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WO2019098230A1 - Matériau de base - Google Patents

Matériau de base Download PDF

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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
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2018/042110
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English (en)
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
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Daikin Industries Ltd
Original Assignee
Daikin Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Daikin Industries Ltd filed Critical Daikin Industries Ltd
Publication of WO2019098230A1 publication Critical patent/WO2019098230A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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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  • Surface Treatment Of Glass (AREA)

Abstract

La présente invention concerne un matériau de base ayant, mise en œuvre sur la surface, une couche de traitement de surface formée à partir d'un composé contenant un groupe perfluoropolyéther, dans lequel le gradient d'une ligne droite d'approximation linéaire, qui est créée sur la base de valeurs de mesure (degrés) de l'angle de contact statique de l'eau par rapport au nombre de fois (fois) qu'un élément de friction est déplacé en va-et-vient, à savoir 0 fois, 1000 fois, 2000 fois, 3000 fois, et 4000 fois (sous réserve que, au nombre maximum de fois, la valeur de mesure de l'angle de contact statique de l'eau est initialement inférieure à 80 degrés), dans un test de frottement dans lequel l'élément de frottement est déplacé en va-et-vient sur la surface du matériau de base à une vitesse de 40 mm/sec, dans une atmosphère ayant une température de 21 °C et une humidité de 65 %, tout en appliquant une charge sur l'élément de frottement de telle sorte qu'une charge de 5N est appliquée sur le matériau de base, est supérieur à -0,0096. L'élément de frottement est formé à partir de silicone qui a été recouverte d'un tissu de test (textile salissant en coton standard FINE ABREX (marque déposée) qui est fabriqué par INNOWEP, et qui a été trempé dans une sueur synthétique comprenant 5,5 g de phosphate trisodique, 10 g de chlorure de sodium, 3,1 g d'acide lactique, 5g de lysine, et 100 ml d'eau distillée).
PCT/JP2018/042110 2017-11-15 2018-11-14 Matériau de base Ceased WO2019098230A1 (fr)

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