阅读说明：本技术 一种量子点封装专用密封胶及其制备方法 (A kind of quantum dot package specific sealant and preparation method thereof ) 是由 成浩冠 张小中 黎松 张亚平 刘兆辉 于 2019-08-27 设计创作，主要内容包括：本发明公开了一种量子点封装专用密封胶及其制备方法,所述量子点封装专用密封胶包括如下按质量份计算的组分：A组份：60～80份有机硅改性环氧树脂；20～40份活性稀释剂；2～5份光产酸剂；0.2～0.6份光敏剂；B组份：60～80份聚氨酯改性有机硅树脂；20～40份丙烯酸酯类活性稀释剂；2～6份自由基光引发剂；其中,所述A组份与B组份的质量比为4:1～1:2。本发明所述的量子点封装专用密封胶与量子点具有良好的相容性、对量子点荧光亮度影响小,耐老化性能优异,粘结性能好,环境可靠性优异。(The invention discloses a kind of quantum dot package specific sealant and preparation method thereof, the quantum dot package specific sealant includes the component calculated in parts by mass as follows: component A: 60~80 parts of modifying epoxy resin by organosilicon；20~40 portions of reactive diluents；2~5 parts of photoacid generators；0.2~0.6 part of photosensitizer；B component: 60~80 parts of polyurethane-modified organic siliconresins；20~40 portions of esters of acrylic acid reactive diluents；2~6 parts of free radical photo-initiations；Wherein, the mass ratio of the component A and B component is 4:1~1:2.Quantum dot package specific sealant of the present invention and quantum dot have good compatibility, influence on quantum dot fluorescence brightness small, and ageing-resistant performance is excellent, and adhesive property is good, and environmental reliability is excellent.)

1. a kind of quantum dot package specific sealant, which is characterized in that including the component calculated in parts by mass as follows:

Component A:

60~80 parts of modifying epoxy resin by organosilicon；

20~40 parts of reactive diluent；

2~5 parts of photoacid generator；

0.2~0.6 part of photosensitizer；

B component:

60~80 parts of polyurethane-modified organic siliconresin；

20~40 parts of esters of acrylic acid reactive diluent；

2~6 parts of free radical photo-initiation；

Wherein, the mass ratio of the component A and B component is 4:1~1:2；

The modifying epoxy resin by organosilicon is Pai Lema EP550, and the polyurethane-modified organic siliconresin is Pai Lema PU2386。

2. quantum dot package specific sealant according to claim 1, which is characterized in that the matter of the component A and B component Amount is than being 4:1~2:1.

3. quantum dot package specific sealant according to claim 1, which is characterized in that the reactive diluent is 3,4- Epoxycyclohexyl-methyl 3,4- epoxycyclohexyl formic acid esters or 3,4- epoxycyclohexyl-methyl 3,4- epoxycyclohexyl formic acid esters with The mixture of poly- [(2- Oxyranyle) -1,2- cyclohexanediol] 2- ethyl -2- (methylol) -1,3- propylene glycol.

4. quantum dot package specific sealant according to claim 3, which is characterized in that the reactive diluent includes 10 ~30 parts of 3,4- epoxycyclohexyl-methyl 3,4- epoxycyclohexyl formic acid esters and 0~20 part of poly- [(2- Oxyranyle) -1,2- ring Hexylene glycol] 2- ethyl -2- (methylol) -1,3- propylene glycol.

5. quantum dot package specific sealant according to claim 1, which is characterized in that the esters of acrylic acid activity is dilute Releasing agent is isobornyl acrylate, tridecyl acrylate, dicyclopentadiene acrylate, two propylene of Tricyclodecane Dimethanol One or more of acid esters.

6. quantum dot package specific sealant according to claim 1, which is characterized in that the photoacid generator is 4- isobutyl Base phenyl -4'- aminomethyl phenyl iodine hexafluorophosphate, diphenyl-(4- phenyl sulphur) phenyl sulfonium hexafluorophosphate, bis- (4,4'- thioethers Triphenyl sulphur) hexafluoro antimonate and diphenyl-(4- phenyl sulphur) phenyl sulfonium hexafluoro antimonate mixture) one of or it is more Kind.

7. quantum dot package specific sealant according to claim 1, which is characterized in that the photosensitizer is 2- isopropyl One of thioxanthone, camphorquinone, cumarin are a variety of.

