WO2019027045A1 - Composition formant un film durci, matériau d'orientation et matériau de contraste de phase - Google Patents

Composition formant un film durci, matériau d'orientation et matériau de contraste de phase Download PDF

Info

Publication number
WO2019027045A1
WO2019027045A1 PCT/JP2018/029248 JP2018029248W WO2019027045A1 WO 2019027045 A1 WO2019027045 A1 WO 2019027045A1 JP 2018029248 W JP2018029248 W JP 2018029248W WO 2019027045 A1 WO2019027045 A1 WO 2019027045A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
cured film
component
mass
parts
Prior art date
Application number
PCT/JP2018/029248
Other languages
English (en)
Japanese (ja)
Inventor
伊藤　潤
Original Assignee
日産化学株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日産化学株式会社 filed Critical 日産化学株式会社
Priority to CN201880064199.0A priority Critical patent/CN111164120A/zh
Priority to KR1020207004627A priority patent/KR102662084B1/ko
Priority to CN202310790480.5A priority patent/CN116789871A/zh
Priority to JP2019534604A priority patent/JP7365003B2/ja
Publication of WO2019027045A1 publication Critical patent/WO2019027045A1/fr

Links

Classifications

    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—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 an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C08F212/22—Oxygen
    • 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
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • 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
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
    • 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
    • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
    • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
    • 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
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers

Definitions

  • the present invention relates to a cured film-forming composition for aligning liquid crystal molecules, an alignment material, and a retardation material.
  • the present invention is useful for producing a patterned retardation material used in a 3D display of a circularly polarized glasses system, and a retardation material used in a circularly polarizing plate used as an antireflection film of an organic EL display.
  • the present invention relates to a cured film-forming composition, an alignment material, and a retardation material.
  • a retardation material is usually disposed on a display element such as a liquid crystal panel that forms an image.
  • a display element such as a liquid crystal panel that forms an image.
  • a plurality of two types of retardation regions having different retardation characteristics are regularly arranged, and constitute a patterned retardation material.
  • a retardation material patterned so as to dispose a plurality of retardation regions having different retardation characteristics as described above will be referred to as a patterned retardation material.
  • the patterned retardation material can be produced, for example, by optically patterning a retardation material composed of a polymerizable liquid crystal as disclosed in Patent Document 1.
  • the optical patterning of the retardation material made of a polymerizable liquid crystal utilizes a photoalignment technique known for forming an alignment material of a liquid crystal panel. That is, a coating film made of a photoalignable material is provided on a substrate, and two types of polarized light having different polarization directions are irradiated to this. Then, a photo alignment film is obtained as an alignment material in which two types of liquid crystal alignment regions having different alignment control directions of liquid crystals are formed.
  • a solution-like retardation material containing a polymerizable liquid crystal is coated on the photoalignment film to realize the alignment of the polymerizable liquid crystal. Thereafter, the oriented polymerizable liquid crystal is cured to form a patterned retardation material.
  • the anti-reflection film of the organic EL display is composed of a linear polarizer and a quarter-wave retarder, and the extraneous light directed to the panel surface of the image display panel is converted into linearly polarized light by the linear polarizer, and the subsequent quarter-wave The light is converted to circularly polarized light by a retardation plate.
  • the extraneous light by this circularly polarized light is reflected by the surface of the image display panel or the like, the rotational direction of the polarization plane is reversed at the time of this reflection.
  • the reflected light is converted by the 1 ⁇ 4 wavelength retardation plate into linearly polarized light in the direction to be blocked by the linear polarization plate and then blocked by the subsequent linear polarization plate, contrary to the time of arrival.
  • outgoing radiation to the outside is significantly suppressed.
  • Patent Document 2 describes that this optical film has reverse dispersion characteristics by constituting a quarter-wave retarder by combining a half-wave plate and a quarter-wave plate.
  • a method of configuring by In this method it is possible to construct an optical film with reverse dispersion characteristics using a liquid crystal material with positive dispersion characteristics in a wide wavelength band for displaying a color image.
  • Patent Documents 3 and 4 As a liquid crystal material applicable to this retardation layer, one having an inverse dispersion characteristic has been proposed (Patent Documents 3 and 4). According to the liquid crystal material having such an inverse dispersion characteristic, instead of forming a 1 ⁇ 4 wavelength retardation plate by combining 2 layers of a 1 ⁇ 2 wavelength plate and a 1 ⁇ 4 wavelength plate, it is possible to use a retardation layer Can be secured by a single layer to ensure reverse dispersion characteristics, whereby an optical film capable of securing a desired retardation in a wide wavelength band can be realized with a simple configuration.
  • An alignment layer is used to align the liquid crystal.
  • a method of forming an alignment layer for example, a rubbing method or a photo-alignment method is known, and the photo-alignment method is capable of quantitative control of alignment processing without generating static electricity and dust which are problems of the rubbing method.
  • an acrylic resin, a polyimide resin, etc. which have photodimerization sites, such as a cinnamoyl group and a chalcone group, in a side chain as an available photoalignment property material are known. It has been reported that these resins exhibit the ability to control the alignment of liquid crystals (hereinafter also referred to as liquid crystal alignment) by irradiating polarized UV light (see Patent Documents 5 to 7).
  • the alignment layer is required to have adhesion to the liquid crystal layer.
  • the liquid crystal layer may be peeled off in the winding step or the like included in the production of the retardation film.
  • JP 2005-49865 A Japanese Patent Application Laid-Open No. 10-68816 U.S. Pat. No. 8,119,026 JP, 2009-179563, A Patent No. 3611342 JP, 2009-058584, A Japanese Patent Publication No. 2001-517719
  • an object of the present invention is made based on the above findings and examination results. That is, an object of the present invention is to provide a cured film-forming composition for providing an alignment material which exhibits good liquid crystal alignment and is excellent in adhesion to a liquid crystal layer.
  • the present inventors conducted intensive studies to achieve the above object, and as a result, (A) a reaction product of a polymer having an epoxy group and a cinnamic acid derivative having a group containing a polymerizable double bond, (B) By selecting a cured film-forming composition based on a crosslinking agent, it has been found that a cured film can be formed which exhibits good liquid crystal alignment and is excellent in adhesion to a liquid crystal layer, thereby completing the present invention.
  • a cured film-forming composition comprising (A) a reaction product of a polymer having an epoxy group and a cinnamic acid derivative having a group having a polymerizable double bond and (B) a crosslinking agent.
  • A a reaction product of a polymer having an epoxy group and a cinnamic acid derivative having a group having a polymerizable double bond
  • B a crosslinking agent
  • the present invention relates to, as a third aspect, the cured film-forming composition according to the first aspect or the second aspect, wherein the cinnamic acid derivative having a group containing the polymerizable double bond is a compound represented by the following formula (1).
  • each of A 1 and A 2 independently represents a hydrogen atom or a methyl group
  • R 1 is the following formula (c-2) (In the formula (c-2), the broken line represents a bond
  • R 101 represents an alkylene group having 1 to 30 carbon atoms, and one or more hydrogen atoms of this alkylene group are replaced by a fluorine atom or an organic group
  • - M 1 is a hydrogen atom which may be substituted by a group selected from the group consisting of O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH- and -CO-
  • a methyl group is represented by R 2 represents a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent fused cyclic group,
  • the present invention relates to the cured film-forming composition as described in any one of the first aspect to the third aspect, wherein the crosslinking agent of the component (B) is a crosslinking agent having a methylol group or an alkoxymethyl group.
  • the first to fourth aspects which further contain a polymer having at least one group selected from the group consisting of (C) hydroxy group, carboxyl group, amido group, amino group, and alkoxysilyl group
  • the present invention relates to a cured film-forming composition according to any one of the above.
  • the present invention relates to the cured film forming composition according to any one of the first aspect to the fifth aspect, which further contains (D) a crosslinking catalyst.
  • the cured film-forming composition according to any one of the first to sixth aspects which contains a compound having at least one group.
  • the fifth to eighth aspects of the fifth to eighth aspects containing 1 part by mass to 400 parts by mass of the component (C) with respect to 100 parts by mass of the total amount of the crosslinking agents of the components (A) and (B)
  • the present invention relates to a cured film-forming composition according to any one of the above.
  • the sixth aspect to the ninth aspect which contain 0.01 parts by mass to 20 parts by mass of the component (D) with respect to 100 parts by mass of the total amount of the crosslinking agents of the components (A) and (B) It is related with the cured film formation composition as described in any one of a viewpoint.
  • the seventh to tenth aspects of the present invention are the seventh to tenth aspects containing 1 part by mass to 100 parts by mass of the component (E) with respect to 100 parts by mass of the total amount of the crosslinking agents
  • the present invention relates to a cured film-forming composition according to any one of the above.
