CN102516916B - Liquid crystal sealant composition - Google Patents
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- CN102516916B CN102516916B CN 201110410932 CN201110410932A CN102516916B CN 102516916 B CN102516916 B CN 102516916B CN 201110410932 CN201110410932 CN 201110410932 CN 201110410932 A CN201110410932 A CN 201110410932A CN 102516916 B CN102516916 B CN 102516916B
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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 by the liquid crystal injection method, the liquid crystal display packaging process has dual mode, a kind of is the vacuum inhalation, namely 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, with the solvent seasoning in the sealing agent, splash into spacer then therein, top glass substrate pressing contraposition, 110～220 ℃ of following hot pressing 10～90 minutes, after near the gap the sealing agent is adjusted, 110～220 ℃ of following hot pressing 10～120 minutes is to solidify fully, inject liquid crystal by 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 etc.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 display screen sealing agent encapsulated liquid crystal display screen of photo-thermal dual cure always, just a step is dripped completion method (ODF processing procedure), in the ODF processing procedure, one by etching the TFT transistor, print and by the mode of silk screen printing or some glue ODF is sealed frame glue on the ITO quartz glass plate of alignment film and form the rectangular seal pattern at glass substrate, 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 finish 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 display screen sealant material of photo-thermal dual cure and the polarity number of liquid crystal material are very approaching, the two has avidity mutually, therefore when making liquid crystal display device with these materials, the component of sealing agent may be dissolved each other with liquid crystal material, cause sealed dose of component of 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.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 and be polluted by water and can cause thickening serious, therefore, must disposable using up.And, a sealing agent with rayed curing, poor water resistance, cohesive strength is low, can't be solidified fully 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 the unreacted light trigger in back and thermal initiator, ionic impurity, silane coupling agent etc.
In the last few years, because the liquid crystal display device (low-voltage type liquid crystal) of low energizing voltage is tended in the implementation of energy-saving consumption-reducing, industry, the low voltage liquid crystal very easily sucks impurity, As time goes on, be 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 ionization 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 is to reduce liquid crystal to the extraction of initiator, but these behaviors not only can not fully suppress liquid crystal to the wash-out of initiator, also cause reaction system to solidify reactivity insufficient or the reduction initiator, cause higher condition of cure, will cause negative impact to liquid crystal.
In addition, as for ionic impurity, report is arranged by 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 etc.
Be used for the curable resin composition of sealing agent and end-blocking material can rough segmentation for by main reagent and solidifying agent being mixed the two liquid types (two-liquid types) of use and containing the liquid type (one-liquid types) of solidifying agent in advance.Although two liquid type compositions can at room temperature solidify, but cured resin (main reagent) and solidifying agent should separately be stored, in use each group component is taken out and mix, therefore storage and processing are very complicated, in addition, because storage period is limited, so each component can not be pre-mixed, need frequent the mixing, thereby cause inefficiency, on the contrary, one liquid type composition, between the shelf lives, reacting in some cases, so need improve storage stability, therefore using under the situation of Resins, epoxy as cured resin, be known with the liquid type curable resin composition of Dyhard RU 100 as solidifying agent, but, 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 to use amine and Resins, epoxy resin affixture as solidifying agent, someone proposes the imidazoles sealed with polymethylmethacrylate as the method for solidifying agent, and using isocyanic ester is the method for amine curing agent powder surface inerting, still, these methods are very complicated, also exist a large amount of unreacted amines are eluted to problem in the unreacted liquid crystal.
