CN104861652B - Thermosetting resin composition, and prepreg and laminated board made from thermosetting resin composition - Google Patents

Thermosetting resin composition, and prepreg and laminated board made from thermosetting resin composition Download PDF

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Publication number
CN104861652B
CN104861652B CN201510282806.9A CN201510282806A CN104861652B CN 104861652 B CN104861652 B CN 104861652B CN 201510282806 A CN201510282806 A CN 201510282806A CN 104861652 B CN104861652 B CN 104861652B
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compound
allyl compound
allyl
curing accelerator
resin combination
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CN104861652A (en
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季立富
谌香秀
戴善凯
黄荣辉
崔春梅
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Suzhou Shengyi Technology Co Ltd
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Suzhou Shengyi Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/5399—Phosphorus bound to nitrogen
    • 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
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal 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
    • 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
    • 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
    • B32B27/18—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
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/50—Phosphorus bound to carbon only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • 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

Abstract

The invention discloses a thermosetting resin composition. The thermosetting resin composition comprises the following solids by weight: (a) a modified bismaleimide prepolymer, (b) a curing accelerator, (c) a fire retardant, and (d) inorganic fillers. A preparation method of the modified bismaleimide prepolymer comprises the following step: heating bismaleimide and a composite allyl compound in a reaction bottle, wherein the composite allyl compound is composed of a first-class allyl compound and a second-class allyl compound, the first-class allyl compound is selected from one or more of diallyl bisphenol A, diallyl bisphenol S, allyl phenoxy resin and diallyl diphenyl ether, and the second-class allyl compound is selected from one or more of diallyl bisphenol A diglycidyl ether, diallyl bisphenol S diglycidyl ether and diallyl diphenyl ether diglycidyl ether. A laminated board integrates high heat resistance, high toughness, low water absorption, excellent dielectric property and good fire resistance.

Description

A kind of compositions of thermosetting resin and the prepreg made using it and laminate
Technical field
The invention belongs to technical field of electronic materials, is related to a kind of compositions of thermosetting resin and is partly consolidated using what it made Change piece and laminate.
Background technology
With the development in electronic unit multifunction, high performance, high reliability and environmentally friendly direction, it is necessary to improve sheet material Heat resistance, to meet Pb-free coating and the repeatedly harsh processing technology of pressing, the heat resistance of traditional FR-4 materials is far from Can meet and require.
Bimaleimide resin is the compound that a class has double activated end group, can in the presence of heating or catalyst With crosslinking curing, with excellent heat resistance, humidity resistance, dielectric properties, good mechanical property and dimensional stability, therefore It is widely used in Aero-Space, electronic apparatus, friendship as High-performance adhesive, resin matrix for advanced composite materials body, insulated paint etc. In numerous high-technology fields such as logical transport.But because there is monomer solubility difference and solidfied material fragility in bimaleimide resin Big the shortcomings of, when being applied to copper-clad plate field, need to be modified it.
At present, conventional method of modifying is that it is changed using aromatic diamines compound or allylic compound Property, crystalline texture is destroyed by chain extension, improve dissolubility and toughness etc..Aromatic diamines compound is anti-by Michael's addition Should realize being modified BMI, modified product has a certain degree of improvement in terms of dissolubility, toughness；But That aromatic diamine toxicity is larger, modified product can only be dissolved in high bp polar solvent (such as DMF, NMP), at the same its Toughness, caking property aspect still suffer from larger room for promotion.And the modified product of allyl compound toughness, caking property, Dissolubility (being soluble in low boiling point solvent, such as PM, butanone, acetone) has further improvement compared with aromatic diamines compound, It is one of method of current bi-maleimide modified main employing.
At present, conventional allylic compound, such as pi-allyl bisphenol-A, pi-allyl bisphenol S, phenol type pi-allyl phenolic aldehyde, Allyl phenol oxygen, aryl allyl alkylphenol etc., however, the bimaleimide resin being modified with these allyl compounds exists Heat resistance, water absorption rate, dielectric properties, flammability, toughness aspect are often attended to one thing and lose sight of another.
