JPH09157418A - Fluorine-based resin laminate improved in surface property and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a fluorine-based resin laminate improved in surface properties without causing problems in appearance by coating one or both surfaces of a plastic film with a fluorine-based resin dispersion and provide a method for producing the laminate. SOLUTION: This fluorine-based resin laminate can simply be produced at a low cost by coating one or both surfaces of a plastic film with a fluorine- based resin dispersion at a regulated concentration, drying the coated surfaces and then curing the laminate at an elevated atmospheric temperature in a heat- treating furnace or adding an organic solvent to the fluorine-based resin in the fluorine-based resin laminate having >=10μm thickness. The resultant laminate is excellent in appearance without any visually recognized crack on the surface.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a fluororesin laminate and a method for producing the same. More specifically, the present invention relates to a fluororesin laminate obtained by laminating a fluororesin layer on one or both sides of a plastic film, and a method for producing the same.

[0002]

2. Description of the Related Art A fluororesin laminate having a fluororesin layer laminated on one or both sides of a plastic film is
It is mainly formed into a tape and wound around a conductor such as copper, and is used for a coil for a motor, a cable or an electric wire for an aircraft. There are various types of this laminate depending on the combination of various thicknesses of the plastic film and the fluororesin layer.
On one or both sides of a 5 μm thick plastic film,
A laminate of fluororesin layers having a thickness of 2.5 μm to 25 μm is mainly used.

Usually, a fluororesin laminate obtained by laminating a fluororesin layer on one or both sides of a plastic film is obtained by laminating a fluororesin film (sheet) and a plastic film. It is manufactured by a method and a coating method in which a fluororesin dispersion (coating solution) is applied to a plastic film, dried, and then the resin layer is cured and cured. As a method for producing such a fluororesin laminate, in the case of a fluororesin laminate having a resin layer having a thickness of less than 10 μm, for example, a fluororesin laminate having a thickness of 2.5 μm, usually a fluororesin dispersion ( It is manufactured by a coating method of applying a coating liquid).

As a method for producing such a fluororesin layer, a fluororesin laminate having a resin layer thickness of less than 10 μm, for example, a fluororesin laminate having a thickness of 2.5 μm is usually used. It is manufactured by a coating method of coating John (coating liquid).

However, in the coating method, it is necessary to devise the coating method, which makes the manufacturing technique difficult. Further, even if the coating itself can be made possible by these measures, there is a problem that remarkable cracks occur on the surface of the finally laminated fluororesin layer.
This was remarkable when a fluorine-based resin layer having a thickness of 0 μm or more was laminated. Then, after the laminated body with such cracks is processed into a tape, when wound around a conductor and heat-sealed, voids are generated due to the cracks, and electric discharge easily occurs in that portion. There is a problem with sex.

Therefore, in general, the fluororesin laminate is superior in quality when it is produced not by the coating method but by the laminating method of laminating the film of the fluororesin.

[0007]

However, when the fluororesin laminate is manufactured by the laminating method, the price of the fluorofilm is higher than that of the dispersion and the measures for preventing wrinkles during lamination are complicated. Therefore, there is a problem that the manufacturing cost is higher than that of the coating method.

Therefore, the present inventors have solved the above-mentioned conventional problems and obtained by applying a fluorine-based resin dispersion on one or both sides of a plastic film, and there is no problem in appearance. As a result of intensive studies for the purpose of providing a resin laminate and a method for producing the same, the present invention has been achieved.

[0009]

The gist of a fluororesin laminate having improved surface properties according to the present invention is that a plastic film and a fluororesin dispersion is applied to one or both surfaces of the plastic film. It is composed of the formed fluororesin layer.

Another aspect of the fluororesin laminate having improved surface properties according to the present invention is formed by applying a fluororesin dispersion to one or both surfaces of a plastic film. Thickness 10
It is composed of a fluorine-based resin layer having a thickness of at least μm.

The main component of the fluororesin dispersion is tetrafluoroethylene resin, vinylidene fluoride resin, vinyl fluoride resin, tetrafluoroethylene-hexanefluoropropylene resin copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether. It is composed of one or more of a resin copolymer and an ethylene-tetrafluoroethylene resin copolymer.

Further, the thermal decomposition temperature of the plastic film is 400 ° C. or higher.

The plastic film is a polyimide film.

The gist of the method for producing a fluororesin laminate having improved surface properties according to the present invention is that a fluororesin dispersion is applied to one or both sides of a plastic film and dried, followed by heat treatment. The purpose is to form a fluororesin by setting the ambient temperature to a high temperature and curing in a furnace.

Another aspect of the method for producing a fluororesin laminate having improved surface properties according to the present invention is that a fluororesin dispersion is applied to one or both sides of a plastic film and dried. After that, the temperature of the atmosphere is raised to a high temperature in a heat treatment furnace and curing is performed to form a fluororesin layer having a thickness of 10 μm or more.

The ambient temperature in the heat treatment furnace is preferably 450 ° C. or higher in the hot air oven and 400 ° C. or higher in the far-red oven.

The other subject matter of the method for producing a fluororesin laminate having improved surface properties according to the present invention is as follows:
This is to form a fluororesin layer by applying a fluororesin dispersion containing an organic solvent added to one or both sides of a plastic film, drying it, and then curing it in a heat treatment furnace.

The other subject matter of the method for producing a fluororesin laminate having improved surface properties according to the present invention is as follows:
Fluorine resin dispersion with organic solvent added is applied to one or both sides of plastic film, dried and then cured in a heat treatment furnace to give a thickness of 10μ.
This is to form a fluorine-based resin layer having a thickness of m or more.

