Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
  • C08L63/10—Epoxy resins modified by unsaturated compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • 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
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
  • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1339—Gaskets; Spacers; Sealing of cells

Definitions

• the present invention relates to a liquid crystal sealant, a method for producing a liquid crystal display panel using the same, and a liquid crystal display panel.
• a liquid crystal display panel has a structure in which a liquid crystal material (hereinafter simply referred to as “liquid crystal”) is sandwiched between two transparent substrates having electrodes provided on the surface, and the periphery thereof is sealed with a liquid crystal sealant.
• liquid crystal a liquid crystal material
• the liquid crystal dropping method includes (1) applying a liquid crystal sealant on a transparent substrate to form a frame, (2) dropping a small amount of liquid crystal in the frame, and (3) superimposing two substrates, (4) A method for producing a panel by curing a liquid crystal sealant.
• a liquid crystal sealant that is cured by light and heat is usually used. For example, after the liquid crystal sealing agent is irradiated with light such as ultraviolet rays and temporarily cured in the step (3), post-curing by heating is performed in the step (4).
• liquid crystal sealant As the liquid crystal sealant, there has been proposed a liquid crystal sealant containing a resin component having both ultraviolet curing properties and thermosetting properties (for example, see Patent Documents 1 and 2).
• a resin component having both ultraviolet curing properties and thermosetting properties for example, see Patent Documents 1 and 2.
• the liquid crystal sealant be a one-component type from the viewpoint of workability.
• curing agent are included in 1 liquid, these will react at the time of a preservation
• the powdery curing agent reacts with the resin composition in a solid liquid. That is, the reaction between the resin composition and the curing agent during storage can be suppressed, and storage stability is improved.
• liquid crystal sealants are required to have storage stability, in recent years, thinning of seal members in liquid crystal panels has been desired. From the viewpoint of thinning the seal member, it is preferable that the liquid crystal sealant does not contain many powder components. When many powder components are contained, the line width at the time of application is affected by the particle size of the powder. If the powder component is included, the viscosity is likely to increase, and it is difficult to apply the liquid crystal sealant in a straight line. Therefore, it is difficult to form a seal member having a thin line width.
• the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a liquid crystal sealant that can form a seal member with a thin line width and is excellent in storage stability.
• the present inventors paid attention to the combination of curing agent components.
• Stable storage stability when selected from solid primary polyamine curing agent, polyhydric phenol curing agent with softening point in the specified range, and secondary polyhydric thiol that is liquid at room temperature. It was found that the property is good. It has also been found that the coating stability is improved because the amount of the powder component can be reduced. The present invention has been made based on such findings.
• the first of the present invention relates to a liquid crystal sealant.
• a liquid crystal sealant comprising (1) a (meth) acryl-modified epoxy resin containing an epoxy group and a (meth) acryl group in the molecule, (2) a curing agent, and (3) a photoinitiator.
• the component (2) is a polyhydric phenol curing agent having a softening point of 50 to 90 ° C., a secondary polyvalent thiol curing agent having a melting point of 23 ° C. or less, and a primary polyvalent amine having a melting point of 60 to 180 ° C.
• a liquid crystal sealing agent comprising two or more kinds of curing agents selected from the group consisting of curing agents and containing 4 to 30 parts by mass of the component (2) with respect to 100 parts by mass of the liquid crystal sealing agent.
• the resin further includes an epoxy resin having two or more epoxy groups in the molecule, and the epoxy resin is selected from the group consisting of a bisphenol type epoxy resin, a biphenyl type epoxy resin, a biphenyl ether type epoxy resin, and a trisphenol type epoxy resin.
• thermoplastic polymer fine particle containing a thermoplastic polymer having a softening point temperature of 50 to 120 ° C. measured by a ring and ball method and having a number average particle diameter of 0.05 to 5 ⁇ m is further included.
• the liquid crystal sealant according to any one of [1] to [5] which contains 1 to 50 parts by mass of a filler with respect to 100 parts by mass of the liquid crystal sealant.
• the liquid crystal sealant according to any one of [1] to [6] which contains 0.1 to 5 parts by mass of an epoxy resin curing catalyst with respect to 100 parts by mass of the liquid crystal sealant.
• the liquid crystal sealant according to any one of [1] to [7] which is used for manufacturing a liquid crystal display panel by a liquid crystal dropping method.
• the second aspect of the present invention relates to a method for manufacturing a liquid crystal display panel.
• a method for producing a liquid crystal display panel comprising a step of photocuring a pattern and then thermally curing the pattern.
• the method for manufacturing a liquid crystal display panel according to [9] wherein the step of forming the seal pattern is a step of forming only the seal pattern without forming a dummy pattern using the liquid crystal sealant.
• the third aspect of the present invention relates to a liquid crystal display panel.
• a display substrate, a counter substrate paired with the display substrate, a frame-shaped sealing member interposed between the display substrate and the counter substrate, and between the display substrate and the counter substrate A liquid crystal layer filled in a space surrounded by the seal member, wherein the seal member is a cured liquid crystal sealant according to any one of [1] to [8] A liquid crystal display panel.
• the liquid crystal sealant of the present invention includes (1) a (meth) acryl-modified epoxy resin containing an epoxy group and a (meth) acryl group in the molecule, (2) a curing agent, and (3) photo initiation. Agent. If necessary, the liquid crystal sealant may further include (1-2) an epoxy resin having two or more epoxy groups in the molecule, (4) (meth) acrylate monomer and / or oligomer, (5) thermoplastic polymer fine particles, (6) A filler, (7) an epoxy resin curing catalyst, and the like may be included.
