CN109694462A - A kind of compositions of thermosetting resin and prepreg, metal-clad laminate and printed circuit board using it - Google Patents

A kind of compositions of thermosetting resin and prepreg, metal-clad laminate and printed circuit board using it Download PDF

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Publication number
CN109694462A
CN109694462A CN201811606732.XA CN201811606732A CN109694462A CN 109694462 A CN109694462 A CN 109694462A CN 201811606732 A CN201811606732 A CN 201811606732A CN 109694462 A CN109694462 A CN 109694462A
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parts
epoxy resin
compositions
curing agent
phenol
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CN201811606732.XA
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CN109694462B (en
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游江
林伟
黄天辉
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Shengyi Technology Co Ltd
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Shengyi Technology Co Ltd
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Priority to PCT/CN2018/125306 priority patent/WO2020133335A1/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • 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
    • B32B15/092—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 comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin 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
    • 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
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4284—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof together with other curing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins

Abstract

The present invention provides a kind of compositions of thermosetting resin and use its prepreg, metal-clad laminate and printed circuit board.Compositions of thermosetting resin includes epoxy resin, phosphorous bis-phenol and the esters curing agent with Formulas I structure.The present invention uses the esters curing agent with Formulas I structure to cooperate with cured epoxy resin with phosphorous bis-phenol, it is main curing agent with phosphorous bis-phenol, impart the excellent dielectric properties of solidfied material, high-fire resistance and bonding force, it is also able to achieve halogen-free flameproof simultaneously, the esters curing agent of convolution I structure, so that not generating secondary hydroxyl isopolarity group in the curing process, solidfied material glass transition temperature can be significantly improved while guaranteeing that dielectric properties are excellent, and contain a large amount of hydrophobic groupings in cured product, solidfied material water absorption rate can be greatly reduced, so that solidfied material dielectric constant and dielectric loss factor are more stable.The laminate and metal-clad laminate of preparation have good heat resistance, moisture-proof, peel strength, dielectric properties and anti-flammability.

Description

A kind of compositions of thermosetting resin and prepreg, metal-clad laminate using it And printed circuit board
Technical field
The invention belongs to printed circuit board technology fields, and in particular to a kind of compositions of thermosetting resin and use the pre- of its Leaching material, metal-clad laminate and printed circuit board.
Background technique
The high speed and multifunction handled with electronic product information, applying frequency are continuously improved, it is desirable that dielectric constant (Dk) and dielectric loss value (Df) is lower and lower, therefore reduce that Dk/Df has become substrate dealer chases hot spot.Simultaneously in the whole world Under the main trend for strengthening " green " " environmental protection ", the hot spot for being developed into industry of halogen-free flame-retardant copper-clad laminate respectively covers copper Foil laminate producer all releases the halogen-free flameproof copper-clad laminate of oneself one after another.
It is optimal choosing using the low Dk/Df curing agent of high content of phosphorus to realize low Dk/Df and halogen-free flameproof simultaneously It selects.Through studying, not only phosphorus content is higher for phosphorous bis-phenol, is able to achieve halogen-free flameproof；The phosphorous bis-phenol is also used as epoxy simultaneously The curing agent of resin, the solidfied material of generation have higher glass transition temperature, excellent dielectric properties, high-fire resistance and High adhesion.But due to ester structure containing phosphonic acids in the phosphorous bis-phenol structure, solidfied material water absorption rate is very high, and high water absorbing capacity not only can Plate dielectric properties are caused obviously to deteriorate because of the moisture absorption, it is also possible to it is heated and quick-fried after the moisture absorption in PCB processing to will lead to substrate Plate.Therefore under the premise of guaranteeing excellent dielectric properties, how to reduce the water absorption rate of phosphorous bis-phenol system and improve solidfied material Glass transition temperature becomes a technical problem.
Copper-clad plate benzoxazine resin commonly used in the trade reduces solidfied material water absorption rate, however the dielectricity of benzoxazine resin Can be poor, the dielectric properties of the meeting phosphorous bis-phenol system of severe exacerbation.
CN104761719A discloses a kind of both-end Quito functional activity ester resin containing PPO main chain, with lower institute The structure shown:Wherein R1 isR2 isSubstituted or unsubstituted Cl-C3 straight chained alkyl or branched alkane Base, allyl or isoolefine propyl；R3For H, allyl or isoolefine propyl；R4、R5、R6、R7It is independently selected from H, substituted or unsubstituted C1-C3 straight chained alkyl or branched alkyl, allyl, isoolefine propyl or-O-R8；R8For substituted or unsubstituted C1-C3 straight chained alkyl Or branched alkyl or substituted or unsubstituted phenyl, n1, n2 are the positive integer greater than 0, and meet 4≤n1+n2≤25, n3, n4 It is equal or different, it independently is 1,2 or 3.By prepreg, the laminate of the compositions of thermosetting resin production containing the active ester And copper-clad plate, there is excellent dielectric properties, humidity resistance, heat resistance and extremely low water absorption rate and higher bending strength. Both-end Quito functional activity ester both ends ester group can react with epoxy resin, however due to the influence of steric hindrance, not It is that all ester groups can be cured crosslinking；Intermediate PPO main chain and R1 structure does not have reactive group (R1ForIt is right) Or solidification crosslinked group is double bond, is never reacted with epoxy resin.Therefore both-end Quito functional activity ester resin The crosslink density reacted with epoxy resin is not high, and intermediate PPO main chain is thermoplastic segments, and thermal expansion coefficient (CTE) is high, most The glass transition temperature of final curing object or plate is lower, thermal expansion coefficient (CTE) is high.
