CN111100463A - Epoxy modified silicone resin composition and application thereof - Google Patents
Epoxy modified silicone resin composition and application thereof Download PDFInfo
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- CN111100463A CN111100463A CN201911361740.7A CN201911361740A CN111100463A CN 111100463 A CN111100463 A CN 111100463A CN 201911361740 A CN201911361740 A CN 201911361740A CN 111100463 A CN111100463 A CN 111100463A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of 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; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/206—Insulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/212—Electromagnetic interference shielding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/552—Fatigue strength
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/71—Resistive to light or to UV
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of 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; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
- C08J2383/06—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Abstract
The invention relates to an epoxy modified silicone resin composition and application thereof. The composition is prepared from the following raw materials in parts by weight: 10-70 parts of epoxy modified organic silicon resin, 10-30 parts of functional resin and 15-100 parts of auxiliary agent, wherein the epoxy modified organic silicon resin has a structure shown in formula I, and R is1Is methyl, ethyl phenyl; r2Is methyl or phenyl; r3Is methyl or phenyl; m is an integer in the range of 1-20; n is an integer in the range of 1 to 20.
Description
Technical Field
The invention relates to the technical field of LEDs (light emitting diodes), in particular to an epoxy modified silicone resin composition and application thereof.
Background
An LED (Light-Emitting Diode) is widely used in the fields of display screens, illumination, radiation Light sources, etc. as a Light source with small volume, high luminous efficiency, low power consumption and long service life. In recent years, with the trend toward miniaturization, thinning, and high-density of LEDs, a packaging method in which components are directly mounted on a printed wiring board has been rapidly developed. With the development of high-luminance LED technology, LEDs have become more highly bright and the amount of heat generated by LED elements has increased. In the past, most of substrates for bearing LED elements are made of epoxy resin, however, the epoxy resin has poor weather resistance, and is subjected to high heat radiation for a long time, so that the color of the substrate is aged and yellowed, the reflectivity of light is reduced, and the LED efficiency is reduced.
CN201410782137 discloses a yellowing resistant resin composition, which comprises the following raw materials: the coating comprises alicyclic epoxy resin, general epoxy resin, cyanate ester resin, glycidyl methacrylate, a curing agent, titanium dioxide, a fluorescent whitening agent, an anti-yellowing agent and the like, and has the advantages of good yellowing resistance, high reflectivity of a base material, high peeling strength between the base material and a metal foil and the like. The material has better weather resistance than epoxy resin by directly adding alicyclic epoxy resin. However, cycloaliphatic epoxy resins are expensive and difficult to meet increasingly stringent performance requirements.
CN201410829372 prepares the silicone resin composition with excellent heat resistance, weather resistance and yellowing resistance by compounding the condensed type silicone resin, a catalyst, a white filler, an auxiliary agent and optionally other components, and applies the condensed type silicone resin to the LED white copper-clad plate to ensure that the LED white copper-clad plate also has excellent heat resistance, weather resistance and yellowing resistance. However, the adhesion of the material is poor.
Disclosure of Invention
Based on the epoxy modified silicone resin composition, the epoxy modified silicone resin composition has good mechanical property, good adhesive property and excellent electrical insulation property, can resist high-temperature aging, ultraviolet light and radiation, and a laminated board prepared by using the epoxy modified silicone resin composition as a raw material can effectively improve the luminous effect of an LED and prolong the service life when being used for a substrate of an LED element.
The specific technical method comprises the following steps:
an epoxy modified silicone resin composition is prepared from the following raw materials in parts by weight:
10 to 70 parts of epoxy modified organic silicon resin,
10-30 parts of functional resin,
15 to 100 portions of auxiliary agent,
the epoxy modified silicone resin has a structure shown in formula I:
formula I
Wherein R is1Is methyl, ethyl or phenyl;
R2is methyl or phenyl;
R3is methyl or phenyl;
m is an integer in the range of 1-20;
n is an integer in the range of 1 to 20.
