CN103865470B - A kind of photocuring edge sealing adhesive - Google Patents
A kind of photocuring edge sealing adhesive Download PDFInfo
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- CN103865470B CN103865470B CN201410048908.XA CN201410048908A CN103865470B CN 103865470 B CN103865470 B CN 103865470B CN 201410048908 A CN201410048908 A CN 201410048908A CN 103865470 B CN103865470 B CN 103865470B
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Abstract
The invention discloses a kind of curable adhesive, specifically a kind of tackiness agent of ultraviolet light polymerization, by mass percentage, its component comprises: matrix resin 10 ~ 75%, assisted resin 5 ~ 50%, the reactive monomer 10 ~ 70% of acrylate, allylic cpd or vinyl compound, adhesion promoter 5 ~ 15%, the light trigger of 1 ~ 10% and the auxiliary agent of 0.5 ~ 10%.Curable adhesive provided by the invention, has quick setting capabilities, high bond strength and low internal stress, and the cured layer of gained is soft, and hydrofluoric acid resistant performance is excellent.
Description
Technical field
The invention of this reality relates to a kind of ultraviolet photo-curing cementing agent, especially relates to one and is applied to the thinning curable adhesive of the etching of the liquid-crystalline glasses of flat-panel monitor (FPD).
Background technology
In flat display field, liquid-crystalline glasses is widely used in the display screen of mobile phone, TV, panel computer etc., liquid-crystalline glasses generally forms single liquid crystal layer by colorized optical filtering face, TFT face and liquid crystal layer, and two-layer single liquid crystal layer is bonded together the complete LCD Panel of composition one.
Mobile phone, the thickness requirement to liquid crystal display such as panel computer is high, and generally the first liquid crystal display thickness prepared is comparatively large, needs to carry out reduction processing.The method of reduction processing is with hydrofluoric acid etch, because liquid-crystalline glasses screen adopts double-sided adhesive to form, easily invade liquid crystal display during hydrofluoric acid etch from gap inner, destroy liquid crystal display, so, need before etching to carry out encapsulation process to the limit of liquid-crystalline glasses, namely use photocuring edge sealing adhesive, irradiate under 365nm ultraviolet, when irradiating UV glue, produce polyreaction, make UV glue produce the effect of solidification sclerosis, thus liquid-crystalline glasses four banding is stopped.If UV glue existing defects in coating process, the bonding effect on liquid-crystalline glasses four limit can be caused not good, cause acid solution to invade liquid crystal display in the process of acid etching inner, destroy liquid crystal display; In addition, damaged due to the ununiformity of glue bond and performance also can the cause liquid-crystalline glasses unbalance stress in process of lapping such as tensile strength is low in the process of lapping after liquid-crystalline glasses etching.
Liquid-crystalline glasses is generally light transmissive material, there is high energy surface, more bonding than being easier to, but liquid-crystalline glasses surface is easier to adsorption moisture again, even bonding rear moisture and moisture also can invade glass interface, replace bonding effect, or glued membrane is absorbed water plastify, second-order transition temperature, cohesive strength and bonding strength decline, thus adhesive failure occurs.Some curable adhesive, in order to reach better higher bonding strength, uses adhesion promoter in a large number in formula.These promotor are generally phosphoric acid ester, and polarity is large, show as initial bond strenght high especially, but excessive polar group enhances water-intake rate, cause permanent adhesive effect decay comparatively large, can not ensure lasting high-adhesive-strength.
Temperature is high to be had a significant impact curable adhesive, and temperature raises, and can accelerate the oxicracking effect of compound, hydrolytic action etc., and actual bonding result also can be caused to decline.
The viscosity of photocuring edge sealing adhesive can affect the bonding effect on liquid-crystalline glasses four limit, if viscosity is lower, though be conducive to the gap between UV glue infiltration glass, but the adhesive property that can affect between glass, cause the loss of adhesion of glass and glue, and in a glue process due to glass between inside and outside pressure reduction bubble can be caused to produce, need twice glue elimination bubble or repair bubble with full-bodied UV glue; If viscosity is too high, though the sticking power of glass and UV glue can be increased, in some glue process, there will be disconnected glue phenomenon, and UV glue to infiltrate the speed in glass gap slow thus affect production efficiency.Existing UV cure shrinkage is higher in addition, and the flexibility of cured film can be caused poor on the one hand, tensile strength is lower, causes the glue at some position and glass that consequently acid solution occurs to peel off and invade liquid crystal display inside in the handling process of reality; Also can cause on the other hand the edge toothing shape of cured film, this phenomenon can cause in follow-up grinding technics because the bonding position unbalance stress of glass and glue is so that glass breakage.