In the art, how guarantee copper-clad plate have higher glass transition temperature while, reduce its water absorption rate, Thermal expansion coefficient and dielectric loss are this field urgent problems to be solved.
Summary of the invention
In view of the deficiencies of the prior art, the present invention intends to provide a kind of compositions of thermosetting resin and use Its prepreg, metal-clad laminate and printed circuit board.Using the compositions of thermosetting resin preparation laminate and cover Metal foil laminate has high glass-transition temperature, low water absorption, low-k, low-dielectric loss factor, high-fire resistance And good anti-flammability, processing performance and chemical resistance.
To achieve this purpose, the present invention adopts the following technical scheme:
In a first aspect, the present invention provides a kind of compositions of thermosetting resin, which is characterized in that the thermosetting resin combination Object includes following component: epoxy resin, phosphorous bis-phenol and esters curing agent；
The esters curing agent has Formulas I structure:
Wherein, R1-R8It is each independently selected from hydrogen atom, C1-C10Aliphatic alkyl, C3-C10Alicyclic alkyl or C6-C10 One of aromatic hydrocarbyl, and it is not all hydrogen atom；
X is selected from-O- ,-S- ,-CH2Or-C (CH3)2One of；
Y is selected from C1-C10Aliphatic alkyl, C3-C10Alicyclic alkyl or C6-C10One of aromatic hydrocarbyl；
N is the integer of 1-10.
The present invention uses the esters curing agent with Formulas I structure to cooperate with cured epoxy resin with phosphorous bis-phenol, with phosphorous pair Phenol is main curing agent, imparts the excellent dielectric properties of solidfied material, high-fire resistance and bonding force, while being also able to achieve Halogen resistance Combustion, the esters curing agent of convolution I structure can guarantee so that not generating secondary hydroxyl isopolarity group in the curing process Solidfied material glass transition temperature is significantly improved while dielectric properties are excellent, and contains a large amount of hydrophobic groupings in cured product, Solidfied material water absorption rate can be greatly reduced, so that solidfied material dielectric constant and dielectric loss factor are more stable.Use the resin group Close prepreg made of object, laminate for printed circuits has high glass-transition temperature, low water absorption, low-k, low Dielectric loss factors, high-fire resistance and good anti-flammability, processing performance and chemical resistance.
In the present invention, the C1-C10Aliphatic alkyl refer to containing 1-10 (such as 1,2,3,4,5,6, 7,8,9 or 10) aliphatic alkyl of carbon atom；Such as can be methyl, ethyl, propyl, butyl, amyl, hexyl, Heptyl, octyl, nonyl or decyl etc..
The C3-C10Alicyclic alkyl refers to containing 3-10 (such as 3,4,5,6,7,8,9 or 10 It is a) alicyclic alkyl of carbon atom；Such as can be cyclopropyl, cyclobutyl, cyclopenta or cyclohexyl etc..
The C6-C10Aromatic hydrocarbyl refers to the rouge containing 6-10 (such as 6,7,8,9 or 10) carbon atoms Fat race alkyl；Such as can be phenyl, benzyl, phenethyl or phenylpropyl etc..
N can be 1,2,3,4,5,6,7,8,9 or 10 in Formulas I.
As the preferred technical solution of the present invention, with the total weight of the epoxy resin, phosphorous bis-phenol and esters curing agent Number is 100 parts of meters, and the compositions of thermosetting resin includes: 40-75 parts of epoxy resin, 15-40 parts of phosphorous bis-phenols and 5-25 Part esters curing agent.
Unless otherwise specified, heretofore described " esters curing agent " each means the esters curing agent with Formulas I structure.
In the present invention, the parts by weight of the epoxy resin can be 40 parts, 42 parts, 45 parts, 48 parts, 50 parts, 52 parts, 55 Part, 58 parts, 60 parts, 62 parts, 65 parts, 68 parts, 70 parts, 75 parts etc..
The parts by weight of the phosphorous bis-phenol can be 15 parts, 16 parts, 18 parts, 20 parts, 22 parts, 23 parts, 25 parts, 26 parts, 28 parts, 30 parts, 32 parts, 33 parts, 35 parts, 38 parts or 40 parts etc..
The parts by weight of the esters curing agent can be 5 parts, 6 parts, 8 parts, 10 parts, 12 parts, 13 parts, 15 parts, 16 parts, 18 Part, 20 parts, 22 parts, 23 parts or 25 parts etc..
The present invention is cooperated under above-mentioned specific ratio by epoxy resin, phosphorous bis-phenol and esters curing agent, energy Enough comprehensive performances for further promoting its solidfied material and laminate prepared therefrom.If the additive amount of epoxy resin is very few, can lead Cause the processing performance of solidfied material and laminate poor；If the additive amount of epoxy resin is excessive, solidfied material and laminate will lead to Glass transition temperature it is lower, dielectric properties are poor.If the additive amount of phosphorous bis-phenol is very few, solidfied material and laminate it is tough Poor, the fire-retardant deficiency of property；If the additive amount of phosphorous bis-phenol is excessive, the glass transition temperature of solidfied material and laminate is low.If The additive amount of the esters curing agent is very few, then for reducing the water absorption rate of cured product or laminate and improving glass transition The effect of temperature is unobvious, if the additive amount of the esters curing agent is excessive, will lead to the brittleness of cured product and laminate It is larger, poor processability.
As the preferred technical solution of the present invention, the epoxy resin is halogen-free epoxy resin.
Preferably, the halogen-free epoxy resin is selected from bisphenol A type epoxy resin, bisphenol f type epoxy resin, o-cresol phenolic aldehyde Epoxy resin, bisphenol A-type novolac epoxy resin, three phenolic novolac epoxy resins, dicyclopentadiene novolac epoxy resin, biphenyl type One of novolac epoxy resin, alkyl benzene-type novolac epoxy resin or naphthol type novolac epoxy resin or at least two group It closes.
