventionally, after the alignment film 204 is formed on the CF overcoat 203, a retardation material 205 obtained from a polymerizable liquid crystal such as a liquid crystal monomer is formed thereon. It was common. That is, after the color filter 202 is formed, it is necessary to further form two layers of the CF overcoat 203 and the alignment film 204, which complicates the manufacturing process.
- a film that serves as both an alignment film and a CF overcoat is required to have a high birefringence. This is because the characteristics of the negative C plate can be imparted by increasing the birefringence.
- a highly transparent acrylic resin is used for the CF overcoat.
- heat resistance and solvent resistance are expressed by hardening an acrylic resin with a heat
- a conventional CF overcoat made of a thermosetting or photocurable acrylic resin can provide transparency and solvent resistance, it can be irradiated with polarized UV light. It has been found that sufficient liquid crystal orientation cannot be exhibited. Therefore, it is understood that the conventional CF overcoat cannot be applied as it is to a film serving as both the alignment film and the CF overcoat.
- the reaction rate of the photodimerization reaction in the acrylic resin can be improved by a large amount of polarized UV exposure of 1 J / cm 2 or more. Therefore, there is a possibility that the orientation of the polymerizable liquid crystal can be improved by increasing the exposure amount.
- the photo-alignment technique has been studied for the purpose of shortening the time for the alignment process in the first place, it is not possible to allow an increase in exposure amount that leads to a longer exposure time.
- the photodimerization reaction for realizing the liquid crystal orientation is not sufficient as a crosslinking reaction, and sufficient heat resistance as a film is realized. It has also been found that it cannot be done. That is, it has been found that the film made of the above acrylic resin undergoes large film shrinkage by the heat treatment for manufacturing the liquid crystal cell when the reaction rate is improved.
- the present invention has been made based on the above knowledge and examination results. That is, the object of the present invention is to align the polymerizable liquid crystal with high sensitivity after thermosetting by utilizing photo-alignment technology, and also has high birefringence, high solvent resistance, heat resistance and high transparency. It is in providing the resin composition shown.
- the first aspect of the present invention is: (A) an acrylic copolymer having a photodimerization site comprising a hydrophobic group and a thermal crosslinking site comprising a hydrophilic group; (B) a polyimide precursor having an aromatic ring moiety; (C) about the component (A) and (B) component and a resin composition containing a crosslinking agent for crosslinking.
- the component (A) is preferably an acrylic copolymer obtained by a polymerization reaction of a monomer mixture containing a monomer having a photodimerization site and a monomer having a thermal crosslinking site.
- the component (A) is an acrylic copolymer obtained by a polymerization reaction of a monomer mixture containing 25 to 90 mol% of a monomer having a photodimerization site with respect to the total amount of all the monomer mixtures.
- a polymer is preferred.
- the photodimerization site of the component (A) is preferably a cinnamoyl group.
- the thermal crosslinking site of the component (A) is preferably a hydroxyl group or a carboxyl group.
- the polyimide precursor of component (B) preferably has a biphenyl structure in the main chain.
- WHEREIN (B) component is a polyimide precursor containing the structural unit obtained from the copolymerization reaction of tetracarboxylic dianhydride and a diamine compound, Comprising: Tetracarboxylic dianhydride and diamine It is preferable that at least one of the compounds has a biphenyl structure.
- the tetracarboxylic dianhydride is preferably biphenyltetracarboxylic dianhydride.
- the component (B) is preferably a polyimide precursor having a trifluoromethyl group in the structural unit.
- the polyimide precursor of component (B) preferably has an alicyclic structure in the main chain.
- WHEREIN (B) component is a polyimide precursor containing the structural unit obtained from the copolymerization reaction of tetracarboxylic dianhydride and a diamine compound, Comprising: Tetracarboxylic dianhydride and diamine It is preferable that at least one of the compounds has an alicyclic structure.
- the crosslinking agent of component (C) is preferably a crosslinking agent having a methylol group or an alkoxymethylol group.
- component (C) it is preferable to contain 10 to 100 parts by mass of component (C) based on 100 parts by mass of the total amount of component (A) and component (B).
- component (D) it is preferable to further contain an acid or a thermal acid generator as component (D).
- component (D) it is preferable to contain 0.1 to 10 parts by mass of component (D) 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 a liquid crystal alignment material characterized by being obtained using the resin composition of the first aspect of the present invention.
- the third aspect of the present invention relates to a retardation material characterized by being formed using a cured film obtained from the resin composition of the first aspect of the present invention.
- a cured film capable of photoalignment of liquid crystal is obtained. It is done.
- liquid crystal aligning material having a high birefringence and excellent in light transmittance, solvent resistance and orientation can be obtained.
- a retardation material that can be arranged in a liquid crystal cell is obtained.
- the contrast ratio can be improved.
- the present invention relates to a resin composition, a liquid crystal alignment material formed using the resin composition, and a retardation material formed using a cured film obtained from the resin composition. More specifically, a resin composition capable of forming a cured film having a high birefringence, high transparency, liquid crystal alignment ability, high solvent resistance, and heat resistance, and the resin composition are used. Liquid crystal aligning material, and a phase difference material formed using the liquid crystal aligning material.
- the resin composition of the present invention is suitable as a film having a function as a CF overcoat in a liquid crystal display, and also has an alignment function with respect to the polymerizable liquid crystal for forming a retardation layer. It is also suitable for forming a layer.
- the resin composition of the present embodiment is a resin composition for forming a thermosetting film having photo-alignment properties, that is, a resin composition for forming a photo-alignment thermosetting film.
- the thermosetting film having photo-alignment means a cured film that is cured by heating and induces alignment performance of liquid crystal by polarized light exposure.
- the resin composition of the present embodiment contains an acrylic copolymer having a photodimerization site and a thermal crosslinking site as the component (A), a polyimide precursor as the component (B), and a crosslinking agent as the component (C). To do.
- the photodimerization site of the acrylic copolymer, which is component (A), consists of a hydrophobic group
- the thermal crosslinking site of the acrylic copolymer consists of a hydrophilic group
- the polyimide precursor which is (B) component has an aromatic ring site
- the crosslinking agent as the component (C) can crosslink the component (A) and the component (B).
- the resin composition of the present embodiment is (A) an acrylic copolymer having a photodimerization site consisting of a hydrophobic group and a thermal crosslinking site consisting of a hydrophilic group; (B) a polyimide precursor having an aromatic ring site; (C) It is comprised containing the crosslinking agent which bridge
- an acid or photoacid generator as the component (D) and / or (E) It can contain a sensitizer as a component.
- liquid crystal alignment performance can be imparted to the cured film obtained using this resin composition by photo-alignment treatment. That is, when the acrylic copolymer as component (A) has a photodimerization site consisting of a hydrophobic group and a thermal cross-linking site consisting of a hydrophilic group, the heat at the thermal cross-linking site described later by heating after coating. The crosslinking reaction proceeds and cures. At this time, the photodimerization site comprising a hydrophobic group exists not only in the vicinity of the surface of the cured film but also in a free state protruding from the surface.
- the component (A) has a thermal crosslinking site.
- This thermal cross-linking site can be made of a hydrophilic group, whereby a thermal cross-linking reaction can be efficiently caused with the later-described (C) cross-linking agent.
- C later-described cross-linking agent.
- a cross-linking site by a thermal reaction can be introduced, so that the number of cross-linking sites can be increased. Therefore, dissolution of the cured film due to the application of the polymerizable liquid crystal solution on the cured film can be prevented. Moreover, it can also suppress that a cured film heat-shrinks in the heating environment in the manufacturing process of a liquid crystal cell.
- the resin composition of this Embodiment can adjust the birefringence of the cured film obtained using this resin composition by containing (B) component. That is, the polyimide precursor of component (B) becomes a polyimide by thermal reaction to form a cured film, but by selecting a molecular structure including a benzene ring structure or a biphenyl structure in the main chain of this polyimide precursor It is possible to impart high birefringence to the cured film. At this time, there is a concern that the light transmittance of the cured film, that is, the transparency may be lowered, but by selecting the molecular structure of the compound constituting the polyimide precursor, it is possible to suppress the decrease in the transmittance. is there.
- the compound constituting the polyimide precursor by selecting a compound having an alicyclic structure as the compound constituting the polyimide precursor, it becomes possible to impart high transparency to the cured film. That is, both high birefringence and high transparency can be imparted to the cured film by appropriately designing the molecular structure of the polyimide precursor.
- the resin composition of this Embodiment can introduce
- the cross-linking reaction between the component (B) and the component (C) can be controlled, and as a result, between the component (A) and the component (C). It is possible to control the crosslinking reaction. As a result, in the entire cured film obtained from the resin composition, an efficient crosslinking reaction by a thermal reaction is realized, and a strong cured film can be formed by introducing a crosslinking site.
