CN106393885B - A kind of fire-retardant copper-clad plate composition containing soft-filler - Google Patents

A kind of fire-retardant copper-clad plate composition containing soft-filler Download PDF

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CN106393885B
CN106393885B CN201610552893.XA CN201610552893A CN106393885B CN 106393885 B CN106393885 B CN 106393885B CN 201610552893 A CN201610552893 A CN 201610552893A CN 106393885 B CN106393885 B CN 106393885B
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fire
structural formula
filler
clad plate
plate composition
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CN106393885A (en
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邓娇容
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Shenzhen Jinhaohui Industrial Development Co., Ltd.
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Shenzhen Jin Hao Hui Mining Development Co Ltd
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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
    • 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
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/045—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • 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
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/308—Heat stability
    • 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
    • B32B2307/536—Hardness
    • 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
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • B32B2307/7145—Rot proof, resistant to bacteria, mildew, mould, fungi
    • 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
    • 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
    • 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
    • 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)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a kind of fire-retardant copper-clad plate composition containing soft-filler, meter in parts by weight includes：Fire retarding epoxide resin addition is 60~90 parts；Soft compounded mix addition is 10~40 parts；Curing agent addition is the 0.5~5% of fire retarding epoxide resin amount；Accelerator addition is the 0.05~1% of fire retarding epoxide resin amount；Amount of solvent is the 30~60% of formula solid amount.The fire retarding epoxide resin includes phosphorous epoxy resin, brominated epoxy resin or the mixture with without phosphorus brominated eopxy resin in any proportion；The chemical composition of soft compounded mix is the powder of element silicon, magnesium elements, aluminium element, antimony element, the eutectic of the oxide of barium element and sulfate, eutectic or mixture.Raw material resources are abundant, cheap, and its growth to multiple-microorganism and mushroom has significant inhibitory action；Mohs' hardness is low, can reduce the abrasion to process equipment, significantly reduce cost.

