WO2019088098A1 - 積層体 - Google Patents
積層体 Download PDFInfo
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- WO2019088098A1 WO2019088098A1 PCT/JP2018/040328 JP2018040328W WO2019088098A1 WO 2019088098 A1 WO2019088098 A1 WO 2019088098A1 JP 2018040328 W JP2018040328 W JP 2018040328W WO 2019088098 A1 WO2019088098 A1 WO 2019088098A1
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- 0 CC(N(C)c1cc(SC*)ccc1)=O Chemical compound CC(N(C)c1cc(SC*)ccc1)=O 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
- B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/02—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions
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- 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
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
- C08L83/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/10—Block or graft copolymers containing polysiloxane sequences
- C09D183/12—Block or graft copolymers containing polysiloxane sequences containing polyether sequences
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2509/00—Household appliances
- B32B2509/10—Refrigerators or refrigerating equipment
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2427/00—Presence of halogenated polymer
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2429/00—Presence of polyvinyl alcohol
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2433/00—Presence of (meth)acrylic polymer
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2461/00—Presence of condensation polymers of aldehydes or ketones
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2463/00—Presence of epoxy resin
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2479/00—Presence of polyamine or polyimide
- C09J2479/08—Presence of polyamine or polyimide polyimide
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2483/00—Presence of polysiloxane
Definitions
- the present invention relates to a laminate and an article comprising the laminate.
- a display assembly, a touch panel assembly, a solar cell assembly, and the like each have, as a constituent material thereof, a laminate in which various base layers are laminated.
- a base material layer such as a liquid crystal panel, a touch panel, an electrode glass, a cover glass, etc., is bonded with an adhesive.
- the laminate as described above may cause the adhesive layer to swell when the article containing it is used for a long time.
- an object of the present invention is to provide a laminate having excellent resistance to chemicals.
- the inventors of the present invention have found that, in a laminate in which a base material layer is bonded with an adhesive, the end face is protected with a perfluoropolyether group-containing compound to obtain chemical It has been found that the resistance to substances is improved, and the present invention has been completed.
- an article comprising the above-mentioned laminate of the present invention.
- the end face is protected by the curable composition containing the perfluoropolyether group-containing compound.
- the laminate of the present invention comprises a first substrate layer, an adhesive layer, and a second substrate layer.
- the first base layer, the adhesive layer, and the second base layer are laminated in this order. That is, the first base material layer and the second base material layer are bonded by the adhesive layer to form a laminate.
- the material which comprises a 1st base material layer and a 2nd base material layer is not specifically limited, For example, it is selected from the group which consists of resin, a metal, a metal oxide, ceramic, and glass.
- acrylic resin polycarbonate-type resin, ABS resin, polyester-type resin, polyimide-type resin, polyamide-type resin, polyolefin type etc. are mentioned.
- the metal oxide is not particularly limited, and examples thereof include ITO (indium tin oxide), anodized aluminum, and the like.
- said ceramic For example, aluminum oxide, a silicon oxide, a zirconium etc. are mentioned.
- the glass is not particularly limited.
- soda lime glass, alkali aluminosilicate glass, borosilicate glass, non-alkali glass, crystal glass, quartz glass are preferable, chemically strengthened soda lime glass, chemically strengthened alkali aluminosilicate Acid salt glass, chemically bonded borosilicate glass and the like.
- the materials constituting the first base layer and the second base layer may be the same or may be different from each other.
- the shapes of the first base layer and the second base layer are not particularly limited, and may be, for example, films or plates.
- the thicknesses of the first base layer and the second base layer are not particularly limited, but for example, are each 0.01 mm or more and 10.0 mm or less, 0.1 mm or more and 5 mm or less, or 0.5 mm or more and 2 mm or less obtain.
- Each of the first base layer and the second base layer may be a single member.
- a touch panel, a cover glass, a scattering prevention film, a liquid crystal panel, an electrode film, a protective sheet and the like can be mentioned.
- the above-mentioned members are a printed circuit board (PCB: Printed Circuit Board) and electronic devices mounted thereon, such as a large scale integrated circuit (LSI: Large Scale Integration), a housing and an electronic device fixed thereto , For example, a speaker, a display module, etc.
- PCB printed Circuit Board
- LSI Large Scale Integration
- the material which comprises the said adhesive bond layer will not be specifically limited if the said 1st base material layer and a 2nd base material layer can be bonded together.
- the material constituting the adhesive layer is not particularly limited.
- various curable types such as a photocurable adhesive such as an ultraviolet curable type, a reactive curable type adhesive, a thermosetting type adhesive, an anaerobic type adhesive, etc.
- An adhesive can be used.
- adhesives are not particularly limited, for example, epoxy resin, acrylic resin, silicone resin, phenol resin, amino resin, polyimide resin, imide resin, polyvinyl resin, polyester resin, PVC (polyvinyl chloride) resin, PVB (polyvinyl butyl resin) And resins such as EVA (ethylene vinyl acetate) resin.
- the thickness of the said adhesive bond layer is not specifically limited, For example, 0.01 mm or more and 1.0 mm or less, 0.05 mm or more and 0.8 mm or less, or 0.1 mm or more and 0.6 mm or less may be sufficient.
- the adhesive layer may be an adhesive sheet, an adhesive sheet, a sheet-like or film-like adhesive, for example, an OCA (optical clear adhesive) film, a liquid adhesive injected and then cured by UV, heat, etc.
- An adhesive (so-called liquid OCA) can be suitably used.
- the laminate can be obtained by bonding the first base material layer and the second base material layer with the adhesive layer.
- the method of bonding is not particularly limited, and the bonding can be performed by a method known in each field.
- the laminate is not particularly limited.
- a laminate of a touch panel and a cover glass by an adhesive layer a laminate of a liquid crystal panel and a cover glass by an adhesive layer, and a laminate of a touch panel and a liquid crystal panel by an adhesive layer
- What combined, what bonded the electrode film and the cover glass with an adhesive layer, and what bonded glass and a scattering prevention film with an adhesive layer etc. are mentioned.
- the end face of the laminate is covered with a layer formed of a curable composition containing a perfluoropolyether group-containing compound (hereinafter also referred to as "PFPE-containing compound"). That is, the end face of the laminate is protected by a layer formed of a curable composition containing a perfluoropolyether group-containing compound.
- PFPE-containing compound a curable composition containing a perfluoropolyether group-containing compound
- the shape and the like of the protective layer are not limited as long as it covers at least a part of the adhesive layer exposed to the end face of the laminate.
- the protective layer covers 50% or more, preferably 80% or more, and more preferably substantially 100% of the surface area of the adhesive layer exposed to the end face of the laminate.
- the protective layer may also cover the end face of the first base layer and the second base layer beyond the adhesive layer area exposed to the end face of the laminate.
- the protective layer may extend beyond the end face of the laminate to the main surface of the laminate, that is, the main surfaces of the first base layer and the second base layer.
- the thickness of the protective layer is not particularly limited, but may be, for example, 10 ⁇ m to 1.0 mm, preferably 20 ⁇ m to 500 ⁇ m, and more preferably 30 ⁇ m to 200 ⁇ m.
- the adhesive layer Since the adhesive layer is exposed in the conventional laminates whose end faces are not protected, contaminants from the outside, for example, machine oil, oil such as oleic acid, water, rain water, sweat, sebum, or acid, alkali, etc.
- the chemical substances of this type may cause problems such as expansion, whitening of the adhesive layer, generation of air bubbles, and peeling of the layer.
- the laminate of the present invention has the above-mentioned protective layer, thereby protecting the adhesive layer from the above-mentioned contaminants and having excellent resistance.
- di- to dodeca-valent organic group means a carbon-containing di- to 10-valent group.
- the di- to deca-valent organic group is not particularly limited, and examples thereof include di- to 10-valent groups obtained by further removing 1 to 9 hydrogen atoms from a hydrocarbon group.
- the divalent organic group is not particularly limited, and examples thereof include divalent groups in which one hydrogen atom is further eliminated from a hydrocarbon group.
- hydrocarbon group means a group containing carbon and hydrogen wherein one hydrogen atom has been eliminated from the molecule.
- a hydrocarbon group is not particularly limited, but is a hydrocarbon group having 1 to 20 carbon atoms which may be substituted by one or more substituents, for example, an aliphatic hydrocarbon group And aromatic hydrocarbon groups.
- the “aliphatic hydrocarbon group” may be linear, branched or cyclic, and may be saturated or unsaturated.
- the hydrocarbon group may also contain one or more ring structures.
- Such a hydrocarbon group may have one or more of N, O, S, Si, an amide, a sulfonyl, a siloxane, a carbonyl, a carbonyloxy and the like in the terminal or molecular chain thereof.
- the substituent of the “hydrocarbon group” is not particularly limited, and for example, a halogen atom; C 1-6 alkyl optionally substituted by one or more halogen atoms Group, C 2-6 alkenyl group, C 2-6 alkynyl group, C 3-10 cycloalkyl group, C 3-10 unsaturated cycloalkyl group, 5- to 10-membered heterocyclyl group, 5- to 10-membered unsaturated heterocyclyl Groups, one or more groups selected from C 6-10 aryl groups and 5-10 membered heteroaryl groups.
- an alkyl group and a phenyl group may be unsubstituted or substituted, unless otherwise specified.
- the substituent of such group is not particularly limited, and one or more groups selected from, for example, a halogen atom, a C 1-6 alkyl group, a C 2-6 alkenyl group and a C 2-6 alkynyl group It can be mentioned.
- PFPE-containing compound is not particularly limited, but typically, it is a perfluoropolyether group-containing silane compound (hereinafter also referred to as "PFPE-containing silane compound") or a perfluorocarbon having a carbon-carbon double bond at the molecular end It is a polyether group containing compound (Hereafter, it is also called "PFPE containing unsaturated compound.”).
- PFPE-containing silane compound a perfluoropolyether group-containing silane compound
- PFPE containing unsaturated compound a polyether group containing compound
- the PFPE-containing silane compound has a Si atom bonded to at least one group selected from the group consisting of a hydroxyl group and a hydrolyzable group at both molecular terminals.
- the PFPE-containing silane compound is at least one compound represented by Formula (A), (B), (C), or (D).
- PFPE is independently at each occurrence: - (OC 6 F 12) a - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 X 10 6) d - (OC 2 F 4) e - (OCF 2) f - Is a group represented by
- a, b, c, d, e and f are each independently an integer of 0 or more and 200 or less, and the sum of a, b, c, d, e and f is at least 1.
- the sum of a, b, c, d, e and f is 5 or more, more preferably 10 or more.
- the sum of a, b, c, d, e and f is 200 or less, more preferably 200 or less, for example 10 or more and 200 or less, more specifically 10 or more and 100 or less.
- X 10 each independently at each occurrence is a hydrogen atom, a fluorine atom or a chlorine atom, preferably a hydrogen atom or a fluorine atom, more preferably a fluorine atom.
- the above a and b are preferably each independently 0 or more and 30 or less, and may be 0 or less.
- each of the above a, b, c and d is independently preferably an integer of 0 or more and 30 or less, more preferably an integer of 20 or less, particularly preferably an integer of 10 or less, and further Preferably it is an integer of 5 or less, and may be zero.
- the sum of a, b, c and d is preferably 30 or less, more preferably 20 or less, still more preferably 10 or less, particularly preferably 5 or less.
- the sum of e and f is preferably 30 or more, more preferably 40 or more, still more preferably 50 or more.
- repeating units may be linear or branched, but are preferably linear.
- - (OC 6 F 12) - is, - (OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2) -, - (OCF (CF 3) CF 2 CF 2 CF 2 CF 2) -, - (OCF 2 CF (CF 3) CF 2 CF 2 CF 2) -, - (OCF 2 CF 2 CF (CF 3) CF 2 CF 2) -, - (OCF 2 CF 2 CF (CF 3) CF 2 CF 2) -, - (OCF 2 CF 2 CF (CF 3) CF 2) - And-(OCF 2 CF 2 CF 2 CF (CF 3 ))-may be used, but-(OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 )-is preferable.
- - (OC 5 F 10) - is, - (OCF 2 CF 2 CF 2 CF 2 CF 2) -, - (OCF (CF 3) CF 2 CF 2 CF 2) -, - (OCF 2 CF (CF 3) It may be CF 2 CF 2 )-,-(OCF 2 CF 2 CF (CF 3 ) CF 2 )-,-(OCF 2 CF 2 CF (CF 3 ))-or the like, preferably-( OCF 2 CF 2 CF 2 CF 2 CF 2) - a.
- - (OC 4 F 8) - is, - (OCF 2 CF 2 CF 2 CF 2) -, - (OCF (CF 3) CF 2 CF 2) -, - (OCF 2 CF (CF 3) CF 2) - , - (OCF 2 CF 2 CF (CF 3)) -, - (OCF 2 CF 3) 2 CF 2) -, - (OCF 2 C (CF 3) 2) -, - (OCF (CF 3) CF ( It may be any of CF 3 )),-(OCF (C 2 F 5 ) CF 2 )-and-(OCF 2 CF (C 2 F 5 ))-, but preferably-(OCF 2 CF 2).
- - (OC 3 F 6) - (i.e., in the above formulas, X 10 is a fluorine atom) is, - (OCF 2 CF 2 CF 2) -, - (OCF (CF 3) CF 2) - and - ( It may be any of OCF 2 CF (CF 3 ))-, but is preferably-(OCF 2 CF 2 CF 2 )-.
- - (OC 2 F 4) - is, - (OCF 2 CF 2) - and - (OCF (CF 3)) - but it may be any of, preferably - (OCF 2 CF 2) - in is there.
- the PFPE is — (OC 3 F 6 ) d — (wherein d is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less) .
- PFPE is — (OCF 2 CF 2 CF 2 ) d — (wherein d is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less) or OCF (CF 3 ) CF 2 ) d — (wherein d is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less).
- PFPE is — (OCF 2 CF 2 CF 2 ) d — (wherein d is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less) .
- the PFPE is — (OC 4 F 8 ) c — (OC 3 F 6 ) d — (OC 2 F 4 ) e — (OCF 2 ) f —, wherein c and d are each independently And e and f are each independently an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less, and c, d, e and The sum of f is at least 5 or more, preferably 10 or more, and the order in which each repeating unit enclosed in parentheses with the subscript c, d, e or f is given is arbitrary in the formula).
- PFPE is, - (OCF 2 CF 2 CF 2 CF 2) c - (OCF 2 CF 2 CF 2) d - (OCF 2 CF 2) e - (OCF 2) f - a.
- PFPE is — (OC 2 F 4 ) e — (OCF 2 ) f — (wherein e and f are each independently 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably Is an integer of 10 or more and 200 or less, and the order in which each repeating unit enclosed in parentheses with the subscript e or f is attached may be arbitrary in the formula).
- e and f are each independently 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably Is an integer of 10 or more and 200 or less, and the order in which each repeating unit enclosed in parentheses with the subscript e or f is attached may be arbitrary in the formula).
- PFPE is a group represented by-(R 6 -R 7 ) j- .
- R 6 is OCF 2 or OC 2 F 4 , preferably OC 2 F 4 .
- R 7 is a group selected from OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 or selected independently from these groups A combination of two or three groups.
- R 7 is a group selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 or from OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 It is a selected group, or a combination of 2 or 3 groups independently selected from these groups.
- the combination of 2 or 3 groups independently selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 is not particularly limited.
- the j is an integer of 2 or more, preferably 3 or more, more preferably 5 or more, and 100 or less, preferably 50 or less.
- OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 may be linear or branched, preferably linear .
- PFPE is preferably, - (OC 2 F 4 -OC 3 F 6) j - or - (OC 2 F 4 -OC 4 F 8) j - is.
- the ratio of e to f (hereinafter referred to as “e / f ratio”) is 0.1 or more and 10 or less, preferably 0.2 or more and 5 or less, and more preferably 0.2 or more and 2 or less More preferably, it is 0.2 or more and 1.5 or less.
- e / f ratio the water repellency, oil repellency and chemical resistance of the cured product obtained from this compound (for example, durability against aqueous solution of salt, acid or basic solution, acetone, oleic acid or hexane) ) Can be further improved.
- the smaller the e / f ratio the better the water repellency, oil repellency and chemical resistance of the cured product.
- the stability of the compound can be further enhanced. The higher the e / f ratio, the better the stability of the compound.
- the e / f ratio is less than 1.0.
- the e / f ratio is preferably 0.10 or more, more preferably 0.20 or more, and still more preferably 0.40 or more.
- the e / f ratio is preferably 0.90 or less, more preferably 0.85 or less, still more preferably 0.80 or less.
- the e / f ratio is preferably 0.10 or more and 1.0 or less, 0.20 or more and 0.90 or less, more preferably 0.40 or more and 0.85 or less, particularly preferably 0.40 or more and 0 .80 or less.
- the e / f ratio is 1.0 or greater.
- the e / f ratio is preferably 1.1 or more, more preferably 1.2 or more.
- the e / f ratio is preferably 10.0 or less, more preferably 5.0 or less, further preferably 2.0 or less, particularly preferably 1.5 or less.
- the e / f ratio is preferably 1.0 or more and 10.0 or less, more preferably 1.0 or more and 5.0 or less, still more preferably 1.0 or more and 2.0 or less, and particularly preferably 1. It is 0 or more and 1.5 or less.
- the number average molecular weight of -PFPE- moiety is not particularly limited, but for example, 500 to 30,000, preferably 1,500 to 30,000, more preferably 2,000 to It is 10,000.
- the above-mentioned number average molecular weight is a value measured by 19 F-NMR.
- the number average molecular weight of the -PFPE- moiety may be in the range of 2000 to 200,000, preferably in the range of 3000 to 100,000.
- the above-mentioned number average molecular weight is a value measured by 19 F-NMR.
- the number average molecular weight of the -PFPE- moiety may be in the range of 1,000 to 3,000, preferably in the range of 2,000 to 3,000.
- the viscosity of the curable composition may be low and the handleability may be good.
- the number average molecular weight of the -PFPE- moiety may be in the range of 5,000 to 10,000, preferably in the range of 6000 to 9000.
- R 13 independently at each occurrence represents a hydroxyl group or a hydrolysable group.
- the hydrolyzable group is as defined above.
- R 14 each independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms.
- each occurrence of R 11 independently represents a hydrogen atom or a halogen atom.
- the halogen atom is preferably an iodine atom, a chlorine atom or a fluorine atom, and more preferably a fluorine atom.
- each occurrence of R 12 independently represents a hydrogen atom or a lower alkyl group.
- the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group and a propyl group.
- R 11 ′ ′ , R 12 ′ ′ , R 13 ′ ′ and R 14 ′ ′ are respectively the same as R 11 , R 12 , R 13 and R 14 .
- the Si atom bonded to at least one group selected from the group consisting of a hydroxyl group and a hydrolysable group is a group in which n1 is an integer of 1 to 3 (-SiR 13 n1 R 14 3- The Si atom contained in ( n1 ) or (-SiR13 " n1 R14 " 3-n1 ) is shown.
- n1 is an integer of 0 to 3 independently for each (-SiR 13 n1 R 14 3-n 1 ) unit or for each (-SiR 13 ′ ′ n1 R 14 ′ 3-n 1 ) unit, Preferably, it is 1 to 3, and more preferably 3.
- at least two n1 are integers of 1 to 3, that is, all n1 are never 0 simultaneously.
- at least one each of R 13 and R 13 ′ ′ is present.
- —SiR 13 n1 R 14 3-n1 structure ie, —SiR 13 moiety
- n1 wherein n1 is 1 or more
- There are at least one each of —SiR 13 ′ ′ n1 R 14 ′ ′ 3-n 1 structures ie, —SiR 13 ′ ′ portions) where is 1 or more.
- Si atoms bonded to at least one group selected from the group consisting of a hydroxyl group and a hydrolyzable group are present at both ends of the molecular main chain. That is, in the formula (A), at least one —SiR 13 n1 R 14 3-n1 structure (that is, —SiR 13 portion) in which n1 is 1 or more, and at least one n1 is 1 or more— SiR 13 ′ ′ n 1 R 14 ′ ′ 3-n 1 structure (ie, —SiR 13 ′ ′ moiety) is present.
- each X 1 independently represents a single bond or a di- to 10-valent organic group.
- said X 1 mainly has a water-repellent property, a surface sliding property and the like, ie, a binding property between a perfluoropolyether part (ie, -PFPE-part) and a substrate. It is understood as a linker linking the provided silane moiety (ie the group bracketed with ⁇ 1). Accordingly, X 1 may be a single bond or any organic group as long as the compound represented by the formula (A) can be stably present.
- a group described as X 1 is bonded to a group represented by PFPE on the left side and a group enclosed in parentheses with ⁇ 1 attached on the right side.
- X 1 can be X e .
- X e represents a single bond or 2-10 divalent organic group, preferably a single bond or -C 6 H 4 -, (i.e. - - phenylene.
- Each R 4 independently represents a hydrogen atom, a phenyl group, or a C 1-6 alkyl group (preferably a methyl group), preferably a hydrogen atom or a methyl group.
- the —C 6 H 4 —, —CO—, —NR 4 — or —SO 2 — is preferably contained in the molecular main chain of the PFPE-containing silane compound.
- X e is more preferably a single bond or -C 6 H 4 -, - CONR 4 -, - CONR 4 -C 6 H 4 -, - CO -, - CO-C 6 H 4 -, - SO 2 NR 4 -, - SO 2 NR 4 -C 6 H 4 -, - SO 2 -, and -SO 2 -C 6 H 4 - represents a 2-10 monovalent organic group having at least one selected from the group consisting of .
- Additional -C 6 H 4 -, - CONR 4 -, - CONR 4 -C 6 H 4 -, - CO -, - CO-C 6 H 4 -, - SO 2 NR 4 -, - SO 2 NR 4 - C 6 H 4 -, - SO 2 -, or -SO 2 -C 6 H 4 - is preferably contained in the molecular backbone of the PFPE-containing silane compound.
- ⁇ 1 is an integer of 1 to 9 and can be changed according to the valence of X 1 .
- [alpha] 1 is the value obtained by subtracting 1 from the valence of X 1.
- ⁇ 1 is 1.
- the above X 1 is preferably a divalent to heptavalent, more preferably a divalent to tetravalent, and still more preferably a divalent organic group.
- X 1 is a divalent to tetravalent organic group, and ⁇ 1 is 1 to 3.
- X 1 is a divalent organic group and ⁇ 1 is 1.
- the formula (A) is represented by the following formula (A ′).
- R 31 represents a single bond,-(CH 2 ) s ' -or o-, m- or p-phenylene group, preferably-(CH 2 ) s'- s ′ is an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and still more preferably 1 or 2.
- X a represents-(X b ) l ' - X b is independently at each occurrence -O-, -S-, o-, m- or p-phenylene, -C (O) O-, -Si (R 33 ) 2 -,-( Si (R 33) 2 O) m '-Si (R 33) 2 -, - CONR 34 -, - O-CONR 34 -, - NR 34 - and - (CH 2)
- n' - is selected from the group consisting of Represents a group R 33 each independently represents a phenyl group, a C 1-6 alkyl group or a C 1-6 alkoxy group, preferably a phenyl group or a C 1-6 alkyl group, more preferably a methyl group
- R 34 independently at each occurrence represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group (preferably a methyl group),
- R 31 and X a are one or more selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group It may be substituted by the substituent of
- l ' is 1.
- X 1 is- (R 31 ) p ' -(X a ) q' -R 32- .
- R 32 represents a single bond,-(CH 2 ) t ' -or o-, m- or p-phenylene group, preferably-(CH 2 ) t'- .
- t ′ is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3.
- R 32 (typically a hydrogen atom in R 32 ) is substituted by one or more substituents selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group It may be done.
- said X 1 is Single bond, C 1-20 alkylene group, -R 31 -X c -R 32- or -X d -R 32- [Wherein, R 31 and R 32 are as defined above. ] It can be.
- the alkylene group, - (C ⁇ H 2 ⁇ ) - a group having the structure, may be substituted or unsubstituted, may be linear or branched.
- X 1 is -X f -, -X f -C 1-20 alkylene group, -X f - (CH 2) s ' -X c -, -X f - (CH 2) s '-X c - (CH 2) t' - -X f -X d- or -X f -X d- (CH 2 ) t ' - It is.
- s 'and t' are as defined above.
- X f is an alkylene group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, such as a methylene group.
- the hydrogen atom in X f may be substituted by one or more substituents selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group, preferably substituted There is.
- X f may be linear or branched, and is preferably linear.
- X 1 is Single bond, C 1-20 alkylene group, -(CH 2 ) s' -X c- , -(CH 2 ) s ' -X c- (CH 2 ) t'- -X d- or -X d- (CH 2 ) t ' - [Wherein, s ′ and t ′ are as defined above. ] It is.
- X c is -O-, -S-, -C (O) O-, -CONR 34 -, -O-CONR 34 -, -Si (R 33 ) 2- , - (Si (R 33) 2 O) m '-Si (R 33) 2 -, -O- (CH 2) u '- (Si (R 33) 2 O) m' -Si (R 33) 2 -, -O- (CH 2) u '-Si (R 33) 2 -O-Si (R 33) 2 -CH 2 CH 2 -Si (R 33) 2 -O-Si (R 33) 2 -, -O- (CH 2) u '-Si (OCH 3) 2 OSi (OCH 3) 2 -, -CONR 34 - (CH 2) u '- (Si (R 33) 2 O) m' -Si (R 33) 2 -, -CONR 34
- X d is -S-, -C (O) O-, -CONR 34 -, -CONR 34 - (CH 2) u '- (Si (R 33) 2 O) m' -Si (R 33) 2 -, -CONR 34 - (CH 2) u '-N (R 34) -, or -CONR 34 - (o-, m- or p- phenylene) -Si (R 33) 2 - [Wherein each symbol is as defined above. ] Represents
- X 1 is -X f -, -X f -C 1-20 alkylene group, -X f - (CH 2) s ' -X c -, -X f - (CH 2) s '-X c - (CH 2) t' - -X f -X d- or -X f -X d- (CH 2 ) t ' - [Wherein, X f , s ′ and t ′ are as defined above.
- X c is, -O-, or -CONR 34 -
- X d is, -CONR 34 -
- R 34 each independently represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group (preferably a methyl group) at each occurrence.
- X 1 is -X f - (CH 2) s ' -X c -, -X f - (CH 2) s '-X c - (CH 2) t' - -X f -X d- or -X f -X d- (CH 2 ) t ' -
- X f , s ′ and t ′ are as defined above.
- X c is, -CONR 34 -
- X d is, -CONR 34 -, R 34 each independently represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group (preferably a methyl group) at each occurrence.
- X 1 is Single bond, C 1-20 alkylene group, -(CH 2 ) s' -X c- (CH 2 ) t ' -or -X d- (CH 2 ) t'- [Wherein each symbol is as defined above. ] It can be.
- said X 1 is Single bond, C 1-20 alkylene group, -(CH 2 ) s ' -O- (CH 2 ) t'- , -(CH 2 ) s' -(Si (R 33 ) 2 O) m ' -Si (R 33 ) 2- (CH 2 ) t'- , - (CH 2) s '-O- (CH 2) u' - (Si (R 33) 2 O) m '-Si (R 33) 2 - (CH 2) t' -, or - (CH 2) s' -O- (CH 2) t '-Si (R 33) 2 - (CH 2) u' -Si (R 33) 2 - (C v H 2v) - [Wherein, R 33 , m ′, s ′, t ′ and u ′ are as defined above, and v is an integer of 1 to 20, preferably an integer of 2 to 6, more
- -(C v H 2v ) - may be linear or branched, and for example, -CH 2- , -CH 2 CH 2- , -CH 2 CH 2 CH 2 -, - CH (CH 3 ) -, - CH (CH 3) CH 2 - may be.
- the X 1 group is substituted by one or more substituents selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group (preferably a C 1-3 perfluoroalkyl group) It may be done.
- the X 1 group may be other than an —O—C 1-6 alkylene group.
