CN103122149B - Optical package high refractive index High-transparency silicon rubber and its preparation method - Google Patents
Optical package high refractive index High-transparency silicon rubber and its preparation method Download PDFInfo
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Abstract
The present invention relates to a kind of optical package high refractive index High-transparency silicon rubber and its preparation method, silicone resin B component, the phenyl of described silicon rubber by the polysiloxane-based component A of phenyl vinyl, containing phenyl vinyl becomes containing the poly-oxygen alkane component C of hydrogen, platinum catalyst component D, catalytic inhibitor component E, modified polyorganosiloxane component F and water-removal agent component G mixed preparing. Described silicon rubber not only specific refractory power up to more than 1.50, and the transparency good, excellent in adhesion, stable performance, can long-term heat-resisting ultraviolet light resistant, the various requirement of LED can be met, be the desirable packaged material of LED. The present invention can be packaged into two component product, and product has good stability in storage, stores and still keeps high transparent in more than 6 months.
Description
Technical field
The present invention relates to Electronic Packaging and Macroscopic single crystal field, refer in particular to a kind of optical package high refractive index High-transparency silicon rubber and its preparation method.
Technical background
LED photodiode, being also called light emitting diode (LightEmittingDiode is abbreviated as LED) is a kind of light emitting semiconductor device that electric energy can be changed into luminous energy. Compared with traditional vacuum lamp bubble etc., Semiconductor LED light source has unrivaled advantage. The working life of semiconductor LED is extremely long, is more than 10 times of traditional lighting utensil, effectively reduces cost; It is low in energy consumption, luminous efficiency height, the saving energy, is the appropriate candidates of future source of energy strategy.
In the process manufacturing LED component, except chip fabrication techniques, fluorescent material manufacturing technology and heat dissipation technology, its luminous efficiency, brightness and work-ing life also will be made a significant impact by the performance of LED encapsulation material. But traditional packaged material epoxy resin is because the deficiency of reliability and resistance to ultraviolet ageing-resistant performance aspect, is not suitable for the power-type LED that development is more and more faster now. Particularly power is at the great power LED product of more than 0.5W-1W, if using traditional epoxy resin to encapsulate, lamp pearl will become and produce serious light and decline and even lost efficacy because the aging Huang of epoxy resin.
Silica gel is because the reasons such as resistance to ultraviolet, color inhibition, high refractive index are used to the encapsulation of power-type LED device. and considering due to aspects such as light extraction efficiency, ageing-resistant, ventilative oxygen permeabilities, the high refractive index silica gel containing phenyl is more and more subject to the attention of industry peer. at present, both at home and abroad that its research is more, achieve certain achievement, market has had the product that some are suitable, the relevant patent of part can also be found, but major part is all about raw-material preparation, such as, patent publication No. CN101891893A patent document discloses " preparation of LED phenyl-based hydrogen-based silicone resin ", only relate to the synthesis preparation of phenyl-based hydrogen-based silicone resin, do not relate to encapsulation silicon rubber and preparation method, and the packaging plastic toughness using phenyl-based hydrogen-based silicone resin to prepare as starting material is poor, and the use of the linear phenyl hydrogen-containing silicon oil related in this patent can suitably reduce cross-linking density, improve toughness.A small amount of patent is had to relate to the preparation of packaged material, such as, patent publication No. CN101717584A patent document discloses " organic silica gel packaging material of great power LED and its preparation method ", only relate to gel-type packaged material and its preparation method, and the deficiency of silicon gel in mechanical property result in it can not be used in the packing forms such as paster, mould top. And these current patents all do not relate to the problem of the extensive concern in the industry such as the cementability of LED encapsulation material, stability in storage.
Summary of the invention
In order to overcome the above-mentioned deficiency of prior art, one aspect of the present invention provides a kind of optical package high refractive index High-transparency silicon rubber, this packaged material has good stability in storage before not using, solidification has high transparent after using, excellent mechanical property, excellent ageing-resistant performance, and LED support is had good cementability. Additionally provide the preparation method of this kind of silicon rubber on the other hand.
