CN109760385B - Copper-clad plate capable of being bent statically, manufacturing method thereof and bending forming method - Google Patents

Copper-clad plate capable of being bent statically, manufacturing method thereof and bending forming method Download PDF

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CN109760385B
CN109760385B CN201711092318.7A CN201711092318A CN109760385B CN 109760385 B CN109760385 B CN 109760385B CN 201711092318 A CN201711092318 A CN 201711092318A CN 109760385 B CN109760385 B CN 109760385B
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copper
clad plate
bending
weight
thermosetting resin
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CN109760385A (en
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刘东亮
杨中强
陈文欣
许永静
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Shengyi Technology Co Ltd
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Shengyi Technology Co Ltd
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Priority to CN201711092318.7A priority Critical patent/CN109760385B/en
Priority to KR1020207010580A priority patent/KR102591030B1/en
Priority to PCT/CN2017/117435 priority patent/WO2019090916A1/en
Priority to TW107106259A priority patent/TWI785011B/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D11/00—Bending not restricted to forms of material mentioned in only one of groups B21D5/00, B21D7/00, B21D9/00; Bending not provided for in groups B21D5/00 - B21D9/00; Twisting
    • B21D11/02—Bending by stretching or pulling over a die
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D11/00—Bending not restricted to forms of material mentioned in only one of groups B21D5/00, B21D7/00, B21D9/00; Bending not provided for in groups B21D5/00 - B21D9/00; Twisting
    • B21D11/22—Auxiliary equipment, e.g. positioning devices
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/02—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments
    • B32B17/04—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments bonded with or embedded in a plastic substance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/061—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/08—Impregnating
    • 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
    • B32B5/02—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
    • B32B5/022—Non-woven fabric
    • 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
    • B32B7/08—Interconnection of layers by mechanical means
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • 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
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/07—Parts immersed or impregnated in a matrix
    • B32B2305/076—Prepregs

Abstract

The invention provides a copper-clad plate capable of being bent statically, a manufacturing method thereof and a bending forming method. The copper-clad plate comprises a copper foil and a thermosetting resin composition impregnated base cloth adhered on the copper foil, wherein the copper-clad plate has the elastic bending modulus of more than 10GPa, the peel strength between 60 and 200 ℃ of more than 1.0N/mm, and after the copper foil is removed, the copper-clad plate has the maximum stress value of more than 400MPa and the fracture strain value of more than 4 percent. The copper-clad plate can be formed into the copper-clad plate with a bending structure through one-time or several-time stamping forming.

Description

Copper-clad plate capable of being bent statically, manufacturing method thereof and bending forming method
Technical Field
The invention relates to the technical field of copper-clad plates, in particular to a copper-clad plate capable of being bent statically, a manufacturing method thereof and a bending forming method thereof.
Background
The copper-clad plate mainly plays a role in mechanical support and electrical connection in the application of the electronic industry, but in the requirements of three-dimensional installation and partial three-dimensional support, the traditional rigid copper-clad plate is easy to break in the bending process due to higher brittleness; the traditional Flexible Copper Clad Laminate (FCCL) has good flexibility, but has insufficient supporting capability and cannot be used for supporting alone. In addition, when the rigid copper clad laminate and the flexible copper clad laminate are combined and applied to be used as a rigid-flex board, the processing procedure is complex, the processing difficulty is high, and the cost is high.
In many electronic products and electromechanical industries, the material is required to be subjected to static bending application, namely, the material is subjected to static bending, namely, the material is bent once during installation, or after the material is bent once, a bending area does not need to swing, namely, the material is static during working and does not swing back and forth like a laser head of a printer; however, even in these static bending fields, the common rigid copper clad laminate cannot meet the use requirements of bending molding in many cases.
Therefore, in many static bending application fields, the copper-clad plate material is required to have the processing capacity of one-time or several-time bending forming, impact stress can be well borne in the bending forming process, cracking and layering are avoided, various three-dimensional bending or concave-convex shapes are punched for fixing, and the subsequent static bending installation and use are facilitated.
Disclosure of Invention
The invention aims to provide a novel rigid and tough copper-clad plate without using a flexible plate (FCCL) and a bending forming method thereof.
The purpose of the invention can be realized by the following technical scheme.
