CN109306040A - A kind of compositions of thermosetting resin, prepreg, metal-clad laminate and the high-frequency circuit board made by it - Google Patents

A kind of compositions of thermosetting resin, prepreg, metal-clad laminate and the high-frequency circuit board made by it Download PDF

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Publication number
CN109306040A
CN109306040A CN201710617174.6A CN201710617174A CN109306040A CN 109306040 A CN109306040 A CN 109306040A CN 201710617174 A CN201710617174 A CN 201710617174A CN 109306040 A CN109306040 A CN 109306040A
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China
Prior art keywords
resin
phosphorous
allyl
phenolic
combination
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CN201710617174.6A
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Chinese (zh)
Inventor
苏民社
杨中强
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Shengyi Technology Co Ltd
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Shengyi Technology Co Ltd
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Application filed by Shengyi Technology Co Ltd filed Critical Shengyi Technology Co Ltd
Priority to CN201710617174.6A priority Critical patent/CN109306040A/en
Priority to PCT/CN2017/109049 priority patent/WO2019019463A1/en
Priority to TW106140388A priority patent/TWI658046B/en
Publication of CN109306040A publication Critical patent/CN109306040A/en
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • 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
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/02—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments
    • B32B17/04—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments bonded with 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
    • 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
    • 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
    • B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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    • 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
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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    • 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
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    • 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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    • B32B5/22—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
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    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/6574—Esters of oxyacids of phosphorus
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • 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
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    • 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
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • 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
    • C08L61/14—Modified phenol-aldehyde condensates
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    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
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    • B32B2260/04—Impregnation, embedding, or binder material
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    • C08L2203/20—Applications use in electrical or conductive gadgets
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Abstract

Prepreg, metal-clad laminate and the high-frequency circuit board that the present invention provides a kind of compositions of thermosetting resin, made by it, the compositions of thermosetting resin include low polarity allylation resin and phosphorous-containing monomers or phosphorous resin.The copper-clad plate and high-frequency circuit board that the present invention is prepared have low-k and dielectric loss, good heat resistance and flame retardant property.

Description

A kind of compositions of thermosetting resin is laminated by prepreg, the clad with metal foil of its production Plate and high-frequency circuit board
Technical field
The invention belongs to technical field of copper clad laminate, be related to a kind of compositions of thermosetting resin, by its production prepreg, Metal-clad laminate and high-frequency circuit board.
Background technique
In recent years, with information communication device high performance, multifunction and the development of networking, in order to transmit and locate Large capacity information is managed, operation signal is intended to high frequency, thus proposes requirement to the material of circuit substrate.
In the existing material for tellite, the excellent epoxy resin of adhesion properties is widely used, however, ring The general dielectric constant of oxygen resin circuit substrate and dielectric loss angle tangent it is higher (dielectric constant be greater than 4, dielectric loss angle tangent 0.02 or so), high frequency characteristics is insufficient, does not adapt to the requirement of signal high frequency.Therefore it is excellent dielectric property must to be developed The low resin of resin, i.e. dielectric constant and dielectric loss angle tangent.
The another kind of thermoplastic fluoroelastomer resinoid (polytetrafluoroethylene (PTFE)) as baseplate material, although dielectric constant and dielectric loss Angle tangent is lower, but the general melting temperature of fluorine resin and melt viscosity are high, and because of its poor mobile performance, it is big to form difficulty.And When making multilayer circuit board, there is the problems such as caking property of processability, dimensional stability and metal coating is insufficient.
Then instead of fluorine resin, the resin material used for printed circuit board for being suitble to high-frequency high-speed purposes is studied.Wherein, resistance to It is attracted attention in thermal conductivity polymeric with the use of the excellent polyphenylene oxide resin of dielectric property.But polyphenylene oxide is similarly melting temperature The high thermoplastic resin with melt viscosity also has many challenges in the application, such as meets electronic building brick because of the presence of these problems It is (such as heat resistance, resistance to be difficult to reach all electrical properties, anti-flammability and mechanical performance while required low dielectric loss angle tangent Chemically, agent of low hygroscopicity etc.).In addition machinability is poor in the fabrication process, will cause scrappage increase, less reliable.
To obtain the circuit board for meeting hyundai electronics Information Technology Development needs, those skilled in the art has been carried out largely Research work, be optimal with expectation in various performances, reliability, the manufacture various aspects such as processability, but effect is undesirable.
In addition, tellite material used in electronic and electrical equipment, it is desirable that reach 94V-0 grades of flame retardant rating, this It is no exception to high-frequency high-speed circuit board material.High-frequency high-speed circuit board generallys use the halogen class material based on bromine and does at present Fire retardant.Although halogen class material flame retardant effect is preferable, some researches show that halogen class material easily discharges irritation in burning With virose gas, such as hydrogen halides, dioxin, it is compromised human health.In some electronic products, there is taboo Only use the circuit board material of halogen class.In recent years, with the raising of people's environmental protection ideas, electronics material used in electronic apparatus Material is intended to non-halogen, all meets fire-retardant requirement in other type fire retardants for seeking can to substitute halogen based flame retardant. It needs to add because its flame retarding efficiency is poor although toxicity problem as halogen containing flame-retardant is not present in metal hydroxide combustion inhibitor Add bigger amount to obtain good flame retardant property, this will lead to poor fluidity when resin mixing, molding, make composite material Processing and mechanical degradation；Big additionally, due to the dielectric constant of metal hydroxides, high-frequency electrical can be brought by making fire retardant with it The decline of base board dielectric properties.Phosphonium flame retardant mostly has the characteristics that low cigarette, nontoxic, not only has good anti-flammability Can, and it is able to suppress the release of smog and toxic gas, compound additive amount is few, the apparent application requirement of flame retardant effect.
CN 103709718A discloses a kind of production method of halogen-less high frequency board substrate, and polyphenylene oxide is used to decide Resin, alkyl-blocked diallyl bisphenol make curing agent, and using the brominated or phosphonium flame retardant of addition type.Wherein use The phosphonium flame retardant of addition type carries out the production of high-frequency copper-clad plate as fire proofing, but revealed several phosphonium flame retardants do not have There is reactive group, be not involved in the intermolecular crosslinking of composite resin, (is less than because the fusing point of these types of phosphonium flame retardant is very low 200 DEG C), with the poor heat resistance of the high-frequency circuit board material of its production, it is high that it is not able to satisfy subsequent conditioning circuit panel element assembling process The requirement of warm soldering reliability.
CN106543228A discloses the resin having the following structure:
However if such resin to be applied to the preparation of copper-clad plate, Then due to that the dielectric properties for the copper-clad plate being prepared can be prevented from meeting the requirements containing hydroxyl polar group in its structure.
CN106366128 discloses a kind of phosphine phenanthrene class compound having the following structure:
It, can be due to however if the compound to be used for the preparation of copper-clad plate Allyl ether structure present in its structure and rearrangement reaction occurs in process, cause to generate secondary hydroxyl polar group Group, can equally prevent the dielectric properties for the copper-clad plate being prepared from meeting the requirements.
Therefore, this field wherein, it is expected that developing one kind can either guarantee there is good flame retardant property, and can be situated between The compositions of thermosetting resin of many aspects such as electrical property, heat resistance acquirement good result.
Summary of the invention
In view of the deficiencies of the prior art, it is an object of the invention to a kind of offer compositions of thermosetting resin, by its production Prepreg, metal-clad laminate and high-frequency circuit board, compositions of thermosetting resin of the invention do not contain polar group (such as hydroxyl), molecular polarity is low, reactivity is high, reduces dielectric constant and the loss of its solidfied material, and can guarantee solid Compound has the performances such as good flame retardant property, good mechanical strength and good high temperature resistant.
In order to achieve that object of the invention, the invention adopts the following technical scheme:
On the one hand, the present invention provides a kind of compositions of thermosetting resin, and the compositions of thermosetting resin includes low polarity Allylation resin and phosphorous-containing monomers or phosphorous resin, the low polarity allylation resin have structure shown in formula I, institute State phosphorous-containing monomers or phosphorous resin have as Formulas I ' shown in structure:
Formulas I and Formulas I ' in, R is linear or branched alkyl group,-O-、 X and Y independently is hydrogen, allyl, straight chained alkyl or branched alkyl；A is straight Chain or branched alkyl, aryl alkyl or the group containing unsaturated double-bond, R' are linear or branched alkyl group,-O-、A' is phosphorous END CAPPED GROUP Group, n are the integer of 1-20.
