Classifications

• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
  • C03C23/0005—Other surface treatment of glass not in the form of fibres or filaments by irradiation
  • C03C23/006—Other surface treatment of glass not in the form of fibres or filaments by irradiation by plasma or corona discharge
• • 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
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/02—Physical, chemical or physicochemical properties
  • B32B7/023—Optical properties
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
  • C03C17/38—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal at least one coating being a coating of an organic material
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
  • C03C23/0075—Cleaning of glass
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
  • G02B1/11—Anti-reflection coatings
  • G02B1/113—Anti-reflection coatings using inorganic layer materials only
  • G02B1/115—Multilayers
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
  • G02B1/14—Protective coatings, e.g. hard coatings
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
  • G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films

Definitions

• This disclosure relates to a method for treating a substrate.
• Patent document 1 describes a method of applying a functional layer to a glass substrate and chemically strengthening the glass substrate by ion exchange, and describes a method of treating the surface of the functional layer with oxygen plasma as one method.
• Patent documents 2 and 3 describe treating the anti-reflective coating surface with plasma, and then treating it with a fluorine-containing silane compound.
• the purpose of this disclosure is to provide a new method for surface treatment of a substrate having an anti-reflective coating.
• a method for treating a substrate having an anti-reflective coating comprising the steps of: carrying out a process for smoothing at least a portion of the surface of the anti-reflective coating; forming a layer containing SiO2 on the surface of the anti-reflective film after the treatment for smoothing at least a portion of the surface of the anti-reflective film; and applying a surface treatment agent to at least a partial area of a surface of the layer containing SiO2 to form a surface treatment layer.
• the treatment for smoothing at least a part of the surface of the anti-reflective film and the formation of the layer containing SiO 2 are carried out so that the amount of OH groups C 1 on the surface of the layer containing SiO 2 is 1.4 times or more the amount of OH groups C 0 on the surface of the anti-reflective film before the treatment for smoothing at least a part of the surface of the anti-reflective film.
• the treatment of smoothing at least a portion of the surface of the anti-reflection coating is carried out by plasma irradiation; The method according to any one of [1] to [4], wherein the voltage in the plasma irradiation is 140 V or more.
• the treatment of smoothing at least a portion of the surface of the anti-reflection coating is carried out by plasma irradiation;
• the treatment of smoothing at least a portion of the surface of the anti-reflection coating is carried out by plasma irradiation;
• the treatment of smoothing at least a portion of the surface of the anti-reflection coating is carried out by plasma irradiation;
• the surface treatment agent contains a fluorine-containing silane compound.
• the fluorine-containing silane compound is represented by the following formula (1) or (2): [Wherein: R F1 at each occurrence is independently Rf 1 -R F -O q - or a fluoroalkyl group; R F2 is —Rf 2 p —R F —O q — or a fluoroalkylene group; Rf 1 , at each occurrence, is independently a C 1-16 alkyl group optionally substituted by one or more fluorine atoms; Rf2 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, independently at each occurrence, is 0 or 1; R Si , in each occurrence, is independently a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent group containing a Si atom to which a monovalent organic group
• the voltage in the plasma irradiation is 100 V or more and 180 V or less,
• the gas flow rate in the plasma irradiation is 40 sccm or more and 60 sccm or less,
• the plasma irradiation time in the plasma irradiation is 100 seconds or more and 700 seconds or less,
• the layer containing electrical SiO2 is formed by deposition
• the surface treatment agent has the following formula (1'): R F1 -X A -R Si (1') [Wherein: R F1 at each occurrence is independently Rf 1 -R F -O q - or a fluoroalkyl group; Rf 1 , at each occurrence, is independently a C 1-16 alkyl group optionally substituted by one or more
• R Si is represented by the following formula: -SiR a1 k1 R b1 l1 R c1 m1 (S3) [Wherein: R a1 is independently at each occurrence -Z 1 -SiR 21 p1 R 22 q1 R 23 r1 ; Z 1 is independently at each occurrence -(CH 2 ) z1 -O-(CH 2 ) z2 -; z1 is an integer from 0 to 6; z2 is an integer from 0 to 6; R 21 is independently at each occurrence -Z 1' -SiR 21' p1' R 22' q1' R 23' r1' ; Z 1′ in each occurrence is independently an oxygen atom or a divalent organic group; The structure depicted as Z 1' is bonded on the right side to (SiR 21' p1' R 22' q1' R 23' r1' ); R 21' is independently at each occurrence -
• This disclosure can provide a new method for treating the surface of a substrate having an anti-reflective coating.
• the treatment method of the present disclosure is a method for treating a substrate provided with an anti-reflective coating, comprising the steps of: carrying out a process for smoothing at least a portion of the surface of the anti-reflective coating; forming a layer containing SiO2 on the surface of the anti-reflective film after the treatment for smoothing at least a portion of the surface of the anti-reflective film; and Applying a surface treatment agent to at least a partial area of the surface of the SiO2- containing layer to form a surface treatment layer;
• the surface treatment agent includes a fluorine-containing silane compound.
• This disclosure can provide a new method for treating the surface of a substrate having an anti-reflective coating.
• Anti-reflective coatings are typically formed by laminating multiple layers with different refractive indices, and may have a rough surface and poor abrasion resistance.
• the layers constituting the anti-reflective coating do not necessarily have good reactivity with silane compounds, and a surface treatment layer formed on such an anti-reflective coating may have poor durability.
• the treatment method of the present disclosure maintains the transparency of a substrate provided with an anti-reflective coating, and can improve the durability, particularly the abrasion resistance, of the surface treatment layer.
• a layer containing SiO 2 is further formed after performing a process to smooth the surface of the anti-reflective film.
• the inventors have found that such a process can flatten the surface of the anti-reflective film and increase the amount of OH groups on the surface of the anti-reflective film.
• a surface treatment agent is further applied to the surface of the layer containing SiO 2 , a surface treatment layer can be formed uniformly and densely, and has excellent durability, especially wear resistance.
• the treatment method disclosed herein is applied to a substrate having an anti-reflective coating.
• the anti-reflective coating can suppress reflection of light incident on the anti-reflective coating surface.
• An anti-reflective film may typically include two or more layers with different refractive indices. By including two or more layers with different refractive indices, incident light may be reflected at the interface between the two layers with different refractive indices, and the reflected light at the different interfaces may cancel each other out, allowing the anti-reflective film as a whole to suppress reflection of incident light.
• the anti-reflective coating may preferably contain one selected from the group consisting of metals, alloys, metal oxides, metal nitrides, metal sulfides, and metal fluorides, and more preferably contain one selected from the group consisting of metals, metal oxides, and metal nitrides.
• the metals include Al, Au, Ag, Cu, Fe, Zn, Cr and Ni, and preferably Al, Au, Ag and Cu.
• the alloys include alloys containing the metals, specifically SUS and brass.
• the metal oxides include SiO2 , TiO2 , Al2O3 , ZrO2 , Nb2O5 , CeO2 , HfO2 , Ta2O5 and ZrTiO3 .
• the metal nitrides include Si3N4 , AlN, SiN and SiAlN.
• the metal sulfides include ZnS .
• the metal fluorides include MgF2 and CeF3 .
• the anti-reflection film may preferably include a high refractive index layer having a relatively high refractive index and a low refractive index layer having a relatively low refractive index.
• the refractive index of the high refractive index layer may be preferably 1.7 or more, more preferably 1.7 to 2.8, and even more preferably 1.8 to 2.6, based on light with a wavelength of 550 nm.
• the refractive index of the low refractive index layer may be preferably less than 1.7, more preferably 1.2 to 1.65, and even more preferably 1.2 to 1.6, based on light with a wavelength of 550 nm.
• the refractive index difference between the high refractive index layer and the low refractive index layer may be preferably 0.5 or more and 1.5 or less, and more preferably 0.7 or more and 1.2 or less.
• the anti-reflection film is a laminate in which the high refractive index layers and the low refractive index layers are alternately laminated.
• the total number of high refractive index layers and low refractive index layers in the anti-reflection film is preferably 3 to 10, more preferably 5 to 8.
• the outermost layer of the anti-reflection film may be either a high refractive index layer or a low refractive index layer, and is preferably a low refractive index layer.
• the arithmetic mean roughness Ra 0 of the antireflective film surface may be preferably 1 nm or more and 50 nm or less, more preferably 2 nm or more and 30 nm or less, and even more preferably 3 nm or more and 10 nm or less.
• the arithmetic mean roughness can be measured in accordance with JIS B 0601.
• the arithmetic mean roughness Ra 0 of the antireflective film surface may be the arithmetic mean roughness of the antireflective film surface before a treatment for smoothing at least a partial region of the surface of the antireflective film is performed.
• the substrate may typically be a transparent substrate, and may be either a resin substrate or a glass substrate, preferably a glass substrate.
• the glass constituting the glass substrate examples include sapphire glass, soda-lime glass, alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass, and quartz glass, and these glasses may be chemically strengthened, but are not limited thereto. More preferred examples of the glass constituting the glass substrate include chemically strengthened soda-lime glass, chemically strengthened alkali aluminosilicate glass, and chemically strengthened borosilicate glass.
• the thickness of the glass substrate can typically be 0.1 mm or more and 1 mm or less.