• the (meth) acryl-modified epoxy resin may be a resin in which the epoxy group of the epoxy resin is modified with a (meth) acryl group.
• it is a (meth) acryl-modified epoxy resin obtained by reacting an epoxy resin and (meth) acrylic acid, for example, in the presence of a basic catalyst.
• the epoxy resin used as a raw material may be a bifunctional or higher functional epoxy resin having two or more epoxy groups in the molecule, for example, bisphenol A type, bisphenol F type, 2,2′-diallyl bisphenol A type, bisphenol AD type.
• Bisphenol type epoxy resins such as hydrogenated bisphenol type; novolak type epoxy resins such as phenol novolak type, cresol novolak type, biphenyl novolak type, and trisphenol novolak type; biphenyl type epoxy resin; naphthalene type epoxy resin .
• the number of functional groups of the epoxy resin used as a raw material is not particularly limited, but the cured product of a (meth) acryl-modified epoxy resin obtained by (meth) acryl modification of a trifunctional or tetrafunctional polyfunctional epoxy resin has a crosslinking density. It is high and the adhesion strength tends to decrease. Therefore, the epoxy resin used as a raw material is preferably a bifunctional epoxy resin.
• bisphenol type epoxy resins such as bisphenol A type and bisphenol F type are particularly preferable.
• the bisphenol type epoxy resin has lower crystallinity than the biphenyl ether type epoxy resin and is excellent in coating stability.
• the epoxy resin used as a raw material is a bifunctional epoxy resin such as a bisphenol A type epoxy resin or a bisphenol F type epoxy resin
• the ratio of the (meth) acrylic group to the epoxy group is 1 or more, preferably 2 or more.
• a (meth) acryl-modified epoxy resin having a low (meth) acryl modification rate and a high epoxy group content tends to be easily dissolved in a liquid crystal.
• a (meth) acryl-modified epoxy resin having an excessively high (meth) acryl modification rate and an epoxy group content that is too low may have low moisture resistance.
• the weight average molecular weight of the (meth) acrylic-modified epoxy resin can be about 300 to about 500.
• the weight average molecular weight of the (meth) acryl-modified epoxy resin is measured by GPC.
• the liquid crystal sealant containing it has both photocuring properties and thermosetting properties.
• the blending amount of the (meth) acryl-modified epoxy resin is preferably 5 to 95 parts by mass and more preferably 10 to 60 parts by mass with respect to 100 parts by mass of the liquid crystal sealant. If it is less than the lower limit, the resin component in the sealing member is small, and the liquid crystal sealability may be insufficient. On the other hand, when the amount is larger than the upper limit, the amount of other components is relatively small, and the curability may be insufficient.
• the liquid crystal sealing agent of the present invention may contain an epoxy resin having two or more epoxy groups in the molecule, if necessary.
• the epoxy resin having two or more epoxy groups in the molecule include at least one kind of 2 selected from the group consisting of a bisphenol type epoxy resin, a biphenyl type epoxy resin, a biphenyl ether type epoxy resin, and a trisphenol type epoxy resin. Functional or trifunctional epoxy resins are included. Only one type of the epoxy resin may be included, or two or more types may be included.
• the above epoxy resin preferably has a softening point of 40 ° C or higher and 150 ° C or lower.
• Such a solid epoxy resin has low solubility and diffusibility in the liquid crystal, and the display characteristics of the obtained liquid crystal panel are good. Furthermore, the moisture resistance of the sealing member obtained by curing the liquid crystal sealing agent is increased.
• the weight average molecular weight of the epoxy resin is 1000 to 10,000, preferably 500 to 5,000. Among these, an aromatic epoxy resin having the above weight average molecular weight is preferable. The weight average molecular weight of the epoxy resin is measured in the same manner as described above.
• aromatic epoxy resin examples include aromatic diols represented by bisphenol A, bisphenol S, bisphenol F, bisphenol AD, and the like; and diols obtained by modifying them with ethylene glycol, propylene glycol, alkylene glycol, and epichlorohydrin.
• the above aromatic epoxy resins include, among others, cresol novolac type epoxy resins, phenol novolac type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, triphenolmethane type epoxy resins, triphenolethane type epoxy resins, trisphenol type epoxy resins.
• Resin, dicyclopentadiene type epoxy resin, diphenyl ether type epoxy resin, and biphenyl type epoxy resin are preferable. One of these may be included, or two or more may be included.
• the compounding amount of the epoxy resin having two or more epoxy groups in the molecule is preferably 1 to 30 parts by mass, and more preferably 3 to 20 parts by mass with respect to 100 parts by mass of the liquid crystal sealant.
• the curing agent is a polyhydric phenol curing agent having a softening point of 50 to 90 ° C., a secondary polyvalent thiol curing agent having a melting point of 23 ° C. or less, and a primary polyvalent amine having a melting point of 60 to 180 ° C. Two or more are selected from the group consisting of curing agents.
• curing agents include the polyhydric phenol curing agent and the secondary polyvalent thiol curing agent; the polyhydric phenol curing agent and the primary polyvalent amine curing agent; and the secondary polyvalent thiol curing agent.
• the primary polyvalent amine curing agent; the polyhydric phenol curing agent, the secondary polyvalent thiol curing agent, and the primary polyvalent amine curing agent may contain a curing agent other than these as long as the effects and objects of the present invention are not impaired.
