Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
  • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
• • 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
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
  • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
  • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
• • 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
• • C—CHEMISTRY; METALLURGY
  • 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
  • C08K5/17—Amines; Quaternary ammonium compounds
• • 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
  • C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
  • C08K5/24—Derivatives of hydrazine
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
• • 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
  • C09K3/00—Materials not provided for elsewhere
  • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
• • 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
  • G02F1/1339—Gaskets; Spacers; Sealing of cells

Definitions

• the present invention relates to a photothermosetting resin composition, a liquid crystal sealant containing the same, a liquid crystal display panel, and a method for manufacturing the same.
• Display panels such as liquid crystals and organic EL are widely used as image display panels for various electronic devices such as mobile phones and personal computers.
• a liquid crystal display panel is formed by two transparent substrates having electrodes on their surfaces, a frame-shaped sealing member sandwiched between them, and a liquid crystal material enclosed in a region surrounded by the sealing members. And have.
• the seal member is required to have high adhesion to the substrate. If the sealing member is peeled off from the substrate, liquid crystal leakage or the like occurs, resulting in poor image display. Therefore, conventionally, a compound having a hydrophilic group (for example, a silane coupling agent) is included in the liquid crystal sealant for forming the seal member, and the hydrophilic group in the seal member and the hydrophilic group existing on the surface of the substrate are combined. By chemically bonding, these adhesions were enhanced.
• a hydrophilic group for example, a silane coupling agent
• Patent Document 1 proposes to include core-shell type particles in the liquid crystal sealant for forming the seal member.
• core-shell structural fine particles F-351 manufactured by Aica Kogyo Co., Ltd.
• F-351 manufactured by Aica Kogyo Co., Ltd.
• a liquid crystal display panel it is common to arrange alignment films on the surfaces of a pair of substrates to orient the liquid crystal in a desired direction. Then, in the conventional liquid crystal display panel, it is common to apply a liquid crystal sealant to the outside of the alignment film arranged on the substrate to form a seal member. Therefore, it is sufficient to improve the adhesion between the substrate and the sealing member, and it is possible to improve the adhesion of the sealing member to the substrate by adding a silane coupling agent or the like as described above.
• the present invention has been made in view of the above problems.
• the present invention provides the following photothermosetting resin composition and a liquid crystal sealant containing the same.
• Photothermosetting containing a curable compound (A) having an ethylenically unsaturated double bond in the molecule, a photopolymerization initiator (B), a latent thermosetting agent (C), and organic fine particles (D). It is a sex resin composition, and the organic fine particles (D) have an outer shell portion and a core portion, and the core portion is at least among a conjugated diene-based rubber and a silicone rubber containing a structural unit derived from a conjugated diene.
• a photothermosetting resin composition comprising one.
• the organic fine particles (D) are composed of the outer shell portion and the core portion, and the core portion contains a conjugated diene-based rubber containing a structural unit derived from a conjugated diene and an aromatic vinyl compound.
• the latent thermosetting agent (C) is one or more selected from the group consisting of an organic acid dihydrazide-based thermal latent curing agent, an amine adduct-based thermal latent curing agent, and a polyamine-based thermal latent curing agent.
• the present invention provides the following method for manufacturing a liquid crystal display panel and a liquid crystal display panel obtained from the manufacturing method.
• a method for manufacturing a liquid crystal display panel which comprises a step of curing the seal pattern.
• the photothermosetting resin composition of the present invention when used as a liquid crystal sealant, a seal member capable of firmly adhering between a pair of substrates can be obtained.
• the photothermosetting resin composition of the present invention contains a curable compound (A) having an ethylenically unsaturated double bond in the molecule, a photopolymerization initiator (B), and a latent thermosetting agent (). It contains C) and specific organic fine particles (D).
• the photothermally curable resin composition of the present invention contains organic fine particles (D) having an outer shell portion and a core portion, and the core portion of the organic fine particles (D) is a structural unit derived from a conjugated diene. Includes either conjugated diene-based rubbers or silicone rubbers.
• the photothermosetting resin composition contains such organic fine particles (D)
• the residual stress generated when the photothermosetting resin composition is applied and cured is relaxed by the core portion of the organic fine particles (D).
• NS Therefore, stress is unlikely to be applied between the substrate and the cured product. That is, even if the alignment film or the like is arranged on the substrate, peeling between the substrate and the photothermosetting resin composition (seal member) is unlikely to occur.
• the organic fine particles (D) can disperse the load. Therefore, stress is less likely to act on the interface between the sealing member and the substrate, and their peeling is suppressed.
• the curable compound (A) may be a compound having an ethylenically unsaturated double bond in the molecule.
• the curable compound (A) may be any of a monomer, an oligomer or a polymer.
• Examples of the curable compound (A) include a compound having a (meth) acryloyl group in the molecule.
