JPH078555B2 - Fluororesin composite - Google Patents

Description

TECHNICAL FIELD The present invention relates to a fluororesin composite having many functionalities.

[Conventional technology]

Fluorocarbon resin has excellent properties such as non-adhesiveness, heat resistance, chemical resistance, and weather resistance. However, since fluorine resin is chemically stable, it is difficult to combine it with other materials and its application is limited. Therefore, a method for compounding another material with a fluorine resin material to impart its function has been studied. As a method for imparting another function to the fluorine resin material, an alkali metal treatment method, a sputtering treatment method, a radiation graft copolymerization method and the like are known.

[Problems to be solved by the invention]

However, the above method has various problems.
The above-mentioned alkali metal treatment method involves dangerous work,
Moreover, there is a possibility of fire. Further, the above-mentioned sputtering treatment method has a problem that it requires a lot of investment for equipment and the like, resulting in high cost, and further, since the sputtering is performed in a vacuum atmosphere, continuous treatment is difficult. Further, the above radiation graft copolymerization method is not so effective as a method for compounding other materials because the fluorine resin has a drawback that radiation resistance is poor, and it is not suitable for equipment. Since a lot of investment is required, there is a problem that the cost becomes high. Further, as a method of compounding another material with a fluororesin material, a method has been proposed in which an organic compound is applied to a fluororesin film, discharge treatment is performed, and then a polymer film is laminated (Japanese Patent Publication No. 47-18440). issue). However, this method is one in which an organic compound is simply applied on the surface of a fluorine resin and subjected to discharge treatment, and the applied organic compound remains liquid after the discharge treatment, and this is dried to form a polymer. The film is laminated. For this reason, the adhesive force between the fluororesin film and the polymer film is not sufficient and is not satisfactory.

The present invention has been made in view of such circumstances, and has other functions (hydrophilicity, adhesiveness) that are safe to manufacture, can be continuously manufactured, are inexpensive, and have a simple manufacturing facility. The purpose is to provide the provided fluorine resin composite.

[Means for solving problems]

In order to achieve the above object, the fluororesin composite of the present invention comprises a surface layer of a fluororesin material obtained by polymerizing a basic monomer comprising at least one of dialkylaminoalkylacrylamide and dialkylaminoalkylmethacrylamide. Take the configuration.

[Action]

That is, the present inventors have conducted research on the development of a compounding method for a fluorine resin material from the viewpoints different from the above methods, and as a result, polymerize a specific basic monomer on the surface layer of the fluorine resin material. Then, they found that the compounding could be realized, and reached the present invention. As a result, the surface of the fluorine resin material is improved in hydrophilicity, and the polymerized specific basic monomer acts as an adhesive, and it is possible to use this to bond other materials. The fluororesin composite of the present invention can be obtained by using a fluororesin material and a specific basic monomer.

The fluorine resin of the fluorine resin material is not particularly limited as long as it is a polymer containing fluorine atoms, and examples thereof include polyvinyl fluoride (PVF), polyvinylidene fluoride (PVdF), and polyvinyl fluoride. Chlortrifluoroethylene (PCTFE), Polytetrafluoroethylene (PTF)
E), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), ethylene-tetrafluoroethylene copolymer (ETFE), ethylene-chlorotrifluoroethylene Copolymer (ECTF
E) and so on.

As the specific basic monomer, a dialkylaminoalkylacrylamide represented by dimethylaminopropylacrylamide and a dialkylaminoalkylmethacrylamide represented by dimethylaminopropylmethacrylamide are used. By forming a polymerized layer using these specific basic monomers, it becomes possible to impart functions such as hydrophilicity and adhesiveness to the fluorine resin surface, which is a feature of the present invention. . These basic monomers are used alone or in combination.

The ratio of the specific basic monomer used is 10% for fluorine resin.
It is preferable to set it in the range of 0.01 to 50 parts with respect to 0 parts by weight (hereinafter abbreviated as “part”).

The fluorine resin composite of the present invention is produced using the above-mentioned raw materials, for example, as follows. That is, the specific basic monomer is diluted as it is or with a solvent, or another polymer is dissolved for the purpose of increasing the viscosity to prepare a basic monomer solution. In this case, you may mix | blend monomers other than the said specific basic monomer as needed.
Next, the above basic monomer solution is treated with a fluorine resin material,
For example, a fluorine resin film, a fluorine resin sheet, or the surface of a molded article is coated and polymerized. Examples of the polymerization method include a method in which a photosensitizer is added to the above solution and ultraviolet irradiation is performed, and a low energy electron beam that does not reach the fluorine resin is irradiated into the solution. However, since the method of irradiating with the radiation of (1) causes a heavy burden of capital investment and the like, the polymerization method of (3) is practical.

The polymerization mechanism of the basic monomer to the fluorine resin material is not graft copolymerization because of the following (a) and (b), but the fluorine resin and the basic monomer (amine).
It is presumed that the adhesive function is imparted by the ionic bond.

The fluorine resin (a) has excellent resistance to ultraviolet rays, and thus radicals are less likely to be generated by irradiation with ultraviolet rays.