Therefore, the heat resistance, high tenacity, low water absorption, superior dielectric performance and the anti-flammability that collect excellent how to be obtained in one The copper-clad plate material of body, is one of this area technical problem urgently to be resolved hurrily.
The content of the invention
The goal of the invention of the present invention is to provide a kind of compositions of thermosetting resin and the prepreg that makes using it and layer Pressing plate.
To achieve the above object of the invention, the technical solution used in the present invention is：A kind of compositions of thermosetting resin, with solid Weight meter, including：
(a) modified bismaleimide prepolymer：100 parts；
(b) curing accelerator：0～5 part；
(c) fire retardant：0～50 part；
(d) inorganic filler：0～200 part；
The preparation method of the modified bismaleimide prepolymer is as follows：According to mass ratio 100：40～200, take respectively BMI, compound allyl compound in reaction bulb, heating response, you can obtain the modified bismaleimide Prepolymer；Wherein, the compound allyl compound is made up of first kind allyl compound and Equations of The Second Kind allyl compound, And the mass ratio of first kind allyl compound and Equations of The Second Kind allyl compound is 0～99:1～100；
The first kind allyl compound selected from diallyl bisphenol, diallyl bisphenol S, allyl phenoxy resin, One or more in diallyl diphenyl ether；
The Equations of The Second Kind allyl compound contracts selected from diallyl bisphenol diglycidyl ether, diallyl bisphenol S two One or more in water glycerin ether, diallyl diphenyl ether diglycidyl ether.
Above, BMI, compound allyl compound are taken in reaction bulb, 120～160 DEG C is heated to, instead Answer 10～150min, you can obtain the modified bismaleimide prepolymer.
The chemical structural formula of the diallyl bisphenol diglycidyl ether is：
The chemical structural formula of the diallyl bisphenol-S diglycidyl ether is：
The chemical structural formula of the diallyl diphenyl ether diglycidyl ether is：
Epoxy resin, cyanate ester resin, benzoxazine colophony, polyphenylene oxide resin can also be included in above-mentioned resin combination In one or more.
The Equations of The Second Kind allyl compound that the present invention is adopted contains epoxide group, improves modified bismaleimide pre-polymerization The dissolubility and storage stability of thing, the pi-allyl in its structure can be polymerized with the double bond in BMI, draw The epoxide group for entering as active end group occur in further heating autohemagglutination or with formula in other resin Composition copolymerization, Improve the reactivity of resin combination and the crosslink density of solidfied material；Simultaneously as what is formed after epoxide group open loop is big Amount ehter bond, improves the toughness of solidfied material.
In above-mentioned technical proposal, the BMI is selected from 4,4 '-diphenyl methane dimaleimide, 4,4 '-two One kind in phenylate BMI, 4,4 '-hexichol isopropyl BMI, 4,4 '-diphenyl sulphone (DPS) BMI Or it is several.
Preferably, the mass ratio of the first kind allyl compound and Equations of The Second Kind allyl compound is 20～60:40 ～80.
In above-mentioned technical proposal, the fire retardant is bromine-containing compound, phosphorus-containing compound, nitrogen-containing compound or siliceous chemical combination Thing.
The bromine-containing compound can select tribromo phenyl maleimide, tetrabromobisphenol A allyl ether, decabrominated dipheny second Alkane, decabrominated dipheny ether, brominated Polystyrene, brominated polycarbonate, tetrabromobisphenol A, brominated epoxy resin.The phosphorous chemical combination Thing can select DOPO or derivatives thereof, phosphorous epoxy resin, phosphorus containing phenolic resin, phosphazene compound, phosphate compound, contain Phosphorus cyanate, phosphorous BMI.The nitrogen-containing compound can select melamine cyanurate.The siliceous chemical combination Thing can select silsesquioxane (POSS), organic silicone powder.
Preferably, the fire retardant can be from one or more in above-mentioned classes of compounds.