• the number of (meth) acryloyl groups per molecule of the compound having the (meth) acryloyl group may be one or two or more.
• the term (meth) acryloyl group means an acryloyl group, a methacryloyl group, or both.
• the description of (meth) acrylate means acrylate, methacrylate, or both.
• the description of (meth) acrylic means acrylic, methacryl, or both.
• curable compound (A) containing one (meth) acryloyl group in one molecule examples include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl ester of (meth) acrylate and the like. Includes (meth) acrylic acid alkyl esters.
• Examples of the curable compound (A) having two or more (meth) acryloyl groups in one molecule include di (meth) acrylates derived from polyethylene glycol, propylene glycol, polypropylene glycol and the like; tris (2-hydroxyethyl) isocia. Nurate-derived di (meth) acrylate; diol-derived di (meth) acrylate obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of neopentyl glycol; 2 mol of ethylene oxide or propylene to 1 mol of bisphenol A.
• the curable compound (A) may further have an epoxy group in the molecule.
• the number of epoxy groups per molecule may be one or two or more.
• the photothermosetting resin composition can be cured by heat. That is, it is possible to use both photocuring and thermosetting together.
• the photothermosetting resin composition has photocurability and thermosetting property, it is possible to efficiently cure the photothermosetting resin composition in a short time.
• An example of a compound having a (meth) acryloyl group and an epoxy group in the molecule is a (meth) acrylic acid glycidyl ester obtained by reacting an epoxy compound and (meth) acrylic acid in the presence of a basic catalyst. included.
• the epoxy compound to be reacted with (meth) acrylic acid may be a polyfunctional epoxy compound having two or more epoxy groups in the molecule, and the crosslink density becomes too high to adhere to the cured product of the photothermosetting resin composition.
• a bifunctional epoxy compound is preferable from the viewpoint of suppressing the decrease in the epoxy compound. Examples of bifunctional epoxy compounds include bisphenol type epoxy compounds (bisphenol A type, bisphenol F type, 2,2'-diallyl bisphenol A type, bisphenol AD type, hydrogenated bisphenol type, etc.), biphenyl type epoxy compounds, and the like. And naphthalene type epoxy compounds are included.
• bisphenol A type and bisphenol F type bisphenol type epoxy compounds are preferable from the viewpoint that the coatability of the photothermally curable resin composition is likely to be improved.
• the curable compound (A) derived from the bisphenol type epoxy compound has advantages such as excellent coatability as compared with the curable compound (A) derived from the biphenyl ether type epoxy compound.
• the curable compound (A) may contain only one of the above compounds, but may contain two or more of the above compounds.
• the curable compound (A) has a compound (A1) having a (meth) acryloyl group in the molecule and no epoxy group, and a compound (A2) having a (meth) acryloyl group and an epoxy group in the molecule. ) And is preferably included.
• the photothermosetting resin composition further contains another curable compound (for example, an epoxy compound) described later, the compatibility between the compound (A1) and the epoxy compound may be low.
• the compound (A2) having an epoxy group is combined, the compatibility of each component in the photothermosetting resin composition is enhanced.
• a hydrophobic compound for example, an epoxy compound
• the content of the compound (A2) having a (meth) acryloyl group and an epoxy group in the molecule is not particularly limited, but is preferably 30% by mass or more with respect to the total amount of the curable compound (A), for example.
• the weight average molecular weight is preferably about 310 to 1000.
• the weight average molecular weight of the curable compound (A) can be measured in terms of polystyrene by, for example, gel permeation chromatography (GPC).
• the content of the curable compound (A) is preferably 40 to 80% by mass, more preferably 50 to 75% by mass, based on the total amount of the photothermosetting resin composition.
• the amount of the curable compound (A) is within the above range, the strength of the obtained cured product (for example, a sealing member) can be increased, and the adhesion between the substrate and the cured product (sealing member) can be enhanced.
• the photopolymerization initiator is not particularly limited as long as it is a compound capable of radically polymerizing the curable compound (A) by irradiation with light.
• it may be a self-cleaving type photopolymerization initiator or a hydrogenated inorganic type photopolymerization initiator.
• self-cleaving self-cleaving photopolymerization initiators include benzyl dimethyls such as alkylphenone compounds (eg 2,2-dimethoxy-1,2-diphenylethane-1-one (BASF IRGACURE 651)).
• hydrogen abstraction initiators examples include benzophenone compounds (eg, benzophenone, o-benzoylmethylbenzoate methyl-4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-.
• benzophenone compounds eg, benzophenone, o-benzoylmethylbenzoate methyl-4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-.
• Methyl-diphenylsulfide acrylicized benzophenone, 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, etc.
