TW200922969A - Surface treating agent, article, and novel fluorine-containing ether compound - Google Patents

Abstract

Disclosed is a surface treating agent which enables to form a coating film which is excellent in water repellency, oil repellency and removability of fat and oil dirt, while exhibiting excellent deterioration resistance under high temperature conditions in the presence of an acid catalyst. Also disclosed are an article treated with such a surface treating agent, and a novel fluorine-containing ether compound (A) which is useful as such a surface treating agent. Specifically disclosed is a surface treating agent characterized by essentially containing a compound (A) represented by the following formula: RF1O(CF2CF2O)aCF2-(Q)b(-(CH2)d-SiLpR3-p)c, and a partially hydrolyzable compound (B) or a partially hydrolyzed product thereof. In this connection, RF1 represents a perfluoro monovalent saturated hydrocarbon group having 1-20 carbon atoms or the like; a represents an integer of 1-200; b represents 0 or 1; Q is absent or a divalent or trivalent linking group; c represents 1 or 2; d represents an integer of 2-6; L represents a hydrolyzable group; R represents a hydrogen atom or a monovalent hydrocarbon group; and p represents an integer of 1-3.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface treatment agent and an article treated with the surface treatment agent, and a novel fluorine-containing ether compound useful as a surface treatment agent. [Prior Art] The fluorine-containing compound is used as a surface treatment agent such as a water and oil repellent film. By applying the compound to the surface of an inorganic substrate such as glass or a resin substrate or a molded article to form a coating film, an article having water repellency and oil repellency can be obtained. As the compound, a compound having a hydrolyzable group bonded to a perfluoroalkyl group and a ruthenium atom (hereinafter referred to as a hydrolyzable group) is known. As the compound, for example, the following compound (1) is used (patent documents 1 and 2 for reference). CF3(CF2)7(CH2)2Si(NCO)3 (1). When the compound (1) is applied to the surface of the substrate, the hydroxyl group or water on the hydrolyzable gene substrate is hydrolyzed to form a sterol group. The compound (1) is partially condensed by a sterol group to form an oligomer, and is rapidly adsorbed on the surface of the substrate to carry out hydrogen bonding. Thereafter, the residual sterol group is subjected to a dehydration condensation reaction with a hydroxyl group on the surface of the substrate to form a strong chemical bond. When the hydrolyzable group is bonded to the substrate, the perfluoroalkyl group is disposed on the atmosphere side. The coating film formed by the compound (1) exhibits water repellency (refer to Patent Document 3). However, the perfluoroalkyl group has high crystallinity, rigidity, and the like, and the coating film formed by the compound (1) is inferior in oil stain removal property. In order to solve the problem of the compound, a perfluoropolyether group is known as a -4-200922969 compound. For the compound, for example, the following compound (2) can be mentioned (patent document 4 for reference). However, s is an integer of 1 or more. CF3CF2CF20-(CF2CF2CF20)s-CF2CF2(CH2)3Si(0CH3)3 (2). The perfluoropolyether gene has a soft structure in which the rigid perfluoroalkyl group is softened by a highly mobile oxygen atom, and the coating film formed by the compound (2) has excellent oil-repellent property and water and oil repellency. However, the compound (2) has the following problems. (i) The coating film formed by the compound (2) is superior to the coating film formed by the compound (丨), but the ratio of the oxygen atom to the carbon atom in the perfluoropolyether group is small. That is, since the segmentation portion of the oxygen atom is small, the mobility of the perfluoropolyether group cannot be said to be sufficient, and the removal of the oil stain is insufficient. (Π) The coating film formed by the compound (2) exhibits sufficient water and oil repellency, and it is necessary to increase the number of s. Therefore, the ratio of the fluorine atom to the compound (2) is larger than that of the compound (丨), and it becomes difficult to dissolve in a non-fluorine-based solvent, and preparation of a high-concentration solution becomes difficult. Further, the compound having a large number of s (2) has a small ratio of the hydrolyzable group, and the adhesion to the surface of the substrate is lowered. The abrasion resistance of the coating film formed by the compound (2) is lowered. (iii) The perfluoropolyether group of the compound (2) is synthesized by ring-opening polymerization of 2,2,3,3-tetrafluorooxetane (Non-patent Document 1 p. 443-444 for reference). However, the transport polymerization of 2,2,3,3-tetrafluorooxetane is difficult to control the molecular weight of the compound (2) because it is carried out by F-ion in the presence of a Lewis acid catalyst. Further, there is a problem that the molecular weight distribution becomes large. -5- 200922969 A compound having a perfluoropolyether group, also known as the following compound (3)~(5buCF3CF2CF20-(CF(CF3)CF20)t-CF(CF3)(CH2)3Si(〇CH3)3 ( 3), (CH30)3Si(CH2)3CF20-(CF2CF20)cr(CF20)r-CF2(CH2)3Si(〇CH3)3 (4) (However, q, r, and t are each independently, and represent an integer of 1 or more (CH3)3Si(CH2)30CH2CF2(0CF2CF2)p(0CF2)q0CF2CH20(CH2)3Si(OCH3)3 (5) (however, p and q are 22). Compound (3) is a perfluoropolyether group. Although the carbon number between oxygen atoms is 2, and -CF3 exists in the side chain, the mobility of the perfluoropolyether group is restricted, and the oil stain removal property is insufficient. The removal of oil stain is based on the mobility of the perfluoropolyether group. It is revealed that the kinematic system is possessed by a segmental carbon atom-a carbon atom between carbon atoms. In the compound (3), _Cf3 exists in the vicinity of the oxygen atom, and the perfluoropoly group is restricted by the steric hindrance of -CF3. The mobility of the ether group, for example, the compound having a perfluoropolyether group in the side chain -CL and the compound having a perfluoropolyether group in the absence of _Cf3 in the side chain, the absolute viscosity, viscosity temperature dependence Greatly different (non-patent document 1 p .454-455 for reference.) The ratio of the compound (4) and the compound (5) to the oxygen atom of the carbon atom in the perfluoropolyether group is large in the side chain-free-CF3, although the high molecular weight perfluoropolymer is polymerized. The acid group has the advantage of being easy to synthesize in the industry, but has the following problems: (1) The perfluoropolyether group is synthesized by photooxidation polymerization of tetrafluoroethylene. The photooxidation synthesis inevitably generates _〇CF2. 〇_structure, q/r is almost 200922969 1.0. The report indicates that the -ocf2o-structure is easily decomposed in the presence of an acid catalyst and under high temperature conditions (Patent Document 5, p. 463, 466 of Non-Patent Document 1) -468, Non-Patent Documents 2 and 3 are referred to.) Therefore, the coating films formed by the compounds (4) and (5) have poor deterioration resistance. (ii) Since both ends have a hydrolyzable group, both ends are fixed to the base. Therefore, the mobility of the perfluoropolyether group is restricted, and the perfluoropolyether group is present in the vicinity of the surface of the substrate and along the surface. Therefore, sufficient water and oil repellency and oil stain removal cannot be exhibited. Glass, display (liquid crystal display, CRT display, projection display, electricity A product such as a display, an EL display, or the like is used under various conditions. Therefore, when a coating film of a compound having a perfluoropolyether group is formed on the surface of the article, it is expected to impart water and oil repellency and oil stain removal property. In the case of the long-term temperature and the range of the humidity, the performance is continued. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei 9-28-663 Japanese Patent Publication No. 298 1 043 [Patent Document 4] JP-A-2000-A No. 2, 00, 196, pp. , John Wiley & Sons Ltd., 1997, p. 443-444, 454-455, 463, 466-468 [Non-Patent Document 2] C. Tonelli, 2 outside, "Linear perfluoropolyalkylether difunctional oligomers: chemistry ' Properties and applications", Journal of 200922969

Fluorine Chemistry, Vol. 95, 999, p. 51-70 [Non-Patent Document 3] P.H. Kasai, "Perfluoropolyethers:

Intramolecular disproportionation", Macromolecules, Vol. 25, 992, p. 679 1 [Problems to be solved] The present invention provides water and oil repellency, oil stain removal, acid catalyst A surface treatment agent for a coating film which is excellent in deterioration resistance under high temperature conditions in the presence of the film. Further, it is an article which is formed of the surface treatment agent and which has excellent water repellency and oil repellency and excellent oil removal property, and which is excellent in resistance to high temperature conditions even in the presence of an acid catalyst. Further, the present invention provides a novel fluorine-containing ether compound which is useful as a surface treating agent. [Means for Solving the Problem] The present invention relates to the following invention. [1] A surface treatment agent characterized by a compound represented by the following formula (A) and a compound (B) which can be partially hydrolyzed with the compound represented by the formula (A), or a formula (A) The partial hydrolysis condensate of the compound (B) which is partially hydrolyzed with the compound represented by the formula (A) is an essential component, RF10(CF2CF20)aCF2-(Q)b(-(CH2)d-SiLpR3-p c(A) but the symbol in the formula indicates the following meaning, RF1: a perfluoromonovalent saturated hydrocarbon group having a carbon number of 1 to 20, or an etheric oxygen atom interposed between a carbon atom of -8-200922969 a perfluoro-valent monovalent saturated hydrocarbon group having 2 to 20 carbon atoms, and the base has no _〇CF20-structured group, a: an integer of 1 to 200, b: 0 or 1, Q: when b is 0, Q is not When b is 1, Q is a linking group of 2 to 3 valence, when e:Q is absent or when c is a divalent linking group, c is 1, and when Q is a 3 valent linking group, c is 2, d : 2 An integer of ～6, L: a hydrolyzable group, R: a hydrogen atom or a monovalent hydrocarbon group, and p: an integer of 1 to 3. [2] The surface treatment agent according to [1], wherein the compound represented by the formula (A) is a compound represented by the following formula (a), RF10(CF2CF2〇)aCF2-X (a), but the symbol in the formula In the following senses, RF1 and a: have the same meaning as the above. 'X: Any one selected from the following formula (XI) to the following formula (X7) (however, L, R, and P have the same meaning as described above), -C(0)NHCH2CH2CH2SiLpR3-p (XI) -CH2〇C(0)NHCH2CH2CH2SiLpR3-p (X2), -CH2OCH2CH2CH2SiLpR3-p (X3), -CF2OCH2CH2CH2SiLpR3-p (X4), -CH2CH2SiLpR3.p (X5), 200922969 -CH2CH2CH2SiLpR3-p (X6), -C(0)N(CH2CH2CH2SiLpR3-p)2 (X7). [3] The surface treatment agent according to [2], wherein X is a group selected from any one of the above formula (XI) to the above formula (X6). [4] The surface treatment agent according to any one of [1] to [3] wherein the molecular weight distribution (Mw/Mn) of the compound represented by the formula (A) is 1.05 to 1.3. [5] The surface treatment agent according to any one of [1] to [4] wherein the compound (Β) is selected to have two or more groups represented by the above formula (XI) to the above formula (Χ7). The compound other than the base is a perfluorohydrocarbon group containing an etheric oxygen atom, and a compound having a structure in which no - 〇CF20-structure is present is an essential component. [6] The surface treatment agent according to any one of [1] to [4] wherein the compound (B) is a compound represented by the following formula (B1) and/or a compound represented by the following formula (B2) is an essential component. , X2-CF20(CF2CF20)uCF2-X2 (B1), [RF30(CF2CF20)v-]zY[-0(CF2CF20)wCF2-X3]x(B2) However, the symbol in the formula indicates the following meaning, X2 X3: each independently represents a group selected from the group represented by the following formula (XI) to the group of the following formula (X7) (however, L, R, and p have the same meanings as described above). -C(0)NHCH2CH2CH2SiLpR3.p (XI), -CH20C(0)NHCH2CH2CH2SiLpR3-p (X2), -CH2OCH2CH2CH2SiLpR3-p (X3), -CF2OCH2CH2CH2SiLpR3-p (X4), -10-200922969 -CH2CH2SiLpR3-p (X5 ), -CH2CH2CH2SiLpR3-p (X6), -C(0)N(CH2CH2CH2SiLpR3-P)2(X7) RF3: a perfluoromonovalent saturated nicotine group having a carbon number of 1 to 20 or an ethericity interposed between one carbon atom The oxygen atom has a carbon number of 2 to 20 and a hydrocarbon group, and the group does not have a -〇CF20-structure group, Y is a (x + z) valence total oxidation saturated nicotine group, or an ether is interposed between carbon atoms. The perfluorination saturation of the (X + Z) valence of the oxygen atom is absent - the base of the 〇CF20-structure, u, v, w: each independently, an integer from 1 to 200. X, z: X is an integer of 2 or more, z is an integer of 0 or more, and is an integer of 3 or more. When z is 2 or more, RF30 (the base of CF2CF may be the same or different, and when X is 2 or more, -0) (CF2CF20) The group represented by wCF2-X3 may be the same or different. [7] The surface treatment composition (B) according to any one of [1] to [6] is a fluorine-free atom and has a fluorene atom. The compound of the structure of the atomic bond 2 is a necessary component. [8] The ratio of the total mass of the surface treatment composition (B) according to any one of [1] to [7] to the total mass of the compound (A) [9] The surface treatment agent organic solvent according to any one of [1] to [8]. [1] The surface treatment agent according to [9], wherein the organic solvent is an organic solvent. The carbon atom is a fluorine-valent monovalent saturated mono-carbon-hydrocarbon group, and yttrium, (x+z) ϊ〇) ν - is represented by hydrazine, wherein more than one water is formed, wherein 0.1 to 5 0 is contained, and the content thereof is non-fluorine- 11 - 200922969 [11] A method for producing a surface-treated substrate, which is characterized in that the surface treatment agent according to any one of [1] to [10] is applied to a surface of a substrate and dried. This surface treatment is carried out. [12] - a compound represented by the following formula (A) (however, the compound has no -Ο CF 2 Ο - structure), RF10(CF2CF20)aCF2-(Q)b(-(CH2)d-SiLpR3-p) c(A) However, the symbol in the formula indicates the following meaning, RF1: a perfluoromonovalent saturated hydrocarbon group having a carbon number of 1 to 20, or a carbon number of 2 to 20 in which an etheric oxygen atom is interposed between carbon atoms and one carbon atom. a perfluoro-monovalent saturated hydrocarbon group, and the group has no -CF20-structured group, a: an integer of 1 to 200, b: 0 or 1, Q: when b is 0, Q does not exist, and b is 1 , Q is a linking group of 2 to 3 valence, c: Q is absent or C is a divalent linking group, c is 1, Q is a 3 valent linking group, c is 2, d: an integer of 2 to 6, L : a hydrolyzable group, R: a hydrogen atom or a monovalent hydrocarbon group, p: an integer of from 1 to 3. [1 3 ] - a compound represented by the following formula (a) (however, the compound has no -0CF20-structure), -12- 200922969 RF1〇(CF2CF2〇)aCF2-X (a) However, the symbol in the formula In the following sense, RF1: a perfluoromonovalent saturated hydrocarbon group having a carbon number of 1 to 20, or a total of 2 to 20 carbon atoms having an etheric oxygen atom interposed between one carbon atom, and a hydrocarbon group, and the groups are not present - 〇CF20 - the basis of the structure, a : an integer from 1 to 200. X: is represented by the following formula (XI), the following formula (X2), the following formula (X6)', and any one selected (however, L is a hydrolyzable group, R is a hydrogen atom group, and P is an integer of 1 to 3). ), -C(0)NHCH2CH2CH2SiLpR3-p(XI), -CH20C(0)NHCH2CH2CH2SiLpR3-p(X2), -CH2CH2CH2SiLpR3.p(X6), -C(0)N(CH2CH2CH2SiLpR3-p)2 (X7). [Effect of the Invention] According to the surface treatment agent of the present invention, it is possible to form a coating film which is excellent in water and oil repellent property and which is deteriorated under high temperature conditions in the presence of an acid catalyst. The article obtained by the method for producing an article of the present invention has an excellent property, excellent oil stain removal property, and is excellent in high-temperature condition resistance in the presence of an acid catalyst. The present invention can provide a novel compound which can be used as the surface treating agent. The fluorine atom monovalent saturated formula (X7) or the monovalent hydrocarbon property of the carbon atom is excellent in oil-resistant resistance, water-repellent and oil-repellent deterioration, fluorine-containing etherification-13-200922969 [Best mode for carrying out the invention] In the present specification, The compound shown in A) is referred to as the compound (A). The compounds represented by other formulas are also expressed in the same manner. Further, in the present specification, the base represented by the formula (X) is referred to as the base (X). The bases shown in other formulas are also expressed in the same manner. In the present specification, the perfluoromonovalent saturated hydrocarbon group means a group in which all hydrogen atoms bonded to a carbon atom of a monovalent saturated hydrocarbon group are replaced by a fluorine atom. The monovalent saturated hydrocarbon group means a group formed by a carbon atom and a hydrogen atom, and has no carbon atom-carbon unsaturated bond group. The perfluoromonovalent saturated hydrocarbon group may have a linear structure, a branched structure, a cyclic structure, a partially branched structure, and a cyclic structure. In the present invention, a linear structure is preferred. The number of carbon atoms of the perfluoromonovalent saturated hydrocarbon group is preferably from 1 to 20, more preferably from 1 to 16. Specific examples of the perfluoromonovalent saturated hydrocarbon group include CF3(CF2)m-. CF3(CF2)m-,

