JP2914079B2 - Manufacturing method of laminate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION This invention relates to a fluorine-based resin and poly
The present invention relates to a method for producing a laminate obtained by laminating an amide resin .

[0002]

2. Description of the Related Art Since fluororesins have excellent corrosion resistance to chemicals, gasoline, etc., laminates obtained by laminating them with thermoplastic resins such as polyamide resins have been used for various purposes. . As such a laminate, for example, a two-layer automotive fuel piping hose in which a fluorine-based resin layer is formed as an inner layer that comes into direct contact with a fuel such as gasoline, and an outer layer made of a polyamide resin is formed on the outer periphery thereof. can give. In producing the laminate, a special pre-bonding treatment is usually performed before a bonding treatment with a urethane-based adhesive, an epoxy-based adhesive, or the like, which is a resin adhesive. This is because the fluororesin is difficult to adhere to, so that it is difficult to obtain a sufficient adhesive strength only by performing an adhesive treatment using the above adhesive, and it is difficult to obtain a practically usable laminate. . As a special pretreatment method for bonding, there is a method of modifying the surface of a fluororesin with a metal sodium complex solution. In this pretreatment method, a fluororesin is immersed in a metal sodium complex solution, and then pulled up.
It is a method of washing and drying. By performing this treatment, strong adhesion between the fluororesin and the thermoplastic resin can be achieved using the above-mentioned adhesive. However, the above method
Since a process such as immersion and cleaning is required, there is a disadvantage that the entire manufacturing process is long and complicated. The metal sodium complex solution is also a problem because it has a problem in safety for the human body. Furthermore, since the waste liquid generated at the time of the washing is also harmful, there is a problem that a large-scale facility for treating the waste liquid is required.

[0003]

As described above, the above-mentioned bonding pretreatment method has various problems, and is a manufacturing method combining the two processing methods of the pretreatment and the bonding treatment with an adhesive. Also, there is a problem that the manufacturing efficiency as a whole is deteriorated. In addition, because of the use of adhesive,
Problems such as safety to the human body such as environmental pollution also occur.

[0004] The present invention has been made in view of such circumstances, and provides a method of manufacturing a laminate having high productivity and capable of imparting excellent adhesive strength to the laminate without using an adhesive. Its purpose is to provide.

[0005]

In order to achieve the above object, the present invention relates to a method for producing a laminate comprising a fluororesin and a polyamide resin , wherein the surface of the fluororesin is reduced under reduced pressure. Plastic <br/> Zuma a step of roughening treated, on Kipu plasma treated fluorine-based on the surface of the resin placing the polyamide resin vulcanizing <br/> heat in the frequency range of 1~100MHz And a step of bonding using melting.

[0006]

In other words, the present inventors have conceived of applying a glow discharge plasma method as a pretreatment for bonding in order to achieve the above object, and have made a series of studies focusing on this.
As a result, when the surface of the fluorine-based resin is subjected to plasma treatment at a frequency in the range of 1 to 100 MHz under a moderately reduced pressure with a low degree of vacuum, the surface of the fluorine-based resin is roughened, and the polyamide resin which is heated and melted is heated. When the laminated body is manufactured by bonding, the polyamide resin melted by heating penetrates into the surface of the roughened fluororesin, so that a high anchoring effect is generated, and the obtained laminated body has excellent adhesive strength. I decided to become. FIG. 2 shows an electron micrograph of the fluororesin surface roughened by the plasma treatment, and FIG. 3 shows an electron micrograph of the untreated fluororesin surface. In addition, plasma treatment under mild pressure reduction and polyamide
The heating and melting treatment of the resin is a simple treatment and does not require any special equipment and equipment. Further, these two processes can be continuous processes. Thereby, excellent adhesive strength can be provided to the laminate without using an adhesive, and high productivity can be realized.

Next, the present invention will be described in detail.

In the method of manufacturing a laminate of the present invention, a plasma treatment is performed under reduced pressure using a fluorine resin and a polyamide resin .

As the above-mentioned fluororesin, copolymers of ethylene and tetrafluoroethylene (ETFE), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (CTFE), copolymers of ethylene and chlorotrifluoroethylene (ECTFE), copolymer of hexafluoropropylene and tetrafluoroethylene (FEP), fluorinated alkoxyethylene resin (PF
A), polytetrafluoroethylene (PTFE) and the like. Among them, it is preferable to use ETFE.

A filler can be added to the above-mentioned fluororesin for the purpose of improving physical properties. Such fillers include titanium oxide, barium sulfate, calcium carbonate, silica, carbon black, magnesium silicate, aluminum silicate, zinc oxide, alumina, calcium sulfate, aluminum sulfate, calcium hydroxide,
Examples include aluminum hydroxide, talc, molybdenum dioxide, whiskers, short fibers, graphite, metal powder, silica sand, pumice powder, slate powder, mica powder, asbestos, glass spheres and the like. The mixing ratio of this filler is usually 100
It is set in the range of 0 to 30 parts by weight (hereinafter abbreviated as "part").

