WO2018117636A1 - Metal laminate and method for manufacturing same - Google Patents

Abstract

The present invention provides a metal laminate and a method for manufacturing the same. The metal laminate comprises: a core layer including a fiber material; and a fluorine-based film laminated on both sides of the core layer; a metal foil laminated on the fluorine-based film, wherein the fluorine-based film comprises a filler. The present invention can provide a metal laminate for ultra-high frequencies which exhibits excellent low dielectric loss characteristics, good heat resistance, adhesion stability, etc. at the same time.

Description

Metal laminate and its manufacturing method

The present invention relates to a metal laminated plate and a method for manufacturing the same, and provides a metal laminated plate for a printed circuit board and a method for manufacturing the same that can be stably operated in a high frequency band.

Recently, signal bands of electronic components such as semiconductor substrates, printed circuit boards, and epoxy molding compounds (EMCs) and information communication devices have increased. The transmission loss of the electrical signal is proportional to the dielectric tangent and frequency. Therefore, the higher the frequency, the greater the transmission loss and the attenuation of the signal, resulting in a lower reliability of the signal transmission. In addition, transfer loss may be converted into heat, which may cause heat generation problems. Thus, in the high frequency range, dielectric materials with very small dielectric tangents are required.

In addition, since the demand for high integration, high microdefinition, high performance, and the like in the semiconductor device and PCB field is increasing, the situation is gradually changing to a situation in which integration of semiconductor devices and high density of printed circuit boards and simplicity of wiring intervals are required. In order to satisfy these characteristics, it is desirable to use a low dielectric constant material for increasing the transmission speed and a low dielectric loss material for reducing the transmission loss.

Metal laminates manufactured using epoxy resins of a metal laminate for manufacturing a printed circuit board may be impregnated with an epoxy resin in a glass fabric, drying the impregnated fibers to remove other organic solvents, and curing the resin. A prepreg generation step for switching to the semi-cured state, and a step of laminating the conductive metal foil.

On the other hand, when manufacturing a metal laminate using a fluorine-based resin, the fluorine-based resin is a thermoplastic resin and has a non-adhesive property that does not adhere well to other materials due to physically very low surface energy, so that the fluorine resin and the conductive metal foil are usually directly attached. Since it was difficult, the method of directly laminating the conductive metal foil on the resin as described above could not be used.

The thermosetting resin having a low melting point on various heat-resistant polymer insulating fluorine resins such as polytetrafluoroethylene (PTFE) resin and resin impregnated with polytetrafluoroethylene in glass fiber tissues for adhesion of fluorine resin with other materials. , An adhesive film or an adhesive is placed and the conductive metal foil is compressed and cured under heating / pressurization as a medium to be laminated.

However, in such a method, there is a problem that the heat resistance, which is a characteristic of the polymer insulating resin, is inferior as three or more impregnation processes are performed, and the process cost increases because high temperature compression must be performed at 350 ° C. for at least 24 hours. There is this.

The present invention is to develop a metal laminated plate for a printed circuit board that can reduce the manufacturing cost according to the simplification of the manufacturing process as well as excellent overall physical properties including low loss coefficient, low dielectric constant, heat resistance suitable for high frequency band.

To this end, in the present invention, by laminating a material having a low dielectric constant and a conductive metal foil on a high heat resistant prepreg and then integrating it by high temperature compression in a short time, an object of the present invention is to provide a metal laminated plate having excellent low dielectric constant and heat resistance and a method of manufacturing the same. It is done.

In addition, the present invention is to produce a laminate by impregnating a material having a high heat resistance on the fiber substrate and then ply-up the fluorine-based film, by laminating a conductive metal foil on the laminate and then integrated by high temperature compression in a short time. It is an object of the present invention to provide a metal laminate and a method of manufacturing the same, which exhibit high adhesion between metal foil and film and low dielectric properties.

In order to achieve the above object, the present invention provides a metal laminated plate to which a low dielectric constant material is applied, and a manufacturing method thereof.