One aspect of the invention provides a copper-clad plate capable of being statically bent, which comprises a copper foil and a thermosetting resin composition impregnation base cloth adhered on the copper foil, wherein the copper-clad plate has an elastic bending modulus of more than 10GPa (preferably more than 12GPa), a peel strength between 60 and 200 ℃ of more than 1.0N/mm, and after the copper foil is removed, has a maximum stress value of more than 400MPa and a fracture strain value of more than 4%.
In certain embodiments, the thermosetting resin composition comprises: a thermosetting resin; a curing agent; a toughening material; and a solvent, wherein the thermosetting resin is 100 parts by weight, the curing agent is 1-50 parts by weight, the toughening material is 20-60 parts by weight, and the solvent is 5-50 parts by weight.
In certain embodiments, the thermosetting resin comprises an epoxy resin, preferably a multifunctional epoxy resin; and/or the curing agent comprises at least one of phenolic resin, amine compound, acid anhydride, imidazole compound, sulfonium salt, dicyandiamide and active ester; and/or the toughening material comprises rubber (preferably rubber with a core-shell structure), phenoxy resin, polyvinyl butyral (PVB), nylon and nano particles (preferably SiO) 2 ，TiO 2 Or CaCO 3 Nanoparticles), olefinic block copolymers (preferably block copolymers of polymethacrylic acid, butadiene and styrene); and/or, the solvent comprises at least one of Dimethylformamide (DMF), ethylene glycol monomethyl ether (MC), propylene glycol methyl ether (PM), Methyl Ethyl Ketone (MEK), toluene, xylene.
In certain embodiments, the base fabric comprises a fiberglass cloth or a non-woven fabric.
Another aspect of the present invention provides a method for manufacturing the above copper-clad plate, wherein the method comprises:
impregnating or coating the base cloth with the thermosetting resin composition, and heating at 100-200 ℃ for 1-10 minutes to form a prepreg;
and (3) attaching the prepreg to the copper foil, and performing hot-pressing curing at the temperature of not more than 180-200 ℃ for 40-120 minutes to form the copper-clad plate.
In another aspect, the invention provides a copper-clad plate bending and forming method, which comprises the following steps: the copper-clad plate of any one of claims 1 to 4 is placed in a die for punch forming, and the die is designed to form a bending structure with a bending angle of 10-90 degrees and a bending radius of 1-25 mm.
In some embodiments, the copper clad laminate is heated to a temperature of 60-200 ℃ prior to being placed in the mold.
In certain embodiments, the conditions of the punch forming include:
1) stamping pressure: 100N-20000N;
2) press molding maintenance time: 2sec or more;
3) temperature of the die: normal temperature (20-35 ℃) or heating to below 100 ℃.
In some embodiments, the forming temperature of the punch forming is the glass transition temperature of the thermosetting resin composition in the copper-clad plate +/-50 ℃, and the setting time is more than or equal to 2 sec.
The invention also provides a copper-clad plate with a bending structure, which is manufactured by one-time or several-time forming by adopting the bending forming method and has a bending angle of 10-90 degrees and a bending radius of 1-25 mm.
The invention may have at least one of the following advantages:
1. the copper-clad plate can be plastically deformed within a certain temperature range under the action of mechanical force, and the shape generated by the original deformation can not be changed when the mechanical force is released and the copper-clad plate is recovered to the normal temperature, so that the copper-clad plate can be fixedly formed, namely, the copper-clad plate has certain rigidity to bear the stress action, generates deformation without breakage, and has deformation strain.
2. The production process flow of the copper-clad plate is simple, a flexible plate (FCCL) is not needed, the efficiency is improved, and the cost is saved.
3. The copper-clad plate has the processing capacity of one-time or several-time bending forming, can better bear impact stress in the bending forming process, does not crack or delaminate, can be punched into various three-dimensional bending or concave-convex shape fixation, and is convenient for subsequent static bending installation and use.
Drawings
Fig. 1 shows five types of stress-strain curves.
FIG. 2 shows a typical stress (F) -strain (L) curve of the CCL of the present invention obtained according to tensile strength and tensile modulus test method.
Fig. 3 shows the bending radius of the copper clad laminate formed by bending in example 1 of the present application.
Fig. 4 shows the bending angle of the copper clad laminate formed by bending in example 1 of the present application.
