ARTICLE WITH SURFACE LAYER

Abstract

To provide an article with a surface layer, that is excellent in fingerprint stain removability, friction resistance, and adhesion to a protective film of the surface layer.

An article with a surface layer, comprising a base material and a surface layer provided on the surface of the base material and characterized in that the surface layer contains groups having —O— between carbon-carbon atoms of a fluoroalkyl group with two or more carbon atoms, and the normalized F intensity obtained by preparing a glass containing 4.96 mass % of fluorine atoms (IGS G4 Fluoride Opal Glass manufactured by Bureau of Analysed Samples Ltd.) as a standard sample, measuring, by an X-ray fluorescence spectrometer, the fluorine atom intensity in the surface layer and the fluorine atom intensity in the standard sample, respectively, and dividing the fluorine atom intensity in the surface layer by the fluorine atom intensity in the standard sample, is from 0.38 to 0.53.

Claims

1. An article with a surface layer, comprising a base material and a surface layer provided on the surface of the base material and characterized in that the surface layer contains groups having —O— between carbon-carbon atoms of a fluoroalkyl group with two or more carbon atoms, and the normalized F intensity in the surface layer obtained by the following method is from 0.38 to 0.53: (Method for Obtaining the Normalized F Intensity) A glass containing 4.96 mass % of fluorine atoms (IGS G4 Fluoride Opal Glass manufactured by Bureau of Analysed Samples Ltd.) is prepared as a standard sample, by an X-ray fluorescence spectrometer, the fluorine atom intensity in the surface layer and the fluorine atom intensity in the standard sample, are measured, respectively, and the fluorine atom intensity in the surface layer is divided by the fluorine atom intensity in the standard sample, whereby the obtained value is adopted as the normalized F intensity.

2. The article with a surface layer according to claim 1, wherein the molecular weight of the groups having —O— between carbon-carbon atoms of the fluoroalkyl group with two or more carbon atoms is from 1,500 to 4,000.

3. The article with a surface layer according to claim 1, wherein the surface layer is a surface layer formed from a fluorinated ether compound having a group having —O— between carbon-carbon atoms of a fluoroalkyl group with two or more carbon atoms, and having a reactive silyl group, or from a fluorinated ether composition containing said fluorinated ether compound.

4. The article with a surface layer according to claim 3, wherein the fluorinated ether compound is a compound represented by the following formula (1):
[R.sup.f—].sub.aQ[-T].sub.b  (1) where R.sup.f is a group having —O— between carbon-carbon atoms of a fluoroalkyl group having two or more carbon atoms (where at least one fluorine atom is bonded to the terminal carbon atom on the Q side), and when there are two or more R.sup.f, the two or more R.sup.f may be the same or different, and Q is an a+b valent linking group, T is —Si(R).sub.3-c(L).sub.c, and when there are two or more T, the two or more T may be the same or different, R is an alkyl group, L is a hydrolyzable group or a hydroxy group, and two or more L in T may be the same or different. a is an integer of at least 1, b is an integer of at least 1, and c is 2 or 3.

5. The article with a surface layer according to claim 4, wherein b is an integer of from 2 to 20.

6. The article with a surface layer according to claim 4, wherein a is an integer from 1 to 6.

7. The article with a surface layer according to claim 4, wherein R.sup.f is a group represented by the following formula (g1):
R.sup.f1—(OR.sup.f2).sub.m—  (g1) where R.sup.11 is a C.sub.1-6 fluoroalkyl group, R.sup.f2 is a C.sub.1-6 fluoroalkylene group (where at least one fluorine atom is bonded to the terminal carbon atom on the Q side of R.sup.f2 bonded to Q), and m is an integer of at least 1, and when m is 2 or more, (OR.sup.f2).sub.m may consist of two or more types of OR.sup.f2.

8. The article with a surface layer according to claim 7, wherein R.sup.f1 is a perfluoroalkyl group.

9. The article with a surface layer according to claim 7, wherein m is an integer of from 4 to 40, and the proportion of perfluoroalkylene groups among all R.sup.f2 is from 60 to 100 mol %.