• thioxanthone compounds eg, thioxanthone, 2-Chlorothioxanthone (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 1-chloro-4-propoxythioxanthone, 1-chloro-4-ethoxythioxanthone (Speedcure CPTX manufactured by Lambson Limited), 2-isopropylxantone (Speedcure ITX manufactured by Lambson Limited) , 4-Isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone (Speedcure DETX manufactured by Lambson Limited), 2,4-dichlorothioxanthone, etc
• the absorption wavelength of the photopolymerization initiator (B) is not particularly limited, and for example, the photopolymerization initiator (B) that absorbs light having a wavelength of 360 nm or more is preferable. Among them, the photopolymerization initiator (B) that absorbs light in the visible light region is more preferable, and the photopolymerization initiator (B) that absorbs light having a wavelength of 360 to 780 nm is more preferable, and the photopolymerization initiator (B) that absorbs light having a wavelength of 360 to 430 nm is more preferable. ) Is particularly preferable.
• Examples of the photopolymerization initiator (B) that absorbs light having a wavelength of 360 nm or more include alkylphenone compounds, acylphosphine oxide compounds, titanosen compounds, oxime ester compounds, thioxanthone compounds, and anthraquinone compounds. , Preferably an oxime ester compound.
• the structure of the photopolymerization initiator (B) can be specified by combining high performance liquid chromatography (HPLC) and liquid chromatography mass spectrometry (LC / MS) with NMR measurement or IR measurement.
• HPLC high performance liquid chromatography
• LC / MS liquid chromatography mass spectrometry
• the molecular weight of the photopolymerization initiator (B) is preferably 200 or more and 5000 or less, for example. When the molecular weight is 200 or more, the photopolymerization initiator (B) is unlikely to elute into the liquid crystal when the photothermosetting resin composition is used as the liquid crystal sealant. On the other hand, when the molecular weight is 5000 or less, the compatibility with the curable compound (A) is enhanced, and the curability of the photothermosetting resin composition tends to be improved.
• the molecular weight of the photopolymerization initiator (B) is more preferably 230 or more and 3000 or less, and further preferably 230 or more and 1500 or less.
• the molecular weight of the photopolymerization initiator (B) can be determined as the "relative molecular weight" of the molecular structure of the main peak detected when analyzed by high performance liquid chromatography (HPLC).
• the main peak refers to the peak with the highest intensity (the peak with the highest peak height) among all the peaks detected at the detection wavelength characteristic of each compound (for example, 400 nm in the case of a thioxanthone compound).
• the relative molecular weight corresponding to the peak peak of the detected main peak can be measured by liquid chromatography-mass spectrometry (LC / MS: Liquid Chromatography Mass Spectrometry).
• the amount of the photopolymerization initiator (B) is preferably 0.01 to 10% by mass with respect to the above-mentioned curable compound (A).
• the amount of the photopolymerization initiator (B) is 0.01% by mass or more with respect to the curable compound (A)
• the curability of the photothermosetting resin composition tends to be good.
• the content of the photopolymerization initiator (B) is 10% by mass or less, the photopolymerization initiator (B) is less likely to be eluted into the liquid crystal when the photothermosetting resin composition is used as the liquid crystal sealant.
• the content of the photopolymerization initiator (B) is more preferably 0.1 to 5% by mass, further preferably 0.1 to 3% by mass, and 0.1 to 2.5 with respect to the curable compound (A). Mass% is particularly preferred.
• Latent thermosetting agent (C) The latent thermosetting agent (C) does not cure the thermosetting compound (A) or other curable compounds described below under normal storage conditions (room temperature, visible light, etc.), but when heat is applied, It is a compound that cures these compounds.
• the photothermosetting resin composition contains the latent thermosetting agent (C)
• the photothermosetting resin composition becomes thermosetting.
• a curing agent capable of curing an epoxy compound hereinafter, also referred to as "epoxy curing agent” is preferable.
• the epoxy curing agent preferably has a melting point of 50 ° C. or higher and 250 ° C. or lower, and has a melting point of 100 ° C. or higher and 200 ° C., from the viewpoint of enhancing the viscosity stability of the photothermosetting resin composition and not impairing the moisture resistance of the cured product.
• the temperature is more preferably 150 ° C. or higher, and further preferably 150 ° C. or higher and 200 ° C. or lower.
• epoxy hardeners are organic acid dihydrazide-based thermal latent curing agents, imidazole-based thermal latent curing agents, dicyandiamide-based thermal latent curing agents, amine adduct-based thermal latent curing agents, and polyamine-based thermal latent curing agents. Contains agents.
• organic acid dihydrazide-based thermal latent curing agents include adipic acid dihydrazide (melting point 181 ° C.), 1,3-bis (hydrazinocarboethyl) -5-isopropylhydranthin (melting point 120 ° C.), 7,11-octa. Includes decadien-1,18-dicarbohydrazide (melting point 160 ° C.), dodecanedioic acid dihydrazide (melting point 190 ° C.), sebacic acid dihydrazide (melting point 189 ° C.) and the like.