Summary of the invention
In the application of macromolecular material, adopt line polymer as main raw mostly.But the high viscosity that line polymer has when high molecule mass, high thixotropic make its field that can't be applied in ask for something low viscosity, low thixotropy and excellent material performance, as the ultraviolet light polymerization field.In recent years, hyperbranched polymer makes this base polymer be subjected to numerous investigators' attention and favor because 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 the three-dimensional structure of inner porous, 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, a large amount of end groups of molecule periphery can be by terminal groups modification to obtain required performance.Therefore, based on the above-mentioned plurality of advantages of hyperbranched polymer, the present invention is by 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, as initiator cleaved fragment or other small molecules of failing to react etc., owing to be subjected to chelating or the adsorption of the intramolecularly nanometer micropore of hyperbranched polymer uniqueness, 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, the hybrid resin system of Resins, epoxy as part (methyl) acrylated, its humidity resistance, cementability has had tangible lifting with respect to traditional UV resin, does not have the disadvantage of Resins, epoxy contaminating fluid crystalline substance again;
4) lower thixotropy index is that light-heat cured system construction brings great convenience, good row's bubble property, and evenly the gluing lines that lubricate have increased stopping property and the work reliability of LCD frame greatly;
5) the molecule periphery in a large number can be for the end group of modification, provide assurance for realizing to the strong bond properties of glass substrate 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 may 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 at branch's access photo-thermal curing group, functional groups such as coupling agent, be used as the material of main part of liquid crystal sealing agent composition, perfectly solved the phenomenon that the liquid crystal that adopts Resins, epoxy to bring as the thermofixation component dissolves each other, simultaneously, connect the photo-thermal curing group at hyperbranched resin, the coupling agent group, with its macromoleization, also solved simultaneously photo-thermal initiator fragment, the disadvantage that coupling agent small molecules etc. are sucked by liquid crystal, 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.
The liquid crystal sealing agent composition that it is material of main part that the inventor has designed with acrylic acid modified hyperbranched organosilicon epoxy resin, but make it contain the group of 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 as follows: a kind of liquid crystal sealing agent composition, this liquid crystal sealing agent composition are the photo-thermal dual cure resin combinations for ODF technology packaging liquid crystal, and the mass parts of its contained component and each component is as follows:
(a) acrylic acid modified hyperbranched organosilicon epoxy resin is 40～80 parts;
(b) coupling agent grafting hyperbranched epoxy resin is 2～15 parts;
(c) Photoepolymerizationinitiater initiater of formation free radical is 0.5～8 part;
(d) the latent epoxy curing agent is 5～25 parts;
(e) filler is 5～40 parts.
Describe each component of liquid crystal sealing agent composition of the present invention below in detail.
(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 by " A2+B3 " is synthetic, carries out epoxidation and acrylated modification then and gets.Wherein " A2 " is dioxane hydroxy phenyl polysilane, represents as general formula (1):
In the formula, R1, R2 all represent phenyl or methyl; P1, P2 represent to comprise the low-grade alkylidene of straight chain, side chain or ring-type of the divalence of 1-10 carbon atom, or arylidene; N represents 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 described isocyano can be selected from the polyisocyanates tripolymer, described 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 ,-Xylene Diisocyanate (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 reliability should contain silane coupling agent in the liquid crystal sealing agent composition of the present invention.But traditional silane coupling agent generally all is 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 reduced the risk that silane coupling agent pollutes liquid crystal.Grafting is selected from silane coupling agent: the 3-glycidoxypropyltrimewasxysilane, 3-glycidoxypropyl methyl dimethoxysilane, 3-glycidoxypropyl methyl dimethoxysilane, the 3-methacryloxypropyl trimethoxy silane, the 3-chloropropylmethyldimethoxysilane, the 3-r-chloropropyl trimethoxyl silane, (3-glycidoxy propyl group) Trimethoxy silane, (3-glycidoxy propyl group methyl) dimethoxy silane, 2-(3,4-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, the 3-aminopropyltriethoxywerene werene, 3-sulfydryl propyl trimethoxy silicane, N-(2-(vinyl benzyl 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 described 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 free radical
Form the Photoepolymerizationinitiater initiater of free radical, refer to be subjected to rayed and the compound that produces free 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 free 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 free radical, be not particularly limited, can use 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 multiplely be used in combination.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 free 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 free radical is preferably 0.5～8 mass parts.Facts have proved that when the content of the Photoepolymerizationinitiater initiater that forms free radical is 0.5 mass parts when above, described liquid crystal sealing agent composition becomes good by the solidified nature that rayed produces; When the content of the Photoepolymerizationinitiater initiater of described formation free radical is 8 mass parts when following, can make the stability of concentration of described liquid crystal sealing agent composition good, can obtain uniform cured body during photocuring.