- the component (A) in the present embodiment is an acrylic copolymer having a photodimerization site and a thermal crosslinking site.
- part of the acrylic copolymer of a component consists of a hydrophobic group, and a thermal-crosslinking site
- part consists of a hydrophilic group.
- acrylic copolymer a copolymer obtained by polymerizing a monomer having an unsaturated double bond such as acrylic ester, methacrylic ester or styrene can be used.
- Acrylic copolymer having a light dimerization site and thermal crosslinking site as the component (A) (hereinafter, also referred to as a specific copolymer.) May be any acrylic copolymer having such a structure, the acrylic copolymer.
- the photodimerization site 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.
- a cinnamoyl group having high transparency in the visible light region and photodimerization reactivity is preferable.
- Particularly preferred cinnamoyl group partial structures are shown in the following formulas [A1] and [A2].
- X 1 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group or a biphenyl group.
- the phenyl group and the biphenyl group may each be substituted with either a halogen atom or a cyano group.
- X 2 represents a hydrogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, or a cyclohexyl group.
- alkyl group a phenyl group having a carbon number of 1-18, a biphenyl group or a cyclohexyl group is a covalent bond, an ether bond, an ester bond may be attached via an amide bond or a urea bond.
- R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a trifluoromethyl group or a cyano group.
- the thermal crosslinking site is a site that is bonded to a crosslinking agent by heating, and specific examples thereof include a hydroxy group, a carboxyl group, or a glycidyl group.
- the acrylic copolymer as 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. More preferably. If the weight average molecular weight is over 200,000, the solubility in a solvent may be lowered, and the handling property may be lowered. On the other hand, if the weight average molecular weight is less than 3,000 and is too small, curing may be insufficient during thermosetting, and solvent resistance and heat resistance may be reduced.
- a monomer having a photodimerization site and a monomer having a thermal crosslinking site are copolymerized. Is preferred.
- 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 favorable transparency in the visible light region and good photodimerization reactivity is preferable.
- a monomer having a cinnamoyl group having a structure represented by the above formula [A1] or [A2] is preferable. Specific examples of such monomers are shown in the following formulas [A3] and [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 may each be substituted with either a halogen atom or a cyano group.
- X 2 represents a hydrogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, or a cyclohexyl group.
- the alkyl group having 1 to 18 carbon atoms, the phenyl group, the biphenyl group, and the cyclohexyl group may be bonded via a covalent bond, an ether bond, an ester bond, an amide bond, or a urea bond.
- X 3 and X 5 each independently represent a single bond, an alkylene group having 1 to 20 carbon atoms, an aromatic ring group or an alicyclic group.
- the alkylene group having 1 to 20 carbon atoms may be linear in branched.
- X 4 and X 6 represent a polymerizable group.
- this polymerizable group examples include acryloyl group, methacryloyl group, styrene group, maleimide group, acrylamide group, and methacrylamide group.
- R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a trifluoromethyl group or a cyano group.
- Examples thereof include 4- (6-methacryloxyhexyl-1-oxy) cinnamic acid methyl ester and 6- (acryloyloxy) hexyl-3- (4-methoxyphenyl) acrylate.
- 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 and 5-methacryloyloxy-6-hydroxynorbornene-2-carboxy
- a specific copolymer when a specific copolymer is obtained, in addition to a monomer having a photodimerization site and a thermal crosslinking site (hereinafter also referred to as a specific functional group), such a monomer can be copolymerized.
- a monomer having no specific functional group can be used in combination.
- the monomer having no specific functional group examples include acrylic ester compounds, methacrylic ester compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds, and vinyl compounds. Specific examples thereof include the following. However, it is not limited to these.
- acrylic ester compounds 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, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 2-aminoethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2- Methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate Over DOO, such as 8-methyl-8-tricyclodecyl acrylate, and 8-
- 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, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2- Methyl-2-adamantyl methacrylate DOO, .gamma.-butyrolactone methacrylate
- Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl carbazole, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo [4.1.0] heptane, 1,2-epoxy-5-hexene and Examples include 1,7-octadiene monoepoxide.
- styrene compound examples include styrene, methylstyrene, chlorostyrene, and bromostyrene.
- maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.
- 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% by weight 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 thermosetting property, and it is difficult to maintain high sensitivity and good liquid crystal alignment.
- the method for obtaining the specific copolymer is not particularly limited.
- a polymerization reaction at a temperature of 50 to 110 ° C. in a solvent in which a monomer having a specific functional group, a monomer having no specific functional group, and a polymerization initiator coexist if desired.
- a specific copolymer can be obtained.
- the solvent used at this time is not particularly limited as long as it dissolves a monomer having a specific functional group, a monomer having no specific functional group, and a polymerization initiator, if desired. This solvent will also be described in the ⁇ Solvent> column described later.
- the specific copolymer obtained by the above method is usually in a solution state dissolved in a solvent. Moreover, the solution of the specific copolymer obtained by the above method is poured into diethyl ether or water under stirring and reprecipitated, and after the generated precipitate is filtered and washed, under normal pressure or reduced pressure, It can be dried at room temperature or heat to obtain a powder of the specific copolymer. By such an operation, the polymerization initiator coexisting with the specific copolymer and the unreacted monomer can be removed, and as a result, a purified powder of the specific copolymer can be 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 may be used 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.
- the component (B) in the present embodiment is a polyimide precursor.
- the polyimide precursor as a component has an aromatic ring part.
- a polyimide precursor having a structural unit represented by the following formula (1) is preferable among the polyimide precursors.
- a 1 is an organic group containing at least one structure having an aromatic ring portion such as a alicyclic structure or a skeleton in which 1 to 3 benzene rings are directly linked, a naphthalene ring skeleton, and an anthracene ring skeleton.
- B 1 is an organic group containing at least one structure having an alicyclic structure or an aromatic ring moiety such as a benzene ring having a trifluoromethyl group or a group containing a trifluoromethyl group
- R 5 and R 6 are Each independently represents a hydrogen atom or an organic group having 1 to 7 carbon atoms.
- at least one of A 1 and B 1 is an organic group including a structure having an aromatic ring moiety.
- a 1 in the formula (1) include organic groups including structures represented by T1 to T9 shown in Table 1 below. However, it is not limited to these.
- B 1 in the formula (1) is an organic group containing at least one benzene ring having an alicyclic structure or a trifluoromethyl group or a group containing a trifluoromethyl group.
- specific examples of the organic group containing a benzene ring having an alicyclic structure or a trifluoromethyl group or a group containing a trifluoromethyl group include organic groups represented by S1 to S7 shown in Table 2 below. Can be mentioned.
- the polyimide precursor as the component (B) may contain other structural units other than the structural unit represented by the above formula (1).
- other structural units are not particularly limited.
- 1 type or multiple types of structural units other than the structural unit represented by Formula (1) may be included.
- the weight average molecular weight of the polyimide precursor as a component is 1000-100000, Preferably it is 1500-60000. If the weight average molecular weight of the polyimide precursor is less than 1000, the solvent resistance may decrease and the orientation sensitivity may decrease. On the other hand, when the weight average molecular weight of a polyimide precursor exceeds 100,000, the viscosity of a solution is too high and handling property falls.
- the polyimide precursor of (B) component is obtained by copolymerizing a tetracarboxylic dianhydride and a diamine compound.
- tetracarboxylic dianhydride examples include a tetracarboxylic dianhydride including at least one alicyclic structure, a tetracarboxylic dianhydride including at least one structure in which 1 to 3 benzene rings are directly connected, or a naphthalene ring.
- a tetracarboxylic dianhydride containing at least one is preferable.
- the acid dianhydride include pyromellitic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid Anhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,5,6-anthracenetetracarboxylic dianhydride 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride and 2,3,3 ′, 4′-biphenyltetracarboxylic Acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohe
- tetracarboxylic dianhydrides other than those described above may be included as the tetracarboxylic dianhydride component.
- other tetracarboxylic dianhydrides may be one kind or plural kinds.
- tetracarboxylic dianhydrides include, for example, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenonetetracarboxylic dianhydride things, bis (3,4-carboxyphenyl) methane dianhydride, bis (3,4-carboxyphenyl) ether dianhydride, bis (3,4-carboxyphenyl) sulfone dianhydride, 2,2 -Bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,5-dicarboxymethyl terephthalic acid dianhydride, 4,6-di-carboxymethyl-isophthalic acid dianhydride, 4- (2,5-dioxo-3-furanyl) phthalic anhydride, 1,4-bis (2,5-
- a diamine compound containing an alicyclic structure or a trifluoromethyl group is preferable, and it may be used in combination with other diamine compounds.