Summary of the invention
Technical problem to be solved by this invention is: provide a kind of tackiness agent in flat panel Liquid Crystal glass thinning process with excellent hydrofluoric acid resistant performance, bonding strength is high, effect is lasting ultraviolet light polymerization.
For solving the problems of the technologies described above, the technical solution adopted in the present invention is: a kind of photocuring edge sealing adhesive, by mass percentage, its component comprises: matrix resin 10 ~ 75%, assisted resin 5 ~ 50%, reactive monomer 10 ~ 70%, adhesion promoter 5 ~ 15%, light trigger 1 ~ 10%, auxiliary agent 0.5 ~ 10%;
Described matrix resin is a kind of or two or more arbitrarily mixture in polyether based polyurethanes acrylate, epoxy acrylate, urethane acrylate, PBAA ester;
Described assisted resin is urethane acrylate or epoxy acrylate;
Described reactive monomer is monofunctional acrylates's ester, bifunctional acrylate, multi-functional acrylate, simple function group allylic cpd, bifunctional allylic cpd, polyfunctional group allylic cpd, monofunctional vinyl's based compound, difunctional vinyl's based compound, the one in polyfunctional group vinyl compound or any two or more mixture.
By mass percentage, its component comprises: matrix resin 35 ~ 60%, assisted resin 8 ~ 30%, reactive monomer 20 ~ 45%, adhesion promoter 6 ~ 10%, light trigger 2 ~ 8%, auxiliary agent 1 ~ 5%.
Described photocuring edge sealing adhesive also comprises pigment or dyestuff 0.5 ~ 8wt%.
Described matrix resin provides the essential property of curable adhesive, there is suitable cohesiveness and acid resistance and stability, the present invention selects polyether based polyurethanes acrylate, epoxy acrylate, urethane acrylate or PBAA ester as matrix resin, this resinoid has suitable cementability and stability, simultaneously the normal more suitable matrix resin as tackiness agent of polyester-based polyurethane acrylate used in its acid and alkali-resistance water tolerance hinge structure.Polyether based polyurethanes acrylate is prepared by polyether polyhydroxy-compound, isocyanic ester, vinylformic acid and acrylate.Polyether polyhydroxy-compound uses conventional polyether glycol, such as polyoxyethylene glycol, polypropylene glycol etc.; Isocyanic ester is 2,4 toluene diisocyanate or isofoer diisocyanate; Crylic acid hydroxy ester is Hydroxyethyl acrylate (HEMA) and vinylformic acid (HPMA); Urethane acrylate can increase solidification layer kindliness, reduce stress shrink, improve sticking power; Epoxy acrylic methyl esters has higher rigidity, tensile strength and thermostability; PBAA ester has good moisture-proof effect, also has good resistance to low temperature simultaneously.
Described assisted resin is urethane acrylate or epoxy acrylate.Assisted resin adds in order to the bulk property adjusting tackiness agent, compensate for some deficiency of matrix resin, such as tensile strength, high temperature resistant character, hardness etc.
Described matrix resin and the functionality of assisted resin are 2 ~ 9, and the number-average molecular weight of matrix resin and assisted resin is 500 ~ 10000.The modest viscosity of these resins, solidification process shrinking percentage is lower, has good film forming and adhesion property.The commercial prod of these resins has CN117, CN118, CN962, CN966J75, CN985B88 etc. of Sartomer company, 6134A-80,615-100,6141H-80 etc. of Changxing chemical company, the Photomer6230 etc. of Cognis company.
Preferred further CN962, CN966J75, CN985B88 and/or 6134A-80 of described resin.
The effect of described reactive monomer is regulation system viscosity, the wettability of promoting tackiness agent and glass, improves curing speed and improve the various performances of solidifying front and back material, as snappiness, hardness etc.In the present invention, reactive monomer is selected from monofunctional acrylates's ester, bifunctional acrylate, multi-functional acrylate, simple function group allylic cpd, bifunctional allylic cpd, polyfunctional group allylic cpd, monofunctional vinyl's based compound, difunctional vinyl's based compound, polyfunctional group vinyl compound and combinations two or more arbitrarily thereof.Monofunctional monomers containing functional group can improve adhesive property in UV cured adhesive, and polyfunctional monomer can improve adhesive property by improving cross-linking density.