• the resin constituting the resin substrate examples include, but are not limited to, polyester resin, acrylic resin, polyolefin resin, polycarbonate resin, polyethersulfone resin, polyarylate resin, polyamide resin, polyimide resin, cellulose resin, and polystyrene resin.
• the thickness of the resin substrate can typically be 0.1 mm or more and 1 mm or less.
• a substrate provided with an anti-reflective coating is subjected to a process for smoothing at least a portion of the surface of the anti-reflective coating (hereinafter also referred to as a "surface smoothing process").
• a surface smoothing process may be any process that improves the smoothness of the surface before and after the process. Examples of such surface smoothing process include ion cleaning process, flame process, and UV ozone process, with ion cleaning process being preferred. The ion cleaning process can remove excess ions that may be present on the anti-reflective coating surface.
• the above-mentioned ion cleaning treatments include corona treatment, plasma treatment, flame treatment and glow treatment, with plasma treatment being preferred.
• the above plasma treatment can typically be carried out by irradiating the surface with plasma.
• the above plasma includes vacuum plasma such as microwave plasma and high frequency plasma; atmospheric pressure plasma, with atmospheric pressure plasma being preferred.
• Process gases used to generate plasma include oxygen, nitrogen, fluorine, hydrogen, argon, and air, with oxygen and/or argon being preferred.
• the voltage in the plasma irradiation may be preferably 100 V or more, more preferably 120 V or more and 240 V or less, even more preferably 140 V or more and 220 V or less, and even more preferably 150 V or more and 180 V or less.
• the surface of the anti-reflective film can be made smoother.
• the current in the plasma irradiation is preferably 0.3 A or more, more preferably 0.5 A to 10 A, even more preferably 1 A to 8 A, and even more preferably 3 A to 6 A.
• the surface of the anti-reflective film can be made smoother.
• the plasma exposure time in the above plasma exposure may be preferably from 100 seconds to 1,000 seconds, more preferably from 100 seconds to 700 seconds.
• the surface of the anti-reflective film can be made smoother, and the transparency of the substrate can be more easily maintained.
• the plasma irradiation time in the above plasma irradiation may be preferably 100 seconds or more and 700 seconds or less.
• the surface of the anti-reflective film can be made smoother and it may become easier to maintain the transparency of the substrate.
• the plasma irradiation time in the plasma irradiation may be preferably 100 seconds or more and 800 seconds or less, more preferably 180 seconds or more and 600 seconds or less.
• the plasma irradiation can be performed at an irradiation distance of preferably 1 mm to 300 mm, more preferably 1.5 mm to 200 mm, and even more preferably 2 mm to 100 mm.
• the irradiation distance can be preferably 1 mm or more, more preferably 1.5 mm or more, and even more preferably 2 mm or more, and preferably 300 mm or less, more preferably 200 mm or less, and even more preferably 100 mm or less.
• the irradiation distance may be the straight-line distance from the plasma emission position to the irradiation target.
• a layer containing SiO 2 is formed on the surface of the anti-reflection film after the above-mentioned surface smoothing treatment.
• the adhesion with a surface treatment agent can be improved.
• the content of SiO 2 may be preferably 80% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less, and even more preferably 95% by mass or more and 100% by mass or less.
• the SiO 2 -containing layer may contain other metal oxides in addition to SiO 2. Examples of such metal oxides include Al 2 O 3 and TiO 2.
• the SiO 2 -containing layer may also contain at least one composite oxide of elements of Groups 4, 5, and 13 of the periodic table.
• the layer containing SiO 2 may be formed by a liquid phase method or a gas phase method, but is not limited thereto.
• the liquid phase method includes, but is not limited to, a sol-gel method, a liquid phase deposition method, a coprecipitation method, etc.
• the gas phase method includes, but is not limited to, a sputtering method, a vapor deposition method, etc.
• the layer containing SiO 2 is preferably formed by a gas phase method, more preferably by a vapor deposition method.
• the vapor deposition method may be a physical vapor deposition method or a chemical vapor deposition method, and is preferably a physical vapor deposition method.
• Examples of the physical vapor deposition method include a sputtering method, an ion-assisted method, and a vacuum vapor deposition method, and preferably an ion-assisted method.
• a film (layer) can be obtained by, typically, physically evaporating the deposition source and depositing it on the deposition target.
• the evaporation of the deposition source can be, typically, performed by irradiating the deposition source with an electron beam (EB irradiation).
• EB irradiation an electron beam
• the acceleration voltage during the electron beam irradiation may be preferably 700 V or more and 1,500 V or less, more preferably 800 V or more and 1,300 V or less, and even more preferably 900 V or more and 1,200 V or less.
• the acceleration current during the electron beam irradiation may be preferably 200 mA or more and 800 mA or less, more preferably 300 mA or more and 700 mA or less, and even more preferably 400 mA or more and 600 mA or less.
• the deposition source may be a metal oxide containing SiO 2.
• the metal oxide may contain Al 2 O 3 , TiO 2, etc. in addition to SiO 2.
• the content of SiO 2 in the deposition source may be preferably 80% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less.
• the deposition source may be heated.
• the temperature of the deposition source may be preferably 600°C or higher and 1,400°C or lower, more preferably 700°C or higher and 1,300°C or lower, and even more preferably 800°C or higher and 1,200°C or lower.
• the deposition may be performed under vacuum.
• the pressure during deposition may be preferably 1.0 ⁇ 10 ⁇ 4 Pa or more and 1.0 ⁇ 10 ⁇ 1 Pa or less, more preferably 1.0 ⁇ 10 ⁇ 3 Pa or more and 5.0 ⁇ 10 ⁇ 2 Pa or less, and even more preferably 1.0 ⁇ 10 ⁇ 2 Pa or more and 3.0 ⁇ 10 ⁇ 2 Pa or less.
• the deposition may be carried out in the presence of an ion assist gas.
• an ion assist gas By allowing the ion assist gas to coexist, the adhesion and film formability of the obtained film to the anti-reflective film (i.e., the anti-reflective film after the surface smoothing treatment) may be improved.
• the ion assist gas may be O2 gas.
• the flow rate of the ion assist gas may be preferably 20 sccm or more and 80 sccm or less, more preferably 30 sccm or more and 70 sccm or less, and even more preferably 40 sccm or more and 60 sccm or less.
• the above-mentioned surface smoothing treatment and formation of the SiO 2 -containing layer can be carried out so that the arithmetic mean roughness Ra 1 of the surface of the SiO 2 -containing layer is preferably 0.1 nm or more and 5 nm or less, more preferably 0.5 nm or more and 4 nm or less, and even more preferably 1 nm or more and 3 nm or less.
• the surface smoothing treatment and the formation of the SiO2 -containing layer can be carried out so that the arithmetic mean roughness Ra 1 of the surface of the SiO2 -containing layer is preferably 50% or less, more preferably 20% or less, and even more preferably 10% or less, for example, 0.2% or more, relative to the arithmetic mean roughness Ra 0 of the antireflection film before the surface smoothing treatment.
• the surface smoothing treatment and the formation of the SiO 2 -containing layer can be carried out so that the amount of OH groups C 1 on the surface of the SiO 2 -containing layer is preferably 1.1 times or more, more preferably 1.4 times or more, even more preferably 2 times or more, and even more preferably 2.5 times or more, relative to the amount of OH groups C 0 on the anti-reflection film surface before the surface smoothing treatment, and can be, for example, 10 times or less.
• the amount of OH groups can be measured by TOF-SIMS.
• the thickness of the SiO 2 -containing layer may be preferably 0.1 nm or more and 10 nm or less, more preferably 1 nm or more and 6 nm or less.
• the thickness of the SiO 2 -containing layer is in this range, the amount of OH groups is secured, the smoothness of the surface is improved, and further, it becomes easier to maintain the transparency of the substrate.
• the thickness of the layer containing SiO 2 may be preferably 0.1 nm or more and 10 nm or less, more preferably 1 nm or more and 6 nm or less.
• the thickness of the layer containing SiO2 may be preferably 0.1 nm or more and 6 nm or less, more preferably 1 nm or more and 3 nm or less.
• a surface treatment layer is formed by applying a surface treatment agent to at least a part of the surface of the SiO2 -containing layer, which can impart one or more properties selected from water repellency, oil repellency, slipperiness, fingerprint resistance, antifouling properties, antireflection properties, and antifogging properties.
• the surface treatment agent can be applied by applying the surface treatment agent to the surface of the display panel so as to coat the surface.
• the coating method is not particularly limited. For example, a wet coating method and a dry coating method can be used, and the wet coating method is preferably used.
• wet coating methods include dip coating, spin coating, brush coating, flow coating, spray coating, roll coating, gravure coating and similar methods, with spray coating being preferred.
• the layer of the surface treatment agent is preferably formed so that the surface treatment agent of the present disclosure is present in the layer together with a catalyst for hydrolysis and dehydration condensation.
• the catalyst may be added to a diluted solution of the surface treatment agent of the present disclosure after diluting the surface treatment agent of the present disclosure with a solvent immediately before applying it to the surface of the substrate.
• 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.
• base catalysts that can be used include ammonia and organic amines.
• the surface treatment agent After the surface treatment agent is applied, it may be dried as necessary. Such drying promotes the hydrolysis and dehydration condensation of the fluorine-containing silane compound described below, and can remove the solvent, etc.