10. The article with a surface layer according to claim 4, wherein Q is a group represented by the formula (g2-1) (where a=d1+d3, and b=d2+d4), a group represented by the formula (g2-2) (where a=e1, and b=e2), a group represented by the formula (g2-3) (where a=1, and b=2), a group represented by the formula (g2-4) (where a=h1, and b=h2), the group represented by the formula (g2-5) (where a=i1, and b=i2), or a group represented by the formula (g2-6) (where a=1 and b=1): ##STR00034## provided that in the formula (g2-1) to formula (g2-6), the A side is bonded to R.sup.f, and the Q.sup.22, Q.sup.23, Q.sup.24, Q.sup.25 or Q.sup.26 side is bonded to T, A is a single bond, —C(O)NR.sup.6—, —C(O)—, —O—, or —SO.sub.2NR.sup.6—, Q.sup.11 is a single bond, —O—, an alkylene group, or a group having —C(O)NR.sup.6—, —C(O)—, —NR.sup.6—, or —O— between carbon-carbon atoms of an alkylene group with two or more carbon atoms, Q.sup.12 is a single bond, an alkylene group, or a group having —C(O)NR.sup.6—, —C(O)—, —NR.sup.6—, or —O— between carbon-carbon atoms of an alkylene group with two or more carbon atoms, and when Q has two or more Q.sup.12, the two or more Q.sup.12 may be the same or different, Q.sup.13 is a single bond (provided that A is limited to —C(O)—), an alkylene group, a group having —C(O)NR.sup.6—, —C(O)—, —NR.sup.6—, or —O— between carbon-carbon atoms of an alkylene group with two or more carbon atoms, or a group having —C(O)— at the terminal of the N-side of an alkylene group, Q.sup.14 is Q.sup.12 when the atom in Z to which Q.sup.14 is bonded is a carbon atom, or Q.sup.13 when the atom in Z to which Q.sup.14 is bonded is a nitrogen atom, and when Q has two or more Q.sup.14, the two or more Q.sup.14 may be the same or different, Q.sup.15 is an alkylene group, or a group having —C(O)NR.sup.6—, —C(O)—, —NR.sup.6—, or —O— between carbon-carbon atoms of an alkylene group with two or more carbon atoms, and when Q has two or more Q.sup.15, the two or more Q.sup.15 may be the same or different, Q.sup.22 is an alkylene group, a group having —C(O)NR.sup.6—, —C(O)—, —NR.sup.6—, or —O— between carbon-carbon atoms of an alkylene group with two or more carbon atoms, a group having —C(O)NR.sup.6—, —C(O)—, —NR.sup.6—, or —O— at the terminal on the side not connected to Si of an alkylene group, or a group having —C(O)NR.sup.6—, —C(O)—, —NR.sup.6—, or —O— between carbon-carbon atoms of an alkylene group with two or more carbon atoms and having C(O)NR.sup.6—, —C(O)—, —NR.sup.6—, or —O— at the terminal on the side not bonded to Si, and when Q has two or more Q.sup.22, the two or more Q.sup.22 may be the same or different, Q.sup.23 is an alkylene group, or a group having —C(O)NR.sup.6—, —C(O)—, —NR.sup.6—, or —O— between carbon-carbon atoms of an alkylene group with two or more carbon atoms, and the two Q.sup.23 may be the same or different, Q.sup.24 is Q.sup.22 when the atom in Z to which Q.sup.24 is bonded is a carbon atom, Q.sup.23 when the atom in Z to which Q.sup.24 is bonded is a nitrogen atom, and when Q has two or more Q.sup.24, the two or more Q.sup.24 may be the same or different, Q.sup.25 is an alkylene group, or a group having —C(O)NR.sup.6—, —C(O)—, —NR.sup.6, or —O— between carbon-carbon atoms of an alkylene group with two or more carbon atoms, and when Q has two or more Q.sup.25, the two or more Q.sup.25s may be the same or different, Q.sup.26 is an alkylene group, or a group having —C(O)NR.sup.6—, —C(O)—, —NR.sup.6 or —O— between carbon-carbon atoms of an alkylene group with two or more carbon atoms, Z is a group having an a+b valent ring structure having a carbon or nitrogen atom to which Q.sup.14 is directly bonded and a carbon or nitrogen atom to which Q.sup.24 is directly bonded, R.sup.1 is a hydrogen atom or an alkyl group, and when Q has two or more R.sup.1, the two or more R.sup.1 may be the same or different, R.sup.2 is a hydrogen atom, a hydroxy group, an alkyl group, or an acyloxy group, R.sup.3 is an alkyl group, R.sup.6 is a hydrogen atom, a C.sub.1-6 alkyl group, or a phenyl group, d1 is an integer of from 0 to 3, d2 is an integer of from 0 to 3, and d1+d2 is an integer of from 1 to 3, d3 is an integer of from 0 to 3, d4 is an integer of from 0 to 3, and d3+d4 is an integer of from 1 to 3, d1+d3 is an integer of from 1 to 5, and d2+d4 is an integer of from 1 to 5, e1 is an integer of from 1 to 3, e2 is an integer of from 1 to 3, and e1+e2 is 3 or 4, h1 is an integer of at least 1, and h2 is an integer of at least 1, and i1 is an integer of from 1 to 3, i2 is an integer from 1 to 3, and i1+i2 is 3 or 4.