8. quantum dot package specific sealant according to claim 1, which is characterized in that the free radical photo-initiation is 2- hydroxy-2-methyl -1- phenyl -1- acetone, 1- hydroxy-cyclohexyl phenyl ketone, benzoin dimethylether, bis- (the 2,4,6- front threes of phenyl One or more of base benzoyl) phosphine oxide.

9. the preparation method of quantum dot package specific sealant described in claim 1-8 any claim, which is characterized in that Include the following steps: to be uniformly mixed component A with B component up to the quantum dot package specific sealant.

Technical field

The present invention relates to quantum dot sealing material fields, in particular it relates to which a kind of quantum dot package specific seals Glue and preparation method thereof.

Background technique

The appearance of technology of quantum dots allows LCD technology upgrading to search out new breakthrough mouth again and pays close attention to by industry.2014 Since year, not only the international big factory such as Samsung, LG produces tv display screen, China's BOE, China by technology of quantum dots The native country starlight electricity Deng manufacturer also announces that quantum dot backlight technology product will import volume production.For at present, quantum dot backlight skill Art carries out large-scale application, and there are still an important bottlenecks, are exactly its main material --- quantum dot life problems.How It is enough to maintain long fluorescence lifetime in external environment for a long time, it is that can quantum dot back light source technique be widely used in being economical, high The key of the display material of effect.

It encapsulates polymer and utilizes high molecular polymer swelling-deswelling effect, by quantum dot diffusion into polymer, directly Package and contact quantum dot are connect, realizes the minute yardstick package isolation to quantum dot nano-particle, isolation quantum dot connects with extraneous Touching, avoids the pollution of moisture, dust etc., extends luminescent properties and the service life of quanta point material.Therefore, encapsulation polymeric material is promoted The water proof oxygen barrier property of material and to the combined strength bination between quantum dot nano particle for extend quantum dot the optical service life It is most important

Currently, the core technology of quantum dot optical film sealing material mainly still rests in external several companies (such as 3M, Tao Shi etc.) in hand, still belong to blank at home, the display screen manufacturing enterprise in downstream can only select external company's cooperation.Due to Following market prospects are boundless, break overseas enterprise and are conducive to the domestic of quantum dot optical film to the monopolization of sealing material Change, improve the technical level of domestic new material industry.For downstream industry, be conducive to improve the manufacturing competition of display screen Power promotes FPD industry in native country quickly of far-reaching significance to the production domesticization development of China's flat-panel monitor production industry.Therefore It is necessary to seek a kind of quantum dot package specific sealant hermetically sealed suitable for quantum dot.

Summary of the invention

The present invention is directed to overcome at least one of the above-mentioned prior art insufficient, a kind of quantum dot package specific sealing is provided Glue, the sealant and quantum dot have good compatibility, influence on quantum dot fluorescence brightness small, and ageing-resistant performance is excellent, Adhesive property is good, and environmental reliability is excellent.

Another object of the present invention is to provide the preparation methods of the quantum dot package specific sealant.

The technical solution adopted by the present invention is as follows:

A kind of quantum dot package specific sealant, including the component calculated in parts by mass as follows:

Component A:

60~80 parts of modifying epoxy resin by organosilicon；

20~40 parts of reactive diluent；

2~5 parts of photoacid generator；

0.2~0.6 part of photosensitizer；

B component:

60~80 parts of polyurethane-modified organic siliconresin；

20~40 parts of esters of acrylic acid reactive diluent；

2~6 parts of free radical photo-initiation；

Wherein, the mass ratio of the component A and B component is 4:1~1:2.

Two resin-light-cured polyurethane modified organic silicone resin the material and have that the application is independently synthesized with Pai Lema Ingredient based on machine epoxy silicone material, is equipped with reactive diluent, photoinitiator, by hybrid UV-curing, keeps sealant real The key performances such as oxygen barrier high water proof, light aging resisting, high transmittance, low haze, low volume contraction, strong cohesive force are showed, have finally had Effect ground solves the problems, such as quantum nanoparticles because the infiltration of water and oxygen causes its performance to decline, and improves the fluorescence longevity of quantum dot Life is cleared away the obstacles for the Industrialization of quantum dot optical film, and then pushes the development of native country FPD industry.

Preferably, the mass ratio of the component A and B component is 4:1~2:1.It is found in experimentation, when component A and B group Part mass ratio when being 4:1~2:1, excellent in compatibility (the bad sealant of compatibility is unfavorable for quantum dot for resin and quantum dot Dispersion, and quantum dot is be easy to cause to quench, influences the service life of quantum dot), stable homogeneous solution can be obtained, and resin is to amount Son point fluorescent brightness influences small, quantum dot fluorescence brightness height.