In compositions of thermosetting resin of the present invention, the low polarity refers to without containing polar group, especially Without containing hydroxyl group, so that resin has lower polarity, high frequency caused by overcoming general thermosetting resin polarity greatly is situated between Electric constant and high defect is lost, at the same can with this configuration in allylic structure realize crosslinking curing, after guaranteeing solidification Mechanical strength, and can guarantee that solidfied material has excellent heat resistance.
In the present invention, the low polarity allylation resin and phosphorous-containing monomers or phosphorous resin without containing hydroxyl (- OH)。
The softening point of the low polarity allylation resin is more than or equal to 60 DEG C in the present invention, it is possible to provide thermosetting property tree The good process operability of oil/fat composition.
Preferably, the R be C1-C6 (such as C1, C2, C3, C4, C5 or C6) straight chained alkyl or C3-C6 (such as C3, C4, C5 or C6) branched alkyl specifically can be-CH2-、 Deng.
Preferably, R is-CH2-、-O-、 X and Y independently is any in hydrogen, allyl, straight chained alkyl or branched alkyl It is a kind of or at least two combination, A be linear or branched alkyl group, aryl alkyl or the group containing unsaturated double-bond.
Preferably, R' is-CH2-、-O-、 X and Y independently is in hydrogen, allyl, straight chained alkyl or branched alkyl Any one or at least two combination, A' be phosphorous end-capping group.
In the present invention, n is the integer of 1-20, for example, n can for 1,2,3,4,5,6,7,8,9,10,11,12,13,14, 15,16,17,18,19 or 20.
Preferably, X and Y independently be C1-C21 (such as C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20 or C21) straight chained alkyl or C3-C21 (such as C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20 or C21) branched alkyl.
Preferably, A be C1-C21 (such as C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20 or C21) straight chained alkyl or C3-C21 (such as C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20 or C21) branched alkyl, specifically can for methyl, ethyl, Propyl, butyl, amyl etc..
Preferably, the aryl alkyl is benzyl, i.e.,
Preferably, the group containing unsaturated double-bond be phenyl,
Preferably, the A' is the group containing DOPO structure, preferably In any one.
Preferably, the low polarity allylation resin is appointing in the compound with the structure as shown in following formula A- formula H It anticipates a kind of or at least two combinations:
Wherein n is the integer of 1-20.
Preferably, the phosphorous-containing monomers or phosphorous resin are the phosphorus monomer or phosphorous resin that phosphorus content is greater than 3%, more preferably Amount is greater than 5% phosphorus monomer or phosphorous resin, and further preferred phosphorus amount is greater than 8% phosphorus monomer or phosphorous resin.Phosphorus content is bigger, It can provide the good flame retardant property of compositions of thermosetting resin.
Preferably, the phosphorous-containing monomers or phosphorous resin are appointing in the compound with the structure as shown in following formula K- formula N It anticipates a kind of or at least two combinations:
Wherein n is the integer of 1-20.
Preferably, the low polarity allylation resin is prepared by the following procedure method and is prepared, the method includes with Lower step:
(1) phenolic compound or phenolic resin shown in Formula II react to obtain allyl shown in formula III with allylation reagents Etherified resin, example reaction equation are as follows:
(2) under protective gas protection, allyl etherization resin shown in formula III is heated, it is anti-that intramolecular rearrangement occurs It should obtain allylation phenolic resin shown in formula IV；
(3) allylation phenolic resin shown in formula III and alkylating reagent or the hydroxyl containing unsaturated double-bond group seal End reagent reacts, and obtains low polarity allylation resin shown in Formulas I；
Wherein, R1For linear or branched alkyl group,-O-、 R2For linear or branched alkyl group,-O-、R3For linear or branched alkyl group, -O-、R is linear or branched alkyl group, - O- orX and Y independently is hydrogen, allyl, straight chained alkyl In branched alkyl any one or at least two combination；A is linear or branched alkyl group, aryl alkyl or contains unsaturated The group of double bond, n are the integer of 1-20.
Preferably, step (1) phenolic compound or phenolic resin are phenol, dihydric phenol, polyphenol or their derivative Resin, preferably phenol, o-cresol, bisphenol-A, Bisphenol F, bisphenol-A, phenolic resin, ortho-cresol novolac resin or ring penta In diene phenolic resin any one or at least two combination.
Preferably, the allylation reagents are allyl silanol, allyl chloride, allyl bromide, bromoallylene, allyl iodide or allyl In base amine any one or at least two combination.
Preferably, the molar ratio of the phenolic compound or phenolic resin and allylation reagents is 1:(0.3~1.2), Such as 1:0.3,1:0.4,1:0.5,1:0.6,1:0.7,1:0.8,1:0.9,1:1,1:1.1 or 1:1.2.
Preferably, step (1) reaction carries out in the presence of a basic, the preferred sodium hydroxide of the alkaline matter, In potassium hydroxide, sodium carbonate or potassium carbonate any one or at least two combination.
Preferably, the alkaline matter rubs with institute's phenolic hydroxy group in step (1) phenolic compound or phenolic resin You than be (0.3~1.4): 1, for example, 0.3:1,0.4:1,0.5:1,0.6:1,0.7:1,0.8:1,0.9:1,1:1,1.1:1, 1.2:1,1.3:1 or 1.4:1.
Preferably, step (1) reaction carries out in the presence of a phase transfer catalyst.
Preferably, the phase transfer catalyst is quaternary ammonium salt-type phase transfer catalyst, preferably tetrabutylammonium chloride, the tetrabutyl Ammonium bromide, benzyltriethylammoinium chloride, 4-butyl ammonium hydrogen sulfate, tri-n-octyl methyl ammonium chloride, dodecyl trimethyl ammonium chloride In myristyl trimethylammonium bromide ammonium chloride any one or at least two combination.
Preferably, the additional amount of the phase transfer catalyst is step (1) described phenolic compound or phenolic resin quality 0.1-5%, such as 0.1%, 0.3%, 0.5%, 0.8%, 1%, 1.3%, 1.5%, 1.8%, 2%, 2.3%, 2.5%, 2.8%, 3%, 3.3%, 3.5%, 3.8%, 4%, 4.3%, 4.5%, 4.8% or 5%.
Preferably, the solvent of step (1) described reaction is any one in alcohols solvent, aromatic hydrocarbon solvent or ketones solvent Kind or at least two combination, preferably any one in ethyl alcohol, propyl alcohol, butanol, toluene or dimethylbenzene or at least two Combination.
Preferably, the additional amount of the solvent is 2-5 times of step (1) described phenolic compound or phenolic resin quality, Such as 2 times, 2.3 times, 2.5 times, 2.8 times, 3 times, 3.3 times, 3.5 times, 3.8 times, 4 times, 4.3 times, 4.5 times, 4.8 times or 5 times.
Preferably, the temperature of step (1) described reaction is 60-90 DEG C, such as 60 DEG C, 63 DEG C, 65 DEG C, 68 DEG C, 70 DEG C, 75 DEG C, 78 DEG C, 80 DEG C, 85 DEG C, 88 DEG C or 90 DEG C.
Preferably, the time of step (1) described reaction is 4-6 hours, for example, 4 hours, 4.3 hours, 4.5 hours, it is 4.8 small When, 5 hours, 5.2 hours, 5.5 hours, 5.8 hours or 6 hours.
Preferably, step (2) protective gas is nitrogen or argon gas.
Preferably, step (2) it is described be heated to be heated to 180-220 DEG C, such as 180 DEG C, 185 DEG C, 190 DEG C, 195 DEG C, 200 DEG C, 205 DEG C, 210 DEG C, 215 DEG C or 220 DEG C.
Preferably, the time of step (2) described reaction is 4-6 hours, for example, 4 hours, 4.3 hours, 4.5 hours, it is 4.8 small When, 5 hours, 5.2 hours, 5.5 hours, 5.8 hours or 6 hours.
Preferably, step (3) alkylating reagent is halogenated alkane, preferably chloromethanes, chloroethanes, chloropropane, neoprene In alkane, bromomethane, bromoethane, N-Propyl Bromide, bromobutane, benzyl bromide or benzyl chloride any one or at least two combination.
