CN111656270A - Sealing agent for liquid crystal display element, vertical conduction material, and liquid crystal display element - Google Patents
Sealing agent for liquid crystal display element, vertical conduction material, and liquid crystal display element Download PDFInfo
- Publication number
- CN111656270A CN111656270A CN201980010330.XA CN201980010330A CN111656270A CN 111656270 A CN111656270 A CN 111656270A CN 201980010330 A CN201980010330 A CN 201980010330A CN 111656270 A CN111656270 A CN 111656270A
- Authority
- CN
- China
- Prior art keywords
- liquid crystal
- crystal display
- display element
- meth
- sealant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 150
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 59
- 239000000463 material Substances 0.000 title abstract description 13
- 238000007789 sealing Methods 0.000 title abstract description 6
- 239000000565 sealant Substances 0.000 claims abstract description 92
- 150000001875 compounds Chemical class 0.000 claims abstract description 69
- 229920005989 resin Polymers 0.000 claims abstract description 23
- 239000011347 resin Substances 0.000 claims abstract description 23
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 20
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 11
- -1 isocyanate compound Chemical group 0.000 claims description 68
- 239000012948 isocyanate Substances 0.000 claims description 21
- 229920001187 thermosetting polymer Polymers 0.000 claims description 16
- 239000010419 fine particle Substances 0.000 claims description 13
- 239000004020 conductor Substances 0.000 claims 2
- 238000001029 thermal curing Methods 0.000 claims 1
- 238000013007 heat curing Methods 0.000 abstract description 20
- 238000003860 storage Methods 0.000 abstract description 14
- 230000007547 defect Effects 0.000 abstract description 9
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- 239000004593 Epoxy Substances 0.000 description 40
- 239000003822 epoxy resin Substances 0.000 description 39
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- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
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- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
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- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
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- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
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- 230000001678 irradiating effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
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- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
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- 229920001515 polyalkylene glycol Polymers 0.000 description 1
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- 150000003077 polyols Chemical class 0.000 description 1
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- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
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- 229920002635 polyurethane Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
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- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
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- AMJYHMCHKZQLAY-UHFFFAOYSA-N tris(2-isocyanatophenoxy)-sulfanylidene-$l^{5}-phosphane Chemical compound O=C=NC1=CC=CC=C1OP(=S)(OC=1C(=CC=CC=1)N=C=O)OC1=CC=CC=C1N=C=O AMJYHMCHKZQLAY-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4028—Isocyanates; Thioisocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3823—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
- C08G18/3834—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing hydrazide or semi-carbazide groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
- C09K3/1021—Polyurethanes or derivatives thereof
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
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- Crystallography & Structural Chemistry (AREA)
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Abstract
The purpose of the present invention is to provide a sealing agent for a liquid crystal display element, which has excellent storage stability and curability, and which can suppress the occurrence of display defects even when used in a thin liquid crystal display element. Further, another object of the present invention is to provide a vertical conduction material and a liquid crystal display element using the sealant for a liquid crystal display element. The present invention is a sealant for a liquid crystal display element, which contains a curable resin and a heat-curing agent, wherein the heat-curing agent contains a compound (A) having the following characteristics (a), (b), (c) and (d), (a) having a hydroxyl-containing hydrazide compound residue, and (b) having an isocyanated groupA compound residue, (c) has a structure represented by the following formula (1), (d) has no isocyanate group, and ＊ is a bonding position in the formula (1),
Description
Technical Field
The present invention relates to a sealant for a liquid crystal display element, which has excellent storage stability and curability and can suppress the occurrence of display defects even when used for a thin liquid crystal display element. The present invention also relates to a vertical conduction material and a liquid crystal display element using the sealant for a liquid crystal display element.
Background
In recent years, as a method for manufacturing a liquid crystal display element such as a liquid crystal display unit, a liquid crystal dropping method called a dropping method using a sealing agent as disclosed in patent documents 1 and 2 has been used from the viewpoint of shortening the tact time and optimizing the amount of liquid crystal used.
In the one drop fill process, first, a frame-shaped seal pattern is formed on one of two substrates with electrodes by dispensing. Next, in a state where the sealant is not cured, fine droplets of liquid crystal are dropped into a frame of the seal pattern, another substrate is stacked under vacuum, and then the sealant is cured to fabricate a liquid crystal display element. This one drop fill process is currently the mainstream of a method for manufacturing a liquid crystal display element.
However, in the modern day in which various mobile devices with liquid crystal panels such as mobile phones and portable game machines are increasingly widespread, miniaturization of the devices is the most demanding issue. As a method for downsizing the device, narrowing of the frame of the liquid crystal display portion, for example, an operation of disposing the position of the sealing portion under the black matrix (hereinafter, also referred to as narrow frame design) is performed.
However, in the narrow-edge design, since the sealant is disposed directly below the black matrix, if the dropping process is performed, light irradiated when the sealant is photocured is blocked, and it is difficult for the light to reach the inside of the sealant, and the curing becomes insufficient in the conventional sealant. As described above, if the curing of the sealant becomes insufficient, there is a problem in that: the uncured sealant component is eluted into the liquid crystal, and liquid crystal contamination is likely to occur.
As described above, when it is difficult to cure the sealant by light, it is conceivable to cure the sealant by heating, and as a method for curing the sealant by heating, an operation of adding a thermosetting agent to the sealant is performed. However, when a heat curing agent having high reactivity to heat is used in order to improve curability of the sealant, storage stability of the resulting sealant may be deteriorated.
In addition, in recent years, thinning of a liquid crystal display element has been advanced, but when a conventional sealant is used for a thin liquid crystal display element, there is a problem that a display failure may occur.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2001-133794
Patent document 2: international publication No. 02/092718
Disclosure of Invention
Problems to be solved by the invention
The purpose of the present invention is to provide a sealing agent for a liquid crystal display element, which has excellent storage stability and curability, and which can suppress the occurrence of display defects even when used in a thin liquid crystal display element. Further, another object of the present invention is to provide a vertical conduction material and a liquid crystal display element using the sealant for a liquid crystal display element.
