WO2019098230A1 - Base material - Google Patents

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Publication number
WO2019098230A1
WO2019098230A1 PCT/JP2018/042110 JP2018042110W WO2019098230A1 WO 2019098230 A1 WO2019098230 A1 WO 2019098230A1 JP 2018042110 W JP2018042110 W JP 2018042110W WO 2019098230 A1 WO2019098230 A1 WO 2019098230A1
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WO
WIPO (PCT)
Prior art keywords
group
ocf
conh
och
friction
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Application number
PCT/JP2018/042110
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French (fr)
Japanese (ja)
Inventor
尚志 三橋
香織 小澤
雅聡 能勢
裕介 渡邊
ピーター ハップフィールド
Original Assignee
ダイキン工業株式会社
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Application filed by ダイキン工業株式会社 filed Critical ダイキン工業株式会社
Publication of WO2019098230A1 publication Critical patent/WO2019098230A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces

Definitions

  • the present invention relates to a substrate, particularly to a substrate having good water repellency on the surface.
  • Patent Document 1 describes a substrate treated with a certain perfluoropolyether group-containing polymer-modified silane as a substrate having excellent water repellency on the surface.
  • An object of the present invention is to provide a substrate having sufficient water repellency, and in particular, capable of maintaining water repellency even when friction is repeatedly applied.
  • the substrate of the present invention is a substrate having a surface treatment layer formed of a compound containing a perfluoropolyether group on the surface, INNOWEP, in which an artificial sweat consisting of test cloth (5.5 g of trisodium phosphate, 10 g of sodium chloride, 10 g of sodium chloride, 3.1 g of lactic acid, 5 g of lysine and 100 ml of distilled water) was soaked under an atmosphere of 21 ° C. and a humidity of 65%.
  • a friction member made of silicone covered with ABREX (R) standard cotton soiling textile FINE with a load of 5 N applied to the substrate, the speed of the friction member being 40 mm / sec.
  • the number of reciprocations of the friction element in the friction test is 0, 1000, 2000, 3000 and 4000 (however, the number of reciprocations is the first measurement of static contact angle of water) Measure the static contact angle of water (the degree) to the number of round trips (times) at which the number of It is -0.0096 than the slope of the linear approximation line that is created based on.
  • the substrate of the invention is A substrate having a surface treatment layer formed of a compound containing a perfluoropolyether group on the surface, INNOWEP, in which an artificial sweat consisting of a test cloth (5.5 g of trisodium phosphate, 10 g of sodium chloride, 10 g of sodium chloride, 3.1 g of lactic acid, 5 g of lysine and 100 ml of distilled water) was soaked under an atmosphere of 21 ° C. and a humidity of 65%.
  • a friction member made of silicone covered with ABREX (R) standard cotton soiling textile FINE with a load of 5 N applied to the substrate, the speed of the friction member being 40 mm / sec.
  • the measured value of the static contact angle of water after 4000 cycles of reciprocation of the friction element in the friction test which reciprocates on the surface is 80 degrees or more.
  • the substrate of the present invention is a substrate having a surface treatment layer formed of a compound containing a perfluoropolyether group on the surface, Test cloth (5.5 g of trisodium phosphate, 10 g of sodium chloride, at an atmosphere of 21 ° C.
  • the number of reciprocations of the friction element is zero, 1000, 2000 and 3000
  • the number of reciprocations is that the static water contact angle measurement value is not 50 degrees at first. The maximum number of times it becomes.)
  • the slope of the linear approximation line is created on the basis of the reciprocating frequency (measurement of the static contact angle of water to times) (degrees) at is -0.0222 greater.
  • a substrate which has sufficient water repellency, and in particular can maintain water repellency even when friction is repeatedly applied.
  • the base material of this embodiment is A substrate having a surface treatment layer formed of a compound containing a perfluoropolyether group on the surface, Under an atmosphere of 21 ° C. and a humidity of 65%, a friction member made of silicone covered with a test cloth is loaded with a load of 5 N to the base material while applying a load of 40 mm / sec.
  • the number of reciprocations of the friction element 0, 1000, 2000, 3000 and 4000 (however, the number of reciprocations is a measurement value of the static contact angle of water)
  • test cloth As the above test cloth, ABREX (registered trademark) standard cotton manufactured by INNOWEP, in which artificial sweat consisting of 5.5 g of trisodium phosphate, 10 g of sodium chloride, 3.1 g of lactic acid, 5 g of lysine and 100 ml of distilled water is immersed.
  • the test cloth is a rectangle having a length of 8 cm on one side and a length of 5 cm on the other side orthogonal to the one side.
  • the surface roughness (Ra) of the ABREX (registered trademark) standard cotton soiling textile FINE manufactured by INNOWEP may be 14 to 21 ⁇ m or 16 to 19 ⁇ m.
  • the test cloth is in a state in which the artificial sweat of the composition has sufficiently penetrated into the cloth.
  • a test cloth can be obtained, for example, by immersing the cloth in artificial sweat of the above composition.
  • the cloth is dipped in the artificial sweat, for example, for 10 seconds to 10 minutes.
  • the cloth after immersion can be used for the said test cloth in the artificial sweat of the said composition, and it is not necessary to perform the removal etc. of the extra artificial sweat adhering to the test cloth.
  • test cloth used is cut into rectangles of 8 cm and 5 cm in side length.
  • a test cloth of the above size may contain about 1 ml (eg, 0.5 to 2.0 ml) of artificial sweat.
  • the silicone contacts the substrate through the test cloth. That is, a test cloth is present on the surface of the friction element in contact with the base material.
  • the above-mentioned test cloth and the above-mentioned silicone may be fixed, for example, using means (for example, adhesives, cords or rubber bands) which can be usually performed.
  • the above-mentioned test cloth and the above-mentioned silicone are fixed so that uneven parts (for example, wrinkles, deflections, etc. which may occur due to uneven distribution of the test cloth) do not exist on the contact surface between the friction element and the substrate.
  • a friction element made of silicone covered with the test cloth for example, a hemispherical one having a diameter of 2.5 cm can be used. In this case, it is the hemispherical projections (convex portions) that rub the substrate in the test.
  • the friction test is performed by repeatedly moving the friction element along the surface of the substrate. Specifically, in the friction test, a friction element covered with the test cloth is placed on the surface of the base under an atmosphere of 21 ° C. and a humidity of 65%, and a load of 5 N is applied to the base Thus, while applying a load, the friction element is reciprocated by a predetermined distance (for example, 20 mm) at a speed of 40 mm / sec. The friction test is performed, for example, by placing the surface of the substrate extending in the vertical direction.
  • ABREX (trademark) test equipment model: standard ABREX (trademark)
  • INNOWEP As a machine used for the said friction test, ABREX (trademark) test equipment (model: standard ABREX (trademark)) by INNOWEP can be mentioned.
  • a friction test is performed on the surface of the substrate. Measure the static contact angle of water on the surface of the substrate every 1000 times of the number of reciprocation of the friction element (ie, the number of frictions), and perform the friction test until the measured value of the static contact angle of water is less than 80 degrees. to continue.
  • the measured value of the static contact angle of water on the surface of the substrate is determined. If the 1000 measurements are less than 80 degrees, the friction test is discontinued. If the measured value of 1000 times is 80 degrees or more, a friction test is further performed, and when the number of reciprocations of the friction element is further 1000 times (that is, 2000 times in total), the water on the surface of the substrate is Determine the static contact angle measurement value of If the 2000 measurements are less than 80 degrees, the friction test is discontinued. In the case where the above 2000 measurements are 80 degrees or more, a friction test is carried out to further measure the static contact angle of water when the number of reciprocations of the friction element is 1000 (ie, a total of 3000). Ask.
  • the friction test is discontinued. If the measured value of 3000 times is 80 degrees or more, the friction test is further performed to obtain the measured value of the static contact angle of water when the number of reciprocations of the friction element is 4000 times. Thereafter, a friction test is performed until the static contact angle of water is less than 80 degrees, and the measured value of the static contact angle of water is obtained every 1000 reciprocations of the friction element.
  • the number of reciprocations makes the number of measurements of static contact angle of water first less than 80 degrees.
  • the measured value of the static contact angle of water after the number of reciprocation times of the friction element is less than 80 degrees
  • the measured value of the static contact angle of water at the number of reciprocations of 0 times and 1000 times Use to form a linear approximation straight line. If the measured value of the static contact angle of water after 1,000 times of reciprocation times of the friction element is 80 degrees or more and the measured value of the static contact angle of water after 2000 reciprocations times is less than 80 degrees
  • a linear approximation straight line is formed using the static contact angle measurements of water at 0 times, 1000 times and 2000 times.
  • the measured value of the static contact angle of water at 2000 times of reciprocation times of the friction element is 80 degrees or more and the measured value of the static contact angle of water at 3000 times of reciprocation times is less than 80 degrees
  • the linear approximation line is formed using the value of 0 times, 1000 times, 2000 times and 3000 times.
  • the measured value of the static contact angle of water at 3000 times of reciprocation of the friction element is 80 degrees or more
  • the static contact angle of water at 0 times, 1000 times, 2000 times, 3000 times and 4000 times of reciprocation times A linear approximation line is formed using the measured values of.
  • the gradient ⁇ of the linear approximation straight line is -0.0096 or more, preferably -0.0085 or more, more preferably -0.0080 or more, still more preferably -0. It is at least, particularly preferably at least ⁇ 0.0060. Even after the above-mentioned friction test, the base material of this embodiment has less decrease in the static contact angle of water on the surface thereof, and the water repellency is less likely to be reduced.
  • the upper limit of the gradient ⁇ is not particularly limited, it may be, for example, less than -0.0001.
  • ⁇ in the linear approximation straight line is, for example, 80 or more, specifically 90 or more, more specifically 100 or more, and more specifically 110 or more, and may be 114 or more. .
  • the gradient ⁇ ′ ′ of the linear approximate straight line is preferably more than ⁇ 0.0096, more preferably ⁇ 0.0085 or more, and still more preferably ⁇ 0.0080 or more. , Particularly preferably ⁇ 0.0070 or more, more preferably ⁇ 0.0060 or more, that is, the substrate according to the present embodiment has static contact with water on its surface even after the above friction test.
  • the upper limit of the gradient ”′ ′ is not particularly limited, but may be, for example, less than ⁇ 0.0001.
  • ⁇ ′ in the linear approximation straight line is, for example, 80 or more, specifically 90 or more, more specifically 100 or more, more specifically 110 or more, and 114 or more. Good.
  • the substrate of this embodiment preferably has a high static contact angle measurement before the friction test (that is, a static contact angle measurement with zero reciprocations).
  • the contact angle of the substrate before the friction test is preferably 80 degrees or more, more preferably 100 degrees or more, particularly preferably 105 degrees or more, and still more preferably 110 degrees or more.
  • the base material of the present embodiment preferably has a static contact angle measurement value of at least 80 degrees, more preferably at least 84 degrees, at a frequency of 4,000 reciprocations of the friction element. Preferably it is 85 degrees or more, Especially preferably, it is 90 degrees or more.
  • a substrate even when the surface of the substrate is rubbed, the water repellency on the surface is good. Thus, such substrates may be particularly useful in applications where friction may occur.
  • the ratio of the static contact angle of water at 4,000 reciprocations of the friction element to the measured value of the static contact angle of water at the reciprocation number of times of the friction element may be 0.70 or more, 0.80 It may be above.
  • the upper limit value of the ratio is not particularly limited, but may be, for example, 1.00 or less, specifically 0.98 or less.
  • the base material of the present embodiment preferably has a static contact angle measurement value of at least 75 degrees, more preferably at least 80 degrees, at a reciprocation frequency of 5,000 times of the friction element. Preferably, it is 85 degrees or more.
  • a substrate even when the surface of the substrate is rubbed, it is possible to maintain particularly good water repellency on the surface. Thus, such substrates may be particularly useful in applications where friction may occur.
  • the dynamic friction coefficient measured in accordance with ASTM D4917 is preferably less than 0.050, and more preferably less than 0.035.
  • the substrate of this embodiment further comprises A test cloth (here, the test cloth is trisodium phosphate) under an atmosphere of 21 ° C. and a humidity of 65% on the surface irradiated with ultraviolet light of wavelength 300 nm to 400 nm at an irradiance of 62 W / m 2 for 300 hours Covered with INNOWEP's ABREX (R) standard cotton soiling textile FINE, soaked with artificial sweat consisting of 5.5 g, sodium chloride 10 g, lactic acid 3.1 g, lysine 5 g and 100 ml distilled water.
  • a test cloth here, the test cloth is trisodium phosphate
  • the number of reciprocations of the friction element is zero. 1000 times, 2000 times and 3000 times (however, the number of reciprocation times is a measure of the static contact angle of water Based on the measured value of static contact angle of water after UV irradiation (degree) to the number of round trips (times) in which the value is first measured less than 50 degrees)
  • the slope of the linear approximation straight line is greater than -0.0222.
  • UV irradiation source for example, a xenon lamp can be used. More specifically, the UV irradiation can be performed by setting the temperature of the black panel of the substrate to 55 degrees and the distance between the lamp and the surface of the substrate irradiated with UV to 29 cm.
  • a measure of the static contact angle of water on the surface prior to the friction test is determined. After that, a friction test is performed on the surface, and the static contact angle of water on the surface of the substrate is measured every 1000 reciprocations of the friction element, and the measured value of the static contact angle of water is less than 50 degrees Continue the friction test until.
  • the friction test after the UV irradiation test is performed as follows.
  • the measured value of the static contact angle of water on the surface that is, the static contact angle of water when the number of reciprocations is zero
  • a friction test is performed on the surface of the substrate after the UV irradiation test.
  • the static contact angle of water on the surface of the substrate is measured every 1000 reciprocations of the friction element, and the friction test is continued until the measured value of the static contact angle of water is less than 50 degrees.
  • the measured value of the static contact angle of water on the surface of the substrate is determined. If the 1000 measurements are less than 50 degrees, the friction test is discontinued. If the measured value of 1000 times is 50 degrees or more, a friction test is further performed, and when the number of reciprocations of the friction element is further 1000 times (ie, 2000 times in total), water on the surface of the substrate Determine the static contact angle measurement value of If the above 2000 measurements are less than 50 degrees, the friction test is discontinued. In the case where the above 2000 measurements are 50 degrees or more, a friction test is further performed, and the static contact angle measurement value of water when the number of reciprocations of the friction element is 1000 times (ie, a total of 3000 times) Ask.
  • the friction test is discontinued.
  • the friction test is further performed to obtain the measured value of the static contact angle of water when the number of reciprocations of the friction element is 4000 times. Thereafter, a friction test is performed until the static contact angle of water is less than 50 degrees, and the measured value of the static contact angle of water is obtained every 1000 reciprocations of the friction element.
  • the relationship between the number of reciprocations x 'of the friction element and the measured value of the static contact angle of water when the number of reciprocations of the friction element is 3000 at maximum is determined. Specifically, it is based on the measurement value (degree) of the static contact angle of water after the UV irradiation test with respect to the number of reciprocation times of the friction element 0 times, 1000 times, 2000 times and 3000 times (times).
  • the number of reciprocations makes the number of measurements of static contact angle of water first less than 50 degrees the maximum. Specifically, when the measured value of the static contact angle of water after the number of reciprocation times of the friction element is less than 50 degrees, the measured value of the static contact angle of water at the number of reciprocations of 0 times and 1000 times Use to form a linear approximation straight line. If the measured value of the static contact angle of water after the number of reciprocation times of the friction element is not less than 50 degrees and the measured value of the static contact angle of water after the 2000 times is less than 50 degrees, the number of reciprocations is 0 times , 1000 and 2000 values are used to form a linear approximation straight line.
  • the gradient ⁇ ′ of the linear approximate straight line after the above-mentioned UV irradiation test is preferably more than ⁇ 0.0222, more preferably ⁇ 0.0200 or more, and still more preferably ⁇ 0. It is more than 0180. Even after such a substrate has been subjected to the above-described friction test, the decrease in static contact angle of water on the surface is small, and the water repellency is unlikely to be reduced.
  • the upper limit of the gradient ’′ is not particularly limited, but may be, for example, less than ⁇ 0.001.
  • ⁇ ′ is, for example, 98 or more, and more specifically, 100 or more.
  • the relationship between the number of reciprocations x 'of the friction element and the measured value of the static contact angle of water when the number of reciprocations of the friction element is at most 6000 times is determined.
  • Linear approximate straight line F ′ ′ ′ x ′ ⁇ ′ ′ ′ x ′ + ⁇ created based on the measured value (degree) of static contact angle of water after UV irradiation test with respect to the number of reciprocations (times) of the friction element Find '''( ⁇ ''' and ⁇ ''are constants).
  • ⁇ ′ ′ ′ is, for example, more than ⁇ 0.0222.
  • ⁇ ′ ′ ′ is, for example, 98 or more, more specifically 100 or more.
  • the measured value of the static contact angle of water after 3,000 reciprocations of the friction element is preferably 50 degrees or more, and is 55 degrees or more It is more preferably 60 degrees or more, particularly preferably 70 degrees or more, and still more preferably 75 degrees or more.
  • the substrate of this embodiment has a surface treatment layer formed of a compound containing a perfluoropolyether group on the surface on at least one surface. That is, it is preferable that the base material of this aspect contains a surface treating agent layer and a base layer.
  • the base layer is, for example, glass, resin (natural or synthetic resin, for example, general plastic material, may be plate, film, or other form), metal (metal such as aluminum, copper, iron, etc.) May be a single substance or a composite such as an alloy), ceramics, semiconductor (silicon, germanium, etc.), fiber (textile, non-woven cloth, etc.), fur, leather, wood, china, stone etc., construction member etc. any appropriate It may be composed of materials.
  • the material constituting the surface of the base layer may be an optical member material such as glass or transparent plastic.
  • some layer (or film) such as a hard coat layer or an antireflective layer may be formed on the surface (the outermost layer) of the base layer.
  • the antireflective layer either a single layer antireflective layer or a multilayer antireflective layer may be used.
  • inorganic substances that can be used for the antireflective layer include SiO 2 , SiO, ZrO 2 , TiO 2 , TiO, Ti 2 O 3 , Ti 2 O 5 , Al 2 O 3 , Ta 2 O 5 , CeO 2 and MgO.
  • the multilayer antireflection layer it is preferable to use SiO 2 and / or SiO in its outermost layer.
  • the article to be manufactured is an optical glass part for a touch panel, it has a thin film using a transparent electrode such as indium tin oxide (ITO) or indium zinc oxide on a part of the surface of the base layer (glass)
  • a transparent electrode such as indium tin oxide (ITO) or indium zinc oxide
  • the base layer may be an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomized film layer, a hard coating film layer, a polarizing film, a phase difference film, or the like depending on its specific specifications.
  • a liquid crystal display module is an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomized film layer, a hard coating film layer, a polarizing film, a phase difference film, or the like depending on its specific specifications.
  • a liquid crystal display module is an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an
  • the base layer comprises glass.
  • the glass examples include soda lime glass, alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass and quartz glass.
  • the glass may be chemically tempered glass, such as chemically tempered soda lime glass, chemically tempered alkali aluminosilicate glass, and chemically tempered borosilicate glass.
  • the chemically strengthened glass is one or more selected from the group consisting of SiO 2 and Al 2 O 3 , Na 2 O, MgO, K 2 O, CaO, BaO, SrO, and B 2 O 3 It may be a glass obtained by chemical strengthening treatment (typically, ion exchange) of a glass for chemical strengthening that contains further oxides.
  • the above-mentioned glass for chemical strengthening contains the above-mentioned oxide in the following proportion (weight percentage based on oxide).
  • SiO 2 60.0 to 80.0%
  • Al 2 O 3 0.5 to 12.0%
  • B 2 O 3 0 to 3.0%
  • MgO 0 to 12.0%
  • CaO 0 to 5.0%
  • SrO 0 to 5.0%
  • BaO 0 to 5.0%
  • Na 2 O 3.0 to 20.0%
  • the chemical strengthening treatment can be performed by a conventionally known method.
  • a glass plate is brought into contact with a melt of a metal salt (for example, potassium nitrate) containing a large ion radius metal ion (typically, K ion) by immersion or the like.
  • a metal salt for example, potassium nitrate
  • the metal ion of small ion radius (typically, Na ion or Li ion) is replaced with the metal ion of large ion radius.
  • the thickness of the compressive stress layer of the chemically strengthened glass may be preferably 35 ⁇ m or more, more preferably 40 ⁇ m or more, and still more preferably 45 ⁇ m or more.
  • the thickness of the compression stress layer of the chemically strengthened glass can be appropriately adjusted by adjusting the conditions for chemically strengthening the glass for chemical strengthening, the composition of the glass for chemical strengthening, and the like.
  • the thickness of the compressive stress layer is the depth of the region in which the compressive stress is formed with reference to the outermost surface of the glass plate.
  • the thickness of the compressive stress layer can be measured by a surface stress meter.
  • the thickness of the compressive stress layer can be measured using a surface stress meter FSM-6000 manufactured by Orihara Mfg. Co., under a 589 nm Na light source under an environment of room temperature 25 ° C. and humidity 60%.
  • the shape of the base layer is not particularly limited.
  • the surface area of the base layer on which the surface treatment agent layer (surface treatment layer) is to be formed may be at least a part of the surface of the base layer, depending on the application and specific specifications of the article to be manufactured. Can be determined appropriately.
  • At least the surface portion may be made of a material originally having a hydroxyl group.
  • a material originally having a hydroxyl group examples include glass, and further, metals (in particular, base metals), ceramics, semiconductors, etc. on which a natural oxide film or a thermal oxide film is formed on the surface.
  • the base layer is pretreated to introduce hydroxyl groups on the surface of the base layer. Can be increased or decreased. Examples of such pretreatment include plasma treatment (eg, corona discharge) and ion beam irradiation.
  • the plasma treatment can introduce or increase hydroxyl groups on the surface of the base layer, and can also be suitably used to clean the surface of the base layer (remove foreign matter and the like).
  • an interfacial adsorbent having a carbon-carbon unsaturated bond group is coated on the surface of the base layer in advance by the LB method (Langmuir-Blodgett method), chemical adsorption method or the like. And then the unsaturated bond is cleaved in an atmosphere containing oxygen, nitrogen and the like.
  • the base layer may be made of a material including at least a silicone compound having one or more other reactive groups such as Si—H groups, or a material containing an alkoxysilane.
  • the surface treatment agent preferably contains a perfluoropolyether group (hereinafter also referred to as "PFPE group”) containing compound, and preferably contains a PFPE group containing silane compound.
  • PFPE group perfluoropolyether group
  • the PFPE-containing silane compound is, for example, a compound represented by (A1), (A2), (B1), (B2), (C1), (C2), (D1) or (D2).
  • di- to dodeca-valent organic group means a carbon-containing di- to 10-valent group.
  • the di- to deca-valent organic group is not particularly limited, and examples thereof include di- to 10-valent groups obtained by further removing 1 to 9 hydrogen atoms from a hydrocarbon group.
  • the divalent organic group is not particularly limited, and examples thereof include divalent groups in which one hydrogen atom is further eliminated from a hydrocarbon group.
  • hydrocarbon group means a group containing carbon and hydrogen wherein one hydrogen atom has been eliminated from the molecule.
  • a hydrocarbon group is not particularly limited, and may be a hydrocarbon group having 1 to 20 carbon atoms which may be substituted by one or more substituents, for example, an aliphatic hydrocarbon group, Aromatic hydrocarbon groups and the like can be mentioned.
  • the “aliphatic hydrocarbon group” may be linear, branched or cyclic, and may be saturated or unsaturated.
  • the hydrocarbon group may also contain one or more ring structures.
  • Such a hydrocarbon group may have one or more of N, O, S, Si, an amide, a sulfonyl, a siloxane, a carbonyl, a carbonyloxy and the like in the terminal or molecular chain thereof.
  • the substituent of the “hydrocarbon group” is not particularly limited, and for example, a halogen atom; C 1-6 alkyl optionally substituted by one or more halogen atoms Group, C 2-6 alkenyl group, C 2-6 alkynyl group, C 3-10 cycloalkyl group, C 3-10 unsaturated cycloalkyl group, 5- to 10-membered heterocyclyl group, 5- to 10-membered unsaturated heterocyclyl Groups, one or more groups selected from C 6-10 aryl groups and 5-10 membered heteroaryl groups.
  • an alkyl group and a phenyl group may be unsubstituted or substituted, unless otherwise specified.
  • the substituent of such group is not particularly limited, and one or more groups selected from, for example, a halogen atom, a C 1-6 alkyl group, a C 2-6 alkenyl group and a C 2-6 alkynyl group are preferable. It can be mentioned.
  • R f independently at each occurrence represents an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms.
  • the "C1-C16 alkyl group" in the C1-C16 alkyl group which may be substituted by one or more fluorine atoms is a branched chain even if it is a straight chain It is preferably a linear or branched alkyl group having 1 to 6 carbon atoms, particularly 1 to 3 carbon atoms, and more preferably a linear alkyl group having 1 to 3 carbon atoms.
  • Rf is preferably an alkyl group having 1 to 16 carbon atoms, which is substituted by one or more fluorine atoms, and more preferably a CF 2 H—C 1-15 fluoroalkylene group or a C 1-16 It is a perfluoroalkyl group, more preferably a C 1-16 perfluoroalkyl group.
  • the perfluoroalkyl group having 1 to 16 carbon atoms may be linear or branched, and preferably has 1 to 6 carbon atoms, particularly 1 to 6 carbon atoms, in a linear or branched chain.
  • PFPE is independently at each occurrence: - (OC 6 F 12) a - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 X 10 6) d - (OC 2 F 4) e - (OCF 2) f - Is a group represented by
  • a, b, c, d, e and f are each independently an integer of 0 or more and 200 or less, and the sum of a, b, c, d, e and f is at least 1.
  • a, b, c, d, e and f are each independently an integer of 0 or more and 100 or less.
  • the sum of a, b, c, d, e and f is 5 or more, more preferably 10 or more.
  • the sum of a, b, c, d, e and f is 200 or less, more preferably 100 or less, for example 10 or more and 200 or less, more specifically 10 or more and 100 or less.
  • the order in which each repeating unit enclosed in parentheses with a, b, c, d, e or f is present is arbitrary in the formula.
  • X 10 each independently at each occurrence is a hydrogen atom, a fluorine atom or a chlorine atom, preferably a hydrogen atom or a fluorine atom, more preferably a fluorine atom.
  • repeating units may be linear or branched, but are preferably linear.
  • - (OC 6 F 12) - is, - (OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2) -, - (OCF (CF 3) CF 2 CF 2 CF 2 CF 2) -, - (OCF 2 CF (CF 3) CF 2 CF 2 CF 2) -, - (OCF 2 CF 2 CF (CF 3) CF 2 CF 2) -, - (OCF 2 CF 2 CF (CF 3) CF 2 CF 2) -, - (OCF 2 CF 2 CF (CF 3) CF 2) - And-(OCF 2 CF 2 CF 2 CF (CF 3 ))-may be used, but-(OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 )-is preferable.
  • - (OC 5 F 10) - is, - (OCF 2 CF 2 CF 2 CF 2 CF 2) -, - (OCF (CF 3) CF 2 CF 2 CF 2) -, - (OCF 2 CF (CF 3) It may be CF 2 CF 2 )-,-(OCF 2 CF 2 CF (CF 3 ) CF 2 )-,-(OCF 2 CF 2 CF (CF 3 ))-or the like, preferably-( OCF 2 CF 2 CF 2 CF 2 CF 2) - a.
  • - (OC 4 F 8) - is, - (OCF 2 CF 2 CF 2 CF 2) -, - (OCF (CF 3) CF 2 CF 2) -, - (OCF 2 CF (CF 3) CF 2) - , - (OCF 2 CF 2 CF (CF 3)) -, - (OCF 2 CF 3) 2 CF 2) -, - (OCF 2 C (CF 3) 2) -, - (OCF (CF 3) CF ( It may be any of CF 3 )),-(OCF (C 2 F 5 ) CF 2 )-and-(OCF 2 CF (C 2 F 5 ))-, but preferably-(OCF 2 CF 2).
  • - (OC 3 F 6) - is, - (OCF 2 CF 2 CF 2) -, - (OCF (CF 3) CF 2) - and - (OCF 2 CF (CF 3 )) - be any of Although preferred, preferred is-(OCF 2 CF 2 CF 2 )-.
  • - (OC 2 F 4) - is, - (OCF 2 CF 2) - and - (OCF (CF 3)) - but it may be any of, preferably - (OCF 2 CF 2) - in is there.
  • the PFPE is — (OC 3 F 6 ) d — (wherein d is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less) .
  • PFPE is — (OCF 2 CF 2 CF 2 ) d — (wherein d is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less) or OCF (CF 3 ) CF 2 ) d — (wherein, d is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less).
  • PFPE is — (OCF 2 CF 2 CF 2 ) d — (wherein d is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less) .
  • the PFPE is — (OC 4 F 8 ) c — (OC 3 F 6 ) d — (OC 2 F 4 ) e — (OCF 2 ) f —, wherein c and d are each independently And e and f are each independently an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less, and c, d, e and The sum of f is at least 5 or more, preferably 10 or more, and the order in which each repeating unit enclosed in parentheses with the subscript c, d, e or f is given is arbitrary in the formula).
  • PFPE is, - (OCF 2 CF 2 CF 2 CF 2) c - (OCF 2 CF 2 CF 2) d - (OCF 2 CF 2) e - (OCF 2) f - a.
  • PFPE is — (OC 2 F 4 ) e — (OCF 2 ) f — (wherein e and f are each independently 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably Is an integer of 10 or more and 200 or less, and the order in which each repeating unit enclosed in parentheses with the subscript e or f is attached may be arbitrary in the formula).
  • PFPE is a group represented by-(R 6 -R 7 ) j- .
  • R 6 is OCF 2 or OC 2 F 4 , preferably OC 2 F 4 .
  • R 7 is a group selected from OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 or selected independently from these groups A combination of two or three groups.
  • R 7 is a group selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 or from OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 It is a selected group, or a combination of 2 or 3 groups independently selected from these groups.
  • the combination of 2 or 3 groups independently selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 is not particularly limited.
  • the j is an integer of 2 or more, preferably 3 or more, more preferably 5 or more, and 100 or less, preferably 50 or less.
  • OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 may be linear or branched, preferably linear .
  • PFPE is preferably, - (OC 2 F 4 -OC 3 F 6) j - or - (OC 2 F 4 -OC 4 F 8) j - is.
  • the ratio of e to f (hereinafter referred to as “e / f ratio”) is 0.1 or more and 10 or less, preferably 0.2 or more and 5 or less, and more preferably 0.2 or more and 2 or less More preferably, it is 0.2 or more and 1.5 or less, and still more preferably 0.2 or more and 0.85 or less.
  • e / f ratio 10 or less, the slipperiness, friction durability and chemical resistance (for example, durability against artificial sweat) of the layer obtained from this compound are further improved.
  • the smaller the e / f ratio the better the slip and friction durability of the layer.
  • the stability of the compound can be further enhanced. The higher the e / f ratio, the better the stability of the compound.
  • the number average molecular weight of -PFPE- moiety is not particularly limited, but for example, 500 to 30,000, preferably 1,500 to 30,000, more preferably 2,000 to It is 10,000.
  • the above-mentioned number average molecular weight is a value measured by 19 F-NMR.
  • the number average molecular weight of -PFPE- moiety is 500 to 30,000, preferably 1,000 to 20,000, more preferably 2,000 to 15,000, still more preferably 2,000 to It may be 10,000, for example 3,000 to 6,000.
  • the number average molecular weight of the -PFPE- moiety may be 4,000 to 30,000, preferably 5,000 to 10,000, more preferably 6,000 to 10,000.
  • R 13 independently at each occurrence represents a hydroxyl group or a hydrolysable group.
  • hydrolyzable group means a group capable of undergoing a hydrolysis reaction, that is, a group capable of leaving a main skeleton of a compound by a hydrolysis reaction.
  • R examples include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl and isobutyl; and substituted alkyl groups such as chloromethyl.
  • an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
  • the hydroxyl group is not particularly limited, but may be formed by hydrolysis of a hydrolyzable group.
  • R 14 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms.
  • each occurrence of R 11 independently represents a hydrogen atom or a halogen atom.
  • the halogen atom is preferably an iodine atom, a chlorine atom or a fluorine atom, and more preferably a fluorine atom.
  • each occurrence of R 12 independently represents a hydrogen atom or a lower alkyl group.
  • the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group and a propyl group.
  • n1 is independently an integer of 0 to 3, preferably 1 to 3, and more preferably 3 for each (-SiR 13 n1 R 14 3-n1 ) unit.
  • at least one n1 is an integer of 1 to 3, that is, all n1 are never 0 simultaneously. In other words, at least one R 13 exists in the formula.
  • At least two Si bonded to a hydroxyl group or a hydrolyzable group are present. That is, in the formulas (A1) and (A2), at least two —SiR 13 n1 R 14 3-n1 structures (ie, —SiR 13 moieties) in which n is 1 or more exist.
  • each X 1 independently represents a single bond or a di- to 10-valent organic group.
  • the said X 1 is a perfluoropolyether part (namely, Rf-PFPE part or -PFPE- part) which mainly provides water repellency, surface slip property, etc. in the compound represented by Formula (A1) and (A2) And a silane moiety that provides the ability to bind to a substrate (ie, a group that is bracketed with .alpha.1).
  • X 1 may be any organic group as long as the compounds represented by formulas (A1) and (A2) can stably exist.
  • X 1 can be X e .
  • X e represents a single bond or 2-10 divalent organic group, preferably a single bond or -C 6 H 4 -, (i.e. - - phenylene.
  • Each R 4 independently represents a hydrogen atom, a phenyl group, or a C 1-6 alkyl group (preferably a methyl group), preferably a hydrogen atom or a methyl group.
  • the —C 6 H 4 —, —CO—, —NR 4 — or —SO 2 — is preferably contained in the molecular main chain of the PFPE-containing silane compound.
  • the molecular main chain represents the relatively longest linking chain in the molecule of the PFPE-containing silane compound.
  • X e is more preferably a single bond or -C 6 H 4 -, - CONR 4 -, - CONR 4 -C 6 H 4 -, - CO -, - CO-C 6 H 4 -, - SO 2 NR 4 -, - SO 2 NR 4 -C 6 H 4 -, - SO 2 -, and -SO 2 -C 6 H 4 - represents a 2-10 monovalent organic group having at least one selected from the group consisting of .
  • Additional -C 6 H 4 -, - CONR 4 -, - CONR 4 -C 6 H 4 -, - CO -, - CO-C 6 H 4 -, - SO 2 NR 4 -, - SO 2 NR 4 - C 6 H 4 -, - SO 2 -, or -SO 2 -C 6 H 4 - is preferably contained in the molecular backbone of the PFPE-containing silane compound.
  • ⁇ 1 is an integer of 1 to 9
  • ⁇ 1 ′ is an integer of 1 to 9.
  • These ⁇ 1 and ⁇ 1 ′ can change according to the valence of X 1 .
  • the sum of ⁇ 1 and ⁇ 1 ′ is the same as the valence of X 1 .
  • [alpha] 1 and [alpha] 1 'sum is 10, for example, [alpha] 1 is 9 and [alpha] 1' is 1, [alpha] 1 is 5 and [alpha] 1 'is 5 or [alpha] 1 is 1 and [alpha] 1, 'Can be nine.
  • ⁇ 1 and ⁇ 1 ′ are 1.
  • [alpha] 1 is the value obtained by subtracting 1 from the valence of X 1.
  • the above X 1 is preferably a divalent to heptavalent, more preferably a divalent to tetravalent, and still more preferably a divalent organic group.
  • X 1 is a divalent to tetravalent organic group
  • ⁇ 1 is 1 to 3
  • ⁇ 1 ′ is 1.
  • X 1 is a divalent organic group
  • ⁇ 1 is 1
  • ⁇ 1 ′ is 1.
  • the formulas (A1) and (A2) are represented by the following formulas (A1 ′) and (A2 ′).
  • R 31 represents a single bond,-(CH 2 ) s ' -or o-, m- or p-phenylene group, preferably-(CH 2 ) s'- s ′ is an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and still more preferably 1 or 2.
  • X a represents-(X b ) l ' - X b is independently at each occurrence -O-, -S-, o-, m- or p-phenylene, -C (O) O-, -Si (R 33 ) 2 -,-( Si (R 33) 2 O) m '-Si (R 33) 2 -, - CONR 34 -, - O-CONR 34 -, - NR 34 - and - (CH 2)
  • n' - is selected from the group consisting of Represents a group R 33 each independently represents a phenyl group, a C 1-6 alkyl group or a C 1-6 alkoxy group, preferably a phenyl group or a C 1-6 alkyl group, more preferably a methyl group
  • R 34 independently at each occurrence represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group (preferably a methyl group),
  • R 31 and X a are one or more selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group It may be substituted by the substituent of
  • X 1 is- (R 31 ) p ' -(X a ) q' -R 32- .
  • R 32 represents a single bond,-(CH 2 ) t ' -or o-, m- or p-phenylene group, preferably-(CH 2 ) t'- .
  • t ′ is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3.
  • R 32 (typically a hydrogen atom in R 32 ) is substituted by one or more substituents selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group It may be done.
  • said X 1 is Single bond, C 1-20 alkylene group, -R 31 -X c -R 32- or -X d -R 32- [Wherein, R 31 and R 32 are as defined above. ] It can be.
  • the alkylene group, - (C ⁇ H 2 ⁇ ) - a group having the structure, may be substituted or unsubstituted, may be linear or branched.
  • X 1 is -X f -, -X f -C 1-20 alkylene group, -X f - (CH 2) s ' -X c -, -X f - (CH 2) s '-X c - (CH 2) t' - -X f -X d- or -X f -X d- (CH 2 ) t ' - It is.
  • s 'and t' are as defined above.
  • X f is an alkylene group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, such as a methylene group.
  • the hydrogen atom in X f may be substituted by one or more substituents selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group, preferably substituted There is.
  • X f may be linear or branched, and is preferably linear.
  • X 1 is Single bond, C 1-20 alkylene group, -(CH 2 ) s' -X c- , -(CH 2 ) s ' -X c- (CH 2 ) t'- -X d- or -X d- (CH 2 ) t ' - [Wherein, s ′ and t ′ are as defined above. ] It is.
  • X c is -O-, -S-, -C (O) O-, -CONR 34 -, -O-CONR 34 -, -Si (R 33 ) 2- , - (Si (R 33) 2 O) m '-Si (R 33) 2 -, -O- (CH 2) u '- (Si (R 33) 2 O) m' -Si (R 33) 2 -, -O- (CH 2) u '-Si (R 33) 2 -O-Si (R 33) 2 -CH 2 CH 2 -Si (R 33) 2 -O-Si (R 33) 2 -, -O- (CH 2) u '-Si (OCH 3) 2 OSi (OCH 3) 2 -, -CONR 34 - (CH 2) u '- (Si (R 33) 2 O) m' -Si (R 33) 2 -, -CONR 34
  • X d is -S-, -C (O) O-, -CONR 34 -, -CONR 34 - (CH 2) u '- (Si (R 33) 2 O) m' -Si (R 33) 2 -, -CONR 34 - (CH 2) u '-N (R 34) -, or -CONR 34 - (o-, m- or p- phenylene) -Si (R 33) 2 - [Wherein each symbol is as defined above. ] Represents
  • X 1 is -X f -, -X f -C 1-20 alkylene group, -X f - (CH 2) s ' -X c -, -X f - (CH 2) s '-X c - (CH 2) t' - -X f -X d- or -X f -X d- (CH 2 ) t ' - [Wherein, X f , s ′ and t ′ are as defined above.
  • X c is, -O-, or -CONR 34 -
  • X d is, -CONR 34 -
  • R 34 each independently represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group (preferably a methyl group) at each occurrence.
  • X 1 is -X f - (CH 2) s ' -X c -, -X f - (CH 2) s '-X c - (CH 2) t' - -X f -X d- or -X f -X d- (CH 2 ) t ' -
  • X f , s ′ and t ′ are as defined above.
  • X c is, -CONR 34 -
  • X d is, -CONR 34 -, R 34 each independently represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group (preferably a methyl group) at each occurrence.
  • X 1 is Single bond, C 1-20 alkylene group, -(CH 2 ) s' -X c- (CH 2 ) t ' -or -X d- (CH 2 ) t'- [Wherein each symbol is as defined above. ] It can be.
  • X 1 is Single bond, C 1-20 alkylene group, -(CH 2 ) s ' -O- (CH 2 ) t'- , -(CH 2 ) s' -(Si (R 33 ) 2 O) m ' -Si (R 33 ) 2- (CH 2 ) t'- , - (CH 2) s '-O- (CH 2) u' - (Si (R 33) 2 O) m '-Si (R 33) 2 - (CH 2) t' -, or - (CH 2) s' -O- (CH 2) t '-Si (R 33) 2 - (CH 2) u' -Si (R 33) 2 - (C v H 2v) - [Wherein, R 33 , m ′, s ′, t ′ and u ′ are as defined above, and v is an integer of 1 to 20, preferably an integer of 2 to 6, more
  • -(C v H 2v ) - may be linear or branched, and for example, -CH 2- , -CH 2 CH 2- , -CH 2 CH 2 CH 2 -, - CH (CH 3 ) -, - CH (CH 3) CH 2 - may be.
  • the X 1 group is substituted by one or more substituents selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group (preferably a C 1-3 perfluoroalkyl group) It may be done.
  • the X 1 group may be other than an —O—C 1-6 alkylene group.
  • the X 1 group includes, for example, the following groups: [Wherein each R 41 independently represents a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C 1-6 alkoxy group, preferably a methyl group; D is -CH 2 O (CH 2 ) 2- , -CH 2 O (CH 2 ) 3- , -CF 2 O (CH 2 ) 3- , -(CH 2 ) 2- , -(CH 2 ) 3- , - (CH 2) 4 -, -CONH- (CH 2 ) 3- , -CON (CH 3 )-(CH 2 ) 3- , -CON (Ph)-(CH 2 ) 3- (wherein, Ph means phenyl), and (Wherein, each R 42 independently represents a hydrogen atom, a C 1-6 alkyl group or a C 1-6 alkoxy group, preferably a methyl group or a methoxy group, more preferably a a methyl
  • X 1 include, for example: Single bond -CH 2 OCH 2- , -CH 2 O (CH 2 ) 2- , -CH 2 O (CH 2 ) 3- , -CH 2 O (CH 2 ) 6- , -CF 2 -CH 2 -O-CH 2- , -CF 2 -CH 2 -O- (CH 2 ) 2- , -CF 2 -CH 2 -O- (CH 2 ) 3- , -CF 2 -CH 2 -O- (CH 2 ) 6- -CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2- , -CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2- , -CH 2 O (CH 2) 3 Si (CH 3) 2 O (Si (CH 3) 2 O) 2 Si (CH 3) 2 (CH 2) 2 -, -, -CH
  • X 1 is -CH 2 OCH 2- , -CH 2 O (CH 2 ) 2- , -CH 2 O (CH 2 ) 3- , -CH 2 O (CH 2 ) 6- , -CF 2 -CH 2 -O-CH 2- , -CF 2 -CH 2 -O- (CH 2 ) 2- , -CF 2 -CH 2 -O- (CH 2 ) 3- , -CF 2 -CH 2 -O- (CH 2 ) 6- -CH 2 OCF 2 CHFOCF 2- , -CH 2 OCF 2 CHFOCF 2 CF 2- , -CH 2 OCF 2 CHFOCF 2 CF 2- , -CH 2 OCF 2 CHFOCF 2 CF 2 CF 2- , -CH 2 OCH 2 CF 2 CF 2 OCF 2- , -CH 2 OCH 2 CF 2 CF 2 OCF 2- , -CH 2 OCH 2 CF 2 CF 2 OCF 2- , -CH 2 OCH 2 CF 2
  • X 1 is -CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 -C (O) NH-CH 2- , -CONH-, -CONH-CH 2- , -CONH- (CH 2 ) 2- , -CONH- (CH 2 ) 3- , -CONH- (CH 2 ) 6- , -CF 2 CONH-, -CF 2 CONHCH 2- , -CF 2 CONH (CH 2 ) 2- , -CF 2 CONH (CH 2 ) 3- , -CF 2 CONH (CH 2 ) 6- , -CON (CH 3 )-(CH 2 ) 3- , -CON (Ph)-(CH 2 ) 3- (wherein Ph means phenyl), -CON (CH 3 )-(CH 2 ) 6- , -CON (Ph)-(CH 2 ) 6- (wherein Ph means phenyl), -CON (CH 3 )-(CH 2 ) 6- , -CON (Ph)
  • X 1 represents X e ′ .
  • X e ′ is a single bond, an alkylene group having 1 to 6 carbon atoms, -R 51 -C 6 H 4 -R 52- , -R 51 -CONR 4 -R 52- , -R 51 -CONR 4 -C 6 H 4 -R 52- , -R 51 -CO-R 52- , -R 51 -CO-C 6 H 4 -R 52- , -R 51 -SO 2 NR 4 -R 52- , -R 51 -SO 2 NR 4 -C 6 H 4 -R 52- , -R 51 -SO 2 -R 52- , or -R 51 -SO 2 -C 6 H 4 -R 52- .
  • R 51 and R 52 each independently represent a single bond or an alkylene group having 1 to 6 carbon atoms, preferably a single bond or an alkylene group having 1 to 3 carbon atoms.
  • R 4 is as defined above.
  • the alkylene group is substituted or unsubstituted, preferably unsubstituted.
  • a halogen atom Preferably a fluorine atom can be mentioned, for example.
  • the alkylene group is linear or branched, and is preferably linear.
  • X e ′ is Single bond, -X f -, 1 to 6 carbon atoms, preferably an alkylene group -X f -C 1-6 alkylene group having 1 to 3 carbon atoms, preferably -X f -C 1-3 alkylene group, more preferably -X f -C 1- 2 alkylene groups, -C 6 H 4 -R 52 ' -, -CONR 4 '-R 52' -, -CONR 4 '-C 6 H 4 -R 52' -, -X f -CONR 4 '-R 52' -, -X f -CONR 4 '-C 6 H 4 -R 52' -, -CO-R 52 ' -, -CO-C 6 H 4 -R 52 ' -, -SO 2 NR 4 '-R 52' -, -SO 2 NR 4 '-C 6 H 4 -R 52' -, -CO-
  • X e ′ is preferably -X f -, An alkylene group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, -X f -C 1-6 alkylene group, preferably -X f -C 1-3 alkylene group, more preferably -X f -C 1-2 alkylene group, -CONR 4 '-R 52' -, -CONR 4 '-C 6 H 4 -R 52' -, -X f -CONR 4 '-R 52' -, -X f -CONR 4 '-C 6 H 4 -R 52' -, -R 51 '-CONR 4' -, -R 51 '-CONR 4' -C 6 H 4 -, -CONR 4 ' -, -CONR 4 '-C 6 H 4 -, -CONR 4 ' -, -CONR 4 '-C 6 H 4 - ,
  • X e ′ is more preferably -CONR 4 '-R 52' -, -CONR 4 '-C 6 H 4 -R 52' -, -X f -CONR 4 '-R 52' -, -X f -CONR 4 '-C 6 H 4 -R 52' -, -R 51 '-CONR 4' -, -R 51 '-CONR 4' -C 6 H 4 -, -CONR 4 ' -, -CONR 4 '-C 6 H 4 - , -X f -CONR 4 '- or -X f -CONR 4,' -C 6 H 4 -, It can be.
  • X e ′ include, for example, Single bond, Perfluoroalkylene groups having 1 to 6 carbon atoms (eg, -CF 2 -,-(CF 2 ) 2-, etc.), An alkylene group having 1 to 6 carbon atoms, -CF 2 -C 1-6 alkylene group, -CONH-, -CONH-CH 2- , -CONH- (CH 2 ) 2- -CONH- (CH 2 ) 3- , -CF 2 -CONH-, -CF 2 CONHCH 2- , -CF 2 CONH (CH 2 ) 2- , -CF 2 CONH (CH 2 ) 3- , -CON (CH 3 )-, -CON (CH 3 )-CH 2- , -CON (CH 3 )-(CH 2 ) 2- -CON (CH 3 )-(CH 2 ) 3- , -CF 2 -CON (CH 3 )-, -CF 2 -CON (CH 3 )-, -CF 2
  • preferable X e ′ is An alkylene group having 1 to 6 carbon atoms, Perfluoroalkylene groups having 1 to 6 carbon atoms (eg, -CF 2 -,-(CF 2 ) 2-, etc.), -CF 2 -C 1-6 alkylene group, -CONH-, -CONH-CH 2- , -CONH- (CH 2 ) 2- , -CONH- (CH 2 ) 3- , -CF 2 CONH-, -CF 2 CONHCH 2- , -CF 2 CONH (CH 2 ) 2- , -CF 2 CONH (CH 2 ) 3- , -CON (CH 3 )-, -CON (CH 3 ) -CH 2- , -CON (CH 3 )-(CH 2 ) 2- , -CON (CH 3 )-(CH 2 ) 3- , -CF 2 -CON (CH 3 )-, -CF 2 -CON (CH 3 ) CH 2- ,
  • more preferable X e ′ is -CONH-, -CONH-CH 2- , -CONH- (CH 2 ) 2- , -CONH- (CH 2 ) 3- , -CF 2 CONH-, -CF 2 CONHCH 2- , -CF 2 CONH (CH 2 ) 2- , -CF 2 CONH (CH 2 ) 3- , -CON (CH 3 )-, -CON (CH 3 ) -CH 2- , -CON (CH 3 )-(CH 2 ) 2- , -CON (CH 3 )-(CH 2 ) 3- , -CF 2 -CON (CH 3 )-, -CF 2 -CON (CH 3 ) CH 2- , -CF 2 -CON (CH 3 )-(CH 2 ) 2- , -CF 2 -CON (CH 3 )-(CH 2 ) 3- , -CH 2 -CONH-, -CH 2 -CONH-CH 2- ,
  • X e ′ is a single bond.
  • a group capable of binding PFPE to a substrate that is, a group enclosed in parentheses with ⁇ 1 in (A1) and (A2) is directly bonded.
  • X 1 is a group represented by the formula:-(R 16 ) x- (CFR 17 ) y- (CH 2 ) z- .
  • x, y and z are each independently an integer of 0 to 10, the sum of x, y and z is 1 or more, and the order of existence of each parenthesized parenthesis is in the formula Is optional.
  • R 16 are each independently at each occurrence, an oxygen atom, a phenylene, carbazolylene, -NR 18 - (wherein, R 18 represents a hydrogen atom or an organic group) or a divalent organic group is there.
  • R 16 is an oxygen atom or a divalent polar group.
  • the “lower alkyl group” is, for example, an alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl or n-propyl, which may be substituted by one or more fluorine atoms.
  • R 17 in each occurrence is independently a hydrogen atom, a fluorine atom or a lower fluoroalkyl group, preferably a fluorine atom.
  • the “lower fluoroalkyl group” is, for example, a fluoroalkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group, It is a pentafluoroethyl group, more preferably a trifluoromethyl group.
  • X 1 is preferably of the formula: — (O) x — (CF 2 ) y — (CH 2 ) z —, wherein x, y and z are as defined above, in parentheses The order of existence of each repeating unit enclosed is arbitrary group in the formula).
  • Examples of the group represented by the above formula:-(O) x- (CF 2 ) y- (CH 2 ) z- include, for example,-(O) x ' -(CH 2 ) z " -O-[(CH 2 ) 2) z '''-O-] z "", and - (O) x' - ( CF 2) y "- (CH 2) z” -O - [(CH 2) z '''-O- Z ′ ′ ′ ′ ′ (wherein, x ′ is 0 or 1, y ′ ′, z ′ ′ and z ′ ′ ′ are each independently an integer of 1 to 10, and z ′ ′ ′ is 0 or 1 The left end of these groups is bonded to the PFPE side.
  • X 1 is —O—CFR 20 — (CF 2 ) e ′ —.
  • the above R 20 each independently represents a fluorine atom or a lower fluoroalkyl group.
  • the lower fluoroalkyl group is, for example, a fluoroalkyl group having 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group or a pentafluoroethyl group, still more preferably trifluoro. It is a methyl group.
  • the above e's are each independently 0 or 1.
  • R 20 is a fluorine atom and e ′ is 1.
  • examples of X 1 groups include: [In the formula, Each R 41 independently represents a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C 1-6 alkoxy group, preferably a methyl group; In each X 1 group, any part of T is attached to PFPE of the molecular backbone: -CH 2 O (CH 2 ) 2- , -CH 2 O (CH 2 ) 3- , -CF 2 O (CH 2 ) 3- , -CH 2- , -(CH 2 ) 2- , -(CH 2 ) 3- , - (CH 2) 4 -, -CONH- (CH 2 ) 3- , -CON (CH 3 )-(CH 2 ) 3- , -CON (Ph)-(CH 2 ) 3- (wherein Ph means phenyl), or [Wherein, R 42 each independently represents a hydrogen atom, a C 1-6 alkyl group or a C 1-6 alkyl group or
  • T's are — (CH 2 ) n ′ ′ (n ′ ′ is an integer from 2 to 6) attached to the group opposite to the PFPE of the molecular main chain, and, if present, the remaining T may be each independently a methyl group, a phenyl group, a C 1-6 alkoxy group or a radical scavenging group or an ultraviolet absorbing group.
  • the radical scavenging group is not particularly limited as long as it can scavenge a radical generated upon irradiation with light, for example, benzophenones, benzotriazoles, benzoates, phenyl salicylates, crotonic acids, malonic esters, organoacrylates And residues of hindered amines, hindered phenols, or triazines.
  • the ultraviolet absorbing group is not particularly limited as long as it can absorb ultraviolet light, and examples thereof include benzotriazoles, hydroxybenzophenones, esters of substituted and unsubstituted benzoic acid or salicylic acid compounds, acrylates or alkoxycinnamates, oxamides, The residue includes oxanilides, benzoxazinones and benzoxazoles.
  • preferred radical scavenging groups or ultraviolet absorbing groups are Can be mentioned.
  • X 1 (and X 3 , X 5 and X 7 described below) may be a trivalent to dodecavalent organic group.
  • X 2 each independently represents a single bond or a divalent organic group at each occurrence.
  • X 2 is preferably an alkylene group having 1 to 20 carbon atoms, and more preferably — (CH 2 ) u — (wherein u is an integer of 0 to 2).
  • t is each independently an integer of 1 to 10. In a preferred embodiment, t is an integer of 1 to 6. In another preferred embodiment, t is an integer of 2 to 10, preferably an integer of 2 to 6.
  • Preferred compounds represented by the formulas (A1) and (A2) have the following formulas (A1 ′) and (A2 ′): [In the formula: Each PFPE is independently of the formula: - (OC 6 F 12) a - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f - (Wherein, a, b, c, d, e and f are each independently an integer of 0 or more and 200 or less, and the sum of a, b, c, d, e and f is at least 1).
  • a group represented by R f independently at each occurrence represents an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms;
  • R 13 independently at each occurrence independently represents a hydroxyl group or a hydrolysable group;
  • R 14 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms at each occurrence;
  • R 11 independently represents at each occurrence a hydrogen atom or a halogen atom;
  • R 12 independently at each occurrence represents a hydrogen atom or a lower alkyl group;
  • n1 is an integer of 1 to 3, preferably 3;
  • X 1 is independently at each occurrence, -O-CFR 20 - (CF 2) e '- a and;
  • R 20 each independently at each occurrence is a fluorine atom or a lower fluoroalkyl group; e
  • the compounds represented by the above formulas (A1) and (A2) can be obtained, for example, by introducing iodine into the terminal using a perfluoropolyether derivative corresponding to the Rf-PFPE- moiety as a raw material, and then introducing —CH 2 CR 12 (X It can be obtained by reacting a vinyl monomer corresponding to 2 -SiR 13 n1 R 14 3-n1 )-.
  • Rf, PFPE, R 13 , R 14 and n 1 are as defined for the above formulas (A1) and (A2).
  • each X 3 independently represents a single bond or a di- to 10-valent organic group.
  • the said X 3 is a perfluoropolyether part (namely, Rf-PFPE part or -PFPE- part) which mainly provides water repellency, surface slip property, etc. in the compound represented by Formula (B1) and (B2) And a silane moiety (specifically, -SiR 13 n 1 R 14 3-n 1 ) that provides the ability to bind to a substrate.
  • X 3 may be any organic group as long as the compounds represented by formulas (B1) and (B2) can stably exist.
  • X 3 represents X e .
  • X e is as defined above.
  • ⁇ 1 is an integer of 1 to 9
  • ⁇ 1 ′ is an integer of 1 to 9.
  • These ⁇ 1 and ⁇ 1 ′ can change according to the valence of X 3 .
  • the sum of ⁇ 1 and ⁇ 1 ′ is the same as the valence of X 3 .
  • X 3 is a 10-valent organic group
  • the sum of ⁇ 1 and ⁇ 1 ′ is 10, for example, ⁇ 1 is 9 and ⁇ 1 ′ is 1, ⁇ 1 is 5 and ⁇ 1 ′ is 5, or ⁇ 1 is 1 and ⁇ 1 'Can be nine.
  • ⁇ 1 and ⁇ 1 ′ are 1.
  • ⁇ 1 is a value obtained by subtracting 1 from the value of the valence of X 3 .
  • the above X 3 is preferably a divalent to heptavalent, more preferably a divalent to tetravalent, more preferably a divalent organic group.
  • X 3 is a divalent to tetravalent organic group
  • ⁇ 1 is 1 to 3
  • ⁇ 1 ′ is 1.
  • X 3 is a divalent organic group
  • ⁇ 1 is 1
  • ⁇ 1 ′ is 1.
  • the formulas (B1) and (B2) are represented by the following formulas (B1 ′) and (B2 ′).
  • Each PFPE is independently of the formula: - (OC 6 F 12) a - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f - (Wherein, a, b, c, d, e and f are each independently an integer of 0 or more and 200 or less, and the sum of a, b, c, d, e and f is at least 1).
  • R f independently at each occurrence represents an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms
  • R 13 independently at each occurrence independently represents a hydroxyl group or a hydrolysable group
  • R 14 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms at each occurrence
  • n1 is an integer of 1 to 3, preferably 3
  • X 3 is —CH 2 O (CH 2 ) 2 —, —CH 2 O (CH 2 ) 3 — or —CH 2 O (CH 2 ) 6 — It is a compound represented by
  • Examples of the X 3, is not particularly limited, examples thereof include the same as described for X 1.