  • the present invention relates to a cured film obtained from the cured film-forming composition according to any one of the first to eleventh aspects.
  • the present invention relates to, as a thirteenth aspect, an alignment material obtained from the cured film-forming composition according to any one of the first to eleventh aspects.
  • the present invention relates to, as a fourteenth aspect, a retardation material which is formed using a cured film obtained from the cured film forming composition according to any one of the first to eleventh aspects.
  • the cured film which shows favorable liquid crystal orientation, and is excellent in adhesiveness with a liquid crystal layer, and a cured film formation composition suitable for the formation can be provided.
  • a cured film formation composition suitable for the formation it is possible to provide an alignment material excellent in liquid crystal alignment and light transmission. Further, according to the present invention, it is possible to provide a retardation material capable of highly accurate optical patterning.
  • the cured film-forming composition of the present invention contains (A) a reaction product of a polymer having an epoxy group and a cinnamic acid derivative having a group containing a polymerizable double bond, and (B) a crosslinking agent.
  • the cured film-forming composition of the present invention further comprises a group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group as the component (C) in addition to the components (A) and (B). It can also contain a polymer having at least one group selected from Furthermore, a crosslinking catalyst can also be contained as (D) component.
  • component (E) at least one group A selected from the group consisting of one or more polymerizable groups and a hydroxy group, a carboxyl group, an amido group, an amino group, and an alkoxysilyl group It can contain a compound having one group. And, as long as the effects of the present invention are not impaired, other additives can be contained. The details of each component will be described below.
  • the component (A) contained in the cured film-forming composition of the present invention is a reaction product of a polymer having an epoxy group and a cinnamic acid derivative having a group containing a polymerizable double bond.
  • the polymer having an epoxy group can be, for example, a polymer of a polymerizable unsaturated compound having an epoxy group or a copolymer of a polymerizable unsaturated compound having an epoxy group and another polymerizable unsaturated compound.
  • polymerizable unsaturated compound having an epoxy group examples include, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl ⁇ -ethyl acrylate, glycidyl ⁇ -n-propyl acrylate, glycidyl ⁇ -n-butyl acrylate, acrylic Acids-3,4-Epoxybutyl, Methacrylic Acid-3,4-Epoxybutyl, Acrylic Acid-6,7-Epoxyheptyl, Methacrylic Acid-6,7-Epoxyheptyl, ⁇ -Ethyl Acrylic Acid-6,7-Epoxy Examples include heptyl, o-vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether and the like.
  • polymerizable unsaturated compounds include (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclic alkyl ester, methacrylic acid aryl ester, acrylic acid aryl ester, unsaturated dicarboxylic acid diester, bicyclo unsaturated compounds, maleimide Compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, and other polymerizable unsaturated compounds can be mentioned.
  • alkyl methacrylates such as hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, diethylene glycol monomethacrylate, 2,3-dihydroxypropyl methacrylate, and the like.
  • Methacryloxyethyl glycoside 4-hydroxyphenyl methacrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate Etc .; as acrylic acid alkyl esters, eg methyl acrylate Over DOO, isopropyl acrylate and the like; as methacrylic acid cyclic alkyl esters such as cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 2,6] decan-8-yl methacrylate, tricyclo [5.2.
  • the copolymerization ratio of the polymerizable unsaturated compound having an epoxy group in the polymer having an epoxy group is preferably 30% by mass or more, and more preferably 50% by mass or more.
  • the synthesis of the polymer having an epoxy group can be carried out by a known radical polymerization method, preferably in the presence of a suitable polymerization initiator in a solvent.
  • a commercial item may be used as a polymer which has an epoxy group.
  • EHPE3150, EHPE3150CE above, Daicel (formerly Daicel Chemical Industries, Ltd.) made
  • UG-4010, UG-4035, UG-4040, UG-4070 above, Toa Synthetic ( ALUFON series, Inc., ECN-1299 (Asahi Kasei Corporation), DEN 431, DEN 438 (above, Dow Chemical Co., Ltd.), jER-152 (Mitsubishi Chemical Co., Ltd.
  • the polymerizable double bond is preferably a carbon-carbon double bond.
  • the group containing a carbon-carbon double bond for example, a vinyl group, a (meth) acryloyl group, an acrylamide group and the like can be mentioned, and a (meth) acryloyl group is preferable.
  • each of A 1 and A 2 independently represents a hydrogen atom or a methyl group
  • R 1 is the following formula (c-2) (In the formula (c-2), the broken line represents a bond
  • R 101 represents an alkylene group having 1 to 30 carbon atoms, and one or more hydrogen atoms of this alkylene group are replaced by a fluorine atom or an organic group
  • - M 1 is a hydrogen atom which may be substituted by a group selected from the group consisting of O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH- and -CO- Or a methyl group is represented by R 2
  • Examples of the divalent aromatic group of R 2 include 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 2,3,5,6- Tetrafluoro-1,4-phenylene group etc .;
  • a divalent alicyclic group of R 2 1,2-cyclopropylene group, 1,3-cyclobutylene group, 1,4-cyclohexylene group etc.
  • the divalent heterocyclic group for R 2 for example, 1,4-pyridine group, 2,5-pyridylene group, 1,4-furanylene group etc .; for the divalent fused cyclic group for R 2 For example, 2,6-naphthylene group etc. can be mentioned respectively.
  • R 2 a 1,4-phenylene group is preferable.
  • Preferred examples of the compound represented by the above formula (1) include the following formulas M1-1 to M1-5. (Wherein, M 1 is a hydrogen atom or a methyl group, s 1 represents the number of methylene groups, and is a natural number of 2 to 9)
  • the compound represented by the said Formula (1) can be synthesize
  • the reaction product of a polymer having an epoxy group and a specific cinnamic acid derivative contained in the liquid crystal aligning agent of the present invention comprises a polymer having an epoxy group as described above and a specific cinnamic acid derivative, preferably a catalyst. It can be synthesized by reacting in the presence, preferably in a suitable organic solvent.
  • the proportion of the cinnamic acid derivative used in the reaction is preferably 0.01 to 1.5 moles, more preferably 0.05 to 1 mole, relative to 1 mole of epoxy groups contained in the polymer having an epoxy group. It is 1.3 mol, more preferably 0.1 to 1.1 mol.
  • an organic catalyst which can be used here a compound known as a so-called curing accelerator which promotes the reaction of an organic base or an epoxy compound with an acid anhydride can be used.
  • organic base examples include primary to secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine and pyrrole; triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, Tertiary organic amines such as diazabicycloundecene; quaternary organic amines such as tetramethyl ammonium hydroxide can be mentioned.
  • primary to secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine and pyrrole
  • triethylamine tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine
  • Tertiary organic amines such as diazabicycloundecene
  • quaternary organic amines such as tetramethyl ammonium hydroxide
  • tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine and 4-dimethylaminopyridine; and quaternary organic amines such as tetramethylammonium hydroxide preferable.
  • the curing accelerator examples include benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, cyclohexyldimethylamine, tertiary amines such as triethanolamine; 2-methylimidazole, 2-n-heptylimidazole , 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 2- Ethyl-4-methylimidazole, 1- (2-cyanoethyl) -2-methylimidazole, 1- (2-cyanoethyl) -2-n-undecylimidazole, 1- (2-cyanoethyl) -2-phenylimidazole, 1 -(2-cyanoethyl) -2-ethyl 4-Methylimidazo
  • quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride and tetra-n-butylammonium chloride.
  • the proportion of the catalyst used is preferably 100 parts by mass or less, more preferably 0.01 to 100 parts by mass, still more preferably 0.1 to 20 parts by mass, with respect to 100 parts by mass of the polymer having an epoxy group.
  • organic solvent a hydrocarbon compound, an ether compound, an ester compound, a ketone compound, an amide compound, an alcohol compound etc. can be mentioned, for example.
  • ether compounds, ester compounds, ketone compounds and alcohol compounds are preferable from the viewpoint of the solubility of the raw materials and products and the ease of purification of the products.
  • the solvent is used in an amount such that the solid concentration (the ratio of the mass of components other than the solvent in the reaction solution to the total mass of the solution) is preferably 0.1% by mass or more, more preferably 5 to 50% by mass Be done.
  • the reaction temperature is preferably 0 to 200 ° C., more preferably 50 to 150 ° C.