Detailed Description
The present invention surprisingly found that: the thermosetting resin composition containing the toughening material is used for impregnating base fabrics such as glass fiber cloth and the like to prepare a prepreg, the prepreg is laminated and compounded with the copper foil, and the copper clad laminate with rigid and tough (or hard and tough) characteristics can be obtained after complete curing.
The stress-strain curve of a material with hard and tough characteristics is shown as curve 2 in fig. 1. In fig. 1, the material properties represented by the respective curves are as follows: 1. hard and brittle; 2. hard and tough; 3. hard and strong; 4. soft and tough; 5. soft and weak.
Based on the discovery, the invention provides a copper-clad plate capable of being statically bent, and a manufacturing method and a bending forming method thereof. Various aspects of the invention are described in detail below.
Copper-clad plate
One aspect of the invention provides a copper-clad plate capable of being statically bent, which comprises a copper foil and base cloth adhered to the copper foil and impregnated by the thermosetting resin composition.
Thermosetting resin composition
In the present invention, the thermosetting resin composition for impregnating the base fabric may comprise: a thermosetting resin; a curing agent; a toughening material; and a solvent.
In certain embodiments, the thermosetting resin may include epoxy resins, phenolic resins, polyimide resins, urea-formaldehyde resins, melamine resins, unsaturated polyesters, polyurethane resins, and the like, with epoxy resins being preferred.
Specific examples of the epoxy resin may include: bisphenol a epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, aralkyl epoxy resin, phenol novolac epoxy resin (phenol novolac type epoxy resin), alkyl novolac epoxy resin (alkyl novolac type epoxy resin), bisphenol epoxy resin, naphthalene epoxy resin, dicyclopentadiene epoxy resin, epoxy compound obtained by condensing phenol compound and aromatic aldehyde having a phenolic hydroxyl group, triglycidyl isocyanurate, alicyclic epoxy resin, and the like. These epoxy resins may be used alone or in combination of two or more kinds depending on the case.
Preferably, the epoxy resin is a polyfunctional epoxy resin containing two or more epoxy groups (preferably three or more epoxy groups) in one molecule. As such an epoxy resin, commercially available epoxy resins, for example, JER1003 (manufactured by Mitsubishi chemical corporation, 7 to 8 methyl groups, bifunctional, molecular weight 1300), EXA-4816 (manufactured by Diegon, molecular weight 824, majority methyl groups, bifunctional), YP50 (manufactured by Nichikomo Metal chemical corporation, molecular weight 60000 to 80000, majority methyl groups, bifunctional), DER593 (manufactured by Dow chemical corporation, polyfunctional epoxy resin), EPIKOTE 157 (manufactured by Resolution, polyfunctional epoxy resin), and the like can be used.
In certain embodiments, the curing agent in the thermosetting resin composition may be determined according to the kind of the thermosetting resin. For the epoxy resin, the curing agent may include at least one of a phenol resin, an amine-based compound, an acid anhydride, an imidazole-based compound, a sulfonium salt, dicyandiamide, and an active ester.
The active ester curing agent is obtained by reacting a phenolic compound, a difunctional carboxylic aromatic compound or an acid halide and a monohydroxy compound which are connected through an aliphatic cyclic hydrocarbon structure. The dosage of the difunctional carboxylic acid aromatic compound or the acid halide is 1mol, the dosage of the phenolic compound connected through the aliphatic cyclic hydrocarbon structure is 0.05-0.75 mol, and the dosage of the monohydroxy compound is 0.25-0.95 mol. The active ester curing agent may include an active ester of the formula:
Figure BDA0001461508580000051
wherein X in the formula is a benzene ring or a naphthalene ring, j is 0 or 1, k is 0 or 1, and n represents an average repeating unit of 0.25-1.25.
In certain embodiments, the curing agent is preferably a phenolic resin, an amine-based compound, an imidazole-based compound, and dicyandiamide. These curing agents may be used alone or in combination of two or more. Specific curing agents may include: phenolic resins (e.g., phenol novolac resins, cresol novolac resins, etc.); diamino Diphenyl Sulfone (DDS); dicyandiamide (DICY); dimethylimidazole (2-MI), and the like.
The curing agent is generally used in an amount of 1 to 50 parts by weight, for example, 1 to 40 parts by weight, or 1 to 30 parts by weight, relative to 100 parts by weight of the thermosetting resin. For epoxy resins, the amount of curing agent can be controlled such that the ratio of epoxy equivalents of the epoxy resin to hydroxyl equivalents of the phenolic resin is 1:1 to 0.95; or the equivalent ratio of the epoxy resin to the amino group is 1: 0.6 to 0.4.
