CN104428710A - Liquid crystal sealing agent and liquid crystal display cell using same - Google Patents
Liquid crystal sealing agent and liquid crystal display cell using same Download PDFInfo
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- CN104428710A CN104428710A CN201380036541.3A CN201380036541A CN104428710A CN 104428710 A CN104428710 A CN 104428710A CN 201380036541 A CN201380036541 A CN 201380036541A CN 104428710 A CN104428710 A CN 104428710A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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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
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/10—Epoxy resins modified by unsaturated compounds
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
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Abstract
Provided is a liquid crystal sealing agent for use in a liquid crystal dropping process which, due to the particularly excellent adherence to an organic film such as an oriented film, does not readily peel from upper/lower substrates even in various environments, and further, has excellent fundamental characteristics as a liquid crystal sealing agent, such as low liquid crystal staining properties and heat resistance. This liquid crystal sealing agent is characterized in that, when the strength of adhesive bonding to an ITO substrate at 25 DEG C after curing for 1 hour under an atmosphere of 120 DEG C, following irradiation of 3000 mJ/cm2 ultraviolet rays, is taken as A [MPa], the strength of adhesive bonding at 120 DEG C after said curing is taken as B [MPa], and the strength of adhesive bonding to an ITO substrate at 25 DEG C after curing with only 3000 mJ/cm2 ultraviolet rays is taken as C [MPa], A, B and C satisfied the relational expressions shown by expressions (1) and (2) below. B >= 0.5 * A (1) C>= 0.3 * A (2)
Description
Technical field
The present invention relates to the liquid crystal sealing agent used in liquid crystal dripping process.More specifically, relate to very excellent liquid crystal sealing agent such as the cementability of the organic film of alignment films etc. and the liquid crystal display using it.
Background technology
Along with the maximization of liquid crystal display in recent years, as the manufacture method of liquid crystal display, propose production higher, so-called liquid crystal dripping process (patent documentation 1,2).This liquid crystal dripping process specifically after liquid crystal is dripped in the inner side being formed at the weir be made up of liquid crystal sealing agent on a substrate, another substrate in the manufacture method making liquid crystal sealing agent solidify thereafter of fitting.
But, in liquid crystal dripping process, before liquid crystal sealing agent solidification, liquid crystal contacts with liquid crystal sealing agent, therefore produces the pressure that causes because of liquid crystal and insert the phenomenon of liquid crystal sealing agent, in the worst case, sometimes can run quickly and burst in the weir be made up of liquid crystal sealing agent, thus throw into question.In order to head it off, need the precision of the amount of dripping improving liquid crystal, even if but like this, when the heating of the curing process as liquid crystal sealing agent, liquid crystal expands, therefore be difficult to suppress completely above-mentioned insertion phenomenon.
In order to suppress above-mentioned insertion phenomenon, proposing the reaction velocity of raising liquid crystal sealing agent, realize the rapid curing from during low temperature or use gelating agent etc. to increase the technology (patent documentation 3,4) of the viscosity of liquid crystal sealing agent when heating.These pressure this respects brought from the expansion of liquid crystal sealing agent antagonism liquid crystal are rational technology, but do not flee from part because this pressure becomes, as a result, vertically, namely peel off the direction of two pieces of substrates to be applied with power, to such an extent as to newly create this bad phenomenon of strippable substrate occurs.
And the liquid crystal sealing agent improving above-mentioned reaction velocity or interpolation gelating agent is large along with the change of time, uses in easiness have problems through being everlasting.
In addition, current, liquid crystal display cells is unconventionally for various equipment.Therefore, need the change of large temperature or can not bad phenomenon be produced to high humility.This characteristic is the equal characteristic be suitable for liquid crystal sealing agent, and requirement can not produce the stripping between substrate because of the change of temperature, in addition, have the characteristic of the immersion of patience or anti-sealing at high humidity.As the method solving this problem, propose use and have (patent documentations 5) such as part (methyl) acrylated epoxy resins of specific character.But, be not perfect material.
In addition, in the liquid crystal panel of narrow frame design in recent years, the line width of liquid crystal sealing agent is comparatively thin, and the problem of bonding strength is than more serious in the past.That is, the line width of liquid crystal sealing agent attenuates, and causes the problem that upper and lower base plate is peeled off after normal temperature and moisture-proof failtests under existing bonding strength.
And recently, design liquid crystal sealing agent being configured in the liquid crystal display on alignment films etc. becomes more and more.But in existing liquid crystal sealing agent, the cementability to such organic film hard to say is sufficient, therefore becomes the problem that will solve.
As above, in the liquid crystal sealing agent of liquid crystal dripping process, there is various problems, although consume energy to go research, the product solving them not yet develops.
In addition, the liquid crystal sealing agent of liquid crystal dripping process needs to be excellent in the general characteristic of low liquid crystal pollution, high-adhesive-strength etc.
Prior art document
Patent documentation
Patent documentation 1: Japanese Laid-Open Patent Publication 63-179323 publication
Patent documentation 2: Japanese Unexamined Patent Publication 10-239694 publication
Patent documentation 3: No. 2011/061910th, International Publication
Patent documentation 4: Japanese Unexamined Patent Publication 2006-23419 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2011-221168 publication.
Summary of the invention
The problem that invention will solve
The present invention proposes liquid crystal sealing agent and uses its liquid crystal display, described liquid crystal sealing agent is the liquid crystal sealing agent used in liquid crystal dripping process, it is particularly excellent on the cementability of the organic film with alignment films etc., therefore under circumstances under be all difficult to the stripping of upper and lower base plate occurs, in lower liquid crystal pollution, thermotolerance etc. as excellent on the fundamental characteristics of liquid crystal sealing agent.
Solve the means of problem
That the present inventor's process is carefully studied as a result, find to establish to irradiate 3000mJ/cm
2ultraviolet after, bonding strength when being after A (MPa), above-mentioned solidification 120 DEG C to the bonding strength of ITO (tin indium oxide) substrate when solidifying 25 DEG C after 1 hour under 120 DEG C of atmosphere is B (MPa), only by 3000mJ/cm
2ultraviolet curing after 25 DEG C time when being C (MPa) to the bonding strength of ITO (tin indium oxide) substrate, above-mentioned A, B and C have the liquid crystal sealing agent of certain relation, to very excellent in the bonding strength of organic film, to such an extent as to make the present invention.
In addition, in this instructions, " (methyl) acrylic acid ((metha) acryl) " means " acrylic acid (acryl) and/or methacrylic acid (methaacryl) ".
Namely the present invention relates to following 1) ~ 13).
