WO2022196764A1 - 液晶シール剤、液晶表示パネルの製造方法および液晶表示パネル - Google Patents
液晶シール剤、液晶表示パネルの製造方法および液晶表示パネル Download PDFInfo
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- WO2022196764A1 WO2022196764A1 PCT/JP2022/012288 JP2022012288W WO2022196764A1 WO 2022196764 A1 WO2022196764 A1 WO 2022196764A1 JP 2022012288 W JP2022012288 W JP 2022012288W WO 2022196764 A1 WO2022196764 A1 WO 2022196764A1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5046—Amines heterocyclic
- C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
- C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2003/1034—Materials or components characterised by specific properties
- C09K2003/1059—Heat-curable materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
- C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09K2200/0625—Polyacrylic esters or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
- C09K2200/0645—Macromolecular organic compounds, e.g. prepolymers obtained otherwise than by reactions involving carbon-to-carbon unsaturated bonds
- C09K2200/0647—Polyepoxides
Definitions
- the present invention relates to a liquid crystal sealant, a method for manufacturing a liquid crystal display panel, and a liquid crystal display panel.
- Display panels such as liquid crystal 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 includes two transparent substrates having electrodes provided on their surfaces, a frame-shaped sealant sandwiched between them, and a liquid crystal material enclosed in a region surrounded by the sealant.
- Patent Document 1 contains a curable resin, a polymerization initiator and a thermosetting agent (dihydrazide type), the storage modulus of the cured product at 25°C is less than 0.8 GPa, and the cured product at 121°C A sealant for a liquid crystal dropping method is disclosed, which has a storage modulus of 0.01 GPa or more.
- the storage elastic modulus of the cured product at 25° C. is less than 0.8 GPa, whereby the impact resistance can be improved, and the storage elastic modulus of the cured product at 121° C. is made 0.01 GPa or more. It is said that the heat and humidity resistance can be improved by this.
- Patent Literature 1 states that the storage modulus can be achieved by including a compound having an epoxy group and a rubber structure in the curable resin.
- Patent Document 2 a curable resin and a polymerization initiator or a thermosetting agent (dihydrazide type) are contained, the storage modulus of the cured product at 25° C. is less than 2.0 GPa, and the cured product has a storage modulus of 25° C.
- a sealant for a liquid crystal dropping method is described, which has a loss elastic modulus at °C of 0.1 GPa or more and 1.0 GPa or less. According to Patent Document 2, by lowering the storage elastic modulus of the cured product and increasing the loss elastic modulus to a certain level or more, the cured product is easily deformed and the shape is easily restored (plastic deformation is less likely to occur.
- Patent Document 2 by using a compound having a polymerizable functional group and a rubber structure as the curable resin, or by blending rubber particles into the sealing agent, the storage modulus and loss It is said that both elastic modulus can be achieved.
- Patent Document 3 a liquid crystal dripping method in which a compound having an epoxy group and an acryloyl group in the molecule is contained, the glass transition temperature measured by the DMA method is 90° C. or less, and the tan ⁇ is 0.5 or more A liquid crystal sealant for liquid crystals is described. Moreover, Patent Document 3 describes that a dihydrazide-based thermosetting agent is used. Patent document 3 states that the sealant has improved flexibility after curing, and can achieve sufficient adhesive strength even in flexible displays and curved displays.
- Patent Document 4 a curable resin, a polymerization initiator or a thermosetting agent, and an inorganic filler having a hydrophobic group on the surface with a content ratio of 15% by mass or more are included, and 25% of the cured product A sealant for a liquid crystal dropping method is described, which has a storage modulus at °C of 2.0 GPa or less.
- Patent Document 2 by setting the storage elastic modulus of the cured product to 2.0 GPa or less at 25° C., it is possible to prevent the panel from peeling off when the liquid crystal display element receives an impact such as being dropped.
- Patent Document 2 describes that a compound having a flexible skeleton such as a ring-opened structure of a cyclic lactone is preferable as the curable resin.
- the inventors of the present invention have found that when a liquid crystal display panel having a cured sealant is subjected to pressure treatment such as polishing, bright spots are generated in the liquid crystal due to the thermosetting agent exuding from the sealant (roughness). The inventors have newly found that there is a problem that the display characteristics are degraded.
- the first disclosure of the present specification has been made in view of the above problems, and the Young's modulus of the cured product is low, and when a liquid crystal display panel having a cured liquid crystal sealant is subjected to pressure treatment It is an object of the present invention to provide a liquid crystal sealing agent that can suppress the occurrence of roughness, a method for manufacturing a liquid crystal display panel using the liquid crystal sealing agent, and a liquid crystal display panel manufactured using the liquid crystal sealing agent. do.
- the cured product has a Young's modulus of 0.5 GPa or more and less than 3.0 GPa measured at 23° C., and an epoxy in the molecule
- One aspect of the present invention for solving the problems related to the second disclosure of the present specification is a cured product having an elongation of 30% or more measured at 23 ° C. and a thickness of 0.6 mm It relates to a liquid crystal sealant having a moisture permeability of less than 50 g/m 2 in an environment of 60° C. and 90 Rh.
- Another aspect of the present invention for solving the above problems is a step of applying the liquid crystal sealing agent onto the alignment film of one of a pair of substrates each having an alignment film to form a seal pattern. a step of dropping a liquid crystal onto the one substrate and within the region of the seal pattern or onto the other substrate while the seal pattern is in an uncured state; and a step of curing the seal pattern.
- Another aspect of the present invention for solving the above problems is a pair of substrates each having an alignment film, a frame-shaped sealing member disposed between the alignment films of the pair of substrates, and the pair of substrates. and a liquid crystal layer filled in a space surrounded by the sealing member between and, wherein the sealing member is a cured product of the liquid crystal sealing agent.
- a liquid crystal sealing agent having a low Young's modulus of a cured product and capable of suppressing the occurrence of roughness when a liquid crystal display panel having the cured liquid crystal sealing agent is subjected to pressure treatment A method for manufacturing a liquid crystal display panel using the liquid crystal sealing agent and a liquid crystal display panel manufactured using the liquid crystal sealing agent are provided.
- (meth)acrylate means acrylate or methacrylate
- (meth)acryloyl group means acryloyl group or methacryloyl group
- (meth)acrylic acid means acrylic acid or methacrylic acid.
- (meth)acrylic acid resin means an acrylic resin or a methacrylic resin.
- Liquid Crystal Sealant One embodiment of the present invention relates to a sealant (hereinafter also simply referred to as "sealant”) for sealing liquid crystal in a liquid crystal display panel.
- thermosetting compound (A) having an epoxy group in the molecule may contain, as a curable resin, a thermosetting compound (A) having two or more epoxy groups in the molecule. In this specification, the thermosetting compound (A) does not include the partial epoxy (meth)acrylate described later.
- thermosetting compound (A) may be any monomer, oligomer or polymer.
- the thermosetting compound (A) can further reduce the moisture permeability of the cured product, improve the display characteristics of the obtained liquid crystal panel, and improve the reliability of the liquid crystal display panel.
- thermosetting compound (A) preferably has a weight average molecular weight of 500 to 10,000, more preferably 500 to 5,000.
- the weight average molecular weight of the thermosetting compound (A) is measured in terms of polystyrene by gel permeation chromatography (GPC).
- the thermosetting compound (A) is preferably a compound having an aromatic ring.
- epoxy compounds having an aromatic ring include aromatic diols represented by bisphenol A, bisphenol S, bisphenol E, bisphenol F, bisphenol AD, etc., or these aromatic diols in ethylene glycol, propylene glycol, alkylene glycol.
- Aromatic polyhydric glycidyl ether compounds obtained by reacting diols modified with Etc. with epichlorohydrin, novolak resins derived from phenol or cresol and formaldehyde, polyphenols represented by polyalkenylphenols and their copolymers, etc.
- thermosetting resin composition (A) may contain only one type of epoxy compound, or may contain two or more types.
- the flexibility of the cured product is enhanced by using an epoxy compound having a structure (rubber structure) having an unsaturated bond or a siloxane structure in the molecule.
- the compound having the rubber structure is likely to be eluted into the liquid crystal and easily cause contamination of the liquid crystal. Therefore, the thermosetting compound (A) preferably has substantially no unsaturated bonds and siloxane structures in its molecule.
- the content of unsaturated bonds or siloxane structures in the molecule is preferably 5% by mass or less, more preferably 1% by mass or less.
- thermosetting compound (A) may be liquid or solid.
- a solid epoxy compound is preferable from the viewpoint of further reducing the moisture permeability 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 defined in JIS K7234 (1986).
- the liquid crystal sealant related to each of the above disclosures is a curable resin having a property ratio of 4.70 or less, a Tg of 250° C. or more and 340° C. or less, and a weight average molecular weight (Mw) of 1,000 or more (B ) may be included.
- the above characteristic ratio is a value that represents the flexibility of a molecule, and is a parameter that indicates that the smaller the molecule, the more rounded it is.
- ⁇ R 0 2 > is the root-mean-square value of all possible end-to-end distances of polymer chains.
- L is the root mean square value of the length of each structural unit that constitutes the polymer chain, and n is the number of structural units.
- the curable compound (B) having a property ratio of 4.70 or less can take a stable structure in a more rounded state than other resins. Therefore, the specific curable compound (B) is normally in a rounded state, but can assume an elongated state when stress is applied to the cured product of the sealant. Since the specific curable compound (B) has a large change in state between the curled state and the stretched state, it easily expands and contracts even after curing. considered to increase. In addition, by ensuring flexibility and elongation with a specific curable compound (B), other materials and compounds having a structure that makes it difficult for moisture to permeate into the molecule can be used as the specific curable compound (B).
- the characteristic ratio of the specific curable compound (B) is preferably 4.70 or less, more preferably 4.50 or less.
- the upper limit of the characteristic ratio of the specific curable compound (B) is not particularly limited, it is preferably 4.30 or more from the viewpoint of further stabilizing the viscosity.
- the above characteristic ratio can be a value calculated by the Bicerano method.
- the Bicerano method is a method for calculating predicted values of resin properties described in Joseph Bicerano, "Prediction of Polymer Properties", Marcel Dekker, New York, 2002.
- the specific curable compound (B) may be, for example, a resin having hydrogen bonds in the molecule, a resin having an ortho-substituted aromatic ring, or a resin having a keto group in the repeating structure portion.
- the specific curable compound (B) may be any curable compound such as a photocurable compound and a thermosetting compound. From the viewpoint of suppressing contamination, it is preferably a photocurable compound.
- the specific curable compound (B) as the photocurable compound is more preferably a compound having an ethylenically unsaturated double bond in the molecule (excluding partial epoxy (meth)acrylate), and the reactivity is A compound having a (meth)acryloyl group is more preferable because it is high.
- the specific curable compound (B) is preferably a curable compound represented by the following general formula (2).
- R 1 represents a divalent residue derived from a polyepoxy compound
- R 2 represents a divalent structure obtained by independently ring-opening a cyclic lactone
- R 3 represents Each independently represents a linear or branched alkylene group having 1 to 6 carbon atoms
- R 4 independently represents a hydrogen atom or a methyl group.
- R 1 is a divalent residue derived from a polyepoxy compound.
- polyepoxy compounds include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol E type epoxy resin and bisphenol F type epoxy resin, hydrogenated bisphenol type epoxy resin, novolak type epoxy resin, biphenyl type epoxy resin, stilbene type epoxy resin, hydroquinone type epoxy resin, naphthalene skeleton type epoxy resin, tetraphenylolethane type epoxy resin, trishydroxyphenylmethane type epoxy resin, dicyclopentadiene phenol type epoxy resin, 3′,4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, etc.
- bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol E type epoxy resin and bisphenol F type epoxy resin, hydrogen
- cycloaliphatic epoxy resin polyglycidyl esters of polybasic acids, such as the diglycidyl ester of hexahydrophthalic anhydride; Sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, pentaerythritol polyglycidyl ether, trimethylolpropane polyglycidyl ether, polypropylene glycol diglycidyl ether, diglycerol polyglycidyl ether, glycerol polyglycidyl ether, hexanediol diglycidyl ether, hydrogenated bisphenol A glycidyl ethers such as diglycidyl ether and cyclohexanedimethanol diglycidyl ether; diene polymer type epoxy resin such as polybutadiene or polyisoprene; glycidylamine-type epoxy resins such as tetraglycidyldia
- R 1 preferably has a divalent structure represented by the following general formula (2).
