FLUORINE-CONTAINING COMPOSITION AND PRODUCTION METHOD THEREFOR

Abstract

A primary object of the present disclosure is to provide: a fluoropolymer composition that has a low refraction index and that comprises a structural unit having a fluorine-containing aliphatic ring, the fluorine-containing aliphatic ring having one, two, or three ethereal oxygen atoms as ring-constituting atoms; a production method therefor; and the like. The present disclosure relates to a fluorine-containing composition comprising two or more fluorine-containing polymers (A), each containing as a main component a structural unit having a fluorine-containing aliphatic ring, the fluorine-containing aliphatic ring having one, two, or three ethereal oxygen atoms as ring-constituting atoms; and the like.

Claims

1. A fluorine-containing composition comprising two or more fluorine-containing polymers (A), the two or more fluorine-containing polymers (A) each containing as a main component a structural unit having a fluorine-containing aliphatic ring, the fluorine-containing aliphatic ring having one, two, or three ethereal oxygen atoms as ring-constituting atoms.

2. The fluorine-containing composition according to claim 1, wherein the composition has a refractive index that is less than the sum of values calculated by multiplying individual refractive indices of the fluorine-containing polymers (A) in the composition by individual mass ratios of the fluorine-containing polymers (A) in the composition to the total mass of the fluorine-containing polymers (A) in the composition.

3. The fluorine-containing composition according to claim 1, wherein the composition has a refractive index that is at least 0.005 less than the largest refractive index among the individual refractive indices of the fluorine-containing polymers (A) in the composition.

4. The fluorine-containing composition according to claim 1, wherein the composition has a haze value of 90 or less.

5. (canceled)

6. The fluorine-containing composition according to claim 1, wherein the fluorine-containing polymers (A) contained in the composition are two or more members selected from the group consisting of fluorine-containing polymers (A1) containing as a main component a structural unit represented by formula (A1): ##STR00032## wherein n and m are each independently 0 or 1, Y is an oxygen atom or CF.sub.2, and R.sup.1 to R.sup.4 are each independently a fluorine atom, a C.sub.1-C.sub.5 perfluoroalkyl group, or a C.sub.1-C.sub.5 perfluoroalkoxy group and fluorine-containing polymers (A2) containing as a main component a structural unit represented by formula (A2): ##STR00033## wherein R.sup.5 to R.sup.8 each represent a fluorine atom, a C.sub.1-C.sub.5 perfluoroalkyl group, or a C.sub.1-C.sub.5 perfluoroalkoxy group.

7. The fluorine-containing composition according to claim 6, wherein the fluorine-containing polymers (A1) are fluorine-containing polymers (A1) containing as a main component a structural unit represented by formula (A1): ##STR00034## wherein R.sup.1 to R.sup.4 each independently represent a fluorine atom, a C.sub.1-C.sub.5 perfluoroalkyl group, or a C.sub.1-C.sub.5 perfluoroalkoxy group.

8. The fluorine-containing composition according to claim 6, wherein the fluorine-containing polymers (A) in the composition are two or more members selected from the fluorine-containing polymers (A1).

9. The fluorine-containing composition according to claim 6, wherein the fluorine-containing polymers (A) in the composition are two or more members selected from the fluorine-containing polymers (A2).

10. The fluorine-containing composition according to claim 6, wherein the fluorine-containing polymers (A) contained in the composition are at least one member selected from the fluorine-containing polymers (A1) and at least one member selected from the fluorine-containing polymers (A2).

11. The fluorine-containing composition according to claim 6, wherein the fluorine-containing polymers (A1) are at least one member selected from the group consisting of fluorine-containing polymers (A1-1) containing as a main component a structural unit represented by formula (A1-1): ##STR00035## and fluorine-containing polymers (A1-2) containing as a main component a structural unit represented by formula (A1-2): ##STR00036##

12. The fluorine-containing composition according to claim 6, wherein in the fluorine-containing polymers (A2), R.sup.5 to R.sup.8 each independently represent a fluorine atom, a trifluoromethyl group, a perfluoroethyl group, or a trifluoromethoxy group.

13. The fluorine-containing composition according to claim 6, wherein the fluorine-containing polymers (A2) are at least one member selected from the group consisting of fluorine-containing polymers (A2-1) containing as a main component a structural unit represented by formula (A2-1): ##STR00037## and fluorine-containing polymers (A2-2) containing as a main component a structural unit represented by formula (A2-2): ##STR00038##

14. A composition comprising two or more fluorine-containing polymers (A) containing as a main component a structural unit having a fluorine-containing aliphatic ring and further containing an aprotic solvent, the fluorine-containing polymers (A) being dissolved in the aprotic solvent, the fluorine-containing aliphatic ring having one, two, or three ethereal oxygen atoms as ring-constituting atoms.