• the secondary polythiol curing agent is liquid at room temperature, and the polyhydric phenol curing agent can be dissolved in other components contained in the liquid crystal sealant. Therefore, when the polyhydric phenol curing agent and the secondary polyvalent thiol curing agent are combined, the liquid crystal sealant does not contain a powder curing agent, and the amount of the powder component can be greatly reduced. Moreover, since these hardening
• the polyhydric phenol curing agent can be dissolved in other components contained in the liquid crystal sealant. Therefore, when the polyhydric phenol curing agent and the primary polyvalent amine curing agent are combined, the amount of the powder component in the liquid crystal sealant can be reduced as compared with the case where only the primary polyvalent amine curing agent is added. .
• the secondary polyvalent thiol curing agent is also liquid at room temperature, when the secondary polyvalent thiol curing agent and the primary polyvalent amine curing agent are combined, only the primary polyvalent amine curing agent is obtained. Compared with the case where it adds, the amount of powder components can be reduced.
• the amount of the powder component in the liquid crystal sealant is increased for the reasons described above. Can be reduced.
• the total amount of the curing agent in the liquid crystal sealant is 4 to 30 parts by mass, and more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the liquid crystal sealant.
• the viscosity stability may be lowered.
• the resin is not sufficiently cured, and the uncured component may be eluted into the liquid crystal, and the display quality and the adhesive strength may be lowered.
• the polyhydric phenol curing agent used in the present invention is a compound having two or more aromatic hydroxyl groups in one molecule, and its softening point is 50 to 90 ° C., preferably 60 to 80 ° C.
• the softening point is within this range, the liquid crystal sealant softens during thermal curing, and (1) (meth) acryl-modified epoxy resin or (1-2) cures an epoxy resin having two or more epoxy groups in the molecule. Can contribute.
• the softening point is less than the lower limit, the viscosity stability of the liquid crystal sealant may be affected. Moreover, when exceeding an upper limit, the said resin may not fully be hardened
• polyhydric phenol curing agent examples include phenol novolac resin and phenol aralkyl resin.
• the phenol novolac resin may be a condensate obtained by condensing phenol or cresol and formalin.
• the phenol aralkyl resin may be a condensate obtained by condensing phenol or cresol and p-xylene diol in the presence of an acid catalyst or a basic catalyst.
• the curing agent may be a product obtained by purifying the above condensate, or may be a commercially available phenol novolac resin or phenol aralkyl resin. These may be included singly or in combination of two or more.
• the blending amount of the polyhydric phenol curing agent is preferably set based on the adhesive strength of the cured product of the liquid crystal sealant and the photocurability of the liquid crystal sealant.
• the polyvalent thiol curing agent is a compound having two or more secondary thiol groups in one molecule, and its melting point is 23 ° C. or less.
• secondary polyvalent thiol compounds examples include mercaptoesters which are ester-based thiol compounds obtained by esterifying a mercaptocarboxylic acid having a secondary mercapto group and a polyhydric alcohol; , Aromatic polythiols; thiol-modified reactive silicone oils and the like. Among these, only 1 type may be contained and 2 or more types may be contained.
• the secondary polyvalent thiol curing agent is preferably a mercaptoester obtained by an esterification reaction of a mercaptocarboxylic acid having a secondary mercapto group and a polyhydric alcohol.
• mercaptocarboxylic acids having a secondary mercapto group include 2-mercaptopropionic acid, 3-mercapbutanoic acid, 2-mercaptobutanoic acid and the like.
• polyhydric alcohols examples include ethanediol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol, etc. .
• Specific examples of mercaptoesters include pentaerythritol tetrakis (3-mercaptobutyrate) and the like.
• the blending amount of the secondary polyvalent thiol curing agent is preferably set based on the viscosity stability of the liquid crystal sealing agent.
• the primary polyamine curing agent is a compound having two or more primary amino groups (—NH 2 ) in the molecule, and has a melting point of 60 to 180 ° C., preferably 70 to 140 ° C.
• the primary amino group also includes a hydrazinyl group.
• the primary polyvalent amine curing agent is solid when the liquid crystal sealant is stored, and is usually powdery.
• Examples of primary polyvalent amine curing agents include organic acid dihydrazide compounds, amine / urea adducts, dicyandiamides, imidazole derivatives, aromatic amines, epoxy-modified polyamines and polyaminoureas. Among these, only 1 type may be contained and 2 or more types may be contained.
• organic acid dihydrazide compounds include adipic acid dihydrazide (melting point 180 ° C.), 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin (melting point 120 ° C.), 7,11-octadecadien-1, 18-dicarbohydrazide (melting point 160 ° C.) and the like are included.
• amine / urea adducts include curing agents commercially available as the Fujicure FXR series.
• the blending amount of the primary polyvalent amine curing agent is preferably set based on the curing rate of the liquid crystal sealant.
• the number average particle diameter is preferably 0.1 to 5 ⁇ m, more preferably 0.5 to 3 ⁇ m.
• the coating stability of the liquid crystal sealant is improved, and a seal member can be formed with a narrow line width.
• it shall be more than a lower limit it can suppress that a primary polyvalent amine hardening
• the number average particle diameter can be specified with a dry particle size distribution meter.
• the photoinitiator is an initiator for photocuring reaction of (1) (meth) acryl-modified epoxy resin, (4) (meth) acrylate monomer and / or oligomer described later.
• the sealant can be temporarily cured by photocuring when manufacturing a liquid crystal panel, and the work becomes easy.
• the photoinitiator can be a known one.