  • the reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours. In this way, a solution is obtained which contains the reaction product of a polymer having an epoxy group and a specific cinnamic acid derivative.
  • This solution may be used as it is for preparation of a liquid crystal aligning agent, or may be used for preparing a liquid crystal aligning agent after isolating a polymer contained in the solution, or after purifying the isolated polymer. You may use for preparation of a liquid crystal aligning agent.
  • the component (B) in the cured film-forming composition of the present invention is a crosslinking agent.
  • the crosslinking agent which is the component (B) is preferably a crosslinking agent having a group capable of forming a crosslink with the thermally crosslinkable functional group of the component (A), such as a methylol group or an alkoxymethyl group. Examples of compounds having these groups include methylol compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine and alkoxymethylated melamine.
  • alkoxymethylated glycoluril examples include, for example, 1,3,4,6-tetrakis (methoxymethyl) glycoluril, 1,3,4,6-tetrakis (butoxymethyl) glycoluril, 1,3,4 , 6-Tetrakis (hydroxymethyl) glycoluril, 1, 3-bis (hydroxymethyl) urea, 1, 1, 3, 3- tetrakis (butoxymethyl) urea, 1, 1, 3, 3- tetrakis (methoxymethyl) Examples thereof include urea, 1,3-bis (hydroxymethyl) -4,5-dihydroxy-2-imidazolinone, and 1,3-bis (methoxymethyl) -4,5-dimethoxy-2-imidazolinone.
  • alkoxymethylated benzoguanamine examples include tetramethoxymethylbenzoguanamine and the like.
  • Nippon Cytech Industries Co., Ltd. formerly Mitsui Cytec Co., Ltd.
  • Cymel registered trademark
  • Sanwa Chemical Co., Ltd. trade name: Nikalac (registered trademark) BX-) 4000, BX-37, BL-60, BX-55H) and the like.
  • alkoxymethylated melamine examples include, for example, hexamethoxymethylmelamine.
  • methoxymethyl type melamine compound (trade name: Cymel (registered trademark) 300, 301, 303, 350), butoxymethyl type melamine Compound (trade name: Mycoat (registered trademark) 506, 508), methoxymethyl type melamine compound (trade name: Nikalac (registered trademark) MW-30, MW-22, MW-22 manufactured by Sanwa Chemical Co., Ltd.
  • it may be a compound obtained by condensing a melamine compound, a urea compound, a glycoluril compound and a benzoguanamine compound in which the hydrogen atom of such an amino group is substituted with a methylol group or an alkoxymethyl group.
  • a melamine compound a urea compound, a glycoluril compound and a benzoguanamine compound in which the hydrogen atom of such an amino group is substituted with a methylol group or an alkoxymethyl group.
  • high molecular weight compounds prepared from melamine compounds and benzoguanamine compounds described in US Pat. No. 6,323,310 can be mentioned.
  • Examples of commercially available products of the melamine compound include trade name: Cymel (registered trademark) 303
  • examples of commercially available products of the benzoguanamine compound include trade name: Cymel (registered trademark) 1123 (above, Nippon Cytech Industries, Ltd. And the like (manufactured by Mitsui
  • hydroxymethyl groups such as N-hydroxymethyl acrylamide, N-methoxymethyl methacrylamide, N-ethoxymethyl acrylamide, N-butoxymethyl methacrylamide or alkoxymethyl groups
  • hydroxymethyl groups such as N-hydroxymethyl acrylamide, N-methoxymethyl methacrylamide, N-ethoxymethyl acrylamide, N-butoxymethyl methacrylamide or alkoxymethyl groups
  • Polymers prepared using acrylamide compounds or methacrylamide compounds substituted with can also be used.
  • polymers for example, poly (N-butoxymethyl acrylamide), a copolymer of N-butoxymethyl acrylamide and styrene, a copolymer of N-hydroxymethyl methacrylamide and methyl methacrylate, N-ethoxymethyl
  • polymers for example, poly (N-butoxymethyl acrylamide), a copolymer of N-butoxymethyl acrylamide and styrene, a copolymer of N-hydroxymethyl methacrylamide and methyl methacrylate, N-ethoxymethyl
  • examples thereof include copolymers of methacrylamide and benzyl methacrylate, and copolymers of N-butoxymethyl acrylamide, benzyl methacrylate and 2-hydroxypropyl methacrylate, and the like.
  • the method for obtaining the polymer as described above is not particularly limited.
  • the specific functional group 1 means a carboxyl group, a glycidyl group, a hydroxy group, an amino group having active hydrogen, a functional group such as a phenolic hydroxy group or an isocyanate group, or a plurality of functional groups selected therefrom. say.
  • preferred combinations of the specific functional group 1 and the functional group possessed by the specific compound and involved in the reaction are a carboxyl group and an epoxy group, a hydroxy group and an isocyanate group, a phenolic hydroxy group and an epoxy group A carboxyl group and an isocyanate group, an amino group and an isocyanate group, or a hydroxy group and an acid chloride.
  • a more preferable combination is a carboxyl group and glycidyl methacrylate, or a hydroxyl group and isocyanate ethyl methacrylate.
  • the weight average molecular weight (in terms of polystyrene) of such a polymer is 1,000 to 500,000, preferably 2,000 to 200,000, more preferably 3,000 to 150,000. More preferably, it is 3,000 to 50,000.
  • crosslinking agents can be used alone or in combination of two or more.
  • the content of the crosslinking agent of the component (B) in the cured film-forming composition of the present invention is preferably 1 part by mass to 500 parts by mass, and more preferably, based on 100 parts by mass of the polymer which is the component (A). 5 parts by mass to 400 parts by mass.
  • the content of the crosslinking agent is too small, the solvent resistance of the cured film obtained from the cured film-forming composition is lowered, and the liquid crystal alignment is lowered. On the other hand, when the content is excessive, the liquid crystal alignment and storage stability may be lowered.
  • the cured film-forming composition of the present invention comprises, as component (C), at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group (hereinafter also referred to as a specific functional group 2) May be contained in the polymer.
  • component (C) at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group (hereinafter also referred to as a specific functional group 2) May be contained in the polymer.
  • polymer which is the component (C) for example, acrylic polymer, polyamic acid, polyimide, polyvinyl alcohol, polyester, polyester polycarboxylic acid, polyether polyol, polyester polyol, polycarbonate polyol, polycaprolactone polyol, polyalkyleneimine, poly Examples thereof include polymers having a linear or branched structure such as allylamine, celluloses (cellulose or derivatives thereof), phenol novolac resin, and melamine formaldehyde resin, and cyclic polymers such as cyclodextrins.
  • the polymer which is the component (C) preferably includes acrylic polymers, hydroxyalkyl cyclodextrins, celluloses, polyether polyols, polyester polyols, polycarbonate polyols and polycaprolactone polyols.
  • the acrylic polymer which is a preferable example of the polymer of the component (C) is a polymer obtained by polymerizing a monomer having an unsaturated double bond such as acrylic acid, methacrylic acid, styrene, vinyl compound, etc.
  • the polymer may be a polymer obtained by polymerizing a monomer containing a monomer having a functional group 2 or a mixture thereof, and the type and the like of the main chain skeleton and side chains of the polymer constituting the acrylic polymer are not particularly limited.
  • a monomer having the specific functional group 2 a monomer having a polyethylene glycol ester group, a monomer having a hydroxyalkyl ester group having 2 to 5 carbon atoms, a monomer having a phenolic hydroxy group, a monomer having a carboxyl group, an amino group And monomers having an alkoxysilyl group and a group represented by Formula 2 above.
  • Examples of the above-described monomer having a polyethylene glycol ester group 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 described above include, for example, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate And 4-hydroxybutyl methacrylate.
  • Examples of the above-mentioned monomer having a phenolic hydroxy group include p-hydroxystyrene, m-hydroxystyrene and o-hydroxystyrene.
  • acrylic acid methacrylic acid
  • vinyl benzoic acid is mentioned, for example.
  • Examples of the above-mentioned monomer having an amino group in the side chain include 2-aminoethyl acrylate, 2-aminoethyl methacrylate, aminopropyl acrylate and aminopropyl methacrylate.
  • Examples of the above-mentioned monomer having an alkoxysilyl group in the side chain include 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane Silane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane and the like can be mentioned.
  • the acrylic polymer which is an example of the component (C)
  • Monomers which do not have any of the represented groups can be used in combination.
  • Such monomers include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds and vinyl compounds.
  • acrylic acid ester compound for example, methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl Acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2- Propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, Beauty, etc. 8-ethyl-8-tricyclodecyl acrylate.
