WO2012011220A1 - Liquid crystal sealing agent and liquid crystal display cell using same - Google Patents
Liquid crystal sealing agent and liquid crystal display cell using same Download PDFInfo
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- WO2012011220A1 WO2012011220A1 PCT/JP2011/003366 JP2011003366W WO2012011220A1 WO 2012011220 A1 WO2012011220 A1 WO 2012011220A1 JP 2011003366 W JP2011003366 W JP 2011003366W WO 2012011220 A1 WO2012011220 A1 WO 2012011220A1
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- WIPO (PCT)
- Prior art keywords
- liquid crystal
- sealing agent
- dropping method
- meth
- mass
- Prior art date
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- LBBRCECFDIEQLT-UHFFFAOYSA-N CC(COc(cc1)c(cccc2)c2c1OC)OC(C=C)=O Chemical compound CC(COc(cc1)c(cccc2)c2c1OC)OC(C=C)=O LBBRCECFDIEQLT-UHFFFAOYSA-N 0.000 description 1
- OJJNKZYYPVTTQD-UHFFFAOYSA-N CCCCOc(cc1)c(cccc2)c2c1OCC(C)OC(C=C)=O Chemical compound CCCCOc(cc1)c(cccc2)c2c1OCC(C)OC(C=C)=O OJJNKZYYPVTTQD-UHFFFAOYSA-N 0.000 description 1
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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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/14—Polymers provided for in subclass C08G
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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
-
- 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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- 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
-
- 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
- G02F2202/00—Materials and properties
- G02F2202/02—Materials and properties organic material
- G02F2202/022—Materials and properties organic material polymeric
- G02F2202/023—Materials and properties organic material polymeric curable
Definitions
- the present invention has good curability even in a light-shielding portion that is a shadow of wiring and is not directly irradiated with ultraviolet rays in a liquid crystal panel, has good curability even with low energy light such as visible light, and extremely
- the present invention relates to a sealing agent for liquid crystal dropping method with low liquid crystal contamination.
- a so-called liquid crystal dropping method with higher mass productivity has been proposed as a method for manufacturing liquid crystal display cells (see Patent Document 1 and Patent Document 2).
- a liquid crystal display cell in which a liquid crystal is sealed is obtained by dropping a liquid crystal inside a weir of a liquid crystal sealing agent formed on one substrate and then bonding the other substrate. It is a manufacturing method.
- the liquid crystal sealant first contacts the liquid crystal in an uncured state, and at that time, the components of the liquid crystal sealant dissolve in the liquid crystal, lowering the specific resistance of the liquid crystal, and displaying near the seal There is a problem that defects occur.
- thermosetting method three methods of a thermosetting method, a photocuring method, and a photothermal curing combined method are considered as methods for curing the liquid crystal sealant after the substrates are bonded together.
- thermosetting method there is a problem that the liquid crystal leaks from the liquid crystal sealant in the middle of curing, which has been reduced in viscosity due to expansion of the liquid crystal due to heating, and a problem that the components of the liquid crystal sealant whose viscosity has been reduced dissolves in the liquid crystal.
- the liquid crystal sealant used in the photocuring method there are two types of cationic polymerization type and radical polymerization type depending on the type of photopolymerization initiator.
- the cationic polymerization type liquid crystal sealing agent see Patent Document 3
- ions are generated during photocuring, so when this is used in a liquid crystal dropping method, the ionic component is eluted in the liquid crystal in the contact state, and the liquid crystal There is a problem of lowering the specific resistance.
- the radical polymerization type liquid crystal sealant (see Patent Document 4) has a problem that the adhesive strength is not sufficient because of the large shrinkage during photocuring.
- thermosetting method and the photocuring method have various problems, and the photothermal curing combined method as shown in Patent Document 5 is considered to be the most practical construction method.
- the photothermal curing combined method is characterized in that the liquid crystal sealant sandwiched between the substrates is irradiated with light to be primarily cured and then heated to be secondarily cured.
- a sealant contains a photoreactive resin, a photoinitiator, a thermosetting resin, and a thermosetting agent.
- the photoreactive resin can be cured with the thermosetting agent.
- thermosetting agent when an epoxy acrylate is used as a photoreactive resin and an organic acid hydrazide is used as a thermosetting agent, the photoreactive resin by Michael addition reaction can be thermoset.
- the photoreactive resin of the light-shielding part that becomes uncured during photocuring can be cured during thermosetting.
- the amount of the thermosetting agent added becomes a problem. That is, when an amount of a thermosetting agent sufficient to cure the thermosetting resin is added in accordance with the exposed portion, the light-shielding portion lacks the thermosetting agent and is insufficiently cured.
- thermosetting agent becomes excessive in the exposed portion, and remains unreacted, resulting in deterioration of the properties of the cured product. Therefore, it cannot be said that the method of curing the uncured photoreactive resin in the light-shielding portion together at the time of heat curing is not so good.
- the liquid crystal seal portion is irradiated with light, and then the liquid crystal display cell is manufactured by heat curing.
- the liquid crystal sealant used in the liquid crystal dripping method has extremely low contamination to the liquid crystal throughout the process, has excellent workability for application to the substrate, bonding properties, and adhesive strength, and has a light-shielding part curability. This is a liquid crystal sealant that can be applied to liquid crystal panels of any design because it is very excellent.
- the present invention provides a liquid crystal sealant having a good curability in a liquid crystal panel which is a shadow of wiring, etc., and is not directly irradiated with ultraviolet rays, and a liquid crystal display cell using the same. To do.
- the present inventors have found that by using a photosensitizer having an acrylic group in the molecule, the reactivity by light can be remarkably improved and the liquid crystal contamination can be suppressed.
- the present invention has been completed. That is, the present invention relates to the following (1) to (17).
- a liquid crystal sealing agent for a liquid crystal dropping method comprising a photosensitizer having (a) (meth) acrylic group in the molecule and (b) a curable resin having (meth) acrylic group.
- the photosensitizer having a (meth) acryl group in the molecule is a reaction product of thioxanthonecarboxylic acid and a glycidyl (meth) acrylate compound or 4-C1-C4 alkoxy-1- (2-
- the liquid crystal sealing agent for a liquid crystal dropping method according to the above (1) which is (meth) acryloxy-2-R 1 -ethoxy) naphthalene (R 1 represents a hydrogen atom or a C1-C2 alkyl group).
- the curable resin (b) is an epoxy (meth) acrylate.
- the liquid crystal sealant of the present invention has little liquid crystal contamination and has good curability even with low energy light such as visible light. Therefore, it has sufficient curability even under the wiring where direct light is difficult to reach, and the light-shielding portion that is not directly irradiated with ultraviolet rays can be cured with a wide width, and even when it is shaded by the wiring, it can be cured uniformly. For this reason, it is possible to secure the degree of freedom of the wiring design of the panel and the degree of freedom of the process of irradiation with visible light, and the manufacture of a highly reliable liquid crystal display panel can be facilitated.
- FIG. 1 is a view of a sample for light-shielding part curing test
- each of 1-1 to 1-3 is a view of the state of the test sample before curing (1-1)
- Fig. 1-2 shows a side view of a test sample in a state where the sealant is cured by irradiating more ultraviolet rays, and shows the curing state of the liquid crystal sealant after curing the liquid crystal sealant by irradiating with ultraviolet rays. It is a figure (1-3).
- FIG. 1-1 Light-shielding part curing test sample before curing sealant as viewed from above FIG. 1
- Light-shielding part Fig. 1 Black sample substrate 2 Chromium plating etched substrate 3 Chrome plating layer 4 on etched substrate 4
- Liquid crystal sealant Fig. 5 shows the curing state of the liquid crystal sealant of the sample for the light-shielding part curing test after curing of the UV ultraviolet ray.
- Figure 5 Cured part of the liquid-crystal sealing agent 6 Uncured part of the liquid-crystal sealing agent 7 , Hardened part of liquid crystal sealant
- any photosensitizer (a) having a (meth) acryl group in the molecule used in the present invention may be used as long as it has a (meth) acryl group and acts as a photosensitizer (a). I can do it.
- the photosensitizer (a) is usually used in combination with a photopolymerization initiator (d) described later.
- the liquid crystal sealant of the present invention may be a liquid crystal sealant containing the photosensitizer (a) alone without the photopolymerization initiator (d).
- Examples of the photosensitizer (a) having a (meth) acryl group include a thioxanthone compound having a (meth) acryl group in a molecule disclosed in JP-A-2004-224993 (JP 2004-224993 A) or JP-A-2008 And 4-alkoxy-1- (2- (meth) acryloxyalkoxy) naphthalene disclosed in -1640 (JP2008-1640 A).
- a reaction product of a glycidyl group-containing (meth) acrylate compound having both a glycidyl group and a (meth) acryl group in one molecule and a thioxanthone carboxylic acid can be mentioned.
- Examples thereof include a reaction product of glycidyl (meth) acrylate or 2-glycidyloxypropyl (meth) acrylate and thioxanthone carboxylic acid.
- the compound examples include 3- (meth) acryloxy-2-hydroxypropyl ester of thioxanthone carboxylic acid and 2- (3-acryloxy-2-hydroxypropoxy) propyl ester of thioxanthone carboxylic acid. Of these, 3- (meth) acryloxy-2-hydroxypropyl ester of thioxanthonecarboxylic acid is more preferable.
