CN104830025B - LED inorganic-organic hybrid composite encapsulation material and preparation method thereof - Google Patents
LED inorganic-organic hybrid composite encapsulation material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of light emitting diode (LED) sealing materials, and discloses an LED inorganic-organic hybrid composite encapsulation material and a preparation method thereof. The encapsulation material comprises the following components in parts by weight: 0.001 to 50 parts of organic silicon-fluorine random copolymer, 0.01 to 5 parts of modified nano SiO2, 0 to 100 parts of epoxy resin, 10 to 150 parts of curing agent, 0.1 to 2.0 parts of promoter, and 0.1 to 20 parts of auxiliary agent. The adopted organic silicon-fluorine random copolymer has excellent transparency, hydrophobicity, surface properties such as anti-fouling performance, etc., and mechanical properties such as tensile performance, and the like. The dispersibility of the modified nano SiO2 is improved, thus the viscosity is enhanced, and the toughness is prominently strengthened. Moreover, aliphatic epoxy resin without any phenyl ring is used, so the ultraviolet aging resistant performance of the expoxy resin is excellent, the thermal deformation temperature is high, and the hygroscopic property is weak. Thus the obtained composite encapsulation material has a better ultraviolet aging resistant performance, excellent mechanical properties, and surface properties.
Description
Technical field
The invention belongs to emitting semiconductor encapsulant technical field, it is combined particularly to a kind of led inorganic-organic hybrid
Encapsulating material and preparation method thereof.
Background technology
Coal, oil, natural gas etc. widely use the modernization having promoted World Economics.But in 21 century, these
The energy quickly consumes so that energy problem becomes one of problem of various countries' overriding concern.The appearance of semiconductor lighting, is one
Very promising high-tech area.Light emitting diode (led), as a kind of solid state light emitter, has light colour purity, and energy consumption is low, the life-span
Long the features such as, therefore it is referred to as " solid-state illumination " energy of led green.
Led is made up of chip, wire, support, conducting resinl, encapsulating material etc..The encapsulating material being currently mainly used has
Epoxy resin and organosilicon.Wherein, epoxy resin has excellent caking property, electrical insulating property, sealing and dielectricity, Er Qiecheng
This is low, formula is flexible and changeable, easy-formation, production efficiency are high, is the mainstay material of the encapsulation such as led, electronic device and integrated circuit.
In cycloaliphatic epoxy resin, epoxy radicals are connected directly between on alicyclic ring, after can forming close rigid molecular structure so that solidifying
Material there is higher heat distortion temperature, and, do not contain phenyl in molecule, therefore there is good ultraviolet aging resistance
Can, but simultaneously, the internal stress producing in solidification process also makes other performance, and as poor in mechanical property, index of refraction is low.Gu and,
During change, there is great amount of hydroxy group to produce, having considerable influence to anti humility performance, thus affecting encapsulation performance.
Organosilicon has the advantages that thermally-stabilised good (si-o bond energy is big), resistance to oxidation, weather-proof, low temperature flexibility are good.With epoxy
Resin has complementarity in performance, can be used for modified epoxy to increase the performances such as the toughness of epoxy resin.Organic fluoride material
C-f key in material has the characteristics that dipole moment is little, degree of polarization is low, and fluoro-containing group has the characteristic of hydrophobic oleophobic, so
Organic fluorine material is carried out modified epoxy, the dielectric constant reducing encapsulating material and water absorption rate can be played, improve its surface
Performance.Inorganic nano-particle has high index of refraction, and may also function as improving encapsulating material crosslinking points, and the mechanics of lifting encapsulation is strong
Degree.But it is poor with epoxy resin compatibility that three of the above filler all there is a problem of, such as simple interpolation is it may occur that reunite and base
Body produces the problem of split-phase, so that producing impact to the light transmittance of prepared led encapsulating material, mechanical property.
Content of the invention
In order to overcome shortcoming and the deficiency of above-mentioned prior art, the primary and foremost purpose of the present invention is to provide a kind of led inorganic
Organic hybrid composite encapsulating material.The present invention passes through to introduce cycloaliphatic epoxy groups in organosilicon fluorine material, simultaneously using band
The silane coupler having cycloaliphatic epoxy groups is to nanometer sio2It is modified, then compound modification of epoxy resin, obtain is compound
Encapsulating material effectively improves toughness, index of refraction, the absorptive compatibility simultaneously improving with cycloaliphatic epoxy resin matrix.
Another object of the present invention is to provide a kind of preparation method of above-mentioned led inorganic-organic hybrid composite encapsulating material.
