CN107686716A - Liquid crystal sealing agent and the liquid crystal display using the liquid crystal sealing agent - Google Patents
Liquid crystal sealing agent and the liquid crystal display using the liquid crystal sealing agent Download PDFInfo
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- CN107686716A CN107686716A CN201710660783.XA CN201710660783A CN107686716A CN 107686716 A CN107686716 A CN 107686716A CN 201710660783 A CN201710660783 A CN 201710660783A CN 107686716 A CN107686716 A CN 107686716A
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- liquid crystal
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
- C09K3/1021—Polyurethanes or derivatives thereof
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- 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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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
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Nonlinear Science (AREA)
- Organic Chemistry (AREA)
- Optics & Photonics (AREA)
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- Crystallography & Structural Chemistry (AREA)
- Mathematical Physics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
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Abstract
Liquid crystal display the present invention relates to liquid crystal sealing agent and using the liquid crystal sealing agent.The present invention proposes to can also apply to flexible display, the display of curved shape and the general characteristic such as low liquid crystal pollution, adhesive strength also excellent liquid crystal drip-injection method liquid crystal sealing agent and liquid crystal display excellent in reliability.A kind of liquid crystal drip-injection method liquid crystal sealing agent, wherein, the liquid crystal drip-injection method liquid crystal sealing agent contains the compound that at least one (A) intramolecular has amino-formate bond, and the liquid crystal drip-injection method with the glass transition temperature determined by DMA methods of the solidfied material of liquid crystal sealing agent is less than 90 DEG C, tan δ are more than 0.5.
Description
Technical field
The present invention relates to the liquid crystal sealing agent for liquid crystal drip-injection method, more specifically, is related to and can also apply to flexibility
The display of display, curved shape, and the general characteristic such as low liquid crystal pollution, adhesive strength also excellent liquid crystal drip-injection method
Use liquid crystal sealing agent.
Background technology
With the maximization of liquid crystal display in recent years, the manufacture method as liquid crystal display, it is proposed that amount
The higher so-called liquid crystal drip-injection method of production property (referring to patent document 1, patent document 2).Specifically, it is liquid crystal as described below
The manufacture method of display unit：Inner side by liquid crystal drip-injection to the cofferdam for the liquid crystal sealing agent being formed on a substrate, then
Another substrate is bonded, thus by sealing liquid crystal.
However, there are the following problems for liquid crystal drip-injection method：Because the liquid crystal sealing agent of its uncured state contacts with liquid crystal, because
This, the now composition dissolving (dissolution) of liquid crystal sealing agent declines the resistance value of liquid crystal into liquid crystal, produces near sealing
Show bad.
In order to solve the problem, photo-thermal is used now and the liquid crystal for being used for liquid crystal drip-injection method is used as by the use of the liquid crystal sealing agent of type
Sealant, and practical (patent document 3,4).Use the liquid crystal drip-injection method of the liquid crystal sealing agent to be characterised by, passed through
Make its one-step solidification to pressing from both sides liquid crystal sealing agent irradiation light between the substrates, its secondary solidification is then made by heating.Root
According to this method, it can utilize light that it is (molten that uncured liquid crystal sealing agent rapid curing can be suppressed into the dissolving of liquid crystal sealing agent composition
Go out) into liquid crystal.In addition, in the case of only photocuring, also produce gluing strong as caused by cure shrinkage during photocuring etc.
The problem of insufficient is spent, but if being photo-thermal and with type, then with advantages below：Secondary solidification can be carried out so as to obtain by heating
To stress relaxation effect, additionally it is possible to solve the above problems.
The liquid crystal drip-injection method of the photo-thermal curing type is practical with liquid crystal sealing agent, and thus, liquid crystal drip-injection method turns into usual
The method used.
In addition, recently in the field of liquid crystal display, carrying out flexible display, there is the display of the shape bent
The exploitation of device.For the substrate for such display, substitute conventional glass using the soft substrate such as plastic foil
Deng rigid substrates (patent document 5).
From such background, liquid crystal drip-injection method is also required with liquid crystal sealing agent follow flexure of substrate etc. this
Sample, i.e. also soft property after hardening.
All the time, from the viewpoint of adhesive strength is improved, the liquid crystal drip-injection method liquid crystal with flexibility has been carried out
The exploitation (patent document 6) of sealant.However, the liquid crystal drip-injection method with enough performances for being adapted to above-mentioned flexible substrate
Not yet realized with liquid crystal sealing agent.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Application 63-179323 publications
Patent document 2：Japanese Unexamined Patent Publication 10-239694 publications
Patent document 3：No. 3583326 publications of Japanese Patent Publication No.
Patent document 4：Japanese Unexamined Patent Publication 2004-61925 publications
Patent document 5：Japanese Unexamined Patent Publication 2012-238005 publications
Patent document 6：Japanese Unexamined Patent Publication 2016-24240 publications
The content of the invention
Invent problem to be solved
The present invention proposes to can also apply to flexible display, the display of curved shape and low liquid crystal pollution, glue
The general characteristics such as viscous intensity also excellent liquid crystal drip-injection method liquid crystal sealing agent.
The means used to solve the problem
The present inventor etc. has found, by having the chemical combination of amino-formate bond containing the intramolecular for being used as specific composition
The thing and glass transition temperature that is determined by DMA methods has specific relation with tan δ, can improve liquid crystal drip-injection method liquid crystal
Flexibility after the solidification of sealant, flexible display, curved shape display in can also realize enough adhesive strengths,
So as to complete the present application.
I.e. the present invention relates to it is following 1)~15).
It should be noted that in this specification, in the case where being recited as " (methyl) acrylic acid ", refer to " acrylic acid "
And/or " methacrylic acid ".In addition, " liquid crystal drip-injection method with liquid crystal sealing agent " is also abbreviated as " liquid crystal sealing agent " sometimes.
In addition, subscript RTM refers to registration mark.
1)
A kind of liquid crystal drip-injection method liquid crystal sealing agent, wherein, the liquid crystal drip-injection method liquid crystal sealing agent contains at least one
Kind (A) intramolecular has the compound of amino-formate bond, and
The liquid crystal drip-injection method is 90 with the glass transition temperature determined by DMA methods of the solidfied material of liquid crystal sealing agent
Below DEG C, tan δ be more than 0.5.
2)
It is above-mentioned 1) as described in liquid crystal drip-injection method liquid crystal sealing agent, wherein, the weight average molecular weight of above-mentioned (A) for 1000 with
On.
3)
It is above-mentioned 1) or 2) as described in liquid crystal drip-injection method liquid crystal sealing agent, wherein, above-mentioned (A) is that intramolecular has 3
The compound of above ester bond.
4)
As it is above-mentioned 1)~3) any one of liquid crystal drip-injection method liquid crystal sealing agent, wherein, the liquid crystal drip-injection method
Also contain (B) hot radical polymerization initiator with liquid crystal sealing agent.
5)
As it is above-mentioned 1)~4) any one of liquid crystal drip-injection method liquid crystal sealing agent, wherein, the liquid crystal drip-injection method
Also contain (C) (methyl) acrylic compounds with liquid crystal sealing agent.
6)
As it is above-mentioned 1)~5) any one of liquid crystal drip-injection method liquid crystal sealing agent, wherein, the liquid crystal drip-injection method
Also contain (D) organic filler with liquid crystal sealing agent.
7)
It is above-mentioned 6) as described in liquid crystal drip-injection method liquid crystal sealing agent, wherein, mentioned component (D) be selected from micro- by polyurethane
In the group that grain, acrylic resin fine-particles, ps particle, styrene olefin copolymer particulate and organic silicone microparticle are formed
One or more kinds of organic fillers.
8)
As it is above-mentioned 1)~7) any one of liquid crystal drip-injection method liquid crystal sealing agent, wherein, the liquid crystal drip-injection method
Also contain (E) inorganic filler with liquid crystal sealing agent.