In above-mentioned technical proposal, the inorganic filler is silica, aluminium hydroxide, Bao Mushi, hydrogen selected from inorganic filler One or more in magnesia, talcum, kaolin, aluminum oxide, Firebrake ZB, polytetrafluorethylepowder powder.
The silica can be spherical, crystal type or fusion.
Preferably, inorganic filler is to carry out surface-treated inorganic filler with silane coupler.The silane coupler It is preferred that end group contains double bond or epoxide group.The inorganic filler being surface-treated by above-mentioned coupling agent is added to resin combination When, because the double bond/epoxide group and modified bismaleimide prepolymer of coupling agent have excellent com-patibilising effect so that overall The viscosity of resin combination rises slowly, and dispersiveness of the filler in resin combination preferably, is efficiently solved because viscosity is big The unmanageable problem of reaction between resin Composition, improves the surface smoothness of prepreg.
In above-mentioned technical proposal, the curing accelerator is selected from tertiary amines curing accelerator, imidazoles curing accelerator, mistake One kind or several in oxide-based curing accelerator, transition metal carboxylate's class curing accelerator, organic phosphates curing accelerator Kind.
Tertiary amines curing accelerator, such as triethylamine, tripropyl amine (TPA)；Imidazoles curing accelerator, such as 2-methylimidazole, 2- phenyl Imidazoles, 2-ethyl-4-methylimidazole；Peroxide curing accelerator, such as benzoyl peroxide, cumyl peroxide；Cross Cross carboxylate metal salt curing accelerator, such as zinc naphthenate, zinc octoate, aluminium acetylacetonate；Organic phosphates curing accelerator, such as three Phenyl phosphorus, triphenyl phosphite.
The present invention is claimed a kind of prepreg made using above-mentioned resin combination simultaneously, by above-mentioned resin combination Glue is made in the dissolving of thing solvent, and then reinforcing material is immersed in above-mentioned glue；Will dipping after reinforcing material Jing 100～ 200 DEG C are toasted 1～10 minute, you can obtain the prepreg.
Described solvent selected from acetone, butanone, methylisobutylketone, N, dinethylformamide, N, N- dimethyl acetamide, One or more in EGME, propylene glycol monomethyl ether.Described reinforcing material can be fine using natural fiber, organic synthesis Dimension, organic fabric or inorganic fabric.
The present invention is claimed a kind of laminate made using above-mentioned resin combination simultaneously, at one by above-mentioned The single or double of prepreg is covered with metal forming, or by least 2 by above-mentioned prepreg superposition after, in its one side or It is two-sided to be covered with metal forming, suppress 2～4 hours at a temperature of 0.2～2MPa pressure and 180～250 DEG C, you can obtain the lamination Plate.
The quantity of the prepreg is the laminate thickness according to customer requirement determining, can be with one or more.Institute Metal forming is stated, can be Copper Foil, or aluminium foil, thickness is not particularly limited.
Because above-mentioned technical proposal is used, the present invention has compared with prior art following advantages：
1. the present invention is using the compound pi-allyl being made up of first kind allyl compound and Equations of The Second Kind allyl compound Compound reacts the Bismaleimide prepolymer for obtaining and has higher reaction as the modifying agent of bimaleimide resin Activity, good dissolubility and storage stability, good toughness after solidification, peel strength is high, water absorption rate is low, dielectric constant is low and protects The excellent heat resistance of BMI has been held, it is the excellent heat resistance of the laminate collection for obtaining, high tenacity, low water absorption, excellent Dielectric properties and anti-flammability can meet the requirement of high-precision electronic baseplate material in one；With energetically realistic meaning；
2. experiment is proved：Prepreg and laminate good toughness that the present invention is obtained, peel strength is high, water absorption rate is low, Jie Electric constant is low and keeps the original excellent heat resistance of BMI, achieves significant effect；Can be applicable to high temperature resistant to resist The fields such as aging, integrated antenna package, high-speed high frequency, have broad application prospects.
