CN102702532A - Method for preparing organosilicone hybrid resin and power type encapsulating material for light-emitting diodes (LED) thereof and application - Google Patents

Method for preparing organosilicone hybrid resin and power type encapsulating material for light-emitting diodes (LED) thereof and application Download PDF

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CN102702532A
CN102702532A CN2012101777916A CN201210177791A CN102702532A CN 102702532 A CN102702532 A CN 102702532A CN 2012101777916 A CN2012101777916 A CN 2012101777916A CN 201210177791 A CN201210177791 A CN 201210177791A CN 102702532 A CN102702532 A CN 102702532A
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CN102702532B (en
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刘伟区
高南
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Guangzhou Chemical Co Ltd of CAS
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Abstract

The invention discloses a method for preparing organosilicone hybrid resin and a power type encapsulating material for light-emitting diodes (LED) thereof and application. According to the method, the organosilicone hybrid resin containing three functional groups of an epoxy group, a fluorin group and a phenyl group is prepared by a cohydrolysis condensation method, and the content of each group in the resin is optimized by controlling the ratios of fluoro alkyl silicane, epoxy alkyl silicane and phenyl silicane, so that the resin is applied to the power type encapsulating material for the LEDs. The prepared encapsulating material has the advantages of epoxy resin and organosilicone, has high performance of high light transmittance and refractive index, low hygroscopicity, high mechanical property and ageing-resistant performance and the like, and the problems of low light output rate, short service life and the like of the LEDs due to dropping caused by low bonding strength and poor mechanical property of the ordinary organosilicone material for encapsulating LEDs are solved. The method for preparing the organosilicone hybrid resin and the power type encapsulating material for the LEDs is simple, and raw materials are readily available and environment-friendly; and the organosilicone hybrid resin can also be used as the raw materials to be applied to processing and preparation of optical lens materials, photovoltaic conversion materials, integrated circuit encapsulating materials, insulating materials, coating materials, adhesives and the like.

Description

The preparation method and the application of a kind of organic-silicon hybridization resin and power LED packaged material thereof
Technical field
The invention belongs to emitting semiconductor packaged material field, be specifically related to the preparation method and the application of a kind of organic-silicon hybridization resin and power LED packaged material thereof.
Technical background
Since first red LED in 1962 come out, LED had passed through 40 years of development, and its packaged type has also successively experienced developmental stage such as stent-type, SMD, power-type LED.In recent years; Increase along with chip power; The demand of solid-state illumination technical development particularly; Optics, calorifics, electricity and physical construction etc. to LED encapsulation have proposed new, higher requirement, correspondingly require the packaged material of LED to have high refractive index, transmittance and thermal conductivity, low-stress and water absorbability, excellent heat-resisting and ultraviolet aging resistance performance etc., to improve optical output power and the work-ing life of LED.
At present, the packaged material used of LED mainly is epoxy resin and organosilicon material.Epoxy resin has excellent adhesiveproperties, electrical insulating property and dielectric properties; And characteristics such as cost is low, prescription is flexible, easy machine-shaping; Thereby used its longer in the past for some time as the LED packaged material; Shortcomings such as that but epoxy resin is prone to is aging, moisture absorption, variable color and property are crisp make it be only limited to lower powered LED packaged material, and can't be applied to the encapsulation of high-capacity LED.Compare with epoxy resin; Organosilicon material has then that transmittance height, Heat stability is good, stability to aging are excellent, internal stress is low and advantage such as water absorbability is little; The ideal that is present high-capacity LED packaged material is selected; But organosilicon material is when having above-mentioned advantage concurrently, has also that cementability is low, specific refractory power is little and shortcoming such as poor mechanical property.Thereby; Be coupling collar epoxy resins and organosilicon material advantage; The research worker has developed and can be used for power-type LED and use the epoxy organosilicon packaged material; Generally be through modifying epoxy resin by organosilicon, or silicone resin, silicone oil, Zylox etc. are carried out addition reaction of silicon with hydrogen with epoxy resin, prepare through curing molding again.Disclosing a kind of like the Japanese Patent that publication number is 2006225515, name is called " Optical semiconductor element sealing material therefore and sealing composition " is the packaged material that the mixture of solidifying agent cured epoxy modified polyorganosiloxane and aliphatics or alicyclic epoxide compound prepares with the acid anhydrides; This material have anti-UV photoaging, cold-resistant thermal shocking, high firmness and with the good characteristics of substrate bonding property, be fit to very much the blueness of the following wavelength glow peak of 500nm and the encapsulation of White LED.
Because epoxy resin and organosilicon biphase consistency are poor, above-mentioned independent physical blending method makes that epoxy and organosilicon are prone to be separated in system, thereby tends to have influence on the homogeneity and the transmittance of packaged material; Simultaneously, epoxy resin and organosilyl specific refractory power are generally not high, the specific refractory power of prepared material also lower usually (about 1.5), and fixing and non-adjustable; In addition, because the existence of epoxy in the material makes it still have the certain moisture performance.Utilize the LED of this type material prepn to be difficult to take into account simultaneously performances such as transmittance, hardness, bonding strength, specific refractory power, stability to aging and water absorbability with the epoxy organosilicon packaged material.
Summary of the invention
In order to overcome and solve the deficiency and the shortcoming of prior art, primary and foremost purpose of the present invention is to provide a kind of organic-silicon hybridization resin.
Another object of the present invention is to provide the preparation method of above-mentioned organic-silicon hybridization resin.
Another object of the present invention is to provide the application of above-mentioned organic-silicon hybridization resin.
Another object of the present invention is to provide a kind of power-type LED to use packaged material, this packaged material contains above-mentioned organic-silicon hybridization resin.
A purpose more of the present invention is to provide the preparation method of above-mentioned packaged material.