Preferably, the halogen-free epoxy resin has Formula II structure:
Wherein, X1、X2And X3It is each independentlyR9Selected from hydrogen atom, replace or Unsubstituted C1-C5Straight chained alkyl or substituted or unsubstituted C3-C5One of branched alkyl；
Y1And Y2It is each independently selected from singly-bound ,-CH2-、 One of, R10Selected from hydrogen atom, Substituted or unsubstituted C1-C5Straight chained alkyl or substituted or unsubstituted C3-C5One of branched alkyl；
M is the integer of 1-10；Such as it can be 1,2,3,4,5,6,7,8,9 or 10.
In the present invention, the C1-C5Straight chained alkyl refers to former containing 1-5 (such as 1,2,3,4 or 5) carbon The straight chained alkyl of son；Such as it can be methyl, ethyl, propyl, butyl or amyl.
The C3-C5Branched alkyl refers to the branched alkyl containing 3-5 (such as 3,4 or 5) carbon atoms；Such as It can be isopropyl, isobutyl group, tert-butyl or isopentyl etc..
Halogen-free epoxy resin degree of functionality with higher and good dielectric properties with Formula II structure, facilitate into one Step improves the glass transition temperature of cured product, reduces dielectric loss and water absorption rate.
As the preferred technical solution of the present invention, the phosphorous bis-phenol has formula III structure:
Wherein k is the integer (such as 2,3,4,5,6,7,8,9,10,12,15,18 or 20 etc.) of 2-20, and preferably 3-10's is whole Number.
Preferably, the weight average molecular weight of the phosphorous bis-phenol is 1000-10000；Such as can be 1000,2000,3000, 4000,5000,6000,7000,8000 or 10000 etc..Preferably 1000-6500, more preferably 1000-4500.
As the preferred technical solution of the present invention, the compositions of thermosetting resin further includes fire retardant.
Preferably, the fire retardant is phosphonium flame retardant.
Preferably, described in terms of by the total weight number of the epoxy resin, phosphorous bis-phenol and esters curing agent for 100 parts The additive amount of phosphonium flame retardant be 0-50 parts, such as can be 0 part, 1 part, 2 parts, 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 35 parts, 40 parts, 45 parts or 50 parts etc.；Further preferably 0-30 parts.
Preferably, the phosphonium flame retardant is selected from three (2,6- 3,5-dimethylphenyl) phosphines, 10- (2,5- dihydroxy phenyl) -9, Miscellaneous -10- phosphine phenanthrene -10- the oxide of 10- dihydro-9-oxy, 2,6- bis- (2,6- 3,5-dimethylphenyl) phosphino- benzene, 10- phenyl -9,10- bis- Hydrogen -9- oxa- -10- phosphine phenanthrene -10- oxide, phenoxy phosphazene compound, phosphate, polyphosphate, phosphonate ester or polyphosphonates One of or at least two combination.
As the preferred technical solution of the present invention, the compositions of thermosetting resin further includes curing accelerator, makes resin Composition solidifies and accelerates the curing rate of resin combination.
Preferably, described in terms of by the total weight number of the epoxy resin, phosphorous bis-phenol and esters curing agent for 100 parts The additive amount of curing accelerator is 0.05-1 parts；Such as can be 0.05 part, 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part or 1 part etc..
Preferably, the curing accelerator is selected from glyoxaline compound, triphenylphosphine, dimethylamino naphthyridine, boron trifluoride One of mono aminoethane or zinc octoate or at least two combination.
Preferably, the glyoxaline compound be selected from 2-methylimidazole, 2-ethyl-4-methylimidazole, 2- phenylimidazole or One of 2- undecyl imidazole or at least two combination.
As the preferred technical solution of the present invention, the compositions of thermosetting resin further includes filler, to further decrease The thermal expansion coefficient (CTE) and water absorption rate of cured product and laminate improve thermal conductivity.
Preferably, described in terms of by the total weight number of the epoxy resin, phosphorous bis-phenol and esters curing agent for 100 parts The additive amount of filler be 0-150 parts, such as can be 0 part, 1 part, 2 parts, 5 parts, 8 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts, 100 parts, 110 parts, 120 parts, 130 parts, 140 parts or 150 parts Deng；Further preferably 0-100 parts.
Preferably, the filler is organic filler and/or inorganic filler.
Preferably, the inorganic filler be selected from silica, aluminium hydroxide, aluminium oxide, talcum powder, aluminium nitride, boron nitride, One of silicon carbide, barium sulfate, barium titanate, strontium titanates, calcium carbonate, calcium silicates, mica, glass fiber powder or at least two Combination.
Preferably, the organic filler be selected from one of polytetrafluorethylepowder powder, polyphenylene sulfide or polyether sulfone powder or At least two combination.
In the present invention, the filler is most preferably silica, such as can be fused silica, crystal type titanium dioxide Silicon, spherical silica or hollow silicon dioxide etc.；In partial size angle value be 1-15 μm, such as can be 1 μm, 2 μm, 3 μm, 5 μm, 6 μm, 8 μm, 10 μm, 12 μm, 13 μm or 15 μm etc.；Further preferably 1-10 μm.The filler of particle diameter distribution within the above range There is preferably dispersibility in compositions of thermosetting resin.
Second aspect, the present invention provide a kind of resin adhesive liquid, and resin adhesive liquid described in the resin adhesive liquid is by such as first party Compositions of thermosetting resin described in face, which is dissolved or dispersed in solvent, to be obtained.