The present invention provides a high heat resistant core layer comprising a fibrous substrate; Fluorine-based film laminated on both sides of the core layer; And a metal foil laminated on the fluorine-based film, wherein the fluorine-based film provides a metal laminate, characterized in that it comprises a filler (filler).

According to one embodiment of the present invention, the fluorine-based film is a fluoropolymer film selected from the group consisting of polytetrafluoroethylene (PTFE), fluoro and ethylene-propylene copolymers and fluorocarbon backbones with perfluoroalkoxy side chains. And, preferably, a perfluoro alkoxy (PFA) film.

According to an example of the present invention, the filler in the fluorine-based film may be included in an amount of 10 to 70% by weight.

According to one embodiment of the present invention, the filler is one of silica (silica), titanium dioxide (TiO ₂ ), alumina (Al ₂ O ₃ ), potassium titanate (K ₂ O ₆ TiO ₂ ), barium oxide (BaO) Can be.

According to an example of the present invention, the core layer may include a resin layer cured by impregnating the fiber substrate in a high heat resistant resin composition.

According to one embodiment of the present invention, the high heat resistant resin composition is bisphenol A (bisphenol A) epoxy, aromatic naphthalene epoxy, biphenyl aralkyl type epoxy, isocyanurate epoxy, cresol noblec (cresol) novlac) type epoxy resin, and high heat resistant epoxy resin.

According to one embodiment of the present invention, the fiber substrate may be spread glass fibers (Spread G / F). Here, the spread glass fibers are glass fibers; And an inorganic binder.

According to one example of the invention, the metal foil is preferably copper foil having a roughness Rz in the range of 0.5 to 5.0 μm.

According to one embodiment of the invention, the coefficient of thermal expansion (CTE) of the metal laminate is preferably 5 to 40 ppm.

According to an example of the present invention, the peel strength (P / S) of the metal foil to the fluorine-based film in the metal laminate is preferably in the range of 0.8 to 1.5 kgf / cm.

In addition, the present invention comprises the steps of (a) impregnating a fiber substrate in the high heat-resistant resin composition and then semi-curing to prepare a core layer, and (b) sequentially stacking a fluorine-based film and a metal foil on the upper and lower surfaces of the core layer, respectively. Then, it provides a method for producing a metal laminate comprising the step of integrating into a high temperature compression process.

In addition, the present invention comprises the steps of (a) laminating a fluorine-based film on the upper and lower surfaces of the core layer, respectively, and (b) laminating metal foils on the upper and lower surfaces of the laminate, respectively, and then integrated into a high temperature compression process. It provides a method for producing a metal laminate comprising the step of. Here, the core layer may include glass fiber.

According to one embodiment of the invention, the high temperature compression process is preferably carried out for 10 minutes to 3 hours at a temperature of 270 to 400 ℃.

Since the metal laminate according to the present invention satisfies a low loss factor, low dielectric properties, heat resistance, and adhesion stability at the same time, the printed circuit board using the same may exhibit excellent high frequency characteristics, good heat resistance, and adhesive stability.

In addition, the manufacturing method of the metal laminated plate according to the present invention is inexpensive processing cost by integrating by high temperature compression in a short time, and because the unique intrinsic properties can be used as it is by minimizing the change in electrical and mechanical properties of low dielectric constant material, high frequency band It is possible to produce a metal laminated plate having a low loss coefficient, which has excellent electrical characteristics, which can operate very stably.

Therefore, the metal laminate of the present invention is a component of a printed circuit board used in a mobile communication device that handles high-frequency signals of 1 GHz or more, network-based electronic devices such as base station devices, servers, routers, and various electrical and electronic devices such as large computers. It can be usefully used as.

1 is a cross-sectional view of a metal laminate according to an embodiment of the present invention.

2 is a cross-sectional view of a metal laminate according to another embodiment of the present invention.