- diamine compounds include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, 1,4 '-Bicyclohexyldiamine, 2,2'-trifluoromethyl-4,4'-diaminobiphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 2, 2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (3-amin
- one or a plurality of other diamine compounds other than the diamine compounds described above can be used.
- Examples of other diamine compounds include bis (4-aminophenyl) sulfone, bis (3-aminophenyl) sulfone, bis (4-amino-3-carboxyphenyl) sulfone, and bis (4-amino-3,5- Dicarboxyphenyl) sulfone, bis [4- (4-amino-3-carboxyphenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] Sulfone, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, bis (4-amino-3,5-dihydroxyphenyl) sulfone, 3,3′-diamino- 4,4'-dichlorodiphenylsulfone, p-phenylenedi
- the blending ratio of the total amount of tetracarboxylic dianhydride (total amount of acid component) and the total amount of diamine compound (total amount of diamine component), that is, ⁇ diamine compound is preferably 0.5 to 1.5.
- the end of the polyimide precursor of the component changes depending on the blending ratio of the acid component and the diamine component, but is not particularly limited in the present embodiment.
- the terminal amino group can be protected by reacting the terminal amino group with a carboxylic acid anhydride.
- carboxylic anhydrides include phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalic anhydride, hydrogenated phthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic acid An acid anhydride, itaconic anhydride, tetrahydrophthalic anhydride, etc. can be mentioned.
- the reaction temperature between the acid component and the diamine component can be selected from -20 to 150 ° C, preferably -5 to 100 ° C.
- a polyimide precursor can be obtained by setting the reaction temperature to 5 to 40 ° C. and the reaction time to 1 to 48 hours.
- the reaction temperature for protecting the terminal amino group with an acid anhydride can be selected from any temperature of ⁇ 20 to 150 ° C., preferably ⁇ 5 to 100 ° C.
- the reaction between the acid component and the diamine component is usually performed in a solvent.
- the solvent that can be used in this case include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, dimethylsulfone, Hexamethyl sulfoxide, m-cresol, ⁇ -butyrolactone, methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate, 2-ethoxy Ethyl propionate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, propylene glycol dimethyl ether Ter, diprop
- the solution containing the polyimide precursor thus obtained can be used as it is for the preparation of a resin composition for forming a thermosetting film.
- the polyimide precursor can also be used after being recovered by precipitation isolation in a poor solvent such as water, methanol and ethanol.
- (C) component of this Embodiment is a crosslinking agent.
- This crosslinking agent can crosslink the component (A) and the component (B).
- crosslinking agent (C) examples include an epoxy compound, a methylol compound or an isocyanate compound, and a methylol compound having two or more methylol groups or alkoxymethylol groups is preferable.
- Specific examples include compounds such as methoxymethylated glycoluril, methoxymethylated benzoguanamine and methoxymethylated melamine. Further, for example, hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, 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) urea, 1,3-bis (hydroxymethyl) -4,5 -Dihydroxy-2-imidazolinone and 1,3-bis (methoxymethyl) -4,5-dimethoxy-2-imidazolinone.
- methoxymethyl type melamine compounds (trade names Cymel 300, Cymel 301, Cymel 303, Cymel 350) manufactured by Nippon Cytec Industries, Ltd., butoxymethyl type melamine compounds (trade names My Coat 506, My Coat 508) ), Compounds such as glycoluril compounds (trade names Cymel 1170, Powderlink 1174), methylated urea resins (trade names UFR65), butylated urea resins (trade names UFR300, U-VAN10S60, U-VAN10R, U-VAN11HV)
- urea / formaldehyde resin high condensation type, trade name becamine J-300S, becamine P-955, becamine N
- DIC Corporation DIC Corporation
- it may be a compound obtained by condensing a melamine compound, urea compound, glycoluril compound and benzoguanamine compound in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group.
- a melamine compound trade name Cymel 303
- the benzoguanamine compound trade name Cymel 1123
- an acrylamide compound substituted with a hydroxymethyl group or an alkoxymethyl group such as N-hydroxymethyl acrylamide, N-methoxymethyl methacrylamide, N-ethoxymethyl acrylamide, N-butoxymethyl methacrylamide, or methacryl
- a polymer produced using an amide compound 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, N-ethoxymethylmethacrylamide and benzyl.
- Examples thereof include a copolymer of methacrylate and a copolymer of N-butoxymethylacrylamide, benzyl methacrylate, and 2-hydroxypropyl methacrylate.
- the weight average molecular weight of such a polymer is, for example, 1,000 to 500,000, for example, 2,000 to 200,000, or 3,000 to 150,000, or 3, 000 to 50,000.
- crosslinking agent of component (C) exemplified above can be used alone or in combination of two or more.
- the content of the crosslinking agent of component (C) in the resin composition of the present embodiment is such that the acrylic copolymer having at least a photodimerization site and a thermal crosslinking site of component (A) and the polyimide precursor of component (B) It is preferable to set it as 10 thru
- the resin composition of this Embodiment can contain an acid or a thermal acid generator as (D) component.
- This component (D) is effective in that the thermosetting property of the resin composition of the present embodiment is promoted.
- the compound is not particularly limited as long as it is a compound that generates an acid.
- 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, trifluoromethanesulfone.
- 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-
- sulfonic acids such as perfluorooctane sulfonic acid, perfluoro (2-ethoxyethane) sulfonic acid, pentafluoroethane sulfonic acid, nonafluorobutane-1-sulfonic acid, and dodecylbenzene sulfonic acid, or hydrates and salts thereof. It is done.
- Examples of the compound that generates an acid by heat include bis (tosyloxy) ethane, bis (tosyloxy) propane, bis (tosyloxy) butane, p-nitrobenzyl tosylate, o-nitrobenzyl tosylate, 1,2,3- Phenylenetris (methylsulfonate), p-toluenesulfonic acid pyridinium salt, p-toluenesulfonic acid morphonium salt, p-toluenesulfonic acid ethyl ester, p-toluenesulfonic acid propyl ester, p-toluenesulfonic acid butyl ester, p- Toluenesulfonic acid isobutyl ester, p-toluenesulfonic acid methyl ester, p-toluenesulfonic acid phenethyl ester, cyanomethyl p
- the content of the component (D) in the resin composition of the present embodiment is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). If it is less than 0.01 parts by mass, the thermosetting property is lowered and the solvent resistance becomes insufficient, and the sensitivity to light irradiation may be lowered. On the other hand, when it exceeds 5 mass parts, the storage stability of a composition may fall.
- ⁇ (E) component In this Embodiment, you may contain a sensitizer as (E) component.
- This component (E) is effective in that it promotes the photodimerization reaction after forming the thermosetting film of the present embodiment.
- Examples of the sensitizer as the component (E) include benzophenone, anthracene, anthraquinone, thioxanthone and derivatives thereof, and nitrophenyl compounds. Of these, benzophenone derivatives and nitrophenyl compounds are particularly preferred. Specific examples include N, N-diethylaminobenzophenone, 2-nitrofluorene, 2-nitrofluorenone, 5-nitroacenaphthene, 9-hydroxymethylanthracene, 4-nitrocinnamic acid or 4-nitrobiphenyl. In particular, N, N-diethylaminobenzophenone which is a derivative of benzophenone is preferable.
- the sensitizer is not limited to the above. The sensitizers can be used alone or in combination of two or more compounds.
- the use ratio of the sensitizer of component (E) in the present embodiment is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts per 100 parts by mass of component (A). Part by mass. If this proportion is less than 0.1 parts by mass, the effect as a sensitizer may not be sufficiently obtained. On the other hand, if it is more than 20 parts by mass, the transmittance may be lowered and the coating film may be roughened.
- the resin composition of the present embodiment can be used in a solution state dissolved in a solvent.
- the solvent to be used is one that dissolves the component (A), the component (B), and the component (C). If necessary, the component (D) and the component (E) are dissolved, and if other additives described below are contained, the component is dissolved. is there.
- the type and structure of the solvent are not particularly limited as long as the solvent has such dissolving ability. Specifically, the solvent used for superposition
- the resin composition of the present embodiment is not limited to the effects of the present invention, and if necessary, a silane coupling agent, a surfactant, a rheology modifier, a pigment, a dye, a storage stabilizer, an antifoaming agent.
- a silane coupling agent such as silane coupling agent, a surfactant, a rheology modifier, a pigment, a dye, a storage stabilizer, an antifoaming agent.
- Other additives such as additives and antioxidants can be included.