As the solvent in the present invention, there is no particular limitation, can select the alcohols such as methanol, ethyl alcohol, butanol, and ethyl is molten Fine agent, butyl cellosolve, ethylene glycol monomethyl ether, carbitol, butyl carbitol etc., acetone, butanone, methyl ethyl ketone, cyclohexanone Equal ketones, the arenes such as toluene, dimethylbenzene, the esters such as ethyl acetate, ethoxyethyl acetate, N, N- dimethyl formyl The nitrogen-containing solvents such as amine, n,N-dimethylacetamide.The above solvent can be used alone, can also two or more mixing make With.It is preferred that the ketones such as acetone, butanone, methyl ethyl ketone, cyclohexanone.The additive amount of the solvent is by those skilled in the art's root It is selected according to oneself experience, so that resin adhesive liquid reaches the viscosity for being suitble to use.
The solvent is preferably butanone (MEK), and the solid content of the glue is preferably 60-70%.
The third aspect, the present invention provide a kind of prepreg, including reinforcing material, and described by being attached to after impregnation drying The compositions of thermosetting resin that first aspect present invention on reinforcing material provides.
In the present invention, prepreg can be prepared with the following method:
It is impregnated with reinforcing material using the resin adhesive liquid of the compositions of thermosetting resin, obtains prepreg after dry.
Wherein, the reinforcing material is preferably glass cloth, and glue impregnation amount is preferably 200-230g/m2, the drying Temperature is preferably 155 DEG C, and the time is preferably 5-10min.
Fourth aspect, the present invention provide a kind of laminate, including one or at least two overlapping third aspect present invention The prepreg of offer.
5th aspect, the present invention provides a kind of metal-clad laminate, the third of the present invention including one or at least overlapped The metal foil of prepreg and the one or both sides being overlying on the outside of the prepreg that aspect provides.
By that first at least will be adhesively-bonded together to form laminate by two prepregs, then again the metal-clad laminate is Metal foil is pasted in laminate one or both sides, the method for finally heated cure under pressure is prepared.
The operation of the heating pressurization can be carried out by laminating machine, and lamination must meet claimed below: the heating being 1. laminated Rate should usually be controlled at 80-120 DEG C of material temperature in 1.5-2.5 DEG C/min；2. the pressure setting being laminated, outer layer material temperature is in 120- 150 DEG C apply full pressure, and full pressure pressure is 350psi or so；3. solidify, material temperature is controlled at 200 DEG C, and keep the temperature 90min.
The metal foil can be copper foil, nickel foil, aluminium foil or SUS foil (stainless steel foil) etc..
6th aspect, the present invention provide a kind of printed circuit board, and the printed circuit board includes at least one as described above Prepreg.
Compared with prior art, the invention has the following advantages:
The present invention uses the esters curing agent with Formulas I structure to cooperate with cured epoxy resin with phosphorous bis-phenol, with phosphorous pair Phenol is main curing agent, imparts the excellent dielectric properties of solidfied material, high-fire resistance, bonding force and toughness, while being also able to achieve nothing Halogen is fire-retardant.The esters curing agent of convolution I structure can be so that do not generate secondary hydroxyl isopolarity group in the curing process Guarantee to significantly improve solidfied material glass transition temperature while dielectric properties are excellent, and contains a large amount of hydrophobic groups in cured product Group, can be greatly reduced solidfied material water absorption rate, make up the problem that phosphorous bis-phenol brings water absorption rate high because of phosphorus content height, so that solidfied material Dielectric constant and dielectric loss factor are more stable.Using the vitrifying for the laminate that the compositions of thermosetting resin is prepared Transition temperature is 172-196 DEG C, thermal expansion coefficient 2.1%-2.8%, water absorption rate 0.20%-0.32%, dielectric constant (1GHz) is 3.48-3.71, and dielectric loss factor (1GHz) is 0.0071-0.0089, and dielectric constant is 3.58- after humidity 3.89, it is moist after dielectric loss factor be 0.0078-0.0105,288 DEG C of layering cream time > 120s, peel strength is 1.38-1.48N/mm drop impact slight crack area is 192-325mm2, difficult to burn reaches V-0 grades, with good heat-resisting Property, moisture-proof, peel strength, dielectric properties and anti-flammability.
Specific embodiment
Below by specific embodiment to further illustrate the technical scheme of the present invention.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.
The source of material involved in the embodiment of the present invention and comparative example/the preparation method is as follows:
(A) halogen-free epoxy resin
(A-1) dicyclopentadiene novolac epoxy resin HP-7200H (big Japanese ink trade name)；
(A-2) biphenyl type novolac epoxy resin NC-3000 (the Japanization pharmacist name of an article)；
(A-3) HP-9900 containing naphthalene epoxy resins (big Japanese ink trade name).
(B) phosphorus curing agent
(B-1) (U.S.'s FRX Polymers trade name, phosphorus content 10.8%, weight average molecular weight are phosphorous bis-phenol OL3001 3000)；
(B-2) (U.S.'s FRX Polymers trade name, phosphorus content 10%, weight average molecular weight are phosphorous bis-phenol OL5000 5000)；
(B-3) phosphorus-containing phenolic aldehyde XZ-92741 (U.S.'s DOW trade name, phosphorus content 9%).