Means for solving the problems
The present invention is a sealant for a liquid crystal display element, comprising a curable resin and a heat-curing agent, wherein the heat-curing agent comprises a compound (A) having the following characteristics (a), (b), (c) and (d),
(a) having a hydroxyl group-containing hydrazide compound residue,
(b) Having an isocyanate compound residue,
(c) Having a structure represented by the following formula (1),
(d) Has no isocyanate group.
That is, the present invention is a sealant for a liquid crystal display element, comprising a curable resin and a heat-curing agent, wherein the heat-curing agent contains a compound having a hydroxyl group-containing hydrazide compound residue, an isocyanate compound residue, and a structure represented by the following formula (1) and having no isocyanate group.
In the formula (1), the bonding position is represented by the formula.
The present invention will be described in detail below.
In response to the thinning of liquid crystal display elements, the use of liquid crystals containing liquid crystal molecules having polar groups such as fluorine groups, chlorine groups, and cyano groups as liquid crystals is becoming increasingly common. The inventor considers that: the reason why a display failure occurs when a conventional sealant is used in a thin liquid crystal display element is that the liquid crystal containing liquid crystal molecules having a polar group as described above has high compatibility with the sealant (particularly, compatibility with a thermosetting agent contained in the sealant), and therefore liquid crystal contamination is likely to occur. Therefore, the present inventors have conducted intensive studies and, as a result, have found that: the present inventors have completed the present invention by providing a sealant for a liquid crystal display element, which has excellent storage stability and curability and can suppress the occurrence of display defects even when used for a thin liquid crystal display element, by using a heat curing agent having a specific structure.
In addition, since the sealant for a liquid crystal display element of the present invention is a sealant having lower compatibility with a conventional liquid crystal that does not include liquid crystal molecules having a polar group, it is possible to suppress the occurrence of display defects in a liquid crystal display element using such a conventional liquid crystal.
The sealant for a liquid crystal display element of the present invention contains a thermosetting agent.
The thermosetting agent includes the compound (a) having the above-described characteristics (a), (b), (c), and (d) (hereinafter, also referred to as "the thermosetting agent according to the present invention"). The sealant for a liquid crystal display element of the present invention is excellent in storage stability and curability by containing the heat-curing agent of the present invention, and can suppress the occurrence of display defects even when used for a thin liquid crystal display element.
In the present specification, the "residue" refers to: the structure of the portion other than the functional group to be bonded in the raw material component. Specifically, the "hydroxyl group-containing hydrazide compound residue" in the above feature (a) of the heat-curing agent of the present invention is: the structure derived from the hydroxyl group-containing hydrazide compound is a structure of a portion other than the hydrazide group in the hydroxyl group-containing hydrazide compound, that is, a structure of a portion remaining without reacting with the isocyanate group. In the feature (b) of the thermosetting agent of the present invention, the "isocyanate compound residue" means: the structure derived from the isocyanate compound is a structure of a portion other than the isocyanate group in the isocyanate compound, that is, a structure of a portion remaining without reacting with a hydrazide group. Since the heat-curing agent of the present invention has the above feature (d), that is, has no isocyanate group, all isocyanate groups of the isocyanate compound contribute to the formation of the structure represented by the above formula (1).
The hydroxyl group-containing hydrazide compound which is a source of the hydroxyl group-containing hydrazide compound residue in the above feature (a) is preferably a compound having a hydroxyl group and 2 or more hydrazide groups in 1 molecule, and the isocyanate compound which is a source of the isocyanate compound residue in the above feature (b) is preferably a compound having 2 or more isocyanate groups in 1 molecule.
The structure represented by the formula (1) in the above feature (c) is derived from a hydrazide group of the above hydroxyl group-containing hydrazide compound and an isocyanate group of the above isocyanate compound. The heat-curing agent of the present invention has the structure represented by formula (1), and thus the obtained sealant for a liquid crystal display element has an excellent effect of achieving both liquid crystal staining properties and curability.
Specific examples of the hydroxyl group-containing hydrazide compound include malic acid dihydrazide, tartaric acid dihydrazide, and 2-hydroxypropane-1, 2, 3-trimethylhydrazide. Among them, malic acid dihydrazide and tartaric acid dihydrazide are preferable.
Specific examples of the isocyanate compound include hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, and toluene diisocyanate. Among them, hexamethylene diisocyanate and isophorone diisocyanate are preferable.
The lower limit of the molecular weight of the thermosetting agent of the present invention is preferably 300. The molecular weight of the heat-curing agent of the present invention is 300 or more, so that the heat-curing agent has sufficient solubility in a curable resin, and the obtained sealant for a liquid crystal display element is more excellent in low liquid crystal contamination. A more preferred lower limit of the molecular weight of the heat-curing agent of the present invention is 350.
From the viewpoint of workability of the obtained sealant for a liquid crystal display element, the upper limit of the molecular weight of the thermosetting agent of the present invention is preferably 2000.
The molecular weight of the heat-curing agent of the present invention is determined by the structural formula for a compound having a definite molecular structure, and may be expressed by a weight average molecular weight for a compound having a wide distribution of polymerization degrees and a compound having an indefinite modified portion. In the present specification, the "weight average molecular weight" is a value obtained by measuring by Gel Permeation Chromatography (GPC) using tetrahydrofuran as a solvent and converting into polystyrene. Examples of the column used for measuring the weight average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko K.K.).
Specifically, the thermosetting agent of the present invention includes, for example, a compound represented by the following formula (2).
In the formula (2), R1Each independently is a hydroxyl group-containing hydrazide compound residue, R2Is the residue of an isocyanate compound.
Examples of the method for producing the thermosetting agent of the present invention include the following methods.
That is, first, the hydroxyl group-containing hydrazide compound was dissolved in toluene in a three-necked flask equipped with a thermometer and a stirrer, and stirred at 60 ℃. After the toluene solution of the isocyanate compound was added dropwise to the obtained solution, the mixture was stirred at 60 ℃ for 6 hours to effect a reaction. The thermosetting agent of the present invention can be obtained by filtering the obtained reaction solution to separate a solid, washing the obtained solid with water, and drying the washed solid.