- 4-alkoxy-1- (2- (meth) acryloxyalkoxy) naphthalene disclosed in JP-A-2008-1640 4-C1-C4 alkoxy-1- (2- (meth) acryloxy-2- R 1 -ethoxy) naphthalene (R 1 represents a hydrogen atom or a C1-C2 alkyl group) is preferred.
- R 1 represents a hydrogen atom or a C1-C2 alkyl group
- (meth) acryl means “acryl” (CH 2 ⁇ CH 2 CO—) and / or “methacryl” (CH (CH 3 ) ⁇ CH 2 CO—). To do.
- a photosensitizer (a) which has a (meth) acryl group As a more preferable compound as a photosensitizer (a) which has a (meth) acryl group, the compound etc. which are represented by following formula (1), (2), (3), etc. are mentioned, for example.
- the compound represented by the above formula (1) can be produced by the method described in JP-A-2004-224993.
- the compounds represented by the above formulas (2) and (3) can be produced by the method described in JP-A-2008-1640.
- the photosensitizer can effectively assist the generation of radicals of the photopolymerization initiator, even with low energy light.
- ordinary photosensitizers are contaminated with liquid crystals and are difficult to use as components constituting liquid crystal sealants.
- liquid crystal contamination can be prevented by using a photosensitizer having a photoreactive group, particularly a (meth) acryl group, in the molecule.
- the photosensitizer having an acrylic group can prevent liquid crystal contamination by being taken into the cured product.
- the content of the photosensitizer (a) having a (meth) acryl group in the molecule is preferably 0.01% by mass to 5% by mass when the entire liquid crystal sealant of the present invention is 100% by mass. More preferably, the content is from 0.1% by mass to 3% by mass, and even more preferably from 0.7% to 3% by mass.
- the photoinitiator (d) used by this invention will not be specifically limited if it is a radical type polymerization initiator.
- benzyldimethyl ketal 1-hydroxycyclohexyl phenyl ketone, diethylthioxanthone, benzophenone, 2-ethylanthraquinone, 2-hydroxy-2-methylpropiophenone, 2-methyl- [4- (methylthio) phenyl] -2-
- Examples include morpholino-1-propane, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like, or a photopolymerization initiator having a (meth) acryl group represented by the following formula (A) described in WO 2006/027982 pamphlet.
- R 1 represents a divalent linear, branched or cyclic lower alkylene group or arylene group having 1 to 10 carbon atoms
- R 2 represents a divalent linear, branched or cyclic group having 1 to 10 carbon atoms
- Ar represents an arylene group
- R 3 represents a hydrogen atom or a methyl group
- X and Y are O or S
- Z is either a hydroxyl group or a morpholino group.
- R 1 or R 2 is preferably a C1-C4 alkylene group.
- preferable photopolymerization initiators include those represented by the following formula (A ′).
- R represents a hydrogen atom or a methyl group
- X and Y each independently represent an oxygen atom or a sulfur atom
- Z represents a hydroxyl group or a morpholino group.
- This compound can be produced by the method described in International Publication WO2006 / 027982 Pamphlet.
- Preferable compounds represented by the above formula (A ′) include compounds in which R is a methyl group, X and Y are oxygen atoms, and Z is a hydroxy group in the above formula.
- the compound can be obtained by reacting 2-methacryloyloxyethyl isocyanate with 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one.
- the content of the photopolymerization initiator (d) is preferably 0.01% by mass to 5% by mass, preferably 0.1% by mass to 3% by mass, when the total liquid crystal sealant of the present invention is 100% by mass. % Is more preferably 0.7 to 3% by mass. If the amount is too small, sufficient curability cannot be obtained. If the amount is too large, contamination of the liquid crystal with the initiator may be a problem.
- the liquid crystal sealing agent of the present invention contains a curable resin (b) having a (meth) acryl group.
- a curable resin (b) having a (meth) acryl group For example, (meth) acrylic ester, epoxy (meth) acrylate, etc. are mentioned.
- (Meth) acrylic esters include benzyl methacrylate, cyclohexyl methacrylate, glycerol dimethacrylate, glycerol triacrylate, EO-modified glycerol triacrylate, pentaerythritol acrylate, trimethylolpropane triacrylate, tris (acryloxyethyl) isocyanurate, dipentaerythritol. Examples include hexaacrylate and phloroglucinol triacrylate.
- Epoxy (meth) acrylate is obtained by a known method by reaction of an epoxy resin and (meth) acrylic acid.
- An epoxy resin more than bifunctional is preferable, for example, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a phenol novolac type epoxy resin , Cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, hydantoin type epoxy resin , Isocyanurate type epoxy resins, phenol novolac type epoxy resins having a triphenolmethane skeleton, and other difunctional phenolic diglycidyl esters such as catechol and resorcinol Ether compound, bi-functional alcohol diglycidyl ethers of, and their
- the ratio of an epoxy group and a (meth) acryl group is not limited, and is appropriately selected from the viewpoint of process compatibility and liquid crystal contamination.
- the content of the (meth) acrylic group-containing curable resin (b) in the liquid crystal sealant is usually about 30 to 80% by mass, preferably about 40 to 70% by mass.
- the liquid crystal sealant of the present invention may contain a component (c) a tertiary amine compound, and by containing the tertiary amine compound, the curability of the light shielding part can be further improved.
- the tertiary amine compound is a compound in which all three hydrogen atoms of ammonia are substituted with hydrocarbon groups, and examples thereof include compounds exemplified in the following formula (4).
- Z 1 to Z 3 are each independently a C1-C4 alkyl group, a hydroxy C1-C4 alkyl group, a hydroxy C1-C4 alkoxy C1-C4 alkyl group, a glycidyl group, or an acryloxy C1-C4 alkyl group.
- an aromatic ring group preferably a C6-C10 aromatic ring group, more preferably a phenyl group
- the C1-C4 alkyl group include methyl, ethyl and the like.
- examples of the hydroxy C1-C4 alkyl group include hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl and the like.
- examples of the hydroxy C1-C4 alkoxy C1-C4 alkyl group include hydroxyethoxymethyl, 2-hydroxyethoxyethyl, 3- (hydroxyethoxy) propyl, 3- (hydroxyethoxy) butyl, 2- (hydroxyethoxy ) Butyl and the like.
- aromatic ring group examples include a naphthyl group, a phenyl group, a C1-C3 alkyl-substituted phenyl group, and a C1-C6 alkoxycarbonyl-substituted phenyl group.
- a compound in which any one of Z 1 to Z 3 is an aromatic ring is one of preferred compounds.
- any one of Z 1 to Z 3 may have an aromatic ring group (preferably a C6 to C10 aromatic ring group, more preferably a C1 to C6 alkoxycarbonyl group or a C1 to C3 alkyl group). Is preferably a phenyl group).
- Particularly preferred are compounds that act as photopolymerization accelerators. Specifically, KAYACURE TRM DMBI, KAYACURE TRM EPA (both manufactured by Nippon Kayaku Co., Ltd.) and the like are commercially available.
- a reactive group such as an acrylic group or an epoxy group in the molecule.
- this compound include N, N-diglycidyl-o-toluidine (GOT: manufactured by Nippon Kayaku Co., Ltd.).
- more preferable compounds include those in which Z 1 to Z 3 in the above formula (4) are C1-C3 alkyl groups or glycidyl groups, and the remaining one is a C1-C6 alkoxycarbonyl group or C1-C3 alkyl group, etc. This is a phenyl group which may have a substituent.
- the adhesive strength can be improved by further using the epoxy resin (e).
- the epoxy resin (e) used is not particularly limited, but is preferably a bifunctional or higher epoxy resin (an epoxy resin having at least two epoxy groups), for example, a bisphenol A type epoxy resin or a bisphenol F type epoxy.
- Resin bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester type Epoxy resin, glycidylamine type epoxy resin, hydantoin type epoxy resin, isocyanurate type epoxy resin, phenol novolac type epoxy resin having triphenolmethane skeleton, other bifunctional Diglycidyl ethers of Nord acids, difunctional alcohols diglycidyl ethers of, and their halides, and the like hydrogenated product.
- bisphenol type epoxy resin or novolac type epoxy resin is preferable from the viewpoint of liquid crystal contamination.
- bisphenol-type epoxy resins are more preferred, and bisphenol A epoxy resins are more preferred.
- the content of the epoxy resin (e) in the liquid crystal sealant is about 1 to 30% by mass, preferably 7 to 30% by mass.
- thermosetting agent (f) used in the liquid crystal sealant of the present invention is not particularly limited, but solid organic acid hydrazide is preferably used.
- examples thereof include trihydrazide, 1,4,5,8-naphthoic acid tetrahydrazide, pyromellitic acid tetrahydrazide and the like.