The object of the invention realizes through following technical scheme:
A kind of organic-silicon hybridization resin has following general molecular formula:
{(R 1) a(R f) b(OH) cSiO (4-a-b-c)/2} x{(R 2) d?R o(OH) e?SiO (3-d-e)/2} y{(R 3) g(R Ph) h(OH) iSiO (4-g-h-i)/2} z；
Wherein, R 1Or R 2Be respectively-CH 3,-CH 2CH 3Or
Figure BDA00001707576200021
In a kind of; R fIt for carbon chain lengths 3～12 fluoro-alkyl; R oFor
Figure BDA00001707576200022
Or In a kind of, R is that carbon chain lengths is 2～8 straight-chain alkyl residue or is 3～10 hydridization straight-chain alkyl residue by the atom number that Sauerstoffatom and carbon atom are formed; R 3For-CH 3Or-CH 2CH 3In a kind of; R PhFor
Figure BDA00001707576200024
In a kind of; A, d or g are respectively 0 or 1; B or h are respectively 1 or 2; C, e or i are respectively 0,1 or 2; X, y or z are respectively 2～100 integer; And a+b+c<4, d+e<3, g+h+i<4.
The preparation method of described organic-silicon hybridization resin comprises following concrete steps:
The mixing liquid of 2～40 mass parts fluorocarbon based silane, 10～90 mass parts epoxy hydrocarbyl si lanes, 100 mass parts phenyl silanes, 5～50 mass parts zero(ppm) water, 0.5～5 mass parts of catalyst and 100～250 mass parts solvent compositions is joined in the reactor drum; Stir; In 60～100 ℃ of reaction 4～24h; Reaction is 5 * 10 with reaction product in vacuum tightness after finishing 3～10 * 10 3Pa, 50～100 ℃ of condition underspins steam 0.5～2.0h remove anhydrate, solvent and by product, obtain the high refractive index organic-silicon hybridization resin that the water white transparency heavy-gravity contains fluorine-based, epoxy group(ing) and three kinds of functional groups of phenyl;
Wherein, described fluorocarbon based silane is CF 3CH 2CH 2SiCH 3(OCH 3) 2, CF 3CH 2CH 2Si (OCH 3), (CF 3CH 2CH 2) 2SiCH 3(OCH 3) 2, C 3F 7CH 2CH 2SiCH 3(OCH 2CH 3) 3, (C 3F 7CH 2CH 2) 2Si (OCH 2CH 3) 2, (C 3F 7CH 2CH 2) 2SiCH 3(OCH 2CH 3) 2, C 6F 5SiCH 3(OCH 2CH 3) 2, (C 6F 5) 2Si (OCH 2CH 3) 2, 3,5-(CF 3) 2C 6H 3SiCH 3(OCH 2CH 3) 2, C 4F 9C 2H 4Si (OCH 3) 3, (CF 3) 2CFCFH (CF 3) CFCH 2CH 2CH 2CH 2Si (OCH 3) 3, (CF 3) 2CFCFH (CF 3) CFCH 2CH 2CH 2CH 2SiCH 3(OCH 3) 2, C 6F 13CH 2CH 2Si (OCH 2CH 3) 3, C 6F 13C 3H 6Si (OCH 3) 3, C 6F 13CH 2CH (CH 3) C 3H 6Si (OCH 3) 3, n-C 8F 17C 2H 4Si (OCH 3) 3(n refers to C in this molecular formula 8For containing the straight chain of 8 carbon atoms) or C 8F 17C 2H 4Si (C 6H 5) (OCH 3) 2In a kind of or at least two kinds mixture;
Described epoxy hydrocarbyl si lanes is OC 6H 9CH 2CH 2Si (OCH 3) 3, OCH 2CHCH 2OC 3H 6Si (OCH 3) 3, OCH 2CHCH 2OC 3H 6SiPh (OCH 2CH 3) 2, OCH 2CHCH 2OC 3H 6Si (OCH 2CH 3) 3, OCH 2CHCH 2OC 3H 6SiCH 3(OCH 2CH 3) 2, OCH 2CHCH 2OC 8H 16Si (OCH 3) 3Or OCH 2CHCH 2OC 4H 8Si (OCH 3) 3In a kind of or at least two kinds mixture;
Described phenyl silane is C 6H 5Si (OCH 2CH 3) 3, CH 3(C 6H 5) Si (OCH 2CH 3) 2, CH 3(C 6H 5) 2SiOCH 2CH 3, (C 6H 5) 2Si (OCH 2CH 3) 2, C 6H 5Si (OCH 3) 3, CH 3(C 6H 5) Si (OCH 3) 2, CH 3(C 6H 5) 2SiOCH 3, (C 6H 5) 2Si (OCH 3) 2, C 6H 5CH 2Si (OCH 2CH 3) 3, C 6H 5CH 2CH 2Si (OCH 3) 3Or (CH 3) 2C 6H 5SiOCH 2CH 3In a kind of or at least two kinds mixture;
Described solvent is ketone, alcohols and ethers;
Preferably, described solvent is 2-butanone, hexone, pimelinketone, ethanol, butanols, THF, 1, the mixture of a kind of in 4-dioxy six alkane or the glycol dimethyl ether or at least two kinds;
Described catalyzer is the carboxylate metal salt;
Preferably, described catalyzer is the mixture of a kind of in dibutyl tin acetate, dibutyl tin dilaurate or the stannous octoate or at least two kinds.
Described organic-silicon hybridization resin at photoelectric conversion material, unicircuit packaged material, insulating material, coated material or sizing agent and power-type LED with the application in the packaged material.
A kind of power-type LED is used packaged material, comprises following components by weight portions:
100 parts of organic-silicon hybridization resins
0.5～50 part in solidifying agent
0～1.0 part of curing catalyst;
0～40 part of auxiliary agent;
Wherein, described solidifying agent is one or both the mixture in anhydrides and the methyl ethyl diketone salt solidifying agent;
Preferably, described solidifying agent is Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, carbic anhydride, methyl carbic anhydride, MALEIC ANHYDRIDE, Pyroglutaric acid, gathers the mixture of a kind of in nonane diacid acid anhydride, aluminium acetylacetonate, methyl ethyl diketone zirconium or the titanium acetylacetone or at least two kinds;
Described curing catalyst is the mixture of a kind of in cetyl trimethylammonium bromide, Trimethyllaurylammonium bromide, tetrabutyl ammonium acetate, Tetrabutyl amonium bromide, the four hexyl brometo de amonios or at least two kinds;
Described auxiliary agent is the mixture of a kind of of strengthening agent, heat conductive filler, skimmer, oxidation inhibitor, light diffusing agent, UV light absorber or thinner or at least two kinds;
Described strengthening agent is one or both the mixture in gas-phase silica or the MQ silicone resin;
Described heat conductive filler is the mixture of a kind of in nano zine oxide, aluminum oxide, silit, aluminium nitride AlN, zirconium carbide or the Graphite Powder 99 or at least two kinds;
Described skimmer is a silicone antifoam agent;
Described oxidation inhibitor is phosphite antioxidant;
Described light diffusing agent is the organosilicon light diffusing agent;
Described UV light absorber is UVNUL MS-40, benzotriazole or hindered amine UV light absorber;
Described thinner is a cycloaliphatic epoxy resin.
Described power-type LED comprises following concrete steps with the preparation method of packaged material:
Get and stir after 100 weight part organic-silicon hybridization resins, 0.5～50 weight part solidifying agent, 0～1.0 weight part curing catalyst and 0～40 weight part auxiliary agent mix; Be to carry out under the condition of 267Pa after the deaeration being cured in vacuum tightness, obtain water white power-type LED and use packaged material by 80～110 ℃/2～4h, 120～140 ℃/2～4h, 150～180 ℃/3～6h program curing.
The present invention mainly adopts cohydrolysis polycondensation method; With fluorocarbon based silane, epoxy hydrocarbyl si lanes and phenyl silane is raw material; Under the catalyzer condition through polycondensation; Prepare containing of homogeneous of fluorine-based, epoxy group(ing) and the organic-silicon hybridization resin of the high refractive index of phenyl trifunctional, this organic-silicon hybridization resin and solidifying agent, curing catalyst and auxiliary agent are cured can be prepared the power-type LED that has epoxy resin and organosilicon advantage concurrently and use the organic-silicon hybridization packaged material.The present invention has solved the easy problem that is separated of epoxy resin and organosilicon through the organic-silicon hybridization resin of the prepared homogeneous of co-hydrolysis; Through fluorine-based and introducing epoxy group(ing); Improve the wet fastness of this packaged material when can be implemented in mechanical property such as the bonding force that increases packaged material, hardness effectively, solving traditional independent introducing epoxy increase material mechanical performance that passes through reduces material water tolerance problem; In addition; The present invention also can be through to the control of the ratio of phenyl silane and then the specific refractory power of effectively regulating packaged material, thereby when not influencing other performances such as packaged material transmittance, effectively improves the performances such as mechanical property, specific refractory power and wet fastness of packaged material bonding force, hardness etc.
The present invention compared with prior art has following advantage and beneficial effect:
(1) encapsulation of organic-silicon hybridization resin of the present invention and power-type LED is simple with the preparation method of organosilicon hybrid material, the starting material environmental protection, conveniently is easy to get.
(2) the present invention introduces epoxy group(ing) in the organic-silicon hybridization resin through the hydrolytie polycondensation method, has solved the easy problem that is separated of epoxy resin and organosilicon.When the preparation packaged material, improve hardness, adhesiveproperties and the mechanical property etc. of material when can effectively keep transmittance.
(3) the present invention is fluorine-based through in the organic-silicon hybridization resin, introducing, and has solved because of independent epoxy group(ing) and has introduced the wet fastness problem that reduces packaged material, has improved its wet fastness.Simultaneously; Ratio through control fluorocarbon based silane, epoxy hydrocarbyl si lanes and phenyl silane; Regulate the performances such as hardness, mechanical strength, specific refractory power and water tolerance of material effectively, and then organosilicon hybrid material is used in the power-type LED encapsulation of preparing excellent combination property.
(4) power-type LED of the present invention's preparation has epoxy resin and organosilyl advantage concurrently with the organic-silicon hybridization packaged material; Have advantages such as high transmission rate and specific refractory power, agent of low hygroscopicity, excellent mechanical property and ageing-resistant performance, solved that the LED encapsulation is low with common organosilicon material bonding strength, poor mechanical property and causing comes off and cause LED light output rate low and problem such as lack work-ing life.
(5) organic-silicon hybridization resin of the present invention can be used as the processing and preparing that starting material are applied to optical lens material, photoelectric conversion material, unicircuit packaged material, insulating material, coated material, sizing agent etc.
Specific embodiment
Below through embodiment the present invention is described in further detail, but embodiment of the present invention is not limited thereto.
Embodiment 1
(1) preparation of organic-silicon hybridization resin
Get 40g CF 3CH 2CH 2Si (OCH 3) 3(Hangzhou Jesse's card chemical industry ltd), 10gOC 6H 9CH 2CH 2Si (OCH 3) 3(Noah's ark (Fugang) chemical material ltd), 100g dimethoxydiphenylsilane (C 6H 5) 2Si (OCH 3) 2(Zhejiang Chemical Industry Science and Technology Group Co.,Ltd), 30g zero(ppm) water, 2.0g dibutyl tin laurate and 150g 2-butanone solvent are warming up to 80 ℃ of reaction 8h after stirring in the round-bottomed flask reactor drum that whisking appliance, reflux exchanger, TM are housed.After question response finishes, be 10 in 50 ℃, vacuum tightness through Rotary Evaporators 4Pa condition underspin steam 2h remove anhydrate, solvent and by product, prepare the thick organic-silicon hybridization resin of water white transparency.
Reach with GPC, FT-IR 1H NMR characterizes the structure of product, and wherein, the number-average molecular weight that GPC surveys product is 17650; In the FT-IR spectrogram, product is at 3401cm -1And 1050-1150cm -1Wide hydroxyl and the charateristic avsorption band of Si-O-Si have appearred respectively in the place, simultaneously at 877cm -1Kept and come from OC 6H 9CH 2CH 2Si (OCH 3) 3In the alicyclic epoxy absorption peak; 1In the H NMR spectrogram, the charateristic avsorption band of phenyl occurred at the 7.3ppm place, the alicyclic epoxy absorption peak has appearred in the 3.1ppm place, and CF 3CH 2CH 2Si (OCH 3) 3In be positioned at 1.9ppm and 0.6ppm charateristic avsorption band then with from OC 6H 9CH 2CH 2Si (OCH 3) 3Absorption peak overlap, this organic-silicon hybridization molecular resin formula of deriving is: { CF 3CH 2CH 2(OH) cSiO 3-c/2} 25{ OC 6H 9CH 2CH 2(OH) eSiO 3-e/2} 5{ (C 6H 5) 2(OH) iSiO 2-i/2} 50;
Wherein, c or e are 0,1 or 2; I is 0 or 1.
(2) preparation of power-type LED packaged material
Getting the prepared organic-silicon hybridization resin of 100g step (1), 20g methyl hexahydrophthalic anhydride solidifying agent, 0.1g Tetrabutyl amonium bromide curing catalyst and 2g gas-phase silica strengthening agent is mixed in the flask and stirs; Placing vacuum tightness is after the vacuum drying oven of 267Pa carries out deaeration; By (promptly 90 ℃ down behind the curing 2h of 90 ℃/2h, 120 ℃/2h, 180 ℃/3h; Be warming up to 120 ℃ and solidify 2h; Being warming up to 180 ℃ at last and solidifying 3h) program curing is cured, and finally obtains the water white transparency cured product, i.e. power-type LED packaged material A.
Embodiment 2
(1) preparation of organic-silicon hybridization resin
Get 2g n-C 8F 17C 2H 4Si (OCH 3) 3(Noah's ark (Fugang) chemical material ltd) (n refers to C in this molecular formula 8For containing the straight chain of 8 carbon atoms), 30g OCH 2CHCH 2OC 3H 6Si (OCH 3) 3(Noah's ark (Fugang) chemical material ltd), 100g C 6H 5Si (OCH 3) 3(Zhejiang Chemical Industry Science and Technology Group Co.,Ltd), 5g zero(ppm) water, 5g stannous octoate and 120g hexone are mixed in the round-bottomed flask reactor drum that whisking appliance, reflux exchanger, TM are housed, and the back that stirs is reacted 24h down at 60 ℃.After question response finishes, be 5 ⅹ 10 in 100 ℃, vacuum tightness through Rotary Evaporators 3Pa condition underspin steam 0.5h remove anhydrate, solvent and by product, prepare the thick organic-silicon hybridization resin of water white transparency.
Use GPC, FT-IR reaches 1H NMR characterizes the structure of product.The number-average molecular weight that GPC surveys product is 24046; In the FT-IR spectrogram, product is at 3415cm -1And 1050-1150cm -1Wide hydroxyl and the charateristic avsorption band of Si-O-Si have appearred respectively in the place, simultaneously at 906cm -1Kept and come from OCH 2CHCH 2OC 3H 6Si (OCH 3) 3In the epoxy group(ing) absorption peak; 1In the H NMR spectrogram, the charateristic avsorption band of phenyl occurred at the 7.3ppm place, the epoxy group(ing) absorption peak has appearred in 2.5ppm and 2.8ppm place, and n-C 8F 17C 2H 4Si (OCH 3) 3Charateristic avsorption band appears at 1.4ppm and 0.6ppm.This organic-silicon hybridization molecular resin formula of deriving is: { n-C 8F 17C 2H 4(OH) cSiO 3-c/2} 2{ OCH 2CHCH 2OC 3H 6(OH) eSiO 3-e/2} 30{ C 6H 5(OH) iSiO 3-i/ 2} 100
Wherein, c, e or i are 0,1 or 2.
(2) preparation of power-type LED packaged material
Getting the prepared organic-silicon hybridization resin of 100g step (1), 10g methyl tetrahydro phthalic anhydride solidifying agent, 0.1g Trimethyllaurylammonium bromide curing catalyst, 1.0g O-hydroxyl-diphenyl ketone UV light absorber, 2.0g nano-ZnO heat conductive filler and 0.5g TNPP phosphite antioxidant component is mixed in the flask and stirs; Placing vacuum tightness is after the vacuum drying oven of 267Pa carries out deaeration; Be cured by 80 ℃/2h, 130 ℃/4h, 180 ℃/3h program curing; Obtain the water white transparency cured product, i.e. power-type LED packaged material B.
Embodiment 3
(1) preparation of organic-silicon hybridization resin
Get 8g C 6F 13C 2H 4Si (OC 2H 5) 3(Harbin avenge good fluorine chemistry of silicones ltd), 90gOCH 2CHCH 2OC 8H 16Si (OCH 3) 3(the good long day chemical industry in Guangzhou trade Co., Ltd), 100g (C 6H 5) 2Si (OCH 3) 2(Zhejiang Chemical Industry Science and Technology Group Co.,Ltd), 40g zero(ppm) water, 1.5g dibutyl tin acetate and 100g 1; 4-dioxy six alkane are mixed in the round-bottomed flask reactor drum that whisking appliance, reflux exchanger, TM are housed, and the back that stirs is reacted 12h down at 70 ℃.After question response finishes, be 7 ⅹ 10 in 80 ℃, vacuum tightness through Rotary Evaporators 3Pa condition underspin steam 1h remove anhydrate, solvent and by product, prepare the thick organic-silicon hybridization resin of water white transparency.
Use GPC, FT-IR reaches 1H NMR characterizes the structure of product.The number-average molecular weight that GPC surveys product is 21525; In the FT-IR spectrogram, product is at 3426cm -1And 1050-1150cm -1Wide hydroxyl and the charateristic avsorption band of Si-O-Si have appearred respectively in the place, simultaneously at 910cm -1Kept and come from OCH 2CHCH 2OC 8H 16Si (OCH 3) 3In the epoxy group(ing) absorption peak; 1In the H NMR spectrogram, the charateristic avsorption band of phenyl occurs at the 7.3ppm place, located to have occurred the epoxy group(ing) absorption peak about 2.4ppm and 2.7ppm, and C 6F 13C 2H 4Si (OC 2H 5) 3Charateristic avsorption band appears at 1.3ppm and 0.6ppm.This organic-silicon hybridization molecular resin formula of deriving is: { C 6F 13C 2H 4(OH) cSiO 3-c/2} 3{ OCH 2CHCH 2OC 8H 16(OH) eSiO 3-e/2} 35{ (C 6H 5) 2(OH) iSiO 2-i / 2} 50
Wherein, c or e are 0,1 or 2; I is 0 or 1.
(2) preparation of power-type LED packaged material
The organic-silicon hybridization resin, the 50g that get 100g step (1) preparation gather nonane diacid anhydride curing agents, 1.0g cetyl trimethylammonium bromide curing catalyst, 27g alicyclic epoxy ERL-4221 thinner, 1.0g HS-025 silicone antifoam agent, 2.0g O-hydroxyl-diphenyl ketone UV light absorber, 2.0g STA-338 phosphite antioxidant, 1.0g GD-210 organosilicon light diffusing agent and 7.0g nanometer Al 2O 3Heat conductive filler is mixed in the flask and stirs; Placing vacuum tightness is after the vacuum drying oven of 267Pa carries out deaeration; Be cured by 110 ℃/2h, 140 ℃/2h, 170 ℃/4h program curing, obtain the water white transparency cured product, i.e. power-type LED hydridization packaged material C.
Embodiment 4
(1) preparation of organic-silicon hybridization resin
Get 20g (CF 3) 2CFCFH (CF 3) CFCH 2CH 2CH 2CH 2Si (OCH 3) 3(Harbin avenge good fluorine chemistry of silicones ltd), 20g OC 6H 9CH 2CH 2Si (OCH 3) 3(Noah's ark (Fugang) chemical material ltd), 100g (C 6H 5) 2Si (OCH 3) 2(Zhejiang Chemical Industry Science and Technology Group Co.,Ltd), 25g zero(ppm) water, 3g dibutyl tin laurate and 250ml solvent butanols are mixed in the round-bottomed flask reactor drum that whisking appliance, reflux exchanger, TM are housed, and the back that stirs is reacted 4h down in 100 ℃.After question response finishes, be 10 in 90 ℃, vacuum tightness through Rotary Evaporators 4Pa condition underspin steam 1h remove anhydrate, solvent and by product, prepare the thick organic-silicon hybridization resin of water white transparency.
Use GPC, FT-IR reaches 1H NMR characterizes the structure of product.The number-average molecular weight that GPC surveys product is 17640; In the FT-IR spectrogram, product is at 3424cm -1And 1050-1150cm -1Wide hydroxyl and the charateristic avsorption band of Si-O-Si have appearred respectively in the place, simultaneously at 875cm -1Kept and come from OC 6H 9CH 2CH 2Si (OCH 3) 3In alicyclic epoxy base absorption peak; 1In the H NMR spectrogram, the charateristic avsorption band of phenyl occurred at the 7.3ppm place, alicyclic epoxy base absorption peak has appearred in the 3.1ppm place, and (CF 3) 2CFCFH (CF 3) CFCH 2CH 2CH 2CH 2Si (OCH 3) 3Charateristic avsorption band appears at 3.6ppm, its be positioned between 0.5ppm and 2.0ppm charateristic avsorption band then with from OC 6H 9CH 2CH 2Si (OCH 3) 3Absorption peak overlap.This organic-silicon hybridization molecular resin formula of deriving is: { (CF 3) 2CFCFH (CF 3) CFCH 2CH 2CH 2CH 2(OH) cSiO 3-c/2} 4{ OC 6H 9CH 2CH 2(OH) eSiO 3-e/ 2} 8{ (C 6H 5) 2(OH) iSiO 2-i/2} 60
Wherein, c or e are 0,1 or 2; I is 0 or 1.
(2) preparation of power-type LED hydridization packaged material
Organic-silicon hybridization resin, the 1.0g methyl ethyl diketone zirconium solidifying agent of getting 100g step (1) preparation are mixed in the flask and stir; Placing vacuum tightness is after the vacuum drying oven of 267Pa carries out deaeration; Be cured by 80 ℃/4h, 120 ℃/4h, 150 ℃/6h program curing; Obtain the water white transparency cured product, i.e. power-type LED packaged material D.
Embodiment 5
(1) preparation of organic-silicon hybridization resin
Get 10g (C 3F 7CH 2CH 2) 2Si (OCH 2CH 3) 2(the chemical ltd of A Faaisha (Tianjin)), 25gOCH 2CHCH 2OC 3H 6SiC 6H 5(OCH 2CH 3) 2(the good long day chemical industry in Guangzhou trade Co., Ltd), 100gC 6H 5Si (OCH 3) 3(Zhejiang Chemical Industry Science and Technology Group Co.,Ltd), 35g zero(ppm) water, the inferior tin of 2.3g octoate catalyst and 200g 1; 4-dioxy six alkane are mixed in the round-bottomed flask reactor drum that whisking appliance, reflux exchanger, TM are housed, and the back that stirs is reacted 12h down in 80 ℃.After question response finishes, be 6 ⅹ 10 in 80 ℃, vacuum tightness through Rotary Evaporators 3Pa condition underspin steam 1h remove anhydrate, solvent and by product, prepare the thick organic-silicon hybridization resin of water white transparency.
Use GPC, FT-IR reaches 1H NMR characterizes the structure of product.The number-average molecular weight that GPC surveys product is 24828; In the FT-IR spectrogram, product is at 3434cm -1And 1050-1150cm -1Wide hydroxyl and the charateristic avsorption band of Si-O-Si have appearred respectively in the place, simultaneously at 906cm -1Kept and come from OCH 2CHCH 2OC 3H 6Si (OCH 3) 3In the epoxy group(ing) absorption peak; 1In the H NMR spectrogram, the charateristic avsorption band of phenyl occurs at the 7.3ppm place, located to have occurred the epoxy group(ing) absorption peak about 2.5ppm and 2.8ppm, and (C 3F 7CH 2CH 2) 2Si (OCH 2CH 3) 2Charateristic avsorption band appears at 1.9ppm and 0.6ppm.Molecular formula based on above this organic-silicon hybridization resin of data derivation is:
{(C 3F 7CH 2CH 2) 2(OH) cSiO 2-c/2} 4{OCH 2CHCH 2OC 3H 6(C 6H 5)(OH) eSiO 2-e/2} 16{C 6H 5(OH) iSiO 3-i/2} 100；
Wherein, c or e are 0 or 1; I is 0,1 or 2.
(2) preparation of power-type LED packaged material
Organic-silicon hybridization resin, 20g phthalic acid anhydride curing agents, 0.1 Tetrabutyl amonium bromide curing catalyst, 0.5g HS-025 silicone antifoam agent, 2.0g O-hydroxyl-diphenyl ketone UV light absorber and the 0.3g triphenyl phosphite oxidation inhibitor of getting 100g step (1) preparation are mixed in the flask and stir; Placing vacuum tightness is after the vacuum drying oven of 267Pa carries out deaeration; Be cured by 90 ℃/2h, 120 ℃/2h, 180 ℃/3h program curing; Obtain the water white transparency cured product, i.e. power-type LED packaged material E.
Embodiment 6
(1) preparation of organic-silicon hybridization resin
Get 8g (CF 3) 2CFCFH (CF 3) CFCH 2CH 2CH 2CH 2SiMe (OCH 3) 2(Harbin avenge good fluorine chemistry of silicones ltd), 22g OC 6H 9CH 2CH 2Si (OCH 3) 3(Noah's ark (Fugang) chemical material ltd), 100g C 6H 5CH 2CH 2Si (OCH 3) 3(Zhejiang Chemical Industry Science and Technology Group Co.,Ltd), 50g zero(ppm) water, 0.5g dibutyl tin acetate and 100g pimelinketone are mixed in the round-bottomed flask reactor drum that whisking appliance, reflux exchanger, TM are housed, and the back that stirs is reacted 16h down in 90 ℃.After question response finishes, be 10 in 90 ℃, vacuum tightness through Rotary Evaporators 4Pa condition underspin steam 1h remove anhydrate, solvent and by product, prepare the thick organic-silicon hybridization resin of water white transparency.
Use GPC, FT-IR reaches 1H NMR characterizes the structure of product.The number-average molecular weight that GPC surveys product is 33408; In the FT-IR spectrogram, product is at 3426cm -1And 1050-1150cm -1Wide hydroxyl and the charateristic avsorption band of Si-O-Si have appearred respectively in the place, simultaneously at 875cm -1Kept and come from OC 6H 9CH 2CH 2Si (OCH 3) 3In alicyclic epoxy base absorption peak; 1In the H NMR spectrogram, the charateristic avsorption band of phenyl occurred at the 7.3ppm place, alicyclic epoxy base absorption peak has appearred in the 3.1ppm place, and (CF 3) 2CFCFH (CF 3) CFCH 2CH 2CH 2CH 2SiCH 3(OCH 3) 2Charateristic avsorption band appears at 3.6ppm, its be positioned between 0.5ppm and 2.0ppm charateristic avsorption band then with from OC 6H 9CH 2CH 2Si (OCH 3) 3Absorption peak overlap.According to above this organic-silicon hybridization molecular resin formula of data derivation be: { (CF 3) 2CFCFH (CF 3) CFCH 2CH 2CH 2CH 2(CH 3) (OH) cSiO 2-c/2} 4{ OC 6H 9CH 2CH 2(OH) eSiO 3-e/2} 15{ C 6H 5CH 2CH 2(OH) iSiO 3-i/2} 80
Wherein, c is 0 or 1; E or i are 0,1 or 2.
(2) preparation of power-type LED packaged material
Organic-silicon hybridization resin, 0.5g aluminium acetylacetonate solidifying agent, 1.0g gas-phase silica strengthening agent, 1.0g TECH-340 silicone antifoam agent and 2.0g 2-Phenylbenzimidazole-5-sulfonic acid UV light absorber of getting 100g step (1) preparation is mixed in the flask and stirs; Placing vacuum tightness is after the vacuum drying oven of 267Pa carries out deaeration; Be cured by 80 ℃/2h, 120 ℃/3h, 160 ℃/4h program curing; Obtain the water white transparency cured product, i.e. power-type LED packaged material F.
The comparative example
(1) preparation of organic-silicon hybridization resin
Get 200g OCH 2CHCH 2OC 3H 6Si (OCH 3) 3(Noah's ark (Fugang) chemical material ltd), 100g C 6H 5CH 2CH 2Si (OCH 3) 3(Zhejiang Chemical Industry Science and Technology Group Co.,Ltd), 80g zero(ppm) water, 1.5g dibutyl tin dilaurate and 200g pimelinketone are mixed in the round-bottomed flask reactor drum that whisking appliance, reflux exchanger, TM are housed, and the back that stirs is reacted 24h down in 80 ℃.After question response finishes, be 10 in 90 ℃, vacuum tightness through Rotary Evaporators 4Pa condition underspin steam 1h remove anhydrate, solvent and by product, prepare the thick organic-silicon hybridization resin of water white transparency.
Use GPC, FT-IR reaches 1H NMR characterizes the structure of product.The number-average molecular weight that GPC surveys product is 29520; In the FT-IR spectrogram, product is at 3324cm -1And 1050-1150cm -1Wide hydroxyl and the charateristic avsorption band of Si-O-Si have appearred respectively in the place, simultaneously at 906cm -1Kept and come from OCH 2CHCH 2OC 3H 6Si (OCH 3) 3In the epoxy group(ing) absorption peak; 1In the H NMR spectrogram, the charateristic avsorption band of phenyl occurred at the 7.3ppm place, the epoxy group(ing) absorption peak has appearred in 2.5ppm and 2.8ppm place.Molecular formula based on above this organic-silicon hybridization resin of data derivation is:
{OCH 2CHCH 2OC 3H 6(OH) eSiO 3-e/2} 100{C 6H 5CH 2CH 2(OH) iSiO 3-i/2} 40
Wherein, e or i are 0,1 or 2.
(2) preparation of power-type LED packaged material
Organic-silicon hybridization resin, the 60g methyl hexahydrophthalic anhydride solidifying agent of getting 100g step (1) preparation are mixed in the flask and stir; Placing vacuum tightness is after the vacuum drying oven of 267Pa carries out deaeration; Be cured by 90 ℃/2h, 140 ℃/2h, 180 ℃/4h program curing; Obtain the water white transparency cured product, i.e. power-type LED packaged material G.
Effect embodiment
The power-type LED that obtains among embodiment 1～6 and the comparative example is carried out the performance of products test with packaged material A～G.Wherein, the method for the performance of test material or standard are as follows:
(1) specific refractory power adopts the ZWA type Abbe refractometer of optical instrument factory, Shanghai to test;
(2) hardness reference standard JB 6148-92 adopts Shore durometer D to test;
(3) surface bonding power records according to the testing method of standard A STM D3359-B;
(4) tensile strength reference standard ASTM D638-08 adopts the RGM-3030 electronic universal tester to test, and gets 6 sample test MVs and obtains;
(5) water-intake rate is tested with reference to method shown in the GB1034-86, and before the test, sample elder generation, soaks 2h and measures relative water-intake rate to constant mass at 50 ℃ of dry 24h in the boiling water;
(6) surface energy is through calculating according to the relation between contact angle and the surface energy (like formula)
γ L1(1+cosθ 1)=2(γ s Dγ L1 D) 1/2+2(γ s Pγ L1 P) 1/2
γ L2(1+cosθ 2)=2(γ s Dγ L2 D) 1/2+2(γ s Pγ L2 P) 1/2
γ s=γ s D+γ s P
Wherein, L 1, L 2Be respectively water, terepthaloyl moietie, θ 1, θ 2Be respectively water, the terepthaloyl moietie contact angle on sample, γ L1, γ L2, γ sBe respectively the surface energy of water, terepthaloyl moietie and sample, γ L1 D, γ L2 D, γ s DBe respectively the London force of water, terepthaloyl moietie and sample, γ L1 P, γ L2 P, γ s PBe respectively the polar forces of water, terepthaloyl moietie and sample; And γ L1=72.8mJ/m 2, γ L2=48mJ/m 2, γ L1 D=21.8mJ/m 2, γ L2 D=29mJ/m 2, γ L1 P=51mJ/m 2, γ L2 P=19mJ/m 2
Contact angle adopts the model of Shanghai Zhongchen digital technology equipment Co., Ltd to test for the JC-2000D contact angle measurement;
(7) transmittance UV 8000 ultraviolet-visible pectrophotometers that adopt Shanghai unit to analyse Instr Ltd. are tested, and thickness of sample is 3mm, and the scope of scanning wavelength is 280～800nm, and the absorbancy of choosing 800nm and 400nm place compares.
With materials A～G through above testing method after, the gained data are shown in table one:
Table one
Figure BDA00001707576200121
Can find out from table one; Along with the variation of contained fluorocarbon based silane, phenyl silane and epoxy radicals silicone hydride ratio in the used organic-silicon hybridization resin of power-type LED packaged material A～G, corresponding packaged material this each item performance is also corresponding changes in specific refractory power, hardness, adhesiveproperties and tensile strength etc.; Increase and contain fluorine atoms structure segmental through fluorocarbon based silane consumption increase, and can make corresponding packaged material reduce water-intake rate and surface energy to a certain extent, and keep the high transmission rate of material simultaneously; With the increase gradually of epoxy silane ratio, the hardness of corresponding packaged material, adhesiveproperties and mechanical property then increase gradually; And when increasing the ratio of phenyl silane, then can improve the specific refractory power of corresponding packaged material effectively.
Among power-type LED packaged material A～F; Specific refractory power can be up to 1.58 (material D); Hardness, tensile strength and surface bonding power best result Bie Keda 50D (material C), 48.5MPa (material C) and 5B (material C), water-intake rate and surface energy can be reduced to 0.09% (materials A) and 14.38mJ/m 2(material D), and still keep the high permeability (> of material; 90%, 800nm).
Power-type LED packaged material G is owing to have only epoxy group(ing) and phenyl in the used organic-silicon hybridization resin among the material G; Therefore compare with materials A～F; Though improved the hardness and the mechanical strength of material to a certain extent, reduced the water tolerance and the surface hydrophobicity of material, and specific refractory power be also lower.
After, epoxy group(ing) fluorine-based through in the organic-silicon hybridization resin, introducing simultaneously and phenyl trifunctional and control three's ratio is applied to the power-type LED packaged material, improve the purpose of the wet fastness of material when can effectively realize increasing the mechanical properties such as bonding force, hardness of material.
Just because of the characteristic of this organic-silicon hybridization resin, it can also be applied to the processing and preparing of optical lens material, photoelectric conversion material, unicircuit packaged material, insulating material, coated material, sizing agent etc. as starting material.
The foregoing description is a preferred implementation of the present invention; But embodiment of the present invention is not restricted to the described embodiments; Other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; All should be the substitute mode of equivalence, be included within protection scope of the present invention.

Claims (8)

1. organic-silicon hybridization resin is characterized in that having following general molecular formula:
{(R 1) a(R f) b(OH) cSiO (4-a-b-c)/2} x{(R 2) d?R o(OH) eSiO (3-d-e)/2} y{(R 3) g(R Ph) h(OH) iSiO (4-g-h-i)/2} z；
Wherein, R 1For-CH 3,-CH 2CH 3Or
Figure FDA00001707576100011
In a kind of;
R 2For-CH 3,-CH 2CH 3Or In a kind of;
R fIt for carbon chain lengths 3～12 fluoro-alkyl;
R oFor
Figure FDA00001707576100013
Or
Figure FDA00001707576100014
In a kind of, R is that carbon chain lengths is 2～8 straight-chain alkyl residue or is 3～10 hydridization straight-chain alkyl residue by the atom number that Sauerstoffatom and carbon atom are formed;
R 3For-CH 3Or-CH 2CH 3In a kind of;
R PhFor In a kind of;
A is 0 or 1; B is 1 or 2; C is 0,1 or 2; D is 0 or 1; E is 0,1 or 2; G is 0 or 1; H is 1 or 2; I is 0,1 or 2; X is 2～100 integer; Y is 2～100 integer; Z is 2～100 integer; And < 4, < 3, g+h+i < 4 for d+e for a+b+c.
2. the preparation method of the described organic-silicon hybridization resin of claim 1 is characterized in that comprising following concrete steps:
The mixing liquid of 2～40 mass parts fluorocarbon based silane, 10～90 mass parts epoxy hydrocarbyl si lanes, 100 mass parts phenyl silanes, 5～50 mass parts zero(ppm) water, 0.5～5 mass parts of catalyst and 100～250 mass parts solvent compositions is joined in the reactor drum; Stir; In 60～100 ℃ of reaction 4～24h; Reaction is 5 ⅹ 10 with reaction product in vacuum tightness after finishing 3～10 ⅹ 10 3Pa, 50～100 ℃ of condition underspins steam 0.5～2.0h remove anhydrate, solvent and by product, obtain water white transparency heavy-gravity organic-silicon hybridization resin;
Described catalyzer is the carboxylate metal salt;
Described solvent is ketone, alcohols and ethers.
3. the preparation method of organic-silicon hybridization resin according to claim 2 is characterized in that: described fluorocarbon based silane is CF 3CH 2CH 2SiCH 3(OCH 3) 2, CF 3CH 2CH 2Si (OCH 3), (CF 3CH 2CH 2) 2SiCH 3(OCH 3) 2, C 3F 7CH 2CH 2SiCH 3(OCH 2CH 3) 3, (C 3F 7CH 2CH 2) 2Si (OCH 2CH 3) 2, (C 3F 7CH 2CH 2) 2SiCH 3(OCH 2CH 3) 2, C 6F 5SiCH 3(OCH 2CH 3) 2, (C 6F 5) 2Si (OCH 2CH 3) 2, 3,5-(CF 3) 2C 6H 3SiCH 3(OCH 2CH 3) 2, C 4F 9C 2H 4Si (OCH 3) 3, (CF 3) 2CFCFH (CF 3) CFCH 2CH 2CH 2CH 2Si (OCH 3) 3, (CF 3) 2CFCFH (CF 3) CFCH 2CH 2CH 2CH 2SiCH 3(OCH 3) 2, C 6F 13CH 2CH 2Si (OCH 2CH 3) 3, C 6F 13C 3H 6Si (OCH 3) 3, C 6F 13CH 2CH (CH 3) C 3H 6Si (OCH 3) 3, n-C 8F 17C 2H 4Si (OCH 3) 3Or C 8F 17C 2H 4Si (C 6H 5) (OCH 3) 2In a kind of or at least two kinds mixture;
Described epoxy hydrocarbyl si lanes is OC 6H 9CH 2CH 2Si (OCH 3) 3, OCH 2CHCH 2OC 3H 6Si (OCH 3) 3, OCH 2CHCH 2OC 3H 6SiPh (OCH 2CH 3) 2, OCH 2CHCH 2OC 3H 6Si (OCH 2CH 3) 3, OCH 2CHCH 2OC 3H 6SiCH 3(OCH 2CH 3) 2, OCH 2CHCH 2OC 8H 16Si (OCH 3) 3Or OCH 2CHCH 2OC 4H 8Si (OCH 3) 3In a kind of or at least two kinds mixture;
Described phenyl silane is C 6H 5Si (OCH 2CH 3) 3, CH 3(C 6H 5) Si (OCH 2CH 3) 2, CH 3(C 6H 5) 2SiOCH 2CH 3, (C 6H 5) 2Si (OCH 2CH 3) 2, C 6H 5Si (OCH 3) 3, CH 3(C 6H 5) Si (OCH 3) 2, CH 3(C 6H 5) 2SiOCH 3, (C 6H 5) 2Si (OCH 3) 2, C 6H 5CH 2Si (OCH 2CH 3) 3, C 6H 5CH 2CH 2Si (OCH 3) 3Or (CH 3) 2C 6H 5SiOCH 2CH 3In a kind of or at least two kinds mixture.
4. the preparation method of organic-silicon hybridization resin according to claim 2; It is characterized in that: described solvent is 2-butanone, hexone, pimelinketone, ethanol, butanols, THF, 1, the mixture of a kind of in 4-dioxy six alkane or the glycol dimethyl ether or at least two kinds;
Described catalyzer is the mixture of a kind of in dibutyl tin acetate, dibutyl tin dilaurate or the stannous octoate or at least two kinds.
Each described organic-silicon hybridization resin of claim 1～4 at photoelectric conversion material, unicircuit packaged material, insulating material, coated material or sizing agent and power-type LED with the application in the packaged material.
6. a power-type LED is used packaged material, it is characterized in that comprising following components by weight portions:
Figure FDA00001707576100021
Wherein, described solidifying agent is one or both mixtures in anhydrides and the methyl ethyl diketone salt solidifying agent;
Described curing catalyst is the mixture of a kind of in cetyl trimethylammonium bromide, Trimethyllaurylammonium bromide, tetrabutyl ammonium acetate, Tetrabutyl amonium bromide, the four hexyl brometo de amonios or at least two kinds;
Described auxiliary agent is the mixture of a kind of of strengthening agent, heat conductive filler, skimmer, oxidation inhibitor, light diffusing agent, UV light absorber or thinner or at least two kinds;
Described strengthening agent is one or both the mixture in gas-phase silica or the MQ silicone resin;
Described heat conductive filler is the mixture of a kind of in nano zine oxide, aluminum oxide, silit, aluminium nitride AlN, zirconium carbide or the Graphite Powder 99 or at least two kinds;
Described skimmer is a silicone antifoam agent;
Described oxidation inhibitor is phosphite antioxidant;
Described light diffusing agent is the organosilicon light diffusing agent;
Described UV light absorber is UVNUL MS-40, benzotriazole or hindered amine UV light absorber;
Described thinner is a cycloaliphatic epoxy resin.
7. power-type LED according to claim 6 is used packaged material, it is characterized in that: described solidifying agent is Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, carbic anhydride, methyl carbic anhydride, MALEIC ANHYDRIDE, Pyroglutaric acid, gather the mixture of a kind of in nonane diacid acid anhydride, aluminium acetylacetonate, methyl ethyl diketone zirconium or the titanium acetylacetone or at least two kinds.
8. the described power-type LED of claim 6 is with the preparation method of packaged material; Comprise following concrete steps: get 100 weight part organic-silicon hybridization resins, 0.5～50 weight part solidifying agent, 0～1.0 weight part curing catalyst and 0～40 weight part auxiliary agent and be mixed in the flask and stir; Be to carry out under the condition of 267Pa after the deaeration being cured in vacuum tightness, obtain water white power-type LED and use packaged material by 80～110 ℃/2～4h, 120～140 ℃/2～4h, 150～180 ℃/3～6h program curing.
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CN115894928A (en) * 2022-11-21 2023-04-04 东莞市雄驰电子有限公司 Preparation method of photocuring epoxy fluorobenzene silicone resin and application of photocuring epoxy fluorobenzene silicone resin in coating
CN115746703B (en) * 2022-11-21 2023-11-10 东莞市雄驰电子有限公司 Photo-curing coating composition prepared based on epoxy fluorobenzene silicone resin, coating method and application
CN115894928B (en) * 2022-11-21 2024-03-12 东莞市雄驰电子有限公司 Preparation method of photo-curing epoxy fluorobenzene silicone resin and application of photo-curing epoxy fluorobenzene silicone resin in paint coating
CN116041709A (en) * 2023-01-16 2023-05-02 陕西科技大学 Preparation method and application of photo-curing phenyl fluorosilicone modified epoxy paint and coating

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