CN112812304A - Prepolymer, packaging resin containing prepolymer and application of packaging resin - Google Patents

Prepolymer, packaging resin containing prepolymer and application of packaging resin Download PDF

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CN112812304A
CN112812304A CN202110015679.1A CN202110015679A CN112812304A CN 112812304 A CN112812304 A CN 112812304A CN 202110015679 A CN202110015679 A CN 202110015679A CN 112812304 A CN112812304 A CN 112812304A
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prepolymer
weight
resin
parts
encapsulating resin
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CN112812304B (en
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谭晓华
单秋菊
于会云
孙绪筠
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Tianjin Degao Huacheng Optoelectronics Technology Co ltd
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Tianjin Degao Huacheng Optoelectronics Technology Co ltd
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Priority to PCT/CN2021/126349 priority patent/WO2022148103A1/en
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    • 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
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • H01L33/483—Containers
    • H01L33/486—Containers adapted for surface mounting
    • 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
    • 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
    • H01L33/58—Optical field-shaping elements
    • H01L33/60—Reflective elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Epoxy Resins (AREA)
  • Silicon Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Led Device Packages (AREA)
  • Sealing Material Composition (AREA)

Abstract

The invention discloses a prepolymer, which is prepared from the following raw materials: (A) a compound having a structure as shown in formula 1, formula 1:
Figure DDA0002886641300000011
wherein R is1、R2、R3Each independently selected from vinyl or epoxy; (B) organosiloxanes containing phenyl and Si-H groups; (C) platinum catalysisAnd (3) preparing. The prepolymer adopts a specific compound to combine with organic silicon, so that the compatibility of the organic silicon and epoxy resin is improved, the process is simple, convenient and easy to operate, the yield is high, and the high-performance packaging resin can be further produced conveniently. The invention also provides an encapsulation resin which comprises epoxy resin, the prepolymer, a curing agent, an adhesive force promoter and a catalyst. The packaging resin is prepared by reacting an epoxy component with a curing agent to generate thermosetting epoxy resin, has excellent performance of resisting light aging of a blue light wave band of 450-470nm, is excellent in heat resistance, easy to package, good in transparency and wide in market prospect.

Description

Prepolymer, packaging resin containing prepolymer and application of packaging resin
Technical Field
The invention relates to the technical field of thermosetting packaging molding materials, in particular to a prepolymer, packaging resin containing the prepolymer and application of the packaging resin.
Background
As a light Emitting semiconductor, an led (light Emitting diode) has become an irreplaceable photoelectric device in the fields of illumination, active RGB display, LCD backlight, vehicle lighting, and the like. The LED lighting and RGB display device packaging mostly adopts an LED packaging structure that a reflecting cup is pre-molded on a resin substrate and a metal support, then liquid packaging materials are poured or filled in the reflecting cup in a dispensing mode, and the packaging materials and the reflecting cup are integrated after thermal curing. The reflecting cup is a carrier of a liquid packaging material, and simultaneously bears the light emission of the reflecting LED chip to form an upward direct-emitting (Top View) single-side light-emitting structure. The white light illuminating device adopts a white reflecting cup package to enhance the light extraction efficiency, and the RGB display device adopts a black reflecting cup to improve the contrast ratio of the display.
The white light LED adopts a blue light chip with the emission wavelength of 450-470nm as a light source, yellow light is emitted by exciting yellow fluorescent powder mixed in the packaging resin, and finally the yellow light and the blue light are synthesized into white light. PPA (polyphthalamide resin) materials are used for the first time as the reflecting cup of the white light device, and the PPA (polyphthalamide) materials are used as thermoplastic materials, so that the PPA materials are easy to injection mold, strong in flexibility, low in cost and the like, and are very suitable for packaging low-power white light LEDs of 0.5-1W. And the blue light chip has strong photodegradation effect on PPA resin to cause yellowing of the material, so that the reflectivity of the reflective cup material is reduced, and the light emitting of the LED chip is damaged. In addition, when the white light LED chip is applied to a lamp, the reflow soldering surface mounting process at the high temperature of 260 ℃ at most needs to be carried out, and the thermoplastic PPA is easy to generate deformation and thermal expansion stress at the high temperature to damage the LED lamp bead.
Later on, thermosetting epoxy resin reflecting cup materials taking triazine derivative epoxy resin or alicyclic epoxy resin as a core component appear on the market, and are called as 'EMC supports'. The epoxy resin does not contain a benzene ring structure, so that the blue light resistance of the EMC bracket is greatly improved compared with that of a PPA material, the reflow soldering resistance and thermal deformation resistance are also excellent due to the thermosetting material, and the white light chip packaged by the material is called as an EMC lamp bead by the industry. Although the EMC reflector cup holder has obvious advantages of blue light resistance and heat resistance compared with PPA thermoplastic materials, the blue light resistance problem still exists in the LED products with stronger power (2-3W), and yellowing of epoxy resin is still a major focus problem under long-term high temperature and blue light irradiation.
Disclosure of Invention
In order to solve the above problems, a first aspect of the present invention provides a prepolymer, which is prepared from the following raw materials:
(A) a compound having a structure as shown in formula 1, formula 1:
Figure BDA0002886641280000021
wherein R is1、R2、R3Each independently selected from vinyl or epoxy;
(B) organosiloxanes containing phenyl and Si-H groups;
(C) a platinum catalyst.
As a preferable technical scheme, the preparation raw material of the prepolymer also comprises (D) an inhibitor.
The second aspect of the present invention provides a method for preparing the prepolymer, which comprises the following steps: melting 100 parts by weight of (A) a compound with a structure shown in formula 1, (B) organosiloxane containing phenyl and Si-H groups, and (D) an inhibitor at 60-150 ℃, uniformly mixing, cooling to 60-120 ℃, adding (C) a platinum catalyst, and stirring for 5-15 hours to obtain a prepolymer.
The third aspect of the invention provides an encapsulation resin, and the preparation raw materials of the encapsulation resin comprise epoxy resin, the prepolymer, a curing agent, an adhesion promoter and a catalyst.
A fourth aspect of the present invention provides a method for producing the encapsulating resin as described above, comprising the steps of: and (3) stirring the epoxy resin and the prepolymer at 100-150 ℃, adding the curing agent, the adhesion promoter and the catalyst, stirring, discharging, cooling, crushing and cake-making to obtain the packaging resin.
