WO2015072534A1 - Composition durcissable, procédé de production d'un film durci, film durci et dispositif d'affichage - Google Patents

Composition durcissable, procédé de production d'un film durci, film durci et dispositif d'affichage Download PDF

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WO2015072534A1
WO2015072534A1 PCT/JP2014/080148 JP2014080148W WO2015072534A1 WO 2015072534 A1 WO2015072534 A1 WO 2015072534A1 JP 2014080148 W JP2014080148 W JP 2014080148W WO 2015072534 A1 WO2015072534 A1 WO 2015072534A1
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group
component
curable composition
compound
mass
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Japanese (ja)
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幹雄 中川
米澤　裕之
健太 山▲ざき▼
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富士フイルム株式会社
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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
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
    • C08F299/065—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes from polyurethanes with side or terminal unsaturations
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H10K59/12—Active-matrix OLED [AMOLED] displays
    • H10K59/124—Insulating layers formed between TFT elements and OLED elements

Definitions

  • the present invention relates to a curable composition, a method for producing a cured film, a cured film, and an organic EL display device and a liquid crystal display device using the cured film.
  • Flat panel displays such as liquid crystal display devices and organic EL display devices are widely used.
  • an electronic component such as a liquid crystal display element, an integrated circuit element, a solid-state imaging element, and an organic EL
  • a flattening film for imparting flatness to the surface of the electronic component, and for preventing deterioration and damage of the electronic component
  • a curable composition is used when forming a protective film or an interlayer insulating film for maintaining insulation.
  • a polarizing plate is provided on a glass substrate, a transparent conductive circuit layer such as indium tin oxide (ITO) and a thin film transistor (TFT) are formed, and covered with an interlayer insulating film to form a back plate.
  • ITO indium tin oxide
  • TFT thin film transistor
  • a polarizing plate is provided on a glass substrate, a pattern of a black matrix layer and a color filter layer is formed as necessary, and a transparent conductive circuit layer and an interlayer insulating film are sequentially formed as a top plate, and this back plate and The liquid crystal is manufactured by enclosing the liquid crystal between the two plates with the upper plate facing the spacer.
  • a conventional curable composition the composition described in patent document 1 or 2 is known.
  • a curable composition capable of obtaining a cured film excellent in adhesion to a substrate, surface roughness of the film surface, and touch panel characteristics under high temperature and high humidity, and the above curable composition It is providing the cured film which hardened the thing, its manufacturing method, and the organic electroluminescent display device and liquid crystal display device which have the said cured film.
  • Component A contains a polymerizable compound having an ethylenically unsaturated bond
  • Component B contains a polymerization initiator
  • Component C contains a blocked isocyanate compound
  • Component D contains an organic solvent, , A urethane (meth) acrylate having 6 or more functional groups, and the ratio of the urethane (meth) acrylate having 6 or more functional groups in the component A is 70 to 100% by mass, and the sum of the component A, the component B and the component C is A curable composition characterized in that the amount is 85% by mass or more based on the total organic solid content of the curable composition;
  • Component B contains an oxime ester compound
  • Component C is a blocked isocyanate compound that protects a compound selected from the group consisting of tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate,
  • Step 1 is the step of applying the curable composition according to any one of ⁇ 1> to ⁇ 6> on the substrate, and Step 2 is to remove the organic solvent from the applied curable composition.
  • the curing step is a step of curing the curable composition from which the organic solvent has been removed with light, and further includes a heat treatment step of heat-treating a cured film obtained by curing the curable composition with light after the curing step.
  • a method for producing a cured film according to ⁇ 7>, ⁇ 9> A cured film obtained by curing the curable composition according to any one of ⁇ 1> to ⁇ 6>, ⁇ 10>
  • the cured film according to ⁇ 9> which is a protective film
  • ⁇ 11> An organic EL display device having the cured film according to ⁇ 9> or ⁇ 10>, ⁇ 12> A liquid crystal display device having the cured film according to ⁇ 9> or ⁇ 10>.
  • a curable composition capable of obtaining a cured film having excellent adhesion to a substrate, surface roughness of the film surface, and touch panel characteristics under high temperature and high humidity, the curable composition is cured.
  • the cured film, the manufacturing method thereof, and the organic EL display device and liquid crystal display device having the cured film can be provided.
  • 1 shows a conceptual diagram of a configuration of an example of an organic EL display device.
  • a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
  • 1 is a conceptual diagram of a configuration of an example of a liquid crystal display device.
  • the schematic sectional drawing of the active matrix substrate in a liquid crystal display device is shown, and it has the cured film 17 which is an interlayer insulation film.
  • 1 is a conceptual diagram illustrating a configuration of an example of a liquid crystal display device having a touch panel function.
  • FIG. 5 shows a conceptual diagram of a configuration of another example of a liquid crystal display device having a touch panel function.
  • the organic EL element in the present invention refers to an organic electroluminescence element.
  • groups atomic groups
  • substitution and non-substitution includes not only those having no substituent but also those having a substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • “(meth) acrylate” represents acrylate and methacrylate
  • “(meth) acryl” represents acryl and methacryl
  • “(meth) acryloyl” represents acryloyl and methacryloyl.
  • “polymerizable compound having an ethylenically unsaturated bond” or the like is also simply referred to as “component A” or the like.
  • “mass%” and “wt%” are synonymous, and “part by mass” and “part by weight” are synonymous. In the present invention, a combination of preferred embodiments is more preferred.
  • the molecular weight of the polymerizable compound having (Component A) an ethylenically unsaturated bond is measured by ESI-MS (electrospray ionization mass spectrometry). Moreover, about a polymer component, it is the weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography when tetrahydrofuran (THF) is used as a solvent. Note that (A) a polymerizable compound having an ethylenically unsaturated bond is measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent for compounds having a molecular weight of 5,001 or more. Polystyrene equivalent weight average molecular weight.
  • GPC gel permeation chromatography
  • the curable composition of the present invention includes (Component A) a polymerizable compound having an ethylenically unsaturated bond, (Component B) a polymerization initiator, and (Component C) a blocked isocyanate.
  • Component A a polymerizable compound having an ethylenically unsaturated bond
  • Component B a polymerization initiator
  • Component C a blocked isocyanate.
  • Component A contains a hexafunctional or higher urethane (meth) acrylate, and the ratio of the above hexafunctional or higher urethane (meth) acrylate in Component A is 70.
  • the total amount of Component A, Component B and Component C is 85% by mass or more based on the total organic solid content of the curable composition.
  • the curable composition of the present invention further comprises (Component E) an alkoxysilane compound, (Component F) inorganic particles, (Component G) (meth) acrylic copolymer, (Component H) mercapto compound, (Component W) interface.
  • Component E an alkoxysilane compound
  • Component F inorganic particles
  • Component G (meth) acrylic copolymer
  • Component H mercapto compound
  • Component W mercapto compound
  • Other components such as an activator may be included.
  • the curable composition of the present invention is preferably a composition in which the strength of the cured product is increased by heat-treating the cured product such as the obtained cured film after polymerization or subsequent to polymerization, It is more preferable that the composition contains a photopolymerization initiator as Component B, and is a composition in which the strength of the cured product is further increased by heat-treating the obtained cured product after polymerization by light.
  • the curable composition of the present invention contains (Component A) a polymerizable compound having an ethylenically unsaturated bond.
  • Component A only needs to have an ethylenically unsaturated bond, and may be a low molecular weight compound, an oligomer, or a polymer.
  • the content of component A is preferably 40% by mass or more, more preferably 50% by mass or more, and further preferably 60% by mass or more, based on the total solid content of the curable composition. It is preferably 70% by mass or more.
  • the upper limit is not particularly defined, but is preferably 99% by mass or less, and more preferably 95% by mass or less, for example.
  • solid content in a curable composition represents the component except volatile components, such as an organic solvent.
  • Component A contains hexafunctional or higher urethane (meth) acrylate, and the ratio of the above hexafunctional or higher urethane (meth) acrylate in Component A is 70 to 100% by mass, and 75 to 100% by mass. It is preferably 90 to 100% by mass, more preferably 95 to 100% by mass. The effect of this invention is more effectively exhibited as it is the said aspect.
  • the content of hexafunctional or higher urethane (meth) acrylate is preferably 40% by mass or more, more preferably 50% by mass or more, and 65% by mass with respect to the total solid content of the curable composition.
  • the upper limit is not particularly defined, but it is preferably 95% by mass or less.