• imidazole-based thermal latent curing agents examples include 2,4-diamino-6- [2'-ethylimidazolyl- (1')]-ethyltriazine (melting point 215-225 ° C.) and 2-phenylimidazole (melting point). 137 to 147 ° C.) and the like.
• dicyandiamide-based thermal latent curing agents examples include dicyandiamide (melting point 209 ° C.) and the like.
• the amine adduct-based thermal latent curing agent is a thermal latent curing agent composed of an additional compound obtained by reacting an amine-based compound having catalytic activity with an arbitrary compound.
• amine adduct-based thermal latent curing agents are Ajinomoto Fine-Techno's Amicure PN-40 (melting point 110 ° C), Ajinomoto Fine-Techno's Amicure PN-23 (melting point 100 ° C), and Ajinomoto Fine-Techno's Amicure PN.
• the polyamine-based thermal latent curing agent is a thermal latent curing agent having a polymer structure obtained by reacting amine and epoxy, and an example thereof is ADEKA Hardener EH4339S (softening point 120 to 130 ° C.) manufactured by ADEKA Corporation. , And ADEKA Hardener EH4357S (softening point 73 to 83 ° C.) and the like.
• the latent thermosetting agent (C) may contain only one type of epoxy curing agent, or may contain two or more types of epoxy curing agent.
• the content of the latent thermosetting agent (C) is preferably 3 to 30% by mass, more preferably 3 to 20% by mass, still more preferably 5 to 20% by mass, based on the total amount of the photothermosetting resin composition.
• the photothermosetting resin composition of the present invention may be a one-component curable resin composition.
• the one-component curable resin composition is excellent in workability because it is not necessary to mix the main agent and the curing agent at the time of use.
• the content of the latent thermosetting agent (C) is preferably 3.8 to 75% by mass, more preferably 3.8 to 50% by mass, and 5 to 40% by mass with respect to the above-mentioned curable compound (A). Is even more preferable.
• the content of the latent thermosetting agent (C) with respect to the curable compound (A) is 3.8% by mass or more, the curability of the curable compound (A) at the time of heating is likely to be enhanced.
• it is 75% by mass or less when the photothermosetting resin composition is used as a liquid crystal sealant, the liquid crystal is less likely to be contaminated by the latent thermosetting agent (C).
• Organic fine particles (D) may be particles having an outer shell portion and a core portion and containing a conjugated diene rubber or a silicone rubber in the core portion.
• the core portion is a region located near the center of the organic fine particles (D) and imparting desired elasticity to the organic fine particles (D).
• the outer shell portion is a layered region arranged on the outermost surface side of the organic fine particles (D) from the core portion, and is a phase of the organic fine particles (D) and other components in the photothermosetting resin composition. It is a layer for increasing solubility.
• the outer shell portion may completely cover the core portion or only a part of the core portion, but it is better that the outer shell portion completely covers the core portion as organic fine particles (D).
• the affinity with other components can be enhanced, and the dispersibility of the organic fine particles (D) is enhanced.
• the organic fine particles (D) another layer may be contained between the outer shell portion and the core portion, but from the viewpoint of easy preparation of the organic fine particles (D), the outer shell portion and the core portion are used. It is preferably composed of. Whether or not the organic fine particles (D) have an outer shell portion and a core portion is specified by, for example, a transmission electron microscope (TEM) or the like after curing the photothermally curable resin composition with light and heat. can.
• TEM transmission electron microscope
• the core may contain at least one of a conjugated diene rubber or a silicone rubber, but may contain both. Further, the core portion may contain components other than these rubbers as long as the object of the present invention and curing are not impaired.
• the conjugated diene-based rubber may contain a structural unit derived from the conjugated diene, may have only a structural unit derived from the conjugated diene, and has the same weight of the conjugated diene and a vinyl monomer copolymerizable with the conjugated diene. It may be a coalescence or the like.
• conjugated diene examples include isoprene, 1,3-butadiene, 2-chloro-1,3-butadiene, 2-methyl-1,3-butadiene, chloroprene and the like.
• the conjugated diene-based rubber may contain only one type of structural unit derived from the conjugated diene, or may contain two or more types.
• the amount of the conjugated diene-derived structural unit in the conjugated diene rubber is preferably 50 to 100% by mass with respect to the total amount of all structural units.
• vinyl monomers copolymerizable with conjugated diene include aromatic vinyl-based monomers such as styrene, ⁇ -methylstyrene, monochlorostyrene and dichlorostyrene; vinylcarboxylic acid-based monomers such as acrylic acid and methacrylic acid; and acrylonitrile.
