JP3533595B2 - Method for manufacturing ultra-thin heat-resistant resin film - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION In response to recent miniaturization and higher density of electronic equipment and peripheral equipment, extremely thin films such as heat-resistant resin thin films used for parts thereof are required. The present invention relates to an extremely thin film that meets such a demand, and a new film manufacturing method that enables its manufacture.

[0002]

2. Description of the Related Art Conventionally, films have been manufactured by various methods. One such calendar method is several pairs of rolls,
A method of molding a resin or the like in a plastic state into a film is widely used in the rubber industry and the like, but a thin film cannot be used because it easily sticks to a roll or is cut. The T-type die method is a method of extruding a molten resin in a film form from a die and immediately cooling it with a chill roll or cold water. In the case of a crystalline polymer such as polypropylene, it is possible to obtain a material having good transparency. it can. The inflation method is a method of extruding a molten resin into a cylindrical shape and at the same time blowing air into the resin to inflate it and process it into a thin film, which is often used for making a polyethylene bag. The solution casting method is a method of casting a resin solution on a belt and evaporating and removing a solvent while moving on the belt to obtain a film, and a uniform thin film can be obtained. The wet casting method is a method in which a resin solution is extruded in a film form from a die into a coagulation bath to obtain a film, which is used for cellophane and the like. A polyester film or polystyrene film produced by the T-die method or the like is biaxially stretched at a temperature equal to or higher than the glass transition point in order to increase tensile strength and the like, and the thickness is thinned by this biaxial stretching. You can also

[0003]

As described above, in the calendering method, a thin film easily sticks to the roll or is cut, and in the T-type die method, when peeling from a cooling roll or applying cold water. Easy to cut. Further, the solution casting method facilitates cutting when peeled from the belt, and the wet casting method facilitates cutting when pulled up from the coagulation bath. By the inflation method and biaxial stretching, it is possible in principle to produce a very thin film, but since it is difficult to finely adjust the air pressure and the stretching speed, a film with a thickness of 5 μm or less is produced. Not not. The first problem to be solved by the present invention is to cope with the recent trend toward miniaturization and high density of electronic devices and their peripheral devices, which is an extremely thin film which has not existed until now.
In particular, it is to provide an extremely thin film of a non-stretchable resin such as a heat resistant resin. A second object is to provide a new film manufacturing method that enables the manufacture of such an extremely thin film and is applicable to the manufacture of a film having a certain thickness.

[0004]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventor has a support made of a thin aluminum plate having a thickness of 0.1 to 2 mm in a range where a heat resistant resin thin film layer is formed on one side. Masking, leaving the surface uncoated, apply a solution of polyamidecarboxylic acid in dimethylacetamide, remove the masking tape, and heat to about 200 ° C to vaporize and remove dimethylacetamide to accelerate the polymerization reaction. Then, a thin film layer of polyimide is formed, and after a frame-shaped fixture is adhered along the peripheral edge of the thin film layer, the support made of a thin aluminum plate is dissolved and removed with an aqueous sodium hydroxide solution. And a method for producing an ultrathin heat-resistant resin film having a thickness of 1 to 2 μm (hereinafter, referred to as “first invention”), and a thickness of 0.1
A support made of a thin aluminum plate of ~ 2 mm is masked while leaving a range for forming a heat-resistant resin thin film layer on one side, and a heat-resistant fluororesin solution is applied to the surface of the unmasked surface, and a masking tape is applied. After removing, about 3
After heating to 50 ° C to evaporate and remove the solvent and melt the heat-resistant fluororesin to form a thin film layer, a frame-shaped fixture is adhered along the periphery of the thin film layer, and then a thin aluminum plate is used. 1 to 2 μm in thickness held by a fixture characterized by dissolving and removing the support with an aqueous solution of sodium hydroxide
The method for producing the ultrathin heat-resistant resin film (hereinafter referred to as "second invention") is proposed.

The support used in the first and second aspects of the invention has an ultrathin heat-resistant resin thin film layer formed on its surface, and when treated with an acid or an alkali, it easily reacts and dissolves. It must be made of a removable material. In general, examples of the inorganic material that easily reacts include salts soluble in water such as salt and carbonates such as calcium carbonate that easily react and dissolve in an acid. However, it is difficult to constantly produce a support having a smooth surface and mechanical strength by a usual method. From such a viewpoint, as the material of the support, metals such as zinc, iron, and copper that are inexpensive and have a high ionization tendency and are easily dissolved in an acid, or zinc, aluminum, tin, lead, which is soluble in both an acid and an alkali, Antimony,
Examples include amphoteric metals such as bismuth. Among them, aluminum is the most suitable as the material of the support because it can be easily formed into a thin plate having a thickness of 0.1 to 2 mm and can be easily dissolved in an aqueous sodium hydroxide solution.

