JPS63218349A - Double layer film and manufacture thereof - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a multilayer film based on polyimide (hereinafter referred to as PI) and a method for producing the same.

(Prior art) In some cases, molded products and laminates are manufactured using molds and hot plates, and in this method, the problem of releasing the resulting product from the molds and hot plates is important. be.

A PI film may be used for this release. PI has excellent film dimensional stability and mechanical properties at high temperatures, and is preferable for mold release when molding is performed at high temperatures.

(Problems to be Solved by the Invention) However, the PI film has a problem in that it has poor durability in terms of releasability and can only be used repeatedly.

Mata and PI films are sometimes wound into a roll around a core as a long product. At this time, since the surface of the PI film is smooth, the upper and lower layers of the film stick together, and even if you try to correct misalignment, wrinkles, etc.
This correction is difficult because the film does not slip between surfaces (the coefficient of friction is large). Due to the poor slippage between the surfaces of the film, there was also the problem of poor workability during rewinding after winding and slitting to cut to a specified width. Scale.

This becomes more noticeable as the film becomes thinner.

In order to improve the slipperiness, attempts have been made to disperse organic lubricants such as paraffin, fatty acid esters, higher alcohols, or inorganic lubricants such as silica powder into the tPI film. However, in the former case, the heat resistance is significantly reduced due to the organic lubricant, and in the latter case, the electrical insulation performance is adversely affected, and the application of the film to electronic equipment and semiconductor parts is likely to be hindered.

(Means for Solving the Problems) In order to solve the above problems of the prior art, the present inventors
As a result of various studies, we decided to create a multilayer structure using PI film and silicone resin or fluororesin.

It was found that a film with excellent slip properties and release durability can be obtained. In addition, we have developed a technology to easily produce a multilayer film with , and have completed the present invention.

That is, the multilayer film according to the present invention is a PI film with a silicone resin layer or a fluororesin layer formed on at least one side.

As the PI film as the base material of the multi-l-film of the present invention, any conventionally known PI film can be used without particular limitation, and a specific example thereof is a reaction product of aromatic tetracarboxylic dianhydride and aromatic diamine. One example is a PI film obtained by converting a certain polyamic acid into an imide. In addition,
Although the thickness of this film is not limited, it is practically preferably about 5 to 150 μflu.

One or both sides of such a PI film are coated with silicone resin or fluororesin (for example, polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer) to provide heat resistance, slipperiness, and mold release properties. A thin layer is provided having a. It has been found that the thickness of the silicone resin or fluororesin layer is preferably about 0.01 to 3 μm from the viewpoint of mold release effect, sliding effect, and prevention of transfer of the 11t-forming resin. However, if desired, it can be formed thinner or thicker than this.

Next, another aspect of the present invention is a compound Il! The film manufacturing method will be described. The method for producing a multilayer film according to the present invention is to apply a silicone resin or fluororesin-containing liquid on one side of a lyamic acid film, and then heat it to imide polyamic acid, which is a component of the film. It is characterized in that a silicone resin layer or a fluororesin layer is formed on the film at the same time as the film is converted.

The polyamic acid film used here can be produced from a polyamic acid solution obtained by reacting, for example, an aromatic tetracarboxylic dianhydride and an aromatic diamine in an organic polar solvent.

Specific examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3,4,4'-benzophenonetetracarboxylic dianhydride, 3°3', 4.
4'-biphenyltetracarboxylic dianhydride, 2,3,
3.4-biphenyltetracarboxylic dianhydride, 2.
3. 6. 7-naphthalenetetracarboxylic dianhydride, 1. 2. 5. 6-naphthalenetetracarboxylic dianhydride-L 4,5t 8-naphthalenetetracarboxylic dianhydride, 2. 2'-bis(3,4-dicarboxyphenyl)propane 2m hydrate, bis(3,4
-dicarboxyphenyl) sulfone dianhydride, and the like.

Specific examples of aromatic diamines include 4゜4-cyanodiphenyl ether, 4.4'-diaminodiphenylmethane, 3.3'-diaminodiphenylmethane, paraphenylenediamine, metaphenylenediamine, benzidine, 3,3' -dizylbenzidine, 3.3'-dimethoxybenzidine, 4゜4-, diaminodiphenylsulfone, 4,4-diaminodiphenylsulfide, 4.4
'-Diaminodiphenylpropane, 2,2-bis(4-
Examples include (4aminophenoxy)phenyl]propane.

Furthermore, as a specific example of the organic polar solvent, N-methyl-2
-pyrrolidone, dimethylacetamide, dimethylformamide, dimethylsulfoxide.

Examples include hexamethylene phosphor triamide. These organic polar solvents include phenols such as cresol, phenol, and xylenol, and hexane.

Benzene, toluene, etc. can also be mixed.

Polyamic acid is produced by reacting aromatic tetracarboxylic dianhydride and aromatic diamine in an organic polar solvent. The monomer concentration when obtaining 1 can be set according to various conditions, but is usually 5.
~30% by weight. Mana.

The reaction temperature is usually 80°C or lower, preferably 5 to 50°C, and one reaction time is about 1 to 20 hours.

A polyamic acid film is obtained by casting the polyamic acid solution thus obtained on a supporting material made of glass, stainless steel, etc., and heating it to remove the solvent. Heating conditions are set depending on the type of solvent, casting thickness, etc. 1 Usually, the temperature is 80 to 250°C and the time is 1 to 60 minutes.

In the present invention, a solution prepared by dissolving or dispersing a silicone resin or a fluororesin in an organic solvent or water is applied to one or both sides of the polyamic acid film thus obtained. The resin concentration in this containing liquid is usually about 1
The amount is 0 to 60% by weight, and the coating on the polyamic acid film is carried out by methods such as dipping, reverse coating, kiss coating, and spray coating.