11. The article with a surface layer according to claim 4, wherein L is a C.sub.1-4 alkoxy group.

12. The article with a surface layer according to claim 1, which is a member that constitutes the finger-touching surface of a touch panel.

Description

EXAMPLES

[0241] In the following, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. In the following, “%” means “mass %” unless otherwise specified. Ex. 1 to 4 and 9 to 12 are Examples of the present invention, and Ex. 5 to 8 and 13 to 16 are Comparative Examples.

Ex. 1

[0242] Compound (4-1) was obtained by referring to the method described in Ex. 7 in Examples in WO2013/121984. The average value of x is 6.

CF.sub.3—(OCF.sub.2CF.sub.2—OCF.sub.2CF.sub.2CF.sub.2CF.sub.2).sub.xOCF.sub.2CF.sub.2—OCF.sub.2CF.sub.2CF.sub.2—CH.sub.2—OH  (4-1)

[0243] Compound (1-1) was obtained in the same manner as in Ex. 1 of Patent Document 2, except that R.sup.f—CH.sub.2—OH in Ex. 1 of Patent Document 2 was changed to compound (4-1). The average value of x is 6. The molecular weight of R.sup.f is 2,400.

##STR00026##
F.sup.f═CF.sub.3—(OCF.sub.2CF.sub.2—OCF.sub.2CF.sub.2CF.sub.2CF.sub.2).sub.xOCF.sub.2CF.sub.2—OCF.sub.2OF.sub.2CF.sub.2—

Ex. 2

[0244] Compound (4-2) was obtained by referring to the method described in Ex. 7 in Examples in WO2013/121984. The average value of x is 9.

CF.sub.3—(OCF.sub.2CF.sub.2—OCF.sub.2CF.sub.2CF.sub.2CF.sub.2).sub.xOCF.sub.2CF.sub.2—OCF.sub.2CF.sub.2CF.sub.2—CH.sub.2—OH  (4-2)

[0245] Compound (1-2) was obtained in the same manner as in Ex. 1 of Patent Document 2, except that R.sup.f—CH.sub.2—OH in Ex. 1 of Patent Document 2 was changed to compound (4-2). The average value of x is 9. The molecular weight of R.sup.f is 3,400.

##STR00027##
R.sup.f═CF.sub.3—(OCF.sub.2CF.sub.2—OCF.sub.2CF.sub.2CF.sub.2CF.sub.2).sub.xOCF.sub.2CF.sub.2—OCF.sub.2CF.sub.2CF.sub.2—

Ex. 3

[0246] Compound (4-3) was obtained by referring to the method described in Ex. 11 of WO2013/121984. The average value of x1 is 7, and the average value of x2 is 8.