In the first and second aspects of the invention, by masking while leaving a range for forming the heat-resistant resin thin film layer on one surface, an ultrathin film of a predetermined size can be manufactured in advance, and the ultrathin film can be produced. It is possible to avoid the complexity of handling such as cutting into a proper size and the occurrence of distortion in the film during the handling. Then, the masking tape used for this masking is removed before the heat-resistant resin of the thin film layer is cured. Therefore,
It is possible to prevent various troubles from occurring due to the heat resistant resin being adhered and cured at unnecessary places or unexpected places.

In the first invention, the heat-resistant resin thin film layer is formed by applying a dimethylacetamide solution of polyamidecarboxylic acid, which is a polyimide precursor of the heat-resistant resin, removing the masking tape, and then heating to about 200.degree. It is formed by vaporizing and removing dimethylacetamide which is a solvent and causing a polymerization reaction to form a polyimide.

In the second invention, the heat-resistant resin thin film layer is formed by applying a heat-resistant fluororesin solution, removing the masking tape, and then heating at about 350 ° C. to vaporize and remove the solvent to melt the heat-resistant fluororesin. It is formed by Among the heat resistant fluororesins used in the second invention, the perfluoroalkoxy resin is most preferred.

In the first and second aspects of the invention, after forming the thin film layer, a frame-shaped fixture is adhered along the peripheral edge of the thin film layer, and then the aluminum thin plate of the support is dissolved and removed with an aqueous sodium hydroxide solution. By preventing the occurrence of cracks and distortions in the ultra-thin film during the process,
Furthermore, by shipping the obtained ultra-thin heat-resistant resin film having a thickness of 2 μm while holding it in the fixture, it is possible to prevent damage during transportation of the ultra-thin film and damage during handling of the recipient. .

[0010]

[Example 1]

(1) Preparation of support As a support, the thickness is 0.1 mm and the size is 110 × 1.
Aluminum plate with 10 mm and glossy surface (JIS
H4000 AlN30H-H18) was used. A masking tape (“ELEP Masking Tape N-380” manufactured by Nitto Denko Corporation) was attached to one surface of the film, and the other surface was used as a film layer forming surface.

(2) Formation of Polyimide Film Layer A thin film of a dimethylacetamide solution of an intermediate polyamidecarboxylic acid obtained by precondensation in dimethylacetamide was thinly applied to the film layer formation surface of the above-mentioned support. The masking tape was removed, and the film was heated and dried at 200 ° C. to form a polyimide film layer having a thickness of 2 μm.

(3) The fixed thickness of the film is 1 mm, the outer shape is 20 × 20 mm, and the outer circumference is 2 mm.
Epoxy thermosetting adhesive is applied to the lower surface of a nickel-plated brass frame-shaped fixture with a 16 x 16 mm window-like hole in the center, leaving the edges of It was pressure-bonded to the film layer produced in 1 above, heated at 120 ° C. for 1 hour to be fixed, and the support was cut along the outer periphery of the frame-shaped fixture to obtain a semi-finished product. In addition, as the frame-shaped fixing tool, one made of stainless steel resistant to acid and alkali is also used.
The size is also determined by the size of the film demanded by the market. Generally, if the film is made wider than necessary, damage due to damage due to carelessness during transportation and handling will increase.

(4) Removal of support The above-mentioned semi-finished product is immersed in a 33 wt% sodium hydroxide aqueous solution heated at 50 ° C. for 30 minutes to remove the support made of aluminum, and washed with water to fix it in a frame shape. A 2 μm-thick polyimide film held by the tool was obtained. For the measurement of the thickness of the obtained polyimide film, a high precision type (repetition precision 0.01 μm) of an electronic micrometer (K103A) manufactured by Anritsu Corporation was used.