- the X 1 group includes, for example, the following groups: [Wherein each R 41 is independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C 1-6 alkoxy group, preferably a methyl group; D is -CH 2 O (CH 2 ) 2- , -CH 2 O (CH 2 ) 3- , -CF 2 O (CH 2 ) 3- , -(CH 2 ) 2- , -(CH 2 ) 3- , - (CH 2) 4 -, -CONH- (CH 2 ) 3- , -CON (CH 3 )-(CH 2 ) 3- , -CON (Ph)-(CH 2 ) 3- (wherein, Ph means phenyl), and (Wherein, each R 42 independently represents a hydrogen atom, a C 1-6 alkyl group or a C 1-6 alkoxy group, preferably a methyl group or a methoxy group, more preferably a a methyl
- X 1 include, for example: Single bond, -CH 2 OCH 2- , -CH 2 O (CH 2 ) 2- , -CH 2 O (CH 2 ) 3- , -CH 2 O (CH 2 ) 6- , -CF 2 -CH 2 -O-CH 2- , -CF 2 -CH 2 -O- (CH 2 ) 2- , -CF 2 -CH 2 -O- (CH 2 ) 3- , -CF 2 -CH 2 -O- (CH 2 ) 6- -CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2- , -CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2- , -CH 2 O (CH 2) 3 Si (CH 3) 2 O (Si (CH 3) 2 O) 2 Si (CH 3) 2 (CH 2) 2 -,
- X 1 is -CH 2 OCH 2- , -CH 2 O (CH 2 ) 2- , -CH 2 O (CH 2 ) 3- , -CH 2 O (CH 2 ) 6- , -CF 2 -CH 2 -O-CH 2- , -CF 2 -CH 2 -O- (CH 2 ) 2- , -CF 2 -CH 2 -O- (CH 2 ) 3- , -CF 2 -CH 2 -O- (CH 2 ) 6- -CH 2 OCF 2 CHFOCF 2- , -CH 2 OCF 2 CHFOCF 2 CF 2- , -CH 2 OCF 2 CHFOCF 2 CF 2- , -CH 2 OCF 2 CHFOCF 2 CF 2 CF 2- , -CH 2 OCH 2 CF 2 CF 2 OCF 2- , -CH 2 OCH 2 CF 2 CF 2 OCF 2- , -CH 2 OCH 2 CF 2 CF 2 OCF 2- , -CH 2 OCH 2 CF 2
- X 1 is -CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 -C (O) NH-CH 2- , -CONH-, -CONH-CH 2- , -CONH- (CH 2 ) 2- , -CONH- (CH 2 ) 3- , -CONH- (CH 2 ) 6- , -CF 2 CONH-, -CF 2 CONHCH 2- , -CF 2 CONH (CH 2 ) 2- , -CF 2 CONH (CH 2 ) 3- , -CF 2 CONH (CH 2 ) 6- , -CON (CH 3 )-(CH 2 ) 3- , -CON (Ph)-(CH 2 ) 3- (wherein Ph means phenyl), -CON (CH 3 )-(CH 2 ) 6- , -CON (Ph)-(CH 2 ) 6- (wherein Ph means phenyl), -CON (CH 3 )-(CH 2 ) 6- , -CON (Ph)
- X 1 represents X e ′ .
- X e ′ is a single bond, an alkylene group having 1 to 6 carbon atoms, -R 51 -C 6 H 4 -R 52- , -R 51 -CONR 4 -R 52- , -R 51 -CONR 4 -C 6 H 4 -R 52 -, - R 51 -CO-R 52 -, - R 51 -CO-C 6 H 4 -R 52 -, - R 51 -SO 2 NR 4 -R 52 -, - R 51 - SO 2 NR 4 -C 6 H 4 -R 52- , -R 51 -SO 2 -R 52- , or -R 51 -SO 2 -C 6 H 4 -R 52- .
- R 51 and R 52 each independently represent a single bond or an alkylene group having 1 to 6 carbon atoms, preferably a single bond or an alkylene group having 1 to 3 carbon atoms.
- R 4 is as defined above.
- the alkylene group is substituted or unsubstituted, preferably unsubstituted.
- a halogen atom Preferably a fluorine atom can be mentioned, for example.
- the alkylene group is linear or branched, and is preferably linear.
- X e ′ is Single bond, -X f -, An alkylene group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, -X f -C 1-6 alkylene group, preferably -X f -C 1-3 alkylene group, more preferably -X f -C 1-2 alkylene group, -C 6 H 4 -R 52 ' -, -CONR 4 '-R 52' -, -CONR 4 '-C 6 H 4 -R 52' -, -X f -CONR 4 '-R 52' -, -X f -CONR 4 '-C 6 H 4 -R 52' -, -CO-R 52 ' -, -CO-C 6 H 4 -R 52 ' -, -SO 2 NR 4 '-R 52' -, -SO 2 NR 4 '-C 6 H 4 -R 52' -, -SO
- X e ′ is preferably -X f -, An alkylene group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, -X f -C 1-6 alkylene group, preferably -X f -C 1-3 alkylene group, more preferably -X f -C 1-2 alkylene group, -CONR 4 '-R 52' -, -CONR 4 '-C 6 H 4 -R 52' -, -X f -CONR 4 '-R 52' -, -X f -CONR 4 '-C 6 H 4 -R 52' -, -R 51 '-CONR 4' -, -R 51 '-CONR 4' -C 6 H 4 -, -CONR 4 ' -, -CONR 4 '-C 6 H 4 -, -CONR 4 ' -, -CONR 4 '-C 6 H 4 - ,
- X e ′ is more preferably -CONR 4 '-R 52' -, -CONR 4 '-C 6 H 4 -R 52' -, -X f -CONR 4 '-R 52' -, -X f -CONR 4 '-C 6 H 4 -R 52' -, -R 51 '-CONR 4' -, -R 51 '-CONR 4' -C 6 H 4 -, -CONR 4 ' -, -CONR 4 '-C 6 H 4 - , -X f -CONR 4 '- or -X f -CONR 4,' -C 6 H 4 -, It can be.
- X e ′ include, for example, Single bond, Perfluoroalkylene groups having 1 to 6 carbon atoms (eg, -CF 2 -,-(CF 2 ) 2-, etc.), An alkylene group having 1 to 6 carbon atoms, -CF 2 -C 1-6 alkylene group, -CONH-, -CONH-CH 2- , -CONH- (CH 2 ) 2- -CONH- (CH 2 ) 3- , -CF 2 -CONH-, -CF 2 CONHCH 2- , -CF 2 CONH (CH 2 ) 2- , -CF 2 CONH (CH 2 ) 3- , -CON (CH 3 )-, -CON (CH 3 ) -CH 2- , -CON (CH 3 )-(CH 2 ) 2- , -CON (CH 3 )-(CH 2 ) 3- , -CF 2 -CON (CH 3 )-, -CF 2 -CON (CH 3 )-,
- preferable X e ′ is An alkylene group having 1 to 6 carbon atoms, Perfluoroalkylene groups having 1 to 6 carbon atoms (eg, -CF 2 -,-(CF 2 ) 2-, etc.), -CF 2 -C 1-6 alkylene group, -CONH-, -CONH-CH 2- , -CONH- (CH 2 ) 2- , -CONH- (CH 2 ) 3- , -CF 2 CONH-, -CF 2 CONHCH 2- , -CF 2 CONH (CH 2 ) 2- , -CF 2 CONH (CH 2 ) 3- , -CON (CH 3 )-, -CON (CH 3 ) -CH 2- , -CON (CH 3 )-(CH 2 ) 2- , -CON (CH 3 )-(CH 2 ) 3- , -CF 2 -CON (CH 3 )-, -CF 2 -CON (CH 3 ) CH 2- ,
- more preferable X e ′ is -CONH-, -CONH-CH 2- , -CONH- (CH 2 ) 2- , -CONH- (CH 2 ) 3- , -CF 2 CONH-, -CF 2 CONHCH 2- , -CF 2 CONH (CH 2 ) 2- , -CF 2 CONH (CH 2 ) 3- , -CON (CH 3 )-, -CON (CH 3 ) -CH 2- , -CON (CH 3 )-(CH 2 ) 2- , -CON (CH 3 )-(CH 2 ) 3- , -CF 2 -CON (CH 3 )-, -CF 2 -CON (CH 3 ) CH 2- , -CF 2 -CON (CH 3 )-(CH 2 ) 2- , -CF 2 -CON (CH 3 )-(CH 2 ) 3- , -CH 2 -CONH-, -CH 2 -CONH-CH 2- ,
- X e ′ is a single bond.
- a group having a binding ability between PFPE and a substrate that is, a group enclosed in parentheses with ⁇ 1 in (A) is directly bonded.
- X 1 is a group represented by the formula:-(R 16 ) x- (CFR 17 ) y- (CH 2 ) z- .
- x, y and z are each independently an integer of 0 to 10, the sum of x, y and z is 1 or more, and the order of existence of each parenthesized parenthesis is in the formula Is optional.
- R 16 are each independently at each occurrence, an oxygen atom, a phenylene, carbazolylene, -NR 18 - (wherein, R 18 represents a hydrogen atom or an organic group) or a divalent organic group is there.
- R 16 is an oxygen atom or a divalent polar group.
- the “lower alkyl group” is, for example, an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group or an n-propyl group, which are substituted by one or more fluorine atoms It is also good.
- R 17 in each occurrence is independently a hydrogen atom, a fluorine atom or a lower fluoroalkyl group, preferably a fluorine atom.
- the “lower fluoroalkyl group” is, for example, a fluoroalkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably trifluoro It is a methyl group, a pentafluoroethyl group, more preferably a trifluoromethyl group.
- X 1 is preferably of the formula: — (O) x — (CF 2 ) y — (CH 2 ) z —, wherein x, y and z are as defined above, in parentheses The order of existence of each repeating unit enclosed is arbitrary group in the formula).
- Examples of the group represented by the above formula:-(O) x- (CF 2 ) y- (CH 2 ) z- include, for example,-(O) x ' -(CH 2 ) z " -O-[(CH 2 ) 2) z '''-O-] z "", and - (O) x' - ( CF 2) y "- (CH 2) z” -O - [(CH 2) z '''-O- Z ′ ′ ′ ′ ′ (wherein, x ′ is 0 or 1, y ′ ′, z ′ ′ and z ′ ′ ′ are each independently an integer of 1 to 10, and z ′ ′ ′ is 0 or 1 The left end of these groups is bonded to the PFPE side.
- X 1 is —O—CFR 20 — (CF 2 ) e ′ —.
- the above R 20 each independently represents a fluorine atom or a lower fluoroalkyl group.
- the lower fluoroalkyl group is, for example, a fluoroalkyl group having 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group or a pentafluoroethyl group, further preferably It is a trifluoromethyl group.
- the above e's are each independently 0 or 1.
- R 20 is a fluorine atom and e ′ is 1.
- examples of X 1 groups include: [In the formula, Each R 41 independently represents a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C 1-6 alkoxy group, preferably a methyl group; In each X 1 group, any part of T is attached to PFPE of the molecular backbone: -CH 2 O (CH 2 ) 2- , -CH 2 O (CH 2 ) 3- , -CF 2 O (CH 2 ) 3- , -CH 2- , -(CH 2 ) 2- , -(CH 2 ) 3- , - (CH 2) 4 -, -CONH- (CH 2 ) 3- , -CON (CH 3 )-(CH 2 ) 3- , -CON (Ph)-(CH 2 ) 3- (wherein Ph means phenyl), or [Wherein, R 42 each independently represents a hydrogen atom, a C 1-6 alkyl group or a C 1-6 alkyl group or
- T's are — (CH 2 ) n ′ ′ (n ′ ′ is an integer from 2 to 6) attached to the group opposite to the PFPE of the molecular main chain, and, if present, the remaining T may be each independently a methyl group, a phenyl group, a C 1-6 alkoxy group or a radical scavenging group or an ultraviolet absorbing group.
- the left side is bonded to the group represented by PFPE and the right side is bonded to the group enclosed in parentheses with ⁇ 1 attached.
- the radical scavenging group is not particularly limited as long as it can scavenge a radical generated upon irradiation with light, for example, benzophenones, benzotriazoles, benzoates, phenyl salicylates, crotonic acids, malonic esters, organoacrylates And residues of hindered amines, hindered phenols, or triazines.
- the ultraviolet absorbing group is not particularly limited as long as it can absorb ultraviolet light, and examples thereof include benzotriazoles, hydroxybenzophenones, esters of substituted and unsubstituted benzoic acid or salicylic acid compounds, acrylates or alkoxycinnamates, oxamides, The residue includes oxanilides, benzoxazinones and benzoxazoles.
- preferred radical scavenging groups or ultraviolet absorbing groups can be mentioned.
- X 1 (and X 3 , X 5 and X 7 described below) may be a trivalent to dodecavalent organic group.
- X 2 each independently represents a single bond or a divalent organic group at each occurrence.
- X 2 is preferably an alkylene group having 1 to 20 carbon atoms, and more preferably — (CH 2 ) u — (wherein u is an integer of 0 to 2).
- t is each independently an integer of 1 to 10. In a preferred embodiment, t is an integer of 1 to 6. In another preferred embodiment, t is an integer of 2 to 10, preferably an integer of 2 to 6.
- the compound represented by the preferred formula (A) has the following formula (A ′): [In the formula: The PFPEs each independently at each occurrence have the formula: - (OC 6 F 12) a - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f - (Wherein, a, b, c, d, e and f are each independently an integer of 0 or more and 200 or less, and the sum of a, b, c, d, e and f is at least 1; The order in which each repeating unit in parentheses is attached with a, b, c, d, e or f is arbitrary in the formula.) A group represented by R 13 independently at each occurrence independently represents a hydroxyl group or a hydrolysable group; R 14 independently represents at each occurrence a hydrogen atom or an alkyl group having 1 to 22 carbon
- the compound represented by formula (A) are, for example, as a raw material a perfluoropolyether derivative corresponding to -PFPE- portion, after introduction of iodine at the end, -CH 2 CR 12 (X 2 -SiR 13 n1 It can be obtained by reacting a vinyl monomer corresponding to R 14 3-n 1 )-.
- PFPE, R 13 , R 13 ′ ′ , R 14 , R 14 ′ ′ and n 1 are as defined for the above formula (A).
- the Si atom bonded to at least one group selected from the group consisting of a hydroxyl group and a hydrolysable group is an integer in which n1 is an integer of 1 to 3 (SiR 13 n 1 R 14 3-n 1 Or a Si atom contained in (-SiR 13 " n1 R 14" 3-n1 ).
- n1 is an integer of 0 to 3 independently for each (-SiR 13 n1 R 14 3-n 1 ) unit or for each (-SiR 13 ′ ′ n1 R 14 ′ 3-n 1 ) unit, preferably Is 1 to 3, more preferably 3.
- at least two n1 are integers of 1 to 3, that is, all n1 are never 0 simultaneously. That is, in the formula, at least two are R 13 or R 13 ′ ′ .
- —SiR 13 n 1 R 14 3-n 1 structure ie, —SiR 13 moiety
- n 1 is 1 or more
- at least two structures selected from the group consisting of —SiR 13 ′ ′ n1 R 14 ′ ′ 3-n 1 structures ie, —SiR 13 ′ ′ moieties in which n 1 is 1 or more.
- At least one Si bonded to a hydroxyl group or a hydrolyzable group is present at each end of the molecular backbone of the PFPE-containing silane compound. That is, at least one SiR 13 moiety is present and at least one SiR 13 ′ ′ moiety is present.
- each X 3 independently represents a single bond or a di- to 10-valent organic group.
- said X 3 mainly has a water-repellent property, a surface slip property and the like, and a bonding ability between a substrate and a perfluoropolyether part (ie, -PFPE-part). It is understood as a linker connecting the provided silane moiety (specifically, -SiR 13 n1 R 14 3-n 1 or -SiR 13 " n 1 R 14" 3- n 1 ).
- X 3 may be a single bond or any organic group as long as the compound represented by the formula (B) can be stably present.
- the left side is bonded to a group represented by PFPE, and the right side is bonded to a group enclosed in parentheses with ⁇ 1 attached.
- X 3 represents X e .
- X e is as defined above.
- ⁇ 1 is an integer of 1 to 9 and can vary depending on the valence of X 3 .
- ⁇ 1 is a value obtained by subtracting 1 from the value of the valence of X 3 .
- ⁇ 1 is 1.
- the above X 3 is preferably a divalent to heptavalent, more preferably a divalent to tetravalent, more preferably a divalent organic group.
- X 3 is a divalent to tetravalent organic group, and ⁇ 1 is 1 to 3.
- X 3 is a divalent organic group and ⁇ 1 is 1.
- the formula (B) is represented by the following formula (B ′).
- Examples of the X 3, is not particularly limited, examples thereof include the same as described for X 1.
- preferred specific X 3 is Single bond, -CH 2 OCH 2- , -CH 2 O (CH 2 ) 2- , -CH 2 O (CH 2 ) 3- , -CH 2 O (CH 2 ) 6- , -CF 2 -CH 2 -O-CH 2- , -CF 2 -CH 2 -O- (CH 2 ) 2- , -CF 2 -CH 2 -O- (CH 2 ) 3- , -CF 2 -CH 2 -O- (CH 2 ) 6- -CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2- , -CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2- , -CH 2 O (CH 2) 3 Si (CH 3) 2 O (Si (CH 3) 2 O) 2 Si (CH 3) 2 (CH 2) 2 -, -CH 2 O (CH
- X 3 is -CH 2 OCH 2- , -CH 2 O (CH 2 ) 2- , -CH 2 O (CH 2 ) 3- , -CH 2 O (CH 2 ) 6- , -CF 2 -CH 2 -O-CH 2- , -CF 2 -CH 2 -O- (CH 2 ) 2- , -CF 2 -CH 2 -O- (CH 2 ) 3- , -CF 2 -CH 2 -O- (CH 2 ) 6- -CH 2 OCF 2 CHFOCF 2- , -CH 2 OCF 2 CHFOCF 2 CF 2- , -CH 2 OCF 2 CHFOCF 2 CF 2- , -CH 2 OCF 2 CHFOCF 2 CF 2 CF 2- , -CH 2 OCH 2 CF 2 CF 2 OCF 2- , -CH 2 OCH 2 CF 2 CF 2 OCF 2- , -CH 2 OCH 2 CF 2 CF 2 OCF 2- , -CH 2 OCH 2 CF 2
- X 3 is -CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 -C (O) NH-CH 2- , -CF 2 -CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 -C (O) NH-CH 2- , -CONH-, -CONH-CH 2- , -CONH- (CH 2 ) 2- , -CONH- (CH 2 ) 3- , -CONH- (CH 2 ) 6- , -CF 2 CONH-, -CF 2 CONHCH 2- , -CF 2 CONH (CH 2 ) 2- , -CF 2 CONH (CH 2 ) 3- , -CF 2 CONH (CH 2 ) 6- , -CON (CH 3 )-(CH 2 ) 3- , -CON (Ph)-(CH 2 ) 3- (wherein Ph means phenyl), -CON (CH 3 )-(CH 2 ) 6- , -CON (Ph)-(CH 2 ) 3-
- X 3 represents X e ′ .
- X e ′ is as defined above.
- X e ′ is a single bond.
- a group having a binding ability between PFPE and a substrate that is, a group which is attached with ⁇ 1 and bracketed in (B) is directly bonded.
- At least two Si bonded to a hydroxyl group or a hydrolyzable group are present. That is, in Formula (B), there are at least two SiR 13 moieties.
- the compound represented by the preferred formula (B) has the following formula (B ′): [In the formula: The PFPEs each independently at each occurrence have the formula: - (OC 6 F 12) a - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f - (Wherein, a, b, c, d, e and f are each independently an integer of 0 or more and 200 or less, and the sum of a, b, c, d, e and f is at least 1; The order in which each repeating unit in parentheses is attached with a, b, c, d, e or f is arbitrary in the formula.) A group represented by R 13 independently at each occurrence independently represents a hydroxyl group or a hydrolysable group; R 14 independently represents at each occurrence a hydrogen atom or an alkyl group having 1 to 22 carbon
- the compound represented by the above formula (B) can be produced by a known method, for example, the method described in JP 2013-117012 A or its improved method.
- PFPE is as defined above.
- X 5 each independently represents a single bond or a di- to 10-valent organic group.
- said X 5 mainly has the ability to bond the substrate with the perfluoropolyether moiety (ie, -PFPE- moiety) which provides water repellency and surface slippage etc. (specifically, -SiR a k1 R b l1 R c m1 group or -SiR a "k1 R b" l1 R c "m1 group) silane unit to provide the solution with a linker connecting. Therefore,
- the X 5 may be a single bond or any organic group as long as the compound represented by the formula (C) can be stably present. structure is described as X 5 is a group left represented by PFPE, based on the right in parentheses are given the .gamma.1, respectively coupled.
- X 5 represents X e .
- X e is as defined above.
- ⁇ 1 is an integer of 1 to 9, and ⁇ 1 may change according to the valence of X 5 .
- ⁇ 1 is a value obtained by subtracting 1 from the value of the valence of X 5 .
- the above X 5 is preferably a divalent to heptavalent, more preferably a divalent to tetravalent, more preferably a divalent organic group.
- X 5 is a divalent to tetravalent organic group, and ⁇ 1 is 1 to 3.
- X 5 is a divalent organic group and ⁇ 1 is 1.
- the formula (C) is represented by the following formula (C ′).
- Examples of X 5 include, but are not limited to, the same as those described for X 1 .
- preferred specific X 5 is Single bond, -CH 2 OCH 2- , -CH 2 O (CH 2 ) 2- , -CH 2 O (CH 2 ) 3- , -CH 2 O (CH 2 ) 6- , -CF 2 -CH 2 -O-CH 2- , -CF 2 -CH 2 -O- (CH 2 ) 2- , -CF 2 -CH 2 -O- (CH 2 ) 3- , -CF 2 -CH 2 -O- (CH 2 ) 6- -CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2- , -CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2- , -CH 2 O (CH 2) 3 Si (CH 3) 2 O (Si (CH 3) 2 O) 2 Si (CH 3) 2 (CH 2) 2 -, -CH 2 O (CH
- X 5 is preferably -CH 2 OCH 2- , -CH 2 O (CH 2 ) 2- , -CH 2 O (CH 2 ) 3- , -CH 2 O (CH 2 ) 6- , -CF 2 -CH 2 -O-CH 2- , -CF 2 -CH 2 -O- (CH 2 ) 2- , -CF 2 -CH 2 -O- (CH 2 ) 3- , -CF 2 -CH 2 -O- (CH 2 ) 6- -CH 2 OCF 2 CHFOCF 2- , -CH 2 OCF 2 CHFOCF 2 CF 2- , -CH 2 OCF 2 CHFOCF 2 CF 2 CF 2- , -CH 2 OCH 2 CF 2 CHFOCF 2 CF 2 CF 2- , -CH 2 OCH 2 CF 2 CF 2 OCF 2- , -CH 2 OCH 2 CF 2 CF 2 OCF 2- , -CH 2 OCH 2 CF 2 CF 2 OCF 2- , -
- X 5 is -CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 -C (O) NH-CH 2- , -CF 2 -CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 -C (O) NH-CH 2- , -CONH-, -CONH-CH 2- , -CONH- (CH 2 ) 2- , -CONH- (CH 2 ) 3- , -CONH- (CH 2 ) 6- , -CF 2 CONH-, -CF 2 CONHCH 2- , -CF 2 CONH (CH 2 ) 2- , -CF 2 CONH (CH 2 ) 3- , -CF 2 CONH (CH 2 ) 6- , -CON (CH 3 )-(CH 2 ) 3- , -CON (Ph)-(CH 2 ) 3- (wherein Ph means phenyl), -CON (CH 3 )-(CH 2 ) 6- , -CON (Ph)-(CH 2 ) 3-
- X 5 represents X e ′ .
- X e ′ is as defined above.
- X e ′ is a single bond.
- a group having a binding ability between PFPE and a substrate that is, a group enclosed in parentheses in the formula (C) with ⁇ 1 attached thereto is directly bonded.
- R a independently represents -Z 3 -SiR 71 p 1 R 72 q 1 R 73 r 1 at each occurrence.
- each Z 3 independently represents an oxygen atom or a divalent organic group.
- the above Z 3 is preferably a divalent organic group, and does not include those forming a siloxane bond with the Si atom at the end of the molecular main chain in the formula (C) (Si atom to which R a is bonded) .
- the above Z 3 is preferably a C 1-6 alkylene group,-(CH 2 ) g -O- (CH 2 ) h- (wherein, g is an integer of 1 to 6 and h is 1 to 6) Or -phenylene- (CH 2 ) i- (wherein i is an integer of 0 to 6), and more preferably a C 1-3 alkylene group.
- These groups may be substituted, for example, by one or more substituents selected from a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group. .
- the above Z 3 is more preferably a linear or branched alkylene group, and still more preferably a linear alkylene group.
- the number of carbon atoms constituting the above Z 3 alkylene group is preferably in the range of 1 to 6, and more preferably in the range of 1 to 3.
- the alkylene group is as described above.
- R 71 independently represents Ra ' at each occurrence.
- R a ′ is as defined in R a .
- the maximum number of Sis linked in a linear fashion via a Z 3 group is five. That is, in the above R a , when at least one R 71 is present, two or more Si atoms linearly linked through the Z 3 group are present in R a , but through such Z 3 group Thus, the number of Si atoms linked in a linear manner is at most five. Note that the "through Z 3 group in R a number of Si atoms linearly linked" is equal to -Z 3 -Si- repetition number of which is connected to a linear during R a become.
- * means a site to be bonded to Si in the main chain, ... indicates that a predetermined group other than Z 3 Si is bonded, ie, all three bonds of Si atoms are ... In this case, it means the end of the repetition of Z 3 Si.
- the number on the right of Si means the appearance number of Si linearly linked via Z 3 group counted from *.
- the chain in which the Z 3 Si repeat is completed in Si 2 is “the number of Si atoms linearly linked via the Z 3 group in R a ” is 2, similarly, Si 3 , And Si 4 and Si 5 in which the Z 3 Si repeat ends are “number of Si atoms linearly linked via Z 3 group in R a ” of 3, 4 and 5, respectively Is one.
- a plurality of Z 3 Si chains are present in R a , but they do not have to have the same length, and may have any length.
- the number of Si atoms linearly linked via the Z 3 group in R a is 1 (left equation) or 2 (all the chains) in all chains. Right).
- the number of Si atoms linearly linked via the Z 3 group in R a is one or two, preferably one.
- each R 72 independently at each occurrence represents a hydroxyl group or a hydrolysable group.
- the "hydrolyzable group” is as defined above.
- R 72 is —OR, wherein R represents a substituted or unsubstituted C 1-3 alkyl group, more preferably a methyl group.
- R 73 each independently represents a hydrogen atom or a lower alkyl group at each occurrence.
- the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
- '(if R a' is absent, R a) terminal of R a in R a in the above q1 is preferably 2 or more, for example 2 or 3, more preferably 3.
- At least one of the terminal parts of R a is —Si (—Z 3 -SiR 72 q1 R 73 r1 ) 2 R 72 q1 ′ R 73 r1 ′ (wherein any one of q1 ′ and r1 ′ Is 1 and the other is 0) or -Si (-Z 3 -SiR 72 q1 R 73 r1 ) 3 , preferably -Si (-Z 3 -SiR 72 q1 R 73 r1 ) 3 (herein And the sum of q1 and r1 is 3.
- (- Z 3 -SiR 72 q1 R 73 r1) units is preferably (-Z 3 -SiR 72 3).
- all the terminal parts of R a may be -Si (-Z 3 -SiR 72 q1 R 73 r1 ) 3 , preferably -Si (-Z 3 -SiR 72 3 ) 3 .
- the ends of the groups represented by (SiR a k1 R b l1 R c m1) is, -Si (-Z 3 -SiR 72 q1 R 73 r1) 2 R b l1 R c m1 ( However, l1 and one of m1 is 1 and the other is 0), -Si (-Z 3 -SiR 72 q1 R 73 r1 ) 2 R 72 q1 ' R 73 r1' (however, either q1 'or r1' Or one is 1 and the other is 0), or -Si (-Z 3 -SiR 72 q1 R 73 r1 ) 3 , preferably -Si (-Z 3 -SiR 72 q1 R 73 r1 ) 3 (Where the sum of q1 and r1 is 3).