CF.sub.3CF.sub.2CF.sub.2—{(OCF.sub.2).sub.x1(OCF.sub.2CF.sub.2).sub.x2}OCF.sub.2—CH.sub.2—OH  (4-3)

[0247] Compound (1-3) was obtained in the same manner as in Ex. 1 of Patent Document 2, except that R.sup.f—CH.sub.2—OH in Ex. 1 of Patent Document 2 was changed to compound (4-3). The average value of x1 is 7, and the average value of x2 is 8. The molecular weight of R.sup.f is 1,900.

##STR00028##
R.sup.f═CF.sub.3CF.sub.2CF.sub.2—[(OCF.sub.2x1(OCF.sub.2CF.sub.2).sub.x2]OCF.sub.2—

Ex. 4

[0248] Compound (4-4) was obtained by referring to the method described in Ex. 9 of WO2018/043166. The average value of x is 15.

CF.sub.3CF.sub.2CF.sub.2—{OCF(CF.sub.3)CF.sub.2}.sub.xOCF(CF.sub.3)—CH.sub.2—OH  (4-4)

[0249] Compound (1-4) was obtained in the same manner as in Ex. 1 of Patent Document 2, except that R.sup.f—CH.sub.2—OH in Ex. 1 of Patent Document 2 was changed to compound (4-4). The average value of x is 15. The molecular weight of R.sup.f is 2,900.

##STR00029##
R.sup.f═CF.sub.3CF.sub.2CF.sub.2—{OCF(CF.sub.3)CF.sub.2}.sub.xOCF(CF.sub.3)—

Ex. 5

[0250] Compound (1-5) was obtained in accordance with the method described in Ex. 3 of Patent Document 1. The average value of x is 13. The molecular weight of R.sup.f is 4,700.

##STR00030##
R.sup.f═CH.sub.3—(OCF.sub.2CF.sub.2—OCF.sub.2CF.sub.2CF.sub.2CF.sub.2).sub.xOCF.sub.2CF.sub.2—OCF.sub.2CFCF.sub.2—

Ex. 6

[0251] Compound (4-6) was obtained by referring to the method described in Ex. 7 in Examples in WO2013/121984. The average value of x is 13.

CF.sub.3—(OCF.sub.2CF.sub.2—OCF.sub.2CF.sub.2CF.sub.2CF.sub.2).sub.xOCF.sub.2CF.sub.2—OCF.sub.2CF.sub.2CF.sub.2—CH.sub.2—OH  (4-6)

[0252] Compound (1-6) was obtained in the same manner as in Ex. 1 of Patent Document 2, except that R.sup.f—CH.sub.2—OH in Ex. 1 of Patent Document 2 was changed to compound (4-6). The average value of x is 13. The molecular weight of R.sup.f is 4,700.

##STR00031##
R.sup.f═CF.sub.3—(OCF.sub.2CF.sub.2—OCF.sub.2CF.sub.2CF.sub.2CF.sub.2).sub.xOCF.sub.2CF.sub.2—OCF.sub.2CF.sub.2CF.sub.2—

Ex. 7

[0253] Compound (4-7) was obtained by referring to the method described in Ex. 7 in Examples in WO2013/121984. The average value of x is 3.

CF.sub.3—(OCF.sub.2CF.sub.2—OCF.sub.2CF.sub.2CF.sub.2CF.sub.2).sub.xOCF.sub.2CF.sub.2—OCF.sub.2CF.sub.2CF.sub.2—CH.sub.2—OH  (4-7)

[0254] Compound (1-7) was obtained in the same manner as in Ex. 1 of Patent Document 2, except that R.sup.f—CH.sub.2—OH in Ex. 1 of Patent Document 2 was changed to compound (4-7). The average value of x is 3. The molecular weight of R.sup.f is 1,400.

##STR00032##
R.sup.f═CF.sub.3—(OCF.sub.2CF.sub.2—OCF.sub.2CF.sub.2CF.sub.2CF.sub.2).sub.xOCF.sub.2CF.sub.2—OCF.sub.2CF.sub.2CF.sub.2—

Ex. 8

[0255] Compound (4-8) was obtained by referring to the method described in Ex. 6-1 in Examples in WO2013/121984. The average value of x is 13.