The invention also provides a prepreg, and the raw material of the prepreg comprises the epoxy modified silicone resin composition.
The invention also provides a laminated board, and the raw material of the laminated board comprises the epoxy modified silicone resin composition or the prepreg.
Compared with the prior art, the invention has the following beneficial effects:
the epoxy modified silicone resin composition is prepared by taking the epoxy modified silicone resin with a specific structure and simultaneously provided with an epoxy group and a silicon oxygen group as one of raw materials and matching with functional resin and an auxiliary agent, can fully exert good mechanical property, adhesive property and excellent electrical insulation property of the epoxy resin, and can fully exert high temperature aging resistance, ultraviolet light resistance and radiation resistance of the silicone resin.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
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. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
An epoxy modified silicone resin composition is prepared from the following raw materials in parts by weight:
10 to 70 parts of epoxy modified organic silicon resin,
10-30 parts of functional resin,
15 to 100 portions of auxiliary agent,
the epoxy modified silicone resin has a structure shown in formula I:
formula I
Wherein the content of the first and second substances,
R1is methyl, ethyl or phenyl;
R2is methyl or phenyl;
R3is methyl or phenyl;
m is an integer in the range of 1-20;
n is an integer in the range of 1 to 20.
The epoxy modified organic silicon resin with the structure has the advantages that the molecular chain segment simultaneously contains the epoxy group and the silicon-oxygen group, so that the epoxy modified organic silicon resin has good mechanical property, bonding property and excellent electrical insulation property, and can resist high-temperature aging, ultraviolet light and radiation.
In the structure of the epoxy modified silicone resin, the molar ratio of the organic substituent (R) to the silicon atom (Si), namely the R/Si value, has a great relationship with the mass of the epoxy modified silicone resin, and the properties of the epoxy modified silicone resin, such as curing property, paint film flexibility, hardness, heat resistance and thermal cracking resistance, can be influenced. Wherein the organic substituent R represents an organic functional group R in the formula I1、R2、R3、-C6H5and-CH3The R/Si value is R1、R2、R3、-C6H5and-CH3The ratio of the total moles to the moles of silicon atoms.
Preferably, the R/Si value is 1.5 to 2.0.
More preferably, the R/Si value is 1.75 to 1.85.
Preferably, the molecular weight of the epoxy-modified silicone resin is 1000-30000.
More preferably, the molecular weight of the epoxy-modified silicone resin is 1000-15000.
The preparation method of the epoxy modified organic silicon resin comprises the following steps:
mixing 100-300 parts of tetramethyltetraphenylcyclotetrasiloxane monomer, 50-250 parts of T-chain organosilicon monomer and 30-100 parts of end-capping agent, heating to 50-80 ℃, then carrying out reduced pressure dehydration for 1-2 h, then adding an acid catalyst accounting for 0.02-0.08 percent of the total weight of the tetramethyltetraphenylcyclotetrasiloxane monomer, the T-chain organosilicon monomer and the end-capping agent, carrying out heat preservation reaction for 4-10 h, adjusting the pH value to 6-7, filtering, carrying out reduced pressure distillation, and removing unreacted monomers to obtain vinyl-terminated organosilicon resin;
adding 10-50 parts of oxidant into 10-50 parts of vinyl-terminated organic silicon resin at the temperature of-5-5 ℃, reacting for 10min-60min at the temperature of 5-10 ℃, then adding 1-10 parts of reducing agent, stirring for 10min-60min, extracting and drying to obtain the epoxy modified organic silicon resin.
In the preparation method, the vinyl-terminated organic silicon resin is prepared by taking a tetramethyl tetraphenyl cyclotetrasiloxane monomer, a T chain organosilicon monomer (an organic silicon trifunctional unit) and an end capping agent as reaction monomers under the action of an acid catalyst. And then, the prepared vinyl-terminated organic silicon resin is further oxidized by using an oxidizing agent, then a reducing agent is added, and redundant oxidizing agent is consumed, so that epoxy modified organic silicon resin is finally obtained, the problem of compatibility between epoxy resin and organic silicon resin in the traditional modification method is solved, and the preparation cost is low.