  • methacrylic acid ester compound examples include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl Methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2- Propyl-2-adamantyl methacrylate, 8-meth Le -8- tricyclodecyl methacrylate, and, 8-e
  • maleimide compound examples include maleimide, N-methyl maleimide, N-phenyl maleimide, and N-cyclohexyl maleimide.
  • styrene compounds include styrene, methylstyrene, chlorostyrene, bromostyrene and the like.
  • vinyl compounds include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.
  • the amount of the monomer having the specific functional group 2 used to obtain the acrylic polymer which is an example of the component (C) is based on the total amount of all the monomers used to obtain the acrylic polymer which is the component (C). And preferably 2 mol% or more. If the monomer having the specific functional group 2 is less than 2 mol%, the solvent resistance of the resulting cured film tends to be insufficient.
  • the method of obtaining the acrylic polymer which is an example of (C) component is not specifically limited,
  • the monomer containing the monomer which has the specific functional group 2, and the monomer which does not have the specific functional group 2 if needed, and a polymerization initiator It is obtained by a polymerization reaction at a temperature of 50.degree. C. to 110.degree. C. in a solvent in the presence of, etc.
  • the solvent to be used is not particularly limited as long as it dissolves the monomer having the specific functional group 2, and the optionally used monomer having no specific functional group 2, the polymerization initiator and the like.
  • the acrylic polymer which is an example of (C) component obtained by the above method is a state of the solution normally melt
  • the powder can be dried at normal temperature or dried by heating under normal pressure or reduced pressure to form a powder of an acrylic polymer which is an example of the component (C).
  • the polymerization initiator coexisting with the acrylic polymer which is an example of the component (C) and unreacted monomers can be removed, and as a result, the acrylic polymer which is an example of the purified component (C) Powder is obtained. If sufficient purification can not be performed by one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.
  • the acrylic polymer which is a preferable example of the component (C) preferably has a weight average molecular weight of 3,000 to 200,000, more preferably 4,000 to 150,000, and still more preferably 5,000 to 100,000. If the weight average molecular weight is more than 200,000 and is too large, the solubility in solvents may be reduced and the handling properties may be reduced. If the weight average molecular weight is less than 3000 and is too low, the curing is insufficient at the time of heat curing And the solvent resistance may be reduced.
  • the weight average molecular weight is a value obtained by gel permeation chromatography (GPC) using polystyrene as a standard material.
  • GPC gel permeation chromatography
  • polyether polyol which is a preferable example of the component (C)
  • polyethylene oxide polypropylene glycol, propylene glycol, bisphenol A, triethylene glycol, polyhydric alcohol such as sorbitol, propylene oxide, polyethylene glycol, polypropylene glycol, etc.
  • polyether polyols include Adeka Polyether P series, G series, EDP series, BPX series, FC series, CM series manufactured by Adeka, 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 And Nonion (registered trademark) LT-221, ST-221, OT-221 and the like.
  • polyester polyol which is a preferable example of (C) component
  • diols such as ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, polypropylene glycol, etc. were made to react with polyvalent carboxylic acids, such as adipic acid, sebacic acid, and isophthalic acid.
  • polyvalent carboxylic acids such as adipic acid, sebacic acid, and isophthalic acid.
  • Specific examples of the polyester polyol include Polylight (registered trademark) OD-X-286, OD-X-102, OD-X-355, OD-X-2330, OD-X-240, OD-X-668, manufactured by DIC.
  • polycaprolactone polyol which is a preferable example of the component (C)
  • a polycaprolactone polyol which is a preferable example of the component (C)
  • a polyhydric alcohol such as trimethylolpropane or ethylene glycol as an initiator
  • Specific examples of the polycaprolactone polyol include Polylight (registered trademark) OD-X-2155, OD-X-640, and OD-X-2568 manufactured by DIC, Plaxel (registered trademark) 205 manufactured by Daicel, 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 component (C) include those obtained by reacting a polyhydric alcohol such as trimethylolpropane or ethylene glycol with diethyl carbonate, diphenyl carbonate, ethylene carbonate or the like.
  • polycarbonate polyols include PLACEL (registered trademark) CD205, CD205PL, CD210, CD220 manufactured by Daicel, C-590, C-1050, C-2050, C-2090, C-3090 and the like manufactured by Kuraray.
  • Preferred examples of the component (C) include celluloses such as hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose, hydroxyalkyl alkyl celluloses such as hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose and hydroxyethyl ethyl cellulose, and cellulose.
  • celluloses such as hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose, and hydroxyalkyl alkyl celluloses such as hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose and hydroxyethyl ethyl cellulose, and cellulose.
  • hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose are preferable.
  • cyclodextrins which are preferable examples of the component (C) include cyclodextrins such as ⁇ -cyclodextrin, ⁇ -cyclodextrin and ⁇ -cyclodextrin, methyl- ⁇ -cyclodextrin, methyl- ⁇ -cyclodextrin and methyl- ⁇ Methylated cyclodextrins such as -cyclodextrin, hydroxymethyl- ⁇ -cyclodextrin, hydroxymethyl- ⁇ -cyclodextrin, hydroxymethyl- ⁇ -cyclodextrin, 2-hydroxyethyl- ⁇ -cyclodextrin, 2-hydroxyethyl- ⁇ -Cyclodextrin, 2-hydroxyethyl- ⁇ -cyclodextrin, 2-hydroxypropyl- ⁇ -cyclodextrin, 2-hydroxypropyl- ⁇ -cyclodextrin, 2-hydroxypropyl- ⁇ -cyclodextrin, 2-hydroxypropyl- ⁇ -
  • melamine formaldehyde resin which is a preferable example of (C) component, resin obtained by polycondensing melamine and formaldehyde is mentioned.
  • the melamine formaldehyde resin of component (C) is preferably an alkylated methylol group formed during the polycondensation of melamine and formaldehyde.
  • a melamine formaldehyde resin of (C) component resin which has a unit structure represented, for example by a following formula is mentioned.
  • R 21 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • n is a natural number representing the number of repeating units.
  • the method for obtaining the melamine formaldehyde resin of the component (C) is not particularly limited, but generally, melamine and formaldehyde are mixed, and after being weakly alkaline using sodium carbonate, ammonia and the like, heating is carried out at 60 ° C to 100 ° C.
  • the methylol group can be alkoxylated by reacting with an alcohol.
  • the weight average molecular weight of the melamine formaldehyde resin of the component (C) is preferably 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 more than 5000, the solubility in the solvent may be reduced and the handling properties may be reduced. If the weight average molecular weight is less than 250 and the amount is too small, the curing is insufficient at the time of heat curing As a result, the effect of improving the solvent resistance may not be sufficiently exhibited.
  • the melamine formaldehyde resin of the component (C) may be used in the form of a liquid, or in the form of a solution in which the purified liquid is redissolved in a solvent described later.
  • a phenol novolak resin which is a preferable example of the component (C)
  • a phenol-formaldehyde polycondensate and the like can be mentioned.
  • the polymer of the component (C) may be used in the form of a powder or in the form of a solution in which the purified powder is redissolved in a solvent described later.
  • the component (C) may be a mixture of two or more of the polymers exemplified as the component (C).
  • the content of component (C) in the cured film-forming composition of the present invention is preferably 100 parts by mass of the total amount of the polymer as component (A) and the crosslinking agent as component (B).
  • the content is 400 parts by mass or less, more preferably 10 parts by mass to 380 parts by mass, and still more preferably 40 parts by mass to 360 parts by mass.
  • the content of the component (C) is excessive, the liquid crystal alignment tends to be deteriorated.
  • the cured film formation composition of this invention can contain the bridge
  • a crosslinking catalyst which is (D) component an acid or a thermal acid generator can be used conveniently, for example.
  • This (D) component is effective in promoting the thermosetting reaction of the cured film-forming composition of the present invention.
  • Specific examples of the component (D) include, as the acid, a sulfonic acid group-containing compound, hydrochloric acid or a salt thereof.
  • the thermal acid generator is not particularly limited as long as it is a compound which is thermally decomposed during heat treatment to generate an acid, that is, a compound which is thermally decomposed at a temperature of 80 ° C. to 250 ° C. to generate an acid. .