Described reactive monomer is one or more in following compound: mono-functional reactive's monomer is as (methyl) 2-ethylhexyl acrylate, (methyl) isobornyl acrylate, (methyl) lauryl acrylate, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) phenoxy ethyl acrylate, (methyl) ethioxy ethoxyethyl group ester, NVP etc., di-functional reactive's monomer is as (methyl) vinylformic acid ethylene glycol bisthioglycolate (methyl) acrylate, butyleneglycol two (methyl) acrylate, hexylene glycol two (methyl) acrylate, tetraethylene-glycol two (methyl) acrylate, dicyclopentadiene acrylate, tripropylene glycol two (methyl) acrylate, polyoxyethylene glycol (200) two (methyl) acrylate, polyoxyethylene glycol (400) two (methyl) acrylate, polyoxyethylene glycol (600) two (methyl) acrylate, polyoxyethylene glycol (800) two (methyl) acrylate, trimethylolpropane allyl ether, polyfunctional group reactive monomer as trimethylolpropane tris (methyl) acrylate, ethoxylated trimethylolpropane three (methyl) acrylate, Viscoat 295, propoxylation trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, pentaerythritol triallyl ether, two season penta 6 alcohol five (methyl) acrylate etc., and some commercial specific functional groups acrylate are as the Photomer4039(phenolic group oxyethyl group 3EO mono acrylic ester of Cognis company), the CD9050(monofunctional acrylate of Sartomer company) etc.
One or more in the preferred Viscoat 295 of described reactive monomer, dicyclopentadiene acrylate, trimethylolpropane tris (methyl) acrylate, ethoxylated trimethylolpropane three (methyl) acrylate, propoxylation trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, two season penta 6 alcohol five (methyl) acrylate; This compounds has good water tolerance.
Described adhesion promoter is selected from one or more the mixture in hydroxyalkyl acrylates, vinylformic acid, the acrylate containing carboxyl functional group, the phosphoric acid ester adhesion promoter containing unsaturated functional group.
Described light trigger is selected from one or more the mixture in scission reaction photoinitiator, hydrogen eliminative reaction mechanism light trigger, visible light initiator or radical photoinitiator.
Described scission reaction photoinitiator is as benzoin ether, benzil ketals, methyl phenyl ketone, acyl group phosphorus oxide light trigger, described hydrogen eliminative reaction mechanism light trigger is as benzophenone and tertiary amine title complex, thioxanthone and derivative thereof, two imidazoles, described visible light initiator is as camphorquinone, described radical photoinitiator is as st-yrax contracting methyl ether (CIBA-GEIGY company trade name Irgacure651), 1-hydroxycyclohexyl phenyl ketone (trade name Irgacure184), 2-hydroxy-2-methyl-1-phenyl-1-acetone (trade name Darocure1173), 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholine-1-acetone (trade name Irgacure907), 2, 4, 6-trimethylbenzoy-dipheny phosphine oxide (trade name TPO), 2-phenyl benzyl-2-dimethyl amine-1-(4-morpholine benzyl phenyl) butanone (trade name Irgacure369).Preferred Irgacure369, Irgacure907 and/or TPO.Light trigger may be used alone, can also be used in combination, and mainly curing speed as requested, bondline thickness determine.
Described adhesion promoter is one or both in modest 1121 adhesion promoters of moral, SartomerCD9051, the A-172 silane coupling agent of union carbide corporation, methacrylic acid phosphoric acid ester.Preferred moral modest 1121 or A-172.
Described auxiliary agent be oxidation inhibitor, flow agent, defoamer, stablizer one or more.Wherein oxidation inhibitor is one or more of hindered phenol compound, phosphite ester compound, thio-based compound and complex class compound; Preferred hindered phenol compound, as BHT, 2246,1010,1076.Stablizer is one or more in ferrocene compounds, anhydrides compound, phenol compound; Ferrocene compounds is ferrocene, methyl ferrocene, ethyl dicyclopentadienyl iron; Anhydrides compound is Tetra hydro Phthalic anhydride, maleic anhydride, succinyl oxide; Phenol compound is Resorcinol, p methoxy phenol, 2,6 ditertiary butyl p cresol.Preferred ferrocene, methyl ferrocene, ethyl dicyclopentadienyl iron, Tetra hydro Phthalic anhydride, Resorcinol and/or p methoxy phenol; Deaerating agent Airex900 or Airex920 etc. of solvent-borne type defoamer 2700 or 3100, the Di Gao company of defoamer Shi Deqian company.Preferred solvent type defoamer 3100.