- aliphatic hydrazide compound examples include form hydrazide, acetohydrazide, propionic acid hydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, pimelic acid dihydrazide, 1,4- Cyclohexane dihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, iminodiacetic acid dihydrazide, N, N'-hexamethylenebissemicarbazide, citric acid trihydrazide, nitriloacetic acid trihydrazide, cyclohexanetricarboxylic acid trihydrazide, 1,3-bis (hydrazinocarbono And dihydrazides having a valine hydantoin skeleton such as ethyl) -5-isopropylhy
- the dihydrazide is preferably a bifunctional dihydrazide from the balance of curing reactivity and latency, and more preferably a dihydrazide of a dicarboxylic acid having two carboxy groups on a C3-C6 hydrocarbon. More preferred is adipic acid dihydrazide or isophthalic acid dihydrazide. In some cases, adipic acid dihydrazide is more preferable.
- a thermosetting agent (f) when such a thermosetting agent (f) is used, when the epoxy equivalent of the epoxy group of the epoxy resin (e) is 1, it is usually about 0.5 to 2.0 equivalent, preferably 0.8 to 1. About 2 equivalents.
- the silane coupling agent (g) can be used to improve the adhesive strength and the moisture resistance reliability.
- silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy Silane, N-phenyl- ⁇ -aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3-amino Propyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl
- Glycidoxypropyl tri-C1 to C3 alkoxysilane or glycidoxypropyl C1 to C3 alkyldiC1 to C3 alkoxysilane is preferred.
- the content of the silane coupling agent (g) in the liquid crystal sealant is preferably 0.05 to 3% by mass when the total liquid crystal sealant of the present invention is 100% by mass.
- the inorganic filler (h) can be used to improve the adhesive strength and the moisture resistance reliability.
- the inorganic filler (h) include fused silica, crystalline silica, silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, magnesium oxide, zirconium oxide, Aluminum hydroxide, magnesium hydroxide, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber, molybdenum disulfide, asbestos, etc., preferably fused silica, crystalline silica, nitriding Silicon, boron nitride, calcium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide, calcium silicate, aluminum silicate, more preferably
- These inorganic fillers may be used in combination of two or more. If the average particle size is too large, it becomes a cause of defects such as inability to form a gap when the upper and lower glass substrates are bonded together when manufacturing a narrow gap liquid crystal cell. Therefore, 3 ⁇ m or less is appropriate, and preferably 2 ⁇ m or less. .
- the particle size can be measured with a laser diffraction / scattering particle size distribution analyzer (dry type) (manufactured by Seishin Enterprise Co., Ltd .; LMS-30).
- the content of the inorganic filler (h) that can be used in the liquid crystal sealant of the present invention in the liquid crystal sealant is usually 10 to 60% by mass, preferably 100% by mass, preferably 100% by mass. 20 to 50% by mass.
- the content of the inorganic filler (h) that can be used in the liquid crystal sealant of the present invention in the liquid crystal sealant is usually 10 to 60% by mass, preferably 100% by mass, preferably 100% by mass. 20 to 50% by mass.
- the liquid crystal sealant of the present invention may further contain additives such as organic fillers, pigments, leveling agents, antifoaming agents and solvents.
- the preferred liquid crystal sealant of the present invention is summarized as follows. 1. Containing 0.01 to 5% by mass of the photosensitizer (a) and 30 to 80% by mass of the curable resin (b), with the balance being (d) a photopolymerization initiator, (e) an epoxy resin, f) A liquid crystal sealing agent comprising at least one selected from the group consisting of a thermosetting agent and (g) a silane coupling agent. 2. (D) The liquid crystal sealing agent according to 1 above, containing 0.01 to 5% by mass of a photopolymerization initiator. 3. 3. 3.
- the liquid crystal seal according to 1 or 2 above comprising (e) 1 to 30% by mass of an epoxy resin and (f) a thermosetting agent in a ratio of 0.5 to 2 equivalents relative to 1 equivalent of epoxy groups of the epoxy resin. Agent. 4).
- the photosensitizer (a) is a reaction product of thioxanthonecarboxylic acid and a glycidyl (meth) acrylate compound or 4-C1-C4 alkoxy-1- (2- (meth) acryloxy-2-R 1 -ethoxy 7.
- the photosensitizer (a) is at least one selected from the group consisting of compounds represented by the formulas (1) to (3). .
- 9. 9 The liquid crystal sealing agent according to any one of 1 to 8, wherein the curable resin (b) is an epoxy (meth) acrylate.
- the liquid crystal sealant of the present invention can be obtained as follows. First, the epoxy resin (e) and / or the silane coupling agent (g) are dissolved and mixed in the component (b) as necessary. Next, the photosensitizer (a) and, if necessary, the photopolymerization initiator (d) are dissolved therein, and further, if necessary, a thermosetting agent (f) and / or an inorganic filler. (H) and, if necessary, an organic filler, an antifoaming agent, a leveling agent, a solvent and the like are added, and uniformly mixed by a known mixing device such as a three roll, sand mill, ball mill, etc.
- the liquid crystal sealant of the present invention can be produced by filtration.
- the liquid crystal display cell of the present invention is a cell in which a pair of substrates having predetermined electrodes formed on a substrate are arranged opposite to each other at a predetermined interval, the periphery is sealed with the liquid crystal sealant of the present invention, and the liquid crystal is sealed in the gap. is there.
- the kind of liquid crystal to be sealed is not particularly limited.
- the substrate is composed of a combination of substrates made of at least one of glass, quartz, plastic, silicon, etc. and having light transmission properties.
- a spacer spacer (gap control material) such as glass fiber
- the liquid crystal sealant is applied to one of the pair of substrates using a dispenser or a screen printing device.
- the liquid crystal is dropped inside the weir of the liquid crystal sealing agent, and the other glass substrate is overlaid in a vacuum to create a gap.
- the liquid crystal seal portion is irradiated with ultraviolet rays by an ultraviolet irradiator to be photocured.
- Ultraviolet irradiation amount is preferably 500mJ / cm 2 ⁇ 6000mJ / cm 2, more preferably the dose of 1000mJ / cm 2 ⁇ 4000mJ / cm 2 is preferred.
- the liquid crystal display cell of the present invention can be obtained by curing at 90 to 130 ° C. for 1 to 2 hours.
- the liquid crystal display cell of the present invention thus obtained has no display defects due to liquid crystal contamination, and has excellent adhesion and moisture resistance reliability.
- the spacer include glass fiber, silica beads, polymer beads and the like.
- the diameter varies depending on the purpose, but is usually 2 to 8 ⁇ m, preferably 4 to 7 ⁇ m.
- the amount used is usually about 0.1 to 4% by mass, preferably 0.5 to 2% by mass, more preferably about 0.9 to 1.5% by mass with respect to 100% by mass of the liquid crystal sealant of the present invention. is there.
- part means “part by mass”
- % means “% by mass”.
- Examples 1-6, Comparative Examples 1-2 Preparation of sealant for liquid crystal dropping method
- the photosensitizer (a), the photopolymerization initiator (d), and, if necessary, a tertiary amine were dissolved by heating.
- a silane coupling agent (g), an inorganic filler (h), a thermosetting agent (f), etc. are added as appropriate, and after stirring, the mixture is dispersed with a three-roll mill, and then a metal mesh is used. Filtration was carried out to prepare sealing agents Examples 1 to 6 and Comparative Examples 1 and 2 for the liquid crystal dropping method.
- Liquid Crystal Contamination Test About 100 mg of each sealing agent for liquid crystal dropping method after irradiating 3000 mJ / cm 2 ultraviolet rays was applied to the bottom of each 10 ml vial. Next, a liquid crystal (MLC-6866-100: manufactured by Merck & Co., Inc.) was added thereto in an amount 10 times the amount of each applied sealing agent. The obtained vial was heated and held at 120 ° C. for 1 hour, and then cooled for 30 minutes until it reached room temperature. Each supernatant (liquid crystal) is separated by decantation, and the electrical resistance value is measured with a digital ultrahigh resistance meter (R8340: manufactured by Advantest Co., Ltd.). Judgment was made based on the criteria.
- MLC-6866-100 manufactured by Merck & Co., Inc.
- Example 1 2.1E + 12, Example 2: 1.6E + 12, Example 3: 1.8E + 12, Example 4: 7.3E + 11, Example 5: 2.3E + 12, Example 6: 6.2E + 11
- each liquid crystal sealant (surface 1 having 5 ⁇ m glass fiber added to the composition shown in FIG. 1) is applied in a circle, bonded using a black matrix substrate as a counter substrate, fixed with a clip, and shown as 1-1 in FIG.
- a sample for light-shielding part curability test was prepared. Each test sample was irradiated with 3000 mJ / cm 2 of ultraviolet light from the side of the glass substrate etched with chromium to cure the sealing agent (1-2 in FIG. 1). Thereafter, the bonded black matrix was peeled off, and the portion shielded from light under chrome was observed with a microscope, and the cured width of the light shielding portion was measured.
- Adhesive strength test 1 g of 5 ⁇ m glass fiber is added as a spacer to 100 g of liquid crystal sealant, and mixed and stirred. After applying this liquid crystal sealing agent on a 50 mm ⁇ 50 mm glass substrate, bonding a 1.5 mm ⁇ 1.5 mm glass piece on the liquid crystal sealing agent, and irradiating 3000 mJ / cm 2 of ultraviolet rays with a UV irradiator, It was cured by putting it in a 120 ° C. oven for 1 hour. The shear adhesive strength of the glass piece was measured with a bond tester (SS-30WD: manufactured by Seishin Shoji Co., Ltd.).
