FLUORINE-CONTAINING ALCOHOL COMPOSITE

Abstract

A fluorine-containing alcohol composite comprising a condensate of a fluorine-containing alcohol represented by the general formula: HO-A-R.sub.F-A-OH [I] (wherein R.sub.F is a group containing a perfluoroalkylene group or a polyfluoroalkylene group having 6 or less carbon atoms and an ether bond, and A is an alkylene group having 1 to 3 carbon atoms), a hydroxyl group-containing polymer, and a zirconium compound. The fluorine-containing alcohol composite, using a fluorine-containing alcohol, does not produce perfluorooctanoic acid and the like when released into the environment and that has a unit easily decomposed into short chain compounds. And also, it exhibits hydrophilic oil repellency.

Claims

1. A fluorine-containing alcohol composite comprising a condensate of a fluorine-containing alcohol represented by the general formula:
HO-A-R.sub.F-A-OH  [I] wherein R.sub.F is a group containing a perfluoroalkylene group or a polyfluoroalkylene group having 6 or less carbon atoms, and an ether bond, and A is an alkylene group having 1 to 3 carbon atoms, a hydroxyl group-containing polymer, and a zirconium compound.

2. The fluorine-containing alcohol composite according to claim 1, wherein organic silicon compound is further comprised.

3. The fluorine-containing alcohol composite according to claim 1, wherein as the fluorine-containing alcohol represented by the general formula [I], a perfluoroalkylene ether diols represented by the general formula:
HO(CH.sub.2).sub.aCF(CF.sub.3)[OCF.sub.2CF(CF.sub.3)].sub.bO(CF.sub.2).sub.cO[CF(CF.sub.3)CF.sub.2O].sub.dCF(CF.sub.3)(CH.sub.2).sub.aOH  [III] wherein a is an integer of 1 to 3, b+d is an integer of 0 to 50, and c is an integer of 1 to 6 is used.

4. The fluorine-containing alcohol composite according to claim 1, wherein the hydroxyl group-containing polymer is polyvinyl alcohol.

5. The fluorine-containing alcohol composite according to claim 1, wherein the zirconium compound is zirconium oxychloride.

6. The fluorine-containing alcohol composite according to claim 2, wherein the organic silicon compound is tetra lower alkyl orthosilicate.

7. A method for producing a condensate, comprising subjecting each of the components according to claim 1 to a condensation reaction using a basic catalyst or an acidic catalyst.

8. The method for producing a condensate according to claim 7, wherein the hydroxyl group-containing polymer is used at a 0.5 to 10 times ratio, and the zirconium compound is used at a 5 times or less ratio, based on the fluorine-containing alcohol.

9. The method for producing a condensate according to claim 7, wherein the organic silicon compound is used at a 5 times or less ratio, based on the fluorine-containing alcohol.

10. The method for producing a condensate according to claim 7, wherein the basic catalyst is an ammonia aqueous solution.

11. The method for producing a condensate according to claim 7, wherein the acidic catalyst is an inorganic acid.

12. A surface treatment agent, comprising the fluorine-containing alcohol composite according to claim 1, as an active ingredient.

13. The surface treatment agent according to claim 12, which exhibits hydrophilic oil repellency.

14. A substrate with a coating film formed from the surface treatment agent according to claim 12.

Description

EXAMPLES

[0052] The following describes the present disclosure with reference to Examples.

Examples Using a Basic Catalyst

Example 1

[0053] In a reaction container with a capacity of 13 ml, 10 mg of a fluorine-containing alcohol:

HOCH.sub.2CF(CF.sub.3)[OCF.sub.2CF(CF.sub.3)].sub.bO(CF.sub.2).sub.2O[CF(CF.sub.3)CFO.sub.2O].sub.dCF(CF.sub.3)CH.sub.2OH [OXF9DOH,b+d=7],

25 mg of polyvinyl alcohol (Kuraray Poval LM10-HD, produced by Kuraray Co., Ltd.), and 4 ml of ethanol were charged, and 1 ml (25 mg as zirconium oxychloride) of an ethanol solution of zirconium oxychloride (concentration: 0.025 g/ml) was added thereto, followed by stirring for 10 minutes. Then, 1 ml of a 25 wt. % ammonia aqueous solution was added as dropwise while stirring, followed by stirring under room temperature conditions for 5 hours.