The purpose of the present invention is realized by following proposal:
A kind of led inorganic-organic hybrid composite encapsulating material, including following components by weight:
The formula of described organic silicon-fluorine random copolymer is as shown in Equation 1:
Wherein: described rfFor fluoric ether, preferably-ch2cf3、-ch2cf2chfcf3、-ch2(cf2)2cf3、-ch2
(cf2)5chf2、-(ch2)2(cf2)5cf3、-ch2(cf2)6cf3, or-ch2(cf2)8cf3；Described r1、r2、r3、r4Can identical or
Different is respectively-h or-ch3；r5For-cnh2n+1, wherein n is 1～17 integer；r6For-coo (ch2)3si(och3)3、-si
(och3)3、-si(och2ch3)3、-si[oc(och3)3]3、-si(oc2h4och3)3Or-sich3(och3)2；
Described r is
In the led inorganic-organic hybrid composite encapsulating material of the present invention, described organic silicon-fluorine random copolymer is by including
The method of following steps prepares:
By 0.01～40 mass parts fluoro-acrylate monomer, 0～50 mass parts cycloaliphatic vinyl epoxy monomer, 0.01～
20 mass parts alkyl acrylates, 0.01～20 part of vinyl silanes and 80～250 mass parts organic solvent a mixing, are heated to
60～100 DEG C, add 0.01～50 part of initiator, react 3～9h, obtain organic silicon-fluorine random copolymer.
Described fluoro-acrylate monomer can be (methyl) acrylic acid trifluoro ethyl ester, (methyl) hexafluorobutyl acrylate, first
Base acrylic acid -2,2,3,3,4,4,4- seven fluoro-butyl ester, (methyl) dodecafluorhe-ptylacrylate, (methyl) acrylic acid ten trifluoro
Monooctyl ester, methacrylic acid -1h, 1h- perfluoro monooctyl ester and 1h, at least one in 1h- perfluor positive decyl acrylate.
Described cycloaliphatic vinyl epoxy monomer can be 3,4- epoxycyclohexyl-methyl methacrylate3,4- epoxycyclohexyl-methyl acrylateWith 4- vinyl epoxy ring
HexaneIn at least one.
Described alkyl acrylate preferably (methyl) acrylic acid methyl ester., ethyl methacrylate, methacrylic acid is different
In propyl ester, n-BMA, isobutyl methacrylate, n octyl methacrylate and 2-Propenoic acid, 2-methyl-, isooctyl ester
At least one.
Described vinyl silanes can be vinyltrimethoxy silane, VTES, vinyl three (2-
Methoxy ethoxy) silane, at least one in methylvinyldimethoxysilane and vinyl tri-tert silane.
Described organic solvent a is preferably oxolane, butanone, ethanol, hexamethylene, toluene, glycol dimethyl ether, isopropyl
At least one in alcohol, 1,4- dioxane and ethyl acetate.
The effect of described initiator be cause fluoro-acrylate monomer, vinyl epoxy monomer, alkyl acrylate and
There is Raolical polymerizable in vinyl silanes, its consumption is catalytic amount, preferably reaction system solid content
0.01～5%.
Described initiator can be azo-initiator or organic peroxy class initiator；It is preferably azo-bis-isobutyl cyanide
(aibn), at least in 2,2'-Azobis(2,4-dimethylvaleronitrile) (abvn), benzoyl peroxide, dilauroyl peroxide and di-t-butyl peroxide
Kind.
Described initiator can first take a small amount of organic solvent a to be formulated as solution and add in reaction system.
Above-mentioned reaction is preferably nitrogen atmosphere, carries out under the conditions of mechanical agitation (500rpm).
Described initiator is preferably gradually added at twice.
After above-mentioned reaction terminates, preferably by product under the conditions of 60～100 DEG C revolving 10～30min to remove solvent
And by-product, obtain product after purification.
In the led inorganic-organic hybrid composite encapsulating material of the present invention, described modified Nano sio2Walked by below including
Rapid method prepares:
By nanometer sio250 mass parts, aliphatic ring TMOS monomer 0.1～50 mass parts, catalyst a0.05～10
Mass parts, the mixing of organic solvent b500～1000 part, 30～120 DEG C of stirring reaction 1～10h obtain modified Nano sio2.
Described nanometer sio2It is preferably gas phase nano sio2, particle diameter is 10～100nm.
Described aliphatic ring TMOS monomer can be oc6h9(ch2)2si(och3)3、oc6h9(ch2)2si
(och2ch3)3And oc6h9(ch2)2sioch3(och2ch3)2In at least one.
