CN107828057A - The silicone-modified epoxy resin preparation method and applications of LED encapsulation - Google Patents
The silicone-modified epoxy resin preparation method and applications of LED encapsulation Download PDFInfo
- Publication number
- CN107828057A CN107828057A CN201711117352.5A CN201711117352A CN107828057A CN 107828057 A CN107828057 A CN 107828057A CN 201711117352 A CN201711117352 A CN 201711117352A CN 107828057 A CN107828057 A CN 107828057A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- silicone
- performed polymer
- modified epoxy
- led encapsulation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 76
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 75
- 238000005538 encapsulation Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229920000642 polymer Polymers 0.000 claims abstract description 57
- 238000012986 modification Methods 0.000 claims abstract description 27
- 230000004048 modification Effects 0.000 claims abstract description 27
- 125000003944 tolyl group Chemical group 0.000 claims abstract description 24
- -1 alkoxy silane Chemical compound 0.000 claims abstract description 20
- 239000005046 Chlorosilane Substances 0.000 claims abstract description 19
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000178 monomer Substances 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 17
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 11
- 229910000077 silane Inorganic materials 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 229920005989 resin Polymers 0.000 claims abstract description 4
- 239000011347 resin Substances 0.000 claims abstract description 4
- 125000002524 organometallic group Chemical group 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000005054 phenyltrichlorosilane Substances 0.000 claims description 11
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 claims description 11
- 239000004593 Epoxy Substances 0.000 claims description 9
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 8
- 239000004848 polyfunctional curative Substances 0.000 claims description 8
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 7
- 230000007062 hydrolysis Effects 0.000 claims description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- 238000013517 stratification Methods 0.000 claims description 7
- 150000008064 anhydrides Chemical class 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 3
- 229960001124 trientine Drugs 0.000 claims description 3
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 3
- 150000001555 benzenes Chemical class 0.000 claims description 2
- 239000012141 concentrate Substances 0.000 claims description 2
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- ADJMNWKZSCQHPS-UHFFFAOYSA-L zinc;6-methylheptanoate Chemical compound [Zn+2].CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O ADJMNWKZSCQHPS-UHFFFAOYSA-L 0.000 claims description 2
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 3
- 229910052760 oxygen Inorganic materials 0.000 claims 3
- 239000001301 oxygen Substances 0.000 claims 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 2
- ZYUVGYBAPZYKSA-UHFFFAOYSA-N 5-(3-hydroxybutan-2-yl)-4-methylbenzene-1,3-diol Chemical compound CC(O)C(C)C1=CC(O)=CC(O)=C1C ZYUVGYBAPZYKSA-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- NHADDZMCASKINP-HTRCEHHLSA-N decarboxydihydrocitrinin Natural products C1=C(O)C(C)=C2[C@H](C)[C@@H](C)OCC2=C1O NHADDZMCASKINP-HTRCEHHLSA-N 0.000 claims 1
- NOKUWSXLHXMAOM-UHFFFAOYSA-N hydroxy(phenyl)silicon Chemical compound O[Si]C1=CC=CC=C1 NOKUWSXLHXMAOM-UHFFFAOYSA-N 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000035939 shock Effects 0.000 abstract description 3
- 238000004382 potting Methods 0.000 abstract description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 9
- 239000005055 methyl trichlorosilane Substances 0.000 description 6
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 229940106691 bisphenol a Drugs 0.000 description 4
- 238000002454 metastable transfer emission spectrometry Methods 0.000 description 3
- VKEQBMCRQDSRET-UHFFFAOYSA-N Methylone Chemical compound CNC(C)C(=O)C1=CC=C2OCOC2=C1 VKEQBMCRQDSRET-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/10—Block or graft copolymers containing polysiloxane sequences
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/005—Processes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/52—Encapsulations
- H01L33/56—Materials, e.g. epoxy or silicone resin
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
Abstract
The present invention relates to the preparation method and applications of a kind of LED potting resins preparation technology and application, the particularly a kind of silicone-modified epoxy resin of LED encapsulation.Note in reactor, add bisphenol A epoxide resin, alkoxy silane, organometallic salt catalysts, reacted 1 hour at 50~150 DEG C, epoxy resin modification performed polymer is made；It is raw material using mixed chlorosilane monomer and organic solvent, prepares methyl phenyl siloxane performed polymer；Epoxy resin modification performed polymer is added in reactor；Methyl phenyl siloxane performed polymer, reacted 2~6 hours under 70~150 DEG C of vacuum conditions, the silicone-modified epoxy resin of LED encapsulation is made.Compared with organic siliconresin, this silicone-modified epoxy resin have with base material cohesive force it is good the characteristics of；Compared with epoxy resin, this silicone-modified epoxy resin has the characteristics of cold-resistant thermal shock, heat-resist.
