CN102516916A - Liquid crystal sealant composition - Google Patents
Liquid crystal sealant composition Download PDFInfo
- Publication number
- CN102516916A CN102516916A CN201110410932XA CN201110410932A CN102516916A CN 102516916 A CN102516916 A CN 102516916A CN 201110410932X A CN201110410932X A CN 201110410932XA CN 201110410932 A CN201110410932 A CN 201110410932A CN 102516916 A CN102516916 A CN 102516916A
- Authority
- CN
- China
- Prior art keywords
- liquid crystal
- sealing agent
- parts
- crystal sealing
- epoxy resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Sealing Material Composition (AREA)
- Epoxy Resins (AREA)
Abstract
The invention provides a liquid crystal sealant composition, which is an ultraviolet/thermal dual curable resin composition for sealing liquid crystal by a one drop fill (ODF) process, and comprises the following components in parts by weight: 40-80 parts of acrylic acid modified hyperbranched organosilicon epoxy resin, 2-15 parts of grafted hyperbranched epoxy resin coupling agent, 0.5-8 parts of photoinitiator, 5-25 parts of latent epoxy resin curing agent, and 5-40 parts of filler. The inventive composition has good coating operability and high bonding strength, solves the problem of contamination to liquid crystal existing in the conventional sealing material, and increases the bonding strength between a substrate and cured liquid crystal sealant, thus a liquid crystal display panel with high display performance and excellent quality can be manufactured, and the production efficiency is greatly improved.
Description
Technical field
The present invention relates to display panels encapsulation technology field, particularly, relate to a kind of liquid crystal sealing agent composition.
Background technology
In recent years, along with the development of miniature electric machines such as broadband propelling, digital camera and mobile telephone, aspect slim, light weight, low power consumption, the demand as the display panels of flat-panel display device is expanded rapidly.
Liquid crystal panel is mainly made through the liquid crystal injection method, and the liquid crystal display packaging process has dual mode, and a kind of is the vacuum inhalation; Promptly an etching TFT transistor, print and adopt the mode of silk screen printing to make a rectangular patterns that has the liquid crystal suction port on the IT0 quartz glass plate of alignment film, prebake under 60～100 ℃ condition then is with the solvent seasoning in the sealing agent; Splash into spacer then therein; Top glass substrate pressing contraposition is 110～220 ℃ of following hot pressing 10～90 minutes, after near the adjustment of the gap the sealing agent; 110～220 ℃ of following hot pressing 10～120 minutes is with completely solidified; Inject liquid crystal through liquid crystal injecting port then, seal liquid crystal injecting port with sealing agent again, to form liquid crystal display device.There is following defective in this kind production method: owing to hot pressing, the inhomogeneous dislocation that causes in gap, the destruction of sealing agent and substrate bonding strength; The foam that the residual solvent thermal expansion forms causes the displacement of the inhomogeneous and sealing agent in gap; Curing sealant needs for a long time; Prebake technology is very complicated; Because the volatilization of solvent makes the sealing agent usable time become very short, injecting liquid crystal needs for a long time or the like.Especially in giant display spare was made, the injection length of liquid crystal had become the bottleneck of entire making process.
For this reason; People study the manufacture craft with the image display sealing agent encapsulated liquid crystal image display of photo-thermal dual cure always, and just a step is dripped completion method (ODF processing procedure), in the ODF processing procedure; One through etching the TFT transistor, print on the ITO quartz glass plate of alignment film and through silk screen printing or the mode of putting glue ODF to be sealed frame glue and on glass substrate, form the rectangular seal pattern; Then spacer and liquid crystal are splashed in the printed rectangle frame vacuumizing and exhausting, top glass substrate contraposition pressing; The UV ultraviolet light polymerization is the position of upper and lower base plate fixedly, adopts the mode that is heating and curing to accomplish whole solidification process then.If substrate bonds, then can make liquid crystal display device with high efficient under the situation of negative pressure.
But; The polarity number of the image display sealant material of photo-thermal dual cure and the polarity number of liquid crystal material are very approaching, and the two has avidity each other, therefore with these material liquid crystal display devices the time; The component of sealing agent may be dissolved each other with liquid crystal material; Cause liquid crystal material to be polluted, cause the liquid crystal cells material orientation of sealing agent periphery chaotic, cause the display abnormality phenomenon to occur by sealant compositions.Particularly relate to uncured sealing agent in the ODF processing procedure and contact with the direct of liquid crystal, ODF envelope frame glue has become a serious problem to the pollution of liquid crystal.In addition, in above-mentioned sealing agent, comprise the sealing agent room temperature storage stability extreme difference of heat-curable component, need under freezing state, store, yet, when thawing or in case thaw, can be caused thickening serious again by the water pollution, therefore, must disposable using up.And, only with rayed solidified sealing agent, poor water resistance, cohesive strength is low, can't completely solidified by the place of light shield.In addition, also there is the problem that mixes with resistates in liquid crystal, and these resistatess comprise: solidify unreacted light trigger in back and thermal initiator, ionic impurity, silane coupling agent etc.
In the last few years, because the implementation of energy-saving consumption-reducing, industry was tended to the liquid crystal display device (low-voltage type liquid crystal) of low energizing voltage property; The low voltage liquid crystal very easily sucks impurity, As time goes on, is easy to form very high dielectric anisotropic; Be easy to cause orientation chaotic, reduce voltage retention, that is: owing to suck uncured light trigger and thermal curing agents; The ionize thing, As time goes on silane coupling agent etc. cause problems such as liquid crystal aligning confusion and voltage retention reduction.
For this reason; People are studying the countermeasure always; As the initiator that reduces the usage quantity of initiator in the system or adopt polymer to be reducing the extraction of liquid crystal to initiator, but these behaviors not only can not fully suppress the wash-out of liquid crystal to initiator, also causes reaction system to solidify insufficient or reduces the reactivity of initiator; Cause higher condition of cure, will cause negative impact liquid crystal.
In addition, as for ionic impurity, report is arranged through water or organic solvent washing sealing agent, end-blocking material and raw material thereof; Negative pressure drying is with the method for deionizing impurity then; But the required operation of this method is very complicated, and this method also can cause some problems in addition: if sealing agent and raw material drying thereof are insufficient, and then can residual solvent; Perhaps in drying process, negative pressure can cause curing of sealing agent or the like.