(d) latent epoxy curing agent
Described latent epoxy curing agent of the present invention refers in room temperature, under the visible rays condition, even mix with hosts such as Resins, epoxy, also preserve state of resin usually, not can with functional group such as epoxy group(ing) reaction, but other functional groups are presented the solidifying agent of reactive behavior by heat or light.The present invention improves the viscosity stability of described liquid crystal sealing agent composition by add the latent epoxy curing agent in described liquid crystal sealing agent composition, also makes described liquid crystal sealing agent composition viscosity stability at room temperature obtain good maintenance.Thereby, when being filled into described liquid crystal sealing agent composition on screen process press or the point gum machine, or when substrate is drawn 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.
The described epoxy curing agent of hiding that contains in the liquid crystal sealing agent composition of the present invention is not particularly limited, and is the latent epoxy curing agent but preferred intramolecularly contains amino amine.Described amine is that the latent epoxy curing agent is selected from one or more the mixture in organic acid dihydrazide compound, imidazoles and derivative thereof, Dyhard RU 100, aromatic amine, epoxide modified polyamine and the poly-Urea,amino-.
In the liquid crystal sealing agent composition of the present 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, described 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 bonding reliability excellence is provided.
(e) filler
Described filler refer to control described liquid crystal sealing agent composition viscosity, improve its cured article intensity, to control its linear expansivity be the weighting agent that purpose is added.The contained filler of liquid crystal sealing agent composition of the present invention is not particularly limited, but the filler that the preferred electron material is used.Described filler can be mineral filler or organic filler.
Described mineral filler is selected from crystalline silica, silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesiumcarbonate, barium sulfate, calcium sulfate, mica, talcum, clay, aluminum oxide, ferric oxide, magnesium oxide, change zinc, zirconium white, aluminium hydroxide, magnesium hydroxide, Calucium Silicate powder, pure aluminium silicate, lithium aluminosilicate, zirconium silicate, barium titanate, granulated glass sphere, glass fibre, carbon fiber, curing aluminium, asbestos etc., fused silica preferably, crystalline silica, silicon nitride, boron nitride, calcium carbonate, barium sulfate, calcium sulfate, kaolin, mica, talcum, clay, aluminum oxide, aluminium hydroxide, Calucium Silicate powder and pure aluminium silicate.Described organic filler is selected from one or more the mixture in multipolymer, polyester micropartical, urethane grain and the rubber particle of multipolymer, vinylbenzene and other monomers of polymethylmethacrylate, polystyrene, methyl methacrylate and other monomers.
In above-mentioned filler, from the preferred mineral filler of viewpoint of low linear expansion, 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.Described mineral filler can be used separately, but also two or more is used in combination.
In 100 parts of described liquid crystal sealing agent compositions, the content of described filler is preferably 5～45 mass parts.When inorganic filler content during less than 5 mass parts, the bond strength of described 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 described liquid crystal sealing agent composition can't form the gap of liquid crystal cells.Preferably, the content of described 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 is not particularly limited the shape of filler, 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 the manufacturing liquid crystal cells, will go up lower glass substrate greater than 3 microns can not fine formation gap when stacked.