• photoinitiators include alkylphenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin compounds, acetophenone compounds, benzophenone compounds, thioxanthone compounds, ⁇ -acyloxime esters Compounds, phenylglyoxylate compounds, benzyl compounds, azo compounds, diphenyl sulfide compounds, organic dye compounds, iron-phthalocyanine compounds, benzoin ether compounds, anthraquinone compounds, and the like.
• alkylphenone compounds include benzyl dimethyl ketals such as 2,2-dimethoxy-1,2-diphenylethane-1-one (IRGACURE 651); 2-methyl-2-morpholino (4-thiomethylphenyl) propane ⁇ -aminoalkylphenones such as 1-one (IIRGACURE 907); ⁇ -hydroxyalkylphenones such as 1-hydroxy-cyclohexyl-phenyl-ketone (IRGACURE 184) and the like.
• acylphosphine oxide-based compound include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.
• the titanocene-based compound includes bis ( ⁇ 5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium and the like.
• oxime ester compounds include 1.2-octanedione-1- [4- (phenylthio) -2- (0-benzoyloxime)] (IRGACURE OXE 01).
• the compounding amount of the photoinitiator is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the liquid crystal sealant.
• curability of (1) (meth) acryl-modified epoxy resin and (4) (meth) acrylate monomer and / or oligomer described later is improved.
• coating of a liquid-crystal sealing compound becomes favorable by setting it as below an upper limit.
• the liquid crystal sealant of the present invention may contain a (meth) acrylate monomer and / or oligomer, if necessary.
• the (meth) acrylate monomer and / or oligomer is contained in the liquid crystal sealing agent, the liquid curing of the liquid crystal sealing agent becomes good, and the workability at the time of manufacturing the liquid crystal panel is improved.
• the type of (meth) acrylate monomer and / or oligomer is not particularly limited as long as the object and effect of the present invention are not impaired.
• Examples of the (meth) acrylate monomer and / or oligomer include the following (meth) acrylate monomer or oligomer.
• Diacrylates and / or dimethacrylates such as polyethylene glycol, propylene glycol and polypropylene glycol; diacrylates and / or dimethacrylates of tris (2-hydroxyethyl) isocyanurate; 4 moles or more of ethylene oxide or propylene per mole of neopentyl glycol Diacrylate and / or dimethacrylate of diol obtained by addition of oxide; diacrylate and / or dimethacrylate of diol obtained by addition of 2 mole of ethylene oxide or propylene oxide to 1 mole of bisphenol A; 1 mole of trimethylolpropane Diol or triacrylate of triol obtained by adding 3 mol or more of ethylene oxide or propylene oxide to Or di- or trimethacrylate; diacrylate and / or dimethacrylate of diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of bisphenol A; tris (2-hydroxyethyl) isocyan
• the blending amount of the (meth) acrylate monomer and / or oligomer is preferably 1 to 50 parts by mass, more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the liquid crystal sealant.
• the liquid crystal sealant of the present invention contains a thermoplastic polymer having a softening point temperature measured by a ring and ball method of 50 to 120 ° C., preferably 70 to 100 ° C., if necessary, and Thermoplastic polymer fine particles having a number average particle diameter of 0.05 to 5 ⁇ m, preferably 0.1 to 3 ⁇ m may be included.
• the number average particle diameter is set to the upper limit value or less, it is possible to prevent the coating stability from being lowered by the thermoplastic polymer fine particles when forming a seal member having a narrow line width.
• the method for measuring the number average particle diameter is the same as that described above.
• thermoplastic polymer fine particles include fine particles obtained by suspension polymerization of a resin containing an epoxy group and a double bond group with a monomer capable of radical polymerization.
• the resin containing an epoxy group and a double bond group include a resin obtained by reacting a bisphenol F type epoxy resin and methacrylic acid in the presence of a tertiary amine.
• radically polymerizable monomers include butyl acrylate, glycidyl methacrylate, and divinylbenzene.
• the blending amount of the thermoplastic polymer fine particles is preferably 5 to 40 parts by mass, more preferably 7 to 30 parts by mass with respect to 100 parts by mass of the liquid crystal sealant. By setting it as such a range, the thermoplastic polymer fine particle can relieve the shrinkage stress at the time of heat-hardening of a liquid-crystal sealing compound, and can form a sealing member with the target line width.
• the liquid crystal sealant of the present invention may further contain a filler.
• the filler can control the viscosity of the liquid crystal sealant, the strength of the seal member obtained by curing the liquid crystal sealant, the linear expansion property, and the like.
• the filler is not particularly limited, and examples thereof include calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, zirconium silicate, iron oxide, titanium oxide, aluminum oxide (alumina), zinc oxide, silicon dioxide, Inorganic fillers such as potassium titanate, kaolin, talc, glass beads, sericite activated clay, bentonite, aluminum nitride, silicon nitride are included. Preferred are silicon dioxide and talc.
• the shape of the filler is not particularly limited, and may be a regular shape such as a spherical shape, a plate shape, or a needle shape, or an irregular shape.
• the filler preferably has an average primary particle size of 1.5 ⁇ m or less and a specific surface area of 0.5 m 2 / g to 20 m 2 / g.
• the average primary particle diameter of the filler is measured by a laser diffraction method described in JIS Z8825-1.
• the specific surface area is measured by the BET method described in JIS Z8830.
• the filling amount of the filler is preferably 1 to 50 parts by mass and more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the liquid crystal sealant.
• the upper limit is exceeded, the amount of the powder component in the liquid crystal sealant increases, and the coating stability may be lowered.
• Epoxy resin curing catalyst The liquid crystal sealant of the present invention may contain an epoxy resin curing catalyst, if necessary.