[0054] 0.35 ml of the obtained reaction solution was added as dropwise on a glass plate (Matsunami Cover Glass (18×18 mm), produced by Matsunami Glass Ind., Ltd.), and dried under room temperature conditions, followed by heat treatment at 150° C. for 2 hours.

[0055] Measurement of Static Contact Angle: [0056] 2 μl of droplets of n-dodecane or water were gently brought into contact with the obtained glass surface, and the contact angle (unit: °) of the attached droplets was measured by the θ/2 method using a contact angle meter (Drop Master 300, produced by Kyowa Interface Science Co., Ltd.). The contact angle with respect to water was measured over time.

[0057] Coating Film Durability Test: [0058] The treated glass plate was cleaned by dipping in ion exchange water for 20 minutes, and then dried under room temperature conditions for 1 day, thereby obtaining a sample after cleaning. The static contact angle of the sample after cleaning was measured.

[0059] Evaluation of Oil Repellency and Hydrophilicity: [0060] Regarding oil repellency, a static contact angle of 40° or more was evaluated as ◯, and 30° or more and less than 40° was evaluated as Δ. Regarding hydrophilicity, a static contact angle of 30° or less was evaluated as ◯, and more than 30° was evaluated as X.

[0061] Regarding the sample before cleaning and after cleaning, the appearance of the glass plate was visually observed and evaluated as follows. Colorless and transparent: ◯; partially discolored or cloudy: Δ; and completely discolored or cloudy: X.

Example 2

[0062] In Example 1, the amount of fluorine-containing alcohol OXF9DOH was changed to 30 mg.

Example 3

[0063] In Example 2, 1 ml (50 mg as TEOS) of an ethanol solution (concentration: 0.05 g/ml) of tetraethyl orthosilicate [TEOS] was further used, and the amount of ethanol was changed to 5 ml.

Example 4

[0064] In Example 1, the same amount (10 mg) of

HOCH.sub.2CF(CF.sub.3)[OCF.sub.2CF(CF.sub.3)].sub.bO(CF.sub.2).sub.2O[CF(CF.sub.3)CFO.sub.2O].sub.dCF(CF.sub.3)CH.sub.2OH [OXF3DOH,b+d=1]

was used as the fluorine-containing alcohol.

Example 5

[0065] In Example 4, 50 mg of TEOS was further used, and the amount of ethanol was changed to 5 ml.

Example 6

[0066] In Example 4, the amount of fluorine-containing alcohol OXF3DOH was changed to 30 mg.

Example 7

[0067] In Example 6, 50 mg of TEOS was further used, and the amount of ethanol was changed to 5 ml.

Examples Using an Acidic Catalyst

Example 8

[0068] In Example 1, the same amount (1 ml) of 0.1N hydrochloric acid was used in place of the 25 wt. % ammonia aqueous solution.

Example 9

[0069] In Example 8, 50 mg of TEOS was further used, and the amount of ethanol was changed to 5 ml.

Example 10

[0070] In Example 8, the amount of fluorine-containing alcohol OXF9DOH was changed to 30 mg.

Example 11

[0071] In Example 10, 50 mg of TEOS was further used, and the amount of ethanol was changed to 5 ml.

Example 12

[0072] In Example 5, the same amount (1 ml) of 0.1N hydrochloric acid was used in place of the 25 wt. % ammonia aqueous solution.

Example 13

[0073] In Example 6, the same amount (1 ml) of 0.1N hydrochloric acid was used in place of the 25 wt. % ammonia aqueous solution.