1) a liquid crystal dripping process liquid crystal sealing agent, wherein, if irradiate 3000mJ/cm
2ultraviolet after, bonding strength when being after A (MPa), described solidification 120 DEG C to the bonding strength of ITO (tin indium oxide) substrate when solidifying 25 DEG C after 1 hour under 120 DEG C of atmosphere is B (MPa), only by 3000mJ/cm
2ultraviolet curing after 25 DEG C time when being C (MPa) to the bonding strength of ITO (tin indium oxide) substrate, described A, B and C meet the relational expression that following formula (1) and (2) represent:
B≧0.5×A (1)
C≧0.3×A (2)。
2) according to above-mentioned 1) described in liquid crystal dripping process liquid crystal sealing agent, wherein, if only by 3000mJ/cm
2ultraviolet curing after 120 DEG C time when being D (MPa) to the bonding strength of ITO (tin indium oxide) substrate, described A and D meets the relational expression represented by following formula (3):
D≧0.3×A (3)。
3) according to above-mentioned 1) or 2) described in liquid crystal dripping process liquid crystal sealing agent, comprise: composition (a) (methyl) acrylated epoxy resins, composition (b) Photoepolymerizationinitiater initiater, the agent of composition (c) inorganic filler and composition (d) organic acid hydrazide compound.
4) according to above-mentioned 3) described in liquid crystal dripping process liquid crystal sealing agent, also comprise: composition (e) hot radical polymerization initiator.
5) according to above-mentioned 4) described in liquid crystal dripping process liquid crystal sealing agent, wherein, mentioned component (e) hot radical polymerization initiator is 1,2-two (trimethylsiloxy group)-1,1,2,2-tetraphenyl ethane.
6) according to above-mentioned 3) to 5) according to any one of liquid crystal dripping process liquid crystal sealing agent, also comprise composition (f) epoxy resin.
7) according to above-mentioned 3) to 6) according to any one of liquid crystal dripping process liquid crystal sealing agent, also comprise composition (g) silane coupling agent.
8) according to above-mentioned 7) described in liquid crystal dripping process liquid crystal sealing agent, wherein, mentioned component (g) is amino silicane coupling agent.
9) according to above-mentioned 7) described in liquid crystal dripping process liquid crystal sealing agent, wherein, mentioned component (g) is the potpourri of amino silicane coupling agent and epoxy silane coupling agent.
10) above-mentioned 3) to 9) according to any one of liquid crystal dripping process liquid crystal sealing agent, also comprise the compound that composition (h) has phenolic hydroxyl group.
11) the liquid crystal dripping process liquid crystal sealing agent above-mentioned 10), wherein, mentioned component (h) is phenol resol resins.
12) a kind of manufacture method of liquid crystal display, wherein, in the liquid crystal display be made up of two pieces of substrates, to be formed on a substrate by above-mentioned 1) to 11) and according to any one of the inner side on weir that forms of liquid crystal dripping process liquid crystal sealing agent drip after liquid crystal, to fit a substrate, utilize thereafter liquid crystal dripping process liquid crystal sealing agent described in ultraviolet and/or heat curing.
13) liquid crystal display, it is by solidifying above-mentioned 1) to 11) according to any one of liquid crystal dripping process liquid crystal sealing agent and the solidfied material obtained is bonding.
Invention effect
Liquid crystal dripping process liquid crystal sealing agent of the present invention with the cementability of the particularly organic film of alignment films etc. on very excellent, be all difficult under circumstances peel off.Therefore, the liquid crystal display making can to use at various environment be embodied as in order to may.In addition, also excellent in the general characteristic of low liquid crystal pollution, thermotolerance, heat-resisting cyclicity, moisture-proof etc., therefore liquid crystal display excellent on long-term reliability can be realized.
Embodiment
Liquid crystal dripping process liquid crystal sealing agent of the present invention is (hereinafter referred to as " liquid crystal sealing agent ".) feature be, be located at irradiate 3000mJ/cm
2ultraviolet after, bonding strength when being after A (MPa), above-mentioned solidification 120 DEG C to the bonding strength of ITO (tin indium oxide) substrate when solidifying 25 DEG C after 1 hour under 120 DEG C of atmosphere is B (MPa), only by 3000mJ/cm
2ultraviolet curing after 25 DEG C time when being C (MPa) to the bonding strength of ITO (tin indium oxide) substrate, above-mentioned A, B and C meet the relational expression represented by following formula (1), (2).
B≧0.5×A (1)
C≧0.3×A (2)
Above-mentioned formula (1) means, at irradiation 3000mJ/cm
2ultraviolet after, under 120 DEG C of atmosphere, solidify the bonding strength under 120 DEG C of atmosphere after 1 hour, be more than 5 one-tenth of the bonding strength under 25 DEG C of atmosphere.There is the liquid crystal sealing agent of this characteristic, in the heating process in the manufacture of liquid crystal display, the stripping of upper and lower base plate can not be produced, stable manufacture can be realized.In addition, as thermal cycle experiment, even if when the state of alternately high temperature and low temperature, also can not strippable substrate be there is and settle out.
In addition, above-mentioned formula (2) means, only irradiates 3000mJ/cm
2ultraviolet and bonding strength under 25 DEG C of atmosphere after solidifying, be irradiate 3000mJ/cm
2ultraviolet after, more than 3 one-tenth of the bonding strength of solidifying under 120 DEG C of atmosphere under 25 DEG C of atmosphere after 1 hour.Cure shrinkage in the Ultraviolet radiation operation of the liquid crystal sealing agent with this characteristic in the manufacture of liquid crystal display is little, even if over an organic film, the stress being added to this organic film also diminishes, therefore can realize excellent cementability.
In addition, the bonding strength A (MPa) to ITO (tin indium oxide) substrate when solidifying 25 DEG C after 1 hour under 120 DEG C of atmosphere after the ultraviolet irradiating 3000mJ/cm2, and only by 3000mJ/cm
2ultraviolet curing after 120 DEG C time when the relational expression that following formula (3) represents is met to the bonding strength D (MPa) of ITO (tin indium oxide) substrate, play effect of the present invention especially significantly.
D≧0.3×A (3)
To the bonding strength of ITO (tin indium oxide) substrate when 25 DEG C, mean the bonding strength under the atmosphere of 25 DEG C.The measuring method of bonding strength uses the bonding strength of shear direction.Such as, ITO (tin indium oxide) substrate at 5cm angle applies a small amount of liquid crystal sealing agent, use the glass-chip (1.5mm angle being cut in EAGLE XG:CORNING Inc. form) at pliers laminating 1.5mm angle.To this experiment slice irradiation ultraviolet radiation 3000mJ/cm
2after, being set as placing 1 hour in the hot-air roaster of 120 DEG C, be heating and curing.Bond's tester (SS-30WD: Xi Jin business joint-stock company) can be used to measure bonding strength to this experiment slice (glass-chip of laminating).The value of the bonding strength obtained like this is defined as A (MPa) in this application.In addition, ITO (tin indium oxide) substrate of use, cuts into 5cm angle by 470 × 370 × 0.7SP30ITO (GEOMATEC joint-stock company) and uses.