A kind of optical package high refractive index High-transparency silicon rubber of the present invention and its preparation method, become containing the poly-oxygen alkane component C of hydrogen, platinum catalyst component D, catalytic inhibitor component E, modified siloxane component F and water-removal agent component G mixed preparing by the silicone resin component A of phenyl vinyl, phenyl vinyl polysiloxane B component, phenyl, and each ingredients weight parts number is as follows:
Component A95-100 part
B component 0-100 part
Component C5-50 part
Component D0.05-1 part
Component E0.1-2 part
Component F0-10 part
Component G0-3 part
Component A is the silicone resin containing phenyl vinyl, silicone resin add the mechanical property that can improve silicon rubber and hardness etc. Its structural formula is as follows: (R1R2R3SiO1/2)a(R4R5SiO2/2)b(R6SiO3/2)c(SiO2)d
Phenyl vinyl polysiloxane described in upper formula is R by two or more structure7mSi(OR7)4-mSilicon monomer mixing polycondensation and become, 0≤m < 4, R1To R6For alkyl, alkene base or aryl, wherein at least one is alkene base, and at least one is phenyl. R7For carbon number is less than the alkyl of 4. 0≤a, b, c, d < 1, and a+b+c+d=1.
Concrete synthesis step is as follows: by siloxanyl monomers and toluene, the mixture of trifluoromethayl sulfonic acid joins in reaction unit, stirs evenly. Then slowly dripping adding distil water, time controling is at 2 hours, and temperature controls at 20-40 DEG C. Slowly temperature is risen to 30-60 DEG C subsequently, continue reaction 2-6 hour. Drip and add divinyl tetramethyl disiloxane. React again 2-6 hour. Then by the heterogeneous system separating funnel layering of reaction gained, get solvent and resin portion, add Calcium Chloride Powder Anhydrous. Reaction 2-4 hour is continued at 80-120 DEG C. Reaction terminates, and the de-low-boiling-point substance of washing filtering obtains phenyl vinyl polysiloxane.
B component is the polyphenylmethyl radical siloxane of ethenyl blocking, and contents of ethylene is at 0.09%-3.9%, and molecular weight is at 1300-62000. Its structure is:
Wherein m, n are integer, and its span is respectively: m=5～200, n=3～300.
Polyphenylmethyl radical siloxane described in upper formula is according to octamethylcyclotetrasiloxane 3-300 molar part, octaphenylcyclotetrasiloxane 5-200 molar part, the ratio of vinyl closure agent 4 molar part prepares, phenyl monomer add the specific refractory power and thermostability that can improve silicone oil, concrete synthesis step is as follows:
(1) by octamethylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, vinyl closure agent, the mixture of catalyzer Tetramethylammonium hydroxide alkali glue and reaction promotor joins in reaction unit, stirs evenly.
(2) individual hour of stirring reaction 1-15 at 50-120 DEG C.
(3) rise above 130 DEG C of decomposition catalysts, under 180-200 DEG C/0.8KPa, then extract low-boiling-point substance and unreacted methyl ring body out.
(4) crude product solvent wash, removes unreacted benzyl ring body, and separation, deviates from solvent at 100-180 DEG C, obtain the polyphenylmethyl radical siloxane of high purity transparent vinyl base end-blocking.
Washing solvent used is benzene, toluene, dimethylbenzene, trichloromethane, tetrachloromethane, methyl alcohol, ethanol, Virahol, ether, vinyl acetic monomer, acetone, pyridine, tetrahydrofuran (THF), dimethyl formamide, the mixture of one or more in N,N-DIMETHYLACETAMIDE.