  • the content of hexafunctional or higher urethane (meth) acrylate is preferably 60% by mass or more, more preferably 70% by mass or more, based on the total organic solid content of the curable composition.
  • the content is more preferably 80% by mass or more, and particularly preferably 80 to 95% by mass.
  • the total organic solid content means a solid content obtained by removing inorganic substances (such as inorganic particles) from the total solid content of the curable composition.
  • the organic solid content of a curable composition is preferable, as for content of 6 or more functional urethane (meth) acrylate, 70 mass% or more is more preferable, and 80 mass% or more is the most preferable.
  • the organic solid content here means the solid content of the organic material excluding organic particles such as polymer particles, inorganic particles such as metal oxide particles, and pigment components such as organic inorganic pigments from the solid content of the composition. Means.
  • the number of (meth) acryloxy groups in the hexafunctional or higher-functional urethane (meth) acrylate is preferably 8 or more, more preferably 10 or more, and still more preferably 12 or more.
  • the effect of this invention is more effectively exhibited as it is the said aspect.
  • the upper limit of the number of the (meth) acryloxy groups is not particularly limited, but is preferably 50 or less, more preferably 30 or less, and still more preferably 20 or less.
  • the curable composition of the present invention may contain only one type of hexafunctional or higher urethane (meth) acrylate, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
  • the molecular weight of the hexafunctional or higher urethane (meth) acrylate is preferably 500 to 20,000, more preferably 650 to 6,000, and still more preferably 800 to 3,000, from the viewpoint of cured film hardness. The effect of this invention is more effectively exhibited as it is the said aspect.
  • the molecular weight of hexafunctional or higher urethane (meth) acrylate is the number average molecular weight in terms of polystyrene of GPC when the molecular weight is 1,000 or more.
  • the (meth) acryloxy group in the hexafunctional or higher urethane (meth) acrylate may be either an acryloxy group or a methacryloxy group, or may be both, but is preferably an acryloxy group.
  • the number of urethane bonds in the hexa- or more functional urethane (meth) acrylate is not particularly limited, but is preferably 1 to 30, more preferably 1 to 20, and still more preferably 2 to 10. It is particularly preferably 2 to 5, and most preferably 2 or 3.
  • the hexafunctional or higher urethane (meth) acrylate is preferably a hexafunctional or higher aliphatic urethane (meth) acrylate.
  • hexafunctional or more urethane (meth) acrylate has an isocyanuric ring structure.
  • the hexafunctional or higher urethane (meth) acrylate is a compound comprising a core portion having one or more urethane bonds and a terminal portion bonded to the core portion and having one or more (meth) acryloxy groups.
  • the core part is more preferably a compound having two or more terminal parts bonded thereto, more preferably a compound having 2 to 5 terminal parts bonded to the core part.
  • a compound in which 2 or 3 of the above terminal moieties are bound to the core part is particularly preferred.
  • the hexafunctional or more urethane (meth) acrylate is preferably a compound having at least a group represented by the following formula (Ae-1) or (Ae-2), and represented by the following formula (Ae-1). It is more preferable that the compound has at least a group.
  • the hexafunctional or higher urethane (meth) acrylate is a compound having two or more groups selected from the group consisting of a group represented by the following formula (Ae-1) and a group represented by the formula (Ae-2) It is more preferable that Further, the terminal portion in the hexafunctional or higher functional urethane (meth) acrylate is preferably a group represented by the following formula (Ae-1) or (Ae-2).
  • R each independently represents an acryloyl group or a methacryloyl group, and a wavy line portion represents a bonding position with another structure.
  • the hexafunctional or higher urethane (meth) acrylate is preferably a compound having at least a group represented by the following formula (Ac-1) or (Ac-2), and represented by the following formula (Ac-1): It is more preferable that the compound has at least the group represented.
  • the above-mentioned core portion in the urethane (meth) acrylate having 6 or more functionalities is represented by the following formula (Ac-1) or (Ac-2) from the viewpoints of hardness, low-temperature curability, adhesion, solvent resistance, and coatability. It is preferable that it is group represented.
  • L 1 to L 4 each independently represents a divalent hydrocarbon group having 2 to 20 carbon atoms, and the wavy line represents the bonding position with another structure Represents.
  • L 1 to L 4 are each independently preferably an alkylene group having 2 to 20 carbon atoms, more preferably an alkylene group having 2 to 10 carbon atoms, and an alkylene group having 4 to 8 carbon atoms. Is more preferable.
  • the alkylene group may have a branched or ring structure, but is preferably a linear alkylene group.
  • the urethane (meth) acrylate having 6 or more functional groups is represented by a group represented by the formula (Ac-1) or the formula (Ac-2), and a formula (Ae-1) or a formula (Ae-2). Particularly preferred are compounds in which two or three groups selected from the group consisting of groups are bonded.
  • hexafunctional or higher urethane (meth) acrylates preferably used in the present invention will be exemplified, but it goes without saying that the present invention is not limited to these.
  • examples of the urethane (meth) acrylate having 6 or more functional groups that can be used in the present invention include urethane addition polymerizable compounds produced by using an addition reaction between an isocyanate and a hydroxyl group, and JP-A-51-37193.
  • examples of such urethane acrylates are described in Japanese Patent Publications, JP-B-2-32293 and JP-B-2-16765, and these descriptions are incorporated in the present specification.
  • Examples include Laromer UA-9048, UA-9050, PR9052, EBECRYL 220, 5129, 8301, KRM8200, 8200AE, and 8452 available from Daicel Ornex Co., Ltd.
  • the curable composition of the present invention is a polymerizable compound having an ethylenically unsaturated bond other than hexafunctional or higher urethane (meth) acrylate (also referred to as “other polymerizable compounds having an ethylenically unsaturated bond”). It may be included but is preferably not included.
  • the polymerizable compound having an ethylenically unsaturated bond other than the hexafunctional or higher urethane (meth) acrylate may be a polymer (for example, a molecular weight of 2,000 or more) or a monomer (for example, a molecular weight of 2,000).
  • a molecular weight of 100 or more and less than 2,000 preferably a molecular weight of 100 or more and less than 2,000
  • a monomer is preferred.
  • a (meth) acrylate compound is preferable.
  • the number of functional groups of the (meth) acrylate compound is preferably 2 to 6, and more preferably 3 to 6.
  • pentaerythritol tri (meth) acrylate pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri ((meth) acryloyloxyethyl) isocyanurate , Trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate ethylene oxide (EO) modified product, dipentaerythritol hexa (meth) acrylate EO modified product, and the like.
  • EO ethylene oxide
  • pentafunctional or lower urethane (meth) acrylate may be included as another polymerizable compound having an ethylenically unsaturated bond.
  • pentafunctional or lower urethane (meth) acrylate include the following compounds.
  • the curable composition of the present invention contains a polymerizable compound having an ethylenically unsaturated bond other than the hexafunctional or higher urethane (meth) acrylate, 0.1 to 20% by mass of the total solid content of the curable composition. It is preferably included in the range of 0.5 to 10% by mass, more preferably in the range of 1 to 5% by mass.
  • the curable composition of the present invention may contain only one type of polymerizable compound having an ethylenically unsaturated bond other than hexafunctional or higher urethane (meth) acrylate, and may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
  • the curable composition of the present invention contains (Component B) a polymerization initiator.
  • the polymerization initiator preferably contains a radical polymerization initiator.
  • the radical polymerization initiator that can be used in the present invention is a compound that can initiate and accelerate polymerization of a hexafunctional or higher urethane (meth) acrylate compound by light and / or heat. Among these, a photopolymerization initiator is preferable, and a photoradical polymerization initiator is more preferable.
  • the “light” is not particularly limited as long as it is an active energy ray capable of imparting energy capable of generating a starting species from the component B by the irradiation, and is widely limited to ⁇ rays, ⁇ rays, X rays, ultraviolet rays. (UV), visible light, electron beam, and the like. Among these, light containing at least ultraviolet rays is preferable.
  • Examples of the photopolymerization initiator include oxime ester compounds, organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocenes.
  • Examples include compounds, hexaarylbiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, onium salt compounds, and acylphosphine (oxide) compounds.
  • oxime ester compounds and hexaarylbiimidazole compounds are preferable from the viewpoint of sensitivity, and oxime ester compounds are more preferable.
  • the oxime ester compound examples include compounds described in JP-A No. 2000-80068, JP-A No. 2001-233842, JP-T No. 2004-534797, JP-A No. 2007-231000, and JP-A No. 2009-134289. Can be used.