It is understood that the R/Si value can be adjusted by controlling the ratio of the reactive monomers.
Preferably, 100-200 parts of tetramethyltetraphenylcyclotetrasiloxane monomer, 50-150 parts of T chain organosilicon monomer and 30-60 parts of end capping agent are mixed, the mixture is heated to 50-80 ℃, then the water is removed under reduced pressure for 1-2 h, then an acid catalyst accounting for 0.02-0.05 percent of the total weight of the tetramethyltetraphenylcyclotetrasiloxane monomer, the T chain organosilicon monomer and the end capping agent is added, the heat preservation reaction is carried out for 4-10 h, the pH value is adjusted to 6-7, and the unreacted monomer is removed through filtration and reduced pressure distillation, so as to obtain the vinyl-terminated organosilicon resin.
Preferably, the tetramethyltetraphenylcyclotetrasiloxane monomer is selected from one or more of 2,2,4, 4-tetramethyl-6, 6,8, 8-tetraphenylcyclotetrasiloxane, 1,5, 5-tetramethyl-1, 3,3, 5-tetraphenylcyclotetrasiloxane and 2,4,6, 8-tetramethyl-2, 4,6, 8-tetraphenylcyclotetrasiloxane.
Preferably, the T-chain organosilicon monomer is selected from any one of methyl tri (dimethylsiloxy) silane, ethyl tri (dimethylsiloxy) silane and phenyl tri (dimethylsiloxy) silane.
Preferably, the capping agent is selected from any one of 1,1,3, 3-tetramethyl-1, 3-divinyldisiloxane, 1, 3-dimethyl-1, 3-diphenyl-1, 3-divinyldisiloxane and 1,1,3, 3-tetraphenyl-1, 3-divinyldisiloxane.
Preferably, the acidic catalyst is selected from any one of sulfuric acid, phosphoric acid, trifluoromethanesulfonic acid, and methylbenzenesulfonic acid.
Preferably, the oxidant is selected from one or more of sodium hypochlorite and dilute sulfuric acid.
Preferably, the reducing agent is sodium sulfite.
The synthetic route of the epoxy modified organic silicon resin is as follows:
polymerization between monomers:
terminating the polymerization reaction by using a capping agent:
epoxidation of vinyl:
it is understood that the functional resin is selected from one or more of epoxy resin and bismaleimide.
The epoxy resin includes, but is not limited to, one or more of alicyclic epoxy resin, hydrogenated bisphenol a epoxy resin, glycidyl ester epoxy resin, cyanuric acid epoxy resin, hydantoin epoxy resin, and the like.
The bismaleimide includes but is not limited to one or more of diphenylmethane bismaleimide, N' -m-phenylene bismaleimide, polyamino bismaleimide and the like.
The auxiliary agent is curing agent, filler, coupling agent, curing accelerator and the like.
In a preferred embodiment, the epoxy modified silicone resin composition is prepared from the following raw materials in parts by weight:
the curing agent includes, but is not limited to, one or more of cyanate ester curing agent, aliphatic polyamine type curing agent, aromatic amine type curing agent, polyamide type curing agent, lewis acid-amine complex type curing agent, acid anhydride type curing agent, phenolic aldehyde type curing agent, and the like.
The filler includes, but is not limited to, one or more of titanium dioxide, silica, magnesium oxide, magnesium hydroxide, talc, mica powder, alumina, silicon carbide, boron nitride, aluminum nitride, molybdenum oxide, barium sulfate, and the like.
The coupling agent includes, but is not limited to, one or more of silane coupling agent, titanate coupling agent, aluminate coupling agent, organic chromium complex coupling agent, and the like.
The curing accelerator includes, but is not limited to, one or more of imidazole type accelerators, peroxide type accelerators, azo type accelerators, tertiary amine type accelerators, phenol type accelerators, organic metal salt accelerators, inorganic metal salt accelerators and the like.
