CN104212167A - Preparation and application of low-cost and low-dielectric constant thermosetting resin - Google Patents

Preparation and application of low-cost and low-dielectric constant thermosetting resin Download PDF

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Publication number
CN104212167A
CN104212167A CN201410445263.3A CN201410445263A CN104212167A CN 104212167 A CN104212167 A CN 104212167A CN 201410445263 A CN201410445263 A CN 201410445263A CN 104212167 A CN104212167 A CN 104212167A
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resin
cyanate
preparation
low
resol
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CN104212167B (en
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余若冰
段家真
龚兆红
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East China University of Science and Technology
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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
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • 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
    • B32B19/00—Layered products comprising a layer of natural mineral fibres or particles, e.g. asbestos, mica
    • B32B19/02—Layered products comprising a layer of natural mineral fibres or particles, e.g. asbestos, mica the layer of fibres or particles being impregnated or embedded in a plastic substance
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
    • 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
    • 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
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions 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 C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • 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
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • 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

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

The invention relates to synthesis of novel phenolic resin (thermoplastic and thermosetting) containing a phenyl ether structure and a method and an application of modified thermosetting resin. The resin is obtained by co-curing reaction of two or three of cyanate ester, epoxy resin and phenolic resin containing the phenyl ether structure. The resin comprises the following raw materials: two or three of cyanate ester, epoxy resin and phenolic resin containing the phenyl ether structure, and the percentage by weight of each component is as follows: the cyanate ester accounts for 10-99%, the epoxy resin accounts for 0%-100% and the novel phenolic resin accounts for 10-100%. The thermosetting resin provided by the invention has excellent dielectric performance and high impact strength and has extensive application prospects in the fields of high-performance printed circuit boards and the like.

