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CN106739376B - A kind of high-peeling strength, halogen-free type CEM-1 copper-clad plates preparation method - Google Patents

A kind of high-peeling strength, halogen-free type CEM-1 copper-clad plates preparation method Download PDF

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Publication number
CN106739376B
CN106739376B CN201611070309.3A CN201611070309A CN106739376B CN 106739376 B CN106739376 B CN 106739376B CN 201611070309 A CN201611070309 A CN 201611070309A CN 106739376 B CN106739376 B CN 106739376B
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parts
copper
resin
epoxy resin
phosphorous
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CN106739376A (en
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刘文江
李宝东
郑宝林
朱义刚
王天堂
徐树民
赵东
周鸥
陈晓鹏
陈长浩
高淑丽
姜晓亮
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SHANDONG JINBAO ELECTRONICS CO Ltd
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Campbell Shandong Branch Of Ltd By Share Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • B32B29/06—Layered products comprising a layer of paper or cardboard specially treated, e.g. surfaced, parchmentised
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/061—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/065—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of paper or cardboard
    • 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
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • B32B29/002—Layered products comprising a layer of paper or cardboard 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
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • B32B29/02—Layered products comprising a layer of paper or cardboard next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Reinforced Plastic Materials (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)

Abstract

The invention belongs to copper-clad plate production technical field more particularly to the preparation methods of a kind of high-peeling strength, halogen-free type CEM-1 copper-clad plates.The present invention does matrix resin with phosphorous epoxy resin and bisphenol A type epoxy resin, phosphorous linear phenolic resin makees curing agent, it is used in combination polyfunctional epoxy resin to increase heat resistance, a certain proportion of aluminium hydroxide is added, improve the tracking resistance index of copper-clad plate, nitrogenous, phosphonium flame retardant is added, improves the flame retardant property of plank using nitrogen phosphorus cooperative mode, reaches FV0Grade.The present invention is by handling filler surface used and size controlling, so that it evenly spreads in resin adhesive liquid, obtain uniform impregnation tablet, improve plank toughness, copper-clad plate obtained is set to reach halogen-free environmental requirement, the content of chlorine and bromine is small, and peel strength is high, and there is excellent anti-creep track property, CTI >=600V.