Described organic solvent b can be ethanol, 1,4- dioxane, toluene, dimethylbenzene, ethyl acetate or acetonitrile.
Described catalyst a can for phosphoric acid, hydrochloric acid, sulphuric acid, acetic acid, dibutyl tin acetate, dibutyl tin dilaurate,
At least one in Tetramethylammonium hydroxide, stannous octoate, butter of tin and TBAH.
After above-mentioned reaction terminates, purification can be carried out to product, system after reaction be carried out cooling down, sucking filtration, with 10～50 matter
Amount part dehydrated alcohol cyclic washing 3～5 times, dries 5～10h at 80～110 DEG C, obtains product after purification.
In the led inorganic-organic hybrid composite encapsulating material of the present invention, described epoxy resin is cycloaliphatic epoxy resin,
Wherein it is preferably model erl-4221, erl-4234, at least one in erl-4206 and erl-4299.
Described firming agent is acid anhydride type curing agent, preferably phthalic anhydride (pa), hexamethylene three anhydride (h-
Tman), carbic anhydride (na), methylnadic anhydride (mna), hexahydro phthalic anhydride (hhpa), methyl hexahydrobenzene
Acid anhydride (mhhpa), 4- methyl hexahydrophthalic anhydride (4-mhhpa), THPA (thpa), 4- methyl tetrahydro phthalic anhydride (4-mthpa), 12
At least one in alkenyl succinic anhydride (ddsa) and poly- Azelaic Acid acid anhydride (papa).
Described accelerator can be quaternary ammonium salt accelerator or tertiary amines accelerator, and wherein preferably quaternary ammonium salt promotes
Agent, more preferably tetrabutyl ammonium bromide (tbab), cetyl trimethylammonium bromide (ctab) and trimethyl bromination
At least one in ammonium (dtab).
Described auxiliary agent is this area conven-tional adjuvants, it may include reinforcing agent, defoamer, antioxidant, light diffusing agent and
At least one in UV absorbent.
Described reinforcing agent is preferably at least one in gas-phase silica and mq silicones.
Described defoamer is preferably organic silicon defoamer.
Described antioxidant is preferably phosphite antioxidant.
Described light diffusing agent is preferably organosilicon diffusant.
Described UV absorbent is preferably benzophenone, benzotriazole or hindered amine UV absorbent.
The present invention also provides a kind of preparation method of above-mentioned led inorganic-organic hybrid composite encapsulating material, has including following
Body step:
By 0.001～50 mass parts organic silicon-fluorine random copolymer, modified nanometer sio of 0.01～5 mass parts2Add 0
In～100 mass parts cycloaliphatic epoxy resins, stir, add 10～150 mass parts firming agent, 0.1～2.0 mass parts to promote
Enter agent and 0.1～20 mass parts auxiliary agent, continue stirring 0.5～3h, vacuum defoamation, 70～100 DEG C of precuring 1 under vacuum
～3h, then at 110～140 DEG C of solidification 2～6h of vacuum, solidifies 2～6h after 150～180 DEG C, obtains led inorganic-organic hybrid
Composite encapsulating material.
Described vacuum defoamation is 3 × 10 preferably in vacuum3Carry out under the conditions of pa.
The present invention, with respect to prior art, has such advantages as and beneficial effect:
(1) present invention passes through radical polymerization, cycloaliphatic epoxy groups is introduced in organic silicon-fluorine random copolymer, overcomes
Easily there is the problem being separated in cycloaliphatic epoxy resin and organic silicon-fluorine, participate in epoxy matrix solidification in the curing process simultaneously
Reaction, in the premise ensureing light transmittance, significantly improves the mechanical properties such as the surface propertys such as hydrophobicity, anti-soil and stretching.
(2) present invention by have cycloaliphatic epoxy groups silane coupler modified after nanometer sio2, its dispersibility
It is improved, and introduces si-o-si key in structure, so that caking property strengthens, toughness is obviously improved.
(3) select the cycloaliphatic epoxy resin without phenyl ring in molecular structure in the present invention, there is ultra-violet absorption amount low
Feature, and then show good anti-ultraviolet ageing performance.And there is higher heat distortion temperature and agent of low hygroscopicity.And have
Machine fluosilicic material and nanometer sio2After hybridization compounding, there is more preferable resistance to UV aging and mechanical property, surface property etc..
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention not limited to this.