Preferably, the reactive diluent is 3,4- epoxycyclohexyl-methyl 3,4- epoxycyclohexyl formic acid esters or 3,4- ring Oxygen cyclohexyl methyl 3,4- epoxycyclohexyl formic acid esters and poly- [(2- Oxyranyle) -1,2- cyclohexanediol] 2- ethyl -2- (hydroxyl Methyl) -1,3- propylene glycol mixture.It is found in experimentation, quantum dot is in different work in modifying epoxy resin by organosilicon Property diluent in dispersity and glue film fluorescent brightness decaying will be different, in 3,4- epoxycyclohexyl-methyl 3,4- epoxy In hexahydrobenzoid acid ester, or in 3,4- epoxycyclohexyl-methyl 3,4- epoxycyclohexyl formic acid esters and poly- [(2- ethylene oxide Base) -1,2- cyclohexanediol] it is well dispersed in 2- ethyl -2- (methylol) -1,3-PD ether mixture, it can obtain Even stablizing solution, and the decaying of glue film fluorescent brightness is less.

It is further preferred that the reactive diluent includes 10~30 parts of 3,4- epoxycyclohexyl-methyls 3,4- epoxy hexamethylene Carbamate and 0~20 part of poly- [(2- Oxyranyle) -1,2- cyclohexanediol] 2- ethyl -2- (methylol) -1,3- propylene glycol Ether.

Preferably, the esters of acrylic acid reactive diluent be isobornyl acrylate, it is tridecyl acrylate, bicyclic One or more of pentadiene acrylate, Tricyclodecane Dimethanol diacrylate.Polyurethane-modified organic siliconresin Middle quantum dot dispersion and fluorescence decay in different activities diluent is also different, finds in experimentation, quantum dot In isobornyl acrylate, tridecyl acrylate, dicyclopentadiene acrylate, Tricyclodecane Dimethanol diacrylate Dispersity is good in, can obtain stable homogeneous solution, and the decaying of glue film fluorescent brightness is also few.It is further preferred that described Esters of acrylic acid reactive diluent is isobornyl acrylate and/or dicyclopentadiene acrylate.

Preferably, the photoacid generator is 4- isobutyl phenenyl -4'- aminomethyl phenyl iodine hexafluorophosphate (IRGACURE 250), diphenyl-(4- phenyl sulphur) phenyl sulfonium hexafluorophosphate (GR-SS-002), bis- (4,4'- thioether triphenyl sulphur) hexafluoros One of mixture (UVI 6976) of stibate and diphenyl-(4- phenyl sulphur) phenyl sulfonium hexafluoro antimonate is a variety of.Its In, UVI 6976 is the mixture containing part triaryl sulfonium salts dimer, and is dissolved in the solution in propene carbonate, Concentration is 50wt.%

Preferably, the photosensitizer be 2- isopropyl thioxanthone (ITX), camphorquinone (CM), one in cumarin (CQ) Kind is a variety of.

Preferably, the free radical photo-initiation be 2- hydroxy-2-methyl -1- phenyl -1- acetone (Darocur 1173), 1- hydroxy-cyclohexyl phenyl ketone (Irgacure 184), benzoin dimethylether (Irgacure 651), bis- (the 2,4,6- front threes of phenyl One or more of base benzoyl) phosphine oxide (Irgacure 819).

The preparation method of the quantum dot package specific sealant, includes the following steps: to mix component A with B component Uniformly up to the quantum dot package specific sealant.Quantum dot package specific sealant described herein is without using appointing What auxiliary agent mixes component A and B component.

Compared with prior art, the invention has the benefit that present invention uses special silicon-modified epoxy trees Rouge and polyurethane-modified organic siliconresin make the sealant prepared have high water proof oxygen barrier property, excellent light fastness aging Can, free radical-cationic hybrid UV-curing technology is used in sealing material, gives full play to free radical and cationic photopolymerization is solid The advantages of change system, effectively avoids respective disadvantage, and imparting sealing material curing rate is fast, property regulation space is big, solid Change the advantages that shrinking percentage is small, adhesive force is strong.

Detailed description of the invention

Fig. 1 is the infrared spectrum of modifying epoxy resin by organosilicon.

Fig. 2 is the infrared spectrum of polyurethane-modified organic siliconresin.

Specific embodiment

The embodiment of the present invention only for illustration, is not considered as limiting the invention.

Raw material used in following embodiment if not otherwise indicated, uniform ordinary commercial products.