The amount of the organic solvent added to the dispersion is 0.01% to 8% based on the total solid content of the fluororesin.
It is to be 0%.

The boiling point of the organic solvent is 60 ° C. or higher.

The ambient temperature in the heat treatment furnace is 350 ° C. or higher in the hot air oven and 300 ° C. or higher in the far-red oven.

Further, the concentration of the fluororesin dispersion is 30% or more.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION The fluororesin laminate having improved surface properties according to the present invention has a fluororesin layer formed by applying a fluororesin dispersion to one or both sides of a plastic film. In spite of being obtained by coating, no severe cracks are observed on the surface of the obtained laminate, which can be realized without any problem in appearance, and the fluororesin laminate can be easily prepared. .

Specifically, for carrying out the manufacturing method of the present invention, for example, an apparatus 10 as shown in FIG. 1 can be used. This device 10 includes a plastic film 12
A film feeding device 14 for feeding the film, a film winding device 16 for winding the completed laminate, a coater roll 18, a doctor knife 20, and a liquid tank 22 for applying a fluororesin dispersion on the film surface. Heat treatment furnace 24 for drying and curing the surface of the film coated with the fluororesin dispersion
It is composed of The heat treatment furnace 24 includes a drying chamber 26 and a heating chamber 28. The heating chamber 28 includes a hot-air oven that heats with hot air, a far-red oven that heats with far-infrared rays, and the like. Reference numeral 30 is a free roll for allowing the film to run well.

Then, in the process of running the plastic film 12 from the film feeding device 14 to the film winding device 16, after coating the fluororesin dispersion (coating liquid) with the coater roll 18, the drying chamber 2
Dry at 6. The coating / drying conditions at this time are
It is not particularly limited and may be appropriately set empirically. Specifically, for example, a clav roll # 80 is used as the coater roll 18, and the line speed is 1 m / min.
In particular, under the condition that the coater roll peripheral speed is 200 rpm, a resin layer having a thickness of 10 μm or more can be finally applied well. The drying conditions are, for example, 100 ° C. and 2
The condition of drying for a minute is set.

The fluororesin used here is not particularly limited either, but tetrafluoroethylene resin,
Vinylidene fluoride resin, vinyl fluoride resin, tetrafluoroethylene-hexanefluoropropylene resin copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether resin copolymer, ethylene-tetrafluoroethylene resin copolymer and the like are preferable, and one kind is preferable. Or two or more types may be used. Especially tetrafluoroethylene / hexafluoropropylene copolymer (FE
It is preferable to use P) as a main component, and to adjust the dispersion to have a viscosity and a concentration according to the coating method.

Here, in the production method of the present invention, it is important to set the concentration and viscosity of the fluororesin dispersion used, and the concentration exceeds 30%, preferably 3%.
With a fluorine resin dispersion of 5% or more, a resin layer of 10 μm or more can be particularly well coated.

The plastic film used in the present invention is not particularly limited, but the thermal decomposition temperature of the film is preferably 400 ° C. or higher because the curing temperature is required to be high, and the polyimide film is preferably used. It can be illustrated, for example,

[0029]

Embedded image

A polyimide film represented by the general formula shown below is preferably used. The polyimide film represented by the general formula (1) has remarkably excellent heat resistance,
It is widely known that it has long-term heat resistance, flame retardancy, chemical resistance, and further has excellent mechanical and electrical properties in a wide temperature range.

Further, in order to control the coating thickness of the resin layer, it is necessary to consider not only the concentration of the fluororesin dispersion but also the viscosity and the coating method, but the liquid viscosity depends on the coating method. It is adjusted appropriately.

Among the fluororesin dispersions that are generally commercially available, the fluororesin solid content is 3
Most of them are 0% to 60%, and the dispersion has a low viscosity of about 10 centipoise, and if it is applied as it is, the dispersion will flow when it is applied to the substrate, so that it cannot be applied well. Therefore, it is necessary to add a thickener to the dispersion in order to give the fluororesin dispersion an appropriate viscosity. As the thickener, Carbopol 934 manufactured by Goodrich was used in this example, but the thickener is not particularly limited to the above thickener.

In addition to the above-described gravure method, for example, a method such as a reverse roll, an air doctor, a blade, etc. can be used as a method for applying the adjusted fluororesin dispersion, and any method can be used. However, a coating liquid whose liquid viscosity and concentration are optimal for the coating method used is used.

After that, after the resin layer is applied and dried, the resin layer is cured in the heating chamber 28 to be hardened. The above conditions should be optimized, that is, the curing temperature and the curing time. The setting is important, and by performing the curing at a high temperature, it is possible to produce a fluororesin laminate having no problem in appearance. The heating chamber 28 may be a hot air oven or a far infrared oven. However, if the curing is performed for a long time at the thermal decomposition temperature of the fluororesin or the plastic film or higher, the deterioration of the properties due to the thermal deterioration of the respective resin, for example, the deterioration of the heat-sealing strength is concerned, so the curing temperature and the curing time. It is also important to pay attention to the upper limit of. The curing temperature and the curing time are appropriately set according to the thermal decomposition temperature of the fluororesin or the plastic film. Specifically, the atmosphere temperature in the heating chamber 28 is 450 ° C. or more in the hot air oven and far infrared. In the oven, the temperature is preferably 400 ° C or higher. The curing time is 1 to 10 minutes at the curing temperature of 400 ° C., preferably 1 to 5 minutes, more preferably 1 to 3 minutes, and 0.5 to 5 at the curing temperature of 450 ° C.
Minutes, preferably 0.5 to 3 minutes, more preferably 0.5 to
One minute. For example, when a fluororesin having a thermal decomposition temperature of 450 ° C. is laminated on one side or both sides of a plastic film having a thermal decomposition temperature of 590 ° C., the temperature is 450 ° C. for 1 to 3 minutes, and the higher temperature is 480 ° C. It is preferably 0.5 to 1 minute.