Specific embodiment
The present invention is further described with reference to embodiment.
Embodiment one：
Take 4,4 '-diphenyl methane dimaleimide 100g, diallyl bisphenol diglycidyl ether 70g (epoxide equivalents In 256g/eq) being put into 500mL reaction bulbs, it is slowly heated to 155 DEG C using oil bath and reacts 30min under the conditions of being kept stirring for, instead Room temperature is cooled to after the completion of answering, modified bismaleimide prepolymer is obtained.
Proper amount of acetone dissolving is added, the glue for obtaining 62% solids content is uniformly mixed, impregnates above-mentioned with E glass-fiber-fabrics Glue, and the prepared prepregs of 5min are dried in 160 DEG C of baking ovens.
By the above-mentioned semi-solid preparation superposition of 8 sanction burr removings, 35 microns of Copper Foil is enclosed up and down, be placed in vacuum hotpressing machine and press Copper-clad plate is obtained.Specific process for pressing is, in 1.5Mpa pressure, to press 4 hours at a temperature of 220 DEG C.The copper clad layers pressure of acquisition Plate performance is as shown in table 1.
Embodiment two：
Take 4,4 '-Diphenyl Ether Bismaleimide 30g, 4,4 '-diphenyl methane dimaleimide 70g, diallyl is double During phenol A 50g, diallyl bisphenol diglycidyl ether 50g (epoxide equivalent 220g/eq) are put into 500mL reaction bulbs, using oil Bath is slowly heated to 140 DEG C and reacts 50min under the conditions of being kept stirring for, and room temperature is cooled to after the completion of reaction, obtains modified span Carry out imide prepolymer.
Proper amount of acetone dissolving is added, the glue for obtaining 62% solids content is uniformly mixed.
Prepreg, copper clad laminate preparation method are with embodiment one.
The copper clad laminate performance of acquisition is as shown in table 1.
Embodiment three：
4 are taken, 4 '-Diphenyl Ether Bismaleimide 100g, allyl phenoxy resin 40g, diallyl bisphenol S two shrinks sweet During oily ether 50g (epoxide equivalent 215g/eq) is put into 500mL reaction bulbs, it is slowly heated to 140 DEG C using oil bath and is kept stirring for bar 60min is reacted under part, room temperature is cooled to after the completion of reaction, obtain modified bismaleimide prepolymer.
Add proper amount of acetone dissolving, add after dissolving completely 23 parts of ring-type phenoxy phosphazene compounds (FP-100, Fushimi Pharmaceutical Co., Ltd), it is uniformly mixed the glue for obtaining 62% solids content.
Prepreg, copper clad laminate preparation method are with embodiment one.
The copper clad laminate performance of acquisition is as shown in table 1.
Example IV：
4 are taken, 4 '-hexichol isopropyl BMI 100g, diallyl bisphenol 30g, diallyl bisphenol two contracts During water glycerin ether 30g (epoxide equivalent 250g/eq) is put into 500mL reaction bulbs, it is slowly heated to 140 DEG C using oil bath and keeps stirring 45min is reacted under the conditions of mixing, room temperature is cooled to after the completion of reaction, obtain modified bismaleimide prepolymer.
Addition proper amount of acetone dissolving, 20 parts of polyfunctional epoxy resins (502H, Japanese chemical drug) of addition after dissolving completely, 0.2 Part triphenyl phosphorus, are uniformly mixed the glue for obtaining 62% solids content.
Prepreg, copper clad laminate preparation method are with embodiment one.
The copper clad laminate performance of acquisition is as shown in table 1.
Embodiment five：
4 are taken, 4 '-diphenyl sulphone (DPS) BMI 100g, diallyl bisphenol S 40g, diallyl diphenyl ether two shrinks During glycerin ether 70g (epoxide equivalent 225g/eq) is put into 500mL reaction bulbs, it is slowly heated to 150 DEG C using oil bath and is kept stirring for Under the conditions of react 30min, room temperature is cooled to after the completion of reaction, obtain modified bismaleimide prepolymer.