Embodiment
The preparation method of liquid crystal sealing agent composition of the present invention is not particularly limited, and can use technique known.In addition, method and the instrument of each composition of mixed liquid crystal encapsulant composition also are not particularly limited, can mix each composition by 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 dimethylbenzene 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
Be that 1: 2 condition joins in the reaction unit with end carboxyl super branched organosilicon modified polyester synthetic among the embodiment 1 and epoxy chloropropane 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, after steaming excessive ECH, adding solvent fully dissolves, slowly drip massfraction at ambient temperature and be 40% aqueous sodium hydroxide solution, room temperature reaction 5h; Again with after certain distilled water washing several times, layering, drying, solvent distillation, obtain hyperbranched epoxy resin (THE), the Resins, epoxy of hyperbranched modification is dissolved in the N-BUTYL ACETATE solvent, slowly drip molar weight and be half vinylformic acid (AA), catalyst n of oxirane value, the mixture of accelerine, stopper MEHQ (HEMQ), 80 ℃ are reacted to acid number and are lower than 5mgKOH/g, namely get acrylic acid modified hyperbranched organosilicon epoxy resin, be designated as HPS-1.
3: synthetic (HPSS-1) of coupling agent grafting hyperbranched epoxy resin
Be that 1: 2 condition joins in the reaction unit with end carboxyl super branched organosilicon modified polyester synthetic among the embodiment 1 and epoxy chloropropane 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, after steaming excessive ECH, adding solvent fully dissolves, slowly drip massfraction at ambient temperature and be 40% aqueous sodium hydroxide solution, room temperature reaction 5h; Again with after certain distilled water washing several times, layering, drying, solvent distillation, obtain hyperbranched epoxy resin (THE), the Resins, epoxy of hyperbranched modification is dissolved in the N-BUTYL ACETATE solvent, slowly drip a certain amount of 3-sulfydryl propyl trimethoxy silicane, then drip molar weight then and be half 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 namely get coupling agent grafting hyperbranched epoxy resin, are designated as HPSS-1.
4: liquid crystal sealing agent composition synthetic
With mixing machine material shown below is carried out pre-mixing, then carrying out mixing with three rollers is below the 5um until solid material.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 (material that synthesizes in 2);
5 parts of HPSS-1 (material that synthesizes 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 dimethylbenzene 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 joined agitator is being housed, thermometer, prolong, in the four-hole boiling flask of logical nitrogen pipe and constant pressure funnel, at normal temperature, under the 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 control is below 45 ℃, measure the content of an isocyano every half an hour, content up to isocyano drops to theoretical value, ratio by amount of substance is Racemic glycidol and the hydroxyethyl methylacrylate of 1: 1 condition adding Theoretical Calculation amount 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 down to 50 ℃, a spot of dehydrated alcohol reaction 20 minutes, decompression extracts excess ethanol, namely gets described acrylic acid modified hyperbranched organosilicon epoxy resin, is designated as HPS-2.
3: synthetic (HPSS-2) of coupling agent grafting hyperbranched epoxy resin
A certain amount of dioxane hydroxyl polyphenylene silane joined agitator is being housed, thermometer, prolong, in the four-hole boiling flask of logical nitrogen pipe and constant pressure funnel, at normal temperature, under the 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 control is below 45 ℃, measure the content of an isocyano every half an hour, content up to isocyano drops to theoretical value, 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 Racemic glycidol and the hydroxyethyl methylacrylate 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 down to 50 ℃, a spot of dehydrated alcohol reaction 20 minutes, decompression extracts excess ethanol, namely get described acrylic acid modified hyperbranched organosilicon epoxy resin, be designated as HPSS-2.
4: liquid crystal sealing agent composition synthetic
With mixing machine material shown below is carried out pre-mixing, then carrying out mixing with three rollers is below the 5um until solid material.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 (material that synthesizes in 2);
10 parts of HPSS-5 (material that synthesizes in 3);
2 parts of 2,4,6-trimethylbenzoyl-diphenyl phosphine oxides (TPO);
15 parts of 2-phenylimidazoles;
30 parts of aluminium sesquioxides.