- R a ′ ′ independently represents —Z 3 —SiR 71 p1 R 72 ′ ′ q1 R 73 r 1 at each occurrence.
- Z 3 , R 71 , R 73 , p1, q1 and r1 are as defined above.
- R 72 ′ ′ has the same meaning as R 72 .
- At least one of the terminal parts of R a ′ ′ is —Si (—Z 3 -SiR 72 ” q 1 R 73 r 1 ) 2 R 72” q 1 ′ R 73 r 1 ′ (wherein q 1 ′ and r 1 ′ Either one is 1 and the other is 0) or -Si (-Z 3 -SiR 72 " q1 R 73 r1 ) 3 , preferably -Si (-Z 3 -SiR 72" q1 R 73 r1 ) 3 (total 3 is here, q1 and r1) in formula, which may be a,.
- (- Z 3 -SiR 72 " units of q1 R 73 r1) is preferably (-Z 3 -SiR 72" 3)
- all the terminal parts of R a are -Si (-Z 3 -SiR 72 " q 1 R 73 r 1 ) 3 , preferably -Si (-Z 3 -SiR 72" 3 ) 3 obtain.
- the end of the group represented by (SiR a " k1 R b" l1 R c " m1 ) is -Si (-Z 3 -SiR 72" q1 R 73 r1 ) 2 R b " l1 R c" m1 (wherein, one of l1 and m1 is 1 and the other is 0), -Si (-Z 3 -SiR 72 " q1 R 73 r1 ) 2 R 72" q1 ' R 73 r1' (where , one of q1 'and r1' is 1 and the other is 0), or -Si (-Z 3 -SiR 72 "q1 R 73 r1) 3, preferably -Si (-Z 3 -SiR 72 ′ ′ q1 R 73 r1 ) 3 (where the sum of q 1 and r 1 is 3).
- At least two Si bonded to a hydroxyl group or a hydrolyzable group are present. That is, there are at least two structures selected from the group consisting of SiR 72 , SiR 72 ′ ′ , SiR b , and SiR b ′ ′ . R b and R b " will be described later.
- At least one Si bonded to a hydroxyl group or a hydrolyzable group is present at each end of the molecular main chain of the PFPE-containing silane compound. That is, there is at least one structure of SiR 72 and / or SiR b and at least one structure of SiR 72 ′ ′ and / or SiR b ′ ′.
- each R b independently represents a hydroxyl group or a hydrolysable group.
- R includes an unsubstituted alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group and an isobutyl group; and a substituted alkyl group such as a chloromethyl group.
- an alkyl group particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
- the hydroxyl group is not particularly limited, but may be formed by hydrolysis of a hydrolyzable group. More preferably, R b is —OR, wherein R represents a substituted or unsubstituted C 1-3 alkyl group, more preferably a methyl group.
- R b ′ ′ is as defined in R b .
- R c independently at each occurrence represents a hydrogen atom or a lower alkyl group.
- the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
- R c ′ ′ has the same meaning as R c .
- k1 is each independently an integer of 0 to 3 at each occurrence; 11 is each independently an integer of 0 to 3 at each occurrence; m1 is each independently at each occurrence Is an integer of 0 to 3.
- SiR a k1 R b l1 R c m1 or every each (SiR a "k1 R b" l1 R c "m1), the sum of k1, l1 and m1 is 3.
- k1 is preferably 1 to 3, and more preferably 3.
- the compounds represented by the above formula (C) can be synthesized, for example, as described in WO 2014/069592.
- PFPE is as defined in the above formula (A).
- each X 7 independently represents a single bond or a di- to 10-valent organic group.
- said X 7 mainly has the ability to bind to the substrate with the perfluoropolyether moiety (that is, -PFPE- moiety), which provides water repellency and surface slippage etc. It is understood as a linker linking the provided moiety (ie the group bracketed with ⁇ 1). Therefore, the X 7 may be a single bond or any organic group as long as the compound represented by the formula (D) can be stably present.
- the left side is bonded to a group represented by PFPE, and the right side is bonded to a group enclosed in parentheses with ⁇ 1.
- X 7 represents X e .
- X e is as defined above.
- ⁇ 1 is an integer of 1 to 9, and ⁇ 1 can change according to the valence of X 7 .
- ⁇ 1 is the value obtained by subtracting 1 from the valence of X 7.
- ⁇ 1 is 1.
- the above-mentioned X 7 is preferably a divalent to heptavalent, more preferably a divalent to tetravalent, more preferably a divalent organic group.
- X 7 is a divalent to tetravalent organic group, and ⁇ 1 is 1 to 3.
- X 7 is a divalent organic group and ⁇ 1 is 1.
- the formula (D) is represented by the following formula (D ′).
- Examples of X 7 include, but are not particularly limited to, the same ones as those described for X 1 .
- preferred specific X 7 is Single bond, -CH 2 OCH 2- , -CH 2 O (CH 2 ) 2- , -CH 2 O (CH 2 ) 3- , -CH 2 O (CH 2 ) 6- , -CF 2 -CH 2 -O-CH 2- , -CF 2 -CH 2 -O- (CH 2 ) 2- , -CF 2 -CH 2 -O- (CH 2 ) 3- , -CF 2 -CH 2 -O- (CH 2 ) 6- -CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2- , -CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2- , -CH 2 O (CH 2) 3 Si (CH 3) 2 O (Si (CH 3) 2 O) 2 Si (CH 3) 2 (CH 2) 2 -, -CH 2 O (CH
- more preferred specific X 7 is -CH 2 OCH 2- , -CH 2 O (CH 2 ) 2- , -CH 2 O (CH 2 ) 3- , -CH 2 O (CH 2 ) 6- , -CF 2 -CH 2 -O-CH 2- , -CF 2 -CH 2 -O- (CH 2 ) 2- , -CF 2 -CH 2 -O- (CH 2 ) 3- , -CF 2 -CH 2 -O- (CH 2 ) 6- -CH 2 OCF 2 CHFOCF 2- , -CH 2 OCF 2 CHFOCF 2 CF 2- , -CH 2 OCF 2 CHFOCF 2 CF 2 CF 2- , -CH 2 OCH 2 CF 2 CHFOCF 2 CF 2 CF 2- , -CH 2 OCH 2 CF 2 CF 2 OCF 2- , -CH 2 OCH 2 CF 2 CF 2 OCF 2- , -CH 2 OCH 2 CF 2 CF 2 OCF 2- ,
- X 7 is -CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 -C (O) NH-CH 2- , -CF 2 -CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 -C (O) NH-CH 2- , -CONH-, -CONH-CH 2- , -CONH- (CH 2 ) 2- , -CONH- (CH 2 ) 3- , -CONH- (CH 2 ) 6- , -CF 2 CONH-, -CF 2 CONHCH 2- , -CF 2 CONH (CH 2 ) 2- , -CF 2 CONH (CH 2 ) 3- , -CF 2 CONH (CH 2 ) 6- , -CON (CH 3 )-(CH 2 ) 3- , -CON (Ph)-(CH 2 ) 3- (wherein Ph means phenyl), -CON (CH 3 )-(CH 2 ) 6- , -CON (Ph)-(CH 2 ) 3-
- X 7 represents X e ′ .
- X e ′ is as defined above.
- X e ′ is a single bond.
- a group having a binding ability between PFPE and a substrate that is, a group which is attached with .delta.1 in parentheses in the formula (D)
- a bonding strength between PFPE and a group enclosed in parentheses with ⁇ 1 becomes stronger.
- a carbon atom directly bonded to PFPE ie, a carbon atom bonded to R d , R e and R f in the parenthesized group attached with ⁇ 1, or R d ′ ′ , R e ′ ′ and R f ′ ′
- the carbon atom bonded to is less in charge bias, and as a result, it is difficult for a nucleophilic reaction or the like to occur at the above carbon atom, and the compound is stably bonded to the substrate. It is advantageous because the friction durability of the layer formed can be further improved.
- R d independently represents -Z 4 -CR 81 p 2 R 82 q 2 R 83 r 2 at each occurrence.
- Z 4 independently represents an oxygen atom or a divalent organic group at each occurrence.
- the above Z 4 is preferably a C 1-6 alkylene group, — (CH 2 ) g —O— (CH 2 ) h — (wherein, g is an integer of 0 to 6, for example, an integer of 1 to 6) H is an integer of 0 to 6, for example, an integer of 1 to 6) or -phenylene- (CH 2 ) i- (wherein i is an integer of 0 to 6), and Preferably, it is a C 1-3 alkylene group. These groups may be substituted, for example, by one or more substituents selected from a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group. .
- R 81 independently represents R d ′ at each occurrence.
- R d ′ is as defined the R d .
- Cs linked in a linear fashion via a Z 4 group are at most 5 pieces. That is, in the above Rd , when at least one R 81 is present, two or more C atoms linked in a straight line via the Z 4 group are present in R d , and such a C 4 group is intervened.
- the maximum number of C atoms linked in a straight chain is five. Note that the "through Z 4 group in R d number of C atoms linearly linked" is equal to the number of repetitions of -Z 4 -C- being linearly linked in a R d Become.
- the number of C atoms linearly linked via the Z 4 group in R d is 1 (left) or 2 (the left expression) in all chains. Right).
- the number of C atoms to be linked via Z 4 groups R d linearized is one or two, preferably one.
- R 82 independently represents -Y-SiR 85 n 2 R 86 3- n 2 at each occurrence.
- Y's each independently represent a divalent organic group at each occurrence.
- Y C 1-6 alkylene group, - (CH 2) g ' -O- (CH 2) h' - (wherein, g 'is from 0 to 6 integer, for example from 1 to 6 H is an integer of 0 to 6, for example, an integer of 1 to 6, or -phenylene- (CH 2 ) i ' -(wherein i' is an integer of 0 to 6) ).
- These groups may be substituted, for example, by one or more substituents selected from a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group. .
- Y can be a C 1-6 alkylene group or -phenylene- (CH 2 ) i ' -.
- the light resistance in particular the UV resistance, may be higher.
- R 85 each independently represents a hydroxyl group or a hydrolyzable group at each occurrence.
- hydrolyzable group examples include those similar to the formula (C).
- R 85 is —OR, wherein R represents a substituted or unsubstituted C 1-3 alkyl group, more preferably an ethyl group or a methyl group, in particular a methyl group.
- R 86 each independently represents a hydrogen atom or a lower alkyl group at each occurrence.
- the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
- n2 is, (- Y-SiR 85 n2 R 86 3-n2) each unit or (-Y-SiR 85 "n2 R 86" 3-n2) independently for each unit, an integer of 0 to 3, preferably Is an integer of 1 to 3, more preferably 2 or 3, particularly preferably 3.
- R 85 ′ ′ and R 86 ′ ′ will be described later.
- the aforementioned R 83 each independently represents a hydrogen atom, a hydroxyl group or a lower alkyl group, preferably a hydrogen atom or a lower alkyl group.
- the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
- '(if R d' is absent, R d) end of R d in R d in the above q2 is preferably 2 or more, for example 2 or 3, more preferably 3.
- At least one of the terminal parts of R d is -C (-Y-SiR 85 n 2 R 86 3- n 2 ) 2 (specifically, C (-Y-SiR 85 n 2 R 86 3- n 2) ) 2 R 83 ) or -C (-Y-SiR 85 n 2 R 86 3- n 2 ) 3 , preferably -C (-Y-SiR 85 n 2 R 86 3- n 2 ) 3 .
- n2 is an integer of 1 to 3.
- (- Y-SiR 85 n2 R 86 3-n2) units is preferably (-Y-SiR 85 3).
- the distal end of the R d are all -C (-Y-SiR 85 n2 R 86 3-n2) 3, may be preferably -C (-Y-SiR 85 3) 3.
- the end of the group represented by (CR d k 2 R e 1 2 R f m 2 ) is C (-Y-SiR 85 n 2 R 86 3- n 2 ) 2 R f , C (-Y-SiR 85 n2 R 86 3-n2) 2 R 83 or C (-Y-SiR 85 n2 R 86 3-n2) 3, preferably a C (-Y-SiR 85 n2 R 86 3-n2) 3.
- n2 is an integer of 1 to 3.
- (- Y-SiR 85 n2 R 86 3-n2) units is preferably (-Y-SiR 85 3).
- all the terminal parts of the above groups may be -C (-Y-SiR 85 n 2 R 86 3- n 2 ) 3 , preferably -C (-Y-SiR 85 3 ) 3 .
- R d ′ ′ independently represents -Z 4 -CR 81 p2 R 82 ′ ′ q 2 R 83 r 2 at each occurrence.
- Z 4 , R 81 , R 83 , p 2, q 2 and r 2 are as defined above.
- R 82 ′ ′ each independently represents -Y-SiR 85 ′ ′ n 2 R 86 ′ ′ 3- n 2 at each occurrence, wherein Y and n 2 are as defined above.
- R 85 ′ ′ and R 86 ′ ′ is as defined for R 85 and R 86 , respectively.
- R d in the above q2 is preferably 2 or more, for example 2 or 3, more preferably 3 is there.
- (- Y-SiR 85 "n2 R 86" 3-n2) units are preferably (-Y-SiR 85 "3 ).
- the distal end of the R d are all -C (-Y-SiR 85 "n2 R 86" 3-n2) 3, may be preferably -C (-Y-SiR 85 "3 ) 3.
- the end of the group represented by (CR d ′ ′ k2 R e ′ ′ l2 R f ′ ′ m2 ) is C (—Y—SiR 85 ′ ′ n2 R 86 ′ ′ 3-n2 ) 2 R f ′ ′ , C (-Y-SiR 85 '' n2 R 86 '' 3- n 2 ) 2 R 83 or C (-Y-SiR 85 '' n 2 R 86 '' 3- n 2 ) 3 , preferably C (-Y-SiR 85 '' n 2 R 86 " 3- n 2 ) 3 .
- n2 is an integer of 1 to 3.
- (- Y-SiR 85 "n2 R 86" 3-n2) units is preferably (-Y-SiR 85 "3)
- the distal end of the base, all - It may be C (-Y-SiR 85 " n2 R 86" 3-n2 ) 3 , preferably -C (-Y-SiR 85 " 3 ) 3 .
- R e independently represents -Y-SiR 85 n 2 R 86 3- n 2 at each occurrence.
- Y, R 85 , R 86 and n 2 are as defined in R 82 above.
- R e ′ ′ independently at each occurrence is —Y—SiR 85 ′ ′ n 2 R 86 ′ ′ 3- n 2 where R 85 ′ ′ , R 86 ′ ′ , Y and n 2 are It is as defined above.
- R f each independently represents a hydrogen atom, a hydroxyl group or a lower alkyl group at each occurrence.
- each R f independently at each occurrence represents a hydrogen atom or a lower alkyl group.
- the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
- R f ′ ′ has the same meaning as R f .
- k2 is independently an integer of 0 to 3 at each occurrence; 12 is an integer of 0 to 3 independently at each occurrence; m2 is independently at each occurrence Is an integer of 0 to 3. However, the sum of k2, l2 and m2 is 3.
- At least one k2 is 2 or 3, preferably 3.
- k2 is 2 or 3, preferably 3.
- l2 is 2 or 3, preferably 3.
- -Y-SiR 85 a group represented by one or more, and more preferably.
- the groups represented by -Y-SiR 85 "there are one or more, 2 or more -Y-SiR One or more carbon atoms bonded to 85 are present, and one or more carbon atoms bonded to two or more —Y—SiR 85 ′ ′ are present.
- the group represented by -C- (Y-SiR 85 n 2 R 86 3- n 2 ) 2 is one or more and -C- (Y-SiR 85 " n 2 R 86" 3- It is preferable that one or more groups represented by n 2 ) 2 exist (wherein n 2 is an integer of 1 to 3).
- n2 is an integer of 1 to 3, and at least one q2 is 2 or 3, or at least one 12 is 2 or 3.
- the compound represented by the said Formula (D) can be manufactured by combining a well-known method.
- the PFPE-containing silane compound is a compound represented by formula (A).
- the PFPE-containing silane compound is a compound represented by Formula (B).
- the PFPE-containing silane compound is a compound represented by Formula (C).
- the PFPE-containing silane compound is a compound represented by Formula (D).
- the PFPE-containing silane compound is represented by Formula (A), (C) or (D).
- the PFPE-containing silane compound has two or more, preferably three or more Si atoms having a hydroxyl group or a hydrolyzable group at at least one end.
- the above-mentioned PFPE-containing silane compound is not particularly limited, but may have a number average molecular weight of 5 ⁇ 10 2 to 1 ⁇ 10 5 . Within this range, it is preferable to have a number average molecular weight of 2,000 to 30,000, more preferably 2,500 to 12,000, still more preferably 3,000 to 6,000. In the present invention, the number average molecular weight is a value measured by 19 F-NMR.
- the PFPE-containing unsaturated compound is a PFPE group-containing compound having a carbon-carbon double bond at both molecular ends.
- the PFPE-containing unsaturated compound is preferably a compound represented by the following formula (I).
- PFPE is as defined above.
- R k1 independently represents a single bond or a divalent organic group at each occurrence.
- R k1 is understood to be a linker which links an alkenyl group with a perfluoro (poly) ether moiety (ie, -PFPE- moiety) which mainly provides water repellency, surface slipperiness and the like. Therefore, the R k1 may be a single bond or any organic group as long as the PFPE-containing compound can be stably present. In the present specification, R k1 is bonded to the group whose left side is represented by PFPE and the right side is bonded to the —CH ⁇ CH 2 moiety of the formula (I).
- R k1 may be the same as X e for the above-mentioned PFPE-containing silane compound (but limited to a divalent one).
- R k1 is understood to be a linker which links an alkenyl group with a perfluoro (poly) ether moiety (ie, -PFPE- moiety) which mainly provides water repellency, surface slipperiness and the like. Therefore, the R k1 may be a single bond or any organic group as long as the PFPE-containing compound can be stably present.
- R k1 can be X e .
- X e represents a single bond or a divalent organic group, preferably a single bond or -C 6 H 4 -, (i.e. - - phenylene.
- a phenylene group.) - CO- (carbonyl group) It represents a divalent organic group having at least one member selected from the group consisting of -NR 4 -and -SO 2- .
- Each R 4 independently represents a hydrogen atom, a phenyl group, or a C 1-6 alkyl group (preferably a methyl group), preferably a hydrogen atom or a methyl group.
- the —C 6 H 4 —, —CO—, —NR 4 — or —SO 2 — is preferably contained in the molecular backbone of the PFPE-containing unsaturated compound.
- the molecular main chain refers to the relatively longest binding chain in the molecule of the PFPE-containing unsaturated compound.
- X e is more preferably a single bond or -C 6 H 4 -, - CONR 4 -, - CONR 4 -C 6 H 4 -, - CO -, - CO-C 6 H 4 -, - SO 2 NR 4 -, - SO 2 NR 4 -C 6 H 4 -, - SO 2 -, and -SO 2 -C 6 H 4 - represents a divalent organic group having at least one selected from the group consisting of.
- Additional -C 6 H 4 -, - CONR 4 -, - CONR 4 -C 6 H 4 -, - CO -, - CO-C 6 H 4 -, - SO 2 NR 4 -, - SO 2 NR 4 - C 6 H 4 -, - SO 2 -, or -SO 2 -C 6 H 4 - is preferably contained in the molecular backbone of the PFPE-containing unsaturated compound.
- R 31 represents a single bond,-(CH 2 ) s ' -or o-, m- or p-phenylene group, preferably-(CH 2 ) s'- s ′ is an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and still more preferably 1 or 2.
- X a represents-(X b ) l ' - X b is independently at each occurrence -O-, -S-, o-, m- or p-phenylene, -C (O) O-, -Si (R 33 ) 2 -,-( Si (R 33) 2 O) m '-Si (R 33) 2 -, - CONR 34 -, - O-CONR 34 -, - NR 34 - and - (CH 2)
- n' - is selected from the group consisting of Represents a group R 33 each independently represents a phenyl group, a C 1-6 alkyl group or a C 1-6 alkoxy group, preferably a phenyl group or a C 1-6 alkyl group, more preferably a methyl group
- R 34 independently at each occurrence represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group (preferably a methyl group),
- R 31 and X a are one or more selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group It may be substituted by the substituent of
- l ' is 1.
- R k1 is- (R 31 ) p ' -(X a ) q' -R 32- .
- R 32 represents a single bond,-(CH 2 ) t ' -or o-, m- or p-phenylene group, preferably-(CH 2 ) t'- .
- t ′ is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3.
- t ′ is an integer of 1 to 6, more preferably an integer of 1 to 3, and for example 1 or 2, more specifically 1.
- R 32 (typically a hydrogen atom in R 32 ) is substituted by one or more substituents selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group It may be done.
- the R k1 is Single bond, C 1-20 alkylene group, -R 31 -X c -R 32- or -X d -R 32- [Wherein, R 31 and R 32 are as defined above. ] It can be.
- the alkylene group, - (C ⁇ H 2 ⁇ ) - a group having the structure, may be substituted or unsubstituted, may be linear or branched.
- R k1 is Single bond, C 1-20 alkylene group, -(CH 2 ) s' -X c- , -(CH 2 ) s ' -X c- (CH 2 ) t'- -X d- or -X d- (CH 2 ) t ' - [Wherein, s ′ and t ′ are as defined above. ] It is.
- R k1 is -X f -, -X f -C 1-20 alkylene group, -X f - (CH 2) s ' -X c -, -X f - (CH 2) s '-X c - (CH 2) t' - -X f -X d- or -X f -X d- (CH 2 ) t ' - It is.
- s 'and t' are as defined above.
- X f is an alkylene group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, such as a methylene group.
- the hydrogen atom in X f may be substituted by one or more substituents selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group, preferably substituted There is.
- X f may be linear or branched, and is preferably linear.
- X c is -O-, -S-, -C (O) O-, -CONR 34 -, -O-CONR 34 -, -Si (R 33 ) 2- , - (Si (R 33) 2 O) m '-Si (R 33) 2 -, -O- (CH 2) u '- (Si (R 33) 2 O) m' -Si (R 33) 2 -, -O- (CH 2) u '-Si (R 33) 2 -O-Si (R 33) 2 -CH 2 CH 2 -Si (R 33) 2 -O-Si (R 33) 2 -, -O- (CH 2) u '-Si (OCH 3) 2 OSi (OCH 3) 2 -, -CONR 34 - (CH 2) u '- (Si (R 33) 2 O) m' -Si (R 33) 2 -, -CONR 34
- X d is -S-, -C (O) O-, -CONR 34 -, -CONR 34 - (CH 2) u '- (Si (R 33) 2 O) m' -Si (R 33) 2 -, -CONR 34 - (CH 2) u '-N (R 34) -, or -CONR 34 - (o-, m- or p- phenylene) -Si (R 33) 2 - [Wherein each symbol is as defined above. ] Represents
- R k1 is -X f -, -X f -C 1-20 alkylene group, -X f - (CH 2) s ' -X c -, -X f - (CH 2) s '-X c - (CH 2) t' - -X f -X d- or -X f -X d- (CH 2 ) t ' - [Wherein, X f , s ′ and t ′ are as defined above.
- X c is, -O-, or -CONR 34 -
- X d is, -CONR 34 -
- R 34 each independently represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group (preferably a methyl group) at each occurrence.
- R k1 is -X f - (CH 2) s ' -X c -, -X f - (CH 2) s '-X c - (CH 2) t' - -X f -X d- or -X f -X d- (CH 2 ) t ' - [Wherein, X f , s ′ and t ′ are as defined above.
- X c is, -O-, or -CONR 34 -
- X d is, -CONR 34 -
- R 34 each independently represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group (preferably a methyl group) at each occurrence.
- R k1 is Single bond, C 1-20 alkylene group, -(CH 2 ) s' -X c- (CH 2 ) t ' -or -X d- (CH 2 ) t'- [Wherein each symbol is as defined above. ] It can be.
- the R k1 is Single bond, C 1-20 alkylene group, -(CH 2 ) s ' -O- (CH 2 ) t'- , -(CH 2 ) s' -(Si (R 33 ) 2 O) m ' -Si (R 33 ) 2- (CH 2 ) t'- , - (CH 2) s '-O- (CH 2) u' - (Si (R 33) 2 O) m '-Si (R 33) 2 - (CH 2) t' -, or - (CH 2) s' -O- (CH 2) t '-Si (R 33) 2 - (CH 2) u' -Si (R 33) 2 - (C v H 2v) - [Wherein, R 33 , m ′, s ′, t ′ and u ′ are as defined above, and v is an integer of 1 to 20, preferably an integer of 2 to 6,
- -(C v H 2v ) - may be linear or branched, and for example, -CH 2- , -CH 2 CH 2- , -CH 2 CH 2 CH 2 -, - CH (CH 3 ) -, - CH (CH 3) CH 2 - may be.
- the R k1 group is substituted by one or more substituents selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group (preferably a C 1-3 perfluoroalkyl group) It may be done.
- the R k1 group may be other than an —O—C 1-6 alkylene group.
- examples of the R k1 group include the following groups: [Wherein each R 41 is independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C 1-6 alkoxy group, preferably a methyl group; D is -CH 2 O (CH 2 ) 2- , -CH 2 O (CH 2 ) 3- , -CF 2 O (CH 2 ) 3- , -(CH 2 ) 2- , -(CH 2 ) 3- , - (CH 2) 4 -, -CONH- (CH 2 ) 3- , -CON (CH 3 )-(CH 2 ) 3- , -CON (Ph)-(CH 2 ) 3- (wherein, Ph means phenyl), and (Wherein, each R 42 independently represents a hydrogen atom, a C 1-6 alkyl group or a C 1-6 alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl
- R k1 include, for example: Single bond, -CH 2 OCH 2- , -CH 2 O (CH 2 ) 2- , -CH 2 O (CH 2 ) 3- , -CH 2 O (CH 2 ) 6- , -CF 2 -CH 2 -O-CH 2- , -CF 2 -CH 2 -O- (CH 2 ) 2- , -CF 2 -CH 2 -O- (CH 2 ) 3- , -CF 2 -CH 2 -O- (CH 2 ) 6- -CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2- , -CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2- , -CH 2 O (CH 2) 3 Si (CH 3) 2 O (Si (CH 3) 2 O) 2 Si (CH 3) 2 (CH 2) 2 -,
- R k1 is -CH 2 OCH 2- , -CH 2 O (CH 2 ) 2- , -CH 2 O (CH 2 ) 3- , -CH 2 O (CH 2 ) 6- , -CF 2 -CH 2 -O-CH 2- , -CF 2 -CH 2 -O- (CH 2 ) 2- , -CF 2 -CH 2 -O- (CH 2 ) 3- , -CF 2 -CH 2 -O- (CH 2 ) 6- -CH 2 OCF 2 CHFOCF 2- , -CH 2 OCF 2 CHFOCF 2 CF 2- , -CH 2 OCF 2 CHFOCF 2 CF 2 CF 2- , -CH 2 OCH 2 CF 2 CHFOCF 2 CF 2 CF 2- , -CH 2 OCH 2 CF 2 CF 2 OCF 2- , -CH 2 OCH 2 CF 2 CF 2 OCF 2- , -CH 2 OCH 2 CF 2 CF 2 OCF 2- , -CH
- R k1 is -CH 2 OCH 2- , -CH 2 O (CH 2 ) 2- , -CH 2 O (CH 2 ) 3- , -CH 2 O (CH 2 ) 6- , -CF 2 -CH 2 -O-CH 2- , -CF 2 -CH 2 -O- (CH 2 ) 2- , -CF 2 -CH 2 -O- (CH 2 ) 3- , -CF 2 -CH 2 -O- (CH 2 ) 6- -CH 2 OCF 2 CHFOCF 2- , -CH 2 OCF 2 CHFOCF 2 CF 2- , -CH 2 OCF 2 CHFOCF 2 CF 2 CF 2- , -CH 2 OCH 2 CF 2 CHFOCF 2 CF 2 CF 2- , -CH 2 OCH 2 CF 2 CF 2 OCF 2- , -CH 2 OCH 2 CF 2 CF 2 OCF 2- , -CH 2 OCH 2 CF 2 CF 2 OCF 2- , -CH
- R k1 represents X e ′ .