[Description of the code]

100, 200: metal laminate

110: prepreg

210: fiber substrate

130, 230: fluorine-based film

170 and 270: metal foil

Hereinafter, with reference to the accompanying drawings will be described an embodiment of the present invention. However, this is presented as an example, by which the present invention is not limited, and the present invention is defined only by the scope of the claims to be described later.

The present invention is to provide a metal laminated plate that can be usefully used in printed circuit boards, especially printed circuit boards for ultra-high frequency applications.

Referring to Figure 1 will be described a metal laminated plate and a method of manufacturing the same according to an embodiment of the present invention.

In one embodiment of the present invention, a core layer including a fiber substrate, a fluorine-based film laminated on both sides of the core layer, and a metal foil laminated on the fluorine-based film, the fluorine-based film on the core layer Provided is a metal laminated plate bonded by high temperature compression.

Here, the core layer means a prepreg including a fiber base, and preferably means a high heat resistant prepreg formed by impregnating a fiber base in the high heat resistant resin composition.

The metal laminate according to the present invention is a high heat-resistant prepreg; A fluorine-based film having a low dielectric constant; And a structure in which a metal foil having low roughness is laminated, and by securing adhesion stability of each layer, the effects of low loss coefficient, low dielectric property, heat resistance, and adhesion stability can be simultaneously given to the printed circuit board using the metal laminate. Can be.

1 schematically shows a cross section of a metal laminate 100 according to an embodiment of the present invention.

First, referring to FIG. 1, the metal laminate 100 includes a prepreg 110 including a fiber base, a fluorine-based film 130 laminated on both surfaces of the prepreg, and a metal foil laminated on the fluorine-based film ( 170).

The prepreg 110 of the present invention includes a fiber substrate and a resin layer cured by impregnating the fiber substrate with the high heat resistant resin composition. Here, the high heat resistant resin composition may be a resin varnish dissolved or dispersed in a solvent.

The fibrous substrate may be arbitrarily bent, and may be used in the art of a conventional inorganic fiber substrate, organic fiber substrate, or a mixed form thereof. What is necessary is just to select the above-mentioned fiber base material based on the use or performance to be used.

Examples of the substrate used in the present invention include inorganic fibers such as E-glass, D-glass, S-glass, NE-glass, T-glass, and Q-glass, and organic fibers such as polyimide, polyamide, polyester, and the like. Mixtures, etc. are selected based on the intended use or performance.

Non-limiting examples of fiber substrates that can be used include glass fibers (inorganic fibers) such as E-glass, D-glass, S-glass, NE-glass, T-glass, Q-glass, and the like; Organic fibers such as glass paper, glass fiber nonwoven fabric, glass cloth, aramid fiber, aramid paper, polyimide, polyamide, polyester, aromatic polyester, fluororesin, and the like; Carbon fibers, paper, inorganic fibers, or a mixture of one or more thereof. The fiber base may be formed of a woven or nonwoven fabric made of the aforementioned fibers, roving, chopped strand mat, surfacing mat, metal fiber, carbon fiber, mineral fiber, or the like. Woven fabrics, nonwoven fabrics, mats, etc. may be mentioned. These base materials can be used individually or in mixture of 2 or more types. In the case of using a reinforced fiber substrate, the stiffness and dimensional stability of the prepreg can be improved. The thickness of this fibrous substrate is not particularly limited and may be, for example, in the range of about 0.01 mm to 0.3 mm.

The high heat resistant resin composition is used to form the prepreg 110, and the prepreg 110 may include a resin layer cured by impregnating the fiber base in the high heat resistant resin composition.

The high heat resistant resin composition used in the present invention is not particularly limited as long as it is a composition excellent in heat resistance known in the art, but is not particularly limited in terms of its chemical composition. For example, bisphenol A epoxy, aromatic naphthalene epoxy, and biphenyl are used. It is preferable to include at least one of an alkyl (biphenyl aralkyl) type epoxy, an isocyanurate epoxy, a cresol novlac type epoxy resin, and a high heat resistant epoxy resin.

