JPH05269918A - Continuous production of fluoroplastic resin copper clad laminated sheet - Google Patents

Abstract

PURPOSE:To produce the laminated sheet with good productivity without performing baking at high temp. CONSTITUTION:When a copper clad laminated sheet is produced using a double belt continuous molding apparatus consisting of a pair of upper and lower endless metal belts 19, 20 and a heating pressure container 21, glass cloths 5-7 subjected to surface treatment by a silane coupling agent having at least one amino group are interposed between long fluoroplastic films 1-4 to laminate the fluoroplastic films and the glass cloths and copper foils 8, 9 are arranged to both surfaces of the obtained laminate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a continuous manufacturing method of a fluorine resin copper clad laminate, and more specifically, a space satellite broadcasting receiving antenna, a receiving converter circuit board, a microstrip ultra high frequency circuit board, and a mobile radio. The present invention relates to a continuous production method of a fluorine resin copper clad laminate suitably used for a circuit board, a pocket bell, a circuit board for other high frequency application equipment and the like.

[0002]

2. Description of the Related Art Conventionally, fluorine resin copper clad laminates have been used in satellite broadcasting, mobile radio fields, etc. due to their excellent high frequency characteristics.
It is used in the communication field that requires the Hz (Gigahertz) band. When making a prepreg of a fluorocarbon resin copper-clad laminate using ordinary tetrafluoroethylene resin, the glass cloth is impregnated with an aqueous fluorocarbon resin dispenser using an impregnation / firing device to remove excess dispersion. It is manufactured by scraping John to make it uniform and then firing it at high temperature.

However, this manufacturing method is
Since it has to be fired at a high temperature of 400 ° C., a special high-temperature firing apparatus is required, and there is a problem that the amount of resin adhered to the glass cloth varies greatly and the plate thickness accuracy of the laminated plate is poor. Further, when manufacturing a copper-clad laminate, a plurality of the pre-pregs are aligned to have a predetermined thickness, a copper foil and a release film are stacked on top of this, and a stainless steel end plate and a cushion material are combined, between the hot plates of the press. A method of stacking 4 to 12 sheets and heating and pressurizing for a certain time is generally adopted, but there is a problem that the number of steps is large and manpower is required.

In order to solve such a problem, in recent years,
Various methods for manufacturing highly productive laminates, in which multiple prepregs are sandwiched between endless belts and continuously heated and pressed, have been investigated, but the method using ordinary prepregs requires the reaction of the impregnating resin required for molding. It takes a long time, and the productivity itself is limited due to restrictions on equipment costs such as heating and pressurizing containers, endless belts, and running costs. For example, when a prepreg is formed by impregnating a commonly used tetrafluoroethylene resin (hereinafter referred to as PTFE resin) into a powder form, the melting point of PTFE is 327 ° C.
Therefore, compression molding conditions of 400 ° C, 50 kg / cm ² and 60 minutes are required. If this is molded using a continuous molding machine, the speed will be extremely low or the heating / pressurizing container will be long. One of these is to increase the speed, and in either case, there remains a problem in terms of productivity.

On the other hand, in Japanese Patent Application Laid-Open No. 1-317727, a metal foil is arranged on a laminated plate in which a glass cloth is interposed between films of a predetermined number of fluorine resin films, and heating and pressure molding is performed. However, since this method is a batch method, the productivity is not sufficient. Furthermore, the laminate obtained by this method is treated with a silane coupling agent. Since the glass cloth which is not used is used, the adhesiveness between the fluorine resin film and the glass cloth is insufficient, and the solder heat resistance,
There was a problem of lack of chemical resistance.

In order to solve the problem of the adhesiveness between the fluorine resin and the glass cloth, the inventors of the present invention use a glass cloth surface-treated with a silane coupling agent having at least one amino group as the glass cloth. , And found that the adhesiveness with fluororesin is remarkably enhanced, and filed a patent application earlier (Japanese Patent Application No. 3-29422).

[0007]

Based on such a technical background, the present invention can produce a fluorine resin copper clad laminate with high productivity without firing at a high temperature, and further,
It is an object of the present invention to provide a manufacturing method capable of manufacturing a fluorine resin copper clad laminate excellent in solder heat resistance and chemical resistance.