- X e ′ is a single bond, an alkylene group having 1 to 6 carbon atoms, -R 51 -C 6 H 4 -R 52- , -R 51 -CONR 4 -R 52- , -R 51 -CONR 4 -C 6 H 4 -R 52 -, - R 51 -CO-R 52 -, - R 51 -CO-C 6 H 4 -R 52 -, - R 51 -SO 2 NR 4 -R 52 -, - R 51 - SO 2 NR 4 -C 6 H 4 -R 52- , -R 51 -SO 2 -R 52- , or -R 51 -SO 2 -C 6 H 4 -R 52- .
- R 51 and R 52 each independently represent a single bond or an alkylene group having 1 to 6 carbon atoms, preferably a single bond or an alkylene group having 1 to 3 carbon atoms.
- R 4 is as defined above.
- the alkylene group is substituted or unsubstituted, preferably unsubstituted.
- a halogen atom Preferably a fluorine atom can be mentioned, for example.
- the alkylene group is linear or branched, and is preferably linear.
- X e ′ is Single bond, -X f -, Alkylene group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, preferably -X f -C 1-6 alkylene group, preferably -X f -C 1-3 alkylene group, more preferably -X f -C 1-2 alkylene group, -C 6 H 4 -R 52 ' -, -CONR 4 '-R 52' -, -CONR 4 '-C 6 H 4 -R 52' -, -X f -CONR 4 '-R 52' -, -X f -CONR 4 '-C 6 H 4 -R 52' -, -CO-R 52 ' -, -CO-C 6 H 4 -R 52 ' -, -SO 2 NR 4 '-R 52' -, -SO 2 NR 4 '-C 6 H 4 -R 52' -, -
- R 4 ′ is a hydrogen atom or a methyl group. ) It can be.
- X e ′ is preferably -X f -, An alkylene group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, -X f -C 1-6 alkylene group, preferably -X f -C 1-3 alkylene group, more preferably -X f -C 1-2 alkylene group, -CONR 4 '-R 52' -, -CONR 4 '-C 6 H 4 -R 52' -, -X f -CONR 4 '-R 52' -, -X f -CONR 4 '-C 6 H 4 -R 52' -, -R 51 '-CONR 4' -, -R 51 '-CONR 4' -C 6 H 4 -, -CONR 4 ' -, -CONR 4 '-C 6 H 4 -, -CONR 4 ' -, -CONR 4 '-C 6 H 4 - ,
- X e ′ is more preferably -CONR 4 '-R 52' -, -CONR 4 '-C 6 H 4 -R 52' -, -X f -CONR 4 '-R 52' -, -X f -CONR 4 '-C 6 H 4 -R 52' -, -R 51 '-CONR 4' -, -R 51 '-CONR 4' -C 6 H 4 -, -CONR 4 ' -, -CONR 4 '-C 6 H 4 - , -X f -CONR 4 '- or -X f -CONR 4,' -C 6 H 4 -, It can be.
- X e ′ include, for example, Single bond, Perfluoroalkylene groups having 1 to 6 carbon atoms (eg, -CF 2 -,-(CF 2 ) 2-, etc.), An alkylene group having 1 to 6 carbon atoms, -CF 2 -C 1-6 alkylene group, -CONH-, -CONH-CH 2- , -CONH- (CH 2 ) 2- , -CONH- (CH 2 ) 3- , -CF 2 -CONH-, -CF 2 CONHCH 2- , -CF 2 CONH (CH 2 ) 2- , -CF 2 CONH (CH 2 ) 3- , -CON (CH 3 )-, -CON (CH 3 )-CH 2- , -CON (CH 3 )-(CH 2 ) 2- -CON (CH 3 )-(CH 2 ) 3- , -CF 2 -CON (CH 3 )-, -CF 2 -CON (CH 3 )-, -
- preferable X e ′ is Perfluoroalkylene groups having 1 to 6 carbon atoms (eg, -CF 2 -,-(CF 2 ) 2-, etc.), An alkylene group having 1 to 6 carbon atoms, -CF 2 -C 1-6 alkylene group, -CONH-, -CONH-CH 2- , -CONH- (CH 2 ) 2- , -CONH- (CH 2 ) 3- , -CF 2 CONH-, -CF 2 CONHCH 2- , -CF 2 CONH (CH 2 ) 2- , -CF 2 CONH (CH 2 ) 3- , -CON (CH 3 )-, -CON (CH 3 ) -CH 2- , -CON (CH 3 )-(CH 2 ) 2- , -CON (CH 3 )-(CH 2 ) 3- , -CF 2 -CON (CH 3 )-, -CF 2 -CON (CH 3 ) CH 2- ,
- more preferable X e ′ is -CONH-, -CONH-CH 2- , -CONH- (CH 2 ) 2- , -CONH- (CH 2 ) 3- , -CF 2 CONH-, -CF 2 CONHCH 2- , -CF 2 CONH (CH 2 ) 2- , -CF 2 CONH (CH 2 ) 3- , -CON (CH 3 )-, -CON (CH 3 ) -CH 2- , -CON (CH 3 )-(CH 2 ) 2- , -CON (CH 3 )-(CH 2 ) 3- , -CF 2 -CON (CH 3 )-, -CF 2 -CON (CH 3 ) CH 2- , -CF 2 -CON (CH 3 )-(CH 2 ) 2- , -CF 2 -CON (CH 3 )-(CH 2 ) 3- , -CH 2 -CONH-, -CH 2 -CONH-CH 2- ,
- X e ′ is a single bond.
- the PFPE 1 and the group capable of binding to the substrate are directly bound.
- R k1 is a group represented by the formula:-(R 16 ) x- (CFR 17 ) y- (CH 2 ) z- .
- x, y and z are each independently an integer of 0 to 10, the sum of x, y and z is 1 or more, and the order of existence of each parenthesized parenthesis is in the formula Is optional.
- R 16 are each independently at each occurrence, an oxygen atom, a phenylene, carbazolylene, -NR 18 - (wherein, R 18 represents a hydrogen atom or an organic group) or a divalent organic group is there.
- R 16 is an oxygen atom or a divalent polar group.
- the “lower alkyl group” is, for example, an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group or an n-propyl group, which are substituted by one or more fluorine atoms It is also good.
- R 17 in each occurrence is independently a hydrogen atom, a fluorine atom or a lower fluoroalkyl group, preferably a fluorine atom.
- the “lower fluoroalkyl group” is, for example, a fluoroalkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably trifluoro It is a methyl group, a pentafluoroethyl group, more preferably a trifluoromethyl group.
- R k1 is preferably of the formula: — (O) x — (CF 2 ) y — (CH 2 ) z —, wherein x, y and z are as defined above, in parentheses The order of existence of each repeating unit enclosed is arbitrary group in the formula).
- Examples of the group represented by the above formula:-(O) x- (CF 2 ) y- (CH 2 ) z- include, for example,-(O) x ' -(CH 2 ) z " -O-[(CH 2 ) 2) z '''-O-] z "", and - (O) x' - ( CF 2) y "- (CH 2) z” -O - [(CH 2) z '''-O- Z ′ ′ ′ ′ ′ (wherein, x ′ is 0 or 1, y ′ ′, z ′ ′ and z ′ ′ ′ are each independently an integer of 1 to 10, and z ′ ′ ′ is 0 or 1 The left end of these groups is bonded to the PFPE side.
- R k1 is —O—CFR 20 — (CF 2 ) e ′ ′ ′ ′ .
- the above R 20 each independently represents a fluorine atom or a lower fluoroalkyl group.
- the lower fluoroalkyl group is, for example, a fluoroalkyl group having 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group or a pentafluoroethyl group, further preferably It is a trifluoromethyl group.
- the above e ′ ′ ′ is each independently 0 or 1.
- R 20 is a fluorine atom and e ′ ′ ′ is 1.
- examples of R k1 groups include 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; In each R k1 group, any part of T is attached to PFPE of the molecular backbone: -CH 2 O (CH 2 ) 2- , -CH 2 O (CH 2 ) 3- , -CF 2 O (CH 2 ) 3- , -CH 2- , -(CH 2 ) 2- , -(CH 2 ) 3- , - (CH 2) 4 -, -CONH- (CH 2 ) 3- , -CON (CH 3 )-(CH 2 ) 3- , -CON (Ph)-(CH 2 ) 3- (wherein Ph means phenyl), or [Wherein, R 42 each independently represents a hydrogen atom, a C 1-6 alkyl group or
- T of 1 is-(CH 2 ) n ′ ′ -(n ′ ′ is an integer of 2 to 6) attached to a group opposite to PFPE of the molecular main chain, and the remaining T if present And each independently may be a methyl group, a phenyl group, a C 1-6 alkoxy group or a radical scavenging group or an ultraviolet absorbing group.
- the radical scavenging group is not particularly limited as long as it can scavenge a radical generated upon irradiation with light, for example, benzophenones, benzotriazoles, benzoates, phenyl salicylates, crotonic acids, malonic esters, organoacrylates And residues of hindered amines, hindered phenols, or triazines.
- the ultraviolet absorbing group is not particularly limited as long as it can absorb ultraviolet light, and examples thereof include benzotriazoles, hydroxybenzophenones, esters of substituted and unsubstituted benzoic acid or salicylic acid compounds, acrylates or alkoxycinnamates, oxamides, The residue includes oxanilides, benzoxazinones and benzoxazoles.
- preferred radical scavenging groups or ultraviolet absorbing groups are Can be mentioned.
- the above-mentioned R k1 for example, -R k2 -CH 2 -, - R k2 -OCH 2 -, - R k2 -CH 2 OCH 2 -, or, -R k2 -CO-NR 1 - Mention may be made of the group represented by Y j2- .
- the divalent organic group is bonded to PFPE on the left side of the above formula (ie, on the R k2 side).
- R k2 is a single bond or a divalent hydrocarbon group having 1 to 15 carbon atoms, and may contain an ether bond.
- the alkylene group which may contain the alkylene group or ether oxygen can be mentioned, for example.
- the alkylene group may be substituted or unsubstituted as described above.
- R k2 is preferably a single bond.
- the above R k2 is a divalent hydrocarbon group, preferably an alkylene group in which at least a part of hydrogen atoms are substituted by fluorine atoms, for example, -CFH-, -CF 2- , -(CF 2 ) 2 -,-(CF 2 ) 3- and the like can be mentioned, and specifically, it is -CF 2- .
- the Y j2 is —CH 2 — or an o, m or p-dimethylsilyl phenylene group represented by the following formula.
- R 1 is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group.
- the substituted or unsubstituted monovalent hydrocarbon group is preferably a monovalent hydrocarbon group having 1 to 12 carbon atoms, and is preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms. More preferable.
- substituted or unsubstituted monovalent hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl and octyl; Aryl groups such as tolyl group; aralkyl groups such as benzyl group and phenylethyl group; and monovalent hydrocarbon groups in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as fluorine atom. .
- R 1 is preferably a hydrogen atom, a methyl group or a phenyl group.
- PFPE-containing unsaturated compounds can include, for example, the following structures.
- PFPE and R k2 are as defined above.
- the PFPE-containing compound is a PFPE-containing silane compound.
- the PFPE-containing compound is a PFPE-containing unsaturated compound.
- the curable composition used in the present invention may further contain a crosslinking agent.
- the crosslinking agent is a PFPE-containing compound (for example, a PFPE-containing silane compound, specifically, a silane moiety having a hydroxyl group or a hydrolyzable group bonded to the Si atom of the PFPE-containing silane compound, carbon of the PFPE-containing unsaturated compound
- the compound is not particularly limited as long as it is a compound having a carbon double bond portion) and a portion capable of performing a crosslinking reaction (condensing reaction) or an addition reaction.
- the physical properties e.g., tensile strength, elastic modulus
- the cross-linking agent is selected from an organosilicon compound having at least two -O-R g3 bonded to a Si atom, and an organosilicon compound having two or more hydrogen atoms (Si-H) bonded to a silicon atom in one molecule. It is preferable that it is at least one selected from the group consisting of R g3 will be described later.
- the crosslinking agent is an organosilicon compound (hereinafter also referred to as a crosslinking agent (1)) having at least two -O-R g3 bonded to a Si atom.
- R g3 is independently at each occurrence a hydrogen atom or a monovalent organic group.
- the monovalent organic group means a group containing a carbon atom.
- the monovalent organic group is not particularly limited, and examples thereof include groups in which one hydrogen atom is further eliminated from a hydrocarbon group.
- the hydrocarbon group is as defined above.
- the crosslinker has a structure different from that of the PFPE-containing silane compound (a) (specifically, the PFPE-containing silane compound (a)).
- Organosilicon compounds having at least two silanol groups in one molecule In the organic silicon compound, the silanol group is preferably present at both ends of the molecular main chain.
- the molecular main chain represents the relatively longest bond chain in the molecule of the organosilicon compound.
- R g1 is each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms.
- R g1 is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl or nonyl Alkyl groups such as decyl group; cycloalkyl groups such as cyclopentyl group, cyclohexyl group and cycloheptyl group; vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, hexenyl group, cyclohexenyl group and the like Alkenyl groups; aryl groups such as phenyl, tolyl, xylyl and
- R g2 is independently at each occurrence independently a substituted or unsubstituted C 1 to C 20 carbon atom, preferably a divalent carbon atom having 2 to 10 carbon atoms It is a hydrogen group.
- R g2 include alkylene groups such as methylene, ethylene, propylene, methylethylene, butylene and hexamethylene; cycloalkylenes such as cyclohexylene, phenylene, tolylene and xylylene And arylene groups such as naphthylene group and biphenylene group; groups in which a part or all of hydrogen atoms of these groups are substituted with a halogen atom or the like; and combinations of these substituted or unsubstituted alkylene groups and arylene groups are exemplified.
- Ru alkylene groups such as methylene, ethylene, propylene, methylethylene, butylene and hexamethylene
- cycloalkylenes such as cyclohexylene, phenylene, tolylene and xylylene
- arylene groups such as naphthylene group and biphenylene group
- groups in which a part or all of hydrogen atoms of these groups are substituted
- R g2 a methylene group, an ethylene group, a propylene group, a butylene group, a hexamethylene group, a cyclohexylene group and a phenylene group are preferable, and an ethylene group, a propylene group, a butylene group and a phenylene group are particularly preferable.
- a compound having a silanol group in the molecule R g1 3 SiO 1/2 , R g1 2 SiO, R g1 SiO 3/2 , and a combination of one or more kinds of SiO 2 units and a silanol group
- the resinous compound comprised by these is mentioned.
- the structural units in the resinous compound may be directly bonded to each other, or may be bonded to each other via a divalent or higher hydrocarbon group.
- ⁇ 1 is independently an integer of 1 or more at each occurrence.
- ⁇ 1 is preferably 2 or more, more preferably 5 or more, preferably 50 or less, more preferably 20 or less.
- the organosilicon compound having at least two silanol groups in one molecule preferably has no PFPE structure in its molecular structure.
- R g3 is as defined above.
- the above R g3 reacts with a portion having a hydroxyl group or a hydrolysable group bonded to a Si atom of the PFPE-containing silane compound represented by the above formula (A), (B), (C) or (D) It is a part to gain.
- the R g3 is preferably a monovalent organic group.
- R g4 is independently at each occurrence a monovalent organic group.
- R g4 is preferably a substituted or unsubstituted monovalent hydrocarbon group, and more preferably a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms.
- R g4 is methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, Alkyl groups such as decyl group; cycloalkyl groups such as cyclopentyl group, cyclohexyl group and cycloheptyl group; aryl groups such as phenyl group, tolyl group, xylyl group and naphthyl group; such as benzyl group, phenylethyl group and phenylpropyl group Aralkyl groups; Alkenyl groups such as vinyl group, allyl group, propenyl group and butenyl group; and groups in which part or all of the hydrogen atoms of these groups are substituted with halogen atom
- R g4 may be a group represented by the following general formula.
- Rf 1 -R g5- In the above formula, Rf 1 is a monovalent fluorinated polyether group.
- Rf 1 above CF 3 O—, CF 3 CF 2 O—, CF 3 CF 2 CF 2 O—, (CF 3 ) 2 CFO—, or CF 3 CF 2 CF 2 CF 2 at the CF 2 end of the above PFPE 2 O- and the like are exemplified.
- R g5 is a divalent organic group.
- the divalent organic group is as defined above.
- R g5 may contain, for example, one or more of an oxygen atom, a nitrogen atom, a silicon atom and a sulfur atom, and may contain an amide bond or a sulfonamide bond, which may be substituted or unsubstituted Or a divalent hydrocarbon group of
- the divalent hydrocarbon group preferably has 2 to 20 carbon atoms.
- substituted or unsubstituted divalent hydrocarbon group which does not intervene an oxygen atom, a nitrogen atom, a silicon atom or a sulfur atom and does not contain an amide bond or a sulfonamide bond
- ethylene groups Alkylene groups such as propylene, methylethylene, butylene and hexamethylene; cycloalkylenes such as cyclohexylene; arylenes such as phenylene, tolylene, xylylene, naphthylene and biphenylene; And combinations thereof with arylene groups; and groups in which part or all of the hydrogen atoms of these alkylene groups and arylene groups are substituted with halogen atoms.
- the oxygen atom is -O-
- the nitrogen atom is -NR g51-
- R g51 is a hydrogen atom or an alkyl or aryl group having 1 to 10 carbon atoms
- -N Silicon atoms may be included as -SiR g52 R g53- (R g52 , R g53 each independently at each occurrence is an alkyl group or aryl group having from 1 to 10 carbon atoms) and a sulfur atom may be included as -S- .
- the following are mentioned as a specific example of such a bivalent hydrocarbon group.
- Me represents a methyl group
- Ph represents a phenyl group
- an Rf 1 group is bonded to the left side (J in each formula).
- ⁇ 2 is independently 2 or 3 at each occurrence, and ⁇ 3 is 2 or 3 independently at each occurrence.
- R g3 and R g4 are as defined above.
- R g6 - is independently at each occurrence, R g8 -R g7 - represents a.
- R g7 independently represents a single bond, an oxygen atom or a divalent organic group at each occurrence.
- the divalent organic group is as described above.
- R g7 is preferably an alkylene group having 1 to 10 carbon atoms, or a group having 1 to 10 carbon atoms and containing a nitrogen atom or an oxygen atom in the main chain.
- R g7 is more preferably An alkylene group having 1 to 3 carbon atoms, CH 2 CH 2 -NH-CH 2 CH 2 CH 2 or CH 2 -O-CH 2 CH 2 CH 2 .
- the above R g8 is a reactive functional group.
- the above R g8 is preferably each independently an amino group, an epoxy group, a methacryl group, a vinyl group, or a mercapto group, and more preferably an amino group.
- ⁇ 4 is an integer of 2 or more, preferably 2 or 3, and more preferably 3.
- ⁇ 5 is an integer of 0 or more, preferably 0 or 1.
- ⁇ 6 is 1 or 2, preferably 1. However, the sum of ⁇ 4, ⁇ 5 and ⁇ 6 is 4.
- ⁇ 4 is 2 or 3
- ⁇ 5 is 0 or 1
- ⁇ 6 is 1 or 2
- ⁇ 5 is 0 and ⁇ 6. Is one.
- the crosslinking agent (1) is a compound represented by the formula (E3) or the formula (E5), more preferably a compound represented by the formula (E3).
- the crosslinking agent does not have a group represented by PFPE in the molecular chain.
- the molecular weight of the crosslinker is 1,000 or less, preferably 600 or less, more preferably 250 or less.
- the lower limit value of the molecular weight of the crosslinking agent may be 50 or more, or 100 or more.
- the crosslinker (1) is tetraethoxysilane, tetratrimethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, dimethyltrimethoxysilane, aminopropyltriethoxysilane, aminopropyltrimethoxysilane It is at least one selected from the group consisting of silane, tridecafluoro-n-octyltriethoxysilane, and tridecafluoro-n-octyltrimethoxysilane.
- the crosslinking agent (1) is preferably used together with the PFPE-containing silane compound.
- the —O—R g3 bonded to the Si atom of the crosslinker (1) and the hydroxyl group or hydrolyzable group bonded to the Si atom of the PFPE-containing silane compound can crosslink (condensate).
- the crosslinker (1) may be contained, for example, 0.1 parts by mass or more, specifically 0.3 parts by mass or more, with respect to 100 parts by mass of the PFPE-containing silane compound in the curable composition of the present embodiment It can be obtained, and can be contained in an amount of 30 parts by mass or less, specifically, 10 parts by mass or less.
- the crosslinking agent (1) can be contained, for example, in an amount of 0.1 to 30 parts by mass with respect to 100 parts by mass of the PFPE-containing silane compound in the curable composition of the present embodiment. It can be contained in 10 to 10 parts by mass, and more specifically, 0.3 to 5.0 parts by mass.
- the crosslinking agent (1) is, for example, 1 mol of -O-R g3 per 1 mol of a hydroxyl group or a hydrolyzable group bonded to the Si atom of the PFPE-containing silane compound in the curable composition of this embodiment. More than 2 mol can be specifically included.
- the crosslinking agent can contain, for example, 30 mol or less of —O—R g3 per 1 mol of a hydroxyl group or a hydrolyzable group bonded to the Si atom of the PFPE-containing silane compound, specifically 20 It can be contained in a molar amount or less, more specifically can be contained in a molar amount of 10 or less.
- R g3 is as defined above.
- the cross-linking agent (1) may contain, for example, -O-R g3 in a range of, for example, 1 to 30 moles relative to 1 mole of hydroxyl group or hydrolyzable group bonded to Si atom of the PFPE containing silane compound. It can be, specifically, in the range of 2 to 20 moles.
- the crosslinking agent (1) can be contained, for example, in the range of 0.1 to 30 parts by mass with respect to 100 parts by mass of the curable composition of the present embodiment, and specifically, 0.3 to 10 parts by mass Range can be included.
- the crosslinking agent is an organosilicon compound having two or more hydrogen atoms (Si-H) bonded to a silicon atom in one molecule (hereinafter, also referred to as a crosslinking agent (2)).
- the Si—H is preferably present at the molecular chain end of the crosslinker.
- the crosslinker (2) has one or more monovalent perfluoroalkyl group, monovalent perfluorooxyalkyl group, divalent perfluoroalkylene group or divalent perfluoro group in the molecular structure. It is preferable to have a fluorine-containing group such as an oxyalkylene group. By having such a structure, the compatibility and dispersibility of the crosslinking agent and the PFPE-containing compound contained in the curable composition of the present embodiment can be improved, and the cured product of the curable composition of the present embodiment The uniformity can be good.
- the number of carbon atoms of the monovalent perfluoroalkyl group is preferably 1 to 20, and more preferably 2 to 10.
- the perfluoroalkyl group may be linear or branched, but is preferably linear.
- Rf "-PFPE 2 - is preferably a group represented by PFPE 2 has the formula: - (OC 6 F 12) a "- (OC 5 F 10) b" - (OC 4 F 8) c "- (OC 3 F 6) d" - (OC 2 F 4) e "- (OCF 2) f ” - Is represented by PFPE 2 may be linear or branched, but is preferably linear.
- a ′ ′, b ′ ′, c ′ ′ and d ′ ′ are each independently an integer of 0 to 30, and e ′ ′ and f ′ ′ are each independently an integer of 1 to 200.
- a ′ ′, b ′ ′, c ′ ′, d ′ ′, e ′ ′ and f ′ ′ are each independently an integer of 0 or more and 30 or less.
- the sum of a ′ ′, b ′ ′, c ′ ′, d ′ ′, e ′ ′ and f ′ ′ is 5 or more, more preferably 10 or more, for example 10 or more and 100 or less.
- the order in which each repeating unit enclosed in parentheses with the subscripts a ′ ′, b ′ ′, c ′ ′, d ′ ′, e ′ ′ or f ′ ′ is given is arbitrary in the formula.
- the ratio of e ′ ′ to f ′ ′ is less than 1.0.
- a ′ ′, b ′ ′, c ′ ′, d ′ ′, e ′ ′ and f ′ ′ may be the same as a, b, c, d, e and f of PFPE, respectively.
- the specific structure of the repeating unit contained in PFPE 2 can mention what was illustrated as a repeating unit of PFPE.
- PFPE 2 is-(OC 4 F 8 ) c " -(OC 3 F 6 ) d" -(OC 2 F 4 ) e " -(OCF 2 ) f" -(wherein, c "and d “Is independently an integer of 0 or more and 30 or less, and e ′ ′ and f ′ ′ are each independently 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less.
- the order in which each repeating unit enclosed in parentheses with the subscript c ′ ′, d ′ ′, e ′ ′ or f ′ ′ is attached is arbitrary in the formula).
- PFPE 2 is, - (OCF 2 CF 2 CF 2 CF 2) c "- (OCF 2 CF 2 CF 2) d" - (OCF 2 CF 2) e "- (OCF 2) f" - is .
- PFPE 2 is — (OC 2 F 4 ) e ′ ′ ⁇ (OCF 2 ) f ′ ′ (wherein e ′ ′ and f ′ ′ each independently is 1 or more and 200 or less, preferably 5 or more. It is an integer of 200 or less, more preferably 10 or more and 200 or less, and the order of existence of each repeating unit enclosed in parentheses with a subscript e "or f" may be arbitrary in the formula) .
- R f ′ ′ independently at each occurrence is a chlorine atom, a fluorine atom, or an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms or chlorine atoms. Represent.
- alkyl group having 1 to 16 carbon atoms in the alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms is a branched or branched straight chain Is preferably a linear or branched alkyl group having 1 to 6 carbon atoms, particularly 1 to 3 carbon atoms, and more preferably a linear alkyl group having 1 to 3 carbon atoms It is.
- Rf ′ ′ is preferably a fluorine atom, or an alkyl group having 1 to 16 carbon atoms substituted by one or more fluorine atoms, more preferably CF 2 H—C 1-15 fluoroalkylene. It is a group or a C 1-16 perfluoroalkyl group, more preferably a C 1-16 perfluoroalkyl group.
- the perfluoroalkyl group having 1 to 16 carbon atoms may be linear or branched, preferably linear or branched, having 1 to 6 carbon atoms, in particular carbon atoms It is a perfluoroalkyl group of 1 to 3 and 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.
- the monovalent perfluorooxyalkyl group Rf "- (OC 2 F 4) e" - (OCF 2) f “- ( wherein, e” and f “are one or more independently It is an integer of 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less, and the existence order of each repeating unit enclosed in parentheses with a subscript e "or f" is arbitrary in the formula Yes).
- the ratio of e ′ ′ to f ′ ′ is preferably 0.10 or more, more preferably 0.20 or more, still more preferably 0.40 or more, and preferably 1 It is less than .00, more preferably not more than 0.85, still more preferably not more than 0.80.
- the ratio of e ′ ′ to f ′ ′ is preferably 0.1 or more and less than 1.0, more preferably 0.20 or more and 0.90 or less, and still more preferably 0.40. It is at least 0.85, particularly preferably at least 0.40 and at most 0.80.
- the number of carbon atoms of the divalent perfluoroalkylene group is preferably 1 to 20, and more preferably 2 to 10.
- the perfluoroalkylene group may be linear or branched, but is preferably linear.
- the above divalent perfluorooxyalkylene group is preferably represented by -PFPE 2- , and-(OC 4 F 8 ) c " -(OC 3 F 6 ) d" -(OC 2 F 4 ) e " It is more preferable that it is a group represented by — (OCF 2 ) f ′ ′ . c ′ ′, d ′ ′, e ′ ′ and f ′ ′ are as defined above.
- the perfluorooxyalkyl group may be linear or branched, but is preferably linear.
- PFPE 2 is as defined above.
- the fluorine-containing group is preferably a monovalent perfluoroalkyl group or a divalent perfluoroalkylene group.
- the fluorine-containing group and the silicon atom may be linked by a divalent organic group.
- the divalent organic group is as defined above.
- the divalent organic group may be an alkylene group, an arylene group or a combination thereof, or a group in which an ether-bonded oxygen atom, an amide bond, a carbonyl bond or the like is interposed in these groups.