In general, the prepreg refers to a sheet-like material obtained by coating a fibrous substrate with a resin composition or by impregnating the fibrous substrate with a resin composition and curing it to B-stage (semicured state) by heating. In addition to the methods described above, the prepreg 110 of the present invention may be prepared by known solvent methods known in the art.

The solvent method is a method of drying after impregnating a fibrous substrate with a resin composition varnish formed by dissolving the resin composition for prepreg formation in an organic solvent. In the case of employing such a solvent method, a resin varnish is generally used. As an example of the method of impregnating a fiber base material in the said resin composition, the method of immersing a base material in a resin varnish, the method of apply | coating a resin varnish to a base material by various coaters, the method of spraying a resin varnish to a base material by spraying, etc. Can be mentioned. At this time, when the fiber base material is immersed in a resin varnish, since the impregnation property of the resin composition with respect to a fiber base material can be improved, it is preferable.

The prepreg 110 of this invention can be manufactured by impregnating the said heat resistant resin composition with the sheet-like fiber base material or glass base material which consists of a fiber, and semi-hardening by heating. In this case, the heat resistant resin composition may be prepared by a resin varnish.

When preparing the said resin varnish, For example, ketones, such as acetone, methyl ethyl ketone, cyclohexanone, an acetic acid, such as ethyl acetate, butyl acetate, a cellosolve acetate, a propylene glycol monomethyl ether acetate, and a carbitol acetate Carbitols such as esters, cellosolves and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran and the like. You may use an organic solvent 1 type or in combination of 2 or more types.

The prepreg 110 of the present invention may be formed through an additional drying process after impregnating the substrate in the resin varnish, wherein the drying may be performed at 20 to 200 ℃. For example, the prepreg 110 of the present invention is impregnated with the substrate in the high heat-resistant resin varnish and heat-dried for 1 to 10 minutes at a temperature in the range of 70 to 170 ℃, the prepreg of the semi-cured state (B-Stage) Legs can be prepared.

The metal laminate 100 according to an embodiment of the present invention includes a fluorine-based film 130 laminated on both surfaces of the prepreg 110 as a material having a low dielectric constant.

Examples of low dielectric constant materials usable in the present invention include fluoropolymers selected from the group consisting of polytetrafluoroethylene (PTFE), fluoro and ethylene-propylene copolymers, and fluorocarbon backbones with perfluoroalkoxy side chains. A film is mentioned, Among them, a perfluoro alkoxy (PFA) film is preferable.

Prior art has been prepared by impregnating polytetrafluoroethylene (PTFE) resin into glass fiber 5-6 times, high temperature / high pressure press process, but the present invention impregnates glass fiber with high heat-resistant resin, high temperature / Manufacturing through high pressure compression process has the advantage of reducing the productivity, manufacturing process cost. In addition, since the filler is prepared by laminating the filler in the fluorine-based film, there is an advantage in that the coefficient of thermal expansion (CTE) is excellent.

Thus, in the present invention, a material having a low dielectric constant, such as perfluoro alkoxy (PFA), such as a fluororesin, is not formed into a prepreg by impregnating a fibrous substrate, but in a film form on the prepreg 110 prepared above. By laminating | stacking, the laminated body 150 of the prepreg 110 and the fluorine-type film 130 is formed.

As described above, the fluoro-based film 130 is preferably a perfluoro alkoxy (PFA) film, the fluorine-based film 130 may include a filler.

The filler is included in the fluorine-based film, it may have an effect of improving the properties such as G / F impregnation, productivity, thermal expansion coefficient (CTE) of the fluorine-based film.

Non-limiting examples of the filler, at least one of silica (silica), titanium dioxide (TiO ₂ ), alumina (Al ₂ O ₃ ), potassium titanate (K ₂ O ₆ TiO ₂ ), barium oxide (BaO) Among these, silica is preferable.

The filler may be included in an amount of 10 to 70% by weight in the fluorine-based film, for example, it is preferably included in an amount of 40% by weight. When the content of the filler in the fluorine-based film is less than 40% by weight can not exhibit a CTE (Z-axis) improvement effect, when included in an amount exceeding 70% by weight is a problem that the film is not formed.

The thickness of the fluorine-based film 130 is not particularly limited, but may be in the range of 25 to 125 μm, preferably 50 μm.

The metal laminate 100 according to an embodiment of the present invention includes a metal foil 170 laminated on the laminate 150 of the prepreg 110 and the fluorine-based film 130.

The metal foil 170 may be made of a conventional metal or alloy known in the art without limitation. At this time, when the metal foil is a copper foil, the metal laminated plate 100 according to the present invention can be used as a copper foil laminate. Preferably, the metal foil 170 is copper foil.

The said copper foil includes all the copper foils manufactured by the rolling method and the electrolytic method. Here, the copper foil may be subjected to rust prevention treatment in order to prevent the surface from being oxidized and corroded.

The metal foil 170 may have a predetermined surface roughness Rz formed on one surface in contact with the fluorine-based film 130. At this time, the surface roughness (Rz) is preferably in the range of 0.5 to 5.0 ㎛. If the surface roughness is less than 0.5 μm, the adhesion between the metal foil 170 and the fluorine-based film 130 is insufficient. In addition, the thickness of the metal foil 170 is not particularly limited, but may be used less than 7 ㎛ in consideration of the thickness and mechanical properties of the final product, preferably may be in the range of 3 to 7 ㎛. Examples of copper foil that can be used include CFL (TZA_B, HFZ_B), Mitsui (HSVSP, MLS-G), Nikko (RTCHP), Furukawa, ILSIN and the like.

A prepreg 110 impregnated by impregnation with a high heat resistant varnish as described above; Fluorine-based film 130; And the metal laminated plate 100 formed by integrally stacked at a high temperature and high pressure after the metal foil 170 is sequentially stacked may have a coefficient of thermal expansion (CTE) of 5 to 40 range.

In addition, the peel strength (P / S) of the metal foil 170 to the fluorine-based film 130 in the metal laminate 100 may be in the range of 0.8 to 1.5 kgf / cm.

An embodiment of the present invention includes a method of manufacturing a metal laminate plate formed by laminating the prepreg and the fluorine-based film described above to form a laminate, and then laminating the metal foil on the laminate and molding the same by a high temperature compression process. .

More specifically, the method of manufacturing a metal laminate 100 according to an embodiment of the present invention comprises the steps of (a) manufacturing a prepreg 110 by impregnating a glass fiber in the high heat-resistant resin composition and then semi-curing; (b) sequentially stacking the fluorine-based film 130 and the metal foil 170 on both surfaces of the prepreg 110, and then performing a high temperature compression process to integrate them. At this time, the high temperature compression process of step (b) is preferably carried out for 10 minutes to 3 hours at a temperature of 270 to 400 ℃.

In addition, one embodiment of the present invention includes a multilayer printed circuit board, preferably a multilayer printed circuit board, including at least one selected from the group consisting of the core layer, the fluorine-based film, and the metal foil described above.

In the present invention, the printed circuit board refers to a printed circuit board laminated by one or more layers by a plating through hole method, a buildup method, or the like, and may be manufactured by a conventional method known in the art. As a preferable example thereof, it can be manufactured by opening a hole in the metal laminated plate 100 according to the present invention to perform through hole plating, and then forming a circuit by etching a metal foil including a plating film.

Hereinafter, a metal laminated plate and a method of manufacturing the same according to another embodiment of the present invention will be described with reference to FIG. 2.

The metal laminate 200 according to another embodiment of the present invention is the same except that the structure of the core layer and the lamination method of the fluorine-based film are different from those of the metal laminate plate 100 described above with reference to FIG. 1. Therefore, the description of the same configuration is omitted for the sake of brevity of the specification.

In another embodiment of the present invention, there is provided a metal laminate comprising a core layer including a fiber substrate, a fluorine-based film laminated on both sides of the core layer, and a metal foil laminated on the fluorine-based film.

Here, the core layer means a fiber base, preferably glass fiber (Spread G / F).

2 is a schematic cross-sectional view of the metal laminate 200 according to another embodiment of the present invention.

The metal laminate 200 according to another embodiment of the present invention may include a fiber base 210, a fluorine-based film 230 laminated on both sides of the fiber base, and a metal foil 270 stacked on the fluorine-based film. Can be.

The fiber substrate 210 may be arbitrarily bent, may be used in the art of conventional flexible inorganic fiber substrates, organic fiber substrates, or a mixture thereof. What is necessary is just to select the above-mentioned fiber base material based on the use or performance to be used.

In another embodiment of the present invention, it is preferable to use spread G / F as the fiber substrate 210. The spread glass fibers are glass fibers; And an inorganic binder.

Spread glass fibers can be prepared by a conventional method, for example, after stirring the glass fiber and the inorganic binder solution to form a mixed solution, to remove the water from the mixed solution to obtain an extract and then to compress and dry the extract It can be prepared by the method.

Here, the inorganic binder is not particularly limited, but may be an aluminum compound produced by neutralizing an acidic solution (eg, aluminum sulfate) and a basic solution (eg, sodium hydroxide) containing aluminum.

The metal laminate 200 according to another embodiment of the present invention includes a fluorine-based film 230 laminated on both surfaces of the fiber substrate 210 as a low dielectric constant material.

Specifically, in the present invention, as described above, it is used as the fluorine-based film 230 in the form of a film so as not to impair the excellent electrical properties and high heat resistance of the material having a low dielectric constant, an example of the fluorine-based film used is perfluoro alkoxy ( PFA) films are preferred.

In the above-described embodiment of the present invention, the prepreg 110 and the fluorine-based film 130 may be formed by laminating the fluorine-based film 130 on the prepreg 110 in a semi-cured state in which the high heat-resistant resin composition is impregnated with the fiber substrate. The laminate 150 is formed.

On the contrary, in another embodiment of the present invention, the laminate 250 of the fiber base 210 and the fluorine film 230 is laminated by stacking the fluorine-based film 230 on both sides of the fiber base 210 by a press process. To form.

In the present embodiment, the metal laminate 200 includes a metal foil 270 laminated on the laminate 250 of the fiber base 210 and the fluorine-based film 230. At this time, the metal foil 270 is laminated on the laminate 250 and then integrated by a high temperature compression process to form the metal laminate 200.

Another embodiment of the present invention includes a method of manufacturing a metal laminated plate that is formed by sequentially laminating the above-described fiber substrate and the fluorine-based film to form a laminate, and then laminating metal foils and molding them by a high temperature compression process.

More specifically, the manufacturing method of the metal laminate 200 according to another embodiment of the present invention (a) to prepare a laminate 250 by laminating the fluorine-based film 230 on the upper and lower surfaces of the fiber base 210, respectively. Making; And (b) stacking the metal foils 270 on the upper and lower surfaces of the laminate, and then integrating the same into a high temperature compression process. At this time, the high temperature compression process of step (b) is preferably carried out for 10 minutes to 3 hours at a temperature of 270 to 400 ℃.

In addition, another embodiment of the present invention includes a laminated printed circuit board, preferably a multilayer printed circuit board, including at least one selected from the group consisting of the fiber substrate, the fluorine-based film, and the metal foil.

As described above, the metal laminate may be prepared from the core layer, the fluorine-based film, and the metal foil according to the present invention. These metal laminates not only had low dielectric constant and dielectric loss, but also had a low coefficient of thermal expansion (CTE) and good adhesion stability (see Table 1 below). Therefore, the metal laminate of the present invention is a network printed circuit board used in mobile communication devices that handle high frequency signals of 1 GHz or more, network-based electronic devices such as base station devices, servers, routers, and various electrical and electronic devices such as large computers. It can be usefully used as a component.

Hereinafter, the present invention will be described in detail with reference to Examples, but the following Examples and Experimental Examples are merely illustrative of one embodiment of the present invention, and the scope of the present invention is not limited to the following Examples and Experimental Examples.

Example 1

1. Preparation of Prepregs

A high heat resistant resin composition was prepared with a high heat resistant epoxy resin composition and a resin varnish was prepared.

The prepared resin varnish was impregnated with a glass fiber having a thickness of 1 to 2 μm, and then dried at 165 ° C. for 1 to 10 minutes to prepare a prepreg in a semi-cured state.

2. Manufacture of Copper Clad Laminates

A 50 µm (0.05T) thick perfluoro alkoxy (PFA) film (40 wt% silica) was laminated on both sides of the prepreg to obtain a laminate.

18 micrometer-thick copper foil was laminated | stacked on both surfaces of the said laminated body, and it pressed at 320 degreeC for 2.5 hours, and obtained the copper clad laminated board of 0.16 mm thickness.

Example 2

A copper foil laminated plate was obtained in the same manner as in Example 1 except that a polytetrafluoro film (50 wt%) was used.

Example 3

1. Preparation of laminate

50 µm thick perfluoro alkoxy (PFA) (40 wt% silica) was sequentially laminated on both sides of the prepared 25 µm thick glass fibers to obtain a laminate.

2. Manufacture of Copper Clad Laminates

The copper foil of 18 micrometers thickness was laminated | stacked on both surfaces of the said laminated body, and it pressed at 320 degreeC for 2.5 hours, and obtained the copper clad laminated board of 0.16 mm thickness.

Comparative Example 1

1. Preparation of Prepregs

The prepared 25 μm-thick glass fibers were impregnated with a polytetrafluoroemulsion three times or more, and then dried at 165 ° C. for 3 to 10 minutes to prepare a polytetrafluoro prepreg.

2. Manufacture of Copper Clad Laminates

18 micrometer-thick copper foil was laminated | stacked on both surfaces of the said polytetrafluoro prepreg, and it pressed at 350 degreeC for 24 hours or more, and obtained the copper foil laminated board of 0.16 mm thickness.

Experimental Example

Properties of Fluorine-Based Films and Copper Clad Laminates

The following experiments were performed on the fluorine-based films and copper foil laminates prepared in Examples 1 to 3 and Comparative Example 1, and the results are shown in Table 1 below.

[Measuring conditions]

1. Tensile Strength (MPa): Measured using UTM equipment according to the test standard of IPC TM-650 2.4.4 / ASTM D3039.

2. Modulus of elasticity (Young Modulus, MPa): Measured using a UTM equipment in accordance with the test standard of IPC TM-650 2.4.4 / ASTM D3039.

3. Elongation (Elong,%): Measured using UTM equipment according to the test standard of IPC TM-650 2.4.4 / ASTM D3039.

4. Thermal expansion coefficient (CTE, ppm): measured using a TMA (Thermo Mechanical Analyzer) equipment in accordance with the test standard of IPC-650 2.4.41.

5. Peel strength (P / S, Hoz): Measured by an adhesive force meter in accordance with the test standard of IPC TM-650.2.4.8.

6. TGA Ash% (Air): TGA (Thermogravimetric) was measured according to the test standard of IPC TM-650.2.4.24.6.

7. S / F @ 288: After putting the laminated body cut | disconnected in the magnitude | size of 5cmX5cm in the solder bath of 288 degreeC, the external appearance change was visually confirmed for 10 minutes.

8. Dielectric constant (Dk): Measured using a material analyzer in accordance with the test standard of IPC TM-650.2.5.5.1.