The content of the heat-curing agent of the present invention is preferably 0.1 part by weight in the lower limit and 20 parts by weight in the upper limit, based on 100 parts by weight of the curable resin. When the content of the heat-curing agent of the present invention is 0.1 part by weight or more, the obtained sealant for a liquid crystal display element is more excellent in curability. By setting the content of the thermosetting agent of the present invention to 20 parts by weight or less, the storage stability of the obtained sealant for a liquid crystal display element becomes more excellent. The content of the thermosetting agent in the present invention is more preferably 1 part by weight at the lower limit, more preferably 18 parts by weight at the upper limit, still more preferably 2 parts by weight at the lower limit, still more preferably 15 parts by weight at the upper limit, still more preferably 3 parts by weight at the lower limit, still more preferably 12 parts by weight at the upper limit, particularly preferably 4 parts by weight at the lower limit, particularly preferably 10 parts by weight at the upper limit, and most preferably 8 parts by weight at the upper limit.
The sealant for a liquid crystal display element of the present invention contains a curable resin.
The curable resin preferably contains an epoxy compound.
Examples of the epoxy compound include bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, 2' -diallylbisphenol a type epoxy resin, hydrogenated bisphenol type epoxy resin, propylene oxide-added bisphenol a type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, thioether type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, o-cresol novolac type epoxy resin, dicyclopentadiene novolac type epoxy resin, biphenol novolac type epoxy resin, glycidylamine type epoxy resin, alkyl polyol type epoxy resin, rubber-modified epoxy resin, glycidyl ester compound, and the like.
Examples of commercially available products among the bisphenol A epoxy resins include jER828EL, jER1004 (both manufactured by Mitsubishi chemical corporation), and EPICLON850 (manufactured by DIC corporation).
Examples of commercially available products among the above bisphenol F-type epoxy resins include jER806, jER4004 (both manufactured by Mitsubishi chemical corporation), EPICLON EXA-830CRP (manufactured by DIC corporation), and the like.
Examples of commercially available products among the bisphenol E-type epoxy resins include EPMIC R710 (manufactured by Mitsui chemical Co., Ltd.).
As a commercially available product among the above bisphenol S type epoxy resins, EPICLON EXA-1514 (available from DIC) and the like can be mentioned.
Examples of commercially available products among the above-mentioned 2, 2' -diallylbisphenol A-type epoxy resins include RE-810NM (manufactured by Nippon chemical Co., Ltd.).
Examples of commercially available products among the above-mentioned hydrogenated bisphenol epoxy resins include EPICLON EXA-7015 (available from DIC).
Examples of commercially available products of the above propylene oxide-added bisphenol A epoxy resins include EP-4000S (manufactured by ADEKA).
Examples of commercially available products among the above resorcinol type epoxy resins include EX-201 (manufactured by Nagase ChemteX Corporation).
Examples of the products commercially available among the biphenyl type epoxy resins include jER YX-4000H (manufactured by Mitsubishi chemical corporation).
Examples of commercially available products among the above thioether-type epoxy resins include YSLV-50TE (NIPPON STEELchemical & Material Co., Ltd.).
Examples of commercially available products among the above diphenyl ether type epoxy resins include YSLV-80DE (manufactured by NIPPONSTEEL Chemical & Material Co., Ltd.).
Examples of commercially available products among the above-mentioned dicyclopentadiene type epoxy resins include EP-4088S (manufactured by ADEKA).
Examples of commercially available products among the naphthalene epoxy resins include EPICLON HP-4032 and EPICLONEXA-4700 (both available from DIC).
Examples of commercially available products among the above phenol novolac epoxy resins include EPICLON-770 (available from DIC).
Examples of commercially available products among the above o-cresol novolac type epoxy resins include EPICLON-670-EXP-S (available from DIC).
Examples of commercially available products among the dicyclopentadiene phenol type epoxy resins include EPICLON HP-7200 (available from DIC).
Examples of commercially available products among the above-mentioned diphenol aldehyde type epoxy resins include NC-3000P (manufactured by Nippon chemical Co., Ltd.).
Examples of commercially available products among the above naphthol novolac type epoxy resins include ESN-165S (NIPPONSTEEL Chemical & Material Co., Ltd.).
Examples of commercially available products among the glycidyl amine type epoxy resins include JeR630 (manufactured by Mitsubishi chemical corporation), EPICLON430 (manufactured by DIC corporation), and TETRAD-X (manufactured by Mitsubishi gas chemical corporation).
Examples of commercially available products among the above-mentioned alkyl polyol type epoxy resins include ZX-1542(NIPPONSTEEL Chemical & Material Co., Ltd., manufactured by Ltd.), EPICLON726 (manufactured by DIC Co., Ltd.), EPOLIGHT 80MFA (manufactured by Kyoho Chemical Co., Ltd.), DENACOL EX-611 (manufactured by Nagase ChemteX Corporation), and the like.
Examples of commercially available products among the rubber-modified epoxy resins include YR-450, YR-207 (both NIPPON STEEL Chemical & Material Co., Ltd.), EPOLEAD PB (manufactured by Daiiol Co., Ltd.), and the like.
Examples of commercially available products among the glycidyl ester compounds include DENACOL EX-147 (manufactured by Nagase ChemteX Corporation).
Examples of other commercially available products among the above epoxy compounds include YDC-1312, YSLV-80XY, YSLV-90CR (all NIPPON STEEL Chemical & Material Co., Ltd.), XAC4151 (manufactured by Asahi Kasei corporation), jER1031, jER1032 (all manufactured by Mitsubishi Chemical corporation), EXA-7120 (manufactured by DIC corporation), TEPIC (manufactured by Nissan Chemical corporation).
As the epoxy compound, a partially (meth) acrylic acid-modified epoxy resin is also suitably used.
In the present specification, the partial (meth) acrylic-modified epoxy resin means: a compound having one or more epoxy groups and (meth) acryloyl groups in 1 molecule, which is obtained by reacting a part of the epoxy groups of an epoxy compound having 2 or more epoxy groups with (meth) acrylic acid.
