WO2018120471A1 - 含有苯并噁嗪的树脂组合物及其制备方法 - Google Patents

含有苯并噁嗪的树脂组合物及其制备方法 Download PDF

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Publication number
WO2018120471A1
WO2018120471A1 PCT/CN2017/078496 CN2017078496W WO2018120471A1 WO 2018120471 A1 WO2018120471 A1 WO 2018120471A1 CN 2017078496 W CN2017078496 W CN 2017078496W WO 2018120471 A1 WO2018120471 A1 WO 2018120471A1
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WIPO (PCT)
Prior art keywords
benzoxazine
weight
resin
epoxy resin
parts
Prior art date
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PCT/CN2017/078496
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English (en)
French (fr)
Inventor
奚龙
李江
许永静
Original Assignee
广东生益科技股份有限公司
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Application filed by 广东生益科技股份有限公司 filed Critical 广东生益科技股份有限公司
Priority to US15/736,887 priority Critical patent/US10513608B2/en
Priority to KR1020177023341A priority patent/KR101963070B1/ko
Publication of WO2018120471A1 publication Critical patent/WO2018120471A1/zh

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    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2363/02—Polyglycidyl ethers of bis-phenols
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/06—Polyhydrazides; Polytriazoles; Polyamino-triazoles; Polyoxadiazoles
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    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
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    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
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    • C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
    • C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2479/06—Polyhydrazides; Polytriazoles; Polyamino-triazoles; Polyoxadiazoles
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • 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
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0346—Organic insulating material consisting of one material containing N
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0104—Properties and characteristics in general
    • H05K2201/012—Flame-retardant; Preventing of inflammation
    • 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
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/06—Lamination
    • H05K2203/068—Features of the lamination press or of the lamination process, e.g. using special separator sheets