Description

A kind of preparation of low cost low-k thermosetting resin and application thereof
Technical field
The present invention relates to polymeric material field, be specifically related to a kind of containing the resol of phenylate structure and the preparation method of modified heat convertible resin thereof.
Background technology
21 century is epoch of electronic information develop rapidly, current information network has entered 4G developmental stage, along with the increase day by day of information processing capacity, propose more and more higher requirement to the information processing capability of electronic product and information transfer rate, therefore electronics and IT products are also towards the direction high speed development of lightening, densification, multifunction, high-frequency high-speed.High-frequency high-speed printed-wiring board (PWB) (PCB) is as the carrier of Signal transmissions, in order to realize the high speed transmitted, the material require for PCB substrate has the performances such as high reliability, high wet fastness, high heat resistance, high dielectric property (low-k and low-dielectric loss), good processibility and low cost.Cyanate ester resin has excellent dielectric properties, high heat resistance and the easy feature such as processing because of it, aerospace, electric etc. in receive much concern, be considered to optimal copper-clad plate matrix resin.But cyanate ester resin exists curing process difference (solidification value is high, the time is long) and the large shortcoming of cured article resin fragility large two, simultaneously the price comparison of cyanate ester resin is expensive, the widespread use of cyanate ester resin of these drawbacks limit.
Therefore, in order to obtain the cyanate of excellent combination property, toughening modifying is the main research of cyanate resin modifier always.
Although adopt high-performance thermosetting resin, thermoplastic resin and rubber and cyanate ester resin to carry out copolymerization or the blended toughness can improving cyanate ester resin, these toughening modifying methods can sacrifice dielectric properties and the resistance toheat of cyanate ester resin.Therefore, the preparation method developing a kind of modified cyanic acid ester resin of high comprehensive performance has important using value, comprises excellent toughness, simple curing process, high heat resistance and excellent dielectric properties.
Polyphenylene oxide resin has low-k and low-dielectric loss, good thermotolerance, agent of low hygroscopicity and good dimensional stability.The present invention develops a kind of novel resol, there is phenylate structure and phenolic hydroxyl structure, there is the characteristic of high molecular simultaneously, thus show the rheological property that solvability is good, melting viscosity is low and excellent, not only solve polyphenylene oxide resin exist melt temperature high, fluidity of molten is poor and be insoluble in the problems such as usual vehicle, and can and cyanate generation copolyreaction, increase consistency.
High molecular weight phenolic resin with phenylate structure is introduced cyanate ester resin by the present invention, due to the effect of phenylate structure in resol and phenolic hydroxyl group, not only can reduce the solidification value of cyanate, and the toughness of cyanate ester resin can be improved, excellent thermotolerance and dielectric properties can also be kept simultaneously.
Epoxy resin not only has excellent adhesive property, the advantages such as good moulding process and low cost, and can react respectively with cyanate ester resin, resol, thus obtains the thermosetting resin of excellent combination property.
The present invention utilizes the high molecular novel phenolic resins containing phenylate structure, by it and cyanate ester resin copolyreaction, introduce epoxy resin simultaneously and prepare terpolymer resin, on the basis keeping former cyanate ester resin excellent dielectric performance and thermotolerance, research and develop a kind of new modified cyanate ester resin with high tenacity, low cost.Also find no relevant report at present.
Summary of the invention
Main contents of the present invention have: the method and the performance specification that provide a kind of novel phenolic resins modified heat convertible resin containing phenylate structure.
Novel phenolic resins involved in the present invention, has reactive behavior, and molecular weight is high and controlled, has fabulous consistency with Modified Cyanate Ester Resin.Epoxy resin not only has excellent adhesive property, good processing and forming technology, the features such as low cost, and can simultaneously with cyanate ester resin and resol generation copolyreaction.The modified cyanic acid ester resin of resol/cyanate ester resin/epoxy resin terpolymer gained has unique constructional feature, there is good wet-hot aging performance, thermal characteristics, dielectric properties and the advantage such as with low cost, have a wide range of applications in fields such as high performance print wiring boards.
Implementation method of the present invention is as follows:
A novel phenolic resins containing phenylate structure, comprise 2 kinds of synthetic methods, novolac resin is characterized in that structural formula is as shown in Figure 1:
In formula n be greater than 7 integer.
Wherein the preparation method of novolac resin is as follows:
Adopt phenol, in the presence of a lewis acid catalyst, the methoxyalkyl phenyl ether oligopolymer synthesized with the method related in Chinese patent application publication number CN101186564A, is obtained by condensation reaction.Idiographic flow is: add in flask by the phenol of melting, methoxyalkyl phenyl ether oligopolymer, after add lewis acid catalyst, stir, at 140 DEG C, 160 DEG C, 180 DEG C next stage heating modes, after reaction, underpressure distillation removes unnecessary phenol and small molecules, collects flaxen residuum in flask and is resol.Weight-average molecular weight is greater than 1000, and free phenol is low.
Wherein the preparation method of heat-reactive phenolic resin is as follows:
Adopt phenol, in the presence of a lewis acid catalyst, the methoxyalkyl phenyl ether oligopolymer synthesized with the method related in Chinese patent application publication number CN101186564A, is obtained by condensation reaction.Idiographic flow is: add in flask by the phenol of melting, methoxyalkyl phenyl ether oligopolymer, after add lewis acid catalyst, stir, at 140 DEG C, 160 DEG C, 180 DEG C next stage heating modes, after reaction, underpressure distillation removes unnecessary phenol and small molecules, collects flaxen residuum in flask.Residuum flaxen in receiving flask is dissolved, then adds formaldehyde and ammoniacal liquor, at 90 DEG C, react 40min, after reduced vacuum removes water molecules, be the solution of heat-reactive phenolic resin.Weight-average molecular weight is greater than 1000, and free phenol is low.
Above 2 kinds of novel phenolic resins containing phenylate structure, can alonely also can compositely use.
The present invention propose modified heat convertible resin, by cyanate, epoxy resin, novel phenolic resins (MPF) 2 kinds or 3 kinds form, the mass percent of its component is:
Cyanate 10% ~ 99%
Epoxy resin 0% ~ 100%
The novel resol (MPF) 10 ~ 100% containing phenylate structure
In the present invention, described cyanate ester monomer comprises: bisphenol A cyanate ester (4,4 '-dicyanate base phenyl-propan, BADCy), bis-phenol L-type cyanate (4,4 '-dicyanate base phenyl-ethane, BEDCy), bis-phenol M type cyanate (4,4 '-[1,3-phenyl two (1-methyl-ethylene)] two phenylcyanate), Novolac Cyanate Eater Resin (PT), alkyl diphenyl ether type cyanate, in alkyl xylol type cyanate etc., any one, can be maybe any one in its prepolymer.
In the present invention, described epoxy resin is that the commercialization epoxy resin of the various trade mark all can use.
The modified heat convertible resin preparation method that the present invention proposes, adopts the mode of melting mixing or solution mixing.
Melting mixing: at 100 ~ 140 DEG C, heating cyanate, epoxy resin, MPF make its melting mixing even, obtain light yellow uncured modified resin.Its curing process is 160 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220 DEG C/2h+240 DEG C/2h.
Solution mixes: by cyanate ester resin, epoxy resin, be dissolved in acetone and other organic solvent containing the resol of phenylate, be made into certain density solution.Its curing process is 160 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220 DEG C/2h+240 DEG C/2h.
Modified heat convertible resin of the present invention is faint yellow light-transmitting solid resin, has good dielectric properties, resistance toheat and mechanical property.Uncured resin be dissolved in acetone and be prepared into certain density glue, can be used for impregnating reinforcing fiber and prepare matrix material.The present invention can be widely used in high performance print circuit card, transparent structure material and high tenacity structure material.
The invention has the advantages that: the introducing of novel phenolic resins, achieve the co-curing behavior of cyanate, resol, epoxy resin, solve the phenomenon that being separated easily appears in traditional modified cyanic acid ester resin, obtain the thermoset resin material of high comprehensive performance; The introducing of epoxy resin can not only improve impact property and can also reduce costs.Meanwhile, the proportionlity of each component and the molecular weight of resol can be made adjustment according to the application requiring of reality.This resin material has a wide range of applications in high-performance circuit board, transparent structure material and high tenacity structure material etc.
The present invention tests the resistance toheat of co-cured resin, dielectric properties and impact property.
Accompanying drawing explanation
Fig. 1 is the structural formula figure of novolac resin;
Fig. 2 is dielectric properties and the impact property data plot of embodiment 1-9.
Embodiment
Embodiment 1
Take epoxy resin (E51) 100g, containing the resol 200g of phenylate structure, be dissolved in acetone and be mixed with the glue that solid content is 60%, then be brushed on 7628 glass-fiber-fabrics and make prepreg, 100 DEG C of baking ovens are put into after at room temperature hanging 24h, to be evaporated point is less than 1%, take out when degree of mobilization is suitable, stack layer by layer, laminate thickness controls at 2.0mm, pressurizes at 140 DEG C, according to 140 DEG C/2h+160 DEG C/2h+180 DEG C/2h+200 DEG C/2h technique solidification, naturally cooling, as requested cutting desired size.
Embodiment 2
Take bisphenol A cyanate ester 90g, containing the resol 10g of phenylate structure, at 120 DEG C, melting mixing is even, pour in pre-heated mould, vacuum outgas 0.5h, is then cured according to the curing process of 160 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220 DEG C/2h+240 DEG C/2h in vacuum drying oven.
Embodiment 3
Take bisphenol A cyanate ester 70g, containing the resol 30g of phenylate structure, at 120 DEG C, melting mixing is even, pour in pre-heated mould, vacuum outgas 0.5h, is then cured according to the curing process of 160 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220 DEG C/2h+240 DEG C/2h in vacuum drying oven.
Embodiment 4
Take bisphenol A cyanate ester 50g, containing the resol 50g of phenylate structure, at 120 DEG C, melting mixing is even, pour in pre-heated mould, vacuum outgas 0.5h, is then cured according to the curing process of 160 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220 DEG C/2h+240 DEG C/2h in vacuum drying oven.
Embodiment 5
Take bisphenol A cyanate ester 70g, epoxy resin (E51) 100g, containing the resol 30g of phenylate structure, at 120 DEG C, melting mixing is even, pour in pre-heated mould, vacuum outgas 0.5h, is then cured according to the curing process of 160 DEG C/1h+180 DEG C/1h+200 DEG C/1h+220 DEG C/1h+240 DEG C/2h in vacuum drying oven.
Embodiment 6
Take bisphenol A cyanate ester 70g, epoxy resin (E51) 50g, containing the resol 30g of phenylate structure, at 120 DEG C, melting mixing is even, and pour in pre-heated mould, vacuum outgas 0.5h, resin curing process is with example 5.
Embodiment 7
Take bisphenol A cyanate ester 70g, epoxy resin (E51) 66g, containing the resol 30g of phenylate structure, at 120 DEG C, melting mixing is even, and pour in pre-heated mould, vacuum outgas 0.5h, resin curing process is with example 5.
Embodiment 8
Take bisphenol A cyanate ester 50g, epoxy resin (E51) 100g, containing the resol 50g of phenylate structure, at 120 DEG C, melting mixing is even, and pour in pre-heated mould, vacuum outgas 0.5h, resin curing process is with example 5.
Embodiment 9
Take bisphenol A cyanate ester 50g, epoxy resin (E51) 66g, containing the resol 50g of phenylate structure, at 120 DEG C, melting mixing is even, and pour in pre-heated mould, vacuum outgas 0.5h, resin curing process is with example 5.

