CN113874462A - 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
- CN113874462A CN113874462A CN202080037785.3A CN202080037785A CN113874462A CN 113874462 A CN113874462 A CN 113874462A CN 202080037785 A CN202080037785 A CN 202080037785A CN 113874462 A CN113874462 A CN 113874462A
- Authority
- CN
- China
- Prior art keywords
- liquid crystal
- crystal display
- display element
- meth
- acrylate
- 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 158
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 35
- 239000000463 material Substances 0.000 title abstract description 13
- 238000007789 sealing Methods 0.000 title description 5
- 239000000565 sealant Substances 0.000 claims abstract description 104
- 150000001875 compounds Chemical class 0.000 claims abstract description 100
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 23
- 229920005989 resin Polymers 0.000 claims abstract description 21
- 239000011347 resin Substances 0.000 claims abstract description 21
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 8
- 238000013007 heat curing Methods 0.000 claims abstract description 7
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- 239000007870 radical polymerization initiator Substances 0.000 claims description 16
- 239000010419 fine particle Substances 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 229920001187 thermosetting polymer Polymers 0.000 claims description 5
- 239000004020 conductor Substances 0.000 claims 2
- 238000011109 contamination Methods 0.000 abstract description 20
- 238000003860 storage Methods 0.000 abstract description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 126
- -1 amine compounds Chemical class 0.000 description 63
- 239000003822 epoxy resin Substances 0.000 description 41
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- 230000015572 biosynthetic process Effects 0.000 description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 239000000758 substrate Substances 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
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Classifications
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
- C09J163/10—Epoxy resins modified by unsaturated compounds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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Abstract
The purpose of the present invention is to provide a sealant for a liquid crystal display element, which has excellent storage stability, adhesion, and low liquid crystal contamination. Further, an 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, comprising a curable resin and a heat-curing agent, wherein the heat-curing agent comprises a hydrazide compoundThe hydrazide compound has a structure represented by the following formula (1-1) and a structure represented by the following formula (1-2). In the formula (1-1), Ar is an aromatic ring, and in the formula (1-2), R1Is a hydrogen atom or a methyl group.
Description
Technical Field
The present invention relates to a sealant for a liquid crystal display element, which is excellent in storage stability, adhesiveness, and low liquid crystal contamination. 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, and another substrate is stacked under vacuum, and then the sealant is cured to produce a liquid crystal display element. This one drop fill process is now the mainstream of a method for manufacturing a liquid crystal display element.
However, in the modern times of widespread use of various mobile devices with liquid crystal panels such as mobile phones and portable game machines, the greatest challenge is to reduce the size of the devices. As a method for downsizing the device, a narrow frame of a liquid crystal display portion is given, and for example, a position of a sealing portion is disposed under a black matrix (hereinafter, also referred to as a narrow frame design).
However, in the narrow bezel design, since the sealant is disposed directly below the black matrix, when the one-drop process is performed, light irradiated when the sealant is photocured is blocked, and the light does not easily reach the inside of the sealant, and thus the conventional sealant is not cured sufficiently. As described above, if the curing of the sealant is insufficient, there is a problem that uncured sealant components are eluted into the liquid crystal and liquid crystal contamination is likely to occur. In particular, in recent years, along with the increase in the polarity of liquid crystals, a sealant is required to have further low liquid crystal contamination.
When it is difficult to photocure the sealant, it is considered 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 highly reactive heat-curing agent is used to improve curability and adhesiveness of the sealant, the storage stability of the resulting sealant may be deteriorated.
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 sealant for a liquid crystal display element, which has excellent storage stability, adhesion, and low liquid crystal contamination. Further, an 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 thermal curing agent, wherein the thermal curing agent comprises a hydrazide compound having a structure represented by the following formula (1-1) and a structure represented by the following formula (1-2).
[ solution 1]
In the formula (1-1), Ar is an aromatic ring, and in the formula (1-2), R1Is a hydrogen atom or a methyl group.
The present invention will be described in detail below.
The inventors of the present invention have conducted extensive studies and found that: by using a thermosetting agent having a specific structure, a sealant for a liquid crystal display element excellent in storage stability, adhesiveness, and low liquid crystal contamination can be obtained, and the present invention has been completed.
The sealant for a liquid crystal display element of the present invention contains a thermosetting agent.
The heat-curing agent contains a hydrazide compound.
The hydrazide compound has a structure represented by the formula (1-1) and a structure represented by the formula (1-2). Hereinafter, the hydrazide compound having the structure represented by the above formula (1-1) and the structure represented by the above formula (1-2) is also referred to as "the hydrazide compound of the present invention". The inclusion of the hydrazide compound of the present invention provides a sealant for a liquid crystal display element which is excellent in all of storage stability, adhesiveness, and low liquid crystal contamination.
The reason why the sealant for a liquid crystal display element obtained by using the hydrazide compound of the present invention is excellent in all of storage stability, adhesiveness, and low liquid crystal contamination is considered as follows.
Namely, it is considered that: by having the structure represented by the above formula (1-1), the softening point of the hydrazide compound can be controlled, and thus the storage stability can be improved. In addition, it can be considered that: by having the structure represented by the above formula (1-2) containing a primary amino group, the adhesiveness of the obtained sealant can be improved. Further, it can be considered that: by having such a structure, the molecular weight of the hydrazide compound becomes high, and thereby elution into the liquid crystal can be suppressed.
The hydrazide compound of the present invention has a preferable lower limit of the proportion of the structure represented by formula (1-1) of 5 mol% and a preferable upper limit of "" 95 mol%. By setting the proportion of the structure represented by the above formula (1-1) to 5 mol% or more, the obtained sealant for a liquid crystal display element is more excellent in storage stability. By setting the proportion of the structure represented by the above formula (1-1) to 95 mol% or less, the obtained sealant for a liquid crystal display element is more excellent in adhesiveness. A more preferable lower limit of the proportion of the structure represented by the above formula (1-1) is 10 mol%, a more preferable upper limit is 90 mol%, and a further more preferable upper limit is 50 mol%.