Description
Technical field
The present invention relates to a kind of LED potting resins preparation technology and application, particularly a kind of LED is encapsulated with silicone-modified
The preparation method and applications of epoxy resin.
Background technology
Bisphenol-A type epoxy resin has that light transmittance is high, mechanical property is good, corrosion-resistant, cost is low, easy to operate etc. excellent
Point, but it crosslink density is high after hardening, internal stress is big, poor impact resistance, easily produced under shortwave radiation and heat effect yellow
Become phenomenon, so requirements of the new power type LED to encapsulating material can not be met.
Organosilicon material has the characteristics that the good transparency, resistant of high or low temperature, weatherability, heat endurance, but exists
The shortcomings that corrosion-resistant, adhesion strength are low, poor mechanical property and cost are high.
Silicone-modified epoxy resin has the advantages of two kinds of materials concurrently, is preferable encapsulating material.
A kind of silane coupler modified epoxy resin of CN201310310813.6 Jiangsu Su Bote new materials and its preparation
Method and application, the patent uses the silane coupler containing amino to epoxy resin modification, because silicone segments are shorter, to tree
The performance boosts such as fat is heat-resisting are limited.
The .7 South China Science ＆ Engineering University of patent application 201611093859 discloses a kind of LED encapsulation aminomethyl phenyl epoxy and changed
The preparation method of property silicone oil, the patent realize modification by the way of Si―H addition reaction, it is desirable to the epoxy resin of specific model, cost
It is higher.
The content of the invention
It is an object of the invention to overcome the deficiency of prior art and provide a kind of heat-resist, cold-resistant thermal shock and with
The preparation method and applications of the good silicone-modified epoxy resin of LED encapsulation of base material cohesive force.
The preparation method of the present invention adopts the following technical scheme that：
A kind of LED encapsulation preparation method of silicone-modified epoxy resin, is prepared as follows：
1）It is prepared by epoxy resin modification performed polymer：
Note in reactor, add the mass parts of bisphenol A epoxide resin 40~80, the mass parts of alkoxy silane 1~30, organic metal salt
The mass parts of catalyst 0.01~1, reacted 1 hour at 50~150 DEG C, epoxy resin modification performed polymer is made；
2）It is prepared by siloxanes performed polymer：
It is raw material using mixed chlorosilane monomer and organic solvent, prepares methyl phenyl siloxane performed polymer；
3）LED encapsulates the preparation with silicone-modified epoxy resin：
The mass parts of epoxy resin modification performed polymer 50~90, the mass of methyl phenyl siloxane performed polymer 10~50 are added in reactor
Part, reacted 2~6 hours under 70~150 DEG C of vacuum conditions, the silicone-modified epoxy resin of LED encapsulation is made.
Relative to prior art, using above-mentioned technical proposal the invention has the advantages that and beneficial effect：
1st, compared with organic siliconresin, this silicone-modified epoxy resin have with base material cohesive force it is good the characteristics of；With epoxy
Resin is compared, and this silicone-modified epoxy resin has the characteristics of cold-resistant thermal shock, heat-resist.
2nd, alkoxy silane is participated in reaction, be more prone to compared to carbon hydroxyl and silicone hydroxyl directly reaction, mild condition.
3rd, siloxanes performed polymer is prepared using chlorosilane raw material, is raw material relative to alkoxy silane, cost is lower.
LED encapsulates the preparation method with silicone-modified epoxy resin, using following preferred scheme：
Bisphenol A epoxide resin is one kind in E20, E44.
Mixed chlorosilane monomer selects phenyl trichlorosilane and dimethyldichlorosilane.
Mixed chlorosilane monomer is from phenyl trichlorosilane and dimethyldichlorosilane and diphenyl dichlorosilane or methyl
One of trichlorosilane carries out mixing match.
In epoxy resin modification pre-polymerization production procedure, alkoxy silane used is from MTMS, methyl
One kind in triethoxysilane, phenyltrimethoxysila,e or phenyl triethoxysilane.