• the epoxy resin curing catalyst is contained in the liquid crystal sealant, the curability of the seal member obtained by curing the liquid crystal sealant is improved, and the adhesive strength of the seal member is also increased.
• the epoxy resin curing catalyst is not particularly limited as long as it does not impair the object and effect of the present invention, and examples thereof include imidazole and derivatives thereof, amines and adducts thereof, and the like.
• the blending amount of the curing catalyst is preferably 0.1 to 5 parts by mass, more preferably 0.5 to 3 parts by mass with respect to 100 parts by mass of the liquid crystal sealant.
• the liquid crystal sealant of the present invention may further include a thermal radical polymerization initiator, a coupling agent such as a silane coupling agent, an ion trapping agent, an ion exchange agent, a leveling agent, and a pigment as necessary. Additives such as dyes, plasticizers and antifoaming agents may be included. In addition, a spacer or the like may be blended to adjust the gap of the liquid crystal panel.
• liquid crystal sealing agent of the present invention contains (1) (meth) acryl-modified epoxy resin, (2) curing agent, and (3) photoinitiator, liquid crystal dripping is often used in combination with photocuring and thermosetting. It is preferably used for a liquid crystal sealant for a construction method.
• the liquid crystal sealing agent for the liquid crystal dropping method preferably further comprises (1-2) an epoxy resin having two or more epoxy groups in the molecule and (4) a (meth) acrylate monomer and / or oligomer, and more preferably ( 5) further includes thermoplastic polymer fine particles, and (6) a filler.
• the viscosity of the liquid crystal sealant of the present invention at 25 ° C. and 2.5 rpm by an E-type viscometer is preferably 30 to 400 Pa ⁇ s, more preferably 50 to 350 Pa ⁇ s.
• a liquid crystal sealant having a viscosity in the above range is excellent in coating stability.
• the liquid crystal sealant of the present invention includes (1) a (meth) acryl-modified epoxy resin containing an epoxy group and a (meth) acryl group in the molecule, (2) a curing agent, (3) A photoinitiator and other components as necessary are uniformly mixed and manufactured.
• the method of uniformly mixing is not particularly limited, but for example, it is preferable to sufficiently knead using three rolls. At that time, it is preferable that the liquid crystal sealant is sufficiently defoamed so that bubbles are not included therein.
• the liquid crystal display panel of the present invention is a display substrate, a counter substrate that is paired with the display substrate, a frame-shaped sealing member interposed between the display substrate and the counter substrate, and a display substrate. And a liquid crystal layer filled in a space surrounded by a seal member between the substrate and the substrate.
• the cured product of the liquid crystal sealant of the present invention can be used as a seal member.
• the display substrate and the counter substrate are both transparent substrates.
• the material of the transparent substrate is not particularly limited, and examples thereof include glass or plastics such as polycarbonate, polyethylene terephthalate, polyethersulfone, and PMMA.
• a matrix-like TFT, a color filter, a black matrix, or the like can be disposed on the surface of the display substrate or the counter substrate.
• An alignment film is further formed on the surface of the display substrate or the counter substrate.
• the alignment film includes a known organic alignment agent or inorganic alignment agent.
• the manufacturing method of the liquid crystal display panel by the liquid crystal dropping method is a1) a first step of forming a seal pattern of the liquid crystal sealant of the present invention on one substrate; a2) a second step of dropping liquid crystal in a region surrounded by the seal pattern of the substrate or a region of the other substrate facing the region surrounded by the seal pattern in a state where the seal pattern is uncured; , a3) a third step of superimposing one substrate and the other substrate via a seal pattern; a4) a fourth step of curing the seal pattern.
• the state in which the seal pattern is uncured means a state in which the curing reaction of the liquid crystal sealant has not progressed to the gel point. Therefore, in the step a2), the seal pattern may be semi-cured by light irradiation or heating in order to suppress dissolution of the liquid crystal sealant in the liquid crystal.
• One substrate and the other substrate are a display substrate or a counter substrate, respectively.
• the liquid crystal sealant of the present invention has a small amount of powder in the curing agent, it is possible to make the seal pattern finer.
• the cross-sectional area of the seal pattern using the liquid crystal sealant of the present invention may be about 1500 to 3000 ⁇ m 2 .
• step a4) only curing by heating may be performed, but it is preferable to perform curing by heating (main curing) after curing by light irradiation (temporary curing).
• main curing main curing
• temporary curing temporary curing
• the photocuring time is, for example, about 10 minutes although it depends on the composition of the liquid crystal sealant.
• the light irradiation energy may be energy that can cure (1) (meth) acryl-modified epoxy resin, (4) (meth) acrylate monomer, and / or oligomer.
• the light is preferably ultraviolet light.
• the thermosetting temperature is 120 ° C., for example, although it depends on the composition of the liquid crystal sealant, and the thermosetting time is about 2 hours.
• the step a3) is often performed under reduced pressure, and the step a4) is often performed at atmospheric pressure.
• the liquid crystal display panel is returned to atmospheric pressure.
• the region surrounded by the two substrates and the liquid crystal sealant is sealed, and a reduced pressure state is maintained. Therefore, in the region surrounded by the liquid crystal sealant, a force acts on the two substrates in the direction in which the substrates are close to each other.
• the atmospheric pressure is released outside the frame of the liquid crystal sealant, no force acts on the two substrates in the direction in which the substrates are close to each other. For this reason, there is a problem that the substrate is bent and the gap becomes wider from the center of the liquid crystal display panel toward the outside of the frame of the liquid crystal sealant. When the gap is uneven in the liquid crystal display panel, the display reliability is lowered.
