CN105128497A - CEM-3 type copper-clad laminated plate base paper manufacturing method - Google Patents

CEM-3 type copper-clad laminated plate base paper manufacturing method Download PDF

Info

Publication number
CN105128497A
CN105128497A CN201510477369.6A CN201510477369A CN105128497A CN 105128497 A CN105128497 A CN 105128497A CN 201510477369 A CN201510477369 A CN 201510477369A CN 105128497 A CN105128497 A CN 105128497A
Authority
CN
China
Prior art keywords
cem
glue
base paper
copper foil
covers
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.)
Pending
Application number
CN201510477369.6A
Other languages
Chinese (zh)
Inventor
张国强
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.)
ZHONGXIN (TAICANG) INSULATION MATERIALS CO Ltd
Original Assignee
ZHONGXIN (TAICANG) INSULATION MATERIALS 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 ZHONGXIN (TAICANG) INSULATION MATERIALS CO Ltd filed Critical ZHONGXIN (TAICANG) INSULATION MATERIALS CO Ltd
Priority to CN201510477369.6A priority Critical patent/CN105128497A/en
Publication of CN105128497A publication Critical patent/CN105128497A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
    • 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
    • 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
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5033—Amines aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • 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
    • B32B2309/12—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
    • C08L2201/02—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

Landscapes

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

Abstract

The present invention provides a CEM-3 type copper-clad laminated plate base paper manufacturing method, which comprises: 1) preparing an impregnating glue liquid; 2) manufacturing a surface material; 3) manufacturing a core material; 4) stacking the obtained surface material and the obtained core material, covering copper foil on the upper surface of the plurality of the stacked base plates, covering a layer of a release film on the bottom surface, and then placing between two stainless steel plates; 5) placing into a laminator, carrying out a heating and pressurization treatment at a heating temperature of 170-175 DEG C under a pressure of 1-2 MPa, maintaining the pressure for 10-15 min, taking out, cutting, and testing to obtain the CEM-3 type copper-clad laminated plate base paper finished product. According to the present invention, the brominated bisphenol A type epoxy resin specially made through the method is matched with a variety of preparations to form the glue liquid, and the manufacturing process and the manufacturing conditions are subjected to the optimized combination so as to obtain the copper-clad laminated plate with characteristics of high temperature resistance and high fire-retardant property.