Preferably, the hydroxy-end capped reagent containing unsaturated double-bond group described in step (3) is that ether can occur with phenolic hydroxyl group Change, the halogenated compound containing unsaturated double-bond group, acid anhydrides or the acyl chlorides of esterification, preferred vinyl benzyl chloride, second Alkenyl benzyl chloride, to vinyl benzyl bromide, vinyl benzyl bromide, acryloyl chloride, acrylic anhydride, methacrylic chloride or methyl In acrylic anhydride any one or at least two combination；
Preferably, phenolic hydroxyl group and alkyl in alkylating reagent in allylation phenolic resin shown in step (3) described formula III Or with the molar ratio of end-capping group in the hydroxy-end capped reagent containing unsaturated double-bond group be 1:(1~1.2), such as 1:1,1: 1.05,1:1.1,1:1.15 or 1:1.2.So that phenolic hydroxyl group is alkyl etherified in the resinous molecular structure that reaction obtains, thus Make nonpolarity hydroxyl group in resin.
Preferably, step (3) reaction carries out in the presence of a basic.
Preferably, the alkaline matter is inorganic base, preferably in sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate Any one or at least two combination.
Preferably, in allylation phenolic resin shown in the alkaline matter and formula III the molar ratio of phenolic hydroxyl group be (1~ 1.4): 1, such as 1:1,1.05:1,1.1:1,1.15:1,1.2:1,1.25:1,1.3:1,1.35:1 or 1.4:1.
Preferably, step (3) reaction carries out in the presence of a phase transfer catalyst.
Preferably, the phase transfer catalyst is quaternary ammonium salt-type phase transfer catalyst, preferably tetrabutylammonium chloride, the tetrabutyl Ammonium bromide, benzyltriethylammoinium chloride, 4-butyl ammonium hydrogen sulfate, tri-n-octyl methyl ammonium chloride, dodecyl trimethyl ammonium chloride In myristyl trimethylammonium bromide ammonium chloride any one or at least two combination.
Preferably, the additional amount of the phase transfer catalyst is step (3) described allylation phenolic resin quality 0.1-5%, for example, 0.1%, 0.3%, 0.5%, 0.8%, 1%, 1.3%, 1.5%, 1.8%, 2%, 2.3%, 2.5%, 2.8%, 3%, 3.3%, 3.5%, 3.8%, 4%, 4.3%, 4.5%, 4.8% or 5%.
Preferably, the solvent of step (3) described reaction is any one in alcohols solvent, aromatic hydrocarbon solvent or ketones solvent Kind or at least two combination, preferably any one in ethyl alcohol, propyl alcohol, butanol, toluene or dimethylbenzene or at least two Combination.
Preferably, the additional amount of the solvent is 2-5 times of step (3) described allylation phenolic resin quality, such as 2 Again, 2.3 times, 2.5 times, 2.8 times, 3 times, 3.3 times, 3.5 times, 3.8 times, 4 times, 4.3 times, 4.5 times, 4.8 times or 5 times.
Preferably, the temperature of step (3) described reaction is 60-90 DEG C, such as 60 DEG C, 63 DEG C, 65 DEG C, 68 DEG C, 70 DEG C, 75 DEG C, 78 DEG C, 80 DEG C, 85 DEG C, 88 DEG C or 90 DEG C.
Preferably, the time of step (3) described reaction is 4-6 hours, for example, 4 hours, 4.3 hours, 4.5 hours, it is 4.8 small When, 5 hours, 5.2 hours, 5.5 hours, 5.8 hours or 6 hours.
Polar hydroxyl and molecular structure stabilized, tool are not contained in the resin being prepared by means of the present invention Have the characteristics that molecular polarity is low, reactivity is high, polar hydroxyl groups will not be generated in the process of its application, avoid production Influence of the raw secondary hydroxyl for the performance of its product.
Preferably, preparation method of the invention is by rearrangement, the hydroxy-end capped reagent containing unsaturated double-bond group to phenol Hydroxyl carries out the combination of end capping reaction, can significantly improve resin softening point, to be more suitable for the preparation of solid-state prepreg, change Kind resin forming processing performance.Typical allyl phenol urea formaldehyde softening point can be improved from 20 DEG C to 90 DEG C.
Preferably, the phosphorous-containing monomers or phosphorous resin are prepared by the following procedure method and are prepared, the method includes with Lower step:
(A) phenolic compound or phenolic resin shown in Formula II react to obtain allyl shown in formula III with allylation reagents Etherified resin, example reaction equation are as follows:
(B) under protective gas protection, allyl etherization resin shown in formula III is heated, it is anti-that intramolecular rearrangement occurs It should obtain allylation phenolic resin shown in formula IV；
(C) allylation phenolic resin shown in formula III reacts with phosphorous capping reagent, obtain Formulas I ' shown in phosphorous list Body or phosphorous resin；
Wherein, R1For linear or branched alkyl group,-O-、 R2For linear or branched alkyl group,-O-、R3For linear or branched alkyl group,-O-、R' is straight chain Or branched alkyl,-O-、 X and Y independently be hydrogen, allyl, straight chained alkyl, in branched alkyl any one or at least two combination；A' is phosphorous End-capping group, n are the integer of 1-20.
Preferably, step (A) phenolic compound or phenolic resin be monohydric phenol, dihydric phenol, polyphenol or they Resins derived therefrom, preferably phenol, o-cresol, bisphenol-A, Bisphenol F, bisphenol-A, phenolic resin, ortho-cresol novolac resin or In cyclopentadiene phenolic resin any one or at least two combination.
Preferably, the allylation reagents are allyl silanol, allyl chloride, allyl bromide, bromoallylene, allyl iodide or allyl In base amine any one or at least two combination.
Preferably, in the phenolic compound or phenolic resin in phenolic hydroxyl group and allylation reagents allyl molar ratio For 1:0.3~1.2, such as 1:0.3,1:0.4,1:0.5,1:0.6,1:0.7,1:0.8,1:0.9,1:1,1:1.1 or 1:1.2.
Preferably, step (A) reaction carries out in the presence of a basic, the preferred sodium hydroxide of the alkaline matter, In potassium hydroxide, sodium carbonate or potassium carbonate any one or at least two combination.
Preferably, the alkaline matter rubs with institute's phenolic hydroxy group in step (A) phenolic compound or phenolic resin You are than being 0.3~1.4:1, such as 0.3:1,0.4:1,0.5:1,0.6:1,0.7:1,0.8:1,0.9:1,1:1,1.1:1,1.2: 1,1.3:1 or 1.4:1.
Preferably, step (A) reaction carries out in the presence of a phase transfer catalyst.
Preferably, the phase transfer catalyst is quaternary ammonium salt-type phase transfer catalyst, preferably tetrabutylammonium chloride, the tetrabutyl Ammonium bromide, benzyltriethylammoinium chloride, 4-butyl ammonium hydrogen sulfate, tri-n-octyl methyl ammonium chloride, dodecyl trimethyl ammonium chloride In myristyl trimethylammonium bromide ammonium chloride any one or at least two combination.
Preferably, the additional amount of the phase transfer catalyst is step (A) described phenolic compound or phenolic resin quality 0.1-5%, such as 0.1%, 0.3%, 0.5%, 0.8%, 1%, 1.3%, 1.5%, 1.8%, 2%, 2.3%, 2.5%, 2.8%, 3%, 3.3%, 3.5%, 3.8%, 4%, 4.3%, 4.5%, 4.8% or 5%.
Preferably, the solvent of step (A) described reaction is any one in alcohols solvent, aromatic hydrocarbon solvent or ketones solvent Kind or at least two combination, preferably any one in ethyl alcohol, propyl alcohol, butanol, toluene or dimethylbenzene or at least two Combination.
Preferably, the additional amount of the solvent is 2-5 times of step (A) described phenolic compound or phenolic resin quality, Such as 2 times, 2.3 times, 2.5 times, 2.8 times, 3 times, 3.3 times, 3.5 times, 3.8 times, 4 times, 4.3 times, 4.5 times, 4.8 times or 5 times.
Preferably, the temperature of step (A) described reaction is 60-90 DEG C, such as 60 DEG C, 63 DEG C, 65 DEG C, 68 DEG C, 70 DEG C, 75 DEG C, 78 DEG C, 80 DEG C, 85 DEG C, 88 DEG C or 90 DEG C.
Preferably, the time of step (A) described reaction is 4-6 hours, for example, 4 hours, 4.3 hours, 4.5 hours, it is 4.8 small When, 5 hours, 5.2 hours, 5.5 hours, 5.8 hours or 6 hours.
Preferably, step (B) protective gas is nitrogen or argon gas.
Preferably, step (B) it is described be heated to be heated to 180-220 DEG C, such as 180 DEG C, 185 DEG C, 190 DEG C, 195 DEG C, 200 DEG C, 205 DEG C, 210 DEG C, 215 DEG C or 220 DEG C.
Preferably, the time of step (B) described reaction is 4-6 hours, for example, 4 hours, 4.3 hours, 4.5 hours, it is 4.8 small When, 5 hours, 5.2 hours, 5.5 hours, 5.8 hours or 6 hours.