9)
As it is above-mentioned 1)~8) any one of liquid crystal drip-injection method liquid crystal sealing agent, wherein, the liquid crystal drip-injection method
Also contain (F) silane coupler with liquid crystal sealing agent.
10)
As it is above-mentioned 1)~9) any one of liquid crystal drip-injection method liquid crystal sealing agent, wherein, the liquid crystal drip-injection method
Also contain (G) epoxide with liquid crystal sealing agent.
11)
As it is above-mentioned 1)~10) any one of liquid crystal drip-injection method liquid crystal sealing agent, wherein, the liquid crystal drip-injection method
Also contain (H) thermal curing agents with liquid crystal sealing agent.
12)
It is above-mentioned 11) as described in liquid crystal drip-injection method liquid crystal sealing agent, wherein, mentioned component (H) is organic acid hydrazides
Compound.
13)
As it is above-mentioned 1)~12) any one of liquid crystal drip-injection method liquid crystal sealing agent, wherein, the liquid crystal drip-injection method
Also contain (I) optical free radical polymerization initiator with liquid crystal sealing agent.
14)
A kind of manufacture method of liquid crystal display, it is characterised in that in the liquid crystal display being made up of two substrates
In, by liquid crystal drip-injection to be formed on a substrate it is above-mentioned 1)~13) any one of liquid crystal drip-injection method liquid crystal it is close
The inner side in the cofferdam of agent is sealed, another substrate is then bonded, is then solidified using heat.
15)
A kind of liquid crystal display, its using will it is above-mentioned 1)~13) any one of liquid crystal sealing agent solidification and obtain
To solidfied material sealed.
Invention effect
The present invention proposes to can also apply to flexible display, the display of curved shape and low liquid crystal pollution, glue
The general characteristics such as viscous intensity also excellent liquid crystal drip-injection method liquid crystal sealing agent.
Embodiment
[(A) intramolecular has the compound of amino-formate bond]
The present invention has the compound of amino-formate bond containing (A) intramolecular.
Amino-formate bond (- NHCOO-) be contribute to solidfied material flexibility functional group, can by with
The compound of NCO (- NCO) obtains with having the addition reaction of the compound of hydroxyl (- OH).It should be noted that
In order to obtain the big and more soft compound of molecular weight, dihydroxy compounds can be used.
For the compound with NCO, the compound with hydroxyl and dihydroxy compounds, Ke Yilie
Citing such as compound illustrated below.
(compound with NCO)
For the compound with NCO, diisocyanate cpd as described below is preferable.
Tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4- trimethyl hexamethylene diisocyanates,
The chain saturated hydrocarbons isocyanates such as 2,4,4- trimethyl hexamethylene diisocyanates；IPDI, norborneol
Alkane diisocyanate, dicyclohexyl methyl hydride diisocyanate, di-2-ethylhexylphosphine oxide (4- cyclohexyl isocyanates), hydrogenated diphenyl methane
The cyclic saturated hydrocarbon isocyanates such as diisocyanate, hydrogenated xylene diisocyanate, hydrogenated toluene diisocyanate；2,4- first
Phenylene diisocyanate, 1,3- XDIs, PPDI, the isocyanide of 3,3 '-dimethyl -4,4 '-two
The aromatic polyisocyanates such as acid esters, 6- isopropyl -1,3- phenyl diisocyanates, 1,5- naphthalene diisocyanates.
(compound with hydroxyl)
For the compound with hydroxyl, described compound can be listed below.
(methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid 1,4- butanediols
Ester, polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, pentaerythrite three (methyl) acrylic acid
Ester, the 6-caprolactone addition product of (methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxyl -3- phenoxy-propyls.
In addition, for as the dihydroxy compounds for lifting molecular weight, for example following example can be enumerated.
PTMEG, polyester-diol, polycaprolactone glycol, PCDL.
In addition, composition (A) can be used as KAYARAD UX-3204, UX-4101, UX-0937 (Nippon Kayaku K. K
Manufacture) obtained from market.
Composition (A) for example can be by using the dihydroxy compounds, the compound with NCO and containing hydroxyl
(methyl) acrylate of base is synthesized into by conventional method.That is, for example by making dihydroxy compounds and there is isocyanide
The compound addition of perester radical and obtain reactant (I), then by making (methyl) acrylate of hydroxyl and reactant (I)
Addition is carried out, obtains polyurethane (methyl) acrylate.
For composition (A), preferable weight-average molecular weight is more than 1000 situation.Weight average molecular weight can for example pass through
Gel permeation chromatography (GPC) etc. and obtain.
The further preferred weight average molecular weight of composition (A) is more than 2000 and less than 15000, and particularly preferred scope is
More than 2500 and less than 10000.
Composition (A) preferably intramolecular also has a case that more than 3 ester bonds (- C (=O) O-).It is same with amino-formate bond
Sample, ester bond also contribute to flexibility, by that can assign higher flexibility with amino-formate bond and use.
The ester bond number of the intramolecular of composition (A) is more preferably more than 4, particularly preferably more than 5.It is not special
The upper limit is limited, is considered from the relation of above-mentioned molecular weight, preferably from about more than 10 and less than about 175.
Such composition (A) for example can be by using polyester-diol, polycaprolactone two for above-mentioned dihydroxy compounds
Alcohol etc. and obtain.It should be noted that KAYARAD UX-3204 (Nippon Kayaku K. K), KAYARAD UX- can be used as
4101 (Nippon Kayaku K. K) obtain from market.
For content as composition (A), it is the mass % of 10 mass %~80 preferably in the total amount of liquid crystal sealing agent, enters
One step is preferably the mass % of 20 mass %~70, the mass % of particularly preferably 25 mass %~60.
[glass transition temperature of solidfied material]
The glass transition temperature determined by DMA methods of the solidfied material of the liquid crystal sealing agent of the present invention is less than 90 DEG C.
It is low by glass transition temperature, the tracing ability increase to flexible base board.
It should be noted that for DMA condition determination, such as use Measurement of Dynamic Viscoelasticity device (DMS-
6100：Seiko electronics nanosecond science and technology Co., Ltd. (SII NanoTechnology Inc.) manufactures), under stretch mode, in frequency
It is measured under conditions of rate 10Hz, 2 DEG C/min of warming temperature.By the ratio of loss modulus and storage modulus (JIS K 7244-
1) loss factor Tan δ are obtained.Temperature when resulting loss factor Tan δ to reach to maximum is as glass transition temperature
Degree.
Only add mentioned component (A) when, it is difficult to realize glass transition temperature be less than 90 DEG C, such as can use add
Add the organic filler of monofunctional compound, addition with flexibility, reactive compounds are changed with the linking group of softness
The various methods such as property are realized.
The further preferred range of the glass transition temperature is less than 85 DEG C, particularly preferably less than 80 DEG C.Lower limit
It is not particularly limited, is about 0 DEG C.
[the tan δ of solidfied material]
The glass tan δ determined by DMA methods of the solidfied material of the liquid crystal sealing agent of the present invention are more than 0.5.Pass through tan δ
For more than 0.5, the tracing ability increase to flexible base board.
The tan δ further preferred ranges are more than 0.55, particularly preferably more than 0.57.The upper limit is not special
Limitation, is about 1.0.