Definitions

  • the invention relates to the technical field of copper clad laminates, in particular to a preparation method of a benzoxazine-containing resin composition and a prepreg and a laminate prepared therefrom.
  • the industry in order to achieve bromine-free flame retardant, the industry usually uses phosphorus-containing resin or flame retardant, combined with nitrogen-containing resin or flame retardant to achieve phosphorus-bromine synergistic and high-efficiency flame retardant.
  • the benzoxazine resin contains nitrogen and, when used in combination with phosphorus, achieves a V-0 rating of UL 94 with a lower phosphorus content.
  • the curing shrinkage rate is low, and the heat and humidity resistance is good, and it is widely used.
  • the ring-opening polymerization of benzoxazine requires higher temperature, which brings difficulties for industrial mass production and becomes a difficult point for its application.
  • the oven temperature of up to 200 ° C promotes the evaporation of the low boiling point acid, and the ring opening and polymerization of the benzoxazine cannot be catalyzed in the pressing process.
  • the high-boiling organic acid remains in the resin composition, which increases the risk of the PCB being heated and delaminated during the manufacturing process. Therefore, there has been a problem with the application of benzoxazine resins.
  • one of the objects of the present invention is to provide a preparation method of a benzoxazine-containing resin composition. And prepregs and laminates made therefrom.
  • an acidic filler By adding an acidic filler to the resin composition containing benzoxazine, the polymerization of benzoxazine and epoxy resin is greatly promoted, and the curing temperature required for benzoxazine and epoxy polymerization is lowered;
  • the laminate prepared by adding the composition with acidic filler has high peeling stability, high glass transition temperature, low water absorption, high heat resistance, high bending strength and good processability, and can achieve a low coefficient of thermal expansion. .
  • the inventors conducted intensive studies and found that the above object can be attained by appropriately mixing an acidic filler with a benzoxazine-containing resin composition to prepare a resin composition.
  • a method for preparing a resin composition containing benzoxazine is:
  • the pH of the acidic filler is between 2 and 6;
  • the benzoxazine-containing resin composition contains an epoxy resin and a benzoxazine resin
  • the epoxy resin contains an epoxy resin A1 having an epoxy equivalent of between 150 and 450 and an epoxy resin A2 having an epoxy equivalent of between 451 and 1000.
  • the ring-opening polymerization reaction of benzoxazine and an epoxy resin can be catalyzed, and the self-crosslinking polymerization of benzoxazine can be promoted, thereby greatly reducing
  • the temperature required for the polymerization of benzoxazine and epoxy in addition, the melting point of the acidic filler can be as high as 1000 ° C or more, it will not be volatilized during the production of copper clad laminate, and will not decompose during PCB processing, and the organic acid is solved.
  • the acidic filler can also lower the CTE of the article in the resin composition, and its retention in the resin composition is beneficial to the reliability of the article.
  • the invention also adopts epoxy resin with different structures and different epoxy equivalents, which ensures the resin composition has high glass transition temperature, good mechanical properties and low water absorption. At the same time, the problem of poor machinability of the resin composition is also improved.
  • the pH of the acidic filler is between 2 and 6, for example 2, 2.5, 3, 3.5, 4, 5 or 6, and the specific values between the above values, limited by space and for simplicity It is contemplated that the present invention is no longer exhaustive of the specific point values included in the scope.
  • the acidic filler is characterized in that the filler and the deionized water are formulated into an aqueous solution at a mass ratio of 1:9, and the pH of the filler is obtained between 2 and 6.
  • the acidic filler has a pH between 4 and 6.
  • the acidic filler is selected from any one or a mixture of at least two of silicon micropowder, quartz powder, mica powder, clay, calcium oxalate or carbon black, wherein a typical but non-limiting mixture is silicon micropowder and Quartz powder, clay and calcium oxalate, carbon black and mica powder.
  • the acidic filler has a particle diameter of between 50 nm and 50 ⁇ m, such as 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, 300 nm, 500 nm, 800 nm, 5 ⁇ m, 10 ⁇ m, 30 ⁇ m, 40 ⁇ m, 45 ⁇ m or 50 ⁇ m, and
  • the specific point values between the above values are limited to the length and for the sake of brevity, the present invention will not exhaustively enumerate the specific point values included in the range.
  • the physical form of the acidic filler is not particularly limited, and may be, for example, a sheet, a rod, a sphere, a hollow sphere, a granule, a fiber or a plate; or a silane coupling agent may be optionally used for the acidic filler. Process it.
  • the acidic filler is added in an amount of 0.05 to 100 parts by weight, such as 0.05 parts by weight, 0.1 parts by weight, based on 100 parts by weight of the organic solid content of the benzoxazine-containing resin composition.
  • the specific point values are not limited to the specific point values included in the scope.
  • the acidic filler is added in an amount of 5 to 60 parts by weight based on 100 parts by weight of the organic solid content of the benzoxazine-containing resin composition.
  • the present invention adopts an acidic filler in an amount of 5 to 60 as a preferred mode.
  • the filler is used in an amount exceeding 60 parts by weight, the resin composition is generally acidic, and the benzoxazine-epoxy system is used.
  • the ring-opening polymerization reaction is obviously accelerated, and the processing window of the resin composition is narrowed; if the amount of the acidic filler is less than 5 parts, the overall acidity of the resin composition is weak, and the catalysis of the benzoxazine-epoxy system is catalyzed. The effect is not obvious.
  • the benzoxazine-containing resin composition contains the following components in an amount of 100 parts by weight based on the organic solid content:
  • (C) flame retardant 1 to 30 parts by weight
  • the weight ratio of the epoxy resins A1 and A2 is 10:1 to 1:10, for example, 10:1, 10:2, 10:3, 10:4, 10:5, 10:6, 10:7, 10:8, 10:9, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9 or 1: 10, and the specific point values between the above values, limited to the length and for the sake of brevity, the present invention no longer exhaustively enumerates the specific point values included in the range, preferably 4:1 to 1:4.
  • the epoxy resin is added in an amount of 5 to 80 parts by weight, for example, 5 parts by weight, 7 parts by weight, 10 parts by weight, 12 parts by weight, 15 parts by weight, 18 parts by weight, 20 parts by weight, and 25 parts by weight.
  • the specific point value included in the range is preferably 20 to 80 parts by weight.
  • the epoxy resin comprises an epoxy resin A1 having an epoxy equivalent of between 150 and 450 and an epoxy resin A2 having an epoxy equivalent of between 451 and 1000.
  • the invention is combined by using epoxy resins with different epoxy equivalents, which not only ensures that the resin composition has a high glass transition temperature, good mechanical properties and low water absorption, but also improves the resin composition. The problem of poor mechanical properties.
  • the epoxy resin A1 is selected from any one or at least a biphenyl epoxy resin, a dicyclopentadiene epoxy resin, a novolac epoxy resin, a naphthalene containing epoxy resin or a germanium containing epoxy resin.
  • the epoxy equivalent may be, for example, 150, 180, 192, 200, 210, 250, 315, 380, 400 or 450, and between the above values
  • the specific point values are limited to the length and for the sake of brevity, the present invention is no longer exhaustive to enumerate the specific point values included in the range.
  • the epoxy resin A2 is selected from any one of a bisphenol A epoxy resin, a bisphenol F epoxy resin, a carboxylated nitrile rubber modified epoxy resin, or an epoxy resin containing an oxazolidinone ring.
  • a mixture of at least two, and an epoxy equivalent of between 451 and 1000 wherein a typical but non-limiting mixture is: bisphenol A epoxy resin and carboxylated nitrile rubber modified epoxy resin, carboxylated nitrile a rubber-modified epoxy resin and an epoxy resin containing an oxazolidinone ring;
  • the epoxy equivalent may be, for example, 451, 455, 480, 492, 500, 610, 720, 810, 861, 900 or 1000, and the above
  • the specific point values between the numerical values are limited to the length and for the sake of brevity, the present invention is no longer exhaustively enumerated.
  • the selection and matching of the epoxy resin and the guiding and controlling of the ring-opening polymerization reaction of the benzoxazine by the acidic filler have synergistic effects on each other, contributing to the realization of a relatively stable peel strength, and the resin composition is improved. Reliability.
  • the benzoxazine resin is added in an amount of 10 to 80 parts by weight, for example, 10 parts by weight, 12 parts by weight, 15 parts by weight, 18 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 45 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight or 80 parts by weight, and specific between the above values
  • Point values limited to length and for the sake of brevity, the present invention is no longer exhaustive to enumerate specific point values included in the ranges, preferably 30 to 65 parts by weight.
  • the benzoxazine resin is selected from the group consisting of bisphenol A type benzoxazine resin, dicyclopentadiene type benzoxazine resin, bisphenol F type benzoxazine resin, and phenolphthalein type benzoxazine.
  • any one or a mixture of at least two of a resin or MDA type benzoxazine resin wherein a typical but non-limiting mixture is: bisphenol A type benzoxazine resin and dicyclopentadiene type benzoxazine Resin, dicyclopentadiene type benzoxazine resin, bisphenol F type benzoxazine resin, bisphenol F type benzoxazine resin and phenolphthalein type benzoxazine resin.
  • R 3 is R 4 is -CH 2 - or Any one of them.
  • R 4 When R 4 is When the structural formula ( ⁇ ) is a bisphenol A type benzoxazine resin monomer; when R 4 is -CH 2 -, the structural formula ( ⁇ ) is a bisphenol F type benzoxazine resin monomer; when R 4 is When the structural formula ( ⁇ ) is a phenolphthalein type benzoxazine resin monomer.
  • the MDA type benzoxazine resin also known as a (4,4'-diaminodiphenylmethane) type benzoxazine resin, has a structure as shown by the formula ( ⁇ ):
  • the flame retardant is added in an amount of 1 to 30 parts by weight, for example, 1 part by weight, 2 parts by weight, 5 parts by weight, 8 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight.
  • Part, 28 parts by weight or 30 parts by weight, and the specific point values between the above values limited to the length and for the sake of brevity, the present invention will not exhaustively enumerate the specific point values included in the range, preferably 3 to 20 weights. Share.
  • the flame retardant is selected from the group consisting of resorcinol-bis(diphenyl phosphate), bisphenol A-bis(diphenyl phosphate), resorcinol-bis(2,6-dimethylphenyl) Any one or a mixture of at least two of a phosphate ester, a methyl dimethyl phosphate or a phosphazene compound, wherein a typical but non-limiting mixture is: resorcinol-bis(diphenyl phosphate) and double Phenol A-bis(diphenyl phosphate), bisphenol A-bis(diphenyl phosphate) and resorcinol-bis(2,6-dimethylphenyl phosphate), resorcinol-bis (2, 6-Dimethylphenyl phosphate) and dimethyl methyl phosphate, dimethyl methyl phosphate and phosphazene compounds.
  • the benzoxazine-containing resin composition further contains an epoxy resin having an epoxy equivalent of more than 1,000, and the specific kind thereof is not particularly limited herein.
  • the benzoxazine-containing resin composition may further contain a non-acidic filler.
  • the non-acidic filler is selected from the group consisting of calcium carbonate, calcium sulfate, aluminum oxide, barium sulfate, ceramic powder, Any one or a mixture of at least two of talc or hydrotalcite, wherein the typical but non-limiting mixtures are: calcium carbonate and calcium sulfate, alumina and barium sulfate, ceramic powder and hydrotalcite.
  • the non-acidic filler is added in an amount of from 0 to 100 parts by weight, such as 1 part by weight, 5 parts by weight, 12 parts by weight, 15 parts by weight, 24 parts by weight, based on 100 parts by weight of the organic solid.