- X represents a single bond, methylene group, methylmethylene group, dimethylmethylene group, methylphenylmethylene group, cyclohexylidene group, sulfonyl group, ether bond or thioether bond.
- X in general formula (2) is preferably a methylene group.
- R 2 is a divalent structure obtained by ring-opening a cyclic lactone.
- the type of the cyclic lactone is not particularly limited, it is preferably a cyclic lactone having 2 or more and 6 or less carbon atoms, and more preferably a cyclic lactone having 4 or more and 6 or less carbon atoms.
- Examples of such cyclic lactones include ⁇ -acetolactone (2 carbon atoms), ⁇ -propiolactone (3 carbon atoms), ⁇ -butyrolactone (4 carbon atoms), ⁇ -valerolactone (5 carbon atoms), and ⁇ -caprolactone ( Carbon number 6) and the like are included.
- R 2 may be substituted.
- R2 is ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -valerolactone, from the viewpoint of increasing the elasticity of the curable compound and increasing the flexibility of the sealant (lowering the Young's modulus). and ⁇ -caprolactone, and more preferably ⁇ -butyrolactone, ⁇ -valerolactone and ⁇ -caprolactone.
- R 2 is a divalent structure represented by the following general formula (3).
- Y is an alkylene group having 2 to 6 carbon atoms, preferably 3 to 6 carbon atoms, more preferably 4 to 6 carbon atoms.
- Y may be substituted.
- substituents include methyl, ethyl, propyl, butyl, pentyl, hexyl, and the like.
- R 2 may repeat a divalent structure obtained by ring-opening the above cyclic lactone (a divalent structure represented by the general formula (3)).
- the number of repetitions at this time is not particularly limited, it is preferably 1 or more and 6 or less, and more preferably 1 or more and 5 or less.
- R 3 is a linear or branched alkylene group having 1 to 6 carbon atoms.
- alkylene groups include ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, hexyl and the like.
- R 3 is preferably an ethyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group.
- a propyl group and an isopropyl group are more preferred.
- Y may be substituted.
- substituents include methyl, ethyl, propyl, butyl, pentyl, hexyl, and the like.
- R4 is a hydrogen atom or a methyl group.
- the curable compound represented by general formula (2) is a bifunctional (meth)acrylic resin having a repeating structure with a keto group and an ortho-substituted benzene ring. According to the findings of the present inventors, the curable compound represented by the general formula (2) having such a structure tends to increase the property ratio. Furthermore, since the curable compound represented by the general formula (2) has a relatively large molecular weight, it is difficult to elute into the liquid crystal, so it is easy to suppress contamination of the liquid crystal due to elute of the sealant into the liquid crystal.
- the curable compound represented by general formula (2) can be synthesized by a known method. For example, a reaction flask is charged with a (meth)acrylate having a hydroxyl group, phthalic anhydride and a cyclic lactone, and in the presence of a polymerization inhibitor, dry air is blown in and these are reacted while stirring under reflux, followed by a polyepoxy compound. is added, dry air is sent in, and the reaction is carried out while stirring under reflux to synthesize the curable compound represented by the general formula (2).
- the specific curable compound (B) has a weight average molecular weight (Mw) of 1000 or more.
- the weight average molecular weight (Mw) is preferably 1000 or more and 2000 or less, more preferably 1200 or more and 1800 or less, and even more preferably 1400 or more and 1600 or less.
- Mw of the specific curable compound (B) is 1000 or more, the flexibility of the cured product can be further improved (the Young's modulus can be reduced from the decrease), and the elongation of the cured product can be further improved. can be enhanced.
- the specific curable compound (B) has an Mw of 2000 or less, the moisture permeability of the sealant can be further reduced.
- the Mw of the specific curable compound (B) is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard.
- the specific curable compound (B) has a glass transition temperature (Tg) of 250° C. or higher and 340° C. or lower, preferably 260 or higher and 320° C. or lower, and more preferably 280 or higher and 310° C. or lower. .
- Tg glass transition temperature
- the glass transition temperature is 250°C or higher, the moisture permeability can be reduced.
- the glass transition temperature is 340° C. or lower, the cured product of the liquid crystal sealant can be made more flexible.
- the sealing agent may contain other curable compounds (C) other than those described above as a curable resin.
- Other curable compounds (C) may be any curable compounds such as photocurable compounds and thermosetting compounds. Examples of other curable compounds (C) include compounds having an ethylenically unsaturated double bond in the molecule (excluding partial epoxy (meth)acrylates).
- curable compounds (C) may be monomers, oligomers or polymers.
- examples of other curable compounds (C) include compounds 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.
- curable compounds containing one (meth)acryloyl group in one molecule include (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate. ) acrylic acid alkyl esters.
- curable compounds having two or more (meth)acryloyl groups in one molecule include di(meth)acrylates and tris(2-hydroxyethyl)isocyanurate derived from polyethylene glycol, propylene glycol, and polypropylene glycol.
- the other curable compound (C) preferably has substantially no unsaturated bonds or siloxane structures in its molecule.
- the content of unsaturated bonds or siloxane structures in the molecule is preferably 5% by mass or less, more preferably 1% by mass or less.
- Partial epoxy (meth)acrylate (D) The sealing agent may contain a partial epoxy (meth)acrylate (D) as a curable resin.
- the partial epoxy (meth)acrylate (D) can enhance the adhesion of the cured sealant to the substrate.
- Partial epoxy (meth)acrylate (D) is a compound having both epoxy and (meth)acryloyl groups in the molecule, and at least one of the epoxy groups possessed by the bifunctional or higher epoxy resin is replaced by (meth) ) is a partially (meth)acryloyl-modified epoxy resin modified with an acryloyl group.
- Partial epoxy (meth)acrylate (D) can be obtained by a known method, for example, a method of reacting a bifunctional or higher functional epoxy resin with (meth)acrylic acid in the presence of a basic catalyst.
- the epoxy resin that is the raw material for the partial epoxy (meth)acrylate (D) may be any epoxy resin that has two or more epoxy groups in the molecule.
- the above epoxy resins include bisphenol type epoxy resins such as bisphenol A type, bisphenol F type, 2,2'-diallyl bisphenol A type, bisphenol AD type, and hydrogenated bisphenol type, phenol novolak type, cresol novolak type, Novolac type epoxy resins such as biphenyl novolac type and trisphenol novolac type, biphenyl type epoxy resins, naphthalene type epoxy resins, and the like are included.
- bisphenol type epoxy resins such as bisphenol A type and bisphenol F type are preferred because they have low crystallinity and high coating stability.
- the epoxy resin may be an epoxy resin having trifunctional, tetrafunctional, or more epoxy groups.
- a bifunctional epoxy resin is preferable from the viewpoint of moderately adjusting the crosslink density to moderately increase the adhesive strength of the cured product to the substrate.
- the ratio of the number of moles of (meth)acryloyl groups to the number of moles of epoxy groups is preferably 1 or more, more preferably 2 or more.
- the partial epoxy (meth)acrylate (D) preferably has a weight average molecular weight (Mw) of 300 or more and 500 or less as measured by gel permeation chromatography (GPC).
- Thermosetting agent (E) The sealant contains a thermosetting compound (A), other curable compounds (C), and a thermosetting agent (E) for curing thermosetting components such as partial epoxy (meth)acrylate (D). It's okay.
- the thermosetting agent (E) is preferably a latent thermosetting agent.
- the latent heat curing agent does not cure the thermosetting compound (A) or other curable compound (C) under normal storage conditions (room temperature, under visible light, etc.), but when heat is applied, these is a compound that cures the compound of
- the thermosetting agent (E) is preferably a curing agent capable of curing an epoxy compound (hereinafter also referred to as "epoxy curing agent").
- the epoxy curing agent preferably has a melting point of 50° C. or higher and 250° C. or lower, and a melting point of 100° C. or higher and 200° C. or higher, from the viewpoint of increasing the viscosity stability of the photothermosetting resin composition and not impairing the moisture resistance of the cured product. ° C. or less is more preferable, and 150° C. or more and 200° C. or less is even more preferable.
- epoxy hardeners examples include dihydrazide thermal latent hardeners, imidazole thermal latent hardeners, dicyandiamide thermal latent hardeners, amine adduct thermal latent hardeners, and polyamine thermal latent hardeners. etc. are included. Among these, dihydrazide-based thermal latent curing agents, imidazole-based thermal latent curing agents, amine adduct-based thermal latent curing agents, and polyamine-based thermal latent curing agents are preferable. Thermal latent curing agents, amine adduct thermal latent curing agents, and polyamine thermal latent curing agents are more preferred, and amine adduct thermal latent curing agents and polyamine thermal latent curing agents are even more preferred.
- dihydrazide thermal latent curing agents examples include dihydrazide adipic acid (melting point 181° C.), 1,3-bis(hydrazinocarboethyl)-5-isopropylhydantoin (melting point 120° C.), 7,11-octadecadiene. -1,18-dicarbohydrazide (melting point 160°C), dodecanedioic acid dihydrazide (melting point 190°C), and sebacic acid dihydrazide (melting point 189°C).
- imidazole thermal latent curing agents examples include 2,4-diamino-6-[2′-ethylimidazolyl-(1′)]-ethyltriazine (melting point 215-225° C.), and 2-phenylimidazole (melting point 137-147°C).
- dicyandiamide-based thermal latent curing agents examples include dicyandiamide (melting point: 209°C).
- the amine adduct-based thermal latent curing agent is a thermal latent curing agent consisting of an addition compound obtained by reacting an amine-based compound with catalytic activity with an arbitrary compound.
- amine adduct-based thermal latent curing agents include Amicure PN-40 (melting point 110°C) manufactured by Ajinomoto Fine-Techno Co., Ltd., Amicure PN-50 (melting point 120°C) manufactured by Ajinomoto Fine-Techno Co., Ltd., Ajinomoto Fine-Techno Co., Ltd.
- Amicure PN-23 (melting point 100°C) manufactured by Ajinomoto Fine-Techno Co., Ltd.
- Amicure PN-31 (melting point 115°C) manufactured by Ajinomoto Fine-Techno Co., Ltd.
- Amicure PN-H (melting point 115°C) manufactured by Ajinomoto Fine-Techno Co., Ltd.
- Amicure manufactured by Ajinomoto Fine-Techno Co., Ltd. MY-24 (melting point 120°C), and Amicure MY-H (melting point 131°C) manufactured by Ajinomoto Fine-Techno Co., Inc. are included.
- a polyamine-based thermal latent curing agent is a thermal latent curing agent having a polymer structure obtained by reacting an amine with an epoxy. ), and ADEKA Hardener EH4357S (softening point 73-83°C) manufactured by ADEKA Corporation.
- Photoinitiator (F) The above sealing agent is used for initiating curing (polymerization) of specific curable compounds (B), other curable compounds (C)), photocurable components such as partial epoxy (meth)acrylates (D), and the like. A photoinitiator (F) may be included.
- the photopolymerization initiator (F) is not particularly limited as long as it is a compound capable of initiating curing (polymerization) of these compounds.
- the photopolymerization initiator (F) may be a radical polymerization initiator, may be a self-cleavage photopolymerization initiator, or may be a hydrogen drawing inorganic photopolymerization initiator.
- self-cleavage photopolymerization initiators include alkylphenone-based compounds, acylphosphine oxide-based compounds, titanocene-based compounds, acetophenone-based compounds, phenylglyoxylate-based compounds, benzoin ether-based compounds, and oxime ester-based compounds. included.
- alkylphenone compounds examples include benzyl dimethyl ketal such as 2,2-dimethoxy-1,2-diphenylethan-1-one (BASF IRGACURE 651), 2-methyl-2-morpholino (4-thio methylphenyl)propan-1-one (BASF IRGACURE 907) and other ⁇ -aminoalkylphenones, and 1-hydroxy-cyclohexyl-phenyl-ketone (BASF IRGACURE 184) and other ⁇ -hydroxyalkylphenones be Examples of the acylphosphine oxide compounds include 2,4,6-trimethylbenzoindiphenylphosphine oxide.
- titanocene compounds examples include bis( ⁇ 5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium and the like. included.
- acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl Propane-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino(4-thiomethylphenyl)propane -1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, and the like.
- Examples of the phenylglyoxylate-based compound include methylphenylglyoxyester and the like.
- examples of the benzoin ether compounds include benzoin, benzoin methyl ether, benzoin isopropyl ether, and the like.