Embodiment 1
(1) preparation of organic silicon-fluorine random copolymer
By 20g trifluoroethyl methacrylate (ch2=c (ch3)cooch2cf3), 1g 3,4- epoxycyclohexyl-methyl third
Olefin(e) acid ester1g vinyltrimethoxy silane, 2g ethyl methacrylate and 35ml toluene composition
Mixing liquid is added in reactor, and in nitrogen atmosphere, mechanical agitation (500rpm) is heated to 90 DEG C, treats temperature constant, to anti-
Answer and in device, add dibenzoyl peroxide (bpo) toluene solution that 7.5ml concentration is 0.09g/ml, after reaction 1h, then to reaction
Add dibenzoyl peroxide (bpo) toluene solution that 2.5ml concentration is 0.09g/ml in device, continue reaction 3h, question response is tied
Shu Hou, in 90 DEG C of revolvings 20min, removes solvent, by-product, obtains organic silicon-fluorine random copolymer.
(2) modified Nano sio2Preparation method
By nanometer sio250g、oc6h9(ch2)2si(och3)320g, catalyst a acetic acid 1g, toluene 700ml are sufficiently mixed all
After even, at 70 DEG C, under mechanical agitation (700rpm), react 3h, cool down sucking filtration, with 50ml dehydrated alcohol cyclic washing 3 times, 100
Dry 10h at DEG C, obtain modified Nano sio2.
(3) preparation of led inorganic-organic hybrid composite encapsulating material
The modified Nano that organic silicon-fluorine random copolymer that 0.2g step (1) is prepared, 1g step (2) prepare
sio2Add in 100g cycloaliphatic epoxy resin erl-4299, after stirring, add 60g epoxy hardener 4- methyl four
The mixed liquor of hydrogen phthalic anhydride (4-mthpa), 0.5g accelerator tetrabutyl ammonium bromide (tbab) and 1g gas-phase silica reinforcing agent, continues
After stirring 1h, it is 3 × 10 in vacuum3Carry out vacuum defoamation under the conditions of pa, be 1 × 10 in 100 DEG C and vacuum4Under the conditions of pa
Precuring 2h, then by 130 DEG C of solidification 6h, the program curing of 170 DEG C of solidification 5h is solidified, and finally gives water white led
Inorganic-organic hybrid composite encapsulating material.
Embodiment 2
(1) preparation of organic silicon-fluorine random copolymer
By 20g Hexafluorobutyl mathacrylate (ch2=c (ch3)cooch2cf2chfcf3), 3g 3,4- epoxycyclohexyl first
Methyl acrylate2g VTES, 3g butyl methacrylate and 40ml have
Machine solvent a1, the mixing liquid of 4- dioxane composition is added in reactor, in a nitrogen atmosphere, mechanical agitation (500rpm)
It is heated to 75 DEG C, treats temperature constant, add the azo-bis-isobutyl cyanide (aibn) 1 that 12ml concentration is 0.07g/ml in reactor,
4- dioxane solution, after reaction 1h, then adds the azo-bis-isobutyl cyanide (aibn) that 4ml concentration is 0.07g/ml in reactor
Isosorbide-5-Nitrae-dioxane solution, continues reaction 3h, after question response terminates, in 80 DEG C of revolvings 20min, removes solvent, by-product, obtains
Organic silicon-fluorine random copolymer.
(2) modified Nano sio2Preparation method
By nanometer sio250g、oc6h9(ch2)2si(och2ch3)318g, catalyst a phosphoric acid 7g, organic solvent b toluene
After 800ml is sufficiently mixed uniformly, under 60 DEG C of mechanical agitation (800rpm), react 3h, cool down sucking filtration, anti-with 50ml dehydrated alcohol
After backwashing is washed 3 times, dries 8h, obtain modified Nano sio at 110 DEG C2.
(3) preparation of led inorganic-organic hybrid composite encapsulating material
The modified Nano that organic silicon-fluorine random copolymer that 2g step (1) is prepared, 2g step (2) prepare
sio2Add in 100g cycloaliphatic epoxy resin erl-4221, after stirring, add 90g epoxy hardener 4- methyl six
Hydrogen phthalic anhydride (4-mhhpa), 0.45g accelerator Dodecyl trimethyl ammonium chloride (dtab) and 2g O-hydroxyl-diphenyl ketone ultraviolet
The mixed liquor of absorbent, after continuing stirring 2h, is 3 × 10 in vacuum3Carry out vacuum defoamation, in 90 DEG C and vacuum under the conditions of pa
Spend for 2 × 103Pa precuring 3h, by 130 DEG C, 6h, then at 180 DEG C, 4h program curing is solidified, and finally gives water white transparency
Led inorganic-organic hybrid composite encapsulating material.