Bonding strength when 120 DEG C is the bonding strength measured under the state that the experiment slice after solidification is heated to 120 DEG C, and measuring method self is same with above-mentioned.As the method being heated to 120 DEG C, the method measuring phases of the measurement mechanism of bonding strength being heated to 120 DEG C is easy.The value of the bonding strength obtained like this is defined as B (MPa) in this application.
Only by 3000mJ/cm
2ultraviolet curing after 25 DEG C time bonding strength to ITO (tin indium oxide) substrate, being to not being heating and curing and bonding strength that the experiment slice that generates is measured in the generative process of experiment slice, is the value measured under the atmosphere of 25 DEG C.In addition, measure self also to carry out as described above.The value of the bonding strength obtained like this is defined as C (MPa) in this application.
Only by 3000mJ/cm
2ultraviolet curing after 120 DEG C time bonding strength to ITO (tin indium oxide) substrate, being to not being heating and curing and bonding strength that the experiment slice that generates is measured in the generative process of experiment slice, is the value measured under the atmosphere of 120 DEG C.In addition, measure self also to carry out as described above.The value of the bonding strength obtained like this is defined as D (MPa) in this application.
The present invention is the liquid crystal sealing agent of liquid crystal dripping process.In liquid crystal dripping process, in the manufacturing process of liquid crystal display, generally there is the operation of Ultraviolet radiation, between the organic film of the liquid crystal sealing agent solidified in this operation and alignment films etc., have accumulated large stress.Therefore, when such liquid crystal dripping process, use liquid crystal sealing agent of the present invention to be very effective.
As long as liquid crystal sealing agent of the present invention has the liquid crystal sealing agent of the liquid crystal dripping process of above-mentioned characteristic, be not particularly limited, the situation containing composition (a) (methyl) acrylated epoxy resins, composition (b) Photoepolymerizationinitiater initiater, the agent of composition (c) inorganic filler and composition (d) organic acid hydrazide compound is particularly preferred mode.Liquid crystal sealing agent containing these compositions, low to the contaminative of liquid crystal, liquid crystal dripping process has excellent characteristic.
Composition (a) (methyl) acrylated epoxy resins obtains by epoxy resin and (methyl) acrylic acid well-known reaction.Such as, by adding (methyl) acrylic acid of set equivalent proportion and catalyzer to epoxy resin (such as, benzyl dimethylamine, triethylamine, benzyltrimethylammonium chloride, triphenylphosphine hydrogen, triphenyl antimonous hydride etc.) and polymerization preventing agent (such as first quinone (methoquinone), quinhydrones, methyl hydroquinone (methylhydroquinone), phenothiazine, dibutyl hydroxy toluene etc.), and carry out such as 80 ~ 110 DEG C of esterifications and obtain.As the epoxy resin of raw material, be not particularly limited, preferably 2 officials can above epoxy resin, such as can enumerate the diglycidyl ether of resorcinol (resorcinol), bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F phenolic type epoxy resin, alicyclic epoxy resin, aliphatics chain epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoins type epoxy resin, isocyanuric acid ester type epoxy resin, there is the phenol novolak type epoxy resin of tris-phenol skeleton, in addition, the 2-glycidyl etherate of two trifunctional phenol classes, the 2-glycidyl etherate of two sense alcohols and halogenide thereof, hydride etc.Wherein, from the viewpoint of liquid crystal pollution, the more preferably diglycidyl ether of bisphenol-type epoxy resin, phenolic resin varnish type epoxy resin, resorcinol (resorcinol).
The amount of mentioned component (a) (methyl) acrylated epoxy resins considers the operability of getable liquid crystal sealing agent, physical property and suitably determining, usually, be about 25 ~ 80 quality % in liquid crystal sealing agent, be preferably 25 ~ 75 quality %.
As long as composition (b) Photoepolymerizationinitiater initiater produces free radical because of the irradiation of ultraviolet, visible ray and starts the compound of chain type polyreaction; be not particularly limited; such as; benzyl dimethyl ketal, 1-hydroxycyclohexylphenylketone, diethyl thioxanthone, benzophenone, 2-EAQ, 2-hydroxy-2-methyl propiophenone, 2-methyl-(4-(methyl mercapto) phenyl)-2-morpholino-1-propane, 2 can be enumerated; 4,6-trimethyl benzoyl diphenyl base phosphine oxide, camphorquinone, 9-Fluorenone, Diphenyl disulfide etc.Specifically, IRGACURE can be exemplified
rTM651,184,2959,127,907,396,379EG, 819,784,754,500, OXE01, OXE02, DAROCURE
rTM1173, LUCIRIN
rTMtPO (more than, BASF AG's system), SEIKUOL
rTMz, BZ, BEE, BIP, BBI (more than, Seiko chemistry joint-stock company) etc.In addition, in this manual, above with " RTM " mean registered trademark.
In addition, from the viewpoint of liquid crystal pollution, be preferably used in molecule and there is (methyl) acrylic, such as, suitably can use the resultant of reaction of 2-methylacryoyloxyethyl isocyanates and 1-[4-(2-hydroxyl-oxethyl)-phenyl]-2-hydroxy-2-methyl-1-propane-1-ketone.This compound can obtain with the method manufacture of No. 2006/027982nd, International Publication record.
The amount of mentioned component (b) Photoepolymerizationinitiater initiater that can use in liquid crystal sealing agent of the present invention, when setting the entirety of liquid crystal sealing agent as 100 quality %, normally 0.01 ~ 15 quality %, is preferably 0.02 ~ 10 quality %.
As the agent of composition (c) inorganic filler, fused silica can be exemplified, crystalline silica, silit, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulphate, calcium sulphate, mica, talcum, clay, aluminium oxide, magnesium oxide, zirconia, aluminium hydroxide, magnesium hydroxide, calcium silicate, alumina silicate, lithium aluminium silicate, zirconium silicate, barium titanate, glass fibre, carbon fiber, molybdenum disulfide, asbestos etc., be preferably fused silica, crystalline silica, silicon nitride, boron nitride, calcium carbonate, barium sulphate, calcium sulphate, mica, talcum, clay, aluminium oxide, aluminium hydroxide, calcium silicate, alumina silicate, be more preferably fused silica, crystalline silica, aluminium oxide, talcum.These inorganic filler agent can mix two or more and use.Particularly when being used as following liquid crystal display bonding agent, when its mean grain size is excessive, when the liquid crystal display of narrow gap manufactures, can not the undesirable element in smooth and easy formation gap etc. when producing the upper lower glass substrate of laminating, therefore less than 3 μm is suitable, be preferably less than 2 μm.Particle diameter can use laser diffraction and scattering formula particle size distribution measurement device (dry type) (SEISHIN enterprise of joint-stock company system; LMS-30) measure.