Preferably, step (C) the phosphorous capping reagent be the miscellaneous -10- phosphine phenanthrene -10- oxide of 9,10- dihydro-9-oxy, 9, Miscellaneous -10- phosphine phenanthrene -10- the oxide of 10- dihydro-9-oxy, the 2- (miscellaneous -6- benzene of 6H- dibenzo (c, e) (1,2) -5- oxa- -6- phosphono Base -1,4- hydroquinone, 2- (miscellaneous -6- phenyl -4- phenol of 6H- dibenzo (c, e) (1,2) -5- oxa- -6- phosphono, 2- (6H- bis- Miscellaneous -6- phenyl -3- the phenol of benzo (c, e) (1,2) -5- oxa- -6- phosphono, 2- (6H- dibenzo (c, e) (1,2) -5- oxa- -6- Miscellaneous -6- phenyl -4- the benzyl alcohol of phosphono or the 2- (miscellaneous -6- phenyl -3- benzene first of 6H- dibenzo (c, e) (1,2) -5- oxa- -6- phosphono In alcohol any one or at least two combination.
Preferably, contain in phenolic hydroxyl group and phosphorous capping reagent in allylation phenolic resin shown in step (C) described formula III The molar ratio of phosphorus END CAPPED GROUP is 1:1~1.2, such as 1:1,1:1.05,1:1.1,1:1.15 or 1:1.2.So that reaction obtained Phenolic hydroxyl group is by phosphorous end-capping group in resinous molecular structure, to make nonpolarity hydroxyl group in resin.
Preferably, step (C) reaction carries out in the presence of a basic.
Preferably, the alkaline matter is inorganic base or organic base, preferably sodium hydroxide, potassium hydroxide, sodium carbonate, carbonic acid In potassium, triethylamine or pyridine any one or at least two combination.
Preferably, in allylation phenolic resin shown in the alkaline matter and formula III the molar ratio of phenolic hydroxyl group be (1~ 1.4): 1, such as 1:1,1.05:1,1.1:1,1.15:1,1.2:1,1.25:1,1.3:1,1.35:1 or 1.4:1.
Preferably, step (C) reaction carries out in the presence of carbon tetrachloride.
Preferably, the carbon tetrachloride and phenolic hydroxyl group mole in allylation phenolic resin shown in step (C) described formula III Than for (1-2): 1, such as 1:1,1.1:1,1.2:1,1.3:1,1.4:1,1.5:1,1.6:1,1.7:1,1.8:1,1.9:1 or 2: 1。
Preferably, the solvent of step (C) described reaction is halogenated hydrocarbon solvent, preferably monochloro methane, methylene chloride, three In chloromethanes or dichloroethanes any one or at least two combination.
Preferably, the additional amount of the solvent is 2-5 times of step (C) described allylation phenolic resin quality, such as 2 Again, 2.3 times, 2.5 times, 2.8 times, 3 times, 3.3 times, 3.5 times, 3.8 times, 4 times, 4.3 times, 4.5 times, 4.8 times or 5 times.
Preferably, the temperature of step (C) described reaction is 0-30 DEG C, such as 0 DEG C, 3 DEG C, 5 DEG C, 8 DEG C, 10 DEG C, 15 DEG C, 18 DEG C, 20 DEG C, 25 DEG C, 28 DEG C or 30 DEG C, preferably 10 DEG C.
Preferably, the time of step (C) described reaction is 4-6 hours, for example, 4 hours, 4.3 hours, 4.5 hours, it is 4.8 small When, 5 hours, 5.2 hours, 5.5 hours, 5.8 hours or 6 hours.
In the present invention, in the rearrangement step of step (2) or step (B), work as R2For When, include the case where that allyl ether therein can be reset, causes The temporary location R of allylation phenolic resin shown in formula IV3In containing due to rearrangement generating allyl, and then in Formulas I or formula It include the allyl that generates in R the or R' unit of product shown in I' due to rearrangement, in order to which the simple of statement will in the present invention The allyl is directly indicated to R3In the corresponding construction of R or R', and substituent group all on phenyl ring is only represented by X, However clear X herein includes the allyl generated due to rearrangement herein, if the R before rearrangement reaction2For Other substituent Xs are had on phenyl ring, After the rearrangement reaction, then in R3Structure Middle X can indicate to reset the combination of other substituent groups before the allyl generated and reaction.Certainly in the rearrangement step, Including R2ForWhen, R2Allyl ether in unit There is a situation where rearrangement reactions, at this point, R after reaction3And the R or X in R' of product with react before allyl shown in formula III R in etherified resin2In X group it is identical.
In the present invention, the phosphorous-containing monomers or impurity in phosphorous resin or by-products content are few, impurity or by-product Content is few, can provide the good dielectric properties of compositions of thermosetting resin and heat resistance.The preferred phosphorous-containing monomers contain The dielectric loss angle tangent of phosphorus resin is less than or equal to 0.0025 (1GHz).
Low polar resin containing allyl unsaturated group has good reactivity.The suitable molecular weight of control can be with Good dissolubility and low melt viscosity, advantageous subsequent impregnation technology operation and lamination flowing are provided.It more can be in multilayer The process of circuit board provides filler ability.
According to the present invention, the phosphorous-containing monomers or phosphorous resin can be used as the above-mentioned low polar resin containing allyl Crosslinking agent, for the above-mentioned low polar resin containing allyl of crosslinking curing.
Preferably, mass percentage of the low polarity allylation resin in the compositions of thermosetting resin is 5%~90%, such as 5%, 8%, 10%, 15%, 18%, 20%, 25%, 30%, 40%, 50%, 60%, 70%, 80% Or 90%.
Preferably, in the compositions of thermosetting resin, the phosphorous-containing monomers or phosphorous resin account for low polarity allyl Change the 20~75% of resin and phosphorous-containing monomers or phosphorous resin gross mass, for example, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70% or 75%.
Preferably, the compositions of thermosetting resin further includes powder filler, and in terms of weight content, the powder filler exists Content in compositions of thermosetting resin be 0%~50%, such as 0%, 1%, 5%, 10%, 20%, 30%, 40% or 50%.
Preferably, the powder filler includes crystalline sillica, fusion silica, spherical silica, two Titanium oxide, strontium titanates, barium titanate, barium strontium titanate, zinc silicate, magnesium silicate, aluminium nitride, boron nitride, silicon nitride, silicon carbide, oxidation Aluminium, magnesia, zirconium oxide, beryllium oxide, aluminium hydroxide, magnesium hydroxide, kaolin, talcum powder, hydrotalcite, calcium silicates, removing powder, Melt silicon powder, clean silicon powder, ball-shaped silicon micro powder, zinc borate, mullite, rutile titanium dioxide, anatase titanium dioxide titanium dioxide Titanium, potassium titanate fibre, polytetrafluorethylepowder powder, pps powder, styrene powder, glass fibre, gathers hollow glass microbead In tetrafluoroethene, polyphenylene sulfide or polyether sulfone any one or at least two combination.The above filler can be used alone or It is used in mixed way, wherein best filler is silica, and (CE minerals is public by adoptable silica filler such as CE44I Department), FB-35 (Denka company), 525 (Sibelco companies).
Preferably, in the partial size of the powder filler angle value be 1-15 μm, such as 1 μm, 3 μm, 5 μm, 7 μm, 9 μm, 10 μm, 12 μm or 15 μm, angle value is 1-10 μm preferably in the partial size of powder filler, and the filler positioned at the partial size section has in resin liquid Good dispersibility.
Preferably, the compositions of thermosetting resin further includes curing initiator.
Curing initiator is selected from the material that can produce free radical.Curing initiator plays the work for accelerating curing cross-linking reaction With, when compositions of thermosetting resin of the invention is heated, curing initiator decomposition generate free radicals, cause thermosetting resin and The strand of phosphorous crosslinking agent crosslinks.
Preferably, it is 0.3-6% that the dosage of the curing initiator, which is the mass percent in compositions of thermosetting resin, Such as 0.3%, 0.5%, 0.8%, 1%, 2%, 3%, 4%, 5% or 6%.
Preferably, the curing initiator is benzoyl peroxide, cumyl peroxide, peroxidized t-butyl perbenzoate In 2,5- bis- (2- ethyihexanoylperoxy) -2,5- dimethylhexane any one or at least two combination.Though arranging above Material listed above is lifted but is not limited to, as long as the material that can be generated free radicals, all can serve as curing initiator use.
