Surface-treated items

Abstract

This article is characterized by: comprising a surface treatment layer formed of a surface treatment agent containing a fluorooxyalkylene group-containing polymer that does not contain a carbonyl bond but has a hydrolysable group in the molecule thereof, and / or a partial hydrolysis-condensation product of the polymer; and having, after a UVC resistance test is perfomed thereon under conditions described below, a static water contact angle of at least 100 degrees. The surface treatment layer has excellent water repellency and UVC resistance. Conditions for the UVC resistance test: The surface treatment layer of the article is irradiated with a total of 216000 μW·h / cm2 of a sterilization ray (UVC) using a sterilization lamp having a maximum emission wavelength of 254 nm.

Description

[Technical Field]

[0001] The present invention provides a surface-treated article that has water repellency and maintains its water repellency even after being irradiated with ultraviolet UVC rays for a specified period of time. Product Regarding. [Background technology]

[0002] In recent years, there has been an increasing demand for technologies that make surfaces less susceptible to fingerprints and easier to clean for items such as smartphones and tablets that are often in direct contact with fingers and cheeks and are therefore prone to stains such as sebum. There is a need for materials that can meet these demands.

[0003] In general, fluorooxyalkylene group-containing compounds have very low surface free energy and therefore possess water- and oil-repellent properties, chemical resistance, lubricity, mold release properties, and stain resistance. These properties have led to a wide range of industrial applications, including water-, oil-, and stain-resistant agents for paper and textiles, lubricants for magnetic recording media, oil repellents for precision instruments, mold release agents, cosmetics, and protective films. However, these properties also mean that they are non-sticky and non-adhesive to other substrates, and while they can be applied to the surface of a substrate, it has been difficult to form a coating that adheres to it.

[0004] Silane coupling agents are well known as agents for bonding organic compounds to the surfaces of substrates such as glass and cloth, and are widely used as coating agents for various substrate surfaces. Silane coupling agents contain an organic functional group and a reactive silyl group (generally a hydrolyzable silyl group such as an alkoxysilyl group) in each molecule. The hydrolyzable silyl group undergoes a self-condensation reaction in the presence of moisture in the air to form a coating. This coating is durable and strong because the hydrolyzable silyl group chemically and physically bonds with the surface of glass, metal, etc.

[0005] Therefore, compositions have been disclosed that use fluorooxyalkylene group-containing polymers in which hydrolyzable silyl groups have been introduced into fluorooxyalkylene group-containing compounds, which can form coatings that easily adhere to substrate surfaces and have water and oil repellency, chemical resistance, lubricity, releasability, antifouling properties, etc. on the substrate surfaces (Patent Documents 1 to 6: JP-A 2008-534696, JP-A 2008-537557, JP-A 2012-072272, JP-A 2012-157856, JP-A 2013-136833, JP-A 2015-199906).

[0006] Furthermore, in recent years, awareness and interest in antibacterial and antiviral measures has increased in line with the spread of the new coronavirus COVID-19. In particular, in facilities where an unspecified number of people use the same item, such as schools and hospitals, there has been an increase in the number of cases where items are regularly exposed to ultraviolet light, especially UVC, as a measure against bacteria and viruses.

[0007] Here, UVC refers to ultraviolet light with a wavelength of 280 nm or less, and UVC sterilization is the safest and most reliable sterilization method compared to other disinfection methods such as alcohol disinfection, chlorine disinfection, and ozone disinfection.

[0008] However, conventional water-repellent substrates do not have sufficient durability against UVC light, and there was a problem that the water-repellent properties deteriorated when sterilized repeatedly with a UVC germicidal lamp.

[0009] In response to this issue, with the recent rise in awareness and interest in antibacterial and antiviral properties, there is a growing demand for products whose water repellency does not deteriorate even after repeated sterilization using UVC germicidal lamps. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] Special Publication No. 2008-534696 [Patent Document 2] Special Publication No. 2008-537557 [Patent Document 3] Japanese Patent Application Laid-Open No. 2012-072272 [Patent Document 4] Japanese Patent Application Laid-Open No. 2012-157856 [Patent Document 5] Japanese Patent Application Laid-Open No. 2013-136833 [Patent Document 6] Japanese Patent Application Laid-Open No. 2015-199906 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 provides a surface-treated article that has water repellency and maintains its water repellency even after being irradiated with UVC for a specified period of time. Product The purpose is to provide. [Means for solving the problem]

[0012] As a result of intensive research to achieve the above object, the present inventors have found that when a surface treatment agent forming a surface treatment layer contains a fluorooxyalkylene group-containing polymer having a hydrolyzable group and / or a partial hydrolysis condensate thereof, and the fluorooxyalkylene group-containing polymer and / or the partial hydrolysis condensate thereof does not contain a carbonyl bond in the molecule, the surface treatment layer has excellent water and oil repellency and UVC resistance, which led to the present invention.

