CN106366998A - Liquid crystal sealing agent and liquid crystal display cell using the same - Google Patents
Liquid crystal sealing agent and liquid crystal display cell using the same Download PDFInfo
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- CN106366998A CN106366998A CN201610491657.1A CN201610491657A CN106366998A CN 106366998 A CN106366998 A CN 106366998A CN 201610491657 A CN201610491657 A CN 201610491657A CN 106366998 A CN106366998 A CN 106366998A
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- liquid crystal
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- injection method
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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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/542—Macromolecular compounds
- C09K19/544—Macromolecular compounds as dispersing or encapsulating medium around the liquid crystal
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/062—Copolymers with monomers not covered by C08L33/06
- C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups
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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
- 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
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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
- 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
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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
- 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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- 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
- G02F1/1341—Filling or closing of cells
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
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- 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
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- 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
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- 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
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- Organic Chemistry (AREA)
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- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
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- General Physics & Mathematics (AREA)
- Mathematical Physics (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Sealing Material Composition (AREA)
- Liquid Crystal (AREA)
Abstract
The invention relates to a liquid crystal sealing agent and a liquid crystal display cell using the same. The invention relates to a crystal liquid sealing agent using heat to perform solidification for liquid crystal instillation. The invention provides a liquid crystal sealing agent for the liquid crystal instillation method which is low in wiring corrosivity, low in crystal pollution and good in resisting dampness and hot. As a result, the liquid crystal sealing agent and the liquid crystal display cell realize high finesse, high speed response, low voltage driving, and long service time. The liquid crystal sealing agent for the liquid crystal instillation method comprises (A) a solidified compound. The (A) solidified compound can be solidified in one hour in 130 DEG temperature without being radiated by ultraviolet ray; water absorption rate is lower than 2.0% according to JIS-K7209 and moisture permeability is 130g/m2*24h according to JIS-K7129.
Description
Technical field
The present invention relates to for the liquid crystal sealing agent of liquid crystal drip-injection method, this liquid crystal sealing agent is solidified using heat.More detailed
For thin, the present invention relates to the wire corrosion after humidity test is extremely low and low liquid crystal pollution, adhesive strength etc. are typically special
The also excellent liquid crystal sealing agent for liquid crystal drip-injection method of property.
Background technology
With the maximization of liquid crystal display in recent years, the manufacture method as liquid crystal display is it is proposed that measure
The higher so-called liquid crystal drip-injection method (referring to patent documentation 1, patent documentation 2) of producing property.Specifically, it is liquid crystal as described below
The manufacture method of display unit: by the inner side of liquid crystal drip-injection to the cofferdam forming liquid crystal sealing agent on one substrate, then
Fit another substrate, thus by sealing liquid crystal.
However, liquid crystal drip-injection method there are the following problems: the liquid crystal sealing agent due to its uncured state is contacted with liquid crystal, because
This, now composition dissolving (dissolution) of liquid crystal sealing agent makes the resistance value of liquid crystal decline in liquid crystal, produces near sealing
Display is bad.
In order to solve this problem, currently use photo-thermal and with the liquid crystal sealing agent of type as the liquid crystal for liquid crystal drip-injection method
Sealant, and practical (patent documentation 3,4).Liquid crystal drip-injection method using this liquid crystal sealing agent is characterised by, by right
The liquid crystal sealing agent irradiation light that clipped by substrate and make its one-step solidification, then its secondary solidification is made by heating.According to this
Method, can suppress liquid crystal sealing agent composition dissolving (dissolution) using light by uncured liquid crystal sealing agent fast setting
To in liquid crystal.Additionally, only in the case of photocuring, also producing the adhesive strength being led to by cure shrinkage during photocuring etc. not enough
Such problem, but if being photo-thermal and using type, then has the advantage that and can be answered by using the secondary solidification of heating
Power relaxing effect is additionally it is possible to solve the above problems.
The liquid crystal sealing agent for liquid crystal drip-injection method of this photo-thermal curing type is practical, and thus, liquid crystal drip-injection method becomes
Commonly used approach.
Practical by above-mentioned liquid crystal drip-injection method, even large-scale liquid crystal display is it is also possible to easily carry out
Manufacture, its result result in the popularization of liquid crystal display.
On the other hand, sometimes there is shortcoming in this liquid crystal drip-injection method in terms of the quality of the liquid crystal display manufacturing.Wherein
One of be in terms of the driving of the liquid crystal after moisture-proof reliability produce defect problem.Even if this problem is by existing liquid
Also the problem that can produce in the liquid crystal display of brilliant injection mode manufacture, but in the liquid crystal being manufactured by liquid crystal drip-injection method
Show particularly significant in unit.In order to solve this problem, various effort have been carried out all the time.For example, by adding heat
Radical polymerization initiator, curing accelerator are improving response rate；Using the low material of the dissolubility in liquid crystal as being constituted into
Grade.
But, even if by these researchs, be also not carried out fully solving the problems referred to above for liquid crystal drip-injection method
Liquid crystal sealing agent.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Application 63-179323 publication
Patent documentation 2: Japanese Unexamined Patent Publication 10-239694 publication
Patent documentation 3: No. 3583326 publications of Japanese Patent No.
Patent documentation 4: Japanese Unexamined Patent Publication 2004-61925 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2004-126211 publication
Patent documentation 6: Japanese Unexamined Patent Publication 2009-8754 publication
Patent documentation 7: International Publication 2008/004455
Content of the invention
Invent problem to be solved
The present invention relates to a kind of liquid crystal sealing agent for liquid crystal drip-injection method utilizing heat to be solidified, present invention proposition one
Kind for liquid crystal drip-injection method liquid crystal sealing agent, the wire corrosion after its humidity test is extremely low and low liquid crystal pollution, glue
The general characteristics such as viscous intensity are also excellent, it is thereby achieved that the High precision of liquid crystal display cells, high-speed response, low-voltage are driven
Dynamicization, long lifetime.
Means for solving the problem
The present inventor has made intensive studies to solve the problems, such as above-mentioned driving defect, it was found that this problem is
Because the wire corrosion after humidity test causes, this wire corrosion be subject to as such utilization ultraviolet under black matrix solidification not
The poisture-penetrability at position after being solidified almost fully and merely with heat and absorptive impact, thus complete the application send out
Bright.
That is, the present invention relates to following 1)～14).It should be noted that in this manual, it is being recited as " (methyl) third
In the case of olefin(e) acid ", refer to " acrylic acid " and/or " methacrylic acid ".In addition, " for the liquid crystal sealing agent of liquid crystal drip-injection method "
Sometimes it is abbreviated as " liquid crystal sealing agent ".
1)
A kind of liquid crystal sealing agent for liquid crystal drip-injection method, it contains (a) curable compound,
The measuring according to jis-k7209 of non-irradiation ultraviolet radiation and solidfied material after only carrying out heat cure in 1 hour at 130 DEG C
Water absorption rate is less than 2.0%, is 130g/m according to the moisture permeability that jis-k7129 measures2Below 24h.
2)
The liquid crystal sealing agent for liquid crystal drip-injection method as described in above-mentioned 1), it also contains the polymerization of (b) hot radical and causes
Agent.
3)
As above-mentioned 1) or 2) as described in the liquid crystal sealing agent for liquid crystal drip-injection method, wherein, mentioned component (b) hot radical
Polymerization initiator is the hot radical polymerization initiator not containing o-o bond (- o-o-) and nitrogen-nitrogen key (- n=n-) in intramolecular.
4)
As above-mentioned 1) to 3) any one of the liquid crystal sealing agent for liquid crystal drip-injection method, its also contain (c) light from
By base polymerization initiator.
5)
As above-mentioned 1) to 4) any one of the liquid crystal sealing agent for liquid crystal drip-injection method, it also contains (d) filler,
This filler is more than 20 mass % in the containing ratio in liquid crystal sealing agent total amount.
6)
As above-mentioned 1) to 5) any one of the liquid crystal sealing agent for liquid crystal drip-injection method, wherein, mentioned component (d)
Mixture for (d-1) organic filler and (d-2) inorganic filler.