In the present specification, the "(meth) acrylic" means acrylic acid or methacrylic acid, and the "(meth) acryloyl" means acryloyl or methacryloyl.
Examples of commercially available products among the partially (meth) acrylic-modified epoxy resins include UVACURE1561 and KRM8287 (both manufactured by Daicel-Allnex LTD.).
The curable resin may contain a (meth) acrylic compound.
Examples of the (meth) acrylic compound include a (meth) acrylate compound, an epoxy (meth) acrylate, and a urethane (meth) acrylate. Among them, epoxy (meth) acrylates are preferable. From the viewpoint of reactivity, the (meth) acrylic compound preferably has 2 or more (meth) acryloyl groups in 1 molecule.
In the present specification, the "(meth) acrylic compound" refers to a compound having a (meth) acryloyl group. The "(meth) acrylate" refers to an acrylate or a methacrylate, and the "epoxy (meth) acrylate" refers to a compound obtained by reacting all epoxy groups in an epoxy compound with (meth) acrylic acid.
Examples of the monofunctional compound among the above-mentioned (meth) acrylate compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexyl (meth) acrylate, and mixtures thereof, Isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ethylcarbitol (meth) acrylate, 2, 2, 2-trifluoroethyl (meth) acrylate, 2, 2, 3, 3-tetrafluoropropyl (meth) acrylate, 1H, 5H-octafluoropentyl (meth) acrylate, and mixtures thereof, Imide (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxyethyl 2-hydroxypropyl phthalate, 2- (meth) acryloyloxyethyl phosphate, glycidyl (meth) acrylate, and the like.
Further, as the 2-functional compound among the above-mentioned (meth) acrylate compounds, there may be mentioned, for example, 1, 3-butanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2-n-butyl-2-ethyl-1, 3-propanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and mixtures thereof, Neopentyl glycol di (meth) acrylate, ethylene oxide-added bisphenol a di (meth) acrylate, propylene oxide-added bisphenol a di (meth) acrylate, ethylene oxide-added bisphenol F di (meth) acrylate, dimethylol dicyclopentadiene di (meth) acrylate, ethylene oxide-modified isocyanuric acid di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, carbonate diol di (meth) acrylate, polyether diol di (meth) acrylate, polyester diol di (meth) acrylate, polycaprolactone diol di (meth) acrylate, polybutadiene diol di (meth) acrylate, and the like.
Further, as the compound having 3 or more functions among the above (meth) acrylate compounds, examples thereof include trimethylolpropane tri (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, caprolactone-modified trimethylolpropane tri (meth) acrylate, ethylene oxide-added isocyanuric acid tri (meth) acrylate, glycerol tri (meth) acrylate, propylene oxide-added glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri (meth) acryloyloxyethyl phosphate, bis (trimethylolpropane) tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.
Examples of the epoxy (meth) acrylate include epoxy (meth) acrylates obtained by reacting an epoxy compound and (meth) acrylic acid in the presence of a basic catalyst according to a conventional method.
As the epoxy compound to be a raw material for synthesizing the epoxy (meth) acrylate, the same epoxy compound as the epoxy compound described as the curable resin contained in the sealant for a liquid crystal display element of the present invention can be used.
Examples of commercially available products among the above epoxy (meth) acrylates include epoxy (meth) acrylate manufactured by Daicel-Allnex LTD., epoxy (meth) acrylate manufactured by Ningmura chemical industries, epoxy (meth) acrylate manufactured by Kyowa chemical company, epoxy (meth) acrylate manufactured by Nagase ChemteX Corporation, and the like.
Examples of the epoxy (meth) acrylate produced by Daicel-Allnex LTD.include EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3708, EBECRYL3800, EBECRYL6040, and EBECRYL RDX 63182.
Examples of the epoxy (meth) acrylate manufactured by Nippon Komura chemical industries include EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD and EMA-1020.
Examples of the EPOXY (meth) acrylate produced by Kyoeisha chemical company include EPOXY ESTER M-600A, EPOXY ESTER 40EM, EPOXY ESTER 70PA, EPOXY ESTER 200PA, EPOXY ESTER 80MFA, EPOXY ESTER 3002M, EPOXY ESTER 3002A, EPOXY ESTER 1600A, EPOXY ESTER 3000M, EPOXYESTER 3000A, EPOXY ESTER 200EA and EPXY ESTER 400 EA.
Examples of the epoxy (meth) acrylate produced by Nagase ChemteX Corporation include DENACOL ACRYLATE DA-141, DENACOL ACRYLATE DA-314, and DENACOLACRYLATE DA-911.
The urethane (meth) acrylate can be obtained, for example, by reacting a (meth) acrylic acid derivative having a hydroxyl group with an isocyanate compound in the presence of a catalytic amount of a tin-based compound.
Examples of the isocyanate compound which becomes a raw material of the urethane (meth) acrylate include isophorone diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4, 4' -diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1, 5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, Xylylene Diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, tetramethylxylylene diisocyanate, 1, 6, 11-undecane triisocyanate, and the like.
Further, as the isocyanate compound which is a raw material of the urethane (meth) acrylate, an isocyanate compound in which a chain obtained by a reaction of a polyol and an excessive amount of the isocyanate compound is extended may be used.
Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, and polycaprolactone diol.
Examples of the (meth) acrylic acid derivative having a hydroxyl group include hydroxyalkyl mono (meth) acrylates, mono (meth) acrylates of diols, mono (meth) acrylates or di (meth) acrylates of triols, epoxy (meth) acrylates, and the like.
Examples of the hydroxyalkyl mono (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
Examples of the dihydric alcohol include ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 3-butanediol, 1, 4-butanediol, and polyethylene glycol.
Examples of the trihydric alcohol include trimethylolethane, trimethylolpropane, glycerol, and the like.
Examples of the epoxy (meth) acrylate include bisphenol a type epoxy acrylates and the like.