Embodiment 3
(1) preparation of organic silicon-fluorine random copolymer
By 16g methacrylic acid -2,2,3,3,4,4,4- seven fluoro-butyl ester (ch2=c (ch3)cooch2(cf2)2cf3)、
8g 4 vinyl epoxy cyclohexane1.5g vinyl three (2- methoxy ethoxy) silane, 3.2g methyl
The mixing liquid of Isobutyl 2-propenoate and 40ml organic solvent a dimethylbenzene composition is added in reactor, in a nitrogen atmosphere, machine
Under the conditions of tool stirring (500rpm), it is heated to 85 DEG C, treats temperature constant, add 12ml concentration to be 0.05g/ml's in reactor
Dibenzoyl peroxide (bpo) xylene solution, after reaction 1h, then adds the mistake that 4ml concentration is 0.05g/ml in reactor
Oxidation dibenzoyl (bpo) xylene solution, continues reaction 3h, after question response terminates, in 90 DEG C of revolvings 10min, remove solvent,
By-product, obtains organic silicon-fluorine random copolymer.
(2) modified Nano sio2Preparation method
By nanometer sio250g、oc6h9(ch2)2sioch3(och2ch3)225g, catalyst a Tetramethylammonium hydroxide 4.5g,
After organic solvent b ethanol 850ml is sufficiently mixed uniformly, under 60 DEG C of mechanical agitation (900rpm), react 2h, cool down sucking filtration, use
50ml dehydrated alcohol cyclic washing 3 times, dries 9h at 100 DEG C, obtains modified Nano sio2.
(3) preparation of led inorganic-organic hybrid composite encapsulating material
The modification that organic silicon-fluorine random copolymer that 15g step (1) is prepared, 1.5g step (2) prepare is received
Rice sio2Add in 100g cycloaliphatic epoxy resin erl-4234, after stirring, add 100g epoxy hardener tetrahydrochysene
Anhydride phthalic acid (thpa), 0.6g accelerator cetyl trimethylammonium bromide (ctab) and 0.5g sta-338 phosphite ester resist
The mixed liquor of oxygen agent, after continuing stirring 2h, is 3 × 10 in vacuum3Carry out vacuum defoamation, in 80 DEG C and vacuum under the conditions of pa
For 1 × 104Pa precuring 3h, by 140 DEG C, 6h, then at 180 DEG C, 4h program curing is solidified, and finally gives water white
Led inorganic-organic hybrid composite encapsulating material.
Embodiment 4
(1) preparation of organic silicon-fluorine random copolymer
By 14g dodecafluoroheptyl methacrylate (ch2=c (ch3)cooch2(cf2)5chf2), 8.4g3,4- epoxy hexamethylene
Methyl acrylate2g methylvinyldimethoxysilane, 0.7g 2-Propenoic acid, 2-methyl-, isooctyl ester
And the mixing liquid of 35ml organic solvent a butanone composition is added in reactor, in nitrogen atmosphere, mechanical agitation (500rpm) adds
Heat, to 70 DEG C, treats temperature constant, adds 2,2'-Azobis(2,4-dimethylvaleronitrile) (abvn) butanone that 7.5ml concentration is 0.07g/ml in reactor
Solution, after reaction 1h, then 2,2'-Azobis(2,4-dimethylvaleronitrile) (abvn) butanone adding 2.5ml concentration to be 0.07g/ml in reactor is molten
Liquid, continues reaction 3h, after question response terminates, in 70 DEG C of revolvings 20min, removes solvent, by-product, obtains organic silicon-fluorine randomly altogether
Polymers.
(2) modified Nano sio2Preparation method
By nanometer sio250g、oc6h9(ch2)2si(och3)316g, catalyst a butter of tin 0.5g, organic solvent b ethanol
After 600ml is sufficiently mixed uniformly, under 70 DEG C of mechanical agitation (700rpm), react 3h, cool down sucking filtration, anti-with 50ml dehydrated alcohol
After backwashing is washed 3 times, dries 9h, obtain modified Nano sio at 100 DEG C2.
(3) preparation of led inorganic-organic hybrid composite encapsulating material
The modified Nano that organic silicon-fluorine random copolymer that 8g step (1) is prepared, 2g step (2) prepare
sio2Add in 100g cycloaliphatic epoxy resin erl-4234, after stirring, add 80g epoxy hardener hexahydro adjacent
Phthalate anhydride (hhpa), 0.4g accelerator tetrabutyl ammonium bromide (tbab) and 1.5g 2-PHENYLBENZIMIDAZOLE-5-SULFONIC ACID ultraviolet
The mixed liquor of light absorbers, after continuing stirring 1h, is 3 × 10 in vacuum3Carry out vacuum defoamation under the conditions of pa, in 100 DEG C and
Vacuum 1000pa is precuring 2h, by 130 DEG C, 4h, then at 160 DEG C, 5h program curing is solidified, and finally gives colourless
Bright led inorganic-organic hybrid composite encapsulating material.