Described filler is pigment or dyestuff.
Described pigment is red pigment, veridian or blue pigments.
Described red pigment is pyrene series pigments, anthraquione pigmentss separately or one of them plant the mixture of pigment and tetrazo system yellow pigment or phosphorus system of India yellow pigment, such as can select the red pigment of following trade(brand)name: Pigment red 7, Pigment red 14, pigment red 41, pigment red 4 8:1, pigment red 4 8:2, pigment red 4 8:3, pigment red 4 8:4, pigment red 146, Pigment red 177, Pigment red 178, Pigment red 184, Pigment red 185, Pigment red 187, Pigment red 200, Pigment red 202, Pigment red 208, pigment red 21 0, Pigment red 246, Pigment red 254, Pigment red 255, Pigment red 264, Pigment red 272 etc.Such as can select the yellow ultramarine of following trade(brand)name: Pigment Yellow 73 1, Pigment Yellow 73 2, Pigment Yellow 73 3, Pigment Yellow 73 4, Pigment Yellow 73 5, Pigment Yellow 73 6, Pigment Yellow 73 10, pigment Yellow 12, pigment yellow 13, pigment Yellow 14, Pigment Yellow 73 15, Pigment Yellow 73 16, pigment yellow 17, Pigment Yellow 73 18, Pigment Yellow 73 24, Pigment Yellow 73 31, Pigment Yellow 73 32, pigment yellow 34, Pigment Yellow 73 35, Pigment Yellow 73 35:1, Pigment Yellow 73 36, Pigment Yellow 73 36:1, Pigment Yellow 73 37, Pigment Yellow 73 37:1, Pigment Yellow 73 40, Pigment Yellow 73 42, Pigment Yellow 73 43, Pigment Yellow 73 53, Pigment Yellow 73 55, Pigment Yellow 73 60, C.I. Pigment Yellow 73 61, Pigment Yellow 73 62, Pigment Yellow 73 63, Pigment Yellow 73 65, Pigment Yellow 73 73, Pigment Yellow 73 74, Pigment Yellow 73 77, pigment yellow 81, pigment yellow 83, Pigment Yellow 73 93, Pigment Yellow 73 94, Pigment Yellow 73 95, Pigment Yellow 73 97, Pigment Yellow 73 98, Pigment Yellow 73 100, Pigment Yellow 73 101, Pigment Yellow 73 104, Pigment Yellow 73 106, Pigment Yellow 73 108, Pigment Yellow 73 109, Pigment Yellow 73 110, Pigment Yellow 73 113, Pigment Yellow 73 114, Pigment Yellow 73 115, Pigment Yellow 73 116, Pigment Yellow 73 117, Pigment Yellow 73 118, Pigment Yellow 73 119, pigment Yellow 12 0, pigment Yellow 12 6, pigment Yellow 12 7, pigment Yellow 12 8, pigment Yellow 12 9, pigment yellow 13 8, pigment yellow 13 9, Pigment Yellow 73 150, Pigment Yellow 73 151, Pigment Yellow 73 152, Pigment Yellow 73 153, pigment yellow 154, Pigment Yellow 73 155, Pigment Yellow 73 156, Pigment Yellow 73 161, Pigment Yellow 73 162, Pigment Yellow 73 164, Pigment Yellow 73 166, Pigment Yellow 73 167, Pigment Yellow 73 168, Pigment Yellow 73 169, pigment yellow 17 0, pigment yellow 17 1, pigment yellow 17 2, pigment yellow 17 3, pigment yellow 17 4, pigment yellow 17 5, pigment yellow 17 6, pigment yellow 17 7, pigment yellow 17 9, Pigment Yellow 73 180, Pigment Yellow 73 181, Pigment Yellow 73 182, Pigment Yellow 73 185, Pigment Yellow 73 187, Pigment Yellow 73 191:1, Pigment Yellow 73 199 etc.
