WO2011016458A1 - 撥水膜形成用組成物、撥水膜付き基体およびその製造方法並びに輸送機器用物品 - Google Patents
撥水膜形成用組成物、撥水膜付き基体およびその製造方法並びに輸送機器用物品 Download PDFInfo
- Publication number
- WO2011016458A1 WO2011016458A1 PCT/JP2010/063118 JP2010063118W WO2011016458A1 WO 2011016458 A1 WO2011016458 A1 WO 2011016458A1 JP 2010063118 W JP2010063118 W JP 2010063118W WO 2011016458 A1 WO2011016458 A1 WO 2011016458A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- water
- compound
- repellent film
- composition
- substrate
- Prior art date
Links
- 0 CCC(C)(CC)N(*)[S+](*C)(*C)C(CC)(CC)C=C* Chemical compound CCC(C)(CC)N(*)[S+](*C)(*C)C(CC)(CC)C=C* 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
-
- C—CHEMISTRY; METALLURGY
- 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
- C09D183/14—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
- C07C69/78—Benzoic acid esters
-
- 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
- C08G77/60—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 in which all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/62—Nitrogen atoms
-
- 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
- C09D183/04—Polysiloxanes
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
-
- 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
- C09D183/16—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 in which all the silicon atoms are connected by linkages other than oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
- C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
- C09K2019/0448—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2219/00—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used
- C09K2219/03—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used in the form of films, e.g. films after polymerisation of LC precursor
Definitions
- the present invention provides a water-repellent film that can form a water-repellent film that has both the property of being easy to remove the adhered water droplets (hereinafter referred to as “water droplet removing property”), wear resistance, and weather resistance.
- the present invention relates to a composition for water, a substrate with a water-repellent film having a water-repellent layer formed from the composition for forming a water-repellent film, a method for producing the same, and an article for transport equipment comprising the substrate with a water-repellent film.
- water-repellent articles treated with the above water-repellent treatment agent or the like for example, articles used in the field of transportation and transportation are strongly imparted with wear resistance and weather resistance in addition to water droplet removability. It has been demanded.
- a coating solution containing fluoroalkylsilane and tetraethoxysilane is applied by a flow coating method to form a water-repellent coating (see Patent Document 3).
- Patent Document 4 water-repellent film-coated articles containing magnesium oxide, calcium oxide, strontium oxide, and boron oxide in a water-repellent film.
- a coating composition containing a light stabilizer having a hydrolyzable silyl group has been proposed (see Patent Document 5).
- a fluorinated organic group having an etheric oxygen bond includes a silane compound bonded to silicon for the purpose of forming a surface treatment layer having water droplet removal property, abrasion resistance, and weather resistance on the surface of the substrate.
- a water-repellent composition (see Patent Document 6) has been proposed.
- Patent Document 1 and Patent Document 2 have a problem that the wear resistance of the water-repellent article is not sufficient because the wear resistance of the dimethyl silicone compound and the alkylsilane compound is low.
- the technique described in Patent Document 3 has a problem that it is not easy to make the film thickness uniform in a large area and is not excellent in mass productivity, and the water drop removability when the surface shape changes during long-term use is reduced. There was a problem that it was easy to do.
- the technique described in Patent Document 5 there is a problem that the light stabilizer is actually deteriorated, the effect does not last for a long time, and the water drop removability tends to decrease.
- a water-repellent article that is excellent in water droplet removal property and has both wear resistance and weather resistance, particularly a water-repellent article that can be applied to transportation equipment is desired.
- the present invention has been made to solve the above-described problems, and has the following configuration.
- the composition for forming a water-repellent film of the present invention contains the following compound (A) and compound (B), or a compound represented by the following general formula (1a) and / or a partially hydrolyzed condensate thereof, and It includes a partial hydrolysis cocondensate with the compound represented by the general formula (2a) and / or a partial hydrolysis condensate thereof.