9. Dielectric loss (Df): measured using a material analyzer in accordance with the test standard of IPC TM-650.2.5.5.1.

		Comparative example	Example 1	Example 2	Example 3
Filler Type		-	SC-2500SQ	SC-2500SQ	SC-2500SQ
Film appearance		Good	Good	bow	Good
Molding appearance		Good	Good	bow	Good
Tensile strength (MPa)		40	85	74	86
Modulus of elasticity (MPa)		2017	2792	2902	2654
Elongation (%)		10	6	5	6
CTE (x / y, ppm)		27	18	12	17
CTE (z, ppm)		200	35	27	34
P / S (Hoz)		1.3 ~ 3.4	1.2	1.05	1.25
TGA Ash% (Air)		-	39	48	39
S / F @ 288		> 10 minutes	> 10 minutes	> 10 minutes	> 10 minutes
10 Ghz	Dk	2.2	2.76	2.85	2.78
	Df	0.001	0.0012	0.0014	0.0012

As a result of the experiment, it was found that the fluorine-based film of the present invention simultaneously exhibited excellent modulus characteristics and dimensional stability (see Table 1 above).

Claims (15)

1. A core layer comprising a fibrous substrate;

   Fluorine-based film laminated on both sides of the core layer; And

   Metal foil laminated on the fluorine-based film

   To include, The fluorine-based film is a metal laminate comprising a filler (filler).
2. The method of claim 1,

   The fluorine-based film is a metal laminated plate is a fluoropolymer film selected from the group consisting of polytetrafluoroethylene (PTFE), a fluoro and ethylene-propylene copolymer and a fluorocarbon backbone having a perfluoroalkoxy side chain.
3. The method of claim 1,

   Wherein the fluorine-based film is a perfluoro alkoxy (PFA) film metal laminate plate.
4. The method of claim 1,

   In the fluorine-based film, the filler is a metal laminate comprising a content of 10 to 70% by weight.
5. The method of claim 1,

   The filler is one of silica (silica), titanium dioxide (TiO ₂ ), alumina (Al ₂ O ₃ ), potassium titanate (K ₂ O ₆ TiO ₂ ), barium oxide (BaO).
6. The method of claim 1

   The core layer is a metal laminated plate comprising a resin layer cured by impregnating a high temperature resistant resin composition with a fiber substrate.
7. The method of claim 6,

   The high heat resistance resin composition is bisphenol A (bisphenol A) type epoxy, aromatic naphthalene epoxy, biphenyl aralkyl type epoxy, isocyanurate epoxy, cresol novlac type epoxy resin, high A metal laminate comprising at least one of heat resistant epoxy resins.
8. The method of claim 1,

   The fiber substrate is a spread glass fiber (Spread G / F) metal laminate.
9. The method of claim 8,

   The spread glass fibers are glass fibers; And an inorganic binder.
10. The method of claim 1,

    The metal foil is a metal laminated plate is a copper foil having a roughness (Rz) in the range of 0.5 to 5.0㎛.
11. The method of claim 1,

    The coefficient of thermal expansion (CTE) of the metal laminated plate is 5 to 40 metal laminated plate.
12. The method of claim 1,

    Peeling strength (P / S) of the metal foil to the fluorine-based film in the metal laminated plate is 0.8 to 1.2 kgf / cm metal laminated plate.
13. (a) impregnating a fibrous substrate in the high heat resistant resin composition and then semi-curing to prepare a core layer; And

    (b) stacking fluorine-based films and metal foils sequentially on the upper and lower surfaces of the core layer, and then integrating the same by a high-temperature compression process;

    The method of manufacturing a metal laminate according to any one of claims 1 to 12.
14. (a) forming a laminate by laminating fluorine-based films on the upper and lower surfaces of the core layer, respectively; And

    (b) stacking metal foils on the upper and lower surfaces of the laminate, and then integrating them by a high temperature compression process;

    The method according to any one of claims 1 to 12, wherein the core layer comprises a spread glass fiber.
15. The method according to claim 13 or 14,

    The high temperature compression process is a method of manufacturing a metal laminated plate is carried out for 10 minutes to 3 hours at a temperature of 270 to 400 ℃.

Images