Examples of commercially available products among the above urethane (meth) acrylates include urethane (meth) acrylates manufactured by east asia synthesis, urethane (meth) acrylates manufactured by Daicel-Allnex ltd., urethane (meth) acrylates manufactured by kokai ltd., urethane (meth) acrylates manufactured by seiko industries, urethane (meth) acrylates manufactured by seiko chemical industries, urethane (meth) acrylates manufactured by coyowa chemical companies, and the like.
Examples of the urethane (meth) acrylates produced by Toyo Synthesis Co.Ltd include M-1100, M-1200, M-1210 and M-1600.
Examples of the urethane (meth) acrylate prepared by Daicel-Allnex LTD.include EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL4858, EBECRYL5129, EBECRYL6700, EBECRYL 8808402, EBECRYL8803, EBECRYL8804, EBECRYL8807 and EBECRYL 9260.
Examples of the urethane (meth) acrylates produced by the above-mentioned Geneva Industrial Co., Ltd include Art Resin UN-330, Art Resin SH-500B, Art Resin UN-1200TPK, Art Resin UN-1255, Art Resin UN-3320HB, Art Resin UN-7100, Art Resin UN-9000A and Art Resin UN-9000H.
Examples of the urethane (meth) acrylates produced by Nikamura chemical industries include U-2HA, U-2PHA, U-3HA, U-4HA, U-6H, U-6HA, U-6LPA, U-10H, U-15HA, U-108A, U-122A, U-122P, U-324A, U-340A, U-340P, U-1084A, U-2061BA, UA-340P, UA-4000, UA-4100, UA-4200, UA-4400, UA-5201P, UA-7100, UA-7200 and UA-W2A.
Examples of the urethane (meth) acrylate manufactured by Kyoeisha chemical company include AH-600, AI-600, AT-600, UA-101T, UA-101T, UA-306H, UA-306I, UA-306T, and the like.
When the curable resin contains the (meth) acrylic compound in addition to the epoxy compound or the partially (meth) acrylic-modified epoxy compound, the ratio of (meth) acryloyl groups in the total of epoxy groups and (meth) acryloyl groups in the curable resin is preferably 30 mol% or more and 95 mol% or less. When the ratio of the (meth) acryloyl group is in this range, the resultant sealant for a liquid crystal display element is more excellent in adhesiveness while suppressing the occurrence of liquid crystal contamination.
From the viewpoint of further suppressing liquid crystal contamination, the curable resin preferably has-OH group, -NH-group, or-NH group2Hydrogen bonding units such as radicals.
The sealant for a liquid crystal display element of the present invention preferably contains a radical polymerization initiator.
Examples of the radical polymerization initiator include a photo radical polymerization initiator which generates radicals by light irradiation and a thermal radical polymerization initiator which generates radicals by heating.
Examples of the photo radical polymerization initiator include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, and thioxanthone compounds.
Specific examples of the photo radical polymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2- (dimethylamino) -2- ((4-methylphenyl) methyl) -1- (4- (4-morpholinophenyl) -1-butanone, 2-dimethoxy-1, 2-diphenylethan-1-one, bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 1- (4- (2-hydroxyethoxy) -phenyl) -2-hydroxy- 2-methyl-1-propan-1-one, 1- (4- (phenylthio) phenyl) -1, 2-octanedione 2- (O-benzoyloxime), 2, 4, 6-trimethylbenzoyldiphenylphosphine oxide, and the like.
The photo radical polymerization initiator may be used alone, or 2 or more kinds may be used in combination.
Examples of the thermal radical polymerization initiator include thermal radical polymerization initiators composed of azo compounds, organic peroxides, and the like. Among them, from the viewpoint of suppressing liquid crystal contamination, an initiator composed of an azo compound (hereinafter, also referred to as "azo initiator") is preferable, and an initiator composed of a polymer azo compound (hereinafter, also referred to as "polymer azo initiator") is more preferable.
The thermal radical polymerization initiator may be used alone, or 2 or more kinds may be used in combination.
In the present specification, the "macromolecular azo compound" refers to a compound having an azo group, which generates a radical capable of curing a (meth) acryloyl group by heat, and which has a number average molecular weight of 300 or more.
The number average molecular weight of the macromolecular azo compound preferably has a lower limit of 1000 and an upper limit of 30 ten thousand. When the number average molecular weight of the macromolecular azo compound is in this range, the compound can be easily mixed with the curable resin while preventing adverse effects on the liquid crystal. The number average molecular weight of the macromolecular azo compound is preferably 5000 as a lower limit, more preferably 10 ten thousand as an upper limit, still more preferably 1 ten thousand as a lower limit, and yet more preferably 9 ten thousand as an upper limit.
In the present specification, the number average molecular weight is a value obtained by measuring by Gel Permeation Chromatography (GPC) using tetrahydrofuran as a solvent and converting into polystyrene. Examples of the column used for measuring the number average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko K.K.).
Examples of the macromolecular azo compound include compounds having a structure in which a plurality of units such as polyalkylene oxide and polydimethylsiloxane are bonded via an azo group.
The polymer azo compound having a structure in which a plurality of polyalkylene oxide units and the like are bonded to each other via an azo group is preferably a compound having a polyethylene oxide structure.
Specific examples of the macromolecular azo compound include a polycondensate of 4, 4 '-azobis (4-cyanovaleric acid) and a polyalkylene glycol, and a polycondensate of 4, 4' -azobis (4-cyanovaleric acid) and a polydimethylsiloxane having a terminal amino group.
Examples of commercially available products of the above-mentioned polymeric azo initiators include VPE-0201, VPE-0401, VPE-0601, VPS-0501 and VPS-1001 (all manufactured by Fuji film and Wako pure chemical industries, Ltd.).
Examples of the azo compound which is not a polymer include V-65 and V-501 (both manufactured by Fuji film and Wako pure chemical industries, Ltd.).
Examples of the organic peroxide include ketone peroxide, peroxyketal, hydrogen peroxide, dialkyl peroxide, peroxyester, diacyl peroxide, peroxydicarbonate, and the like.