Example 14

[0074] In Example 7, the same amount (1 ml) of 0.1N hydrochloric acid was used in place of the 25 wt. % ammonia aqueous solution.

Comparative Example Using a Basic Catalyst

Comparative Example 1

[0075] In Example 1, polyvinyl alcohol was not used.

Comparative Example 2

[0076] In Example 1, polyvinyl alcohol was not used and 50 mg of TEOS was used.

Comparative Example 3

[0077] In Example 2, polyvinyl alcohol was not used.

Comparative Example 4

[0078] In Example 3, polyvinyl alcohol was not used.

Comparative Example 5

[0079] In Example 4, polyvinyl alcohol was not used.

Comparative Example 6

[0080] In Example 5, polyvinyl alcohol was not used.

Comparative Example 7

[0081] In Example 6, polyvinyl alcohol was not used.

Comparative Example Using an Acidic Catalyst

Comparative Example 8

[0082] In Example 8, polyvinyl alcohol was not used.

Comparative Example 9

[0083] In Example 9, polyvinyl alcohol was not used.

Comparative Example 10

[0084] In Example 10, polyvinyl alcohol was not used.

Comparative Example 11

[0085] In Example 11, polyvinyl alcohol was not used.

Comparative Example 12

[0086] In Example 12, polyvinyl alcohol and TEOS were not used.

Comparative Example 13

[0087] In Example 12, polyvinyl alcohol was not used.

Comparative Example 14

[0088] In Example 13, polyvinyl alcohol was not used.

Comparative Example 15

[0089] In Example 14, polyvinyl alcohol was not used.

[0090] The results obtained in the above Examples and Comparative Examples are shown in the following Table 1.