Be used for the curable resin composition of sealing agent and end-blocking material can rough segmentation for through with the two liquid types (two-liquid types) of main reagent and solidifying agent mixing use with contain the liquid type (one-liquid types) of solidifying agent in advance.Although two liquid type compsns can at room temperature solidify, cured resin (main reagent) and solidifying agent should separately be stored, and each group component is taken out mix in use, and therefore storage and processing are very complicated; In addition, because storage period is limited, so can not each component be pre-mixed; Need frequent the mixing, thereby cause inefficiency, opposite; One liquid type compsn is reacting between the shelf lives in some cases, so need improve storage stability; Therefore using under the situation of epoxy resin as cured resin, known as a liquid type curable resin composition of solidifying agent with Dyhard RU 100, still; The resin combination requirement is not less than 160 ℃ problem of solidification, can not satisfy the quick-setting requirement of low temperature that always requires in recent years like this, for this reason; Someone proposes with amine and epoxy resin resin affixture as solidifying agent, and the imidazoles that the someone proposes to seal with polymethylmethacrylate is as the method for solidifying agent, and using isocyanic ester is the method for amine curing agent powder surface inerting; But these methods are very complicated, also exist a large amount of unreacted amines are eluted to the problem in the unreacted liquid crystal.
Summary of the invention
In the application of macromolecular material, adopt line polymer mostly as main raw.But HV, high thixotropic that line polymer is had when high molecule mass make its field that can't be applied in ask for something LV, low thixotropy and excellent material performance, like the ultraviolet light polymerization field.In recent years, hyperbranched polymer makes this base polymer receive numerous investigators' attention and favor because of having novel structure, particular performances and potential application prospect, is regarded as the important directions of 21 century polymer science development.The development of UV-curing technology on simple linear polymer, also rapid permeability has arrived the hyperbranched polymer field thereupon.Compare with line polymer, hyperbranched polymer has inner porous three-dimensional structure, and a large amount of end group of surface enrichment, and this makes hyperbranched polymer have preferable reactive behavior.Hyperbranched polymer has unique intramolecularly nanometer micropore, can chelating ion, and the absorption small molecules; Owing to have highly branched structure, hyperbranched polymer is difficult to crystallization, also do not have chain and twine, thereby its solvability, consistency also improves greatly; Compare with the linear molecule of identical relative molecular mass, super branched molecule compact construction (lower mean square radius of gyration and hydrodynamic radius), molten state viscosity is lower, lower thixotropy; In addition, the peripheral a large amount of end groups of molecule can be through terminal groups modification to obtain required performance.Therefore, based on the above-mentioned plurality of advantages of hyperbranched polymer, the present invention is through the design distinctive molecular structure, and the hyperbranched polymer of development light-Thermocurable can obtain following corresponding advantage as the liquid-crystal display sealing material:
1) high reactive behavior can realize fast setting, enhances productivity;
2) fragment ion that is difficult to avoid after the sealing material curing is residual; Like initiator cleaved fragment or other small molecules of failing to react etc.; Owing to receive the chelating or the adsorption of the unique intramolecularly nanometer micropore of hyperbranched polymer; Be difficult to by elution in liquid crystal, reduce the possibility of polluting liquid crystal to a great extent;
3) moisture-proof heat; Adhesiveproperties is excellent to be the resin combination of the light-heat cured system space that provides more choices; Made things convenient for the performance adjustment of sealing resin composition, like the hybrid resin system of the epoxy resin of part (methyl) acrylated, its humidity resistance; Cementability has had tangible lifting with respect to traditional U V resin, does not have the brilliant disadvantage of epoxy resin contaminating fluid again;
4) lower thixotropy index is that light-heat cured system construction brings great convenience, good row's bubble property, and evenly lubricated gluing lines have increased the stopping property and the work reliability of LCD frame greatly;
5) the peripheral end group that can supply modification in a large number of molecule; To the strong bond properties of glass substrate assurance is provided for realizing on the one hand; On the other hand; For light-heat cured system of realizing sealing material provides convenience, the high molecular for the multiple various functional aids that possibly pollute liquid crystal provides advantageous conditions simultaneously.
In addition, the present invention adopts " A2+B3 " one kettle way synthesis of super branched polymkeric substance, and method is simple, need not loaded down with trivial details purifying consuming time and sepn process, greatly reduces cost.
The present invention adopts one kettle way to synthesize hyperbranched photo-thermal curing resin combination; And in branch, insert functional groups such as photo-thermal curing group, coupling agent, and be used as the material of main part of liquid crystal sealing agent composition, perfectly solved the phenomenon that the liquid crystal that adopts epoxy resin to bring as the thermofixation component dissolves each other; Simultaneously; On hyperbranched resin, connect photo-thermal curing group, coupling agent group,, also solved the disadvantage that photo-thermal initiator fragment, coupling agent small molecules etc. are sucked by liquid crystal simultaneously its macromoleization; Hyperbranched polymer has lower structural compactness than linear polymer simultaneously; Lower thixotropy index, better chelating adsorption is highly suitable for the sealing liquid crystal of ODF processing procedure.
It is the liquid crystal sealing agent composition of material of main part that the inventor has designed with acrylic acid modified hyperbranched organosilicon epoxy resin, but makes its group that contains photochemical and thermal reaction simultaneously, reactive high; Solubleness to liquid crystal is low; Well solve the liquid crystal pollution problem that the conventional seals material exists, strengthened the bonding strength of the cured article of substrate and liquid crystal sealing agent, reduced the curing energy; Energy-saving consumption-reducing has also improved production efficiency greatly
Technical scheme of the present invention is following: a kind of liquid crystal sealing agent composition, this liquid crystal sealing agent composition are the photo-thermal dual cure resin combinations that is used for ODF technology packaging liquid crystal, and the mass parts of its contained component and each component is following:
(a) acrylic acid modified hyperbranched organosilicon epoxy resin is 40～80 parts;
(b) coupling agent grafting hyperbranched epoxy resin is 2～15 parts;
(c) form 0.5～8 part of the Photoepolymerizationinitiater initiater of radical;
(d) the latent epoxy curing agent is 5～25 parts;
(e) filler is 5～40 parts.
Specify each component of liquid crystal sealing agent composition according to the invention below.
(a) acrylic acid modified hyperbranched organosilicon epoxy resin
The acrylic acid modified hyperbranched organosilicon epoxy resin that uses among the present invention is that the method through " A2+B3 " is synthetic, carries out epoxidation and acrylated modification then and gets.Wherein " A2 " is dioxane hydroxy phenyl polysilane, representes like general formula (1):
In the formula, R1, R2 all represent phenyl or methyl; P1, P2 represent to comprise straight chain, side chain or the cyclic low-grade alkylidene of the divalence of 1-10 carbon atom, or arylidene; N representes the integer of 1-20 scope.