The lower limit of the content of the radical polymerization initiator is preferably 0.1 part by weight and the upper limit is preferably 30 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the radical polymerization initiator is in this range, the obtained sealant for a liquid crystal display element is more excellent in storage stability and curability while suppressing contamination of liquid crystal. The content of the radical polymerization initiator is more preferably 1 part by weight at the lower limit, more preferably 10 parts by weight at the upper limit, and still more preferably 5 parts by weight at the upper limit.
The sealant for a liquid crystal display element of the present invention may contain a filler for the purpose of improving viscosity, improving adhesiveness by a stress dispersion effect, improving a linear expansion coefficient, improving moisture resistance of a cured product, and the like.
As the filler, an inorganic filler or an organic filler can be used.
Examples of the inorganic filler include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, smectite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, calcium carbonate, magnesium hydroxide, aluminum nitride, silicon nitride, barium sulfate, and calcium silicate.
Examples of the organic filler include polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, and acrylic polymer fine particles.
The fillers may be used alone, or 2 or more of them may be used in combination.
The lower limit of the content of the filler in 100 parts by weight of the sealant for a liquid crystal display element of the present invention is preferably 10 parts by weight, and the upper limit is preferably 70 parts by weight. When the content of the filler is in this range, the effect of improving the adhesiveness and the like can be further improved without deteriorating the coating property and the like. The lower limit of the content of the filler is more preferably 20 parts by weight, and the upper limit is more preferably 60 parts by weight.
The sealant for a liquid crystal display element of the present invention may contain a silane coupling agent. The silane coupling agent mainly functions as an adhesion aid for satisfactorily adhering the sealant to a substrate or the like.
As the silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane and the like are suitably used. These silane coupling agents have an excellent effect of improving adhesion to a substrate or the like, and are chemically bonded to a curable resin, thereby suppressing the outflow of the curable resin into a liquid crystal.
The silane coupling agents may be used alone, or 2 or more of them may be used in combination.
The content of the silane coupling agent in 100 parts by weight of the sealant for a liquid crystal display element of the present invention preferably has a lower limit of 0.1 part by weight and an upper limit of 10 parts by weight. When the content of the silane coupling agent is in this range, the effect of improving the adhesiveness is further enhanced while suppressing the occurrence of liquid crystal contamination. The lower limit of the content of the silane coupling agent is more preferably 0.3 part by weight, and the upper limit is more preferably 5 parts by weight.
The sealant for a liquid crystal display element of the present invention may contain a light-shading agent. By containing the light-shading agent, the sealant for a liquid crystal display element of the present invention can be suitably used as a light-shielding sealant.
Examples of the light-shading agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. Among them, titanium black is preferable.
The titanium black has a higher transmittance for light in the vicinity of the ultraviolet region, particularly at a wavelength of 370nm to 450nm, than the average transmittance for light at a wavelength of 300nm to 800 nm. That is, the titanium black is a light-shading agent having the following properties: the sealant for a liquid crystal display element of the present invention is provided with light-shielding properties by sufficiently shielding light having a wavelength in the visible light region, while transmitting light having a wavelength in the vicinity of the ultraviolet region. Therefore, by using an initiator that can initiate a reaction by light having a wavelength at which the transmittance of the titanium black is high as the photo radical polymerization initiator, the photocurability of the sealant for a liquid crystal display element of the present invention can be further increased. On the other hand, the light-shading agent contained in the sealant for a liquid crystal display element of the present invention is preferably a high-insulating material, and titanium black is also suitable as a high-insulating light-shading agent.
The optical density (OD value) of the titanium black per 1 μm is preferably 3 or more, and more preferably 4 or more. The higher the light-shielding property of the titanium black, the better, and the preferable upper limit of the OD value of the titanium black is not particularly limited, but is usually 5 or less.
The above titanium black exhibits a sufficient effect without being surface-treated, but titanium black whose surface is treated with an organic component such as a coupling agent, or titanium black whose surface is coated with an inorganic component such as silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, or magnesium oxide, or the like, may be used. Among them, titanium black treated with an organic component is preferable from the viewpoint of further improving the insulation properties.
Further, since a liquid crystal display element produced using the sealant for a liquid crystal display element of the present invention containing the titanium black as a light-shielding agent has sufficient light-shielding properties, it is possible to realize: a liquid crystal display element having high contrast without light leakage and excellent image display quality.
Examples of commercially available products among the above titanium blacks include titanium black manufactured by mitsubishi integrated materials corporation, and titanium black manufactured by gibberella chemical corporation.
Examples of the titanium black manufactured by Mitsubishi Integrated materials include 12S, 13M-C, 13R-N and 14M-C.
Examples of the titanium black manufactured by red spike formation company include Tilack D.
The lower limit of the specific surface area of the titanium black is preferably 13m2A preferred upper limit of 30 m/g2A more preferred lower limit is 15m2A more preferred upper limit is25m2/g。
The volume resistance of the titanium black is preferably 0.5 Ω · cm at the lower limit, 3 Ω · cm at the upper limit, 1 Ω · cm at the lower limit, and 2.5 Ω · cm at the upper limit.
The primary particle size of the light-shading agent is not particularly limited as long as it is not more than the distance between the substrates of the liquid crystal display element, and the lower limit is preferably 1nm, and the upper limit is preferably 5000 nm. By setting the primary particle size of the light-shielding agent in this range, the light-shielding property can be further improved without deteriorating the coatability and the like of the obtained sealant for a liquid crystal display element. The lower limit of the primary particle diameter of the light-shading agent is more preferably 5nm, the upper limit is more preferably 200nm, the lower limit is more preferably 10nm, and the upper limit is more preferably 100 nm.
The primary particle size of the light-shading agent can be measured by dispersing the light-shading agent in a solvent (water, organic solvent, etc.) using NICOMP 380ZLS (manufactured by particleasing SYSTEMS).