[0008]

That is, according to the present invention, when a copper clad laminate is manufactured by using a double belt continuous molding apparatus having a pair of upper and lower endless metal belts and a heating / pressurizing container, The fluororesin film and the glass cloth are laminated by interposing a glass cloth surface-treated with a silane coupling agent having at least one amino group between the fluororesin films, and the copper foil is then coated on at least one side thereof. The gist is a continuous manufacturing method of a fluorine resin copper-clad laminate characterized by being arranged.

The present invention will be described in detail below.

In the present invention, the fluorine resin film includes tetrafluoroethylene resin, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer resin, tetrafluoroethylene / hexafluoropropylene copolymer resin, tetrafluoride. All fluorine resins such as ethylene-ethylene copolymer resin and trifluoroethylene chloride resin can be used.
A film composed of a tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer resin and a tetrafluoroethylene / hexafluoropropylene copolymer resin is preferable.

The thickness of the fluorine resin film is not particularly limited, but a thickness of 0.01 to 1 mm is preferable, and a thickness of 0.05 to 5 mm is preferable.
A thickness of 0.3 mm is particularly preferable. Also, the number of films may be one, but a plurality of films may be used as one set.

The silane coupling agent used in the present invention is a silane coupling agent having at least one amino group in its structure. For example, 3-aminopropyltriethoxysilane as an aliphatic aminosilane,
N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, etc., urea-based aminosilane, γ-ureidopropyltriethoxysilane, etc., aromatic aminosilane, γ-phenylaminopropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl)-
γ-aminopropyltrimethoxysilane, N-β- (N
-Benzylaminoethyl) -γ-aminopropyltrimethoxysilane and the like, N-β as a cationic aminosilane
Examples thereof include-(N-benzylaminoethyl) -γ-aminopropyltrimethoxysilane-hydrochloride and N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane-hydrochloride.

As the glass cloth, E glass (non-alkali glass for electric use) cloth, S glass (high strength glass)
Examples thereof include cloth, D glass cloth, quartz glass cloth, silica glass (low dielectric glass) cloth, C glass (chemically containing alkali glass) cloth, and E glass cloth is particularly preferable.

Further, it is preferable that the single fiber diameter of the glass fiber constituting the glass cloth used in the present invention is 3 to 15 μm, and the thickness of the glass cloth is 20 to 250.
It is preferably μm. If the single yarn diameter is smaller than 3 μm, it tends to be broken and difficult to handle. On the other hand, if the single yarn diameter exceeds 15 μm, the surface smoothness of the laminated plate may be easily deteriorated. Further, when the thickness of the glass cloth is less than 20 μm, the strength of the glass cloth becomes weak, and it becomes difficult to handle it in the surface treatment and molding process. On the other hand, when the thickness of the glass cloth exceeds 250 μm, the thickness is secured. Therefore, it is necessary to use a glass fiber having a large fiber diameter, the surface smoothness of the laminated plate is likely to deteriorate, and the silane coupling agent tends to be difficult to impregnate into the glass cloth.

The amount of the silane coupling agent attached to the glass cloth is 0.05 to 0.6 with respect to the glass cloth.
It is preferably in the range of 0.08 to 0.3% by weight, especially 0.08 to 0.3% by weight.
If the amount adhering to the glass cloth is less than 0.05% by weight, the moisture absorption resistance may not be improved, and if it exceeds 0.6% by weight, the adhesion between the fluororesin film and the glass cloth may deteriorate. It will be easier.

The surface treatment method of the glass cloth is not particularly limited. For example, the silane coupling agent is dissolved in water to form a treatment solution, and the glass cloth is immersed in the treatment solution or the treatment solution is sprayed on the glass cloth. After applying, squeeze with a padder roll and heat-treat. The heat treatment conditions are 80 to 17
Heating at 0 ° C. for 2 to 15 minutes is preferable from the viewpoint of drying and crosslinking curing reaction of the silane coupling agent. From the viewpoint of workability, the treatment liquid concentration is preferably 0.1 to 5.0% by weight.

Next, the present invention will be described with reference to FIG.

First, four long fluororesin films 1
5 to 4, a glass cloth surface-treated with a silane coupling agent having at least one amino group between the films.
7 to 7 are passed through the guide rolls 10 to 16 and then the copper foils 8 and 9 are attached to each other with the use of the rolls 17 and 18. Next, the endless metal belts 19 and 2 paired up and down
It is sandwiched between 0 and is heated and pressed while passing through the heating and pressing container 21 to be continuously molded to form a long laminated body. Further, the copper clad laminate is conveyed and cut into a predetermined size by a cutting machine 22 to form a copper clad laminate.