The fifth aspect of the invention provides an encapsulating resin for a white reflecting cup, which is prepared from 100 parts by weight of the encapsulating resin and 50-400 parts by weight of titanium dioxide.
The sixth aspect of the invention provides an application of the packaging resin for the white reflecting cup, which is used for a white LED device with power of 1-3W.
The seventh aspect of the invention provides an encapsulating resin for a black reflecting cup, which is prepared from 100 parts by weight of the encapsulating resin and 1-30 parts by weight of carbon black.
An eighth aspect of the present invention provides a use of the above-mentioned packaging resin for black reflector cups, for surface mount SMT light emitting devices of outdoor RGB display screens.
A ninth aspect of the present invention provides an LED device having a reflective cup structure obtained by injection molding of a metal frame or a resin substrate and an encapsulating resin as described above.
Has the advantages that: the invention provides a prepolymer, which adopts a specific compound to combine with organic silicon, increases the compatibility of the organic silicon and epoxy resin, has simple and convenient process, easy operation and high yield, and is convenient for further producing high-performance packaging resin. The packaging resin disclosed by the invention is prepared into thermosetting epoxy resin through the reaction of an epoxy component and a curing agent, has excellent performance of resisting light aging of a blue light wave band of 450-470nm, is excellent in heat resistance, easy to package, good in transparency and wide in market prospect.
Drawings
In order to further explain the advantages of the prepolymer, the packaging resin containing the prepolymer and the application of the packaging resin provided by the invention, the accompanying drawings are provided, and it should be noted that the accompanying drawings provided by the invention are only selected individual examples from all the accompanying drawings and are not intended to limit the claims, and all other corresponding diagrams obtained through the accompanying drawings provided by the application should be considered to be within the protection scope of the application.
FIG. 1 shows the results of the UV resistance test of example 9 of the present invention and comparative example 1.
FIG. 2 shows the results of the UV resistance tests of example 16 of the present invention and comparative example 2.
Detailed Description
The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
When a parameter is expressed herein as a range, preferred range, or as a range defined by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
Approximating language, as used herein throughout the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes portions that are literally received for modification without substantial change in the basic function to which the invention is related. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.
The present invention is described below by way of specific embodiments, but is not limited to the specific embodiments given below.
In order to solve the above problems, a first aspect of the present invention provides a prepolymer prepared from the raw materials comprising:
(A) a compound having a structure as shown in formula 1, formula 1:
Figure BDA0002886641280000041
wherein R is1、R2、R3Each independently selected from vinyl or epoxy;
(B) organosiloxanes containing phenyl and Si-H groups;
(C) a platinum catalyst.
In some preferred embodiments, R is1、R2、R3At least one of which is vinyl; further preferably, R is1、R2、R3At least one of which is a vinyl group and at least one of which is an epoxy group.
As examples of (A) the compound having a structure represented by the formula 1, DA-MGIC (diallyl monoglycidyl isocyanurate, CAS number: 20395-16-8), MA-DGIC (monoallyl diglycidyl isocyanurate, CAS number: 69731-45-9) are specifically exemplified.
In some preferred embodiments, the phenyl group in the (B) organosiloxane having phenyl and Si — H groups is located in a side chain of the organosiloxane.
In some preferred embodiments, the (B) organosiloxane containing phenyl and Si-H groups has Si-H groups located in the side chains and/or end groups of the organosiloxane.
The organosiloxane of the present invention may be commercially available, for example, RH-309 manufactured by Ningbo Runza Gaoka materials science and technology Co., Ltd, a benzene-based crosslinking agent series product manufactured by Anbia Special Silicone (Nantong) Co., Ltd, and the like.
In some preferred embodiments, the molar ratio of the Si-H group content in the (B) phenyl and Si-H group-containing organosiloxane to the vinyl group content in the (A) compound having the structure shown in the formula 1 is (0.2-1): 1; more preferably, the molar ratio of the Si-H group content in the phenyl and Si-H group-containing organosiloxane (B) to the vinyl group content in the compound (A) having the structure shown in the formula 1 is (0.25-0.95): 1.
in order to solve the problem that the packaging epoxy resin is easy to yellow in an LED product, the inventor introduces a siloxane structure into the material, and because the Si-O-Si siloxane structural bond energy of the organic silicon is larger than the C-C bond energy of the epoxy resin, the yellowing can be effectively improved, and meanwhile, the heat resistance of the material is improved, however, the organic siloxane and the epoxy resin have larger property difference, and the compatibility between the organic siloxane and the epoxy resin is poor. The inventor finds that the compatibility of the organic siloxane in an epoxy resin system can be greatly improved by preparing a prepolymer from a specific epoxy compound and the organic siloxane and introducing the prepolymer into the packaging resin, so that the operating performance and the UV resistance of the packaging resin are improved. The inventor has further unexpectedly found that the organosilicon containing phenyl groups is beneficial to reducing the processing viscosity of the packaging resin and facilitating the packaging operation, the phenyl groups are easy to be oxidized to form quinone, the material is yellowed, however, the steric effect of the phenyl groups can reduce the interaction force among molecular chains and increase the migration performance of the molecular chains, and therefore, in order to balance the operability and the UV resistance of the material, the proportion of the raw materials of the prepolymer needs to be controlled within a certain range.
The platinum catalyst of the present invention is used for catalyzing the addition reaction between the silicon hydrogen bond and the double bond, and is commercially available, for example, a platinum catalyst of kast.
In some preferred embodiments, the platinum catalyst (C) is used in an amount of 0.05 to 1 wt% based on the compound (A) having the structure of formula 1; further preferably, the amount of the platinum catalyst (C) is 0.1-0.5 wt% of the compound (A) having the structure shown in the formula 1.
From the viewpoint of adjusting the degree of reaction, in some preferred embodiments, the starting materials for preparing the prepolymer further include (D) an inhibitor.
The inhibitor used in the present invention is not particularly limited in kind for reducing the chemical reaction rate, and may be any one known to those skilled in the art, for example, maleate ester inhibitor, fumarate ester inhibitor, organophosphine inhibitor, acetylene inhibitor, etc.