(C) co-curing agent
(C-1a) with the esters curing agent of Formulas I structure, structure are as follows:
Wherein average repeat unit n is 1.25；
Preparation method is as follows:
In the flask for being equipped with thermometer, dropping funel, blender put into 2mol (568.78g) bisphenol-A and 1500g tetrahydrofuran, is passed through nitrogen, and stirring is to being completely dissolved.Then, investment 1mol (203.02g) paraphthaloyl chloride stirring Then dissolution controls system temperature at 20 DEG C hereinafter, being slowly added dropwise and (being greater than 0.5 hour) 2mol (202.38g) triethylamine (triethylamine/tetrahydrofuran solution dropwise addition for being configured to 20%).Then, continue to be stirred to react 2~3 hours at 20 DEG C or less.It connects , 2mol (381.25g) 2- naphthoyl chloride is put into, system temperature is controlled at 15 DEG C hereinafter, 2mol is then slowly added dropwise (202.38g) triethylamine (triethylamine/tetrahydrofuran solution dropwise addition for being configured to 20%), continues to be stirred to react 2 at 15 DEG C or less ~5 hours.It stands after the reaction was completed, is filtered to remove triethylamine hydrochloride solid, carries out vacuum distillation concentration in solution, then again Methanol is added, resin product is precipitated, filtering, being washed with water to the pH value of final water layer is 7, and again with methanol washing is then so dry that produce Object.The ester equivalent of prepared active ester resin is 252g/eq according to feed ratio.
(C-1b) with the esters curing agent of Formulas I structure, structure are as follows:
Wherein average repeat unit n is 1.25；
Preparation method is as follows:
In the flask for being equipped with thermometer, dropping funel, blender put into 2mol (568.78g) bisphenol-A and 1500g tetrahydrofuran, is passed through nitrogen, and stirring is to being completely dissolved.Then, investment 1mol (203.02g) paraphthaloyl chloride stirring Then dissolution controls system temperature at 20 DEG C hereinafter, being slowly added dropwise and (being greater than 0.5 hour) 2mol (202.38g) triethylamine (triethylamine/tetrahydrofuran solution dropwise addition for being configured to 20%).Then, continue to be stirred to react 2~3 hours at 20 DEG C or less.It connects , 2mol (281.14g) chlorobenzoyl chloride is put into, system temperature is controlled at 15 DEG C hereinafter, 2mol is then slowly added dropwise (202.38g) triethylamine (triethylamine/tetrahydrofuran solution dropwise addition for being configured to 20%), continues to be stirred to react 2 at 15 DEG C or less ~5 hours.It stands after the reaction was completed, is filtered to remove triethylamine hydrochloride solid, carries out vacuum distillation concentration in solution, then again Methanol is added, resin product is precipitated, filtering, being washed with water to the pH value of final water layer is 7, and again with methanol washing is then so dry that produce Object.The ester equivalent of prepared active ester resin is 226g/eq according to feed ratio.
(C-1c) with the esters curing agent of Formulas I structure, structure are as follows:
Wherein average repeat unit n is 1.25；
Preparation method is as follows:
In the flask for being equipped with thermometer, dropping funel, blender put into 2mol (512.66g) tetramethyl Bisphenol F and 1500g tetrahydrofuran, is passed through nitrogen, and stirring is to being completely dissolved.Then, investment 1mol (203.02g) paraphthaloyl chloride stirring Then dissolution controls system temperature at 20 DEG C hereinafter, being slowly added dropwise and (being greater than 0.5 hour) 2mol (202.38g) triethylamine (triethylamine/tetrahydrofuran solution dropwise addition for being configured to 20%).Then, continue to be stirred to react 2~3 hours at 20 DEG C or less.It connects , 2mol (157g) chloroacetic chloride is put into, system temperature is controlled at 15 DEG C hereinafter, 2mol (202.38g) three is then slowly added dropwise Ethamine (triethylamine/tetrahydrofuran solution dropwise addition for being configured to 20%), continues to be stirred to react 2~5 hours at 15 DEG C or less.Reaction It stands after the completion, is filtered to remove triethylamine hydrochloride solid, carries out vacuum distillation concentration in solution, then add methanol precipitation Resin product, filtering, being washed with water to the pH value of final water layer is 7, again with methanol washing, then dry product.Prepared The ester equivalent of active ester resin is 181g/eq according to feed ratio.
(C-2) a kind of esters curing agent V-575 (Japanese UNITIKA trade name), structure is as follows:
Wherein average repeat unit n is 1.25；
(C-3) dicyclopentadiene phenolic active ester HPC-8000T65 (big Japanese ink trade name)；
(C-4) bisphenol A cyanate ester prepolymer CE01PS (Yangzhou apocalypse trade name)；
(C-5) dicyclopentadiene type benzoxazine LZ 8260N70 (HUNTSMAN trade name).
(D) additive flame retardant
Phenoxy phosphazene compound SPB-100 (Mitsubishi trade name).
(E) curing accelerator
4-dimethylaminopyridine (the wide flourish commodity chemical name of Japan).
(F) filler
(F-1) ball-type silicon powder (average grain diameter is 1-10 μm, 99% or more purity)；
(F-2) aluminium oxide (average grain diameter is 1-10 μm, 99% or more purity).
Embodiment 1-16
Embodiment 1-16 provides compositions of thermosetting resin glue, the prepreg using it and copper-clad plate, and preparation method is such as Under:
(1) preparation of compositions of thermosetting resin glue:
With MEK solvent by component (B) phosphorus curing agent, the agent of (C) co-curing and (D) phenoxy phosphazene compound SPB-100 It is configured to the solution that solid content is 60%, 50% and 25% respectively, is added sequentially in 1000mL beaker, sequentially adds (A) Halogen-free epoxy resin and (F) filler are added appropriate (E) curing accelerator 4-dimethylaminopyridine, adjust gelation time (GT) To 200-300s, it is 65% that MEK solvent, which is added, by solid content control, continues to stir 2h curing, obtains thermosetting resin combination Composition glue liquid；
Wherein, the type and dosage (based on parts by weight) of each component are as shown in table 1, table 2.