- the liquid crystal sealant of the present invention has good curability even in light of weak energy such as leaked light in a light shielding portion where direct ultraviolet rays do not reach, thereby widening the range of liquid crystal panel design. High reliability can be guaranteed.
- the liquid crystal sealant of the present invention is less contaminated with liquid crystal and can cure the light-shielding part where ultraviolet rays do not reach with a considerable width, even if there is a part where ultraviolet rays etc. are not directly exposed behind the wiring, it can seal well Since the agent can be uniformly cured and the adhesive strength of the cured sealant is also excellent, it is very useful as a liquid crystal sealant.
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Abstract
Description
即ち本発明は、次の(1)~(17)に関するものである。 As a result of intensive studies, the present inventors have found that by using a photosensitizer having an acrylic group in the molecule, the reactivity by light can be remarkably improved and the liquid crystal contamination can be suppressed. The present invention has been completed.
That is, the present invention relates to the following (1) to (17).
(2)(a)(メタ)アクリル基を分子内に有する光増感剤がチオキサントンカルボン酸とグリシジル(メタ)アクリレート化合物との反応生成物または4-C1ーC4アルコキシ-1-(2-(メタ)アクリルオキシ-2-R1-エトキシ)ナフタレン(R1は水素原子またはC1ーC2アルキル基を表す)である上記(1)に記載の液晶滴下工法用液晶シール剤。
(3) 前記(a)(メタ)アクリル基を分子内に有する光増感剤が少なくとも下記式(1)乃至(3)で表される化合物の何れかである上記(1)に記載の液晶滴下工法用液晶シール剤。
式(1)
式(2)
式(3)
(1) A liquid crystal sealing agent for a liquid crystal dropping method comprising a photosensitizer having (a) (meth) acrylic group in the molecule and (b) a curable resin having (meth) acrylic group.
(2) (a) The photosensitizer having a (meth) acryl group in the molecule is a reaction product of thioxanthonecarboxylic acid and a glycidyl (meth) acrylate compound or 4-C1-C4 alkoxy-1- (2- ( The liquid crystal sealing agent for a liquid crystal dropping method according to the above (1), which is (meth) acryloxy-2-R 1 -ethoxy) naphthalene (R 1 represents a hydrogen atom or a C1-C2 alkyl group).
(3) The liquid crystal according to (1), wherein the photosensitizer (a) having a (meth) acryl group in the molecule is at least one of compounds represented by the following formulas (1) to (3): Liquid crystal sealant for dripping method.
Formula (1)
Formula (2)
Formula (3)
(5)更に(d)光重合開始剤を含有する上記(1)~(4)のいずれか一項に記載の液晶滴下工法用液晶シール剤。
(6) 前記光重合開始剤(d)が分子内に(メタ)アクリル基を有する光重合開始剤である上記(5)に記載の液晶滴下工法用液晶シール剤。
(7) 前記硬化性樹脂(b)がエポキシ(メタ)アクリレートである上記(1)~(6)のいずれか一項に記載の液晶滴下工法用液晶シール剤。
(8) 前記硬化性樹脂(b)がレゾルシンジグリシジルエーテルとアクリル酸の反応生成物である上記(1)~(6)のいずれか一項に記載の液晶滴下工法用液晶シール剤。
(9) 更に(e)エポキシ樹脂、(f)熱硬化剤を含有する上記(1)~(8)のいずれか一項に記載の液晶滴下工法用液晶シール剤。
(10) 更に(g)シランカップリング剤を含む、上記(1)~(9)のいずれか一項に記載の液晶滴下工法用液晶シール剤。
(11) 更に(h)無機フィラーを含有する上記(1)~(10)のいずれか一項に記載の液晶滴下工法用液晶シール剤。
(12) 液晶シール剤の全体に対して、前記光増感剤(a)を0.01~5質量%および前記硬化性樹脂(b)を30~80質量%含む上記(1)に記載の液晶滴下工法用液晶シール剤。 (4) The liquid crystal sealing agent for a liquid crystal dropping method according to any one of (1) to (3), further comprising (c) a tertiary amine compound.
(5) The liquid crystal sealing agent for a liquid crystal dropping method according to any one of (1) to (4), further comprising (d) a photopolymerization initiator.
(6) The liquid crystal sealing agent for a liquid crystal dropping method according to the above (5), wherein the photopolymerization initiator (d) is a photopolymerization initiator having a (meth) acryl group in the molecule.
(7) The liquid crystal sealing agent for a liquid crystal dropping method according to any one of the above (1) to (6), wherein the curable resin (b) is an epoxy (meth) acrylate.
(8) The liquid crystal sealing agent for a liquid crystal dropping method according to any one of the above (1) to (6), wherein the curable resin (b) is a reaction product of resorcin diglycidyl ether and acrylic acid.
(9) The liquid crystal sealant for a liquid crystal dropping method according to any one of (1) to (8), further comprising (e) an epoxy resin and (f) a thermosetting agent.
(10) The liquid crystal sealant for a liquid crystal dropping method according to any one of (1) to (9), further comprising (g) a silane coupling agent.
(11) The liquid crystal sealant for a liquid crystal dropping method according to any one of (1) to (10), further comprising (h) an inorganic filler.
(12) The liquid crystal sealant according to (1), wherein the photosensitizer (a) is 0.01 to 5% by mass and the curable resin (b) is 30 to 80% by mass with respect to the entire liquid crystal sealant. Liquid crystal sealant for liquid crystal dropping method.
(14) 更に、(e)エポキシ樹脂を1~30質量%および(f)熱硬化剤をエポキシ樹脂のエポキシ基1当量に対して、0.5~2当量含有する上記(12)または(13)に記載の液晶滴下工法用液晶シール剤。
(15) 更に(g)シランカップリング剤を0.05~3質量%および(h)無機フィラーを10~60質量%含有する上記(12)~(14)のいずれか一項に記載の液晶滴下工法用液晶シール剤。
(16) 更に(c)3級アミン化合物を0~6質量%含有する上記(12)~(15)のいずれか一項に記載の液晶滴下工法用液晶シール剤。
(17) 上記1乃至16の何れか1項に記載の液晶滴下工法用液晶シール剤を硬化して得られる硬化物でシールされた液晶表示セル。 (13) The liquid crystal sealing agent for a liquid crystal dropping method according to the above (12), further comprising (d) 0.01 to 5% by mass of a photopolymerization initiator.
(14) The above (12) or (13) further comprising (e) 1 to 30% by mass of an epoxy resin and (f) 0.5 to 2 equivalents of a thermosetting agent with respect to 1 equivalent of epoxy groups of the epoxy resin. Liquid crystal sealing agent for liquid crystal dropping method as described in).
(15) The liquid crystal according to any one of (12) to (14), further comprising (g) 0.05 to 3% by mass of a silane coupling agent and (h) 10 to 60% by mass of an inorganic filler. Liquid crystal sealant for dripping method.
(16) The liquid crystal sealing agent for a liquid crystal dropping method according to any one of the above (12) to (15), further comprising (c) a tertiary amine compound in an amount of 0 to 6% by mass.
(17) A liquid crystal display cell sealed with a cured product obtained by curing the liquid crystal sealing agent for a liquid crystal dropping method according to any one of 1 to 16 above.
The liquid crystal sealant of the present invention has little liquid crystal contamination and has good curability even with low energy light such as visible light. Therefore, it has sufficient curability even under the wiring where direct light is difficult to reach, and the light-shielding portion that is not directly irradiated with ultraviolet rays can be cured with a wide width, and even when it is shaded by the wiring, it can be cured uniformly. For this reason, it is possible to secure the degree of freedom of the wiring design of the panel and the degree of freedom of the process of irradiation with visible light, and the manufacture of a highly reliable liquid crystal display panel can be facilitated.