In some preferred embodiments, the inhibitor is selected from one or more of 3, 7, 11-trimethyldodecyn-3-ol (CAS number: 1604-35-9, TMDO for short), 3, 5-dimethyl-1-hexyn-3-ol, 3, 6-dimethyl-1-heptyn-3-ol, diethyl fumarate, ethynl cyclohexanol (CAS number: 78-27-3), methyl butynol (CAS number: 115-19-5), methyl maleate.
In some preferred embodiments, the inhibitor (D) is used in an amount of 0 to 0.1 wt% of (A) the compound having the structure represented by formula 1, except 0; further preferably, the amount of the inhibitor (D) is 0.01-0.05 wt% of the compound (A) with the structure shown in the formula 1.
The second aspect of the present invention provides a method for preparing the prepolymer, comprising the following steps: melting 100 parts by weight of (A) a compound with a structure shown in formula 1, (B) organosiloxane containing phenyl and Si-H groups, and (D) an inhibitor at 60-150 ℃, uniformly mixing, cooling to 60-120 ℃, adding (C) a platinum catalyst, and stirring for 5-15 hours to obtain a prepolymer.
The third aspect of the present invention provides an encapsulating resin, which is prepared from the following raw materials: epoxy resin, the prepolymer, the curing agent, the adhesion promoter and the catalyst.
From the viewpoint of improving compatibility of the epoxy resin with the prepolymer, in some preferred embodiments, the epoxy resin is selected from one or more of a group consisting of triglycidyl isocyanurate (TGIC, CAS No.: 2451-62-9), alicyclic epoxy resin (CAS No.: 3130-19-6), hydrogenated bisphenol A epoxy resin; further preferably, the epoxy resin is tris-epoxypropyl isocyanurate and/or a cycloaliphatic epoxy resin.
From the viewpoint of balancing the operation performance and the UV resistance of the packaging resin, in some preferred embodiments, the weight ratio of the epoxy resin to the prepolymer is (3-20): 1; further preferably, the weight ratio of the epoxy resin to the prepolymer is (4-10): 1.
in some preferred embodiments, the curing agent is an anhydride curing agent; further preferably, the acid anhydride curing agent is selected from one or a mixture of more of phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, hydrogenated pyromellitic dianhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tung oil anhydride, dodecenyl succinic anhydride, nadic anhydride, methylnadic anhydride, glutaric anhydride, hydrogenated methylnadic anhydride, methylcyclohexene tetracarboxylic dianhydride, polyazelaic anhydride, polysebacic anhydride, 1, 4, 5, 6-tetrabromophthalic anhydride.
In some preferred embodiments, the anhydride curing agent is used in a molar ratio of the anhydride group content to the epoxy group content of the system of (0.8-1): 1 is calculated. The epoxy group content of the system is the sum of the epoxy group contents of the epoxy resin and the prepolymer.
In some preferred embodiments, the adhesion promoter is selected from the group consisting of gamma-methacryloxypropyltrimethoxysilane, gamma-methacryloxypropylmethyldimethoxysilane, gamma-methacryloxypropylmethyldiethoxysilane, gamma- (2, 3-glycidoxy) propyltriethoxysilane, gamma- (2, 3-glycidoxy) propylmethyldimethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2, 4, 6, 8-tetrakis [2- (3, 4-epoxycyclohexylethyl) tetramethylcyclotetrasiloxane, 2, 4, 6-tris [2- (3, 4-epoxycyclohexylethyl) ] tetramethylcyclotetrasiloxane, gamma-methacryloxypropyltrimethoxysilane, gamma-2, 3-epoxypropylmethyldimethoxysilane, gamma-2, 3-epoxypropyltriethoxysilane, gamma-2, 4, 6-tetrakis [2- (3, 4-epoxycyclohexylethyl) ] tetramethylcyclotetrasiloxane, gamma-epoxypropyltrimethoxysilane, gamma-, One or more of bis [2- (3, 4-epoxycyclohexylethyl) ] tetramethylcyclotetrasiloxane, 2, 4, 6, 8-tetramethyl- [2- (3, 4-epoxycyclohexylethyl) ] cyclotetrasiloxane, 2, 4, 6, 8-tetramethyl-2, 4, 6, 8-tetrakis [3- (oxiranylmethoxy) propyl ] cyclotetrasiloxane and 2, 4, 6, 8-tetramethyl-2- [3- (oxiranylmethoxy) propyl ] cyclotetrasiloxane.
In some preferred embodiments, the amount of the adhesion promoter is 0.01 to 5 wt% of the total amount of the epoxy resin and the prepolymer; further preferably, the amount of the adhesion promoter is 0.05 to 3 wt% of the total amount of the epoxy resin and the prepolymer.
In some preferred embodiments, the catalyst is selected from the group consisting of triphenylphosphine, methyltrioctylphosphonium dimethylphosphate, tetrabutylphosphonium acetate, methyltributylphosphonium dimethylphosphate, benzyltriphenylphosphonium chloride, tetrabutylphosphonium chloride, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, benzimidazole, and mixtures of one or more thereof.
In some preferred embodiments, the amount of the catalyst is 0.01 to 5 wt% of the total amount of the epoxy resin, the prepolymer and the curing agent; further preferably, the amount of the catalyst is 0.1-1 wt% of the total amount of the epoxy resin, the prepolymer and the curing agent.
In some preferred embodiments, the raw materials for preparing the encapsulation resin further comprise at least one of pigments, inorganic fillers, antioxidants and ultraviolet absorbers.
The pigment can be titanium dioxide, carbon black and the like, and the addition amount of the pigment can be 1-400 wt% of the total amount of the epoxy resin, the prepolymer and the curing agent; the inorganic filler can be silicon dioxide, alumina, calcium carbonate, kaolin and the like, and the addition amount can be 50-800 wt% of the total amount of the epoxy resin, the prepolymer and the curing agent; the antioxidant can be 2, 6-di-tert-butyl-4-methylphenol, antioxidant 1010, antioxidant 1076 and the like, and the addition amount can be 0.01-5 wt% of the total amount of the epoxy resin, the prepolymer and the curing agent; as the ultraviolet resistant absorbent, UV-326, UV-531, UV-234, UV-320, etc. can be given, and the addition amount can be 0.01-5 wt% of the total amount of the epoxy resin, the prepolymer and the curing agent.