The amount of mentioned component (c) inorganic filler agent, when setting the entirety of liquid crystal sealing agent of the present invention as 100 quality %, is generally 1 ~ 60 quality %, is preferably 5 ~ 50 quality %.When the amount of mentioned component (c) inorganic filler agent is very few, bonding strength declines, and moisture-proof reliability is also deteriorated in addition, also has the situation that the decline of the bonding strength after moisture absorption also becomes large.On the other hand, when the amount of mentioned component (c) inorganic filler agent is too much, when being used as liquid crystal display bonding agent, existing can not the situation in gap of forming unit.
Composition (d) organic acid hydrazide compound, can make organic acid and hydrazine reaction obtain, have-NHNH
2and so on the aromatic series of functional group or aliphatic compound.As aromatic hydrazide, terephthaldehyde's acid dihydrazide (terephthalic dihydrazide), isophthalic dihydrazide, 2 can be exemplified, 6-naphthoic acid two hydrazides (2,6-naphthoic acid dihydrazide), 2,6-pyridine two hydrazides, 1,2,4-benzene three hydrazides (benzenetrihydrazide), 1,4,5,8-naphthoic acid four hydrazides (Isosorbide-5-Nitrae, 5,8-naphthoic acid tetrahydrazide), Pyromellitic Acid four hydrazides (pyromellitic acidtetrahydrazide) etc.In addition, as aliphatics hydrazide compound, formylhydrazine (formicacid hydrazide) can be exemplified, acethydrazide, propionic acid hydrazides (propanoic acid hydrazide), grass acid dihydrazide, acid dihydrazide, amber acid dihydrazide, glutaric, adipic dihydrazide, heptandioic acid two hydrazides, sebacic dihydrazide, 1, 4-cyclohexane two hydrazides, winestone acid dihydrazide, apple acid dihydrazide, iminodiacetic acid two hydrazides, N, the two semicarbazides of N '-hexa-methylene, citric acid three hydrazides, nitriloacetic acids three hydrazides, cyclohexanetricarboxylic acid three hydrazides, 1, the hydantoins skeletons such as two (Hydrazinocarbonyl the ethyl)-5-isopropyl hydantoins of 3-, preferably there is the dihydrazide compound of valine hydantoins skeleton (carbon atom of hydantoins ring is the skeleton with isopropyl displacement), the compound etc. of isocyanuric acid skeleton.As the compound with isocyanuric acid skeleton, such as can exemplify three (1-Hydrazinocarbonyl methyl) isocyanuric acid ester, three (2-Hydrazinocarbonyl ethyl) isocyanuric acid ester, three (2-Hydrazinocarbonyl ethyl) isocyanuric acid ester, three (3-Hydrazinocarbonyl propyl group) isocyanuric acid ester, two (2-Hydrazinocarbonyl ethyl) isocyanuric acid ester etc.From the balance of solidification reactivity and potentiality, be preferably isophthalic dihydrazide, acid dihydrazide, adipic dihydrazide, three (1-Hydrazinocarbonyl methyl) isocyanuric acid ester, three (2-Hydrazinocarbonyl ethyl) isocyanuric acid ester, three (2-Hydrazinocarbonyl ethyl) isocyanuric acid ester, three (3-Hydrazinocarbonyl propyl group) isocyanuric acid ester, particularly preferred acid dihydrazide, sebacic dihydrazide, three (2-Hydrazinocarbonyl ethyl) chlorinated isocyanurates.As amount when use mentioned component (d) organic acid hydrazide compound, when the total amount of composition (a) (methyl) acrylated epoxy resins is 100 Quality Mgmt Dept, situation preferably containing 1 ~ 20 Quality Mgmt Dept, be more preferably 2 ~ 10 Quality Mgmt Dept, also can mix two or more and use.
Liquid crystal sealing agent of the present invention can contain composition (e) hot radical polymerization initiator as required.
Composition (e) hot radical polymerization initiator can utilize heating to generate free radical, as long as start the compound of chain type polyreaction, be not particularly limited, organic peroxide, azo-compound, styrax compound, benzoin ether compound, aceotphenone compound, benzo pinacol etc. can be exemplified, preferably use benzo pinacol.Such as, as organic peroxide, KAYAMEK
rTMa, M, R, L, LH, SP-30C, PERDOX CH-50L, BC-FF, CADOX B-40ES, PERDOX14, TRIGONOX
rTM22-70E, 23-C70,121,121-50E, 121-LS50E, 21-LS50E, 42,42LS, KAYAESTER
rTMp-70, TMPO-70, CND-C70, OO-50E, AN, KAYABUTYL
rTMb, PERDOX 16, KAYACARBON
rTMbIC-75, AIC-75 (above, chemical drug Akzo joint-stock company), PERMEK
rTMn, H, S, F, D, G, PERHEXA
rTMh, HC, PER TMH, C, V, 22, MC, PERCURE
rTMaH, AL, HB, PERBUTYL
rTMh, C, ND, L, PERCUMYL
rTMh, D, PEROYL
rTMiB, IPP, PEROCTA
rTMnD (above, You joint-stock company) etc. can be used as commercially available product and starts with.In addition, as azo-compound, VA-044, V-070, VPE-0201, VSP-1001 etc. (more than, and light pure pharmaceutical worker's industry joint-stock company) etc. can be used as commercially available product and obtain.
As mentioned component (e) hot radical polymerization initiator, the preferably hot radical polymerization initiator (comprising the material of benzo pinacol through chemically modifying) of benzo pinacol system.Specifically, it is benzo pinacol, 1, 2-dimethoxy-1, 1, 2, 2-tetraphenyl ethane, 1, 2-diethoxy-1, 1, 2, 2-tetraphenyl ethane, 1, 2-hexichol Oxy-1, 1, 2, 2-tetraphenyl ethane, 1, 2-dimethoxy-1, 1, 2, 2-tetra-(4-aminomethyl phenyl) ethane, 1, 2-hexichol Oxy-1, 1, 2, 2-tetra-(4-methoxyphenyl) ethane, 1, two (trimethylsiloxy group)-1 of 2-, 1, 2, 2-tetraphenyl ethane, 1, two (the triethyl siloxy)-1 of 2-, 1, 2, 2-tetraphenyl ethane, 1, two (the t-Butyldimethylsilanyloxy)-1 of 2-, 1, 2, 2-tetraphenyl ethane, 1-hydroxyl-2-trimethylsiloxy group-1, 1, 2, 2-tetraphenyl ethane, 1-hydroxyl-2-triethyl siloxy-1, 1, 2, 2-tetraphenyl ethane, 1-hydroxyl-2-t-Butyldimethylsilanyloxy-1, 1, 2, 2-tetraphenyl ethane etc.Preferred 1-hydroxyl-2-trimethylsiloxy group-1,1,2,2-tetraphenyl ethane, 1-hydroxyl-2-triethyl siloxy-1,1,2,2-tetraphenyl ethane, 1-hydroxyl-2-t-Butyldimethylsilanyloxy-1,1,2,2-tetraphenyl ethane, 1,2-two (trimethylsiloxy group)-1,1,2,2-tetraphenyl ethane, is more preferably 1-hydroxyl-2-trimethylsiloxy group-1,1,2,2-tetraphenyl ethane, 1, two (trimethylsiloxy group)-1,1,2 of 2-, 2-tetraphenyl ethane, be particularly preferably two (trimethylsiloxy group)-1,1 of 1,2-, 2,2-tetraphenyl ethane.
