SOFT WATER- AND OIL-REPELLENT COMPRISING FLUORINE-CONTAINING POLYMER AS ACTIVE INGREDIENT

Abstract

A soft water- and oil-repellent comprising, as an active ingredient, a copolymer of a perfluoropolyether alcohol (meth)acrylic acid derivative represented by the general formula:

CH.sub.2═CR.sub.1COOCH.sub.2CF(CF.sub.3)[OCF.sub.2CF(CF.sub.3)].sub.nOC.sub.3F.sub.7  [I]

(wherein R.sub.1 is a hydrogen atom or a methyl group, and n is an integer of 1 to 20), and a (meth)acrylic acid ester represented by the general formula:

CH.sub.2═CR.sub.1COOR.sub.2  [II]

(wherein R.sub.1 is a hydrogen atom or a methyl group, and R.sub.2 is an alkyl group, an alkoxyalkyl group, a cycloalkyl group, an aryl group, or an aralkyl group) and having a glass transition temperature Tg of 51 to 120° C. The soft water- and oil-repellent gives a coating film formed from a coating agent which closely follows the deformation of rubber or resin, and exhibits water- and oil-repellency.

Claims

1. A soft water- and oil-repellent comprising, as an active ingredient, a copolymer of:
CH.sub.2═CHCOOCH.sub.2CF(CF.sub.3)[OCF.sub.2CF(CF.sub.3)]OC.sub.3F.sub.7, and a (meth)acrylic acid ester represented by the general formula:
CH.sub.2═CR.sub.1COOR.sub.2  [II] wherein R.sub.1 is a hydrogen atom or a methyl group, and R.sub.2 is an alkyl group, an alkoxyalkyl group, a cycloalkyl group, an aryl group, or an aralkyl group, and having a glass transition temperature Tg of 51 to 120° C.

2. (canceled)

3. The soft water- and oil-repellent according to claim 1, wherein the (meth)acrylic acid ester having a glass transition temperature of 51 to 120° C. is methyl methacrylate or ethyl methacrylate.

4. The soft water- and oil-repellent according to claim 1, wherein the (meth)acrylic acid ester is copolymerized at a ratio of 5 to 30 wt. % in the copolymer.

5. The soft water- and oil-repellent according to claim 1, which is prepared as an organic solvent solution.

6. The soft water- and oil-repellent according to claim 5, which is prepared as a fluorine-containing organic solvent solution.

7. A soft water- and oil-repellent, which comprises an organic solvent solution of a copolymer of a perfluoropolyether alcohol (meth)acrylic acid derivative represented by the general formula:
CH.sub.2═CR.sub.1COOCH.sub.2CF(CF.sub.3)[OCF.sub.2CF(CF.sub.3)].sub.nOC.sub.3F.sub.7  [I] wherein R.sub.1 is a hydrogen atom or a methyl group, and n is an integer of 1 to 20, and a (meth)acrylic acid ester represented by the general formula:
CH.sub.2═CR.sub.1COOR.sub.2  [II] wherein R.sub.1 is a hydrogen atom or a methyl group, and R.sub.2 is an alkyl group, an alkoxyalkyl group, a cycloalkyl group, an aryl group, or an aralkyl group, and having a glass transition temperature Tg of 51 to 120° C., and which is applied to a rubber product.

8. The soft water- and oil-repellent according to claim 7, which is applied to elastic resin product.

9. A rubber product surface-coated with the soft water- and oil-repellent according to claim 7.

10. An elastic resin product surface-coated with the soft water- and oil-repellent according to claim 8.

Description

EXAMPLES

[0050] The following describes the present disclosure with reference to Examples.

Example 1

[0051] The following components were charged in a 50-ml capacity glass reaction container equipped with a condenser and a thermometer:

TABLE-US-00001 CH.sub.2═CHCOOCH.sub.2CF(CF.sub.3)[OCF.sub.2CF(CF.sub.3)]OC.sub.3F.sub.7 8.04 g [PO-3-AC] CH.sub.2═C(CH.sub.3)COOCH.sub.3 (Tg: 105° C.) 0.64 g Solvent (Novec 7300, produced by 3M; C.sub.4F.sub.9OCH.sub.3) 17.72 g Azobisisobutyronitrile 44.3 mg

[0052] While stirring the mixture, the copolymerization reaction was carried out at 70° C. for 21 hours, thereby obtaining a polymerization reaction solution having a solid matters content of 28.6 wt. %.

[0053] The same solvent was added to the polymerization reaction solution to adjust its solid matters content to 10 wt. %. The resultant was spin-coated on an EPDM substrate (15.0×30.0×2.0 mm) at a rotational speed of 1000 rpm for 10 seconds, and baked at 120° C. for 10 minutes in an oven, thereby producing a test sample. A softness test, a water- and oil-repellent test and a tackiness test are conducted to the test sample, and evaluating it according to the following evaluation criteria.

Softness Test Method:

[0054] The test sample was 10 to 80% stretched by a tensile tester, the progress of stretching was observed using a microscope to observe cracks etc. in the coating film, and evaluation was carried out according to the following criteria.