The fourth aspect of the present invention provides a method for preparing the above encapsulation resin, comprising the steps of: taking epoxy resin and the prepolymer, stirring at 150-200 ℃, cooling to 100-150 ℃, adding a curing agent, an adhesion promoter and a catalyst, stirring, discharging, cooling, crushing and cake making to obtain the packaging resin.
The fifth aspect of the invention provides a packaging resin for a white reflecting cup, which is prepared from the raw materials of 100 parts by weight of the packaging resin and 50-400 parts by weight of titanium dioxide.
The sixth aspect of the invention provides an application of the packaging resin for the white reflecting cup, which is used for a white LED device with power of 1-3W.
The seventh aspect of the invention provides an encapsulating resin for a black reflecting cup, which is prepared from 100 parts by weight of the encapsulating resin and 1-30 parts by weight of carbon black.
An eighth aspect of the present invention provides a use of the above-mentioned packaging resin for black reflector cups, for surface mount SMT light emitting devices of outdoor RGB display screens.
A ninth aspect of the present invention provides an LED device, wherein a reflective cup structure is obtained by injection molding of a metal frame or a resin substrate and the above encapsulation resin. The reflecting cup is a carrier when the LED is cast and packaged by the liquid pouring sealant, and is a reflecting material for forming single-side light emitting of the LED, and the reflecting cup is formed by the packaging resin, so that the heat resistance and the light aging resistance of an LED device can be improved.
Examples
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
Example 1
Example 1 provides a prepolymer, 100 weight portions DA-MGIC (diallyl monoglycidyl isocyanurate, CAS number: 20395-16-8) and RH-SH309 (phenyl hydrogen-containing organosiloxane, hydrogen content 0.87%, available from Ningbo Runzhen GaoXin materials science and technology Co., Ltd.), 0.05 weight portions 3, 7, 11-trimethyl dodecyn-3-ol (CAS number: 1604-35-9, TMDO for short) are melted at 100 ℃ for 0.5h, mixed uniformly, cooled to 90 ℃, added with 0.5 weight portions PT5000 (platinum catalyst, concentration 5000ppm, available from Shenzhen Junchi science and technology Co., Ltd.), and stirred for 10h to obtain the prepolymer.
In this example, the molar ratio of the SiH content in RH-SH309 to the vinyl content in DA-MGIC was 0.95: 1 calculated amount of RH-SH 309.
Example 2
Example 2 provides a prepolymer prepared by melting 100 parts by weight of MA-DGIC (monoallyl diglycidyl isocyanurate, CAS number: 69731-45-9) and RH-SH309 (phenyl hydrogen-containing organosiloxane, hydrogen content 0.87%, available from Ningbo Runzhen GaoXin materials science and technology Co., Ltd.), 0.05 part by weight of 3, 7, 11-trimethyldodecyn-3-ol (CAS number: 1604-35-9, TMDO for short) at 100 deg.C for 0.5h, mixing well, cooling to 90 deg.C, adding 0.5 part by weight of PT5000 (platinum catalyst, concentration 5000ppm, available from Shenzhen Jun science and technology Co., Ltd.), and stirring for 10 h.
In this example, the molar ratio of the SiH content in RH-SH309 to the vinyl content in MA-DGIC was 0.95: 1 calculated amount of RH- -SH 309.
Example 3
Example 3 provides a prepolymer prepared by melting 100 parts by weight of MA-DGIC (monoallyl diglycidyl isocyanurate, CAS number: 69731-45-9) and RH-SH309 (phenyl hydrogen-containing organosiloxane, hydrogen content 0.87%, available from Ningbo Runzhen GaoXin materials science and technology Co., Ltd.), 0.05 part by weight of 3, 7, 11-trimethyldodecyn-3-ol (CAS number: 1604-35-9, TMDO for short) at 90 deg.C for 0.5h, mixing well, cooling to 80 deg.C, adding 0.5 part by weight of PT5000 (platinum catalyst, concentration 5000ppm, available from Shenzhen Jun science and technology Co., Ltd.), and stirring for 8 h.
In this example, the molar ratio of the SiH content in RH-SH309 to the vinyl content in MA-DGIC was 0.5: 1 calculated amount of RH-SH 309.
Example 4
Example 4 provides a prepolymer, 100 weight portions DA-MGIC (diallyl monoglycidyl isocyanurate, CAS number: 20395-16-8) and RH-SH309 (phenyl hydrogen-containing organosiloxane, hydrogen content 0.87%, available from Ningbo Runzhen GaoXin materials science and technology Co., Ltd.), 0.05 weight portions 3, 7, 11-trimethyl dodecyn-3-ol (CAS number: 1604-35-9, TMDO for short) are melted at 90 ℃ for 0.5h, mixed uniformly, cooled to 80 ℃, added with 0.5 weight portions PT5000 (platinum catalyst, concentration 5000ppm, available from Shenzhen Jun science and technology Co., Ltd.), and stirred for 8h to obtain the prepolymer.
In this example, the molar ratio of the SiH content in RH-SH309 to the vinyl content in DA-MGIC was 0.25: 1 calculated amount of RH-SH 309.
Example 5
Example 5 provides a prepolymer, 100 weight portions DA-MGIC (diallyl monoglycidyl isocyanurate, CAS number: 20395-16-8) and XL-2460 (phenyl hydrogen-containing organosiloxane, SiH content: 3.85mmol/g, from Nantong Special organosilicon Co., Ltd.), 0.05 weight portions 3, 7, 11-trimethyldodecyn-3-ol (CAS number: 1604-35-9, abbreviated as O) are melted at 90 ℃ for 0.5h, mixed uniformly, cooled to 80 ℃, added with 0.1 weight portion PT5000 (platinum catalyst, concentration 5000ppm, from Shenzhen science and technology Co., Ltd.), and stirred for 6h to obtain the prepolymer.
In this example, the molar ratio of the SiH content in XL-2460 to the vinyl content in DA-MGIC was 0.5: 1 calculated amount of XL-2460.