Description

A kind of high-peeling strength, halogen-free type CEM-1 copper-clad plates preparation method
Technical field
The invention belongs to copper-clad plate production technical field more particularly to a kind of high-peeling strength, halogen-free type CEM-1 copper-clad plates Preparation method.
Background technology
The anti-flammability of copper-clad plate is important one of the security performance of electronic product.For a long time, printed circuit board base material master It to be carried out using halogen fire-retardant.However, since last century the eighties, Switzerland, Germany, Japan and other countries researcher grind Studying carefully discovery, it will produce poisonous gas and carcinogen in combustion, have hidden danger to environment and health of human body.Therefore it grinds It is trend of the times to study carefully and produce and use halogen-free flame-retardant printed circuit base material.
It realizes that the halogen-free flameproof of CEM-1 copper-clad plates, general way are to do matrix resin with phosphorous epoxy at present, nothing is added Machine or organic nitrogenous flame ratardant are achieved the purpose that fire-retardant using nitrogen phosphorus synergistic effect.But that there are production costs is high for above-mentioned technique, The problems such as CTI is relatively low, peel strength is low, poor processability.
Invention content
The present invention in view of the deficiency of the prior art, provides a kind of high-peeling strength, halogen-free type CEM-1 copper-clad plates Preparation method.
The technical solution that the present invention solves above-mentioned technical problem is as follows：A kind of high-peeling strength, halogen-free type CEM-1 copper-clad plates Preparation method, steps are as follows：
(1) glass cloth resin emulsion is prepared：By 20-30 parts of phosphorous epoxy resins, 25-40 parts of bisphenol A type epoxy resins, 2-3 parts of amine curing agents, 0.1-0.3 parts of imidazoles, 15-20 parts of aluminium hydroxides, 10-15 parts of nitrogenous flame ratardants, 0.06-0.15 parts of silicon Alkane coupling agent and 10-15 parts of solvent mixing, stir evenly；
(2) bleached wood pulp paper resin emulsion is prepared：By 10-20 parts of phosphorous epoxy resins, 15-20 parts of bisphenol type epoxies Resin, 15-20 parts of phosphorous linear phenolic resins, 5-8 parts of polyfunctional epoxy resins, 15-20 parts of tung oil modified phenolic resins, 0.05-0.2 parts of imidazoles, 10-15 parts of phosphonium flame retardants, 10-15 nitrogenous flame ratardants and 10-20 parts of solvent mixing, stir evenly；
(3) resin emulsion made from step (1) is two-sided coated in E-glass cloth, it is dried under the conditions of 150-170 DEG C Dry 90-120s, control gel content are 41 ± 2%, fluidity 8-12%, gel 150-180s, and glass cloth impregnation tablet is made；
(4) resin emulsion made from step (2) is two-sided coated in bleached wood pulp paper, it is dried under the conditions of 150-170 DEG C 60-90s, control gel content are 59 ± 2%, fluidity 2-6%, volatile matter≤1%, and bleaching wood is made in gel 110-140s Starch paper impregnation tablet；
(5) bleached wood pulp paper impregnation tablet made from several steps (4) is taken to be superimposed, on it, lower two sides it is each It is superimposed the glass cloth impregnation tablet obtained by a step (3), finally a copper foil is respectively covered with two-sided or is covered with one in single side Copper foil is opened, hot pressing 60-90min under the conditions of 15-35MPa, 170-180 DEG C is cooling, and CEM-1 copper-clad plates are made.
The beneficial effects of the invention are as follows：
1, polyfunctional epoxy resin is added in the present invention in resin, improves the crosslink density of resin, is used in combination phosphorous linear Curing agent of the phenolic resin as epoxy resin, can reduce the dosage of phosphorous epoxy resin, not only met anti-flammability but also met resistance to It is hot, while peel strength is improved, reduce production cost.
2, phosphorous epoxy resin and bisphenol A type epoxy resin of the invention do matrix resin, and phosphorous linear phenolic resin is done Curing agent is used in combination polyfunctional epoxy resin to increase heat resistance, a certain proportion of aluminium hydroxide is added, and the resistance to electricity for improving copper-clad plate rises Trace index adds nitrogenous, phosphonium flame retardant, improves the flame retardant property of plank using nitrogen phosphorus cooperative mode, reaches FV0Grade.