  • preferred specific X 3 is Single bond, -CH 2 OCH 2- , -CH 2 O (CH 2 ) 2- , -CH 2 O (CH 2 ) 3- , -CH 2 O (CH 2 ) 6- , -CF 2 -CH 2 -O-CH 2- , -CF 2 -CH 2 -O- (CH 2 ) 2- , -CF 2 -CH 2 -O- (CH 2 ) 3- , -CF 2 -CH 2 -O- (CH 2 ) 6- -CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2- , -CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2- , -CH 2 O (CH 2) 3 Si (CH 3) 2 O (Si (CH 3) 2 O) 2 Si (CH 3) 2 (CH 2) 2 -, -CH 2 O (CH
  • X 3 is -CH 2 OCH 2- , -CH 2 O (CH 2 ) 2- , -CH 2 O (CH 2 ) 3- , -CH 2 O (CH 2 ) 6- , -CF 2 -CH 2 -O-CH 2- , -CF 2 -CH 2 -O- (CH 2 ) 2- , -CF 2 -CH 2 -O- (CH 2 ) 3- , -CF 2 -CH 2 -O- (CH 2 ) 6- -CH 2 OCF 2 CHFOCF 2- , -CH 2 OCF 2 CHFOCF 2 CF 2- , -CH 2 OCF 2 CHFOCF 2 CF 2- , -CH 2 OCF 2 CHFOCF 2 CF 2 CF 2- , -CH 2 OCH 2 CF 2 CF 2 OCF 2- , -CH 2 OCH 2 CF 2 CF 2 OCF 2- , -CH 2 OCH 2 CF 2 CF 2 OCF 2- , -CH 2 OCH 2 CF 2
  • X 3 is -CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 -C (O) NH-CH 2- , -CF 2 -CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 -C (O) NH-CH 2- , -CONH-, -CONH-CH 2- , -CONH- (CH 2 ) 2- , -CONH- (CH 2 ) 3- , -CONH- (CH 2 ) 6- , -CF 2 CONH-, -CF 2 CONHCH 2- , -CF 2 CONH (CH 2 ) 2- , -CF 2 CONH (CH 2 ) 3- , -CF 2 CONH (CH 2 ) 6- , -CON (CH 3 )-(CH 2 ) 3- , -CON (Ph)-(CH 2 ) 3- (wherein Ph means phenyl), -CON (CH 3 )-(CH 2 ) 6- , -CON (Ph)-(CH 2 ) 3-
  • X 3 represents X e ′ .
  • X e ′ is as defined above.
  • X e ′ is a single bond.
  • a group having a binding ability between PFPE and a substrate that is, a group enclosed in parentheses with ⁇ 1 in (B1) and (B2) is directly bonded.
  • At least two Si bonded to a hydroxyl group or a hydrolyzable group are present. That is, in the formulas (B1) and (B2), at least two structures of SiR 13 exist.
  • Preferred compounds represented by the formulas (B1) and (B2) have the following formulas (B1 ′) and (B2 ′): [In the formula: Each PFPE is independently of the formula: - (OC 6 F 12) a - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f - (Wherein, a, b, c, d, e and f are each independently an integer of 0 or more and 200 or less, and the sum of a, b, c, d, e and f is at least 1).
  • a group represented by R f independently at each occurrence represents an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms;
  • R 13 independently at each occurrence independently represents a hydroxyl group or a hydrolysable group;
  • R 14 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms at each occurrence;
  • n1 is an integer of 1 to 3, preferably 3;
  • X 3 is —CH 2 O (CH 2 ) 2 —, —CH 2 O (CH 2 ) 3 — or —CH 2 O (CH 2 ) 6 —.
  • the compounds represented by the above formulas (B1) and (B2) can be produced by a known method, for example, the method described in JP 2013-117012 A or its improved method.
  • Rf and PFPE are as defined for the above formulas (A1) and (A2).
  • each X 5 independently represents a single bond or a di- to 10-valent organic group.
  • the X 5 has the formula (C1) and in the compounds represented by (C2), perfluoropolyether portion which mainly provide water repellency and surface slipperiness, etc. (i.e., Rf-PFPE unit or -PFPE- parts)
  • Rf-PFPE unit or -PFPE- parts perfluoropolyether portion which mainly provide water repellency and surface slipperiness, etc.
  • silane unit that provides a binding capability to a substrate is understood as a linker linking.
  • X 5 may be any organic group as long as the compounds represented by formulas (C1) and (C2) can stably exist.
  • X 5 represents X e .
  • X e is as defined above.
  • ⁇ 1 is an integer of 1 to 9
  • ⁇ 1 ′ is an integer of 1 to 9.
  • These ⁇ 1 and ⁇ 1 ′ may change according to the valence of X 5 .
  • the sum of ⁇ 1 and ⁇ 1 ′ is the same as the valence of X 5 .
  • X 5 is a 10-valent organic group
  • the sum of ⁇ 1 and ⁇ 1 ′ is 10, for example, ⁇ 1 is 9 and ⁇ 1 ′ is 1, ⁇ 1 is 5 and ⁇ 1 ′ is 5, or ⁇ 1 is 1 and ⁇ 1 'Can be nine.
  • ⁇ 1 and ⁇ 1 ′ are 1.
  • ⁇ 1 is a value obtained by subtracting 1 from the value of the valence of X 5 .
  • the above X 5 is preferably a divalent to heptavalent, more preferably a divalent to tetravalent, more preferably a divalent organic group.
  • X 5 is a divalent to tetravalent organic group
  • ⁇ 1 is 1 to 3 and ⁇ 1 ′ is 1.
  • X 5 is a divalent organic group
  • ⁇ 1 is 1
  • ⁇ 1 ′ is 1.
  • the formulas (C1) and (C2) are represented by the following formulas (C1 ′) and (C2 ′).
  • Examples of X 5 include, but are not particularly limited to, the same ones as described for X 1 .
  • preferred specific X 5 is Single bond, -CH 2 OCH 2- , -CH 2 O (CH 2 ) 2- , -CH 2 O (CH 2 ) 3- , -CH 2 O (CH 2 ) 6- , -CF 2 -CH 2 -O-CH 2- , -CF 2 -CH 2 -O- (CH 2 ) 2- , -CF 2 -CH 2 -O- (CH 2 ) 3- , -CF 2 -CH 2 -O- (CH 2 ) 6- -CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2- , -CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2- , -CH 2 O (CH 2) 3 Si (CH 3) 2 O (Si (CH 3) 2 O) 2 Si (CH 3) 2 (CH 2) 2 -, -CH 2 O (CH
  • X 5 is preferably -CH 2 OCH 2- , -CH 2 O (CH 2 ) 2- , -CH 2 O (CH 2 ) 3- , -CH 2 O (CH 2 ) 6- , -CF 2 -CH 2 -O-CH 2- , -CF 2 -CH 2 -O- (CH 2 ) 2- , -CF 2 -CH 2 -O- (CH 2 ) 3- , -CF 2 -CH 2 -O- (CH 2 ) 6- -CH 2 OCF 2 CHFOCF 2- , -CH 2 OCF 2 CHFOCF 2 CF 2- , -CH 2 OCF 2 CHFOCF 2 CF 2 CF 2- , -CH 2 OCH 2 CF 2 CHFOCF 2 CF 2 CF 2- , -CH 2 OCH 2 CF 2 CF 2 OCF 2- , -CH 2 OCH 2 CF 2 CF 2 OCF 2- , -CH 2 OCH 2 CF 2 CF 2 OCF 2- , -
  • X 5 is -CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 -C (O) NH-CH 2- , -CF 2 -CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 -C (O) NH-CH 2- , -CONH-, -CONH-CH 2- , -CONH- (CH 2 ) 2- , -CONH- (CH 2 ) 3- , -CONH- (CH 2 ) 6- , -CF 2 CONH-, -CF 2 CONHCH 2- , -CF 2 CONH (CH 2 ) 2- , -CF 2 CONH (CH 2 ) 3- , -CF 2 CONH (CH 2 ) 6- , -CON (CH 3 )-(CH 2 ) 3- , -CON (Ph)-(CH 2 ) 3- (wherein Ph means phenyl), -CON (CH 3 )-(CH 2 ) 6- , -CON (Ph)-(CH 2 ) 3-
  • X 5 represents X e ′ .
  • X e ′ is as defined above.
  • X e ′ is a single bond.
  • a group capable of binding PFPE to a substrate that is, a group which is attached with ⁇ 1 and bracketed in (C1) and (C2) is directly bonded.
  • R a independently represents -Z 3 -SiR 71 p 1 R 72 q 1 R 73 r 1 at each occurrence.
  • each Z 3 independently represents an oxygen atom or a divalent organic group.
  • the above Z 3 is preferably a divalent organic group, and forms a siloxane bond with the Si atom at the end of the molecular main chain in the formula (C1) or the formula (C2) (Si atom to which R a is bonded) Do not include what you do.
  • the above Z 3 is preferably a C 1-6 alkylene group,-(CH 2 ) g -O- (CH 2 ) h- (wherein, g is an integer of 1 to 6 and h is 1 to 6) Or -phenylene- (CH 2 ) i- (wherein i is an integer of 0 to 6), and more preferably a C 1-3 alkylene group.
  • These groups may be substituted, for example, by one or more substituents selected from a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group. .
  • the above Z 3 is more preferably a linear or branched alkylene group, and still more preferably a linear alkylene group.
  • the number of carbon atoms constituting the above-mentioned alkylene group of Z 3 is preferably in the range of 1 to 6, and more preferably in the range of 1 to 3.
  • the alkylene group is as described above.
  • R 71 independently represents Ra ' at each occurrence.
  • R a ′ is as defined in R a .
  • the maximum number of Sis linked in a linear fashion via a Z 3 group is five. That is, in the above R a , when at least one R 71 is present, two or more Si atoms linearly linked through the Z 3 group are present in R a , but through such Z 3 group Thus, the number of Si atoms linked in a linear manner is at most five. Note that the "through Z 3 group in R a number of Si atoms linearly linked" is equal to -Z 3 -Si- repetition number of which is connected to a linear during R a become.
  • * means a site to be bonded to Si in the main chain, ... indicates that a predetermined group other than Z 3 Si is bonded, that is, all three bonds of Si atoms are ... In this case, it means the end of the repetition of Z 3 Si.
  • the number on the right of Si means the appearance number of Si linearly linked via Z 3 group counted from *. That is, the chain in which the Z 3 Si repeat is completed in Si 2 is “the number of Si atoms linearly linked via the Z 3 group in R a ” is 2, similarly, Si 3 , And Si 4 and Si 5 in which the Z 3 Si repeat ends are “number of Si atoms linearly linked via Z 3 group in R a ” of 3, 4 and 5, respectively Is one.
  • a plurality of Z 3 Si chains are present in R a , but they do not have to have the same length, and may have any length.
  • the number of Si atoms linearly linked via the Z 3 group in R a is 1 (left equation) or 2 (all the chains) in all chains. Right).
  • the number of Si atoms linearly linked via the Z 3 group in R a is 1 or 2, preferably 1.
  • each R 72 independently at each occurrence represents a hydroxyl group or a hydrolysable group.
  • the "hydrolyzable group” is as defined above.
  • R 72 is —OR, wherein R represents a substituted or unsubstituted C 1-3 alkyl group, more preferably a methyl group.
  • R 73 each independently represents a hydrogen atom or a lower alkyl group at each occurrence.
  • the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
  • '(if R a' is absent, R a) terminal of R a in R a in the above q1 is preferably 2 or more, for example 2 or 3, more preferably 3.
  • At least one of the terminal parts of R a is -Si (-Z 3 -SiR 72 q1 R 73 r1 ) 2 or -Si (-Z 3 -SiR 72 q1 R 73 r1 ) 3 , preferably- It may be Si (-Z 3 -SiR 72 q1 R 73 r1 ) 3 .
  • (- Z 3 -SiR 72 q1 R 73 r1) units is preferably (-Z 3 -SiR 72 3).
  • all the terminal parts of R a may be -Si (-Z 3 -SiR 72 q1 R 73 r1 ) 3 , preferably -Si (-Z 3 -SiR 72 3 ) 3 .
  • At least one q1 is an integer of 1 to 3, that is, at least one R 72 is present.
  • At least two Si bonded to a hydroxyl group or a hydrolyzable group are present. That is, there are at least two structures of SiR 72 and / or SiR b .
  • each R b independently represents a hydroxyl group or a hydrolysable group.
  • R includes an unsubstituted alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group and an isobutyl group; and a substituted alkyl group such as a chloromethyl group.
  • an alkyl group particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
  • the hydroxyl group is not particularly limited, but may be formed by hydrolysis of a hydrolyzable group. More preferably, R b is —OR, wherein R represents a substituted or unsubstituted C 1-3 alkyl group, more preferably a methyl group.
  • R c independently at each occurrence represents a hydrogen atom or a lower alkyl group.
  • the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
  • k1 is each independently an integer of 0 to 3 at each occurrence; 11 is each independently an integer of 0 to 3 at each occurrence; m1 is each independently at each occurrence Is an integer of 0 to 3.
  • SiR a k1 R b l1 R c m1 each, the sum of k1, l1 and m1 is 3.
  • k1 is preferably 1 to 3, and more preferably 3.
  • the compounds represented by the above formulas (C1) and (C2) have, for example, an unsaturated bond at the end after introducing a hydroxyl group at the end using a perfluoropolyether derivative corresponding to the Rf-PFPE- moiety as a raw material A group is introduced, a group having this unsaturated bond is reacted with a silyl derivative having a halogen atom, and further a hydroxyl group at the end of the silyl group is introduced followed by a group having an unsaturated bond, and the last introduced unsaturated It can be obtained by reacting a group having a bond with a silyl derivative. For example, it can be synthesized as described in WO 2014/069592.
  • Rf and PFPE are as defined in the above formulas (A1) and (A2).
  • each X 7 independently represents a single bond or a di- to 10-valent organic group.
  • the said X 7 is a perfluoropolyether part (namely, Rf-PFPE part or -PFPE- part) which mainly provides water repellency, surface slip property, etc. in the compound represented by Formula (D1) and (D2) And a portion that provides the ability to bind to a substrate (ie, a group that is enclosed in parentheses with a ⁇ 1 attached thereto).
  • the X 7 may be any organic group as long as the compounds represented by the formulas (D1) and (D2) can stably exist.
  • X 7 represents X e .
  • X e is as defined above.
  • ⁇ 1 is an integer of 1 to 9
  • ⁇ 1 ′ is an integer of 1 to 9.
  • These ⁇ 1 and ⁇ 1 ′ can change according to the valence of X 7 .
  • the sum of ⁇ 1 and ⁇ 1 ′ is the same as the valence of X 7 .
  • X 7 is a 10-valent organic group
  • the sum of ⁇ 1 and ⁇ 1 ′ is 10, for example, ⁇ 1 is 9 and ⁇ 1 ′ is 1, ⁇ 1 is 5 and ⁇ 1 ′ is 5, or ⁇ 1 is 1 and ⁇ 1 'Can be nine.
  • ⁇ 1 and ⁇ 1 ′ are 1.
  • ⁇ 1 is the value obtained by subtracting 1 from the valence of X 7.
  • the above-mentioned X 7 is preferably a divalent to heptavalent, more preferably a divalent to tetravalent, more preferably a divalent organic group.
  • X 7 is a divalent to tetravalent organic group, ⁇ 1 is 1 to 3 and ⁇ 1 ′ is 1.
  • X 7 is a divalent organic group
  • ⁇ 1 is 1
  • ⁇ 1 ′ is 1.
  • the formulas (D1) and (D2) are represented by the following formulas (D1 ′) and (D2 ′).
  • Examples of X 7 include, but are not particularly limited to, the same ones as those described for X 1 .
  • preferred specific X 7 is Single bond, -CH 2 OCH 2- , -CH 2 O (CH 2 ) 2- , -CH 2 O (CH 2 ) 3- , -CH 2 O (CH 2 ) 6- , -CF 2 -CH 2 -O-CH 2- , -CF 2 -CH 2 -O- (CH 2 ) 2- , -CF 2 -CH 2 -O- (CH 2 ) 3- , -CF 2 -CH 2 -O- (CH 2 ) 6- -CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2- , -CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2- , -CH 2 O (CH 2) 3 Si (CH 3) 2 O (Si (CH 3) 2 O) 2 Si (CH 3) 2 (CH 2) 2 -, -CH 2 O (CH
  • more preferred specific X 7 is -CH 2 OCH 2- , -CH 2 O (CH 2 ) 2- , -CH 2 O (CH 2 ) 3- , -CH 2 O (CH 2 ) 6- , -CF 2 -CH 2 -O-CH 2- , -CF 2 -CH 2 -O- (CH 2 ) 2- , -CF 2 -CH 2 -O- (CH 2 ) 3- , -CF 2 -CH 2 -O- (CH 2 ) 6- -CH 2 OCF 2 CHFOCF 2- , -CH 2 OCF 2 CHFOCF 2 CF 2- , -CH 2 OCF 2 CHFOCF 2 CF 2 CF 2- , -CH 2 OCH 2 CF 2 CHFOCF 2 CF 2 CF 2- , -CH 2 OCH 2 CF 2 CF 2 OCF 2- , -CH 2 OCH 2 CF 2 CF 2 OCF 2- , -CH 2 OCH 2 CF 2 CF 2 OCF 2- ,
  • X 7 is -CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 -C (O) NH-CH 2- , -CF 2 -CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 -C (O) NH-CH 2- , -CONH-, -CONH-CH 2- , -CONH- (CH 2 ) 2- , -CONH- (CH 2 ) 3- , -CONH- (CH 2 ) 6- , -CF 2 CONH-, -CF 2 CONHCH 2- , -CF 2 CONH (CH 2 ) 2- , -CF 2 CONH (CH 2 ) 3- , -CF 2 CONH (CH 2 ) 6- , -CON (CH 3 )-(CH 2 ) 3- , -CON (Ph)-(CH 2 ) 3- (wherein Ph means phenyl), -CON (CH 3 )-(CH 2 ) 6- , -CON (Ph)-(CH 2 ) 3-
  • X 7 represents X e ′ .
  • X e ′ is as defined above.
  • X e ′ is a single bond.
  • a group capable of binding PFPE to a substrate that is, a group enclosed in parentheses with ⁇ 1 in (D1) and (D2)
  • a bonding strength between PFPE and a group enclosed in parentheses with ⁇ 1 becomes stronger.
  • carbon atoms directly bonded to PFPE that is, carbon atoms bonded to R d , R e and R f in the parenthesized group attached with ⁇ 1 have less charge bias, and as a result, the above carbon Nucleophilic reactions and the like are unlikely to occur at atoms, and the compound is considered to be stably bound to the substrate.
  • Such a structure is advantageous because it can further improve the friction durability of the layer formed by the PFPE silane compound.
  • R d independently represents -Z 4 -CR 81 p 2 R 82 q 2 R 83 r 2 at each occurrence.
  • Z 4 independently represents an oxygen atom or a divalent organic group at each occurrence.
  • the above Z 4 is preferably a C 1-6 alkylene group, — (CH 2 ) g —O— (CH 2 ) h — (wherein, g is an integer of 0 to 6, for example, an integer of 1 to 6) H is an integer of 0 to 6, for example, an integer of 1 to 6) or -phenylene- (CH 2 ) i- (wherein i is an integer of 0 to 6), and Preferably, it is a C 1-3 alkylene group. These groups may be substituted, for example, by one or more substituents selected from a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group. .
  • R 81 independently represents R d ′ at each occurrence.
  • R d ′ is as defined the R d .
  • Cs linked in a linear fashion via a Z 4 group are at most 5 pieces. That is, in the above Rd , when at least one R 81 is present, two or more C atoms linked in a straight line via the Z 4 group are present in R d , and such a C 4 group is intervened.
  • the maximum number of C atoms linked in a straight chain is five. Note that the "through Z 4 group in R d number of C atoms linearly linked" is equal to the number of repetitions of -Z 4 -C- being linearly linked in a R d Become.
  • the number of C atoms linearly linked via the Z 4 group in R d is 1 (left) or 2 (the left expression) in all chains. Right).
  • the number of C atoms to be linked via Z 4 groups R d linearized is one or two, preferably one.
  • R 82 independently represents -Y-SiR 85 n 2 R 86 3- n 2 at each occurrence.
  • Y's each independently represent a divalent organic group at each occurrence.
  • Y C 1-6 alkylene group, - (CH 2) g ' -O- (CH 2) h' - (wherein, g 'is from 0 to 6 integer, for example from 1 to 6 H is an integer of 0 to 6, for example, an integer of 1 to 6, or -phenylene- (CH 2 ) i ' -(wherein i' is an integer of 0 to 6) ).
  • These groups may be substituted, for example, by one or more substituents selected from a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group. .
  • Y can be a C 1-6 alkylene group or -phenylene- (CH 2 ) i ' -.
  • the light resistance in particular the UV resistance, may be higher.
  • R 85 each independently represents a hydroxyl group or a hydrolyzable group at each occurrence.
  • hydrolyzable group examples include those similar to formulas (C1) and (C2).
  • R 85 is —OR, wherein R represents a substituted or unsubstituted C 1-3 alkyl group, more preferably an ethyl group or a methyl group, in particular a methyl group.
  • R 86 each independently represents a hydrogen atom or a lower alkyl group at each occurrence.
  • the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
  • n2 independently represents an integer of 0 to 3, preferably an integer of 1 to 3, more preferably 2 or 3, and particularly preferably 3 for each (-Y-SiR 85 n2 R 86 3-n2 ) unit It is.
  • R 83 each independently represents a hydrogen atom, a hydroxyl group or a lower alkyl group at each occurrence.
  • the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
  • the sum of p2, q2 and r2 is 3 for each (-Z 4 -CR 81 p2 R 82 q2 R 83 r 2 ).
  • '(if R d' is absent, R d) end of R d in R d in the above q2 is preferably 2 or more, for example 2 or 3, more preferably 3.
  • At least one of the terminal parts of R d is preferably —C (—Y—SiR 85 n 2 R 86 3- n 2 ) 2 or —C (—Y—SiR 85 n 2 R 86 3- n 2 ) 3 , preferably May be -C (-Y-SiR 85 n2 R 86 3-n2 ) 3 .
  • (- Y-SiR 85 n2 R 86 3-n2) units is preferably (-Y-SiR 85 3).
  • the distal end of the R d1 are all -C (-Y-SiR 85 n2 R 86 3-n2) 3, may be preferably -C (-Y-SiR 85 3) 3.
  • R e independently represents -Y-SiR 85 n 2 R 86 3- n 2 at each occurrence.
  • Y, R 85 , R 86 and n 2 are as defined in R 82 above.
  • R f each independently represents a hydrogen atom, a hydroxyl group or a lower alkyl group at each occurrence.
  • the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
  • k2 is independently an integer of 0 to 3 at each occurrence; 12 is an integer of 0 to 3 independently at each occurrence; m2 is independently at each occurrence Is an integer of 0 to 3. However, the sum of k2, l2 and m2 is 3.
  • At least one k2 is 2 or 3, preferably 3.
  • k2 is 2 or 3, preferably 3.
  • l2 is 2 or 3, preferably 3.
  • two or more groups represented by -Y-SiR 85 are present. More preferably, one or more carbon atoms bonded to two or more -Y-SiR 85 are present. That is, it is preferable that one or more groups represented by —C— (Y—SiR 85 n 2 R 86 3- n 2 ) 2 exist (in the formula, n 2 is an integer of 1 to 3).
  • n2 is an integer of 1 to 3, and at least one q2 is 2 or 3, or at least one 12 is 2 or 3. That is, there are at least two -Y-SiR 85 n2 R 86 3-n2 groups in the formula.
  • the PFPE-containing silane compound represented by Formula (D1) or Formula (D2) can be produced by combining known methods.
  • the compound represented by the formula (D1 ′) in which X 7 is divalent can be produced as follows, but not limited thereto.
  • the above-mentioned PFPE-containing silane compound is not particularly limited, but may have a number average molecular weight of 5 ⁇ 10 2 to 1 ⁇ 10 5 . Within this range, having a number average molecular weight of 2,000 to 30,000, more preferably 2,500 to 12,000, still more preferably 3,000 to 6,000 is from the viewpoint of friction durability. preferable. In the present invention, the number average molecular weight is a value measured by 19 F-NMR.
  • the PFPE-containing silane compound is a compound represented by any one of formulas (C1), (C2), (D1) or (D2) above.
  • the surface treatment agent may be diluted with a solvent.
  • the water content contained in the said solvent is 20 mass ppm or less.
  • the water content can be measured using the Karl Fischer method. By such a water content, the storage stability of the surface treatment agent can be improved.
  • the surface treatment agent may contain other components in addition to the PFPE-containing silane compound.
  • Such other components are not particularly limited, but for example, (non-reactive) fluoropolyether compounds which can be understood as fluorine-containing oils, preferably perfluoro (poly) ether compounds (hereinafter referred to as “containing” "Fluorine oil”), silicone compound (non-reactive) which may be understood as silicone oil (hereinafter referred to as "silicone oil”), catalyst, lower alcohol, transition metal, halide ion, non-covalently in molecular structure Examples thereof include compounds containing an atom having an electron pair.
  • R f 5 represents a C 1-16 alkyl group (preferably a C 1-16 perfluoroalkyl group) which may be substituted by one or more fluorine atoms
  • R f 6 represents Rf 5 and Rf 6 each represents a C 1-16 alkyl group (preferably a C 1-16 perfluoroalkyl group) which may be substituted by one or more fluorine atoms, a fluorine atom or a hydrogen atom; And more preferably each independently a C 1-3 perfluoroalkyl group.
  • a ′, b ′, c ′ and d ′ each represent the number of repeating units of four types of perfluoro (poly) ethers constituting the main skeleton of the polymer, and are each independently an integer of 0 or more and 300 or less;
  • the sum of a ′, b ′, c ′ and d ′ is at least 1, preferably 1 to 300, more preferably 20 to 300.
  • the order in which each repeating unit enclosed in parentheses with a subscript a ', b', c 'or d' is given is arbitrary in the formula.
  • - (OC 4 F 8) - is, - (OCF 2 CF 2 CF 2 CF 2) -, - (OCF (CF 3) CF 2 CF 2) -, - (OCF 2 CF (CF 3) CF 2) -, - (OCF 2 CF 2 CF (CF 3)) -, - (OCF 2 C (CF 3) 2) -, - (OCF (CF 3 ) CF (CF 3 ) —, — (OCF (C 2 F 5 ) CF 2 ) — and — (OCF 2 CF (C 2 F 5 )) —, which may be any of - (OCF 2 CF 2 CF 2 CF 2) - a.
  • - (OC 3 F 6) - is, - (OCF 2 CF 2 CF 2) -, - (OCF (CF 3) CF 2) - and - (OCF 2 CF (CF 3 )) - be any of Well, preferably-(OCF 2 CF 2 CF 2 )-.
  • -(OC 2 F 4 )- may be either-(OCF 2 CF 2 )-or-(OCF (CF 3 ))-, but is preferably-(OCF 2 CF 2 )-.
  • Examples of the perfluoro (poly) ether compound represented by the above general formula (1) include a compound represented by any one of the following general formulas (1a) and (1b) (one or a mixture of two or more) May be mentioned.
  • Rf 5 and Rf 6 are as described above; in formula (1a), b ′ ′ is an integer of 1 or more and 100 or less; in formula (1b), a ′ ′ and b ′ ′ are Each is independently an integer of 1 or more and 30 or less, and c ′ ′ and d ′ ′ are each independently an
  • the fluorine-containing oil may have a number average molecular weight of 1,000 to 30,000.
  • the number average molecular weight of the compound represented by the formula (1a) is preferably 2,000 to 8,000. By having such a number average molecular weight, high surface slipperiness can be obtained.
  • the number average molecular weight of the compound represented by formula (1b) is 3,000 to 8,000. In another embodiment, the number average molecular weight of the compound represented by formula (1b) is 8,000 to 30,000.
  • the fluorine-containing oil is, for example, 0 to 500 parts by mass, preferably 0 to 100 parts by mass, more preferably 1 to 50 parts by mass, further preferably 100 parts by mass of the PFPE-containing silane compound. It may be contained in 1 to 5 parts by mass.
  • the fluorine-containing oil may be a compound represented by the general formula Rf′-F (wherein Rf ′ is a C 5-16 perfluoroalkyl group).
  • Rf ′ is a C 5-16 perfluoroalkyl group
  • a chloro trifluoro ethylene oligomer may be sufficient.
  • the compound represented by Rf′-F and the chlorotrifluoroethylene oligomer are preferable in that high affinity is obtained with the above perfluoro (poly) ether group-containing silane compound in which Rf is a C 1-16 perfluoroalkyl group. .
  • the fluorine-containing oil contributes to the improvement of the surface slipperiness of the surface treatment layer.
  • silicone oil for example, a linear or cyclic silicone oil having a siloxane bond of 2,000 or less can be used.
  • Linear silicone oils may be so-called straight silicone oils and modified silicone oils.
  • Straight silicone oils include dimethyl silicone oil, methyl phenyl silicone oil and methyl hydrogen silicone oil.
  • modified silicone oil include those obtained by modifying a straight silicone oil with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol and the like.
  • the cyclic silicone oil may, for example, be a cyclic dimethylsiloxane oil.
  • such silicone oil is, for example, 0 to 50 parts by mass, preferably 0 to 50 parts by mass, with respect to 100 parts by mass of the PFPE-containing silane compound (in the case of two or more, the total of them, the same applies hereinafter). It may be contained in 5 parts by mass.
  • the silicone oil contributes to the improvement of the surface slipperiness of the surface treatment layer.
  • the catalyst examples include acids (eg, acetic acid, trifluoroacetic acid etc.), bases (eg, ammonia, triethylamine, diethylamine etc.), transition metals (eg, Ti, Ni, Sn etc.) and the like.
  • acids eg, acetic acid, trifluoroacetic acid etc.
  • bases eg, ammonia, triethylamine, diethylamine etc.
  • transition metals eg, Ti, Ni, Sn etc.
  • the catalyst promotes the hydrolysis and dehydration condensation of the fluorine-containing silane compound and promotes the formation of the surface treatment layer.
  • Examples of the lower alcohol as the other component include alcohol compounds having 1 to 6 carbon atoms.
  • Chloride ion etc. are mentioned as said halide ion.
  • Compounds containing an atom having a noncovalent electron pair in the above molecular structure include diethylamine, triethylamine, aniline, pyridine, hexamethylphosphoramide, N, N-diethylacetamide, N, N-diethylformamide, N, N Dimethylacetamide, N-methylformamide, N, N-dimethylformamide, N-methylpyrrolidone, tetramethylurea, dimethylsulfoxide (DMSO), tetramethylene sulfoxide, methylphenyl sulfoxide, diphenyl sulfoxide and the like. Of these compounds, dimethyl sulfoxide or tetramethylene sulfoxide is preferably used.
  • tetraethoxysilane methyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltriacetoxysilane and the like can also be mentioned.
  • the above-mentioned surface treatment agent is a compound containing the above-mentioned other component fluorine-containing oil, silicone oil, catalyst, lower alcohol, transition metal, halide ion, atom having non-covalent electron pair in molecular structure Does not contain
  • the surface treatment agent may be impregnated into a porous material such as a porous ceramic material, metal fiber such as steel wool, and made into a pellet.
  • a porous material such as a porous ceramic material, metal fiber such as steel wool, and made into a pellet.
  • the said pellet can be used for vacuum evaporation, for example.
  • Formation of the base material containing the layer which consists of the said surface treatment agent, and a base layer can be manufactured as follows, for example.
  • the base layer is as described above.
  • any layer (or film) such as a hard coat layer or an antireflective layer is formed on the surface (the outermost layer) of the base layer, these layers (or films) are formed of these layers (or films)
  • the surface of the target surface referred to as a treated layer in this paragraph
  • the ion cleaning may be performed, for example, by irradiating the surface of the layer to be treated with an ion beam using oxygen gas and / or an inert gas (eg, argon, xenon, nitrogen, etc.).
  • An ion gun can be used for the irradiation.
  • organic substances and the like are removed from the surface of the layer to be treated, and the antireflective layer can be more firmly adhered to the layer to be treated.
  • the ion cleaning may be performed using, for example, a mixed gas of oxygen gas and argon gas.
  • a mixed gas of oxygen gas and argon gas As the mixed gas, a gas containing 5 to 100 cc / min of oxygen gas and 5 to 100 cc / min of argon gas is preferably used, 20 to 50 cc / min of oxygen gas, and 10 to 40 cc / min of argon gas. It is more preferable to use a gas containing it, and it is further preferable to use a gas containing 30 to 40 cc / min of oxygen gas and 10 to 20 cc / min of argon gas.
  • the irradiation with the ion beam is preferably performed for 10 to 600 seconds, more preferably for 50 to 400 seconds, and still more preferably for 200 to 300 seconds.
  • the ion cleaning is performed by irradiating the ion beam for 200 to 300 seconds using a gas containing 30 to 40 cc / min of oxygen gas and 10 to 20 cc / min of argon gas.
  • the antireflective layer may be formed by vapor deposition (e.g., vacuum evaporation) (e.g., on the surface of glass or the like).
  • the thickness of the antireflective layer e.g, a silicon dioxide film
  • the thickness of the antireflective layer can be, for example, less than 10 nm, specifically, 3 to 8 nm, more specifically, 4.5 nm. With such a thickness, it is possible to form a substrate having a surface treatment layer having better friction durability.
  • the surface of the base layer is ion cleaned.
  • the ion cleaning may be performed, for example, by irradiating the surface of the base layer with an ion beam using oxygen gas and / or an inert gas (eg, argon, xenon, nitrogen, etc.).
  • An ion gun can be used for the irradiation.
  • the ion cleaning of the surface of the base layer may be performed, for example, using a mixed gas of oxygen gas and argon gas.
  • a mixed gas of oxygen gas and argon gas As the mixed gas, a gas containing 5 to 100 cc / min of oxygen gas and 5 to 100 cc / min of argon gas is preferably used, 20 to 50 cc / min of oxygen gas, and 10 to 40 cc / min of argon gas. It is more preferable to use a gas containing it, and it is further preferable to use a gas containing 25 to 40 cc / min of oxygen gas and 15 to 30 cc / min of argon gas.
  • the irradiation with the ion beam is preferably performed for 1 to 200 seconds, more preferably for 1 to 100 seconds, and still more preferably for 5 to 40 seconds.
  • the ion cleaning of the surface of the base layer is performed by irradiating an ion beam for 5 to 40 seconds with a gas containing 25 to 40 cc / min of oxygen gas and 15 to 30 cc / min of argon gas.
  • a film of the surface treatment agent is formed on the surface of the base layer after ion cleaning, and this film is post-treated as necessary, thereby forming a surface treatment layer from the surface treatment agent.
  • the film formation of the surface treatment agent can be carried out by applying the above-mentioned surface treatment agent to the surface of the base layer so as to cover the surface.
  • the coating method is not particularly limited. For example, wet coating and dry coating can be used.
  • wet coating methods include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating and similar methods.
  • dry coating methods include vapor deposition (usually vacuum evaporation), sputtering, CVD and similar methods.
  • deposition method usually, vacuum deposition method
  • CVD method include plasma-CVD, optical CVD, thermal CVD and similar methods.
  • the heat treatment is preferably performed at 60 ° C. or higher, more preferably 100 ° C. or higher, and still more preferably 140 ° C. or higher.
  • the heat treatment is preferably performed at 300 ° C. or less, more preferably 250 ° C. or less, and still more preferably 200 ° C. or less.
  • the heat treatment is preferably performed at a temperature in the range of 60 to 300 ° C., more preferably at a temperature in the range of 80 to 200 ° C., and still more preferably at a temperature in the range of 100 to 180 ° C.
  • the heat treatment is preferably performed for 5 minutes or more, more preferably for 15 minutes or more, and still more preferably for 30 minutes or more.
  • the heat treatment is preferably performed for 600 minutes or less, more preferably for 300 minutes or less, still more preferably for 90 minutes or less, and may be performed for 70 minutes or less.
  • the heat treatment is preferably performed for 5 to 300 minutes, more preferably for 15 to 120 minutes, and still more preferably for 30 to 90 minutes.
  • the heat treatment is preferably performed at a temperature in the range of 60 to 200 ° C. for 5 to 200 minutes, and more preferably at a temperature in the range of 100 to 180 ° C. for 15 to 90 minutes.
  • the ion cleaning of the base layer is carried out using a gas containing 20 to 40 cc / min of oxygen gas and 10 to 30 cc / min of argon gas at a temperature in the range of 10 to 40.degree. Irradiation is carried out for ⁇ 300 seconds, then a layer consisting of a surface treatment agent is formed, and heat treatment is carried out at a temperature in the range of 100 ⁇ 180 ° C. for 15 ⁇ 90 minutes.
  • the surface treatment is preferably performed using ethanol. Specifically, 1 to 2 ml of ethanol per one (specifically, one Kimwipe (120 mm ⁇ 215 mm)) prepared by spotting and mixing Kim Wipes (registered trademark) Wiper S-200 (manufactured by Nippon Paper Industries Co., Ltd.) Wipe the surface of the formed film with a mixture of stains). More specifically, the surface of the formed film is wiped back and forth 20 times using Kim wipe wiped with ethanol. Thereafter, the surface of the film is wiped off using a Kimwipe (registered trademark) wiper S-200 prepared separately. By performing such treatment, the substrate of the present invention can contribute to the improvement of the abrasion resistance.
  • the surface treatment layer derived from the film of the surface treatment agent is formed on the surface of the base layer.
  • the surface treatment layer thus obtained has low chargeability.
  • this surface treatment layer also depends on the composition of the surface treatment agent to be used, but prevents the adhesion of stains such as fingerprints, etc., depending on the water repellency, oil repellency and stain resistance. ) Waterproofness (prevents water ingress to electronic parts etc.), surface slipperiness (or lubricity, for example, the wipeability of dirt such as fingerprints, excellent touch feeling to fingers), friction durability, transparency, etc. And may be suitably utilized as a functional thin film.
  • the base material of this aspect can be used also for the optical material which has a surface treatment layer in the outermost layer.
  • optical material in addition to optical materials related to displays as exemplified later, a wide variety of optical materials are preferably mentioned: For example, cathode ray tube (CRT; eg, TV, personal computer monitor), liquid crystal display, plasma display, Displays such as organic EL displays, inorganic thin film EL dot matrix displays, rear projection displays, fluorescent display tubes (VFDs), field emission displays (FEDs) or protective plates of those displays, or reflections on those surfaces Those with a protective film treatment.
  • CTR cathode ray tube
  • LCD liquid crystal display
  • FEDs field emission displays
  • An article having a surface treatment layer obtained by the present aspect is not particularly limited, but may be an optical member.
  • optical members include: lenses such as glasses; front protective plates for displays such as PDPs and LCDs; anti-reflection plates; polarizing plates; anti-glare plates; devices such as mobile phones and personal digital assistants Touch panel sheet or its cover glass; disc surface of optical disc such as Blu-ray (registered trademark) disc, DVD disc, CD-R, MO, etc .; optical fiber; display surface of watch, etc.
  • the article having the surface treatment layer obtained by the present aspect may be a medical device or a medical material.
  • the thickness of the surface treatment layer is not particularly limited. In the case of an optical member, the thickness of the surface treatment layer is in the range of 1 to 50 nm, preferably 1 to 30 nm, more preferably 1 to 15 nm. Optical performance, surface slipperiness, friction durability and antifouling property It is preferable from the point of
  • An article having a surface treatment layer formed of the above surface treatment agent preferably has a surface resistance value of 10 12 ⁇ or less, more preferably 10 10 ⁇ or less, still more preferably 10 9 ⁇ or less, for example 10 8 ⁇ or less. It can. By lowering the surface resistance, the chargeability of the article can be reduced.
  • an article having a surface treatment layer formed of the above surface treatment agent may have a surface resistance value of preferably 10 6 ⁇ or more, more preferably 10 7 ⁇ or more, and still more preferably 10 8 ⁇ or more. By increasing the surface resistance value, for example, in a capacitive touch panel or the like, the operation of the touch panel can be secured.
  • an article having a surface treatment layer formed of the surface treatment agent may have a surface resistance value of 10 6 ⁇ or more and 10 12 ⁇ or less, more preferably 10 8 ⁇ or more and 10 10 ⁇ or less.
  • the base material of this embodiment is A substrate having a surface treatment layer formed of a compound containing a perfluoropolyether group on the surface, Test cloth (here, the test cloth is an artificial sweat consisting of 5.5 g of trisodium phosphate, 10 g of sodium chloride, 3.1 g of lactic acid, 5 g of lysine and 100 ml of distilled water under an atmosphere of 21 ° C. and a humidity of 65%.
  • the measured value of the static contact angle of water after the number of times of reciprocation of the friction element in the friction test in which the friction element is reciprocated on the surface at a speed of 40 mm / sec is 80 degrees or more.
  • description overlapping with the description of the embodiment 1, such as the friction test and the static contact angle of water, may be omitted.
  • the base material of this embodiment preferably has a measured value of static contact angle of water at 4,000 reciprocations of the friction element, preferably 84 degrees or more, more preferably 85 degrees or more, still more preferably 90 degrees or more It is.
  • a measured value of static contact angle of water at 4,000 reciprocations of the friction element preferably 84 degrees or more, more preferably 85 degrees or more, still more preferably 90 degrees or more It is.
  • the water repellency on the surface is good.
  • such substrates may be particularly useful in applications where friction may occur.
  • the base material of this aspect has a high measured value of the contact angle before the friction test.
  • the contact angle of the substrate before the friction test is preferably 80 degrees or more, more preferably 100 degrees or more, particularly preferably 105 degrees or more, and still more preferably 110 degrees or more.
  • the ratio of the static contact angle of water at 4,000 reciprocations of the friction element to the measured value of the static contact angle of water at the reciprocation number of times of the friction element may be 0.70 or more, 0.80 It may be above.
  • the upper limit value of the ratio is not particularly limited, but may be, for example, 1.00 or less, specifically 0.98 or less.
  • the dynamic friction coefficient measured in accordance with ASTM D4917 is preferably less than 0.050, and more preferably less than 0.035.
  • the substrate of this embodiment further comprises A test cloth (here, the test cloth is trisodium phosphate) under an atmosphere of 21 ° C. and a humidity of 65% on the surface irradiated with ultraviolet light of wavelength 300 nm to 400 nm at an irradiance of 62 W / m 2 for 300 hours Covered with INNOWEP's ABREX (R) standard cotton soiling textile FINE, soaked with artificial sweat consisting of 5.5 g, sodium chloride 10 g, lactic acid 3.1 g, lysine 5 g and 100 ml distilled water.
  • a test cloth here, the test cloth is trisodium phosphate
  • the number of reciprocations of the friction element is zero. 1000 times, 2000 times and 3000 times (however, the number of reciprocation times is a measure of the static contact angle of water Based on the measured value of static contact angle of water after UV irradiation (degree) to the number of round trips (times) in which the value is first measured less than 50 degrees)
  • the slope of the linear approximation straight line is greater than -0.0222.
  • the UV irradiation test is as described in Aspect 1 above.
  • the substrate of the present embodiment may include a layer consisting of a surface treatment agent on at least one surface. That is, it is preferable that the base material of this aspect contains the layer which consists of surface treatment agents, and a base layer.
  • the surface treatment layer and the base layer are as described in Aspect 1 above.
  • the base material of this embodiment is A substrate having a surface treatment layer formed of a compound containing a perfluoropolyether group on the surface, A test cloth (here, the test cloth is trisodium phosphate) under an atmosphere of 21 ° C. and a humidity of 65% on the surface irradiated with ultraviolet light of wavelength 300 nm to 400 nm at an irradiance of 62 W / m 2 for 300 hours Covered with INNOWEP's ABREX (R) standard cotton soiling textile FINE, soaked with artificial sweat consisting of 5.5 g, sodium chloride 10 g, lactic acid 3.1 g, lysine 5 g and 100 ml distilled water.
  • the number of reciprocations of the friction element is zero. 1000 times, 2000 times and 3000 times (however, the number of reciprocation times is a measure of the static contact angle of water Based on the measured value of static contact angle of water after UV irradiation (degree) to the number of round trips (times) in which the value is first measured less than 50 degrees)
  • the slope of the linear approximation straight line is greater than -0.0222.
  • description overlapping with the description of the embodiment 1, such as the friction test and the static contact angle of water, may be omitted.
  • the base material of this embodiment has a static contact angle of water measured at a frequency of 50 degrees or more after 3000 reciprocations of the friction element in the friction test.
  • the base material of this aspect has a high measured value of the contact angle before the friction test.
  • the contact angle of the substrate before the friction test is preferably 80 degrees or more, more preferably 100 degrees or more, particularly preferably 105 degrees or more, and still more preferably 110 degrees or more.
  • the ratio of the static contact angle of water at the number of reciprocation times of the friction element to the measured value of the static contact angle of water at the reciprocation times of the friction element is 0.35 or more Or 0.50 or more.
  • the upper limit value of the ratio is not particularly limited, but may be, for example, 1.00 or less, specifically 0.98 or less.
  • the dynamic friction coefficient measured in accordance with ASTM D4917 is preferably less than 0.050, and more preferably less than 0.035.
  • the substrate of the present embodiment may include a layer consisting of a surface treatment agent on at least one surface. That is, it is preferable that the base material of this aspect contains the layer which consists of surface treatment agents, and a base layer.
  • the surface treatment layer and the base layer are as described in Aspect 1 above.
  • the present invention will be more specifically described through the following examples, but the present invention is not limited to these examples.
  • the order in which the repeating units (CF 2 O) and (CF 2 CF 2 O) constituting the perfluoropolyether are present is arbitrary.
  • all the chemical formulas shown below show average compositions.
  • the PFPE-containing silane compounds used in the examples and comparative examples are as follows.
  • Example 1 Compound (A) was dissolved in hydrofluoroether (Novec HFE 7200 manufactured by 3M) to a concentration of 20 wt% to prepare a surface treatment agent 1.
  • the surface treatment agent 1 was vacuum deposited on a chemically strengthened glass ("Gorilla" glass, 0.7 mm thick, manufactured by Corning).
  • Compound (A) was evaporated (containing 0.8 mg).
  • the chemically strengthened glass with vapor deposition film was heat treated at a temperature of 150 ° C. for 60 minutes, and finally, surface treated with ethanol to form a surface treated layer, and a substrate having a surface treated layer on the surface was formed. .
  • Example 5 A surface-treated layer was formed in the same manner as in Example 1 except that compounds (B) to (E) were used instead of compound (A), and a substrate having a surface-treated layer on the surface was formed. .
  • the surface treatment agent 1 was vacuum deposited on a chemically strengthened glass ("Gorilla" glass, 0.7 mm thick, manufactured by Corning).
  • the surface treatment agent 1 that is, containing 0.8 mg of the compound (A) was vapor-deposited on one surface of the chemically strengthened glass (68 mm ⁇ 142 mm). Thereafter, the chemically strengthened glass with a deposited film is allowed to stand for 24 hours in an atmosphere of a temperature of 21 ° C. and a humidity of 65%, and finally surface treated with ethanol to form a surface treated layer, and a surface treated layer on the surface.
  • the chemically strengthened glass with a deposited film is allowed to stand for 24 hours in an atmosphere of a temperature of 21 ° C. and a humidity of 65%, and finally surface treated with ethanol to form a surface treated layer, and a surface treated layer on the surface.
  • Friction Durability Test The friction durability test was conducted as follows.
  • the static contact angle of water of the surface treatment layer was measured in a state where nothing was touched to the surface yet (friction number 0).
  • a substrate having a surface treatment layer was attached to the surface obtained in the above-mentioned Example or Comparative Example in an INNOWEP ABREX (registered trademark) tester (model: standard ABREX (registered trademark)).
  • the surface of the silicone friction pad provided in the ABREX® tester was covered with a test cloth.
  • As a test cloth one obtained by immersing ABREX (registered trademark) standard cotton soiling textile FINE) manufactured by INNOWEP in artificial sweat of the following composition was used.
  • a load of 5 N was applied to the above-mentioned friction element, and in the state where the load was applied, the friction element was reciprocated at a speed of 40 mm / sec and a friction distance of 20 mm.
  • the substrates formed in Examples 1 to 5 were found to have excellent slip properties.
  • a super xenon weather meter type SX75 (Suga Test Instruments Co., Ltd.) is used as the base material having a surface treatment layer on the surface formed in the above-mentioned Examples and Comparative Examples.
  • the irradiation conditions were: irradiance of 62 W / m 2 at a wavelength of 300 nm to 400 nm, the black panel temperature of the base was 55 ° C., and the distance between the lamp and the surface of the base was 29 cm.
  • the static contact angle of the water of the surface treatment layer was measured in a state where nothing was touched yet on the surface (friction number of times 0).
  • ABREX (registered trademark) tester model: standard ABREX (registered trademark) manufactured by INNOWEP
  • a substrate having a surface treatment layer on the surface obtained in the above examples and comparative examples and then UV
  • the substrate subjected to the irradiation test was attached.
  • the surface of the silicone friction element provided in the ABREX (registered trademark) testing machine was covered with a test cloth (ABREX (registered trademark) standard cotton soiling textile FINE manufactured by INNOWEP) immersed in the artificial sweat of the composition described above.
  • a load of 5 N was applied to the above-mentioned friction element, and in the state where the load was applied, the friction element was reciprocated at a speed of 40 mm / sec and a friction distance of 20 mm.
  • the substrate of the present invention can be used in various fields where water repellency is required on the surface of the substrate.

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Abstract

The present invention provides a base material having, provided to the surface, a surface treatment layer formed from a perfluoropolyether group-containing compound, wherein the gradient of a linear approximation straight line, which is created on the basis of measurement values (degrees) of the static contact angle of water relative to the number of times (times) a friction element is moved back and forth, namely 0 times, 1000 times, 2000 times, 3000 times, and 4000 times (with the caveat that, at the maximum number of times, the measurement value of the static contact angle of water is initially less than 80 degrees), in a friction test in which the friction element is moved back and forth on the surface of the base material at a speed of 40 mm/sec, in an atmosphere having a temperature of 21˚C and a humidity of 65%, while applying a load to the friction element such that a load of 5N is applied to the base material, is over -0.0096. The friction element is formed from silicone which has been covered with a testing fabric (ABREX (registered trademark) standard cotton soiling textile FINE which is made by INNOWEP, and which has been soaked in a synthetic sweat comprising 5.5 g of trisodium phosphate, 10 g of sodium chloride, 3.1 g of lactic acid, 5g of lysine, and 100 ml of distilled water).

Description

基材Base material
　本発明は、基材、特に表面における撥水性の良好な基材に関する。 The present invention relates to a substrate, particularly to a substrate having good water repellency on the surface.
　従来、表面における優れた撥水性を有する基材が、求められている。例えば、特許文献１には、表面における優れた撥水性を有する基材として、ある種のパーフルオロポリエーテル基含有ポリマー変性シランで処理された基材が記載されている。 Heretofore, a substrate having excellent water repellency on the surface has been sought. For example, Patent Document 1 describes a substrate treated with a certain perfluoropolyether group-containing polymer-modified silane as a substrate having excellent water repellency on the surface.
特開２０１６－２０４６５６号公報JP, 2016-204656, A
　特許文献１に記載のような表面処理基材は、例えばタッチパネル、携帯電話もしくはスマートフォンの操作画面などの用途において用いられているが、これらの用途では摩擦耐久性が求められ、近年その要求は高まっている。しかしながら、特許文献１に記載のような表面処理基材は、次第に高まる摩擦耐久性向上の要求に応えるには、もはや必ずしも十分とは言えない。本発明は、十分な撥水性を有し、特に摩擦を繰り返し与えられた場合であっても、撥水性を維持できる基材を提供することを目的とする。 Although the surface-treated substrate as described in Patent Document 1 is used in applications such as touch panels, operation screens of mobile phones or smartphones, for example, friction durability is required for these applications, and in recent years the demand has increased. ing. However, the surface-treated substrate as described in Patent Document 1 is no longer sufficient to meet the increasing demand for improvement in friction durability. An object of the present invention is to provide a substrate having sufficient water repellency, and in particular, capable of maintaining water repellency even when friction is repeatedly applied.
　本発明の第１の要旨によれば、本発明の基材は
　表面にパーフルオロポリエーテル基含有化合物から形成された表面処理層を有する基材であって、
　２１℃および湿度６５％の雰囲気下において、試験用布（リン酸三ナトリウム５．５ｇ、塩化ナトリウム１０ｇ、乳酸３．１ｇ、リシン５ｇおよび蒸留水１００ｍｌからなる人工汗を浸漬させた、ＩＮＮＯＷＥＰ社製のＡＢＲＥＸ（登録商標）　ｓｔａｎｄａｒｄ　ｃｏｔｔｏｎ　ｓｏｉｌｉｎｇ　ｔｅｘｔｉｌｅ　ＦＩＮＥ）で覆われたシリコーンよりなる摩擦子に、基材に対して５Ｎの荷重がかかるように、負荷をかけながら、該摩擦子を４０ｍｍ／秒の速度で表面上を往復する摩擦試験における、該摩擦子の往復回数０回、１０００回、２０００回、３０００回、および４０００回（ただし、該往復回数は、水の静的接触角の測定値が最初に８０度未満になった回数を最大とする。）での往復回数（回）に対する水の静的接触角の測定値（度）に基づいて作成される線形近似直線の勾配が－０．００９６超である。 According to the first aspect of the present invention, the substrate of the present invention is a substrate having a surface treatment layer formed of a compound containing a perfluoropolyether group on the surface,
INNOWEP, in which an artificial sweat consisting of test cloth (5.5 g of trisodium phosphate, 10 g of sodium chloride, 10 g of sodium chloride, 3.1 g of lactic acid, 5 g of lysine and 100 ml of distilled water) was soaked under an atmosphere of 21 ° C. and a humidity of 65%. Of a friction member made of silicone covered with ABREX (R) standard cotton soiling textile FINE) with a load of 5 N applied to the substrate, the speed of the friction member being 40 mm / sec. In the friction test that reciprocates on the surface, the number of reciprocations of the friction element in the friction test is 0, 1000, 2000, 3000 and 4000 (however, the number of reciprocations is the first measurement of static contact angle of water) Measure the static contact angle of water (the degree) to the number of round trips (times) at which the number of It is -0.0096 than the slope of the linear approximation line that is created based on.
　本発明の第２の要旨によれば、本発明の基材は、
　表面にパーフルオロポリエーテル基含有化合物から形成された表面処理層を有する基材であって、
　２１℃および湿度６５％の雰囲気下において、試験用布（リン酸三ナトリウム５．５ｇ、塩化ナトリウム１０ｇ、乳酸３．１ｇ、リシン５ｇおよび蒸留水１００ｍｌからなる人工汗を浸漬させた、ＩＮＮＯＷＥＰ社製のＡＢＲＥＸ（登録商標）　ｓｔａｎｄａｒｄ　ｃｏｔｔｏｎ　ｓｏｉｌｉｎｇ　ｔｅｘｔｉｌｅ　ＦＩＮＥ）で覆われたシリコーンよりなる摩擦子に、基材に対して５Ｎの荷重がかかるように、負荷をかけながら、該摩擦子を４０ｍｍ／秒の速度で表面上を往復する摩擦試験における、該摩擦子の往復回数４０００回における水の静的接触角の測定値が、８０度以上である。 According to a second aspect of the invention, the substrate of the invention is
A substrate having a surface treatment layer formed of a compound containing a perfluoropolyether group on the surface,
INNOWEP, in which an artificial sweat consisting of a test cloth (5.5 g of trisodium phosphate, 10 g of sodium chloride, 10 g of sodium chloride, 3.1 g of lactic acid, 5 g of lysine and 100 ml of distilled water) was soaked under an atmosphere of 21 ° C. and a humidity of 65%. Of a friction member made of silicone covered with ABREX (R) standard cotton soiling textile FINE) with a load of 5 N applied to the substrate, the speed of the friction member being 40 mm / sec. The measured value of the static contact angle of water after 4000 cycles of reciprocation of the friction element in the friction test which reciprocates on the surface is 80 degrees or more.
　本発明の第３の要旨によれば、本発明の基材は
　表面にパーフルオロポリエーテル基含有化合物から形成された表面処理層を有する基材であって、
　波長３００ｎｍ～４００ｎｍの紫外線が、放射照度６２Ｗ／ｍ２で３００時間照射された表面において、２１℃および湿度６５％の雰囲気下において、試験用布（リン酸三ナトリウム５．５ｇ、塩化ナトリウム１０ｇ、乳酸３．１ｇ、リシン５ｇおよび蒸留水１００ｍｌからなる人工汗を浸漬させた、ＩＮＮＯＷＥＰ社製のＡＢＲＥＸ（登録商標）　ｓｔａｎｄａｒｄ　ｃｏｔｔｏｎ　ｓｏｉｌｉｎｇ　ｔｅｘｔｉｌｅ　ＦＩＮＥ）で覆われたシリコーンよりなる摩擦子に、基材に対して５Ｎの荷重がかかるように、負荷をかけながら、該摩擦子を４０ｍｍ／秒の速度で往復する摩擦試験における、該摩擦子の往復回数０回、１０００回、２０００回、および３０００回（ただし、該往復回数は、水の静的接触角の測定値が最初に測定値が５０度未満になった回数を最大とする。）での往復回数（回）に対する水の静的接触角の測定値（度）に基づいて作成される線形近似直線の勾配が－０．０２２２超である。 According to a third aspect of the present invention, the substrate of the present invention is a substrate having a surface treatment layer formed of a compound containing a perfluoropolyether group on the surface,
Test cloth (5.5 g of trisodium phosphate, 10 g of sodium chloride, at an atmosphere of 21 ° C. and a humidity of 65% on a surface irradiated with ultraviolet light of wavelength 300 nm to 400 nm at an irradiance of 62 W / m 2 for 300 hours A friction member made of silicone covered with INNOWEP's ABREX (R) standard cotton soiling textile FINE) impregnated with artificial sweat consisting of 3.1 g of lactic acid, 5 g of lysine and 100 ml of distilled water In the friction test in which the friction element is reciprocated at a speed of 40 mm / sec while applying a load such that a load of 5 N is applied, the number of reciprocations of the friction element is zero, 1000, 2000 and 3000 The number of reciprocations is that the static water contact angle measurement value is not 50 degrees at first. The maximum number of times it becomes.) The slope of the linear approximation line is created on the basis of the reciprocating frequency (measurement of the static contact angle of water to times) (degrees) at is -0.0222 greater.
　本発明によれば、十分な撥水性を有し、特に摩擦を繰り返し与えられた場合であっても、撥水性を維持できる基材が提供される。 According to the present invention, there is provided a substrate which has sufficient water repellency, and in particular can maintain water repellency even when friction is repeatedly applied.
　以下、本発明の基材について説明する。 Hereinafter, the base material of the present invention will be described.
（態様１）
　本態様の基材は、
　表面にパーフルオロポリエーテル基含有化合物から形成された表面処理層を有する基材であって、
　２１℃および湿度６５％の雰囲気下において、試験用布で覆われたシリコーンよりなる摩擦子に、基材に対して５Ｎの荷重がかかるように、負荷をかけながら、該摩擦子を４０ｍｍ／秒の速度で表面上を往復する摩擦試験における、該摩擦子の往復回数０回、１０００回、２０００回、３０００回、および４０００回（ただし、該往復回数は、水の静的接触角の測定値が最初に８０度未満になった回数を最大とする。）での往復回数（回）に対する水の静的接触角の測定値（度）に基づいて作成される線形近似直線の勾配が－０．００９６超である。 (Aspect 1)
The base material of this embodiment is
A substrate having a surface treatment layer formed of a compound containing a perfluoropolyether group on the surface,
Under an atmosphere of 21 ° C. and a humidity of 65%, a friction member made of silicone covered with a test cloth is loaded with a load of 5 N to the base material while applying a load of 40 mm / sec. In the friction test which reciprocates on the surface at the speed of 0, the number of reciprocations of the friction element 0, 1000, 2000, 3000 and 4000 (however, the number of reciprocations is a measurement value of the static contact angle of water) The slope of the linear approximation straight line created based on the measured value of static contact angle of water (degrees) to the number of reciprocations (times) when the first becomes less than 80 degrees)-0 It is over .0096.