7)
As above-mentioned 1) to 6) any one of the liquid crystal sealing agent for liquid crystal drip-injection method, wherein, mentioned component (d-
2) inorganic filler is more than 20 mass % in the containing ratio in liquid crystal sealing agent total amount.
8)
As above-mentioned 1) to 7) any one of the liquid crystal sealing agent for liquid crystal drip-injection method, wherein, mentioned component (a)
Curable compound is epoxy (methyl) acrylate compounds.
9)
As above-mentioned 1) to 7) any one of the liquid crystal sealing agent for liquid crystal drip-injection method, wherein, mentioned component (a)
Curable compound is the mixture of epoxy (methyl) acrylate compounds and epoxide.
10)
As above-mentioned 1) to 9) any one of the liquid crystal sealing agent for liquid crystal drip-injection method, it also contains (e) thermosetting
Agent.
11)
The liquid crystal sealing agent for liquid crystal drip-injection method as described in above-mentioned 10), wherein, mentioned component (e) thermal curing agents are
Organic hydrazides.
12)
As above-mentioned 1) to 11) any one of the liquid crystal sealing agent for liquid crystal drip-injection method, it also contains (f) silane
Coupling agent.
13)
A kind of manufacture method of liquid crystal display is it is characterised in that by liquid crystal drip-injection to the liquid crystal comprising two substrates
Form above-mentioned 1) on one substrate in display unit to 12) any one of the sealing liquid crystal for liquid crystal drip-injection method
The inner side in the cofferdam of agent, another substrate of then fitting, then solidified using light and/or heat.
14)
A kind of liquid crystal display, it utilizes above-mentioned 1) to 12) any one of the liquid for liquid crystal drip-injection method
Solidfied material obtained from brilliant sealant cures is sealed.
Invention effect
The liquid crystal sealing agent for liquid crystal drip-injection method of the present invention can suppress wire corrosion and low liquid to greatest extent
Brilliant contaminative, adhesive strength are also excellent, exceedingly useful accordingly, as liquid crystal sealing agent used for liquid crystal display element.
Brief description
Fig. 1 is the figure of the solidification width illustrating light shielding part.The central authorities of the glass substrate after chrome plating is etched
Coating with the addition of the liquid crystal sealing agent of 5 μm of glass fibre of 1 weight %, is used black matrix substrate to be pasted as opposite substrate
Close, and be fixed (ultraviolet pre-irradiation) using clip.Glass substrate side after Xiang Qicong is etched to chromium is irradiated
3000mj/cm2Ultraviolet, then will laminating two strippable substrates, by microscope to the part being blocked below chromium
Confirmed, and measured the solidification width of light shielding part.
Specific embodiment
The liquid crystal sealing agent of the present invention contains (a) curable compound.
As long as composition (a) is just not particularly limited using the compound that light or heat carry out polyreaction, example can be enumerated
As: there is the curable compound of (methyl) acryloyl group, there is curable compound of epoxy radicals etc..
The curable compound with (methyl) acryloyl group can be enumerated for example: (methyl) acrylate, epoxy (first
Base) acrylate etc..As (methyl) acrylate, can enumerate: benzyl methacrylate, cyclohexyl methacrylate, sweet
The modified glycerol tri-acrylate of oily dimethylacrylate, glycerol tri-acrylate, eo, pentaerythritol acrylate, three hydroxyls
Propane tri, isocyanuric acid three (acryloyl-oxyethyl) ester, dipentaerythritol acrylate, phloroglucinol
Triacrylate etc..Epoxy (methyl) acrylate can by epoxide with (methyl) acrylic acid reaction using known
Method obtain.As the epoxide becoming raw material, it is not particularly limited, preferably epoxide more than difunctionality,
Can enumerate for example: Bisphenol A Type epoxide, Bisphenol-f epoxide, bis-phenol s type epoxide, phenol novolac are clear
Paint shaped epoxide, cresol novolak type epoxy compound, bis-phenol a novolak type epoxy compounds, bis-phenol f phenolic aldehyde are clear
Paint shaped epoxide, cycloaliphatic epoxy, aliphatic chain epoxide, glycidyl ester type epoxy compound,
Glycidyl amine epoxy compound, hydantoin type epoxide, isocyanurate type epoxide, there are three oxybenzenes
Two contractings of the bifunctional phenols such as the phenol novolak-type epoxy compound of methylmethane skeleton and catechol, resorcinol
Water glycerol etherate, the 2-glycidyl etherate of difunctionality alcohols and their halogenide, hydride etc..Wherein, from liquid crystal
From the viewpoint of contaminative, preferably there is the epoxide of resorcinol skeleton, such as resorcinolformaldehyde resin etc..
In addition, epoxy radicals are not limited with the ratio of (methyl) acryloyl group, from the viewpoint of operation adaptability and liquid crystal pollution
Suitably select.
Accordingly, it is preferred that the curable compound with (methyl) acryloyl group is that have (methyl) acryloyl group, also have
There are the curable compound of resorcinol skeleton, for example, acrylate of resorcinolformaldehyde resin, resorcinol two
The methacrylate of glycidyl ether.
As the curable compound with epoxy radicals, epoxide can be enumerated.Do not have as this epoxide
It is particularly limited to, preferably epoxide more than difunctionality, can enumerate for example: Bisphenol A Type epoxide, Bisphenol-f ring
Oxygen compound, bis-phenol s type epoxide, phenol novolak-type epoxy compound, cresol novolak type epoxy compound,
Bis-phenol a novolak type epoxy compounds, bis-phenol f novolak type epoxy compounds, cycloaliphatic epoxy, aliphatic chain
Shape epoxide, glycidyl ester type epoxy compound, glycidyl amine epoxy compound, hydantoin type epoxy compound
Thing, isocyanurate type epoxide, have three oxybenzene methylmethane skeletons phenol novolak-type epoxy compound and
The 2-glycidyl etherate of bifunctional phenols, the 2-glycidyl etherate of difunctionality alcohols and their halogenide, hydrogenation
Thing etc..Wherein, from the viewpoint of liquid crystal pollution, more preferably biphenol type epoxy compound, nobolak type epoxy
Compound.
The curable compound with (methyl) acryloyl group, the curable compound with epoxy radicals can also mix to be made
With two or more, it is the especially excellent of the present application that (methyl) acrylate epoxy compound is used in mixed way with epoxide
One of mode of choosing.
The content of the composition (a) in the liquid crystal sealing agent of the present invention is usually 30～75 mass %, is preferably 40～65 matter
Amount %, in addition, particularly by epoxide and (methyl) acrylate epoxy compound and with the case of, composition (a)
In the content of epoxide be usually 3～30 mass %, be preferably 5～20 mass %, more preferably 8～15 mass %.
With regard to the liquid crystal sealing agent of the present invention, non-irradiation ultraviolet radiation and the solidification after only carrying out heat cure in 1 hour at 130 DEG C
The water absorption rate measuring according to jis-k7209 (d method) of thing is that less than 2.0% (wherein, experimental condition uses 60 DEG C, 90% ring
Border).This is because: the moisture absorbed in liquid crystal sealing agent promotes decomposing and decomposing of the Organic substance in liquid crystal sealing agent
Product, foreign ion transport to outside liquid crystal sealing agent.
This water absorption rate is preferably less than 1.8%, more preferably less than 1.6%.
With regard to the liquid crystal sealing agent of the present invention, non-irradiation ultraviolet radiation and the solidification after only carrying out heat cure in 1 hour at 130 DEG C
The moisture permeability by the method mensure according to jis-k7129 (a method) of thing is 130g/m2Below 24h.This is because: pass through
The impact that the moisture of liquid crystal sealing agent produces to wire corrosion is big.It should be noted that using systech illinois company
During the lyssyl80-5000 manufacturing, the mensure according to jis-k7129 (a method) can be carried out.It should be noted that setting examination
Test and carry out under temperature 60 C.
This moisture permeability is preferably 110g/m2Below 24h, more preferably 90g/m2Below 24h.
