CN107793699A - A kind of preparation method of the copper-clad plate prepregs of high-toughness halogen-free CEM 3 - Google Patents

A kind of preparation method of the copper-clad plate prepregs of high-toughness halogen-free CEM 3 Download PDF

Info

Publication number
CN107793699A
CN107793699A CN201610755435.6A CN201610755435A CN107793699A CN 107793699 A CN107793699 A CN 107793699A CN 201610755435 A CN201610755435 A CN 201610755435A CN 107793699 A CN107793699 A CN 107793699A
Authority
CN
China
Prior art keywords
preparation
halogen
copper
free
prepreg
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201610755435.6A
Other languages
Chinese (zh)
Other versions
CN107793699B (en
Inventor
李清亮
吴兰中
李子龙
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SHANGHAI GUOJI ELECTRONIC MATERIAL CO Ltd
Original Assignee
SHANGHAI GUOJI ELECTRONIC MATERIAL CO Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by SHANGHAI GUOJI ELECTRONIC MATERIAL CO Ltd filed Critical SHANGHAI GUOJI ELECTRONIC MATERIAL CO Ltd
Priority to CN201610755435.6A priority Critical patent/CN107793699B/en
Publication of CN107793699A publication Critical patent/CN107793699A/en
Application granted granted Critical
Publication of CN107793699B publication Critical patent/CN107793699B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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
    • 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
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/02—Coating on the layer surface on 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • 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
    • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/02—Temperature
    • 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
    • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/04—Time
    • 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
    • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/12—Pressure
    • 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
    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Reinforced Plastic Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention discloses a kind of preparation method of the copper-clad plate prepregs of high-toughness halogen-free CEM 3, it comprises the following steps：The glue solution for copper-clad plate of high-toughness halogen-free CEM 3 is coated on electronic-grade glass fiber cloth, then dries, produces veneer prepreg；The glue solution for copper-clad plate of high-toughness halogen-free CEM 3 is coated on glass felt, then dries, produces sandwich prepreg；The glue solution for copper-clad plate of high-toughness halogen-free CEM 3, its raw material include following components in parts by weight：75~120 parts of novolac epoxy resin, 300~450 parts of flame-retardant modified liquid halogen-free epoxy resin, 150~250 parts of flame-retardant modified solid-state halogen-free epoxy resins, 25~50 parts of curing agent, 0.10~0.30 part of curing accelerator and 100~200 parts of organic solvents.Prepreg obtained by the preparation method of the present invention, not only with good heat resistance, chemical resistance, moreover it is possible to reduce pollution on the environment.

