WO2023140105A1 - Article antisalissure - Google Patents

Article antisalissure Download PDF

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Publication number
WO2023140105A1
WO2023140105A1 PCT/JP2023/000026 JP2023000026W WO2023140105A1 WO 2023140105 A1 WO2023140105 A1 WO 2023140105A1 JP 2023000026 W JP2023000026 W JP 2023000026W WO 2023140105 A1 WO2023140105 A1 WO 2023140105A1
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Prior art keywords
independently
group
occurrence
integer
formula
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PCT/JP2023/000026
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English (en)
Japanese (ja)
Inventor
真介 大下
健 前平
真人 内藤
真奈美 片岡
尚志 三橋
孝史 野村
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ダイキン工業株式会社
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Priority to CN202380014974.2A priority Critical patent/CN118369206A/zh
Publication of WO2023140105A1 publication Critical patent/WO2023140105A1/fr

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    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • 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
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides

Definitions

  • the present disclosure relates to antifouling articles.
  • a layer obtained from a surface treatment agent containing a fluorine-containing silane compound (hereinafter also referred to as a "surface treatment layer") is provided as a so-called functional thin film on various substrates such as glass, plastic, fiber, sanitary goods, and building materials (Patent Documents 1 and 2).
  • the fluorine-containing silane compound described in Patent Document 1 or Patent Document 2 can provide a surface treatment layer having excellent functions, but there is a demand for an article having a surface treatment layer with higher friction durability.
  • An object of the present disclosure is to provide an article having a surface treatment layer with higher friction durability.
  • the present disclosure includes the following aspects. [1] a substrate; an intermediate layer located on the substrate; a surface treatment layer positioned on the intermediate layer and formed of a surface treatment agent containing a fluorine-containing silane compound; The article, wherein the intermediate layer comprises a Ce-containing layer. [2] The article according to [1] above, wherein the Ce-containing layer further contains Si. [3] The article according to [1] or [2] above, wherein the Ce-containing layer includes a composite oxide containing Si and Ce. [4] The article according to [2] or [3] above, wherein the Ce-containing layer has a molar ratio of Si to Ce of 10:90 to 99.99:0.01.
  • the intermediate layer further contains an alkali metal or alkaline earth metal.
  • the concentration of the alkali metal and alkaline earth metal in the intermediate layer is 0.1 to 30 mol %.
  • the Ce-containing layer has a thickness of 0.1 to 100 nm.
  • the intermediate layer comprises a Ce-containing layer.
  • the intermediate layer further includes a silicon oxide layer on the Ce-containing layer.
  • each R F1 is independently Rf 1 —R F —O q —;
  • R F2 is -Rf 2 p -R F -O q -;
  • each Rf 1 is independently a C 1-16 alkyl group optionally substituted by one or more fluorine atoms;
  • Rf 2 is a C 1-6 alkylene group optionally substituted by one or more fluorine atoms;
  • each R F is independently a divalent fluoropolyether group;
  • p is 0 or 1;
  • each q is independently 0 or 1;
  • R Si is each independently a monovalent group containing a Si atom to which a hydroxyl group, a hydrolyzable group, a hydrogen atom or a monovalent organic group is bonded; at least one R Si is a monovalent organic group is bonded; at least one R Si is a monovalent organic group is bonded; at least one R Si is a monovalent organic group is bonded; at least one R Si
  • R F is each independently represented by the formula: - (OC 6 F 12 ) a - (OC 5 F 10 ) b - (OC 4 F 8 ) c - (OC 3 R Fa 6 ) d - (OC 2 F 4 ) e - (OCF 2 ) f - [Wherein, each R Fa is independently a hydrogen atom, a fluorine atom or a chlorine atom, a, b, c, d, e and f are each independently an integer of 0 to 200, the sum of a, b, c, d, e and f is 1 or more, and the order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e or f in the formula is arbitrary.
  • R Fa is a fluorine atom.
  • R F is, at each occurrence independently, the following formula (f1), (f2), (f3), (f4), (f5) or (f6): -(OC 3 F 6 ) d -(OC 2 F 4 ) e - (f1) [Wherein, d is an integer of 1 to 200, and e is 0 or 1.
  • c and d are each independently an integer of 0 to 30; e and f are each independently an integer from 1 to 200; the sum of c, d, e and f is an integer from 10 to 200; The order of existence of each repeating unit bracketed with subscript c, d, e or f is arbitrary in the formula.
  • R 6 is OCF 2 or OC 2 F 4 ;
  • R7 is a group selected from OC2F4 , OC3F6 , OC4F8 , OC5F10 and OC6F12 , or a combination of two or three groups selected from these groups;
  • g is an integer from 2 to 100;
  • R 6 is OCF 2 or OC 2 F 4 ;
  • R7 is a group selected from OC2F4 , OC3F6 , OC4F8 , OC5F10 and OC6F12 or a combination of two or three groups independently selected from these groups;
  • R 6' is OCF 2 or OC 2 F 4 ;
  • R 7′ is a group selected from OC 2 F 4 , OC 3 F 6 ,
  • e is an integer of 1 or more and 200 or less
  • a, b, c, d and f are each independently an integer of 0 or more and 200 or less, and the order of existence of each repeating unit bracketed with a, b, c, d, e or f is arbitrary in the formula.
  • f is an integer of 1 or more and 200 or less
  • a, b, c, d and e are each independently an integer of 0 or more and 200 or less, and the order of existence of each repeating unit bracketed with a, b, c, d, e or f is arbitrary in the formula.
  • R Si is represented by the following formula (S1), (S2), (S3), (S4) or (S5): [In the formula: R 11 is independently at each occurrence a hydroxyl group or a hydrolyzable group; R 12 is independently at each occurrence a hydrogen atom or a monovalent organic group; n1 is an integer of 0 to 3 independently for each (SiR 11 n1 R 12 3-n1 ) unit; X 11 is independently at each occurrence a single bond or a divalent organic group; R 13 is independently at each occurrence a hydrogen atom or a monovalent organic group; t is independently at each occurrence an integer greater than or equal to 2; R 14 is independently at each occurrence a hydrogen atom, a halogen atom or —X 11 —SiR 11 n1 R 12 3-n1 ; each occurrence of R 15 is independently a single bond, an oxygen atom,
  • X A is each independently a single bond or a divalent organic group, The article according to any one of [11] to [15] above, wherein ⁇ , ⁇ , and ⁇ are 1.
  • X A is each independently a trivalent organic group, ⁇ is 1 and ⁇ is 2, or ⁇ is 2 and ⁇ is 1, ⁇ is 2; The article according to any one of [11] to [15] above.
  • [18] The article according to any one of [1] to [17] above, wherein the substrate is a glass substrate.
  • Articles of the present disclosure comprise a substrate, an intermediate layer positioned on the substrate; a surface treatment layer formed from a surface treatment agent containing a fluorine-containing silane compound located on the intermediate layer;
  • the intermediate layer includes a Ce-containing layer.
  • Substrates that can be used in the present disclosure include, for example, glass, resin (natural or synthetic resin, such as general plastic materials), metals, ceramics, semiconductors (silicon, germanium, etc.), fibers (textiles, non-woven fabrics, etc.), fur, leather, wood, ceramics, stones, etc., building members, etc., sanitary products, and any appropriate material.
  • resin natural or synthetic resin, such as general plastic materials
  • metals ceramics
  • semiconductors silicon, germanium, etc.
  • fibers textiles, non-woven fabrics, etc.
  • fur leather, wood, ceramics, stones, etc., building members, etc.
  • sanitary products and any appropriate material.
  • the material forming the surface of the substrate may be a material for optical members, such as glass or transparent plastic.
  • some layer such as a hard coat layer or an antireflection layer may be formed on the surface (outermost layer) of the substrate.
  • the antireflection layer may be either a single antireflection layer or a multi-layer antireflection layer.
  • inorganic materials that can be used for the antireflection layer include SiO2 , SiO, ZrO2, TiO2 , TiO, Ti2O3 , Ti2O5 , Al2O3 , Ta2O5 , Ta3O5 , Nb2O5, HfO2, Si3N4 , CeO2 , MgO , Y 2 O 3 , SnO 2 , MgF 2 , WO 3 and the like.
  • inorganic substances may be used alone or in combination of two or more (for example, as a mixture).
  • SiO 2 and/or SiO for the outermost layer.
  • a transparent electrode such as a thin film using indium tin oxide (ITO) or indium zinc oxide, may be provided on a part of the surface of the substrate (glass).
  • the substrate may have 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 retardation film, a liquid crystal display module, and the like, depending on its specific specifications.
  • the surface of the substrate does not have any layer as described above. That is, the intermediate layer is provided in direct contact with the substrate.
  • the shape of the base material is not particularly limited, and may be, for example, plate-like, film, or other forms.
  • the surface region of the base material on which the surface treatment layer is to be formed may be at least part of the surface of the base material, and can be appropriately determined according to the application and specific specifications of the article to be manufactured.
  • At least the surface portion of such a substrate may consist of a material that originally has hydroxyl groups.
  • materials include glass, metals (particularly base metals), ceramics, and semiconductors on which a natural oxide film or thermal oxide film is formed.
  • hydroxyl groups can be introduced or increased on the surface of the base material by subjecting the base material to some pretreatment.
  • pretreatment include plasma treatment (eg, corona discharge) and ion beam irradiation. Plasma treatment can introduce or increase hydroxyl groups on the substrate surface, and can also be suitably used to clean the substrate surface (remove foreign matter and the like).
  • Another example of such a pretreatment is a method in which an interfacial adsorbent having a carbon-carbon unsaturated bond group is formed in advance in the form of a monomolecular film on the substrate surface by the LB method (Langmuir-Blodgett method), a chemisorption method, or the like, and then the unsaturated bond is cleaved in an atmosphere containing oxygen, nitrogen, or the like.
  • At least the surface portion of such a substrate may consist of a material containing another reactive group, such as a silicone compound having one or more Si—H groups, or an alkoxysilane.
  • the substrate is glass.
  • glass sapphire glass, soda lime glass, alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass, and quartz glass are preferable, and chemically strengthened soda lime glass, chemically strengthened alkali aluminosilicate glass, and chemically bonded borosilicate glass are particularly preferable.
  • the intermediate layer is positioned on the base material.
  • the durability of the surface treatment layer can be improved.
  • Durability means weather resistance, abrasion resistance, and the like.
  • the intermediate layer may be formed in contact with the base material, or may be formed on the base material via another layer. In a preferred embodiment, the intermediate layer is formed in contact with the substrate.
  • the intermediate layer includes a Ce-containing layer.
  • a Ce-containing layer means a layer containing cerium (Ce) atoms.
  • the Ce is preferably contained in the Ce-containing layer as an oxide.
  • the oxide may be a composite oxide with other metal atoms.
  • composite oxides include oxides of multiple elements forming a homogeneous phase, so-called solid solutions, as well as oxides of multiple elements forming a heterogeneous phase.
  • the composite oxide is preferably composed of a solid solution forming a homogeneous phase.
  • the Ce-containing layer is made of cerium oxide.
  • the cerium oxide may contain those with different oxidation states.
  • the cerium oxide is CeO2 .
  • the Ce-containing layer may further contain other metal atoms. These metal atoms may exist as individual oxides, or may exist as composite oxides with Ce or as composite oxides containing no Ce.
  • metal atoms also include metalloid atoms such as B, Si, Ge, Sb, As, and Te.
  • the other metal atoms may be, for example, one or more atoms selected from transition metals of Groups 3 to 11 and typical metal elements of Groups 12 to 15 of the periodic table.
  • the other metal atoms are preferably group 3 to group 11 transition metal atoms, more preferably group 3 to group 7 transition metal atoms, and still more preferably group 4 to 6 transition metal atoms.
  • the other metal atoms may be one or more metal atoms selected from the group consisting of Si, Y, Ru, In, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc, and Bi.
  • the Ce-containing layer further contains Si.
  • the Ce and Si are contained in the Ce-containing layer as composite oxides. That is, the Ce-containing layer contains a composite oxide containing Ce and Si.
  • the Ce and Si are contained in the Ce-containing layer as separate oxides.
  • the oxides may include those with different oxidation states.
  • the cerium oxide is CeO2 and the silicon oxide is SiO2 .
  • the metal atoms contained in the Ce-containing layer are substantially only Si and Ce.
  • the metal atoms contained in the Ce-containing layer are substantially only Si and Ce" allow the Ce-containing layer to contain other metal atoms as unavoidable minor components.
  • the molar ratio of Si and Ce in the Ce-containing layer can be 10:90-99.99:0.01 (Si:Ce), preferably 40:60-99.99:0.01, more preferably 60:40-99:1, even more preferably 90:10-99:1, and particularly preferably 90:10-98:2.
  • Si:Ce 10:90-99.99:0.01
  • the durability of the surface treatment layer is improved.
  • the molar ratio of Si and Ce may be the average value.
  • the composition and ratio of the intermediate layer such as the Ce-containing layer can be determined by surface analysis.