[(B) hot radical polymerization initiator]
The liquid crystal sealing agent of the present invention can contain hot radical polymerization initiator as composition (B).The hot radical gathers
As long as initiator is closed to produce free radical by heating and trigger the compound of chain polymerization to be then not particularly limited, can
To enumerate：Organic peroxide, azo-compound, benzoin compound, benzoin ether compound, acetophenone compound, benzene frequency
Any alcohol etc., preferably using benzpinacol.For example, for as organic peroxide, can be obtained in the form of commercially available product
KayamekRTM A、M、R、L、LH、SP-30C、Perkadox CH-50L、BC-FF、Cadox B-40ES、Perkadox 14、
TrigonoxRTM 22-70E、23-C70、121、121-50E、121-LS50E、21-LS50E、42、42LS、KayaesterRTM
P-70、TMPO-70、CND-C70、OO-50E、AN、KayabutylRTM B、Perkadox 16、KayacarbonRTM BIC-75、
AIC-75 (manufacture of chemical drug AKZO Co., Ltd.), PermekRTMN、H、S、F、D、G、PerhexaRTM H、HC、TMH、C、V、22、
MC、PercureRTM AH、AL、HB、PerbutylRTM H、C、ND、L、PercumylRTM H、D、PeroylRTM IB、IPP、
PeroctaRTMND (Japan Oil Co's manufacture) etc..In addition, for as azo-compound, can be obtained in the form of commercially available product
Obtain VA-044, V-070, VPE-0201, VSP-1001 (Wako Pure Chemical Industries, Ltd.'s manufacture) etc..It should be noted that this
In specification, subscript RTM refers to registration mark.
As composition (B), preferably heat of the intramolecular without o-o bond (- O-O-) or nitrogen-nitrogen key (- N=N-) freely
Base polymerization initiator.Intramolecular has the hot radical polymerization initiator of o-o bond (- O-O-), nitrogen-nitrogen key (- N=N-) in life
Substantial amounts of oxygen, nitrogen are produced during into free radical, therefore, is solidified with remaining alveolate state in liquid crystal sealing agent,
There is a possibility that the characteristic such as adhesive strength reduces.The hot radical polymerization initiator of particularly preferred benzpinacol class is (including to benzene frequency
Material obtained from which alcohol is chemically modified).Specifically, can enumerate：Benzpinacol, 1,2- dimethoxy -1,1,2,
2- tetraphenyls ethane, 1,2- diethoxy -1,1,2,2- tetraphenyls ethane, 1,2- hexichol Oxy-1s, 1,2,2- tetraphenyls ethane,
1,2- dimethoxys -1,1,2,2- four (4- aminomethyl phenyls) ethane, 1,2- hexichol Oxy-1s, 1,2,2- tetra- (4- methoxyphenyls)
Double (the trimethylsiloxy) -1,1,2,2- tetraphenyls ethane of ethane, 1,2-, double (the silicohetane alkoxies) -1 of 1,2-,
Double (t-butyldimethylsilyloxy the base) -1,1,2,2- tetraphenyls ethane of 1,2,2- tetraphenyls ethane, 1,2-, 1- hydroxyls -2-
Trimethylsiloxy -1,1,2,2- tetraphenyls ethane, 1- hydroxyl -2- triethyl-silicane Oxy-1s, 1,2,2- tetraphenyls
Ethane, 1- hydroxyl -2- t-butyldimethylsilyloxy bases -1,1,2,2- tetraphenyl ethane etc., preferably 1- hydroxyls -2- front threes
Base siloxy -1,1,2,2- tetraphenyls ethane, 1- hydroxyl -2- triethyl-silicane Oxy-1s, 1,2,2- tetraphenyls ethane,
1- hydroxyl -2- t-butyldimethylsilyloxy base -1,1,2,2- tetraphenyls ethane, 1,2- double (trimethylsiloxies) -
1,1,2,2- tetraphenyl ethane, more preferably 1- hydroxyls -2- trimethylsiloxies -1,1,2,2- tetraphenyl ethane,
1,2- double (trimethylsiloxy) -1,1,2,2- tetraphenyl ethane, double (the trimethyl silyl oxygen of particularly preferably 1,2-
Base) -1,1,2,2- tetraphenyl ethane.
Above-mentioned benzpinacol is commercially available by Tokyo HuaCheng Industry Co., Ltd, Wako Pure Chemical Industries, Ltd. etc..It is in addition, right
The hydroxyl of benzpinacol, which carries out etherificate, easily to be synthesized by known method.In addition, the hydroxyl to benzpinacol
Carry out silicyl etherificate can by by corresponding benzpinacol and various silylating agents in base catalysts such as pyridines
In the presence of the method that heats be synthesized into.For silylating agent, commonly known conduct front three can be enumerated
Double (the trimethyl silyls of trim,ethylchlorosilane (TMCS), HMDS (HMDS), N, O- of base silylating agent
Base) trifluoroacetamide (BSTFA), the chlorotriethyl silane (TECS) as triethylsilyl agent, as the tert-butyl group two
T-butyldimethylsilyl (TBMS) of methyl silicane base agent etc..These reagents can be from the markets such as silicon derivative manufacturers
It is readily available.For the reacting dose of silylating agent, it is preferably relative to 1 mole of the hydroxyl as subject compound
1.0 times moles~5.0 times moles.More preferably 1.5 times moles~3.0 times moles.During less than 1.0 times moles, reaction effect
Rate is poor, and the reaction time is elongated, therefore can promote to thermally decompose.During more than 5.0 times moles, separated in recovery and be deteriorated or be difficult to pure
Change.
For composition (B), particle diameter is attenuated and be uniformly dispersed.It is narrow manufacturing when its average grain diameter is excessive
The undesirable element that can not form gap etc. well in lower glass substrate in fitting can be turned into during the liquid crystal display in gap,
Therefore preferably less than 5 μm, more preferably less than 3 μm.In addition, though can unrestrictedly attenuate, but generally lower limit is about 0.1
μm.Particle diameter can utilize laser diffraction/scattering formula particle size distribution device (dry type), and (Seishin enterprises of Co., Ltd. manufacture；
LMS-30) determine.
It is the matter of 0.0001 mass %~10 preferably in the total amount of liquid crystal sealing agent for content as composition (B)
Measure %, the mass % of more preferably 0.0005 mass %~5 mass %, particularly preferably 0.001 mass %~3.
[(C) (methyl) acrylic compounds]
The liquid crystal sealing agent of the present application can contain (methyl) acrylic compounds as composition (C).(here,
" (methyl) acrylic acid " refers to " acrylic acid " and/or " methacrylic acid "；Similarly hereinafter).For composition (C), example can be enumerated
Such as：(methyl) acrylate compounds, epoxy (methyl) acrylate compounds etc..
It should be noted that the chemical combination of composition (A) is not included in (methyl) acrylic compounds as composition (C)
Thing.
For concrete example as (methyl) acrylic compounds, it can enumerate：N- acryloyl-oxyethyls hexahydro is adjacent
BIDA, acryloyl morpholine, (methyl) acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid 4- hydroxybutyls, hexamethylene-
1,4- dimethanols list (methyl) acrylate, (methyl) tetrahydrofurfuryl acrylate, (methyl) acrylate, phenyl gather
Ethyoxyl (methyl) acrylate, (methyl) acrylic acid 2- hydroxyl -3- phenoxy-propyls, o-phenyl phenol monosubstituted ethoxy (methyl)
Acrylate, o-phenyl phenol polyethoxy (methyl) acrylate, (methyl) acrylic acid are to cumylphenoxy ethyl ester, (methyl)
Isobornyl acrylate, (methyl) acrylic acid tribromophenoxy ethyl ester, (methyl) acrylic acid tetrahydrochysene dicyclopentadiene base ester,
(methyl) propylene acid dihydride dicyclopentadiene base ester, (methyl) propylene acid dihydride dicyclopentadiene base epoxide ethyl ester, 1,4-
Butanediol two (methyl) acrylate, 1,6-HD two (methyl) acrylate, 1,9- nonanediols two (methyl) acrylate,
Tricyclodecane Dimethanol (methyl) acrylate, bisphenol-A polyethoxy two (methyl) acrylate, (first of polymer with bis phenol A propoxyl group two
Base) acrylate, Bisphenol F polyethoxy two (methyl) acrylate, ethylene glycol two (methyl) acrylate, polyethylene glycol two
(methyl) acrylate, isocyanuric acid three (acryloyl-oxyethyl) ester, pentaerythrite four (methyl) acrylate, two seasons penta 4
Alcohol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate, tripentaerythritol six (methyl) acrylate, three seasons
Penta tetrol five (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, (first of trimethylolpropane polyethoxy three
Base) acrylate, two contracting trimethylolpropane four (methyl) acrylate, neopentyl glycol and 3-hydroxypivalic acid ester two propylene
The monomer classes such as the diacrylate of 6-caprolactone addition product of the ester of acid esters or neopentyl glycol and 3-hydroxypivalic acid.It is preferred that it can arrange
Lift：N- acryloyl-oxyethyls hexahydrophthalic phthalimide, (methyl) acrylate, (methyl) propylene acid dihydride
Dicyclopentadiene base epoxide ethyl ester.