The liquid crystal sealing agent of the present invention can realize curing rate, curing degree using (b) hot radical polymerization initiator
Raising.
As long as hot radical polymerization initiator produces free radical by heating and causes the chemical combination of chain polymerization
Thing is just not particularly limited, and can enumerate: organic peroxide, azo-compound, benzoin compound, benzoin ether chemical combination
Thing, acetophenone compound, benzpinacol etc., preferably use benzpinacol.For example, as organic peroxide, can be with commercially available
The form of product obtains kayamekrtma、m、r、l、lh、sp-30c、perkadox ch-50l、bc-ff、cadox b-40es、
perkadox 14、trigonoxrtm22-70e、23-c70、121、121-50e、121-ls50e、21-ls50e、42、42ls、
kayaesterrtmp-70、tmpo-70、cnd-c70、oo-50e、an、kayabutylrtmb、perkadox 16、
kayacarbonrtmBic-75, aic-75 (chemical medicine akzo Co. Ltd. system), permekrtmn、h、s、f、d、g、perhexartm
h、hc、per tmh、c、v、22、mc、percurertmah、al、hb、perbutylrtmh、c、nd、l、percumylrtmh、d、
peroylrtmib、ipp、peroctartmNd (Japan Oil Co's system) etc..
In addition, as azo-compound, va-044, v-070, vpe-0201, vsp- can be obtained in the form of commercially available product
1001 (Wako Pure Chemical Industries, Ltd.'s systems) etc..It should be noted that in this manual, upper target rtm refers to registrar
Mark.
As composition (b), preferably do not have in intramolecular the heat of o-o bond (- o-o-) or nitrogen-nitrogen key (- n=n-) from
By base polymerization initiator.This is because: in intramolecular, there is o-o bond (- o-o-) or the hot radical of nitrogen-nitrogen key (- n=n-)
Polymerization initiator produces substantial amounts of oxygen, nitrogen when generating free radical, therefore, it is possible to remain bubble in liquid crystal sealing agent
State solidified, make the characteristics such as adhesive strength reduce.The hot radical polymerization initiator of particularly preferably benzpinacol class (wraps
Include material obtained from benzpinacol is chemically modified).Specifically, can enumerate: benzpinacol, 1,2- dimethoxy
Base -1,1,2,2- tetraphenyl ethane, 1,2- diethoxy -1,1,2,2- tetraphenyl ethane, 1,2- hexichol Oxy-1,1,2,2- tetra-
Diphenylphosphino ethane, 1,2- dimethoxy -1,1,2,2- four (4- aminomethyl phenyl) ethane, 1,2- hexichol Oxy-1,1,2,2- tetra- (4- first
Phenyl) ethane, double (the trimethylsiloxy) -1,1,2,2- tetraphenyl ethane of 1,2-, the double (triethyl-silicane of 1,2-
Epoxide) -1,1,2,2- tetraphenyl ethane, 1,2- double (t-butyldimethylsilyloxy base) -1,1,2,2- tetraphenyl ethane, 1-
Hydroxyl -2- trimethylsiloxy -1,1,2,2- tetraphenyl ethane, 1- hydroxyl -2- triethyl-silicane Oxy-1,1,2,2-
Tetraphenyl ethane, 1- hydroxyl -2- t-butyldimethylsilyloxy base -1,1,2,2- tetraphenyl ethane etc., preferably 1- hydroxyl -
2- trimethylsiloxy -1,1,2,2- tetraphenyl ethane, 1- hydroxyl -2- triethyl-silicane Oxy-1,1,2,2- tetra- benzene
Double (the trimethyl silyl of base ethane, 1- hydroxyl -2- t-butyldimethylsilyloxy base -1,1,2,2- tetraphenyl ethane, 1,2-
Epoxide) -1,1,2,2- tetraphenyl ethane, more preferably 1- hydroxyl -2- trimethylsiloxy -1,1,2,2- tetraphenyl second
Double (trimethylsiloxy) -1 of alkane, 1,2-, 1,2,2- tetraphenyl ethane, the double (trimethyl silyl of particularly preferably 1,2-
Epoxide) -1,1,2,2- tetraphenyl ethane.
Above-mentioned benzpinacol is commercially available by Tokyo HuaCheng Industry Co., Ltd, Wako Pure Chemical Industries, Ltd. etc..In addition, it is right
The hydroxyl of benzpinacol is carried out etherificate and easily can be synthesized by known method.In addition, the hydroxyl to benzpinacol
Carry out silicyl etherificate can pass through corresponding benzpinacol and various silylating agent in base catalysts such as pyridines
In the presence of heating method be synthesized into.As silylating agent, can enumerate commonly known as trimethyl first
The trim,ethylchlorosilane (tmcs) of silane-based agent, hexamethyldisiloxane (hmds), n, double (trimethyl silyl) three of o-
Fluoroacetic acid amide (bstfa), the chlorotriethyl silane (tecs) as triethylsilyl agent, as tertbutyldimethylsilyl chloride
T-butyldimethylsilyl (tbms) of silane-based agent etc..These reagent easily can obtain from the markets such as silicon derivative manufacturer
?.As the response magnitude of silylating agent, it is preferably 1.0～5.0 times moles with respect to 1 mole of the hydroxyl of subject compound.
More preferably 1.5～3.0 times moles.During less than 1.0 times moles, reaction efficiency is poor, and the response time is elongated, therefore can promote heat point
Solution.During more than 5.0 times moles, separate when reclaiming and be deteriorated or be difficult to purification.
Composition (b) preferable particle size is thin and is uniformly dispersed.When its mean diameter is excessive, in the liquid crystal display manufacturing narrow gap
During unit, the undesirable element in gap etc. when becoming lower glass substrate in laminating, cannot be formed well, therefore preferably 5 μm with
Under, more preferably less than 3 μm.Furthermore it is possible to unrestrictedly attenuate, but usual lower limit is about 0.1 μm.Particle diameter can utilize laser
Diffraction/scattering formula particle size distribution device (dry type) (セ イ シ Application enterprise of Co., Ltd. system；Lms-30) measuring.
As the content of composition (b), in the total amount of liquid crystal sealing agent, preferably 0.0001～10 mass %, more preferably
For 0.0005～5 mass %, particularly preferably 0.001～3 mass %.
The liquid crystal sealing agent of the present invention can use that photo-thermal made by (c) optical free radical polymerization initiator and the liquid crystal with type is close
Envelope agent.
As long as optical free radical polymerization initiator is produced free radical and causes chain poly- by irradiation ultraviolet radiation, visible ray
The compound closing reaction is just not particularly limited, and can enumerate for example: benzil dimethyl ketal, 1- hydroxycyclohexylphenyl first
Ketone, diethyl thioxanthone, benzophenone, 2-ethyl-anthraquinone, 2- hydroxy-2-methyl propiophenone, 2- methyl-[4- (methyl mercapto) benzene
Base] -2- morpholino -1- propane, 2,4,6- trimethyl benzoyl diphenyl base phosphine oxide, camphorquinone, 9-Fluorenone, Diphenyl disulfide
Ether etc..Specifically, can enumerate: irgacurertm651、184、2959、127、907、369、379eg、819、784、754、
500、oxe01、oxe02、darocurertm1173、lucirinrtmTpo (being basf company system), seikuolrtmz、bz、
Bee, bip, bbi (being Seiko KCC system) etc..
In addition, from the viewpoint of liquid crystal pollution, be preferably used in intramolecular and have the light of (methyl) acryloyl group from
By base polymerization initiator, for example, preferably use 2- methacryloxyethyl isocyanates and 1- [4- (2- hydroxyl-oxethyl)
Phenyl] -2- hydroxy-2-methyl -1- propane -1- ketone product.This compound can pass through International Publication No. 2006/
No. 027982 record method manufacture and obtain.
In addition, from improve because wiring, black matrix and the viewpoint of the curable of the light shielding part that light cannot substantially arrive at is gone out
Send out, the extinction coefficient under the 350nm being preferably measured in acetonitrile are 500ml g-1The situation of more than cm.For example,
irgacurertm651、907、369、379eg、819、784、oxe01、oxe02、lucirinrtmTpo (is basf company
System), diethyl thioxanthone, benzophenone etc..
In the liquid crystal sealing agent of the present invention, spendable composition (c) optical free radical polymerization initiator is in liquid crystal sealing agent
Content in the total amount of the liquid crystal sealing agent of the present invention be usually 0.1～20 mass %, be preferably 0.2～15 mass %.
The liquid crystal sealing agent of the present invention can realize the raising of adhesive strength using (d) filler.This filler can be (d-
1) organic filler, can also for (d-2) inorganic filler, can also be its mixture, but due to each having difference in functionality, therefore
It is preferably the situation of both mixture.
In the total amount of liquid crystal sealing agent, the containing ratio of (d) filler is usually 5～70 mass %, is preferably 10～60 matter
Amount %.Additionally, when the containing ratio of (d) filler is more than 20 mass %, particularly marked degree playing the effect of the present application, especially
It is preferably 20～50 mass %.
As composition (d-1) organic filler, can enumerate for example: carbamate microgranule, acrylic fine particles, styrene
Microgranule, styrene alkene microgranule and organic silicone microparticle.It should be noted that as organic silicone microparticle preferred kmp-594, kmp-
597th, kmp-598 (SHIN-ETSU HANTOTAI's chemical industry system), trefilrtmE-5500,9701, ep-2001 (Dong Li Dow Corning Corporation system), make
For carbamate microgranule preferred jb-800t, hb-800bk (Negami Chemical Ind Co., Ltd.), preferred as styrene particulate
rabalonrtmT320c, t331c, sj4400, sj5400, sj6400, sj4300c, sj5300c, sj6300c (Mitsubishi Chemical
System), as the preferred septon of styrene alkene microgranulertmseps2004、seps2063.
These organic fillers can be used alone it is also possible to and with two or more.Further, it is possible to use two or more formation
Nucleocapsid structure.Wherein, preferably acrylic fine particles, organic silicone microparticle.
In the case of using aforesaid propylene acids microgranule, preferably comprise two kinds of acrylic rubbers nucleocapsid structure third
The situation of olefin(e) acid class rubber, particularly preferred stratum nucleare is n-butyl acrylate, and shell is the acrylic compounds rubber of methyl methacrylate
Glue.It is with zefiacrtmThe form of f-351 is sold by Eike Kogyo K.K..
In addition, as above-mentioned organic silicone microparticle, can enumerate: organopolysiloxane crosslinking powder, straight chain dimethyl gather
Silicone cross-linked powder etc..In addition, as composite silicone rubber, can be set forth in above-mentioned silicone rubber surface be coated to siliconated
The composite silicone rubber of compound (such as organic poly sesquisiloxane compound).In these microgranules, particularly preferred straight chain dimethyl gathers
The silicone rubber of silicone cross-linked powder or the comprehensive silicon rubber of the coating straight chain dimethyl polysiloxane cross-linked powder of organo-silicon compound
Glue microgranule.These organic silicone microparticles can be used alone it is also possible to and with two or more.Additionally, it is preferable that rubber powder
Shape can be few spherical for the increase of viscosity after adding.In the liquid crystal sealing agent of the present invention using composition (d) in the case of,
It is usually 5～50 mass % in the total amount of liquid crystal sealing agent, be preferably 5～40 mass %.
As composition (d-2) inorganic filler, can enumerate: silicon dioxide, carborundum, silicon nitride, boron nitride, Calcium Carbonate,
Magnesium carbonate, barium sulfate, calcium sulfate, Muscovitum, Talcum, clay, aluminium oxide, magnesium oxide, zirconium oxide, aluminium hydroxide, magnesium hydroxide, silicon
Sour calcium, aluminium silicate, lithium aluminium silicate, Zirconium orthosilicate., Barium metatitanate., glass fibre, carbon fiber, molybdenum bisuphide, asbestos etc., preferably can arrange
Lift fused silica, crystalline silica, silicon nitride, boron nitride, Calcium Carbonate, barium sulfate, calcium sulfate, Muscovitum, Talcum, glue
Soil, aluminium oxide, aluminium hydroxide, calcium silicates, aluminium silicate, preferably silicon dioxide, aluminium oxide, Talcum.These inorganic fillers are permissible
It is used in mixed way two or more.
When the mean diameter of inorganic filler is excessive, when manufacturing the liquid crystal cells of narrow gap, become in upper and lower glass of fitting
The undesirable element in gap etc. cannot be formed well, therefore, the mean diameter of inorganic filler the following is suitable for 2000nm during substrate
When, preferably below 1000nm, more preferably below 300nm.In addition, the preferred lower limit of the mean diameter of inorganic filler is
About 10nm, even more preferably about 100nm.Particle diameter can utilize laser diffraction/scattering formula particle size distribution device (dry type) (strain formula meeting
セ イ シ Application enterprise of society system；Lms-30) it is measured.
In the liquid crystal sealing agent of the present invention using inorganic filler in the case of, in the total amount of liquid crystal sealing agent can be
About 10～about 50 mass %, when the content of inorganic filler is more than 20 mass %, the effect of the present application is more notable.Especially excellent
Elect 20～50 mass % as.
The liquid crystal sealing agent of the present invention can contain (e) thermal curing agents.
Thermal curing agents are different from mentioned component (b) hot radical polymerization initiator, refer to not produce free radical by heating
Thermal curing agents.Specifically, the thing carrying out necleophilic reaction by lone pair, intramolecular anion can be enumerated
Matter, for example polynary amine, polyatomic phenol, organic hydrazide compound etc..But, it is not limited to this.Wherein, particularly preferably use
Organic hydrazide compound.Can enumerate for example: as terephthaldehyde's acid dihydrazide of aromatic hydrazide, M-phthalic acid two acyl
Hydrazine, 2,6- naphthalenedicarboxylic acid two hydrazides, 2,6- pyridine two hydrazides, 1,2,4- benzene three hydrazides, 1,4,5,8 naphthalenetetracarboxylic acid four hydrazides, all
Benzenetetracarboxylic acid four hydrazides etc..In addition, if being aliphatic hydrazide compound, then can enumerate for example: formylhydrazine, acethydrazide, propionyl
Hydrazine, careless acid dihydrazide, acid dihydrazide, succinum acid dihydrazide, glutaric, adipic dihydrazide, 1,5-pentanedicarboxylic acid. two acyl
Hydrazine, sebacic dihydrazide, 1,4- hexamethylene two hydrazides, winestone acid dihydrazide, Fructus Mali pumilae acid dihydrazide, iminodiacetic acid two acyl
Hydrazine, n, n '-hexamethylene bis semicarbazides, citric acid three hydrazides, nitrilotriacetic acid(NTA) three hydrazides, hexamethylene tricarboxylic acid three hydrazides,
Double (Hydrazinocarbonyl ethyl) -5- isopropyl hydantoin of 1,3- etc. has hydantoin skeleton, preferably has acyl in L-Valine second
The dihydrazide compound of urea skeleton (carbon atom of hydantoin ring replaced by isopropyl after skeleton), isocyanuric acid three (1- hydrazine
Base carbonvlmethyl) ester, isocyanuric acid three (2- Hydrazinocarbonyl ethyl) ester, isocyanuric acid three (1- Hydrazinocarbonyl ethyl) ester, isocyanide
Urea acid three (3- Hydrazinocarbonyl propyl group) ester, isocyanuric acid two (2- Hydrazinocarbonyl ethyl) ester etc..From solidification reactivity and latency
Balance set out, preferably isophthalic dihydrazide, acid dihydrazide, adipic dihydrazide, isocyanuric acid three (1- diazanyl
Carbonvlmethyl) ester, isocyanuric acid three (1- Hydrazinocarbonyl ethyl) ester, isocyanuric acid three (2- Hydrazinocarbonyl ethyl) ester, isocyanide urea
Sour three (3- Hydrazinocarbonyl propyl group) ester, particularly preferably isocyanuric acid three (2- Hydrazinocarbonyl ethyl) ester.
Composition (e) can be used alone it is also possible to mix two or more.Using composition in the liquid crystal sealing agent of the present invention
In the case of (e), in liquid crystal sealing agent total amount, usually 0.1～10 mass %, preferably 1～5 mass %.
The silane coupler that the liquid crystal sealing agent of the present invention can add as composition (f) to realize adhesive strength, moisture-proof
The raising of property.
As composition (f), can enumerate: 3- glycidoxypropyltrime,hoxysilane, 3- glycidoxypropyl group first
Base dimethoxysilane, 3- glycidoxypropyl diethoxy silane, 2- (3,4- epoxycyclohexyl) ethyl trimethoxy
Base silane, n- phenyl-gamma-amino propyl trimethoxy silicane, n- (2- amino-ethyl) -3- amino propyl methyl dimethoxy silicon
Alkane, n- (2- amino-ethyl) -3- amino propyl methyl trimethoxy silane, APTES, 3- sulfydryl third
Base trimethoxy silane, vinyltrimethoxy silane, n- (2- (vinyl-benzylamino) ethyl) -3- aminopropyl trimethoxy
Base silane hydrochlorate, 3- methacryloxypropyl trimethoxy silane, 3- chloropropylmethyldimethoxysilane, 3- chlorine third
Base trimethoxy silane etc..These silane couplers are with forms such as kbm series, kbe series by Shin-Etsu Chemial Co., Ltd
Deng selling, therefore can easily obtain from market.In the liquid crystal sealing agent of the present invention using composition (f) in the case of, in liquid
It is preferably 0.05～3 mass % in brilliant sealant total amount.
The curing accelerators such as organic acid, imidazoles, freedom can also be coordinated as needed in the liquid crystal sealing agent of the present invention
The additives such as base polymerization inhibitor, pigment, levelling agent, defoamer, solvent.
As above-mentioned curing accelerator, organic acid, imidazoles etc. can be enumerated.
As organic acid, organic carboxyl acid, organic phosphoric acid etc., the preferably situation of organic carboxyl acid can be enumerated.Specifically,
Can enumerate: phthalic acid, M-phthalic acid, p-phthalic acid, trimellitic acid, benzophenone tetracarboxylic, furandicarboxylic acid
Deng aromatic carboxylic acid, succinic acid, adipic acid, dodecanedioic acid, decanedioic acid, thio-2 acid, cyclohexane cyclohexanedimethanodibasic, isocyanuric acid
Three (2- carboxymethyl group) ester, isocyanuric acid three (2- carboxy ethyl) ester, isocyanuric acid three (2- carboxypropyl) ester, isocyanuric acid two
(2- carboxy ethyl) ester etc..
In addition, as imidazolium compoundss, can enumerate: 2-methylimidazole, 2- phenylimidazole, 2- undecyl imidazole, 2-
Heptadecyl imidazole, 2- phenyl -4-methylimidazole, 1- benzyl -2- phenylimidazole, 1 benzyl 2 methyl imidazole, 1- cyano group second
Base -2-methylimidazole, 1- cyano ethyl -2- phenylimidazole, 1- cyano ethyl -2- undecyl imidazole, 2,4- diaminourea -6-
(2 '-Methylimidazole. (1 ')) ethyl s-triazine, 2,4- diaminourea -6- (2 '-undecyl imidazole (1 ')) ethyl s-triazine, 2,4-
Diaminourea -6- (2 '-ethyl -4-methylimidazole (1 ')) ethyl s-triazine, 2,4- diaminourea -6- (2 '-Methylimidazole. (1 ')) second
Base s-triazine-isocyanuric acid adduct, the 2:3 adduct of 2-methylimidazole-isocyanuric acid, 2- phenylimidazole-isocyanuric acid add
Compound, 2- phenyl -3,5- hydroxymethyl-imidazole, 2- phenyl -4- methylol -5- Methylimidazole., 1- cyano ethyl -2- phenyl -3,
5- dicyano ethoxyl methyl imidazoles etc..
In the liquid crystal sealing agent of the present invention using curing accelerator in the case of, in the total amount of liquid crystal sealing agent generally
For 0.1～10 mass %, it is preferably 1～5 mass %.
As above-mentioned radical polymerization inhibitor, as long as being polymerized and draw with by optical free radical polymerization initiator, hot radical
Send out the radical reaction of generation such as agent and suppress the compound being polymerized just to be not particularly limited, it is possible to use quinones, piperidines, be subject to
Resistance phenols, nitrous base class etc..Specifically, can enumerate: naphthoquinone, 2 hydroxy naphthalene quinone, 2 methyl naphthoquinone, 2- methoxynaphthoquinone,
2,2,6,6- tetramethyl piperidine -1- oxygen-derived free radicals, 2,2,6,6- tetramethyl -4- hydroxy piperidine -1- oxygen-derived free radicals, 2,2,6,6- tetra-
Methyl -4- methoxy piperide -1- oxygen-derived free radicals, 2,2,6,6- tetramethyl -4- Phenoxypiperidines -1- oxygen-derived free radicals, hydroquinone, 2- first
Base hydroquinone, 2- methoxyhydroquinon, 1,4-benzoquinone, butylated hydroxyanisol, 2,6- di-t-butyl -4- ethyl -phenol, 2,6- bis- uncle
Butyl cresol, β-(3,5- di-tert-butyl-hydroxy phenyl) propanoic acid stearyl ester, 2,2 '-di-2-ethylhexylphosphine oxide (4- ethyl -6- tert-butyl group
Phenol), 4,4 '-thiobiss (3 methy 6 tert butyl phenol), 4,4 '-butylidene-bis(3-methyl-6-t-butyl phenol), 3,
Double [1,1- dimethyl -2- [β-(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) propionyloxy] ethyl] -2,4,8,10- four oxygen of 9-
Miscellaneous spiral shell [5.5] hendecane, four [methylene -3- (3 ', 5 '-di-t-butyl -4 '-hydroxy-phenylpropionic acid ester) methane, 1,3,5- tri-
(3 ', 5 '-di-t-butyl -4 '-hydroxybenzyl)-guanamine, 4,6- (1h, 3h, 5h) triketone, p methoxy phenol, 4- methoxy
Base -1- naphthols, phenothiazine, the aluminium salt of n- nitrosophenylhydroxylamine, trade name adk stab la-81, trade name adk
Stabla-82 (Asahi Denka Co., Ltd.'s system) etc., but it is not limited to this.Wherein, preferably naphthoquinone class, hydroquinones, nitrous base class,
The radical polymerization inhibitor of piperazines, more preferably naphthoquinone, 2 hydroxy naphthalene quinone, hydroquinone, 2,6 ditertiary butyl p cresol,
Polystop 7300p (Hakuto KK's system), most preferably polystop 7300p (Hakuto KK's system).
As the content of radical polymerization inhibitor, in the liquid crystal sealing agent total amount of the present invention, preferably 0.0001～1
Quality %, more preferably 0.001～0.5 mass %, particularly preferably 0.01～0.2 mass %.
As one of the method for the liquid crystal sealing agent obtaining the present invention, there is method as follows.First, become at (a)
Heating for dissolving (c) composition as needed in point.It is then cooled to room temperature, be then added as needed on (f) composition, then add (b)
Composition, (d) composition, (e) composition and defoamer, levelling agent, solvent etc., using known mixing arrangement such as three-roller, sand
Grinding machine, ball mill etc. equably mix, and are filtered using wire netting, thus, it is possible to manufacture the liquid crystal sealing agent of the present invention.
Between the liquid crystal display of the present invention is by specifying a pair of substrate being formed with regulation electrode on substrate
Configure every opposite, around used the liquid crystal sealing agent sealing of the present invention, and betwixt enclose liquid crystal in gap and obtain.The liquid enclosed
Brilliant species is not particularly limited.Here, substrate is by comprising glass, quartz, plastics, silicon etc. and at least one substrate has printing opacity
Property combination substrate constitute.As its manufacture method, the liquid crystal sealing agent of the present invention adds glass fibre thing at equal intervals
(gap control material), then using point gum machine or silk-screen printing device etc., this liquid crystal sealing agent is applied in this pair of substrate
A substrate on, then carry out precuring at 80 DEG C～120 DEG C as needed.Then, in the cofferdam of this liquid crystal sealing agent
Inner side dispenser method, another glass substrate overlapping, carries out gap and is formed in a vacuum.After forming gap, 90 DEG C～130
Solidify 1 hour～2 hours at DEG C, thus, it is possible to obtain the liquid crystal display of the present invention.In addition, making as photo-thermal and with type
With in the case of, carry out photocuring using ultraviolet irradiation machine to liquid crystal sealing agent portion irradiation ultraviolet radiation.Ultraviolet irradiation amount
It is preferably 500～10000mj/cm2, more preferably 1000～6000mj/cm2Irradiation dose.Then as needed, 90 DEG C～
Solidify 1 hour～2 hours at 130 DEG C, thus, it is possible to obtain the liquid crystal display of the present invention.The liquid of the present invention so obtaining
Brilliant display unit does not have that the display being caused by liquid crystal pollution is bad, and adhesivity, moisture-proof reliability are excellent.As sept, can
To enumerate such as glass fibre, silicon dioxide microballon, polymer microbeads etc..Its diameter is different according to purpose, usually 2 μm～
8 μm, preferably 4 μm～7 μm.Its usage amount is with respect to liquid crystal sealing agent 100 mass % typically about 0.1～about 4 of the present invention
Quality %, preferably from about 0.5～about 2 mass %, more preferably about 0.9～about 1.5 mass %.
The liquid crystal sealing agent of the present invention has the effect reducing wire corrosion.Its result can eliminate the drive after humidity test
Dynamic defect.In addition, low liquid crystal pollution is also excellent, additionally, the various solidfied material characteristic such as the adhesive strength of its solidfied material, thermostability
Also excellent.According to above-mentioned, by using the liquid crystal sealing agent of the present invention, it is capable of the excellent liquid crystal display of reliability.
In addition, also meet that voltage retention is high using the liquid crystal display that the liquid crystal sealing agent of the present invention makes, ion concentration low this
Sample as characteristic necessary to liquid crystal display.
Embodiment
Hereinafter, by embodiment, the present invention is illustrated in more detail, but the present invention is not limited to embodiment.Need
Illustrate, record as long as no special, " part " and " % " herein is quality criteria.
[synthesis example 1]
[synthesis of the full acrylate of resorcinolformaldehyde resin]
[operation 1]
Resorcinol 5500g, epoxy chlorine is added in the flask being provided with thermometer, Dropping funnel, condensing tube, agitator
Propane 37000g, tetramethyl ammonium chloride 500g, dissolve under agitation, and are warming up to 70 DEG C.Then, added with 100 minutes substeps
Laminar sodium hydroxide 4000g, then carries out the rear reaction of 1 hour at 70 DEG C.After reaction terminates, water 15000g is added to carry out
Washing, is then distilled off epoxychloropropane of surplus etc. under 130 DEG C, decompression from oil reservoir.Methyl is added in residue
Isobutyl ketone 22200g is dissolved, and is warming up to 70 DEG C.Add 30% sodium hydrate aqueous solution 1000g under agitation,
Carry out reaction in 1 hour, then carry out three washings with water 5550g, and methyl-isobutyl first is distilled off under 180 DEG C, decompression
Ketone, thus obtain resorcinolformaldehyde resin 10550g.The epoxide equivalent of obtained epoxide is 129g/eq.
[operation 2]
The resorcinolformaldehyde resin 181.2g obtaining in above-mentioned synthesis example 1 is dissolved in toluene 266.8g,
Add the dibenzylatiooluene 0.8g as polymerization inhibitor wherein, and be warming up to 60 DEG C.Then, the 100% of epoxy radicals are added
The acrylic acid 117.5g of equivalent, then heats to 80 DEG C, adds the trimethyl ammonium chloride 0.6g as catalysts wherein,
And in 98 DEG C of stir abouts 30 hours.Obtained reactant liquor is washed, and distills out toluene, thus obtain as target
Acrylate compound 253g of resorcinolformaldehyde resin.
[synthesis example 2]
[synthesis of the full acrylate of Bisphenol A Type epoxide]
Bisphenol A Type epoxide 282.5g (ProductName: yd-8125, Nippon Steel Chemical Co., Ltd's system) is dissolved in
Toluene 266.8g, adds the dibenzylatiooluene 0.8g as polymerization inhibitor wherein, and is warming up to 60 DEG C.Then, add ring
The acrylic acid 117.5g of 100% equivalent of epoxide, then heats to 80 DEG C, adds the trimethyl as catalysts wherein
Ammonium chloride 0.6g, and in 98 DEG C of stir abouts 30 hours, thus obtaining reactant liquor.This reactant liquor is washed, and is distilled off
Toluene, thus obtains acrylate compound 395g of the Bisphenol A Type epoxide as target.
[synthesis example 3]
[synthesis of double (the trimethylsiloxy) -1,1,2,2- tetraphenyl ethane of 1,2-]
Commercially available benzpinacol (Tokyo HuaCheng Industry Co., Ltd's system) 100 parts (0.28 moles) is made to be dissolved in dimethyl formyl
In 350 parts of amine.It is added thereto to 32 parts of pyridine (0.4 mole) as base catalyst, the bstfa as silylating agent
150 parts of (Shin-Etsu Chemial Co., Ltd's system) (0.58 mole), is warming up to 70 DEG C, and stirs 2 hours.By the reactant liquor obtaining
Cooling, adds 200 parts of water while stirring, so that product is precipitated and makes unreacted silylating agent inactivation.To precipitate
Product filtration separation, then fully wash.Then, the product obtaining is dissolved in acetone, adds water and make its recrystallization, carry out
Purification.Obtain double (the trimethylsiloxy) -1,1,2,2- 105.6 parts of (yields of tetraphenyl ethane of 1,2- as target
88.3%).
Using hplc (high performance liquid chromatography) analyze as a result, purity be 99.0% (area percentage).
[embodiment 1～5, the preparation of comparative example 1～4]
With the ratio shown in table 1 below to the compound of synthesis in synthesis example 1, the compound synthesizing in synthesis example 2
Etc. curable compound (composition (a)) middle addition optical free radical polymerization initiator (composition (c)), and in 90 DEG C of heating for dissolving.Cold
But to room temperature, and hot radical polymerization initiator (composition (b)), silane coupler (composition (f)), thermal curing agents (composition are added
(e)), organic filler (composition (d-1)), inorganic filler (composition (d-2)) etc., be stirred, then make it using three-roll mill
Dispersion, and filtered using wire netting (635 mesh), prepare liquid crystal drip-injection method sealant (embodiment 1～5, comparative example 1
～4).
[water absorption rate mensure]
The liquid crystal sealing agent manufacturing in embodiment, comparative example is sandwiched in system in polyethylene terephthalate (pet) film
Become the thin film that thickness is 100 μm, this thin film is put in 130 DEG C of baking ovens makes it solidify in 1 hour, by the stripping of pet film after solidification
Obtain sealant cures film, be then cut to the strip of 20mm × 50mm, thus make sample strip.Make the sample strip obtaining
Stablize 24 hours according to jis-k7209d method under conditions of 25 DEG C, 50%rh, then measure initial weight, 60 DEG C, 90%
It is made to absorb water under conditions of rh 24 hours, then gravimetry, it is set as weight after water suction.Calculated by following formula after mensure
Water absorption rate.
Water absorption rate (%)=((weight (g)-initial weight (g) after water suction)/initial weight (g)) × 100 (%)
[moisture permeability mensure]
Sealant cures film is produced by the method same with water absorption rate, and cuts into the square shape of 90mm × 90mm
Shape, makes sample strip.This sample strip is utilized according to jis-k7129a method with the moisture permeability of systech illinois company manufacture
Measure the mensure that device lyssy l80-5000 carries out moisture permeability under 60 DEG C of temperature conditionss.