The ratio of the structure represented by the above formula (1-2) in the hydrazide compound of the present invention has a preferable lower limit of 5 mol% and a preferable upper limit of 95 mol%. By setting the proportion of the structure represented by the above formula (1-2) to 5 mol% or more, the obtained sealant for a liquid crystal display element is more excellent in adhesiveness. By setting the proportion of the structure represented by the above formula (1-2) to 95 mol% or less, the obtained sealant for a liquid crystal display element is more excellent in storage stability. A more preferable lower limit of the proportion of the structure represented by the above formula (1-2) is 10 mol%, a more preferable upper limit is 90 mol%, and a further preferable lower limit is 50 mol%.
The hydrazide compound of the present invention may have other structures in addition to the structure represented by the above formula (1-1) and the structure represented by the above formula (1-2).
The hydrazide compound of the present invention preferably further has a structure represented by the following formula (2) as the other structure. By having the structure represented by the following formula (2), the obtained sealant for a liquid crystal display element is more excellent in adhesiveness.
[ solution 2]
In the formula (2), R2Is a hydrogen atom or a methyl group, R3is-C (═ O) OR4Group (R)4Hydrogen atom OR alkyl group having 1 to 10 carbon atoms), -CN group, -OR5Group (R)5An alkyl group having 1 to 10 carbon atoms), or a hydrogen atom.
The hydrazide compound of the present invention has a preferable lower limit of the weight average molecular weight of 2000 and a preferable upper limit of 20 ten thousand. By making the weight average molecular weight 2000 or more, the obtained sealant for a liquid crystal display element is more excellent in low liquid crystal contamination. By setting the weight average molecular weight to 20 ten thousand or less, the obtained sealant for a liquid crystal display element is more excellent in handling property. The lower limit of the weight average molecular weight is more preferably 4000, and the upper limit is more preferably 10 ten thousand.
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 for measuring the weight average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko K.K.).
The preferred lower limit of the softening point of the hydrazide compound of the present invention is 65 ℃ and the preferred upper limit is 200 ℃. By setting the softening point of the hydrazide compound of the present invention to 65 ℃ or higher, the obtained sealant for a liquid crystal display element is more excellent in storage stability. By setting the softening point of the hydrazide compound of the present invention to 200 ℃ or lower, the obtained sealant for a liquid crystal display element is more excellent in adhesiveness. A more preferred lower limit of the softening point of the hydrazide compound of the present invention is 90 ℃ and a more preferred upper limit is 160 ℃.
The softening point can be determined by the ring and ball method in accordance with JIS K2207.
Examples of the method for producing the hydrazide compound of the present invention include the following methods.
That is, first, a compound represented by the following formula (3-1) and a compound represented by the following formula (3-2) are dissolved in a solvent such as tetrahydrofuran, and the resulting solution is reacted with stirring while heating in the presence of a polymerization initiator such as azobisisobutyronitrile and the like while performing nitrogen substitution. The obtained reaction product was concentrated and then reprecipitated in an ethanol solution to obtain an intermediate polymer compound. The obtained intermediate polymer compound and hydrazine hydrate are dissolved in a solvent such as tetrahydrofuran, and reacted under reflux. After the reaction is completed, the reaction mixture is concentrated to separate the solid component, whereby the hydrazide compound of the present invention can be obtained.
In addition, in addition to the compound represented by the following formula (3-1) and the compound represented by the following formula (3-2), a compound represented by the following formula (4) may be used.
[ solution 3]
In the formula (3-1), Ar is an aromatic ring, and in the formula (3-2), R1Is a hydrogen atom or a methyl group, R6An alkyl group having 1 to 10 carbon atoms.
[ solution 4]
In the formula (4), R2Is a hydrogen atom or a methyl group, R3is-C (═ O) OR4Group (R)4Hydrogen atom OR alkyl group having 1 to 10 carbon atoms), -CN group, -OR5Group (R)5An alkyl group having 1 to 10 carbon atoms), or a hydrogen atom.
The content of the hydrazide compound of the present invention is preferably 1 part by weight at the lower limit and 20 parts by weight at the upper limit with respect to 100 parts by weight of the curable resin. By setting the content of the hydrazide compound of the present invention to 1 part by weight or more, the obtained sealant for a liquid crystal display element is more excellent in curability and adhesiveness. By setting the content of the hydrazide compound of the present invention to 20 parts by weight or less, the obtained sealant for a liquid crystal display element is more excellent in storage stability and low liquid crystal contamination. The more preferable lower limit of the content of the hydrazide compound of the present invention is 2 parts by weight, and the more preferable upper limit is 15 parts by weight.
The sealant for a liquid crystal display element of the present invention may contain other heat curing agents in addition to the hydrazide compound of the present invention within a range not to impair the object of the present invention.
Examples of the heat-curing agent include organic acid hydrazides, imidazole derivatives, amine compounds, polyphenol compounds, and acid anhydrides.
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 of the bisphenol A epoxy resin include jER828EL, jER1004 (both manufactured by Mitsubishi chemical corporation), EPICLON850 (manufactured by DIC corporation), and the like.
Examples of commercially available products of the bisphenol F type epoxy resin include jER806, jER4004 (both manufactured by Mitsubishi chemical corporation), EPICLON EXA-830CRP (manufactured by DIC corporation), and the like.
Examples of commercially available products of the bisphenol E epoxy resin include EPOMIK R710 (manufactured by mitsui chemical corporation).