- Compound (A) at least one etheric oxygen selected from the group consisting of a compound represented by the following general formula (1a), a partially hydrolyzed condensate thereof, and a compound represented by the following general formula (1b) No fluorine-containing organosilicon compound R f1 —Y—Si (R 11 ) r (X 1 ) 3-r (1a)
- R f1 represents a perfluoroalkyl group which does not contain an etheric oxygen atom between carbon-carbon atoms having 1 to 20 carbon atoms, which may have a ring structure, Is a divalent organic group not containing a fluorine atom having 1 to 6 carbon atoms, R 11 is independently a hydrogen atom or a hydrocarbon group not containing a fluorine atom having 1 to 6 carbon atoms, and X 1 is independently A halogen atom, an alkoxy group or an isocyanate group, r is an integer of 0 to 2, R 1 is a hydrogen atom or a hydrocarbon group containing 1 to 3 carbon atoms and b is 1 to 100 (An integer is shown respectively.)
- Compound (B) containing at least one etheric oxygen selected from the group consisting of a compound represented by the following general formula (2a), a partially hydrolyzed condensate thereof, and a compound represented by the following general formula (2b) Fluorine-containing organosilicon compound R f2 —W—Z—Si (R 12 ) p (X 2 ) 3-p (2a)
- R f2 is a perfluoroalkyl in which an etheric oxygen atom may be inserted between carbon-carbon atoms having 1 to 20 carbon atoms which may have a ring structure
- W represents —O— (CF 2 CF 2 O) a —CF 2 —
- a represents an integer of 1 to 200
- Z represents a divalent organic group
- R 12 independently represents , A hydrogen atom or a hydrocarbon group containing no fluorine atom having 1 to 6 carbon atoms
- X 2 is independently a halogen atom, an alkoxy group or an isocyanate group
- p is an integer of 0 to 2
- R 2 is A hydrogen atom or a hydrocarbon group not containing a fluorine atom having 1 to 3 carbon atoms
- c is an integer of 1 to 100.
- the substrate with a water repellent film of the present invention is a substrate with a water repellent film having a substrate and a water repellent film on at least a part of the surface of the substrate, and the water repellent film is composed of one or more layers. And the outermost layer has a water-repellent layer formed using the water-repellent film-forming composition of the present invention.
- the water repellent film-forming composition of the present invention is applied to the surface of the substrate or the surface of the layer that is formed in advance on the surface of the substrate and forms the lowermost layer of the outermost layer.
- a method for producing a substrate with a water-repellent film according to the present invention which comprises a step of forming a water-repellent layer by curing.
- the present invention also provides an article for transport equipment comprising the substrate with a water repellent film of the present invention.
- the composition for forming a water-repellent film of the present invention it is possible to form a water-repellent film that has excellent water droplet removability and also has both abrasion resistance and weather resistance.
- the substrate with a water-repellent film of the present invention having a water-repellent layer formed using this composition for forming a water-repellent film and an article for transport equipment comprising the substrate with a water-repellent film are provided with water droplet removability and abrasion resistance. Excellent in weatherability and weather resistance.
- a substrate with a water-repellent film that is excellent in water droplet removability, abrasion resistance, and weather resistance can be obtained.
- the composition for forming a water-repellent film of the present invention is at least selected from the group consisting of a compound represented by the above general formula (1a), a partially hydrolyzed condensate thereof, and a compound represented by the above general formula (1b).
- composition for forming a water-repellent film of the present invention comprises a compound represented by the above general formula (1a) and / or a partial hydrolysis condensate thereof and a compound represented by the above general formula (2a) and / or its A partial hydrolysis cocondensate with a partial hydrolysis condensate is included.
- the excellent water droplet removability of the water repellent film (water repellent layer in the substrate with the water repellent film of the present invention) formed using the water repellent film forming composition of the present invention is the molecular structure of the compound (B). Is due to. More specifically, the fluorine-containing organic group containing an etheric oxygen atom contained in the compound (B) contributes to the improvement of the mobility or falling property of water droplets on the coating surface in the water-repellent film. In addition, by adding the compound (A) to the water repellent film-forming composition of the present invention, the water-repellent film removability and its wear resistance and weather resistance are enhanced.