1 ブラックマトリックス基板
2 クロムメッキをエッチングした基板
3 エッチングした基板面上のクロムメッキ層
4 液晶シール剤
1-2 遮光部硬化試験用サンプルを横から見た図
1 ブラックマトリックス基板
2 クロムメッキをエッチングした基板
3 エッチングした基板上のクロムメッキ層
4 液晶シール剤
UV 紫外線
1-3 シール剤硬化後の遮光部硬化試験用サンプルの液晶シール剤の硬化状況を示す図
5 液晶シール剤の硬化部分
6 液晶シール剤の未硬化部分
7 クロム層の下の遮光部において、液晶シール剤の硬化した部分 1-1: Light-shielding part curing test sample before curing sealant as viewed from above FIG. 1
Fig. 5 shows the curing state of the liquid crystal sealant of the sample for the light-shielding part curing test after curing of the UV ultraviolet ray. Figure 5 Cured part of the liquid-
(メタ)アクリル基を有する光増感剤(a)としては、例えば特開2004-224993(JP2004-224993 A)に開示されている分子中に(メタ)アクリル基を有するチオキサントン化合物または特開2008-1640(JP2008-1640 A)に開示されている4-アルコキシ-1-(2-(メタ)アクリルオキシアルコキシ)ナフタレン等を挙げることが出来る。
より具体的には特開2004-224993に開示の化合物として、例えば1分子中にグリシジル基と(メタ)アクリル基の両者を有するグリシジル基含有(メタ)アクリレート化合物とチオキサントンカルボン酸の反応生成物を挙げることができる。例えば、グリシジル(メタ)アクリレートまたは2-グリシジルオキシプロピル(メタ)アクリレートとチオキサントンカルボン酸の反応生成物等を挙げることが出来る。具体的な化合物としてはチオキサントンカルボン酸の3-(メタ)アクリルオキシ-2-ヒドロキシプロピルエステルまたはチオキサントンカルボン酸の2-(3-アクリルオキシ-2-ヒドロキシプロポキシ)プロピルエステルなどを挙げることが出来る。これらの中で、チオキサントンカルボン酸の3-(メタ)アクリルオキシ-2-ヒドロキシプロピルエステルはより好ましい。
特開2008-1640に開示されている4-アルコキシ-1-(2-(メタ)アクリルオキシアルコキシ)ナフタレンとしては、4-C1ーC4アルコキシ-1-(2-(メタ)アクリルオキシ-2-R1-エトキシ)ナフタレン(R1は水素原子またはC1-C2アルキル基を表す)が好ましい。
なお、本明細書に置いて、「(メタ)アクリル」の用語は「アクリル」(CH2=CH2CO-)及び/又は「メタクリル」(CH(CH3)=CH2CO-)を意味する。 Any photosensitizer (a) having a (meth) acryl group in the molecule used in the present invention may be used as long as it has a (meth) acryl group and acts as a photosensitizer (a). I can do it. In the liquid crystal sealing agent of the present invention, the photosensitizer (a) is usually used in combination with a photopolymerization initiator (d) described later. However, if there is no hindrance, the liquid crystal sealant of the present invention may be a liquid crystal sealant containing the photosensitizer (a) alone without the photopolymerization initiator (d).
Examples of the photosensitizer (a) having a (meth) acryl group include a thioxanthone compound having a (meth) acryl group in a molecule disclosed in JP-A-2004-224993 (JP 2004-224993 A) or JP-A-2008 And 4-alkoxy-1- (2- (meth) acryloxyalkoxy) naphthalene disclosed in -1640 (JP2008-1640 A).
More specifically, as a compound disclosed in JP-A-2004-224993, for example, a reaction product of a glycidyl group-containing (meth) acrylate compound having both a glycidyl group and a (meth) acryl group in one molecule and a thioxanthone carboxylic acid. Can be mentioned. Examples thereof include a reaction product of glycidyl (meth) acrylate or 2-glycidyloxypropyl (meth) acrylate and thioxanthone carboxylic acid. Specific examples of the compound include 3- (meth) acryloxy-2-hydroxypropyl ester of thioxanthone carboxylic acid and 2- (3-acryloxy-2-hydroxypropoxy) propyl ester of thioxanthone carboxylic acid. Of these, 3- (meth) acryloxy-2-hydroxypropyl ester of thioxanthonecarboxylic acid is more preferable.
As 4-alkoxy-1- (2- (meth) acryloxyalkoxy) naphthalene disclosed in JP-A-2008-1640, 4-C1-C4 alkoxy-1- (2- (meth) acryloxy-2- R 1 -ethoxy) naphthalene (R 1 represents a hydrogen atom or a C1-C2 alkyl group) is preferred.
In this specification, the term “(meth) acryl” means “acryl” (CH 2 ═CH 2 CO—) and / or “methacryl” (CH (CH 3 ) ═CH 2 CO—). To do.
As a more preferable compound as a photosensitizer (a) which has a (meth) acryl group, the compound etc. which are represented by following formula (1), (2), (3), etc. are mentioned, for example.
通常、光増感剤は低エネルギーの光であっても有効に、光重合開始剤のラジカルの発生を助ける事ができる。しかし、通常の光増感剤は液晶に対して汚染性を有し、液晶シール剤を構成する成分としては使用困難である。しかしながら、本発明においては、分子内に光反応性基、特に(メタ)アクリル基を有する光増感剤を使用することによって、液晶汚染を防止する事ができることを見出したもので、該(メタ)アクリル基を有する光増感剤は硬化物に取り込まれることにより液晶汚染を防止する事ができると考えられる。
この分子内に(メタ)アクリル基を有する光増感剤(a)の含有量としては本発明の液晶シール剤の全体を100質量%とした場合、0.01質量%から5質量%が好ましく、より好ましくは0.1質量%から3質量%であり、更に好ましくは0.7~3質量%である。 The compound represented by the above formula (1) can be produced by the method described in JP-A-2004-224993. The compounds represented by the above formulas (2) and (3) can be produced by the method described in JP-A-2008-1640.
Usually, the photosensitizer can effectively assist the generation of radicals of the photopolymerization initiator, even with low energy light. However, ordinary photosensitizers are contaminated with liquid crystals and are difficult to use as components constituting liquid crystal sealants. However, in the present invention, it has been found that liquid crystal contamination can be prevented by using a photosensitizer having a photoreactive group, particularly a (meth) acryl group, in the molecule. ) It is considered that the photosensitizer having an acrylic group can prevent liquid crystal contamination by being taken into the cured product.
The content of the photosensitizer (a) having a (meth) acryl group in the molecule is preferably 0.01% by mass to 5% by mass when the entire liquid crystal sealant of the present invention is 100% by mass. More preferably, the content is from 0.1% by mass to 3% by mass, and even more preferably from 0.7% to 3% by mass.
式(A)
式中、R1は炭素数1乃至10の二価の直鎖、分岐または環状の低級アルキレン基あるいはアリーレン基を示し、R2は炭素数1乃至10の二価の直鎖、分岐または環状の低級アルキレン基あるいはアリーレン基を示し、Arはアリーレン基を示し、R3は水素原子またはメチル基を示す。またX,YはO又はSであり、Zはヒドロキシル基又はモルホリノ基の何れか一方である。
上記R1またはR2としてはC1-C4アルキレン基が好ましい。 Moreover, the photoinitiator (d) used by this invention will not be specifically limited if it is a radical type polymerization initiator. For example, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, diethylthioxanthone, benzophenone, 2-ethylanthraquinone, 2-hydroxy-2-methylpropiophenone, 2-methyl- [4- (methylthio) phenyl] -2- Examples include morpholino-1-propane, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like, or a photopolymerization initiator having a (meth) acryl group represented by the following formula (A) described in WO 2006/027982 pamphlet. be able to.
Formula (A)
In the formula, R 1 represents a divalent linear, branched or cyclic lower alkylene group or arylene group having 1 to 10 carbon atoms, and R 2 represents a divalent linear, branched or cyclic group having 1 to 10 carbon atoms. A lower alkylene group or an arylene group, Ar represents an arylene group, and R 3 represents a hydrogen atom or a methyl group; X and Y are O or S, and Z is either a hydroxyl group or a morpholino group.
R 1 or R 2 is preferably a C1-C4 alkylene group.
式中Rは水素原子またはメチル基、X及びYはそれぞれ独立に酸素原子または硫黄原子、Zは水酸基またはモルフォリノ基を表す。
この化合物は国際公開WO2006/027982パンフレット記載の方法にて製造することができる。上記式(A’)で表される好ましい化合物としては、上記式において、Rがメチル基、X及びYが酸素原子、Zがヒドロキシ基である化合物を挙げることができる。該化合物は2-メタクリロイルオキシエチルイソシアネートと1-[4-(2-ヒドロキシエトキシ)-フェニル]-2-ヒドロキシ-2-メチル-1-プロパン-1-オンとの反応で得ることができる。 From the viewpoint of liquid crystal contamination, it is preferable to use a photopolymerization initiator having a (meth) acryl group in the molecule. For example, preferable photopolymerization initiators include those represented by the following formula (A ′).
In the formula, R represents a hydrogen atom or a methyl group, X and Y each independently represent an oxygen atom or a sulfur atom, and Z represents a hydroxyl group or a morpholino group.
This compound can be produced by the method described in International Publication WO2006 / 027982 Pamphlet. Preferable compounds represented by the above formula (A ′) include compounds in which R is a methyl group, X and Y are oxygen atoms, and Z is a hydroxy group in the above formula. The compound can be obtained by reacting 2-methacryloyloxyethyl isocyanate with 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one.
また、(メタ)アクリル基を有する硬化性樹脂(b)の液晶シール剤中に占める含有率は、通常30~80質量%程度であり、好ましくは40~70質量%程度である。 The liquid crystal sealing agent of the present invention contains a curable resin (b) having a (meth) acryl group. For example, (meth) acrylic ester, epoxy (meth) acrylate, etc. are mentioned. (Meth) acrylic esters include benzyl methacrylate, cyclohexyl methacrylate, glycerol dimethacrylate, glycerol triacrylate, EO-modified glycerol triacrylate, pentaerythritol acrylate, trimethylolpropane triacrylate, tris (acryloxyethyl) isocyanurate, dipentaerythritol. Examples include hexaacrylate and phloroglucinol triacrylate. Epoxy (meth) acrylate is obtained by a known method by reaction of an epoxy resin and (meth) acrylic acid. Although it does not specifically limit as an epoxy resin used as a raw material, An epoxy resin more than bifunctional is preferable, for example, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a phenol novolac type epoxy resin , Cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, hydantoin type epoxy resin , Isocyanurate type epoxy resins, phenol novolac type epoxy resins having a triphenolmethane skeleton, and other difunctional phenolic diglycidyl esters such as catechol and resorcinol Ether compound, bi-functional alcohol diglycidyl ethers of, and their halides, and the like hydrogenated product. Among these, from the viewpoint of liquid crystal contamination, more preferred is resorcin diglycidyl ether. Moreover, the ratio of an epoxy group and a (meth) acryl group is not limited, and is appropriately selected from the viewpoint of process compatibility and liquid crystal contamination.