Example 6
Example 6 provides a prepolymer, 100 weight portions DA-MGIC (diallyl monoglycidyl isocyanurate, CAS number: 20395-16-8) and XL-2460 (phenyl hydrogen-containing organosiloxane, SiH content: 3.85mmol/g, from Nantong Special organosilicon Co., Ltd.), 0.05 weight portions 3, 7, 11-trimethyldodecyn-3-ol (CAS number: 1604-35-9, abbreviated as O) are melted at 90 ℃ for 0.5h, mixed uniformly, cooled to 80 ℃, added with 0.1 weight portion PT5000 (platinum catalyst, concentration 5000ppm, from Shenzhen science and technology Co., Ltd.), and stirred for 6h to obtain the prepolymer.
In this example, the molar ratio of the SiH content in XL-2460 to the vinyl content in DA-MGIC was 0.95: 1 calculated amount of XL-2460.
Example 7
Example 7 provides a prepolymer, 100 parts by weight of DA-MGIC (diallyl monoglycidyl isocyanurate, CAS number: 20395-16-8) and XL-2460 (phenyl hydrogen-containing organosiloxane, SiH content: 3.85mmol/g, available from Nantong Special organosilicon Co., Ltd.), 0.05 part by weight of 3, 7, 11-trimethyldodecyn-3-ol (CAS number: 1604-35-9, abbreviated as O) were melted at 90 ℃ for 0.5h, mixed well and cooled to 80 ℃ and 0.1 part by weight of PT5000 (platinum catalyst, concentration 5000ppm, available from Shenzhen science technologies Co., Ltd.), stirred for 6h to obtain a prepolymer.
In this example, the molar ratio of the SiH content in XL-2460 to the vinyl content in DA-MGIC was 0.25: 1 calculated amount of XL-2460.
Example 8
Example 8 provides a prepolymer prepared by melting 100 parts by weight of MA-DGIC (monoallyl diglycidyl isocyanurate, CAS number: 69731-45-9) and XL-2460 (organosiloxane, SiH content: 3.85mmol/g, obtained from Nantong Special Silicone Co., Ltd.), 0.05 part by weight of 3, 7, 11-trimethyldodecyn-3-ol (CAS number: 1604-35-9, TMDO for short) at 90 ℃ for 0.5 hour, mixing them uniformly, cooling to 80 ℃, adding 0.1 part by weight of PT5000 (platinum catalyst, concentration 5000ppm, obtained from Junchi scientific Co., Ltd., Shenzhen), and stirring for 6 hours.
In this example, the molar ratio of the SiH content in XL-2460 to the vinyl content in MA-DGIC was 0.5: 1 calculated amount of XL-2460.
The inventors found in the comparison of examples 1 to 8 that under the same experimental conditions, the reaction of DA-MGIC with organosiloxane proceeds more easily than the reaction of MA-DGIC with silicone, and the reaction involving XL-2460 proceeds more easily than the reaction involving RH 309. The ease of the reaction is determined by the length of the reaction time and the temperature of the reaction, and if the reaction time is long and the temperature of the reaction is high, the operability is poor, and the results of the operability evaluation are excellent, good, and poor in order from easy to difficult, and the operability and yield (epoxy equivalent weight measured by the titration method) of examples 1 to 8 are shown in table 1.
TABLE 1
Examples Operability of Yield of
Example 1 Difference (D) 55％
Example 2 Difference (D) 50％
Examples3 Good effect 65％
Example 4 Good effect 70％
Example 5 Is excellent in 95％
Example 6 Is excellent in 90％
Example 7 Is excellent in 95％
Example 8 Is excellent in 85％
Example 9
Example 9 provides an encapsulating resin, which is prepared by taking 90 parts by weight of tris (glycidyl isocyanurate) (TGIC, CAS number: 2451-62-9), 0.05 parts by weight of 2, 6-di-tert-butyl-4-methylphenol (CAS number: 2409-55-4) and 10 parts by weight of the prepolymer in example 2, stirring at 180 ℃ for 0.5h, cooling to 130 ℃, adding 150 parts by weight of hexahydrophthalic dianhydride (CAS number: 85-42-7), 0.05 parts by weight of 3-mercaptopropyltrimethoxysilane (CAS number: 4420-74-0) and 0.5 parts by weight of 2-ethyl-4-methylimidazole (CAS number: 931-36-2), stirring, discharging, cooling, crushing and patting to obtain the encapsulating resin.
Example 10
Example 10 provides an encapsulating resin prepared by mixing 90 parts by weight of tris (epoxypropylisocyanurate) (TGIC, CAS No.: 2451-62-9), 0.05 parts by weight of 2, 6-di-t-butyl-4-methylphenol (CAS No.: 2409-55-4), 10 parts by weight of the prepolymer of example 4 at 180 ℃ for 0.5 hour, cooling to 130 ℃, adding 150 parts by weight of hexahydrophthalic acid dianhydride (CAS No.: 85-42-7), 0.25 parts by weight of γ -methacryloxypropylmethyldimethoxysilane (CAS No.: 14513-34-9), 0.25 parts by weight of γ - (2, 3-epoxypropoxy) propylmethyldimethoxysilane (CAS No.: 65799-47-5), 0.5 parts by weight of 2-ethyl-4-methylimidazole (CAS No.: 65931-36-2), stirring, discharging, cooling, crushing and cake making to obtain the packaging resin.
Example 11
Example 11 provides an encapsulating resin prepared by mixing 90 parts by weight of tris (epoxypropylisocyanurate) (TGIC, CAS No.: 2451-62-9), 0.05 parts by weight of 2, 6-di-t-butyl-4-methylphenol (CAS No.: 2409-55-4), 10 parts by weight of the prepolymer of example 6 at 150 ℃ for 0.5 hour, cooling to 130 ℃, adding 150 parts by weight of hexahydrophthalic acid dianhydride (CAS No.: 85-42-7), 0.25 parts by weight of gamma- (2, 3-epoxypropoxy) propyltriethoxysilane (CAS No.: 2602-34-8), 0.25 parts by weight of gamma-methacryloxypropylmethyldiethoxysilane (CAS No.: 65100-04-1), 0.5 parts by weight of 2-ethyl-4-methylimidazole (CAS No.: 931-36-2), stirring, discharging, cooling, crushing and cake making to obtain the packaging resin.