Description

A kind of CEM-3 type covers the manufacture method of copper foil laminates base paper
Technical field
The present invention relates to the manufacture method that a kind of CEM-3 type covers copper foil laminates base paper.
Background technology
Copper-clad laminate (CopperCladLaminate, CCL), also known as covering copper foil laminates base paper, be that electronic glass-fiber cloth or other reinforcing material are soaked with resin, one side or the two-sided a kind of board-like material made coated with Copper Foil and through hot pressing, referred to as copper-clad plate.The printed circuit board of various multi-form, difference in functionality, is all carry out selectively processing in copper-clad plate, etch, hole and the operation such as copper facing, makes different printed circuits.Interconnection, insulation and support are mainly play a part to printed circuit board, the transmission speed of signal in circuit, energy loss and characteristic impedance etc. are had a great impact, therefore, processability, manufacture level, manufacturing cost and long-term reliability in the performance of printed circuit board, quality, manufacture and stability depend on copper-clad plate to a great extent.
At present, the manufacturing process of copper-clad laminate is as follows:
Resins synthesis and glue prepare-and reinforcing material impregnation and oven dry-impregnation material shear and inspection-impregnation material and copper foil lamination-hot-forming-cutting-test package.
Wherein, glue is formed by resin and multiple additives such as the formulated in combination such as curing agent, promoter, solvent, resin is as the main component in glue, the performance of resin determines the performance of glue to a great extent, glue is as being coated on the outer field important materials of reinforcing material, determine the property indices of copper-clad laminate to a great extent, at present, the resin that manufacture copper-clad laminate is comparatively commonly used has phenolic resins, epoxy resin, unsaturated polyester resin, Teflon resin, polyimide resin, cyanate ester resin, BT resin etc.
But there is following defect in these epoxy resin above-mentioned:
(1), time not toughness reinforcing, solidfied material is generally partially crisp, and antistripping, cracking resistance, shock resistance are poor.
(2) little to material (as polyethylene, polypropylene, the fluoroplastics etc.) bonding force that polarity is little.First must carry out surface activation process.
(3) some raw material such as reactive diluent, curing agent etc. has toxicity in various degree and excitant.Should avoid selecting during component design as far as possible, during constructing operation, forced ventilation and protection should be added.
To this, there is following solution at present:
Chinese patent 201110435665.1 provides one and covers copper foil laminates base paper resin combination, comprising: the epoxy resin of 100 mass parts; The high performance resin of 50 ~ 200 mass parts; The polytetrafluoroethylene (PTFE) of 10 ~ 50 mass parts, described polytetrafluoroethylene (PTFE) is through surface treatment; The inorganic filler of 20 ~ 100 mass parts, described inorganic filler is through surface treatment; The curing agent of 0 ~ 50 mass parts.This patent application adopts high performance resin to carry out modification to epoxy resin, improves heat resistance and the dielectric properties of resin combination; Adopt surface treated polytetrafluoroethylene (PTFE), under the prerequisite ensureing resistance to elevated temperatures, dielectric properties and the fire resistance of composition can be improved, and reduce the moisture pick-up properties of composition; Adopt surface treated inorganic filler, the thermal expansivity of composition can be reduced, be applicable to high frequency, high heat-resistingly cover copper foil laminates base paper, the requirement of printed circuit board processing and assembling can be met.Wherein, described epoxy resin is one or more in bisphenol A epoxide resin, bisphenol F epoxy resin, phenol aldehyde type epoxy resin and biphenyl type phenolic resins.Described high performance resin is one or more in cyanate ester resin, modified polyphenylene ether resin, benzoxazine colophony and bimaleimide resin.Curing agent is 4, in 4 '-DADPS, MDA, diaminodiphenyl ether, triazine modification Nitrogen-containing Phenolic Resins and acid anhydrides one or more
But, the epoxy resin of the high performance resin modification that it adopts, but owing to there is a large amount of phenyl ring, making to cover the copper foil laminates base paper marks rising property of resistance to leak source can be poor.And, adopt modified epoxy like this, during sheet fabrication, need higher solidification temperature; In addition, at normal temperatures also can slow reaction, thus make to make bonding sheet storage period and greatly shorten, in addition, system does not possess the function that ultraviolet light stops yet.
Summary of the invention
For solving above-mentioned Problems existing, a kind of CEM-3 type is the object of the present invention is to provide to cover the manufacture method of copper foil laminates base paper, adopt special brominated bisphenol-A type epoxy resin to coordinate with several formulations and form glue, and by the optimum organization to manufacturing process, manufacturing condition, obtain copper-clad laminate that is high temperature resistant, high flame resistance.
For achieving the above object, technical scheme of the present invention is:
CEM-3 type covers a manufacture method for copper foil laminates base paper, comprises the steps:
1) dipping glue is prepared
1.1 preparation brominated bisphenol-A type epoxy resin
Tetrabromobisphenol A and epoxychloropropane are joined in reactor, after at room temperature stirring 25 ~ 30min, be heated to 50 ~ 60 DEG C, drip the 20%NaOH aqueous solution, dropwise in 30 ~ 60min, 70 ~ 90 DEG C are warming up to after dropwising, reaction 1 ~ 2h, adds distilled water and toluene, is stirred to dissolving, separatory, vacuum distillation obtains described brominated bisphenol-A type epoxy resin;
1.2 preparation glues
Get dimethyl formamide and ethylene glycol diglycidylether mix and blend obtains solvent, curing agent, described brominated bisphenol-A type epoxy resin, promoter, silane coupler, inorganic filler and endurable active toughener is added successively in gained solvent, stir, after slaking 10 ~ 15h, obtain described fabric dipping glue, solids content 75 ~ 80wt% in glue, sends into a glue groove stand-by;
2) fabric is manufactured
Get the alkali-free glass fiber cloth of rolling, uncoiling, dipping process is carried out by the glue groove having described fabric dipping glue with the speed of 70 ~ 80m/min, send into drying chamber to dry, obtain prepreg, gel duration 170 ~ 210s, bake out temperature 90 ~ 100 DEG C, drying time 2 ~ 5min, obtains fabric after cutting;
3) core material is manufactured
Get the glass fiber paper of rolling, uncoiling, carry out soaking process with the speed of 60 ~ 70m/min by the glue groove having described core material dipping glue, after completing, then carry out secondary dipping process with the speed of 60 ~ 70m/min by the glue groove having described fabric dipping glue, after completing, feeding drying chamber is dried, obtain prepreg, gel duration 170 ~ 210s, bake out temperature 90 ~ 100 DEG C, drying time 2 ~ 5min, obtains core material after cutting;
4) by gained fabric and core material stacked, and the some upper surface of base plate after stacked cover Copper Foils, and bottom surface is placed on after padding one deck mould release membrance again between two corrosion resistant plates;
5) put into laminating machine and carry out heating pressurized treatments, heating-up temperature is 170 ~ 175 DEG C, pressure is 1 ~ 2MPa, pressurize 10 ~ 15min, take out, cut, after inspection, obtain described CEM-3 type and cover copper foil laminates base paper product.
Wherein, the storage condition of described prepreg is: temperature less than 25 DEG C, relative humidity less than 50%.Copper thickness 18 μm or 35 μm.The surface of Copper Foil should be bright and clean, must not have obvious fold, oxidation spot, cut, pit, pit and stain.305g/m 2and the porosity of above Copper Foil requires that break is no more than 8 in 300ram × 300mm area; At 0.5m 2on area, the hole gross area of Copper Foil is no more than the area of a circle that diameter is 0.125mm.Alkali-free glass fiber cloth alkalinity (representing with Na20)≤0.5%.
Further, step 1) described in the mass volume ratio of tetrabromobisphenol A and epoxychloropropane be 1:1.5 ~ 3, g/ml; The mass volume ratio of described tetrabromobisphenol A and the 20%NaOH aqueous solution is 1:1.5 ~ 2, g/ml; The mass volume ratio of described tetrabromobisphenol A and toluene is 1:2 ~ 3, g/ml; The mass volume ratio of described tetrabromobisphenol A and distilled water is 1:1 ~ 2, g/ml.
Separately, step 1) in described glue, each constituent mass percentage is as follows: brominated bisphenol-A type epoxy resin: 50 ~ 60wt%, solvent: 25 ~ 35wt%, curing agent: 8 ~ 11wt%, promoter: 3 ~ 5wt%, silane coupler: 2 ~ 4wt%, inorganic filler: 1 ~ 2wt%, endurable active toughener: 1 ~ 2wt%.
Preferably, step 1) in described glue, each constituent mass percentage is as follows: brominated bisphenol-A type epoxy resin: 52wt%, solvent: 28wt%, curing agent: 10wt%, promoter: 3wt%, silane coupler: 3wt%, inorganic filler: 2wt%, endurable active toughener: 2wt%.
Separately having, step 1) volume ratio of dimethyl formamide and ethylene glycol diglycidylether is 1:1 in described solvent.
Again, step 1) described curing agent is aromatic amine curing agent or linear phenolic resin.
Wherein, described aromatic amine curing agent is MDA (DDM) or DADPS (DDS).
Further, step 1) described promoter is imidazoles promoter or benzyl dimethylamine.
And described imidazoles promoter is glyoxal ethyline, 2-ethyl-4-methylimidazole or 2-phenylimidazole.
Separately, step 1) described endurable active toughener is polybutadiene or polyurethane.
Again, step 1) described inorganic filler is selected from one in aluminium hydroxide, talcum powder, calcium carbonate, silicon powder and kaolin.
Beneficial effect of the present invention is:
Adopt brominated bisphenol-A type epoxy resin, the adhesivity of enhancement layer pressing plate and anti-flammability; Using aromatic amine curing agent or linear phenolic resin as curing agent, wherein, all contain stable benzene ring structure in the molecular structure of aromatic amine curing agent, amido is directly connected with phenyl ring, due to the main obstacle effect of phenyl ring, little with the curing cross-linking reaction specific activity fatty amine of epoxy resin; Due to the existence of phenyl ring, laminate is made to have higher heat resistance and good resistance to water, electrical property and mechanical property; Using imidazoles promoter or benzyl dimethylamine as promoter, the solidification temperature of composition epoxy resin of the present invention can be reduced, promote curing rate, thus reduce hardening time, reduce energy resource consumption; With polybutadiene or polyurethane for endurable active toughener, can effectively improve glue toughness, promote peel strength; With silane coupler to glue modifying surface, make its surface in close Organic, can be uniformly dispersed in the epoxy, give full play to its resistance to elevated temperatures.