In epoxy resin modification pre-polymerization production procedure, organometallic salt catalysts used be zinc naphthenate, cobalt naphthenate,
One kind in zinc Isoocatanoate, zinc octoate or dibutyl tin laurate.
Methyl phenyl siloxane performed polymer is prepared according to following quality proportioning：Phenyl trichlorosilane, diphenyl dichlorosilane,
Methyl trichlorosilane, dimethyldichlorosilane in mass ratio 1~20:0~10:0~10:1~20 mixing, benzene series
The quality of organic solvent is 1~3 times of mixed chlorosilane monomer mass, and the quality of water is mixed chlorosilane monomer mass
0.5~4 times.
The specific preparation method of methyl phenyl siloxane performed polymer is：
A, hydrolyze
Production water is added in reactor, mixed chlorosilane monomer and organic solvent at the uniform velocity add reactor after being uniformly mixed according to a ratio
In；Control 20~50 DEG C of hydrolysis temperature；Stratification after charging, hydrochloric acid is separated；
B, wash
Methyl phenyl siloxane performed polymer containing organic solvent is washed to neutrality；30~60 DEG C of washing temperature.
C, concentrate
Solvent-laden methyl phenyl siloxane performed polymer is subjected to continuous concentration under vacuum conditions, methylbenzene is made in abjection solvent
Radical siloxane performed polymer.
LED encapsulation material is solidified under amine or the effect of anhydrides epoxy hardener.
Amine epoxy hardener selects diethylenetriamine or triethylene tetramine；Anhydrides epoxy hardener selects methyl hexahydro
Phthalic anhydride.
Embodiment：
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.Below
Embodiment test result is with reference to following testing standard：
Paint and varnish paint film draws lattice measuring paint film adhesion, GB/T 9286-1998.
The measure GBT 1735-2009 of paint and varnish heat resistance.
Paint film impact resistance assay method GB1732-93.
Embodiment one：
It is prepared by epoxy resin modification performed polymer：In reactor, E44 epoxy resin 60g, MTES 9g, two are added
Dibutyl tin laurate 0.01g, 70 DEG C are reacted 1 hour, and epoxy resin modification performed polymer 64g is made.
Phenyl trichlorosilane 50g, diphenyl dichlorosilane 5g, methyl trichlorosilane 10g, dimethyldichlorosilane 15g, with
200g xylene solvents are well mixed, and production water 100g are added in reactor, mixed chlorosilane monomer and organic solvent are even
Speed is added in reactor, controls 40 DEG C of hydrolysis temperature.Stratification after charging, in being washed to after hydrochloric acid is separated with 30 DEG C
Property.Solvent methyl phenyl siloxane performed polymer will be contained under vacuum conditions and carry out continuous concentration, aminomethyl phenyl is made in abjection solvent
Siloxanes performed polymer 45g.
Epoxy resin modification performed polymer 64g, methyl phenyl siloxane performed polymer 45g, 140 DEG C of vacuum bars are added in reactor
2-6 hours are reacted under part, the silicone-modified epoxy resin of LED encapsulation is made.
Product performance index：
Adhesive force：1 grade.
Heat resistance（250℃）：4h passes through.
Impact resistance：50cm.
In actual application, obtained silicone-modified epoxy resin mixes with amine or anhydrides epoxy hardener
Close uniformly after, can use as encapsulating material, be matched according to being actually needed, for example, silicone-modified epoxy resin and
The quality proportioning of amine selects 10：1 ratio.
Amine epoxy hardener selects diethylenetriamine or triethylene tetramine；Anhydrides epoxy hardener selects methyl hexahydro
Phthalic anhydride.
Embodiment two：
It is prepared by epoxy resin modification performed polymer：In reactor, E20 epoxy resin 80g, MTES 4g, two are added
Dibutyl tin laurate 0.02g, 80 DEG C are reacted 1 hour, and epoxy resin modification performed polymer 82g is made.
The specific performance of E20 bisphenol A epoxide resins：It is yellowish to brown color transparent solid；Color and luster number -- 8；Softening point
64---76；Epoxide equivalent/100 gram：0.18--0.23；Organochlorine equivalent/100 gram：0.02；Inorganic chlorine equivalent/100 gram
0.001；The % of volatile matter equivalent 1；Market can be bought.
