ANTIFOULING ARTICLE

Abstract

The present invention provides a novel antifouling article comprising a base material, a diamond-like carbon layer and an antifouling coating layer which is formed on the diamond-like carbon layer from a surface treating agent comprising a perfluoropolyether group-containing compound and having high acid resistant and alkaline resistant.

Claims

1. An antifouling article comprising a base material, a diamond-like carbon layer and an antifouling coating layer which is formed on the diamond-like carbon layer from a surface treating agent comprising a perfluoropolyether group-containing compound or a perfluoroalkyl group-containing compound.

2. The antifouling article according to claim 1 comprising a base material, a diamond-like carbon layer and an antifouling coating layer which is formed on the diamond-like carbon layer from a surface treating agent comprising one or more fluorine-containing compounds of any of formulae (A1), (A2), (B1) and (B2):
(Rf-PFPE).sub.α′-X.sup.3—(Y-A).sub.α  (A1)
(A-Y).sub.α—X.sup.3-PFPE-X.sup.3—(Y-A).sub.α  (A2)
(R.sup.91—Rf′).sub.β—X.sup.6—(Y-A).sub.β  (B1)
(A-Y).sub.β—X.sup.6—Rf′—X.sup.6—(Y-A).sub.β  (B2) wherein: A is each independently at each occurrence —OH, —SH, —COOH, —COSH, —CONH.sub.2, —P(O)(OH).sub.2, —OP(O)(OH).sub.2, —NR.sup.1.sub.2, ##STR00004## R.sup.1 is each independently a hydrogen atom or a lower alkyl group; X.sup.1 is O or S; M.sub.1 and M.sub.2 are each independently a hydrogen atom or an alkali metal; Y is each independently at each occurrence a single bond or a divalent organic group; Rf is each independently an alkyl group having 1-16 carbon atoms which may be substituted by one or more fluorine atoms; PFPE is each independently —(OC.sub.4F.sub.8).sub.a—(OC.sub.3F.sub.6).sub.b—(OC.sub.2F.sub.4).sub.c—(OCF.sub.2).sub.d, wherein a, b, c and d are each independently an integer of 0 or more and 200 or less, the sum of a, b, c and d is 1 or more, and the occurrence order of the respective repeating units in parentheses with the subscript a, b, c or d is not limited in the formula; X.sup.3 is each independently a single bond or a 2-10 valent organic group; α is each independently an integer of 1-9; α′ is each independently an integer of 1-9; X.sup.6 is each independently a single bond or a 2-10 valent organic group; β is each independently an integer of 1-9; β′ is each independently an integer of 1-9; R.sup.91 is a fluorine atom, —CHF.sub.2 or —CF.sub.3; and Rf′ is a perfluoroalkylene group having 1-20 carbon atoms.

3. The antifouling article according to claim 2 wherein A is —SH, —P(O)(OH).sub.2, —OP(O)(OH).sub.2, —NR.sup.1.sub.2, or ##STR00005##

4. The antifouling article according to claim 2 wherein Rf is a perfluoroalkyl group having 1-16 carbon atoms.

5. The antifouling article according to claim 2 wherein PFPE is following formula (a) or (b): (a) —(OC.sub.3F.sub.6).sub.b— in formula (a), b is an integer of one or more and 200 or less; (b) —(OC.sub.4F.sub.8).sub.a—(OC.sub.3F.sub.6).sub.b—(OC.sub.2F.sub.4).sub.c—(OCF.sub.2).sub.d— in formula (b), a and b are each independently an integer of 0 or more and 30 or less, c and d are each independently an integer of one or more and 200 or less, the sum of a, b, c and d is an integer of 10 or more and 200 or less, and the occurrence order of the respective repeating units in parentheses with the subscript a, b, c or d is not limited in the formula.

6. The antifouling article according to claim 2 wherein in PFPE: —(OC.sub.4F.sub.8).sub.a— is —(OCF.sub.2CF.sub.2CF.sub.2CF.sub.2).sub.a—, —(OC.sub.3F.sub.6).sub.b— is —(OCF.sub.2CF.sub.2CF.sub.2).sub.b—, and —(OC.sub.2F.sub.4).sub.c— is —(OCF.sub.2CF.sub.2).sub.c—.

7. The antifouling article according to claim 2 wherein X.sup.3 and X.sup.6 are a divalent organic group, α and β are 1, and a′ and (3′ are 1.

8. The antifouling article according to claim 2 wherein X.sup.3 and X.sup.6 are each independently a group of —(R.sup.31).sub.p′—(X.sup.a).sub.q′—R.sup.32— wherein: R.sup.31 is a single bond, —(CH.sub.2).sub.s′— (wherein s′ is an integer of 1-20) or an o-, m- or p-phenylene group; R.sup.32 is a single bond, —(CH.sub.2).sub.t′— (wherein t′ is an integer of 1-20) or an o-, m- or p-phenylene group; X.sup.a is —(X.sup.b).sub.r′— (wherein r′ is an integer of 1-10); X.sup.b is each independently at each occurrence a group selected from the group consisting of —O—, —S—, an o-, m- or p-phenylene group, —NR.sup.34— and —(CH.sub.2).sub.n′— (wherein n′ is an integer of 1-20); R.sup.34 is each independently at each occurrence a hydrogen atom, a phenyl group or a C.sub.1-6 alkyl group; p′ is 0 or 1; q′ is 0 or 1; the occurrence order of the respective repeating units in parentheses with the subscript p′ and q′ is not limited in the formula, and R.sup.31, R.sup.32 and X.sup.a may be substituted by one or more substituents selected from a fluorine atom, a C.sub.1-3 alkyl group and a C.sub.1-3 fluoroalkyl group.

9. The antifouling article according to claim 2 wherein X.sup.3 and X.sup.6 are each independently selected from the group consisting of: —CH.sub.2OCH.sub.2—, —CH.sub.2O(CH.sub.2).sub.2—, —CH.sub.2O(CH.sub.2).sub.3—, —CH.sub.2O(CH.sub.2).sub.6—, —CH.sub.2—, —(CH.sub.2).sub.2—, —(CH.sub.2).sub.3—, —(CH.sub.2).sub.4—, and —(CH.sub.2).sub.6—.

10. The antifouling article according to claim 2 wherein R.sup.91 is a fluorine atom or CF.sub.3.

11. The antifouling article according to claim 2 wherein the fluorine-containing compound is at least one compound of any of formulae (A1) and (A2).

12. The antifouling article according to claim 2 wherein the fluorine-containing compound is at least one compound of any of formulae (B1) and (B2).

13. The antifouling article according to claim 2 wherein the surface treating agent further comprises one or more components selected form a fluorine-containing oil, a silicone oil, and a catalyst.

14. The antifouling article according to claim 13 wherein the fluorine-containing oil is one or more compounds of formula (3):
Rf.sup.1—(OC.sub.4F.sub.8).sub.a′—(OC.sub.3F.sub.6).sub.b′—(OC.sub.2F.sub.4).sub.c′—(OCF.sub.2).sub.d′—Rf.sup.2   (3) wherein: Rf.sup.1 is an alkyl group having 1-16 carbon atoms which may be substituted by one or more fluorine atoms; Rf.sup.2 is an alkyl group having 1-16 carbon atoms which may be substituted by one or more fluorine atoms, a fluorine atom or a hydrogen atom; a′, b′, c′ and d′ are the repeating number of each of four repeating units of the perfluoro(poly)ether which constitute a main backbone of the polymer, and are each independently an integer of 0 or more and 300 or less, the sum of a′, b′, c′ and d′ is 1 or more, and the occurrence order of the respective repeating units in parentheses with the subscript a′, b′, c′ and d′ is not limited in the formula.

15. The antifouling article according to claim 13 wherein the fluorine-containing oil is one or more compounds of the formula (3a) or (3b):
Rf.sup.1—(OCF.sub.2CF.sub.2CF.sub.2).sub.b″—Rf.sup.2   (3a)
Rf.sup.2—(OCF.sub.2CF.sub.2CF.sub.2CF.sub.2).sub.a″—(OCF.sub.2CF.sub.2CF.sub.2).sub.b″—(OCF.sub.2CF.sub.2).sub.c″—(OCF.sub.2).sub.d″—Rf.sup.2   (3b) wherein: Rf.sup.1 is an alkyl group having 1-16 carbon atoms which may be substituted by one or more fluorine atoms; Rf.sup.2 is an alkyl group having 1-16 carbon atoms which may be substituted by one or more fluorine atoms, a hydrogen atom or a fluorine atom; and in the formula (3a), b″ is an integer of 1 or more and 100 or less; in the formula (3b), a″ and b″ are each independently an integer of 0 or more and 30 or less, and c″ and d″ are each independently an integer of 1 or more and 300 or less; and the occurrence order of the respective repeating units in parentheses with the subscript a″, b″, c″ or d″ is not limited in the formula.

16. The antifouling article according to claim 1 wherein the base material is a glass or a sapphire glass.

17. The antifouling article according to claim 16 wherein the glass is a glass selected from the group consisting of a soda-lime glass, an alkali aluminosilicate glass, a borosilicate glass, a non-alkaline glass, a crystal glass and a quartz glass.