Description

A kind of preparation method of high-toughness halogen-free CEM-3 copper-clad plate prepregs
Technical field
Present invention relates particularly to a kind of preparation method of high-toughness halogen-free CEM-3 copper-clad plate prepregs.
Background technology
Copper-clad laminate (Copper Clad Laminate, CCL) is the main material for manufacturing printed circuit board (PCB) Material, therefore be also any electronic product complete machine, the indispensable base electronic material of part.With the rapid development of PCB industries, The market demand of high-performance copper coated foil plate increasingly increases, all-round developing in the green epoch, and the today to reach its maturity, except The performances such as the heat resistance of product, TG values, CTE value receive much concern outer, and toughness, PCB processabilities, the caking property of material also become one The individual emphasis that everybody pays close attention to, the harmony of copper-clad plate substrate performance develop into the important development for developing new copper-clad plate material Trend.
As electronic product now is light, thin, short, small and digitized demand, miniaturization, multi-functional, high-performance and height can By spending into mainstream development direction, PCB is caused to move towards fine pattern, high density, high multiple stratification, the line in PCB industry productions The requirement of the techniques such as width, line-spacing, aperture, hole wall also increasingly develops towards highly integrated, high density, high multilayer direction.Such as main flow High density interconnection laminated plates (HDI) require its micro- guide hole aperture in below 6mil, micro- guide hole orifice ring ring footpath 0.35mm with Under, contactor density is in 130in/m2More than, wiring density is in l170in/m2More than, line width/line-spacing in below 0.1mm/0.1mm, And high-order HDI (more than Floor 12) is then subjected to the special process such as the multiple hot pressing of high-order and more accurate careful manufacturing process will Ask.It is especially unleaded to carry out in an all-round way and the hair at full speed of surface mounting technology (SMT) with the development of high-density installation technology Exhibition, PCB processing with the installation of complete machine accessory, material bear repeatedly thermal shock number and temperature all conventional need is more than ever Height, everything is all eventually converted into the huge challenge of high-performance copper coated foil plate unfailing performance.
CEM-3 (Composite Epoxy Material Grade-3) be a kind of performance level, price between CEM-1 and Compound copper-clad laminate between FR-4, it is using epoxy resin glass fiber fabric base bonding sheet as fabric, epoxy resin Chopped Strand Mat Base bonding sheet core material, single or double covering copper foil after hot pressing form.Because core material uses non-woven Chopped Strand Mat as strengthening material Material, CEM-3 mechanical strength is between FR-4 and paper-based copper-coated board (CEM-1), and its bending strength is than full glass-fiber-fabric knot The FR-4 of structure is lower slightly.Epoxy resin is used for CEM-3 preparation as the formula of glue, can improve CEM-3 toughness.To improve The anti-flammability of epoxide resin polymer, at present to the flame-retardant modified mainly based on halogen system of epoxy resin, and this based epoxy resin Environment can be polluted, be unfavorable for environmental protection.
The content of the invention
The technical problem to be solved in the present invention is to overcome the toughness of CEM-3 copper-clad plates in the prior art low, not environmentally The deficiencies of, there is provided a kind of high-toughness halogen-free CEM-3 glue solution for copper-clad plate, prepreg and copper-clad plate and preparation method thereof.This Invention mainly using the toughness of heat-resist, excellent heat conductivity novolac epoxy resin increase sheet material, selects composite curing system, Prepare high-toughness halogen-free CEM-3 copper-clad plates.Product base material possesses good high tenacity, heat resistance, thermal conductivity, combination property also table It is existing excellent.
The present invention is that solve above-mentioned technical problem by following technical proposals：
The invention provides a kind of high-toughness halogen-free CEM-3 glue solution for copper-clad plate, and it includes each group of following parts by weight Part：75~120 parts of novolac epoxy resin, 300~450 parts of flame-retardant modified liquid halogen-free epoxy resin, 150~250 parts it is fire-retardant Modified solid-state halogen-free epoxy resin, 25~50 parts of curing agent, 0.10~0.30 part of curing accelerator and 100~200 parts are organic Solvent.