Proper amount of acetone dissolving is added, 100 parts of preparing spherical SiO 2s are added after dissolving completely, be uniformly mixed and obtain 62% The glue of solids content.
Prepreg, copper clad laminate preparation method are with embodiment one.
The copper clad laminate performance of acquisition is as shown in table 1.
Comparative example one：
4 are taken, 4 '-diphenyl methane dimaleimide resin 100g, diallyl bisphenol 100g are put into 500mL reactions In bottle, it is slowly heated to 140 DEG C using oil bath and reacts 50min under the conditions of being kept stirring for, room temperature is cooled to after the completion of reaction, obtains To modified bismaleimide prepolymer.Proper amount of acetone dissolving is added, the glue for obtaining 62% solids content is uniformly mixed.
Prepreg, copper clad laminate preparation method are with embodiment one.The copper clad laminate performance of acquisition is as shown in table 1.
Comparative example two：
4 are taken, 4 '-diphenyl methane dimaleimide resin 100g, pi-allyl novolac glycidyl ethers 100g are put into In 500mL reaction bulbs, it is slowly heated to 140 DEG C using oil bath and reacts 50min under the conditions of being kept stirring for, cools down after the completion of reaction To room temperature, modified bismaleimide prepolymer is obtained.
Proper amount of acetone dissolving is added, the glue for obtaining 62% solids content is uniformly mixed.
Prepreg, copper clad laminate preparation method are with embodiment one.The copper clad laminate performance of acquisition is as shown in table 1.
Table 1 is using the laminate properties obtained by different embodiments and comparative example
Partial test method of the present invention is specific as follows：
Measurement thickness of sample is 1.6mm, is 8 7628 glass-fiber-fabrics with this structure.
Humidity resistance：Using pressure cooker gluten substitute, sheet material is through 121 DEG C of continuously cookings 180 of pressure cooker (0.105MPA) After minute, observation layering, cream time in 288 DEG C of scolding tin of immersion；
Impact flexibility：Using 5512 Apparatus for Impacting at low-temp, Apparatus for Impacting at low-temp height of the fall 45cm, whereabouts weight weight 1kg.If sheet material impacts Cross pattern afterwards is clear and elongated, illustrates that the toughness of sheet material is better；Conversely, cross pattern is obscured or without cross pattern, illustrates sheet material Poor toughness, fragility is big, be specifically divided into it is excellent, good, in, differ from four grades.
From table 1 it follows that compared with comparative example one (individually using diallyl bisphenol), the obtained plate of the present invention Material has good toughness, Tg after solidification high, peel strength height and the low advantage of water absorption rate.
Compared with documents two (individually adopting pi-allyl novolac glycidyl ethers), the obtained sheet material of the present invention has solid Good toughness, water absorption rate be low after change and the low advantage of dielectric constant.Mainly caused by two aspects with the difference of documents two：It is first First, because the rigid radical density in phenolic resin main framing structure is larger and without rotatable group, causes its solidfied material toughness It is poor；On the other hand, pi-allyl phenolic aldehyde during etherificate due to steric effect, the hydroxyl in the middle of molecule not completely etherificate and Reaction is difficult, causes remaining hydroxyl groups in solidfied material, and hydroxyl belongs to polar group, easily causes solidfied material water absorption rate greatly and dielectric is normal Number is higher.
In sum, the obtained copper-clad plate collection of the present invention excellent heat resistance, high tenacity, low water absorption, superior dielectric The fields such as anti-aging high temperature resistant, integrated antenna package, high-speed high frequency can be can be applicable to anti-flammability in one.
Above example, not imposes any restrictions to the content of the composition of the present invention, every technology according to the present invention Any trickle amendment, equivalent variations and modification that essence or composition composition or content are made to above example, still fall within In the range of technical solution of the present invention.