15. The composition according to claim 14, wherein a resin composition obtained by drying the composition to a solid has a refractive index that is less than the sum of values calculated by multiplying individual refractive indices of the fluorine-containing polymers (A) in the composition by individual mass ratios of the fluorine-containing polymers (A) in the composition to the total mass of the fluorine-containing polymers (A) in the composition.

16. The composition according to claim 14, wherein a resin composition obtained by drying the composition to a solid has a refractive index that is at least 0.005 less than the largest refractive index among the individual refractive indices of the fluorine-containing polymers (A) in the composition.

17. The composition according to claim 14, wherein the aprotic solvent is at least one solvent selected from the group consisting of perfluoroaromatic compounds, perfluorotrialkylamines, perfluoroalkanes, hydrofluorocarbons, perfluorocyclic ethers, and hydrofluoroethers.

18. The composition according to claim 14, wherein the aprotic solvent is a hydrofluoroether.

19.-21. (canceled)

22. The composition according to claim 14, wherein the aprotic solvent is at least one member selected from the group consisting of CF.sub.3CF.sub.2CF.sub.2CF.sub.2OCH.sub.3, CF.sub.3CF.sub.2CF(CF.sub.3)OCH.sub.3, CF.sub.3CF.sub.2CF.sub.2CF.sub.2OC.sub.2H.sub.5, CF.sub.3CF.sub.2CF(CF.sub.3)OC.sub.2H.sub.5, CF.sub.3CH.sub.2OCF.sub.2CHF.sub.2, C.sub.2F.sub.5CF(OCH.sub.3)C.sub.3F.sub.7, (CF.sub.3).sub.2CHOCH.sub.3, (CF.sub.3).sub.2CFOCH.sub.3, CHF.sub.2CF.sub.2OCH.sub.2CF.sub.3, CHF.sub.2CF.sub.2CH.sub.2OCF.sub.2CHF.sub.2, CF.sub.3CHFCF.sub.2OCH.sub.3, and CF.sub.3CHFCF.sub.2OCF.sub.3.

23. The composition according to claim 14, wherein the total content of the two or more fluorine-containing polymers (A) dissolved in the aprotic solvent is in the range of 20 mass % to 65 mass % based on the mass of the composition.

24. The composition according to claim 14, wherein the fluorine-containing polymers (A) in the composition are two or more members selected from the group consisting of fluorine-containing polymers (A1) containing as a main component a structural unit represented by formula (A1): ##STR00039## wherein n and m are each independently 0 or 1, Y is an oxygen atom or CF.sub.2, and R.sup.1 to R.sup.4 independently represent a fluorine atom, a C.sub.1-C.sub.5 perfluoroalkyl group, or a C.sub.1-C.sub.5 perfluoroalkoxy group; and fluorine-containing polymers (A2) containing as a main component a structural unit represented by formula (A2): ##STR00040## wherein R.sup.5 to R.sup.8 each independently represent a fluorine atom, a C.sub.1-C.sub.5 perfluoroalkyl group, or a C.sub.1-C.sub.5 perfluoroalkoxy group.

25. The composition according to claim 24, wherein the fluorine-containing polymers (A1) are fluorine-containing polymers (A1) containing as a main component a structural unit represented by formula (A1): ##STR00041## wherein R.sup.1 to R.sup.4 each independently represent a fluorine atom, a C.sub.1-C.sub.5 perfluoroalkyl group, or a C.sub.1-C.sub.5 perfluoroalkoxy group.

26. The composition according to claim 24, wherein the fluorine-containing polymers (A) in the composition are two or more members selected from the fluorine-containing polymers (A1).

27. The composition according to claim 24, wherein the fluorine-containing polymers (A) in the composition are two or more members selected from the fluorine-containing polymers (A2).

28. The composition according to claim 24, wherein the fluorine-containing polymers (A) in the composition are at least one member selected from the fluorine-containing polymers (A1) and at least one member selected from the fluorine-containing polymers (A2).

29. The composition according to claim 24, wherein the fluorine-containing polymers (A1) are at least one member selected from the group consisting of fluorine-containing polymers (A1-1) containing as a main component a structural unit represented by formula (A1-1): ##STR00042## and fluorine-containing polymers (A1-2) containing as a main component a structural unit represented by formula (A1-2): ##STR00043##

30. The composition according to claim 24, wherein in the fluorine-containing polymers (A2), R.sup.5 to R.sup.8 each independently represent a fluorine atom, a trifluoromethyl group, a perfluoroethyl group or a trifluoromethoxy group.

31. The composition according to claim 24, wherein the fluorine-containing polymers (A2) are at least one member selected from the group consisting of fluorine-containing polymers (A2-1) containing as a main component a structural unit represented by formula (A2-1): ##STR00044## and fluorine-containing polymers (A2-2) containing as a main component a structural unit represented by formula (A2-2) ##STR00045##

32. A method for producing a fluorine-containing composition comprising two or more fluorine-containing polymers (A) containing as a main component a structural unit having a fluorine-containing aliphatic ring, the method comprising mixing the two or more fluorine-containing polymers (A) in an aprotic solvent, the fluorine-containing aliphatic ring having one, two, or three ethereal oxygen atoms as ring-constituting atoms.

33. The method according to claim 32, wherein the aprotic solvent is at least one solvent selected from the group consisting of perfluoroaromatic compounds, perfluorotrialkylamines, perfluoroalkanes, hydrofluorocarbons, perfluorocyclic ethers, and hydrofluoroethers.

34. The method according to claim 32, wherein the aprotic solvent is a hydrofluoroether.

35.-38. (canceled)

39. The method according to claim 32, wherein in the step of mixing the two or more fluorine-containing polymers (A) in the aprotic solvent, the aprotic solvent is used in an amount of 100 to 5000 parts by mass based on the total mass of the two or more fluorine-containing polymers (A) taken as 100 parts by mass.

40. (canceled)

41. The method according to claim 32, wherein the fluorine-containing polymers (A) in the composition are two or more members selected from the group consisting of fluorine-containing polymers (A1) containing as a main component a structural unit represented by formula (A1): ##STR00046## wherein n and m are each independently 0 or 1, Y is an oxygen atom or CF.sub.2, and R.sup.1 to R.sup.4 independently represent a fluorine atom, a C.sub.1-C.sub.5 perfluoroalkyl group, or a C.sub.1-C.sub.5 perfluoroalkoxy group and fluorine-containing polymers (A2) containing as a main component a structural unit represented by formula (A2): ##STR00047## wherein R.sup.5 to R.sup.8 each independently represent a fluorine atom, a C.sub.1-C.sub.5 perfluoroalkyl group, or a C.sub.1-C.sub.5 perfluoroalkoxy group.

42. The method according to claim 41, wherein the fluorine-containing polymers (A1) are fluorine-containing polymers (A1) containing as a main component a structural unit represented by formula (A1): ##STR00048## wherein R.sup.1 to R.sup.4 each independently represent a fluorine atom, a C.sub.1-C.sub.5 perfluoroalkyl group, or a C.sub.1-C.sub.5 perfluoroalkoxy group.

43. The method according to claim 41, wherein the fluorine-containing polymers (A) in the composition are two or more members selected from the fluorine-containing polymers (A1).

44. The method according to claim 41, wherein the fluorine-containing polymers (A) in the composition are two or more members selected from the fluorine-containing polymers (A2).

45. The method according to claim 41, wherein the fluorine-containing polymers (A) in the composition are at least one member selected from the fluorine-containing polymers (A1) and at least one member selected from the fluorine-containing polymers (A2).

46. The method according to claim 41, wherein the fluorine-containing polymers (A1) are at least one member selected from the group consisting of fluorine-containing polymers (A1-1) containing as a main component a structural unit represented by formula (A1-1): ##STR00049## and fluorine-containing polymers (A1-2) containing as a main component a structural unit represented by formula (A1-2): ##STR00050##

47. The method according to claim 41, wherein in the fluorine-containing polymers (A2), R.sup.5 to R.sup.8 each independently represent a fluorine atom, a trifluoromethyl group, a perfluoroethyl group or a trifluoromethoxy group.

48. The method according to claim 41, wherein the fluorine-containing polymers (A2) are at least one member selected from the group consisting of fluorine-containing polymers (A2-1) containing as a main component a structural unit represented by formula (A2-1): ##STR00051## and fluorine-containing polymers (A2-2) containing as a main component a structural unit represented by formula (A2-2): ##STR00052##

49. An optical device comprising the fluorine-containing composition of claim 1.

50. An anti-reflection film comprising the fluorine-containing composition of claim 1.

51. A lens comprising the fluorine-containing composition of claim 1.

52. A pellicle membrane comprising the fluorine-containing composition of claim 1.

53. A sealant comprising the fluorine-containing composition of claim 1.

54. A plastic optical fiber comprising the fluorine-containing composition of claim 1.

Description

EXAMPLES

[0254] An embodiment of the present disclosure is described in more detail below with reference to Examples; however, the present disclosure is not limited to these.

[0255] Teflon? AF copolymer is a copolymer containing a structural unit (A1-1) as a main component and further containing a structural unit (B-1). Hyflon? AD is a copolymer containing a structural unit (A1-2) as a main component and further containing a structural unit (B-1).

[0256] Novec 7100 is a mixed solution of methyl nonafluorobutyl ether and methyl nonafluoroisobutyl ether, produced by 3M Japan Limited.

Refractive Index

[0257] The refractive index of sheet samples obtained in the Examples below was measured at 23? C. using an Abbe refractometer (NAR-1T SOLID) produced by Atago Co., Ltd. The wavelength was a wavelength approximate to D-line because of the use of the LED attached to the device.

Haze Value

[0258] The haze value of the sheet samples obtained in the Examples below was measured using a COH 7700 color spectrophotometer/haze meter, produced by Nippon Denshoku Industries. Each sample had a size of 20 mm?20 mm and a thickness of 500 to 600 ?m.

Transparency

[0259] Each sample with a thickness of 0.5 mm was placed on a base material. When the base material could be visually recognized through the sample, the sample was evaluated as transparent.

Comparative Example 1

[0260] After 1.5 g of a Teflon? AF copolymer and 3.5 g of a homopolymer of the structural unit (A2-1) were fully mixed in powder form in a plastic bag, the resulting composition was melted into a sheet at 270? C. Since the obtained sheet was cloudy (haze value: 95.7), the refractive index was not measured.

Comparative Example 2

[0261] After 1.5 g of a Hyflon? AD copolymer and 3.5 g of a homopolymer of the structural unit (A2-1) were fully mixed in powder form in a plastic bag, the resulting composition was melted into a sheet at 270? C. Since the obtained sheet was cloudy (haze value: 96.9), the refractive index was not measured.

Example 1

[0262] After 0.5 g of a Teflon? AF copolymer and 4.5 g of a homopolymer of the structural unit (A2-1) were dissolved in 45 g of Novec 7100 in a 100 mL polyethylene bottle, the resulting solution was slowly dried overnight at room temperature in saturated steam of Novec 7100 to obtain a colorless transparent (haze value: 17.5) fluorine-containing composition in the form of a sheet. The obtained sheet had a refractive index of 1.328.

Example 2

[0263] After 1.5 g of a Teflon? AF copolymer and 3.5 g of a homopolymer of the structural unit (A2-1) were dissolved in 45 g of Novec 7100 in a 100 mL polyethylene bottle, the resulting solution was slowly dried overnight at room temperature in saturated steam of Novec 7100 to obtain a colorless transparent (haze value: 19.2) fluorine-containing composition in the form of a sheet. The obtained sheet had a refractive index of 1.318.

Example 3

[0264] After 1.5 g of a Hyflon? AD copolymer and 3.5 g of a homopolymer of the structural unit (A2-1) were dissolved in 45 g of Novec 7100 in a 100 mL polyethylene bottle, the resulting solution was slowly dried overnight at room temperature in saturated steam of Novec 7100 to obtain a colorless transparent (haze value: 54.5) fluorine-containing composition in the form of a sheet. The obtained sheet had a refractive index of 1.317.

[0265] Table 1 shows the formulations of the compositions produced in the above Comparative Examples and Examples, refractive indices, etc. For reference, refractive indices of the polymers used as starting materials are also shown in Table 1. The theoretical refractive indices were calculated from the refractive indices and the content ratio of the polymers of each composition. By mixing the Teflon? AF copolymer or the Hyflon? AD copolymer with the homopolymer of the structural unit (A2-1), the refractive index of the homopolymer of the structural unit (A2-1) was successfully reduced.

TABLE-US-00001 TABLE 1 Measured Theoretical refractive Component 1 Component 2 Mixing Mixed refractive index Item Component mass % Component mass % method state index Component Reference Teflon? AF 100 1.307 data Reference Hyflon? AD 100 1.327 data Reference Homopolymer 100 1.334 data of A2-1 Comparative Teflon? AF 30 Homopolymer 70 Powder Cloudy Example 1 of A2-1 mixing Comparative Hyflon? AD 30 Homopolymer 70 Powder Cloudy Example 2 of A2-1 mixing Example 1 Teflon? AF 10 Homopolymer 90 Solution Colorless and 1.331 1.328 of A2-1 mixing transparent Example 2 Teflon? AF 30 Homopolymer 70 Solution Colorless and 1.326 1.318 of A2-1 mixing transparent Example 3 Hyflon? AD 30 Homopolymer 70 Solution Colorless and 1.332 1.317 of A2-1 mixing transparent