Wherein, the flame-retardant modified liquid halogen-free epoxy resin and the flame-retardant modified solid-state halogen-free epoxy resin can use Various conventional use of flame-retardant modified halogen-free epoxy resins in the glue solution for copper-clad plate of this area.The flame-retardant modified liquid halogen-free Epoxy resin is preferably DOPO type liquid halogen-free fire retarding epoxide resins.The flame-retardant modified solid-state halogen-free epoxy resin is preferably For DOPO type solid-state Halogenless fire retarded epoxy resins.The performance indications of the DOPO types liquid halogen-free fire retarding epoxide resin are preferably For：Epoxide number 320-360g/eg, the viscosity at 25 DEG C are 1800-3000mPas, phosphorus content 3.1%.The DOPO types are consolidated The performance indications of state Halogenless fire retarded epoxy resin are preferably：Epoxide number 970-1070g/eg, the viscosity at 150 DEG C is 8000- 11000mPa·s。
Wherein, the curing agent can be curing agent commonly used in the art, preferably dicyandiamide (DICY).
Wherein, the curing accelerator can be curing accelerator commonly used in the art, preferably diphenyl-imidazole (2PI)。
Wherein, the solvent is solvent commonly used in the art, preferably acetone, butanone, dimethylformamide (DMF) one or more and in propylene glycol monomethyl ether.When the solvent is acetone, butanone, dimethylformamide and propane diols first During ether, the acetone, butanone, the weight ratio of dimethylformamide and propylene glycol monomethyl ether are preferably 1：1：6：1.
Present invention also offers a kind of preparation method of high-toughness halogen-free CEM-3 glue solution for copper-clad plate, and it includes following step Suddenly：
(1) curing agent, the curing accelerator and the solvent are mixed, stirring is to dissolving to obtain mixture A；
(2) the mixture A is mixed with the Halogen resin, stir to obtain mixture B；
(3) under agitation, the mixture B and the novolac epoxy resin are mixed, with 2200~2800rpm's Speed is sheared, and high-toughness halogen-free CEM-3 glue solution for copper-clad plate is produced after curing.
In the present invention, each raw material components are such as this in the preparation method of the high-toughness halogen-free CEM-3 glue solution for copper-clad plate Glue is prepared described in component in invention.
In step (1), the method and condition of the stirring can be this area conventional method and condition.The stirring when Between so that the curing agent and the curing accelerator are completely dissolved and are defined, preferably 3~5 hours.The rotating speed of the stirring Preferably 900~1400rpm.
In step (2), the method and condition of the stirring can be this area conventional method and condition.The stirring when Between so that the curing agent and the curing accelerator are completely dissolved and are defined, preferably 3~5 hours.The rotating speed of the stirring Preferably 1000~1500rpm.
In step (3), the method and condition of the shearing can be this area conventional method and condition.The shearing when Between preferably 1.0~2.0 hours.The rotating speed of the shearing is preferably in 2300~2700rpm steps (3), the curing Method and condition can be this area conventional method and condition.Described curing is preferably turned with 1000~1600rpm Speed stirring 8~12 hours；More preferably it is 9~12 hours.
Present invention also offers a kind of preparation method of high-toughness halogen-free CEM-3 copper-clad plate prepregs, it is included such as Lower step：The high-toughness halogen-free CEM-3 glue solution for copper-clad plate is coated on reinforcing material, then dries, produces；The enhancing Material is electronic-grade glass fiber cloth or glass felt.
Described electronic-grade glass fiber cloth and glass felt is conventional use of prepreg raw material in this area.Press Common sense in the field, when the reinforcing material is electronic-grade glass fiber cloth, the high-toughness halogen-free CEM-3 copper-clad plates are solid with half Change piece is veneer prepreg；When the reinforcing material is glass felt, the high-toughness halogen-free CEM-3 copper-clad plate semi-solid preparations Piece is sandwich prepreg.
It is preferred that in the preparation of the veneer prepreg, the coating device therefor is vertical gluing machine, the painting The speed covered is 16~23m/min；More preferably it is 18~20m/min.
It is preferred that in the preparation of the sandwich prepreg, the sandwich material coating device therefor is horizontal gluing machine； The speed of the coating is 9~13m/min；More preferably it is 10~12m/min.
It is preferred that the temperature of the drying is 180~205 DEG C；More preferably it is 190~200 DEG C.
Present invention also offers a kind of preparation method by the high-toughness halogen-free CEM-3 copper-clad plate prepregs is made The prepreg obtained.
Wherein, the electronic-grade glass fiber cloth can be electronic-grade glass fiber cloth commonly used in the art, preferably For electronic-grade glass fiber cloth 7628.The glass felt can be glass felt commonly used in the art, preferably 105g glass Felt.