Gained CEM-3 type covers copper foil laminates base paper and has good heat resistance, dielectric properties, fire resistance, processing characteristics, lower hot expansibility and lower moisture pick-up properties, electrical insulation capability is stablized, flatness is good, smooth surface, without pit, thickness deviation standard, be applicable to the product being applied to high-performance electronic insulating requirements, as FPC stiffening plate, PCB drilling liner plate, glass meson, potentiometer carbon film printed glass fiberboard, accurate pinion gear (wafer grinding), precision measurement sheet material, electrically (electrical equipment) apparatus insulated stay dividing plate, insulating pad, transformer insulated plate, motor insulation member, lapping gears, electronic switch insulation board etc.
Detailed description of the invention
A kind of CEM-3 type of the present invention covers the manufacture method of copper foil laminates base paper, comprises the steps:
1) dipping glue is prepared
1.1 preparation brominated bisphenol-A type epoxy resin
Tetrabromobisphenol A and epoxychloropropane are joined in reactor, after at room temperature stirring 25 ~ 30min, be heated to 50 ~ 60 DEG C, drip the 20%NaOH aqueous solution, dropwise in 30 ~ 60min, 70 ~ 90 DEG C are warming up to after dropwising, reaction 1 ~ 2h, adds distilled water and toluene, is stirred to dissolving, separatory, vacuum distillation obtains described brominated bisphenol-A type epoxy resin;
1.2 preparation glues
Get dimethyl formamide and ethylene glycol diglycidylether mix and blend obtains solvent, curing agent, described brominated bisphenol-A type epoxy resin, promoter, silane coupler, inorganic filler and endurable active toughener is added successively in gained solvent, stir, after slaking 10 ~ 15h, obtain described fabric dipping glue, solids content 75 ~ 80wt% in glue, sends into a glue groove stand-by;
2) fabric is manufactured
Get the alkali-free glass fiber cloth of rolling, uncoiling, dipping process is carried out by the glue groove having described fabric dipping glue with the speed of 70 ~ 80m/min, send into drying chamber to dry, obtain prepreg, gel duration 170 ~ 210s, bake out temperature 90 ~ 100 DEG C, drying time 2 ~ 5min, obtains fabric after cutting;
3) core material is manufactured
Get the glass fiber paper of rolling, uncoiling, carry out soaking process with the speed of 60 ~ 70m/min by the glue groove having described core material dipping glue, after completing, then carry out secondary dipping process with the speed of 60 ~ 70m/min by the glue groove having described fabric dipping glue, after completing, feeding drying chamber is dried, obtain prepreg, gel duration 170 ~ 210s, bake out temperature 90 ~ 100 DEG C, drying time 2 ~ 5min, obtains core material after cutting;
4) by gained fabric and core material stacked, and the some upper surface of base plate after stacked cover Copper Foils, and bottom surface is placed on after padding one deck mould release membrance again between two corrosion resistant plates;
5) put into laminating machine and carry out heating pressurized treatments, heating-up temperature is 170 ~ 175 DEG C, pressure is 1 ~ 2MPa, pressurize 10 ~ 15min, take out, cut, after inspection, obtain described CEM-3 type and cover copper foil laminates base paper product.
Wherein, the storage condition of described prepreg is: temperature less than 25 DEG C, relative humidity less than 50%.Copper thickness 18 μm or 35 μm.The surface of Copper Foil should be bright and clean, must not have obvious fold, oxidation spot, cut, pit, pit and stain.305g/m 2and the porosity of above Copper Foil requires that break is no more than 8 in 300ram × 300mm area; At 0.5m 2on area, the hole gross area of Copper Foil is no more than the area of a circle that diameter is 0.125mm.Alkali-free glass fiber cloth alkalinity (representing with Na20)≤0.5%.
Further, step 1) described in the mass volume ratio of tetrabromobisphenol A and epoxychloropropane be 1:1.5 ~ 3, g/ml; The mass volume ratio of described tetrabromobisphenol A and the 20%NaOH aqueous solution is 1:1.5 ~ 2, g/ml; The mass volume ratio of described tetrabromobisphenol A and toluene is 1:2 ~ 3, g/ml; The mass volume ratio of described tetrabromobisphenol A and distilled water is 1:1 ~ 2, g/ml.
Separately, step 1) in described glue, each constituent mass percentage is as follows: brominated bisphenol-A type epoxy resin: 50 ~ 60wt%, solvent: 25 ~ 35wt%, curing agent: 8 ~ 11wt%, promoter: 3 ~ 5wt%, silane coupler: 2 ~ 4wt%, inorganic filler: 1 ~ 2wt%, endurable active toughener: 1 ~ 2wt%.
Preferably, step 1) in described glue, each constituent mass percentage is as follows: brominated bisphenol-A type epoxy resin: 52wt%, solvent: 28wt%, curing agent: 10wt%, promoter: 3wt%, silane coupler: 3wt%, inorganic filler: 2wt%, endurable active toughener: 2wt%.
Separately having, step 1) volume ratio of dimethyl formamide and ethylene glycol diglycidylether is 1:1 in described solvent.
Again, step 1) described curing agent is aromatic amine curing agent or linear phenolic resin.
Wherein, described aromatic amine curing agent is MDA (DDM) or DADPS (DDS).
Further, step 1) described promoter is imidazoles promoter or benzyl dimethylamine.
And described imidazoles promoter is glyoxal ethyline, 2-ethyl-4-methylimidazole or 2-phenylimidazole.
Separately, step 1) described endurable active toughener is polybutadiene or polyurethane.
Again, step 1) described inorganic filler is selected from one in aluminium hydroxide, talcum powder, calcium carbonate, silicon powder and kaolin.