　上記試験用布としては、リン酸三ナトリウム５．５ｇ、塩化ナトリウム１０ｇ、乳酸３．１ｇ、リシン５ｇおよび蒸留水１００ｍｌからなる人工汗を浸漬させた、ＩＮＮＯＷＥＰ社製のＡＢＲＥＸ（登録商標）　ｓｔａｎｄａｒｄ　ｃｏｔｔｏｎ　ｓｏｉｌｉｎｇ　ｔｅｘｔｉｌｅ　ＦＩＮＥを用いる。上記試験用布は、一辺の長さが８ｃｍであり、該一辺に直交する他辺の長さが５ｃｍの矩形である。 As the above test cloth, ABREX (registered trademark) standard cotton manufactured by INNOWEP, in which artificial sweat consisting of 5.5 g of trisodium phosphate, 10 g of sodium chloride, 3.1 g of lactic acid, 5 g of lysine and 100 ml of distilled water is immersed. Use soiling textile FINE. The test cloth is a rectangle having a length of 8 cm on one side and a length of 5 cm on the other side orthogonal to the one side.
　上記ＩＮＮＯＷＥＰ社製のＡＢＲＥＸ（登録商標）　ｓｔａｎｄａｒｄ　ｃｏｔｔｏｎ　ｓｏｉｌｉｎｇ　ｔｅｘｔｉｌｅ　ＦＩＮＥは、糸密度が、縦糸：２７０±１０本／ｄｍ、横糸：２７０±１０本／ｄｍ、かつ、糸番手が、縦糸：２９５±１０ｄｔｘ、横糸：２９５±１０ｄｔｘ、かつ、撚り数が、縦糸：２９５±１０Ｔ/ｍ、横糸：２９５±１０Ｔ/ｍ、かつ密度が１７０±１０ｇ／ｍ２のコットンからなり、ＩＥＣ規格６０４５６のＡ．３．１．２に記載の組成物により汚染された布である。 Yarn density: 270 ± 10 yarns / dm, weft yarn: 270 ± 10 yarns / dm, yarn count: warp yarn: 295 ± 10 dtx , Yarn: 295 ± 10 dtx, and the number of twists is cotton of warp: 295 ± 10 T / m, weft: 295 ± 10 T / m, and density is 170 ± 10 g / m 2 , and A. It is a cloth contaminated by the composition described in 3.1.2.
　上記ＩＮＮＯＷＥＰ社製のＡＢＲＥＸ（登録商標）　ｓｔａｎｄａｒｄ　ｃｏｔｔｏｎ　ｓｏｉｌｉｎｇ　ｔｅｘｔｉｌｅ　ＦＩＮＥの表面粗さ（Ｒａ）は、１４～２１μｍであってもよく、１６～１９μｍであってもよい。 The surface roughness (Ra) of the ABREX (registered trademark) standard cotton soiling textile FINE manufactured by INNOWEP may be 14 to 21 μm or 16 to 19 μm.
　上記試験用布は、上記布に上記組成の人工汗が十分に浸透した状態にある。このような試験用布は、例えば、上記組成の人工汗に上記布を浸漬することによって得られる。上記布は、例えば、１０秒～１０分間上記人工汗に浸漬される。なお、上記試験用布は、上記組成の人工汗に浸漬後の布を用いることができ、試験用布に付着している余分の人工汗の除去などを行う必要はない。 The test cloth is in a state in which the artificial sweat of the composition has sufficiently penetrated into the cloth. Such a test cloth can be obtained, for example, by immersing the cloth in artificial sweat of the above composition. The cloth is dipped in the artificial sweat, for example, for 10 seconds to 10 minutes. In addition, the cloth after immersion can be used for the said test cloth in the artificial sweat of the said composition, and it is not necessary to perform the removal etc. of the extra artificial sweat adhering to the test cloth.
　上記試験用布は、辺の長さが８ｃｍおよび５ｃｍの矩形に切断したものを用いる。上記の大きさの試験用布には、約１ｍｌ（例えば、０．５～２．０ｍｌ）の人工汗が含まれ得る。 The test cloth used is cut into rectangles of 8 cm and 5 cm in side length. A test cloth of the above size may contain about 1 ml (eg, 0.5 to 2.0 ml) of artificial sweat.
　上記シリコーンは、試験用布を介して基材と接触する。即ち、上記摩擦子の基材と接触する面には、試験用布が存在する。上記試験用布と上記シリコーンとは、例えば、通常行われ得る手段（例えば接着剤、紐や輪ゴム）を用いて固定されていてもよい。但し、上記試験用布および上記シリコーンは、摩擦子と基材との接触面において凹凸部（例えば、試験用布の偏在により生じ得るシワ、たわみなど）は存在しないように固定されている。 The silicone contacts the substrate through the test cloth. That is, a test cloth is present on the surface of the friction element in contact with the base material. The above-mentioned test cloth and the above-mentioned silicone may be fixed, for example, using means (for example, adhesives, cords or rubber bands) which can be usually performed. However, the above-mentioned test cloth and the above-mentioned silicone are fixed so that uneven parts (for example, wrinkles, deflections, etc. which may occur due to uneven distribution of the test cloth) do not exist on the contact surface between the friction element and the substrate.
　上記試験用布で覆われたシリコーンよりなる摩擦子としては、例えば、直径２．５ｃｍの半球状のものを用いることができる。この場合、試験において基材を摩擦するのは、上記半球状の突起部（凸部）である。 As a friction element made of silicone covered with the test cloth, for example, a hemispherical one having a diameter of 2.5 cm can be used. In this case, it is the hemispherical projections (convex portions) that rub the substrate in the test.
　上記摩擦試験は、上記摩擦子を基材の表面に沿うように反復移動させて行う。具体的には、上記摩擦試験は、２１℃および湿度６５％の雰囲気下において、基材の表面に、上記試験用布で覆われた摩擦子を設置し、基材に対して５Ｎの荷重がかかるように、負荷をかけながら、該摩擦子を４０ｍｍ／秒の速度で、所定の距離（例えば２０ｍｍ）を往復させることによって行う。上記摩擦試験は、例えば、基材の表面が鉛直方向に沿って延在するように設置して行う。 The friction test is performed by repeatedly moving the friction element along the surface of the substrate. Specifically, in the friction test, a friction element covered with the test cloth is placed on the surface of the base under an atmosphere of 21 ° C. and a humidity of 65%, and a load of 5 N is applied to the base Thus, while applying a load, the friction element is reciprocated by a predetermined distance (for example, 20 mm) at a speed of 40 mm / sec. The friction test is performed, for example, by placing the surface of the substrate extending in the vertical direction.
　上記摩擦試験に用いる機械としては、ＩＮＮＯＷＥＰ社製ＡＢＲＥＸ（登録商標）試験機（型式：ｓｔａｎｄａｒｄ　ＡＢＲＥＸ（登録商標））を挙げることができる。 As a machine used for the said friction test, ABREX (trademark) test equipment (model: standard ABREX (trademark)) by INNOWEP can be mentioned.
　以下において、上記摩擦試験をより具体的に説明する。 Hereinafter, the above-mentioned friction test will be described more specifically.
　まず、摩擦試験前の基材について、その表面における水の静的接触角の測定値（往復回数０回における水の静的接触角の測定値）を得る。 First, for the substrate before the friction test, a measurement value of the static contact angle of water on the surface (measurement value of the static contact angle of water at zero reciprocation times) is obtained.
　その後、基材の該表面において、摩擦試験を実施する。摩擦子の往復回数（即ち摩擦回数）１０００回毎に、基材の表面における水の静的接触角を測定し、水の静的接触角の測定値が８０度未満となるまで、摩擦試験を続ける。 Thereafter, a friction test is performed on the surface of the substrate. Measure the static contact angle of water on the surface of the substrate every 1000 times of the number of reciprocation of the friction element (ie, the number of frictions), and perform the friction test until the measured value of the static contact angle of water is less than 80 degrees. to continue.
　より具体的には、摩擦子の往復回数が１０００回となったときに、基材の表面における水の静的接触角の測定値を求める。上記１０００回の測定値が８０度未満である場合には、摩擦試験を中止する。上記１０００回の測定値が８０度以上である場合には、さらに摩擦試験を行い、摩擦子の往復回数がさらに１０００回（即ち、計２０００回）となったときに、基材の表面における水の静的接触角の測定値を求める。上記２０００回の測定値が８０度未満の場合には、摩擦試験を中止する。上記２０００回の測定値が８０度以上の場合には、さらに摩擦試験を行い、摩擦子の往復回数がさらに１０００回（即ち、計３０００回）の場合の水の静的接触角の測定値を求める。上記３０００回の測定が８０度未満の場合には、摩擦試験を中止する。上記３０００回の測定値が８０度以上の場合には、さらに摩擦試験を行い、摩擦子の往復回数が４０００回の場合の水の静的接触角の測定値を求める。以下、水の静的接触角が８０度未満となるまで摩擦試験を行い、摩擦子の往復回数１０００回毎に水の静的接触角の測定値を求める。 More specifically, when the number of reciprocations of the friction element reaches 1000, the measured value of the static contact angle of water on the surface of the substrate is determined. If the 1000 measurements are less than 80 degrees, the friction test is discontinued. If the measured value of 1000 times is 80 degrees or more, a friction test is further performed, and when the number of reciprocations of the friction element is further 1000 times (that is, 2000 times in total), the water on the surface of the substrate is Determine the static contact angle measurement value of If the 2000 measurements are less than 80 degrees, the friction test is discontinued. In the case where the above 2000 measurements are 80 degrees or more, a friction test is carried out to further measure the static contact angle of water when the number of reciprocations of the friction element is 1000 (ie, a total of 3000). Ask. If the above 3000 measurements are less than 80 degrees, the friction test is discontinued. If the measured value of 3000 times is 80 degrees or more, the friction test is further performed to obtain the measured value of the static contact angle of water when the number of reciprocations of the friction element is 4000 times. Thereafter, a friction test is performed until the static contact angle of water is less than 80 degrees, and the measured value of the static contact angle of water is obtained every 1000 reciprocations of the friction element.
　次いで、上記の摩擦試験において得られた水の静的接触角の測定値と、摩擦子の往復回数との関係を求める。 Next, the relationship between the measured value of the static contact angle of water obtained in the above-described friction test and the number of reciprocations of the friction element is determined.
　一の態様において、摩擦子の往復回数が最大４０００回における、摩擦子の往復回数ｘ（回）と水の静的接触角の測定値との関係を求める。具体的には、該摩擦子の往復回数０回、１０００回、２０００回、３０００回、および４０００回での往復回数に対する水の静的接触角の測定値（度）に基づいて作成される線形近似直線Ｆｘ＝ηｘ＋θ（ηおよびθは定数）を求める。 In one aspect, the relationship between the number of reciprocations of the friction element x (times) and the measured value of the static contact angle of water when the number of reciprocations of the friction element is at most 4000 times is determined. Specifically, a linear created based on the measurement value (degree) of the static contact angle of water with respect to the number of reciprocation times of the friction element 0, 1000, 2000, 3000 and 4000 times. An approximate straight line F x = ηx + θ (where η and θ are constants) is determined.
　ただし、該往復回数は、水の静的接触角の測定値が最初に８０度未満になった回数を最大とする。具体的には、摩擦子の往復回数１０００回における水の静的接触角の測定値が８０度未満である場合には、往復回数０回および１０００回における水の静的接触角の測定値を用いて線形近似直線を形成する。摩擦子の往復回数１０００回における水の静的接触角の測定値が８０度以上であり、往復回数２０００回における水の静的接触角の測定値が８０度未満である場合には、往復回数０回、１０００回、および２０００回における水の静的接触角の測定値を用いて線形近似直線を形成する。摩擦子の往復回数２０００回における水の静的接触角の測定値が８０度以上であり、往復回数３０００回における水の静的接触角の測定値が８０度未満である場合には、往復回数０回、１０００回、２０００回および３０００回の値を用いて線形近似直線を形成する。摩擦子の往復回数３０００回における水の静的接触角の測定値が８０度以上である場合には、往復回数０回、１０００回、２０００回、３０００回および４０００回における水の静的接触角の測定値を用いて線形近似直線を形成する。 However, the number of reciprocations makes the number of measurements of static contact angle of water first less than 80 degrees. Specifically, when the measured value of the static contact angle of water after the number of reciprocation times of the friction element is less than 80 degrees, the measured value of the static contact angle of water at the number of reciprocations of 0 times and 1000 times Use to form a linear approximation straight line. If the measured value of the static contact angle of water after 1,000 times of reciprocation times of the friction element is 80 degrees or more and the measured value of the static contact angle of water after 2000 reciprocations times is less than 80 degrees A linear approximation straight line is formed using the static contact angle measurements of water at 0 times, 1000 times and 2000 times. If the measured value of the static contact angle of water at 2000 times of reciprocation times of the friction element is 80 degrees or more and the measured value of the static contact angle of water at 3000 times of reciprocation times is less than 80 degrees The linear approximation line is formed using the value of 0 times, 1000 times, 2000 times and 3000 times. When the measured value of the static contact angle of water at 3000 times of reciprocation of the friction element is 80 degrees or more, the static contact angle of water at 0 times, 1000 times, 2000 times, 3000 times and 4000 times of reciprocation times A linear approximation line is formed using the measured values of.
　本態様の基材においては、上記の線形近似直線の勾配ηが－０．００９６超であり、好ましくは－０．００８５以上であり、より好ましくは－０．００８０以上、さらに好ましくは－０．００７０以上、特に好ましくは－０．００６０以上である。本態様の基材は、上記摩擦試験を行った後においても、その表面における水の静的接触角の低下が少なく、撥水性が低下しにくい。上記勾配ηの上限は特に限定されないが、例えば－０．０００１未満であってもよい。 In the base material of the present embodiment, the gradient η of the linear approximation straight line is -0.0096 or more, preferably -0.0085 or more, more preferably -0.0080 or more, still more preferably -0. It is at least, particularly preferably at least −0.0060. Even after the above-mentioned friction test, the base material of this embodiment has less decrease in the static contact angle of water on the surface thereof, and the water repellency is less likely to be reduced. Although the upper limit of the gradient η is not particularly limited, it may be, for example, less than -0.0001.
　上記線形近似直線におけるθは、例えば８０以上であり、具体的には９０以上であり、より具体的には１００以上であり、さらに具体的には１１０以上であり、１１４以上であってもよい。 Θ in the linear approximation straight line is, for example, 80 or more, specifically 90 or more, more specifically 100 or more, and more specifically 110 or more, and may be 114 or more. .
　別の態様において、摩擦子の往復回数が最大１００００回における、摩擦子の往復回数ｘ（回）と水の静的接触角の測定値との関係を求める。具体的には、該摩擦子の往復回数ｘ（回）に対する水の静的接触角の測定値（度）に基づいて作成される線形近似直線Ｆ”ｘ＝η”ｘ＋θ”（η”およびθ”は定数）を求める。ただし、該往復回数は、水の静的接触角の測定値が最初に８０度未満になった回数を最大とする。摩擦試験、水の静的接触角の測定値については、上記と同意義である。 In another aspect, the relationship between the number of reciprocations of the friction element x (times) and the measured value of the static contact angle of water when the number of reciprocations of the friction element is up to 10000 is determined. Specifically, a linear approximate straight line F ′ ′ x = η′′x + θ ′ ′ (η ′ ′ and θ) created based on the measured value (degree) of the static contact angle of water with respect to the number of reciprocations x (times) of the friction element Is a constant. However, the number of reciprocations is maximized the number of measurements of static contact angle of water initially less than 80 degrees. Friction test, measurement of static contact angle of water Is as defined above.
　本態様の基材においては、上記の線形近似直線の勾配η”が、好ましくは－０．００９６超であり、より好ましくは－０．００８５以上であり、さらに好ましくは－０．００８０以上であり、特に好ましくは－０．００７０以上であり、さらに好ましくは－０．００６０以上である。即ち、本態様の基材は、上記摩擦試験を行った後においても、その表面における水の静的接触角の低下が少なく、撥水性が低下しにくい。上記勾配η”の上限は特に限定されないが、例えば－０．０００１未満であってもよい。 In the base material of the present embodiment, the gradient η ′ ′ of the linear approximate straight line is preferably more than −0.0096, more preferably −0.0085 or more, and still more preferably −0.0080 or more. , Particularly preferably −0.0070 or more, more preferably −0.0060 or more, that is, the substrate according to the present embodiment has static contact with water on its surface even after the above friction test. The upper limit of the gradient ”′ ′ is not particularly limited, but may be, for example, less than −0.0001.
　上記線形近似直線におけるθ”は、例えば８０以上であり、具体的には９０以上であり、より具体的には１００以上であり、さらに具体的には１１０以上であり、１１４以上であってもよい。 Θ ′ in the linear approximation straight line is, for example, 80 or more, specifically 90 or more, more specifically 100 or more, more specifically 110 or more, and 114 or more. Good.
　本態様の基材は、摩擦試験前の静的接触角の測定値（即ち、往復回数０回の静的接触角の測定値）が高いことが好ましい。摩擦試験前の基材の接触角は、８０度以上であることが好ましく、１００度以上であることがより好ましく、１０５度以上であることが特に好ましく、１１０度以上であることがさらに好ましい。 The substrate of this embodiment preferably has a high static contact angle measurement before the friction test (that is, a static contact angle measurement with zero reciprocations). The contact angle of the substrate before the friction test is preferably 80 degrees or more, more preferably 100 degrees or more, particularly preferably 105 degrees or more, and still more preferably 110 degrees or more.
　本態様の基材は、摩擦試験において、摩擦子の往復回数４０００回における水の静的接触角の測定値が、好ましくは、８０度以上であり、より好ましくは、８４度以上であり、さらに好ましくは８５度以上であり、特に好ましくは、９０度以上である。このような基材では、基材の表面が摩擦された場合であっても、その表面における撥水性が良好である。すなわち、摩擦の生じ得る用途において、このような基材は特に有用であり得る。 In the friction test, the base material of the present embodiment preferably has a static contact angle measurement value of at least 80 degrees, more preferably at least 84 degrees, at a frequency of 4,000 reciprocations of the friction element. Preferably it is 85 degrees or more, Especially preferably, it is 90 degrees or more. In such a substrate, even when the surface of the substrate is rubbed, the water repellency on the surface is good. Thus, such substrates may be particularly useful in applications where friction may occur.
　摩擦子の往復回数０回の水の静的接触角の測定値に対する、摩擦子の往復回数４０００回における水の静的接触角の割合は、０．７０以上にあってもよく、０．８０以上にあってもよい。上記割合の上限値は、特に限定されないが、例えば１．００以下、具体的には０．９８以下であってもよい。このような基材では、基材の表面が摩擦された場合であっても、その表面における撥水性を良好に維持できる。すなわち、摩擦の生じ得る用途において、このような基材は特に有用であり得る。 The ratio of the static contact angle of water at 4,000 reciprocations of the friction element to the measured value of the static contact angle of water at the reciprocation number of times of the friction element may be 0.70 or more, 0.80 It may be above. The upper limit value of the ratio is not particularly limited, but may be, for example, 1.00 or less, specifically 0.98 or less. With such a substrate, even when the surface of the substrate is rubbed, the water repellency on the surface can be well maintained. Thus, such substrates may be particularly useful in applications where friction may occur.
　本態様の基材は、摩擦試験において、摩擦子の往復回数５０００回における水の静的接触角の測定値が、好ましくは、７５度以上であり、より好ましくは、８０度以上であり、さらに好ましくは、８５度以上である。このような基材では、基材の表面が摩擦された場合であっても、その表面における撥水性を特に良好に維持できる。すなわち、摩擦の生じ得る用途において、このような基材は特に有用であり得る。 In the friction test, the base material of the present embodiment preferably has a static contact angle measurement value of at least 75 degrees, more preferably at least 80 degrees, at a reciprocation frequency of 5,000 times of the friction element. Preferably, it is 85 degrees or more. With such a substrate, even when the surface of the substrate is rubbed, it is possible to maintain particularly good water repellency on the surface. Thus, such substrates may be particularly useful in applications where friction may occur.
　本態様の基材において、ＡＳＴＭ　Ｄ４９１７に準拠して測定される動摩擦係数が、０．０５０未満であることが好ましく、０．０３５未満であることがより好ましい。 In the base material of this embodiment, the dynamic friction coefficient measured in accordance with ASTM D4917 is preferably less than 0.050, and more preferably less than 0.035.
　好ましい態様において、本態様の基材は、さらに、
　波長３００ｎｍ～４００ｎｍの紫外線が、放射照度６２Ｗ／ｍ２で３００時間照射された表面において、２１℃および湿度６５％の雰囲気下において、試験用布（ここで、試験用布は、リン酸三ナトリウム５．５ｇ、塩化ナトリウム１０ｇ、乳酸３．１ｇ、リシン５ｇおよび蒸留水１００ｍｌからなる人工汗を浸漬させた、ＩＮＮＯＷＥＰ社製のＡＢＲＥＸ（登録商標）　ｓｔａｎｄａｒｄ　ｃｏｔｔｏｎ　ｓｏｉｌｉｎｇ　ｔｅｘｔｉｌｅ　ＦＩＮＥである。）で覆われたシリコーンよりなる摩擦子に、基材に対して５Ｎの荷重がかかるように、負荷をかけながら、該摩擦子を４０ｍｍ／秒の速度で往復する摩擦試験における、該摩擦子の往復回数０回、１０００回、２０００回、および３０００回（ただし、該往復回数は、水の静的接触角の測定値が最初に測定値が５０度未満になった回数を最大とする。）での往復回数（回）に対する紫外線照射後の水の静的接触角の測定値（度）に基づいて作成される線形近似直線の勾配が－０．０２２２超である。 In a preferred embodiment, the substrate of this embodiment further comprises
A test cloth (here, the test cloth is trisodium phosphate) under an atmosphere of 21 ° C. and a humidity of 65% on the surface irradiated with ultraviolet light of wavelength 300 nm to 400 nm at an irradiance of 62 W / m 2 for 300 hours Covered with INNOWEP's ABREX (R) standard cotton soiling textile FINE, soaked with artificial sweat consisting of 5.5 g, sodium chloride 10 g, lactic acid 3.1 g, lysine 5 g and 100 ml distilled water. In the friction test in which the friction element is reciprocated at a speed of 40 mm / sec while applying a load of 5 N to the base material to the friction element made of silicone, the number of reciprocations of the friction element is zero. 1000 times, 2000 times and 3000 times (however, the number of reciprocation times is a measure of the static contact angle of water Based on the measured value of static contact angle of water after UV irradiation (degree) to the number of round trips (times) in which the value is first measured less than 50 degrees) The slope of the linear approximation straight line is greater than -0.0222.
　紫外線（ＵＶ）の照射源としては、例えば、キセノンランプを用いることができる。上記ＵＶの照射は、より具体的には、基材のブラックパネル温度を５５度とし、ランプとＵＶの照射される基材の表面との距離を２９ｃｍとして行うことができる。 As an ultraviolet (UV) irradiation source, for example, a xenon lamp can be used. More specifically, the UV irradiation can be performed by setting the temperature of the black panel of the substrate to 55 degrees and the distance between the lamp and the surface of the substrate irradiated with UV to 29 cm.
　上記のようにＵＶを基材の表面に照射した後、摩擦試験前の該表面における水の静的接触角の測定値を求める。その後、該表面において摩擦試験を行い、摩擦子の往復回数１０００回毎に、基材の表面における水の静的接触角を測定し、水の静的接触角の測定値が５０度未満となるまで、摩擦試験を続ける。 After irradiating the surface of the substrate with UV as described above, a measure of the static contact angle of water on the surface prior to the friction test is determined. After that, a friction test is performed on the surface, and the static contact angle of water on the surface of the substrate is measured every 1000 reciprocations of the friction element, and the measured value of the static contact angle of water is less than 50 degrees Continue the friction test until.
　具体的には、ＵＶ照射試験後の摩擦試験は、以下のように行う。 Specifically, the friction test after the UV irradiation test is performed as follows.
　まず、ＵＶ照射試験後の基材で有り、かつ、摩擦試験前の基材について、その表面における水の静的接触角の測定値（即ち、往復回数０回のときの水の静的接触角の測定値）を得る。 First, for the substrate after the UV irradiation test and before the friction test, the measured value of the static contact angle of water on the surface (that is, the static contact angle of water when the number of reciprocations is zero) Measurement value of
　その後、ＵＶ照射試験後の基材の表面に対して、摩擦試験を実施する。摩擦子の往復回数１０００回毎に、基材の表面における水の静的接触角を測定し、水の静的接触角の測定値が５０度未満となるまで、摩擦試験を続ける。 Thereafter, a friction test is performed on the surface of the substrate after the UV irradiation test. The static contact angle of water on the surface of the substrate is measured every 1000 reciprocations of the friction element, and the friction test is continued until the measured value of the static contact angle of water is less than 50 degrees.
　より具体的には、摩擦子の往復回数が１０００回となったときに、基材の表面における水の静的接触角の測定値を求める。上記１０００回の測定値が５０度未満である場合には、摩擦試験を中止する。上記１０００回の測定値が５０度以上である場合には、さらに摩擦試験を行い、摩擦子の往復回数がさらに１０００回（即ち、計２０００回）となったときに、基材の表面における水の静的接触角の測定値を求める。上記２０００回の測定値が５０度未満の場合には、摩擦試験を中止する。上記２０００回の測定値が５０度以上の場合には、さらに摩擦試験を行い、摩擦子の往復回数がさらに１０００回（即ち、計３０００回）の場合の水の静的接触角の測定値を求める。上記３０００回の測定値が５０度未満の場合には、摩擦試験を中止する。上記３０００回の測定値が５０度以上の場合には、さらに摩擦試験を行い、摩擦子の往復回数が４０００回の場合の水の静的接触角の測定値を求める。以下、水の静的接触角が５０度未満となるまで摩擦試験を行い、摩擦子の往復回数１０００回毎に水の静的接触角の測定値を求める。 More specifically, when the number of reciprocations of the friction element reaches 1000, the measured value of the static contact angle of water on the surface of the substrate is determined. If the 1000 measurements are less than 50 degrees, the friction test is discontinued. If the measured value of 1000 times is 50 degrees or more, a friction test is further performed, and when the number of reciprocations of the friction element is further 1000 times (ie, 2000 times in total), water on the surface of the substrate Determine the static contact angle measurement value of If the above 2000 measurements are less than 50 degrees, the friction test is discontinued. In the case where the above 2000 measurements are 50 degrees or more, a friction test is further performed, and the static contact angle measurement value of water when the number of reciprocations of the friction element is 1000 times (ie, a total of 3000 times) Ask. If the 3000 readings are less than 50 degrees, the friction test is discontinued. In the case where the measured value of 3000 times is 50 degrees or more, the friction test is further performed to obtain the measured value of the static contact angle of water when the number of reciprocations of the friction element is 4000 times. Thereafter, a friction test is performed until the static contact angle of water is less than 50 degrees, and the measured value of the static contact angle of water is obtained every 1000 reciprocations of the friction element.
　次いで、上記の摩擦試験において得られたＵＶ照射後の水の静的接触角の測定値と、摩擦子の往復回数との関係を求める。 Next, the relationship between the measured value of the static contact angle of water after UV irradiation obtained in the above-mentioned friction test and the number of reciprocations of the friction element is determined.
　一の態様において、摩擦子の往復回数が最大３０００回における、摩擦子の往復回数ｘ’（回）と水の静的接触角の測定値との関係を求める。具体的には、該摩擦子の往復回数０回、１０００回、２０００回、および３０００回での往復回数（回）に対するＵＶ照射試験後の水の静的接触角の測定値（度）に基づいて作成される線形近似直線Ｆ’ｘ’＝η’ｘ’＋θ’（η’およびθ’は定数）を求める。 In one aspect, the relationship between the number of reciprocations x 'of the friction element and the measured value of the static contact angle of water when the number of reciprocations of the friction element is 3000 at maximum is determined. Specifically, it is based on the measurement value (degree) of the static contact angle of water after the UV irradiation test with respect to the number of reciprocation times of the friction element 0 times, 1000 times, 2000 times and 3000 times (times). linear approximation line F 'x' is generated Te = η'x '+ θ' (η ' and theta' is a constant) is obtained.
　ただし、該往復回数は、水の静的接触角の測定値が最初に測定値が５０度未満になった回数を最大とする。具体的には、摩擦子の往復回数１０００回における水の静的接触角の測定値が５０度未満である場合には、往復回数０回および１０００回における水の静的接触角の測定値を用いて線形近似直線を形成する。摩擦子の往復回数１０００回における水の静的接触角の測定値が５０度以上であり、２０００回における水の静的接触角の測定値が５０度未満である場合には、往復回数０回、１０００回、および２０００回の値を用いて線形近似直線を形成する。 However, the number of reciprocations makes the number of measurements of static contact angle of water first less than 50 degrees the maximum. Specifically, when the measured value of the static contact angle of water after the number of reciprocation times of the friction element is less than 50 degrees, the measured value of the static contact angle of water at the number of reciprocations of 0 times and 1000 times Use to form a linear approximation straight line. If the measured value of the static contact angle of water after the number of reciprocation times of the friction element is not less than 50 degrees and the measured value of the static contact angle of water after the 2000 times is less than 50 degrees, the number of reciprocations is 0 times , 1000 and 2000 values are used to form a linear approximation straight line.
　本態様の基材においては、上記のＵＶ照射試験後の線形近似直線の勾配η’が好ましくは－０．０２２２超であり、より好ましくは－０．０２００以上であり、さらに好ましくは－０．０１８０以上である。このような基材は、上記摩擦試験を行った後においても、その表面における水の静的接触角の低下が少なく、撥水性が低下しにくい。上記勾配η’の上限は特に限定されないが、例えば－０．００１未満であってもよい。 In the substrate of this embodiment, the gradient η ′ of the linear approximate straight line after the above-mentioned UV irradiation test is preferably more than −0.0222, more preferably −0.0200 or more, and still more preferably −0. It is more than 0180. Even after such a substrate has been subjected to the above-described friction test, the decrease in static contact angle of water on the surface is small, and the water repellency is unlikely to be reduced. The upper limit of the gradient ’′ is not particularly limited, but may be, for example, less than −0.001.
　上記θ’は、例えば、９８以上であり、より具体的には１００以上である。 The above θ ′ is, for example, 98 or more, and more specifically, 100 or more.
　一の態様において、摩擦子の往復回数が最大６０００回における、摩擦子の往復回数ｘ’（回）と水の静的接触角の測定値との関係を求める。該摩擦子の往復回数（回）に対するＵＶ照射試験後の水の静的接触角の測定値（度）に基づいて作成される線形近似直線Ｆ'''ｘ'＝η'''ｘ'＋θ'''（η'''およびθ'''は定数）を求める。 In one aspect, the relationship between the number of reciprocations x 'of the friction element and the measured value of the static contact angle of water when the number of reciprocations of the friction element is at most 6000 times is determined. Linear approximate straight line F ′ ′ ′ x ′ = η ′ ′ ′ ′ x ′ + θ created based on the measured value (degree) of static contact angle of water after UV irradiation test with respect to the number of reciprocations (times) of the friction element Find '''(η''' and θ '''are constants).
　上記線形近似直線においてη'''は、例えば、－０．０２２２超である。θ'''は、例えば、９８以上であり、より具体的には１００以上である。 In the linear approximation straight line, η ′ ′ ′ is, for example, more than −0.0222. θ ′ ′ ′ is, for example, 98 or more, more specifically 100 or more.
　本態様の基材は、上記ＵＶ照射試験後の摩擦試験において、摩擦子の往復回数３０００回における水の静的接触角の測定値が、５０度以上であることが好ましく、５５度以上であることがより好ましく、６０度以上であることがさらに好ましく、７０度以上であることが特に好ましく、７５度以上であることがさらに好ましい。 In the substrate according to this aspect, in the friction test after the UV irradiation test, the measured value of the static contact angle of water after 3,000 reciprocations of the friction element is preferably 50 degrees or more, and is 55 degrees or more It is more preferably 60 degrees or more, particularly preferably 70 degrees or more, and still more preferably 75 degrees or more.
　本態様の基材は、少なくとも１の表面において、表面にパーフルオロポリエーテル基含有化合物から形成された表面処理層を有する。即ち、本態様の基材は、表面処理剤層と、ベース層とを含むことが好ましい。 The substrate of this embodiment has a surface treatment layer formed of a compound containing a perfluoropolyether group on the surface on at least one surface. That is, it is preferable that the base material of this aspect contains a surface treating agent layer and a base layer.
　上記ベース層は、例えばガラス、樹脂（天然または合成樹脂、例えば一般的なプラスチック材料であってよく、板状、フィルム、その他の形態であってよい）、金属（アルミニウム、銅、鉄等の金属単体または合金等の複合体であってよい）、セラミックス、半導体（シリコン、ゲルマニウム等）、繊維（織物、不織布等）、毛皮、皮革、木材、陶磁器、石材等、建築部材等、任意の適切な材料で構成され得る。 The base layer is, for example, glass, resin (natural or synthetic resin, for example, general plastic material, may be plate, film, or other form), metal (metal such as aluminum, copper, iron, etc.) May be a single substance or a composite such as an alloy), ceramics, semiconductor (silicon, germanium, etc.), fiber (textile, non-woven cloth, etc.), fur, leather, wood, china, stone etc., construction member etc. any appropriate It may be composed of materials.
　例えば、製造すべき物品が光学部材である場合、ベース層の表面を構成する材料は、光学部材用材料、例えばガラスまたは透明プラスチックなどであってよい。また、製造すべき物品が光学部材である場合、ベース層の表面（最外層）に何らかの層（または膜）、例えばハードコート層や反射防止層などが形成されていてもよい。反射防止層には、単層反射防止層および多層反射防止層のいずれを使用してもよい。反射防止層に使用可能な無機物の例としては、ＳｉＯ２、ＳｉＯ、ＺｒＯ２、ＴｉＯ２、ＴｉＯ、Ｔｉ２Ｏ３、Ｔｉ２Ｏ５、Ａｌ２Ｏ３、Ｔａ２Ｏ５、ＣｅＯ２、ＭｇＯ、Ｙ２Ｏ３、ＳｎＯ２、ＭｇＦ２、ＷＯ３などが挙げられる。これらの無機物は、単独で、またはこれらの２種以上を組み合わせて（例えば混合物として）使用してもよい。多層反射防止層とする場合、その最外層にはＳｉＯ２および／またはＳｉＯを用いることが好ましい。製造すべき物品が、タッチパネル用の光学ガラス部品である場合、透明電極、例えば酸化インジウムスズ（ＩＴＯ）や酸化インジウム亜鉛などを用いた薄膜を、ベース層（ガラス）の表面の一部に有していてもよい。また、ベース層は、その具体的仕様等に応じて、絶縁層、粘着層、保護層、装飾枠層（Ｉ－ＣＯＮ）、霧化膜層、ハードコーティング膜層、偏光フィルム、相位差フィルム、および液晶表示モジュールなどを有していてもよい。 For example, when the article to be manufactured is an optical member, the material constituting the surface of the base layer may be an optical member material such as glass or transparent plastic. When the article to be manufactured is an optical member, some layer (or film) such as a hard coat layer or an antireflective layer may be formed on the surface (the outermost layer) of the base layer. For the antireflective layer, either a single layer antireflective layer or a multilayer antireflective layer may be used. Examples of inorganic substances that can be used for the antireflective layer include SiO 2 , SiO, ZrO 2 , TiO 2 , TiO, Ti 2 O 3 , Ti 2 O 5 , Al 2 O 3 , Ta 2 O 5 , CeO 2 and MgO. , Y 2 O 3 , SnO 2 , MgF 2 , WO 3 and the like. These inorganic substances may be used alone or in combination of two or more of them (for example, as a mixture). If the multilayer antireflection layer, it is preferable to use SiO 2 and / or SiO in its outermost layer. When the article to be manufactured is an optical glass part for a touch panel, it has a thin film using a transparent electrode such as indium tin oxide (ITO) or indium zinc oxide on a part of the surface of the base layer (glass) It may be In addition, the base layer may be an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomized film layer, a hard coating film layer, a polarizing film, a phase difference film, or the like depending on its specific specifications. And a liquid crystal display module.
　好ましい態様において、ベース層はガラスを含む。 In a preferred embodiment, the base layer comprises glass.
　上記ガラスとしては、ソーダライムガラス、アルカリアルミノケイ酸塩ガラス、ホウ珪酸ガラス、無アルカリガラス、クリスタルガラス、石英ガラスが挙げられる。 Examples of the glass include soda lime glass, alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass and quartz glass.
　一の態様において、上記ガラスは、化学強化ガラス、例えば化学強化したソーダライムガラス、化学強化したアルカリアルミノケイ酸塩ガラス、および化学強化したホウ珪酸ガラスであり得る。 In one aspect, the glass may be chemically tempered glass, such as chemically tempered soda lime glass, chemically tempered alkali aluminosilicate glass, and chemically tempered borosilicate glass.
　好ましい態様において、上記化学強化ガラスは、ＳｉＯ２、およびＡｌ２Ｏ３、Ｎａ２Ｏ、ＭｇＯ、Ｋ２Ｏ、ＣａＯ、ＢａＯ、ＳｒＯ、およびＢ２Ｏ３からなる群から選択される１つまたはそれ以上の酸化物を含む化学強化用ガラスを化学強化処理（典型的には、イオン交換）して得られるガラスであり得る。 In a preferred embodiment, the chemically strengthened glass is one or more selected from the group consisting of SiO 2 and Al 2 O 3 , Na 2 O, MgO, K 2 O, CaO, BaO, SrO, and B 2 O 3 It may be a glass obtained by chemical strengthening treatment (typically, ion exchange) of a glass for chemical strengthening that contains further oxides.
　好ましい態様において、上記化学強化用ガラスは、上記酸化物を、下記の割合（酸化物基準の重量百分率）で含有する。
　　　ＳｉＯ２：６０．０～８０．０％
　　　Ａｌ２Ｏ３：０．５～１２．０％
　　　Ｂ２Ｏ３：０～３．０％
　　　ＭｇＯ：０～１２．０％
　　　ＣａＯ：０～５．０％
　　　ＳｒＯ：０～５．０％
　　　ＢａＯ：０～５．０％
　　　Ｎａ２Ｏ：３．０～２０．０％
　　　Ｋ２Ｏ：０～１０．０％ In a preferred embodiment, the above-mentioned glass for chemical strengthening contains the above-mentioned oxide in the following proportion (weight percentage based on oxide).
SiO 2 : 60.0 to 80.0%
Al 2 O 3 : 0.5 to 12.0%
B 2 O 3 : 0 to 3.0%
MgO: 0 to 12.0%
CaO: 0 to 5.0%
SrO: 0 to 5.0%
BaO: 0 to 5.0%
Na 2 O: 3.0 to 20.0%
K 2 O: 0 to 10.0%
　化学強化処理は、従来公知の方法によって行うことができる。例えば、化学強化処理においては、大きなイオン半径の金属イオン（典型的には、Ｋイオン）を含む金属塩（例えば、硝酸カリウム）の融液に、浸漬などによってガラス板を接触させることにより、ガラス板中の小さなイオン半径の金属イオン（典型的には、ＮａイオンまたはＬｉイオン）が大きなイオン半径の金属イオンと置換される。 The chemical strengthening treatment can be performed by a conventionally known method. For example, in a chemical strengthening process, a glass plate is brought into contact with a melt of a metal salt (for example, potassium nitrate) containing a large ion radius metal ion (typically, K ion) by immersion or the like. The metal ion of small ion radius (typically, Na ion or Li ion) is replaced with the metal ion of large ion radius.
　一の態様において、上記化学強化ガラスの圧縮応力層の厚みは、好ましくは３５μｍ以上、より好ましくは４０μｍ以上、さらに好ましくは４５μｍ以上であり得る。 In one aspect, the thickness of the compressive stress layer of the chemically strengthened glass may be preferably 35 μm or more, more preferably 40 μm or more, and still more preferably 45 μm or more.
　上記化学強化ガラスの圧縮応力層の厚みは、化学強化用ガラスを化学強化する際の条件、化学強化用ガラスの組成等を調整することにより、適宜調整することができる。 The thickness of the compression stress layer of the chemically strengthened glass can be appropriately adjusted by adjusting the conditions for chemically strengthening the glass for chemical strengthening, the composition of the glass for chemical strengthening, and the like.
　ここに、圧縮応力層の厚みとは、ガラス板最表面を基準として圧縮応力が形成されている領域の深さである。かかる圧縮応力層の厚みは、表面応力計により測定することができる。例えば、圧縮応力層の厚みは、室温２５℃、湿度６０％の環境下、５８９ｎｍのＮａ光源にて、折原製作所社製表面応力計ＦＳＭ－６０００を用いて測定することができる。 Here, the thickness of the compressive stress layer is the depth of the region in which the compressive stress is formed with reference to the outermost surface of the glass plate. The thickness of the compressive stress layer can be measured by a surface stress meter. For example, the thickness of the compressive stress layer can be measured using a surface stress meter FSM-6000 manufactured by Orihara Mfg. Co., under a 589 nm Na light source under an environment of room temperature 25 ° C. and humidity 60%.
　ベース層の形状は特に限定されない。また、表面処理剤からなる層（表面処理層）を形成すべきベース層の表面領域は、ベース層の表面の少なくとも一部であればよく、製造すべき物品の用途および具体的仕様等に応じて適宜決定され得る。 The shape of the base layer is not particularly limited. The surface area of the base layer on which the surface treatment agent layer (surface treatment layer) is to be formed may be at least a part of the surface of the base layer, depending on the application and specific specifications of the article to be manufactured. Can be determined appropriately.
　かかるベース層としては、少なくともその表面部分が、水酸基を元々有する材料から成るものであってよい。かかる材料としては、ガラスが挙げられ、また、表面に自然酸化膜または熱酸化膜が形成される金属（特に卑金属）、セラミックス、半導体等が挙げられる。あるいは、樹脂等のように、水酸基を有していても十分でない場合や、水酸基を元々有していない場合には、ベース層に何らかの前処理を施すことにより、ベース層の表面に水酸基を導入したり、増加させたりすることができる。かかる前処理の例としては、プラズマ処理（例えばコロナ放電）や、イオンビーム照射が挙げられる。プラズマ処理は、ベース層の表面に水酸基を導入または増加させ得ると共に、ベース層の表面を清浄化する（異物等を除去する）ためにも好適に利用され得る。また、かかる前処理の別の例としては、炭素－炭素不飽和結合基を有する界面吸着剤をＬＢ法（ラングミュア－ブロジェット法）や化学吸着法等によって、ベース層の表面に予め単分子膜の形態で形成し、その後、酸素や窒素等を含む雰囲気下にて不飽和結合を開裂する方法が挙げられる。 As such a base layer, at least the surface portion may be made of a material originally having a hydroxyl group. Examples of such a material include glass, and further, metals (in particular, base metals), ceramics, semiconductors, etc. on which a natural oxide film or a thermal oxide film is formed on the surface. Alternatively, as in the case of resin or the like, when having hydroxyl groups is not sufficient, or when it does not originally have hydroxyl groups, the base layer is pretreated to introduce hydroxyl groups on the surface of the base layer. Can be increased or decreased. Examples of such pretreatment include plasma treatment (eg, corona discharge) and ion beam irradiation. The plasma treatment can introduce or increase hydroxyl groups on the surface of the base layer, and can also be suitably used to clean the surface of the base layer (remove foreign matter and the like). In addition, as another example of such pretreatment, an interfacial adsorbent having a carbon-carbon unsaturated bond group is coated on the surface of the base layer in advance by the LB method (Langmuir-Blodgett method), chemical adsorption method or the like. And then the unsaturated bond is cleaved in an atmosphere containing oxygen, nitrogen and the like.
　またあるいは、かかるベース層としては、少なくともその表面部分が、別の反応性基、例えばＳｉ－Ｈ基を１つ以上有するシリコーン化合物や、アルコキシシランを含む材料から成るものであってもよい。 Alternatively, the base layer may be made of a material including at least a silicone compound having one or more other reactive groups such as Si—H groups, or a material containing an alkoxysilane.
　上記表面処理剤は、パーフルオロポリエーテル基（以下、「ＰＦＰＥ基」ともいう）含有化合物を含み、ＰＦＰＥ基含有シラン化合物を含むことが好ましい。 The surface treatment agent preferably contains a perfluoropolyether group (hereinafter also referred to as "PFPE group") containing compound, and preferably contains a PFPE group containing silane compound.
　上記ＰＦＰＥ含有シラン化合物は、例えば、（Ａ１）、（Ａ２）、（Ｂ１）、（Ｂ２）、（Ｃ１）、（Ｃ２）、（Ｄ１）または（Ｄ２）で表される化合物である。
Figure JPOXMLDOC01-appb-C000001
 The PFPE-containing silane compound is, for example, a compound represented by (A1), (A2), (B1), (B2), (C1), (C2), (D1) or (D2).
Figure JPOXMLDOC01-appb-C000001
　以下、上記式（Ａ１）、（Ａ２）、（Ｂ１）、（Ｂ２）、（Ｃ１）、（Ｃ２）、（Ｄ１）および（Ｄ２）で表されるＰＦＰＥ含有シラン化合物について説明する。 The PFPE-containing silane compounds represented by the above formulas (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2) will be described below.
　本明細書において用いられる場合、「２～１０価の有機基」とは、炭素を含有する２～１０価の基を意味する。かかる２～１０価の有機基としては、特に限定されないが、炭化水素基からさらに１～９個の水素原子を脱離させた２～１０価の基が挙げられる。２価の有機基としては、特に限定されるものではないが、炭化水素基からさらに１個の水素原子を脱離させた２価の基が挙げられる。 As used herein, "di- to dodeca-valent organic group" means a carbon-containing di- to 10-valent group. The di- to deca-valent organic group is not particularly limited, and examples thereof include di- to 10-valent groups obtained by further removing 1 to 9 hydrogen atoms from a hydrocarbon group. The divalent organic group is not particularly limited, and examples thereof include divalent groups in which one hydrogen atom is further eliminated from a hydrocarbon group.
　本明細書において用いられる場合、「炭化水素基」とは、炭素および水素を含む基であって、分子から１個の水素原子を脱離させた基を意味する。かかる炭化水素基としては、特に限定されるものではないが、１つまたはそれ以上の置換基により置換されていてもよい、炭素数１～２０の炭化水素基、例えば、脂肪族炭化水素基、芳香族炭化水素基等が挙げられる。上記「脂肪族炭化水素基」は、直鎖状、分枝鎖状または環状のいずれであってもよく、飽和または不飽和のいずれであってもよい。また、炭化水素基は、１つまたはそれ以上の環構造を含んでいてもよい。尚、かかる炭化水素基は、その末端または分子鎖中に、１つまたはそれ以上のＮ、Ｏ、Ｓ、Ｓｉ、アミド、スルホニル、シロキサン、カルボニル、カルボニルオキシ等を有していてもよい。 As used herein, "hydrocarbon group" means a group containing carbon and hydrogen wherein one hydrogen atom has been eliminated from the molecule. Such a hydrocarbon group is not particularly limited, and may be a hydrocarbon group having 1 to 20 carbon atoms which may be substituted by one or more substituents, for example, an aliphatic hydrocarbon group, Aromatic hydrocarbon groups and the like can be mentioned. The “aliphatic hydrocarbon group” may be linear, branched or cyclic, and may be saturated or unsaturated. The hydrocarbon group may also contain one or more ring structures. Such a hydrocarbon group may have one or more of N, O, S, Si, an amide, a sulfonyl, a siloxane, a carbonyl, a carbonyloxy and the like in the terminal or molecular chain thereof.
　本明細書において用いられる場合、「炭化水素基」の置換基としては、特に限定されないが、例えば、ハロゲン原子；１個またはそれ以上のハロゲン原子により置換されていてもよい、Ｃ１－６アルキル基、Ｃ２－６アルケニル基、Ｃ２－６アルキニル基、Ｃ３－１０シクロアルキル基、Ｃ３－１０不飽和シクロアルキル基、５～１０員のヘテロシクリル基、５～１０員の不飽和ヘテロシクリル基、Ｃ６－１０アリール基および５～１０員のヘテロアリール基から選択される１個またはそれ以上の基が挙げられる。 As used herein, the substituent of the “hydrocarbon group” is not particularly limited, and for example, a halogen atom; C 1-6 alkyl optionally substituted by one or more halogen atoms Group, C 2-6 alkenyl group, C 2-6 alkynyl group, C 3-10 cycloalkyl group, C 3-10 unsaturated cycloalkyl group, 5- to 10-membered heterocyclyl group, 5- to 10-membered unsaturated heterocyclyl Groups, one or more groups selected from C 6-10 aryl groups and 5-10 membered heteroaryl groups.
　本明細書において、アルキル基およびフェニル基は、特記しない限り、非置換であっても、置換されていてもよい。かかる基の置換基としては、特に限定されないが、例えば、ハロゲン原子、Ｃ１－６アルキル基、Ｃ２－６アルケニル基およびＣ２－６アルキニル基から選択される１個またはそれ以上の基が挙げられる。 In the present specification, an alkyl group and a phenyl group may be unsubstituted or substituted, unless otherwise specified. The substituent of such group is not particularly limited, and one or more groups selected from, for example, a halogen atom, a C 1-6 alkyl group, a C 2-6 alkenyl group and a C 2-6 alkynyl group are preferable. It can be mentioned.
　式（Ａ１）および（Ａ２）：
Figure JPOXMLDOC01-appb-C000002
 Formulas (A1) and (A2):
Figure JPOXMLDOC01-appb-C000002
　上記式中、Ｒｆは、各出現において独立して、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１～１６のアルキル基を表す。 In the above formulae, R f independently at each occurrence represents an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms.
　上記１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１～１６のアルキル基における「炭素数１～１６のアルキル基」は、直鎖であっても、分枝鎖であってもよく、好ましくは、直鎖または分枝鎖の炭素数１～６、特に炭素数１～３のアルキル基であり、より好ましくは直鎖の炭素数１～３のアルキル基である。 The "C1-C16 alkyl group" in the C1-C16 alkyl group which may be substituted by one or more fluorine atoms is a branched chain even if it is a straight chain It is preferably a linear or branched alkyl group having 1 to 6 carbon atoms, particularly 1 to 3 carbon atoms, and more preferably a linear alkyl group having 1 to 3 carbon atoms.
　上記Ｒｆは、好ましくは、１個またはそれ以上のフッ素原子により置換されている炭素数１～１６のアルキル基であり、より好ましくはＣＦ２Ｈ－Ｃ１－１５フルオロアルキレン基またはＣ１－１６パーフルオロアルキル基であり、さらに好ましくはＣ１－１６パーフルオロアルキル基である。 The above Rf is preferably an alkyl group having 1 to 16 carbon atoms, which is substituted by one or more fluorine atoms, and more preferably a CF 2 H—C 1-15 fluoroalkylene group or a C 1-16 It is a perfluoroalkyl group, more preferably a C 1-16 perfluoroalkyl group.
　該炭素数１～１６のパーフルオロアルキル基は、直鎖であっても、分枝鎖であってもよく、好ましくは、直鎖または分枝鎖の炭素数１～６、特に炭素数１～３のパーフルオロアルキル基であり、より好ましくは直鎖の炭素数１～３のパーフルオロアルキル基、具体的には－ＣＦ３、－ＣＦ２ＣＦ３、または－ＣＦ２ＣＦ２ＣＦ３である。 The perfluoroalkyl group having 1 to 16 carbon atoms may be linear or branched, and preferably has 1 to 6 carbon atoms, particularly 1 to 6 carbon atoms, in a linear or branched chain. a 3 perfluoroalkyl group, more preferably a perfluoroalkyl group having 1-3 carbon atoms, straight-chain, specifically is -CF 3, -CF 2 CF 3 or -CF 2 CF 2 CF 3, .
　上記式中、ＰＦＰＥは、各出現において独立して、
－（ＯＣ６Ｆ１２）ａ－（ＯＣ５Ｆ１０）ｂ－（ＯＣ４Ｆ８）ｃ－（ＯＣ３Ｘ１０ ６）ｄ－（ＯＣ２Ｆ４）ｅ－（ＯＣＦ２）ｆ－
で表される基である。式中、ａ、ｂ、ｃ、ｄ、ｅおよびｆは、それぞれ独立して０以上２００以下の整数であって、ａ、ｂ、ｃ、ｄ、ｅおよびｆの和は少なくとも１である。好ましくは、ａ、ｂ、ｃ、ｄ、ｅおよびｆは、それぞれ独立して、０以上１００以下の整数である。好ましくは、ａ、ｂ、ｃ、ｄ、ｅおよびｆの和は５以上であり、より好ましくは１０以上である。好ましくは、ａ、ｂ、ｃ、ｄ、ｅおよびｆの和は２００以下であり、より好ましくは１００以下であり、例えば１０以上２００以下であり、より具体的には１０以上１００以下である。また、ａ、ｂ、ｃ、ｄ、ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。Ｘ１０は、各出現においてそれぞれ独立して、水素原子、フッ素原子または塩素原子であり、好ましくは水素原子またはフッ素原子であり、より好ましくはフッ素原子である。 In the above formula, PFPE is independently at each occurrence:
- (OC 6 F 12) a - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 X 10 6) d - (OC 2 F 4) e - (OCF 2) f -
Is a group represented by In the formula, a, b, c, d, e and f are each independently an integer of 0 or more and 200 or less, and the sum of a, b, c, d, e and f is at least 1. Preferably, a, b, c, d, e and f are each independently an integer of 0 or more and 100 or less. Preferably, the sum of a, b, c, d, e and f is 5 or more, more preferably 10 or more. Preferably, the sum of a, b, c, d, e and f is 200 or less, more preferably 100 or less, for example 10 or more and 200 or less, more specifically 10 or more and 100 or less. In addition, the order in which each repeating unit enclosed in parentheses with a, b, c, d, e or f is present is arbitrary in the formula. X 10 each independently at each occurrence is a hydrogen atom, a fluorine atom or a chlorine atom, preferably a hydrogen atom or a fluorine atom, more preferably a fluorine atom.
　これら繰り返し単位は、直鎖状であっても、分枝鎖状であってもよいが、好ましくは直鎖状である。例えば、－（ＯＣ６Ｆ１２）－は、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ（ＣＦ３）ＣＦ２ＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ（ＣＦ３）ＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ（ＣＦ３）ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ（ＣＦ３）ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ（ＣＦ３））－等であってもよいが、好ましくは－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２）－である。－（ＯＣ５Ｆ１０）－は、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ（ＣＦ３）ＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ（ＣＦ３）ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ（ＣＦ３）ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ（ＣＦ３））－等であってもよいが、好ましくは－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２）－である。－（ＯＣ４Ｆ８）－は、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ（ＣＦ３）ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ（ＣＦ３）ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ（ＣＦ３））－、－（ＯＣ（ＣＦ３）２ＣＦ２）－、－（ＯＣＦ２Ｃ（ＣＦ３）２）－、－（ＯＣＦ（ＣＦ３）ＣＦ（ＣＦ３））－、－（ＯＣＦ（Ｃ２Ｆ５）ＣＦ２）－および－（ＯＣＦ２ＣＦ（Ｃ２Ｆ５））－のいずれであってもよいが、好ましくは－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２）－である。－（ＯＣ３Ｆ６）－は、－（ＯＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ（ＣＦ３）ＣＦ２）－および－（ＯＣＦ２ＣＦ（ＣＦ３））－のいずれであってもよいが、好ましくは－（ＯＣＦ２ＣＦ２ＣＦ２）－である。また、－（ＯＣ２Ｆ４）－は、－（ＯＣＦ２ＣＦ２）－および－（ＯＣＦ（ＣＦ３））－のいずれであってもよいが、好ましくは－（ＯＣＦ２ＣＦ２）－である。 These repeating units may be linear or branched, but are preferably linear. For example, - (OC 6 F 12) - is, - (OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2) -, - (OCF (CF 3) CF 2 CF 2 CF 2 CF 2) -, - (OCF 2 CF (CF 3) CF 2 CF 2 CF 2) -, - (OCF 2 CF 2 CF (CF 3) CF 2 CF 2) -, - (OCF 2 CF 2 CF 2 CF (CF 3) CF 2) - And-(OCF 2 CF 2 CF 2 CF 2 CF (CF 3 ))-may be used, but-(OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 )-is preferable. - (OC 5 F 10) - is, - (OCF 2 CF 2 CF 2 CF 2 CF 2) -, - (OCF (CF 3) CF 2 CF 2 CF 2) -, - (OCF 2 CF (CF 3) It may be CF 2 CF 2 )-,-(OCF 2 CF 2 CF (CF 3 ) CF 2 )-,-(OCF 2 CF 2 CF 2 CF (CF 3 ))-or the like, preferably-( OCF 2 CF 2 CF 2 CF 2 CF 2) - a. - (OC 4 F 8) - is, - (OCF 2 CF 2 CF 2 CF 2) -, - (OCF (CF 3) CF 2 CF 2) -, - (OCF 2 CF (CF 3) CF 2) - , - (OCF 2 CF 2 CF (CF 3)) -, - (OC (CF 3) 2 CF 2) -, - (OCF 2 C (CF 3) 2) -, - (OCF (CF 3) CF ( It may be any of CF 3 )),-(OCF (C 2 F 5 ) CF 2 )-and-(OCF 2 CF (C 2 F 5 ))-, but preferably-(OCF 2 CF 2). CF 2 CF 2 )-. - (OC 3 F 6) - is, - (OCF 2 CF 2 CF 2) -, - (OCF (CF 3) CF 2) - and - (OCF 2 CF (CF 3 )) - be any of Although preferred, preferred is-(OCF 2 CF 2 CF 2 )-. Also, - (OC 2 F 4) - is, - (OCF 2 CF 2) - and - (OCF (CF 3)) - but it may be any of, preferably - (OCF 2 CF 2) - in is there.
　一の態様において、上記ＰＦＰＥは、－（ＯＣ３Ｆ６）ｄ－（式中、ｄは１以上２００以下、好ましくは５以上２００以下、より好ましくは１０以上２００以下の整数である）である。好ましくは、ＰＦＰＥは、－（ＯＣＦ２ＣＦ２ＣＦ２）ｄ－（式中、ｄは１以上２００以下、好ましくは５以上２００以下、より好ましくは１０以上２００以下の整数である）または－（ＯＣＦ（ＣＦ３）ＣＦ２）ｄ－（式中、ｄは１以上２００以下、好ましくは５以上２００以下、より好ましくは１０以上２００以下の整数である）である。より好ましくは、ＰＦＰＥは、－（ＯＣＦ２ＣＦ２ＣＦ２）ｄ－（式中、ｄは１以上２００以下、好ましくは５以上２００以下、より好ましくは１０以上２００以下の整数である）である。 In one aspect, the PFPE is — (OC 3 F 6 ) d — (wherein d is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less) . Preferably, PFPE is — (OCF 2 CF 2 CF 2 ) d — (wherein d is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less) or OCF (CF 3 ) CF 2 ) d — (wherein, d is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less). More preferably, PFPE is — (OCF 2 CF 2 CF 2 ) d — (wherein d is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less) .