  • Parts by weight, 48 parts by weight, 56 parts by weight, 78 parts by weight, 89 parts by weight or 100 parts by weight, and the specific values between the above values, are limited in scope and for the sake of brevity, the present invention is not exhaustively enumerated. The specific point value included.
  • the benzoxazine-containing resin composition may further contain (D) a curing accelerator, wherein the organic solid content of the benzoxazine-containing resin composition is 100 parts by weight.
  • the curing accelerator is added in an amount of 0.1 to 1 part by weight, for example, 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight, 0.5 parts by weight, 0.6 parts by weight, 0.7 parts by weight, 0.8 parts by weight, 0.9 parts by weight or 1 part by weight, and the specific point values between the above values, and the present invention is not limited to the specific point values included in the range, for the sake of brevity and for the sake of brevity.
  • the curing accelerator is selected from the group consisting of an imidazole accelerator and a derivative thereof, a pyridine accelerator, a Lewis acid accelerator, or a mixture of at least two, of which a typical but non-limiting mixture It is an imidazole-promoting gold and pyridine accelerator, a pyridine accelerator, a Lewis acid accelerator, an imidazole accelerator, and a Lewis acid accelerator.
  • the imidazole promoter is selected from any one or at least two of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole or 2-undecylimidazole. mixture.
  • the curing accelerator is beneficial to curing reaction of the epoxy resin and the benzoxazine resin and the curing agent to form a uniform three-dimensional network structure to achieve better physical properties. It can also promote the decrease of the concentration of groups such as hydroxyl group (-OH) and epoxy group, and help the resin composition to achieve better dielectric properties and lower dielectric constant and dielectric loss.
  • a second object of the present invention is to provide a benzoxazine-containing resin composition
  • a benzoxazine-containing resin composition comprising an epoxy resin, a benzoxazine resin and an acidic filler, wherein the acidic filler has a pH of between 2 and 6,
  • the epoxy resin contains an epoxy resin A1 having an epoxy equivalent of between 150 and 450 and an epoxy resin A2 having an epoxy equivalent of between 451 and 1000.
  • the benzoxazine-containing resin composition may optionally contain an epoxy resin, a benzoxazine resin, and an acidic filler, optionally containing one of the objects of the present invention.
  • a flammable agent an epoxy resin having an epoxy equivalent of more than 1000, a non-acidic filler, a curing accelerator, and the like, and each component and content contained in the resin composition can be exemplarily referred to as one of the objects of the present invention.
  • the benzoxazine-containing resin composition may further contain various additives, and specific examples thereof include an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant, or a lubricant. Wait. These additives may be used singly or in combination of two or more.
  • the present invention also provides a prepreg comprising the resin composition prepared according to the method of one of the objects of the present invention or the resin composition of the second object, and a reinforcing material; the reinforcing material used is not particularly
  • the limitation may be organic fiber, inorganic fiber woven cloth or non-woven fabric.
  • the organic fiber may be selected from aramid nonwoven fabric, and the inorganic fiber woven fabric may be E-glass fabric, D-glass fabric, S-glass fabric, T-glass fabric, NE-glass fabric. Or quartz cloth.
  • the thickness of the reinforcing material is not particularly limited.
  • the thickness of the woven fabric and the nonwoven fabric is preferably 0.01 to 0.2 mm, and preferably is subjected to a fiber opening treatment and a surface treatment of a silane coupling agent, in order to provide good water resistance.
  • the silane coupling agent is preferably any one or a mixture of at least two of an epoxy silane coupling agent, an aminosilane coupling agent or a vinyl silane coupling agent.
  • the prepreg is obtained by impregnating the above composite material by impregnation with the above composite material at 100 to 250 ° C for 1 to 15 minutes.
  • the copper-clad laminate for a printed circuit board of the present invention comprises a laminate obtained by bonding two or more prepregs together by heat and pressure, and bonded to one or both sides of the laminate.
  • the above copper foil; the copper clad laminate lamination needs to meet the following requirements: 1.
  • the heating rate of lamination is generally controlled at a temperature of 80-160 ° C at a temperature of 1.0 to 3.0 ° C / min; Pressure setting, the outer layer material temperature is applied at 80-100 ° C, the full pressure is about 300 psi; 3, when curing, the control material temperature is 185 ° C, and the temperature is kept for 90 min; the covered metal foil except copper foil
  • nickel foil, aluminum foil, SUS foil, etc. may be used, and the material is not limited.
  • the present invention has at least the following beneficial effects:
  • the present invention greatly promotes the polymerization of benzoxazine and an epoxy resin by adding an acidic filler to the resin composition, and lowers the curing temperature required for benzoxazine and epoxy polymerization, thereby making benzo
  • the reaction of oxazine and epoxy is more complete;
  • the laminate of the present invention produced by using the resin composition to which the acidic filler is added has high peeling stability, high glass transition temperature, low water absorption, high heat resistance, high bending strength, and good process. Processability and low coefficient of thermal expansion;
  • the invention is compounded by using epoxy resins of different structures and different epoxy equivalents, thereby not only ensuring a high glass transition temperature of the resin composition, good mechanical properties and low water absorption, but also further improving The problem of poor machinability of the resin composition;
  • the present invention can be mutually selected by selecting and matching epoxy resins and adding acidic fillers. A synergistic effect is produced to help achieve a more stable peel strength and improve the reliability of the resin composition.
  • the parts represent parts by weight, and the % represents "% by weight”.
  • A1 a biphenyl type epoxy resin of the type NC-3000H purchased from Nippon Kayaku, epoxy equivalent of 288;
  • A2 a phenolic epoxy resin of the type EPPN-501H purchased from Nippon Kayaku, epoxy equivalent 166;
  • A3 bisphenol F type epoxy resin of KF21 type purchased from Shanghai Shi Yue, epoxy equivalent 540;
  • A4 bisphenol A type epoxy resin of type BE504ELM65 purchased from Changchun resin, epoxy equivalent 890;
  • A5 epoxy resin selected from Nippon Steel Chemical Model YDF-2004, epoxy equivalent 1005;
  • C1 A product of the model SPB-100 purchased from Otsuka Chemical Co., Ltd. of Japan;
  • E1 2-phenylimidazole purchased from the four countries of Japan.
  • laminates for printed circuit boards were prepared as follows, and the prepared laminates were subjected to performance tests.
  • the preparation method of the laminate for printed circuit board comprises:
  • step 2 8 pieces of prepreg and 2 pieces of one ounce (35 ⁇ m thick) metal foil are laminated together;
  • the operating conditions of the lamination are: controlling the heating rate when the temperature is 80-140 ° C When the temperature of the outer layer is 80-100 ° C, the full pressure is applied, and the full pressure is about 350 psi; when curing, the temperature of the control material is 195 ° C, and the temperature is kept for more than 60 min.
  • the measurement was carried out in accordance with the DSC method specified in 2.4.25 of IPC-TM-650.
  • the test temperature was 174 °C.
  • Instrument manufacturer American TA. N2 environment, heating rate 10 ° C / min.
  • the measurement was carried out in accordance with the method specified in 2.4.24 of IPC-TM-650.
  • Example 1 was compared with Comparative Example 1, and after the addition of the acidic filler in Example 1, the resin DSC starting temperature and the resin were not added in Comparative Example 1 The peak temperature is low, and the obtained plate has a higher glass transition temperature, longer dipping time resistance, lower water absorption rate and higher peel strength.
  • Example 2 Comparing Example 2 with Comparative Examples 2-4, after adding an acidic filler having a pH of 4.0 in Example 2, an acidic filler having a pH greater than 6.0 was added in Comparative Example 2-3 and a non-additive was added in Comparative Example 4.
  • acidic fillers the DSC initial temperature and peak temperature of the resin are lower, and the resulting plate glass transition The temperature is higher, the dipping time is longer, and the peel strength is higher.
  • the transition temperature is higher, the dipping time is longer, the water absorption rate is lower, and the peel strength is higher.
  • the present invention can make the resin DSC starting temperature by adding an acidic filler having a pH between 2 and 6 compared to other pH range fillers. And the peak temperature is low, and the board has better performance.
  • Example 2 is compared with Comparative Example 8-10, and epoxy resin and epoxy equivalent medium having an epoxy equivalent of between 150 and 450 are added in Example 2.
  • the epoxy resin between 451 and 1000 when only epoxy resin having an epoxy equivalent of between 150 and 450 is added in comparison with Comparative Examples 8 and 10, the water absorption rate is lower and the peel strength is more excellent;
  • the initial temperature and peak temperature of the resin DSC are both low, and the glass transition temperature of the obtained plate is high, and V can be achieved.
  • Example 4 Comparing Example 4 with Comparative Example 5-6, in Example 4, an epoxy resin having an epoxy equivalent of between 150 and 450 and an epoxy resin having an epoxy equivalent of between 451 and 1000 were used.
  • two kinds of epoxy resins having an epoxy equivalent of between 150 and 450 were added, which have better solder resistance, low water absorption and higher peel strength; two kinds are added in comparison with Comparative Example 6.
  • Epoxy resin with epoxy equivalent between 451 and 1000 the resin DSC has lower initial temperature and peak temperature, and the obtained plate has higher glass transition temperature, longer dipping time and lower water absorption. Has a more excellent peel strength.
  • Example 8 Comparing Example 8 with Comparative Examples 11-13, in Example 8, an epoxy resin having an epoxy equivalent of between 150 and 450 and an epoxy resin having an epoxy equivalent of between 451 and 1000 were used. Comparison In Example 11, an epoxy resin having an epoxy equivalent of more than 1000 was added, and the resin DSC initial temperature and peak temperature were both lower, and the obtained plate had a higher glass transition temperature and a lower water absorption rate; compared with Comparative Example 12 Epoxy resin with an epoxy equivalent of between 150 and 450 and an epoxy resin having an epoxy equivalent of greater than 1000 and Comparative Example 13 with an epoxy resin having an epoxy equivalent of between 451 and 1000 and an epoxy equivalent of greater than 1000 Epoxy resin, its resin DSC start temperature and peak temperature are lower, glass transition temperature is higher, water absorption rate is lower.
  • the present invention greatly promotes the polymerization of benzoxazine and epoxy resin by adding an acidic filler to the resin composition, and reduces the curing required for benzoxazine and epoxy polymerization.
  • the temperature makes the reaction of benzoxazine and epoxy more complete;
  • the laminate prepared by using the resin composition added with the acidic filler of the present invention has high peeling stability, high glass transition temperature, low water absorption, High heat resistance, high bending strength and good processability, and can achieve a low coefficient of thermal expansion; at the same time, the present invention not only ensures that the resin composition has a comparative advantage by using epoxy resins of different structures and different epoxy equivalents.
  • the high glass transition temperature, better mechanical properties and lower water absorption rate further improve the problem of poor machinability of the resin composition;
  • the invention can be mutually matched by the selection and matching of the epoxy resin and the addition of the acidic filler. Produce synergies to help achieve Stable peel strength improves the reliability of the resin composition.