It is commercially available that above-mentioned benzo pinacol changes into Industry Stock Company and Guang Chun medicine Industry Stock Company etc. by Tokyo.In addition, the compound of the hydroxyl of etherificate benzo pinacol, can utilize well-known method easily to synthesize.In addition, the hydroxyl of benzo pinacol is carried out to the compound of silylation etherificate, the method that corresponding benzo pinacol and various silane-based agent can be utilized to carry out heating under the base catalyst of pyridine etc. is synthesized into.As silane-based agent, the generally known trimethyl chlorosilane as TMS agent (TMCS), hexamethyldisilazane (HMDS), two (TMS) trifluoroacetamide (BSTFA) of N, O-or as the chlorotriethyl silane (TECS) of triethyl silyl agent, the t-butyl methyl silane (TBMS) etc. as t-butyldimethylsilane base agent can be exemplified.These reagent easily can obtain from the market of silicon derivative manufacturer etc.As the reacting dose of silane-based agent, it is preferably 1.0 ~ 5.0 times moles to the hydroxyl 1 mole of subject compound.Be more preferably 1.5 ~ 3.0 times moles.Than 1.0 times moles, reaction efficiency worsens at least, and the reaction time is elongated, therefore facilitates thermal decomposition.Be separated when reclaiming at most than 5.0 times moles and be deteriorated, refine and become difficulty.
Composition (e) hot radical polymerization initiator preferably makes particle diameter attenuate, and disperses equably.When its mean grain size is excessive, when the liquid crystal display of narrow gap manufactures, produces the undesirable element of gap formation when successfully can not carry out lower glass substrate on fitting etc., therefore be preferably less than 5 μm, be more preferably less than 3 μm.In addition, also have no relations even if infinitely attenuate, usual lower limit is about 0.1 μm.Particle diameter can use laser diffraction and scattering formula particle size distribution measurement device (dry type) (SEISHIN enterprise of joint-stock company system; LMS-30) measure.
The amount of composition (e) hot radical polymerization initiator, when setting liquid crystal sealing agent of the present invention entirety as 100 quality %, is preferably about 0.001 ~ 0.5 quality %.
Liquid crystal sealing agent of the present invention can contain composition (f) epoxy resin as required.
Composition (f) epoxy resin is not particularly limited, preferably low to the contaminative of liquid crystal, dissolubility.As the example of suitable epoxy resin, bisphenol A type epoxy resin can be exemplified, bisphenol f type epoxy resin, bisphenol-s epoxy resin, the diglycidyl ether of resorcinol (resorcinol), phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F phenolic type epoxy resin, alicyclic epoxy resin, aliphatics chain epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoins type epoxy resin, isocyanuric acid ester type epoxy resin, there is the phenol novolak type epoxy resin of tris-phenol skeleton, in addition, the 2-glycidyl etherate of two trifunctional phenol classes, the 2-glycidyl etherate of two sense alcohols, and halogenide, hydride etc.
The amount of composition (f) epoxy resin considers the operability of liquid crystal sealing agent, physical property and suitably determining, usually, is about 25 ~ 80 quality % in liquid crystal sealing agent, is preferably 25 ~ 75 quality %.In addition, composition (f) epoxy resin in the summation of composition (a) (methyl) acrylated epoxy resins and composition (f) epoxy resin accounts for 1 ~ 30 quality %, this is one of optimal way of the present invention, is more preferably 5 quality % ~ 15 quality %.
Liquid crystal sealing agent of the present invention can use composition (g) silane coupling agent to realize the raising of further bonding strength.As composition (g) silane coupling agent, amino silicane coupling agent, epoxy silane coupling agent, mercaptosilane coupling agents, vinyl silicane coupling agent, acrylic silane coupling agent, methacryl silanes coupling agent, ureido silane coupling agent etc. can be enumerated.Wherein, preferred amino silicane coupling agent, epoxy silane coupling agent, when also with amino silicane coupling agent and epoxy silane coupling agent, play effect of the present invention more significantly.As the concrete example of silane coupling agent, as epoxy silane coupling agent, 3-(2 can be exemplified, 3-epoxy third oxygen) propyl trimethoxy silicane (3-glycidoxypropyltrimethoxysilane), 3-(2, 3-epoxy third oxygen) hydroxypropyl methyl dimethoxysilane, 3-(2, 3-epoxy third oxygen) hydroxypropyl methyl diethoxy silane, 2-(3, 4-epoxycyclohexyl) ethyl trimethoxy silane etc., as amino silicane coupling agent, N-phenyl-gamma-amino propyl trimethoxy silicane can be exemplified, N-(2-amino-ethyl) 3-amino propyl methyl dimethoxysilane, N-(2-amino-ethyl) 3-amino propyl methyl trimethoxy silane, N-2-(amino-ethyl)-3-TSL 8330, APTES, N-(2-(vinyl-benzylamino) ethyl) 3-TSL 8330 hydrochloride etc., 3-mercaptopropyi trimethoxy silane etc. can be exemplified as mercaptosilane coupling agents, as vinyl silicane coupling agent energy exemplified by vinyl trimethoxy silane etc., as acrylic silane coupling agent, 3-acryloxypropyl trimethoxy silane etc. can be exemplified, 3-methyl allyl acyloxypropyl trimethoxysilane etc. can be exemplified as methacryl silanes coupling agent, as ureido silane coupling agent, 3-ureidopropyltriethoxysilane etc. can be exemplified.These silane coupling agent is serial etc. by sale such as chemical industry joint-stock companies of SHIN-ETSU HANTOTAI as KBM series, KBE, therefore can easily obtain from market.Wherein, preferred silane coupling agent is N-2-(amino-ethyl)-3-TSL 8330 (KBM-603, chemical industry joint-stock company of SHIN-ETSU HANTOTAI), 3-(2,3-epoxy third oxygen) propyl trimethoxy silicane (S-510, nitrogen joint-stock company), more preferably and by both situation.The amount of composition (g) silane coupling agent, when setting the entirety of liquid crystal sealing agent of the present invention as 100 quality %, be 0.05 ~ 3 quality % is suitable.