Description

A kind of fire-retardant copper-clad plate composition containing soft-filler
Technical field
The invention belongs to printed substrate (PCB) design and manufacturing field, more particularly to a kind of making containing soft-filler Fire-retardant copper-clad plate composition.
Background technology
In the late five decades, the lead of solder, soldering paste etc and its alloy etc. electronics PCB plating, HASL, welding and The manufacture fields such as assembling are widely used.If these leaded electronic products are in manufacture, processing, accumulating and waste procedures In it is mishandling, lead and its lead ion will be infiltrated through in soil and water source, polluted and by foods such as fish, shrimp, vegetables The materials such as chain, breathing, drinking-water circulation approach enters human body.Lead can accumulate in blood of human body, can cause when reaching finite concentration Poisoning, it is even dull-witted to show as hyperactivity, absent minded, hypophrenia；Digestive system can cause poor appetite, stomachache, Diarrhoea or constipation etc.；Hemopoietic system shows as anaemia, zinc-deficiency；Hypoevolutism etc. can be caused to child.So as to 90 years 20th century In generation, causes the great attention of scientist and national governments.
2 months 2003 No. 13, European Union has promulgated that RoHS and WEEE two are instructed greatly, it is desirable to " new to launch from 1 day July in 2006 Electrical and electronic product to European market must not contain：Lead, mercury, cadmium, Cr VI, PBBs (PBB) and PBDEs (PBDE) 6 kinds of noxious materials such as ".And as world's factory and the China of world's PCB yield first, inherently follow European step closely Cut down, realize unleaded.
In printed substrate (PCB) manufacturing, for the popularization of adapted to leadless solder, the heat-resisting of copper-clad plate must be accordingly improved Property, the coefficient of expansion that reduces, early stage, the way of industry was typically in resin substrate formula to add SiO2、Al2O3、Al(OH)3、 Mg(OH)2Deng mineral filler or inorganic filler, but above filler has a common feature, and Mohs' hardness is higher.Industry is accustomed to Hardness is divided into three sections by property：Mohs' hardness 10-8 is high rigidity, Mohs' hardness 7-4 is middle hardness, and Mohs' hardness is low hard below 3 Spend (flexible material), the copper-clad plate containing middle high Mohs' hardness filler is in Drilling operation and gong profile to brill nozzle and the mill of gong knife Damage is very big, and shared cost ratio is higher.
Therefore, it is the development trend of adapted to leadless solder, the copper-clad plate and prepreg for developing flexible material turn into industry One inevitable choice on boundary, develop soft-filler and it is carried out the problem of physics and chemical modification can not only improve abrasion, Cost can be reduced, moreover it is possible to improve the thermal coefficient of expansion of copper-clad plate, bending strength, dimensional stability etc., therefore promise well.
The content of the invention
The defects of it is an object of the invention to overcome prior art printed substrate (PCB) high rigidity, to reduce to boring nozzle And the abrasion of gong knife, so as to reduce processing cost, increase economic efficiency, there is provided the one kind for meeting environmental requirement contains soft-filler system The fire-retardant copper-clad plate composition made, in order to solve the above technical problems, the present invention provides following technical scheme：
A kind of fire-retardant copper-clad plate composition containing soft-filler, counting its first layer proportioning in parts by weight includes：
Fire retarding epoxide resin, addition are 60~90 parts；
Soft compounded mix, addition are 10~40 parts；
Curing agent, addition are the 0.5~5% of fire retarding epoxide resin amount；
Accelerator, addition are the 0.05~1% of fire retarding epoxide resin amount；
Solvent, addition are the 30~60% of formula solid amount.
The fire retarding epoxide resin includes phosphorous epoxy resin, brominated epoxy resin or with without phosphorus brominated eopxy resin by any The mixture of ratio.
The phosphorous epoxy resin is the appointing to structural formula (3) of the structural formula (1) with following A types side chain or Type B side chain What a kind of or structural formula (1) arbitrary proportion into structural formula (3) mixture：
(n=1-1000, the present invention are hereafter herewith worth scope) (1)
Or
Or
The brominated epoxy resin has any one or structural formula (4) and structural formula of structural formula (4) and structural formula (5) (5) mixture of arbitrary proportion in：
The without phosphorus brominated eopxy resin has structural formula (6) to any one of structural formula (14) structure or structural formula (6) to structural formula (14) arbitrary proportion mixture：
A kind of fire-retardant copper-clad plate composition containing soft-filler, the soft compounded mix match for the second layer, including but It is not limited to eutectic, eutectic or the mixing of element silicon, magnesium elements, aluminium element, antimony element, the oxide of barium element and sulfate The powder of body, is counted in parts by weight：
Aluminium element, with Al2O3Meter content is 26%-82% or more preferably 55%-80%；
Barium element, content is counted as 4-47% or more preferably 10%-30% using BaO；
Magnesium elements, content is counted as 12%-81% or more preferably 50%-80% using MgO；
Antimony element, with Sb2O3Meter content is 7-75% or more preferably 20%-50%；
Element silicon, with SiO2Meter content is 17%-73% or more preferably 40%-70%；
Sulfate, with SO4 -2Meter content is 3-29% or more preferably 5%-14%.
The characteristic of the powder shows as average grain diameter D50Less than 8 microns and D97It is more than less than 24 microns, Heng Shi whiteness 85th, Mohs' hardness is less than DDGS in 2.3, water and is less than 0.10%, pH value 6-9, light transmittance more than 88, moisture less than 1%.
The curing agent includes dicyandiamide, 4,4 MDAs (DDM), 4, the 4 diaminourea hexichol of structural formula (15) Any one of the aromatic series diphenylamines such as ether (DDE), 4,4 diaminodiphenylsulfones (DDS) or the mixture of arbitrary proportion.
The accelerator includes 2-methylimidazole, 2-ethyl-4-methylimidazole, N- methylimidazoles, 2- phenylimidazoles, three It is fluorinated boron amide mono aminoethane, any one of boric acid or the mixture of arbitrary proportion.
The solvent includes dimethylformamide, acetone, butanone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetic acid Fat, any one of ethylene glycol monomethyl ether or the mixture of arbitrary proportion.
