WO2017170701A1 - 重合性組成物、硬化物及びディスプレイ用光学フィルム並びに硬化物を製造する方法 - Google Patents
重合性組成物、硬化物及びディスプレイ用光学フィルム並びに硬化物を製造する方法 Download PDFInfo
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- WO2017170701A1 WO2017170701A1 PCT/JP2017/012919 JP2017012919W WO2017170701A1 WO 2017170701 A1 WO2017170701 A1 WO 2017170701A1 JP 2017012919 W JP2017012919 W JP 2017012919W WO 2017170701 A1 WO2017170701 A1 WO 2017170701A1
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- 0 C*C1(C=C(CCC(ON=C(Cc2ccccc2C)[C@](C2)c3ccccc3N2c2ccccc2F)=O)C**1)N=O Chemical compound C*C1(C=C(CCC(ON=C(Cc2ccccc2C)[C@](C2)c3ccccc3N2c2ccccc2F)=O)C**1)N=O 0.000 description 3
- QIGVVGMRUDBTLQ-HPNDGRJYSA-N CCC(O/N=C(\Cc1c(C)cccc1)/c(c1ccccc11)c[n]1-c1ccccc1[N+]([O-])=O)=O Chemical compound CCC(O/N=C(\Cc1c(C)cccc1)/c(c1ccccc11)c[n]1-c1ccccc1[N+]([O-])=O)=O QIGVVGMRUDBTLQ-HPNDGRJYSA-N 0.000 description 2
- NYQBCQRCLGIIAJ-UHFFFAOYSA-N CC(C(Oc1ccc(CCC(Oc(cc2)c(C)cc2OC(c(cc2)ccc2OC(C=C)=O)O)=O)cc1)=O)=C Chemical compound CC(C(Oc1ccc(CCC(Oc(cc2)c(C)cc2OC(c(cc2)ccc2OC(C=C)=O)O)=O)cc1)=O)=C NYQBCQRCLGIIAJ-UHFFFAOYSA-N 0.000 description 1
- XFHZOQRKDRRPFB-YYDJUVGSSA-N CC(C1)(/C(/Cc2ccccc2C)=N/OC(C)=O)c2ccccc2N1c1ccc[o]1 Chemical compound CC(C1)(/C(/Cc2ccccc2C)=N/OC(C)=O)c2ccccc2N1c1ccc[o]1 XFHZOQRKDRRPFB-YYDJUVGSSA-N 0.000 description 1
- MNMCIYFMZOBRKO-KBFKOYTBSA-N CC(C1)C(OC(C(CC2)C=C[C@H]2OCCCCOC(C=C)=O)=O)=CC=C1OC(C(CC1)CCC1OCCCCOC(C=C)O)=O Chemical compound CC(C1)C(OC(C(CC2)C=C[C@H]2OCCCCOC(C=C)=O)=O)=CC=C1OC(C(CC1)CCC1OCCCCOC(C=C)O)=O MNMCIYFMZOBRKO-KBFKOYTBSA-N 0.000 description 1
- VKUHBYBBJPPTHL-WEMUOSSPSA-N CC(O/N=C(\Cc1c(C)cccc1)/C(c(c1ccccc11)c[n]1-c1ccccc1F)=O)=O Chemical compound CC(O/N=C(\Cc1c(C)cccc1)/C(c(c1ccccc11)c[n]1-c1ccccc1F)=O)=O VKUHBYBBJPPTHL-WEMUOSSPSA-N 0.000 description 1
- FXJCMXLHBSHOPH-DARPEHSRSA-N CC(O/N=C(\Cc1c(C)cccc1)/c1c[n](-c2ccc[s]2)c2ccccc12)=O Chemical compound CC(O/N=C(\Cc1c(C)cccc1)/c1c[n](-c2ccc[s]2)c2ccccc12)=O FXJCMXLHBSHOPH-DARPEHSRSA-N 0.000 description 1
- BKHGNPWBLIMOQJ-XTCLZLMSSA-N CC(O/N=C(\Cc1ccccc1C)/c(c1ccccc11)c[n]1-c1ccccn1)=O Chemical compound CC(O/N=C(\Cc1ccccc1C)/c(c1ccccc11)c[n]1-c1ccccn1)=O BKHGNPWBLIMOQJ-XTCLZLMSSA-N 0.000 description 1
- RYGPGOBJOTZJGM-XLVZBRSZSA-N CC(c1ccccc1-[n]1c2ccccc2c(C(/C(/Cc2c(C)cccc2)=N/OC(C)=O)=O)c1)=O Chemical compound CC(c1ccccc1-[n]1c2ccccc2c(C(/C(/Cc2c(C)cccc2)=N/OC(C)=O)=O)c1)=O RYGPGOBJOTZJGM-XLVZBRSZSA-N 0.000 description 1
- FDXGBNUWZHOSQB-XAYXJRQQSA-N CC1(O/N=C(\Cc2c(C)cccc2)/C(c(c2ccccc22)c[n]2-c2ccccc2[N+]([O-])=O)=O)OC1 Chemical compound CC1(O/N=C(\Cc2c(C)cccc2)/C(c(c2ccccc22)c[n]2-c2ccccc2[N+]([O-])=O)=O)OC1 FDXGBNUWZHOSQB-XAYXJRQQSA-N 0.000 description 1
- AABTZGTXKNUOSJ-JQJRJOTLSA-N Cc1c(C/C(/C(C(C2)c3ccccc3N2c(cc2)ccc2C(c2ccccc2)=O)=O)=N\OC(c2ccccc2)=O)cccc1 Chemical compound Cc1c(C/C(/C(C(C2)c3ccccc3N2c(cc2)ccc2C(c2ccccc2)=O)=O)=N\OC(c2ccccc2)=O)cccc1 AABTZGTXKNUOSJ-JQJRJOTLSA-N 0.000 description 1
- PJODDDYHLPBHTN-RIHQVDFKSA-N Cc1c(C/C(/C(c(c2ccccc22)c[n]2-c(cc2)ccc2C#N)=O)=N\OC(c2ccccc2)=O)cccc1 Chemical compound Cc1c(C/C(/C(c(c2ccccc22)c[n]2-c(cc2)ccc2C#N)=O)=N\OC(c2ccccc2)=O)cccc1 PJODDDYHLPBHTN-RIHQVDFKSA-N 0.000 description 1
- MAOOQFXWIFTFLK-XLVZBRSZSA-N Cc1c(C/C(/c2c[n](-c3ccc[s]3)c3ccccc23)=N\OC(c2ccccc2)=O)cccc1 Chemical compound Cc1c(C/C(/c2c[n](-c3ccc[s]3)c3ccccc23)=N\OC(c2ccccc2)=O)cccc1 MAOOQFXWIFTFLK-XLVZBRSZSA-N 0.000 description 1
- UCJPTDIELQNUNV-UHFFFAOYSA-N Cc1cc(C)c(C([O](c2ccccc2)(c2ccccc2)=O)=O)c(C)c1 Chemical compound Cc1cc(C)c(C([O](c2ccccc2)(c2ccccc2)=O)=O)c(C)c1 UCJPTDIELQNUNV-UHFFFAOYSA-N 0.000 description 1
- MGYAWZGHUYVSIE-GKPLWNPISA-N Cc1ccccc1C/C(/c(c1ccccc11)c[n]1-c1ccccn1)=N\OC(c1ccccc1)=O Chemical compound Cc1ccccc1C/C(/c(c1ccccc11)c[n]1-c1ccccn1)=N\OC(c1ccccc1)=O MGYAWZGHUYVSIE-GKPLWNPISA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
- C08F220/302—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and two or more oxygen atoms in the alcohol moiety
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0066—Flame-proofing or flame-retarding additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
- C08K5/3417—Five-membered rings condensed with carbocyclic rings
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/372—Sulfides, e.g. R-(S)x-R'
- C08K5/3725—Sulfides, e.g. R-(S)x-R' containing nitrogen
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/13363—Birefringent elements, e.g. for optical compensation
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
- C09K2019/0448—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate
Definitions
- the present invention relates to a polymerizable composition containing a liquid crystalline compound having a polymerizable functional group (hereinafter also referred to as a polymerizable liquid crystal compound) and a radical polymerization initiator, and more specifically, substituted with a halogen atom as the polymerizable group.