Described veridian is the mixture of halogenated phthalocyanines series pigments, tetrazo system yellow pigment or India's phosphorus system yellow pigment and halogenated phthalocyanines series pigments; Phthualocyanine pigment is as pigment green 36, and yellow pigment is one in azo type pigment, azo condensed type pigment, heterocyclic pigment or its combination.Such as can select the yellow pigment of following trade(brand)name: Pigment Yellow 73 1, Pigment Yellow 73 2, Pigment Yellow 73 3, Pigment Yellow 73 4, Pigment Yellow 73 5, Pigment Yellow 73 6, Pigment Yellow 73 10, pigment Yellow 12, pigment yellow 13, pigment Yellow 14, Pigment Yellow 73 15, Pigment Yellow 73 16, pigment yellow 17, Pigment Yellow 73 18, Pigment Yellow 73 24, Pigment Yellow 73 31, Pigment Yellow 73 32, pigment yellow 34, Pigment Yellow 73 35, Pigment Yellow 73 35:1, Pigment Yellow 73 36, Pigment Yellow 73 36:1, Pigment Yellow 73 37, Pigment Yellow 73 37:1, Pigment Yellow 73 40, Pigment Yellow 73 42, Pigment Yellow 73 43, Pigment Yellow 73 53, Pigment Yellow 73 55, Pigment Yellow 73 60, C.I. Pigment Yellow 73 61, Pigment Yellow 73 62, Pigment Yellow 73 63, Pigment Yellow 73 65, Pigment Yellow 73 73, Pigment Yellow 73 74, Pigment Yellow 73 77, pigment yellow 81, pigment yellow 83, Pigment Yellow 73 93, Pigment Yellow 73 94, Pigment Yellow 73 95, Pigment Yellow 73 97, Pigment Yellow 73 98, Pigment Yellow 73 100, Pigment Yellow 73 101, Pigment Yellow 73 104, Pigment Yellow 73 106, Pigment Yellow 73 108, Pigment Yellow 73 109, Pigment Yellow 73 110, Pigment Yellow 73 113, Pigment Yellow 73 114, Pigment Yellow 73 115, Pigment Yellow 73 116, Pigment Yellow 73 117, Pigment Yellow 73 118, Pigment Yellow 73 119, pigment Yellow 12 0, pigment Yellow 12 6, pigment Yellow 12 7, pigment Yellow 12 8, pigment Yellow 12 9, pigment yellow 13 8, pigment yellow 13 9, Pigment Yellow 73 150, Pigment Yellow 73 151, Pigment Yellow 73 152, Pigment Yellow 73 153, pigment yellow 154, Pigment Yellow 73 155, Pigment Yellow 73 156, Pigment Yellow 73 161, Pigment Yellow 73 162, Pigment Yellow 73 164, Pigment Yellow 73 166, Pigment Yellow 73 167, Pigment Yellow 73 168, Pigment Yellow 73 169, pigment yellow 17 0, pigment yellow 17 1, pigment yellow 17 2, pigment yellow 17 3, pigment yellow 17 4, pigment yellow 17 5, pigment yellow 17 6, pigment yellow 17 7, pigment yellow 17 9, Pigment Yellow 73 180, Pigment Yellow 73 181, Pigment Yellow 73 182, Pigment Yellow 73 185, Pigment Yellow 73 187, Pigment Yellow 73 191:1, Pigment Yellow 73 199 etc., or the mixture of one or more pigment can be used.
Described blue pigments is the mixture of halogenated phthalocyanines series pigments, halogenated phthalocyanines series pigments and dioxazines violet pigment; The such as blue pigments of following trade(brand)name: pigment Blue 15: 1, pigment Blue 15: 2, pigment Blue 15: 3, pigment Blue 15: 3, pigment Blue 15: 4, pigment Blue 15: 6, pigment blue 16, pigment blue 17, Pigment blue 21, Pigment blue 22, Pigment blue, Pigment blue 64, Pigment blue 76 etc., violet pigment is as pigment violet 19, pigment Violet 23.
Described UV photocuring edge sealing adhesive preparation process is: add matrix resin and stablizer in a reservoir, stirring and dissolving, add reactive monomer and light trigger again, stirring and dissolving, then assisted resin, reactive monomer and auxiliary agent is added, stirring and dissolving, finally adds defoamer, namely obtains UV photocuring edge sealing adhesive after mixing and stirring.