- a divalent organic group for example, -CH 2 CH 2- , -CH 2 CH 2 CH 2- , -CH 2 CH 2 CH 2 OCH 2- , -CH 2 CH 2 CH 2 -NH-CO-, -CH 2 CH 2 CH 2 -N (Ph) -CO- (wherein Ph is a phenyl group), -CH 2 CH 2 CH 2 -N (CH 3 ) -CO-, -CH 2 CH 2 CH 2 -O-CO- And groups having 2 to 12 carbon atoms such as The divalent organic group is bonded to the Si atom on the left side and to the fluorine-containing group on the right side.
- the monovalent substituent which is bonded to a silicon atom of the crosslinking agent (2) and which is other than the fluorine-containing group is, for example, a methyl group, an ethyl group, a propyl group or a butyl group, Alkyl group such as hexyl group, cyclohexyl group, octyl group and decyl group; alkenyl group such as vinyl group and allyl group; aryl group such as phenyl group, tolyl group and naphthyl group; aralkyl group such as benzyl group and phenylethyl group and the like
- the organosilicon compound (B) does not have an alkoxy group and an epoxy group as a substituent bonded to a silicon atom.
- the crosslinking agent (2) may be cyclic, linear, three-dimensional or any combination thereof.
- the number of silicon atoms contained in the crosslinking agent (2) is not particularly limited, but may usually be about 2 to 60, preferably about 3 to 30.
- examples of the crosslinking agent (2) include the following compounds. One of these compounds may be used alone, or two or more thereof may be used in combination.
- PFPE 2 is as defined above independently of each other at the same time (in the following formulas, the group represented by PFPE 2 is bonded to the group represented by R f at the terminal oxygen atom) .); Rf ′ ′ is independently at each occurrence and as defined above; R k3 is each independently an alkyl group having 1 to 10 carbon atoms, or an alkoxy group represented by OR k7 in each occurrence, preferably a methyl group or an alkoxy group represented by OR k7 , More preferably a methyl group; R k4 each independently at each occurrence is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group represented by OR k7 , preferably a hydrogen atom or OR k7 An alkoxy group, more preferably a hydrogen atom; R k5 each independently at each occurrence is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group represented by OR k7 .
- R k8 is, - (O- (CH 2) ⁇ 5) ⁇ 6 - represented by (wherein, is an oxygen atom - (CR k6 2) bonded to the group represented by [alpha] 1); ⁇ 1 is independently an integer of 1 to 10, preferably 2 or 3, each independently at each occurrence; ⁇ 2 is independently an integer of 1 to 50, preferably 10 at each occurrence; ⁇ 3 is each independently an integer of 1 to 50, preferably an integer of 3 to 5 at each occurrence; ⁇ 4 is, independently at each occurrence, an integer of 1 to 50, preferably an integer of 3 to 5; ⁇ 5 is an integer of 1 to 6, preferably 1 to 3, more preferably 1; ⁇ 6 is 0 or 1;
- the content of the crosslinking agent (2) may be an effective amount for curing the PFPE-containing compound.
- the said crosslinking agent (2) it is preferable to use the said crosslinking agent (2) with PFPE containing unsaturated compound. In this case, an addition reaction can occur due to the carbon-carbon double bond of the Si—H and PFPE containing unsaturated compound of the crosslinker (2).
- the content of the crosslinking agent (2) is such that the hydrogen atom (hydrosilyl group, ie, SiH group) bonded to the silicon atom contained in the crosslinking agent is 0 per 1 mol of the alkenyl group contained in the PFPE containing unsaturated compound It is preferably in the range of 0.5 to 5.0 moles, and more preferably in the range of 0.8 to 3.0 moles.
- the curable composition of this embodiment can contribute to the formation of a cured product having an appropriate degree of crosslinking, and can reduce foaming upon curing.
- the crosslinker is an organosilicon compound (crosslinker (1)) having at least two -O-R g3 bonded to a Si atom.
- R g3 is as defined above.
- the crosslinker is an organosilicon compound (crosslinker (2)) having two or more hydrogen atoms (Si-H) bonded to a silicon atom in one molecule.
- the crosslinking agent may be used alone or in combination of two or more.
- the curable composition used in the present invention may further contain a catalyst.
- the condensation reaction between the PFPE-containing compound and the crosslinking agent is promoted by the catalyst.
- metal catalysts organic acid catalysts, inorganic acid catalysts, base catalysts (for example, ammonia, triethylamine, diethylamine etc.) can be used.
- base catalysts for example, ammonia, triethylamine, diethylamine etc.
- organic acid catalyst examples include compounds having a carboxylic acid, a sulfonic acid, and a phosphoric acid. Specifically, acetic acid, trifluoroacetic acid, methanesulfonic acid, toluene benzenesulfonic acid, alkyl phosphoric acid Etc. can be mentioned.
- Examples of the inorganic acid catalyst include hydrochloric acid and sulfuric acid.
- the metal-based catalyst preferably contains a transition metal atom.
- the catalyst is preferably a metal catalyst.
- examples of the metal atom contained in the metal-based catalyst include titanium, zirconium, and tin. Among these metal atoms, it is preferable to use titanium or zirconium.
- the metal-based catalyst preferably has an alkoxide (—O—R h ) as a ligand.
- an alkoxide —O—R h
- the condensation reaction between the PFPE-containing compound (for example, PFPE-containing silane compound) and the crosslinking agent is promoted.
- the metal-based catalyst as described above can be easily dissolved or dispersed in the curable composition, and can contribute to the promotion of a uniform reaction.
- the curable composition of the present embodiment containing the metal-based catalyst as described above can contribute to the formation of a cured product of a highly transparent curable composition containing few foreign substances.
- the R h is preferably an alkyl group having 1 to 4 carbon atoms.
- the condensation reaction is particularly promoted by using a catalyst having an alkyl group as described above.
- the R h is more preferably an alkyl group having 1 to 3 carbon atoms.
- the alkyl group having 1 to 3 carbon atoms is a methyl group, an ethyl group, an n-propyl group or an i-propyl group.
- the catalyst of this embodiment is preferably used together with a PFPE-containing silane compound.
- the catalyst of this embodiment is preferably used together with the PFPE-containing silane compound and the crosslinking agent (1).
- the content of the catalyst is preferably 0.05 parts by mass or more, and more preferably 0.07 parts by mass or more, with respect to 100 parts by mass of the PFPE-containing silane compound in the curable composition.
- the catalyst is preferably contained in an amount of 1.0 parts by mass or less, and more preferably 0.7 parts by mass or less, based on 100 parts by mass of the PFPE-containing silane compound in the curable composition of the present embodiment.
- the catalyst is preferably contained in an amount of 0.05 to 1.0 parts by mass, preferably 0.07 to 0.7 parts by mass, per 100 parts by mass of the PFPE-containing silane compound in the curable composition. It is more preferable that
- the catalyst can include at least one metal atom selected from the group consisting of platinum, rhodium, ruthenium, iridium, and palladium.
- platinum or a platinum compound is preferably used as the catalyst.
- Such a catalyst is advantageous in terms of reducing the cost of the catalyst and the availability.
- platinum compound examples include chloroplatinic acid or a complex of chloroplatinic acid and an olefin such as ethylene, a complex of alcohol or vinylsiloxane, metal platinum supported on silica, alumina, carbon or the like.
- RhCl (PPh 3 ) 3 RhCl (CO) (PPh 3 ) 2 , Ru 3 (CO) 12 , IrCl (CO) (PPh 3 ) 2 , Pd ( PPh 3 ) 4 etc.
- Ph is a phenyl group.
- the catalyst may be used in solid form when the catalyst is solid, but in order to obtain a more uniform cured product, a solution of chloroplatinic acid or a complex dissolved in a suitable solvent is not contained in PFPE. It is preferable to use it in compatibility with the saturated compound.
- the catalyst is preferably used together with the PFPE-containing unsaturated compound.
- the catalyst is preferably used together with the PFPE-containing unsaturated compound and the crosslinking agent (2).
- the catalyst in the curable composition, may be contained in an effective amount capable of contributing to the reaction, for example, an effective amount capable of contributing to the reaction as a hydrosilylation reaction catalyst.
- the content of the catalyst may be increased or decreased depending on the desired curing rate.
- the above-mentioned catalyst is usually preferably contained in an amount of 0.1 to 500 ppm (in terms of metal atom) per 100 parts by mass of the PFPE-containing compound (A).
- the catalyst can act as a hydrosilylation reaction catalyst.
- the hydrosilylation reaction catalyst can promote the addition reaction of the alkenyl group in the PFPE-containing unsaturated compound and the hydrogen atom (hydrosilyl group) bonded to the silicon atom in the crosslinking agent.
- the catalyst may be used alone or in combination of two or more.
- the curable composition used in the present invention may further contain a solvent. By including the solvent, the handleability of the composition is improved.
- the formed layer can be a continuous thin film.
- such a curable composition can contribute to formation of the thin film of arbitrary film thickness.
- the solvent is preferably contained in an amount of 300 parts by mass or less, more preferably 200 parts by mass or less, and 100 parts by mass or less based on 100 parts by mass of the total amount of the fluorine-containing silane compound, the organosilicon compound and the catalyst. It is further preferred that The solvent is contained in an amount of 1 part by mass or more, preferably 20 parts by mass or more, more preferably 50 parts by mass or more, based on 100 parts by mass of the total amount of the fluorine-containing silane compound, the organosilicon compound and the catalyst. More preferable.
- the solvent is preferably contained in a range of 1 to 300 parts by mass, more preferably 20 to 200 parts by mass, with respect to 100 parts by mass of the total amount of the PFPE-containing compound, the crosslinking agent and the catalyst. More preferably, it is included in the range of up to 100 parts by mass.
- preferred solvents are fluorine atom-containing solvents.
- the fluorine atom-containing solvent it is preferable to use at least one selected from the group consisting of ethyl perfluorobutyl ether and methyl perfluorobutyl ether. By using such a solvent, the storage stability of the curable composition of the present invention is improved.
- the curable composition comprises a homogeneous film (herein referred to as "homogeneous film” as described above by including a PFPE-containing compound, a crosslinking agent, a catalyst and a solvent). Formation) may be possible.
- a continuous film means a film which has no uncoated area such as a pinhole.
- thin films eg, 0.1 to 100 ⁇ m, specifically 1 to 50 ⁇ m
- any film thickness can be formed.
- a gel-like cured product can be formed.
- a curable composition may be suitable for use as, for example, a sealing material or the like.
- the water content in the solvent is preferably 100 mass ppm or less, and more preferably 50 mass ppm or less.
- the lower limit of the water content contained in the solvent is not particularly limited, and is, for example, 1 mass ppm or more.
- the water content can be measured using the Karl Fischer method. By such a water content, the storage stability of the curable composition can be improved.
- the water content contained in the curable composition of this invention is 20 mass ppm or less with respect to this composition.
- the lower limit value of the water content contained in the curable composition is not particularly limited, but substantially no water may be contained (for example, 0 mass ppm).
- the water content can be measured using the Karl Fischer method. By such a water content, the storage stability of the curable composition can be improved. By setting it as the above water content, stability (for example, storage stability) of the curable composition of this invention can be improved.
- the viscosity of the curable composition of the present invention is preferably in the range of 5 to 1000 mPa ⁇ s.
- the viscosity of the curable composition is more preferably 500 mPa ⁇ s or less, still more preferably 300 mPa ⁇ s or less, still more preferably 100 mPa ⁇ s or less, and 60 mPa ⁇ s or less More preferably, the viscosity is 50 mPa ⁇ s or less.
- the viscosity of the curable composition is more preferably 3 mPa ⁇ s or more, and still more preferably 5 mPa ⁇ s or more.
- the viscosity of the cured product-forming composition is in the range of 3 to 500 mPa ⁇ s, and more preferably in the range of 5 to 300 mPa ⁇ s.
- the curable composition of the present invention can be further improved in handleability by having the viscosity as described above.
- the viscosity is a viscosity at 25 ° C. of a B-type viscometer, and can be measured in accordance with JIS K7117-1: 1999.
- the PFPE-containing compound is a PFPE-containing unsaturated compound
- the crosslinking agent is an organosilicon compound having two or more hydrogen atoms (Si-H) bonded to a silicon atom in one molecule
- the catalyst is a metal-based catalyst comprising at least one selected from the group consisting of platinum, rhodium, ruthenium, iridium and palladium, preferably platinum or a platinum compound.
- the curable composition preferably further includes an organosilicon compound having one or more hydrolyzable groups bonded to a silicon atom in one molecule (hereinafter, also referred to as “organosilicon compound (3)”) May be included.
- organosilicon compound (3) can function as an adhesion-imparting agent that can impart self-adhesion to the curable composition.
- the hydrolyzable group is as defined above.
- the organic silicon compounds (3) may be used alone or in combination of two or more.
- the organosilicon compound (3) may have one or more monovalent perfluoroalkyl groups or monovalent perfluorooxyalkyl groups.
- the compatibility and dispersibility of the organosilicon compound (3) contained in the curable composition and the PFPE-containing unsaturated compound can be particularly good, and a cured product of the curable composition Uniformity can be good.
- the organic silicon compound (3) may have one or more hydrogen atoms directly linked to a silicon atom in one molecule from the viewpoint of addition reactivity with the PFPE-containing unsaturated compound.
- the organosilicon compound (3) is preferably an organosiloxane or trialkoxysilane having one or more alkoxysilyl groups bonded to a silicon atom via a carbon atom or a carbon atom and an oxygen atom.
- the siloxane skeleton of the organosiloxane in the organosilicon compound (3) may be cyclic, linear, branched or a combination thereof.
- organosiloxane those represented by the following general formula can be used.
- j1 is independently preferably an integer of 0 to 50, and more preferably an integer of 0 to 20 at each occurrence.
- j 2 is preferably an integer of 0 to 50, and more preferably an integer of 0 to 20, independently at each occurrence.
- j3 is independently preferably an integer of 1 to 50, and more preferably an integer of 1 to 20 at each occurrence.
- j4 is independently preferably an integer of 0 to 50, and more preferably an integer of 0 to 20 at each occurrence.
- j5 is preferably independently at each occurrence an integer of 0 to 50, and more preferably an integer of 0 to 20.
- the sum of j1, j2, j3, j4 and j5 is an integer such as to satisfy a polystyrene equivalent weight average molecular weight of 500 to 20,000 by gel permeation chromatography (GPC).
- R j1 each independently at each occurrence is a halogen-substituted or unsubstituted monovalent hydrocarbon group.
- the number of carbon atoms contained in the halogen-substituted or unsubstituted monovalent hydrocarbon group of R j1 is preferably in the range of 1 to 10, and more preferably in the range of 1 to 8.
- Specific examples of such a monovalent hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl and octyl; and aryls such as phenyl and tolyl.
- aralkyl groups such as benzyl group and phenylethyl group
- the monovalent hydrocarbon group is more preferably a methyl group.
- R j2 represents an alkoxysilyl group bonded to a silicon atom via a carbon atom or a carbon atom and an oxygen atom, specifically, And -R j5 -Si (OR j6 ) 3 or a group represented by the following formula.
- R j5 is a divalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 4 carbon atoms, specifically methylene, ethylene, propylene, butylene, hexylene, cyclohexylene, Or an alkylene group such as an octylene group
- R j6 is a monovalent hydrocarbon group having 1 to 8 carbon atoms, particularly 1 to 4 carbon atoms, and specifically, an alkyl such as a methyl group, an ethyl group or an n-propyl group It is a group.
- R j7 is a monovalent hydrocarbon group having 1 to 8 carbon atoms, particularly 1 to 4 carbon atoms, and specifically an alkyl group such as a methyl group, an ethyl group or an n-propyl group, and R j8 is It is a hydrogen atom or a methyl group, and k is an integer of 2 to 10.
- R j3 has the following general formula: -Z j1 -Rf j1 Is a group represented by The right side of Z j1 is coupled to R f j1 .
- Z j1 is, - (CH 2) j6 - , or - (CH 2) j7 -X j1 - ( wherein, X j1 is -OCH 2 -, or -Y j1 -NR j9 -CO-
- Y j1 is -CH 2 -or the following structural formula: Or o- , m- or p-dimethylsilyl phenylene group (in the above formula, a phenylene group is bonded to an N atom), and R j9 is a hydrogen atom, substituted or unsubstituted, preferably having 1 to 12 carbon atoms And particularly 1 to 10 monovalent hydrocarbon groups.
- Rf j1 represents a monovalent perfluoroalkyl group or a monovalent perfluorooxyalkyl group.
- the monovalent perfluoroalkyl group or the monovalent perfluorooxyalkyl group is as defined above.
- the R j4 is an epoxy group bonded to a silicon atom via a carbon atom or a carbon atom and an oxygen atom, and specific examples thereof include the following groups.
- R j10 is a divalent hydrocarbon group of 1 to 10, especially 1 to 5 carbon atoms which may be intervened by an oxygen atom, and more specifically a methylene group, an ethylene group, a propylene group, a butylene Group, alkylene group such as hexylene group, cyclohexylene group, octylene group etc.
- organosiloxane used as the organosilicon compound (3) include those represented by the following structural formulas.
- the group represented by PFPE 2 is bonded to the group represented by Rf at the terminal oxygen atom.
- Me represents a methyl group
- p, q and r are each independently an integer of 0 or more at each occurrence.
- PFPE 2 and Rf are as defined above.
- the trialkoxysilane used as the organosilicon compound (3) is not particularly limited, but vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-aminopropyl Trimethoxysilane, 3- (methacryloxypropyl) trimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-phenyl -3-Aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, etc. Alkoxy groups, as well as silanes having reactive organic groups in the same molecule, perfluoropropyltrimethoxysilane, etc. Including Tsu-containing
- the compounding amount of the organosilicon compound (3) is preferably in the range of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the PFPE-containing unsaturated compound. Is more preferred.
- the curable composition has sufficient adhesiveness and may have appropriate flowability and curability. Such curable compositions may have good physical hardness.
- the curable composition when the curable composition contains the PFPE-containing unsaturated compound, the crosslinking agent (2), and the organosilicon compound (3), the curable composition further comprises a hydrolysis catalyst (hereinafter referred to as “hydrolysis catalyst (E Also referred to as “)”.
- the hydrolysis catalyst has a catalytic function to enhance the hydrolyzability of the organosilicon compound (3).
- the above hydrolysis catalyst is not particularly limited as long as it does not inhibit the addition curing property of the composition, but, for example, organic titanium compounds such as titanium tetraisopropoxide, titanium tetranormal butoxide, titanium tetraacetylacetonate, etc .; zirconium tetranorpropoxide Organozirconium compounds such as zirconium tetranormal butoxide and zirconium tetraacetylacetonate; organotin compounds such as dibutyltin dilaurate, dibutyltin diacetate and dibutyltin acetylacetonate; aluminum trisacetylacetonate, aluminum trisethylacetoacetate; Organic aluminum compounds such as isopropoxy aluminum ethyl acetoacetate; other acidic catalysts, basic catalysts, etc.
- organic titanium compounds such as titanium tetraisopropoxide, titanium tetranormal butoxide, titanium te
- the said hydrolysis catalyst may use 1 type, and may use 2 or more types together.
- the compounding amount of the above-mentioned hydrolysis catalyst is preferably in the range of 0.001 to 5 parts by mass, and more preferably in the range of 0.01 to 1 parts by mass with respect to 100 parts by mass of the PFPE-containing unsaturated compound. preferable.
- the said hydrolysis catalyst can exhibit a sufficient catalytic effect by being included in said range in the curable composition of this aspect.
- the curable composition of the present embodiment may have appropriate fluidity.
- the hydrolysis catalyst can be prevented from curing in the form of gel.
- the curable composition used in the present invention may further contain a compound represented by the following Formula (A1), (B1), (C1) or (D1).
- R f independently at each occurrence represents an alkyl group of 1 to 16 carbon atoms which may be substituted by 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 by one or more fluorine atoms is a branched or branched straight chain Is preferably a linear or branched alkyl group having 1 to 6 carbon atoms, particularly 1 to 3 carbon atoms, and more preferably a linear alkyl group having 1 to 3 carbon atoms It is.
- Rf is preferably an alkyl group having 1 to 16 carbon atoms which is substituted by one or more fluorine atoms, more preferably a CF 2 H—C 1-15 fluoroalkylene group or a C 1 ⁇ group. It is a 16 perfluoroalkyl group, more preferably a C 1-16 perfluoroalkyl group.
- the perfluoroalkyl group having 1 to 16 carbon atoms may be linear or branched, preferably linear or branched, having 1 to 6 carbon atoms, in particular carbon atoms It is a perfluoroalkyl group of 1 to 3 and 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.
- ⁇ 1 is an integer of 1 to 9
- ⁇ 1 ′ is an integer of 1 to 9.
- ⁇ 1 ′ may vary depending on the valence of X 1 .
- the sum of ⁇ 1 and ⁇ 1 ′ is the same as the valence of X 1 .
- [alpha] 1 and [alpha] 1 'sum is 10, for example, [alpha] 1 is 9 and [alpha] 1' is 1, [alpha] 1 is 5 and [alpha] 1 'is 5 or [alpha] 1 is 1 and [alpha] 1, 'Can be nine.
- ⁇ 1 and ⁇ 1 ′ are 1.
- the above X 1 is preferably a divalent to heptavalent, more preferably a divalent to tetravalent, and still more preferably a divalent organic group.
- X 1 is a divalent to tetravalent organic group
- ⁇ 1 is 1 to 3
- ⁇ 1 ′ is 1.
- X 1 is a divalent organic group
- ⁇ 1 is 1
- ⁇ 1 ′ is 1.
- n1 ' is independently an integer of 0 to 3, preferably 1 to 3, and more preferably, for each (-SiR 13 n1' R 14 3-n1 ' ) unit. It is three.
- at least one n1 ' is an integer of 1 to 3, that is, all n1' are never 0 simultaneously.
- at least one R 13 exists.
- ⁇ 1 is an integer of 1 to 9
- ⁇ 1 ′ is an integer of 1 to 9.
- These ⁇ 1 and ⁇ 1 ′ can change according to the valence of X 3 .
- the sum of ⁇ 1 and ⁇ 1 ′ is the same as the valence of X 3 .
- X 3 is a 10-valent organic group
- the sum of ⁇ 1 and ⁇ 1 ′ is 10, for example, ⁇ 1 is 9 and ⁇ 1 ′ is 1, ⁇ 1 is 5 and ⁇ 1 ′ is 5, or ⁇ 1 is 1 and ⁇ 1 'Can be nine.
- X 3 is a divalent organic group
- ⁇ 1 and ⁇ 1 ′ are 1.
- X 3 is a single bond
- ⁇ 1 and ⁇ ′ 1 are 1.
- the above X 3 is preferably a divalent to heptavalent, more preferably a divalent to tetravalent, more preferably a divalent organic group.
- X 3 is a divalent to tetravalent organic group
- ⁇ 1 is 1 to 3
- ⁇ 1 ′ is 1.
- X 3 is a divalent organic group
- ⁇ 1 is 1 and ⁇ 1 ′ is 1.
- n1 ' is as defined in (A1).
- ⁇ 1 is an integer of 1 to 9
- ⁇ 1 ′ is an integer of 1 to 9.
- These ⁇ 1 and ⁇ 1 ′ may change according to the valence of X 5 .
- the sum of ⁇ 1 and ⁇ 1 ′ is the same as the valence of X 5 .
- X 5 is a 10-valent organic group
- the sum of ⁇ 1 and ⁇ 1 ′ is 10, for example, ⁇ 1 is 9 and ⁇ 1 ′ is 1, ⁇ 1 is 5 and ⁇ 1 ′ is 5, or ⁇ 1 is 1 and ⁇ 1 'Can be nine.
- X 5 is a divalent organic group
- ⁇ 1 and ⁇ 1 ′ are 1.
- X 5 is a single bond
- ⁇ 1 and ⁇ ′ 1 are 1.
- the above X 5 is preferably a divalent to heptavalent, more preferably a divalent to tetravalent, more preferably a divalent organic group.
- X 5 is a divalent to tetravalent organic group
- ⁇ 1 is 1 to 3 and ⁇ 1 ′ is 1.
- X 5 is a divalent organic group
- ⁇ 1 is 1 and ⁇ 1 ′ is 1.
- ⁇ 1 is an integer of 1 to 9
- ⁇ 1 ′ is an integer of 1 to 9.
- These ⁇ 1 and ⁇ 1 ′ can change according to the valence of X 7 .
- the sum of ⁇ 1 and ⁇ 1 ′ is the same as the valence of X 7 .
- X 7 is a 10-valent organic group
- the sum of ⁇ 1 and ⁇ 1 ′ is 10, for example, ⁇ 1 is 9 and ⁇ 1 ′ is 1, ⁇ 1 is 5 and ⁇ 1 ′ is 5, or ⁇ 1 is 1 and ⁇ 1 'Can be nine.
- X 7 is a divalent organic group
- ⁇ 1 and ⁇ 1 ′ are 1.
- X 7 is a single bond
- ⁇ 1 and ⁇ ′ 1 are 1.
- the above-mentioned X 7 is preferably a divalent to heptavalent, more preferably a divalent to tetravalent, more preferably a divalent organic group.
- X 7 is a divalent to tetravalent organic group, ⁇ 1 is 1 to 3 and ⁇ 1 ′ is 1.
- X 7 is a divalent organic group, ⁇ 1 is 1 and ⁇ 1 ′ is 1.
- the compound represented by Formula (A1), (B1), (C1) or (D1) is a compound represented by Formula (A1), (C1) or (D1) preferable.
- the adhesion to the substrate can be improved by using such a silane compound.
- a compound represented by the formulas (A), (B), (C) and (D) (hereinafter also referred to as "component (1)"), Formulas (A1), (B1), (B1), (B1), (B1), (B1), (B1), (C1), and (D1)
- the compound represented by C1) and (D1) is 0.1 mol% or more and 35 mol% or less.
- the lower limit of the content of the compounds represented by formulas (A1), (B1), (C1) and (D1) relative to the total of components (1) and (2) is preferably 0.1 mol%, more preferably It may preferably be 0.2 mol%, more preferably 0.5 mol%, even more preferably 1 mol%, particularly preferably 2 mol%, especially 5 mol%.
- the upper limit of the content of the compounds represented by formulas (A1), (B1), (C1), and (D1) to the total of components (1) and (2) is preferably 35 mol%, more preferably It may be 30 mole%, more preferably 20 mole%, even more preferably 15 mole% or 10 mole%.
- the compound represented by the formulas (A1), (B1), (C1) and (D1) relative to the total of the components (1) and (2) is preferably 0.1 mol% or more and 30 mol% or less, more preferably It is preferably 0.1 to 20 mol%, more preferably 0.2 to 10 mol%, still more preferably 0.5 to 10 mol%, particularly preferably 1 to 10 mol%. It is the mole% or less, for example, 2 mole% or more and 10 mole% or less, or 5 mole% or more and 10 mole% or less.
- the curable composition of the present invention can contribute to the formation of a cured product having good friction durability.
- the combination of the component (1) and the component (2) is preferably a combination of a compound represented by the formula (A) and a compound represented by the formula (A1), a table of the formula (B) Of the compound represented by the formula (B1), the combination of the compound represented by the formula (C) and the compound represented by the formula (C1), the compound represented by the formula (D) It is a combination of compounds represented by D1).
- the compounds represented by the formula (A) and the formula (A1) are preferably t is an integer of 2 or more, more preferably an integer of 2 to 10, and still more preferably an integer of 2 to 6.
- t is an integer of 2 or more, more preferably an integer of 2 to 10, and still more preferably an integer of 2 to 6.
- the compounds represented by the formula (C) and the formula (C1) preferably have k1 of 2 or 3, more preferably 3.
- the compounds represented by formula (C) is terminated, -Si- (Z 3 -SiR 72 3 ) 2, -Si- (Z 3 -SiR 72 "3) 2, -Si- (Z It has a structure represented by 3 -SiR 72 3 ) 3 or -Si- (Z 3 -SiR 72 ′ ′ 3 ) 3 , and more preferably —Si— (Z 3 —SiR 72 3 ) 3 or —Si— (Z 3 -SiR 72 "3) has a structure represented by 3; compound of formula (C1) is terminated, -Si- (Z 3 -SiR 72 3 ) 2, or, -Si - (Z 3 -SiR 72 3) it has a structure represented by 3, more preferably by a -Si- (Z 3 -SiR 72 3) having a structure represented by the 3-terminal such structures.