• Vinyl cyanized monomers such as methacrylonitrile; vinyl halide monomers such as vinyl chloride and vinyl bromide; vinyl acetate; alken monomers such as ethylene, propylene, butylene and isobutylene; diallylphthalate, triallyl cyanurate, triallyl Contains polyfunctional monomers such as isocyanurate and divinylbenzene.
• the conjugated diene-based rubber may contain only one type of structural unit derived from these vinyl monomers, or may contain two or more types of structural units.
• the amount of the structural unit derived from the vinyl monomer in the conjugated diene rubber is preferably 0 to 50% by mass with respect to the total amount of all the structural units.
• conjugated diene rubber examples include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene butadiene rubber (SBR), styrene isoprene butadiene rubber (SIBR), and ethylene propylene diene rubber (EPDM).
• NR natural rubber
• IR isoprene rubber
• BR butadiene rubber
• SBR styrene butadiene rubber
• SIBR styrene isoprene butadiene rubber
• EPDM ethylene propylene diene rubber
• Chloroprene rubber (CR), acrylonitrile butadiene rubber (NBR) and other diene rubbers are included.
• silicone rubber examples include rubber obtained by polymerizing a siloxane-based monomer, a siloxane-based monomer, and a copolymer of a siloxane-based monomer and a copolymerizable vinyl monomer.
• siloxane-based monomers examples include siloxane monomers having two alkyl and / or aryl groups such as dimethylsiloxane, diethylsiloxane, methylphenylsiloxane, diphenylsiloxane, and dimethylsiloxane-diphenylsiloxane; siloxane having one alkyl or aryl. Contains monomers and the like.
• the vinyl monomer copolymerizable with the siloxane-based monomer is the same as the vinyl monomer copolymerizable with the conjugated diene described above.
• the core of the organic fine particles (D) preferably contains a conjugated diene-based rubber among the above, and further preferably contains a structural unit derived from the conjugated diene and an aromatic vinyl compound (the above-mentioned aromatic vinyl monomer).
• an aromatic vinyl compound the above-mentioned aromatic vinyl monomer.
• SBR styrene-butadiene rubber
• the amount of the core portion in the entire organic fine particles (D) is preferably 60 to 90% by mass, more preferably 80 to 90% by mass.
• the ratio of the core portion in the organic fine particles (D) is in the above range, sufficient elasticity can be obtained in the cured product of the photothermosetting resin composition.
• the adhesive strength between the seal member obtained from the curable resin composition and the substrate of the liquid crystal display panel is sufficiently increased.
• the content of the nucleus in the organic fine particles (D) can be measured from the absorbance ratio of the spectrum of infrared spectroscopic analysis and the like.
• the shape of the core portion is not particularly limited, but a spherical shape is preferable from the viewpoint of making the particle size uniform.
• the outer shell portion of the organic fine particles (D) is a layer having an affinity with the above-mentioned core portion and capable of enhancing the dispersibility of the organic fine particles (D) in the photothermosetting resin composition. If there is, there is no particular limitation.
• the outer shell portion can be a polymer of a (meth) acrylate monomer or a vinyl monomer. Such an outer shell portion can be formed, for example, by forming the above-mentioned core portion and then polymerizing a (meth) acrylate monomer or a vinyl monomer around the core portion.
• Examples of (meth) acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, and stearyl (.
• Alkyl (meth) acrylates such as meta) acrylates and behenyl (meth) acrylates; aromatic ring-containing (meth) acrylates such as phenoxyethyl (meth) acrylates and benzyl (meth) acrylates; 2-hydroxyethyl (meth) acrylates, 4- Hydroxyalkyl (meth) acrylates such as hydroxybutyl (meth) acrylate; glycidyl (meth) acrylates such as glycidyl (meth) acrylate and glycidylalkyl (meth) acrylate; alkoxyalkyl (meth) acrylates; allyl (meth) acrylate , Allylalkyl (meth) acrylates such as allylalkyl (meth) acrylates; polyfunctional (meth) such as monoethylene glycol di (meth) acrylates, triethylene glycol di (meth) acrylates, tetraethylene glyco
• examples of vinyl monomers include the same monomers as vinyl monomers copolymerizable with the above-mentioned conjugated diene.
• the outer shell portion preferably contains a polymer having one or more structures selected from the group consisting of a methyl methacrylate structure, a styrene structure, an acrylonitrile structure, and a glycidyl structure.
• a polymer having one or more structures selected from the group consisting of a methyl methacrylate structure, a styrene structure, an acrylonitrile structure, and a glycidyl structure.
• the amount of the outer shell portion in the entire organic fine particles (D) is preferably 10 to 40% by mass, more preferably 10 to 20% by mass.
• the ratio of the outer shell portion in the organic fine particles (D) is in the above range, the dispersibility of the organic fine particles (D) becomes good.
• the content of the outer shell portion in the organic fine particles (D) can be measured from the absorbance ratio of the spectrum of infrared spectroscopic analysis and the like.