  • the oxime ester compound is preferably a compound represented by the following formula (1) or formula (2).
  • Ar represents an aromatic group or heteroaromatic group
  • R 1 represents an alkyl group, an aromatic group or an alkyloxy group
  • R 2 represents a hydrogen atom or an alkyl group. Further, R 2 may be bonded to an Ar group to form a ring.
  • Ar represents an aromatic group or a heteroaromatic group, and is preferably a group obtained by removing one hydrogen atom from a benzene ring, naphthalene ring or carbazole ring, and a naphthalenyl group or carbazoyl group which forms a ring together with R 2 More preferred.
  • R 1 represents an alkyl group, an aromatic group or an alkyloxy group, preferably a methyl group, an ethyl group, a benzyl group, a phenyl group, a naphthyl group, a methoxy group or an ethoxy group, and a methyl group, an ethyl group, a phenyl group or a methoxy group Groups are more preferred.
  • R 2 represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a substituted alkyl group, and more preferably a hydrogen atom, a substituted alkyl group that forms a ring with Ar, or a toluenethioalkyl group.
  • the oxime ester compound is more preferably a compound represented by the following formula (3), formula (4) or formula (5).
  • R 1 represents an alkyl group, an aromatic group or an alkoxy group
  • X represents —CH 2 —, —C 2 H 4 —, —O— or —S—
  • R 3 independently represents a halogen atom
  • R 4 are each independently an alkyl group, a phenyl group, an alkyl-substituted amino group, an arylthio group, an alkylthio group, an alkoxy group, an aryloxy group or a halogen atom
  • R 5 Represents a hydrogen atom, an alkyl group or an aryl group
  • R 6 represents an alkyl group
  • n1 and n2 each independently represents an integer of 0 to 6
  • n3 represents an integer of 0 to 5.
  • R 1 represents an alkyl group, an aromatic group or an alkoxy group, and a group represented by R 11 —X′-alkylene group— (R 11 represents an alkyl group or an aryl group, and X ′ represents a sulfur atom or an oxygen atom.
  • R 11 is preferably an aryl group, more preferably a phenyl group.
  • the alkyl group and aryl group as R 11 may be substituted with a halogen atom (preferably a fluorine atom, a chlorine atom or a bromine atom) or an alkyl group.
  • X is preferably a sulfur atom.
  • R 3 and R 4 can be bonded at any position on the aromatic ring.
  • R 4 represents an alkyl group, a phenyl group, an alkyl-substituted amino group, an arylthio group, an alkylthio group, an alkoxy group, an aryloxy group or a halogen atom, preferably an alkyl group, a phenyl group, an arylthio group or a halogen atom, an alkyl group, an arylthio group A group or a halogen atom is more preferred, and an alkyl group or a halogen atom is still more preferred.
  • the alkyl group an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group or an ethyl group is more preferable.
  • R 4 As a halogen atom, a chlorine atom, a bromine atom, or a fluorine atom is preferable.
  • the number of carbon atoms in R 4 is preferably 0 to 50, more preferably 0 to 20.
  • R 5 represents a hydrogen atom, an alkyl group or an aryl group, and an alkyl group is preferable.
  • the alkyl group an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group or an ethyl group is more preferable.
  • aryl group an aryl group having 6 to 10 carbon atoms is preferable.
  • R 6 represents an alkyl group, preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group or an ethyl group.
  • n1 and n2 each represent the number of substitutions of R 3 on the aromatic ring in formula (3) or formula (4), and n3 represents the number of substitutions of R 4 on the aromatic ring in formula (5).
  • n1 to n3 are each independently preferably an integer of 0 to 2, and more preferably 0 or 1.
  • oxime ester compounds preferably used in the present invention are shown below. However, it goes without saying that the oxime ester compounds used in the present invention are not limited to these. Me represents a methyl group and Ph represents a phenyl group.
  • organic halogenated compounds include: Wakabayashi et al., “Bull Chem. Soc. Japan” 42, 2924 (1969), US Pat. No. 3,905,815, Japanese Patent Publication No. 46-4605. JP, 48-34881, JP 55-3070, JP 60-239736, JP 61-169835, JP 61-169837, JP 62-58241, JP-A 62-212401, JP-A 63-70243, JP-A 63-298339, P. Examples include compounds described in Hut “Journal of Heterocyclic Chemistry” 1 (No. 3), (1970), and in particular, oxazole compounds substituted with a trihalomethyl group and s-triazine compounds.
  • hexaarylbiimidazole compounds include, for example, JP-B-6-29285, US Pat. Nos. 3,479,185, 4,311,783, and 4,622,286. Examples include various compounds described in the specification.
  • acylphosphine (oxide) compounds include monoacylphosphine oxide compounds and bisacylphosphine oxide compounds. Specific examples include Irgacure 819, Darocur 4265, Darocur TPO, etc. manufactured by Ciba Specialty Chemicals. Can be mentioned.
  • a polymerization initiator can be used 1 type or in combination of 2 or more types.
  • the total amount of the polymerization initiator in the curable composition of the present invention is preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass, based on the total solid content in the composition.
  • the content is more preferably 1 to 10% by mass, and particularly preferably 2 to 5% by mass.
  • the total amount of the polymerization initiator in the curable composition of the present invention is 0.5 to 30% by mass with respect to the total solid content in the composition. Is preferably 1 to 20% by mass, more preferably 1 to 10% by mass, and particularly preferably 2 to 5% by mass.
  • a sensitizer can be added to the curable composition of the present invention.
  • Typical sensitizers that can be used in the present invention include those disclosed in Crivello [JV Crivello, Adv. In Polymer Sci., 62, 1 (1984)]. Examples include pyrene, perylene, acridine orange, thioxanthone, 2-chlorothioxanthone, benzoflavin, N-vinylcarbazole, 9,10-dibutoxyanthracene, anthraquinone, coumarin, ketocoumarin, phenanthrene, camphorquinone, and phenothiazine derivatives.
  • the sensitizer is preferably added in a proportion of 50 to 200% by mass with respect to the polymerization initiator.
  • the curable composition of the present invention contains (Component C) a blocked isocyanate compound.
  • component C a blocked isocyanate compound.
  • the blocked isocyanate compound is not particularly limited as long as it is a compound having a blocked isocyanate group, but is preferably a compound having two or more blocked isocyanate groups in one molecule from the viewpoint of curability.
  • the upper limit of the number of blocked isocyanate groups is not particularly defined, but is preferably 6 or less.
  • the skeleton of the blocked isocyanate compound is not particularly limited and may be any as long as it has two isocyanate groups in one molecule, and may be aliphatic, alicyclic or aromatic.
  • Polyisocyanate may be used.
  • a compound, a multimer thereof, and a prepolymer type skeleton compound derived from these compounds can be preferably used.
  • blocked isocyanate compounds that protect a compound selected from the group consisting of tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and multimers thereof.
  • a blocked isocyanate compound in which a compound selected from the group consisting of hexamethylene diisocyanate, isophorone diisocyanate, and multimers thereof is protected is more preferable.
  • the isocyanate compound multimer is not particularly limited as long as it is a dimer or higher multimer, and examples thereof include biuret bodies, isocyanurate bodies, and adduct bodies, and biuret bodies are preferred.
  • Examples of the matrix structure of the blocked isocyanate compound in the curable composition of the present invention include biuret type, isocyanurate type, adduct type, and bifunctional prepolymer type.
  • Examples of the blocking agent that forms the block structure of the blocked isocyanate compound include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds. be able to.
  • oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, or pyrazole compounds are preferable, oxime compounds and lactam compounds are more preferable, oxime compounds are more preferable, and methyl ethyl ketone oxime is more preferable.
  • oxime compound include oxime and ketoxime, and specific examples include acetoxime, formaldoxime, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, and benzophenone oxime.
  • lactam compound include ⁇ -caprolactam and ⁇ -butyrolactam.
  • Examples of the phenol compound include phenol, naphthol, cresol, xylenol, and halogen-substituted phenol.
  • Examples of the alcohol compound include methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, and alkyl lactate.
  • Examples of the amine compound include primary amines and secondary amines, which may be aromatic amines, aliphatic amines, and alicyclic amines, and examples thereof include aniline, diphenylamine, ethyleneimine, and polyethyleneimine.
  • Examples of the active methylene compound include diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate and the like.
  • Examples of the pyrazole compound include pyrazole, methylpyrazole, dimethylpyrazole and the like.