• the drying of the precursor layer is preferably carried out at a temperature of 0°C or higher and 60°C or lower, more preferably 5°C or higher and 50°C or lower, and even more preferably 10°C or higher and 30°C or lower, and is preferably carried out for a period of 1 hour or higher and 48 hours or lower, more preferably 3 hours or higher and 24 hours or lower, and even more preferably 6 hours or higher and 12 hours or lower.
• the thickness of the surface treatment layer is not particularly limited. From the viewpoints of optical performance, abrasion resistance, and antifouling properties, the thickness of the surface treatment layer is preferably in the range of 1 to 50 nm, 1 to 30 nm, and preferably 1 to 15 nm.
• the surface treatment agent preferably contains a fluorine-containing silane compound.
• the fluorine-containing silane compound is a compound containing at least a fluorine-containing group and a silane, and is preferably represented by the following formula (1) or (2): [Wherein: 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 , at each occurrence, is independently a C 1-16 alkyl group optionally substituted by one or more fluorine atoms; Rf2 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, independently at each occurrence, is 0 or 1; R Si , in each occurrence, is independently a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent group containing a Si atom to which
• R F1 is, independently at each occurrence, Rf 1 -R F -O q - or a fluoroalkyl group.
• R F1 is preferably Rf 1 -R F -O q -, and in another embodiment, R F1 is preferably a fluoroalkyl group.
• the compound represented by formula (1) contains a fluoropolyether group and corresponds to a fluoropolyether group-containing silane compound.
• R F2 is -Rf 2 p -R F -O q - or a fluoroalkylene group.
• R F2 is preferably Rf 2 p -R F -O q -, and in another embodiment, R F2 is preferably a fluoroalkylene group.
• the compound represented by formula (2) contains a fluoropolyether group and corresponds to a fluoropolyether group-containing silane compound.
• Rf 1 at each occurrence is independently a C 1-16 alkyl group optionally substituted with one or more fluorine atoms.
• the "C 1-16 alkyl group" in the above-mentioned C 1-16 alkyl group optionally substituted by one or more fluorine atoms may be a straight chain or a branched chain, and is preferably a straight chain or branched chain C 1-6 alkyl group, particularly a C 1-3 alkyl group, and more preferably a straight chain C 1-6 alkyl group, particularly a C 1-3 alkyl group.
• Rf 1 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, and even more preferably a C 1-16 perfluoroalkyl group.
• the above C 1-16 perfluoroalkyl group may be linear or branched, and is preferably a linear or branched C 1-6 perfluoroalkyl group, in particular a C 1-3 perfluoroalkyl group, and more preferably a linear C 1-6 perfluoroalkyl group, in particular a C 1-3 perfluoroalkyl group, specifically -CF 3 , -CF 2 CF 3 , or -CF 2 CF 2 CF 3 .
• Rf2 is a C 1-6 alkylene group optionally substituted with one or more fluorine atoms.
• C 1-6 alkylene group in the above-mentioned C 1-6 alkylene group optionally substituted by one or more fluorine atoms may be a straight chain or a branched chain, and is preferably a straight chain or branched chain C 1-3 alkylene group, and more preferably a straight chain C 1-3 alkylene group.
• Rf 2 is preferably a C 1-6 alkylene group substituted with one or more fluorine atoms, more preferably a C 1-6 perfluoroalkylene group, and even more preferably a C 1-3 perfluoroalkylene group.
• the C 1-6 perfluoroalkylene group may be linear or branched, and is 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 embodiment, p is 0. In another embodiment, p is 1.
• q is, independently at each occurrence, 0 or 1. In one embodiment, q is 0. In another embodiment, q is 1.
• RF is, independently at each occurrence, a divalent fluoropolyether group.
• RF is preferably the following: -(OC h1 R Fa 2h1 ) h3 -(OC h2 R Fa 2h2-2 ) h4 - [Wherein: R Fa at each occurrence is independently 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 equal to or greater than 0; h4 is an integer equal to or greater than 0; However, the number of repeating units of h3 and h4 is 1 or more, preferably 2 or more, and more preferably 5 or more, and the order of the repeating units enclosed in parentheses with h3 and h4 is arbitrary in the formula. It may contain a group represented by:
• RF can be linear or branched.
• RF is preferably 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: R Fa at each occurrence 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, and the sum of a, b, c, d, e, and f is 1 or more.
• each repeating unit enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula. However, when all R Fa are hydrogen atoms or chlorine atoms, at least one of a, b, c, e, and f is 1 or more.] It is a group represented by the following formula:
• R Fa is preferably a hydrogen atom or a fluorine atom, more preferably a fluorine atom, provided that when all R Fa 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 each preferably be independently 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, and even more preferably 60 or less, and may be, for example, 50 or less or 30 or less.
• repeating units may be linear or branched, and may contain a ring structure.
• -(OC 6 F 12 )- is -(OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 )-, -(OCF(CF 3 )CF 2 CF 2 CF 2 )-, -(OCF 2 CF(CF 3 )CF 2 CF 2 CF 2 )-, -(OCF 2 CF 2 CF (CF 3 )CF 2 CF 2 )-, -(OCF 2 CF 2 CF 2 CF (CF 3 )CF 2 )-, etc. may be used.
• -(OC 5 F 10 )- is -(OCF 2 CF 2 CF 2 CF 2 CF 2 )-, -(OCF(CF 3 )CF 2 CF 2 CF 2 )-, -(OCF 2 CF(CF 3 )CF 2 CF 2 )-, -(OCF 2 CF 2 CF(CF 3 )CF 2 )-, -(OCF 2 CF 2 CF(CF 3 ))-, etc. may be used.
• - ( OC4F8 )- may be any of -( OCF2CF2CF2CF2 )-, -(OCF( CF3 ) CF2CF2 ) - , - ( OCF2CF ( CF3 ) CF2 )-, - ( OCF2CF2CF ( CF3 ))-, -(OC(CF3)2CF2)-, -(OCF2C(CF3)2 ) - , -(OCF(CF3)CF(CF3 ) ) - , - ( OCF ( C2F5 ) CF2 )- and -( OCF2CF ( C2F5 ))-.
• -(OC 3 F 6 )- (i.e., in the above formula, R 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 any of -(OCF 2 CF 2 )- and -(OCF(CF 3 ))-.
• the repeating unit is linear. By making the repeating unit linear, the surface slip properties, abrasion resistance, etc. of the surface treatment layer can be improved.
• the repeating unit is branched. By making the repeating unit branched, the dynamic friction coefficient of the surface treatment layer can be increased.
• R F can include a ring structure.
• the ring structure may be a three-, four-, five-, or six-membered ring as shown below.
• the ring structure may preferably be a four-membered ring, a five-membered ring, or a six-membered ring, more preferably a four-membered ring or a six-membered ring.
• the repeating unit having a ring structure may preferably be the following unit:
• the repeating unit is linear. By making the repeating unit linear, the surface slip properties, abrasion resistance, etc. of the surface treatment layer can be improved.
• the repeating unit is branched. By making the repeating unit branched, the dynamic friction coefficient of the surface treatment layer can be increased.
• R F is, independently at each occurrence, a group represented by any one of the following formulas (f1) to (f6): -(OC 3 F 6 ) d - (OC 2 F 4 ) e - (f1) [In the formula, d is an integer from 1 to 200, and e is 0 or 1.] -(OC 4 F 8 ) c - (OC 3 F 6 ) d - (OC 2 F 4 ) e - (OCF 2 ) f - (f2) [In the formula, c and d each independently represent an integer of 0 or more and 30 or less, and e and f each independently represent an integer of 1 or more and 200 or less, the sum of c, d, e, and f is 2 or more; The order of occurrence of each repeat unit enclosed in parentheses with the subscript c, d, e, or f is arbitrary in the formula.
• R6 is OCF2 or OC2F4
• 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
• R6 ' is OCF2 or OC2F4
• R 7′ is a group selected from OC 2 F 4 , OC 3 F 6 ,
• d is preferably an integer of 5 to 200, more preferably 10 to 100, further preferably 15 to 50, for example, 25 to 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 ).
• (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 is 0.
• e is 1.
• e and f are each independently an integer of preferably 5 to 200, more preferably 10 to 200.
• 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 -(OCF 2 CF 2 CF 2 CF 2 ) c -(OCF 2 CF 2 CF 2 ) d -(OCF 2 CF 2 ) e -(OCF 2 ) f -.
• the formula (f2) may be a group represented by -(OC 2 F 4 ) e -(OCF 2 ) f -.
• R6 is preferably OC2F4 .
• R7 is preferably a group selected from OC2F4 , OC3F6 , and OC4F8 , or a combination of two or three groups independently selected from these groups , and more preferably a group selected from OC3F6 and OC4F8 .
• the combination of two or three groups independently selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 is not particularly limited, and examples thereof include -OC 2 F 4 OC 3 F 6 -, -OC 2 F 4 OC 4 F 8 -, -OC 3 F 6 OC 2 F 4 -, -OC 3 F 6 OC 3 F 6 -, -OC 3 F 6 OC 4 F 8 -, -OC 4 F 8 OC 4 F 8 -, -OC 4 F 8 OC 3 F 6 -, -OC 4 F 8 OC 2 F 4 -, -OC 2 F 4 OC 2 F 4 OC 3 F 6 -, -OC 2 F 4 OC 2 F 4 OC 3 F 6 -, -OC 2 F 4 OC 2 F 4 OC 4 F 8 -, -OC 2 F 4 OC 3 F 6 -, -OC 2 F 4 OC 2 F 4 OC 4 F 8 -, -OC 2 F 4 OC 3 F 6 -,
• g is preferably an integer of 3 or more, more preferably 5 or more.