  • a surface analysis method X-ray photoelectron spectroscopy, time-of-flight secondary ion mass spectrometry, or the like can be used. Typically, X-ray photoelectron spectroscopy is used.
  • XPS X-ray photoelectron spectroscopy
  • the measurement conditions for the XPS analysis include a monochromatic AlK ⁇ ray of 25 W for the X-ray source, a photoelectron detection area of 1400 ⁇ m ⁇ 300 ⁇ m, a photoelectron detection angle of 20 degrees to 90 degrees (for example, 20 degrees, 45 degrees, and 90 degrees), a pass energy of 23.5 eV, and Ar ions as the sputtered ions.
  • the composition of the laminate can be obtained by observing the peak areas of C1s, O1s, F1s, Si2p orbitals, and appropriate orbitals of other metals, and calculating the atomic ratios of carbon, oxygen, fluorine, silicon, and other metals using the above apparatus and measurement conditions.
  • Suitable orbitals for other metals include, for example, the 1s orbital for atomic number 5 (B), the 2p orbital for atomic numbers 13-14, 21-31 (Al-Si, Sc-Ga), the 3d orbital for atomic numbers 32-33, 39-52, and 58 (Ge-As, Y-Te, Ce), and the 4f orbital for atomic numbers 72-83 (Hf-Bi).
  • the measurement conditions for the XPS analysis are as follows: monochromatic AlK ⁇ rays at 25 W are used as the X-ray source, the photoelectron detection area is 1400 ⁇ m ⁇ 300 ⁇ m, the photoelectron detection angle is in the range of 20 degrees to 90 degrees (eg, 20 degrees, 45 degrees, 90 degrees), the pass energy is 23.5 eV, and Ar ions can be used as the sputtered ions.
  • the intermediate layer is etched 1 to 100 nm in terms of SiO 2 by sputtering with Ar ions, and the peak areas of O1s, Si2p orbitals, and appropriate orbitals of other metals are observed at each depth after etching, and the composition inside the intermediate layer can be obtained by calculating the atomic ratios of oxygen, silicon, and other metals.
  • Suitable orbitals for other metals include, for example, the 1s orbital for atomic number 5 (B), the 2p orbital for atomic numbers 13-14, 21-31 (Al-Si, Sc-Ga), the 3d orbital for atomic numbers 32-33, 39-52, and 58 (Ge-As, Y-Te, Ce), and the 4f orbital for atomic numbers 72-83 (Hf-Bi).
  • the detection depth can be adjusted as appropriate. For example, a shallow angle close to 20 degrees allows the detection depth to be about 3 nm, while a deep angle close to 90 degrees allows the detection depth to be about 10 and several nm.
  • the composition of the intermediate layer can be calculated by calculating the detected amount of Si in the base material from the detected amount of specific atoms in the base material, for example, when the base material is glass, metal atoms (e.g., Al, Na, K, B, Ca, Mg, Sn, etc.) contained in trace amounts, and subtracting it from the measurement results.
  • metal atoms e.g., Al, Na, K, B, Ca, Mg, Sn, etc.
  • the intermediate layer may further contain an alkali metal or an alkaline earth metal, preferably an alkali metal.
  • an alkali metal in the intermediate layer, the friction durability, weather resistance, etc. of the surface treatment layer are improved.
  • the alkali metal and alkaline earth metal contained in the intermediate layer may be contained in the Ce-containing layer, may be contained in another layer, or may be contained in both of these layers.
  • the alkali metal and alkaline earth metal in the intermediate layer may exist uniformly, or may segregate on the surface of the intermediate layer (surface treatment layer side). Preferably, the alkali metal and alkaline earth metal in the intermediate layer are segregated on the surface of the intermediate layer.
  • the above alkali metals include Li, Na, K, Rb, Cs, and Fr.
  • the alkali metal is preferably Na or K, more preferably Na.
  • the alkaline earth metals include Be, Mg, Ca, Sr, Ba, and Ra.
  • the alkali metal is preferably Mg or Ca.
  • the content of alkali metals and alkaline-earth metals in the intermediate layer is not particularly limited, but can be preferably 0.1 to 30 mol%, more preferably 0.1 to 20 mol%, still more preferably 0.1 to 15 mol%, still more preferably 0.5 to 15 mol%, for example, 1.0 to 15 mol% or 1.0 to 10 mol%, based on the total of all metal atoms contained in the intermediate layer.
  • the friction durability of the surface treatment layer is further improved.
  • the intermediate layer may be a single layer or multiple layers.
  • the boundary between layers in the intermediate layer is a portion where the composition clearly differs in the thickness direction, and the layers above and below the boundary are regarded as different layers.
  • a portion where the composition gradually changes with a gradient in the thickness direction is not a boundary, but is regarded as one layer.
  • the intermediate layer is a single layer.
  • the intermediate layer is a single layer
  • the intermediate layer is a Ce-containing layer.
  • the Ce-containing layer preferably contains Si and Ce.
  • Si atoms are preferably present on the surface in contact with the surface treatment layer.
  • the concentration gradient of Si preferably increases gradually toward the surface treatment layer side.
  • the concentration gradient of Si preferably increases gradually toward the surface treatment layer side.
  • the intermediate layer is multilayer.
  • the intermediate layer When the intermediate layer is multi-layered, the intermediate layer includes a Ce-containing layer and a Si-containing layer.
  • the intermediate layer consists of a Ce-containing layer and a Si-containing layer.
  • the intermediate layer further includes a Si-containing layer on the Ce-containing layer. That is, the intermediate layer includes a Ce-containing layer located on the substrate side and a Si-containing layer located on the Ce-containing layer and in contact with the surface treatment layer.
  • the intermediate layer consists of a Ce-containing layer located on the substrate and a Si-containing layer located in direct contact with the Ce-containing layer.
  • the thickness of the intermediate layer (in the case of multiple layers, the total thickness of all layers) is not particularly limited, but can be, for example, 1.0 nm or more, preferably 2.0 nm or more, and more preferably 3.0 nm or more. By setting the thickness of the intermediate layer to 1.0 nm or more, the effect of improving the friction durability and weather resistance of the surface treatment layer can be obtained more reliably.
  • the thickness of the intermediate layer (in the case of multiple layers, the total thickness of all layers) is not particularly limited, but may be, for example, 120 nm or less, preferably 60 nm or less, more preferably 25 nm or less, even more preferably 15 nm or less, and particularly preferably 10 nm or less.
  • the thickness of the intermediate layer can be preferably 1.0 to 120 nm, more preferably 2.0 to 60 nm, even more preferably 2.0 to 25 nm, still more preferably 3.0 nm to 10 nm.
  • the thickness of the Ce-containing layer is not particularly limited, it can be, for example, 0.1 nm or more, preferably 1.0 nm or more, more preferably 2.0 nm or more, and still more preferably 3.0 nm or more.
  • the thickness of the Ce-containing layer is not particularly limited, but may be, for example, 100 nm or less, preferably 50 nm or less, more preferably 20 nm or less, even more preferably 10 nm or less, and particularly preferably 5 nm or less.
  • the Ce-containing layer may preferably have a thickness of 0.1 to 100 nm, more preferably 1.0 to 50 nm, even more preferably 2.0 to 20 nm, still more preferably 3.0 nm to 10 nm.
  • the thickness of the layer containing other metals is not particularly limited, but may be, for example, 0.1 nm or more, preferably 1.0 nm or more, more preferably 2.0 nm or more, and even more preferably 3.0 nm or more.
  • the thickness of the layer containing the other metal is not particularly limited, but may be, for example, 100 nm or less, preferably 50 nm or less, more preferably 20 nm or less, even more preferably 10 nm or less, and particularly preferably 5 nm or less.
  • the thickness of the layer containing the other metal may preferably be 0.1-100 nm, more preferably 1.0-50 nm, still more preferably 2.0-20 nm, still more preferably 3.0-10 nm.
  • the thickness of the Si-containing layer is not particularly limited, but may be, for example, 0.1 nm or more, preferably 1.0 nm or more, more preferably 2.0 nm or more, and even more preferably 3.0 nm or more.
  • the thickness of the Si-containing layer is not particularly limited, but may be, for example, 100 nm or less, preferably 50 nm or less, more preferably 20 nm or less, even more preferably 10 nm or less, and particularly preferably 5 nm or less.
  • the thickness of the Si-containing layer can be preferably 0.1-100 nm, more preferably 1.0-50 nm, even more preferably 2.0-20 nm, still more preferably 3.0-10 nm.
  • the intermediate layer comprises a Ce-containing layer positioned on the substrate and a Si-containing layer positioned in direct contact with the Ce-containing layer, the Ce-containing layer having a thickness of 0.1 to 20 nm, preferably 1.0 to 10 nm, and the Si-containing layer having a thickness of 0.1 to 20 nm, preferably 1.0 to 10 nm.
  • each layer can be measured by combining XPS analysis and sputtering. Specifically, the thickness of the layer can be measured by analyzing the depth direction and measuring the depth of the sputtering ring with the location where the composition clearly changes as the boundary of each layer.
  • the method for forming the intermediate layer is not particularly limited, for example, sputtering, ion beam assist, vacuum deposition (preferably electron beam heating method), CVD (chemical vapor deposition), atomic layer deposition, etc. can be used, and vacuum deposition or sputtering is preferably used.
  • sputtering method a sputtering method using a DC (direct current) sputtering method, an AC (alternating current) sputtering method, an RF (radio frequency) sputtering method, an RAS (radical assist) sputtering method, or the like can be used.
  • DC direct current
  • AC alternating current
  • RF radio frequency
  • RAS radio assist
  • the substrate When forming a film by a sputtering method, the substrate is placed in a chamber with a mixed gas atmosphere of inert gas and oxygen gas, and a target is selected as the intermediate layer forming material so as to have a desired composition to form the film.
  • the type of inert gas in the chamber is not particularly limited, and various inert gases such as argon and helium can be used.
  • the pressure in the chamber due to the mixed gas of inert gas and oxygen gas is not particularly limited, but it is easy to set the surface roughness of the film to be formed within a preferable range by setting it in the range of 0.5 Pa or less. This is considered to be due to the reason shown below. That is, when the pressure in the chamber due to the mixed gas of the inert gas and the oxygen gas is 0.5 Pa or less, the mean free path of the film-forming molecules is ensured, and the film-forming molecules reach the substrate with more energy. Therefore, rearrangement of the film-forming molecules is promoted, and it is considered that a film having a relatively dense and smooth surface can be formed.
  • the lower limit of the pressure in the chamber due to the mixed gas of inert gas and oxygen gas is not particularly limited, but is preferably 0.1 Pa or more, for example.
  • a film-forming material containing cerium oxide is used in the film-forming method for the intermediate layer.
  • the film-forming material contains silicon oxide and cerium oxide.
  • the molar ratio of silicon atoms to cerium atoms is preferably 10:90 to 99.99:0.01 (Si:Ce), more preferably 10:90 to 99:1, still more preferably 10:90 to 95:5, even more preferably 20:80 to 90:10, and particularly preferably 40:60 to 80:20.
  • Si:Ce silicon:90 to 99.99:0.01
  • the durability of the surface treatment layer is improved.
  • Preparation of film-forming material Specific examples of the form of the film-forming material include powder, melt, sintered body, granules, and crushed bodies, and from the viewpoint of handleability, melts, sintered bodies, and granules are preferable.
  • the melt means a solid obtained by melting the film-forming material powder at a high temperature and then cooling and solidifying it.
  • the sintered body means a solid obtained by firing the powder of the film-forming material, and if necessary, instead of the powder of the film-forming material, the powder may be pressed to form a compact.
  • a granule means a solid obtained by kneading a powder of a film-forming material and a liquid medium (for example, water or an organic solvent) to obtain particles, and then drying the particles.
  • the film-forming material can be manufactured, for example, by the following method. - A method of mixing silicon oxide powder and cerium oxide powder to obtain a film-forming material powder. - A method of obtaining granules of the film-forming material by kneading the powder of the film-forming material and water to obtain particles, followed by drying the particles.
  • silicon for example, powder made of silicon oxide, silica sand, silica gel
  • cerium oxide for example, powder of cerium oxide, carbonate, sulfate, nitrate, oxalate, hydroxide
  • a method of obtaining a melt by melting a powder containing silicon (e.g., powder of silicon oxide, silica sand, silica gel) and a powder containing cerium (e.g., cerium oxide powder, carbonate, sulfate, nitrate, oxalate, hydroxide) at high temperature and then cooling and solidifying the melt.
  • a method of obtaining a sintered body by reacting an alkoxide or chloride containing silicon (e.g. tetramethoxysilane, tetraethoxysilane, tetraisopropylsilane, tetrachlorosilane) with an alkoxide containing cerium (e.g.
  • cerium isopropoxide and water, and drying the resulting oxide solid, followed by press molding and firing.
  • a method of obtaining a sintered body by reacting either one of silicon and cerium with an oxide in the case of using the above alkoxide, drying the obtained oxide solid, press-molding it, and then sintering it. etc. can be considered.