In certain embodiments, the toughening material comprises at least one of rubber, phenoxy resin, polyvinyl butyral (PVB), nylon, nanoparticles, olefinic block copolymers. These toughening materials are selected according to compatibility with thermosetting resins such as epoxy resins, toughening effect (to achieve a corresponding stress strain requirement (described later)), and the like. Among them, the rubber is preferably a rubber having a core-shell structure, such as methylmethacrylate-butadiene-styrene (MBS) core-shell type copolymer resin, rubber-epoxy type core-shell resin, etc., and representative thereof commercially include M-521, MX-395, etc. of Bell-source in Japan. The nanoparticles comprise SiO 2 ，TiO 2 Or CaCO 3 Nanoparticles and the like, the particle diameter of which is generally 10 to 500 nm. Olefinic block copolymers are block copolymers formed by the copolymerization of different types of olefins, for example, block copolymers of polymethacrylic acid, butadiene and styrene.
The toughening materials may be used singly or in combination of two or more. For example, the nanoparticles can be used in combination with another toughening material (e.g., core shell rubber, phenoxy resin, PVB, nylon, olefinic block copolymer, or mixtures thereof) in a weight ratio of 1:10 to 2: 1.
To achieve good toughening, the total amount of toughening materials used is generally from 20 to 60 parts by weight, for example, from 20 to 50 parts by weight, or from 30 to 60 parts by weight, per 100 parts by weight of the thermosetting resin.
In certain embodiments, the solvent may include at least one of Dimethylformamide (DMF), ethylene glycol methyl ether (MC), propylene glycol methyl ether (PM), propylene glycol methyl ether acetate (PMA), cyclohexanone, Methyl Ethyl Ketone (MEK), toluene, xylene. The solvent is generally used in an amount of 5 to 50 parts by weight, for example, 10 to 50 parts by weight, 20 to 50 parts by weight, etc., relative to 100 parts by weight of the thermosetting resin, to form a dope having a viscosity of 300-600 cPa.s.
In certain embodiments, the thermosetting resin composition may further contain fillers or auxiliaries and the like, such as flame retardants, leveling agents, colorants, dispersants, coupling agents, foaming agents and the like, within a range in which the effects of the present invention are not lost. Wherein the flame retardant can be one or more of organic flame retardant such as tetrabromobisphenol A, DOPO and phosphate.
-base cloth-
In certain embodiments, the base fabric comprises a fiberglass cloth or a non-woven fabric. The glass fiber cloth can be selected from 7628, 2116, 1080, 106, 1037, 1027, 1017 and other specifications.
-copper foil-
In some embodiments, the copper foil can be selected from 1OZ, 1/2OZ, 1/3OZ, and the like.
Copper clad laminate capable of being bent statically
The copper-clad plate capable of being statically bent can be plastically deformed within a certain temperature range under the action of mechanical force, and the shape generated by the original deformation cannot be changed when the mechanical force is released and the copper-clad plate is restored to the normal temperature, so that the copper-clad plate can be fixedly formed.
In certain embodiments, the copper clad laminate has a flexural modulus of elasticity >10GPa, a peel strength between 60-200 ℃ of greater than 1.0N/mm, and, after removal of the copper foil, a maximum stress value of greater than 400MPa and a strain at break value of greater than 4%.
The stress strain value is measured by the following tensile strength and tensile modulus test methods.
The method for testing the tensile strength and the tensile modulus of the material comprises the following steps:
A. test devices and/or materials
-material testing machine
A tensile compression tester according to ISO3384 standard, which can operate the tensile clamp at a stable speed. The error of the load measurement system does not exceed +/-1%.
An etching system capable of completely removing the metal-clad foil.
Vernier calipers (to the nearest 0.02mm) or micrometers (to the nearest 0.002mm)
-test sample
(1) Size and shape
The dimensions of the test specimen are 250mm × 25mm, the thickness of the test specimen is preferably 0.4mm, and the edge of the test specimen should be free from defects such as cracks, delamination and the like, otherwise, the test specimen is ground by sand paper or an equivalent tool (the edge is not formed into a round angle).