Further, by adding an organic solvent to the dispersion having the adjusted concentration, the fluororesin laminate according to the present invention can be produced without cracks. The amount of the organic solvent added is 0.01% to 80%, preferably 0.05% to 50%, and more preferably 0.1% to 35% with respect to the solid content of the fluororesin. Is preferred. Also,
The boiling point of the organic solvent is 60 ° C or higher, preferably 8
The temperature is preferably 0 ° C. or higher, more preferably 100 ° C. or higher. By using a dispersion containing such an organic solvent, a resin layer having a thickness of 10 μm or more can be finally and satisfactorily applied.

The organic solvent used in the present invention is not particularly limited, but specifically, ethanol, DMF,
Water-soluble substances such as NMP and glycerin alone or 2
Used in combination of more than one species. These boiling points are 6
0 ° C or higher, preferably 80 ° C or higher, more preferably 100
It is preferable that the temperature is not lower than ° C.

By adding these high-boiling point organic solvents, it is possible to make the evaporation components in the dispersion have a range of evaporation temperature, and as a result, cracks on the surface of the FEP layer in the dried state are generated. It is speculated that you can control a lot. Furthermore, after drying FEP
Since the generation of cracks on the surface of the layer is suppressed, there is an advantage that curing can be performed at a relatively low temperature. Note that the above effect does not appear in an organic solvent having a low boiling point.

When an organic solvent is added to the fluororesin dispersion, the curing temperature of the heating chamber 28 can be set in a wider appropriate temperature range as compared with the case where no organic solvent is added. 3 for hot air oven
The temperature is 50 ° C or higher, preferably 400 ° C or higher, and in the case of a far-infrared oven, it is 300 ° C or higher, preferably 350 ° C or higher, and more preferably 400 ° C or higher. In addition, at the same curing time as that required for curing when no organic solvent is added, 50 ° C
Can be cured at low temperatures. Therefore, curing can be performed at a lower temperature and in a similar short period of time as compared with the case where no organic solvent is added. The fluororesin laminate according to the present invention can be produced without cracks by curing under the same temperature conditions as when the organic solvent is not added. If the curing temperature is too high, a gas that is more toxic than the fluororesin may be generated, and it is desirable that the curing be performed at a low temperature in a short time.

The present invention makes it possible to manufacture a fluororesin laminate by coating, which is difficult to conceive from the conventional concept, and particularly to manufacture a fluororesin laminate having a thickness of 10 μm or more. Specifically, by optimizing the treatment conditions of the concentration management of the fluororesin dispersion, by coating the fluororesin dispersion, by performing the curing temperature at a higher temperature, or by adding an organic solvent It is possible to cure at low temperature, suppress the generation of cracks, and particularly obtain a fluororesin laminate of 10 μm or more. According to such a manufacturing method, it is possible to produce a fluororesin laminate which is free from severe cracks and does not appear to be cloudy with the naked eye. Incidentally, under the microscope observation, linear scratches are seen on the whole of the laminated body which seems to be turbid, and it is confirmed that there are severe cracks, but in the laminated body obtained by the production method of the present invention, Has almost no such scratches,
It was confirmed that there were almost no cracks even at the microscope level. Therefore, the appearance is very good and the quality such as electric insulation is also good.

As described above, according to the present invention, the thickness is 2 μm.
Or more, preferably 5 μm or more, more preferably 1
A fluorine-based resin laminate having a thickness of 0 μm or more has a remarkable effect of suppressing the occurrence of cracks, and is obtained in good appearance and quality.

Further, the present invention is manufactured by coating using a fluororesin dispersion which is cheaper than a fluororesin film, and the line speed of the coating process can be easily increased as compared with the laminating method. Therefore, it is possible to improve the manufacturing efficiency. Furthermore, by further adding an organic solvent to the concentration-adjusted fluororesin dispersion, the generation of cracks can be prevented, and the fluororesin laminate can be manufactured even at a relatively low temperature. As a result, the fluororesin laminate obtained by the production method of the present invention can be significantly reduced in cost as compared with the laminate obtained by the conventional laminating method.

Although one example of the embodiment of the method for producing a fluororesin laminate according to the present invention has been described above, the present invention is not limited to these examples. In addition to the above examples, the fluororesin dispersion is repeatedly applied and dried to apply the fluororesin to the film surface, especially 1
It may be formed to a thickness of 0 μm or more and cured and cured as described above without any problem in appearance. Specifically, apply and dry the fluororesin dispersion once,
There is a method of curing after the second coating / drying, a method of drying once after coating and curing, then a method of drying after the second coating and then curing again. When using three or more kinds of fluororesin dispersions, A combination of the above two methods is also possible. It is also possible to apply the same type of dispersion several times.

Instead of the laminate having the resin layer on one side of the film as described above, a laminate having the resin layers on both sides of the film may be manufactured. In this case, for example, the fluororesin dispersion may be applied to both sides of the film at the same time and dried, or may be applied to each side and dried, and then both sides may be simultaneously cured. Further, as described above, after obtaining a laminate having a resin layer on one surface, then, similarly forming a resin layer on the other surface, etc., the present invention is within the scope not departing from the spirit of the present invention. Based on the knowledge of the above, various improvements, changes and modifications can be made.