  • the film-forming material further contains an alkali metal or alkaline earth metal, preferably an alkali metal, in addition to silicon oxide and cerium oxide.
  • the above alkali metals and alkaline earth metals are contained in the form of ions, oxides, or salts.
  • the above alkali metals and alkaline earth metals are contained in an amount of preferably 0.1 to 30 mol%, more preferably 0.1 to 20 mol%, still more preferably 0.1 to 15 mol%, still more preferably 0.5 to 15 mol%, for example 1.0 to 15 mol% or 1.0 to 10 mol%, based on the total amount of silicon atoms, cerium atoms and alkali metals and alkaline earth metals.
  • concentration of the alkali metal in the film forming material within the above range, the friction durability, weather resistance, etc. of the surface treatment layer are improved.
  • the film-forming material is a vapor deposition material.
  • the surface treatment layer is located on the intermediate layer.
  • the surface treatment layer is positioned directly above the intermediate layer, that is, in contact with the intermediate layer.
  • the surface treatment layer can be formed from a surface treatment agent containing a fluorine-containing silane compound.
  • monovalent organic group means a monovalent group containing carbon.
  • the monovalent organic group is not particularly limited, it may be a hydrocarbon group or a derivative thereof.
  • a derivative of a hydrocarbon group means a group having one or more of N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc. at the end of the hydrocarbon group or in the molecular chain.
  • organic group when it shows simply as an "organic group”, it means a monovalent organic group.
  • the “divalent to decavalent organic group” means a divalent to decavalent group containing carbon.
  • Such a divalent to decavalent organic group is not particularly limited, but includes a divalent to decavalent group in which 1 to 9 hydrogen atoms are further eliminated from an organic group.
  • the divalent organic group is not particularly limited, but includes a divalent group in which one hydrogen atom is further eliminated from the organic group.
  • hydrocarbon group means a group containing carbon and hydrogen from which one hydrogen atom has been removed from a hydrocarbon.
  • Such hydrocarbon groups include, but are not limited to, C 1-20 hydrocarbon groups, such as aliphatic hydrocarbon groups, aromatic hydrocarbon groups, etc., which may be substituted with one or more substituents.
  • the above “aliphatic hydrocarbon group” may be linear, branched or cyclic, and may be saturated or unsaturated. Hydrocarbon groups may also contain one or more ring structures.
  • the substituents of the "hydrocarbon group” are not particularly limited, but for example, a halogen atom, a C 1-6 alkyl group optionally substituted by one or more halogen atoms, a C 2-6 alkenyl group, a C 2-6 alkynyl group, a C 3-10 cycloalkyl group, a C 3-10 unsaturated cycloalkyl group, a 5- to 10-membered heterocyclyl group, a 5- to 10-membered unsaturated heterocyclyl group, C One or more groups selected from 6-10 aryl groups and 5-10 membered heteroaryl groups are included.
  • hydrolyzable group means a group capable of undergoing a hydrolysis reaction, ie, a group capable of being detached from the backbone of a compound by a hydrolysis reaction.
  • the fluorine-containing silane compound is represented by the following formula (1) or (2): [In the formula: R F1 is independently at each occurrence Rf 1 -R F -O q -; R F2 is -Rf 2 p -R F -O q -; Rf 1 is independently at each occurrence a C 1-16 alkyl group optionally substituted by one or more fluorine atoms; Rf 2 is a C 1-6 alkylene group optionally substituted by one or more fluorine atoms; R F is independently at each occurrence a divalent fluoropolyether group; p is 0 or 1; q is independently 0 or 1 at each occurrence; R Si is independently at each occurrence a monovalent group comprising a Si atom bonded with a hydroxyl group, a hydrolyzable group, a hydrogen atom or a monovalent organic group; at least one R Si is a monovalent group comprising a Si atom to which a hydroxyl group or a hydro
  • each occurrence of R F1 is independently Rf 1 —R F —O q —.
  • R F2 is -Rf 2 p -R F -O q -.
  • Rf 1 at each occurrence is independently a C 1-16 alkyl group optionally substituted by one or more fluorine atoms.
  • the "C 1-16 alkyl group" in the C 1-16 alkyl group optionally substituted by one or more fluorine atoms may be linear or branched, preferably a linear or branched C 1-6 alkyl group, particularly a C 1-3 alkyl group, more preferably a linear C 1-6 alkyl group, particularly a C 1-3 alkyl group.
  • Rf 1 above is preferably a C 1-16 alkyl group substituted with one or more fluorine atoms, more preferably a CF 2 H—C 1-15 perfluoroalkylene group, still more preferably a C 1-16 perfluoroalkyl group.
  • the C 1-16 perfluoroalkyl group may be linear or branched, preferably a linear or branched C 1-6 perfluoroalkyl group, especially a C 1-3 perfluoroalkyl group, more preferably a linear C 1-6 perfluoroalkyl group, especially a C 1-3 perfluoroalkyl group, specifically -CF 3 , -CF 2 CF 3 or -CF 2 CF 2 CF. 3 .
  • Rf 2 is a C 1-6 alkylene group optionally substituted by one or more fluorine atoms.
  • C 1-6 alkylene group in the C 1-6 alkylene group optionally substituted by one or more fluorine atoms may be linear or branched, preferably a linear or branched C 1-3 alkylene group, more preferably a linear C 1-3 alkylene group.
  • Rf 2 above is preferably a C 1-6 alkylene group substituted with one or more fluorine atoms, more preferably a C 1-6 perfluoroalkylene group, still more preferably a C 1-3 perfluoroalkylene group.
  • the C 1-6 perfluoroalkylene group may be linear or branched, preferably a linear or branched C 1-3 perfluoroalkylene group, more preferably a linear C 1-3 perfluoroalkylene group, specifically -CF 2 -, -CF 2 CF 2 -, or -CF 2 CF 2 CF 2 -.
  • p is 0 or 1. In one aspect, p is zero. In another aspect, p is 1.
  • q is 0 or 1 independently at each occurrence. In one aspect, q is zero. In another aspect q is 1.
  • each occurrence of RF is independently a divalent fluoropolyether group.
  • R F is preferably: - (OC h1 R Fa 2h1 ) h3 - (OC h2 R Fa 2h2-2 ) h4 -
  • R Fa is independently at each occurrence a hydrogen atom, a fluorine atom, or a chlorine atom
  • h1 is an integer from 1 to 6
  • h2 is an integer from 4 to 8
  • h3 is an integer of 0 or more
  • h4 is an integer of 0 or more
  • the composition of h3 and h4 is 1 or more, preferably 2 or more, more preferably 5 or more
  • the order of existence of each repeating unit enclosed in parentheses with h3 and h4 is arbitrary in the formula.
  • It may contain a group represented by
  • R F can be linear or branched.
  • R F preferably has the formula: - (OC 6 F 12 ) a - (OC 5 F 10 ) b - (OC 4 F 8 ) c - (OC 3 R Fa 6 ) d - (OC 2 F 4 ) e - (OCF 2 ) f - [In the formula: R Fa is independently at each occurrence a hydrogen atom, a fluorine atom, or a chlorine atom; a, b, c, d, e and f are each independently integers from 0 to 200, and the sum of a, b, c, d, e and f is 1 or more.
  • each repeating unit bracketed with a, b, c, d, e or f is arbitrary in the formula. However, when all RFa are hydrogen atoms or chlorine atoms, at least one of a, b, c, e and f is 1 or more. ] is a group represented by
  • RFa is preferably a hydrogen atom or a fluorine atom, more preferably a fluorine atom. However, when all RFa are hydrogen atoms or chlorine atoms, at least one of a, b, c, e and f is 1 or more.
  • a, b, c, d, e and f may preferably each independently be an integer from 0 to 100.
  • the sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, and may be, for example, 15 or more or 20 or more.
  • the sum of a, b, c, d, e and f is preferably 200 or less, more preferably 100 or less, still more preferably 60 or less, and may be, for example, 50 or less or 30 or less.
  • repeating units may be linear or branched.
  • -( OC6F12 )- is -( OCF2CF2CF2CF2CF2 )-, -(OCF(CF3 ) CF2CF2CF2CF2)-, -( OCF2CF ( CF3)CF2CF2CF2) -, -(OCF 2 CF 2 CF(CF 3 )CF 2 CF 2 ) - , - ( OCF 2 CF 2 CF 2 CF ( CF 3 ) CF 2 ) - , -(OCF 2 CF 2 CF 2 CF 2 CF (CF 3 ))-, and the like.
  • -( OC5F10 )- is -( OCF2CF2CF2CF2 ) -, -(OCF( CF3 ) CF2CF2CF2 )-, -( OCF2CF ( CF3)CF2CF2)-, -(OCF2CF2CF (CF 3 ) CF 2 ) - , -( OCF 2 CF 2 CF 2 CF ( CF 3 ) )-, and the like.
  • -( OC4F8 )- is -( OCF2CF2CF2CF2 )-, -(OCF ( CF3) CF2CF2 ) -, -(OCF2CF( CF3 )CF2)-, -(OCF2CF2CF( CF3 ) )-, -(OC(C F 3 ) 2 CF 2 )-, -( OCF 2 C ( CF 3 ) 2 ) -, -(OCF( CF 3 ) CF(CF 3 ))-, -(OCF(C 2 F 5 )CF 2 )- and -(OCF 2 CF(C 2 F 5 ))-.
  • -(OC 3 F 6 )- (that is, in the above formula, R 3 Fa is a fluorine atom) may be any of -(OCF 2 CF 2 CF 2 )-, -(OCF(CF 3 )CF 2 )- and -(OCF 2 CF(CF 3 ))-.
  • -(OC 2 F 4 )- may be either -(OCF 2 CF 2 )- or -(OCF(CF 3 ))-.
  • the repeating unit is linear. By making the repeating unit linear, it is possible to improve the surface lubricity, abrasion resistance, etc. of the surface treatment layer.
  • the repeating unit is branched. By branching the repeating unit, the dynamic friction coefficient of the surface treatment layer can be increased.
  • R F can include a ring structure.
  • the ring structure may be the following three-membered ring, four-membered ring, five-membered ring, or six-membered ring. [In the formula, * indicates a binding position. ]
  • the ring structure is preferably a four-, five- or six-membered ring, more preferably a four- or six-membered ring.
  • the repeating unit having a ring structure can preferably be the following units. [In the formula, * indicates a binding position. ]
  • each occurrence of R 1 F is independently a group represented by any one of the following formulas (f1) to (f6). -(OC 3 F 6 ) d -(OC 2 F 4 ) e - (f1) [Wherein, d is an integer of 1 to 200, and e is 0 or 1.
  • R 6 is OCF 2 or OC 2 F 4 ; R7 is a group selected from OC2F4 , OC3F6 , OC4F8 , OC5F10 and OC6F12 or a combination of two or three groups independently selected from these groups; g is an integer from 2 to 100; ]; —(R 6 —R 7 ) g —R r —(R 7′ —R 6′ ) g′ ⁇ (f4) [wherein R 6 is OCF 2 or OC 2 F 4 ; R7 is a group selected from OC2F4 , OC3F6 , OC4F8 , OC5F10 and OC6F12 or a combination of two or three groups independently selected from these groups; R 6' is OCF 2 or OC 2 F 4 ; R 7′ is a group selected from OC 2 F 4 , OC 3 F 6 ,
  • e is an integer of 1 or more and 200 or less
  • a, b, c, d and f are each independently an integer of 0 or more and 200 or less, and the order of existence of each repeating unit bracketed with a, b, c, d, e or f in the formula is arbitrary.
  • f is an integer of 1 or more and 200 or less
  • a, b, c, d and e are each independently an integer of 0 or more and 200 or less, and the order of existence of each repeating unit bracketed with a, b, c, d, e or f in the formula is arbitrary.
  • d is preferably an integer of 5-200, more preferably 10-100, still more preferably 15-50, for example 25-35.
  • OC 3 F 6 in the above formula (f1) is preferably (OCF 2 CF 2 CF 2 ), (OCF(CF 3 )CF 2 ) or (OCF 2 CF(CF 3 )), more preferably (OCF 2 CF 2 CF 2 ).
  • e is zero.
  • e is 1.
  • (OC 2 F 4 ) in the above formula (f1) is preferably (OCF 2 CF 2 ) or (OCF(CF 3 )), more preferably (OCF 2 CF 2 ).
  • e and f are each independently an integer of preferably 5-200, more preferably 10-200. Also, the sum of c, d, e and f is preferably 5 or more, more preferably 10 or more, and may be, for example, 15 or more or 20 or more.
  • the above formula (f2) is preferably a group represented by - ( OCF2CF2CF2CF2 ) c- ( OCF2CF2CF2 ) d- ( OCF2CF2 ) e- ( OCF2 ) f- .
  • formula (f2) may be a group represented by -(OC 2 F 4 ) e -(OCF 2 ) f -.
  • R 6 is preferably OC 2 F 4 .
