CN112063350B - Sealant composition and use - Google Patents

Sealant composition and use Download PDF

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CN112063350B
CN112063350B CN202010947361.2A CN202010947361A CN112063350B CN 112063350 B CN112063350 B CN 112063350B CN 202010947361 A CN202010947361 A CN 202010947361A CN 112063350 B CN112063350 B CN 112063350B
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epoxy
meth
resin
epoxy resin
acrylate
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CN112063350A (en
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马晓明
李晓雷
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Suzhou Runbang Semiconductor Material Technology Co ltd
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Suzhou Runbang Semiconductor Material Technology Co ltd
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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
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • 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
    • C09J147/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Abstract

The invention relates to the technical field of sealants, in particular to a sealant composition and application thereof. The sealant composition includes: part of (methyl) acrylic acid modified epoxy resin, epoxy (methyl) acrylate, epoxy resin, photoinitiator, coupling agent, thermal curing agent, filler and liquid 1, 2-polybutadiene modified resin; the structural formula of the liquid 1, 2-polybutadiene improved resin is as follows:
Figure DDA0002675753880000011
wherein: r 1 Selected from H, hydroxyl, epoxy,
Figure DDA0002675753880000012
Any one or more of; r 2 Selected from H, hydroxyl, epoxy,

Description

Sealant composition and use
Technical Field
The invention relates to the technical field of sealants, in particular to a sealant composition and application thereof.
Background
As a method for manufacturing a liquid crystal display element, a liquid crystal dropping method called a dropping process using a photo-thermal curing type sealing agent containing a curable resin, a photopolymerization initiator, and a thermal curing agent is used from the viewpoint of shortening the tact time (tact time) and optimizing the amount of liquid crystal used.
In the modern days in which various mobile devices with liquid crystal panels such as mobile phones and portable game machines are becoming widespread, the narrow frame of the liquid crystal display section is inevitably designed in order to increase the display area of the display screen and to make the display more beautiful.
Because of the narrow border designIs/are as followsThe width of the display screen and the sealant is gradually narrowed, so that the adhesion of the display screen is insufficient. In the reliability test (high temperature and high humidity test), there was a problem that moisture entered the display screen and poor display occurred.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, it is an object of the present invention to provide a sealant composition and use for solving the problems of the prior art.
To achieve the above objects and other related objects, the present invention is achieved by the following technical solutions.
In one aspect, the present invention provides a sealant composition comprising: part of (methyl) acrylic acid modified epoxy resin, epoxy (methyl) acrylate, epoxy resin, photoinitiator, coupling agent, thermal curing agent, filler and liquid 1, 2-polybutadiene modified resin;
the structural formula of the liquid 1, 2-polybutadiene improved resin is as follows:
Figure BDA0002675753870000011
wherein: r 1 Selected from H, hydroxyl, epoxy,
Figure BDA0002675753870000012
Any one or more of; r is 2 Selected from H, hydroxyl, epoxy group,
Figure BDA0002675753870000021
Any one or more of; the value of n is 1-10.
In some embodiments of the invention, the hydroxyl group is selected from alcoholic hydroxyl groups.
In some embodiments of the present invention, the liquid 1, 2-polybutadiene improving resin has the formula:
Figure BDA0002675753870000022
in some embodiments of the present invention, the liquid 1, 2-polybutadiene improving resin has the formula:
Figure BDA0002675753870000023
formula (Ib) wherein n ═ n 1 +n 2 ；n 1 /n 2 ＝1/4～1/2；
In some embodiments of the present invention, the liquid 1, 2-polybutadiene improving resin has the formula:
Figure BDA0002675753870000024
in some embodiments of the present invention, the raw materials of the sealant composition comprise, in parts by weight:
Figure BDA0002675753870000025
Figure BDA0002675753870000031
in some embodiments of the present invention, the partial (meth) acrylic-modified epoxy resin has 1 or more epoxy groups and 1 or more (meth) acryloyloxy groups in 1 molecule.
In some embodiments of the present invention, the partial (meth) acrylic modified epoxy resin has a grafting ratio of 50 to 100%.
In some embodiments of the present invention, the epoxy (meth) acrylate is a compound obtained by reacting all epoxy groups in an epoxy resin with (meth) acrylic acid.
In some embodiments of the invention, the epoxy resin is selected from the group consisting of bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, 2' -diallylbisphenol A type epoxy resins, hydrogenated bisphenol type epoxy resins, propylene oxide addition bisphenol A type epoxy resins, resorcinol type epoxy resins, biphenyl type epoxy resins, thioether type epoxy resins, diphenyl ether type epoxy resins, dicyclopentadiene type epoxy resins, one or more combinations of naphthalene-based epoxy resin, phenol novolac-based epoxy resin, o-cresol novolac-based epoxy resin, dicyclopentadiene novolac-based epoxy resin, biphenol novolac-based epoxy resin, naphthalene phenol novolac-based epoxy resin, glycidyl amine-based epoxy resin, alkyl polyol-based epoxy resin, rubber-modified epoxy resin, glycidyl ester compound, and bisphenol a-based episulfide resin.
In some embodiments of the present invention, the photoinitiator is selected from one or more of benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, and thioxanthone.
In some embodiments of the present invention, the thermal curing agent is selected from one or more of organic acid hydrazide, imidazole derivative, amine compound, polyhydric phenol compound, and acid anhydride.
In some embodiments of the invention, the coupling agent is selected from silane coupling agents; the silane coupling agent is selected from one or more of gamma-aminopropyl trimethoxy silane, gamma-mercapto propyl trimethoxy silane, gamma-glycidoxy propyl trimethoxy silane and gamma-isocyanate propyl trimethoxy silane.
In some embodiments of the invention, the filler is selected from organic fillers and/or inorganic fillers.
In some embodiments of the invention, the thermal curing agent is selected from organic acid hydrazides.
In some embodiments of the invention, the inorganic filler is selected from the group consisting of talc, asbestos, silica, diatomaceous earth, smectite, bentonite, calcium carbonate, magnesium carbonate, alumina, montmorillonite, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, magnesium hydroxide, aluminum hydroxide, glass beads, silicon nitride, barium sulfate, gypsum, calcium silicate, sericite activated clay, aluminum nitride, and combinations of one or more thereof.
In some embodiments of the invention, the organic filler is selected from the group consisting of polyester microparticles, polyurethane microparticles, vinyl polymer microparticles, acrylic polymer microparticles, and combinations of one or more thereof.
In another aspect, the present invention provides a method for preparing the sealant composition of the present invention, which comprises mixing a part of (meth) acrylic acid modified epoxy resin, epoxy (meth) acrylate, epoxy resin, photoinitiator, coupling agent, thermal curing agent, filler and liquid 1, 2-polybutadiene modified resin.
In some embodiments of the invention, the photoinitiator is added into the epoxy resin and dissolved at 120-180 ℃; adding liquid 1, 2-polybutadiene improved resin, partial (methyl) acrylic acid modified epoxy resin and epoxy (methyl) acrylate coupling agent, and stirring for 30-60 minutes under vacuum; adding a filler, and stirring for 30-60 minutes under vacuum; cooling to 25 ℃, adding a curing agent, and stirring for 30-60 minutes in vacuum when the temperature is not lower than 28 ℃.
In another aspect, the present invention provides the use of the sealant composition of the present invention in a liquid crystal display element.
In another aspect, the present invention provides a liquid crystal display element comprising the sealant composition of the present invention.
Compared with the prior art, the invention has the beneficial effects that:
the added liquid 1, 2-polybutadiene improves the resin, the tail end of the resin is modified by epoxy or acrylic acid, the Tg of the resin is improved while the adhesive force is improved, the water resistance is improved, and the effect of preventing water from entering a display screen in a reliability test is achieved. In addition, the miscibility with existing resins is better. However, the addition of the inorganic powder increases the viscosity of the sealant and reduces the coatability of the sealant, and the above problems do not exist in the present application.
Detailed Description
Through a large number of experiments, the applicant of the invention unexpectedly discovers that the elasticity and the strength of the resin improved by adding the liquid 1, 2-polybutadiene can improve the glass transition temperature (Tg) of the resin and increase the water resistance while improving the adhesive force, and the effect of preventing moisture from entering a display screen in a reliability test can be realized. On this basis, the present application has been completed. Specifically, the method comprises the following steps:
the invention provides a sealant composition, which comprises a part of (methyl) acrylic acid modified epoxy resin, epoxy (methyl) acrylate, epoxy resin, a photoinitiator, a coupling agent, a thermal curing agent, a filler and a liquid 1, 2-polybutadiene improved resin.
In the sealant composition provided by the invention, the structural formula of the liquid 1, 2-polybutadiene improved resin is as follows:
Figure BDA0002675753870000041
wherein:
R 1 selected from H, hydroxyl, epoxy,
Figure BDA0002675753870000051
Any one or more of;
R 2 selected from H, hydroxyl, epoxy group,
Figure BDA0002675753870000052
Any one or more of;
the value of n is 1-10. In some embodiments, n can take on a value of, for example, 1 to 10, 1 to 3, 3 to 5, 5 to 8, or 8 to 10.
The invention provides a sealant compositionThe hydroxyl group in the liquid 1, 2-polybutadiene improving resin may be, for example, an alcoholic hydroxyl group, more specifically, may be-CH 2 CH 2 OH。
In one embodiment, the liquid 1, 2-polybutadiene improving resin has the structural formula:
Figure BDA0002675753870000053
the number average molecular weight (Mn) of the formula (Ia) is 1000 to 3000. More specifically, the molecular weight may be 1000 to 1500, 1500 to 2000, 2000 to 2500, or 2500 to 3000. The structural formula belongs to molecular chain end and OH modified vinyl; hydrogenated Tg: -25 to-15 ℃. The structural formula is composed of hydrocarbon chains, so that hydrophobicity is increased, and water resistance is improved, and the structural formula is better applied to sealing materials. For example, the product may be a G series product of Japanese Caoda. More preferably, it may be Rachycentron canadum G-1000, G-2000, or G-3000.
In a second embodiment, the liquid 1, 2-polybutadiene improving resin has the formula:
Figure BDA0002675753870000054
in the formula (Ib), n is n 1 +n 2 ；n 1 /n 2 1/4-1/2, for example n 1 /n 2 May be 1/3. About 25% of the butadiene units in the molecular chain are epoxidized and can be used as a modifier to increase the toughness of the epoxy resin in curing (adhesion, coating). The number average molecular weight (Mn) is 1300-2200. The structural formula belongs to molecular chain end, H modified vinyl and epoxy Tg: -16 to-7 ℃. For example, JP series products of Japanese Caoda are available. More specifically, JP-200 or JP-100 may be used.
In a third embodiment, the liquid 1, 2-polybutadiene improving resin has the structural formula:
Figure BDA0002675753870000061
in the formula (ic), the series in which an acrylic group is introduced via hydroxyl groups at both terminals is mainly used for adhesive purposes. By virtue of TDI (toluene diisocyanate), each molecule contains 4 urethane groups (2 at one end and 4 at both ends). The urethane moiety, when cured, combines with hydrogen, helping to improve the strength of the adhesive. The number average molecular weight (Mn) is 2000-3000, 2000-2500, or 2500-3000. The structural formula belongs to the molecular chain end; urethane methyl propyl acid; modifying vinyl; no epoxy Tg: -15 to-5 ℃. For example, it may be TE series products of Japanese Cao, and more specifically, it may be Japanese Cao TE-2000.
In the present specification, the term "part of the (meth) acrylic acid-modified epoxy resin" and the term "epoxy (meth) acrylate" as used herein means acrylic acid or methacrylic acid.
