Article having surface treatment layer

Abstract

An article including a base material of zirconium oxide, an intermediate layer located on the base material, and a surface treating layer formed from a surface treating agent containing a fluorine-containing silane compound located on the intermediate layer, wherein the intermediate layer includes one or more metal oxides. Also disclosed is a process for forming the surface treating layer and a process for producing the article.

Claims

1. An article comprising a base material of zirconium oxide, an intermediate layer located on the base material, and a surface treating layer formed from a surface treating agent comprising a fluorine-containing silane compound located on the intermediate layer, wherein the intermediate layer comprises one or more metal oxides, and a total thickness of the intermediate layers is 80 nm or less.

2. The article according to claim 1 wherein the intermediate layer comprises silicon oxide.

3. The article according to claim 1 wherein the intermediate layer comprises silicon oxide and aluminum oxide.

4. The article according to claim 1 wherein the intermediate layer is composed of a plurality of metal oxide layers.

5. The article according to claim 1 wherein the intermediate layer is composed of a plurality of metal oxide layers, the metal oxide layer contacting to the base material is an aluminum oxide layer, and the metal oxide layer contacting to the surface treating layer is a silicon oxide layer.

6. The article according to claim 1 wherein the article is a housing, a glassframe or a jewelry article.

7. The article according to claim 1 wherein the total thickness of the intermediate layers is 50 nm or less.

8. The article according to claim 1 wherein the total thickness of the intermediate layers is 40 nm or less.

9. The article according to claim 1 wherein the intermediate layer comprises silicon oxide or aluminum oxide.

10. The article according to claim 9 wherein the intermediate layer further comprises zirconium oxide.

11. The article according to claim 1 wherein the fluorine-containing silane compound is one or more compounds of the general formula (A1), (A2), (B1), (B2), (C1), (C2), (D1) or (D2): ##STR00018## wherein: PFPE is each independently at each occurrence a group of the formula:
—(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 0-200, the sum of a, b, c and d is at least one, 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; Rf is each independently at each occurrence an alkyl group having 1-16 carbon atoms which may be substituted by one or more fluorine atoms; R.sup.1 is each independently at each occurrence a hydrogen atom or an alkyl group having 1-22 carbon atoms; R.sup.2 is each independently at each occurrence a hydroxyl group or a hydrolyzable group; R.sup.11 is each independently at each occurrence a hydrogen atom or a halogen atom; R.sup.12 is each independently at each occurrence a hydrogen atom or a lower alkyl group; n is, independently per a unit (—SiR.sup.1.sub.nR.sup.2.sub.3-n), an integer of 0-3; there is at least one R.sup.2 in the formulae (A1), (A2), (B1) and (B2); X.sup.1 is each independently a single bond or a 2-10 valent organic group; X.sup.2 is each independently at each occurrence a single bond or a divalent organic group; t is each independently at each occurrence an integer of 1-10; α is each independently an integer of 1-9; α′ is each independently an integer of 1-9; X.sup.5 is each independently a single bond or a 2-10 valent organic group; β is each independently an integer of 1-9; β′ is an integer of 1-9; X.sup.7 is each independently a single bond or a 2-10 valent organic group; γ is each independently an integer of 1-9; γ′ is an integer of 1-9; R.sup.a is each independently at each occurrence —Z—SiR.sup.7 1.sub.pR.sup.7 2.sub.q R.sup.7 3.sub.r; Z is each independently at each occurrence an oxygen atom or a divalent organic group; R.sup.7 1 is each independently at each occurrence R.sup.a′; R.sup.a′ has the same definition as that of R.sup.a; in R.sup.a, the number of Si atoms which are straightly linked via the Z group is up to five; R.sup.7 2 is each independently at each occurrence a hydroxyl group or a hydrolyzable group; R.sup.7 3 is each independently at each occurrence a hydrogen atom or a lower alkyl group; p is each independently at each occurrence an integer of 0-3; q is each independently at each occurrence an integer of 0-3; r is each independently at each occurrence an integer of 0-3; in each —Z—SiR.sup.7 1.sub.pR.sup.7 2.sub.qR.sup.7 3.sub.r, the sum of p, q and r is 3, and there is at least one R.sup.7 2 in the formula (C1) and (C2); R.sup.b is each independently at each occurrence a hydroxyl group or a hydrolyzable group; R.sup.c is each independently at each occurrence a hydrogen atom or a lower alkyl group; k is each independently at each occurrence an integer of 1-3; l is each independently at each occurrence an integer of 0-2; m is each independently at each occurrence an integer of 0-2; the sum of k, 1 and m is 3 in each unit in parentheses with the subscript y; X.sup.9 is each independently a single bond or a 2-10 valent organic group; δ is each independently an integer of 1-9; δ′ is an integer of 1-9; R.sup.d is each independently at each occurrence —Z′—CR.sup.8 1.sub.p′R.sup.8 2.sub.q′R.sup.8 3.sub.r′; Z′ is each independently at each occurrence an oxygen atom or a divalent organic group; R.sup.81 is each independently at each occurrence R.sup.d′; R.sup.d′ has the same definition as that of R.sup.d; in R.sup.d, the number of C atoms which are straightly linked via the Z′ group is up to five; R.sup.82 is each independently at each occurrence —Y—SiR.sup.85.sub.j R.sup.86.sub.3-j; Y is each independently at each occurrence a divalent organic group; R.sup.85 is each independently at each occurrence a hydroxyl group or a hydrolyzable group; R.sup.86 is each independently at each occurrence a hydrogen atom or a lower alkyl group; j is an integer of 1-3 independently per unit —Y—SiR.sup.85.sub.jR.sup.86.sub.3-j; R.sup.83 is each independently at each occurrence a hydrogen atom or a lower alkyl group; p′ is each independently at each occurrence an integer of 0-3; q′ is each independently at each occurrence an integer of 0-3; r′ is each independently at each occurrence an integer of 0-3; R.sup.e is each independently at each occurrence —Y—SiR.sup.85.sub.jR.sup.86.sub.3-j; R.sup.f is each independently at each occurrence a hydrogen atom or a lower alkyl group; k′ is each independently at each occurrence an integer of 0-3; l′ is each independently at each occurrence an integer of 0-3; and m′ is each independently at each occurrence an integer of 0-3; with the proviso that in the formula at least one q′ is 2 or 3, or at least one 1′ is 2 or 3.