- the fluorine atom of the fluorine-containing organic group containing an etheric oxygen atom is the said water-repellent film.
- High molecular chain mobility resulting from a structure in which surface energy is reduced and etheric oxygen atoms are linked contributes to efficient orientation of fluorine atoms in the water-repellent film. That is, it is considered that the high molecular chain mobility makes it possible to change the orientation of fluorine atoms corresponding to the movement of the water droplets on the surface of the water-repellent film, and as a result, the water droplets fall.
- the fluorine-containing organic group which does not have an etheric oxygen atom in the conventionally proposed surface treatment agent also contains a fluorine atom, the surface energy of the treatment layer formed from the surface treatment agent can be reduced.
- the fluorine-containing organic group having no etheric oxygen atom has a very rigid structure, the fluorine atoms present on the surface are difficult to change in orientation and cannot follow the movement of water droplets. For this reason, water drops are likely to fall down in a certain area, but it is difficult to fall down in another area, and the water drops are caught somewhere, and the fallability of the water drops is considered to be low.
- the compound (A) contained in the composition for forming a water repellent film of the present invention is a compound represented by the following general formula (1a), a partially hydrolyzed condensate thereof, and a compound represented by the following general formula (1b) It is a fluorine-containing organosilicon compound not containing at least one etheric oxygen selected from the group consisting of:
- the partial hydrolysis condensate of the compound represented by the following general formula (1a) will be described later. First, the compound (A) that is not a partial hydrolysis-condensation product will be described.
- the compound (A) may be composed only of the compound represented by the above formula (1a), may be composed only of the compound represented by the above formula (1b), or may be composed of a mixture thereof. Good.
- R f1 represents a perfluoroalkyl group that does not contain an etheric oxygen atom between carbon-carbon atoms having 1 to 20 carbon atoms, which may have a ring structure.
- R f1 may have a straight chain structure, a branched structure, a cyclic structure, or a structure partially having a branched structure and a cyclic structure as long as the above conditions are satisfied. Good. Specific examples of such R f1 include the following groups.
- C y F represents a perfluorocyclohexyl group.
- a d F represents a perfluoroadamantyl group.
- m and n each represents an integer of 0 to 15.
- R f1 in the present invention CF 3 (CF 2 ) 1 — is preferable, and a linear structure is more preferable. Further, preferred carbon number in R f1 is 3 to 8.
- Y which is a group that connects R f1 and a silicon atom, is a divalent organic group that does not contain a fluorine atom having 1 to 6 carbon atoms. There are no restrictions.
- Y is preferably — (CH 2 ) i — (i represents an integer of 1 to 6), —CONH (CH 2 ) j — (j represents an integer of 1 to 5) and —CONH And a divalent organic group selected from (CH 2 ) q NH (CH 2 ) 5-k — (k represents an integer of 1 to 4), and more preferably — (CH 2 ) 2 —, — CONH (CH 2 ) 3 —, —CONH (CH 2 ) 2 NH (CH 2 ) 3 — and the like can be mentioned.
- R 11 each independently represents a hydrogen atom or a hydrocarbon group containing no fluorine atom having 1 to 6 carbon atoms.
- R 11 is preferably a hydrocarbon group having 1 to 4 carbon atoms, a methyl group or an ethyl group is particularly preferred.
- R 11 is preferably a hydrogen atom.
- X 1 represents a halogen atom, an alkoxy group or an isocyanate group. These are all hydrolyzable groups. X 1 when r is 0 or 1 may be the same or different. X 1 is preferably a chlorine atom, an alkoxy group having 1 to 4 carbon atoms or an isocyanate group, and particularly preferably a chlorine atom. r is an integer of 0 to 2, but 0 or 1 is preferable because of excellent adhesion and durability of the formed layer.
- R 1 each independently represents a hydrogen atom or a hydrocarbon group not containing a fluorine atom having 1 to 3 carbon atoms. R 1 is preferably a hydrogen atom from the viewpoint of improving reactivity.
- b represents an integer of 1 to 100.