Because ring-opening polymerization is active and the reason of monomer conversion, reaction has certain benzyl ring body to remain after terminating, and the boiling point of benzyl ring body is at 400-500 DEG C, it is very difficult to removed by unreacted benzyl ring body by the method for traditional high-temperature vacuum extracting. So we use suitable solvent to be purified by crude product, reduce benzyl ring body to the impact of the performances such as mechanics, electricity, thermostability.
Component C is that phenyl contains the poly-oxygen alkane of hydrogen, and its structure is:
Wherein m, n, p are integer, its span respectively: m=1-60, n=1-35, p=0-40, R are H or CH3. Use the phenyl of linear phenyl hydrogen-containing silicon oil instead of dendroid can reduce the fragility of packaging plastic as linking agent containing hydrogen resin.
Phenyl described in upper formula is according to octamethylcyclotetrasiloxane 0-40 molar part containing the poly-oxygen alkane of hydrogen, and octaphenylcyclotetrasiloxane 1-60 molar part, tetramethyl-ring tetrasiloxane 1-35 molar part, the ratio of closure agent 4 molar part prepares. Wherein closure agent is hexamethyldisiloxane, one or more in 1-hydrogen base-1,1,3,3,3-pentamethyl disiloxane and 1,3-bis-hydrogen base-1,1,3,3-tetramethyl disiloxane. Concrete synthesis step is as follows:
By octamethylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, tetramethyl-ring tetrasiloxane, closure agent, the mixture of catalyzer Zeo-karb and toluene joins in reaction unit, stirs evenly. Add N2, shield, reduce the generation of side reaction, at 40-80 DEG C, react 6h. Reaction terminates, and filters out Zeo-karb, and normal pressure boils off solvent. Vacuumize, keep progressively being warming up to 210 DEG C when vacuum, after removing low-boiling-point substance and remaining solvent, be cooled to room temperature. Crude product solvent wash, removes unreacted benzyl ring body, separation, deviates from solvent and adds gac and stir evenly, then filter, obtain the transparent methyl and phenyl hydrogen-containing silicon oil of high purity at 100-180 DEG C.
Washing solvent used is benzene, toluene, dimethylbenzene, trichloromethane, tetrachloromethane, methyl alcohol, ethanol, Virahol, ether, vinyl acetic monomer, acetone, pyridine, tetrahydrofuran (THF), dimethyl formamide, the mixture of one or more in N,N-DIMETHYLACETAMIDE. Use Zeo-karb more convenient as catalyst operation, decrease the troublesome last handling process using strong acid to make catalyzer.
Component D platinum catalyst is platinum complex, thermoplastic silicone resin parcel platinum complex, the platinum complex of diethyl phthalate coordination, Platinic chloride, the H of vinyl siloxanes coordination2PtCl6Aqueous isopropanol, H2PtCl6Tetrahydrofuran solution, dicyclopentadiene platinum dichloride, Pt (PPh3)4、Cp2PtCl4In the mixture of one or more. General by the dilution of silicone oil or solvent, in catalyzer, the content of platinum is 1000-15000ppm, it is possible to commercial.The more big reaction of the usage quantity of catalyzer is more fast, solidifies more complete, but the catabiosis such as yellow change also more easily occur, it is necessary to suitably add according to service condition.
Component E catalytic inhibitor is 3-Phenyl-1-butyn-3-ol, 3-methyl isophthalic acid-butine-3-alcohol, 1-acetylene-1-hexalin, 1,3-divinyl-1,3-dimethyl-1,3-phenylbenzene sily oxide, 1,3-divinyl-1,1,3,3-tetramethyl disiloxane, azotoluene, nitrogen benzide, one or more in azoformamide.
Component F modified polyorganosiloxane is the polysiloxane containing polarity adhesion promoting groups such as epoxy group(ing), alkoxyl group, ester groups, and its structure is:
R1, R1'For methyl, hydrogen base or phenyl, 0≤n < 100. R2, R3, R4For the one in methyl, phenyl, hydrogen base, alkoxyl group, epoxy group(ing), glycidyl ether deriveding group, 1,2-epoxy-cyclohexane-4-ethyl, carboxylic acid group, acid anhydrides end group, lactan end group. The introducing of the polar groups such as epoxy group(ing) can increase system to the cementability of LED support.