• the above 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 either linear or branched, and are 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 those described in the above formula (f3) and have the same embodiments.
• R 6 ' , R 7 ' and g ' have the same meanings as those described in the above formula (f3) and have the same embodiments.
• R r is preferably
• e is preferably an integer of 1 or more and 100 or less, more preferably an integer of 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 an integer of 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.
• the R F is a group represented by the formula (f1).
• the RF is a group represented by the formula (f2).
• the R F is a group represented by the formula (f3).
• the R F is a group represented by the formula (f4).
• the R F is a group represented by the formula (f5).
• the R F is a group represented by the formula (f6).
• the fluorine-containing silane compound contained in the surface treatment layer preferably contains a structure represented by the above formula (f1), (f2), (f3), (f5) or (f6), more preferably contains a structure represented by the above formula (f1) or (f2), and even more preferably contains a structure represented by the above formula (f1), from the viewpoint of the slipperiness of the surface treatment layer.
• the fluorine-containing silane compound that may be contained in the surface treatment layer preferably contains a structure represented by the above formula (f1), (f2), (f3), (f4), (f5) or (f6), more preferably contains a structure represented by the above formula (f1) or (f2), and even more preferably contains a structure represented by the above formula (f2).
• 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, even more preferably 0.2 to 1.5, and even more preferably 0.2 to 0.85.
• e/f ratio 10 the slipperiness, abrasion resistance, and chemical resistance (e.g., durability against artificial sweat) of the surface treatment layer obtained from this compound are further improved.
• the smaller the e/f ratio the more the slipperiness and abrasion resistance of the surface treatment layer are improved.
• the e/f ratio 0.1 or more the stability of the compound can be further improved. The larger the e/f ratio, the more the stability of the compound is improved.
• the fluoroalkyl group represented by R F1 is a group in which hydrogen atoms contained in an alkyl group are replaced with fluorine atoms, and may be linear or branched.
• the fluoroalkyl group represented by R F1 is preferably a C 1-50 fluoroalkyl group, more preferably a C 1-20 fluoroalkyl group, and even more preferably a C 1-16 fluoroalkyl group, and may be, for example, a C 1-10 fluoroalkyl group, further a C 1-6 fluoroalkyl group, and particularly a C 1-3 fluoroalkyl group.
• the fluoroalkyl group represented by R F1 is a perfluoroalkyl group in which all hydrogen atoms are replaced with fluorine atoms.
• the perfluoroalkyl group is preferably a linear or branched C 1-50 perfluoroalkyl group, more preferably a linear or branched C 1-20 perfluoroalkyl group, and even more preferably a linear or branched C 1-16 perfluoroalkyl group, and may be, for example, a linear or branched C 1-10 perfluoroalkyl group, further a linear or branched C 1-6 perfluoroalkyl group, and particularly a linear or branched C 1-3 perfluoroalkyl group.
• the fluoroalkylene group represented by R F2 is a group in which hydrogen atoms contained in an alkylene group are replaced with fluorine atoms, and may be linear or branched.
• the fluoroalkylene group represented by R F2 is preferably a C 1-50 fluoroalkylene group, more preferably a C 1-20 fluoroalkylene group, and even more preferably a C 1-16 fluoroalkylene group, and may be, for example, a C 1-10 fluoroalkylene group, further a C 1-6 fluoroalkylene group, and particularly a C 1-3 fluoroalkylene group.
• the fluoroalkylene group represented by R F2 is a perfluoroalkylene group in which all hydrogen atoms are replaced with fluorine atoms.
• the perfluoroalkylene group is preferably a linear or branched C 1-50 perfluoroalkylene group, more preferably a linear or branched C 1-20 perfluoroalkylene group, and even more preferably a linear or branched C 1-16 perfluoroalkylene group, and may be, for example, a linear or branched C 1-10 perfluoroalkylene group, further a linear or branched C 1-6 perfluoroalkylene group, and particularly a linear or branched C 1-3 perfluoroalkylene group.
• the number average molecular weight of the RF1 and RF2 portions is not particularly limited, but is, 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 RF1 and RF2 are values measured by 19F -NMR.
• the number average molecular weight of the RF1 and RF2 portions may be from 500 to 30,000, preferably from 1,000 to 20,000, more preferably from 2,000 to 15,000, even more preferably from 2,000 to 10,000, for example, from 3,000 to 6,000.
• the number average molecular weight of the RF1 and RF2 portions can be from 4,000 to 30,000, preferably from 5,000 to 10,000, and more preferably from 6,000 to 10,000.
• R 3 Si is independently in each occurrence a monovalent group containing a Si atom having a hydroxyl group, a hydrolyzable group, a hydrogen atom, or a monovalent organic group bonded thereto, and at least one R 3 Si is a monovalent group containing a Si atom having a hydroxyl group or a hydrolyzable group bonded thereto.
• hydrolyzable group refers to a group that can undergo a hydrolysis reaction, i.e., a group that can be eliminated from the main skeleton of a compound by a hydrolysis reaction.
• R 1 Si is a monovalent group containing a Si atom having a hydroxyl group or a hydrolyzable group bonded thereto.
• R Si is represented by the following formula (S1), (S2), (S3), or (S4): It is a group represented by the following formula:
• R 11 at each occurrence is independently a hydroxyl group or a hydrolyzable group.
• R 11 is preferably, independently at each occurrence, a hydrolyzable group.
• R j includes unsubstituted alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group; and substituted alkyl groups such as a chloromethyl group.
• an alkyl group particularly an unsubstituted alkyl group, is preferred, and a methyl group or an ethyl group is more preferred.
• R j is a methyl group, and in another embodiment, R j is an ethyl group.
• R 12 is independently at each occurrence 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.
• 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)
• at least one (SiR 11 n1 R 12 3-n1 ) unit in which n1 is 1 to 3 is present in the terminal R Si portion of formula (1) and formula (2) (hereinafter, also simply referred to as the "terminal portion" of formula (1) and formula ( 2 ) ). That is, in such a terminal portion, all n1s do not become 0 at the same time.
• at least one Si atom to which a hydroxyl group or a hydrolyzable group is bonded is present in the terminal portion of formula (1) and formula (2).
• n1 is preferably an integer of 1 to 3, more preferably 2 to 3, and further preferably 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.
• a divalent organic group is preferably -R 28 -O x -R 29 - (wherein R 28 and R 29 are, independently at each occurrence, a single bond or a C 1-20 alkylene group, and x is 0 or 1).
• Such a C 1-20 alkylene group may be linear or branched, but is preferably linear.
• Such a C 1-20 alkylene group is preferably a C 1-10 alkylene group, more preferably a C 1-6 alkylene group, and even more preferably a C 1-3 alkylene group.
• X 11 is independently at each occurrence -C 1-6 alkylene-O-C 1-6 alkylene- or -O-C 1-6 alkylene-.
• X11 each occurrence, is independently a single bond or a straight-chain C1-6 alkylene group, preferably a single bond or a straight-chain C1-3 alkylene group, more preferably a single bond or a straight-chain C1-2 alkylene group, and even more preferably a straight-chain C1-2 alkylene group.
• R 13 is independently at each occurrence a hydrogen atom or a monovalent organic group.
• the monovalent organic group is preferably a C 1-20 alkyl group.
• the C 1-20 alkyl group may be linear or branched, but is preferably linear.
• R 13 is independently at each occurrence a hydrogen atom or a straight chain C 1-6 alkyl group, preferably a hydrogen atom or a straight chain C 1-3 alkyl group, preferably a hydrogen atom or a methyl group.
• t is, independently at each occurrence, an integer of 2 or greater.
• t is independently in each occurrence an integer from 2 to 10, preferably an integer from 2 to 6.
• R 14 is independently at each occurrence 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, and more preferably a fluorine atom.
• R 14 is a hydrogen atom.
• R 15 in each occurrence 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.
• R 15 at each occurrence is independently an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or an alkyleneoxy group having 1 to 6 carbon atoms.
• R 15 is a single bond.
• formula (S1) is formula (S1-a) below.
• R 11 , R 12 , R 13 , X 11 , and n1 are as defined above in formula (S1); t1 and t2, each independently in each occurrence, are an integer greater than or equal to 1, preferably an integer from 1 to 10, more preferably an integer from 2 to 10, for example an integer from 1 to 5 or an integer from 2 to 5;
• the order of occurrence of each repeating unit enclosed in parentheses with t1 and t2 is arbitrary in the formula.
• formula (S1) is the following formula (S1-b): [In the formula, R 11 , R 12 , R 13 , X 11 , n1 and t are the same as defined in the above formula (S1)]
• R a1 is independently at each occurrence -Z 1 -SiR 21 p1 R 22 q1 R 23 r1 .
• Z1 's are each independently an oxygen atom or a divalent organic group in each occurrence.
• the right side is bonded to ( SiR21p1R22q1R23r1 ) .
• Z1 is a divalent organic group.
• Z 1 does not include any that forms a siloxane bond with the Si atom to which Z 1 is bonded.