- examples of the oxime ester compounds include 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzoyloxime)] (manufactured by BASF IRGACURE OXE01), and ethanone-1-[9 -ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(0-acetyloxime) (IRGACURE OXE02 manufactured by BASF) and the like.
- Examples of hydrogen abstraction type photopolymerization initiators include benzophenone-based compounds, thioxanthone-based compounds, anthraquinone-based compounds, and benzyl-based compounds.
- Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate-4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenylsulfide, acrylated benzophenone, 3,3′,4,4′-tetra(t-butylperoxycarbonyl)benzophenone, 3,3′-dimethyl-4-methoxybenzophenone, and the like.
- thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, 1-chloro-4-ethoxythioxanthone (Speedcure CPTX manufactured by Lambson Limited), and 2-isopropylxanthone (Lambson Limited).
- Speedcure ITX 4-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone (Speedcure DETX manufactured by Lambson Limited), 2,4-dichlorothioxanthone, and (2-carboxymethoxythioxanthone)-(poly Tetramethylene glycol 250) diester (OMNIPOL TX manufactured by IGM) and the like are included.
- anthraquinone compounds examples include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone, 2-hydroxyanthraquinone (manufactured by Tokyo Chemical Industry Co., Ltd. 2-Hydroxyanthraquinone), 2,6 -Dihydroxyanthraquinone (Anthraflavic Acid manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 2-hydroxymethylanthraquinone (2-(Hydroxymethyl)anthraquinone manufactured by Junsei Chemical Co., Ltd.).
- the absorption wavelength of the photopolymerization initiator (F) is not particularly limited, and for example, it can be a photopolymerization initiator that absorbs light with a wavelength of 360 nm or longer. Among them, it is more preferable to absorb light in the visible light region, more preferably a photopolymerization initiator that absorbs light with a wavelength of 360 nm or more and 780 nm or less, and a photopolymerization initiator that absorbs light with a wavelength of 360 nm or more and 430 nm or less is particularly preferable. preferable.
- oxime ester compounds are preferred.
- the molecular weight of the photopolymerization initiator (F) can be, for example, 200 or more and 5000 or less. When the molecular weight of the photopolymerization initiator (F) is 200 or more, the photopolymerization initiator (F) is less likely to elute into the liquid crystal. On the other hand, when the molecular weight of the photopolymerization initiator (F) is 5000 or less, the compatibility with various curable resins is enhanced, and the curability of the sealant tends to be favorable.
- the molecular weight of the photopolymerization initiator (F) is more preferably 230 or more and 3000 or less, even more preferably 230 or more and 1500 or less.
- the molecular weight of the photopolymerization initiator (F) can be determined as the "relative molecular mass" of the molecular structure of the main peak detected when analyzed by high performance liquid chromatography (HPLC).
- a sample solution is prepared by dissolving the photopolymerization initiator (F) in THF (tetrahydrofuran), and high performance liquid chromatography (HPLC) measurement is performed. Then, the area percentage of the detected peaks (the ratio of the area of each peak to the sum of the areas of all peaks) is obtained, and the presence or absence of the main peak is confirmed.
- the main peak is the peak with the highest intensity (peak with the highest peak height) among all peaks detected at a detection wavelength characteristic of each compound (for example, 400 nm for thioxanthone compounds).
- the relative molecular mass corresponding to the peak apex of the detected main peak can be measured by Liquid Chromatography Mass Spectrometry (LC/MS).
- the sealant may contain an inorganic filler (G).
- the inorganic filler (G) imparts predetermined hardness and linear expansibility to the cured product, and also suppresses permeation of moisture and the like through the interior of the cured product, thereby further reducing the moisture permeability of the cured product.
- inorganic fillers (G) include calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, zirconium silicate, iron oxide, titanium oxide, titanium nitride, aluminum oxide (alumina), zinc oxide, silicon dioxide ( silica), potassium titanate, kaolin, talc, glass beads, sericite-activated clay, bentonite, aluminum nitride, and silicon nitride. Of these, silicon dioxide and talc are preferred.
- the shape of the inorganic filler (G) may be a regular shape such as a spherical shape, a plate shape, or a needle shape, or may be an irregular shape.
- the average primary particle size of the inorganic filler (G) is preferably 1.5 ⁇ m or less.
- the specific surface area of the inorganic filler (G) is preferably 0.5 m 2 /g or more and 20 m 2 /g or less.
- the average primary particle size of the inorganic filler (F) can be measured by the laser diffraction method described in JIS Z8825 (2013).
- the specific surface area of the filler can be measured by the BET method described in JIS Z8830 (2013).
- the sealant includes thermal radical generators, organic fine particles, coupling agents such as silane coupling agents, ion trapping agents, ion exchange agents, leveling agents, pigments, dyes, and sensitizers. , plasticizers and defoamers.
- thermal radical polymerization initiator examples include organic peroxides, azo compounds, benzoins, benzoin ethers, and acetophenones.
- the organic fine particles can reduce the residual stress when the sealant is applied.
- the organic fine particles have an elastic core containing conjugated diene rubber, silicone rubber, etc., and an outer shell made of a polymer such as (meth)acrylate, vinyl monomer, or epoxy monomer that enhances compatibility with other components. and the organic fine particles.
- silane coupling agents examples include vinyltrimethoxysilane, ⁇ -(meth)acryloxypropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, and the like.
- the sealing agent may further contain a spacer or the like for adjusting the gap of the liquid crystal display panel.
- liquid crystal sealant for each disclosure 2-1. First Disclosure 2-1-1. Description of liquid crystal sealant
- the first disclosure in this specification is that the cured product has a low Young's modulus and suppresses the occurrence of roughness when a liquid crystal display panel having a cured liquid crystal sealant is subjected to pressure treatment.
- the present invention relates to a liquid crystal sealant that can
- the sealing agent has a Young's modulus of 0.5 GPa or more and less than 3.0 GPa as measured at 23 ° C. of the cured product, and contains a thermosetting compound (A) having an epoxy group in the molecule and water at 20 ° C. and a thermosetting agent (E) having a solubility of 5 g/100 g or less.
- the Young's modulus is preferably 0.5 GPa or more and 2.0 GPa or less, more preferably 0.5 GPa or more and 1.5 GPa or less, and even more preferably 0.5 GPa or more and 1.0 GPa or less.
- the flexibility of the sealant can be further increased, the drop resistance of the liquid crystal display panel can be increased, and the moisture permeability can be decreased, so that the reliability of the liquid crystal display panel can be increased. .
- the above Young's modulus is a Young's modulus measured by the following method.
- the sealant is applied on the release paper to a thickness of 100 ⁇ m using an applicator. After that, the applied sealant was placed in a nitrogen-purging container and purged with nitrogen for 5 minutes, then irradiated with light of 3000 mJ/cm 2 (light calibrated by a sensor with a wavelength of 365 nm), and further heated at 120° C. for 1 hour. to produce a cured film.
- a sealant having the above Young's modulus can be prepared by various methods. For example, an epoxy resin containing silicone, an epoxy resin having polyethylene glycol or polypropylene glycol, an epoxy resin having a urethane bond, an epoxy resin having a rubber structure, or the like is used as the thermosetting compound (A), and the content ratio is adjusted.
- the above properties can be imparted to the sealant by a method of Alternatively, the above properties can be imparted to the sealant by using a resin having a relatively long alkyl group or using a flexible compound having an aromatic ring in the molecule.
- a sealant having a low Young's modulus of the cured product has the property that the cured product of the sealant is less likely to crack when pressure treatment is performed after curing. Therefore, a sealant having a Young's modulus of a cured product within the above range is useful for applications in which a pressure treatment is applied, such as polishing a substrate after curing to thin a liquid crystal display panel.
- a pressure treatment such as polishing a substrate after curing to thin a liquid crystal display panel.
- a liquid crystal display panel that has been pressurized after curing bright spots (roughness) may occur in the liquid crystal due to the thermosetting agent seeping out from the sealant.
- a liquid crystal display panel that is not pressurized does not have roughness.
- thermosetting agent which has improved mobility when heated, is attracted to moisture in the liquid crystal and seeps into the liquid crystal. It is believed that the exuded thermosetting agent aggregates in the liquid crystal due to pressure treatment or vibration during polishing, resulting in bright spots (roughness).
- thermosetting agent (E) a hydrophobic thermosetting agent that satisfies the condition that the solubility in water at 20° C. is 5 g/100 g or less is used as the thermosetting agent (E).
- the solubility of the thermosetting agent (E) is a value measured as follows. 100 g of water and a predetermined amount of curing agent are placed in a 300 mL beaker and mixed and stirred for 2 hours. Then, the amount of the thermosetting agent (E) added to the water is gradually reduced, and when the addition of the thermosetting agent (E), mixing and stirring, and visual judgment are performed, it is judged to have dissolved for the first time. Let the density
- the liquid crystal sealing agent was heated at 25° C. to 120° C. ( It is preferable that the time required for G′ and G′′ to match when left still in an atmosphere of constant temperature) is 450 seconds or less, more preferably 440 seconds or less, and 430 seconds. Seconds or less is more preferable.
- the point where G′ and G′′ coincide is also called a gelling point, and is the point at which the overall behavior of the composition changes from liquid (G′′ is dominant) to solid (G′ is dominant). be. Then, when the gelling point is exceeded, G' rises sharply and the composition rapidly hardens. For a given composition, the shorter the time it takes to reach the gelling point when heated, the easier the composition is to cure at that heating temperature.
- the hydrophobic thermosetting agent used in the present disclosure suppresses the generation of bright spots (roughness), but has a high affinity with hydrophobic liquid crystal molecules during curing (during heating). Therefore, it tends to leak into the liquid crystal as conventionally known.
- the liquid crystal sealant is intended to be curable at a low temperature in order to increase the selectability of the substrate, the liquid crystal sealant is often cured by heating at a low temperature for a long time. In order to suppress excessive seepage of the thermosetting agent by heating for a long time, it is preferable that the liquid crystal sealing compound can be cured in a short time even at a low temperature.
- a liquid crystal sealant that takes a short time to reach the gelation point can be prepared by various methods.
- the heat curing agent (E) selected below, the use of a polyfunctional epoxy resin, the addition of a thermal radical generator, etc. can be used to reduce the time required to reach the gelling point. It can be shortened to the above range.
- the sealant has a moisture permeability of less than 50 g/m 2 in an environment of 60° C. and 90% Rh when cured to a thickness of 0.6 mm.
- the moisture permeability is the moisture permeability measured by the following method.
- the sealant is applied on the release paper with an applicator to a thickness of 300 ⁇ m. After that, the applied sealant was placed in a nitrogen-purging container and purged with nitrogen for 5 minutes, then irradiated with light of 3000 mJ/cm 2 (light calibrated by a sensor with a wavelength of 365 nm), and further heated at 120° C. for 1 hour. to produce a cured film.
- a sealant having the above moisture permeability can be prepared by various methods.
- the above properties can be imparted to the sealant by using a flexible compound having an aromatic ring in the molecule or a compound having a stable rounded structure.
- the sealing agent preferably contains a curable resin, a photopolymerization initiator or thermosetting agent for curing the curable resin, and other substances such as an inorganic filler.
- the viscosity of the sealing agent at 25°C and 2.5 rpm of an E-type viscometer is preferably 200 Pa ⁇ s or more and 450 Pa ⁇ s or less, more preferably 300 Pa ⁇ s or more and 400 Pa ⁇ s or less.
- the sealant can be applied easily by a dispenser.
- a heat curing agent (E) having a solubility in water at 20° C. of 5 g/100 g or less is used as the heat curing agent (E).
- Thermosetting compound (A) having two or more epoxy groups in the molecule, specific curable compound (B), other curable compound (C), partial epoxy (meth)acrylate (D), photopolymerization initiation Agents (F), inorganic fillers (G), and other materials can be widely used.
- the type of resin may be appropriately selected such that the Young's modulus of the cured product measured at 23° C. is 0.5 GPa or more and less than 3.0 GPa.
- the thermosetting compound (A) can adjust various physical properties of the liquid crystal sealant.
- an epoxy resin containing silicone, an epoxy resin having polyethylene glycol or polypropylene glycol, an epoxy resin having a urethane bond, an epoxy resin having a rubber structure, or the like can be used as the thermosetting compound (A).
- the Young's modulus of the cured product can be reduced.
- the content of the thermosetting compound (A) is preferably 3 parts by mass or more and 30 parts by mass or less when the total mass of the curable resin is 100 parts by mass.