As the polyamide resin , it is preferable to use nylon 6, nylon 66, nylon 11, nylon 12, etc., which are excellent in properties such as abrasion resistance .

A plasticizer may be added to the polyamide resin in order to improve processing characteristics and lower the melting temperature. Examples of the plasticizer include sulfonamides and oxybenzoic esters. The mixing ratio of this plasticizer is usually 0 to 20 with respect to 100 parts of the polyamide resin.
Set to the range of the part. Further, a filler used for a fluorine-based resin can be blended.

[0013] The plasma treatment under the reduced pressure is 0.1 to 1
This is a process using a high-frequency power supply in an atmosphere of 0 Torr. The method for producing the laminate of the present invention using the above-mentioned fluorine-based resin and polyamide resin is performed, for example, as follows. That is, first, as shown in FIG. 1, the film-like fluororesin 10 is placed in the plasma processing chamber 7. Then, 1 × 10 ⁻⁵ to 1
After the pressure was reduced to a range of × 10 ^-2 Torr, a plasma processing gas was introduced to reduce the internal pressure of the plasma processing chamber 7 to 0.1.
-10 Torr, preferably 0.1-1 Torr
Set to the range of r. The gas, Ar commonly used in the plasma treatment, it is possible to use a gas such as CF _4, it is preferable to use a mixed gas of a nitrogen-containing gas or N ₂ and H _2, such as N ₂ . When plasma processing a surface of a fluorine-based resin using this gas, now nitrogen atom is introduced into the processing surface, polyamide resins
This is because the adhesiveness with the resin is remarkably excellent. Then, a high-frequency power supply 12 is applied to the electrodes 8 and 9 at a frequency in the range of 1 to 100 MHz, and a glow is applied between the electrodes 8 and 9 at an output of 10 to 300 W, preferably 50 to 200 W. The plasma processing is performed by generating the discharge. The treatment time is appropriately determined depending on the type or size of the fluororesin, etc.
It is set in the range of 180 to 180 seconds, preferably in the range of 5 to 60 seconds. On the other hand, a film-like polyamide resin is prepared, and one surface thereof is heated and melted. The conditions for the heating and melting are appropriately determined depending on the melting point of the polyamide resin and the like. Then, the plasma-treated fluororesin and the heat-melted polyamide resin are brought into contact with each other at a pressure of 0.1 to 30 kgf / c in a state where the treated surfaces are in contact with each other.
By cooling to room temperature while pressing with a press under the conditions of m ² and a time of 0.5 to 10 minutes, a laminate made of a fluorine-based resin and a polyamide resin can be produced. The bonding portion of the thus obtained laminate is
Since the molten polyamide resin has penetrated into the fluororesin surface roughened by the plasma treatment, a high anchoring effect comes to occur, and the obtained laminate has excellent adhesive strength. Become. In FIG. 1, 1 and 2 indicate gas cylinders, 3, 4 and 13 indicate valves, 5 indicates a variable valve, 6 indicates a pressure gauge, and 11 indicates a matching box.

[0014] The plasma treatment and the heating and melting treatment are as follows.
By performing the following, continuous processing can be performed. That is, first, after the plasma treatment of the fluororesin surface, the polyamide resin is placed on the surface and melted by heating, immediately pressed under the above conditions, and then cooled to room temperature. In this way, it is possible to continuously manufacture a laminate.

Although the above-described manufacturing method has been described by taking a method of manufacturing a sheet-like laminate as an example, the present invention is not limited to this, and other laminates such as a hose-like laminate may be applied to the surface of a fluororesin. After plasma treatment, a poly
The present invention can be applied by continuously extruding an amide resin .

[0016]

As described above, the present invention provides a plasma treatment at a specific frequency on the surface of a fluororesin under reduced pressure,
A polyamide resin is arranged on this surface, and the polyamide resin is bonded by utilizing the heat melting of the polyamide resin . As a result, the surface of the fluororesin roughened by the plasma treatment was heated and melted.
The polyamide resin penetrates and adheres, and a high adhesion state can be obtained by the anchoring effect.
In addition, since no adhesive is used and no metal sodium complex solution is required, there is no problem in safety, and special equipment such as waste liquid treatment is not required. Therefore, it is possible to keep the equipment cost low. In addition, the plasma treatment and the heat melting treatment used in the present invention are simple and can be performed continuously, so that the production efficiency of the laminate can be improved. Therefore, if the present invention is applied to, for example, a method of manufacturing a hose for an automobile fuel pipe having a laminated structure, a hose having excellent adhesive strength and corrosion resistance can be provided at a low price.