Preferably, the compositions of thermosetting resin further includes other thermosetting resins, other described thermosetting resins are excellent Monomer or low molecule copolymer of the choosing with unsaturated double-bond or unsaturated three key, further preferred 1,2- polybutadiene, The polyphenylene oxide resin of allyl capped, the polyphenylene oxide resin of acrylate ended, ethenyl blocking polyphenylene oxide resin, maleic acid Copolymer resin (butadiene styrene resin), the triallyl trimerization of polyphenylene oxide resin, 1,2- butadiene resin and styrene that acid anhydride blocks Isocyanates, triallyl cyanurate, divinylbenzene, polyfunctional acrylic ester, bismaleimide, ethenyl blocking Silane resin or allyl capped silane resin in any one or at least two combination, be not limited to above arrange The resin material of act.
On the other hand, the present invention provides a kind of resin adhesive liquid, and the resin adhesive liquid is by thermosetting property tree of the present invention Oil/fat composition is dissolved or dispersed in solvent and obtains.
Preferably, the solvent is one of ketone, hydro carbons, ethers, esters or aprotic solvent or at least two Combination, preferably acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), toluene, dimethylbenzene, methanol, ethyl alcohol, primary alconol, ethylene glycol list first Ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, ethyl acetate, N,N-dimethylformamide or N, N- diethylformamide One of or at least two mixture.The solvent can be used alone, and can also be used in mixed way.The additive amount of solvent can be by Those skilled in the art determine according to the viscosity of selected resin, make the modest viscosity for obtaining resin adhesive liquid, convenient for solidification, originally Invention is not construed as limiting this.
On the other hand, the present invention provides a kind of prepreg, and the prepreg includes reinforcing material and by impregnation drying Adhere to compositions of thermosetting resin as described above thereon afterwards.
In the present invention, the reinforcing material is textile sheet, preferably braided glass fibre cloth.It is specifiable to have E- Glass glass fabric, NE-glass glass fabric, Q-glass glass fabric etc., model include 7628 types, 2116 types, 1080 types, 106 types, 104 types, commercially available glass cloth specification and model all can be used for the production of resin combination of the present invention, It is not limited to the above specifiable glass cloth model.Textile sheet can also include the cloth of organic fibrage, specifiable There are PTFE fiber cloth, aramid fiber woven cloth etc..
On the other hand, the present invention provides a kind of laminate, and the laminate includes an at least prepreg as described above.
On the other hand, the present invention provides a kind of metal-clad laminate, and the metal-clad laminate is including one or extremely The prepregs as described above of few two overlappings, and the prepreg after overlapping one or both sides metal foil.
On the other hand, the present invention provides a kind of high-frequency circuit board, and the high-frequency circuit board includes one or at least two folded The prepreg as described above closed.
Compared with prior art, the invention has the following beneficial effects:
(1) present invention is big caused high using general thermosetting resin polarity is overcome using low polarity allylation resin Frequency dielectric constant and high defect is lost, at the same can with this configuration in allylic structure realize crosslinking curing, guarantee solidification Mechanical strength afterwards, and can guarantee that solidfied material has excellent heat resistance.
(2) flame retardant property of compositions of thermosetting resin can be improved in heretofore described phosphorous-containing monomers or phosphorous resin, It can be used as the crosslinking agent of above-mentioned low polarity allylation resin, be used for the low polarity allylation resin of crosslinking curing, and described Phosphorous-containing monomers or phosphorous resin have excellent dissolution performance, lower melt viscosity, it is good to impart compositions of thermosetting resin Good performance of technical process.
(3) heretofore described low polarity allylation resin and the phosphorous-containing monomers or phosphorous resin are improving copper-clad plate Heat resistance and dielectric properties in terms of play good synergistic effect.
(4) be easier to by compositions of thermosetting resin production prepreg of the invention, with the copper-clad plate of its production and High-frequency circuit board, dielectric constant and dielectric loss angle tangent are low, and technological operation is convenient, therefore thermosetting resin combination of the invention Object is suitable for making the circuit board of high frequency electronic equipment.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.Those skilled in the art should be bright , the described embodiments are merely helpful in understanding the present invention, should not be regarded as a specific limitation of the invention.
Constituent source such as the following table 1 in thermoset composition selected by the embodiment of the present invention:
Table 1
Manufacturer Name of product or the trade mark Material content
sabic SA9000 The polyphenylene oxide of acrylate ended
Self-control Propyl is etherified allyl ortho-cresol novolac resin
Self-control Butyl is etherified allyl phenol urea formaldehyde
Self-control Methacrylated allyl phenol urea formaldehyde
Self-control Phosphorous esterification diallyl bisphenol
Self-control Phosphorous esterification allyl phenol urea formaldehyde
Self-control Phosphorous esterification allyl ortho-cresol novolac resin
Sibelco 525 Silicon powder
Shanghai Gaoqiao DCP Cumyl peroxide
Shanghai it is macro and 1080 glass fabrics Thickness 0.05mm, base weight 48g/m2
Preparation example 1
250g toluene is added in three mouthfuls of reaction flasks, 118g ortho-cresol novolac resin is added in reaction flask, after stirring and dissolving, 100g sodium hydrate aqueous solution is added, adds 1g tetrabutylammonium bromide.After temperature is constant, it is molten that 153g chloropropene is slowly added dropwise Liquid stops reaction, washing after reaction 4 hours, then removes toluene to get allyl etherization ortho-cresol novolac resin is arrived.
The 159g allyl etherization ortho-cresol novolac resin of preparation is put into reaction flask, 200 DEG C or more is heated to and reacts 4 Hour, obtain dark-brown allyl ortho-cresol novolac resin.
300g toluene is added in reaction flask, the 159g allyl ortho-cresol novolac resin of preparation is put into reaction flask, is stirred After mixing dissolution, 100g sodium hydrate aqueous solution is added.After temperature is constant, 157g chloropropane is slowly added dropwise, reaction stops after 4 hours It only reacts, washs, then remove solvent and water and be etherified allyl ortho-cresol novolac resin, Mn 1230, knot to get to propyl Structure is as follows:
Preparation example 2
300g n-butanol is added in three mouthfuls of reaction flasks, 114g linear phenol-aldehyde resin is added in reaction flask, after stirring and dissolving, 56g potassium hydroxide is added.153g bromopropene solution is slowly added dropwise, then stops reaction after temperature reaction 4 hours.Filtering, washing, Remove remaining solvent and water again to get allyl etherization phenolic resin is arrived.
The 141g allyl etherization phenolic resin of preparation is put into reaction flask, heating progress rearrangement reaction, cooling discharge, Obtain brown viscous liquid i.e. allyl phenol urea formaldehyde.
402g n-butanol is added in reaction flask, 141g allyl phenol urea formaldehyde is put into reaction flask, after stirring and dissolving, is added Enter 104g sodium carbonate.171g chlorobutane solution is slowly added dropwise, then stops reaction after temperature reaction 6 hours.Filtering, washing, then It removes solvent and water and is etherified allyl phenol urea formaldehyde to get to butyl, Mn 1080, structure is as follows:
Preparation example 3
300g n-butanol is added in three mouthfuls of reaction flasks, 114g linear phenol-aldehyde resin is added in reaction flask, after stirring and dissolving, 56g potassium hydroxide is added.153g bromopropene solution is slowly added dropwise, then stops reaction after temperature reaction 4 hours.Filtering, washing, Remove remaining solvent and water again to get allyl etherization phenolic resin is arrived.
The 141g allyl etherization phenolic resin of preparation is put into reaction flask, heating progress rearrangement reaction, cooling discharge, Obtain brown viscous liquid i.e. allyl phenol urea formaldehyde.
402g n-butanol is added in reaction flask, the 141g allyl phenol urea formaldehyde of preparation is put into reaction flask, stirs molten 102g triethylamine is added in Xie Hou.80g methacrylic acid anhydride solution is slowly added dropwise, then stops reaction after temperature reaction 6 hours, Washing, then solvent and water are removed to get to methacrylated allyl phenol urea formaldehyde, Mn 1250, structure is as follows It is shown:
Preparation example 4
188g acetone is added in three mouthfuls of reaction flasks, 228g bisphenol-A is added in reaction flask, after stirring and dissolving, 106g is added Sodium carbonate.153g chloropropene solution is slowly added dropwise, then stops reaction after temperature reaction 4 hours.Filtering removes most of molten Agent, washing, then remaining solvent and water are removed to get tetrabutyl ammonium bromide is arrived.
The 134g tetrabutyl ammonium bromide of preparation is put into reaction flask, heating carries out rearrangement reaction 6 hours, cools down out Material, obtains brown viscous liquid i.e. diallyl bisphenol.