[0013] Therefore, the present invention provides the following: Product provide. [1] An article having a surface-treated layer formed from a surface treatment agent containing a fluorooxyalkylene group-containing polymer having a hydrolyzable group and / or a partial hydrolysis condensate thereof, which does not contain a carbonyl bond in the molecule, The fluorooxyalkylene group-containing polymer having a hydrolyzable group is represented by the following formula (2): [ka] [Wherein Rf is -C d F2d -O-(CF2O) p (C2F4O) q (C3F6O) r (C4F8O) s (C5F 10 O) t (C6F 12 O) u -C d F 2d - (wherein d is independently an integer of 0 to 5 for each unit, p, q, r, s, t, and u are each independently an integer of 0 to 150, the sum of p, q, r, s, t, and u is at least 1, and each of these units may be linear or branched. Furthermore, each of the repeating units shown in parentheses with p, q, r, s, t, and u may be bonded randomly), and A 1 is a monovalent fluorine-containing hydrocarbon group whose terminal is CF3- or CF2H- and which may contain an oxygen atom, or D, where D is a monovalent group represented by the following formula (3): [ka] [However, Q is an ether bond. , Shi oxane bond , Shi Z is a tri- to octavalent group selected from a silicon atom, a nitrogen atom, and a tri- to octavalent organopolysiloxane residue having a siloxane bond; α is an integer of 2 to 7; and W is independently a group represented by the following formula (1): [ka] (In the formula, R is an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydrolyzable group, a is 2 or 3, Y is a single bond, or A group selected from the group consisting of alkylene groups having 1 to 10 carbon atoms, alkylene groups having 1 to 10 carbon atoms in which some of the hydrogen atoms have been substituted with fluorine atoms, alkylene groups containing an arylene group having 6 to 8 carbon atoms, divalent groups in which alkylene groups are bonded to each other via a silalkylene structure or a silarylene structure, and divalent groups in which alkylene groups are bonded to each other via a linear divalent organopolysiloxane residue having 2 to 10 silicon atoms. ) is a monovalent hydrolyzable silyl group-containing group represented by the following formula: and an article to be subjected to UVC sterilization disinfection, characterized in that the static contact angle of water after undergoing a UVC resistance test under the following conditions is 100 degrees or more. <Conditions for UVC resistance test> Using a germicidal lamp with a maximum emission wavelength of 254 nm, germicidal rays (UVC) were applied to the surface treatment layer of the item at a total of 216,000 μW·h / cm 2 Irradiate. [2] The article according to [1], wherein Q in the formula (3) is an alkylene group having 2 to 4 carbon atoms which may contain an ether bond, or a single bond. [3] The article according to [2], wherein Z in the formula (3) is a trivalent or tetravalent group selected from a silicon atom, a nitrogen atom, and a trivalent or tetravalent organopolysiloxane residue having a siloxane bond, and α is 2 or 3. [ 4 〕 The article according to [1], wherein the fluorooxyalkylene group-containing polymer having a hydrolyzable group is any one of the following: [ka] (In the formula, A 1 , Rf is the same as above.) [ 5 〕 An article having a surface-treated layer formed from a surface treatment agent containing a fluorooxyalkylene group-containing polymer having a hydrolyzable group and / or a partial hydrolysis condensate thereof, which does not contain a carbonyl bond in the molecule, The fluorooxyalkylene group-containing polymer having a hydrolyzable group is represented by the following formula (4): [ka] [Wherein Rf is the same as above, A 2 is a monovalent fluorine-containing hydrocarbon group whose terminal is CF3- or CF2H- and which may contain an oxygen atom, or G, where G is a monovalent group represented by the following formula (5). [ka] [W independently represents the following formula (1)] [ka] (In the formula, R is an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydrolyzable group, a is 2 or 3, Y is a single bond, or A group selected from the group consisting of alkylene groups having 1 to 10 carbon atoms, alkylene groups having 1 to 10 carbon atoms in which some of the hydrogen atoms have been substituted with fluorine atoms, alkylene groups containing an arylene group having 6 to 8 carbon atoms, divalent groups in which alkylene groups are bonded to each other via a silalkylene structure or a silarylene structure, and divalent groups in which alkylene groups are bonded to each other via a linear divalent organopolysiloxane residue having 2 to 10 silicon atoms. ) wherein J is a single bond or an oxygen atom, B is —OS, and S is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a group represented by the following formula (6): [ka] (In the formula, T represents a divalent hydrocarbon group having 2 to 20 carbon atoms, a divalent silalkylene group, or a diorganosilylene group, which may contain one or more bonds selected from the group consisting of a siloxane bond, a silalkylene bond, a silarylene bond, and a diorganosilylene group; L represents independently a divalent hydrocarbon group having 1 to 4 carbon atoms; E represents a monovalent hydrocarbon group having 1 to 6 carbon atoms or W; and l represents an integer of 0 to 20.) is a monovalent group represented by the formula: and an article to be subjected to UVC sterilization disinfection, characterized in that the static contact angle of water after undergoing a UVC resistance test under the following conditions is 100 degrees or more. <Conditions for UVC resistance test> Using a germicidal lamp with a maximum emission wavelength of 254 nm, germicidal rays (UVC) were applied to the surface treatment layer of the item at a total of 216,000 μW·h / cm 2 Irradiate. [6] The article according to [5], wherein T in the formula (6) is a divalent hydrocarbon group having 2 to 20 carbon atoms which may contain a diorganosilylene group, a divalent silalkylene group, or a diorganosilylene group; L is an alkylene group having 1 to 4 carbon atoms; and E is an alkyl group having 1 to 4 carbon atoms, a phenyl group, or W. [7] The article according to [6], wherein the S is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a phenyl group, or a group represented by the formula (6). [ 8 〕 The fluorooxyalkylene group-containing polymer having a hydrolyzable group is any one of the following: 5 ] The article described in [ka] (In the formula, A 2 , Rf is the same as above.) [ 9 〕 The surface treatment agent further comprises a compound represented by the following formula (7): [ka] [Wherein Rf is -C d F 2d -O-(CF2O) p (C2F4O) q (C3F6O) r (C4F8O) s (C5F 10 O) t (C6F 12 O) u -C d F 2d - (wherein d is independently an integer of 0 to 5 for each unit, p, q, r, s, t, and u are each independently an integer of 0 to 150, the sum of p, q, r, s, t, and u is at least 1, and each of these units may be linear or branched. Furthermore, each of the repeating units shown in parentheses with p, q, r, s, t, and u may be bonded randomly), and A 3 each independently represents a monovalent fluorine-containing hydrocarbon group which may contain an oxygen atom and which has a terminal CF3- or CF2H-; -OR 3 , or -PO(OR 3 )2(However, R 3 is a hydrogen atom or a monovalent hydrocarbon group. [1] or [ 5 ] The article described in [Effects of the Invention]

[0014] According to the present invention, it is possible to provide an article whose water repellency, i.e., stain resistance, is resistant to deterioration even when repeatedly subjected to sterilization and disinfection by UVC irradiation. DETAILED DESCRIPTION OF THE INVENTION

[0015] The present invention will be described in detail below. The article of the present invention has a water-repellent surface treatment layer formed using a surface treatment agent containing a fluorooxyalkylene group-containing polymer having a specific hydrolyzable group and / or a partial hydrolysis condensate thereof, as described below, and is characterized by having a static water contact angle of 100 degrees or more after a UVC resistance test under specific conditions. The static water contact angle after the UVC resistance test is 100 degrees or more, preferably 105 degrees or more, and more preferably 110 degrees or more. The static water contact angle is measured using a contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd.) with 2 μL of water. The static water contact angle is the static water contact angle of the surface treatment layer of the article.

[0016] The above UVC resistance test was carried out using a germicidal lamp with a maximum emission wavelength of 254 nm, and irradiating the surface treatment layer of the item with germicidal rays at a total of 216,000 μW·h / cm 2 This UVC resistance test is carried out by irradiating the surface treatment layer of the article with germicidal rays using a germicidal lamp with a maximum emission wavelength of 254 nm at a germicidal irradiance of 900 μW / cm 2 For example, a GL-10W lamp (sterilizing radiation output 2.7W) is used, and the distance between the lamp and the surface treatment layer of the article is set to 11 cm (sterilizing radiation irradiance 900 μW / cm 2 ) and irradiate with sterilizing rays for a total of 240 hours. Note that, at this time, the surface treatment layer may be wiped with a fluorine-based solvent such as HFE-7200 (manufactured by 3M, ethyl perfluorobutyl ether), dried, and the static contact angle of water on the surface treatment layer may be measured repeatedly every 48 hours of irradiation.

[0017] The material of the article (i.e., substrate) on which the surface treatment layer of the present invention is provided (treated with the surface treatment agent) is not particularly limited, and may be made of any appropriate material such as paper, cloth, metal and its oxides, glass, resin, or ceramic. Among these, glass is preferred because it can maintain excellent water repellency for a long period of time.

[0018] Examples of the glass include inorganic glass, organic glass, alkali-containing glass such as alkali aluminum silicate glass and soda lime glass, alkali-free glass such as borosilicate glass, sapphire glass, crystal glass, and quartz glass.

[0019] The metals include iron, copper, aluminum, stainless steel, nickel, chromium, molybdenum, etc., and may be simple metals or composites such as alloys of these metals. Examples of the oxides (metal oxides) include iron oxide (iron trioxide, iron tetroxide), copper oxide, aluminum oxide (alumina), nickel oxide, chromium oxide, and molybdenum oxide.

[0020] Examples of the resin include cellulose-based resins such as triacetyl cellulose (TAC), polyolefins such as polyethylene, polypropylene, ethylene-propylene copolymer, and ethylene-vinyl acetate copolymer (EVA), cyclic polyolefins, modified polyolefins, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, polyimide, polyamideimide, polycarbonate, poly-(4-methylpentene-1), ionomers, acrylic resins, polymethyl methacrylate, acrylic-styrene copolymers (AS resins), butadiene-styrene copolymers, ethylene-vinyl alcohol copolymers (EVOH), polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polycyclohexane terephthalate (PCT), polyethers, and polyolefins. Examples of the thermosetting or thermoplastic organic resin include terketone (PEK), polyether ether ketone (PEEK), polyetherimide, polyacetal (POM), polyphenylene oxide, modified polyphenylene oxide, polyarylate, aromatic polyester (liquid crystal polymer), polytetrafluoroethylene, polyvinylidene fluoride, other fluorine-based resins, various thermoplastic elastomers such as styrene-based, polyolefin-based, polyvinyl chloride-based, polyurethane-based, fluororubber-based, and chlorinated polyethylene-based elastomers, epoxy resin, phenolic resin, urea resin, melamine resin, unsaturated polyester, silicone resin, polyurethane, and the like, as well as copolymers, blends, and polymer alloys mainly made from these, and these can be used alone or in combination of two or more (for example, as a laminate of two or more layers).