3, the present invention to filler surface used by carrying out processing and size controlling so that it evenly spreads to resin glue In liquid, uniform impregnation tablet being obtained, improving plank toughness, copper-clad plate obtained is made to reach halogen-free environmental requirement, chlorine and bromine Content is small, and peel strength is high, and has excellent anti-creep track property, CTI >=600V.
Based on the above technical solution, the present invention can also be improved as follows.
Further, the epoxide equivalent of the phosphorous epoxy resin described in step (1) and step (2) is 250-450g/eq, is contained Phosphorus amount is 2-5%.
Further, the solvent described in step (1) and step (2) is dimethylformamide, acetone, methyl ethyl ketone, ethylene glycol One or more of monomethyl ether, cyclohexanone, propylene glycol monomethyl ether, ethyl alcohol or toluene mix.
Further, the epoxide equivalent of the bisphenol A type epoxy resin described in step (1) is 400-500g/eq；
The amine curing agent is in dicyandiamide, diamino hexichol alkane, diamino hexichol alum or diaminodiphenyl ether One or two mixing；
The aluminium hydroxide is 0.6-1.0 μm and 2-5 μm of two kinds of grain size mixes.
Further, the epoxide number of the bisphenol A type epoxy resin described in step (2) is 0.48-0.54, molecular weight 350- 400；
The phosphorus content of the phosphorous linear phenolic resin is 8-10%, hydroxyl equivalent 325-375g/eq, and softening point is 118-130℃；
The polyfunctional epoxy resin is phenol type novolac epoxy resin, o-cresol type novolac epoxy resin, bisphenol A-type One or more of novolac epoxy resin, biphenyl type novolac epoxy resin or three phenolic novolac epoxy resins mix；
Free phenol≤2.5% of the tung oil modified phenolic resin, gel time are 80-90s/160 DEG C.
Further, the nitrogenous flame ratardant described in step (1) and step (2) is melamine polyphosphate, melamine One or more of cyanurate or poly- ammonium polyphosphate mix.
Further, the phosphonium flame retardant described in step (2) is phosphoric acid ester, phosphonate ester, DOPO and derivative or ODOPB One or more of mixing.
Further, the phosphonium flame retardant described in step (2) is triphenyl phosphate, tricresyl phosphate, tricresyl phosphate Diphenyl ester, triisopropyl phenyl phosphate, melamine phosphate, N- methylol propionamide methyl phosphonates or methylphosphonic acid diformazan One or more of ester mixes.
Further, the gel content refers to the percentage that impregnation accounts for impregnation tablet weight with the pure solid of resin emulsion；Institute The fluidity stated refers to impregnation resin emulsion in 70 ± 5kg/cm2Pressure, the weight that flows out at 160 ± 2 DEG C account for impregnation use The percentage of resin emulsion total weight
Specific implementation mode
Principles and features of the present invention are described below in conjunction with example, the given examples are served only to explain the present invention, and It is non-to be used to limit the scope of the present invention.
Embodiment 1
A kind of high-peeling strength, halogen-free type CEM-1 copper-clad plates preparation method, steps are as follows：
(1) glass cloth resin emulsion is prepared：By 20 parts of phosphorous epoxy resins, 40 parts of bisphenol A type epoxy resins, 2.35 parts Dicyandiamide, 0.12 part of imidazoles, 15 parts of aluminium hydroxides, 15 parts of melamine polyphosphates, 0.12 part of silane coupling agent and 10 part third Ketone mixes, and stirs evenly；
(2) bleached wood pulp paper resin emulsion is prepared：By 12 parts of phosphorous epoxy resins, 20 parts of bisphenol A type epoxy resins, 18 Part phosphorous linear phenolic resin, 7 parts of phenol type novolac epoxy resins, 16 parts of tung oil modified phenolic resins, 0.2 part of imidazoles, 12 parts Triphenyl phosphate, 12 parts of melamine polyphosphates and 15 parts of acetone mixing, stir evenly；
(3) resin emulsion made from step (1) is two-sided coated in E-glass cloth, it is dried under the conditions of 150-170 DEG C Dry 110s, control gel content are 40.45%, and glass cloth impregnation tablet is made in fluidity 8.98%, gel 163s；
(4) resin emulsion made from step (2) is two-sided coated in bleached wood pulp paper, it is dried under the conditions of 150-170 DEG C 74s, control gel content is 58.49%, fluidity 4.56%, volatile matter 0.56%, and bleached wood pulp paper is made in gel 124s Impregnation tablet；
(5) bleached wood pulp paper impregnation tablet made from 6 steps (4) is taken to be superimposed, on it, lower two sides is respectively superimposed Glass cloth impregnation tablet obtained by one step (3), finally in the two-sided copper foil for being respectively covered with a thickness and being 35 μm, in 15- Hot pressing 60-90min under the conditions of 35MPa, 170-180 DEG C, it is cooling, CEM-1 copper-clad plates are made.