12. The article according to claim 11 wherein PFPE is each independently a group of the following formulae (a)-(c):
—(OC.sub.3F.sub.6).sub.b—  (a) in the formula (a), b is an integer of 1-200;
—(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—  (b) in the formula (b), a and b are each independently an integer of 0-30, c and d are each independently an integer of 1-200, the sum of a, b, c and d is an integer of 10-200, 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;
—(R.sup.1 9-R.sup.1 8).sub.n″—  (c) in the formula (c), R.sup.1 9 is OCF.sub.2 or OC.sub.2F.sub.4, R.sup.1 8 is each independently a group selected from OC.sub.2F.sub.4, OC.sub.3F.sub.6 and OC.sub.4F.sub.8, or a combination of 2 or 3 groups independently selected from these groups, and n″ is an integer of 2-100.

13. The article according to claim 11 wherein in PFPE:
—OC.sub.4F.sub.8— is —OCF.sub.2CF.sub.2CF.sub.2CF.sub.2—;
—OC.sub.3F.sub.6— is —OCF.sub.2CF.sub.2CF.sub.2—, and
OC.sub.2F.sub.4— is OCF.sub.2CF.sub.2—.

14. The article according to claim 11 wherein the surface treating agent further comprises one or more components selected from a fluorine-containing oil, a silicone oil and a catalyst.

15. The article according to claim 14 wherein the fluorine containing oil is one or more compounds of the 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)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; and a′, b′, c′ and d′ are the repeating number of each of four repeating units of perfluoropolyether which constitute a main backbone of the polymer, and are each independently an integer of 0-300, 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.

16. The article according to claim 14 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  (3 a)
Rf.sup.1—(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: Re.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; in the formula (3a), b″ is an integer of 1-100; in the formula (3b), a″ and b″ are each independently an integer of 0-30, and c″ and d″ are each independently an integer of 1-300; 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.

17. A process for producing the article according to claim 1, forming the intermediate layer from one or more metal oxides on the base material of zirconium oxide, and then, forming the surface treating layer from a surface treating agent comprising a fluorine-containing silane compound on the intermediate layer.

18. The process according to claim 17 wherein the formation of the intermediate layer is performed by forming an aluminum oxide layer on the base material of zirconium oxide, and then forming a silicon oxide layer on the aluminum oxide layer.