Example 12
Example 12 provides an encapsulating resin prepared by mixing 90 parts by weight of tris (epoxypropylisocyanurate) (TGIC, CAS number: 2451-62-9), 0.05 parts by weight of 2, 6-di-tert-butyl-4-methylphenol (CAS number: 2409-55-4), 10 parts by weight of the prepolymer of example 7, stirring at 180 ℃ for 0.5 hour, cooling to 130 ℃, adding 150 parts by weight of hexahydrophthalic acid dianhydride (CAS number: 85-42-7), 1 part by weight of beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane (CAS number: 3388-04-3), 1 part by weight of 2, 4, 6, 8-tetrakis [2- (3, 4-epoxycyclohexylethyl) ] tetramethylcyclotetrasiloxane (CAS number: 121225-98-7), 1 part by weight of 3-mercaptopropyltriethoxysilane (CAS number: 14814-09-6), 0.5 part by weight of 2-ethyl-4-methylimidazole (CAS number: 931-36-2), stirring, discharging, cooling, crushing, and cake-making to obtain the encapsulating resin.
Example 13
Example 13 provides an encapsulating resin prepared by mixing 90 parts by weight of tris (epoxypropylisocyanurate) (TGIC, CAS No.: 2451-62-9), 0.05 parts by weight of 2, 6-di-t-butyl-4-methylphenol (CAS No.: 2409-55-4), 10 parts by weight of the prepolymer of example 8 at 180 ℃ for 0.5 hour, cooling to 130 ℃, adding 150 parts by weight of hexahydrophthalic acid dianhydride (CAS No.: 85-42-7), 0.05 parts by weight of gamma-methacryloxypropyltrimethoxysilane (CAS No.: 2530-85-0), 0.05 parts by weight of 2, 4, 6, 8-tetrakis [2- (3, 4-epoxycyclohexylethyl) ] tetramethylcyclotetrasiloxane (CAS No.: 121225-98-7), 0.5 parts by weight of 2-ethyl-4-methylimidazole (CAS No.: 931-36-2), stirring, discharging, cooling, crushing and cake making to obtain the packaging resin.
Example 14
Example 14 provides an encapsulating resin prepared by mixing 85 parts by weight of tris (epoxypropylisocyanurate) (TGIC, CAS No.: 2451-62-9), 0.05 parts by weight of 2, 6-di-t-butyl-4-methylphenol (CAS No.: 2409-55-4), 15 parts by weight of the prepolymer of example 7 at 180 ℃ for 0.5 hour, cooling to 130 ℃ and adding 130 parts by weight of hexahydrophthalic acid dianhydride (CAS No.: 85-42-7), 0.025 parts by weight of gamma-methacryloxypropyltrimethoxysilane (CAS No.: 2530-85-0), 0.05 parts by weight of 2, 4, 6, 8-tetramethyl-2, 4, 6, 8-tetrakis [3- (oxiranylmethoxy) propyl ] cyclotetrasiloxane (CAS No.: 60665-85-2), 0.5 parts by weight of 2-ethyl-4-methylimidazole 931 (CAS No.: 36-2), stirring, discharging, cooling, crushing and cake making to obtain the packaging resin.
Example 15
Example 15 provides an encapsulating resin prepared by mixing 80 parts by weight of tris (epoxypropylisocyanurate) (TGIC, CAS No.: 2451-62-9), 0.05 parts by weight of 2, 6-di-t-butyl-4-methylphenol (CAS No.: 2409-55-4), 20 parts by weight of the prepolymer of example 7 at 180 ℃ for 0.5 hour, cooling to 130 ℃, adding 110 parts by weight of hexahydrophthalic acid dianhydride (CAS No.: 85-42-7), 0.05 parts by weight of gamma-methacryloxypropyltrimethoxysilane (CAS No.: 2530-85-0), 0.05 parts by weight of 2, 4, 6, 8-tetramethyl-2- [3- (oxiranylmethoxy) propyl ] cyclotetrasiloxane (CAS No.: 61614-55-9), 0.5 parts by weight of 2-ethyl-4-methylimidazole (CAS No.: 931-36-2), stirring, discharging, cooling, crushing and cake making to obtain the packaging resin.
Example 16
Example 16 provides an encapsulating resin prepared by stirring 90 parts by weight of an alicyclic epoxy resin A (bis (7-oxabicyclo [4.1.0] 3-heptamethyl) oxalate), 0.05 part by weight of 2, 6-di-tert-butyl-4-methylphenol (CAS No.: 2409-55-4), and 10 parts by weight of the prepolymer of example 2 at 180 ℃ for 0.5 hour, cooling to 130 ℃, adding 110 parts by weight of hexahydrophthalic dianhydride (CAS No.: 85-42-7), 0.025 part by weight of gamma-methacryloxypropyltrimethoxysilane (CAS No.: 2530-85-0), 0.025 part by weight of gamma-methacryloxypropylmethyldiethoxysilane (CAS No.: 65100-04-1), and 0.5 part by weight of 2-ethyl-4-methylimidazole (CAS No.: 931-36-2), stirring, discharging, cooling, crushing and cake making to obtain the packaging resin.
Example 17
Example 17 provides an encapsulating resin, which comprises 90 parts by weight of a cycloaliphatic epoxy resin A, 0.05 part by weight of 2, 6-di-tert-butyl-4-methylphenol (CAS number: 2409-55-4), 10 parts by weight of the prepolymer of example 4, stirring at 180 ℃ for 0.5h, cooling to 130 ℃, adding 110 parts by weight of hexahydrophthalic acid dianhydride (CAS number: 85-42-7), 0.025 parts by weight of gamma-methacryloxypropyltrimethoxysilane (CAS number: 2530-85-0), 0.025 parts by weight of gamma-methacryloxypropylmethyldiethoxysilane (CAS number: 65100-04-1) and 0.5 parts by weight of 2-ethyl-4-methylimidazole (CAS number: 931-36-2), stirring, discharging, cooling, crushing and beating to obtain the packaging resin.
Example 18
Example 18 provides an encapsulating resin prepared by mixing 90 parts by weight of a cycloaliphatic epoxy resin A, 0.05 part by weight of 2, 6-di-tert-butyl-4-methylphenol (CAS No.: 2409-55-4), 10 parts by weight of the prepolymer of example 7, stirring at 180 ℃ for 0.5h, cooling to 130 ℃, adding 110 parts by weight of hexahydrophthalic acid dianhydride (CAS number: 85-42-7), 0.025 parts by weight of gamma-methacryloxypropyltrimethoxysilane (CAS number: 2530-85-0), 0.025 parts by weight of gamma-methacryloxypropylmethyldiethoxysilane (CAS number: 65100-04-1) and 0.5 parts by weight of 2-ethyl-4-methylimidazole (CAS number: 931-36-2), stirring, discharging, cooling, crushing and beating to obtain the packaging resin.