- the resin composition of the present embodiment comprises an (A) component, an acrylic copolymer having a photodimerization site and a thermal crosslinking site, a (B) component polyimide precursor, and a (C) component crosslinking agent. If desired, it may contain one or more of an acid or thermal acid generator as component (D), a sensitizer as component (E), and other additives. And a resin composition is normally used as a solution which these melt
- the blending ratio of the component (A) to the component (B) is preferably 5:95 to 60:40 in terms of parts by mass. If the content of the component (A) is too small than this blending ratio, there is a concern that cause alignment defects. On the other hand, when the content of the component (A) is too larger than this blending ratio, the birefringence becomes small and the coating film may become cloudy.
- the hydroxyl group value of the component (A) is usually from 1 to 3 mmol / g, since (B) the acid value of the component is usually 2 to 4 mmol / g, among the above-mentioned range, the component (A) and (B )
- the blending ratio of the component is further in the range of 5:95 to 40:60, the orientation component is bleed in the upper layer, the orientation sensitivity is increased, and a higher birefringence is obtained.
- the hydroxyl group value of component (A) is the number of mmols of potassium hydroxide required to neutralize acetic acid necessary for acetylating the free hydroxyl group contained in 1 g of component (A).
- the acid value of (B) component means the mmol number of potassium hydroxide required to neutralize the free acid group contained in 1 g of (B) component.
- Preferred examples of the resin composition of the present embodiment are as follows. [1]: A resin composition containing 10 to 100 parts by mass of component (C) based on 100 parts by mass of the total amount of component (A) and component (B). [2]: A resin composition containing 10 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). [3]: Based on 100 parts by mass of the total amount of component (A) and component (B), 10 to 100 parts by mass of component (C), 0.01 to 5 parts by mass of component (D), and solvent A resin composition to contain.
- the ratio of the solid content in the resin composition of the present embodiment is not particularly limited as long as each component is uniformly dissolved in the solvent, but the general solid content ratio is 1 to 80% by mass. is there. Among these, Preferably it is 3 thru
- solid content means what remove
- the method for preparing the resin composition of the present embodiment is not particularly limited. For example, there can be mentioned a method in which the component (A) is dissolved in a solvent, and the component (B), and further the components (C) and (D) are mixed in this solution at a predetermined ratio to obtain a uniform solution. In addition, in an appropriate stage of the preparation method, other additives may be added and mixed as necessary.
- an acrylic polymer solution obtained by a polymerization reaction in a solvent can be used as it is.
- the component (A), the component (B), the component (C), the component (D), and the like are added to the solution of the component (A) as described above to obtain a uniform solution.
- a solvent may be further added for the purpose of adjusting the concentration.
- the solvent used in the process of producing the acrylic polymer and the solvent used for concentration adjustment when preparing the resin composition may be the same solvent, and different appropriate solvents may be selected and used. May be.
- the solution of the resin composition of the present embodiment prepared as described above is preferably used after being filtered using a filter having a pore size of about 0.2 ⁇ m.
- a coating film can be formed by the following method. First, the resin composition is applied onto the substrate by a method such as spin coating, flow coating, roll coating, slit coating, spin coating following the slit, ink jet coating, or printing. Subsequently, a coating film can be formed by predrying (prebaking) with a hot plate or oven. Then, a cured film is formed by heat-treating (post-baking) this coating film.
- prebaking predrying
- post-baking heat-treating
- a silicon / silicon dioxide-coated substrate for example, a silicon / silicon dioxide-coated substrate, a silicon nitride substrate, a glass substrate, a quartz substrate, an ITO substrate, or the like can be used.
- a substrate coated with a metal such as aluminum, molybdenum, or chromium can be used.
- a resin film such as a triacetyl cellulose film, a polyester film, and an acrylic film can be used as the substrate.
- a heating temperature and a heating time appropriately selected from the range of a temperature of 70 to 160 ° C. and a time of 0.3 to 60 minutes are employed.
- the heating temperature and the heating time are preferably 80 to 140 ° C. and 0.5 to 10 minutes.
- a heating temperature appropriately selected from the temperature range of 140 to 250 ° C. according to the heating method and the like can be adopted.
- the heating time may be 5 to 30 minutes on the hot plate, and 30 to 90 minutes in the oven.
- the thickness of the cured film can be set to, for example, 0.1 to 30 ⁇ m, and can be appropriately selected in consideration of the level difference of the substrate to be used and the optical and electrical properties.
- the cured film thus obtained can function as a liquid crystal alignment layer for aligning a liquid crystal alignment material, that is, a compound having liquid crystallinity, by performing polarized light irradiation.
- the polarized light used for polarized light irradiation is preferably polarized UV (ultraviolet).
- polarized UV ultraviolet light having a wavelength of 150 to 450 nm is usually used.
- linearly polarized light is irradiated from the perpendicular or oblique direction to the cured film at room temperature or in a heated state.
- the configuration in which the phase difference material is arranged inside the liquid crystal cell can improve the contrast ratio of the liquid crystal cell as compared with the conventional configuration in which the phase difference material is arranged outside the liquid crystal cell.
- the retardation material for example, a liquid crystal monomer having a polymerizable group or a composition containing the same is used.
- the substrate on which the liquid crystal alignment layer is formed is a film, it is useful as an optically anisotropic film.
- Such retardation materials include materials having orientation such as horizontal orientation, cholesteric orientation, vertical orientation, hybrid orientation, and biaxial orientation, and can be used properly according to the required retardation.
- the two substrates having the liquid crystal alignment layer formed as described above are bonded so that the liquid crystal alignment layers face each other via a spacer, and then liquid crystal is injected between these substrates.
- a liquid crystal display element in which liquid crystal is aligned can be obtained.
- the resin composition of the present embodiment can be suitably used for constituting various optical anisotropic films and liquid crystal display elements.
- the resin composition of the present embodiment is also useful as 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. is there.
- TFT thin film transistor
- CF overcoat material the overcoat material of the color filter (CF)
- it is also suitable as a material for forming an interlayer insulating film of a TFT type liquid crystal element, an insulating film of an organic EL element, and the like.
- the obtained CF overcoat not only flattens the steps of the color filter but also functions as a liquid crystal alignment material. Therefore, it can be used as a CF overcoat having orientation.
- FIG. 1 is a schematic configuration diagram of a liquid crystal cell according to the present embodiment.
- the liquid crystal layer 108 is sandwiched between two substrates 101 and 111.
- An ITO 110 and an alignment film 109 are formed on the substrate 111.
- a color filter 102, a CF overcoat 103, a retardation material 105, an ITO 106, and an alignment film 107 are formed in this order.
- the CF overcoat 103 also functions as an alignment film, a film corresponding to the alignment film 204 in FIG. 2 can be dispensed with.
- the number average molecular weight and the weight average molecular weight of the acrylic copolymer obtained according to 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 supplied at a flow rate of 1 ml / The measurement was performed under the condition that the column was eluted in a column (column temperature: 40 ° C.).
- Mn number average molecular weight
- Mw weight average molecular weight
- Mn and Mw of the polyimide precursor were obtained by using a GPC apparatus (Shodex (registered trademark) columns KD803 and KD805) manufactured by Shodex and eluting solvent N, N, -dimethylformamide (as an additive, lithium bromide-hydrated).
- Mn and Mw below were expressed polyethylene glycol at polyethylene oxide conversion value.
- or Comparative Example 4 were prepared with the composition shown in Table 3, and the solvent tolerance, the transmittance
- a retardation material solution composed of a liquid crystal monomer was applied onto the substrate using a spin coater, and then prebaked on a hot plate at 80 ° C. for 60 seconds to form a coating film having a thickness of 1.4 ⁇ m.
- the coating film on the substrate was exposed to 1,000 mJ / cm 2 of UV light in a nitrogen atmosphere to cure the retardation material.
- the thus prepared substrate was sandwiched between polarizing plates, the phase difference state of the cured retardation material was confirmed, and the exposure amount of polarized UV necessary for the cured film to exhibit orientation was determined to obtain the orientation sensitivity.
- the thing which does not show orientation even if exposed to 3000 mJ / cm ⁇ 2 > UV light was set as x.
- Table 4 shows the results of the above evaluation.
- the alignment sensitivity was high. Therefore, it turned out that the composition of Example 1 thru
- the cured film formed from the composition of Comparative Example 1 has a low birefringence and solvent resistance, and requires 300 times the amount of exposure as in Examples 1 to 3 to exhibit orientation. It was.
- the cured films formed from the compositions of Comparative Examples 2 to 4 exhibited high birefringence and solvent resistance, but did not exhibit orientation.
- the cured film obtained from the resin composition of the present invention has a high birefringence and is excellent in light transmittance, solvent resistance, and orientation. Therefore, according to the resin composition of the present invention, it is possible to provide a cured film having excellent properties as described above, that is, a liquid crystal alignment material, and further, it is possible to form a retardation material. It was.