" B3 " for containing the compound of three active function groups, and active function groups is one or more the combination in isocyano, carboxyl or the acid anhydrides, and said isocyano can be selected from the polyisocyanates tripolymer, said acid anhydrides is selected from trimellitic acid 1,2-anhydride.Wherein, the polyisocyanates tripolymer can be selected from tolylene diisocyanate (TDI) tripolymer, diphenylmethanediisocyanate (MDI) tripolymer, hexamethylene diisocyanate (HDI) tripolymer, isophorone diisocyanate (IPDI) tripolymer, hydrogenated diphenyl methane diisocyanate (HMDI) tripolymer ,-XDI (XDI) tripolymer etc.
(b) coupling agent grafting hyperbranched epoxy resin
In order to improve bond strength, the liquid crystal sealing material that acquisition has good moisture-resistant safety should contain silane coupling agent in the liquid crystal sealing agent composition according to the invention.But traditional silane coupling agent generally all is a micromolecular compound, sucks the disadvantage of polluting liquid crystal thereby exist by liquid crystal.For this reason, coupling agent grafting hyperbranched epoxy resin of the present invention be with in (a), " A2+B3 " reaction products therefrom grafted silane coupling agent obtains, thereby avoided silane coupling agent to be sucked by liquid crystal, greatly reduce the risk that silane coupling agent pollutes liquid crystal.Grafting is selected from silane coupling agent: 3-glycidoxypropyltrimewasxysilane, 3-glycidoxypropyl methyl dimethoxysilane, 3-glycidoxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxy silane, 3-chloropropylmethyldimethoxysilane, 3-r-chloropropyl trimethoxyl silane, (3-glycidoxy propyl group) Trimethoxy silane, (3-glycidoxy propyl group methyl) dimethoxy silane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, N-phenyl-gamma-amino propyl trimethoxy silicane, N-(2-amino-ethyl) 3-aminopropyl methyl dimethoxysilane, N-(2-amino-ethyl) 3-aminopropyl methyltrimethoxy silane, 3-aminopropyltriethoxywerene werene, 3-sulfydryl propyl trimethoxy silicane, N-(2-(vinyl benzyl is amino) ethyl) 3-TSL 8330 hydrochloride etc.Above-mentioned silane coupling agent can use separately, but also two or more mix use.
In order to obtain better bond strength, the preferred silane coupling agent that contains amino, epoxy group(ing) or sulfydryl that uses.
In the said liquid crystal sealing agent composition of 100 mass parts, the content of coupling agent grafting hyperbranched epoxy resin is preferably 2～15 parts.
(c) Photoepolymerizationinitiater initiater of formation radical
Form the Photoepolymerizationinitiater initiater of radical, be meant the compound that receives rayed and produce radical, that is, absorb luminous energy, decompose, produce the compound of free radical activity kind.The liquid crystal sealing agent that contains the Photoepolymerizationinitiater initiater of this formation radical is because can solidify by rayed, so when being used under the liquid crystal drop mode, can shortening the set time of liquid crystal sealing agent, thereby can realize the raising of productivity.Form the Photoepolymerizationinitiater initiater of radical, not special the qualification can be used known compound.Based compounds such as bitter almond oil camphor based compound, acetophenone compounds, benzophenone compound, thioxanthone compounds, a-acyl group oxime ester compound, bitter almond oil camphor compounds, benzoin ether compounds, benzoyl formic acid ester compound, benzene idol phthalein compounds, azo based compound, green onion quinones, diphenyl sulfide based compound, acyl group phosphorus oxide based compound, organic pigment based compound, iron-phthalein for example.These compounds can use separately, also can multiple combination use.Preferably, preferably the wavelength around the 365nm is had susceptibility, less relatively to the influence of liquid crystal property, the Photoepolymerizationinitiater initiater that perhaps forms radical pollutes the less compound of possibility of liquid crystal.
In the described liquid crystal sealing agent composition of 100 mass parts, the content that forms the Photoepolymerizationinitiater initiater of radical is preferably 0.5～8 mass parts.Facts have proved that when the content of the Photoepolymerizationinitiater initiater that forms radical is 0.5 mass parts when above, said liquid crystal sealing agent composition becomes good by the solidified nature that rayed produces; When the content of the Photoepolymerizationinitiater initiater of said formation radical is 8 mass parts when following, can make the stability of concentration of said liquid crystal sealing agent composition good, can obtain uniform cured body during photocuring.
(d) latent epoxy curing agent
Said latent epoxy curing agent of the present invention is meant in room temperature, under the visible rays condition; Even mix with hosts such as epoxy resin; Also preserve state of resin usually, not can with functional group such as epoxy group(ing) reaction, but through heat or light other functional groups are presented the solidifying agent of reactive behavior.The present invention improves the viscosity stability of said liquid crystal sealing agent composition through in said liquid crystal sealing agent composition, adding the latent epoxy curing agent, also makes said liquid crystal sealing agent composition viscosity stability at room temperature obtain good maintenance.Thereby, when being filled into said liquid crystal sealing agent composition on screen process press or the point gum machine, or when on substrate, drawing seal pattern, can use long-term and stably.In addition, prolong the work-ing life of liquid crystal sealing agent composition, also can improve productivity in the display panels manufacturing.
Not special qualification of containing in the liquid crystal sealing agent composition of the present invention of the said epoxy curing agent of hiding is the latent epoxy curing agent but preferred intramolecularly contains amino amine.Said amine is that the latent epoxy curing agent is selected from organic acid dihydrazide compound, imidazoles and verivate thereof, Dyhard RU 100, aromatic amine, epoxide modified polyamine and gathers one or more the mixture in the Urea,amino-.
In the liquid crystal sealing agent composition according to the invention, if the latent epoxy curing agent mean particle size that contains is excessive, when making the liquid crystal cells in narrow gap, can cause when last lower glass substrate is laminated to each other together can not fine formation gap problem.Therefore, described latent epoxy curing agent mean particle size is preferably greater than 0.2 micron but be less than or equal to 3 microns, is more preferably less than or equals 2 microns.Similarly, said latent epoxy curing agent maximum particle size preferably is less than or equal to 7 microns, is more preferably less than or equals 4 microns.In addition, the median size of latent epoxy curing agent mean particle size should not be less than or equal to 0.2 micron yet.