The resin content of the veneer prepreg is generally 31~35wt%.The resin content of the sandwich prepreg Generally 28~33wt%.The gel time of the veneer prepreg is generally 120~140s, and the gel time of glue is general For 230~260s.The fluidity of the veneer prepreg is generally 18~24%.The fluidity of sandwich prepreg is generally 22~30%.The fugitive constituent of the veneer prepreg is less than 0.5%, and such as 0.3%, the volatile matter of the sandwich prepreg It is less than 0.5%, such as 0.3%.By common sense in the field, sandwich prepreg need not determine gel time.
Present invention also offers a kind of preparation method of high-toughness halogen-free CEM-3 copper-clad plates, it comprises the following steps：
(1) folded in the both sides of several sandwich prepregs and match somebody with somebody several described veneer prepregs, obtain core, so Copper foil is covered with the one or both sides face of core afterwards, obtains semifinished sheet；
(2) semifinished sheet is subjected to hot pressing compacting, produces copper-clad plate.
In the present invention, the folded method for stacking prepreg with for copper-clad plate preparation technology field routine, it is usually With size and shape identical, several prepregs are neatly stacked, i.e. what each side of prepreg was all alignd stacks.This It is described folded with not needing pressure in invention, it is described folded with typically following four big principles：Gel content high level matches with low level principle, cloth type one Cause principle, symmetrical configuration principle and left and right collocating principle.
In step (2), the method and condition of the hot pressing compacting can be this area conventional method and condition.By this area General knowledge, after configuring steel plate and brown paper successively on copper foil before hot pressing compacting, then hot pressing compacting is carried out, after hot pressing compacting, Remove brown paper and steel plate.The number of the brown paper is generally 18~20.
The pressure of the hot pressing compacting is preferably 20~34kg/cm2；More preferably it is 27~32kg/cm2。
The temperature of the hot pressing compacting is preferably 130~200 DEG C；More preferably it is 160~190 DEG C.
The time of the hot pressing compacting is preferably 130~150min.
In the present invention, the preparation method of the high-toughness halogen-free CEM-3 copper-clad plates, follow-up sharp processing is typically also carried out And inspection process, to ensure the quality of product.
Present invention also offers a kind of high tenacity as obtained by the preparation method of the high-toughness halogen-free CEM-3 copper-clad plates Halogen CEM-3 copper-clad plates.
It on the basis of common sense in the field is met, above-mentioned each optimum condition, can be combined, it is each preferably real to produce the present invention Example.
Agents useful for same and raw material of the present invention are commercially available.The positive effect of the present invention is：
1st, this has been used in glue of the invention, prepreg and the preparation method of high-toughness halogen-free CEM-3 copper-clad plates The glue of invention, and their preparation method technique is simple, cost is low, consistent, fraction defective is low, the controllability of technique is strong, Suitable for producing in enormous quantities.
2nd, high-toughness halogen-free CEM-3 copper-clad plates of the invention meet production technologies of the downstream PCB to sheet material toughness, comprehensive Can be good, especially Halogen, toughness, heat-resisting, mechanical strength, thickness evenness are preferable, such as bromine content (PPm), less than 500, Industry is fully meet than standard value 900；T-288 ＞ 60min, than general more than high 50 times of FR-4 halogen-free copper-clad plates.The present invention's High-toughness halogen-free CEM-3 copper-clad plates are not stratified, non-foaming in thermal stress test.
Brief description of the drawings
Fig. 1 is the sample photo of the falling weight impact test of effect example 1.Wherein, left side is to cover copper made from embodiment 3 Plate；Right side is similar common CEM-3 copper-clad plates.
Embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to described reality Apply among a scope.The experimental method of unreceipted actual conditions in the following example, conventionally and condition, or according to business Product specification selects.
Embodiment 1
First, high-toughness halogen-free CEM-3 glue solution for copper-clad plate preparation methods are planted：
Composition of raw materials：