Known in epoxy (methyl) acrylate compounds can be utilized by the reaction of epoxy resin and (methyl) acrylic acid
Method and obtain.Epoxy resin as raw material is not particularly limited, preferably epoxy resin more than 2 functions, can be with
Enumerate for example：Resorcinolformaldehyde resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol S type epoxy tree
Fat, phenol novolak type epoxy resin, cresol novolak type epoxy resin, phenol novolak type epoxy resin, bisphenol A novolac type epoxy resin, bis-phenol
F phenolic resin varnish type epoxy resins, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester type epoxy resin, contracting
Water glyceramine type epoxy resin, hydantoins type epoxy resin, isocyanurate type epoxy resin, there are three oxybenzene methylmethane bones
The 2-glycidyl etherificate of the bifunctional phenols such as the phenol novolak type epoxy resin and catechol of frame, resorcinol
Thing, the 2-glycidyl etherate of difunctionality alcohols and their halide, hydride etc..Wherein, from liquid crystal pollution
Viewpoint consideration, preferably bisphenol A type epoxy resin, resorcinolformaldehyde resin.In addition, epoxy radicals and (methyl) acryloyl group
Ratio it is not restricted, can be properly selected from the viewpoint of process adaptability and liquid crystal pollution.
Composition (C) can be used alone, and can also mix two or more.In the liquid crystal sealing agent of the present invention, using
In the case of composition (C), in the total amount of liquid crystal sealing agent, usually 10 mass %~80 mass %, preferably 20 mass %
~70 mass %.
[(D) organic filler]
The liquid crystal sealing agent of the present application can contain organic filler as composition (D).As above-mentioned organic filler
Speech, can be enumerated for example：Polyurethane particulate, acrylic resin fine-particles, ps particle, styrene olefin copolymer particulate
And organic silicone microparticle.It should be noted that organic silicone microparticle preferred KMP-594, KMP-597, KMP-598 (SHIN-ETSU HANTOTAI's chemical industry
Manufacture), TrefilRTME-5500,9701, EP-2001 (manufacture of Dong Li Dow Corning Corporations), the preferred JB-800T of polyurethane particulate,
HB-800BK (Negami Chemical Ind Co., Ltd.), the preferred Rabalon of ps particleRTM T320C、T331C、SJ4400、
SJ5400, SJ6400, SJ4300C, SJ5300C, SJ6300C (Mitsubishi Chemical's manufacture), styrene olefin copolymer particulate is preferred
SEPTONRTMSEPS2004、SEPS2063。
These organic fillers can be used alone, can also and with two or more.Further, it is possible to use two or more formation
Core shell structure.Wherein, preferably acrylic resin fine-particles, organic silicone microparticle.
In the case of using aforesaid propylene acid resin particulate, the nucleocapsid knot of two kinds of acrylic rubbers is preferably included
The situation of the acrylic rubber of structure, particularly preferred stratum nucleare is polyacrylic acid N-butyl and shell is polymethyl methacrylate.
It is as ZEFIACRTMF-351 is sold by Eike Kogyo K.K..
In addition, for as above-mentioned organic silicone microparticle, can enumerate：Organopolysiloxane crosslinking powder, straight chain diformazan
Based polysiloxane crosslinking powder etc..In addition, as composite silicone rubber, can enumerate organic in the covering of the surface of above-mentioned silicon rubber
The composite silicone rubber of silicones (such as organic poly sesquisiloxane resin).In these particulates, particularly preferred straight chain dimethyl gathers
The comprehensive silicon rubber of the straight chain dimethyl polysiloxane cross-linked powder of silicon rubber or the organic siliconresin covering of silicone cross-linked powder
Glue particulate.These organic silicone microparticles can be used alone, can also and with two or more.Additionally, it is preferred that the shape of rubber powder
Can be the viscosity after addition increase it is few spherical.In the liquid crystal sealing agent of the present invention, in the situation using composition (D)
Under, in the total amount of liquid crystal sealing agent, the mass % of the usually mass % of 5 mass %~50, preferably 5 mass %~40.
[(E) inorganic filler]
The liquid crystal sealing agent of the present invention can contain inorganic filler as composition (E).It is inorganic as what is contained in the present invention
For filler, it can enumerate：Silica, carborundum, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate,
Mica, talcum, clay, aluminum oxide, magnesia, zirconium oxide, aluminium hydroxide, magnesium hydroxide, calcium silicates, alumina silicate, lithium aluminium silicate,
Zirconium silicate, barium titanate, glass fibre, carbon fiber, molybdenum disulfide, asbestos etc., it can preferably enumerate：Fused silica, crystallization
Silica, silicon nitride, boron nitride, calcium carbonate, barium sulfate, calcium sulfate, mica, talcum, clay, aluminum oxide, aluminium hydroxide, silicon
Sour calcium, alumina silicate, preferably silica, aluminum oxide, talcum.These inorganic fillers can be used in mixed way two or more.
If the average grain diameter of inorganic filler is excessive, can turn into when manufacturing the liquid crystal cells of narrow gap in fitting up and down
The undesirable element in gap etc. can not be formed during glass substrate well, therefore, average grain diameter be below 2000nm be it is appropriate, it is excellent
Elect below 1000nm, more preferably below 300nm as.Additionally, it is preferred that lower limit be about 10nm, more preferably about
100nm.Particle diameter can pass through laser diffraction/scattering formula particle size distribution device (dry type) (Seishin enterprises of Co., Ltd. system
Make；LMS-30) it is measured.
In the liquid crystal sealing agent of the present invention, in the case of using inorganic filler, in the total amount of liquid crystal sealing agent, lead to
Often it is the mass % of 5 mass %~50, the mass % of preferably 5 mass %~40.It is less than 5 mass % feelings in the content of inorganic filler
Under condition, the adhesive strength of glass substrate is reduced, moisture-proof reliability is also deteriorated in addition, therefore the adhesive strength after moisture absorption sometimes
Reduce and also become big.In addition, in the case where the content of inorganic filler is higher than 50 mass %, because filer content is excessive, therefore have
When be difficult to crushing so as to which the gaps of liquid crystal cells can not be formed.
[(F) silane coupler]
The liquid crystal sealing agent of the present invention can realize adhesive strength, resistance to by adding silane coupler as composition (F)
Moist raising.
For composition (F), it can enumerate：3- glycidoxypropyltrime,hoxysilanes, 3- glycidoxies third
Ylmethyl dimethoxysilane, 3- glycidoxypropyls diethoxy silane, 2- (3,4- epoxycyclohexyls) ethyl three
Methoxy silane, N- phenyl-gamma-amino propyl trimethoxy silicane, N- (2- amino-ethyls) -3- amino propyl methyl dimethoxies
Base silane, N- (2- amino-ethyls) -3- amino propyl methyls trimethoxy silane, APTES, 3- mercaptos
Base propyl trimethoxy silicane, vinyltrimethoxy silane, N- (2- (vinyl-benzylamino) ethyl) -3- aminopropyls three
Methoxy silane hydrochloride, 3- methacryloxypropyl trimethoxy silanes, 3- chloropropylmethyldimethoxysilanes, 3-
R-chloropropyl trimethoxyl silane etc..These silane couplers are in the form of KBM series, KBE series etc. by SHIN-ETSU HANTOTAI's chemical industry strain formula
Commercial firm etc. sells, therefore easily can be obtained from market.In the liquid crystal sealing agent of the present invention, in the feelings using composition (F)
It is preferably the mass % of 0.05 mass %~3 in liquid crystal sealing agent total amount under condition.