(2) preparation of prepreg:
It is ready to 6 2116 glass cloth (manufacturer: stopping Bell Co. in Taiwan), size: 320mm*380mm, it first will be upper It states compositions of thermosetting resin glue to be coated on every glass cloth, make glue Sized glass cloth and is stained with resin on two surfaces, so Two surfaces are struck off and are removed part glue by the folder axis of roll-in by the glass cloth after infiltration afterwards, by glass cloth and removal solvent The sum of resin composition weight afterwards is controlled in 200-230g/m2, the glass cloth presoaked is obtained, puts it into 155 DEG C later 6-8min is toasted in baking oven, obtains prepreg.
(3) production of copper-clad plate:
Prepare 2 with a thickness of 35 μm, the electrolytic copper foil having a size of 410mm*410mm (manufacturer: Suzhou Feitian), by 6 Zhang Shangshu prepreg gathers into folds, and keeps 4 angle alignments, and respectively cover the electrolysis being ready in the prepreg upper and lower surface folded Copper foil is put into laminating machine, and lamination is carried out as follows: the heating rate being 1. laminated should be controlled at 80-120 DEG C of material temperature 1.5-2.5℃/min；2. the pressure setting being laminated, outer layer material temperature applies full pressure at 120-150 DEG C, and full pressure pressure is 350psi； 3. solidify, material temperature is controlled at 200 DEG C, and keep the temperature 90min, obtain copper-clad plate.
Comparative example 1
Comparative example 1 and the difference of embodiment 7 are that the type of component (B) phosphorus curing agent is different, 3 institute of table specific as follows Show.
Comparative example 2-5
Comparative example 2-5 and the difference of embodiment 5 are that the type of component (C) curing agent is different, shown in table 3 specific as follows.
Comparative example 6-9
Comparative example 6-9 and the difference of embodiment 16 are that the type of component (C) curing agent is different, 3 institute of table specific as follows Show.
The performance of the copper-clad plate provided respectively above-described embodiment and comparative example is tested, and testing standard/method is as follows:
(a) glass transition temperature (Tg): according to differential scanning calorimetry (DSC), according to IPC-TM-650 2.4.25 institute Defined DSC method is measured.
(b) thermal expansion coefficient (CTE)
It is measured according to the Z-direction CTE test method of IPC-TM-650 2.4.24 defined.
(c) water imbibition
100mm × 100mm sample is placed in the climatic chamber of 85 DEG C of temperature, humidity 85% after handling 168h, test The water absorption rate of sample after processing.
(d) dielectric constant, dielectric loss factor
According to the resonance method for using stripline runs, the dielectric loss under 1GHz is measured according to IPC-TM-650 2.5.5.5, is situated between The electrical loss factor.
(e) dielectric constant, dielectric loss factor (after moist)
Sample is placed in the climatic chamber of 85 DEG C of temperature, humidity 85% after handling 168h, according still further to IPC-TM-650 2.5.5.5 the dielectric loss under measurement 1GHz, dielectric loss factor.
(f) resistance to dip solderability
Layering cream time is observed according to IPC-TM-650 2.4.13.1.
(g) peel strength
According to the experiment condition of " after thermal stress " in IPC-TM-650 2.4.8 method, the removing for testing metallic cover layer is strong Degree.
(h) drop impact slight crack area
Tested using drop hammer impact testing machine, test method: height of the fall 1m, weight of dropping hammer are 0.75kg, and release is fallen Hammer, test plate torn surface product.Plate slight crack size can tentatively reflect the toughness superiority and inferiority of plate, it is, in general, that slight crack Area is smaller to show that plate toughness is better.
(i) difficult to burn
It is measured according to 94 vertical combustion of UL.
The performance for the copper-clad plate that the various embodiments described above and comparative example provide is as shown in following table 1-3:
Table 1
Table 2
Table 3
It was found from the physical data of table 1-3: embodiment 1-9 uses 5-25 parts of esters curing agent and 15- with Formulas I structure 40-75 parts of halogen-free epoxy resins of 40 parts of phosphorous bis-phenol composite curings, obtained plate have high Tg, low CTE, low water absorption, Excellent dielectric properties, high-fire resistance and peel strength and excellent toughness, while being also able to achieve V-0 grades of halogen-free flameproof.
It is bicyclic using the esters curing agent with Formulas I structure and phosphorous 78 parts of bis-phenol OL3001 composite curing in embodiment 10 Pentadiene novolac epoxy resin HP-7200H is preferably used since the dosage of dicyclopentadiene novolac epoxy resin HP-7200H exceeds Measure range, lead to reaction not exclusively, final plate Tg decreases, CTE and water absorption rate is all increased, dielectric properties are poor and Heat resistance is not ideal enough.
It is bicyclic using the esters curing agent with Formulas I structure and phosphorous 38 parts of bis-phenol OL3001 composite curing in embodiment 11 Pentadiene novolac epoxy resin HP-7200H, plate have higher Tg and lower CTE, but since epoxy resin is insufficient, solid Agent is excessive, and final plate water absorption rate is higher, dielectric properties are poor and heat resistance is not ideal enough.
It is bicyclic using the esters curing agent and 42 parts of phosphorous bis-phenol OL3001 composite curings with Formulas I structure in embodiment 12 Pentadiene novolac epoxy resin HP-7200H, since the dosage of the phosphorous bis-phenol OL3001 of curing agent exceeds preferred amount ranges, most Soleplate material Tg is slightly lower and water absorption rate is high, and plate dielectric properties deteriorate serious after the moisture absorption.