Liquid crystal sealing agent composition of the present invention can contain multiple above-mentioned latent epoxy resin curing agent.In the liquid crystal sealing agent composition of the present invention that 100 quality are divided, the content of latent epoxy resin curing agent is preferably 5～25 mass parts.Such liquid crystal sealing agent composition has excellent viscosity stability, can be used for making the display panels that provides bonding safety excellent.
(e) filler
Said filler be meant with the viscosity of controlling said liquid crystal sealing agent composition, improve its cured article intensity, to control its linear expansivity be the weighting agent that purpose is added.Not special qualification of filler that liquid crystal sealing agent composition according to the invention is contained, but the filler that the preferred electron material is used.Said filler can be mineral filler or organic filler.
Said mineral filler is selected from crystalline silica, silit, silicon nitride, SP 1, lime carbonate, magnesiumcarbonate, permanent white, calcium sulfate, mica, talcum, clay, aluminum oxide, red stone, Natural manganese dioxide, change zinc, zirconium white, white lake, Marinco H, Calucium Silicate powder, pure aluminium silicate, lithium aluminosilicate, zirconium silicate, barium titanate, granulated glass sphere, spun glass, thomel, curing aluminium, asbestos etc., fused silica preferably, crystalline silica; Silicon nitride, SP 1, lime carbonate; Permanent white, calcium sulfate, kaolin, mica; Talcum, clay, aluminum oxide; White lake, Calucium Silicate powder and pure aluminium silicate.Said organic filler is selected from one or more the mixture in polymethylmethacrylate, PS, TEB 3K and other monomeric multipolymers, vinylbenzene and other monomeric multipolymers, polyester micropartical, urethane grain and the rubber particle.
In above-mentioned filler, from the preferred mineral filler of viewpoint of low linear expansion property, maintenance shape.Be untreated in the surface or surface-treated inorganic particles filler can use.Surface-treated inorganic particles filler can be selected methoxylation, trimethyl silylization, octyl group silylanizing for use, or also can select for use with silicone oil and carry out surface-treated inorganic particles filler.Said mineral filler can be used separately, but also two or more combination is used.
In 100 parts of said liquid crystal sealing agent compositions, the content of said filler is preferably 5～45 mass parts.When inorganic filler content during less than 5 mass parts, the bond strength of said liquid crystal sealing agent composition and glass substrate descends, and because moistureproof poor reliability, the bond strength after the moisture absorption can reduce.When inorganic filler content surpassed 45 mass parts, too high because of inorganic filler content, so mineral filler was difficult to crushing, and said liquid crystal sealing agent composition can't form the gap of liquid crystal cells.Preferably, the content of said filler is 20～35 mass parts.The sealing agent that contains the filler of above-mentioned scope can obtain anti-water vapour permeability, bonding force, give effects such as thixotropy.
The present invention does not limit the shape of filler is special, can be setting or amorphous such as spherical, tabular, needle-like.The mean particle size that is used for mineral filler of the present invention is for being less than or equal to 3 microns, if mean particle size, during making liquid crystal cells, will go up lower glass substrate greater than 3 microns can not fine formation gap when range upon range of.
Embodiment
The preparation method of liquid crystal sealing agent composition of the present invention is not special to be limited, and can use technique known.In addition; The method of each composition of mixed liquid crystal encapsulant composition and instrument are not special yet to be limited; Can mix each composition through arbitrary method, use known mixing machine, for example double-arm stirrer, roll-type mixing roll, twin screw extruder, ball milling mixing roll, planetary stirring machine.Mixed mixture filters with strainer, removes impurity.Then, implement vacuum defoamation and handle, sealing is filled in vial or the plastic containers, stores as required, transports.
Embodiment one
1: synthetic (HP) of end carboxyl super branched organosilicon modified polyester
(trimellitic acid 1,2-anhydride) TMA and dioxane hydroxyl polyphenylene silane (DHPS) (n (TMA): n (DHPS)=22: 21) by theoretical calculated amount add in the four-hole boiling flask of belt stirrer, temperature regulating device and water trap; Add YLENE and catalyst for esterification reaction; Be warming up to 140 ℃ of reaction 5h, steam solvent and obtain the end carboxyl super branched organosilicon modified polyester that acid number is the 224.02mgKOH/g faint yellow solid.
2: synthetic (HPS-1) of acrylic acid modified hyperbranched organosilicon epoxy resin
Is that 1: 2 condition joins in the reaction unit with end carboxyl super branched organosilicon modified polyester of synthetic and epoxy chloropropane among the embodiment 1 by the ratio of carboxyl and the amount of substance of epoxy chloropropane; Add an amount of phase-transfer catalyst then; Be warming up to 110～120 ℃ of reaction 2h, steam excessive ECH after, add solvent and fully dissolve; Slowly drip massfraction at ambient temperature and be 40% aqueous sodium hydroxide solution, room temperature reaction 5h; With after certain zero(ppm) water washing several times, layering, drying, solvent distillation obtain hyperbranched epoxy resin (THE) again; The epoxy resin of hyperbranched modification is dissolved in the N-BUTYL ACETATE solvent; Slowly dripping molar weight is half the vinylformic acid (AA), catalyst n of oxirane value, the mixture of accelerine, stopper MEHQ (HEMQ), and 80 ℃ are reacted to acid number and are lower than 5mgKOH/g; Promptly get acrylic acid modified hyperbranched organosilicon epoxy resin, be designated as HPS-1.
3: synthetic (HPSS-1) of coupling agent grafting hyperbranched epoxy resin
Is that 1: 2 condition joins in the reaction unit with end carboxyl super branched organosilicon modified polyester of synthetic and epoxy chloropropane among the embodiment 1 by the ratio of carboxyl and the amount of substance of epoxy chloropropane; Add an amount of phase-transfer catalyst then; Be warming up to 110～120 ℃ of reaction 2h, steam excessive ECH after, add solvent and fully dissolve; Slowly drip massfraction at ambient temperature and be 40% aqueous sodium hydroxide solution, room temperature reaction 5h; Again with after certain zero(ppm) water washing several times; Layering, drying, solvent distillation; Obtain hyperbranched epoxy resin (THE), the epoxy resin of hyperbranched modification is dissolved in the N-BUTYL ACETATE solvent, slowly drip a certain amount of 3-sulfydryl propyl trimethoxy silicane; Then dripping molar weight then is half the vinylformic acid (AA), catalyst n of oxirane value; The mixture of accelerine, stopper MEHQ (HEMQ), 80 ℃ are reacted and are lower than 5mgKOH/g to acid number and promptly get coupling agent grafting hyperbranched epoxy resin, are designated as HPSS-1.