TABLE-US-00001 TABLE 1 Static contact angle before cleaning(°) Static contact angle Water (min) oil after cleaning({circumflex over ( )}) Example Dodecane 0 5 10 15 20 25 30 repellency hydrophilicity Dodecane Example 1 61 92 18 11 0 0 0 0 ∘ ∘ 83 Example 2 61 84 21 15 0 0 0 0 ∘ ∘ 63 Example 3 60 80 21 15 0 0 0 0 ∘ ∘ 85 Example 4 58 83 33 28 24 20 15 0 ∘ ∘ 40 Example 5 59 82 32 26 24 17 18 0 ∘ ∘ 44 Example 6 57 75 31 27 21 16 13 0 ∘ ∘ 42 Example 7 57 75 31 27 22 18 14 0 ∘ ∘ 46 Example 8 58 103 45 31 24 18 17 16 ∘ ∘ 59 Example 9 58 112 23 16 11 0 0 03 ∘ ∘ 58 Example 10 61 101 43 37 34 32 27 27 ∘ ∘ 58 Example 11 61 124 54 34 25 23 19 18 ∘ ∘ 57 Example 12 48 110 65 44 33 29 26 27 ∘ ∘ 36 Example 13 47 103 53 35 27 23 21 18 ∘ ∘ 18 Example 14 52 95 68 50 42 42 31 26 ∘ ∘ 43 Comparative 60 100 100 96 93 93 93 93 ∘ x 81 Example 1 Comparative 82 86 87 87 83 83 83 83 ∘ x 61 Example 2 Comparative 57 81 76 73 70 70 70 70 ∘ x 60 Example 3 Comparative 59 93 78 67 63 63 83 83 ∘ x 59 Example 4 Comparative 39 94 92 91 91 91 81 91 Δ x 52 Example 5 Comparative 49 85 79 76 74 69 65 68 ∘ x 50 Example 6 Comparative 42 87 87 85 85 85 85 85 ∘ x 40 Example 7 Comparative 58 80 70 74 69 64 64 64 ∘ x 40 Example 8 Comparative 49 103 92 92 92 92 92 92 ∘ x 83 Example 9 Comparative 55 83 64 64 64 64 84 84 ∘ x 32 Example 10 Comparative 52 78 75 71 71 71 71 71 ∘ x 54 Example 11 Comparative 36 58 52 48 48 42 36 36 Δ x 42 Example 12 Comparative 49 70 67 67 67 67 67 67 ∘ x 49 Example 13 Comparative 64 64 60 59 57 57 57 57 ∘ x 50 Example 14 Comparative 42 68 61 61 61 61 81 81 ∘ x 42 Example 15 Static contact angle Appearance of after cleaning({circumflex over ( )}) modified glass Water (min) oil Before After Example 0 5 10 15 20 25 30 repellency hydrophilicity cleaning cleaning Example 1 100 28 24 22 18 18 13 ∘ ∘ ∘ ∘ Example 2 101 34 29 27 24 21 10 ∘ ∘ ∘ ∘ Example 3 73 33 28 23 20 18 12 ∘ ∘ ∘ ∘ Example 4 80 15 11 0 0 0 0 ∘ ∘ ∘ ∘ Example 5 73 12 0 0 0 0 0 ∘ ∘ ∘ ∘ Example 6 71 18 12 0 0 0 0 ∘ ∘ ∘ ∘ Example 7 85 11 0 0 0 0 0 ∘ ∘ ∘ ∘ Example 8 113 56 38 30 26 20 17 ∘ ∘ ∘ ∘ Example 9 102 15 8 0 0 0 0 ∘ ∘ ∘ ∘ Example 10 107 46 39 35 32 27 23 ∘ ∘ ∘ ∘ Example 11 106 45 32 27 25 21 20 ∘ ∘ ∘ ∘ Example 12 80 47 36 28 25 22 18 Δ ∘ ∘ ∘ Example 13 65 40 31 25 22 18 16 Δ ∘ ∘ ∘ Example 14 85 40 34 30 28 23 23 ∘ ∘ ∘ ∘ Comparative 94 81 78 74 71 71 71 ∘ x ∘ ∘ Example 1 Comparative 98 78 75 72 65 66 65 ∘ x ∘ ∘ Example 2 Comparative 95 84 84 79 75 72 72 ∘ x ∘ ∘ Example 3 Comparative 89 81 79 76 72 67 67 ∘ x ∘ ∘ Example 4 Comparative 71 65 82 58 53 47 47 ∘ x ∘ ∘ Example 5 Comparative 65 58 58 51 47 47 47 ∘ x ∘ ∘ Example 6 Comparative 68 54 61 58 53 47 47 ∘ x ∘ ∘ Example 7 Comparative 88 75 71 64 61 61 61 ∘ x ∘ ∘ Example 8 Comparative 103 95 92 92 92 92 92 ∘ x ∘ ∘ Example 9 Comparative 87 74 70 70 70 70 70 Δ x ∘ ∘ Example 10 Comparative 78 50 85 85 65 65 65 ∘ x ∘ ∘ Example 11 Comparative 56 50 45 43 35 35 35 ∘ x ∘ ∘ Example 12 Comparative 74 70 65 65 65 65 65 ∘ x ∘ ∘ Example 13 Comparative 75 58 57 57 57 57 57 ∘ x ∘ ∘ Example 14 Comparative 67 81 56 56 56 56 58 ∘ x Δ Δ Example 15

Examples 15 to 19

[0091] The anti-fog properties of the glass plates obtained in Examples 4 to 7 and 9 were evaluated in the following manner.

[0092] A beaker was filled with boiling water (about 90° C.), and each of the coated glass plates was placed above (3 cm above) the beaker. The glass plates not clouded with steam were evaluated as ◯, and the glass plates clouded with steam were evaluated as X.

[0093] The results obtained are shown in the following Table 2.

TABLE-US-00002 TABLE 2 Coated glass Before After Example plates Example cleaning cleaning 15 4 ◯ ◯ 16 5 ◯ ◯ 17 6 ◯ ◯ 18 7 ◯ ◯ 19 9 ◯ ◯