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Abstract

一种含有苯并噁嗪的树脂组合物的制备方法及由其制成的预浸料和层压板，所述含有苯并噁嗪的树脂组合物的制备方法为：向含有苯并噁嗪的树脂组合物中添加酸性填料；所述含有苯并噁嗪的树脂组合物中含有苯并噁嗪树脂以及环氧当量介于150～450之间的环氧树脂A1和环氧当量介于451～1000之间的环氧树脂A2。通过在树脂组合物中添加酸性填料，极大地促进了苯并噁嗪和环氧树脂的聚合反应，降低了苯并噁嗪和环氧聚合所需的固化温度；使用该添加有酸性填料的树脂组合物制作的层压板具有高的抗剥稳定性、高玻璃化转变温度、低吸水率、高耐热性、高弯曲强度和良好的工艺加工性，并能实现低热膨胀系数。

Description

一种含有苯并噁嗪的树脂组合物的制备方法及由其制成的预浸料和层压板 技术领域
本发明涉及覆铜板技术领域，尤其涉及一种含有苯并噁嗪的树脂组合物的制备方法及由其制成的预浸料和层压板。
背景技术
在电子材料行业，为实现无溴阻燃，业内通常采用含磷的树脂或阻燃剂，配合含氮的树脂或阻燃剂实现磷-溴协同高效阻燃。苯并噁嗪树脂中含有氮元素，与磷元素复配使用时，可以较低的磷含量实现UL 94的V-0等级。加之固化收缩率低，耐湿热性能佳，得到了广泛使用。然而，由于苯并噁嗪树脂结构特点，苯并噁嗪的开环聚合需要较高的温度，为工业化批量生产带来了困难，成为了其应用的难点。
业内学者对上述难题进行了很多研究，其工作主要集中在胺类固化剂，酚醛树脂，有机酸等物质对苯并噁嗪反应的影响和机理探讨。对于印制电路基板(覆铜板，copper clad laminate)行业而言，这些研究成果很难直接进行转化应用。原因在于：胺类固化剂耐热性不佳，制成的半成品储存期限较短；酚醛树脂虽然耐热性较好，介电性能较差，剥离强度较低；有机酸对苯并噁嗪的开环作用明显，在覆铜板生产过程中，最高超过200℃的烘箱温度促使低沸点酸挥发完毕，在压合制程无法催化苯并噁嗪的开环和聚合。而高沸点有机酸则会在树脂组合物中残留，在制作过程中增加了PCB板受热分层爆板的风险。因此，对于苯并噁嗪树脂的应用，一直存在难题。
发明内容
基于此，本发明的目的之一在于提供含有苯并噁嗪的树脂组合物的制备方 法及由其制成的预浸料和层压板。通过在含有苯并噁嗪的树脂组合物中添加酸性填料，极大地促进了苯并噁嗪和环氧树脂的聚合反应，降低了苯并噁嗪和环氧聚合所需的固化温度；使用该添加有酸性填料的组合物制作的层压板具有高的抗剥稳定性、高玻璃化转变温度、低吸水率、高耐热性、高弯曲强度和良好的工艺加工性，并能实现低热膨胀系数。
发明人为实现上述目的，进行了反复深入的研究，结果发现：通过将酸性填料与含有苯并噁嗪的树脂组合物适当混合从而进行树脂组合物的制备，可达到上述目的。
为了实现上述目的，本发明采用了如下技术方案：
一种含有苯并噁嗪的树脂组合物的制备方法，所述方法为：
向含有苯并噁嗪的树脂组合物中添加酸性填料，酸性填料的pH值在2～6之间；
所述含有苯并噁嗪的树脂组合物中含有环氧树脂和苯并噁嗪树脂；
所述环氧树脂含有环氧当量介于150～450之间的环氧树脂A1和环氧当量介于451～1000之间的环氧树脂A2。
本发明中通过向含有苯并噁嗪的树脂组合物中添加酸性填料，可以催化苯并噁嗪和环氧树脂的开环聚合反应，又能促进苯并噁嗪自身交联聚合，极大地降低了苯并噁嗪和环氧聚合所需的温度；另外，酸性填料的熔点可高达1000℃以上，在覆铜板生产过程中受热不会挥发，在PCB加工中也不会分解，解决了有机酸和普通无机酸在树脂中的弱点；再有，酸性填料在树脂组合物中还能降低制品的CTE，其在树脂组合物中保留下来对制品的可靠性有益。
本发明还采用了不同结构和不同环氧当量的环氧树脂进行配合使用，其在保证树脂组合物具有较高玻璃化转变温度，较好的力学性能，较低吸水率的同 时，还改善了树脂组合物机械加工性差的难题。
根据本发明，所述酸性填料的pH值在2～6之间，例如2、2.5、3、3.5、4、5或6，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
本发明中，所述酸性填料的特征是：将该填料与去离子水按1∶9的质量比配制成水溶液，对其进行测定从而得到该填料的pH值在2～6之间。
优选地，所述酸性填料的pH值在4～6之间。
根据本发明，所述酸性填料选自硅微粉、石英粉、云母粉、黏土、草酸钙或炭黑中的任意一种或至少两种的混合物，其中典型但非限制性的混合物为硅微粉和石英粉、黏土和草酸钙、炭黑和云母粉。
本发明中，所述酸性填料的粒径在50nm～50μm之间，例如50nm、60nm、70nm、80nm、90nm、100nm、300nm、500nm、800nm、5μm、10μm、30μm、40μm、45μm或50μm，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
对于所述酸性填料的物理形态，本发明不做特殊限定，例如可以是片材、棒状、球形、空心球形、粒状、纤维状或板状等；也可以选择性以硅烷偶联剂对酸性填料进行处理。
根据本发明，以所述含有苯并噁嗪的树脂组合物中有机固形物为100重量份计，所述酸性填料的添加量为0.05～100重量份，例如0.05重量份、0.1重量份、1重量份、10重量份、20重量份、30重量份、40重量份、55重量份、60重量份、65重量份、70重量份、80重量份、90重量份或100重量份，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
优选地，以所述含有苯并噁嗪的树脂组合物中有机固形物为100重量份计，所述酸性填料的添加量为5～60重量份。
本发明采用酸性填料的添加量为5～60作为优选方式，经发明人研究发现，若所述填料使用量超过60重量份，树脂组合物整体酸性较强，苯并噁嗪-环氧体系的开环聚合反应明显加快，会使得树脂组合物的加工工艺窗口变窄；若所述酸性填料使用量低于5份，树脂组合物整体酸性较弱，对苯并噁嗪-环氧体系的催化作用不明显。
根据本发明，所述含有苯并噁嗪的树脂组合物中，以有机固形物为100重量份计，含有如下组分：
(A)环氧树脂：5～80重量份；
(B)苯并噁嗪树脂：10～80重量份；
(C)阻燃剂：1～30重量份；
所述环氧树脂中，环氧树脂A1和A2的重量比为10∶1～1∶10，例如10∶1、10∶2、10∶3、10∶4、10∶5、10∶6、10∶7、10∶8、10∶9、1∶1、1∶2、1∶3、1∶4、1∶5、1∶6、1∶7、1∶8、1∶9或1∶10，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值，优选4∶1～1∶4。
本发明中，所述环氧树脂的添加量为5～80重量份，例如5重量份、7重量份、10重量份、12重量份、15重量份、18重量份、20重量份、25重量份、30重量份、45重量份、50重量份、60重量份、70重量份或80重量份，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值，优选为20～80重量份。
根据本发明，所述环氧树脂含有环氧当量介于150～450之间的环氧树脂A1和环氧当量介于451～1000之间的环氧树脂A2。
本发明通过采用不同环氧当量的环氧树脂进行组合，其不仅保证了树脂组合物具有较高的玻璃化转变温度、较好的力学性能和较低的吸水率，同时还改善了树脂组合物机械性差的问题。
本发明中，所述环氧树脂A1选自联苯环氧树脂、双环戊二烯环氧树脂、酚醛型环氧树脂、含萘环氧树脂或含蒽环氧树脂中的任意一种或至少两种的混合物，且环氧当量介于150～450之间；其中典型但非限制性的混合物为：联苯环氧树脂和双环戊二烯环氧树脂、双环戊二烯环氧树脂和含萘环氧树脂、含萘环氧树脂和含蒽环氧树脂；所述环氧当量例如可以是150、180、192、200、210、250、315、380、400或450，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
本发明中，所述环氧树脂A2选自双酚A环氧树脂、双酚F环氧树脂、羧基丁腈橡胶改性环氧树脂或含有噁唑烷酮环的环氧树脂中的任意一种或至少两种的混合物，且环氧当量介于451～1000之间；其中典型但非限制性的混合物为：双酚A环氧树脂和羧基丁腈橡胶改性环氧树脂、羧基丁腈橡胶改性环氧树脂和含有噁唑烷酮环的环氧树脂；所述环氧当量例如可以是451、455、480、492、500、610、720、810、861、900或1000，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