The content of the (meth) acrylic group-containing curable resin (b) in the liquid crystal sealant is usually about 30 to 80% by mass, preferably about 40 to 70% by mass.
ここで3級アミン化合物とは、アンモニアの水素原子が3つとも炭化水素基で置換された化合物であり、例えば下記式(4)に例示する化合物が挙げられる。
(4)
式(4)中、Z1~Z3はそれぞれ独立に、C1-C4アルキル基、ヒドロキシC1-C4アルキル基、ヒドロキシC1-C4アルコキシC1-C4アルキル基、グリシジル基、アクリルオキシC1~C4アルキル基、または、置換基としてC1~C6アルコキシカルボニル基またはC1~C3アルキル基を有してもよい芳香環基(好ましくはC6~C10芳香環基、更に好ましくはフェニル基)を表わす。
上記C1-C4アルキル基の例としては、メチル、エチル等が挙げられる。同様に、上記ヒドロキシC1-C4アルキル基の例としては、ヒドロキシメチル、ヒドロキシエチル、3-ヒドロキシプロピル、2-ヒドロキシプロピル、4-ヒドロキシブチル、3-ヒドロキシブチル、2-ヒドロキシブチル等が挙げられる。同様に、上記ヒドロキシC1-C4アルコキシC1-C4アルキル基の例としては、ヒドロキシエトキシメチル、2-ヒドロキシエトキシエチル、3-(ヒドロキシエトキシ)プロピル、3-(ヒドロキシエトキシ)ブチル、2-(ヒドロキシエトキシ)ブチル等が挙げられる。上記の芳香環基としては、ナフチル基、フェニル基、C1-C3アルキル置換フェニル基、C1~C6アルコキシカルボニル置換フェニル基等を挙げることが出来る。 The liquid crystal sealant of the present invention may contain a component (c) a tertiary amine compound, and by containing the tertiary amine compound, the curability of the light shielding part can be further improved.
Here, the tertiary amine compound is a compound in which all three hydrogen atoms of ammonia are substituted with hydrocarbon groups, and examples thereof include compounds exemplified in the following formula (4).
(4)
In formula (4), Z 1 to Z 3 are each independently a C1-C4 alkyl group, a hydroxy C1-C4 alkyl group, a hydroxy C1-C4 alkoxy C1-C4 alkyl group, a glycidyl group, or an acryloxy C1-C4 alkyl group. Or an aromatic ring group (preferably a C6-C10 aromatic ring group, more preferably a phenyl group) which may have a C1-C6 alkoxycarbonyl group or a C1-C3 alkyl group as a substituent.
Examples of the C1-C4 alkyl group include methyl, ethyl and the like. Similarly, examples of the hydroxy C1-C4 alkyl group include hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl and the like. Similarly, examples of the hydroxy C1-C4 alkoxy C1-C4 alkyl group include hydroxyethoxymethyl, 2-hydroxyethoxyethyl, 3- (hydroxyethoxy) propyl, 3- (hydroxyethoxy) butyl, 2- (hydroxyethoxy ) Butyl and the like. Examples of the aromatic ring group include a naphthyl group, a phenyl group, a C1-C3 alkyl-substituted phenyl group, and a C1-C6 alkoxycarbonyl-substituted phenyl group.
更に、当該3級アミン化合物による液晶汚染を防止する観点から、分子内にアクリル基、エポキシ基といった反応性基を有することも好ましい態様である。この化合物としては、例えばN,N-ジグリシジル-o-トルイジン(GOT:日本化薬株式会社製)等が挙げられる。
以上から、より好ましい化合物としては、上記式(4)におけるZ1~Z3の2つがC1-C3アルキル基、またはグリシジル基、残りの1つがC1~C6アルコキシカルボニル基またはC1~C3アルキル基等の置換基を有してもよいフェニル基である。 A compound in which any one of Z 1 to Z 3 is an aromatic ring is one of preferred compounds. For example, any one of Z 1 to Z 3 may have an aromatic ring group (preferably a C6 to C10 aromatic ring group, more preferably a C1 to C6 alkoxycarbonyl group or a C1 to C3 alkyl group). Is preferably a phenyl group). Particularly preferred are compounds that act as photopolymerization accelerators. Specifically, KAYACURE TRM DMBI, KAYACURE TRM EPA (both manufactured by Nippon Kayaku Co., Ltd.) and the like are commercially available.
Furthermore, from the viewpoint of preventing liquid crystal contamination by the tertiary amine compound, it is also a preferred embodiment to have a reactive group such as an acrylic group or an epoxy group in the molecule. Examples of this compound include N, N-diglycidyl-o-toluidine (GOT: manufactured by Nippon Kayaku Co., Ltd.).
From the above, more preferable compounds include those in which Z 1 to Z 3 in the above formula (4) are C1-C3 alkyl groups or glycidyl groups, and the remaining one is a C1-C6 alkoxycarbonyl group or C1-C3 alkyl group, etc. This is a phenyl group which may have a substituent.
該エポキシ樹脂(e)の液晶シール剤中に占める含有量(液晶シール剤全体に対する含有割合:以下同じ)は、1~30質量%程度、好ましくは7~30質量%である。 In the liquid crystal sealing agent of the present invention, the adhesive strength can be improved by further using the epoxy resin (e). The epoxy resin (e) used is not particularly limited, but is preferably a bifunctional or higher epoxy resin (an epoxy resin having at least two epoxy groups), for example, a bisphenol A type epoxy resin or a bisphenol F type epoxy. Resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester type Epoxy resin, glycidylamine type epoxy resin, hydantoin type epoxy resin, isocyanurate type epoxy resin, phenol novolac type epoxy resin having triphenolmethane skeleton, other bifunctional Diglycidyl ethers of Nord acids, difunctional alcohols diglycidyl ethers of, and their halides, and the like hydrogenated product. Among these, bisphenol type epoxy resin or novolac type epoxy resin is preferable from the viewpoint of liquid crystal contamination. In some cases, bisphenol-type epoxy resins are more preferred, and bisphenol A epoxy resins are more preferred.
The content of the epoxy resin (e) in the liquid crystal sealant (content ratio with respect to the whole liquid crystal sealant: the same shall apply hereinafter) is about 1 to 30% by mass, preferably 7 to 30% by mass.
硬化反応性と潜在性のバランスから好ましくは2官能であるジヒドラジドであり、より好ましくは、C3-C6炭化水素上に2つのカルボキシ基を有するジカルボン酸のジヒドラジドが好ましい。更に好ましくはアジピン酸ジヒドラジドまたはイソフタル酸ジヒドラジドである。また、場合により、アジピン酸ジヒドラジドが更に好ましい。かかる熱硬化剤(f)を使用する場合、エポキシ樹脂(e)のエポキシ基のエポキシ当量を1とした場合、通常0.5~2.0当量程度であり、好ましくは0.8~1.2当量程度である。 The thermosetting agent (f) used in the liquid crystal sealant of the present invention is not particularly limited, but solid organic acid hydrazide is preferably used. For example, the aromatic hydrazide salicylic acid hydrazide, benzoic acid hydrazide, 1-naphthoic acid hydrazide, terephthalic acid dihydrazide, isophthalic acid dihydrazide, 2,6-naphthoic acid dihydrazide, 2,6-pyridinedihydrazide, 1,2,4-benzene Examples thereof include trihydrazide, 1,4,5,8-naphthoic acid tetrahydrazide, pyromellitic acid tetrahydrazide and the like. Examples of the aliphatic hydrazide compound include form hydrazide, acetohydrazide, propionic acid hydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, pimelic acid dihydrazide, 1,4- Cyclohexane dihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, iminodiacetic acid dihydrazide, N, N'-hexamethylenebissemicarbazide, citric acid trihydrazide, nitriloacetic acid trihydrazide, cyclohexanetricarboxylic acid trihydrazide, 1,3-bis (hydrazinocarbono And dihydrazides having a valine hydantoin skeleton such as ethyl) -5-isopropylhydantoin.
The dihydrazide is preferably a bifunctional dihydrazide from the balance of curing reactivity and latency, and more preferably a dihydrazide of a dicarboxylic acid having two carboxy groups on a C3-C6 hydrocarbon. More preferred is adipic acid dihydrazide or isophthalic acid dihydrazide. In some cases, adipic acid dihydrazide is more preferable. When such a thermosetting agent (f) is used, when the epoxy equivalent of the epoxy group of the epoxy resin (e) is 1, it is usually about 0.5 to 2.0 equivalent, preferably 0.8 to 1. About 2 equivalents.