- b represents the number of units of silicon-nitrogen bond of the compound represented by the formula (1b), and in the present invention, 1 to 50 is preferable from the viewpoint of coatability.
- the compound (A) may be used alone or in combination of two or more.
- the compound (A) used in the present invention can be produced by a general method. Moreover, since there exists a commercial item as a compound (A), it is also possible to use such a commercial item for this invention.
- the compound (B) contained in the composition of the present invention is at least selected from the group consisting of a compound represented by the following general formula (2a), a partially hydrolyzed condensate thereof, and a compound represented by the following general formula (2b). It is a fluorine-containing organosilicon compound containing one kind of etheric oxygen.
- the partial hydrolysis-condensation product of the compound represented by the following general formula (2a) will be described later. First, the compound (B) that is not a partial hydrolysis-condensation product will be described.
- the compound (B) may be composed only of the compound represented by the above formula (2a), may be composed only of the compound represented by the above formula (2b), or may be composed of a mixture thereof. Good.
- R f2 is a perfluoroalkyl group having 1 to 20 carbon atoms (which may have a ring structure, and an etheric oxygen atom is inserted between the carbon-carbon atoms. May be used).
- the perfluoroalkyl group having 1 to 20 carbon atoms represented by R f2 may have a straight chain structure, a branched structure, or a cyclic structure. It may have a structure. Specific examples of such R f2 include the following groups.
- C y F represents a perfluorocyclohexyl group.
- a d F represents a perfluoroadamantyl group.
- m and n each represents an integer of 0 to 15.
- R f2 in the present invention CF 3 (CF 2 ) m — is preferable, and a linear structure is more preferable. Further, the number of carbon atoms in R f2 is preferably 1 to 16, particularly preferably 1 to 8.
- the perfluoroalkyl group in which an etheric oxygen atom is inserted between carbon-carbon atoms refers to a group in which an etheric oxygen atom is inserted between carbon-carbon atoms of the perfluoroalkyl group.
- a perfluoro (oxyethylene) group that is, —OCF 2 CF 2 —
- the perfluoro (oxyethylene) group is It is regarded as a perfluoro (oxyethylene) group in W in the formula.
- this perfluoro (oxyethylene) group is not continuous with the perfluoro (oxyethylene) group in W, it is a perfluoro (oxyethylene) group in R f2 .
- the etheric oxygen atom in R f2 may form a perfluoro (oxypropylene) group, but the perfluoro (oxypropylene) group has a trifluoromethyl group in the side chain, so that the intended effect is sufficiently obtained. There is a possibility that it cannot be demonstrated. Therefore, when the number of etheric oxygen atoms inserted into R f2 is 2 or more, a structure in which a unit of perfluoro (oxyethylene) group is repeated 2 or more is preferable.
- the perfluoroalkyl group having an etheric oxygen atom inserted therein preferably has no —OCF 2 O— structure.
- the absence of the —OCF 2 O— structure means that the structure cannot be detected by ordinary analytical methods ( 19 F-NMR (nuclear magnetic resonance), etc.).
- R f2 has a structure in which two or more perfluoro (oxyethylene) group units are repeated, —OCF 2 O— is often formed at one end of the structure.
- the —OCF 2 O— structure in R f2 is unstable and may cause a decrease in heat resistance.
- the number of oxygen atoms inserted is preferably 1 to 7, and more preferably 1 to 4.
- the position where the oxygen atom is inserted is between a carbon atom-carbon atom single bond, and the number of carbon atoms present between the oxygen atoms is 2 or more.
- W is a divalent organic group represented by —O— (CF 2 CF 2 O) a —CF 2 —, and a is an integer of 1 to 200 Indicates.
- a is preferably an integer of 3 to 50, more preferably 4 to 25, and still more preferably 5 to 10.
- Z represents a divalent organic group.
- the divalent organic group preferably has 10 or less carbon atoms and may have a hetero atom such as an oxygen atom or a nitrogen atom.