Description

EXAMPLES

(1) Hereinbefore, the article of the present invention is described in detail through Examples. However, the present invention is not limited to Examples.

Preparative Example

(2) The fluorine-containing compound of the following formula (average composition) was dissolved in hydrofluoroether (Novec HFE7200 manufactured by Sumitomo 3M Ltd.)) such that the concentration was 20 wt % to prepare surface-treating agent.

(3) CF.sub.2O(CF.sub.2CF.sub.2O).sub.2 0(CF.sub.2O).sub.1 6CF.sub.2CH.sub.2OCH.sub.2CH.sub.2CH.sub.2CH.sub.2Si[CH.sub.2CH.sub.2Si(OCH.sub.3).sub.3].sub.3

(4) It is noted that in an average composition, although 0.17 repeating units of (CF.sub.2CF.sub.2CF.sub.2CF.sub.2O) and 0.18 repeating unit of (CF.sub.2CF.sub.2CF.sub.2O) were contained, these repeating units were omitted since these amount were slight.

Examples 1-11

(5) The metal oxide shown in the following table was deposited on a base material of zirconium oxide (7 cm×5 cm) at the prescribed thickness by Electron Beam Deposition to form an intermediate layer. Next, the surface treating agent prepared above was deposited on the intermediate layer at the prescribed amount to form a layer of the surface treating agent. Then, the base material on which the surface treating agent was formed was stood at 20° C. under an ambient of humidity of 65% for 24 hours. Thereby, the layer of the surface treating agent was cured and the surface-treating layer was obtained.

Comparative Example 1

(6) The surface-treating layer was formed similarly to the above example except that the surface treating agent was directly deposited without the formation of the intermediate layer on the base material of zirconium oxide.

(7) Evaluation

(8) Evaluation of Friction Durability

(9) A static water contact angle of the surface-treating layers of Examples 1-11 and Comparative Example 1 was measured. The static water contact angle was measured for 1 μL of water by using a contact angle measuring instrument (manufactured by KYOWA INTERFACE SCIENCE Co., Ltd.).

(10) Firstly, as an initial evaluation, the static water contact angle of the surface-treating layer of which the surface had not still contacted with anything after formation thereof was measured (the number of rubbing is zero).

(11) Then, as an evaluation of the friction durability, a steel wool friction durability evaluation was performed. Specifically, the base material on which the surface-treating layer was formed was horizontally arranged, and then, a steel wool (grade No. 0000, dimensions: 10 mm×10 mm) was contacted with the exposed surface of the surface-treating layer and a load of 1000 gf was applied thereon. Then, the steel wool was shuttled while applying the load (distance: 120 mm (reciprocation), rate: 60 rpm). The evaluation was stopped when the measured value of the contact angle became to be less than 100 degree. The number of reciprocation is shown in the following table at the time of becoming the contact angle less than 100 degree.

(12) Appearance Evaluation

(13) The surface of the base material was evaluated after the deposition. The evaluation criteria are as follows:

(14) ∘: It looks smooth, and the surface reflection was not observed.

(15) Δ: Some surface reflection was observed.

(16) x: It looks unsmooth, and the surface reflection was observed.

(17) TABLE-US-00001 TABLE 1 Intermediate layer Metal Surface oxide treating (Left layer side is Thickness Surface Thickness base of treating of Evaluation material layer agent layer Durability side) (nm) (mg) (nm) (times) Appearance Example 1 SiO.sub.2 13 60 15 2000 ∘ Example 2 SiO.sub.2 30 120 30 2000 ∘ Example 3 Al.sub.2O.sub.3 40 120 30 2000 ∘ Example 4 Al.sub.2O.sub.3/SiO.sub.2 10/13 60 15 2000 ∘ Example 5 Al.sub.2O.sub.3/SiO.sub.2 40/13 60 15 2000 ∘ Example 6 Al.sub.2O.sub.3/SiO.sub.2 13/13 120 30 5000 ∘ Example 7 Al.sub.2O.sub.3/SiO.sub.2 15/15 120 30 7000 ∘ Example 8 Al.sub.2O.sub.3/SiO.sub.2 20/20 120 30 7000 ∘ Example 9 Al.sub.2O.sub.3/SiO.sub.2/ 20/20/20/ 120 30 2000 ∘ Al.sub.2O.sub.3/SiO.sub.2 20 Example ZrO.sub.2/Al.sub.2O.sub.3/ 10/10/13 60 15 2000 ∘ 10 SiO.sub.2 Example ZrO.sub.2/Al.sub.2O.sub.3/ 40/10/13 120 30 3000 Δ 11 SiO.sub.2 Comparative — — 60 15 1000 x Example 1

(18) As seen from the above results, it was confirmed that the friction durability was improved by forming the intermediate layer of the metal oxide on the base material of zirconium oxide.