Example 2 In the same manner as in Example 1, a support having a polyimide film layer having a thickness of 2 μm formed on one surface was cut into a size of 15 × 20 mm to obtain a thickness of 2
mm, 30 × 40 mm, place the polyimide film layer on the center of the upper surface of the acrylic plate fixture toward the acrylic plate fixture, fix with masking tape, cut out the central part of the masking tape, and make a 7 × 10 mm window. A semi-finished product was opened, and a polyimide film having a thickness of 2 μm held by an acrylic plate fixture and a masking tape was obtained in the same manner as in Example 1. In addition, because it is fixed to the acrylic plate fixture,
The size of the polyimide film cut on the support along with the support is determined by how wide the market demands the film. Moreover, when the support is dissolved and removed, the portion of the portion covered with the masking tape near the window is dissolved and removed, but the entire portion is prevented from being dissolved and removed.

2 Production of Perfluoroalkoxy Resin Film [Example 3] A primer-less perfluoroalkoxy resin solution (“RD1” (tentative name) manufactured by Daikin Co., Ltd.) was thinly applied on one surface of a support similar to that in Example 1. Apply, remove the masking tape, and heat to 350 ° C to a thickness of 1 μm.
A perfluoroalkoxy resin thin film layer having a thickness of 1 μm is adhered to an acrylic plate fixture with a masking tape together with an aluminum thin plate and is held in the same manner as in Example 2 to produce a perfluoroalkoxy resin thin film layer. An alkoxy resin film was obtained.

Example 4 In the same manner as in Example 3, a primerless perfluoroalkoxy resin solution was thinly applied to one surface of the support, and the masking tape was removed.
By heating to 350 ° C. to form a thin film layer of perfluoroalkoxy resin having a thickness of 2 μm, the frame-shaped fixture was adhered, the support was dissolved and removed in the same manner as in Example 1, and the frame-shaped fixture was formed. A retained perfluoroalkoxy resin film having a thickness of 2 μm was obtained.

3 Production of Heat-Resistant Polyurethane Film [Reference Example 1] A heat-resistant urethane solution (Takelac E-manufactured by Takeda Pharmaceutical Co., Ltd. was used on one side of a support similar to that used in Example 1.
365) thinly and remove the masking tape,
It is heated and dried at 50 ° C. to form a thin film layer of a heat-resistant polyurethane resin having a thickness of 2 μm, which is adhered to a frame-shaped fixture in the same manner as in Example 1, the support is dissolved and removed, and the thickness retained by the fixture is fixed. A heat resistant polyurethane film having a length of 2 μm was obtained.

[Reference Example 2] In the same manner as in Reference Example 1, a thin film layer of a heat-resistant polyurethane resin having a thickness of 2 μm was formed on one surface of a support, treated in the same manner as in Example 2, and treated with a masking tape to obtain an acrylic plate. Thickness of 2μ glued to and held by fixture
A heat resistant polyurethane film of m was obtained.

[0019]

Since the method for producing an ultrathin heat-resistant resin film according to the present invention has the above-mentioned structure, the ultrathin heat-resistant resin film which can cope with the miniaturization and high density of the electronic-related equipment on the market. It will enable the future provision of electronic-related equipment industry and further enhance the convenience of communication in social life.

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Claims (2)

(57) [Claims] 1. A support made of a thin aluminum plate having a thickness of 0.1 to 2 mm is masked except for a region where a heat-resistant resin thin film layer is formed on one surface, and a polyamide carvone is provided on the surface of the unmasked surface. After applying the dimethylacetamide solution of acid and removing the masking tape,
After heating to 0 ° C to vaporize and remove dimethylacetamide to accelerate the polymerization reaction to form a polyimide thin film layer, a frame-shaped fixture is adhered along the periphery of the thin film layer, and then a thin aluminum plate is removed. Method for producing an ultrathin heat-resistant resin film having a thickness of 1 to 2 μm, which is held by a fixture, which comprises dissolving and removing the supporting material with an aqueous sodium hydroxide solution. 2. A support made of a thin aluminum plate having a thickness of 0.1 to 2 mm is masked except for the area where a heat-resistant resin thin film layer is formed on one surface, and the surface of the unmasked surface is heat-resistant. After applying the fluororesin solution and removing the masking tape, it is heated to about 350 ° C. to vaporize and remove the solvent and melt the heat-resistant fluororesin to form a thin film layer,
A frame-shaped fixture is adhered along the periphery of the thin film layer, and then the support made of a thin aluminum plate is dissolved and removed with an aqueous sodium hydroxide solution. Method for producing ultra-thin heat-resistant resin film of 2 μm