4: liquid crystal sealing agent composition synthetic
With mixing machine material shown in following is carried out pre-mixing, then use three rollers carry out mixing until solid material as 5um below.Then after the strainer filtration said composition with aperture 10um, carry out the vacuum defoamation processing and obtain liquid crystal sealing agent composition.
50 parts of HPS-1 (synthetic material in 2);
5 parts of HPSS-1 (synthetic material in 3);
5 parts of 1-hydroxyl-cyclohexyl-phenyl ketone (IRGACURE 184);
15 parts of adipic dihydrazides (ADH);
25 parts of spherical silicon dioxides.
Embodiment two
1: synthetic (HP) of end carboxyl super branched organosilicon modified polyester
(trimellitic acid 1,2-anhydride) TMA and dioxane hydroxyl polyphenylene silane (DHPS) (n (TMA): n (DHPS)=22: 21) by theoretical calculated amount add in the four-hole boiling flask of belt stirrer, temperature regulating device and water trap; Add YLENE and catalyst for esterification reaction; Be warming up to 140 ℃ of reaction 5h, steam solvent and obtain the end carboxyl super branched organosilicon modified polyester that acid number is the 224.02mgKOH/g faint yellow solid.
2: synthetic (HPS-2) of acrylic acid modified hyperbranched organosilicon epoxy resin
A certain amount of dioxane hydroxyl polyphenylene silane is joined in the four-hole boiling flask that whisking appliance, TM, prolong, logical nitrogen pipe and constant pressure funnel are housed, under normal temperature, agitation condition, from constant pressure funnel, slowly splash into the IPDI tripolymer of 1: 1 amount of substance; After dropwising, slowly heat up, temperature of reaction is controlled at below 45 ℃; Every at a distance from the content of measuring an isocyano half a hour, drop to theoretical value up to the content of isocyano, be Racemic glycidol and the Rocryl 400 that 1: 1 condition adds the Theoretical Calculation amount by the ratio of amount of substance then; Add appropriate amount of catalysts dibutyl tin laurate and stopper, be warmed up to 65～750C after dripping off gradually, detect the content of free isocyano; With the content of free isocyano less than 0.5% as reaction end; When treating that a bottle interior temperature is reduced to 50 ℃, a spot of absolute ethyl alcohol reaction 20 minutes, decompression extracts excess ethanol; Promptly get said acrylic acid modified hyperbranched organosilicon epoxy resin, be designated as HPS-2.
3: synthetic (HPSS-2) of coupling agent grafting hyperbranched epoxy resin
A certain amount of dioxane hydroxyl polyphenylene silane is joined in the four-hole boiling flask that whisking appliance, TM, prolong, logical nitrogen pipe and constant pressure funnel are housed, under normal temperature, agitation condition, from constant pressure funnel, slowly splash into the IPDI tripolymer of 1: 1 amount of substance; After dropwising, slowly heat up, temperature of reaction is controlled at below 45 ℃; Every at a distance from the content of measuring an isocyano half a hour, drop to theoretical value up to the content of isocyano, be that 1: 8 condition adds the 3-aminopropyltriethoxywerene werene by the ratio of isocyano and siloxanes coupling agent amount of substance then; Then the ratio by amount of substance is the Racemic glycidol and the Rocryl 400 of 1: 1 condition adding Theoretical Calculation amount; Add appropriate amount of catalysts dibutyl tin laurate and stopper, be warmed up to 65～750C after dripping off gradually, detect the content of free isocyano; With the content of free isocyano less than 0.5% as reaction end; When treating that a bottle interior temperature is reduced to 50 ℃, a spot of absolute ethyl alcohol reaction 20 minutes, decompression extracts excess ethanol; Promptly get said acrylic acid modified hyperbranched organosilicon epoxy resin, be designated as HPSS-2.
4: liquid crystal sealing agent composition synthetic
With mixing machine material shown in following is carried out pre-mixing, then use three rollers carry out mixing until solid material as 5um below.Then after the strainer filtration said composition with aperture 10um, carry out the vacuum defoamation processing and obtain liquid crystal sealing agent composition.
45 parts of HPS-2 (synthetic material in 2);
10 parts of HPSS-5 (synthetic material in 3);
2,4,2 parts of 6-trimethylbenzoyl-diphenyl phosphine oxides (TPO);
15 parts of 2-phenylimidazoles;
30 parts of aluminium sesquioxides.
Above content is to combine concrete preferred implementation to the further explain that the present invention did, and can not assert that practical implementation of the present invention is confined to these explanations.For the those of ordinary skill of technical field under the present invention, under the prerequisite that does not break away from the present invention's design, its framework form can be flexible and changeable, can the subseries product.Just make some simple deduction or replace, all should be regarded as belonging to the scope of patent protection that the present invention is confirmed by claims of being submitted to.
Claims (10)
1. liquid crystal sealing agent composition, it is characterized in that: this liquid crystal sealing agent composition is the photo-thermal dual cure resin combination that is used for ODF technology sealing liquid crystal, and the mass parts of its contained component and each component is following:
(a) acrylic acid modified hyperbranched organosilicon epoxy resin is 40～80 parts;
(b) coupling agent grafting hyperbranched epoxy resin is 2～15 parts;
(c) light trigger is 0.5～8 part;
(d) the latent epoxy curing agent is 5～25 parts;
(e) filler is 5～40 parts.
2. liquid crystal sealing agent composition as claimed in claim 1 is characterized in that: said (a) acrylic acid modified hyperbranched organosilicon epoxy resin is the method synthesis of super branched resin through " A2+B3 ", carries out epoxidation and acrylated then and obtains;
Wherein " A2 " is dioxane hydroxy phenyl polysilane, its as a result general formula represent like (1):
In the formula, R1, R2 all represent phenyl or methyl; P1, P2 represent to comprise straight chain, side chain or the cyclic low-grade alkylidene of the divalence of 1-10 carbon atom, or arylidene; N representes the integer of 1-20 scope.
" B3 " for containing the compound of three active function groups, active function groups is isocyano, carboxyl or acid anhydrides.