• a method of providing another frame (dummy seal) outside the frame (main seal) made of a liquid crystal sealant is generally used (for example, Japanese Patent Laid-Open No. 2002-2002). -328382).
• the area outside the main seal that is, the region between the main seal and the dummy seal is also in a reduced pressure state.
• the liquid crystal sealant contains many powder components, the liquid crystal sealant is hard, and it is difficult to deform as described above.
• the liquid crystal sealant of the present invention has a low powder component content and high flexibility of the liquid crystal sealant. Therefore, it is possible to manufacture a liquid crystal display panel by forming only a seal pattern necessary for sealing a liquid crystal without forming a dummy seal pattern.
• the liquid crystal sealant of the present invention can be used not only for the method for producing a liquid crystal surface panel by the liquid crystal dropping method described above but also for the method for producing a liquid crystal display panel by a liquid crystal injection method.
• the manufacturing method of the liquid crystal display panel by the liquid crystal injection method is b1) a first step of forming a seal pattern of the liquid crystal sealant of the present invention on one substrate; b2) a second step of superimposing one substrate and the other substrate via a seal pattern; b3) a third step of thermosetting the seal pattern to obtain a liquid crystal injection cell having an injection port for injecting liquid crystal; b4) a fourth step of injecting the liquid crystal into the liquid crystal injection cell through the injection port; b5) a fifth step of sealing the inlet.
• a liquid crystal injection cell is prepared. First, two transparent substrates (for example, glass plates) are prepared. Then, a seal pattern is formed on one substrate with a liquid crystal sealant. After the other substrate is superimposed on the surface of the substrate where the seal pattern is formed, the seal pattern may be cured. At this time, it is necessary to provide an injection port for injecting liquid crystal in a part of the liquid crystal injection cell, but the injection port may be provided with a part of the opening when drawing the seal pattern. Moreover, after forming the seal pattern, the seal pattern at a desired location may be removed to provide an injection port.
• thermosetting conditions in step b3) are, for example, about 2 to 5 hours at 150 ° C., depending on the composition of the liquid crystal sealant.
• the step b4) can be performed according to a known method in which the inside of the liquid crystal injection cell obtained in the steps b1) to b3) is evacuated and the liquid crystal is sucked from the injection port of the liquid crystal injection cell. Good.
• the liquid crystal sealant may be cured after being sealed in the injection port of the liquid crystal injection cell.
• the liquid crystal sealant of the present invention has good coatability and can form a seal member in a thin pattern.
• the adhesive strength is good, and the viscosity stability during storage is also excellent.
• a liquid crystal display panel having excellent gap stability between substrates can be obtained by forming only a seal pattern necessary for sealing liquid crystal without forming a dummy seal pattern. It is also possible.
• the number of epoxy groups contained in the raw material bisphenol F type epoxy resin is 1 mol.
• the number of methacryl groups contained in the methacrylic acid to be reacted is 0.70 mol. Therefore, the methacrylic acid-modified bisphenol F type epoxy resin obtained is a 70% partially methacrylic product.
• Example 1 50 parts by mass of a methacrylic acid-modified bisphenol F type epoxy resin (70% partially methacrylic product) obtained in Synthesis Example 1, 4 parts by mass of a polyhydric phenol curing agent A (Mitsui Chemicals Co., Ltd .: Millex 3L, softening point 71 ° C.) Parts, secondary polyvalent thiol curing agent B (manufactured by Showa Denko KK: PE-1) 8 parts by mass, primary polyvalent amine curing agent D (manufactured by ADEKA; EH-5057, melting point 80 ° C.) 4 parts by mass, light
• an initiator 1 part by mass of a photo radical polymerization initiator (Ciba Geigy: Irgacure 651), 2 parts by mass of a curing catalyst (Shikoku Kasei Co., Ltd .: 2MAOK), 20 parts by mass of thermoplastic polymer fine particles (G351: F351), and filling
• Example 2 Liquid crystal seal in the same manner as in Example 1 except that 8 parts by mass of the polyhydric phenol curing agent A, 8 parts by mass of the primary polyvalent amine curing agent D, and 0 parts by mass of the secondary polyvalent thiol curing agent. An agent was obtained. Moreover, it was 320 Pa.s when the viscosity (initial viscosity) was measured by the method mentioned later.
• Example 3 Liquid crystal seal in the same manner as in Example 1 except that 8 parts by mass of the polyhydric phenol curing agent A, 8 parts by mass of the secondary polyvalent thiol curing agent B, and 0 parts by mass of the primary polyvalent amine curing agent. An agent was obtained. Moreover, it was 250 Pa.s when the viscosity (initial viscosity) was measured by the method mentioned later.
• Example 4 A liquid crystal sealant was obtained in the same manner as in Example 1 except that 8 parts by mass of the secondary polyvalent thiol curing agent B and 8 parts by mass of the primary polyvalent amine curing agent D were used. Moreover, it was 260 Pa.s when the viscosity (initial viscosity) was measured by the method mentioned later.
• Example 5 The amount of the methacrylic acid-modified bisphenol F-type epoxy resin (70% partially methacrylic product) obtained in Synthesis Example 1 is 40 parts by mass, the amount of the polyhydric phenol curing agent A is 7 parts by mass, and the secondary polyvalent thiol. Except for the amount of curing agent B being 14 parts by mass, the amount of primary polyvalent amine curing agent D being 7 parts by mass, the amount of thermoplastic polymer fine particles being 19 parts by mass, and the amount of filler being 9 parts by mass. A liquid crystal sealant was obtained in the same manner as in Example 1. Further, the viscosity (initial viscosity) measured by the method described later was 210 Pa ⁇ s.