本発明の好ましい液晶シール剤をまとめると次の通りである。
1.前記光増感剤(a)を0.01~5質量%および前記硬化性樹脂(b)を30~80質量%含み、残部として、(d)光重合開始剤、(e)エポキシ樹脂と(f)熱硬化剤、および(g)シランカップリング剤からなる群から選ばれる少なくとも1種を含む液晶シール剤。
2.(d)光重合開始剤を0.01~5質量%含む上記1に記載の液晶シール剤。
3.(e)エポキシ樹脂を1~30質量%および(f)熱硬化剤をエポキシ樹脂のエポキシ基1当量に対して、0.5~2当量の割合で含有する上記1または2に記載の液晶シール剤。
4.(g)シランカップリング剤を0.05~3質量%含有する上記1~3の何れか一項に記載の液晶シール剤。
5.(h)無機フィラーを10~60質量%含有する上記1~4の何れか一項に記載の液晶シール剤。
6.更に(c)3級アミン化合物を0~6質量%、好ましくは0.1~5質量%含有する上記1~5の何れか一項に記載の液晶シール剤。
7.前記光増感剤(a)が、チオキサントンカルボン酸とグリシジル(メタ)アクリレート化合物との反応生成物または4-C1ーC4アルコキシ-1-(2-(メタ)アクリルオキシ-2-R1-エトキシ)ナフタレン(R1は水素原子またはC1ーC2アルキル基を表す)である上記1~6の何れか一項に記載の液晶シール剤。
8.前記光増感剤(a)が、前記式(1)~(3)で表される化合物からなる群から選ばれる少なくとも1つである上記1~7の何れか一項に記載の液晶シール剤。
9.前記硬化性樹脂(b)がエポキシ(メタ)アクリレートである上記1~8の何れか一項に記載の液晶シール剤。 If necessary, the liquid crystal sealant of the present invention may further contain additives such as organic fillers, pigments, leveling agents, antifoaming agents and solvents.
The preferred liquid crystal sealant of the present invention is summarized as follows.
1. Containing 0.01 to 5% by mass of the photosensitizer (a) and 30 to 80% by mass of the curable resin (b), with the balance being (d) a photopolymerization initiator, (e) an epoxy resin, f) A liquid crystal sealing agent comprising at least one selected from the group consisting of a thermosetting agent and (g) a silane coupling agent.
2. (D) The liquid crystal sealing agent according to 1 above, containing 0.01 to 5% by mass of a photopolymerization initiator.
3. 3. The liquid crystal seal according to 1 or 2 above, comprising (e) 1 to 30% by mass of an epoxy resin and (f) a thermosetting agent in a ratio of 0.5 to 2 equivalents relative to 1 equivalent of epoxy groups of the epoxy resin. Agent.
4). (G) The liquid crystal sealing agent according to any one of 1 to 3 above, containing 0.05 to 3% by mass of a silane coupling agent.
5. (H) The liquid crystal sealing agent according to any one of 1 to 4 above, containing 10 to 60% by mass of an inorganic filler.
6). The liquid crystal sealing agent according to any one of 1 to 5 above, further comprising (c) a tertiary amine compound in an amount of 0 to 6% by mass, preferably 0.1 to 5% by mass.
7. The photosensitizer (a) is a reaction product of thioxanthonecarboxylic acid and a glycidyl (meth) acrylate compound or 4-C1-C4 alkoxy-1- (2- (meth) acryloxy-2-R 1 -
8). 8. The liquid crystal sealant according to any one of 1 to 7, wherein the photosensitizer (a) is at least one selected from the group consisting of compounds represented by the formulas (1) to (3). .
9. 9. The liquid crystal sealing agent according to any one of 1 to 8, wherein the curable resin (b) is an epoxy (meth) acrylate.
11.(d)光重合開始剤が前記式(A’)で表される(メタ)アクリル基を有する重合開始剤である上記1~10の何れか一項に記載の液晶シール剤。
12.(e)エポキシ樹脂がビスフェノール型エポキシ樹脂またはノボラック型エポキシ樹脂である上記1~11の何れか一項に記載の液晶シール剤。
13.(f)熱硬化剤がジヒドラジドである上記1~12の何れか一項に記載の液晶シール剤。
14.(c)3級アミン化合物が前記式(4)におけるZ1~Z3の2つがC1-C3アルキル基、またはグリシジル基、残りの1つが置換基としてC1~C6アルコキシカルボニル基またはC1~C3アルキル基を有してもよいフェニル基である3級アミンである上記6~13の何れか一項に記載の液晶シール剤。 10. 10. The liquid crystal sealant according to 9 above, wherein the epoxy (meth) acrylate is a reaction product of resorcin diglycidyl ether and (meth) acrylic acid.
11. (D) The liquid crystal sealant according to any one of the above 1 to 10, wherein the photopolymerization initiator is a polymerization initiator having a (meth) acryl group represented by the formula (A ′).
12 (E) The liquid crystal sealant according to any one of the above 1 to 11, wherein the epoxy resin is a bisphenol type epoxy resin or a novolac type epoxy resin.
13. (F) The liquid crystal sealing agent according to any one of 1 to 12 above, wherein the thermosetting agent is dihydrazide.
14 (C) In the tertiary amine compound, two of Z 1 to Z 3 in the formula (4) are C1-C3 alkyl groups or glycidyl groups, and the remaining one is a C1-C6 alkoxycarbonyl group or C1-C3 alkyl as a substituent. 14. The liquid crystal sealing agent according to any one of 6 to 13, which is a tertiary amine which is a phenyl group which may have a group.
まず(b)成分に、必要に応じ、エポキシ樹脂(e)および/またはシランカップリング剤(g)を溶解混合する。次いで、そこに光増感剤(a)及び、必要に応じ、光重合開始剤(d)を溶解し、更に、そこに、必要に応じ、熱硬化剤(f)、および/または無機充填剤(h)、並びに、必要に応じ有機フィラー、消泡剤、及びレベリング剤、溶剤等を添加し、公知の混合装置、例えば3本ロール、サンドミル、ボールミル等により均一に混合し、金属メッシュ等で、濾過することにより本発明の液晶シール剤を製造することができる。 The liquid crystal sealant of the present invention can be obtained as follows.
First, the epoxy resin (e) and / or the silane coupling agent (g) are dissolved and mixed in the component (b) as necessary. Next, the photosensitizer (a) and, if necessary, the photopolymerization initiator (d) are dissolved therein, and further, if necessary, a thermosetting agent (f) and / or an inorganic filler. (H) and, if necessary, an organic filler, an antifoaming agent, a leveling agent, a solvent and the like are added, and uniformly mixed by a known mixing device such as a three roll, sand mill, ball mill, etc. The liquid crystal sealant of the present invention can be produced by filtration.
(液晶滴下工法用のシール剤の調製)
下記表1に示す割合で各樹脂成分を混合攪拌した後、光増感剤(a)、光重合開始剤(d)、必要に応じて、第3級アミンを加熱溶解させた。その後、必要に応じて、シランカップリング剤(g)、無機フィラー(h)、熱硬化剤(f)等を適宜添加し、攪拌した後、3本ロールミルにて分散させた後、金属メッシュで濾過し、液晶滴下工法用シール剤実施例1~6、比較例1~2を調製した。 Examples 1-6, Comparative Examples 1-2
(Preparation of sealant for liquid crystal dropping method)
After mixing and stirring each resin component in the ratio shown in Table 1 below, the photosensitizer (a), the photopolymerization initiator (d), and, if necessary, a tertiary amine were dissolved by heating. Thereafter, if necessary, a silane coupling agent (g), an inorganic filler (h), a thermosetting agent (f), etc. are added as appropriate, and after stirring, the mixture is dispersed with a three-roll mill, and then a metal mesh is used. Filtration was carried out to prepare sealing agents Examples 1 to 6 and Comparative Examples 1 and 2 for the liquid crystal dropping method.
それぞれの10mlバイアル瓶の底に、3000mJ/cm2の紫外線を照射した後の各液晶滴下工法用シール剤を100mg程度塗布した。次いで、そこに、液晶(MLC-6866-100:メルク株式会社製)を、塗布した各シール剤の10倍量加えた。得られたバイアル瓶を加熱して、120℃で1時間保持した後、室温になるまで、30分冷却した。それぞれの上澄み(液晶)をデカンテーションにて分け取り、デジタル超高抵抗計(R8340:株式会社アドバンテスト製)にて電気抵抗値を測定し、シール剤なしのものの値に対する比抵抗値で、以下の基準により判定を行った。
○ 1.0E+12以上
△ 1.0E+11以上1.0E+12未満
× 1.0E+11未満
なお、比抵抗値の「1.0E+12」は「1.0×1012」を表し、他の記載も同様である。
各実施例における比抵抗値は、それぞれ、下記の通りであった。
実施例1:2.1E+12、実施例2:1.6E+12、実施例3:1.8E+12、実施例4:7.3E+11、実施例5:2.3E+12、実施例6:6.2E+11 Liquid Crystal Contamination Test About 100 mg of each sealing agent for liquid crystal dropping method after irradiating 3000 mJ / cm 2 ultraviolet rays was applied to the bottom of each 10 ml vial. Next, a liquid crystal (MLC-6866-100: manufactured by Merck & Co., Inc.) was added thereto in an
○ 1.0E + 12 or more Δ 1.0E + 11 or more and less than 1.0E + 12 × less than 1.0E + 11 The specific resistance value “1.0E + 12” represents “1.0 × 10 12 ”, and the other descriptions are also the same.