CH.sub.3—(OCF.sub.2CFH—OCF.sub.2CF.sub.2CF.sub.2CH.sub.2).sub.xOCF.sub.2CFH—OCF.sub.2CF.sub.2CF.sub.2—CH.sub.2—OH  (4-8)

[0256] In a 50 mL eggplant flask, 8.0 g of compound (4-8), 0.34 g of allyl bromide, 0.08 g of tetrabutylammonium bromide and 0.60 g of a 48 mass % potassium hydroxide solution were put, and the mixture was stirred at 80° C. for 5 hours. The mixture was cooled to 23° C., 10 g of AC-6000 was put, and the mixture was washed twice with water. The obtained crude solution was purified by silica gel column chromatography to obtain 7.9 g of compound (2-8). The average value of x is 13.

CH.sub.3—(OCF.sub.2CFH—OCF.sub.2CF.sub.2CF.sub.2CH.sub.2).sub.xOCF.sub.2CFH—OCF.sub.2CF.sub.2CF.sub.2—CH.sub.2—OCH.sub.2CH═CH.sub.2   (2-8)

[0257] In a 10 mL glass sample bottle, 6.0 g of compound (2-8), 0.06 g of a xylene solution of platinum/1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2 mass %), 1.01 g of HSi(OCH.sub.3).sub.3, 0.02 g of aniline, 1.0 g of 1,3-bis(trifluoromethyl)benzene (manufactured by Tokyo Chemical Industry Co., Ltd.), were put, and the mixture was stirred at 40° C. for 8 hours. After completion of the reaction, the solvent, etc. were removed under reduced pressure, followed by filtration through a membrane filter of 1.0 μm pore size to obtain 6.5 g of compound (1-8). The average value of x is 13. The molecular weight of R.sup.f is 4000.

##STR00033##
R.sup.f═CH.sub.3—(OCF.sub.2CFH—OCF.sub.2CF.sub.2CF.sub.2CH.sub.2).sub.xOCF.sub.2CFH—OCF.sub.2CF.sub.2CF.sub.2—

Ex. 9

Synthesis Example 9-0

[0258] Compound (9-0) was obtained in accordance with the method described in Ex. 2 (specifically Ex. 2-3) in Examples in WO2013/121984.

CF.sub.3(OCF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CF.sub.2).sub.mOCF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2—C(═O)OCH.sub.3  (9-0)

[0259] Average value of m: 13

Synthesis Example 9-1

[0260] In a 100 mL eggplant flask, 50 g of compound (9-0), 50 g of AC2000 and 1.5 g of H.sub.2NCH.sub.2(C═O)CH(CH.sub.2CH═CH.sub.2).sub.2 were put, and the mixture was stirred at 40° C. for 6 hours. The reaction crude solution was then purified by silica gel chromatography to obtain 26 g of the desired compound (9-1).

CF.sub.3(OCF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CF.sub.2).sub.mOCF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2—CH.sub.2NHCH.sub.2(C═O)CH(CH.sub.2CH═CH.sub.2).sub.2  (9-1)

[0261] NMR spectrum of compound (9-1):

[0262] .sup.1H-NMR: 6.4(1H), 5.6(2H), 4.9(4H), 3.2(2H), 2.0(4H), 1.6(1H)

[0263] .sup.19F-NMR: −55(3F), −82(34F), −87(32F), −115(2F), −126(34F)

Synthesis Example 9-2

[0264] Into a 300 mL three-necked flask equipped with a Dimroth condenser, 26 g of compound (9-1) and 46 g of 1,3-bistrifluoromethylbenzene were added under a dry nitrogen atmosphere, and the mixture was stirred under an ice bath. Then, 7 mL of a 2.5 M lithium aluminum hydride-tetrahydrofuran solution was slowly added, and the mixture was stirred at room temperature for 30 minutes. Then, sodium sulfate decahydrate was added until foaming disappeared, and the solid was removed by Celite filtration. The obtained filtrate was concentrated to obtain 25 g of the desired compound (9-2).

CF.sub.3(OCF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CF.sub.2).sub.mOCF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2—CH.sub.2NHCH.sub.2CH.sub.2CH(CH.sub.2CH═CH.sub.2).sub.2  (9-2)

[0265] NMR spectrum of compound (9-2).