Modifying epoxy resin by organosilicon described in following embodiment is Pai Lema EP550, and laboratory prepared on a small scale Journey is as follows:

(1) one is added in 250ml four round flask (being furnished with spherical condensation tube, thermometer, nitrogen tube, dropping funel) Quantitative UVR-6100, four (dimethyl silicon substrate) ortho-silicates (si-h bond and unsaturated double-bond ratio be 1 ︰ 1.1) and 30ml first The chloroplatinic acid-catalysis agent solution prepared is added when temperature is 30 DEG C and 50 DEG C (in advance twice for benzene, after mixing stirring heating Chloroplatinic acid is dissolved with isopropanol), it is reacted under the conditions of 75 DEG C, is sampled every certain time and carry out FTIR test, double bond in spectrogram It is reaction end that characteristic absorption peak (1637-1640cm-1), which disappears, obtains epoxy-modified containing hydrogen silicone oil；

(2) one is added in 250ml four round flask (being furnished with spherical condensation tube, thermometer, nitrogen tube, dropping funel) The mixed solution of quantitative above-mentioned epoxy-modified containing hydrogen silicone oil and toluene, vinyl silicon is dropped evenly with dropping funel into system The mixed solution of oily (Mn=1000~2000) and toluene, be added a certain amount of catalyst chloroplatinic acid and hydroquinone of polymerization retarder into Row reacts, and 4~5h is reacted under the conditions of 75 DEG C~85 DEG C, discharging is cooled to room temperature, obtains modifying epoxy resin by organosilicon, wherein urging Agent chloroplatinic acid dosage is the 0.3% of reaction monomers quality, and polymerization inhibitor is the 0.1% of monomer mass, in vinyl silicone oil not It is saturated n (Si-H) ︰ n (C=C)=1.0 ︰ 1.1 of double bond and epoxy-modified containing hydrogen silicone oil.

The infrared spectrum of prepared modifying epoxy resin by organosilicon is shown in Fig. 1.Have Fig. 1 it is found that double bond stretching vibration peak All vanish from sight with the stretching vibration peak of C-H in double bond, and the characteristic peak and Si- of Si-C, Si-O, epoxy has occurred OCH₃The characteristic peak and 2920cm of middle C-H^-1Methylene stretching vibration absworption peak is inhaled at place, thus proves silicon-modified epoxy tree Rouge is successfully prepared.

Polyurethane-modified organic siliconresin group is happy Ma PU2386 described in following embodiment, and laboratory prepares on a small scale Process is as follows:

The α that will be measured, alpha, omega-dihydroxy polydimethyl siloxane, polyethylene glycol 400, isophorone diisocyanate (control N (NCO) ︰ n (OH)=4 ︰ 1) processed sequentially adds in the four-hole boiling flask with reflux condensing tube, and starting blender stirring, oil bath adds Heat；Catalyst DBTDL, the 3~4h of insulation reaction after being to slowly warm up to 60~65 DEG C of 0.05% (mass fraction) are added at 40 DEG C, Using the isocyanate content in di-n-butylamine method monitoring system, when it reaches 5%~8%, HEA is added dropwise, and (control is surplus Remaining n (NCO) ︰ n (OH)=1: 1.1~1.2) progress end capping reaction, 40 DEG C of dropping temperature, time for adding 0.5h, after being added dropwise (75 ± 2) DEG C insulation reaction is to slowly warm up to isocyanate groups end of reaction, obtains the organic silicon polyurethane of double bond sealing end Resin.

The infrared spectrum of prepared polyurethane-modified organic siliconresin is shown in Fig. 2.As shown in Figure 2, do not occur in spectrogram 2270cm^-1- NCO the characteristic peak at place illustrates not have in system to occur free-NCO group；809cm^-1The C=C occurred that The infrared signature absorption peak of unsaturated double-bond illustrates to be successfully connected photo curable C=C on polymer molecular chain；1542cm^-1Place Absorption peak be N-H plain bending vibration peak；1042cm^-1The peak that place occurs is the stretching vibration absworption peak of Si-O-Si； 3361cm^-1The absorption peak at place is the stretching vibration peak of N-H on carbamate；1730cm^-1The absorption peak at place belongs to C=O's Stretching vibration；2957cm^-1It is nearby the stretching vibration peak for being saturated C-H, illustrates to contain-CH in polymer₃,-CH₂-；1456cm^-1 There is absorption to illustrate to contain phenyl ring in polymer, it follows that polymerization is originated in expected structure.