  • Examples of the mercaptan compound include alkyl mercaptans and aryl mercaptans.
  • the blocked isocyanate compound that can be used in the curable composition of the present invention is commercially available.
  • Coronate AP Stable M Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (above, Japan) Polyurethane Industry Co., Ltd.)
  • Takenate B-830, B-815N, B-820NSU, B-842N, B-84N, B-870N, B-874N, B-882N Mitsubishi Chemicals, Inc.
  • the content of the blocked isocyanate compound in the curable composition of the present invention is preferably in the range of 0.1 to 20% by mass, and preferably 0.5 to 10% by mass with respect to the total solid content of the curable composition. More preferably, it is contained in a range of 1 to 5% by mass.
  • the content of the blocked isocyanate compound in the curable composition of the present invention is preferably in the range of 0.1 to 20% by mass with respect to the total organic solid content of the curable composition, 0.5 to 10 More preferably, it is contained in the range of 1% by mass, and more preferably in the range of 1-5% by mass.
  • the weight ratio of component A to component C in the curable composition of the present invention is preferably 100: 1 to 10: 1, more preferably 50: 1 to 10: 1, and 20: 1 to More preferably, it is 10: 1.
  • the total amount of component A, component B, and component C is preferably 85% by mass or more, more preferably 90% by mass or more, and 95% by mass with respect to the total organic solid content of the curable composition. % Or more is more preferable.
  • the curable composition of the present invention may contain only one type of blocked isocyanate compound, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
  • the curable composition of the present invention contains an organic solvent. It is preferable that the curable composition of this invention is prepared as a solution which melt
  • the organic solvent used in the curable composition of the present invention known solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl.
  • Ethers propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, butylene glycol diacetates, dipropylene glycol dialkyl ethers, Dipropylene glycol monoalkyl ether acetates, alcohols, esters, ketones, Bromide, lactones and the like.
  • these solvents reference can be made to paragraph 0062 of JP-A-2009-098616.
  • propylene glycol monomethyl ether acetate diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, 1,3-butylene glycol diacetate, cyclohexanol acetate, propylene glycol diacetate, and tetrahydrofurfuryl alcohol are preferable.
  • the boiling point of the solvent is preferably 100 ° C. to 300 ° C., more preferably 120 ° C. to 250 ° C. from the viewpoint of applicability.
  • the organic solvent which can be used for this invention can be used individually by 1 type or in combination of 2 or more types. It is also preferred to use solvents having different boiling points in combination.
  • the content of the organic solvent in the curable composition of the present invention is 100 to 3,000 parts by mass per 100 parts by mass of the total solid content of the curable composition from the viewpoint of adjusting the viscosity to be suitable for coating. It is preferably 200 to 2,000 parts by mass, more preferably 250 to 1,000 parts by mass.
  • the solid content concentration in the curable composition of the present invention is preferably 3 to 50% by mass, and more preferably 20 to 40% by mass.
  • the viscosity of the curable composition of the present invention is preferably 1 to 200 mPa ⁇ s, more preferably 2 to 100 mPa ⁇ s, and most preferably 3 to 80 mPa ⁇ s.
  • the viscosity is preferably measured at 25 ⁇ 0.2 ° C. using a RE-80L rotational viscometer manufactured by Toki Sangyo Co., Ltd., for example.
  • the rotation speed during measurement is preferably 100 rpm for less than 5 mPa ⁇ s, 50 rpm for 5 mPa ⁇ s to less than 10 mPa ⁇ s, 20 rpm for 10 mPa ⁇ s to less than 30 mPa ⁇ s, and 10 rpm for 30 mPa ⁇ s or more.
  • the curable composition of the present invention preferably contains (Component E) an alkoxysilane compound.
  • the alkoxysilane compound that can be used in the curable composition of the present invention includes a base material, for example, a silicon compound such as silicon, silicon oxide, and silicon nitride, a metal such as gold, copper, molybdenum, titanium, and aluminum, and an insulating film. It is preferable that it is a compound which improves the adhesiveness of. Specifically, a known silane coupling agent or the like is also effective.
  • a silane coupling agent having an ethylenically unsaturated bond is preferred.
  • the silane coupling agent include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -glycidoxypropyltrialkoxysilane, ⁇ -glycidoxypropyl dialkoxysilane, and ⁇ -methacryloxypropyl.
  • ⁇ -methacryloxypropyltrialkoxysilane, ⁇ -acryloxypropyltrialkoxysilane, vinyltrialkoxysilane, or ⁇ -glycidoxypropyltrialkoxysilane is more preferable. These can be used alone or in combination of two or more. Examples of commercially available products include KBM-403 and KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.
  • the content of the alkoxysilane compound in the curable composition of the present invention is preferably 0.1 to 30 parts by mass and more preferably 2 to 20 parts by mass with respect to 100 parts by mass in total of the total solid content of the curable composition. 2 to 15 parts by mass is more preferable. Only one type of alkoxysilane compound may be included, or two or more types may be included. When two or more types are included, the total amount is preferably within the above range.
  • the curable composition of the invention preferably contains inorganic particles.
  • the hardness (strength) of the cured film becomes more excellent.
  • substrate can be improved by containing an inorganic particle.
  • the average particle size of the inorganic particles used in the present invention is preferably 1 to 200 nm, more preferably 5 to 100 nm, and most preferably 5 to 50 nm.
  • the average particle diameter is an arithmetic average obtained by measuring the particle diameter of 200 arbitrary particles with an electron microscope. When the particle shape is not spherical, the maximum outer diameter is taken as the particle diameter of the particle.
  • the porosity of the inorganic particles is preferably less than 10%, more preferably less than 3%, and most preferably no void.
  • the porosity of the particle is an arithmetic average of 200 of the area ratio between the void portion of the cross-sectional image obtained by an electron microscope and the entire particle.
  • inorganic particles Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, Nb, Mo, W, Zn, B, Al Metal oxide particles containing atoms such as Si, Ge, Sn, Pb, Sb, Bi, and Te are preferable.
  • Silicon oxide, titanium oxide, titanium composite oxide, zinc oxide, zirconium oxide, indium / tin oxide, antimony / Tin oxide is more preferable, silicon oxide, titanium oxide, titanium composite oxide, zirconium oxide is more preferable, silicon oxide or titanium oxide is the stability of particles, availability, hardness of the cured film, transparency, This is particularly preferable from the viewpoint of adjusting the refractive index.
  • a silica is mentioned preferably and a silica particle is mentioned more preferably.
  • the silica particles are not particularly limited as long as they are inorganic oxide particles containing silicon dioxide, and particles containing silicon dioxide or a hydrate thereof as a main component (preferably 80% by mass or more) are preferable.
  • grains may contain the aluminate as a minor component (for example, less than 5 mass%). Examples of the aluminate that may be contained as a minor component include sodium aluminate and potassium aluminate.
  • the silica particles may contain inorganic salts such as sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonium hydroxide, and organic salts such as tetramethylammonium hydroxide.
  • Colloidal silica is exemplified as an example of such a compound.
  • a dispersion medium of colloidal silica Any of water, an organic solvent, and these mixtures may be sufficient. These may be used individually by 1 type and can also use 2 or more types together.
  • the particles can be used as a dispersion prepared by mixing and dispersing in a suitable dispersant and solvent using a mixing device such as a ball mill or a rod mill.
  • the content of the inorganic particles is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and still more preferably 10 parts by mass or more per 100 parts by mass of the total solid content of the curable composition. Moreover, 80 mass parts or less are preferable, 50 mass parts or less are more preferable, 40 mass parts or less are further more preferable, and 30 mass parts or less are especially preferable.
  • One type of inorganic particles may be included, or two or more types may be included. When two or more types are included, the total amount is preferably within the above range.
  • the curable composition of the present invention may comprise (Component G) (meth) acrylic copolymer.
  • Monomers to be copolymerized with (meth) acrylic acid include styrene, methyl (meth) acrylate, ethyl (meth) acrylate, (alkylene substituted at the ⁇ -position such as styrene and ⁇ -methylstyrene, ( Meth) propyl acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, vinyl acetate, acrylonitrile, (meth) acrylamide, glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl ethyl acrylate, crotonyl glycidyl ether, Crotonic acid glycidyl ether, (meth) acrylic acid chloride, benzyl (meth) (meth) acrylic acid chloride,
  • component G in the curable composition of the present invention is preferably 1 to 20% by mass, more preferably 1 to 15% by mass, and still more preferably 1 to 10% by mass.