A kind of fire-retardant copper-clad plate composition containing soft-filler, wherein the preparation method bag containing soft compounded mix glue Include three steps：
The first step, matched by first layer and epoxy resin, curing agent, curing accelerator and organic solvent are stirred, it is raw Produce the epoxy resin adhesive liquid that can solidify under 40 DEG C of -110 DEG C of high temperature；
Second step, second layer proportioning is then pressed under high shear dispersion admixture and adds soft compounded mix.
3rd step, take the techniques such as impregnation technology or lamination to glue glass cloth with this kind of glue, prepare double-sided copper-clad Plate.
Compared with prior art, the present invention has the advantages that：
Main chemical composition is element silicon, magnesium elements, aluminium element, antimony element, the oxide of barium element and sulfate The powder of eutectic, eutectic or mixture, raw material resources are abundant, cheap, have special layer structure, exist in layer strong Strong covalent bond effect, interlayer have between electrostatic attraction and laminate and interlayer anion that electrostatic attraction, hydrogen bond etc. to be present non-common Valence link weak interaction, therefore there is certain heat endurance；Its growth to multiple-microorganism and mushroom has significant suppression Effect；Mohs' hardness is low, can reduce the abrasion to process equipment, significantly reduce processing cost.
Brief description of the drawings
Fig. 1 is that 2-1 of the embodiment of the present invention bores nozzle wear results photo；
Fig. 2 is that 2-2 of the embodiment of the present invention bores nozzle wear results photo；
Fig. 3 is that 2-2 of the embodiment of the present invention bores nozzle wear results photo；
Fig. 4 is that 3-1 of the embodiment of the present invention bores nozzle wear results photo；
Fig. 5 is that 3-2 of the embodiment of the present invention bores nozzle wear results photo；
Fig. 6 is that 3-3 of the embodiment of the present invention bores nozzle wear results photo.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention It is further elaborated.It should be appreciated that specific embodiment described herein is not intended to limit only to explain the present invention The fixed present invention.
First group of embodiment (1.1-1.12)
The chemistry of the soft compounded mix of embodiment 1.1-1.12 acquisitions by weight percentage is summarized in the following table 1 Composition proportion and hardness.
Second group of embodiment (2.1-2.3)
Summarize in table 2 below embodiment 2.1-2.3 acquisition with printed substrate made from soft compounded mix (PCB) glue formula：
Soft compounded mix：Weight is respectively accounted for using the soft compounded mix obtained by first group of embodiment (1.1 and 1.7) 50% mixes.
Fire retarding epoxide resin：Epoxide equivalent is 268g/Eq.
Curing agent：Dicyandiamide (DICY, purity>99.5%).
Accelerator：2-methylimidazole (2-MI, purity>99.0%).
Solvent：Acetone, one kind in dimethylformamide (DMF) or two kinds.
The proportioning of above-mentioned substance is shown in Table listed by 2.
Preparation method containing soft compounded mix glue, including three steps：
The first step, it is formulated by table 2 and epoxy resin, curing agent, curing accelerator and organic solvent is stirred, production can The epoxy resin adhesive liquid solidified under 60 DEG C of -100 DEG C of high temperature；
Second step, soft compounded mix is then added under high shear dispersion admixture.
3rd step, glued with this kind of glue by glass cloth, the technique such as lamination, prepare double face copper.Copper-clad plate is surveyed Test result is shown in Table 4.
Comparative example (3.1~3.3)
According to the method for second group of embodiment (2.1-2.3), using the formula shown in table 3 prepare aluminum oxide, aluminium hydroxide, Silicon powder fills epoxy resin adhesive liquid composite.Wherein, alumina particle is about 0.8 μm, volume density 3.9g/cm3.Hydrogen Aluminum oxide footpath is about 1.8 μm, volume density 2.4g/cm3；Silicon powder average grain diameter is 6.5 μm.Specific surface area>0.65m2/g, Loose thickness is 0.75g/cm3, purity>99.5%.
Glued with this kind of glue by glass cloth, the technique such as lamination, prepare double face copper.Copper-clad plate test result is shown in Table 5.
Method of testing：
(1) glass transition temperature (Tg), method of testing use differential scanning calorimetry (DSC).
(2) thermally stratified layer time (T-288), method of testing use thermomechanical analysis (TMA).
(3) thermal coefficient of expansion (CTE), method of testing use thermomechanical analysis (TMA).
(4) flammability, by U.S. UL94 standard vertical combustion methods.
(5) 3000 holes are bored, nozzle wear results is bored and sees Fig. 1 to Fig. 6.
The above described is only a preferred embodiment of the present invention, any formal limitation not is made to the present invention, it is all It is any simple modification, equivalent change and modification made according to the technical spirit of the present invention to above example, still falls within In the range of technical solution of the present invention.
The first group of embodiment and second group of embodiment of the present invention has the advantages that and is：
Main chemical composition is element silicon, magnesium elements, aluminium element, antimony element, the oxide of barium element and sulfate The powder of eutectic, eutectic or mixture, raw material resources are abundant, cheap, have special layer structure, exist in layer strong Strong covalent bond effect, interlayer have between electrostatic attraction and laminate and interlayer anion that electrostatic attraction, hydrogen bond etc. to be present non-common Valence link weak interaction, therefore there is certain heat endurance；With special chemical composition, it is to multiple-microorganism and mushroom Growth have significant inhibitory action；Mohs' hardness is low, can reduce the abrasion to process equipment, significantly reduce processing cost.
1 soft compounded mix of table (chemical composition proportioning and hardness by weight percentage)
1 soft compounded mix of (Continued) table (chemical composition proportioning and hardness by weight percentage)
The glue formula of 2 soft compounded mix of table filling
The formula for the glue that the aluminum oxide of table 3, aluminium hydroxide, silicon powder are filled
The embodiment copper-clad plate test result of table 4
The comparative example copper-clad plate test result of table 5