The compound that liquid crystal sealing agent of the present invention can use composition (h) to have phenolic hydroxyl group realizes the raising of further bonding strength.As the compound with phenolic hydroxyl group, can exemplify with bisphenol-A, tetrabromobisphenol A, Bisphenol F, bisphenol S, 4, 4-xenol, 2, 2, 6, 6-tetramethyl-4, 4-xenol, 2, 2-methylene-bis-(4-methyl-6-tert-butylphenol), trihydroxy benzene methylmethane, pyrogallol, there is the phenols of diisopropylidene skeleton, have 1, the phenols of the fluorene skeleton of 1-bis--4-hydroxy phenyl fluorenes etc., the polyphenyl phenolic compounds of phenolated polybutadiene etc., phenol, cresols class, ethylbenzene phenols, butyl benzene phenols, octyl phenol class, bisphenol-A, allyl benzene phenols, brominated bisphenol A, Bisphenol F, bisphenol S, the various phenol of aphthols etc. are the novolac resin of raw material, have the phenol resol resins of xylylene skeleton, have the phenol resol resins of bicyclopentadiene skeleton, have the phenol resol resins of the phenol resol resins of fluorene skeleton etc., phenol, cresols class, ethylbenzene phenols, butyl benzene phenols, octyl phenol class etc.Wherein be preferably phenol resol resins.
Liquid crystal sealing agent of the present invention also can use monomer and/or the oligomer of (methyl) acrylate as required.As such monomer, oligomer, dipentaerythritol and (methyl) acrylic acid reactant, dipentaerythritol caprolactone and (methyl) acrylic acid reactant etc. can be exemplified, as long as the material low to the contaminative of liquid crystal, there is no particular restriction.
Liquid crystal sealing agent of the present invention can also coordinate the adjuvant of the curing accelerator of organic acid, imidazoles etc., organic filler or pigment, levelling agent, defoamer, solvent etc. as required.
As the example of method obtaining liquid crystal sealing agent of the present invention, by method as follows.First, to composition (a) (methyl) acrylated epoxy resins heating for dissolving composition (b) Photoepolymerizationinitiater initiater and composition (f) epoxy resin, composition (h) have the compound of phenolic hydroxyl group as required.After cool to room temperature, the agent of adding ingredient (c) inorganic filler, composition (d) organic acid hydrazide compound, adding ingredient (e) hot radical polymerization initiator, composition (g) silane coupling agent as required, add organic filler, defoamer and levelling agent, solvent etc. again, known mixing arrangement such as three rollers, sand mill, bowl mill etc. are utilized to mix equably, and filter with metallic screen, thus liquid crystal sealing agent of the present invention can be manufactured.
In liquid crystal display of the present invention, and it is arranged opposite by set interval to form a pair substrate of set electrode at substrate, with liquid crystal sealing agent sealing of the present invention around, and gap is enclosed liquid crystal and is formed betwixt.The kind of the liquid crystal enclosed is not particularly limited.Here, substrate be made up of glass, quartz, plastics, silicon etc. at least one in there is the combination of transmitance substrate form.As its method for making, add the spacer (clearance control material) of glass fibre etc. to liquid crystal sealing agent of the present invention after, after this liquid crystal sealing agent such as coating such as side's use divider, silk-screen printing device etc. of this pair substrate, solidify at 80 ~ 120 DEG C as required temporarily.Thereafter, drip the inner side to the weir be made up of this liquid crystal sealing agent liquid crystal, in a vacuum a superimposed glass substrate again, produces gap.After gap is formed, by 90 ~ 130 DEG C of solidifications 1 ~ 2 hour, liquid crystal display of the present invention can be obtained.In addition, when when using by type as photo-thermal, utilizing ultraviolet irradiation machine to liquid crystal sealing agent portion irradiation ultraviolet radiation and make its photocuring.Ultraviolet irradiation amount is preferably 500 ~ 6000mJ/cm
2, be more preferably 1000 ~ 4000mJ/cm
2.Thereafter solidify 1 ~ 2 hour at 90 ~ 130 DEG C as required, liquid crystal display of the present invention can be obtained.The liquid crystal display of the present invention obtained like this, not because the display that liquid crystal pollution causes is bad, excellent in cementability, moisture-proof reliability.As spacer, such as, can exemplify glass fibre, silica bead, polymeric beads etc.Its diameter is different according to object, is generally 2 ~ 8 μm, is preferably 4 ~ 7 μm.Its use amount is generally 0.1 ~ 4 quality % to liquid crystal sealing agent of the present invention, is preferably 0.5 ~ 2 quality %, is more preferably about 0.9 ~ 1.5 quality %.
Liquid crystal sealing agent of the present invention because of the bonding strength after ultraviolet solidification high, in addition the difference of the bonding strength under normal temperature and the bonding strength under heating atmosphere is little, therefore excellent in adhesion to the organic film of alignment films etc., the manufacture of stable liquid crystal display and the liquid crystal display of long-term reliability excellence can be realized.In addition, the solidfied material of liquid crystal sealing agent of the present invention is also stablized thermal cycle experiment, and also excellent in thermotolerance, moisture-proof, therefore can realize liquid crystal display excellent in reliability.In addition, heat resistance confirms by measuring glass transition temperature, therefore moisture resistance properties is placed on the bonding strength after under high humidity environment to determine by measuring.And liquid crystal sealing agent of the present invention is also few to the stripping of the liquid crystal of constituent, therefore the display that can reduce liquid crystal display is bad.In addition, also excellent in storage stability, therefore be suitable for the manufacture of liquid crystal display.In addition, the voltage retention of the liquid crystal display using liquid crystal sealing agent of the present invention to generate is high, and as the liquid crystal display that ion concentration is low, the characteristic of needs is also enough.
[embodiment]
Below, utilize embodiment, comparative example illustrates in greater detail the present invention, but the present invention is not limited to embodiment.In addition, as recorded without special, " part " and " % " is quality criteria herein.
[synthesis example 1]
[synthesis of the epoxy acrylate of bisphenol A type epoxy resin]
Bisphenol A type epoxy resin 282.5g (goods name: YD-8125, Nippon Steel chemistry joint-stock company) is dissolved into toluene 266.8g, and adds dibutyl hydroxy toluene 0.2g to it and forbid agent as polymerization, be warmed up to till 60 DEG C.Thereafter, add the acrylic acid 117.5g of 100% equivalent of epoxy radicals, be warmed up to till 80 DEG C further, add the trimethyl ammonium chloride 0.2g as catalysts to it, and 98 DEG C of stir abouts 30 hours, obtain reactant liquor.By washing this reactant liquor and removing toluene, obtain the epoxy acrylate 540g of the biphenol A type as target.
