AMORPHOUS FLUORINE-CONTAINING RESIN COMPOSITION AND A MANUFACTURING METHOD OF THIN FILMS

Abstract

[Object of this Invention] To provide the amorphous fluorine-containing resin composition that has superior film-forming ability, and has a small impact on the global environment due to its very small global warming potential, and can fully satisfy the requirement from the perspective of the environmental protection of the earth; and to provide the article that contains the coating that is formed from the thin films that are made from this amorphous fluorine-containing resin. composition.

Claims

1. An amorphous fluorine-containing resin composition comprising amorphous fluorine-containing resin dissolved in alkoxy perfluoroalkene, wherein the number of carbon atoms in the perfluoroalkene group of said alkoxy perfluoroalkene is from 5-8, and wherein said amorphous fluorine-containing resin is at least one resin selected from the group consisting of copolymer of tetrafluoroethylene and perfluoro(dimethyl dioxole), and copolymer of tetrafluoroethylene and perfluoro(butenyl vinyl ether).

2. (canceled)

3. (canceled)

4. The amorphous fluorine-containing resin composition as described in claim 1, wherein said alkoxy perfluoroalkene is methoxy perfluoroalkene.

5. The amorphous fluorine-containing resin composition as described in claim 4, wherein methoxy perfluoroalkene is methoxy perfluoroheptene.

6. The amorphous fluorine resin composition as described in claim 1, wherein the heat of fusion of the amorphous fluorine-containing resin is less than 3 J/g when measured at a heating rate of 10 C./min by a differential scanning calorimetry.

7. (canceled)

8. The amorphous fluorine-containing resin composition as described in claim 1, wherein the amorphous fluorine-containing resin is 0.01-10 wt % of the composition.

9. A method of forming a thin films of amorphous fluorine-containing resin on a base material, comprising applying to said base material an amorphous fluorine-containing resin composition of claim 1 and drying the coated based material, thereby forming a thin film of said amorphous fluorine-containing resin on said base material.

10. An article that contains a coating that is formed from the composition as described in claim 1.

Description

EMBODIMENTS

[0066] In the following paragraphs, the embodiments are given to further explain this invention in detail, but this invention is not limited to these embodiments.

[0067] The test of the physical properties in this invention was carried out by the following methods.

(1) Solubility

[0068] 19.8 g fluorine-containing solvent and 0.2 g fluorine-containing resin were placed in the sample tube (50 mL), by an ultrasonic treatment over a period of about 180 minutes at 50 C., based on the combined weight of the resin and the solvent, 1 wt % composition was created. After the treatment, the composition was left standing for 10 minutes at 50 C., and then the state of the obtained composition was visually observed.

[0069] The state in the sample tube after the ultrasonic treatment was evaluated in accordance with the following criteria.

[0070] Soluble: cloudiness and precipitation cannot be observed

[0071] Insoluble: cloudiness and precipitation at the bottom can be observed

(2) Film-Forming Ability

[0072] On one side of the glass plate in the size of 76 mm26 mm, 2 mL solution of the fluorine-containing resin was applied, after any excess solution was removed by tilting the glass plate at 90, the plate was dried for 3 hours at 60 C., and then the state of the obtained coating film was visually observed.

[0073] The state of the coating film after drying was evaluated in accordance with the following criteria.

[0074] : it was a good coating film

[0075] X: unevenness was observed

[0076] The Table 1 shows the global warming potential and the boiling point of the fluorinated solvent that is conventionally used and the amorphous fluorine-containing resin composition of this invention. The value of the conventional fluorinated solvent was transcribed from the report that was published, while the value of the solvent of this invention was the value calculated by the applicant for methoxy perfluoroheptane, which is described in the following Embodiment 1. In addition, the (Global Warming Potential GWP) is based on the carbon dioxide, and refers to a number that indicates how much potential of global warming other greenhouse gas has; and GWP is an estimated value of the ratio of the integrated value (that is to say, the impact on global warming) of the radiation energy that is applied to the earth in a given period of time to O.sub.2 at the time when the greenhouse gas in the unit mass is released into the atmosphere.