(2) Quantity and sampling
When the coefficient of variation is less than 5%, ten specimens, five pieces in the longitudinal direction and five pieces in the transverse direction (cut out on the whole sample plate or platelet) are used for each batch. When the dispersion coefficient is larger than 5%, the number of samples in each direction cannot be less than 10, and 10 valid samples are guaranteed.
(3) All the metal covering layer is etched and removed by an etching method.
B. Tensile test procedure
Measuring the dimensions of the sample
The width and thickness of the test specimen were measured and recorded, with the width being accurate to 0.02mm and the thickness being accurate to 0.002 mm.
-measuring
(1) And clamping the sample to make the center line of the sample consistent with the alignment center line of the upper clamp and the lower clamp.
(2) The distance between the upper clamp and the lower clamp is adjusted to be 125mm +/-0.5 mm.
(3) The loading speed was 12.5 mm/min.
(4) The tensile modulus calculation was set at a fraction between 0.05% and 0.25% strain.
(5) The test was performed and stress-strain curves were plotted.
(6) Specimens with significant internal defects should be discarded.
(7) The specimen should be rejected if the specimen breaks in the fixture or if the specimen breaks less than 10mm from the clamped position.
C. Computing
The tensile strength of each specimen was calculated as follows
Figure BDA0001461508580000071
In the formula:
τ T : tensile strength, MPa
F: breaking or maximum load, N
b: width of specimen in mm
d: thickness of the sample in mm
The tensile modulus of elasticity of each specimen was calculated as follows
Figure BDA0001461508580000072
In the formula:
E t : tensile modulus of elasticity, MPa
σ ": tensile stress value measured at 0.25% epsilon ∈ strain, MPa
σ': tensile stress value measured at 0.05% ε strain, (. epsilon.'), MPa
-calculating the average tensile strength and the tensile modulus of elasticity in MPa.
Fig. 2 shows a typical stress-strain curve of the copper clad laminate obtained according to the tensile strength and tensile modulus test method described above. As shown in FIG. 2, the copper clad laminate of the present invention (after etching to remove the metal capping layer) has a maximum stress value of more than 400MPa and a fracture strain value of more than 4%.
Method for manufacturing copper-clad plate
The copper-clad plate can be manufactured according to the following method:
preparation of prepregs
The base cloth is impregnated or coated with the thermosetting resin composition in the form of the glue of the present invention, and then heated at 100-200 ℃ for 1-10 minutes (e.g., 3-10 minutes) to obtain a prepreg (a semi-cured B-stage state). The resin content of the prepreg can be controlled to be between 40 and 70 wt%, and the resin fluidity of the prepreg can be controlled to be between 10 and 30%.
Preparation of copper clad laminate
And laminating the cut prepreg on a copper foil, carrying out hot pressing at the heating rate of 1-3 ℃/min, keeping the pressure at the maximum of 300-500PSI, and keeping the temperature at the maximum of 180-200 ℃ for 30-120 minutes (such as 60-120 minutes) to obtain the copper-clad plate.
Copper-clad plate bending forming method
The invention also provides a copper-clad plate bending and forming method, which comprises the following steps: and putting the copper-clad plate into a die for punch forming.
In certain embodiments, the die is pre-designed with different bend radii (2-50mm) and bend angles (10-90 °).
In certain embodiments, the copper clad laminate is heated to a temperature of 60-200 ℃ prior to being placed in the mold.
In some embodiments, the press molding temperature is + -50 deg.C (preferably + -30 deg.C) of the glass transition temperature of the thermosetting resin composition in the copper-clad laminate, and the setting time is 2sec or more.
In certain embodiments, the conditions of the stamping forming include:
1) stamping pressure: 100N-20000N;
2) press molding maintenance time: 2sec or more;
3) temperature of the die: normal temperature (20-35 ℃) or heating to below 100 ℃.
In certain embodiments, other clamp parameters may include: the mold clamping rate is 0 to 2000mm/min, and the upper limit of the mold clamping pressure value is 100 to 20000N.
In certain embodiments, the number of copper clad laminate layers subjected to stamping forming can be 4-14 layers, and the thickness can be 0.2 mm-1 mm.
In certain embodiments, one or more stamping presses may be performed to achieve various bending forms.
Copper-clad plate with bending structure
In another aspect, the invention provides a copper-clad plate with a bending structure, which can be manufactured by the bending forming method.
In certain embodiments, the copper-clad plate has a bending angle of 10 to 90 ° and a bending radius of 1mm to 25 mm.