Claims (10)

1. the novel phenolic resins containing phenylate structure, comprise 2 kinds of synthetic methods: wherein the preparation method of novolac resin is for adopting phenol, in the presence of a lewis acid catalyst, the methoxyalkyl phenyl ether oligopolymer synthesized with the method related in Chinese patent application publication number CN101186564A, obtained by condensation reaction, its weight-average molecular weight is greater than 1000, and free phenol is low; Wherein the novolac resin of above-mentioned preparation dissolves in a solvent by the preparation method of heat-reactive phenolic resin, then formaldehyde and ammoniacal liquor is added, 40min is reacted at 90 DEG C, after reduced vacuum removes water molecules, be the solution of heat-reactive phenolic resin, its heat cured resol weight-average molecular weight is greater than 1000, and free phenol is low.
2. a modified heat convertible resin, it is characterized in that by cyanate, epoxy resin, the novel resol containing phenylate structure 2 kinds or 3 kinds form, the mass percent of its component is:
Cyanate 10 ~ 99%
Epoxy resin 0% ~ 100%
The novel resol (MPF) 10 ~ 100% containing phenylate structure.
3. the novel phenolic resins containing phenylate structure according to claim 1, can alonely also can compositely use.
4. modified cyanic acid ester co-cured resin according to claim 2, it is characterized in that described cyanate ester monomer comprises: in bisphenol A cyanate ester, bis-phenol L-type cyanate, bis-phenol M type cyanate, Novolac Cyanate Eater Resin, alkyl diphenyl ether type cyanate, alkyl xylol type cyanate any one, can be maybe any one in its prepolymer.
5. the preparation method of a modified cyanic acid ester co-cured resin as claimed in claim 2, it is characterized in that adopting melt mixing methods, namely at 100 ~ 140 DEG C, heat cyanate, epoxy resin, make its melting mixing even containing the resol of phenylate, through degassed, solidification treatment, obtains the cyanate ester resin of modification.
6. the preparation method of a modified cyanic acid ester co-cured resin as claimed in claim 2, it is characterized in that adopting solution mixing method, by cyanate ester resin, epoxy resin, be dissolved in acetone and other organic solvent containing the resol of phenylate, be made into certain density solution.
7. the preparation method of the modified cyanic acid ester co-cured resin according to claim 5,6, is characterized in that in melting mixing and solution mixing, and the curing process of modified resin adopts 160 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220 DEG C/2h+240 DEG C/2h.
8. the preparation method of the modified cyanic acid ester co-cured resin according to claim 5,6, is characterized in that this co-cured resin has the advantages such as cost is low, manufacture craft is simple.
9. the preparation method of the modified cyanic acid ester co-cured resin according to claim 5,6, is characterized in that this co-cured resin has the feature such as low-k and low-dielectric loss.
10. the preparation method of the modified cyanic acid ester co-cured resin according to claim 5,6, is characterized in that this co-cured resin has good toughness and higher thermotolerance.
CN201410445263.3A 2014-09-03 2014-09-03 A kind of preparation and its application of low cost low-k thermosetting resin Active CN104212167B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115490993A (en) * 2022-10-28 2022-12-20 西安西电电工材料有限责任公司 Epoxy resin composition, preparation method and epoxy glass cloth laminated board
CN115785359A (en) * 2022-11-23 2023-03-14 聚实(上海)新材料有限公司 Novel modified RF resin emulsion for fiber framework material impregnation liquid RFL and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5264500A (en) * 1991-07-30 1993-11-23 Allied-Signal Inc. APT resins

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5264500A (en) * 1991-07-30 1993-11-23 Allied-Signal Inc. APT resins

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHAO LIN ET AL: "High performance cyanate ester resins/reactive porous polymeric microsphere systems with low-temperature processability", 《COMPOSITES SCIENCE AND TECHNOLOGY》 *
易继涛: "酚醛改性二苯醚衍生物树脂的研制及其应用", 《绝缘材料通讯》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115490993A (en) * 2022-10-28 2022-12-20 西安西电电工材料有限责任公司 Epoxy resin composition, preparation method and epoxy glass cloth laminated board
CN115490993B (en) * 2022-10-28 2024-03-01 西安西电电工材料有限责任公司 Epoxy resin composition, preparation method and epoxy glass cloth laminated board
CN115785359A (en) * 2022-11-23 2023-03-14 聚实(上海)新材料有限公司 Novel modified RF resin emulsion for fiber framework material impregnation liquid RFL and preparation method thereof

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