- the content of the thermosetting compound (A) is 3 parts by mass or more, the moisture permeability of the cured product can be further reduced, and the display characteristics of the resulting liquid crystal panel can be improved.
- the content of the thermosetting compound (A) is 30 parts by mass or less, the flexibility of the cured product can be sufficiently increased (the Young's modulus can be sufficiently decreased), and drop resistance can be increased.
- the content of the thermosetting compound (A) is preferably 10 parts by mass or more and 30 parts by mass or less, more preferably 10 parts by mass or more and 25 parts by mass or less.
- the specific curable compound (B) makes the cured product of the liquid crystal sealant easier to expand and contract.
- cracking of the cured sealant can be easily suppressed when the liquid crystal display panel containing the cured sealant is subjected to pressure treatment.
- the curable compound represented by the general formula (2) is used as the specific curable compound (B)
- the effect of making the cured product easier to stretch is remarkable.
- the content of the specific curable compound (B) is preferably 40 parts by mass or more and 90 parts by mass or less when the total mass of the curable resin is 100 parts by mass.
- the content of the specific curable compound (B) is 40 parts by mass or more, the flexibility is sufficiently increased (the Young's modulus is sufficiently lowered), and the liquid crystal panel is resistant to impact such as dropping. It is possible to further increase resistance and to further suppress cracking of the cured product of the sealant when the liquid crystal display panel is subjected to pressure treatment.
- the content of the specific curable compound (B) is 90 parts by mass or less, the humidity resistance of the cured product can be further enhanced, and the display characteristics of the liquid crystal panel can be further enhanced.
- the content of the specific curable compound (B) is preferably 50 parts by mass or more and 80 parts by mass or less.
- the other curable compound (C) can be used, for example, to impart photocurability to the liquid crystal sealant using a photocurable compound.
- Various physical properties of the liquid crystal sealant can also be adjusted by selecting other curable compounds (C).
- the content of the other curable compound (C) is preferably an amount that is 0 parts by mass or more and less than 50 parts by mass when the total mass of the curable resin is 100 parts by mass, and 5 parts by mass or more and 40 parts by mass. It is more preferable that the amount is equal to or less than parts by mass.
- the content of the curable compound containing one (meth)acryloyl group in one molecule is 10 parts by mass when the total mass of the curable resin is 100 parts by mass.
- the amount is preferably less than 5 parts by mass, more preferably 5 parts by mass or less, further preferably 1 part by mass or less, and 0.1 parts by mass or less. is particularly preferred.
- the lower limit of the content of the curable compound containing one (meth)acryloyl group in one molecule can be 0 parts by mass.
- the partial epoxy (meth)acrylate (D) can increase the adhesion of the cured sealant to the substrate.
- the partial epoxy (meth)acrylate (D) can improve the adhesiveness of the cured product, but it is difficult to improve the flexibility of the cured product. Therefore, from the viewpoint of increasing the flexibility of the cured product, the content of the partial epoxy (meth)acrylate (D) is preferably as low as possible. From the above viewpoint, the content of the partial epoxy (meth)acrylate (D) is preferably less than 10 parts by mass when the total mass of the curable resin is 100 parts by mass, and is 5 parts by mass or less. The amount is more preferably 1 part by mass or less, and particularly preferably 0.1 part by mass or less. The lower limit of the content of the partial epoxy (meth)acrylate (D) may be 0 parts by mass.
- the thermosetting agent (E) is a hydrophilic thermosetting agent whose solubility in water at 20°C is 5 g/100 g or less.
- solubility of the thermosetting agent (E) is 5 g/100 g or less, it is possible to suppress the attraction of the thermosetting agent due to moisture in the liquid crystal during heat curing, thereby suppressing the generation of bright spots (roughness).
- the solubility is more preferably 3 g/100 g or less, and even more preferably less than 1 g/100 g.
- the lower limit of the solubility is not particularly limited, it can be 3 g/100 g or more.
- the hydrophilic heat curing agent (E) is preferably an imidazole heat latent curing agent, an amine adduct heat latent curing agent, or a polyamine heat latent curing agent. It is believed that these thermosetting agents are less likely to ooze out into the liquid crystal and can more effectively suppress the occurrence of bright spots (roughness). From the viewpoint of more effectively suppressing the generation of bright spots (roughness), the hydrophilic heat curing agent (E) is preferably a polyamine-based heat latent curing agent.
- the hydrophilic thermosetting agent (E) preferably has a melting point of 50° C. or higher and 250° C. or lower from the viewpoint of increasing the viscosity stability of the thermosetting resin composition and not impairing the moisture resistance of the cured product.
- the melting point is more preferably 70° C. or higher and 150° C. or lower, and more preferably 80° C. or higher and 120° C. or lower.
- imidazole-based thermal latent curing agents examples include 2-phenylimidazole (melting point 137-147°C).
- examples of commercially available imidazole-based thermal latent curing agents include 2P4MHZ-PW manufactured by Shikoku Kasei Kogyo Co., Ltd. and the like.
- the amine adduct-based thermal latent curing agent is a thermal latent curing agent consisting of an addition compound obtained by reacting an amine-based compound with catalytic activity with an arbitrary compound.
- amine adduct-based thermal latent curing agents include Amicure PN-40 (melting point 110°C) manufactured by Ajinomoto Fine-Techno Co., Ltd., Amicure PN-50 (melting point 120°C) manufactured by Ajinomoto Fine-Techno Co., Ltd., Ajinomoto Fine-Techno Co., Ltd.
- Amicure PN-23 (melting point 100°C) manufactured by Ajinomoto Fine-Techno Co., Ltd.
- Amicure PN-31 (melting point 115°C) manufactured by Ajinomoto Fine-Techno Co., Ltd.
- Amicure PN-H (melting point 115°C) manufactured by Ajinomoto Fine-Techno Co., Ltd.
- Amicure manufactured by Ajinomoto Fine-Techno Co., Ltd. MY-24 (melting point 120°C), and Amicure MY-H (melting point 131°C) manufactured by Ajinomoto Fine-Techno Co., Inc. are included.
- a polyamine-based thermal latent curing agent is a thermal latent curing agent having a polymer structure obtained by reacting an amine with an epoxy. ), and ADEKA Hardener EH4357S (softening point 73-83°C) manufactured by ADEKA Corporation.
- the content of the hydrophilic thermosetting agent (E) is preferably 10 parts by mass or more and 200 parts by mass or less when the total mass of the thermosetting compound (A) is 100 parts by mass. More preferably, the amount is 50 parts by mass or more and 160 parts by mass or less, and more preferably 70 parts by mass or more and 120 parts by mass or less.
- the content of the thermosetting agent (E) is 10 parts by mass or more, the curability of the thermosetting compound (A) is likely to be enhanced.
- the content of the hydrophilic thermosetting agent (E) is 200 parts by mass or less, the generation of bright spots (roughness) due to the hydrophilic thermosetting agent (E) exuding into the liquid crystal is further suppressed. It's easy to do.
- Photopolymerization initiator (F) is a specific curable compound (B), other curable compounds (C)), partial epoxy (meth) acrylate (D) such as photocurable components such as curing (polymerization) can be started.
- the content of the photopolymerization initiator (F) is the total amount of photocurable compounds (for example, the partial epoxy (meth)acrylate (D) described above, the specific curable compound (B) and other curable compounds (C)).
- the content of the photopolymerization initiator (F) is preferably 0.01 part by mass or more and 10 parts by mass or less when the mass is 100 parts by mass. When the content of the photopolymerization initiator (F) is 10 parts by mass or less, the contamination of the liquid crystal due to the photopolymerization initiator (F) eluting into the liquid crystal is further suppressed.
- the content of the photopolymerization initiator (F) is more preferably 0.1 parts by mass or more and 5 parts by mass or less, further preferably 0.1 parts by mass or more and 3 parts by mass or less, It is particularly preferable that the amount is 0.1 parts by mass or more and 2.5 parts by mass or less.
- the inorganic filler (G) imparts predetermined hardness and linear expansibility to the cured product, and also suppresses the permeation of moisture and the like through the inside of the cured product, further reducing the moisture permeability of the cured product.
- the content of the inorganic filler (G) is preferably 10 parts by mass or more and 60 parts by mass or less when the total mass of the curable resin is 100 parts by mass, and is 20 parts by mass or more and 55 parts by mass.
- the amount is more preferably 20 parts by mass or more and 50 parts by mass or less, and particularly preferably 20 parts by mass or more and 30 parts by mass or less.
- the content of the inorganic filler (G) is preferably within the above range.
- the liquid crystal sealing agent in the present disclosure includes the above-described thermal radical generators, organic fine particles, coupling agents such as silane coupling agents, ion trapping agents, ion exchange agents, leveling agents, pigments, dyes, sensitizers, plasticizers and Antifoaming agents and the like may also be included.
- coupling agents such as silane coupling agents, ion trapping agents, ion exchange agents, leveling agents, pigments, dyes, sensitizers, plasticizers and Antifoaming agents and the like may also be included.
- the content of the thermal radical polymerization initiator is preferably 0.01 parts by weight or more and 5.0 parts by weight or less when the total weight of the sealing agent is 100 parts by weight.
- the content of the thermal radical polymerization initiator is preferably 0.01 parts by mass or more and 5.0 parts by weight or less when the total weight of the sealing agent is 100 parts by weight.
- the content of the organic fine particles is preferably 5 parts by mass or more and 17 parts by mass or less when the total mass of the sealant is 100 parts by weight.
- the content of the organic fine particles is 5 parts by mass or more, the adhesive strength between the cured product and the substrate can be further increased.
- the content of the organic fine particles is 17 parts by mass or less, the amount of other components (for example, a curable resin) is sufficiently increased, and the strength of the cured product can be further increased.
- the content of the silane coupling agent is preferably 0.01 parts by mass or more and 5 parts by mass or less when the total mass of the sealing agent is 100 parts by weight.
- the adhesive strength between the cured product and the substrate can be further increased.
- the total amount of the above-mentioned other components is preferably 0.1 parts by mass or more and 50 parts by mass or less when the total mass of the sealant is 100 parts by mass.
- the viscosity of the sealant is less likely to increase excessively, and the coating stability of the sealant is less likely to be impaired.
- the Young's modulus of the cured product measured at 23° C. is 0.5 GPa or more and less than 3.0 GPa, a thermosetting compound (A) having an epoxy group in the molecule; and a thermosetting agent (E), wherein the thermosetting agent (E) is a thermosetting agent having a solubility in water at 20° C. of 5 g/100 g or less. Liquid crystal sealant.
- the heat curing agent (E) is at least one heat curing agent selected from the group consisting of imidazole heat latent curing agents, amine adduct heat latent curing agents, and polyamine heat latent curing agents. be, The liquid crystal sealant according to [1].
- Second Disclosure 2-2-1 Problems Related to Second Disclosure
- the sealant is required to be more flexible so that it can be bent with a smaller curvature.
- increasing the flexibility (elongation rate) of the sealant after curing increases the moisture permeability, which may reduce the long-term reliability of the liquid crystal.
- the second disclosure of the present specification has been made in view of the above problems, and includes a liquid crystal sealing agent whose cured product has high flexibility and low moisture permeability, and a method for manufacturing a liquid crystal display panel using the liquid crystal sealing agent. and a liquid crystal display panel manufactured using the liquid crystal sealant.
- the second disclosure in this specification relates to a liquid crystal sealant in which the cured product has high flexibility and low moisture permeability.
- the cured product of the sealing agent has an elongation of 30% or more when measured at 23°C, and a cured product having a thickness of 0.6 mm has a moisture permeability of 50 g/m in an environment of 60°C and 90 Rh. less than 2 .
- the above elongation rate is an elongation rate measured by the following method.
- the sealant is applied on the release paper to a thickness of 100 ⁇ m using an applicator. After that, the applied sealant was placed in a nitrogen-purging container and purged with nitrogen for 5 minutes, then irradiated with light of 3000 mJ/cm 2 (light calibrated by a sensor with a wavelength of 365 nm), and further heated at 120° C. for 1 hour. to produce a cured film.
- the moisture permeability is the elongation rate measured by the following method.
- the sealant is applied on the release paper with an applicator to a thickness of 300 ⁇ m. After that, the applied sealant was placed in a nitrogen-purging container and purged with nitrogen for 5 minutes, then irradiated with light of 3000 mJ/cm 2 (light calibrated by a sensor with a wavelength of 365 nm), and further heated at 120° C. for 1 hour. to produce a cured film.
- a sealant having the above properties can be prepared by various methods.