Lead to inert gas shielding in there-necked flask, 300g methylene chloride is added, the 134g diallyl bisphenol of preparation is put into In reaction flask, after stirring and dissolving, 40g sodium hydroxide is added, and 152g carbon tetrachloride is added.230g 2- (6H- bis- is slowly added dropwise Miscellaneous -6- phenyl -4- the phenol of benzo (c, e) (1,2) -5- oxa- -6- phosphono reacts 4 hours, stops reaction, and sodium hydroxide is added Aqueous solution is washed to neutrality, then is washed for several times, removes remaining solvent and water to get to phosphorous esterification diallyl bisphenol, Structure is as follows:
Preparation example 5
300g n-butanol is added in three mouthfuls of reaction flasks, 114g linear phenol-aldehyde resin is added in reaction flask, after stirring and dissolving, 56g potassium hydroxide is added.153g bromopropene solution is slowly added dropwise, then stops reaction after temperature reaction 4 hours.Filtering, washing, Remove remaining solvent and water again to get allyl etherization phenolic resin is arrived.
The 141g allyl etherization phenolic resin of preparation is put into reaction flask, heating carries out rearrangement reaction 4 hours, cooling Discharging, obtains brown viscous liquid i.e. allyl phenol urea formaldehyde.
Lead to inert gas shielding in there-necked flask, 350g methylene chloride is added, the 141g diallyl bisphenol of preparation is put into In reaction flask, after stirring and dissolving, 72g triethylamine is added, and 152g carbon tetrachloride is added.After temperature is down to 30 DEG C or less, delay (miscellaneous -6- phenyl -4- phenol of 6H- dibenzo (c, e) (1,2) -5- oxa- -6- phosphono reacts 4 hours, stops slow dropwise addition 230g 2- It only reacts, sodium hydrate aqueous solution is added and washs to neutrality, then washs for several times, it is phosphorous to get arriving to remove remaining solvent and water It is esterified allyl phenol urea formaldehyde, Mn 1300, structure is as follows:
Preparation example 6
250g toluene is added in three mouthfuls of reaction flasks, 118g ortho-cresol novolac resin is added in reaction flask, after stirring and dissolving, It is added 100g sodium hydrate aqueous solution (concentration 40%), adds 1g tetrabutylammonium bromide.After temperature is constant, it is slowly added dropwise Then 153g chloropropene solution stops reaction, washing after temperature reaction 4 hours, then remove solvent to get adjacent to allyl etherization Cresol novolac resin.
The 159g allyl etherization ortho-cresol novolac resin of preparation is put into reaction flask, it is small that heating carries out rearrangement reaction 4 When, cooling discharge, obtaining brownish semi solid is allyl ortho-cresol novolac resin.
Lead to inert gas shielding in there-necked flask, 350g methylene chloride is added, the 159g diallyl bisphenol of preparation is put into In reaction flask, after stirring and dissolving, 103g pyridine is added, and 152g carbon tetrachloride is added.230g 2- (6H- dibenzo is slowly added dropwise Miscellaneous -6- phenyl -3- the phenol of (c, e) (1,2) -5- oxa- -6- phosphono reacts 4 hours, stops reaction, and it is water-soluble that sodium hydroxide is added Liquid is washed to neutrality, then is washed for several times, removes remaining solvent and water to get phosphorous esterification allyl o-cresol phenolic aldehyde tree is arrived Rouge, Mn 1200, structure is as follows:
Embodiment 1
Propyl prepared by 80 parts by weight preparation examples 1 is etherified allyl ortho-cresol novolac resin, the preparation example 4 of 20 parts by weight The phosphorous esterification diallyl bisphenol of preparation, the silica (525) of 85 parts by weight, the initiator DCP mixing of 6.5 parts by weight, It is adjusted to suitable viscosity with solvent toluene, is uniformly mixed, makes filler is uniform to be dispersed in resin, glue is made.With 1080 glass fabrics impregnate the above glue, and then prepreg is made after removing solvent in drying.Admittedly by eight manufactured half Change piece to be superimposed, cover the copper foil of 1oz (ounce) thickness in its two sides, carry out solidifying for 2 hours in press, solidifying pressure is 50kg/cm2, solidification temperature is 190 DEG C, and physical data is as shown in table 2.
Embodiment 2-4
Manufacture craft and embodiment 1 are identical, and assistant crosslinking agent bismaleimide or polyphenylene oxide, thermosetting resin group is added The proportion for closing object is as shown in table 2.
Embodiment 5
Butyl prepared by 80 parts by weight preparation examples 2 is etherified allyl phenol urea formaldehyde, prepared by the preparation example 5 of 20 parts by weight Phosphorous esterification allyl phenol urea formaldehyde, the silica (525) of 85 parts by weight, the initiator DCP mixing of 6.5 parts by weight, use are molten Agent toluene is adjusted to suitable viscosity, is uniformly mixed, and makes filler is uniform to be dispersed in resin, and glue is made.With 1080 glass Glass fiber cloth impregnates the above glue, and then prepreg is made after removing solvent in drying.By eight manufactured prepreg phases Overlapping, covers the copper foil of 1oz (ounce) thickness in its two sides, carries out solidifying for 2 hours in press, solidifying pressure 50kg/ cm2, solidification temperature is 190 DEG C, and physical data is as shown in table 2.
Embodiment 6
Methacrylated allyl phenol urea formaldehyde prepared by 80 parts by weight preparation examples 3, the preparation example 6 of 20 parts by weight The phosphorous esterification allyl ortho-cresol novolac resin of preparation, the silica (525) of 85 parts by weight, the initiator of 6.5 parts by weight DCP mixing, is adjusted to suitable viscosity with solvent toluene, is uniformly mixed, make filler is uniform to be dispersed in resin, and glue is made Liquid.The above glue is impregnated with 1080 glass fabrics, then prepreg is made after removing solvent in drying.It is manufactured by eight Prepreg is superimposed, and covers the copper foil of 1oz (ounce) thickness in its two sides, carries out solidifying for 2 hours in press, solidifying pressure For 50kg/cm2, solidification temperature is 190 DEG C, and physical data is as shown in table 3.
Embodiment 7
Manufacture craft and embodiment 1 are identical, only add a small amount of phosphorous esterification diallyl bisphenol, material mixture ratio such as 3 institute of table Show.
Comparative example 1-2
Manufacture craft and embodiment 1 are identical, remove phosphorous esterification diallyl bisphenol or with allyl phenol urea formaldehyde and DOPO, material mixture ratio are as shown in table 3.
Table 2
Material and performance Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5
SA9000 0 0 5 0
Propyl is etherified allyl ortho-cresol novolac resin 80 50 65 35
Butyl is etherified allyl phenol urea formaldehyde 80
Methacrylated allyl phenol urea formaldehyde
Phosphorous esterification diallyl bisphenol 20 40 30 65
Phosphorous esterification allyl phenol urea formaldehyde 20
Phosphorous esterification allyl ortho-cresol novolac resin
525 85 240 85 120 85
Bismaleimide BM-3000 0 10 0 15 0
DCP 2 2 2 2 2
1080 glass fabrics 80.7 125 78 85 80.7
Dielectric constant (10GHZ) 3.78 3.86 3.93 3.95 4.03
Dielectric loss angle tangent (10GHZ) 0.0053 0.0056 0.0056 0.0057 0.0056
Resistance to dip solderability 288 DEG C, (second) > 120 > 120 > 120 > 120 > 120
Glass transition temperature (DEG C) (DSC) 160 220 173 225 210
Anti-flammability V-1 V-0 V-1 V-0 V-1
Glass-impregnated operation It is good It is good It is good It is good It is good
Table 3
Physical Property Analysis
It can be seen that the copper-clad plate of embodiment 1-7 preparation than comparative example 1 from the physical data result of table 2 and table 3 and compare Copper-clad plate prepared by example 2 has better heat resistance and dielectric properties, illustrates in the heat resistance and dielectric for promoting copper-clad plate Aspect of performance, low polarity allylation resin and phosphorous-containing monomers or phosphorous resin play synergistic effect.
It can be seen that from the physical data result of table 2 when in ratio range of the present invention bismaleimide being added, it can be with Obtain better heat resistance.
The Applicant declares that the present invention is explained by the above embodiments compositions of thermosetting resin of the invention and its answering With, but the present invention is not limited to the above embodiments, that is, does not mean that the present invention must rely on above-described embodiment and could implement.Institute Belong to those skilled in the art it will be clearly understood that any improvement in the present invention, to the equivalence replacement of raw material selected by the present invention And addition, selection of concrete mode of auxiliary element etc., all of which fall within the scope of protection and disclosure of the present invention.