18. The antifouling article according to claim 1 which is an optical member.

Description

EXAMPLES

Example 1

[0130] The diamond-like carbon layer was formed on a chemical strengthening glass (Gorilla glass manufactured by Corning Incorporated; thickness: 0.7 mm) by using methane as a raw material gas in a plasma CVD apparatus. Subsequently, 0.4 mg of an amino group-containing perfluoropoyether compound (A) having the following average composition per one plate of the chemical strengthening glass (55 mm×100 mm) was vacuum-deposited on the diamond-like carbon layer by resistance heating in a vacuum deposition apparatus. Then, the extra surface-treating agent remaining on the treated surface was removed with ethanol to obtain the antifouling coating layer.

[0131] Amino group-containing perfluoropoyether compound (A)

[0132] CF.sub.3CF.sub.2CF.sub.2O(CF.sub.2CF.sub.2CF.sub.2O).sub.21CF.sub.2CF.sub.2CH.sub.2NH.sub.2

Example 2

[0133] The antifouling coating layer was formed similarly to Example 1 except that phosphoric group-containing perfluoropoyether compound (B) having the following average composition was used in place of compound (A).

[0134] Phosphoric group-containing perfluoropoyether compound (B)

[0135] CF.sub.3CF.sub.2CF.sub.2O(CF.sub.2CF.sub.2CF.sub.2O).sub.21CF.sub.2CF.sub.2CH.sub.2OP(O)(OH).sub.2

Comparative Example 1

[0136] A silicon dioxide film was formed on a chemical strengthening glass (Gorilla glass manufactured by Corning Incorporated; thickness: 0.7 mm) by an electron beam evaporation method and 0.4 mg of silane group-containing perfluoropoyether compound (C) having the following average composition per one plate of the chemical strengthening glass (55 mm×100 mm) was vacuum-deposited on the silicon dioxide film by resistance heating. Then, the extra surface-treating agent remaining on the treated surface was removed with ethanol to obtain the antifouling coating layer.

[0137] Silane group-containing perfluoropoyether compound (C)

[0138] CF.sub.3CF.sub.2CF.sub.2O(CF.sub.2CF.sub.2CF.sub.2O).sub.20CF.sub.2CF.sub.2CH.sub.2OCH.sub.2CH.sub.2CH.sub.2Si(OCH.sub.3).sub.3

Comparative Example 2

[0139] A silicon dioxide film was formed on a chemical strengthening glass (Gorilla glass manufactured by Corning Incorporated; thickness: 0.7 mm) by an electron beam evaporation method and 0.4 mg of the following amino propyl triethoxysilane (D) per one plate of the chemical strengthening glass (55 mm×100 mm) was vacuum-deposited on the silicon dioxide film by resistance heating, and further 0.4 mg of silane group-containing perfluoropoyether compound (C) per one plate of the chemical strengthening glass (55 mm×100 mm) was deposited. Then, the extra surface-treating agent remaining on the treated surface was removed with ethanol to obtain the antifouling coating layer.

[0140] Amino propyl triethoxysilane (D)

[0141] NH.sub.2CH.sub.2CH.sub.2CH.sub.2Si(OC.sub.2H.sub.5).sub.3

[0142] Evaluation of Artificial Perspiration Resistant

[0143] For the antifouling coating layers formed on the diamond-like carbon layer in Examples 1 and 2 and Comparative Examples 1 and 2, artificial perspiration resistant was evaluated. Specifically, the base materials on which the antifouling coating layer was formed were immersed in an artificial perspiration having the following composition. The base materials were pulled out of the artificial perspiration for every 48 hours, 168 hours, 504 hours, and 840 hours at 60° C., and the surfaces were washed with distilled water and ethanol. Then, the static water contact angle (degree) was measured. The evaluation was stopped when the measured value of the contact angle became to be less than 100 degree. The results are shown in Table 3 (in the table, symbol “-” means “not measured”).

[0144] Composition of artificial perspiration

Disodium hydrogen phosphate anhydrous: 2 g
Sodium chloride: 20 g
85% lactic acid: 2 g
Histidine hydrochloride: 5 g
Distilled water: 1 kg

TABLE-US-00001 TABLE 1 Contact angle (degree) Immersion Comparative Comparative time (hour) Example 1 Example 2 Example 1 Example 2 0 113 115 114 113 48 112 111 109 110 168 112 111 100 106 504 112 109  88 101 840 111 108 — 96

[0145] As understood from Table 1, it was confirmed that the antifouling coating layer of Examples 1 and 2 had excellent perspiration resistant. The reason for this is considered that the function is maintained since the bond between the diamond-like carbon layer on the surface of the base material and the fluorine-containing compound is not likely to be affected by an alkaline environment. On the other hand, in Comparative Examples 1 and 2, the bond between the diamond-like carbon layer and the fluorine-containing compound (C) is sensitive to a hydrolysis reaction under the alkaline environment of artificial perspiration since the bond is a Si—O—Si bond.

INDUSTRIAL APPLICABILITY

[0146] The present invention can be suitably used for forming the surface-treating layer on a surface of various base materials, in particular an optical member.