In certain embodiments, the copper clad laminate may be made by one or several molding passes.
The technical solution of the present invention is further described below with reference to specific examples. These examples are illustrative only and are not intended to limit the scope of the present invention.
Example 1:
1. glue solution preparation: 5 parts by weight of rubber (Japanese Brillouin M-521), 10 parts by weight of core-shell rubber (Japanese Brillouin MX-395) and 20 parts by weight of nano SiO 2 (winning bond Nanopol A710) as a toughening material was mixed with 100 parts by weight of a multifunctional epoxy resin (Dow chemical DER593 resin) and a phenolic resin (Dow chemical XZ92741 resin) was added so that the epoxy equivalent to hydroxyl equivalent ratio was 1:1 and a proper amount of MEK organic solvent are prepared into glue solution, and the viscosity of the glue solution is controlled to be between 300-600 cPAS.
2. Manufacturing a prepreg: the glue is firstly used for dipping the glass fiber cloth (2116 glass fiber cloth) for gluing, and then the glass fiber cloth is put into an oven for heating and baking for 3 to 10 minutes at the temperature of 100-.
3. Manufacturing a copper-clad plate: selecting 1OZ copper foil, combining with the prepreg, placing into a laminating machine, heating at a rate of 1-3 ℃/min, pressing at a maximum pressure of 300-.
4. And (3) bending and forming: (1) firstly, heating the copper-clad plate to 60 ℃; (2) and (3) after the temperature of the heated copper-clad plate is stable, putting the copper-clad plate into a stamping machine, pressing the copper-clad plate for 5 seconds under the pressure of 10000N, then opening the die, and taking out the copper-clad plate. The bending radius and the bending angle of the resulting copper-clad plate are shown in fig. 3 and 4.
5. The copper-clad plate is tested for appearance, elastic modulus, thermal shock (288 ℃/10S), reflow soldering (maximum stable 280 ℃) and other related characteristics, and the stress strain value is determined according to the tensile strength and tensile modulus testing method described in the specification.
Example 2:
a copper-clad plate was produced in the same manner as in example 1, except for the following glue solution configuration.
Glue solution preparation: selecting 20 parts by weight of phenol oxygen (HEXION company 53BH35) and 10 parts by weight of core-shell rubber CSR (Japanese Brillouin MX-395) as toughening materials, mixing with 100 parts by weight of multifunctional epoxy resin (Resolution company EPIKOTE 157 resin), adding 2.5 parts by weight of dicyandiamide and a proper amount of DMF organic solvent, preparing into glue solution, and controlling the viscosity of the glue solution to be suitable for dipping and gluing glass fibers.
And (3) bending and forming: (1) firstly, heating the copper-clad plate to 120 ℃; (2) and (3) after the temperature of the heated copper-clad plate is stable, putting the copper-clad plate into a die stamping machine, pressing for 100 seconds at the pressure of 100N, then opening the die, and taking out the copper-clad plate. The bending radius and the bending angle of the copper clad laminate were the same as those of example 1.
The appearance, modulus of elasticity, stress strain value, thermal shock, reflow soldering, and the like were measured according to the method described in example 1.
Example 3:
a copper-clad plate was produced in the same manner as in example 1, except for the following glue solution configuration.
Glue solution preparation: 20 parts of PVB (Nako B90) and 8 parts of nano SiO by weight are selected 2 (winning bond Nanopolo A710) and 5 parts by weight of a block copolymer (Achima)
Figure BDA0001461508580000101
Figure BDA0001461508580000102
M52N) is a toughening material, and is mixed with 100 parts by weight of multifunctional epoxy resin (DER 593 resin of DOW chemical company), 3 parts by weight of dicyandiamide and a proper amount of DMF or PM organic solvent are added to prepare a glue solution, and the viscosity of the glue solution is controlled between 300-.
And (3) bending and forming: (1) firstly, heating the copper-clad plate to 200 ℃; (2) and (3) after the temperature of the heated copper-clad plate is stable, putting the copper-clad plate into a die stamping machine, pressing for 2 seconds under 20000N pressure, then opening the die, and taking out the copper-clad plate. The bending radius and the bending angle of the copper clad laminate were the same as those of example 1.
The appearance, modulus of elasticity, stress strain value, thermal shock, reflow soldering, and the like were measured according to the method described in example 1.