- the resin composition according to the present invention is very useful as an optically anisotropic film or a liquid crystal alignment material for a liquid crystal display element, and further, a protective film in various displays such as a thin film transistor (TFT) type liquid crystal display element and an organic EL element, It is also suitable as a material for forming a cured film such as a flattening film and an insulating film, particularly as a material for forming an interlayer insulating film of a TFT type liquid crystal element, a protective film for a color filter or an insulating film for an organic EL element.
- TFT thin film transistor
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Nonlinear Science (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Liquid Crystal (AREA)
- Polarising Elements (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
(A)疎水性基からなる光二量化部位と親水性基からなる熱架橋部位とを有するアクリル共重合体と、
(B)芳香環部位を有するポリイミド前駆体と、
(C)(A)成分と(B)成分とを架橋する架橋剤とを含有する樹脂組成物に関する。
(A) 疎水性基からなる光二量化部位と、親水性基からなる熱架橋部位とを有するアクリル共重合体と、
(B) 芳香環部位を有するポリイミド前駆体と、
(C) (A)成分と(B)成分とを架橋する架橋剤とを含有して構成されたものである。
尚、このとき、硬化膜の光透過性、すなわち透明性が低下する懸念があるが、ポリイミド前駆体を構成する化合物の分子構造を選択することで、透過率の低下を抑制することが可能である。例えば、このポリイミド前駆体を構成する化合物として脂環構造を有する化合物を選択することで、硬化膜に高い透明性を付与することが可能となる。つまり、ポリイミド前駆体の分子構造を適宜設計することによって、硬化膜に高い複屈折性と高い透明性の両方を付与することができる。
本実施の形態の(A)成分は、光二量化部位および熱架橋部位を有するアクリル共重合体である。(A)成分のアクリル共重合体の光二量化部位は、疎水性基からなり、熱架橋部位は、親水性基からなる。次に、これらについて具体例を挙げて説明する。
(A)成分としての光二量化部位および熱架橋部位を有するアクリル共重合体(以下、特定共重合体とも言う。)は、か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および側鎖の種類などについて特に限定はされない。
R1、R2、R3および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またはシアノ基を表す。
R1、R2、R3および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またはシアノ基を表す。例えば、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及び6-(アクリロイルオキシ)ヘキシル-3-(4-メトキシフェニル)アクリレートなどが挙げられる。
また、上記方法で得られた特定共重合体の溶液を、攪拌下のジエチルエーテルや水などに投入して再沈殿させ、生成した沈殿物を濾過・洗浄した後に、常圧または減圧下で、常温乾燥または加熱乾燥し、特定共重合体の粉体とすることができる。そうした操作により、特定共重合体と共存する重合開始剤および未反応のモノマーを除去することができ、その結果、精製した特定共重合体の粉体が得られる。一度の操作で充分に精製できない場合は、得られた粉体を溶剤に再溶解させ、上記の操作を繰り返し行えばよい。
また、本実施の形態においては、(A)成分の特定共重合体は、複数種の特定共重合体の混合物であってもよい。
本実施の形態における(B)成分は、ポリイミド前駆体である。(B)成分としてのポリイミド前駆体は芳香環部位を有する。高い複屈折率を達成するためには、ポリイミド前駆体の中でも下記式(1)で表される構造単位を有するポリイミド前駆体が好ましい。
本実施の形態において、(B)成分のポリイミド前駆体は、テトラカルボン酸二無水物とジアミン化合物とを共重合させることにより得られる。
本実施の形態の(C)成分は架橋剤である。この架橋剤は、(A)成分と(B)成分を架橋するものとすることができる。
本実施の形態の樹脂組成物は、(D)成分として、酸または熱酸発生剤を含有することができる。この(D)成分は、本実施の形態の樹脂組成物の熱硬化性を促進させる点で有効である。
本実施の形態においては、(E)成分として増感剤を含有してもよい。この(E)成分は、本実施の形態の熱硬化膜形成後の光二量化反応を促進する点で有効である。
本実施の形態の樹脂組成物は、溶剤に溶解した溶液状態で用いることができる。用いる溶剤は、(A)成分(B)成分、および(C)成分を溶解するものである。また、必要に応じて、(D)成分や(E)成分が含有される場合はそれらを溶解するものであり、また、後述するその他の添加剤が含有される場合はそれを溶解するものである。かかる溶解能を有する溶剤であれば、その種類および構造などは特に限定されるものではない。具体的には、(A)成分または(B)成分の重合に用いる溶剤を挙げることができる。これらの溶剤は、1種単独でまたは2種以上の組合せで使用することができる。
さらに、本実施の形態の樹脂組成物は、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、消泡剤および酸化防止剤などの他の添加剤を含有することができる。
本実施の形態の樹脂組成物は、(A)成分である、光二量化部位および熱架橋部位を有するアクリル共重合体、(B)成分であるポリイミド前駆体、(C)成分である架橋剤を含有し、所望により、(D)成分である酸または熱酸発生剤、(E)成分である増感剤、さらに、その他の添加剤のうちの1種以上を含有することができる。そして、樹脂組成物は、通常、これらが溶剤に溶解した溶液として用いられる。
なお、(A)成分のヒドロキシル基価は通常1乃至3mmol/gであり、(B)成分の酸価は通常2乃至4mmol/gであるので、上記範囲のうち、(A)成分と(B)成分を配合比をさらに5:95乃至40:60の範囲にした場合は、上層に配向成分がブリードし配向感度が上がり、さらに高い複屈折率が得られる。
ここで、(A)成分のヒドロキシル基価とは、(A)成分1g中に含まれる遊離のヒドロキシル基をアセチル化するために必要な酢酸を中和するのに要する水酸化カリウムのmmol数をいう。また、(B)成分の酸価とは、(B)成分1g中に含まれる遊離の酸基を中和するのに要する水酸化カリウムのmmol数をいう。
[1]:(A)成分と(B)成分の合計量100質量部に基づいて、10乃至100質量部の(C)成分を含有する樹脂組成物。
[2]:(A)成分と(B)成分の合計量100質量部に基づいて、10乃至100質量部の(C)成分、および溶剤を含有する樹脂組成物。
[3]:(A)成分と(B)成分の合計量100質量部に基づいて、10乃至100質量部の(C)成分、0.01乃至5質量部の(D)成分、および溶剤を含有する樹脂組成物。
本実施の形態の樹脂組成物を用い、次のような方法により塗膜を形成できる。
まず、基板上に、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または印刷などの方法によって、樹脂組成物を塗布する。次いで、ホットプレートまたはオーブンなどで予備乾燥(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。
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>
HEMA:2-ヒドロキシエチルメタクリレート
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
<ポリイミド前駆体>
BPDA:3,3’,4,4’-ビフェニルテトラカルボン酸二無水物
ODPA:4,4’-オキシジフタル酸無水物
CBDA:1,2,3,4-シクロブタンテトラカルボン酸二無水物
TFMB:2,2’-トリフルオロメチル-4,4’-ジアミノビフェニル
<架橋剤>
CYM:サイメル303(三井サイテック製)
<酸または熱酸発生剤>
PTSA:p-トルエンスルホン酸1水和物
<溶剤>
CHN:シクロヘキサノン
NMP:N-メチルピロリドン
また、ポリイミド前駆体のMnおよびMwは、Shodex社製GPC装置(Shodex(登録商標)カラムKD803およびKD805)を用い、溶出溶媒N,N,-ジメチルホルムアミド(添加剤として、臭化リチウム-水和物(LiBr・H2O)が30mmol/L、リン酸・無水結晶(o-リン酸)が30mmol/L、テトラヒドロフランが10ml/L)を流量1ml/分でカラム中に(カラム温度50℃)流して溶離させるという条件で測定した。なお、下記のMnおよびMwは、ポリエチレングリコール、ポリエチレンオキシド換算値にて表した。
CIN 42.0g、HEMA 18.0g、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アクリル重合体溶液(固形分濃度27質量%を得た)(P1)。得られたアクリル重合体のMnは8,500、Mwは16,500であった。
TFMB 16.0gをNMP 114.1gに溶解した。その後、BPDA 12.5gを加え40℃にて20時間反応させることによりポリイミド前駆体溶液(固形分濃度20質量%を得た)(P2)。得られたポリイミド前駆体のMnは12,600、Mwは27,500であった。
TFMB 5.1gをNMP 72.2gに溶解した。その後、ODPA 4.7gを加え室温にて20時間反応させることによりポリイミド前駆体溶液(固形分濃度12質量%を得た)(P3)。得られたポリイミド前駆体のMnは7,000、Mwは15,800であった。
TFMB 233.8gをNMP 2111.6gに溶解した。その後、CBDA 142.9gを加え室温にて20時間反応させることによりポリイミド前駆体溶液(固形分濃度15質量%を得た)(P4)。得られたポリイミド前駆体のMnは12,400、Mwは43,000であった。
表3に示す組成にて実施例1乃至実施例3および比較例1乃至比較例4の各組成物を調製し、それぞれについて、溶剤耐性、透過率、配向性並びに複屈折率の評価を行った。
