WO2019090916A1 - Plaque de placage de cuivre pliée à l'état statique, et procédé de fabrication associé et procédé de mise en forme de courbure - Google Patents

Plaque de placage de cuivre pliée à l'état statique, et procédé de fabrication associé et procédé de mise en forme de courbure Download PDF

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Publication number
WO2019090916A1
WO2019090916A1 PCT/CN2017/117435 CN2017117435W WO2019090916A1 WO 2019090916 A1 WO2019090916 A1 WO 2019090916A1 CN 2017117435 W CN2017117435 W CN 2017117435W WO 2019090916 A1 WO2019090916 A1 WO 2019090916A1
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Prior art keywords
copper clad
clad laminate
copper
weight
thermosetting resin
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PCT/CN2017/117435
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English (en)
Chinese (zh)
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刘东亮
杨中强
陈文欣
许永静
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广东生益科技股份有限公司
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Priority to KR1020207010580A priority Critical patent/KR102591030B1/ko
Publication of WO2019090916A1 publication Critical patent/WO2019090916A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • 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
    • B32B15/20—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

Definitions

  • the invention relates to the technical field of copper clad laminates, in particular to a copper clad plate which can be statically bent, a manufacturing method thereof and a bending forming method.
  • CCL mainly plays the role of mechanical support and electrical connection.
  • the traditional rigid CCL is more brittle and easy to break during bending; traditional
  • the flexible copper clad laminate (FCCL) has good bending properties, it has insufficient supporting ability and cannot be used alone for support.
  • FCCL flexible copper clad laminate
  • the processing procedure is complicated, the processing is difficult, and the cost is high.
  • static bending means that only one bending is required during installation, or the bending region does not need to be swung after one bending, that is, working It is stationary and does not oscillate back and forth like the laser head of a printer; however, even in these static bending fields, in many cases, ordinary rigid copper clad laminates cannot meet the requirements for bending forming.
  • the present invention aims to provide a novel rigid and tough copper clad laminate which does not require the use of a flexible board (FCCL) and a bending forming method thereof, which can be plastically deformed under a certain temperature range and mechanical force. When the mechanical force is released and the temperature is restored to normal temperature, the shape resulting from the original deformation does not change, and the molding can be fixed.
  • FCCL flexible board
  • the object of the present invention can be achieved by the following technical solutions.
  • One aspect of the present invention provides a statically bendable copper clad laminate comprising a copper foil and a thermosetting resin composition impregnated base cloth adhered to the copper foil, the elastic bending modulus of the copper clad laminate >10 GPa (preferably >12 GPa), the peel strength between 60-200 ° C is greater than 1.0 N/mm, and After removing the copper foil, it has a maximum stress value greater than 400 MPa and a fracture strain value greater than 4%.
  • the thermosetting resin composition comprises: a thermosetting resin; a curing agent; a toughening material; and a solvent, wherein the curing agent is 1 to 50 parts by weight, based on 100 parts by weight of the thermosetting resin, and the toughening material
  • the solvent is 5 to 50 parts by weight, and the solvent is 5 to 50 parts by weight.
  • the thermosetting resin comprises an epoxy resin, preferably a polyfunctional epoxy resin; and/or the curing agent comprises a phenolic resin, an amine compound, an acid anhydride, an imidazole compound, a phosphonium salt, a dicyandiamide At least one of an amine, an active ester; and/or the toughening material comprises rubber (preferably a core-shell rubber), a phenolic resin, polyvinyl butyral (PVB), nylon, nanoparticles (preferred) At least one of SiO 2 , TiO 2 , or CaCO 3 nanoparticles), an olefinic block copolymer (preferably a block copolymer of polymethacrylic acid, butadiene, and styrene); and/or the solvent It includes at least one of dimethylformamide (DMF), ethylene glycol monomethyl ether (MC), propylene glycol methyl ether (PM), methyl ethyl ketone (MEK), tolu
  • DMF
  • the base fabric comprises a fiberglass cloth or a nonwoven fabric.
  • Another aspect of the present invention provides a method of fabricating the above copper clad laminate, the method comprising:
  • Impregnating or coating the base fabric with a thermosetting resin composition and heating at 100-200 ° C for 1-10 minutes to form a prepreg;
  • the prepreg is attached to a copper foil, and is subjected to hot press curing at a temperature not exceeding 180 to 200 ° C for 40 to 120 minutes to form a copper clad laminate.
  • a copper clad plate bending forming method comprising: placing the copper clad plate according to any one of claims 1 to 4 into a mold, and performing the press forming, the mold being designed for A curved structure having a bending angle of 10 to 90° and a bending radius of 1 mm to 25 mm is formed.
  • the copper clad laminate is heated to a temperature of 60-200 °C prior to placement in the mold.
  • the conditions of the press forming include:
  • Mold temperature normal temperature (20 ⁇ 35 ° C), or heated to below 100 ° C.
  • the forming temperature of the press forming is a glass transition temperature of ⁇ 50 ° C of the thermosetting resin composition in the copper clad laminate, and the setting time is ⁇ 2 sec.
  • Still another aspect of the present invention provides a copper clad laminate having a curved structure, which adopts the above bend
  • the bending forming method which is produced by one or several moldings, has a bending angle of 10 to 90° and a bending radius of 1 mm to 25 mm.
  • the copper clad laminate of the invention can be plastically deformed under a certain temperature range and mechanical force, and the shape generated by the original deformation does not change when the mechanical force is released and returns to the normal temperature, and can be fixedly formed, that is, has a certain rigidity. Deformation is induced by stress-bearing without breaking, and has a deformation strain.
  • FCCL production process is simple, no need to use flexible board (FCCL), improve efficiency and save costs.
  • the copper clad laminate has the processing capability of one or several bending forming, can withstand the impact stress better during the bending forming process, does not crack, does not delaminate, and punches out various three-dimensional bending or concave-convex shapes to facilitate subsequent static Bend installation use.
  • Figure 1 shows five types of stress-strain curves.
  • Figure 2 shows a typical stress (F)-strain (L) curve of the copper clad laminate of the present invention obtained according to the tensile strength and tensile modulus test methods.
  • Fig. 3 is a view showing the bending radius of the bent copper clad laminate in the first embodiment of the present application.
  • Fig. 4 is a view showing the bending angle of the bent copper clad laminate in the first embodiment of the present application.
  • the present invention surprisingly finds that a prepreg is obtained by impregnating a base fabric such as a glass fiber cloth with a thermosetting resin composition containing a toughening material, and the prepreg is laminated with a copper foil to form a rigid and toughness (or Hard and tough) copper clad board.
  • the stress-strain curve of a material having a hard and tough property is shown as curve 2 in FIG.
  • the material properties represented by each curve are as follows: 1. Hard and brittle; 2. Hard and tough; 3. Hard and strong; 4. Soft and tough; 5. Soft and weak.
  • the present invention provides a copper clad plate which can be statically bent, a manufacturing method thereof and a bending forming method.
  • a manufacturing method thereof a manufacturing method thereof and a bending forming method.
  • One aspect of the present invention provides a statically bendable copper clad laminate comprising a copper foil and a base fabric adhered to the copper foil impregnated with the above-described thermosetting resin composition.
  • thermosetting resin composition for impregnating the base fabric may comprise: a thermosetting resin; a curing agent; a toughening material; and a solvent.
  • the thermosetting resin may include an epoxy resin, a phenol resin, a polyimide resin, a urea resin, a melamine resin, an unsaturated polyester, a polyurethane resin, etc., among which an epoxy resin is preferred.
  • the epoxy resin may include: bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, aralkyl epoxy resin, phenol novolak type epoxy resin (phenol novolac Type epoxy resin, alkylphenol novolac type epoxy resin, bisphenol epoxy resin, naphthalene epoxy resin, dicyclopentadiene epoxy resin, phenolic compound and phenolic hydroxyl group An epoxide obtained by condensing an aromatic aldehyde, a triglycidyl isocyanurate, an alicyclic epoxy resin or the like. These epoxy resins may be used singly or in combination of two or more kinds depending on the case.
  • the epoxy resin is a polyfunctional epoxy resin containing two or more epoxy groups (preferably three or more epoxy groups) in one molecule.
  • an epoxy resin can be used as a commercially available epoxy resin, for example, JER1003 (manufactured by Mitsubishi Chemical Corporation, methyl group is 7 to 8, difunctional, molecular weight is 1300), EXA-4816 (manufactured by Di Aisheng Co., Ltd., molecular weight) 824, most methyl, difunctional), YP50 (manufactured by Nippon Steel Sumitomo Metal Chemical Co., Ltd., molecular weight 60,000 to 80,000, most methyl, bifunctional), DER 593 (manufactured by Dow Chemical, polyfunctional epoxy resin), EPIKOTE 157 (manufactured by Resolution, polyfunctional epoxy resin).
  • the curing agent in the thermosetting resin composition may depend on the kind of the thermosetting resin.
  • the curing agent may include at least one of a phenol resin, an amine compound, an acid anhydride, an imidazole compound, a phosphonium salt, dicyandiamide, and an active ester.
  • the active ester curing agent is obtained by reacting a phenolic compound linked by an aliphatic cyclic hydrocarbon structure, a difunctional carboxylic acid aromatic compound or an acid halide, and a monohydroxy compound.
  • the amount of the difunctional carboxylic acid aromatic compound or acid halide is 1 mol
  • the amount of the phenolic compound linked by the aliphatic cyclic hydrocarbon structure is 0.05 to 0.75 mol
  • the amount of the monohydroxy compound is 0.25 to 0.95 mol.
  • the active ester curing agent may comprise an active ester of the formula:
  • X is a benzene or naphthalene ring
  • j is 0 or 1
  • k is 0 or 1
  • n represents an average repeating unit of 0.25 to 1.25.
  • the curing agent is preferably a phenolic resin, an amine compound, an imidazole compound, and dicyandiamide.
  • these curing agents can be used singly or in combination of two or more.
  • Specific curing agents may include: phenolic resins (eg, phenol novolac resin, cresol novolac resin, etc.); diaminodiphenyl sulfone (DDS); dicyandiamide (DICY); dimethylimidazole (2-MI), etc. .
  • the curing agent is usually used in an amount of 1 to 50 parts by weight, based on 100 parts by weight of the thermosetting resin, and may be, for example, 1 to 40, or 1 to 30 parts by weight.
  • the amount of the curing agent can be controlled such that the epoxy equivalent of the epoxy resin and the hydroxyl equivalent ratio of the phenolic resin are 1:1 to 0.95; or the epoxy resin to amino equivalent ratio is 1:0.6 to 0.4. .
  • 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 a thermosetting resin such as an epoxy resin, a toughening effect (to achieve a corresponding stress strain requirement value (see subsequent description)), and the like.
  • the rubber is preferably a rubber having a core-shell structure, such as a methyl methacrylate-butadiene-styrene (MBS) core-shell copolymer resin, a rubber-epoxy core-shell resin, etc., which is representatively commercially available.
  • the nanoparticles include SiO 2 , TiO 2 , or CaCO 3 nanoparticles, etc., and have a particle diameter of generally 10 to 500 nm.
  • the olefinic block copolymers are block copolymers formed by copolymerization of different kinds of olefins, such as block copolymers of polymethacrylic acid, butadiene and styrene.
  • the toughening materials may be used singly or in combination of two or more.
  • the nanoparticles can be combined with another toughening material (eg, core shell rubber, phenolic resin, PVB, nylon, olefinic block copolymer, or mixtures thereof) in a weight ratio of 1:10 to 2:1. use.
  • another toughening material eg, core shell rubber, phenolic resin, PVB, nylon, olefinic block copolymer, or mixtures thereof
  • the toughening material is generally used in an amount of usually 20 to 60 parts by weight, for example, 20 to 50 parts by weight, or 30 to 60 parts by weight, per 100 parts by weight of the thermosetting resin.
  • the solvent may include dimethylformamide (DMF), ethylene glycol methyl ether (MC), propylene glycol methyl ether (PM), propylene glycol methyl ether acetate (PMA), cyclohexanone, methyl ethyl ketone ( MEK), at least one of toluene and xylene.
  • the amount of solvent used is relative to 100 parts by weight of the thermosetting resin Typically, it is 5 to 50 parts by weight, for example, 10 to 50, 20 to 50 parts by weight, etc., to form a glue having a viscosity of 300 to 600 cPa ⁇ s.
  • the thermosetting resin composition may further contain a filler or an auxiliary agent or the like, such as a flame retardant, a leveling agent, a coloring agent, a dispersing agent, a coupling agent, etc., within a range not detracting from the effects of the present invention.
  • a filler or an auxiliary agent or the like such as a flame retardant, a leveling agent, a coloring agent, a dispersing agent, a coupling agent, etc.
  • the flame retardant may be an organic flame retardant such as one or more of tetrabromobisphenol A, DOPO, and phosphate.
  • the base fabric comprises a fiberglass cloth or a nonwoven fabric.
  • Glass fiber cloth can be selected from various specifications such as 7628, 2116, 1080, 106, 1037, 1027, and 1017.
  • the copper foil may be selected from different specifications such as 1OZ, 1/2OZ, 1/3OZ, and the like.
  • the statically bendable copper clad plate of the invention can be plastically deformed under a certain temperature range and mechanical force, and the shape generated by the original deformation does not change when the mechanical force is released and returns to the normal temperature, and can be fixedly formed.
  • the copper clad laminate has an elastic flexural modulus of >10 GPa, a peel strength between 60-200 ° C greater than 1.0 N/mm, and a maximum stress value greater than 400 MPa and greater than 4 after removal of the copper foil. % fracture strain value.
  • test device / or material
  • the size of the sample is 250mm ⁇ 25mm, and the thickness of the sample is recommended to be 0.4mm.
  • the edge of the sample should be free of cracks, delamination and other defects, otherwise it will be sanded with sandpaper or equivalent tools (the edges are not rounded).
  • the dispersion coefficient is less than 5%, ten samples per batch, five in the vertical direction and five in the lateral direction (cut on the whole sample plate or small plate).
  • the dispersion coefficient is greater than 5%, the number of samples in each direction shall not be less than 10, and 10 effective samples are guaranteed.
  • the width is accurate to 0.02mm
  • the thickness is accurate to 0.002mm.
  • the loading speed is 12.5 mm/min.
  • Figure 2 shows a typical stress-strain curve of a copper clad laminate obtained according to the above tensile strength and tensile modulus test methods.
  • the copper clad laminate of the present invention (after etching to remove the metal clad layer) has a maximum stress value of more than 400 MPa and a strain at break value of more than 4%.
  • the copper clad laminate of the present invention can be produced as follows:
  • the base fabric is impregnated or coated with the thermosetting resin composition in the form of a glue of the present invention, and then heated at 100 to 200 ° C for 1-10 minutes (for example, 3 to 10 minutes) to obtain a prepreg (semi-cured B-stage state).
  • the resin content of the prepreg can be controlled between 40 and 70% by weight, and the resin flow of the prepreg can be controlled between 10 and 30%.
  • the cut prepreg is laminated on a copper foil, hot pressed at a temperature increase rate of 1-3 ° C / min, pressure up to 300-500 PSI, and maintained at a maximum temperature of 180-200 ° C for 30-120 minutes (eg 60- 120 minutes), get a copper clad laminate.
  • Another aspect of the present invention provides a method for bending a copper clad laminate, the method comprising: placing the aforementioned copper clad laminate into a mold for press forming.
  • the mold is pre-formed at different bend radii (2-50 mm) and bend angle (10-90°).
  • the copper clad laminate is heated to a temperature of 60-200 °C prior to placement in the mold.
  • the molding temperature of the press forming is a glass transition temperature of the thermosetting resin composition in the copper clad laminate of ⁇ 50 ° C (preferably ⁇ 30 ° C), and the setting time is ⁇ 2 sec.
  • the conditions for stamp forming include:
  • Mold temperature normal temperature (20 ⁇ 35 ° C), or heated to below 100 ° C.
  • other clamping parameters may include a clamping rate of 0 to 2000 mm/min and an upper clamping pressure value of 100 to 20000 N.
  • the number of layers of the copper clad laminate that is stamped may be from 4 to 14 layers and may range from 0.2 mm to 1 mm.
  • one or more press formings can be performed to achieve various bend forming.
  • Still another aspect of the present invention provides a copper clad laminate having a curved structure which can be produced by the above-described bending forming method.
  • the copper clad laminate has a bend angle of 10 to 90° and a bend radius of 1 mm to 25 mm.
  • the copper clad laminate can be fabricated by one or several moldings.
  • Glue configuration 5 parts by weight of rubber (Japan Kouyuan M-521), 10 parts by weight of core-shell rubber (Japan Kaneka MX-395) and 20 parts by weight of nano-SiO 2 (Evonik Nanoopol A 710) were selected.
  • As a toughening material it is mixed with 100 parts by weight of a polyfunctional epoxy resin (Dow Chemical DER593 resin), and a phenol resin (Dow Chemical XZ92741 resin) is added so that the epoxy equivalent ratio to the hydroxyl equivalent ratio is 1:1.
  • the right amount of MEK organic solvent, configured as a glue to control the viscosity of the glue between 300-600 cPaS.
  • Prepreg production firstly glue the above-mentioned glue-impregnated glass fiber cloth (2116 glass fiber cloth), and then put it into an oven and heat-bake at 100-200 °C for 3-10 minutes to make the above resin composition reach the semi-cured B-stage state. .
  • CCL production use 1OZ copper foil, combined with the above prepreg, put into the laminating machine,
  • the heating rate is 1-3 ° C / min
  • the pressure of the platen is 300-500 PSI
  • the maximum temperature of the material is 180-200 ° C for 60-120 minutes.
  • a copper clad laminate was produced in the same manner as in Example 1 except for the following glue configuration.
  • Glue configuration 20 parts by weight of phenol oxygen (HEXION 53BH35) and 10 parts by weight of core-shell rubber CSR (Japan Kaneka MX-395) are used as the toughening material, and 100 parts by weight of multifunctional epoxy resin (Resolution)
  • the company's EPIKOTE 157 resin is mixed and added with 2.5 parts by weight of dicyandiamide, and an appropriate amount of DMF organic solvent, which is configured as a glue.
  • the viscosity of the glue is controlled for glass fiber impregnation.
  • Bending forming (1) heating the copper clad laminate to 120 ° C first; (2) heating the copper clad laminate to a stable temperature, placing it in a die press, pressing at 100 N for 100 seconds, and then opening the mold to take out the copper clad laminate.
  • the bending radius and bending angle of the copper clad laminate are the same as in the first embodiment.
  • a copper clad laminate was produced in the same manner as in Example 1 except for the following glue configuration.
  • Glue configuration 20 parts by weight of PVB (American Solutia B90), 8 parts by weight of nano-SiO 2 (Evonik Nanoopolo A 710) and 5 parts by weight of block copolymer (Arkoma Nanostrength) ) is a toughened material, mixed with 100 parts by weight of a polyfunctional epoxy resin (DOW Chemical Co., Ltd. DER593 resin), and added with 3 parts by weight of dicyandiamide, and an appropriate amount of DMF or PM organic solvent, configured as a glue, controlled The viscosity of the glue is between 300-600 cPaS.
  • Bending forming (1) heating the above copper clad laminate to 200 ° C; (2) heating the copper clad plate to stabilize the temperature Thereafter, it was placed in a die press, pressed at 20000 N for 2 seconds, and then opened again to take out the copper clad laminate.
  • the bending radius and bending angle of the copper clad laminate are the same as in the first embodiment.
  • a copper clad laminate was produced in the same manner as in Example 1 except for the following glue configuration.
  • Glue configuration 20 parts by weight of nylon (such as DuPont ST801A) and 8 parts by weight of nano-SiO 2 (Evonik Nano 710) are mixed with 100 parts by weight of polyfunctional epoxy resin (DOW Chemical DER 593 resin). And adding phenolic resin (EPIKURE YLH129B65 of Resolution company) according to epoxy equivalent and hydroxyl equivalent 1:1, and the appropriate amount of MEK organic solvent, configured as a glue, and controlling the viscosity of the glue between 300-600 cPaS.
  • nylon such as DuPont ST801A
  • nano-SiO 2 Engelnik Nano 710
  • Bending forming (1) heating the copper clad laminate to 100 ° C first; (2) heating the copper clad laminate to a stable temperature, placing it in a die press, pressing at 10000 N for 10 seconds, and then opening the mold to take out the copper clad laminate.
  • the bending radius and bending angle of the copper clad laminate are the same as in the first embodiment.
  • a copper clad laminate was produced in the same manner as in Example 1 except for the following glue configuration.
  • Glue configuration 25 parts by weight of block copolymer (Arkema Nanostrength) And 8 parts by weight of nano-SiO 2 (Evonik Nanoopol 710) as a toughening material, mixed with 100 parts by weight of cyanate tree (Huifeng HF-10) grease, and added with 20 parts by weight of phenolic resin (RESOLUTION)
  • the company's EPIKURE YLH129B65), as well as the right amount of MEK organic solvent, is configured as a glue to control the viscosity of the glue between 300-600 cPaS.
  • Bending forming (1) heating the copper clad laminate to 200 ° C first; (2) heating the copper clad laminate to a stable temperature, placing it in a die press, pressing at 10000 N for 20 seconds, and then opening the mold to take out the copper clad laminate.
  • the bending radius and bending angle of the copper clad laminate are the same as in the first embodiment.
  • a copper clad laminate was produced in the same manner as in Example 1 except for the following glue configuration.
  • Glue configuration 20 parts by weight of phenolic resin (Nippon Steel Chemical ERF-001), 10 parts by weight of PVB (American Solutia B90) and 5 parts by weight of nano-SiO 2 (Evonik Nanoopolo A 710) are used as the addition a tough material mixed with 50 parts by weight of PPO resin (Saab Foundation MX90) and 100 parts by weight of epoxy resin (DOW Chemical DER 593 resin), and 20 parts by weight of phenolic resin (EPIKURE YLH129B65 from RESOLUTION), and Appropriate amount of MEK organic solvent, configured as a glue, to control the viscosity of the glue between 300-600 cPaS.
  • Bending forming (1) heating the copper clad laminate to 100 ° C first; (2) heating the copper clad laminate to a stable temperature, placing it in a die press, pressing at 10000 N for 50 seconds, and then opening the mold to take out the copper clad laminate.
  • the bending radius and bending angle of the copper clad laminate are the same as in the first embodiment.
  • a copper clad laminate and a bent molding were produced in the same manner as in Example 1 except for the following glue configuration, and the corresponding properties were tested.
  • Glue configuration 100 parts by weight of polyfunctional epoxy resin (DOW Chemical DER593 resin), 2-3 parts by weight of dicyandiamide, and appropriate amount of DMF organic solvent are added to configure the glue to control the viscosity of the glue at 300-600 cPaS. between.
  • a copper clad laminate and a bent molding were produced in the same manner as in Example 1 except for the following glue configuration, and the corresponding properties were tested.
  • Glue configuration 10 parts by weight of nitrile rubber (Japanese Kaneka M-521) and 100 parts by weight of polyfunctional epoxy resin (DOW Chemical DER 593 resin) are mixed, and 2-3 parts by weight of dicyandiamide is added, and Appropriate amount of DMF organic solvent, configured as a glue, to control the viscosity of the glue between 300-600 cPaS.
  • test results are compared as follows:

Abstract

L'invention concerne une plaque de placage de cuivre pliée dans un état statique, et un procédé de fabrication associé, ainsi qu'un procédé de mise en forme de courbure. La plaque de placage de cuivre comprend une feuille de cuivre et un substrat enrobé de composite de résine thermodurcissable collé sur la feuille de cuivre, le module d'élasticité en flexion de la plaque de placage de cuivre étant supérieur à 10 GPa, la résistance au pelage à 60 °C-200 °C étant supérieure à 1,0 N/mm, et après élimination de la feuille de cuivre, la valeur de contrainte maximale étant supérieure à 400 MPa et la valeur de contrainte de fracture étant supérieure à 4 %. La plaque de placage de cuivre peut être mise en forme par un ou plusieurs poinçonnages pour former une plaque de placage de cuivre ayant une structure courbée.
PCT/CN2017/117435 2017-11-08 2017-12-20 Plaque de placage de cuivre pliée à l'état statique, et procédé de fabrication associé et procédé de mise en forme de courbure WO2019090916A1 (fr)

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KR20200055027A (ko) 2020-05-20
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