- the group represented by -Si- (Z 3 -SiR 72 3 ) 2 or -Si- (Z 3 -SiR 72 ′ ′ 3 ) 2 is specifically In -Si-R a 2 R b l1 R c m1, a group R a is represented by -Z 3 -SiR 72 3, the sum is 1 l1 and m1, In —Si—R a ′ ′ 2 R b ′ ′ 1 1 R c ′ ′ m 1 , R a ′ ′ is a group represented by —Z 3 —SiR 72 ′ ′ 3 and the total of l 1 and m 1 is 1; In -Si-R 71 2 R 72 q1 R 73 r1, a group R 71 is represented by -Z 3 -SiR 72 3, the
- the compounds represented by Formula (D) and Formula (D1) preferably have 12 of 2 or 3, more preferably 3.
- the compounds represented by the formula (D) is terminated, -C- (Y-SiR 85 3 ) 2, -C- to (Y-SiR 85 "3) 2 ( specifically, -C -(Y-SiR 85 3 ) 2 R 83 , -C- (Y-SiR 85 3 ) 2 R f , -C- (Y-SiR 85 ′ ′ 3 ) 2 R 83 , -C- (Y-SiR 85 ′ ′ 3 ) 2 R 83 ), -C- (Y-SiR 85 ) 3 , or -C- (Y-SiR 85 ′ ′ ) 3 structure, more preferably —C- (Y-SiR 85 ) 3 or —
- the compound represented by the formula (D1) has a C- (Y-SiR 85 ′ ′ ) 3 structure; the compound represented by the formula (D1) has, at the end, —C— (Y—SiR 85 3
- the curable composition used in the present invention may further contain other components.
- the other components are not particularly limited, and for example, (non-reactive) fluoropolyether compounds which can be understood as fluorine-containing oils, preferably perfluoro (poly) ether compounds (hereinafter referred to as “fluorine-containing compounds”) Stabilizers (dehydraters, molecular sieves, magnesium sulfate or methyl orthoformate), viscosity modifiers, fillers, fluorescent agents, storage stabilizers, fillers, colorants, heat resistance improvers, improvement of cold resistance An agent, a rust inhibitor, an adhesion improver, a liquid reinforcing agent, a polymerization initiator and the like may be contained.
- Rf 5 represents a C 1-16 alkyl group (preferably a C 1-16 perfluoroalkyl group) which may be substituted by one or more fluorine atoms
- R f 6 represents ,
- a C 1-16 alkyl group (preferably a C 1-16 perfluoroalkyl group) which may be substituted by one or more fluorine atoms, a fluorine atom or a hydrogen atom
- R f 5 and R f 6 is more preferably each independently a C 1-3 perfluoroalkyl group.
- a ′, b ′, c ′ and d ′ each represent the number of repeating units of four types of perfluoro (poly) ethers constituting the main skeleton of the polymer, and are each independently an integer of 0 or more and 300 or less;
- the sum of a ′, b ′, c ′ and d ′ is at least 1, preferably 1 to 300, more preferably 20 to 300.
- the order in which each repeating unit enclosed in parentheses with a subscript a ', b', c 'or d' is given is arbitrary in the formula.
- - (OC 4 F 8) - is, - (OCF 2 CF 2 CF 2 CF 2) -, - (OCF (CF 3) CF 2 CF 2) -, - (OCF 2 CF (CF 3) CF 2) -, - (OCF 2 CF 2 CF (CF 3)) -, - (OCF 2 C (CF 3) 2) -, - (OCF (CF 3 ) CF (CF 3 ) —, — (OCF (C 2 F 5 ) CF 2 ) — and — (OCF 2 CF (C 2 F 5 )) —, which may be any of - (OCF 2 CF 2 CF 2 CF 2) - a.
- - (OC 3 F 6) - is, - (OCF 2 CF 2 CF 2) -, - (OCF (CF 3) CF 2) - and - (OCF 2 CF (CF 3 )) - be any of Well, preferably-(OCF 2 CF 2 CF 2 )-.
- -(OC 2 F 4 )- may be either-(OCF 2 CF 2 )-or-(OCF (CF 3 ))-, but is preferably-(OCF 2 CF 2 )-.
- Rf 5 and Rf 6 are as described above; in formula (IIIa), b ′ ′ is an integer of 1 or more and 100 or less; in formula (IIIb), a ′ ′ and b ′ ′ are Each is independently an integer of 1 or more and 30 or less, and c ′ ′ and
- the fluorine-containing oil may have a number average molecular weight of 1,000 to 30,000.
- the number average molecular weight of the compound represented by the formula (IIIa) is preferably 2,000 to 8,000.
- the number average molecular weight of the compound represented by formula (IIIb) is 3,000 to 8,000.
- the number average molecular weight of the compound represented by formula (IIIb) is 8,000 to 30,000.
- the fluorine-containing oil is, for example, 0 to 500 parts by mass, preferably 0 to 100 parts by mass, more preferably 1 to 50 parts by mass, more preferably 100 parts by mass of the PFPE-containing silane compound. May be included in 1 to 5 parts by mass.
- the fluorine-containing oil may be a compound represented by the general formula Rf′-F (wherein Rf ′ is a C 5-16 perfluoroalkyl group).
- Rf ′ is a C 5-16 perfluoroalkyl group
- a chloro trifluoro ethylene oligomer may be sufficient.
- the compound represented by Rf′-F and the chlorotrifluoroethylene oligomer are preferable in that high affinity is obtained with the above perfluoro (poly) ether group-containing silane compound in which Rf is a C 1-16 perfluoroalkyl group. .
- Examples of the above-mentioned storage stabilizer include methyltrimethoxysilane, methyltripropenoxysilane, vinyltributanoxylsilane, methyltriacetoxysilane and the like.
- filler examples include fibrous fillers such as asbestos, glass fibers and organic fibers.
- Examples of the colorant include pigments and dyes.
- heat resistance improver examples include bengara and cerium oxide.
- ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -methacryloxypropylmethyldiethoxy Silane, N- ⁇ - (aminoethyl) - ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -chloropropyltrimethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -isocyanatopropyltriethoxysilane Silane etc. can be mentioned.
- liquid reinforcing agents mention may be made of reticulated polysiloxane consisting of triorganosiloxy units and SiO 2 units.
- polymerization initiator examples include azo initiators such as azobisisobutyronitrile, methyl azoisobutyrate, and azobisdimethylvaleronitrile; benzoyl peroxide, potassium persulfate, ammonium persulfate, benzophenone derivative, phosphine oxide derivative, benzoketone derivative And phenyl thioether derivatives, azide derivatives, diazo derivatives, disulfide derivatives and the like can be used.
- azo initiators such as azobisisobutyronitrile, methyl azoisobutyrate, and azobisdimethylvaleronitrile
- benzoyl peroxide potassium persulfate, ammonium persulfate, benzophenone derivative, phosphine oxide derivative, benzoketone derivative And phenyl thioether derivatives, azide derivatives, diazo derivatives, disulfide derivatives and the like can be used.
- These polymerization initiators may
- a protective layer is formed on the end face of the laminate.
- the treatment method is not particularly limited.
- the curable composition is applied to the end face of the laminate, and the heat treatment or light irradiation is performed as needed to cure the curable composition. It will be.
- the adhesiveness of the protective layer formed from a curable composition can be improved by giving a primer treatment with respect to a process part as needed prior to the process by a curable composition.
- the laminated body which has the 1st base material layer of this invention, an adhesive bond layer, and a 2nd base material layer was demonstrated, the laminated body of this invention may have a further layer.
- it may further have a second adhesive layer and a third base layer.
- the laminate of the present invention is used for various articles. Accordingly, the present invention also provides an article comprising the laminate of the present invention.
- Examples of the article include a touch panel, a display, an electronic element adhered on an electronic substrate, a smartphone, an electronic component taped to a metal housing of a tablet PC, a refrigerator, a surface of a home appliance such as a washing machine The operation panel etc. which were fixed with the adhesive tape are mentioned.
- PFPE Cured Composition Example 1 Preparation of end face protective agent 100 parts by weight of PFPE-containing compound A, 1 part by weight of tetraethoxysilane as a crosslinking agent, and 0.5 parts by weight of tetraisopropoxytitanium as a curing catalyst are weighed in a glass container for mixing, Stirring was performed using a stirrer to prepare a curable composition.
- a slide glass / adhesive film / slide glass laminate was prepared by sandwiching two slide glasses with a transparent adhesive film (LUCIACS CS9864 manufactured by Nitto Denko Corporation) with a thickness of 100 ⁇ m.
- the PFPE cured composition was applied to the end face of the laminate by a syringe, and allowed to stand at a temperature of 25 ° C. for 24 hours for curing to prepare a laminate having the end face protected.
- the prepared sample was immersed in oleic acid, placed in an electric furnace at 70 ° C. and heated for 1 week, and the state of the laminate was visually confirmed.
- the distance between the slide glasses of the laminate before and after immersion, and the weight change rate of the entire laminate were calculated. The case of no weight change is considered to be 0%.
- Example 2 A sample was prepared and evaluated in the same manner as in Example 1 except that PFPE-containing compound B was used.
- Example 3 Preparation of end face protective agent 4 parts by weight of compound D as a crosslinking agent and 100 parts by weight of PFPE-containing compound C, and 1,3-divinyl-1,1,3,3-tetramethyldi as a curing catalyst 0.4 parts by weight of a xylene solution containing 2% of a Pt complex of siloxane was weighed in a glass container for mixing, and stirred and mixed to prepare a curable composition.
- a sample was prepared and evaluated in the same manner as in Example 1 except that the obtained cured composition was used for edge protection and curing conditions after coating were performed at 100 ° C. for 2 hours.
- Comparative Example 1 The laminate was evaluated without a protective layer.
- the laminate of the present invention is excellent in chemical resistance and can be used in various applications.
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Abstract
Description
第1基材層、接着剤層、および第2基材層が、この順に積層された積層体であって、
前記積層体の端面が、パーフルオロポリエーテル基含有化合物を含む硬化性組成物より形成された層により覆われている、積層体
を提供する。
-(OC6F12)a-(OC5F10)b-(OC4F8)c-(OC3X10 6)d-(OC2F4)e-(OCF2)f-
で表される基である。式中、a、b、c、d、eおよびfは、それぞれ独立して0以上200以下の整数であって、a、b、c、d、eおよびfの和は少なくとも1である。好ましくは、a、b、c、d、eおよびfの和は5以上であり、より好ましくは10以上である。好ましくは、a、b、c、d、eおよびfの和は200以下であり、より好ましくは200以下であり、例えば10以上200以下であり、より具体的には10以上100以下である。また、a、b、c、d、eまたはfを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。X10は、各出現においてそれぞれ独立して、水素原子、フッ素原子または塩素原子であり、好ましくは水素原子またはフッ素原子であり、より好ましくはフッ素原子である。
-(R31)p’-(Xa)q’-
[式中:
R31は、単結合、-(CH2)s’-またはo-、m-もしくはp-フェニレン基を表し、好ましくは-(CH2)s’-であり、
s’は、1~20の整数、好ましくは1~6の整数、より好ましくは1~3の整数、さらにより好ましくは1または2であり、
Xaは、-(Xb)l’-を表し、
Xbは、各出現においてそれぞれ独立して、-O-、-S-、o-、m-もしくはp-フェニレン基、-C(O)O-、-Si(R33)2-、-(Si(R33)2O)m’-Si(R33)2-、-CONR34-、-O-CONR34-、-NR34-および-(CH2)n’-からなる群から選択される基を表し、
R33は、各出現においてそれぞれ独立して、フェニル基、C1-6アルキル基またはC1-6アルコキシ基を表し、好ましくはフェニル基またはC1-6アルキル基であり、より好ましくはメチル基であり、
R34は、各出現においてそれぞれ独立して、水素原子、フェニル基またはC1-6アルキル基(好ましくはメチル基)を表し、
m’は、各出現において、それぞれ独立して、1~100の整数、好ましくは1~20の整数であり、
n’は、各出現において、それぞれ独立して、1~20の整数、好ましくは1~6の整数、より好ましくは1~3の整数であり、
l’は、1~10の整数、好ましくは1~5の整数、より好ましくは1~3の整数であり、
p’は、0または1であり、
q’は、0または1であり、
ここに、p’およびq’の少なくとも一方は1であり、p’またはq’を付して括弧でくくられた各繰り返し単位の存在順序は任意である]
で表される2価の基が挙げられる。ここに、R31およびXa(典型的にはR31およびXaの水素原子)は、フッ素原子、C1-3アルキル基およびC1-3フルオロアルキル基から選択される1個またはそれ以上の置換基により置換されていてもよい。
単結合、
C1-20アルキレン基、
-R31-Xc-R32-、または
-Xd-R32-
[式中、R31およびR32は、上記と同意義である。]
であり得る。なお、アルキレン基とは、-(CδH2δ)-構造を有する基であり、置換または非置換であってよく、直鎖状または分枝鎖状であってもよい。
-Xf-、
-Xf-C1-20アルキレン基、
-Xf-(CH2)s’-Xc-、
-Xf-(CH2)s’-Xc-(CH2)t’-
-Xf-Xd-、または
-Xf-Xd-(CH2)t’-
である。式中、s’およびt’は、上記と同意義である。
上記式中、Xfは、炭素原子数1~6、好ましくは炭素原子数1~4、より好ましくは炭素原子数1~2のアルキレン基、例えばメチレン基である。Xf中の水素原子は、フッ素原子、C1-3アルキル基およびC1-3フルオロアルキル基から選択される1個またはそれ以上の置換基により置換されていてもよく、好ましくは置換されている。Xfは、直鎖状または分枝鎖状であってもよく、好ましくは直鎖状である。
単結合、
C1-20アルキレン基、
-(CH2)s’-Xc-、
-(CH2)s’-Xc-(CH2)t’-
-Xd-、または
-Xd-(CH2)t’-
[式中、s’およびt’は、上記と同意義である。]
である。
-O-、
-S-、
-C(O)O-、
-CONR34-、
-O-CONR34-、
-Si(R33)2-、
-(Si(R33)2O)m’-Si(R33)2-、
-O-(CH2)u’-(Si(R33)2O)m’-Si(R33)2-、
-O-(CH2)u’-Si(R33)2-O-Si(R33)2-CH2CH2-Si(R33)2-O-Si(R33)2-、
-O-(CH2)u’-Si(OCH3)2OSi(OCH3)2-、
-CONR34-(CH2)u’-(Si(R33)2O)m’-Si(R33)2-、
-CONR34-(CH2)u’-N(R34)-、または
-CONR34-(o-、m-またはp-フェニレン)-Si(R33)2-
[式中、R33、R34およびm’は、上記と同意義であり、
u’は1~20の整数、好ましくは2~6の整数、より好ましくは2~3の整数である。]を表す。Xcは、好ましくは-O-である。
-S-、
-C(O)O-、
-CONR34-、
-CONR34-(CH2)u’-(Si(R33)2O)m’-Si(R33)2-、
-CONR34-(CH2)u’-N(R34)-、または
-CONR34-(o-、m-またはp-フェニレン)-Si(R33)2-
[式中、各記号は、上記と同意義である。]
を表す。
-Xf-、
-Xf-C1-20アルキレン基、
-Xf-(CH2)s’-Xc-、
-Xf-(CH2)s’-Xc-(CH2)t’-
-Xf-Xd-、または
-Xf-Xd-(CH2)t’-
[式中、Xf、s’およびt’は、上記と同意義である。]
であり、
Xcが、-O-、または-CONR34-、
Xdが、-CONR34-、
R34は、各出現においてそれぞれ独立して、水素原子、フェニル基またはC1-6アルキル基(好ましくはメチル基)を表す。]
で表される基である。
-Xf-(CH2)s’-Xc-、
-Xf-(CH2)s’-Xc-(CH2)t’-
-Xf-Xd-、または
-Xf-Xd-(CH2)t’-
[式中、Xf、s’およびt’は、上記と同意義である。]
であり、
Xcが、-CONR34-、
Xdが、-CONR34-、
R34は、各出現においてそれぞれ独立して、水素原子、フェニル基またはC1-6アルキル基(好ましくはメチル基)を表す。]
で表される基である。
単結合、
C1-20アルキレン基、
-(CH2)s’-Xc-(CH2)t’-、または
-Xd-(CH2)t’-
[式中、各記号は、上記と同意義である。]
であり得る。
単結合、
C1-20アルキレン基、
-(CH2)s’-O-(CH2)t’-、
-(CH2)s’-(Si(R33)2O)m’-Si(R33)2-(CH2)t’-、
-(CH2)s’-O-(CH2)u’-(Si(R33)2O)m’-Si(R33)2-(CH2)t’-、または
-(CH2)s’-O-(CH2)t’-Si(R33)2 -(CH2)u’-Si(R33)2-(CvH2v)-
[式中、R33、m’、s’、t’およびu’は、上記と同意義であり、vは1~20の整数、好ましくは2~6の整数、より好ましくは2~3の整数である。]
である。
Dは、
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CF2O(CH2)3-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-CONH-(CH2)3-、
-CON(CH3)-(CH2)3-、
-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、および
から選択される基であり、
Eは、-(CH2)ne-(neは2~6の整数)であり、
Dは、分子主鎖のPFPEに結合し、Eは、PFPEと反対の基に結合する。]
単結合、
-CH2OCH2-、
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CH2O(CH2)6-、
-CF2-CH2-O-CH2-、
-CF2-CH2-O-(CH2)2-、
-CF2-CH2-O-(CH2)3-、
-CF2-CH2-O-(CH2)6-、
-CH2O(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-、
-CH2OCF2CHFOCF2-、
-CH2OCF2CHFOCF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-、
-CH2OCH2CF2CF2OCF2-、
-CH2OCH2CF2CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF2CF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF2-、
-CH2OCH2CHFCF2OCF2CF2-、
-CH2OCH2CHFCF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CH2OCH2(CH2)7CH2Si(OCH3)2OSi(OCH3)2(CH2)2Si(OCH3)2OSi(OCH3)2(CH2)2-、
-CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)3-、
-CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)3-、
-CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)2-、
-CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)2-、
-(CH2)2-Si(CH3)2-(CH2)2-、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-(CH2)5-、
-(CH2)6-、
-CF2-、
-(CF2)2-、
-CF2-CH2-、
-CF2-(CH2)2-、
-CF2-(CH2)3-、
-CF2-(CH2)4-、
-CF2-(CH2)5-、
-CF2-(CH2)6-、
-CO-
-CONH-
-CONH-CH2-、
-CONH-(CH2)2-、
-CONH-(CH2)3-、
-CONH-(CH2)6-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CON(CH3)-(CH2)3-、
-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CON(CH3)-(CH2)6-、
-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CONH-(CH2)2NH(CH2)3-、
-CONH-(CH2)6NH(CH2)3-、
-CH2O-CONH-(CH2)3-、
-CH2O-CONH-(CH2)6-、
-S-(CH2)3-、
-(CH2)2S(CH2)3-、
-CONH-(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-、
-C(O)O-(CH2)3-、
-C(O)O-(CH2)6-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)2-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)3-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-CH2-、
-OCH2-、
-O(CH2)3-、
-OCFHCF2-、
-CH2OCH2-、
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CH2O(CH2)6-、
-CF2-CH2-O-CH2-、
-CF2-CH2-O-(CH2)2-、
-CF2-CH2-O-(CH2)3-、
-CF2-CH2-O-(CH2)6-、
-CH2OCF2CHFOCF2-、
-CH2OCF2CHFOCF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-、
-CH2OCH2CF2CF2OCF2-、
-CH2OCH2CF2CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF2CF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF2-、
-CH2OCH2CHFCF2OCF2CF2-、
-CH2OCH2CHFCF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-(CH2)5-、
-(CH2)6-、
-CF2-、
-(CF2)2-、
-CF2-CH2-、
-CF2-(CH2)2-、
-CF2-(CH2)3-、
-CF2-(CH2)4-、
-CF2-(CH2)5-、
-CF2-(CH2)6-、
-CONH-、
-CONH-CH2-、
-CONH-(CH2)2-、
-CONH-(CH2)3-、
-CONH-(CH2)6-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CON(CH3)-(CH2)3-、
-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CON(CH3)-(CH2)6-、
-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CONH-(CH2)2NH(CH2)3-、
-CONH-(CH2)6NH(CH2)3-、
-CH2O-CONH-(CH2)3-、
-CH2O-CONH-(CH2)6-、
-OCH2-、
-O(CH2)3-、または
-OCFHCF2-、
であることが好ましい。
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CONH-、
-CONH-CH2-、
-CONH-(CH2)2-、
-CONH-(CH2)3-、
-CONH-(CH2)6-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CON(CH3)-(CH2)3-、
-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CON(CH3)-(CH2)6-、
-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CONH-(CH2)2NH(CH2)3-、
-CONH-(CH2)6NH(CH2)3-、
である。
単結合、
-Xf-、
炭素原子数1~6、好ましくは炭素原子数1~3のアルキレン基、
-Xf-C1-6アルキレン基、好ましくは-Xf-C1-3アルキレン基、より好ましくは
-Xf-C1-2アルキレン基、
-C6H4-R52’-、
-CONR4’-R52’-、
-CONR4’-C6H4-R52’-、
-Xf-CONR4’-R52’-、
-Xf-CONR4’-C6H4-R52’-、
-CO-R52’-、
-CO-C6H4-R52’-、
-SO2NR4’-R52’-、
-SO2NR4’-C6H4-R52’-、
-SO2-R52’-、
-SO2-C6H4-R52’-、
-R51’-C6H4-、
-R51’-CONR4’-、
-R51’-CONR4’-C6H4-、
-R51’-CO-、
-R51’-CO-C6H4-、
-R51’-SO2NR4’-、
-R51’-SO2NR4’-C6H4-、
-R51’-SO2-、
-R51’-SO2-C6H4-、
-C6H4-
-CONR4’-、
-CONR4’-C6H4-、
-Xf-CONR4’-、
-Xf-CONR4’-C6H4-、
-CO-、
-CO-C6H4-、
-SO2NR4’-、
-SO2NR4’-C6H4-
-SO2-、または
-SO2-C6H4-
(式中、R51’およびR52’は、それぞれ独立して、炭素原子数1~6、好ましくは炭素原子数1~3の直鎖のアルキレン基であり、上記したように、上記アルキレン基は、置換または非置換であり、上記アルキレン基の置換基としては、例えばハロゲン原子、好ましくはフッ素原子を挙げることができる。
R4’は、水素原子またはメチル基である。)
であり得る。
-Xf-、
炭素原子数1~6、好ましくは炭素原子数1~3のアルキレン基、
-Xf-C1-6アルキレン基、好ましくは-Xf-C1-3アルキレン基、より好ましくは
-Xf-C1-2アルキレン基、
-CONR4’-R52’-、
-CONR4’-C6H4-R52’-、
-Xf-CONR4’-R52’-、
-Xf-CONR4’-C6H4-R52’-、
-R51’-CONR4’-、
-R51’-CONR4’-C6H4-、
-CONR4’-、
-CONR4’-C6H4-、
-Xf-CONR4’-、
-Xf-CONR4’-C6H4-、
-R51’-CONR4’-、または
-R51’-CONR4’-C6H4-、
であり得る。式中、Xf、R4’、R51’およびR52’は、それぞれ上記と同意義である。
-CONR4’-R52’-、
-CONR4’-C6H4-R52’-、
-Xf-CONR4’-R52’-、
-Xf-CONR4’-C6H4-R52’-、
-R51’-CONR4’-、
-R51’-CONR4’-C6H4-、
-CONR4’-、
-CONR4’-C6H4-、
-Xf-CONR4’-、または
-Xf-CONR4’-C6H4-、
であり得る。
単結合、
炭素原子数1~6のパーフルオロアルキレン基(例えば、-CF2-、-(CF2)2-等)、
炭素原子数1~6のアルキレン基、
-CF2-C1-6アルキレン基、
-CONH-、
-CONH-CH2-、
-CONH-(CH2)2-
-CONH-(CH2)3-、
-CF2-CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CON(CH3)-、
-CON(CH3)-CH2-、
-CON(CH3)-(CH2)2-、