Examples of commercially available products of the bisphenol S type epoxy resin include EPICLON EXA-1514 (available from DIC).
Examples of commercially available products of the 2, 2' -diallylbisphenol A-type epoxy resin include RE-810NM (manufactured by Nippon chemical Co., Ltd.).
Examples of commercially available products of the hydrogenated bisphenol epoxy resin include EPICLON EXA-7015 (available from DIC).
Examples of commercially available products of the above propylene oxide-added bisphenol A epoxy resin include EP-4000S (manufactured by ADEKA).
Examples of commercially available products of the above resorcinol type epoxy resins include EX-201 (manufactured by Nagase ChemteX Corporation).
Examples of the commercially available biphenyl-type epoxy resin include jER YX-4000H (manufactured by mitsubishi chemical corporation).
Examples of commercially available products of the thioether-type epoxy resin include YSLV-50TE (manufactured by NIPPON STEEL Chemical & Material Co., Ltd.).
Examples of commercially available products of the above diphenyl ether type epoxy resins include YSLV-80DE (manufactured by NIPPON STEEL Chemical & Material Co., Ltd.).
Examples of commercially available products of the above-mentioned dicyclopentadiene type epoxy resin include EP-4088S (manufactured by ADEKA).
Examples of the naphthalene epoxy resin include EPICLON HP-4032 and EPICLON EXA-4700 (both available from DIC).
Examples of the commercially available phenol novolac epoxy resin include EPICLON-770 (available from DIC).
Examples of the commercially available products of the o-cresol novolac-type epoxy resin include EPICLON-670-EXP-S (available from DIC).
Examples of commercially available products of the dicyclopentadiene phenol type epoxy resin include EPICLON HP-7200 (available from DIC).
Examples of the commercially available products of the above-mentioned diphenolaldehyde type epoxy resin include NC-3000P (manufactured by Nippon chemical Co., Ltd.).
Examples of commercially available products of the naphthol novolac type epoxy resins include ESN-165S (manufactured by NIPPON STEEL Chemical & Material Co., Ltd.).
Examples of commercially available products of the glycidyl amine type epoxy resin 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 of the above-mentioned alkyl polyol type epoxy resin include ZX-1542(NIPPON STEEL Chemical & Material Co., Ltd.), EPICLON726(DIC Co., Ltd.), Eplight 80MFA (Kyoho Chemical Co., Ltd.), Denacol EX-611(Nagase ChemteX Corporation) and the like.
Examples of commercially available products of the rubber-modified epoxy resin include YR-450, YR-207 (both NIPPON STEEL Chemical & Material Co., Ltd.), EpoleedPB (DAICEL Co., Ltd.), and the like.
Examples of commercially available products of the glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase ChemteX Corporation).
Examples of other commercially available products of the above epoxy compounds include YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by NIPPON STEEL Chemical & Material Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Co., Ltd.), jER1031, jER1032 (all manufactured by Mitsubishi Chemical Co., Ltd.), EXA-7120 (manufactured by Nissan Chemical Co., Ltd.), TEPIC (manufactured by Nissan Chemical Co., Ltd.).
As the epoxy compound, a partially (meth) acrylic acid-modified epoxy resin can also be suitably used.
In the present specification, the term "partially (meth) acrylic-modified epoxy resin" means: a compound having 1 or more epoxy groups and 1 or more (meth) acryloyl groups in 1 molecule, respectively, 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 term "(meth) acrylic" refers to acrylic acid or methacrylic acid, and the term "(meth) acryloyl" refers to acryloyl or methacryloyl.
Examples of commercially available products of the partially (meth) acrylic-modified epoxy resin include UVACURE1561 and KRM8287 (both manufactured by DAICEL ALLNEX).
The curable resin may contain a (meth) acrylic compound.
Examples of the (meth) acrylic compound include: (meth) acrylate compounds, epoxy (meth) acrylates, urethane (meth) acrylates, and the like. Among them, epoxy (meth) acrylates are preferable. From the viewpoint of reactivity, the (meth) acrylic compound is preferably a compound having 2 or more (meth) acryloyl groups in 1 molecule.
In the present specification, the "(meth) acrylic compound" means 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 in the (meth) acrylate compound include: methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-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, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-butyl (meth) acrylate, n-butyl (2-butyl (meth) acrylate, n-butyl (acrylate, n-butyl (2-butyl acrylate, n-butyl (meth) acrylate, n-butyl acrylate, n-butyl (meth) acrylate, n-butyl acrylate, n-butyl (meth) acrylate, n-butyl (meth) acrylate, n-butyl acrylate, n-butyl (meth) acrylate, n-butyl (2-acrylate, n-butyl acrylate, n-acrylate, n, 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, imide (meth) acrylate, dimethylaminoethyl (meth) acrylate, N-butylaminoethyl (meth) acrylate, N-2, N-ethylmethacrylate, N-butylaminoethyl (meth) acrylate, N-butylaminoethyl (meth) acrylate, N-2, N-butylaminoethyl (meth) acrylate, N, diethylaminoethyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxyethyl 2-hydroxypropyl phthalate, 2- (meth) acryloyloxyethyl phosphate, glycidyl (meth) acrylate, and the like.
Examples of the 2-functional compound in the (meth) acrylate compound include: 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, neopentyl glycol di (meth) acrylate, ethylene oxide addition bisphenol A di (meth) acrylate, propylene glycol di (meth) acrylate, ethylene oxide addition bisphenol A di (meth) acrylate, propylene glycol di (meth) acrylate, ethylene oxide addition bisphenol A di (meth) acrylate, propylene glycol di (meth) acrylate, ethylene oxide, propylene glycol di (meth) acrylate, and ethylene oxide addition bisphenol A acrylate, and the like, Propylene oxide-added bisphenol a di (meth) acrylate, ethylene oxide-added bisphenol F di (meth) acrylate, dimethylol dicyclopentadienyl 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.
