WO2019090916A1

WO2019090916A1 - Copper cladding plate bent in static state, and method for manufacturing same and bend shaping method

Info

Publication number: WO2019090916A1
Application number: PCT/CN2017/117435
Authority: WO
Inventors: 刘东亮; 杨中强; 陈文欣; 许永静
Original assignee: 广东生益科技股份有限公司
Priority date: 2017-11-08
Filing date: 2017-12-20
Publication date: 2019-05-16
Also published as: TW201918379A; TWI785011B; CN109760385A; KR20200055027A; KR102591030B1; CN109760385B

Abstract

Disclosed are a copper cladding plate bent in a static state, and a method for manufacturing same and a bend shaping method. The copper cladding plate comprises copper foil and a thermosetting resin composite dipped substrate adhered on the copper foil, wherein the flexural modulus of elasticity, of the copper cladding plate is greater than 10 GPa, the peeling strength at 60°C-200°C is greater than 1.0 N/mm, and after removing the copper foil, the maximum stress value is greater than 400 MPa and the fracture strain value is greater than 4%.The copper cladding plate can be shaped by punching one or more times to form a copper cladding plate having a bent structure.

Description

Statically bendable copper clad plate, manufacturing method thereof and bending forming method

Technical field

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.

Background technique

In the application of electronic industry, CCL mainly plays the role of mechanical support and electrical connection. However, in the requirements of three-dimensional installation and partial three-dimensional support, the traditional rigid CCL is more brittle and easy to break during bending; traditional Although the flexible copper clad laminate (FCCL) has good bending properties, it has insufficient supporting ability and cannot be used alone for support. In addition, when a rigid copper clad laminate and a flexible copper clad laminate are used as a soft and hard bonded panel, the processing procedure is complicated, the processing is difficult, and the cost is high.

In many electronic products and electromechanical industries, there is a requirement for static bending applications of materials. The so-called 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.

Therefore, in many fields of static bending, it is required to have one or several bending forming processing capabilities for the copper clad material, and it can withstand the impact stress in the bending forming process, without cracking, delamination, and rushing out of various kinds. The three-dimensional bending or concave-convex shape is fixed for subsequent static bending installation.

Summary of the invention

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.

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%.

In some embodiments, 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.

In certain embodiments, 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), toluene, and xylene.

In certain embodiments, 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.

According to still another aspect of the present invention, there is provided a copper clad plate bending forming method, the 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.

In certain embodiments, the copper clad laminate is heated to a temperature of 60-200 °C prior to placement in the mold.

In certain embodiments, the conditions of the press forming include:

1) Stamping pressure: 100N-20000N;

2) Press-form type maintenance time: ≥ 2 sec;

3) Mold temperature: normal temperature (20 ~ 35 ° C), or heated to below 100 ° C.

In some embodiments, 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 invention may have at least one of the following advantages:

1. 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.

2, CCL production process is simple, no need to use flexible board (FCCL), improve efficiency and save costs.

3. 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.

DRAWINGS

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.

Detailed ways

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. In Figure 1, 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.

Based on the above findings, the present invention provides a copper clad plate which can be statically bent, a manufacturing method thereof and a bending forming method. Various aspects of the invention are described in detail below.

CCL

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 -

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 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.

Specific examples of 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.

Preferably, the epoxy resin is a polyfunctional epoxy resin containing two or more epoxy groups (preferably three or more epoxy groups) in one molecule. Such 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).

In some embodiments, the curing agent in the thermosetting resin composition may depend on the kind of the thermosetting resin. For the epoxy 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, and 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:

Wherein X is a benzene or naphthalene ring, j is 0 or 1, k is 0 or 1, and n represents an average repeating unit of 0.25 to 1.25.

In certain embodiments, 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. For the epoxy resin, 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. .

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 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. Among them, 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. Including Japan's Zhongyuan company's M-521, MX-395 and so on. 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. For example, 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.

In order to achieve a good toughening effect, 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.