　別の態様において、ＰＦＰＥは、－（ＯＣ４Ｆ８）ｃ－（ＯＣ３Ｆ６）ｄ－（ＯＣ２Ｆ４）ｅ－（ＯＣＦ２）ｆ－（式中、ｃおよびｄは、それぞれ独立して０以上３０以下の整数であり、ｅおよびｆは、それぞれ独立して１以上２００以下、好ましくは５以上２００以下、より好ましくは１０以上２００以下の整数であり、ｃ、ｄ、ｅおよびｆの和は少なくとも５以上、好ましくは１０以上であり、添字ｃ、ｄ、ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である）である。好ましくは、ＰＦＰＥは、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２）ｃ－（ＯＣＦ２ＣＦ２ＣＦ２）ｄ－（ＯＣＦ２ＣＦ２）ｅ－（ＯＣＦ２）ｆ－である。一の態様において、ＰＦＰＥは、－（ＯＣ２Ｆ４）ｅ－（ＯＣＦ２）ｆ－（式中、ｅおよびｆは、それぞれ独立して１以上２００以下、好ましくは５以上２００以下、より好ましくは１０以上２００以下の整数であり、添字ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である）であってもよい。 In another embodiment, the PFPE is — (OC 4 F 8 ) c — (OC 3 F 6 ) d — (OC 2 F 4 ) e — (OCF 2 ) f —, wherein c and d are each independently And e and f are each independently an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less, and c, d, e and The sum of f is at least 5 or more, preferably 10 or more, and the order in which each repeating unit enclosed in parentheses with the subscript c, d, e or f is given is arbitrary in the formula). Preferably, PFPE is, - (OCF 2 CF 2 CF 2 CF 2) c - (OCF 2 CF 2 CF 2) d - (OCF 2 CF 2) e - (OCF 2) f - a. In one aspect, PFPE is — (OC 2 F 4 ) e — (OCF 2 ) f — (wherein e and f are each independently 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably Is an integer of 10 or more and 200 or less, and the order in which each repeating unit enclosed in parentheses with the subscript e or f is attached may be arbitrary in the formula).
　さらに別の態様において、ＰＦＰＥは、－（Ｒ６－Ｒ７）ｊ－で表される基である。式中、Ｒ６は、ＯＣＦ２またはＯＣ２Ｆ４であり、好ましくはＯＣ２Ｆ４である。式中、Ｒ７は、ＯＣ２Ｆ４、ＯＣ３Ｆ６、ＯＣ４Ｆ８、ＯＣ５Ｆ１０およびＯＣ６Ｆ１２から選択される基であるか、あるいは、これらの基から独立して選択される２または３つの基の組み合わせである。好ましくは、Ｒ７は、ＯＣ２Ｆ４、ＯＣ３Ｆ６およびＯＣ４Ｆ８から選択される基であるか、ＯＣ３Ｆ６、ＯＣ４Ｆ８、ＯＣ５Ｆ１０およびＯＣ６Ｆ１２から選択される基であるか、あるいは、これらの基から独立して選択される２または３つの基の組み合わせである。ＯＣ２Ｆ４、ＯＣ３Ｆ６およびＯＣ４Ｆ８から独立して選択される２または３つの基の組み合わせとしては、特に限定されないが、例えば－ＯＣ２Ｆ４ＯＣ３Ｆ６－、－ＯＣ２Ｆ４ＯＣ４Ｆ８－、－ＯＣ３Ｆ６ＯＣ２Ｆ４－、－ＯＣ３Ｆ６ＯＣ３Ｆ６－、－ＯＣ３Ｆ６ＯＣ４Ｆ８－、－ＯＣ４Ｆ８ＯＣ４Ｆ８－、－ＯＣ４Ｆ８ＯＣ３Ｆ６－、－ＯＣ４Ｆ８ＯＣ２Ｆ４－、－ＯＣ２Ｆ４ＯＣ２Ｆ４ＯＣ３Ｆ６－、－ＯＣ２Ｆ４ＯＣ２Ｆ４ＯＣ４Ｆ８－、－ＯＣ２Ｆ４ＯＣ３Ｆ６ＯＣ２Ｆ４－、－ＯＣ２Ｆ４ＯＣ３Ｆ６ＯＣ３Ｆ６－、－ＯＣ２Ｆ４ＯＣ４Ｆ８ＯＣ２Ｆ４－、－ＯＣ３Ｆ６ＯＣ２Ｆ４ＯＣ２Ｆ４－、－ＯＣ３Ｆ６ＯＣ２Ｆ４ＯＣ３Ｆ６－、－ＯＣ３Ｆ６ＯＣ３Ｆ６ＯＣ２Ｆ４－、および－ＯＣ４Ｆ８ＯＣ２Ｆ４ＯＣ２Ｆ４－等が挙げられる。上記ｊは、２以上、好ましくは３以上、より好ましくは５以上であり、１００以下、好ましくは５０以下の整数である。上記式中、ＯＣ２Ｆ４、ＯＣ３Ｆ６、ＯＣ４Ｆ８、ＯＣ５Ｆ１０およびＯＣ６Ｆ１２は、直鎖または分枝鎖のいずれであってもよく、好ましくは直鎖である。この態様において、ＰＦＰＥは、好ましくは、－（ＯＣ２Ｆ４－ＯＣ３Ｆ６）ｊ－または－（ＯＣ２Ｆ４－ＯＣ４Ｆ８）ｊ－である。 In yet another embodiment, PFPE is a group represented by-(R 6 -R 7 ) j- . In the formula, R 6 is OCF 2 or OC 2 F 4 , preferably OC 2 F 4 . Wherein R 7 is a group selected from OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 or selected independently from these groups A combination of two or three groups. Preferably, R 7 is a group selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 or from OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 It is a selected group, or a combination of 2 or 3 groups independently selected from these groups. The combination of 2 or 3 groups independently selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 is not particularly limited. For example, -OC 2 F 4 OC 3 F 6- , -OC 2 F 4 OC 4 F 8 - , - OC 3 F 6 OC 2 F 4 -, - OC 3 F 6 OC 3 F 6 -, - OC 3 F 6 OC 4 F 8 -, - OC 4 F 8 OC 4 F 8 -, - OC 4 F 8 OC 3 F 6 -, - OC 4 F 8 OC 2 F 4 -, - OC 2 F 4 OC 2 F 4 OC 3 F 6 -, - OC 2 F 4 OC 2 F 4 OC 4 F 8 -, - OC 2 F 4 OC 3 F 6 OC 2 F 4 -, - OC 2 F 4 OC 3 F 6 OC 3 F 6 -, - OC 2 F 4 OC 4 F 8 OC 2 F 4 -, -OC 3 F 6 OC 2 F 4 OC 2 F 4 -,-OC 3 F 6 OC 2 F 4 OC 3 F 6 -, - OC 3 F 6 OC 3 F 6 OC 2 F 4 -, and -OC 4 F 8 OC 2 F 4 OC 2 F 4 - , and the like. The j is an integer of 2 or more, preferably 3 or more, more preferably 5 or more, and 100 or less, preferably 50 or less. In the above formula, OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 may be linear or branched, preferably linear . In this embodiment, PFPE is preferably, - (OC 2 F 4 -OC 3 F 6) j - or - (OC 2 F 4 -OC 4 F 8) j - is.
　ＰＦＰＥにおいて、ｆに対するｅの比（以下、「ｅ／ｆ比」という）は、０．１以上１０以下であり、好ましくは０．２以上５以下であり、より好ましくは０．２以上２以下であり、さらに好ましくは０．２以上１．５以下であり、さらにより好ましくは０．２以上０．８５以下である。ｅ／ｆ比を１０以下にすることにより、この化合物から得られる層の滑り性、摩擦耐久性および耐ケミカル性（例えば、人工汗に対する耐久性）がより向上する。ｅ／ｆ比がより小さいほど、上記層の滑り性および摩擦耐久性はより向上する。一方、ｅ／ｆ比を０．１以上にすることにより、化合物の安定性をより高めることができる。ｅ／ｆ比がより大きいほど、化合物の安定性はより向上する。 In PFPE, the ratio of e to f (hereinafter referred to as “e / f ratio”) is 0.1 or more and 10 or less, preferably 0.2 or more and 5 or less, and more preferably 0.2 or more and 2 or less More preferably, it is 0.2 or more and 1.5 or less, and still more preferably 0.2 or more and 0.85 or less. By making the e / f ratio 10 or less, the slipperiness, friction durability and chemical resistance (for example, durability against artificial sweat) of the layer obtained from this compound are further improved. The smaller the e / f ratio, the better the slip and friction durability of the layer. On the other hand, by setting the e / f ratio to 0.1 or more, the stability of the compound can be further enhanced. The higher the e / f ratio, the better the stability of the compound.
　上記ＰＦＰＥ含有シラン化合物において、－ＰＦＰＥ－部分の数平均分子量は、特に限定されるものではないが、例えば５００～３０，０００、好ましくは１，５００～３０，０００、より好ましくは２，０００～１０，０００である。上記数平均分子量は、１９Ｆ－ＮＭＲにより測定される値とする。 In the above-mentioned PFPE-containing silane compound, the number average molecular weight of -PFPE- moiety is not particularly limited, but for example, 500 to 30,000, preferably 1,500 to 30,000, more preferably 2,000 to It is 10,000. The above-mentioned number average molecular weight is a value measured by 19 F-NMR.
　別の態様において、－ＰＦＰＥ－部分の数平均分子量は、５００～３０，０００、好ましくは１，０００～２０，０００、より好ましくは２，０００～１５，０００、さらにより好ましくは２，０００～１０，０００、例えば３，０００～６，０００であり得る。 In another embodiment, the number average molecular weight of -PFPE- moiety is 500 to 30,000, preferably 1,000 to 20,000, more preferably 2,000 to 15,000, still more preferably 2,000 to It may be 10,000, for example 3,000 to 6,000.
　別の態様において、－ＰＦＰＥ－部分の数平均分子量は、４，０００～３０，０００、好ましくは５，０００～１０，０００、より好ましくは６，０００～１０，０００であり得る。 In another embodiment, the number average molecular weight of the -PFPE- moiety may be 4,000 to 30,000, preferably 5,000 to 10,000, more preferably 6,000 to 10,000.
　上記式中、Ｒ１３は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表す。 In the above formulae, R 13 independently at each occurrence represents a hydroxyl group or a hydrolysable group.
　上記「加水分解可能な基」とは、本明細書において用いられる場合、加水分解反応を受け得る基を意味し、すなわち、加水分解反応により、化合物の主骨格から脱離し得る基を意味する。加水分解可能な基の例としては、－ＯＲ、－ＯＣＯＲ、－Ｏ－Ｎ＝ＣＲ２、－ＮＲ２、－ＮＨＲ、ハロゲン（これら式中、Ｒは、置換または非置換の炭素数１～４のアルキル基を示す）などが挙げられ、好ましくは－ＯＲ（即ち、アルコキシ基）である。Ｒの例には、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基などの非置換アルキル基；クロロメチル基などの置換アルキル基が含まれる。それらの中でも、アルキル基、特に非置換アルキル基が好ましく、メチル基またはエチル基がより好ましい。水酸基は、特に限定されないが、加水分解可能な基が加水分解して生じたものであってよい。 The above "hydrolyzable group" as used herein means a group capable of undergoing a hydrolysis reaction, that is, a group capable of leaving a main skeleton of a compound by a hydrolysis reaction. Examples of hydrolyzable groups include —OR, —OCOR, —O—N = CR 2 , —NR 2 , —NHR, halogen (in these formulas, R represents substituted or unsubstituted C 1 to 4 carbon atoms) And the like) and the like, and preferably -OR (that is, an alkoxy group). Examples of R include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl and isobutyl; and substituted alkyl groups such as chloromethyl. Among them, an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable. The hydroxyl group is not particularly limited, but may be formed by hydrolysis of a hydrolyzable group.
　上記式中、Ｒ１４は、各出現においてそれぞれ独立して、水素原子または炭素数１～２２のアルキル基、好ましくは炭素数１～４のアルキル基を表す。 In the above formulas, R 14 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms.
　上記式中、Ｒ１１は、各出現において、それぞれ独立して、水素原子またはハロゲン原子を表す。ハロゲン原子は、好ましくはヨウ素原子、塩素原子またはフッ素原子であり、より好ましくはフッ素原子である。 In the above formulas, each occurrence of R 11 independently represents a hydrogen atom or a halogen atom. The halogen atom is preferably an iodine atom, a chlorine atom or a fluorine atom, and more preferably a fluorine atom.
　上記式中、Ｒ１２は、各出現において、それぞれ独立して、水素原子または低級アルキル基を表す。低級アルキル基は、好ましくは炭素数１～２０のアルキル基であり、より好ましくは炭素数１～６のアルキル基であり、例えばメチル基、エチル基、プロピル基等が挙げられる。 In the above formulas, each occurrence of R 12 independently represents a hydrogen atom or a lower alkyl group. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group and a propyl group.
　上記式中、ｎ１は、（－ＳｉＲ１３ ｎ１Ｒ１４ ３－ｎ１）単位毎に独立して、０～３の整数であり、好ましくは１～３であり、より好ましくは３である。式中、少なくとも１つのｎ１が１～３の整数であり、即ち、すべてのｎ１が同時に０になることはない。換言すれば、式中、少なくとも１つはＲ１３が存在する。 In the above formula, n1 is independently an integer of 0 to 3, preferably 1 to 3, and more preferably 3 for each (-SiR 13 n1 R 14 3-n1 ) unit. In the formula, at least one n1 is an integer of 1 to 3, that is, all n1 are never 0 simultaneously. In other words, at least one R 13 exists in the formula.
　一の態様において、式（Ａ１）および（Ａ２）において、水酸基または加水分解可能な基に結合したＳｉが少なくとも２つ存在する。即ち、式（Ａ１）および（Ａ２）において、ｎが１以上である－ＳｉＲ１３ ｎ１Ｒ１４ ３－ｎ１構造（即ち、－ＳｉＲ１３部分）が少なくとも２つ存在する。 In one embodiment, in the formulas (A1) and (A2), at least two Si bonded to a hydroxyl group or a hydrolyzable group are present. That is, in the formulas (A1) and (A2), at least two —SiR 13 n1 R 14 3-n1 structures (ie, —SiR 13 moieties) in which n is 1 or more exist.
　上記式中、Ｘ１は、それぞれ独立して、単結合または２～１０価の有機基を表す。当該Ｘ１は、式（Ａ１）および（Ａ２）で表される化合物において、主に撥水性および表面滑り性等を提供するパーフルオロポリエーテル部（即ち、Ｒｆ－ＰＦＰＥ部または－ＰＦＰＥ－部）と、基材との結合能を提供するシラン部（即ち、α１を付して括弧でくくられた基）とを連結するリンカーと解される。従って、当該Ｘ１は、式（Ａ１）および（Ａ２）で表される化合物が安定に存在し得るものであれば、いずれの有機基であってもよい。 In the above formulas, each X 1 independently represents a single bond or a di- to 10-valent organic group. The said X 1 is a perfluoropolyether part (namely, Rf-PFPE part or -PFPE- part) which mainly provides water repellency, surface slip property, etc. in the compound represented by Formula (A1) and (A2) And a silane moiety that provides the ability to bind to a substrate (ie, a group that is bracketed with .alpha.1). Accordingly, X 1 may be any organic group as long as the compounds represented by formulas (A1) and (A2) can stably exist.
　別の態様において、Ｘ１は、Ｘｅであり得る。Ｘｅは、単結合または２～１０価の有機基を表し、好ましくは、単結合または－Ｃ６Ｈ４－（すなわち－フェニレン－。以下、フェニレン基を示す。）、－ＣＯ－（カルボニル基）、－ＮＲ４－および－ＳＯ２－からなる群より選ばれる少なくとも１つを有する２～１０価の有機基を表す。上記Ｒ４は、それぞれ独立して、水素原子、フェニル基、またはＣ１～６アルキル基（好ましくはメチル基）を表し、好ましくは水素原子、またはメチル基である。上記の－Ｃ６Ｈ４－、－ＣＯ－、－ＮＲ４－または－ＳＯ２－は、ＰＦＰＥ含有シラン化合物の分子主鎖中に含まれることが好ましい。ここで、分子主鎖とは、ＰＦＰＥ含有シラン化合物の分子中で相対的に最も長い結合鎖を表す。 In another aspect, X 1 can be X e . X e represents a single bond or 2-10 divalent organic group, preferably a single bond or -C 6 H 4 -, (i.e. - - phenylene. Hereinafter, a phenylene group.) - CO- (carbonyl group And 2) to a decavalent organic group having at least one selected from the group consisting of -NR 4 -and -SO 2- . Each R 4 independently represents a hydrogen atom, a phenyl group, or a C 1-6 alkyl group (preferably a methyl group), preferably a hydrogen atom or a methyl group. The —C 6 H 4 —, —CO—, —NR 4 — or —SO 2 — is preferably contained in the molecular main chain of the PFPE-containing silane compound. Here, the molecular main chain represents the relatively longest linking chain in the molecule of the PFPE-containing silane compound.
　Ｘｅは、より好ましくは、単結合または－Ｃ６Ｈ４－、－ＣＯＮＲ４－、－ＣＯＮＲ４－Ｃ６Ｈ４－、－ＣＯ－、－ＣＯ－Ｃ６Ｈ４－、－ＳＯ２ＮＲ４－、－ＳＯ２ＮＲ４－Ｃ６Ｈ４－、－ＳＯ２－、および－ＳＯ２－Ｃ６Ｈ４－からなる群より選ばれる少なくとも１つを有する２～１０価の有機基を表す。上記の－Ｃ６Ｈ４－、－ＣＯＮＲ４－、－ＣＯＮＲ４－Ｃ６Ｈ４－、－ＣＯ－、－ＣＯ－Ｃ６Ｈ４－、－ＳＯ２ＮＲ４－、－ＳＯ２ＮＲ４－Ｃ６Ｈ４－、－ＳＯ２－、または－ＳＯ２－Ｃ６Ｈ４－は、ＰＦＰＥ含有シラン化合物の分子主鎖中に含まれることが好ましい。 X e is more preferably a single bond or -C 6 H 4 -, - CONR 4 -, - CONR 4 -C 6 H 4 -, - CO -, - CO-C 6 H 4 -, - SO 2 NR 4 -, - SO 2 NR 4 -C 6 H 4 -, - SO 2 -, and -SO 2 -C 6 H 4 - represents a 2-10 monovalent organic group having at least one selected from the group consisting of . Additional -C 6 H 4 -, - CONR 4 -, - CONR 4 -C 6 H 4 -, - CO -, - CO-C 6 H 4 -, - SO 2 NR 4 -, - SO 2 NR 4 - C 6 H 4 -, - SO 2 -, or -SO 2 -C 6 H 4 - is preferably contained in the molecular backbone of the PFPE-containing silane compound.
　上記式中、α１は１～９の整数であり、α１’は１～９の整数である。これらα１およびα１’は、Ｘ１の価数に応じて変化し得る。式（Ａ１）においては、α１およびα１’の和は、Ｘ１の価数と同じである。例えば、Ｘ１が１０価の有機基である場合、α１およびα１’の和は１０であり、例えばα１が９かつα１’が１、α１が５かつα１’が５、またはα１が１かつα１’が９となり得る。また、Ｘ１が２価の有機基である場合、α１およびα１’は１である。式（Ａ２）においては、α１はＸ１の価数から１を引いた値である。 In the above formula, α1 is an integer of 1 to 9, and α1 ′ is an integer of 1 to 9. These α1 and α1 ′ can change according to the valence of X 1 . In formula (A1), the sum of α1 and α1 ′ is the same as the valence of X 1 . For example, when X 1 is a 10-valent organic group, [alpha] 1 and [alpha] 1 'sum is 10, for example, [alpha] 1 is 9 and [alpha] 1' is 1, [alpha] 1 is 5 and [alpha] 1 'is 5 or [alpha] 1 is 1 and [alpha] 1, 'Can be nine. When X 1 is a divalent organic group, α 1 and α 1 ′ are 1. In formula (A2), [alpha] 1 is the value obtained by subtracting 1 from the valence of X 1.
　上記Ｘ１は、好ましくは２～７価であり、より好ましくは２～４価であり、さらに好ましくは２価の有機基である。 The above X 1 is preferably a divalent to heptavalent, more preferably a divalent to tetravalent, and still more preferably a divalent organic group.
　一の態様において、Ｘ１は２～４価の有機基であり、α１は１～３であり、α１’は１である。 In one embodiment, X 1 is a divalent to tetravalent organic group, α 1 is 1 to 3 and α 1 ′ is 1.
　別の態様において、Ｘ１は２価の有機基であり、α１は１であり、α１’は１である。この場合、式（Ａ１）および（Ａ２）は、下記式（Ａ１’）および（Ａ２’）で表される。
Figure JPOXMLDOC01-appb-C000003
 In another embodiment, X 1 is a divalent organic group, α 1 is 1, and α 1 ′ is 1. In this case, the formulas (A1) and (A2) are represented by the following formulas (A1 ′) and (A2 ′).
Figure JPOXMLDOC01-appb-C000003
　上記Ｘ１の例としては、特に限定するものではないが、例えば、下記式：
　　　－（Ｒ３１）ｐ’－（Ｘａ）ｑ’－
［式中：
　Ｒ３１は、単結合、－（ＣＨ２）ｓ’－またはｏ－、ｍ－もしくはｐ－フェニレン基を表し、好ましくは－（ＣＨ２）ｓ’－であり、
　ｓ’は、１～２０の整数、好ましくは１～６の整数、より好ましくは１～３の整数、さらにより好ましくは１または２であり、
　Ｘａは、－（Ｘｂ）ｌ’－を表し、
　Ｘｂは、各出現においてそれぞれ独立して、－Ｏ－、－Ｓ－、ｏ－、ｍ－もしくはｐ－フェニレン基、－Ｃ（Ｏ）Ｏ－、－Ｓｉ（Ｒ３３）２－、－（Ｓｉ（Ｒ３３）２Ｏ）ｍ’－Ｓｉ（Ｒ３３）２－、－ＣＯＮＲ３４－、－Ｏ－ＣＯＮＲ３４－、－ＮＲ３４－および－（ＣＨ２）ｎ’－からなる群から選択される基を表し、
　Ｒ３３は、各出現においてそれぞれ独立して、フェニル基、Ｃ１－６アルキル基またはＣ１－６アルコキシ基を表し、好ましくはフェニル基またはＣ１－６アルキル基であり、より好ましくはメチル基であり、
　Ｒ３４は、各出現においてそれぞれ独立して、水素原子、フェニル基またはＣ１－６アルキル基（好ましくはメチル基）を表し、
　ｍ’は、各出現において、それぞれ独立して、１～１００の整数、好ましくは１～２０の整数であり、
　ｎ’は、各出現において、それぞれ独立して、１～２０の整数、好ましくは１～６の整数、より好ましくは１～３の整数であり、
　ｌ’は、１～１０の整数、好ましくは１～５の整数、より好ましくは１～３の整数であり、
　ｐ’は、０または１であり、
　ｑ’は、０または１であり、
　ここに、ｐ’およびｑ’の少なくとも一方は１であり、ｐ’またはｑ’を付して括弧でくくられた各繰り返し単位の存在順序は任意である］
で表される２価の基が挙げられる。ここに、Ｒ３１およびＸａ（典型的にはＲ３１およびＸａの水素原子）は、フッ素原子、Ｃ１－３アルキル基およびＣ１－３フルオロアルキル基から選択される１個またはそれ以上の置換基により置換されていてもよい。 Although it does not specifically limit as an example of said X 1 , For example, following formula:
-(R 31 ) p ' -(X a ) q'-
[In the formula:
R 31 represents a single bond,-(CH 2 ) s ' -or o-, m- or p-phenylene group, preferably-(CH 2 ) s'-
s ′ is an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and still more preferably 1 or 2.
X a represents-(X b ) l ' -
X b is independently at each occurrence -O-, -S-, o-, m- or p-phenylene, -C (O) O-, -Si (R 33 ) 2 -,-( Si (R 33) 2 O) m '-Si (R 33) 2 -, - CONR 34 -, - O-CONR 34 -, - NR 34 - and - (CH 2) n' - is selected from the group consisting of Represents a group
R 33 each independently represents a phenyl group, a C 1-6 alkyl group or a C 1-6 alkoxy group, preferably a phenyl group or a C 1-6 alkyl group, more preferably a methyl group And
R 34 independently at each occurrence represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group (preferably a methyl group),
m 'is each independently an integer of 1 to 100, preferably an integer of 1 to 20 at each occurrence;
n 'is independently at each occurrence an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3,
l ′ is an integer of 1 to 10, preferably an integer of 1 to 5, and more preferably an integer of 1 to 3,
p 'is 0 or 1 and
q 'is 0 or 1 and
Here, at least one of p 'and q' is 1, and the existence order of each repeating unit enclosed in parentheses with p 'or q' is arbitrary.]
The bivalent group represented by these is mentioned. Here, R 31 and X a (typically, a hydrogen atom of R 31 and X a ) are one or more selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group It may be substituted by the substituent of
　好ましくは、上記Ｘ１は、－（Ｒ３１）ｐ’－（Ｘａ）ｑ’－Ｒ３２－である。Ｒ３２は、単結合、－（ＣＨ２）ｔ’－またはｏ－、ｍ－もしくはｐ－フェニレン基を表し、好ましくは－（ＣＨ２）ｔ’－である。ｔ’は、１～２０の整数、好ましくは２～６の整数、より好ましくは２～３の整数である。ここに、Ｒ３２（典型的にはＲ３２中の水素原子）は、フッ素原子、Ｃ１－３アルキル基およびＣ１－３フルオロアルキル基から選択される１個またはそれ以上の置換基により置換されていてもよい。 Preferably, the above X 1 is- (R 31 ) p ' -(X a ) q' -R 32- . R 32 represents a single bond,-(CH 2 ) t ' -or o-, m- or p-phenylene group, preferably-(CH 2 ) t'- . t ′ is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3. Here, R 32 (typically a hydrogen atom in R 32 ) is substituted by one or more substituents selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group It may be done.
　好ましくは、上記Ｘ１は、
単結合、
Ｃ１－２０アルキレン基、
－Ｒ３１－Ｘｃ－Ｒ３２－、または
－Ｘｄ－Ｒ３２－
［式中、Ｒ３１およびＲ３２は、上記と同意義である。］
であり得る。なお、アルキレン基とは、－（ＣδＨ２δ）－構造を有する基であり、置換または非置換であってよく、直鎖状または分枝鎖状であってもよい。 Preferably, said X 1 is
Single bond,
C 1-20 alkylene group,
-R 31 -X c -R 32- or -X d -R 32-
[Wherein, R 31 and R 32 are as defined above. ]
It can be. Note that the alkylene group, - (C δ H 2δ) - a group having the structure, may be substituted or unsubstituted, may be linear or branched.
　さらに好ましくは、上記Ｘ１は、
－Ｘｆ－、
－Ｘｆ－Ｃ１－２０アルキレン基、
－Ｘｆ－（ＣＨ２）ｓ’－Ｘｃ－、
－Ｘｆ－（ＣＨ２）ｓ’－Ｘｃ－（ＣＨ２）ｔ’－
－Ｘｆ－Ｘｄ－、または
－Ｘｆ－Ｘｄ－（ＣＨ２）ｔ’－
である。式中、ｓ’およびｔ’は、上記と同意義である。
　上記式中、Ｘｆは、炭素原子数１～６、好ましくは炭素原子数１～４、より好ましくは炭素原子数１～２のアルキレン基、例えばメチレン基である。Ｘｆ中の水素原子は、フッ素原子、Ｃ１－３アルキル基およびＣ１－３フルオロアルキル基から選択される１個またはそれ以上の置換基により置換されていてもよく、好ましくは置換されている。Ｘｆは、直鎖状または分枝鎖状であってもよく、好ましくは直鎖状である。 More preferably, X 1 is
-X f -,
-X f -C 1-20 alkylene group,
-X f - (CH 2) s ' -X c -,
-X f - (CH 2) s '-X c - (CH 2) t' -
-X f -X d- or -X f -X d- (CH 2 ) t ' -
It is. In the formula, s 'and t' are as defined above.
In the above formula, X f is an alkylene group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, such as a methylene group. The hydrogen atom in X f may be substituted by one or more substituents selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group, preferably substituted There is. X f may be linear or branched, and is preferably linear.
　より好ましくは、上記Ｘ１は、
単結合、
Ｃ１－２０アルキレン基、
－（ＣＨ２）ｓ’－Ｘｃ－、
－（ＣＨ２）ｓ’－Ｘｃ－（ＣＨ２）ｔ’－
－Ｘｄ－、または
－Ｘｄ－（ＣＨ２）ｔ’－
［式中、ｓ’およびｔ’は、上記と同意義である。］
である。 More preferably, X 1 is
Single bond,
C 1-20 alkylene group,
-(CH 2 ) s' -X c- ,
-(CH 2 ) s ' -X c- (CH 2 ) t'-
-X d- or -X d- (CH 2 ) t ' -
[Wherein, s ′ and t ′ are as defined above. ]
It is.
　上記式中、Ｘｃは、
－Ｏ－、
－Ｓ－、
－Ｃ（Ｏ）Ｏ－、
－ＣＯＮＲ３４－、
－Ｏ－ＣＯＮＲ３４－、
－Ｓｉ（Ｒ３３）２－、
－（Ｓｉ（Ｒ３３）２Ｏ）ｍ’－Ｓｉ（Ｒ３３）２－、
－Ｏ－（ＣＨ２）u’－（Ｓｉ（Ｒ３３）２Ｏ）ｍ’－Ｓｉ（Ｒ３３）２－、
－Ｏ－（ＣＨ２）u’－Ｓｉ（Ｒ３３）２－Ｏ－Ｓｉ（Ｒ３３）２－ＣＨ２ＣＨ２－Ｓｉ（Ｒ３３）２－Ｏ－Ｓｉ（Ｒ３３）２－、
－Ｏ－（ＣＨ２）u’－Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２－、
－ＣＯＮＲ３４－（ＣＨ２）u’－（Ｓｉ（Ｒ３３）２Ｏ）ｍ’－Ｓｉ（Ｒ３３）２－、
－ＣＯＮＲ３４－（ＣＨ２）u’－Ｎ（Ｒ３４）－、または
－ＣＯＮＲ３４－（ｏ－、ｍ－またはｐ－フェニレン）－Ｓｉ（Ｒ３３）２－
［式中、Ｒ３３、Ｒ３４およびｍ’は、上記と同意義であり、
　ｕ’は１～２０の整数、好ましくは２～６の整数、より好ましくは２～３の整数である。］を表す。Ｘｃは、好ましくは－Ｏ－である。 In the above formula, X c is
-O-,
-S-,
-C (O) O-,
-CONR 34 -,
-O-CONR 34 -,
-Si (R 33 ) 2- ,
- (Si (R 33) 2 O) m '-Si (R 33) 2 -,
-O- (CH 2) u '- (Si (R 33) 2 O) m' -Si (R 33) 2 -,
-O- (CH 2) u '-Si (R 33) 2 -O-Si (R 33) 2 -CH 2 CH 2 -Si (R 33) 2 -O-Si (R 33) 2 -,
-O- (CH 2) u '-Si (OCH 3) 2 OSi (OCH 3) 2 -,
-CONR 34 - (CH 2) u '- (Si (R 33) 2 O) m' -Si (R 33) 2 -,
-CONR 34 - (CH 2) u '-N (R 34) -, or -CONR 34 - (o-, m- or p- phenylene) -Si (R 33) 2 -
[Wherein, R 33 , R 34 and m ′ are as defined above,
u ′ is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3. Represents]. X c is preferably -O-.
　上記式中、Ｘｄは、
－Ｓ－、
－Ｃ（Ｏ）Ｏ－、
－ＣＯＮＲ３４－、
－ＣＯＮＲ３４－（ＣＨ２）u’－（Ｓｉ（Ｒ３３）２Ｏ）ｍ’－Ｓｉ（Ｒ３３）２－、
－ＣＯＮＲ３４－（ＣＨ２）u’－Ｎ（Ｒ３４）－、または
－ＣＯＮＲ３４－（ｏ－、ｍ－またはｐ－フェニレン）－Ｓｉ（Ｒ３３）２－
［式中、各記号は、上記と同意義である。］
を表す。 In the above formula, X d is
-S-,
-C (O) O-,
-CONR 34 -,
-CONR 34 - (CH 2) u '- (Si (R 33) 2 O) m' -Si (R 33) 2 -,
-CONR 34 - (CH 2) u '-N (R 34) -, or -CONR 34 - (o-, m- or p- phenylene) -Si (R 33) 2 -
[Wherein each symbol is as defined above. ]
Represents
　特に好ましくは、上記Ｘ１は、
－Ｘｆ－、
－Ｘｆ－Ｃ１－２０アルキレン基、
－Ｘｆ－（ＣＨ２）ｓ’－Ｘｃ－、
－Ｘｆ－（ＣＨ２）ｓ’－Ｘｃ－（ＣＨ２）ｔ’－
－Ｘｆ－Ｘｄ－、または
－Ｘｆ－Ｘｄ－（ＣＨ２）ｔ’－
［式中、Ｘｆ、ｓ’およびｔ’は、上記と同意義である。］
であり、
　Ｘｃが、－Ｏ－、または－ＣＯＮＲ３４－、
　Ｘｄが、－ＣＯＮＲ３４－、
　Ｒ３４は、各出現においてそれぞれ独立して、水素原子、フェニル基またはＣ１－６アルキル基（好ましくはメチル基）を表す。］
で表される基である。 Particularly preferably, X 1 is
-X f -,
-X f -C 1-20 alkylene group,
-X f - (CH 2) s ' -X c -,
-X f - (CH 2) s '-X c - (CH 2) t' -
-X f -X d- or -X f -X d- (CH 2 ) t ' -
[Wherein, X f , s ′ and t ′ are as defined above. ]
And
X c is, -O-, or -CONR 34 -,
X d is, -CONR 34 -,
R 34 each independently represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group (preferably a methyl group) at each occurrence. ]
Is a group represented by
　一の態様において、上記Ｘ１は、
－Ｘｆ－（ＣＨ２）ｓ’－Ｘｃ－、
－Ｘｆ－（ＣＨ２）ｓ’－Ｘｃ－（ＣＨ２）ｔ’－
－Ｘｆ－Ｘｄ－、または
－Ｘｆ－Ｘｄ－（ＣＨ２）ｔ’－
［式中、Ｘｆ、ｓ’およびｔ’は、上記と同意義である。］
であり、
　Ｘｃが、－ＣＯＮＲ３４－、
　Ｘｄが、－ＣＯＮＲ３４－、
　Ｒ３４は、各出現においてそれぞれ独立して、水素原子、フェニル基またはＣ１－６アルキル基（好ましくはメチル基）を表す。］
で表される基である。 In one embodiment, X 1 is
-X f - (CH 2) s ' -X c -,
-X f - (CH 2) s '-X c - (CH 2) t' -
-X f -X d- or -X f -X d- (CH 2 ) t ' -
[Wherein, X f , s ′ and t ′ are as defined above. ]
And
X c is, -CONR 34 -,
X d is, -CONR 34 -,
R 34 each independently represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group (preferably a methyl group) at each occurrence. ]
Is a group represented by
　より好ましくは、上記Ｘ１は、
単結合、
Ｃ１－２０アルキレン基、
－（ＣＨ２）ｓ’－Ｘｃ－（ＣＨ２）ｔ’－、または
－Ｘｄ－（ＣＨ２）ｔ’－
［式中、各記号は、上記と同意義である。］
であり得る。 More preferably, X 1 is
Single bond,
C 1-20 alkylene group,
-(CH 2 ) s' -X c- (CH 2 ) t ' -or -X d- (CH 2 ) t'-
[Wherein each symbol is as defined above. ]
It can be.
　さらにより好ましくは、上記Ｘ１は、
単結合、
Ｃ１－２０アルキレン基、
－（ＣＨ２）ｓ’－Ｏ－（ＣＨ２）ｔ’－、
－（ＣＨ２）ｓ’－（Ｓｉ（Ｒ３３）２Ｏ）ｍ’－Ｓｉ（Ｒ３３）２－（ＣＨ２）ｔ’－、
－（ＣＨ２）ｓ’－Ｏ－（ＣＨ２）u’－（Ｓｉ（Ｒ３３）２Ｏ）ｍ’－Ｓｉ（Ｒ３３）２－（ＣＨ２）ｔ’－、または
－（ＣＨ２）ｓ’－Ｏ－（ＣＨ２）ｔ’－Ｓｉ（Ｒ３３）２ －（ＣＨ２）u’－Ｓｉ（Ｒ３３）２－（ＣvＨ２v）－
［式中、Ｒ３３、ｍ’、ｓ’、ｔ’およびｕ’は、上記と同意義であり、ｖは１～２０の整数、好ましくは２～６の整数、より好ましくは２～３の整数である。］
である。 Even more preferably, X 1 is
Single bond,
C 1-20 alkylene group,
-(CH 2 ) s ' -O- (CH 2 ) t'- ,
-(CH 2 ) s' -(Si (R 33 ) 2 O) m ' -Si (R 33 ) 2- (CH 2 ) t'- ,
- (CH 2) s '-O- (CH 2) u' - (Si (R 33) 2 O) m '-Si (R 33) 2 - (CH 2) t' -, or - (CH 2) s' -O- (CH 2) t '-Si (R 33) 2 - (CH 2) u' -Si (R 33) 2 - (C v H 2v) -
[Wherein, R 33 , m ′, s ′, t ′ and u ′ are as defined above, and v is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably 2 to 3] It is an integer. ]
It is.
　上記式中、－（ＣvＨ２v）－は、直鎖であっても、分枝鎖であってもよく、例えば、－ＣＨ２－、－ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ２ＣＨ２－、－ＣＨ（ＣＨ３）－、－ＣＨ（ＣＨ３）ＣＨ２－であり得る。 In the above formulae,-(C v H 2v ) -may be linear or branched, and for example, -CH 2- , -CH 2 CH 2- , -CH 2 CH 2 CH 2 -, - CH (CH 3 ) -, - CH (CH 3) CH 2 - may be.
　上記Ｘ１基は、フッ素原子、Ｃ１－３アルキル基およびＣ１－３フルオロアルキル基（好ましくは、Ｃ１－３パーフルオロアルキル基）から選択される１個またはそれ以上の置換基により置換されていてもよい。 The X 1 group is substituted by one or more substituents selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group (preferably a C 1-3 perfluoroalkyl group) It may be done.
　一の態様において、Ｘ１基は、－Ｏ－Ｃ１－６アルキレン基以外であり得る。 In one aspect, the X 1 group may be other than an —O—C 1-6 alkylene group.
　別の態様において、Ｘ１基としては、例えば下記の基が挙げられる：
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000005
 ［式中、Ｒ４１は、それぞれ独立して、水素原子、フェニル基、炭素数１～６のアルキル基、またはＣ１－６アルコキシ基、好ましくはメチル基であり；
　Ｄは、
－ＣＨ２Ｏ（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３－、
－ＣＦ２Ｏ（ＣＨ２）３－、
－（ＣＨ２）２－、
－（ＣＨ２）３－、
－（ＣＨ２）4－、
－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）３－（式中、Ｐｈはフェニルを意味する）、および
Figure JPOXMLDOC01-appb-C000006
 （式中、Ｒ４２は、それぞれ独立して、水素原子、Ｃ１－６のアルキル基またはＣ１－６のアルコキシ基、好ましくはメチル基またはメトキシ基、より好ましくはメチル基を表す。）
から選択される基であり、
　Ｅは、－（ＣＨ２）ｎｅ－（ｎｅは２～６の整数）であり、
　Ｄは、分子主鎖のＰＦＰＥに結合し、Ｅは、ＰＦＰＥと反対の基に結合する。］ In another embodiment, the X 1 group includes, for example, the following groups:
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000005
 [Wherein each R 41 independently represents a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C 1-6 alkoxy group, preferably a methyl group;
D is
-CH 2 O (CH 2 ) 2- ,
-CH 2 O (CH 2 ) 3- ,
-CF 2 O (CH 2 ) 3- ,
-(CH 2 ) 2- ,
-(CH 2 ) 3- ,
- (CH 2) 4 -,
-CONH- (CH 2 ) 3- ,
-CON (CH 3 )-(CH 2 ) 3- ,
-CON (Ph)-(CH 2 ) 3- (wherein, Ph means phenyl), and
Figure JPOXMLDOC01-appb-C000006
 (Wherein, each R 42 independently represents a hydrogen atom, a C 1-6 alkyl group or a C 1-6 alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group).
Is a group selected from
E is- (CH 2 ) ne- (ne is an integer of 2 to 6),
D is attached to the PFPE of the molecular backbone and E is attached to the opposite group to the PFPE. ]
　上記Ｘ１の具体的な例としては、例えば：
単結合
－ＣＨ２ＯＣＨ２－、
－ＣＨ２Ｏ（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３－、
－ＣＨ２Ｏ（ＣＨ２）６－、
－ＣＦ２－ＣＨ２－Ｏ－ＣＨ２－、
－ＣＦ２－ＣＨ２－Ｏ－（ＣＨ２）２－、
－ＣＦ２－ＣＨ２－Ｏ－（ＣＨ２）３－、
－ＣＦ２－ＣＨ２－Ｏ－（ＣＨ２）６－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）３Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）１０Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２０Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－Ｃ（Ｏ）ＮＨ－ＣＨ２－、
－ＣＨ２ＯＣＨ２（ＣＨ２）７ＣＨ２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）２－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）３－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ２ＣＨ３）２ＯＳｉ（ＯＣＨ２ＣＨ３）２（ＣＨ２）３－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）２－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ２ＣＨ３）２ＯＳｉ（ＯＣＨ２ＣＨ３）２（ＣＨ２）２－、
－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－、
－ＣＨ２－、
－（ＣＨ２）２－、
－（ＣＨ２）３－、
－（ＣＨ２）４－、
－（ＣＨ２）５－、
－（ＣＨ２）６－、
－ＣＦ２－、
－（ＣＦ２）２－、
－ＣＦ２－ＣＨ２－、
－ＣＦ２－（ＣＨ２）２－、
－ＣＦ２－（ＣＨ２）３－、
－ＣＦ２－（ＣＨ２）４－、
－ＣＦ２－（ＣＨ２）５－、
－ＣＦ２－（ＣＨ２）６－、
－ＣＯ－
－ＣＯＮＨ－
－ＣＯＮＨ－ＣＨ２－、
－ＣＯＮＨ－（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＯＮＨ－（ＣＨ２）６－、
－ＣＦ２ＣＯＮＨ－、
－ＣＦ２ＣＯＮＨＣＨ２－、
－ＣＦ２ＣＯＮＨ（ＣＨ２）２－、
－ＣＦ２ＣＯＮＨ（ＣＨ２）３－、
－ＣＦ２ＣＯＮＨ（ＣＨ２）６－、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）３－（式中、Ｐｈはフェニルを意味する）、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）６－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）６－（式中、Ｐｈはフェニルを意味する）、
－ＣＦ２－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＦ２－ＣＯＮ（Ｐｈ）－（ＣＨ２）３－（式中、Ｐｈはフェニルを意味する）、
－ＣＦ２－ＣＯＮ（ＣＨ３）－（ＣＨ２）６－、
－ＣＦ２－ＣＯＮ（Ｐｈ）－（ＣＨ２）６－（式中、Ｐｈはフェニルを意味する）、
－ＣＯＮＨ－（ＣＨ２）２ＮＨ（ＣＨ２）３－、
－ＣＯＮＨ－（ＣＨ２）６ＮＨ（ＣＨ２）３－、
－ＣＨ２Ｏ－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＨ２Ｏ－ＣＯＮＨ－（ＣＨ２）６－、
－Ｓ－（ＣＨ２）３－、
－（ＣＨ２）２Ｓ（ＣＨ２）３－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）３Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）１０Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２０Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－Ｃ（Ｏ）Ｏ－（ＣＨ２）３－、
－Ｃ（Ｏ）Ｏ－（ＣＨ２）６－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－ＣＨ（ＣＨ３）－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－（ＣＨ２）３－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－ＣＨ（ＣＨ３）－ＣＨ２－、
－ＯＣＨ２－、
－Ｏ（ＣＨ２）３－、
－ＯＣＦＨＣＦ２－、
Figure JPOXMLDOC01-appb-C000007
 などが挙げられる。 Specific examples of the above X 1 include, for example:
Single bond -CH 2 OCH 2- ,
-CH 2 O (CH 2 ) 2- ,
-CH 2 O (CH 2 ) 3- ,
-CH 2 O (CH 2 ) 6- ,
-CF 2 -CH 2 -O-CH 2- ,
-CF 2 -CH 2 -O- (CH 2 ) 2- ,
-CF 2 -CH 2 -O- (CH 2 ) 3- ,
-CF 2 -CH 2 -O- (CH 2 ) 6-
-CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2- ,
-CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2- ,
-CH 2 O (CH 2) 3 Si (CH 3) 2 O (Si (CH 3) 2 O) 2 Si (CH 3) 2 (CH 2) 2 -,
-CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 3 Si (CH 3 ) 2 (CH 2 ) 2- ,
-CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 10 Si (CH 3 ) 2 (CH 2 ) 2- ,
-CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 20 Si (CH 3 ) 2 (CH 2 ) 2- ,
-CH 2 OCF 2 CHFOCF 2- ,
-CH 2 OCF 2 CHFOCF 2 CF 2- ,
-CH 2 OCF 2 CHFOCF 2 CF 2 CF 2- ,
-CH 2 OCH 2 CF 2 CF 2 OCF 2- ,
-CH 2 OCH 2 CF 2 CF 2 OCF 2 CF 2- ,
-CH 2 OCH 2 CF 2 CF 2 OCF 2 CF 2 CF 2- ,
-CH 2 OCH 2 CF 2 CF 2 OCF (CF 3) CF 2 OCF 2 -,
-CH 2 OCH 2 CF 2 CF 2 OCF (CF 3) CF 2 OCF 2 CF 2 -,
-CH 2 OCH 2 CF 2 CF 2 OCF (CF 3) CF 2 OCF 2 CF 2 CF 2 -,
-CH 2 OCH 2 CHFCF 2 OCF 2- ,
-CH 2 OCH 2 CHFCF 2 OCF 2 CF 2- ,
-CH 2 OCH 2 CHFCF 2 OCF 2 CF 2 CF 2- ,
-CH 2 OCH 2 CHFCF 2 OCF ( CF 3) CF 2 OCF 2 -,
-CH 2 OCH 2 CHFCF 2 OCF ( CF 3) CF 2 OCF 2 CF 2 -,
-CH 2 OCH 2 CHFCF 2 OCF (CF 3 ) CF 2 OCF 2 CF 2 CF 2-
-CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 -C (O) NH-CH 2- ,
-CH 2 OCH 2 (CH 2 ) 7 CH 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 2- ,
-CH 2 OCH 2 CH 2 CH 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 3- ,
-CH 2 OCH 2 CH 2 CH 2 Si (OCH 2 CH 3 ) 2 OSi (OCH 2 CH 3 ) 2 (CH 2 ) 3- ,
-CH 2 OCH 2 CH 2 CH 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 2- ,
-CH 2 OCH 2 CH 2 CH 2 Si (OCH 2 CH 3 ) 2 OSi (OCH 2 CH 3 ) 2 (CH 2 ) 2- ,
-(CH 2 ) 2 -Si (CH 3 ) 2- (CH 2 ) 2- ,
-CH 2- ,
-(CH 2 ) 2- ,
-(CH 2 ) 3- ,
- (CH 2) 4 -,
-(CH 2 ) 5- ,
-(CH 2 ) 6- ,
-CF 2- ,
-(CF 2 ) 2- ,
-CF 2 -CH 2- ,
-CF 2- (CH 2 ) 2- ,
-CF 2- (CH 2 ) 3- ,
-CF 2 - (CH 2) 4 -,
-CF 2- (CH 2 ) 5- ,
-CF 2- (CH 2 ) 6- ,
-CO-
-CONH-
-CONH-CH 2- ,
-CONH- (CH 2 ) 2- ,
-CONH- (CH 2 ) 3- ,
-CONH- (CH 2 ) 6- ,
-CF 2 CONH-,
-CF 2 CONHCH 2- ,
-CF 2 CONH (CH 2 ) 2- ,
-CF 2 CONH (CH 2 ) 3- ,
-CF 2 CONH (CH 2 ) 6- ,
-CON (CH 3 )-(CH 2 ) 3- ,
-CON (Ph)-(CH 2 ) 3- (wherein Ph means phenyl),
-CON (CH 3 )-(CH 2 ) 6- ,
-CON (Ph)-(CH 2 ) 6- (wherein Ph means phenyl),
-CF 2 -CON (CH 3 )-(CH 2 ) 3- ,
-CF 2 -CON (Ph)-(CH 2 ) 3- (wherein, Ph means phenyl),
-CF 2 -CON (CH 3 )-(CH 2 ) 6- ,
-CF 2 -CON (Ph)-(CH 2 ) 6- (wherein, Ph means phenyl),
-CONH- (CH 2 ) 2 NH (CH 2 ) 3- ,
-CONH- (CH 2 ) 6 NH (CH 2 ) 3- ,
-CH 2 O-CONH- (CH 2 ) 3- ,
-CH 2 O-CONH- (CH 2 ) 6- ,
-S- (CH 2 ) 3- ,
-(CH 2 ) 2 S (CH 2 ) 3- ,
-CONH- (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2- ,
-CONH- (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2- ,
-CONH- (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 2 Si (CH 3 ) 2 (CH 2 ) 2- ,
-CONH- (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 3 Si (CH 3 ) 2 (CH 2 ) 2- ,
-CONH- (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 10 Si (CH 3 ) 2 (CH 2 ) 2- ,
-CONH- (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 20 Si (CH 3 ) 2 (CH 2 ) 2- ,
-C (O) O- (CH 2 ) 3- ,
-C (O) O- (CH 2 ) 6- ,
-CH 2 -O- (CH 2 ) 3 -Si (CH 3 ) 2- (CH 2 ) 2 -Si (CH 3 ) 2- (CH 2 ) 2- ,
-CH 2 -O- (CH 2 ) 3 -Si (CH 3 ) 2- (CH 2 ) 2 -Si (CH 3 ) 2 -CH (CH 3 )-,
-CH 2 -O- (CH 2 ) 3 -Si (CH 3 ) 2- (CH 2 ) 2 -Si (CH 3 ) 2- (CH 2 ) 3- ,
-CH 2 -O- (CH 2 ) 3 -Si (CH 3 ) 2- (CH 2 ) 2 -Si (CH 3 ) 2 -CH (CH 3 ) -CH 2- ,
-OCH 2-
-O (CH 2 ) 3- ,
-OCFHCF 2- ,
Figure JPOXMLDOC01-appb-C000007
 Etc.
　上記の中では、Ｘ１は、
－ＣＨ２ＯＣＨ２－、
－ＣＨ２Ｏ（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３－、
－ＣＨ２Ｏ（ＣＨ２）６－、
－ＣＦ２－ＣＨ２－Ｏ－ＣＨ２－、
－ＣＦ２－ＣＨ２－Ｏ－（ＣＨ２）２－、
－ＣＦ２－ＣＨ２－Ｏ－（ＣＨ２）３－、
－ＣＦ２－ＣＨ２－Ｏ－（ＣＨ２）６－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－Ｃ（Ｏ）ＮＨ－ＣＨ２－、
－ＣＨ２－、
－（ＣＨ２）２－、
－（ＣＨ２）３－、
－（ＣＨ２）４－、
－（ＣＨ２）５－、
－（ＣＨ２）６－、
－ＣＦ２－、
－（ＣＦ２）２－、
－ＣＦ２－ＣＨ２－、
－ＣＦ２－（ＣＨ２）２－、
－ＣＦ２－（ＣＨ２）３－、
－ＣＦ２－（ＣＨ２）４－、
－ＣＦ２－（ＣＨ２）５－、
－ＣＦ２－（ＣＨ２）６－、
－ＣＯＮＨ－、
－ＣＯＮＨ－ＣＨ２－、
－ＣＯＮＨ－（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＯＮＨ－（ＣＨ２）６－、
－ＣＦ２ＣＯＮＨ－、
－ＣＦ２ＣＯＮＨＣＨ２－、
－ＣＦ２ＣＯＮＨ（ＣＨ２）２－、
－ＣＦ２ＣＯＮＨ（ＣＨ２）３－、
－ＣＦ２ＣＯＮＨ（ＣＨ２）６－、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）３－（式中、Ｐｈはフェニルを意味する）、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）６－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）６－（式中、Ｐｈはフェニルを意味する）、
－ＣＦ２－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＦ２－ＣＯＮ（Ｐｈ）－（ＣＨ２）３－（式中、Ｐｈはフェニルを意味する）、
－ＣＦ２－ＣＯＮ（ＣＨ３）－（ＣＨ２）６－、
－ＣＦ２－ＣＯＮ（Ｐｈ）－（ＣＨ２）６－（式中、Ｐｈはフェニルを意味する）、
－ＣＯＮＨ－（ＣＨ２）２ＮＨ（ＣＨ２）３－、
－ＣＯＮＨ－（ＣＨ２）６ＮＨ（ＣＨ２）３－、
－ＣＨ２Ｏ－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＨ２Ｏ－ＣＯＮＨ－（ＣＨ２）６－、
－ＯＣＨ２－、
－Ｏ（ＣＨ２）３－、または
－ＯＣＦＨＣＦ２－、
であることが好ましい。 In the above, X 1 is
-CH 2 OCH 2- ,
-CH 2 O (CH 2 ) 2- ,
-CH 2 O (CH 2 ) 3- ,
-CH 2 O (CH 2 ) 6- ,
-CF 2 -CH 2 -O-CH 2- ,
-CF 2 -CH 2 -O- (CH 2 ) 2- ,
-CF 2 -CH 2 -O- (CH 2 ) 3- ,
-CF 2 -CH 2 -O- (CH 2 ) 6-
-CH 2 OCF 2 CHFOCF 2- ,
-CH 2 OCF 2 CHFOCF 2 CF 2- ,
-CH 2 OCF 2 CHFOCF 2 CF 2 CF 2- ,
-CH 2 OCH 2 CF 2 CF 2 OCF 2- ,
-CH 2 OCH 2 CF 2 CF 2 OCF 2 CF 2- ,
-CH 2 OCH 2 CF 2 CF 2 OCF 2 CF 2 CF 2- ,
-CH 2 OCH 2 CF 2 CF 2 OCF (CF 3) CF 2 OCF 2 -,
-CH 2 OCH 2 CF 2 CF 2 OCF (CF 3) CF 2 OCF 2 CF 2 -,
-CH 2 OCH 2 CF 2 CF 2 OCF (CF 3) CF 2 OCF 2 CF 2 CF 2 -,
-CH 2 OCH 2 CHFCF 2 OCF 2- ,
-CH 2 OCH 2 CHFCF 2 OCF 2 CF 2- ,
-CH 2 OCH 2 CHFCF 2 OCF 2 CF 2 CF 2- ,
-CH 2 OCH 2 CHFCF 2 OCF ( CF 3) CF 2 OCF 2 -,
-CH 2 OCH 2 CHFCF 2 OCF ( CF 3) CF 2 OCF 2 CF 2 -,
-CH 2 OCH 2 CHFCF 2 OCF ( CF 3) CF 2 OCF 2 CF 2 CF 2 -,
-CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 -C (O) NH-CH 2- ,
-CH 2- ,
-(CH 2 ) 2- ,
-(CH 2 ) 3- ,
- (CH 2) 4 -,
-(CH 2 ) 5- ,
-(CH 2 ) 6- ,
-CF 2- ,
-(CF 2 ) 2- ,
-CF 2 -CH 2- ,
-CF 2- (CH 2 ) 2- ,
-CF 2- (CH 2 ) 3- ,
-CF 2 - (CH 2) 4 -,
-CF 2- (CH 2 ) 5- ,
-CF 2- (CH 2 ) 6- ,
-CONH-,
-CONH-CH 2- ,
-CONH- (CH 2 ) 2- ,
-CONH- (CH 2 ) 3- ,
-CONH- (CH 2 ) 6- ,
-CF 2 CONH-,
-CF 2 CONHCH 2- ,
-CF 2 CONH (CH 2 ) 2- ,
-CF 2 CONH (CH 2 ) 3- ,
-CF 2 CONH (CH 2 ) 6- ,
-CON (CH 3 )-(CH 2 ) 3- ,
-CON (Ph)-(CH 2 ) 3- (wherein Ph means phenyl),
-CON (CH 3 )-(CH 2 ) 6- ,
-CON (Ph)-(CH 2 ) 6- (wherein Ph means phenyl),
-CF 2 -CON (CH 3 )-(CH 2 ) 3- ,
-CF 2 -CON (Ph)-(CH 2 ) 3- (wherein, Ph means phenyl),
-CF 2 -CON (CH 3 )-(CH 2 ) 6- ,
-CF 2 -CON (Ph)-(CH 2 ) 6- (wherein, Ph means phenyl),
-CONH- (CH 2 ) 2 NH (CH 2 ) 3- ,
-CONH- (CH 2 ) 6 NH (CH 2 ) 3- ,
-CH 2 O-CONH- (CH 2 ) 3- ,
-CH 2 O-CONH- (CH 2 ) 6- ,
-OCH 2-
-O (CH 2 ) 3- , or -OCFHCF 2- ,
Is preferred.
　上記の中では、より好ましくは、Ｘ１は、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－Ｃ（Ｏ）ＮＨ－ＣＨ２－、
－ＣＯＮＨ－、
－ＣＯＮＨ－ＣＨ２－、
－ＣＯＮＨ－（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＯＮＨ－（ＣＨ２）６－、
－ＣＦ２ＣＯＮＨ－、
－ＣＦ２ＣＯＮＨＣＨ２－、
－ＣＦ２ＣＯＮＨ（ＣＨ２）２－、
－ＣＦ２ＣＯＮＨ（ＣＨ２）３－、
－ＣＦ２ＣＯＮＨ（ＣＨ２）６－、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）３－（式中、Ｐｈはフェニルを意味する）、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）６－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）６－（式中、Ｐｈはフェニルを意味する）、
－ＣＦ２－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＦ２－ＣＯＮ（Ｐｈ）－（ＣＨ２）３－（式中、Ｐｈはフェニルを意味する）、
－ＣＦ２－ＣＯＮ（ＣＨ３）－（ＣＨ２）６－、
－ＣＦ２－ＣＯＮ（Ｐｈ）－（ＣＨ２）６－（式中、Ｐｈはフェニルを意味する）、
－ＣＯＮＨ－（ＣＨ２）２ＮＨ（ＣＨ２）３－、
－ＣＯＮＨ－（ＣＨ２）６ＮＨ（ＣＨ２）３－、
である。 Among the above, more preferably, X 1 is
-CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 -C (O) NH-CH 2- ,
-CONH-,
-CONH-CH 2- ,
-CONH- (CH 2 ) 2- ,
-CONH- (CH 2 ) 3- ,
-CONH- (CH 2 ) 6- ,
-CF 2 CONH-,
-CF 2 CONHCH 2- ,
-CF 2 CONH (CH 2 ) 2- ,
-CF 2 CONH (CH 2 ) 3- ,
-CF 2 CONH (CH 2 ) 6- ,
-CON (CH 3 )-(CH 2 ) 3- ,
-CON (Ph)-(CH 2 ) 3- (wherein Ph means phenyl),
-CON (CH 3 )-(CH 2 ) 6- ,
-CON (Ph)-(CH 2 ) 6- (wherein Ph means phenyl),
-CF 2 -CON (CH 3 )-(CH 2 ) 3- ,
-CF 2 -CON (Ph)-(CH 2 ) 3- (wherein, Ph means phenyl),
-CF 2 -CON (CH 3 )-(CH 2 ) 6- ,
-CF 2 -CON (Ph)-(CH 2 ) 6- (wherein, Ph means phenyl),
-CONH- (CH 2 ) 2 NH (CH 2 ) 3- ,
-CONH- (CH 2 ) 6 NH (CH 2 ) 3- ,
It is.
　より好ましい態様において、Ｘ１は、Ｘｅ’を表す。Ｘｅ’は、単結合、炭素数１～６のアルキレン基、－Ｒ５１－Ｃ６Ｈ４－Ｒ５２－、－Ｒ５１－ＣＯＮＲ４－Ｒ５２－、－Ｒ５１－ＣＯＮＲ４－Ｃ６Ｈ４－Ｒ５２－、－Ｒ５１－ＣＯ－Ｒ５２－、－Ｒ５１－ＣＯ－Ｃ６Ｈ４－Ｒ５２－、－Ｒ５１－ＳＯ２ＮＲ４－Ｒ５２－、－Ｒ５１－ＳＯ２ＮＲ４－Ｃ６Ｈ４－Ｒ５２－、－Ｒ５１－ＳＯ２－Ｒ５２－、または－Ｒ５１－ＳＯ２－Ｃ６Ｈ４－Ｒ５２－である。Ｒ５１およびＲ５２は、それぞれ独立して、単結合または炭素数１～６のアルキレン基を表し、好ましくは単結合または炭素数１～３のアルキレン基である。Ｒ４は上記と同意義である。上記アルキレン基は、置換または非置換であり、好ましくは非置換である。上記アルキレン基の置換基としては、例えばハロゲン原子、好ましくはフッ素原子を挙げることができる。上記アルキレン基は、直鎖状または分枝鎖状であり、直鎖状であることが好ましい。 In a more preferred embodiment, X 1 represents X e ′ . X e ′ is a single bond, an alkylene group having 1 to 6 carbon atoms, -R 51 -C 6 H 4 -R 52- , -R 51 -CONR 4 -R 52- , -R 51 -CONR 4 -C 6 H 4 -R 52- , -R 51 -CO-R 52- , -R 51 -CO-C 6 H 4 -R 52- , -R 51 -SO 2 NR 4 -R 52- , -R 51 -SO 2 NR 4 -C 6 H 4 -R 52- , -R 51 -SO 2 -R 52- , or -R 51 -SO 2 -C 6 H 4 -R 52- . R 51 and R 52 each independently represent a single bond or an alkylene group having 1 to 6 carbon atoms, preferably a single bond or an alkylene group having 1 to 3 carbon atoms. R 4 is as defined above. The alkylene group is substituted or unsubstituted, preferably unsubstituted. As a substituent of the said alkylene group, a halogen atom, Preferably a fluorine atom can be mentioned, for example. The alkylene group is linear or branched, and is preferably linear.
　さらに好ましい態様において、Ｘｅ’は、
単結合、
－Ｘｆ－、
炭素数１～６、好ましくは炭素数１～３のアルキレン基
－Ｘｆ－Ｃ１－６アルキレン基、好ましくは－Ｘｆ－Ｃ１－３アルキレン基、より好ましくは－Ｘｆ－Ｃ１－２アルキレン基、
－Ｃ６Ｈ４－Ｒ５２’－、
－ＣＯＮＲ４’－Ｒ５２’－、
－ＣＯＮＲ４’－Ｃ６Ｈ４－Ｒ５２’－、
－Ｘｆ－ＣＯＮＲ４’－Ｒ５２’－、
－Ｘｆ－ＣＯＮＲ４’－Ｃ６Ｈ４－Ｒ５２’－、
－ＣＯ－Ｒ５２’－、
－ＣＯ－Ｃ６Ｈ４－Ｒ５２’－、
－ＳＯ２ＮＲ４’－Ｒ５２’－、
－ＳＯ２ＮＲ４’－Ｃ６Ｈ４－Ｒ５２’－、
－ＳＯ２－Ｒ５２’－、
－ＳＯ２－Ｃ６Ｈ４－Ｒ５２’－、
－Ｒ５１’－Ｃ６Ｈ４－、
－Ｒ５１’－ＣＯＮＲ４’－、
－Ｒ５１’－ＣＯＮＲ４’－Ｃ６Ｈ４－、
－Ｒ５１’－ＣＯ－、
－Ｒ５１’－ＣＯ－Ｃ６Ｈ４－、
－Ｒ５１’－ＳＯ２ＮＲ４’－、
－Ｒ５１’－ＳＯ２ＮＲ４’－Ｃ６Ｈ４－、
－Ｒ５１’－ＳＯ２－、
－Ｒ５１’－ＳＯ２－Ｃ６Ｈ４－、
－Ｃ６Ｈ４－
－ＣＯＮＲ４’－、
－ＣＯＮＲ４’－Ｃ６Ｈ４－、
－Ｘｆ－ＣＯＮＲ４’－、
－Ｘｆ－ＣＯＮＲ４’－Ｃ６Ｈ４－、
－ＣＯ－、
－ＣＯ－Ｃ６Ｈ４－、
－ＳＯ２ＮＲ４’－、
－ＳＯ２ＮＲ４’－Ｃ６Ｈ４－
－ＳＯ２－、または
－ＳＯ２－Ｃ６Ｈ４－
（式中、Ｒ５１’およびＲ５２’は、それぞれ独立して、炭素数１～６、好ましくは炭素数１～３の直鎖のアルキレン基であり、上記したように、上記アルキレン基は、置換または非置換であり、上記アルキレン基の置換基としては、例えばハロゲン原子、好ましくはフッ素原子を挙げることができる。
　Ｒ４’は、水素原子またはメチルである。）
であり得る。 In a further preferred embodiment X e ′ is
Single bond,
-X f -,
1 to 6 carbon atoms, preferably an alkylene group -X f -C 1-6 alkylene group having 1 to 3 carbon atoms, preferably -X f -C 1-3 alkylene group, more preferably -X f -C 1- 2 alkylene groups,
-C 6 H 4 -R 52 ' -,
-CONR 4 '-R 52' -,
-CONR 4 '-C 6 H 4 -R 52' -,
-X f -CONR 4 '-R 52' -,
-X f -CONR 4 '-C 6 H 4 -R 52' -,
-CO-R 52 ' -,
-CO-C 6 H 4 -R 52 ' -,
-SO 2 NR 4 '-R 52' -,
-SO 2 NR 4 '-C 6 H 4 -R 52' -,
-SO 2 -R 52 ' -,
-SO 2 -C 6 H 4 -R 52 ' -,
-R 51 '-C 6 H 4 - ,
-R 51 '-CONR 4' -,
-R 51 '-CONR 4' -C 6 H 4 -,
-R 51 ' -CO-,
-R 51 '-CO-C 6 H 4 -,
-R 51 '-SO 2 NR 4' -,
-R 51 '-SO 2 NR 4' -C 6 H 4 -,
-R 51 ' -SO 2- ,
-R 51 '-SO 2 -C 6 H 4 -,
-C 6 H 4 -
-CONR 4 ' -,
-CONR 4 '-C 6 H 4 - ,
-X f -CONR 4 ' -,
-X f -CONR 4 '-C 6 H 4 -,
-CO-,
-CO-C 6 H 4 -,
-SO 2 NR 4 ' -,
-SO 2 NR 4 '-C 6 H 4 -
-SO 2 -, or -SO 2 -C 6 H 4 -
(Wherein, R 51 ′ and R 52 ′ each independently represent a linear alkylene group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, and as described above, the above-mentioned alkylene group is It is substituted or unsubstituted, and as the substituent of the above-mentioned alkylene group, for example, a halogen atom, preferably a fluorine atom can be mentioned.
R 4 ′ is a hydrogen atom or methyl. )
It can be.
　上記の中で、Ｘｅ’は、好ましくは、
－Ｘｆ－、
炭素原子数１～６、好ましくは炭素原子数１～３のアルキレン基、
－Ｘｆ－Ｃ１－６アルキレン基、好ましくは－Ｘｆ－Ｃ１－３アルキレン基、より好ましくは－Ｘｆ－Ｃ１－２アルキレン基、
－ＣＯＮＲ４’－Ｒ５２’－、
－ＣＯＮＲ４’－Ｃ６Ｈ４－Ｒ５２’－、
－Ｘｆ－ＣＯＮＲ４’－Ｒ５２’－、
－Ｘｆ－ＣＯＮＲ４’－Ｃ６Ｈ４－Ｒ５２’－、
－Ｒ５１’－ＣＯＮＲ４’－、
－Ｒ５１’－ＣＯＮＲ４’－Ｃ６Ｈ４－、
－ＣＯＮＲ４’－、
－ＣＯＮＲ４’－Ｃ６Ｈ４－、
－Ｘｆ－ＣＯＮＲ４’－、
－Ｘｆ－ＣＯＮＲ４’－Ｃ６Ｈ４－、
－Ｒ５１’－ＣＯＮＲ４’－、または
－Ｒ５１’－ＣＯＮＲ４’－Ｃ６Ｈ４－、
であり得る。式中、Ｘｆ、Ｒ４’、Ｒ５１’およびＲ５２’は、それぞれ上記と同意義である。 Among the above, X e ′ is preferably
-X f -,
An alkylene group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms,
-X f -C 1-6 alkylene group, preferably -X f -C 1-3 alkylene group, more preferably -X f -C 1-2 alkylene group,
-CONR 4 '-R 52' -,
-CONR 4 '-C 6 H 4 -R 52' -,
-X f -CONR 4 '-R 52' -,
-X f -CONR 4 '-C 6 H 4 -R 52' -,
-R 51 '-CONR 4' -,
-R 51 '-CONR 4' -C 6 H 4 -,
-CONR 4 ' -,
-CONR 4 '-C 6 H 4 - ,
-X f -CONR 4 ' -,
-X f -CONR 4 '-C 6 H 4 -,
-R 51 '-CONR 4' -, or -R 51 '-CONR 4' -C 6 H 4 -,
It can be. In the formulae, X f , R 4 ′ , R 51 ′ and R 52 ′ are as defined above.
　上記の中で、Ｘｅ’は、より好ましくは、
－ＣＯＮＲ４’－Ｒ５２’－、
－ＣＯＮＲ４’－Ｃ６Ｈ４－Ｒ５２’－、
－Ｘｆ－ＣＯＮＲ４’－Ｒ５２’－、
－Ｘｆ－ＣＯＮＲ４’－Ｃ６Ｈ４－Ｒ５２’－、
－Ｒ５１’－ＣＯＮＲ４’－、
－Ｒ５１’－ＣＯＮＲ４’－Ｃ６Ｈ４－、
－ＣＯＮＲ４’－、
－ＣＯＮＲ４’－Ｃ６Ｈ４－、
－Ｘｆ－ＣＯＮＲ４’－、または
－Ｘｆ－ＣＯＮＲ４’－Ｃ６Ｈ４－、
であり得る。 In the above, X e ′ is more preferably
-CONR 4 '-R 52' -,
-CONR 4 '-C 6 H 4 -R 52' -,
-X f -CONR 4 '-R 52' -,
-X f -CONR 4 '-C 6 H 4 -R 52' -,
-R 51 '-CONR 4' -,
-R 51 '-CONR 4' -C 6 H 4 -,
-CONR 4 ' -,
-CONR 4 '-C 6 H 4 - ,
-X f -CONR 4 '- or -X f -CONR 4,' -C 6 H 4 -,
It can be.
　本態様において、Ｘｅ’の具体例としては、例えば、
単結合、
炭素原子数１～６のパーフルオロアルキレン基（例えば、－ＣＦ２－、－（ＣＦ２）２－等）、
炭素数１～６のアルキレン基、
－ＣＦ２－Ｃ１－６アルキレン基、
－ＣＯＮＨ－、
－ＣＯＮＨ－ＣＨ２－、
－ＣＯＮＨ－（ＣＨ２）２－
－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＦ２－ＣＯＮＨ－、
－ＣＦ２ＣＯＮＨＣＨ２－、
－ＣＦ２ＣＯＮＨ（ＣＨ２）２－、
－ＣＦ２ＣＯＮＨ（ＣＨ２）３－、
－ＣＯＮ（ＣＨ３）－、
－ＣＯＮ（ＣＨ３）－ＣＨ２－、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）２－
－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＦ２－ＣＯＮ（ＣＨ３）－、
－ＣＦ２－ＣＯＮ（ＣＨ３）ＣＨ２－、
－ＣＦ２－ＣＯＮ（ＣＨ３）－（ＣＨ２）２－、
－ＣＦ２－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＨ２－ＣＯＮＨ－、
－ＣＨ２－ＣＯＮＨ－ＣＨ２－、
－ＣＨ２－ＣＯＮＨ－（ＣＨ２）２－、
－ＣＨ２－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＦ２－ＣＨ２－ＣＯＮＨ－、
－ＣＦ２－ＣＨ２－ＣＯＮＨ－ＣＨ２－、
－ＣＦ２－ＣＨ２－ＣＯＮＨ－（ＣＨ２）２－、
－ＣＦ２－ＣＨ２－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＯＮＨ－Ｃ６Ｈ４－、
－ＣＯＮ（ＣＨ３）－Ｃ６Ｈ４－、
－ＣＨ２－ＣＯＮ（ＣＨ３）－ＣＨ２－、
－ＣＨ２－ＣＯＮ（ＣＨ３）－（ＣＨ２）２－、
－ＣＨ２－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＯＮ（ＣＨ３）－Ｃ６Ｈ４－、
－ＣＦ２－ＣＯＮＨ－Ｃ６Ｈ４－、
－ＣＦ２－ＣＯＮ（ＣＨ３）－Ｃ６Ｈ４－、
－ＣＦ２－ＣＨ２－ＣＯＮ（ＣＨ３）－ＣＨ２－、
－ＣＦ２－ＣＨ２－ＣＯＮ（ＣＨ３）－（ＣＨ２）２－、
－ＣＦ２－ＣＨ２－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＦ２－ＣＯＮ（ＣＨ３）－Ｃ６Ｈ４－、
－ＣＯ－、
－ＣＯ－Ｃ６Ｈ４－、
－Ｃ６Ｈ４－、
－ＳＯ２ＮＨ－、
－ＳＯ２ＮＨ－ＣＨ２－、
－ＳＯ２ＮＨ－（ＣＨ２）２－、
－ＳＯ２ＮＨ－（ＣＨ２）３－、
－ＳＯ２ＮＨ－Ｃ６Ｈ４－、
－ＳＯ２Ｎ（ＣＨ３）－、
－ＳＯ２Ｎ（ＣＨ３）－ＣＨ２－、
－ＳＯ２Ｎ（ＣＨ３）－（ＣＨ２）２－、
－ＳＯ２Ｎ（ＣＨ３）－（ＣＨ２）３－、
－ＳＯ２Ｎ（ＣＨ３）－Ｃ６Ｈ４－、
－ＳＯ２－、
－ＳＯ２－ＣＨ２－、
－ＳＯ２－（ＣＨ２）２－、
－ＳＯ２－（ＣＨ２）３－、または
－ＳＯ２－Ｃ６Ｈ４－
などが挙げられる。 In the present embodiment, specific examples of X e ′ include, for example,
Single bond,
Perfluoroalkylene groups having 1 to 6 carbon atoms (eg, -CF 2 -,-(CF 2 ) 2-, etc.),
An alkylene group having 1 to 6 carbon atoms,
-CF 2 -C 1-6 alkylene group,
-CONH-,
-CONH-CH 2- ,
-CONH- (CH 2 ) 2-
-CONH- (CH 2 ) 3- ,
-CF 2 -CONH-,
-CF 2 CONHCH 2- ,
-CF 2 CONH (CH 2 ) 2- ,
-CF 2 CONH (CH 2 ) 3- ,
-CON (CH 3 )-,
-CON (CH 3 ) -CH 2- ,
-CON (CH 3 )-(CH 2 ) 2-
-CON (CH 3 )-(CH 2 ) 3- ,
-CF 2 -CON (CH 3 )-,
-CF 2 -CON (CH 3 ) CH 2- ,
-CF 2 -CON (CH 3 )-(CH 2 ) 2- ,
-CF 2 -CON (CH 3 )-(CH 2 ) 3- ,
-CH 2 -CONH-,
-CH 2 -CONH-CH 2- ,
-CH 2 -CONH- (CH 2 ) 2- ,
-CH 2 -CONH- (CH 2 ) 3- ,
-CF 2 -CH 2 -CONH-,
-CF 2 -CH 2 -CONH-CH 2- ,
-CF 2 -CH 2 -CONH- (CH 2 ) 2- ,
-CF 2 -CH 2 -CONH- (CH 2 ) 3- ,
-CONH-C 6 H 4 -,
-CON (CH 3) -C 6 H 4 -,
-CH 2 -CON (CH 3 ) -CH 2- ,
-CH 2 -CON (CH 3 )-(CH 2 ) 2- ,
-CH 2 -CON (CH 3 )-(CH 2 ) 3- ,
-CON (CH 3) -C 6 H 4 -,
-CF 2 -CONH-C 6 H 4 -,
-CF 2 -CON (CH 3) -C 6 H 4 -,
-CF 2 -CH 2 -CON (CH 3 ) -CH 2- ,
-CF 2 -CH 2 -CON (CH 3 )-(CH 2 ) 2- ,
-CF 2 -CH 2 -CON (CH 3 )-(CH 2 ) 3- ,
-CF 2 -CON (CH 3) -C 6 H 4 -,
-CO-,
-CO-C 6 H 4 -,
-C 6 H 4 -,
-SO 2 NH-,
-SO 2 NH-CH 2- ,
-SO 2 NH- (CH 2 ) 2- ,
-SO 2 NH- (CH 2 ) 3- ,
-SO 2 NH-C 6 H 4 -,
-SO 2 N (CH 3 )-,
-SO 2 N (CH 3 ) -CH 2- ,
-SO 2 N (CH 3 )-(CH 2 ) 2- ,
-SO 2 N (CH 3 )-(CH 2 ) 3- ,
-SO 2 N (CH 3) -C 6 H 4 -,
-SO 2- ,
-SO 2 -CH 2- ,
-SO 2- (CH 2 ) 2- ,
-SO 2 - (CH 2) 3 -, or -SO 2 -C 6 H 4 -
Etc.
　上記列挙の中で、好ましいＸｅ’としては、
炭素原子数１～６のアルキレン基、
炭素原子数１～６のパーフルオロアルキレン基（例えば、－ＣＦ２－、－（ＣＦ２）２－等）、
－ＣＦ２－Ｃ１－６アルキレン基、
－ＣＯＮＨ－、
－ＣＯＮＨ－ＣＨ２－、
－ＣＯＮＨ－（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＦ２ＣＯＮＨ－、
－ＣＦ２ＣＯＮＨＣＨ２－、
－ＣＦ２ＣＯＮＨ（ＣＨ２）２－、
－ＣＦ２ＣＯＮＨ（ＣＨ２）３－、
－ＣＯＮ（ＣＨ３）－、
－ＣＯＮ（ＣＨ３）－ＣＨ２－、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）２－、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＦ２－ＣＯＮ（ＣＨ３）－、
－ＣＦ２－ＣＯＮ（ＣＨ３）ＣＨ２－、
－ＣＦ２－ＣＯＮ（ＣＨ３）－（ＣＨ２）２－、
－ＣＦ２－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＨ２－ＣＯＮＨ－、
－ＣＨ２－ＣＯＮＨ－ＣＨ２－、
－ＣＨ２－ＣＯＮＨ－（ＣＨ２）２－、
－ＣＨ２－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＦ２－ＣＨ２－ＣＯＮＨ－、
－ＣＦ２－ＣＨ２－ＣＯＮＨ－ＣＨ２－、
－ＣＦ２－ＣＨ２－ＣＯＮＨ－（ＣＨ２）２－、
－ＣＦ２－ＣＨ２－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＯＮＨ－Ｃ６Ｈ４－、
－ＣＯＮ（ＣＨ３）－Ｃ６Ｈ４－、
－ＣＨ２－ＣＯＮ（ＣＨ３）－ＣＨ２－、
－ＣＨ２－ＣＯＮ（ＣＨ３）－（ＣＨ２）２－、
－ＣＨ２－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＯＮ（ＣＨ３）－Ｃ６Ｈ４－
－ＣＦ２－ＣＯＮＨ－Ｃ６Ｈ４－、
－ＣＦ２－ＣＯＮ（ＣＨ３）－Ｃ６Ｈ４－、
－ＣＦ２－ＣＨ２－ＣＯＮ（ＣＨ３）－ＣＨ２－、
－ＣＦ２－ＣＨ２－ＣＯＮ（ＣＨ３）－（ＣＨ２）２－、
－ＣＦ２－ＣＨ２－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＦ２－ＣＯＮ（ＣＨ３）－Ｃ６Ｈ４－、
などが挙げられる。 In the above list, preferable X e ′ is
An alkylene group having 1 to 6 carbon atoms,
Perfluoroalkylene groups having 1 to 6 carbon atoms (eg, -CF 2 -,-(CF 2 ) 2-, etc.),
-CF 2 -C 1-6 alkylene group,
-CONH-,
-CONH-CH 2- ,
-CONH- (CH 2 ) 2- ,
-CONH- (CH 2 ) 3- ,
-CF 2 CONH-,
-CF 2 CONHCH 2- ,
-CF 2 CONH (CH 2 ) 2- ,
-CF 2 CONH (CH 2 ) 3- ,
-CON (CH 3 )-,
-CON (CH 3 ) -CH 2- ,
-CON (CH 3 )-(CH 2 ) 2- ,
-CON (CH 3 )-(CH 2 ) 3- ,
-CF 2 -CON (CH 3 )-,
-CF 2 -CON (CH 3 ) CH 2- ,
-CF 2 -CON (CH 3 )-(CH 2 ) 2- ,
-CF 2 -CON (CH 3 )-(CH 2 ) 3- ,
-CH 2 -CONH-,
-CH 2 -CONH-CH 2- ,
-CH 2 -CONH- (CH 2 ) 2- ,
-CH 2 -CONH- (CH 2 ) 3- ,
-CF 2 -CH 2 -CONH-,
-CF 2 -CH 2 -CONH-CH 2- ,
-CF 2 -CH 2 -CONH- (CH 2 ) 2- ,
-CF 2 -CH 2 -CONH- (CH 2 ) 3- ,
-CONH-C 6 H 4 -,
-CON (CH 3) -C 6 H 4 -,
-CH 2 -CON (CH 3 ) -CH 2- ,
-CH 2 -CON (CH 3 )-(CH 2 ) 2- ,
-CH 2 -CON (CH 3 )-(CH 2 ) 3- ,
-CON (CH 3) -C 6 H 4 -
-CF 2 -CONH-C 6 H 4 -,
-CF 2 -CON (CH 3) -C 6 H 4 -,
-CF 2 -CH 2 -CON (CH 3 ) -CH 2- ,
-CF 2 -CH 2 -CON (CH 3 )-(CH 2 ) 2- ,
-CF 2 -CH 2 -CON (CH 3 )-(CH 2 ) 3- ,
-CF 2 -CON (CH 3) -C 6 H 4 -,
Etc.
　上記列挙の中で、より好ましいＸｅ’としては、
－ＣＯＮＨ－、
－ＣＯＮＨ－ＣＨ２－、
－ＣＯＮＨ－（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＦ２ＣＯＮＨ－、
－ＣＦ２ＣＯＮＨＣＨ２－、
－ＣＦ２ＣＯＮＨ（ＣＨ２）２－、
－ＣＦ２ＣＯＮＨ（ＣＨ２）３－、
－ＣＯＮ（ＣＨ３）－、
－ＣＯＮ（ＣＨ３）－ＣＨ２－、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）２－、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＦ２－ＣＯＮ（ＣＨ３）－、
－ＣＦ２－ＣＯＮ（ＣＨ３）ＣＨ２－、
－ＣＦ２－ＣＯＮ（ＣＨ３）－（ＣＨ２）２－、
－ＣＦ２－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＨ２－ＣＯＮＨ－、
－ＣＨ２－ＣＯＮＨ－ＣＨ２－、
－ＣＨ２－ＣＯＮＨ－（ＣＨ２）２－、
－ＣＨ２－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＦ２－ＣＨ２－ＣＯＮＨ－、
－ＣＦ２－ＣＨ２－ＣＯＮＨ－ＣＨ２－、
－ＣＦ２－ＣＨ２－ＣＯＮＨ－（ＣＨ２）２－、
－ＣＦ２－ＣＨ２－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＯＮＨ－Ｃ６Ｈ４－、
－ＣＯＮ（ＣＨ３）－Ｃ６Ｈ４－、
－ＣＨ２－ＣＯＮ（ＣＨ３）－ＣＨ２－、
－ＣＨ２－ＣＯＮ（ＣＨ３）－（ＣＨ２）２－、
－ＣＨ２－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＯＮ（ＣＨ３）－Ｃ６Ｈ４－
－ＣＦ２－ＣＯＮＨ－Ｃ６Ｈ４－、
－ＣＦ２－ＣＯＮ（ＣＨ３）－Ｃ６Ｈ４－、
－ＣＦ２－ＣＨ２－ＣＯＮ（ＣＨ３）－ＣＨ２－、
－ＣＦ２－ＣＨ２－ＣＯＮ（ＣＨ３）－（ＣＨ２）２－、
－ＣＦ２－ＣＨ２－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、または
－ＣＦ２－ＣＯＮ（ＣＨ３）－Ｃ６Ｈ４－、
などが挙げられる。 In the above list, more preferable X e ′ is
-CONH-,
-CONH-CH 2- ,
-CONH- (CH 2 ) 2- ,
-CONH- (CH 2 ) 3- ,
-CF 2 CONH-,
-CF 2 CONHCH 2- ,
-CF 2 CONH (CH 2 ) 2- ,
-CF 2 CONH (CH 2 ) 3- ,
-CON (CH 3 )-,
-CON (CH 3 ) -CH 2- ,
-CON (CH 3 )-(CH 2 ) 2- ,
-CON (CH 3 )-(CH 2 ) 3- ,
-CF 2 -CON (CH 3 )-,
-CF 2 -CON (CH 3 ) CH 2- ,
-CF 2 -CON (CH 3 )-(CH 2 ) 2- ,
-CF 2 -CON (CH 3 )-(CH 2 ) 3- ,
-CH 2 -CONH-,
-CH 2 -CONH-CH 2- ,
-CH 2 -CONH- (CH 2 ) 2- ,
-CH 2 -CONH- (CH 2 ) 3- ,
-CF 2 -CH 2 -CONH-,
-CF 2 -CH 2 -CONH-CH 2- ,
-CF 2 -CH 2 -CONH- (CH 2 ) 2- ,
-CF 2 -CH 2 -CONH- (CH 2 ) 3- ,
-CONH-C 6 H 4 -,
-CON (CH 3) -C 6 H 4 -,
-CH 2 -CON (CH 3 ) -CH 2- ,
-CH 2 -CON (CH 3 )-(CH 2 ) 2- ,
-CH 2 -CON (CH 3 )-(CH 2 ) 3- ,
-CON (CH 3) -C 6 H 4 -
-CF 2 -CONH-C 6 H 4 -,
-CF 2 -CON (CH 3) -C 6 H 4 -,
-CF 2 -CH 2 -CON (CH 3 ) -CH 2- ,
-CF 2 -CH 2 -CON (CH 3 )-(CH 2 ) 2- ,
-CF 2 -CH 2 -CON (CH 3 ) - (CH 2) 3 -, or -CF 2 -CON (CH 3) -C 6 H 4 -,
Etc.
　一の態様において、Ｘｅ’は、単結合である。本態様において、ＰＦＰＥと基材との結合能を有する基（即ち、（Ａ１）および（Ａ２）においては、α１を付して括弧でくくられた基）とが直接結合している。 In one embodiment, X e ′ is a single bond. In this embodiment, a group capable of binding PFPE to a substrate (that is, a group enclosed in parentheses with α1 in (A1) and (A2)) is directly bonded.
　さらに別の態様において、Ｘ１は、式：－（Ｒ１６）ｘ－（ＣＦＲ１７）ｙ－（ＣＨ２）ｚ－で表される基である。式中、ｘ、ｙおよびｚは、それぞれ独立して、０～１０の整数であり、ｘ、ｙおよびｚの和は１以上であり、括弧でくくられた各繰り返し単位の存在順序は式中において任意である。 In yet another embodiment, X 1 is a group represented by the formula:-(R 16 ) x- (CFR 17 ) y- (CH 2 ) z- . In the formula, x, y and z are each independently an integer of 0 to 10, the sum of x, y and z is 1 or more, and the order of existence of each parenthesized parenthesis is in the formula Is optional.
　上記式中、Ｒ１６は、各出現においてそれぞれ独立して、酸素原子、フェニレン、カルバゾリレン、－ＮＲ１８－（式中、Ｒ１８は、水素原子または有機基を表す）または２価の有機基である。好ましくは、Ｒ１６は、酸素原子または２価の極性基である。 In the above formula, R 16 are each independently at each occurrence, an oxygen atom, a phenylene, carbazolylene, -NR 18 - (wherein, R 18 represents a hydrogen atom or an organic group) or a divalent organic group is there. Preferably, R 16 is an oxygen atom or a divalent polar group.
　上記「２価の極性基」としては、特に限定されないが、－Ｃ（Ｏ）－、－Ｃ（＝ＮＲ１９）－、および－Ｃ（Ｏ）ＮＲ１９－（これらの式中、Ｒ１９は、水素原子または低級アルキル基を表す）が挙げられる。当該「低級アルキル基」は、例えば、炭素数１～６のアルキル基、例えばメチル、エチル、ｎ－プロピルであり、これらは、１個またはそれ以上のフッ素原子により置換されていてもよい。 The above “divalent polar group” is not particularly limited, but —C (O) —, —C (= NR 19 ) —, and —C (O) NR 19 — (in these formulas, R 19 is , A hydrogen atom or a lower alkyl group). The “lower alkyl group” is, for example, an alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl or n-propyl, which may be substituted by one or more fluorine atoms.
　上記式中、Ｒ１７は、各出現においてそれぞれ独立して、水素原子、フッ素原子または低級フルオロアルキル基であり、好ましくはフッ素原子である。当該「低級フルオロアルキル基」は、例えば、炭素数１～６、好ましくは炭素数１～３のフルオロアルキル基、好ましくは炭素数１～３のパーフルオロアルキル基、より好ましくはトリフルオロメチル基、ペンタフルオロエチル基、さらに好ましくはトリフルオロメチル基である。 In the above formulae, R 17 in each occurrence is independently a hydrogen atom, a fluorine atom or a lower fluoroalkyl group, preferably a fluorine atom. The “lower fluoroalkyl group” is, for example, a fluoroalkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group, It is a pentafluoroethyl group, more preferably a trifluoromethyl group.
　この態様において、Ｘ１は、好ましくは、式：－（Ｏ）ｘ－（ＣＦ２）ｙ－（ＣＨ２）ｚ－（式中、ｘ、ｙおよびｚは、上記と同意義であり、括弧でくくられた各繰り返し単位の存在順序は式中において任意である）で表される基である。 In this embodiment, X 1 is preferably of the formula: — (O) x — (CF 2 ) y — (CH 2 ) z —, wherein x, y and z are as defined above, in parentheses The order of existence of each repeating unit enclosed is arbitrary group in the formula).
　上記式：－（Ｏ）ｘ－（ＣＦ２）ｙ－（ＣＨ２）ｚ－で表される基としては、例えば、－（Ｏ）ｘ’－（ＣＨ２）ｚ”－Ｏ－［（ＣＨ２）ｚ’’’－Ｏ－］ｚ””、および－（Ｏ）ｘ’－（ＣＦ２）ｙ”－（ＣＨ２）ｚ”－Ｏ－［（ＣＨ２）ｚ’’’－Ｏ－］ｚ””（式中、ｘ’は０または１であり、ｙ”、ｚ”およびｚ’’’は、それぞれ独立して、１～１０の整数であり、ｚ””は、０または１である）で表される基が挙げられる。なお、これらの基は左端がＰＦＰＥ側に結合する。 Examples of the group represented by the above formula:-(O) x- (CF 2 ) y- (CH 2 ) z- include, for example,-(O) x ' -(CH 2 ) z " -O-[(CH 2 ) 2) z '''-O-] z "", and - (O) x' - ( CF 2) y "- (CH 2) z" -O - [(CH 2) z '''-O- Z ′ ′ ′ ′ (wherein, x ′ is 0 or 1, y ′ ′, z ′ ′ and z ′ ′ ′ are each independently an integer of 1 to 10, and z ′ ′ ′ ′ is 0 or 1 The left end of these groups is bonded to the PFPE side.
　別の好ましい態様において、Ｘ１は、－Ｏ－ＣＦＲ２０－（ＣＦ２）ｅ’－である。 In another preferred embodiment, X 1 is —O—CFR 20 — (CF 2 ) e ′ —.
　上記Ｒ２０は、それぞれ独立して、フッ素原子または低級フルオロアルキル基を表す。ここで低級フルオロアルキル基は、例えば炭素数１～３のフルオロアルキル基、好ましくは炭素数１～３のパーフルオロアルキル基、より好ましくはトリフルオロメチル基、ペンタフルオロエチル基、更に好ましくはトリフルオロメチル基である。 The above R 20 each independently represents a fluorine atom or a lower fluoroalkyl group. Here, the lower fluoroalkyl group is, for example, a fluoroalkyl group having 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group or a pentafluoroethyl group, still more preferably trifluoro. It is a methyl group.
　上記ｅ’は、それぞれ独立して、０または１である。 The above e's are each independently 0 or 1.
　一の具体例において、Ｒ２０はフッ素原子であり、ｅ’は１である。 In one embodiment, R 20 is a fluorine atom and e ′ is 1.
　さらに別の態様において、Ｘ１基の例として、下記の基が挙げられる：
Figure JPOXMLDOC01-appb-C000008
 ［式中、
　Ｒ４１は、それぞれ独立して、水素原子、フェニル基、炭素数１～６のアルキル基、またはＣ１－６アルコキシ基、好ましくはメチル基であり；
　各Ｘ１基において、Ｔのうち任意のいくつかは、分子主鎖のＰＦＰＥに結合する以下の基：
－ＣＨ２Ｏ（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３－、
－ＣＦ２Ｏ（ＣＨ２）３－、
－ＣＨ２－、
－（ＣＨ２）２－、
－（ＣＨ２）３－、
－（ＣＨ２）4－、
－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）３－（式中、Ｐｈはフェニルを意味する）、または
Figure JPOXMLDOC01-appb-C000009
 ［式中、Ｒ４２は、それぞれ独立して、水素原子、Ｃ１－６のアルキル基またはＣ１－６のアルコキシ基、好ましくはメチル基またはメトキシ基、より好ましくはメチル基を表す。］
であり、別のＴのいくつかは、分子主鎖のＰＦＰＥと反対の基に結合する－（ＣＨ２）ｎ”－（ｎ”は２～６の整数）であり、存在する場合、残りのＴは、それぞれ独立して、メチル基、フェニル基、Ｃ１－６アルコキシ基またはラジカル捕捉基もしくは紫外線吸収基であり得る。 In yet another embodiment, examples of X 1 groups include:
Figure JPOXMLDOC01-appb-C000008
 [In the formula,
Each R 41 independently represents a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C 1-6 alkoxy group, preferably a methyl group;
In each X 1 group, any part of T is attached to PFPE of the molecular backbone:
-CH 2 O (CH 2 ) 2- ,
-CH 2 O (CH 2 ) 3- ,
-CF 2 O (CH 2 ) 3- ,
-CH 2- ,
-(CH 2 ) 2- ,
-(CH 2 ) 3- ,
- (CH 2) 4 -,
-CONH- (CH 2 ) 3- ,
-CON (CH 3 )-(CH 2 ) 3- ,
-CON (Ph)-(CH 2 ) 3- (wherein Ph means phenyl), or
Figure JPOXMLDOC01-appb-C000009
 [Wherein, R 42 each independently represents a hydrogen atom, a C 1-6 alkyl group or a C 1-6 alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group. ]
And some of the other T's are — (CH 2 ) n ′ ′ (n ′ ′ is an integer from 2 to 6) attached to the group opposite to the PFPE of the molecular main chain, and, if present, the remaining T may be each independently a methyl group, a phenyl group, a C 1-6 alkoxy group or a radical scavenging group or an ultraviolet absorbing group.
　ラジカル捕捉基は、光照射で生じるラジカルを捕捉できるものであれば特に限定されないが、例えばベンゾフェノン類、ベンゾトリアゾール類、安息香酸エステル類、サリチル酸フェニル類、クロトン酸類、マロン酸エステル類、オルガノアクリレート類、ヒンダードアミン類、ヒンダードフェノール類、またはトリアジン類の残基が挙げられる。 The radical scavenging group is not particularly limited as long as it can scavenge a radical generated upon irradiation with light, for example, benzophenones, benzotriazoles, benzoates, phenyl salicylates, crotonic acids, malonic esters, organoacrylates And residues of hindered amines, hindered phenols, or triazines.
　紫外線吸収基は、紫外線を吸収できるものであれば特に限定されないが、例えばベンゾトリアゾール類、ヒドロキシベンゾフェノン類、置換および未置換安息香酸もしくはサリチル酸化合物のエステル類、アクリレートまたはアルコキシシンナメート類、オキサミド類、オキサニリド類、ベンゾキサジノン類、ベンゾキサゾール類の残基が挙げられる。 The ultraviolet absorbing group is not particularly limited as long as it can absorb ultraviolet light, and examples thereof include benzotriazoles, hydroxybenzophenones, esters of substituted and unsubstituted benzoic acid or salicylic acid compounds, acrylates or alkoxycinnamates, oxamides, The residue includes oxanilides, benzoxazinones and benzoxazoles.
　好ましい態様において、好ましいラジカル捕捉基または紫外線吸収基としては、
Figure JPOXMLDOC01-appb-C000010
が挙げられる。 In a preferred embodiment, preferred radical scavenging groups or ultraviolet absorbing groups are
Figure JPOXMLDOC01-appb-C000010
Can be mentioned.
　この態様において、Ｘ１（および、下記するＸ３、Ｘ５およびＸ７）は、３～１０価の有機基であり得る。 In this embodiment, X 1 (and X 3 , X 5 and X 7 described below) may be a trivalent to dodecavalent organic group.
　上記式中、Ｘ２は、各出現においてそれぞれ独立して、単結合または２価の有機基を表す。Ｘ２は、好ましくは、炭素数１～２０のアルキレン基であり、より好ましくは、－（ＣＨ２）ｕ－（式中、ｕは、０～２の整数である）である。 In the above formulae, X 2 each independently represents a single bond or a divalent organic group at each occurrence. X 2 is preferably an alkylene group having 1 to 20 carbon atoms, and more preferably — (CH 2 ) u — (wherein u is an integer of 0 to 2).
　上記式中、ｔは、それぞれ独立して、１～１０の整数である。好ましい態様において、ｔは１～６の整数である。別の好ましい態様において、ｔは２～１０の整数であり、好ましくは２～６の整数である。 In the above formulae, t is each independently an integer of 1 to 10. In a preferred embodiment, t is an integer of 1 to 6. In another preferred embodiment, t is an integer of 2 to 10, preferably an integer of 2 to 6.
　好ましい式（Ａ１）および（Ａ２）で示される化合物は、下記式（Ａ１’）および（Ａ２’）：
Figure JPOXMLDOC01-appb-C000011
 ［式中：
　ＰＦＰＥは、それぞれ独立して、式：
－（ＯＣ６Ｆ１２）ａ－（ＯＣ５Ｆ１０）ｂ－（ＯＣ４Ｆ８）ｃ－（ＯＣ３Ｆ６）ｄ－（ＯＣ２Ｆ４）ｅ－（ＯＣＦ２）ｆ－
（式中、ａ、ｂ、ｃ、ｄ、ｅおよびｆは、それぞれ独立して０以上２００以下の整数であって、ａ、ｂ、ｃ、ｄ、ｅおよびｆの和は少なくとも１である。ａ、ｂ、ｃ、ｄ、ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。）
で表される基であり； 
　Ｒｆは、各出現においてそれぞれ独立して、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１～１６のアルキル基を表し；
　Ｒ１３は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し；
　Ｒ１４は、各出現においてそれぞれ独立して、水素原子または炭素数１～２２のアルキル基を表し；
　Ｒ１１は、各出現においてそれぞれ独立して、水素原子またはハロゲン原子を表し；
　Ｒ１２は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
　ｎ１は、１～３の整数であり、好ましくは３であり；
　Ｘ１は、各出現においてそれぞれ独立して、－Ｏ－ＣＦＲ２０－（ＣＦ２）ｅ’－であり；
　Ｒ２０は、各出現においてそれぞれ独立して、フッ素原子または低級フルオロアルキル基であり；
　ｅ’は、各出現においてそれぞれ独立して、０または１であり；
　Ｘ２は、－（ＣＨ２）ｕ－であり；
　ｕは、各出現においてそれぞれ独立して、０～２の整数であり；
　ｔは、各出現においてそれぞれ独立して、２～１０の整数である。］
で表される化合物である。 Preferred compounds represented by the formulas (A1) and (A2) have the following formulas (A1 ′) and (A2 ′):
Figure JPOXMLDOC01-appb-C000011
 [In the formula:
Each PFPE is independently of the formula:
- (OC 6 F 12) a - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f -
(Wherein, a, b, c, d, e and f are each independently an integer of 0 or more and 200 or less, and the sum of a, b, c, d, e and f is at least 1). The order in which each repeating unit in parentheses is attached with a, b, c, d, e or f is arbitrary in the formula.)
A group represented by
R f independently at each occurrence represents an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms;
R 13 independently at each occurrence independently represents a hydroxyl group or a hydrolysable group;
R 14 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms at each occurrence;
R 11 independently represents at each occurrence a hydrogen atom or a halogen atom;
R 12 independently at each occurrence represents a hydrogen atom or a lower alkyl group;
n1 is an integer of 1 to 3, preferably 3;
X 1 is independently at each occurrence, -O-CFR 20 - (CF 2) e '- a and;
R 20 each independently at each occurrence is a fluorine atom or a lower fluoroalkyl group;
e 'is independently at each occurrence either 0 or 1;
X 2 is-(CH 2 ) u- ;
u is each independently an integer of 0 to 2 at each occurrence;
t is an integer of 2 to 10 independently at each occurrence. ]
It is a compound represented by
　上記式（Ａ１）および（Ａ２）で表される化合物は、例えば、Ｒｆ－ＰＦＰＥ－部分に対応するパーフルオロポリエーテル誘導体を原料として、末端にヨウ素を導入した後、－ＣＨ２ＣＲ１２（Ｘ２－ＳｉＲ１３ ｎ１Ｒ１４ ３－ｎ１）－に対応するビニルモノマーを反応させることにより得ることができる。 The compounds represented by the above formulas (A1) and (A2) can be obtained, for example, by introducing iodine into the terminal using a perfluoropolyether derivative corresponding to the Rf-PFPE- moiety as a raw material, and then introducing —CH 2 CR 12 (X It can be obtained by reacting a vinyl monomer corresponding to 2 -SiR 13 n1 R 14 3-n1 )-.
　式（Ｂ１）および（Ｂ２）：
Figure JPOXMLDOC01-appb-C000012
 Formulas (B1) and (B2):
Figure JPOXMLDOC01-appb-C000012
　上記式（Ｂ１）および（Ｂ２）中、Ｒｆ、ＰＦＰＥ、Ｒ１３、Ｒ１４およびｎ１は、上記式（Ａ１）および（Ａ２）に関する記載と同意義である。 In the above formulas (B1) and (B2), Rf, PFPE, R 13 , R 14 and n 1 are as defined for the above formulas (A1) and (A2).
　上記式中、Ｘ３は、それぞれ独立して、単結合または２～１０価の有機基を表す。当該Ｘ３は、式（Ｂ１）および（Ｂ２）で表される化合物において、主に撥水性および表面滑り性等を提供するパーフルオロポリエーテル部（即ち、Ｒｆ－ＰＦＰＥ部または－ＰＦＰＥ－部）と、基材との結合能を提供するシラン部（具体的には、－ＳｉＲ１３ ｎ１Ｒ１４ ３－ｎ１）とを連結するリンカーと解される。従って、当該Ｘ３は、式（Ｂ１）および（Ｂ２）で表される化合物が安定に存在し得るものであれば、いずれの有機基であってもよい。 In the above formulae, each X 3 independently represents a single bond or a di- to 10-valent organic group. The said X 3 is a perfluoropolyether part (namely, Rf-PFPE part or -PFPE- part) which mainly provides water repellency, surface slip property, etc. in the compound represented by Formula (B1) and (B2) And a silane moiety (specifically, -SiR 13 n 1 R 14 3-n 1 ) that provides the ability to bind to a substrate. Accordingly, X 3 may be any organic group as long as the compounds represented by formulas (B1) and (B2) can stably exist.
　別の態様において、Ｘ３は、Ｘｅを表す。Ｘｅは、上記と同意義である。 In another aspect, X 3 represents X e . X e is as defined above.
　上記式中のβ１は、１～９の整数であり、β１’は、１～９の整数である。これらβ１およびβ１’は、Ｘ３の価数に応じて変化し得る。式（Ｂ１）において、β１およびβ１’の和は、Ｘ３の価数と同じである。例えば、Ｘ３が１０価の有機基である場合、β１およびβ１’の和は１０であり、例えばβ１が９かつβ１’が１、β１が５かつβ１’が５、またはβ１が１かつβ１’が９となり得る。また、Ｘ３が２価の有機基である場合、β１およびβ１’は１である。式（Ｂ２）において、β１はＸ３の価数の値から１を引いた値である。 In the above formula, β1 is an integer of 1 to 9, and β1 ′ is an integer of 1 to 9. These β1 and β1 ′ can change according to the valence of X 3 . In Formula (B1), the sum of β1 and β1 ′ is the same as the valence of X 3 . For example, when X 3 is a 10-valent organic group, the sum of β1 and β1 ′ is 10, for example, β1 is 9 and β1 ′ is 1, β1 is 5 and β1 ′ is 5, or β1 is 1 and β1 'Can be nine. Further, when X 3 is a divalent organic group, β 1 and β 1 ′ are 1. In Formula (B2), β1 is a value obtained by subtracting 1 from the value of the valence of X 3 .
　上記Ｘ３は、好ましくは２～７価、より好ましくは２～４価、さらに好ましくは２価の有機基である。 The above X 3 is preferably a divalent to heptavalent, more preferably a divalent to tetravalent, more preferably a divalent organic group.
　一の態様において、Ｘ３は２～４価の有機基であり、β１は１～３であり、β１’は１である。 In one embodiment, X 3 is a divalent to tetravalent organic group, β 1 is 1 to 3 and β 1 ′ is 1.
　別の態様において、Ｘ３は２価の有機基であり、β１は１であり、β１’は１である。この場合、式（Ｂ１）および（Ｂ２）は、下記式（Ｂ１’）および（Ｂ２’）で表される。
Figure JPOXMLDOC01-appb-C000013
 In another embodiment, X 3 is a divalent organic group, β 1 is 1 and β 1 ′ is 1. In this case, the formulas (B1) and (B2) are represented by the following formulas (B1 ′) and (B2 ′).
Figure JPOXMLDOC01-appb-C000013
［式中：
　ＰＦＰＥは、それぞれ独立して、式：
－（ＯＣ６Ｆ１２）ａ－（ＯＣ５Ｆ１０）ｂ－（ＯＣ４Ｆ８）ｃ－（ＯＣ３Ｆ６）ｄ－（ＯＣ２Ｆ４）ｅ－（ＯＣＦ２）ｆ－
（式中、ａ、ｂ、ｃ、ｄ、ｅおよびｆは、それぞれ独立して０以上２００以下の整数であって、ａ、ｂ、ｃ、ｄ、ｅおよびｆの和は少なくとも１である。添字ａ、ｂ、ｃ、ｄ、ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。）
で表される基であり；
　Ｒｆは、各出現においてそれぞれ独立して、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１～１６のアルキル基を表し；
　Ｒ１３は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し；
　Ｒ１４は、各出現においてそれぞれ独立して、水素原子または炭素数１～２２のアルキル基を表し；
　ｎ１は、１～３の整数であり、好ましくは３であり；
　Ｘ３は、－ＣＨ２Ｏ（ＣＨ２）２－、－ＣＨ２Ｏ（ＣＨ２）３－または－ＣＨ２Ｏ（ＣＨ２）６－である］
で表される化合物である。 [In the formula:
Each PFPE is independently of the formula:
- (OC 6 F 12) a - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f -
(Wherein, a, b, c, d, e and f are each independently an integer of 0 or more and 200 or less, and the sum of a, b, c, d, e and f is at least 1). The order in which each repeating unit enclosed in parentheses with the subscripts a, b, c, d, e or f is given is arbitrary in the formula.)
A group represented by
R f independently at each occurrence represents an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms;
R 13 independently at each occurrence independently represents a hydroxyl group or a hydrolysable group;
R 14 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms at each occurrence;
n1 is an integer of 1 to 3, preferably 3;
X 3 is —CH 2 O (CH 2 ) 2 —, —CH 2 O (CH 2 ) 3 — or —CH 2 O (CH 2 ) 6 —
It is a compound represented by
　上記Ｘ３の例としては、特に限定するものではないが、例えば、Ｘ１に関して記載したものと同様のものが挙げられる。 Examples of the X 3, is not particularly limited, examples thereof include the same as described for X 1.
　中でも、好ましい具体的なＸ３は、
単結合、
－ＣＨ２ＯＣＨ２－、
－ＣＨ２Ｏ（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３－、
－ＣＨ２Ｏ（ＣＨ２）６－、
－ＣＦ２－ＣＨ２－Ｏ－ＣＨ２－、
－ＣＦ２－ＣＨ２－Ｏ－（ＣＨ２）２－、
－ＣＦ２－ＣＨ２－Ｏ－（ＣＨ２）３－、
－ＣＦ２－ＣＨ２－Ｏ－（ＣＨ２）６－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）３Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）１０Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２０Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－Ｃ（Ｏ）ＮＨ－ＣＨ２－、
－ＣＨ２ＯＣＨ２（ＣＨ２）７ＣＨ２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）２－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）３－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ２ＣＨ３）２ＯＳｉ（ＯＣＨ２ＣＨ３）２（ＣＨ２）３－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）２－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ２ＣＨ３）２ＯＳｉ（ＯＣＨ２ＣＨ３）２（ＣＨ２）２－、
－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－、
－ＣＨ２－、
－（ＣＨ２）２－、
－（ＣＨ２）３－、
－（ＣＨ２）４－、
－（ＣＨ２）５－、
－（ＣＨ２）６－、
－ＣＦ２－、
－（ＣＦ２）２－、
－ＣＦ２－ＣＨ２－、
－ＣＦ２－（ＣＨ２）２－、
－ＣＦ２－（ＣＨ２）３－、
－ＣＦ２－（ＣＨ２）４－、
－ＣＦ２－（ＣＨ２）５－、
－ＣＦ２－（ＣＨ２）６－、
－ＣＯ－
－ＣＯＮＨ－
－ＣＯＮＨ－ＣＨ２－、
－ＣＯＮＨ－（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＯＮＨ－（ＣＨ２）６－、
－ＣＦ２ＣＯＮＨ－、
－ＣＦ２ＣＯＮＨＣＨ２－、
－ＣＦ２ＣＯＮＨ（ＣＨ２）２－、
－ＣＦ２ＣＯＮＨ（ＣＨ２）３－、
－ＣＦ２ＣＯＮＨ（ＣＨ２）６－、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）３－（式中、Ｐｈはフェニルを意味する）、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）６－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）６－（式中、Ｐｈはフェニルを意味する）、
－ＣＦ２－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＦ２－ＣＯＮ（Ｐｈ）－（ＣＨ２）３－（式中、Ｐｈはフェニルを意味する）、
－ＣＦ２－ＣＯＮ（ＣＨ３）－（ＣＨ２）６－、
－ＣＦ２－ＣＯＮ（Ｐｈ）－（ＣＨ２）６－（式中、Ｐｈはフェニルを意味する）、
－ＣＯＮＨ－（ＣＨ２）２ＮＨ（ＣＨ２）３－、
－ＣＯＮＨ－（ＣＨ２）６ＮＨ（ＣＨ２）３－、
－ＣＨ２Ｏ－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＨ２Ｏ－ＣＯＮＨ－（ＣＨ２）６－、
－Ｓ－（ＣＨ２）３－、
－（ＣＨ２）２Ｓ（ＣＨ２）３－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）３Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）１０Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２０Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－Ｃ（Ｏ）Ｏ－（ＣＨ２）３－、
－Ｃ（Ｏ）Ｏ－（ＣＨ２）６－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－ＣＨ（ＣＨ３）－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－（ＣＨ２）３－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－ＣＨ（ＣＨ３）－ＣＨ２－、
－ＯＣＨ２－、
－Ｏ（ＣＨ２）３－、
－ＯＣＦＨＣＦ２－、
Figure JPOXMLDOC01-appb-C000014
 などが挙げられる。 Among them, preferred specific X 3 is
Single bond,
-CH 2 OCH 2- ,
-CH 2 O (CH 2 ) 2- ,
-CH 2 O (CH 2 ) 3- ,
-CH 2 O (CH 2 ) 6- ,
-CF 2 -CH 2 -O-CH 2- ,
-CF 2 -CH 2 -O- (CH 2 ) 2- ,
-CF 2 -CH 2 -O- (CH 2 ) 3- ,
-CF 2 -CH 2 -O- (CH 2 ) 6-
-CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2- ,
-CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2- ,
-CH 2 O (CH 2) 3 Si (CH 3) 2 O (Si (CH 3) 2 O) 2 Si (CH 3) 2 (CH 2) 2 -,
-CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 3 Si (CH 3 ) 2 (CH 2 ) 2- ,
-CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 10 Si (CH 3 ) 2 (CH 2 ) 2- ,
-CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 20 Si (CH 3 ) 2 (CH 2 ) 2- ,
-CH 2 OCF 2 CHFOCF 2- ,
-CH 2 OCF 2 CHFOCF 2 CF 2- ,
-CH 2 OCF 2 CHFOCF 2 CF 2 CF 2- ,
-CH 2 OCH 2 CF 2 CF 2 OCF 2- ,
-CH 2 OCH 2 CF 2 CF 2 OCF 2 CF 2- ,
-CH 2 OCH 2 CF 2 CF 2 OCF 2 CF 2 CF 2- ,
-CH 2 OCH 2 CF 2 CF 2 OCF (CF 3) CF 2 OCF 2 -,
-CH 2 OCH 2 CF 2 CF 2 OCF (CF 3) CF 2 OCF 2 CF 2 -,
-CH 2 OCH 2 CF 2 CF 2 OCF (CF 3) CF 2 OCF 2 CF 2 CF 2 -,
-CH 2 OCH 2 CHFCF 2 OCF 2- ,
-CH 2 OCH 2 CHFCF 2 OCF 2 CF 2- ,
-CH 2 OCH 2 CHFCF 2 OCF 2 CF 2 CF 2- ,
-CH 2 OCH 2 CHFCF 2 OCF ( CF 3) CF 2 OCF 2 -,
-CH 2 OCH 2 CHFCF 2 OCF ( CF 3) CF 2 OCF 2 CF 2 -,
-CH 2 OCH 2 CHFCF 2 OCF (CF 3 ) CF 2 OCF 2 CF 2 CF 2-
-CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 -C (O) NH-CH 2- ,
-CH 2 OCH 2 (CH 2 ) 7 CH 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 2- ,
-CH 2 OCH 2 CH 2 CH 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 3- ,
-CH 2 OCH 2 CH 2 CH 2 Si (OCH 2 CH 3 ) 2 OSi (OCH 2 CH 3 ) 2 (CH 2 ) 3- ,
-CH 2 OCH 2 CH 2 CH 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 2- ,
-CH 2 OCH 2 CH 2 CH 2 Si (OCH 2 CH 3 ) 2 OSi (OCH 2 CH 3 ) 2 (CH 2 ) 2- ,
-(CH 2 ) 2 -Si (CH 3 ) 2- (CH 2 ) 2- ,
-CH 2- ,
-(CH 2 ) 2- ,
-(CH 2 ) 3- ,
- (CH 2) 4 -,
-(CH 2 ) 5- ,
-(CH 2 ) 6- ,
-CF 2- ,
-(CF 2 ) 2- ,
-CF 2 -CH 2- ,
-CF 2- (CH 2 ) 2- ,
-CF 2- (CH 2 ) 3- ,
-CF 2 - (CH 2) 4 -,
-CF 2- (CH 2 ) 5- ,
-CF 2- (CH 2 ) 6- ,
-CO-
-CONH-
-CONH-CH 2- ,
-CONH- (CH 2 ) 2- ,
-CONH- (CH 2 ) 3- ,
-CONH- (CH 2 ) 6- ,
-CF 2 CONH-,
-CF 2 CONHCH 2- ,
-CF 2 CONH (CH 2 ) 2- ,
-CF 2 CONH (CH 2 ) 3- ,
-CF 2 CONH (CH 2 ) 6- ,
-CON (CH 3 )-(CH 2 ) 3- ,
-CON (Ph)-(CH 2 ) 3- (wherein Ph means phenyl),
-CON (CH 3 )-(CH 2 ) 6- ,
-CON (Ph)-(CH 2 ) 6- (wherein Ph means phenyl),
-CF 2 -CON (CH 3 )-(CH 2 ) 3- ,
-CF 2 -CON (Ph)-(CH 2 ) 3- (wherein, Ph means phenyl),
-CF 2 -CON (CH 3 )-(CH 2 ) 6- ,
-CF 2 -CON (Ph)-(CH 2 ) 6- (wherein, Ph means phenyl),
-CONH- (CH 2 ) 2 NH (CH 2 ) 3- ,
-CONH- (CH 2 ) 6 NH (CH 2 ) 3- ,
-CH 2 O-CONH- (CH 2 ) 3- ,
-CH 2 O-CONH- (CH 2 ) 6- ,
-S- (CH 2 ) 3- ,
-(CH 2 ) 2 S (CH 2 ) 3- ,
-CONH- (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2- ,
-CONH- (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2- ,
-CONH- (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 2 Si (CH 3 ) 2 (CH 2 ) 2- ,
-CONH- (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 3 Si (CH 3 ) 2 (CH 2 ) 2- ,
-CONH- (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 10 Si (CH 3 ) 2 (CH 2 ) 2- ,
-CONH- (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 20 Si (CH 3 ) 2 (CH 2 ) 2- ,
-C (O) O- (CH 2 ) 3- ,
-C (O) O- (CH 2 ) 6- ,
-CH 2 -O- (CH 2 ) 3 -Si (CH 3 ) 2- (CH 2 ) 2 -Si (CH 3 ) 2- (CH 2 ) 2- ,
-CH 2 -O- (CH 2 ) 3 -Si (CH 3 ) 2- (CH 2 ) 2 -Si (CH 3 ) 2 -CH (CH 3 )-,
-CH 2 -O- (CH 2 ) 3 -Si (CH 3 ) 2- (CH 2 ) 2 -Si (CH 3 ) 2- (CH 2 ) 3- ,
-CH 2 -O- (CH 2 ) 3 -Si (CH 3 ) 2- (CH 2 ) 2 -Si (CH 3 ) 2 -CH (CH 3 ) -CH 2- ,
-OCH 2-
-O (CH 2 ) 3- ,
-OCFHCF 2- ,
Figure JPOXMLDOC01-appb-C000014
 Etc.
　上記の中では、Ｘ３は、
－ＣＨ２ＯＣＨ２－、
－ＣＨ２Ｏ（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３－、
－ＣＨ２Ｏ（ＣＨ２）６－、
－ＣＦ２－ＣＨ２－Ｏ－ＣＨ２－、
－ＣＦ２－ＣＨ２－Ｏ－（ＣＨ２）２－、
－ＣＦ２－ＣＨ２－Ｏ－（ＣＨ２）３－、
－ＣＦ２－ＣＨ２－Ｏ－（ＣＨ２）６－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－Ｃ（Ｏ）ＮＨ－ＣＨ２－、
－ＣＦ２－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－Ｃ（Ｏ）ＮＨ－ＣＨ２－、
－ＣＨ２－、
－（ＣＨ２）２－、
－（ＣＨ２）３－、
－（ＣＨ２）４－、
－（ＣＨ２）５－、
－（ＣＨ２）６－、
－ＣＦ２－、
－（ＣＦ２）２－、
－ＣＦ２－ＣＨ２－、
－ＣＦ２－（ＣＨ２）２－、
－ＣＦ２－（ＣＨ２）３－、
－ＣＦ２－（ＣＨ２）４－、
－ＣＦ２－（ＣＨ２）５－、
－ＣＦ２－（ＣＨ２）６－、
－ＣＯＮＨ－、
－ＣＯＮＨ－ＣＨ２－、
－ＣＯＮＨ－（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＯＮＨ－（ＣＨ２）６－、
－ＣＦ２ＣＯＮＨ－、
－ＣＦ２ＣＯＮＨＣＨ２－、
－ＣＦ２ＣＯＮＨ（ＣＨ２）２－、
－ＣＦ２ＣＯＮＨ（ＣＨ２）３－、
－ＣＦ２ＣＯＮＨ（ＣＨ２）６－、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）３－（式中、Ｐｈはフェニルを意味する）、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）６－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）６－（式中、Ｐｈはフェニルを意味する）、
－ＣＦ２－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＦ２－ＣＯＮ（Ｐｈ）－（ＣＨ２）３－（式中、Ｐｈはフェニルを意味する）、
－ＣＦ２－ＣＯＮ（ＣＨ３）－（ＣＨ２）６－、
－ＣＦ２－ＣＯＮ（Ｐｈ）－（ＣＨ２）６－（式中、Ｐｈはフェニルを意味する）、
－ＣＯＮＨ－（ＣＨ２）２ＮＨ（ＣＨ２）３－、
－ＣＯＮＨ－（ＣＨ２）６ＮＨ（ＣＨ２）３－、
－ＣＨ２Ｏ－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＨ２Ｏ－ＣＯＮＨ－（ＣＨ２）６－、
－ＯＣＨ２－、
－Ｏ（ＣＨ２）３－、
－ＯＣＦＨＣＦ２－、
であることが好ましい。 In the above, X 3 is
-CH 2 OCH 2- ,
-CH 2 O (CH 2 ) 2- ,
-CH 2 O (CH 2 ) 3- ,
-CH 2 O (CH 2 ) 6- ,
-CF 2 -CH 2 -O-CH 2- ,
-CF 2 -CH 2 -O- (CH 2 ) 2- ,
-CF 2 -CH 2 -O- (CH 2 ) 3- ,
-CF 2 -CH 2 -O- (CH 2 ) 6-
-CH 2 OCF 2 CHFOCF 2- ,
-CH 2 OCF 2 CHFOCF 2 CF 2- ,
-CH 2 OCF 2 CHFOCF 2 CF 2 CF 2- ,
-CH 2 OCH 2 CF 2 CF 2 OCF 2- ,
-CH 2 OCH 2 CF 2 CF 2 OCF 2 CF 2- ,
-CH 2 OCH 2 CF 2 CF 2 OCF 2 CF 2 CF 2- ,
-CH 2 OCH 2 CF 2 CF 2 OCF (CF 3) CF 2 OCF 2 -,
-CH 2 OCH 2 CF 2 CF 2 OCF (CF 3) CF 2 OCF 2 CF 2 -,
-CH 2 OCH 2 CF 2 CF 2 OCF (CF 3) CF 2 OCF 2 CF 2 CF 2 -,
-CH 2 OCH 2 CHFCF 2 OCF 2- ,
-CH 2 OCH 2 CHFCF 2 OCF 2 CF 2- ,
-CH 2 OCH 2 CHFCF 2 OCF 2 CF 2 CF 2- ,
-CH 2 OCH 2 CHFCF 2 OCF ( CF 3) CF 2 OCF 2 -,
-CH 2 OCH 2 CHFCF 2 OCF ( CF 3) CF 2 OCF 2 CF 2 -,
-CH 2 OCH 2 CHFCF 2 OCF ( CF 3) CF 2 OCF 2 CF 2 CF 2 -,
-CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 -C (O) NH-CH 2- ,
-CF 2 -CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 -C (O) NH-CH 2- ,
-CH 2- ,
-(CH 2 ) 2- ,
-(CH 2 ) 3- ,
- (CH 2) 4 -,
-(CH 2 ) 5- ,
-(CH 2 ) 6- ,
-CF 2- ,
-(CF 2 ) 2- ,
-CF 2 -CH 2- ,
-CF 2- (CH 2 ) 2- ,
-CF 2- (CH 2 ) 3- ,
-CF 2 - (CH 2) 4 -,
-CF 2- (CH 2 ) 5- ,
-CF 2- (CH 2 ) 6- ,
-CONH-,
-CONH-CH 2- ,
-CONH- (CH 2 ) 2- ,
-CONH- (CH 2 ) 3- ,
-CONH- (CH 2 ) 6- ,
-CF 2 CONH-,
-CF 2 CONHCH 2- ,
-CF 2 CONH (CH 2 ) 2- ,
-CF 2 CONH (CH 2 ) 3- ,
-CF 2 CONH (CH 2 ) 6- ,
-CON (CH 3 )-(CH 2 ) 3- ,
-CON (Ph)-(CH 2 ) 3- (wherein Ph means phenyl),
-CON (CH 3 )-(CH 2 ) 6- ,
-CON (Ph)-(CH 2 ) 6- (wherein Ph means phenyl),
-CF 2 -CON (CH 3 )-(CH 2 ) 3- ,
-CF 2 -CON (Ph)-(CH 2 ) 3- (wherein, Ph means phenyl),
-CF 2 -CON (CH 3 )-(CH 2 ) 6- ,
-CF 2 -CON (Ph)-(CH 2 ) 6- (wherein, Ph means phenyl),
-CONH- (CH 2 ) 2 NH (CH 2 ) 3- ,
-CONH- (CH 2 ) 6 NH (CH 2 ) 3- ,
-CH 2 O-CONH- (CH 2 ) 3- ,
-CH 2 O-CONH- (CH 2 ) 6- ,
-OCH 2-
-O (CH 2 ) 3- ,
-OCFHCF 2- ,
Is preferred.
　上記の中では、より好ましくは、Ｘ３は、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－Ｃ（Ｏ）ＮＨ－ＣＨ２－、
－ＣＦ２－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－Ｃ（Ｏ）ＮＨ－ＣＨ２－、
－ＣＯＮＨ－、
－ＣＯＮＨ－ＣＨ２－、
－ＣＯＮＨ－（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＯＮＨ－（ＣＨ２）６－、
－ＣＦ２ＣＯＮＨ－、
－ＣＦ２ＣＯＮＨＣＨ２－、
－ＣＦ２ＣＯＮＨ（ＣＨ２）２－、
－ＣＦ２ＣＯＮＨ（ＣＨ２）３－、
－ＣＦ２ＣＯＮＨ（ＣＨ２）６－、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）３－（式中、Ｐｈはフェニルを意味する）、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）６－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）６－（式中、Ｐｈはフェニルを意味する）、
－ＣＦ２－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＦ２－ＣＯＮ（Ｐｈ）－（ＣＨ２）３－（式中、Ｐｈはフェニルを意味する）、
－ＣＦ２－ＣＯＮ（ＣＨ３）－（ＣＨ２）６－、
－ＣＦ２－ＣＯＮ（Ｐｈ）－（ＣＨ２）６－（式中、Ｐｈはフェニルを意味する）、
－ＣＯＮＨ－（ＣＨ２）２ＮＨ（ＣＨ２）３－、
－ＣＯＮＨ－（ＣＨ２）６ＮＨ（ＣＨ２）３－、
である。 Among the above, more preferably, X 3 is
-CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 -C (O) NH-CH 2- ,
-CF 2 -CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 -C (O) NH-CH 2- ,
-CONH-,
-CONH-CH 2- ,
-CONH- (CH 2 ) 2- ,
-CONH- (CH 2 ) 3- ,
-CONH- (CH 2 ) 6- ,
-CF 2 CONH-,
-CF 2 CONHCH 2- ,
-CF 2 CONH (CH 2 ) 2- ,
-CF 2 CONH (CH 2 ) 3- ,
-CF 2 CONH (CH 2 ) 6- ,
-CON (CH 3 )-(CH 2 ) 3- ,
-CON (Ph)-(CH 2 ) 3- (wherein Ph means phenyl),
-CON (CH 3 )-(CH 2 ) 6- ,
-CON (Ph)-(CH 2 ) 6- (wherein Ph means phenyl),
-CF 2 -CON (CH 3 )-(CH 2 ) 3- ,
-CF 2 -CON (Ph)-(CH 2 ) 3- (wherein, Ph means phenyl),
-CF 2 -CON (CH 3 )-(CH 2 ) 6- ,
-CF 2 -CON (Ph)-(CH 2 ) 6- (wherein, Ph means phenyl),
-CONH- (CH 2 ) 2 NH (CH 2 ) 3- ,
-CONH- (CH 2 ) 6 NH (CH 2 ) 3- ,
It is.
　別の好ましい態様において、Ｘ３は、Ｘｅ’を表す。Ｘｅ’は、上記と同意義である。 In another preferred embodiment, X 3 represents X e ′ . X e ′ is as defined above.
　一の態様において、Ｘｅ’は、単結合である。本態様において、ＰＦＰＥと基材との結合能を有する基（即ち、（Ｂ１）および（Ｂ２）においては、β１を付して括弧でくくられた基）とが直接結合している。 In one embodiment, X e ′ is a single bond. In this embodiment, a group having a binding ability between PFPE and a substrate (that is, a group enclosed in parentheses with β1 in (B1) and (B2)) is directly bonded.
　一の態様において、式（Ｂ１）および（Ｂ２）において、水酸基または加水分解可能な基に結合したＳｉが少なくとも２つ存在する。即ち、式（Ｂ１）および（Ｂ２）において、ＳｉＲ１３の構造が少なくとも２つ存在する。 In one embodiment, in the formulas (B1) and (B2), at least two Si bonded to a hydroxyl group or a hydrolyzable group are present. That is, in the formulas (B1) and (B2), at least two structures of SiR 13 exist.
　好ましい式（Ｂ１）および（Ｂ２）で示される化合物は、下記式（Ｂ１’）および（Ｂ２’）：
Figure JPOXMLDOC01-appb-C000015
 ［式中：
　ＰＦＰＥは、それぞれ独立して、式：
－（ＯＣ６Ｆ１２）ａ－（ＯＣ５Ｆ１０）ｂ－（ＯＣ４Ｆ８）ｃ－（ＯＣ３Ｆ６）ｄ－（ＯＣ２Ｆ４）ｅ－（ＯＣＦ２）ｆ－
（式中、ａ、ｂ、ｃ、ｄ、ｅおよびｆは、それぞれ独立して０以上２００以下の整数であって、ａ、ｂ、ｃ、ｄ、ｅおよびｆの和は少なくとも１である。添字ａ、ｂ、ｃ、ｄ、ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。）
で表される基であり；
　Ｒｆは、各出現においてそれぞれ独立して、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１～１６のアルキル基を表し；
　Ｒ１３は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し；
　Ｒ１４は、各出現においてそれぞれ独立して、水素原子または炭素数１～２２のアルキル基を表し；
　ｎ１は、１～３の整数であり、好ましくは３であり；
　Ｘ３は、－ＣＨ２Ｏ（ＣＨ２）２－、－ＣＨ２Ｏ（ＣＨ２）３－または－ＣＨ２Ｏ（ＣＨ２）６－である。］
で表される化合物である。 Preferred compounds represented by the formulas (B1) and (B2) have the following formulas (B1 ′) and (B2 ′):
Figure JPOXMLDOC01-appb-C000015
 [In the formula:
Each PFPE is independently of the formula:
- (OC 6 F 12) a - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f -
(Wherein, a, b, c, d, e and f are each independently an integer of 0 or more and 200 or less, and the sum of a, b, c, d, e and f is at least 1). The order in which each repeating unit enclosed in parentheses with the subscripts a, b, c, d, e or f is given is arbitrary in the formula.)
A group represented by
R f independently at each occurrence represents an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms;
R 13 independently at each occurrence independently represents a hydroxyl group or a hydrolysable group;
R 14 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms at each occurrence;
n1 is an integer of 1 to 3, preferably 3;
X 3 is —CH 2 O (CH 2 ) 2 —, —CH 2 O (CH 2 ) 3 — or —CH 2 O (CH 2 ) 6 —. ]
It is a compound represented by
　上記式（Ｂ１）および（Ｂ２）で表される化合物は、公知の方法、例えば特開２０１３－１１７０１２号公報に記載の方法またはその改良方法により製造することができる。 The compounds represented by the above formulas (B1) and (B2) can be produced by a known method, for example, the method described in JP 2013-117012 A or its improved method.
　式（Ｃ１）および（Ｃ２）：
Figure JPOXMLDOC01-appb-C000016
 Formulas (C1) and (C2):
Figure JPOXMLDOC01-appb-C000016
　上記式（Ｃ１）および（Ｃ２）中、ＲｆおよびＰＦＰＥは、上記式（Ａ１）および（Ａ２）に関する記載と同意義である。 In the above formulas (C1) and (C2), Rf and PFPE are as defined for the above formulas (A1) and (A2).
　上記式中、Ｘ５は、それぞれ独立して、単結合または２～１０価の有機基を表す。当該Ｘ５は、式（Ｃ１）および（Ｃ２）で表される化合物において、主に撥水性および表面滑り性等を提供するパーフルオロポリエーテル部（即ち、Ｒｆ－ＰＦＰＥ部または－ＰＦＰＥ－部）と、基材との結合能を提供するシラン部（具体的には、－ＳｉＲａ ｋ１Ｒｂ ｌ１Ｒｃ ｍ１基）とを連結するリンカーと解される。従って、当該Ｘ５は、式（Ｃ１）および（Ｃ２）で表される化合物が安定に存在し得るものであれば、いずれの有機基であってもよい。 In the above formulae, each X 5 independently represents a single bond or a di- to 10-valent organic group. The X 5 has the formula (C1) and in the compounds represented by (C2), perfluoropolyether portion which mainly provide water repellency and surface slipperiness, etc. (i.e., Rf-PFPE unit or -PFPE- parts) When (specifically, -SiR a k1 R b l1 R c m1 group) silane unit that provides a binding capability to a substrate is understood as a linker linking. Accordingly, X 5 may be any organic group as long as the compounds represented by formulas (C1) and (C2) can stably exist.
　別の態様において、Ｘ５は、Ｘｅを表す。Ｘｅは、上記と同意義である。 In another aspect, X 5 represents X e . X e is as defined above.
　上記式中のγ１は、１～９の整数であり、γ１’は、１～９の整数である。これらγ１およびγ１’は、Ｘ５の価数に応じて変化し得る。式（Ｃ１）において、γ１およびγ１’の和は、Ｘ５の価数と同じである。例えば、Ｘ５が１０価の有機基である場合、γ１およびγ１’の和は１０であり、例えばγ１が９かつγ１’が１、γ１が５かつγ１’が５、またはγ１が１かつγ１’が９となり得る。また、Ｘ５が２価の有機基である場合、γ１およびγ１’は１である。式（Ｃ２）において、γ１はＸ５の価数の値から１を引いた値である。 In the above formula, γ1 is an integer of 1 to 9, and γ1 ′ is an integer of 1 to 9. These γ1 and γ1 ′ may change according to the valence of X 5 . In formula (C1), the sum of γ1 and γ1 ′ is the same as the valence of X 5 . For example, when X 5 is a 10-valent organic group, the sum of γ1 and γ1 ′ is 10, for example, γ1 is 9 and γ1 ′ is 1, γ1 is 5 and γ1 ′ is 5, or γ1 is 1 and γ1 'Can be nine. When X 5 is a divalent organic group, γ 1 and γ 1 ′ are 1. In Formula (C2), γ1 is a value obtained by subtracting 1 from the value of the valence of X 5 .
　上記Ｘ５は、好ましくは２～７価、より好ましくは２～４価、さらに好ましくは２価の有機基である。 The above X 5 is preferably a divalent to heptavalent, more preferably a divalent to tetravalent, more preferably a divalent organic group.
　一の態様において、Ｘ５は２～４価の有機基であり、γ１は１～３であり、γ１’は１である。 In one embodiment, X 5 is a divalent to tetravalent organic group, γ 1 is 1 to 3 and γ 1 ′ is 1.
　別の態様において、Ｘ５は２価の有機基であり、γ１は１であり、γ１’は１である。この場合、式（Ｃ１）および（Ｃ２）は、下記式（Ｃ１’）および（Ｃ２’）で表される。
Figure JPOXMLDOC01-appb-C000017
 In another embodiment, X 5 is a divalent organic group, γ 1 is 1 and γ 1 ′ is 1. In this case, the formulas (C1) and (C2) are represented by the following formulas (C1 ′) and (C2 ′).
Figure JPOXMLDOC01-appb-C000017
　上記Ｘ５の例としては、特に限定するものではないが、例えば、Ｘ１に関して記載したものと同様のものが挙げられる。 Examples of X 5 include, but are not particularly limited to, the same ones as described for X 1 .
　中でも、好ましい具体的なＸ５は、
単結合、
－ＣＨ２ＯＣＨ２－、
－ＣＨ２Ｏ（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３－、
－ＣＨ２Ｏ（ＣＨ２）６－、
－ＣＦ２－ＣＨ２－Ｏ－ＣＨ２－、
－ＣＦ２－ＣＨ２－Ｏ－（ＣＨ２）２－、
－ＣＦ２－ＣＨ２－Ｏ－（ＣＨ２）３－、
－ＣＦ２－ＣＨ２－Ｏ－（ＣＨ２）６－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）３Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）１０Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２０Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－Ｃ（Ｏ）ＮＨ－ＣＨ２－、
－ＣＨ２ＯＣＨ２（ＣＨ２）７ＣＨ２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）２－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）３－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ２ＣＨ３）２ＯＳｉ（ＯＣＨ２ＣＨ３）２（ＣＨ２）３－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）２－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ２ＣＨ３）２ＯＳｉ（ＯＣＨ２ＣＨ３）２（ＣＨ２）２－、
－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－、
－ＣＨ２－、
－（ＣＨ２）２－、
－（ＣＨ２）３－、
－（ＣＨ２）４－、
－（ＣＨ２）５－、
－（ＣＨ２）６－、
－ＣＦ２－、
－（ＣＦ２）２－、
－ＣＦ２－ＣＨ２－、
－ＣＦ２－（ＣＨ２）２－、
－ＣＦ２－（ＣＨ２）３－、
－ＣＦ２－（ＣＨ２）４－、
－ＣＦ２－（ＣＨ２）５－、
－ＣＦ２－（ＣＨ２）６－、
－ＣＯ－
－ＣＯＮＨ－
－ＣＯＮＨ－ＣＨ２－、
－ＣＯＮＨ－（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＯＮＨ－（ＣＨ２）６－、
－ＣＦ２ＣＯＮＨ－、
－ＣＦ２ＣＯＮＨＣＨ２－、
－ＣＦ２ＣＯＮＨ（ＣＨ２）２－、
－ＣＦ２ＣＯＮＨ（ＣＨ２）３－、
－ＣＦ２ＣＯＮＨ（ＣＨ２）６－、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）３－（式中、Ｐｈはフェニルを意味する）、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）６－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）６－（式中、Ｐｈはフェニルを意味する）、
－ＣＦ２－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＦ２－ＣＯＮ（Ｐｈ）－（ＣＨ２）３－（式中、Ｐｈはフェニルを意味する）、
－ＣＦ２－ＣＯＮ（ＣＨ３）－（ＣＨ２）６－、
－ＣＦ２－ＣＯＮ（Ｐｈ）－（ＣＨ２）６－（式中、Ｐｈはフェニルを意味する）、
－ＣＯＮＨ－（ＣＨ２）２ＮＨ（ＣＨ２）３－、
－ＣＯＮＨ－（ＣＨ２）６ＮＨ（ＣＨ２）３－、
－ＣＨ２Ｏ－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＨ２Ｏ－ＣＯＮＨ－（ＣＨ２）６－、
－Ｓ－（ＣＨ２）３－、
－（ＣＨ２）２Ｓ（ＣＨ２）３－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）３Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）１０Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２０Ｓｉ（ＣＨ３）２（ＣＨ２）２－
－Ｃ（Ｏ）Ｏ－（ＣＨ２）３－、
－Ｃ（Ｏ）Ｏ－（ＣＨ２）６－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－ＣＨ（ＣＨ３）－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－（ＣＨ２）３－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－ＣＨ（ＣＨ３）－ＣＨ２－、
－ＯＣＨ２－、
－Ｏ（ＣＨ２）３－、
－ＯＣＦＨＣＦ２－、
Figure JPOXMLDOC01-appb-C000018
 などが挙げられる。 Among them, preferred specific X 5 is
Single bond,
-CH 2 OCH 2- ,
-CH 2 O (CH 2 ) 2- ,
-CH 2 O (CH 2 ) 3- ,
-CH 2 O (CH 2 ) 6- ,
-CF 2 -CH 2 -O-CH 2- ,
-CF 2 -CH 2 -O- (CH 2 ) 2- ,
-CF 2 -CH 2 -O- (CH 2 ) 3- ,
-CF 2 -CH 2 -O- (CH 2 ) 6-
-CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2- ,
-CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2- ,
-CH 2 O (CH 2) 3 Si (CH 3) 2 O (Si (CH 3) 2 O) 2 Si (CH 3) 2 (CH 2) 2 -,
-CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 3 Si (CH 3 ) 2 (CH 2 ) 2- ,
-CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 10 Si (CH 3 ) 2 (CH 2 ) 2- ,
-CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 20 Si (CH 3 ) 2 (CH 2 ) 2- ,
-CH 2 OCF 2 CHFOCF 2- ,
-CH 2 OCF 2 CHFOCF 2 CF 2- ,
-CH 2 OCF 2 CHFOCF 2 CF 2 CF 2- ,
-CH 2 OCH 2 CF 2 CF 2 OCF 2- ,
-CH 2 OCH 2 CF 2 CF 2 OCF 2 CF 2- ,
-CH 2 OCH 2 CF 2 CF 2 OCF 2 CF 2 CF 2- ,
-CH 2 OCH 2 CF 2 CF 2 OCF (CF 3) CF 2 OCF 2 -,
-CH 2 OCH 2 CF 2 CF 2 OCF (CF 3) CF 2 OCF 2 CF 2 -,
-CH 2 OCH 2 CF 2 CF 2 OCF (CF 3) CF 2 OCF 2 CF 2 CF 2 -,
-CH 2 OCH 2 CHFCF 2 OCF 2- ,
-CH 2 OCH 2 CHFCF 2 OCF 2 CF 2- ,
-CH 2 OCH 2 CHFCF 2 OCF 2 CF 2 CF 2- ,
-CH 2 OCH 2 CHFCF 2 OCF ( CF 3) CF 2 OCF 2 -,
-CH 2 OCH 2 CHFCF 2 OCF ( CF 3) CF 2 OCF 2 CF 2 -,
-CH 2 OCH 2 CHFCF 2 OCF (CF 3 ) CF 2 OCF 2 CF 2 CF 2-
-CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 -C (O) NH-CH 2- ,
-CH 2 OCH 2 (CH 2 ) 7 CH 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 2- ,
-CH 2 OCH 2 CH 2 CH 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 3- ,
-CH 2 OCH 2 CH 2 CH 2 Si (OCH 2 CH 3 ) 2 OSi (OCH 2 CH 3 ) 2 (CH 2 ) 3- ,
-CH 2 OCH 2 CH 2 CH 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 2- ,
-CH 2 OCH 2 CH 2 CH 2 Si (OCH 2 CH 3 ) 2 OSi (OCH 2 CH 3 ) 2 (CH 2 ) 2- ,
-(CH 2 ) 2 -Si (CH 3 ) 2- (CH 2 ) 2- ,
-CH 2- ,
-(CH 2 ) 2- ,
-(CH 2 ) 3- ,
- (CH 2) 4 -,
-(CH 2 ) 5- ,
-(CH 2 ) 6- ,
-CF 2- ,
-(CF 2 ) 2- ,
-CF 2 -CH 2- ,
-CF 2- (CH 2 ) 2- ,
-CF 2- (CH 2 ) 3- ,
-CF 2 - (CH 2) 4 -,
-CF 2- (CH 2 ) 5- ,
-CF 2- (CH 2 ) 6- ,
-CO-
-CONH-
-CONH-CH 2- ,
-CONH- (CH 2 ) 2- ,
-CONH- (CH 2 ) 3- ,
-CONH- (CH 2 ) 6- ,
-CF 2 CONH-,
-CF 2 CONHCH 2- ,
-CF 2 CONH (CH 2 ) 2- ,
-CF 2 CONH (CH 2 ) 3- ,
-CF 2 CONH (CH 2 ) 6- ,
-CON (CH 3 )-(CH 2 ) 3- ,
-CON (Ph)-(CH 2 ) 3- (wherein Ph means phenyl),
-CON (CH 3 )-(CH 2 ) 6- ,
-CON (Ph)-(CH 2 ) 6- (wherein Ph means phenyl),
-CF 2 -CON (CH 3 )-(CH 2 ) 3- ,
-CF 2 -CON (Ph)-(CH 2 ) 3- (wherein, Ph means phenyl),
-CF 2 -CON (CH 3 )-(CH 2 ) 6- ,
-CF 2 -CON (Ph)-(CH 2 ) 6- (wherein, Ph means phenyl),
-CONH- (CH 2 ) 2 NH (CH 2 ) 3- ,
-CONH- (CH 2 ) 6 NH (CH 2 ) 3- ,
-CH 2 O-CONH- (CH 2 ) 3- ,
-CH 2 O-CONH- (CH 2 ) 6- ,
-S- (CH 2 ) 3- ,
-(CH 2 ) 2 S (CH 2 ) 3- ,
-CONH- (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2- ,
-CONH- (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2- ,
-CONH- (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 2 Si (CH 3 ) 2 (CH 2 ) 2- ,
-CONH- (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 3 Si (CH 3 ) 2 (CH 2 ) 2- ,
-CONH- (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 10 Si (CH 3 ) 2 (CH 2 ) 2- ,
-CONH- (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 20 Si (CH 3 ) 2 (CH 2 ) 2-
-C (O) O- (CH 2 ) 3- ,
-C (O) O- (CH 2 ) 6- ,
-CH 2 -O- (CH 2 ) 3 -Si (CH 3 ) 2- (CH 2 ) 2 -Si (CH 3 ) 2- (CH 2 ) 2- ,
-CH 2 -O- (CH 2 ) 3 -Si (CH 3 ) 2- (CH 2 ) 2 -Si (CH 3 ) 2 -CH (CH 3 )-,
-CH 2 -O- (CH 2 ) 3 -Si (CH 3 ) 2- (CH 2 ) 2 -Si (CH 3 ) 2- (CH 2 ) 3- ,
-CH 2 -O- (CH 2 ) 3 -Si (CH 3 ) 2- (CH 2 ) 2 -Si (CH 3 ) 2 -CH (CH 3 ) -CH 2- ,
-OCH 2-
-O (CH 2 ) 3- ,
-OCFHCF 2- ,
Figure JPOXMLDOC01-appb-C000018
 Etc.
　上記の中では、Ｘ５は、好ましくは、
－ＣＨ２ＯＣＨ２－、
－ＣＨ２Ｏ（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３－、
－ＣＨ２Ｏ（ＣＨ２）６－、
－ＣＦ２－ＣＨ２－Ｏ－ＣＨ２－、
－ＣＦ２－ＣＨ２－Ｏ－（ＣＨ２）２－、
－ＣＦ２－ＣＨ２－Ｏ－（ＣＨ２）３－、
－ＣＦ２－ＣＨ２－Ｏ－（ＣＨ２）６－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－Ｃ（Ｏ）ＮＨ－ＣＨ２－、
－ＣＦ２－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－Ｃ（Ｏ）ＮＨ－ＣＨ２－、
－ＣＨ２－、
－（ＣＨ２）２－、
－（ＣＨ２）３－、
－（ＣＨ２）４－、
－（ＣＨ２）５－、
－（ＣＨ２）６－、
－ＣＦ２－、
－（ＣＦ２）２－、
－ＣＦ２－ＣＨ２－、
－ＣＦ２－（ＣＨ２）２－、
－ＣＦ２－（ＣＨ２）３－、
－ＣＦ２－（ＣＨ２）４－、
－ＣＦ２－（ＣＨ２）５－、
－ＣＦ２－（ＣＨ２）６－、
－ＣＯＮＨ－、
－ＣＯＮＨ－ＣＨ２－、
－ＣＯＮＨ－（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＯＮＨ－（ＣＨ２）６－、
－ＣＦ２ＣＯＮＨ－、
－ＣＦ２ＣＯＮＨＣＨ２－、
－ＣＦ２ＣＯＮＨ（ＣＨ２）２－、
－ＣＦ２ＣＯＮＨ（ＣＨ２）３－、
－ＣＦ２ＣＯＮＨ（ＣＨ２）６－、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）３－（式中、Ｐｈはフェニルを意味する）、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）６－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）６－（式中、Ｐｈはフェニルを意味する）、
－ＣＦ２－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＦ２－ＣＯＮ（Ｐｈ）－（ＣＨ２）３－（式中、Ｐｈはフェニルを意味する）、
－ＣＦ２－ＣＯＮ（ＣＨ３）－（ＣＨ２）６－、
－ＣＦ２－ＣＯＮ（Ｐｈ）－（ＣＨ２）６－（式中、Ｐｈはフェニルを意味する）、
－ＣＯＮＨ－（ＣＨ２）２ＮＨ（ＣＨ２）３－、
－ＣＯＮＨ－（ＣＨ２）６ＮＨ（ＣＨ２）３－、
－ＣＨ２Ｏ－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＨ２Ｏ－ＣＯＮＨ－（ＣＨ２）６－、
－ＯＣＨ２－、
－Ｏ（ＣＨ２）３－、
－ＯＣＦＨＣＦ２－、
であることが好ましい。 Among the above, X 5 is preferably
-CH 2 OCH 2- ,
-CH 2 O (CH 2 ) 2- ,
-CH 2 O (CH 2 ) 3- ,
-CH 2 O (CH 2 ) 6- ,
-CF 2 -CH 2 -O-CH 2- ,
-CF 2 -CH 2 -O- (CH 2 ) 2- ,
-CF 2 -CH 2 -O- (CH 2 ) 3- ,
-CF 2 -CH 2 -O- (CH 2 ) 6-
-CH 2 OCF 2 CHFOCF 2- ,
-CH 2 OCF 2 CHFOCF 2 CF 2- ,
-CH 2 OCF 2 CHFOCF 2 CF 2 CF 2- ,
-CH 2 OCH 2 CF 2 CF 2 OCF 2- ,
-CH 2 OCH 2 CF 2 CF 2 OCF 2 CF 2- ,
-CH 2 OCH 2 CF 2 CF 2 OCF 2 CF 2 CF 2- ,
-CH 2 OCH 2 CF 2 CF 2 OCF (CF 3) CF 2 OCF 2 -,
-CH 2 OCH 2 CF 2 CF 2 OCF (CF 3) CF 2 OCF 2 CF 2 -,
-CH 2 OCH 2 CF 2 CF 2 OCF (CF 3) CF 2 OCF 2 CF 2 CF 2 -,
-CH 2 OCH 2 CHFCF 2 OCF 2- ,
-CH 2 OCH 2 CHFCF 2 OCF 2 CF 2- ,
-CH 2 OCH 2 CHFCF 2 OCF 2 CF 2 CF 2- ,
-CH 2 OCH 2 CHFCF 2 OCF ( CF 3) CF 2 OCF 2 -,
-CH 2 OCH 2 CHFCF 2 OCF ( CF 3) CF 2 OCF 2 CF 2 -,
-CH 2 OCH 2 CHFCF 2 OCF ( CF 3) CF 2 OCF 2 CF 2 CF 2 -,
-CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 -C (O) NH-CH 2- ,
-CF 2 -CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 -C (O) NH-CH 2- ,
-CH 2- ,
-(CH 2 ) 2- ,
-(CH 2 ) 3- ,
- (CH 2) 4 -,
-(CH 2 ) 5- ,
-(CH 2 ) 6- ,
-CF 2- ,
-(CF 2 ) 2- ,
-CF 2 -CH 2- ,
-CF 2- (CH 2 ) 2- ,
-CF 2- (CH 2 ) 3- ,
-CF 2 - (CH 2) 4 -,
-CF 2- (CH 2 ) 5- ,
-CF 2- (CH 2 ) 6- ,
-CONH-,
-CONH-CH 2- ,
-CONH- (CH 2 ) 2- ,
-CONH- (CH 2 ) 3- ,
-CONH- (CH 2 ) 6- ,
-CF 2 CONH-,
-CF 2 CONHCH 2- ,
-CF 2 CONH (CH 2 ) 2- ,
-CF 2 CONH (CH 2 ) 3- ,
-CF 2 CONH (CH 2 ) 6- ,
-CON (CH 3 )-(CH 2 ) 3- ,
-CON (Ph)-(CH 2 ) 3- (wherein Ph means phenyl),
-CON (CH 3 )-(CH 2 ) 6- ,
-CON (Ph)-(CH 2 ) 6- (wherein Ph means phenyl),
-CF 2 -CON (CH 3 )-(CH 2 ) 3- ,
-CF 2 -CON (Ph)-(CH 2 ) 3- (wherein, Ph means phenyl),
-CF 2 -CON (CH 3 )-(CH 2 ) 6- ,
-CF 2 -CON (Ph)-(CH 2 ) 6- (wherein, Ph means phenyl),
-CONH- (CH 2 ) 2 NH (CH 2 ) 3- ,
-CONH- (CH 2 ) 6 NH (CH 2 ) 3- ,
-CH 2 O-CONH- (CH 2 ) 3- ,
-CH 2 O-CONH- (CH 2 ) 6- ,
-OCH 2-
-O (CH 2 ) 3- ,
-OCFHCF 2- ,
Is preferred.
　上記の中では、より好ましくは、Ｘ５は、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－Ｃ（Ｏ）ＮＨ－ＣＨ２－、
－ＣＦ２－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－Ｃ（Ｏ）ＮＨ－ＣＨ２－、
－ＣＯＮＨ－、
－ＣＯＮＨ－ＣＨ２－、
－ＣＯＮＨ－（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＯＮＨ－（ＣＨ２）６－、
－ＣＦ２ＣＯＮＨ－、
－ＣＦ２ＣＯＮＨＣＨ２－、
－ＣＦ２ＣＯＮＨ（ＣＨ２）２－、
－ＣＦ２ＣＯＮＨ（ＣＨ２）３－、
－ＣＦ２ＣＯＮＨ（ＣＨ２）６－、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）３－（式中、Ｐｈはフェニルを意味する）、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）６－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）６－（式中、Ｐｈはフェニルを意味する）、
－ＣＦ２－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＦ２－ＣＯＮ（Ｐｈ）－（ＣＨ２）３－（式中、Ｐｈはフェニルを意味する）、
－ＣＦ２－ＣＯＮ（ＣＨ３）－（ＣＨ２）６－、
－ＣＦ２－ＣＯＮ（Ｐｈ）－（ＣＨ２）６－（式中、Ｐｈはフェニルを意味する）、
－ＣＯＮＨ－（ＣＨ２）２ＮＨ（ＣＨ２）３－、
－ＣＯＮＨ－（ＣＨ２）６ＮＨ（ＣＨ２）３－、
である。 Among the above, more preferably, X 5 is
-CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 -C (O) NH-CH 2- ,
-CF 2 -CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 -C (O) NH-CH 2- ,
-CONH-,
-CONH-CH 2- ,
-CONH- (CH 2 ) 2- ,
-CONH- (CH 2 ) 3- ,
-CONH- (CH 2 ) 6- ,
-CF 2 CONH-,
-CF 2 CONHCH 2- ,
-CF 2 CONH (CH 2 ) 2- ,
-CF 2 CONH (CH 2 ) 3- ,
-CF 2 CONH (CH 2 ) 6- ,
-CON (CH 3 )-(CH 2 ) 3- ,
-CON (Ph)-(CH 2 ) 3- (wherein Ph means phenyl),
-CON (CH 3 )-(CH 2 ) 6- ,
-CON (Ph)-(CH 2 ) 6- (wherein Ph means phenyl),
-CF 2 -CON (CH 3 )-(CH 2 ) 3- ,
-CF 2 -CON (Ph)-(CH 2 ) 3- (wherein, Ph means phenyl),
-CF 2 -CON (CH 3 )-(CH 2 ) 6- ,
-CF 2 -CON (Ph)-(CH 2 ) 6- (wherein, Ph means phenyl),
-CONH- (CH 2 ) 2 NH (CH 2 ) 3- ,
-CONH- (CH 2 ) 6 NH (CH 2 ) 3- ,
It is.
　別の好ましい態様において、Ｘ５は、Ｘｅ’を表す。Ｘｅ’は、上記と同意義である。 In another preferred embodiment, X 5 represents X e ′ . X e ′ is as defined above.
　一の態様において、Ｘｅ’は、単結合である。本態様において、ＰＦＰＥと基材との結合能を有する基（即ち、（Ｃ１）および（Ｃ２）においては、γ１を付して括弧でくくられた基）とが直接結合している。 In one embodiment, X e ′ is a single bond. In this embodiment, a group capable of binding PFPE to a substrate (that is, a group which is attached with γ1 and bracketed in (C1) and (C2)) is directly bonded.
　上記式中、Ｒａは、各出現においてそれぞれ独立して、－Ｚ３－ＳｉＲ７１ ｐ１Ｒ７２ ｑ１Ｒ７３ ｒ１を表す。 In the above formulae, R a independently represents -Z 3 -SiR 71 p 1 R 72 q 1 R 73 r 1 at each occurrence.
　式中、Ｚ３は、各出現においてそれぞれ独立して、酸素原子または２価の有機基を表す。 In the formula, each Z 3 independently represents an oxygen atom or a divalent organic group.
　上記Ｚ３は、好ましくは、２価の有機基であり、式（Ｃ１）または式（Ｃ２）における分子主鎖の末端のＳｉ原子（Ｒａが結合しているＳｉ原子）とシロキサン結合を形成するものを含まない。 The above Z 3 is preferably a divalent organic group, and forms a siloxane bond with the Si atom at the end of the molecular main chain in the formula (C1) or the formula (C2) (Si atom to which R a is bonded) Do not include what you do.
　上記Ｚ３は、好ましくは、Ｃ１－６アルキレン基、－（ＣＨ２）ｇ－Ｏ－（ＣＨ２）ｈ－（式中、ｇは、１～６の整数であり、ｈは、１～６の整数である）または、－フェニレン－（ＣＨ２）ｉ－（式中、ｉは、０～６の整数である）であり、より好ましくはＣ１－３アルキレン基である。これらの基は、例えば、フッ素原子、Ｃ１－６アルキル基、Ｃ２－６アルケニル基、およびＣ２－６アルキニル基から選択される１個またはそれ以上の置換基により置換されていてもよい。紫外線耐久性が特に良好な観点からは、上記Ｚ３は、より好ましくは、直鎖状または分枝鎖状のアルキレン基であり、さらに好ましくは直鎖状のアルキレン基である。上記Ｚ３のアルキレン基を構成する炭素数は、好ましくは１～６の範囲にあり、より好ましくは１～３の範囲にある。なお、アルキレン基については上記のとおりである。 The above Z 3 is preferably a C 1-6 alkylene group,-(CH 2 ) g -O- (CH 2 ) h- (wherein, g is an integer of 1 to 6 and h is 1 to 6) Or -phenylene- (CH 2 ) i- (wherein i is an integer of 0 to 6), and more preferably a C 1-3 alkylene group. These groups may be substituted, for example, by one or more substituents selected from a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group. . From the viewpoint of particularly good ultraviolet light durability, the above Z 3 is more preferably a linear or branched alkylene group, and still more preferably a linear alkylene group. The number of carbon atoms constituting the above-mentioned alkylene group of Z 3 is preferably in the range of 1 to 6, and more preferably in the range of 1 to 3. The alkylene group is as described above.
　式中、Ｒ７１は、各出現においてそれぞれ独立して、Ｒａ’を表す。Ｒａ’は、Ｒａと同意義である。 In the formula, R 71 independently represents Ra ' at each occurrence. R a ′ is as defined in R a .
　Ｒａ中、Ｚ３基を介して直鎖状に連結されるＳｉは最大で５個である。即ち、上記Ｒａにおいて、Ｒ７１が少なくとも１つ存在する場合、Ｒａ中にＺ３基を介して直鎖状に連結されるＳｉ原子が２個以上存在するが、かかるＺ３基を介して直鎖状に連結されるＳｉ原子の数は最大で５個である。なお、「Ｒａ中のＺ３基を介して直鎖状に連結されるＳｉ原子の数」とは、Ｒａ中において直鎖状に連結される－Ｚ３－Ｓｉ－の繰り返し数と等しくなる。 In R a , the maximum number of Sis linked in a linear fashion via a Z 3 group is five. That is, in the above R a , when at least one R 71 is present, two or more Si atoms linearly linked through the Z 3 group are present in R a , but through such Z 3 group Thus, the number of Si atoms linked in a linear manner is at most five. Note that the "through Z 3 group in R a number of Si atoms linearly linked" is equal to -Z 3 -Si- repetition number of which is connected to a linear during R a Become.
　例えば、下記にＲａ中においてＺ３基を介してＳｉ原子が連結された一例を示す。
Figure JPOXMLDOC01-appb-C000019
 For example, an example in which the Si atoms are connected via a Z 3 group in a R a below.
Figure JPOXMLDOC01-appb-C000019
　上記式において、＊は、主鎖のＳｉに結合する部位を意味し、…は、Ｚ３Ｓｉ以外の所定の基が結合していること、即ち、Ｓｉ原子の３本の結合手がすべて…である場合、Ｚ３Ｓｉの繰り返しの終了箇所を意味する。また、Ｓｉの右肩の数字は、＊から数えたＺ３基を介して直鎖状に連結されたＳｉの出現数を意味する。即ち、Ｓｉ２でＺ３Ｓｉ繰り返しが終了している鎖は「Ｒａ中のＺ３基を介して直鎖状に連結されるＳｉ原子の数」が２個であり、同様に、Ｓｉ３、Ｓｉ４およびＳｉ５でＺ３Ｓｉ繰り返しが終了している鎖は、それぞれ、「Ｒａ中のＺ３基を介して直鎖状に連結されるＳｉ原子の数」が３、４および５個である。なお、上記の式から明らかなように、Ｒａ中には、Ｚ３Ｓｉ鎖が複数存在するが、これらはすべて同じ長さである必要はなく、それぞれ任意の長さであってもよい。 In the above formula, * means a site to be bonded to Si in the main chain, ... indicates that a predetermined group other than Z 3 Si is bonded, that is, all three bonds of Si atoms are ... In this case, it means the end of the repetition of Z 3 Si. Moreover, the number on the right of Si means the appearance number of Si linearly linked via Z 3 group counted from *. That is, the chain in which the Z 3 Si repeat is completed in Si 2 is “the number of Si atoms linearly linked via the Z 3 group in R a ” is 2, similarly, Si 3 , And Si 4 and Si 5 in which the Z 3 Si repeat ends are “number of Si atoms linearly linked via Z 3 group in R a ” of 3, 4 and 5, respectively Is one. As is apparent from the above formula, a plurality of Z 3 Si chains are present in R a , but they do not have to have the same length, and may have any length.
　好ましい態様において、下記に示すように、「Ｒａ中のＺ３基を介して直鎖状に連結されるＳｉ原子の数」は、すべての鎖において、１個（左式）または２個（右式）である。
Figure JPOXMLDOC01-appb-C000020
 In a preferred embodiment, as shown below, “the number of Si atoms linearly linked via the Z 3 group in R a ” is 1 (left equation) or 2 (all the chains) in all chains. Right).
Figure JPOXMLDOC01-appb-C000020
　一の態様において、Ｒａ中のＺ３基を介して直鎖状に連結されるＳｉ原子の数は１個または２個、好ましくは１個である。 In one embodiment, the number of Si atoms linearly linked via the Z 3 group in R a is 1 or 2, preferably 1.
　式中、Ｒ７２は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表す。「加水分解可能な基」は、上記と同意義である。 In the formula, each R 72 independently at each occurrence represents a hydroxyl group or a hydrolysable group. The "hydrolyzable group" is as defined above.
　好ましくは、Ｒ７２は、－ＯＲ（式中、Ｒは、置換または非置換のＣ１－３アルキル基、より好ましくはメチル基を表す）である。 Preferably, R 72 is —OR, wherein R represents a substituted or unsubstituted C 1-3 alkyl group, more preferably a methyl group.
　式中、Ｒ７３は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表す。該低級アルキル基は、好ましくは炭素数１～２０のアルキル基、より好ましくは炭素数１～６のアルキル基、さらに好ましくはメチル基である。 In the formulae, R 73 each independently represents a hydrogen atom or a lower alkyl group at each occurrence. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
　式中、ｐ１は、各出現においてそれぞれ独立して、０～３の整数であり；ｑ１は、各出現においてそれぞれ独立して、０～３の整数であり；ｒ１は、各出現においてそれぞれ独立して、０～３の整数である。ただし、（－Ｚ３－ＳｉＲ７１ ｐ１Ｒ７２ ｑ１Ｒ７３ ｒ１）毎において、ｐ１、ｑ１およびｒ１の和は３である。 In the formula, p1 is each independently an integer of 0 to 3 at each occurrence; q1 is each independently an integer of 0 to 3 at each occurrence; r1 is each independently at each occurrence Is an integer of 0 to 3. However, the sum of p1, q1 and r1 is 3 for each (-Z 3 -SiR 71 p1 R 72 q1 R 73 r1 ).
　好ましい態様において、Ｒａ中の末端のＲａ’（Ｒａ’が存在しない場合、Ｒａ）において、上記ｑ１は、好ましくは２以上、例えば２または３であり、より好ましくは３である。 In a preferred embodiment, '(if R a' is absent, R a) terminal of R a in R a in the above q1 is preferably 2 or more, for example 2 or 3, more preferably 3.
　好ましい態様において、Ｒａの末端部の少なくとも１つは、－Ｓｉ（－Ｚ３－ＳｉＲ７２ ｑ１Ｒ７３ ｒ１）２または－Ｓｉ（－Ｚ３－ＳｉＲ７２ ｑ１Ｒ７３ ｒ１）３、好ましくは－Ｓｉ（－Ｚ３－ＳｉＲ７２ ｑ１Ｒ７３ ｒ１）３であり得る。式中、（－Ｚ３－ＳｉＲ７２ ｑ１Ｒ７３ ｒ１）の単位は、好ましくは（－Ｚ３－ＳｉＲ７２ ３）である。さらに好ましい態様において、Ｒａの末端部は、すべて－Ｓｉ（－Ｚ３－ＳｉＲ７２ ｑ１Ｒ７３ ｒ１）３、好ましくは－Ｓｉ（－Ｚ３－ＳｉＲ７２ ３）３であり得る。 In a preferred embodiment, at least one of the terminal parts of R a is -Si (-Z 3 -SiR 72 q1 R 73 r1 ) 2 or -Si (-Z 3 -SiR 72 q1 R 73 r1 ) 3 , preferably- It may be Si (-Z 3 -SiR 72 q1 R 73 r1 ) 3 . Wherein, (- Z 3 -SiR 72 q1 R 73 r1) units is preferably (-Z 3 -SiR 72 3). In a further preferred embodiment, all the terminal parts of R a may be -Si (-Z 3 -SiR 72 q1 R 73 r1 ) 3 , preferably -Si (-Z 3 -SiR 72 3 ) 3 .
　上記式（Ｃ１）および（Ｃ２）においては、少なくとも１つのｑ１が１～３の整数であり、すなわち、少なくとも１つのＲ７２が存在する。 In the above formulas (C1) and (C2), at least one q1 is an integer of 1 to 3, that is, at least one R 72 is present.
　一の態様において、式（Ｃ１）および（Ｃ２）においては、水酸基または加水分解可能な基に結合したＳｉが少なくとも２つ存在する。即ち、ＳｉＲ７２および／またはＳｉＲｂの構造が少なくとも２つ存在する。 In one embodiment, in the formulas (C1) and (C2), at least two Si bonded to a hydroxyl group or a hydrolyzable group are present. That is, there are at least two structures of SiR 72 and / or SiR b .
　上記式中、Ｒｂは、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表す。 In the above formulas, each R b independently represents a hydroxyl group or a hydrolysable group.
　上記Ｒｂは、好ましくは、水酸基、－ＯＲ、－ＯＣＯＲ、－Ｏ－Ｎ＝Ｃ（Ｒ）２、－Ｎ（Ｒ）２、－ＮＨＲ、ハロゲン（これら式中、Ｒは、置換または非置換の炭素数１～４のアルキル基を示す）であり、より好ましくは－ＯＲである。Ｒは、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基などの非置換アルキル基；クロロメチル基などの置換アルキル基が含まれる。それらの中でも、アルキル基、特に非置換アルキル基が好ましく、メチル基またはエチル基がより好ましい。水酸基は、特に限定されないが、加水分解可能な基が加水分解して生じたものであってよい。より好ましくは、Ｒｂは、－ＯＲ（式中、Ｒは、置換または非置換のＣ１－３アルキル基、より好ましくはメチル基を表す）である。 The above R b is preferably a hydroxyl group, —OR, —OCOR, —O—N = C (R) 2 , —N (R) 2 , —NHR, halogen (in these formulas, R is substituted or unsubstituted) (Indicating an alkyl group having 1 to 4 carbon atoms), and more preferably -OR. R includes an unsubstituted alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group and an isobutyl group; and a substituted alkyl group such as a chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable. The hydroxyl group is not particularly limited, but may be formed by hydrolysis of a hydrolyzable group. More preferably, R b is —OR, wherein R represents a substituted or unsubstituted C 1-3 alkyl group, more preferably a methyl group.
　上記式中、Ｒｃは、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表す。該低級アルキル基は、好ましくは炭素数１～２０のアルキル基、より好ましくは炭素数１～６のアルキル基、さらに好ましくはメチル基である。 In the above formulae, R c independently at each occurrence represents a hydrogen atom or a lower alkyl group. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
　式中、ｋ１は、各出現においてそれぞれ独立して、０～３の整数であり；ｌ１は、各出現においてそれぞれ独立して、０～３の整数であり；ｍ１は、各出現においてそれぞれ独立して、０～３の整数である。ただし、（ＳｉＲａ ｋ１Ｒｂ ｌ１Ｒｃ ｍ１）毎において、ｋ１、ｌ１およびｍ１の和は、３である。 In the formula, k1 is each independently an integer of 0 to 3 at each occurrence; 11 is each independently an integer of 0 to 3 at each occurrence; m1 is each independently at each occurrence Is an integer of 0 to 3. However, in (SiR a k1 R b l1 R c m1) each, the sum of k1, l1 and m1 is 3.
　一の態様において、ｋ１は、１～３であることが好ましく、３であることがより好ましい。 In one aspect, k1 is preferably 1 to 3, and more preferably 3.
　上記式（Ｃ１）および（Ｃ２）で表される化合物は、例えば、Ｒｆ－ＰＦＰＥ－部分に対応するパーフルオロポリエーテル誘導体を原料として、末端に水酸基を導入した後、末端に不飽和結合を有する基を導入し、この不飽和結合を有する基とハロゲン原子を有するシリル誘導体とを反応させ、さらにこのシリル基に末端に水酸基、次いで不飽和結合を有する基を導入し、最後に導入した不飽和結合を有する基とシリル誘導体とを反応させることにより得ることができる。例えば、国際公開第２０１４／０６９５９２号に記載のように合成することができる。 The compounds represented by the above formulas (C1) and (C2) have, for example, an unsaturated bond at the end after introducing a hydroxyl group at the end using a perfluoropolyether derivative corresponding to the Rf-PFPE- moiety as a raw material A group is introduced, a group having this unsaturated bond is reacted with a silyl derivative having a halogen atom, and further a hydroxyl group at the end of the silyl group is introduced followed by a group having an unsaturated bond, and the last introduced unsaturated It can be obtained by reacting a group having a bond with a silyl derivative. For example, it can be synthesized as described in WO 2014/069592.
　式（Ｄ１）および（Ｄ２）：
Figure JPOXMLDOC01-appb-I000021
Formulas (D1) and (D2):
Figure JPOXMLDOC01-appb-I000021
　上記式（Ｄ１）および（Ｄ２）中、ＲｆおよびＰＦＰＥは、上記式（Ａ１）および（Ａ２）に関する記載と同意義である。 In the above formulas (D1) and (D2), Rf and PFPE are as defined in the above formulas (A1) and (A2).
　上記式中、Ｘ７は、それぞれ独立して、単結合または２～１０価の有機基を表す。当該Ｘ７は、式（Ｄ１）および（Ｄ２）で表される化合物において、主に撥水性および表面滑り性等を提供するパーフルオロポリエーテル部（即ち、Ｒｆ－ＰＦＰＥ部または－ＰＦＰＥ－部）と、基材との結合能を提供する部（即ち、δ１を付して括弧でくくられた基）とを連結するリンカーと解される。従って、当該Ｘ７は、式（Ｄ１）および（Ｄ２）で表される化合物が安定に存在し得るものであれば、いずれの有機基であってもよい。 In the above formulae, each X 7 independently represents a single bond or a di- to 10-valent organic group. The said X 7 is a perfluoropolyether part (namely, Rf-PFPE part or -PFPE- part) which mainly provides water repellency, surface slip property, etc. in the compound represented by Formula (D1) and (D2) And a portion that provides the ability to bind to a substrate (ie, a group that is enclosed in parentheses with a δ1 attached thereto). Accordingly, the X 7 may be any organic group as long as the compounds represented by the formulas (D1) and (D2) can stably exist.
　別の態様において、Ｘ７は、Ｘｅを表す。Ｘｅは、上記と同意義である。 In another aspect, X 7 represents X e . X e is as defined above.
　上記式中、δ１は１～９の整数であり、δ１’は１～９の整数である。これらδ１およびδ１’は、Ｘ７の価数に応じて変化し得る。式（Ｄ１）においては、δ１およびδ１’の和は、Ｘ７の価数と同じである。例えば、Ｘ７が１０価の有機基である場合、δ１およびδ１’の和は１０であり、例えばδ１が９かつδ１’が１、δ１が５かつδ１’が５、またはδ１が１かつδ１’が９となり得る。また、Ｘ７が２価の有機基である場合、δ１およびδ１’は１である。式（Ｄ２）においては、δ１はＸ７の価数から１を引いた値である。 In the above formula, δ 1 is an integer of 1 to 9, and δ 1 ′ is an integer of 1 to 9. These δ1 and δ1 ′ can change according to the valence of X 7 . In formula (D1), the sum of δ1 and δ1 ′ is the same as the valence of X 7 . For example, when X 7 is a 10-valent organic group, the sum of δ1 and δ1 ′ is 10, for example, δ1 is 9 and δ1 ′ is 1, δ1 is 5 and δ1 ′ is 5, or δ1 is 1 and δ1 'Can be nine. When X 7 is a divalent organic group, δ 1 and δ 1 ′ are 1. In formula (D2), δ1 is the value obtained by subtracting 1 from the valence of X 7.
　上記Ｘ７は、好ましくは２～７価、より好ましくは２～４価、さらに好ましくは２価の有機基である。 The above-mentioned X 7 is preferably a divalent to heptavalent, more preferably a divalent to tetravalent, more preferably a divalent organic group.
　一の態様において、Ｘ７は２～４価の有機基であり、δ１は１～３であり、δ１’は１である。 In one embodiment, X 7 is a divalent to tetravalent organic group, δ 1 is 1 to 3 and δ 1 ′ is 1.
　別の態様において、Ｘ７は２価の有機基であり、δ１は１であり、δ１’は１である。この場合、式（Ｄ１）および（Ｄ２）は、下記式（Ｄ１’）および（Ｄ２’）で表される。
Figure JPOXMLDOC01-appb-C000022
 In another embodiment, X 7 is a divalent organic group, δ 1 is 1 and δ 1 ′ is 1. In this case, the formulas (D1) and (D2) are represented by the following formulas (D1 ′) and (D2 ′).
Figure JPOXMLDOC01-appb-C000022
　上記Ｘ７の例としては、特に限定するものではないが、例えば、Ｘ１に関して記載したものと同様のものが挙げられる。 Examples of X 7 include, but are not particularly limited to, the same ones as those described for X 1 .
　中でも、好ましい具体的なＸ７は、
単結合、
－ＣＨ２ＯＣＨ２－、
－ＣＨ２Ｏ（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３－、
－ＣＨ２Ｏ（ＣＨ２）６－、
－ＣＦ２－ＣＨ２－Ｏ－ＣＨ２－、
－ＣＦ２－ＣＨ２－Ｏ－（ＣＨ２）２－、
－ＣＦ２－ＣＨ２－Ｏ－（ＣＨ２）３－、
－ＣＦ２－ＣＨ２－Ｏ－（ＣＨ２）６－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）３Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）１０Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２０Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－Ｃ（Ｏ）ＮＨ－ＣＨ２－、
－ＣＨ２ＯＣＨ２（ＣＨ２）７ＣＨ２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）２－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）３－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ２ＣＨ３）２ＯＳｉ（ＯＣＨ２ＣＨ３）２（ＣＨ２）３－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）２－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ２ＣＨ３）２ＯＳｉ（ＯＣＨ２ＣＨ３）２（ＣＨ２）２－、
－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－、
－ＣＨ２－、
－（ＣＨ２）２－、
－（ＣＨ２）３－、
－（ＣＨ２）４－、
－（ＣＨ２）５－、
－（ＣＨ２）６－、
－ＣＦ２－、
－（ＣＦ２）２－、
－ＣＦ２－ＣＨ２－、
－ＣＦ２－（ＣＨ２）２－、
－ＣＦ２－（ＣＨ２）３－、
－ＣＦ２－（ＣＨ２）４－、
－ＣＦ２－（ＣＨ２）５－、
－ＣＦ２－（ＣＨ２）６－、
－ＣＯ－、
－ＣＯＮＨ－
－ＣＯＮＨ－ＣＨ２－、
－ＣＯＮＨ－（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＯＮＨ－（ＣＨ２）６－、
－ＣＦ２ＣＯＮＨ－、
－ＣＦ２ＣＯＮＨＣＨ２－、
－ＣＦ２ＣＯＮＨ（ＣＨ２）２－、
－ＣＦ２ＣＯＮＨ（ＣＨ２）３－、
－ＣＦ２ＣＯＮＨ（ＣＨ２）６－、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）３－（式中、Ｐｈはフェニルを意味する）、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）６－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）６－（式中、Ｐｈはフェニルを意味する）、
－ＣＦ２－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＦ２－ＣＯＮ（Ｐｈ）－（ＣＨ２）３－（式中、Ｐｈはフェニルを意味する）、
－ＣＦ２－ＣＯＮ（ＣＨ３）－（ＣＨ２）６－、
－ＣＦ２－ＣＯＮ（Ｐｈ）－（ＣＨ２）６－（式中、Ｐｈはフェニルを意味する）、
－ＣＯＮＨ－（ＣＨ２）２ＮＨ（ＣＨ２）３－、
－ＣＯＮＨ－（ＣＨ２）６ＮＨ（ＣＨ２）３－、
－ＣＨ２Ｏ－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＨ２Ｏ－ＣＯＮＨ－（ＣＨ２）６－、
－Ｓ－（ＣＨ２）３－、
－（ＣＨ２）２Ｓ（ＣＨ２）３－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）３Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）１０Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２０Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－Ｃ（Ｏ）Ｏ－（ＣＨ２）３－、
－Ｃ（Ｏ）Ｏ－（ＣＨ２）６－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－ＣＨ（ＣＨ３）－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－（ＣＨ２）３－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－ＣＨ（ＣＨ３）－ＣＨ２－、
－ＯＣＨ２－、
－Ｏ（ＣＨ２）３－、
－ＯＣＦＨＣＦ２－、
Figure JPOXMLDOC01-appb-C000023
 などが挙げられる。 Among them, preferred specific X 7 is
Single bond,
-CH 2 OCH 2- ,
-CH 2 O (CH 2 ) 2- ,
-CH 2 O (CH 2 ) 3- ,
-CH 2 O (CH 2 ) 6- ,
-CF 2 -CH 2 -O-CH 2- ,
-CF 2 -CH 2 -O- (CH 2 ) 2- ,
-CF 2 -CH 2 -O- (CH 2 ) 3- ,
-CF 2 -CH 2 -O- (CH 2 ) 6-
-CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2- ,
-CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2- ,
-CH 2 O (CH 2) 3 Si (CH 3) 2 O (Si (CH 3) 2 O) 2 Si (CH 3) 2 (CH 2) 2 -,
-CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 3 Si (CH 3 ) 2 (CH 2 ) 2- ,
-CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 10 Si (CH 3 ) 2 (CH 2 ) 2- ,
-CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 20 Si (CH 3 ) 2 (CH 2 ) 2- ,
-CH 2 OCF 2 CHFOCF 2- ,
-CH 2 OCF 2 CHFOCF 2 CF 2- ,
-CH 2 OCF 2 CHFOCF 2 CF 2 CF 2- ,
-CH 2 OCH 2 CF 2 CF 2 OCF 2- ,
-CH 2 OCH 2 CF 2 CF 2 OCF 2 CF 2- ,
-CH 2 OCH 2 CF 2 CF 2 OCF 2 CF 2 CF 2- ,
-CH 2 OCH 2 CF 2 CF 2 OCF (CF 3) CF 2 OCF 2 -,
-CH 2 OCH 2 CF 2 CF 2 OCF (CF 3) CF 2 OCF 2 CF 2 -,
-CH 2 OCH 2 CF 2 CF 2 OCF (CF 3) CF 2 OCF 2 CF 2 CF 2 -,
-CH 2 OCH 2 CHFCF 2 OCF 2- ,
-CH 2 OCH 2 CHFCF 2 OCF 2 CF 2- ,
-CH 2 OCH 2 CHFCF 2 OCF 2 CF 2 CF 2- ,
-CH 2 OCH 2 CHFCF 2 OCF ( CF 3) CF 2 OCF 2 -,
-CH 2 OCH 2 CHFCF 2 OCF ( CF 3) CF 2 OCF 2 CF 2 -,
-CH 2 OCH 2 CHFCF 2 OCF ( CF 3) CF 2 OCF 2 CF 2 CF 2 -,
-CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 -C (O) NH-CH 2- ,
-CH 2 OCH 2 (CH 2 ) 7 CH 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 2- ,
-CH 2 OCH 2 CH 2 CH 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 3- ,
-CH 2 OCH 2 CH 2 CH 2 Si (OCH 2 CH 3 ) 2 OSi (OCH 2 CH 3 ) 2 (CH 2 ) 3- ,
-CH 2 OCH 2 CH 2 CH 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 2- ,
-CH 2 OCH 2 CH 2 CH 2 Si (OCH 2 CH 3 ) 2 OSi (OCH 2 CH 3 ) 2 (CH 2 ) 2- ,
-(CH 2 ) 2 -Si (CH 3 ) 2- (CH 2 ) 2- ,
-CH 2- ,
-(CH 2 ) 2- ,
-(CH 2 ) 3- ,
- (CH 2) 4 -,
-(CH 2 ) 5- ,
-(CH 2 ) 6- ,
-CF 2- ,
-(CF 2 ) 2- ,
-CF 2 -CH 2- ,
-CF 2- (CH 2 ) 2- ,
-CF 2- (CH 2 ) 3- ,
-CF 2 - (CH 2) 4 -,
-CF 2- (CH 2 ) 5- ,
-CF 2- (CH 2 ) 6- ,
-CO-,
-CONH-
-CONH-CH 2- ,
-CONH- (CH 2 ) 2- ,
-CONH- (CH 2 ) 3- ,
-CONH- (CH 2 ) 6- ,
-CF 2 CONH-,
-CF 2 CONHCH 2- ,
-CF 2 CONH (CH 2 ) 2- ,
-CF 2 CONH (CH 2 ) 3- ,
-CF 2 CONH (CH 2 ) 6- ,
-CON (CH 3 )-(CH 2 ) 3- ,
-CON (Ph)-(CH 2 ) 3- (wherein Ph means phenyl),
-CON (CH 3 )-(CH 2 ) 6- ,
-CON (Ph)-(CH 2 ) 6- (wherein Ph means phenyl),
-CF 2 -CON (CH 3 )-(CH 2 ) 3- ,
-CF 2 -CON (Ph)-(CH 2 ) 3- (wherein, Ph means phenyl),
-CF 2 -CON (CH 3 )-(CH 2 ) 6- ,
-CF 2 -CON (Ph)-(CH 2 ) 6- (wherein, Ph means phenyl),
-CONH- (CH 2 ) 2 NH (CH 2 ) 3- ,
-CONH- (CH 2 ) 6 NH (CH 2 ) 3- ,
-CH 2 O-CONH- (CH 2 ) 3- ,
-CH 2 O-CONH- (CH 2 ) 6- ,
-S- (CH 2 ) 3- ,
-(CH 2 ) 2 S (CH 2 ) 3- ,
-CONH- (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2- ,
-CONH- (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2- ,
-CONH- (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 2 Si (CH 3 ) 2 (CH 2 ) 2- ,
-CONH- (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 3 Si (CH 3 ) 2 (CH 2 ) 2- ,
-CONH- (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 10 Si (CH 3 ) 2 (CH 2 ) 2- ,
-CONH- (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 20 Si (CH 3 ) 2 (CH 2 ) 2- ,
-C (O) O- (CH 2 ) 3- ,
-C (O) O- (CH 2 ) 6- ,
-CH 2 -O- (CH 2 ) 3 -Si (CH 3 ) 2- (CH 2 ) 2 -Si (CH 3 ) 2- (CH 2 ) 2- ,
-CH 2 -O- (CH 2 ) 3 -Si (CH 3 ) 2- (CH 2 ) 2 -Si (CH 3 ) 2 -CH (CH 3 )-,
-CH 2 -O- (CH 2 ) 3 -Si (CH 3 ) 2- (CH 2 ) 2 -Si (CH 3 ) 2- (CH 2 ) 3- ,
-CH 2 -O- (CH 2 ) 3 -Si (CH 3 ) 2- (CH 2 ) 2 -Si (CH 3 ) 2 -CH (CH 3 ) -CH 2- ,
-OCH 2-
-O (CH 2 ) 3- ,
-OCFHCF 2- ,
Figure JPOXMLDOC01-appb-C000023
 Etc.
　上記の中で、より好ましい具体的なＸ７は、
－ＣＨ２ＯＣＨ２－、
－ＣＨ２Ｏ（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３－、
－ＣＨ２Ｏ（ＣＨ２）６－、
－ＣＦ２－ＣＨ２－Ｏ－ＣＨ２－、
－ＣＦ２－ＣＨ２－Ｏ－（ＣＨ２）２－、
－ＣＦ２－ＣＨ２－Ｏ－（ＣＨ２）３－、
－ＣＦ２－ＣＨ２－Ｏ－（ＣＨ２）６－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－Ｃ（Ｏ）ＮＨ－ＣＨ２－、
－ＣＦ２－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－Ｃ（Ｏ）ＮＨ－ＣＨ２－、
－ＣＨ２－、
－（ＣＨ２）２－、
－（ＣＨ２）３－、
－（ＣＨ２）４－、
－（ＣＨ２）５－、
－（ＣＨ２）６－、
－ＣＦ２－、
－（ＣＦ２）２－、
－ＣＦ２－ＣＨ２－、
－ＣＦ２－（ＣＨ２）２－、
－ＣＦ２－（ＣＨ２）３－、
－ＣＦ２－（ＣＨ２）４－、
－ＣＦ２－（ＣＨ２）５－、
－ＣＦ２－（ＣＨ２）６－、
－ＣＯＮＨ－、
－ＣＯＮＨ－ＣＨ２－、
－ＣＯＮＨ－（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＯＮＨ－（ＣＨ２）６－、
－ＣＦ２ＣＯＮＨ－、
－ＣＦ２ＣＯＮＨＣＨ２－、
－ＣＦ２ＣＯＮＨ（ＣＨ２）２－、
－ＣＦ２ＣＯＮＨ（ＣＨ２）３－、
－ＣＦ２ＣＯＮＨ（ＣＨ２）６－、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）３－（式中、Ｐｈはフェニルを意味する）、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）６－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）６－（式中、Ｐｈはフェニルを意味する）、
－ＣＦ２－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＦ２－ＣＯＮ（Ｐｈ）－（ＣＨ２）３－（式中、Ｐｈはフェニルを意味する）、
－ＣＦ２－ＣＯＮ（ＣＨ３）－（ＣＨ２）６－、
－ＣＦ２－ＣＯＮ（Ｐｈ）－（ＣＨ２）６－（式中、Ｐｈはフェニルを意味する）、
－ＣＯＮＨ－（ＣＨ２）２ＮＨ（ＣＨ２）３－、
－ＣＯＮＨ－（ＣＨ２）６ＮＨ（ＣＨ２）３－、
－ＣＨ２Ｏ－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＨ２Ｏ－ＣＯＮＨ－（ＣＨ２）６－、
－ＯＣＨ２－、
－Ｏ（ＣＨ２）３－、
－ＯＣＦＨＣＦ２－、
であることが好ましい。 Among the above, more preferred specific X 7 is
-CH 2 OCH 2- ,
-CH 2 O (CH 2 ) 2- ,
-CH 2 O (CH 2 ) 3- ,
-CH 2 O (CH 2 ) 6- ,
-CF 2 -CH 2 -O-CH 2- ,
-CF 2 -CH 2 -O- (CH 2 ) 2- ,
-CF 2 -CH 2 -O- (CH 2 ) 3- ,
-CF 2 -CH 2 -O- (CH 2 ) 6-
-CH 2 OCF 2 CHFOCF 2- ,
-CH 2 OCF 2 CHFOCF 2 CF 2- ,
-CH 2 OCF 2 CHFOCF 2 CF 2 CF 2- ,
-CH 2 OCH 2 CF 2 CF 2 OCF 2- ,
-CH 2 OCH 2 CF 2 CF 2 OCF 2 CF 2- ,
-CH 2 OCH 2 CF 2 CF 2 OCF 2 CF 2 CF 2- ,
-CH 2 OCH 2 CF 2 CF 2 OCF (CF 3) CF 2 OCF 2 -,
-CH 2 OCH 2 CF 2 CF 2 OCF (CF 3) CF 2 OCF 2 CF 2 -,
-CH 2 OCH 2 CF 2 CF 2 OCF (CF 3) CF 2 OCF 2 CF 2 CF 2 -,
-CH 2 OCH 2 CHFCF 2 OCF 2- ,
-CH 2 OCH 2 CHFCF 2 OCF 2 CF 2- ,
-CH 2 OCH 2 CHFCF 2 OCF 2 CF 2 CF 2- ,
-CH 2 OCH 2 CHFCF 2 OCF ( CF 3) CF 2 OCF 2 -,
-CH 2 OCH 2 CHFCF 2 OCF ( CF 3) CF 2 OCF 2 CF 2 -,
-CH 2 OCH 2 CHFCF 2 OCF ( CF 3) CF 2 OCF 2 CF 2 CF 2 -,
-CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 -C (O) NH-CH 2- ,
-CF 2 -CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 -C (O) NH-CH 2- ,
-CH 2- ,
-(CH 2 ) 2- ,
-(CH 2 ) 3- ,
- (CH 2) 4 -,
-(CH 2 ) 5- ,
-(CH 2 ) 6- ,
-CF 2- ,
-(CF 2 ) 2- ,
-CF 2 -CH 2- ,
-CF 2- (CH 2 ) 2- ,
-CF 2- (CH 2 ) 3- ,
-CF 2 - (CH 2) 4 -,
-CF 2- (CH 2 ) 5- ,
-CF 2- (CH 2 ) 6- ,
-CONH-,
-CONH-CH 2- ,
-CONH- (CH 2 ) 2- ,
-CONH- (CH 2 ) 3- ,
-CONH- (CH 2 ) 6- ,
-CF 2 CONH-,
-CF 2 CONHCH 2- ,
-CF 2 CONH (CH 2 ) 2- ,
-CF 2 CONH (CH 2 ) 3- ,
-CF 2 CONH (CH 2 ) 6- ,
-CON (CH 3 )-(CH 2 ) 3- ,
-CON (Ph)-(CH 2 ) 3- (wherein Ph means phenyl),
-CON (CH 3 )-(CH 2 ) 6- ,
-CON (Ph)-(CH 2 ) 6- (wherein Ph means phenyl),
-CF 2 -CON (CH 3 )-(CH 2 ) 3- ,
-CF 2 -CON (Ph)-(CH 2 ) 3- (wherein, Ph means phenyl),
-CF 2 -CON (CH 3 )-(CH 2 ) 6- ,
-CF 2 -CON (Ph)-(CH 2 ) 6- (wherein, Ph means phenyl),
-CONH- (CH 2 ) 2 NH (CH 2 ) 3- ,
-CONH- (CH 2 ) 6 NH (CH 2 ) 3- ,
-CH 2 O-CONH- (CH 2 ) 3- ,
-CH 2 O-CONH- (CH 2 ) 6- ,
-OCH 2-
-O (CH 2 ) 3- ,
-OCFHCF 2- ,
Is preferred.
　上記の中では、より好ましくは、Ｘ７は、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－Ｃ（Ｏ）ＮＨ－ＣＨ２－、
－ＣＦ２－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－Ｃ（Ｏ）ＮＨ－ＣＨ２－、
－ＣＯＮＨ－、
－ＣＯＮＨ－ＣＨ２－、
－ＣＯＮＨ－（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＯＮＨ－（ＣＨ２）６－、
－ＣＦ２ＣＯＮＨ－、
－ＣＦ２ＣＯＮＨＣＨ２－、
－ＣＦ２ＣＯＮＨ（ＣＨ２）２－、
－ＣＦ２ＣＯＮＨ（ＣＨ２）３－、
－ＣＦ２ＣＯＮＨ（ＣＨ２）６－、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）３－（式中、Ｐｈはフェニルを意味する）、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）６－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）６－（式中、Ｐｈはフェニルを意味する）、
－ＣＦ２－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＦ２－ＣＯＮ（Ｐｈ）－（ＣＨ２）３－（式中、Ｐｈはフェニルを意味する）、
－ＣＦ２－ＣＯＮ（ＣＨ３）－（ＣＨ２）６－、
－ＣＦ２－ＣＯＮ（Ｐｈ）－（ＣＨ２）６－（式中、Ｐｈはフェニルを意味する）、
－ＣＯＮＨ－（ＣＨ２）２ＮＨ（ＣＨ２）３－、
－ＣＯＮＨ－（ＣＨ２）６ＮＨ（ＣＨ２）３－、
である。 Among the above, more preferably, X 7 is
-CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 -C (O) NH-CH 2- ,
-CF 2 -CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 -C (O) NH-CH 2- ,
-CONH-,
-CONH-CH 2- ,
-CONH- (CH 2 ) 2- ,
-CONH- (CH 2 ) 3- ,
-CONH- (CH 2 ) 6- ,
-CF 2 CONH-,
-CF 2 CONHCH 2- ,
-CF 2 CONH (CH 2 ) 2- ,
-CF 2 CONH (CH 2 ) 3- ,
-CF 2 CONH (CH 2 ) 6- ,
-CON (CH 3 )-(CH 2 ) 3- ,
-CON (Ph)-(CH 2 ) 3- (wherein Ph means phenyl),
-CON (CH 3 )-(CH 2 ) 6- ,
-CON (Ph)-(CH 2 ) 6- (wherein Ph means phenyl),
-CF 2 -CON (CH 3 )-(CH 2 ) 3- ,
-CF 2 -CON (Ph)-(CH 2 ) 3- (wherein, Ph means phenyl),
-CF 2 -CON (CH 3 )-(CH 2 ) 6- ,
-CF 2 -CON (Ph)-(CH 2 ) 6- (wherein, Ph means phenyl),
-CONH- (CH 2 ) 2 NH (CH 2 ) 3- ,
-CONH- (CH 2 ) 6 NH (CH 2 ) 3- ,
It is.
　より好ましい態様において、Ｘ７は、Ｘｅ’を表す。Ｘｅ’は、上記と同意義である。 In a more preferred embodiment, X 7 represents X e ′ . X e ′ is as defined above.
　一の態様において、Ｘｅ’は、単結合である。本態様において、ＰＦＰＥと基材との結合能を有する基（即ち、（Ｄ１）および（Ｄ２）においては、δ１を付して括弧でくくられた基）とが直接結合している。このような構造を有することによって、ＰＦＰＥとδ１を付して括弧でくくられた基との結合力がより強くなると考えられる。また、ＰＦＰＥと直接結合する炭素原子（即ち、δ１を付して括弧でくくられた基においてＲｄ 、ＲｅおよびＲｆと結合する炭素原子）は電荷の偏りが少なく、その結果、上記炭素原子において求核反応等が生じにくく、当該化合物は基材と安定に結合すると考えられる。このような構造は、ＰＦＰＥシラン化合物により形成される層の摩擦耐久性をより向上させることができｒので、有利である。 In one embodiment, X e ′ is a single bond. In this embodiment, a group capable of binding PFPE to a substrate (that is, a group enclosed in parentheses with δ1 in (D1) and (D2)) is directly bonded. By having such a structure, it is considered that the bonding strength between PFPE and a group enclosed in parentheses with δ1 becomes stronger. In addition, carbon atoms directly bonded to PFPE (that is, carbon atoms bonded to R d , R e and R f in the parenthesized group attached with δ1) have less charge bias, and as a result, the above carbon Nucleophilic reactions and the like are unlikely to occur at atoms, and the compound is considered to be stably bound to the substrate. Such a structure is advantageous because it can further improve the friction durability of the layer formed by the PFPE silane compound.
　上記式中、Ｒｄは、各出現においてそれぞれ独立して、－Ｚ４－ＣＲ８１ ｐ２Ｒ８２ ｑ２Ｒ８３ ｒ２を表す。 In the above formulae, R d independently represents -Z 4 -CR 81 p 2 R 82 q 2 R 83 r 2 at each occurrence.
　式中、Ｚ４は、各出現においてそれぞれ独立して、酸素原子または２価の有機基を表す。 In the formula, Z 4 independently represents an oxygen atom or a divalent organic group at each occurrence.
　上記Ｚ４は、好ましくは、Ｃ１－６アルキレン基、－（ＣＨ２）ｇ－Ｏ－（ＣＨ２）ｈ－（式中、ｇは、０～６の整数、例えば１～６の整数であり、ｈは、０～６の整数、例えば１～６の整数である）または、－フェニレン－（ＣＨ２）ｉ－（式中、ｉは、０～６の整数である）であり、より好ましくはＣ１－３アルキレン基である。これらの基は、例えば、フッ素原子、Ｃ１－６アルキル基、Ｃ２－６アルケニル基、およびＣ２－６アルキニル基から選択される１個またはそれ以上の置換基により置換されていてもよい。 The above Z 4 is preferably a C 1-6 alkylene group, — (CH 2 ) g —O— (CH 2 ) h — (wherein, g is an integer of 0 to 6, for example, an integer of 1 to 6) H is an integer of 0 to 6, for example, an integer of 1 to 6) or -phenylene- (CH 2 ) i- (wherein i is an integer of 0 to 6), and Preferably, it is a C 1-3 alkylene group. These groups may be substituted, for example, by one or more substituents selected from a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group. .
　式中、Ｒ８１は、各出現においてそれぞれ独立して、Ｒｄ’を表す。Ｒｄ’は、Ｒｄと同意義である。 In the formula, R 81 independently represents R d ′ at each occurrence. R d ′ is as defined the R d .
　Ｒｄ中、Ｚ４基を介して直鎖状に連結されるＣは最大で５個である。即ち、上記Ｒｄにおいて、Ｒ８１が少なくとも１つ存在する場合、Ｒｄ中にＺ４基を介して直鎖状に連結されるＣ原子が２個以上存在するが、かかるＺ４基を介して直鎖状に連結されるＣ原子の数は最大で５個である。なお、「Ｒｄ中のＺ４基を介して直鎖状に連結されるＣ原子の数」とは、Ｒｄ中において直鎖状に連結される－Ｚ４－Ｃ－の繰り返し数と等しくなる。 In Rd , Cs linked in a linear fashion via a Z 4 group are at most 5 pieces. That is, in the above Rd , when at least one R 81 is present, two or more C atoms linked in a straight line via the Z 4 group are present in R d , and such a C 4 group is intervened. The maximum number of C atoms linked in a straight chain is five. Note that the "through Z 4 group in R d number of C atoms linearly linked" is equal to the number of repetitions of -Z 4 -C- being linearly linked in a R d Become.
　好ましい態様において、下記に示すように、「Ｒｄ中のＺ４基を介して直鎖状に連結されるＣ原子の数」は、すべての鎖において、１個（左式）または２個（右式）である。
Figure JPOXMLDOC01-appb-C000024
 In a preferred embodiment, as shown below, “the number of C atoms linearly linked via the Z 4 group in R d ” is 1 (left) or 2 (the left expression) in all chains. Right).
Figure JPOXMLDOC01-appb-C000024
　一の態様において、ＲｄのＺ４基を介して直鎖状に連結されるＣ原子の数は１個または２個、好ましくは１個である。 In one embodiment, the number of C atoms to be linked via Z 4 groups R d linearized is one or two, preferably one.
　式中、Ｒ８２は、各出現においてそれぞれ独立して、－Ｙ－ＳｉＲ８５ ｎ２Ｒ８６ ３－ｎ２を表す。 In the formula, R 82 independently represents -Y-SiR 85 n 2 R 86 3- n 2 at each occurrence.
　Ｙは、各出現においてそれぞれ独立して、２価の有機基を表す。 Y's each independently represent a divalent organic group at each occurrence.
　好ましい態様において、Ｙは、Ｃ１－６アルキレン基、－（ＣＨ２）ｇ’－Ｏ－（ＣＨ２）ｈ’－（式中、ｇ’は、０～６の整数、例えば１～６の整数であり、ｈ’は、０～６の整数、例えば１～６の整数である）または、－フェニレン－（ＣＨ２）ｉ’－（式中、ｉ’は、０～６の整数である）である。これらの基は、例えば、フッ素原子、Ｃ１－６アルキル基、Ｃ２－６アルケニル基、およびＣ２－６アルキニル基から選択される１個またはそれ以上の置換基により置換されていてもよい。 In a preferred embodiment, Y, C 1-6 alkylene group, - (CH 2) g ' -O- (CH 2) h' - ( wherein, g 'is from 0 to 6 integer, for example from 1 to 6 H is an integer of 0 to 6, for example, an integer of 1 to 6, or -phenylene- (CH 2 ) i ' -(wherein i' is an integer of 0 to 6) ). These groups may be substituted, for example, by one or more substituents selected from a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group. .
　一の態様において、Ｙは、Ｃ１－６アルキレン基または－フェニレン－（ＣＨ２）ｉ’－であり得る。Ｙが上記の基である場合、光耐性、特に紫外線耐性がより高くなり得る。 In one aspect, Y can be a C 1-6 alkylene group or -phenylene- (CH 2 ) i ' -. When Y is the above radical, the light resistance, in particular the UV resistance, may be higher.
　上記Ｒ８５は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表す。 R 85 each independently represents a hydroxyl group or a hydrolyzable group at each occurrence.
　上記「加水分解可能な基」とは、式（Ｃ１）および（Ｃ２）と同様のものが挙げられる。 Examples of the above-mentioned "hydrolyzable group" include those similar to formulas (C1) and (C2).
　好ましくは、Ｒ８５は、－ＯＲ（式中、Ｒは、置換または非置換のＣ１－３アルキル基、より好ましくはエチル基またはメチル基、特にメチル基を表す）である。 Preferably, R 85 is —OR, wherein R represents a substituted or unsubstituted C 1-3 alkyl group, more preferably an ethyl group or a methyl group, in particular a methyl group.
　上記Ｒ８６は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表す。該低級アルキル基は、好ましくは炭素数１～２０のアルキル基、より好ましくは炭素数１～６のアルキル基、さらに好ましくはメチル基である。 R 86 each independently represents a hydrogen atom or a lower alkyl group at each occurrence. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
　ｎ２は、（－Ｙ－ＳｉＲ８５ ｎ２Ｒ８６ ３－ｎ２）単位毎に独立して、０～３の整数を表し、好ましくは１～３の整数、より好ましくは２または３、特に好ましくは３である。 n2 independently represents an integer of 0 to 3, preferably an integer of 1 to 3, more preferably 2 or 3, and particularly preferably 3 for each (-Y-SiR 85 n2 R 86 3-n2 ) unit It is.
　上記Ｒ８３は、各出現においてそれぞれ独立して、水素原子、水酸基または低級アルキル基を表す。該低級アルキル基は、好ましくは炭素数１～２０のアルキル基、より好ましくは炭素数１～６のアルキル基、さらに好ましくはメチル基である。 R 83 each independently represents a hydrogen atom, a hydroxyl group or a lower alkyl group at each occurrence. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
　式中、ｐ２は、各出現においてそれぞれ独立して、０～３の整数であり；ｑ２は、各出現においてそれぞれ独立して、０～３の整数であり；ｒ２は、各出現においてそれぞれ独立して、０～３の整数である。ただし、（－Ｚ４－ＣＲ８１ ｐ２Ｒ８２ ｑ２Ｒ８３ ｒ２）毎において、ｐ２、ｑ２およびｒ２の和は３である。 In which p2 is independently at each occurrence an integer of 0 to 3; q2 is independently at each occurrence an integer of 0 to 3; r2 is independently at each occurrence Is an integer of 0 to 3. However, the sum of p2, q2 and r2 is 3 for each (-Z 4 -CR 81 p2 R 82 q2 R 83 r 2 ).
　好ましい態様において、Ｒｄ中の末端のＲｄ’（Ｒｄ’が存在しない場合、Ｒｄ）において、上記ｑ２は、好ましくは２以上、例えば２または３であり、より好ましくは３である。 In a preferred embodiment, '(if R d' is absent, R d) end of R d in R d in the above q2 is preferably 2 or more, for example 2 or 3, more preferably 3.
　好ましい態様において、Ｒｄの末端部の少なくとも１つは、－Ｃ（－Ｙ－ＳｉＲ８５ ｎ２Ｒ８６ ３－ｎ２）２または－Ｃ（－Ｙ－ＳｉＲ８５ ｎ２Ｒ８６ ３－ｎ２）３、好ましくは－Ｃ（－Ｙ－ＳｉＲ８５ ｎ２Ｒ８６ ３－ｎ２）３であり得る。式中、（－Ｙ－ＳｉＲ８５ ｎ２Ｒ８６ ３－ｎ２）の単位は、好ましくは（－Ｙ－ＳｉＲ８５ ３）である。さらに好ましい態様において、Ｒｄ１の末端部は、すべて－Ｃ（－Ｙ－ＳｉＲ８５ ｎ２Ｒ８６ ３－ｎ２）３、好ましくは－Ｃ（－Ｙ－ＳｉＲ８５ ３）３であり得る。 In a preferred embodiment, at least one of the terminal parts of R d is preferably —C (—Y—SiR 85 n 2 R 86 3- n 2 ) 2 or —C (—Y—SiR 85 n 2 R 86 3- n 2 ) 3 , preferably May be -C (-Y-SiR 85 n2 R 86 3-n2 ) 3 . Wherein, (- Y-SiR 85 n2 R 86 3-n2) units is preferably (-Y-SiR 85 3). In a further preferred embodiment, the distal end of the R d1 are all -C (-Y-SiR 85 n2 R 86 3-n2) 3, may be preferably -C (-Y-SiR 85 3) 3.
　上記式中、Ｒｅは、各出現においてそれぞれ独立して、－Ｙ－ＳｉＲ８５ ｎ２Ｒ８６ ３－ｎ２を表す。ここに、Ｙ、Ｒ８５、Ｒ８６およびｎ２は、上記Ｒ８２における記載と同意義である。 In the above formulae, R e independently represents -Y-SiR 85 n 2 R 86 3- n 2 at each occurrence. Here, Y, R 85 , R 86 and n 2 are as defined in R 82 above.
　上記式中、Ｒｆは、各出現においてそれぞれ独立して、水素原子、水酸基または低級アルキル基を表す。該低級アルキル基は、好ましくは炭素数１～２０のアルキル基、より好ましくは炭素数１～６のアルキル基、さらに好ましくはメチル基である。 In the above formulae, R f each independently represents a hydrogen atom, a hydroxyl group or a lower alkyl group at each occurrence. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
　式中、ｋ２は、各出現においてそれぞれ独立して、０～３の整数であり；ｌ２は、各出現においてそれぞれ独立して、０～３の整数であり；ｍ２は、各出現においてそれぞれ独立して、０～３の整数である。ただし、ｋ２、ｌ２およびｍ２の和は３である。 In the formula, k2 is independently an integer of 0 to 3 at each occurrence; 12 is an integer of 0 to 3 independently at each occurrence; m2 is independently at each occurrence Is an integer of 0 to 3. However, the sum of k2, l2 and m2 is 3.
　一の態様において、少なくとも１つのｋ２は２または３であり、好ましくは３である。 In one embodiment, at least one k2 is 2 or 3, preferably 3.
　一の態様において、ｋ２は２または３であり、好ましくは３である。 In one embodiment, k2 is 2 or 3, preferably 3.
　一の態様において、ｌ２は２または３であり、好ましくは３である。 In one embodiment, l2 is 2 or 3, preferably 3.
　上記式（Ｄ１）および（Ｄ２）において、－Ｙ－ＳｉＲ８５で表される基が２以上存在する。より好ましくは、２以上の－Ｙ－ＳｉＲ８５に結合した炭素原子が１以上存在する。即ち、－Ｃ－（Ｙ－ＳｉＲ８５ ｎ２Ｒ８６ ３－ｎ２）２で表される基が１以上存在することが好ましい（式中、ｎ２は１～３の整数である。）。 In the above formulas (D1) and (D2), two or more groups represented by -Y-SiR 85 are present. More preferably, one or more carbon atoms bonded to two or more -Y-SiR 85 are present. That is, it is preferable that one or more groups represented by —C— (Y—SiR 85 n 2 R 86 3- n 2 ) 2 exist (in the formula, n 2 is an integer of 1 to 3).
　上記式（Ｄ１）および（Ｄ２）中、ｎ２は１～３の整数であり、および、少なくとも１つのｑ２は２または３であるか、あるいは、少なくとも１つのｌ２は２または３である。即ち、式中、少なくとも２つの－Ｙ－ＳｉＲ８５ ｎ２Ｒ８６ ３－ｎ２基が存在する。 In the above formulas (D1) and (D2), n2 is an integer of 1 to 3, and at least one q2 is 2 or 3, or at least one 12 is 2 or 3. That is, there are at least two -Y-SiR 85 n2 R 86 3-n2 groups in the formula.
　式（Ｄ１）または式（Ｄ２）で表されるＰＦＰＥ含有シラン化合物は、公知の方法を組み合わせることにより製造することができる。例えば、Ｘ７が２価である式（Ｄ１’）で表される化合物は、限定するものではないが、以下のようにして製造することができる。 The PFPE-containing silane compound represented by Formula (D1) or Formula (D2) can be produced by combining known methods. For example, the compound represented by the formula (D1 ′) in which X 7 is divalent can be produced as follows, but not limited thereto.
　ＨＯ－Ｘ７－Ｃ（ＹＯＨ）３（式中、Ｘ７およびＹは、それぞれ独立して、２価の有機基である。）で表される多価アルコールに、二重結合を含有する基（好ましくはアリル）、およびハロゲン（好ましくはブロモ）を導入して、Ｈａｌ－Ｘ７－Ｃ（Ｙ－Ｏ－Ｒ－ＣＨ＝ＣＨ２）３（式中、Ｈａｌはハロゲン、例えばＢｒであり、Ｒは二価の有機基、例えばアルキレン基である。）で表される二重結合含有ハロゲン化物を得る。次いで、末端のハロゲンと、ＲＰＦＰＥ－ＯＨ（式中、ＲＰＦＰＥは、パーフルオロポリエーテル基含有基である。）で表されるパーフルオロポリエーテル基含有アルコールとを反応させて、ＲＰＦＰＥ－Ｏ－Ｘ７－Ｃ（Ｙ－Ｏ－Ｒ－ＣＨ＝ＣＨ２）３を得る。次いで、末端の－ＣＨ＝ＣＨ２と、ＨＳｉＣｌ３およびアルコールまたはＨＳｉＲ８５ ３と反応させて、ＲＰＦＰＥ－Ｏ－Ｘ７－Ｃ（Ｙ－Ｏ－Ｒ－ＣＨ２－ＣＨ２－ＳｉＲ８５ ３）３を得ることができる。 A group containing a double bond to a polyhydric alcohol represented by HO-X 7 -C (YOH) 3 (wherein, X 7 and Y each independently represent a divalent organic group) (Preferably allyl) and halogen (preferably bromo) are introduced into Hal-X 7 -C (Y-O-R-CH = CH 2 ) 3 , wherein Hal is a halogen such as Br, R is a divalent organic group such as an alkylene group)) to obtain a double bond-containing halide represented by Then, the terminal halogen and the perfluoropolyether group-containing alcohol represented by R PFPE -OH (wherein R PFPE is a perfluoropolyether group-containing group) are reacted to obtain R PFPE- OX 7 -C (Y-O-R-CH = CH 2 ) 3 is obtained. Then, by reacting the terminal -CH = CH 2 with HSiCl 3 and alcohol or HSiR 85 3 , R PFPE -O-X 7 -C (Y-O-R-CH 2 -CH 2 -SiR 85 3 ) You can get three .
　上記したＰＦＰＥ含有シラン化合物は、特に限定されるものではないが、５×１０２～１×１０５の数平均分子量を有し得る。かかる範囲のなかでも、２，０００～３０，０００、より好ましくは２，５００～１２，０００、さらに好ましくは３，０００～６，０００の数平均分子量を有することが、摩擦耐久性の観点から好ましい。なお、本発明において、数平均分子量は、１９Ｆ－ＮＭＲにより測定される値とする。 The above-mentioned PFPE-containing silane compound is not particularly limited, but may have a number average molecular weight of 5 × 10 2 to 1 × 10 5 . Within this range, having a number average molecular weight of 2,000 to 30,000, more preferably 2,500 to 12,000, still more preferably 3,000 to 6,000 is from the viewpoint of friction durability. preferable. In the present invention, the number average molecular weight is a value measured by 19 F-NMR.
　好ましくは、上記ＰＦＰＥ含有シラン化合物は、上記式（Ｃ１）、（Ｃ２）、（Ｄ１）または（Ｄ２）のいずれかで表される化合物である。 Preferably, the PFPE-containing silane compound is a compound represented by any one of formulas (C1), (C2), (D1) or (D2) above.
　上記表面処理剤は、溶媒で希釈されていてもよい。このような溶媒としては、特に限定するものではないが、例えば：
　パーフルオロヘキサン、ＣＦ３ＣＦ２ＣＨＣｌ２、ＣＦ３ＣＨ２ＣＦ２ＣＨ３、ＣＦ３ＣＨＦＣＨＦＣ２Ｆ５、１，１，１，２，２，３，３，４，４，５，５，６，６－トリデカフルオロオクタン、１，１，２，２，３，３，４－ヘプタフルオロシクロペンタン（（ゼオローラＨ（商品名）等）、Ｃ４Ｆ９ＯＣＨ３、Ｃ４Ｆ９ＯＣ２Ｈ５、ＣＦ３ＣＨ２ＯＣＦ２ＣＨＦ２、Ｃ６Ｆ１３ＣＨ＝ＣＨ２、キシレンヘキサフルオリド、パーフルオロベンゼン、メチルペンタデカフルオロヘプチルケトン、トリフルオロエタノール、ペンタフルオロプロパノール、ヘキサフルオロイソプロパノール、ＨＣＦ２ＣＦ２ＣＨ２ＯＨ、メチルトリフルオロメタンスルホネート、トリフルオロ酢酸およびＣＦ３Ｏ（ＣＦ２ＣＦ２Ｏ）ｍ１（ＣＦ２Ｏ）ｎ１ＣＦ２ＣＦ３［式中、ｍ１およびｎ１は、それぞれ独立して０以上１０００以下の整数であり、ｍ１またはｎ１を付して括弧でくくられた各繰り返し単位の存在順序は式中において任意であり、但しｍ１およびｎ１の和は１以上である。］、１，1－ジクロロ－２，３，３，３－テトラフルオロ－１－プロペン、１，２－ジクロロ－１，３，３，３－テトラフルオロ－１－プロペン、１，２－ジクロロ－３，３，３－トリフルオロ－１－プロペン、１，１－ジクロロ－３，３，３－トリフルオロ－１－プロペン、１，１，２－トリクロロ―３，３，３－トリフルオロ－１－プロペン、１，１，１，４，４，４－ヘキサフルオロ－２－ブテンからなる群から選択されるフッ素原子含有溶媒等が挙げられる。これらの溶媒は、単独で、または、２種以上の混合物として用いることができる。 The surface treatment agent may be diluted with a solvent. Such solvent is not particularly limited, but, for example:
Perfluorohexane, CF 3 CF 2 CHCl 2 , CF 3 CH 2 CF 2 CH 3 , CF 3 CHF CHFC 2 F 5 , 1,1,1,2,2,3,3,4,4,5,5,6 , 6-tridecafluorooctane, 1,1,2,2,3,3,4-heptafluorocyclopentane (such as Zeorora H (trade name)), C 4 F 9 OCH 3 , C 4 F 9 OC 2 H 5 , CF 3 CH 2 OCF 2 CHF 2 , C 6 F 13 CH = CH 2 , xylene hexafluoride, perfluorobenzene, methyl pentadecafluoroheptyl ketone, trifluoroethanol, pentafluoropropanol, hexafluoroisopropanol, HCF 2 CF 2 CH 2 OH, methyl trifluoromethanesulfonate, trifluoroacetate and CF 3 O (C During 2 CF 2 O) m1 (CF 2 O) n1 CF 2 CF 3 [ wherein m1 and n1, are each independently zero or greater than 1,000 integer bracketed bear the m1 or n1 The order of existence of each repeating unit is arbitrary in the formula, provided that the sum of m1 and n1 is 1 or more.], 1,1-dichloro-2,3,3,3-tetrafluoro-1-propene, 1 , 2-Dichloro-1,3,3,3-tetrafluoro-1-propene, 1,2-dichloro-3,3,3-trifluoro-1-propene, 1,1-dichloro-3,3,3,3 -Trifluoro-1-propene, 1,1,2-trichloro-3,3,3-trifluoro-1-propene, 1,1,1,4,4,4-hexafluoro-2-butene group Solvents containing fluorine atoms selected from These solvents can be used alone or as a mixture of two or more.
　上記溶媒中に含まれる水分含有量は、２０質量ｐｐｍ以下であることが好ましい。上記水分含有量は、カールフィッシャー法を用いて測定することができる。このような水分含有量であることによって、表面処理剤の保存安定性が向上し得る。 It is preferable that the water content contained in the said solvent is 20 mass ppm or less. The water content can be measured using the Karl Fischer method. By such a water content, the storage stability of the surface treatment agent can be improved.
　上記表面処理剤は、上記ＰＦＰＥ含有シラン化合物に加え、他の成分を含んでいてもよい。かかる他の成分としては、特に限定されるものではないが、例えば、含フッ素オイルとして理解され得る（非反応性の）フルオロポリエーテル化合物、好ましくはパーフルオロ（ポリ）エーテル化合物（以下、「含フッ素オイル」と言う）、シリコーンオイルとして理解され得る（非反応性の）シリコーン化合物（以下、「シリコーンオイル」と言う）、触媒、低級アルコール、遷移金属、ハロゲン化物イオン、分子構造内に非共有電子対を有する原子を含む化合物などが挙げられる。 The surface treatment agent may contain other components in addition to the PFPE-containing silane compound. Such other components are not particularly limited, but for example, (non-reactive) fluoropolyether compounds which can be understood as fluorine-containing oils, preferably perfluoro (poly) ether compounds (hereinafter referred to as “containing” "Fluorine oil"), silicone compound (non-reactive) which may be understood as silicone oil (hereinafter referred to as "silicone oil"), catalyst, lower alcohol, transition metal, halide ion, non-covalently in molecular structure Examples thereof include compounds containing an atom having an electron pair.
　上記含フッ素オイルとしては、特に限定されるものではないが、例えば、以下の一般式（１）で表される化合物（パーフルオロ（ポリ）エーテル化合物）が挙げられる。
　Ｒｆ５－（ＯＣ４Ｆ８）ａ’－（ＯＣ３Ｆ６）ｂ’－（ＯＣ２Ｆ４）ｃ’－（ＯＣＦ２）ｄ’－Ｒｆ６　　　・・・（１）
　式中、Ｒｆ５は、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１～１６アルキル基（好ましくは、Ｃ１―１６のパーフルオロアルキル基）を表し、Ｒｆ６は、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１～１６アルキル基（好ましくは、Ｃ１－１６パーフルオロアルキル基）、フッ素原子または水素原子を表し、Ｒｆ５およびＲｆ６は、より好ましくは、それぞれ独立して、Ｃ１－３パーフルオロアルキル基である。
　ａ’、ｂ’、ｃ’およびｄ’は、ポリマーの主骨格を構成するパーフルオロ（ポリ）エーテルの４種の繰り返し単位数をそれぞれ表し、互いに独立して０以上３００以下の整数であって、ａ’、ｂ’、ｃ’およびｄ’の和は少なくとも１、好ましくは１～３００、より好ましくは２０～３００である。添字ａ’、ｂ’、ｃ’またはｄ’を付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である。これら繰り返し単位のうち、－（ＯＣ４Ｆ８）－は、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ（ＣＦ３）ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ（ＣＦ３）ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ（ＣＦ３））－、－（ＯＣ（ＣＦ３）２ＣＦ２）－、－（ＯＣＦ２Ｃ（ＣＦ３）２）－、－（ＯＣＦ（ＣＦ３）ＣＦ（ＣＦ３））－、－（ＯＣＦ（Ｃ２Ｆ５）ＣＦ２）－および－（ＯＣＦ２ＣＦ（Ｃ２Ｆ５））－のいずれであってもよいが、好ましくは－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２）－である。－（ＯＣ３Ｆ６）－は、－（ＯＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ（ＣＦ３）ＣＦ２）－および－（ＯＣＦ２ＣＦ（ＣＦ３））－のいずれであってもよく、好ましくは－（ＯＣＦ２ＣＦ２ＣＦ２）－である。－（ＯＣ２Ｆ４）－は、－（ＯＣＦ２ＣＦ２）－および－（ＯＣＦ（ＣＦ３））－のいずれであってもよいが、好ましくは－（ＯＣＦ２ＣＦ２）－である。 Although it does not specifically limit as said fluorine-containing oil, For example, the compound (perfluoro (poly) ether compound) represented by following General formula (1) is mentioned.
Rf 5- (OC 4 F 8 ) a ' -(OC 3 F 6 ) b' -(OC 2 F 4 ) c ' -(OCF 2 ) d'- Rf 6 (1)
In the formula, R f 5 represents a C 1-16 alkyl group (preferably a C 1-16 perfluoroalkyl group) which may be substituted by one or more fluorine atoms, and R f 6 represents Rf 5 and Rf 6 each represents a C 1-16 alkyl group (preferably a C 1-16 perfluoroalkyl group) which may be substituted by one or more fluorine atoms, a fluorine atom or a hydrogen atom; And more preferably each independently a C 1-3 perfluoroalkyl group.
a ′, b ′, c ′ and d ′ each represent the number of repeating units of four types of perfluoro (poly) ethers constituting the main skeleton of the polymer, and are each independently an integer of 0 or more and 300 or less; The sum of a ′, b ′, c ′ and d ′ is at least 1, preferably 1 to 300, more preferably 20 to 300. The order in which each repeating unit enclosed in parentheses with a subscript a ', b', c 'or d' is given is arbitrary in the formula. Among these repeating units, - (OC 4 F 8) - is, - (OCF 2 CF 2 CF 2 CF 2) -, - (OCF (CF 3) CF 2 CF 2) -, - (OCF 2 CF (CF 3) CF 2) -, - (OCF 2 CF 2 CF (CF 3)) -, - (OC (CF 3) 2 CF 2) -, - (OCF 2 C (CF 3) 2) -, - (OCF (CF 3 ) CF (CF 3 ) —, — (OCF (C 2 F 5 ) CF 2 ) — and — (OCF 2 CF (C 2 F 5 )) —, which may be any of - (OCF 2 CF 2 CF 2 CF 2) - a. - (OC 3 F 6) - is, - (OCF 2 CF 2 CF 2) -, - (OCF (CF 3) CF 2) - and - (OCF 2 CF (CF 3 )) - be any of Well, preferably-(OCF 2 CF 2 CF 2 )-. -(OC 2 F 4 )-may be either-(OCF 2 CF 2 )-or-(OCF (CF 3 ))-, but is preferably-(OCF 2 CF 2 )-.
　上記一般式（１）で表されるパーフルオロ（ポリ）エーテル化合物の例として、以下の一般式（１ａ）および（１ｂ）のいずれかで示される化合物（１種または２種以上の混合物であってよい）が挙げられる。
　Ｒｆ５－（ＯＣＦ２ＣＦ２ＣＦ２）ｂ’’－Ｒｆ６　　　　　　　　　・・・（１ａ）
　Ｒｆ５－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２）ａ’’－（ＯＣＦ２ＣＦ２ＣＦ２）ｂ’’－（ＯＣＦ２ＣＦ２）ｃ’’－（ＯＣＦ２）ｄ’’－Ｒｆ６　　　　　　　・・・（１ｂ）
　これら式中、Ｒｆ５およびＲｆ６は上記の通りであり；式（１ａ）において、ｂ’’は１以上１００以下の整数であり；式（１ｂ）において、ａ’’およびｂ’’は、それぞれ独立して１以上３０以下の整数であり、ｃ’’およびｄ’’はそれぞれ独立して１以上３００以下の整数である。添字ａ’’、ｂ’’、ｃ’’、ｄ’’を付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である。 Examples of the perfluoro (poly) ether compound represented by the above general formula (1) include a compound represented by any one of the following general formulas (1a) and (1b) (one or a mixture of two or more) May be mentioned.
Rf 5- (OCF 2 CF 2 CF 2 ) b '' -Rf 6 (1a)
Rf 5- (OCF 2 CF 2 CF 2 CF 2 ) a '' -(OCF 2 CF 2 CF 2 ) b '' -(OCF 2 CF 2 ) c '' -(OCF 2 ) d '' -Rf 6 (1b)
In these formulas, Rf 5 and Rf 6 are as described above; in formula (1a), b ′ ′ is an integer of 1 or more and 100 or less; in formula (1b), a ′ ′ and b ′ ′ are Each is independently an integer of 1 or more and 30 or less, and c ′ ′ and d ′ ′ are each independently an integer of 1 or more and 300 or less. The order in which each repeating unit enclosed in parentheses with the subscripts a ′ ′, b ′ ′, c ′ ′ and d ′ ′ is given is arbitrary in the formula.
　上記含フッ素オイルは、１，０００～３０，０００の数平均分子量を有していてよい。特に、式（１ａ）で表される化合物の数平均分子量は、２，０００～８，０００であることが好ましい。かかる数平均分子量を有することにより、高い表面滑り性を得ることができる。一の態様において、式（１ｂ）で表される化合物の数平均分子量は、３，０００～８，０００である。別の態様において、式（１ｂ）で表される化合物の数平均分子量は、８，０００～３０，０００である。 The fluorine-containing oil may have a number average molecular weight of 1,000 to 30,000. In particular, the number average molecular weight of the compound represented by the formula (1a) is preferably 2,000 to 8,000. By having such a number average molecular weight, high surface slipperiness can be obtained. In one embodiment, the number average molecular weight of the compound represented by formula (1b) is 3,000 to 8,000. In another embodiment, the number average molecular weight of the compound represented by formula (1b) is 8,000 to 30,000.
　上記表面処理剤中、含フッ素オイルは、上記ＰＦＰＥ含有シラン化合物１００質量部に対して、例えば０～５００質量部、好ましくは０～１００質量部、より好ましくは１～５０質量部、さらに好ましくは１～５質量部で含まれ得る。 In the surface treatment agent, the fluorine-containing oil is, for example, 0 to 500 parts by mass, preferably 0 to 100 parts by mass, more preferably 1 to 50 parts by mass, further preferably 100 parts by mass of the PFPE-containing silane compound. It may be contained in 1 to 5 parts by mass.
　また、別の観点から、含フッ素オイルは、一般式Ｒｆ’－Ｆ（式中、Ｒｆ’はＣ５－１６パーフルオロアルキル基である。）で表される化合物であってよい。また、クロロトリフルオロエチレンオリゴマーであってもよい。Ｒｆ’－Ｆで表される化合物およびクロロトリフルオロエチレンオリゴマーは、ＲｆがＣ１－１６パーフルオロアルキル基である上記パーフルオロ（ポリ）エーテル基含有シラン化合物と高い親和性が得られる点で好ましい。 From another point of view, the fluorine-containing oil may be a compound represented by the general formula Rf′-F (wherein Rf ′ is a C 5-16 perfluoroalkyl group). Moreover, a chloro trifluoro ethylene oligomer may be sufficient. The compound represented by Rf′-F and the chlorotrifluoroethylene oligomer are preferable in that high affinity is obtained with the above perfluoro (poly) ether group-containing silane compound in which Rf is a C 1-16 perfluoroalkyl group. .
　含フッ素オイルは、表面処理層の表面滑り性を向上させるのに寄与する。 The fluorine-containing oil contributes to the improvement of the surface slipperiness of the surface treatment layer.
　上記シリコーンオイルとしては、例えばシロキサン結合が２，０００以下の直鎖状または環状のシリコーンオイルを用い得る。直鎖状のシリコーンオイルは、いわゆるストレートシリコーンオイルおよび変性シリコーンオイルであってよい。ストレートシリコーンオイルとしては、ジメチルシリコーンオイル、メチルフェニルシリコーンオイル、メチルハイドロジェンシリコーンオイルが挙げられる。変性シリコーンオイルとしては、ストレートシリコーンオイルを、アルキル、アラルキル、ポリエーテル、高級脂肪酸エステル、フルオロアルキル、アミノ、エポキシ、カルボキシル、アルコールなどにより変性したものが挙げられる。環状のシリコーンオイルは、例えば環状ジメチルシロキサンオイルなどが挙げられる。 As the silicone oil, for example, a linear or cyclic silicone oil having a siloxane bond of 2,000 or less can be used. Linear silicone oils may be so-called straight silicone oils and modified silicone oils. Straight silicone oils include dimethyl silicone oil, methyl phenyl silicone oil and methyl hydrogen silicone oil. Examples of the modified silicone oil include those obtained by modifying a straight silicone oil with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol and the like. The cyclic silicone oil may, for example, be a cyclic dimethylsiloxane oil.
　上記表面処理剤中、かかるシリコーンオイルは、上記ＰＦＰＥ含有シラン化合物１００質量部（２種以上の場合にはこれらの合計、以下も同様）に対して、例えば０～５０質量部、好ましくは０～５質量部で含まれ得る。 In the surface treatment agent, such silicone oil is, for example, 0 to 50 parts by mass, preferably 0 to 50 parts by mass, with respect to 100 parts by mass of the PFPE-containing silane compound (in the case of two or more, the total of them, the same applies hereinafter). It may be contained in 5 parts by mass.
　シリコーンオイルは、表面処理層の表面滑り性を向上させるのに寄与する。 The silicone oil contributes to the improvement of the surface slipperiness of the surface treatment layer.
　上記触媒としては、酸（例えば酢酸、トリフルオロ酢酸等）、塩基（例えばアンモニア、トリエチルアミン、ジエチルアミン等）、遷移金属（例えばＴｉ、Ｎｉ、Ｓｎ等）等が挙げられる。 Examples of the catalyst include acids (eg, acetic acid, trifluoroacetic acid etc.), bases (eg, ammonia, triethylamine, diethylamine etc.), transition metals (eg, Ti, Ni, Sn etc.) and the like.
　触媒は、上記含フッ素シラン化合物の加水分解および脱水縮合を促進し、表面処理層の形成を促進する。 The catalyst promotes the hydrolysis and dehydration condensation of the fluorine-containing silane compound and promotes the formation of the surface treatment layer.
　上記他の成分としての低級アルコールとしては、炭素数１～６のアルコール化合物が挙げられる。 Examples of the lower alcohol as the other component include alcohol compounds having 1 to 6 carbon atoms.
　上記遷移金属としては、白金、ルテニウム、ロジウム等が挙げられる。 Platinum, ruthenium, rhodium etc. are mentioned as said transition metal.
　上記ハロゲン化物イオンとしては、塩化物イオン等が挙げられる。 Chloride ion etc. are mentioned as said halide ion.
　上記分子構造内に非共有電子対を有する原子を含む化合物しては、ジエチルアミン、トリエチルアミン、アニリン、ピリジン、ヘキサメチルホスホルアミド、Ｎ，Ｎ－ジエチルアセトアミド、Ｎ，Ｎ－ジエチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチルホルムアミド、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ－メチルピロリドン、テトラメチル尿素、ジメチルスルホキシド（ＤＭＳＯ）、テトラメチレンスルホキシド、メチルフェニルスルホキシド、ジフェニルスルホキシド等を挙げられる。これらの化合物の中で、ジメチルスルホキシド、またはテトラメチレンスルホキシドを用いることが好ましい。 Compounds containing an atom having a noncovalent electron pair in the above molecular structure include diethylamine, triethylamine, aniline, pyridine, hexamethylphosphoramide, N, N-diethylacetamide, N, N-diethylformamide, N, N Dimethylacetamide, N-methylformamide, N, N-dimethylformamide, N-methylpyrrolidone, tetramethylurea, dimethylsulfoxide (DMSO), tetramethylene sulfoxide, methylphenyl sulfoxide, diphenyl sulfoxide and the like. Of these compounds, dimethyl sulfoxide or tetramethylene sulfoxide is preferably used.
　他の成分としては、上記以外に、例えば、テトラエトキシシラン、メチルトリメトキシシラン、３－アミノプロピルトリメトキシシラン、３－グリシドキシプロピルトリメトキシシラン、メチルトリアセトキシシラン等も挙げられる。 As other components, in addition to the above, for example, tetraethoxysilane, methyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltriacetoxysilane and the like can also be mentioned.
　一の態様において、上記表面処理剤は、上記他の成分である含フッ素オイル、シリコーンオイル、触媒、低級アルコール、遷移金属、ハロゲン化物イオン、分子構造内に非共有電子対を有する原子を含む化合物を含まない。 In one aspect, the above-mentioned surface treatment agent is a compound containing the above-mentioned other component fluorine-containing oil, silicone oil, catalyst, lower alcohol, transition metal, halide ion, atom having non-covalent electron pair in molecular structure Does not contain
　上記表面処理剤は、多孔質物質、例えば多孔質のセラミック材料、金属繊維、例えばスチールウールを綿状に固めたものに含浸させて、ペレットとすることができる。当該ペレットは、例えば、真空蒸着に用いることができる。 The surface treatment agent may be impregnated into a porous material such as a porous ceramic material, metal fiber such as steel wool, and made into a pellet. The said pellet can be used for vacuum evaporation, for example.
　上記表面処理剤からなる層とベース層とを含む基材の形成は、例えば以下のようにして製造できる。 Formation of the base material containing the layer which consists of the said surface treatment agent, and a base layer can be manufactured as follows, for example.
　まず、ベース層を準備する。ベース層については上記のとおりである。 First, prepare the base layer. The base layer is as described above.
　ベース層の表面（最外層）に何らかの層（または膜）、例えばハードコート層や反射防止層などが形成される場合、これらの層（または膜）は、これらの層（または膜）の形成される表面（本段落において、被処理層と称する）の表面をイオンクリーニング後に形成されることが好ましい。上記イオンクリーニングは、例えば、酸素ガス、および／または不活性ガス（例えば、アルゴン、キセノン、窒素など）を用いてイオンビームを被処理層の表面に照射することによって行い得る。上記照射にはイオン銃を用いることができる。イオンクリーニングすることにより、被処理層の表面から有機物などが除去され、反射防止層が被処理層に、より強固に接着し得る。 When any layer (or film) such as a hard coat layer or an antireflective layer is formed on the surface (the outermost layer) of the base layer, these layers (or films) are formed of these layers (or films) It is preferable that the surface of the target surface (referred to as a treated layer in this paragraph) be formed after ion cleaning. The ion cleaning may be performed, for example, by irradiating the surface of the layer to be treated with an ion beam using oxygen gas and / or an inert gas (eg, argon, xenon, nitrogen, etc.). An ion gun can be used for the irradiation. By ion cleaning, organic substances and the like are removed from the surface of the layer to be treated, and the antireflective layer can be more firmly adhered to the layer to be treated.
　上記イオンクリーニングは、例えば、酸素ガスとアルゴンガスの混合ガスを用いて行い得る。上記混合ガスとしては、酸素ガスを５～１００ｃｃ／分、およびアルゴンガスを５～１００ｃｃ／分含むガスを用いることが好ましく、酸素ガスを２０～５０ｃｃ／分、およびアルゴンガスを１０～４０ｃｃ／分含むガスを用いることがより好ましく、酸素ガスを３０～４０ｃｃ／分、およびアルゴンガスを１０～２０ｃｃ／分含むガスを用いることがさらに好ましい。 The ion cleaning may be performed using, for example, a mixed gas of oxygen gas and argon gas. As the mixed gas, a gas containing 5 to 100 cc / min of oxygen gas and 5 to 100 cc / min of argon gas is preferably used, 20 to 50 cc / min of oxygen gas, and 10 to 40 cc / min of argon gas. It is more preferable to use a gas containing it, and it is further preferable to use a gas containing 30 to 40 cc / min of oxygen gas and 10 to 20 cc / min of argon gas.
　上記イオンビームの照射は、１０～６００秒間照射することが好ましく、５０～４００秒間照射することがより好ましく、２００～３００秒間照射することがさらに好ましい。 The irradiation with the ion beam is preferably performed for 10 to 600 seconds, more preferably for 50 to 400 seconds, and still more preferably for 200 to 300 seconds.
　好ましい態様において、上記イオンクリーニングは、酸素ガスを３０～４０ｃｃ／分、およびアルゴンガスを１０～２０ｃｃ／分含むガスを用いて、イオンビームを２００～３００秒間照射する。 In a preferred embodiment, the ion cleaning is performed by irradiating the ion beam for 200 to 300 seconds using a gas containing 30 to 40 cc / min of oxygen gas and 10 to 20 cc / min of argon gas.
　ベース層の表面に反射防止層が形成される場合、反射防止層は（例えばガラスなどの表面に）蒸着（例えば、真空蒸着）により形成されたものであり得る。上記反射防止層（例えば二酸化ケイ素膜）の厚みは、例えば１０ｎｍ未満とすることができ、具体的には３～８ｎｍ、より具体的には４．５ｎｍとすることができる。このような厚みとすることによって、より摩擦耐久性の良好な表面処理層を有する基材を形成し得る。 When an antireflective layer is formed on the surface of the base layer, the antireflective layer may be formed by vapor deposition (e.g., vacuum evaporation) (e.g., on the surface of glass or the like). The thickness of the antireflective layer (eg, a silicon dioxide film) can be, for example, less than 10 nm, specifically, 3 to 8 nm, more specifically, 4.5 nm. With such a thickness, it is possible to form a substrate having a surface treatment layer having better friction durability.
　その後、ベース層の表面をイオンクリーニングする。イオンクリーニングは、例えば、酸素ガス、および／または不活性ガス（例えば、アルゴン、キセノン、窒素など）を用いてイオンビームをベース層の表面に照射することによって行い得る。上記照射にはイオン銃を用いることができる。イオンクリーニングすることにより、ベース層の表面から有機物などが除去され、表面処理剤からなる層がベース層に、より強固に接着し得る。 Thereafter, the surface of the base layer is ion cleaned. The ion cleaning may be performed, for example, by irradiating the surface of the base layer with an ion beam using oxygen gas and / or an inert gas (eg, argon, xenon, nitrogen, etc.). An ion gun can be used for the irradiation. By ion cleaning, organic substances and the like are removed from the surface of the base layer, and the layer made of the surface treatment agent can be more firmly adhered to the base layer.
　上記ベース層の表面のイオンクリーニングは、例えば、酸素ガスとアルゴンガスの混合ガスを用いて行い得る。上記混合ガスとしては、酸素ガスを５～１００ｃｃ／分、およびアルゴンガスを５～１００ｃｃ／分含むガスを用いることが好ましく、酸素ガスを２０～５０ｃｃ／分、およびアルゴンガスを１０～４０ｃｃ／分含むガスを用いることがより好ましく、酸素ガスを２５～４０ｃｃ／分、およびアルゴンガスを１５～３０ｃｃ／分含むガスを用いることがさらに好ましい。 The ion cleaning of the surface of the base layer may be performed, for example, using a mixed gas of oxygen gas and argon gas. As the mixed gas, a gas containing 5 to 100 cc / min of oxygen gas and 5 to 100 cc / min of argon gas is preferably used, 20 to 50 cc / min of oxygen gas, and 10 to 40 cc / min of argon gas. It is more preferable to use a gas containing it, and it is further preferable to use a gas containing 25 to 40 cc / min of oxygen gas and 15 to 30 cc / min of argon gas.
　上記ベース層の表面のイオンクリーニングにおいて、上記イオンビームの照射は、１～２００秒間照射することが好ましく、１～１００秒間照射することがより好ましく、５～４０秒間照射することがさらに好ましい。 In the ion cleaning of the surface of the base layer, the irradiation with the ion beam is preferably performed for 1 to 200 seconds, more preferably for 1 to 100 seconds, and still more preferably for 5 to 40 seconds.
　好ましい態様において、上記ベース層の表面のイオンクリーニングは、酸素ガスを２５～４０ｃｃ／分、およびアルゴンガスを１５～３０ｃｃ／分含むガスを用いて、イオンビームを５～４０秒間照射する。 In a preferred embodiment, the ion cleaning of the surface of the base layer is performed by irradiating an ion beam for 5 to 40 seconds with a gas containing 25 to 40 cc / min of oxygen gas and 15 to 30 cc / min of argon gas.
　イオンクリーニング後のベース層の表面に、上記表面処理剤の膜を形成し、この膜を必要に応じて後処理し、これにより、上記表面処理剤から表面処理層を形成する。 A film of the surface treatment agent is formed on the surface of the base layer after ion cleaning, and this film is post-treated as necessary, thereby forming a surface treatment layer from the surface treatment agent.
　上記表面処理剤の膜形成は、上記の表面処理剤をベース層の表面に対して、該表面を被覆するように適用することによって実施できる。被覆方法は、特に限定されない。例えば、湿潤被覆法および乾燥被覆法を使用できる。 The film formation of the surface treatment agent can be carried out by applying the above-mentioned surface treatment agent to the surface of the base layer so as to cover the surface. The coating method is not particularly limited. For example, wet coating and dry coating can be used.
　湿潤被覆法の例としては、浸漬コーティング、スピンコーティング、フローコーティング、スプレーコーティング、ロールコーティング、グラビアコーティングおよび類似の方法が挙げられる。 Examples of wet coating methods include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating and similar methods.
　乾燥被覆法の例としては、蒸着（通常、真空蒸着）、スパッタリング、ＣＶＤおよび類似の方法が挙げられる。蒸着法（通常、真空蒸着法）の具体例としては、抵抗加熱、電子ビーム、マイクロ波等を用いた高周波加熱、イオンビームおよび類似の方法が挙げられる。ＣＶＤ方法の具体例としては、プラズマ－ＣＶＤ、光学ＣＶＤ、熱ＣＶＤおよび類似の方法が挙げられる。 Examples of dry coating methods include vapor deposition (usually vacuum evaporation), sputtering, CVD and similar methods. Specific examples of the deposition method (usually, vacuum deposition method) include resistance heating, high frequency heating using an electron beam, microwave and the like, an ion beam, and similar methods. Specific examples of the CVD method include plasma-CVD, optical CVD, thermal CVD and similar methods.
　更に、常圧プラズマ法による被覆も可能である。 Furthermore, coating by the atmospheric pressure plasma method is also possible.
　その後、加熱処理を行う。 After that, heat treatment is performed.
　上記加熱処理は、６０℃以上で行うことが好ましく、１００℃以上で行うことがより好ましく、１４０℃以上で行うことがさらに好ましい。上記加熱処理は、３００℃以下で行うことが好ましく、２５０℃以下で行うことがより好ましく、２００℃以下で行うことがさらに好ましい。 The heat treatment is preferably performed at 60 ° C. or higher, more preferably 100 ° C. or higher, and still more preferably 140 ° C. or higher. The heat treatment is preferably performed at 300 ° C. or less, more preferably 250 ° C. or less, and still more preferably 200 ° C. or less.
　上記加熱処理は、６０～３００℃の範囲の温度で行うことが好ましく、８０～２００℃の範囲の温度で行うことがより好ましく、１００～１８０℃の範囲の温度で行うことがさらに好ましい。 The heat treatment is preferably performed at a temperature in the range of 60 to 300 ° C., more preferably at a temperature in the range of 80 to 200 ° C., and still more preferably at a temperature in the range of 100 to 180 ° C.
　上記加熱処理は、５分以上行うことが好ましく、１５分以上行うことがより好ましく、３０分以上行うことがさらに好ましい。上記加熱処理は、６００分以下行うことが好ましく、３００分以下行うことがより好ましく、９０分以下行うことがさらに好ましく、７０分以下行ってもよい。 The heat treatment is preferably performed for 5 minutes or more, more preferably for 15 minutes or more, and still more preferably for 30 minutes or more. The heat treatment is preferably performed for 600 minutes or less, more preferably for 300 minutes or less, still more preferably for 90 minutes or less, and may be performed for 70 minutes or less.
　上記加熱処理は、５～３００分間行うことが好ましく、１５～１２０分間行うことがより好ましく、３０～９０分間行うことがさらに好ましい。 The heat treatment is preferably performed for 5 to 300 minutes, more preferably for 15 to 120 minutes, and still more preferably for 30 to 90 minutes.
　上記加熱処理は、６０～２００℃の範囲の温度において５～２００分間行うことが好ましく、１００～１８０℃の範囲の温度において１５～９０分間行うことがより好ましい。 The heat treatment is preferably performed at a temperature in the range of 60 to 200 ° C. for 5 to 200 minutes, and more preferably at a temperature in the range of 100 to 180 ° C. for 15 to 90 minutes.
　好ましい態様においては、ベース層のイオンクリーニングを、酸素ガスを２０～４０ｃｃ／分、およびアルゴンガスを１０～３０ｃｃ／分含むガスを用いて、１０～４０℃の範囲の温度で、イオンビームを１０～３００秒間照射し、その後、表面処理剤からなる層を形成し、加熱処理を１００～１８０℃の範囲の温度において１５～９０分間行う。 In a preferred embodiment, the ion cleaning of the base layer is carried out using a gas containing 20 to 40 cc / min of oxygen gas and 10 to 30 cc / min of argon gas at a temperature in the range of 10 to 40.degree. Irradiation is carried out for ̃300 seconds, then a layer consisting of a surface treatment agent is formed, and heat treatment is carried out at a temperature in the range of 100 ̃180 ° C. for 15 ̃90 minutes.
　その後、形成された膜の表面処理を行うことが好ましい。表面処理は、エタノールを用いて行うことが好ましい。具体的には、キムワイプ（登録商標）ワイパーＳ－２００（日本製紙クレシア株式会社製）にエタノールをしみ混ませたもの（具体的には、キムワイプ１枚（１２０ｍｍ×２１５ｍｍ）あたりエタノールを１～２ｍｌしみ混ませたもの）を用いて、形成された膜の表面を拭く。より具体的には、形成された膜の表面を、上記エタノールをしみ混ませたキムワイプを用いて２０往復させ拭く。その後、別途用意したキムワイプ（登録商標）ワイパーＳ－２００を用いて、膜の表面をから拭きする。このような処理を行うことにより、本発明の基材は、耐摩擦性の向上に寄与し得る。 Thereafter, it is preferable to carry out surface treatment of the formed film. The surface treatment is preferably performed using ethanol. Specifically, 1 to 2 ml of ethanol per one (specifically, one Kimwipe (120 mm × 215 mm)) prepared by spotting and mixing Kim Wipes (registered trademark) Wiper S-200 (manufactured by Nippon Paper Industries Co., Ltd.) Wipe the surface of the formed film with a mixture of stains). More specifically, the surface of the formed film is wiped back and forth 20 times using Kim wipe wiped with ethanol. Thereafter, the surface of the film is wiped off using a Kimwipe (registered trademark) wiper S-200 prepared separately. By performing such treatment, the substrate of the present invention can contribute to the improvement of the abrasion resistance.
　上記のようにして、ベース層の表面に、上記表面処理剤の膜に由来する表面処理層が形成される。これにより得られる表面処理層は、帯電性が低い。また、この表面処理層は、低帯電性であることに加えて、使用する表面処理剤の組成にもよるが、撥水性、撥油性、防汚性（例えば指紋等の汚れの付着を防止する）、防水性（電子部品等への水の浸入を防止する）、表面滑り性（または潤滑性、例えば指紋等の汚れの拭き取り性や、指に対する優れた触感）、摩擦耐久性、透明性などを有し得、機能性薄膜として好適に利用され得る。 As described above, the surface treatment layer derived from the film of the surface treatment agent is formed on the surface of the base layer. The surface treatment layer thus obtained has low chargeability. In addition to the low chargeability, this surface treatment layer also depends on the composition of the surface treatment agent to be used, but prevents the adhesion of stains such as fingerprints, etc., depending on the water repellency, oil repellency and stain resistance. ) Waterproofness (prevents water ingress to electronic parts etc.), surface slipperiness (or lubricity, for example, the wipeability of dirt such as fingerprints, excellent touch feeling to fingers), friction durability, transparency, etc. And may be suitably utilized as a functional thin film.
　すなわち本態様の基材は、表面処理層を最外層に有する光学材料にも用い得る。 That is, the base material of this aspect can be used also for the optical material which has a surface treatment layer in the outermost layer.
　光学材料としては、後記に例示するようなディスプレイ等に関する光学材料のほか、多種多様な光学材料が好ましく挙げられる：例えば、陰極線管（ＣＲＴ；例えば、ＴＶ、パソコンモニター）、液晶ディスプレイ、プラズマディスプレイ、有機ＥＬディスプレイ、無機薄膜ＥＬドットマトリクスディスプレイ、背面投写型ディスプレイ、蛍光表示管（ＶＦＤ）、電界放出ディスプレイ（ＦＥＤ；Ｆｉｅｌｄ Ｅｍｉｓｓｉｏｎ Ｄｉｓｐｌａｙ）などのディスプレイ又はそれらのディスプレイの保護板、またはそれらの表面に反射防止膜処理を施したもの。 As the optical material, in addition to optical materials related to displays as exemplified later, a wide variety of optical materials are preferably mentioned: For example, cathode ray tube (CRT; eg, TV, personal computer monitor), liquid crystal display, plasma display, Displays such as organic EL displays, inorganic thin film EL dot matrix displays, rear projection displays, fluorescent display tubes (VFDs), field emission displays (FEDs) or protective plates of those displays, or reflections on those surfaces Those with a protective film treatment.
　本態様によって得られる表面処理層を有する物品は、特に限定されるものではないが、光学部材であり得る。光学部材の例には、次のものが挙げられる：眼鏡などのレンズ；ＰＤＰ、ＬＣＤなどのディスプレイの前面保護板、反射防止板、偏光板、アンチグレア板；携帯電話、携帯情報端末などの機器のタッチパネルシートまたはそのカバーガラス；ブルーレイ（Ｂｌｕ－ｒａｙ（登録商標））ディスク、ＤＶＤディスク、ＣＤ－Ｒ、ＭＯなどの光ディスクのディスク面；光ファイバー；時計の表示面など。 An article having a surface treatment layer obtained by the present aspect is not particularly limited, but may be an optical member. Examples of optical members include: lenses such as glasses; front protective plates for displays such as PDPs and LCDs; anti-reflection plates; polarizing plates; anti-glare plates; devices such as mobile phones and personal digital assistants Touch panel sheet or its cover glass; disc surface of optical disc such as Blu-ray (registered trademark) disc, DVD disc, CD-R, MO, etc .; optical fiber; display surface of watch, etc.
　また、本態様によって得られる表面処理層を有する物品は、医療機器または医療材料であってもよい。 In addition, the article having the surface treatment layer obtained by the present aspect may be a medical device or a medical material.
　表面処理層の厚さは、特に限定されない。光学部材の場合、表面処理層の厚さは、１～５０ｎｍ、好ましくは１～３０ｎｍ、より好ましくは１～１５ｎｍの範囲であることが、光学性能、表面滑り性、摩擦耐久性および防汚性の点から好ましい。 The thickness of the surface treatment layer is not particularly limited. In the case of an optical member, the thickness of the surface treatment layer is in the range of 1 to 50 nm, preferably 1 to 30 nm, more preferably 1 to 15 nm. Optical performance, surface slipperiness, friction durability and antifouling property It is preferable from the point of
　上記表面処理剤から形成される表面処理層を有する物品は、好ましくは１０１２Ω以下、より好ましくは１０１０Ω以下、さらに好ましくは１０９Ω以下、例えば１０８Ω以下の表面抵抗値を有し得る。表面抵抗値を低くすることにより、物品の帯電性を低減することができる。また、上記表面処理剤から形成される表面処理層を有する物品は、好ましくは１０６Ω以上、より好ましくは１０７Ω以上、さらに好ましくは１０８Ω以上の表面抵抗値を有し得る。表面抵抗値を大きくすることにより、例えば静電容量方式のタッチパネルなどにおいて、タッチパネルの動作を担保することができる。好ましい態様において、上記表面処理剤から形成される表面処理層を有する物品は、１０６Ω以上１０１２Ω以下、より好ましくは１０８Ω以上１０１０Ω以下の表面抵抗値を有し得る。 An article having a surface treatment layer formed of the above surface treatment agent preferably has a surface resistance value of 10 12 Ω or less, more preferably 10 10 Ω or less, still more preferably 10 9 Ω or less, for example 10 8 Ω or less. It can. By lowering the surface resistance, the chargeability of the article can be reduced. In addition, an article having a surface treatment layer formed of the above surface treatment agent may have a surface resistance value of preferably 10 6 Ω or more, more preferably 10 7 Ω or more, and still more preferably 10 8 Ω or more. By increasing the surface resistance value, for example, in a capacitive touch panel or the like, the operation of the touch panel can be secured. In a preferred embodiment, an article having a surface treatment layer formed of the surface treatment agent may have a surface resistance value of 10 6 Ω or more and 10 12 Ω or less, more preferably 10 8 Ω or more and 10 10 Ω or less.
（態様２）
　本態様の基材は、
　表面にパーフルオロポリエーテル基含有化合物から形成された表面処理層を有する基材であって、
　２１℃および湿度６５％の雰囲気下において、試験用布（ここで、試験用布は、リン酸三ナトリウム５．５ｇ、塩化ナトリウム１０ｇ、乳酸３．１ｇ、リシン５ｇおよび蒸留水１００ｍｌからなる人工汗を浸漬させた、ＩＮＮＯＷＥＰ社製のＡＢＲＥＸ（登録商標）　ｓｔａｎｄａｒｄ　ｃｏｔｔｏｎ　ｓｏｉｌｉｎｇ　ｔｅｘｔｉｌｅ　ＦＩＮＥである。）で覆われたシリコーンよりなる摩擦子に、基材に対して５Ｎの荷重がかかるように、負荷をかけながら、該摩擦子を４０ｍｍ／秒の速度で表面上を往復する摩擦試験における、該摩擦子の往復回数４０００回における水の静的接触角の測定値が、８０度以上である。 (Aspect 2)
The base material of this embodiment is
A substrate having a surface treatment layer formed of a compound containing a perfluoropolyether group on the surface,
Test cloth (here, the test cloth is an artificial sweat consisting of 5.5 g of trisodium phosphate, 10 g of sodium chloride, 3.1 g of lactic acid, 5 g of lysine and 100 ml of distilled water under an atmosphere of 21 ° C. and a humidity of 65%. Is applied so that a load of 5 N is applied to the substrate on the friction element made of silicone covered with ABREX (R) standard cotton soiling textile FINE manufactured by INNOWEP, in which However, the measured value of the static contact angle of water after the number of times of reciprocation of the friction element in the friction test in which the friction element is reciprocated on the surface at a speed of 40 mm / sec is 80 degrees or more.
　本態様の説明において、摩擦試験、および水の静的接触角等、態様１の記載と重複する記載は省略することがある。 In the description of the present embodiment, description overlapping with the description of the embodiment 1, such as the friction test and the static contact angle of water, may be omitted.
　本態様の基材は、摩擦子の往復回数４０００回における水の静的接触角の測定値が、好ましくは８４度以上であり、より好ましくは８５度以上であり、さらに好ましくは、９０度以上である。このような基材では、基材の表面が摩擦された場合であっても、その表面における撥水性が良好である。すなわち、摩擦の生じ得る用途において、このような基材は特に有用であり得る。 The base material of this embodiment preferably has a measured value of static contact angle of water at 4,000 reciprocations of the friction element, preferably 84 degrees or more, more preferably 85 degrees or more, still more preferably 90 degrees or more It is. In such a substrate, even when the surface of the substrate is rubbed, the water repellency on the surface is good. Thus, such substrates may be particularly useful in applications where friction may occur.
　本態様の基材は、摩擦試験前の接触角の測定値が高いことが好ましい。摩擦試験前の基材の接触角は、８０度以上であることが好ましく、１００度以上であることがより好ましく、１０５度以上であることが特に好ましく、１１０度以上であることがさらに好ましい。 It is preferable that the base material of this aspect has a high measured value of the contact angle before the friction test. The contact angle of the substrate before the friction test is preferably 80 degrees or more, more preferably 100 degrees or more, particularly preferably 105 degrees or more, and still more preferably 110 degrees or more.
　摩擦子の往復回数０回の水の静的接触角の測定値に対する、摩擦子の往復回数４０００回における水の静的接触角の割合は、０．７０以上にあってもよく、０．８０以上にあってもよい。上記割合の上限値は、特に限定されないが、例えば１．００以下、具体的には０．９８以下であってもよい。このような基材では、基材の表面が摩擦された場合であっても、その表面における撥水性を良好に維持できる。すなわち、摩擦の生じ得る用途において、このような基材は特に有用であり得る。 The ratio of the static contact angle of water at 4,000 reciprocations of the friction element to the measured value of the static contact angle of water at the reciprocation number of times of the friction element may be 0.70 or more, 0.80 It may be above. The upper limit value of the ratio is not particularly limited, but may be, for example, 1.00 or less, specifically 0.98 or less. With such a substrate, even when the surface of the substrate is rubbed, the water repellency on the surface can be well maintained. Thus, such substrates may be particularly useful in applications where friction may occur.
　本態様の基材において、ＡＳＴＭ　Ｄ４９１７に準拠して測定される動摩擦係数が、０．０５０未満であることが好ましく、０．０３５未満であることがより好ましい。 In the base material of this embodiment, the dynamic friction coefficient measured in accordance with ASTM D4917 is preferably less than 0.050, and more preferably less than 0.035.
　好ましい態様において、本態様の基材は、さらに、
　波長３００ｎｍ～４００ｎｍの紫外線が、放射照度６２Ｗ／ｍ２で３００時間照射された表面において、２１℃および湿度６５％の雰囲気下において、試験用布（ここで、試験用布は、リン酸三ナトリウム５．５ｇ、塩化ナトリウム１０ｇ、乳酸３．１ｇ、リシン５ｇおよび蒸留水１００ｍｌからなる人工汗を浸漬させた、ＩＮＮＯＷＥＰ社製のＡＢＲＥＸ（登録商標）　ｓｔａｎｄａｒｄ　ｃｏｔｔｏｎ　ｓｏｉｌｉｎｇ　ｔｅｘｔｉｌｅ　ＦＩＮＥである。）で覆われたシリコーンよりなる摩擦子に、基材に対して５Ｎの荷重がかかるように、負荷をかけながら、該摩擦子を４０ｍｍ／秒の速度で往復する摩擦試験における、該摩擦子の往復回数０回、１０００回、２０００回、および３０００回（ただし、該往復回数は、水の静的接触角の測定値が最初に測定値が５０度未満になった回数を最大とする。）での往復回数（回）に対する紫外線照射後の水の静的接触角の測定値（度）に基づいて作成される線形近似直線の勾配が－０．０２２２超である。 In a preferred embodiment, the substrate of this embodiment further comprises
A test cloth (here, the test cloth is trisodium phosphate) under an atmosphere of 21 ° C. and a humidity of 65% on the surface irradiated with ultraviolet light of wavelength 300 nm to 400 nm at an irradiance of 62 W / m 2 for 300 hours Covered with INNOWEP's ABREX (R) standard cotton soiling textile FINE, soaked with artificial sweat consisting of 5.5 g, sodium chloride 10 g, lactic acid 3.1 g, lysine 5 g and 100 ml distilled water. In the friction test in which the friction element is reciprocated at a speed of 40 mm / sec while applying a load of 5 N to the base material to the friction element made of silicone, the number of reciprocations of the friction element is zero. 1000 times, 2000 times and 3000 times (however, the number of reciprocation times is a measure of the static contact angle of water Based on the measured value of static contact angle of water after UV irradiation (degree) to the number of round trips (times) in which the value is first measured less than 50 degrees) The slope of the linear approximation straight line is greater than -0.0222.
　ＵＶの照射試験については、上記態様１に記載のとおりである。 The UV irradiation test is as described in Aspect 1 above.
　本態様の基材は、少なくとも１の表面において、表面処理剤からなる層を含み得る。即ち、本態様の基材は、表面処理剤からなる層と、ベース層とを含むことが好ましい。表面処理層、ベース層については、上記態様１に記載のとおりである。 The substrate of the present embodiment may include a layer consisting of a surface treatment agent on at least one surface. That is, it is preferable that the base material of this aspect contains the layer which consists of surface treatment agents, and a base layer. The surface treatment layer and the base layer are as described in Aspect 1 above.
（態様３）
　本態様の基材は、
　表面にパーフルオロポリエーテル基含有化合物から形成された表面処理層を有する基材であって、
　波長３００ｎｍ～４００ｎｍの紫外線が、放射照度６２Ｗ／ｍ２で３００時間照射された表面において、２１℃および湿度６５％の雰囲気下において、試験用布（ここで、試験用布は、リン酸三ナトリウム５．５ｇ、塩化ナトリウム１０ｇ、乳酸３．１ｇ、リシン５ｇおよび蒸留水１００ｍｌからなる人工汗を浸漬させた、ＩＮＮＯＷＥＰ社製のＡＢＲＥＸ（登録商標）　ｓｔａｎｄａｒｄ　ｃｏｔｔｏｎ　ｓｏｉｌｉｎｇ　ｔｅｘｔｉｌｅ　ＦＩＮＥである。）で覆われたシリコーンよりなる摩擦子に、基材に対して５Ｎの荷重がかかるように、負荷をかけながら、該摩擦子を４０ｍｍ／秒の速度で往復する摩擦試験における、該摩擦子の往復回数０回、１０００回、２０００回、および３０００回（ただし、該往復回数は、水の静的接触角の測定値が最初に測定値が５０度未満になった回数を最大とする。）での往復回数（回）に対する紫外線照射後の水の静的接触角の測定値（度）に基づいて作成される線形近似直線の勾配が－０．０２２２超である。 (Aspect 3)
The base material of this embodiment is
A substrate having a surface treatment layer formed of a compound containing a perfluoropolyether group on the surface,
A test cloth (here, the test cloth is trisodium phosphate) under an atmosphere of 21 ° C. and a humidity of 65% on the surface irradiated with ultraviolet light of wavelength 300 nm to 400 nm at an irradiance of 62 W / m 2 for 300 hours Covered with INNOWEP's ABREX (R) standard cotton soiling textile FINE, soaked with artificial sweat consisting of 5.5 g, sodium chloride 10 g, lactic acid 3.1 g, lysine 5 g and 100 ml distilled water. In the friction test in which the friction element is reciprocated at a speed of 40 mm / sec while applying a load of 5 N to the base material to the friction element made of silicone, the number of reciprocations of the friction element is zero. 1000 times, 2000 times and 3000 times (however, the number of reciprocation times is a measure of the static contact angle of water Based on the measured value of static contact angle of water after UV irradiation (degree) to the number of round trips (times) in which the value is first measured less than 50 degrees) The slope of the linear approximation straight line is greater than -0.0222.
　本態様の説明において、摩擦試験、および水の静的接触角等、態様１の記載と重複する記載は省略することがある。 In the description of the present embodiment, description overlapping with the description of the embodiment 1, such as the friction test and the static contact angle of water, may be omitted.
　本態様の基材は、上記ＵＶ照射試験後の摩擦試験において、摩擦子の往復回数３０００回における水の静的接触角の測定値が、５０度以上であることが好ましい。 In the friction test after the above-mentioned UV irradiation test, it is preferable that the base material of this embodiment has a static contact angle of water measured at a frequency of 50 degrees or more after 3000 reciprocations of the friction element in the friction test.
　本態様の基材は、摩擦試験前の接触角の測定値が高いことが好ましい。摩擦試験前の基材の接触角は、８０度以上であることが好ましく、１００度以上であることがより好ましく、１０５度以上であることが特に好ましく、１１０度以上であることがさらに好ましい。 It is preferable that the base material of this aspect has a high measured value of the contact angle before the friction test. The contact angle of the substrate before the friction test is preferably 80 degrees or more, more preferably 100 degrees or more, particularly preferably 105 degrees or more, and still more preferably 110 degrees or more.
　ＵＶ照射試験後の基材において、摩擦子の往復回数０回の水の静的接触角の測定値に対する、摩擦子の往復回数３０００回における水の静的接触角の割合は、０．３５以上にあってもよく、０．５０以上にあってもよい。上記割合の上限値は、特に限定されないが、例えば１．００以下、具体的には０．９８以下であってもよい。このような基材では、基材の表面が摩擦された場合であっても、その表面における撥水性を良好に維持できる。すなわち、摩擦の生じ得る用途において、このような基材は特に有用であり得る。 In the substrate after the UV irradiation test, the ratio of the static contact angle of water at the number of reciprocation times of the friction element to the measured value of the static contact angle of water at the reciprocation times of the friction element is 0.35 or more Or 0.50 or more. The upper limit value of the ratio is not particularly limited, but may be, for example, 1.00 or less, specifically 0.98 or less. With such a substrate, even when the surface of the substrate is rubbed, the water repellency on the surface can be well maintained. Thus, such substrates may be particularly useful in applications where friction may occur.
　本態様の基材において、ＡＳＴＭ　Ｄ４９１７に準拠して測定される動摩擦係数が、０．０５０未満であることが好ましく、０．０３５未満であることがより好ましい。 In the base material of this embodiment, the dynamic friction coefficient measured in accordance with ASTM D4917 is preferably less than 0.050, and more preferably less than 0.035.
　本態様の基材は、少なくとも１の表面において、表面処理剤からなる層を含み得る。即ち、本態様の基材は、表面処理剤からなる層と、ベース層とを含むことが好ましい。表面処理層、ベース層については、上記態様１に記載のとおりである。 The substrate of the present embodiment may include a layer consisting of a surface treatment agent on at least one surface. That is, it is preferable that the base material of this aspect contains the layer which consists of surface treatment agents, and a base layer. The surface treatment layer and the base layer are as described in Aspect 1 above.
　本発明について、以下の実施例を通じてより具体的に説明するが、本発明はこれら実施例に限定されるものではない。なお、本実施例において、パーフルオロポリエーテルを構成する繰り返し単位（ＣＦ２Ｏ）、および（ＣＦ２ＣＦ２Ｏ）の存在順序は任意である。また、以下に示される化学式はすべて平均組成を示す。 The present invention will be more specifically described through the following examples, but the present invention is not limited to these examples. In the present example, the order in which the repeating units (CF 2 O) and (CF 2 CF 2 O) constituting the perfluoropolyether are present is arbitrary. Moreover, all the chemical formulas shown below show average compositions.
　実施例および比較例で用いるＰＦＰＥ含有シラン化合物は以下のとおりである。
・パーフルオロポリエーテル基含有シラン化合物（Ａ）：
　　CF3O(CF2CF2O)20(CF2O)28CF2CH2CH2CH2Si[CH2CH2Si(OCH3)3]3
・パーフルオロポリエーテル基含有シラン化合物（Ｂ）：
　　CF3O(CF2CF2O)20(CF2O)16CF2CH2CH2CH2Si[CH2CH2Si(OCH3)3]3
・パーフルオロポリエーテル基含有シラン化合物（Ｃ）：
　　CF3O(CF2CF2O)19(CF2O)28CF2CONHCH2C[CH2CH2CH2Si(OCH3)3]3
・パーフルオロポリエーテル基含有シラン化合物（Ｄ）：
　　CF3O(CF2CF2O)20(CF2O)16CF2CONHCH2C[CH2CH2CH2Si(OCH3)3]3
・パーフルオロポリエーテル基含有シラン化合物（Ｅ）：
　　CF3O(CF2CF2O)20(CF2O)16CF2CH2CH2CH2Si[CH2CH2CH2Si(OCH3)3]3 The PFPE-containing silane compounds used in the examples and comparative examples are as follows.
Perfluoropolyether group-containing silane compound (A):
CF 3 O (CF 2 CF 2 O) 20 (CF 2 O) 28 CF 2 CH 2 CH 2 CH 2 Si [CH 2 CH 2 Si (OCH 3) 3] 3
Perfluoropolyether group-containing silane compounds (B):
CF 3 O (CF 2 CF 2 O) 20 (CF 2 O) 16 CF 2 CH 2 CH 2 CH 2 Si [CH 2 CH 2 Si (OCH 3) 3] 3
Perfluoropolyether group-containing silane compound (C):
CF 3 O (CF 2 CF 2 O) 19 (CF 2 O) 28 CF 2 CONHCH 2 C [CH 2 CH 2 CH 2 Si (OCH 3) 3] 3
Perfluoropolyether group-containing silane compounds (D):
CF 3 O (CF 2 CF 2 O) 20 (CF 2 O) 16 CF 2 CONHCH 2 C [CH 2 CH 2 CH 2 Si (OCH 3) 3] 3
Perfluoropolyether group-containing silane compounds (E):
CF 3 O (CF 2 CF 2 O) 20 (CF 2 O) 16 CF 2 CH 2 CH 2 CH 2 Si [CH 2 CH 2 CH 2 Si (OCH 3) 3] 3
（実施例１）
　化合物（Ａ）を、濃度２０ｗｔ％になるように、ハイドロフルオロエーテル（スリーエム社製、ノベックＨＦＥ７２００）に溶解させて、表面処理剤１を調製した。 Example 1
Compound (A) was dissolved in hydrofluoroether (Novec HFE 7200 manufactured by 3M) to a concentration of 20 wt% to prepare a surface treatment agent 1.
　上記表面処理剤１を化学強化ガラス（コーニング社製、「ゴリラ」ガラス、厚さ０．７ｍｍ）上に真空蒸着した。真空蒸着の処理条件は、まず、圧力７．０×１０－４Ｐａで、この化学強化ガラス表面を、２４０秒間イオンクリーニング（Ｏ２ガス／Ａｒガス＝３５／１５ｃｃ／分）処理し、続いて、圧力３．０×１０－３Ｐａとし、二酸化ケイ素を４．５ｎｍの厚さで、この化学強化ガラスの表面に蒸着させて二酸化ケイ素膜を形成した。次に、その表面を２０秒間イオンクリーニング（Ｏ２ガス／Ａｒガス＝３０／２０ｃｃ／分）処理し、その後、化学強化ガラス１枚（６８ｍｍ×１４２ｍｍ）あたり、表面処理剤１を４ｍｇ（即ち、化合物（Ａ）を０．８ｍｇ含有）蒸着させた。その後、蒸着膜付き化学強化ガラスを、温度１５０℃で６０分間加熱処理し、最後に、エタノールで表面処理することで、表面処理層を形成し、表面に表面処理層を有する基材を形成した。 The surface treatment agent 1 was vacuum deposited on a chemically strengthened glass ("Gorilla" glass, 0.7 mm thick, manufactured by Corning). The processing conditions of vacuum deposition are, first, that this chemically strengthened glass surface is subjected to ion cleaning (O 2 gas / Ar gas = 35/15 cc / min) at a pressure of 7.0 × 10 −4 Pa for 240 seconds, and then Under a pressure of 3.0 × 10 −3 Pa, silicon dioxide was vapor-deposited on the surface of this chemically strengthened glass at a thickness of 4.5 nm to form a silicon dioxide film. Next, the surface is subjected to an ion cleaning (O 2 gas / Ar gas = 30/20 cc / min) for 20 seconds, and then 4 mg of the surface treating agent 1 (that is, one sheet of chemically strengthened glass (68 mm × 142 mm)). Compound (A) was evaporated (containing 0.8 mg). Thereafter, the chemically strengthened glass with vapor deposition film was heat treated at a temperature of 150 ° C. for 60 minutes, and finally, surface treated with ethanol to form a surface treated layer, and a substrate having a surface treated layer on the surface was formed. .
（実施例２～５）
　化合物（Ａ）に代えて、化合物（Ｂ）～化合物（Ｅ）を用いた以外は、実施例１と同様にして、表面処理層を形成し、表面に表面処理層を有する基材を形成した。 (Examples 2 to 5)
A surface-treated layer was formed in the same manner as in Example 1 except that compounds (B) to (E) were used instead of compound (A), and a substrate having a surface-treated layer on the surface was formed. .
（比較例１）
　上記表面処理剤１を化学強化ガラス（コーニング社製、「ゴリラ」ガラス、厚さ０．７ｍｍ）上に真空蒸着した。真空蒸着の処理条件は、まず、圧力７．０×１０－４Ｐａで、この化学強化ガラス表面を、２４０秒間イオンクリーニング（Ｏ２ガス／Ａｒガス＝３５／１５ｃｃ／分）処理し、続いて、圧力３．０×１０－３Ｐａとし、二酸化ケイ素を４．５ｎｍの厚さで、この化学強化ガラスの表面に蒸着させて二酸化ケイ素膜を形成した。次に、その表面に化学強化ガラス１枚（６８ｍｍ×１４２ｍｍ）あたり、表面処理剤１を４ｍｇ（即ち、化合物（Ａ）を０．８ｍｇ含有）蒸着させた。その後、蒸着膜付き化学強化ガラスを、温度２１℃および湿度６５％の雰囲気下で２４時間静置し、最後に、エタノールで表面処理することで、表面処理層を形成し、表面に表面処理層を有する基材を形成した。 (Comparative example 1)
The surface treatment agent 1 was vacuum deposited on a chemically strengthened glass ("Gorilla" glass, 0.7 mm thick, manufactured by Corning). The processing conditions of vacuum deposition are, first, that this chemically strengthened glass surface is subjected to ion cleaning (O 2 gas / Ar gas = 35/15 cc / min) at a pressure of 7.0 × 10 −4 Pa for 240 seconds, and then Under a pressure of 3.0 × 10 −3 Pa, silicon dioxide was vapor-deposited on the surface of this chemically strengthened glass at a thickness of 4.5 nm to form a silicon dioxide film. Next, 4 mg of the surface treatment agent 1 (that is, containing 0.8 mg of the compound (A)) was vapor-deposited on one surface of the chemically strengthened glass (68 mm × 142 mm). Thereafter, the chemically strengthened glass with a deposited film is allowed to stand for 24 hours in an atmosphere of a temperature of 21 ° C. and a humidity of 65%, and finally surface treated with ethanol to form a surface treated layer, and a surface treated layer on the surface. To form a substrate having
（比較例２～５）
　化合物（Ａ）に代えて、化合物（Ｂ）～化合物（Ｅ）を用いた以外は、比較例１と同様にして、表面処理層を形成し、表面に表面処理層を有する基材を形成した。 (Comparative examples 2 to 5)
A surface-treated layer was formed in the same manner as in Comparative Example 1 except that compounds (B) to (E) were used instead of compound (A), and a substrate having a surface-treated layer on the surface was formed. .
　実施例および比較例で得られた表面処理層の評価は以下のように行った。 The evaluation of the surface treatment layer obtained in Examples and Comparative Examples was performed as follows.
・水の静的接触角の測定
　水の静的接触角の測定は、接触角測定装置（協和界面科学社製）を用いて、水２μＬにて２１℃、６５％湿度の環境下で実施した。 -Measurement of static contact angle of water Measurement of static contact angle of water was carried out in an environment of 21 ° C and 65% humidity with 2 μL of water using a contact angle measurement device (manufactured by Kyowa Interface Science Co., Ltd.) .
・摩擦耐久性試験
　摩擦耐久性試験は以下のように行った。 Friction Durability Test The friction durability test was conducted as follows.
　まず、初期評価として、表面処理層形成後、その表面に未だ何も触れていない状態で、表面処理層の水の静的接触角を測定した（摩擦回数０回）。 First, as an initial evaluation, after the formation of the surface treatment layer, the static contact angle of water of the surface treatment layer was measured in a state where nothing was touched to the surface yet (friction number 0).
　次いで、ＩＮＮＯＷＥＰ社製ＡＢＲＥＸ（登録商標）試験機（型式：ｓｔａｎｄａｒｄ　ＡＢＲＥＸ（登録商標））に、上記の実施例または比較例にて得られた表面に表面処理層を有する基材を取り付けた。ＡＢＲＥＸ（登録商標）試験機に備え付けのシリコーン摩擦子の表面を試験用布で覆った。試験用布としては、ＩＮＮＯＷＥＰ社製　ＡＢＲＥＸ（登録商標）　ｓｔａｎｄａｒｄ　ｃｏｔｔｏｎ　ｓｏｉｌｉｎｇ　ｔｅｘｔｉｌｅ　ＦＩＮＥ）を、以下の組成の人工汗に浸漬したものを用いた。上記摩擦子に５Ｎの荷重を付与し、荷重を加えた状態で摩擦子を速度４０ｍｍ／秒、摩擦距離２０ｍｍで往復させた。摩擦子の往復回数（摩擦回数）１０００回毎に、水の静的接触角の測定値が８０度未満となるまで摩擦試験を行い、それぞれにおいて水の静的接触角の測定値を測定した。
・人工汗の組成
　　リン酸三ナトリウム：５．５ｇ
　　塩化ナトリウム：１０ｇ
　　乳酸：３．１ｇ
　　リシン：５ｇ
　　蒸留水：１００ｍｌ Next, a substrate having a surface treatment layer was attached to the surface obtained in the above-mentioned Example or Comparative Example in an INNOWEP ABREX (registered trademark) tester (model: standard ABREX (registered trademark)). The surface of the silicone friction pad provided in the ABREX® tester was covered with a test cloth. As a test cloth, one obtained by immersing ABREX (registered trademark) standard cotton soiling textile FINE) manufactured by INNOWEP in artificial sweat of the following composition was used. A load of 5 N was applied to the above-mentioned friction element, and in the state where the load was applied, the friction element was reciprocated at a speed of 40 mm / sec and a friction distance of 20 mm. The friction test was carried out until the measured value of the static contact angle of water became less than 80 degrees every 1000 times of the number of reciprocations of the friction element (number of times of friction), and the measured value of static contact angle of water was measured in each case.
・ Composition of artificial sweat Trisodium phosphate: 5.5 g
Sodium chloride: 10 g
Lactic acid: 3.1 g
Ricin: 5 g
Distilled water: 100 ml
　実施例および比較例で得られた静的接触角の測定結果を、表１に示す（表中、記号「－」は測定せず）。 The measurement results of the static contact angle obtained in Examples and Comparative Examples are shown in Table 1 (in the table, the symbol "-" is not measured).
Figure JPOXMLDOC01-appb-T000025
Figure JPOXMLDOC01-appb-T000025
　表１の静的接触角の測定値および摩擦回数に基づいて、摩擦回数と水の静的接触角の測定値との関係を求めた。摩擦回数が最大４０００回のときの、摩擦子の往復回数ｘに対する、水の静的接触角の測定値Ｆｘの関係を表す線形近似直線（ηおよびθは定数）、および、摩擦回数が最大１００００回のときの、摩擦子の往復回数ｘに対する、水の静的接触角の測定値Ｆ”ｘの関係を表す線形近似直線Ｆ”ｘ＝η”ｘ＋θ”（η”およびθ”は定数）の式を表２にそれぞれ示す。 Based on the measured values of the static contact angle and the number of frictions in Table 1, the relationship between the number of frictions and the measured value of the static contact angle of water was determined. A linear approximate straight line (η and θ is a constant) representing the relationship between the static contact angle measurement value F x of the water to the number of reciprocations x of the friction element when the number of frictions is at most 4000, and the number of frictions is the maximum when the 10000, for round trips x of Masatsuko, "linear approximation representing the relationship x linear F" measure F of the static contact angle of water x = η "x + θ" (η " and theta" is a constant) The formulas of are shown in Table 2 respectively.
Figure JPOXMLDOC01-appb-T000026
Figure JPOXMLDOC01-appb-T000026
・表面滑り性評価（動摩擦係数の測定）
　実施例にて形成された表面に表面処理層を有する基材について、表面性測定機（Ｌａｂｔｈｉｎｋ社製　ＦＰＴ－１）を用いて、摩擦子として紙を使用し、ＡＳＴＭ　Ｄ４９１７に準拠して、動摩擦係数（－）を測定した。具体的には、実施例および比較例で形成された基材を水平に配置し、摩擦子である紙（２ｃｍ×２ｃｍ）を基材の表面の露出上面に接触させ、その上に２００ｇｆの荷重を付与した。その後、荷重を加えた状態で、摩擦子である紙を２００ｍｍ／秒の速度で平行移動させて、動摩擦係数を測定した。結果を、表３に示す。 ・ Surface slip evaluation (measurement of dynamic coefficient of friction)
Using a surface property measuring machine (FPT-1 manufactured by Labthink), using a paper as a friction element, for a base material having a surface treatment layer on the surface formed in the example, the dynamic friction according to ASTM D4917 The factor (-) was measured. Specifically, the substrates formed in the examples and comparative examples are arranged horizontally, and a friction element paper (2 cm × 2 cm) is brought into contact with the exposed upper surface of the surface of the substrate, and a load of 200 gf is applied thereon. Granted. Thereafter, the paper, which is a friction element, was moved in parallel at a speed of 200 mm / sec with a load applied, and the dynamic friction coefficient was measured. The results are shown in Table 3.
Figure JPOXMLDOC01-appb-T000027
Figure JPOXMLDOC01-appb-T000027
　上記のように、実施例１～５で形成された基材は、優れた滑り性を有することが分かった。 As mentioned above, the substrates formed in Examples 1 to 5 were found to have excellent slip properties.
・ＵＶ照射試験およびＵＶ照射後の摩耗耐久性試験
　上記の実施例および比較例にて形成された表面に表面処理層を有する基材に、スーパーキセノンウェザーメーター　型式ＳＸ７５（スガ試験機株式会社）を用いて、７．５ｋｗの水冷式キセノンランプを３００時間照射した。照射条件は、波長３００ｎｍ～４００ｎｍにおいて放射照度６２Ｗ／ｍ２、基材のブラックパネル温度は、５５度で、ランプと基材の表面との距離は、２９ｃｍとした。 -UV irradiation test and abrasion durability test after UV irradiation A super xenon weather meter type SX75 (Suga Test Instruments Co., Ltd.) is used as the base material having a surface treatment layer on the surface formed in the above-mentioned Examples and Comparative Examples. Using a 7.5 kw water-cooled xenon lamp for 300 hours. The irradiation conditions were: irradiance of 62 W / m 2 at a wavelength of 300 nm to 400 nm, the black panel temperature of the base was 55 ° C., and the distance between the lamp and the surface of the base was 29 cm.
　その後、ＵＶ照射後の基材について、その表面に未だ何も触れていない状態で、表面処理層の水の静的接触角を測定した（摩擦回数０回）。 Thereafter, with respect to the substrate after UV irradiation, the static contact angle of the water of the surface treatment layer was measured in a state where nothing was touched yet on the surface (friction number of times 0).
　次いで、ＩＮＮＯＷＥＰ社製ＡＢＲＥＸ（登録商標）試験機（型式：ｓｔａｎｄａｒｄ　ＡＢＲＥＸ（登録商標））に、上記実施例および比較例にて得られた表面に表面処理層を有する基材であって、その後ＵＶ照射試験を行った基材を取り付けた。ＡＢＲＥＸ（登録商標）試験機に備え付けのシリコーン摩擦子の表面を、上記した組成の人工汗に浸漬した試験用布（ＩＮＮＯＷＥＰ社製　ＡＢＲＥＸ（登録商標）　ｓｔａｎｄａｒｄ　ｃｏｔｔｏｎ　ｓｏｉｌｉｎｇ　ｔｅｘｔｉｌｅ　ＦＩＮＥ）で覆った。上記摩擦子に５Ｎの荷重を付与し、荷重を加えた状態で摩擦子を速度４０ｍｍ／秒、摩擦距離２０ｍｍで往復させた。摩擦子の往復回数（摩擦回数）１０００回毎に、水の静的接触角の測定値が５０度未満となるまで摩擦試験を行い、それぞれにおいて水の静的接触角の測定値を測定した。結果を表４に示す（表中、記号「－」は測定せず）。 Next, ABREX (registered trademark) tester (model: standard ABREX (registered trademark)) manufactured by INNOWEP, a substrate having a surface treatment layer on the surface obtained in the above examples and comparative examples, and then UV The substrate subjected to the irradiation test was attached. The surface of the silicone friction element provided in the ABREX (registered trademark) testing machine was covered with a test cloth (ABREX (registered trademark) standard cotton soiling textile FINE manufactured by INNOWEP) immersed in the artificial sweat of the composition described above. A load of 5 N was applied to the above-mentioned friction element, and in the state where the load was applied, the friction element was reciprocated at a speed of 40 mm / sec and a friction distance of 20 mm. The friction test was carried out until the measured value of the static contact angle of water was less than 50 degrees every 1000 times of the number of reciprocation of the friction element (number of times of friction), and the measured value of static contact angle of water was measured in each case. The results are shown in Table 4 (in the table, the symbol "-" is not measured).
Figure JPOXMLDOC01-appb-T000028
Figure JPOXMLDOC01-appb-T000028
　表４の静的接触角の測定値および摩擦回数に基づいて、摩擦回数最大３０００回のときの摩擦子の往復回数ｘに対する、水の静的接触角の測定値Ｆ’ｘの関係を表す線形近似直線Ｆ’ｘ＝η’ｘ＋θ’（η’およびθ’は定数）、および、摩擦回数最大６０００回のときの摩擦子の往復回数ｘに対する、水の静的接触角の測定値Ｆ'''ｘの関係を表す線形近似直線Ｆ'''ｘ＝η'''ｘ＋θ'''（η'''およびθ'''は定数）を求めた。線形近似直線の式を表５に示す。 Based on the measured values of static contact angle and the number of frictions in Table 4, the relationship representing the measured value of the static contact angle of water F ' x against the number of reciprocations x of the friction element at the maximum number of frictions of 3000 Measured value F ′ ′ of static contact angle of water with respect to approximate straight line F ′ x = '′ x + θ ′ (where η ′ and θ ′ are constants) and the number of reciprocations x of the friction element at the maximum number of frictions of 6000 'linear approximation straight line representing the relationship x F''' x = η '''x + θ''' (η ''' and theta''' is a constant) was determined. The equation of the linear approximation straight line is shown in Table 5.
Figure JPOXMLDOC01-appb-T000029
Figure JPOXMLDOC01-appb-T000029
　本発明の基材は、基材の表面において撥水性が求められる様々な分野に用い得る。 The substrate of the present invention can be used in various fields where water repellency is required on the surface of the substrate.

Claims (9)

  1. 　表面にパーフルオロポリエーテル基含有化合物から形成された表面処理層を有する基材であって、
    　２１℃および湿度６５％の雰囲気下において、試験用布（リン酸三ナトリウム５．５ｇ、塩化ナトリウム１０ｇ、乳酸３．１ｇ、リシン５ｇおよび蒸留水１００ｍｌからなる人工汗を浸漬させた、ＩＮＮＯＷＥＰ社製のＡＢＲＥＸ（登録商標）　ｓｔａｎｄａｒｄ　ｃｏｔｔｏｎ　ｓｏｉｌｉｎｇ　ｔｅｘｔｉｌｅ　ＦＩＮＥ）で覆われたシリコーンよりなる摩擦子に、基材に対して５Ｎの荷重がかかるように、負荷をかけながら、該摩擦子を４０ｍｍ／秒の速度で表面上を往復する摩擦試験における、該摩擦子の往復回数０回、１０００回、２０００回、３０００回、および４０００回（ただし、該往復回数は、水の静的接触角の測定値が最初に８０度未満になった回数を最大とする。）での往復回数（回）に対する水の静的接触角の測定値（度）に基づいて作成される線形近似直線の勾配が－０．００９６超である基材。     A substrate having a surface treatment layer formed of a compound containing a perfluoropolyether group on the surface,
    INNOWEP, in which an artificial sweat consisting of test cloth (5.5 g of trisodium phosphate, 10 g of sodium chloride, 10 g of sodium chloride, 3.1 g of lactic acid, 5 g of lysine and 100 ml of distilled water) was soaked under an atmosphere of 21 ° C. and a humidity of 65%. Of a friction member made of silicone covered with ABREX (R) standard cotton soiling textile FINE) with a load of 5 N applied to the substrate, the speed of the friction member being 40 mm / sec. In the friction test that reciprocates on the surface, the number of reciprocations of the friction element in the friction test is 0, 1000, 2000, 3000 and 4000 (however, the number of reciprocations is the first measurement of static contact angle of water) Measure the static contact angle of water (the degree) to the number of round trips (times) at which the number of Substrate slope of the linear approximation line to be created is -0.0096 greater based on.
  2. 　表面にパーフルオロポリエーテル基含有化合物から形成された表面処理層を有する基材であって、
    　２１℃および湿度６５％の雰囲気下において、試験用布（リン酸三ナトリウム５．５ｇ、塩化ナトリウム１０ｇ、乳酸３．１ｇ、リシン５ｇおよび蒸留水１００ｍｌからなる人工汗を浸漬させた、ＩＮＮＯＷＥＰ社製のＡＢＲＥＸ（登録商標）　ｓｔａｎｄａｒｄ　ｃｏｔｔｏｎ　ｓｏｉｌｉｎｇ　ｔｅｘｔｉｌｅ　ＦＩＮＥ）で覆われたシリコーンよりなる摩擦子に、基材に対して５Ｎの荷重がかかるように、負荷をかけながら、該摩擦子を４０ｍｍ／秒の速度で表面上を往復する摩擦試験における、該摩擦子の往復回数４０００回における水の静的接触角の測定値が、８０度以上である、基材。     A substrate having a surface treatment layer formed of a compound containing a perfluoropolyether group on the surface,
    INNOWEP, in which an artificial sweat consisting of test cloth (5.5 g of trisodium phosphate, 10 g of sodium chloride, 10 g of sodium chloride, 3.1 g of lactic acid, 5 g of lysine and 100 ml of distilled water) was soaked under an atmosphere of 21 ° C. and a humidity of 65%. Of a friction member made of silicone covered with ABREX (R) standard cotton soiling textile FINE) with a load of 5 N applied to the substrate, the speed of the friction member being 40 mm / sec. A substrate, wherein the static contact angle of water after 4000 cycles of reciprocation of the friction element in the friction test reciprocated on the surface is 80 degrees or more.
  3. 　往復回数４０００回における水の静的接触角の測定値が、８０度以上である、請求項１に記載の基材。 The substrate according to claim 1, wherein the measured static contact angle of water after 4000 cycles of reciprocation is 80 degrees or more.
  4. 　ＡＳＴＭ　Ｄ４９１７に準拠して測定される動摩擦係数が、０．０５０未満である、請求項１～３のいずれかに記載の基材。 The substrate according to any one of claims 1 to 3, wherein the dynamic friction coefficient measured according to ASTM D4917 is less than 0.050.
  5. 　ＡＳＴＭ　Ｄ４９１７に準拠して測定される動摩擦係数が、０．０３５未満である、請求項１～４のいずれかに記載の基材。 The substrate according to any one of claims 1 to 4, wherein the dynamic friction coefficient measured according to ASTM D4917 is less than 0.035.
  6. 　表面にパーフルオロポリエーテル基含有化合物から形成された表面処理層を有する基材であって、
    　波長３００ｎｍ～４００ｎｍの紫外線が、放射照度６２Ｗ／ｍ２で３００時間照射された表面において、２１℃および湿度６５％の雰囲気下において、試験用布（リン酸三ナトリウム５．５ｇ、塩化ナトリウム１０ｇ、乳酸３．１ｇ、リシン５ｇおよび蒸留水１００ｍｌからなる人工汗を浸漬させた、ＩＮＮＯＷＥＰ社製のＡＢＲＥＸ（登録商標）　ｓｔａｎｄａｒｄ　ｃｏｔｔｏｎ　ｓｏｉｌｉｎｇ　ｔｅｘｔｉｌｅ　ＦＩＮＥ）で覆われたシリコーンよりなる摩擦子に、基材に対して５Ｎの荷重がかかるように、負荷をかけながら、該摩擦子を４０ｍｍ／秒の速度で往復する摩擦試験における、該摩擦子の往復回数０回、１０００回、２０００回、および３０００回（ただし、該往復回数は、水の静的接触角の測定値が最初に測定値が５０度未満になった回数を最大とする。）での往復回数（回）に対する水の静的接触角の測定値（度）に基づいて作成される線形近似直線の勾配が－０．０２２２超である基材。     A substrate having a surface treatment layer formed of a compound containing a perfluoropolyether group on the surface,
    Test cloth (5.5 g of trisodium phosphate, 10 g of sodium chloride, at an atmosphere of 21 ° C. and a humidity of 65% on a surface irradiated with ultraviolet light of wavelength 300 nm to 400 nm at an irradiance of 62 W / m 2 for 300 hours A friction member made of silicone covered with INNOWEP's ABREX (R) standard cotton soiling textile FINE) impregnated with artificial sweat consisting of 3.1 g of lactic acid, 5 g of lysine and 100 ml of distilled water In the friction test in which the friction element is reciprocated at a speed of 40 mm / sec while applying a load such that a load of 5 N is applied, the number of reciprocations of the friction element is zero, 1000, 2000 and 3000 The number of reciprocations is that the static water contact angle measurement value is not 50 degrees at first. A group of linear approximations with a slope greater than -0.0222, based on the measured value of the static contact angle of water (degrees) with respect to the number of round trips (times) Material.
  7. 　往復回数３０００回における水の静的接触角の測定値が、５０度以上である、請求項６に記載の基材。 The substrate according to claim 6, wherein the measured static contact angle of water after 3,000 reciprocations is 50 degrees or more.
  8. 　ＡＳＴＭ　Ｄ４９１７に準拠して測定される動摩擦係数が、０．０５０未満である、請求項６または７に記載の基材。 The substrate according to claim 6 or 7, wherein the dynamic friction coefficient measured according to ASTM D4917 is less than 0.050.
  9. 　ＡＳＴＭ　Ｄ４９１７に準拠して測定される動摩擦係数が、０．０３５未満である、請求項６～８のいずれか１項に記載の基材。 The substrate according to any one of claims 6 to 8, wherein the dynamic friction coefficient measured according to ASTM D4917 is less than 0.035.
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