In the present invention, the preparation embodiment of brominated bisphenol-A type epoxy resin is as follows:
Embodiment 1
Tetrabromobisphenol A and epoxychloropropane are joined in reactor, after at room temperature stirring 25min, be heated to 60 DEG C, drip the 20%NaOH aqueous solution, dropwise in 30min, 70 DEG C are warming up to after dropwising, reaction 2h, adds distilled water and toluene, is stirred to dissolving, separatory, vacuum distillation obtains described brominated bisphenol-A type epoxy resin;
Embodiment 2
Tetrabromobisphenol A and epoxychloropropane are joined in reactor, after at room temperature stirring 30min, be heated to 50 DEG C, drip the 20%NaOH aqueous solution, dropwise in 60min, 80 DEG C are warming up to after dropwising, reaction 1.5h, adds distilled water and toluene, is stirred to dissolving, separatory, vacuum distillation obtains described brominated bisphenol-A type epoxy resin;
Embodiment 3
Tetrabromobisphenol A and epoxychloropropane are joined in reactor, after at room temperature stirring 28min, be heated to 60 DEG C, drip the 20%NaOH aqueous solution, dropwise in 50min, 75 DEG C are warming up to after dropwising, reaction 2h, adds distilled water and toluene, is stirred to dissolving, separatory, vacuum distillation obtains described brominated bisphenol-A type epoxy resin;
Embodiment 4
Tetrabromobisphenol A and epoxychloropropane are joined in reactor, after at room temperature stirring 27min, be heated to 58 DEG C, drip the 20%NaOH aqueous solution, dropwise in 55min, 85 DEG C are warming up to after dropwising, reaction 1h, adds distilled water and toluene, is stirred to dissolving, separatory, vacuum distillation obtains described brominated bisphenol-A type epoxy resin;
Embodiment 5
Tetrabromobisphenol A and epoxychloropropane are joined in reactor, after at room temperature stirring 30min, be heated to 54 DEG C, drip the 20%NaOH aqueous solution, dropwise in 4min, 79 DEG C are warming up to after dropwising, reaction 2h, adds distilled water and toluene, is stirred to dissolving, separatory, vacuum distillation obtains described brominated bisphenol-A type epoxy resin;
Table 1 is the raw materials consumption list of brominated bisphenol-A type epoxy resin in the embodiment of the present invention 1 ~ 5.
Table 1
In the present invention, the preparation embodiment of glue is as follows:
Embodiment 6
Get dimethyl formamide and ethylene glycol diglycidylether mix and blend obtains solvent, linear phenolic resin, embodiment 1 gained brominated bisphenol-A type epoxy resin, glyoxal ethyline, silane coupler and polybutadiene is added successively in gained solvent, stir, after slaking 10h, obtain described glue, solids content 75wt% in glue, sends into glue groove stand-by;
Embodiment 7
Get dimethyl formamide and ethylene glycol diglycidylether mix and blend obtains solvent, MDA, embodiment 2 gained brominated bisphenol-A type epoxy resin, benzyl dimethylamine, silane coupler and polyurethane is added successively in gained solvent, stir, after slaking 15h, obtain described glue, solids content 80wt% in glue, sends into glue groove stand-by;
Embodiment 8
Get dimethyl formamide and ethylene glycol diglycidylether mix and blend obtains solvent, curing agent, embodiment 3 gained brominated bisphenol-A type epoxy resin, 2-ethyl-4-methylimidazole, silane coupler and polybutadiene is added successively in gained solvent, stir, after slaking 15h, obtain described glue, solids content 78wt% in glue, sends into glue groove stand-by;
Embodiment 9
Get dimethyl formamide and ethylene glycol diglycidylether mix and blend obtains solvent, DADPS, embodiment 4 gained brominated bisphenol-A type epoxy resin, 2-phenylimidazole, silane coupler and polybutadiene is added successively in gained solvent, stir, after slaking 14h, obtain described glue, solids content 78wt% in glue, sends into glue groove stand-by;
Embodiment 10
Get dimethyl formamide and ethylene glycol diglycidylether mix and blend obtains solvent, DADPS, embodiment 5 gained brominated bisphenol-A type epoxy resin, promoter, silane coupler and active polyurethane is added successively in gained solvent, stir, after slaking 13h, obtain described glue, solids content 77wt% in glue, sends into glue groove stand-by;
Table 2 is amounts of components list each in glue described in the embodiment of the present invention 6 ~ 10.
Table 2. (unit wt%)
Brominated bisphenol-A Solvent Curing agent Promoter Silane coupled Active toughness reinforcing
Type epoxy resin Agent Agent
Embodiment 6 52 28 10 3 3 4
Embodiment 7 60 25 8 3 2 2
Embodiment 8 50 32 11 4 1 2
Embodiment 9 51 31 9 5 3 1
Embodiment 10 53 30 10 3 1 3
It is as shown in table 3 that the embodiment of the present invention manufactures the process conditions that described CEM-3 type covers in copper foil laminates base paper.Wherein embodiment 11 ~ 15 adopts embodiment 6 ~ 10 to prepare the glue of gained.
Table 3
The embodiment of the present invention 6 ~ 10 configure the performance parameter of fabric glue is as shown in table 4.
Table 4
The performance parameter that the embodiment of the present invention 11 ~ 15 manufacture gained CEM-1 type covers copper foil laminates base paper is as shown in table 6.
Table 6
It should be noted that, above embodiment is only in order to illustrate technical scheme of the present invention and unrestricted.Although with reference to preferred embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that, can modify to the technical scheme of invention or equivalent replacement, and not depart from the scope of technical solution of the present invention, it all should be encompassed in right of the present invention.

Claims (10)

1. CEM-3 type covers a manufacture method for copper foil laminates base paper, it is characterized in that, comprises the steps:
Preparation dipping glue
Preparation brominated bisphenol-A type epoxy resin
Tetrabromobisphenol A and epoxychloropropane are joined in reactor, after at room temperature stirring 25 ~ 30min, be heated to 50 ~ 60 DEG C, drip the 20%NaOH aqueous solution, dropwise in 30 ~ 60min, 70 ~ 90 DEG C are warming up to after dropwising, reaction 1 ~ 2h, adds distilled water and toluene, is stirred to dissolving, separatory, vacuum distillation obtains described brominated bisphenol-A type epoxy resin;
Preparation glue
Get dimethyl formamide and ethylene glycol diglycidylether mix and blend obtains solvent, curing agent, described brominated bisphenol-A type epoxy resin, promoter, silane coupler, inorganic filler and endurable active toughener is added successively in gained solvent, stir, after slaking 10 ~ 15h, obtain described fabric dipping glue, solids content 75 ~ 80wt% in glue, sends into a glue groove stand-by;
Manufacture fabric
Get the alkali-free glass fiber cloth of rolling, uncoiling, dipping process is carried out by the glue groove having described fabric dipping glue with the speed of 70 ~ 80m/min, send into drying chamber to dry, obtain prepreg, gel duration 170 ~ 210s, bake out temperature 90 ~ 100 DEG C, drying time 2 ~ 5min, obtains fabric after cutting;
Manufacture core material
Get the glass fiber paper of rolling, uncoiling, carry out soaking process with the speed of 60 ~ 70m/min by the glue groove having described core material dipping glue, after completing, then carry out secondary dipping process with the speed of 60 ~ 70m/min by the glue groove having described fabric dipping glue, after completing, feeding drying chamber is dried, obtain prepreg, gel duration 170 ~ 210s, bake out temperature 90 ~ 100 DEG C, drying time 2 ~ 5min, obtains core material after cutting;
By gained fabric and core material stacked, and the some upper surface of base plate after stacked cover Copper Foils, and bottom surface is placed on after padding one deck mould release membrance again between two corrosion resistant plates;
Put into laminating machine and carry out heating pressurized treatments, heating-up temperature is 170 ~ 175 DEG C, pressure is 1 ~ 2MPa, pressurize 10 ~ 15min, take out, cut, after inspection, obtain described CEM-3 type and cover copper foil laminates base paper product.
2. CEM-3 type according to claim 1 covers the manufacture method of copper foil laminates base paper, it is characterized in that, step 1) described in the mass volume ratio of tetrabromobisphenol A and epoxychloropropane be 1:1.5 ~ 3, g/ml; The mass volume ratio of described tetrabromobisphenol A and the 20%NaOH aqueous solution is 1:1.5 ~ 2, g/ml; The mass volume ratio of described tetrabromobisphenol A and toluene is 1:2 ~ 3, g/ml; The mass volume ratio of described tetrabromobisphenol A and distilled water is 1:1 ~ 2, g/ml.
3. CEM-3 type according to claim 1 covers the manufacture method of copper foil laminates base paper, it is characterized in that, step 1) in described glue, each constituent mass percentage is as follows: brominated bisphenol-A type epoxy resin: 50 ~ 60wt%, solvent: 25 ~ 35wt%, curing agent: 8 ~ 11wt%, promoter: 3 ~ 5wt%, silane coupler: 2 ~ 4wt%, inorganic filler: 1 ~ 2wt%, endurable active toughener: 1 ~ 2wt%.
4. CEM-3 type according to claim 1 covers the manufacture method of copper foil laminates base paper, it is characterized in that, step 1) in described glue, each constituent mass percentage is as follows: brominated bisphenol-A type epoxy resin: 52wt%, solvent: 28wt%, curing agent: 10wt%, promoter: 3wt%, silane coupler: 3wt%, inorganic filler: 2wt%, endurable active toughener: 2wt%.
5. the CEM-3 type according to claim 1 or 3 or 4 covers the manufacture method of copper foil laminates base paper, it is characterized in that, step 1) volume ratio of dimethyl formamide and ethylene glycol diglycidylether is 1:1 in described solvent.
6. the CEM-3 type according to claim 1 or 3 or 4 covers the manufacture method of copper foil laminates base paper, it is characterized in that, step 1) described curing agent is aromatic amine curing agent or linear phenolic resin.
7. the CEM-3 type according to claim 1 or 3 or 4 covers the manufacture method of copper foil laminates base paper, it is characterized in that, step 1) described promoter is imidazoles promoter or benzyl dimethylamine.
8. CEM-3 type according to claim 7 covers the manufacture method of copper foil laminates base paper, it is characterized in that, described imidazoles promoter is glyoxal ethyline, 2-ethyl-4-methylimidazole or 2-phenylimidazole.
9. the CEM-3 type according to claim 1 or 3 or 4 covers the manufacture method of copper foil laminates base paper, it is characterized in that, step 1) described endurable active toughener is polybutadiene or polyurethane.
10. the CEM-3 type according to claim 1 or 3 or 4 covers the manufacture method of copper foil laminates base paper, it is characterized in that, step 1) described inorganic filler is selected from one in aluminium hydroxide, talcum powder, calcium carbonate, silicon powder and kaolin.
CN201510477369.6A 2015-08-06 2015-08-06 CEM-3 type copper-clad laminated plate base paper manufacturing method Pending CN105128497A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510477369.6A CN105128497A (en) 2015-08-06 2015-08-06 CEM-3 type copper-clad laminated plate base paper manufacturing method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510477369.6A CN105128497A (en) 2015-08-06 2015-08-06 CEM-3 type copper-clad laminated plate base paper manufacturing method