It is bicyclic using the esters curing agent and 8 parts of phosphorous bis-phenol OL3001 composite curings with Formulas I structure in embodiment 13 Pentadiene novolac epoxy resin HP-7200H, since the phosphorous bis-phenol OL3001 additive amount of curing agent is lower, epoxy resin is excessively solid Change not exclusively, final plate CTE is higher and dielectric properties are general.
It is bicyclic using 27 parts of esters curing agent with Formulas I structure and phosphorous bis-phenol OL3001 composite curing in embodiment 14 Pentadiene novolac epoxy resin HP-7200H, plate has high Tg, low CTE, low water absorption and excellent dielectric properties, but is used to The drop impact test slight crack area for characterizing toughness is excessive, and plate poor toughness is unfavorable for the PCB processing in downstream.
It is bicyclic using 3 parts of esters curing agent with Formulas I structure and phosphorous bis-phenol OL3001 composite curing in embodiment 15 Pentadiene novolac epoxy resin HP-7200H, final plate Tg be relatively low, CTE high and water absorption rate are high, plate dielectric properties after the moisture absorption Deteriorate serious.
Esters curing agent and phosphorous bis-phenol OL3001 composite curing bicyclic penta 2 with Formulas I structure are used in embodiment 16 Alkene novolac epoxy resin HP-7200H does not add filler, and the CTE and water absorption rate of plate are increased, but are remained at more satisfactory Level, while plate has high Tg, excellent dielectric properties, heat resistance and toughness.
As described above, being prepared compared with general Halogen laminate using compositions of thermosetting resin provided by the invention Laminate there is higher Tg, lower CTE, lower water absorption rate, superior dielectric properties and peel strength, heat-resisting Property, toughness, be suitable for high-speed applications field.In addition content of halogen of the present invention can reach difficult within the scope of JPCA Halogen standard requirements V-0 standard in combustion property test UL94, there is environmental protection.
Esters curing agent and phosphorus-containing phenolic aldehyde XZ-92741 composite curing dicyclopentadiene in comparative example 1 with Formulas I structure Novolac epoxy resin HP-7200H, since phosphorus-containing phenolic aldehyde reactivity is too low, final plate Tg is low, CTE high and dielectric properties and Poor heat resistance.
Esters curing agent V-575 and phosphorous bis-phenol OL3001 composite curing dicyclopentadiene phenolic aldehyde ring are used in comparative example 2 Oxygen resin HP-7200H, plate has high Tg, low CTE, excellent heat resistance and toughness, but dielectric properties are general, water absorption rate compared with Dielectric properties after the high and plate moisture absorption are poor.
Dicyclopentadiene phenolic active ester HPC-8000T65 and phosphorous bis-phenol OL3001 composite curing are used in comparative example 3 Dicyclopentadiene novolac epoxy resin HP-7200H, final plate have excellent dielectric properties, but Tg is relatively low, water absorption rate is high and Plate dielectric properties deteriorate serious after the moisture absorption.
Bisphenol A cyanate ester prepolymer CE01PS and phosphorous bis-phenol OL3001 composite curing bicyclic penta are used in comparative example 4 Diene novolac epoxy resin HP-7200H, plate has high Tg, low CTE, excellent dielectric properties and heat resistance, but water absorption rate is high And the dielectric properties after the plate moisture absorption are poor.
It is double using dicyclopentadiene type benzoxazine LZ 8260N70 and phosphorous bis-phenol OL3001 composite curing in comparative example 5 Cyclopentadiene novolac epoxy resin HP-7200H, plate has low water absorption, excellent dielectric constant and heat resistance, but Tg is inclined Low, CTE and dielectric loss factor are high.
Esters curing agent V-575 and phosphorous bis-phenol OL3001 composite curing dicyclopentadiene phenolic aldehyde ring are used in comparative example 6 Oxygen resin HP-7200H, does not add filler, and plate has high Tg, low CTE and excellent dielectric constant, but water absorption rate height and plate Dielectric properties after the moisture absorption are poor, and heat resistance is also undesirable.
Dicyclopentadiene phenolic active ester HPC-8000T65 and phosphorous bis-phenol OL3001 composite curing are used in comparative example 7 Dicyclopentadiene novolac epoxy resin HP-7200H, does not add filler, and final plate has an excellent dielectric properties, but Tg it is low, Plate dielectric properties deteriorate serious after CTE high, water absorption rate height and the moisture absorption.
Bisphenol A cyanate ester prepolymer CE01PS and phosphorous bis-phenol OL3001 composite curing bicyclic penta are used in comparative example 8 Diene novolac epoxy resin HP-7200H, does not add filler, and plate has high Tg, low CTE, excellent dielectric properties and heat-resisting Property, but the dielectric properties after water absorption rate height and the plate moisture absorption are poor.
It is double using dicyclopentadiene type benzoxazine LZ8260N70 and phosphorous bis-phenol OL3001 composite curing in comparative example 9 Cyclopentadiene novolac epoxy resin HP-7200H, does not add filler, and plate has low water absorption and excellent dielectric constant, palette Material Tg is relatively low, CTE and dielectric loss factor are higher, and heat resistance is undesirable.
The Applicant declares that the foregoing is merely a specific embodiment of the invention, but protection scope of the present invention not office It is limited to this, it should be clear to those skilled in the art, any to belong to those skilled in the art and take off in the present invention In the technical scope of dew, any changes or substitutions that can be easily thought of, and 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 following component: asphalt mixtures modified by epoxy resin Rouge, phosphorous bis-phenol and esters curing agent；
The esters curing agent has Formulas I structure:
Wherein, R1-R8It is each independently selected from hydrogen atom, C1-C10Aliphatic alkyl, C3-C10Alicyclic alkyl or C6-C10Fragrance One of race's alkyl, and it is not all hydrogen atom；
X is selected from-O- ,-S- ,-CH2Or-C (CH3)2One of；
Y is selected from C1-C10Aliphatic alkyl, C3-C10Alicyclic alkyl or C6-C10One of aromatic hydrocarbyl；
N is the integer of 1-10.