3. liquid crystal sealing agent composition as claimed in claim 2 is characterized in that: the said compound that contains isocyano is selected from the polyisocyanates tripolymer, and the said compound that contains acid anhydrides is selected from trimellitic acid 1,2-anhydride.Wherein, the polyisocyanates tripolymer can be selected from tolylene diisocyanate (TDI) tripolymer, diphenylmethanediisocyanate (MDI) tripolymer, hexamethylene diisocyanate (HDI) tripolymer, isophorone diisocyanate (IPDI) tripolymer, hydrogenated diphenyl methane diisocyanate (HMDI) tripolymer ,-one or more compsn in XDI (XDI) tripolymer.
4. liquid crystal sealing agent composition as claimed in claim 2 is characterized in that: said (b) coupling agent grafting hyperbranched epoxy resin is the method synthesis of super branched resin through " A2+B3 ", and the grafting coupling agent obtains.
5. liquid crystal sealing agent composition as claimed in claim 4 is characterized in that: described grafting coupling agent is obtained by the silane coupling agent grafting that contains amino or sulfydryl.
6. like claim 4 or 5 described liquid crystal sealing agent compositions; It is characterized in that: described grafting is selected from a kind of in (3-glycidoxy propyl group) Trimethoxy silane, (3-glycidoxy propyl group methyl) dimethoxy silane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, N-phenyl-gamma-amino propyl trimethoxy silicane, N-(2-amino-ethyl) 3-aminopropyl methyl dimethoxysilane, N-(2-amino-ethyl) 3-aminopropyl methyltrimethoxy silane, 3-aminopropyltriethoxywerene werene, 3-sulfydryl propyl trimethoxy silicane, N-(2-(vinyl benzyl is amino) ethyl) 3-TSL 8330 hydrochloride or several compsn with coupling agent.
7. liquid crystal sealing agent composition as claimed in claim 1; It is characterized in that; Described (c) light trigger is preferable over the light trigger that can form radical, comprises bitter almond oil camphor based compound, acetophenone compounds, benzophenone compound, thioxanthone compounds, α-acyl group oxime ester compound, bitter almond oil camphor compounds, benzoin ether compounds, benzoyl formic acid ester compound, benzil compounds, azo based compound, green onion quinones, diphenyl sulfide based compound, acyl group phosphorus oxide based compound, organic pigment based compound, iron-phthalocyanine based compound etc.These can use separately, perhaps also can multiple combination use.
8. liquid crystal sealing agent composition as claimed in claim 1; It is characterized in that; Described (d) latent epoxy curing agent be intramolecularly to contain amino amine be latent epoxy resin curing agent, said amine is that the latent epoxy curing agent is selected from organic acid dihydrazide compound, imidazoles and verivate thereof, Dyhard RU 100, aromatic amine, epoxide modified polyamine and gathers one or more the mixture in the Urea,amino-; Described latent epoxy curing agent mean particle size is greater than 0.2 micron but be less than or equal to 3 microns.
9. liquid crystal sealing agent composition as claimed in claim 1 is characterized in that, described (e) filler is selected from mineral filler or organic filler; Said mineral filler is selected from crystalline silica, silit, silicon nitride, SP 1, lime carbonate, magnesiumcarbonate, permanent white, calcium sulfate, mica, talcum, clay, aluminum oxide, red stone, Natural manganese dioxide, change zinc, zirconium white, white lake, Marinco H, Calucium Silicate powder, pure aluminium silicate, lithium aluminosilicate, zirconium silicate, barium titanate, granulated glass sphere, spun glass, thomel, curing aluminium, asbestos etc., fused silica preferably, crystalline silica; Silicon nitride, SP 1, lime carbonate; Permanent white, calcium sulfate, kaolin, mica; Talcum, clay, aluminum oxide; White lake, Calucium Silicate powder and pure aluminium silicate; Said organic filler is selected from one or more the mixture in polymethylmethacrylate, PS, TEB 3K and other monomeric multipolymers, vinylbenzene and other monomeric multipolymers, polyester micropartical, urethane grain and the rubber particle.
10. liquid crystal sealing agent composition as claimed in claim 1 is characterized in that, the mean particle size of said mineral filler is less than or equal to 3 microns.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110410932 CN102516916B (en) | 2011-12-12 | 2011-12-12 | Liquid crystal sealant composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110410932 CN102516916B (en) | 2011-12-12 | 2011-12-12 | Liquid crystal sealant composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102516916A true CN102516916A (en) | 2012-06-27 |
| CN102516916B CN102516916B (en) | 2013-08-14 |
Family
ID=46287994
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110410932 Active CN102516916B (en) | 2011-12-12 | 2011-12-12 | Liquid crystal sealant composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102516916B (en) |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102888199A (en) * | 2012-09-17 | 2013-01-23 | 北京京东方光电科技有限公司 | Frame sealing glue and preparation method and application thereof |
| CN103395974A (en) * | 2013-08-09 | 2013-11-20 | 句容骏成电子有限公司 | Glass frame, making method thereof, and hot pressing method utilizing glass frame |
| CN105219254A (en) * | 2015-11-04 | 2016-01-06 | 天通银厦新材料有限公司 | A kind of sol-gel toughner and preparation method thereof and utilize the technique of the toughness reinforcing sapphire substrate of this sol-gel toughner |
| CN106019726A (en) * | 2016-07-11 | 2016-10-12 | 合肥通泰光电科技有限公司 | Frame rubber for liquid crystal display and production technique thereof |
| JP2016218447A (en) * | 2015-05-25 | 2016-12-22 | 積水化学工業株式会社 | Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element |
| CN106405946A (en) * | 2016-11-29 | 2017-02-15 | 深圳市华星光电技术有限公司 | Sealant curing method and liquid crystal panel manufacturing method |
| WO2017031775A1 (en) * | 2015-08-25 | 2017-03-02 | 深圳市华星光电技术有限公司 | Branched organosilicon material and method for preparing liquid crystal display panel |