TABLE-US-00001 TABLE 1 Global Warming Potential Fluorine-containing solvent Global Warming Potential Boiling point Methoxy perfluoroheptene <10 (Note 2) 110 C. 1,1,1,2,3,4,5,5,5- 1,640 (Note 1) 55 C. decafluoropentane Methoxy perfluorohexane 200 (Note 3) 98 C. F(CF.sub.2).sub.6OCH.sub.3 (Note 1) 2007 Fourth Assessment Report from the Intergovernmental Panel on Climate Change (Abbreviated: IPCC) (Note 2) Calculated by the applicant (Note 3) From Table 2 of Patent Application Publication No. 2010-164043

Preparation Example 1

Preparation of the TFE/PEVE Copolymer (the Content of PEVE is 56 wt %)

[0077] In a one gallon (3.8 L) reactor, 2400 mL deionized water, the surfactant, and the polymerization initiator was used, 323 g PEVE was supplied, by the reaction with TFE, the dispersion solution of which the content of solid materials was 5 wt % was obtained. The generated copolymer was washed clean using the deionized water, and then dried for 1.5 hours at 150 C. The composition of the generated copolymer that was measured by 19 F-nuclear magnetic resonance (NMR) spectrum analysis was TFE/PEVE =44/56 by weight. The melting point of this TFE/PEVE copolymer was not detected by DSC, and the glass transition temperature was 20 C.

Embodiment 1

[0078] 19.8 g methoxy perfluoroheptene, 0.2 g TFE/PEVE copolymer (the content of PEVE was 56 wt %) as the fluorine-containing polymer were placed in the sample tube (50 mL), by an ultrasonic treatment over a period of about 180 minutes at 50 C., based on the combined weight of the resin and the solvent, 1 wt % composition was created. The film-manufacturing ability of the obtained composition was tested. The results are shown in Table 2. It is understood that the fluorine-containing polymer was dissolved to form the solution.

[0079] The methoxy perfluoroheptene that was used was the mixture of the isomers, the constitution of the mixture of the isomers shown in paragraph [0016] was 49% isomer (3), 20% (4), 20% (7), 6% (6), and the remaining percentage for other isomers.

Embodiment 2

[0080] Teflon (registered trademark) AF 1600 as the fluorine-containing polymer was used, and the same procedures as Embodiment 1 were conducted. The results are shown in Table 2.

Embodiment 3

[0081] Teflon (registered trademark) AF 2400 as the fluorine-containing polymer was used, and the same procedures as in Embodiment 1 were conducted. The results are shown in Table 2.

Embodiment 4

[0082] 19.8 g methoxy perfluoroheptene that was used in Embodiment 1, 0.1 g TFE/PEVE copolymer (the content of PEVE is 56 wt %) as the fluorine-containing polymer, and 0.1 g Teflon (registered trademark) AF 1600 were placed in the sample tube (50 mL), by the ultrasonic treatment over a period of about 180 minutes at 50 C., based on the combined weight of the resin and the solvent, 1 wt % composition was created. The film-forming ability of the obtained composition was tested. The results are shown in Table 2. It is understood that the fluorine-containing polymer was dissolved to form the solution.

Embodiment 5

[0083] The TFE/PEVE copolymer as fluorine-containing polymer (the content of PEVE is 56 wt %) as the fluorine-containing polymer and Teflon (registered trademark) AF 2400 were used, and the same procedures as Embodiment 4 were conducted. The results are shown in Table 2.

Comparative Example 1

[0084] 1,1,1,2,3,4,5,5,5-Decafluoropentane as the solvent (manufactured by Dupont-Mitsui Fluorochemicals Co., Ltd., Vertrel (registered trademark) XF) was used, and the same procedures as Embodiment 1 were conducted. The results are shown in Table 2.

Comparative Example 2

[0085] 1,1,1,2,3,4,5,5,5-Decafluoropentane as the solvent (manufactured by Dupont-Mitsui Fluorochemicals Co., Ltd., Vertrel (registered trademark) XF) was used, and the same procedures as Embodiment 2 were conducted. The results are shown in Table 2.

Comparative Example 3

[0086] Nonafluorobutyl methyl ether as the solvent (manufactured by 3M Company, Novec (registered trademark) HFE-7100) was used, and the same procedures as Embodiment 2 were conducted. The results are shown in Table 2.