• the shape of the organic fine particles (D) is not particularly limited, but is preferably substantially spherical.
• the average particle size is preferably 0.1 to 0.8 ⁇ m, more preferably 0.1 to 0.6 ⁇ m.
• the average particle size can be measured by a microscope method, specifically, an image analysis of an electron microscope. More specifically, the liquid crystal sealant is image-analyzed, 50 organic fillers having a particle size of 1 ⁇ m or less are selected, and the average value when the particle size is measured is taken as the average particle size.
• the content of the organic fine particles (D) is preferably 5 to 17% by mass, more preferably 7 to 16% by mass, still more preferably 9 to 15% by mass, based on the total amount of the photothermosetting resin composition.
• the amount of the organic fine particles is 5% by mass or more, when the photothermosetting resin composition is used as a liquid crystal sealant, the adhesive strength between the cured product (seal member) and the substrate becomes high.
• the content of the organic fine particles (D) is 17% by mass or less, the amount of other components (for example, the curable compound (A)) becomes sufficient, and the strength of the cured product (sealing member) increases.
• the photothermosetting resin composition of the present invention may further contain an inorganic filler (E), if necessary.
• the photothermosetting resin composition contains the inorganic filler (E)
• the viscosity of the photothermosetting resin composition, the strength of the cured product, the linear expansion property, and the like tend to be improved.
• Examples of the inorganic filler (E) include calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, zirconium silicate, iron oxide, titanium oxide, titanium nitride, aluminum oxide (alumina), zinc oxide, and silicon dioxide.
• the shape of the inorganic filler (E) may be a fixed shape such as a spherical shape, a plate shape, a needle shape, or a non-fixed shape.
• the average primary particle size of the inorganic filler (E) is preferably 1.5 ⁇ m or less, and the specific surface area is more preferably 0.5 to 20 m 2 / g.
• the average primary particle size of the inorganic filler (E) can be measured by the laser diffraction method described in JIS Z8825-1.
• the specific surface area of the filler can be measured by the BET method described in JIS Z8830.
• the content of the inorganic filler (E) is preferably 1 to 45% by mass with respect to the total amount of the photothermosetting resin composition.
• the content of the inorganic filler (E) is more preferably 3 to 30% by mass with respect to the photothermosetting resin composition.
• thermosetting resin composition may further contain a thermosetting compound.
• thermosetting compound is a compound different from the above-mentioned curable compound (A).
• thermosetting compounds include epoxy compounds having an epoxy group in the molecule.
• the epoxy compound may be any of a monomer, an oligomer or a polymer.
• the photothermosetting resin composition contains an epoxy compound, the display characteristics of the obtained liquid crystal panel are improved, and the moisture resistance of the cured product (seal member) is further enhanced.
• the epoxy compound has an aromatic ring.
• the weight average molecular weight of the epoxy compound is preferably 500 to 10000, more preferably 1000 to 5000.
• the weight average molecular weight of the epoxy compound is measured by gel permeation chromatography (GPC) in terms of polystyrene.
• aromatic epoxy compounds include aromatic diols typified by bisphenol A, bisphenol S, bisphenol F, bisphenol AD and the like, and diols obtained by modifying these aromatic diols with ethylene glycol, propylene glycol, alkylene glycol and the like.
• Aromatic polyhydric glycidyl ether compound obtained by reaction with epichlorohydrin polyphenols represented by phenol or novolak resin derived from cresol and formaldehyde, polyalkenylphenol and copolymers thereof, and epichlorohydrin.
• the novolak type polyvalent glycidyl ether compound obtained by the reaction; glycidyl ether compounds of xylylene phenol resin and the like are included.
• cresol novolac type epoxy compound cresol novolac type epoxy compound, phenol novolac type epoxy compound, bisphenol A type epoxy compound, bisphenol F type epoxy compound, triphenol methane type epoxy compound, triphenol ethane type epoxy compound, trisphenol type epoxy compound, dicyclopentadiene type.
• Epoxy compounds, diphenyl ether type epoxy compounds or biphenyl type epoxy compounds are preferable.
• the photothermosetting resin composition may contain only one type of epoxy compound, or may contain two or more types of epoxy compounds.
• the epoxy compound may be liquid or solid.
• a solid epoxy compound is preferable from the viewpoint of easily increasing the moisture resistance of the cured product.
• the softening point of the solid epoxy compound is preferably 40 ° C. or higher and 150 ° C. or lower. The softening point can be measured by the ring-and-ball method specified in JIS K7234.
• the content of the thermosetting compound is preferably 3 to 20% by mass with respect to the thermosetting resin composition.
• the amount of the thermosetting compound is 3% by mass or more, it is easy to satisfactorily increase the moisture resistance of the cured product (seal member) of the thermosetting resin composition.