Resin：100 parts of novolac epoxy resin, 400 parts of flame-retardant modified liquid halogen-free epoxy resin, flame-retardant modified solid-state Halogen 200 parts of epoxy resin；Here modified epoxy is DOPO type Halogenless fire retarded epoxy resins, name of product：DOPO types, epoxy Value：8.3-9.4 (Eq/kg), viscosity 27 DEG C (mPas)：2000-5000；Here flame-retardant modified solid epoxy resin is DOPO Type Halogenless fire retarded epoxy resin, name of product：DOPO types, epoxide number：970-1070 (g/eg), viscosity 150 DEG C (mPas)： 8000-11000；
Curing agent：40 parts of dicyandiamide (DICY)；
Curing accelerator：0.20 part of 2- phenylimidazoles (C-2 substitutions)；
Solvent：150 parts of organic solvent (acetone：Butanone：DMF：Propylene glycol monomethyl ether=1：1：6：1).
Preparation method：Curing agent, accelerator and solvent are mixed, 4 hours are stirred completely to dissolving with 1000rpm rotating speed Obtain mixture A；(2) mixture A and flame-retardant modified liquid halogen-free epoxy resin, flame-retardant modified solid-state halogen-free epoxy resin are mixed Close, 5 hours are stirred to the mixture B that stirs to obtain with 1300rpm rotating speed；(3) under agitation, by mixture B and phenol Formaldehyde epoxy resin mixes, and with 2300rpm rotating speed high-speed stirred 2 hours, is stirred 10 hours and is cured with 1000rpm rotating speed After produce, the gel time of glue is 230s.
2nd, high-toughness halogen-free CEM-3 copper-clad plates
Preparation method：1. glue：Using gluing machine in 2 electronic-grade glass fiber cloths 7628 (doing panel overlay material) and 1 Open and above-mentioned obtained high-toughness halogen-free CEM-3 glue solution for copper-clad plate is coated on 105g glass felts (doing sandwich)；The baking of gluing machine Box temperature degree is 190 DEG C, and the speed of facing material gluing is 20m/min, obtains 2 prepregs, the resin content of the prepreg For 32wt%, the gel time of the prepreg is 130s, and the fluidity of the prepreg is 22%, the volatilization of the prepreg Part is 0.3%.The speed of sandwich material gluing is 11m/min, obtains 1 prepreg, the resin content of the prepreg is 29wt%, the fluidity of the prepreg is 26%, and the fugitive constituent of the prepreg is 0.3%；
2. lamination：3 prepregs are folded and matched somebody with somebody, it is two-sided to be all covered with copper foil, obtain semi-finished product；
3. described semi-finished product are carried out into hot pressing compacting, the temperature of hot pressing compacting is 190 DEG C, and the pressure of hot pressing compacting is 30kg/cm2, the time of hot pressing compacting is 143min, is produced.
Gained copper-clad plate is subjected to performance measurement, the results are shown in Table 1.
The performance parameter of copper-clad plate in the embodiment 1 of table 1
From table 1, the copper-clad plate combination property obtained by embodiment 1 is good.
Embodiment 2
First, high-toughness halogen-free CEM-3 glue solution for copper-clad plate preparation methods are planted：
Composition of raw materials：
Resin：80 parts of novolac epoxy resin, 300 parts of flame-retardant modified liquid halogen-free epoxy resin, flame-retardant modified solid-state Halogen 150 parts of epoxy resin；Here fire-retardant modified epoxy resin is DOPO type Halogenless fire retarded epoxy resins, name of product：DOPO types, Epoxide number：8.3-9.4 (Eq/kg), viscosity 27 DEG C (mPas)：2000-5000；Here flame-retardant modified solid epoxy resin is DOPO type Halogenless fire retarded epoxy resins, name of product：DOPO types, epoxide number：970-1070 (g/eg), 150 DEG C of (mPa of viscosity s)：8000-11000；
Curing agent：30 parts of dicyandiamide (DICY)；
Curing accelerator：0.20 part of 2- phenylimidazoles (C-2 substitutions)；
Solvent：120 parts of organic solvent (acetone：Butanone：Dimethylformamide：Propylene glycol monomethyl ether=1：1：6：1).
Preparation method：Curing agent, accelerator and solvent are mixed, 4 hours are stirred completely to dissolving with 1000rpm rotating speed Obtain mixture A；(2) mixture A and flame-retardant modified liquid halogen-free epoxy resin, flame-retardant modified solid-state halogen-free epoxy resin are mixed Close, 5 hours are stirred to the mixture B that stirs to obtain with 1300rpm rotating speed；(3) under agitation, by mixture B and phenol Formaldehyde epoxy resin mixes, and with 2500rpm rotating speed high-speed stirred 2 hours, is stirred 9 hours and is cured with 1000rpm rotating speed After produce, the gel time of glue is 245s.
2nd, high-toughness halogen-free CEM-3 copper-clad plates
Preparation method：1. glue：Using gluing machine in 2 electronic-grade glass fiber cloths 7628 (doing panel overlay material) and 1 Open and above-mentioned obtained high-toughness halogen-free CEM-3 glue solution for copper-clad plate is coated on 105g glass felts (doing sandwich)；The baking of gluing machine Box temperature degree is 195 DEG C, and the speed of facing material gluing is 20m/min, obtains 2 prepregs；The resin content of the prepreg is 32wt%, the gel time of the prepreg is 133s, and the fluidity of the prepreg is 21%, the fugitive constituent of the prepreg For 0.3%.The speed of sandwich material gluing is 12m/min, obtains 1 prepreg, and the resin content of the prepreg is 30wt%, The fluidity of the prepreg is 27%, and the fugitive constituent of the prepreg is 0.3%.