  • R7 is preferably a group selected from OC2F4 , OC3F6 and OC4F8 , or a combination of two or three groups independently selected from these groups , more preferably a group selected from OC3F6 and OC4F8 .
  • Said g is preferably an integer of 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.
  • the above formula (f3) is preferably -(OC 2 F 4 -OC 3 F 6 ) g - or -(OC 2 F 4 -OC 4 F 8 ) g -.
  • R 6 , R 7 and g have the same meanings as in formula (f3) above, and have the same aspects.
  • R 6′ , R 7′ and g′ have the same meanings as R 6 , R 7 and g in formula (f3) above, respectively, and have the same aspects.
  • R r is preferably [In the formula, * indicates a binding position. ] and more preferably [In the formula, * indicates a binding position. ] is.
  • e is preferably an integer of 1 or more and 100 or less, more preferably 5 or more and 100 or less.
  • the sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example 10 or more and 100 or less.
  • f is preferably an integer of 1 or more and 100 or less, more preferably 5 or more and 100 or less.
  • the sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example 10 or more and 100 or less.
  • R F is a group represented by the formula (f1).
  • R F is a group represented by the formula (f2).
  • R F is a group represented by the formula (f3) or (f4).
  • R F is a group represented by the formula (f3).
  • R F is a group represented by the formula (f4).
  • R F is a group represented by the formula (f5).
  • R F is a group represented by the formula (f6).
  • the ratio of e to f (hereinafter referred to as "e/f ratio”) is 0.1 to 10, preferably 0.2 to 5, more preferably 0.2 to 2, still more preferably 0.2 to 1.5, and even more preferably 0.2 to 0.85.
  • e/f ratio the ratio of e to f
  • the slipperiness, wear resistance and chemical resistance (for example, durability against artificial perspiration) of the surface treatment layer obtained from this compound are further improved.
  • the smaller the e/f ratio the more improved the sliding property and abrasion resistance of the surface treatment layer.
  • the stability of the compound can be further enhanced. The higher the e/f ratio, the more stable the compound.
  • the number average molecular weights of the R 1 F1 and R 2 F2 moieties are not particularly limited, but are, for example, 500 to 30,000, preferably 1,500 to 30,000, and more preferably 2,000 to 10,000.
  • the number average molecular weights of R F1 and R F2 are values measured by 19 F-NMR.
  • the R F1 and R F2 moieties may have a number average molecular weight of 500 to 30,000, preferably 1,000 to 20,000, more preferably 2,000 to 15,000, even more preferably 2,000 to 10,000, such as 3,000 to 6,000.
  • the number average molecular weight of the R F1 and R F2 moieties can be from 4,000 to 30,000, preferably from 5,000 to 10,000, more preferably from 6,000 to 10,000.
  • each occurrence of R Si is independently a monovalent group containing a Si atom to which a hydroxyl group, a hydrolyzable group, a hydrogen atom or a monovalent organic group is bonded, and at least one R Si is a monovalent group containing a Si atom to which a hydroxyl group or a hydrolyzable group is bonded.
  • hydrolyzable group means a group capable of undergoing a hydrolysis reaction, that is, a group capable of being eliminated from the main skeleton of a compound by a hydrolysis reaction.
  • R 3 Si is a monovalent group containing a Si atom to which a hydroxyl group or hydrolyzable group is attached.
  • R Si is represented by the following formula (S1), (S2), (S3), (S4), or (S5): It is a group represented by
  • each occurrence of R 11 is independently a hydroxyl group or a hydrolyzable group.
  • R 11 is preferably independently at each occurrence a hydrolyzable group.
  • R j include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; and substituted alkyl groups such as chloromethyl group.
  • an alkyl group particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
  • R j is a methyl group, and in another aspect R j is an ethyl group.
  • each occurrence of R 12 is independently a hydrogen atom or a monovalent organic group.
  • a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.
  • the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, even more preferably a methyl group.
  • n1 is an integer of 0 to 3 independently for each (SiR 11 n1 R 12 3-n1 ) unit.
  • R Si is a group represented by formula (S1) or (S2)
  • n1 is preferably an integer of 1 to 3, more preferably 2 to 3, still more preferably 3, independently for each (SiR 11 n1 R 12 3-n1 ) unit.
  • X 11 at each occurrence is independently a single bond or a divalent organic group.
  • divalent organic groups are preferably -R 28 -O x -R 29 - (wherein R 28 and R 29 are each independently at each occurrence a single bond or a C 1-20 alkylene group and x is 0 or 1).
  • Such C 1-20 alkylene groups may be straight chain or branched, but are preferably straight chain.
  • Such C 1-20 alkylene groups are preferably C 1-10 alkylene groups, more preferably C 1-6 alkylene groups, still more preferably C 1-3 alkylene groups.
  • X 11 is independently at each occurrence -C 1-6 alkylene-O-C 1-6 alkylene- or -O-C 1-6 alkylene-.
  • each occurrence of X 11 is independently a single bond or a straight chain C 1-6 alkylene group, preferably a single bond or a straight chain C 1-3 alkylene group, more preferably a single bond or a straight chain C 1-2 alkylene group, still more preferably a straight chain C 1-2 alkylene group.
  • each occurrence of R 13 is independently a hydrogen atom or a monovalent organic group.
  • Such monovalent organic groups are preferably C 1-20 alkyl groups.
  • Such C 1-20 alkyl groups may be straight chain or branched, but are preferably straight chain.
  • R 13 is independently at each occurrence a hydrogen atom or a linear C 1-6 alkyl group, preferably a hydrogen atom or a linear C 1-3 alkyl group, preferably a hydrogen atom or a methyl group.
  • t is an integer of 2 or more independently at each occurrence.
  • t is independently an integer of 2-10, preferably an integer of 2-6 at each occurrence.
  • each occurrence of R 14 is independently a hydrogen atom, a halogen atom or —X 11 —SiR 11 n1 R 12 3-n1 .
  • a halogen atom is preferably an iodine atom, a chlorine atom or a fluorine atom, more preferably a fluorine atom.
  • R 14 is a hydrogen atom.
  • each occurrence of R 15 is independently a single bond, an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or an alkyleneoxy group having 1 to 6 carbon atoms.
  • each occurrence of R 15 is independently an oxygen atom, a C 1-6 alkylene group, or a C 1-6 alkyleneoxy group.
  • R 15 is a single bond.
  • formula (S1) is the following formula (S1-a).
  • R 11 , R 12 , R 13 , X 11 , and n1 have the same meanings as described in formula (S1) above;
  • t1 and t2 are each independently at each occurrence an integer of 1 or greater, preferably an integer of 1 to 10, more preferably an integer of 2 to 10, such as an integer of 1 to 5 or an integer of 2 to 5;
  • the order of existence of each repeating unit bracketed with t1 and t2 is arbitrary in the formula.
  • formula (S1) is the following formula (S1-b). [Wherein, R 11 , R 12 , R 13 , X 11 , n1 and t have the same meanings as described in formula (S1) above]
  • each occurrence of R a1 is independently —Z 1 —SiR 21 p1 R 22 q1 R 23 r1 .
  • Z 1 is independently an oxygen atom or a divalent organic group.
  • the right side is bound to (SiR 21 p1 R 22 q1 R 23 r1 ).
  • Z 1 is a divalent organic group.
  • Z 1 does not include those that form a siloxane bond with the Si atom to which Z 1 is bonded.
  • (Si—Z 1 —Si) in formula (S3) does not contain a siloxane bond.
  • the above Z 1 is preferably a C 1-6 alkylene group, -(CH 2 ) z1 -O-(CH 2 ) z2 - (wherein z1 is an integer of 0 to 6, such as an integer of 1 to 6, and z2 is an integer of 0 to 6, such as an integer of 1 to 6) or -(CH 2 ) z3 -phenylene-(CH 2 ) z4 - (wherein z3 is an integer of 0 to 6) , for example an integer from 1 to 6, and z4 is an integer from 0 to 6, for example an integer from 1 to 6).
  • Such C 1-6 alkylene groups may be straight chain or branched, but are preferably straight chain.
  • These groups may be substituted by one or more substituents selected from, for example, fluorine atoms, C 1-6 alkyl groups, C 2-6 alkenyl groups and C 2-6 alkynyl groups, but are preferably unsubstituted.
  • Z 1 is a C 1-6 alkylene group or -(CH 2 ) z3 -phenylene-(CH 2 ) z4 -, preferably -phenylene-(CH 2 ) z4 -.
  • Z 1 is such a group, higher light resistance, especially UV resistance, can be obtained.
  • Z 1 above is a C 1-3 alkylene group.
  • Z 1 can be -CH 2 CH 2 CH 2 -.
  • Z 1 can be -CH 2 CH 2 -.
  • R 21 above is independently at each occurrence —Z 1′ —SiR 21′ p1′ R 22′ q1′ R 23′ r1′ .
  • Z 1′ is independently an oxygen atom or a divalent organic group.
  • the right side is bound to (SiR 21′ p1′ R 22′ q1′ R 23′ r1′ ).
  • Z 1' is a divalent organic group.
  • Z 1' does not include those that form a siloxane bond with the Si atom to which Z 1' is bonded.
  • (Si—Z 1′ —Si) in formula (S3) does not contain a siloxane bond.
  • the above Z 1′ is preferably a C 1-6 alkylene group, —(CH 2 ) z1′ —O—(CH 2 ) z2′ — (wherein z1′ is an integer of 0 to 6, such as an integer of 1 to 6, and z2′ is an integer of 0 to 6, such as an integer of 1 to 6), or —(CH 2 ) z3′ —phenylene-(CH 2 ) z4′ — (wherein z3 ' is an integer from 0 to 6, such as an integer from 1 to 6, and z4' is an integer from 0 to 6, such as an integer from 1 to 6).
  • Such C 1-6 alkylene groups may be linear or branched, but are preferably linear.
  • These groups may be substituted with one or more substituents selected from, for example, fluorine atoms, C 1-6 alkyl groups, C 2-6 alkenyl groups and C 2-6 alkynyl groups, but are preferably unsubstituted.
  • Z 1' is a C 1-6 alkylene group or -(CH 2 ) z3' -phenylene-(CH 2 ) z4' -, preferably -phenylene-(CH 2 ) z4' -.
  • Z 1′ is such a group, it can have higher light resistance, especially UV resistance.
  • Z 1′ above is a C 1-3 alkylene group.
  • Z 1' can be -CH 2 CH 2 CH 2 -.
  • Z 1' can be -CH 2 CH 2 -.
  • R 21′ above is independently at each occurrence —Z 1′′ —SiR 22′′ q1′′ R 23′′ r1′′ .
  • Z 1′′ is independently an oxygen atom or a divalent organic group.
  • the right side is bound to (SiR 22′′ q1′′ R 23′′ r1′′ ).
  • Z 1′′ is a divalent organic group.
  • Z 1′′ does not include those that form a siloxane bond with the Si atom to which Z 1′′ is bonded.
  • Si—Z 1′′ —Si does not contain a siloxane bond.
  • Z 1" is preferably C 1-6 an alkylene group, —(CH 2 ) z1” -O-(CH 2 ) z2” - (wherein z1′′ is an integer from 0 to 6, such as an integer from 1 to 6, and z2′′ is an integer from 0 to 6, such as an integer from 1 to 6) or –(CH 2 ) z3” -phenylene-(CH 2 ) z4” - (wherein z3′′ is an integer from 0 to 6, such as an integer from 1 to 6, and z4′′ is an integer from 0 to 6, such as an integer from 1 to 6).
  • An alkylene group may be straight-chained or branched, but is preferably straight-chained. These groups are, for example, fluorine atoms, C 1-6 alkyl group, C 2-6 an alkenyl group, and C 2-6 It is optionally substituted by one or more substituents selected from alkynyl groups, but is preferably unsubstituted.
  • Z 1′′ is a C 1-6 alkylene group or -(CH 2 ) z3′′ -phenylene-(CH 2 ) z4′′ -, preferably -phenylene-(CH 2 ) z4′′ -.
  • Z 1′′ is such a group, it can be more light-resistant, especially UV-resistant.
  • Z 1′′ is a C 1-3 alkylene group. In one aspect, Z 1′′ can be —CH 2 CH 2 CH 2 —. In another aspect, Z 1′′ can be —CH 2 CH 2 —.
  • R 22′′ above is independently a hydroxyl group or a hydrolyzable group.
  • R 22 ′′ above is preferably independently at each occurrence a hydrolyzable group.
  • R. j examples include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; and substituted alkyl groups such as chloromethyl group.
  • an alkyl group particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
  • R j is a methyl group, and in another aspect, R j is an ethyl group.
  • Each occurrence of R 23 ′′ above is independently a hydrogen atom or a monovalent organic group.
  • Such monovalent organic groups are monovalent organic groups excluding the above hydrolyzable groups.
  • the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, and even more preferably a methyl group.
  • q1′′ is independently at each occurrence an integer from 0 to 3
  • the at least one r1′′ is independently at each occurrence an integer from 0 to 3.
  • the sum of q1′′ and r1′′ is 3 in units of (SiR 22′′ q1′′ R 23′′ r1′′ ).
  • q1′′ is an integer of preferably 1 to 3, more preferably 2 to 3, still more preferably 3, independently for each (SiR 22′′ q1′′ R 23′′ r1′′ ) unit.
  • R 22′ is independently a hydroxyl group or a hydrolyzable group.
  • R 22' is preferably independently at each occurrence a hydrolyzable group.
  • R 22′ is preferably —OR j , —OCOR j , —ON ⁇ CR j 2 , —NR j 2 , —NHR j , —NCO, or halogen (wherein R j represents a substituted or unsubstituted C 1-4 alkyl group), more preferably —OR j (i.e., an alkoxy group) at each occurrence independently.
  • R j include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; and substituted alkyl groups such as chloromethyl group.
  • an alkyl group particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
  • R j is a methyl group, and in another aspect R j is an ethyl group.
  • Each occurrence of R 23′ above is independently a hydrogen atom or a monovalent organic group.
  • a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.
  • the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, even more preferably a methyl group.
  • p1′ is independently an integer of 0 to 3 at each occurrence
  • q1′ is independently an integer of 0 to 3 at each occurrence
  • r1′ is independently an integer of 0 to 3 at each occurrence.
  • the sum of p', q1' and r1' is 3 in the unit of (SiR 21' p1' R 22' q1' R 23' r1' ).
  • p1' is 0.
  • p1' may be an integer of 1 to 3, an integer of 2 to 3, or 3 independently for each (SiR 21' p1' R 22' q1' R 23' r1' ) unit. In a preferred embodiment, p1' is 3.
  • q1' is an integer of 1 to 3, preferably an integer of 2 to 3, more preferably 3, independently for each (SiR 21' p1' R 22' q1' R 23' r1' ) unit.
  • p1′ is 0 and q1′ is an integer of 1 to 3, preferably an integer of 2 to 3, more preferably 3, for each (SiR 21′ p1′ R 22′ q1′ R 23′ r1′ ) unit.
  • R 22 above is independently a hydroxyl group or a hydrolyzable group.
  • R 22 is preferably independently at each occurrence a hydrolyzable group.
  • R j include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; and substituted alkyl groups such as chloromethyl group.
  • an alkyl group particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
  • R j is a methyl group, and in another aspect R j is an ethyl group.
  • Each occurrence of R 23 above is independently a hydrogen atom or a monovalent organic group.
  • a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.
  • the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, even more preferably a methyl group.
  • p1 is independently at each occurrence an integer of 0 to 3
  • q1 is at each occurrence independently an integer from 0 to 3
  • r1 is at each occurrence independently an integer of 0 to 3.
  • the sum of p1, q1 and r1 is 3 in units of (SiR 21 p1 R 22 q1 R 23 r1 ).
  • p1 is 0.
  • p1 may be an integer of 1 to 3, an integer of 2 to 3, or 3 independently for each (SiR 21 p1 R 22 q1 R 23 r1 ) unit. In a preferred embodiment, p1 is 3.
  • q1 is an integer of 1 to 3, preferably an integer of 2 to 3, more preferably 3, independently for each (SiR 21 p1 R 22 q1 R 23 r1 ) unit.
  • p1 is 0 and q1 is an integer of 1 to 3, preferably an integer of 2 to 3, more preferably 3, independently for each (SiR 21 p1 R 22 q1 R 23 r1 ) unit.
  • each occurrence of R b1 is independently a hydroxyl group or a hydrolyzable group.
  • R b1 above is preferably independently at each occurrence a hydrolyzable group.
  • R j include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; and substituted alkyl groups such as chloromethyl group.
  • an alkyl group particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
  • R j is a methyl group, and in another aspect R j is an ethyl group.
  • each occurrence of R c1 is independently a hydrogen atom or a monovalent organic group.
  • a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.
  • the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, still more preferably a methyl group.
  • k1 is independently an integer of 0 to 3 at each occurrence
  • l1 is independently an integer of 0 to 3 at each occurrence
  • m1 is independently an integer of 0 to 3 at each occurrence.
  • the sum of k1, l1 and m1 is 3 in units of (SiR a1 k1 R b1 l1 R c1 m1 ).
  • k1 is independently an integer of 1 to 3, preferably 2 or 3, more preferably 3 for each (SiR a1 k1 R b1 l1 R c1 m1 ) unit. In a preferred embodiment, k1 is 3.
  • R Si is a group represented by formula (S3), preferably at the terminal portion of formulas (1) and (2), there are at least two Si atoms to which hydroxyl groups or hydrolyzable groups are bonded.
  • the group represented by formula (S3) is -Z 1 -SiR 22 q1 R. 23 r1 (Wherein, q1 is an integer of 1 to 3, preferably 2 or 3, more preferably 3, and r1 is an integer of 0 to 2.), -Z 1' -SiR 22' q1' R. 23' r1' (Wherein, q1' is an integer of 1 to 3, preferably 2 or 3, more preferably 3, and r1' is an integer of 0 to 2.), or -Z 1" -SiR 22" q1” R.
  • Z. 1 , Z 1' , Z 1" , R 22 , R 23 , R 22' , R 23' , R 22" , and R 23" has the same meaning as above.
  • At least one, preferably all R 21′ , if present, q1′′ is an integer from 1 to 3, preferably 2 or 3, more preferably 3.
  • R 21 if R 21 is present, at least one, preferably all R 21 , p1′ is 0 and q1′ is an integer of 1 to 3, preferably 2 or 3, more preferably 3.
  • p1 is 0 and q1 is an integer of 1 to 3, preferably 2 or 3, more preferably 3, in at least one, preferably all R a1 , if present, in formula (S3 ) .
  • k1 is 2 or 3, preferably 3, p1 is 0, and q1 is 2 or 3, preferably 3, in formula (S3).
  • R d1 is independently at each occurrence -Z 2 -CR 31 p2 R 32 q2 R 33 r2 .
  • Z 2 is independently at each occurrence a single bond, an oxygen atom, or a divalent organic group.
  • the right side is bound to (CR 31 p2 R 32 q2 R 33 r2 ).
  • Z 2 is a divalent organic group.
  • the above Z 2 is preferably a C 1-6 alkylene group, -(CH 2 ) z5 -O-(CH 2 ) z6 - (wherein z5 is an integer of 0 to 6, such as an integer of 1 to 6, and z6 is an integer of 0 to 6, such as an integer of 1 to 6) or -(CH 2 ) z7 -phenylene-(CH 2 ) z8 - (wherein z7 is an integer of 0 to 6) , for example an integer from 1 to 6, and z8 is an integer from 0 to 6, for example an integer from 1 to 6).
  • Such C 1-6 alkylene groups may be linear or branched, but are preferably linear.
  • These groups may be substituted with one or more substituents selected from, for example, fluorine atoms, C 1-6 alkyl groups, C 2-6 alkenyl groups and C 2-6 alkynyl groups, but are preferably unsubstituted.
  • Z 2 is a C 1-6 alkylene group or -(CH 2 ) z7 -phenylene-(CH 2 ) z8 -, preferably -phenylene-(CH 2 ) z8 -.
  • Z2 is such a group, it can be more light-resistant, especially UV-resistant.
  • Z 2 above is a C 1-3 alkylene group.
  • Z 2 can be -CH 2 CH 2 CH 2 -.
  • Z 2 can be -CH 2 CH 2 -.
  • R 31 is independently at each occurrence -Z 2' -CR 32' q2' R 33' r2' .
  • Z 2' at each occurrence is independently a single bond, an oxygen atom or a divalent organic group.
  • the right side is bound to (CR 32′ q2′ R 33′ r2′ ).
  • the above Z 2′ is preferably a C 1-6 alkylene group, —(CH 2 ) z5′ —O—(CH 2 ) z6′ — (wherein z5′ is an integer of 0 to 6, such as an integer of 1 to 6, and z6′ is an integer of 0 to 6, such as an integer of 1 to 6), or —(CH 2 ) z7′ —phenylene-(CH 2 ) z8′ — (wherein z7 ' is an integer from 0 to 6, such as an integer from 1 to 6, and z8' is an integer from 0 to 6, such as an integer from 1 to 6).
  • Such C 1-6 alkylene groups may be linear or branched, but are preferably linear.
  • These groups may be substituted with one or more substituents selected from, for example, fluorine atoms, C 1-6 alkyl groups, C 2-6 alkenyl groups and C 2-6 alkynyl groups, but are preferably unsubstituted.
  • Z 2' is a C 1-6 alkylene group or -(CH 2 ) z7' -phenylene-(CH 2 ) z8' -, preferably -phenylene-(CH 2 ) z8' -.
  • Z 2' is such a group, it can be more light-resistant, especially UV-resistant.
  • Z 2′ above is a C 1-3 alkylene group.
  • Z 2' can be -CH 2 CH 2 CH 2 -.
  • Z 2' can be -CH 2 CH 2 -.
  • R 32′ is independently —Z 3 —SiR 34 n2 R 35 3-n2 .
  • Z 3 is independently a single bond, an oxygen atom, or a divalent organic group.
  • the right side is bound to (SiR 34 n2 R 35 3-n2 ).
  • Z3 is an oxygen atom.
  • Z 3 is a divalent organic group.
  • the above Z 3 is preferably a C 1-6 alkylene group, —(CH 2 ) z5′′ —O—(CH 2 ) z6′′ — (wherein z5′′ is an integer of 0 to 6, such as an integer of 1 to 6, and z6′′ is an integer of 0 to 6, such as an integer of 1 to 6) or –(CH 2 ) z7′′ –phenylene-(CH 2 ) z8′′ – (wherein z7′′ is an integer from 0 to 6, such as an integer from 1 to 6, and z8′′ is an integer from 0 to 6, such as an integer from 1 to 6).
  • Such C 1-6 alkylene groups may be linear or branched, but are preferably linear.
  • These groups may be substituted with one or more substituents selected from, for example, fluorine atoms, C 1-6 alkyl groups, C 2-6 alkenyl groups and C 2-6 alkynyl groups, but are preferably unsubstituted.
  • Z 3 is a C 1-6 alkylene group or -(CH 2 ) z7′′ -phenylene-(CH 2 ) z8′′ -, preferably -phenylene-(CH 2 ) z8′′ -.
  • Z 3 is such a group, higher light resistance, especially UV resistance, can be achieved.
  • Z 3 above is a C 1-3 alkylene group.
  • Z 3 can be -CH 2 CH 2 CH 2 -.
  • Z 3 can be -CH 2 CH 2 -.
  • R 34 above is independently a hydroxyl group or a hydrolyzable group.
  • R 34 is preferably independently at each occurrence a hydrolyzable group.
  • R 34 is preferably —OR j , —OCOR j , —ON ⁇ CR j 2 , —NR j 2 , —NHR j , —NCO, or halogen (wherein R j represents a substituted or unsubstituted C 1-4 alkyl group), more preferably —OR j (i.e., an alkoxy group), each independently at each occurrence.
  • R j include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; and substituted alkyl groups such as chloromethyl group.
  • an alkyl group particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
  • R j is a methyl group, and in another aspect R j is an ethyl group.
  • Each occurrence of R 35 above is independently a hydrogen atom or a monovalent organic group.
  • a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.
  • the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, still more preferably a methyl group.
  • n2 is an integer of 0 to 3 independently for each (SiR 34 n2 R 35 3-n2 ) unit.
  • R 1 Si is a group represented by formula (S4)
  • n2 is preferably an integer of 1 to 3, more preferably 2 to 3, still more preferably 3, independently for each (SiR 34 n2 R 35 3-n2 ) unit.
  • Each occurrence of R 33′ above is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group.
  • a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.
  • the monovalent organic group is preferably a C 1-20 alkyl group or —(C s H 2s ) t1 —(O—C s H 2s ) t2 (wherein s is an integer of 1 to 6, preferably an integer of 2 to 4, t1 is 1 or 0, preferably 0, t2 is an integer of 1 to 20, preferably an integer of 2 to 10, more preferably an integer of 2 to 6 ), more preferably a C 1-20 alkyl group, still more preferably a C 1-6 alkyl group, and particularly preferably a methyl group.
  • R 33' is a hydroxyl group.
  • R 33' is a monovalent organic group, preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group.
  • Each occurrence of q2' is independently an integer from 0 to 3, and each occurrence of r2' is independently an integer from 0 to 3.
  • the sum of q2' and r2' is 3 in the unit of (CR 32' q2' R 33' r2' ).
  • q2' is preferably an integer of 1 to 3, more preferably 2 to 3, still more preferably 3, independently for each (CR 32' q2' R 33' r2' ) unit.
  • R 32 is independently at each occurrence -Z 3 -SiR 34 n2 R 35 3-n2 .
  • Such —Z 3 —SiR 34 n2 R 35 3-n2 has the same meaning as described for R 32′ above.
  • Each occurrence of R 33 above is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group.
  • a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.
  • the monovalent organic group is preferably a C 1-20 alkyl group or —(C s H 2s ) t1 —(O—C s H 2s ) t2 (wherein s is an integer of 1 to 6, preferably 2 to 4, t1 is 1 or 0, preferably 0, t2 is an integer of 1 to 20, preferably an integer of 2 to 10, more preferably an integer of 2 to 6. ), more preferably a C 1-20 alkyl group, still more preferably a C 1-6 alkyl group, and most preferably a methyl group.
  • R 33 is a hydroxyl group.
  • R 33 is a monovalent organic group, preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group.
  • p2 is independently at each occurrence an integer of 0 to 3
  • q2 is independently at each occurrence an integer from 0 to 3
  • r2 is at each independently at each occurrence an integer of 0 to 3.
  • the sum of p2, q2 and r2 is 3 in the unit of (CR 31 p2 R 32 q2 R 33 r2 ).
  • p2 is 0.
  • p2 may be an integer of 1 to 3, an integer of 2 to 3, or 3 independently for each (CR 31 p2 R 32 q2 R 33 r2 ) unit. In preferred embodiments, p2 is three.
  • q2 is an integer of 1 to 3, preferably an integer of 2 to 3, more preferably 3 for each (CR 31 p2 R 32 q2 R 33 r2 ) unit.
  • p2 is 0 and q2 is an integer of 1 to 3, preferably an integer of 2 to 3, more preferably 3, independently for each (CR 31 p2 R 32 q2 R 33 r2 ) unit.
  • R e1 above is independently —Z 3 —SiR 34 n2 R 35 3-n2 .
  • Such —Z 3 —SiR 34 n2 R 35 3-n2 has the same meaning as described for R 32′ above.
  • Each occurrence of R f1 above is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group.
  • a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.
  • the monovalent organic group is preferably a C 1-20 alkyl group or —(C s H 2s ) t1 —(O—C s H 2s ) t2 (wherein s is an integer of 1 to 6, preferably an integer of 2 to 4, t1 is 1 or 0, preferably 0, t2 is an integer of 1 to 20, preferably an integer of 2 to 10, more preferably an integer of 2 to 6. ), more preferably a C 1-20 alkyl group, still more preferably a C 1-6 alkyl group, and particularly preferably a methyl group.
  • R f1 is a hydroxyl group.
  • R f1 is a monovalent organic group, preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group.
  • k2 is independently an integer of 0 to 3 at each occurrence
  • l2 is independently an integer of 0 to 3 at each occurrence
  • m2 is independently an integer from 0 to 3 at each occurrence.
  • the sum of k2, l2 and m2 is 3 in units of (CR d1 k2 R e1 l2 R f1 m2 ).
  • R Si is a group represented by the formula (S4), preferably at the terminal portion of the formulas (1) and (2), there are at least two Si atoms to which a hydroxyl group or a hydrolyzable group is bonded.
  • the N2 is 1 to 3, 2 or 3 preferably 3 (SIR 34 N2 R 35 3 -N2 ), 2 or 27, 2-9, 2-9, for example, in each end of equation (1) and equation (2).
  • n2 is an integer from 1 to 3, preferably 2 or 3, more preferably 3, in formula (S4), at least one, preferably all R 32' , if present.
  • n2 is an integer from 1 to 3, preferably 2 or 3, more preferably 3.
  • R e1 if R e1 is present, at least one, preferably all R a1 , n2 is an integer from 1 to 3, preferably 2 or 3, more preferably 3.
  • k2 is 0, l2 is 2 or 3, preferably 3, and n2 is 2 or 3, preferably 3, in formula (S4).
  • R g1 and R h1 above are each independently at each occurrence -Z 4 -SiR 11 n1 R 12 3-n1 , -Z 4 -SiR a1 k1 R b1 l1 R c1 m1 , -Z 4 -CR d1 k2 R e1 l2 R f1 m2 .
  • R 11 , R 12 , R a1 , R b2 , R c1 , R d1 , R e1 , R f1 , n1, k1, l1, m1, k2, l2, and m2 have the same meanings as above.
  • R g1 and R h1 are each independently —Z 4 —SiR 11 n1 R 12 3-n1 .
  • Z 4 is independently a single bond, an oxygen atom, or a divalent organic group.
  • the right side is bound to (SiR 11 n1 R 12 3-n1 ).
  • Z 4 is an oxygen atom.
  • Z 4 is a divalent organic group.
  • the above Z 4 is preferably a C 1-6 alkylene group, —(CH 2 ) z5′′ —O—(CH 2 ) z6′′ — (wherein z5′′ is an integer of 0 to 6, such as an integer of 1 to 6, and z6′′ is an integer of 0 to 6, such as an integer of 1 to 6) or –(CH 2 ) z7′′ –phenylene-(CH 2 ) z8′′ – (wherein z7′′ is an integer from 0 to 6, such as an integer from 1 to 6, and z8′′ is an integer from 0 to 6, such as an integer from 1 to 6).
  • Such C 1-6 alkylene groups may be linear or branched, but are preferably linear.
  • These groups may be substituted with one or more substituents selected from, for example, fluorine atoms, C 1-6 alkyl groups, C 2-6 alkenyl groups and C 2-6 alkynyl groups, but are preferably unsubstituted.
  • Z 4 is a C 1-6 alkylene group or -(CH 2 ) z7′′ -phenylene-(CH 2 ) z8′′ -, preferably -phenylene-(CH 2 ) z8′′ -.
  • Z 3 is such a group, higher light resistance, especially UV resistance, can be achieved.
  • Z 4 above is a C 1-3 alkylene group.
  • Z 4 can be -CH 2 CH 2 CH 2 -.
  • Z 4 can be -CH 2 CH 2 -.
  • R Si is a group represented by formula (S2), (S3), (S4) or (S5). These compounds can form a surface treatment layer having high surface lubricity.
  • R Si is a group represented by formula (S3), (S4) or (S5). Since these compounds have a plurality of hydrolyzable groups at one end, they can form a surface treatment layer that strongly adheres to a substrate and has high abrasion resistance.
  • R Si is a group represented by formula (S3) or (S4). Since these compounds can have a plurality of hydrolyzable groups branched from one Si atom or C atom at one end, they can form a surface treatment layer with even higher abrasion resistance.
  • R Si is a group represented by formula (S1).
  • R Si is a group represented by formula (S2).
  • R Si is a group represented by formula (S3).
  • R Si is a group represented by formula (S4).
  • R Si is a group represented by formula (S5).
  • X A is understood to be a linker that connects the fluoropolyether portions (R F1 and R F2 ) that mainly provide water repellency and surface slipperiness and the portion (R Si ) that provides bonding ability to the substrate. Therefore, XA may be a single bond or any group as long as the compounds represented by formulas (1) and (2) can exist stably.
  • ⁇ is an integer of 1-9
  • ⁇ is an integer of 1-9.
  • ⁇ is an integer of 1-9.
  • ⁇ and ⁇ can vary depending on the valence of XA .
  • the sum of ⁇ and ⁇ is the same as the valence of XA .
  • X A is a 10-valent organic group
  • ⁇ and ⁇ are 1 when X A is a divalent organic group.
  • ⁇ is an integer of 1-9. ⁇ can vary depending on the valence of X A. That is, ⁇ is the value obtained by subtracting 1 from the valence of XA .
  • each X A is independently a single bond or a divalent to decavalent organic group
  • the divalent to decavalent organic group in X A above is preferably a divalent to octavalent organic group.
  • such divalent to decavalent organic groups are preferably divalent to tetravalent organic groups, more preferably divalent organic groups.
  • such divalent to decavalent organic groups are preferably trivalent to octavalent organic groups, more preferably trivalent to hexavalent organic groups.
  • X A is a single bond or a divalent organic group, ⁇ is 1 and ⁇ is 1.
  • X A is a single bond or a divalent organic group and ⁇ is one.
  • X A is a tri- to hexavalent organic group, ⁇ is 1 and ⁇ is 2-5.
  • X A is a 3-6 valent organic group and ⁇ is 2-5.
  • X A is a trivalent organic group, ⁇ is 1 and ⁇ is 2.
  • X A is a trivalent organic group and ⁇ is two.
  • formulas (1) and (2) are represented by formulas (1') and (2') below.
  • X A is a single bond.
  • X A is a divalent organic group.
  • X A is, for example, a single bond or the following formula: -(R 51 ) p5 -(X 51 ) q5 -
  • R 51 represents a single bond, —(CH 2 ) s5 — or an o-, m- or p-phenylene group, preferably —(CH 2 ) s5 —, s5 is an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, even more preferably 1 or 2;
  • X 51 represents -(X 52 ) l5 -, X 52 is independently at each occurrence -O-, -S-, o-, m- or p-phenylene group, -C(O)O-, -Si(R 53 ) 2 -, -(Si(R 53 ) 2 O) m5 -Si(R 53 ) 2 -, -CONR 54 -, -O-CONR 54 -, -
  • X A (typically a hydrogen atom of X A ) may be substituted with one or more substituents selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group. In preferred embodiments, X A is not substituted by these groups.
  • each X A above is independently -(R 51 ) p5 -(X 51 ) q5 -R 52 -.
  • R 52 represents a single bond, -(CH 2 ) t5 - or an o-, m- or p-phenylene group, preferably -(CH 2 ) t5 -.
  • t5 is an integer of 1-20, preferably an integer of 2-6, more preferably an integer of 2-3.
  • R 52 (typically the hydrogen atom of R 52 ) may be substituted with one or more substituents selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group. In preferred embodiments, R 56 is not substituted by these groups.
  • X A are each independently single bond, a C 1-20 alkylene group, —R 51 —X 53 —R 52 —, or —X 54 —R 5 —
  • R 51 and R 52 have the same meanings as above, X53 is -O-, -S-, -C(O)O-, -CONR 54- , -O-CONR 54- , —Si(R 53 ) 2 —, —(Si(R 53 ) 2 O) m5 —Si(R 53 ) 2 —, —O—(CH 2 ) u5 —(Si(R 53 ) 2 O) m5 —Si(R 53 ) 2 —, —O—(CH 2 ) u5 —Si(R 53 ) 2 —O—Si(R 53 ) 2 —CH 2 CH 2 —Si(R 53 ) 2 —O—Si(R 53 ) 2 —CH 2 CH 2 —
  • X54 is -S-, -C(O)O-, -CONR 54- , -O-CONR 54- , —CONR 54 —(CH 2 ) u5 —(Si(R 54 ) 2 O) m5 —Si(R 54 ) 2 —, -CONR 54 -(CH 2 ) u5 -N(R 54 )-, or -CONR 54 -(o-, m- or p-phenylene)-Si(R 54 ) 2 - (In the formula, each symbol has the same meaning as above.) represents ] can be
  • the above X A are each independently single bond, a C 1-20 alkylene group, —(CH 2 ) s5 —X 53 —, —(CH 2 ) s5 —X 53 —(CH 2 ) t5 — -X 54 -, or -X 54 -(CH 2 ) t5 - [In the formula, X 53 , X 54 , s5 and t5 have the same meanings as above. ] is.
  • X A are each independently single bond, a C 1-20 alkylene group, —(CH 2 ) s5 —X 53 —(CH 2 ) t5 —, or —X 54 —(CH 2 ) t5 — [In the formula, each symbol has the same meaning as described above. ] can be
  • each of the above X A is independently a single bond C 1-20 alkylene group, —(CH 2 ) s5 —X 53 —, or —(CH 2 ) s5 —X 53 —(CH 2 ) t5 —
  • X 53 is -O-, -CONR 54 -, or -O-CONR 54 -;
  • s5 is an integer from 1 to 20, t5 is an integer from 1 to 20;
  • t5 is an integer from 1 to 20;
  • each of the above X A is independently —(CH 2 ) s5 —O—(CH 2 ) t5 — -CONR54- ( CH2 ) t5-
  • R 54 at each occurrence independently represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group; s5 is an integer from 1 to 20, t5 is an integer from 1 to 20; ] can be
  • each of the X A is independently single bond, a C 1-20 alkylene group, —(CH 2 ) s5 —O—(CH 2 ) t5 —, —(CH 2 ) s5 —(Si(R 53 ) 2 O) m5 —Si(R 53 ) 2 —(CH 2 ) t5 —, - ( CH2 ) s5 -O-( CH2 ) u5- (Si( R53 ) 2O ) m5 -Si( R53 ) 2- ( CH2 ) t5- or -( CH2 ) s5 - O- ( CH2 )t5-Si(R53)2-( CH2 ) u5 -Si( R53 ) 2- ( CvH 2v )- [In the formula, R 53 , m5, s5, t5 and u5 have the same meanings as above, and v5 is an integer of 1 to 20,
  • -(C v H 2v )- may be linear or branched, for example -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH(CH 3 )-, -CH(CH 3 )CH 2 -.
  • Each X A may be independently substituted with 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). In one aspect, X A is unsubstituted.
  • X A is bonded to R F1 or R F2 on the left side of each formula, and is bonded to R Si on the right side.
  • each X A can independently be other than a —O—C 1-6 alkylene group.
  • X A includes, for example, the following groups: [wherein each R 41 is independently 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 -, where Ph means phenyl, and (In the formula, 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
  • X A above include: single bond, —CH 2 OCH 2 —, —CH 2 O(CH 2 ) 2 —, —CH 2 O(CH 2 ) 3 —, —CH 2 O(CH 2 ) 4 —, —CH 2 O(CH 2 ) 5 —, —CH 2 O(CH 2 ) 6 —, —CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —, —CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 —, —CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 2 Si(CH 3 ) 2 (CH 2 ) 2 —, —CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 2 Si(CH 3 ) 2 (CH
  • each X A is independently a group of the formula: -(R 16 ) x1 -(CFR 17 ) y1 -(CH 2 ) z1 -.
  • x1, y1 and z1 are each independently an integer of 0 to 10
  • the sum of x1, y1 and z1 is 1 or more
  • the order of existence of each parenthesized repeating unit is arbitrary in the formula.
  • each occurrence of R 16 is independently an oxygen atom, phenylene, carbazolylene, —NR 18 — (wherein R 18 represents a hydrogen atom or an organic group) or a divalent organic group.
  • R 18 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, n-propyl, which may be substituted with one or more fluorine atoms.
  • each occurrence of R 17 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 a fluoroalkyl group having 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group, a pentafluoroethyl group, and still more preferably a trifluoromethyl group.
  • examples of X A include the groups: [In the formula, each R 41 is independently 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 A group any one of the T's are attached to R F1 or R F2 of the molecular backbone: —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 - (where Ph means phenyl), or [In the formula, each R 42 independently represents a hydrogen atom, a C
  • Ts are attached to the R Si of the molecular backbone and, if present, the remaining Ts are each independently a methyl group, a phenyl group, a C 1-6 alkoxy group or a radical scavenging group or a UV absorbing group.
  • the radical-scavenging group is not particularly limited as long as it can scavenge radicals generated by light irradiation, but examples include residues of benzophenones, benzotriazoles, benzoic acid esters, phenyl salicylates, crotonic acids, malonic acid esters, organoacrylates, hindered amines, hindered phenols, or triazines.
  • the ultraviolet absorbing group is not particularly limited as long as it can absorb ultraviolet rays, but examples include benzotriazoles, hydroxybenzophenones, esters of substituted and unsubstituted benzoic acid or salicylic acid compounds, acrylates or alkoxycinnamates, oxamides, oxanilides, benzoxazinones, and benzoxazole residues.
  • preferred radical-scavenging groups or UV-absorbing groups include: is mentioned.
  • each X A can independently be a trivalent to decavalent organic group.
  • examples of X A include the groups: [wherein R 25 , R 26 and R 27 are each independently a divalent to hexavalent organic group, R 25 is bound to at least one R 2 F1 and R 26 and R 27 are each bound to at least one R 2 Si . ]
  • R 25 above is a single bond, a C 1-20 alkylene group, a C 3-20 cycloalkylene group, a C 5-20 arylene group, -R 57 -X 58 -R 59 -, -X 58 -R 59 -, or -R 57 -X 58 -.
  • R 57 and R 59 above are each independently a single bond, a C 1-20 alkylene group, a C 3-20 cycloalkylene group, or a C 5-20 arylene group.
  • X 58 above is -O-, -S-, -CO-, -O-CO- or -COO-.
  • R 26 and R 27 are each independently a hydrocarbon or a group having at least one atom selected from N, O and S in the end or main chain of the hydrocarbon, preferably a C 1-6 alkyl group, -R 36 -R 37 -R 36 -, -R 36 -CHR 38 2 - and the like.
  • each R 36 is independently a single bond or an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms.
  • R 37 is N, O or S, preferably N or O.
  • R 38 is -R 45 -R 46 -R 45 -, -R 46 -R 45 - or -R 45 -R 46 -.
  • each R 45 is independently an alkyl group having 1 to 6 carbon atoms.
  • R 46 is N, O or S, preferably O.
  • each X A can independently be a trivalent to decavalent organic group.
  • examples of X A include: [In the formula, X a is a single bond or a divalent organic group. ] A group represented by
  • X a above is a single bond or a divalent linking group that directly bonds to the isocyanuric ring.
  • X a is preferably a single bond, an alkylene group, or a divalent group containing at least one bond selected from the group consisting of an ether bond, an ester bond, an amide bond and a sulfide bond, and more preferably a single bond, an alkylene group having 1 to 10 carbon atoms, or a divalent hydrocarbon group having 1 to 10 carbon atoms containing at least one bond selected from the group consisting of an ether bond, an ester bond, an amide bond and a sulfide bond.
  • the above X a is not particularly limited, but specifically, -CH 2 -, -C 2 H 4 -, -C 3 H 6 -, -C 4 H 8 -, -C 4 H 8 -O -CH 2 -, -CO-O-CH 2 -CH (OH)-CH 2 -, -(CF 2 ) n5 - (n5 is an integer of 0 to 4), -(CF 2 ) n5 -(CH 2 ) m5 -(n5 and m5 are each independently an integer of 0 to 4.), -CF 2 CF 2 CH 2 OCH 2 CH (OH)CH 2 -, -CF 2 CF 2 CH 2 OCH 2 CH(OSi(OCH 3 ) 3 )CH 2 - etc.
  • each X A can independently be a divalent or trivalent organic group.
  • the fluorine-containing silane compound represented by formula (1) or formula (2) is not particularly limited, but may have an average molecular weight of 5 ⁇ 10 2 to 1 ⁇ 10 5 . Among these ranges, from the viewpoint of wear resistance, it is preferable to have an average molecular weight of 2,000 to 32,000, more preferably 2,500 to 12,000.
  • the "average molecular weight” refers to the number average molecular weight, and the “average molecular weight” is a value measured by 19 F-NMR.
  • the fluorine-containing silane compound in the surface treatment agent of the present disclosure is a compound represented by formula (1).
  • the fluorine-containing silane compound in the surface treatment agent of the present disclosure is a compound represented by formula (2).
  • the fluorine-containing silane compound in the surface treatment agent of the present disclosure is the compound represented by formula (1) and the compound represented by formula (2).
  • the compound represented by formula (2) is preferably 0.1 mol% or more and 35 mol% or less with respect to the total of the compound represented by formula (1) and the compound represented by formula (2).
  • the lower limit of the content of the compound represented by formula (2) with respect to the total of the compound represented by formula (1) and the compound represented by formula (2) is preferably 0.1 mol%, more preferably 0.2 mol%, still more preferably 0.5 mol%, still more preferably 1 mol%, particularly preferably 2 mol%, and particularly preferably 5 mol%.
  • the upper limit of the content of the compound represented by formula (2) with respect to the total of the compound represented by formula (1) and the compound represented by formula (2) is preferably 35 mol%, more preferably 30 mol%, still more preferably 20 mol%, and even more preferably 15 mol% or 10 mol%.
  • the compound represented by formula (2) to the total of the compound represented by formula (1) and the compound represented by formula (2) is preferably 0.1 mol% or more and 30 mol% or less, more preferably 0.1 mol% or more and 20 mol% or less, still more preferably 0.2 mol% or more and 10 mol% or less, even more preferably 0.5 mol% or more and 10 mol% or less, particularly preferably 1 mol% or more and 10 mol% or less, for example 2 mol% or more and 10 mol% or less, or 5 mol% or more and 10 mol% or more. mol% or less.
  • By setting the content of the compound represented by formula (2) within such a range it is possible to further improve wear resistance.
  • the surface treatment agent of the present disclosure contains two or more fluorine-containing silane compounds represented by formula (1) or (2).
  • the surface treatment agent of the present disclosure contains two or more fluorine-containing silane compounds represented by formula (1) or (2).
  • the surface treatment agent of the present disclosure includes two or more fluorine-containing silane compounds represented by formula (1) or (2), wherein R Si is a group selected from formulas (S1), (S2), (S3), (S4), and (S5) and is a group different from each other. Including fluorine-containing silane compounds having different R Si can further improve friction durability.
  • the surface treatment agent of the present disclosure includes a fluorine-containing silane compound represented by formula (1) or (2), in which R Si is a group represented by formula (S1), and a fluorine-containing silane compound represented by formula (1) or (2), in which R Si is a group selected from formulas (S3), (S4) and (S5).
  • Friction durability can be further improved by using together a fluorine-containing silane compound represented by formula (1) or (2), wherein R Si is a group represented by formula (S1), and a fluorine - containing silane compound represented by formula (1) or (2), wherein R Si is a group selected from formulas (S3), (S4) and (S5).
  • the surface treatment agent of the present disclosure includes a fluorine-containing silane compound represented by formula (1) or (2), wherein R Si is a group represented by formula (S1), and a fluorine-containing silane compound represented by formula (1) or (2), wherein R Si is a group selected from formulas (S3) and (S4).
  • Friction durability can be further improved by using together a fluorine-containing silane compound represented by formula (1) or (2), in which R Si is a group represented by formula (S1), and a fluorine-containing silane compound represented by formula (1) or (2), in which R Si is a group selected from formulas (S3 ) and (S4).
  • the surface treatment agent of the present disclosure includes a fluorine-containing silane compound represented by formula (1) or (2), in which R Si is a group represented by formula (S1), and a fluorine-containing silane compound represented by formula (1) or (2), in which R Si is a group represented by formula (S3).
  • a fluorine -containing silane compound represented by formula (1) or (2) in which R Si is a group represented by formula (S1) and a fluorine-containing silane compound represented by formula (1) or (2) in which R Si is a group represented by formula (S3) can further improve friction durability.
  • the surface treatment agent of the present disclosure includes a fluorine-containing silane compound represented by formula (1) or (2), in which R Si is a group represented by formula (S1), and a fluorine-containing silane compound represented by formula (1) or (2), in which R Si is a group represented by formula (S4).
  • Friction durability can be further improved by using together a fluorine-containing silane compound represented by formula (1) or (2) in which R Si is a group represented by formula (S1) and a fluorine-containing silane compound represented by formula (1) or (2) in which R Si is a group represented by formula (S4).
  • the compound represented by the above formula (1) or (2) can be obtained, for example, by a method known per se, such as the methods described in International Publication No. 97/07155, JP-A-2008-534696, JP-A-2014-218639, JP-A-2017-82194, and the like.
  • the content of the compound represented by the above formula (1) or (2) is preferably 0.01 to 50.0% by mass, more preferably 0.1 to 30.0% by mass, still more preferably 1.0 to 25.0% by mass, and particularly preferably 5.0 to 20.0% by mass, relative to the entire surface treatment agent.
  • the surface treatment agent of the present disclosure may include a solvent, a (non-reactive) fluoropolyether compound, preferably a perfluoro(poly)ether compound, which can be understood as a fluorine-containing oil (hereinafter collectively referred to as "fluorine-containing oil”), a (non-reactive) silicone compound which can be understood as silicone oil (hereinafter referred to as "silicone oil”), alcohols, compatibilizers, catalysts, surfactants, polymerization inhibitors, sensitizers, and the like.
  • fluorine-containing oil fluorine-containing oil
  • silicone oil silicone oil
  • solvents examples include aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, and mineral spirits; aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, and solvent naphtha; Esters such as ethyl acetate, ethyl-2-hydroxybutyrate, ethyl acetoacetate, amyl acetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate; Glycol ethers such as acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol
  • fluorine-containing oil examples include, but are not limited to, compounds represented by the following general formula (3) (perfluoro(poly)ether compounds).
  • Rf 5 represents a C 1-16 alkyl group optionally substituted by one or more fluorine atoms (preferably a C 1-16 perfluoroalkyl group)
  • Rf 6 represents a C 1-16 alkyl group optionally substituted by one or more fluorine atoms (preferably a C 1-16 perfluoroalkyl group)
  • Rf 5 and Rf 6 are more preferably each independently It is a C 1-3 perfluoroalkyl group.
  • a', b', c' and d' each represent the number of four types of repeating units of the perfluoro(poly)ether constituting the main skeleton of the polymer, and are independently integers of 0 or more and 300 or less, and the sum of a', b', c' and d' is at least 1, preferably 1 to 300, more preferably 20 to 300.
  • the order of existence of each repeating unit enclosed in parentheses with subscript a', b', c' or d' 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 ))-,- (OC(CF 3 ) 2 CF 2 )-, -(OCF 2 C(CF 3 ) 2 )-, -(OCF(CF 3 ) CF ( CF 3 ) ) -, -(OCF(C 2 F 5 )CF 2 )- and (OCF 2 CF(C 2 F 5 ))-, but preferably -(O CF 2 CF 2 CF 2 CF 2 )—.
  • -(OC 3 F 6 )- may be any of -(OCF 2 CF 2 CF 2 )-, -(OCF(CF 3 )CF 2 )- and (OCF 2 CF(CF 3 ))-, 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 compounds represented by the above general formula (3) include compounds represented by any of the following general formulas (3a) and (3b) (one or a mixture of two or more).
  • Rf 5 -(OCF 2 CF 2 CF 2 ) b′′ -Rf 6 (3a) Rf5- ( OCF2CF2CF2 ) a" -( OCF2CF2CF2 ) b" - ( OCF2CF2 ) c " -( OCF2 ) d " -Rf6 ( 3b )
  • Rf 5 and Rf 6 are as described above; in formula (3a), b'' is an integer of 1 to 100; in formula (3b), a'' and b'' are each independently an integer of 0 to 30, and c'' and d'' are each independently an integer of 1 to 300. .
  • the fluorine-containing oil may be a compound represented by the general formula Rf 3 —F (wherein Rf 3 is a C 5-16 perfluoroalkyl group). It may also be a chlorotrifluoroethylene oligomer.
  • the fluorine-containing oil may have an average molecular weight of 500-10,000.
  • the molecular weight of the fluorine-containing oil can be measured using GPC.
  • the fluorine-containing oil may be contained in an amount of, for example, 0.01-50% by mass, preferably 0.1-30% by mass, for example, 1-15% by mass, relative to the surface treatment agent of the present disclosure.
  • the surface treatment agent of the present disclosure is substantially free of fluorine-containing oil.
  • substantially free of fluorine-containing oil means that it does not contain fluorine-containing oil at all, or may contain a very small amount of fluorine-containing oil.
  • the average molecular weight of the fluorine-containing oil may be larger than the average molecular weight of the fluorine-containing silane compound. With such an average molecular weight, particularly when the surface treatment layer is formed by a vacuum deposition method, it is possible to obtain more excellent abrasion resistance and surface lubricity.
  • the average molecular weight of the fluorine-containing oil may be smaller than the average molecular weight of the fluorine-containing silane compound. With such an average molecular weight, it is possible to form a cured product having high abrasion resistance and high surface slipperiness while suppressing deterioration in the transparency of the surface treatment layer obtained from such a compound.
  • the fluorine-containing oil contributes to improving the surface lubricity of the layer formed by the surface treatment agent of the present disclosure.
  • silicone oil for example, linear or cyclic silicone oil having 2,000 or less siloxane bonds can be used.
  • Linear silicone oils may be so-called straight silicone oils and modified silicone oils.
  • straight silicone oils include dimethylsilicone oil, methylphenylsilicone oil, and methylhydrogensilicone oil.
  • Modified silicone oils include those obtained by modifying straight silicone oils with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol and the like.
  • Cyclic silicone oil includes, for example, cyclic dimethylsiloxane oil.
  • such a silicone oil may be contained in an amount of, for example, 0 to 300 parts by mass, preferably 50 to 200 parts by mass, based on a total of 100 parts by mass of the fluorine-containing silane compound of the present disclosure (the sum of these in the case of two or more types, the same shall apply hereinafter).
  • Silicone oil contributes to improving the surface lubricity of the surface treatment layer.
  • the alcohols include non-fluorine alcohols having 1 to 6 carbon atoms, such as methanol, ethanol, iso-propanol, and tert-butanol. By adding these alcohols to the surface treating agent, the stability of the surface treating agent is improved and the compatibility between the perfluorinated silane compound and the solvent is improved.
  • compatibilizing agent examples include fluorine-substituted alcohols such as 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoro-1-propanol or 2,2,3,3,4,4,5,5-octafluoro- 1 -pentanol, preferably fluorine-substituted alcohols having a terminal CF H, fluorine-substituted aryls such as 1,3-bis(trifluoromethyl)benzene, and preferably fluorine-substituted benzene.
  • fluorine-substituted alcohols such as 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoro-1-propanol or 2,2,3,3,4,4,5,5-octafluoro- 1 -pentanol
  • fluorine-substituted alcohols having a terminal CF H fluorine-substituted aryls such as 1,3-bis(trifluoromethyl)
  • 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 hydrolysis and dehydration condensation of the fluorine-containing silane compound of the present disclosure and promotes formation of a layer formed by the surface treatment agent of the present disclosure.
  • Other components include, in addition to the above, tetraethoxysilane, methyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltriacetoxysilane, and the like.
  • the surface treatment agent of the present disclosure can be made into pellets by impregnating a porous material, such as a porous ceramic material, metal fiber, such as steel wool, into a flocculated material.
  • a porous material such as a porous ceramic material, metal fiber, such as steel wool
  • the pellet can be used, for example, for vacuum deposition.
  • the surface treatment agent of the present disclosure may contain trace amounts of impurities such as Pt, Rh, Ru, 1,3-divinyltetramethyldisiloxane, triphenylphosphine, NaCl, KCl, and silane condensates.
  • impurities such as Pt, Rh, Ru, 1,3-divinyltetramethyldisiloxane, triphenylphosphine, NaCl, KCl, and silane condensates.
  • the thickness of the surface treatment layer is not particularly limited.
  • the thickness of the layer is preferably in the range of 1 to 50 nm, 1 to 30 nm, preferably 1 to 15 nm, from the viewpoint of optical performance, surface slipperiness, friction durability and antifouling properties.
  • the surface treatment layer can be formed, for example, by forming a layer of the surface treatment agent on the intermediate layer and post-treating this layer as necessary.
  • the layer formation of the surface treatment agent can be carried out by applying the surface treatment agent to the surface of the intermediate layer so as to cover the surface.
  • a coating method is not particularly limited. For example, wet coating methods and dry coating methods can be used.
  • wet coating methods include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating and similar methods.
  • Examples of dry coating methods include vapor deposition (usually vacuum deposition), sputtering, CVD and similar methods.
  • vapor deposition methods usually vacuum vapor deposition methods
  • Specific examples of vapor deposition methods include resistance heating, electron beams, high-frequency heating using microwaves, ion beams, and similar methods.
  • Examples of CVD methods include plasma-CVD, optical CVD, thermal CVD, and similar methods.
  • the surface treatment may be diluted with a solvent before being applied to the intermediate layer.
  • the surface treatment agent When using the dry coating method, the surface treatment agent may be subjected to the dry coating method as it is, or may be diluted with the above solvent and then subjected to the dry coating method.
  • the layer formation of the surface treatment agent is preferably carried out so that the surface treatment agent is present in the layer together with a catalyst for hydrolysis and dehydration condensation.
  • the catalyst may be added to the diluted solution of the surface treatment agent immediately before the surface treatment agent is diluted with a solvent and applied to the surface of the intermediate layer.
  • the surface treatment agent added with the catalyst may be vapor-deposited (usually vacuum vapor deposition) as it is, or a metal porous body such as iron or copper may be vapor-deposited (usually vacuum vapor-deposited) using a pellet-like substance in which the surface treatment agent added with the catalyst is impregnated.
  • Any suitable acid or base can be used as the catalyst.
  • acid catalysts that can be used include acetic acid, formic acid, and trifluoroacetic acid.
  • a basic catalyst for example, ammonia, organic amines, and the like can be used.
  • a layer derived from the surface treatment agent is formed on the surface of the intermediate layer to produce the article of the present disclosure.
  • the surface treatment layer thus obtained has high friction durability.
  • the layer may have water repellency, oil repellency, antifouling properties (for example, to prevent the adhesion of stains such as fingerprints), waterproofness (to prevent water from entering electronic components, etc.), surface slipperiness (or lubricity, such as the ability to wipe off stains such as fingerprints, and excellent tactile sensation on fingers), etc., and can be suitably used as a functional thin film.
  • the article of the present disclosure may further be an optical material having the surface treatment layer as the outermost layer.
  • optical members include the following: lenses for eyeglasses; front protective plates, antireflection plates, polarizing plates, anti-glare plates for displays such as PDP and LCD; touch panel sheets for devices such as mobile phones and personal digital assistants;
  • the articles of the present disclosure may be medical devices or medical materials.
  • the article of the present disclosure has an intermediate layer containing a Ce-containing layer on a base material, and a surface treatment layer formed thereon from a surface treatment agent containing a fluorine-containing silane compound, thereby having high friction durability and high weather resistance.
  • Gorilla Glass 5 manufactured by Corning Incorporated
  • a thickness of 0.8 mm, 66.0 mm x 142.0 mm, chemically strengthened, and surface polished was used.
  • a surface treatment layer was formed on the intermediate layer to obtain a glass substrate with a surface treatment layer. Details are as follows.
  • vapor deposition material As for the vapor deposition material of the single composition of SiO 2 and Ta 2 O 5 , the vapor deposition material manufactured by Canon Optron was purchased and used as the CeO 2 vapor deposition material manufactured by Sanwa Abrasive Industry Co., Ltd. Separately, vapor deposition materials having Si and Ce molar ratios of 95:5 and 90:10 were prepared and used. The molar ratio of Si and Ce was determined by X-ray fluorescence (XRF) analysis.
  • XRF X-ray fluorescence
  • the intermediate layer was deposited by electron beam evaporation (Examples 1-7, Comparative Examples 1, 3, and 4) or sputtering (Comparative Example 2).
  • Electron beam evaporation was performed as follows. SiO 2 alone, CeO 2 alone, Ta 2 O 5 alone, or both SiO 2 and CeO 2 were placed in the vacuum deposition apparatus, and the vacuum deposition apparatus was evacuated to a pressure of 3.0 ⁇ 10 ⁇ 3 Pa or less. Next, on Gorilla Glass 5 (manufactured by Corning), the conditions are set for each example, and a single layer of film forming material 1 shown in Table 1 below is formed, or layers of film forming material 1 and film forming material 2 are laminated to form an intermediate layer.
  • the sputtering method was performed as follows. A silicon target and a tantalum target were placed in a DC sputtering apparatus, and while introducing a mixed gas of argon and oxygen into the chamber, the deposition rate ratio (Si/Ta) was set to 9/1, and an intermediate layer composed of a composite oxide of silicon and tantalum having a thickness of 40 nm was deposited.
  • the surface treatment layer was formed using an apparatus capable of resistance heating vapor deposition. Specifically, 0.09 g of the surface treatment agent was filled in a resistance heating boat in a vacuum deposition apparatus, and the inside of the vacuum deposition apparatus was evacuated to a pressure of 3.0 ⁇ 10 ⁇ 3 Pa or less. Then, by raising the temperature of the resistance heating boat, a vapor deposition film was formed on the glass on which the intermediate layer was formed. Next, the vapor-deposited film-coated glass was allowed to stand in an atmosphere at a temperature of 150° C. for 30 minutes, and then allowed to cool to room temperature to form a surface-treated layer on the glass, and the surface-treated layer-coated glass substrates of Examples 1 to 7 and Comparative Examples 1 to 4 were obtained.
  • Friction element A surface (1 cm in diameter) of the silicone rubber product shown below was covered with cotton immersed in artificial sweat having the composition shown below, and this was used as a friction element.
  • Composition of artificial sweat Anhydrous disodium hydrogen phosphate: 2 g Sodium chloride: 20g 85% lactic acid: 2g Histidine hydrochloride: 5g Distilled water: 1 kg
  • Silicone rubber products A silicone rubber plug SR-51 manufactured by Tigers Polymer was processed into a cylindrical shape with a diameter of 1 cm and a thickness of 1 cm.
  • Example 5 (Accelerated weather resistance test evaluation) The glass substrates of Example 5 and Comparative Example 4 were subjected to an accelerated weather resistance test by xenon lamp irradiation.
  • the xenon irradiation was performed using a xenon lamp (manufactured by Suga Test Instruments Co., Ltd., irradiance of 180 W/m 2 at 300 to 400 nm), and the temperature of the plate on which the glass substrate was placed was 63°C.
  • Xenon irradiation was performed continuously, but when measuring the static contact angle of water, the glass substrate was once taken out, and the surface treatment layer was wiped with a Kimwipe (trade name, manufactured by Jujo Kimberly Co., Ltd.) saturated with pure water 5 times and then wiped with another Kimwipe sufficiently soaked with ethanol 5 times and dried. The static contact angle of water was measured immediately thereafter.
  • a Kimwipe trade name, manufactured by Jujo Kimberly Co., Ltd.
  • the static contact angle of water was measured before xenon irradiation on the glass substrate after the formation of the surface treatment layer (irradiation time: 0 hours). After that, the static contact angle of water was measured for each of the surface treatment layers after being irradiated with xenon for a predetermined time. The evaluation was performed from the start of xenon irradiation until the static contact angle of water fell below 90 degrees, or until the cumulative irradiation time was 1858 hours. Table 2 shows the results.
  • the article of the present disclosure can be suitably used in a wide variety of applications, such as optical members.

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Abstract

La présente invention concerne un article comprenant une couche intermédiaire positionnée sur un substrat, et une couche de traitement de surface qui est positionnée sur la couche intermédiaire et formée à partir d'un agent de traitement de surface comprenant un composé silane contenant du fluor, la couche intermédiaire comprenant une couche contenant du Ce.
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