-CON(CH3)-(CH2)3-、
-CF2-CON(CH3)-、
-CF2-CON(CH3)CH2-、
-CF2-CON(CH3)-(CH2)2-、
-CF2-CON(CH3)-(CH2)3-、
-CH2-CONH-、
-CH2-CONH-CH2-、
-CH2-CONH-(CH2)2-、
-CH2-CONH-(CH2)3-、
-CF2-CH2-CONH-、
-CF2-CH2-CONH-CH2-、
-CF2-CH2-CONH-(CH2)2-、
-CF2-CH2-CONH-(CH2)3-、
-CONH-C6H4-、
-CON(CH3)-C6H4-、
-CH2-CON(CH3)-CH2-、
-CH2-CON(CH3)-(CH2)2-、
-CH2-CON(CH3)-(CH2)3-、
-CON(CH3)-C6H4-、
-CF2-CONH-C6H4-、
-CF2-CON(CH3)-C6H4-、
-CF2-CH2-CON(CH3)-CH2-、
-CF2-CH2-CON(CH3)-(CH2)2-、
-CF2-CH2-CON(CH3)-(CH2)3-、
-CF2-CON(CH3)-C6H4-、
-CO-、
-CO-C6H4-、
-C6H4-、
-SO2NH-、
-SO2NH-CH2-、
-SO2NH-(CH2)2-、
-SO2NH-(CH2)3-、
-SO2NH-C6H4-、
-SO2N(CH3)-、
-SO2N(CH3)-CH2-、
-SO2N(CH3)-(CH2)2-、
-SO2N(CH3)-(CH2)3-、
-SO2N(CH3)-C6H4-、
-SO2-、
-SO2-CH2-、
-SO2-(CH2)2-、
-SO2-(CH2)3-、または
-SO2-C6H4-
などが挙げられる。
炭素原子数1~6のアルキレン基、
炭素原子数1~6のパーフルオロアルキレン基(例えば、-CF2-、-(CF2)2-等)、
-CF2-C1-6アルキレン基、
-CONH-、
-CONH-CH2-、
-CONH-(CH2)2-、
-CONH-(CH2)3-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CON(CH3)-、
-CON(CH3)-CH2-、
-CON(CH3)-(CH2)2-、
-CON(CH3)-(CH2)3-、
-CF2-CON(CH3)-、
-CF2-CON(CH3)CH2-、
-CF2-CON(CH3)-(CH2)2-、
-CF2-CON(CH3)-(CH2)3-、
-CH2-CONH-、
-CH2-CONH-CH2-、
-CH2-CONH-(CH2)2-、
-CH2-CONH-(CH2)3-、
-CF2-CH2-CONH-、
-CF2-CH2-CONH-CH2-、
-CF2-CH2-CONH-(CH2)2-、
-CF2-CH2-CONH-(CH2)3-、
-CONH-C6H4-、
-CON(CH3)-C6H4-、
-CH2-CON(CH3)-CH2-、
-CH2-CON(CH3)-(CH2)2-、
-CH2-CON(CH3)-(CH2)3-、
-CON(CH3)-C6H4-
-CF2-CONH-C6H4-、
-CF2-CON(CH3)-C6H4-、
-CF2-CH2-CON(CH3)-CH2-、
-CF2-CH2-CON(CH3)-(CH2)2-、
-CF2-CH2-CON(CH3)-(CH2)3-、
-CF2-CON(CH3)-C6H4-、
などが挙げられる。
-CONH-、
-CONH-CH2-、
-CONH-(CH2)2-、
-CONH-(CH2)3-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CON(CH3)-、
-CON(CH3)-CH2-、
-CON(CH3)-(CH2)2-、
-CON(CH3)-(CH2)3-、
-CF2-CON(CH3)-、
-CF2-CON(CH3)CH2-、
-CF2-CON(CH3)-(CH2)2-、
-CF2-CON(CH3)-(CH2)3-、
-CH2-CONH-、
-CH2-CONH-CH2-、
-CH2-CONH-(CH2)2-、
-CH2-CONH-(CH2)3-、
-CF2-CH2-CONH-、
-CF2-CH2-CONH-CH2-、
-CF2-CH2-CONH-(CH2)2-、
-CF2-CH2-CONH-(CH2)3-、
-CONH-C6H4-、
-CON(CH3)-C6H4-、
-CH2-CON(CH3)-CH2-、
-CH2-CON(CH3)-(CH2)2-、
-CH2-CON(CH3)-(CH2)3-、
-CON(CH3)-C6H4-
-CF2-CONH-C6H4-、
-CF2-CON(CH3)-C6H4-、
-CF2-CH2-CON(CH3)-CH2-、
-CF2-CH2-CON(CH3)-(CH2)2-、
-CF2-CH2-CON(CH3)-(CH2)3-、または
-CF2-CON(CH3)-C6H4-、
などが挙げられる。
R41は、それぞれ独立して、水素原子、フェニル基、炭素原子数1~6のアルキル基、またはC1-6アルコキシ基、好ましくはメチル基であり;
各X1基において、Tのうち任意のいくつかは、分子主鎖のPFPEに結合する以下の基:
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CF2O(CH2)3-、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-CONH-(CH2)3-、
-CON(CH3)-(CH2)3-、
-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、または
であり、別のTのいくつかは、分子主鎖のPFPEと反対の基に結合する-(CH2)n”-(n”は2~6の整数)であり、存在する場合、残りのTは、それぞれ独立して、メチル基、フェニル基、C1-6アルコキシ基またはラジカル捕捉基もしくは紫外線吸収基であり得る。なお、上記態様においても、X1として記載している基において、左側がPFPEで表される基に、右側がα1を付して括弧でくくられた基に、それぞれ結合する。
PFPEは、各出現においてそれぞれ独立して、式:
-(OC6F12)a-(OC5F10)b-(OC4F8)c-(OC3F6)d-(OC2F4)e-(OCF2)f-
(式中、a、b、c、d、eおよびfは、それぞれ独立して0以上200以下の整数であって、a、b、c、d、eおよびfの和は少なくとも1であり、a、b、c、d、eまたはfを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。)
で表される基であり;
R13は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し;
R14は、各出現においてそれぞれ独立して、水素原子または炭素原子数1~22のアルキル基を表し;
R11は、各出現においてそれぞれ独立して、水素原子またはハロゲン原子を表し;
R12は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し;
R11”、R12”、R13”、R14”は、それぞれ、R11、R12、R13、R14と同意義であり;
n1は、1~3の整数であり、好ましくは3であり;
X1は、各出現においてそれぞれ独立して、-O-CFR20-(CF2)e’-であり;
R20は、各出現においてそれぞれ独立して、フッ素原子または低級フルオロアルキル基であり;
e’は、各出現においてそれぞれ独立して、0または1であり;
X2は、-(CH2)u-であり;
uは、各出現においてそれぞれ独立して、0~2の整数であり;
tは、各出現においてそれぞれ独立して、2~10の整数である。]
で表される化合物である。
単結合、
-CH2OCH2-、
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CH2O(CH2)6-、
-CF2-CH2-O-CH2-、
-CF2-CH2-O-(CH2)2-、
-CF2-CH2-O-(CH2)3-、
-CF2-CH2-O-(CH2)6-、
-CH2O(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-、
-CH2OCF2CHFOCF2-、
-CH2OCF2CHFOCF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-、
-CH2OCH2CF2CF2OCF2-、
-CH2OCH2CF2CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF2CF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF2-、
-CH2OCH2CHFCF2OCF2CF2-、
-CH2OCH2CHFCF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CH2OCH2(CH2)7CH2Si(OCH3)2OSi(OCH3)2(CH2)2Si(OCH3)2OSi(OCH3)2(CH2)2-、
-CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)3-、
-CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)3-、
-CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)2-、
-CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)2-、
-(CH2)2-Si(CH3)2-(CH2)2-、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-(CH2)5-、
-(CH2)6-、
-CF2-、
-(CF2)2-、
-CF2-CH2-、
-CF2-(CH2)2-、
-CF2-(CH2)3-、
-CF2-(CH2)4-、
-CF2-(CH2)5-、
-CF2-(CH2)6-、
-CO-、
-CONH-、
-CONH-CH2-、
-CONH-(CH2)2-、
-CONH-(CH2)3-、
-CONH-(CH2)6-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CON(CH3)-(CH2)3-、
-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CON(CH3)-(CH2)6-、
-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CONH-(CH2)2NH(CH2)3-、
-CONH-(CH2)6NH(CH2)3-、
-CH2O-CONH-(CH2)3-、
-CH2O-CONH-(CH2)6-、
-S-(CH2)3-、
-(CH2)2S(CH2)3-、
-CONH-(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-、
-C(O)O-(CH2)3-、
-C(O)O-(CH2)6-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)2-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)3-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-CH2-、
-OCH2-、
-O(CH2)3-、
-OCFHCF2-、
-CH2OCH2-、
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CH2O(CH2)6-、
-CF2-CH2-O-CH2-、
-CF2-CH2-O-(CH2)2-、
-CF2-CH2-O-(CH2)3-、
-CF2-CH2-O-(CH2)6-、
-CH2OCF2CHFOCF2-、
-CH2OCF2CHFOCF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-、
-CH2OCH2CF2CF2OCF2-、
-CH2OCH2CF2CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF2CF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF2-、
-CH2OCH2CHFCF2OCF2CF2-、
-CH2OCH2CHFCF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CF2-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-(CH2)5-、
-(CH2)6-、
-CF2-、
-(CF2)2-、
-CF2-CH2-、
-CF2-(CH2)2-、
-CF2-(CH2)3-、
-CF2-(CH2)4-、
-CF2-(CH2)5-、
-CF2-(CH2)6-、
-CONH-、
-CONH-CH2-、
-CONH-(CH2)2-、
-CONH-(CH2)3-、
-CONH-(CH2)6-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CON(CH3)-(CH2)3-、
-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CON(CH3)-(CH2)6-、
-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CONH-(CH2)2NH(CH2)3-、
-CONH-(CH2)6NH(CH2)3-、
-CH2O-CONH-(CH2)3-、
-CH2O-CONH-(CH2)6-、
-OCH2-、
-O(CH2)3-、
-OCFHCF2-、
であることが好ましい。
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CF2-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CONH-、
-CONH-CH2-、
-CONH-(CH2)2-、
-CONH-(CH2)3-、
-CONH-(CH2)6-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CON(CH3)-(CH2)3-、
-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CON(CH3)-(CH2)6-、
-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CONH-(CH2)2NH(CH2)3-、
-CONH-(CH2)6NH(CH2)3-、
である。
PFPEは、各出現においてそれぞれ独立して、式:
-(OC6F12)a-(OC5F10)b-(OC4F8)c-(OC3F6)d-(OC2F4)e-(OCF2)f-
(式中、a、b、c、d、eおよびfは、それぞれ独立して0以上200以下の整数であって、a、b、c、d、eおよびfの和は少なくとも1であり、a、b、c、d、eまたはfを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。)
で表される基であり;
R13は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し;
R14は、各出現においてそれぞれ独立して、水素原子または炭素原子数1~22のアルキル基を表し;
R13”、およびR14”は、それぞれ、R13、およびR14と同意義であり;
n1は、1~3の整数であり、好ましくは3であり;
X3は、-CH2O(CH2)2-、-CH2O(CH2)3-または-CH2O(CH2)6-である。]
で表される化合物である。
単結合、
-CH2OCH2-、
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CH2O(CH2)6-、
-CF2-CH2-O-CH2-、
-CF2-CH2-O-(CH2)2-、
-CF2-CH2-O-(CH2)3-、
-CF2-CH2-O-(CH2)6-、
-CH2O(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-、
-CH2OCF2CHFOCF2-、
-CH2OCF2CHFOCF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-、
-CH2OCH2CF2CF2OCF2-、
-CH2OCH2CF2CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF2CF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF2-、
-CH2OCH2CHFCF2OCF2CF2-、
-CH2OCH2CHFCF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CH2OCH2(CH2)7CH2Si(OCH3)2OSi(OCH3)2(CH2)2Si(OCH3)2OSi(OCH3)2(CH2)2-、
-CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)3-、
-CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)3-、
-CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)2-、
-CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)2-、
-(CH2)2-Si(CH3)2-(CH2)2-、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-(CH2)5-、
-(CH2)6-、
-CF2-、
-(CF2)2-、
-CF2-CH2-、
-CF2-(CH2)2-、
-CF2-(CH2)3-、
-CF2-(CH2)4-、
-CF2-(CH2)5-、
-CF2-(CH2)6-、
-CO-、
-CONH-、
-CONH-CH2-、
-CONH-(CH2)2-、
-CONH-(CH2)6-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CONH-(CH2)3-、
-CON(CH3)-(CH2)3-、
-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CON(CH3)-(CH2)6-、
-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CONH-(CH2)2NH(CH2)3-、
-CONH-(CH2)6NH(CH2)3-、
-CH2O-CONH-(CH2)3-、
-CH2O-CONH-(CH2)6-、
-S-(CH2)3-、
-(CH2)2S(CH2)3-、
-CONH-(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-、
-C(O)O-(CH2)3-、
-C(O)O-(CH2)6-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)2-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)3-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-CH2-、
-OCH2-、
-O(CH2)3-、
-OCFHCF2-、
-CH2OCH2-、
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CH2O(CH2)6-、
-CF2-CH2-O-CH2-、
-CF2-CH2-O-(CH2)2-、
-CF2-CH2-O-(CH2)3-、
-CF2-CH2-O-(CH2)6-、
-CH2OCF2CHFOCF2-、
-CH2OCF2CHFOCF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-、
-CH2OCH2CF2CF2OCF2-、
-CH2OCH2CF2CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF2CF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF2-、
-CH2OCH2CHFCF2OCF2CF2-、
-CH2OCH2CHFCF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CF2-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-(CH2)5-、
-(CH2)6-、
-CF2-、
-(CF2)2-、
-CF2-CH2-、
-CF2-(CH2)2-、
-CF2-(CH2)3-、
-CF2-(CH2)4-、
-CF2-(CH2)5-、
-CF2-(CH2)6-、
-CONH-、
-CONH-CH2-、
-CONH-(CH2)2-、
-CONH-(CH2)3-、
-CONH-(CH2)6-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CON(CH3)-(CH2)3-、
-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CON(CH3)-(CH2)6-、
-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CONH-(CH2)2NH(CH2)3-、
-CONH-(CH2)6NH(CH2)3-、
-CH2O-CONH-(CH2)3-、
-CH2O-CONH-(CH2)6-、
-OCH2-、
-O(CH2)3-、
-OCFHCF2-、
であることが好ましい。
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CF2-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CONH-、
-CONH-CH2-、
-CONH-(CH2)2-、
-CONH-(CH2)3-、
-CONH-(CH2)6-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CON(CH3)-(CH2)3-、
-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CON(CH3)-(CH2)6-、
-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CONH-(CH2)2NH(CH2)3-、
-CONH-(CH2)6NH(CH2)3-、
である。
単結合、
-CH2OCH2-、
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CH2O(CH2)6-、
-CF2-CH2-O-CH2-、
-CF2-CH2-O-(CH2)2-、
-CF2-CH2-O-(CH2)3-、
-CF2-CH2-O-(CH2)6-、
-CH2O(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-、
-CH2OCF2CHFOCF2-、
-CH2OCF2CHFOCF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-、
-CH2OCH2CF2CF2OCF2-、
-CH2OCH2CF2CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF2CF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF2-、
-CH2OCH2CHFCF2OCF2CF2-、
-CH2OCH2CHFCF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CH2OCH2(CH2)7CH2Si(OCH3)2OSi(OCH3)2(CH2)2Si(OCH3)2OSi(OCH3)2(CH2)2-、
-CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)3-、
-CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)3-、
-CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)2-、
-CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)2-、
-(CH2)2-Si(CH3)2-(CH2)2-、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-(CH2)5-、
-(CH2)6-、
-CF2-、
-(CF2)2-、
-CF2-CH2-、
-CF2-(CH2)2-、
-CF2-(CH2)3-、
-CF2-(CH2)4-、
-CF2-(CH2)5-、
-CF2-(CH2)6-、
-CO-、
-CONH-、
-CONH-CH2-、
-CONH-(CH2)2-、
-CONH-(CH2)3-、
-CONH-(CH2)6-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CON(CH3)-(CH2)3-、
-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CON(CH3)-(CH2)6-、
-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CONH-(CH2)2NH(CH2)3-、
-CONH-(CH2)6NH(CH2)3-、
-CH2O-CONH-(CH2)3-、
-CH2O-CONH-(CH2)6-、
-S-(CH2)3-、
-(CH2)2S(CH2)3-、
-CONH-(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-、
-C(O)O-(CH2)3-、
-C(O)O-(CH2)6-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)2-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)3-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-CH2-、
-OCH2-、
-O(CH2)3-、
-OCFHCF2-、
-CH2OCH2-、
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CH2O(CH2)6-、
-CF2-CH2-O-CH2-、
-CF2-CH2-O-(CH2)2-、
-CF2-CH2-O-(CH2)3-、
-CF2-CH2-O-(CH2)6-、
-CH2OCF2CHFOCF2-、
-CH2OCF2CHFOCF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-、
-CH2OCH2CF2CF2OCF2-、
-CH2OCH2CF2CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF2CF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF2-、
-CH2OCH2CHFCF2OCF2CF2-、
-CH2OCH2CHFCF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CF2-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-(CH2)5-、
-(CH2)6-、
-CF2-、
-(CF2)2-、
-CF2-CH2-、
-CF2-(CH2)2-、
-CF2-(CH2)3-、
-CF2-(CH2)4-、
-CF2-(CH2)5-、
-CF2-(CH2)6-、
-CONH-、
-CONH-CH2-、
-CONH-(CH2)2-、
-CONH-(CH2)3-、
-CONH-(CH2)6-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CON(CH3)-(CH2)3-、
-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CON(CH3)-(CH2)6-、
-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CONH-(CH2)2NH(CH2)3-、
-CONH-(CH2)6NH(CH2)3-、
-CH2O-CONH-(CH2)3-、
-CH2O-CONH-(CH2)6-、
-OCH2-、
-O(CH2)3-、
-OCFHCF2-、
であることが好ましい。
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CF2-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CONH-、
-CONH-CH2-、
-CONH-(CH2)2-、
-CONH-(CH2)3-、
-CONH-(CH2)6-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CON(CH3)-(CH2)3-、
-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CON(CH3)-(CH2)6-、
-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CONH-(CH2)2NH(CH2)3-、
-CONH-(CH2)6NH(CH2)3-、
である。
CH2=CH-Rk1-PFPE-Rk1-CH=CH2 (I)
-(R31)p’-(Xa)q’-
[式中:
R31は、単結合、-(CH2)s’-またはo-、m-もしくはp-フェニレン基を表し、好ましくは-(CH2)s’-であり、
s’は、1~20の整数、好ましくは1~6の整数、より好ましくは1~3の整数、さらにより好ましくは1または2であり、
Xaは、-(Xb)l’-を表し、
Xbは、各出現においてそれぞれ独立して、-O-、-S-、o-、m-もしくはp-フェニレン基、-C(O)O-、-Si(R33)2-、-(Si(R33)2O)m’-Si(R33)2-、-CONR34-、-O-CONR34-、-NR34-および-(CH2)n’-からなる群から選択される基を表し、
R33は、各出現においてそれぞれ独立して、フェニル基、C1-6アルキル基またはC1-6アルコキシ基を表し、好ましくはフェニル基またはC1-6アルキル基であり、より好ましくはメチル基であり、
R34は、各出現においてそれぞれ独立して、水素原子、フェニル基またはC1-6アルキル基(好ましくはメチル基)を表し、
m’は、各出現においてそれぞれ独立して、1~100の整数、好ましくは1~20の整数であり、
n’は、各出現においてそれぞれ独立して、1~20の整数、好ましくは1~6の整数、より好ましくは1~3の整数であり、
l’は、1~10の整数、好ましくは1~5の整数、より好ましくは1~3の整数であり、
p’は、0または1であり、
q’は、0または1であり、
ここに、p’およびq’の少なくとも一方は1であり、p’またはq’を付して括弧でくくられた各繰り返し単位の存在順序は任意である]
で表される2価の基が挙げられる。ここに、R31およびXa(典型的にはR31およびXaの水素原子)は、フッ素原子、C1-3アルキル基およびC1-3フルオロアルキル基から選択される1個またはそれ以上の置換基により置換されていてもよい。
単結合、
C1-20アルキレン基、
-R31-Xc-R32-、または
-Xd-R32-
[式中、R31およびR32は、上記と同意義である。]
であり得る。なお、アルキレン基とは、-(CδH2δ)-構造を有する基であり、置換または非置換であってよく、直鎖状または分枝鎖状であってもよい。
単結合、
C1-20アルキレン基、
-(CH2)s’-Xc-、
-(CH2)s’-Xc-(CH2)t’-
-Xd-、または
-Xd-(CH2)t’-
[式中、s’およびt’は、上記と同意義である。]
である。
-Xf-、
-Xf-C1-20アルキレン基、
-Xf-(CH2)s’-Xc-、
-Xf-(CH2)s’-Xc-(CH2)t’-
-Xf-Xd-、または
-Xf-Xd-(CH2)t’-
である。式中、s’およびt’は、上記と同意義である。
上記式中、Xfは、炭素原子数1~6、好ましくは炭素原子数1~4、より好ましくは炭素原子数1~2のアルキレン基、例えばメチレン基である。Xf中の水素原子は、フッ素原子、C1-3アルキル基およびC1-3フルオロアルキル基から選択される1個またはそれ以上の置換基により置換されていてもよく、好ましくは置換されている。Xfは、直鎖状または分枝鎖状であってもよく、好ましくは直鎖状である。
-O-、
-S-、
-C(O)O-、
-CONR34-、
-O-CONR34-、
-Si(R33)2-、
-(Si(R33)2O)m’-Si(R33)2-、
-O-(CH2)u’-(Si(R33)2O)m’-Si(R33)2-、
-O-(CH2)u’-Si(R33)2-O-Si(R33)2-CH2CH2-Si(R33)2-O-Si(R33)2-、
-O-(CH2)u’-Si(OCH3)2OSi(OCH3)2-、
-CONR34-(CH2)u’-(Si(R33)2O)m’-Si(R33)2-、
-CONR34-(CH2)u’-N(R34)-、または
-CONR34-(o-、m-またはp-フェニレン)-Si(R33)2-
[式中、R33、R34およびm’は、上記と同意義であり、
u’は1~20の整数、好ましくは2~6の整数、より好ましくは2~3の整数である。]を表す。Xcは、好ましくは-O-である。
-S-、
-C(O)O-、
-CONR34-、
-CONR34-(CH2)u’-(Si(R33)2O)m’-Si(R33)2-、
-CONR34-(CH2)u’-N(R34)-、または
-CONR34-(o-、m-またはp-フェニレン)-Si(R33)2-
[式中、各記号は、上記と同意義である。]
を表す。
-Xf-、
-Xf-C1-20アルキレン基、
-Xf-(CH2)s’-Xc-、
-Xf-(CH2)s’-Xc-(CH2)t’-
-Xf-Xd-、または
-Xf-Xd-(CH2)t’-
[式中、Xf、s’およびt’は、上記と同意義である。]
であり、
Xcが、-O-、または-CONR34-、
Xdが、-CONR34-、
R34は、各出現においてそれぞれ独立して、水素原子、フェニル基またはC1-6アルキル基(好ましくはメチル基)を表す。]
で表される基である。
-Xf-(CH2)s’-Xc-、
-Xf-(CH2)s’-Xc-(CH2)t’-
-Xf-Xd-、または
-Xf-Xd-(CH2)t’-
[式中、Xf、s’およびt’は、上記と同意義である。]
であり、
Xcが、-O-、または-CONR34-、
Xdが、-CONR34-、
R34は、各出現においてそれぞれ独立して、水素原子、フェニル基またはC1-6アルキル基(好ましくはメチル基)を表す。]
で表される基である。
単結合、
C1-20アルキレン基、
-(CH2)s’-Xc-(CH2)t’-、または
-Xd-(CH2)t’-
[式中、各記号は、上記と同意義である。]
であり得る。
単結合、
C1-20アルキレン基、
-(CH2)s’-O-(CH2)t’-、
-(CH2)s’-(Si(R33)2O)m’-Si(R33)2-(CH2)t’-、
-(CH2)s’-O-(CH2)u’-(Si(R33)2O)m’-Si(R33)2-(CH2)t’-、または
-(CH2)s’-O-(CH2)t’-Si(R33)2 -(CH2)u’-Si(R33)2-(CvH2v)-
[式中、R33、m’、s’、t’およびu’は、上記と同意義であり、vは1~20の整数、好ましくは2~6の整数、より好ましくは2~3の整数である。]
である。
Dは、
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CF2O(CH2)3-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-CONH-(CH2)3-、
-CON(CH3)-(CH2)3-、
-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、および
から選択される基であり、
Eは、-(CH2)ne-(neは2~6の整数)であり、
Dは、分子主鎖のPFPE1に結合し、Eは、PFPE1と反対の基に結合する。]
単結合、
-CH2OCH2-、
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CH2O(CH2)6-、
-CF2-CH2-O-CH2-、
-CF2-CH2-O-(CH2)2-、
-CF2-CH2-O-(CH2)3-、
-CF2-CH2-O-(CH2)6-、
-CH2O(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-、
-CH2OCF2CHFOCF2-、
-CH2OCF2CHFOCF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-、
-CH2OCH2CF2CF2OCF2-、
-CH2OCH2CF2CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF2CF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF2-、
-CH2OCH2CHFCF2OCF2CF2-、
-CH2OCH2CHFCF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CH2OCH2(CH2)7CH2Si(OCH3)2OSi(OCH3)2(CH2)2Si(OCH3)2OSi(OCH3)2(CH2)2-、
-CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)3-、
-CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)3-、
-CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)2-、
-CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)2-、
-(CH2)2-Si(CH3)2-(CH2)2-、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-(CH2)5-、
-(CH2)6-、
-CF2-、
-(CF2)2-、
-CF2-CH2-、
-CF2-(CH2)2-、
-CF2-(CH2)3-、
-CF2-(CH2)4-、
-CF2-(CH2)5-、
-CF2-(CH2)6-、
-CO-、
-CONH-、
-CONH-CH2-、
-CONH-(CH2)2-、
-CONH-(CH2)3-、
-CONH-(CH2)6-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CON(CH3)-(CH2)3-、
-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CON(CH3)-(CH2)6-、
-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CONH-(CH2)2NH(CH2)3-、