[0266] .sup.1H-NMR: 6.0(2H), 5.3(4H), 3.5(2H), 2.9(2H), 2.3(4H), 1.8(1H)

[0267] .sup.19F-NMR: −55(3F), −82(34F), −87(32F), −115(2F), −126(34F)

Synthesis Example 9-3

[0268] Into a 50 mL three-necked flask under a dry nitrogen atmosphere, 10 g of compound (9-2), 1.1 g of triethylamine and 10 g of 1,3-bistrifluoromethylbenzene were added and while stirring at room temperature, 1.0 g of Cl(C═O)CH(CH.sub.2CH═CH.sub.2).sub.2 was added. The mixture was stirred at room temperature for 24 hours. Then, the reaction crude solution was purified by silica gel chromatography to obtain 2.7 g of the desired compound (9-3).

CF.sub.3(OCF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CF.sub.2).sub.mOCF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2—CH.sub.2N[CH.sub.2CH.sub.2CH(CH.sub.2CH═CH.sub.2).sub.2](C═O)CH(CH.sub.2CH═CH.sub.2).sub.2  (9-3)

[0269] NMR spectrum of compound (9-3):

[0270] .sup.1H-NMR: 5.8 (4H), 5.0 (8H), 4.3 (2H), 3.5 (2H), 3.0 (1H), 2.5 (2H), 2.3 (2H), 2.2 (2H)

[0271] .sup.19F-NMR: −55 (3F), −82 (34F), −87 (32F), −115 (2F), −126 (34F)

Synthesis Example 9-4

[0272] Into a nitrogen-substituted 10 mL eggplant flask, 1.0 g of compound (9-3), 0.004 g of a xylene solution of platinum/1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 3 mass %), 0.009 g of aniline and 1.0 g of AC-6000 were added, and then, 0.14 g of trimethoxysilane was added, followed by stirring at 40° C. for 4 hours. Then, the solvent was removed to obtain 1.1 g of compound (1-9).

CF.sub.3(OCF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2CF.sub.2).sub.mOCF.sub.2CF.sub.2OCF.sub.2CF.sub.2CF.sub.2—CH.sub.2N[CH.sub.2CH(CH.sub.2CH.sub.2C H2Si(OCH.sub.3).sub.3).sub.2](C═O)CH[CH.sub.2CH.sub.2CH.sub.2Si(OCH.sub.3).sub.3].sub.2  (1-9)

[0273] NMR spectrum of compound (1-9):

[0274] .sup.1H-NMR: 4.5 (2H), 3.8 (36H), 3.0 (1H), 2.0 (3H), 1.7 (8H), 1.5 (8H), 0.7 (8H)

[0275] .sup.19F-NMR: −55 (3F), −82 (34F), −87 (32F), −115 (2F), −126 (34F) The average of m was 13.

Ex. 11 to 19: Production and Evaluation of Article with Surface Layer

[0276] A base material was surface treated by using each compound obtained in Ex. 1 to 9 to obtain an article with a surface layer in Ex. 11 to 19. As the surface treating methods, the following dry coating and wet coating methods were used for each Ex. As the base material, chemically strengthened glass was used. The obtained article was evaluated by using the following methods. The results are shown in Table 1.

(Dry Coating Method)

[0277] Dry coating was conducted by using a vacuum deposition apparatus (manufactured by ULVAC, VTR350M) (vacuum deposition method). 0.5 g of each compound obtained in Ex. 1 to 8 was filled into a molybdenum boat in the vacuum deposition apparatus, and the inside of the vacuum deposition apparatus was evacuated to 1×10.sup.−3 Pa or lower. The boat in which the compound was placed, was heated at a temperature-raising rate of 10° C./min or less, and when the deposition rate by a crystal oscillation film thickness meter exceeded 1 nm/sec, the shutter was opened to start film formation on the surface of the base material. When the film thickness reached about 50 nm, the shutter was closed to terminate the film deposition on the surface of the base material. The base material on which the compound was deposited was heat-treated at 200° C. for 30 minutes, and then washed with dichloropentafluoropropane (manufactured by AGC Inc., AK-225) to obtain an article having a surface layer on the surface of the base material.