実施例1乃至実施例3および比較例1乃至比較例4の各組成物を、シリコンウェハにスピンコータを用いて塗布した後、温度80℃で120秒間ホットプレート上においてプリベークを行った。その後、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して、膜厚2.0μmの硬化膜を形成した。膜厚は、VEECO社製 DEKTAK150を用いて測定した。
次に、この硬化膜をCHNまたは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または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3および比較例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を用いて塗布した後、温度80℃で120秒間ホットプレート上においてプリベークを行った。その後、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して、膜厚2.0μmの硬化膜を形成した。膜厚は、VEECO社製 DEKTAK150を用いて測定した。
次に、この硬化膜について、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、波長400nm時の透過率を測定した。
実施例1乃至実施例3および比較例1乃至比較例4の各組成物を、ITO基板上にスピンコータを用いて塗布した後、温度80℃で120秒間ホットプレート上においてプリベークを行った。その後、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して、膜厚2.0μmの硬化膜を形成した。膜厚は、VEECO社製 DEKTAK150を用いて測定した。
次に、偏光UVとして波長313nmの直線偏光を、ITO基板上の硬化膜に対して垂直となる方向から照射した。次いで、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を用いて塗布し、その後、80℃で60秒間ホットプレート上でプリベークを行って、膜厚1.4μmの塗膜を形成した。次に、この基板上の塗膜に対して、窒素雰囲気下で1,000mJ/cm2のUV光を露光し、位相差材料を硬化させた。こうして作製した基板を偏光板に挟み、硬化した位相差材料の位相差状態を確認し、硬化膜が配向性を示すのに必要な偏光UVの露光量を求めて配向感度とした。また、3,000mJ/cm2のUV光を露光しても配向性を示さないものを×とした。
実施例1乃至実施例3および比較例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を用いて塗布した後、温度80℃で120秒間ホットプレート上においてプリベークを行った。その後、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2.0μmの硬化膜を形成した。膜厚は、VEECO社製 DEKTAK150を用いて測定した。
この硬化膜について、位相差フィルム測定装置(AXOMETRICS Inc.製Axo Scan)を用いて波長590nm時の複屈折率を測定した。
以上の評価を行った結果を表4に示す。
Claims (17)
- (A)疎水性基からなる光二量化部位と親水性基からなる熱架橋部位とを有するアクリル共重合体と、
(B)芳香環部位を有するポリイミド前駆体と、
(C)該(A)成分と該(B)成分とを架橋する架橋剤とを含有する樹脂組成物。 - 前記(A)成分は、光二量化部位を有するモノマーと熱架橋部位を有するモノマーとを含むモノマー混合物の重合反応により得られるアクリル共重合体であることを特徴とする請求項1に記載の樹脂組成物。
- 前記(A)成分は、全モノマー混合物の合計量に対し、光二量化部位を有するモノマーを25モル%乃至90モル%含むモノマー混合物の重合反応により得られるアクリル共重合体であることを特徴とする請求項2に記載の樹脂組成物。
- 前記(A)成分の光二量化部位は、シンナモイル基であることを特徴とする請求項1乃至請求項3のいずれか1項に記載の樹脂組成物。
- 前記(A)成分の熱架橋部位は、ヒドロキシル基またはカルボキシル基であることを特徴とする請求項1乃至請求項4のいずれか1項に記載の樹脂組成物。
- 前記(B)成分のポリイミド前駆体は、主鎖にビフェニル構造を有することを特徴とする請求項1乃至請求項5のいずれか1項に記載の樹脂組成物。
- 前記(B)成分は、テトラカルボン酸二無水物とジアミン化合物との共重合反応により得られる構造単位を含むポリイミド前駆体であって、該テトラカルボン酸二無水物及び該ジアミン化合物の少なくとも一方にビフェニル構造を有することを特徴とする請求項6に記載の樹脂組成物。
- 前記テトラカルボン酸二無水物は、ビフェニルテトラカルボン酸二無水物であることを特徴とする請求項7に記載の樹脂組成物。
- 前記(B)成分は、前記構造単位にトリフルオロメチル基を有するポリイミド前駆体であることを特徴とする請求項7または請求項8に記載の樹脂組成物。
- 前記(B)成分のポリイミド前駆体は、主鎖に脂環構造を有することを特徴とする請求項1乃至9のいずれか1項に記載の樹脂組成物。
- 前記(B)成分は、テトラカルボン酸二無水物とジアミン化合物との共重合反応により得られる構造単位を含むポリイミド前駆体であって、該テトラカルボン酸二無水物及び該ジアミン化合物の少なくとも一方に脂環構造を有することを特徴とする請求項10に記載の樹脂組成物。
- 前記(C)成分の架橋剤は、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ことを特徴とする請求項1乃至請求項11のいずれか1項に記載の樹脂組成物。
- 前記(A)成分と前記(B)成分の合計量100質量部に基づいて、10乃至100質量部の前記(C)成分を含有することを特徴とする請求項1乃至請求項12のいずれか1項に記載の樹脂組成物。
- さらに(D)成分として酸または熱酸発生剤を含有することを特徴とする請求項1乃至請求項13のいずれか1項に記載の樹脂組成物。
- 前記(A)成分と前記(B)成分の合計量100質量部に基づいて、0.1乃至10質量部の前記(D)成分を含有することを特徴とする請求項14に記載の樹脂組成物。
- 請求項1乃至請求項15のいずれか1項に記載の樹脂組成物を用いて得られることを特徴とする液晶配向材。
- 請求項1乃至請求項15のいずれか1項に記載の樹脂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。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201180038557.9A CN103052680B (zh) | 2010-08-05 | 2011-08-05 | 树脂组合物、液晶取向材及相位差材 |
KR1020137005540A KR101844738B1 (ko) | 2010-08-05 | 2011-08-05 | 수지 조성물, 액정 배향재 및 위상차재 |
JP2012527789A JP5835586B2 (ja) | 2010-08-05 | 2011-08-05 | 樹脂組成物、液晶配向材および位相差材 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010-176347 | 2010-08-05 | ||
JP2010176347 | 2010-08-05 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012018121A1 true WO2012018121A1 (ja) | 2012-02-09 |
Family
ID=45559616
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2011/067969 WO2012018121A1 (ja) | 2010-08-05 | 2011-08-05 | 樹脂組成物、液晶配向材および位相差材 |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP5835586B2 (ja) |
KR (1) | KR101844738B1 (ja) |
CN (1) | CN103052680B (ja) |
TW (1) | TWI535773B (ja) |
WO (1) | WO2012018121A1 (ja) |
Cited By (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013191251A1 (ja) * | 2012-06-20 | 2013-12-27 | 日産化学工業株式会社 | 硬化膜形成組成物、配向材および位相差材 |
JP2014084355A (ja) * | 2012-10-22 | 2014-05-12 | Jnc Corp | 光配向性を有する熱硬化性組成物 |
WO2014104320A1 (ja) * | 2012-12-27 | 2014-07-03 | 日産化学工業株式会社 | 硬化膜形成組成物、配向材および位相差材 |
WO2015019962A1 (ja) * | 2013-08-09 | 2015-02-12 | 日産化学工業株式会社 | 硬化膜形成組成物、配向材および位相差材 |
JPWO2013054673A1 (ja) * | 2011-10-14 | 2015-03-30 | 大日本印刷株式会社 | パターン位相差フィルム及びその製造方法 |
JP2015518239A (ja) * | 2012-03-30 | 2015-06-25 | エルジー・ケム・リミテッド | 有機電子素子用基板 |
WO2016031917A1 (ja) * | 2014-08-28 | 2016-03-03 | 日産化学工業株式会社 | 硬化膜形成組成物、配向材および位相差材 |
US9285679B2 (en) | 2012-03-27 | 2016-03-15 | Fujifilm Corporation | Actinic ray-sensitive or radiation-sensitive composition, and resist film, resist-coated mask blanks, resist pattern forming method and photomask each using the composition |
JP2016079189A (ja) * | 2014-10-09 | 2016-05-16 | Dic株式会社 | 光配向膜用の共重合体 |
JPWO2014042216A1 (ja) * | 2012-09-12 | 2016-08-18 | 日産化学工業株式会社 | 配向材の製造方法、配向材、位相差材の製造方法および位相差材 |
EP2735946A3 (en) * | 2012-11-23 | 2016-11-30 | Shanghai Tianma Micro-electronics Co., Ltd. | In-cell touch panel and touch display device |
WO2017099041A1 (ja) * | 2015-12-11 | 2017-06-15 | コニカミノルタ株式会社 | ポリイミドフィルム、フレキシブルプリント基板、led照明装置等 |
CN106980233A (zh) * | 2012-07-12 | 2017-07-25 | 日产化学工业株式会社 | 形成固化膜的组合物、取向材及相位差材 |