  • the curable composition of the present invention preferably contains (Component H) a mercapto compound.
  • a mercapto compound By containing a mercapto compound, the obtained cured film has excellent film strength.
  • a monofunctional mercapto compound or a polyfunctional mercapto compound is preferably used.
  • the monofunctional mercapto compound either an aliphatic mercapto compound or an aromatic mercapto compound can be used. From the viewpoint of film strength, an aromatic mercapto compound is preferable.
  • monofunctional aliphatic mercapto compounds include 1-octanethiol, 1-dodecanethiol, ⁇ -mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, Examples thereof include n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, stearyl-3-mercaptopropionate.
  • monofunctional aromatic mercapto compound those represented by the following formula (I) are preferable.
  • X S represents an oxygen atom, a sulfur atom or N—R S
  • R S represents a hydrogen atom, an alkyl group or an aryl group
  • A represents a heterocycle together with N ⁇ C—X S Represents an atomic group to be formed.
  • R S represents a hydrogen atom, an alkyl group or an aryl group.
  • alkyl group include linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms, such as straight chain having 1 to 12 carbon atoms, branched or carbon atoms having 3 to 12 carbon atoms.
  • a cyclic alkyl group of several 5 to 10 is more preferable.
  • Specific examples thereof include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group.
  • aryl group examples include those having 1 to 3 benzene rings forming a condensed ring in addition to those having a monocyclic structure, and those having a benzene ring and a 5-membered unsaturated ring forming a condensed ring. it can.
  • phenyl group examples include phenyl group, naphthyl group, anthryl group, phenanthryl group, indenyl group, acenaphthenyl group, fluorenyl group and the like. In these, a phenyl group and a naphthyl group are more preferable.
  • alkyl groups and aryl groups may further have a substituent.
  • substituents that can be introduced include a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and 2 to 2 carbon atoms.
  • A represents an atomic group that forms a heterocycle with N ⁇ C—X S.
  • atoms constituting this atomic group include a carbon atom, a nitrogen atom, a hydrogen atom, a sulfur atom, and a selenium atom.
  • the heterocycle formed by A and N ⁇ C—X S may further have a substituent, and examples of the substituent that can be introduced include substituents that can be introduced into the alkyl group and aryl group. The same thing is mentioned.
  • the monofunctional aromatic mercapto compound is more preferably a compound represented by the following formulas (II) to (V).
  • R S1 represents a hydrogen atom or an aryl group
  • X S1 independently represents a hydroxyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkyl group or an aryl group
  • R S2 represents an alkyl group or an aryl group
  • n represents an integer of 0 to 4
  • m represents an integer of 0 to 5.
  • the halogen atom in the formulas (II) to (V) is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
  • Examples of the alkoxy group and aryloxy group in the formulas (II) to (V) include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butyloxy group, a pentyloxy group, a hexyloxy group, a dodecyloxy group, and a benzyloxy group.
  • the alkyl group in the formulas (II) to (V) is synonymous with the alkyl group represented by R S in the formula (I), and its preferred range is also the same.
  • the aryl group in the formulas (II) to (V) has the same meaning as the aryl group represented by R S in the formula (I), and the preferred range thereof is also the same.
  • Each group in formula (II) to formula (V) may further have a substituent, and the substituent can be introduced into the alkyl group or aryl group represented by R S in formula (I). These are the same as those listed as examples of the substituent.
  • n and m are preferably 0 from the viewpoint of solubility in an organic solvent.
  • the following compounds are more preferred. When these compounds are used, the film strength increases and the storage stability is also good.
  • Component H is preferably a polyfunctional mercapto compound from the viewpoint of adhesion to the substrate.
  • the polyfunctional mercapto compound means a compound having two or more mercapto groups (thiol groups) in the molecule.
  • a low molecular compound having a molecular weight of 100 or more is preferable, specifically, a molecular weight of 100 to 1,500 is more preferable, and 150 to 1,000 is still more preferable.
  • the number of functional groups of the polyfunctional mercapto compound is preferably 2 to 10 functions, more preferably 2 to 8 functions, and even more preferably 2 to 4 functions. When the number of functional groups is large, the film strength is excellent, while when the number of functional groups is small, the storage stability is excellent. In the case of the said range, these can be made compatible.
  • aliphatic polyfunctional mercapto compound a compound having two or more groups represented by the following formula (S-1) is preferable.
  • R 1S represents a hydrogen atom or an alkyl group
  • a 1S represents —CO— or —CH 2 —
  • the wavy line represents a bonding position with another structure.
  • the alkyl group for R 1S in formula (S-1) is a linear, branched, or cyclic alkyl group, and the carbon number is preferably 1 to 16, more preferably 1 to 10.
  • Specific examples of the alkyl group include methyl group, ethyl group, propyl group, i-propyl group, butyl group, s-butyl group, t-butyl group, pentyl group, hexyl group, 2-ethylhexyl group and the like.
  • R 1S is particularly preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, or an i-propyl group, and most preferably a methyl group or an ethyl group.
  • the polyfunctional mercapto compound is particularly preferably a compound represented by the following formula (S-2) having a plurality of groups represented by the above formula (S-1).
  • R 1S independently represents a hydrogen atom or an alkyl group
  • a 1S independently represents —CO— or —CH 2 —
  • L 1S represents an nS-valent linking group.
  • NS represents an integer of 2 to 6. From the viewpoint of synthesis, it is preferred that all R 1S are the same group, and all A 1S are preferably the same group.
  • R 1S in formula (S-2) has the same meaning as R 1S in formula (S-1), and the preferred range is also the same.
  • nS is preferably an integer of 2 to 4.
  • L 1S as the nS-valent linking group in the formula (S-2) is, for example, a divalent linking group such as — (CH 2 ) mS — (mS represents an integer of 2 to 6), trimethylol, etc.
  • a trivalent linking group such as an isocyanuric ring having three propane residues, — (CH 2 ) pS — (pS represents an integer of 2 to 6)
  • a tetravalent linking group such as a pentaerythritol residue
  • five And hexavalent linking groups such as a divalent linking group and a dipentaerythritol residue.
  • polyfunctional mercapto compound a secondary thiol is more preferable.
  • polyfunctional mercapto compound examples include ethylene glycol bisthiopropionate, butanediol bisthiopropionate, trimethylolpropane tris (3-mercaptopropionate), and tris [(3-mercaptopropionyloxy) ethyl].
  • polyfunctional mercapto compounds include pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyryloxyethyl)- 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione is preferred, and pentaerythritol tetrakis (3-mercaptobutyrate) is more preferred.
  • a mercapto compound may be used individually by 1 type, or may use 2 or more types together.
  • the content of the mercapto compound is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, based on the total solid content of the curable composition. More preferably, it is 1 to 5% by mass. It is excellent in the point of coexistence with film
  • the curable composition of the present invention may contain a surfactant.
  • a surfactant any of anionic, cationic, nonionic, or amphoteric surfactants can be used, but a preferred surfactant is a nonionic surfactant.
  • the surfactant is preferably a nonionic surfactant, and more preferably a fluorosurfactant.
  • commercially available products such as MegaFuck F142D, F172, F173, F176, F177, F183, F479, F482, F554, and F780 are commercially available.
  • F781, F781-F, R30, R08, F-472SF, BL20, R-61, R-90 (manufactured by DIC Corporation), Florard FC-135, FC-170C, FC-430, FC-431, Novec FC-4430 (manufactured by Sumitomo 3M Limited), Asahi Guard AG7105, 7000, 950, 7600, Surflon S-112, S-113, S-131, S -141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-1 05, SC-106 (manufactured by Asahi Glass Co., Ltd.), F-top EF351, 352, 801, 802 (manufactured by Mitsubishi Materials Denka Kasei), and Footgent 250 (manufactured by Neos Co., Ltd.).
  • KP manufactured by Shin-Etsu Chemical Co., Ltd.
  • Polyflow manufactured by Kyoeisha Chemical Co., Ltd.
  • F-Top manufactured by Mitsubishi Materials Denka Kasei Co., Ltd.
  • MegaFuck manufactured by DIC Corporation
  • FLORARD manufactured by Sumitomo 3M Co., Ltd.
  • Asahi Guard manufactured by Surflon (manufactured by Asahi Glass Co., Ltd.)