[synthesis example 2]
[synthesis of the epoxy methacrylates of bisphenol A type epoxy resin]
Bisphenol A type epoxy resin 282.5g (goods name: YD-8125, Nippon Steel chemistry joint-stock company) is dissolved into toluene 266.8g, and adds dibutyl hydroxy toluene 0.2g to it and forbid agent as polymerization, be warmed up to till 60 DEG C.Thereafter, add the methacrylic acid 141.1g of 100% equivalent of epoxy radicals, be warmed up to 80 DEG C further, add as the trimethyl ammonium chloride 0.2g of catalysts to it, 98 DEG C of stir abouts 30 hours, obtain reactant liquor.Wash this reactant liquor and remove toluene, obtaining the epoxy acrylate 540g of the bisphenol A-type as target.
[synthesis example 3]
[synthesis of the epoxy acrylate of resorcinol diglycidyl ether]
Resorcinol diglycidyl ether 181.2g (nagase chemtex joint-stock company) is dissolved into toluene 266.8g, and adds dibutyl hydroxy toluene 0.8g to it and forbid agent as polymerization, be warmed up to till 60 DEG C.Thereafter, add the acrylic acid 117.5g of 100% equivalent of epoxy radicals, be warmed up to 80 DEG C further, add as the trimethyl ammonium chloride 0.6g of catalysts to it, 98 DEG C of stir abouts 30 hours, obtain reactant liquor.Wash this reactant liquor and remove toluene, obtaining the epoxy acrylate 293g of the resorcinol diglycidyl ether as target.
[embodiment 1 ~ 3, comparative example 1 ~ 2]
There is to composition (a) (methyl) acrylated epoxy resins heating for dissolving composition (b) Photoepolymerizationinitiater initiater, composition (f) epoxy resin, composition (h) in the ratio shown in following table 1 compound of phenolic hydroxyl group, and after cool to room temperature, the agent of adding ingredient (c) inorganic filler, composition (d) organic acid hydrazide compound, composition (e) hot radical polymerization initiator, composition (h) have the compound of phenolic hydroxyl group, with three roller Homogeneous phase mixing.Next the liquid crystal sealing agent modulating embodiment 1 ~ 3 is filtered with metallic screen.In addition, utilize the same material shown in operation mixture table 1, and modulate the liquid crystal sealing agent of comparative example 1 ~ 2.
[bonding strength of ITO (tin indium oxide) substrate is measured]
Add glass fibre (PF-50S: the NEG joint-stock company) 1g of 5 μm at the liquid crystal sealing agent 100g obtained as spacer and carry out mix and blend.This liquid crystal sealing agent is coated to ITO (tin indium oxide) substrate (470 × 370 × 0.7SP30ITO:geomatec joint-stock company) of 50mm × 50mm, this liquid crystal sealing agent to be fitted the glass sheet (1.5mm angle being cut in EAGLEXG:CORNING Inc. form) of 1.5mm × 1.5mm, under the condition obtaining above-mentioned A (MPa), B (MPa), C (MPa), D (MPa), measure shear bond strength.Result is as shown in table 1.
[bonding strength to organic film]
To glass substrate spin coater coated with orientation film liquid (PIA-5540-05A; Nitrogen joint-stock company), carry out the calcining of 90 seconds with 60 DEG C of heat dishes, burn till 1 hour at 220 DEG C of baking ovens.The glass substrate of this band alignment films is cut into 2 kinds of 25mm × 25mm, 25mm × 30mm, carries out cleaning in 80 seconds with UV ozone cleaning device (UVD-25U03: Japanese UV machine company limited system).After UV ozone treatment, 25mm × 25mm is with glass substrate divider or the screen process press coated with liquid crystal sealant of alignment films, and the 25mm × 30mm that fits is with the glass substrate of alignment films, utilizes UV irradiating machine to irradiate 3000mJ/cm
2ultraviolet after, drop into baking oven and heat curing 1 hour at 120 DEG C.The experiment slice of pressing people to obtain by straight line pin (pin) from sealed end the bonding strength to the position of 2mm is measured with Bond's tester (SS-30WD: Xi Jin business joint-stock company).Result is as shown in table 1.
[table 1]
1. synthesized by synthesis example 1
2. by the 2-in-1 one-tenth of synthesis example
3. synthesized by synthesis example 3
4. the method recorded by No. 2006/027982nd, International Publication is synthesized
5. SS-15 (Osaka Kasei Co., Ltd.'s system)
6. SPC (Asahi Chemical Ind)
7. IXE-100 (Toagosei Co., Ltd)
8. D-600 (Japanese talcum Co., Ltd. system)
9. SDH (Japanese fine chemistry industry Co., Ltd. system)
10. the method recorded by International Publication No. 2011/06190 instructions is synthesized
yD-8125 (new day MTR chemistry (strain) Inc.)
kBM-603 (Shin-Etsu Chemial Co., Ltd's system)
sila-Ace S-510 (CHISSO joint-stock company)
pN-152 (Nippon Kayaku K. K's system)
pARALOID EXL-2655 (Rohm and Haas Inc.)
pET-30 (Nippon Kayaku K. K's system)
According to the result of table 1, confirm that the liquid crystal sealing agent of embodiment 1 ~ 3 is very strong to the bonding strength of alignment films, i.e. organic film.Therefore, even the design of liquid crystal display that liquid crystal sealing agent of the present invention applies in alignment films, also liquid crystal display excellent in reliability can be realized.
[utilizability in industry]
Liquid crystal sealing agent of the present invention particularly on the cementability of the organic film with alignment films etc. very, be all difficult under circumstances peel off.Therefore, the liquid crystal display used under circumstances can be realized.In addition, also excellent in the general characteristic of low liquid crystal pollution, thermotolerance, heat-resisting cyclicity, moisture-proof etc., therefore the liquid crystal display of long-term reliability aspect excellence can be realized.
Claims (13)
1. a liquid crystal dripping process liquid crystal sealing agent, wherein, if irradiate 3000mJ/cm
2ultraviolet after, bonding strength when being after A (MPa), described solidification 120 DEG C to the bonding strength of ITO (tin indium oxide) substrate when solidifying 25 DEG C after 1 hour under 120 DEG C of atmosphere is B (MPa), only by 3000mJ/cm
2ultraviolet curing after 25 DEG C time when being C (MPa) to the bonding strength of ITO (tin indium oxide) substrate, described A, B and C meet the relational expression that following formula (1) and (2) represent:
B≧0.5×A (1)
C≧0.3×A (2)。
2. liquid crystal dripping process liquid crystal sealing agent according to claim 1, wherein, if only by 3000mJ/cm
2ultraviolet curing after 120 DEG C time when being D (MPa) to the bonding strength of ITO (tin indium oxide) substrate, described A and D meets the relational expression that following formula (3) represents:
D≧0.3×A (3)。
3. liquid crystal dripping process liquid crystal sealing agent according to claim 1 and 2, comprises: composition (a) (methyl) acrylated epoxy resins, composition (b) Photoepolymerizationinitiater initiater, the agent of composition (c) inorganic filler and composition (d) organic acid hydrazide compound.