The fire-retardant of copper-clad plate obtained reaches FV0Grade, 288 DEG C of resistance to dip solderability >=20s, peel strength >=1.90N/mm are resistance to Tracking index CTI >=600V, chlorine element and bromo element content≤700ppm.
Embodiment 2
A kind of high-peeling strength, halogen-free type CEM-1 copper-clad plates preparation method, steps are as follows：
(1) glass cloth resin emulsion is prepared：By 25 parts of phosphorous epoxy resins, 36 parts of bisphenol A type epoxy resins, 2.5 parts Diamino hexichol alkane and diamino hexichol alum, 0.2 part of imidazoles, 16 parts of aluminium hydroxides, 13 parts of melamine cyanurates, 0.1 part Silane coupling agent and 10 parts of ethyl alcohol mixing, stir evenly；
(2) bleached wood pulp paper resin emulsion is prepared：By 16 parts of phosphorous epoxy resins, 18 parts of bisphenol A type epoxy resins, 16 The phosphorous linear phenolic resin of part, 7 parts of o-cresol type novolac epoxy resins, 18 parts of tung oil modified phenolic resins, 0.18 part of imidazoles, 13 Part N- methylol propionamides methyl phosphonate, 13 parts of melamine cyanurates and 16 parts of ethyl alcohol mixing, stir evenly；
(3) resin emulsion made from step (1) is two-sided coated in E-glass cloth, it is dried under the conditions of 150-170 DEG C Dry 100s, control gel content are 41.37%, and glass cloth impregnation tablet is made in fluidity 9.04%, gel 163s；
(4) resin emulsion made from step (2) is two-sided coated in bleached wood pulp paper, it is dried under the conditions of 150-170 DEG C 70s, control gel content is 59.7%, fluidity 5.34%, volatile matter 0.37%, and bleached wood pulp paper is made in gel 118s Impregnation tablet；；
(5) bleached wood pulp paper impregnation tablet made from 6 steps (4) is taken to be superimposed, on it, lower two sides is respectively superimposed Glass cloth impregnation tablet obtained by one step (3) is finally covered with one 35 μm of copper foil, in 15-35MPa, 170- in single side Hot pressing 60-90min under the conditions of 180 DEG C, it is cooling, CEM-1 copper-clad plates are made.
The fire-retardant of copper-clad plate obtained reaches FV0Grade, 288 DEG C of resistance to dip solderability >=20s, peel strength >=1.90N/mm are resistance to Tracking index CTI >=600V, chlorine element and bromo element content≤700ppm.
Embodiment 3
A kind of high-peeling strength, halogen-free type CEM-1 copper-clad plates preparation method, steps are as follows：
(1) glass cloth resin emulsion is prepared：By 30 parts of phosphorous epoxy resins, 30 parts of bisphenol A type epoxy resins, 2.0 parts Diamino hexichol alkane, 0.3 part of imidazoles, 18 parts of aluminium hydroxides, 12 parts of melamine polyphosphates and melamine cyanurate, 0.15 part of silane coupling agent and 12 parts of cyclohexanone mixing, stir evenly；
(2) bleached wood pulp paper resin emulsion is prepared：By 10 parts of phosphorous epoxy resins, 16 parts of bisphenol A type epoxy resins, 17 Part phosphorous linear phenolic resin, 8 parts of biphenyl type novolac epoxy resins, 16 parts of tung oil modified phenolic resins, 0.1 part of imidazoles, 15 parts ODOPB, 14 parts of melamine polyphosphates and melamine cyanurate, 20 parts of cyclohexanone mixing, stir evenly；
(3) resin emulsion made from step (1) is two-sided coated in E-glass cloth, it is dried under the conditions of 150-170 DEG C Dry 115s, control gel content are 41.67%, and glass cloth impregnation tablet is made in fluidity 8.67%, gel 172s；
(4) resin emulsion made from step (2) is two-sided coated in bleached wood pulp paper, it is dried under the conditions of 150-170 DEG C 86s, control gel content is 59.45%, fluidity 3.99%, volatile matter 0.64%, and bleached wood pulp paper is made in gel 136s Impregnation tablet；
(5) bleached wood pulp paper impregnation tablet made from 6 steps (4) is taken to be superimposed, on it, lower two sides is respectively superimposed Glass cloth impregnation tablet obtained by one step (3), finally in the two-sided copper foil for being respectively covered with a thickness and being 35 μm, in 15- Hot pressing 60-90min under the conditions of 35MPa, 170-180 DEG C, it is cooling, CEM-1 copper-clad plates are made.
The fire-retardant of copper-clad plate obtained reaches FV0Grade, 288 DEG C of resistance to dip solderability >=20s, peel strength >=1.90N/mm are resistance to Tracking index CTI >=600V, chlorine element and bromo element content≤700ppm.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all the present invention spirit and Within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention.