Then, heating is performed next. This heating causes the conversion of the polyamic acid to PI and the evaporation of volatile components such as ring-closed water generated during the conversion.

The organic melt adhesive or water in the containing liquid evaporates, and a silicone resin or fluororesin is baked onto the surface of the produced PI film to form a layer. Incidentally, if an organic polar solvent remains in the polyamic acid film, the solvent also evaporates during this heating. Therefore, this heating is typically performed at a temperature of 2
00-400℃.

The test is carried out for a period of 1 to 120 minutes.

(Example) Hereinafter, it will be explained in more detail with reference to Examples.

Example I 20 ff1 titfl of 4°4-diaminodiphenyl ether was dissolved in 220 parts by weight of N-methyl-2-pyrrolidone, and while cooling and stirring, pyromellitic dianhydride 21 was dissolved.
．． 8 parts by weight was gradually added and the reaction was continued for another hour (temperature 2
(maintained below 0℃), then add the above and Kanji pyrrolidone 200
Dilute by adding parts by weight to obtain a polyamic acid solution with a viscosity of 200 centipoise (B-type viscometer, temperature 30°C).

This solution was cast onto a glass plate and heated at 100°C for 1
The film was sequentially heated at 50° C. for 10 minutes and at 200° C. for 10 minutes, and then peeled off from the glass plate to obtain a polyamic acid film with a groove of 50 μm in thickness.

Next, one side of this film was spray-coated with a silicone resin-containing liquid and heated at 400°C for 1 hour to form a composite film (silicone resin 11M, thickness approximately 0.1 μm).
) was obtained.

As the above-mentioned liquid, a toluene solution (concentration 0.1% by weight) of a silicone resin (manufactured by Shin-Etsu Silicone Co., Ltd., trade name KS-707) was used.

Also, fix the four sides of the film when heating.

Prevented heat shrinkage.

When this multilayer film was used as a template during the production of a heat-resistant laminate, it was possible to use it repeatedly more than 10 times under working conditions of 300"C x 60 minutes.

In addition, the surface roughness Ra) of the silicone resin layer forming surface of the multilayer film with is 0.003μ groove, and the friction coefficient is 0.12.
This value did not change even after heating at 300° C. for 12 hours, indicating that the slipperiness and durability were outstanding. Note 2
The surface roughness and friction coefficient were measured using a surface roughness profile measuring device (manufactured by Tokyo Seimitsu Co., Ltd., Surfcom 550A) and a friction coefficient measuring device (manufactured by Toyo Seiki Co., Ltd., EFM-4).

Comparative Example 1 A PI film was obtained in the same manner as in Example 1 except that no release agent was applied.

When the PI film was subjected to a mold release test under the same conditions as in Example 1, it was found that the film partially stuck to the laminate during the second use, resulting in a significant decrease in template formability. Sometimes the film was damaged.

Further, the surface roughness of this film was 0.003μ, and the coefficient of friction was 0.4.

Comparative Example 2 One side of the PI film of Comparative Example 1 was coated with paraffin wax. The surface roughness of the coated surface was 0.004 μm, and the M friction coefficient was 0.15. When this was heated at 300"C for 12 hours, the surface roughness did not change, but the friction coefficient increased to 0.40. However, the smoothness decreased.

Example 2 20 parts by weight of diaminodiphenyl ether was dissolved in 196 parts by weight of dimethylacetamide, 29.4 parts by weight of biphenyltetracarboxylic dianhydride was gradually added with stirring, and after the viscosity increased, the mixture was heated to 60 to 80°C. The mixture was reacted for 20 hours to obtain a polyamic acid solution.

This solution is cast onto a stainless steel endless belt,
After heating at a temperature of 150° C. for 20 minutes, it is peeled off from the belt to obtain a long polyamic acid film with a groove of 30 μm in thickness.

Next, this film is dipped in a fluororesin-containing liquid, and the containing liquid is applied to both sides of the film.

Burn (7' Yupon Co., trade name: Teflon 120) was used.

Thereafter, this film was heated at 300° C. for 30 minutes while restraining the width direction with a pin tenter to obtain a multilayer film (FJ: resin layer thickness approximately 0.3 μrIL).

When this film was used for mold release during the production of silicone rubber molded products, no change was observed even after repeated use 100 times under working conditions of 200°C x 30 minutes.

In addition, the surface roughness of the surface on which the fluororesin resin 11 is formed of this 1 m film is 0.006μ, and the coefficient of friction is 0.30, and these values do not change even after heating at 200°C for 96 hours. The slipperiness and durability were simple.

Comparative Example 3 A PI film was obtained in the same manner as in Example 1 except that no boat-forming agent was applied.

When this PI film was subjected to a mold release test under the same conditions as in Example 2, it was difficult to peel off on the 5th use and broke on the 6th use.

Further, the surface roughness of this film was 0.004 μm, and the JIll friction coefficient was 0.35.

(Effects of the Invention) Since the present invention completely forms a silicone resin layer or fluororesin # on the surface of the PI film, it not only has improved slipperiness as shown in the above Examples and Comparative Examples. It is possible to provide a multilayer film that has excellent template durability and can be used repeatedly as a template. Furthermore, according to the method of the present invention, a multilayer film using PI as a base material can be easily produced.

Claims (2)

[Claims] (1) A multilayer film in which a silicone resin layer or a fluororesin layer is formed on at least one side of a polyimide film. (2) By applying a silicone resin or fluororesin-containing liquid on at least one side of a polyamic acid film and then heating, the polyamic acid that is a component of the film is converted into an imide, and the silicone resin is applied onto the film. A method for producing a multilayer film, characterized by forming a layer or a fluororesin layer.