• (Si-Z 1 -Si) does not include 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, for example an integer of 1 to 6, and z2 is an integer of 0 to 6, for example 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 of 1 to 6, and z4 is an integer of 0 to 6, for example an integer of 1 to 6).
• Such a C 1-6 alkylene group may be linear or branched, but is preferably linear.
• These groups may be substituted with one or more substituents selected from, for example, a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group, 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, light resistance, particularly ultraviolet resistance, may be improved.
• Z 1 is a C 1-3 alkylene group. In one embodiment, Z 1 can be -CH 2 CH 2 CH 2 -. In another embodiment, Z 1 can be -CH 2 CH 2 -.
• R 21 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 in each occurrence.
• the right side is bonded to (SiR 21 ' p1 ' R 22 ' q1 ' R 23 ' r1 ' ).
• Z 1′ is a divalent organic group.
• Z 1 ' does not include any that forms a siloxane bond with the Si atom to which Z 1 ' is bonded.
• Z 1 ' does not include any that forms a siloxane bond with the Si atom to which Z 1 ' is bonded.
• Si-Z 1 ' -Si does not include 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, for example an integer of 1 to 6, and z2' is an integer of 0 to 6, for example 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 of 1 to 6, and z4' is an integer of 0 to 6, for example an integer of 1 to 6).
• Such a C 1-6 alkylene group may be linear or branched, but is preferably linear.
• These groups may be substituted with one or more substituents selected from, for example, a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group, 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, light resistance, particularly ultraviolet resistance, may be improved.
• Z 1' is a C 1-3 alkylene group. In one embodiment, Z 1' can be -CH 2 CH 2 CH 2 -. In another embodiment, Z 1' can be -CH 2 CH 2 -.
• R 21′ is independently —Z 1′′ —SiR 22′′ q1′′ R 23′′ r1′′ .
• Z 1′′ is independently an oxygen atom or a divalent organic group at each occurrence.
• the right side is bonded to (SiR 22′′ q1′′ R 23′′ r1′′ ).
• Z 1′′ is a divalent organic group.
• Z 1′′ does not include any that forms a siloxane bond with the Si atom to which Z 1′′ is bonded.
• Z 1′′ does not include any that forms a siloxane bond with the Si atom to which Z 1′′ is bonded.
• Si—Z 1′′ —Si does not include a siloxane bond.
• the above Z1 " is preferably a C1-6 alkylene group, -( CH2 ) z1" -O-( CH2 ) z2" - (wherein z1" is an integer of 0 to 6, for example an integer of 1 to 6, and z2" is an integer of 0 to 6, for example an integer of 1 to 6), or -( CH2 ) z3" -phenylene-( CH2 ) z4" - (wherein z3" is an integer of 0 to 6, for example an integer of 1 to 6, and z4" is an integer of 0 to 6, for example an integer of 1 to 6).
• Such a C1-6 alkylene group may be linear or branched, but is preferably linear.
• These groups may be substituted with one or more substituents selected from, for example, a fluorine atom, a C1-6 alkyl group, a C2-6 alkenyl group, and a C2-6 alkynyl group, 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, light resistance, particularly ultraviolet resistance, may be improved.
• 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 -.
• Each occurrence of R 22 ′′ is independently a hydroxyl group or a hydrolyzable group.
• R 22 ′′ is, independently at each occurrence, a hydrolyzable group.
• R j includes unsubstituted alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group; and substituted alkyl groups such as a chloromethyl group.
• an alkyl group, particularly an unsubstituted alkyl group is preferred, and a methyl group or an ethyl group is more preferred.
• R j is a methyl group, and in another embodiment, R j is an ethyl group.
• Each occurrence of R 23 ′′ is independently a hydrogen atom or a monovalent organic group.
• a monovalent organic group is a monovalent organic group 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.
• the above q1" is independently an integer of 0 to 3 in each occurrence, and the above r1" is independently an integer of 0 to 3 in each occurrence.
• the sum of q1" and r1" is 3 in the (SiR 22" q1" R 23" r1" ) unit.
• q1′′ is preferably an integer of 1 to 3, more preferably 2 to 3, and further preferably 3, independently for each (SiR 22′′ q1′′ R 23′′ r1′′ ) unit.
• Each occurrence of R 22′ is independently a hydroxyl group or a hydrolyzable group.
• R 22' is preferably, independently at each occurrence, a hydrolyzable group.
• an alkyl group particularly an unsubstituted alkyl group, is preferred, and a methyl group or an ethyl group is more preferred.
• R j is a methyl group, and in another embodiment, R j is an ethyl group.
• Each occurrence of R 23′ is independently a hydrogen atom or a monovalent organic group.
• a monovalent organic group is a monovalent organic group 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.
• p1' is independently in each occurrence an integer of 0 to 3
• q1' is independently in each occurrence an integer of 0 to 3
• r1' is independently in each occurrence an integer of 0 to 3.
• the sum of p', q1' and r1' is 3 in the (SiR 21' p1' R 22' q1' R 23' r1' ) unit.
• p1' is 0.
• p1' may be, independently for each (SiR 21' p1' R 22' q1' R 23' r1' ) unit, an integer from 1 to 3, an integer from 2 to 3, or 3. In a preferred embodiment, p1' is 3.
• R 22 is preferably, independently at each occurrence, a hydrolyzable group.
• an alkyl group particularly an unsubstituted alkyl group, is preferred, and a methyl group or an ethyl group is more preferred.
• R j is a methyl group, and in another embodiment, R j is an ethyl group.
• Each occurrence of R 23 is independently a hydrogen atom or a monovalent organic group.
• a monovalent organic group is a monovalent organic group other than the hydrolyzable group.
• 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.
• p1 is independently in each occurrence an integer of 0 to 3
• q1 is independently in each occurrence an integer of 0 to 3
• r1 is independently in each occurrence an integer of 0 to 3.
• the sum of p1, q1 and r1 is 3 in the (SiR 21 p1 R 22 q1 R 23 r1 ) unit.
• q1 is independently an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3 for each (SiR 21 p1 R 22 q1 R 23 r1 ) unit.
• p1 is 0, and q1 is independently an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3, for each (SiR 21 p1 R 22 q1 R 23 r1 ) unit.
• R b1 at each occurrence is independently a hydroxyl group or a hydrolyzable group.
• R j includes unsubstituted alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group; and substituted alkyl groups such as a chloromethyl group.
• an alkyl group, particularly an unsubstituted alkyl group is preferred, and a methyl group or an ethyl group is more preferred.
• R j is a methyl group, and in another embodiment, R j is an ethyl group.
• R c1 is independently a hydrogen atom or a monovalent organic group in each occurrence.
• 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.
• k1 is independently in each occurrence an integer of 0 to 3
• l1 is independently in each occurrence an integer of 0 to 3
• m1 is independently in each occurrence an integer of 0 to 3.
• the sum of k1, l1 and m1 is 3 in the (SiR a1 k1 R b1 l1 R c1 m1 ) unit.
• k1 is independently for each (SiR a1 k1 R b1 l1 R c1 m1 ) unit an integer from 1 to 3, preferably 2 or 3, more preferably 3. In a preferred embodiment, k1 is 3.
• R Si is a group represented by formula (S3), preferably, at least two Si atoms to which a hydroxyl group or a hydrolyzable group is bonded are present in the terminal portion of formula (1) and formula (2).
• the group represented by formula (S3) has any one of -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 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 , Z 1' , Z 1" , R 22 , R 23 , R 22' , R 23' , R 22'' , and R 23'' are as defined above.
• q1′′ is an integer of 1 to 3, preferably 2 or 3, and more preferably 3, in at least one, and preferably all, R 21′ .
• 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 21 .
• k1 is 2 or 3, preferably 3, p1 is 0, and q1 is 2 or 3, preferably 3.
• R d1 is independently at each occurrence -Z 2 -CR 31 p2 R 32 q2 R 33 r2 .
• Z2 each occurrence is independently a single bond, an oxygen atom, or a divalent organic group .
• the right side bonds to ( CR31p2R32q2R33r2 ) .
• Z2 is a divalent organic group.
• 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, for example an integer of 1 to 6, and z6 is an integer of 0 to 6, for example 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 of 1 to 6, and z8 is an integer of 0 to 6, for example an integer of 1 to 6).
• Such a C 1-6 alkylene group may be linear or branched, but is preferably linear.
• These groups may be substituted with one or more substituents selected from, for example, a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group, 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, light resistance, particularly ultraviolet resistance, may be improved.
• Z 2 is a C 1-3 alkylene group. In one embodiment, Z 2 can be -CH 2 CH 2 CH 2 -. In another embodiment, 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' in each occurrence is independently a single bond, an oxygen atom or a divalent organic group.
• the right side is bonded 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, for example an integer of 1 to 6, and z6' is an integer of 0 to 6, for example 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 of 1 to 6, and z8' is an integer of 0 to 6, for example an integer of 1 to 6).
• Such a C 1-6 alkylene group may be linear or branched, but is preferably linear.
• These groups may be substituted with one or more substituents selected from, for example, a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group, 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, light resistance, particularly ultraviolet resistance, may be improved.
• Z 2' is a C 1-3 alkylene group. In one embodiment, Z 2' can be -CH 2 CH 2 CH 2 -. In another embodiment, Z 2' can be -CH 2 CH 2 -.