Claims (5)

1. the preparation method of a kind of high-peeling strength, halogen-free type CEM-1 copper-clad plates, which is characterized in that steps are as follows：
(1) glass cloth resin emulsion is prepared：By 20-30 parts of phosphorous epoxy resins, 25-40 parts of bisphenol A type epoxy resins, 2-3 Part amine curing agent, 0.1-0.3 parts of imidazoles, 15-20 parts of aluminium hydroxides, 10-15 parts of nitrogenous flame ratardants, 0.06-0.15 parts of silane Coupling agent and 10-15 parts of solvent mixing, stir evenly；
(2) bleached wood pulp paper resin emulsion is prepared：By 10-20 parts of phosphorous epoxy resins, 15-20 parts of bisphenol A type epoxy resins, 15-20 parts of phosphorous linear phenolic resins, 5-8 parts of polyfunctional epoxy resins, 15-20 parts of tung oil modified phenolic resins, 0.05-0.2 Part imidazoles, 10-15 parts of phosphonium flame retardants, 10-15 nitrogenous flame ratardants and 10-20 parts of solvents mixing, stir evenly；
(3) resin emulsion made from step (1) is two-sided coated in E-glass cloth, dry 90- under the conditions of 150-170 DEG C 120s, control gel content are 41 ± 2%, fluidity 8-12%, gel 150-180s, and glass cloth impregnation tablet is made；
(4) resin emulsion made from step (2) is two-sided coated in bleached wood pulp paper, dry 60- under the conditions of 150-170 DEG C 90s, control gel content are 59 ± 2%, fluidity 2-6%, volatile matter≤1%, and bleached wood pulp paper is made in gel 110-140s Impregnation tablet；
(5) bleached wood pulp paper impregnation tablet made from several steps (4) is taken to be superimposed, on it, lower two sides is respectively superimposed Glass cloth impregnation tablet obtained by one step (3) is finally respectively covered with a copper foil or is covered with a copper in single side two-sided Foil, hot pressing 60-90min under the conditions of 15-35MPa, 170-180 DEG C is cooling, and CEM-1 copper-clad plates are made；
The epoxide equivalent of phosphorous epoxy resin described in step (1) and step (2) is 250-450g/eq, phosphorus content 2- 5%；
Solvent described in step (1) and step (2) is dimethylformamide, acetone, methyl ethyl ketone, glycol monoethyl ether, hexamethylene One or more of ketone, propylene glycol monomethyl ether, ethyl alcohol or toluene mix；
The epoxide equivalent of bisphenol A type epoxy resin described in step (1) is 400-500g/eq；
The amine curing agent is one kind in dicyandiamide, diamino hexichol alkane, diamino hexichol alum or diaminodiphenyl ether Or two kinds of mixing；
The aluminium hydroxide is 0.6-1.0 μm and 2-5 μm of two kinds of grain size mixes；
The epoxide number of bisphenol A type epoxy resin described in step (2) is 0.48-0.54, molecular weight 350-400；
The phosphorus content of the phosphorous linear phenolic resin is 8-10%, hydroxyl equivalent 325-375g/eq, softening point 118- 130℃；
The polyfunctional epoxy resin is phenol type novolac epoxy resin, o-cresol type novolac epoxy resin, bisphenol A-type phenolic aldehyde One or more of epoxy resin, biphenyl type novolac epoxy resin or three phenolic novolac epoxy resins mix；
Free phenol≤2.5% of the tung oil modified phenolic resin, gel time are 80-90s/160 DEG C.
2. preparation method according to claim 1, which is characterized in that nitrogenous fire-retardant described in step (1) and step (2) Agent is the mixing of one or more of melamine polyphosphate, melamine cyanurate or poly- ammonium polyphosphate.
3. preparation method according to claim 1, which is characterized in that the phosphonium flame retardant described in step (2) is phosphoric acid Esters, phosphonate ester, DOPO and the mixing of one or more of derivative or ODOPB.
4. preparation method according to claim 1 or 3, which is characterized in that the phosphonium flame retardant described in step (2) is phosphorus Triphenyl phosphate ester, tricresyl phosphate, phosphate toluene diphenyl ester, triisopropyl phenyl phosphate, melamine phosphate, N- methylols One or more of propionamide methyl phosphonate or dimethyl methyl phosphonate mix.
5. preparation method according to claim 1, which is characterized in that the gel content refers to that impregnation resin emulsion is pure Solid accounts for the percentage of impregnation tablet weight；The fluidity refers to impregnation resin emulsion in 70 ± 5kg/cm2Pressure, The weight flowed out at 160 ± 2 DEG C accounts for the percentage of impregnation resin emulsion total weight.
CN201611070309.3A 2016-11-26 2016-11-26 A kind of high-peeling strength, halogen-free type CEM-1 copper-clad plates preparation method Active CN106739376B (en)