WO2018043467A1 (ja) * | 2016-08-31 | 2018-03-08 | 富士フイルム株式会社 | 樹脂組成物およびその応用 |
JP2019502943A (ja) * | 2015-11-11 | 2019-01-31 | ロリク・テクノロジーズ・アーゲーRolic Technologies Ag | 光配列性材料の組成物 |
JP2019112607A (ja) * | 2017-12-22 | 2019-07-11 | Dic株式会社 | 重合性化合物及びそれを含有する液晶組成物 |
CN112812347A (zh) * | 2021-02-23 | 2021-05-18 | 深圳市新纶科技股份有限公司 | 一种光学薄膜材料及其制备方法、偏光片 |
CN114685791A (zh) * | 2022-03-02 | 2022-07-01 | 江苏环峰电工材料有限公司广州分公司 | 一种结构可控的聚酰亚胺聚合物及其制备方法 |
KR20230004846A (ko) | 2020-06-03 | 2023-01-06 | 후지필름 가부시키가이샤 | 감광성 수지 조성물, 경화막, 적층체, 경화막의 제조 방법, 및, 반도체 디바이스 |
WO2023026982A1 (ja) * | 2021-08-24 | 2023-03-02 | 株式会社カネカ | 樹脂組成物、成形体およびフィルム |
WO2023085325A1 (ja) * | 2021-11-10 | 2023-05-19 | 株式会社カネカ | 樹脂組成物、成形体およびフィルム |
WO2023100806A1 (ja) * | 2021-11-30 | 2023-06-08 | 株式会社カネカ | フィルムおよびその製造方法、ならびに画像表示装置 |
WO2023195525A1 (ja) * | 2022-04-08 | 2023-10-12 | 株式会社カネカ | フィルムおよびその製造方法、ならびに画像表示装置 |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102205664B1 (ko) | 2014-06-02 | 2021-01-22 | 삼성디스플레이 주식회사 | 액정 표시 장치 제조 방법 |
TWI693470B (zh) * | 2015-06-30 | 2020-05-11 | 日商富士軟片股份有限公司 | 感光性樹脂組成物、硬化膜的製造方法、硬化膜及液晶顯示裝置 |
CN105199387B (zh) * | 2015-10-12 | 2018-03-27 | 深圳市华星光电技术有限公司 | 配向膜材料及配向膜的制造方法 |
WO2019146611A1 (ja) * | 2018-01-29 | 2019-08-01 | 富士フイルム株式会社 | 感光性樹脂組成物、樹脂、硬化膜、積層体、硬化膜の製造方法、半導体デバイス |
JP2019159009A (ja) * | 2018-03-09 | 2019-09-19 | シャープ株式会社 | 液晶表示装置、液晶表示装置の製造方法、及び、位相差層用モノマー材料 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0411652B2 (ja) * | 1983-12-08 | 1992-03-02 | Howa Machinery Ltd | |
JP2002069180A (ja) * | 2000-08-30 | 2002-03-08 | Chisso Corp | ポリアミド酸、ポリイミド、該ポリイミド膜を用いた液晶配向膜、および該配向膜を用いた液晶表示素子 |
JP2006091290A (ja) * | 2004-09-22 | 2006-04-06 | Nitto Denko Corp | 液晶材料を配向させるための配向膜の製造方法、得られた配向膜、配向液晶膜、光学フィルムおよび画像表示装置 |
JP2009282341A (ja) * | 2008-05-23 | 2009-12-03 | Jsr Corp | 液晶配向剤、液晶配向膜の形成方法および液晶表示素子 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR970003683B1 (ko) * | 1993-09-28 | 1997-03-21 | 제일합섬 주식회사 | 액정디스플레이 컬러필터용 감광성 수지 조성물 |
JP4369533B2 (ja) * | 1994-09-29 | 2009-11-25 | ロリク アーゲー | 液晶配向層を製造するためのクマリン及びキノリノン誘導体 |
US6107427A (en) * | 1995-09-15 | 2000-08-22 | Rolic Ag | Cross-linkable, photoactive polymer materials |
EP1219651A1 (en) * | 2000-12-29 | 2002-07-03 | Rolic AG | Photoactive copolymer |
DE60308510D1 (de) * | 2002-05-23 | 2006-11-02 | Nissan Chemical Ind Ltd | Flüssigkristall-ausrichtungsmittel, flüssigkristall-ausrichtungsfilme und flüssigkristall-anzeigeeinrichtungen |
AU2003302749A1 (en) * | 2002-12-06 | 2004-07-29 | Huntsman Advanced Materials (Switzerland) Gmbh | Crosslinkable, photoactive polymers and their use |
KR101133479B1 (ko) * | 2003-10-23 | 2012-04-10 | 닛산 가가쿠 고교 가부시키 가이샤 | 액정 배향 처리제 및 액정 표시 소자 |
KR101388998B1 (ko) * | 2006-06-15 | 2014-04-24 | 닛산 가가쿠 고교 가부시키 가이샤 | 환구조를 갖는 고분자 화합물을 함유하는 포지티브형 감광성 수지조성물 |
CN101679633B (zh) * | 2007-06-15 | 2012-09-19 | 日产化学工业株式会社 | 热固化膜形成用树脂组合物 |
JP5459520B2 (ja) * | 2009-06-23 | 2014-04-02 | 日産化学工業株式会社 | 光配向性を有する熱硬化膜形成組成物 |
WO2011010635A1 (ja) * | 2009-07-21 | 2011-01-27 | 日産化学工業株式会社 | 光配向性を有する熱硬化膜形成組成物 |
-
2011
- 2011-08-05 JP JP2012527789A patent/JP5835586B2/ja active Active
- 2011-08-05 KR KR1020137005540A patent/KR101844738B1/ko active IP Right Grant
- 2011-08-05 TW TW100127999A patent/TWI535773B/zh active
- 2011-08-05 WO PCT/JP2011/067969 patent/WO2012018121A1/ja active Application Filing
- 2011-08-05 CN CN201180038557.9A patent/CN103052680B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0411652B2 (ja) * | 1983-12-08 | 1992-03-02 | Howa Machinery Ltd | |
JP2002069180A (ja) * | 2000-08-30 | 2002-03-08 | Chisso Corp | ポリアミド酸、ポリイミド、該ポリイミド膜を用いた液晶配向膜、および該配向膜を用いた液晶表示素子 |
JP2006091290A (ja) * | 2004-09-22 | 2006-04-06 | Nitto Denko Corp | 液晶材料を配向させるための配向膜の製造方法、得られた配向膜、配向液晶膜、光学フィルムおよび画像表示装置 |
JP2009282341A (ja) * | 2008-05-23 | 2009-12-03 | Jsr Corp | 液晶配向剤、液晶配向膜の形成方法および液晶表示素子 |
Cited By (41)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPWO2013054673A1 (ja) * | 2011-10-14 | 2015-03-30 | 大日本印刷株式会社 | パターン位相差フィルム及びその製造方法 |
US9720154B2 (en) | 2011-10-14 | 2017-08-01 | Dai Nippon Printing Co., Ltd. | Patterned phase difference film and method for manufacturing same |
US9638848B2 (en) | 2011-10-14 | 2017-05-02 | Dai Nippon Printing Co., Ltd. | Patterned phase difference film and method for manufacturing same |
US9285679B2 (en) | 2012-03-27 | 2016-03-15 | Fujifilm Corporation | Actinic ray-sensitive or radiation-sensitive composition, and resist film, resist-coated mask blanks, resist pattern forming method and photomask each using the composition |
US9590197B2 (en) | 2012-03-30 | 2017-03-07 | Lg Chem, Ltd. | Substrate for organic electronic device |
JP2015518239A (ja) * | 2012-03-30 | 2015-06-25 | エルジー・ケム・リミテッド | 有機電子素子用基板 |
WO2013191251A1 (ja) * | 2012-06-20 | 2013-12-27 | 日産化学工業株式会社 | 硬化膜形成組成物、配向材および位相差材 |
JPWO2013191251A1 (ja) * | 2012-06-20 | 2016-05-26 | 日産化学工業株式会社 | 硬化膜形成組成物、配向材および位相差材 |
KR20150023557A (ko) * | 2012-06-20 | 2015-03-05 | 닛산 가가쿠 고교 가부시키 가이샤 | 경화막 형성 조성물, 배향재 및 위상차재 |
CN104379666A (zh) * | 2012-06-20 | 2015-02-25 | 日产化学工业株式会社 | 固化膜形成用组合物、取向材以及相位差材 |