• R 32′ is independently —Z 3 —SiR 34 n2 R 35 3-n2 .
• Z3 is independently a single bond, an oxygen atom or a divalent organic group in each occurrence.
• the right side is bonded to (SiR 34 n2 R 35 3-n2 ).
• Z3 is an oxygen atom.
• Z3 is a divalent organic group.
• Z 3 above is preferably a C 1-6 alkylene group, -(CH 2 ) z5" -O-(CH 2 ) z6" - (wherein z5" is an integer of 0 to 6, for example an integer of 1 to 6, and z6" is an integer of 0 to 6, for example 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 of 1 to 6, and z8" is an integer of 0 to 6, for example an integer of 1 to 6).
• Such a C 1-6 alkylene group may be linear or branched, but is preferably linear.
• These groups may be substituted with one or more substituents selected from, for example, a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group, 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, light resistance, particularly ultraviolet resistance, may be improved.
• Z 3 is a C 1-3 alkylene group. In one embodiment, Z 3 can be -CH 2 CH 2 CH 2 -. In another embodiment, Z 3 can be -CH 2 CH 2 -.
• R 34 is independently a hydroxyl group or a hydrolyzable group.
• R 34 is preferably, independently at each occurrence, a hydrolyzable group.
• R j includes unsubstituted alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group; and substituted alkyl groups such as a chloromethyl group.
• an alkyl group particularly an unsubstituted alkyl group, is preferred, and a methyl group or an ethyl group is more preferred.
• R j is a methyl group, and in another embodiment, R j is an ethyl group.
• Each occurrence of R 35 is independently a hydrogen atom or a monovalent organic group.
• a monovalent organic group is a monovalent organic group excluding the hydrolyzable group.
• 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.
• n2 is independently an integer from 0 to 3 for each (SiR n2 R 35 3-n2 ) unit.
• R Si is a group represented by formula (S4)
• at least one (SiR n2 R 35 3-n2 ) unit in which n2 is 1 to 3 is present in the terminal portion of formula (1) and formula (2). That is, in such terminal portion, all n2's do not become 0 at the same time.
• at least one Si atom to which a hydroxyl group or a hydrolyzable group is bonded is present in the terminal portion of formula (1) and formula (2).
• n2 is preferably an integer of 1 to 3, more preferably 2 or 3, and further preferably 3, independently for each (SiR 34 n2 R 35 3-n2 ) unit.
• Each occurrence of R 33′ is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group, the monovalent organic group being a monovalent organic group other than the hydrolyzable groups.
• 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, and 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.
• the above q2' is independently in each occurrence an integer of 0 to 3, and the above r2' is independently in each occurrence an integer of 0 to 3.
• the sum of q2' and r2' is 3 in the (CR 32' q2' R 33' r2' ) unit.
• q2' is preferably an integer of 1 to 3, more preferably 2 to 3, and further preferably 3, independently for each (CR 32' q2' R 33' r2' ) unit.
• R 32 at each occurrence, is independently -Z 3 -SiR 34 n2 R 35 3-n2 , which is the same as defined above for R 32' .
• Each occurrence of R 33 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 groups.
• 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 independently in each occurrence an integer of 1 to 6, preferably an integer of 2 to 4, t1 is 1 or 0, preferably 0, and 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.
• p2 is independently in each occurrence an integer of 0 to 3
• q2 is independently in each occurrence an integer of 0 to 3
• r2 is independently in each occurrence an integer of 0 to 3.
• the sum of p2, q2 and r2 is 3 in the (CR 31 p2 R 32 q2 R 33 r2 ) unit.
• p2 is 0.
• p2 may be, independently at each (CR 31 p2 R 32 q2 R 33 r2 ) unit, an integer from 1 to 3, an integer from 2 to 3, or 3.
• q2 is independently an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3 for each (CR 31 p2 R 32 q2 R 33 r2 ) unit.
• p2 is 0, and q2 is independently an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3, for each (CR 31 p2 R 32 q2 R 33 r2 ) unit.
• R e1 is independently -Z 3 -SiR 34 n2 R 35 3-n2 , where -Z 3 -SiR 34 n2 R 35 3-n2 has the same meaning as described above for R 32' .
• Each occurrence of R f1 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 groups.
• 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, and 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 in each occurrence an integer of 0 to 3
• l2 is independently in each occurrence an integer of 0 to 3
• m2 is independently in each occurrence an integer of 0 to 3.
• the sum of k2, l2 and m2 is 3 in the (CR d1 k2 R e1 l2 R f1 m2 ) unit.
• R Si is a group represented by formula (S4), preferably, at least two Si atoms to which a hydroxyl group or a hydrolyzable group is bonded are present in the terminal portion of formula (1) and formula (2).
• n2 is an integer of 1 to 3, preferably 2 or 3, and more preferably 3, in at least one, and preferably all, R 32′ .
• n2 is an integer of 1 to 3, preferably 2 or 3, and more preferably 3, in at least one, and preferably all, R 32 .
• n2 is an integer of 1 to 3, preferably 2 or 3, and more preferably 3, in at least one, preferably all, R a1 .
• k2 is 0, l2 is 2 or 3, preferably 3, and n2 is 2 or 3, preferably 3.
• R g1 and R h1 each independently in each occurrence are -Z 4 -SiR 11 n1 R 12 3-n1 , -Z 4 -SiR a1 k1 R b1 l1 R c1 m1 , and -Z 4 -CR d1 k2 R e1 l2 R f1 m2 , where R 11 , R 12 , R a1 , R b2 , R c1 , R d1 , R e1 , R f1 , n1, k1, l1, m1, k2, l2, and m2 are as defined above.
• R g1 and R h1 are each independently --Z 4 --SiR 11 n1 R 12 3-n1 .
• Z4 is independently a single bond, an oxygen atom or a divalent organic group in each occurrence.
• the right side is bonded to (SiR 11 n1 R 12 3-n1 ).
• Z4 is an oxygen atom.
• Z4 is a divalent organic group.
• Z 4 above is preferably a C 1-6 alkylene group, -(CH 2 ) z5" -O-(CH 2 ) z6" - (wherein z5" is an integer of 0 to 6, for example an integer of 1 to 6, and z6" is an integer of 0 to 6, for example 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 of 1 to 6, and z8" is an integer of 0 to 6, for example an integer of 1 to 6).
• Such a C 1-6 alkylene group may be linear or branched, but is preferably linear.
• These groups may be substituted with one or more substituents selected from, for example, a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group, 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, light resistance, particularly ultraviolet resistance, may be improved.
• Z 4 is a C 1-3 alkylene group. In one embodiment, Z 4 can be -CH 2 CH 2 CH 2 -. In another embodiment, 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 slip properties.
• R Si is a group represented by formula (S3), (S4) or (S5). These compounds have multiple hydrolyzable groups at one end, and therefore can form a surface treatment layer that adheres strongly to a substrate and has high abrasion resistance.
• R Si is a group represented by formula (S3) or (S4). These compounds can have multiple hydrolyzable groups branched from one Si atom or C atom at one end, and therefore can form a surface treatment layer with even higher abrasion resistance.
• R 3 Si is a group represented by formula (S1).
• R 3 Si is a group represented by formula (S2).
• R 3 Si is a group represented by formula (S3).
• R 3 Si is a group represented by formula (S4).
• R 3 Si is a group represented by formula (S5).
• XA is understood to be a linker that connects the fluoropolyether portion (R F1 and R F2 ) that mainly provides water repellency and surface slipperiness, etc., to the portion (R Si ) that provides the ability to bind to a substrate. Therefore, XA may be a single bond or any other group as long as the compounds represented by formulas (1) and (2) can exist stably.
• ⁇ is an integer of 1 to 9
• ⁇ is an integer of 1 to 9.
• ⁇ and ⁇ can change depending on the valence of XA .
• the sum of ⁇ and ⁇ is the same as the valence of XA .
• XA is a decavalent organic group
• the sum of ⁇ and ⁇ is 10, and for example, ⁇ is 9 and ⁇ is 1, ⁇ is 5 and ⁇ is 5, or ⁇ is 1 and ⁇ is 9.
• ⁇ and ⁇ are 1.
• ⁇ is an integer of 1 to 9. ⁇ can change depending on the valence of X A. That is, ⁇ is a value obtained by subtracting 1 from the valence of X A.
• Each XA is independently a single bond or a divalent to decavalent organic group
• the divalent to decavalent organic group in XA is preferably a divalent to octavalent organic group.
• the divalent to decavalent organic group is preferably a divalent to tetravalent organic group, more preferably a divalent organic group.
• the divalent to decavalent organic group is preferably a trivalent to octavalent organic group, more preferably a trivalent to hexavalent organic group.
• X 1 A is a single bond or a divalent organic group, ⁇ is 1 and ⁇ is 1.
• X 1 A is a single bond or a divalent organic group and ⁇ is 1.
• XA is a trivalent to hexavalent organic group, ⁇ is 1, and ⁇ is 2-5.
• XA is a trivalent to hexavalent organic group and ⁇ is 2 to 5.
• X 1 A is a trivalent organic group, ⁇ is 1 and ⁇ is 2.
• XA is a trivalent organic group and ⁇ is 2.
• XA is a divalent organic group.