FIG. 1 shows an example of manufacturing a double-sided copper-clad laminate using four fluororesin films and three glass cloths. In FIG. 1, a long film and a long glass cloth are used. By adjusting the number of rolls, it is possible to produce a laminated plate composed of a desired number of films and glass cloth.
It is also possible to obtain a single-sided copper-clad laminate by setting either the upper or lower laminated roll for copper foil.

[0020]

EXAMPLES The present invention will be specifically described below with reference to examples.

Reference Example 1 So-called heat cleaning treatment E glass cloth 116T (single yarn diameter:
7 μm, weaving density: 60 warps / 25 mm, 58 wefts / 2
5 mm, thickness: 100 μm, manufactured by Unitika Ltd., and silane coupling agent, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane (SZ6032, manufactured by Toray Silicone Co., Ltd.) as an active ingredient 4 g.
/ Little, immersed in a treatment solution adjusted to pH 5.0, squeezed with a padder roll, and heat treated at 130 ° C for 5 minutes to obtain a surface-treated glass cloth.

Reference Example 2 γ-Phenylaminopropyltrimethoxysilane (SZ6083, manufactured by Toray Silicone Co., Ltd.) was used as a silane coupling agent, and a treatment liquid adjusted to an active ingredient of 4 g / liter and pH of 3.0 was used. In the same manner as in Reference Example 1, a surface-treated glass cloth was obtained.

Reference Example 3 Methyltrimethoxysilane (KBM13, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as a silane coupling agent, and the active ingredient 5 was used.
A surface-treated glass cloth was obtained in the same manner as in Reference Example 1 except that the treatment liquid adjusted to an aqueous solution of g / liter, pH 4.5 was used.

Reference Example 4 Tridecafluorooctyltrimethoxysilane (TSL8257, manufactured by Toshiba Silicone Co., Ltd.) as a silane coupling agent was dissolved in a mixed solution of 70% by weight of water and 30% by weight of isopropyl alcohol to obtain 4 g of active ingredient / liter. A surface-treated glass cloth was obtained in the same manner as in Reference Example 1 except that this was used as the treatment liquid.

Example 1 As a fluorine resin film, a tetrafluorinated ethylene / perfluoroalkyl vinyl ether copolymer resin film having a thickness of 250 μm (Neoflon PFA, manufactured by Daikin Industries, Ltd.)
As shown in FIG. 1, three sheets of the surface-treated glass cloth obtained in Reference Example 1 were passed through respective guide rolls as shown in FIG. 1, and then 18 μm copper foil (3EC,
Mitsui Mining & Smelting Co., Ltd.) is supplied up and down, combined with a matching roll and sent to an endless metal belt, and continuously molded by heating and pressing for 10 minutes at 390 ° C., 40 kg / cm ² in a heating and pressing container, thickness 1 A .13 mm double-sided copper clad laminate was obtained.

Example 2 The thickness was the same as in Example 1 except that the surface-treated glass cloth obtained in Reference Example 2 was used as the surface-treated glass cloth.
A 1.13 mm double-sided copper clad laminate was obtained.

Example 3 As a fluorine resin film, a tetrafluoroethylene / hexafluoropropylene copolymer resin film (Neotron FEP, manufactured by Daikin Industries, Ltd.) having a thickness of 250 μm was used.
A double-sided copper-clad laminate having a thickness of 1.13 mm was obtained in the same manner as in Example 1.

Example 4 As a fluorine resin film, a 250 μm thick tetrafluoroethylene / hexafluoropropylene copolymer resin film (Neoflon FEP, manufactured by Daikin Industries, Ltd.) was obtained as a surface-treated glass cloth in Reference Example 2. A double-sided copper-clad laminate having a thickness of 1.13 mm was obtained in the same manner as in Example 1 except that the surface-treated glass cloth was used.