| CN106543648A (en) * | 2016-12-07 | 2017-03-29 | 江苏科技大学 | Modified epoxy resin-based super-weather-resistant composite material for bus duct |
| WO2017118226A1 (en) * | 2016-01-04 | 2017-07-13 | 京东方科技集团股份有限公司 | Frame sealant composition and application thereof |
| CN106957662A (en) * | 2015-11-25 | 2017-07-18 | 住友化学株式会社 | Liquid-crystal composition |
| CN107033823A (en) * | 2017-06-16 | 2017-08-11 | 无锡嘉联电子材料有限公司 | Nano-rubber is modified LED backlight moisture-heat-proof epoxy and preparation method thereof |
| CN107090261A (en) * | 2017-06-16 | 2017-08-25 | 无锡嘉联电子材料有限公司 | A kind of hyperbranched modified epoxy two component fast dry glue and its preparation method and application |
| CN107189361A (en) * | 2017-05-20 | 2017-09-22 | 合肥市惠科精密模具有限公司 | A kind of high-performance visible light liquid crystal sealing agent |
| CN107255893A (en) * | 2013-03-06 | 2017-10-17 | 积水化学工业株式会社 | Sealant for liquid crystal dripping process, up and down conductive material and liquid crystal display cells |
| CN107556964A (en) * | 2017-09-22 | 2018-01-09 | 深圳市联灏新材料技术开发有限公司 | A kind of quanta point material sealant composition of radiation-hardenable |
| CN108102453A (en) * | 2017-12-28 | 2018-06-01 | 邓艳 | A kind of epoxy resin filler |
| CN111205815A (en) * | 2020-03-12 | 2020-05-29 | 东莞市联灏新材料技术开发有限公司 | A UV hybrid curable OLED encapsulant composition |
| CN111338137A (en) * | 2020-04-14 | 2020-06-26 | Tcl华星光电技术有限公司 | Display panel and manufacturing method thereof |
| CN111771160A (en) * | 2018-07-10 | 2020-10-13 | 积水化学工业株式会社 | Sealing agent for liquid crystal element, vertical conduction material, and liquid crystal element |
| CN112760074A (en) * | 2021-02-26 | 2021-05-07 | 烟台信友新材料有限公司 | High-toughness and heat and humidity resistant double-component epoxy transparent conductive adhesive and preparation method thereof |
| CN113248636A (en) * | 2021-06-21 | 2021-08-13 | 贵州师范学院 | Thioxanthone visible light initiator, preparation method and application |
| TWI774777B (en) * | 2017-06-06 | 2022-08-21 | 日商日本化藥股份有限公司 | Adhesives 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 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6460797B2 (en) * | 2013-11-13 | 2019-01-30 | 積水化学工業株式会社 | Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10123542A (en) * | 1996-10-15 | 1998-05-15 | Matsushita Electric Ind Co Ltd | Liquid crystal display element and its production |
| CN1703458A (en) * | 2002-11-01 | 2005-11-30 | 三井化学株式会社 | Sealant composition for liquid crystal and process for producing liquid-crystal display panel with the same |
| CN101475682A (en) * | 2009-01-15 | 2009-07-08 | 苏州海博特树脂科技有限公司 | Preparation method of silicon-containing hyperbranched epoxy resin |
| CN101974143A (en) * | 2010-10-14 | 2011-02-16 | 华南理工大学 | Organic silicon modified epoxy acrylate aqueous dispersion and preparation method thereof |
| CN102220106A (en) * | 2011-05-20 | 2011-10-19 | 广州宏昌胶粘带厂 | UV-curable organosilicon pressure-sensitive adhesive composition |
-
2011
- 2011-12-12 CN CN 201110410932 patent/CN102516916B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10123542A (en) * | 1996-10-15 | 1998-05-15 | Matsushita Electric Ind Co Ltd | Liquid crystal display element and its production |
| CN1703458A (en) * | 2002-11-01 | 2005-11-30 | 三井化学株式会社 | Sealant composition for liquid crystal and process for producing liquid-crystal display panel with the same |
| CN101475682A (en) * | 2009-01-15 | 2009-07-08 | 苏州海博特树脂科技有限公司 | Preparation method of silicon-containing hyperbranched epoxy resin |
| CN101974143A (en) * | 2010-10-14 | 2011-02-16 | 华南理工大学 | Organic silicon modified epoxy acrylate aqueous dispersion and preparation method thereof |
| CN102220106A (en) * | 2011-05-20 | 2011-10-19 | 广州宏昌胶粘带厂 | UV-curable organosilicon pressure-sensitive adhesive composition |
Cited By (37)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102888199B (en) * | 2012-09-17 | 2014-06-18 | 北京京东方光电科技有限公司 | Frame sealing glue and preparation method and application thereof |
| US9023911B2 (en) | 2012-09-17 | 2015-05-05 | Beijing Boe Optoelectronics Technology Co., Ltd. | Frame sealant, process for preparing same and use thereof |
| CN102888199A (en) * | 2012-09-17 | 2013-01-23 | 北京京东方光电科技有限公司 | Frame sealing glue and preparation method and application thereof |
| CN107255893A (en) * | 2013-03-06 | 2017-10-17 | 积水化学工业株式会社 | Sealant for liquid crystal dripping process, up and down conductive material and liquid crystal display cells |
| CN103395974A (en) * | 2013-08-09 | 2013-11-20 | 句容骏成电子有限公司 | Glass frame, making method thereof, and hot pressing method utilizing glass frame |
| CN103395974B (en) * | 2013-08-09 | 2015-11-04 | 句容骏成电子有限公司 | A kind of glass frame and preparation method thereof and utilize the hot-press method of glass frame |
| JP2016218447A (en) * | 2015-05-25 | 2016-12-22 | 積水化学工業株式会社 | Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element |
| GB2556587A (en) * | 2015-08-25 | 2018-05-30 | Shenzhen China Star Optoelect | Branched organosilicon material and method for preparing liquid crystal display panel |
| RU2683825C1 (en) * | 2015-08-25 | 2019-04-02 | Шэньчжэнь Чайна Стар Оптоэлектроникс Текнолоджи Ко., Лтд. | Branched organosilicon polymer and a method of making liquid crystal display panels for information display |
| WO2017031775A1 (en) * | 2015-08-25 | 2017-03-02 | 深圳市华星光电技术有限公司 | Branched organosilicon material and method for preparing liquid crystal display panel |
| GB2556587B (en) * | 2015-08-25 | 2020-09-02 | Shenzhen China Star Optoelect | A branched organosilicon material, and method for manufacturing liquid crystal display panels |
| US10377950B2 (en) | 2015-08-25 | 2019-08-13 | Shenzhen China Star Optoelectronics Technology Co., Ltd. | Branched organosilicon material, and method for manufacturing liquid crystal display panels |
| CN105219254A (en) * | 2015-11-04 | 2016-01-06 | 天通银厦新材料有限公司 | A kind of sol-gel toughner and preparation method thereof and utilize the technique of the toughness reinforcing sapphire substrate of this sol-gel toughner |
| CN106957662A (en) * | 2015-11-25 | 2017-07-18 | 住友化学株式会社 | Liquid-crystal composition |
| WO2017118226A1 (en) * | 2016-01-04 | 2017-07-13 | 京东方科技集团股份有限公司 | Frame sealant composition and application thereof |