  • the above-mentioned acid include, for example, hydrochloric acid or a salt thereof; methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, camphor Sulfonic acid, trifluoromethanesulfonic acid, p-phenolsulfonic acid, 2-naphthalenesulfonic acid, mesitylenesulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, 1H, Sulfonic acid group-containing compounds such as 1H, 2H, 2H-perfluorooctanesulfonic acid, perfluoro (2-ethoxyethane) sulfonic acid
  • a compound capable of generating an acid by heat for example, bis (tosyloxy) ethane, bis (tosyloxy) propane, bis (tosyloxy) butane, p-nitrobenzyl tosylate, o-nitrobenzyl tosylate, -Phenylene tris (methyl sulfonate), p-toluenesulfonic acid pyridinium salt, p-toluenesulfonic acid morpholinium 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, cyan
  • the content of the component (D) in the cured film-forming composition of the present invention is preferably 0.01 parts by mass with respect to 100 parts by mass of the total amount of the polymer as the component (A) and the crosslinking agent of the component (B).
  • the amount is from 20 parts by mass to 20 parts by mass, more preferably 0.1 parts by mass to 15 parts by mass, and still more preferably 0.5 parts by mass to 10 parts by mass.
  • component (E) at least one group A selected from the group consisting of one or more polymerizable groups and a hydroxy group, a carboxyl group, an amido group, an amino group, and an alkoxysilyl group or the group A It can also contain compounds having at least one group to react. This acts as a component that improves the adhesion of the formed cured film (hereinafter, also referred to as an adhesion improving component).
  • the adhesion of the alignment material to the layer of the polymerizable liquid crystal is improved,
  • the crosslinkable reaction site of the polymerizable functional group and the orienting material can be linked by covalent bond.
  • the phase difference material of the present embodiment formed by laminating the cured polymerizable liquid crystal on the alignment material of the present embodiment can maintain strong adhesion even under high temperature and high quality conditions, peeling etc. It can show high resistance to
  • component (E) monomers and polymers having a group selected from a hydroxy group and an N-alkoxymethyl group and a polymerizable group are preferable.
  • a compound having a hydroxy group and a (meth) acrylic group a compound having an N-alkoxymethyl group and a (meth) acrylic group, an N-alkoxymethyl group and a (meth) acrylic group And the like. Specific examples are shown below.
  • the polyfunctional acrylate (Hereafter, it is also called a hydroxy group containing polyfunctional acrylate.) Containing a hydroxy group can be mentioned.
  • the hydroxy group-containing polyfunctional acrylate which is an example of the component (E) include pentaerythritol triacrylate and dipentaerythritol pentaacrylate.
  • the compound which has one acryl group and one or more hydroxy groups is also mentioned as an example of (E) component.
  • Preferred examples of such compounds having one acrylic group and one or more hydroxy groups are listed.
  • the compound of (E) component is not limited to the following compound example.
  • R 11 represents a hydrogen atom or a methyl group, and m represents an integer of 1 to 10).
  • the N of an N-alkoxymethyl group that is, the nitrogen atom of an amide, a nitrogen atom of a thioamide, a nitrogen atom of a urea, a nitrogen atom of a thiourea, a nitrogen atom of a urethane, a nitrogen atom of a urethane, a nitrogen atom of a nitrogen-containing heterocyclic ring And a nitrogen atom etc.
  • a nitrogen atom of an amide, a nitrogen atom of a thioamide, a nitrogen atom of a urea, a nitrogen atom of a thiourea, a nitrogen atom of a urethane, a nitrogen atom of a urethane, a nitrogen bonded adjacent to a nitrogen atom of a nitrogen-containing heterocyclic ring A structure in which an alkoxymethyl group is bonded to a nitrogen atom selected from atoms and the like can be mentioned.
  • any one having the above-mentioned group may be used, and preferably, for example, a compound represented by the following formula (X1) can be mentioned.
  • R 31 represents a hydrogen atom or a methyl group
  • R 32 represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms
  • alkyl group examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, 1-methyl-n -Butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl- n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl- n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-
  • the compound represented by the above formula (X1) include N-hydroxymethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-butoxymethyl (meth)
  • An acrylamide compound or a methacrylamide compound substituted with a hydroxymethyl group or an alkoxymethyl group such as acrylamide may be mentioned.
  • (meth) acrylamide means both methacrylamide and acrylamide.
  • a compound represented by the following formula (X2) is preferably exemplified.
  • R 51 represents a hydrogen atom or a methyl group.
  • R 52 represents an alkyl group having 2 to 20 carbon atoms, a monovalent aliphatic ring group having 5 to 6 carbon atoms, or a monovalent aliphatic group containing an aliphatic ring having 5 to 6 carbon atoms,
  • the structure may contain an ether bond.
  • R 53 represents a linear or branched alkylene group having 2 to 20 carbon atoms, a divalent aliphatic ring group having 5 to 6 carbon atoms, or a divalent containing an aliphatic ring having 5 to 6 carbon atoms And an ether bond may be included in the structure.
  • R 54 is a linear or branched divalent to pentavalent aliphatic group having 1 to 20 carbon atoms, a divalent to ninth divalent aliphatic ring group having 5 to 6 carbon atoms, or 5 carbon atoms And a divalent to nine-valent aliphatic group containing one to six aliphatic rings, wherein one methylene group or a plurality of non-adjacent methylene groups of these groups may be replaced by an ether bond.
  • Z is> NCOO- or -OCON ⁇ (where, "-" indicates that there is one bond, and ">" or " ⁇ " indicates that there are two bonds, and Indicates that an alkoxymethyl group (ie, -OR52 group) is bonded to any one bond.
  • r is a natural number of 2 or more and 9 or less.
  • alkylene group having 2 to 20 carbon atoms in the definition of R 53 include divalent groups in which one hydrogen atom is further removed from the alkyl group having 2 to 20 carbon atoms. Further, as a specific example of the divalent to decavalent aliphatic group having 1 to 20 carbon atoms in the definition of R 54 , 1 to 8 hydrogen atoms are further removed from the alkyl group having 1 to 20 carbon atoms Divalent to 9-valent groups may be mentioned.
  • the alkyl group having 1 carbon atom is a methyl group, and specific examples of the alkyl group having 2 to 20 carbon atoms include ethyl group, n-propyl group, i-propyl group, n-butyl group and i-butyl group.
  • an alkylene group having 2 to 10 carbon atoms is preferable, and it is particularly preferable that R 53 is an ethylene group and R 54 is a hexylene group from the viewpoint of availability of raw materials.
  • alkyl group having 1 to 20 carbon atoms in the definition of R 52 include the specific examples of the alkyl group having 2 to 20 carbon atoms in the definition of R 53 and a methyl group.
  • an alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group, an ethyl group, an n-propyl group or an n-butyl group is particularly preferable.
  • a natural number of 2 or more and 9 or less can be mentioned, and among them, 2 to 6 is preferable.
  • the content of the component (E) in the cured film-forming composition of the embodiment of the present invention is preferably 1 part by mass with respect to 100 parts by mass of the total amount of the polymer as the component (A) and the crosslinking agent of the component (B).
  • the amount is 100 parts by mass, and more preferably 5 parts by mass to 70 parts by mass.
  • the cured film-forming composition of the present invention is used mainly in the form of a solution dissolved in a solvent.
  • the solvent used at that time should just be able to dissolve the (A) component, the (B) component and, if necessary, the (C) component, the (D) component, the (E) component and / or other additives described later,
  • the type, structure, etc. are not particularly limited.
  • the solvent include, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-methyl-1-butanol, n-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol propyl ether, propylene glycol propyl ether acetate, Toluene, xylene, methyl Ethyl ketone, isobutyl methyl ketone, cyclopentanone, ethylene
  • the cured film-forming composition of the present invention contains the polymer of component (A) and the crosslinking agent of component (B), and optionally the polymer of component (C), the crosslinking catalyst of component (D) and the component (E) adhesion It is a composition which can contain an accelerator and further other additives as long as the effect of the present invention is not impaired. And, usually, they are used in the form of a solution dissolved in a solvent.
  • the preferable example of the cured film formation composition of this invention is as follows. [1] A cured film-forming composition containing 1 part by mass to 500 parts by mass of the (B) component based on 100 parts by mass of the (A) component and the (A) component.
  • a cured film-forming composition comprising 1 to 400 parts by mass of the component (C) with respect to 100 parts by mass of the total amount of [3]