[0044]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. The boiling points of the organic solvents used in the examples are NMP: 202 ° C., DMF: 153 ° C., acetone: 56 ° C., methanol: 64.5 ° C., glycerin: 2
90 ° C.

[0045]

Example 1 54.0 g of pure water, Carbopol 934
Weigh 0.50 g of (Goodrich, viscosity modifier),
Stir for 15 minutes with a mixer. Next, 0.90 g of aqueous ammonia (25 to 28 wt%) was added, and the mixture was subsequently stirred with a mixer for 2 minutes. Then, 100 g of water-dispersed tetrafluoroethylene / hexafluoropropylene copolymer (FEP) (ND-1 manufactured by Daikin Co., Ltd.) was added as a fluorine-based resin dispersion and stirred for 15 minutes to obtain a resin concentration of 35% and a viscosity. A 23.0 poise fluororesin dispersion (coating liquid) was obtained. FE
The thermal decomposition temperature of P is 480 ° C.

Then, using a device as shown in FIG. 1, a 25 μm thick polyimide film (trade name Apical 25AH; bell) was prepared so that the FEP layer had a solid content of 12.5 μm. Fuchi Kagaku Kogyo Co., Ltd. (thermal decomposition temperature 580 ° C or higher) is applied to one side and dried, and then cured in a hot air oven at an atmospheric temperature of 450 ° C for 3 minutes to form a 12.5 μm thick single-sided fluororesin. A laminated body was produced. Regarding the equipment specifications and coating / drying conditions, a gravure roll No. 80 was used as the coater roll, the line speed was 1 m / min, the coater roll peripheral speed was 200 rpm, and the drying condition was 10
It was set to 0 ° C. for 2 minutes. No cracks were visually observed on the surface of the fluororesin layer of the completed laminate. The processing conditions and the presence or absence of cracks are summarized in Table 1.

[0047]

[Table 1]

[0048]

Example 2 Example 1 was repeated except that pure water was 6.0 g, Carbopol 934 (manufactured by Goodrich, viscosity adjusting agent) was 0.27 g, and ammonia water (25 to 28 wt%) was 0.48 g. Similarly, a fluororesin dispersion (coating solution) having a resin concentration of 50% and a viscosity of 50.0 poise was obtained.
Using the obtained fluororesin dispersion, a single-sided fluororesin laminate having a thickness of 12.5 μm was produced under the same conditions as in Example 1. No cracks were visually observed on the surface of the fluororesin layer of the completed laminate. The processing conditions and the presence or absence of cracks are summarized in Table 1.

[0049]

[Example 3] Using the same fluororesin dispersion (resin concentration 50%) as in Example 2, coating and drying were performed under the same conditions as in Example 1, and then at a temperature of 480 ° C in a hot air oven. Curing was performed for 0.5 minutes to prepare a 12.5 μm-thick single-sided fluororesin laminate. No cracks were visually observed on the surface of the fluororesin layer of the completed laminate. The processing conditions and the presence or absence of cracks are summarized in Table 1.

[0050]

[Example 4] The procedure of Example 1 was repeated except that the coating thickness of the fluororesin dispersion was changed to prepare a 5 μm thick single-sided fluororesin laminate. No cracks were visually observed on the surface of the fluororesin layer of the completed laminate. Table 1 shows the processing conditions and the presence or absence of cracks.
Summarized in

[0051]

Comparative Example 1 Pure water 76.7 g, Carbopol 934
(Manufactured by Goodrich Co., Ltd., viscosity modifier) was 0.62 g, and ammonia water (25 to 28 wt%) was 1.11 g, except that the resin concentration was 30% and the viscosity was 20.
A 0-poise fluororesin dispersion (coating liquid) was obtained. Using the obtained fluororesin dispersion,
A single-sided fluororesin laminate having a thickness of 12.5 μm was produced under the same conditions as in Example 1. The completed laminated body looked turbid, and the surface of the fluororesin layer had severe cracks visually recognizable. The processing conditions and the presence or absence of cracks are summarized in Table 1.

[0052]

[Comparative Example 2] 19.0 g of pure water, Carbopol 934
(Manufactured by Goodrich, viscosity modifier) was 0.20 g, and ammonia water (25 to 28 wt%) was 0.36 g, except that the resin concentration was 45% and the viscosity was 10.
A 0-poise fluororesin dispersion (coating liquid) was obtained. Using the obtained fluororesin dispersion,
After coating and drying under the same conditions as in Example 1, curing was performed in a hot air oven at an ambient temperature of 400 ° C. for 5 minutes, and 1
A single-sided fluororesin laminate having a thickness of 2.5 μm was produced. The completed laminated body looked turbid, and the surface of the fluororesin layer had severe cracks visually recognizable. The processing conditions and the presence or absence of cracks are summarized in Table 1.

[0053]

[Comparative Example 3] Using the same fluororesin dispersion (resin concentration 50%) as in Example 2, coating and drying were carried out under the same conditions as in Example 2, and then at a temperature of 400 ° C in a hot air oven. Curing was carried out for 5 minutes to prepare a 12.5 μm-thick single-sided fluororesin laminate. The completed laminated body looked turbid, and the surface of the fluororesin layer had severe cracks visually recognizable. The processing conditions and the presence or absence of cracks are summarized in Table 1.

[0054]

[Example 5] Using the same fluororesin dispersion (resin concentration 35%) as in Example 1, coating and drying were carried out under the same conditions as in Example 1, and then the atmosphere temperature was 400 ° C in a far-red oven. And cured for 5 minutes to prepare a 12.5 μm thick single-sided fluororesin laminate. No cracks were visually observed on the surface of the fluororesin layer of the completed laminate. The processing conditions and the presence or absence of cracks are summarized in Table 2.