Phenyl trichlorosilane 60g, diphenyl dichlorosilane 3g, methyl trichlorosilane 20g, dimethyldichlorosilane 27g, with
240g dimethylbenzene organic solvents are well mixed, and production water 120g, chlorosilane monomer and organic solvent after mixing are added in reactor
At the uniform velocity add in reactor, control 30 DEG C of hydrolysis temperature.Stratification after charging, it is washed to after hydrochloric acid is separated with 40 DEG C
It is neutral.Solvent methyl phenyl siloxane performed polymer will be contained under vacuum conditions and carry out continuous concentration, methylbenzene is made in abjection solvent
Radical siloxane performed polymer 60g.
Epoxy resin modification performed polymer 82g, methyl phenyl siloxane performed polymer 60g, 140 DEG C of vacuum bars are added in reactor
2-6 hours are reacted under part, the silicone-modified epoxy resin of LED encapsulation is made.
Product performance index：
Adhesive force：1 grade
Heat resistance（250℃）：4h passes through
Impact resistance：50cm.
Embodiment three：
It is prepared by epoxy resin modification performed polymer：In reactor, E44 epoxy resin 70g, MTMS 6g, two are added
Dibutyl tin laurate 0.01g, 70 DEG C are reacted 1 hour, and epoxy resin modification performed polymer 76g is made.
Phenyl trichlorosilane 45g, diphenyl dichlorosilane 5g, methyl trichlorosilane 15g, dimethyldichlorosilane 15g, with
200g dimethylbenzene is well mixed, and production water 100g is added in reactor, chlorosilane monomer and organic solvent at the uniform velocity add after mixing
In reactor, 40 DEG C of hydrolysis temperature is controlled.Stratification after charging, neutrality is washed to 30 DEG C after hydrochloric acid is separated.
Solvent methyl phenyl siloxane performed polymer will be contained under vacuum state and carry out continuous concentration, methyl phenyl siloxane is made in abjection solvent
Performed polymer 45g.
Epoxy resin modification performed polymer 76g, methyl phenyl siloxane performed polymer 45g, 140 DEG C of vacuum bars are added in reactor
2-6 hours are reacted under part, the silicone-modified epoxy resin of LED encapsulation is made.
Product performance index：
Adhesive force：1 grade.
Heat resistance（250℃）：4h passes through.
Impact resistance：50cm.
Example IV：
It is prepared by epoxy resin modification performed polymer：In reactor, E44 epoxy resin 50g, phenyl triethoxysilane 6g, two are added
Dibutyl tin laurate 0.01g, 70 DEG C are reacted 1 hour, and epoxy resin modification performed polymer 56g is made.
Phenyl trichlorosilane 45g, diphenyl dichlorosilane 5g, methyl trichlorosilane 15g, dimethyldichlorosilane 15g, with
200g dimethylbenzene organic solvents are well mixed, and production water 80g are added in reactor, chlorosilane monomer and organic solvent are even after mixing
Speed is added in reactor, controls 40 DEG C of hydrolysis temperature.Stratification after charging, in being washed to after hydrochloric acid is separated with 30 DEG C
Property.Solvent methyl phenyl siloxane performed polymer will be contained under vacuum conditions and carry out continuous concentration, aminomethyl phenyl is made in abjection solvent
Siloxanes performed polymer 45g.
Epoxy resin modification performed polymer 56g, methyl phenyl siloxane performed polymer 45g, 140 DEG C of vacuum bars are added in reactor
2-6 hours are reacted under part, the silicone-modified epoxy resin of LED encapsulation is made.
Product performance index：
Adhesive force：1 grade.
Heat resistance（250℃）：4h passes through.
Impact resistance：50cm.
Embodiment five：
It is prepared by epoxy resin modification performed polymer：In reactor, E44 epoxy resin 70g, MTES 7g, two are added
Dibutyl tin laurate 0.01g, 70 DEG C are reacted 1 hour, and epoxy resin modification performed polymer 77g is made.
Phenyl trichlorosilane 40g, diphenyl dichlorosilane 5g, methyl trichlorosilane 15g, dimethyldichlorosilane 20g, with
200g dimethylbenzene organic solvents are well mixed, and production water 100g, chlorosilane monomer and organic solvent after mixing are added in reactor
At the uniform velocity add in reactor, control 40 DEG C of hydrolysis temperature.Stratification after charging, it is washed to after hydrochloric acid is separated with 30 DEG C
It is neutral.Solvent methyl phenyl siloxane performed polymer will be contained under vacuum conditions and carry out continuous concentration, methylbenzene is made in abjection solvent
Radical siloxane performed polymer 45g.