[0021] Examples of the ceramic include sintered bodies of metal oxides such as silica, alumina, titania, germania, tin oxide, zinc oxide, manganese oxide, and zirconia, barium titanate, hydroxyapatite, silicon nitride, aluminum nitride, boron nitride, silicon carbide, and silicate minerals.

[0022] The shape of the article is not particularly limited. The surface region of the article on which the surface treatment layer is to be formed may be at least a part of the surface, and may be appropriately determined depending on the application and specific specifications of the article of the present invention, but it is preferable that the surface treatment layer be on the outermost surface.

[0023] Suitable articles on which a surface treatment layer is provided (treated with a surface treatment agent) include car navigation systems, mobile phones, smartphones, digital cameras, digital video cameras, PDAs, portable audio players, car audio, game machines, eyeglass lenses, camera lenses, lens filters, sunglasses, medical devices such as gastroscopes, copiers, PCs, liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, anti-reflection films, and other optical articles.

[0024] Furthermore, suitable articles to be provided with a surface treatment layer (treated with a surface treatment agent) include sanitary products such as bathtubs and washbasins, window glass or tempered glass for automobiles, trains, aircraft, etc., headlamp covers, exterior wall building materials, and kitchen building materials.

[0025] The surface treatment agent forming the surface treatment layer contains a fluorooxyalkylene group-containing polymer having a hydrolyzable group and / or a partial hydrolysis condensate thereof. By containing a fluorooxyalkylene group-containing polymer having a hydrolyzable group and / or a partial hydrolysis condensate thereof, the surface treatment agent can impart excellent water repellency and adhesion to articles made of various materials.

[0026] The surface treatment agent contains a fluorooxyalkylene group-containing polymer having a hydrolyzable group and / or a partial hydrolysis condensate thereof, and the fluorooxyalkylene group-containing polymer and / or the partial hydrolysis condensate thereof does not contain a carbonyl bond in the molecule.

[0027] As a result of investigations by the present inventors, it was found that when the surface treatment agent forming the surface treatment layer contains a fluorooxyalkylene group-containing polymer having a hydrolyzable group and / or a partial hydrolysis condensate thereof, the UVC resistance of the surface treatment layer is significantly affected by the type of chemical bond that the fluorooxyalkylene group-containing polymer and / or its partial hydrolysis condensate have in the molecule. Specifically, it was found that when the fluorooxyalkylene group-containing polymer having a hydrolyzable group and / or its partial hydrolysis condensate have a carbonyl bond in the molecule, the UVC resistance of the surface treatment layer is poor (i.e., the static contact angle of water after the above-mentioned UVC resistance test is less than 100°), and when the carbonyl bond is not contained, the UVC resistance of the surface treatment layer is excellent (i.e., the static contact angle of water after the above-mentioned UVC resistance test is 100° or more). The present invention was made based on this finding.

[0028] Furthermore, the fluorooxyalkylene group-containing polymer having a hydrolyzable group has at least one, preferably 1 to 3, terminals in the molecule thereof represented by the following formula (1): [ka] (In the formula, R is an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydrolyzable group, a is 2 or 3, and Y is a single bond or a divalent hydrocarbon group which may have one or more bonds selected from a fluorine atom, a silicon atom, and a siloxane bond.) It is preferable that the compound has at least two, preferably 2 to 3 (i.e., at least 2, preferably 2 to 9, more preferably 2 to 6 in the molecule) groups (hydrolyzable silyl group-containing groups) represented by the formula: b F 2b O) m It is preferable that the polyfluorooxyalkylene structure has the following formula: - (wherein b is independently an integer of 1 to 6 for each unit, and m is an integer of 1 to 250).

[0029] In the above formula (1), X's are hydrolyzable groups which may be different from one another. Examples of such X's include alkoxy groups having 1 to 10 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, and tert-butoxy; alkoxy-substituted alkoxy groups having 2 to 10 carbon atoms, such as methoxymethoxy, methoxyethoxy, ethoxymethoxy, and ethoxyethoxy; acyloxy groups having 2 to 10 carbon atoms, such as acetoxy and propionoxy; alkenyloxy groups having 2 to 10 carbon atoms, such as vinyloxy, allyloxy, propenoxy, and isopropenoxy; and halogen groups, such as chlorine, bromine, and iodo. Among these, methoxy, ethoxy, isopropenoxy, and chlorine are preferred.

[0030] In the above formula (1), R is an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a phenyl group, with a methyl group and an ethyl group being particularly preferred. In the above formula (1), a is 2 or 3, and 3 is preferred from the viewpoints of reactivity and adhesion to the substrate.

[0031] In the above formula (1), Y is a single bond or a divalent hydrocarbon group preferably having 1 to 20 carbon atoms, which may have one or more bonds selected from a fluorine atom, a silicon atom, and a siloxane bond. The divalent hydrocarbon group which may have one or more bonds selected from a fluorine atom, a silicon atom, and a siloxane bond is a group selected from the group consisting of alkylene groups having 1 to 10 carbon atoms, alkylene groups having 1 to 10 carbon atoms in which some of the hydrogen atoms are substituted with fluorine atoms, alkylene groups containing an arylene group having 6 to 8 carbon atoms (alkylene-arylene groups), divalent groups in which alkylene groups are bonded to each other via a silalkylene structure or a silarylene structure, and divalent groups in which alkylene groups are bonded to each other via a linear divalent organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic divalent organopolysiloxane residue having 3 to 10 silicon atoms.

[0032] Specific examples of Y other than a single bond include the following: In the following structure, it is preferable that the bond on the right side is bonded to Si. [ka]

[0033] Examples of the group in the above formula (1) include the following. [ka]

[0034] Also, the above-(C b F 2b O) m In the polyfluorooxyalkylene structure represented by -, b is independently an integer of 1 to 6, preferably an integer of 1 to 4 for each unit, and m is an integer of 1 to 250, preferably an integer of 1 to 140.

[0035] Above-C b F 2b Examples of the repeating unit represented by O- include units represented by the following formulas. -CF2O-, -CF2CF2O-, -CF2CF2CF2O-, -CF(CF3)CF2O-, -CF2CF2CF2CF2O-, -CF2CF2CF2CF2CF2CF2O-, -C(CF3)2O- Among these, the repeating units represented by the following formula are particularly preferred. -CF2O-, -CF2CF2O-

[0036] The polyfluorooxyalkylene structure may be composed of one type of the repeating units or a combination of two or more types.

[0037] For example, the fluorooxyalkylene group-containing polymer having a hydrolyzable group is preferably a fluorooxyalkylene group-containing polymer represented by the following formula (2) or (4). [ka] [Wherein Rf is -C d F 2d -O-(CF2O) p (C2F4O) q (C3F6O) r (C4F8O) s (C5F 10 O) t (C6F 12 O) u -C d F 2d - (wherein d is independently an integer of 0 to 5 for each unit, p, q, r, s, t, and u are each independently an integer of 0 to 150, the sum of p, q, r, s, t, and u is at least 1, and each of these units may be linear or branched. Furthermore, each of the repeating units shown in parentheses with p, q, r, s, t, and u may be bonded randomly), and A 1 is a monovalent fluorine-containing hydrocarbon group whose terminal is CF3- or CF2H- and which may contain an oxygen atom, or D, where D is a monovalent group represented by the following formula (3): [ka] [wherein Q is a divalent organic group or a single bond, Z is a trivalent to octavalent group, α is an integer of 2 to 7, and W is independently a monovalent hydrolyzable silyl group-containing group represented by the above formula (1)] [ka] [Wherein Rf is the same as above, A 2 is a monovalent fluorine-containing hydrocarbon group whose terminal is CF3- or CF2H- and which may contain an oxygen atom, or G, where G is a monovalent group represented by the following formula (5). [ka] [wherein W is the same as above, J is a single bond or an oxygen atom, B is a hydrogen atom or —OS, and S is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a group represented by the following formula (6): [ka] (In the formula, T is a single bond or a divalent group, L is independently a divalent hydrocarbon group having 1 to 4 carbon atoms, E is a monovalent hydrocarbon group having 1 to 6 carbon atoms or W, and l is an integer of 0 to 20.) is a monovalent group represented by the formula:

[0038] First, the fluorooxyalkylene group-containing polymer represented by the following formula (2) will be described. [ka]

[0039] In the above formula (2), Rf is -C d F 2d -O-(CF2O) p (C2F4O) q (C3F6O) r (C4F8O) s (C5F 10 O) t (C6F 12 O) u -C d F 2d- is a divalent polyfluorooxyalkylene structure (perfluorooxyalkylene structure)-containing group represented by the formula: -, and d is independently an integer of 0 to 5 for each unit, preferably an integer of 0 to 2, and more preferably 0 or 1. p, q, r, s, t, and u are each independently an integer of 0 to 150, preferably an integer of 0 to 100, more preferably an integer of 0 to 60, and even more preferably an integer of 0 to 10. From the viewpoint of water / oil repellency and scratch resistance, the sum of p, q, r, s, t, and u is at least 1, preferably 2 to 250, more preferably 3 to 200, even more preferably 7 to 150, and particularly preferably 10 to 120. Each of these units may be linear or branched. The repeating units shown in parentheses with p, q, r, s, t, and u may be randomly bonded.