[0055]

[Table 2]

[0056]

[Example 6] Using the same fluororesin dispersion (resin concentration 50%) as in Example 2, coating and drying were performed under the same conditions as in Example 1, and then the ambient temperature was 450 ° C in a far-red oven. Was cured for 1 minute to prepare a 12.5 μm-thick single-sided fluororesin laminate. No cracks were visually observed on the surface of the fluororesin layer of the completed laminate. The processing conditions and the presence or absence of cracks are summarized in Table 2.

[0057]

[Example 7] Using the same fluororesin dispersion (resin concentration 50%) as in Example 2, coating and drying were performed under the same conditions as in Example 1, and then the ambient temperature was 480 ° C in a far-red oven. Was cured for 0.5 minutes to prepare a 12.5 μm-thick single-sided fluororesin laminate. No cracks were visually observed on the surface of the fluororesin layer of the completed laminate. The processing conditions and the presence or absence of cracks are summarized in Table 2.

[0058]

Comparative Example 4 32.5 g of pure water, Carbopol 934
(Manufactured by Goodrich, viscosity modifier) was 0.40 g, and ammonia water (25 to 28 wt%) was 0.72 g, except that the resin concentration was 40% and the viscosity was 19.
A 0-poise fluororesin dispersion (coating liquid) was obtained. Using the obtained fluororesin dispersion,
After coating and drying under the same conditions as in Example 1, curing was performed in a far-red oven at an ambient temperature of 350 ° C. for 5 minutes, and 1
A single-sided fluororesin laminate having a thickness of 2.5 μm was produced. The completed laminated body looked turbid, and the surface of the fluororesin layer had severe cracks visually recognizable. The processing conditions and the presence or absence of cracks are summarized in Table 2.

[0059]

[Embodiment 8] 617.5 g of pure water, Carbopol 934
Weigh 5.32g (made by Goodrich, viscosity modifier),
The mixture was stirred for 30 minutes with a mixer. Next, 9.50 g of aqueous ammonia (25 to 28 wt%) was added, and the mixture was subsequently stirred for 3 minutes with a mixer. Thereafter, 1900 g of a water-dispersed tetrafluoroethylene / hexafluoropropylene copolymer (FEP) (ND-1 manufactured by Daikin) was added as a fluorine resin dispersion, and DMF was added.
Was added and stirred for 15 minutes. The organic solvent weight% to the fluorine resin solid content was 5.0%, the resin concentration was 40%,
A fluororesin dispersion (coating liquid) having a viscosity of 2 to 3 poise was obtained. The thermal decomposition temperature of FEP is 480 ° C.

Then, using a device as shown in FIG. 1, a 25 μm thick polyimide film (trade name Apical 25AH; Kanegafuchi Chemical Co., Ltd.) was used so that the FEP layer had a solid content of 15 μm. Coated on one side of Kogyo Co., Ltd. (thermal decomposition temperature of 580 ° C. or higher) and dried (100 ° C.-1 minute), and then cured in a hot air oven at an atmospheric temperature of 400 ° C. for 3 minutes, 15
A single-sided fluororesin laminate having a thickness of μm was produced. Regarding the equipment specifications and coating / drying conditions, use a gravure roll No. 80 as the coater roll and set the line speed to 1
m / min, the coater roll peripheral speed was 200 rpm, and the drying conditions were 100 ° C. and 2 minutes. No cracks were visually observed on the surface of the fluororesin layer of the completed laminate. The processing conditions and the presence or absence of cracks are summarized in Table 3.

[0061]

[Table 3]

[0062]

Example 9 The same procedure as in Example 8 was conducted except that the amount of DMF added was changed to 177.3 g, the organic solvent weight% was 17.3%, the resin concentration was 40%, and 2 to 2.
A 5 poise fluororesin dispersion (coating liquid) was obtained. Using the obtained fluororesin dispersion, a single-sided fluororesin laminate having a thickness of 15 μm was produced under the same conditions as in Example 8. No cracks were visually observed on the surface of the fluororesin layer of the completed laminate. The processing conditions and the presence or absence of cracks are summarized in Table 3.

[0063]

[Example 10] Fluorine of 2 to 3 poise with 5.0% by weight of an organic solvent based on the solid content of a fluororesin, 40% of a resin concentration, and 2 to 3 poises of fluorine, in the same manner as in Example 8 except that the amount of NMP added was 50.5 g. A resin dispersion (coating liquid) was obtained.
Using the obtained fluororesin dispersion, a single-sided fluororesin laminate having a thickness of 15 μm was produced under the same conditions as in Example 8. No cracks were visually observed on the surface of the fluororesin layer of the completed laminate. The processing conditions and the presence or absence of cracks are summarized in Table 3.

[0064]

Example 11 The same procedure as in Example 8 was conducted except that the amount of NMP added was changed to 177.3 g, the organic solvent weight% was 17.3%, the resin concentration was 40%, and 2 to 2% with respect to the solid content of the fluororesin.
A 5 poise fluororesin dispersion (coating liquid) was obtained. Using the obtained fluororesin dispersion, a single-sided fluororesin laminate having a thickness of 15 μm was produced under the same conditions as in Example 8. No cracks were visually observed on the surface of the fluororesin layer of the completed laminate. The processing conditions and the presence or absence of cracks are summarized in Table 3.