Epoxy resin modification performed polymer 77g, methyl phenyl siloxane performed polymer 45g, 140 DEG C of vacuum bars are added in reactor
2-6 hours are reacted under part, the silicone-modified epoxy resin of LED encapsulation is made.
Product performance index：
Adhesive force：1 grade.
Heat resistance（250℃）：4h passes through.
Impact resistance：50cm.
Claims (10)
1. a kind of LED encapsulation preparation method of silicone-modified epoxy resin, is prepared as follows：
1）It is prepared by epoxy resin modification performed polymer：
Note in reactor, add the mass parts of bisphenol A epoxide resin 40~80, the mass parts of alkoxy silane 1~30, organic metal salt
The mass parts of catalyst 0.01~1, reacted 1 hour at 50~150 DEG C, epoxy resin modification performed polymer is made；
2）It is prepared by siloxanes performed polymer：
It is raw material using mixed chlorosilane monomer and organic solvent, prepares methyl phenyl siloxane performed polymer；
3）LED encapsulates the preparation with silicone-modified epoxy resin：
The mass parts of epoxy resin modification performed polymer 50~90, the mass of methyl phenyl siloxane performed polymer 10~50 are added in reactor
Part, reacted 2~6 hours under 70~150 DEG C of vacuum conditions, the silicone-modified epoxy resin of LED encapsulation is made.
2. the preparation method of the silicone-modified epoxy resin of LED encapsulation according to claim 1, it is characterised in that：It is double
Phenol A epoxy resin is one kind in E20, E44.
3. the preparation method of the silicone-modified epoxy resin of LED encapsulation according to claim 1, it is characterised in that：
Mixed chlorosilane monomer selects phenyl trichlorosilane and dimethyldichlorosilane.
4. the preparation method of the silicone-modified epoxy resin of LED encapsulation according to claim 1, it is characterised in that：
Mixed chlorosilane monomer is from phenyl trichlorosilane and dimethyldichlorosilane and diphenyl dichlorosilane or methyl trichlorine
One of silane carries out mixing match.
5. the preparation method of the silicone-modified epoxy resin of LED encapsulation according to claim 1, it is characterised in that：Ring
In oxygen resin modified pre-polymerization production procedure, alkoxy silane used is from MTMS, methyltriethoxy silane
One kind in alkane, phenyltrimethoxysila,e or phenyl triethoxysilane.
6. the preparation method of the silicone-modified epoxy resin of LED encapsulation according to claim 1, it is characterised in that：Ring
In oxygen resin modified pre-polymerization production procedure, organometallic salt catalysts used be zinc naphthenate, cobalt naphthenate, zinc Isoocatanoate,
One kind in zinc octoate or dibutyl tin laurate.
7. the preparation method of the silicone-modified epoxy resin of LED encapsulation according to claim 3 or 4, it is characterised in that：
Methyl phenyl siloxane performed polymer is prepared according to following quality proportioning：Phenyl trichlorosilane, diphenyl dichlorosilane, methyl trichlorine
Silane, dimethyldichlorosilane in mass ratio 1~20:0~10:0~10:1~20 mixing, benzene series organic solvent
Quality be 1~3 times of mixed chlorosilane monomer mass, the quality of water is the 0.5~4 of mixed chlorosilane monomer mass
Times.
8. the preparation method of the silicone-modified epoxy resin of LED encapsulation according to claim 1, it is characterised in that：First
The specific preparation method of base phenyl siloxane performed polymer is：
A, hydrolyze
Production water is added in reactor, mixed chlorosilane monomer and organic solvent at the uniform velocity add reactor after being uniformly mixed according to a ratio
In；Control 20~50 DEG C of hydrolysis temperature；Stratification after charging, hydrochloric acid is separated；
B, wash
Methyl phenyl siloxane performed polymer containing organic solvent is washed to neutrality；30~60 DEG C of washing temperature；
C, concentrate
Solvent-laden methyl phenyl siloxane performed polymer is subjected to continuous concentration under vacuum conditions, methylbenzene is made in abjection solvent
Radical siloxane performed polymer.
9. a kind of described LED such as any one in claim 1 to 8 encapsulates the application with silicone-modified epoxy resin,
It is characterized in that：LED encapsulation material is solidified under amine or the effect of anhydrides epoxy hardener.
10. the application of the silicone-modified epoxy resin of LED encapsulation according to claim 9, it is characterised in that：Amine ring
Oxygen curing agent selects diethylenetriamine or triethylene tetramine；Anhydrides epoxy hardener selects methyl hexahydrophthalic anhydride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711117352.5A CN107828057B (en) | 2017-11-13 | 2017-11-13 | Preparation method and application of siloxane modified epoxy resin for LED packaging |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711117352.5A CN107828057B (en) | 2017-11-13 | 2017-11-13 | Preparation method and application of siloxane modified epoxy resin for LED packaging |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107828057A true CN107828057A (en) | 2018-03-23 |
| CN107828057B CN107828057B (en) | 2021-01-29 |
Family
ID=61655245
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711117352.5A Active CN107828057B (en) | 2017-11-13 | 2017-11-13 | Preparation method and application of siloxane modified epoxy resin for LED packaging |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107828057B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108727981A (en) * | 2018-07-11 | 2018-11-02 | 合肥铭佑高温技术有限公司 | A kind of high-temperature service high-temperature resistant coating and preparation method thereof |
| CN112251014A (en) * | 2020-08-24 | 2021-01-22 | 安徽众博新材料有限公司 | Epoxy resin system-based photoelectric coupler packaging composite material and preparation method thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4359566A (en) * | 1981-01-15 | 1982-11-16 | Dow Corning Corporation | Silicone-epoxy coating compositions |
| CN1313871A (en) * | 1999-06-17 | 2001-09-19 | 荒川化学工业株式会社 | Epoxy resin composition and process for producing silane-modified epoxy resin |
| KR100587480B1 (en) * | 2005-05-06 | 2006-06-09 | 국도화학 주식회사 | Epoxy modified with alcoxysilane |
| JP2006229910A (en) * | 2005-02-15 | 2006-08-31 | Nikkei Denki Kk | Manufacturing method of super heat-resistant bobbin material for voice coil |
| JP2011021078A (en) * | 2009-07-14 | 2011-02-03 | Jsr Corp | Organopolysiloxane, and curable composition comprising the same and manufacturing method for the same |
| CN102076734A (en) * | 2008-07-03 | 2011-05-25 | 旭化成化学株式会社 | Modified resin composition, method for producing the same, and curable resin composition containing the same |
| CN102782014A (en) * | 2010-03-02 | 2012-11-14 | 日本化药株式会社 | Process for production of organopolysiloxane, organopolysiloxane obtained by the process, and composition that contains the organopolysiloxane |
| JP5086710B2 (en) * | 2007-07-06 | 2012-11-28 | 昭和電工株式会社 | Modified organopolysiloxane, process for producing the same, composition containing the same, and composition for encapsulating light emitting diode |
| CN103360603A (en) * | 2013-06-21 | 2013-10-23 | 深圳市森日有机硅材料有限公司 | Phenyl vinyl silicone resin for packaging LED (light-emitting diode) and preparation method thereof |
| CN106905703A (en) * | 2017-03-27 | 2017-06-30 | 北京化工大学 | A kind of preparation method of epoxy modified silicone resin exotic material |
-
2017
- 2017-11-13 CN CN201711117352.5A patent/CN107828057B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4359566A (en) * | 1981-01-15 | 1982-11-16 | Dow Corning Corporation | Silicone-epoxy coating compositions |
| CN1313871A (en) * | 1999-06-17 | 2001-09-19 | 荒川化学工业株式会社 | Epoxy resin composition and process for producing silane-modified epoxy resin |
| JP2006229910A (en) * | 2005-02-15 | 2006-08-31 | Nikkei Denki Kk | Manufacturing method of super heat-resistant bobbin material for voice coil |
| KR100587480B1 (en) * | 2005-05-06 | 2006-06-09 | 국도화학 주식회사 | Epoxy modified with alcoxysilane |
| JP5086710B2 (en) * | 2007-07-06 | 2012-11-28 | 昭和電工株式会社 | Modified organopolysiloxane, process for producing the same, composition containing the same, and composition for encapsulating light emitting diode |
| CN102076734A (en) * | 2008-07-03 | 2011-05-25 | 旭化成化学株式会社 | Modified resin composition, method for producing the same, and curable resin composition containing the same |
| JP2011021078A (en) * | 2009-07-14 | 2011-02-03 | Jsr Corp | Organopolysiloxane, and curable composition comprising the same and manufacturing method for the same |
| CN102782014A (en) * | 2010-03-02 | 2012-11-14 | 日本化药株式会社 | Process for production of organopolysiloxane, organopolysiloxane obtained by the process, and composition that contains the organopolysiloxane |
| CN103360603A (en) * | 2013-06-21 | 2013-10-23 | 深圳市森日有机硅材料有限公司 | Phenyl vinyl silicone resin for packaging LED (light-emitting diode) and preparation method thereof |
| CN106905703A (en) * | 2017-03-27 | 2017-06-30 | 北京化工大学 | A kind of preparation method of epoxy modified silicone resin exotic material |
Non-Patent Citations (4)
| Title |
|---|
| 方高: ""LED封装用硅树脂的研究进展"", 《广州化工》 * |
| 朱化雨等: ""一种聚苯基甲基硅氧烷改性环氧树脂耐高温防腐蚀涂料的制备研究"", 《化工新型材料》 * |
| 李美江等: ""聚甲基苯基硅氧烷改性双酚Ｆ环氧树脂及其粘接性能的研究"", 《杭州师范大学学报（自然科学版）》 * |
| 章基凯: "《有机硅材料》", 31 October 1999, 中国物资出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108727981A (en) * | 2018-07-11 | 2018-11-02 | 合肥铭佑高温技术有限公司 | A kind of high-temperature service high-temperature resistant coating and preparation method thereof |
| CN112251014A (en) * | 2020-08-24 | 2021-01-22 | 安徽众博新材料有限公司 | Epoxy resin system-based photoelectric coupler packaging composite material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107828057B (en) | 2021-01-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102977553A (en) | Epoxy/silicone polymer composite material, and preparation method and application thereof | |
| CN101857789B (en) | Epoxy silsesquioxane/epoxy resin hybridized glue for packaging photoelectric devices and preparation method thereof | |
| CN103102687B (en) | One-component room curing sealing material and preparation method thereof | |
| CN102559048A (en) | Preparation method of epoxy-modified insulated thermal-conductive high-temperature resistant organosilicon coating and its products | |
| CN101591422A (en) | A kind of preparation method of reactive fluid rubber-epoxide resin polymer | |
| CN101619169A (en) | Heat-curable silicone resin-epoxy resin composition, and premolded package molded from same | |
| CN106433034B (en) | A kind of preparation method of amino functional carbon nano tube/epoxy resin composite material | |
| CN107828057A (en) | The silicone-modified epoxy resin preparation method and applications of LED encapsulation | |
| CN104292755B (en) | High-molecule LED (Light-Emitting Diode) packaging material and preparation method thereof | |
| CN102782000B (en) | Resin composition for sealing an optical semiconductor and optical semiconductor device using said resin composition | |
| CN102585226A (en) | Preparation method for thermoset high temperature resistant methyl phenyl silicone resin | |
| CN103897643A (en) | Room-temperature cured high heat-proof epoxy adhesive | |
| CN104231633A (en) | Conductive grapheme and organic silicon resin composite material | |
| CN104356894A (en) | Preparation method of high-temperature-resistant organic silicon modified unsaturated polyester resin coating | |
| CN104347530A (en) | Encapsulant with base for use in semiconductor encapsulation, semiconductor apparatus, and method for manufacturing semiconductor apparatus | |
| CN108350150A (en) | Composition epoxy resin | |
| CN102516501A (en) | Photo-curing material for manufacturing light-emitting diode (LED) lens | |
| CN103608408B (en) | Curable compositions | |
| CN110305609A (en) | A kind of bi-component flexible compound epoxy resin adhesive | |
| CN101089048B (en) | Epoxy-organic silicon mixed resin combination and luminous semiconductor device | |
| CN106497475A (en) | A kind of adhesive for one side glass cloth reinforcement low resin mica tape and preparation method thereof | |
| CN106750329B (en) | Preparation method of high water resistance fluorine-silicon modified epoxy resin | |
| CN110128782A (en) | Compatible anticorrosive composition epoxy resin of a kind of copper wire and preparation method thereof | |
| CN106867202A (en) | A kind of composition epoxy resin | |
| CN101705074B (en) | High temperature screw thread fastening glue and production method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 063305 Nanpu Development Zone, Hebei, Tangshan City Patentee after: Tangshan Sanyou Silicon Industry Co.,Ltd. Address before: 063305 Nanpu Development Zone, Hebei, Tangshan City Patentee before: SANYOU SILICON INDUSTRY Co.,Ltd. |
|
| CP01 | Change in the name or title of a patent holder |