Compared with prior art, the present invention has following beneficial effect:
1) the present invention selects one in polyether based polyurethanes acrylate, urethane acrylate, epoxy acrylate, PBAA ester or its mixture as matrix resin, curable adhesive of the present invention is made to be provided with suitable cementability and stability, the normal more suitable matrix resin as tackiness agent of urethane acrylate used in its acid and alkali-resistance water tolerance hinge structure, wherein the employing of PBAA ester also add the lower temperature resistance of curable adhesive of the present invention;
2) assisted resin of the present invention is bulk property in order to adjust tackiness agent and adds, compensate for matrix resin in tensile strength, heatproof character, some of the aspects such as hardness is not enough, significantly improves the performance of the aspects such as the tackiness of tackiness agent, heatproof;
3) hinge structure, the present invention has also selected the esters of acrylic acid reactive monomer of water-tolerant, makes curable adhesive of the present invention still remain good bonding strength under high humidity or hot and humid condition;
4) curable adhesive provided by the invention, has the stickiness more more excellent than the curable adhesive of prior art, especially has high bonding strength to glass, and high-temp resisting high-humidity resisting, and acid resistance is excellent, has broad application prospects.
Accompanying drawing explanation
Fig. 1 is crenellated phenomena test comparison figure after solidification;
Fig. 2 is coating test comparison figure.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with case study on implementation, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
The embodiment of the present invention provides the preparation method that a kind of more existing edge sealing adhesive bonding strength etching that is higher, that be applicable to liquid-crystalline glasses is thinning, can improve the edge sealing adhesive of yield, comprises the following steps: stirred at lower than the temperature of 30 DEG C by each raw material of the described edge sealing adhesive of preparation; The proportioning of each raw material of the described edge sealing adhesive of described preparation is: matrix resin 30 ~ 50%, assisted resin 10 ~ 30%, reactive monomer 25% ~ 45%, adhesion promoter 6 ~ 10%, light trigger 3% ~ 5%, auxiliary agent 2% ~ 5%, pigment or dyestuff 0.5% ~ 5%; Be uniformly mixed preparing the above-mentioned raw materials mixed at the temperature of 20 DEG C ~ 50 DEG C.
Tested viscosity, if test result does not meet the viscosity threshold of setting, then adjusts viscosity to described viscosity threshold, the range of viscosities of the edge sealing adhesive that namely viscosity threshold of described setting obtains.Viscosity is the significant parameter determining edge sealing adhesive performance, and viscosity is too large, is unfavorable for the coating of edge sealing adhesive; And the too little acid solution that cannot prevent of viscosity is impacted and invades inside liquid crystal, therefore the viscosity of edge sealing adhesive need meet the viscosity threshold of setting, and one is preferably in embodiment, and viscosity threshold was set as 300 ~ 2000 milli handkerchief seconds.
Embodiment 1
Polyurethane acroleic acid light-cured resin 46%, the light trigger 369 of polyether based polyurethanes acrylate 8%, 1%, trimethylolpropane tris (methyl) acrylate 15%, tetramethylolmethane three (methyl) acrylate 15%, containing the phosphoric acid ester adhesion promoter 6% of unsaturated functional group, auxiliary agent 2% and pigment P.R.2547%, be uniformly mixed and get final product.
Embodiment 2
The edge sealing adhesive that the embodiment of the present invention also provides another edge sealing adhesive preparation method and the method to obtain, is with difference in embodiment 1, and each raw material composition preparing this edge sealing adhesive is different, specific as follows with proportioning (mass percent):
Polyether based polyurethanes acrylate 40%, the light trigger 369 of epoxy acrylic 15%, 2%, trimethylolpropane tris (methyl) acrylate 18%, ethoxylated trimethylolpropane three (methyl) acrylate 16%, containing acrylate adhesion promoter 6% and other auxiliary agents 3% of carboxyl functional group, be uniformly mixed and get final product.
Embodiment 3
The embodiment of the present invention also provides the edge sealing adhesive that in the 3rd, edge sealing adhesive preparation method and the method obtain, and is with the difference part of embodiment 1 and 2, and each raw material composition and the proportioning (mass percent) of preparing this edge sealing adhesive are as follows:
Polyurethane acroleic acid light-cured resin 50%, the light trigger 907 of PBAA ester 15%, 2%, ethoxylated trimethylolpropane three (methyl) acrylate 10%, tetramethylolmethane three (methyl) acrylate 14%, acrylate adhesion promoter 3% containing carboxyl functional group, the phosphoric acid ester adhesion promoter 3% containing unsaturated functional group and other auxiliary agents 3%, be uniformly mixed and get final product.