本发明中通过环氧树脂的选择搭配，以及酸性填料对苯并噁嗪开环聚合反应的引导和控制，其相互之间产生协同作用，有助于实现较稳定的剥离强度，提升树脂组合物的可靠性。
根据本发明，所述苯并噁嗪树脂的添加量为10～80重量份，例如10重量份、12重量份、15重量份、18重量份、20重量份、25重量份、30重量份、45重量份、50重量份、60重量份、70重量份或80重量份，以及上述数值之间的具体 点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值，优选为30～65重量份。
本发明中，所述苯并噁嗪树脂选自双酚A型苯并噁嗪树脂、双环戊二烯型苯并噁嗪树脂、双酚F型苯并噁嗪树脂、酚酞型苯并噁嗪树脂或MDA型苯并噁嗪树脂中的任意一种或至少两种的混合物，其中典型但非限制性的混合物为：双酚A型苯并噁嗪树脂和双环戊二烯型苯并噁嗪树脂、双环戊二烯型苯并噁嗪树脂和双酚F型苯并噁嗪树脂、双酚F型苯并噁嗪树脂和酚酞型苯并噁嗪树脂。
所述双酚A型苯并噁嗪树脂单体和双酚F型苯并噁嗪树脂单体、酚酞型苯并噁嗪树脂单体的结构如式(α)所示：
Figure PCTCN2017078496-appb-000001
式(α)
其中，R3为
Figure PCTCN2017078496-appb-000002
R4为
Figure PCTCN2017078496-appb-000003
-CH2-或
Figure PCTCN2017078496-appb-000004
中的任意1种。
当R4为
Figure PCTCN2017078496-appb-000005
时，结构式(α)为双酚A型苯并噁嗪树脂单体；当R4为-CH2-时，结构式(α)为双酚F型苯并噁嗪树脂单体；当R4为
Figure PCTCN2017078496-appb-000006
时，结构式(α)为酚酞型苯并噁嗪树脂单体。
所述MDA型苯并噁嗪树脂，又称(4，4’-二胺基二苯甲烷)型苯并噁嗪树脂，其结构如式(β)所示：
Figure PCTCN2017078496-appb-000007
式(β)
所述双环戊二烯苯并噁嗪树脂单体的结构式如(γ)所示：
Figure PCTCN2017078496-appb-000008
如(γ)
根据本发明，所述阻燃剂的添加量为1～30重量份，例如1重量份、2重量份、5重量份、8重量份、10重量份、15重量份、20重量份、25重量份、28重量份或30重量份，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值，优选为3～20重量份。
本发明中，所述阻燃剂选自间苯二酚-双(磷酸二苯酯)、双酚A-双(磷酸二苯酯)、间苯二酚-双(2，6-二甲苯基磷酸酯)、甲基磷酸二甲酯或磷腈化合物中的任意一种或至少两种的混合物，其中典型但非限制性的混合物为：间苯二酚-双(磷酸二苯酯)和双酚A-双(磷酸二苯酯)、双酚A-双(磷酸二苯酯)和间苯二酚-双(2，6-二甲苯基磷酸酯)、间苯二酚-双(2，6-二甲苯基磷酸酯)和甲基磷酸二甲酯、甲基磷酸二甲酯和磷腈化合物。
本发明中，所述含有苯并噁嗪的树脂组合物中还含有环氧当量大于1000的环氧树脂，其具体种类在此不做特殊限定。
优选地，所述含有苯并噁嗪的树脂组合物中还可以含有非酸性填料。
优选地，所述非酸性填料选自碳酸钙、硫酸钙、氧化铝、硫酸钡、陶瓷粉、 滑石粉或水滑石中的任意一种或至少两种的混合物，其中典型但非限制性的混合物为：碳酸钙和硫酸钙、氧化铝和硫酸钡、陶瓷粉和水滑石。
优选地，以有机固形物为100重量份计，所述非酸性填料的添加量为0～100重量份，例如1重量份、5重量份、12重量份、15重量份、24重量份、35重量份、48重量份、56重量份、78重量份、89份或100重量份，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
根据本发明，所述含有苯并噁嗪的树脂组合物中还可以含有(D)固化促进剂，以所述含有苯并噁嗪的树脂组合物中有机固形物为100重量份计，所述固化促进剂的添加量为0.1～1重量份，例如0.1重量份、0.2重量份、0.3重量份、0.4重量份、0.5重量份、0.6重量份、0.7重量份、0.8重量份、0.9重量份或1重量份，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
本发明中，所述固化促进剂选自咪唑类促进剂及其衍生物，吡啶类促进剂，路易斯酸类促进剂中的任意一种或至少两种的混合物，其中典型但非限制性的混合物为咪唑类促进金和吡啶类促进剂、吡啶类促进剂和路易斯酸类促进剂、咪唑类促进剂和路易斯酸类促进剂。
优选地，所述咪唑类促进剂选自2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑或2-十一烷基咪唑中的任意一种或至少两种的混合物。
所述固化促进剂有益于环氧树脂和苯并噁嗪树脂以及固化剂进行固化反应，形成均匀的三维网状分子结构，达到较佳的物性。并能促进羟基(-OH)和环氧基等基团浓度的下降，帮助树脂组合物实现较佳的介电性能，降低介电常数和介电损耗。
本发明的目的之二在于提供了一种含有苯并噁嗪的树脂组合物，其含有环氧树脂、苯并噁嗪树脂和酸性填料，所述酸性填料的pH值在2～6之间，所述环氧树脂含有环氧当量介于150～450之间的环氧树脂A1和环氧当量介于451～1000之间的环氧树脂A2。
本领域技术人员可以明了，所述含有苯并噁嗪的树脂组合物中除了包含环氧树脂、苯并噁嗪树脂和酸性填料外，还可以任选地含有本发明目的之一所述的阻燃剂、环氧当量大于1000的环氧树脂、非酸性填料、固化促进剂等组分，且所述树脂组合物中含有的各个组分和含量均可示例性地参考本发明目的之一所述的范围。
本发明所述的“含有”，意指其除所述组份外，还可以包括其他组份，这些其他组份赋予所述树脂组合物不同的特性。除此之外，本发明所述的“含有”，还可以替换为封闭式的“为”或“由……组成”。
例如，所述含有苯并噁嗪的树脂组合物还可以含有各种添加剂，作为具体例，可以举出抗氧剂、热稳定剂、抗静电剂、紫外线吸收剂、颜料、着色剂或润滑剂等。这些添加剂可以单独使用，也可以两种或者两种以上混合使用。
对于本发明中未进一步限定的含有苯并噁嗪的树脂组合物的制备步骤，本领域技术人员可以参考现有的树脂组合物的制备方法，结合实际情况进行选择，本发明不做特殊限定。
本发明还提供了一种预浸料，其含有根据本发明目的之一所述方法制备得到的树脂组合物或目的之二所述的树脂组合物，以及增强材料；所使用的增强材料无特别的限定，可以为有机纤维、无机纤维编织布或无纺布。所述的有机纤维可以选择芳纶无纺布，所述的无机纤维编织布可以为E-玻纤布、D-玻纤布、S-玻纤布、T玻纤布、NE-玻纤布或石英布。所述增强材料的厚度无特别限定， 处于层压板有良好的尺寸稳定性的考虑，所述编织布及无纺布厚度优选0.01～0.2mm，且最好是经过开纤处理及硅烷偶联剂表面处理的，为了提供良好的耐水性和耐热性，所述硅烷偶联剂优选为环氧硅烷偶联剂、氨基硅烷偶联剂或乙烯基硅烷偶联剂中的任意一种或至少两种的混合物。将增强材料通过含浸上述的复合材料，在100～250℃条件下，烘烤1～15分钟得到所述预浸料。
本发明的印刷电路板用覆铜箔层压板包括通过加热和加压，使两片或两片以上的预浸料粘合在一起而制成的层压板、粘合在层压板的一面或两面以上的铜箔；所述的覆铜箔层压需满足以下要求：1、层压的升温速率通常在料温80-160℃时的升温速度应控制在1.0～3.0℃/min；2、层压的压力设置，外层料温在80～100℃时施加满压，满压压力为300psi左右；3、固化时，控制料温在185℃，并保温90min；所覆盖的金属箔除铜箔外，还可以是镍箔、铝箔及SUS箔等，其材质不限。
与现有技术相比，本发明至少具有以下有益效果：
(1)本发明通过在树脂组合物中添加酸性填料，极大地促进了苯并噁嗪和环氧树脂的聚合反应，降低了苯并噁嗪和环氧聚合所需的固化温度，使苯并噁嗪和环氧的反应更完全；
(2)本发明通过使用该添加有酸性填料的树脂组合物制作的层压板具有高的抗剥稳定性、高玻璃化转变温度、低吸水率、高耐热性、高弯曲强度和良好的工艺加工性，并能实现低热膨胀系数；
(3)本发明通过采用不同结构和不同环氧当量的环氧树脂进行配合，不仅保证了树脂组合物具有较高玻璃化转变温度，较好的力学性能和较低吸水率，还进一步改善了树脂组合物机械加工性差的难题；
(4)本发明通过对环氧树脂的选择搭配以及酸性填料的添加，其相互间可 产生协同增效作用，从而有助于实现较稳定的剥离强度，提升树脂组合物的可靠性。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。