  • a cured film-forming composition containing 1 part by mass to 500 parts by mass of the component (B) and a solvent based on 100 parts by mass of the component (A) and the component (A).
  • the compounding ratio in the case of using the cured film formation composition of this invention as a solution, a preparation method, etc. are explained in full detail below.
  • the ratio of solid content in the cured film-forming composition of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, but is 1% by mass to 60% by mass, and preferably 2
  • the content is 50% by mass, more preferably 2% by mass to 20% by mass.
  • solid content means what remove
  • the method for preparing the cured film-forming composition of the present invention is not particularly limited.
  • a preparation method for example, the solution of the component (A) dissolved in a solvent, the component (B), and further, the components (C), (D), (E) and the like are mixed at a predetermined ratio and homogeneous.
  • the method of making it into a solution, or the method of adding and mixing other additives as needed at the appropriate stage of this preparation method may be mentioned.
  • the solution of the specific copolymer (polymer) obtained by the polymerization reaction in a solvent can be used as it is.
  • component (B), component (C), component (D), component (E) and the like are added to the solution of component (A) in the same manner as described above to obtain a uniform solution.
  • a solvent may be additionally added for the purpose of adjusting the concentration.
  • the solvent used in the process of producing the component (A) and the solvent used for adjusting the concentration of the cured film-forming composition may be the same or different.
  • the solution of the cured film forming composition of the present invention is used as 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, a quartz substrate, ITO Substrates, etc.) and film substrates (eg, triacetyl cellulose (TAC) film, polycarbonate (PC) film, cycloolefin polymer (COP) film, cycloolefin copolymer (COC) film, polyethylene terephthalate (PET) film, acrylic film, polyethylene film Coating film is formed on a resin film such as a film by bar coating, spin coating, flow coating, roll coating, slit coating, slit coating followed by spin coating, inkjet coating, printing, etc. Relieved Dried by heating with a plate or an oven or the like, it is possible to form a resin film such as a film by bar coating, spin
  • the conditions for the heating and drying may be such that the crosslinking reaction by the crosslinking agent proceeds to such an extent that the components of the cured film (alignment material) do not elute in the polymerizable liquid crystal solution applied thereon.
  • a heating temperature and a heating time appropriately selected from the range of 200 ° C. and 0.4 minutes to 60 minutes are employed.
  • the heating temperature and the heating time are preferably 70 ° C. to 160 ° C., for 0.5 minutes to 10 minutes.
  • the film thickness of the cured film (alignment material) formed using the curable composition of the present invention is, for example, 0.05 ⁇ m to 5 ⁇ m, and is appropriately determined in consideration of the difference in level of the substrate used and the optical and electrical properties. It can be selected.
  • the alignment material formed from the cured film composition of the present invention has solvent resistance and heat resistance, a retardation material such as a polymerizable liquid crystal solution having vertical alignment property is coated on the alignment material. And alignment on the alignment material. Then, by curing the retardation material in the oriented state as it is, the retardation material can be formed as a layer having optical anisotropy. And when the board
  • the cured film formation composition of this invention can be used suitably for manufacture of various retardation material (retardation film), a liquid crystal display element, etc.
  • the molecular weight of the acrylic copolymer in the polymerization example is as follows using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) manufactured by Shodex Corp. and a column (KD-803, KD-805) manufactured by Shodex Corp. And measured.
  • the following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are expressed in terms of polystyrene.
  • Standard sample for calibration curve preparation Standard polystyrene manufactured by Showa Denko (molecular weight about 197,000, 55, 100, 12, 800, 3, 950, 1, 260, 580).
  • Synthesis Example 1 5.2 g of the acrylic polymer (P1) having an epoxy group obtained in polymerization example 1, 12.0 g of CIN 1, 0.1 g of ethyltriphenylphosphonium bromide as a reaction catalyst, 0.2 g of dibutylhydroxytoluene as a polymerization inhibitor It was dissolved in 0. 0g and reacted at 100 ° C for 20 hours. This solution was gradually dropped into 1000 g of diethyl ether to precipitate a solid, which was filtered and dried under reduced pressure to obtain a polymer (PA-1). The epoxy value of the obtained polymer was measured to confirm that the epoxy group disappeared.
  • PA-1 polymer
  • Synthesis Example 2 5.2 g of the acrylic polymer (P1) having an epoxy group obtained in polymerization example 1, 11.0 g of CIN2, 0.1 g of ethyltriphenylphosphonium bromide as a reaction catalyst, 0.2 g of dibutylhydroxytoluene as a polymerization inhibitor It was dissolved in 0. 0g and reacted at 100 ° C for 20 hours. This solution was gradually dropped into 1000 g of diethyl ether to precipitate a solid, which was filtered and dried under reduced pressure to obtain a polymer (PA-2). The epoxy value of the obtained polymer was measured to confirm that the epoxy group disappeared.
  • Synthesis Example 3 5.2 g of the acrylic polymer (P1) having an epoxy group obtained in polymerization example 1, 12.0 g of CIN 3, 0.1 g of ethyltriphenylphosphonium bromide as a reaction catalyst, 0.2 g of dibutylhydroxytoluene as a polymerization inhibitor It was dissolved in 0. 0g and reacted at 100 ° C for 20 hours. This solution was gradually dropped into 1000 g of diethyl ether to precipitate a solid, which was filtered and dried under reduced pressure to obtain a polymer (PA-3). The epoxy value of the obtained polymer was measured to confirm that the epoxy group disappeared.
  • Synthesis Example 5 5.2 g of the acrylic polymer (P1) having an epoxy group obtained in polymerization example 1, 10.0 g of CIN 1, 2.0 g of CIN 4, 0.1 g of ethyltriphenylphosphonium bromide as a reaction catalyst, dibutyl hydroxytoluene as a polymerization inhibitor 0.2 g of PM was dissolved in 70.0 g of PM and reacted at 100 ° C. for 20 hours. This solution was gradually dropped into 1000 g of diethyl ether to precipitate a solid, which was filtered and dried under reduced pressure to obtain a polymer (PA-5). The epoxy value of the obtained polymer was measured to confirm that the epoxy group disappeared.
  • Synthesis Example 6 5.2 g of the acrylic polymer (P1) having an epoxy group obtained in polymerization example 1, 6.5 g of CIN 4, and 0.1 g of ethyltriphenylphosphonium bromide as a reaction catalyst are dissolved in 48.0 g of PM, and the reaction is carried out at 100 ° C. for 20 hours It was made to react. This solution was gradually dropped into 500 g of diethyl ether to precipitate a solid, which was filtered and dried under reduced pressure to obtain a polymer (PA-6). The epoxy value of the obtained polymer was measured to confirm that the epoxy group disappeared.
  • Example, Comparative Example> Each cured film formation composition of the Example and the comparative example was prepared with the composition shown in Table 1. Next, a cured film was formed using each retardation material formation composition, and evaluation of orientation and adhesiveness was performed about each obtained cured film.
  • the coating film was exposed at 300 mJ / cm 2 to prepare a retardation material.
  • the phase difference material on the manufactured substrate is sandwiched between a pair of polarizing plates, and the expression state of the phase difference characteristic of the phase difference material is observed, and the phase difference is expressed without defects ⁇ , the phase difference is not expressed
  • the thing was described in the column of "orientation" as x.
  • the evaluation results are summarized in Table 2 later.
  • the coating film was exposed at 300 mJ / cm 2 to prepare a retardation material.
  • This retardation material was incised with a cutter knife so as to be 10 ⁇ 10 squares at intervals of 1 mm in length and width.
  • a cellophane tape peel test was conducted using scotch tape on the incisions. The evaluation results were “adhesion”, and 100 squares were left without peeling, and those with even 1 square were marked ⁇ . The evaluation results are summarized in Table 2 later.
  • the alignment material obtained using the cured film-forming composition of the example exhibited good alignment and adhesion.
  • the alignment material obtained by using the cured film forming composition of the comparative example showed a good alignment, but no adhesion was obtained.
  • the cured film-forming composition according to the present invention is very useful as a material for forming an alignment material for forming a liquid crystal alignment film of a liquid crystal display element or an optically anisotropic film provided inside or outside of a liquid crystal display element.
  • it is suitable as a material for a retardation material of a circularly polarizing plate used as an antireflective film for IPS-LCDs and organic EL displays.