Example 4:
a copper-clad plate was produced in the same manner as in example 1, except for the following glue solution configuration.
Glue solution preparation: selecting 20 weight parts of nylon (such as DuPont ST801A in USA) and 8 weight parts of nano SiO 2 (winning Nanopol A710), mixing with 100 weight parts of multifunctional epoxy resin (DOW chemical DER593 resin), adding phenolic resin (EPIKURE YLH129B65 of Resolution company) and a proper amount of MEK organic solvent according to the epoxy equivalent and hydroxyl equivalent of 1:1, preparing into glue solution, and controlling the viscosity of the glue solution between 300 and 600 cPAS.
And (3) bending and forming: (1) firstly, heating the copper-clad plate to 100 ℃; (2) and (3) after the temperature of the heated copper-clad plate is stable, putting the copper-clad plate into a die stamping machine, pressing for 10 seconds at 10000N pressure, then opening the die, and taking out the copper-clad plate. The bending radius and the bending angle of the copper clad laminate were the same as those of example 1.
The appearance, modulus of elasticity, stress strain value, thermal shock, reflow soldering, and the like were measured according to the method described in example 1.
Example 5:
a copper-clad plate was produced in the same manner as in example 1, except for the following glue solution configuration.
Glue solution preparation: selecting 25 weight parts of block copolymer (Acoma)
Figure BDA0001461508580000111
M52N) and 8 parts by weight of nano SiO 2 (winning Nanopol A710) is taken as a toughening material, is mixed with 100 parts by weight of cyanate ester resin (HF-10 of Huiyou corporation), and is added with 20 parts by weight of phenolic resin (EPIKURE YLH129B65 of RESOLUTION corporation) and a proper amount of MEK organic solvent to prepare glue solution, and the viscosity of the glue solution is controlled between 300 and 600 cPAS.
And (3) bending and forming: (1) firstly, heating the copper-clad plate to 200 ℃; (2) and (3) after the temperature of the heated copper-clad plate is stable, putting the copper-clad plate into a die stamping machine, pressing the copper-clad plate for 20 seconds at 10000N pressure, then opening the die, and taking out the copper-clad plate. The bending radius and the bending angle of the copper clad laminate were the same as those of example 1.
The appearance, modulus of elasticity, stress strain value, thermal shock, reflow soldering, and the like were measured according to the method described in example 1.
Example 6:
a copper-clad plate was produced in the same manner as in example 1, except for the following glue solution configuration.
Glue solution preparation: selecting 20 weight parts of phenoxy resin (Nissie iron chemical ERF-001), 10 weight parts of PVB (U.S. Konno B90) and 5 weight parts of nano SiO 2 (winning Nanopolo A710) is used as a toughening material, and is mixed with 50 weight parts of PPO resin (MX 90 from Shabo base company) and 100 weight parts of epoxy resin (DOW chemical DER593 resin), 20 weight parts of phenolic resin (EPIKURE YLH129B65 from RESOLUTION company) and a proper amount of MEK organic solvent are added to prepare a glue solution, and the viscosity of the glue solution is controlled to be between 300 and 600 cPAS.
And (3) bending and forming: (1) firstly, heating the copper-clad plate to 100 ℃; (2) and (3) after the temperature of the heated copper-clad plate is stable, putting the copper-clad plate into a die stamping machine, pressing for 50 seconds at 10000N pressure, then opening the die, and taking out the copper-clad plate. The bending radius and the bending angle of the copper clad laminate were the same as those of example 1.
The appearance, modulus of elasticity, stress strain value, thermal shock, reflow soldering, and the like were measured according to the method described in example 1.
Comparative example 1:
except for the following glue solution configuration, the copper clad laminate was manufactured and bent in the same manner as in example 1, and the corresponding properties were tested.
Glue solution preparation: selecting 100 weight parts of multifunctional epoxy resin (DOW chemical DER593 resin), adding 2-3 weight parts of dicyandiamide and a proper amount of DMF organic solvent to prepare glue solution, and controlling the viscosity of the glue solution between 300 and 600 cPAS.
Comparative example 2:
except for the following glue solution configuration, the copper clad laminate was manufactured and bent in the same manner as in example 1, and the corresponding properties were tested.