CyF-(CF2)n-,

AdF-(CF2)n-. However, m represents an integer of 0 to 19, and an integer of 0 to 15 is particularly preferably an integer of 0 to 6. C/ represents a perfluorocyclohexyl group. AdF stands for perfluoroadamantanethyl. η represents an integer from 0 to 15.

The perfluoromonovalent _ and a hydrocarbon group in which an etheric oxygen atom is interposed between carbon atoms and carbon atoms means a group in which an etheric oxygen atom is interposed between a carbon atom and a carbon atom of the perfluoromonovalent saturated hydrocarbon group. The perfluoro group in which an etheric oxygen atom is inserted is a structure in which the structure of the structure cannot be detected by a usual analytical method (I9F-NMR -14-200922969, etc.). When an etheric oxygen atom is present between the carbon atom and the carbon atom, the number of oxygen atoms to be inserted is preferably from 1 to 7, more preferably from 1 to 4. The position at which the oxygen atom is inserted is between a single bond of a carbon atom and a carbon atom, and the number of carbon atoms existing between the oxygen atoms is 2 or more. <Compound (A) > The compound (A) in the invention is a compound represented by the following formula. RF10(CF2CF20)aCF2-(Q)"-(CH2)d-SiLpR3-p)c (a). a is - (CF2CF20) - the number of units, an integer from 1 to 200, preferably from 2 to 100, 3 to 50 is better, 5 to 25 is better. b is 0 or 1. Q does not exist when b is 0. That is, when b is 0, CF2 is directly bonded to _(CH2)d-. b is 1 In the case where Q is a divalent linking group or a trivalent linking group, the linking group means a group in which an atom or an atom group is bonded via the group. Q is preferably an organic linking group having one or more carbon atoms. When the Q is a divalent linking group, it is 1, and when q is a trivalent linking group, it is 1. c is 1 or 2 when b is 1. b is 0, and c is 1 is a compound (A): Compound (A"). The compound (A) wherein b is 1, c is 1 and Q is a divalent linking group is the following compound (A-2) (however, Q1 is a divalent linking group). The compound (A) wherein b is 1, wherein c is 2 and Q is a trivalent linking group is the following compound (A-3) (however, Q2 is a trivalent linking group). RF10(CF2CF20)aCF2-(CH2)d-SiLpR3-p (A-1). RHCKCFaCFaOhCFi-Q^CHOd-SiLpRs-p (A-2). -15- 200922969 RF10(CF2CF20)aCF2-Q2(-(CH2)d-SiLpR3-p)2 (A·3). In the compound (A), d is preferably 3 to 6, more preferably 3. When the number of d is too small, the decomposition temperature of the compound tends to decrease, and if the number of d is too large, the weather resistance tends to decrease. The RF1 is preferably a perfluoroalkyl group having 1 to 20 carbon atoms, more preferably a group having 1 to 16 carbon atoms, and more preferably a group having 1 to 4 carbon atoms. Further RF1 is preferably based on a linear chain. RF1 is preferably CF3(CF2)m-, and CF3-, CF3CF2-, CF3(CF2)2-, or CF3(CF2)5- is more preferable. Rf1 is preferably cf3(cf2)5- from the viewpoint of water repellency and oil repellency, and CF3- and CF3CF2- are preferred from the viewpoint of recovery of liquid phase direct fluorination which is one of the production steps of the compound. The compound (A) of the present invention is preferably a compound in the absence of -0 C F 2 ◦-structure. Therefore, when RF1 has a group having an etheric oxygen atom, it is preferable to design the structure in which the terminal portion of the bond of RF1 is not -〇CF2-. Q is a divalent linking group or a trivalent linking group. q is preferably a group having a nitrogen atom or an etheric oxygen atom at the end of the -(CH2)d- linkage. The Q1 of the 2-valent linkage is preferably -ConH-, -CH2OCONH-, -CH20-, -CF20-. The q2 of the linking group of the trivalent is preferably _c(〇)N = (however, the extension by N = not the double bond means 2 single bonds). L is a hydrolyzable group. L is a group which becomes a hydroxyl group by a hydrolysis reaction. Namely, the terminal of the compound is hydrolyzed to form a Si-〇H group (sterol group), and further, an intermolecular reaction is formed to form a S i _ 〇 _ s i bond. L' may, for example, be an organic group in which a hydrogen atom of a hydroxyl group is removed from a unit alcohol, a halogen atom, a brewing group, an isooxy acid ester group, or an organic group of a hydrogen atom-16-200922969 from which an amine group is removed from an amine compound. L is industrially easy to manufacture, and is preferably a carbon number of 1 to 4 carbon atoms, a halogen atom or an isocyanate group, a problem of gas release during coating, and preservation stability. The alkoxy group or the isocyanate group of 1 to 4 is more preferable, and the alkoxy group having 1 to 4 carbon atoms is more preferable, and the ethoxy group is particularly preferable when long-term storage stability is required, and the aging time at the time of coating is short time. The methoxy group is particularly preferred. R is a hydrogen atom or a monovalent hydrocarbon group. The monovalent hydrocarbon group may, for example, be an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group, and an alkyl group is preferred from the viewpoint of easiness of synthesis. P is an integer of 1 to 3. p is preferably 2 or 3, and 3 is particularly preferred. The compound (A) can be strongly bonded to the surface of the substrate by the presence of a plurality of L in the molecule. The compound (A) of the present invention has -SiLpR3_p (hereinafter, referred to as hydrolyzable alkylene group) is indirectly bonded to RF 1 〇(CF 2 CF 2 〇) ac F 2 -, and -(CH2)d- The base of the formula or the structure of the base interval of -Q_(CH2)dj is shown. With this configuration, there is an advantage that the decomposition temperature of the compound (A) is increased and the heat resistance is improved. In particular, the structure of the divalent hydrocarbon group represented by the hydrazine atom bond _(CH2)d- of the hydrolyzable decyl group is an essential component, and the weather resistance of the compound can be improved. In particular, d is 3 to 6 Especially when it is 3, it has the advantage of improved weather resistance. The hydrolyzable alkylene group may, for example, be the group described below. -Si(OCH3)3, -Si(OCH2CH3)3, -Si(NCO)3, -17-200922969-SiCl3'-Si(NH2)gCl3-g. However, g is an integer of 1 to 3. The compound (A) may be one type of compound or a mixture of two or more types of compounds. The mixture may, for example, be a mixture of two or more compounds containing RF 1 or a different. The average enthalpy of a in the mixture is preferably 5 to 20. The molecular weight of the compound (A) is preferably from 600 to 2,500, more preferably from 800 to 1,500. When the compound (A) is a mixture of two or more kinds of compounds, the number average molecular weight of the compound (A) is preferably from 600 to 2,500, more preferably from 800 to 1,500. When the compound (A) is a mixture of two or more kinds of compounds, the molecular weight distribution (Mw/Mn) of the compound (A) is preferably 1.05 to 1 -3, more preferably 1.05 to 1.15. When the molecular weight and molecular weight distribution of the compound (A) are in this range, the viscosity of the compound (A) is low, the amount of evaporation is small, and the uniformity in the dissolution of the solvent is excellent. The number average molecular weight and molecular weight distribution of the compound (A) can be measured by colloidal permeation chromatography, and the measurement conditions are as described in the examples below. In the present invention, the compound (A) is -(Q)b(-(CH2)d-SiLpR3-p). The following compound (a) having a structure represented by the group (X1) is preferred. RHOCCFzCFWhCFyX1 (a). X1 represents a group selected from the group (XI) to the group (X7). -C(0)NHCH2CH2CH2SiLpR3-P (XI), -CH20C(0)NHCH2CH2CH2SiLpR3-P (X2), -CH2OCH2CH2CH2SiLpR3-p (X3), -CF2〇CH2CH2CH2SiLpR3-p (X4), -18- 200922969 -CH2CH2SiLpR3-p (X5), -CH2CH2CH2SiLpR3-p (X6), -C(0)N(CH2CH2CH2SiLpR3-p)2 (X7). X1 is preferably a group (XI), a group (X2), a group (X6) or a group (X7), and the group (XI), the group (X2) or the group (X7) is particularly preferred. When X1 is a group (XI), it is preferable from the viewpoint of high production efficiency, excellent testability of the compound (a), and excellent acid resistance. When X 1 is a group (X 2), it is preferable from the viewpoint of excellent productivity. When X 1 is a group (X 6 ), it is preferable from the viewpoint of excellent chemical stability. When X1 is a group (X7), it is preferable from the viewpoint of excellent adhesion to a substrate. Further, a preferred form of the compound (a) is common to the form of the compound (A) (except for the group (X1)). The compound (a) 'is preferably the following compounds (A1) to (A7), respectively. The production method of these compounds will be described later. RF10(CF2CF2〇)aCF2C(0)NHCH2CH2CH2SiLpR3_p (A1) RF10(CF2CF20)aCF2CH20C(0)NHCH2CH2CH2SiLpR3.p (A2) RFI0(CF2CF2〇)aCF2CH2OCH2CH2CH2SiLpR3-p (A3) RF10(CF2CF20)aCF2CF20CH2CH2CH2SiLpR3-p (A4) RF10( CF2CF2〇)aCF2CH2CH2SiLpR3-p(A5) RF10(CF2CF20)aCF2CH2CH2CH2SiLpR3_p(A6) RF10(CF2CF20)aCF2C(0)N(CH2CH2CH2SiLpR3-p)2(A7) Further, compounds (Al)~(A7) are -SiLpR3.p The compound which is partially -SiL3 is preferable, the compound in which L is an alkoxy group having 1 to 4 carbon atoms is particularly preferable, and the compound in which L is a methoxy group or an ethoxy group is more preferable. -19-200922969 Specific examples of the compound (a) include, for example, the following compounds and a compound in which the terminal -Si(OCH3)3 group is -Si(OCH2CH3)3. CF30(CF2CF20)aCF2-C(0)NHCH2CH2CH2Si(0CH3)3, CF3CF20(CF2CF20)aCF2-C(0) NHCH2CH2CH2Si(OCH3)3, CF3CF2CF20(CF2CF20)aCF2-C(0) NHCH2CH2CH2Si(OCH3)3, CF30( CF2CF20)aCF2-CH20C(0) NHCH2CH2CH2Si(OCH3)3, CF30(CF2CF20)aCF2-CH20CH2CH2CH2Si(0CH3)3, CF30(CF2CF20)aCF2-CF20CH2CH2CH2Si(〇CH3)3, CF30(CF2CF20)aCF2-CH2CH2Si(0CH3)3 CF3〇(CF2CF20)aCF2-CH2CH2CH2Si(OCH3)3, CF3〇(CF2CF20)aCF2-C(0)N(CH2CH2CH2Si(CH3)3)2. The compound O) can be produced by a method similar to the method described in International Publication No. WO 02/004397, etc., by a polyethyl methacrylate-based hydrocarbon ether having a carbon skeleton corresponding to RFI0 (CF2CF20) aCF2-. Polyethylene glycol of raw materials has various structures and molecular weights are sold in the market, and can be obtained inexpensively and easily. Further, it is easy to synthesize by ring-opening polymerization of an alcohol having a hydrocarbon skeleton equivalent to rf1〇H and a epoxide. Even if the same ring-opening polymerization 'polyethylene glycol' is different from the above compound (2), it is easy to control the molecular weight. The compound (A) in the present invention can be produced by the following production method. However, in the formula, the R group is not the same as the RF1, or the fluorine atom of the rfi is - 20 - 200922969 or the group substituted by the hydrogen atom is inserted in the alkyl group or between the carbon atoms and one carbon atom. An alkyl group having an etheric oxygen atom is preferred. Rb is a monovalent total gas organic group, preferably a perfluoroarea or a perfluoroalkyl group having an etheric oxygen atom interposed between carbon atoms and carbon atoms. Re is an alkyl group. The meaning of the other symbols is the same as that in the compound (A). The preferred form is also the same. (Method for Producing Compound (A1)) The compound (A1) can be produced through the following steps (a) to (e). (a) Step: a step of reacting the compound (D1) with the compound (D2) to obtain a compound (D3). In the case of the compound (D 1), a mixture of two or more kinds having a different number is easily obtained. When the compound (D1) is a mixture, the compound obtained after the step (a) is also a mixture of two or more kinds of -(CH2CH20)-unit number. (8) [1] R1〇(CH2CH2〇)aCH2CH2〇H + RbCOF (D1) (D2) * R1〇(CH2CH2〇)aCH2CH2pCORb (D3) (b) Step: Perfluorination of compound (d 3 ) gives the following The step of the compound (d 4). The perfluorination may, for example, be a liquid phase vaporization in which a reaction is carried out by introducing F2 into a liquid phase. [Chemical 2] -► (b) R10(CH2CH2〇)aCH2CH2〇CORb (D3) RF10(CF2CF2〇)aCF2CF2〇CORb (D4) -21 - 200922969 (C) Step: Compound (D4), ester bond The step of decomposing the reaction to give the compound (D 5 ). [Chemical 3]

RF10(CF2CF2〇)aCF2CF2〇CORb-RF10(CF2CF2〇)aCF2COF (W) (〇) (D5) (d) Step: esterifying compound (D5) with compound (D6) to obtain compound (D 7) step. The esterification reaction can be carried out in accordance with a known method (for example, the method described in the specification of U.S. Patent No. 3,810,874). Further, the compound (D7) may be obtained by subjecting the compound (D4) to a transesterification reaction with ReOH. RF10{CF2CF2〇)aCF2COORc (D7) (d) RF1〇(CF2CF2〇)a〇F2COF + Rc〇H (D5) (D6) (e) Step: Compound (D 7) and Compound (D) 8) Carrying out the reaction 'The step of obtaining the compound (A1) by removing the by-product Re〇H to the outside of the system.

Re〇H is difficult to remove completely because of the polar solvent. However, 'Re〇H has a small amount of residual, and during the long-term storage of the compound (A1), the chemical equilibrium shift due to the condensation reaction of the hydrolyzable sand alkyl group has the stability of the compound-22-200922969 (A1). advantage. RF10(CF2CF2〇)aCF2C00Rc + NH2CH2CH2CH2 - SiLpR3*p (D7) (e) (D8) RF10(CF2CF2〇)aCF2C(0)NHCH2CH2CH2—SiLpRg-p (A1) (Method for producing compound (A7) The compound (A7) is produced in the step (e) by the step (e-Ι) of changing the compound (D8) to the following compound (DS-1). (e-Ι) step; a step of reacting the compound (D7) with the compound (D8-1) to remove the by-product Re Ο Η to the compound (A 7 ). The compound (D 8 -1) used in the step (e - 1 ) is a compound (D8) Since the reactivity is low, it is preferred to carry out the reaction by distilling off the by-products under reduced pressure, etc. RF10(CF2CF20)aCF2C00Rc(D7) + HN(CH2CH2CH2SiLpR3_p)2 (D8-1) ->RF10( CF2CF2〇)aCF2C(〇)N(CH2CH2CH2SiLpR3-p)2 (A7) (Production Method of Compound (A2)) The compound (A2) is subjected to the following step (f) by using the compound (D7) obtained in the above step (d). a method (manufacturing method (1)) produced by the method of (g) or a compound (D5) obtained by the above step (c), followed by hydrolysis, and also -23-200922969 to obtain a compound (D9) Next, the method of the (g) step (manufacturing method (Part 2)) is preferably produced. (Manufacturing method of the compound (A2) (Part 1)) (f) Step: Performing the reduction of the compound (D 7) and the ester bond The step of decomposing the reaction to obtain the compound (D9). The reduction can be carried out by the method described in the paragraph [〇〇21] of JP-A-10-72568. The reduction is carried out using NaBH4, boron-THF, lithium aluminum hydride, or the like. It is preferred to carry out the reducing agent, and it is better to use NaBH4 with moderate reactivity in the industry. [Chem. 6]

RF10(CF2CF20)aCF2C00Rc -► RF1〇(CF2CF2〇)aCF2CH2OH (D7) (f> (D9) (g) Step: simultaneously drop the catalyst and compound (D 1 1 ) in compound (D9) to The step of obtaining the compound (A2). In this step, no by-products are produced. [Chemical 7] RF10(CF2CF20)aCF2CH20H + OCN-CH2CH2CH2—SiLpR3-p (D9) (D11) RF10(CF2CF2〇)aCF2CH2〇C( 0}NHCH2CH2CH2—-SiLpRa^, (A2) (Production method of compound (A2) (Part 2)) -24 - 200922969 Hydrolysis of compound (D 5 ) gives the following compound (D), followed by reduction of compound ( The compound (D9) is obtained by D1 0), followed by the method of the above step (g). The hydrolysis can be carried out according to a known method (for example, the method described in the specification of U.S. Patent No. 3 8 1 0 8 4). It can be implemented by the method described in paragraph [0021] of the Japanese Patent Publication No. 10-7256-1, etc. RF10(CF2CF20)aCF2C0F (D5) - RFI0(CF2CF20)aCF2C00H (D10) - RF 丨0(CF2CF20)aCF2CH20H (D9) - Compound (A2) (Manufacturing Method of Compound (A3)) Compound (A3) can be produced by subject (D9) to (h) (h) Step: In the compound (D9) obtained by the above method, a catalyst (sodium hydride, potassium t-butoxide or the like) and a compound (D 12) are simultaneously dropped to obtain a compound (A3). [化8]

NaH IT RF10(CF2CF20)aCF2CH20H 十Ch-CH2CH2CH2—SiLpR3_p (D9) (D12) R 〇(CF2CF2〇)aCF2CH2〇CH2CH2CH2-SiLpR^ (A3) (Manufacturing Method of Compound (A4)) -25- 200922969 The compound (D5) can be subjected to the steps (1) to (1) to produce the step (1): the compound obtained by the above method (.5) is the same as the KF temple: heating is carried out, and male and propylene are reacted to obtain an unsaturated grouping port. Step (D 1 3 ). RFi〇(CF2CF2C)aCF2COF + CH2=CHCH2-Br (D5) KF _ RFi〇(CF2cFz〇)aCF2CF2OCH2CH=CH2 (0 (D13) (j) Step: Compound (D13) with compound (D 1 4) The step of carrying out the hydrogen evolution reaction to obtain the compound (A 4 ), and the reaction of the compound (A 4 ), RF10(CF2CF2〇)aCF2CF2OCH2CH=CH2 + H-SiLpR3-p (D13) (°14) _^ RFi〇(cF2CF2〇)aCF2CF2 〇CH2CH2CH2-SiLpR3.p Ο) (A4) (Method for Producing Compound (A5)) The Lil compound (A5) can be used to carry out the step (k) to (m) of the compound (D5) in the step 11 (k): The obtained compound (D5) is reacted with 12 or reacted to convert -C〇F into a ten-M compound. Step -26 - 200922969 RF10(CF2CF20)aCF2l (D15) RF10(CF2CF2O)aCF2C0F + l2 or Lil (D5) (1) Step: by blowing the ethylene compound gas by the compound (D 15) obtained by the above method, heating, decomposing the previously prepared free radical generating agent to generate free radicals in the system, and adjusting the polymerization reaction (telomerization) to obtain the step of the compound (D 16 ). RF10(CF2CF2〇)aCF2l + CH2=CH2 (D15) ♦ RF10(GF2CF2〇)aCF2CH2CH2l (D16) (m) Step: By removing HI from compound (D1 6), an unsaturated group is obtained. The step of the compound (D 17). RF10(CF2CF20>aCF2CH2CH2l-gas RF10(CF2CF2〇)aCF2CH=CH2 (D16) <m> (D17) (η) Step: Compound (D 17) is subjected to hydrazine hydrogenation reaction with compound (d 14) Step of obtaining the compound (A5) -27- 200922969 化ρ10(ΟΡ2ΟΡ2〇)3〇^Η=ΟΗ2 + H-SiLpR3-p (D17) (D14) RF10(CF2CF20)aCF2CH2CH2—SiLpR3-p (A5 (Production Method of Compound (A6) (Part 1)) (〇) Step: By adding allylic acetate to the compound (D 15) obtained by the above method, heating is carried out to decompose the previously prepared free radical generator The step of generating a radical in the system and adjusting the polymerization reaction to obtain the compound (D 18). [Chem. 15] RM0(CF2CF20)aCF2CH2CHICH2OC(0)CH3 (D18) RF10(CF2CF2〇)aCfr2* + CH2= CHCH20C(0)CH3 (D15) (9) (p) Step: a step of obtaining an unsaturated group-containing compound (D19) by dehalogenation from the compound (D 18). [Chem. 16] RF10(CF2CF2〇)aCF2CH2CHICH2 〇C(0)CH3 (D18) Zn -► RF10(CF2CF2〇)aCF2CH2CH=CH2 -28- 200922969 (q) Step: Hydrogenation of hydrazine by compound (c»19) and compound (D14) Should produce the compound (A6) of. [Formula 17] RF10 (CF2CF20) aCF2CH2CH = CH2 + Η-SiLpR3.p (D19) (Ρ) (D14)

RF10(CF2CF2〇)aCF2CH2CH2CH2-Sili)R3H (Αβ) In the production of the compound (A5) and the compound (A6), it is preferred to carry out purification to sufficiently remove the iodine-containing compound. When the compound (?5) or the compound (?6) is used in an electronic device in the state of residual iodine, iodine is generated as ions during a long period of time, and the gold or copper wiring is broken. (Method for Producing Compound (Α6) (Part 2)) A method for obtaining a compound (Α6) in a high recovery ratio without using a production method of a hydrogenation reaction with heat generation, or the following method. For example, the compound (D9) can be reacted with CF3CF2CF2CF2SO2Cl to obtain a compound (D 9 - 2 ). Then, l i I is reacted in a polar solvent such as acetone to obtain a compound (D 9 - 3 ). Further, a compound having a double bond and a hydrolyzable alkylene group such as a compound represented by the formula CH2 = CHSi(OCH3)3 is reacted to obtain the following compound (D 9 - 4 ), followed by deiodination by zinc to obtain The method of the compound (D 9 - 5 ). According to this method, the objective compound (D 9 - 5 ) can be obtained in a tube recovery ratio. -29- 200922969 RF10(CF2CF20)aCF2CH20S02CF2CF2CF2CF3(D9-2) RF10(CF2CF20)aCF2CH2I (D9-3) RF10(CF2CF20)aCF2CH2CH2CH(Si(0CH3)3)-I(D9-4) RF10(CF2CF20)aCF2CH2(CH2CH (Si(0CH3)3)-H(D9-5) The compound (A) in the present invention can be used as a surface treatment agent (lubricant, antifouling agent, water and oil repellent agent, fingerprint removing performance imparting agent, a useful compound such as a detergent-imparting agent, a release agent, a surface modifier, etc., that is, a compound (A) having no structure (A), which is in the presence of an acid catalyst, and is placed in the presence of an acid catalyst. Under high temperature conditions, a coating film having excellent deterioration resistance can be formed. Further, since a perfluoropolyether group is provided, a coating film excellent in water repellency and oil repellency can be formed. Further, the carbon number between oxygen atoms in the perfluoropolyether group is 2. When the side chain does not have -CF 3 , the perfluoropolyether group has high mobility and can form a coating film excellent in oil stain removal property. Further, the compound (A), even if the number of the -(CF2CF2〇)-unit is small, It is still possible to form a coating film excellent in water repellency and oil repellency. Therefore, when the number of -(CF2CF2〇)_ units is reduced, it becomes soluble in a non-fluorine-based solvent, and a high-concentration solution The process is easy to change. Further, the adhesion to the surface of the substrate is improved, and the abrasion resistance of the coating film formed by the compound (A) is improved. Further, the compound (A) having the -(CF2CF2〇)_ unit and the prior art The compound is easy to manufacture and easy to control the molecular weight. The present invention also provides a novel compound (A) which is useful as a surface treating agent. <Compound (B) -30- 200922969 In the present invention, it is a compound (A) And a composition of the other compound (B), and the composition is used as a surface treatment agent, etc. The surface treatment agent of the present invention contains the compound (A) and the compound (B) which can be partially hydrolyzed with the compound (A) as essential components. Further, the surface treating agent of the present invention is a partially hydrolyzed condensate of the compound (A) and the compound (B) which is partially hydrolyzable with the compound (A). The compound (B) is derived from the compound (A). The compound (B) may be one of a fluorine-containing compound and a non-fluorine-based compound, and may be used alone or in combination of two or more. When the compound (B) is used in one type, Fluorine compounds are better When two or more kinds are used, a fluorine-containing compound is preferably an essential component. When the compound (B) is a non-fluorine-based compound, a non-fluorine-based hydrolyzable decane compound, a non-fluorine-based polyazide or the like is preferable. The non-fluorine-based hydrolyzable decane compound is particularly preferable. The adhesion of the coating film obtained by the surface treatment agent to the substrate can be improved by using the compound (B) '. The compound (B) is partially hydrolyzable with the compound (A). a compound having a hydrolyzable group. The number of the hydrolyzable groups in the compound (B) is preferably 1 or more and 2 to 4 is preferred. Further, the hydrolyzable group is preferably a hydrolyzable decyl group, and is particularly preferably the same as the group represented by the above formula -SiLpR3_p (but in the formula [, the ruler and p have the same meanings as defined above). When the compound (B) is a compound having a group represented by the formula -SiLpR3-p, the structure of the group may be the same as or different from the compound (A) for the compound (B).

The group represented by the formula -SiLpR3_p in the π-substance (B) is preferably the same as the compound (a) and l and R-31 - 200922969, and P is the same or a different base. Further, the compound (B) is preferably a compound having a group represented by the above formula (X1) to formula (?7), and a structure other than the group is preferably a compound having a structure different from the compound (A). Further, the compound (B) is a compound having a structure represented by the above formula (χ1) to (X7), and a compound having an all-performing group containing an etheric oxygen atom different from the compound (a). It is better. (Fluorinated hydrolyzable decane (B)) The compound (B) has a fluorine atom and a fluorine-containing one having two or more hydrolyzable oxime groups represented by the formula - SiLpR3_p from the viewpoint of excellent chemical stability. The hydrolyzable decane compound is preferred, and it is particularly preferable to have a hydrolyzable hydrolyzable decane having two or more hydrolyzable decyl group having a formula of _siLpR3_p and having a -OCFaO-structure. The fluorine-containing hydrolyzable decane (B) has a group selected from two or more groups represented by the formula (XI) to the formula (X7), and the structure other than the group is an ether-containing oxygen atom. A compound having a fluorohydrocarbon group and a structure in which no _〇CF2〇-structure is present is preferred. The compound which is preferably a fluorine-containing hydrolyzable decane (B) is the following compound (B1) or the following compound (B2). X2-CF20(CF2CF20)uCF2-X2 (B1) [RF30(CF2CF20)v.]zY[.〇(CF2CF20)wCF2-X3]x (B2) X2 represents selected from base (XI) to base (X7) Any base. X2 -32 - 200922969 The preferred form is the same as that described in χ1. u denotes the number of -(CF2cf2〇)_ units, which is an integer from 1 to 200, preferably from 2 to 100, more preferably from 3 to 50, and even more preferably from 5 to 2 5 . RF3 represents a perfluoroalkyl group having 1 to 20 carbon atoms or a perfluoroalkyl group having an etheric oxygen atom interposed between carbon atoms and carbon atoms (but having no structure of -〇CF2o-). The preferred form of rF3 is the same as that described by rfi. X3 represents a group selected from the group (XI) to the group (X7). The preferred form of X3 is the same as that described for X1. u, V, w are independent, indicating - (CF2CF2〇) - the number of units, an integer from 3 to 200, preferably an integer from 3 to 100, an integer from 3 to 70, and an integer from 5 to 50. good. (Compound (B1)) In terms of the compound (B1), the following compounds (B1-1) to (B1-7) are preferred. R3.pLpSiCH2CH2CH2NHC(0)-CF20(CF2CF20)uCF2-C(0) NHCH2CH2CH2SiLpR3-p (B1-1), R3-pLpSiCH2CH2CHNHC(0)0CH2-CF20(CF2CF20)u CF2-CH20C(0)NHCH2CH2CH2SiLpR3-p (Bl -2), R3-pLpSiCH2CH2CH20CH2-CF20(CF2CF20)uCF2-CH2 OCH2CH2CH2SiLpR3-p (Bl-3), R3-pLpSiCH2CH2CH20CF2-CF20(CF2CF20)uCF2-CF2OCH2CH2CH2SiLpR3_p (Bl-4)' R3-pLpSiCH2CH2-CF20(CF2CF20)uCF2 -CH2CH2SiLpR3 - p -33- 200922969 (Bl-5), R3-PLpSiCH2CH2CH2-CF20(CF2CF20)uCF2-CH2CH2CH2SiLpR3.p (Bb6), (R3-PLpSiCH2CH2CH2)2NC(0)-CF20(CF2CF20)uCF2-C (0) N(CH2CH2CH2SiLpR3-P)2 (Bl-7). Further, the compound (B1) to (Bl-7) is preferably a compound having a -SiLpR3-p moiety of -SiL3, and a compound of L having an alkoxy group having 1 to 4 carbon atoms is particularly preferred, and L is a methoxy group or The ethoxylated compound is even better. The compound (B1) can be produced according to the method described in International Publication No. 2004/03 5656, and the like, and the compound can be obtained as an intermediate, and can be obtained in the same manner as the method for producing the compound (A). FC(0)CF2〇(CF2CF2〇)uCF2COF 'CH3C(0)0CF20(CF2CF20)UCF2C0〇CH3, HOCH2CF20(CF2CF2〇)uCF2CH2OH, ICF20(CF2CF20)uCF2l, and the like. (Compound (B 2 )) The compound (B2) is a group of x monovalent groups (Y〇(CF2CF20)w 〇?2-3) and z valence groups (rF3o(cf2cf2o)v- a compound of which Y is the (X + Z) valence group. (X + Z) is an integer of 3 or more, and is preferably an integer of 3 to 20, and an integer of 3 to 10 is more preferable, and 3 or 4 is particularly preferable from the viewpoint of easiness of synthesis. X is an integer of 2 or more, preferably an integer of 3 to 2 ’. An integer of 3 to 10 is more preferable, and 3 or 4 is particularly preferable. -34- 200922969 Z is an integer above ’' is preferably an integer of 〇~17, 整~7 is better integer, 0 (ie, base (Rf3〇(CF2CF20)v-) does not exist.) or 】 is particularly good. The group in which X is 2 or more (-0(CF2CF20)wCF2-X3) may be the same or different, and the group in which z is 2 or more (RF30(CF2CF2〇)v_) may be the same or different. Y is a perfluorinated saturated hydrocarbon group of (x + z) valence or a perfluorinated saturated hydrocarbon group having an etheric oxygen atom interposed between carbon atoms and carbon atoms (however, it does not have a -0CF20-structure). The carbon number of Y is preferably from 1 to 50, more preferably from 1 to 20, and particularly preferably from 3 to 5. When Y has an etheric oxygen atom, the number of ether oxygen atoms is 1 or more, and preferably 1 to 3. The etheric oxygen atom is present between the carbon atoms and one carbon atom, and no etheric oxygen atom is present at the terminal portion of γ. Further, the etheric oxygen atom of Y is not bonded to the carbon atom at the end of Y. In the Y aspect, a perfluorinated saturated hydrocarbon group having an (x + z) valence of an etheric oxygen atom is preferred, and a group having a trivalent or tetravalent value is preferred. In terms of the trivalent Y, the perfluoroalkane-triyl group is preferred. The carbon number of the base is preferably from 1 to 2, and particularly preferably from 3 to 5. In terms of the Y price of tetravalent, a perfluoroalkane-tetrayl group is preferred. The carbon number of the base is preferably from 1 to 20, particularly preferably from 3 to 5. Further, the compound (B 2 ) is a compound in which z is 0, Y is a trivalent group (Β2-1), ζ is 1, and Υ is a trivalent group (Β2-2), ζ is 〇, The compound (Β2-3) in which γ is a tetravalent group, and the compound (Β 2 · 4) in which Υ is a tetravalent group is preferable. -35- 200922969 However, γ3 is a perfluoroalkane-triyl group. Γ4 is a perfluoroalkane-tetrayl' and the definitions of the other groups are the same as described above. RF3 and X3 are the same as the above-mentioned preferred forms. Y3[-〇(CF2CF20)WCF2-X3]3 (B2-1). [Rf30(CF2CF20)v-]Y3[-0(CF2CF20)wCF2-X3]2(B2-2) 〇 Y4[-0(CF2CF20)wCF2-X3]4 (B2-3). [Rf30(CF2CF20)v-]Y4[-0(CF2CF20)wCF2-X3]3(B2-4) ο Υ3 (perfluoroalkane-triyl) may, for example, be the following group. [Chem. 18]

-CF.-CF-CF

CFa-CF - CF Y4 (perfluoroalkane-tetrayl) may, for example, be the group described below. ?F* cf2-c-cf* cf2 Other examples of compounds such as compound (B 2) are shown. -36-200922969 Specific examples of the compound (B2) include the following compounds. [Chem. 20]

?X τ6χ gx"cf2>·, (CFjJkGx /CF /{CF2>kGx c Fj

(CFj)kGz ?f2gz ?z <3x<CF2)k, CF /(CF2>kGx si C w C F2 F2 F2 F2 GxCFi CF2Gx

However, the base (Gx) is -0 (CF2CF20) wCF2-X3, and the base (Gz) is RF30(CF2CF20)v-. k is an integer of 1 to 10, and when there are two or more k in the same molecule, they may be the same or different. The compound (B2) is produced according to the method described in International Publication No. 20 05/06 8 5 4 or the like, and the compound is obtained by the same method as the method for producing the compound (A). -37- 200922969 [rF3o(cf2cf2o)v-]zy[-o(cf2cf2o)wcf2cof]x, [RF30(CF2CF20)v-]zY[-0(CF2CF20)wCF2C00CH3]x' [rF3o(cf2cf2o)v-] Zy[-o(cf2cf2o)wcf2ch2oh]x, [rF3o(cf2cf2o)v-]zy[-o(cf2cf2o)wcf2i]x, etc. The ratio of the compound (B) is preferably from 0.1 to 50% by mass, more preferably from 1:1 to 25% by mass based on the total mass of the compound (A). The fluorine-containing hydrolyzable decane (B) is preferably a compound having a group represented by the formula -SiLpR3-p of the compound (A). When the compound (A) is a compound having a group (XI) to (X6), it is preferred to use a compound (Β) having the same group (Χ1) to (Χ6) as the group, and the same group (XI) is used. (化合物6) The compound (Β1) or the compound (Β2) is preferred. (Non-fluorine-based hydrolyzable decane (Β)) When the compound (Β) is a non-fluorine-based compound, it is a non-fluorine-based hydrolysis of a compound having a structure having no fluorine atom and having two or more hydrolyzable groups bonded to a ruthenium atom. Sex decane (Β) is preferred. The non-fluorine-based hydrolyzable decane (Β) promotes high adhesion of the compound (Α) and/or the compound (Β) to the substrate, and high crosslinking of the compounds. In the surface treatment agent of the present invention, 'as a compound (Β), a fluorine-containing hydrolyzable decane (Β) and a non-fluorine-based hydrolyzable decane (Β) are preferred. In terms of the hydrolyzable group, an alkoxy group, a chlorine atom, an isocyanate group or the like is preferred. From the viewpoint of easy control of the reaction, an alkoxy group is more preferable. The hydrolyzable group in the non-fluorine-based hydrolyzable sand garden is preferably the same as the hydrolyzable group in the compound (Α) and the fluorine-containing hydrolyzable decane (Β). -38-200922969 The number of the hydrolyzable groups in the non-fluorine-based hydrolyzable decane (B) is 2 or more from the viewpoint of the crosslinkable reaction, and more preferably 4 or more. The non-fluorine-based hydrolyzable decane (B) is a compound represented by SiLsR4_s (however, s is an integer of 1 to 4, preferably 2 to 4, more preferably 4, L and R are the same meanings as described above), or A partially hydrolyzed condensate of the compound is preferred. The non-fluorine-based hydrolyzable compound (B) is preferably tetramethoxynonane, tetraethoxydecane, tetraisocyanate decane, tetrachlorodecane, methyl decanoate or ethyl decanoate. The ratio of the non-fluorine-based hydrolyzable sand chamber (B) to the total amount of the compound (A) and the fluorine-containing hydrolyzable decane compound is preferably 〇·1 to i 〇 times the mass, and 0.1 to 4 times the mass is better. ~4 times the quality is especially good. By this amount range, the effect of high adhesion and high cross-linking of the coating film is sufficiently exhibited, and the alkali resistance of the coating film is also improved. (Partially hydrolyzed condensate) In the surface treatment agent of the present invention, the compound (B) is contained as a compound different from the compound (A), and may be contained as a partial hydrolysis condensate with the compound (A). 'And it is better to include both. The partially hydrolyzed condensate is obtained by hydrolyzing a part of the hydrolyzable group of the compound (A) or the compound (B) in the presence of an organic solvent, a catalyst and water. The hydrolyzable decane compound preferably has the same type of the hydrolyzable group of the compound (A) and the compound (B) in such a manner that the polymer is not formed locally. -39- 200922969 Partially hydrolyzed cocondensate containing compound (A) and compound (B), preferably compound (A), fluorine-containing compound (B) in the presence of an organic solvent, a catalyst and water A part of the hydrolyzable group of the mixture of the non-fluorodecane compound (B) is obtained by hydrolysis treatment. When the composition is hydrolyzed in advance, it becomes easy to carry out a bond formation reaction between the coating film and the substrate, and it is easy to exhibit long-term durability. The acid catalyst used in the hydrolysis treatment is preferably an acid catalyst, and from the viewpoint of volatility, hydrochloric acid is preferred. When an alkali catalyst is used, the control of hydrolysis becomes difficult. Further, in order to prevent the film from remaining and exhibit long-term durability, it is preferred to use a volatile acid catalyst. Water is preferably added in an amount of 1 to 3 equivalents to the hydrolyzable group. If it is less than 1 time, the hydrolysis is difficult to proceed sufficiently. More than 3 equivalents, the composition becomes easily separated from water. In the hydrolysis treatment, the organic solvent is preferably an alcohol (methanol or the like). The surface treatment agent of the present invention described above is an essential component of the partially hydrolyzed condensate containing the compound (A) or the compound (A) or a mixture of the compound (A), and forms a water repellent refusal. A coating film excellent in oil resistance, oil stain removal property, and deterioration resistance under high temperature conditions in the presence of an acid catalyst. <Surface treatment agent> The surface treatment agent of the present invention may contain other components than the compound (A), the compound (B), and the partial hydrolysis condensate. Other components include, for example, a medium and an additive. -40- 200922969 (Media) The surface treatment agent of the present invention is preferably one containing an organic solvent. The surface treatment agent containing an organic solvent may be in the form of a solution, a suspension, or an emulsion, preferably a solution. The organic solvent may, for example, be a fluorine-based organic solvent or a non-fluorine-based organic solvent. Fluorine-based organic solvent, perfluorotripropylamine, perfluorotributylamine, ?111〇14丨1161^(3]'^ system), \^11^61 (made by DuPont), 2,2 Fluorocarbons such as 3,3-tetrafluoropropanol and 2,2,2-trifluoroethanol are preferred. Among them, fluoroalcohols such as 2,2,3,3-tetrafluoropropanol and 2,2,2-trifluoroethanol are preferred in the hydrolysis reaction of the compound (A) which is subjected to the subsequent reaction. As the non-fluorine-based organic solvent, for example, hydrocarbons, alcohols, ketones, ethers, esters, chlorinated hydrocarbons, etc., the solvent of the compounds (A) and (B) can be dissolved and used. The organic solvent is preferably a non-fluorine-based organic solvent, and among them, an alcohol such as methanol or ethanol is preferably subjected to a hydrolysis reaction such as the compound (A) which is subjected to a subsequent reaction. The compound (A) and the compound (B) contained in the surface treatment agent of the present invention are easily dissolved in a non-fluorine-based organic solvent to form a uniform composition. The ratio of the non-fluorine-based solvent is preferably 70% by mass or more based on the total mass of the organic solvent, and particularly preferably 40% to 1% by mass. The organic solvent may be used singly or in combination of two or more kinds as a mixed solvent. When an azeotropic composition is present in the mixed solvent, it is preferred to use the composition. When the hydrolysis reaction such as the compound (A) is carried out, it is preferred to add -41 - 200922969 catalyst and water to the organic solvent. As the organic solvent, a non-fluorine-based solvent is preferred, and an alcohol is particularly preferred. When a fluorine-based solvent is used, it is preferred to use a fluorocarbon, and it is preferred to use a fluorocarbon or an alcohol. The ratio of the two solvents is not particularly specified, but it is preferably adjusted to a mixing ratio in which all components are not phase-separated. The amount of the organic solvent is preferably 0.01 to 50% by mass based on the total mass of the composition of the compound (A), and more preferably 5% by mass. (Additive) The surface treating agent of the present invention may contain an additive. The additive is preferably added for the purpose of improving the durability and performance of the coating film formed by the surface treatment agent, and examples thereof include silicone rubber, ultrafine metal oxide (aluminum oxide, magnesium oxide, chromium oxide, etc.), various resins. (epoxy resin, unsaturated polyester resin, urethane resin, etc.) and the like. The additive to be added for the purpose of improving the workability of coating film formation may, for example, be an surfactant or the like. The amount of the surfactant added is preferably 0.01 to 5% by mass based on the total mass of the composition. The additive may be used alone or in combination of two or more. <Application> The use of the surface treatment agent of the present invention is, for example, a surface modifier which is treated by a method such as coating on a surface of a substrate to change the surface properties of the substrate, an adhesive for a semiconductor element, and an anti-reflection film. Reflective film, additives for various materials, and the like. Further, the surface treating agent of the present invention can be used as a surface treating agent or as an additive to other surface modifying agents. When the amount is -42 to 200922969, the total amount of the compound (A) and the compound (B) is preferably 0.01 to 5% by mass based on the total mass of the other surface treatment agent. The surface modifying agent may, for example, be a surface modifying agent such as a lubricant, an antifouling agent, a water and oil repellent, a fingerprint removal performance imparting agent, a detergency imparting agent, a release agent, or a wire coating material. The water-repellent and oil-repellent agent may, for example, be a water repellent such as paper or cloth, a protective coating agent for a semiconductor (a moisture-proof coating agent, a soldering inhibitor, etc.), an ink repellent for a printing machine such as inkjet printing, or a coating material. The additive, the water repellent agent for the window glass for conveying materials, and the like. When a water repellent agent for a window glass for a conveyor material is used, the thickness of the water repellent film is preferably 3 to 100 nm, more preferably 5 to 50 nm. Further, the water-repellent film has a surface roughness (Ra) of preferably 50 nm or less, more preferably 20 nm or less. In terms of easy-to-cleanness imparting agents, such as glass partition walls, shop windows, display cabinets, slabs, furniture, etc. When the easy-to-cleanness-imparting agent is applied, the sebum, the oil-based pen, the water-based pen, the graffiti, and the like are easily removed, and when the water is wiped, no wiping marks are generated, and it is not necessary to dry the wipe. The adhesive for a semiconductor element may, for example, be an adhesive for a lead on chip tape or the like. The additives for various materials are added to other agents to impart the properties of the surface treating agent of the present invention on the surface of the film formed by the agent. For example, an additive for a material for a film, an additive for a material for an antireflection film for a display, and the like. Due to the addition of the material for the film, the film can be provided with a low reflection function. The antireflection film can be imparted with fingerprint removal property by adding it to the material for an antireflection film for a display. -43- 200922969 <Item> The article of the present invention is an article having a coating film formed using the surface treating agent of the present invention on the surface of the substrate. The material of the substrate may, for example, be glass, stone, metal, resin or the like. Specific examples of the substrate include, for example, a stamper die, an injection molding die, a lighting member, and an optical member (an antireflection film, an optical filter, an optical lens, a spectacle lens, a spectroscope, a mirror, a mirror, etc.). Solar cells, touch panels, photosensitive drums, fixed drums, window glass for conveyor materials, window glass for construction, various films (film capacitors, anti-reflection films for glass windows, etc.), suitable for displays (liquid crystal displays, CRT displays) An optical functional component on the surface of the display screen, such as a projection television, a plasma display, an EL display, etc., a display device in which the optical functional component is bonded to the surface of the display display screen, and the like. The coating film formed using the surface treatment agent is a strong coating film and has high adhesion to the substrate. Further, the coating film is excellent in transparency, low in refractive index, and excellent in heat resistance and chemical resistance. The thickness of the coating film is preferably 〇 01~5 0 μιη. Specific examples of the article include, for example, an optical recording read head that is coated with a surface treatment agent as a lubricant on the surface of the read head to reduce friction with the disk; and is coated with a surface treatment agent such as glass. An optical material for an antifouling property; a window glass for a conveyor material which imparts antifouling properties by surface coating of a surface treatment agent; and a window glazing for construction which imparts antifouling property by surface coating of a surface treatment agent. The method of producing the article of the present invention is a method of coating a surface of a substrate at a surface to form a coating film. The method for forming the coating film is preferably, for example, the following method (1) or from the viewpoint of high adhesion to the substrate and formation of a strong coating film. Method (1): A method of applying a surface treatment agent to a surface of a substrate (2): a method of chemically reacting a surface after applying a surface treatment agent to a surface of the substrate. Examples of the coating method include a roll coating method, a casting method, a dip spin coating method, a spray coating method, a flow coating method, a Squeegee coating method, a water casting method, a die coating method, and a cloth coating method. Langmuir-Blodgett method, vacuum evaporation method, and the like. The uniform coating film is preferably a spin coating method, a dip coating method, or a method, and a mass production method is preferably a spray coating method, a flow coating method, a coating method, or a die coating method. When coating by spin coating or dipping, it is preferred to use a composition containing an organic solvent. When the surface treatment agent contains an organic solvent composition, the organic solvent is preferably an organic solvent having a boiling point suitable for the coating method. The concentration of the compound (A) and the other components in the organic solvent-containing composition is preferably adjusted in accordance with the thickness of the coating film. For example, in the case of the coating of 2 5 Onm, the amount of the organic solvent-containing composition (A), the compound (B), and other components is preferably 1.5 to 3.0. In the treatment of the surface treatment agent, the substrate surface treatment method may be, for example, an acid treatment such as hydrofluoric acid or hydrochloric acid; the hydrogen oxygen method (2), and the method (2) may be ί. For the coating method of the substrate, the image of the squeegee, the smear, and the vacuum squeegee, the squeegee coating method, the treatment of the material (Β), and the thickness of the compound. Pre-sodium hydrolyzate -45- 200922969 Alkali treatment of liquid, potassium hydroxide aqueous solution, etc.; cesium fluoride, oxidizing treatment, etc. By the method (2) 'the surface of the glass substrate, the resin substrate having a hydroxyl group such as a polyvinyl alcohol, a polyvinyl butyral or a vinyl ester copolymer After the surface treatment agent is applied to the surface of the substrate, it is preferred to maintain the coating film at 〜150 ° C. In particular, the hydroxyl group on the surface of the glass or the resin material having a hydroxyl group and the hydrolyzable decyl group form a decane bond generation device. The reaction product (A) between the hydrolyzable alkylene group-containing compound (A) and other compounds can form a coating film which is adhered to the substrate. The article of the present invention as described above is formed by coating the surface of the surface material. Since the film has a water- and oil-repellent property and an oil-stained catalyst, and the deterioration resistance under high-temperature conditions is excellent, the method for producing the article of the present invention can be produced by forming a coating film on the surface treatment agent of the base fabric. [Examples] [Examples] Hereinafter, the present invention will be described in detail by way of examples, but the examples of the present invention are defined by the examples.钸 钸 钸 钸Etc.) or tree-acetic acid to form a film, in the atmosphere, in the case of 50, and may be, and the high compatibility, strong treatment agent in the base removal, acid coating film. The surface oiliness and oil resistance of the material are excellent. The temperature is not -46-200922969 (abbreviation) TMS: tetramethyl decane, R-1 1 3 : CC12FCC1F2, R-225: dichloropentafluoropropane, DBTDL: Butyltin dilaurate, CFE-419 : CC1F2CC1FCF20CF2CF2C1, L : liter, Μη: number average molecular weight,

Mw: mass average molecular weight,

Rf : -CFCCFnOCF^FiCFnOCFzCFzCFs. a : The compound with a is a compound of two or more compounds different from each other. a is an integer selected from 1 to 2 00, and the average 値 is an integer of 化合物 η 化合物 of the compound, dl, d2, and d3: the compound having dl to d3 is two kinds different from dl to d3 値The above compounds are formed. Dl~d3 is an integer selected from 1 to 200, and the average 値 is an integer of 化合物η値 of the compound. (Measurement of Μη) Μη is measured by GPC. The measurement of GPC is carried out in accordance with the method described in JP-A-2001-2908. Specifically, the mobile phase used a mixed solvent of R-225 (ASAHIKLINAK-225 SECGradel) and hexafluoroisopropyl alcohol (HFIP) (R-22 5 /HFIP = 99/l capacity ratio). The analysis column used was a PLgel MIXED-E column (manufactured by Polymer Laboratories Co., Ltd.) and two in-line links were -47-200922969. In the molecule, the standard sample used for the measurement of the molecular weight distribution (Mw/Mn) is less than 1.1, and the four kinds of perfluoropolyethers having a molecular weight of 2000 to 10000 and the molecular weight distribution (Mw/Mn) are 13 分子量. Perfluoropolyether. The detector uses an evaporative light scattering detector to make the mobile phase flow rate 1 _0 mL / min, and the column temperature is 37 dead gpc. (Contact angle) Five drops of water having a diameter of about 2 μί or hexadecane 'measured contact angle' were placed on the surface of the article coating film to determine the average enthalpy of five turns. The water contact angle of the untreated soda lime glass plate was about 30 degrees. (water drop angle) Keep the article horizontal, and after dropping 50 μί of water droplets on the surface of the coated film, the article is slowly tilted, and the angle between the article and the horizontal plane (falling angle) when the water drop starts to fall is measured. The smaller the falling angle, the better the water drop is. (Abrasion resistance) Using a round-trip traverse tester (manufactured by Ν Ν Τ), the surface of the coating film was subjected to an abrasion test with a flannel, a load of 1 kg, and a wear rate of 30,000. And the water drop angle. (Alkali resistance) The article was immersed in an aqueous solution of sodium hydroxide at pH 13 for 2 hours. After the article is washed and dried, the water contact angle of the surface of the coating film of the article and the water drop angle of -48-200922969 are measured. (Removal of oil stain) On the surface of the coating film of the article, after the oil is artificially emulsified with oleic acid, it is wiped off with a cellulose-based non-woven fabric (made by Asahi Kasei Co., Ltd., and smashed insult M-3) with a certain load. Visually determine the ease of wiping off the oil. ° S The following. 〇: The oil can be completely removed. △: Wipe marks of residual oil stains. X: The oil cannot be removed. [Example 1] [Example 1-1] Production Example of Compound (D 3 -1) In a flask, the following compound (D 1 -1) (commercially available polyethylene oxide monomethyl ether, a) was added. The average 値: 7.3.) 25g, 20g of R-225, 1.2g of NaF, and 1.6g of pyridine, while maintaining the internal temperature at a temperature below 1 〇 °C, stirring vigorously, and pumping in nitrogen. In the flask, 4 6.6 g of the following compound (D2-1) was dripped for 3.0 hours while maintaining the internal temperature at 5 ° C or lower. After the completion of the dropwise addition, the mixture was stirred at 5 (TC for 12 hours, and stirred at room temperature for 24 hours to recover a crude liquid. The crude liquid was filtered under reduced pressure, and the recovered liquid was applied to a vacuum dryer (50 ° C, 5.0 t rr. Drying for 12 hours to obtain a crude liquid. The crude liquid was dissolved in 100 mL of R-22 5 and washed with 1 000 mL of saturated baking soda water three times to recover the organic phase. Magnesium sulfate was added to the organic phase. After stirring for 1 hour, magnesium sulfate was removed by filtration under reduced pressure, and -49-200922969 R-22 5 was distilled off from the recovered liquid to obtain 56.1 g of a compound which was liquid at room temperature. The following compound (D3-l) (average a: 7.3). CH30[CH2CH20]aCH2CH20H (D1-1), FC(0)-Rf (D2-1), CH30[CH2CH2〇]aCH2CH2OC(0)- Rf (D3-1) NMR spectrum of the compound (D3-1); 'H-NMROOOjMHz, solvent: CDC13, standard: TMS) S (ppm): 4.2, 4.35, 4_4, 4.75. 19F-NMR (282.7MHz, solvent: CDC13, reference: CFCl3) 5 (ppm): - 7 9 · 5, - 8 0 · 0, - 8 2.5 ~ 8 5.0, -1 2 8 · 0 ~ -129.2 -131.5, -144.5. [Example 1-2] Production Example of Compound (D 4-1): In a 3000 mL Hertzite autoclave, 1 to 560 g of R-1 1 3 was added and stirred, and maintained at 2 5 °C. At the gas outlet of the autoclave, a cooler maintained at 20 ° C, a NaF particle-filled layer, and a cooler maintained at -20 ° C were vertically disposed. Further, it is set to return the agglutination liquid to the liquid return line for the autoclave from a cooler maintained at -20T:. After the nitrogen gas was blown in the autoclave for 1 hour, the fluorine gas was diluted with nitrogen gas to 1 〇% (hereinafter, referred to as 10% fluorine gas). The flow rate was 2 4.8 L / hr. 1 hour blowing in. In the autoclave, 10% of the fluorine gas was blown at the same flow rate, and 27.5 g of the compound (D3 -1) was dissolved in a solution of 1350 g of R-113 for 30 hours. Connected -50 - 200922969 In the autoclave, 10% of the fluorine gas was blown at the same flow rate, and 12 mL of R-1 13 was injected. At this time, the internal temperature is changed to 40. (:. Connect Lu' to inject 6 mL of R-1 1 3 solution in which 1% by mass of dissolved benzene is dissolved. Further, after the gas is blown in for 1 〇 hours, the nitrogen gas is subjected to i. After the completion of the reaction, the solvent was dried under vacuum (6 (TC, 6 - 0 hr.) to distill off to yield 45.4 g of the compound which was liquid at room temperature.

As a result of NMR analysis, it was confirmed that the total number of hydrogen atoms of the compound (D3-1) Q·9 % was replaced by a fluorine atom, and the following compound (D4-1) was mainly contained. CF30[CF2CF20]aCF2CF2〇C(0)-Rf (D4-1). N M R spectrum of compound (D 4 - 1 ); iH-NMROOOjMHz, solvent: R-1 13, standard: TMS, & standard. Nitrobenzene) §^卩111): 5.9~6.4. 19F-NMR (282.7MHz, solvent: R-113, standard: CFci 1 3 , internal standard · hexabenzene) δ(ρριη): 12.7, -54.9' -77.5 ~ -80.0 ' -81.5 , -82.2 , -84.5 , -87.5, -89.7 '-129' -13 1.5, -135.0~-139.0, -144.5. [Example 1-3] Production Example of Compound (D 5 - 1): A 50 mL eggplant-shaped flask to which a stir bar was placed was sufficiently subjected to nitrogen substitution. Into an eggplant-shaped flask, 1,1,3,4-tetrachlorohexafluorobutane 5. 〇g, KF 0.05g, and compound (D 4 -1) 2.0 g were added and vigorously stirred to maintain 1 2 0 °C. . At the outlet of the eggplant flask, a cooler maintained at 20 °C and a dry ice-ethanol cooling tube were placed in a vertical position. After 8 hours, the internal temperature of the eggplant flask was lowered to room temperature. Then, in the cooling -51 - 200922969 tube, the vacuum pump was set to maintain a pressure in the system, and the solvent and by-products were distilled off. After 3 hours, 0.86 g of a compound which was liquid at room temperature was obtained. As a result of NMR analysis of the compound, it was confirmed that the total number of ester bonds of the compound (D4-1) was 99% by the fluorine atom, and the following compound (D5-1) was the main product. CF30[CF2CF20]aCF2C0F (D5-1). NMR spectrum of the compound (D5-1); iH-NMRpOOIMHz, solvent: R-113, standard: TMS, internal standard: nitrobenzene) δ (ρρηι): 5.9 to 6.4. 19F-NMR (282.7MHz, solvent ί: R-113, standard: CFC13, internal standard: hexafluorobenzene) δ(ρρπι): 12.7, -54.9, -78.1, -87.5, -89.7, -135.0~-139.0 . [Example 1-4] Production example (1) of the compound (D7-1): Into an eggplant-shaped flask to which 40 g of the compound (D5-1) was added, 20.0 g of yttrium-lanthanum 13 was added to maintain the internal temperature at 25 t. Stirring vigorously. In the eggplant-shaped flask, 20. Og of ethanol was allowed to drip while maintaining the internal temperature at 25 ° C or higher. After 8 hours, the stirring was stopped, and the crude liquid was subjected to pressure filtration to remove KF. Then, R-1 13 and excess ethanol were completely removed from the recovered liquid by an evaporator to obtain 43 g of a compound which was liquid at room temperature. As a result of NMR analysis of this compound, it was confirmed that the total number of acid fluorides of the compound (D5-1) was esterified, and the following compound (D 7 -1) was a main product. CF30[CF2CF20]aCF2C(0)0CH2CH3 (D7-1). NMR spectrum of compound (D 7 -1); iH-NMROOOWMHz, solvent: R-113, standard: TMS, internal -52- 200922969 standard: nitrobenzene) δ(ρριη) ·· 1.27, 4.27, 5.9 ~ heart 4. 19F-NMR (2 8 2.7 MHz, solvent: r_U3, some push 'CpCl3, internal standard: hexafluorobenzene) δ (ρρηι): -54.9, -78.5, 5 -89.7, -135.0~-139.0. [Example 1-5] Production Example (2) of Compound (D7-1): A 300 mL eggplant-shaped flask to which a stir bar was placed was sufficiently substituted with heat. Into an eggplant-shaped flask, 40 g of ethanol, 5 μL of NaF, and R - 225 (50 g) were added. After dropping the compound in a flask, the mixture was vigorously stirred while being inflated at room temperature. The eggplant flask outlet was sealed with nitrogen. After 8 hours, a vacuum pump was placed in the cooling tube to maintain the pressure in the system, and excess ethanol and CH3CH20C(0)-Rf formed by the exchange were distilled off. After 24 hours, a compound 2 6 · 8 g which was liquid at room temperature was obtained. As a result of NMR analysis of the compound, it was confirmed that the total amount of the ester group of the compound (D 4 -1 ) was transesterified, and the compound (D7-1) was a main product. NMR spectrum of the compound (D7-1); A-NMROOOjMHz, solvent: R-113, standard: TMS, internal standard: nitrobenzene) 3 (卩?111): 1_27, 4.27'5.9 to 6.4. 19F-NMR (2 8 2.7 MHz, solvent: R·1 13, reference: CFC13, internal standard: hexafluorobenzene) δ (ρριη): -54.9' -78.5' -87.5' -89.7 , -135.0 to -139.0. [Example 1 - 6] Production Example of Compound (D 9 -1): -53- 200922969 A 300 mL eggplant-shaped flask to which a stir bar was placed was placed in an eggplant-shaped flask, and 2-propanol 30 g, R-225 NaBH4 was added. 4.1g. The eggplant flask outlet was sealed with nitrogen. The 26.2 g was diluted in 30 g of R-225, and the mixture was added dropwise. After 8 hours, a vacuum pump was placed in the cooling tube to distill off the solvent. After 24 hours, the salt of the eggplant-shaped calcined product was dropped while dropping 0.2 of the predetermined salt 2, and stirring was continued for 6 hours. The organic extract was washed three times, separated into two layers to recover the organic phase magnesium sulfate 1. 〇g, and after stirring for 12 hours, magnesium was added, and R-22 5 was distilled off from the recovered liquid by an evaporator to obtain a compound 24.8. g. The total amount of the ester group of the NMR analysis of the compound (D7-1) was reduced to give the following compound. CF30[CF2CF20]aCF2CH20H (D9-1). NMR spectrum of the compound (D9-1); 'H-NMROOOjMHz, dissolved lj: R-113, part standard: nitrobenzene) δ (ρριη): 2.6' 3.92, 5.9, 19F-NMR (282.7 MHz, solvent: R-113, internal standard: hexafluorobenzene) δ (ρριη): -54.9, -79.8 -89.7, -135.0~-139.0. [Example 2] A production example of the compound (Α1-1) was sufficiently substituted with nitrogen. 50.0 g, and 'the compound (D 7 -1 ) ' was added to a reduced pressure vessel at a room temperature, and 500 g of an R-225 degree aqueous solution was added to the reduced pressure bottle. The purpose is to distill 500g of distilled water. The organic phase was added by pressure filtration to remove the sulfuric acid at room temperature as a liquid fruit, and it was confirmed that the compound (D9-1) was the main raw standard: TMS, internal ~6 · 4 ° Reference: CFC13, , -87_5, -54- 200922969 in 100 mL In the round bottom flask, 33.1 g of the compound (D7-1) and 3.7 g of the following compound (D8-1) were added, and the mixture was stirred at room temperature for 2 hours. After the completion of the reaction, the unreacted compound (D 8 -1) and the by-produced ethanol were evaporated under reduced pressure to obtain a compound 3 2.3 g at room temperature. From the NMR analysis result of the compound, it was confirmed that 95.0 mol% of -CF2C(0)0CH2CH3 in the compound (d7-1) was converted to -CF2C(0)NHCH2CH2CH2Si(0CH3)3, which was none-(〇CF2〇). - a compound of the unit. That is, the following compound (A 1 -1 ) is a main product. The molecular weight distribution of the compound (A1-1) was 1.16. NMR spectrum of NH2CH2CH2CH2Si(OCH3)3 (D8-1), CF30[CF2CF20]aCF2C(0)NH(CH2)3Si(0CH3)3(Al-1) ο compound (Α1-1); 1H-NMR (300.4MHz) Solvent: R-113, basis: TMS) 6 (ppm): 0.51, 1.60, 3.05 > 3.41, 3.67, 7.20. 19F-NMR (282.65 MHz, solvent: R-113, standard: CFCl3) 5 (ppm): - 5 4.9, - 7 8.0, - 8 8 _ 2, - 8 9 · 7. [Example 3] Production Example of Compound (A2-1): In a 25 OmL round bottom flask, 10 g of the compound (D9-1) and the catalyst DBTDL were added under a nitrogen atmosphere. 〇3g was dissolved in CFE-419. A 25.0 g solution was used to maintain the internal temperature below 5 °C. In a round bottom flask, 3 g of a commercially available compound (Dll-1) dissolved in 10% of CFE-419 was slowly dropped over 1 hour, and stirred for about 12 hours. The excess compound -55-200922969 (D11-1) and CFE-419 were distilled off under reduced pressure to give 10.7 g of a compound which was liquid at room temperature. The NMR analysis result of the compound confirmed that 99.1 mol% of -CF2CH2OH in the compound (D, ;!) was converted to -CF2CH2OC(〇)NH(CH2)3Si(OCH3)3, and was -(〇CF2〇) _ Unit of the compound. Namely, the following compound (A2-1) is the main product. As a result of analysis by GPC, the η of the compound (A2-1) was 1110. (0) C=NCH2CH2CH2Si(0CH3)3 (D11-1), CF30[CF2CF20]aCF2CH20C(0)NH(CH2)3Si(0CH3)3 (A2-1) ° NMR spectrum of compound (A2-1); JH - NMR pOOj MHz, solvent: R-113, standard: TMS) 6 (ppm): 0·85, 1.82, 3-20, 3.80, 4.10, 5.90. 19F-NMR (2 82.65 MHz, solvent: R-113, standard: CFCl3) 3 (ppm): -54_9, -79_5, -88.2, -89.7. [Example 4] Production Example of Compound (A3-1) In a 250 mL round bottom flask, sodium hydride 〇. 3 6 g was placed in a nitrogen atmosphere, and washed with 25 mL of hexane, and hexane was recovered. After the operation was further repeated twice, the residual hexane was distilled off under reduced pressure. Into a round bottom flask, 2 5 · 0 g of C F E - 4 1 9 was added to maintain the internal temperature below 5 °C. In a round bottom flask, a solution of the compound (D9-1) dissolved in 25.0 g of CFE-419 was slowly dripped for 1 hour and stirred for about 1 hour. Into a round bottom flask, 0.85 g of the following compound (D12-1) was added dropwise, and the mixture was stirred at room temperature for -2 to -2, 22,219, for 2 hours, and then heated to reflux for 72 hours. After the completion of the reflux, the mixture was cooled to room temperature, and the unreacted sodium hydride and the by-produced sodium chloride were filtered under pressure, and the CFE-419 and the excess compound (D12-1) were distilled off under reduced pressure to obtain a room temperature. The liquid compound was 10.7 g. As a result of N M R analysis of this compound, it was confirmed that 98.5 mol% of -CF2CH2OH in the compound (D 9 -1) was converted to -CF2CH20(CH2)3Si(0CH3)3, and was a compound of no -(〇CF20)-unit. That is, the following compound (A3-1) is a main product. As a result of analysis by GPC, the compound (A3-1) had a Μη of 1 100 and a molecular weight distribution of 1 _ 15 . CClH2CH2CH2Si(OCH3)3 (D12-1), CF30[CF2CF20]aCF2CH20(CH2)3Si(OCH3)3 (A3-1). NMR spectrum of the compound (A3-1); W-NMROOO. 4 MHz, solvent: R-113, s.: TMS) S (ppm): 0.76, 1.79, 3.36, 3.8, 5.6. 19F-NMR (282.65 MHz, solvent: R-113, standard: CFC! 3) S (ppm): -54·9 '-80.8 '-88.2 '-89.7. [Example 5] Production Example of Compound (Α6 -1 ) · In a 250 mL round bottom flask, a solution of 50 g of a compound (D9-1) dissolved in R-225 in a nitrogen atmosphere was added. The internal temperature is maintained below 5 °C. In a round bottom flask, a solution of CF 3 CF 2 CF 2 CF 2 S 〇 2 C 15 15 § dissolved in R - 2 2 5 1 5.0 g was slowly dripped for 1 hour and stirred for about 12 hours. After R-22 5 was distilled off under reduced pressure, the crude product was subjected to a two-layer separation from -57 to 200922969, and the lower layer was recovered to obtain a compound (D 9 _ 2) 5 8 g which was liquid at room temperature. The NMR analysis result of the compound confirmed that 99.8 mol% of -CF2CH2OH in the compound (d9-1) was converted to -CF2CH20SO2CF2CF2CF2CF3, and was a _(〇CF2〇)-unit of the formula CF30[CF2CF20]aCF2CH20S02(CF2) The compound represented by 3CF3. Then, (D 9 · 2 ) 50 g was placed in a 4-necked flask equipped with a stirrer, a dropping funnel, a reflux condenser and a thermometer, and the mixture was stirred for 1 hour. Further, i5g of Lil was added, and the temperature was raised to 60 ° C while continuing the scrambler for 3 hours. After completion of the reaction, the mixture was cooled, and the Li salt was filtered off, and the lower layer was taken out from the liquid phase divided into two layers using a liquid separation funnel. After washing this several times with acetone, the R-225' dissolved in 0 L was filtered to remove fine insolubles. The volatile matter was completely distilled off under reduced pressure from the obtained solution to obtain 43 g of Compound (D9-3) which was liquid at room temperature. The NMR analysis result of the compound confirmed that 99.5 mol% of -CF2CH20S02CF2CF2CF2CF3 in the compound (D9-2) was converted to -CF2CH2I, and was a compound represented by the formula CF30[CF2CF20]a CF2CH2I without -(0CF20)-unit. Into a 4-neck flask equipped with a stirrer, a dropping funnel, a reflux condenser, and a thermometer, '(D9_3) 4 〇g was added, and 100 g of R-225 was added as a solvent, and the mixture was stirred for 1 hour. Further, 0·5 g of di-u-butyl peroxide was added, and after nitrogen substitution was sufficiently carried out in the system, 25 g of vinyltrichloromethane was dropped through a dropping funnel under a nitrogen stream. After the completion of the dropwise addition, the temperature inside the system was raised to 1,200 ° C, and the reaction was carried out for 4 hours. After the completion of the reaction, the volatiles were completely distilled off under reduced pressure to obtain a compound j-58-200922969 (D9-4) 39 g which was liquid at room temperature. The NMR analysis result of the compound confirmed that 99.0 mol% of -CF2CH2I in the compound (d9-3) was converted to -CF2CH2(CH2CH(Si(OCH3)3))x-1, and was a compound having no _(〇CF2〇) unit. . To a 200-mL four-necked flask equipped with a stirrer, a dropping funnel, a reflux condenser, and a thermometer, 35 g of D9-4 and 5 g of R_225 were placed, and 2.5 g of zinc was vigorously stirred and dispersed. The system was cooled in an ice water bath, and anhydrous ethanol i 〇g was dropped under a nitrogen stream. After the completion of the dropwise addition, the ice water bath was removed, and the reaction was carried out for 2 hours under reflux under heating. After completion of the reaction, the insoluble matter was filtered off, and the lower layer was taken out from the liquid phase separated into two layers by a separatory funnel. After the obtained solution was washed three times with absolute ethanol, the volatile matter was completely stirred under reduced pressure to obtain 30 g of a compound (D9-5) which was liquid at room temperature. The 纟_ & NMR analysis confirmed that 99-9 mol% of -CF2CH2 (CH2CH(Si(OCH3)3))xI in the compound (D9-4) was converted to -CF2CH2 (CH2CH(Si(OCH3)3) ) xH, and is a compound in which -(〇CF 2 〇) _ unit is absent. That is, it is a mixture of a compound containing X of the following compound (A6-1) and having an average enthalpy of 1. As a result of analysis by GPC, the Μ η of the compound (A 6 -1 ) was 1 1 0 0, and analyzed by 1 η - N M R , and the average enthalpy of X was 1.4. The molecular weight distribution of the compound (Α6-1) was 1.09. NMR spectrum of CF30[CF2CF20]aCF2CH2(CH2CH(Si(0CH3)2))xH(A6-1) compound (A6-1); -59- 200922969]H-NMR (300_4MHz, solvent: R-113, basis: TMS) 5 (ppm): 0.76, 1.6 to 2_6, 3.8, 5.1. 19F-NMR (282.65 MHz, solvent: R-113, ept.: CFCl3) S (ppm): -54.9, -78.8 '-88.2, -89.7. [Example 6] Production Example of Compound (A7-1): To a 100 mL round bottom flask, 50.0 g of a compound (D7-1) and 16.2 g of the following compound (D8-2) were added, and the mixture was stirred at 60 °C. The pressure is directly lowered to 100 mmHg, and the by-produced ethanol is discharged. After completion of the reaction, the unreacted compound (D 8 -1) and the by-product ethanol were extracted and removed in hexane (100 ml) to obtain 64.5 g of a compound which was liquid at room temperature. As a result of NMR analysis of the compound, 95.0 mol% of -CF2C(0)0CH2CH3 in the compound (D7-2) was converted to -CF2C(0)N((CH2)3Si(0CH3)3)2, and it did not exist. The following compound (A7-1) of the -(OCf2〇)-unit is a main product. The molecular weight distribution of the compound (A7-1) is 1.21. NH((CH2)3Si(OCH3)3)2 (D8-2), CF30[CF2CF2〇]aCF2C(0)N((CH2)3Si(〇CH3)3)2 (A7-1) ο Compound (Α7- 1) NMR spectrum; 1H-NMR (300.4 MHz, solvent: R-113, standard · TMS) S (ppm): 0.56 ' 1.57, 3.1, 3.41. 19F-NMR (282.65 MHz, solvent: R-113, standard: CFCl3) 5 (ppm): -54.9, -72.5, -77.7, -88.2, -89.7. -60-200922969 [Example 7] Production Example of Compound (B) [Example 7-1] Production Example of Compound (B n _ ;}): The following compound (b-Ο) (commercially available polyethylene oxide) was used. The average enthalpy of alcohol and u: 8.3), as in the method described in International Publication No. 2004/03 5 6 % (Example 1) to (Example 4), the following compound (b_丨) was obtained. Average 値· 8.5). Using the compound (b-1), the following compound (b-2) was obtained in the same manner as in the method described in International Publication No. 20CM/03 5 656 (Example 5). In place of the compound (D7-1), a compound 6.5 g which was liquid at room temperature was obtained in the same manner as in Example 2 except that 15.5 g of the compound (b-2) was used. The NMR analysis result of the compound confirmed that 98.0 mol% of -CF2C(0)0CH3 in the compound (b-2) was converted to -CF2C(0)NHCH2CH2CH2Si(0CH3)3, and was absent - (〇cf2〇) - the compound of the unit. Namely, the following compound (B11-1) is the main product. Hoch2ch2o[ch2ch2o]uch2ch2oh (b-0), ch3oc(o)cf2o[cf2cf2o]ucf2c(o)och3 (bl), H0CH2CF20[CF2CF20]uCF2CH20H (b-2), (CH30)3Si(CH2)3NHC(0) CF20[CF2CF20]u CF2C(0)NH(CH2)3Si(0CH3)3 (Bll-I). NMR spectrum of the compound (B1 1-1); iH-NMR pOOj MHz, solvent: R-113, mp.: TMS) 6 (ppm): 0.5 1 '1.60, 3.05' 3.41, 3.67 '7_20. -61 - 200922969 l9F-NMR (2 82_65MHz, solvent: R-113, standard: CFCl3) S (ppm): -78.0, -88_2, -89.7. [Example 7 - 2] Production Example of Compound (b 1 2 -1): The following compound (b3) was obtained in the same manner as the method described in International Publication No. 2005/068534 (Example 11-1), and then The compound (b3) is reduced to give the following compound (b4). However, the average 値 of dl+d2 + d3 is 27.0. In place of the compound (D9-1), 10.5 g of a compound which was liquid at room temperature was obtained in the same manner as in Example 3 except that 10 g of the compound (b4) was used. The NMR analysis result of the compound confirmed that 99.1 mol% of -CF2CH2OH in the compound (b4) was converted to a -CF2CH20C(0)NH(CH2)3Si(0CH3)3 structure, and was absent-(ocF2〇)-single a compound of bismuth. Namely, the following compound (β^) is the main product. As a result of analysis by GPC, the compound (Bnui Mn is 3200 ° -62 - 200922969 [Chem. 21] CF2〇(CF2CF20)diCF2C〇2CH3 FC^--0(CF2CF20)d2CF2C〇2CH3 (b3) CF20(CF2CF20)d3CF2C02CH3

CF2〇(CF2CF2〇)diCF2CH2〇H FC-0(CF2CF2〇)d2CF2CH2〇H (4)

, CF20 (CF2CF20) d3CF2CH20H

CF2〇(CF2CF2〇)diCF2CH2〇C(0)NH(CH2)3Si(OCH3)3 FC——0(CF2CF20)d2CF2CH2〇C(0)NH(CH2)3Si(OCH3)3 (B12-1) GF20( NMR spectrum of CF2CF20)d3CF2CH2〇C(0)NH(CH2)3Si(OCH3)3 compound (B12-1); iH-NMRpOOjMHz, solvent: R-U3, basis: TMS)6 (ppm): 0.85, 1.82, 3.20, 3.80, 4.10, 5.90. 19F-NMR (282.65 MHz, solvent: R-113, standard: CFCl3) 5 (ppm): - 7 9 · 5, - 8 8.2, - 8 9 · 7.

[Example 8] Composition 1 containing compound (Al-1) and compound (B1 1-1) In a glass container provided with a stirrer or a thermometer, 48.5 g of methanol (manufactured by Junsei Chemical Co., Ltd.) and 0.37 g of a 10% nitric acid aqueous solution were added. Stir at 25 ° C for 1 。. A mixture of 1.35 g of the compound (Al-1) and 0.15 g of the compound (B11) was slowly added to the glass vessel, and the mixture was stirred at 25 ° C -63 - 200922969 for 1 hour to obtain a composition 1. The surface was honed with cerium oxide, and the composition 1 was applied by spin coating on a dried clean glass substrate (100 mm x 100 mm x 3.5 mm), and maintained at 1 day and night (24 hours) at room temperature. (2 0 to 2 5 (()), relative humidity 40 to 60%, to obtain article 1. Regarding article 1, the contact angle, water fall angle, abrasion resistance, alkali resistance, and oil stain removal were evaluated. 1. Item 1 has excellent water and oil repellency, abrasion resistance, alkali resistance, and oil stain removal. [Example 9] Composition 2 containing compound (A 1 - 1 ) and compound (B 1 1-1) 2 In a glass container equipped with a stirrer or a thermometer, 48.5 g of methanol (manufactured by Junsei Chemical Co., Ltd.) and 10 g of a 10% aqueous solution of nitric acid were added, and the mixture was stirred at 25 ° C for 1 minute. In a glass container, a compound was slowly added. (A)1, 0.34 g, 0.04 g of the compound (B11-1), and 1.13 g of tetramethoxynonane, and stirred at 50 ° C for 3 hours to obtain a composition 2. Substituted composition 1, composition was used. In the same manner as in Example 8, except for the object 2, the article 2 was obtained. With respect to the article 2, the contact angle, the water fall angle, and the abrasion resistance were evaluated. The results of the removal of properties, alkali resistance and oil stains are shown in Table 1. The article 2 has excellent water and oil repellency, abrasion resistance, and oil stain removal. [Example 1 〇] Containing compound (A 1 -1) and compound (B 1 2 -)) The compound (B 1 1-1) of the compound 3 was obtained by using the compound (b 1 2 -1) 0. 〇2 g, and the composition was obtained in the same manner as in -64-200922969 Example 9. 3. In place of the composition 1, the article 3 was obtained in the same manner as in Example 8 except for the composition 3. The article 3 was evaluated for the contact angle and the removal property of the oil stain. The results are shown in Table 1. The article 3 has excellent water and oil repellency and oil stain. [Example 1 1 (Comparative Example)] The composition of the compound (B 1 2 -1) is substituted for the total amount of the compound (A 1 - 1 ) and the compound (B 1 1 - 1 ), and is used. Compound (B12-1) was obtained in the same manner as in Example 9 except for the compound (B12-1). In the same manner as in Example 9, except for the composition 1, the article 4 was obtained in the same manner as in the example 8. The article 4 was evaluated for the removal of the contact angle and the oil stain. The results are shown in Table 1. The water and oil repellency of the article 4 was poor. [Example 12 (Comparative Example)] The composition of the compound (2) In a glass container equipped with a stirrer and a thermometer, 19 g of R-2652, compound (2) (manufactured by Daikin Industries, Ltd., opto〇l DSX) lg were added, and the mixture was stirred at 25 t for 1 minute to obtain a composition 5. The article 5 was obtained in the same manner as in Example 8 except for the composition 5 except for the composition 1. With respect to the article 5, the contact angle, the water fall angle, the abrasion resistance, the alkali resistance, and the oil stain removal property were evaluated. The oil stain of the article 5 is poorly removed. [Example 13] An example of the composition 6 containing the compound (A6-1) and the compound (B1 1-1)-65-200922969 In the same manner as in Example 8, the compound (A) is used, and the compound (A6) is used. -1) 0,4 g to obtain the article 6 by modulating the composition 6'. Regarding the article 6, the results of evaluating the contact angle and the removal of the oil stain are shown in Table 1. The article 6 has excellent water and oil repellency and oil stain removal properties. [Example 14] Example of the composition 7 containing the compound (A 7 -1) and the compound (B 1 1-1) In the same manner as in Example 8, the compound (A 1 -1 ) was substituted, and the compound (A7-1) was used. The composition 7 was prepared in the same manner as in Example 8 except for 0.4 g to obtain an article 7. Regarding the article 7, the results of evaluating the contact angle and the removal of the oil stain are shown in Table 1. The article 7 has excellent water repellency and oil repellency and oil stain removal property. [Table 1] Contact angle (degrees) Water drop angle (degrees) Abrasion resistance (degrees) Alkali resistance (degrees) Oil removal of water hexadecane 8 111 70 14 109/14 109/26 Example 9 109 65 12 106/15 100/27 Example 10 109 64 - _ Example 11 (Comparative) 92 55 - - Example 12 (Comparative) 113 62 8 110/16 104/30 Δ Example 13 110 60 13 109/ 15 107/27 Example 14 113 65 10 111/15 109/27 〇The number of wear resistance and alkali resistance 「 means "water contact angle / water fall angle". -66- 200922969 [Example 1 5] Stability test example [Example 1 5 -1] Stability test of compound (A): About the compound (A) obtained in the above Examples 2 to 6, in a nitrogen atmosphere (100 inL/min) Next, after raising the temperature from 25 ° C to 50 ° C in a ratio of 10 ° C / min, the mass of the compound (D9-1 ) 25 mg was reduced to carry out a stability test by the method described on the differential thermal scale. As a result, no mass is reduced and it is almost constant. The stability test of 25 mg of the compound (A) was carried out in the presence of 0.5 g of an acid catalyst γ-alumina fine powder (manufactured by Nippon Chemical Co., Ltd., N-611N). As a result, the degree of quality reduction was the same as that in the case of no acid catalyst, showing excellent stability. [Example 15-2] Stability Test of Compound (B): The results of the same test as in the case of the compound (B 11-1) and the compound (B 12-1) obtained in the above Example 7 were also carried out in the same manner as in Example 15-1. No quality reduction, almost certain. Similarly, even in the presence of γ-alumina fine powder, the stability test was carried out, and there was no mass reduction, showing excellent stability. [Example 1 5 - 3] Test Example for Stability of Perfluoropolyether (Reference Example): Using a known perfluoropolyether (manufactured by AUSIMONT, f〇mB. LINZ DiOL4000), the stability test was carried out in the same manner. . As a result, the ether was decomposed in the presence of γ-alumina fine powder at a temperature of 250 ° C for a while to become a low molecular weight compound and gasified. -67 - 200922969 [Industrial Applicability] The surface treatment agent of the present invention is used as a surface treatment agent for imparting a lubricant, an antifouling agent, a water and oil repellent agent, a fingerprint removing performance imparting agent, and an easy-cleaning property. An imparting agent, a releasing agent, a surface modifying agent, and the like. The specification of the Japanese Patent Application No. 2007-178330, the entire disclosure of which is hereby incorporated by reference in its entirety in its entirety in its entirety in -68-

Claims (1)

200922969 X. Patent Application No. 1. A surface treatment agent characterized by a compound represented by the following formula (A) and a compound (B) which can be partially hydrolyzed with the compound represented by the formula (A), or the following formula ( The partial hydrolysis condensate of the compound represented by A) and the compound (B) which can be partially hydrolyzed with the compound represented by the formula (A) is an essential component, RF10(CF2CF20)aCF2-(Q)b(-(CH2) d-SiLpR3.p)c (A) but the symbol in the formula indicates the following meaning, RF1: a perfluoromonovalent saturated hydrocarbon group having a carbon number of 1 to 20, or an etheric oxygen atom interposed between carbon atoms and carbon atoms. a perfluoroindene saturated hydrocarbon group having a carbon number of 2 to 20, and the group has no -〇CF20 - structure group, a: an integer of 1 to 200, b: 0 or 1, Q: when b is 0, 'Q When b is 1, when Q is 1, Q is a linking group of 2 to 3, and c:Q is not present or Q is a divalent linking group. When ^^ is a trivalent linking group, c is 2, d: an integer of 2 to 6, L: a hydrolyzable group, R: a hydrogen atom or a monovalent hydrocarbon group, p: an integer of 1 to 3. 2. The surface treatment agent according to claim 1, wherein the compound represented by the formula (A) is a compound represented by the following formula (a), RF10(CF2CF20)aCF2-X(a)-69-200922969 However, The symbol in the formula indicates the following meanings 'rf1 and a: have the same meaning as the above' X: the base selected by the following formula (XI) to the following formula (x7) (but 'L, R, and P and the foregoing In the same sense, -C(0)NHCH2CH2CH2SiLpR3-P (XI) -CH20C(0)NHCH2CH2CH2SiLpR3.p (X2), -CH2OCH2CH2CH2SiLpR3-p (X3), -CF2OCH2CH2CH2SiLpR3-p (X4), -CH2CH2SiLpR3_p (X5), -CH 2 CH 2 CH 2 S i L p R 3. p (X6) ' _C(0)N(CH2CH2CH2SiLpR3-p)2(X7). The surface treating agent of claim 2, wherein X is a group selected from the above formula (XI) to the above formula (X6). 4. The surface treatment agent of any one of claims 1 to 3, wherein the molecular weight distribution (Mw/Mn) of the compound represented by the formula (A) is 1.05 to 1.3. The surface treatment agent of any one of the above-mentioned formulas (1) to 4, wherein the compound (B) is selected from two or more groups represented by the above formula (XI) to the above formula (X7). The structure other than the group is a perfluorohydrocarbon group containing an etheric oxygen atom, and a compound having a structure in which no _〇CF2〇_ structure is present is an essential component. 6. The surface treatment agent according to any one of claims 1 to 4, wherein the compound (B) is a compound represented by the following formula (B1) and/or a compound represented by the following formula (B2) is an essential component. , -70- 200922969 X2-CF20(CF2CF20)uCF2-X2 (Bl), [RF30(CF2CF20)v-]zY[-〇(CF2CF2〇)wCF2-X3]x (B2) However, the symbol in the formula indicates In the meaning, X2 and X3 are each independently, and each of them is selected from the group represented by the following formula (XI) to the group represented by the following formula (X7) (however, L, R, and p are the same as the above) Meaning), -C(0)NHCH2CH2CH2SiLpR3-p (XI), -CH20C(0)NHCH2CH2CH2SiLpR3-p (X2), -CH2OCH2CH2CH2SiLpR3.p (X3), -CF2OCH2CH2CH2SiLpR3.p (X4), -CH2CH2SiLpR3-p (X5) , CH2CH2CH2SiLpR3 — p (X6), -C(0)N(CH2CH2CH2SiLpR3-p)2(X7) RF3 : a perfluoromonovalent saturated hydrocarbon group having a carbon number of 1 to 2 fluorene or an ether inserted between carbon atoms and one carbon atom a peroxyl monovalent saturated hydrocarbon group having 2 to 20 carbon atoms of the oxygen atom and the absence of the group - 〇CF20 - a structural group, Y being a (X + Z) valence of a perfluorinated saturated hydrocarbon group, or a carbon atom - an etheric oxygenogen is inserted between carbon atoms (x + z) valence of a perfluorinated saturated hydrocarbon group, and the groups are absent - 〇CF20 - a structural group, u, v, w: each independently, an integer from 1 to 200 'X, Z: X is An integer of 2 or more, 2 is an integer of 0 or more, and (x + z) is an integer of 3 or more. When z is 2 or more, the radicals represented by Rf3〇(CF2CF2〇)v_ may be the same or different, and X is The surface treatment agent of any one of the above-mentioned items of the first to sixth aspects of the invention, wherein the compound (the compound of the formula (CF2CF2)) is the same or different. B) A compound having a structure in which two or more hydrolyzable groups are bonded to a ruthenium atom without a fluorine atom is an essential component. 〜1质量质量。 The ratio of the total mass of the compound (B) to the total mass of the compound (a) is 0. 1~5 0% by mass. 9. The surface treatment agent according to any one of claims 1 to 8, which contains an organic solvent. 10. The surface treatment agent of claim 9, wherein the organic solvent is a non-fluorine-based organic solvent. A method for producing a surface-treated substrate, which is characterized in that the surface treatment agent according to any one of claims 1 to 10 is applied to a surface of a substrate and dried. Surface treatment. 1 2. A compound represented by the following formula (A) (however, the compound has no -0CF20-structure), RF10(CF2CF20)aCF2-(Q)b(-(CH2)d-SiLpR3-p)c(A) However, the symbol in the formula indicates the following meaning 'RF1: a perfluoromonovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a perfluorocarbon having 2 to 20 carbon atoms having an etheric oxygen atom interposed between carbon atoms and carbon atoms a monovalent saturated hydrocarbon group, and the groups are absent - 〇CF2〇-structured base 'a: an integer from 1 to 200' b ·· 0 or 1, Q: when b is 0, Q does not exist when 'b is 1 'Q is a link of 2 to 3 valences 5-72- 200922969 c:Q does not exist or (c is 2 when the price is 2, and c is 2 when the Q is 3 valence linkage, d: 2~ An integer of 6 , L : a hydrolyzable group, R: a hydrogen atom or a monovalent hydrocarbon group, p: an integer of 1 to 3. 13. A compound represented by the following formula (&) (but, no -CFF20 in the compound) Structure), RF1〇(CF2CF20)aCF2-X (a) However, the symbol in the formula indicates the following meaning, RF1: a perfluoroindene saturated hydrocarbon group having a carbon number of 1 to 20 or inserted between carbon atoms and carbon atoms a perfluoro-valent monovalent saturated hydrocarbon group having 2 to 20 carbon atoms of an etheric oxygen atom, and these The base does not exist - 〇CF20 - the basis of the structure, a : an integer of 1 to 200, X: any one selected by the following formula (XI), the following formula (X2), the following formula (X6), and the following formula (X7) a group (however, L is a hydrolyzable group, R is a hydrogen atom or a monovalent hydrocarbon group, p is an integer of 1 to 3), -C(0)NHCH2CH2CH2SiLpR3-P(XI), -CH20C(0)NHCH2CH2CH2SiLpR3-p ( X2), •CH2CH2CH2SiLpR3-p (X6), -C(0)N(CH2CH2CH2SiLpR3-p)2 (X7). -73- 200922969 VII. Designated representative map: (1) The designated representative figure in this case is: None (2) ), the representative symbol of the representative figure is a simple description: no eight, if there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: none