(Wet Coating Method)

[0278] By mixing each compound obtained in Ex. 1 to 8 with C.sub.4F.sub.90C.sub.2H.sub.5 (Novec (registered trademark) 7200 manufactured by 3M) as a medium, a coating liquid with a solid concentration of 0.05% was prepared. The base material was dipped in the coating liquid and left for 30 minutes, whereupon the base material was pulled up (dip coating method). The coating film was dried at 200° C. for 30 minutes and then washed with AK-225 to obtain an article having a surface layer on the surface of the base material.

(Evaluation Methods)

[0279] <Method for Obtaining the Normalized F Intensity>

[0280] Glass containing 4.96 mass % of fluorine atoms (IGS G4 Fluoride Opal Glass manufactured by Bureau of Analysed Samples Ltd.) was used as a standard sample. Using an X-ray fluorescence analyzer (manufactured by Rigaku, ZSX100e), under conditions of measurement diameter: 30 mm, measurement line: F-Kα, filter: OUT, slit: standard, spectral crystal: RX35 (manufactured by Rigaku), detector: PC, PHA: 100-300, peak angle: 38.794 deg. (20 sec), and B.G. angle: 43.000 deg. (10 sec), the fluorine atom intensity in the surface layer and the fluorine atom intensity in the standard sample were measured. The normalized F intensity in the surface layer of the base material was calculated by dividing the fluorine atom intensity in the surface layer by the fluorine atom intensity in the standard sample. Here, as the standard sample, one having been cleaned with ASAHIKLIN (registered trademark) AE-3000 manufactured by AGC Inc. and dried thoroughly before measurement, was used.

<Fingerprint Stain Removability>

[0281] After an artificial fingerprint liquid (liquid consisting of oleic acid and squalene) was applied to the flat surface of a silicon rubber plug, an excess oil was wiped off with a non-woven cloth (BEMCOT (registered trademark) M-3, manufactured by Asahi Kasei Corporation) to prepare a fingerprint stamp. The fingerprint stamp was placed on the surface layer and pressed with a load of 9.8 N for 10 seconds. The haze at the position where the fingerprint adhered, was measured by a haze meter and adopted as the initial value. The position where the fingerprint adhered, was wiped off by using a reciprocating traverse tester (manufactured by K.N.T.) attached with tissue paper, at a load of 4.9 N. The haze value was measured for every wiping reciprocation, and the number of wiping times where the haze became down to 10% or less of the initial value, was measured. The fewer the number of wiping times, the easier it is to remove the fingerprint stain, and the better the fingerprint stain wiping property. The evaluation standards are as follows.

[0282] ⊚ (Excellent): The number of wiping times is 3 times or less.

[0283] ◯ (Good): The number of wiping times is from 4 to 5 times.

[0284] Δ (Acceptable): The number of wiping times is from 6 to 8 times.

[0285] x (Unacceptable): The number of wiping times is 9 times or more.

<Friction Resistance>

[0286] With respect to the surface layer, by using a reciprocating traverse tester (manufactured by K.N.T.) in accordance with JIS L0849:2013 (ISO 105-X12:2001), a felt (JIS L 3201:2002 R33W) was reciprocated 15,000 times at a load of 9.8 N, a friction length of 4 cm, and a speed of 40 rpm, whereupon the friction resistance was evaluated. For the friction resistance, the above evaluation test for fingerprint removability was conducted on the sample after the above friction, and the fingerprint removability was evaluated using the same evaluation standards. The better the fingerprint removability after the friction resistance test, the smaller the decrease in performance due to friction and the better the friction resistance.

<Adhesion>

[0287] An acrylic adhesive layer of a polyvinyl chloride film having the acrylic adhesive layer (manufactured by Nitto Denko Corporation, ELEP MASKING N-380, tape width: 50 mm) was adhered to the surface layer, and then, in accordance with JIS K6854-1:1999 (ISO 8510-1:1990), the 90-degree peeling force was measured at the time of peeling the polyvinyl chloride film at a peeling speed of 100 mm/min under the condition of 23° C. by using a 90-degree peeling tester (manufactured by Nisshin Kagaku Co., Ltd.). The evaluation standards are as follows. The greater the peeling force, the better the adhesion.