- the present invention relates to a polymerizable composition containing a polymerizable liquid crystal compound having an acryl group or a methacryl group, and a compound having an oxime ester group and a diphenyl sulfide skeleton or an indole skeleton.
- the polymerizable composition of the present invention has excellent effects on solvent solubility and orientation control, and a cured product obtained by polymerizing the polymerizable composition is excellent in orientation retention and transparency, and has a retardation film and a polarizing plate. And an optical film for display typified by a light polarizing prism.
- an optical anisotropic body including a liquid crystal substance in order to obtain stable and uniform optical characteristics, a uniform alignment state of liquid crystal molecules in a liquid crystal state is fixed semi-permanently and mechanically. It is essential to provide a cured product that is thermally stable and has a high glass transition temperature (hereinafter referred to as “Tg”) and excellent orientation.
- Tg glass transition temperature
- a cured product can be obtained by applying a polymerizable composition to a substrate and polymerizing it.
- a method in which a polymerizable composition is dissolved in a solvent is applied. Is preferably used. If the polymerizable composition is insoluble in the solvent, the alignment control of the liquid crystal compound is greatly hindered, and therefore the solvent solubility of the polymerizable composition is required to be good.
- the polymerizable liquid crystal material is prepared by adding a polymerization initiator that is initiated by energy rays such as ultraviolet rays, and has a composition using an acylphosphine oxide compound as an initiator in Patent Document 1 below. Things are illustrated. Moreover, the following patent document 2 and patent document 3 are disclosing the composition characterized by using various oxime ester compounds as an initiator. Patent Document 4 below discloses a polymerizable composition containing a polymerizable liquid crystal compound and a radical polymerization initiator, and an oxime ester compound having a carbazole skeleton as the photopolymerization initiator. .
- an object of the present invention is to provide a polymerizable composition which is excellent in curability and the obtained cured product is excellent in orientation retention, heat resistance and transparency.
- the present invention includes a compound (A) represented by the following general formula (I), a compound (B1) having an indole skeleton and an oxime ester group, and a compound (B2) having a diphenyl sulfide skeleton and an oxime ester group.
- the present invention provides a polymerizable composition containing one or more selected compounds (B).
- R 1 and R 2 each independently represents a hydrogen atom, a methyl group or a halogen atom
- Ring A 1 , Ring A 2 and Ring A 3 each independently represent a benzene ring, a cyclohexane ring, a cyclohexene ring, a naphthalene ring or a phenanthrene ring, —CH ⁇ in these rings may be substituted with —N ⁇ , and —CH 2 — in these rings may be substituted with —S— or —O—
- Z 1 , Z 2 and Z 3 each independently represent a cyano group, a halogen atom or an alkyl group having 1 to 8 carbon atoms
- the hydrogen atom of the alkyl group may be substituted with a halogen atom or a cyano group
- the methylene group of the alkyl group may be substituted with —O— or —CO— under the condition that the oxygen atom is not adjacent.
- the present invention provides the compound (A) in which in the above general formula (I) or (II), L 1 is — (CH 2 ) p —, —CH ⁇ CH—, — (CH 2 ) p O— , —CH ⁇ CHCH 2 O—, — (CH 2 ) p COO—, — (CH 2 ) p OCO—O— or — (CH 2 ) q O (CH 2 ) r O—.
- the present invention also provides the polymerizable composition, wherein the compound (A) is a compound in which the ring A 1 and the ring A 3 are a benzene ring or a naphthalene ring in the general formula (I) or (II). Is.
- the present invention also provides the polymerizable composition, wherein the compound (B1) having an indole skeleton and an oxime ester group is a compound represented by the following general formula (III).
- R 11 and R 12 each independently represent R 21 , OR 21 , COR 21 , SR 21 , CONR 22 R 23 or CN;
- R 21 , R 22 and R 23 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms or a group having 2 to 20 carbon atoms containing a heterocyclic ring;
- the hydrogen atoms of the groups represented by R 21 , R 22 and R 23 are further R 31 , OR 31 , COR 31 , SR 31 , NR 32 R 33 , CONR 32 R 33 , —NR 32 —OR 33 , —NCOR 32.
- R 31 , R 32 and R 33 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms or a group having 2 to 20 carbon atoms containing a heterocyclic ring, The hydrogen atom of the group represented by R 31 , R 32 and R 33 may be further substituted with a hydroxyl group, a nitro group, CN, a halogen atom, a hydroxyl group or a carboxyl group,
- the methylene groups of the groups represented by R 21 , R 22 , R 23 , R 31 , R 32 and R 33 are —O—, —S—, —COO—, —OCO—, —NR 34 —, —NR 34
- R 14 , R 15 , R 16 and R 17 are each independently R 21 , OR 21 , SR 21 , COR 24 , CONR 25 R 26 , NR 22 COR 21 , OCOR 21 , COOR 24 , SCOR 21 , OCSR 21.
- R 24 , R 25 and R 26 represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms
- R 18 is R 21 , OR 21 , SR 21 , COR 21 , CONR 22 R 23 , NR 22 COR 21 , OCOR 21 , COOR 21 , SCOR 21 , OCSR 21 , COSR 21 , CSOR 21 , hydroxyl group, CN or halogen atom Represents n represents 0 or 1.
- the present invention also provides a polymerizable composition in which the compound (B2) having the diphenyl sulfide skeleton and oxime ester group is a compound represented by the following general formula (IV).
- R 41 and R 42 each independently represent R 51 , OR 51 , COR 51 , SR 51 , CONR 52 R 53 or CN;
- R 51 , R 52 and R 53 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms or a group having 2 to 20 carbon atoms containing a heterocyclic ring,
- the hydrogen atom of the substituent represented by R 51 , R 52 and R 53 is further OR 61 , COR 61 , SR 61 , NR 62 R 63 , CONR 62 R 63 , —NR 62 —OR 63 , —NCOR 62 —OCOR 63 , —C ( ⁇ N—OR 61 ) —R 62 , —C ( ⁇ N—OCOR 61 ) —R 62 , CN, halogen atom or COOR 61 may be substituted,
- oxygen atoms may be substituted with — or —CSO— under the condition that oxygen atoms are not adjacent to each other, and R 69 represents a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a carbon atom number containing 2 to 20 carbon atoms containing a heterocyclic ring.
- the present invention also provides the polymerizable composition further containing an optically active compound.
- this invention provides the method of manufacturing hardened
- this invention provides the optical film for displays which uses the hardened
- the compound (A) used in the polymerizable composition of the present invention is a compound represented by the above general formula (I).
- L 1 , L 2 , L 3 and L 4 are each independently a direct bond, —COO—, —OCO—, — (CE 2 ) p —.
- a, b and c are each ring a 1 A number of substituents in the ring A 2 and ring A 3, when the number of six-membered ring contained in a single ring or a condensed ring are each substituted and t, a, b and c are each independently 0 or 2t + 2 or less, b represents an integer of 1 or more, p represents each independently an integer of 1 to 8, and q and r each independently represents an integer of 1 to 3.