- the compound (B) is obtained by reacting a compound having R f2 —W— with a compound having a silicon atom (that is, the functional group at the silicon atom side end of W and the functional group of the compound having a silicon atom).
- Z is preferably a divalent organic group formed by a reaction between such a reactive group-containing organic group bonded to a silicon atom and the reactive group bonded to the terminal of W.
- a compound in which Z is an alkylene group can be obtained by bonding a compound having an alkenyl group at the silicon atom side end of W and a silicon compound having a hydrogen atom bonded to the silicon atom by a hydrosilylation reaction.
- Preferred Z is a divalent organic group formed by a reaction between a functional group at the silicon atom side terminal of W and a functional group of a compound having a silicon atom.
- the reactive group bonded to the difluoromethylene group at the terminal of W include a reactive group having a carbonyl group such as a carboxyl group, a halocarbonyl group, and an alkoxycarbonyl group, and a hydroxymethyl group.
- examples of the reactive group in the compound having a silicon atom include a reactive group possessed by an organic group bonded to the silicon atom.
- chlorine bonded to a carbon atom such as an amino group in a 3-aminopropyl group, N- (2-aminoethyl) -3-aminopropyl group, an isocyanate group such as a 3-isocyanatopropyl group, or a 3-chloropropyl group
- examples thereof include an atomic group, an epoxy group such as a 3-glycidyloxypropyl group, a hydroxyl group such as a 3-hydroxypropyl group, and a mercapto group such as a 3-mercaptooxypropyl group.
- Z represented by —CONHC 3 H 6 — is formed by the reaction of a reactive group having a carbonyl group with a 3-aminopropyl group.
- Z includes —CONHC 3 H 6 —, —CONHC 2 H 4 —, —CH 2 OCONHC 3 H 6 —, —COCH 2 CH (OH) CH 2 OC 3 H 6 —, —CH 2 OCH 2 CH (OH ) Any divalent selected from CH 2 OC 3 H 6- , -CH 2 OC 3 H 6- , -CF 2 OC 3 H 6- , -C 2 H 4 -and -C 3 H 6- Organic groups are preferred. Among these, —CONHC 3 H 6 —, —CONHC 2 H 4 —, and —C 2 H 4 — are preferable.
- R 12 in each of the above formulas (2a) and (2b) include the same groups as R 11 in the above formulas (1a) and (1b). Preferred embodiments are also the same as described above.
- Examples of X 2 in formula (2a) include the same groups as X 1 in formula (1a). Preferred embodiments are also the same as described above. P in the formula (2a) is an integer of 0 to 2, but 0 or 1 is preferable because of excellent adhesion and durability of the formed layer.
- R 2 in formula (2b) examples include the same groups as R 1 in formula (1b). Preferred embodiments are also the same as described above.
- c represents the number of units of the silicon-nitrogen bond of the compound represented by the formula (2b). In the present invention, 1 to 50 is preferable from the viewpoint of coatability.
- the compound (B) may be used alone or in combination of two or more.
- the compound (B) used in the present invention can be produced by a known method.
- the compounds (B1) to (B6) can be specifically produced by the method described in WO2009-008380.
- the compound represented by the general formula (1a) and the compound represented by the general formula (2a) may each be a partially hydrolyzed condensate.
- the partially hydrolyzed condensate is an oligomer (a product formed by hydrolyzing all or part of a hydrolyzable silyl group in a solvent in the presence of a catalyst such as an acid catalyst or an alkali catalyst and water, and then dehydrating and condensing it). Multimer).
- the degree of condensation (degree of multimerization) of this partially hydrolyzed condensate must be such that the product is dissolved in the solvent.
- the compound (A) contained in the composition for forming a water-repellent film of the present invention may be a partially hydrolyzed condensate of the compound represented by the general formula (1a).
- the compound (B) May be a partially hydrolyzed condensate of the compound represented by the general formula (2a).
- these may each include an unreacted compound represented by the general formula (1a) and a compound represented by the general formula (2a).
- composition for forming a water-repellent film of the present invention contains the compound (A) and the compound (B).