The sealant composition provided by the invention comprises 20-70 parts by weight of partial (methyl) acrylic acid modified epoxy resin. In some embodiments, the partially (meth) acrylic-modified epoxy resin may also be 20-30 parts, 30-40 parts, 40-50 parts, 50-60 parts, or 60-70 parts. The partial (meth) acrylic-modified epoxy resin is a resin having 1 or more epoxy groups and 1 or more (meth) acryloyloxy groups in the molecule. The partially (meth) acrylic-modified epoxy resin can be obtained, for example, by reacting a part of epoxy groups of an epoxy resin having 2 or more epoxy groups with (meth) acrylic acid. Further, the grafting ratio of the partial (methyl) acrylic acid modified epoxy resin is 50-100%, 50-60%, 60-70%, 70-80%, 80-90%, or 90-100%. The grafting ratio is the ratio of the amount of monomer or polymer branch linked to the graft copolymer to the total amount of monomer or polymer branch to be grafted initially charged in the graft copolymerization. Specifically, the partially (meth) acrylic-modified epoxy resin may be, for example, bisphenol A-type partial epoxy (meth) acrylate, bisphenol F-type partial epoxy (meth) acrylate, bisphenol S-type partial epoxy (meth) acrylate, 2' -diallylbisphenol A-type partial epoxy (meth) acrylate, hydrogenated bisphenol-type partial epoxy (meth) acrylate, propylene oxide-added bisphenol A-type partial epoxy (meth) acrylate, resorcinol-type partial epoxy (meth) acrylate, biphenyl-type partial epoxy (meth) acrylate, thioether-type partial epoxy (meth) acrylate, diphenyl ether-type partial epoxy (meth) acrylate, dicyclopentadiene-type partial epoxy (meth) acrylate, naphthalene-type partial epoxy (meth) acrylate, phenol novolac-type partial epoxy (meth) acrylate, hydrogenated bisphenol-type partial epoxy (meth) acrylate, or hydrogenated bisphenol A-type partial epoxy (meth) acrylate, O-cresol novolak-type partial epoxy (meth) acrylate, dicyclopentadiene novolak-type partial epoxy (meth) acrylate, biphenol novolak-type partial epoxy (meth) acrylate, naphthalene phenol novolak-type partial epoxy (meth) acrylate, glycidyl amine-type partial epoxy (meth) acrylate, alkyl polyol-type partial epoxy (meth) acrylate, rubber-modified partial epoxy (meth) acrylate.
Further, the molecular weight of the partially (meth) acrylic modified epoxy resin may be, for example, 300 to 3000, 300 to 500, 500 to 1000, 1000 to 2000, or 2000 to 3000. . In the present specification, the "molecular weight" is a molecular weight determined from a structural formula for a compound having a definite molecular structure, but may be expressed by using a weight average molecular weight for a compound having a wide distribution of polymerization degrees and a compound having an indefinite modification site.
The sealant composition provided by the invention further comprises 10-40 parts of epoxy (methyl) acrylate by weight. In some embodiments, the epoxy (meth) acrylate may also be 10-20 parts, 20-30 parts, or 30-40 parts. The epoxy (meth) acrylate is not particularly limited, and examples thereof include compounds obtained by reacting (meth) acrylic acid with an epoxy resin according to a conventional method in the presence of a basic catalyst. The epoxy (meth) acrylate may be, for example, the above-mentioned epoxy (meth) acrylate having a functionality of 2 or less, and examples thereof include epoxy (meth) acrylates obtained by reacting an epoxy resin having a functionality of 2 or less with (meth) acrylic acid in the presence of a basic catalyst according to a conventional method. More specifically, the epoxy (meth) acrylate may be, for example, bisphenol A epoxy (meth) acrylate, bisphenol F epoxy (meth) acrylate, bisphenol S epoxy (meth) acrylate, 2' -diallylbisphenol A epoxy (meth) acrylate, hydrogenated bisphenol type epoxy (meth) acrylate, propylene oxide addition bisphenol A epoxy (meth) acrylate, resorcinol type epoxy (meth) acrylate, biphenyl type epoxy (meth) acrylate, thioether type epoxy (meth) acrylate, diphenyl ether type epoxy (meth) acrylate, dicyclopentadiene type epoxy (meth) acrylate, naphthalene type epoxy (meth) acrylate, phenol novolak type epoxy (meth) acrylate, o-cresol novolak type epoxy (meth) acrylate, dicyclopentadiene novolak type epoxy (meth) acrylate, styrene-butadiene-styrene-co-styrene-butadiene-styrene-butadiene-styrene copolymer, One or a combination of two or more of biphenyl novolak-type epoxy (meth) acrylate, naphthol novolak-type epoxy (meth) acrylate, glycidyl amine-type epoxy (meth) acrylate, alkyl polyol-type epoxy (meth) acrylate, rubber-modified epoxy (meth) acrylate, and the like.
Further, the epoxy (meth) acrylate may have a molecular weight of, for example, 500 to 5000, 500 to 1000, 1000 to 2000, 2000 to 3000, 3000 to 4000, or 4000 to 5000. In the present specification, the "molecular weight" is a molecular weight determined from a structural formula for a compound having a definite molecular structure, but may be expressed by using a weight average molecular weight for a compound having a wide distribution of polymerization degrees and a compound having an indefinite modification site.
The epoxy resin (including the exemplified portion) for synthesizing the partially (meth) acrylic-modified epoxy resin and the epoxy (meth) acrylate is not particularly limited, and examples of the epoxy resin having a functionality of 2 or less include bisphenol a-type epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, 2' -diallylbisphenol a-type epoxy resin, hydrogenated bisphenol-type epoxy resin, propylene oxide-adduct 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, naphthalene-phenol novolac-type epoxy resin, naphthalene-type epoxy resin, phenol novolac-type epoxy resin, and the like, One or a combination of plural kinds of glycidyl amine type epoxy resin, alkyl polyol type epoxy resin, rubber modified type epoxy resin, glycidyl ester compound, bisphenol A type episulfide resin and the like.
Further, the weight average molecular weight of the raw epoxy resin of the synthetic partially (meth) acrylic acid modified epoxy resin and the epoxy (meth) acrylate epoxy resin may be, for example, 200 to 2000, 200 to 500, 500 to 1000, 1000 to 1500, or 1500 to 2000.
The sealant composition provided by the present invention further comprises 10 to 40 parts by weight of an epoxy resin, and in some embodiments, the epoxy resin may also be 10 to 20 parts, 20 to 30 parts, or 30 to 40 parts. Among them, the epoxy resin is not particularly limited, for example, the epoxy resin composition may be one or a combination of two or more of bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, 2' -diallylbisphenol a type epoxy resin, hydrogenated bisphenol type epoxy resin, propylene oxide adduct bisphenol a type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, thioether type epoxy resin, diphenylether 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, naphthol phenol novolac type epoxy resin, glycidyl amine type epoxy resin, alkyl polyol type epoxy resin, rubber modified type epoxy resin, glycidyl ester compound, bisphenol a type sulfide resin, and the like.
Further, the weight average molecular weight of the epoxy resin used in the sealant composition may be, for example, 200 to 2000, 200 to 500, 500 to 1000, 1000 to 1500, or 1500 to 2000.