[0065]

Example 12 The same procedure as in Example 8 except that the amount of glycerin added was 50.5 g, and the amount of the organic solvent was 5.0% by weight based on the solid content of the fluororesin, the resin concentration was 40%, and the fluorine content was 2 to 3 poises. A resin dispersion (coating liquid) was obtained. Using the obtained fluororesin dispersion,
A single-sided fluororesin laminate having a thickness of 15 μm was produced under the same conditions as in Example 8. No cracks were visually observed on the surface of the fluororesin layer of the completed laminate. The processing conditions and the presence or absence of cracks are summarized in Table 3.

[0066]

Example 13 The same procedure as in Example 8 was conducted except that the amount of glycerin added was changed to 177.3 g, the organic solvent weight% was 17.3% with respect to the solid content of the fluororesin, and the resin concentration was 40%.
A 2.5-poise fluororesin dispersion (coating liquid) was obtained. Using the obtained fluororesin dispersion, a single-sided fluororesin laminate having a thickness of 15 μm was produced under the same conditions as in Example 8. No cracks were visually observed on the surface of the fluororesin layer of the completed laminate.
The processing conditions and the presence or absence of cracks are summarized in Table 3.

[0067]

Comparative Example 5 A fluororesin dispersion (coating liquid) having a resin concentration of 40% and a viscosity of 3 to 4 poises was obtained in the same manner as in Example 8 except that the organic solvent was not added. Using the obtained fluororesin dispersion, a single-sided fluororesin laminate having a thickness of 15 μm was produced under the same conditions as in Example 8. The completed laminated body looked turbid, and the surface of the fluororesin layer had severe cracks visually recognizable. The processing conditions and the presence or absence of cracks are summarized in Table 3.

[0068]

[Comparative Example 6] 60.0 g of pure water, Carbopol 934
Weigh 18.5 g (made by Goodrich, viscosity modifier),
The mixture was stirred for 30 minutes with a mixer. Then ammonia water (25
˜28 wt%) was added, and the mixture was continuously stirred for 3 minutes. Then, as a fluororesin dispersion, tetrafluoroethylene / hexafluoroethylene copolymer (FEP) dispersed in water (ND-1 manufactured by Daikin).
1000g and stirred for 30 minutes to give a resin concentration of 50%,
A fluororesin dispersion (coating liquid) having a viscosity of 60 to 70 poise was obtained. Using the obtained fluororesin dispersion, a single-sided fluororesin laminate having a thickness of 15 μm was produced under the same conditions as in Example 8. The completed laminated body looked turbid, and the surface of the fluororesin layer had severe cracks visually recognizable. The processing conditions and the presence or absence of cracks are summarized in Table 3.

[0069]

[Comparative Example 7] 767.0 g of pure water and Carbopol 934
6.2 g of (Viscosity modifier manufactured by Goodrich) was weighed and stirred with a mixer for 30 minutes. Then ammonia water (25 ~
28 wt%) was added, and the mixture was continuously stirred for 3 minutes. Then, as a fluororesin dispersion, tetrafluoroethylene / hexafluoroethylene copolymer (FEP) dispersed in water (ND-1 manufactured by Daikin).
1000g and stirred for 30 minutes, resin concentration 30%,
A fluororesin dispersion (coating liquid) having a viscosity of 10 poise was obtained. Using the obtained fluororesin dispersion, a single-sided fluororesin laminate having a thickness of 15 μm was produced under the same conditions as in Example 8. The completed laminated body looked turbid, and the surface of the fluororesin layer had severe cracks visually recognizable. The processing conditions and the presence or absence of cracks are summarized in Table 3.

[0070]

[Comparative Example 8] 440.0 g of pure water, Carbopol 934
Weigh 1.45 g (made by Goodrich, viscosity modifier),
The mixture was stirred for 30 minutes with a mixer. Then ammonia water (25
(About 28 wt%) was added and then the mixture was stirred for 3 minutes. Then, a fluororesin dispersion of tetrafluoroethylene / hexafluoroethylene copolymer (FEP) dispersed in water (ND-manufactured by Daikin).
100 g of 1) was added and stirred for 30 minutes to obtain a resin concentration of 10
%, And a viscosity of 6 to 7 poise was obtained as a fluororesin dispersion (coating liquid). Using the obtained fluororesin dispersion, a single-sided fluororesin laminate having a thickness of 15 μm was produced under the same conditions as in Example 8. The completed laminated body looked turbid, and the surface of the fluororesin layer had severe cracks visually recognizable. The processing conditions and the presence or absence of cracks are summarized in Table 3.

[0071]

Comparative Example 9 A fluororesin dispersion (coating solution) having a resin concentration of 40% and a viscosity of 3 to 4 poise was obtained in the same manner as in Example 8 except that the organic solvent was not added. Using the obtained fluororesin dispersion, a 5 μm thick single-sided fluororesin laminate was prepared under the same conditions as in Example 8.
The completed laminate looked turbid, and some visible cracks were observed on the surface of the fluororesin-based fat layer. The processing conditions and the presence or absence of cracks are summarized in Table 3.

[0072]

Example 14 The procedure of Example 8 was repeated, except that the amount of acetone added was 50.5 g, and the amount of the organic solvent was 5% by weight, the resin concentration was 40%, and the fluorine content was 2 to 2.5 poise. A resin dispersion was obtained. The obtained (coating liquid) was obtained. Using the obtained fluororesin dispersion, a 15-μm fluororesin laminate was prepared under the same conditions as in Example 8. The completed laminate looked a little cloudy, and some visible cracks were observed on the surface of the fluororesin layer. The processing conditions and the presence or absence of cracks are summarized in Table 3.