A prepreg comprises the epoxy modified silicone resin composition as a raw material.
It will be appreciated that the method of making the prepreg comprises the steps of:
and covering the surface of the reinforcing material with the resin composition by adopting an impregnation method, and heating until semi-curing to obtain the prepreg.
Preferably, the semi-curing process parameters are as follows: heating to 130 ℃ and keeping the temperature at 250 ℃ for 2-10 min.
It should be understood that the reinforcement material is a well-known inorganic or organic fibrous material, and the inorganic fibrous reinforcement substrate includes, but is not limited to, glass fibers (including different types E, NE, D, S, T, etc.), carbon fibers, silicon carbide fibers, asbestos fibers, and the like. Organic fiber reinforced substrates include, but are not limited to, nylon, ultra-high molecular weight polyethylene fibers, aramid fibers, polyimide fibers, polyester fibers, cotton fibers, and the like.
A laminated board comprises the epoxy modified silicone resin composition or the prepreg.
It will be appreciated that the method of making the laminate comprises the steps of:
several of the above prepregs were laminated.
Preferably, the lamination process parameters are: at a temperature of 150 ℃ and a temperature of 300 ℃ and a pressure of 10kgf/cm2-30kgf/cm2And hot-press forming for 100-300 min under the condition that the vacuum degree is less than 2 kPa.
The "plurality of the prepregs" means at least one of the prepregs.
In particular, in the lamination, a metal-copper-clad laminate may be obtained by laminating a plurality of prepregs, that is, a laminate, which is clad with a metal copper foil on one side or both sides.
Preferably, the metal copper foil has a thickness of 3 μm to 35 μm.
In the following, reference will be made to specific examples, which are intended to illustrate the invention and, unless otherwise indicated, to show all of the starting materials available from commercial sources.
Hydrogenated bisphenol A epoxy resin is available from national institutes and is available in the model number ST-1000.
Cycloaliphatic epoxy resin is available from xylonite, type 2021P.
Bismaleimides are available from KI-Chemical under the model BMI-70.
Silicone resins are commercially available at high force, model SC 2006.
Example 1
This example provides a white epoxy-modified silicone resin composition, a prepreg, and a laminate, which are prepared as follows:
70 parts of epoxy modified silicon resin, 10 parts of hydrogenated bisphenol A epoxy resin and 5 parts of anhydride curing agent are dissolved in a mixed solvent of butanone, toluene and propylene glycol methyl ether in sequence, wherein the butanone, the toluene and the propylene glycol methyl ether are mixed according to the mass ratio of 1:1: 1. Under the condition of stirring, 10 parts of titanium dioxide, 25 parts of silicon dioxide, 0.1 part of silane coupling agent and 2 parts of 2-methylimidazole are added, and stirring is continued to obtain uniform glue solution, namely the epoxy modified silicone resin composition.
2116 glass fiber cloth (basis weight 105 g/m)2) And (3) soaking the epoxy modified silicon resin composition, and baking the epoxy modified silicon resin composition in a hot air circulation oven at 180 ℃ for 3min to obtain a prepreg with the resin content of 50%.
Laminating 4 sheets of prepreg, covering each of the upper and lower surfaces of the laminate with a sheet of electrolytic copper foil having a thickness of 12 μm, placing the laminate in a vacuum press machine with a programmable temperature and pressure control, and keeping the laminate in a vacuum state at 25kgf/cm2Curing at 200 ℃ for 100 minutes under the pressure of (1) to obtain a copper clad laminate with a thickness of 0.4 mm.
Example 2
This example provides a white epoxy-modified silicone resin composition, a prepreg, and a laminate, which are prepared as follows:
dissolving 10 parts of epoxy modified silicon resin, 30 parts of alicyclic epoxy resin and 30 parts of anhydride curing agent in a mixed solvent of butanone, toluene and propylene glycol methyl ether in sequence, wherein the butanone, the toluene and the propylene glycol methyl ether are mixed according to the mass ratio of 1:1: 1. Under the condition of stirring, 10 parts of titanium dioxide, 10 parts of alumina, 40 parts of silicon dioxide, 2 parts of silane coupling agent and 0.1 part of 2-methylimidazole are added, and stirring is continued to obtain uniform glue solution, namely the epoxy modified silicone resin composition.
2116 glass fiber cloth (basis weight 105 g/m)2) And (3) soaking the epoxy modified silicon resin composition, and baking the epoxy modified silicon resin composition in a hot air circulation oven at 180 ℃ for 3min to obtain a prepreg with the resin content of 55%.
Laminating 4 sheets of prepreg, covering each of the upper and lower surfaces of the laminate with a sheet of electrolytic copper foil having a thickness of 12 μm, placing the laminate in a vacuum press machine with a programmable temperature and pressure control, and keeping the laminate in a vacuum state at 25kgf/cm2Curing at 200 ℃ for 100 minutes under the pressure of (1) to obtain a copper clad laminate with a thickness of 0.4 mm.
Example 3
This example provides a white epoxy-modified silicone resin composition, a prepreg, and a laminate, which are prepared as follows:
dissolving 50 parts of epoxy modified silicone resin, 20 parts of bismaleimide and 20 parts of phenolic curing agent in a mixed solvent of butanone, toluene and propylene glycol methyl ether in sequence, wherein the butanone, the toluene and the propylene glycol methyl ether are mixed according to a mass ratio of 1:1: 1. Under the condition of stirring, 10 parts of titanium dioxide, 10 parts of alumina, 25 parts of silicon dioxide, 0.5 part of silane coupling agent, 0.5 part of 2-methylimidazole and 0.7 part of dicumyl peroxide are added, and stirring is continued to obtain a uniform glue solution, namely the epoxy modified silicon resin composition.
2116 glass fiber cloth (basis weight 105 g/m)2) And (3) soaking the epoxy modified silicon resin composition, and baking the epoxy modified silicon resin composition in a hot air circulation oven at 180 ℃ for 3min to obtain a prepreg with the resin content of 50%.
Laminating 4 sheets of prepreg, covering each of the upper and lower surfaces of the laminate with a sheet of electrolytic copper foil having a thickness of 12 μm, placing the laminate in a vacuum press machine with a programmable temperature and pressure control, and keeping the laminate in a vacuum state at 25kgf/cm2Curing at 200 ℃ for 100 minutes under the pressure of (1) to obtain a copper clad laminate with a thickness of 0.4 mm.
Example 4
This example provides a white epoxy-modified silicone resin composition, a prepreg, and a laminate, which are prepared as follows:
dissolving 50 parts of epoxy modified silicon resin, 10 parts of alicyclic epoxy resin and 15 parts of anhydride curing agent in a mixed solvent of butanone, toluene and propylene glycol methyl ether in sequence, wherein the butanone, the toluene and the propylene glycol methyl ether are mixed according to the mass ratio of 1:1: 1. Under the condition of stirring, 10 parts of titanium dioxide, 10 parts of alumina, 0.2 part of silane coupling agent and 0.8 part of 2-methylimidazole are added, and stirring is continued to obtain uniform glue solution, namely the epoxy modified silicone resin composition.
2116 glass fiber cloth (basis weight 105 g/m)2) And (3) soaking the epoxy modified silicon resin composition, and baking the epoxy modified silicon resin composition in a hot air circulation oven at 180 ℃ for 3min to obtain a prepreg with the resin content of 50%.
Laminating 4 sheets of prepreg, covering each of the upper and lower surfaces of the laminate with a sheet of electrolytic copper foil having a thickness of 12 μm, placing the laminate in a vacuum press machine with a programmable temperature and pressure control, and keeping the laminate in a vacuum state at 25kgf/cm2Curing at 200 ℃ for 100 minutes under the pressure of (1) to obtain a copper clad laminate with a thickness of 0.4 mm.
Comparative example 1
The comparative example provides a white epoxy modified silicone resin composition, a prepreg and a laminate, the preparation method comprising:
40 parts of alicyclic epoxy resin and 30 parts of anhydride curing agent are dissolved in a mixed solvent of butanone, toluene and propylene glycol methyl ether in sequence, wherein the butanone, the toluene and the propylene glycol methyl ether are mixed according to the mass ratio of 1:1: 1. Under the condition of stirring, 10 parts of titanium dioxide, 10 parts of alumina, 40 parts of silicon dioxide, 2 parts of silane coupling agent and 0.1 part of 2-methylimidazole are added, and stirring is continued to obtain uniform glue solution, namely the epoxy modified silicone resin composition.
2116 glass fiber cloth (basis weight 105 g/m)2) And (3) soaking the epoxy modified silicon resin composition, and baking the epoxy modified silicon resin composition in a hot air circulation oven at 180 ℃ for 3min to obtain a prepreg with the resin content of 50%.
Laminating 4 sheets of prepreg, covering each of the upper and lower surfaces of the laminate with a sheet of electrolytic copper foil having a thickness of 12 μm, placing the laminate in a vacuum press machine with a programmable temperature and pressure control, and keeping the laminate in a vacuum state at 25kgf/cm2Curing at 200 ℃ for 100 minutes under the pressure of (1) to obtain a copper clad laminate with a thickness of 0.4 mm.
Comparative example 2
The comparative example provides a white epoxy modified silicone resin composition, a prepreg and a laminate, the preparation method comprising:
dissolving 100 parts of organic silicon resin and 1 part of dibutyltin dilaurate in a mixed solvent of butanone, toluene and propylene glycol methyl ether in sequence, wherein the butanone, the toluene and the propylene glycol methyl ether are mixed according to the mass ratio of 1:1: 1. Under the condition of stirring, 10 parts of titanium dioxide, 10 parts of alumina and 0.7 part of silane coupling agent are added, and stirring is continued to obtain uniform glue solution.
Will 2116 glass fiber cloth (basis weight 105 g/m)2) Soaking in the above glue solution, and baking in hot air circulation oven at 180 deg.C for 3min to obtain prepreg with resin content of 50%.
Laminating 4 sheets of prepreg, covering each of the upper and lower surfaces of the laminate with a sheet of electrolytic copper foil having a thickness of 12 μm, placing the laminate in a vacuum press machine with a programmable temperature and pressure control, and keeping the laminate in a vacuum state at 25kgf/cm2Curing at 200 ℃ for 100 minutes under the pressure of (1) to obtain a copper clad laminate with a thickness of 0.4 mm.
Performance testing
The products obtained in examples 1 to 4 and comparative examples 1 to 2 were subjected to the following performance tests, and the test results are shown in Table 1.
Peel strength: the test method was performed according to IPC-TM-6502.4.8.
High temperature yellowing resistance test: etching the copper-clad plate to obtain a white laminated plate, cutting the obtained white laminated plate into samples of 4inch and 4inch, baking the samples in an oven at 200 ℃, wherein the baking time is 4h, 24h and 72h respectively, and then testing the reflectivity and whiteness of the samples respectively, and comparing the samples with the samples which are not baked.
And (3) weather resistance test: etching the copper-clad plate to obtain a white laminated plate, cutting the obtained white laminated plate into a 4inch by 4inch sample, placing the sample in an ultraviolet light aging-resistant test box, and testing the change of reflectivity and whiteness after placing the sample for 500 hours, 750 hours and 1000 hours at 85 ℃.
TABLE 1
The epoxy modified silicone resin compositions prepared in the embodiments 1 to 4 have high peel strength and good mechanical properties, can keep good whiteness for a long time after curing, and the laminated sheet prepared by using the epoxy modified silicone resin compositions as raw materials has high-temperature yellowing resistance and weather resistance, and can effectively improve the light-emitting effect of an LED and prolong the service life when being used as a substrate of an LED element.
Compared with example 2, comparative example 1 does not add epoxy modified silicone resin, but replaces with alicyclic epoxy resin of the same weight, while the cost is increased, its high temperature yellowing resistance and weatherability are far inferior to example 2, illustrate that the addition of epoxy modified silicone resin has important effect on the improvement of the weatherability of the composition and even the laminate. Comparative example 2, which uses the silicone resin material alone, has a poor peel strength.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (12)
1. The epoxy modified silicone resin composition is characterized by being prepared from the following raw materials in parts by weight:
10 to 70 parts of epoxy modified organic silicon resin,
10-30 parts of functional resin,
15 to 100 portions of auxiliary agent,
the epoxy modified silicone resin has a structure shown in formula I:
wherein R is1Is methyl, ethyl or phenyl;
R2is methyl or phenyl;
R3is methyl or phenyl;
m is an integer in the range of 1-20;
n is an integer in the range of 1 to 20.
2. The epoxy modified silicone composition of claim 1, wherein the functional resin is selected from one or more of epoxy resins and bismaleimides.
3. The epoxy-modified silicone composition according to claim 2, wherein the epoxy resin is selected from one or more of a cycloaliphatic epoxy resin, a hydrogenated bisphenol a epoxy resin, a glycidyl ester epoxy resin, a cyanuric acid epoxy resin, and a hydantoin epoxy resin.
4. The epoxy modified silicone composition of claim 2, wherein the bismaleimide is selected from one or more of diphenylmethane bismaleimide, N' -m-phenylene bismaleimide, and polyaminobismaleimide.
5. The epoxy-modified silicone resin composition according to any one of claims 1 to 4, wherein the auxiliary agent is one or more selected from the group consisting of a curing agent, a filler, a coupling agent and a curing accelerator.
6. The epoxy modified silicone resin composition according to claim 5, characterized by being prepared from the following raw materials in parts by weight:
7. the epoxy-modified silicone resin composition according to claim 6, wherein the curing agent is one or more selected from the group consisting of cyanate ester curing agents, aliphatic polyamine-type curing agents, aromatic amine-type curing agents, polyamide-type curing agents, Lewis acid-amine complex-type curing agents, acid anhydride-type curing agents, and phenolic curing agents.
8. The epoxy modified silicone composition of claim 6, wherein the filler is selected from one or more of titanium dioxide, silica, magnesium oxide, magnesium hydroxide, talc, mica powder, alumina, silicon carbide, boron nitride, aluminum nitride, molybdenum oxide, and barium sulfate.
9. The epoxy modified silicone composition of claim 6, wherein the coupling agent is selected from one or more of a silane based coupling agent, a titanate coupling agent, an aluminate coupling agent, and an organochromium complex coupling agent.
10. The epoxy-modified silicone resin composition according to claim 6, wherein the curing accelerator is one or more selected from the group consisting of imidazole accelerators, peroxide accelerators, azo accelerators, tertiary amine accelerators, phenol accelerators, organic metal salt accelerators and inorganic metal salt accelerators.
11. A prepreg characterized in that a raw material of the prepreg comprises the epoxy-modified silicone resin composition according to any one of claims 1 to 10.
12. A laminate characterized in that a raw material for the laminate comprises the epoxy-modified silicone composition according to any one of claims 1 to 10, or the prepreg according to claim 11.
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| CN201911361740.7A CN111100463A (en) | 2019-12-26 | 2019-12-26 | Epoxy modified silicone resin composition and application thereof |
| PCT/CN2020/088416 WO2021128691A1 (en) | 2019-12-26 | 2020-04-30 | Epoxy-modified silicone resin composition and use thereof |
| TW109119872A TWI767249B (en) | 2019-12-26 | 2020-06-12 | Epoxy modified silicon resin composition and use thereof |
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| TW202124537A (en) | 2021-07-01 |
| WO2021128691A1 (en) | 2021-07-01 |
| TWI767249B (en) | 2022-06-11 |
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