Embodiment 5
(1) preparation of organic silicon-fluorine random copolymer
By 10g methacrylic acid ten trifluoro monooctyl ester (ch2=c (ch3)coo(ch2)2(cf2)5cf3), 10g3,4- epoxide ring
Hexyl methyl methacrylate3g vinyl tri-tert silane, 0.5g 1-Octyl acrylate and
The mixing liquid of 30ml organic solvent a hexamethylene composition is added in reactor, in nitrogen atmosphere, mechanical agitation (500rpm) bar
It is heated to 70 DEG C under part, treats temperature constant, add the dilauroyl peroxide that 7.5ml concentration is 0.08g/ml in reactor
(lpo) cyclohexane solution, after reaction 1h, then adds the dilauroyl peroxide that 2.5ml concentration is 0.08g/ml in reactor
(lpo) cyclohexane solution, continues reaction 3h, after question response terminates, in 80 DEG C of revolvings 15min, removes solvent, by-product, obtains
Organic silicon-fluorine random copolymer.
(2) modified Nano sio2Preparation method
By nanometer sio250g、oc6h9(ch2)2si(och2ch3)325g, catalyst a dibutyl tin dilaurate 0.06g, have
After machine solvent b dimethylbenzene 900ml is sufficiently mixed uniformly, under 50 DEG C of mechanical agitation (800rpm), react 3h, cool down sucking filtration, use
50ml dehydrated alcohol cyclic washing 3 times, dries 7h at 110 DEG C, obtains modified Nano sio2.
(3) preparation of led inorganic-organic hybrid composite encapsulating material
The modified Nano that organic silicon-fluorine random copolymer that 15g step (1) is prepared, 3g step (2) prepare
sio2Add in 100g cycloaliphatic epoxy resin erl-4221, after stirring, add 120g epoxy hardener methyl to receive
Dick anhydride (mna), 0.6g accelerator Dodecyl trimethyl ammonium chloride (dtab) and 2g triphenyl phosphite antioxidant mixed
Close liquid, after continuing stirring 1h, be 3 × 10 in vacuum3Carry out vacuum defoamation, in 90 DEG C and vacuum 3 × 10 under the conditions of pa4pa
For precuring 3h, by 120 DEG C, 4h, then at 170 DEG C, 5h program curing is solidified, and finally gives water white led inorganic
Organic hybrid composite encapsulating material.
Embodiment 6
(1) preparation of organic silicon-fluorine random copolymer
By 15g hexafluorobutyl acrylate (ch2=chcooch2cf2chfcf3), 22.5g 4 vinyl epoxy cyclohexane1g vinyltrimethoxy silane, 4.5g isopropyl methacrylate and 60ml organic solvent a ethanol group
The mixing liquid becoming is added in reactor, in a nitrogen atmosphere, under the conditions of mechanical agitation (500rpm), is heated to 70 DEG C, treats
Temperature constant, adds 2,2'-Azobis(2,4-dimethylvaleronitrile) (abvn) ethanol solution that 15ml concentration is 0.06g/ml in reactor, reacts 1h
Afterwards, add 2,2'-Azobis(2,4-dimethylvaleronitrile) (abvn) ethanol solution that 5ml concentration is 0.06g/ml then in reactor, continue reaction 3h,
After question response terminates, in 70 DEG C of revolvings 20min, remove solvent, by-product, obtain organic silicon-fluorine random copolymer.
(2) modified Nano sio2Preparation method
By nanometer sio250g、oc6h9(ch2)2sioch3(och2ch3)215g, catalyst a stannous octoate 2g, organic solvent b
After ethanol 600ml is sufficiently mixed uniformly, under 60 DEG C of magnetic agitation, react 3h, cool down sucking filtration, repeatedly washed with 30ml dehydrated alcohol
Wash 3 times, dry 7h at 100 DEG C, obtain modified Nano sio2.