• the content of the thermosetting compound is 20% by mass or less, the photothermosetting resin composition is unlikely to have an excessive increase in viscosity.
• the amount of the thermosetting compound is more preferably 3 to 15% by mass, still more preferably 4 to 15% by mass, based on the thermosetting resin composition.
• the content of the thermosetting compound is preferably 3.8 to 50% by mass, more preferably 5 to 30% by mass, based on the curable compound (A).
• the content of the thermosetting compound with respect to the curable compound (A) is 3.8% by mass or more, the moisture resistance of the cured product and the adhesive strength to the glass substrate are further enhanced.
• it is 50% by mass or less, the compatibility with the curable compound (A) tends to be good at the time of production.
• thermosetting resin composition of the present invention contains, if necessary, a thermal radical polymerization initiator, a coupling agent such as a silane coupling agent, an ion trapping agent, an ion exchanger, a leveling agent, a pigment, a dye, and an increase. Additives such as sensitizers, plasticizers and antifoaming agents may be further included.
• silane coupling agents examples include vinyltrimethoxysilane, ⁇ - (meth) acryloxipropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, and the like.
• the content of the silane coupling agent is preferably 0.01 to 5% by mass with respect to the curable compound (A). When the content of the silane coupling agent is 0.01% by mass or more, the cured product of the photothermosetting resin composition tends to have sufficient adhesiveness.
• the photothermosetting resin composition of the present invention may further include a spacer or the like for adjusting the gap of the liquid crystal display panel.
• the total amount of other components is preferably 1 to 50% by mass with respect to the total amount of the photothermosetting resin composition.
• the total amount of the other components is 50% by mass or less, the viscosity of the photothermosetting resin composition is unlikely to increase excessively, and the coating stability of the photothermosetting resin composition is less likely to be impaired.
• the viscosity of the photothermosetting resin composition of the present invention at 25 ° C. and 2.5 rpm of the E-type viscometer is preferably 200 to 450 Pa ⁇ s, more preferably 300 to 400 Pa ⁇ s. .. When the viscosity is in the above range, the applicability of the photothermosetting resin composition by the dispenser becomes good.
• the photothermosetting resin composition of the present invention can be used, for example, as a sealing agent.
• the photothermally curable resin composition is particularly suitable as a display element sealant used for sealing display elements such as liquid crystal display elements, organic EL elements, and LED elements.
• the photothermosetting resin composition of the present invention is very suitable as a liquid crystal sealant for the liquid crystal dropping method because it does not easily contaminate the liquid crystal.
• the liquid crystal display panel of the present invention has a frame-shaped seal arranged between a pair of substrates (display substrate and facing substrate) each having an alignment film and the alignment films of the pair of substrates. It includes a member and a liquid crystal layer filled in a space surrounded by the sealing member between a pair of substrates.
• the sealing member is a cured product of the above-mentioned photothermosetting resin composition (liquid crystal sealing agent).
• Both the display board and the facing board are transparent boards.
• the material of the transparent substrate may be an inorganic material such as glass, or may be a plastic such as polycarbonate, polyethylene terephthalate, polyether sulfone, and PMMA.
• a matrix-like TFT, a color filter, a black matrix, or the like may be arranged on the surface of the display substrate or the facing substrate.
• An alignment film is further arranged on the surface of the display substrate or the facing substrate.
• the alignment film includes a known organic alignment agent or inorganic alignment agent.
• the sealing member obtained from a general liquid crystal sealing agent may have low adhesion to these alignment films.
• the above-mentioned photothermosetting resin composition liquid crystal sealant
• the above-mentioned photothermosetting resin composition can relax the residual stress generated in the seal member during curing and can absorb the stress applied to the liquid crystal display panel from the outside. Therefore, even if the sealing member is arranged in the region where the alignment film is formed, peeling is unlikely to occur at these interfaces. Therefore, the liquid crystal display panel of the present invention can realize a narrow frame.
• the liquid crystal display panel is manufactured by using the liquid crystal sealant of the present invention.
• the method for manufacturing a liquid crystal display panel generally includes a liquid crystal dropping method and a liquid crystal injection method, but the liquid crystal display panel of the present invention is preferably manufactured by the liquid crystal dropping method.
• the manufacturing method of the liquid crystal display panel by the liquid crystal dropping method is 1) A step of applying the above-mentioned liquid crystal sealant on the alignment film of one of the pair of substrates each having an alignment film to form a seal pattern. 2) A step of dropping the liquid crystal on one substrate, in the region surrounded by the seal pattern, or on the other substrate in a state where the seal pattern is uncured. 3) A process of superimposing one substrate and the other substrate via a seal pattern, 4) Includes a step of curing the seal pattern.
• the state in which the seal pattern is uncured means a state in which the curing reaction of the liquid crystal sealant has not progressed to the gel point. Therefore, in the step 2), the seal pattern may be semi-cured by irradiating or heating the seal pattern in order to suppress the dissolution of the liquid crystal sealant in the liquid crystal.