Claims (10)

1. a kind of compositions of thermosetting resin, which is characterized in that the compositions of thermosetting resin includes low polarity allylation Resin and phosphorous-containing monomers or phosphorous resin, the low polarity allylation resin have structure shown in formula I, the phosphorous list Body or phosphorous resin have as Formulas I ' shown in structure:
Formulas I and Formulas I ' in, R is linear or branched alkyl group,-O-、 X and Y independently is hydrogen, allyl, straight chained alkyl, appointing in branched alkyl It anticipates a kind of or at least two combinations；A is that linear or branched alkyl group, aryl alkyl or the group containing unsaturated double-bond, R' are Linear or branched alkyl group,-O-、 A' is phosphorous end-capping group, and n is the integer of 1-20.
2. compositions of thermosetting resin according to claim 1, which is characterized in that R is-CH2-、 -O-、N is 1-20 Integer, X and Y independently are the combination of any one or at least two in hydrogen, allyl, straight chained alkyl or branched alkyl, A For linear or branched alkyl group, aryl alkyl or contain the group of unsaturated double-bond；
Preferably, R' is-CH2-、-O-、 X and Y independently is in hydrogen, allyl, straight chained alkyl or branched alkyl Any one or at least two combination, A' be phosphorous end-capping group；
Preferably, the aryl alkyl is benzyl；
Preferably, the group containing unsaturated double-bond be phenyl,
Preferably, the A' is the group containing DOPO structure, preferably In any one；
Preferably, the low polarity allylation resin is any one in the compound with the structure as shown in following formula A- formula H Kind or at least two combination:
Wherein n is the integer of 1-20；
Preferably, the phosphorous-containing monomers or phosphorous resin are the phosphorus monomer or phosphorous resin that phosphorus content is greater than 3%, and more preferably amount is big In 5% phosphorus monomer or phosphorous resin, further preferred phosphorus amount is greater than 8% phosphorus monomer or phosphorous resin；
Preferably, the phosphorous-containing monomers or phosphorous resin are any one in the compound with the structure as shown in following formula K- formula N Kind or at least two combination:
Wherein n is the integer of 1-20.
3. compositions of thermosetting resin according to claim 1 or 2, which is characterized in that the low polarity allylation tree Rouge is prepared by the following procedure method and is prepared, and the described method comprises the following steps:
(1) phenolic compound or phenolic resin shown in Formula II react to obtain allyl etherization shown in formula III with allylation reagents Resin, example reaction equation are as follows:
(2) under protective gas protection, allyl etherization resin shown in formula III is heated, intramolecular rearrangement occurs and reacts To allylation phenolic resin shown in formula IV；
(3) allylation phenolic resin shown in formula III and alkylating reagent or the hydroxy-end capped examination containing unsaturated double-bond group Agent reacts, and obtains low polarity allylation resin shown in Formulas I；
Wherein, R1For linear or branched alkyl group,-O-、 R2For linear or branched alkyl group,-O-、R3For linear or branched alkyl group,-O-、R is straight Chain or branched alkyl,- O- or X and Y independently be hydrogen, allyl, straight chained alkyl, in branched alkyl any one or at least two combination；A be straight chain or Branched alkyl, aryl alkyl or the group containing unsaturated double-bond, n are the integer of 1-20；
Preferably, step (1) phenolic compound or phenolic resin are phenol, dihydric phenol, polyphenol or their resins derived therefrom, Preferably phenol, o-cresol, bisphenol-A, Bisphenol F, bisphenol-A, phenolic resin, ortho-cresol novolac resin or cyclopentadiene phenol In urea formaldehyde any one or at least two combination；
Preferably, the allylation reagents are allyl silanol, allyl chloride, allyl bromide, bromoallylene, allyl iodide or allyl amine In any one or at least two combination；
Preferably, the molar ratio of the phenolic compound or phenolic resin and allylation reagents is 1:(0.3~1.2)；
Preferably, step (1) reaction carries out in the presence of a basic, the preferred sodium hydroxide of the alkaline matter, hydrogen-oxygen Change potassium, in sodium carbonate or potassium carbonate any one or at least two combination；
Preferably, the molar ratio of the alkaline matter and institute's phenolic hydroxy group in step (1) described phenolic compound or phenolic resin For (0.3~1.4): 1；
Preferably, step (1) reaction carries out in the presence of a phase transfer catalyst；
Preferably, the phase transfer catalyst is quaternary ammonium salt-type phase transfer catalyst, preferably tetrabutylammonium chloride, tetrabutyl phosphonium bromide Ammonium, benzyltriethylammoinium chloride, 4-butyl ammonium hydrogen sulfate, tri-n-octyl methyl ammonium chloride, dodecyl trimethyl ammonium chloride or ten In tetraalkyl trimethylammonium bromide ammonium chloride any one or at least two combination；
Preferably, the additional amount of the phase transfer catalyst is step (1) described phenolic compound or phenolic resin quality 0.1-5%；
Preferably, the solvent of step (1) described reaction be alcohols solvent, aromatic hydrocarbon solvent or ketones solvent in any one or In at least two combination, preferably ethyl alcohol, propyl alcohol, butanol, toluene or dimethylbenzene any one or at least two combination；
Preferably, the additional amount of the solvent is 2-5 times of step (1) described phenolic compound or phenolic resin quality；
Preferably, the temperature of step (1) described reaction is 60-90 DEG C；
Preferably, the time of step (1) described reaction is 4-6 hours；
Preferably, step (2) protective gas is nitrogen or argon gas；
Preferably, it is heated to be described in step (2) and is heated to 180-220 DEG C；
Preferably, the time of step (2) described reaction is 4-6 hours；
Preferably, step (3) alkylating reagent is halogenated alkane, preferably chloromethanes, chloroethanes, chloropropane, chlorobutane, bromine In methane, bromoethane, N-Propyl Bromide, bromobutane, benzyl bromide or benzyl chloride any one or at least two combination；
Preferably, the hydroxy-end capped reagent containing unsaturated double-bond group described in step (3) is that etherificate, ester can occur with phenolic hydroxyl group Change the halogenated compound containing unsaturated double-bond group, acid anhydrides or the acyl chlorides of reaction, preferred vinyl benzyl chloride, vinyl benzyl Base chlorine, to vinyl benzyl bromide, vinyl benzyl bromide, acryloyl chloride, acrylic anhydride, methacrylic chloride or methacrylic acid In acid anhydride any one or at least two combination；
Preferably, in allylation phenolic resin shown in step (3) described formula III in phenolic hydroxyl group and alkylating reagent alkyl or with The molar ratio of end-capping group is 1:(1~1.2 in hydroxy-end capped reagent containing unsaturated double-bond group)；
Preferably, step (3) reaction carries out in the presence of a basic；
Preferably, the alkaline matter is inorganic base or organic base, preferably sodium hydroxide, potassium hydroxide, sodium carbonate, carbonic acid In potassium, triethylamine or pyridine any one or at least two combination；
Preferably, the molar ratio of the alkaline matter and phenolic hydroxyl group in allylation phenolic resin shown in formula III is (1~1.4): 1；
Preferably, step (3) reaction carries out in the presence of a phase transfer catalyst；
Preferably, the phase transfer catalyst is quaternary ammonium salt-type phase transfer catalyst, preferably tetrabutylammonium chloride, tetrabutyl phosphonium bromide Ammonium, benzyltriethylammoinium chloride, 4-butyl ammonium hydrogen sulfate, tri-n-octyl methyl ammonium chloride, dodecyl trimethyl ammonium chloride or ten In tetraalkyl trimethylammonium bromide ammonium chloride any one or at least two combination；
Preferably, the additional amount of the phase transfer catalyst is the 0.1- of step (3) described allylation phenolic resin quality 5%；
Preferably, the solvent of step (3) described reaction be alcohols solvent, aromatic hydrocarbon solvent or ketones solvent in any one or In at least two combination, preferably ethyl alcohol, propyl alcohol, butanol, toluene or dimethylbenzene any one or at least two combination；
Preferably, the additional amount of the solvent is 2-5 times of step (3) described allylation phenolic resin quality；
Preferably, the temperature of step (3) described reaction is 60-90 DEG C；
Preferably, the time of step (3) described reaction is 4-6 hours；
Preferably, the phosphorous-containing monomers or phosphorous resin are prepared by the following procedure method and are prepared, and the method includes following steps It is rapid:
(A) phenolic compound or phenolic resin shown in Formula II react to obtain allyl etherization shown in formula III with allylation reagents Resin, example reaction equation are as follows:
(B) under protective gas protection, allyl etherization resin shown in formula III is heated, intramolecular rearrangement occurs and reacts To allylation phenolic resin shown in formula IV；
(C) allylation phenolic resin shown in formula III reacts with phosphorous capping reagent, obtain Formulas I ' shown in phosphorous-containing monomers or Phosphorous resin；
Wherein, R1For linear or branched alkyl group,-O-、 R2For linear or branched alkyl group,-O-、R3For linear or branched alkyl group,-O-、R' is straight chain Or branched alkyl,-O-、 X and Y independently be hydrogen, allyl, straight chained alkyl, in branched alkyl any one or at least two combination；A' is phosphorous End-capping group, n are the integer of 1-20；
Preferably, step (A) phenolic compound or phenolic resin are phenol, dihydric phenol, polyphenol or their resins derived therefrom, Preferably phenol, o-cresol, bisphenol-A, Bisphenol F, bisphenol-A, phenolic resin, ortho-cresol novolac resin or cyclopentadiene phenol In urea formaldehyde any one or at least two combination；
Preferably, the allylation reagents are allyl silanol, allyl chloride, allyl bromide, bromoallylene, allyl iodide or allyl amine In any one or at least two combination；
Preferably, the molar ratio of allyl is 1 in phenolic hydroxyl group and allylation reagents in the phenolic compound or phenolic resin: 0.3~1.2；
Preferably, step (A) reaction carries out in the presence of a basic, the preferred sodium hydroxide of the alkaline matter, hydrogen-oxygen Change potassium, in sodium carbonate or potassium carbonate any one or at least two combination；
Preferably, the molar ratio of the alkaline matter and institute's phenolic hydroxy group in step (A) described phenolic compound or phenolic resin For 0.3~1.4:1；
Preferably, step (A) reaction carries out in the presence of a phase transfer catalyst；
Preferably, the phase transfer catalyst is quaternary ammonium salt-type phase transfer catalyst, preferably tetrabutylammonium chloride, tetrabutyl phosphonium bromide Ammonium, benzyltriethylammoinium chloride, 4-butyl ammonium hydrogen sulfate, tri-n-octyl methyl ammonium chloride, dodecyl trimethyl ammonium chloride or ten In tetraalkyl trimethylammonium bromide ammonium chloride any one or at least two combination；
Preferably, the additional amount of the phase transfer catalyst is step (A) described phenolic compound or phenolic resin quality 0.1-5%；
Preferably, the solvent of step (A) described reaction be alcohols solvent, aromatic hydrocarbon solvent or ketones solvent in any one or In at least two combination, preferably ethyl alcohol, propyl alcohol, butanol, toluene or dimethylbenzene any one or at least two combination；
Preferably, the additional amount of the solvent is 2-5 times of step (A) described phenolic compound or phenolic resin quality；
Preferably, the temperature of step (A) described reaction is 60-90 DEG C；
Preferably, the time of step (A) described reaction is 4-6 hours；
Preferably, step (B) protective gas is nitrogen or argon gas；
Preferably, it is heated to be described in step (B) and is heated to 180-220 DEG C；
Preferably, the time of step (B) described reaction is 4-6 hours；
Preferably, step (C) the phosphorous capping reagent is the miscellaneous -10- phosphine phenanthrene -10- oxide of 9,10- dihydro-9-oxy, 9,10- Miscellaneous -10- phosphine phenanthrene -10- the oxide of dihydro-9-oxy, the 2- (miscellaneous -6- phenyl-of 6H- dibenzo (c, e) (1,2) -5- oxa- -6- phosphono 1,4- hydroquinone, 2- (miscellaneous -6- phenyl -4- phenol of 6H- dibenzo (c, e) (1,2) -5- oxa- -6- phosphono, 2- (6H- hexichol And miscellaneous -6- phenyl -3- the phenol of (c, e) (1,2) -5- oxa- -6- phosphono, 2- (6H- dibenzo (c, e) (1,2) -5- oxa- -6- phosphine Miscellaneous -6- phenyl -4- the benzyl alcohol of acyl or the 2- (miscellaneous -6- phenyl -3- benzyl alcohol of 6H- dibenzo (c, e) (1,2) -5- oxa- -6- phosphono In any one or at least two combination；
Preferably, phenolic hydroxyl group and phosphorous envelope in phosphorous capping reagent in allylation phenolic resin shown in step (C) described formula III The molar ratio of end group is 1:1~1.2；
Preferably, step (C) reaction carries out in the presence of a basic；
Preferably, the alkaline matter be inorganic base or organic base, preferably sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, In triethylamine or pyridine any one or at least two combination；
Preferably, the molar ratio of the alkaline matter and phenolic hydroxyl group in allylation phenolic resin shown in formula III is (1~1.4): 1；
Preferably, step (C) reaction carries out in the presence of carbon tetrachloride；
Preferably, the carbon tetrachloride is with phenolic hydroxyl group molar ratio in allylation phenolic resin shown in step (C) described formula III (1-2):1；
Preferably, the solvent of step (C) described reaction is halogenated hydrocarbon solvent, preferably monochloro methane, methylene chloride, three chloromethanes In alkane or dichloroethanes any one or at least two combination；
Preferably, the additional amount of the solvent is 2-5 times of step (C) described allylation phenolic resin quality；
Preferably, the temperature of step (C) described reaction is 0-30 DEG C；
Preferably, the time of step (C) described reaction is 4-6 hours.
4. compositions of thermosetting resin according to any one of claim 1-3, which is characterized in that the low polarity allyl Mass percentage of the base resin in the compositions of thermosetting resin is 5%~90%；
Preferably, in the compositions of thermosetting resin, the phosphorous-containing monomers or phosphorous resin account for low polarity allylation tree The 20~75% of rouge and phosphorous-containing monomers or phosphorous resin gross mass.
5. compositions of thermosetting resin described in any one of -4 according to claim 1, which is characterized in that the thermosetting resin Composition further includes powder filler；
Preferably, angle value is 1-15 μm in the partial size of the powder filler, and angle value is 1-10 μm preferably in the partial size of powder filler；
Preferably, weight percentage of the powder filler in compositions of thermosetting resin is 0%~50%；
Preferably, the compositions of thermosetting resin further includes curing initiator；
Preferably, it is 0.3-6% that the dosage of the curing initiator, which is the mass percent in compositions of thermosetting resin,；
Preferably, the curing initiator be benzoyl peroxide, cumyl peroxide, peroxidized t-butyl perbenzoate or 2, In 5- bis- (2- ethyihexanoylperoxy) -2,5- dimethylhexane any one or at least two combination；
Preferably, the compositions of thermosetting resin further includes other thermosetting resins, other described thermosetting resins preferably band There are the monomer or low molecule copolymer of unsaturated double-bond or unsaturated three keys, further preferred 1,2- polybutadiene, allyl The polyphenylene oxide resin of base sealing end, the polyphenylene oxide resin of acrylate ended, the polyphenylene oxide resin of ethenyl blocking, maleic anhydride envelope The polyphenylene oxide resin at end, the copolymer resin (butadiene styrene resin) of 1,2- butadiene resin and styrene, triallyl trimerization isocyanide Acid esters, triallyl cyanurate, divinylbenzene, polyfunctional acrylic ester, bismaleimide, ethenyl blocking silicon In alkane resin or the silane resin of allyl capped any one or at least two combination.
6. a kind of resin adhesive liquid, which is characterized in that the resin adhesive liquid is by thermosetting according to any one of claims 1 to 5 Property resin combination, which is dissolved or dispersed in solvent, to be obtained.
7. a kind of prepreg, which is characterized in that the prepreg includes reinforcing material and adheres to thereon after being dried by impregnation Compositions of thermosetting resin according to any one of claims 1 to 5.
8. a kind of laminate, which is characterized in that the laminate includes an at least prepreg as claimed in claim 7.
9. a kind of metal-clad laminate, which is characterized in that the metal-clad laminate includes one or at least two overlapping Prepreg as claimed in claim 7, and the prepreg after overlapping one or both sides metal foil.
10. a kind of high-frequency circuit board, which is characterized in that the high-frequency circuit board includes one or at least two overlapping such as right It is required that prepreg described in 7.
CN201710617174.6A 2017-07-26 2017-07-26 A kind of compositions of thermosetting resin, prepreg, metal-clad laminate and the high-frequency circuit board made by it Pending CN109306040A (en)

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