Component G water-removal agent is 1, hexamethylene-diisocyanate, tolylene diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate, Methyl benzenesulfonyl isocyanate, triallyl isocyanurate, triethyl orthoformate, ethyl acetate, one or more in ethyl formate. After preparing product glue, in storage process, the moisture that the components such as resin, containing hydrogen silicone oil, modified polyorganosiloxane easily absorb in air causes product muddy, and this greatly have impact on the performance of product.
The specific refractory power of component A, B, C, F is between 1.48-1.56, and refractive index difference each other is within 0.04. Refractive index difference between the main raw materials such as A, B, C, F is crossed conference and is caused system generation turbid phenomenon.
The mol ratio of formula medium vinyl and silicon hydrogen base is 1:1.05-1.8, and the mol ratio of vinyl and silicon hydrogen is in this scope, and the mechanical property obtaining silicon rubber is best.
Actual product is divided into two portions to pack, and obtains first part by blended for A, B, D component, obtains second section by blended for A, B, C, E, F, G component. During actual use, first part and second section are mixed in the ratio of 1:1, stir even final vacuum deaeration 10-20min, sulfuration 3 hours at 150 DEG C, obtain high refractive index High-transparency silicon rubber packaged material, it is possible to be directly used in the encapsulation of LED.
The high refractive index High-transparency silicon rubber prepared by the present invention can be applicable to the demand of the multiple LED forms such as paster, mould top, COB.
Compared with prior art, useful effect is as follows in the present invention:
Suitable phenyl polysiloxane and the linear use containing hydrogen phenyl silicone oil significantly improve the mechanical property of silicon rubber so that silicon rubber can keep certain toughness while being ensured tensile strength and hardness.
The building-up process of phenyl silicone oil uses the catalyzer Tetramethylammonium hydroxide silicon alkoxide being easy to high temperature and removing, decreases the introducing of metal ion, ensure that the purity of silicone oil. And use the method for purification to be removed by remaining benzyl ring body, further ensure the purity of silicone oil, thus ensure that the property improved of the performances such as silicon rubber mechanics, electricity.
The building-up process of silicone oil and silicone resin uses benzyl ring body or Alkoxy monomeric, instead of chlorosilane monomer, which reduces the introducing of chlorion, it is possible to ensure the ageing-resistant performance of silicon rubber well, and greatly simplifie aftertreatment technology.
Adding of the modified with polar polysiloxane such as epoxy group(ing), alkoxyl group can improve packaged material to a great extent to the cementability of LED support. And add the stability in storage that water-retaining agent can improve product. This is both the great problem that domestic industry faces.
The silicon rubber of the present invention is by the introducing of phenyl, it is possible to make specific refractory power bring up to more than 1.50. And very well, the light transmittance at 450nm wavelength place is more than 90% for the transparency. Mechanical property is excellent, and ageing-resistant performance is good, and the cementability of LED support is better, product can standing storage, be the ideal material of LED.
Embodiment
Embodiment 1
(1) component A phenyl vinyl polysiloxane (PhSiO is prepared3/2)0.55(Ph2SiO2/2)0.02(Me3SiO1/2)0.22(ViMe2SiO1/2)0.21Its contents of ethylene is 5wt%, specific refractory power is 1.518, method is as follows: the mixture of precise hexamethyldisiloxane 81.8, phenylbenzene diethoxy silane 25g, phenyl triethoxysilane 606g, toluene 500g and trifluoromethayl sulfonic acid 0.6g joins in 2L flask, stirs, slowly drip adding distil water at 25 DEG C, dripping amount of water is 45.5g, after dripping, slowly temperature is risen to 50 DEG C, continue reaction 3 hours. Then 1,3-divinyl-1,1,3,3-tetramethyl disiloxane 89.7g is added. Temperature rises to 60 DEG C of reactions 3 hours. Then by the heterogeneous system separating funnel layering of reaction gained, get solvent and resin portion, add Calcium Chloride Powder Anhydrous. Reaction 2 hours is continued at 100 DEG C. Reaction terminates, and washing filtering takes off low-boiling-point substance, obtains component A.