The sealant composition provided by the invention further comprises 1-10 parts of a photoinitiator according to parts by weight. In some specific embodiments, the photoinitiator may also be 1-2 parts, 2-4 parts, 4-6 parts, 6-8 parts, or 8-10 parts. Wherein the photoinitiator is selected from one or more of benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, thioxanthone and the like. Examples of commercially available products of the above photoinitiator include: IRGACURE 184, IRGACURE369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, and Lucirin TPO (all manufactured by BASF corporation); NCI-930 (manufactured by ADEKA corporation); SPEEDCURE EMK (manufactured by Japan Siber Hegner), benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether (all manufactured by Tokyo chemical Co., Ltd.), and the like.
Further, benzophenone compounds such as benzophenone, methyl o-benzoylbenzoate, and α -diketone initiators such as butanedione, benzyl, and acetonaphthophenone, etc. Benzoin ether compounds such as benzoin, benzoin diethyl ether and the like.
The sealant composition provided by the invention further comprises 1-10 parts of a coupling agent by weight. In some embodiments, the coupling agent may also be 1-2 parts, 2-4 parts, 4-6 parts, 6-8 parts, or 8-10 parts. The coupling agent is not particularly limited, and is, for example, one or a combination of two or more selected from the group consisting of γ -aminopropyltrimethoxysilane, γ -mercaptopropyltrimethoxysilane, γ -glycidoxypropyltrimethoxysilane, and γ -isocyanatopropyltrimethoxysilane, because the coupling agent has an excellent effect of improving the adhesion to a substrate or the like and can inhibit the outflow of the curable resin into the liquid crystal by chemically bonding to the curable resin.
In the sealant composition provided by the invention, the sealant composition further comprises 1-10 parts by weight of a thermal curing agent. In some specific embodiments, the thermal curing agent can be 1-2 parts, 2-4 parts, 4-6 parts, 6-8 parts, or 8-10 parts. The heat-curing agent is not particularly limited, and examples thereof include one or a combination of two or more of organic acid hydrazide, imidazole derivative, amine compound, polyhydric phenol compound, and acid anhydride; further preferably, the thermal curing agent is selected from organic acid hydrazides. More specifically, the organic acid hydrazide is selected from one or more of 1, 3-bis (hydrazinocarbonylethyl) -5-isopropylhydantoin, sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide and the like. Examples of the additives include commercially available products, and examples thereof include SDH, MDH, ADH (available from Otsuka chemical Co., Ltd.); ajicure VDH, Ajicure VDH-J, Ajicure UDH (all Ajinomoto Fine Techno Co., Inc.).
The sealant composition provided by the invention further comprises 10-50 parts of a filler by weight. In some specific embodiments, the filler can be 10-20 parts, 20-30 parts, 30-40 parts, or 40-50 parts. Wherein the filler is selected from organic fillers and/or inorganic fillers. Further, the inorganic filler may be selected from one or a combination of more of talc, asbestos, silica, diatomaceous earth, smectite, bentonite, calcium carbonate, magnesium carbonate, alumina, montmorillonite, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, magnesium hydroxide, aluminum hydroxide, glass beads, silicon nitride, barium sulfate, gypsum, calcium silicate, sericite activated clay, aluminum nitride, and the like. The organic filler may be selected from one or a combination of more of polyester microparticles, polyurethane microparticles, vinyl polymer microparticles, acrylic polymer microparticles, and the like.
The sealant composition provided by the invention further comprises 1-30 parts of liquid 1, 2-polybutadiene improved resin by weight. In some specific embodiments, the liquid 1, 2-polybutadiene improving resin may be 1-5 parts, 5-10 parts, 10-20 parts, or 20-30 parts.
In a specific embodiment, the raw materials of the sealant composition comprise the following components in parts by weight:
Figure BDA0002675753870000091
Figure BDA0002675753870000101
the second aspect of the present invention provides a method for preparing the sealant composition according to the first aspect of the present invention, comprising mixing a part of (meth) acrylic acid modified epoxy resin, epoxy (meth) acrylate, epoxy resin, photoinitiator, coupling agent, thermal curing agent, filler, liquid 1, 2-polybutadiene modified resin.
Specifically, the method provided by the invention comprises the steps of firstly adding a photoinitiator into epoxy resin, dissolving the photoinitiator for 30-60 minutes at 120-180 ℃, adding liquid 1, 2-polybutadiene to improve the resin after confirming that the photoinitiator is completely dissolved, partially stirring the (meth) acrylic acid modified epoxy resin, epoxy (meth) acrylate and a coupling agent for 30-60 minutes under vacuum, and confirming that the photoinitiator and the coupling agent are completely mixed. Adding a filler, and stirring for 30-60 minutes under vacuum. And (3) after stirring, standing the stirring kettle, adding a thermal curing agent after the temperature of the stirring kettle is reduced to 25 ℃, and stirring for 30-60 minutes under vacuum under the condition that the temperature of the stirring kettle is controlled not to exceed 28 ℃. And finally, grinding by three rollers (the gap of the rollers is controlled below 5 um), filtering (the filtering precision is more than 5 um), and filling the finished product.
In a third aspect, the present invention provides the use of a sealant composition according to the first aspect of the present invention in a liquid crystal display element.
In a fourth aspect, the present invention provides a liquid crystal display element comprising the sealant composition according to the first aspect of the present invention.
In the liquid crystal display element provided by the invention, the sealant composition can be suitable for manufacturing the liquid crystal display element by a liquid crystal dropping method.
In the liquid crystal display device provided by the present invention, the method for manufacturing the liquid crystal display device of the present invention by a liquid crystal dropping method is specifically, for example, the following method: a step of forming a rectangular seal pattern on a substrate with the sealant composition of the present invention or the like by screen printing, dispensing coating, or the like; a step of applying a liquid crystal in a state where the sealant composition of the present invention is not cured to the entire surface of the frame of the transparent substrate by dropping fine liquid droplets, and immediately superposing the other substrates; and a step of pre-curing the sealant by irradiating the seal pattern portion of the sealant for liquid crystal display element of the present invention with light such as ultraviolet rays; and a step of heating the precured sealant to perform main curing.
In the liquid crystal display element provided by the invention, the substrate is a flexible substrate, for example. More specifically, for example, plastic substrates such as polyethylene terephthalate, polyester, poly (meth) acrylate, polycarbonate, and polyether sulfone are used. The sealant composition of the present invention can also be used for bonding a general glass substrate. The substrate is usually formed with a transparent electrode made of indium oxide or the like, an alignment film made of polyimide or the like, an inorganic ion shielding film, or the like.
In conclusion, the invention has the beneficial effects that:
compared with the prior art, the added liquid 1, 2-polybutadiene improves the resin by modifying the tail end of the resin with epoxy or acrylic acid, so that the Tg of the resin is improved while the adhesive force is improved, the water resistance is improved, and the effect of preventing moisture from entering a display screen when a reliability test is achieved. In addition, the miscibility with existing resins is better. However, the addition of the inorganic powder increases the viscosity of the sealant and reduces the coatability of the sealant, and the above problems do not exist in the present application.
The following description of the embodiments of the present invention is provided for illustrative purposes, and other advantages and effects of the present invention will become apparent to those skilled in the art from the present disclosure.
Before the present embodiments are further described, it is to be understood that the scope of the invention is not limited to the particular embodiments described below; it is also to be understood that the terminology used in the examples is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention. Test methods in which specific conditions are not specified in the following examples are generally carried out under conventional conditions or under conditions recommended by the respective manufacturers.
When numerical ranges are given in the examples, it is understood that both endpoints of each of the numerical ranges and any value therebetween can be selected unless the invention otherwise indicated. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition to the specific methods, devices, and materials used in the examples, the invention may be practiced using any method, device, and material that is similar or equivalent to the methods, devices, and materials described in examples herein, in addition to those described in prior art practice and the description herein.
Wherein, the epoxy resin: bisphenol A epoxy resin was purchased from DAICEL-ALLNEX LTD. manufacturer EB3700 model.
Photoinitiator (2): IR-651 Benzoin diethyl ether was purchased from BASF.
Coupling agent: 3-glycidoxypropyltrimethoxysilane was purchased from KBM-403 manufactured by shin-Etsu chemical Co.
Thermal curing agent: sebacic dihydrazide is available from Otsuka chemical company, Inc. under the ADH model.
Bisphenol A partial epoxy (meth) acrylate and bisphenol A epoxy (meth) acrylate, if commercially available, may be provided as a manufacturer model, if prepared, synthetic methods are provided.
Preparation of a part of methacrylic acid modified bisphenol A epoxy resin:
while blowing air, 1000 parts by weight of bisphenol A type epoxy resin (product of Mitsubishi chemical, "jER 828 EL"), 2 parts by weight of p-ethoxyphenol as a polymerization inhibitor, 2 parts by weight of triethylamine as a reaction catalyst, and 253 parts by weight of methacrylic acid were refluxed and stirred at 90 ℃ for 5 hours to be reacted. 100 parts by weight of the obtained reaction product was filtered to obtain 50% of a part of a methacrylic acid-modified bisphenol A type epoxy resin.
Bisphenol A epoxy (meth) acrylate
While blowing air, 1000 parts by weight of bisphenol A type epoxy resin (product of Mitsubishi chemical, "jER 828 EL"), 2 parts by weight of p-ethoxyphenol as a polymerization inhibitor, 2 parts by weight of triethylamine as a reaction catalyst, and 506 parts by weight of methacrylic acid were refluxed and stirred at 90 ℃ for 5 hours to be reacted. 100 parts by weight of the obtained reaction product was filtered to obtain 100% partially methacrylic acid-modified bisphenol A epoxy resin.
Example 1
The raw materials of the sealant composition comprise the following components in parts by weight:
Figure BDA0002675753870000121
wherein the liquid 1, 2-polybutadiene improves the molecular chain ends of the resin; h modified vinyl; epoxy Tg; -7 ℃. The product is named as Nichio JP-200.
In a planetary stirring apparatus, first, IR-651 benzoin diethyl ether was added to a denatured bisphenol A epoxy resin and dissolved at 160 ℃ for 30 minutes, and after it was confirmed that all of IR-651 benzoin diethyl ether was dissolved, a liquid 1, 2-polybutadiene modified resin was added, bisphenol A partial epoxy (meth) acrylate and bisphenol A epoxy (meth) acrylate, and a coupling agent 3-glycidoxypropyltrimethoxysilane were stirred under vacuum for 30 to 60 minutes, and it was confirmed that all of them were mixed. Adding filler silicon dioxide, and stirring for 30-60 min under vacuum. And (3) after stirring, standing the stirring kettle, adding a thermal curing agent, namely the sebacic dihydrazide after the temperature of the stirring kettle is reduced to 25 ℃, and stirring for 30-60 minutes under vacuum under the condition that the temperature of the stirring kettle is controlled not to exceed 28 ℃. And finally, grinding by three rollers (the clearance of the rollers is controlled below 5 um), filtering (the filtering precision is more than 5 um), and filling the finished product.
Example 2
The raw materials of the sealant composition comprise the following components in parts by weight:
Figure BDA0002675753870000122
Figure BDA0002675753870000131
wherein the liquid 1, 2-polybutadiene improves the molecular chain ends of the resin; h modified vinyl; epoxy Tg; -7 ℃. The product is named as Ricao JP-200.
In a planetary stirring apparatus, first, IR-651 benzoin diethyl ether was added to a denatured bisphenol A epoxy resin and dissolved at 160 ℃ for 30 minutes, and after confirming that all of the IR-651 benzoin diethyl ether was dissolved, a liquid 1, 2-polybutadiene modified resin, bisphenol A partial epoxy (meth) acrylate, bisphenol A epoxy (meth) acrylate, and a coupling agent 3-glycidoxypropyltrimethoxysilane were added and stirred under vacuum for 30 to 60 minutes, and after confirming that all were mixed. Adding filler silicon dioxide, and stirring for 30-60 minutes under vacuum. And (3) after stirring, standing the stirring kettle, adding a thermal curing agent, namely the sebacic dihydrazide after the temperature of the stirring kettle is reduced to 25 ℃, and stirring for 30-60 minutes under vacuum under the condition that the temperature of the stirring kettle is controlled not to exceed 28 ℃. And finally, grinding by three rollers (the gap of the rollers is controlled below 5 um), filtering (the filtering precision is more than 5 um), and filling the finished product.
Example 3
The sealant composition comprises the following raw materials in parts by weight:
Figure BDA0002675753870000132
wherein the liquid 1, 2-polybutadiene improves the molecular chain ends of the resin; h modified vinyl; epoxy Tg; -7 ℃. The product is named as Ricao JP-200.
In a planetary stirring apparatus, first, IR-651 benzoin diethyl ether was added to a denatured bisphenol A epoxy resin and dissolved at 160 ℃ for 30 minutes, and after it was confirmed that all of IR-651 benzoin diethyl ether was dissolved, a liquid 1, 2-polybutadiene modified resin was added, bisphenol A partial epoxy (meth) acrylate and bisphenol A epoxy (meth) acrylate, and a coupling agent 3-glycidoxypropyltrimethoxysilane were stirred under vacuum for 30 to 60 minutes, and it was confirmed that all of them were mixed. Adding filler silicon dioxide, and stirring for 30-60 minutes under vacuum. And (3) after stirring, standing the stirring kettle, adding a thermal curing agent sebacic dihydrazide after the temperature of the stirring kettle is reduced to 25 ℃, and stirring for 30-60 minutes under vacuum under the condition that the temperature of the stirring kettle is controlled not to exceed 28 ℃. And finally, grinding by three rollers (the gap of the rollers is controlled below 5 um), filtering (the filtering precision is more than 5 um), and filling the finished product.
Example 4
The raw materials of the sealant composition comprise the following components in parts by weight:
Figure BDA0002675753870000141
wherein the liquid 1, 2-polybutadiene improves the molecular chain ends of the resin; h modified vinyl; epoxy Tg; -16 ℃. The product is named as Ricao JP-100.
In a planetary stirring apparatus, first, IR-651 benzoin diethyl ether was added to a denatured bisphenol A epoxy resin and dissolved at 160 ℃ for 30 minutes, and after confirming that all of the IR-651 benzoin diethyl ether was dissolved, a liquid 1, 2-polybutadiene modified resin, bisphenol A partial epoxy (meth) acrylate, bisphenol A epoxy (meth) acrylate, and a coupling agent 3-glycidoxypropyltrimethoxysilane were added and stirred under vacuum for 30 to 60 minutes, and after confirming that all were mixed. Adding filler silicon dioxide, and stirring for 30-60 min under vacuum. And (3) after stirring, standing the stirring kettle, adding a thermal curing agent sebacic dihydrazide after the temperature of the stirring kettle is reduced to 25 ℃, and stirring for 30-60 minutes under vacuum under the condition that the temperature of the stirring kettle is controlled not to exceed 28 ℃. And finally, grinding by three rollers (the gap of the rollers is controlled below 5 um), filtering (the filtering precision is more than 5 um), and filling the finished product.
Example 5
The sealant composition comprises the following raw materials in parts by weight:
Figure BDA0002675753870000142
Figure BDA0002675753870000151
wherein the liquid 1, 2-polybutadiene improves the molecular chain ends of the resin; urethane methyl propyl acid; modifying vinyl; no epoxy Tg; -9 ℃. The product is named as NiCao TE-2000.
In a planetary stirring apparatus, first, IR-651 benzoin diethyl ether was added to a denatured bisphenol A epoxy resin and dissolved at 160 ℃ for 30 minutes, and after it was confirmed that all of IR-651 benzoin diethyl ether was dissolved, a liquid 1, 2-polybutadiene modified resin was added, bisphenol A partial epoxy (meth) acrylate and bisphenol A epoxy (meth) acrylate, and a coupling agent 3-glycidoxypropyltrimethoxysilane were stirred under vacuum for 30 to 60 minutes, and it was confirmed that all of them were mixed. Adding filler silicon dioxide, and stirring for 30-60 minutes under vacuum. And (3) after stirring, standing the stirring kettle, adding a thermal curing agent sebacic dihydrazide after the temperature of the stirring kettle is reduced to 25 ℃, and stirring for 30-60 minutes under vacuum under the condition that the temperature of the stirring kettle is controlled not to exceed 28 ℃. And finally, grinding by three rollers (the gap of the rollers is controlled below 5 um), filtering (the filtering precision is more than 5 um), and filling the finished product.
Example 6
The raw materials of the sealant composition comprise the following components in parts by weight:
Figure BDA0002675753870000152
wherein the liquid 1, 2-polybutadiene improves the molecular chain ends of the resin; OH-modified vinyl; hydrogenated Tg; -25 ℃. The product is named as Nichio G-1000.
In a planetary stirring apparatus, first, IR-651 benzoin diethyl ether was added to a denatured bisphenol A epoxy resin and dissolved at 160 ℃ for 30 minutes, and after it was confirmed that all of IR-651 benzoin diethyl ether was dissolved, a liquid 1, 2-polybutadiene modified resin was added, bisphenol A partial epoxy (meth) acrylate and bisphenol A epoxy (meth) acrylate, and a coupling agent 3-glycidoxypropyltrimethoxysilane were stirred under vacuum for 30 to 60 minutes, and it was confirmed that all of them were mixed. Adding filler silicon dioxide, and stirring for 30-60 minutes under vacuum. And (3) after stirring, standing the stirring kettle, adding a thermal curing agent sebacic dihydrazide after the temperature of the stirring kettle is reduced to 25 ℃, and stirring for 30-60 minutes under vacuum under the condition that the temperature of the stirring kettle is controlled not to exceed 28 ℃. And finally, grinding by three rollers (the gap of the rollers is controlled below 5 um), filtering (the filtering precision is more than 5 um), and filling the finished product.
Example 7
The raw materials of the sealant composition comprise the following components in parts by weight:
Figure BDA0002675753870000161
wherein the liquid 1, 2-polybutadiene modifies the molecular chain ends of the resin; OH-modified vinyl; hydrogenated Tg; -19 ℃. The product is named as Nichio G-2000.
In a planetary stirring apparatus, first, IR-651 benzoin diethyl ether was added to a denatured bisphenol A epoxy resin and dissolved at 160 ℃ for 30 minutes, and after confirming that all of the IR-651 benzoin diethyl ether was dissolved, a liquid 1, 2-polybutadiene modified resin, bisphenol A partial epoxy (meth) acrylate, bisphenol A epoxy (meth) acrylate, and a coupling agent 3-glycidoxypropyltrimethoxysilane were added and stirred under vacuum for 30 to 60 minutes, and after confirming that all were mixed. Adding filler silicon dioxide, and stirring for 30-60 minutes under vacuum. And (3) after stirring, standing the stirring kettle, adding a thermal curing agent, namely the sebacic dihydrazide after the temperature of the stirring kettle is reduced to 25 ℃, and stirring for 30-60 minutes under vacuum under the condition that the temperature of the stirring kettle is controlled not to exceed 28 ℃. And finally, grinding by three rollers (the clearance of the rollers is controlled below 5 um), filtering (the filtering precision is more than 5 um), and filling the finished product.
Example 8
The raw materials of the sealant composition comprise the following components in parts by weight:
Figure BDA0002675753870000162
Figure BDA0002675753870000171
wherein the liquid 1, 2-polybutadiene improves the molecular chain ends of the resin; OH modified vinyl; hydrogenated Tg; -15 ℃. The product is named as Nichio G-3000.
In a planetary stirring apparatus, first, IR-651 benzoin diethyl ether was added to a denatured bisphenol A epoxy resin and dissolved at 160 ℃ for 30 minutes, and after confirming that all of the IR-651 benzoin diethyl ether was dissolved, a liquid 1, 2-polybutadiene modified resin, bisphenol A partial epoxy (meth) acrylate, bisphenol A epoxy (meth) acrylate, and a coupling agent 3-glycidoxypropyltrimethoxysilane were added and stirred under vacuum for 30 to 60 minutes, and after confirming that all were mixed. Adding filler silicon dioxide, and stirring for 30-60 min under vacuum. And (3) after stirring, standing the stirring kettle, adding a thermal curing agent, namely the sebacic dihydrazide after the temperature of the stirring kettle is reduced to 25 ℃, and stirring for 30-60 minutes under vacuum under the condition that the temperature of the stirring kettle is controlled not to exceed 28 ℃. And finally, grinding by three rollers (the gap of the rollers is controlled below 5 um), filtering (the filtering precision is more than 5 um), and filling the finished product.
Comparative example 1
The raw materials of the sealant composition comprise the following components in parts by weight:
Figure BDA0002675753870000172
in a planetary stirring apparatus, first, IR-651 benzoin diethyl ether was added to a denatured bisphenol A epoxy resin and the mixture was dissolved at 160 ℃ for 30 minutes, and after confirming that IR-651 benzoin diethyl ether was completely dissolved, bisphenol A partial epoxy (meth) acrylate and bisphenol A epoxy (meth) acrylate were added, and 3-glycidoxypropyltrimethoxysilane as a coupling agent was added and the mixture was stirred under vacuum for 30 to 60 minutes, and it was confirmed that the mixture was completely mixed. Adding filler silicon dioxide, and stirring for 30-60 minutes under vacuum. And (3) after stirring, standing the stirring kettle, adding a thermal curing agent sebacic dihydrazide after the temperature of the stirring kettle is reduced to 25 ℃, and stirring for 30-60 minutes under vacuum under the condition that the temperature of the stirring kettle is controlled not to exceed 28 ℃. And finally, grinding by three rollers (the gap of the rollers is controlled below 5 um), filtering (the filtering precision is more than 5 um), and filling the finished product.
Comparative example 2
The raw materials of the sealant composition comprise the following components in parts by weight:
Figure BDA0002675753870000181
wherein the liquid 1, 2-polybutadiene modifies the molecular chain ends of the resin; h modified vinyl; epoxy Tg; -7 ℃. The product is named as Ricao JP-200.
In a planetary stirring apparatus, first, IR-651 benzoin diethyl ether was added to a denatured bisphenol A epoxy resin and dissolved at 160 ℃ for 30 minutes, and after confirming that all of the IR-651 benzoin diethyl ether was dissolved, a liquid 1, 2-polybutadiene modified resin, bisphenol A partial epoxy (meth) acrylate, bisphenol A epoxy (meth) acrylate, and a coupling agent 3-glycidoxypropyltrimethoxysilane were added and stirred under vacuum for 30 to 60 minutes, and after confirming that all were mixed. Adding filler silicon dioxide, and stirring for 30-60 minutes under vacuum. And (3) after stirring, standing the stirring kettle, adding a thermal curing agent sebacic dihydrazide after the temperature of the stirring kettle is reduced to 25 ℃, and stirring for 30-60 minutes under vacuum under the condition that the temperature of the stirring kettle is controlled not to exceed 28 ℃. And finally, grinding by three rollers (the clearance of the rollers is controlled below 5 um), filtering (the filtering precision is more than 5 um), and filling the finished product.
Table 1 shows the relevant performance data for the sealant compositions obtained in the examples and comparative examples
Figure BDA0002675753870000182
Figure BDA0002675753870000191
Figure BDA0002675753870000201
The test method comprises the following steps:
1. adhesion property
A very small amount of the sealant for a liquid crystal display element obtained in each of examples and comparative examples was placed in the center of a polyethylene terephthalate (PET) film (linetec co., ltd. product, "PET 5011") of 20mm × 50mm, and the same size of PET5011 was overlaid thereon, and the sealant for a liquid crystal display element was pressed and spread. In this state, the lamp was irradiated with 100mW/cm for 30 seconds using a metal halide lamp 2 After UV irradiation (wavelength: 365nm), the plate was heated at 120 ℃ for 1 hour to prepare an adhesion test piece. The adhesion strength of the obtained adhesion test piece was measured using EZgraph (manufactured by Shimadzu corporation). Further, an adhesion test piece was similarly prepared using a glass substrate instead of PET5011, and the adhesion strength was measured.
The adhesiveness to the PET film was evaluated as "O" when the adhesiveness was 3.5kg/cm or more, as "Delta" when the adhesiveness was 3.0kg/cm or more and less than 3.5kg/cm, and as "X" when the adhesiveness was less than 3.0 kg/cm.
2. Reliability in high temperature and high humidity
Each of the liquid crystal display elements obtained in examples and comparative examples was coated in a thickness of 200 to 300 μm in the form of a smooth release film by a coater, and the resulting coating was irradiated with a metal halide lamp for 30 seconds at a rate of 100mW/cm 2 After ultraviolet light (wavelength: 365nm), the cured film was heated at 120 ℃ for 1 hour to obtain a cured film for moisture permeability measurement. A cup for moisture permeability test was produced by the method of moisture permeability test method (cup method) for moisture-proof packaging material according to JIS Z0208, the obtained cured film for moisture permeability measurement was mounted, and the film was put into a constant temperature and humidity oven at 60 ℃ and 90% RH to measure the moisture permeability for 24 hours.
The obtained value of moisture permeability is less than 20g/m 2 It was marked as "O" and was 20g/m 2 Above and below 40g/m 2 When written as "Δ", it was 40g/m 2 The moisture permeability resistance was evaluated by marking as "x" in the above.
3. Contamination of liquid crystal
1 part by weight of spacer particles (MICRO PEARL SI-H050, manufactured by WATERPOCHOLOGICAL INDUSTRIAL Co., Ltd.) were dispersed in 100 parts by weight of each of the sealants for liquid crystal display elements obtained in examples and comparative examples, and the resultant was applied by dispensing a sealant having a line width of 1mm so that a display portion thereof became 45mm × 55mm on one of two substrates (75 mm in length, 75mm in width and 0.7mm in thickness) provided with a rubbed alignment film and a transparent electrode.
Next, minute droplets of liquid crystal (JC-5004 LA, manufactured by CHISSO CORPORATION) were applied dropwise to the entire inner surface of the frame of the sealant of the substrate with transparent electrode, another substrate with color filter having transparent electrode was immediately bonded, and the sealant portion was irradiated with 100mW/cm for 30 seconds using a metal halide lamp 2 After ultraviolet light (wavelength: 365nm), the resultant was heated at 120 ℃ for 1 hour to obtain a liquid crystal display element.
After the operation test for 100 hours was performed on the obtained liquid crystal display element, the alignment of liquid crystal in the vicinity of the sealant was visually confirmed to be disturbed in a state where a voltage of 1000 hours was applied at 80 ℃.
Alignment disorder was judged by color unevenness on the display part, and low liquid crystal contamination was evaluated by "o" when no alignment disorder was present, by "Δ" when the length of alignment disorder was 1% or less of the length of the sealant, and by "x" when the length of alignment disorder was 1% or more of the length of the sealant, depending on the degree of color unevenness.
Note that the liquid crystal display element evaluated as "o" is a level that has no problem at all in practical use, "Δ" is a level that may cause a problem depending on the display design of the liquid crystal display element, and "x" is a level that is not suitable for practical use.
4. Coatability
The rubber tube was filled with the rubber, and after defoaming in a vacuum defoaming machine, it was coated with a coater with a coating cross-sectional area controlled at 2000um or less for 1 hour, and the number of broken threads was counted, and the number of broken threads was rated as O from 0 to 3 and X from 3 to 5 to Δ 5.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which may be made by those skilled in the art without departing from the spirit and scope of the present invention as defined in the appended claims.

Claims (7)

1. A sealant composition, the sealant composition comprising: part of (methyl) acrylic acid modified epoxy resin, epoxy (methyl) acrylate, EB3700, photoinitiator, coupling agent, thermal curing agent, filler and liquid 1, 2-polybutadiene modified resin;
the liquid 1, 2-polybutadiene improved resin is one or two of the following structural formula (Ib) and formula (ic):
Figure FDA0003718573660000011
wherein n is 1 /n 2 1/4-1/2; the number average molecular weight of formula (Ib) is 1300-2200;
Figure FDA0003718573660000012
the number average molecular weight of formula (ic) is 2000-3000;
the sealant composition comprises the following raw materials in parts by weight:
Figure FDA0003718573660000013
2. the sealant composition of claim 1 further comprising any one or more of the following conditions:
A1) the part of the (meth) acrylic acid-modified epoxy resin has 1 or more epoxy groups and 1 or more (meth) acryloyloxy groups in 1 molecule;
A2) the grafting rate of the partial (methyl) acrylic acid modified epoxy resin is 50-100%;
A3) the epoxy (meth) acrylate is a compound obtained by reacting all epoxy groups in an epoxy resin with (meth) acrylic acid;
A4) the photoinitiator is one or more of benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds and thioxanthone;
A5) the thermal curing agent is selected from one or more of organic acid hydrazide, imidazole derivative, amine compound, polyhydric phenol compound and acid anhydride;
A6) the coupling agent is selected from one or more of gamma-aminopropyl trimethoxy silane, gamma-mercapto propyl trimethoxy silane, gamma-glycidoxypropyl trimethoxy silane and gamma-isocyanate propyl trimethoxy silane;
A7) the filler is selected from organic fillers and/or inorganic fillers.
3. The sealant composition of claim 2 wherein said thermal curing agent is selected from the group consisting of organic acid hydrazides;
and/or, the inorganic filler is selected from one or more of talc, asbestos, silica, diatomite, smectite, bentonite, calcium carbonate, magnesium carbonate, alumina, montmorillonite, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, magnesium hydroxide, aluminum hydroxide, glass beads, silicon nitride, barium sulfate, gypsum, calcium silicate, sericite activated clay and aluminum nitride;
and/or, the organic filler is selected from one or more of polyester particles, polyurethane particles, vinyl polymer particles and acrylic polymer particles.
4. A method of preparing a sealant composition according to any one of claims 1 to 3, comprising mixing a part of the (meth) acrylic acid-modified epoxy resin, epoxy (meth) acrylate, EB3700, a photoinitiator, a coupling agent, a thermal curing agent, a filler, and a liquid 1, 2-polybutadiene improving resin.
5. The method for preparing the sealant composition according to claim 4, wherein the photoinitiator is first dissolved in EB3700 at 120 to 180 ℃;
adding liquid 1, 2-polybutadiene improved resin, partial (methyl) acrylic acid modified epoxy resin, epoxy (methyl) acrylate and a coupling agent, and stirring for 30-60 minutes under vacuum;
adding the filler, and stirring for 30-60 minutes under vacuum;
and cooling to 25 ℃, adding a thermal curing agent, and stirring for 30-60 minutes in vacuum when the temperature is not lower than 28 ℃.
6. Use of the sealant composition according to any one of claims 1 to 3 in a liquid crystal display element.
7. A liquid crystal display element comprising the sealant composition according to any one of claims 1 to 3.
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CN113088233A (en) * 2021-03-24 2021-07-09 Tcl华星光电技术有限公司 Frame glue material, display panel and manufacturing method thereof
CN114262594A (en) * 2021-12-24 2022-04-01 南京华生皓光电科技有限公司 Sealant composition

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CN109073937A (en) * 2016-09-29 2018-12-21 积水化学工业株式会社 Sealing material for liquid crystal display device, upper and lower conductive material and liquid crystal display element
CN109294460A (en) * 2018-10-25 2019-02-01 山东大学 A kind of UV solidification Liquid optical clear adhesive of color inhibition and preparation method thereof
CN109988541A (en) * 2018-12-17 2019-07-09 瑞声科技(新加坡)有限公司 Adhesive

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109073937A (en) * 2016-09-29 2018-12-21 积水化学工业株式会社 Sealing material for liquid crystal display device, upper and lower conductive material and liquid crystal display element
CN109294460A (en) * 2018-10-25 2019-02-01 山东大学 A kind of UV solidification Liquid optical clear adhesive of color inhibition and preparation method thereof
CN109988541A (en) * 2018-12-17 2019-07-09 瑞声科技(新加坡)有限公司 Adhesive

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