2. lamination：6 prepregs are folded and matched somebody with somebody, it is two-sided to be all covered with copper foil, obtain semi-finished product；
3. described semi-finished product are carried out into hot pressing compacting, the temperature of hot pressing compacting is 195 DEG C, and the pressure of hot pressing compacting is 30kg/cm2, the time of hot pressing compacting is 145min, is produced.Gained copper-clad plate is subjected to performance measurement, the results are shown in Table 2.
The performance parameter of the copper-clad plate of the embodiment 2 of table 2
From table 2, the copper-clad plate combination property obtained by embodiment 2 is good.
Embodiment 3
First, high-toughness halogen-free CEM-3 glue solution for copper-clad plate preparation methods are planted：
Composition of raw materials：
Resin：120 parts of novolac epoxy resin, 450 parts of flame-retardant modified liquid halogen-free epoxy resin, flame-retardant modified solid-state Halogen 250 parts of epoxy resin；Here fire-retardant modified epoxy resin is DOPO type Halogenless fire retarded epoxy resins, name of product：DOPO types, Epoxide number：8.3-9.4 (Eq/kg), viscosity 27 DEG C (mPas)：2000-5000；Here flame-retardant modified solid epoxy resin is DOPO type Halogenless fire retarded epoxy resins, name of product：DOPO types, epoxide number：970-1070 (g/eg), 150 DEG C of (mPa of viscosity s)：8000-11000；
Curing agent：50 parts of dicyandiamide (DICY)；
Curing accelerator：0.30 part of 2- phenylimidazoles (C-2 substitutions)；
Solvent：200 parts of organic solvent (acetone：Butanone：Dimethylformamide：Propylene glycol monomethyl ether=1：1：6：1).
Preparation method：Curing agent, accelerator and solvent are mixed, 4 hours are stirred completely to dissolving with 1000rpm rotating speed Obtain mixture A；(2) mixture A and flame-retardant modified liquid halogen-free epoxy resin, flame-retardant modified solid-state halogen-free epoxy resin are mixed Close, 4 hours are stirred to the mixture B that stirs to obtain with 1300rpm rotating speed；(3) under agitation, by mixture B and phenol Formaldehyde epoxy resin mixes, and with 2400rpm rotating speed high-speed stirred 2 hours, is stirred 12 hours and is cured with 1600rpm rotating speed After produce, the gel time of glue is 260s.
2nd, high-toughness halogen-free CEM-3 copper-clad plates
Preparation method：1. glue：Using gluing machine in 2 electronic-grade glass fiber cloths 7628 (doing panel overlay material) and 1 Open and above-mentioned obtained high-toughness halogen-free CEM-3 glue solution for copper-clad plate is coated on 105g glass felts (doing sandwich)；The baking of gluing machine Box temperature degree is 200 DEG C, and the speed of facing material gluing is 21m/min, obtains 2 prepregs；The resin content of the prepreg is 33wt%, the gel time of the prepreg is 135s, and the fluidity of the prepreg is 20%, the fugitive constituent of the prepreg For 0.3%.The speed of sandwich material gluing is 11m/min, obtains 1 prepreg, and the resin content of the prepreg is 31wt%, The fluidity of the prepreg is 29%, and the fugitive constituent of the prepreg is 0.3%.
2. lamination：6 prepregs are folded and matched somebody with somebody, it is two-sided to be all covered with copper foil, obtain semi-finished product；
3. described semi-finished product are carried out into hot pressing compacting, the temperature of hot pressing compacting is 185 DEG C, and the pressure of hot pressing compacting is 31kg/cm2, the time of hot pressing compacting is 148min, is produced.
Effect example 1
The high-toughness halogen-free CEM-3 copper-clad plates of embodiment 3 are subjected to performance detection, its main performance result see the table below table 3 It is shown.Other embodiment product effect is similar.Detection method is common detection methods.
The performance parameter of the copper-clad plate of the embodiment 3 of table 3
Falling weight impact test (toughness test experiment)
Laboratory apparatus：ISO Impact Tester, brand BYK Gardner, model 5512；
Laboratory sample：Base material thickness 1.0mm~1.1mm, 7628 × 1+105g of matrix structure felt × 1+7628 × 1ply；
Experimentation：Sample after etching is installed by instrument requirements, will drop hammer the position that is fixed on 20mm height, make it Freely falling body hits material, and the cross crack caused by shock material that drops hammer is more clear, illustrates toughness of material, Punch effects more It is good.Fig. 1 is the sample photo of falling weight impact test.It will be seen from figure 1 that copper-clad plate (Fig. 1 obtained by the embodiment of the present invention 3 The left side) toughness be substantially better than the similar common CEM-3 copper-clad plates material in market (on the right of Fig. 1).