[0288] ⊚ (Excellent): The peeling force is 550 mN/50 mm or more.

[0289] ◯ (Good): The peeling force is at least 370 mN/50 mm and less than 550 mN/50 mm.

[0290] Δ (acceptable): The peeling force is at least 250 mN/50 mm and less than 370 mN/50 mm.

[0291] x (Unacceptable): The peeling force is less than 250 mN/50 mm.

TABLE-US-00001 TABLE 1 Dry coating Wet coating Fingerprint Fingerprint stain Friction Normalized stain Friction Normalized Ex. Compound removability resistance Adhesion F intensity removability resistance Adhesion F intensity 11 (1-1) ◯ ◯ ◯ 0.46 ◯ ◯ ◯ 0.47 12 (1-2) ⊚ ⊚ Δ 0.52 ⊚ ◯ Δ 0.49 13 (1-3) ◯ ◯ ◯ 0.42 ◯ ◯ ⊚ 0.39 14 (1-4) ◯ ◯ ◯ 0.51 ◯ ◯ ◯ 0.49 15 (1-5) ⊚ ⊚ X 0.62 ⊚ ⊚ X 0.66 16 (1-6) ◯ ◯ X 0.58 ◯ ◯ X 0.61 17 (1-7) X X ⊚ 0.23 X X ⊚ 0.22 18 (1-8) Δ X ⊚ 0.36 Δ X ⊚ 0.34 19 (1-9) ⊚ ◯ ◯ 0.50 ⊚ ◯ ◯ 0.44

[0292] Ex. 11 to 14 and 19, in which the normalized F intensity in the surface layer was from 0.38 to 0.53, were confirmed to be excellent in fingerprint stain removability, friction resistance and adhesion to the protective film.

INDUSTRIAL APPLICABILITY

[0293] The article with a surface layer of the present invention can be used as various articles that are required to have water and oil repellency. As the surface layer, for example, a surface protective coating for a display input device such as a touch panel; a surface protective coating for a transparent glass or transparent plastic component; an antifouling coating for kitchen; a water- and moisture-repellent coating or antifouling coating for an electronic device, a heat exchanger, a battery, etc.; an antifouling coating for toiletries; a coating for a component that requires liquid repellency while conducting; a water repellent/waterproof/sliding coating for a heat exchanger; a surface low-friction coating for a vibrating sieve or cylinder interior; etc., may be mentioned. More specific examples of use include front protection plates of displays, anti-reflection plates, polarizing plates, anti-glare plates, or ones having anti-reflection film treatment applied to their surfaces; touch panel sheets or touch panel displays of devices such as cell phones, mobile information terminals, etc.; surface protective coatings for various devices with display input devices that can be operated on the screen by a person's finger or palm, such as touch panel sheets or touch panel displays for mobile phones, mobile information terminals, etc.; decorative building materials around water in toilets, bathrooms, washrooms, kitchens, etc.; waterproof coatings for circuit boards; waterproof or water repellent coatings for heat exchangers; waterproof or water repellent coatings for solar cells; waterproof or water repellent coatings for printed circuit boards; waterproof or water repellent coatings for electronic equipment housings or electronic components; insulation improvement coatings for power transmission lines; waterproof or water repellent coatings for various filters; waterproof coatings for radio wave absorbers or sound absorbers; stain-proof coatings for baths, kitchen equipment or toiletries; waterproof/water repellency/sliding coatings for heat exchangers; surface low friction coatings for vibrating sieves or cylinder interiors; surface protective coatings for machine parts, vacuum equipment parts, bearing parts, automobile parts, tools, etc.

[0294] This application is a continuation of PCT Application No. PCT/JP2020/027727, filed on Jul. 16, 2020, which is based upon and claims the benefit of priority from Japanese Patent Application No. 2019-133052 filed on Jul. 18, 2019. The contents of those applications are incorporated herein by reference in their entireties.