(2) component C methyl and phenyl hydrogen-containing silicon oil H (Me) is prepared2SiO(Ph2SiO2/2)11(Me2SiO2/2)22(MeHSiO2/2)21Si(Me)2H, specific refractory power 1.486, hydrogen content 0.46%, method is as follows: by octamethylcyclotetrasiloxane 198g, octaphenylcyclotetrasiloxane 255g, tetramethyl-ring tetrasiloxane 147.6g, tetramethyl disiloxane 15.84g, the mixture of catalyzer Zeo-karb and toluene joins in reaction unit, stirs evenly. Add N2, shield, reduce the generation of side reaction, at 60 DEG C, react 6h. Reaction terminates, and filters out Zeo-karb, and normal pressure boils off solvent. Vacuumize, keep progressively being warming up to 210 DEG C when vacuum, after removing low-boiling-point substance and remaining solvent, be cooled to room temperature. Crude product solvent wash, removes unreacted benzyl ring body, separation, deviates from solvent and adds gac and stir evenly, then filter, obtain component C at 160-180 DEG C.
(3) getting above-mentioned gained component A 26g, B component is 0, D component platinum complex catalyst 0.03g, blended first part; Getting above-mentioned gained component A 9g, B component is 0, component C 17g, component E 1,3-divinyl-1,1,3,3-tetramethyl disiloxane 0.09g, and F, G component is 0, blended second section; First part and second section being mixed in the ratio of 1:1, stir even final vacuum deaeration 10-20min, sulfuration 3 hours at 150 DEG C, obtain the silicon rubber that specific refractory power is 1.506, Shore A hardness is 90. In 10mm light path cuvette, wavelength is 450nm place transmittance is 89%. It is 0.25MPa with the stripping strength of PPA (LED support material) plastic plate. In product, blended for A, B, C, E, F, G component second section obtained being surveyed after room temperature storage 14d transmittance, in 10mm light path cuvette, wavelength is 450nm place transmittance is 80%.
Embodiment 2
(1) component A phenyl vinyl polysiloxane (PhSiO is prepared3/2)0.55(Ph2SiO2/2)0.02(Me3SiO1/2)0.33(ViMe2SiO1/2)0.1Its contents of ethylene is 2.5wt%, specific refractory power is 1.512, method is as follows: the mixture of precise hexamethyldisiloxane 122.7, phenylbenzene diethoxy silane 25g, phenyl triethoxysilane 606g, toluene 500g and trifluoromethayl sulfonic acid 0.6g joins in 2L flask, stirs, slowly drip adding distil water at 25 DEG C, dripping amount of water is 45.5g, after dripping, slowly temperature is risen to 50 DEG C, continue reaction 3 hours.Then 1,3-divinyl-1,1,3,3-tetramethyl disiloxane 42.7g is added. Temperature rises to 60 DEG C of reactions 3 hours. Then by the heterogeneous system separating funnel layering of reaction gained, get solvent and resin portion, add Calcium Chloride Powder Anhydrous. Reaction 2 hours is continued at 100 DEG C. Reaction terminates, and washing filtering takes off low-boiling-point substance, obtains A group.
(2) polyphenylmethyl radical siloxane Vi (Me) of B component ethenyl blocking is prepared2SiO(Ph2SiO2/2)38(Me2SiO2/2)84Si(Me)2Vi, contents of ethylene 0.386%, specific refractory power 1.513, method is as follows: by the octamethylcyclotetrasiloxane 330g after processed, octaphenylcyclotetrasiloxane 405g, 1, 3-divinyl-1, 1, 3, 3-tetramethyl disiloxane 9.9g, the mixture of Tetramethylammonium hydroxide alkali glue 22g and reaction promotor 73.5g joins with mechanical stirrer, thermometer, in four mouthfuls of flasks of nitrogen protection device and condensing works, oil bath is heated, in nitrogen protection, under normal pressure, material in flask is risen to 90 DEG C from room temperature, at 90 DEG C, polyreaction is after 7 hours, it is warming up to 160 DEG C of decomposition catalysts one hour, it is down to room temperature. using solvent wash polymkeric substance, be placed in separating funnel, static, layering, removes lower floor's liquid, and at 160-180 DEG C, low pressure deviates from solvent, is cooled to room temperature, and in 10mm light path cuvette, wavelength is 450nm place transmittance is 92%.
(3) above-mentioned gained component A 14.54g, B component 4.85g is got, gained component A (PhSiO in embodiment 13/2)0.55(Ph2SiO2/2)0.02(Me3SiO1/2)0.22(ViMe2SiO1/2)0.2114.54g, D component platinum complex catalyst 0.03g, blended first part; Get above-mentioned gained component A 6.46g, B component 2.15g, gained component A (PhSiO in embodiment 13/2)0.55(Ph2SiO2/2)0.02(Me3SiO1/2)0.22(ViMe2SiO1/2)0.216.46g, component C 17.85g, component E 1-acetylene-1-hexalin 0.02g, F component epoxy terminal groups modification silicone oil 1g, G component triallyl isocyanurate 0.01g, blended second section; First part and second section are mixed in the ratio of 1:1, stirs even final vacuum deaeration 10-20min. Sulfuration 3 hours at 150 DEG C, obtain the silicon rubber that specific refractory power is 1.508, and Shore A hardness is 55. In 10mm light path cuvette, wavelength is 450nm place transmittance is 91%. It is 0.93MPa with the stripping strength of PPA (LED support material) plastic plate. In product, blended for A, B, C, E, F, G component second section obtained being surveyed after room temperature storage 14d transmittance, in 10mm light path cuvette, wavelength is 450nm place transmittance is 90%.
Embodiment 3
Gained component A (PhSiO in Example 13/2)0.55(Ph2SiO2/2)0.02(Me3SiO1/2)0.22(ViMe2SiO1/2)0.2114.16g, gained component A (PhSiO in embodiment 23/2)0.55(Ph2SiO2/2)0.02(Me3SiO1/2)0.33(ViMe2SiO1/2)0.19.44g, gained B component Vi (Me) in embodiment 22SiO(Ph2SiO2/2)38(Me2SiO2/2)84Si(Me)2Vi9.44g, D component platinum complex catalyst 0.03g, blended first part; Gained A group (PhSiO in Example 13/2)0.55(Ph2SiO2/2)0.02(Me3SiO1/2)0.22(ViMe2SiO1/2)0.216.84g, gained component A (PhSiO in embodiment 23/2)0.55(Ph2SiO2/2)0.02(Me3SiO1/2)0.33(ViMe2SiO1/2)0.14.56g, gained B component Vi (Me) in embodiment 22SiO(Ph2SiO2/2)38(Me2SiO2/2)84Si(Me)2Vi4.56g, gained component C H (Me) in embodiment 12SiO(Ph2SiO2/2)11(Me2SiO2/2)22(MeHSiO2/2)21Si(Me)2H16.1g, component E 1-acetylene-1-hexalin 0.02g, F component epoxy terminal groups modification silicone oil 1g, G component triallyl isocyanurate 0.01g, blended second section; First part and second section are mixed in the ratio of 1:1, stirs even final vacuum deaeration 10-20min. Sulfuration 3 hours at 150 DEG C, obtain the silicon rubber that specific refractory power is 1.509, and Shore A hardness is 70. In 10mm light path cuvette, wavelength is 450nm place transmittance is 91%. It is 0.95MPa with the stripping strength of PPA (LED support material) plastic plate. In product, blended for A, B, C, E, F, G component second section obtained being surveyed after room temperature storage 14d transmittance, in 10mm light path cuvette, wavelength is 450nm place transmittance is 91%.