4. liquid crystal dripping process liquid crystal sealing agent according to claim 3, also comprises: composition (e) hot radical polymerization initiator.
5. liquid crystal dripping process liquid crystal sealing agent according to claim 4, wherein, described composition (e) hot radical polymerization initiator is 1,2-two (trimethylsiloxy group)-1,1,2,2-tetraphenyl ethane.
6. the liquid crystal dripping process liquid crystal sealing agent according to any one of claim 3 ~ 5, also comprises: composition (f) epoxy resin.
7. the liquid crystal dripping process liquid crystal sealing agent according to any one of claim 3 ~ 6, also comprises: composition (g) silane coupling agent.
8. liquid crystal dripping process liquid crystal sealing agent according to claim 7, wherein, described composition (g) silane coupling agent is amino silicane coupling agent.
9. liquid crystal dripping process liquid crystal sealing agent according to claim 7, wherein, described composition (g) silane coupling agent is the potpourri of amino silicane coupling agent and epoxy silane coupling agent.
10. the liquid crystal dripping process liquid crystal sealing agent according to any one of claim 3 ~ 9, also comprises: composition (h) has the compound of phenolic hydroxyl group.
11. liquid crystal dripping process liquid crystal sealing agents according to claim 10, wherein, the compound that described composition (h) has phenolic hydroxyl group is phenol resol resins.
The manufacture method of 12. 1 kinds of liquid crystal displays, wherein, in the liquid crystal display be made up of two pieces of substrates, after liquid crystal is dripped in the inner side on the weir formed to the liquid crystal dripping process liquid crystal sealing agent according to any one of claim 1 to 11 be formed on a substrate, to fit another substrate, utilize thereafter liquid crystal dripping process liquid crystal sealing agent described in ultraviolet and/or heat curing.
13. 1 kinds of liquid crystal displays, wherein, the solidfied material that described liquid crystal display is obtained by the liquid crystal dripping process liquid crystal sealing agent solidified according to any one of claim 1 to 11 is bonding.
Applications Claiming Priority (3)
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| JP2012156706 | 2012-07-12 | ||
| JP2012-156706 | 2012-07-12 | ||
| PCT/JP2013/069186 WO2014010731A1 (en) | 2012-07-12 | 2013-07-12 | Liquid crystal sealing agent and liquid crystal display cell using same |
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| CN104428710A true CN104428710A (en) | 2015-03-18 |
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| JP (1) | JP6249946B2 (en) |
| KR (1) | KR20150036253A (en) |
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| CN114369210A (en) * | 2021-12-25 | 2022-04-19 | 天津市新丽华色材有限责任公司 | Acrylic acid modified epoxy resin, preparation method thereof, copper-free silver mirror back protective coating and preparation method thereof |
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|---|---|---|---|---|
| JP2002317172A (en) * | 2001-04-20 | 2002-10-31 | Nippon Kayaku Co Ltd | Sealing medium resin composition for liquid crystal display |
| JP2006039096A (en) * | 2004-07-26 | 2006-02-09 | Three Bond Co Ltd | Composition for liquid crystal display device |
| CN102428138A (en) * | 2009-05-19 | 2012-04-25 | 专业技术资源公司 | Encapsulant compositions, methods of manufacture and uses thereof |
| CN102472928A (en) * | 2009-07-01 | 2012-05-23 | 日本化药株式会社 | Liquid crystal sealing agent for liquid crystal dropping method and liquid crystal display cell using same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2846842B2 (en) * | 1995-06-22 | 1999-01-13 | 松下電器産業株式会社 | Liquid crystal sealing material and liquid crystal display device |
| JPH1171458A (en) * | 1996-08-14 | 1999-03-16 | Asahi Optical Co Ltd | Transparent resin and composite with adhesiveness, ultraviolet-curable composition for coating film formation, anti-reflection glass with scattering prevention function, cushioning material, ultraviolet-cutting sheet, ultraviolet-cutting filter for television, filter for vdt, and high-refractive-index primer composition and production of lens with primer using the primer composition |
| JP4532883B2 (en) * | 2003-06-04 | 2010-08-25 | 積水化学工業株式会社 | Photocurable resin composition, liquid crystal display element sealing agent, liquid crystal display element sealing agent, liquid crystal display element vertical conduction material, and liquid crystal display device |
| JP4391177B2 (en) * | 2003-09-17 | 2009-12-24 | 株式会社リコー | Sealant for photo-curable display element |
| JP4645804B2 (en) * | 2004-10-06 | 2011-03-09 | 株式会社スリーボンド | Curable composition for liquid crystal display device |
| WO2011063082A2 (en) * | 2009-11-20 | 2011-05-26 | 3M Innovative Properties Company | Surface-modified adhesives |
| CN103003742A (en) * | 2010-07-20 | 2013-03-27 | 日本化药株式会社 | Liquid crystal sealing agent and liquid crystal display cell using same |
-
2013
- 2013-07-11 TW TW102124978A patent/TW201420735A/en unknown
- 2013-07-12 CN CN201380036541.3A patent/CN104428710A/en active Pending
- 2013-07-12 KR KR20157002384A patent/KR20150036253A/en not_active Application Discontinuation
- 2013-07-12 JP JP2014524897A patent/JP6249946B2/en active Active
- 2013-07-12 WO PCT/JP2013/069186 patent/WO2014010731A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002317172A (en) * | 2001-04-20 | 2002-10-31 | Nippon Kayaku Co Ltd | Sealing medium resin composition for liquid crystal display |
| JP2006039096A (en) * | 2004-07-26 | 2006-02-09 | Three Bond Co Ltd | Composition for liquid crystal display device |
| CN102428138A (en) * | 2009-05-19 | 2012-04-25 | 专业技术资源公司 | Encapsulant compositions, methods of manufacture and uses thereof |
| CN102472928A (en) * | 2009-07-01 | 2012-05-23 | 日本化药株式会社 | Liquid crystal sealing agent for liquid crystal dropping method and liquid crystal display cell using same |
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| WO2014010731A1 (en) | 2014-01-16 |
| TW201420735A (en) | 2014-06-01 |
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| JP6249946B2 (en) | 2017-12-20 |
| JPWO2014010731A1 (en) | 2016-06-23 |
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Application publication date: 20150318 |