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Application Number Priority Date Filing Date Title
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CN109354827B (en) * 2018-09-30 2021-03-05 陕西生益科技有限公司 Halogen-containing antimony-free resin composition, prepreg using same, laminated board and printed circuit board
CN109370172B (en) * 2018-10-26 2021-09-14 北京科方创业科技企业孵化器有限公司 Halogen-free flame-retardant PET material and preparation method thereof
CN111234734B (en) * 2020-02-27 2020-11-24 招远春鹏电子科技有限公司 Environment-friendly glue solution for flexible copper-clad plate and preparation method thereof
CN111572131B (en) * 2020-05-28 2022-06-21 山东金宝电子股份有限公司 Preparation method of CEM-1 copper-clad plate with high heat resistance and high reliability
CN111806001A (en) * 2020-07-08 2020-10-23 山东金宝电子股份有限公司 Preparation method of dip-soldering-resistant high-flexibility CEM-1 copper-clad plate
CN114103372A (en) * 2021-11-30 2022-03-01 山东金宝电子股份有限公司 Preparation method of high-heat-resistance halogen-free CEM-1 copper-clad plate
CN116080213A (en) * 2022-11-11 2023-05-09 山东金宝电子有限公司 Preparation method of high-heat-conductivity and high-heat-resistance CEM-3 copper-clad plate for LED

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102585440A (en) * 2012-01-16 2012-07-18 广州宏仁电子工业有限公司 High-CTI (comparative tracking index) halogen-free flame retardant resin composition for copper-clad laminate
CN103059517A (en) * 2012-12-31 2013-04-24 金安国纪科技股份有限公司 Environmentally-friendly copper-clad plate glue solution, copper-clad plate and preparation method thereof
CN103182831A (en) * 2013-04-02 2013-07-03 陕西生益科技有限公司 Preparation technology of copper-clad laminate based on halogen-free flame-retardant resin compositions
CN104999740A (en) * 2015-07-24 2015-10-28 山东金宝电子股份有限公司 Preparation method for high-CTI halogen-free type CEM-3 copper-clad plate

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102585440A (en) * 2012-01-16 2012-07-18 广州宏仁电子工业有限公司 High-CTI (comparative tracking index) halogen-free flame retardant resin composition for copper-clad laminate
CN103059517A (en) * 2012-12-31 2013-04-24 金安国纪科技股份有限公司 Environmentally-friendly copper-clad plate glue solution, copper-clad plate and preparation method thereof
CN103182831A (en) * 2013-04-02 2013-07-03 陕西生益科技有限公司 Preparation technology of copper-clad laminate based on halogen-free flame-retardant resin compositions
CN104999740A (en) * 2015-07-24 2015-10-28 山东金宝电子股份有限公司 Preparation method for high-CTI halogen-free type CEM-3 copper-clad plate

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