[0040] The divalent polyfluorooxyalkylene structure-containing group of Rf can be specifically represented by the following structure. [ka] (In the formula, p', q', r', s', t', and u' each independently represent an integer of 1 to 150, the upper limit of the sum of p', q', r', s', t', and u' is 250, and each of these units may be linear or branched. Furthermore, each of the repeating units shown in parentheses followed by p', q', r', s', t', and u' may be bonded randomly. d' is independently an integer of 0 to 5 for each unit, and each of these units may be linear or branched.)

[0041] The above formula (2); A 1 -Rf-D, A 1 is a monovalent fluorine-containing hydrocarbon group whose terminal is CF3- or CF2H- and which may contain an oxygen atom, or D (i.e., -QZ(W) α The fluorooxyalkylene group-containing polymer represented by formula (2) is 1is a monovalent fluorine-containing hydrocarbon group which has a terminal CF3- or CF2H- and may contain an oxygen atom, the polymer is a fluorooxyalkylene group-containing polymer (single-terminated polymer) having at least two hydrolyzable silyl groups at one end of the molecular chain, and A 1 D (expressed as -QZ(W) in Equation (3)) α ), the resulting polymer is a fluorooxyalkylene group-containing polymer (double-ended polymer) having at least two hydrolyzable silyl groups at each of the molecular chain ends.

[0042] The monovalent fluorine-containing hydrocarbon group which has a terminal CF3- or CF2H- and which may contain an oxygen atom is preferably a fluoroalkyl group having 1 to 6 carbon atoms.

[0043] Such an A 1 Examples of the monovalent fluorine-containing hydrocarbon group which has a terminal group of CF3- or CF2H- and which may contain an oxygen atom include the following groups. [ka]

[0044] The above formula (2); A 1 In —Rf-D, D is a monovalent group represented by the following formula (3). [ka]

[0045] In the above formula (3), Q is a divalent organic group or a single bond, and Q other than a single bond is preferably an unsubstituted or substituted divalent hydrocarbon group having 2 to 15 carbon atoms which may contain one or more bonds selected from the group consisting of an ether bond, a sulfide bond, a siloxane bond, a triazine bond, a silphenylene bond, and a silalkylene bond (for example, a silethylene bond), and more preferably an unsubstituted or fluorine-substituted divalent hydrocarbon group having 2 to 12 carbon atoms which may contain such a bond.

[0046] Examples of Q other than a single bond include the following groups: In the following structure, it is preferred that the left bond is bonded to Rf and the right bond is bonded to Z. [ka] (In the formula, i is an integer of 2 to 4.)

[0047] The above formula (3);-QZ(W) α In the formula, Z is a trivalent to octavalent group, and Z is preferably a trivalent to octavalent, preferably tri- or tetravalent organopolysiloxane residue selected from a trivalent to octavalent organopolysiloxane residue having a silicon atom, a nitrogen atom, and a siloxane bond, preferably a linear organopolysiloxane residue having 2 to 13 silicon atoms, more preferably 2 to 5 silicon atoms, or a branched or cyclic organopolysiloxane residue having 3 to 13 silicon atoms, more preferably 3 to 5 silicon atoms. The trivalent to octavalent organopolysiloxane residue may also contain a silalkylene structure such as a silethylene structure in which two silicon atoms are bonded via an alkylene group such as an ethylene group, i.e., Si-(CH2) n It may contain —Si (in the above formula, n is an integer of 2 to 6, preferably an integer of 2 to 4).

[0048] Here, examples of the trivalent to octavalent organopolysiloxane residue having a siloxane bond include those shown below. [ka] (In the formula, R 1 is an alkyl group having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, and more preferably an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 10 carbon atoms, such as a phenyl group; R 1 may be the same or different. g is an integer of 3 to 8, preferably 3 or 4, h is an integer of 3 to 8, preferably 3 or 4, j is an integer of 0 to 8, preferably 0 or 1, h+j is an integer of 3 to 13, preferably an integer of 3 to 5, and k is 2 or 3. [ka] [In the formula, R 4 are independently R 1 Or the following formula (a) [ka] (In the formula, R 1 is the same as above, j1 is an integer of 1 to 6, preferably 1, and the bond on the left side is bonded to Si. is a group represented by R 5 are independently a single bond or the following formula (b): [ka] (In the formula, R 4 is the same as above, and R 2 is an alkylene group having 1 to 4 carbon atoms, such as a methylene group, an ethylene group, a propylene group (trimethylene group, methylethylene group), or an arylene group having 6 to 10 carbon atoms, such as a phenylene group. j2 is an integer of 0 to 6, preferably an integer of 0 to 3, and j3 is an integer of 0 to 6, preferably an integer of 0 to 2, and the repeating units shown in parentheses may be bonded randomly. The bond on the left side bonds to Si. is a group represented by R 4 At least one of the formulas is (a).

[0049] Examples of Z include silicon atoms, nitrogen atoms, and the following (linear, cyclic, or branched chain organopolysiloxane residues or organopolysiloxane silalkylene residues): [ka] [ka] [ka]

[0050] The above formula (3);-QZ(W) αIn the formula (1), W is independently a monovalent hydrolyzable silyl group-containing group represented by the formula (1).

[0051] The above formula (3);-QZ(W) α In the formula, α, which represents the number of Ws, is an integer of 2 to 7, and preferably 2 or 3.

[0052] The group in the above formula (3): -QZ(W) α (i.e., D in formula (2)) includes the following. [ka]

[0053] Examples of the fluorooxyalkylene group-containing polymer represented by the above formula (2) include the following: 1 , Rf is the same as above. [ka]

[0054] Next, the fluorooxyalkylene group-containing polymer represented by the following formula (4) will be described. [ka] In the above formula (4), Rf is the same as above, and examples thereof include those similar to those exemplified as Rf in the above formula (2).

[0055] The above formula (4); A 2 -Rf-G, A 2 is a monovalent fluorine-containing hydrocarbon group having a terminal CF3- or CF2H- and optionally containing an oxygen atom, or G (i.e., a monovalent group represented by formula (5); -C(-B)(-JW)2, which will be described later). The fluorooxyalkylene group-containing polymer represented by formula (4) can be prepared by 2is a monovalent fluorine-containing hydrocarbon group which has a terminal CF3- or CF2H- and may contain an oxygen atom, the polymer is a fluorooxyalkylene group-containing polymer (single-terminated polymer) having at least two hydrolyzable silyl groups at one end of the molecular chain, and A 2 When G is -C(-B)(-JW)2 represented by formula (5), the resulting polymer is a fluorooxyalkylene group-containing polymer (double-ended polymer) having at least two hydrolyzable silyl groups at each of the molecular chain ends.

[0056] The monovalent fluorine-containing hydrocarbon group which has a terminal CF3- or CF2H- and which may contain an oxygen atom is preferably a fluoroalkyl group having 1 to 6 carbon atoms.