The embodiment of the present invention provides preparation method and the sealed plastic box obtained according to the method, the bad incidence of glue of breaking when glue is low, the neat in edge of UV glue after solidification, without crenellated phenomena, and cured film has excellent snappiness and tensile strength, thus it is inner that acid solution can be avoided to invade liquid crystal display, but also the breakage rate of glass in grinding step can be reduced, improve the high yield of product.
For the superiority of edge sealing adhesive of the present invention is described better, as shown in Fig. 1 ~ 2, following is a list the result that edge sealing adhesive that the embodiment of the present invention 1 to 3 provides and existing edge sealing adhesive carry out coating and stripping strength contrast experiment.
Concrete test condition is as follows: experiment employing 2.5 generation line liquid-crystalline glasses, adopts edge sealing adhesive provided by the invention and existing edge sealing adhesive in the experiment of this contrast test, and some glue process adopts manually puts glue.
The test result of contrast experiment is as follows:
The first, after solidification, crenellated phenomena test comparison result as shown in Figure 1, as can be seen from Figure 1: edge sealing adhesive of the present invention (upper figure) does not have zigzag fashion in the cured film at liquid-crystalline glasses edge; And existing edge sealing adhesive (figure below) has obvious sawtooth pattern in the cured film at liquid-crystalline glasses edge, four limits of whole liquid-crystalline glasses are almost taken.The bonding unbalance stress of liquid-crystalline glasses and cured film can be caused to cause liquid-crystalline glasses easily film to occur in handling process for the crenellated phenomena of this degree and glass is peeled off, and liquid crystal display is inner or grinding is damaged to cause acid solution to invade.
The second, as shown in Figure 2, existing edge sealing adhesive (upper figure) there will be the discontinuous coating of the edge sealing adhesive glue that breaks to coating test comparison result when glue bad, incidence higher (10% ~ 15%); Edge sealing adhesive of the present invention (figure below) is when applying, and discontinuous coating breaks the bad incidence of glue very low (<1%).Edge sealing adhesive of the present invention can keep good continuity in coating situation, but, the viscosity of existing edge sealing adhesive is generally large than described viscosity threshold, with edge sealing adhesive of the present invention when identical coating speed applies, disconnected glue bad phenomenon happens occasionally, and existing edge sealing adhesive can keep good continuity in coating situation.
3rd, acid resistance test comparison result is as shown in table 1, is tested by the acid etch of same level, and the etch resistant time of edge sealing adhesive of the present invention is greater than 80min; And the etch resistant test same period average of traditional edge sealing adhesive is less than 60min.As can be seen here, edge sealing adhesive bonding strength of the present invention is higher than existing edge sealing adhesive.
Table 1
| Edge sealing adhesive classification | Embodiment 1 | Embodiment 2 | Embodiment 3 | Existing edge sealing adhesive |
| Acidproof etching time | 90min | 85min | 95min | 50min |
The above; be only the specific embodiment of the present invention, but protection scope of the present invention is not limited thereto, is anyly familiar with those skilled in the art in the technical scope that the present invention discloses; change can be expected easily or replace, all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claim.
Claims (10)
1. a photocuring edge sealing adhesive, by mass percentage, its component comprises: polyether based polyurethanes acrylate 10 ~ 75%, assisted resin 5 ~ 50%, reactive monomer 10 ~ 70%, adhesion promoter 5 ~ 15%, light trigger 1 ~ 10%, auxiliary agent 0.5 ~ 10%;
Described assisted resin is a kind of or two or more arbitrarily mixture in polyether based polyurethanes acrylate, epoxy acrylic, PBAA ester;
Described reactive monomer is a kind of or two or more arbitrarily mixture in trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, ethoxylated trimethylolpropane three (methyl) acrylate;
Described matrix resin and the functionality of assisted resin are 2 ~ 9, and the number-average molecular weight of matrix resin and assisted resin is 500 ~ 10000;
Described auxiliary agent is one or more in oxidation inhibitor, flow agent, defoamer, stablizer.
2. a kind of photocuring edge sealing adhesive according to claim 1, it is characterized in that: by mass percentage, its component comprises: matrix resin 35 ~ 60%, assisted resin 8 ~ 30%, reactive monomer 20 ~ 45%, adhesion promoter 6 ~ 10%, light trigger 2 ~ 8%, auxiliary agent 1 ~ 5%.