In certain embodiments, 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.

In some embodiments, 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. Foaming agent, etc. The flame retardant may be an organic flame retardant such as one or more of tetrabromobisphenol A, DOPO, and phosphate.

-Kibbu -

In certain embodiments, 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.

- copper foil -

In some embodiments, the copper foil may be selected from different specifications such as 1OZ, 1/2OZ, 1/3OZ, and the like.

- Statically bendable copper clad laminate -

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.

In certain embodiments, 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.

The above stress and strain values were measured by the following tensile strength and tensile modulus test methods.

Test method for tensile strength and tensile modulus of materials:

A, test device / or material

-Material testing machine

An ISO3384 standard tensile compression tester that can operate at a steady rate. The error of the load measurement system does not exceed ±1%.

- An etching system capable of completely removing the metal foil.

- Vernier caliper (accurate to 0.02mm) or micrometer (accurate to 0.002mm)

- sample

(1) Size and shape

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).

(2) Quantity and sampling

When 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). When 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.

(3) All metal cladding layers are removed by etching using an etching method.

B, tensile test procedure

- Measuring sample size

Measure and record the width and thickness of the specimen, the width is accurate to 0.02mm, and the thickness is accurate to 0.002mm.

-measuring

(1) Hold the sample so that the center line of the sample matches the alignment center line of the upper and lower clamps.

(2) Adjust the distance between the upper and lower clamps to make it 125mm ± 0.5mm.

(3) The loading speed is 12.5 mm/min.

(4) When setting the tensile elastic modulus, take the part between 0.05% and 0.25% of the strain.

(5) Test and draw a stress-strain curve.

(6) Specimens with obvious internal defects shall be discarded.

(7) The specimen is broken in the fixture or the distance from the clamp at the break of the specimen is less than 10mm and should be invalidated.

C, calculation

- Calculate the tensile strength of each sample as follows

In the formula:

τ _T : tensile strength, MPa

F: breaking load or maximum load, N

b: sample width, mm

d: sample thickness, mm

- Calculate the tensile modulus of elasticity of each sample as follows

In the formula:

E _t : tensile modulus of elasticity, MPa

σ′′: tensile stress value measured at strain ε′′=0.25% ε, MPa

σ': tensile stress value measured at strain ε' = 0.05% ε, MPa

- Calculate the average tensile strength and tensile modulus of elasticity in MPa.

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. As shown in FIG. 2, 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%.

Method of making a copper clad laminate

The copper clad laminate of the present invention can be produced as follows:

- Making prepreg -

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%.

- Making copper clad laminates -

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.

Copper clad plate bending forming method

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.

In certain embodiments, the mold is pre-formed at different bend radii (2-50 mm) and bend angle (10-90°).

In certain embodiments, 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.

In certain embodiments, the conditions for stamp forming include:

1) Stamping pressure: 100N-20000N;

2) Press-form type maintenance time: ≥ 2 sec;

In some embodiments, 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.

In certain embodiments, 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.

In certain embodiments, one or more press formings can be performed to achieve various bend forming.

Copper clad laminate with curved structure

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.

In certain embodiments, the copper clad laminate has a bend angle of 10 to 90° and a bend radius of 1 mm to 25 mm.

In certain embodiments, the copper clad laminate can be fabricated by one or several moldings.

The technical solutions of the present invention are further described below in conjunction with specific embodiments. These examples are merely illustrative and are not intended to limit the scope of the invention.

Example 1:

1. 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. And the right amount of MEK organic solvent, configured as a glue, to control the viscosity of the glue between 300-600 cPaS.

2. 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. .

3, 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, and the maximum temperature of the material is 180-200 ° C for 60-120 minutes.

4. Bending forming: (1) heating the copper clad laminate to 60 ° C first; (2) heating the copper clad plate to a stable temperature, putting it into a die press, pressing it at 10000 N for 5 seconds, then opening the mold and taking out the cover. Copper plate. The bending radius and bending angle of the obtained copper clad laminate are shown in Figs. 3 and 4 .

5. Test the appearance, modulus of elasticity, thermal shock (288 ° C / 10 S), reflow soldering (maximum stability of 280 ° C) and other related properties of the above copper clad laminate, and test according to the tensile strength and tensile modulus described in the specification. The method measures the stress strain value.

Example 2:

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.

The relevant characteristics such as apparent, elastic modulus, stress and strain value, thermal shock, reflow, and the like were tested in accordance with the method described in Example 1.

Example 3:

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.

Example 4:

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.

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.

Example 5:

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.

Example 6

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.

Comparative Example 1:

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.

Comparative Example 2:

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.

The test results are compared as follows:

The above is only a part of the embodiments of the present invention, and various other changes and modifications may be made by those skilled in the art according to the technical solutions and technical ideas of the present invention, and all such changes and modifications should belong to The scope of the claims of the present invention.

The present invention is described by the above-described embodiments, but the present invention is not limited to the above detailed methods, and it is not intended that the present invention must be implemented by the above detailed methods. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitution of the various materials of the products of the present invention, addition of auxiliary components, selection of specific means, and the like, are all within the scope of the present invention.

Claims

A copper plate which can be statically bent, characterized in that the copper clad plate comprises a copper foil and a thermosetting resin composition impregnated on the copper foil, the elastic bending modulus of the copper clad plate is >10 GPa The peel strength between 60 and 200 ° C is greater than 1.0 N/mm, and after removing the copper foil, has a maximum stress value greater than 400 MPa and a fracture strain value greater than 4%.
The copper clad laminate according to claim 1, wherein the thermosetting resin composition comprises: a thermosetting resin; a curing agent; a toughening material; and a solvent, wherein the curing agent is 1 to 100 parts by weight of the thermosetting resin. 50 parts by weight, the toughening material is 20 to 60 parts by weight, and the solvent is 5 to 50 parts by weight.
The copper clad laminate according to claim 2, wherein the thermosetting resin comprises an epoxy resin, preferably a polyfunctional epoxy resin; and/or the curing agent comprises a phenol resin, an amine compound, an acid anhydride, an imidazole system At least one of a compound, a phosphonium salt, a dicyandiamide, an active ester; and/or the toughening material comprises a rubber (preferably a core-shell rubber), a phenolic resin, polyvinyl butyral (PVB) At least one of nylon, nanoparticle (preferably 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 includes 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 copper clad laminate according to claim 1, wherein the base fabric comprises a glass cloth or a nonwoven fabric.
A method of producing a copper clad laminate according to any one of claims 1 to 4, wherein the method comprises:

The base fabric is impregnated or coated with a thermosetting resin composition, and heated at 100 to 200 ° C for 1 to 10 minutes to form a prepreg;

The prepreg is bonded to a copper foil, and is subjected to hot press curing at a temperature of 180 to 200 ° C for 30 to 120 minutes to form a copper clad laminate.
A copper clad plate bending forming method, characterized in that the method comprises: putting a copper clad plate according to any one of claims 1 to 4 into a mold for press forming, the mold designing for forming a bending angle It is a curved structure with a bending radius of 1 mm to 25 mm of 10 to 90°.
The method according to claim 6, wherein the copper clad laminate is heated to a temperature of 60 to 200 ° C before being placed in the mold.
The method of claim 7 wherein said conditions for stamp forming comprise:

1) Stamping pressure: 100 ~ 20000N;

2) Press-form type maintenance time: ≥ 2 sec;

3) Mold temperature: normal temperature (20 ~ 35 ° C), or heated to below 100 ° C.
The method according to claim 6, wherein the molding 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.
A copper clad laminate having a curved structure, characterized in that the copper clad laminate having a curved structure is produced by one or several times of molding by the method according to any one of claims 7 to 9, and the bending angle thereof is It is 10 to 90° and has a bending radius of 1 to 25 mm.