INDUSTRIAL APPLICABILITY

(19) The present invention is suitably applied for forming the surface treating layer having high friction durability on the base material of zirconium oxide.

(20) The present invention includes following embodiments:

(21) Embodiment 1. An article comprising

(22) a base material of zirconium oxide,

(23) an intermediate layer located on the base material, and

(24) a surface treating layer formed from a surface treating agent comprising a fluorine-containing silane compound located on the intermediate layer,

(25) wherein the intermediate layer comprises one or more metal oxides.

(26) Embodiment 2. The article according to Embodiment 1 wherein the intermediate layer comprises silicon oxide or aluminum oxide.

(27) Embodiment 3. The article according to Embodiment 1 or 2 wherein the intermediate layer comprises silicon oxide.

(28) Embodiment 4. The article according to any one of Embodiments 1-3 wherein the intermediate layer comprises silicon oxide and aluminum oxide.

(29) Embodiment 5. The article according to any one of Embodiments 2-4 wherein the intermediate layer further comprises zirconium oxide.

(30) Embodiment 6. The article according to any one of Embodiments 1-5 wherein the intermediate layer is composed of a plurality of metal oxide layers.

(31) Embodiment 7. The article according to any one of Embodiments 1-6 wherein

(32) the intermediate layer is composed of a plurality of metal oxide layers,

(33) the metal oxide layer contacting to the base material is an aluminum oxide layer, and

(34) the metal oxide layer contacting to the surface treating layer is a silicon oxide layer.

(35) Embodiment 8. The article according to any one of Embodiments 1-7 wherein the fluorine-containing silane compound is one or more compounds of the general formula (A1), (A2), (B1), (B2), (C1), (C2), (D1) or (D2):

(36) ##STR00017##
wherein:

(37) PFPE is each independently at each occurrence a group of the formula:

(38) —(OC.sub.4F.sub.8).sub.a—(OC.sub.3F.sub.6).sub.b—(OC.sub.2 F.sub.4).sub.c—(OCF.sub.2).sub.d—

(39) wherein a, b, c and d are each independently an integer of 0-200, the sum of a, b, c and d is at least one, 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;

(40) Rf is each independently at each occurrence an alkyl group having 1-16 carbon atoms which may be substituted by one or more fluorine atoms;

(41) R.sup.1 is each independently at each occurrence a hydrogen atom or an alkyl group having 1-22 carbon atoms;

(42) R.sup.2 is each independently at each occurrence a hydroxyl group or a hydrolyzable group;

(43) R.sup.11 is each independently at each occurrence a hydrogen atom or a halogen atom;

(44) R.sup.12 is each independently at each occurrence a hydrogen atom or a lower alkyl group;

(45) n is, independently per a unit (—SiR.sup.1R.sup.2.sub.3-n), an integer of 0-3;

(46) there is at least one R.sup.2 in the formulae (A1), (A2), (B1) and (B2);

(47) X.sup.1 is each independently a single bond or a 2-10 valent organic group;

(48) X.sup.2 is each independently at each occurrence a single bond or a divalent organic group;

(49) t is each independently at each occurrence an integer of 1-10;

(50) α is each independently an integer of 1-9;

(51) α′ is each independently an integer of 1-9;

(52) X.sup.5 is each independently a single bond or a 2-10 valent organic group;

(53) β is each independently an integer of 1-9;

(54) β′ is an integer of 1-9;

(55) X.sup.7 is each independently a single bond or a 2-10 valent organic group;

(56) γ is each independently an integer of 1-9;

(57) γ′ is an integer of 1-9;

(58) R.sup.a is each independently at each occurrence —Z—SiR.sup.7 1.sub.p R.sup.7 2.sub.q R.sup.7 3.sub.r;

(59) Z is each independently at each occurrence an oxygen atom or a divalent organic group;

(60) R.sup.7 1 is each independently at each occurrence R.sup.a′;

(61) R.sup.a′ has the same definition as that of R.sup.a;

(62) in R.sup.a, the number of Si atoms which are straightly linked via the Z group is up to five;

(63) R.sup.7 2 is each independently at each occurrence a hydroxyl group or a hydrolyzable group;

(64) R.sup.7 3 is each independently at each occurrence a hydrogen atom or a lower alkyl group;

(65) p is each independently at each occurrence an integer of 0-3;

(66) q is each independently at each occurrence an integer of 0-3;

(67) r is each independently at each occurrence an integer of 0-3;

(68) in each —Z—SiR.sup.7 1.sub.p R.sup.7 2.sub.q R.sup.7 3.sub.r, the sum of p, q and r is 3, and there is at least one R.sup.7 2 in the formula (C1) and (C2);

(69) R.sup.b is each independently at each occurrence a hydroxyl group or a hydrolyzable group;

(70) R.sup.c is each independently at each occurrence a hydrogen atom or a lower alkyl group;

(71) k is each independently at each occurrence an integer of 1-3;

(72) l is each independently at each occurrence an integer of 0-2;

(73) m is each independently at each occurrence an integer of 0-2;

(74) the sum of k, 1 and m is 3 in each unit in parentheses with the subscript y;

(75) X.sup.9 is each independently a single bond or a 2-10 valent organic group;

(76) δ is each independently an integer of 1-9;

(77) δ′ is an integer of 1-9;

(78) R.sup.d is each independently at each occurrence —Z′—CR.sup.8 1.sub.p′R.sup.8 2.sub.q′R.sup.8 3.sub.r′;

(79) Z′ is each independently at each occurrence an oxygen atom or a divalent organic group;

(80) R.sup.81 is each independently at each occurrence R.sup.d;

(81) R.sup.d′ has the same definition as that of R.sup.d;

(82) in R.sup.d, the number of C atoms which are straightly linked via the Z′ group is up to five;

(83) R.sup.82 is each independently at each occurrence —Y-Sir.sup.85.sub.jR.sup.86.sub.3-j;

(84) Y is each independently at each occurrence a divalent organic group;

(85) R.sup.85 is each independently at each occurrence a hydroxyl group or a hydrolyzable group;

(86) R.sup.86 is each independently at each occurrence a hydrogen atom or a lower alkyl group;

(87) j is an integer of 1-3 independently per unit —Y—SiR.sup.85.sub.jR.sup.86.sub.3-j;

(88) R.sup.83 is each independently at each occurrence a hydrogen atom or a lower alkyl group;

(89) p′ is each independently at each occurrence an integer of 0-3;

(90) q′ is each independently at each occurrence an integer of 0-3;

(91) r′ is each independently at each occurrence an integer of 0-3;

(92) R.sup.e is each independently at each occurrence —Y—SiR.sup.85.sub.jR.sup.86.sub.3-j;

(93) R.sup.f is each independently at each occurrence a hydrogen atom or a lower alkyl group;

(94) k′ is each independently at each occurrence an integer of 0-3;

(95) l′ is each independently at each occurrence an integer of 0-3; and

(96) m′ is each independently at each occurrence an integer of 0-3;

(97) with the proviso that in the formula at least one q′ is 2 or 3, or at least one 1′ is 2 or 3.

(98) Embodiment 9. The article according to Embodiment 8 wherein PFPE is each independently a group of the following formulae (a)-(c):

(99) (a) —(OC.sub.3F.sub.6).sub.b—

(100) in the formula (a), b is an integer of 1-200;

(101) (b) —(OC.sub.4 F.sub.8).sub.a—(OC.sub.3 F.sub.6).sub.b—(OC.sub.2 F.sub.4).sub.c—(OCF.sub.2).sub.d—

(102) in the formula (b), a and b are each independently an integer of 0-30, c and d are each independently an integer of 1-200, the sum of a, b, c and d is an integer of 10-200, 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;

(103) (c) —(R.sup.19-R.sup.18).sub.n″—

(104) in the formula (c), R.sup.19 is OCF.sub.2 or OC.sub.2 F.sub.4, R.sup.18 is each independently a group selected from OC.sub.2 F.sub.4, OC.sub.3 F.sub.6 and OC.sub.4 F.sub.8, or a combination of 2 or 3 groups independently selected from these groups, and n″ is an integer of 2-100.