(B) The basic monomer polymerized layer of the fluororesin composite of the present invention swells when immersed in hot water at a temperature of 90 ° C. for 24 hours, peels off when rubbed with a brush, and the exposed fluororesin surface repels water. . In the case of graft copolymerization, the phenomenon of repelling water does not occur.

The fluororesin composite thus obtained is one in which a specific basic monomer polymerization layer is formed on the surface of the fluororesin material, and the polymerization layer makes the surface of the fluororesin material hydrophilic. Has been modified to. Moreover, it is possible to bond other materials by using the specific basic monomer polymerized layer as an adhesive layer.

〔The invention's effect〕

As described above, since the fluororesin composite of the present invention is formed by polymerizing the specific basic monomer on the surface of the fluororesin material, the surface of the composite mainly composed of the fluororesin material is hydrophilic. It is becoming more adhesive. Therefore, the above-mentioned specific basic monomer polymerized layer can be used as an adhesive layer to firmly bond other materials, whereby the adhesiveness, conductivity, hydrophilicity, antibacterial property of other materials, Many properties such as wear resistance can be self-made. In addition, just by polymerizing a specific basic monomer on the surface of the fluororesin material, the fluorine-based acidic decomposition gas generated by thermal decomposition during the molding or use of the fluororesin composite does not cause the basic monomer monomer to decompose. It has the effect of being captured as a united body. Therefore, when the fluorine resin composite of the present invention is used for a printed circuit board or the like, it is very useful because it can prevent the corrosion of the conductor.

Next, examples will be described together with comparative examples.

[Example 1] A PFA film having a thickness of 80 µm was coated with a mixed solution of 100 parts of dimethylaminopropylacrylamide and 1.5 parts of benzophenone to a thickness of 50 µm, and a 2 KW high pressure mercury lamp was used, and the distance between the solution coating surface and the high pressure mercury lamp was 20 cm. Then, irradiation was performed for 10 minutes to form a polymerized layer on the surface of the PFA film. Next, a 50 μm thick ethylene-ethyl acrylate copolymer (EEA) (manufactured by Nippon Unicar Co., Ltd., MB-830) was pasted through the above-mentioned polymerized layer, and was pressed through a heat roll having a surface temperature of 100 ° C. to form a three-layer structure. An adhesive sheet of was obtained. This is further 50μ thick
Surface temperature of 1 obtained with copper foil and EEA
A printed circuit board was prepared by passing it between hot rolls at 00 ° C. When the adhesive force between PFA and EEA of this printed circuit board was measured, it was 2.4 Kg / cm and had sufficient adhesive force. Further, it is understood that the PFA hydrophilic film was obtained because the basic monomer polymerized layer was easily wet with water.

Example 2 A 50 μm thick FEP film was used in place of the PFA film. A FEP film was obtained in the same manner as in Example 1 except for the above. In the obtained FEP film, the basic monomer polymerized layer was sufficiently adhered to the FEP film, and the polymerized layer was easily wet with water. Therefore, it can be seen that the FEP hydrophilic film was obtained.

Example 3 Instead of the PFA film, an ETFE film having a thickness of 80 μm was used. A hydrophilic film of ETFE was obtained in the same manner as in Example 1 except for the above. In the obtained hydrophilic film of ETFE, the basic monomer polymerized layer was sufficiently adhered to the ETFE film, and the polymerized layer was easily wet with water. Therefore, it can be seen that the hydrophilic film of ETFE was obtained.

[Comparative example]

A solution was prepared by dissolving 2 parts of benzoyl peroxide in 100 parts of ethyl acrylate. This is a 100 μm thick P
A CTFE film was coated to a thickness of 10 μm, the coated surface was covered with a polyimide film from above, and heated at 180 ° C. for 30 minutes for polymerization. Next, the polyimide film was removed. Then, the film having the polymer layer formed thereon has a thickness of 50 μm.
m ethylene-ethyl acrylate copolymer film (EEA) (manufactured by Nippon Unicar Co., Ltd., MB-830) was pasted together and pressed through a hot roll having a surface temperature of 100 ° C. to obtain an adhesive sheet having a three-layer structure. This is further processed with a copper foil with a thickness of 50 μm and
A printed circuit board was prepared by passing it together with EEA through hot rolls with a surface temperature of 100 ° C. When the adhesive strength between PCTFE and EEA of this printed circuit board was measured in the same manner as in Example 1, the adhesive strength between PCTFE and EEA of the printed circuit board was little.
It was only 5g / cm.

Using the product of Example 1 and the product of Comparative Example obtained as described above, a corrosion test of copper foil was performed. When the product of Example 1 and the product of Comparative Example were heated at 80 ° C. for 200 hours, a patina portion was generated in the copper foil part of the product of Comparative Example, but no change was observed in the product of Example 1 and the product of the metal such as copper foil It was also found that it is effective in preventing corrosion.

Claims (1)

[Claims] 1. A fluororesin composite comprising a surface layer of a fluororesin material obtained by polymerizing a basic monomer comprising at least one of dialkylaminoalkylacrylamide and dialkylaminoalkylmethacrylamide.