[0073]

[Example 15] The same procedure as in Example 8 except that the amount of acetone added was 177.3 g, and the organic solvent weight% was 17.3%, the resin concentration was 40%, and
A fluororesin dispersion of 2.5 poise was obtained.
The obtained (coating liquid) was obtained. Using the obtained fluororesin dispersion, a single-sided fluororesin laminate having a thickness of 15 μm was produced under the same conditions as in Example 8. The completed laminate looked a little cloudy, and some visible cracks were observed on the surface of the fluororesin layer. The processing conditions and the presence or absence of cracks are summarized in Table 3.

[0074]

[Example 16] The same procedure as in Example 8 except that the amount of methanol added was 50.5 g, and the organic solvent weight% was 5.0%, the resin concentration was 40%, and the amount of 2-2.
A 5 poise fluororesin dispersion was obtained. The obtained (coating liquid) was obtained. Using the obtained fluororesin dispersion, a single-sided fluororesin laminate having a thickness of 15 μm was produced under the same conditions as in Example 8. The completed laminate looked a little cloudy, and some visible cracks were observed on the surface of the fluororesin layer. The processing conditions and the presence or absence of cracks are summarized in Table 3.

[0075]

Example 17 The same procedure as in Example 8 was conducted except that the amount of methanol added was changed to 177.3 g, the organic solvent weight% was 17.3%, the resin concentration was 40%, and the solid content of the fluororesin was 2%.
A fluororesin dispersion of ˜2.5 poise was obtained. The obtained (coating liquid) was obtained. 15 μm under the same conditions as in Example 8 using the obtained fluororesin dispersion
A thick single-sided fluororesin laminate was prepared. The completed laminate looked a little cloudy, and some visible cracks were observed on the surface of the fluororesin layer. The processing conditions and the presence or absence of cracks are summarized in Table 3.

[0076]

[Example 18] The same procedure as in Example 8 except that the amount of DMF added was 177.3 g, and the organic solvent weight% was 17.3%, the resin concentration was 40%, and
A fluororesin dispersion of 2.5 poise was obtained.
The obtained (coating liquid) was obtained. A single-sided fluororesin laminate having a thickness of 25 μm was produced under the same conditions as in Example 8 using the obtained fluororesin dispersion. The completed laminate looked a little cloudy, and some visible cracks were observed on the surface of the fluororesin layer. The processing conditions and the presence or absence of cracks are summarized in Table 3.

[0077]

Example 19 440.0 g of pure water, Carbopol 93
1.45 g of 4 (manufactured by Goodrich, viscosity modifier) was weighed and stirred with a mixer for 30 minutes. Then 2.61 g of ammonia water (25-28 wt%) was added, and then 3
Minutes. Then, tetrafluoroethylene / hexafluoroethylene copolymer (FEP) dispersed in water as a fluororesin dispersion (N manufactured by Daikin Co., Ltd.
100 g of D-1) was added and stirred for 30 minutes, 2.7 g of DMF was added and stirred for 15 minutes, and the organic solvent weight% to the fluororesin solid content was 5.0%, the resin concentration was 10%, and the viscosity was 6 to. A 7-poise fluororesin dispersion (coating liquid) was obtained. Using the obtained fluororesin dispersion, a single-sided fluororesin laminate having a thickness of 15 μm was produced under the same conditions as in Example 8. No cracks were visually observed on the surface of the fluororesin of the completed laminate. The processing conditions and the presence or absence of cracks are summarized in Table 3.

[0078]

[Example 20] The procedure of Example 8 was repeated except that the coating thickness of the fluororesin dispersion was changed to prepare a single-sided fluororesin laminate having a thickness of 5 µm. No cracks were visually observed on the surface of the fluororesin layer of the completed laminate. The processing conditions and the presence or absence of cracks are summarized in Table 3.

[0079]

Example 21 Using a fluororesin dispersion synthesized in the same manner as in Example 8, drying conditions were set to 100 ° C. for 1 minute, and further curing was performed in a hot air oven at 450 ° C. for 3 minutes to prepare a 15 μm thick single-sided surface. A fluororesin laminate was prepared. No cracks were visually observed on the surface of the fluororesin layer of the completed laminate. The processing conditions and the presence or absence of cracks are summarized in Table 4.

[0080]

[Table 4]

[0081]

Example 22 Using a fluororesin dispersion synthesized in the same manner as in Example 9, drying conditions were set to 100 ° C. for 1 minute, and curing was further performed in a hot air oven at 450 ° C. for 3 minutes to give a 15 μm thick single-sided surface. A fluororesin laminate was prepared. No cracks were visually observed on the surface of the fluororesin layer of the completed laminate. The processing conditions and the presence or absence of cracks are summarized in Table 4.

[0082]

Twenty-third Embodiment Using a fluororesin dispersion synthesized in the same manner as in the eighth embodiment, the drying conditions are 100 ° C. and 1 minute, and further curing is performed in the far-red oven at 400 ° C. for 3 minutes to obtain a film having a thickness of 15 μm. A single-sided fluororesin laminate was prepared. No cracks were visually observed on the surface of the fluororesin layer of the completed laminate. The processing conditions and the presence or absence of cracks are summarized in Table 4.

[0083]

Example 24 Using a fluororesin dispersion synthesized in the same manner as in Example 9, drying conditions were set to 100 ° C. for 1 minute, and further curing was performed in a far-red oven at 400 ° C. for 3 minutes to obtain a film having a thickness of 15 μm. A single-sided fluororesin laminate was prepared. No cracks were visually observed on the surface of the fluororesin layer of the completed laminate. The processing conditions and the presence or absence of cracks are summarized in Table 4.