[evaluation of the electrode corrosion under high temperature and humidity test]
Using the liquid crystal sealing agent manufacturing in embodiment, comparative example, produce the evaluation liquid crystal list that cell gap is 5 μm
Unit, carries out confirming to the electrode corrosion under high-temperature high-humidity test.Its test method is as described below.
Add the glass fibre 0.02g of 5 μm of the diameter as sept and carry out mixing and stir in each 2g of liquid crystal sealing agent
Mix deaeration, be filled in 5ml syringe.On the glass substrate with ito transparency electrode using point gum machine (shotmaster300:
Musashi high-tech Co. Ltd. system) the rectangle sealing carrying out 30mm × 40mm in the liquid crystal sealing agent of syringe will be pre-charged with
The coating of pattern, then instils the microdroplet of liquid crystal (mlc-3007: Merck Co. Ltd. system) in seal pattern inframe.Then will
Sept (natco spacer kseb-525f:natco Co. Ltd. system: 5 μm of the gap width after laminating) distribution, heat in face
Be fixed on another ito glass substrate, using laminating apparatus in a vacuum with liquid crystal drip-injection before after baseplate-laminating, so
Backward atmosphere opening and form gap.In order to assume the wiring light shielding part that sealing middle-ultraviolet lamp is difficult to irradiate, using metal halogen
Compound lamp (Ushio Electric Inc's system) irradiates low irradiation dose 500mj/cm2(with 100mw/cm2Irradiate 5 seconds) ultraviolet
And make seal pattern semi-solid preparation, then put into 1 hour in 130 DEG C of baking ovens, thus make seal pattern heat cure, produce evaluation and use
Liquid crystal cells.Just applying 10v, 100hz using functional generator (fg-281: Co., Ltd.'s texio technology system)
In the state of string wave voltage by obtained evaluation with liquid crystal cells put into 60 DEG C, 90%rh hot and humid under the conditions of 240 little
When, then with sealing, micro- sem observation is carried out to evaluation, thus carry out the evaluation of electrode corrosion with following benchmark.
Zero: the corrosion of ito electrode is not observed in sealing periphery.
△: slightly observe the corrosion of ito electrode in sealing periphery.
×: the corrosion of ito electrode is observed in sealing periphery.
[liquid crystal pollution evaluation]
For each liquid crystal sealing agent manufacturing in embodiment, comparative example, smear in the bottom of 10ml bottle that to open about 100mg close
Envelope agent, then, adds the liquid crystal (mlc-3007: Merck Co. Ltd. system) of 10 times amount of each sealant being coated with from top.
Obtained bottle is heated, keeps 1 hour at 130 DEG C, then cooling 30 minutes is to reaching room temperature.Will be each by decantation
From the supernatant of liquid crystal take out separately, measure electricity using digital ultra-high resistance meter (r8340: Co., Ltd.'s advantest system)
Resistance, based on the resistivity value of the value of the liquid crystal relative to no sealant, is judged by following benchmark.
Zero: 5.0 × 1012More than
△: 5.0 × 1011Less than 5.0 × 1012
×: less than 5.0 × 1011
[evaluation of light shielding part curable]
As shown in figure 1, central authorities' coating of the glass substrate after chrome plating is etched with the addition of 3 μ of 1 weight %
The liquid crystal sealing agent of the glass fibre of m, is used black matrix substrate to be fitted as opposite substrate, and is fixed using clip
(ultraviolet pre-irradiation).3000mj/cm is irradiated in glass substrate side after Xiang Qicong is etched to chromium2Ultraviolet, then
By two strippable substrates of laminating, by microscope, the part being blocked below chromium is confirmed, measure consolidating of light shielding part
Change width
More than zero: 30 μm
△: 10 μm less than 30 μm
×: less than 10 μm
[table 1]
The full acrylate (synthesis example 1) of a-1: resorcinolformaldehyde resin
The full acrylate (synthesis example 2) of a-2: Bisphenol A Type epoxide
Dipentaerythritol acrylate (Nippon Kayaku K. K's system: the dpca- of a-3: caprolactone modification (6 moles)
60)
A-4: Bisphenol-a Epoxy Resin (Nippon Kayaku K. K's system: re-310s)
A-5: Bisphenol-a Epoxy Resin high molecular body (aurification length of schooling: yd-012 lives in Nippon Steel)
A-6: ethylene-oxide-modified bis-phenol s type epoxy resin (close by the method according to No. 4211942 records of Japanese Patent No.
Become)
(synthesis example 3 utilizes jet mill to double (the trimethylsiloxy) -1,1,2,2- tetraphenyl ethane of b-1:1,2-
Micropowder is broken into the material after 1.9 μm of mean diameter)
Condensation polymer (the molecular weight: 2000) (and light pure medicine work of b-2:4,4'- azo two (4- cyanopentanoic acid) and Polyethylene Glycol
Industry Co. Ltd. system: vpe-0201)
C-1:2- methacryloxyethyl isocyanates and 1- [4- (2- hydroxyl-oxethyl) phenyl] -2- hydroxyl -2 first
The product of base -1- propane -1- ketone
(by the method synthesis of No. 2006/027982 record of International Publication)
C-2:1,2- acetyl caproyl, (basf manufactures 1- [4- (thiophenyl) -2- (o- benzoyl oxime)]: irgacure oxe-
01)
C-3:2,4- diethyl thioxanthone (Nippon Kayaku K. K's system: detx-s)
D-1-1: polymethacrylate organic fine particles (Eike Kogyo K.K.'s system: f-351s)
D-2-1: preparing spherical SiO 2 (Shin-Etsu Chemial Co., Ltd's system: x-24-9163a)
D-2-2: preparing spherical SiO 2 (Tokuyama Corp's system: サ Application シ Le ssp-07dm)
E-1: isocyanuric acid three (2- Hydrazinocarbonyl ethyl) ester micropowder minces
(Co., Ltd. Japan finechem system: hcic, be broken into the material after 1.5 μm using jet mill micropowder)
F-1:3- glycidoxypropyltrime,hoxysilane (jnc Co. Ltd. system: sila-ace s-510)
F-2:n-2 (amino-ethyl) APTES (Shin-Etsu Chemial Co., Ltd's system: kbm-
603)
O-1: nitrous base class piperidine derivative (Hakuto KK's system: polystop 7300p)
O-2: isocyanuric acid three (2- carboxy ethyl) ester
(Shikoku Chem's system: cic acid, be broken into 1.5 μm of mean diameter using jet mill micropowder after
Material)
According to the result of table 1, the water absorption rate of the solidfied material obtaining merely with heat, moisture permeability are certain value below example
1～5 shows no wire corrosion and the also excellent result of low liquid crystal pollution.On the other hand, the liquid crystal described in comparative example
There is wire corrosion in sealant, have problems in terms of the long-term reliability of liquid crystal display.It can be said that: the application sends out
Bright is the excellent liquid crystal sealing agent of reliability after humidity test, and the liquid crystal display being manufactured using this liquid crystal sealing agent
Reliability also excellent.
Industrial applicability
The impact that the liquid crystal sealing agent of the present invention produces to liquid crystal display characteristic is minimum, therefore, it is possible to realize liquid crystal display
The High precision of element, high-speed response, low voltage drive, long lifetime.In addition, adhesive strength, moisture-proof reliability are excellent,
Therefore, it is possible to realize the manufacture of the high liquid crystal display cells of reliability.
Claims (14)
1. a kind of liquid crystal sealing agent for liquid crystal drip-injection method, it contains (a) curable compound,
Non- irradiation ultraviolet radiation and suction solidfied material, measuring according to jis-k7209 after only carrying out heat cure in 1 hour at 130 DEG C
Water rate is less than 2.0%, is 130g/m according to the moisture permeability that jis-k7129 measures2Below 24h.
2. it is used for the liquid crystal sealing agent of liquid crystal drip-injection method as claimed in claim 1, it also contains the polymerization of (b) hot radical and causes
Agent.