(3) preparation of led inorganic-organic hybrid composite encapsulating material
The modified Nano that organic silicon-fluorine random copolymer that 25g step (1) is prepared, 1g step (2) prepare
sio2Add in 100g cycloaliphatic epoxy resin erl-4299, after stirring, add 130g epoxy hardener laurylene
Base succinic anhydrides (ddsa), 0.7g accelerator cetyl trimethylammonium bromide (ctab) and 2.5g triphenyl phosphite antioxidant
Mixed liquor, continue stirring 1h after, vacuum be 3 × 103Carry out vacuum defoamation under the conditions of pa, be 5 in 100 DEG C and vacuum
×103Pa precuring 3h, by 150 DEG C, 4h, then at 170 DEG C, 4h program curing is solidified, and finally gives water white led
Inorganic-organic hybrid composite encapsulating material.
Effect example
The led inorganic-organic hybrid composite encapsulating material that embodiment 1～6 is prepared carries out performance test, and result is shown in
Table 1.Wherein, the method for the performance of test material or standard are as follows:
(1) refractive index is tested using the zwa type Abbe refractometer of Shanghai optical instrument factory；
(2) light transmittance is tested using the uv8000 ultraviolet-uisible spectrophotometer of Shanghai Yuan Xi Instrument Ltd.,
Thickness of sample is 3mm, and the scope of scanning wavelength is 280～800nm, chooses the absorbance at 800nm and 400nm and is compared；
(3) contact angle test adopts jc2000d contact angle/interfacial tension measuring instrument, is carried out using angulation analysis sessile drop method
Test；
(4) water absorption rate is tested with reference to method shown in gb1034-86, and before test, sample is first dried 24h to matter at 50 DEG C
Amount is constant, soaks 24h and measure relative water-intake rate in boiling water；
(5) hardness reference standard jb 6148-92 is tested using Shore durometer d；
(6) tensile strength test reference standard is astm d638-08, using Rui Geer Instrument Ltd. of Shenzhen
Rgm-3030 type electronic universal tester is tested, and takes 5 sample tests to be averagely worth to.
(7) surface cohesive force records according to the method for testing of standard astm c3359-b.
The performance indications of table 1led inorganic-organic hybrid composite encapsulating material
As it can be seen from table 1 it is the index of refraction of led inorganic-organic hybrid composite encapsulating material of the present invention, contact angle, water-fast
Property, tensile property can be adjusted by different proportionings and reaction condition, you can prepare required difference by above means
The led encapsulating material of performance, obtains having the led encapsulating material of mechanical property, excellent in optical properties concurrently.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not subject to above-described embodiment
Limit, other any spirit without departing from the present invention and the change made under principle, modification, replacement, combine, simplify,
All should be equivalent substitute mode, be included within protection scope of the present invention.
Claims (9)
1. a kind of led inorganic-organic hybrid composite encapsulating material is it is characterised in that include following components by weight:
The formula of described organic silicon-fluorine random copolymer is as shown in Equation 1:
Wherein: described rfFor fluoric ether, for-ch2cf3、-ch2cf2chfcf3、-ch2(cf2)2cf3、-ch2(cf2)5chf2、-
(ch2)2(cf2)5cf3、-ch2(cf2)6cf3, or-ch2(cf2)8cf3；Described r1、r2、r3、r4The difference that may be the same or different
For-h or-ch3；r5For-cnh2n+1, wherein n is 1～17 integer；r6For-coo (ch2)3si(och3)3、-si(och3)3、-si
(och2ch3)3、-si[oc(och3)3]3、-si(oc2h4och3)3Or-sich3(och3)2；
Described r is
2. led inorganic-organic hybrid composite encapsulating material according to claim 1 is it is characterised in that described organic silicon-fluorine
Random copolymer is prepared by the method comprising the following steps:
By 0.01～40 mass parts fluoro-acrylate monomer, 0～50 mass parts cycloaliphatic vinyl epoxy monomer, 0.01～20 matter
Amount part alkyl acrylate, 0.01～20 part of vinyl silanes and 80～250 mass parts organic solvent a mixing, it is heated to 60～
100 DEG C, add 0.01～50 part of initiator, react 3～9h, obtain organic silicon-fluorine random copolymer；Described cycloaliphatic vinyl
Epoxy monomer consumption is not 0.