-CONH-(CH2)6NH(CH2)3-、
-CH2O-CONH-(CH2)3-、
-CH2O-CONH-(CH2)6-、
-S-(CH2)3-、
-(CH2)2S(CH2)3-、
-CONH-(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-、
-C(O)O-(CH2)3-、
-C(O)O-(CH2)6-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)2-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)3-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-CH2-、
-OCH2-、
-O(CH2)3-、
-OCFHCF2-、
-CH2OCH2-、
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CH2O(CH2)6-、
-CF2-CH2-O-CH2-、
-CF2-CH2-O-(CH2)2-、
-CF2-CH2-O-(CH2)3-、
-CF2-CH2-O-(CH2)6-、
-CH2OCF2CHFOCF2-、
-CH2OCF2CHFOCF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-、
-CH2OCH2CF2CF2OCF2-、
-CH2OCH2CF2CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF2CF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF2-、
-CH2OCH2CHFCF2OCF2CF2-、
-CH2OCH2CHFCF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-(CH2)5-、
-(CH2)6-、
-CF2-、
-(CF2)2-、
-CF2-CH2-、
-CF2-(CH2)2-、
-CF2-(CH2)3-、
-CF2-(CH2)4-、
-CF2-(CH2)5-、
-CF2-(CH2)6-、
-CONH-、
-CONH-CH2-、
-CONH-(CH2)2-、
-CONH-(CH2)3-、
-CONH-(CH2)6-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CON(CH3)-(CH2)3-、
-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CON(CH3)-(CH2)6-、
-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CONH-(CH2)2NH(CH2)3-、
-CONH-(CH2)6NH(CH2)3-、
-CH2O-CONH-(CH2)3-、
-CH2O-CONH-(CH2)6-、
-OCH2-、
-O(CH2)3-、
-OCFHCF2-、
であることが好ましい。
-CH2OCH2-、
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CH2O(CH2)6-、
-CF2-CH2-O-CH2-、
-CF2-CH2-O-(CH2)2-、
-CF2-CH2-O-(CH2)3-、
-CF2-CH2-O-(CH2)6-、
-CH2OCF2CHFOCF2-、
-CH2OCF2CHFOCF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-、
-CH2OCH2CF2CF2OCF2-、
-CH2OCH2CF2CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF2CF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF2-、
-CH2OCH2CHFCF2OCF2CF2-、
-CH2OCH2CHFCF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、
-CONH-、
-CONH-CH2-、
-CONH-(CH2)2-、
-CONH-(CH2)3-、
-CONH-(CH2)6-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CF2CONH(CH2)6-、
-CON(CH3)-(CH2)3-、
-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CON(CH3)-(CH2)6-、
-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)3-、
-CF2-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CF2-CON(CH3)-(CH2)6-、
-CF2-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CONH-(CH2)2NH(CH2)3-、
-CONH-(CH2)6NH(CH2)3-、
であることが好ましい。
単結合、
-Xf-、
炭素原子数1~6、好ましくは炭素原子数1~3のアルキレン基
-Xf-C1-6アルキレン基、好ましくは-Xf-C1-3アルキレン基、より好ましくは
-Xf-C1-2アルキレン基、
-C6H4-R52’-、
-CONR4’-R52’-、
-CONR4’-C6H4-R52’-、
-Xf-CONR4’-R52’-、
-Xf-CONR4’-C6H4-R52’-、
-CO-R52’-、
-CO-C6H4-R52’-、
-SO2NR4’-R52’-、
-SO2NR4’-C6H4-R52’-、
-SO2-R52’-、
-SO2-C6H4-R52’-、
-R51’-C6H4-、
-R51’-CONR4’-、
-R51’-CONR4’-C6H4-、
-R51’-CO-、
-R51’-CO-C6H4-、
-R51’-SO2NR4’-、
-R51’-SO2NR4’-C6H4-、
-R51’-SO2-、
-R51’-SO2-C6H4-、
-C6H4-
-CONR4’-、
-CONR4’-C6H4-、
-Xf-CONR4’-、
-Xf-CONR4’-C6H4-、
-CO-、
-CO-C6H4-、
-SO2NR4’-、
-SO2NR4’-C6H4-、
-SO2-、または
-SO2-C6H4-
(式中、R51’およびR52’は、それぞれ独立して、炭素原子数1~6、好ましくは炭素原子数1~3の直鎖のアルキレン基である。上記したように、上記アルキレン基は、置換または非置換であり、上記アルキレン基の置換基としては、例えばハロゲン原子、好ましくはフッ素原子を挙げることができる。
R4’は、水素原子またはメチル基である。)
であり得る。
-Xf-、
炭素原子数1~6、好ましくは炭素原子数1~3のアルキレン基、
-Xf-C1-6アルキレン基、好ましくは-Xf-C1-3アルキレン基、より好ましくは
-Xf-C1-2アルキレン基、
-CONR4’-R52’-、
-CONR4’-C6H4-R52’-、
-Xf-CONR4’-R52’-、
-Xf-CONR4’-C6H4-R52’-、
-R51’-CONR4’-、
-R51’-CONR4’-C6H4-、
-CONR4’-、
-CONR4’-C6H4-、
-Xf-CONR4’-、
-Xf-CONR4’-C6H4-、
-R51’-CONR4’-、または
-R51’-CONR4’-C6H4-、
であり得る。式中、Xf、R4’、R51’およびR52’は、それぞれ上記と同意義である。
-CONR4’-R52’-、
-CONR4’-C6H4-R52’-、
-Xf-CONR4’-R52’-、
-Xf-CONR4’-C6H4-R52’-、
-R51’-CONR4’-、
-R51’-CONR4’-C6H4-、
-CONR4’-、
-CONR4’-C6H4-、
-Xf-CONR4’-、または
-Xf-CONR4’-C6H4-、
であり得る。
単結合、
炭素原子数1~6のパーフルオロアルキレン基(例えば、-CF2-、-(CF2)2-等)、
炭素原子数1~6のアルキレン基、
-CF2-C1-6アルキレン基、
-CONH-、
-CONH-CH2-、
-CONH-(CH2)2-、
-CONH-(CH2)3-、
-CF2-CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CON(CH3)-、
-CON(CH3)-CH2-、
-CON(CH3)-(CH2)2-
-CON(CH3)-(CH2)3-、
-CF2-CON(CH3)-、
-CF2-CON(CH3)CH2-、
-CF2-CON(CH3)-(CH2)2-、
-CF2-CON(CH3)-(CH2)3-、
-CH2-CONH-、
-CH2-CONH-CH2-、
-CH2-CONH-(CH2)2-、
-CH2-CONH-(CH2)3-、
-CF2-CH2-CONH-、
-CF2-CH2-CONH-CH2-、
-CF2-CH2-CONH-(CH2)2-、
-CF2-CH2-CONH-(CH2)3-、
-CONH-C6H4-、
-CON(CH3)-C6H4-、
-CH2-CON(CH3)-CH2-、
-CH2-CON(CH3)-(CH2)2-、
-CH2-CON(CH3)-(CH2)3-、
-CON(CH3)-C6H4-、
-CF2-CONH-C6H4-、
-CF2-CON(CH3)-C6H4-、
-CF2-CH2-CON(CH3)-CH2-、
-CF2-CH2-CON(CH3)-(CH2)2-、
-CF2-CH2-CON(CH3)-(CH2)3-、
-CF2-CON(CH3)-C6H4-、
-CO-、
-CO-C6H4-、
-C6H4-、
-SO2NH-、
-SO2NH-CH2-、
-SO2NH-(CH2)2-、
-SO2NH-(CH2)3-、
-SO2NH-C6H4-、
-SO2N(CH3)-、
-SO2N(CH3)-CH2-、
-SO2N(CH3)-(CH2)2-、
-SO2N(CH3)-(CH2)3-、
-SO2N(CH3)-C6H4-、
-SO2-、
-SO2-CH2-、
-SO2-(CH2)2-、
-SO2-(CH2)3-、または
-SO2-C6H4-
などが挙げられる。
炭素原子数1~6のパーフルオロアルキレン基(例えば、-CF2-、-(CF2)2-等)、
炭素原子数1~6のアルキレン基、
-CF2-C1-6アルキレン基、
-CONH-、
-CONH-CH2-、
-CONH-(CH2)2-、
-CONH-(CH2)3-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CON(CH3)-、
-CON(CH3)-CH2-、
-CON(CH3)-(CH2)2-、
-CON(CH3)-(CH2)3-、
-CF2-CON(CH3)-、
-CF2-CON(CH3)CH2-、
-CF2-CON(CH3)-(CH2)2-、
-CF2-CON(CH3)-(CH2)3-、
-CH2-CONH-、
-CH2-CONH-CH2-、
-CH2-CONH-(CH2)2-、
-CH2-CONH-(CH2)3-、
-CF2-CH2-CONH-、
-CF2-CH2-CONH-CH2-、
-CF2-CH2-CONH-(CH2)2-、
-CF2-CH2-CONH-(CH2)3-、
-CONH-C6H4-、
-CON(CH3)-C6H4-、
-CH2-CON(CH3)-CH2-、
-CH2-CON(CH3)-(CH2)2-、
-CH2-CON(CH3)-(CH2)3-、
-CON(CH3)-C6H4-
-CF2-CONH-C6H4-、
-CF2-CON(CH3)-C6H4-、
-CF2-CH2-CON(CH3)-CH2-、
-CF2-CH2-CON(CH3)-(CH2)2-、
-CF2-CH2-CON(CH3)-(CH2)3-、
-CF2-CON(CH3)-C6H4-、
などが挙げられる。
-CONH-、
-CONH-CH2-、
-CONH-(CH2)2-、
-CONH-(CH2)3-、
-CF2CONH-、
-CF2CONHCH2-、
-CF2CONH(CH2)2-、
-CF2CONH(CH2)3-、
-CON(CH3)-、
-CON(CH3)-CH2-、
-CON(CH3)-(CH2)2-、
-CON(CH3)-(CH2)3-、
-CF2-CON(CH3)-、
-CF2-CON(CH3)CH2-、
-CF2-CON(CH3)-(CH2)2-、
-CF2-CON(CH3)-(CH2)3-、
-CH2-CONH-、
-CH2-CONH-CH2-、
-CH2-CONH-(CH2)2-、
-CH2-CONH-(CH2)3-、
-CF2-CH2-CONH-、
-CF2-CH2-CONH-CH2-、
-CF2-CH2-CONH-(CH2)2-、
-CF2-CH2-CONH-(CH2)3-、
-CONH-C6H4-、
-CON(CH3)-C6H4-、
-CH2-CON(CH3)-CH2-、
-CH2-CON(CH3)-(CH2)2-、
-CH2-CON(CH3)-(CH2)3-、
-CON(CH3)-C6H4-
-CF2-CONH-C6H4-、
-CF2-CON(CH3)-C6H4-、
-CF2-CH2-CON(CH3)-CH2-、
-CF2-CH2-CON(CH3)-(CH2)2-、
-CF2-CH2-CON(CH3)-(CH2)3-、または
-CF2-CON(CH3)-C6H4-、
などが挙げられる。
R41は、それぞれ独立して、水素原子、フェニル基、炭素原子数1~6のアルキル基、またはC1-6アルコキシ基、好ましくはメチル基であり;
各Rk1基において、Tのうち任意のいくつかは、分子主鎖のPFPEに結合する以下の基:
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CF2O(CH2)3-、
-CH2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-CONH-(CH2)3-、
-CON(CH3)-(CH2)3-、
-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、または
であり、別のTの1が、分子主鎖のPFPEと反対の基に結合する-(CH2)n”-(n”は2~6の整数)であり、存在する場合、残りのTは、それぞれ独立して、メチル基、フェニル基、C1-6アルコキシ基またはラジカル捕捉基もしくは紫外線吸収基であり得る。
・Rg3が水素原子である有機化合物、即ち、1分子中にシラノール基を少なくとも2有する有機ケイ素化合物、
・後述する式(E3)~(E5)で表される有機ケイ素化合物
等を挙げることができる。
上記有機ケイ素化合物において、上記シラノール基は、分子主鎖の両末端に存在することが好ましい。ここで、分子主鎖とは、該有機ケイ素化合物の分子中で相対的に最も長い結合鎖を表す。
である。
Rf1-Rg5-
上記式中、Rf1は1価のフッ素化ポリエーテル基である。上記Rf1としては、上記PFPEのCF2末端にCF3O-、CF3CF2O-、CF3CF2CF2O-、(CF3)2CFO-、またはCF3CF2CF2CF2O-等が結合された構造のものが例示される。
炭素原子数1~3のアルキレン基、
CH2CH2-NH-CH2CH2CH2、または
CH2-O-CH2CH2CH2である。
-(OC6F12)a”-(OC5F10)b”-(OC4F8)c”-(OC3F6)d”-(OC2F4)e”-(OCF2)f”-
で表される。PFPE2は、直鎖状であっても、分枝鎖状であってもよいが、好ましくは直鎖状である。
上記式中、a”、b”、c”およびd”は、それぞれ独立して0以上30以下の整数であり、e”およびf”は、それぞれ独立して1以上200以の整数である。好ましくは、a”、b”、c”、d”、e”およびf”は、それぞれ独立して、0以上30以下の整数である。好ましくは、a”、b”、c”、d”、e”およびf”の和は5以上であり、より好ましくは10以上、例えば10以上100以下である。添字a”、b”、c”、d”、e”またはf”を付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である。上記f”に対するe”の比は、1.0未満である。
-CH2CH2-、
-CH2CH2CH2-、
-CH2CH2CH2OCH2-、
-CH2CH2CH2-NH-CO-、
-CH2CH2CH2-N(Ph)-CO-(但し、Phはフェニル基である。)、
-CH2CH2CH2-N(CH3)-CO-、
-CH2CH2CH2-O-CO-
等の炭素原子数2~12の基が挙げられる。上記2価の有機基は、左側においてSi原子に、右側においてフッ素含有基にそれぞれ結合する。
PFPE2は、各出現においてそれぞれ独立して、上記と同意義であり(なお、以下の式において、PFPE2で表される基は、末端の酸素原子において、Rfで表される基に結合する。);
Rf”は、各出現においてそれぞれ独立して、上記と同意義であり;
Rk3は、各出現においてそれぞれ独立して、炭素原子数1~10のアルキル基、またはORk7で表されるアルコキシ基であり、好ましくは、メチル基またはORk7で表されるアルコキシ基であり、より好ましくはメチル基であり;
Rk4は、各出現においてそれぞれ独立して、水素原子、炭素原子数1~10のアルキル基、またはORk7で表されるアルコキシ基であり、好ましくは、水素原子、またはORk7で表されるアルコキシ基であり、より好ましくは水素原子であり;
Rk5は、各出現においてそれぞれ独立して、水素原子、炭素原子数1~10のアルキル基、またはORk7で表されるアルコキシ基であり、好ましくは、水素原子、またはORk7で表されるアルコキシ基であり、より好ましくは水素原子であり;
Rk6は、各出現においてそれぞれ独立して、水素原子、フッ素原子、1以上の水素原子がフッ素原子に置換されたアルキレン基であり、好ましくは、水素原子であり;
Rk7は、各出現においてそれぞれ独立して、炭素原子数1~10のアルキル基であり、好ましくは、炭素原子数1~6のアルキレン基であり;
上記1以上の水素原子がフッ素原子に置換されたアルキレン基に含まれる炭素原子数は、1~8であることが好ましく、1~6であることがより好ましく;
Rk8は、-(O-(CH2)α5)α6-で表され(ここで、酸素原子が-(CRk6 2)α1で表される基に結合する);
α1は、各出現においてそれぞれ独立して、1~10の整数、好ましくは2または3であり;
α2は、各出現においてそれぞれ独立して、1~50の整数、好ましくは10であり;
α3は、各出現においてそれぞれ独立して、1~50の整数、好ましくは3~5の整数であり;
α4は、各出現においてそれぞれ独立して、1~50の整数、好ましくは3~5の整数であり;
α5は、1~6の整数、好ましくは1~3、より好ましくは1であり;
α6は、0または1である。
パーフルオロヘキサン、CF3CF2CHCl2、CF3CH2CF2CH3、CF3CHFCHFC2F5、1,1,1,2,2,3,3,4,4,5,5,6,6-トリデカフルオロオクタン、1,1,2,2,3,3,4-ヘプタフルオロシクロペンタン((ゼオローラH(商品名)等)、C4F9OCH3、C4F9OC2H5、CF3CH2OCF2CHF2、C6F13CH=CH2、キシレンヘキサフルオリド、パーフルオロベンゼン、メチルペンタデカフルオロヘプチルケトン、トリフルオロエタノール、ペンタフルオロプロパノール、ヘキサフルオロイソプロパノール、HCF2CF2CH2OH、メチルトリフルオロメタンスルホネート、トリフルオロ酢酸およびCF3O(CF2CF2O)m1(CF2O)n1CF2CF3[式中、m1およびn1は、それぞれ独立して0以上1000以下の整数であり、m1またはn1を付して括弧でくくられた各繰り返し単位の存在順序は式中において任意であり、但しm1およびn1の和は1以上である。]、1,1-ジクロロ-2,3,3,3-テトラフルオロ-1-プロペン、1,2-ジクロロ-1,3,3,3-テトラフルオロ-1-プロペン、1,2-ジクロロ-3,3,3-トリフルオロ-1-プロペン、1,1-ジクロロ-3,3,3-トリフルオロ-1-プロペン、1,1,2-トリクロロ―3,3,3-トリフルオロ-1-プロペン、1,1,1,4,4,4-ヘキサフルオロ-2-ブテン、エチルパーフルオロブチルエーテル、およびメチルパーフルオロブチルエーテルからなる群から選択されるフッ素原子含有溶剤等が挙げられる。これらの溶剤は、単独で、または、2種以上の混合物として用いることができる。
-Rj5-Si(ORj6)3、または、下記式で表される基を挙げることができる。
-Zj1-Rfj1
で表される基である。なお、Zj1は、右側がRfj1に結合する。
[式中、Zj1は、-(CH2)j6-、または-(CH2)j7-Xj1-(式中、Xj1は-OCH2-、または-Yj1-NRj9-CO-(式中、Yj1は-CH2-または下記構造式:
上記-Si-(Z3-SiR72 3)2または-Si-(Z3-SiR72” 3)2で表される基は、具体的には、
-Si-Ra 2Rb l1Rc m1において、Raが-Z3-SiR72 3で表される基であり、l1およびm1の合計が1である、
-Si-Ra” 2Rb” l1Rc” m1において、Ra”が-Z3-SiR72” 3で表される基であり、l1およびm1の合計が1である、
-Si-R71 2R72 q1R73 r1において、R71が-Z3-SiR72 3で表される基であり、q1およびr1の合計が1である、または
-Si-R71 2R72” q1R73 r1において、R71が-Z3-SiR72 3で表される基であり、q1およびr1の合計が1である、を挙げることができる。
Rf5-(OC4F8)a’-(OC3F6)b’-(OC2F4)c’-(OCF2)d’-Rf6 ・・・(III)
式中、Rf5は、1個またはそれ以上のフッ素原子により置換されていてもよい炭素原子数1~16アルキル基(好ましくは、C1―16のパーフルオロアルキル基)を表し、Rf6は、1個またはそれ以上のフッ素原子により置換されていてもよい炭素原子数1~16アルキル基(好ましくは、C1-16パーフルオロアルキル基)、フッ素原子または水素原子を表し、Rf5およびRf6は、より好ましくは、それぞれ独立して、C1-3パーフルオロアルキル基である。
a’、b’、c’およびd’は、ポリマーの主骨格を構成するパーフルオロ(ポリ)エーテルの4種の繰り返し単位数をそれぞれ表し、互いに独立して0以上300以下の整数であって、a’、b’、c’およびd’の和は少なくとも1、好ましくは1~300、より好ましくは20~300である。添字a’、b’、c’またはd’を付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である。これら繰り返し単位のうち、-(OC4F8)-は、-(OCF2CF2CF2CF2)-、-(OCF(CF3)CF2CF2)-、-(OCF2CF(CF3)CF2)-、-(OCF2CF2CF(CF3))-、-(OC(CF3)2CF2)-、-(OCF2C(CF3)2)-、-(OCF(CF3)CF(CF3))-、-(OCF(C2F5)CF2)-および-(OCF2CF(C2F5))-のいずれであってもよいが、好ましくは-(OCF2CF2CF2CF2)-である。-(OC3F6)-は、-(OCF2CF2CF2)-、-(OCF(CF3)CF2)-および-(OCF2CF(CF3))-のいずれであってもよく、好ましくは-(OCF2CF2CF2)-である。-(OC2F4)-は、-(OCF2CF2)-および-(OCF(CF3))-のいずれであってもよいが、好ましくは-(OCF2CF2)-である。
Rf5-(OCF2CF2CF2)b’’-Rf6 ・・・(IIIa)
Rf5-(OCF2CF2CF2CF2)a’’-(OCF2CF2CF2)b’’-(OCF2CF2)c’’-(OCF2)d’’-Rf6 ・・・(IIIb)
これら式中、Rf5およびRf6は上記の通りであり;式(IIIa)において、b’’は1以上100以下の整数であり;式(IIIb)において、a’’およびb’’は、それぞれ独立して1以上30以下の整数であり、c’’およびd’’はそれぞれ独立して1以上300以下の整数である。添字a’’、b’’、c’’、d’’を付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である。
・PFPE硬化組成物の調製
実施例1
・端面保護剤の調製
PFPE含有化合物A100重量部、架橋剤としてテトラエトキシシラン1重量部、および硬化触媒として、テトライソプロパキシチタン0.5重量部を混合用のガラス容器に秤量し、マグネチックスターラーを用いて撹拌を行い、硬化性組成物を調製した。
PFPE含有化合物A
(C2H5O)3SiCH2CH2CH2NHCOCF2-(OC2F4)e-(OCF2)f-CF2CONHCH2CH2CH2Si(OC2H5)3
(式中、e=45、f=38)
2枚のスライドガラスを厚み100μmの透明接着フィルム(日東電工社製LUCIACS CS9864)で挟みスライドガラス/接着フィルム/スライドガラスの積層体を作製した。該積層体の端面に上記PFPE硬化組成物をシリンジにて塗布し、25℃の温度にて24時間静置し硬化させ、端面が保護された積層体を調製した。
作製したサンプルをオレイン酸中に浸漬させ、70℃の電気炉に入れ1週間加熱した後に積層体の状態を目視にて確認した。また浸漬前後での積層体のスライドガラス間の距離、積層体全体の重量変化率を算出した。重量変化が全くなかった場合を0%とする。
PFPE含有化合物Bを用いた以外は実施例1と同様の方法でサンプルを調製、評価を行った。
PFPE含有化合物B
H((CH3O)3SiCHCH2)3CF2-(OC2F4)e-(OCF2)f-CF2(CH2CHSi(OCH3)3)3H
(式中、e=40、f=58、e/f=0.7)
・端面保護剤の調製
PFPE含有化合物Cを100重量部に対して、架橋剤として化合物Dを4重量部、および、硬化触媒として1,3-ジビニル-1,1,3,3-テトラメチルジシロキサンのPt錯体を2%含むキシレン溶液0.4重量部を、混合用のガラス容器に秤量し、撹拌混合を行い、硬化性組成物を調製した。
PFPE含有化合物C
CH2=CHCH2OCH2CF2(OCF2CF(CF3))mOCF2CF2O(CF(CF3)CF2O)n-CF2CH2OCH2CH=CH2
(式中、m+n=54)
化合物D
積層体に保護層無しで評価を実施した。
Claims (8)
- 第1基材層、接着剤層、および第2基材層が、この順に積層された積層体であって、
前記積層体の端面が、パーフルオロポリエーテル基含有化合物を含む硬化性組成物より形成された層により覆われている、積層体。 - 前記パーフルオロポリエーテル基含有化合物が、パーフルオロポリエーテル基含有シラン化合物である、請求項1に記載の積層体。
- 前記パーフルオロポリエーテル基含有シラン化合物が、式(A)、(B)、(C)、または(D):
[式中:
PFPEは、各出現においてそれぞれ独立して、式:
-(OC6F12)a-(OC5F10)b-(OC4F8)c-(OC3X10 6)d-(OC2F4)e-(OCF2)f-
(式中、a、b、c、d、eおよびfは、それぞれ独立して0以上200以下の整数であって、a、b、c、d、eおよびfの和は少なくとも1であり、a、b、c、d、eまたはfを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意であり、X10は、各出現においてそれぞれ独立して、水素原子、フッ素原子または塩素原子である。)
で表される基であり;
R13は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し;
R14は、各出現においてそれぞれ独立して、水素原子または炭素原子数1~22のアルキル基を表し;
R11は、各出現においてそれぞれ独立して、水素原子またはハロゲン原子を表し;
R12は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し;
R11”、R12”、R13”、およびR14”は、それぞれ、R11、R12、R13、およびR14と同意義であり;
n1は、(-SiR13 n1R14 3-n1)単位毎または(-SiR13” n1R14” 3-n1)単位毎に独立して、0~3の整数であり;
ただし、式(A)、および(B)において、各出現においてそれぞれ独立して、R13およびR13”からなる群より選ばれる基が少なくとも2存在し;
X1は、各出現においてそれぞれ独立して、単結合または2~10価の有機基を表し;
X2は、各出現においてそれぞれ独立して、単結合または2価の有機基を表し;
tは、各出現においてそれぞれ独立して、1~10の整数であり;
α1は、各出現においてそれぞれ独立して、1~9の整数であり;
X3は、各出現においてそれぞれ独立して、単結合または2~10価の有機基を表し;
β1は、各出現においてそれぞれ独立して、1~9の整数であり;
X5は、各出現においてそれぞれ独立して、単結合または2~10価の有機基を表し;
γ1は、各出現においてそれぞれ独立して、1~9の整数であり;
Raは、各出現においてそれぞれ独立して、-Z3-SiR71 p1R72 q1R73 r1を表し;
Z3は、各出現においてそれぞれ独立して、酸素原子または2価の有機基を表し;
R71は、各出現においてそれぞれ独立して、Ra’を表し;
Ra’は、Raと同意義であり;
Ra中、Z3基を介して直鎖状に連結されるSiは最大で5個であり;
R72は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し;
R73は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し;
p1は、各出現においてそれぞれ独立して、0~3の整数であり;
q1は、各出現においてそれぞれ独立して、0~3の整数であり;
r1は、各出現においてそれぞれ独立して、0~3の整数であり;
Ra”は、各出現においてそれぞれ独立して、-Z3-SiR71 p1R72” q1R73 r1を表し;
R72”は、R72と同意義であり;
ただし、(-Z3-SiR71 p1R72 q1R73 r1)毎、または(-Z3-SiR71 p1R72” q1R73 r1)毎において、p1、q1およびr1の和は3であり、式(C)において、少なくとも1つのq1が1~3の整数であり;
Rbは、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し;
Rcは、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し;
Rb”、およびRc”は、それぞれ、Rb、およびRcと同意義であり;
k1は、各出現においてそれぞれ独立して、0~3の整数であり;
l1は、各出現においてそれぞれ独立して、0~3の整数であり;
m1は、各出現においてそれぞれ独立して、0~3の整数であり;
ただし、(SiRa k1Rb l1Rc m1)毎、または(SiRa” k1Rb” l1Rc” m1)毎において、k1、l1およびm1の和は3であり;
(C)において、Rb、Rb”、R72、およびR72”からなる群より選ばれる基が少なくとも2存在し;
X7は、それぞれ独立して、単結合または2~10価の有機基を表し;
δ1は、それぞれ独立して、1~9の整数であり;
Rdは、各出現においてそれぞれ独立して、-Z4-CR81 p2R82 q2R83 r2を表し;
Z4は、各出現においてそれぞれ独立して、酸素原子または2価の有機基を表し;
R81は、各出現においてそれぞれ独立して、Rd’を表し;
Rd’は、Rdと同意義であり;
Rd中、Z4基を介して直鎖状に連結されるCは最大で5個であり;
R82は、各出現においてそれぞれ独立して、-Y-SiR85 n2R86 3-n2を表し;
Yは、各出現においてそれぞれ独立して、2価の有機基を表し;
R85は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し;
R86は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し;
R83は、各出現においてそれぞれ独立して、水素原子、水酸基または低級アルキル基を表し;
p2は、各出現においてそれぞれ独立して、0~3の整数であり;
q2は、各出現においてそれぞれ独立して、0~3の整数であり;
r2は、各出現においてそれぞれ独立して、0~3の整数であり;
Rd”は、各出現においてそれぞれ独立して、-Z4-CR81 p2R82” q2R83 r2を表し;
R82”は、-Y-SiR85” n2R86” 3-n2を表し;
ただし、(-Z4-CR81 p2R82 q2R83 r2)毎または(-Z4-CR81 p2R82” q2R83 r2)毎において、p2、q2およびr2の和は3であり;
n2は、(-Y-SiR85 n2R86 3-n2)単位毎または(-Y-SiR85” n2R86” 3-n2)単位毎に独立して、0~3の整数を表し;
R85”、およびR86”は、それぞれ、R85、およびR86と同意義であり;
Reは、各出現においてそれぞれ独立して、-Y-SiR85 n2R86 3-n2を表し;
Re”は、各出現においてそれぞれ独立して、-Y-SiR85” n2R86” 3-n2を表し;
Rfは、各出現においてそれぞれ独立して、水素原子、水酸基または低級アルキル基を表し;
Rf”は、Rfと同意義であり;
k2は、各出現においてそれぞれ独立して、0~3の整数であり;
l2は、各出現においてそれぞれ独立して、0~3の整数であり;
m2は、各出現においてそれぞれ独立して、0~3の整数であり;
ただし、(CRd k2Re l2Rf m2)毎または(CRd” k2Re” l2Rf” m2)毎において、k2、l2およびm2の和は3であり、式(D)において、n2が1以上である-Y-SiR85 n2R86 3-n2で表される基およびn2が1以上である-Y-SiR85” n2R86” 3-n2で表される基からなる群より選ばれる基が2以上存在する。]
で表される少なくとも1種のパーフルオロポリエーテル基含有シラン化合物である、請求項2に記載の積層体。 - 前記パーフルオロポリエーテル基含有化合物が、分子末端に炭素-炭素二重結合を有するパーフルオロポリエーテル基含有化合物である、請求項1に記載の積層体。
- 分子末端に炭素-炭素二重結合を有するパーフルオロポリエーテル基含有化合物が、以下の式:
CH2=CH-Rk1-PFPE-Rk1-CH=CH2 (I)
[式中:
PFPEは、各出現においてそれぞれ独立して、式:
-(OC6F12)a-(OC5F10)b-(OC4F8)c-(OC3X10 6)d-(OC2F4)e-(OCF2)f-
(式中、a、b、c、d、eおよびfは、それぞれ独立して0以上200以下の整数であって、a、b、c、d、eおよびfの和は少なくとも1であり、a、b、c、d、eまたはfを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意であり、X10は、各出現においてそれぞれ独立して、水素原子、フッ素原子または塩素原子である。)
で表される基であり;
各出現においてそれぞれ独立して、単結合、または2価の有機基である。]
で表される化合物である、請求項4に記載の積層体。 - 前記接着剤が、エポキシ樹脂、アクリル樹脂、シリコーン樹脂、フェノール樹脂、ポリイミド樹脂、イミド樹脂、ポリビニルクロライド樹脂、ポリビニルブチラル樹脂、エチレンビニルアセテート樹脂から選択される樹脂を含む接着剤である、請求項1~5のいずれか1項に記載の積層体。
- 第1基材層および第2基材層が、それぞれ独立して、樹脂、金属、金属酸化物、セラミックおよびガラスからなる群から選択される材料から構成される基材層である、請求項1~6のいずれか1項に記載の積層体。
- 請求項1~7のいずれか1項に記載の積層体を有して成る物品。
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| US (1) | US20200392369A1 (ja) |
| EP (1) | EP3705287A4 (ja) |
| JP (2) | JP6970208B2 (ja) |
| KR (1) | KR102296530B1 (ja) |
| CN (1) | CN111295281A (ja) |
| TW (1) | TWI763946B (ja) |
| WO (1) | WO2019088098A1 (ja) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113199831A (zh) * | 2020-01-30 | 2021-08-03 | 普因特工程有限公司 | 层叠形阳极氧化膜结构物 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US11691387B2 (en) * | 2020-04-24 | 2023-07-04 | Point Engineering Co., Ltd. | Laminated anodic aluminum oxide structure, guide plate of probe card using same, and probe card having same |
| KR102472421B1 (ko) | 2022-05-06 | 2022-12-01 | 주식회사 엘시스 | 축산질병 예방 및 통제 관리를 위한 ict 기반의 지능형 스마트 안전 축사 제어 시스템 |
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- 2018-10-30 KR KR1020207011772A patent/KR102296530B1/ko active Active
- 2018-10-30 EP EP18874523.6A patent/EP3705287A4/en active Pending
- 2018-10-30 US US16/757,958 patent/US20200392369A1/en active Pending
- 2018-10-30 JP JP2019550412A patent/JP6970208B2/ja active Active
- 2018-10-30 WO PCT/JP2018/040328 patent/WO2019088098A1/ja not_active Ceased
- 2018-10-31 TW TW107138626A patent/TWI763946B/zh active
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2021
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Also Published As
| Publication number | Publication date |
|---|---|
| EP3705287A1 (en) | 2020-09-09 |
| TW201936706A (zh) | 2019-09-16 |
| KR20200057065A (ko) | 2020-05-25 |
| EP3705287A4 (en) | 2021-07-28 |
| JP2022001439A (ja) | 2022-01-06 |
| TWI763946B (zh) | 2022-05-11 |
| CN111295281A (zh) | 2020-06-16 |
| JP6970208B2 (ja) | 2021-11-24 |
| KR102296530B1 (ko) | 2021-09-02 |
| US20200392369A1 (en) | 2020-12-17 |
| JPWO2019088098A1 (ja) | 2020-07-16 |
| JP7198891B2 (ja) | 2023-01-04 |
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