Examples of the 3-or more-functional compound in the (meth) acrylate compound 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 those obtained by reacting an epoxy compound with (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 above epoxy (meth) acrylate, the same epoxy compounds as those mentioned above 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 of the epoxy (meth) acrylate include epoxy (meth) acrylate manufactured by DAICEL ALLNEX, epoxy (meth) acrylate manufactured by Newzhou chemical industries, epoxy (meth) acrylate manufactured by Kyowa chemical Corporation, and epoxy (meth) acrylate manufactured by Nagase ChemteX Corporation.
Examples of the epoxy (meth) acrylate manufactured by DAICEL ALLNEX 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, EPOXY ESTER 3000A, EPOXY ESTER 200EA, and EPOXY ESTER 400 EA.
Examples of the epoxy (meth) acrylate produced by Nagase ChemteX Corporation include DENACOL ACRYLATE DA-141, DENACOL ACRYLATE DA-314, and DENACOL ACRYLATE DA-911.
The urethane (meth) acrylate can be obtained, for example, by reacting a (meth) acrylic derivative having a hydroxyl group with an isocyanate compound in the presence of a catalytic amount of a tin 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, triphenylphosphorothioate, tetramethylxylylene diisocyanate, 1,6, 11-undecane triisocyanate, and the like.
Further, as the isocyanate compound which becomes a raw material of the urethane (meth) acrylate, a chain-extended isocyanate compound obtained by a reaction of a polyol and an excessive amount of an isocyanate compound can also 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 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.
Examples of commercially available products of the urethane (meth) acrylates include urethane (meth) acrylates manufactured by east asia synthesis company, urethane (meth) acrylates manufactured by DAICEL ALLNEX company, urethane (meth) acrylates manufactured by seiko industries, urethane (meth) acrylates manufactured by seiko chemical companies, and urethane (meth) acrylates manufactured by coyowa chemical companies.
Examples of the urethane (meth) acrylates manufactured by Toyo Synthesis Co.Ltd include M-1100, M-1200, M-1210 and M-1600.
Examples of the urethane (meth) acrylate produced by DAICEL ALLNEX include EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL4858, EBECRYL5129, EBECRYL6700, EBECRYL8402, EBECRYL8803, EBECRYL8804, EBECRYL8807 and EBECRYL 9288060.
Examples of the urethane (meth) acrylates available from the above-mentioned Geneva industries include Artressin UN-330, Artressin SH-500B, Artressin UN-1200TPK, Artressin UN-1255, Artressin UN-3320HB, Artressin UN-7100, Artressin UN-9000A, and Artressin 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-101I, 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 contains the partially (meth) acrylic-modified epoxy compound, the ratio of the (meth) acryloyl group in the total of the epoxy group and the (meth) acryloyl group in the curable resin is preferably 30 mol% or more and 95 mol% or less. By setting the ratio of the (meth) acryloyl group in this range, the occurrence of liquid crystal contamination is suppressed, and the obtained sealant for a liquid crystal display element has more excellent adhesiveness.
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 further contains a photo radical polymerization initiator.
Examples of the photo radical polymerization initiator include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, thioxanthone compounds, and the like.
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.
The content of the photo radical polymerization initiator is preferably 0.5 parts by weight at the lower limit and 10 parts by weight at the upper limit with respect to 100 parts by weight of the curable resin. When the content of the photo radical polymerization initiator is in this range, the obtained sealant for a liquid crystal display element can suppress liquid crystal contamination and is more excellent in storage stability and photocurability. A more preferable lower limit of the content of the photo radical polymerization initiator is 1 part by weight, and a more preferable upper limit is 7 parts by weight.
The sealant for a liquid crystal display element of the present invention may contain a thermal radical polymerization initiator.
Examples of the thermal radical polymerization initiator include 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 polymeric azo compound (hereinafter, also referred to as "polymeric 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 has a preferred lower limit of 1000 and a preferred upper limit of 30 ten thousand. When the number average molecular weight of the macromolecular azo compound is in this range, adverse effects on the liquid crystal can be prevented, and the compound can be easily mixed with the curable resin. The number average molecular weight of the macromolecular azo compound is preferably 5000 at a lower limit, 10 ten thousand at a higher limit, 1 ten thousand at a higher limit, and 9 ten thousand at a higher 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 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: a macromolecular azo compound 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 via an azo group is preferably a polymer azo 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 initiator 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 peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, peroxyesters, diacylperoxides, and peroxydicarbonates.
The content of the thermal radical polymerization initiator is preferably 0.1 part by weight at the lower limit and 10 parts by weight at the upper limit with respect to 100 parts by weight of the curable resin. When the content of the thermal radical polymerization initiator is in this range, the obtained sealant for a liquid crystal display element suppresses liquid crystal contamination and is excellent in storage stability and thermosetting property. A more preferable lower limit of the content of the thermal radical polymerization initiator is 0.3 parts by weight, and a more preferable upper limit is 5 parts by weight.
The sealant for a liquid crystal display element of the present invention may contain a filler for the purpose of increasing 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, calcium silicate, and the like.
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. By setting the content of the filler within this range, the effects such as improvement of adhesion can be further enhanced without deteriorating coatability 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 a sealing agent for a liquid crystal display element to a substrate or the like.
As the silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane and the like can be suitably used. These silane coupling agents have an excellent effect of improving adhesion to a substrate or the like, and can inhibit the outflow of a curable resin into a liquid crystal by chemically bonding with the curable resin.
The silane coupling agents may be used alone, or 2 or more of them may be used in combination.
The preferable lower limit of 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 is 0.1 part by weight, and the preferable upper limit is 10 parts by weight. When the content of the silane coupling agent is in this range, the effect of suppressing the occurrence of liquid crystal contamination and improving the adhesiveness is more excellent. A more preferable lower limit of the content of the silane coupling agent is 0.3 parts by weight, and a more preferable upper limit is 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 titanium black exhibits a sufficient effect without being surface-treated, but titanium black having a surface treated with an organic component such as a coupling agent, or titanium black having a surface treated with an inorganic component such as silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, or magnesium oxide, or the like can 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 of the titanium black include titanium black manufactured by mitsubishi integrated materials corporation and titanium black manufactured by red ear 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 ear formation corporation include titanium black D.
The lower limit of the specific surface area of the titanium black is preferably 13m2A preferred upper limit is 30m2A more preferred lower limit is 15m2A more preferred upper limit is 25m2/g。
The volume resistivity of the titanium black has a preferred lower limit of 0.5 Ω · cm, a preferred upper limit of 3 Ω · cm, a more preferred lower limit of 1 Ω · cm, and a more preferred upper limit of 2.5 Ω · cm.
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 preferably 5nm, the upper limit thereof is preferably 200nm, the lower limit thereof is more preferably 10nm, and the upper limit thereof 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 PARTICLE SIZING SYSTEMS).
The preferable lower limit of the content of the light-shading agent in 100 parts by weight of the sealant for a liquid crystal display element of the present invention is 5 parts by weight, and the preferable upper limit is 80 parts by weight. By setting the content of the light-shading agent within this range, it is possible to exhibit more excellent light-shading properties without significantly reducing the adhesiveness, strength after curing, and drawing properties of the obtained sealant for a liquid crystal display element. The content of the light-shading agent is preferably 10 parts by weight at the lower limit, 70 parts by weight at the upper limit, 30 parts by weight at the lower limit, and 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 in which a curable resin, a thermal curing agent, and a thermal radical polymerization initiator added as needed are mixed using a mixer.
Examples of the mixer include a homomixer, a universal mixer, a planetary mixer, a kneader, and a three-roll mixer.
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. Such a 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, the fine particles having the conductive metal layer formed on the surface of the resin fine particles are preferable because the fine particles can be electrically connected without damaging the transparent substrate or the like due to the excellent elasticity of the resin fine particles.
Further, 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.
The liquid crystal display element of the present invention is preferably a liquid crystal display element of narrow frame design. 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 on a substrate with the sealant for a liquid crystal display element of the present invention by screen printing, dispenser application, or the like is performed; next, a step of applying a minute droplet of liquid crystal to the entire inner surface of the frame of the seal pattern by dripping while the sealant for a liquid crystal display element of the present invention is uncured, and immediately superposing another substrate; then, by performing a step of heating and curing the sealant, a liquid crystal display element can be obtained by performing the above-described steps. 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
The present invention can provide a sealant for a liquid crystal display element which is excellent in storage stability, adhesiveness, and low liquid crystal contamination. 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 3-necked flask equipped with a reflux condenser, a thermometer and a stirrer, 208.3g (2.0 mol) of styrene (manufactured by fuji film & Wako pure chemical industries, Ltd.) and 172.1g (2.0 mol) of methyl acrylate (manufactured by Tokyo chemical industries, Ltd.) were dissolved in 300mL of tetrahydrofuran. To the resulting solution, 16.4g (0.1 mol) of azobisisobutyronitrile was added as a polymerization initiator, and the mixture was stirred at 80 ℃ for 1 hour while nitrogen substitution was performed to effect a reaction. The obtained reaction product was concentrated and reprecipitated in an ethanol solution to obtain an intermediate polymer compound.
113g (2.3 mol) of the obtained intermediate polymer compound and hydrazine hydrate were dissolved in 200mL of tetrahydrofuran in a 3-neck flask equipped with a reflux condenser, a thermometer and a stirrer, and the reaction was carried out under reflux for 3 hours. After the reaction, the reaction mixture was concentrated to separate a solid component, thereby obtaining compound a.
According to1H-NMR, MS and FT-IR confirmed that the obtained compound A had a structure represented by the above formula (1-1) (Ar is phenyl) and a structure represented by the above formula (1-2) (R)1Is a hydrogen atom), and a structure (R) represented by the above formula (2)2Is a hydrogen atom, R3is-C (═ O) OCH3Group) of a compound. Further, the obtained compound A had a structure represented by the above formula (1-1) in an amount of 50 mol%. Further, the weight average molecular weight of the obtained compound a was 15000 and the softening point was 130 ℃.
(Synthesis of Compound B)
Compound B was obtained as the hydrazide compound of the present invention in the same manner as in the above "(synthesis of compound a)", except that the stirring time at 80 ℃ with stirring was changed to 4 hours while replacing nitrogen.
In addition, according to1H-NMR, MS and FT-IR confirmed that the obtained compound B had a structure represented by the above formula (1-1) (Ar is phenyl) or a structure represented by the above formula (1-2) (R)1Is a hydrogen atom), and a structure (R) represented by the above formula (2)2Is a hydrogen atom, R3is-C (═ O) OCH3Group) of a compound. Further, the compound B obtained had a structure represented by the above formula (1-1) in an amount of 50 mol%. Further, the weight average molecular weight of the obtained compound B was 7 ten thousand, and the softening point was 147 ℃.
(Synthesis of Compound C)
Compound C was obtained as the hydrazide compound of the present invention in the same manner as in the above "(synthesis of compound a)", except that the stirring time when stirring at 80 ℃ was changed to 0.5 hours while replacing nitrogen.
In addition, according to1H-NMR, MS and FT-IR confirmed that the obtained compound C had a structure represented by the above formula (1-1) (Ar is phenyl) or a structure represented by the above formula (1-2) (R)1Is a hydrogen atom), and a structure (R) represented by the above formula (2)2Is a hydrogen atom, R3is-C (═ O) OCH3Group) of a compound. Further, the obtained compound C had a structure represented by the above formula (1-1) in an amount of 50 mol%. Further, the weight average molecular weight of the obtained compound C was 3000, and the softening point was 92 ℃.
(Synthesis of Compound D)
Compound D was obtained as the hydrazide compound of the present invention in the same manner as in the above "(Synthesis of Compound A)" except that the loading of styrene was changed to 416.6g (4.0 mol), the loading of methyl acrylate was changed to 86.0g (1.0 mol), and the loading of hydrazine hydrate was changed to 60g (1.2 mol).
In addition, according to1H-NMR, MS and FT-IR confirmed that the obtained compound D had a structure represented by the above formula (1-1) (Ar is phenyl) or a structure represented by the above formula (1-2) (R)1Is a hydrogen atom), and a structure (R) represented by the above formula (2)2Is a hydrogen atom, R3is-C (═ O) OCH3Group) of a compound. Further, the compound D thus obtained had a structure represented by the above formula (1-1) in an amount of 80 mol%. Further, the weight average molecular weight of the obtained compound D was 25000, and the softening point was 156 ℃.
(Synthesis of Compound E)
The same procedure as in the above "(synthesis of compound a)" was repeated except that the loading of styrene was changed to 494.7g (4.75 mol), the loading of methyl acrylate was changed to 21.5g (0.25 mol), and the loading of hydrazine hydrate was changed to 20g (0.4 mol), to obtain compound E as the hydrazide compound of the present invention.
In addition, according to1H-NMR, MS and FT-IR confirmed that the obtained compound E had a structure represented by the above formula (1-1) (Ar is phenyl) and a structure represented by the above formula (1-2) (R)1Is a hydrogen atom), and a structure (R) represented by the above formula (2)2Is a hydrogen atom, R3is-C (═ O) OCH3Group) of a compound. Further, the obtained compound E had a structure represented by the above formula (1-1) in an amount of 95 mol%. Further, the weight average molecular weight of the obtained compound E was 24000, and the softening point was 200 ℃.
(Synthesis of Compound F)
Compound F was obtained as the hydrazide compound of the present invention in the same manner as in the above "(Synthesis of Compound A)" except that the loading of styrene was changed to 26.0g (0.25 mol), the loading of methyl acrylate was changed to 408.7g (4.75 mol), and the loading of hydrazine hydrate was changed to 275g (5.5 mol).
In addition, according to1H-NMR, MS and FT-IR confirmed that the obtained compound F had a structure represented by the above formula (1-1) (Ar is phenyl) and a structure represented by the above formula (1-2) (R)1Is a hydrogen atom), and a structure (R) represented by the above formula (2)2Is a hydrogen atom, R3is-C (═ O) OCH3Group) of a compound. Further, the compound F thus obtained had a structure represented by the above formula (1-1) in an amount of 5 mol%. Further, the weight average molecular weight of the obtained compound F was 16000, and the softening point was 69 ℃.
(Synthesis of Compound G)
In a 3-necked flask equipped with a reflux condenser, a thermometer and a stirrer, 86.1g (1.0 mol) of methyl acrylate (manufactured by Tokyo chemical industry Co., Ltd.) and 116.1g (1.0 mol) of 2-hydroxyethyl acrylate (manufactured by Tokyo chemical industry Co., Ltd.) were dissolved in 150mL of tetrahydrofuran. To the resulting solution, 16.4g (0.1 mol) of azobisisobutyronitrile was added as a polymerization initiator, and the mixture was stirred at 80 ℃ for 2 hours while nitrogen substitution was performed to effect a reaction. The obtained reaction product was concentrated and reprecipitated in an ethanol solution to obtain an intermediate polymer compound.
113g (2.3 mol) of the obtained intermediate polymer compound and hydrazine hydrate were dissolved in 100mL of methanol and 10mL of water in a 3-neck flask equipped with a reflux condenser, a thermometer and a stirrer, and the reaction was carried out under reflux for 3 hours. After the reaction, the reaction mixture was concentrated to separate a solid component, thereby obtaining compound G.
According to1H-NMR, MS and FT-IR confirmed that the obtained compound G was a compound represented by the following formula (5). Further, the weight average molecular weight of the obtained compound G was 12000, and the softening point was 64 ℃.
[ solution 5]
In the formula (5), m and n are the number of repetitions.
Examples 1 to 10 and comparative examples 1 to 3
The respective materials were mixed with a planetary mixer (manufactured by Thinky, kokura de zai (japanese: あわとり tailang)) at the mixing ratios described in tables 1 and 2, and then further mixed with a three-roll mixer, thereby preparing the respective sealants for liquid crystal display elements of examples 1 to 10 and comparative examples 1 to 3.
< evaluation >
The following evaluations were performed on the respective liquid crystal display element sealants obtained in examples and comparative examples. The results are shown in tables 1 and 2.
(storage stability)
The initial viscosity immediately after production and the viscosity after 1 week of storage at 25 ℃ after production were measured for each of the liquid crystal display element sealants obtained in examples and comparative examples. The storage stability was evaluated by setting (viscosity after storage)/(initial viscosity) as the thickening ratio, and setting the thickening ratio to be less than 1.1 as "excellent", the thickening ratio to be 1.1 or more and less than 1.5 as "good", the thickening ratio to be 1.5 or more and less than 2.0 as "Δ", and the thickening ratio to be 2.0 or more as "x".
The viscosity of the sealant for liquid crystal display elements was measured using an E-type viscometer ("DV-III" manufactured by BROOK FIELD) at 25 ℃ and a rotation speed of 1.0 rpm.
(adhesiveness)
The liquid crystal display elements obtained in examples and comparative examples were each filled with a sealant in a syringe for dispensing ("PSY" manufactured by Musashi Engineering Co., Ltd.)-10E "), and performing defoaming treatment. The sealant for liquid crystal display element after the defoaming treatment was dispensed in four directions to the inner side of 30mm from the end of the glass substrate (150mm × 150mm) by a dispenser ("SHOTMASTER 300" manufactured by Musashi Engineering), and the other glass substrate (110mm × 110mm) was laminated under vacuum. Irradiating with high-pressure mercury lamp at 100mW/cm2The liquid crystal display element sealant was precured with ultraviolet rays for 30 seconds, and then heated at 120 ℃ for 1 hour to thermally cure the liquid crystal display element sealant, thereby obtaining an adhesion test piece. A metal rod having a radius of 5mm was pressed into the end of the substrate of the obtained adhesion test piece at a speed of 5mm/min, and the strength (kgf) at which peeling of the panel occurred was measured to calculate the adhesion force (kg/cm).
The adhesiveness was evaluated by designating the case where the adhesiveness was 3.5kg/cm or more as "excellent", the case where the adhesiveness was 3.0kg/cm or more and less than 3.5kg/cm as "o", the case where the adhesiveness was 2.0kg/cm or more and less than 3.0kg/cm as "Δ", and the case where the adhesiveness was less than 2.0kg/cm as "x".
(Low liquid Crystal contamination (NI Point))
In a sample bottle, 0.1g of each of the liquid crystal display element sealants obtained in examples and comparative examples and 1g of liquid crystal ("4-pentyl-4-cyanobiphenyl" manufactured by tokyo chemical industry co., Ltd.) were charged. The sample bottle was put into an oven at 120 ℃ for 1 hour, and after allowing to stand and returning to 25 ℃, the liquid crystal portion was taken out and filtered with a 0.2 μm filter to prepare a liquid crystal sample for evaluation. 10mg of the obtained liquid crystal sample for evaluation was sealed in an aluminum sample pan, and NI point was measured using a differential scanning calorimeter ("DSC-Q100") under a temperature rise rate of 5 ℃/min. Note that, the sealant for a liquid crystal display element and 10mg of the liquid crystal which was not in contact were sealed in an aluminum sample plate, and the NI point was measured under the condition of a temperature rise rate of 5 ℃/min, and the result was regarded as a blank group.
The low liquid crystal contamination was evaluated by designating the difference between the NI point measured using the liquid crystal sample for evaluation and the NI point of the blank group as "very good" when the difference was-2 ℃ or more, as "good" when the difference was-3 ℃ or more and less than-2 ℃, as "Δ", and as "poor" when the difference was-5 ℃ or more and less than-3 ℃, and as "poor".
(display Property of liquid Crystal display element)
1 part by weight of spacer particles having an average particle diameter of 5 μm (Micropearl SI-H050, manufactured by hydroprocess chemical industries, Ltd.) was dispersed in 100 parts by weight of each of the liquid crystal display element sealants obtained in examples and comparative examples, and the resulting mixture was filled in a syringe and defoamed by a centrifugal defoaming machine (Awatron AW-1). Using a dispenser, the sealant for the liquid crystal display element after the defoaming treatment is applied to the nozzle diameter
One of 2 substrates with an alignment film and ITO was coated in a frame shape under conditions of a nozzle gap (Japanese: ノズルギャップ) of 42 μm, a discharge pressure of a syringe of 100 to 400kPa, and a coating speed of 60 mm/sec. At this time, the discharge pressure was adjusted so that the line width of the sealant for liquid crystal display element became about 1.5 mm. Next, a minute droplet of liquid crystal ("4-pentyl-4-cyanobiphenyl" manufactured by tokyo chemical industry) was applied dropwise to the entire inner surface of the frame of the liquid crystal display element sealant on the substrate on which the liquid crystal display element sealant was applied, and the other substrate was bonded under vacuum. Immediately after the bonding, the sealant portion for liquid crystal display element was irradiated with 100mW/cm using a metal halide lamp2Ultraviolet ray (2) for 30 seconds, the sealant for the liquid crystal display element was precured. Subsequently, the resultant was heated at 120 ℃ for 1 hour to perform main curing, thereby producing a liquid crystal display element.
For each of the liquid crystal display element sealants obtained in examples and comparative examples, 3 liquid crystal display elements were produced, and for each of the liquid crystal display elements obtained, disturbance in liquid crystal alignment in the vicinity of the liquid crystal display element sealant immediately after the production of the liquid crystal display element was visually observed. The alignment disorder was judged by color unevenness of the display portion, and the display performance of the liquid crystal display element was evaluated by taking "excellent" as a case where no display unevenness was observed at all in the peripheral portion of the liquid crystal display element, taking "o" as a case where a slightly light display unevenness was observed, taking "Δ" as a case where a clear, thick display unevenness was present, and taking "x" as a case where the clear, thick display unevenness was spread not only in the peripheral portion but also in the central portion.
Industrial applicability
The present invention can provide a sealant for a liquid crystal display element which is excellent in storage stability, adhesiveness, and low liquid crystal contamination. 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 (8)
1. A sealant for a liquid crystal display element, comprising a curable resin and a thermosetting agent, wherein,
the heat-curing agent comprises a hydrazide compound,
the hydrazide compound has a structure represented by the following formula (1-1) and a structure represented by the following formula (1-2),
in the formula (1-1), Ar is an aromatic ring, and in the formula (1-2), R1Is a hydrogen atom or a methyl group.