2. compositions of thermosetting resin according to claim 1, which is characterized in that with the epoxy resin, phosphorous bis-phenol Be 100 parts of meters with the total weight number of esters curing agent, the compositions of thermosetting resin include: 40-75 parts of epoxy resin, 15-40 parts of phosphorous bis-phenols and 5-25 parts of esters curing agent.
3. compositions of thermosetting resin according to claim 1 or 2, which is characterized in that the epoxy resin is Halogen ring Oxygen resin；
Preferably, the halogen-free epoxy resin is selected from bisphenol A type epoxy resin, bisphenol f type epoxy resin, o-cresol epoxy novolac Resin, bisphenol A-type novolac epoxy resin, three phenolic novolac epoxy resins, dicyclopentadiene novolac epoxy resin, biphenyl type phenolic aldehyde One of epoxy resin, alkyl benzene-type novolac epoxy resin or naphthol type novolac epoxy resin or at least two combination；
Preferably, the halogen-free epoxy resin has Formula II structure:
Wherein, X1、X2And X3It is each independentlyR9Selected from hydrogen atom, substituted or unsubstituted C1-C5Straight chained alkyl or substituted or unsubstituted C3-C5One of branched alkyl, Y1And Y2It is each independently selected from list Key ,-CH2-、 One of, R10Selected from hydrogen atom, Substituted or unsubstituted C1-C5Straight chained alkyl or substituted or unsubstituted C3-C5One of branched alkyl；M is the whole of 1-10 Number.
4. compositions of thermosetting resin according to claim 1-3, which is characterized in that the phosphorous bis-phenol has Structure shown in formula III:
Wherein k is the integer of 2-20, the preferably integer of 3-10；
Preferably, the weight average molecular weight of the phosphorous bis-phenol independently is 1000-10000, preferably 1000-6500, more preferably For 1000-4500.
5. compositions of thermosetting resin according to claim 1-4, which is characterized in that the thermosetting resin group Closing object further includes fire retardant；
Preferably, the fire retardant is phosphonium flame retardant；
Preferably, described phosphorous in terms of by the total weight number of the epoxy resin, phosphorous bis-phenol and esters curing agent for 100 parts The additive amount of fire retardant is 0-50 parts, further preferably 0-30 parts；
Preferably, the phosphonium flame retardant is selected from three (2,6- 3,5-dimethylphenyl) phosphines, 10- (2,5- dihydroxy phenyl) -9,10- bis- Hydrogen -9- oxa- -10- phosphine phenanthrene -10- oxide, 2,6- bis- (2,6- 3,5-dimethylphenyl) phosphino- benzene, 10- phenyl -9,10- dihydro -9- In oxa- -10- phosphine phenanthrene -10- oxide, phenoxy phosphazene compound, phosphate, polyphosphate, phosphonate ester or polyphosphonates It is a kind of or at least two combination；
Preferably, the compositions of thermosetting resin further includes curing accelerator；
It preferably, is the solidification in terms of 100 parts by the total weight number of the epoxy resin, phosphorous bis-phenol and esters curing agent The additive amount of promotor is 0.05-1 parts；
Preferably, the curing accelerator is selected from glyoxaline compound, triphenylphosphine, dimethylamino naphthyridine, boron trifluoride list second One of amine or zinc octoate or at least two combination；
Preferably, the glyoxaline compound is selected from 2-methylimidazole, 2-ethyl-4-methylimidazole, 2- phenylimidazole or 2- ten One of one alkyl imidazole or at least two combination；
Preferably, the compositions of thermosetting resin further includes filler；
It preferably, is the filler in terms of 100 parts by the total weight number of the epoxy resin, phosphorous bis-phenol and esters curing agent Additive amount be 0-150 parts, further preferably 0-100 parts；
Preferably, the filler is organic filler and/or inorganic filler；
Preferably, the inorganic filler is selected from silica, aluminium hydroxide, aluminium oxide, talcum powder, aluminium nitride, boron nitride, carbonization One of silicon, barium sulfate, barium titanate, strontium titanates, calcium carbonate, calcium silicates, mica, glass fiber powder or at least two group It closes；
Preferably, the organic filler is selected from one of polytetrafluorethylepowder powder, polyphenylene sulfide or polyether sulfone powder or at least Two kinds of combination；
Preferably, the filler is silica, and angle value is 1-15 μm, further preferably 1-10 μm in partial size.
6. a kind of resin adhesive liquid, which is characterized in that resin adhesive liquid described in the resin adhesive liquid is will be any in such as claim 1-5 Compositions of thermosetting resin described in, 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 described by being attached to after impregnation drying Compositions of thermosetting resin as described in any one in claim 1-5 on reinforcing material.
8. a kind of laminate, which is characterized in that the laminate includes the as claimed in claim 7 of one or at least two overlapping Prepreg.
9. a kind of metal-clad laminate, which is characterized in that the metal-clad laminate include one or at least overlap as The metal foil of prepreg as claimed in claim 7 and the one or both sides being overlying on the outside of the prepreg.
10. a kind of printed circuit board, which is characterized in that the printed circuit board includes at least one as claimed in claim 7 Prepreg.
CN201811606732.XA 2018-12-26 2018-12-26 Thermosetting resin composition, and prepreg, metal foil-clad laminate and printed circuit board using same Active CN109694462B (en)

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