Claims (10)

1. a kind of preparation method of high-toughness halogen-free CEM-3 copper-clad plate prepregs, it is characterised in that it includes following step Suddenly：High-toughness halogen-free CEM-3 glue solution for copper-clad plate is coated on electronic-grade glass fiber cloth, is then dried, it is solid to produce veneer half Change piece；
Or, high-toughness halogen-free CEM-3 glue solution for copper-clad plate is coated on glass felt, then dry, produce sandwich prepreg；
The high-toughness halogen-free CEM-3 glue solution for copper-clad plate, it is made by following raw materials, and the raw material includes following weight parts Component：75~120 parts of novolac epoxy resin, 300~450 parts of flame-retardant modified liquid halogen-free epoxy resin, 150~250 parts of resistances The modified solid-state halogen-free epoxy resin of combustion, 25~50 parts of curing agent, 0.10~0.30 part of curing accelerator and 100~200 parts have Solvent.
2. preparation method as claimed in claim 1, it is characterised in that the flame-retardant modified liquid halogen-free epoxy resin is DOPO Type liquid halogen-free fire retarding epoxide resin；
And/or the flame-retardant modified solid-state halogen-free epoxy resin is DOPO type solid-state Halogenless fire retarded epoxy resins；
And/or the curing agent is dicyandiamide；
And/or the curing accelerator is diphenyl-imidazole；
And/or the organic solvent is the one or more in acetone, butanone, dimethylformamide and propylene glycol monomethyl ether.
3. preparation method as claimed in claim 1, it is characterised in that the acetone, butanone, dimethylformamide and propane diols The weight ratio of methyl ether is 1：1：6：1.
4. the preparation method as described in any one of claims 1 to 3, it is characterised in that the fire-retardant ring of DOPO types liquid halogen-free The performance indications of oxygen tree fat are：Epoxide number 320-360g/eg, the viscosity at 25 DEG C is 1800-3000mPas, and phosphorus content is 3.1%；
And/or the performance indications of the DOPO types solid-state Halogenless fire retarded epoxy resin are：Epoxide number 970-1070g/eg, 150 DEG C Under viscosity be 8000-11000mPas.
5. the preparation method as described in any one of claims 1 to 3, it is characterised in that the high-toughness halogen-free CEM-3 copper-clad plates With glue, it is made by following method：
(1) curing agent, the curing accelerator and the solvent are mixed, stirring is to dissolving to obtain mixture A；
(2) the mixture A is mixed with the Halogen resin, stir to obtain mixture B；
(3) under agitation, the mixture B and the novolac epoxy resin are mixed, with 2200~2800rpm speed Sheared, high-toughness halogen-free CEM-3 glue solution for copper-clad plate is produced after curing.
6. preparation method as claimed in claim 5, it is characterised in that in step (1), the time of the stirring is small for 3~5 When；
And/or in step (1), the rotating speed of the stirring is 900~1400rpm；
And/or in step (2), the time of the stirring is 3~5 hours；
And/or in step (2), the rotating speed of the stirring is 1000~1500rpm；
And/or in step (3), the time of the shearing is 1.0~2.0 hours；
And/or in step (3), rotating speed more 2300~2700rpm of the shearing；
And/or in step (3), described curing is to be stirred 8~12 hours with 1000~1600rpm rotating speed.
7. preparation method as claimed in claim 1, it is characterised in that the electronic-grade glass fiber cloth is that E-glass is fine Tie up cloth 7628；
And/or the glass felt is 105g glass felts；
And/or in the preparation of the veneer prepreg, the coating device therefor is vertical gluing machine；
And/or in the preparation of the sandwich prepreg, the coating device therefor is horizontal gluing machine.
8. preparation method as claimed in claim 7, it is characterised in that in the preparation of the veneer prepreg, the painting The speed covered is 16~23m/min；
And/or in the preparation of the sandwich prepreg, the speed of the coating is 9~13m/min.
9. preparation method as claimed in claim 8, it is characterised in that in the preparation of the veneer prepreg, the painting The speed covered is 18~20m/min.
10. preparation method as claimed in claim 8, it is characterised in that in the preparation of the sandwich prepreg, the painting The speed covered is 10~12m/min.
CN201610755435.6A 2016-08-29 2016-08-29 Preparation method of prepreg for high-toughness halogen-free CEM-3 copper-clad plate Active CN107793699B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610755435.6A CN107793699B (en) 2016-08-29 2016-08-29 Preparation method of prepreg for high-toughness halogen-free CEM-3 copper-clad plate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610755435.6A CN107793699B (en) 2016-08-29 2016-08-29 Preparation method of prepreg for high-toughness halogen-free CEM-3 copper-clad plate