- the above properties can be imparted to the sealant by using a flexible compound having an aromatic ring in the molecule or by using the specific curable compound (B) described above.
- the liquid crystal sealant related to the second disclosure includes the thermosetting compound (A) having two or more epoxy groups in the molecule described above, and the specific curable compound (B). , Other curable compounds (C), partial epoxy (meth)acrylates (D), thermal curing agents (E), photoinitiators (F), inorganic fillers (G), and other materials widely used be able to.
- the elongation of the cured product measured at 23 ° C. is 30% or more, and the moisture permeability of the cured product with a thickness of 0.6 mm at 60 ° C. and 90 Rh is less than 50 g / m 2 .
- the type of resin may be appropriately selected so that
- thermosetting compound (A) can adjust various physical properties of the liquid crystal sealant.
- the content of the thermosetting compound (A) is preferably 3 parts by mass or more and 30 parts by mass or less when the total mass of the curable resin is 100 parts by mass.
- the content of the thermosetting compound (A) is 3 parts by mass or more, the moisture permeability of the cured product can be further reduced, and the display characteristics of the resulting liquid crystal panel can be improved.
- the content of the thermosetting compound (A) is 30 parts by mass or less, the elongation and flexibility of the cured product can be sufficiently enhanced.
- the content of the thermosetting compound (A) is preferably 10 parts by mass or more and 30 parts by mass or less, more preferably 10 parts by mass or more and 25 parts by mass or less.
- the specific curable compound (B) assumes a curled state and an extended state according to the expansion and contraction of the sealant, thereby making the expansion and contraction of the sealant easier, increasing the elongation of the cured product, and curing it.
- the specific curable compound (B) assumes a curled state and an extended state according to the expansion and contraction of the sealant, thereby making the expansion and contraction of the sealant easier, increasing the elongation of the cured product, and curing it.
- the curable compound represented by the general formula (2) is used as the specific curable compound (B)
- the effect of making the cured product easier to stretch is remarkable.
- the content of the specific curable compound (B) is preferably 40 parts by mass or more and 90 parts by mass or less when the total mass of the curable resin is 100 parts by mass.
- the content of the specific curable compound (B) is 40 parts by mass or more, the elongation and flexibility of the cured product can be sufficiently enhanced.
- the content of the specific curable compound (B) is 90 parts by mass or less, the humidity resistance of the cured product can be further enhanced, and the display characteristics of the liquid crystal panel can be further enhanced. From the above viewpoint, the content of the specific curable compound (B) is more preferably 50 parts by mass or more and 80 parts by mass or less.
- the other curable compound (C) can be used, for example, to impart photocurability to the liquid crystal sealant using a photocurable compound.
- Various physical properties of the liquid crystal sealant can also be adjusted by selecting other curable compounds (C).
- the content of the other curable compound (C) is preferably an amount that is 0 parts by mass or more and less than 50 parts by mass when the total mass of the curable resin is 100 parts by mass, and 5 parts by mass or more and 40 parts by mass. It is more preferable that the amount is equal to or less than parts by mass.
- the content of the curable compound containing one (meth)acryloyl group in one molecule is 10 parts by mass when the total mass of the curable resin is 100 parts by mass.
- the amount is preferably less than 5 parts by mass, more preferably 5 parts by mass or less, further preferably 1 part by mass or less, and 0.1 parts by mass or less. is particularly preferred.
- the lower limit of the content of the curable compound containing one (meth)acryloyl group in one molecule can be 0 parts by mass.
- the partial epoxy (meth)acrylate (D) can increase the adhesion of the cured sealant to the substrate.
- the partial epoxy (meth)acrylate (D) can improve the adhesiveness of the cured product, but it is difficult to improve the flexibility of the cured product. Therefore, from the viewpoint of increasing the flexibility of the cured product, the content of the partial epoxy (meth)acrylate (D) is preferably as low as possible. From the above viewpoint, the content of the partial epoxy (meth)acrylate (D) is preferably less than 10 parts by mass when the total mass of the curable resin is 100 parts by mass, and is 5 parts by mass or less. The amount is more preferably 1 part by mass or less, and particularly preferably 0.1 part by mass or less. The lower limit of the content of the partial epoxy (meth)acrylate (D) may be 0 parts by mass.
- thermosetting agent (E) can cure thermosetting components such as thermosetting compounds (A), other curable compounds (C), and partial epoxy (meth)acrylates (D).
- the content of the thermosetting agent (E) is preferably 3 parts by mass or more and 75 parts by mass or less when the total mass of the thermosetting compound (A) is 100 parts by mass, and is 3 parts by mass or more.
- the amount is more preferably 50 parts by mass or less, and more preferably 5 parts by mass or more and 40 parts by mass or less.
- the content of the thermosetting agent (E) is 3 parts by mass or more, the curability of the thermosetting compound (A) is likely to be enhanced.
- the content of the thermosetting agent (E) is 75 parts by mass or less, contamination of the liquid crystal due to elution of the thermosetting agent (E) into the liquid crystal can be more easily suppressed.
- thermosetting agent (E) when the liquid crystal sealing agent of 25 was heated at 120 ° C. is preferably 450 seconds or less, more preferably 440 seconds or less, and even more preferably 430 seconds or less. Similar to the first disclosure.
- Photopolymerization initiator (F) is a specific curable compound (B), other curable compounds (C)), partial epoxy (meth) acrylate (D) such as photocurable components such as curing (polymerization) can be started.
- the amount of photoinitiator (F) is the total weight of photocurable compounds (e.g., partial epoxy (meth)acrylate (D) described above, specific curable compounds (B) and other curable compounds (C) When is 100 parts by mass, it is preferable that the amount is 0.01 parts by mass or more and 10 parts by mass or less.
- the content of the photopolymerization initiator (F) is 0.01 parts by mass or more
- the content of the photopolymerization initiator (F) is 10 parts by mass or less, contamination of the liquid crystal due to elution of the photopolymerization initiator (F) into the liquid crystal is further suppressed.
- the content of the photopolymerization initiator (F) is more preferably 0.1 parts by mass or more and 5 parts by mass or less, further preferably 0.1 parts by mass or more and 3 parts by mass or less. .1 parts by mass or more and 2.5 parts by mass or less is particularly preferable.
- the inorganic filler (G) imparts predetermined hardness and linear expansibility to the cured product, and also suppresses the permeation of moisture and the like through the inside of the cured product, further reducing the moisture permeability of the cured product.
- the content of the inorganic filler (G) is preferably 30 parts by mass or more and 500 parts by mass or less when the total mass of the curable resin is 100 parts by mass, and is 50 parts by mass or more and 250 parts by mass.
- the amount is more preferably 70 parts by mass or more and 200 parts by mass or less, and particularly preferably 100 parts by mass or more and 200 parts by mass or less.
- the content of the inorganic filler (G) is preferably within the above range.
- the liquid crystal sealing agent in the present disclosure includes the above-described thermal radical generators, organic fine particles, coupling agents such as silane coupling agents, ion trapping agents, ion exchange agents, leveling agents, pigments, dyes, sensitizers, plasticizers and Antifoaming agents and the like may also be included.
- coupling agents such as silane coupling agents, ion trapping agents, ion exchange agents, leveling agents, pigments, dyes, sensitizers, plasticizers and Antifoaming agents and the like may also be included.
- the content of the thermal radical polymerization initiator is preferably 0.01 parts by weight or more and 5.0 parts by weight or less when the total weight of the sealing agent is 100 parts by weight.
- the content of the thermal radical polymerization initiator is preferably 0.01 parts by mass or more and 5.0 parts by weight or less when the total weight of the sealing agent is 100 parts by weight.
- the content of the organic fine particles is preferably 5 parts by mass or more and 17 parts by mass or less when the total mass of the sealant is 100 parts by weight.
- the content of the organic fine particles is 5 parts by mass or more, the adhesive strength between the cured product and the substrate can be further increased.
- the content of the organic fine particles is 17 parts by mass or less, the amount of other components (for example, a curable resin) is sufficiently increased, and the strength of the cured product can be further increased.
- the content of the silane coupling agent is preferably 0.01 parts by mass or more and 5 parts by mass or less when the total mass of the sealing agent is 100 parts by weight.
- the adhesive strength between the cured product and the substrate can be further increased.
- the total amount of other components is preferably 0.1 parts by mass or more and 50 parts by mass or less when the total mass of the sealant is 100 parts by mass.
- the viscosity of the sealant is less likely to increase excessively, and the coating stability of the sealant is less likely to be impaired.
- the elongation of the cured product measured at 23° C. is 30% or more, and A cured product with a thickness of 0.6 mm has a moisture permeability of less than 50 g/m 2 in an environment of 60 ° C. and 90 Rh. Liquid crystal sealant.
- the curable compound (B) having a characteristic ratio of 4.70 or less, a Tg of 250° C. or more and 340° C. or less, and a weight average molecular weight (Mw) of 1000 or more, according to [1] or [2]. liquid crystal sealant.
- thermosetting compound excluding partial epoxy (meth)acrylate) (A) having an epoxy group in the molecule and a thermosetting agent (E), according to any one of [1] to [5].
- thermosetting agent excluding partial epoxy (meth)acrylate
- thermosetting agent E
- the heat curing agent (E) is selected from the group consisting of a dihydrazide heat latent curing agent, an imidazole heat latent curing agent, an amine adduct heat latent curing agent, and a polyamine heat latent curing agent.
- Liquid crystal sealant according to [6] which is at least one thermosetting agent.
- thermosetting compound (A) is a thermosetting compound having a bisphenol F skeleton in its molecule.
- Liquid crystal display panel and manufacturing method thereof includes a pair of substrates (a display substrate and a counter substrate) each having an alignment film, and a frame-shaped substrate disposed between the alignment films of the pair of substrates.
- the present invention relates to a liquid crystal display panel including a sealing member and a liquid crystal layer filled in a space surrounded by the sealing member between a pair of substrates.
- the seal member is a cured product of the sealant (liquid crystal sealant) relating to each of the above disclosures.
- Both the display substrate and the counter substrate are transparent substrates.
- the material of the transparent substrate may be an inorganic material such as glass, or a plastic such as polycarbonate, polyethylene terephthalate, polyethersulfone, or PMMA.
- a matrix TFT, a color filter, a black matrix, etc. may be arranged on the surface of the display substrate or the counter substrate.
- An alignment film is further arranged on the surface of the display substrate or the counter substrate.
- the alignment film includes known organic alignment agents and inorganic alignment agents.
- a liquid crystal display panel is manufactured using the liquid crystal sealant of the present invention.
- Liquid crystal display panels are generally manufactured by 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 dripping method is 1) A step of applying the liquid crystal sealing compound described above to the alignment film of one substrate of a pair of substrates each having an alignment film to form a seal pattern; 2) a step of dropping liquid crystal onto one substrate and within a region surrounded by the seal pattern, or onto the other substrate, while the seal pattern is in an uncured state; 3) a step of superimposing one substrate and the other substrate via a seal pattern; 4) 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 gelation point. Therefore, in step 2), the seal pattern may be semi-cured by light irradiation or heating in order to suppress the dissolution of the liquid crystal sealant into the liquid crystal.
- the one substrate and the other substrate are respectively a display substrate and a counter substrate.
- step 4 curing by light irradiation and subsequent curing by heating may be performed. Since the liquid crystal sealant can be cured in a short time by curing by light irradiation, dissolution into the liquid crystal can be suppressed. By combining curing by light irradiation and curing by heating, damage to the liquid crystal layer due to light can be reduced as compared with curing by light irradiation alone.
- the light to be irradiated is appropriately selected according to the type of the photopolymerization initiator (F) in the sealing agent, but is preferably light in the visible light region, for example, light having a wavelength of 370 nm or more and 450 nm or less. . This is because the light of the above wavelength causes relatively little damage to the liquid crystal material and drive electrodes.
- a known light source that emits ultraviolet light or visible light can be used for light irradiation. When irradiating with visible light, 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 that can cure the specific curable compound (B).
- the photocuring time depends on the composition of the liquid crystal sealant, but is, for example, about 10 minutes.
- the heat curing temperature is, for example, 120° C., and the heat curing time is about 2 hours, although it depends on the composition of the sealant. can be about an hour.
- the pressurizing treatment can be, for example, a treatment of thinning the substrate by polishing.
- the conditions of the pressurizing treatment are not particularly limited, but for example, 5 sets of 7 minutes at a load of 80 N can be used.