Next, examples will be described together with comparative examples.

[0018]

Examples 1 and 2 A sheet-like laminate made of ETFE and nylon 12 was prepared according to the above-mentioned method.
That is, first, as shown in FIG. 1, an ETFE film having a thickness of 300 μm was placed in the plasma processing chamber 7. Then, after reducing the pressure to 10 ^-2 Torr by the vacuum pump 14, the first embodiment introduces N ₂ gas, and the second embodiment introduces a mixed gas of N ₂ and H ₂ to reduce the internal pressure of the plasma processing chamber 7. ,
It was set to 0.5 Torr. And the frequency 13.56
Glow discharge plasma was generated under the conditions of MHz and an output of 100 W, and plasma treatment was performed for 5 seconds. On the other hand, thickness 2
mm nylon film 12 was prepared.
It was heated and melted at 45 ° C. Next, the above-mentioned plasma-treated ETFE and the heat-melted nylon 12 were placed in contact with each other by 2 kg in a state where the treated surfaces were in contact with each other.
After pressing with a press machine under conditions of f / cm ² and 3 minutes, the resultant was cooled to room temperature to produce a desired sheet-like laminate.

[0019]

Comparative Example No plasma treatment was performed. Other than that,
The same operation as in Examples 1 and 2 was performed to produce a sheet-like laminate.

The sheet-like laminates of Examples 1 and 2 and Comparative Example thus obtained were subjected to a peeling test, a gasoline immersion test and a heat aging test by the following methods. The results are shown in Table 1 below.

[Peeling Test] A 90 ° peel test was performed. That is, as shown in FIG. 4, the peeled end of the partially peeled ETFE film 10 is perpendicularly (90 °) to the nylon 12 layer 15 using a strograph (manufactured by Toyo Seiki Co., Ltd.)
The film was pulled at a peel speed of 50 mm / min (in the direction of arrow A), and the peel strength was measured.

[Gasoline immersion test] The sheet laminate subjected to the above-mentioned peel test was immersed in gasoline at a temperature of 40 ° C for 168 hours, and then subjected to a 90 ° peel test again by the above-mentioned measuring method.

[Heat Aging Test] The sheet laminate subjected to the above-mentioned peel test was heated at 125 ° C. for 168 hours, and again subjected to the 90 ° peel test by the above-mentioned measuring method.

[0024]

[Table 1]

From the above Table 1, it can be seen that the sheet-like laminates of Examples 1 and 2 have high adhesive strength, and the peel strength after gasoline immersion and heat aging is almost the same as the initial peel strength. It turns out that there is no. In the measurement of the peel strength, the adhesive portion was not broken, and the ETFE film was broken and cut. In contrast, the comparative example was not bonded.

[Brief description of the drawings]

FIG. 1 is a configuration diagram of a plasma processing apparatus used in the present invention.

FIG. 2 is an electron micrograph showing a crystal structure of a fluorine-based resin surface subjected to the plasma treatment of the present invention.

FIG. 3 is an electron micrograph showing a crystal structure of an untreated fluororesin surface.

FIG. 4 is an explanatory diagram showing a method for measuring peel strength.

Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // B29K 27:12 77:00 B29L 9:00 23:00 C08L 27:12 (72) Inventor Eiichi Oumi Komaki City, Aichi Prefecture Gezu 3600 Tokai Rubber Industries Co., Ltd. (56) References JP-A-3-114829 (JP, A) JP-A-5-245989 (JP, A) JP-A-61-141532 (JP, A) JP JP-A-2-127442 (JP, A) JP-A-59-53542 (JP, A) JP-A-1-304130 (JP, A) JP-A-4-145139 (JP, A) JP-A-5-318553 (JP , A) Japanese Patent Publication No. 2-54848 (JP, B2) (58) Fields investigated (Int. Cl. ⁶ , DB name) B29C 65/02-65/74 B29C 47/02-47/04 B32B 27/00 -27/34 B32B 31/00-31/30 C08J 5/12 CEW C08J 7/00 306

Claims (2)

(57) [Claims] 1. A method for producing a laminate comprising a fluororesin and a polyamide resin laminated, wherein the surface of the fluororesin is subjected to plasma treatment under reduced pressure at a frequency in the range of 1 to 100 MHz. preparation of the laminate to the steps of to roughened, characterized in that a step of adhering by use of the heat-melted placing the polyamide resin on the surface of the upper Kipu plasma treated fluororesin . 2. A plasma processing, preparation of the laminate according to claim 1, wherein the plasma treatment is performed under a nitrogen-containing gas atmosphere.