• XA is, for example, a single bond or the following formula: -(R 51 ) p5 -(X 51 ) q5 - [Wherein: R 51 represents a single bond, —(CH 2 ) s5 —, or an o-, m-, or p-phenylene group, and is preferably —(CH 2 ) s5 —; s5 is an integer from 1 to 20, preferably an integer from 1 to 6, more preferably an integer from 1 to 3, even more preferably 1 or 2; X 51 represents -(X 52 ) l5 -; X 52 , in each occurrence, independently represents a group selected from the group consisting of -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 -,
• 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 a preferred embodiment, X A is not substituted with these groups.
• each of the XA's is independently -( R51 ) p5- ( X51 ) q5 - R52- .
• R52 represents a single bond, -( CH2 ) t5- or an o-, m- or p-phenylene group, and is preferably -( CH2 ) t5- .
• t5 is an integer of 1 to 20, preferably an integer of 2 to 6, and more preferably an integer of 2 to 3.
• R52 (typically the hydrogen atom of R52 ) may be substituted with one or more substituents selected from a fluorine atom, a C1-3 alkyl group, and a C1-3 fluoroalkyl group.
• R56 is not substituted with these groups.
• each XA is independently Single bond, a C 1-20 alkylene group, -R 51 -X 53 -R 52 -, or -X 54 -R 52 - [In the formula, R 51 and R 52 are as defined 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-( CH2 ) u5 -Si( R53 ) 2 -O-Si( R53 ) 2 - CH2CH2- Si ( R53 ) 2 -O-Si( R53 ) 2- , -O-(CH
• each XA is independently Single bond, a C 1-20 alkylene group, -(CH 2 ) s5 -X 53 -, -(CH 2 ) s5 -X 53 -(CH 2 ) t5 - -X54- or -X54- ( CH2 ) t5- [In the formula, X 53 , X 54 , s5 and t5 are as defined above.] It is.
• each XA is 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 above.] It could be.
• each XA is independently a single bond C 1-20 alkylene group, -(CH 2 ) s5 -X 53 - or -(CH 2 ) s5 -X 53 -(CH 2 ) t5 - [Wherein, X 53 is —O—, —CONR 54 —, or —O—CONR 54 —; R 54 independently represents a hydrogen atom, a phenyl group, or a C 1-6 alkyl group at each occurrence; s5 is an integer from 1 to 20, t5 is an integer from 1 to 20. It could be.
• each XA is independently -(CH 2 ) s5 -O-(CH 2 ) t5 - -CONR 54 -(CH 2 ) t5 - [Wherein, R 54 independently represents a hydrogen atom, a phenyl group, or a C 1-6 alkyl group at each occurrence; s5 is an integer from 1 to 20, t5 is an integer from 1 to 20. It could be.
• each XA 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 -, -(CH 2 ) s5 -O-(CH 2 ) u5 -(Si(R 53 ) 2 O) m5 -Si(R 53 ) 2 -(CH 2 ) t5 -, or -(CH 2 ) s5 -O-(CH 2 ) t5 -Si(R 53 ) 2 -(CH 2 ) u5 -Si ( R53 ) 2- ( CvH2v )- [In the formula, R 53 , m5, s5, t5 and u5 are defined as above, and v5 is an integer of
• Each of the X 1 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 embodiment, X 1 A is unsubstituted.
• each formula of XA above is bonded to R F1 or R F2
• the right side is bonded to R Si .
• XA includes, for example, the following groups: [In the formula, each R 41 independently represents a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C 1-6 alkoxy group, preferably a methyl group; 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 -, -( CH2 ) 4- , -CONH-(CH 2 ) 3 -, -CON( CH3 )-( CH2 ) 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
• XA Specific examples 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 (
• XA is each independently a group represented by the formula: -(R 16 ) x1 -(CFR 17 ) y1 -(CH 2 ) z1 -, where x1, y1 and z1 are each independently an integer of 0 to 10, the sum of x1, y1 and z1 is 1 or more, and the order of occurrence of each repeat unit enclosed in parentheses in the formula is arbitrary.
• R 16 is independently at each occurrence 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, and n-propyl, which may be substituted with one or more fluorine atoms.
• R 17 is independently at each occurrence 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 even more preferably a trifluoromethyl group.
• examples of XA include the following groups: [Wherein, R 41 is each 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 XA group, any one of T's may be the following group bonded to RF1 or RF2 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 -, -( CH2 ) 4- , -CONH-(CH 2 ) 3 -, -CON( CH3 )-( CH2 ) 3- , -CON(Ph)-(CH 2 ) 3 -, where Ph is phenyl, or [In the formula, each R 42 independently represents a hydrogen atom, a pheny
• the ultraviolet absorbing group is not particularly limited as long as it can absorb ultraviolet light, but examples include residues of benzotriazoles, hydroxybenzophenones, esters of substituted and unsubstituted benzoic acid or salicylic acid compounds, acrylates or alkoxycinnamates, oxamides, oxanilides, benzoxazinones, and benzoxazoles.
• preferred radical scavenging groups or UV absorbing groups include groups represented by the following formula:
• each X 1 A may independently be a trivalent to decavalent organic group.
• R 25 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 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 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 at the end or in the main chain of the hydrocarbon, preferably a C 1-6 alkyl group, -R 36 -R 37 -R 36 -, -R 36 -CHR 38 2 -, etc.
• R 36 is each 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 -.
• R 45 is each independently an alkyl group having 1 to 6 carbon atoms.
• R 46 is N, O or S, preferably O.
• examples of XA include the following: [In the formula, Xa is a single bond or a divalent organic group.] Examples of the group represented by the formula:
• Xa is a single bond or a divalent linking group directly bonded to the isocyanuric ring.
• Xa 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 organic group having 1 to 10 carbon atoms and containing at least one bond selected from the group consisting of an ether bond, an ester bond, an amide bond, and a sulfide bond.
• Xa is represented by the following formula: -(CX 121 X 122 ) x1 -(X a1 ) y1 -(CX 123 X 124 ) z1 - (wherein X 121 to X 124 each independently represent H, F, OH, or —OSi(OR 121 ) 3 (wherein each of the three R 121 's each independently represent an alkyl group having 1 to 4 carbon atoms);
• the above X a1 is preferably —O— or —C( ⁇ O)O—.
• the above Xa is represented by the following formula: -(CF 2 ) m11 -(CH 2 ) m12 -O-(CH 2 ) m13 - (In the formula, m11 is an integer of 1 to 3, m12 is an integer of 1 to 3, and m13 is an integer of 1 to 3.) A group represented by -(CF 2 ) m14 -(CH 2 ) m15 -O-CH 2 CH(OH)-(CH 2 ) m16 - (In the formula, m14 is an integer of 1 to 3, m15 is an integer of 1 to 3, and m16 is an integer of 1 to 3.) A group represented by -(CF 2 ) m17 -(CH 2 ) m18 - (In the formula, m17 is an integer of 1 to 3, and m18 is an integer of 1 to 3.) A group represented by -(CF 2 ) m19 -(CH 2 ) m20 -O-CH 2 CH (OSi(OC
• the above Xa is not particularly limited, but specifically includes —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 XA may independently be a di- or trivalent organic group.
• the fluorine-containing silane compound represented by the above formula (1) or formula (2) may have an average molecular weight of, but is not particularly limited to, 5 x 10 2 to 1 x 10 5. Within this range, from the viewpoint of wear resistance, it is preferable for the average molecular weight to be 2,000 to 32,000, more preferably 2,500 to 12,000. Note that this "average molecular weight” refers to a number average molecular weight, and the “average molecular weight” is a value measured by 19 F-NMR.
• the content of the fluorine-containing silane compound represented by the above formula (1) or (2) may be preferably 90% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less, based on a total of 100% by mass of the above fluorine-containing silane compounds.
• the surface treatment agent may further contain a solvent.
• a solvent By containing a solvent, the composition becomes easier to handle.
• the formed layer can be a continuous thin film.
• such a composition can contribute to the formation of a thin film of any thickness.
• alkyl perfluoroalkyl ethers perfluoroalkyl groups and alkyl groups may be linear or branched), or CF 3 CH 2 OCF 2 CHF 2 (e.g., Asahiklin (registered trademark) AE-3000 manufactured by Asahi Glass Co., Ltd.).
• solvents can be used alone or as a mixture of two or more kinds.
• hydrofluoroethers are preferred, and perfluorobutyl methyl ether (C 4 F 9 OCH 3 ) and/or perfluorobutyl ethyl ether (C 4 F 9 OC 2 H 5 ) are particularly preferred.
• the boiling point (atmospheric pressure) of the above solvent may preferably be less than 105°C, more preferably 90°C or less, and even more preferably 80°C or less.
• the lower limit of the boiling point is not particularly limited, but may be, for example, 30°C or higher, preferably 50°C or higher.
• the content of the solvent is preferably 50 to 99.7% by mass, more preferably 60 to 99.7% by mass, even more preferably 70 to 99.7% by mass, and particularly preferably 80 to 99.7% by mass, based on a total of 100% by mass of the surface treatment agent.
• the surface treatment agent of the present disclosure may further include a (non-reactive) fluoropolyether compound that can be understood as a fluorine-containing oil, preferably a perfluoro(poly)ether compound (collectively referred to below as "fluorine-containing oil”), a (non-reactive) silicone compound that can be understood as a silicone oil (hereinafter referred to as "silicone oil”), alcohols, catalysts, surfactants, polymerization inhibitors, sensitizers, etc.