In order to obtain crack-free laminates according to Examples 1 to 7 and Comparative Examples 1 to 4, the resin concentration of the fluororesin dispersion (coating liquid) exceeds 30%, preferably 35. %, And it is important that the curing temperature is 450 ° C. or higher in the hot air oven and 400 ° C. or higher in the far-infrared oven. Also, if the curing temperature is high, there is no crack even if the curing time is short. It can be seen that a laminate is obtained. It is considered that a shorter curing time is preferable in view of the deterioration of the characteristics of the resin due to the thermal deterioration caused by the curing at a high temperature. In addition, according to Examples 8 to 20 and Comparative Examples 5 to 9, in the system in which the organic solvent is added, the addition of the organic solvent has an effect of suppressing the occurrence of cracks without performing a curing treatment at a high temperature, Further, it can be seen that the higher the boiling point of the organic solvent is, the less the occurrence of cracks occurs. Further, it is understood from Examples 21 to 24 that a fluorine-based resin laminate having no mud crack can be obtained even by adding an organic solvent and curing at a high temperature.

[0085]

INDUSTRIAL APPLICABILITY As described above, the present invention realizes production by a coating method in a method for producing a laminate having a fluororesin layer formed on one or both sides of a plastic film. Since a laminated body can be obtained by applying a cheaper fluororesin dispersion than the conventional laminating method, it is possible to manufacture at a lower cost than the conventional laminating method. Specifically, after applying and drying the concentration-adjusted fluororesin dispersion (coating liquid),
By curing at high temperature or by adding an organic solvent to the dispersion whose concentration has been adjusted, coating and drying, and then curing, a laminate excellent in appearance with almost no cracks on the surface of the fluororesin layer is obtained. The fluororesin laminate obtained by the production method of the present invention can be expected to have excellent electrical reliability when used as wire insulation.

[Brief description of the drawings]

FIG. 1 is an explanatory view showing an apparatus for carrying out a method for producing a fluororesin laminate according to the present invention.

[Explanation of symbols]

 10: Fluorine-based resin laminate manufacturing apparatus 12; Plastic film 14; Film feeding apparatus 16; Film winding apparatus 18; Coater roll 24; Heat treatment furnace 26; Drying room 28; Heating room (hot air oven or far-infrared oven)

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location B05D 7/24 302 B05D 7/24 302L B32B 27/30 B32B 27/30 D

Claims (14)

[Claims] 1. A fluororesin having improved surface properties, comprising a plastic film and a fluororesin layer formed by applying a fluororesin dispersion to one or both surfaces of the plastic film. Resin laminate. 2. A plastic film, and a fluororesin layer having a thickness of 10 μm or more formed by applying a fluororesin dispersion on one or both surfaces of the plastic film. The fluororesin laminate having the improved surface properties described in 1. 3. The main component of the fluororesin layer is tetrafluoroethylene resin, vinylidene fluoride resin, vinyl fluoride resin, tetrafluoroethylene-hexanefluoropropylene resin copolymer, tetrafluoroethylene-
1 of perfluoroalkyl vinyl ether resin copolymer and ethylene-tetrafluoroethylene resin copolymer
The fluororesin laminate having improved surface properties according to claim 1 or 2, wherein the fluororesin laminate is composed of one or more species. 4. The fluorine-based resin laminate with improved surface properties according to claim 1, wherein the plastic film has a thermal decomposition temperature of 400 ° C. or higher. 5. The plastic film is a polyimide film, as claimed in any one of claims 1 to 4.
5. A fluororesin laminate having an improved surface property according to any one of 1. 6. A fluororesin dispersion is applied to one or both sides of a plastic film and dried, and then the fluororesin is laminated by curing in a heat treatment furnace at a high ambient temperature. A method for producing a fluororesin laminate having improved surface properties. 7. A fluororesin having a thickness of 10 μm or more by coating a fluororesin dispersion on one or both sides of a plastic film and drying it, and then curing the plastic film in a heat treatment furnace at a high ambient temperature. A layer is formed, The manufacturing method of the fluororesin laminated body with the improved surface property of Claim 6 characterized by the above-mentioned. 8. The atmosphere temperature in the heat treatment furnace is preferably 450 ° C. or higher in a hot air oven and 400 ° C. or higher in a far-red oven, according to any one of claims 6 to 7. A method for producing a fluororesin laminate having improved surface properties. 9. A fluororesin layer is formed by applying a fluororesin dispersion containing an organic solvent to one or both sides of a plastic film, drying it, and then curing it in a heat treatment furnace. A method for producing a fluororesin laminate having improved surface properties as described in 1. 10. A fluororesin dispersion containing an organic solvent added to one or both sides of a plastic film, dried and then cured in a heat treatment furnace to form a fluororesin layer having a thickness of 10 μm or more. The method for producing a fluororesin laminate having improved surface properties according to claim 9, wherein 11. The amount of the organic solvent added to the dispersion is 0.01% to 80% based on the total solid content of the fluorinated resin.
%, And the method for producing a fluororesin laminate having improved surface properties according to claim 9 or 10. 12. The method for producing a fluororesin laminate having improved surface properties according to claim 9, wherein the organic solvent has a boiling point of 60 ° C. or higher. 13. The atmosphere temperature in the heat treatment furnace is
350 ° C or higher in hot air oven, 30 in far-red oven
It is 0 degreeC or more, The claim 9 or claim 1 characterized by the above-mentioned.
2. The method for producing a fluororesin laminate having an improved surface property according to any one of 2 above. 14. The method for producing a fluororesin laminate having improved surface properties according to claim 6, wherein the concentration of the fluororesin dispersion is 30% or more. Method.