TABLE-US-00002 TABLE 2 comparison of the solubility of the amorphous fluorine-containing resin composition Solvent Polymer Solubility Embodiment 1 Methoxy TFE/PEVE Soluble perfluoroheptene Embodiment 2 Methoxy Teflon AF 1600 Soluble perfluoroheptene Embodiment 3 Methoxy Teflon AF 2400 Soluble perfluoroheptene Embodiment 4 Methoxy TFE/PEVE, and Soluble perfluoroheptene Teflon AF 1600 Embodiment 5 Methoxy TFE/PEVE, and Soluble perfluoroheptene Teflon AF 2400 Comparative 1,1,1,2,2,3,4,5,5,5- TFE/PEVE Insoluble Example 1 decafluoropentane Comparative 1,1,1,2,2,3,4,5,5,5- Teflon AF 1600 Insoluble Example 2 decafluoropentane Comparative Nonafluorobutyl Teflon AF 1600 Insoluble Example 3 methyl ether

Embodiment 6-10

Test of the Film-Forming Ability

[0087] It is possible to form the uniform thin film without any pinholes by the method wherein the composition that was obtained in accordance with Embodiment 1-5 was applied on the glass plate, and then dried for 3 hours at 60 C. The state of the obtained coating film was visually observed. The results are shown in Table 3.

[0088] The state of the coating film after drying was evaluated in accordance with the following standard.

[0089] : it was a good coating film

[0090] X: unevenness was observed

Embodiment 11

[0091] 19.0 g methoxy perfluoroheptene and 1.0 g Teflon (registered trademark) AF 2400 as the fluorine-containing polymer were placed in the sample tube (50 mL), by the ultrasonic treatment over a period of about 180 minutes at 50 C., based on the combined weight of the resin and the solvent, 5 wt % solution was created. This solution was applied on the glass plate, and then dried for 3 hours at 100 C. The state of the obtained coating film was visually observed. The results are shown in Table 3.

Comparative Example 6-8

[0092] The dispersion solution that was obtained in accordance with Comparative Example 1-3 was applied on the glass plate, and then dried for 3 hours at 60 C. to form the thin films. The pinholes were observed in the obtained coating film. The results are shown in Table 3.

TABLE-US-00003 TABLE 3 comparison of the film-forming ability of the amorphous fluorine-containing resin composition Film Film- thick- forming ness Solvent Polymer ability (m) Embodiment 6 Methoxy TFE/PEVE 2.0 perfluoroheptene Embodiment 7 Methoxy Teflon 5.0 perfluoroheptene AF 1600 Embodiment 8 Methoxy Teflon 5.0 perfluoroheptene AF 2400 Embodiment 9 Methoxy TFE/PEVE, 3.5 perfluoroheptene Teflon AF 1600 Embodiment 10 Methoxy TFE/PEVE, 3.0 perfluoroheptene Teflon AF 2400 Embodiment 11 Methoxy Teflon 30.0 perfluoroheptene AF 2400 Comparative 1,1,1,2,2,3,4,5,5,5- TFE/PEVE X Example 4 decafluoropentane Comparative 1,1,1,2,2,3,4,5,5,5- Teflon X Example 5 decafluoropentane AF 1600 Comparative Nonafluorobutyl Teflon X Example 6 methyl ether AF 1600

[Applicability in the Industry]

[0093] In accordance with this invention, the amorphous fluorine-containing resin composition that has superior film-forming ability and has a small impact on the global environment is provided.

[0094] In accordance with this invention, the amorphous fluorine-containing resin composition and the manufacturing method of that thin film are provided, wherein it is possible to form the thin films of the amorphous fluorine-containing resin in a way that the thin films of the amorphous fluorine-containing resin is formed on the surface of the article without giving any adverse impact to the global warming, the used solvent is removed immediately from the surface of the thin films, and no damage is caused to the surface of the covered article by the hot air, and so on.

[0095] By the method of using the amorphous fluorine-containing resin composition of this invention to form the thin films, which will have no adverse impact on the global warming, it is possible to utilize various characteristics of the amorphous fluorine-containing resin composition to form the thin films quickly on the surface of the target article.

[0096] In accordance with this invention, the amorphous fluorine-containing resin composition that dissolves the amorphous fluorine-containing resin in alkoxy fluoroalkene is provided.