Above content be in conjunction with concrete preferred implementation to further describing that the present invention does, can not assert that concrete enforcement of the present invention is confined to these explanations.For the general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, its framework form can be flexible and changeable, can the subseries product.Just make some simple deduction or replace, all should be considered as belonging to the scope of patent protection that the present invention is determined by claims of submitting to.
Claims (9)
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 for ODF technology sealing liquid crystal, and the mass parts of its contained component and each component is as follows:
Described (a) acrylic acid modified hyperbranched organosilicon epoxy resin is the method synthesis of super branched resin by " A2+B3 ", carries out epoxidation and acrylated then and obtains;
Wherein " A2 " is dioxane hydroxy phenyl polysilane, and its general structure is represented as (1):
In the formula, R
1And R
2Represent phenyl respectively; P
1, P
2Expression comprises the low-grade alkylidene of straight chain, side chain or ring-type of the divalence of 1-10 carbon atom; N represents 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.
2. liquid crystal sealing agent composition as claimed in claim 1, it is characterized in that: the described compound that contains isocyano is selected from polyisocyanate trimer, the described compound that contains acid anhydrides is selected from trimellitic acid 1,2-anhydride, wherein, polyisocyanate trimer is selected from tolylene diisocyanate (TDI) tripolymer, diphenylmethanediisocyanate (MDI) tripolymer, hexamethylene diisocyanate (HDI) tripolymer, isophorone diisocyanate (IPDI) tripolymer, hydrogenated diphenyl methane diisocyanate (HMDI) tripolymer, between-one or more composition in Xylene Diisocyanate (XDI) tripolymer.
3. liquid crystal sealing agent composition as claimed in claim 1, it is characterized in that: described (b) coupling agent grafting hyperbranched epoxy resin is the method synthesis of super branched resin by " A2+B3 ", the grafting coupling agent obtains.
4. liquid crystal sealing agent composition as claimed in claim 3 is characterized in that: described grafting coupling agent is obtained by the silane coupling agent grafting that contains amino or sulfydryl.
5. as claim 3 or 4 described liquid crystal sealing agent compositions, it is characterized in that: described grafting is selected from a kind of in 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 amino) ethyl) the 3-TSL 8330 hydrochloride or several composition with coupling agent.
6. liquid crystal sealing agent composition as claimed in claim 1; it is characterized in that; described (c) light trigger is selected the light trigger that can form free radical for use, is selected from the bitter almond oil camphor based compound; acetophenone compounds; benzophenone compound; the thioxanthone compounds; α-acyl group oxime ester compound; the benzoin ether compounds; the benzoyl formic acid ester compound; the benzil compounds; the azo based compound; the green onion quinones; the diphenyl sulfide based compound; acyl group phosphorus oxide based compound; the organic pigment based compound; the combination of one or more in iron-phthalocyanine based compound.
7. 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, described amine is that the latent epoxy curing agent is selected from one or more the mixture in organic acid dihydrazide compound, imidazoles and derivative thereof, Dyhard RU 100, aromatic amine, epoxide modified polyamine and the poly-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.
8. 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; Described mineral filler is selected from crystalline silica, silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesiumcarbonate, barium sulfate, calcium sulfate, mica, talcum, clay, aluminum oxide, ferric oxide, magnesium oxide, zirconium white, aluminium hydroxide, magnesium hydroxide, Calucium Silicate powder, pure aluminium silicate, lithium aluminosilicate, zirconium silicate, barium titanate, granulated glass sphere, glass fibre, carbon fiber, curing aluminium, asbestos, fused silica and kaolin; Described organic filler is selected from one or more the mixture in multipolymer, polyester micropartical, urethane grain and the rubber particle of multipolymer, vinylbenzene and other monomers of polymethylmethacrylate, polystyrene, methyl methacrylate and other monomers.
9. liquid crystal sealing agent composition as claimed in claim 8 is characterized in that, the mean particle size of described mineral filler is less than or equal to 3 microns.
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