[(G) epoxide]
The liquid crystal sealing agent of the present application can contain epoxide as composition (G).As epoxide, and
It is not particularly limited, preferably epoxides more than 2 functions, can enumerates for example：Resorcinolformaldehyde resin, bis-phenol
A types epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenol novolak type epoxy resin, cresol novolac are clear
Paint shaped epoxy resin, phenol novolak type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F phenolic type epoxy resin, alicyclic epoxy resin,
Aliphatic chain epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoins type ring oxygen tree
Fat, isocyanurate type epoxy resin, the phenol novolak type epoxy resin with three oxybenzene methylmethane skeletons and adjacent benzene
The 2-glycidyl etherate of the bifunctional phenols such as diphenol, resorcinol, the 2-glycidyl etherate of difunctionality alcohols and
Their halide, hydride etc..Wherein, from the viewpoint of liquid crystal pollution, preferably bisphenol A type epoxy resin, isophthalic two
Phenol diglycidyl ether.
It should be noted that in the epoxide as composition (G), the compound not comprising composition (A).
Composition (G) can be used alone, and can also mix two or more.In the liquid crystal sealing agent of the present invention, using
In the case of composition (G), in liquid crystal sealing agent total amount, the usually mass % of 5 mass %~50, preferably 5 mass %~30
Quality %.
[(H) thermal curing agents]
The liquid crystal sealing agent of the present invention contains thermal curing agents as composition (H).It polymerize with mentioned component (B) hot radical and draws
It is different to send out agent, composition (H) refers to the thermal curing agents that free radical is not produced because of heating.Specifically, can enumerate by non-common
The material of necleophilic reaction is carried out to the anion of, intramolecular with electronics, for example polynary amine, polyatomic phenol, organic can be enumerated
Sour hydrazide compound etc..But not limited to this.Wherein, particularly preferably organic acid hydrazide compound is used.It can enumerate for example：As
Terephthaldehyde's acid dihydrazide, isophthalic dihydrazide, the hydrazides of 2,6- naphthalenedicarboxylic acids two, the acyl of 2,6- pyridines two of aromatic hydrazide
Hydrazine, the hydrazides of 1,2,4- benzene three, the hydrazides of 1,4,5,8 naphthalenetetracarboxylic acid four, the hydrazides of pyromellitic acid four etc..In addition, if it is aliphatic acyl
Hydrazine compound, then it can enumerate for example：Formylhydrazine, acethydrazide, propionyl hydrazine, careless acid dihydrazide, acid dihydrazide, butanedioic acid two
Hydrazides, glutaric, adipic dihydrazide, the hydrazides of pimelic acid two, sebacic dihydrazide, the hydrazides of 1,4- hexamethylenes two, wine
Stone acid dihydrazide, apple acid dihydrazide, the hydrazides of iminodiacetic acid two, N, N '-hexamethylene bis semicarbazides, citric acid trigalloyl
Acyl in double (Hydrazinocarbonyl the ethyl) -5- isopropyl second of hydrazine, the hydrazides of NTA three, the hydrazides of hexamethylene tricarboxylic acid three, 1,3-
With hydantoins skeleton, preferably with valine hydantoins skeleton, (carbon atom of hydantoins ring is taken urea etc. by isopropyl
Generation after skeleton) dihydrazide compound, isocyanuric acid three (1- Hydrazinocarbonyls methyl) ester, (the 2- Hydrazinocarbonyls of isocyanuric acid three
Ethyl) ester, isocyanuric acid three (1- Hydrazinocarbonyls ethyl) ester, isocyanuric acid three (3- Hydrazinocarbonyls propyl group) ester, isocyanuric acid be double
(2- Hydrazinocarbonyls ethyl) ester etc..From solidification reactivity and the balance of latency, preferably isophthalic dihydrazide, third
Dihydrazi, adipic dihydrazide, isocyanuric acid three (1- Hydrazinocarbonyls methyl) ester, (the 1- Hydrazinocarbonyl second of isocyanuric acid three
Base) ester, isocyanuric acid three (2- Hydrazinocarbonyls ethyl) ester, isocyanuric acid three (3- Hydrazinocarbonyls propyl group) ester, it is particularly preferably different
Cyanurate three (2- Hydrazinocarbonyls ethyl) ester.
Composition (H) can be used alone, and can also mix two or more.In the liquid crystal sealing agent of the present invention, using
In the case of composition (H), in liquid crystal sealing agent total amount, the usually mass % of 0.1 mass %~10, preferably 1 mass %~5
Quality %.
[(I) optical free radical polymerization initiator]
The liquid crystal sealing agent of the present application can contain optical free radical polymerization initiator as composition (I).As light certainly
For base polymerization initiator, as long as produce free radical or acid by irradiating ultraviolet or visible ray and trigger chain polymerization
The compound of reaction is then not particularly limited, and can enumerate for example：Benzil dimethyl ketal, 1- hydroxycyclohexylphenyl first
Ketone, diethyl thioxanthone, benzophenone, 2- EAQs, 2- hydroxy-2-methyls propiophenone, 2- methyl-[4- (methyl mercapto) benzene
Base] -2- morpholino -1- propane, 2,4,6- trimethyl benzoyl diphenyl bases phosphine oxide, camphorquinone, 9-Fluorenone, Diphenyl disulfide
Ether etc..Specifically, can enumerate：IRGACURERTM 651、184、2959、127、907、369、379EG、819、784、754、
500、OXE01、OXE02、DAROCURERTM 1173、LUCIRINRTMTPO (being BASF AG's manufacture), SEIKUOLRTM
Z, BZ, BEE, BIP, BBI (being the manufacture of Seiko KCC) etc..
In addition, from the viewpoint of liquid crystal pollution, preferably have the light of (methyl) acryloyl group free using intramolecular
Base polymerization initiator, such as preferably use 2- methacryloxyethyls isocyanates and 1- [4- (2- hydroxyl-oxethyls) benzene
Base] -2- hydroxy-2-methyl -1- propane -1- ketone reaction product.The compound can pass through International Publication No. 2006/027982
Method described in number is manufactured and obtained.
In the liquid crystal sealing agent of the present invention, in the case where using composition (I), in liquid crystal sealing agent total amount, generally
For the mass % of 0.001 mass %~3, the mass % of preferably 0.002 mass %~2.
In the liquid crystal sealing agent of the present invention, the curing accelerators such as organic acid, imidazoles, freedom can also be coordinated as needed
The additives such as base polymerization inhibitor, pigment, levelling agent, defoamer, solvent.
[curing accelerator]
For above-mentioned curing accelerator, it can enumerate：Organic acid, imidazoles etc..
For organic acid, it can enumerate：The situation of organic carboxyl acid, organic phosphoric acid etc., preferably organic carboxyl acid.Specifically
For, it can enumerate：Phthalic acid, M-phthalic acid, terephthalic acid (TPA), trimellitic acid, benzophenone tetracarboxylic, furans two
The aromatic carboxylic acids such as formic acid, butanedioic acid, adipic acid, dodecanedioic acid, decanedioic acid, thio-2 acid, cyclohexane cyclohexanedimethanodibasic, isocyanide
Urea acid three (carboxymethyl group) ester, isocyanuric acid three (2- carboxy ethyls) ester, isocyanuric acid three (3- carboxypropyls) ester, isocyanuric acid
Two (2- carboxy ethyls) esters etc..