(105) Embodiment 10. The article according to Embodiment 8 or 9 wherein in PFPE:

(106) OC.sub.4 F.sub.8— is —OCF.sub.2 CF.sub.2 CF.sub.2 CF.sub.2—,

(107) OC.sub.3 F.sub.6— is —OCF.sub.2 CF.sub.2 CF.sub.2—, and

(108) OC.sub.2 F.sub.4— is —OCF.sub.2 CF.sub.2.

(109) Embodiment 11. The article according to any one of Embodiments 8-10 wherein the surface treating agent further comprises one or more components selected form a fluorine-containing oil, a silicone oil and a catalyst.

(110) Embodiment 12. The article according to Embodiment 11 wherein the fluorine containing oil is one or more compounds of the formula (3):

(111) Rf.sup.1—(OC.sub.4 F.sub.8).sub.a′—(OC.sub.3F.sub.6).sub.b′—(OC.sub.2 F.sub.4).sub.c′—(OCF.sub.2).sub.d′—RF.sup.2 (3)

(112) wherein:

(113) Rf.sup.1 is an alkyl group having 1-16 carbon atoms which may be substituted by one or more fluorine atoms;

(114) 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; and

(115) a′, b′, c′ and d′ are the repeating number of each of four repeating units of perfluoropolyether which constitute a main backbone of the polymer, and are each independently an integer of 0-300, 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.

(116) Embodiment 13. The article according to Embodiment 11 or 12 wherein the fluorine containing oil is one or more compounds of the formula (3a) or (3b):

(117) Rf.sup.1—(OCF.sub.2 CF.sub.2 CF.sub.2).sub.b″-Rf.sup.2 (3a)

(118) Rf.sup.1—(OCF.sub.2 CF.sub.2 CF.sub.2 CF.sub.2).sub.a″—(OCF.sub.2 CF.sub.2 CF.sub.2).sub.b″—(OCF.sub.2 CF.sub.2).sub.c″—(OCF.sub.2).sub.d″—Rf.sup.2 (3b)

(119) wherein:

(120) Rf.sup.1 is an alkyl group having 1-16 carbon atoms which may be substituted by one or more fluorine atoms;

(121) 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;

(122) in the formula (3a), b″ is an integer of 1-100;

(123) in the formula (3b), a″ and b″ are each independently an integer of 0-30, and c″ and d″ are each independently an integer of 1-300; and

(124) the occurrence order of the respective repeating units in parentheses with the subscript a″, b″, c″ or d″ is not limited in the formula.

(125) Embodiment 14. The article according to any one of Embodiments 1-13 wherein the article is a housing, a glassframe or a jewelry article.

(126) Embodiment 15. A process for forming a surface treating layer from a surface treating agent comprising a fluorine-containing silane compound on a base material of zirconium oxide, comprising:

(127) forming an intermediate layer from one or more metal oxides on the base material of zirconium oxide, and then forming the surface treating layer from a surface treating agent comprising a fluorine-containing silane compound on the intermediate layer.

(128) Embodiment 16. The process according to Embodiment 15 wherein the intermediate layer comprises silicon oxide or aluminum oxide.

(129) Embodiment 17. The process according to Embodiment 15 or 16 wherein the intermediate layer comprises silicon oxide.

(130) Embodiment 18. The process according to any one of Embodiments 15-17 wherein the intermediate layer comprises silicon oxide and aluminum oxide.

(131) Embodiment 19. The process according to any one of Embodiments 15-18 wherein the intermediate layer further comprises zirconium oxide.

(132) Embodiment 20. The process according to any one of Embodiments 15-19 wherein the formation of the intermediate layer is performed by forming an aluminum oxide layer on the base material of zirconium oxide, and then forming a silicon oxide layer on the aluminum oxide layer.

(133) Embodiment 21. A process for producing an article comprising

(134) a base material of zirconium oxide,

(135) an intermediate layer located on the base material, and

(136) a surface treating layer formed from a surface treating agent comprising a fluorine-containing silane compound located on the intermediate layer, comprising:

(137) forming an intermediate layer from one or more metal oxides on the base material of zirconium oxide, and then, forming the surface treating layer from a surface treating agent comprising a fluorine-containing silane compound on the intermediate layer.

(138) Embodiment 22. The process according to Embodiment 21 wherein the formation of the intermediate layer is performed by forming an aluminum oxide layer on the base material of zirconium oxide, and then forming a silicon oxide layer on the aluminum oxide layer.