3. it is used for the liquid crystal sealing agent of liquid crystal drip-injection method as claimed in claim 2, wherein, described composition (b) hot radical gathers
Closing initiator is the hot radical polymerization initiator not containing o-o bond (- o-o-) and nitrogen-nitrogen key (- n=n-) in intramolecular.
4. it is used for the liquid crystal sealing agent of liquid crystal drip-injection method as claimed any one in claims 1 to 3, it also contains (c) light certainly
By base polymerization initiator.
5. the liquid crystal sealing agent for liquid crystal drip-injection method as any one of Claims 1-4, it also contains (d) filler,
This filler is more than 20 mass % in the containing ratio in liquid crystal sealing agent total amount.
6. it is used for the liquid crystal sealing agent of liquid crystal drip-injection method as claimed in claim 5, wherein, described composition (d) is that (d-1) is organic
Filler and the mixture of (d-2) inorganic filler.
7. it is used for the liquid crystal sealing agent of liquid crystal drip-injection method, wherein, the inorganic filler of described composition (d-2) as claimed in claim 6
It is more than 20 mass % in the containing ratio in liquid crystal sealing agent total amount.
8. the liquid crystal sealing agent for liquid crystal drip-injection method as any one of claim 1 to 7, wherein, described composition (a)
Curable compound is epoxy (methyl) acrylate compounds.
9. the liquid crystal sealing agent for liquid crystal drip-injection method as any one of claim 1 to 7, wherein, described composition (a)
Curable compound is the mixture of epoxy (methyl) acrylate compounds and epoxide.
10. it is used for the liquid crystal sealing agent of liquid crystal drip-injection method as claimed in any one of claims 1-9 wherein, it also contains (e) thermosetting
Agent.
11. liquid crystal sealing agents being used for liquid crystal drip-injection method as claimed in claim 10, wherein, described composition (e) thermal curing agents
For organic hydrazides.
12. liquid crystal sealing agents for liquid crystal drip-injection method as any one of claim 1 to 11, it also contains (f) silicon
Alkane coupling agent.
A kind of 13. manufacture methods of liquid crystal display are it is characterised in that by liquid crystal drip-injection to the liquid crystal comprising two substrates
Show the sealing liquid crystal for liquid crystal drip-injection method being formed in unit any one of claim 1 to 12 on one substrate
The inner side in the cofferdam of agent, another substrate of then fitting, then solidified using light and/or heat.
A kind of 14. liquid crystal displays, it utilizes the liquid being used for liquid crystal drip-injection method any one of claim 1 to 12
Solidfied material obtained from brilliant sealant cures is sealed.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015-143863 | 2015-07-21 | ||
| JP2015143863 | 2015-07-21 |
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| CN106366998A true CN106366998A (en) | 2017-02-01 |
| CN106366998B CN106366998B (en) | 2021-05-18 |
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ID=57880773
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610491657.1A Expired - Fee Related CN106366998B (en) | 2015-07-21 | 2016-06-29 | Liquid crystal sealing agent and liquid crystal display cell using the same |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6860299B2 (en) |
| KR (1) | KR20170012038A (en) |
| CN (1) | CN106366998B (en) |
| TW (1) | TWI682991B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110818882A (en) * | 2019-11-26 | 2020-02-21 | 中国科学院苏州纳米技术与纳米仿生研究所南昌研究院 | Environment-friendly tackifier and preparation method and application thereof |
| CN112595433A (en) * | 2020-12-23 | 2021-04-02 | 西安和其光电科技股份有限公司 | Glue sealing system and method for optical fiber sensing probe |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018133733A (en) | 2017-02-16 | 2018-08-23 | 株式会社フジクラ | Wireless communication system and wireless communication method |
| CN110231726B (en) * | 2019-07-29 | 2022-01-25 | Tcl华星光电技术有限公司 | Frame glue moisture permeability measuring device and frame glue moisture permeability measuring method |
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| CN1346375A (en) * | 1999-12-14 | 2002-04-24 | 三井化学株式会社 | Sealing agent for liquid-crystal display, cell, composition for sealing agent for liquid-crystal display cell, and liquid-crystal display element |
| CN104471471A (en) * | 2012-07-17 | 2015-03-25 | 日本化药株式会社 | Liquid-crystal sealant and lcd cell using same |
| CN104516154A (en) * | 2013-09-30 | 2015-04-15 | 日本化药株式会社 | Liquid crystal sealing agent and liquid crystal display cell using same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0820627B2 (en) | 1987-01-20 | 1996-03-04 | 松下電器産業株式会社 | Liquid crystal display element manufacturing method |
| JPH10239694A (en) | 1997-02-24 | 1998-09-11 | Hitachi Ltd | Manufacturing method of liquid crystal display device |
| 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 |
| JP2002069160A (en) * | 1999-12-14 | 2002-03-08 | Mitsui Chemicals Inc | Sealing agent for liquid crystal display cell, composition for sealing agent for liquid crystal display cell and liquid crystal display element |
| TWI298412B (en) * | 2000-06-21 | 2008-07-01 | Mitsui Chemicals Inc | |
| JP2002088228A (en) * | 2000-09-14 | 2002-03-27 | Mitsui Chemicals Inc | Sealant composition for liquid crystal display element and production process of liquid crystal display element |
| JP2004061925A (en) | 2002-07-30 | 2004-02-26 | Nippon Kayaku Co Ltd | Liquid crystal sealing agent and liquid crystal display cell using the same |
| JP2004126211A (en) | 2002-10-02 | 2004-04-22 | Mitsui Chemicals Inc | Resin composition for sealing liquid crystal, and method of manufacturing liquid crystal display panel |
| EP1674919A1 (en) * | 2003-10-17 | 2006-06-28 | Nippon Kayaku Kabushiki Kaisha | Sealant for liquid crystal, liquid-crystal display made with the same, and process for produicng the display |
| JP5268235B2 (en) | 2006-07-05 | 2013-08-21 | 日本化薬株式会社 | Liquid crystal sealant and liquid crystal display cell using the same |
| JP5139735B2 (en) | 2007-06-26 | 2013-02-06 | 積水化学工業株式会社 | Sealant for liquid crystal dropping method, vertical conduction material, and liquid crystal display element |
| JP6253638B2 (en) * | 2013-03-21 | 2017-12-27 | 日本化薬株式会社 | Liquid crystal sealant and liquid crystal display cell using the same |
-
2016
- 2016-05-13 TW TW105114858A patent/TWI682991B/en not_active IP Right Cessation
- 2016-06-29 CN CN201610491657.1A patent/CN106366998B/en not_active Expired - Fee Related
- 2016-06-30 JP JP2016130455A patent/JP6860299B2/en active Active
- 2016-07-13 KR KR1020160088620A patent/KR20170012038A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1346375A (en) * | 1999-12-14 | 2002-04-24 | 三井化学株式会社 | Sealing agent for liquid-crystal display, cell, composition for sealing agent for liquid-crystal display cell, and liquid-crystal display element |
| CN104471471A (en) * | 2012-07-17 | 2015-03-25 | 日本化药株式会社 | Liquid-crystal sealant and lcd cell using same |
| CN104516154A (en) * | 2013-09-30 | 2015-04-15 | 日本化药株式会社 | Liquid crystal sealing agent and liquid crystal display cell using same |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110818882A (en) * | 2019-11-26 | 2020-02-21 | 中国科学院苏州纳米技术与纳米仿生研究所南昌研究院 | Environment-friendly tackifier and preparation method and application thereof |
| CN110818882B (en) * | 2019-11-26 | 2021-11-23 | 江西省纳米技术研究院 | Environment-friendly tackifier and preparation method and application thereof |
| CN112595433A (en) * | 2020-12-23 | 2021-04-02 | 西安和其光电科技股份有限公司 | Glue sealing system and method for optical fiber sensing probe |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20170012038A (en) | 2017-02-02 |
| CN106366998B (en) | 2021-05-18 |
| JP6860299B2 (en) | 2021-04-14 |
| TW201708488A (en) | 2017-03-01 |
| JP2017027041A (en) | 2017-02-02 |
| TWI682991B (en) | 2020-01-21 |
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