US10000701B2 (en) | 2012-06-20 | 2018-06-19 | Nissan Chemical Industries, Ltd. | Cured-film formation composition, orientation material, and retardation material |
KR102021775B1 (ko) | 2012-06-20 | 2019-09-17 | 닛산 가가쿠 가부시키가이샤 | 경화막 형성 조성물, 배향재 및 위상차재 |
CN106980233B (zh) * | 2012-07-12 | 2021-07-13 | 日产化学工业株式会社 | 形成固化膜的组合物、取向材及相位差材 |
CN106980233A (zh) * | 2012-07-12 | 2017-07-25 | 日产化学工业株式会社 | 形成固化膜的组合物、取向材及相位差材 |
JPWO2014042216A1 (ja) * | 2012-09-12 | 2016-08-18 | 日産化学工業株式会社 | 配向材の製造方法、配向材、位相差材の製造方法および位相差材 |
JP2014084355A (ja) * | 2012-10-22 | 2014-05-12 | Jnc Corp | 光配向性を有する熱硬化性組成物 |
EP2735946A3 (en) * | 2012-11-23 | 2016-11-30 | Shanghai Tianma Micro-electronics Co., Ltd. | In-cell touch panel and touch display device |
US10437363B2 (en) | 2012-11-23 | 2019-10-08 | Shanghai Tianma Micro-electronics Co., Ltd. | In-cell touch panel and touch display device |
US9727155B2 (en) | 2012-11-23 | 2017-08-08 | Shanghai Tianma Micro-electronics Co., Ltd. | In-cell touch panel and touch display device |
WO2014104320A1 (ja) * | 2012-12-27 | 2014-07-03 | 日産化学工業株式会社 | 硬化膜形成組成物、配向材および位相差材 |
KR20160040193A (ko) * | 2013-08-09 | 2016-04-12 | 닛산 가가쿠 고교 가부시키 가이샤 | 경화막 형성조성물, 배향재 및 위상차재 |
KR102246723B1 (ko) * | 2013-08-09 | 2021-05-03 | 닛산 가가쿠 가부시키가이샤 | 경화막 형성조성물, 배향재 및 위상차재 |
WO2015019962A1 (ja) * | 2013-08-09 | 2015-02-12 | 日産化学工業株式会社 | 硬化膜形成組成物、配向材および位相差材 |
JPWO2015019962A1 (ja) * | 2013-08-09 | 2017-03-02 | 日産化学工業株式会社 | 硬化膜形成組成物、配向材および位相差材 |
WO2016031917A1 (ja) * | 2014-08-28 | 2016-03-03 | 日産化学工業株式会社 | 硬化膜形成組成物、配向材および位相差材 |
JPWO2016031917A1 (ja) * | 2014-08-28 | 2017-06-15 | 日産化学工業株式会社 | 硬化膜形成組成物、配向材および位相差材 |
JP2016079189A (ja) * | 2014-10-09 | 2016-05-16 | Dic株式会社 | 光配向膜用の共重合体 |
JP2019502943A (ja) * | 2015-11-11 | 2019-01-31 | ロリク・テクノロジーズ・アーゲーRolic Technologies Ag | 光配列性材料の組成物 |
WO2017099041A1 (ja) * | 2015-12-11 | 2017-06-15 | コニカミノルタ株式会社 | ポリイミドフィルム、フレキシブルプリント基板、led照明装置等 |
WO2018043467A1 (ja) * | 2016-08-31 | 2018-03-08 | 富士フイルム株式会社 | 樹脂組成物およびその応用 |
JPWO2018043467A1 (ja) * | 2016-08-31 | 2019-08-08 | 富士フイルム株式会社 | 樹脂組成物およびその応用 |
JP2019112607A (ja) * | 2017-12-22 | 2019-07-11 | Dic株式会社 | 重合性化合物及びそれを含有する液晶組成物 |
JP7070122B2 (ja) | 2017-12-22 | 2022-05-18 | Dic株式会社 | 重合性化合物及びそれを含有する液晶組成物 |
KR20230004846A (ko) | 2020-06-03 | 2023-01-06 | 후지필름 가부시키가이샤 | 감광성 수지 조성물, 경화막, 적층체, 경화막의 제조 방법, 및, 반도체 디바이스 |
CN112812347A (zh) * | 2021-02-23 | 2021-05-18 | 深圳市新纶科技股份有限公司 | 一种光学薄膜材料及其制备方法、偏光片 |
WO2023026982A1 (ja) * | 2021-08-24 | 2023-03-02 | 株式会社カネカ | 樹脂組成物、成形体およびフィルム |
WO2023085325A1 (ja) * | 2021-11-10 | 2023-05-19 | 株式会社カネカ | 樹脂組成物、成形体およびフィルム |
WO2023100806A1 (ja) * | 2021-11-30 | 2023-06-08 | 株式会社カネカ | フィルムおよびその製造方法、ならびに画像表示装置 |
CN114685791A (zh) * | 2022-03-02 | 2022-07-01 | 江苏环峰电工材料有限公司广州分公司 | 一种结构可控的聚酰亚胺聚合物及其制备方法 |
CN114685791B (zh) * | 2022-03-02 | 2023-10-03 | 江苏环峰电工材料有限公司 | 一种结构可控的聚酰亚胺聚合物及其制备方法 |
WO2023195525A1 (ja) * | 2022-04-08 | 2023-10-12 | 株式会社カネカ | フィルムおよびその製造方法、ならびに画像表示装置 |
Also Published As
Publication number | Publication date |
---|---|
JP5835586B2 (ja) | 2015-12-24 |
CN103052680A (zh) | 2013-04-17 |
JPWO2012018121A1 (ja) | 2013-10-28 |
TW201224043A (en) | 2012-06-16 |
CN103052680B (zh) | 2016-05-25 |
TWI535773B (zh) | 2016-06-01 |
KR20130097175A (ko) | 2013-09-02 |
KR101844738B1 (ko) | 2018-04-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5835586B2 (ja) | 樹脂組成物、液晶配向材および位相差材 | |
JP5382346B2 (ja) | 熱硬化膜形成用樹脂組成物 | |
JP5466872B2 (ja) | 液晶配向剤、及びそれから形成される液晶配向膜とその製造方法、並びに該配向膜を具える液晶表示素子 | |
JP6618043B2 (ja) | 液晶配向剤、液晶配向膜及び液晶表示素子 | |
TWI637043B (zh) | Liquid crystal display element, liquid crystal alignment film, and liquid crystal alignment treatment agent | |
WO2014185412A1 (ja) | 横電界駆動型液晶表示素子用液晶配向膜を有する基板の製造方法 | |
KR20120094460A (ko) | 광배향성을 갖는 열경화막 형성 조성물 | |
JP6008152B2 (ja) | 樹脂組成物、液晶配向材および位相差材 | |
TWI633128B (zh) | Composition, liquid crystal alignment treatment agent, liquid crystal alignment film, and liquid crystal display element | |
TWI627202B (zh) | Composition, liquid crystal alignment treatment agent, liquid crystal alignment film, and liquid crystal display element | |
TWI402284B (zh) | 液晶光配向劑與使用該對光配向劑製造的液晶光配向膜 | |
JP2016103011A (ja) | 液晶配向剤、液晶配向膜及び液晶表示素子 | |
TWI490610B (zh) | Liquid crystal aligning agent and liquid crystal display element | |
WO2020045549A1 (ja) | 液晶配向剤、液晶配向膜、及び液晶表示素子 | |
KR101736885B1 (ko) | 열경화막 형성용 폴리에스테르 조성물 | |
JP2011184508A (ja) | ポリイミド樹脂硬化膜及び光学補償部材 | |
JP7424318B2 (ja) | 液晶配向剤、液晶配向膜、及び液晶表示素子 | |
KR101736902B1 (ko) | 열경화막 형성용 폴리에스테르 조성물 | |
JP2017142453A (ja) | 液晶配向膜の製造方法、液晶配向膜及び液晶表示素子 | |
CN113939764A (zh) | 液晶取向剂、液晶取向膜及液晶元件 | |
KR102597729B1 (ko) | 액정 배향제, 액정 배향막, 및 액정 표시 소자 | |
WO2024080351A1 (ja) | 液晶配向剤、液晶配向膜及び液晶表示素子 | |
CN114207085A (zh) | 液晶取向剂、液晶取向膜及液晶元件 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201180038557.9 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11814746 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2012527789 Country of ref document: JP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20137005540 Country of ref document: KR Kind code of ref document: A |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 11814746 Country of ref document: EP Kind code of ref document: A1 |