Example 5 As a fluorine resin film, a tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer resin film having a thickness of 250 μm (Neoflon PFA, manufactured by Daikin Industries, Ltd.)
2 sheets of the surface-treated glass cloth obtained in Reference Example 1 were passed through the respective guide rolls between the films by using the apparatus shown in FIG. 1, and at the same time, 18 μm copper foil (J
(TC, manufactured by Nippon Mining Co., Ltd.) is fed up and down, combined with a matching roll and sent to an endless metal belt, and continuously molded by heating and pressing at 380 ° C., 35 kg / cm ² for 8 minutes in a heating and pressing container, and thickness. A 0.81 mm double-sided copper clad laminate was obtained.

Example 6 The thickness was the same as in Example 5 except that the surface-treated glass cloth obtained in Reference Example 2 was used as the surface-treated glass cloth.
A 0.81 mm double-sided copper clad laminate was obtained.

Comparative Example 1 The thickness was the same as in Example 1 except that the surface-treated glass cloth obtained in Reference Example 3 was used as the surface-treated glass cloth.
A 1.13 mm double-sided copper clad laminate was obtained.

Comparative Example 2 The thickness was the same as in Example 1 except that the surface-treated glass cloth obtained in Reference Example 4 was used as the surface-treated glass cloth.
A 1.13 mm double-sided copper clad laminate was obtained.

Comparative Example 3 The thickness was the same as in Example 1 except that a glass cloth not surface-treated was used in place of the surface-treated glass cloth.
A 1.13 mm double-sided copper clad laminate was obtained.

The obtained copper clad laminate was evaluated as a laminate by the following method, and the results are shown in Table 1. As is clear from Table 1, according to the present invention, it is possible to obtain a laminated plate having excellent characteristics.

Plate Thickness Accuracy A sample having a size of 200 × 200 mm was prepared according to JISC-6481, and the plate thickness was measured using a plate thickness meter Microfine-Σ (manufactured by Union Tool Co., Ltd.). Volume resistivity and surface resistance A sample of a predetermined size was prepared according to JISC-6481, and a vibrating lead electrometer TR was prepared.
It was measured using -84M (manufactured by Takeda Riken).

Dielectric constant and dielectric loss tangent LP Impedance Analyzer 4194A (manufactured by Yokogawa Hiyuretsu Pats Card) according to JIS C-6481
Was used to measure the value at 1 MHz. Solder heat resistance After laminating the laminate with a pretreatment (121 ° C, 2atm for 1 hour), soak it in a solder bath at 260 ° C for 30 seconds,
The appearance was evaluated by visual observation. ○ ── No abnormality △ ── Partially blistered × ── Blistered entirely

Peel Strength A sample of a predetermined size was prepared according to JIS C-6481 and measured using a precision universal tester 2020 (manufactured by Intesco). Thermal expansion coefficient Using a sample of 6 × 6 mm, TMA-50 (manufactured by Shimadzu Corporation) was used to raise the temperature at 2 ° C./minute, and the thermal expansion coefficient in the Z-axis direction was obtained from the thermal expansion curve in the range of 50 to 250 ° C. I asked.

Water absorption rate According to JIS C-6481, it was determined from the weight difference before and after the moisture absorption treatment (E-24 / 50 + D-24 / 23). Surface Hardness (Barcol Hardness) A 70 × 70 mm size sample was prepared in accordance with JISK-7060 and measured using a Barcol hardness meter GYZJ934-1 (manufactured by Barber Kolman).

[0039]

[Table 1]

[0040]

As is apparent from the above description, according to the present invention, it is possible to produce a fluorine resin copper clad laminate with high productivity without firing at a high temperature, and to obtain an excellent low dielectric constant. It is possible to manufacture a fluororesin copper-clad laminate having characteristics, solder heat resistance, chemical resistance, and high plate thickness accuracy.

[Brief description of drawings]

FIG. 1 is a schematic explanatory view of a continuous molding apparatus of the present invention.

[Explanation of symbols]

 1 to 4 Fluorocarbon resin film 5 to 7 Glass cloth 8, 9 Copper foil 10 to 16 Guide roll 17, 18 Laminating roll 19, 20 Endless belt 21 Heating / pressurizing container 22 Cutting machine

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Claims (1)

[Claims] 1. When a copper clad laminate is manufactured using a double belt continuous forming apparatus having a pair of upper and lower endless metal belts and a heating and pressing container, an amino group is provided between long fluororesin films. A fluororesin film and a glass cloth are laminated with a glass cloth surface-treated with a silane coupling agent having at least one of the above is interposed, and then a copper foil is disposed on at least one side thereof. Continuous production method for resin copper clad laminates.