Example 19
Example 19 provides an encapsulating resin prepared by mixing 90 parts by weight of alicyclic epoxy resin A, 0.05 part by weight of 2, 6-di-t-butyl-4-methylphenol (CAS No.: 2409-55-4), 10 parts by weight of the prepolymer of example 8, stirring at 180 ℃ for 0.5h, cooling to 130 ℃, adding 110 parts by weight of hexahydrophthalic acid dianhydride (CAS number: 85-42-7), 0.025 parts by weight of gamma-methacryloxypropyltrimethoxysilane (CAS number: 2530-85-0), 0.025 parts by weight of gamma-methacryloxypropylmethyldiethoxysilane (CAS number: 65100-04-1) and 0.5 parts by weight of 2-ethyl-4-methylimidazole (CAS number: 931-36-2), stirring, discharging, cooling, crushing and beating to obtain the packaging resin.
Comparative example 1
Comparative example 1 provides an encapsulating resin, taking 90 parts by weight of tris (epoxypropyl) isocyanurate (TGIC, CAS number: 2451-62-9), 0.05 parts by weight of 2, 6-di-tert-butyl-4-methylphenol (CAS number: 2409-55-4), stirring at 180 ℃ for 0.5h, cooling to 130 ℃, adding 150 parts by weight of hexahydrophthalic acid dianhydride (CAS number: 85-42-7), 0.05 parts by weight of 3-mercaptopropyltrimethoxysilane (CAS number: 4420-74-0) and 0.5 parts by weight of 2-ethyl-4-methylimidazole (CAS number: 931-36-2), stirring, discharging, cooling, crushing and patting to obtain the encapsulating resin.
Comparative example 2
Comparative example 2 provides an encapsulating resin obtained by taking 90 parts by weight of alicyclic epoxy resin A, 0.05 part by weight of 2, 6-di-tert-butyl-4-methylphenol (CAS No.: 2409-55-4), stirring at 180 ℃ for 0.5 hour, cooling to 130 ℃, adding 110 parts by weight of hexahydrophthalic acid dianhydride (CAS No.: 85-42-7), 0.025 part by weight of gamma-methacryloxypropyltrimethoxysilane (CAS No.: 2530-85-0), 0.025 part by weight of gamma-methacryloxypropylmethyldiethoxysilane (CAS No.: 65100-04-1), and 0.5 part by weight of 2-ethyl-4-methylimidazole (CAS No.: 931-36-2), stirring, discharging, cooling, pulverizing, and patting.
The workability of examples 9 to 19 and comparative examples 1 to 2 was evaluated, the chips were encapsulated with the encapsulating resins of the examples, and if the encapsulating resin did not encapsulate the chips or the melt viscosity was too high, the workability was not good, and the results of the evaluation of the workability were excellent, better, and worse in the order of good to bad, and the workability of examples 9 to 19 and comparative examples 1 to 2 is shown in table 2.
The transparencies of the examples 9-19 and the comparative examples 1-2 are evaluated, the packaging resin is preheated, extruded into a die cavity, molded and cured for 300s at 160 ℃, and then cured for 2-4 hours at 150-170 ℃ to obtain a test sample sheet with uniform thickness (200 +/-10 um), and whether the molded sample sheet is transparent or milky is observed, wherein the evaluation results of the transparencies are sequentially divided into excellent, better and poor transparency according to the sequence of transparency, translucency and milky, and the transparencies of the examples 9-19 and the comparative examples 1-2 are shown in Table 2.
The UV resistance of examples 9-19 and comparative examples 1-2 was evaluated, the molded samples were uniformly placed in a UV irradiator as test samples, and the color contrast aging state after 1 hour of irradiation was measured using a color difference meter, and the larger the b value, the worse the UV light decay resistance, and the results are shown in Table 2.
TABLE 2
Examples Operability of Transparency of UV resistance After UV test b
Example 9 Is excellent in Difference (D) Is excellent in 5-6
Example 10 Is excellent in Is excellent in Is preferably used 6-7
Example 11 Is excellent in Is excellent in Is preferably used 6-7
Example 12 Is preferably used Is preferably used Is preferably used 6-7
Example 13 Is preferably used Is preferably used Is preferably used 6-7
Example 14 Is excellent in Is preferably used Is preferably used 6-7
Example 15 Is excellent in Is preferably used Is preferably used 6-7
Example 16 Is excellent in Is excellent in Is excellent in 5-6
Example 17 Is excellent in Is excellent in Is preferably used 7-9
Example 18 Is excellent in Is excellent in Is preferably used 7-9
Example 19 Is excellent in Is excellent in Is preferably used 7-9
Comparative example 1 Is excellent in Is preferably used Good effect 6-7
Comparative example 2 Is excellent in Is excellent in Good effect 7-8
The blue light decay resistance test of the UV lamp of example 9 and comparative example 1, and the blue light decay resistance test of example 16 and comparative example 2 show that the encapsulation resin obtained by adding the prepolymer disclosed by the invention has better UV light decay resistance, and the effect can be seen from figures 1 and 2.
The inventor finds that, in a tris (glycidyl isocyanurate) system, one of the examples 1 to 8 can be selected arbitrarily according to a large number of experimental results in the research and development process, and the packaging resin with excellent performance can be obtained according to the conditions of the example 9, and the LED white light chip with blue light resistance can be obtained by packaging the LED chip with the packaging resin.
In the research and development process, the inventor finds that in an alicyclic epoxy resin system, one of the examples 1-8 can be arbitrarily selected, and the packaging resin with excellent performance can be obtained according to the conditions of the example 16, and the LED white light chip with blue light resistance can be obtained by packaging the LED chip with the packaging resin.
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.

Claims (10)

1. A prepolymer is characterized by comprising the following preparation raw materials:
(A) a compound having a structure as shown in formula 1, formula 1:
Figure FDA0002886641270000011
wherein R is1、R2、R3Each independently selected from vinyl or epoxy;
(B) organosiloxanes containing phenyl and Si-H groups;
(C) a platinum catalyst.