以下所述是本发明实施例的具体实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明实施例原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也视为本发明实施例的保护范围。
下面分多个实施例对本发明实施例进行进一步的说明。本发明实施例不限定于以下的具体实施例。在不改变权利要求的范围内，可以适当的进行变更实施。
下文中如无特别说明，其份代表重量份，其％代表“重量％”。
实施例和对比例涉及的材料及牌号信息如下：
(A)环氧树脂：
A1：购于日本化药的型号为NC-3000H的联苯型环氧树脂，环氧当量288；
A2：购于日本化药的型号为EPPN-501H的酚醛环氧树脂，环氧当量166；
A3：购于上海势越的型号为KF21的双酚F型环氧树脂，环氧当量540；
A4：购于长春树脂的型号为BE504ELM65的双酚A型环氧树脂，环氧当量890；
A5：选自新日铁化学型号为YDF-2004的环氧树脂，环氧当量1005；
(B)苯并噁嗪树脂：
B1：购于亨斯迈的型号为LZ8290H62的产品；
B2：购于东材科技型号为D125的产品；
(C)阻燃剂
C1：购于日本大塚化学株式会社的型号为SPB-100的产品；
C2：购于日本大八化学的型号为PX-200的产品；
(D)填料
D1：购于江苏联瑞的球形二氧化硅DQ-1030，pH＝4.0；
D2：购于江苏联瑞的球形二氧化硅DQ-1028L，pH＝5.8；
D3：购于梧州颖丰矿业型号为3000目气流石英粉，pH＝3.0；
D4：购于安徽格锐云母粉GD-2，pH＝5.0；
D5：购于天津星龙泰化工产品科技有限公司的炭黑，pH＝3.0；
D6：购于蚌埠鑫源的勃姆石BG-615，pH＝6.8；
D7：购于矽比科的二氧化硅MEGASIL525，pH＝6.5；
D8：购于日本admatechs球形硅微粉SC2500-SEJ，pH＝8.0；
(E)固化促进剂
E1：购于日本四国化成的2-苯基咪唑。
将实施例和对比例提供的树脂组合物，按照如下方法制备印制电路用层压板，并对制备得到的层压板进行性能测试。
所述印制电路用层压板的制备方法包括：
①通过加热和加压作用使一张或一张以上的预浸料粘合在一起，制成的层压板；
②在步骤①制得的层压板的一面或两面上粘合金属箔；
③在层压机中进行层压；
在步骤②的过程中，使用8片预浸料和2片一盎司(35μm厚)的金属箔叠合在一起；
在步骤③的过程中，层压的操作条件为：料温80～140℃时，控制升温速率 为1.5～2.5℃/min；外层料温80-100℃时，施加满压，满压压力为350psi左右；固化时，控制料温在195℃，并保温60min以上。
实施例和对比例提供的树脂组合物的配方及性能测试结果见表1～4。
表1
Figure PCTCN2017078496-appb-000009
Figure PCTCN2017078496-appb-000010
表2
Figure PCTCN2017078496-appb-000011
Figure PCTCN2017078496-appb-000012
表3
Figure PCTCN2017078496-appb-000013
表4
Figure PCTCN2017078496-appb-000014
性能测试的项目及具体方法为：
(a)玻璃化转变温度：
根据差示扫描量热法，按照IPC-TM-650中2.4.25所规定的DSC方法进行测定。
(b)耐燃烧性：
依据UL94法测定。
(c)吸水性：
按照IPC-TM-650中的2.6.2.1所规定的方法进行测定。
(d)胶水GT
测试温度174℃。
(e)树脂DSC反应曲线测试：
仪器商：美国TA。N2环境，升温速率10℃/min。
(f)剥离强度：
按照IPC-TM-650中的2.4.8所规定的方法进行测定。
(g)热膨胀系数：
按照IPC-TM-650中的2.4.24所规定的方法进行测定。
物性分析：
(1)从表1～4可以看出，将实施例1与对比例1进行比较，实施例1中添加酸性填料后，相比对比例1中未添加酸性填料时，树脂DSC起始温度和峰值温度都较低，其制得的板材玻璃化转变温度较高，耐浸焊时间较长，吸水率较低，剥离强度更高。
将实施例2与对比例2-4进行比较，实施例2中添加pH值在4.0的酸性填料后，相比对比例2-3中添加pH值大于6.0的酸性填料以及对比例4中添加非酸性填料时，树脂DSC起始温度和峰值温度都较低，其制得的板材玻璃化转变 温度较高，耐浸焊时间较长，剥离强度更高。
将实施例2与对比例7进行比较，实施例2中添加酸性填料后，相比对比例7未添加酸性填料时，树脂DSC起始温度和峰值温度都较低，其制得的板材玻璃化转变温度较高，耐浸焊时间较长，吸水率较低，剥离强度更高。
通过上述实施例1-2和对比例1-4和7可以看出，本发明通过添加pH在2～6之间的酸性填料，相比其他pH值范围的填料，可以使树脂DSC起始温度和峰值温度都较低，并使板材具有更优异的性能。
(2)从表1～4还可以看出，将实施例2与对比例8-10进行比较，实施例2中添加环氧当量介于150～450之间的环氧树脂和环氧当量介于451～1000之间的环氧树脂，相比对比例8和10仅添加环氧当量介于150～450之间的环氧树脂时，其吸水率更低，具有更优异的剥离强度；相比对比例9中仅添加环氧当量介于451～1000之间的环氧树脂时，树脂DSC起始温度和峰值温度都较低，其制得的板材玻璃化转变温度较高，能达到V-0级阻燃，耐浸焊时间较长，吸水率较低，具有更优异的剥离强度。
将实施例4与对比例5-6进行比较，实施例4中采用添加环氧当量介于150～450之间的环氧树脂和环氧当量介于451～1000之间的环氧树脂，相比对比例5中添加两种环氧当量介于150～450之间的环氧树脂，其具有更优异的耐浸焊性，吸水率低并且剥离强度更高；相比对比例6中添加两种环氧当量介于451～1000之间的环氧树脂，树脂DSC起始温度和峰值温度都较低，其制得的板材玻璃化转变温度较高，耐浸焊时间较长，吸水率较低，具有更优异的剥离强度。
将实施例8与对比例11-13进行比较，实施例8中采用添加环氧当量介于150～450之间的环氧树脂和环氧当量介于451～1000之间的环氧树脂，相比对比 例11中添加环氧当量大于1000的环氧树脂，其树脂DSC起始温度和峰值温度都较低，其制得的板材玻璃化转变温度较高，吸水率较低；相比对比例12采用环氧当量介于150～450之间的环氧树脂和环氧当量大于1000的环氧树脂以及对比例13采用环氧当量介于451～1000之间的环氧树脂和环氧当量大于1000的环氧树脂，其树脂DSC起始温度和峰值温度都较低，玻璃化转变温度较高，吸水率较低。
通过上述实施例2、4和8与对比例5-6和对比例8-13可以看出，本发明中采用添加环氧当量介于150～450之间的环氧树脂和环氧当量介于451～1000之间的环氧树脂，这两种环氧树脂之间具有协同增效作用，其共同作用使得板材具有更优异的性能。
(3)通过实施例1和3与实施例6和9进行比较可以看出，当实施例1和3中将环氧当量介于150～450之间的环氧树脂和环氧当量介于451～1000之间的环氧树脂的重量比控制在4∶1～1∶4范围内时，相比实施例6和9中将两者范围控制在该范围之外时，其制得的板材具有更高的玻璃化转变温度。
通过上述实施例可以看出，本发明通过在树脂组合物中添加酸性填料，极大地促进了苯并噁嗪和环氧树脂的聚合反应，降低了苯并噁嗪和环氧聚合所需的固化温度，使苯并噁嗪和环氧的反应更完全；本发明通过使用该添加有酸性填料的树脂组合物制作的层压板具有高的抗剥稳定性、高玻璃化转变温度、低吸水率、高耐热性、高弯曲强度和良好的工艺加工性，并能实现低热膨胀系数；同时，本发明通过采用不同结构和不同环氧当量的环氧树脂进行配合，不仅保证了树脂组合物具有较高玻璃化转变温度，较好的力学性能和较低吸水率，还进一步改善了树脂组合物机械加工性差的难题；本发明通过对环氧树脂的选择搭配以及酸性填料的添加，其相互间可产生协同增效作用，从而有助于实现较 稳定的剥离强度，提升树脂组合物的可靠性。
应该注意到并理解，在不脱离后附的权利要求所要求的本发明的精神和范围的情况下，能够对上述详细描述的本发明做出各种修改和改进。因此，要求保护的技术方案的范围不受所给出的任何特定示范教导的限制。
申请人声明，本发明通过上述实施例来说明本发明的详细方法，但本发明并不局限于上述详细方法，即不意味着本发明必须依赖上述详细方法才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。