Abstract

Le problème à la base de la présente invention concerne une composition de formation de film durci pour obtenir un matériau d'orientation qui présente une bonne aptitude à l'orientation de cristaux liquides et une adhérence supérieure à une couche de cristaux liquides. La solution selon l'invention porte sur une composition de formation de film durci contenant (A) un produit de réaction d'un polymère comprenant un groupe époxy et d'un dérivé d'acide cinnamique comprenant un groupe présentant une double liaison polymérisable et (B) un agent de réticulation ; et un film durci, un matériau d'orientation et un matériau de contraste de phase qui sont obtenus à partir de celle-ci.
PCT/JP2018/029248 2017-08-03 2018-08-03 Composition formant un film durci, matériau d'orientation et matériau de contraste de phase WO2019027045A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN201880064199.0A CN111164120A (zh) 2017-08-03 2018-08-03 固化膜形成用组合物、取向材及相位差材
KR1020207004627A KR102662084B1 (ko) 2017-08-03 2018-08-03 경화막 형성 조성물, 배향재 및 위상차재
CN202310790480.5A CN116789871A (zh) 2017-08-03 2018-08-03 固化膜形成用组合物、取向材及相位差材
JP2019534604A JP7365003B2 (ja) 2017-08-03 2018-08-03 硬化膜形成組成物、配向材および位相差材

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017-151140 2017-08-03
JP2017151140 2017-08-03

Publications (1)

Publication Number Publication Date
WO2019027045A1 true WO2019027045A1 (fr) 2019-02-07

Family

ID=65232884

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/029248 WO2019027045A1 (fr) 2017-08-03 2018-08-03 Composition formant un film durci, matériau d'orientation et matériau de contraste de phase

Country Status (4)

Country Link
JP (1) JP7365003B2 (fr)
CN (2) CN111164120A (fr)
TW (1) TWI794261B (fr)
WO (1) WO2019027045A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016147987A1 (fr) * 2015-03-13 2016-09-22 日産化学工業株式会社 Composition de formation de film durci, matériau d'alignement et matériau de différence de phase
JP2017016116A (ja) * 2015-06-30 2017-01-19 富士フイルム株式会社 感光性樹脂組成物、硬化膜の製造方法、硬化膜および液晶表示装置

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101874225B (zh) * 2007-11-27 2012-12-05 Jsr株式会社 液晶取向剂、液晶取向膜的形成方法以及液晶显示元件
JP5790156B2 (ja) * 2010-07-15 2015-10-07 Jsr株式会社 位相差フィルム用液晶配向剤、位相差フィルム用液晶配向膜、位相差フィルム及びその製造方法
KR101989195B1 (ko) * 2012-01-23 2019-06-13 스미또모 가가꾸 가부시키가이샤 조성물 및 광학 필름
JP6146100B2 (ja) * 2012-06-21 2017-06-14 Jsr株式会社 液晶配向剤、液晶配向膜、位相差フィルム、液晶表示素子及び位相差フィルムの製造方法
CN106062009B (zh) * 2014-02-28 2018-03-27 日产化学工业株式会社 固化膜形成用组合物、取向材料及相位差材料
JP6658213B2 (ja) * 2015-06-30 2020-03-04 Jsr株式会社 視野角補償フィルム、視野角補償フィルムの製造方法、偏光板、液晶表示素子及び有機ｅｌ素子

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016147987A1 (fr) * 2015-03-13 2016-09-22 日産化学工業株式会社 Composition de formation de film durci, matériau d'alignement et matériau de différence de phase
JP2017016116A (ja) * 2015-06-30 2017-01-19 富士フイルム株式会社 感光性樹脂組成物、硬化膜の製造方法、硬化膜および液晶表示装置

Also Published As

Publication number Publication date
JP7365003B2 (ja) 2023-10-19
TW201920320A (zh) 2019-06-01
CN111164120A (zh) 2020-05-15
JPWO2019027045A1 (ja) 2020-09-24
TWI794261B (zh) 2023-03-01
KR20200037278A (ko) 2020-04-08
CN116789871A (zh) 2023-09-22

Similar Documents

Publication Publication Date Title
US9823400B2 (en) Cured film formation composition, orientation material, and retardation material
US9823401B2 (en) Cured film formation composition, orientation material, and retardation material
JP6823295B2 (ja) Ｎ−アルコキシメチル基を有する繰り返し単位及び重合性のｃ＝ｃ二重結合を含む側鎖を有する繰り返し単位を含むポリマー
TW201602144A (zh) 硬化膜形成組成物、配向材及相位差材
JP7260853B2 (ja) 硬化膜形成組成物、配向材および位相差材
KR20200135968A (ko) 경화막 형성 조성물, 배향재 및 위상차재
TWI822746B (zh) 硬化膜形成組成物、配向材料及相位差材料
CN110461887B (zh) 固化膜形成用组合物、取向材及相位差材
JP7365003B2 (ja) 硬化膜形成組成物、配向材および位相差材
KR102662084B1 (ko) 경화막 형성 조성물, 배향재 및 위상차재
JPWO2015030004A1 (ja) 硬化膜形成組成物、配向材および位相差材
WO2021106858A1 (fr) Composition filmogène durcie, matériau d'alignement et matériau à différence de phase
WO2023157934A1 (fr) Composition de résine pour films de photo-alignement thermodurcissables
WO2020184463A1 (fr) Agent d'alignement de cristaux liquides pour photo-alignement, matériau d'alignement et matériau de différence de phase

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18841969

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2019534604

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20207004627

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 18841969

Country of ref document: EP

Kind code of ref document: A1