  • PolyFox manufactured by OMNOVA
  • the surfactant includes a structural unit A and a structural unit B represented by the following formula (W), and has a polystyrene-reduced weight average molecular weight (Mw) of 1 measured by gel permeation chromatography using tetrahydrofuran as a solvent.
  • W polystyrene-reduced weight average molecular weight
  • Mw polystyrene-reduced weight average molecular weight
  • a copolymer having a molecular weight of 1,000 or more and 10,000 or less can be given.
  • R W1 and R W3 each independently represent a hydrogen atom or a methyl group
  • R W2 represents a linear alkylene group having 1 to 4 carbon atoms
  • R W4 represents a hydrogen atom or 1 carbon atom.
  • L W represents an alkylene group having 3 to 6 carbon atoms
  • p and q are mass percentages representing a polymerization ratio
  • p is a numerical value of 10% by mass to 80% by mass.
  • Q represents a numerical value of 20% by mass to 90% by mass
  • r represents an integer of 1 to 18, and s represents an integer of 1 to 10.
  • L W is preferably a branched alkylene group represented by the following formula (W-2).
  • R W5 in formula (W-2) represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to the coated surface. Two or three alkyl groups are more preferred.
  • the weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.
  • the content of the surfactant in the curable composition of the present invention is preferably 0.001 to 5.0 parts by mass with respect to 100 parts by mass in the total solid content of the curable composition. More preferred is 01 to 2.0 parts by mass. Only one type of surfactant may be included, or two or more types of surfactants may be included. When two or more types are included, the total amount is preferably within the above range.
  • the curable composition of the present invention may contain other components such as a plasticizer, a polymerization inhibitor, a thermal acid generator, an acid multiplier, an antioxidant, an epoxy compound, and an oxetane compound. it can.
  • these components for example, those described in JP2009-98616A, JP2009-244801A, and other known ones can be used.
  • various ultraviolet absorbers described in “New Development of Polymer Additives (Nikkan Kogyo Shimbun Co., Ltd.)”, metal deactivators, and the like may be added to the curable composition of the present invention.
  • the curable resin composition of the present invention may contain an antioxidant.
  • an antioxidant a well-known antioxidant can be contained. By adding an antioxidant, there is an advantage that coloring of the cured film can be prevented, or a decrease in film thickness due to decomposition can be reduced, and heat resistant transparency is excellent.
  • antioxidants include phosphorus antioxidants, amides, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, Examples thereof include nitrates, sulfites, thiosulfates, and hydroxylamine derivatives.
  • phenolic antioxidants hindered amine antioxidants, phosphorus antioxidants, and sulfur antioxidants are particularly preferable from the viewpoint of coloring the cured film and reducing the film thickness, with phenolic antioxidants being the most preferred. preferable.
  • These may be used individually by 1 type and may mix 2 or more types. Specific examples include the compounds described in paragraphs 0026 to 0031 of JP-A-2005-29515, and the compounds described in paragraphs 0106 to 0116 of JP-A-2011-227106. Embedded in the book.
  • Preferred commercial products include ADK STAB AO-60, ADK STAB AO-80, ADK STAB AO-412S (above, manufactured by ADEKA Corporation), IRGANOX 1035, and IRGANOX 1098 (above, manufactured by BASF).
  • the content of the antioxidant is not particularly limited, but is preferably 0.01 to 10% by mass and preferably 0.02 to 5% by mass with respect to the total solid content of the curable composition. More preferably, it is 0.05 to 4% by mass.
  • the curable resin composition of the present invention may contain a polymerization inhibitor.
  • a polymerization inhibitor is used to perform hydrogen donation (or hydrogen donation), energy donation (or energy donation), electron donation (or electron donation), etc. to the polymerization initiation radical component generated from the polymerization initiator by exposure. It is a substance that plays a role of deactivating polymerization initiation radicals and prohibiting polymerization initiation.
  • compounds described in paragraphs 0154 to 0173 of JP2007-334322A can be used.
  • Preferable compounds include phenothiazine, phenoxazine, hydroquinone, hydroquinone monomethyl ether, and 3,5-dibutyl-4-hydroxytoluene.
  • the content of the polymerization inhibitor is not particularly limited, but is preferably 0.0001 to 5% by mass with respect to the total solid content of the curable composition.
  • the total content of component A is preferably 40 to 99% by mass and the content of component B is 0.5 to 30% by mass with respect to the total solid content of the curable composition of the present invention.
  • the content of component C is preferably 0.1 to 20% by mass
  • the content of component E is preferably 0 to 30% by mass
  • the content of component F is 0 to 50% by mass.
  • the content of component G is preferably 0 to 20% by mass
  • the content of component H is preferably 0 to 15% by mass
  • the content of component W is 0 to 5% by mass.
  • the content of component D is preferably 100 to 3,000 parts by mass per 100 parts by mass of the total solid content of the curable composition.
  • the content of component A is preferably 40 to 80% by mass and the content of component B is 0.5 to 30% by mass with respect to the total organic solid content of the curable composition of the present invention.
  • the content of component C is preferably 0.1 to 20% by mass.
  • the total amount of component A, component B, and component C is preferably 85% by mass or more, more preferably 90% by mass or more, and 95% by mass with respect to the total organic solid content of the curable composition. % Or more is more preferable.
  • the curable composition of the present invention may contain other components such as a plasticizer, a thermal acid generator, and an acid multiplication agent as necessary.
  • these components for example, those described in JP2009-98616A, JP2009-244801A, and other known ones can be used.
  • various ultraviolet absorbers described in “New Development of Polymer Additives (Nikkan Kogyo Shimbun Co., Ltd.)”, metal deactivators, and the like may be added to the curable composition of the present invention.
  • the curable composition of the present invention does not contain polymer particles.
  • the cured product of the present invention is a cured product obtained by curing the curable composition of the present invention.
  • the cured product is preferably a cured film.
  • cured material of this invention is the hardened
  • the method for producing a cured product of the present invention is not particularly limited as long as it is a method for producing a cured product by curing the curable composition of the present invention, but preferably includes the following steps 1 to 3.
  • the method for producing a cured product of the present invention more preferably includes the following steps 1 to 4.
  • the method for producing a cured product of the present invention is preferably a method for producing a cured film.
  • the curable composition of the present invention is preferably applied onto a substrate to form a wet film containing a solvent.
  • the substrate Before applying the curable composition to the substrate, the substrate can be cleaned such as alkali cleaning or plasma cleaning. Furthermore, the substrate surface can be treated with hexamethyldisilazane or the like after cleaning the substrate. By performing this treatment, the adhesiveness of the curable composition to the substrate tends to be improved.
  • the substrate include inorganic substrates, resins, and resin composite materials.
  • the inorganic substrate include glass, quartz, silicon, silicon nitride, and a composite substrate in which molybdenum, titanium, aluminum, copper, or the like is vapor-deposited on such a substrate.
  • the resins include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamideimide, polyetherimide, poly Fluorine resins such as benzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester, cyclic polyolefin, aromatic Substrate made of synthetic resin such as aromatic ether, maleimide-olefin, cellulose, episulfide resin It is below. These substrates are rarely used in the above-described form, and usually, a multilayer laminated structure such as a TFT element is
  • the substrate preferably includes a metal film formed by sputtering.
  • the metal is preferably titanium, copper, aluminum, indium, tin, manganese, nickel, cobalt, molybdenum, tungsten, chromium, silver, neodymium and oxides or alloys thereof, molybdenum, titanium, aluminum, copper and More preferably, these alloys are used.
  • a metal and a metal oxide may be used individually by 1 type, or may use multiple types together.
  • the coating method on the substrate is not particularly limited.
  • a method such as an inkjet method, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, a slit and spin method, or a printing method may be used. it can.
  • the solvent removal step (2) it is preferable to remove the solvent from the applied film by vacuum (vacuum) and / or heating to form a dry coating film on the substrate.
  • the heating conditions for the solvent removal step are preferably 70 to 130 ° C. and about 30 to 300 seconds.
  • a polymerization initiating species is generated from the polymerization initiator by light and / or heat, polymerization is performed, and the curable composition from which the organic solvent has been removed is cured.
  • it is preferably a step of curing at least by light.
  • the light irradiation means that can be used in the step (3) is not particularly limited as long as it can be cured, but a mercury lamp, a metal halide lamp, a light emitting diode (LED), a laser diode (LD), a gas / solid laser, and the like can be used. Can be mentioned.
  • the amount of exposure in the step (3) is not particularly limited, but is preferably 50 to 3,000 mJ / cm 2 .