Claims (10)

  1. 一种含有苯并噁嗪的树脂组合物的制备方法，其特征在于，所述方法为：
    向含有苯并噁嗪的树脂组合物中添加酸性填料，酸性填料的pH值在2～6之间；
    所述含有苯并噁嗪的树脂组合物中含有环氧树脂和苯并噁嗪树脂；
    所述环氧树脂含有环氧当量介于150～450之间的环氧树脂A1和环氧当量介于451～1000之间的环氧树脂A2。
  2. 如权利要求1所述的方法，其特征在于，所述酸性填料的pH值在4～6之间；
    优选地，以所述含有苯并噁嗪的树脂组合物中有机固形物为100重量份计，所述酸性填料的添加量为0.05～100重量份，优选5～60重量份；
    优选地，所述酸性填料选自硅微粉、石英粉、云母粉、黏土、草酸钙或炭黑中的任意一种或至少两种的混合物；
    优选地，所述酸性填料的粒径为50nm～50μm。
  3. 如权利要求1或2所述的方法，其特征在于，所述含有苯并噁嗪的树脂组合物中，以有机固形物为100重量份计，含有如下组分：
    (A)环氧树脂：5～80重量份；
    (B)苯并噁嗪树脂：10～80重量份；
    (C)阻燃剂：1～30重量份；
    所述环氧树脂中，环氧树脂A1和A2的重量比为10∶1～1∶10，优选4∶1～1∶4。
  4. 如权利要求3所述的方法，其特征在于，所述含有苯并噁嗪的树脂组合物中，环氧树脂的含量为20～80重量份；
    优选地，所述环氧树脂A1选自联苯环氧树脂、双环戊二烯环氧树脂、酚醛型环氧树脂、含萘环氧树脂或含蒽环氧树脂中的任意一种或至少两种的混合物， 且环氧当量介于150～450之间；
    优选地，所述环氧树脂A2选自双酚A环氧树脂、双酚F环氧树脂、羧基丁腈橡胶改性环氧树脂或含有噁唑烷酮环的环氧树脂中的任意一种或至少两种的混合物，且环氧当量介于451～1000之间。
  5. 如权利要求3或4所述的方法，其特征在于，所述含有苯并噁嗪的树脂组合物中，苯并噁嗪树脂的含量为30～65重量份；
    优选地，所述苯并噁嗪树脂选自双酚A型苯并噁嗪树脂、双环戊二烯型苯并噁嗪树脂、双酚F型苯并噁嗪树脂、酚酞型苯并噁嗪树脂或MDA型苯并噁嗪树脂中的任意一种或至少两种的混合物。
  6. 如权利要求3-5之一所述的方法，其特征在于，所述含有苯并噁嗪的树脂组合物中，阻燃剂的含量为3～20重量份；
    优选地，所述阻燃剂选自间苯二酚-双(磷酸二苯酯)、双酚A-双(磷酸二苯酯)、间苯二酚-双(2，6-二甲苯基磷酸酯)、甲基磷酸二甲酯或磷腈化合物中的任意一种或至少两种的混合物。
  7. 如权利要求3-6之一所述的方法，其特征在于，所述含有苯并噁嗪的树脂组合物中还含有环氧当量大于1000的环氧树脂；
    优选地，所述含有苯并噁嗪的树脂组合物中还含有非酸性填料；
    优选地，所述非酸性填料选自碳酸钙、硫酸钙、氧化铝、硫酸钡、陶瓷粉、滑石粉或水滑石中的任意一种或至少两种的混合物；
    优选地，以有机固形物为100重量份计，所述非酸性填料的添加量为0～100重量份；
    优选地，所述含有苯并噁嗪的树脂组合物中还含有(D)固化促进剂；
    优选地，以所述含有苯并噁嗪的树脂组合物中有机固形物为100重量份计， 所述固化促进剂的添加量为0.1～1重量份；
    优选地，所述固化促进剂选自咪唑类促进剂及其衍生物、吡啶类促进剂或路易斯酸类促进剂中的任意一种或至少两种的混合物。
  8. 一种如权利要求1-7之一所述的方法制备的含有苯并噁嗪的树脂组合物，其特征在于，
    所述含有苯并噁嗪的树脂组合物中含有环氧树脂、苯并噁嗪树脂和酸性填料，所述酸性填料的pH值在2～6之间，所述环氧树脂含有环氧当量介于150～450之间的环氧树脂A1和环氧当量介于451～1000之间的环氧树脂A2；
    优选地，所述酸性填料的pH值在4～6之间；
    优选地，以所述含有苯并噁嗪的树脂组合物中有机固形物为100重量份计，所述酸性填料的添加量为0.05～100重量份，优选5～60重量份；
    优选地，所述酸性填料选自硅微粉、石英粉、云母粉、黏土、草酸钙或炭黑中的任意一种或至少两种的混合物；
    优选地，所述酸性填料的粒径为50nm～50μm；
    优选地，所述含有苯并噁嗪的树脂组合物中，以有机固形物为100重量份计，含有如下组分：
    (A)环氧树脂：5～80重量份；
    (B)苯并噁嗪树脂：10～80重量份；
    (C)阻燃剂：1～30重量份；
    以及，酸性填料的添加量为0.05～100重量份；
    所述环氧树脂中，环氧树脂A1和A2的重量比为10∶1～1∶10，优选为4∶1～1∶4；
    优选地，所述环氧树脂的含量为20～80重量份；
    优选地，所述环氧树脂A1选自联苯环氧树脂、双环戊二烯环氧树脂、酚醛 型环氧树脂、含萘环氧树脂或含蒽环氧树脂中的任意一种或至少两种的混合物，且环氧当量介于150～450之间；
    优选地，所述环氧树脂A2选自双酚A环氧树脂、双酚F环氧树脂、羧基丁腈橡胶改性环氧树脂或含有噁唑烷酮环的环氧树脂中的任意一种或至少两种的混合物，且环氧当量介于451～1000之间；
    优选地，所述苯并噁嗪树脂的含量为30～65重量份；
    优选地，所述苯并噁嗪树脂选自双酚A型苯并噁嗪树脂、双环戊二烯型苯并噁嗪树脂、双酚F型苯并噁嗪树脂、酚酞型苯并噁嗪树脂或MDA型苯并噁嗪树脂中的任意一种或至少两种的混合物；
    优选地，所述阻燃剂的含量为3～20重量份；
    优选地，所述阻燃剂选自间苯二酚-双(磷酸二苯酯)、双酚A-双(磷酸二苯酯)、间苯二酚-双(2，6-二甲苯基磷酸酯)、甲基磷酸二甲酯或磷腈化合物中的任意一种或至少两种的混合物；
    优选地，所述含有苯并噁嗪的树脂组合物还包含环氧当量大于1000的环氧树脂；
    优选地，所述含有苯并噁嗪的树脂组合物中还含有非酸性填料；
    优选地，所述非酸性填料选自碳酸钙、硫酸钙、氧化铝、硫酸钡、陶瓷粉、滑石粉或水滑石中的任意一种或至少两种的混合物；
    优选地，以有机固形物为100重量份计，非酸性填料的添加量为0～100重量份；
    优选地，所述含有苯并噁嗪的树脂组合物中还含有(D)固化促进剂；
    优选地，以所述含有苯并噁嗪的树脂组合物中有机固形物为100重量份计，所述固化促进剂的添加量为0.1～1重量份；
    优选地，所述固化促进剂选自咪唑类促进剂及其衍生物、吡啶类促进剂或路易斯酸类促进剂中的任意一种或至少两种的混合物。
  9. 一种预浸料，其含有根据权利要求1-7之一所述的方法制得的树脂组合物或含有根据权利要求8所述的树脂组合物。
  10. 一种层压板或印制电路板，其包括至少1张如权利要求9所述的预浸料。
PCT/CN2017/078496 2016-12-30 2017-03-29 含有苯并噁嗪的树脂组合物及其制备方法 WO2018120471A1 (zh)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10246588B1 (en) 2017-09-18 2019-04-02 Taiwan Union Technology Corporation Solvent-free resin composition and uses of the same
CN116410680A (zh) * 2021-12-30 2023-07-11 洛阳尖端技术研究院 吸波胶黏剂组合物及吸波胶黏剂、吸波胶膜