• fluorine-containing oil preferably a perfluoro(poly)ether compound (collectively referred to below as "fluorine-containing oil")
• silicone oil a silicone oil
• the other components are different from the fluorine-containing silane compound and solvent described above.
• Rf 5 represents a C 1-16 alkyl group (preferably a C 1-16 perfluoroalkyl group) optionally substituted by one or more fluorine atoms
• Rf 6 represents a C 1-16 alkyl group (preferably a C 1-16 perfluoroalkyl group) optionally substituted by one or more fluorine atoms, a fluorine atom or a hydrogen atom
• Rf 5 and Rf 6 are more preferably each independently a C 1-3 perfluoroalkyl group.
• -(OC 4 F 8 )- may be any of -(OCF 2 CF 2 CF 2 CF 2 )-, -(OCF(CF 3 )CF 2 CF 2 )-, -(OCF 2 CF(CF 3 )CF 2 )-, -(OCF 2 CF 2 CF(CF 3 ))-, -(OCF 2 C(CF 3 ) 2 )-, -(OCF(CF 3 )CF(CF 3 ))-, -(OCF(C 2 F 5 )CF 2 )- and (OCF 2 CF(C 2 F 5 ))-, preferably -(OCF 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 ))-, and
• Rf5 and Rf6 are as defined above; in formula (4a), b" is an integer of 1 or more and 100 or less; in formula (4b), a" and b" are each independently an integer of 0 or more and 30 or less, and c" and d" are each independently an integer of 1 or more and 300 or less.
• the order of occurrence of each repeating unit enclosed in parentheses with the subscripts a", b", c", and d" is arbitrary in the formula.
• 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), or may be a chlorotrifluoroethylene oligomer.
• the fluorine-containing oil may have a number average molecular weight of preferably 1000 or more, more preferably 1500 or more, and even more preferably 2000 or more.
• the fluorine-containing oil may also have a number average molecular weight of preferably 30000 or less, more preferably 20000 or less, and even more preferably 10000 or less.
• the molecular weight of the fluorine-containing oil may be measured using GPC.
• the fluorine-containing oil may be contained in an amount of, for example, 0 to 50% by mass, preferably 0 to 30% by mass, and more preferably 0 to 5% by mass, relative to the surface treatment agent.
• the surface treatment agent of the present disclosure is substantially free of fluorine-containing oil. "Substantially free of fluorine-containing oil” means that the surface treatment agent does not contain any fluorine-containing oil, or may contain a very small amount of fluorine-containing oil.
• the number average molecular weight of the fluorine-containing oil may be smaller than the number average molecular weight of the fluorine-containing silane compound.
• the fluorinated oil contributes to improving the surface slipperiness of the layer formed by the surface treatment agent of the present disclosure.
• the silicone oil may be, for example, a linear or cyclic silicone oil having 2,000 or less siloxane bonds.
• the linear silicone oil may be so-called straight silicone oil or modified silicone oil.
• straight silicone oil include dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil.
• modified silicone oil include straight silicone oil modified with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol, etc.
• Examples of cyclic silicone oil include cyclic dimethylsiloxane oil.
• such silicone oil can be contained in an amount of, for example, 0 to 300 parts by mass, preferably 50 to 200 parts by mass, per 100 parts by mass of the total of the fluorine-containing silane compounds of the present disclosure (if there are two or more types, the total of these, the same applies below).
• Silicone oil helps improve the surface slipperiness of the surface treatment layer.
• the alcohols include alcohols having 1 to 6 carbon atoms which may be substituted with one or more fluorine atoms, such as methanol, ethanol, isopropanol, tert-butanol, CF 3 CH 2 OH, CF 3 CF 2 CH 2 OH, and (CF 3 ) 2 CHOH. Addition of these alcohols to the surface treatment agent improves the stability of the surface treatment agent and also improves the compatibility of the fluorine-containing silane compound with the solvent.
• fluorine atoms such as methanol, ethanol, isopropanol, tert-butanol, CF 3 CH 2 OH, CF 3 CF 2 CH 2 OH, and (CF 3 ) 2 CHOH.
• the alcohols are preferably contained in the surface treatment agent in an amount of 0.1 to 5 times, more preferably 0.5 to 3 times, and even more preferably 0.8 to 1.2 times the molar ratio of the metal compound.
• the catalyst may be an acid (e.g., acetic acid, trifluoroacetic acid, etc.), a base (e.g., ammonia, triethylamine, diethylamine, etc.), or a transition metal (e.g., Ti, Ni, Sn, etc.).
• an acid e.g., acetic acid, trifluoroacetic acid, etc.
• a base e.g., ammonia, triethylamine, diethylamine, etc.
• a transition metal e.g., Ti, Ni, Sn, etc.
• the catalyst promotes the hydrolysis and dehydration condensation of the fluorine-containing silane compound of the present disclosure, and promotes the formation of the layer formed by the surface treatment agent of the present disclosure.
• the present disclosure provides a new surface treatment method for a substrate having an anti-reflective coating, and in one embodiment, the transparency of the substrate having an anti-reflective coating can be maintained and the durability, particularly the abrasion resistance, of the surface treatment layer can be improved. Therefore, the surface treatment method disclosed herein can be preferably used for various substrates, for example, substrates in electronic devices.
• Such electronic devices include portable terminal devices such as smartphones, tablets, notebook PCs, and cameras; wearable devices such as smart watches; and display devices such as televisions, liquid crystal displays, organic EL displays, and inorganic EL displays.
• an AR substrate having a structure of glass substrate/ Si3N4 / SiO2 / Si3N4 / SiO2 / Si3N4 / SiO2 (AR1 substrate) and an AR substrate having a structure of glass substrate/ Si3N4 / SiO2 / Si3N4 / SiO2 / Si3N4 / SiO2 / Si3N4 / SiO2 (AR2 substrate ) were used.
• Comparative Example 1 Using a 1300 ⁇ deposition apparatus manufactured by Optorun, only the surface treatment agent was deposited on the AR1 substrate without carrying out either surface smoothing treatment or SiO2 film formation.
• Examples 1 to 3 Using a 1300 ⁇ deposition apparatus manufactured by Optorun, a SiO 2 film was not formed on the AR1 substrate, and only a plasma treatment using Ar gas was performed under the conditions shown in Table 1, after which a surface treatment agent was deposited.
• Examples 4 to 14 Using a 1300 ⁇ deposition apparatus manufactured by Optorun, plasma treatment with Ar gas and SiO2 film formation were performed on the AR1 substrate under the conditions shown in Table 1, and then the surface treatment agent was deposited.
• Comparative Example 2 Using a 1900 ⁇ deposition apparatus manufactured by Shincron, only the surface treatment agent was deposited on the AR2 substrate without carrying out either surface smoothing treatment or SiO2 film formation.
• Example 15 Using a 1900 ⁇ deposition apparatus manufactured by Shincron, no SiO2 film was formed on the AR2 substrate, and only plasma treatment with O2 gas was performed under the conditions shown in Table 1, after which a surface treatment agent was deposited.
• Examples 16 to 21 Using a 1900 ⁇ deposition apparatus manufactured by Shincron, plasma treatment with O2 gas and formation of a SiO2 film were carried out on the AR2 substrate under the conditions shown in Table 1, and then the surface treatment agent was deposited.
• the treated substrates were evaluated as follows. ⁇ Wear resistance> The substrate on which the surface treatment layer was formed was placed horizontally, and steel wool (count #0000, dimensions 10 mm x 10 mm) was brought into contact with the exposed upper surface of the surface treatment layer, and a load of 1,000 gf was applied thereon. Thereafter, the steel wool was moved back and forth while the load was applied (distance: 30 mm (reciprocation), speed: 60 rpm). The static contact angle (degrees) of water was measured every certain number of reciprocations. When the measured contact angle value became less than 95 degrees, the evaluation was stopped. The number of reciprocations at which the measured value became less than 95 degrees is shown in the table below.
• the transmittance of the substrate on which the surface treatment layer was formed was measured in accordance with ISO 14782 using a haze meter NDH 7000SP (manufactured by Nippon Denshoku Industries Co., Ltd.).
• Examples 4 to 14 in which the surface smoothing treatment was performed by plasma irradiation using Ar as the process gas, it was confirmed that a substrate having excellent wear resistance and optical properties could be obtained by setting the plasma irradiation time to 700 seconds or less. In addition, in Examples 4 to 14, it was confirmed that particularly good wear resistance and optical properties could be obtained when the thickness of the layer containing SiO 2 was in the range of 1 to 6 nm.
• Examples 18 to 23 in which the surface smoothing treatment was performed by plasma irradiation using O2 as the process gas it was confirmed that a substrate having excellent abrasion resistance and optical properties could be obtained by setting the plasma irradiation time to 180 to 600 seconds.
• Examples 16 to 21 it was confirmed that particularly good abrasion resistance and optical properties could be obtained when the thickness of the layer containing SiO2 was in the range of 1 to 3 nm.
• the present disclosure provides a new surface treatment method for a substrate having an anti-reflective coating, and in one embodiment, the transparency of the substrate having an anti-reflective coating can be maintained, and the durability, particularly the abrasion resistance, of the surface treatment layer can be improved. Therefore, the surface treatment method disclosed herein can be preferably used for various substrates, for example, substrates for electronic devices.

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