• Example 6 The amount of the methacrylic acid-modified bisphenol F type epoxy resin (70% partially methacrylic product) obtained in Synthesis Example 1 is 56 parts by mass, the amount of polyhydric phenol curing agent A is 1 part by mass, and the secondary polyvalent thiol.
• a liquid crystal sealant was obtained. Moreover, it was 300 Pa.s when the viscosity (initial viscosity) was measured by the method mentioned later.
• Example 7 Instead of polyhydric phenol curing agent A, 4 parts by mass of polyhydric phenol curing agent B (manufactured by DIC: TD2131, softening point 80 ° C.) is used, and the amount of secondary polyhydric thiol curing agent B is 8 parts by mass.
• a liquid crystal sealant was obtained in the same manner as in Example 1 except that the amount of the polyvalent amine curing agent D was 4 parts by mass. Moreover, it was 250 Pa.s when the viscosity (initial viscosity) was measured by the method mentioned later.
• Example 8 Instead of the polyhydric phenol curing agent A, 4 parts by mass of the polyhydric phenol curing agent C (manufactured by Mitsubishi Chemical Corporation: 170 softening point 90 ° C.) is used, and the amount of the secondary polyhydric thiol curing agent B is 8 parts by mass.
• a liquid crystal sealing agent was obtained in the same manner as in Example 1 except that the amount of the polyvalent amine curing agent D was changed to 4 parts by mass. Further, when the viscosity (initial viscosity) was measured by the method described later, it was 255 Pa ⁇ s.
• Example 9 The amount of the phenol curing agent A is 4 parts by mass, the amount of the secondary polyvalent thiol curing agent B is 8 parts by mass, and the polyvalent amine curing agent A (manufactured by Nippon Hydrazine: ADH, melting point) as the primary polyvalent amine curing agent.
• a liquid crystal sealant was obtained in the same manner as in Example 1 except that 4 parts by mass of 180 ° C.) and 4 parts by mass of the polyvalent amine curing agent D were used. Moreover, it was 270 Pa.s when the viscosity (initial viscosity) was measured by the method mentioned later.
• Example 10 The amount of the phenol curing agent A is 4 parts by mass, the amount of the secondary polyvalent thiol curing agent B is 8 parts by mass, and the polyvalent amine curing agent B (manufactured by Fuji Kasei Kogyo: Fujicure FXR- 1020, melting point 125 ° C.) was used in the same manner as in Example 1 except that 4 parts by mass and 4 parts by mass of polyvalent amine curing agent D were used to obtain a liquid crystal sealant. Moreover, it was 260 Pa.s when the viscosity (initial viscosity) was measured by the method mentioned later.
• the viscosity initial viscosity
• Example 11 4 parts by mass of phenol curing agent A, 8 parts by mass of secondary polyvalent thiol curing agent B, polyvalent amine curing agent C as a primary polyvalent amine curing agent (manufactured by Ajinomoto Fine Techno Co .: VDH, melting point)
• a liquid crystal sealant was obtained in the same manner as in Example 1 except that 4 parts by mass of 120 ° C. was used. Moreover, it was 250 Pa.s when the viscosity (initial viscosity) was measured by the method mentioned later.
• Example 1 A liquid crystal sealant was obtained in the same manner as in Example 1 except that 16 parts by mass of the phenol curing agent A as a curing agent and 0 parts by mass of the secondary polyvalent thiol curing agent and the primary polyvalent amine curing agent were obtained. . Moreover, it was 350 Pa.s when the viscosity (initial viscosity) was measured by the method mentioned later.
• Example 2 A liquid crystal sealant was prepared in the same manner as in Example 1 except that 16 parts by mass of the secondary polyvalent thiol curing agent B as the curing agent and 0 parts by mass of the polyhydric phenol curing agent and the primary polyvalent amine curing agent were used. Obtained. Further, the viscosity (initial viscosity) measured by the method described later was 210 Pa ⁇ s.
• Example 3 A liquid crystal sealant was prepared in the same manner as in Example 1 except that the primary polyvalent amine curing agent D was 16 parts by mass and the polyhydric phenol curing agent and the secondary polyvalent thiol curing agent were 0 parts by mass. Obtained. Further, when the viscosity (initial viscosity) was measured by the method described later, it was 370 Pa ⁇ s.
• Example 6 A liquid crystal sealant was obtained in the same manner as in Example 1 except that 8 parts by mass of a primary polyvalent thiol curing agent (manufactured by Sakai Chemical Co., Ltd .: TMMP (trimethylolpropane mercaptopropionic acid)) was used as the polyvalent thiol curing agent. Further, when the viscosity (initial viscosity) was measured by the method described later, it was 260 Pa ⁇ s.
• TMMP trimethylolpropane mercaptopropionic acid
• Example 7 A liquid crystal sealing agent was obtained in the same manner as in Example 1 except that the phenol curing agent D (manufactured by DIC: TD2090, softening point 100 ° C.) was used as the polyhydric phenol curing agent. Moreover, it was 270 Pa.s when the viscosity (initial viscosity) was measured by the method mentioned later.
• the phenol curing agent D manufactured by DIC: TD2090, softening point 100 ° C.
• the discharge pressure was 0.3 MPa
• the cross-sectional area was 3000 ⁇ m 2
• the coating speed was 100 mm / s.
