WO2016190047A1 - Procédé de fabrication d'article comprenant une couche de traitement de surface - Google Patents

Procédé de fabrication d'article comprenant une couche de traitement de surface Download PDF

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Publication number
WO2016190047A1
WO2016190047A1 PCT/JP2016/063273 JP2016063273W WO2016190047A1 WO 2016190047 A1 WO2016190047 A1 WO 2016190047A1 JP 2016063273 W JP2016063273 W JP 2016063273W WO 2016190047 A1 WO2016190047 A1 WO 2016190047A1
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Prior art keywords
independently
integer
group
occurrence
silicon oxide
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PCT/JP2016/063273
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English (en)
Japanese (ja)
Inventor
尚志 三橋
香織 小澤
雅聡 能勢
康雄 伊丹
雅人 森嶋
蒙懿 王
一希 山田
布瀬　暁志
円華 乙骨
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ダイキン工業株式会社
東京エレクトロン株式会社
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Application filed by ダイキン工業株式会社, 東京エレクトロン株式会社 filed Critical ダイキン工業株式会社
Priority to CN201680029344.2A priority Critical patent/CN107614257A/zh
Priority to KR1020177021085A priority patent/KR20180001556A/ko
Priority to JP2017520584A priority patent/JP6601492B2/ja
Publication of WO2016190047A1 publication Critical patent/WO2016190047A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • 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
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/42—Silicides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/56—After-treatment

Definitions

  • the present invention relates to a method for producing an article having a surface treatment layer, particularly an article having a surface treatment layer obtained from a surface treatment agent containing a fluorine-containing silane compound.
  • Patent Document 1 describes a perfluoropolyether group-containing silane compound having a hydrolyzable group bonded to a Si atom at the molecular terminal or terminal part.
  • Patent Document 1 on the outermost surface of the substrate, forming a SiO 2 layer, by applying a surface treatment agent comprising a fluorine-containing silane compound in the SiO 2 layer on, to form a surface treatment layer.
  • the surface treatment layer is required to have high durability so as to provide a desired function to the base material over a long period of time. Since the layer obtained from the surface treatment agent containing a perfluoropolyether group-containing silane compound can exhibit the above-described functions even in a thin film, it is suitable for optical members such as glasses and touch panels that require optical transparency or transparency. In particular, these applications are required to further improve the friction durability.
  • Patent Document 1 As described in Patent Document 1, as a pretreatment when forming a surface treatment layer, a method of forming a SiO 2 layer on the outermost surface of a substrate and then applying a surface treatment agent thereon is known.
  • PVD method Physical Vapor Deposition
  • the present inventors may not have sufficient friction durability and sweat durability. I noticed.
  • an object of the present invention is to provide a method capable of producing an article having a surface treatment layer having more excellent friction durability and sweat durability (that is, acid and alkali resistance).
  • CVD Chemical Vapor Deposition
  • a substrate A silicon oxide layer located on the substrate; A method for producing an article comprising a surface treatment layer formed on the silicon oxide layer, Forming a silicon oxide layer using a chemical vapor deposition method, and forming a surface treatment layer on the obtained silicon oxide layer using a surface treatment agent containing a fluorine-containing silane compound; A manufacturing method is provided.
  • a silicon oxide layer is formed, and a surface treatment layer is formed thereon, thereby having water repellency, oil repellency, antifouling properties, and excellent
  • An article comprising a surface treatment layer having friction resistance and sweat resistance can be produced.
  • the article manufactured by the manufacturing method of the present invention comprises a base material, a silicon oxide layer located on the base material, and a surface treatment layer formed on the silicon oxide layer.
  • Substrates that can be used in the present invention include, for example, glass, sapphire glass, resin (natural or synthetic resin, such as a general plastic material, and may be a plate, film, or other form), metal ( It may be a single metal such as aluminum, copper, iron or a composite of an alloy, etc.), ceramics, semiconductor (silicon, germanium, etc.), fiber (woven fabric, non-woven fabric, etc.), fur, leather, wood, ceramics, stone, etc. It can be composed of any suitable material, such as a building member.
  • the substrate is glass.
  • soda lime glass alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass, and quartz glass are preferable, chemically strengthened soda lime glass, chemically strengthened alkali aluminosilicate glass, and chemical bond Particularly preferred is borosilicate glass.
  • the shape of the substrate is not particularly limited. Further, the surface region of the substrate on which the silicon oxide layer and the surface treatment layer are to be formed may be at least part of the substrate surface, and is appropriately determined according to the use and specific specifications of the article to be manufactured. obtain.
  • Some layer (or film) such as a hard coat layer or an antireflection layer may be formed on the surface of the substrate.
  • the antireflection layer either a single-layer antireflection layer or a multilayer antireflection layer may be used.
  • inorganic materials that can be used for the antireflection layer include SiO 2 , SiO, ZrO 2 , TiO 2 , TiO, Ti 2 O 3 , Ti 2 O 5 , Al 2 O 3 , Ta 2 O 5 , CeO 2 , MgO. , Y 2 O 3 , SnO 2 , MgF 2 , WO 3 and the like. These inorganic substances may be used alone or in combination of two or more thereof (for example, as a mixture).
  • the article to be manufactured is an optical glass component for a touch panel
  • a thin film using a transparent electrode such as indium tin oxide (ITO) or indium zinc oxide is provided on a part of the surface of the substrate (glass).
  • the base material is an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomized film layer, a hard coating film layer, a polarizing film, a phase difference film, And a liquid crystal display module or the like.
  • the substrate may be pretreated before forming the silicon oxide layer on the substrate.
  • the pretreatment By performing the pretreatment, the adhesion between the base material and the silicon oxide layer is improved, and higher friction durability can be obtained.
  • the pretreatment is not particularly limited, and examples thereof include washing with an oxidant solution such as H 2 O 2 and H 2 SO 4 or an alcohol such as ethanol. Washing with a mixed solution of H 2 O 2 / H 2 SO 4 / H 2 O (1 to 5: 1 to 5: 1 to 20) or ethanol is preferable, and a mixture of H 2 O 2 / H 2 SO 4 / H 2 O is preferable. More preferred is washing with a solution.
  • SiO x silicon oxide
  • the silicon oxide layer is formed by a CVD method.
  • the CVD method is a method of forming a non-volatile film by supplying a raw material in a gaseous state and reacting it on the surface of a substrate.
  • Specific examples of the CVD method include plasma CVD, optical CVD, thermal CVD, and similar methods.
  • plasma CVD is used.
  • oxygen gas is preferably used as the oxygen source in the CVD method.
  • the carrier gas in the CVD method is appropriately selected according to the type of the CVD method, and for example, an inert gas such as nitrogen gas, argon gas, helium gas, or hydrogen gas is used.
  • the conditions for forming the silicon oxide layer by the CVD method are appropriately set according to the type of CVD method used, the thickness of the silicon oxide layer, and the like.
  • the silicon oxide layer is formed by plasma CVD, it is preferably performed under the following conditions.
  • RF (Radio Frequency) power density 0.5 to 2.0 W / cm 2 , preferably 0.7 to 1.5 W / cm 2 , for example 1.0 W / cm 2 ;
  • Substrate temperature 100-400 ° C., preferably 150-300 ° C., for example 200 ° C .;
  • Process pressure 50 to 500 Pa, preferably 100 to 300 Pa, for example 150 to 200 Pa;
  • the silicon oxide layer formed by the above CVD method may have a surface roughness (Ra: centerline average roughness) of preferably 0.2 nm or less, more preferably 0.15 nm or less.
  • the Ra is defined in JIS B0601: 1982.
  • the silicon oxide layer formed by the CVD method is preferably at least partly, more preferably 50% or more of the whole silicon oxide layer, and still more preferably 80% or more of the whole silicon oxide layer.
  • the amorphous state in the silicon oxide layer can be confirmed by measuring the intensity of a diffraction peak caused by a crystal by an X-ray diffraction method (XRD).
  • the silicon oxide layer formed by the CVD method preferably has a density of 2.25g / cm 3 ⁇ 2.60g / cm 3, more preferably 2.30g / cm 3 ⁇ 2.50g / cm 3 , even more preferably a density of 2.35g / cm 3 ⁇ 2.45g / cm 3, for example a density of 2.38g / cm 3 ⁇ 2.42g / cm 3.
  • the density of the silicon oxide layer can be measured by an X-ray reflectometry (XRR) method.
  • the silicon oxide layer formed by the CVD method has a hydrogen concentration in the film of preferably 1 at% or more, for example, 2 at% or more, 3 at% or more, 4 at% or more, or 5 at% or more, preferably 10 at% or less, For example, it is 9 at% or less, 8 at% or less, 7 at% or less, or 6 at% or less.
  • the hydrogen concentration in the film is 1 to 10 at%, 2 to 10 at%, 3 to 10 at%, 4 to 10 at%, or 5 to 10 at%, or 1 to 9 at%, 1 to 8 at%, 1 to 7 at%, or 1 It can be ⁇ 6 at%, alternatively 2-9 at%, 3-8 at%, 4-7 at%, or 5-6 at%.
  • the hydrogen concentration in the silicon oxide layer can be measured by Rutherford Backscattering Spectrometry (RBS).
  • the Si / O composition ratio (mol ratio) in the silicon oxide layer formed by the CVD method can be 1.5 or less, and preferably is greater than 0.5.
  • the Si / O composition ratio is preferably 0.6 to 1.5, more preferably 0.7 to 1.3, such as 0.7 to 1.2, 0.8 to 1.3 or 0.8 to 1. .2.
  • the Si / O composition ratio in the silicon oxide layer can be measured by a Rutherford Backscattering Spectrometry (RBS) method.
  • the silicon oxide layer may be pretreated before forming the surface treatment layer on the obtained silicon oxide layer.
  • the adhesion between the silicon oxide layer and the surface treatment layer is improved, and higher friction durability can be obtained.
  • Examples of the pretreatment include ion cleaning.
  • the ion cleaning is not particularly limited, but oxygen ion cleaning and argon ion cleaning are preferable, and oxygen ion cleaning is more preferable.
  • Ion cleaning conditions may vary depending on the type of gas used, but oxygen ion cleaning is performed under the following conditions. However, the ion cleaning is not limited to the following conditions as long as impurities on the silicon oxide layer can be removed.
  • Oxygen ion cleaning conditions Accelerating voltage: 500 to 1500V, preferably 800 to 1200V, typically 1000V Acceleration current: 100 to 1000 mA, preferably 300 to 700 mA, typically 500 mA Gas amount: 10 to 100 sccm, preferably 30 to 70 sccm, typically 50 sccm Pressure: 1 ⁇ 10 ⁇ 3 Pa to 1 ⁇ 10 ⁇ 1 Pa, preferably 1 ⁇ 10 ⁇ 2 Pa to 5 ⁇ 10 ⁇ 2 Pa, typically 2 ⁇ 10 ⁇ 2 Pa
  • a surface treatment layer is formed on the silicon oxide layer obtained above using a surface treatment agent containing a fluorine-containing silane compound.
  • the fluorine-containing silane compound preferably contains a perfluoropolyether group.
  • PFPE has the formula: -(OC 4 F 8 ) a- (OC 3 F 6 ) b- (OC 2 F 4 ) c- (OCF 2 ) d-
  • a, b, c and d are each independently an integer of 0 to 200, and the sum of a, b, c and d is at least 1, and the subscripts a, b, c or d
  • hydrocarbon group means a group containing carbon and hydrogen, and a group in which one hydrogen atom has been eliminated from a hydrocarbon.
  • Such hydrocarbon group is not particularly limited, but may be a hydrocarbon group having 1 to 20 carbon atoms which may be substituted by one or more substituents, such as an aliphatic hydrocarbon group, An aromatic hydrocarbon group etc. are mentioned.
  • the “aliphatic hydrocarbon group” may be linear, branched or cyclic, and may be either saturated or unsaturated.
  • the hydrocarbon group may also contain one or more ring structures.
  • Such a hydrocarbon group may have one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy and the like at its terminal or molecular chain.
  • the substituent of the “hydrocarbon group” is not particularly limited, but includes, for example, a halogen atom; C 1-6 alkyl optionally substituted by one or more halogen atoms Group, C 2-6 alkenyl group, C 2-6 alkynyl group, C 3-10 cycloalkyl group, C 3-10 unsaturated cycloalkyl group, 5-10 membered heterocyclyl group, 5-10 membered unsaturated heterocyclyl And one or more groups selected from a group, a C 6-10 aryl group and a 5-10 membered heteroaryl group.
  • divalent to decavalent organic group means a divalent to decavalent group containing carbon.
  • a divalent to decavalent organic group is not particularly limited, and examples thereof include divalent to decavalent groups in which 1 to 9 hydrogen atoms are further eliminated from a hydrocarbon group.
  • the divalent organic group is not particularly limited, and examples thereof include a divalent group in which one hydrogen atom is further eliminated from a hydrocarbon group.
  • perfluoropolyether group-containing silane compounds represented by the above formulas (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2) will be described below. .
  • — (OC 4 F 8 ) — represents — (OCF 2 CF 2 CF 2 CF 2 ) —, — (OCF (CF 3 ) CF 2 CF 2 ) —, — (OCF 2 CF (CF 3 ) CF 2 )-,-(OCF 2 CF 2 CF (CF 3 ))-,-(OC (CF 3 ) 2 CF 2 )-,-(OCF 2 C (CF 3 ) 2 )-,-(OCF (CF 3 ) CF (CF 3 ))-,-(OCF (C 2 F 5 ) CF 2 )-and-(OCF 2 CF (C 2 F 5 ))-may be used, but preferably — (OCF 2 CF 2 CF 2 CF 2 ) —.
  • -(OC 3 F 6 )- is any of-(OCF 2 CF 2 CF 2 )-,-(OCF (CF 3 ) CF 2 )-and-(OCF 2 CF (CF 3 ))- Preferably, it is — (OCF 2 CF 2 CF 2 ) —.
  • — (OC 2 F 4 ) — may be any of — (OCF 2 CF 2 ) — and — (OCF (CF 3 )) —, preferably — (OCF 2 CF 2 ) —. is there.
  • PFPE is — (OC 3 F 6 ) b — (wherein b is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200),
  • — (OCF 2 CF 2 CF 2 ) b — (wherein b is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200) or — (OCF (CF 3 ) CF 2 ) b — (wherein b is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200), more preferably — (OCF 2 CF 2 CF 2 ) b- (wherein b is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200).
  • PFPE has the following structure:-(OC 4 F 8 ) a- (OC 3 F 6 ) b- (OC 2 F 4 ) c- (OCF 2 ) d- (wherein a and b are each independently And c and d are each independently an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200, and the subscripts a, b, c Or the order of presence of each repeating unit in parentheses with d attached is arbitrary in the formula), preferably — (OCF 2 CF 2 CF 2 CF 2 ) a — (OCF 2 CF 2 CF 2 ) b- (OCF 2 CF 2 ) c- (OCF 2 ) d- .
  • PFPE is — (OC 2 F 4 ) c — (OCF 2 ) d — (wherein c and d are each independently 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably Is an integer of 10 or more and 200 or less, and the order of presence of each repeating unit in parentheses with the subscript c or d is arbitrary in the formula).
  • PFPE is a group represented by — (OC 2 F 4 —R 15 ) n ′′ —.
  • R 15 represents OC 2 F 4 , OC 3 F 6 and OC 4 F.
  • 8 is a group selected from, or independent of .OC 2 F 4, OC 3 F 6 and OC 4 F 8 is a combination of two or three groups independently selected from these groups The combination of 2 or 3 groups selected is not particularly limited.
  • n ′′ is an integer of 2 to 100, preferably an integer of 2 to 50 is there.
  • OC 2 F 4 , OC 3 F 6 and OC 4 F 8 may be either linear or branched, preferably linear.
  • the PFPE is preferably — (OC 2 F 4 —OC 3 F 6 ) n ′′ — or — (OC 2 F 4 —OC 4 F 8 ) n ′′ —.
  • Rf represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms.
  • alkyl group having 1 to 16 carbon atoms in the alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms may be linear or branched. Preferably, it is a linear or branched alkyl group having 1 to 6 carbon atoms, particularly 1 to 3 carbon atoms, and more preferably a linear alkyl group having 1 to 3 carbon atoms.
  • Rf is preferably an alkyl group having 1 to 16 carbon atoms, which is substituted with one or more fluorine atoms, more preferably a CF 2 H—C 1-15 fluoroalkylene group, still more preferably Is a perfluoroalkyl group having 1 to 16 carbon atoms.
  • the perfluoroalkyl group having 1 to 16 carbon atoms may be linear or branched, and preferably has 1 to 6 carbon atoms, particularly 1 to 6 carbon atoms. 3 perfluoroalkyl group, more preferably a linear perfluoroalkyl group having 1 to 3 carbon atoms, specifically —CF 3 , —CF 2 CF 3 , or —CF 2 CF 2 CF 3 . .
  • R 1 independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, at each occurrence.
  • R 2 independently represents a hydroxyl group or a hydrolyzable group at each occurrence.
  • R examples include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; substituted alkyl groups such as chloromethyl group.
  • an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
  • the hydroxyl group is not particularly limited, but may be a group produced by hydrolysis of a hydrolyzable group.
  • R 11 independently represents a hydrogen atom or a halogen atom at each occurrence.
  • the halogen atom is preferably an iodine atom, a chlorine atom or a fluorine atom, more preferably a fluorine atom.
  • R 12 each independently represents a hydrogen atom or a lower alkyl group.
  • the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group.
  • n is independently an integer of 0 to 3, preferably 0 to 2, more preferably 0 for each (-SiR 1 n R 2 3-n ) unit. However, in the formula, all n are not 0 simultaneously. In other words, at least one R 2 is present in the formula.
  • ⁇ is an integer of 1 to 9
  • ⁇ ′ is an integer of 1 to 9.
  • These ⁇ and ⁇ ′ can vary depending on the valence of X 1 .
  • the sum of ⁇ and ⁇ ′ is the same as the valence of X 1 .
  • X 1 is a 10-valent organic group
  • the sum of ⁇ and ⁇ ′ is 10, for example, ⁇ is 9 and ⁇ ′ is 1, ⁇ is 5 and ⁇ ′ is 5, or ⁇ is 1 and ⁇ 'Can be nine.
  • ⁇ and ⁇ ′ are 1.
  • alpha is a value obtained by subtracting 1 from the valence of X 1.
  • X 1 is preferably 2 to 7 valent, more preferably 2 to 4 valent, and still more preferably a divalent organic group.
  • X 1 is a divalent to tetravalent organic group
  • ⁇ is 1 to 3
  • ⁇ ′ is 1.
  • X 1 is a divalent organic group
  • ⁇ is 1
  • ⁇ ′ is 1.
  • the formulas (A1) and (A2) are represented by the following formulas (A1 ′) and (A2 ′).
  • Examples of X 1 are not particularly limited, but for example, the following formula: -(R 31 ) p ' -(X a ) q'- [Where: R 31 represents a single bond, — (CH 2 ) s ′ — or o-, m- or p-phenylene group, preferably — (CH 2 ) s ′ — s ′ is an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and even more preferably 1 or 2.
  • X a represents-(X b ) l ' - X b is independently at each occurrence —O—, —S—, o—, m- or p-phenylene, —C (O) O—, —Si (R 33 ) 2 —, — ( Si (R 33 ) 2 O) m ′ —Si (R 33 ) 2 —, —CONR 34 —, —O—CONR 34 —, —NR 34 — and — (CH 2 ) n ′ —
  • R 33 each independently represents a phenyl group, a C 1-6 alkyl group or a C 1-6 alkoxy group, preferably a phenyl group or a C 1-6 alkyl group, and more preferably a methyl group.
  • R 34 each independently represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group (preferably a methyl group) at each occurrence;
  • m ′ is independently an integer of 1 to 100, preferably an integer of 1 to 20, at each occurrence,
  • n ′ is independently an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, at each occurrence.
  • X 1 is — (R 31 ) p ′ — (X a ) q ′ —R 32 —.
  • R 32 represents a single bond, — (CH 2 ) t ′ — or o-, m- or p-phenylene group, and preferably — (CH 2 ) t ′ —.
  • t ′ is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3.
  • R 32 (typically a hydrogen atom of R 32 ) is substituted with one or more substituents selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group. It may be.
  • X 1 is A C 1-20 alkylene group, -R 31 -X c -R 32- , or -X d -R 32- [Wherein, R 31 and R 32 are as defined above. ] It can be.
  • said X 1 is A C 1-20 alkylene group, -(CH 2 ) s' -X c- , -(CH 2 ) s ' -X c- (CH 2 ) t'- -X d- , or -X d- (CH 2 ) t ' - [Wherein, s ′ and t ′ are as defined above]. ] It is.
  • X c is -O-, -S-, -C (O) O-, -CONR 34 -, -O-CONR 34 -, -Si (R 33 ) 2- , -(Si (R 33 ) 2 O) m ' -Si (R 33 ) 2- , —O— (CH 2 ) u ′ — (Si (R 33 ) 2 O) m ′ —Si (R 33 ) 2 —, —O— (CH 2 ) u ′ —Si (R 33 ) 2 —O—Si (R 33 ) 2 —CH 2 CH 2 —Si (R 33 ) 2 —O—Si (R 33 ) 2 —, —O— (CH 2 ) u ′ —Si (OCH 3 ) 2 OSi (OCH 3 ) 2 —, —CONR 34 — (CH 2 ) u ′ — (Si (Si (OC
  • X d is -S-, -C (O) O-, -CONR 34 -, —CONR 34 — (CH 2 ) u ′ — (Si (R 33 ) 2 O) m ′ —Si (R 33 ) 2 —, —CONR 34 — (CH 2 ) u ′ —N (R 34 ) —, or —CONR 34 — (o-, m- or p-phenylene) -Si (R 33 ) 2 — [Wherein each symbol is as defined above. ] Represents.
  • said X 1 is A C 1-20 alkylene group, — (CH 2 ) s ′ —X c — (CH 2 ) t ′ —, or —X d — (CH 2 ) t ′ — [Wherein each symbol is as defined above. ] It can be.
  • said X 1 is A C 1-20 alkylene group, — (CH 2 ) s ′ —O— (CH 2 ) t ′ —, - (CH 2) s' - (Si (R 33) 2 O) m '-Si (R 33) 2 - (CH 2) t' -, — (CH 2 ) s ′ —O— (CH 2 ) u ′ — (Si (R 33 ) 2 O) m ′ —Si (R 33 ) 2 — (CH 2 ) t ′ —, or — (CH 2 ) s′— O— (CH 2 ) t ′ —Si (R 33 ) 2 — (CH 2 ) u ′ —Si (R 33 ) 2 — (C v H 2v ) —
  • R 33 , m ′, s ′, t ′ and u ′ are as defined above, and v is
  • — (C v H 2v ) — may be linear or branched.
  • the X 1 group is 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). May be.
  • the X 1 group can be other than an —O—C 1-6 alkylene group.
  • examples of X 1 groups include the following groups: [Wherein, each R 41 independently represents a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C 1-6 alkoxy group, preferably a methyl group; D is —CH 2 O (CH 2 ) 2 —, —CH 2 O (CH 2 ) 3 —, —CF 2 O (CH 2 ) 3 —, -(CH 2 ) 2- , -(CH 2 ) 3- , - (CH 2) 4 -, -CONH- (CH 2 ) 3- , -CON (CH 3 )-(CH 2 ) 3- , —CON (Ph) — (CH 2 ) 3 — (wherein Ph represents 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 group, more
  • X 1 include, for example: —CH 2 O (CH 2 ) 2 —, —CH 2 O (CH 2 ) 3 —, —CH 2 O (CH 2 ) 6 —, —CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2 —, -CH 2 O (CH 2) 3 Si (CH 3) 2 OSi (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -, -CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 2 Si (CH 3 ) 2 (CH 2 ) 2- , —CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 3 Si (CH 3 ) 2 (CH 2 ) 2 —, —CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 3 Si (CH 3 ) 2 (CH
  • X 1 is a group represented by the formula: — (R 16 ) x — (CFR 17 ) y — (CH 2 ) z —.
  • x, y and z are each independently an integer of 0 to 10, the sum of x, y and z is 1 or more, and the order in which each repeating unit enclosed in parentheses is in the formula Is optional.
  • R 16 is independently an oxygen atom, phenylene, carbazolylene, —NR 26 — (wherein R 26 represents a hydrogen atom or an organic group) or a divalent organic group at each occurrence. is there.
  • R 16 is an oxygen atom or a divalent polar group.
  • the “divalent polar group” is not particularly limited, but —C (O) —, —C ( ⁇ NR 27 ) —, and —C (O) NR 27 — (in these formulas, R 27 is Represents a hydrogen atom or a lower alkyl group).
  • the “lower alkyl group” is, for example, an alkyl group having 1 to 6 carbon atoms, for example, methyl, ethyl, n-propyl, and these may be substituted with one or more fluorine atoms.
  • R 71 represents R a ′ independently at each occurrence.
  • R a ′ has the same meaning as R a .
  • Si is connected to the linear through the Z group is a five at the maximum. That is, in the above R a , when at least one R 71 is present, there are two or more Si atoms linearly linked via a Z group in R a , The maximum number of Si atoms connected in a chain is five.
  • the "number of Si atoms linearly linked via a Z group in R a" is equal to -Z-Si- repeating number of which is connected to a linear during R a.
  • * means a site bonded to Si of the main chain, and ... means that a predetermined group other than ZSi is bonded, that is, all three bonds of Si atoms are ... In this case, it means the end point of ZSi repetition.
  • the number on the right shoulder of Si means the number of appearances of Si connected in a straight line through the Z group counted from *. That is, the chain in which ZSi repeat is completed in Si 2 has “the number of Si atoms linearly linked through the Z group in Ra ”, and similarly, Si 3 , Si 4 And the chain in which the ZSi repetition is completed in Si 5 has “number of Si atoms linearly linked through the Z group in R a ” being 3, 4 and 5, respectively.
  • R a but ZSi chain there are multiple, they need not be all the same length, each may be of any length.
  • the number of Si atoms connected linearly via the Z group in R a is one (left formula) or two (right formula) in all chains. Formula).
  • the number of Si atoms connected in a straight chain via a Z group in R a is 1 or 2, preferably 1.
  • R 72 independently represents a hydroxyl group or a hydrolyzable group at each occurrence.
  • hydrolyzable group as used herein means a group capable of undergoing a hydrolysis reaction.
  • hydrolyzable groups include —OR, —OCOR, —O—N ⁇ C (R) 2 , —N (R) 2 , —NHR, halogen (wherein R is substituted or unsubstituted Represents an alkyl group having 1 to 4 carbon atoms), preferably —OR (alkoxy group).
  • R include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; substituted alkyl groups such as chloromethyl group.
  • an alkyl group particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
  • the hydroxyl group is not particularly limited, but may be a group produced by hydrolysis of a hydrolyzable group.
  • R b represents a hydroxyl group or a hydrolyzable group independently at each occurrence.
  • R b is preferably a hydroxyl group, —OR, —OCOR, —O—N ⁇ C (R) 2 , —N (R) 2 , —NHR, halogen (in these formulas, R is substituted or unsubstituted)
  • An alkyl group having 1 to 4 carbon atoms preferably —OR.
  • R includes an unsubstituted alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group; and a substituted alkyl group such as a chloromethyl group.
  • Preferred compounds represented by the formulas (C1) and (C2) are represented by the following formulas (C1 ′′) and (C2 ′′): [Where: Each PFPE is independently of the formula: -(OC 4 F 8 ) a- (OC 3 F 6 ) b- (OC 2 F 4 ) c- (OCF 2 ) d- Wherein a, b, c and d are each independently an integer of 0 to 200, and the sum of a, b, c and d is at least 1, and the subscripts a, b, c or d The order of existence of each repeating unit with parentheses attached with is arbitrary in the formula.) A group represented by: Rf independently represents each alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms at each occurrence; X 7 represents —CH 2 O (CH 2 ) 2 —, —CH 2 O (CH 2 ) 3 — or —CH 2 O (CH 2
  • X 9 each independently represents a single bond or a divalent to 10-valent organic group.
  • the X 9 is a perfluoropolyether part (ie, Rf-PFPE part or -PFPE-part) mainly providing water repellency and surface slipperiness in the compounds represented by the formulas (D1) and (D2). It is understood that this is a linker that connects a moiety that provides a binding ability to the substrate (that is, a group that is bracketed with ⁇ ). Therefore, X 9 may be any organic group as long as the compounds represented by formulas (D1) and (D2) can exist stably.
  • ⁇ is an integer of 1 to 9
  • ⁇ ′ is an integer of 1 to 9.
  • [delta] and [delta] ' may vary depending on the valence of X 9.
  • the sum of [delta] and [delta] ' is the same as the valence of X 9.
  • X is a 10-valent organic group
  • the sum of ⁇ and ⁇ ′ is 10, for example, ⁇ is 9 and ⁇ ′ is 1, ⁇ is 5 and ⁇ ′ is 5, or ⁇ is 1 and ⁇ ′.
  • X 9 is a divalent organic group
  • ⁇ and ⁇ ′ are 1.
  • [delta] is a value obtained by subtracting 1 from the valence of X 9.
  • X 9 is preferably 2 to 7 valent, more preferably 2 to 4 valent, and still more preferably a divalent organic group.
  • X 9 is a divalent organic group, ⁇ is 1 and ⁇ ′ is 1.
  • the formulas (D1) and (D2) are represented by the following formulas (D1 ′) and (D2 ′).
  • Examples of X 9 are not particularly limited, and examples thereof include those similar to those described with respect to X 1 .
  • preferable specific X 9 is —CH 2 O (CH 2 ) 2 —, —CH 2 O (CH 2 ) 3 —, —CH 2 O (CH 2 ) 6 —, —CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2 —, -CH 2 O (CH 2) 3 Si (CH 3) 2 OSi (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -, -CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 2 Si (CH 3 ) 2 (CH 2 ) 2- , —CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 3 Si (CH 3 ) 2 (CH 2 ) 2 —, —CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 3 Si (CH 3 ) 2 (CH 2
  • R d independently represents —Z 2 —CR 81 p2 R 82 q2 R 83 r2 at each occurrence.
  • Z 2 represents an oxygen atom or a divalent organic group independently at each occurrence.
  • Z 2 is preferably a C 1-6 alkylene group, — (CH 2 ) g —O— (CH 2 ) h — (wherein g is an integer of 0 to 6, for example, an integer of 1 to 6). And h is an integer from 0 to 6, for example an integer from 1 to 6, or -phenylene- (CH 2 ) i- (where i is an integer from 0 to 6), and more A C 1-3 alkylene group is preferred. These groups may be substituted with, for example, one or more substituents selected from a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group. .
  • R 81 independently represents R d ′ at each occurrence.
  • R d ′ has the same meaning as R d .
  • R d the maximum number of C linked in a straight chain via the Z 2 group is 5. That is, the in R d, when R 81 is present at least one, but Si atoms linked in R d in Z 2 group via a linear there are two or more, via such Z 2 group The maximum number of C atoms connected in a straight line is five.
  • the phrase "through the Z 2 group in R d number of C atoms linearly linked" is equal to the number of repetitions of -Z 2 -C- being linearly linked in a R d Become. This is the same as the description regarding R a in the formulas (C1) and (C2).
  • R 82 represents —Y—SiR 85 n2 R 86 3-2n .
  • Y represents a divalent organic group independently at each occurrence.
  • Y is a C 1-6 alkylene group, — (CH 2 ) g ′ —O— (CH 2 ) h ′ — (wherein g ′ is an integer from 0 to 6, for example from 1 to 6 Is an integer, h ′ is an integer from 0 to 6, for example, an integer from 1 to 6, or —phenylene- (CH 2 ) i ′ — (where i ′ is an integer from 0 to 6) ).
  • These groups may be substituted with, for example, one or more substituents selected from a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group. .
  • R 5 represents a hydroxyl group or a hydrolyzable group independently at each occurrence.
  • hydrolyzable group as used herein means a group capable of undergoing a hydrolysis reaction.
  • hydrolyzable groups include —OR, —OCOR, —O—N ⁇ C (R) 2 , —N (R) 2 , —NHR, halogen (wherein R is substituted or unsubstituted Represents an alkyl group having 1 to 4 carbon atoms), preferably —OR (alkoxy group).
  • R include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; substituted alkyl groups such as chloromethyl group.
  • an alkyl group particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
  • the hydroxyl group is not particularly limited, but may be a group produced by hydrolysis of a hydrolyzable group.
  • n2 independently represents an integer of 0 to 3, preferably an integer of 1 to 3, more preferably 2 or 3, and even more preferably, for each unit (-Y-SiR 85 n2 R 86 3-n2 ). 3.
  • R 83 represents a hydrogen atom or a lower alkyl group independently at each occurrence.
  • the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
  • At least one of the terminal ends of R d is —C (—Y—SiR 85 q2 R 86 r2 ) 2 or —C (—Y—SiR 85 q2 R 86 r2 ) 3 , preferably —C ( may be -Y-SiR 85 q2 R 86 r2 ) 3.
  • (- Y-SiR 85 q2 R 86 r2) units is preferably (-Y-SiR 85 3).
  • the terminal portions of R d may be all —C (—Y—SiR 85 q2 R 86 r2 ) 3 , preferably —C (—Y—SiR 85 3 ) 3 .
  • R f independently represents a hydrogen atom or a lower alkyl group at each occurrence.
  • the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
  • the perfluoro (poly) ether group-containing silane compound represented by the formula (D1) or the formula (D2) can be produced by combining known methods.
  • the compound represented by the formula (D1 ′) in which X is divalent is not limited, but can be produced as follows.
  • a group containing a double bond preferably a polyhydric alcohol represented by HO—X—C (YOH) 3 (wherein X and Y are each independently a divalent organic group)) Is allyl), and halogen (preferably bromo), and Hal—X—C (Y—O—R—CH ⁇ CH 2 ) 3 (where Hal is halogen, eg Br, R is A double bond-containing halide represented by a valent organic group such as an alkylene group.
  • R PFPE —OH a perfluoropolyether group-containing alcohol represented by R PFPE —OH (wherein R PFPE is a perfluoropolyether group-containing group), and R PFPE ⁇ O—X—C (Y—O—R—CH ⁇ CH 2 ) 3 is obtained.
  • the terminal —CH ⁇ CH 2 is then reacted with HSiCl 3 and alcohol or HSiR 85 3 to give R PFPE —O—X—C (Y—O—R—CH 2 —CH 2 —SiR 85 3 ) 3 Can be obtained.
  • the “number average molecular weight” is measured by GPC (gel permeation chromatography) analysis.
  • the surface treatment agent used in the present invention may be diluted with a solvent.
  • a solvent is not particularly limited.
  • Rf 1 represents a C 1-16 alkyl group (preferably a C 1-16 perfluoroalkyl group) optionally substituted by one or more fluorine atoms
  • Rf 2 represents 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 1 and Rf 2 Are more preferably each independently a C 1-3 perfluoroalkyl group.
  • the perfluoropolyether compound represented by the above general formula (3) may be a compound represented by any one of the following general formulas (3a) and (3b) (one kind or a mixture of two or more kinds).
  • Rf 1 and Rf 2 are as described above; in formula (3a), b ′′ is an integer of 1 to 100; in formula (3b), a ′′ and b ′′ are Each independently represents an integer of 0 or more and 30 or less, for example, 1 or more and 30 or less, and c ′′ and d ′′ are each independently an integer of 1 or more and 300 or less.
  • the order of existence of each repeating unit with subscripts a ′′, b ′′, c ′′, d ′′ and parentheses is arbitrary in the formula.
  • the fluorine-containing oil may have an average molecular weight of 1,000 to 30,000. Thereby, high surface slipperiness can be obtained.
  • the fluorine-containing oil is based on a total of 100 parts by mass of the perfluoropolyether group-containing silane compound (in the case of two or more, respectively, the same applies to the following). For example, 0 to 500 parts by mass, preferably 0 to 400 parts by mass, more preferably 5 to 300 parts by mass.
  • the compound represented by the general formula (3a) and the compound represented by the general formula (3b) may be used alone or in combination. It is preferable to use the compound represented by the general formula (3b) rather than the compound represented by the general formula (3a) because higher surface slip properties can be obtained.
  • the mass ratio of the compound represented by the general formula (3a) and the compound represented by the general formula (3b) is preferably 1: 1 to 1:30, and preferably 1: 1 to 1 : 10 is more preferable. According to such a mass ratio, a surface treatment layer having an excellent balance between surface slipperiness and friction durability can be obtained.
  • the fluorine-containing oil contains one or more compounds represented by the general formula (3b).
  • the mass ratio of the sum of the perfluoropolyether group-containing silane compounds in the surface treatment agent to the compound represented by the formula (3b) is preferably 10: 1 to 1:10, and preferably 4: 1 to 1: 4 is more preferable.
  • the average molecular weight of the compound represented by the formula (3a) is preferably 2,000 to 8,000.
  • the average molecular weight of the compound represented by the formula (3b) is preferably 8,000 to 30,000.
  • the average molecular weight of the compound represented by formula (3b) is preferably 3,000 to 8,000.
  • 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).
  • a chlorotrifluoroethylene oligomer may be sufficient.
  • the compound represented by Rf 3 -F and the chlorotrifluoroethylene oligomer are a compound represented by a fluorine-containing compound having a carbon-carbon unsaturated bond at the molecular end, the terminal of which is a C 1-16 perfluoroalkyl group. This is preferable in that high affinity can be obtained.
  • Fluorine-containing oil contributes to improving the surface slipperiness of the surface treatment layer.
  • the silicone oil for example, a linear or cyclic silicone oil having a siloxane bond of 2,000 or less can be used.
  • the linear silicone oil may be so-called straight silicone oil and modified silicone oil.
  • the straight silicone oil include dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil.
  • modified silicone oil include those obtained by modifying straight silicone oil with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol and the like.
  • Examples of the cyclic silicone oil include cyclic dimethylsiloxane oil.
  • the catalyst accelerates the hydrolysis and dehydration condensation of the perfluoropolyether group-containing silane compound and promotes the formation of the surface treatment layer.
  • a film of a surface treatment agent containing a fluorine-containing silane compound is formed on the surface of the silicon oxide layer, and this film is post-treated as necessary, whereby the surface treatment is performed.
  • the method of forming a layer is mentioned.
  • the film formation of the surface treatment agent can be performed by applying the surface treatment agent to the surface of the silicon oxide layer so as to cover the surface.
  • the coating method is not particularly limited. For example, wet coating methods and dry coating methods can be used.
  • wet coating methods include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating and similar methods.
  • the CVD method include plasma-CVD, optical CVD, thermal CVD, and similar methods.
  • the PVD method is preferable, and the evaporation method such as resistance heating evaporation or electron beam evaporation is preferable, and electron beam evaporation is more preferable.
  • the PVD method a surface treatment layer having higher friction durability can be obtained.
  • the surface treatment agent used in the present invention can be diluted with a solvent and then applied to the substrate surface.
  • the following solvents are preferably used: C 5-12 perfluoroaliphatic hydrocarbons (eg, perfluorohexane, perfluoromethyl) Cyclohexane and perfluoro-1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (eg bis (trifluoromethyl) benzene); polyfluoroaliphatic hydrocarbons (eg C 6 F 13 CH 2 CH 3 (eg Asahi Culin (registered trademark AC-6000) manufactured by Asahi Glass Co., Ltd., 1,1,2,2,3,4,4-heptafluorocyclopentane (for example, ZEOLOR (registered trademark) H manufactured by Nippon Zeon Co., Ltd.) Hydrofluorocarbon (H
  • the surface treatment agent used in the present invention may be directly subjected to the dry coating method, or may be diluted with the above-described solvent and then subjected to the dry coating method.
  • the solvent in the surface treatment agent may be removed in advance. By removing the solvent, a surface treatment layer having higher friction durability can be obtained.
  • the temperature during distillation under reduced pressure is preferably 0 to 200 ° C., more preferably 10 to 80 ° C.
  • the pressure at the time of distillation under reduced pressure is preferably 1 ⁇ 10 ⁇ 4 Pa to 1 ⁇ 10 3 Pa, more preferably 1 ⁇ 10 ⁇ 2 Pa to 1 ⁇ 10 2 Pa.
  • the film formation is preferably carried out so that the surface treatment agent is present in the film together with a catalyst for hydrolysis and dehydration condensation.
  • a catalyst for hydrolysis and dehydration condensation for simplicity, in the case of the wet coating method, after diluting the surface treatment agent with a solvent, the catalyst may be added to the diluted solution of the surface treatment agent immediately before application to the substrate surface.
  • the catalyst-treated surface treatment agent is directly vapor-deposited (usually vacuum deposition), or a pellet form in which a porous metal such as iron or copper is impregnated with the catalyst-treated surface treatment agent. Vapor deposition (usually vacuum deposition) may be performed using a substance.
  • any suitable acid or base can be used for the catalyst.
  • the acid catalyst for example, acetic acid, formic acid, trifluoroacetic acid and the like can be used.
  • a base catalyst ammonia, organic amines, etc. can be used, for example.
  • the membrane is post-treated as necessary.
  • this post-processing is not specifically limited, For example, a water supply and drying heating may be implemented sequentially, and it may be implemented as follows in detail.
  • the method for supplying moisture is not particularly limited, and for example, methods such as dew condensation due to a temperature difference between the precursor film (and the substrate) and the surrounding atmosphere, or spraying of steam (steam) may be used.
  • the supply of moisture is, for example, 0 to 250 ° C., preferably 60 ° C. or higher, more preferably 100 ° C. or higher, preferably 180 ° C. or lower, more preferably 150 ° C. or lower.
  • the pressure at this time is not specifically limited, it can be simply a normal pressure.
  • Post-processing can be performed as described above. It should be noted that such post-treatment can be performed to further improve friction durability, but is not essential for producing the articles of the present invention. For example, after applying the surface treatment agent to the substrate surface, it may be left still.
  • the surface treatment layer derived from the film of the surface treatment agent of the present invention is formed on the surface of the substrate, and the article of the present invention is manufactured.
  • the surface treatment layer obtained by this has high friction durability.
  • this surface treatment layer has water repellency, oil repellency, antifouling properties (for example, preventing adhesion of dirt such as fingerprints), depending on the composition of the surface treatment agent used.
  • As a functional thin film it can be waterproof (to prevent water from entering electronic parts, etc.), surface slippery (or lubricity, for example, wiping off dirt such as fingerprints, and excellent touch to fingers). It can be suitably used.
  • the article obtained by the present invention is not particularly limited, but may be an optical member.
  • the optical member include the following optical members: For example, a cathode ray tube (CRT: eg, TV, personal computer monitor), liquid crystal display, plasma display, organic EL display, inorganic thin film EL dot matrix display, rear projection type Display such as display, fluorescent display tube (VFD), field emission display (FED), front protective plate, antireflection plate, polarizing plate, antiglare plate, or antireflection film treatment on the surface of these displays Lenses such as eyeglasses; Touch panel sheets for devices such as mobile phones and personal digital assistants; Disc surfaces of optical discs such as Blu-ray (registered trademark) discs, DVD discs, CD-Rs, and MOs; Optical fa Eber: Clock display surface.
  • Articles obtained by the present invention can further include ceramic products, coated surfaces, fabric products, leather products, medical products, plasters, etc.
  • the article obtained by the present invention may be a medical device or a medical material.
  • the thickness of the surface treatment layer is not particularly limited. In the case of an optical member, the thickness of the surface treatment layer is in the range of 1 to 50 nm, preferably 1 to 30 nm, more preferably 1 to 15 nm. Optical performance, surface slipperiness, friction durability, and antifouling properties From the point of view, it is preferable.
  • the above-mentioned article of the present invention has high friction durability and high acid-alkali resistance, and depending on the composition of the surface treatment agent used, water repellency, oil repellency, antifouling (for example, adhesion of dirt such as fingerprints) ), Waterproofness (preventing water intrusion into electronic parts, etc.), surface slipperiness (or lubricity, for example, wiping off dirt such as fingerprints, and excellent touch feeling to fingers).
  • the article of the present invention is characterized in that a silicon oxide layer on which a surface treatment layer is formed is formed by a chemical vapor deposition method, and this feature provides excellent surface slip and acid-alkali resistance.
  • a silicon oxide layer on which a surface treatment layer is formed is formed by a chemical vapor deposition method, and this feature provides excellent surface slip and acid-alkali resistance.
  • a silicon oxide layer having a specific Ra By forming a silicon oxide layer by a CVD method, a silicon oxide layer having a specific Ra, a silicon oxide layer having an amorphous structure, a silicon oxide layer having a specific density, or a specific hydrogen concentration in the film A silicon oxide layer can be formed.
  • the present invention provides a substrate, a silicon oxide layer located on the substrate, An article comprising a surface treatment layer formed on the silicon oxide layer, Provided is an article characterized in that the silicon oxide layer has a surface roughness (Ra: center line average roughness) of 0.2 nm or less.
  • Ra can be 0.15 nm or less.
  • the present invention provides a substrate, a silicon oxide layer located on the substrate, An article comprising a surface treatment layer formed on the silicon oxide layer, An article is provided wherein at least a portion of the silicon oxide layer is amorphous.
  • the silicon oxide layer may be amorphous at 50% or more of the entire silicon oxide layer, more preferably 80% or more of the entire silicon oxide layer.
  • the density of the silicon oxide layer is 2.30g / cm 3 ⁇ 2.50g / cm 3, preferably a density of 2.35g / cm 3 ⁇ 2.45g / cm 3, for example 2.38g / Cm 3 to 2.42 g / cm 3 .
  • the present invention provides a substrate, a silicon oxide layer located on the substrate, An article comprising a surface treatment layer formed on the silicon oxide layer, Provided is an article characterized in that the hydrogen concentration in the film of the silicon oxide layer is 1 to 10 at%.
  • the hydrogen concentration in the film of the silicon oxide layer is 2 at% or more, 3 at% or more, 4 at% or more or 5 at% or more, 9 at% or less, 8 at% or less, 7 at% or less or 6 at% or less.
  • the hydrogen concentration in the silicon oxide layer is 1 to 10 at%, 2 to 10 at%, 3 to 10 at%, 4 to 10 at%, or 5 to 10 at%, or 1 to 9 at%, 1 to 8 at%, 1 It can be ⁇ 7 at% or 1 to 6 at%, or 2 to 9 at%, 3 to 8 at%, 4 to 7 at%, or 5 to 6 at%.
  • the present invention provides a substrate, a silicon oxide layer located on the substrate, An article comprising a surface treatment layer formed on the silicon oxide layer, There is provided an article characterized in that the Si / O composition ratio (mol ratio) in the silicon oxide layer is 0.6 to 1.5.
  • the Si / O composition ratio in the silicon oxide layer may be 1.5 or less, preferably greater than 0.5.
  • the Si / O composition ratio is preferably 0.6 to 1.5, more preferably 0.7 to 1.3, such as 0.7 to 1.2, 0.8 to 1.3 or 0.8 to 1. .2.
  • Comparative Example 1 The silicon oxide layer and the surface treatment layer were formed on the substrate in the same manner as in Example 1 except that the silicon oxide layer was formed by the PVD method (electron beam (EB) deposition) instead of being formed by the CVD method.
  • Friction durability evaluation The static contact angle of water was measured for the surface treatment layers of Examples 1 to 3 and Comparative Examples 1 to 3 described above. The static contact angle of water was measured with 1 ⁇ L of water using a contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd.).
  • steel wool friction durability evaluation was carried out as friction durability evaluation. Specifically, the base material on which the surface treatment layer is formed is horizontally arranged, and steel wool (count # 0000, dimensions 5 mm ⁇ 10 mm ⁇ 10 mm) is brought into contact with the exposed upper surface of the surface treatment layer, and 1,000 gf of the steel wool is placed thereon. A load was applied, and then the steel wool was reciprocated with the load applied (distance: 120 mm (reciprocation), speed: 60 rpm). The static contact angle (degree) of water was measured at every fixed number of reciprocations. The evaluation was stopped when the measured value of the contact angle was less than 100 degrees. The results are shown in the table below.
  • Comparative Example 4 Except that 0.25 mg of surface treating agent (that is, containing 0.05 mg of a perfluoropolyether group-containing silane compound) was vapor deposited per piece of chemically strengthened glass (55 mm ⁇ 100 mm), the same as Comparative Example 3 An article having a silicon oxide and a surface treatment layer on the substrate was obtained. The film thickness of the silicon oxide layer measured with an ellipsometer was 15 nm.
  • Example 1 to 3 in which the silicon oxide layer was formed using the CVD method were superior in friction durability to Comparative Examples 1 to 3 using the PVD method, It was confirmed that Example 4 was superior to Comparative Example 4 and superior in acid and alkali durability. That is, by forming the surface treatment layer on the silicon oxide layer formed by the CVD method, it is possible to form a surface treatment layer having better friction durability and more excellent acid and alkali resistance. Was confirmed.
  • the present invention can be suitably used for producing an article comprising a surface treatment layer having high friction durability and acid and alkali resistance on the surface.

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Abstract

La présente invention concerne un procédé de fabrication d'un article comprenant un substrat, une couche d'oxyde de silicium positionnée sur le substrat et une couche de traitement de surface formée sur la couche d'oxyde de silicium, le procédé de fabrication comprenant les étapes consistant à former la couche d'oxyde de silicium au moyen d'un procédé de dépôt chimique en phase vapeur et à former la couche de traitement de surface sur la couche d'oxyde de silicium obtenue au moyen d'un agent de traitement de surface comprenant un composé de silane contenant du fluor.