Publications (1)

Publication Number Publication Date
CN105128497A true CN105128497A (en) 2015-12-09

Family

ID=54714226

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510477369.6A Pending CN105128497A (en) 2015-08-06 2015-08-06 CEM-3 type copper-clad laminated plate base paper manufacturing method

Country Status (1)

Country Link
CN (1) CN105128497A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110863360A (en) * 2019-12-06 2020-03-06 清远凯荣德玻璃纤维有限公司 Preparation process of high-temperature-resistant and corrosion-resistant electronic-grade glass fiber cloth
CN113715432A (en) * 2020-05-25 2021-11-30 杭州鸿禾电子科技有限公司 High-insulation GPO-3 epoxy glass fiber cloth laminated board and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1966572A (en) * 2005-11-16 2007-05-23 广东生益科技股份有限公司 Resin composition and its uses in adhesive sheet and copper-cladded plate
CN101423649A (en) * 2008-12-15 2009-05-06 山东金宝电子股份有限公司 Resin composition and method for preparing silver paste hole filled flame retardant type paper base copper clad laminate by using the same
CN102310607A (en) * 2011-07-08 2012-01-11 浙江华正新材料股份有限公司 Copper-clad plate with low-dielectric constant
CN102775733A (en) * 2012-08-09 2012-11-14 广东生益科技股份有限公司 Thermosetting resin composition as well as prepreg and copper clad laminate made from thermosetting resin composition
CN103213356A (en) * 2013-04-12 2013-07-24 江阴市明康绝缘玻纤有限公司 Preparation method of bisphenol A modified paper-base glass cloth copper-clad foil single-sided copper-clad plate

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1966572A (en) * 2005-11-16 2007-05-23 广东生益科技股份有限公司 Resin composition and its uses in adhesive sheet and copper-cladded plate
CN101423649A (en) * 2008-12-15 2009-05-06 山东金宝电子股份有限公司 Resin composition and method for preparing silver paste hole filled flame retardant type paper base copper clad laminate by using the same
CN102310607A (en) * 2011-07-08 2012-01-11 浙江华正新材料股份有限公司 Copper-clad plate with low-dielectric constant
CN102775733A (en) * 2012-08-09 2012-11-14 广东生益科技股份有限公司 Thermosetting resin composition as well as prepreg and copper clad laminate made from thermosetting resin composition
CN103213356A (en) * 2013-04-12 2013-07-24 江阴市明康绝缘玻纤有限公司 Preparation method of bisphenol A modified paper-base glass cloth copper-clad foil single-sided copper-clad plate

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
李红强: "《胶粘原理、技术及应用》", 31 January 2014 *
黄玉媛: "《精细化工配方常用原料手册》", 30 March 1998 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110863360A (en) * 2019-12-06 2020-03-06 清远凯荣德玻璃纤维有限公司 Preparation process of high-temperature-resistant and corrosion-resistant electronic-grade glass fiber cloth
CN110863360B (en) * 2019-12-06 2020-06-30 清远凯荣德玻璃纤维有限公司 Preparation process of high-temperature-resistant and corrosion-resistant electronic-grade glass fiber cloth
CN113715432A (en) * 2020-05-25 2021-11-30 杭州鸿禾电子科技有限公司 High-insulation GPO-3 epoxy glass fiber cloth laminated board and preparation method thereof

Similar Documents

Publication Publication Date Title
CN105150662A (en) Manufacturing method of epoxy glass-cloth-matrix copper clad laminate
JP6754999B2 (en) Resin composition, low dielectric constant resin sheet, prepreg, metal foil laminated board, high frequency circuit board and multilayer wiring board
US4659425A (en) Continuous process for the manufacture of printed circuit boards
JPH0443930B2 (en)
CN103642446A (en) Lead-free high heat-resisting copper-clad board and preparation method thereof
KR20160126043A (en) Halogen-Free Flame-Retardant Resin Composition
US20160244471A1 (en) Phenoxycyclotriphosphazene active ester, halogen-free resin composition and uses thereof
EP2752449A1 (en) Halogen-free resin composition and method for preparation of copper clad laminate with same
CN103059510A (en) Compositions useful for preparing composites and composites produced therewith
CN103980708A (en) Halogen-free flame-retardant thermosetting resin composition of integrated circuit, prepreg and laminate
CN101885900A (en) Resin composition, bonding sheet and copper-clad plate made using same, manufacturing method thereof
CN104559888A (en) Copper-clad plate applicable to production of high multi-layer PCB (printed circuit board) and preparation method of copper-clad plate
CN104559068A (en) Thermosetting resin composition as well as preparation method and application thereof
CN103802394A (en) Copper-clad plate suitable for lead-free process and preparation method of copper-clad laminate
TW201609946A (en) Epoxy resin composition, resin sheet, and prepreg, and metal-clad laminate board, printed circuit board, and semiconductor device
CN103980667A (en) Thermosetting resin composition of integrated circuit, prepreg and laminate
JPS6250303B2 (en)
CN109719967B (en) High-toughness high-Tg lead-free copper-clad plate and preparation method thereof
CN105128497A (en) CEM-3 type copper-clad laminated plate base paper manufacturing method
CN105058946B (en) Manufacturing method for CEM-1 type copper clad laminate
JP6112452B2 (en) Double-sided metal-clad laminate and method for producing the same
CN115651335B (en) Resin composition and prepreg and copper-clad plate containing resin composition
US5976699A (en) Insulating adhesive for multilayer printed circuit board
JP2001261791A (en) Epoxy resin composition, prepreg and laminated plate
CN103978768A (en) Preparation method for bisphenol A modified phenolic paper-based single-side copper-clad plate

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20151209