The content of the light-shading agent in 100 parts by weight of the sealant for liquid crystal display elements of the present invention preferably has a lower limit of 5 parts by weight and an upper limit of 80 parts by weight. When the content of the light-shading agent is within this range, the obtained sealant for a liquid crystal display element can exhibit more excellent light-shading properties without significantly reducing the adhesiveness, strength after curing, and drawing properties of the sealant. The content of the light-shading agent is more preferably 10 parts by weight at the lower limit, more preferably 70 parts by weight at the upper limit, still more preferably 30 parts by weight at the lower limit, and still more preferably 60 parts by weight at the upper limit.
The sealant for a liquid crystal display element of the present invention may further contain additives such as a stress relaxation agent, a reactive diluent, a thixotropic agent, a spacer, a curing accelerator, an antifoaming agent, a leveling agent, and a polymerization inhibitor, as required.
Examples of the method for producing the sealant for a liquid crystal display element of the present invention include a method of mixing a curable resin, a thermosetting agent, and a radical polymerization initiator added as needed, using a mixer.
Examples of the mixer include a homomixer, a universal mixer, a planetary mixer, a kneader, and a triple roll mill.
By adding conductive fine particles to the sealant for a liquid crystal display element of the present invention, a vertical conduction material can be produced. The vertical conduction material containing the sealant for a liquid crystal display element of the present invention and conductive fine particles is also one aspect of the present invention.
As the conductive fine particles, for example, metal balls, fine particles in which a conductive metal layer is formed on the surface of resin fine particles, or the like can be used. Among these, fine particles having a conductive metal layer formed on the surface of the resin fine particles are preferable because the resin fine particles have excellent elasticity and can be electrically connected without damaging the transparent substrate or the like.
A liquid crystal display element using the sealant for a liquid crystal display element of the present invention or the vertical conduction material of the present invention is also one aspect of the present invention.
Since the sealant for a liquid crystal display element of the present invention has low compatibility with liquid crystal molecules having a polar group, the sealant has a more significant effect of suppressing display defects than conventional sealants when the liquid crystal display element of the present invention is a liquid crystal display element using a liquid crystal containing liquid crystal molecules having a polar group. That is, the liquid crystal display element of the present invention is preferably formed using a liquid crystal containing liquid crystal molecules having a polar group.
Examples of the polar group of the liquid crystal molecule include a fluoro group, a chloro group, and a cyano group.
The liquid crystal display element of the present invention is preferably a narrow-frame liquid crystal display element. Specifically, the width of the frame portion around the liquid crystal display unit is preferably 2mm or less.
The coating width of the sealant for a liquid crystal display element of the present invention when the liquid crystal display element of the present invention is manufactured is preferably 1mm or less.
The sealant for a liquid crystal display element of the present invention can be suitably used for manufacturing a liquid crystal display element by a liquid crystal dropping process.
Examples of a method for manufacturing the liquid crystal display element of the present invention by a liquid crystal dropping method include the following methods.
First, a step of forming a frame-shaped seal pattern of the sealant for a liquid crystal display element of the present invention on a substrate by screen printing, dispenser application, or the like is performed. Next, a step of applying fine droplets of liquid crystal dropwise to the entire surface of the frame of the seal pattern in an uncured state of the sealant for a liquid crystal display element of the present invention and immediately stacking the other substrate is performed. Then, a liquid crystal display element can be obtained by a method of performing a step of heating and curing the sealant. Further, before the step of heating and curing the sealant, a step of pre-curing the sealant by irradiating the seal pattern portion with light such as ultraviolet rays may be performed.
Effects of the invention
According to the present invention, a sealant for a liquid crystal display element which is excellent in storage stability and curability and can suppress the occurrence of display defects even when used for a thin liquid crystal display element can be provided. Further, according to the present invention, a vertical conduction material and a liquid crystal display element using the sealant for a liquid crystal display element can be provided.
Detailed Description
The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.
(Synthesis of Compound A)
In a three-necked flask equipped with a thermometer and a stirrer, 16.2 parts by weight of malic acid dihydrazide was dissolved in 100 parts by weight of toluene, and the mixture was stirred at 60 ℃. To the resulting solution was added dropwise a solution prepared by dissolving 3.4 parts by weight of hexamethylene diisocyanate in 50 parts by weight of toluene at a dropping rate of 5mL/min, followed by stirring at 60 ℃ for 6 hours to effect a reaction. The obtained reaction solution was filtered to separate a solid, and the obtained solid was washed with water and dried to obtain compound a as a thermosetting agent according to the present invention.
It was confirmed by MS and FT-IR that: the resulting compound A is of the formula(2) A compound represented by (R)1Is a malic acid dihydrazide residue, R2Is a hexamethylene diisocyanate residue).
(Synthesis of Compound B)
Compound B, which is a heat-curing agent of the present invention, was obtained in the same manner as in the above "(synthesis of compound a)" except that 16.2 parts by weight of malic acid dihydrazide was changed to 17.8 parts by weight of tartaric acid dihydrazide.
Note that, from MS and FT-IR, it was confirmed that: the obtained compound B is a compound (R) represented by the formula (2)1Is tartaric acid dihydrazide residue, R2Is a hexamethylene diisocyanate residue).
(Synthesis of Compound C)
Compound C as the heat-curing agent of the present invention was obtained in the same manner as in the above "(synthesis of compound a)", except that 3.4 parts by weight of hexamethylene diisocyanate was changed to 4.4 parts by weight of isophorone diisocyanate.
Note that, from MS and FT-IR, it was confirmed that: the obtained compound C is a compound (R) represented by the formula (2)1Is a malic acid dihydrazide residue, R2Is an isophorone diisocyanate residue).
(Synthesis of Compound D)
Compound D, which is a compound having a hydrazide compound residue containing no hydroxyl group and an isocyanate compound residue, was obtained in the same manner as in the above "(synthesis of compound a)" except that 16.2 parts by weight of malic acid dihydrazide was changed to 13.2 parts by weight of malonic acid dihydrazide.
It was confirmed by MS and FT-IR that: the obtained compound D is the same as R in the formula (2)1The equivalent part is the residue of malonic acid dihydrazide and R2A substantial portion is a hexamethylene diisocyanate residue.
(examples 1 to 9 and comparative examples 1 to 4)
The respective materials were mixed with a planetary mixer (manufactured by Thinky, "ぁわとり tailang") according to the mixing ratios shown in tables 1 and 2, and then mixed with a three-roll mill to prepare the respective sealants for liquid crystal display elements of examples 1 to 9 and comparative examples 1 to 4.
< evaluation >
The following evaluations were performed on the sealants for liquid crystal display elements obtained in examples and comparative examples. The results are shown in tables 1 and 2.
(storage stability)
The sealant for liquid crystal display elements obtained in examples and comparative examples was measured for initial viscosity immediately after production and viscosity after 48 hours of storage in an atmosphere of 25 ℃ and 50% RH after production. Storage stability was evaluated by assuming that (viscosity after storage)/(initial viscosity) was a thickening ratio, assuming that the thickening ratio was less than 1.2 as "o", assuming that the thickening ratio was 1.2 or more and less than 1.3 as "Δ", and assuming that the thickening ratio was 1.3 or more as "x".
The viscosity of the sealant was measured at 25 ℃ and a rotation speed of 1.0rpm using an E-type viscometer (manufactured by BROOK FIELD, "DV-III").
(curing Property)
Each of the liquid crystal display elements obtained in examples and comparative examples was spot-coated with a sealant on one of 2 transparent substrates, the other transparent substrate was overlapped, and then irradiated with 100mW/cm using a metal halide lamp2Ultraviolet light for 30 seconds. Then, the resultant was heated at 120 ℃ for 1 hour to thermally cure the sealant for liquid crystal display element. The transparent substrate was peeled off, the cured product remaining on the transparent substrate was measured by an infrared spectrometer (available from Agilent Technologies, Inc. "UMA 600"), and the curing rate was calculated from the measurement result obtained and the measurement result before curing, which was measured in advance, by the following formula.
Curing ratio (%) < 100 × (1- (peak area of epoxy group after curing)/(peak area of epoxy group before curing))
Curability was evaluated by assuming that the curing rate was 90% or more as "o", that the curing rate was 70% or more and less than 90% as "Δ", and that the curing rate was less than 70% as "x".
(display Property of liquid Crystal display element)
Each of the liquid crystal display element sealants obtained in examples and comparative examples was applied to one of the two substrates with the polished alignment film and the transparent electrode by a dispenser so as to draw a square frame, thereby forming a seal pattern. A sealant for a liquid crystal display element is applied in dots on the inner side of the formed seal pattern.
Next, a minute droplet of liquid crystal (manufactured by tokyo chemical industry, "4-pentyl-4-biphenylcarbonitrile") containing liquid crystal molecules having a cyano group as a polar group was dropped onto the entire surface of the frame of the sealant applied to the substrate with the transparent electrode, and the other substrate was stacked in a vacuum. After the vacuum was released, the sealed portion of the outer frame was irradiated with 100mW/cm using a metal halide lamp2Ultraviolet light for 30 seconds. At this time, a mask is provided for the dot-coated sealant for liquid crystal display element so as not to be irradiated with ultraviolet rays. Then, liquid crystal annealing was performed at 120 ℃ for 1 hour to thermally cure the sealant for liquid crystal display element, thereby obtaining a liquid crystal display element.
After the obtained liquid crystal display element was applied with a voltage for 500 hours in an environment of 60 ℃ and 90% RH, disturbance of liquid crystal alignment (display unevenness) around the dispensed sealant for the liquid crystal display element was visually observed in the energized state.
"x" indicates a case where no display unevenness occurs; a case where the display unevenness occurred but disappeared immediately after the occurrence was assumed to be "o"; "Δ" represents a case where the display unevenness with a distance to the seal edge of 1mm or less remained; the display performance of the liquid crystal display element was evaluated by setting "x" to the case where the display unevenness was left with a distance of more than 1mm to the seal edge.
[ Table 1]
[ Table 2]
Industrial applicability
The present invention can provide a sealant for a liquid crystal display element, which has excellent storage stability and curability and can suppress the occurrence of display defects even when used for a thin liquid crystal display element. Further, according to the present invention, a vertical conduction material and a liquid crystal display element using the sealant for a liquid crystal display element can be provided.
Claims (6)
1. A sealant for a liquid crystal display element, comprising a curable resin and a thermosetting agent, wherein,
the thermal curing agent contains a compound (A) having the following characteristics (a), (b), (c) and (d),
(a) having a hydroxyl group-containing hydrazide compound residue,
(b) Having an isocyanate compound residue,
(c) Having a structure represented by the following formula (1),
(d) Having no isocyanate group, a high molecular weight,
in the formula (1), the bonding position is represented by the formula.
2. The sealant for a liquid crystal display element according to claim 1, wherein the hydroxyl group-containing hydrazide compound which is a source of the hydroxyl group-containing hydrazide compound residue in the feature (a) is a compound having a hydroxyl group and 2 or more hydrazide groups in 1 molecule, and,
the isocyanate compound which is a source of the isocyanate compound residue in the feature (b) is a compound having 2 or more isocyanate groups in 1 molecule.
3. The sealant for a liquid crystal display element according to claim 1 or 2, wherein a content of the compound (a) is 0.1 part by weight or more and 20 parts by weight or less in 100 parts by weight of the curable resin.
4. A vertically conducting material comprising the sealant for liquid crystal display element according to claim 1, 2 or 3 and conductive fine particles.
5. A liquid crystal display element, which is obtained by using the sealant for a liquid crystal display element according to claim 1, 2 or 3 or the vertically conducting material according to claim 4.
6. The liquid crystal display element according to claim 5, which is formed using a liquid crystal containing liquid crystal molecules having a polar group.
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| JP2018-100692 | 2018-05-25 | ||
| JP2018100692 | 2018-05-25 | ||
| PCT/JP2019/018916 WO2019225376A1 (en) | 2018-05-25 | 2019-05-13 | Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element |
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| TWI813686B (en) | 2023-09-01 |
| CN111656270B (en) | 2024-06-21 |
| WO2019225376A1 (en) | 2019-11-28 |
| TW202003623A (en) | 2020-01-16 |
| KR20210012994A (en) | 2021-02-03 |
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