[0057] Such an A 2 Examples of the monovalent fluorine-containing hydrocarbon group which has a terminal group of CF3- or CF2H- and which may contain an oxygen atom include the following groups. [ka]

[0058] The above formula (4); A 2 In —Rf-G, G is a monovalent group represented by the following formula (5). [ka] In the above formula (5), W is the same as above, and examples thereof include those similar to those exemplified for W in the above formula (3). In addition, J is a single bond or an oxygen atom.

[0059] In the above formula (5); -C(-B)(-JW)2, B is a hydrogen atom or -OS, and S is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a monovalent group represented by the following formula (6): [ka]

[0060] Here, examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms for S include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and octyl groups; alkenyl groups such as vinyl and allyl groups; aryl groups such as phenyl and tolyl groups; and aralkyl groups such as benzyl and phenylethyl groups, with alkyl groups having 1 to 3 carbon atoms and phenyl groups being preferred.

[0061] The above formula (6); -T-(LO) l In -E, T represents a single bond or a divalent group, and is preferably a single bond, or a divalent hydrocarbon group having 2 to 20 carbon atoms which may contain one or more bonds selected from the group consisting of a siloxane bond, a silalkylene bond (e.g., a silethylene bond or a silpropylene bond), a silarylene bond (e.g., a silphenylene bond), and a diorganosilylene group (e.g., a dialkylsilylene group such as a dimethylsilylene group, or a dialkoxysilylene group such as a dimethoxysilylene group), a divalent siloxane bond, a silalkylene group, or a diorganosilylene group.

[0062] Examples of the silalkylene bond, silalkylene group, and silarylene bond are shown below. [ka] (In the formula, R 1 is an alkyl group having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, and more preferably an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 10 carbon atoms, such as a phenyl group; R 1 may be the same or different. 2 is an alkylene group having 1 to 4 carbon atoms, such as a methylene group, an ethylene group, or a propylene group (trimethylene group, methylethylene group), or an arylene group having 6 to 10 carbon atoms, such as a phenylene group.

[0063] Specific examples of T other than a single bond include those shown below. In the following structures, it is preferable that the bond on the right side is bonded to L or E. [ka]

[0064] The above formula (6); -T-(LO) l In -E, L is independently a divalent hydrocarbon group having 1 to 4 carbon atoms, such as an alkylene group, including a methylene group, an ethylene group, a propylene group (trimethylene group, methylethylene group), a butylene group (tetramethylene group), etc., and the carbon numbers may be single or mixed.

[0065] The above formula (6); -T-(LO) l In -E, l is an integer of 0 to 20, preferably an integer of 0 to 10, more preferably an integer of 0 to 6. When (LO) is present, l is preferably 1 or more, particularly preferably 2 or more.

[0066] The above formula (6); -T-(LO) l In -E, E is an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a monovalent hydrocarbon group having 1 to 6 carbon atoms, such as a phenyl group, or W, where W is the same as defined above and can be exemplified by the same groups as those exemplified for W in formula (3) above.

[0067] The above formula (6); -T-(LO) l Examples of the monovalent group represented by -E (that is, S) include those shown below. [ka]

[0068] Examples of the monovalent group represented by the above formula (5): -C(-B)(-JW)2 (that is, G in formula (4)) include those shown below. [ka] [ka]

[0069] Examples of the fluorooxyalkylene group-containing polymer represented by the above formula (4) include the following: 2 , Rf is the same as above. [ka] [ka]

[0070] Furthermore, the surface treatment agent may be a mixture (i.e., a fluorooxyalkylene group-containing polymer composition) that further contains a fluorooxyalkylene group-containing polymer that does not contain a hydrolyzable silyl group, as represented by the following formula (7), in addition to the above-mentioned fluorooxyalkylene group-containing polymer and / or partial hydrolysis condensate thereof having a hydrolyzable group, preferably a fluorooxyalkylene group-containing polymer and / or partial hydrolysis condensate of the polymer that contains at least two hydrolyzable silyl groups: [ka] [In the formula, Rf is the same as above, and examples thereof include those exemplified as Rf in the formula (2) above. A 3 each independently represents a monovalent fluorine-containing hydrocarbon group which may contain an oxygen atom and which has a terminal CF3- or CF2H-; -OR 3 , or -PO(OR 3 )2(However, R 3 is a hydrogen atom or a monovalent hydrocarbon group (an alkyl group having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group, and more preferably an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 10 carbon atoms, such as a phenyl group).

[0071] where A 3 Examples of the monovalent fluorine-containing hydrocarbon group which may contain an oxygen atom and whose terminal is CF3- or CF2H- include the following groups. [ka] Also, A3 -OR 3 , -PO(OR 3 Examples of the )2 include -OH, -OCH3, and -PO(OH)2.

[0072] Examples of the fluorooxyalkylene group-containing polymer represented by the above formula (7) include those shown below. [ka] (In the formula, p", q", r", s", t", and u" each independently represent an integer of 0 to 150, the sum of p", q", r", s", t", and u" is 12 to 250, and each of these units may be linear or branched. Furthermore, each repeating unit shown in parentheses with p", q", r", s", t", and u" may be bonded randomly.)

[0073] The surface treatment agent typically contains at least one fluorooxyalkylene group-containing polymer having at least two hydrolyzable silyl groups at one molecular chain terminal, as represented by the above formula (2) or (4), and / or a partial hydrolysis condensate of such a polymer (single-terminated polymer), or at least one fluorooxyalkylene group-containing polymer having at least two hydrolyzable silyl groups at each of the molecular chain terminals, as represented by the above formula (2) or (4), and / or a partial hydrolysis condensate of such a polymer (double-terminated polymer), or contains a mixture of at least one single-terminated polymer and at least one double-terminated polymer (fluorooxyalkylene group-containing polymer mixture) among these, or preferably contains a mixture of any of these further containing a fluorooxyalkylene group-containing polymer represented by the above formula (7) (fluorooxyalkylene group-containing polymer composition). The mixing ratio (molar ratio) of the one-terminated polymer to the both-terminated polymer in the fluorooxyalkylene group-containing polymer mixture is preferably 5:95 to 100:0, more preferably 25:75 to 100:0, still more preferably 50:50 to 100:0, and particularly preferably 60:40 to 100:0.

[0074] In the fluorooxyalkylene group-containing polymer composition having a hydrolyzable group contained in the surface treatment agent, the mixing ratio of the one-terminal polymer and / or both-terminal polymer and the fluorooxyalkylene group-containing polymer represented by formula (7) is not particularly limited, but usually, the ratio of the fluorooxyalkylene group-containing polymer represented by formula (7) to the entire fluorooxyalkylene group-containing polymer composition consisting of the one-terminal polymer and / or both-terminal polymer and the fluorooxyalkylene group-containing polymer represented by formula (7) is desirably 0.01 to 30 mol %, particularly 0.1 to 10 mol %.

[0075] The number average molecular weight of the one-terminal polymer, both-terminal polymer, fluorooxyalkylene group-containing polymer mixture, or fluorooxyalkylene group-containing polymer composition contained in the surface treatment agent is preferably in the range of 1,000 to 20,000, more preferably 2,000 to 10,000, and particularly preferably 3,000 to 8,000, from the viewpoint of forming a film having excellent water and oil repellency and scratch resistance.

[0076] The surface treatment layer is formed by treating the surface of the target article with a predetermined surface treatment agent. The surface treatment agent contains the above-mentioned fluorooxyalkylene group-containing polymer having a hydrolyzable group and / or its partial hydrolysis condensate. If necessary, it may contain a hydrolysis condensation catalyst, such as an organotin compound (e.g., dibutyltin dimethoxide, dibutyltin dilaurate), an organotitanium compound (e.g., tetra-n-butyl titanate), an organic acid (e.g., acetic acid, methanesulfonic acid, fluorine-modified carboxylic acid), or an inorganic acid (e.g., hydrochloric acid, sulfuric acid). Among these, acetic acid, tetra-n-butyl titanate, dibutyltin dilaurate, fluorine-modified carboxylic acid, etc. are particularly desirable. The amount of the catalyst added is typically 0.01 to 5 parts by mass, particularly 0.1 to 1 part by mass, per 100 parts by mass of the fluorooxyalkylene group-containing polymer having a hydrolyzable group and / or its partial hydrolysis condensate, preferably the fluorooxyalkylene group-containing polymer containing at least two hydrolyzable silyl groups and / or the partial hydrolysis condensate of the polymer.

[0077] The surface treatment agent for forming the surface treatment layer may contain a solvent, such as a fluorine-modified aliphatic hydrocarbon solvent (e.g., perfluoroheptane or perfluorooctane), a fluorine-modified olefin solvent (e.g., methoxyperfluoroheptene), a fluorine-modified aromatic hydrocarbon solvent (e.g., m-xylene hexafluoride, benzotrifluoride, or 1,3-trifluoromethylbenzene), a fluorine-modified ether solvent (e.g., methyl perfluorobutyl ether, ethyl perfluorobutyl ether, or perfluoro(2-butyltetrahydrofuran)), a fluorine-modified alkylamine solvent (e.g., perfluorotributylamine or perfluorotripentylamine), a hydrocarbon solvent (e.g., petroleum benzine, mineral spirits, toluene, or xylene), or a ketone solvent (e.g., acetone, methyl ethyl ketone, or methyl isobutyl ketone). Among these, fluorine-modified solvents (referred to as fluorine-based solvents) are desirable in terms of solubility, wettability, etc., and 1,3-trifluoromethylbenzene, m-xylene hexafluoride, perfluoro(2-butyltetrahydrofuran), perfluorotributylamine, and ethyl perfluorobutyl ether are particularly preferred.

[0078] Two or more of the above solvents may be mixed, and it is preferable to uniformly dissolve the fluorooxyalkylene group-containing polymer having a hydrolyzable group and / or its partial hydrolysis condensate. The optimum concentration of the fluorooxyalkylene group-containing polymer to be dissolved in the solvent is not limited and may be appropriately selected depending on the method of use of the surface treatment agent. The fluorooxyalkylene group-containing polymer having a hydrolyzable group and / or its partial hydrolysis condensate is usually dissolved in the solvent to a concentration of 0.01 to 30 mass%, preferably 0.02 to 25 mass%, and more preferably 0.05 to 20 mass%.

[0079] The surface treatment layer is applied to the substrate using the surface treatment agent 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. For example, in the case of direct coating (brushing, dipping, spraying, etc.), the curing temperature is preferably 25 to 150°C, particularly 25 to 120°C, for 0.5 to 48 hours, particularly 12 to 24 hours. In the case of application by vapor deposition, the curing temperature is preferably 25 to 150°C, particularly 25 to 120°C, for 0.5 to 48 hours, particularly 12 to 24 hours. Curing may also be performed under humid conditions. The thickness of the surface treatment layer is appropriately selected depending on the type of substrate, but is usually 5 to 30 nm, particularly 8 to 20 nm. The thickness of the surface treatment layer can be measured by, for example, spectral reflectance measurement, X-ray reflectance measurement, spectroscopic ellipsometry measurement, X-ray fluorescence measurement, etc.

[0080] [Method for improving UVC resistance of water-repellent articles] The method of the present invention for improving the UVC resistance of a water-repellent article is characterized in that the article has, on at least a part of its surface, a surface treatment layer formed from a surface treatment agent containing a fluorooxyalkylene group-containing polymer having a hydrolyzable group and / or a partial hydrolyzed condensate thereof, wherein the fluorooxyalkylene group-containing polymer and / or the partial hydrolyzed condensate thereof does not contain a carbonyl bond in the molecule. Here, the article in the method of the present invention for improving the UVC resistance of a water-repellent article refers to the article of the present invention described above, and the UVC resistance of the article is improved by applying a surface treatment layer formed from the specific surface treatment agent described above to at least a portion of the surface of the article. [Example]

[0081] The present invention will be described in more detail below with reference to Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited to the following Examples. In the following examples, the film thickness is a value measured by spectroscopic ellipsometry using a spectroscopic ellipsometer.

[0082] [Synthesis Example 1] A mixture consisting of 80 mol % of the compound of formula (1a) and 20 mol % of the compound of formula (1b) shown below was used in the following synthesis. [ka]

[0083] 50 g of a mixture consisting of 80 mol % of the compound of formula (1a) and 20 mol % of the compound of formula (1b) was dissolved in a mixed solvent of 40 g of Asahiklin AC6000 (manufactured by AGC) and 20 g of methanol. After stirring at 60°C for 4 hours, the lower layer was removed and the solvent was distilled off under reduced pressure to obtain 47 g of a liquid product. The resulting product was 19 F-NMR confirmed that the product was a mixture consisting of 80 mol % of the compound of the following formula (1c) and 20 mol % of the compound of formula (1d). [ka]

[0084] A reaction vessel was charged with 48 g of a mixture consisting of 80 mol % of the compound of formula (1c) and 20 mol % of the compound of formula (1d), 48 g of allyl magnesium chloride, 40 g of Asahiklin AC6000 (manufactured by AGC), and 40 g of perfluorohexane (PF5060, manufactured by 3M), and the mixture was stirred at 50°C for 2 hours. After that, an appropriate amount of hydrochloric acid was added and the mixture was stirred, and then thoroughly washed with water. Furthermore, the lower layer was removed, and the solvent was distilled off under reduced pressure, yielding 40 g of a liquid product. The resulting product was 19 F-NMR and 1 It was confirmed by 1 H-NMR that the product was a mixture consisting of 80 mol % of the compound of the following formula (1e) and 20 mol % of the compound of formula (1f). [ka]

[0085] A mixture of 40 g of 80 mol % of the compound of formula (1e) and 20 mol % of the compound of formula (1f), 15 g of Asahiklin AC6000 (manufactured by AGC), 2.4 g of trimethoxysilane, 0.015 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (4.5 × 10 as Pt alone) -8 The mixture was stirred at 80°C for 3 hours. The solvent and unreacted materials were then distilled off under reduced pressure to obtain 23 g of a liquid product. 1 1 H-NMR confirmed that the product was a mixture A consisting of 80 mol % of the compound of formula (1g) shown below and 20 mol % of the compound of formula (1h). [ka]

[0086] [Synthesis Example 2] The compound of formula (2a) shown below was used in the following synthesis. [ka]

[0087] 50 g of the compound of formula (2a) above was dissolved in a mixed solvent of 5 g of 1,3-trifluoromethylbenzene and 20 g of methanol. After stirring at 60°C for 4 hours, the lower layer was removed and the solvent was distilled off under reduced pressure to obtain 40 g of a liquid product. The resulting product was 19 F-NMR confirmed that the compound was the compound of the following formula (2b). [ka]

[0088] 40 g of the compound of formula (2b), 36 g of allyl magnesium chloride, and 30 g of Asahiklin AC6000 (AGC) were placed in a reaction vessel and stirred at 60°C for 2 hours. After that, an appropriate amount of hydrochloric acid was added and stirred, and then thoroughly washed with water. Furthermore, the lower layer was removed and the solvent was distilled off under reduced pressure, yielding 30 g of a liquid product. The resulting product was 19 F-NMR and 1 It was confirmed by 1 H-NMR that the compound was the compound of the following formula (2c). [ka]

[0089] A reaction vessel was charged with 30 g of the compound of formula (2c), 15 g of 1,3-trifluoromethylbenzene, 2.4 g of trimethoxysilane, and 0.015 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (4.5 × 10 as Pt alone). -8 The mixture was stirred at 80°C for 3 hours. The solvent and unreacted materials were then distilled off under reduced pressure to obtain 25 g of a liquid product. 1 It was confirmed by 1 H-NMR that the compound was Compound B of formula (2d) shown below. [ka]

[0090] [Synthesis Example 3] 30 g of the compound of formula (2c) above, 30 g of 1,3-trifluoromethylbenzene, 7.8 g of diethylene glycol 2-bromoethyl methyl ether, and 0.07 g of tetrabutylammonium iodide were mixed. Subsequently, 6.2 g of potassium hydroxide was added, and the mixture was aged at 60°C for 11 hours. After that, an appropriate amount of hydrochloric acid was added, and the mixture was stirred, and then thoroughly washed with water. Furthermore, the lower layer was removed, and the solvent was distilled off under reduced pressure, yielding 28 g of a liquid product. The resulting product was 19 F-NMR and 1 It was confirmed by 1 H-NMR that the compound was the compound of the following formula (3a). [ka]

[0091] 25 g of the compound of the above formula (3a), 15 g of 1,3-trifluoromethylbenzene, 2.4 g of trimethoxysilane, 0.015 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (2.5 × 10 as Pt alone) -8 The mixture was stirred at 80°C for 3 hours. The solvent and unreacted materials were then distilled off under reduced pressure to obtain 23 g of a liquid product. 1 It was confirmed by 1 H-NMR that the compound was Compound C of formula (3b) shown below. [ka]

[0092] [Synthesis Example 4] 30 g of the compound of formula (2c) above, 30 g of 1,3-trifluoromethylbenzene, 2.7 g of allyl bromide, and 0.06 g of tetrabutylammonium iodide were mixed. Subsequently, 2.4 g of potassium hydroxide was added, and the mixture was stirred at 60°C for 11 hours. After that, an appropriate amount of hydrochloric acid was added, and the mixture was stirred, and then thoroughly washed with water. Furthermore, the lower layer was removed, and the solvent was distilled off, yielding 28 g of a liquid product. The resulting product was 19 F-NMR and 1 It was confirmed by 1 H-NMR that the compound was the compound of the following formula (4a). [ka]

[0093] 25 g of the compound of the above formula (4a), 15 g of 1,3-trifluoromethylbenzene, 3.6 g of trimethoxysilane, 0.023 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (4.5 × 10 as Pt alone) -8 The mixture was stirred at 80°C for 3 hours. The solvent and unreacted materials were then distilled off under reduced pressure to obtain 23 g of a liquid product. 1 It was confirmed by 1 H-NMR that the compound was Compound D of formula (4b) shown below. [ka]

[0094] [Synthesis Example 5] The compound of formula (5a) shown below was used in the following synthesis. [ka]

[0095] Compound E (42 g of a liquid product) of formula (5b) shown below was synthesized in the same manner as in Synthesis Example 2, except that the compound of formula (5a) (50 g) was used as a starting material instead of the compound of formula (2b) used in Synthesis Example 2. [ka]

[0096] [Synthesis Example 6] The compound of formula (6a) shown below was used in the following synthesis. [ka]

[0097] Compound F (44 g of a liquid product) of formula (6b) shown below was synthesized in the same manner as in Synthesis Example 2, except that the compound of formula (6a) (50 g) was used as a starting material instead of the compound of formula (2b) used in Synthesis Example 2. [ka]

[0098] [Synthesis Example 7] The compound of formula (7a) shown below was used in the following synthesis. [ka]

[0099] Compound G of formula (7b) shown below (76 g of a liquid product) was synthesized in the same manner as in Synthesis Example 2, except that the compound of formula (7a) (100 g) was used as a starting material instead of the compound of formula (2b) used in Synthesis Example 2. [ka]

[0100] [Synthesis Example 8] 40 g of the compound of formula (7a), 5.9 g of butenyl magnesium bromide, and 30 g of Asahiklin AC6000 (AGC) were placed in a reaction vessel and stirred at 60°C for 2 hours. After that, an appropriate amount of hydrochloric acid was added and stirred, and then thoroughly washed with water. Furthermore, the lower layer was removed and the solvent was distilled off under reduced pressure, yielding 30 g of a liquid product. The resulting product was 19 F-NMR and 1 It was confirmed by 1 H-NMR that the compound was the compound of the following formula (8a). [ka]

[0101] 30 g of the compound of formula (8a) above, 30 g of 1,3-trifluoromethylbenzene, 3.3 g of allyl bromide, and 0.06 g of tetrabutylammonium iodide were mixed. Subsequently, 3.9 g of potassium hydroxide was added, and the mixture was stirred at 60°C for 18 hours. After that, an appropriate amount of hydrochloric acid was added, and the mixture was stirred, and then thoroughly washed with water. Furthermore, the lower layer was removed, and the solvent was distilled off, yielding 28 g of a liquid product. The resulting product was 19 F-NMR and 1 It was confirmed by 1 H-NMR that the compound was the compound of the following formula (8b). [ka]

[0102] 25 g of the compound of formula (8b) above, 30 g of 1,3-trifluoromethylbenzene, 3.4 g of trimethoxysilane, 0.015 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (4.5 × 10 as Pt alone)-8 The mixture was stirred at 80°C for 3 hours. The solvent and unreacted materials were then distilled off under reduced pressure to obtain 23 g of a liquid product. 1 It was confirmed by H-NMR that the compound was Compound H of formula (8c) shown below. [ka]

[0103] [Examples 1 to 8] The mixture A and compounds B to H obtained in Synthesis Examples 1 to 8 were dissolved in HFE-7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 20 mass % to prepare a surface treatment agent.

[0104] [Comparative Example 1] The following formula [ka] A surface treatment agent was prepared by dissolving a compound CX represented by the following formula in HFE-7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 20 mass %.

[0105] Comparative Example 2 The following formula [ka] A surface treatment agent was prepared by dissolving a compound CY represented by the following formula in HFE-7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 20 mass %.

[0106] Comparative Example 3 The following formula [ka] A surface treatment agent was prepared by dissolving a compound CZ represented by the following formula in HFE-7200 (manufactured by 3M, ethyl perfluorobutyl ether) to a concentration of 20 mass %.

[0107] [Formation of hardened coating] Each of the surface treatment agents of Examples 1 to 8 and Comparative Examples 1 to 3 was vacuum-deposited onto glass (Corning Gorilla) with a 10 nm thick SiO2 film formed on the outermost surface (treatment conditions: pressure: 2.0 × 10 -2 The coating was cured for 12 hours in an atmosphere of 25°C and 50% humidity (Pa, heating temperature: 700°C) to form a cured film with a thickness of 10 nm, and a glass sample was prepared.

[0108] [UVC resistance test] The glass samples produced using the surface treatment agents of Examples 1 to 8 and Comparative Examples 1 to 3 were subjected to a UVC resistance test under the following conditions. <UVC resistance test> The surface treatment layer of the glass sample was irradiated with germicidal rays (UVC) using a GL-10W lamp (germicidal radiation output 2.7 W, maximum emission wavelength 254 nm) at a distance of 11 cm from the lamp. The germicidal radiation irradiance in this case was 900 μW / cm. 2 This becomes: Although UVC irradiation was performed continuously, when measuring the static contact angle of water, the glass sample was temporarily removed and the surface treatment layer was wiped five times with a tissue thoroughly soaked in HFE-7200 (3M, ethyl perfluorobutyl ether), then allowed to dry, after which the static contact angle of water was measured.

[0109] [Water repellency evaluation] The static water contact angle (water repellency) of the surface treatment layer of the glass sample to be measured was measured using a contact angle meter Drop Master (manufactured by Kyowa Interface Science Co., Ltd.) (droplet: 2 μL, temperature: 25°C, humidity: 40%). The static water contact angle (water repellency) of each glass sample was measured by the following procedure. First, as an initial evaluation, the static contact angle of water on the glass sample after the surface treatment layer was formed was measured before UVC irradiation (UVC irradiation time 0 hours). Thereafter, the static contact angle of water on the surface treatment layer after UVC irradiation was measured every 48 hours. The evaluation was continued every 48 hours from the start of UVC irradiation until the static contact angle of water fell below 80 degrees or until the cumulative irradiation time reached 240 hours. The results are shown in Table 1.

[0110] [Table 1]

[0111] As a result of the above, both the Examples and Comparative Examples showed good water repellency in the initial stage (0 hours of UVC irradiation time). In Examples 1 to 8, the static contact angle of water hardly decreased even after 240 hours of cumulative irradiation time in the UVC resistance test, demonstrating high UVC resistance. On the other hand, in Comparative Examples 1 to 3, the static contact angle of water fell below 80 degrees before the cumulative irradiation time reached 240 hours, demonstrating low UVC resistance.

Claims

1. An article having a surface-treated layer formed from a surface treatment agent containing a fluorooxyalkylene group-containing polymer and / or a partial hydrolysis condensate thereof, the polymer not containing a carbonyl bond in the molecule and having a hydrolyzable group, The fluorooxyalkylene group-containing polymer having a hydrolyzable group is represented by the following formula (2): 【Chemistry 1】 [wherein Rf is —C d F 2d -O-(CF 2 O) p (C 2 F 4 O) q (C 3 F 6 O) r (C 4 F 8 O) s (C 5 F 10 O) t (C 6 F 12 O) u -C d F 2d -(wherein d is independently an integer of 0 to 5 for each unit, p, q, r, s, t, and u are each independently an integer of 0 to 150, the sum of p, q, r, s, t, and u is at least 1, and each of these units may be linear or branched. Furthermore, each of the repeating units shown in parentheses with p, q, r, s, t, and u may be bonded randomly), and A 1 ends in CF 3 - or CF 2 a monovalent fluorine-containing hydrocarbon group which is H- and may contain an oxygen atom, or D, where D is a monovalent group represented by the following formula (3): 【Chemistry 2】 [wherein Q is a single bond or an unsubstituted or substituted divalent hydrocarbon group having 2 to 15 carbon atoms which may contain one or more bonds selected from the group consisting of an ether bond, a siloxane bond, a silphenylene bond, and a silalkylene bond; Z is a trivalent to octavalent group selected from a silicon atom, a nitrogen atom, and a trivalent to octavalent organopolysiloxane residue having a siloxane bond; α is an integer of 2 to 7; and W is independently a group represented by the following formula (1): 【Transformation 3】 (In the formula, R is an alkyl group or phenyl group having 1 to 4 carbon atoms, X is independently a hydrolyzable group, a is 2 or 3, and Y is a single bond or a group selected from the group consisting of an alkylene group having 1 to 10 carbon atoms, an alkylene group having 1 to 10 carbon atoms in which some of the hydrogen atoms are substituted with fluorine atoms, an alkylene group containing an arylene group having 6 to 8 carbon atoms, a divalent group in which alkylene groups are bonded to each other via a silalkylene structure or a silarylene structure, and a divalent group in which alkylene groups are bonded to each other via a linear divalent organopolysiloxane residue having 2 to 10 silicon atoms.) is a monovalent hydrolyzable silyl group-containing group represented by the following formula: and an article to be subjected to UVC sterilization and disinfection, characterized in that the static contact angle of water after a UVC resistance test under the following conditions is 100 degrees or more. <Conditions for UVC resistance test> Using a germicidal lamp with a maximum emission wavelength of 254 nm, germicidal rays (UVC) were applied to the surface treatment layer of the article at a total of 216,000 μW h / cm 2 Irradiate.

2. The article according to claim 1, wherein Q in formula (3) is an alkylene group having 2 to 4 carbon atoms which may contain an ether bond, or a single bond.

3. The article described in claim 2, wherein Z in formula (3) is a trivalent or tetravalent group selected from a silicon atom, a nitrogen atom, and a trivalent or tetravalent organopolysiloxane residue having a siloxane bond, and α is 2 or 3.

4. 2. The article according to claim 1, wherein the fluorooxyalkylene group-containing polymer having a hydrolyzable group is any one of the following: 【Chemistry 4】 (In the formula, A 1 , Rf is the same as above.)

5. An article having a surface-treated layer formed from a surface treatment agent containing a fluorooxyalkylene group-containing polymer having a hydrolyzable group and / or a partial hydrolysis condensate thereof, which does not contain a carbonyl bond in the molecule, The fluorooxyalkylene group-containing polymer having a hydrolyzable group is represented by the following formula (4): 【Transformation 5】 [wherein Rf is the same as above, A 2 ends in CF 3 - or CF 2 a monovalent fluorine-containing hydrocarbon group which is H- and may contain an oxygen atom, or G, where G is a monovalent group represented by the following formula (5): 【Transformation 6】 [wherein W independently represents the following formula (1)] 【Transformation 7】 (In the formula, R is an alkyl group or phenyl group having 1 to 4 carbon atoms, X is independently a hydrolyzable group, a is 2 or 3, and Y is a single bond or a group selected from the group consisting of an alkylene group having 1 to 10 carbon atoms, an alkylene group having 1 to 10 carbon atoms in which some of the hydrogen atoms are substituted with fluorine atoms, an alkylene group containing an arylene group having 6 to 8 carbon atoms, a divalent group in which alkylene groups are bonded to each other via a silalkylene structure or a silarylene structure, and a divalent group in which alkylene groups are bonded to each other via a linear divalent organopolysiloxane residue having 2 to 10 silicon atoms.) wherein J is a single bond or an oxygen atom, B is —OS, and S is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a group represented by the following formula (6): 【Transformation 8】 (In the formula, T represents a divalent hydrocarbon group having 2 to 20 carbon atoms, a divalent silalkylene group, or a diorganosilylene group, which may contain one or more bonds selected from the group consisting of a siloxane bond, a silalkylene bond, a silarylene bond, and a diorganosilylene group; L represents independently a divalent hydrocarbon group having 1 to 4 carbon atoms; E represents a monovalent hydrocarbon group having 1 to 6 carbon atoms or W; and l represents an integer from 0 to 20.) is a monovalent group represented by the following formula: and an article to be subjected to UVC sterilization and disinfection, characterized in that the static contact angle of water after a UVC resistance test under the following conditions is 100 degrees or more. <Conditions for UVC resistance test> Using a germicidal lamp with a maximum emission wavelength of 254 nm, germicidal rays (UVC) were applied to the surface treatment layer of the article at a total of 216,000 μW h / cm 2 Irradiate.

6. The article described in claim 5, wherein T in formula (6) is a divalent hydrocarbon group having 2 to 20 carbon atoms which may contain a diorganosilylene group, a divalent silalkylene group, or a diorganosilylene group, L is an alkylene group having 1 to 4 carbon atoms, and E is an alkyl group having 1 to 4 carbon atoms, a phenyl group, or W.

7. The article according to claim 6, wherein S is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a phenyl group, or a group represented by formula (6).

8. 6. The article according to claim 5, wherein the fluorooxyalkylene group-containing polymer having a hydrolyzable group is any one of the following: 【Chemistry 9】 (In the formula, A 2 , Rf is the same as above.)

9. The surface treatment agent further comprises a compound represented by the following formula (7): 【Chemistry 10】 [wherein Rf is —C d F 2d -O-(CF 2 O) p (C 2 F 4 O) q (C 3 F 6 O) r (C 4 F 8 O) s (C 5 F 10 O) t (C 6 F 12 O) u -C d F 2d -(wherein d is independently an integer of 0 to 5 for each unit, p, q, r, s, t, and u are each independently an integer of 0 to 150, the sum of p, q, r, s, t, and u is at least 1, and each of these units may be linear or branched. Furthermore, each of the repeating units shown in parentheses with p, q, r, s, t, and u may be bonded randomly), and A 3 are independently terminated with CF 3 - or CF 2 a monovalent fluorine-containing hydrocarbon group which is H— and which may contain an oxygen atom, —OR 3 , or -PO(OR 3 ) 2 (However, R 3 is a hydrogen atom or a monovalent hydrocarbon group.

6. The article according to claim 1, which contains a fluorooxyalkylene group-containing polymer represented by the formula:

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