• One substrate and the other substrate are a display board or a facing board, respectively.
• step 4 only curing by light irradiation may be performed, but curing by heating may be performed after curing by light irradiation.
• the liquid crystal sealant can be cured in a short time, so that dissolution in the liquid crystal can be suppressed.
• damage to the liquid crystal layer due to light can be reduced as compared with the case where only curing by light irradiation is performed.
• the light to be irradiated is appropriately selected according to the type of the photopolymerization initiator (B) in the above-mentioned liquid crystal sealant (photothermosetting resin composition), but light in the visible light region is preferable, for example, wavelengths 370 to 370 to. Light of 450 nm is preferable. This is because light having the above wavelength causes relatively little damage to the liquid crystal material and the driving electrode.
• a known light source that emits ultraviolet rays or visible light can be used.
• a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, a xenon lamp, a fluorescent lamp, or the like can be used.
• the light irradiation energy may be any energy as long as the curable compound (A) can be cured.
• the photocuring time depends on the composition of the liquid crystal sealant, but is, for example, about 10 minutes.
• thermosetting temperature depends on the composition of the liquid crystal sealant, but is, for example, 120 ° C., and the thermosetting time is about 2 hours.
• Curable compound (A-1) > 160 g of liquid bisphenol F-type epoxy resin (Epototo YDF-8170C, manufactured by Toto Kasei Co., Ltd., epoxy equivalent 160 g / eq), 0.1 g of polymerization inhibitor (p-methoxyphenol), 0.2 g of catalyst (triethanolamine) , And 43.0 g of methacrylic acid were charged into the flask. Then, dry air was sent in, and the reaction was carried out for 5 hours while refluxing and stirring at 90 ° C. The obtained compound was washed with ultrapure water 20 times to obtain a partially modified methacrylic acid bisphenol F type epoxy resin (curable compound (A-1)).
• curable compound (A-4) As the curable compound (A-4), an acrylic resin (polyethylene glycol diacrylate, light acrylate 14EG-A, manufactured by Kyoeisha Chemical Co., Ltd.) was used.
• a monomer mixed solution in which 23 parts by mass of styrene, 19 parts by mass of methyl methacrylate, 12 parts by mass of acrylonitrile and 15 parts by mass of glycidyl methacrylate were mixed in advance was continuously added dropwise into the reaction solution over 3 hours. After completion of the dropping, aging was carried out for 3 hours. After completion of aging, the obtained aqueous emulsion was cooled to room temperature, and then an organic fine particle (D-1) having an average particle size of 0.2 ⁇ m was obtained using a spray dryer.
• a monomer mixed solution prepared by mixing 23 parts by mass of styrene, 23.3 parts by mass of methyl methacrylate, 12 parts by mass of acrylonitrile, and 10.8 parts by mass of n-butyl methacrylate in advance is continuously added dropwise into the reaction solution over 3 hours. did. After completion of the dropping, aging was carried out for 3 hours. After completion of aging, the obtained aqueous emulsion was cooled to room temperature, and then an organic fine particle (D-2) having an average particle size of 0.2 ⁇ m was obtained using a spray dryer.
• Examples 2 to 6 and Comparative Examples 1 to 6> A photothermosetting resin composition was prepared in the same manner as in Example 1 except that the composition was changed to that shown in Table 1.
• the two laminated glass substrates are held in a light-shielding box for 1 minute , then irradiated with light containing visible light of 3000 mJ / cm 2 (light having a wavelength of 370 to 450 nm), and further heated at 120 ° C. for 1 hour. Then, a test piece was obtained.
• a portion 4.5 mm from the corner (outside of the line) of the seal pattern of the obtained test piece is vertically pressed at a speed of 5 mm / min using an indentation tester (Model210, manufactured by Intesco) to form a photothermosetting resin composition.
• the stress when the cured product of the object was peeled off was measured.
• the adhesive strength was determined by dividing the stress by the line width of the cured product. The results are shown in Table 1.
• Examples 1 to 6 of Table 1 one or more selected from the group consisting of a rubber having an outer shell portion and a core portion and having a structural unit derived from a conjugated diene in the core portion and a silicone rubber.
• the results of the adhesive strength test were all good. It is considered that the residual stress generated when the photothermosetting resin composition is cured is relaxed by the organic fine particles (D), and the organic fine particles (D) disperse the stress when the stress is applied from the outside. Therefore, in Examples 1 to 6, it is presumed that peeling at the interface between the cured product and the substrate was unlikely to occur.
• the photothermosetting resin composition of the present invention a cured product having high adhesiveness to various substrates can be obtained. Therefore, the photothermosetting resin composition is very useful as a sealant or the like for various liquid crystal display devices.

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