3. a kind of photocuring edge sealing adhesive according to claim 1 and 2, it is characterized in that: described photocuring edge sealing adhesive also comprises pigment or dyestuff, its mass percentage is 0.5 ~ 8%.
4. a kind of photocuring edge sealing adhesive according to claim 1 and 2, is characterized in that: described adhesion promoter is selected from one or more the mixture in hydroxyalkyl acrylates, vinylformic acid, the acrylate containing carboxyl functional group, the phosphoric acid ester adhesion promoter containing unsaturated functional group.
5. a kind of photocuring edge sealing adhesive according to claim 1, is characterized in that: described light trigger is selected from one or more the mixture in the title complex of benzoin ether, benzil ketals, methyl phenyl ketone, acylphosphine oxide, benzophenone and tertiary amine, thioxanthone, thioxanthone derivative, two imidazoles, camphorquinone.
6. a photocuring edge sealing adhesive, by mass percentage, its component comprises: polyurethane acroleic acid light-cured resin 10 ~ 75%, assisted resin 5 ~ 50%, reactive monomer 10 ~ 70%, adhesion promoter 5 ~ 15%, light trigger 1 ~ 10%, auxiliary agent 0.5 ~ 10%;
Described assisted resin is a kind of or two or more arbitrarily mixture in polyether based polyurethanes acrylate, epoxy acrylic, PBAA ester;
Described reactive monomer is a kind of or two or more arbitrarily mixture in trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, ethoxylated trimethylolpropane three (methyl) acrylate;
Described matrix resin and the functionality of assisted resin are 2 ~ 9, and the number-average molecular weight of matrix resin and assisted resin is 500 ~ 10000;
Described auxiliary agent is one or more in oxidation inhibitor, flow agent, defoamer, stablizer.
7. a kind of photocuring edge sealing adhesive according to claim 6, it is characterized in that: by mass percentage, its component comprises: matrix resin 35 ~ 60%, assisted resin 8 ~ 30%, reactive monomer 20 ~ 45%, adhesion promoter 6 ~ 10%, light trigger 2 ~ 8%, auxiliary agent 1 ~ 5%.
8. a kind of photocuring edge sealing adhesive according to claim 6 or 7, is characterized in that: described photocuring edge sealing adhesive also comprises pigment or dyestuff, and its mass percentage is 0.5 ~ 8%.
9. a kind of photocuring edge sealing adhesive according to claim 6 or 7, is characterized in that: described adhesion promoter is selected from one or more the mixture in hydroxyalkyl acrylates, vinylformic acid, the acrylate containing carboxyl functional group, the phosphoric acid ester adhesion promoter containing unsaturated functional group.
10. a kind of photocuring edge sealing adhesive according to claim 6, is characterized in that: described light trigger is selected from one or more the mixture in the title complex of benzoin ether, benzil ketals, methyl phenyl ketone, acylphosphine oxide, benzophenone and tertiary amine, thioxanthone, thioxanthone derivative, two imidazoles, camphorquinone.
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| CN201410048908.XA CN103865470B (en) | 2014-02-12 | 2014-02-12 | A kind of photocuring edge sealing adhesive |
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| CN201410048908.XA CN103865470B (en) | 2014-02-12 | 2014-02-12 | A kind of photocuring edge sealing adhesive |
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| CN103865470A CN103865470A (en) | 2014-06-18 |
| CN103865470B true CN103865470B (en) | 2016-04-06 |
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| CN201410048908.XA Active CN103865470B (en) | 2014-02-12 | 2014-02-12 | A kind of photocuring edge sealing adhesive |
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| JP6481167B2 (en) * | 2015-04-09 | 2019-03-13 | 協立化学産業株式会社 | Photocurable adhesive composition |
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| CN106047269A (en) * | 2016-05-26 | 2016-10-26 | 惠晶显示科技（苏州）有限公司 | Acid-resistant alkali-resistant UV (ultraviolet) glass edge sealing adhesive |
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| CN112280440A (en) * | 2019-07-25 | 2021-01-29 | 上海飞凯光电材料股份有限公司 | UV adhesive coating, preparation method thereof and preparation method of coated workpiece |
| CN112063356B (en) * | 2020-09-16 | 2022-06-03 | 东莞市派乐玛新材料技术开发有限公司 | Ultraviolet curing adhesive and preparation method and application thereof |
| WO2023135855A1 (en) * | 2022-01-12 | 2023-07-20 | 積水フーラー株式会社 | Composition for thin layer glass temporary fixation |
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