In addition, for as imidazolium compounds, can enumerate：2-methylimidazole, 2- phenylimidazoles, 2- undecyl miaows
Azoles, 2- heptadecyl imidazoles, 2- phenyl -4-methylimidazole, 1- benzyl -2- phenylimidazoles, 1 benzyl 2 methyl imidazole, 1- cyanogen
Base Ethyl-2-Methyl imidazoles, 1- cyano ethyl -2- phenylimidazoles, 1- cyano ethyl -2- undecyl imidazoles, 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 '))
Ethyl s-triazine-isocyanuric acid adduct, the 2 of 2-methylimidazole-isocyanuric acid：3 addition products, 2- phenylimidazoles-isocyanuric acid
Addition product, 2- phenyl -3,5- hydroxymethyl-imidazoles, 2- phenyl -4- methylol -5- methylimidazoles, 1- cyano ethyl -2- phenyl -
3,5- dicyano ethoxyl methyl imidazoles etc..
In the liquid crystal sealing agent of the present invention, in the case of using curing accelerator, in the total amount of liquid crystal sealing agent,
The mass % of the usually mass % of 0.1 mass %~10, preferably 1 mass %~5.
[radical polymerization inhibitor]
For above-mentioned radical polymerization inhibitor, as long as with being gathered by optical free radical polymerization initiator, hot radical
The compound closed radical reaction caused by initiator etc. and suppress polymerization is then not particularly limited, and can use quinones, piperidines
Class, Hinered phenols, nitrous base class etc..Specifically, can enumerate：Naphthoquinones, 2 hydroxy naphthalene quinone, 2 methyl naphthoquinone, 2- methoxyl groups
Naphthoquinones, 2,2,6,6- tetramethyl piperidine -1- oxides, 2,2,6,6- tetramethyl -4- hydroxy piperidine -1- oxides, 2,2,6,6-
Tetramethyl -4- methoxy piperide -1- oxides, 2,2,6,6- tetramethyl -4- Phenoxypiperidines -1- oxides, quinhydrones, 2- methyl
Quinhydrones, 2- methoxyhydroquinons, 1,4-benzoquinone, butylated hydroxyanisol, 2,6- di-t-butyl -4- ethyl -phenols, bis- tertiary fourths of 2,6-
Base cresols, β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid stearyl ester, 2,2 '-di-2-ethylhexylphosphine oxide (4- ethyl -6- tert-butyl benzenes
Phenol), 4,4 '-thiobis (3 methy 6 tert butyl phenol), 4,4 '-butylidene-bis(3-methyl-6-t-butyl phenol), 3,9-
Double oxa-s of [1,1- dimethyl -2- [β-(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionyloxy] ethyl] -2,4,8,10- four
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- methoxyl groups -1-
Naphthols, phenthazine, the aluminium salt of N- nitrosophenylhydroxylamines, trade name ADK STAB LA-81, trade name ADK STAB LA-82
(Asahi Denka Co., Ltd.'s manufacture) etc., but not limited to this.Wherein, preferably naphthoquinones class, hydroquinones, nitrous base class, piperazines from
By base polymerization inhibitor, more preferably naphthoquinones, 2 hydroxy naphthalene quinone, quinhydrones, BHT, POLYSTOP 7300P
(Hakuto KK's manufacture), most preferably POLYSTOP 7300P (Hakuto KK's manufacture).
It is preferably 0.0001 in the liquid crystal sealing agent total amount of the present invention for the content of radical polymerization inhibitor
The mass % of quality %~1 mass %, more preferably 0.001 mass %~0.5, particularly preferably 0.01 mass %~0.2
Quality %.
For one of the method for the liquid crystal sealing agent for obtaining the present invention, there is method as follows.First, will
(A) composition and (C) composition as needed, (G) composition, (I) composition dissolve by heating.Room temperature is then cooled to, then basis
Need to add (B) composition, (D) composition, (E) composition, (F) composition, (H) composition, defoamer and levelling agent, solvent etc., utilize
Known mixing arrangement equably mixes such as three-roller, sand mill, ball mill, and is filtered using wire netting, thus
The liquid crystal sealing agent of the present invention can be manufactured.
The liquid crystal display of the present invention by by a pair of substrates formed with regulation electrode on substrate between defined
Every relative configuration, the liquid crystal sealing agent of the surrounding present invention is sealed, and enclose liquid crystal in gap therebetween and obtain.Enclosed
The species of liquid crystal is not particularly limited.Here, substrate comprising glass, quartz, plastics, silicon etc. and at least one substrate by having thoroughly
The substrate of the combination of photosensitiveness is formed.For its manufacture method, glass fibre etc. is added in the liquid crystal sealing agent of the present invention
Sept (gap control material), it is then using point gum machine (デ ィ ス ペ Application サ ー) or silk-screen printing device etc. that the liquid crystal is close
Envelope agent is applied on a substrate in a pair of substrates, then, carries out precuring (Provisional at 80 DEG C~120 DEG C as needed
Hardening).Then, in the inner side dispenser method in the cofferdam of the liquid crystal sealing agent, another overlapping glass substrate, is carried out in a vacuum
Gap is formed.After forming gap, solidify 1 hour~2 hours at 90 DEG C~130 DEG C, it is hereby achieved that the liquid crystal of the present invention
Display unit.In addition, in the case where being used as photo-thermal and with type, irradiated using ultraviolet irradiation machine to liquid crystal sealing agent portion
Ultraviolet and carry out photocuring.Ultraviolet irradiation amount is preferably 500mJ/cm2~6000mJ/cm2, more preferably 1000mJ/cm2
~4000mJ/cm2Exposure.Then solidify 1 hour~2 hours at 90 DEG C~130 DEG C as needed, it is hereby achieved that
The liquid crystal display of the present invention.The liquid crystal display of the invention obtained in this way is not present to be drawn by liquid crystal pollution
The display risen is bad, and adhesivity, moisture-proof are excellent in reliability.For sept, it can enumerate for example：Glass fibre, dioxy
SiClx microballon, polymer microbeads etc..Its diameter is different according to purpose, usually 2 μm~8 μm, preferably 4 μm~7 μm.It makes
Dosage is typically about the mass parts of 0.1 mass parts~about 4 relative to the mass parts of liquid crystal sealing agent 100 of the present invention, and preferably from about 0.5
The mass parts of the mass parts of mass parts~about 2, more preferably about 0.9 mass parts~about 1.5.
The thermosetting of the liquid crystal sealing agent of the present invention is very good, rapid curing in the heating process in liquid crystal drip-injection method,
The adhesivity of its solidfied material is excellent, and liquid crystal pollution is good, therefore by using the liquid crystal sealing agent of the present invention, can be made
Liquid crystal display excellent in reliability.
Embodiment
Hereinafter, the present invention is illustrated in further detail by embodiment, but the invention is not restricted to embodiment.Need
Illustrate, recorded as long as no special, " part " and " % " herein is quality criteria.
[synthesis example 1：The synthesis of the full acryloyl compound of bisphenol A type epoxy resin]
By 282.5g bisphenol A type epoxy resin (ProductNames：YD-8125, Nippon Steel Chemical Co., Ltd's manufacture) it is dissolved in
In 266.8g toluene, dibutyl hydroxy toluenes of the 0.8g as polymerization inhibitor is added wherein, and be warming up to 60 DEG C.Then, add
The acrylic acid 117.5g of 100% equivalent of epoxy radicals, further heat up to 80 DEG C, add 0.6g wherein as catalysts
Trimethylammonium chloride, stir about 30 hours at 98 DEG C, so as to obtain reaction solution.The reaction solution is washed, steamed
Toluene is removed in distillation, resulting in epoxy acrylates of the 395g as the bisphenol A-type of target.