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107353594A (zh) * 2017-07-24 2017-11-17 无锡南理工科技发展有限公司 一种可固化树脂共混组合物及其应用
CN109161194A (zh) * 2018-08-17 2019-01-08 巢湖市翔宇渔具有限公司 一种钓竿用高强韧性复合材料
CN110845823B (zh) * 2018-08-21 2022-06-14 平高集团有限公司 一种苯并噁嗪改性环氧树脂绝缘材料、环氧浇注绝缘部件及其制备方法
JP2021154732A (ja) * 2020-03-25 2021-10-07 日立金属株式会社 軟磁性合金薄帯の積層体の製造方法
CN113248865B (zh) * 2021-05-10 2023-10-27 泰安市中研复合材料科技有限公司 一种可快速固化的苯并噁嗪树脂体系和一种复合材料

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8173040B2 (en) * 2009-05-08 2012-05-08 Samsung Electronics Co., Ltd. Composition including benzoxazine-based compound for forming board and board fabricated using the same
CN102850545A (zh) * 2012-10-10 2013-01-02 四川大学 一种高韧性高耐热性聚苯并噁嗪/双马来酰亚胺共混树脂及其制备方法
US9005761B2 (en) * 2011-12-22 2015-04-14 Elite Material Co., Ltd. Halogen-free resin composition and its application for copper clad laminate and printed circuit board
CN105482452A (zh) * 2015-12-25 2016-04-13 广东生益科技股份有限公司 一种无卤树脂组合物以及含有它的预浸料、层压板和印制电路板
CN105542394A (zh) * 2015-12-23 2016-05-04 陕西生益科技有限公司 一种无卤树脂组合物及其应用

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05310889A (ja) 1992-05-07 1993-11-22 Hitachi Chem Co Ltd エポキシ樹脂組成物
JP2005272672A (ja) 2004-03-25 2005-10-06 Toray Ind Inc 難燃剤マスターバッチ、熱硬化性樹脂組成物、プリプレグおよび繊維強化複合材料
CN102093666B (zh) * 2010-12-23 2012-09-26 广东生益科技股份有限公司 无卤树脂组合物及使用其的无卤覆铜板的制作方法
CN103013046B (zh) * 2012-12-13 2014-07-16 广东生益科技股份有限公司 一种无卤阻燃树脂组合物及其用途
KR102375986B1 (ko) * 2015-03-13 2022-03-17 닛테츠 케미컬 앤드 머티리얼 가부시키가이샤 옥사졸리돈 고리 함유 에폭시 수지, 그 제조 방법, 에폭시 수지 조성물, 및 경화물

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8173040B2 (en) * 2009-05-08 2012-05-08 Samsung Electronics Co., Ltd. Composition including benzoxazine-based compound for forming board and board fabricated using the same
US9005761B2 (en) * 2011-12-22 2015-04-14 Elite Material Co., Ltd. Halogen-free resin composition and its application for copper clad laminate and printed circuit board
CN102850545A (zh) * 2012-10-10 2013-01-02 四川大学 一种高韧性高耐热性聚苯并噁嗪/双马来酰亚胺共混树脂及其制备方法
CN105542394A (zh) * 2015-12-23 2016-05-04 陕西生益科技有限公司 一种无卤树脂组合物及其应用
CN105482452A (zh) * 2015-12-25 2016-04-13 广东生益科技股份有限公司 一种无卤树脂组合物以及含有它的预浸料、层压板和印制电路板

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ZENG, MING ET AL.: "Research Progress of Catalytic and Curing Behaviour of Benzoxazines", PROCEEDINGS OF THE 14TH COPPER CLAD LAMINATE TECHNOLOGY, 24 September 2013 (2013-09-24), pages 207 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10246588B1 (en) 2017-09-18 2019-04-02 Taiwan Union Technology Corporation Solvent-free resin composition and uses of the same
CN116410680A (zh) * 2021-12-30 2023-07-11 洛阳尖端技术研究院 吸波胶黏剂组合物及吸波胶黏剂、吸波胶膜

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