2. The prepolymer of claim 1, wherein the prepolymer is prepared from starting materials further comprising (D) an inhibitor.
3. A method of preparing a prepolymer as claimed in claim 2, comprising the steps of: melting 100 parts by weight of (A) a compound with a structure shown in formula 1, (B) organosiloxane containing phenyl and Si-H groups, and (D) an inhibitor at 60-150 ℃, uniformly mixing, cooling to 60-120 ℃, adding (C) a platinum catalyst, and stirring for 5-15 hours to obtain a prepolymer.
4. An encapsulating resin, characterized in that the preparation raw material of the encapsulating resin comprises epoxy resin, the prepolymer of claim 1 or 2, a curing agent, an adhesion promoter and a catalyst.
5. A method for preparing the encapsulating resin according to claim 4, comprising the steps of: and (3) stirring the epoxy resin and the prepolymer at 150-200 ℃, cooling to 100-150 ℃, adding the curing agent, the adhesion promoter and the catalyst, stirring, discharging, cooling, crushing and cake making to obtain the packaging resin.
6. An encapsulating resin for a white reflecting cup, characterized in that the raw materials for the preparation thereof comprise 100 parts by weight of the encapsulating resin according to claim 4 and 50 to 400 parts by weight of titanium dioxide.
7. The use of the encapsulating resin for a white reflecting cup according to claim 6 for a white LED device having a power of 1 to 3W.
8. An encapsulating resin for a black reflecting cup, characterized in that the raw materials for the preparation thereof comprise 100 parts by weight of the encapsulating resin according to claim 4 and 1-30 parts by weight of carbon black.
9. The use of the packaging resin for black reflector cups as claimed in claim 8, wherein it is used for surface mount SMT light emitting devices of outdoor RGB display screens.
10. An LED device characterized in that it is a reflection cup structure obtained by injection molding of a metal frame or a resin substrate with the encapsulating resin of claim 4.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022148103A1 (en) * 2021-01-07 2022-07-14 天津德高化成光电科技有限责任公司 Prepolymer, encapsulating resin containing same, and use of encapsulating resin

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115491038A (en) * 2022-09-16 2022-12-20 广州市矽友新材料科技有限公司 Halogen-free platinum flame retardant for silicone rubber and preparation method thereof
CN116178890A (en) * 2022-11-30 2023-05-30 深圳伊帕思新材料科技有限公司 Thermosetting resin composition, prepreg for PCB and copper-clad plate for PCB

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008143954A (en) * 2006-12-06 2008-06-26 Jsr Corp Isocyanuric ring-containing polymer, method for producing the same, and composition containing the same
CN103205125A (en) * 2012-01-16 2013-07-17 信越化学工业株式会社 Thermosetting Resin Composition For Semiconductor Encapsulation And Encapsulated Semiconductor Device
CN104583264A (en) * 2012-08-31 2015-04-29 新日铁住金化学株式会社 Epoxy silicone resin and curable resin composition employing same
WO2020130012A1 (en) * 2018-12-18 2020-06-25 住友ベークライト株式会社 Thermosetting resin composition for lds and method for producing semiconductor device

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI433875B (en) * 2008-01-28 2014-04-11 Shinetsu Chemical Co Diglygidylisocyanurylmodified organopolysiloxane and composition including the organopolysiloxane
JP5489280B2 (en) * 2010-04-07 2014-05-14 信越化学工業株式会社 Epoxy composition for optical semiconductor encapsulation
JP5557324B2 (en) * 2010-09-01 2014-07-23 信越化学工業株式会社 Die bond agent and optical semiconductor device
JP5938040B2 (en) * 2011-07-13 2016-06-22 株式会社ダイセル Curable epoxy resin composition
JP2013159776A (en) * 2012-02-09 2013-08-19 Adeka Corp Silicon-containing curable white resin composition, cured product thereof, and optical semiconductor package and reflecting material using the cured product
JP6068965B2 (en) * 2012-12-07 2017-01-25 株式会社カネカ Modified polyhedral polysiloxane, curable composition containing the same, and method for producing modified polyhedral polysiloxane
CN104745142A (en) * 2013-12-27 2015-07-01 蓝星有机硅（上海）有限公司 Curable silicon rubber composition used for LED package
JP6358016B2 (en) * 2014-09-29 2018-07-18 Jnc株式会社 Thermosetting resin composition
WO2016054781A1 (en) * 2014-10-09 2016-04-14 Henkel (China) Company Limited An organopolysiloxane prepolymer and a curable organopolysiloxane composition comprising the same
WO2016112487A1 (en) * 2015-01-13 2016-07-21 Henkel (China) Company Limited Organopolysiloxane prepolymer and curable organopolysiloxane composition comprising same
WO2017110468A1 (en) * 2015-12-24 2017-06-29 Jnc株式会社 Heat-curable resin composition
JP2019065058A (en) * 2016-02-08 2019-04-25 クラスターテクノロジー株式会社 Curable epoxy resin composition for white reflector and cured product thereof, substrate for mounting optical semiconductor element, optical semiconductor device and production methods thereof
WO2018135557A1 (en) * 2017-01-23 2018-07-26 株式会社ダイセル Curable epoxy resin composition
CN112812304B (en) * 2021-01-07 2023-05-12 天津德高化成光电科技有限责任公司 Prepolymer, packaging resin containing prepolymer and application of packaging resin

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008143954A (en) * 2006-12-06 2008-06-26 Jsr Corp Isocyanuric ring-containing polymer, method for producing the same, and composition containing the same
CN103205125A (en) * 2012-01-16 2013-07-17 信越化学工业株式会社 Thermosetting Resin Composition For Semiconductor Encapsulation And Encapsulated Semiconductor Device
CN104583264A (en) * 2012-08-31 2015-04-29 新日铁住金化学株式会社 Epoxy silicone resin and curable resin composition employing same
WO2020130012A1 (en) * 2018-12-18 2020-06-25 住友ベークライト株式会社 Thermosetting resin composition for lds and method for producing semiconductor device

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022148103A1 (en) * 2021-01-07 2022-07-14 天津德高化成光电科技有限责任公司 Prepolymer, encapsulating resin containing same, and use of encapsulating resin

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