PCT/JP2016/063273 2015-05-22 2016-04-27 Procédé de fabrication d'article comprenant une couche de traitement de surface WO2016190047A1 (fr)

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WO2019069642A1 (fr) * 2017-10-03 2019-04-11 信越化学工業株式会社 Élément hydrophobe et oléophobe et procédé pour fabriquer un élément hydrophobe et oléophobe
WO2019098230A1 (fr) * 2017-11-15 2019-05-23 ダイキン工業株式会社 Matériau de base
WO2019120879A1 (fr) * 2017-12-22 2019-06-27 BSH Hausgeräte GmbH Objet muni d'un revêtement anti-adhésif omniphobe résistant aux températures élevées et procédé de fabrication dudit objet
WO2019189071A1 (fr) * 2018-03-26 2019-10-03 日本電気硝子株式会社 Substrat doté d'un film antireflet, stratifié et procédé de production de stratifié
CN110582471A (zh) * 2017-04-25 2019-12-17 康宁股份有限公司 具有润滑性防指纹涂层的玻璃、玻璃陶瓷和陶瓷制品及其制造方法
WO2020039795A1 (fr) * 2018-08-20 2020-02-27 信越化学工業株式会社 Élément hydrophobe et oléophobe et procédé de fabrication d'un élément hydrophobe et oléophobe
WO2020137992A1 (fr) * 2018-12-26 2020-07-02 Ａｇｃ株式会社 Substrat avec couche hydrofuge et oléofuge ainsi que procédé de fabrication de celui-ci, et matériau de dépôt en phase vapeur
WO2020171091A1 (fr) * 2019-02-22 2020-08-27 Ａｇｃ株式会社 Substrat en verre fixé à une couche de prévention de contamination et procédé de fabrication d'un substrat en verre fixé à une couche de prévention de contamination
EP3569673A4 (fr) * 2017-01-12 2020-09-02 Daikin Industries, Ltd. Agent de traitement de surface comprenant un composé contenant un groupe perfluoro(poly)éther
CN113905883A (zh) * 2019-05-22 2022-01-07 大金工业株式会社 防污基材
WO2023013476A1 (fr) * 2021-08-05 2023-02-09 信越化学工業株式会社 Article ayant une couche de surface hydrofuge et oléofuge
WO2023013477A1 (fr) * 2021-08-05 2023-02-09 信越化学工業株式会社 Article ayant une couche de surface hydrofuge et oléofuge
JP7386084B2 (ja) 2017-05-08 2023-11-24 コーニング インコーポレイテッド 光学コーティングおよび耐引掻性コーティングの上に耐久性のつるつるした指紋防止コーティングを有するガラス、ガラスセラミックおよびセラミック物品、並びにその製造方法
TWI833695B (zh) 2017-05-08 2024-03-01 美商康寧公司 具有在光學及抗刮塗層上之耐久性光滑抗指紋塗層之玻璃, 玻璃陶瓷及陶瓷製品及其製造方法
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EP3569673A4 (fr) * 2017-01-12 2020-09-02 Daikin Industries, Ltd. Agent de traitement de surface comprenant un composé contenant un groupe perfluoro(poly)éther
US20200002567A1 (en) * 2017-03-17 2020-01-02 Daikin Industries, Ltd. Silane compound containing perfluoro (poly ) ether group
KR102262121B1 (ko) * 2017-03-17 2021-06-09 다이킨 고교 가부시키가이샤 퍼플루오로(폴리)에테르기 함유 실란 화합물
JP2019070100A (ja) * 2017-03-17 2019-05-09 ダイキン工業株式会社 パーフルオロ（ポリ）エーテル基含有シラン化合物
WO2018169002A1 (fr) * 2017-03-17 2018-09-20 ダイキン工業株式会社 Composé silane contenant un groupe perfluoro(poly)éther
US11814537B2 (en) 2017-03-17 2023-11-14 Daikin Industries, Ltd. Silane compound containing perfluoro (poly ) ether group
KR20190104614A (ko) * 2017-03-17 2019-09-10 다이킨 고교 가부시키가이샤 퍼플루오로(폴리)에테르기 함유 실란 화합물
CN110582471A (zh) * 2017-04-25 2019-12-17 康宁股份有限公司 具有润滑性防指纹涂层的玻璃、玻璃陶瓷和陶瓷制品及其制造方法
CN110582471B (zh) * 2017-04-25 2022-06-03 康宁股份有限公司 具有润滑性防指纹涂层的玻璃、玻璃陶瓷和陶瓷制品及其制造方法
TWI833695B (zh) 2017-05-08 2024-03-01 美商康寧公司 具有在光學及抗刮塗層上之耐久性光滑抗指紋塗層之玻璃, 玻璃陶瓷及陶瓷製品及其製造方法
JP7386084B2 (ja) 2017-05-08 2023-11-24 コーニング インコーポレイテッド 光学コーティングおよび耐引掻性コーティングの上に耐久性のつるつるした指紋防止コーティングを有するガラス、ガラスセラミックおよびセラミック物品、並びにその製造方法
CN111163936A (zh) * 2017-10-03 2020-05-15 信越化学工业株式会社 防水防油构件和防水防油构件的制造方法
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WO2019069642A1 (fr) * 2017-10-03 2019-04-11 信越化学工業株式会社 Élément hydrophobe et oléophobe et procédé pour fabriquer un élément hydrophobe et oléophobe
JP2019089332A (ja) * 2017-11-15 2019-06-13 ダイキン工業株式会社 基材
WO2019098230A1 (fr) * 2017-11-15 2019-05-23 ダイキン工業株式会社 Matériau de base
WO2019120879A1 (fr) * 2017-12-22 2019-06-27 BSH Hausgeräte GmbH Objet muni d'un revêtement anti-adhésif omniphobe résistant aux températures élevées et procédé de fabrication dudit objet
JPWO2019189071A1 (ja) * 2018-03-26 2021-04-01 日本電気硝子株式会社 アンチグレア膜付き基板、積層体、及び積層体の製造方法
JP7188439B2 (ja) 2018-03-26 2022-12-13 日本電気硝子株式会社 積層体の製造方法
WO2019189071A1 (fr) * 2018-03-26 2019-10-03 日本電気硝子株式会社 Substrat doté d'un film antireflet, stratifié et procédé de production de stratifié
JPWO2020039795A1 (ja) * 2018-08-20 2021-08-12 信越化学工業株式会社 撥水撥油部材及び撥水撥油部材の製造方法
JP7211423B2 (ja) 2018-08-20 2023-01-24 信越化学工業株式会社 撥水撥油部材及び撥水撥油部材の製造方法
WO2020039795A1 (fr) * 2018-08-20 2020-02-27 信越化学工業株式会社 Élément hydrophobe et oléophobe et procédé de fabrication d'un élément hydrophobe et oléophobe
WO2020137992A1 (fr) * 2018-12-26 2020-07-02 Ａｇｃ株式会社 Substrat avec couche hydrofuge et oléofuge ainsi que procédé de fabrication de celui-ci, et matériau de dépôt en phase vapeur
WO2020171091A1 (fr) * 2019-02-22 2020-08-27 Ａｇｃ株式会社 Substrat en verre fixé à une couche de prévention de contamination et procédé de fabrication d'un substrat en verre fixé à une couche de prévention de contamination
CN113905883B (zh) * 2019-05-22 2024-01-05 大金工业株式会社 防污基材
CN113905883A (zh) * 2019-05-22 2022-01-07 大金工业株式会社 防污基材
US11971519B2 (en) 2020-07-09 2024-04-30 Corning Incorporated Display articles with antiglare surfaces and thin, durable antireflection coatings
US11977206B2 (en) 2020-07-09 2024-05-07 Corning Incorporated Display articles with diffractive, antiglare surfaces and thin, durable antireflection coatings
WO2023013477A1 (fr) * 2021-08-05 2023-02-09 信越化学工業株式会社 Article ayant une couche de surface hydrofuge et oléofuge
WO2023013476A1 (fr) * 2021-08-05 2023-02-09 信越化学工業株式会社 Article ayant une couche de surface hydrofuge et oléofuge

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