- Thermosetting compound (A) having an epoxy group in the molecule Thermosetting compound (A-1): Propylene oxide-modified bisphenol A type epoxy resin (manufactured by ADEKA Corporation, ADEKA RESIN EP-4000S ("ADEKA RESIN” and "ADEKA RESIN EP” are registered trademarks of the company)) - Thermosetting compound (A-2): bisphenol F type epoxy resin (manufactured by ADEKA Corporation, ADEKA RESIN EP-4901 - Thermosetting compound (A-3): rubber-modified (EPR-modified) bisphenol F type epoxy resin (ADEKA Corporation, ADEKA RESIN EPR-4030)
- curable compounds (C) Other curable compounds (C-1): bisphenol A type epoxy acrylate (EBECRYL 3700 manufactured by Daicel Allnex Co., Ltd. ("EBECRYL” is a registered trademark of the company)) Curable compound (C-2): 2-hydroxybutyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., light ester HOB)
- Thermosetting agent 2-2-1 Thermosetting agent (E) - Thermal curing agent (E-1): polyamine-based thermal latent curing agent (manufactured by ADEKA Co., Ltd., EH-4357S (solubility: less than 1g/100g)) - Thermal curing agent (E-2): imidazole-based thermal latent curing agent (manufactured by ADEKA Corporation, EH-4344S (solubility: 1 g/100 g or more and 5 g/100 g or less)) - Thermal curing agent (E-3): Dihydrazide-based thermal latent curing agent (manufactured by Japan Finechem Co., Ltd., dihydrazide adipic acid (ADH) (solubility: 9 g/100 g)) - Thermal curing agent (E-4): dihydrazide-based thermal latent curing agent (manufactured by Japan Finechem Co., Ltd.
- thermosetting agents (E-1) to (E-4) The solubility of the thermosetting agents (E-1) to (E-4) was measured by the method shown below.
- thermosetting agent (E) 100 g of water and a predetermined amount of curing agent were placed in a 300 mL beaker and mixed and stirred for 2 hours. Then, the amount of the thermosetting agent (E) added to the water is gradually reduced, and when the addition of the thermosetting agent (E), mixing and stirring, and visual judgment are performed, it is judged to have dissolved for the first time.
- the concentration of the thermosetting agent (E) obtained was defined as the solubility.
- Photoinitiator (F) ⁇ Photopolymerization initiator (F-1): manufactured by BASF, OXE-02 ⁇ Photopolymerization initiator (F-2): Omnipol-TX manufactured by IGM ("Omnipol” is a registered trademark of the company)
- Inorganic filler (G) Silica particles: SO-C1 manufactured by Admatechs Co., Ltd.
- Thermal radical generator (1) water-soluble azo polymerization initiator (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., V-501)
- Thermal radical generator (2) water-soluble azo polymerization initiator (VA-086, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
- Fine particle polymer polymethacrylate ester-based organic fine particles (Zefiac F351 manufactured by Aica Kogyo Co., Ltd. (“Zefiac” is a registered trademark of Nippon Zeon Co., Ltd.))
- Silane coupling agent Shin-Etsu Chemical Co., Ltd., KBM403
- the epoxy equivalent of the resin component having an epoxy group was determined according to JIS K7236 (2001).
- Tg glass transition temperature
- Table 1 shows the above physical properties.
- sealant 80 parts by mass of thermosetting compound (A-1), 520 parts by mass of curable compound (B-1), 60 parts by mass of other curable compound (C-1), 80 parts by mass of Thermosetting agent (E-1), 5 parts by mass of photopolymerization initiator (F-1), 175 parts by mass of silica particles, 70 parts by mass of fine particle polymer, and 10 parts by mass of silane coupling agent, three A sealant (1) was obtained by sufficiently mixing the mixture with a roll so as to obtain a uniform liquid.
- Sealant (2) to Sealant (14) were obtained in the same manner, except that the types and blending amounts of the materials used were changed as shown in Tables 2 to 4.
- Tables 2 to 4 show the compositions of sealant (1) to sealant (14). In addition, the numerical value described about each component shows a mass part unless there is particular notice.
- the resulting sealant was placed on release paper. was applied in a thickness of 100 ⁇ m using an applicator. After that, the applied sealant was placed in a nitrogen-purging container and purged with nitrogen for 5 minutes, then irradiated with light of 3000 mJ/cm 2 (light calibrated by a sensor with a wavelength of 365 nm), and further heated at 120° C. for 1 hour. Then, a cured film was produced.
- ⁇ Drop characteristics> Using a dispenser (Shotmaster, manufactured by Musashi Engineering), the resulting sealant was applied onto a 140 mm ⁇ 70 mm glass substrate (RT-DM88-PIN, manufactured by EHC) on which a transparent electrode and an alignment film were formed in advance. A square seal pattern of 135 mm ⁇ 65 mm (cross-sectional area of 3500 ⁇ m 2 ) was formed as a seal.
- a liquid crystal material (MLC-6609-000, manufactured by Merck & Co.) corresponding to the content of the panel after bonding was precisely dropped into the frame of the main seal using a dispenser. After that, the paired glass substrates were bonded together under reduced pressure and then exposed to the atmosphere. Then, after holding the two laminated glass substrates in a light-shielding box for 1 minute, only the liquid crystal portion was masked with a substrate coated with a black matrix. 450 nm light) and further heated at 120° C. for 1 hour to cure the main seal and obtain a liquid crystal display panel.
- MLC-6609-000 manufactured by Merck & Co.
- the resulting liquid crystal display panel was dropped from a height of 50 mm, and when there was no liquid crystal leakage due to peeling or cracking of the cell, a drop test was performed by repeatedly dropping the panel at positions raised by 50 mm at a time with the upper limit of 500 mm. After the test, the cells were visually observed, and the drop characteristics were evaluated according to the following criteria. ⁇ Liquid crystal leakage due to peeling or cracking of the cell is not confirmed up to 500 mm ⁇ Liquid crystal leakage is confirmed in the liquid crystal display panel at a height of 300 mm or more and less than 500 mm ⁇ Liquid crystal leakage is confirmed in the liquid crystal display panel at a height of less than 300 mm
- ⁇ Moisture Permeability> The resulting sealant was applied to a release paper in a thickness of 300 ⁇ m using an applicator. After that, the applied sealant was placed in a nitrogen-purging container and purged with nitrogen for 5 minutes, then irradiated with light of 3000 mJ/cm 2 (light calibrated by a sensor with a wavelength of 365 nm), and further heated at 120° C. for 1 hour. Then, a cured film was produced.
- ⁇ Display characteristics (prevention of graininess)> The resulting sealant was applied to a 40 mm ⁇ 45 mm glass substrate (RT-DM88, manufactured by EHC Co., Ltd.) on which a transparent electrode and a hardened layer were formed using a dispenser (Shot Master, manufactured by Musashi Engineering Co., Ltd.).
- RT-DM88 40 mm ⁇ 45 mm glass substrate
- a dispenser Shot Master, manufactured by Musashi Engineering Co., Ltd.
- -PIN a square seal pattern of 35 mm ⁇ 35 mm (cross-sectional area of 3500 ⁇ m 2 ) was formed as a main seal
- a square seal pattern of 38 mm ⁇ 38 mm was formed around the outer circumference.
- an amount of liquid crystal material (MLC-7026-100, manufactured by Merck Co., Ltd.) was precisely dropped into the frame of the main seal using a dispenser in an amount corresponding to the content of the liquid crystal in the liquid crystal display panel to be obtained. It was allowed to stand for 100 minutes or 10 minutes. Then, the glass substrate and the glass substrate forming a pair with the glass substrate were bonded together under a reduced pressure of 4 Pa, and then released to the atmospheric pressure. After holding the two laminated glass substrates in a light-shielding box for 1 minute, the main seal was masked with a square black matrix of 36 mm ⁇ 36 mm with a bare substrate. The glass substrate was irradiated with 1 J/cm 2 .
- the display characteristics of the obtained liquid crystal panel were evaluated according to the following criteria.
- (circle) bright spots (roughness) are observed in the sample left to stand for 100 minutes, but no bright spots (roughness) are found in the sample left to stand for 10 minutes.
- ⁇ Bright spots (roughness) are observed on both the sample left at rest for 100 minutes and the sample left at rest for 10 minutes.
- Tables 2 to 4 show the evaluation results of Young's modulus, drop characteristics, moisture permeability, display characteristics, and applicability of sealant (1) to sealant (14).
- the amount of the thermosetting compound (A) having an epoxy group in the molecule with respect to the total mass of the curable resin (column "(A) amount / total curable resin"), the amount of the curable resin
- the amount of the specific curable compound (B) relative to the total mass (“(B) amount/total curable resin” column)
- the partial epoxy (meth)acrylate relative to the total mass of the curable resin contained in the liquid crystal sealant
- the amount of (D) (column of "amount of (D)/total curable resin") is shown.
- thermosetting compound (A) having a Young's modulus of 0.5 GPa or more and less than 3.0 GPa measured at 23° C. and having an epoxy group in the molecule
- thermosetting agent (E) is a thermosetting agent having a solubility in water at 20° C. of 5 g/100 g or less
- a liquid crystal sealing agent is used to pressurize the liquid crystal panel element. It was possible to suppress the occurrence of bright spots (roughness) when
- sealant 80 parts by mass of thermosetting compound (A-1), 520 parts by mass of curable compound (B-1), 120 parts by mass of other curable compound (C-1), 20 parts by mass of Thermosetting agent (E-5), 5 parts by mass of photopolymerization initiator (F-1), 175 parts by mass of silica particles, 70 parts by mass of fine particle polymer, and 10 parts by mass of silane coupling agent, three A sealant (21) was obtained by sufficiently mixing the mixture with a roll so as to form a uniform liquid.
- Sealant (22) to Sealant (33) were obtained in the same manner, except that the types and blending amounts of the materials used were changed as shown in Tables 5 and 6.
- compositions of the sealing agents (21) to (33) are shown in Tables 5 and 6.
- numerical value described about each component shows a mass part unless there is particular notice.
- ⁇ Elongation rate> The resulting sealant was applied to a release paper with a thickness of 100 ⁇ m using an applicator. After that, the applied sealant was placed in a nitrogen-purging container and purged with nitrogen for 5 minutes, then irradiated with light of 3000 mJ/cm 2 (light calibrated by a sensor with a wavelength of 365 nm), and further heated at 120° C. for 1 hour. Then, a cured film was produced.
- ⁇ Flexibility> The obtained cured film was cut into strips (length 50 mm, width 10 mm), which were then bent along a mandrel having a diameter of 1.0 mm or 1.5 mm and fixed for 10 seconds. The cured film was removed from the mandrel and allowed to rest on a flat table for 1 minute. After that, the state of the cured film was visually observed, and the flexibility was evaluated according to the following criteria. ⁇ No deformation such as cracks or breaks for mandrels with a diameter of 1.0 mm or 1.5 mm. No deformation such as cracks or breaks ⁇ No cracks in the mandrel with a diameter of 1.5 mm but some deformation such as breakage ⁇ A crack occurred in the mandrel with a diameter of 1.5 mm
- ⁇ Moisture Permeability> The resulting sealant was applied to a release paper in a thickness of 300 ⁇ m using an applicator. After that, the applied sealant was placed in a nitrogen-purging container and purged with nitrogen for 5 minutes, then irradiated with light of 3000 mJ/cm 2 (light calibrated by a sensor with a wavelength of 365 nm), and further heated at 120° C. for 1 hour. Then, a cured film was produced.
- Tables 5 and 6 show the evaluation results of the elongation rate, flexibility, moisture permeability, and liquid crystal contamination of the sealing agents (22) to (33).
- the amount of the thermosetting compound (A) having an epoxy group in the molecule with respect to the total mass of the curable resin (column "(A) amount / total curable resin")
- the amount of the curable resin The amount of the specific curable compound (B) relative to the total mass (column "(B) amount/total curable resin")
- the amount of partial epoxy (meth)acrylate (D) relative to the total mass of the curable resin column of "(D) amount/total of curable resin”).
- liquid crystal sealant of the present invention was able to achieve both high flexibility and low moisture permeability.
- the present invention is very useful for application to various liquid crystal display panels.