[0055] ⊚: No cracks or wrinkles when 0% returned [0056] No cracks when +40% stretched

[0057] ∘: No cracks or wrinkles when 0% returned [0058] No cracks when +20% stretched

[0059] Δ: No cracks or wrinkles when 0% returned [0060] No cracks when +10% stretched

[0061] X: Cracks and wrinkles are observed when 0% returned [0062] Water- and oil-repellent test method:

[0063] The test sample was subjected to a contact angle measurement method using Dropmaster DM500 (produced by Kyowa Interface Science Co., Ltd.). Two types of test liquids, water and hexadecane, were used. The evaluation criteria was as shown below.

[0064] Water-repellent test (pure water)

[0065] ⊚: A contact angle of 110° or more

[0066] ∘: A contact angle of 105° to 109°

[0067] Δ: A contact angle of 100° to 104°

[0068] X: A contact angle of 99° or less

[0069] Oil-repellent test (hexadecane)

[0070] ⊚: A contact angle of 70° or more

[0071] ∘: A contact angle of 65° to 69°

[0072] Δ: A contact angle of 60° to 64°

[0073] X: A contact angle of 59° or less

Tackiness Test Method:

[0074] The state of the coating film when the test sample was lightly touched with a finger was evaluated according to the following evaluation criteria.

[0075] ⊚: Tack-free

[0076] ◯: Nearly fingerprint remained

[0077] Δ: Slightly tacky

[0078] X: Nearly stringy

Example 2

[0079] In Example 1, 8.25 g of

CH.sub.2═C(CH.sub.3)COOCH.sub.2CF(CF.sub.3)[OCF.sub.2CF(CF.sub.3)]OC.sub.3F.sub.7  [PO-3-MAC]

[0080] was used in place of PO-3-AC. Further, the amount of solvent was changed to 18.15 g, and the amount of polymerization initiator was changed to 44.2 mg, thereby obtaining a polymerization reaction solution having a solid matters content of 31.3 wt. %.

Example 3

[0081] In Example 2, 0.73 g of ethyl methacrylate (Tg: 65° C.) was used in place of methyl methacrylate. Further, the amount of solvent was changed to 18.35 g, and the amount of polymerization initiator was changed to 44.0 mg, thereby obtaining a polymerization reaction solution having a solid matters content of 31.3 wt. %.

Example 4

[0082] In Example 2, the amount of P0-3-MAC was changed to 8.26 g, and further 54.8 mg of 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (Karenz MOI-BP, produced by Showa Denko K.K.) was used as a crosslinkable monomer. In addition, the amount of solvent was changed to 18.26 g, and the amount of polymerization initiator was changed to 44.7 mg, thereby obtaining a polymerization reaction solution having a solid matters content of 31.9 wt. %.

Comparative Example 1

[0083] In Example 1, 10.73 g of

CH.sub.2═CH(CH.sub.3)COOC.sub.5F.sub.10CH.sub.2C.sub.6F.sub.13  [fluorine-containing monomer A]

was used in place of P0-3-AC, and methyl methacrylate was not used. Further, the amount of solvent was changed to 21.83 g, and the amount of polymerization initiator was changed to 37.1 mg, thereby obtaining a polymerization reaction solution having a solid matters content of 33.0 wt. %.

Comparative Example 2

[0084] In Example 1, 8.26 g of

CH.sub.2═CHCOOCH.sub.2CH.sub.2C.sub.6F.sub.13  [FAMAC-6]

was used in place of P0-3-AC, and methyl methacrylate was not used. Further, the amount of solvent was changed to 26.45 g, and the amount of polymerization initiator was changed to 61.9 mg, thereby obtaining a polymerization reaction solution having a solid matters content of 34.6 wt. %.

Comparative Example 3

[0085] In Example 2, 28.1 mg of 2-hydroxyethyl acrylate [2HEA] was additionally used as a crosslinkable monomer. Further, the amount of solvent was changed to 18.21 g, and the amount of polymerization initiator was changed to 44.6 mg. However, since 2HEA was poorly compatible with the solvent Novec 7300, the product became cloudy and solidified, and the various characteristics could not be measured.

Comparative Example 4

[0086] In Example 1, 0.82 g of n-butyl acrylate (Tg: −49° C.) was used in place of methyl methacrylate. Further, the amount of solvent was changed to 18.09 g. However, the product was a liquid material without solid matters, and the various characteristics could not be measured.

Comparative Example 5

[0087] In Example 2, 0. 91 g of n-butyl methacrylate (Tg: 20° C.) was used in place of methyl methacrylate. Further, the amount of solvent was changed to 17.91 g, thereby obtaining a polymerization reaction solution having a solid matters content of 27.6 wt. %.

[0088] Following Table shows the results obtained respectively in the above Examples 1 to 4 and Comparative Examples 1 to 2 and 5.

TABLE-US-00002 TABLE Water- Oil- Softness repellent repellent Tackiness Example test test test test Example 1 ⊚ ⊚ ⊚ Δ Example 2 ◯ ⊚ ◯ ⊚ Example 3 ◯ ⊚ ⊚ ⊚ Example 4 ◯ ◯ ◯ ⊚ Comparative Example 1 X ⊚ ⊚ ⊚ Comparative Example 2 X ⊚ ⊚ ⊚ Comparative Example 5 X ⊚ ◯ ◯