Fluorine-containing ether composition, coating liquid and article

Abstract

To provide a fluorine-containing ether composition capable of forming a surface layer excellent in water drop slip property.SOLUTION: A fluorine-containing ether composition is a composition containing a fluorine-containing ether compound (A) and a fluorine-containing ether compound (B), in which the compound (A) and the compound (B) each has a poly(oxyperfluoroalkylene) chain, a perfluoroalkyl group bonded to one terminal thereof and a group represented by formula (I), in the combination of the compound (A) and the compound (B) contained in the composition, the carbon number of the perfluoroalkyl group of the compound (A) is smaller than the carbon number of the perfluoroalkyl group of the compound (B), and a content of the compound (A) is 30-95 mass% to the total of the compound (A) and the compound (B). In formula (I):SiRnL3-n, L is a hydroxyl group or a hydrolyzable group, R is a hydrogen atom or a monovalent hydrocarbon group, and n is an integer of 0-2.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a fluorinated ether composition, a coating liquid, and an article. [Background technology]

[0002] Fluorine-containing compounds are used as surface treatment agents, etc., because they exhibit high lubricity, water repellency, oil repellency, etc. For example, when a surface layer is formed on the surface of a substrate using the surface treatment agent, lubricity, water repellency, oil repellency, etc. are imparted, making it easier to wipe off dirt on the substrate surface and improving dirt removability. Among fluorine-containing compounds, fluorine-containing ether compounds having a poly(oxyperfluoroalkylene) chain in which an ether bond (-O-) exists in the middle of the perfluoroalkyl chain are excellent in removing dirt such as oil and fat.

[0003] As a fluorine-containing ether compound, one having a hydrolyzable silyl group has been proposed. Such a fluorine-containing ether compound is used in applications requiring a long-term maintenance of the performance of preventing the deterioration of water and oil repellency even when rubbed repeatedly with fingers (abrasion resistance) and the performance of easily removing fingerprints attached to the surface by wiping (fingerprint stain removability), for example, as a surface treatment agent for members constituting the surface touched by fingers of a touch panel.

[0004] As the fluorine-containing ether compound, for example, the following fluorine-containing ether compounds have been proposed. A fluorine-containing ether compound (Patent Document 1) has a poly(oxyperfluoroalkylene) group unit having 1 to 3 groups (α) consisting of at least one kind of oxyperfluoroalkylene group having 1 to 2 carbon atoms and 1 to 3 groups (β) consisting of at least one kind of oxyperfluoroalkylene group having 3 to 6 carbon atoms, has a poly(oxyperfluoroalkylene) chain formed by linking two or more of the units, and has a hydrolyzable silyl group at at least one end of the poly(oxyperfluoroalkylene) chain via a linking group. Furthermore, Patent Document 1 discloses a composition containing 95% by mass or more of the above-mentioned fluorinated ether compound, and a mixture containing two kinds of the above-mentioned fluorinated ether compounds. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2013 / 121984 Summary of the Invention [Problem to be solved by the invention]

[0006] However, the present inventors have found that the surface layer formed from the fluorinated ether compound, composition or mixture described in Patent Document 1 has insufficient water droplet sliding property. Note that water droplet sliding property refers to the property of water droplets easily sliding down an inclined surface (small rolling angle and / or fast sliding speed). An object of the present invention is to provide a fluorinated ether composition and a coating liquid capable of forming a surface layer excellent in water droplet sliding property, and an article having a surface layer excellent in water droplet sliding property. [Means for solving the problem]

[0007] The present invention provides a fluorinated ether composition, a coating liquid and an article having the following configurations [1] to

[15] . [1] A composition comprising a fluorinated ether compound (A) and a fluorinated ether compound (B), The fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) each have a poly(oxyperfluoroalkylene) chain, a perfluoroalkyl group bonded to one end of the chain, and a group represented by the following formula (I): In a combination of the fluorinated ether compound (A) and the fluorinated ether compound (B) contained in the composition, the number of carbon atoms in the perfluoroalkyl group of the fluorinated ether compound (A) is smaller than the number of carbon atoms in the perfluoroalkyl group of the fluorinated ether compound (B), A fluorinated ether composition, characterized in that the content of said fluorinated ether compound (A) is 30 to 95 mass% based on the total content of said fluorinated ether compound (A) and said fluorinated ether compound (B). -SiR n L 3-n (I) where L is a hydroxyl group or a hydrolyzable group, R is a hydrogen atom or a monovalent hydrocarbon group; n is an integer from 0 to 2; When n is 0 or 1, (3-n) L's may be the same or different. When n is 2, n R's may be the same or different. The groups represented by the formula (I) that the fluorinated ether compound (A) and the fluorinated ether compound (B) have may be the same or different.

[0008] [2] The fluorine-containing ether composition according to [1], wherein the perfluoroalkyl group in the fluorine-containing ether compound (A) has 1 to 19 carbon atoms, and the perfluoroalkyl group in the fluorine-containing ether compound (B) has 2 to 20 carbon atoms. [3] The fluorine-containing ether composition according to [1] or [2], wherein the perfluoroalkyl group of the fluorine-containing ether compound (A) has 1 carbon atom and the perfluoroalkyl group of the fluorine-containing ether compound (B) has 2 or 3 carbon atoms, or the perfluoroalkyl group of the fluorine-containing ether compound (A) has 2 carbon atoms and the perfluoroalkyl group of the fluorine-containing ether compound (B) has 3 carbon atoms. [4] The fluorinated ether composition according to any of [1] to [3], wherein each of the fluorinated ether compound (A) and the fluorinated ether compound (B) has 1 to 3 groups represented by the formula (I). [5] The fluorinated ether composition according to any of [1] to [4], wherein each of the fluorinated ether compound (A) and the fluorinated ether compound (B) has 1 to 3 poly(oxyperfluoroalkylene) chains.

[0009] [6] The fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) are both fluorine-containing ether compounds represented by the following formula (A / B), and in the combination of the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) contained in the composition, R f The number of carbon atoms in the fluorine-containing ether compound (B) is f A fluorine-containing ether composition of [1], wherein the number of carbon atoms is less than that of [R f -OQR PF -] r Z[-SiR n L 3-n ] s (A / B) However, R f is a perfluoroalkyl group, and when r is 2 or more, the r perfluoroalkyl groups are the same perfluoroalkyl group, Q is a single bond, an oxyfluoroalkylene group containing one or more hydrogen atoms, or a polyoxyfluoroalkylene group formed by bonding 2 to 5 of the oxyfluoroalkylene groups, and the oxyfluoroalkylene groups constituting the group may all be the same or different; R PF is a poly(oxyperfluoroalkylene) chain, Z is a linking group having a valence of (r+s), -SiR n L 3-n is a group represented by the formula (I), and when s is 2 or more, the s groups represented by the formula (I) are the same group, Each of r and s is an integer of 1 or more, and r+s is 8 or less. [7] The fluorinated ether composition according to [6], wherein the r is 1 to 3. [8] The fluorinated ether composition according to [6] or [7], wherein s is 1 to 3.

[0010] [9] A fluorinated ether composition comprising a fluorinated ether compound (A1) represented by the following formula (A1) and a fluorinated ether compound (B1) represented by the following formula (B1), wherein the content of the fluorinated ether compound (A1) is 30 to 95 mass% based on the total amount of the fluorinated ether compound (A1) and the fluorinated ether compound (B1): [R fa -OQ a -R PFa -] r1 Z a [-SiR a n1 L a 3-n1 ] s1 (A1) [R fb -OQ b -R PFb -] r2 Z b [-SiR b n2 L b 3-n2 ] s2 (B1) However, R fa and R fb is a perfluoroalkyl group, and R fa The number of carbon atoms in R fb The number of carbon atoms is less than that of Q a and Q b represents a single bond, an oxyfluoroalkylene group containing one or more hydrogen atoms, or a polyoxyfluoroalkylene group formed by bonding 2 to 5 of the oxyfluoroalkylene groups, and the oxyfluoroalkylene groups constituting the group may all be the same or different, R PFa and R PFb is a poly(oxyperfluoroalkylene) chain, Z a is a (r1+s1)-valent linking group, Z b is a (r2+s2)-valent linking group, L a and L b is a hydroxyl group or a hydrolyzable group, R a and R b is a hydrogen atom or a monovalent hydrocarbon group, n1 and n2 are integers from 0 to 2, (3-n1) Ls where n1 is 0 or 1 a , (3-n) Ls where n2 is 0 or 1 b may be the same or different, When n1 is 2, n1 R a , n2 R when n2 is 2 b may be the same or different, r1 and r2 are integers of 1 or more, and when r1 is 2 or more, r1 R fa , Q a and R PFa may be the same or different, and when r2 is 2 or more, r2 R fb , Q b and R PFb may be the same or different, s1 and s2 are integers of 1 or more, and when s1 is 2 or more, s1 of [-SiR a n1 L a 3-n1 ] may be the same or different, and when s2 is 2 or more, s2 [-SiR b n2 L b 3-n2 ] may be the same or different.

[0011]

[10] When r1 in the formula (A1) is 2 or more, r1 R fa The fluorine-containing ether composition of [9], wherein

[11] When r2 in the formula (A2) is 2 or more, r2 R fbThe fluorine-containing ether composition of [9] or

[10] , wherein

[12] R in the above formula (A1) fa The number of carbon atoms is 1 to 19, and R in the formula (B1) fb The fluorinated ether composition according to any one of [9] to

[11] , wherein the carbon number is 2 to 20.

[13] R in the above formula (A1) fa The number of carbon atoms is 1, and R in the formula (B1) fb The number of carbon atoms in R in the formula (A1) is 2 or 3. fa The number of carbon atoms is 2, and R in the formula (B1) fb The fluorinated ether composition according to any one of [9] to

[12] , wherein the carbon number is 3.

[0012]

[14] A coating liquid comprising the fluorinated ether composition according to any one of the above [1] to

[13] and a liquid medium.

[15] An article having a surface layer formed from the fluorinated ether composition according to any one of [1] to

[13] above. Effect of the Invention

[0013] The fluorinated ether composition and coating liquid of the present invention can form a surface layer that is excellent in water droplet sliding property. The article of the present invention has a surface layer that is excellent in water droplet sliding property. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] In this specification, a compound represented by formula (1) is referred to as compound (1), and a group represented by formula (I) is referred to as group (I). Compounds or groups represented by other formulas are also referred to in the same manner. In addition, the chemical formula of an oxyperfluoroalkylene group is represented by writing the oxygen atom to the right of the perfluoroalkylene group. The term "surface layer" refers to a layer formed on the surface of a substrate.

[0015] [Fluorine-containing ether composition] The fluorine-containing ether composition of the present invention (hereinafter also referred to as "the composition") contains a fluorine-containing ether compound (A) (hereinafter also referred to as "compound (A)") and a fluorine-containing ether compound (B) (hereinafter also referred to as "compound (B)"). As described below, the composition does not contain a liquid medium. The composition may consist of compound (A) and compound (B), and may contain fluorine-containing ether compounds other than compound (A) and compound (B) and impurities other than compound (A), compound (B) and other fluorine-containing ether compounds, as described below. Compound (A) and compound (B) each have a poly(oxyperfluoroalkylene) chain (hereinafter, “R PF A perfluoroalkyl group (hereinafter referred to as "R f and a group represented by the following formula (I) (hereinafter also referred to as "group (I)").

[0016] -SiR n L 3-n (I) where L is a hydroxyl group or a hydrolyzable group, R is a hydrogen atom or a monovalent hydrocarbon group; n is an integer from 0 to 2; When n is 0 or 1, (3-n) L's may be the same or different. When n is 2, the n R's may be the same or different.

[0017] R of compound (A) f The number of carbon atoms in the R f The number of carbon atoms in the R PF Chain and R f As the fluorine-containing ether compound having a group and a group (I), f It contains two types of groups with different carbon numbers, which gives the surface layer excellent water droplet sliding properties. R of each of compound (A) and compound (B) PF The chain and the group (I) may each be the same or different.

[0018] (R f basis) R f The carbon number of the group is preferably 1 to 20, more preferably 1 to 10, further preferably 1 to 6, and particularly preferably 1 to 3, in that the surface layer has better lubricity and abrasion resistance. Therefore, R of compound (A) f The carbon number of the group is 1 to 19, and R f The carbon number of the R group is preferably 2 to 20. f The carbon number of the group is 1 to 9, and R f It is more preferable that the carbon number of the R group is 2 to 10. f The carbon number of the group is 1 to 5, and R f It is more preferable that the carbon number of the R group is 2 to 6. f The carbon number of the group is 1, and R f The carbon number of the group is 2 or 3, or the R f The carbon number of the group is 2, and R f It is particularly preferred that the group has 3 carbon atoms. R f The group may be branched or linear, preferably linear. f Examples of the group include CF3-, CF3CF2-, CF3CF2CF2-, and the like, with CF3- and CF3CF2- being particularly preferred.

[0019] R of compound (A) f The number of groups is R PF The number of chains is the same as that of the compound (A). f When the group has two or more, each R f The groups may all be the same or different, and preferably are the same. Similarly, R of compound (B) f The number of groups is R PF The number of chains is the same as that of the compound (B). f When the group has two or more, each R fThe groups may all be the same or different, and preferably are the same. However, R of compound (A) f R with the largest number of carbon atoms f The number of carbon atoms in the R f R with the smallest carbon number of the groups f The number of carbon atoms in the group is less than that of the

[0020] R f The combination of groups is R f The group is CF3-, and the R f The combination of the group CF3CF2-, R f The group is CF3-, and the R f A combination of CF3CF2CF2- groups, R f The group is CFCF-, and the R f A combination of the group CF3CF2CF2- is preferred, and the R f The group is CF3-, and the R f Particularly preferred is the combination of groups CF3CF2-.

[0021] R f The group is typically connected to the R PF Attached to one end of the chain. The linking group is preferably the group (II). That is, R PF At one end of the chain, R f It is preferable that the left side of group (II) is R f Attaches to the group. -OQ- ···(II) Here, Q is a single bond, an oxyfluoroalkylene group containing one or more hydrogen atoms, or a polyoxyfluoroalkylene group formed by bonding 2 to 5 (preferably 2 to 4) of the oxyfluoroalkylene groups. The oxyfluoroalkylene groups constituting the group may all be the same or different.

[0022] Q is an oxyfluoroalkylene group having a hydrogen atom or a polyoxyfluoroalkylene group formed by bonding 2 to 5 of the oxyfluoroalkylene groups, so that the solubility of the compound (A) and the compound (B) in a liquid medium is increased. Therefore, the compound (A) and the compound (B) are less likely to aggregate in the coating liquid, and also, after being applied to the surface of the substrate, the compound (A) and the compound (B) are less likely to aggregate during drying, so that the appearance of the surface layer is further improved. The oxyfluoroalkylene group for Q preferably has 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms, and particularly preferably 2 or 3 carbon atoms. The number of hydrogen atoms in the oxyfluoroalkylene group is at least 1, preferably at least 2, and particularly preferably at least 3, from the viewpoint of excellent appearance of the surface layer. The number of hydrogen atoms in the oxyfluoroalkylene group is preferably at most (the number of carbon atoms in Q)×2, and particularly preferably at most (the number of carbon atoms in Q), from the viewpoint of further excellent water and oil repellency of the surface layer. The oxyfluoroalkylene group may be an oxyfluoroalkylene group having no branched structure, or may be an oxyfluoroalkylene group having a branched structure. In view of the fact that the surface layer has further excellent wear resistance and lubricity, an oxyfluoroalkylene group having no branched structure is preferred. In a group formed by bonding 2 to 5 oxyfluoroalkylene groups, the 2 to 5 oxyfluoroalkylene groups may be the same or different. From the viewpoint of ease of production of compound (A) and compound (B), Q is preferably a single bond or a group selected from the group consisting of -CHFCF2OCH2CF2O-, -CF2CHFCF2OCH2CF2O-, -CF2CF2CHFCF2OCH2CF2O-, -CF2CF2OCHFCF2OCH2CF2O-, -CF2CF2OCF2CF2OCHFCF2OCH2CF2OCH2CF2O-, -CF2CH2OCH2CF2O-, and -CF2CF2OCF2CH2OCH2CF2O- (wherein the left side is bonded to O).

[0023] (R PF chain) R PFThe chain may be, for example, R represented by the following formula (1): PF Chains are mentioned. (R F O) m1 (1) However, R F is a perfluoroalkylene group, m1 is an integer from 2 to 200; (R F O) m1 R has two or more different carbon numbers. F It may consist of O.

[0024] R F The number of carbon atoms in the alkyl group is preferably 1 to 6, and more preferably 1 to 4, from the viewpoint of providing a surface layer with even better abrasion resistance and fingerprint removability, and is particularly preferably 1 to 2, from the viewpoint of providing a surface layer with even better abrasion resistance. A perfluoroalkylene group having 3 to 4 carbon atoms is particularly preferred, from the viewpoint of providing a surface layer with even better abrasion resistance. R F The alkyl group may be either branched or linear, and is preferably linear in that the surface layer has better abrasion resistance and lubricity.

[0025] m1 is an integer of 2 to 200, preferably an integer of 5 to 150, and particularly preferably an integer of 10 to 80. When m1 is equal to or greater than the lower limit of the above range, the surface layer has excellent water and oil repellency. When m1 is equal to or less than the upper limit of the above range, the surface layer has excellent abrasion resistance. That is, when the number average molecular weights of the compound (A) and the compound (B) are too large, the number of groups (I) present per unit molecular weight decreases, and the abrasion resistance decreases.

[0026] (R F O) m1 In the formula, there are two or more R with different carbon numbers. F If O is present, then each R F The bonding order of O is not limited. For example, two types of R F When O is present, two types of R F The O's may be arranged randomly, alternatingly, or in blocks.

[0027] (R F O)m1 As for the surface layer, {(CF2O) m11 (CF2CF2O) m12}, (CF2CF2O) m13 , (CF2CF2CF2O) m14 , (CF2CF2O-CF2CF2CF2CF2O) m15 is preferred, {(CF2O) m11 (CF2CF2O) m12}, (CF2CF2O-CF2CF2CF2CF2O) m15 is more preferred, (CF2CF2O-CF2CF2CF2CF2O) m15 is particularly preferred. Here, m11 is an integer of 1 or more, m12 is an integer of 1 or more, (m11+m12) is an integer of 2 to 200, and the bonding order of m11 CF2O and m12 CF2CF2O is not limited. m13 and m14 are each an integer of 2 to 200, and m15 is an integer of 1 to 100. m15 is preferably an integer of 2 to 100.

[0028] R of each of compound (A) and compound (B) PF The number of chains may be one or more. From the viewpoint of abrasion resistance, 1 to 3 chains are preferable, and 1 to 2 chains are particularly preferable. PF The number of chains, and therefore R f By having one or more groups, the surface layer has excellent water droplet sliding properties, water and oil repellency, durability, fingerprint stain removal properties, and lubricity. PF When the number of chains is equal to or less than the upper limit of the above range, the appearance of the surface layer is excellent. Compound (A) and compound (B) are R PF If there are two or more chains, each R PF The strands may be the same or different.

[0029] (Group (I)) In group (I), L is a hydroxyl group or a hydrolyzable group. A hydrolyzable group is a group that becomes a hydroxyl group through a hydrolysis reaction. That is, when L is a hydrolyzable group, Si-L of the group (I) becomes a silanol group (Si-OH) through a hydrolysis reaction. Examples of the hydrolyzable group include an alkoxy group, a halogen atom, an acyl group, an isocyanate group (-NCO), etc. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms.

[0030] From the viewpoint of ease of production of compounds (A) and (B), L is preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom. As a halogen atom, a chlorine atom is particularly preferred. As L, from the viewpoint of less outgassing during coating and excellent storage stability of compounds (A) and (B), an alkoxy group having 1 to 4 carbon atoms is preferred, an ethoxy group is particularly preferred when long-term storage stability of compounds (A) and (B) is required, and a methoxy group is particularly preferred when the reaction time after coating is short.

[0031] R is a hydrogen atom or a monovalent hydrocarbon group. Examples of the monovalent hydrocarbon group include saturated hydrocarbon groups such as an alkyl group and a cycloalkyl group, and alkenyl groups such as an allyl group, with saturated hydrocarbon groups being preferred. The monovalent hydrocarbon group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms, in terms of ease of production of compound (A) and compound (B).

[0032] n is preferably 0 or 1, particularly preferably 0. When a plurality of Ls exist in one group (I), the adhesion to the substrate becomes stronger, and the durability of the surface layer becomes even more excellent. When n is 0 or 1, the (3-n) L's may be the same or different. For example, some of the L's may be hydrolyzable groups and the remaining L's may be hydroxyl groups.

[0033] As the group (I), Si(OCH3)3, SiCH3(OCH3)2, Si(OCH2CH3)3, SiCl3, Si(OCOCH3)3, and Si(NCO)3 are preferred. From the viewpoint of ease of handling in industrial production, Si(OCH3)3 is particularly preferred.

[0034] The number of groups (I) possessed by each of the compound (A) and the compound (B) may be 1 or 2 or more. From the viewpoint of further improving the water droplet sliding property of the surface layer, 1 to 3 groups are preferred, and from the viewpoint of further improving the abrasion resistance of the surface layer, 2 or 3 groups are particularly preferred. When compound (A) or compound (B) has two or more groups (I), all of the groups (I) may or may not be the same group. From the viewpoint of ease of production of compound (A), it is preferable that all of the groups (I) are the same group.

[0035] The number average molecular weight (Mn) of each of the compound (A) and the compound (B) is preferably from 2,000 to 20,000, more preferably from 2,500 to 15,000, and particularly preferably from 3,000 to 10,000. When the number average molecular weight is within the above range, the abrasion resistance is excellent. The number average molecular weight (Mn) is measured by the method described in the Examples section below.

[0036] When the surface layer is formed by a dry coating method, it is preferable that the difference between the number average molecular weight (Mn) of the compound (A) and the number average molecular weight (Mn) of the compound (B) is small. In the case of the dry coating method, the smaller the molecular weight, the more likely it is that the compound (A) and the compound (B) will evaporate first and be deposited on the substrate. The smaller the difference in number average molecular weight (Mn), the less likely it is that unevenness in the distribution of the compound (A) and the compound (B) will occur in the surface layer that is formed. The difference between the number average molecular weight (Mn) of the compound (A) and the number average molecular weight (Mn) of the compound (B) is preferably 2,000 or less, particularly preferably 1,000 or less. When the surface layer is formed by a wet coating method, even if there is a difference between the number average molecular weight (Mn) of compound (A) and the number average molecular weight (Mn) of compound (B), uneven distribution of compound (A) and compound (B) is unlikely to occur in the formed surface layer, and therefore the difference therebetween is not particularly limited. The dry coating method and the wet coating method will be described in detail later.

[0037] Compound (A) and compound (B) are R PF chain, R fThere are no particular limitations on the fluorine-containing ether compound, so long as it has the group (I) and the group (I). For example, it can be appropriately selected from known fluorine-containing ether compounds such as the fluorine-containing ether compounds described in the following documents and commercially available fluorine-containing ether compounds. JP 2013-91047 A, JP 2014-80473 A, WO 2013 / 042732 A, WO 2013 / 042733 A, WO 2013 / 121984 A, WO 2013 / 121985 A, WO 2013 / 121986 A, WO 2014 / 163004 A, WO 2014 / 175124, International Publication No. 2015 / 087902, JP 2013-227279 A, ​​JP 2013-241569 A, JP 2013-256643 A, JP 2014-15609 A, JP 2014-37548 A, JP 2014-65884 A, JP 2014-210258 A, JP 2014-21 8639, JP 2015-200884 A, JP 2015-221888 A, WO 2013 / 146112 A, WO 2013 / 187432 A, WO 2014 / 069592 A, WO 2015 / 099085 A, WO 2015 / 166760 A, JP 2013-144726 A, JP 2014-77836 A, JP 2013-117012 A, JP 2014-214194 A, JP 2014-198822 A, JP 2015-129230 A, JP 2015-196723 A, JP 2015-13983 A, JP 2015-199915 A, JP 2015-199906 A, and the like.

[0038] R PF chain, R f group and group (I), R f Examples of fluorine-containing ether compounds having a CF3- group include OPTOOL (registered trademark) UD509 manufactured by Daikin Industries, Ltd., and KY-178, KY-185, and KY-1900 manufactured by Shin-Etsu Chemical Co., Ltd. R PF chain, R f group and group (I), R fExamples of the fluorine-containing ether compound having a CF3CF2CF2- group include OPTOOL DSX and AES manufactured by Daikin Industries, Ltd., DOW CORNING (registered trademark) 2634 COATING manufactured by Dow Corning Toray Co., Ltd., and KY-108 manufactured by Shin-Etsu Chemical Co., Ltd. Of these, the present composition is a compound (A) having a fluorine-containing ether compound which is CF3-, and R f The compound (B) may contain a fluorine-containing ether compound having a CF3CF2CF2- group.

[0039] In the present composition, each of compound (A) and compound (B) may be a single compound consisting of one type of compound, or a mixture consisting of two or more types of compounds. In this specification, fluorine-containing ether compounds, which are identical except for the distribution in the number of repeating oxyperfluoroalkylene groups in the poly(oxyperfluoroalkylene) chain, are regarded as a single compound. For example, R PF The chain is {(CF2O) m11 (R f2 O) m12 In the case of a compound which is the same except for having a distribution in m11 and m12, the compound group is regarded as a fluorine-containing ether compound which is a single compound.

[0040] Both the compound (A) and the compound (B) are preferably fluorine-containing ether compounds represented by the following formula (A / B). R in the formula (A / B) below f R f In the combination of compound (A) and compound (B) contained in the present composition, R f The number of carbon atoms in compound (B) is f The number of carbon atoms is smaller than that of R. PF is the above R PF represents the chain, Q and SiR n L 3-n is the same as above. [R f -OQR PF -] r Z[-SiRn L 3-n ] s (A / B) However, R f is a perfluoroalkyl group, and when r is 2 or more, the r perfluoroalkyl groups are the same perfluoroalkyl group, Q is a single bond, an oxyfluoroalkylene group containing one or more hydrogen atoms, or a polyoxyfluoroalkylene group formed by bonding 2 to 5 of the oxyfluoroalkylene groups, and the oxyfluoroalkylene groups constituting the group may all be the same or different; R PF is a poly(oxyperfluoroalkylene) chain, Z is a linking group having a valence of (r+s), -SiR n L 3-n is a group represented by the formula (I), and when s is 2 or more, the s groups represented by the formula (I) are the same group, Each of r and s is an integer of 1 or more, and r+s is 8 or less.

[0041] The r is the R PF The number of chains, and therefore R f It represents the number of groups and is an integer of 1 or more. As described above, from the viewpoint of abrasion resistance, r is preferably an integer of 1 to 3, and particularly preferably 1 or 2. The s represents the number of groups (I), and is preferably 1 to 3 in terms of providing a surface layer with even better water droplet sliding properties, as described above, and is particularly preferably 2 or 3 in terms of providing a surface layer with even better abrasion resistance. From the above viewpoints, r+s is preferably 2-6, and particularly preferably 3-5. The (r+s)-valent linking group Z is the Z a , Z b Preferred are linking groups represented by the following formula: and examples thereof include substituted or unsubstituted hydrocarbon groups, groups having groups or atoms other than hydrocarbon groups between carbon atoms or at the terminals of substituted or unsubstituted hydrocarbon groups, and organopolysiloxane groups. Preferred Z is the preferred Z described below. a Or Z bis the same linking group as

[0042] <Preferred embodiment> A preferred embodiment of the present composition is one in which compound (A) is a fluorinated ether compound (A1) (hereinafter also referred to as "compound (A1)") represented by the following formula (A1), and compound (B) is a fluorinated ether compound (B1) (hereinafter also referred to as "compound (B1)") represented by the following formula (B1). That is, the composition of this embodiment contains compound (A1) and compound (B1), and the content of compound (A1) is 30 to 95 mass% based on the total of compound (A1) and compound (B1).

[0043] [R fa -OQ a -R PFa -] r1 Z a [-SiR a n1 L a 3-n1 ] s1 (A1) [R fb -OQ b -R PFb -] r2 Z b [-SiR b n2 L b 3-n2 ] s2 (B1) However, R fa and R fb is R f R fa The number of carbon atoms in R fb The number of carbon atoms is less than that of Q a and Q b represents a single bond, an oxyfluoroalkylene group containing one or more hydrogen atoms, or a polyoxyfluoroalkylene group formed by bonding 2 to 5 of the oxyfluoroalkylene groups, and the oxyfluoroalkylene groups constituting the group may all be the same or different, R PFa and R PFb is R PF It is a chain, Z a is a (r1+s1)-valent linking group, Z b is a (r2+s2)-valent linking group, L a and L b is a hydroxyl group or a hydrolyzable group, R a and R b is a hydrogen atom or a monovalent hydrocarbon group, n1 and n2 are integers from 0 to 2, (3-n1) Ls where n1 is 0 or 1 a , (3-n) Ls where n2 is 0 or 1 b may be the same or different, When n1 is 2, n1 R a , n2 R when n2 is 2 b may be the same or different, r1 and r2 are integers of 1 or more, and when r1 is 2 or more, r1 R fa , Q a and R PFa may be the same or different, and when r2 is 2 or more, r2 R fb , Q b and R PFb may be the same or different, s1 and s2 are integers of 1 or more, and when s1 is 2 or more, s1 of [-SiR a n1 L a 3-n1 ] may be the same or different, and when s2 is 2 or more, s2 [-SiR b n2 L b 3-n2 ] may be the same or different.

[0044] R f The groups are the same as those described above, and the preferred embodiments are also the same. When r1 is 2 or more, r1 R faPreferably, the carbon numbers are the same, and from the viewpoint of ease of production, the groups are preferably the same, that is, groups having the same carbon numbers and the same chemical structures. For example, when r1 is 2, two R fa is CF3CF2CF2- (two R fa Although the number of carbon atoms is the same, the chemical structures are different, and the combinations CF3CF2CF2- and CF3CF(CF3)- are not the same. When r2 is 2 or more, r2 R fb Preferably, the carbon numbers are the same, and from the viewpoint of ease of production, the groups are preferably the same, that is, groups having the same carbon numbers and the same chemical structures. In this embodiment, the surface layer is further excellent in lubricity and abrasion resistance, so that R fa The carbon number of R is 1 to 19. fb R preferably has 2 to 20 carbon atoms. fa The number of carbon atoms is 1 to 9, R fb More preferably, R has 2 to 10 carbon atoms. fa The number of carbon atoms is 1 to 5, R fb More preferably, R has 2 to 6 carbon atoms. fa The number of carbon atoms is 1, R fb has 2 or 3 carbon atoms, or R fa The number of carbon atoms is 2, R fb It is particularly preferable that the carbon number is 3.

[0045] Q a and Q b is the same as Q in the above group (II), and preferred embodiments are also the same. R PFa and R PFb R PF The chains are the same as above, and the preferred embodiments are also the same. L a and L b is the same as L in the above group (I), and preferred embodiments are also the same. R a and R b is the same as R in the above group (I), and preferred embodiments are also the same. n1 and n2 are the same as n in the above group (I), and preferred embodiments are also the same. The preferred values ​​of r1 and r2 are R PF The preferred numbers of the chains are the same as those of the chains. That is, from the viewpoint of abrasion resistance, r1 and r2 are preferably 1 to 3, and more preferably 1 or 2. The preferred values ​​of s1 and s2 are the same as the preferred numbers of the groups (I) in the compounds (A) and (B). That is, s1 and s2 are preferably 1 to 3, and particularly preferably 2 to 3, from the viewpoint of excellent water droplet sliding properties of the surface layer.

[0046] Z a Examples of the substituted or unsubstituted hydrocarbon group include a (r1+s1)-valent substituted or unsubstituted hydrocarbon group, a (r1+s1)-valent group having a group or atom other than a hydrocarbon group between carbon atoms and / or at the terminal of a substituted or unsubstituted hydrocarbon group, and a (r1+s1)-valent organopolysiloxane group. Z b As for the valence, it is Z except that it has a valence of (r2+s2). a The same can be mentioned.

[0047] Examples of unsubstituted hydrocarbon groups include linear or branched saturated hydrocarbon groups, aromatic hydrocarbon cyclic groups (e.g., groups in which (a+b) hydrogen atoms have been removed from an aromatic hydrocarbon ring such as a benzene ring or a naphthalene ring), groups consisting of a combination of linear or branched saturated hydrocarbon groups and aromatic hydrocarbon cyclic groups (e.g., groups in which an alkyl group is bonded as a substituent to the aromatic hydrocarbon cyclic group, groups in which an arylene group such as a phenylene group is present between carbon atoms or / and at the end of the saturated hydrocarbon group, etc.), and groups consisting of a combination of two or more aromatic hydrocarbon cyclic groups. Among these, linear or branched saturated hydrocarbon groups are preferred. Substituted hydrocarbon groups are groups in which some or all of the hydrogen atoms of a hydrocarbon group are substituted with a substituent. Examples of the substituent include a hydroxyl group, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, an amino group, a nitro group, a cyano group, and an aminocarbonyl group.

[0048] Examples of groups or atoms other than the hydrocarbon group that are present between carbon atoms of the hydrocarbon group or / and at the terminals include an ethereal oxygen atom (-O-), a thioethereal sulfur atom (-S-), a nitrogen atom (-N<), a silicon atom (>Si<), a carbon atom (>C<), -N(R 15 )-, -C(O)N(R 15 )-, -OC(O)N(R 15 )-, -Si(R 16 )(R 17 )-, organopolysiloxane group, -C(O)-, -C(O)-O-, -C(O)-S-, etc., where R 15 is a hydrogen atom, an alkyl group, or a phenyl group, and R 16 ~R 17 each independently represents an alkyl group or a phenyl group. The organopolysiloxane group may be linear, branched, or cyclic.

[0049] <Preferable form of compound (A1)> As the compound (A1), at least one selected from the group consisting of the following compounds (A11), (A12) and (A13) is preferable, in that the surface layer has even better abrasion resistance and fingerprint stain removability.

[0050] "Compound (A11)" The compound (A11) is represented by the following formula (A11). R fa -OQ a -R PFa -Q 32a -[C(O)N(R 33a )] p1 -R 34a -C[-R 35a -SiR a n1 L a 3-n1 ]3···(A11) However, R fa , Q a , R PFa , R a , L a and n1 are as defined above, Q32a is a fluoroalkylene group or a group having an ether oxygen atom between carbon atoms of a fluoroalkylene group having two or more carbon atoms, R 33a is a hydrogen atom or an alkyl group, p1 is 0 or 1, R 34a is a single bond, an alkylene group, or the end of an alkylene group (except for C[-R 35a -SiR a n1 L a 3-n1 ]3. A group having an ethereal oxygen atom at the end of the alkylene group having two or more carbon atoms, a group having an ethereal oxygen atom between the carbon atoms of the alkylene group having two or more carbon atoms (provided that C[-R 35a -SiR a n1 L a 3-n1 ]3.) and a group having an ether oxygen atom between carbon atoms, R 35a is an alkylene group, a group having an ethereal oxygen atom at the terminal of an alkylene group (excluding the terminal bonded to Si), or a group having an ethereal oxygen atom between carbon atoms of an alkylene group having two or more carbon atoms, Three [-R 35a -SiR a n1 L a 3-n1 ] may be the same or different.

[0051] Compound (A11) is a compound represented by the above formula (A1), in which r1 is 1, s1 is 3, and Z is -Q 32a -[C(O)N(R 33a )] p1 -R 34a -C[-R 35a -]3 is a compound.

[0052] Q 32aIn the above, the fluoroalkylene group is preferably a perfluoroalkylene group or a fluoroalkylene group containing one or more hydrogen atoms. 32a As the alkyl group, a perfluoroalkylene group, a fluoroalkylene group containing one or more hydrogen atoms, a group having an ethereal oxygen atom between the carbon-carbon atoms of a perfluoroalkylene group having two or more carbon atoms, or a group having an ethereal oxygen atom between the carbon-carbon atoms of a fluoroalkylene group having two or more carbon atoms and containing one or more hydrogen atoms is preferred.

[0053] If p1 is 0, then Q 32a is preferably a perfluoroalkylene group, and the perfluoroalkylene group preferably does not have a branched structure. 32a If is a perfluoroalkylene group having no branched structure, the surface layer will have even better abrasion resistance and lubricity. If p1 is 0, then Q 32a is R PFa is {(CF2O) m11 (CF2CF2O) m12} or (CF2CF2O) m13 is typically a perfluoroalkylene group having one carbon atom, and R PFa (CF2CF2CF2O) m14 is typically a perfluoroalkylene group having 2 carbon atoms, and R PFa (CF2CF2O-CF2CF2CF2CF2O) m15 When it is, it is typically a linear perfluoroalkylene group having 3 carbon atoms.

[0054] If p1 is 1, then Q 32a Examples of the group include the following groups. (i) A perfluoroalkylene group. (ii)-R F CH2O-(where R F is a perfluoroalkylene group. PFa and a fluoroalkylene group (which may have an ether oxygen atom between carbon atoms) containing one or more hydrogen atoms on the side bonded to C(O)N(R33 ) a group on the side bonding to the

[0055] Q of (ii) 32a As the group, the following groups are preferred from the viewpoint of ease of production of compound (A11). -R F CH2O-CF2CHFOCF2CF2CF2-, -R F CH2O-CF2CHFCF2OCF2CF2-, -R F CH2O-CF2CHFCF2OCF2CF2CF2-, -R F CH2O-CF2CHFOCF2CF2CF2OCF2CF2-. Q 32a When the compound (A11) does not have a branched structure, a surface layer having excellent durability and lubricity can be formed.

[0056] [C(O)N(R 33a )] p1 The properties of the fluorine-containing ether compound are almost the same whether p1 in the group is 0 or 1. When p is 1, the compound has an amide bond, but 32a [C(O)N(R 33a By having at least one fluorine atom bonded to the carbon atom at the end of the bond with )], the polarity of the amide bond is reduced, and the water and oil repellency of the surface layer is less likely to decrease. Whether p1 is 0 or 1 can be selected from the viewpoint of ease of production. [C(O)N(R 33a )] p1 R in the group 33a From the viewpoint of ease of production of compound (A11), a hydrogen atom is preferred as the substituent. R 33a When the group is an alkyl group, the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms.

[0057] If p1 is 0, R 34a From the viewpoint of ease of production of compound (A11), a group selected from the group consisting of a single bond, -CH2O-, -CH2OCH2-, -CH2OCH2CH2O- and -CH2OCH2CH2OCH2- (wherein the left side is Q 32a ) is preferred. If p1 is 1, R 34a From the viewpoint of ease of production of compound (A11), a group selected from the group consisting of a single bond, -CH2- and -CH2CH2- is preferred.

[0058] R 35a From the viewpoint of ease of production of compound (A11), a group selected from the group consisting of -CH2CH2-, -CH2CH2CH2-, -CH2OCH2CH2CH2-, and -OCH2CH2CH2- (wherein the right side is bonded to Si) is preferred. R 35a In terms of excellent light resistance of the surface layer, it is particularly preferable that the water- and oil-repellent layer does not have an ether oxygen atom. In touch panels for outdoor use (digital signage such as vending machines and guide boards), in-vehicle touch panels, etc., light resistance is required for the water- and oil-repellent layer. Three R in compound (A11) 35a may be the same or different.

[0059] Examples of the compound (A11) include the compound of the following formula: This compound is preferred in that it is easy to produce industrially, easy to handle, and provides a surface layer with excellent water and oil repellency, abrasion resistance, fingerprint stain removability, lubricity, and appearance.

[0060] [ka]

[0061] [ka]

[0062] In these formulas, W is R fa -OQ a -R PFa Preferred forms of W are the above-mentioned preferred R fa , Q a and R PFa It is a combination of Q 32a The preferred ranges are as described above.

[0063] "Compound (A12)" The compound (A12) is represented by the following formula (A12). R fa -OQ a -R PFa -R 42a -R 43a -N[-R 44a -SiR a n1 L a 3-n1 ]2···(A12) However, R fa , Q a , R PFa , R a , L a and n1 are as defined above, R 42a is a perfluoroalkylene group, R 43a is a single bond, an alkylene group, a group having an ethereal oxygen atom or -NH- at the alkylene group terminal (excluding the terminal bonding to N), a group having an ethereal oxygen atom or -NH- between a carbon-carbon atom of an alkylene group having two or more carbon atoms, or a group having an ethereal oxygen atom or -NH- between the terminal (excluding the terminal bonding to N) and a carbon-carbon atom of an alkylene group having two or more carbon atoms, R 44a is an alkylene group or an alkylene group having two or more carbon atoms and having an ether oxygen atom or -NH- between carbon atoms, Two [-R 44a -SiR a n1 L a 3-n1 ] may be the same or different.

[0064] Compound (A12) is a compound represented by the above formula (A1), in which r1 is 1, s1 is 2, and Z is -R 42a -R 43a -N[-R 44a -]2 is a compound.

[0065] R 42a R is preferably a perfluoroalkylene group having no branched structure. 42a If is a perfluoroalkylene group having no branched structure, the surface layer will have even better abrasion resistance and lubricity. R 42a is R PFa is {(CF2O) m11 (CF2CF2O) m12} or (CF2CF2O) m13 is typically a perfluoroalkylene group having one carbon atom, and R PFa (CF2CF2CF2O) m14 is typically a perfluoroalkylene group having 2 carbon atoms, and R PFa (CF2CF2O-CF2CF2CF2CF2O) m15 When it is, it is typically a linear perfluoroalkylene group having 3 carbon atoms.

[0066] R 43a From the viewpoint of ease of production of compound (A12), a group selected from the group consisting of -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2OCH2CH2- and -CH2NHCH2CH2- (wherein the left side is R 42a ) is preferred. R 43a Since it does not have an ester bond which has high polarity and is insufficient in chemical resistance and light resistance, the initial water repellency, chemical resistance and light resistance of the surface layer are excellent.

[0067] R 44a From the viewpoint of ease of production of compound (A12), -CH2CH2CH2- or -CH2CH2OCH2CH2CH2- (wherein the right side is bonded to Si) is preferred. R 44a Since it does not have an ester bond which has high polarity and is insufficient in chemical resistance and light resistance, the initial water repellency, chemical resistance and light resistance of the surface layer are excellent. R 44a From the viewpoint of excellent light resistance of the surface layer, it is particularly preferable that the compound does not have an etheric oxygen atom. Two R in compound (A12) 44a may or may not be the same group.

[0068] Examples of the compound (A12) include the compound of the following formula: This compound is preferred because it is easy to produce industrially, easy to handle, and has excellent water and oil repellency, abrasion resistance, fingerprint stain removability, lubricity, chemical resistance, and light resistance.

[0069] [ka]

[0070] In these formulas, W is R fa -OQ a -R PFa Preferred forms of W are the above-mentioned preferred R fa , Q a and R PFa It is a combination of R 42a The preferred ranges are as described above.

[0071] "Compound (A13)" The compound (A13) is represented by the following formula (A13). [R fa -OQ a -R PFa -R 51a -R 52a -O-] e1 Z 3a [-OR 53a -SiR a n1 L a 3-n1 ] f1 (A13) However, R fa , Q a , R PFa , R a , L a and n1 are as defined above, R 51a is a linear perfluoroalkylene group, R 52ais an alkylene group, Z 3a represents an (e1+f1)-valent hydrocarbon group or an (e1+f1)-valent group having two or more carbon atoms and having one or more etheric oxygen atoms between carbon atoms of the hydrocarbon group, R 53a is an alkylene group, e1 is an integer equal to or greater than 1, f1 is an integer equal to or greater than 1, (e1+f1) is 3 or more, When e1 is 2 or more, e1 R fa are all the same group, and e1 Q a , R PFa , R 51a and R 52a may be the same or different, When f1 is 2 or more, f1 [-OR 53 -SiR n L 3-n ] may be the same or different.

[0072] Compound (A13) is a compound represented by the above formula (A1), in which r1 is e1, s1 is f1, and Z is [-R 51a -R 52a -O-] e1 Z 3a [-OR 53a -] f1 It is a compound of the formula:

[0073] R 51a For example, R PFa is {(CF2O) m11 (CF2CF2O) m12} or (CF2CF2O) m13 is typically -CF2-, and R PFa (CF2CF2CF2O) m14 is typically -CFCF-, and R PFa (CF2CF2O-CF2CF2CF2CF2O) m15 When it is, it is typically -CF2CF2CF2-. R 51aWhen the compound (A13) is linear, a surface layer having excellent abrasion resistance and lubricity can be formed.

[0074] R 52a From the viewpoint of ease of production of the compound (A13), an alkylene group having 1 to 4 carbon atoms is preferable, and -CH2- is particularly preferable.

[0075] R fa -OQ a -R PFa -R 51a As the - group, the group (R f -1), group (R f -2), or a group (R f -3) is preferred. R f11 O{(CF2O) m21 (CF2CF2O) m22}CF2- (R f -1) R f11 OCHFCF2OCH2CF2O{(CF2O) m21 (CF2CF2O) m22}CF2- (R f -2) R f11 O(CF2CF2OCF2CF2CF2CF2O) m25 CF2CF2OCF2CF2CF2- (R f -3) However, R f11 represents a linear perfluoroalkyl group having 1 to 20 carbon atoms; m21 and m22 each represent an integer of 1 or more, m21+m22 represents an integer of 2 to 200, and the bonding order of m21 CF2O and m22 CF2CF2O is not limited; and m25 represents an integer of 1 to 100.

[0076] Z 3a Examples of the hydroxyl group include a residue obtained by removing hydroxyl groups from a polyhydric alcohol having (e1+f1) hydroxyl groups. Z 3aSpecific examples of Z include the following groups: 3a As R, a residue obtained by removing a hydroxyl group from a polyhydric alcohol having a primary hydroxyl group is preferred from the viewpoint of excellent reactivity of the hydroxyl group, and a group (Z-1), a group (Z-2), or a group (Z-3) is particularly preferred from the viewpoint of easy availability of the raw material. 4 is an alkyl group, preferably a methyl group or an ethyl group.

[0077] [ka]

[0078] R 53a From the viewpoint of ease of production of compound (A13), an alkylene group having 3 to 14 carbon atoms is preferred. Furthermore, from the viewpoint of less generation of by-products in which allyl groups (-CHCH=CH2) are isomerized partially or entirely to inner olefins (-CH=CHCH3) during hydrosilylation in the production of compound (A13) described below, an alkylene group having 4 to 10 carbon atoms is particularly preferred.

[0079] The preferred values ​​of e1 and f1 are similar to the preferred values ​​of r1 and r2, respectively.

[0080] Examples of the compound (A13) include compounds (1-1) to (1-6) of the following formulae: These compounds are preferred because they are easy to produce industrially, easy to handle, and provide a surface layer with excellent water and oil repellency, abrasion resistance, fingerprint stain removability, lubricity, and appearance.

[0081] [ka]

[0082] In these formulas, W is R fa -OQ a -R PFa Preferred forms of W are the above-mentioned preferred R fa , Q a and R PFa It is a combination of R51a The preferred forms are as described above.

[0083] <Preferable form of compound (B1)> As the compound (B1), at least one selected from the group consisting of the following compounds (B11), (B12) and (B13) is preferable, in that the surface layer has even better abrasion resistance and fingerprint stain removability.

[0084] "Compound (B11)" The compound (B11) is represented by the following formula (B11). R fb -OQ b -R PFb -Q 32b -[C(O)N(R 33b )] p2 -R 34b -C[-R 35b -SiR b n2 L b 3-n2 ]3···(B11) However, R fa , Q b , R PFb , R b , L b and n2 are as defined above, Q 32b is a fluoroalkylene group or a group having an ether oxygen atom between carbon atoms of a fluoroalkylene group having two or more carbon atoms, R 33b is a hydrogen atom or an alkyl group, p2 is 0 or 1; R 34b is a single bond, an alkylene group, or the end of an alkylene group (except for C[-R 35b -SiR b n2 L b 3-n2 ]3. A group having an ethereal oxygen atom at the end of the alkylene group having two or more carbon atoms, a group having an ethereal oxygen atom between the carbon atoms of the alkylene group having two or more carbon atoms (provided that C[-R 35b -SiRb n2 L b 3-n2 ]3.) and a group having an ether oxygen atom between carbon atoms, R 35b is an alkylene group, a group having an ethereal oxygen atom at the terminal of an alkylene group (excluding the terminal bonded to Si), or a group having an ethereal oxygen atom between carbon atoms of an alkylene group having two or more carbon atoms, Three [-R 35b -SiR b n2 L b 3-n2 ] may be the same or different.

[0085] Compound (B11) is a compound represented by the above formula (B1), in which r2 is 1, s2 is 3, and Z b Ga-Q 32b -[C(O)N(R 33b )] p2 -R 34b -C[-R 35b -]3 is a compound.

[0086] Q 32b , R 33b , p2, R 34b , R 35b are respectively Q in the above formula (A11). 32a , R 33a , p1, R 34a , R 35a The same applies to the preferred embodiments.

[0087] "Compound (B12)" The compound (B12) is represented by the following formula (B12). R fb -OQ b -R PFb -R 42b -R 43b -N[-R 44b -SiR n2 L 3-n2 ]2···(B12) However, R fa , Q b , RPFb , R b , L b and n2 are as defined above, R 42b is a perfluoroalkylene group, R 43b is a single bond, an alkylene group, a group having an ethereal oxygen atom or -NH- at the alkylene group terminal (excluding the terminal bonding to N), a group having an ethereal oxygen atom or -NH- between a carbon-carbon atom of an alkylene group having two or more carbon atoms, or a group having an ethereal oxygen atom or -NH- between the terminal (excluding the terminal bonding to N) and a carbon-carbon atom of an alkylene group having two or more carbon atoms, R 44b is an alkylene group or an alkylene group having two or more carbon atoms and having an ether oxygen atom or -NH- between carbon atoms, Two [-R 44b -SiR b n2 L b 3-n2 ] may not be the same group.

[0088] Compound (B12) is a compound represented by the above formula (B1), in which r2 is 1, s2 is 2, and Z b -R 42b -R 43b -N[-R 44b -]2 is a compound.

[0089] R 42b , R 43b , R 44b are R in the above formula (A12), 42a , R 43a , R 44a The same applies to the preferred embodiments.

[0090] "Compound (B13)" The compound (B13) is represented by the following formula (B13). [R fb -OQ b -R PFb -R 51b -R52b -O-] e2 Z 3b [-OR 53b -SiR b n2 L b 3-n2 ] f2 (B13) However, R fa , Q b , R PFb , R b , L b and n2 are as defined above, R 51b is a linear perfluoroalkylene group, R 52b is an alkylene group, Z 3b is an (e2+f2)-valent hydrocarbon group or an (e2+f2)-valent group having two or more carbon atoms and having one or more etheric oxygen atoms between carbon atoms of the hydrocarbon group, R 53b is an alkylene group, e2 is an integer equal to or greater than 1, f2 is an integer equal to or greater than 1, (e2+f2) is 3 or more, When e2 is 2 or more, e2 R fb are all the same group, and e2 Q b , R PFb , R 51b and R 52b may be the same or different, When f2 is 2 or more, f2 [-OR 53b -SiR b n2 L b 3-n2 ] may be the same or different.

[0091] Compound (B13) is a compound represented by the above formula (B1), in which r2 is e2, s2 is f2, and Z b [-R 51b -R 52b -O-] e2 Z 3b [-OR 53b -]f2 It is a compound of the formula:

[0092] R 51b , R 52b , Z 3b , R 53b , e2, and f2 are each R in formula (A13). 51a , R 52a , Z 3a , R 53a , e1, and f1, and preferred embodiments are also the same.

[0093] (Other fluorine-containing ether compounds) The present composition may further contain a fluorine-containing ether compound other than the compound (A) and the compound (B). Other fluorine-containing ether compounds include, for example, fluorine-containing ether compounds having a poly(oxyperfluoroalkylene) chain and no group (I) (hereinafter also referred to as compound (C)).

[0094] An example of the compound (C) is the compound (C1). A 31 -OQ 51 -(R F3 O) m30 -[Q 52 -O] p3 -A 32 (C1) However, A 31 and A 32 are each independently a perfluoroalkyl group having 1 to 20 carbon atoms; Q 51 is a single bond, a fluoroalkylene group not having a branched structure containing one or more hydrogen atoms, or the end of a fluoroalkylene group not having a branched structure containing one or more hydrogen atoms (provided that A 31 A group having an ether oxygen atom between carbon-carbon atoms of a fluoroalkylene group having 2 or more carbon atoms and not having a branched structure containing one or more hydrogen atoms (excluding the terminal bonded to -O). 31-Excluding the terminal bonded to -O.) and a group having an ether oxygen atom between carbon atoms (however, the number of oxygen atoms is 10 or less);Q 52 is a fluoroalkylene group not having a branched structure containing one or more hydrogen atoms, or a group having an ether oxygen atom between carbon atoms of a fluoroalkylene group having two or more carbon atoms not having a branched structure containing one or more hydrogen atoms (however, the number of oxygen atoms is 10 or less); R F3 is a perfluoroalkylene group having no branched structure; m30 is an integer of 2 to 200; (R F3 O) m30 R has two or more different carbon numbers. F3 O; p3 may consist of Q 51 is 0 if it is a single bond, and Q 51 is not a single bond, the value is 1.

[0095] The compound (C1) may be produced by a known production method or may be a commercially available product. 51 Commercially available examples of compound (C1) in which p is a single bond and p3 is 0 include FOMBLIN (registered trademark) M, FOMBLIN (registered trademark) Y, and FOMBLIN (registered trademark) Z (all manufactured by Solvay Solexis), Krytox (registered trademark) (manufactured by DuPont), and Demnum (registered trademark) (manufactured by Daikin Industries, Ltd.).

[0096] The present composition may contain impurities other than compound (A), compound (B) and other fluorinated ether compounds. Examples of impurities other than compound (A), compound (B) and other fluorinated ether compounds include compounds that are unavoidable in the production of compound (A), compound (B) and other fluorinated ether compounds.

[0097] (Composition of the composition) In the present composition, among the compound (A) and the compound (B), R f The content of the group having the fewer carbon atoms is 30 to 95 mass %, preferably 40 to 90 mass %, and particularly preferably 40 to 80 mass %, based on the total amount of the compound (A) and the compound (B).f When the content of the group having the fewer carbon atoms is within the above range, the surface layer has excellent water droplet sliding properties.

[0098] In the present composition, the total amount of the compound (A) and the compound (B) is preferably 10% by mass or more, particularly preferably 20% by mass or more, based on the total mass of the present composition. The upper limit is not particularly limited, and may be 100% by mass.

[0099] [Coating Liquid] The coating liquid of the present invention (hereinafter also referred to as the present coating liquid) contains the present composition and a liquid medium. The present coating liquid may be in a liquid state, and may be a solution or a dispersion. The present coating liquid is only required to contain the present composition, and may contain impurities such as by-products generated in the manufacturing process of compound (A), compound (B), and the like. The concentration of the present composition in the present coating liquid is preferably from 0.001 to 50% by mass, more preferably from 0.05 to 30, further preferably from 0.05 to 10, and particularly preferably from 0.1 to 1% by mass.

[0100] The liquid medium is preferably an organic solvent. The organic solvent may be a fluorine-based organic solvent, a non-fluorine-based organic solvent, or may contain both.

[0101] Examples of the fluorine-based organic solvent include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, and fluoroalcohols. The fluorinated alkane is preferably a compound having 4 to 8 carbon atoms. Commercially available products include, for example, C6F 13 H (Asahi Glass Co., Ltd., Asahiklin (registered trademark) AC-2000), C6F 13 Examples include C2H5 (Asahiklin (registered trademark) AC-6000, manufactured by Asahi Glass Co., Ltd.) and C2F5CHFCHFCF3 (Bertrel (registered trademark) XF, manufactured by Chemours). Examples of the fluorinated aromatic compounds include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, and bis(trifluoromethyl)benzene. The fluoroalkyl ether is preferably a compound having a carbon number of 4 to 12. Examples of commercially available products include CF3CH2OCF2CF2H (manufactured by Asahi Glass Co., Ltd., Asahiklin (registered trademark) AE-3000), C4F9OCH3 (manufactured by 3M, Novec (registered trademark) 7100), C4F9OC2H5 (manufactured by 3M, Novec (registered trademark) 7200), and C2F5CF(OCH3)C3F7 (manufactured by 3M, Novec (registered trademark) 7300). Examples of the fluorinated alkylamine include perfluorotripropylamine and perfluorotributylamine. Examples of fluoroalcohols include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, and hexafluoroisopropanol. As the non-fluorinated organic solvent, a compound consisting only of hydrogen atoms and carbon atoms, and a compound consisting only of hydrogen atoms, carbon atoms and oxygen atoms are preferred, and examples thereof include hydrocarbon organic solvents, alcohol organic solvents, ketone organic solvents, ether organic solvents and ester organic solvents. The present coating liquid preferably contains 50 to 99.999 mass % of the liquid medium, more preferably 70 to 99.5 mass %, further preferably 90 to 99.5 mass %, and particularly preferably 99 to 99.9 mass %.

[0102] The present coating liquid may contain, in addition to the present composition and the liquid medium, other components within the scope of not impairing the effects of the present invention. Examples of other components include known additives such as acid catalysts and base catalysts that promote the hydrolysis and condensation reaction of hydrolyzable silyl groups. The content of other components in the present coating liquid is preferably 10% by mass or less, particularly preferably 1% by mass or less.

[0103] The solids concentration of the present coating liquid is preferably from 0.001 to 50% by mass, more preferably from 0.05 to 30, further preferably from 0.05 to 10, and particularly preferably from 0.01 to 1% by mass. The solid content concentration of the coating liquid is a value calculated from the mass of the coating liquid before heating and the mass after heating in a convection dryer at 120° C. for 4 hours. The concentration of the present composition can be calculated from the solids concentration and the amounts of the present composition, solvent, and the like charged.

[0104] [Goods] The article of the present invention has a surface layer formed from the present composition on the surface of a substrate.

[0105] (Surface layer) In this composition, when L in group (I) in compound (A) and compound (B) is a hydrolyzable group, the group (I) undergoes hydrolysis to form a silanol group (Si-OH), which reacts with other molecules to form a Si-O-Si bond, or the silanol group undergoes a dehydration condensation reaction with a hydroxyl group (substrate-OH) on the surface of the substrate to form a chemical bond (substrate-O-Si). Therefore, the surface layer contains compound (A) and compound (B) in a state in which a part or all of the group (I) of each of compound (A) and compound (B) has undergone hydrolysis. When L in group (I) is a hydroxyl group, the above reaction proceeds without going through a hydrolysis reaction.

[0106] The thickness of the surface layer is preferably 1 to 100 nm, and particularly preferably 1 to 50 nm. When the thickness of the surface layer is equal to or greater than the lower limit of the above range, the effect of the surface treatment is easily obtained. When the thickness of the surface layer is equal to or less than the upper limit of the above range, the utilization efficiency is high. The thickness of the surface layer can be calculated from the vibration period of the interference pattern obtained by obtaining an interference pattern of reflected X-rays by X-ray reflectance method using an X-ray diffractometer for thin film analysis (manufactured by RIGAKU, ATX-G).

[0107] (base material) The substrate in the present invention is not particularly limited as long as it is a substrate that is required to be imparted with lubricity and water and oil repellency. Materials for the substrate include metal, resin, glass, sapphire, ceramic, stone, and composite materials thereof. Glass may be chemically strengthened. An undercoat film such as a SiO2 film may be formed on the surface of the substrate. The substrate is preferably a substrate for a touch panel, a substrate for a display, or a substrate for a spectacle lens, and is particularly preferably a substrate for a touch panel. The substrate for a touch panel has light-transmitting properties. "Having light-transmitting properties" means that the normal incidence visible light transmittance according to JIS R3106:1998 (ISO 9050:1990) is 25% or more. The material of the substrate for a touch panel is preferably glass or a transparent resin.

[0108] (Production method of the article) The article of the present invention can be produced, for example, by the following method. A method for obtaining the article of the present invention, comprising treating the surface of a substrate with the present composition by a dry coating method. A method of applying the coating liquid to the surface of a substrate by a wet coating method and drying the coating liquid to obtain the article of the present invention.

[0109] <Dry coating method> The composition can be used as is in a dry coating method, and is suitable for forming a surface layer having excellent adhesion by a dry coating method. Dry coating methods include vacuum deposition, CVD, sputtering, etc. Vacuum deposition is particularly preferred from the viewpoint of suppressing decomposition of compound (A) and compound (B) and from the viewpoint of the simplicity of the device. In vacuum deposition, a pellet-shaped material in which a metal porous body such as iron or steel is impregnated with the present composition or the present coating liquid may be used.

[0110] The temperature during the vacuum deposition is preferably from 20 to 300°C, particularly preferably from 30 to 200°C. The pressure during vacuum deposition is 1×10 -1 Pa or less is preferable, and 1×10 -2Pa or less is particularly preferred.

[0111] <Wet coating method> Examples of the wet coating method include spin coating, wipe coating, spray coating, squeegee coating, dip coating, die coating, inkjet coating, flow coating, roll coating, casting, the Langmuir-Blodgett method, and gravure coating.

[0112] <Post-processing> In order to improve the abrasion resistance of the surface layer, if necessary, an operation for promoting the reaction of the compound (A) and the compound (B) with the substrate may be carried out, such as heating, humidification, light irradiation, etc. For example, by heating a substrate on which a surface layer has been formed in an atmosphere containing moisture, it is possible to promote reactions such as the hydrolysis reaction of hydrolyzable silyl groups to silanol groups, the reaction of hydroxyl groups and the like on the substrate surface with silanol groups, and the formation of siloxane bonds through condensation reactions of silanol groups. After the surface treatment, compounds in the surface layer that are not chemically bonded to other compounds or the substrate may be removed as necessary. Specific methods include, for example, pouring a solvent onto the surface layer, wiping it off with a cloth soaked in the solvent, etc.

[0113] [Action and Effect] The present composition and the present coating liquid contain compound (A) and compound (B), among which R f Since the content of compound (A) having a smaller number of carbon atoms in the group is 30 to 95 mass % based on the total of compound (A) and compound (B), a surface layer having excellent water droplet sliding properties can be formed. Compound (A) and compound (B) are each R PF R at one end of the chain f The R PF The other end of the chain has a group (I). When a surface layer is formed on a substrate using the compound (A) and the compound (B) having such a structure, R f The R group tends to be oriented on the opposite side to the substrate.f By orienting the groups on the side opposite to the substrate side, the surface energy of the formed surface layer is lowered. In addition, R of each of compound (A) and compound (B) f The carbon number of the R groups is different, so that the surface layer has R groups with different carbon numbers. f It is believed that the groups are dispersed and arranged at a specific ratio to form a physical or physical micro-uneven structure, which further enhances the water repellency of the surface layer, reduces the contact angle and sliding angle of water droplets, and exhibits excellent water droplet sliding properties.

[0114] [Application] The use of the composition, the coating liquid and the article is not particularly limited. For example, they can be used in display input devices such as touch panels, surface protection coatings for transparent glass or transparent plastic (acrylic, polycarbonate, etc.) members, antifouling coatings for kitchens, water-repellent, moisture-proof and antifouling coatings for electronic devices, heat exchangers, batteries, etc., antifouling coatings for toiletries, coatings for members that require electrical conductivity and liquid repellency, water-repellent, waterproof and water-slip coatings for heat exchangers, low-friction surface coatings for the inside of vibrating sieves and cylinders, etc. More specific examples of use include front protective plates, anti-reflection plates, polarizing plates, anti-glare plates for displays, or those with an anti-reflection coating applied to their surfaces; various devices with display input devices that allow operations on the screen with a human finger or palm, such as touch panel sheets and touch panel displays for devices such as mobile phones and personal digital assistants; decorative building materials for wet areas such as toilets, baths, washrooms, and kitchens; waterproof coatings for wiring boards; water-repellent and waterproof coatings for heat exchangers, water-repellent coatings for solar cells, waterproof and water-repellent coatings for printed wiring boards, waterproof and water-repellent coatings for electronic device housings and electronic components, coatings to improve the insulation of power transmission lines, waterproof and water-repellent coatings for various filters, waterproof coatings for radio wave absorbing materials and sound absorbing materials, anti-fouling coatings for baths, kitchen equipment, and toiletries; water-repellent, waterproof, and water-slip coatings for heat exchangers; low-friction surface coatings for vibrating sieves and the inside of cylinders, etc.; surface protective coatings for machine parts, vacuum equipment parts, bearing parts, automobile parts, tools, etc.

[0115] Because of the above effects, the composition, the coating liquid and the article are suitable for use in applications requiring water droplet sliding properties, such as stain-resistant coatings for kitchens, water- and moisture-proof coatings and stain-resistant coatings for heat exchangers, stain-resistant coatings for toiletries, coatings for components that require electrical conductivity and liquid repellency, water-repellent, waterproof and water-slip coatings for heat exchangers, etc. EXAMPLES

[0116] The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. In the following, "%" means "% by mass" unless otherwise specified. Among Examples 1 to 10, Examples 3 to 9 are working examples, and Examples 1 to 2 and 10 are comparative examples.

[0117] [Physical properties and evaluation] (number average molecular weight) The number average molecular weight of the fluorinated ether compound is 1 H-NMR and 19 The number of oxyperfluoroalkylene groups (average value) was calculated based on the number of end groups by F-NMR. The end groups are, for example, groups (I) or R f It is based on

[0118] (Water droplet falling angle) A 50 μL drop of water was dropped onto the surface (surface layer) of an article held horizontally, and then the article was gradually tilted, and the angle (falling angle) between the article and the horizontal plane when the drop began to fall was measured.

[0119] (Sliding speed of water droplets) The angle (inclination angle) between the surface of the article and the horizontal plane was set at 40°, and a 50 μL water droplet was dropped onto the surface (surface layer) of the article, and the time it took for the water droplet to travel 50 mm was measured. This travel time was taken as the sliding speed.

[0120] [Synthesis Example 1] Compound (14I-1) was obtained according to the method described in Example 6 of WO 2013 / 121984. CF3-O-(CF2CF2O-CF2CF2CF2CF2O)x3 (CF2CF2O)-CF2CF2CF2-C(O)OCH3...(14I-1) Compound (14I-1): Average number of units x3 is 13, number average molecular weight is 4,700.

[0121] 9.0 g of compound (14I-1) and 0.45 g of H2N-CH2-C(CH2CH=CH2)3 were placed in a 50 mL eggplant flask and stirred for 12 hours. NMR confirmed that all of compound (14I-1) was converted to compound (17I-1). In addition, methanol was produced as a by-product. The resulting solution was diluted with 9.0 g of CF3CH2OCF2CF2H (manufactured by Asahi Glass Co., Ltd., AE-3000) and purified by silica gel column chromatography (developing solvent: AE-3000) to obtain 7.6 g of compound (17I-1) (yield 84%). CF3-O-(CF2CF2O-CF2CF2CF2CF2O) x3 (CF2CF2O)-CF2CF2CF2-C(O)NH-CH2-C(CH2CH=CH2)3...(17I-1) Compound (17I-1): Average number of units x3 is 13, number average molecular weight is 4,800.

[0122] In a 10 mL PFA sample tube, 6.0 g of compound (17I-1), 0.07 g of a xylene solution of platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 2%), 0.78 g of HSi(OCH3)3, 0.02 g of dimethyl sulfoxide, and 0.49 g of 1,3-bis(trifluoromethyl)benzene (Tokyo Chemical Industry Co., Ltd.) were placed and stirred for 10 hours at 40°C. After the reaction was completed, the solvent was distilled off under reduced pressure, and the mixture was filtered through a membrane filter with a 1.0 μm pore size to obtain 6.7 g of compound (A-1) (yield 100%). CF3-O-(CF2CF2O-CF2CF2CF2CF2O) x3 (CF2CF2O)-CF2CF2CF2-C(O)NH-CH2-C[CH2CH2CH2-Si(OCH3)3]3...(A-1)

[0123] NMR spectrum of compound (A-1); 1 H-NMR (300.4MHz, solvent: CDCl3, standard: TMS) δ (ppm): 0.8 (6H), 1.3-1.6 (12H), 3.4 (2H), 3.7 (27H). 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -55.2 (3F), -82.1 (54F), -88.1 (54F), -90.2 (2F), -119.4 (2F), -125.4 (52F), -126.2 (2F). Average value of number of units x3: 13, number average molecular weight of compound (A-1): 5,100.

[0124] [Synthesis Example 2] Compound (14I-2) was obtained according to the method described in Example 2 of WO 2013 / 121984. CF3CF2-O-(CF2CF2O-CF2CF2CF2CF2O) x4 (CF2CF2O)-CF2CF2CF2-C(O)OCH3...(14I-2) Compound (14I-2): Average number of units x4 is 13, number average molecular weight is 4,800.

[0125] The procedure of Example 1-2 was repeated except that compound (14I-2) was used instead of compound (14I-1), to obtain 8.4 g of compound (17I-2) (yield 93%). CF3CF2-O-(CF2CF2O-CF2CF2CF2CF2O) x4 (CF2CF2O)-CF2CF2CF2-C(O)NH-CH2-C(CH2CH=CH2)3...(17I-2) Compound (17I-2): Average number of units x4 is 13, number average molecular weight is 4,900.

[0126] The procedure of Example 1-3 was repeated except that compound (17I-2) was used instead of compound (17I-1), to obtain 6.7 g of compound (B-1) (yield 100%). CF3CF2-O-(CF2CF2O-CF2CF2CF2CF2O) x4(CF2CF2O)-CF2CF2CF2-C(O)NH-CH2-C[CH2CH2CH2-Si(OCH3)3]3...(B-1)

[0127] NMR spectrum of compound (B-1); 1 H-NMR (300.4MHz, solvent: CDCl3, standard: TMS) δ (ppm): 0.8 (6H), 1.3-1.6 (12H), 3.4 (2H), 3.7 (27H). 19 F-NMR (282.7 MHz, solvent: CDCl3, standard: CFCl3) δ (ppm): -84.0 (54F), -88.2 (3F), -89.2 (58F), -119.7 (2F), -126.5 (54F). Average value of number of units x4: 13, number average molecular weight of compound (B-1): 5,200.

[0128] [Examples 1 to 10] The compounds (A-1) and (B-1) were mixed in the mass ratio shown in Table 1 to prepare compositions, which were then subjected to the following evaluations. However, in Example 1, only the compound (A-1) was used, and in Example 2, only the compound (B-1) was used.

[0129] (evaluation) The surface of a substrate was treated with each of the compounds or compositions obtained in Examples 1 to 10 to obtain an article having a surface layer on the surface of the substrate. The surface treatment method used in each example was the dry coating method and the wet coating method described below. Chemically strengthened glass (Dragontrail) was used as the substrate. The water contact angle and the water droplet sliding speed of the obtained article were evaluated. The results are shown in Table 1.

[0130] <Dry coating method> Dry coating was performed using a vacuum deposition apparatus (VTR-350M, manufactured by ULVAC Corporation) (vacuum deposition method). 0.5 g of each of the compounds or compositions obtained in Examples 1 to 10 was loaded into a molybdenum boat in the vacuum deposition apparatus, and the inside of the vacuum deposition apparatus was heated to 1×10 -3The boat on which the composition was placed was heated at a rate of 10°C / min or less, and when the deposition rate measured by a quartz crystal oscillator film thickness gauge exceeded 1 nm / sec, the shutter was opened to start film formation on the surface of the substrate. When the film thickness reached about 50 nm, the shutter was closed to end film formation on the surface of the substrate. The substrate on which the composition was deposited was heat-treated at 120°C for 30 minutes and washed with AK-225 to obtain an article having a surface layer on the surface of the substrate.

[0131] <Wet coating method> Each compound or composition obtained in Examples 1 to 10 was mixed with C4F9OC2H5 (3M, Novec (registered trademark) 7200) as a liquid medium to prepare a coating liquid with a solid content concentration of 0.05%. A substrate was dipped in the coating liquid, left for 30 minutes, and then pulled out (dip coating method). The coating film was dried at 120°C for 30 minutes and washed with AK-225 to obtain an article having a surface layer on the surface of the substrate.

[0132] [Table 1]

[0133] The compositions of Examples 3 to 9, which contained compound (A-1) and compound (B-1) in an amount of 30 to 95 mass% based on the total amount of compound (A-1), had lower sliding angles and faster sliding speeds and were excellent in the water droplet sliding properties of the surface layer, compared to Examples 1 and 2, in which compound (A-1) and compound (B-1) were used alone, respectively. The water droplet sliding property of the surface layer in Example 10, in which the content of compound (A-1) was less than 30 mass % based on the total amount of these, was equivalent to that of Example 1.

[0134] (Examples 11 to 20) Commercially available CF3O{(CF2CF2O) m (CF2O) n The following compound (A-2) was obtained using a compound represented by}CF2CH2OH (wherein the average value of m is 20 and the average value of n is 21) according to the methods described in Synthesis Examples 11 to 15 of Japanese Patent No. 5761305. CF3-O-{(CF2CF2O) 20 -(CF2O) 21}-CF2CH2OCH2CH2CH2-Si[CH2CH2CH2-Si(OCH3)3]3··· (A-2) Furthermore, according to the method described in Example 1 of WO 2017 / 038830, the following compound (B-2) was obtained. CF3CF2CF2-O-(CF2CF2O)2{(CF2O) 21 (CF2CF2O) 20}-CF2-CH2OCH2-C[CH2OCH2CH2CH2-Si(OCH3)3]3...(B-2) The above compound (A-2) and compound (B-2) were used to dry coat a substrate in the same manner as in Examples 1 to 10, and the resulting articles were evaluated for their sliding angle and sliding speed. The results are shown in Table 2.

[0135] [Table 2]

[0136] The compositions of Examples 13 to 19, which contained compound (A-2) and compound (B-2) in an amount of 30 to 90 mass% of the total of compound (A-2), had lower sliding angles and faster sliding speeds and were excellent in the water droplet sliding properties of the surface layer, compared to Examples 11 and 12, in which compound (A-2) or compound (B-2) was used alone, respectively. The water droplet sliding property of the surface layer in Example 20, in which the content of compound (A-2) was less than 30 mass % based on the total amount of these, was equivalent to that of Example 11. [Industrial Applicability]

[0137] The composition and the coating liquid can be used in various applications where lubricity and water- and oil-repellency are required. For example, they can be used in display input devices such as touch panels, surface protection coatings for transparent glass or transparent plastic parts, antifouling coatings for kitchens, water- and moisture-repellent and antifouling coatings for electronic devices, heat exchangers, batteries, etc., and antifouling coatings for toiletries, coatings for parts that require electrical conductivity and liquid repellency, water-repellent, waterproof, and water-slip coatings for heat exchangers, and low-friction surface coatings for the inside of vibrating sieves and cylinders, etc. The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2017-024879, filed on February 14, 2017, are hereby incorporated by reference as the disclosure of the specification of the present invention.

Claims

1. A composition comprising a fluorinated ether compound (A) and a fluorinated ether compound (B), The fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) are both fluorine-containing ether compounds represented by the following formula (A / B): In the combination of the fluorinated ether compound (A) and the fluorinated ether compound (B) contained in the composition, the number of carbon atoms of R f in the fluorinated ether compound (A) is smaller than the number of carbon atoms of R f in the fluorinated ether compound (B); A fluorinated ether composition characterized in that the content of the fluorinated ether compound (A) is 30 to 95 mass% based on the total amount of the fluorinated ether compound (A) and the fluorinated ether compound (B). [R f -O-Q-R PF -] r Z [-SiR n L 3-n ] s ... (A / B) wherein R f is a perfluoroalkyl group, and when r is 2 or more, the r perfluoroalkyl groups are the same perfluoroalkyl group; Q is a single bond, an oxyfluoroalkylene group containing one or more hydrogen atoms, or a polyoxyfluoroalkylene group formed by bonding 2 to 5 of the oxyfluoroalkylene groups, and the oxyfluoroalkylene groups constituting the group may all be the same or different, R PF is a poly(oxyperfluoroalkylene) chain; Z is a (r+s)-valent linking group; the (r+s)-valent linking group is (i) a substituted or unsubstituted hydrocarbon group, (ii) a group having a group or atom other than a hydrocarbon group between carbon atoms of the substituted or unsubstituted hydrocarbon group or / and at the terminal, or (iii) an organopolysiloxane group; the unsubstituted hydrocarbon group is a linear or branched saturated hydrocarbon group, the substituted hydrocarbon group is a linear or branched saturated hydrocarbon group in which some or all of the hydrogen atoms have been substituted with substituents, and the substituents are each independently a hydroxyl group, a halogen atom, an amino group, a nitro group, a cyano group, or an aminocarbonyl group; groups or atoms other than the hydrocarbon group present between carbon atoms of the hydrocarbon group or / and at the terminals are each independently an ethereal oxygen atom, a thioethereal sulfur atom, a nitrogen atom, a silicon atom, a carbon atom, —N(R 15 )—, —C(O)N(R 15 )—, —OC(O)N(R 15 )—, —Si(R 16 )(R 17 )—, an organopolysiloxane group, —C(O)—, —C(O)—O—, or —C(O)—S—; R 15 is a hydrogen atom, an alkyl group, or a phenyl group; R 16 to R 17 are each independently an alkyl group or a phenyl group; the organopolysiloxane group may be linear, branched, or cyclic; L is a hydroxyl group or a hydrolyzable group; R is a hydrogen atom or a monovalent hydrocarbon group; n is an integer from 0 to 2, When n is 0 or 1, (3-n) Ls may be the same or different; When n is 2, n R's may be the same or different, r is an integer of 1 or more, (i) s in the fluorinated ether compound (A) is 2 and s in the fluorinated ether compound (B) is 2, (ii) s in the fluorinated ether compound (A) is 2 and s in the fluorinated ether compound (B) is 3, or (iii) s in the fluorinated ether compound (A) is 3 and s in the fluorinated ether compound (B) is 2, r+s is 3 to 8; In the fluorinated ether compound (A) in which s is 2, the (r+s)-valent linking group is a group having a nitrogen atom and —C(O)—, In the fluorinated ether compound (B) in which s is 2, the (r+s)-valent linking group is a group having a nitrogen atom and —C(O)—, The [—SiR n L 3-n ] groups in the fluorine-containing ether compound (A) and the fluorine-containing ether compound (B) may be the same or different.

2. 2. The fluorine-containing ether composition according to claim 1, wherein R f in said fluorine-containing ether compound (A) has 1 to 19 carbon atoms, and R f in said fluorine-containing ether compound (B) has 2 to 20 carbon atoms.

3. 3. The fluorinated ether composition according to claim 1 or 2, wherein Rf in said fluorinated ether compound (A) has 1 carbon atom and Rf in said fluorinated ether compound (B) has 2 or 3 carbon atoms, or wherein Rf in said fluorinated ether compound (A) has 2 carbon atoms and Rf in said fluorinated ether compound (B) has 3 carbon atoms.

4. The fluorine-containing ether composition according to any one of claims 1 to 3, wherein r is 1 to 3.

5. A fluorinated ether composition comprising a fluorinated ether compound (A1) represented by the following formula (A1) and a fluorinated ether compound (B1) represented by the following formula (B1), wherein the content of the fluorinated ether compound (A1) is 30 to 95 mass% based on the total amount of the fluorinated ether compound (A1) and the fluorinated ether compound (B1): [R ｆａ -O-Q ａ -R ＰＦａ -] ｒ１ Z ａ [-SiR ａ ｎ１ L ａ ３－ｎ１ ] ｓ１ ・・・(A1) [R ｆｂ -O-Q ｂ -R ＰＦｂ -] ｒ２ Z ｂ [-SiR ｂ ｎ２ L ｂ ３－ｎ２ ] ｓ２ ・・・(B1) However, R ｆａ and R ｆｂ is a perfluoroalkyl group, and R ｆａ The number of carbon atoms in R ｆｂ The number of carbon atoms is less than that of Q ａ and Q ｂ represents a single bond, an oxyfluoroalkylene group containing one or more hydrogen atoms, or a polyoxyfluoroalkylene group formed by bonding 2 to 5 of the oxyfluoroalkylene groups, and the oxyfluoroalkylene groups constituting the group may all be the same or different, R ＰＦａ and R ＰＦｂ is a poly(oxyperfluoroalkylene) chain, Z ａ is a (r1+s1)-valent linking group, the (r1+s1)-valent linking group is (i) a substituted or unsubstituted hydrocarbon group, (ii) a group having a group or atom other than a hydrocarbon group between carbon atoms of the substituted or unsubstituted hydrocarbon group or / and at the terminal, or (iii) an organopolysiloxane group; Z ｂ is a (r2+s2)-valent linking group, the (r2+s2)-valent linking group is (i) a substituted or unsubstituted hydrocarbon group, (ii) a group having a group or atom other than a hydrocarbon group between carbon atoms of the substituted or unsubstituted hydrocarbon group or / and at the terminal, or (iii) an organopolysiloxane group, the unsubstituted hydrocarbon group is a linear or branched saturated hydrocarbon group, the substituted hydrocarbon group is a linear or branched saturated hydrocarbon group in which some or all of the hydrogen atoms have been substituted with substituents, and the substituents are each independently a hydroxyl group, a halogen atom, an amino group, a nitro group, a cyano group, or an aminocarbonyl group; groups or atoms other than the hydrocarbon group present between carbon atoms of the hydrocarbon group or / and at the terminals are each independently an ethereal oxygen atom, a thioethereal sulfur atom, a nitrogen atom, a silicon atom, a carbon atom, —N(R 15 )—, —C(O)N(R 15 )—, —OC(O)N(R 15 )—, —Si(R 16 )(R 17 )—, an organopolysiloxane group, —C(O)—, —C(O)—O—, or —C(O)—S—; R 15 is a hydrogen atom, an alkyl group, or a phenyl group; R 16 to R 17 are each independently an alkyl group or a phenyl group; the organopolysiloxane group may be linear, branched, or cyclic; L ａ and L ｂ is a hydroxyl group or a hydrolyzable group, R ａ and R ｂ is a hydrogen atom or a monovalent hydrocarbon group, n1 and n2 are integers from 0 to 2, (3-n1) L when n1 is 0 or 1 ａ , (3-n2) L when n2 is 0 or 1 ｂ may be the same or different, When n1 is 2, n1 R ａ , when n2 is 2, n2 R ｂ may be the same or different, r1 and r2 are integers of 1 or more, and when r1 is 2 or more, r1 R ｆａ , Q ａ and R ＰＦａ may be the same or different, and when r2 is 2 or more, r2 R ｆｂ , Q ｂ and R ＰＦｂ may be the same or different, (i) s1 is 2 and s2 is 2, or (ii) s1 is 2 and s2 is 3, or (iii) s1 is 3 and s2 is 2; In the fluorinated ether compound (A1) in which s1 is 2, the (r1+s1)-valent linking group is a group having a nitrogen atom and —C(O)—, In the fluorine-containing ether compound (B1) in which s2 is 2, the (r2+s2)-valent linking group is a group having a nitrogen atom and —C(O)—, s1 [-SiR ａ ｎ１ L ａ ３－ｎ１ ] may be the same or different, and s two [—SiR ｂ ｎ２ L ｂ ３－ｎ２ ] may be the same or different.

6. When r1 in the formula (A1) is 2 or more, r1 R ｆａ The fluorine-containing ether composition according to claim 5, wherein are the same.

7. When r2 in the formula (B1) is 2 or more, r2 R ｆｂ The fluorinated ether composition according to claim 5 or 6, wherein

8. R in the formula (A1) ｆａ The number of carbon atoms in the formula (B1) is 1 to 19, ｆｂ The fluorine-containing ether composition according to any one of claims 5 to 7, wherein the carbon number of the formula is 2 to 20.

9. R in the formula (A1) ｆａ The number of carbon atoms in the formula (B1) is 1, ｆｂ or R in formula (A1) has 2 or 3 carbon atoms. ｆａ The number of carbon atoms is 2, and R in the formula (B1) ｆｂ The fluorine-containing ether composition according to any one of claims 5 to 8, wherein the number of carbon atoms is 3.

10. A coating liquid comprising the fluorinated ether composition according to any one of claims 1 to 9 and a liquid medium.

11. An article having a surface layer formed from the fluorinated ether composition according to any one of claims 1 to 9.