• the shape of the obtained seal pattern was evaluated as follows. 50 frame types with no seal breakage or seal fading: ⁇ (Excellent) 48-49 frame molds with no seal breakage or seal fading: ⁇ (Excellent) Less than 48 frame molds with no seal breakage or seal fading: ⁇ (Inferior)
• the liquid crystal sealant obtained in the above examples and comparative examples was prepared by using a dispenser (shot master: manufactured by Musashi Engineering Co., Ltd.) with a transparent electrode and an alignment film formed in advance.
• a 35 mm ⁇ 40 mm square seal pattern (cross-sectional area 3500 ⁇ m 2 ) (main seal) was formed on a glass substrate (EHC, RT-DM88-PIN).
• a square seal pattern 38 mm ⁇ 43 mm square seal pattern
• a liquid crystal material (MLC-119000-000: manufactured by Merck & Co., Inc.) corresponding to the internal volume of the panel after bonding was precisely dropped into the main seal frame with a dispenser.
• a pair of glass substrates was bonded together under reduced pressure, and then bonded to the atmosphere. Then, the two bonded glass substrates were held in a light shielding box for 3 minutes, then irradiated with 2000 mJ / cm 2 of ultraviolet light, and further heated at 100 ° C. for 1 hour.
• the obtained liquid crystal display panel was stored in a thermostatic bath at 70 ° C. and 95% RH for 500 hours. Color unevenness generated in the liquid crystal around the seal portion before and after storage was visually observed. The case where no color unevenness was confirmed was rated as ⁇ (very excellent); the case where almost no color unevenness was confirmed was evaluated as ⁇ (excellent); the confirmed result as ⁇ ;
• the taken out liquid crystal display panel was driven with an applied voltage of 5 V by a DC power supply device.
• the display characteristics of the liquid crystal display panel were evaluated depending on whether the liquid crystal display function in the vicinity of the liquid crystal sealant functions normally from the beginning of driving. As for the display characteristics, ⁇ (excellent) when the liquid crystal display function can be exhibited normally until sealing, ⁇ (good) when abnormality of the liquid crystal display function is confirmed near 0.1 mm when sealing, ⁇ (slightly inferior) when the liquid crystal display function abnormality is confirmed in the vicinity of 0.1 mm and less than 0.3 mm, and the display function abnormality is confirmed in the vicinity of 0.3 mm when the seal is exceeded.
• X Inferior).
• Adhesive strength In the above 3), the plane tensile strength of the liquid crystal display panel sample after storage in a thermostat was measured at a tensile speed of 2 m / min using a tensile tester (manufactured by Intesco). Adhesiveness was evaluated as follows. Adhesive strength of 20 MPa or more: ⁇ (Excellent) Adhesive strength is 15 MPa or more and less than 20 MPa: ⁇ (excellent) Adhesive strength is 7 MPa or more and less than 15 MPa: ⁇ (slightly inferior) Adhesive strength is less than 7 MPa: x (inferior)
• a polyhydric phenol curing agent having a softening point of 50 to 90 ° C. a secondary polyvalent thiol curing agent having a melting point of 23 ° C. or less, and a primary polyvalent amine curing agent having a melting point of 60 to 180 ° C.
• a polyhydric phenol curing agent having a softening point of 50 to 90 ° C. a secondary polyvalent thiol curing agent having a melting point of 23 ° C. or less
• a primary polyvalent amine curing agent having a melting point of 60 to 180 ° C When two or more kinds of curing agents selected from the group are used, it can be seen that the viscosity stability, seal coatability, adhesive strength, display state, high temperature and high humidity reliability, and gap accuracy are all excellent. examples 1 to 11).
• Example 1 when only the polyhydric phenol curing agent having a softening point of 50 to 90 ° C. is used (Comparative Example 1), the adhesive strength is low, and the display state and the high temperature and high humidity reliability are slightly higher than those of Examples 1 to 11. Ya inferior.
• Comparative Example 2 when only a secondary polyvalent thiol curing agent having a melting point of 23 ° C. or less was used (Comparative Example 2), all of Example 1 were used for viscosity stability, adhesive strength, display state, and high temperature and high humidity reliability. inferior to 11.
• Comparative Example 3 when only a primary polyvalent amine curing agent having a melting point of 60 to 180 ° C. is used (Comparative Example 3), the viscosity stability is low, and the seal coating property and the gap accuracy are lowered.
• a polyhydric phenol curing agent having a softening point of 50 to 90 ° C selected from the group consisting of a polyhydric phenol curing agent having a softening point of 50 to 90 ° C, a secondary polyvalent thiol curing agent having a melting point of 23 ° C or lower, and a primary polyvalent amine curing agent having a melting point of 60 to 180 ° C.
• a polyhydric phenol curing agent having a softening point of 50 to 90 ° C a secondary polyvalent thiol curing agent having a melting point of 23 ° C or lower
• a primary polyvalent amine curing agent having a melting point of 60 to 180 ° C Even when two or more kinds of curing agents are used, when the amount is less than 4 parts by mass with respect to 100 parts by mass of the liquid crystal sealant (Comparative Example 5), the adhesive strength, the display state, In addition, high temperature and high humidity reliability is reduced.
• the liquid crystal sealant of the present invention has few powder components derived from the curing agent, the coating stability can be improved even when the liquid crystal sealant is applied to form a thin seal member. Moreover, since it is excellent in adhesive strength and viscosity stability, a liquid crystal panel excellent in display reliability can be provided. For this reason, the liquid-crystal sealing compound of this invention is suitable for manufacture of a liquid crystal display panel.

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