Claims (8)

  1. A kind of 1. fire-retardant copper-clad plate composition containing soft-filler, it is characterised in that：Meter includes in parts by weight：
    Fire retarding epoxide resin, addition are 60~90 parts；
    Soft compounded mix, addition are 10~40 parts；
    Curing agent, addition are the 0.5~5% of fire retarding epoxide resin amount；
    Accelerator, addition are the 0.05~1% of fire retarding epoxide resin amount；
    Solvent, addition are the 30~60% of formula solid amount；
    Wherein, according to weight, the soft compounded mix is by 50% the first mixed fillers and the second of 50% Mixed fillers form, according to weight, first mixed fillers by 11.7% BaO, 81% MgO and 7.3% SO4 2-Composition, according to weight, second mixed fillers by 78.3% MgO and 21.7% Sb2O3Composition.
  2. 2. the fire-retardant copper-clad plate composition according to claim 1 containing soft-filler, it is characterised in that：The flame retardant epoxy Resin includes phosphorous epoxy resin, brominated epoxy resin or the mixture with without phosphorus brominated eopxy resin in any proportion.
  3. 3. the fire-retardant copper-clad plate composition according to claim 1 containing soft-filler, it is characterised in that：The curing agent bag Include the dicyandiamide, 4,4 MDAs, 4,4 diaminodiphenyl ethers and 4 of structural formula (15), appointing in 4 diaminodiphenylsulfones What a kind of or arbitrary proportion mixture.
  4. 4. the fire-retardant copper-clad plate composition according to claim 1 containing soft-filler, it is characterised in that：The accelerator bag Include 2-methylimidazole, 2-ethyl-4-methylimidazole, N- methylimidazoles, 2- phenylimidazoles, borontrifluoride boron amide mono aminoethane, boric acid Any or arbitrary proportion mixture.
  5. 5. the fire-retardant copper-clad plate composition according to claim 1 containing soft-filler, it is characterised in that：The solvent includes Dimethylformamide, acetone, butanone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether amyl acetate, any the one of ethylene glycol monomethyl ether The mixture of kind or arbitrary proportion.
  6. 6. the fire-retardant copper-clad plate composition according to claim 2 containing soft-filler, it is characterised in that：The phosphorous epoxy Resin is that any one or structural formula (1) of the structural formula (1) with following A types side chain or Type B side chain to structural formula (3) are extremely tied The mixture of arbitrary proportion in structure formula (3)：
    (n=1-1000, the present invention are hereafter herewith worth scope) (1)
    Or
    Or
  7. 7. the fire-retardant copper-clad plate composition according to claim 2 containing soft-filler, it is characterised in that：It is described to contain brominated eopxy Resin has any one of structural formula (4) and structural formula (5) or the mixing of arbitrary proportion in structural formula (4) and structural formula (5) Thing：
  8. 8. the fire-retardant copper-clad plate composition according to claim 2 containing soft-filler, it is characterised in that：The without phosphorus bromine ring Oxygen tree fat has structural formula (6) any to any one of structural formula (14) structure or structural formula (6) to structural formula (14) The mixture of ratio：
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CN111499193B (en) * 2020-04-20 2022-08-26 王新宇 Soft silicon composite filler for copper-clad plate and preparation method thereof
CN112625632A (en) * 2020-11-27 2021-04-09 江西省宏瑞兴科技股份有限公司 Epoxy resin adhesive with high phase ratio electric leakage tracking index and preparation method thereof

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