Publications (2)

Publication Number Publication Date
CN107793699A true CN107793699A (en) 2018-03-13
CN107793699B CN107793699B (en) 2021-06-25

Family

ID=61529259

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610755435.6A Active CN107793699B (en) 2016-08-29 2016-08-29 Preparation method of prepreg for high-toughness halogen-free CEM-3 copper-clad plate

Country Status (1)

Country Link
CN (1) CN107793699B (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1488672A (en) * 2003-08-01 2004-04-14 广州宏昌电子材料工业有限公司 Halogen-free flame-retarding epoxy resin composition containing phosphor and nitrogen and preimpregnated material and laminate containing same
US20130161080A1 (en) * 2011-12-22 2013-06-27 Yu-Te Lin Halogen-free resin composition and its application for copper clad laminate and printed circuit board
CN103214794A (en) * 2013-05-17 2013-07-24 宏昌电子材料股份有限公司 Halogen-free epoxy resin composition for copper-clad plate and application thereof
CN105038135A (en) * 2015-08-30 2015-11-11 王新峰 Epoxy resin for phosphorus-nitrogen composite modified copper-clad plate and production technology thereof
CN105542394A (en) * 2015-12-23 2016-05-04 陕西生益科技有限公司 Halogen-free resin composition and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1488672A (en) * 2003-08-01 2004-04-14 广州宏昌电子材料工业有限公司 Halogen-free flame-retarding epoxy resin composition containing phosphor and nitrogen and preimpregnated material and laminate containing same
US20130161080A1 (en) * 2011-12-22 2013-06-27 Yu-Te Lin Halogen-free resin composition and its application for copper clad laminate and printed circuit board
CN103214794A (en) * 2013-05-17 2013-07-24 宏昌电子材料股份有限公司 Halogen-free epoxy resin composition for copper-clad plate and application thereof
CN105038135A (en) * 2015-08-30 2015-11-11 王新峰 Epoxy resin for phosphorus-nitrogen composite modified copper-clad plate and production technology thereof
CN105542394A (en) * 2015-12-23 2016-05-04 陕西生益科技有限公司 Halogen-free resin composition and application thereof

Also Published As

Publication number Publication date
CN107793699B (en) 2021-06-25

Similar Documents

Publication Publication Date Title
CN102226033B (en) Epoxy resin composition as well as prepreg and metal-foil-clad laminated board manufactured by using same
CN103980708B (en) Halogen-free flame-retardant thermosetting resin composition of integrated circuit, prepreg and laminate
CN107778772A (en) A kind of preparation method of the copper-clad plates of high-toughness halogen-free CEM 3
CN103980704B (en) Halogen-free resin composition, prepreg and laminate for high-frequency high-speed substrate
US10364332B2 (en) High Tg epoxy formulation with good thermal properties
CN104109347B (en) A kind of halogen-free thermosetting resin composite, prepreg and laminate
CN107498952A (en) Meta-aramid fibers/all-glass paper base copper-clad laminate and its manufacture method
CN103980667B (en) Integrated circuit compositions of thermosetting resin, prepreg and laminate
CN103897350B (en) A kind of compositions of thermosetting resin and use its prepreg made and laminate
CN103724936B (en) Improve the Halogen-free low dielectric epoxy resin composition of shock resistance
CN103963386B (en) Metal-based copper-clad plate and preparation method thereof
CN107778771A (en) A kind of preparation method of the glue solution for copper-clad plate of high-toughness halogen-free CEM 3
CN107771418A (en) A kind of copper-clad plates of high-toughness halogen-free CEM 3
CN107791649A (en) A kind of glue solution for copper-clad plate of high-toughness halogen-free CEM 3
CN106189083A (en) The copper-clad plate that a kind of glass fabric strengthens
CN106084667A (en) A kind of high-k composition epoxy resin and application thereof
CN107793699A (en) A kind of preparation method of the copper-clad plate prepregs of high-toughness halogen-free CEM 3
CN107778770A (en) A kind of copper-clad plate prepregs of high-toughness halogen-free CEM 3
CN104589667A (en) Preparation method and application of bonding sheet for copper clad laminate
KR100867906B1 (en) Laminate composition for producing reduced curl flat thin core laminate
CN111031662A (en) High-flexibility high-TG (glass transition temperature) lead-free copper-clad plate and preparation method thereof
US7255927B2 (en) Laminate composition
TWI650363B (en) Polymer resin composition and its application in high frequency circuit boards
CN106189082B (en) A kind of fire retarded epoxy resin composition and application thereof
CN106366850A (en) Lapping carrier

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant