Fluoropolyether-modified amidosilane compound, surface treatment agent composition and article

Abstract

To provide a fluoropolyether-modified amidosilane compound usable as a surface treatment agent which can be applied to the surface of an article without substantially using a fluorine-based solvent and imparts excellent surface characteristics to a cured product surface, a surface treatment agent composition mainly comprising the fluoropolyether-modified amidosilane compound and / or a partial hydrolysis condensation thereof and an article having a cured film of the surface treatment agent composition.SOLUTION: There is provided a fluoropolyether-modified amidosilane compound represented by the following formula (1): (Rf is a bivalent perfluoropolyether group having a number-average molecular weight of 1500 to 20000, Z is a divalent linking group containing at least one Si-O-Si bond, M is a hydrolyzable group selected from an alkoxy group having 1 to 10 carbon atoms, an alkoxy alkoxy group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms and a halogen atom, R is a monovalent hydrocarbon group having 1 to 6 carbon atoms and a is 2 or 3.)SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a novel fluoropolyether-modified amidosilane compound that provides a cured coating film that is excellent in water and oil repellency, releasability, stain resistance, etc., a surface treatment agent composition containing this amidosilane compound and / or a partial hydrolysis condensate thereof as an essential component, and an article having a cured coating film of this surface treatment agent composition. [Background technology]

[0002] Generally, fluoropolyether group-containing compounds have very small surface energy and therefore have properties such as water and oil repellency, chemical resistance, lubricity, release property, stain resistance, etc. Taking advantage of these properties, they are widely used industrially as water and oil repellency and stain resistance agents for the surfaces of a wide range of materials such as glass, metal, resin, paper, and fiber, as lubricants for magnetic recording media, oil repellents for precision instruments, release agents, cosmetics, protective films, etc.

[0003] However, these properties also indicate that the material is non-adhesive and non-adhesive to other substrates, and although it could be applied to the surface of a substrate, it was not possible to form a coating and adhere it to the substrate.

[0004] On the other hand, silane coupling agents are well known as agents that bond organic compounds to the surfaces of substrates such as glass and cloth. Silane coupling agents have an organic functional group and a reactive silyl group (generally an alkoxysilyl group) in one molecule. The alkoxysilyl group undergoes an autohydrolysis condensation reaction with moisture in the air to become siloxane, forming a coating. At the same time, it chemically and physically bonds with the surfaces of glass, metal, etc., forming a durable, strong coating. Taking advantage of this property, silane coupling agents are widely used as coating agents for the surfaces of various substrates.

[0005] Taking advantage of these characteristics, Japanese Patent Laid-Open Publication No. 2000-327772 (Patent Document 1) discloses a fluoroamidosilane compound as shown in the following formula, which is dissolved in perfluorohexane and then coated and cured to impart the properties of perfluoropolyether (PFPE) to the glass surface. [ka]

[0006] Furthermore, JP 2002-121277 A (Patent Document 2) discloses a compound having the following group as a compound with superior durability and lubricity, and imparts the properties of perfluoropolyether to the glass surface by applying a coating liquid in which the compound is dissolved in perfluoro(2-butyltetrahydrofuran) and curing the coating liquid. [ka]

[0007] To use these compounds to impart the properties of perfluoropolyether to the surface of a material, it is better to have a structure with as high a fluorine content as possible, i.e., a long-chain fluoropolyether structure. However, compounds with a high fluorine content have extremely poor solubility in non-fluorine compounds (non-fluorine solvents), and therefore it is necessary to mix a low-molecular-weight volatile component containing fluorine, i.e., a fluorine-based solvent, in order to apply the compound uniformly to the surface of the material.

[0008] Meanwhile, in recent years, restrictions on low-molecular-weight fluorine compounds such as PFOS (perfluorooctane sulfonate) and PFOA (perfluorooctanoic acid) have been strengthened due to concerns about the environment, bioaccumulation, toxicity, etc., and the use of fluorine-based solvents requires specialized removal equipment different from that for general organic solvents, strengthened safety measures for workers, etc. Furthermore, fluorine-based solvents are more expensive than general non-fluorine-based solvents, and there is a demand to reduce the amount of fluorine-based solvents used from a cost perspective as well.

[0009] Due to this social background, in recent years, there has been a trend toward significant restrictions on the amount of fluorine-based solvents that can be used and the working environment, and there is a demand for compounds that can impart the excellent properties of fluorine polymers (fluoropolyether group-containing compounds) to the surface of cured products without using fluorine-based solvents. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] JP 2000-327772 A [Patent Document 2] JP 2002-121277 A Summary of the Invention [Problem to be solved by the invention]

[0011] The present invention has been made in view of the above circumstances, and has an object to provide a fluoropolyether-modified amidosilane compound that can be applied to the surface of an article substantially without using a fluorine-based solvent and that can be used as a surface treatment agent capable of imparting excellent surface properties to the surface of the cured product; a coating composition (surface treatment agent composition) containing the fluoropolyether-modified amidosilane compound and / or a partial hydrolyzed condensate thereof as a main component; and an article having a cured coating formed from the fluoropolyether-modified amidosilane compound and / or a partial hydrolyzed condensate thereof. [Means for solving the problem]

[0012] As a result of extensive research to achieve the above-mentioned object, the inventors have discovered that a novel fluoropolyether-modified amidosilane compound represented by the following general formula (1) can be diluted and coated with an organic solvent not containing fluorine atoms, and that by drying and curing the resulting coating film, it is possible to impart excellent perfluoropolyether properties such as water and oil repellency and antifouling properties to the surface of a material, thereby completing the present invention. [ka] (In the formula, Rf is a divalent perfluoropolyether group having a number average molecular weight of 1,500 to 20,000; each Z is independently a divalent linking group containing at least one Si-O-Si bond; each M is independently a hydrolyzable group selected from the group consisting of an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, and a halogen atom; each R is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms; and a is 2 or 3.)

[0013] Accordingly, the present invention provides the following fluoropolyether-modified amidosilane compound, surface treatment agent composition, and article. [1] The following general formula (1) [ka] (In the formula, Rf is a divalent perfluoropolyether group having a number average molecular weight of 1,500 to 20,000; each Z is independently a divalent linking group containing at least one Si-O-Si bond; each M is independently a hydrolyzable group selected from the group consisting of an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, and a halogen atom; each R is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms; and a is 2 or 3.) The fluoropolyether-modified amidosilane compound is represented by the formula: [2] The fluoropolyether-modified amidosilane compound according to [1], wherein in the above general formula (1), Rf is represented by the following general formula (2): -CF(Y)-O-Rf 1 -CF(Y)- (2) (Wherein, Y is F or CF3, and Rf 1 consists of repeating units selected from one or more of the following perfluorooxyalkylene units.) -CF2O- -CF2CF2O- -CF2CF2CF2O- -CF(CF3)CF2O- -CF2CF(CF3)O- -CF2CF2CF2CF2O- -CF2CF2CF2CF2CF2O- -CF2CF2CF2CF2CF2CF2CF2O- -CF2CF2OCF2CF2CF2CF2O- [3] The fluoropolyether-modified amidosilane compound according to [1] or [2], wherein in the above general formula (1), Rf is any one of the following: -CF2O(CF2O) p (CF2CF2O) q CF2- (In the formula, p is an integer of 10 to 300, q is an integer of 5 to 170, and p+q is an integer of 15 to 470 such that the number average molecular weight of Rf is 1,500 to 20,000, and the arrangement of each repeating unit is random.) [ka] (In the formula, s and t are independently integers of 1 to 120, and s+t is an integer of 2 to 240 such that the number average molecular weight of Rf is 1,500 to 20,000, u is an integer of 1 to 6, and v is an integer of 0 to 10.) -CF2CF2O[CF2CF2CF2O] w CF2CF2- (In the formula, w is an integer of 8 to 119.) -C z F 2z O(CF2CF2O) x (CF2CF2CF2CF2O) y C z F 2z - (In the formula, x is an integer of 2 to 300, y is an integer of 2 to 80, and x+y is an integer of 4 to 380 such that the number average molecular weight of Rf is 1,500 to 20,000. z is independently 1 or 2 for each unit. The arrangement of each repeating unit is random.) [4] The fluoropolyether-modified amidosilane compound according to any one of [1] to [3], wherein in the above general formula (1), Z is a divalent linking group represented by the following formula (3): [ka] (In the formula, m is an integer of 2 to 10, n is an integer of 2 to 10, and l is an integer of 1 to 6.) [5] The fluoropolyether-modified amidosilane compound according to any one of [1] to [4], wherein, in the above general formula (1), Z is represented by the following formula, and a is 3: [ka] [6] The fluoropolyether-modified amidosilane compound according to any one of [1] to [5], wherein in the above general formula (1), M is an alkoxy group having 1 to 10 carbon atoms. [7] A surface treatment agent composition containing a non-volatile fluorine-containing organic compound, wherein the non-volatile fluorine-containing organic compound contains 80 mass% or more of the fluoropolyether-modified amidosilane compound and / or its partial hydrolysis condensate according to any one of [1] to [6]. [8] The surface treatment agent composition according to [7], wherein the average fluorine content of the non-volatile fluorine-containing organic compound is 40 to 65 mass %. [9] The surface treatment agent composition according to [7] or [8], further comprising an organic solvent having a boiling point of 25 to 260°C, wherein the content of the fluoropolyether-modified amidosilane compound and / or its partial hydrolysis condensate in the surface treatment agent composition is 0.01 to 95 mass%.

[10] The surface treatment composition according to [9], wherein the organic solvent does not contain a fluorine atom.

[11] An article having a cured coating of the surface treatment composition according to any one of [7] to

[10] . Effect of the Invention

[0014] The novel fluoropolyether-modified amidosilane compound of the present invention can be diluted and coated with an organic solvent that does not contain fluorine atoms. By applying a surface treatment agent composition containing the amidosilane compound and / or its partial hydrolysis condensate as a main component to the surface of an article and drying and curing the coating to obtain a cured coating, it is possible to impart excellent perfluoropolyether properties, such as water and oil repellency and stain resistance, to the surface of the material. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] The present invention will be described in detail below. The fluoropolyether-modified amidosilane compound of the present invention is represented by the following general formula (1). [ka] (In the formula, Rf is a divalent perfluoropolyether group having a number average molecular weight of 1,500 to 20,000; each Z is independently a divalent linking group containing at least one Si-O-Si bond; each M is independently a hydrolyzable group selected from the group consisting of an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, and a halogen atom; each R is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms; and a is 2 or 3.)

[0016] In the above general formula (1), Rf is a divalent perfluoropolyether group having a number average molecular weight of 1,500 to 20,000, preferably 1,500 to 10,000. If the number average molecular weight of Rf is less than 1,500, the fluorine content in the compound is too low, making it difficult to impart perfluoropolyether properties, and if it exceeds 20,000, the structure of the fluorine-containing group (perfluoropolyether group) becomes too long, making it difficult to dissolve in a non-fluorine-based solvent.

[0017] In the present invention, the molecular weight (or the degree of polymerization or the number of repeating units) can be determined as a number average molecular weight (or number average degree of polymerization) in terms of polystyrene or polymethyl methacrylate by gel permeation chromatography (GPC) analysis using a fluorinated solvent as a developing solvent. Preferably, 1 H-NMR analysis and 19 It is the number average molecular weight (or number average degree of polymerization) calculated from the characteristic peak intensity ratio between the terminal structure and the main chain structure of the fluoropolyether-modified amidosilane compound based on F-NMR analysis (hereinafter the same).

[0018] Rf is particularly preferably a divalent perfluoropolyether group represented by the following general formula (2). -CF(Y)-O-Rf 1 -CF(Y)- (2)

[0019] In the general formula (2), Y is F or CF3, and Rf 1 is composed of repeating units selected from one or more of the following perfluorooxyalkylene units: The number of repeating units is such that the number average molecular weight of Rf satisfies 1,500 to 20,000. -CF2O- -CF2CF2O- -CF2CF2CF2O- -CF(CF3)CF2O- -CF2CF(CF3)O- -CF2CF2CF2CF2O- -CF2CF2CF2CF2CF2O- -CF2CF2CF2CF2CF2CF2CF2O- -CF2CF2OCF2CF2CF2CF2O-

[0020] In particular, Rf in the above general formula (1) (or the above general formula (2); -CF(Y)-O-Rf 1 As the divalent perfluoropolyether group represented by --CF(Y)--, those represented by the following formula are preferred. -CF2O(CF2O) p (CF2CF2O)q CF2-, [ka] -CF2CF2O[CF2CF2CF2O] w CF2CF2-, -C z F 2z O(CF2CF2O) x (CF2CF2CF2CF2O) y C z F 2z -

[0021] In the above formula, p is an integer of 10 to 300, preferably an integer of 10 to 100. q is an integer of 5 to 170, preferably an integer of 10 to 100. p+q is an integer of 15 to 470, and is a number that satisfies the number average molecular weight of Rf of 1,500 to 20,000, preferably an integer of 17 to 300, and is more preferably an integer of 20 to 200. If p and q are smaller than these ranges, it becomes difficult to give sufficient perfluoropolyether properties, and if they are larger than these ranges, the solubility in organic solvents (particularly organic solvents not containing fluorine atoms) with a boiling point of 25 to 260°C (hereinafter the same applies to solubility) decreases. Furthermore, the value of q / p is preferably 0.7 to 1.5, more preferably 0.8 to 1.2. If it is less than 0.7, the durability of the fluoropolyether structure decreases, and if it is more than 1.5, the polymer loses flexibility and its solubility decreases. Note that the arrangement of each repeating unit shown in parentheses with p and q is random.

[0022] In the above formula, s and t are independently integers of 1 to 120, preferably integers of 5 to 60, and s+t is an integer of 2 to 240, where the number average molecular weight of Rf is 1,500 to 20,000, preferably an integer of 4 to 119, where the number average molecular weight of Rf is 1,500 to 20,000, more preferably an integer of 10 to 100, and even more preferably an integer of 15 to 100. If s+t is smaller than this, it becomes difficult to impart sufficient perfluoropolyether properties, and if it is larger than this, the solubility is greatly reduced, u is an integer of 1 to 6, preferably an integer of 2 to 4, and v is an integer of 0 to 10, preferably an integer of 1 to 4.

[0023] In the above formula, w is an integer of 8 to 119, and preferably an integer of 10 to 100. If it is smaller than this range, it becomes difficult to impart sufficient perfluoropolyether properties, and if it is larger than this range, the solubility decreases.

[0024] In the above formula, x is an integer of 2 to 300, preferably an integer of 2 to 100, y is an integer of 2 to 80, preferably an integer of 2 to 60, and x+y is an integer of 4 to 380. Among them, the number average molecular weight of Rf is a number that satisfies 1,500 to 20,000, preferably an integer of 5 to 163, and the number average molecular weight of Rf is 1,500 to 20,000, and more preferably an integer of 6 to 140, and the number average molecular weight of Rf is 1,500 to 20,000. If x and y are smaller than these ranges, it becomes difficult to give sufficient perfluoropolyether properties, and if they are larger than these ranges, the solubility decreases. z is independently 1 or 2 for each unit. In addition, the arrangement of each repeating unit shown in the parentheses with x and y is random, but the sequence of -CF2CF2OCF2CF2CF2CF2O- may be a repeating structure.

[0025] These repeating units of the above groups may contain, in addition to the exemplified repeating units, a fluoroalkyl ether structure having 1 to 6 carbon atoms within a range that does not affect the solubility or properties imparted to the surface treatment agent composition, specifically within a range of 0 to 3 mol %, due to reasons such as the production method and purification method.

[0026] In the above general formula (1), each Z is independently a divalent linking group containing at least one Si-O-Si bond, particularly a linking group containing a linear diorganopolysiloxane structure, and is particularly preferably represented by the following formula (3): In the following structure, it is preferable that the bond on the left side is bonded to N and the bond on the right side is bonded to Si. [ka] (In the formula, m is an integer of 2 to 10, and preferably an integer of 2 to 6, n is an integer of 2 to 10, and preferably an integer of 2 to 6, and l is an integer of 1 to 6, and preferably an integer of 1 to 3.)

[0027] The structure represented by formula (3) can be exemplified by the structure shown below. In the structure shown below, the bond on the left side is bonded to N, and the bond on the right side is bonded to Si. [ka] Among the structures represented by formula (3), the structures shown below are particularly preferred. [ka]

[0028] In the above general formula (1), each M is independently a hydrolyzable group selected from the group consisting of an alkoxy group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, preferably 2 to 4 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, preferably 2 to 7 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, preferably 2 to 6 carbon atoms, and a halogen atom. Specific examples of the hydrolyzable group include alkoxy groups such as methoxy group, ethoxy group, propoxy group, and isopropoxy group, alkoxyalkoxy groups such as methoxymethoxy group, methoxyethoxy group, ethoxymethoxy group, and ethoxyethoxy group, acyloxy groups such as acetoxy group, alkenyloxy groups such as isopropenoxy group, and halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom, among which, in particular, methoxy group, ethoxy group, methoxymethoxy group, and acetoxy group are preferable.

[0029] In the above general formula (1), R is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms. Specific examples of the R include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, and hexyl, cycloalkyl groups such as cyclohexyl, alkenyl groups such as vinyl, allyl, and propenyl, and phenyl groups, with a methyl group being particularly preferred.

[0030] In the above general formula (1), a is 2 or 3, with 3 being particularly preferred.

[0031] As a specific method for synthesizing such a fluoropolyether-modified amidosilane compound, for example, the following method can be shown.

[0032] As a first method, a compound represented by the following general formula (4) [ka] (In the formula, Rf is the same as above, and R 1 are independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and d is independently an integer of 0 to 8 for each unit, provided that the linking CH2=CR1 C d H 2d The total number of carbon atoms in each is 2 to 10.) The four alkenyl groups of a fluoropolyetheramide compound having two alkenyl groups at each of the molecular chain ends (four alkenyl groups in the molecule), each of which is represented by the following general formula (5): [ka] (In the formula, M, R, l, n, and a are the same as above.) One example of a method is to add, by hydrosilylation addition reaction, the SiH group of an organosiloxane compound having a SiH group (a hydrogen atom bonded to a silicon atom) at one end of the molecular chain and a hydrolyzable silyl group at the other end.

[0033] As a second method, a fluoropolyetheramide compound having two alkenyl groups at each of both ends of the molecular chain (four alkenyl groups in the molecule) represented by the above general formula (4) is mixed with an excess amount of a compound represented by the following general formula (6) in terms of molar equivalent to the four alkenyl groups: [ka] (In the formula, l is the same as above.) The organosiloxane compound having SiH groups (hydrogen atoms bonded to silicon atoms) at both ends of the molecular chain, represented by the following general formula (7), is then added with one of the SiH groups by hydrosilylation addition reaction, and the remaining compound represented by the above general formula (6) is removed to obtain [ka] (In the formula, Rf, m, and l are the same as above.) The compound represented by the following general formula (8) is added to the SiH groups at both ends of the molecular chain of the compound represented by the following general formula (8): [ka] (In the formula, M, R, and a are the same as above, and R 2 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and e is an integer of 0 to 8, provided that the linking CH2=CR2 C e H 2e The total number of carbon atoms is 2 to 10. The compound can be synthesized by adding an alkenyl group to an alkenyl-containing hydrolyzable silane compound represented by the following formula (I):

[0034] Here, the fluoropolyether amide compound having two alkenyl groups at each of both molecular chain terminals (four in the molecule) represented by the above general formula (4) can be synthesized, for example, by reacting a fluoropolyether carboxylic acid derivative represented by the following general formula (9) with an amine compound having two terminal alkenyl-containing monovalent hydrocarbon groups represented by the following general formula (10) using a known amidation technique. [ka] (In the formula, Rf is the same as above, and X is independently a leaving group, for example, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, or an isopropoxy group, or a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.) [CH2=CR 1 C d H 2d ]2-NH (10) (In the formula, R 1 , d is the same as above, except that the linking CH2=CR 1 C d H 2d The total number of carbon atoms in each is 2 to 10.)

[0035] Specific examples of the fluoropolyether carboxylic acid derivative represented by the general formula (9) include those shown below. [ka] (In the formula, Rf is the same as above.)

[0036] Specific examples of the amine compound having two terminal alkenyl-containing monovalent hydrocarbon groups represented by general formula (10) include diallylamine, di(3-butenyl)amine, di(4-pentenyl)amine, and di(5-hexenyl)amine.

[0037] In the reaction of the compound represented by the general formula (9) with the compound represented by the general formula (10), it is convenient to add a solvent, a reaction catalyst, etc., as necessary, to the compound represented by the general formula (9) which is particularly an carboxylic acid halide, and then stir or heat and stir. Here, the heating conditions are preferably 0 to 150°C, particularly 20 to 100°C, for 5 minutes to 200 hours, particularly 30 minutes to 24 hours.

[0038] The amount of the compound represented by general formula (10) used in the above reaction is desirably 1 to 5 moles, preferably 1 to 1.5 moles, when the number of moles of the COX group contained in the compound represented by general formula (9) is taken as 1. If it is less than 1 mole, unreacted terminal groups remain, and if it is more than 5 moles, the burden of removing the unreacted compound represented by general formula (10) becomes large.

[0039] The above reaction can be carried out without the presence of a solvent by thoroughly stirring the reaction system, but may be diluted with a solvent if necessary. In this case, a solvent that dissolves both the compound represented by the general formula (9) and the compound represented by the general formula (10) can be used as the dilution solvent, but the solvent is preferably one that has a boiling point equal to or higher than the target reaction temperature, does not inhibit the reaction, and is soluble in the compound represented by the general formula (9) used in the reaction, the compound represented by the general formula (10), and the compound represented by the general formula (4) produced at the reaction temperature. As such a solvent, for example, a partially fluorine-modified solvent such as a fluorine-modified aromatic hydrocarbon solvent such as m-xylene hexafluoride or benzotrifluoride, or a fluorine-modified ether solvent such as methyl perfluorobutyl ether is preferable, and m-xylene hexafluoride is particularly preferable.

[0040] When a solvent is used, the amount of the solvent used is preferably 5 to 2,000 parts by mass, and more preferably 50 to 500 parts by mass, relative to 100 parts by mass of the compound represented by formula (9). If the amount is less than this, the effect of dilution by the solvent becomes weak, and if the amount is more, the degree of dilution becomes too high, which may lead to a decrease in the reaction rate.

[0041] When a reaction catalyst is used, any known one may be used, but tertiary amines such as trialkylamines such as triethylamine that form salts with the HX (X is the same as above) to be eliminated, diazabicycloundecene, diazabicyclononene, etc., and mixtures thereof are preferable. When a reaction catalyst is used, the amount used is preferably 1 to 5 times the molar amount, more preferably 1 to 2 times the molar amount, of the amount of HX to be eliminated. If the reaction catalyst is used in an amount less than 1 time by molar, HX that does not form a salt remains and may be difficult to remove, whereas if the amount is more than 5 times by molar, the excess catalyst may be difficult to remove.

[0042] After completion of the reaction, it is preferable to remove the unreacted compound represented by the formula (10), the reaction catalyst, the solvent, etc. by a known method such as distillation under reduced pressure, extraction, adsorption, etc.

[0043] Examples of the fluoropolyetheramide compound having two alkenyl groups at each of both molecular chain terminals (four in the molecule) represented by the above general formula (4) include the compounds shown below. [ka] (In the formula, Rf is the same as above.)

[0044] Examples of organosiloxane compounds having a SiH group (a hydrogen atom bonded to a silicon atom) at one end of the molecular chain and a hydrolyzable silyl group at the other end, as represented by the above general formula (5), include those shown below. [ka]

[0045] Examples of organosiloxane compounds having SiH groups (hydrogen atoms bonded to silicon atoms) at both molecular chain terminals, represented by the above general formula (6), include those shown below. [ka]

[0046] The reaction between the compound represented by the above formula (4) and the compound represented by the above formula (5) or formula (6) is carried out by a known hydrosilylation reaction. This hydrosilylation (addition) reaction is carried out by mixing the compound represented by the above formula (4) and the compound represented by the above formula (5) or formula (6), and in the presence of a platinum group metal-based addition reaction catalyst, at a reaction temperature of 50 to 150°C, preferably 60 to 120°C, for 1 minute to 48 hours, particularly 10 minutes to 12 hours. If the reaction temperature is too low, the reaction may stop before proceeding sufficiently, and if the reaction temperature is too high, the reaction may become uncontrollable due to the temperature rise caused by the hydrosilylation reaction heat, and bumping or decomposition of the raw materials may occur.

[0047] The reaction ratio of the compound represented by the above formula (4) and the compound represented by the above formula (5) is preferably 1 to 2 times, particularly 1 to 1.5 times, the moles of the compound represented by formula (5) relative to the total moles of the alkenyl groups of the compound represented by formula (4). If the amount of the compound represented by formula (5) is less than this, a compound with an alkenyl group remaining at one end of the compound represented by formula (4) is generated as a by-product. If the amount of the compound represented by formula (5) is more than this, the uniformity of the reaction solution decreases and the reaction rate becomes unstable. In addition, when removing the unreacted compound represented by formula (5) after the reaction, it becomes necessary to make the conditions of heating, decompression, extraction, etc. stricter as the amount of unreacted increases.

[0048] The reaction ratio of the compound represented by the above formula (4) and the compound represented by the above formula (6) is preferably an excess amount, i.e., 2 to 20 times the molar equivalent, particularly 4 to 10 times the molar equivalent, of the compound represented by formula (6) relative to the total moles of the alkenyl groups of the compound represented by formula (4). If the amount of the compound represented by formula (6) is less than this amount, a compound in which both terminal SiH groups of the compound represented by formula (6) react with the alkenyl groups of the compound represented by formula (4) is generated as a by-product, and the target product cannot be obtained. If the amount of the compound represented by formula (6) is too much, the uniformity of the reaction solution decreases and the reaction rate becomes unstable. In addition, when removing the unreacted compound represented by formula (6) after the reaction, it becomes necessary to make the conditions of heating, decompression, extraction, etc. stricter as the amount of unreacted increases.

[0049] Examples of the compound represented by the general formula (7) obtained by reacting a fluoropolyetheramide compound represented by the general formula (4) having two alkenyl groups at each of both molecular chain terminals (four alkenyl groups per molecule) with a compound represented by the general formula (6) include the compounds shown below. [ka] (In the formula, Rf is the same as above.)

[0050] Examples of the alkenyl-containing hydrolyzable silane compound represented by the above general formula (8) to be reacted with the above general formula (7) include the compounds shown below. [ka]

[0051] The reaction between the compound represented by the above formula (7) and the compound represented by the above formula (8) is carried out by a known hydrosilylation reaction. This hydrosilylation (addition) reaction is carried out by mixing the compound represented by the above formula (7) and the compound represented by the above formula (8) in the presence of a platinum group metal-based addition reaction catalyst at a reaction temperature of 50 to 150°C, preferably 60 to 120°C, for 1 minute to 48 hours, particularly 10 minutes to 12 hours. If the reaction temperature is too low, the reaction may stop before proceeding sufficiently, and if the reaction temperature is too high, the reaction may become uncontrollable due to the temperature rise caused by the hydrosilylation reaction heat, and bumping or decomposition of the raw materials may occur.

[0052] The reaction ratio of the compound represented by the above formula (7) and the compound represented by the above formula (8) is preferably 1 to 5 times, particularly 1 to 1.5 times, the molar amount of the compound represented by formula (8) relative to the total molar amount of the SiH groups of the compound represented by formula (7). If the amount of the compound represented by formula (8) is less than this amount, a compound with a remaining SiH group is generated as a by-product, and the target product cannot be obtained. If the amount of the compound represented by formula (8) is more than this amount, the uniformity of the reaction solution decreases and the reaction rate becomes unstable. In addition, when removing the unreacted compound represented by formula (8) after the reaction, the conditions of heating, decompression, extraction, etc. must be made stricter as the amount of unreacted increases.

[0053] The addition reaction catalyst used in the hydrosilylation (addition) reaction may be, for example, a compound containing a platinum group metal such as platinum, rhodium, or palladium. Among them, a compound containing platinum is preferred, and it may be a complex of chloroplatinic acid and alcohol or vinylsiloxane, such as hexachloroplatinic acid (IV) acid hexahydrate, platinum carbonylvinylmethyl complex, chloroplatinic acid (platinum)-divinyltetramethyldisiloxane complex, chloroplatinic acid (platinum)-cyclovinylmethylsiloxane complex, or chloroplatinic acid (platinum)-octylaldehyde / octanol complex, or platinum supported on activated carbon. The amount of the addition reaction catalyst to be added is preferably an amount such that the metal content is 0.1 to 5,000 ppm by mass, and more preferably 0.2 to 1,000 ppm by mass, relative to the compound represented by formula (4) or formula (7).

[0054] The hydrosilylation (addition) reaction can be carried out without the presence of a solvent, but may be diluted with a solvent as necessary. In this case, the dilution solvent may be a widely used organic solvent such as toluene, xylene, isooctane, etc., but it is preferable to use a solvent whose boiling point is equal to or higher than the target reaction temperature, which does not inhibit the reaction, and in which the compounds used in the reaction and the product are soluble at the reaction temperature. As such a solvent, for example, a partially fluorine-modified solvent such as a fluorine-modified aromatic hydrocarbon solvent such as m-xylene hexafluoride or benzotrifluoride, or a fluorine-modified ether solvent such as methyl perfluorobutyl ether is preferable, and m-xylene hexafluoride is particularly preferable. When a solvent is used, the amount used is preferably 5 to 2,000 parts by mass, more preferably 40 to 500 parts by mass, based on 100 parts by mass of the compound represented by formula (4) or formula (7). If the amount is less than this, the effect of dilution by the solvent becomes weak, and if the amount is more, the degree of dilution becomes too high, which may lead to a decrease in the reaction rate.

[0055] After completion of the above hydrosilylation (addition) reaction, it is preferable to remove the unreacted compound represented by formula (5), formula (6) or formula (8), catalyst residues, dilution solvent, etc. by a known method such as vacuum distillation, extraction, adsorption, etc.

[0056] In particular, when the fluoropolyether-modified amidosilane compound represented by formula (1) is finally isolated, if the compound contains a fluorine-containing solvent having a boiling point of 260° C. or less at normal pressure, such as m-xylene hexafluoride, benzotrifluoride, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, 3-methoxyperfluoro(3-methylpentane), or 2-(trifluoromethyl)-3-ethoxydodecafluorohexane, it is preferable to remove the fluorine-containing solvent so that the amount is less than 1 mass% of the entire fluoropolyether-modified amidosilane compound represented by formula (1).

[0057] Here, the content of the fluorine-containing solvent having a boiling point of 260° C. or less at normal pressure is, for example, 19 F-NMR spectrum or 1 It can be calculated from the NMR measurement results, based on the H-NMR spectrum, by adding an internal standard substance to the fluoropolyether-modified amidosilane compound represented by the above general formula (1) as necessary. Alternatively, it can be simply determined by a heat loss test under conditions where the non-volatile content of each solvent is less than 1 mass%.

[0058] As the fluoropolyether-modified amidosilane compound represented by the above general formula (1) obtained as described above, the following compounds can be exemplified. [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0059] In the above formula, Rf a can be exemplified by the same as Rf above, but is preferably one represented by any of the following formulae. [ka] [ka] -CF2O(CF2O) p1 (CF2CF2O) q1 CF2- (In the formula, the average value of s1+t1 is 15 to 100, the average value of p1+q1 is 15 to 80, and q1 / p1 is 0.8 to 1.2. The arrangement of each repeating unit shown in parentheses with p1 and q1 is random.)

[0060] The fluoropolyether-modified amidosilane compound represented by formula (1) of the present invention is as described above. These compounds are high molecular weight compounds that do not have a boiling point at normal pressure (atmospheric pressure) and are non-volatile when used in the surface treatment composition of the present invention.

[0061] A further embodiment of the present invention is a method for using a surface treatment agent composition containing a fluoropolyether-modified amidosilane compound represented by formula (1) and / or a partial hydrolysis condensate thereof, which is applied to various surfaces, as a surface treatment agent composition containing a nonvolatile fluorine-containing organic compound that imparts excellent properties such as water repellency, oil repellency, antifouling property, fingerprint resistance, fingerprint removability, slipperiness, abrasion resistance, scratch resistance, solvent resistance, chemical resistance, liquid droplet sliding property, snow adhesion sliding property, ice adhesion sliding property, antifogging property, surface leveling property, release property, low refractive index, and antireflection to the surface.

[0062] The surface treatment composition of the present invention imparts the properties of the fluoropolyether-modified amidosilane compound represented by formula (1) and / or its partial hydrolysis condensate to the surface of various substrates. The surface treatment composition of the present invention is a surface treatment composition containing a non-volatile fluorine-containing organic compound, characterized in that the non-volatile fluorine-containing organic compound contains the fluoropolyether-modified amidosilane compound represented by formula (1) and / or its partial hydrolysis condensate. Here, non-volatile means that it does not volatilize when heated at 260°C under atmospheric pressure. For example, impurities contained in raw materials and by-products generated in the manufacturing process may remain or be mixed into the surface treatment composition.

[0063] Such impurities and by-products that may be mixed in include, specifically, the raw materials and intermediates used and the impurities contained therein, those having a structure in which a part of the Rf group is not fluorinated, and those having the following general formula (11): [ka] (In the formula, Y is a monovalent group, and examples of such groups include a hydrogen atom, a fluorine atom, a carboxyl group and its salts, a hydroxyl group, an ester group, an amide group, and a formyl group.) a fluoropolyether-modified amidosilane compound represented by formula (1) or a compound represented by formula (11) represented by formula (12), a R 3-a ] groups are replaced with other functional groups.

[0064] It is not a practical problem if these contaminants are present to the extent that they do not significantly affect the solubility of the fluoropolyether-modified amidosilane compound represented by formula (1) and / or its partial hydrolysis condensate or the surface properties that can be imparted. However, in order to maintain the properties imparted, the surface treatment agent composition of the present invention preferably contains 80 mass% or more of the fluoropolyether-modified amidosilane compound represented by formula (1) and / or its partial hydrolysis condensate in the non-volatile components. For the same reason, it is preferable that the fluorine content in the non-volatile components is 40 to 65 mass% when measured. The fluorine content is determined by the standard substance or the like used in the non-volatile components. 19 It can be calculated from F-NMR or by elemental analysis of the non-volatile matter.

[0065] The surface treatment agent composition of the present invention is desirably diluted in advance with a solvent, and the solvent is not particularly limited as long as it can uniformly dissolve the fluoropolyether-modified amidosilane compound represented by formula (1) and / or its partial hydrolysis condensate, but from the viewpoint of storage stability and convenience in drying after coating, it is desirable for the boiling point to be in the range of 25 to 260° C., particularly 45 to 150° C. If the boiling point is lower than this range, the storage stability is reduced and it becomes difficult for workers to take measures against volatile matters, and if it is higher than this range, the drying process becomes difficult.

[0066] Specific examples of such solvents include fluorine-modified aliphatic hydrocarbon solvents (perfluoroheptane, perfluorooctane, etc.), fluorine-modified aromatic hydrocarbon solvents (m-xylene hexafluoride, etc.), fluorine-modified ether solvents (methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro(2-butyltetrahydrofuran), etc.), fluorine-modified alkylamine solvents (perfluorotributylamine, perfluorotripentylamine, etc.), and solvents that do not contain fluorine atoms, specifically hydrocarbon solvents (hexane, heptane, octane, isopropyl alcohol, etc.). octane, isononane, isodecane, pentamethylheptane, petroleum benzine, toluene, xylene, etc.), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, etc.), ether solvents (diisopropyl ether, dibutyl ether, monoglyme, diglyme, tetrahydrofuran, 2-methyltetrahydrofuran, cyclopentyl methyl ether), ester solvents (ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate), propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, etc.

[0067] Among these, in order to fully utilize the properties of the fluoropolyether-modified amidosilane compound represented by formula (1) of the present invention and / or its partial hydrolysis condensate, a solvent not containing a fluorine atom is preferable. The above-mentioned solvents may be used alone or in combination of two or more.

[0068] The optimal concentration of the fluoropolyether-modified amidosilane compound represented by formula (1) and / or its partial hydrolysis condensate to be dissolved in a solvent varies depending on the treatment method, and may be an amount that is easy to weigh. When dissolved in a solvent, the content of the fluoropolyether-modified amidosilane compound represented by formula (1) and / or its partial hydrolysis condensate in the surface treatment agent composition is preferably 0.01 to 95 mass%. Among these, in the case of direct coating, the content of the fluoropolyether-modified amidosilane compound and / or its partial hydrolysis condensate represented by formula (1) is preferably 0.01 to 10 mass%, particularly 0.05 to 5 mass%, based on the total mass of the solvent and the fluoropolyether-modified amidosilane compound and / or its partial hydrolysis condensate, and in the case of vapor deposition treatment, it is not necessary to dissolve in a solvent, and in the case of dissolving in a solvent, the content of the fluoropolyether-modified amidosilane compound and / or its partial hydrolysis condensate represented by formula (1) is preferably 1 to 95 mass%, particularly 3 to 30 mass%, based on the total mass of the solvent and the fluoropolyether-modified amidosilane compound and / or its partial hydrolysis condensate. In addition, these dilutions may be used by diluting a solution diluted to a certain concentration in advance to the required concentration each time it is used.

[0069] The surface treatment composition of the present invention can be applied to a substrate by a known method such as brushing, dipping, spraying, or vapor deposition. The heating method during vapor deposition may be either resistance heating or electron beam heating, and is not particularly limited. The curing temperature varies depending on the curing method, but is preferably in the range of 20 to 200°C when applied by dipping or vapor deposition. Curing may also be performed under humid conditions. The thickness of the cured coating is appropriately selected depending on the type of substrate, but is usually 0.1 to 100 nm, particularly 1 to 20 nm.

[0070] In addition, the general form of use of the surface treatment composition of the present invention can be applied to any substrate as long as the layer of the surface treatment composition of the present invention adheres or bonds after curing, and examples of such substrates include paper, cloth, metal and its oxide, leather, synthetic leather, resin, wood, glass, SiO2-treated glass and resin film, ceramic (pottery), quartz, sapphire substrate, stone, and other various materials, as well as coating surfaces formed by coating these substrates with various paints, etc. These can be used on the surfaces of any form, such as films, plates, and molded members.

[0071] Specifically, the cured coating (cured resin layer) obtained by the surface treatment agent composition of the present invention can be used for the surfaces and display parts, operation parts, etc. of various devices such as tablet computers, notebook PCs, mobile phones, smartphones, and other portable (communication) information terminals, digital media players, digital cameras, digital video cameras, and electronic book readers; watch-type and eyeglasses-type wearable computers; wearable sensors for the human body or animals, such as heart rate monitors and pulse rate monitors; various flat panel displays, such as head-mounted displays, liquid crystal displays, plasma displays, organic electroluminescence (EL) displays, rear projection displays, fluorescent display tubes (VFDs), field emission projection displays, CRTs, toner-based displays, and quantum dot (QD) displays; and TV screens and other display and operation device surfaces and various optical films used inside these devices; GPS display and recording devices; navigation devices for automobiles, etc.; control panels for automobiles, etc.; automatic cash withdrawal and deposit devices, automatic cash dispensers, vending machines, digital signage (electronic billboards), security system terminals, POS terminals, relays, etc. Various controllers such as remote controllers, display input devices such as panel switches for in-vehicle devices, glossy surfaces of pianos and furniture, architectural stone surfaces such as marble, surfaces of furniture, decorative building materials for wet areas such as toilets, baths and washrooms, sanitary ware, protective glass for displaying art works, show windows, showcases, covers for photo frames, wristwatches, exteriors and interiors of cosmetic containers, exteriors of decorative items, exteriors of decorative item containers, window glass for various vehicles such as automobiles and trains, resin and metal parts for the interior and exterior of various vehicles such as automobiles and trains, overcoats for vehicle paint, indoor and outdoor signs, advertising displays Used as paint films and surface protection films for signs, road signs, guide plates, the light-emitting parts of indoor and outdoor lighting fixtures, coatings for the display parts of various traffic signals and LED signs, display parts of electronic mirrors for automobiles, outdoor painting of various buildings, window glass and interior and exterior decoration of transportation devices such as trains and aircraft, peripheral parts of ink nozzles for various printing printers, peripheral parts of material discharge nozzles for various 3D printers, transparent glass or transparent plastic (acrylic, polycarbonate, etc.) parts such as automobile headlights and taillights, cover parts for automotive sensors such as millimeter wave radar, various mirror parts, etc.

[0072] It can also be used as a surface protective coating for optical components and optical devices such as eyeglass lenses, prisms, lens sheets, pellicle films, polarizing plates, optical filters, lenticular lenses, Fresnel lenses, anti-reflection films, various camera lenses, various lens filters, optical fibers, and optical couplers.

[0073] The surface treatment composition of the present invention provides a cured coating film having excellent antifouling, water repellency, oil repellency, and fingerprint resistance on the surface by applying it to the surface of a substrate and curing it. This makes it difficult for various substrates to be stained by rain, sand dust, pollen, animal droppings, insect collisions, various industrial oils, food oils, seasonings, fingerprints, sebum, sweat, and other human oils, cosmetics, graffiti with ink or paint, etc., and even if stains are attached, it has excellent wipeability, and even if adhesives such as gum and stickers are attached, they can be easily removed. Therefore, the surface treatment composition containing 80% by mass or more of the fluoropolyether-modified amidosilane compound and / or its partial hydrolysis condensate of the present invention is useful for forming a protective film on various substrates. EXAMPLES

[0074] The present invention will be specifically described below with reference to Synthesis Examples, Synthesis Examples, Synthesis Comparative Examples, Examples and Comparative Examples, but the present invention is not limited to the following Synthesis Examples and Examples.

[0075] [Synthesis Example 1] In a four-neck flask equipped with a stirrer and a reflux device, the following formula (12) was added: [ka] ( 19 The average value of s2+t2 obtained from F-NMR was 32.5, the number average molecular weight of the divalent perfluoropolyether group obtained based on this was 5,821, and the -COF group concentration obtained by calculation was 0.000344 mol / g. (0.515 mol as -COF group), 67.6 g (0.70 mol) of diallylamine, and 52.4 g (0.52 mol) of triethylamine were charged and mixed with stirring at 50° C. The IR measurement of the reaction solution after 4 hours showed that the peak intensity was 1,780 cm -1 The carbonyl group absorption of the acid fluoride disappears, and a new absorption at 1,685 cm -1 It was confirmed that absorption originating from the carbonyl group of the amide group occurred. Next, 36.8 g of calcium carbonate was added, and the temperature was raised to 95° C. while continuing stirring. After reaching 95° C., stirring was continued for 1 hour, and then cooled. The reaction solution cooled to room temperature was heated and reduced in pressure at 150° C. / 0.8 kPa in a rotary evaporator until no distillate was left. The components obtained after cooling the flask were stirred for 2 hours with 1,000 g of fluorine solvent PF-5060 manufactured by 3M Japan, 15 g of activated carbon, and 15 g of adsorbent Kyoward 700 manufactured by Kyowa Interface Science, and pressure filtered with NA-500 filter plate manufactured by Advantec Toyo Co., Ltd. The obtained filtrate was distilled under reduced pressure at 120° C. / 0.8 kPa in a rotary evaporator, and 1,445 g of a colorless transparent liquid was obtained. The obtained compound was 19 F-NMR, 1 The results of H-NMR and IR measurements confirmed that the compound was represented by the following formula (I). [ka] ( 19 The average value of s2+t2 determined from F-NMR is 32.5.

[0076] [Synthesis Example 2] The amount of the mixture is calculated according to the following formula (13): [ka] ( 19 The average value of s3+t3 obtained from F-NMR was 20.8, and the number average molecular weight of the divalent perfluoropolyether group obtained based on this was 3,879, and the calculated COF group concentration was 0.000515 mol / g. The same procedure as in Synthesis Example 1 was repeated except that 1,500 g (0.77 mol as -COF group) of the compound represented by the following formula (II) was used, 92.5 g (0.95 mol) of diallylamine, and 95.3 g (0.94 mol) of triethylamine were used, to obtain 1,513 g of a colorless, transparent liquid compound represented by the following formula (II). [ka] ( 19 The average value of s3+t3 determined from F-NMR is 20.8.)

[0077] [Synthesis Example 1] Into a four-neck flask equipped with a stirrer and a reflux device, 600 g of the compound of the above formula (I) (0.40 mol as allyl group), 240 g of m-xylene hexafluoride, and 0.6 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (1.5×10 -6 The mixture was heated to 85° C. under a nitrogen atmosphere while stirring. [ka] After stirring for 2 hours, the reaction mixture was cooled to room temperature and cooled to room temperature. 1 H-NMR was measured. 1 As a result of H-NMR measurement, it was confirmed that the allyl group of the compound of formula (I) had disappeared, and the heating was stopped and the solution was cooled. After cooling, the solution was filtered through a PTFE filter having a pore size of 0.2 m, and then distilled under reduced pressure at 150°C / 1.3 kPa under nitrogen bubbling to obtain 692 g of a pale yellow transparent liquid. 19 F-NMR, 1 The results of H-NMR and IR measurements confirmed that neither the compound represented by formula (III) nor the solvent m-xylene hexafluoride remained, and only the compound represented by formula (IV) below was present. [ka] ( 19The average value of s2+t2 obtained from F-NMR is 32.5, and the average fluorine content obtained from this is 55.8% by mass.

[0078] [Synthesis Example 2] A pale yellow transparent liquid (701 g) was obtained in the same manner as in Synthesis Example 1, except that 600 g (0.60 moles as allyl group) of the compound of formula (II) was used instead of the compound of formula (I) and the amount of the compound of formula (III) was 174 g (0.62 moles). 19 F-NMR, 1 The results of H-NMR and IR measurements confirmed that neither the compound represented by (III) above nor the solvent m-xylene hexafluoride remained, and only the compound represented by the following formula (V) remained. [ka] ( 19 The average value of s3+t3 determined from F-NMR is 20.8, and the average fluorine content calculated from this is 50.9% by mass.

[0079] [Comparative Synthesis Example 1] Into a four-neck flask equipped with a stirrer and a reflux device, 60 g of the compound of the above formula (I) (0.040 mol as allyl group), 100 g of m-xylene hexafluoride, and 0.2 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (0.5×10 -6 The mixture was heated to 80°C while stirring under a nitrogen atmosphere. 13g (0.11 mol) of trimethoxysilane was added dropwise to the mixture, and stirring was continued for 8 hours. 1 H-NMR was measured. 1 As a result of H-NMR measurement, it was confirmed that the allyl group of the compound of formula (I) had disappeared, and the heating was stopped and the solution was cooled. After cooling, the solution was filtered through a PTFE filter having a pore size of 0.2 m, and then distilled under reduced pressure at 100°C / 1.3 kPa under nitrogen bubbling to obtain 61 g of a pale yellow transparent liquid. 19 F-NMR, 1The results of H-NMR and IR measurements confirmed that neither the above trimethoxysilane nor the solvent m-xylene hexafluoride remained, and only the compound represented by the following formula (VI) was present. [ka] ( 19 The average value of s2+t2 obtained from F-NMR is 32.5, and the average fluorine content obtained from this is 61.2% by mass.

[0080] [Examples 1 and 2 and Comparative Example 1] Solubility check: 16 g of each of the compounds represented by the above formulae (IV), (V), and (VI) obtained in Synthesis Examples 1 and 2 and Synthesis Comparative Example 1 and 64 g of each of the dehydrated solvents shown in Table 1 were uniformly mixed by stirring in a sealed 100 ml transparent vial, and the mixture was allowed to stand at 20°C, after which the appearance was visually confirmed. Transparent and uniformly dissolved products were evaluated as "○", and those that were not compatible and separated were evaluated as "×". The results are shown in Table 1.

[0081] [Table 1]

[0082] [Examples 3 and 4 and Comparative Example 2] The compounds represented by the above formulas (IV) and (V) obtained in Synthesis Examples 1 and 2 were diluted to 0.1% by mass with dehydrated isopropyl acetate to form a solution (surface treatment composition), and a slide glass was immersed for 10 seconds, and then lifted at 150 mm / min. The slide glass was then held in a thermohygrostat at 80° C. and 80% humidity for 4 hours to obtain a cured coating of the above compound (film thickness: 6 nm). The water contact angle (water repellency) and antifouling properties (marker repelling property, marker wipeability) of the obtained coating surface (cured coating) and uncoated glass were evaluated by the following method.

[0083] [Evaluation of water repellency] A contact angle meter (DropMaster, manufactured by Kyowa Interface Science Co., Ltd.) was used to measure the water contact angle 1 second after a 2 μL droplet of water was dropped onto the cured coating or glass surface. The average value of N=5 was recorded as the measured value. The results are shown in Table 2.

[0084] [Evaluation of marker repelling properties] A straight line was drawn on the cured coating or the glass surface with a magic marker (Zebra Corp., Hi-Mackie Bold), and the repellency was evaluated by visual observation. The results are shown in Table 2.

[0085] [Evaluation of marker wipeability] A straight line was drawn on the cured coating or glass surface with a marker pen (Zebra Corporation's Hi-Mackie bold), and after one minute it was lightly rubbed three times with tissue paper. If no trace of the marker remained, it was rated as "can be wiped off", and if a trace remained, it was rated as "cannot be wiped off". The results are shown in Table 2.

[0086] [Table 2]

Claims

1. The following general formula (1) 【Chemistry 1】 (In the formula, Rf is a divalent perfluoropolyether group having a number average molecular weight of 1,500 to 20,000; each Z is independently a divalent linking group containing one Si-O-Si bond; each M is independently a hydrolyzable group selected from the group consisting of an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, and a halogen atom; each R is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms; and a is 2 or 3.) The fluoropolyether-modified amidosilane compound is represented by the formula:

2. 2. The fluoropolyether-modified amidosilane compound according to claim 1, wherein in the above general formula (1), Rf is represented by the following general formula (2): -CF(Y)-O-Rf 1 -CF(Y)- (2) (Wherein, Y is F or CF 3 and Rf 1 is composed of repeating units selected from one or more of the following perfluorooxyalkylene units: -CF 2 O- -CF 2 CF 2 O- -CF 2 CF 2 CF 2 O- -CF(CF 3 )CF 2 O- -CF 2 CF(CF 3 )O- -CF 2 CF 2 CF 2 CF 2 O- -CF 2 CF 2 CF 2 CF 2 CF 2 O- -CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 O- -CF 2 CF 2 OCF 2 CF 2 CF 2 CF 2 O-

3. 3. The fluoropolyether-modified amidosilane compound according to claim 1, wherein in the general formula (1), Rf is any one of the following: -CF 2 O(CF 2 O) p (CF 2 CF 2 O) q CF 2 - (In the formula, p is an integer of 10 to 300, q is an integer of 5 to 170, and p+q is an integer of 15 to 470 such that the number average molecular weight of Rf is 1,500 to 20,000, and the arrangement of each repeating unit is random.) 【Chemistry 2】 (In the formula, s and t are independently integers of 1 to 120, and s+t is an integer of 2 to 240 such that the number average molecular weight of Rf is 1,500 to 20,000, u is an integer of 1 to 6, and v is an integer of 0 to 10.) -CF 2 CF 2 O[CF 2 CF 2 CF 2 O] w CF 2 CF 2 - (In the formula, w is an integer from 8 to 119.) -C z F 2z O(CF 2 CF 2 O) x (CF 2 CF 2 CF 2 CF 2 O) y C z F 2z - (In the formula, x is an integer of 2 to 300, y is an integer of 2 to 80, and x+y is an integer of 4 to 380 such that the number average molecular weight of Rf is 1,500 to 20,000. z is independently 1 or 2 for each unit. The arrangement of each repeating unit is random.)

4. The fluoropolyether-modified amidosilane compound according to any one of claims 1 to 3, wherein in the general formula (1), Z is a divalent linking group containing a diorganopolysiloxane structure consisting of only one Si-O-Si bond.

5. The fluoropolyether-modified amidosilane compound according to any one of claims 1 to 4, wherein in the general formula (1), M is an alkoxy group having 1 to 10 carbon atoms.

6. A surface treatment agent composition containing a non-volatile fluorine-containing organic compound, wherein the non-volatile fluorine-containing organic compound contains 80 mass% or more of the fluoropolyether-modified amidosilane compound and / or its partial hydrolysis condensate according to any one of claims 1 to 5.

7. The surface treatment composition according to claim 6, wherein the average fluorine content of the nonvolatile fluorine-containing organic compound is 40 to 65 mass %.

8. The surface treatment agent composition according to claim 6 or 7, further comprising an organic solvent having a boiling point of 25 to 260°C, wherein the content of the fluoropolyether-modified amidosilane compound and / or its partial hydrolysis condensate in the surface treatment agent composition is 0.01 to 95 mass%.

9. 9. The surface treatment composition according to claim 8, wherein the organic solvent does not contain a fluorine atom.

10. An article having a cured coating of the surface treatment composition according to any one of claims 6 to 9.

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