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Abstract
Description
特許文献1~特許文献5に記載のように、落下などによる衝撃への耐性を高めるため、硬化後の柔軟性を高めた(ヤング率を低下させた)シール剤が種々研究されている。近年、液晶表示パネルをより薄膜化することが要望されており、薄膜化のために、シール剤の硬化後に基板であるガラス板を研磨して薄くすることもある。柔軟性の向上により、液晶表示パネル内部の部材への応力や擦れを低減するため、液晶表示パネルのさらなる薄膜化も可能となると期待されている。
本発明の一実施形態は、液晶表示パネルにおいて液晶を封入するためのシール剤(以下、単に「シール剤」ともいう。)に関する。
まず、本明細書における各開示に関する液晶シール剤に共通して用いられ得る材料について説明する。各開示に記載の液晶シール剤は、それぞれの開示における条件を満たすように、下記材料を適宜選択し、組み合わせて用いることができる。また、これらの材料は、各開示に記載の液晶シール剤に必須の材料ではなく、それぞれの開示における条件を満たす限りにおいて、様々な材料の組み合わせが許容される。
1-1-1―1.分子内にエポキシ基を有する熱硬化性化合物(A)
上記各開示に関する液晶シール剤は、硬化性樹脂として、分子内に2個以上のエポキシ基を有する熱硬化性化合物(A)を含んでもよい。なお、本明細書において、熱硬化性化合物(A)には、後述する部分エポキシ(メタ)アクリレートは含まれない。
上記各開示に関する液晶シール剤は、硬化性樹脂として、特性比が4.70以下、Tgが250℃以上340℃以下、かつ重量平均分子量(Mw)が1,000以上である硬化性樹脂(B)を含んでいてもよい。
ビスフェノールA型エポキシ樹脂、ビスフェノールE型エポキシ樹脂およびビスフェノールF型エポキシ樹脂などのビスフェノール型エポキシ樹脂、
水添ビスフェノール型エポキシ樹脂、
ノボラック型エポキシ樹脂、
ビフェニル型エポキシ樹脂、
スチルベン型エポキシ樹脂、
ハイドロキノン型エポキシ樹脂、
ナフタレン骨格型エポキシ樹脂、
テトラフェニロールエタン型エポキシ樹脂、
トリスヒドロキシフェニルメタン型エポキシ樹脂、
ジシクロペンタジエンフェノール型エポキシ樹脂、
3',4'-エポキシシクロヘキシルメチル-3,4-エポキシシクロヘキサンカルボキシレート、2,2-ビス(ヒドロキシメチル)-1-ブタノールの1,2-エポキシ-4-(2-オキシラニル)シクロヘキサン付加物などの脂環式エポキシ樹脂、
ヘキサヒドロ無水フタル酸のジグリシジルエステルなどの多塩基酸のポリグリシジルエステル、
ソルビトールポリグリシジルエーテル、ソルビタンポリグリシジルエーテル、ペンタエリスリトールポリグリシジルエーテル、トリメチロールプロパンポリグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、ジグリセロールポリグリシジルエーテル、グリセロールポリグリシジルエーテル、ヘキサンジオールジグリシジルエーテル、水添ビスフェノールAジグリシジルエーテルおよびシクロヘキサンジメタノールジグリシジルエーテルなどのグリシジルエーテル、
ポリブタジエンまたはポリイソプレン等のジエンポリマー型エポキシ樹脂、
テトラグリシジルジアミノジフェニルメタン、テトラグリシジルビスアミノメチルシクロヘキサン、ジグリシジルアニリン、テトラグリシジルメタキシリレンジアミンなどのグリシジルアミン型エポキシ樹脂、
トリアジンまたはヒダントインなどの複素環含有エポキシ樹脂、
などが含まれる。
上記シール剤は、硬化性樹脂として、上記以外のその他の硬化性化合物(C)を含んでいてもよい。その他の硬化性化合物(C)は、光硬化性化合物および熱硬化性化合物などのいかなる硬化性化合物であってもよい。その他の硬化性化合物(C)の例には、分子内にエチレン性不飽和二重結合を有する化合物(部分エポキシ(メタ)アクリレートを除く)が含まれる。
上記シール剤は、硬化性樹脂として、部分エポキシ(メタ)アクリレート(D)を含んでもよい。部分エポキシ(メタ)アクリレート(D)は、シール剤の硬化物の、基板への接着性を高めることができる。
上記シール剤は、熱硬化性化合物(A)、その他の硬化性化合物(C)、部分エポキシ(メタ)アクリレート(D)などの熱硬化性成分を硬化させるための熱硬化剤(E)を含んでもよい。
上記シール剤は、特定の硬化性化合物(B)、その他の硬化性化合物(C))、部分エポキシ(メタ)アクリレート(D)などの光硬化性成分などの硬化(重合)を開始させるための光重合開始剤(F)を含んでいてもよい。
上記シール剤は、無機充填材(G)を含んでいてもよい。無機充填材(G)は、硬化物に所定の硬度や線膨張性を付与するほか、硬化物の内部を通しての水分等の透過を抑制し、硬化物の透湿性をより低下させることができる。
上記シール剤は、上述した各成分のほかに、熱ラジカル発生剤、有機微粒子、シランカップリング剤などのカップリング剤、イオントラップ剤、イオン交換剤、レベリング剤、顔料、染料、増感剤、可塑剤および消泡剤などを含んでいてもよい。
2-1.第1の開示
2-1―1.液晶シール剤の説明
本明細書における第1の開示は、硬化物のヤング率が低く、かつ、硬化した液晶シール剤を有する液晶表示パネルに加圧処理を施したときのザラの発生を抑制することができる液晶シール剤に関する。
計算式:
透湿量=(試験後重量-試験前重量)×フィルム厚み/(フィルム面積×100)
第1の開示に関する液晶シール剤には、熱硬化剤(E)として20℃における水への溶解度が5g/100g以下の熱硬化剤を用いるほか、上述した分子内に2個以上のエポキシ基を有する熱硬化性化合物(A)、特定の硬化性化合物(B)、その他の硬化性化合物(C)、部分エポキシ(メタ)アクリレート(D)、光重合開始剤(F)、無機充填材(G)、およびその他の材料を広く使用することができる。その際に、硬化物の23℃で測定したヤング率が0.5GPa以上3.0GPa未満となるように、樹脂の種類を適宜選択する等すればよい。
上述した第1の開示によれば、たとえば以下の液晶シール剤が提供される。
分子内にエポキシ基を有する熱硬化性化合物(A)と、
熱硬化剤(E)と、を含み、 前記熱硬化剤(E)は、20℃における水への溶解度が5g/100g以下の熱硬化剤である、
液晶シール剤。
[1]に記載の液晶シール剤。
(一般式(2)中、R1は多価エポキシ化合物に由来する2価の残基を示し、R2は独立して環状ラクトンを開環させて得られる2価の構造を示し、R3は独立して炭素数1以上6以下の直鎖状または分岐鎖を有するアルキレン基を示し、R4は独立して水素原子またはメチル基を示す。)
前記硬化性樹脂100質量部に対する、前記無機充填剤(G)の含有量は、20質量部以上55質量部以下である、
[1]~[6]のいずれかに記載の液晶シール剤。
2-2-1第2の開示に関する課題
ところで、特許文献1~特許文献5に記載のように、落下などによる衝撃への耐性を高めるため、硬化後の柔軟性を高めたシール剤が種々研究されている。ここで、液晶表示パネルの種類によっては、シール剤にはより小さい曲率の曲げに対応できるように、柔軟性をさらに高めることが要求されている。一方で、本発明者らの新たな知見によると、シール剤の硬化後の柔軟性(伸び率)を高めると、透湿性が高まり、液晶の長期信頼性を低下させることがある。
本明細書における第2の開示は、硬化物が高い柔軟性および低い透湿性を有する液晶シール剤に関する。
計算式:
透湿量=(試験後重量-試験前重量)×フィルム厚み/(フィルム面積×100)
第2の開示に関する液晶シール剤には、上述した分子内に2個以上のエポキシ基を有する熱硬化性化合物(A)、特定の硬化性化合物(B)、その他の硬化性化合物(C)、部分エポキシ(メタ)アクリレート(D)、熱硬化剤(E)、光重合開始剤(F)、無機充填材(G)、およびその他の材料を広く使用することができる。その際に、その硬化物の、23℃で測定した伸び率が30%以上となり、かつ、その厚さ0.6mmの硬化物の60℃、90Rh環境下における透湿量が50g/m2未満となるように、樹脂の種類を適宜選択する等すればよい。
上述した第2の開示によれば、たとえば以下の液晶シール剤が提供される。
厚さ0.6mmの硬化物の60℃、90Rh環境下における透湿量が50g/m2未満である、
液晶シール剤。
前記硬化性樹脂100質量部に対する、部分エポキシ(メタ)アクリレート(A)の含有量が10質量部以下である、[1]に記載の液晶シール剤。
(一般式(1)中、R1は多価エポキシ化合物に由来する2価の残基を示し、R2は独立して環状ラクトンを開環させて得られる2価の構造を示し、R3は独立して炭素数1以上6以下の直鎖状または分岐鎖を有するアルキレン基を示し、R4は独立して水素原子またはメチル基を示す。)
前記硬化性樹脂100質量部に対する、一般式(1)で示される硬化性化合物(B)の含有量が40質量部以上90質量部以下である、[4]に記載の液晶シール剤。
前記硬化性樹脂100質量部に対する、無機充填材(G)の含有量が50質量部以上250質量部以下である、[1]~[8]のいずれかに記載の液晶シール剤。
本発明の他の実施形態は、それぞれ配向膜を有する一対の基板(表示基板および対向基板)と、当該一対の基板の配向膜どうしの間に配置された枠状のシール部材と、一対の基板の間の前記シール部材で囲まれた空間に充填された液晶層と、を含む、液晶表示パネルに関する。上記液晶表示パネルは、上記シール部材が、上述の各開示に関するシール剤(液晶シール剤)の硬化物である。
1)それぞれ配向膜を有する一対の基板の、一方の基板の配向膜上に、上述の液晶シール剤を塗布し、シールパターンを形成する工程と、
2)シールパターンが未硬化の状態において、一方の基板上、かつシールパターンで囲まれた領域内、または他方の基板上に、液晶を滴下する工程と、
3)一方の基板および他方の基板を、シールパターンを介して重ね合わせる工程と、
4)シールパターンを硬化させる工程とを含む。
1.特定の硬化性化合物(B)の合成
<合成例1:硬化性化合物(B-1)>
(BisA型アクリル樹脂)
反応フラスコにヒドロキシエチルアクリレート116g、重合禁止剤としてp-メトキシフェノール0.2g、無水フタル酸148gならびにε-カプロラクトン342gをフラスコ内に仕込み、乾燥空気を送り込んで90℃で還流撹拌しながら6時間反応させた。続いてビスフェノールAジグリシジルエーテル170gを加え、同様に90℃で還流撹拌しながら6時間反応させた。得られた化合物を超純水にて20回洗浄し、硬化性化合物B-1を得た。
(BisA型メタクリル樹脂)
反応フラスコにヒドロキシエチルメタクリレート130g、重合禁止剤としてp-メトキシフェノール0.2g、無水フタル酸148gならびにε-カプロラクトン342gをフラスコ内に仕込み、乾燥空気を送り込んで90℃で還流撹拌しながら6時間反応させた。続いてビスフェノールAジグリシジルエーテル170gを加え、同様に90℃で還流撹拌しながら6時間反応させた。得られた化合物を超純水にて20回洗浄し、硬化性化合物B-2を得た。
(BisF型アクリル樹脂)
反応フラスコにヒドロキシエチルアクリレート116g、重合禁止剤としてp-メトキシフェノール0.2g、無水フタル酸148gならびにε-カプロラクトン342gをフラスコ内に仕込み、乾燥空気を送り込んで90℃で還流撹拌しながら6時間反応させた。続いてビスフェノールFジグリシジルエーテル156gを加え、同様に90℃で還流撹拌しながら6時間反応させた。得られた化合物を超純水にて20回洗浄し、硬化性化合物B-3を得た。
(BisF型メタクリル樹脂)
反応フラスコにヒドロキシエチルメタクリレート130g、重合禁止剤としてp-メトキシフェノール0.2g、無水フタル酸148gならびにε-カプロラクトン342gをフラスコ内に仕込み、乾燥空気を送り込んで90℃で還流撹拌しながら6時間反応させた。続いてビスフェノールFジグリシジルエーテル156gを加え、同様に90℃で還流撹拌しながら6時間反応させた。得られた化合物を超純水にて20回洗浄し、硬化性化合物B-4を得た。