- L 4 is a direct bond, — (CE 2 ) p —, —CE ⁇ CE—, —O (CE 2 ) p —, —OCE 2 CE ⁇ CE—, —C ⁇ C—, —OCO (CE 2 ) p It is preferably —, —OCO—O (CE 2 ) p —, or —O (CE 2 ) q O (CE 2 ) r —.
- the compound represented by the general formula (I) and the compound represented by the general formula (II) satisfy one or both of the following conditions (a) and (b) in a wide temperature range. It is preferable in that a liquid crystal phase is expressed and a uniform liquid crystal alignment state is obtained.
- L 4 is — (CH 2 ) p —, —CH ⁇ CH—, —O (CH 2 ) p —, —OCH 2 CH ⁇ CH—, —OCO (CH 2 ) p —, —OCO— A group represented by O (CH 2 ) p — or —O (CH 2 ) q O (CH 2 ) r —.
- L 1 and L 4 may be symmetric or asymmetric. As an example of the case of symmetry here, for example, when L 1 and L 4 are also a direct bond, L 1 is — (CH 2 ) p O—, and L 4 is —O (CH 2 ) p. -, And p of two groups is the same number. Similarly, L 2 and L 3 may be symmetric or asymmetric.
- the methylene group in the group may be substituted with —O— or —CO—, and examples of the group in which the methylene group in the alkyl group is substituted with —O— or —CO— include acetyl, acetonyl , Butan-2-one-1-yl, butan-3-one-1-yl, cyclohexane-4-one-1-yl, trichloroacetyl, trifluoroacetyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, s -Butoxy, t-butoxy, isobutoxy, amyloxy, isoamyloxy, t-amyloxy, hexyloxy, cyclohexyloxy, heptyloxy, isoheptyloxy, t-heptyloxy, n-octyloxy, isooctyloxy, t-octyloxy, 2-ethy
- the compound (A) represented by the general formula (I) a compound that exhibits a liquid crystal phase at a specific temperature or a compound that exhibits a liquid crystal phase at a specific temperature after polymerization is used in a polymerizable composition. This is useful because a cured product having good orientation can be obtained.
- the compound (A) may exhibit a liquid crystal phase at least near room temperature, specifically at 30 ° C. or less. It is particularly preferable that the liquid crystal phase is exhibited at 25 ° C. or lower. It is also preferred that the compound (A) exhibits a liquid crystal phase at any temperature below this upper limit. Whether the compound (A) shows a liquid crystal phase can be confirmed by observation with a polarizing microscope, differential scanning calorimetry, X-ray diffraction measurement, and the like.
- compounds (A) represented by the general formula (I) or (II) compounds in which the ring A 1 and the ring A 3 are benzene rings or naphthalene rings are easy to synthesize, and are excellent in orientation and solvent solubility.
- a compound in which at least one of ring A 1 and ring A 3 is a naphthalene ring is preferable because of excellent heat resistance in addition to the above characteristics.
- R 1 and R 2 in the above general formula (I) or (II) are a hydrogen atom or a methyl group are preferable because they are easy to produce and the resulting polymerizable composition has high curability.
- Specific examples of the compound (A) that can be used in the polymerizable composition of the present invention include the following compound Nos. 1-No. 30. However, the present invention is not limited by the following compounds.
- the production method of the compound (A) is not particularly limited, and can be produced by applying a known reaction.
- methacrylic acid halide or acrylic acid halide can be esterified with phenol.
- the carboxylic acid group of a compound having a methacryloyl group or an acryloyl group can be produced by mesylating with methanesulfonyl chloride and then esterifying with a compound having a phenol group.
- the compound (B) used in the polymerizable composition of the present invention is at least one selected from the group consisting of a compound (B1) having an indole skeleton and an oxime ester group and a compound (B2) having a diphenyl sulfide skeleton and an oxime ester group. Containing the compound. Further, the compound (B1) having an indole skeleton and an oxime ester group and the compound (B2) having a diphenyl sulfide skeleton and an oxime ester group exist in geometric isomers and optical isomers, but they are not distinguished from each other. Represents one or a mixture of two or more of these isomers, and is not limited to a structure showing a specific isomer.
- the polymerizable composition in which the compound (B2) having a diphenyl sulfide skeleton and an oxime ester group is a compound represented by the general formula (IV) has high sensitivity, and the obtained cured product is excellent in transparency. preferable.
- the hydrocarbon group having 30 to 30 is not particularly limited, but preferably an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, It represents a cycloalkylalkyl group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, etc., and has good sensitivity when used as a polymerization initiator.
- the aryl And an aryl alkyl group having 7 to 10 carbon atoms is more preferred.
- alkyl group having 1 to 20 carbon atoms and the alkyl group having 1 to 20 carbon atoms represented by R 24 to R 26 in the general formula (III) include, for example, methyl, ethyl, propyl, isopropyl Butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl Hexadecyl, octadecyl, icosyl and the like.
- alkyl group having 1 to 10 carbon atoms examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl , 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl and isodecyl and the like.
- the cycloalkylalkyl group having 4 to 20 carbon atoms means a group having 4 to 20 carbon atoms in which a hydrogen atom of the alkyl group is substituted with a cycloalkyl group.
- Examples of the cycloalkylalkyl group having 4 to 10 carbon atoms include cyclopropylmethyl , Cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctylmethyl, cyclononylmethyl, 2-cyclobutylethyl, 2-cyclopentylethyl, 2-cyclohexylethyl, 2-cycloheptylethyl, 2-cyclooctylethyl , 3-cyclobutylpropyl, 3-cyclopentylpropyl, 3-cyclohexylpropyl, 3-cycloheptylpropyl, 4-cyclobutylbutyl, 4-cyclopentylbutyl, 4-cyclohexylbutyl, etc. It is.
- Examples of the aryl group of 6 to 10 include phenyl, tolyl, xylyl, ethylphenyl, naphthyl and the like, phenyl, biphenylyl, naphthyl substituted with one or more of the above alkyl groups, the above alkenyl groups, carboxyl groups, halogen atoms, etc. , Anthril, etc., eg 4 Chlorophenyl, 4-carboxyphenyl, 4-vinylphenyl, 4-methylphenyl, 2,4,6-trimethylphenyl, and the like.
- the arylalkyl group having 7 to 30 carbon atoms means a group having 7 to 30 carbon atoms in which a hydrogen atom of the alkyl group is substituted with an aryl group.
- benzyl, ⁇ -methylbenzyl, ⁇ , ⁇ -dimethylbenzyl, phenylethyl, naphthylpropyl and the like are mentioned.
- the above arylalkyl group having 7 to 20 carbon atoms means that the hydrogen atom of the alkyl group is an aryl group.
- substituted is meant a group having from 7 to 30 carbon atoms. Examples include benzyl, ⁇ -methylbenzyl, ⁇ , ⁇ -dimethylbenzyl, phenylethyl and the like.
- Examples of the group having 2 to 20 carbon atoms containing a heterocyclic ring include pyrrolyl, pyridyl, pyridylethyl, pyrimidyl, pyridazyl, piperazyl, piperidyl, pyranyl, pyranylethyl, pyrazolyl, triazyl, triazylmethyl, pyrrolidyl, quinolyl, isoquinolyl , Imidazolyl, benzimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isoxazolyl, indolyl, morpholinyl, thiomorpholinyl, 2-pyrrolidinone-1 -Yl, 2-piperidone-1-yl
- each R independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
- Z represents a direct bond or an alkylene group having 1 to 6 carbon atoms. Means that the group represented by these formulas is bonded to an adjacent group at the * moiety.
- R 13 and R 17 in the general formula (III), R 13 and R 18 , R 14 and R 15 , R 15 and R 16 , R 16 and R 17 , and R 52 and R in the general formula (IV) 53 and R 62 and R 63 are, as the ring formed in combination, for example, cyclopentane, cyclohexane, cyclopentene, benzene, pyrrolidine, pyrrole, piperazine, morpholine, thiomorpholine, tetrahydropyridine, such as lactone ring and the lactam ring Examples thereof include 5- to 7-membered rings and condensed rings such as naphthalene and anthracene.
- R 13 in the general formula (III) is an aryl group having 6 to 30 carbon atoms
- the sensitivity is high, and the obtained cured product is excellent in transparency, and is easy to manufacture and obtain. It is more preferable because there is. Further, it is preferable from the viewpoint of good sensitivity that at least one hydrogen atom in the aryl group having 6 to 30 carbon atoms is substituted with a nitro group, CN or a halogen atom.
- R 11 is R 21 and R 21 is an alkyl group having 1 to 10 carbon atoms from the viewpoint of excellent solvent solubility.
- R 12 is a R 21, R 21 are as a methyl group, an ethyl group or a phenyl group, when used as a polymerization initiator, from the viewpoint of excellent curability.
- R 14 to R 17 are R 21 or CN and R 21 is a hydrogen atom, and particularly those in which R 14 to R 17 are a hydrogen atom are preferable because synthesis is easy.
- a compound in which R 18 is R 21 and R 21 is a hydrogen atom is preferable because synthesis is easy.
- R 44 is a group represented by the general formula (V).
- a compound in which X 2 in V) is —O— or —OCO— is preferred because of high sensitivity and easy production.
- a compound in which X 3 in the general formula (V) is an alkyl group having 1 to 10 carbon atoms and the methylene group in the alkyl group is substituted with —O— is preferable because of excellent developability.
- X 3 in the general formula (V) is preferably an alkyl group having 1 to 10 carbon atoms substituted with a hydroxyl group or a carboxyl group from the viewpoint of low liquid crystal contamination.
- the production method of the compound (B) is not particularly limited, and can be produced by applying a known reaction.
- an indole compound or a diphenyl sulfide compound is acylated with an acid chloride, It can be produced by reacting an acid anhydride or acid chloride after oximation with hydroxylamine.
- W 1 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may have a branch, an alkoxy group having 1 to 8 carbon atoms which may have a branch, or a carbon which may have a branch.
- An alkenyl group having 2 to 8 atoms, an alkenyloxy group having 2 to 8 carbon atoms that may be branched, an alkoxyalkyl group having 2 to 8 carbon atoms that may be branched, and a carbon that may be branched Represents an alkanoyloxy group having 2 to 8 atoms or an alkoxycarbonyl group having 2 to 8 carbon atoms that may have a branch, and W 3 represents a cyano group, a halogen atom, or a carbon atom that may have a branch having 1 to 8 alkyl group, alkoxycarbonyl group having 2 to 8 carbon atoms which if there have is alkanoyloxy group or a branched C 2 -C 8 when
- Known radical polymerization initiators include, for example, benzoyl peroxide, 2,2′-azobisisobutyronitrile, benzoin ethers, benzophenones, acetophenones, benzyl ketals, diaryl iodonium salts, triaryl sulfonium salts, Diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium tetra (pentafluorophenyl) borate, 4-methoxyphenylphenyliodonium tetrafluoroborate, 4-methoxyphenylphenyliodonium hexafluorophosphonate, 4 -Methoxyphenylphenyliodonium hexafluoroarsenate, bis (4-tert-butyl Phenyl
- radical polymerization initiator commercially available radical polymerization initiators can be used.
- N-1414, N-1717, N-1919, NCI-831, NCI-930 manufactured by ADEKA
- IRGACURE 369 IRGACURE 907
- IRGACURE OXE 01 IRGACURE OXE 02
- benzoyl peroxide and the like can be mentioned, and these polymerization initiators can be used alone or in combination of two or more.
- the content is preferably 50 parts by mass or less with respect to 100 parts by mass of the compound (B), 30 It is more preferable that the amount is not more than part by mass.
- the polymerizable composition of the present invention preferably exhibits a liquid crystal phase at least near room temperature, specifically 30 ° C. or less, and particularly preferably exhibits a liquid crystal phase at 25 ° C. or less, as an optical material. This is more preferable.
- the liquid crystal phase is preferably displayed at any temperature below the temperature. Examples of the method for confirming the liquid crystal phase in the polymerizable composition include the same methods as those for confirming the liquid crystal phase in the compound.
- another monomer (a compound having an ethylenically unsaturated bond) used as necessary may be dissolved in a solvent together with the radical polymerization initiator to form a solution. it can.
- Examples of the other monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, s-butyl (meth) acrylate, and t-butyl (meth) acrylate.
- the content of the other monomer is the above compound (A) and the above compound (B). Is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, based on 100 parts by mass of the total amount.
- radical polymerization initiator and sensitizer can be preferably used.
- the sensitizer include thioxanthone, phenothiazine, chlorothioxanthone, xanthone, anthracene, diphenylanthracene, and lupine.
- the addition amount thereof is 10 parts by mass or less with respect to 100 parts by mass of the total amount of the compound (A) and the compound (B), respectively. Is preferably 5 parts by mass or less, and more preferably in the range of 0.1 to 3 parts by mass.
- solvent examples include benzene, toluene, xylene, mesitylene, n-butylbenzene, diethylbenzene, tetralin, methoxybenzene, 1,2-dimethoxybenzene, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexane.
- the solvent may be a single compound or a mixture. Among these solvents, those having a boiling point of 60 to 250 ° C. are preferable, and those having a boiling point of 60 to 180 ° C. are particularly preferable. If the temperature is lower than 60 ° C., the solvent is volatilized in the coating process and the film thickness is likely to be uneven. If the temperature is higher than 250 ° C., the solvent remains even if the pressure is reduced in the solvent removal process, In some cases, the orientation may be reduced.
- the optically active compound that may be contained in the polymerizable composition refers to a pair of three-dimensional compound cocoons (enantiomers) that have an asymmetric carbon in the molecule and are in a mirror image relationship with each other. Means a compound having the property of rotating the polarization plane.
- the amount is preferably in the range of 0.1 to 100 parts by mass with respect to 100 parts by mass of the total amount of the compound (A) and the compound (B), and 1 to 50 parts by mass. Is more preferable.
- the optically active compound include the following compound No. 384-No. 395.
- the polymerizable composition of the present invention may further contain a surfactant having an excluded volume effect distributed on the air interface side.
- a surfactant those capable of easily applying the polymerizable composition to a support substrate or the like and controlling the alignment of the liquid crystal phase are preferable.
- the above storage stabilizer can impart the effect of improving the storage stability of the polymerizable composition.
- examples of the stabilizer that can be used include hydroquinone, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, 2-naphthylamines, and 2-hydroxynaphthalenes.
- the antioxidant is not particularly limited and a known compound can be used. Examples thereof include hydroquinone, 2,6-di-t-butyl-p-cresol, 2,6-di-t-butylphenol, Examples thereof include phenyl phosphite and trialkyl phosphite.
- the ultraviolet absorber is not particularly limited, and a known compound can be used.
- a salicylic acid ester compound for example, a benzophenol compound, a benzotriazole compound, a cyanoacrylate compound, a nickel complex compound, or the like What gave absorption ability can be used.
- the inorganic material examples include ceramics, fluorine phlogopite, fluorine tetrasilicon mica, teniolite, fluorine vermiculite, fluorine hectorite, hectorite, saponite, stevensite, montmorillonite, beidellite, kaolinite, frypontite, ZnO, TiO 2 , CeO 2, Al 2 O 3, Fe 2 O 3, ZrO 2, MgF 2, SiO 2, SrCO 3, Ba (OH) 2, Ca (OH) 2, Ga (OH) 3, Al (OH) 3, Mg (OH) 2 and Zr (OH) 4 are included.
- fine particles such as calcium carbonate needle-like crystals have optical anisotropy, and the optical anisotropy of the polymer can be adjusted by such fine particles.
- the organic substance include carbon nanotubes, fullerenes, dendrimers, polyvinyl alcohol, polymethacrylate, and polyimide.
- a method for producing a cured product using the polymerizable composition of the present invention will be described.
- a method for producing the cured product of the present invention for example, after dissolving the polymerizable composition in a solvent, it is applied to a support substrate and the solvent is removed in a state where liquid crystal molecules in the polymerizable composition are aligned. Then, it can be obtained by polymerizing by irradiation with energy rays.
- a known method can be used, such as a curtain coating method, an extrusion coating method, a roll coating method, a spin coating method, A dip coating method, a bar coating method, a spray coating method, a slide coating method, a printing coating method, a casting film forming method, and the like can be used.
- the film thickness of the cured product of the present invention is appropriately selected depending on the application and the like, but is preferably 0.005 to 30 ⁇ m, more preferably 0.01 to 20 ⁇ m, and particularly preferably 0.05 to 15 ⁇ m. Selected.
- the method of aligning liquid crystal molecules by the above method and then curing the polymerizable composition by the method described below is preferable because a cured product excellent in liquid crystal alignment control can be produced.
- a known method using light, electromagnetic waves or heat can be applied.
- the polymerization reaction by light or electromagnetic wave include radical polymerization, anionic polymerization, cationic polymerization, coordination polymerization, and living polymerization. According to these polymerization reactions, it is easy to perform polymerization under conditions where the polymerizable composition exhibits a liquid crystal phase. It is also preferable to crosslink while applying a magnetic field or electric field.
- the liquid crystal (co) polymer formed on the support substrate may be used as it is, or may be used after being peeled off from the support substrate or transferred to another support substrate as necessary.
- the light from the light source may be irradiated to the polymerizable composition as it is, or the specific wavelength (or specific wavelength region) selected by the filter may be irradiated to the polymerizable composition.
- Preferred irradiation energy density is 2 ⁇ 5000mJ / cm 2, more preferred range is 10 ⁇ 3000mJ / cm 2, particularly preferred range is 100 ⁇ 2000mJ / cm 2.
- Preferred illuminance is 0.1 ⁇ 5000mW / cm 2, more preferably illuminance is 1 ⁇ 2000mW / cm 2.
- preferable irradiation temperature is 100 degrees C or less. Polymerization due to heat can occur at a temperature of 100 ° C. or higher, so that good alignment may not be obtained.
- Example 1 to 4 and Comparative Examples 1 to 4 Compound No. 1 or No. 6 was dissolved in 4.0 g of 2-butanone. 101, no. 235 or Comparative Compound No. 1-No. 0.03 g of No. 4 was added and completely dissolved. The obtained solutions were filtered through a 0.45 ⁇ m filter to obtain polymerizable compositions of Examples 1 to 4 and Comparative Examples 1 to 4, respectively. Details are shown in [Table 1].
- the obtained cured product was subjected to confirmation of the optical structure of the surface using an OPTIPHOT2-POL (Nikon) polarizing microscope.
- the case where the orientation is uniform and the orientation defect is not confirmed is A
- the surface is transparent
- the portion where the orientation unevenness is partially confirmed is B
- the case where crystallization or orientation unevenness is confirmed is C It was.
- those having an orientation evaluation of A are preferred.
- the polymerizable compositions of Comparative Evaluation Examples 5 to 7 have low curability, large retardation changes after the heat test, and poor curability and heat resistance. I was able to confirm.
- the polymerizable composition of the present invention (Evaluation Examples 5 to 8) is uniformly cured, has a uniform orientation, has a small retardation change after the heat test, and exhibits a good curability, orientation and heat resistance. It was confirmed that it was excellent in performance.
- compound (A) compound no. It was confirmed that those using No. 1 were excellent in heat resistance. Therefore, it is clear that the polymerizable composition of the present invention and the cured product produced using the polymerizable composition are useful for an optical film for display.
- the polymerizable composition of the present invention is excellent in curability (particularly photocurability), solvent solubility, and compatibility with other liquid crystal compounds.
- the cured product of the present invention produced by photopolymerization with orientation control in a state where the polymerizable composition exhibits a liquid crystal phase is excellent in orientation controllability, transparency, heat resistance, etc., and as an optical film for display. It is particularly useful.
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Abstract
Description
本発明が解決しようとする問題点は、硬化性に優れ、得られる硬化物が配向保持、耐熱性及び透明性に優れる重合性組成物が、これまでなかったということである。
環A1、環A2及び環A3は、それぞれ独立に、ベンゼン環、シクロヘキサン環、シクロヘキセン環、ナフタレン環又はフェナントレン環を表し、
これらの環中の-CH=は-N=で置換される場合もあり、これらの環中の-CH2-は-S-又は-O-で置換される場合もあり、
Z1、Z2及びZ3は、それぞれ独立に、シアノ基、ハロゲン原子又は炭素原子数1~8のアルキル基を表し、
該アルキル基の水素原子はハロゲン原子又はシアノ基で置換される場合もあり、該アルキル基のメチレン基は酸素原子が隣り合わない条件で-O-又は-CO-で置換される場合もあり、
L1及びL2は、それぞれ独立に、直接結合、-COO-、-(CE2)p-、-CE=CE-、-(CE2)pO-、-CE=CECE2O-、-C≡C-、-(CE2)pCOO-、-(CE2)pOCO-O-又は-(CE2)qO(CE2)rO-を表し、L3及びL4は、それぞれ独立に、直接結合、-OCO-、-(CE2)p-、-CE=CE-、-O(CE2)p-、-OCE2CE=CE-、-C≡C-、-OCO(CE2)p-、-OCO-O(CE2)p-又は-O(CE2)qO(CE2)r-を表し、
L1及びL4におけるEは、水素原子、メチル基又はエチル基を表し、
L2及びL3におけるEは、水素原子を表し、
複数あるEは同一である場合もあり、異なる場合もあり、
a、b及びcはそれぞれ環A1、環A2及び環A3における置換基の数であって、それぞれの置換される単環又は縮合環に含まれる6員環の数をtとすると、a、b及びcはそれぞれ独立に0以上2t+2以下の整数で、かつbは1以上の整数を表し、
pは、それぞれ独立に、1~8の整数を表し、
q及びrは、それぞれ独立に、1~3の整数を表す。)
該アルキル基の水素原子はハロゲン原子又はシアノ基で置換される場合もあり、
該アルキル基のメチレン基は、酸素原子が隣り合わない条件で-O-又は-CO-で置換される場合もあり、R3及びR4の少なくともどちらか一方は、水素原子以外の置換基を表す。)
(これらの式中、pは1~8の整数を表し、q及びrは、それぞれ独立に、1~3の整数を表す。)
R21、R22及びR23は、それぞれ独立に、水素原子、炭素原子数1~30の炭化水素基又は複素環を含有する炭素原子数2~20の基を表し、
R21、R22及びR23で表わされる基の水素原子は、更にR31、OR31、COR31、SR31、NR32R33、CONR32R33、-NR32-OR33、-NCOR32-OCOR33、NR32COR31、OCOR31、COOR31、SCOR31、OCSR31、COSR31、CSOR31、水酸基、ニトロ基、CN、ハロゲン原子、又はCOOR31で置換される場合もあり、
R31、R32及びR33は、それぞれ独立に、水素原子、炭素原子数1~30の炭化水素基又は複素環を含有する炭素原子数2~20の基を表し、
R31、R32及びR33で表される基の水素原子は、更に水酸基、ニトロ基、CN、ハロゲン原子、水酸基又はカルボキシル基で置換される場合もあり、
R21、R22、R23、R31、R32及びR33で表される基のメチレン基は、-O-、-S-、-COO-、-OCO-、-NR34-、-NR34COO-、-OCONR34-、-SCO-、-COS-、-OCS-又は-CSO-により酸素原子が隣り合わない条件で置換される場合もあり、
R34は、水素原子、炭素原子数1~30の炭化水素基又は複素環を含有する炭素原子数2~20の基を表し、
R13は、水素原子、炭素原子数1~30の炭化水素基又は複素環を含有する炭素原子数2~20の基を表し、また、R13とR17、R13とR18、R14とR15、R15とR16及びR16とR17はそれぞれ結合して環を形成している場合もあり、
R13で表わされる基の水素原子は、更にR31、OR31、COR31、SR31、NR32R33、CONR32R33、-NR32-OR33、-NCOR32-OCOR33、NR32COR31、OCOR31、COOR31、SCOR31、OCSR31、COSR31、CSOR31、水酸基、ニトロ基、CN、ハロゲン原子、又はCOOR31で置換される場合もあり、
R14、R15、R16及びR17は、それぞれ独立に、R21、OR21、SR21、COR24、CONR25R26、NR22COR21、OCOR21、COOR24、SCOR21、OCSR21、COSR24、CSOR21、水酸基、CN又はハロゲン原子を表し、
R24、R25及びR26は、水素原子又は炭素原子数1~20のアルキル基を表し、
R18は、R21、OR21、SR21、COR21、CONR22R23、NR22COR21、OCOR21、COOR21、SCOR21、OCSR21、COSR21、CSOR21、水酸基、CN又はハロゲン原子を表し、
nは、0又は1を表す。)
R51、R52及びR53は、それぞれ独立に、水素原子、炭素原子数1~30の炭化水素基又は複素環を含有する炭素原子数2~20の基を表し、
R51、R52及びR53で表わされる置換基の水素原子は、更にOR61、COR61、SR61、NR62R63、CONR62R63、-NR62-OR63、-NCOR62-OCOR63、-C(=N-OR61)-R62、-C(=N-OCOR61)-R62、CN、ハロゲン原子又はCOOR61で置換される場合もあり、
R51、R52、R53、R61、R62及びR63で表される置換基のメチレン基は、-O-、-S-、-COO-、-OCO-、-NR64-、-NR64COO-、-OCONR64-、-SCO-、-COS-、-OCS-又は-CSO-により酸素原子が隣り合わない条件で置換される場合もあり、
R61、R62及びR63は、それぞれ独立に、水素原子、炭素原子数1~30の炭化水素基又は複素環を含有する炭素原子数2~20の基を表し、
R61、R62及びR63で表される置換基の水素原子は、更にCN、ハロゲン原子、水酸基又はカルボキシル基で置換される場合もあり、
R64は、水素原子、炭素原子数1~30の炭化水素基又は複素環を含有する炭素原子数2~20の基を表し、
R52とR53及びR62とR63はそれぞれ結合して環を形成している場合もあり、
R43は、R54、OR54、SR54、COR54、CONR55R56、NR55COR54、OCOR54、COOR54、SCOR54、OCSR54、COSR54、CSOR54、CN又はハロゲン原子を表し、R44は、R54、OR54、SR54、COR54、CONR55R56、NR55COR54、OCOR54、COOR54、SCOR54、OCSR54、COSR54、CSOR54、CN、ハロゲン原子、OH、COOH又は下記一般式(V)で表される基を表し、
R54、R55及びR56は、それぞれ独立に、水素原子、炭素原子数1~30の炭化水素基又は複素環を含有する炭素原子数2~20の基を表し、
f及びgは、それぞれ独立に、0~4の整数を表す。)
X3は、1~3個のR70で置換された炭素原子数1~30の炭化水素基又は複素環を含有する炭素原子数2~20の基を表し、
X3中のメチレン基は、-O-、-S-、-COO-、-OCO-、-NR69-、-NR69COO-、-OCONR69-、-SCO-、-COS-、-OCS-又は-CSO-により酸素原子が隣り合わない条件で置換される場合もあり、R69は、水素原子、炭素原子数1~30の炭化水素基又は複素環を含有する炭素原子数2~20の基を表し、
R70は、OR71、SR71、CONR72R73、NR72COR73、OCOR71、COOR71、SCOR71、OCSR71、COSR71、CSOR71、CN又はハロゲン原子を表し、
R71、R72及びR73は、それぞれ独立に、水素原子又は炭素原子数1~30の炭化水素基を表す。式中の*は、*部分で、隣接する基と結合することを意味する。)
本発明の重合性組成物に用いられる化合物(A)は、上記一般式(I)で表される化合物である。
(a)L1が、-(CH2)p-、-CH=CH-、-(CH2)pO-、-CH=CHCH2O-、-(CH2)pCOO-、-(CH2)pOCO-O-又は-(CH2)qO(CH2)rO-で表される基である。
(b)L4が、-(CH2)p-、-CH=CH-、-O(CH2)p-、-OCH2CH=CH-、-OCO(CH2)p-、-OCO-O(CH2)p-又は-O(CH2)qO(CH2)r-で表される基である。
L1とL4とは対称である場合もあり、非対称である場合もある。ここでいう対称である場合の例としては、例えばL1とL4とも直接結合である場合や、L1が-(CH2)pO-であり、L4が-O(CH2)p-であり、二つの基のpが同数である場合が挙げられる。同様に、L2とL3とは対称である場合もあり、非対称である場合もある。
本発明の重合性組成物に用いられる化合物(B)は、インドール骨格及びオキシムエステル基を有する化合物(B1)並びにジフェニルスルフィド骨格及びオキシムエステル基を有する化合物(B2)よりなる群から選ばれる少なくとも1の化合物を含有する。
また、上記インドール骨格及びオキシムエステル基を有する化合物(B1)並びにジフェニルスルフィド骨格及びオキシムエステル基を有する化合物(B2)は、幾何異性体及び光学異性体が存在するが、これらを区別するものではなく、これら異性体の一種又は二種以上の混合物を表すものであり、特定の異性体を示した構造に限定するものではない。
また、上記一般式(III)中のR11が、R21であり、R21が、炭素原子数1~10のアルキル基であるものは、溶剤溶解性に優れる点から好ましい。また、R12が、R21であり、R21が、メチル基、エチル基又はフェニル基であるものは、重合開始剤として用いた場合、硬化性に優れる点から好ましい。また、R14~R17がR21又はCNであり、R21が、水素原子であるもの、特にR14~R17が水素原子であるものが、合成が容易なので好ましい。また、R18がR21であり、R21が水素原子であるものは、合成が容易なので好ましい。
(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、ベンジル(メタ)アクリレート、1-フェニルエチル(メタ)アクリレート、2-フェニルエチル(メタ)アクリレート、フルフリル(メタ)アクリレート、ジフェニルメチル(メタ)アクリレート、ナフチル(メタ)アクリレート、ペンタクロルフェニル(メタ)アクリレート、2-クロルエチル(メタ)アクリレート、メチル-α-クロル(メタ)アクリレート、フェニル-α-ブロモ(メタ)アクリレート、トリフルオロエチル(メタ)アクリレート、テトラフルオロプロピル(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、1,4-ブタンジオールジ(メタ)アクリレート、1,6-ヘキサンジオールジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート等の(メタ)アクリル酸エステル、ジアセトンアクリルアミド、スチレン、ビニルトルエン及びジビニルベンゼン等が挙げられる。
また、炭酸カルシウムの針状結晶などの微粒子は光学異方性を有し、このような微粒子によって重合体の光学異方性を調節できる。上記有機物としては、例えばカーボンナノチューブ、フラーレン、デンドリマー、ポリビニルアルコール、ポリメタクリレート及びポリイミド等が挙げられる。
本発明の硬化物を製造する方法としては、例えば、上記重合性組成物を溶剤に溶解した後、支持基板に塗布して、重合性組成物中の液晶分子を配向させた状態で脱溶剤し、次いでエネルギー線を照射して重合することにより得ることができる。
化合物No.1又はNo.6の1.0gを2-ブタノン4.0gに溶解させ、更に化合物No.101、No.235又は比較化合物No.1~No.4の0.03gを添加、完全に溶解させた。得られた溶液を、0.45μmフィルターで濾過して、実施例1~4及び比較例1~4の重合性組成物をそれぞれ得た。詳細を[表1]に示す。
重合性組成物No.1~4又は比較重合性組成物No.1~4を、ガラス基板上にスピンコート(500rpm、2秒間、900rpm、5秒間)し、ホットプレートを用いて、90℃で90秒間プリベークを行った後、23℃で40秒間冷却した。その後、高圧水銀ランプを用いて100mJ/cm2を照射し評価サンプルを作成した。得られたサンプルの400nmにおける透過率を測定した。透過率が97%以上のものをAとし、97%未満のものをBとした。ディスプレイ用光学フィルム等に代表される用途では透過率の評価がAの物が好ましい。評価結果を[表2]に示す。
重合性組成物No.1~4又は比較重合性組成物No.2~4を、スピンコーターを使用して、ラビング処理したポリイミド付ガラス基板上に塗工し、100℃に設定したホットプレート上で3分間乾燥させた。室温に戻し3分間放置後、高圧水銀灯(120W/cm)で20秒間照射し硬化させ、各重合性組成物の硬化物である重合膜をそれぞれ得た(膜厚が約1μmになるようにスピンコーターの回転数及び時間を調整した。)。得られた各硬化物を以下の手法により評価した。
得られた硬化物をOPTIPHOT2-POL(ニコン社製)偏光顕微鏡を使用し、表面の光学組織の確認を実施した。配向が一様であり、配向欠陥が確認されないものをAとし、表面が透明であるが、一部配向ムラが確認されるものをBとし、結晶化や配向ムラ等が確認されるものをCとした。ディスプレイ用光学フィルム等に代表される用途では配向性の評価がAの物が好ましい。
得られた硬化物の表面硬化性を目視で確認した。均一に硬化しており、タックも残っていないものをAとし、均一に硬化しているが、若干タックが残っているものをBとし、全面にタックが残り、表面がベトついているものをCとした。ディスプレイ用光学フィルム等に代表される用途では硬化性の評価がAの物が好ましい。
得られた硬化物について、OPTIPHOT2-POL(ニコン社製)偏光顕微鏡を用いてセナルモン法に基づく複屈折測定法に従い、室温25℃で波長546nmにおけるリターデーションを測定した。更にその硬化物を150℃オーブンで30分放置後、室温に冷却し上記方法に準じてリターデーションを測定し、下記式にて変化率を算出した。(変化率が小さい程熱による光学物性変化が小さく、耐熱性が高いと言える。)
(リターデーション変化率/%)=100-(リターデーション(耐熱試験後)/リターデーション(耐熱試験前)×100)
これに対し、本発明の重合性組成物(評価例5~8)は、均一に硬化し、配向性が一様であり、耐熱試験後のリターデーション変化も小さく、硬化性、配向性及び耐熱性に優れることが確認できた。特に化合物(A)として化合物No.1を用いたものは耐熱性に優れることが確認できた。
よって本発明の重合性組成物及び重合性組成物を用いて製造した硬化物が、ディスプレイ用光学フィルムに対して有用であることは明らかである。
Claims (10)
- 下記一般式(I)で表される化合物(A)と、インドール骨格及びオキシムエステル基を有する化合物(B1)並びにジフェニルスルフィド骨格及びオキシムエステル基を有する化合物(B2)よりなる群から選ばれる1つ以上の化合物(B)とを含有する重合性組成物。
環A1、環A2及び環A3は、それぞれ独立に、ベンゼン環、シクロヘキサン環、シクロヘキセン環、ナフタレン環又はフェナントレン環を表し、
これらの環中の-CH=は-N=で置換される場合もあり、これらの環中の-CH2-は-S-又は-O-で置換される場合もあり、
Z1、Z2及びZ3は、それぞれ独立に、シアノ基、ハロゲン原子又は炭素原子数1~8のアルキル基を表し、
該アルキル基の水素原子はハロゲン原子又はシアノ基で置換される場合もあり、該アルキル基のメチレン基は酸素が隣り合わない条件で-O-又は-CO-で置換される場合もあり、
L1及びL2は、それぞれ独立に、直接結合、-COO-、-(CE2)p-、-CE=CE-、-(CE2)pO-、-CE=CECE2O-、-C≡C-、-(CE2)pCOO-、-(CE2)pOCO-O-又は-(CE2)qO(CE2)rO-を表し、L3及びL4は、それぞれ独立に、直接結合、-OCO-、-(CE2)p-、-CE=CE-、-O(CE2)p-、-OCE2CE=CE-、-C≡C-、-OCO(CE2)p-、-OCO-O(CE2)p-又は-O(CE2)qO(CE2)r-を表し、
L1及びL4におけるEは、水素原子、メチル基又はエチル基を表し、
L2及びL3におけるEは、水素原子を表し、
複数あるEは同一である場合もあり、異なる場合もあり、
a、b及びcはそれぞれ環A1、環A2及び環A3における置換基の数であって、それぞれの置換される単環又は縮合環に含まれる6員環の数をtとすると、a、b及びcはそれぞれ独立に0以上2t+2以下の整数で、かつbは1以上の整数を表し、
pは、それぞれ独立に、1~8の整数を表し、
q及びrは、それぞれ独立に、1~3の整数を表す。) - 化合物(A)が、以下の(a)及び(b)の条件の一方又は両方を満たす請求項1又は2に記載の重合性組成物。
(a)L1が、-(CH2)p-、-CH=CH-、-(CH2)pO-、-CH=CHCH2O-、-(CH2)pCOO-、-(CH2)pOCO-O-又は-(CH2)qO(CH2)rO-で表される基である。
(b)L4が、-(CH2)p-、-CH=CH-、-O(CH2)p-、-OCH2CH=CH-、-OCO(CH2)p-、-OCO-O(CH2)p-又は-O(CH2)qO(CH2)r-で表される基である。
(これらの式中、pは1~8の整数を表し、q及びrは、それぞれ独立に、1~3の整数を表す。) - 化合物(A)における環A1及び環A3がそれぞれ独立にベンゼン環又はナフタレン環である請求項1~3の何れか一項に記載の重合性組成物。
- 上記インドール骨格及びオキシムエステル基を有する化合物(B1)が、下記一般式(III)で表される化合物である請求項1~4の何れか一項に記載の重合性組成物。
R21、R22及びR23は、それぞれ独立に、水素原子、炭素原子数1~30の炭化水素基又は複素環を含有する炭素原子数2~20の基を表し、
R21、R22及びR23で表わされる基の水素原子は、更にR31、OR31、COR31、SR31、NR32R33、CONR32R33、-NR32-OR33、-NCOR32-OCOR33、NR32COR31、OCOR31、COOR31、SCOR31、OCSR31、COSR31、CSOR31、水酸基、ニトロ基、CN、ハロゲン原子、又はCOOR31で置換される場合もあり、
R31、R32及びR33は、それぞれ独立に、水素原子、炭素原子数1~30の炭化水素基又は複素環を含有する炭素原子数2~20の基を表し、
R31、R32及びR33で表される基の水素原子は、更に水酸基、ニトロ基、CN、ハロゲン原子、水酸基又はカルボキシル基で置換される場合もあり、
R21、R22、R23、R31、R32及びR33で表される基のメチレン基は、-O-、-S-、-COO-、-OCO-、-NR34-、-NR34COO-、-OCONR34-、-SCO-、-COS-、-OCS-又は-CSO-により酸素原子が隣り合わない条件で置換される場合もあり、
R34は、水素原子、炭素原子数1~30の炭化水素基又は複素環を含有する炭素原子数2~20の基を表し、
R13は、水素原子、炭素原子数1~30の炭化水素基又は複素環を含有する炭素原子数2~20の基を表し、また、R13とR17、R13とR18、R14とR15、R15とR16及びR16とR17はそれぞれ結合して環を形成している場合もあり、
R13で表わされる基の水素原子は、更にR31、OR31、COR31、SR31、NR32R33、CONR32R33、-NR32-OR33、-NCOR32-OCOR33、NR32COR31、OCOR31、COOR31、SCOR31、OCSR31、COSR31、CSOR31、水酸基、ニトロ基、CN、ハロゲン原子、又はCOOR31で置換される場合もあり、
R14、R15、R16及びR17は、それぞれ独立に、R21、OR21、SR21、COR24、CONR25R26、NR22COR21、OCOR21、COOR24、SCOR21、OCSR21、COSR24、CSOR21、水酸基、CN又はハロゲン原子を表し、
R24、R25及びR26は、水素原子又は炭素原子数1~20のアルキル基を表し、
R18は、R21、OR21、SR21、COR21、CONR22R23、NR22COR21、OCOR21、COOR21、SCOR21、OCSR21、COSR21、CSOR21、水酸基、CN又はハロゲン原子を表し、
nは、0又は1を表す。) - 上記ジフェニルスルフィド骨格及びオキシムエステル基を有する化合物(B2)が、下記一般式(IV)で表される化合物である請求項1~5の何れか一項に記載の重合性組成物。
R51、R52及びR53は、それぞれ独立に、水素原子、炭素原子数1~30の炭化水素基又は複素環を含有する炭素原子数2~20の基を表し、
R51、R52及びR53で表わされる置換基の水素原子は、更にOR61、COR61、SR61、NR62R63、CONR62R63、-NR62-OR63、-NCOR62-OCOR63、-C(=N-OR61)-R62、-C(=N-OCOR61)-R62、CN、ハロゲン原子又はCOOR61で置換される場合もあり、
R51、R52、R53、R61、R62及びR63で表される置換基のメチレン基は、-O-、-S-、-COO-、-OCO-、-NR64-、-NR64COO-、-OCONR64-、-SCO-、-COS-、-OCS-又は-CSO-により酸素原子が隣り合わない条件で置換される場合もあり、
R61、R62及びR63は、それぞれ独立に、水素原子、炭素原子数1~30の炭化水素基又は複素環を含有する炭素原子数2~20の基を表し、
R61、R62及びR63で表される置換基の水素原子は、更にCN、ハロゲン原子、水酸基又はカルボキシル基で置換される場合もあり、
R64は、水素原子、炭素原子数1~30の炭化水素基又は複素環を含有する炭素原子数2~20の基を表し、
R52とR53及びR62とR63はそれぞれ結合して環を形成している場合もあり、
R43は、R54、OR54、SR54、COR54、CONR55R56、NR55COR54、OCOR54、COOR54、SCOR54、OCSR54、COSR54、CSOR54、CN又はハロゲン原子を表し、R44は、R54、OR54、SR54、COR54、CONR55R56、NR55COR54、OCOR54、COOR54、SCOR54、OCSR54、COSR54、CSOR54、CN、ハロゲン原子、OH、COOH又は下記一般式(V)で表される基を表し、
R54、R55及びR56は、それぞれ独立に、水素原子、炭素原子数1~30の炭化水素基又は複素環を含有する炭素原子数2~20の基を表し、
f及びgは、それぞれ独立に、0~4の整数を表す。)
X3は、1~3個のR70で置換された炭素原子数1~30の炭化水素基又は複素環を含有する炭素原子数2~20の基を表し、
X3中のメチレン基は、-O-、-S-、-COO-、-OCO-、-NR69-、-NR69COO-、-OCONR69-、-SCO-、-COS-、-OCS-又は-CSO-により酸素原子が隣り合わない条件で置換される場合もあり、
R69は、水素原子、炭素原子数1~30の炭化水素基又は複素環を含有する炭素原子数2~20の基を表し、
R70は、OR71、SR71、CONR72R73、NR72COR73、OCOR71、COOR71、SCOR71、OCSR71、COSR71、CSOR71、CN又はハロゲン原子を表し、
R71、R72及びR73は、それぞれ独立に、水素原子又は炭素原子数1~30の炭化水素基を表す。式中の*は、*部分で、隣接する基と結合することを意味する。) - 光学活性化合物を含有する請求項1~6の何れか一項に記載の重合性組成物。
- 請求項1~7の何れか一項に記載の重合性組成物を用いて硬化物を製造する方法。
- 請求項1~7の何れか一項に記載の重合性組成物の硬化物。
- 請求項9に記載の硬化物を使用してなるディスプレイ用光学フィルム。
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JP2018509342A JP6894429B2 (ja) | 2016-03-30 | 2017-03-29 | 重合性組成物、硬化物及びディスプレイ用光学フィルム並びに硬化物を製造する方法 |
EP17775235.9A EP3438134B1 (en) | 2016-03-30 | 2017-03-29 | Polymerizable composition, cured object, optical film for display, and process for producing cured object |
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TWI834627B (zh) * | 2017-12-13 | 2024-03-11 | 日商艾迪科股份有限公司 | 化合物、潛在性鹼產生劑、含有該化合物之感光性樹脂組合物、硬化物、及硬化物之製造方法 |
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KR20240000709A (ko) * | 2022-06-24 | 2024-01-03 | 삼성에스디아이 주식회사 | 유기발광소자 봉지용 조성물 및 이로부터 제조된 유기층을 포함하는 유기발광소자 표시장치 |
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EP3438134B1 (en) | 2021-05-05 |
EP3438134A1 (en) | 2019-02-06 |
TWI742060B (zh) | 2021-10-11 |
KR102281732B1 (ko) | 2021-07-26 |
JP6894429B2 (ja) | 2021-06-30 |
TW201807051A (zh) | 2018-03-01 |
EP3438134A4 (en) | 2019-11-13 |
CN108602907B (zh) | 2021-04-09 |
KR20180128896A (ko) | 2018-12-04 |
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