3. led inorganic-organic hybrid composite encapsulating material according to claim 2 it is characterised in that: described fluorine-containing third
Acrylic monomer is (methyl) acrylic acid trifluoro ethyl ester, (methyl) hexafluorobutyl acrylate, methacrylic acid -2,2,3,3,4,4,4-
Seven fluoro-butyl ester, (methyl) dodecafluorhe-ptylacrylate, (methyl) perluorooctyl acrylate, methacrylic acid -1h, 1h- is complete
Fluoro monooctyl ester and 1h, at least one in 1h- perfluor positive decyl acrylate；
Described cycloaliphatic vinyl epoxy monomer is 3,4- epoxycyclohexyl-methyl methacrylate, 3,4- epoxycyclohexyl
At least one in methacrylate and 4 vinyl epoxy cyclohexane；
Described alkyl acrylate is (methyl) acrylic acid methyl ester., ethyl methacrylate, isopropyl methacrylate, methyl
At least one in n-butyl acrylate, isobutyl methacrylate, n octyl methacrylate and 2-Propenoic acid, 2-methyl-, isooctyl ester；
Described vinyl silanes are vinyltrimethoxy silane, VTES, vinyl three (2- methoxyl group
Ethyoxyl) silane, at least one in methylvinyldimethoxysilane and vinyl tri-tert silane.
4. led inorganic-organic hybrid composite encapsulating material according to claim 2 it is characterised in that: described is organic molten
Agent a is oxolane, butanone, ethanol, hexamethylene, toluene, glycol dimethyl ether, isopropanol, 1,4- dioxane and acetic acid second
At least one in ester；
Described initiator be azo-initiator or organic peroxy class initiator, be azo-bis-isobutyl cyanide, 2,2'-Azobis(2,4-dimethylvaleronitrile),
At least one in benzoyl peroxide, dilauroyl peroxide and di-t-butyl peroxide.
5. led inorganic-organic hybrid composite encapsulating material according to claim 1 is it is characterised in that described modified Nano
sio2Prepared by the method comprising the following steps:
By nanometer sio250 mass parts, aliphatic ring TMOS monomer 0.1～50 mass parts, catalyst a 0.05～10 mass
Part, 500～1000 parts of mixing of organic solvent b, 30～120 DEG C of stirring reaction 1～10h obtain modified Nano sio2.
6. led inorganic-organic hybrid composite encapsulating material according to claim 5 it is characterised in that: described nanometer sio2
For gas phase nano sio2, particle diameter is 10～100nm；
Described aliphatic ring TMOS monomer is oc6h9(ch2)2si(och3)3、oc6h9(ch2)2si(och2ch3)3With
oc6h9(ch2)2sioch3(och2ch3)2In at least one；
Described organic solvent b is ethanol, 1,4- dioxane, toluene, dimethylbenzene, ethyl acetate or acetonitrile；
Described catalyst a is phosphoric acid, hydrochloric acid, sulphuric acid, acetic acid, dibutyl tin acetate, dibutyl tin dilaurate, tetramethyl
At least one in ammonium hydroxide, stannous octoate, butter of tin and TBAH.
7. led inorganic-organic hybrid composite encapsulating material according to claim 1 it is characterised in that: described asphalt mixtures modified by epoxy resin
Fat is cycloaliphatic epoxy resin；Described firming agent is acid anhydride type curing agent；Described accelerator be quaternary ammonium salt accelerator or
Tertiary amines accelerator；Described auxiliary agent is included in reinforcing agent, defoamer, antioxidant, light diffusing agent and UV absorbent extremely
Few one kind.
8. led inorganic-organic hybrid composite encapsulating material according to claim 1 it is characterised in that: described asphalt mixtures modified by epoxy resin
Fat is model erl-4221, erl-4234, at least one in erl-4206 and erl-4299；
Described firming agent is phthalic anhydride, hexamethylene three anhydride, carbic anhydride, methylnadic anhydride, hexahydro
Phthalic anhydride, methyl hexahydrophthalic anhydride, THPA, 4- methyl tetrahydro phthalic anhydride, dodecenylsuccinic anhydride and poly- Azelaic Acid
At least one in acid anhydride；
Described accelerator is in tetrabutyl ammonium bromide, cetyl trimethylammonium bromide and Dodecyl trimethyl ammonium chloride
At least one.
9. the preparation method of the led inorganic-organic hybrid composite encapsulating material described in a kind of any one according to claim 1～8,
It is characterized in that including step in detail below:
By 0.001～50 mass parts organic silicon-fluorine random copolymer, modified nanometer sio of 0.01～5 mass parts2Add 100 mass
In part cycloaliphatic epoxy resin, stir, add 10～150 mass parts firming agent, 0.1～2.0 mass parts accelerator and 0.1
～20 mass parts auxiliary agents, continuation stirring 0.5～3h, vacuum defoamation, 70～100 DEG C of precuring 1～3h under vacuum, then at
110～140 DEG C of solidification 2～6h of vacuum, solidify 2～6h after 150～180 DEG C, obtain led inorganic-organic hybrid composite package material
Material.
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