Claims (7)

1. a kind of compositions of thermosetting resin, it is characterised in that with solid weight meter, including：
(a) modified bismaleimide prepolymer：100 parts；
(b) curing accelerator：0 ~ 5 part；
(c) fire retardant：0 ~ 50 part；
(d) inorganic filler：0 ~ 200 part；
The preparation method of the modified bismaleimide prepolymer is as follows：According to mass ratio 100：40 ~ 200, span is taken respectively Come acid imide, compound allyl compound in reaction bulb, heating response, you can obtain the modified bismaleimide pre-polymerization Thing；
Wherein, the compound allyl compound is made up of first kind allyl compound and Equations of The Second Kind allyl compound, and The mass ratio of first kind allyl compound and Equations of The Second Kind allyl compound is 20 ~ 60:40~80；
The first kind allyl compound is selected from diallyl bisphenol, diallyl bisphenol S, allyl phenoxy resin, diene One or more in propyl group diphenyl ether；
The Equations of The Second Kind allyl compound shrinks sweet selected from diallyl bisphenol diglycidyl ether, diallyl bisphenol S two One or more in oily ether, diallyl diphenyl ether diglycidyl ether.
2. resin combination according to claim 1, it is characterised in that：The BMI is selected from 4,4 '-hexichol Methane BMI, 4,4 '-Diphenyl Ether Bismaleimide, 4,4 '-hexichol isopropyl BMI, 4,4 '-two One or more in benzene sulfone BMI.
3. resin combination according to claim 1, it is characterised in that：The fire retardant be bromine-containing compound, containing phosphatization Compound, nitrogen-containing compound or silicon-containing compound.
4. resin combination according to claim 1, it is characterised in that：The inorganic filler is dioxy selected from inorganic filler In SiClx, aluminium hydroxide, Bao Mushi, magnesium hydroxide, talcum, kaolin, aluminum oxide, Firebrake ZB, polytetrafluorethylepowder powder one Plant or several.
5. resin combination according to claim 1, it is characterised in that：The curing accelerator promotees selected from tertiary amines solidification Enter agent, imidazoles curing accelerator, peroxide curing accelerator, transition metal carboxylate's class curing accelerator, organophosphor One or more in class curing accelerator.
6. it is a kind of using resin combination as claimed in claim 1 make prepreg, it is characterised in that：By claim Glue is made in resin combination solvent dissolving described in 1, and then reinforcing material is immersed in above-mentioned glue；To increase after dipping Strong 100 ~ 200 DEG C of material Jing is toasted 1 ~ 10 minute, you can obtain the prepreg.
7. it is a kind of using resin combination as claimed in claim 1 make laminate, it is characterised in that：At one by right The single or double for requiring the prepreg described in 6 is covered with metal forming, or solid by half described in claim 6 by least 2 After changing piece superposition, metal forming is covered with its single or double, compacting 2 ~ 4 is little at a temperature of 0.2 ~ 2MPa pressure and 180 ~ 250 DEG C When, you can obtain the laminate.
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CN106243430B (en) * 2016-08-29 2018-04-06 苏州生益科技有限公司 A kind of compositions of thermosetting resin and the prepreg and laminate using its making
JP6723934B2 (en) * 2017-01-25 2020-07-15 信越化学工業株式会社 Silicone composition, release paper and release film
CN109306040A (en) * 2017-07-26 2019-02-05 广东生益科技股份有限公司 A kind of compositions of thermosetting resin, prepreg, metal-clad laminate and the high-frequency circuit board made by it
CN109306044A (en) * 2017-07-26 2019-02-05 郑州大学 A kind of intrinsic flame-retarded resin of low polarity and its preparation method and application
CN108384236A (en) * 2018-03-16 2018-08-10 苏州生益科技有限公司 A kind of resin combination and the low flow prepreg using its preparation
CN109929109A (en) * 2019-03-19 2019-06-25 武汉理工大学 A kind of high tenacity high-low temperature resistant Bismaleimides resin pre-polymer and preparation method thereof
CN110643321B (en) * 2019-09-24 2022-03-29 苏州益可泰电子材料有限公司 Electronic material glue solution and application thereof
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