The specific resistance values in the respective examples were as follows.
Example 1: 2.1E + 12, Example 2: 1.6E + 12, Example 3: 1.8E + 12, Example 4: 7.3E + 11, Example 5: 2.3E + 12, Example 6: 6.2E + 11
クロムメッキをしたガラス基板のクロムメッキを、中央に1本線(幅0.8cm)を残してエッチングしたガラス基板を用いて、それぞれの基板の中央に、各液晶シール剤(表1に示す組成のものに5μmのグラスファイバーを1w%添加したもの)を円形に塗付し、対向基板としてブラックマトリックス基板を用いて貼りあわせ、クリップで固定し、図1の1-1に示す遮光部硬化性試験用サンプルを作成した。この試験用サンプルのそれぞれに、クロムをエッチングしたガラス基板側から、3000mJ/cm2の紫外線を照射し、シール剤を硬化した(図1の1-2)。その後、貼り合わせたブラックマトリックスを剥がし、クロムの下で遮光されていた部分を顕微鏡で観察し、遮光部の硬化幅を測定した。 Light-shielding part curability test Using a glass substrate etched with chrome plating on a chrome-plated glass substrate leaving a single line (width 0.8 cm) in the center, each liquid crystal sealant (
液晶シール剤100gにスペーサーとして5μmのグラスファイバー1gを添加して混合撹拌を行う。この液晶シール剤を50mm×50mmのガラス基板上に塗布し、その液晶シール剤上に1.5mm×1.5mmのガラス片を貼り合わせUV照射機により3000mJ/cm2の紫外線を照射した後、120℃オーブンに1時間投入して硬化させた。そのガラス片のせん断接着強度をボンドテスター(SS-30WD:西進商事株式会社製)にて測定した。 Adhesive strength test 1 g of 5 μm glass fiber is added as a spacer to 100 g of liquid crystal sealant, and mixed and stirred. After applying this liquid crystal sealing agent on a 50 mm × 50 mm glass substrate, bonding a 1.5 mm × 1.5 mm glass piece on the liquid crystal sealing agent, and irradiating 3000 mJ / cm 2 of ultraviolet rays with a UV irradiator, It was cured by putting it in a 120 ° C. oven for 1 hour. The shear adhesive strength of the glass piece was measured with a bond tester (SS-30WD: manufactured by Seishin Shoji Co., Ltd.).
Claims (17)
- (a)(メタ)アクリル基を分子内に有する光増感剤および(b)(メタ)アクリル基を有する硬化性樹脂を含有する液晶滴下工法用液晶シール剤。 (A) A liquid crystal sealant for a liquid crystal dropping method containing a photosensitizer having a (meth) acryl group in the molecule and (b) a curable resin having a (meth) acryl group.
- (a)(メタ)アクリル基を分子内に有する光増感剤がチオキサントンカルボン酸とグリシジル(メタ)アクリレート化合物との反応生成物または4-C1ーC4アルコキシ-1-(2-(メタ)アクリルオキシ-2-R1-エトキシ)ナフタレン(R1は水素原子またはC1ーC2アルキル基を表す)である請求項1に記載の液晶滴下工法用液晶シール剤。 (A) A photosensitizer having a (meth) acryl group in the molecule is a reaction product of thioxanthonecarboxylic acid and a glycidyl (meth) acrylate compound or 4-C1-C4 alkoxy-1- (2- (meth) acrylic The liquid crystal sealing agent for a liquid crystal dropping method according to claim 1, which is oxy-2-R 1 -ethoxy) naphthalene (R 1 represents a hydrogen atom or a C1-C2 alkyl group).
- 前記(a)(メタ)アクリル基を分子内に有する光増感剤が少なくとも下記式(1)乃至(3)で表される化合物の何れかである請求項1に記載の液晶滴下工法用液晶シール剤。
式(1)
式(2)
式(3)
The liquid crystal for a liquid crystal dropping method according to claim 1, wherein the photosensitizer (a) having a (meth) acryl group in the molecule is at least one of the compounds represented by the following formulas (1) to (3). Sealing agent.
Formula (1)
Formula (2)
Formula (3)
- 更に(c)3級アミン化合物を含有する請求項1に記載の液晶滴下工法用液晶シール剤。 The liquid crystal sealing agent for liquid crystal dropping method according to claim 1, further comprising (c) a tertiary amine compound.
- 更に(d)光重合開始剤を含有する請求項1に記載の液晶滴下工法用液晶シール剤。 Furthermore, (d) The liquid-crystal sealing compound for liquid crystal dropping methods of Claim 1 containing a photoinitiator.
- 前記光重合開始剤(d)が分子内に(メタ)アクリル基を有する光重合開始剤である請求項5に記載の液晶滴下工法用液晶シール剤。 The liquid crystal sealing agent for a liquid crystal dropping method according to claim 5, wherein the photopolymerization initiator (d) is a photopolymerization initiator having a (meth) acryl group in the molecule.
- 前記硬化性樹脂(b)がエポキシ(メタ)アクリレートである請求項5に記載の液晶滴下工法用液晶シール剤。 The liquid crystal sealing agent for a liquid crystal dropping method according to claim 5, wherein the curable resin (b) is an epoxy (meth) acrylate.
- 前記硬化性樹脂(b)がレゾルシンジグリシジルエーテルとアクリル酸の反応生成物である請求項5に記載の液晶滴下工法用液晶シール剤。 The liquid crystal sealing agent for a liquid crystal dropping method according to claim 5, wherein the curable resin (b) is a reaction product of resorcin diglycidyl ether and acrylic acid.
- 更に(e)エポキシ樹脂、(f)熱硬化剤を含有する請求項5に記載の液晶滴下工法用液晶シール剤。 The liquid crystal sealing agent for a liquid crystal dropping method according to claim 5, further comprising (e) an epoxy resin and (f) a thermosetting agent.
- 更に(g)シランカップリング剤を含む、請求項5に記載の液晶滴下工法用液晶シール剤。 The liquid crystal sealing agent for liquid crystal dropping method according to claim 5, further comprising (g) a silane coupling agent.
- 更に(h)無機フィラーを含有する請求項5に記載の液晶滴下工法用液晶シール剤。 Furthermore, the liquid-crystal sealing compound for liquid crystal dropping methods of Claim 5 which contains an inorganic filler further (h).
- 液晶シール剤の全体に対して、前記光増感剤(a)を0.01~5質量%および前記硬化性樹脂(b)を30~80質量%含む請求項1に記載の液晶滴下工法用液晶シール剤。 The liquid crystal dropping method according to claim 1, comprising 0.01 to 5% by mass of the photosensitizer (a) and 30 to 80% by mass of the curable resin (b) with respect to the entire liquid crystal sealant. Liquid crystal sealant.
- 更に、(d)光重合開始剤を0.01~5質量%を含む請求項12に記載の液晶滴下工法用液晶シール剤。 The liquid crystal sealing agent for a liquid crystal dropping method according to claim 12, further comprising 0.01 to 5% by mass of (d) a photopolymerization initiator.
- 更に、(e)エポキシ樹脂を1~30質量%および(f)熱硬化剤をエポキシ樹脂のエポキシ基1当量に対して、0.5~2当量含有する請求項13に記載の液晶滴下工法用液晶シール剤。 The liquid crystal dropping method according to claim 13, further comprising (e) 1 to 30% by mass of an epoxy resin and (f) 0.5 to 2 equivalents of a thermosetting agent with respect to 1 equivalent of epoxy groups of the epoxy resin. Liquid crystal sealant.
- 更に(g)シランカップリング剤を0.05~3質量%および(h)無機フィラーを10~60質量%含有する請求項14に記載の液晶滴下工法用液晶シール剤。 15. The liquid crystal sealing agent for a liquid crystal dropping method according to claim 14, further comprising (g) 0.05 to 3% by mass of a silane coupling agent and (h) 10 to 60% by mass of an inorganic filler.
- 更に(c)3級アミン化合物を0~6質量%含有する請求項15に記載の液晶滴下工法用液晶シール剤。 The liquid crystal sealing agent for a liquid crystal dropping method according to claim 15, further comprising (c) a tertiary amine compound in an amount of 0 to 6% by mass.
- 請求項1乃至16の何れか1項に記載の液晶滴下工法用液晶シール剤を硬化して得られる硬化物でシールされた液晶表示セル。 A liquid crystal display cell sealed with a cured product obtained by curing the liquid crystal sealing agent for a liquid crystal dropping method according to any one of claims 1 to 16.
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JP2012525299A JP5651177B2 (en) | 2010-07-20 | 2011-06-14 | Liquid crystal sealant and liquid crystal display cell using the same |
CN201180035057XA CN103003742A (en) | 2010-07-20 | 2011-06-14 | Liquid crystal sealing agent and liquid crystal display cell using same |
KR1020127033462A KR20130140544A (en) | 2010-07-20 | 2011-06-14 | Liquid crystal sealing agent and liquid crystal display cell using same |
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Also Published As
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JPWO2012011220A1 (en) | 2013-09-09 |
CN103003742A (en) | 2013-03-27 |
JP5651177B2 (en) | 2015-01-07 |
KR20130140544A (en) | 2013-12-24 |
TW201204749A (en) | 2012-02-01 |
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