| US10465100B2 (en) | 2016-01-04 | 2019-11-05 | Boe Technology Group Co., Ltd. | Sealant composition and application thereof |
| CN106019726A (en) * | 2016-07-11 | 2016-10-12 | 合肥通泰光电科技有限公司 | Frame rubber for liquid crystal display and production technique thereof |
| CN106405946A (en) * | 2016-11-29 | 2017-02-15 | 深圳市华星光电技术有限公司 | Sealant curing method and liquid crystal panel manufacturing method |
| CN106543648A (en) * | 2016-12-07 | 2017-03-29 | 江苏科技大学 | Modified epoxy resin-based super-weather-resistant composite material for bus duct |
| CN106543648B (en) * | 2016-12-07 | 2019-06-18 | 江苏科技大学 | A kind of modified epoxy resin-based super weather-resistant composite material for bus duct |
| CN107189361A (en) * | 2017-05-20 | 2017-09-22 | 合肥市惠科精密模具有限公司 | A kind of high-performance visible light liquid crystal sealing agent |
| TWI774777B (en) * | 2017-06-06 | 2022-08-21 | 日商日本化藥股份有限公司 | Adhesives for Electronic Parts |
| CN107090261A (en) * | 2017-06-16 | 2017-08-25 | 无锡嘉联电子材料有限公司 | A kind of hyperbranched modified epoxy two component fast dry glue and its preparation method and application |
| CN107033823A (en) * | 2017-06-16 | 2017-08-11 | 无锡嘉联电子材料有限公司 | Nano-rubber is modified LED backlight moisture-heat-proof epoxy and preparation method thereof |
| CN107556964A (en) * | 2017-09-22 | 2018-01-09 | 深圳市联灏新材料技术开发有限公司 | A kind of quanta point material sealant composition of radiation-hardenable |
| CN107556964B (en) * | 2017-09-22 | 2021-01-26 | 东莞市联灏新材料技术开发有限公司 | Radiation-curable quantum dot material sealant composition |
| CN108102453A (en) * | 2017-12-28 | 2018-06-01 | 邓艳 | A kind of epoxy resin filler |
| CN111771160A (en) * | 2018-07-10 | 2020-10-13 | 积水化学工业株式会社 | Sealing agent for liquid crystal element, vertical conduction material, and liquid crystal element |
| CN111205815B (en) * | 2020-03-12 | 2022-02-01 | 东莞市联灏新材料技术开发有限公司 | OLED sealant composition capable of being cured in UV hybrid mode |
| CN111205815A (en) * | 2020-03-12 | 2020-05-29 | 东莞市联灏新材料技术开发有限公司 | A UV hybrid curable OLED encapsulant composition |
| CN111338137A (en) * | 2020-04-14 | 2020-06-26 | Tcl华星光电技术有限公司 | Display panel and manufacturing method thereof |
| CN111338137B (en) * | 2020-04-14 | 2022-02-22 | Tcl华星光电技术有限公司 | Display panel and manufacturing method thereof |
| US12085816B2 (en) | 2020-04-14 | 2024-09-10 | Tcl China Star Optoelectronics Technology Co., Ltd. | Display panel and method for manufacturing same |
| 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 |
| CN112760074A (en) * | 2021-02-26 | 2021-05-07 | 烟台信友新材料有限公司 | High-toughness and heat and humidity resistant double-component epoxy transparent conductive adhesive and preparation method thereof |
| CN113248636A (en) * | 2021-06-21 | 2021-08-13 | 贵州师范学院 | Thioxanthone visible light initiator, preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102516916B (en) | 2013-08-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102516916B (en) | Liquid crystal sealant composition | |
| JP5547642B2 (en) | Liquid crystal sealant, liquid crystal display panel using the same, manufacturing method thereof, and liquid crystal display device | |
| TW201100489A (en) | Curing resin composition, sealing material for liquid crystal display device and liquid crystal display device | |
| CN101836157B (en) | Sealing material for liquid crystal dispensing method, transfer material and liquid crystal displays | |
| CN107828359A (en) | Frame glue composition and display device | |
| CN101369098B (en) | Curing resin composition, sealing material for liquid crystal display device and liquid crystal display device | |
| CN103242799A (en) | Low-viscosity, rapidly-curing and high-flexibility double-component condensed type pouring silica gel and preparation method for same | |
| JP5571436B2 (en) | Liquid crystal sealant, liquid crystal display panel manufacturing method using the same, and liquid crystal display panel | |
| CN102197334B (en) | Sealant for liquid crystal dropping process, vertically conducting material, and liquid crystal display element | |
| CN103443698B (en) | Sealant for liquid crystal dripping process, upper and lower conductive material and liquid crystal display cells | |
| CN106462014A (en) | Sealing agent for liquid crystal dropping methods, vertically conducting material and liquid crystal display element | |
| JP4575297B2 (en) | Liquid crystal sealant, liquid crystal display device using the same, and method for manufacturing the device | |
| CN103468160A (en) | Modified carbon nano tube function master batch and frame sealing gel as well as preparation methods thereof, liquid crystal display panel and liquid crystal display | |
| JP2008019303A (en) | Liquid crystal sealing agent and liquid crystal display cell using the same | |
| JPH1115005A (en) | Liquid crystal display device and method of manufacturing the same | |
| CN103229094B (en) | Sealant for liquid crystal dropping technique, method for producing sealant for liquid crystal dropping technique, vertical conducting material, and liquid crystal display element | |
| CN105900003A (en) | Sealant for one-drop filling process, vertically conductive material, and liquid crystal display element | |
| CN102827352A (en) | Heat curing agent and preparation method thereof, frame sealing adhesive, display panel and display device | |
| CN106398557A (en) | Frame adhesive | |
| JP4668538B2 (en) | Curable resin composition, sealing agent for liquid crystal dropping method, vertical conduction material, and liquid crystal display element | |
| CN110408350A (en) | A kind of UV glue and preparation method thereof for encapsulation | |
| JP2008096710A (en) | Liquid crystal sealing agent, method for manufacturing liquid crystal display panel using the same and liquid crystal display panel | |
| CN100398621C (en) | Curing resin composition and sealants and end-sealing materials for displays | |
| KR20120096492A (en) | Cationic curing liquid crystal sealant and liquid crystal display element | |
| JP3857281B2 (en) | Curable resin composition for liquid crystal display element |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |