CN106751507B - A kind of high heat epoxy and combinations thereof and application - Google Patents
A kind of high heat epoxy and combinations thereof and application Download PDFInfo
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- CN106751507B CN106751507B CN201611148525.5A CN201611148525A CN106751507B CN 106751507 B CN106751507 B CN 106751507B CN 201611148525 A CN201611148525 A CN 201611148525A CN 106751507 B CN106751507 B CN 106751507B
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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
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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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
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/061—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of metal
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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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
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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
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/08—Impregnating
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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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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1477—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing nitrogen
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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
- B32B2307/30—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
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
- B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
-
- 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
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The present invention relates to modified epoxy technical fields, more particularly to a kind of high heat epoxy and combinations thereof and application, after high heat epoxy is dissolved by heating in reactive tank by straight chain type epoxy resin, 25-60 parts of brominated epoxy resins and the 10-25 parts of isocyanates that parts by weight are 15-45 parts, the catalyst for being 0.5-5:100 with the mass ratio of isocyanates is added, after being warming up to 170-190 DEG C of reaction 1.5-4.5 hours, multifunctional novolac epoxy resin is added and is blended to obtain.Have the characteristics that low viscosity, easy impregnation, using acetone soln and the composition that phenolic resin, promotor are re-dubbed of the above-mentioned high heat epoxy being prepared convenient for operation, the printed circuit laminate being prepared by the composition, with high heat resistance, low water absorption, caking property is good, the requirement of good flame resistance and suitable leadless process, can be widely applied to high performance electronic material.
Description
Technical field
The present invention relates to modified epoxy technical fields, and in particular to a kind of high heat epoxy and combinations thereof and
Using.
Background technique
As PCB industry develops rapidly, copper-clad plate industry is flourishing, and the market demand of high performance copper clad laminate is increasingly
Increase.In today that the unleaded epoch are all-round developing and reach its maturity, in addition to the performances such as the caking property of product, Tg value, CTE value are standby
Concerned outer, heat resistance, toughness, the PCB processing performance of material also become the emphasis of everybody concern, copper-clad plate substrate performance it is equal
The sexual development that weighs becomes the important trend for developing novel copper-clad plate material.
The FR-4 copper-clad plate of early stage is since solidfied material crosslink density is lower, and generally only 130 DEG C of glass transition temperature (Tg)
Level, thermal decomposition temperature (Td:5%Weight Loss) is generally 310 DEG C or so, can be in the past lead jointing epoch
It uses, but enters the pb-free solder epoch, to meet the requirement of high welding temperature, it is unable to do what one wishes.
With gradually increasing for mankind's environmental consciousness, the use of heavy metal by the control being increasingly stringenter or even is forbidden making
With.On 2 13rd, 2003, " the electrical and electronic product waste instruction case (WEEE) " of European Union and " about in electronic electric equipment
In be forbidden to use certain Hazardous Substances Directive cases (ROHS) " formal announce.It is pointed out in the two instruction cases: from July 1st, 2006
It rises, is invested in the new electronics and electric product in market, cannot include lead, mercury, cadmium, Cr VI, poly- dibromodiphenyl ether or poly- bromine connection
The harmful substances such as benzene." two instructions " provides powerful driving force, present epoxy to the unleaded PCB substrate material of popularization and use
The copper-clad plate of plexiglas cloth is free of lead originally, but since the solder that downstream PCB factory uses is leypewter, does not meet ROHS
Requirement.For adapted to leadless processing procedure, welding material used in the back segment assembly welding processing procedure of PCB will be by traditional tin-lead conjunction
Gold switchs to unleaded Tin Silver Copper Alloy, and the fusing point of such alloy material is also improved by 183 DEG C to 217 DEG C, and the temperature of wave-soldering is then
It is improved by 230 DEG C to 260 DEG C, in addition, the circuit of printed circuit board is sent out toward high density with the lightness of electronic instrument and equipment
Exhibition, the densification of printed circuit make more microelectronic component installations on a printed circuit, and this requires extend circuit board
The immersed solder time, so that the heat resistance to printed circuit board is put forward higher requirements.
Summary of the invention
In view of this, it is necessary to for above-mentioned problem, provide a kind of with good flame-retardance, wellability and caking property
Meanwhile the high heat epoxy and combinations thereof for effectively improving heat resistance, and provide using the high heat epoxy
The method that the composition of composition prepares laminate.
To achieve the above object, the present invention takes technical solution below:
High heat epoxy of the invention, straight chain type epoxy resin, 25-60 parts of brominations by parts by weight for 15-45 parts
After epoxy resin and 10-25 parts of isocyanates dissolve by heating in reactive tank, being added with the mass ratio of isocyanates is 0.5-5:
100 catalyst after being warming up to 170-190 DEG C of reaction 1.5-4.5 hours, is added multifunctional novolac epoxy resin and is blended to obtain.
Further, the high heat epoxy, by 25-45 parts of straight chain type epoxy resin, 35-50 parts of brominated epoxies
After resin and 15-20 parts of isocyanates dissolve by heating in reactive tank, being added with the mass ratio of isocyanates is 3.5-5:100's
Catalyst is warming up to 150-180 DEG C of reaction 3.5-4.5 hours, adds multifunctional novolac epoxy resin and is blended to obtain.
Further, the high heat epoxy is the five-ring heterocycles structure for including the formation of C, N, O element；Bromine content is
20-25%, epoxide equivalent 315-345g/eq.
Further, the catalyst is quaternary ammonium salt, imidazoles or quaternary phosphonium salt.
Further, the straight chain type epoxy resin is selected from BPF type or BPA Linear epoxy resin；
The polyfunctional epoxy resin is selected from o-cresol formaldehyde epoxy resin, linear phenolic epoxy resin, BPA type epoxy novolac
At least one of resin, four phenolic group ethane, four glycidol ether；
The brominated epoxy resin is selected from the High Bromine epoxy Resin or multifunctional resin modified that bromine content is greater than 40%
Low brominated epoxy of the bromine content less than 38%.
Further, the isocyanates is toluene di-isocyanate(TDI) (TDI), methyl diphenylene diisocyanate (MDI)
Or one or both of polymeric MDI.
A kind of composition of high heat epoxy, parts by weight composition are as follows: the acetone soln 120- of high heat epoxy
130 parts, 30-45 parts of phenolic resin, 0.005~0.01 part of promotor；The acetone soln of the high heat epoxy is above-mentioned
High heat epoxy be dissolved in acetone formed solid content be 79-81% solution.
Further, the phenolic resin is selected from bisphenol A type phenolic resin, linear phenolic resin, linear o-cresol first
One or both of urea formaldehyde or biphenyl type phenolic resin.
Further, the promotor is imidazoles promotor, including imidazoles, 2-methylimidazole, 2- ethyl -4- methyl
Imidazoles, 1- amino-ethyl -2-methylimidazole, 1- cyanoethyl substituted imidazole and its addition product.
The composition of above-mentioned high heat epoxy is applied to the method for preparing printed circuit laminate, comprising:
Step (1) makes the combination with butanone (MEK) or the composition of propylene glycol monomethyl ether (PM) adjustment high heat epoxy
Object solid content is 45-55%, as varnish gum liquid；Glass fabric is immersed in varnish gum liquid, by 170-
180 DEG C several minutes of heated baking, make it is dry after glass of the prepreg melting viscosity between 800-1600Pa.s, after dipping
Fiber cloth becomes prepreg；
Step (2) places copper foil in the one or both sides of the resulting a piece of prepreg of step (1), or multi-disc is presoaked
Stain body is stacked together, then the one or both sides of the prepreg after stacking place copper foil；
Step (3) is by the prepreg after the resulting placement copper foil of step (2) in 20-35Kg/cm2Pressurization, 80-240 DEG C
After heating 130-170min, gradually cooling can be obtained printed circuit laminate.
The invention has the benefit that
High heat resistance resin of the invention itself has good high heat resistance, can be into one after phenolic resin use of arranging in pairs or groups
Step improves the heat resistance of plate.High heat epoxy composition of the invention is low, easy with viscosity to be impregnated with, convenient for the spy of operation
Point, the prepreg good appearance manufactured with it；According to copper clad laminate obtained by the present invention, it can reach high heat resistance (Tg≤160
DEG C, Td≤360 DEG C, PCT test 4h≤6min), low water absorption, caking property is good, the requirement of good flame resistance and suitable leadless process,
It can be widely applied to high performance electronic material.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with the embodiment of the present invention, to this hair
Bright technical solution work further clearly and completely describes.It should be noted that described embodiment is only the present invention one
Section Example, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not doing
Every other embodiment obtained under the premise of creative work out, shall fall within the protection scope of the present invention.
Resin 1
High heat epoxy synthesis of the invention are as follows: 30 parts of straight chain type epoxy resin, 35 parts of height are added in reactive tank
Then the catalyst tetramethyl ammonium chloride (mass ratio with MDI is added in brominated eopxy resin and 20 parts of isocyanates (MDI) rising temperature for dissolving
For 3.5:100), it is warming up to 170-190 DEG C of reaction 4.0-4.5 hours, 18 parts of o-cresol formaldehyde epoxy resins is added and is blended, obtain
High heat epoxy adds the solution that acetone solution is 80% at solid content after cooling.The high heat epoxy being prepared
Bromine content be 21-24%, epoxide equivalent is between 315-318g/eq.
Resin 2
High heat epoxy synthesis of the invention are as follows: 40 parts of straight chain type epoxy resin, 55 parts of height are added in reactive tank
Then the catalyst tetramethyl ammonium chloride (mass ratio with MDI is added in brominated eopxy resin and 15 parts of isocyanates (MDI) rising temperature for dissolving
For 4.8:100), it is warming up to 170-190 DEG C of reaction 4.0-4.5 hours, 10 parts of linear phenolic epoxy resins is added and is blended, obtain
The solution that high heat epoxy, cooling plus acetone solution are 80% at solid content.The high heat epoxy bromine being prepared
Content is 22-25%, and epoxide equivalent is between 325-330g/eq.
Resin 3
High heat epoxy synthesis of the invention are as follows: 40 parts of straight chain type epoxy resin, 35 parts of height are added in reactive tank
Then the catalyst tetramethyl ammonium chloride (mass ratio with MDI is added in brominated eopxy resin and 10 parts of isocyanates (MDI) rising temperature for dissolving
For 4.0:100), it is warming up to 170-190 DEG C of reaction 3.5-4.0 hours, 13 parts of BPA type novolac epoxy resins is added and is blended, obtain
To high heat epoxy, cooling plus acetone solution are 80% at solid content.High heat epoxy bromine content is 22-24%,
Epoxide equivalent is between 315-320g/eq.
Resin 4
For the FR-4 resin GEBR454A80 of HongChang Electronic Materials Co., Ltd's production.
Embodiment 1
Using resin based on ingredient (resin 1) of the invention, collocation curing agent is linear phenolic resin GERH833K65
With promotor 2-methylimidazole, the composition of high heat epoxy is obtained.The specific parts by weight composition of composition are as follows: 125 parts of trees
1,57 parts of linear phenolic resin curing agent GERH833K65 of rouge, 0.01 part of promotor 2-MI (PHR)；With butanone (MEK) or the third two
The composition solid content that alcohol methyl ether (PM) adjusts high heat epoxy is 55%, varnish gum liquid is obtained, by 7628 glass
Glass fiber cloth is impregnated in above-mentioned varnish gum liquid, then at 170-180 DEG C of temperature, in, adjustment several minutes dry containing dipping machine
Drying time is controlled, glass fabric of the prepreg melting viscosity after making drying between 800-1600Pa.s, after dipping
As prepreg, finally 8 prepregs are stacked layer by layer between the copper foil of 35 μ m-thick of two panels, in 25Kg/cm2Pressure, temperature
Degree control is as follows:
After heating pressurization, the copper clad laminate of 1.6mm thickness can be obtained.Tg≤160 DEG C of this product, Td≤360 DEG C are resistance to
It is hot preferable.See Table 2 for details for function.
Embodiment 2
Using resin based on ingredient (resin 1) of the invention, arrange in pairs or groups bisphenol A type phenolic resin GERH832K65 and promotion
Agent 2-methylimidazole obtains the composition of high heat epoxy.The specific parts by weight composition of composition are as follows: 125 parts of resins 1,54
Part bisphenol A type phenolic resin GERH832K65,0.01 part of promotor 2-MI (PHR)；The production substrate process of embodiment 1 is repeated,
Tg≤160 DEG C of products obtained therefrom, Td≤360 DEG C, heat resistance are preferable.See Table 2 for details for function.
Embodiment 3
Using resin based on ingredient (resin 2) of the invention, arrange in pairs or groups linear phenolic resin GERH833K65 and promotor
2-methylimidazole obtains high heat epoxy composition.The specific parts by weight composition of composition are as follows: 125 parts of resins, 2,57 parts of lines
Property phenolic resin GERH833K65,0.01 part of promotor 2-MI (PHR)；Repeat the production substrate process of embodiment 1, products obtained therefrom
Tg≤160 DEG C, Td≤360 DEG C, heat resistance is preferable.See Table 2 for details for function.
Embodiment 4
Using resin based on ingredient (resin 2) of the invention, collocation curing agent be linear phenolic resin GERH833K65,
Bisphenol A phenolic resin GERH832K65 and promotor 2-methylimidazole, obtain the composition of high heat epoxy.Composition tool
Body is parts by weight composition are as follows: 125 parts of resins, 2,34 parts of novolac curing agent GERH833K65,23 parts of bisphenol A phenolic resins
GERH832K65,0.01 part of promotor 2-MI (PHR)；Repeat the production substrate process of embodiment 1, Tg≤160 of products obtained therefrom
DEG C, Td≤360 DEG C, heat resistance is preferable.See Table 2 for details for function.
Embodiment 5
Using resin based on ingredient (resin 3) of the invention, collocation curing agent be linear phenolic resin GERH833K65,
Bisphenol A phenolic resin GERH832K65 and promotor 2-methylimidazole, obtain the composition of high heat epoxy.Composition tool
Body weight part composition are as follows: 125 parts of resins, 3,26 parts of novolac curing agent GERH833K65,21 parts of bisphenol A phenolic resins
GERH832K65,0.01 part of promotor 2-MI (PHR)；Repeat the production substrate process of embodiment 1, Tg≤160 of products obtained therefrom
DEG C, Td≤360 DEG C, heat resistance is preferable.See Table 2 for details for function.
Comparative example 1
Using resin based on 125 parts of resins 4 (GEBR454A80), 25 parts of dicyandiamides of arranging in pairs or groups are as curing agent, and 0.01 part
Promotor 2-methylimidazole repeats embodiment 1 and makes substrate process, and the heat resistance of products obtained therefrom is poor.See Table 2 for details for function.
The composition Con trolling index parameter area of the high heat epoxy prepared in the present invention, see the table below shown in 1:
The composition index parameter of 1 high heat epoxy of table
The performance indicator data for the printed circuit laminate that the present invention is prepared are detailed in the following table 2:
2 printed circuit laminate performance indicator data of table
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 1 |
| Glass transition temperature (DEG C) | 163 | 165 | 165 | 165 | 166 | 137 |
| Strength of glass (1b/in) | 9.5 | 9.3 | 9.9 | 10 | 10 | 10 |
| PCT plate bursting (120 DEG C of 4h, min) | ≧6 | ≧6 | ≧6 | ≧6 | ≧6 | ≦1 |
| T288(min) | ≧30 | ≧30 | ≧30 | ≧30 | ≧30 | ≦5 |
| Flame resistance | 94V-0 | 94V-0 | 94V-0 | 94V-0 | 94V-0 | 94V-0 |
| Thermal decomposition temperature (DEG C, 5%Loss) | 361 | 366 | 365 | 365 | 368 | 308 |
From the embodiment of the present invention in table 2 it is found that using high heat resistance asphalt mixtures modified by epoxy resin of the invention compared with comparative example performance
Rouge, arrange in pairs or groups curing agent linear phenolic resin or bisphenol A phenolic resin, the plate of production have the spies such as good fire-retardant, high-fire resistance
Point.
Raw material used in 1.1 above-described embodiments
GERH832K65 is the bisphenol A type phenolic resin of HongChang Electronic Materials Co., Ltd's production, and solid content is
65%
GERH833K65 is the linear phenolic resin of HongChang Electronic Materials Co., Ltd's production, and solid content is all
65%.
Curing agent: dicyandiamide, 10wt% are dissolved in dimethylformamide (DMF).
Curing accelerator 2-MI (PHR): 2-methylimidazole.
Glass fabric is 7628 cloth.
The performance metrics explanation of 1.2 printed circuit laminates
1) it glass transition temperature (Tg, DEG C): is measured according to the 2.4.25 of IPC-TM-650.
2) it peel strength (1b/in): is measured according to the 2.4.8 of IPC-TM-650.
3) PCT plate bursting (min): under 2 atmospheric pressure, in 120 DEG C of pressure cooker, boiling 4 hours, then by sample in 288
DEG C tin furnace impregnate, observe separation time.
4) T288 tests (min): using TMA method test sample separation time.
5) it flame resistance: is measured according to UL-94 vertical combustion.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
Limitations on the scope of the patent of the present invention therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Protect range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of high heat epoxy, which is characterized in that by parts by weight be 15-45 parts straight chain type epoxy resin, 25-60 parts
After brominated epoxy resin and 10-25 parts of isocyanates dissolve by heating in reactive tank, addition and the mass ratio of isocyanates are
The catalyst of 0.5-5:100 after being warming up to 170-190 DEG C of reaction 1.5-4.5 hours, is added multifunctional novolac epoxy resin and is blended
It arrives.
2. high heat epoxy according to claim 1, which is characterized in that the high heat epoxy, by 25-45
After the straight chain type epoxy resin, 35-50 parts of brominated epoxy resins and 15-20 parts of isocyanates of part dissolve by heating in reactive tank,
The catalyst for being 3.5-5:100 with the mass ratio of isocyanates is added, is warming up to 150-180 DEG C of reaction 3.5-4.5 hours, adds
Multifunctional novolac epoxy resin is blended to obtain.
3. high heat epoxy according to claim 1 or 2, which is characterized in that the high heat epoxy is packet
Include the five-ring heterocycles structure of C, N, O element formation；Bromine content is 20-25%, epoxide equivalent 315-345g/eq.
4. high heat epoxy according to claim 1 or 2, which is characterized in that the catalyst be quaternary ammonium salt, imidazoles or
Quaternary phosphonium salt.
5. high heat epoxy according to claim 1 or 2, which is characterized in that the straight chain type epoxy resin is selected from
BPF type or BPA Linear epoxy resin；
The polyfunctional epoxy resin is selected from o-cresol formaldehyde epoxy resin, linear phenolic epoxy resin, BPA type epoxy novolac tree
At least one of rouge, four phenolic group ethane, four glycidol ether；
The brominated epoxy resin is selected from High Bromine epoxy Resin of the bromine content greater than 40% or multifunctional resin modified bromine contains
Measure the low brominated epoxy less than 38%.
6. high heat epoxy according to claim 1 or 2, which is characterized in that the isocyanates be TDI, MDI or
One or both of polymeric MDI.
7. a kind of composition of high heat epoxy, which is characterized in that parts by weight composition are as follows: the acetone of high heat epoxy
120-130 parts of solution, 30-45 parts of phenolic resin, 0.005~0.01 part of promotor；The acetone of the high heat epoxy is molten
Liquid be high heat epoxy described in any one of the claims 1-6 be dissolved in acetone formed solid content be 79-
81% solution.
8. the composition of high heat epoxy according to claim 7, which is characterized in that the phenolic resin is selected from
One of bisphenol A type phenolic resin, linear phenolic resin, linear o-cresol formaldehyde resin or biphenyl type phenolic resin or two
Kind；
The promotor is imidazoles promotor, including imidazoles, 2-methylimidazole, 2-ethyl-4-methylimidazole, 1- amino second
Base -2-methylimidazole, 1- cyanoethyl substituted imidazole and its addition product.
9. a kind of composition of high heat epoxy described in claim 7 or 8 is in the application for preparing printed circuit laminate.
10. the side that a kind of composition using high heat epoxy described in claim 7 or 8 prepares printed circuit laminate
Method, comprising:
Step (1) makes the composition solid content with butanone or the composition of propylene glycol monomethyl ether adjustment high heat epoxy
For 45-55%, as varnish gum liquid；Glass fabric is immersed in varnish gum liquid, by 170-180 DEG C of heated baking
Several minutes, for the prepreg melting viscosity after making drying between 800-1600Pa.s, the glass fabric after dipping becomes pre-
Impregnating；
Step (2) places copper foil in the one or both sides of the resulting a piece of prepreg of step (1), or by multi-disc prepreg
It is stacked together, then the one or both sides placement copper foil of the prepreg after stacking；
Step (3) is by the prepreg after the resulting placement copper foil of step (2) in 20-35Kg/cm2Pressurization, 80-240 DEG C of heating
After 130-170min, gradually cooling can be obtained printed circuit laminate.
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| CN108192294A (en) * | 2017-12-29 | 2018-06-22 | 纽宝力精化(广州)有限公司 | A kind of cyanate modified resin of low Dk/Df values and preparation method thereof |
| CN108192291A (en) * | 2017-12-29 | 2018-06-22 | 纽宝力精化(广州)有限公司 | High-fire resistance aluminum substrate composition epoxy resin and preparation method and application |
| CN109094166B (en) * | 2018-08-24 | 2020-12-22 | 山东金宝电子股份有限公司 | Preparation method of high-Tg copper-clad plate |
| CN112266576A (en) * | 2020-11-04 | 2021-01-26 | 纽宝力精化(广州)有限公司 | Brominated epoxy resin composition for paper substrate |
| CN115044173B (en) * | 2022-07-11 | 2023-03-21 | 中山超分子新材料有限公司 | Corrosion-resistant high-elasticity composite fiber and preparation method thereof |
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| EP2284004A1 (en) * | 2009-08-13 | 2011-02-16 | Nan Ya Plastics Corp. | Electric circuit board composition and a method of preparing circuit board |
| CN103044858A (en) * | 2012-12-21 | 2013-04-17 | 上海南亚覆铜箔板有限公司 | Thermosetting resin composition, preparation method and use thereof |
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| CN105820717A (en) * | 2016-05-31 | 2016-08-03 | 宝华（黄山）新材料技术有限公司 | Epoxy powder coating with toughness and high temperature resistance |
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| EP2284004A1 (en) * | 2009-08-13 | 2011-02-16 | Nan Ya Plastics Corp. | Electric circuit board composition and a method of preparing circuit board |
| CN103044858A (en) * | 2012-12-21 | 2013-04-17 | 上海南亚覆铜箔板有限公司 | Thermosetting resin composition, preparation method and use thereof |
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