  • a step of exposing the entire surface from the viewpoint of improving the film hardness may be included.
  • energy exposure of about 50 to 3,000 mJ / cm 2 with a mercury lamp or an LED lamp.
  • (3) pattern exposure can be performed in the curing step, and (3) development step can be performed after the curing step.
  • the pattern exposure method is preferably a method using a mask or a direct drawing method using a laser or the like. It is preferable from the viewpoint of promoting curing that the light irradiation such as the entire surface exposure and pattern exposure in the step (3) is performed in a state where oxygen is blocked.
  • Examples of means for blocking oxygen include exposure in a nitrogen atmosphere and provision of an oxygen blocking film.
  • a known method or a known developer can be used.
  • the pattern exposure method and the development method described in JP 2011-186398 A and JP 2013-83937 A can be suitably used.
  • the heating temperature when curing by heat is preferably 180 ° C. or lower, more preferably 150 ° C. or lower, and further preferably 130 ° C. or lower.
  • the lower limit is preferably 80 ° C. or higher, more preferably 90 ° C. or higher.
  • the heating method is not particularly limited, and a known method can be used. For example, a hot plate, an oven, an infrared heater, etc. are mentioned.
  • the heating time is preferably about 1 to 30 minutes in the case of a hot plate, and about 20 to 120 minutes in other cases. Within this range, the substrate and the device can be cured without damage.
  • the heating can be performed at a lower temperature at the beginning and later at a higher temperature (addition of a middle baking step. For example, heating at 90 ° C. for 30 minutes first and then heating at 120 ° C. for 30 minutes later) .
  • cured material of this invention includes the process (heat treatment process, post-baking process) of heat-processing hardened
  • the cured product obtained by curing the curable composition of the present invention can obtain a cured product with higher strength by performing a heat treatment.
  • the temperature for the heat treatment is preferably 100 ° C. to 180 ° C., more preferably 110 ° C. to 150 ° C.
  • the time for the heat treatment is not particularly limited, but is preferably 1 minute to 360 minutes, more preferably 10 minutes to 240 minutes, and further preferably 30 minutes to 120 minutes.
  • the said heat processing may be performed continuously by hardening with light and / or heat, and may be performed sequentially.
  • the cured film of the present invention can be suitably used as a protective film or an interlayer insulating film.
  • a cured film having sufficient hardness can be obtained, for example, a cured film having a pencil hardness of 2H or more can be obtained. Since the protective film formed by curing the curable composition of the present invention is excellent in cured film properties, it is useful for applications in organic EL display devices and liquid crystal display devices.
  • a resist pattern formed using the curable composition of the present invention is used as a partition as a structural member of a MEMS device. Used as part of it.
  • MEMS devices include parts such as SAW filters, BAW filters, gyro sensors, display micro shutters, image sensors, electronic paper, inkjet heads, biochips, and sealants. More specific examples are exemplified in JP-T-2007-522531, JP-A-2008-250200, JP-A-2009-263544, and the like.
  • the curable composition of the present invention is excellent in flatness and transparency, for example, the bank layer (16) and the planarization film (57) described in FIG. 2 of JP-A-2011-107476, JP-A-2010-
  • a chemical film (12), a pixel isolation insulating film (14), and the like can also be used to form a chemical film (12), a pixel isolation insulating film (14), and the like.
  • spacers for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant color filters for the liquid crystal display device, color filter protective films, facsimiles, electronic copying machines, imaging of on-chip color filters such as solid-state image sensors It can also be suitably used for a microlens of an optical system or an optical fiber connector.
  • the organic EL display device of the present invention has the cured film of the present invention.
  • the organic EL display device of the present invention is not particularly limited except that it has a planarizing film and an interlayer insulating film formed using the curable composition of the present invention, and various known organic materials having various structures.
  • An EL display device and a liquid crystal display device can be given.
  • specific examples of TFT (Thin-Film Transistor) included in the organic EL display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
  • FIG. 1 is a conceptual diagram of an example of an organic EL display device.
  • a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
  • a bottom gate type TFT 1 is formed on a glass substrate 6, and an insulating film 3 made of Si 3 N 4 is formed so as to cover the TFT 1.
  • a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height: 1.0 ⁇ m) connected to the TFT 1 through the contact hole is formed on the insulating film 3.
  • the wiring 2 is used to connect the TFT 1 with an organic EL element formed between the TFTs 1 or in a later process.
  • a planarizing film 4 is formed on the insulating film 3 in a state where the unevenness due to the wiring 2 is embedded.
  • a bottom emission type organic EL element is formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7.
  • the first electrode 5 corresponds to the anode of the organic EL element.
  • An insulating film 8 having a shape covering the periphery of the first electrode 5 is formed.
  • a hole transport layer, an organic light-emitting layer, and an electron transport layer are sequentially deposited through a desired pattern mask, and then a first layer made of Al is formed on the entire surface above the substrate.
  • An active matrix organic material in which two electrodes are formed and sealed by bonding using a sealing glass plate and an ultraviolet curable epoxy resin, and each organic EL element is connected to a TFT 1 for driving it.
  • An EL display device is obtained.
  • the liquid crystal display device of the present invention has the cured film of the present invention.
  • the liquid crystal display device of the present invention is not particularly limited except that it has a protective film, a planarizing film, and an interlayer insulating film formed using the curable composition of the present invention, and is known in various structures.
  • a liquid crystal display device can be mentioned.
  • specific examples of TFTs (Thin-Film Transistors) included in the liquid crystal display device of the present invention include amorphous silicon-TFTs, low-temperature polysilicon-TFTs, and oxide semiconductor TFTs. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
  • Liquid crystal driving methods that can be taken by the liquid crystal display device of the present invention include a TN (Twisted Nematic) method, a VA (Virtual Alignment) method, an IPS (In-Place-Switching) method, an FFS (Fringe Field Switching) method, and an OCB (OCB) method. (Optically Compensated Bend) method.
  • the cured film of the present invention can also be used in a COA (Color Filter on Array) type liquid crystal display device.
  • the organic insulating film (115) disclosed in JP-A-2005-284291 and JP-A-2005 -346054 can be used as the organic insulating film (212).
  • the alignment method of the liquid crystal alignment film that the liquid crystal display device of the present invention can take include a rubbing alignment method and a photo alignment method.
  • the polymer orientation may be supported by a PSA (Polymer Sustained Alignment) technique described in JP-A Nos. 2003-149647 and 2011-257734.
  • the curable composition of this invention and the cured film of this invention are not limited to the said use, but can be used for various uses.
  • a protective film for example, in addition to a planarization film and an interlayer insulating film, it is suitable for a protective film, a spacer for keeping the thickness of a liquid crystal layer in a liquid crystal display device constant, a microlens provided on a color filter in a solid-state imaging device, Can be used.
  • FIG. 2 is a conceptual cross-sectional view showing an example of the active matrix type liquid crystal display device 10.
  • the color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel includes all pixels disposed between two glass substrates 14 and 15 having a polarizing film attached thereto.
  • the elements of the TFT 16 corresponding to are arranged.
  • Each element formed on the glass substrate is wired with an ITO transparent electrode 19 that forms a pixel electrode through a contact hole 18 formed in the cured film 17.
  • an RGB color filter 22 in which a liquid crystal 20 layer and a black matrix are arranged is provided.
  • the light source of the backlight is not particularly limited, and a known light source can be used.
  • the liquid crystal display device can be a 3D (stereoscopic) type or a touch panel type. Further, it can be made flexible, and used as the second interlayer insulating film (48) described in JP2011-145686A and the interlayer insulating film (520) described in JP2009-258758A. Can do.
  • FIG. 3 is a conceptual diagram of an example of a liquid crystal display device having a touch panel function.
  • the cured film of the present invention is preferably applied to a protective film between the layers in FIG. 3, and is also preferably applied to an interlayer insulating film that separates the detection electrodes of the touch panel.
  • reference numeral 110 denotes a pixel substrate
  • 140 denotes a liquid crystal layer
  • 120 denotes a counter substrate
  • 130 denotes a sensor unit.
  • the pixel substrate 110 includes a polarizing plate 111, a transparent substrate 112, a common electrode 113, an insulating layer 114, a pixel electrode 115, and an alignment film 116 in order from the lower side of FIG.
  • the counter substrate 120 includes an alignment film 121, a color filter 122, and a transparent substrate 123 in order from the lower side of FIG.
  • the sensor unit 130 includes a retardation film 124, an adhesive layer 126, and a polarizing plate 127.