2. The sealant for a liquid crystal display element according to claim 1, wherein a proportion of the structure represented by the formula (1-1) in the hydrazide compound is 5 mol% or more and 95 mol% or less.
3. The sealant for liquid crystal display elements according to claim 1 or 2, wherein the hydrazide compound further has a structure represented by the following formula (2),
in the formula (2), R2Is a hydrogen atom or a methyl group, R3is-C (═ O) OR4Group, -CN group, -OR5A radical or a hydrogen atom, wherein R4Is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R5An alkyl group having 1 to 10 carbon atoms.
4. The sealant for a liquid crystal display element according to claim 1,2 or 3, wherein the hydrazide compound has a weight average molecular weight of 2000 or more and 20 ten thousand or less.
5. The sealant for a liquid crystal display element according to claim 1,2, 3, or 4, wherein the hydrazide compound has a softening point of 65 ℃ or more and 200 ℃ or less.
6. The sealant for a liquid crystal display element according to claim 1,2, 3, 4, or 5, further comprising a photo radical polymerization initiator.
7. A vertically conducting material comprising the sealant for liquid crystal display element according to claim 1,2, 3, 4, 5 or 6 and conductive fine particles.
8. A liquid crystal display element, which is obtained by using the sealant for a liquid crystal display element according to claim 1,2, 3, 4, 5 or 6 or the vertically conducting material according to claim 7.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019163155 | 2019-09-06 | ||
| JP2019-163155 | 2019-09-06 | ||
| PCT/JP2020/031221 WO2021044842A1 (en) | 2019-09-06 | 2020-08-19 | Sealing agent for liquid crystal display elements, vertical conduction material, and liquid crystal display element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113874462A true CN113874462A (en) | 2021-12-31 |
| CN113874462B CN113874462B (en) | 2024-04-26 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202080037785.3A Active CN113874462B (en) | 2019-09-06 | 2020-08-19 | Sealing agent for liquid crystal display element, vertically conductive material, and liquid crystal display element |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP6821102B1 (en) |
| KR (1) | KR20220058488A (en) |
| CN (1) | CN113874462B (en) |
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|---|---|---|---|---|
| FR1212707A (en) * | 1955-08-16 | 1960-03-25 | Ciba Geigy | New polymerization products containing hydrazides or modified hydrazides of unsaturated copolymerizable acids as structural elements |
| US4544733A (en) * | 1983-11-21 | 1985-10-01 | Ajinomoto Co., Inc. | Latent curing agents for epoxy resins |
| JPS6481842A (en) * | 1987-09-24 | 1989-03-28 | Mitsubishi Yuka Badische | Stable dispersion/dissolution of water-sparingly soluble hydrazide group-containing copolymer in aqueous liquid |
| JP2004061925A (en) * | 2002-07-30 | 2004-02-26 | Nippon Kayaku Co Ltd | Liquid crystal sealing agent and liquid crystal display cell using the same |
| CN101585929A (en) * | 2009-06-25 | 2009-11-25 | 嘉兴荣泰雷帕司绝缘材料有限公司 | Hydrazide latency improving curing agent and preparation method thereof |
| KR20100028162A (en) * | 2008-09-04 | 2010-03-12 | 동우 화인켐 주식회사 | Curable resin composition and liquid crystal display device |
| JP2017223828A (en) * | 2016-06-15 | 2017-12-21 | 三井化学株式会社 | Sealant for liquid crystal dropping method, liquid crystal display panel, and method for manufacturing liquid crystal display panel |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3583326B2 (en) | 1999-11-01 | 2004-11-04 | 協立化学産業株式会社 | Sealant for dripping method of LCD panel |
| EP1405888A1 (en) | 2001-05-16 | 2004-04-07 | Sekisui Chemical Co., Ltd. | Curing resin composition and sealants and end-sealing materials for displays |
| JP6730133B2 (en) * | 2015-09-02 | 2020-07-29 | 積水化学工業株式会社 | Liquid crystal display element sealant, vertical conduction material and liquid crystal display element |
-
2020
- 2020-08-19 JP JP2020552920A patent/JP6821102B1/en active Active
- 2020-08-19 KR KR1020217028250A patent/KR20220058488A/en unknown
- 2020-08-19 CN CN202080037785.3A patent/CN113874462B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1212707A (en) * | 1955-08-16 | 1960-03-25 | Ciba Geigy | New polymerization products containing hydrazides or modified hydrazides of unsaturated copolymerizable acids as structural elements |
| US4544733A (en) * | 1983-11-21 | 1985-10-01 | Ajinomoto Co., Inc. | Latent curing agents for epoxy resins |
| JPS6481842A (en) * | 1987-09-24 | 1989-03-28 | Mitsubishi Yuka Badische | Stable dispersion/dissolution of water-sparingly soluble hydrazide group-containing copolymer in aqueous liquid |
| JP2004061925A (en) * | 2002-07-30 | 2004-02-26 | Nippon Kayaku Co Ltd | Liquid crystal sealing agent and liquid crystal display cell using the same |
| KR20100028162A (en) * | 2008-09-04 | 2010-03-12 | 동우 화인켐 주식회사 | Curable resin composition and liquid crystal display device |
| CN101585929A (en) * | 2009-06-25 | 2009-11-25 | 嘉兴荣泰雷帕司绝缘材料有限公司 | Hydrazide latency improving curing agent and preparation method thereof |
| JP2017223828A (en) * | 2016-06-15 | 2017-12-21 | 三井化学株式会社 | Sealant for liquid crystal dropping method, liquid crystal display panel, and method for manufacturing liquid crystal display panel |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20220058488A (en) | 2022-05-09 |
| JP6821102B1 (en) | 2021-01-27 |
| JPWO2021044842A1 (en) | 2021-09-27 |
| CN113874462B (en) | 2024-04-26 |
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