その他の材料として、以下の材料を用いた。
2-1-1.分子内にエポキシ基を有する熱硬化性化合物(A)
・熱硬化性化合物(A-1):プロピレンオキサイド変性ビスフェノールA型エポキシ樹脂(ADEKA株式会社製、アデカレジンEP-4000S(「アデカレジン」および「アデカレジンEP」は同社の登録商標))
・熱硬化性化合物(A-2):ビスフェノールF型エポキシ樹脂(ADEKA株式会社製、アデカレジンEP-4901
・熱硬化性化合物(A-3):ゴム変性(EPR変性)ビスフェノールF型エポキシ樹脂(ADEKA株式会社製、アデカレジンEPR-4030)
・その他の硬化性化合物(C―1):ビスフェノールA型エポキシアクリレート(ダイセル・オルネクス株式会社製、EBECRYL 3700(「EBECRYL」は同社の登録商標))
・硬化性化合物(C-2):2-ヒドロキシブチルメタクリレート(共栄社化学株式会社製、ライトエステルHOB)
・ダイセル・オルネクス株式会社製、KRM8287(「KRM」は同社の登録商標)
2-2-1.熱硬化剤(E)
・熱硬化剤(E-1):ポリアミン系熱潜在性硬化剤(株式会社ADEKA製、EH-4357S(溶解度:1g/100g未満))
・熱硬化剤(E-2):イミダゾール系熱潜在性硬化剤(株式会社ADEKA製、EH-4344S(溶解度:1g/100g以上5g/100g以下))
・熱硬化剤(E-3):ジヒドラジド系熱潜在性硬化剤(株式会社日本ファインケム社製、アジピン酸ジヒドラジド(ADH)(溶解度:9g/100g))
・熱硬化剤(E-4):ジヒドラジド系熱潜在性硬化剤(株式会社日本ファインケム製、マロン酸ジヒドラジド(MDH)(溶解度10g/100g))
・熱硬化剤(E-5):アミンアダクト系熱潜在性硬化剤(味の素ファインテクノ株式会社製、アミキュアPN-50(「アミキュア」は味の素株式会社の登録商標))
・熱硬化剤(E-6):ジヒドラジド系熱潜在性硬化剤(味の素ファインテクノ株式会社製、アミキュアVDH)
(測定方法)
300mLのビーカーに水100gと所定量の硬化剤を入れて2時間混合撹拌させた後、目視で透明になっている状態を溶解と判断した。そして、水への熱硬化剤(E)の添加量を徐々に少なくして、熱硬化剤(E)の添加、混合攪拌および目視での判断を行っていったときの、はじめて溶解と判断された熱硬化剤(E)の濃度を、上記溶解度とした。
・光重合開始剤(F-1):BASF社製、OXE-02
・光重合開始剤(F-2):IGM社製、Omnipol-TX(「Omnipol」は同社の登録商標)
・シリカ粒子:株式会社アドマテックス製、SO-C1
・熱ラジカル発生剤(1):水溶性アゾ重合開始剤(富士フィルム和光純薬株式会社製、V-501)
・熱ラジカル発生剤(2):水溶性アゾ重合開始剤(富士フィルム和光純薬株式会社製、VA-086)
・微粒子ポリマー:ポリメタクリル酸エステル系有機微粒子(アイカ工業株式会社製、ゼフィアックF351(「ゼフィアック」は日本ゼオン株式会社の登録商標))
・シランカップリング剤:信越化学工業株式会社製、KBM403
上述した各樹脂成分の重量平均分子量(Mw)を、ゲルパーミエーションクロマトグラフィー(GPC)によって求めた。
1―1.シール剤の調製
80質量部の熱硬化性化合物(A-1)、520質量部の硬化性化合物(B-1)、60質量部のその他の硬化性化合物(C―1)、80質量部の熱硬化剤(E-1)、5質量部の光重合開始剤(F-1)、175質量部のシリカ粒子、70質量部の微粒子ポリマー、および10質量部のシランカップリング剤を、三本ロールを用いて均一な液になるように十分混合して、シール剤(1)を得た。
上記調製したシール剤(1)~シール剤(14)について、ヤング率、破断伸び率、落下特性、透湿量、表示特性、低温硬化性および塗布性を以下の方法で評価した。
得られたシール剤を、離型紙のうえ。にアプリケーターを用いて100μmの厚みで塗布した。その後、塗布したシール剤を窒素置換用の容器に入れて窒素パージを5分実施したのち、3000mJ/cm2(波長365nmセンサーで校正した光)の光を照射し、さらに120℃で1時間加熱して、硬化フィルムを作製した。
得られたシール剤を、ディスペンサー(ショットマスター、武蔵エンジニアリング製)を用いて、透明電極と配向膜が予め形成された140mm×70mmガラス基板(RT-DM88-PIN、EHC社製)上に、メインシールとして135mm×65mmの四角形のシールパターン(断面積3500μm2)を形成した。
◎ 500mmまでセルに剥がれや割れによる液晶漏れが確認されない
○ 300mm以上500mm未満の高さで液晶表示パネルに液晶漏れが確認された
× 300mm未満の高さで液晶表示パネルに液晶漏れが確認された
得られたシール剤を、離型紙のうえにアプリケーターを用いて300μmの厚みで塗布した。その後、塗布したシール剤を窒素置換用の容器に入れて窒素パージを5分実施したのち、3000mJ/cm2(波長365nmセンサーで校正した光)の光を照射し、さらに120℃で1時間加熱して、硬化フィルムを作製した。
計算式:
透湿量=(試験後重量-試験前重量)×フィルム厚み/(フィルム面積×100)
得られたシール剤を、ディスペンサー(武蔵エンジニアリング株式会社製、ショットマスター)を用いて、透明電極と配硬膜とが形成された40mm×45mmのガラス基板(株式会社イーエッチシー製、RT-DM88-PIN)上に、メインシールとして35mm×35mmの四角形のシールパターン(断面積3500μm2)と、その外周に38mm×38mmの四角形のシールパターンとを形成した。
◎ 100分間静置したものおよび10分間静置したもののいずれにも、輝点(ザラ)が確認されない。
○ 100分間静置したものには輝点(ザラ)が確認されるが、10分間静置したものには輝点(ザラ)が確認されない。
× 100分間静置したものおよび10分間静置したもののいずれにも、輝点(ザラ)が確認される。
動的粘弾性測定装置(レオメータ)により貯蔵弾性率(G’)および損失弾性率(G’’)を測定しながら、25℃のシール剤を120℃(定温)の雰囲気中に静香置して加熱した。このときの、加熱開始からG’とG’’とが一致するまでの時間を測定した。
2-1.シール剤の調製
80質量部の熱硬化性化合物(A-1)、520質量部の硬化性化合物(B-1)、120質量部のその他の硬化性化合物(C-1)、20質量部の熱硬化剤(E-5)、5質量部の光重合開始剤(F-1)、175質量部のシリカ粒子、70質量部の微粒子ポリマー、および10質量部のシランカップリング剤を、三本ロールを用いて均一な液になるように十分混合して、シール剤(21)を得た。
上記調製したシール剤(21)~シール剤(33)について、伸び率、屈曲性、透湿量、および液晶汚染性を以下の方法で評価した。
得られたシール剤を、離型紙のうえにアプリケーターを用いて100μmの厚みで塗布した。その後、塗布したシール剤を窒素置換用の容器に入れて窒素パージを5分実施したのち、3000mJ/cm2(波長365nmセンサーで校正した光)の光を照射し、さらに120℃で1時間加熱して、硬化フィルムを作製した。
得られた硬化フィルムを短冊状(長さ50mm、幅10mm)にカットした後、直径1.0mmあるいは1.5mmの心棒に沿って折り曲げて10秒間固定した。硬化フィルムを心棒から外し、平らな台のうえに1分間静止させた。その後、硬化フィルムの状態を目視で観察し、以下の基準により、屈曲性を評価した。
◎ 直径1.0mmおよび直径1.5mmの心棒に対して割れや折れ等の変形が無い
○ 直径1.0mmの心棒に対して折れ等の変形があるものの、直径1.5mmの心棒に対して割れや折れ等の変形が無い
△ 直径1.5mmの心棒に対して割れはないものの折れ等の変形がある
× 直径1.5mmの心棒に対して割れが発生した
得られたシール剤を、離型紙のうえにアプリケーターを用いて300μmの厚みで塗布した。その後、塗布したシール剤を窒素置換用の容器に入れて窒素パージを5分実施したのち、3000mJ/cm2(波長365nmセンサーで校正した光)の光を照射し、さらに120℃で1時間加熱して、硬化フィルムを作製した。
計算式:
透湿量=(試験後重量-試験前重量)×フィルム厚み/(フィルム面積×100)
0.03gの得られたシール剤と、0.3gの液晶(メルク社製、MLC-7026-100)とを1mlのビーカーに秤量し、120℃で1hr加熱した。加熱により汚染された液晶のネマティック-等方性液体相転移温度(NI点)と加熱前の汚染されていない液晶のNI点と、を比較してその差(ΔNI点)を算出した。なお、液晶汚染性の低い液晶シール剤を用いた場合、ΔNI点の絶対値は小さくなる。
得られたΔNI点をもとに、以下の基準でシール剤を評価した。
〇 ΔNI点が2.0℃以内である
× ΔNI点が2.0℃より大きい
Claims (14)
- 硬化物の、23℃で測定したヤング率が0.5GPa以上3.0GPa未満であり、
分子内にエポキシ基を有する熱硬化性化合物(A)と、
熱硬化剤(E)と、を含み、前記熱硬化剤(E)は、20℃における水への溶解度が5g/100g以下の熱硬化剤である、
液晶シール剤。 - 前記熱硬化剤(E)は、イミダゾール系熱潜在性硬化剤、アミンアダクト系熱潜在性硬化剤、およびポリアミン系熱潜在性硬化剤からなる群より選ばれる少なくとも一種の熱硬化剤である、
請求項1に記載の液晶シール剤。 - 動的粘弾性測定装置(レオメータ)により貯蔵弾性率(G’)および損失弾性率(G’’)を測定しながら、25℃の上記液晶シール剤を120℃で加熱したときの、G’とG’’とが一致するまでの時間が、450秒以下である、請求項1または2に記載の液晶シール剤。
- 特性比が4.7以下、Tgが250℃以上340℃以下、かつ重量平均分子量(Mw)が1000以上である硬化性化合物(B)を含む、請求項1~3のいずれか1項に記載の液晶シール剤。
- 硬化性樹脂100質量部に対する、前記硬化性化合物(B)の含有量が40質量部以上90質量部以下である、請求項4または5に記載の液晶シール剤。
- 硬化性樹脂および無機充填剤(G)を有し、
前記硬化性樹脂100質量部に対する、前記無機充填剤(G)の含有量は、20質量部以上55質量部以下である、
請求項1~6のいずれか1項に記載の液晶シール剤。 - 厚さ0.6mmの硬化物の60℃、90%Rhの環境下における透湿量が50g/m2未満である、請求項1~7のいずれか1項に記載の液晶シール剤。
- 配向膜をそれぞれ有する一対の基板の、一方の基板の前記配向膜上に、請求項1~8のいずれか1項に記載の液晶シール剤を塗布し、シールパターンを形成する工程と、
前記シールパターンが未硬化の状態において、前記一方の基板上かつ前記シールパターンの領域内、または他方の基板に液晶を滴下する工程と、
前記一方の基板および前記他方の基板を、前記シールパターンを介して重ね合わせる工程と、
前記シールパターンを硬化させる工程と、
を含む、
液晶表示パネルの製造方法。 - 前記シールパターンを硬化させる工程において、前記シールパターンに光を照射して前記シールパターンを硬化させる、請求項9に記載の液晶表示パネルの製造方法。
- 前記シールパターンに照射する光は、可視光領域の光を含む、請求項10に記載の液晶表示パネルの製造方法。
- 前記シールパターンを硬化させる工程において、光が照射された後の前記シールパターンをさらに加熱する、請求項10または11に記載の液晶表示パネルの製造方法。
- 前記シールパターンを硬化させる工程の後に、前記基板に加圧処理を施す工程を有する、請求項9~12のいずれか1項に記載の液晶表示パネルの製造方法。
- 配向膜をそれぞれ有する一対の基板と、
前記一対の基板の前記配向膜の間に配置された枠状のシール部材と、
前記一対の基板の間の前記シール部材で囲まれた空間に充填された液晶層と、を含み、
前記シール部材が、請求項1~8のいずれか1項に記載の液晶シール剤の硬化物である、
液晶表示パネル。
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