Glue solution preparation: 10 parts by weight of nitrile butadiene rubber (Japanese Brillouin M-521) and 100 parts by weight of multifunctional epoxy resin (DOW chemical DER593 resin) are mixed, 2-3 parts by weight of dicyandiamide and a proper amount of DMF organic solvent are added to prepare a glue solution, and the viscosity of the glue solution is controlled to be between 300-.
The test results are given in the following table:
Figure BDA0001461508580000121
Figure BDA0001461508580000131
the above are only some embodiments of the present invention, and it is obvious to those skilled in the art that other various changes and modifications can be made according to the technical solution and technical idea of the present invention, and all such changes and modifications should fall within the scope of the claims of the present invention.
The present invention is illustrated in detail by the examples described above, but the present invention is not limited to the details described above, i.e., it is not intended that the present invention be implemented by relying on the details described above. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of the raw materials of the product of the present invention, and the addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (12)

1. The copper-clad plate capable of being bent statically is characterized by comprising a copper foil and a thermosetting resin composition impregnation base cloth adhered on the copper foil, wherein the copper-clad plate has the elastic bending modulus of more than 10GPa, the peel strength between 60 and 200 ℃ of more than 1.0N/mm, and after the copper foil is removed, the copper-clad plate has the maximum stress value of more than 400Mpa and the fracture strain value of more than 4 percent,
wherein the thermosetting resin composition comprises: a thermosetting resin; a curing agent; a toughening material; and a solvent, wherein the thermosetting resin is 100 parts by weight, the curing agent is 1-50 parts by weight, the toughening material is 20-60 parts by weight, and the solvent is 5-50 parts by weight,
wherein the thermosetting resin comprises an epoxy resin;
wherein the curing agent comprises at least one of phenolic resin, amine compound, acid anhydride, imidazole compound, sulfonium salt and active ester;
wherein the toughening material comprises the combination of nanoparticles and at least one of rubber, phenoxy resin, polyvinyl butyral, nylon and olefinic block copolymer with a core-shell structure;
wherein the nanoparticles are used in combination with at least one of rubber, phenoxy resin, polyvinyl butyral, nylon, olefinic block copolymers in a weight ratio of 1:10 to 2: 1.
2. The copper-clad plate according to claim 1, wherein the epoxy resin is a multifunctional epoxy resin.
3. The copper-clad plate of claim 1, wherein the nanoparticles comprise SiO 2 ，TiO 2 Or CaCO 3 Nanoparticles.
4. The copper-clad plate according to claim 1, wherein the olefinic block copolymer comprises a block copolymer of polymethacrylic acid, butadiene and styrene.
5. The copper-clad plate according to claim 1, wherein the solvent comprises at least one of dimethylformamide, ethylene glycol methyl ether, propylene glycol methyl ether acetate, cyclohexanone, methyl ethyl ketone, toluene, and xylene.
6. The copper-clad plate of claim 1, wherein the base fabric comprises a glass fiber cloth or a non-woven fabric.
7. A method for manufacturing the copper-clad plate according to any one of claims 1 to 6, wherein the method comprises the following steps:
impregnating or coating the base cloth with the thermosetting resin composition, and heating at 100-200 ℃ for 1-10 minutes to form a prepreg;
and (3) attaching the prepreg to a copper foil, and performing hot-pressing curing at the temperature of 180-200 ℃ for 30-120 minutes to form the copper-clad plate.
8. A copper-clad plate bending forming method is characterized by comprising the following steps: the copper-clad plate of any one of claims 1 to 6 is placed into a die for punch forming, and the die is designed for forming a bending structure with a bending angle of 10-90 degrees and a bending radius of 1-25 mm.
9. The method according to claim 8, wherein the copper-clad plate is heated to a temperature of 60-200 ℃ before being placed in a mold.
10. The method of claim 9, wherein the stamping forming conditions comprise:
1) stamping pressure: 100 to 20000N;
2) press molding maintenance time: 2sec or more;
3) temperature of the die: normal temperature, or heating to below 100 deg.C.
11. The method according to claim 8, wherein the forming temperature of the punch forming is the glass transition temperature of the thermosetting resin composition in the copper-clad plate +/-50 ℃, and the setting time is not less than 2 sec.
12. The copper-clad plate with the bending structure is characterized in that the copper-clad plate with the bending structure is manufactured by one-time or several-time molding by adopting the method of any one of claims 9 to 11, the bending angle is 10-90 degrees, and the bending radius is 1-25 mm.
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