  • reference numeral 125 denotes a sensor detection electrode.
  • the cured film of the present invention includes an insulating layer (114) (also referred to as an interlayer insulating film) in the pixel substrate portion, various protective films (not shown), various protective films (not shown) in the pixel substrate portion, and a counter substrate portion. Can be used for various protective films (not shown), various protective films (not shown) for the sensor portion, and the like.
  • a statically driven liquid crystal display device can display a pattern with high designability by applying the present invention.
  • the present invention can be applied as an insulating film of a polymer network type liquid crystal as described in JP-A-2001-125086.
  • FIG. 4 is a conceptual diagram of the configuration of another example of a liquid crystal display device having a touch panel function.
  • a lower display panel 200 corresponding to a thin film transistor display panel provided with a thin film transistor (TFT) 440, and a color filter display panel provided with a plurality of color filters 330 on the surface facing the lower display panel 200 and facing the lower display panel 200.
  • TFT thin film transistor
  • the liquid crystal layer 400 formed between the lower display panel 200 and the upper display panel 300.
  • the liquid crystal layer 400 includes liquid crystal molecules (not shown).
  • the lower display panel 200 is disposed on the first insulating substrate 210, the thin film transistor (TFT) disposed on the first insulating substrate 210, the insulating film 280 formed on the upper surface of the thin film transistor (TFT), and the insulating film 280.
  • a pixel electrode 290 is included.
  • the thin film transistor (TFT) may include a gate electrode 220, a gate insulating film 240 covering the gate electrode 220, a semiconductor layer 250, ohmic contact layers 260 and 262, a source electrode 270, and a drain electrode 272.
  • a contact hole 282 is formed in the insulating film 280 so that the drain electrode 272 of the thin film transistor (TFT) is exposed.
  • the upper display panel 300 is disposed on one surface of the second insulating substrate 310, the light shielding members 320 arranged in a matrix, the color filter 330 disposed on the second insulating substrate 310, and the color filter 330. And a common electrode 370 for applying a voltage to the liquid crystal layer 400 corresponding to the pixel electrode 290 of the lower display panel 200.
  • a sensing electrode 410, an insulating film 420, a driving electrode 430, and a protective film 280 are disposed on the other surface of the second insulating substrate 310.
  • the sensing electrode 410, the insulating film 420, the drive electrode 430, and the like, which are constituent elements of the touch screen are formed together. be able to.
  • a cured film obtained by curing the curable composition of the present invention can be suitably used for the insulating film 420.
  • Synthesis of A-9 Synthesis and purification were conducted in the same manner as in Synthesis Example 1 except that the hexamethylene diisocyanate trimer in Synthesis Example 1 was changed to hexamethylene diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.). A 10-functional urethane acrylate A-9 was obtained.
  • A-1 NK Oligo U-15HA (manufactured by Shin-Nakamura Chemical Co., Ltd., 15 functional groups)
  • A-2 UA-306H (manufactured by Kyoeisha Chemical Co., Ltd., 6 functional groups)
  • A-3 Laromer UA-9050 (manufactured by BASF, 8 functional groups)
  • A-4 NK Oligo U-10HA (manufactured by Shin-Nakamura Chemical Co., Ltd., 10 functional groups)
  • A-8 Compound synthesized according to Synthesis Example 1 (Synthetic product, 15 functional groups)
  • A-7 [Other polymerizable compounds having an ethylenically unsaturated bond] A-7: A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd., dipentaerythritol hexaacrylate, functional group number 6)
  • B-1 Compound B-1 below (Synthetic product, oxime ester compound)
  • B-2 Irgacure 379 (manufactured by BASF), acetophenone compound
  • F-1 PMA-ST (manufactured by Nissan Chemical Co., Ltd., silica fine particles, average particle size of 10 to 15 nm)
  • F-2 MIBK-ST-L (Nissan Chemical Co., Ltd., silica fine particles, average particle size 40-50 nm)
  • H-1 Karenz MT-PE1 (manufactured by Showa Denko KK)
  • H-2 Mercaptobenzothiazole (Tokyo Chemical Industry Co., Ltd.)
  • I-1 Irganox 1035 (manufactured by BASF)
  • I-2 Hydroquinone monomethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • reaction solution was added dropwise to 150 ml of distilled water cooled to 0 ° C., and the precipitated solid was subjected to suction filtration, washed with 200 ml of isopropyl alcohol cooled to 0 ° C., dried, and then compound B-1 (yield 19.5 g, yield). 99%).
  • Examples 1 to 41 and Comparative Examples 1 to 8) ⁇ Preparation of curable composition> As shown in Tables 1 to 4 below, each component was blended and stirred to obtain a solvent solution, which was filtered through a polytetrafluoroethylene filter having a pore size of 0.3 ⁇ m. Examples 1-41 and Comparative Example 1 Each of -8 curable compositions was obtained.
  • the unit of each component in the following Tables 1 to 4 is parts by mass excluding the ratio of component A + component B + component C in the organic solid content. Moreover, the mass part of solid content conversion is shown except an organic solvent.
  • a liquid crystal display device schematically shown in FIG. 4 was prepared using the compositions of the examples and comparative examples as protective films.
  • the protective film (insulating film, 420) was ink-jet coated with the curable composition obtained in each example of the present invention, pre-baked at 100 ° C. for 120 seconds, and 500 mJ / cm with a high-pressure mercury lamp. 2 (i-line conversion) light irradiation was performed, and further, baking was performed in an oven at 125 ° C. for 60 minutes.
  • the other part of the display device was manufactured according to Japanese Patent Laid-Open No. 2013-168125. After lighting for 1,000 hours under conditions of 60 ° C.
  • the cured film obtained by curing the curable composition of the present invention has adhesion to the substrate, surface roughness of the film surface, and touch panel under high temperature and high humidity. It was excellent in characteristics.

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Abstract

La présente invention a pour objectif de fournir une composition durcissable à l'aide de laquelle on puisse obtenir un film durci ayant une excellente adhérence à des substrats, une excellente rugosité superficielle de la surface du film, et des propriétés d'écran tactile à haute température et en présence d'une humidité élevée ; un film durci qui est obtenu par durcissement de la composition durcissable, et un procédé pour sa production ; et un dispositif d'affichage EL organique et un dispositif d'affichage à cristaux liquides qui comprend le film durci. Cette composition durcissable comprend un composé polymérisable ayant en tant que composant (A) une liaison à insaturation éthylénique, en tant que composant (B) un amorceur de polymérisation, en tant que composant (C) un composé isocyanate bloqué et en tant que composant (D) un solvant organique, le composant (A) comprenant un (méth)acrylate d'uréthanne hexafonctionnel ou à fonctionnalité plus élevée, la proportion du (méth)acrylate d'uréthanne hexafonctionnel ou à fonctionnalité plus élevée dans le composant (A) étant de 70 à 100 % en masse, et la quantité totale des composants (A), (B) et (C) étant de 85 % en masse ou plus par rapport à l'extrait sec organique total de la composition durcissable.
PCT/JP2014/080148 2013-11-15 2014-11-14 Composition durcissable, procédé de production d'un film durci, film durci et dispositif d'affichage WO2015072534A1 (fr)

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KR102679740B1 (ko) * 2022-01-25 2024-06-28 케이피엑스케미칼 주식회사 일액형 열경화성 수지 조성물 및 이를 포함하는 기능성 막

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WO2008140018A1 (fr) * 2007-05-11 2008-11-20 Sekisui Chemical Co., Ltd. Composition de résine durcissable destinée à un séparateur de colonnes, séparateur de colonnes, et élément d'affichage à cristaux liquides
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JP2009222799A (ja) * 2008-03-13 2009-10-01 Sekisui Chem Co Ltd カラムスペーサ用硬化性樹脂組成物、カラムスペーサ及び液晶表示素子

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WO2008140018A1 (fr) * 2007-05-11 2008-11-20 Sekisui Chemical Co., Ltd. Composition de résine durcissable destinée à un séparateur de colonnes, séparateur de colonnes, et élément d'affichage à cristaux liquides
JP2009086660A (ja) * 2007-09-12 2009-04-23 Dainippon Printing Co Ltd 光学積層体、その製造方法、偏光板及び画像表示装置
JP2009222799A (ja) * 2008-03-13 2009-10-01 Sekisui Chem Co Ltd カラムスペーサ用硬化性樹脂組成物、カラムスペーサ及び液晶表示素子

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