Embodiment 4
Gained A group (PhSiO in Example 13/2)0.55(Ph2SiO2/2)0.02(Me3SiO1/2)0.22(ViMe2SiO1/2)0.2114.81g, gained component A (PhSiO in embodiment 23/2)0.55(Ph2SiO2/2)0.02(Me3SiO1/2)0.33(ViMe2SiO1/2)0.19.87g, gained B component Vi (Me) in embodiment 22SiO(Ph2SiO2/2)38(Me2SiO2/2)84Si(Me)2Vi9.87g, D component platinum complex catalyst 0.03g, blended first part; Gained A group (PhSiO in Example 13/2)0.55(Ph2SiO2/2)0.02(Me3SiO1/2)0.22(ViMe2SiO1/2)0.216.19g, gained component A (PhSiO in embodiment 23/2)0.55(Ph2SiO2/2)0.02(Me3SiO1/2)0.33(ViMe2SiO1/2)0.14.13g, gained B component Vi (Me) in embodiment 22SiO(Ph2SiO2/2)38(Me2SiO2/2)84Si(Me)2Vi4.13g, gained component C H (Me) in embodiment 12SiO(Ph2SiO2/2)11(Me2SiO2/2)22(MeHSiO2/2)21Si(Me)2H19.1g, component E 1-acetylene-1-hexalin 0.02g, F component epoxy terminal groups modification silicone oil 1g, G component triallyl isocyanurate 0.01g, blended second section; First part and second section are mixed in the ratio of 1:1, stirs even final vacuum deaeration 10-20min. Sulfuration 3 hours at 150 DEG C, obtain the silicon rubber that specific refractory power is 1.508, and Shore A hardness is 52. In 10mm light path cuvette, wavelength is 450nm place transmittance is 91%. It is 0.90MPa with the stripping strength of PPA (LED support material) plastic plate. In product, blended for A, B, C, E, F, G component second section obtained being surveyed after room temperature storage 14d transmittance, in 10mm light path cuvette, wavelength is 450nm place transmittance is 91%.
Claims (5)
1. an optical package high refractive index High-transparency silicon rubber, it is characterized in that: become by containing the silicone resin component A of phenyl vinyl, phenyl vinyl polysiloxane B component, phenyl hydrogen containing siloxane component C, platinum catalyst component D, catalytic inhibitor component E, modified siloxane component F and water-removal agent component G mixed preparing, and each ingredients weight parts number is as follows:
Component A95-100 part
B component is greater than 0 and is less than or equal to 100 parts
Component C5-50 part
Component D0.05-1 part
Component E0.1-2 part
Component F is greater than 0 and is less than or equal to 10 parts
Component G is greater than 0 and is less than or equal to 3 parts
Described component A is: containing the silicone resin of phenyl vinyl, and its structural formula is as follows:
(R1R2R3SiO1/2)a(R4R5SiO2/2)b(R6SiO3/2)c(SiO2)d
R1To R6For alkyl, alkene base or aryl, wherein at least one is alkene base, and at least one is phenyl, 0≤a, b, d < 1,0 < c < 1 and a+b+c+d=1;
Described B component is: the polyphenylmethyl radical siloxane of ethenyl blocking, and contents of ethylene is at 0.09wt%-3.9wt%, and molecular weight is at 1300-62000, and its structure is:
Wherein m, n are integer, and its span is respectively: m=5～200, n=3～300,
Described component C is: phenyl hydrogen containing siloxane, and its structure is:
Wherein m, n, p are integer, its span respectively: m=1-60, n=1-35, p=0-40, R are H or CH3,
Described D component platinum catalyst is: the platinum complex of vinyl siloxanes coordination, thermoplastic silicone resin parcel platinum complex, the platinum complex of diethyl phthalate coordination, Platinic chloride, H2PtCl6Aqueous isopropanol, H2PtCl6Tetrahydrofuran solution, dicyclopentadiene platinum dichloride, Pt (PPh3)4、Cp2PtCl4In the mixture of one or more;
Described component E catalytic inhibitor is: 3-Phenyl-1-butyn-3-ol, 3-methyl isophthalic acid-butine-3-alcohol, 1-acetylene-1-hexalin; 1,3-divinyl-1,3-dimethyl-1; 3-phenylbenzene sily oxide, 1,3-divinyl-1; 1; 3,3-tetramethyl disiloxane, azotoluene; nitrogen benzide, one or more in azoformamide;
Described F component modification polysiloxane is the polysiloxane containing epoxy group(ing), alkoxyl group, ester group polarity adhesion promoting groups, and its structure is:
R1, R1'For methyl, hydrogen base or phenyl, 0≤n < 100, R2, R3, R4For the one of methyl, phenyl, hydrogen base, alkoxyl group, epoxy group(ing), glycidyl ether deriveding group, carboxylic acid group, acid anhydrides end group, lactan end group;
Described G component water-removal agent is tolylene diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate, Methyl benzenesulfonyl isocyanate, triallyl isocyanurate, triethyl orthoformate, ethyl acetate, one or more in ethyl formate.
2. high refractive index High-transparency silicon rubber according to claim 1, it is characterised in that:
Described component A is containing the silicone resin of phenyl vinyl, and described phenyl vinyl polysiloxane is R by two or more structure7mSi(OR7)4-mSilicon monomer mixing polycondensation and become, wherein, R7For carbon number is less than the alkyl of 4,0≤m < 4;
The polyphenylmethyl radical siloxane of described B component ethenyl blocking; contents of ethylene is at 0.09wt%-3.9wt%; molecular weight is at 1300-62000; described polyphenylmethyl radical siloxane is according to octamethylcyclotetrasiloxane 3-300 molar part; octaphenylcyclotetrasiloxane 5-200 molar part; the ratio of vinyl closure agent 4 molar part prepares, and in phenyl silicone, the content of monomer octaphenylcyclotetrasiloxane is lower than 100ppm;
Described component C phenyl hydrogen containing siloxane is according to octamethylcyclotetrasiloxane 0-40 molar part, octaphenylcyclotetrasiloxane 1-60 molar part, tetramethyl-ring tetrasiloxane 1-35 molar part, the ratio of closure agent 4 molar part prepares, wherein closure agent is hexamethyldisiloxane, 1-hydrogen base-1,1,3,3,3-pentamethyl disiloxane and 1,3-bis-hydrogen base-1,1,3, one or more in 3-tetramethyl disiloxane, in phenyl silicone, the content of monomer octaphenylcyclotetrasiloxane is lower than 100ppm.
3. high refractive index High-transparency silicon rubber according to claim 1 and 2, it is characterised in that: the mol ratio of formula medium vinyl and silicon hydrogen base is 1:1.05-1.8.
4. high refractive index High-transparency silicon rubber according to claim 1 and 2, it is characterised in that the specific refractory power of described component A, B, C, F is between 1.48-1.56, and refractive index difference each other is within 0.04.
5. according to the preparation method of described high refractive index High-transparency silicon rubber arbitrary in claim 1-4, it is characterized in that actual product is divided into two portions to pack, first part is obtained by blended for A, B, D component, second section is obtained by blended for A, B, C, E, F, G component, during actual use, first part and second section are mixed in the ratio of 1:1, stir even final vacuum deaeration 10-20min, sulfuration 3 hours at 150 DEG C, obtain high refractive index High-transparency silicon rubber packaged material, it is possible to be directly used in the encapsulation of LED.
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