[synthesis example 2：The synthesis of the part propylene acylate of bisphenol A type epoxy resin]
836g bisphenol A type epoxy resins (RE-310S of Nippon Kayaku K. K's manufacture) are dissolved in 1000g toluene
In, dibutyl hydroxy toluenes of the 3g as polymerization inhibitor is added wherein, and is warming up to 60 DEG C.Then, the 50% of epoxy radicals is added
The acrylic acid 165g (Nippon Shokubai Co., Ltd's manufacture) and 5g of equivalent are as the tripropyl ammonium hydroxide of catalysts
40% aqueous solution, stir about 10 hours at 98 DEG C, so as to obtain reaction solution.The reaction solution is washed, is distilled off
Toluene, the part propylene that resulting in 995g as target are acylated bisphenol A type epoxy resin.
[synthesis example 3：The synthesis of the part propylene acylate of bisphenol f type epoxy resin]
495g bisphenol f type epoxy resins (RE-304S of Nippon Kayaku K. K's manufacture) are dissolved in 600g toluene,
Dibutyl hydroxy toluenes of the 1.8g as polymerization inhibitor is added wherein, and is warming up to 60 DEG C.Then, add epoxy radicals 50% is worked as
The acrylic acid 105g (Nippon Shokubai Co., Ltd's manufacture) and 3g of amount are as the tripropyl ammonium hydroxide of catalysts
40% aqueous solution, stir about 10 hours at 98 DEG C, so as to obtain reaction solution.The reaction solution is washed, is distilled off
Toluene, the part propylene that resulting in 594g as target are acylated bisphenol f type epoxy resin.
[synthesis example 4：The synthesis of double (the trimethylsiloxy) -1,1,2,2- tetraphenyl ethane of 1,2-]
100 parts of (0.28 mole) commercially available benzpinacols (Tokyo chemical conversion manufacture) are made to be dissolved in 350 parts of dimethylformamides.
32 parts (0.4 moles) are added wherein as the pyridine of base catalyst, 150 parts (0.58 moles) as silylating agent
BSTFA (SHIN-ETSU HANTOTAI's chemical industry manufacture), is warming up to 70 DEG C, stirs 2 hours.Resulting reaction solution is cooled down, stirred
While add 200 parts of water, precipitate product, at the same make unreacted silylating agent inactivate.Product after precipitation is carried out
It is separated by filtration, then fully washes.Then resulting product is dissolved in acetone, adding water makes its recrystallization, goes forward side by side
Purifying is gone.Double (the trimethylsiloxy) -1,1,2,2- tetraphenyl ethane of 105.6 parts of 1,2- as target are obtained
(yield 88.3%).
[preparation of embodiment 1~6, comparative example 1~3]
Composition (A), ring are added in (methyl) acrylic compounds (composition (C)) with the ratio shown in table 1 below
Oxygen compound (composition (G)), optical free radical polymerization initiator (composition (I)), are dissolved by heating at 90 DEG C.Room temperature is cooled to, is added
Enter hot radical polymerization initiator (composition (B)), organic filler (composition (D)), inorganic filler (E), thermal curing agents (composition
(H)), silane coupler (composition (F)) etc., and be stirred, then make it scattered with three-roller, entered with wire netting (635 mesh)
Row filtering, so as to be prepared for liquid crystal drip-injection method sealant (embodiment 1~6, comparative example 1~3).
[evaluation of embodiment 1~6, comparative example 1~3]
[glass transition temperature and mechanical loss coefficient tan δ assay method]
The liquid crystal sealing agent manufactured in embodiment, comparative example is clipped between polyethylene terephthalate (PET) film
The film that thickness is 100 μm is made, the film is shone with metal halide lamp (excellent prosperous (USHIO) Electric Co., Ltd of will manufactures)
Penetrate 3000mJ/cm2(with 100mW/cm2Irradiation 30 seconds) ultraviolet, then putting into 120 DEG C of baking oven makes its solidification in 40 minutes.
PET film is peeled off after solidification and obtains sealant cures film, is then cut to 50mm × 5mm strip so as to obtain sample
Piece.The sample strip is utilized into Measurement of Dynamic Viscoelasticity device (DMS-6100：Seiko electronics nanosecond science and technology Co., Ltd. (SII
NanoTechnology Inc.) manufacture) stretch mode surveyed under conditions of frequency 10Hz, 2 DEG C/min of warming temperature
It is fixed, loss factor tan δ are obtained by the ratio of loss modulus and storage modulus (JIS K 7244-1).By resulting loss factor
Temperature when tan δ reach maximum is as glass transition temperature.
[elastic modulus detection]
The liquid crystal sealing agent manufactured for embodiment and comparative example, is sandwiched polyethylene terephthalate (PET)
In film, the film of 100 μm of thickness is made, to film metal halide lamp (excellent prosperous (USHIO) the Electric Co., Ltd system of will
Make) irradiation 3000mJ/cm2(with 100mW/cm2Irradiation 30 seconds) ultraviolet make its solidification, then put into 40 in 120 DEG C of baking oven
Minute makes its solidification, and PET film is peeled off and obtains sealant cures film, is then cut into dumbbell shaped test film (overall length
75mm, overall width 10mm, the length 50mm of narrow parallel portion, width 5mm, thickness 0.1mm) and it is used as sample strip.It is right
Resulting test film, using Tensilon universal testing machines (Co., Ltd. A＆D manufactures, RTG-1210), at room temperature (22 DEG C)
Under, tension test is carried out with test speed 3mm/ minutes, springform is calculated by the tension in proportional limit and the result of strain
Amount.
[elongation at break]
The liquid crystal sealing agent manufactured for embodiment and comparative example, is sandwiched polyethylene terephthalate (PET)
In film, the film of 100 μm of thickness is made, to film metal halide lamp (excellent prosperous (USHIO) the Electric Co., Ltd system of will
Make) irradiation 3000mJ/cm2(with 100mW/cm2Irradiation 30 seconds) ultraviolet make its solidification, then put into 40 in 120 DEG C of baking oven
Minute makes its solidification, and PET film is peeled off and obtains sealant cures film, is then cut into dumbbell shaped test film (overall length
75mm, overall width 10mm, the length 50mm of narrow parallel portion, width 5mm, thickness 0.1mm) and it is used as sample strip.It is right
Resulting test film, using Tensilon universal testing machines (Co., Ltd. A＆D manufactures, RTG-1210), at room temperature (22 DEG C)
Under, tension test is carried out with test speed 3mm/ minutes, elongation is calculated by the incrementss of the distance of parallel portion.
[folding test]
Sealant cures film is made by the method same with elasticity modulus measuring method, and cuts into length 50mm, width
5mm, thickness 0.1mm rectangle are spent, so as to obtain sample strip.By resulting sample strip with cause its turn into half length
25mm mode bending, and secure 10 seconds.The uncracked situation of test film is evaluated as zero, the situation that test film ruptures is commented
Valency for ×.
[adhesive strength]
The liquid crystal sealing agent manufactured for embodiment and comparative example, is sandwiched polyethylene terephthalate (PET)
In film, the film of 100 μm of thickness is made, to film metal halide lamp (excellent prosperous (USHIO) the Electric Co., Ltd system of will
Make) irradiation 3000mJ/cm2(with 100mW/cm2Irradiation 30 seconds) ultraviolet make its solidification, then put into 40 in 120 DEG C of baking oven
Minute makes its solidification.Length 50mm, width 5mm, thickness 0.1mm rectangle are cut into, so as to obtain sample strip.By obtained by
Sample strip bending in a manner of causing it to turn into length 25mm of half, and secure 10 seconds.Sample is observed, will be tried
Test the situation that piece does not rupture and do not peeled off from PET film and be evaluated as zero, test film is not ruptured but the situation of PET film stripping is evaluated as
△, test film rupture and PET film situation about also peeling off are evaluated as ×.
Table 1
A-1：(Nippon Kayaku K. K manufactures polyester urethane acrylate：KAYARAD UX-3204)
A-2：(Nippon Kayaku K. K manufactures polycaprolactone type urethane acrylate：KAYARAD UX-
4101)
A-3：(Nippon Kayaku K. K manufactures polyetherurethane acrylate：KAYARAD UX-0937)
B-1：Double (the trimethylsiloxy) -1,1,2,2- tetraphenyls ethane (synthesis examples 4 of 1,2-；Use airslide disintegrating mill
(jet mill) finely pulverized material into 1.9 μm of average grain diameter)
C-1：The full acryloyl compound (synthesis example 1) of bisphenol A type epoxy resin
C-2：The part propylene acylate (synthesis example 2) of bisphenol A type epoxy resin
C-3：The part propylene acylate (synthesis example 3) of bisphenol f type epoxy resin
C-4：Acrylic acid neighbour's phenylphenoxy ethyl ester (trade name " manufacture of Miramer M-1142 " MIWON companies)
D-1：(Eike Kogyo K.K. manufactures polymethacrylate organic fine particles：F-351S)
F-1：(JNC Corporation manufactures 3- glycidoxypropyltrime,hoxysilanes：Sila-Ace S-510)
F-2：(Shin-Etsu Chemial Co., Ltd manufactures N- (2- aminoethyls) -3- aminopropyl triethoxysilanes：KBM-
603)
G-1：(Nippon Kayaku K. K manufactures bisphenol A type epoxy resin：RE-310S)
H-1：(Japan of Co., Ltd. fine chemistry manufacture of isocyanuric acid three (2- Hydrazinocarbonyls ethyl) finely pulverized product of ester：
HCIC, with the finely pulverized material into 1.5 μm of average grain diameter of airslide disintegrating mill)
H-2：Sebacic dihydrazide (Japan of Co., Ltd. fine chemistry manufacture：SDH)
I-1：2- methacryloxyethyls isocyanates and 1- [4- (2- hydroxyl-oxethyls) phenyl] -2- hydroxyls -2-
The reaction product (being synthesized by the method described in International Publication No. 2006/027982) of methyl isophthalic acid-propane -1- ketone
I-2：(BASF Co., Ltd. manufactures 1- [4- (thiophenyl) phenyl] -1,2- octanediones 2- (O- benzoyls oxime)：
IRGACURE OXE-01)
I-3：(BASF Co., Ltd. manufactures 2,4,6- trimethyl benzoyl diphenyl bases phosphine oxide：IRGACURE TPO)
O-1：(Hakuto KK manufactures nitrous base class piperidine derivative：POLYSTOP 7300P)
O-2：(Shikoku Chem manufactures isocyanuric acid three (2- carboxy ethyls) ester：CIC acid, with air-flow powder
The finely pulverized material into 1.5 μm of average grain diameter of broken machine)
By the results verification of table 1：Containing intramolecular there is the compound of amino-formate bond, solidfied material to pass through DMA
The glass transition temperature of method measure is less than 90 DEG C, the modulus of elasticity for the liquid crystal sealing agent of the invention that tan δ are more than 0.5
Low and when being broken elongation is also big, thus in bend test, adhesive test compared with the liquid crystal sealing agent of comparative example table
Reveal good result.
Industrial applicability
The liquid crystal sealing agent of the present invention can also be applied to flexible display, the display of curved shape, and gluing strong
The general characteristics such as degree are also excellent, therefore can realize the high liquid crystal display of reliability.
Claims (15)
1. a kind of liquid crystal drip-injection method liquid crystal sealing agent, wherein, the liquid crystal drip-injection method liquid crystal sealing agent contains at least one
(A) intramolecular has the compound of amino-formate bond, and
The liquid crystal drip-injection method with the glass transition temperature determined by DMA methods of the solidfied material of liquid crystal sealing agent for 90 DEG C with
Under, tan δ be more than 0.5.
2. liquid crystal drip-injection method liquid crystal sealing agent as claimed in claim 1, wherein, the weight average molecular weight of (A) is 1000
More than.
3. liquid crystal drip-injection method liquid crystal sealing agent as claimed in claim 1 or 2, wherein, (A) is that intramolecular has 3
The compound of above ester bond.
4. such as liquid crystal drip-injection method liquid crystal sealing agent according to any one of claims 1 to 3, wherein, the liquid crystal drip-injection method
Also contain (B) hot radical polymerization initiator with liquid crystal sealing agent.
5. such as liquid crystal drip-injection method liquid crystal sealing agent according to any one of claims 1 to 4, wherein, the liquid crystal drip-injection method
Also contain (C) (methyl) acrylic compounds with liquid crystal sealing agent.
6. such as liquid crystal drip-injection method liquid crystal sealing agent according to any one of claims 1 to 5, wherein, the liquid crystal drip-injection method
Also contain (D) organic filler with liquid crystal sealing agent.
7. liquid crystal drip-injection method liquid crystal sealing agent as claimed in claim 6, wherein, the composition (D) is selected from by polyurethane
In the group that particulate, acrylic resin fine-particles, ps particle, styrene olefin copolymer particulate and organic silicone microparticle are formed
One or more kinds of organic fillers.
8. such as liquid crystal drip-injection method liquid crystal sealing agent according to any one of claims 1 to 7, wherein, the liquid crystal drip-injection method
Also contain (E) inorganic filler with liquid crystal sealing agent.
9. such as liquid crystal drip-injection method liquid crystal sealing agent according to any one of claims 1 to 8, wherein, the liquid crystal drip-injection method
Also contain (F) silane coupler with liquid crystal sealing agent.
10. such as liquid crystal drip-injection method liquid crystal sealing agent according to any one of claims 1 to 9, wherein, the liquid crystal drip-injection method
Also contain (G) epoxide with liquid crystal sealing agent.
11. such as liquid crystal drip-injection method liquid crystal sealing agent according to any one of claims 1 to 10, wherein, the liquid crystal drip-injection
Method liquid crystal sealing agent also contains (H) thermal curing agents.
12. liquid crystal drip-injection method liquid crystal sealing agent as claimed in claim 11, wherein, the composition (H) is organic acid hydrazides
Compound.
13. the liquid crystal drip-injection method liquid crystal sealing agent as any one of claim 1~12, wherein, the liquid crystal drip-injection
Method liquid crystal sealing agent also contains (I) optical free radical polymerization initiator.
14. a kind of manufacture method of liquid crystal display, it is characterised in that in the liquid crystal display being made up of two substrates
In, by the liquid crystal drip-injection method liquid crystal any one of liquid crystal drip-injection to the claim 1~13 being formed on a substrate
The inner side in the cofferdam of sealant, another substrate is then bonded, is then solidified using heat.
15. a kind of liquid crystal display, it is obtained using the liquid crystal sealing agent any one of claim 1~13 is solidified
To solidfied material sealed.
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| JP2016153382A JP6744167B2 (en) | 2016-08-04 | 2016-08-04 | Liquid crystal sealant and liquid crystal display cell using the same |
| JP2016-153382 | 2016-08-04 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110529594A (en) * | 2019-07-26 | 2019-12-03 | 中国航空工业集团公司济南特种结构研究所 | A kind of sealant localization method carrying out multistage sealing using soft material |
| CN111690367A (en) * | 2019-03-15 | 2020-09-22 | 日本化药株式会社 | Sealant for display and liquid crystal display |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7332263B2 (en) * | 2019-12-05 | 2023-08-23 | 日本化薬株式会社 | Adhesive for electronic parts |
| JP7332264B2 (en) * | 2019-12-05 | 2023-08-23 | 日本化薬株式会社 | Adhesive for electronic parts |
| JP7432492B2 (en) * | 2020-12-11 | 2024-02-16 | 日本化薬株式会社 | Liquid crystal sealant for liquid crystal dripping method |
| JP7489911B2 (en) * | 2020-12-11 | 2024-05-24 | 日本化薬株式会社 | Liquid crystal sealant for liquid crystal dripping method |
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Also Published As
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| CN107686716B (en) | 2021-12-24 |
| JP2018022053A (en) | 2018-02-08 |
| KR20180016272A (en) | 2018-02-14 |
| JP6744167B2 (en) | 2020-08-19 |
| KR102436297B1 (en) | 2022-08-24 |
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