- the said compound (A) and the compound (B) may contain the compound demonstrated above in the composition for water-repellent film formation of this invention as it is.
- the composition for forming a water-repellent film of the present invention comprises compound (A) as a compound represented by general formula (1a) and / or a partially hydrolyzed condensate thereof, and compound (B) as represented by general formula (2a).
- the compound is preferably contained as a partially hydrolyzed condensate and / or a partially hydrolyzed condensate thereof, and in that case, it is more preferably contained as a partially hydrolyzed cocondensate of compound (A) and compound (B).
- the partially hydrolyzed cocondensate of the compound (A) and the compound (B) is the same as described above, and all or one of the hydrolyzable silyl groups in the presence of a catalyst such as an acid catalyst or an alkali catalyst in a solvent.
- a catalyst such as an acid catalyst or an alkali catalyst in a solvent.
- the degree of condensation (degree of multimerization) of this partially hydrolyzed cocondensate must be such that the product is soluble in the solvent.
- the partial hydrolysis cocondensate here is a compound represented by the general formula (1a) as a compound (A) and / or a partial hydrolysis condensate thereof, and a general formula (2a) as a compound (B). These are produced by reacting these in a solvent containing the compound and / or its partial hydrolysis-condensation product, and may contain unreacted compound (A) or compound (B). .
- a compound represented by the general formula (1a) (not a partially hydrolyzed condensate) is used as the compound (A), and a general formula ( It is preferable to use a compound represented by 2a) (not a partially hydrolyzed condensate thereof).
- the partially hydrolyzed cocondensate of the compound (A) and the compound (B) is a compound represented by a predetermined amount of the general formula (1a) and / or a partially hydrolyzed condensate thereof and a predetermined amount of the general formula (2a).
- a catalyst such as an acid catalyst or an alkali catalyst and water for a predetermined time.
- the acid catalyst hydrochloric acid, nitric acid, acetic acid, sulfuric acid, phosphoric acid, sulfonic acid, methanesulfonic acid, p-toluenesulfonic acid and the like can be used.
- the alkali catalyst sodium hydroxide, potassium hydroxide, ammonia or the like can be used.
- water necessary for hydrolysis can be present in the reaction system.
- the reaction can be promoted by heating in the presence of a catalyst and water, if the reaction proceeds too much, the degree of condensation may increase and the product may become insoluble in the solvent.
- the reaction is preferably performed at room temperature.
- the obtained solution of the partially hydrolyzed cocondensate can be used as it is as the composition for forming a water-repellent film of the present invention.
- a water repellent film having higher performance can be formed by using the partial hydrolysis cocondensate.
- the water repellent film is composed of a hydrolysis cocondensate of both compounds, A film in which units derived from both compounds are uniformly distributed is obtained.
- the hydrolysis cocondensate of both compounds is formed in a relatively short time. There is a possibility that the uniformity of the distribution of units derived from both compounds may be reduced. It is considered that this uniformity is improved by preparing in advance a partially hydrolyzed cocondensate containing units derived from both compounds.
- the composition ratio of the active ingredient in the composition for forming a water-repellent film of the present invention can be determined from the amounts of the compound (A) and the compound (B) to be used.
- a composition ratio can be determined by the ratio of both the compounds used in order to manufacture a composition.
- the composition for forming a water-repellent film of the present invention contains the partially hydrolyzed cocondensate, it is difficult to measure the composition ratio of the active ingredient in the partially hydrolyzed cocondensate.
- the composition ratio of an active ingredient shall be determined with the raw material composition before manufacturing a partial hydrolysis cocondensate.
- the composition ratio of the active ingredient is determined from the amounts of the compound (A) and the compound (B) used as raw materials for the partially hydrolyzed cocondensate.
- the composition ratios of the unit of the compound represented by the general formula (1a) and the unit of the compound represented by the general formula (2a) in the condensate are assumed to be the same as the composition ratios of both raw material compounds used.
- the content ratio of the compound (B) in the composition for forming a water-repellent film of the present invention is represented by [compound (B)] / [compound (A) + compound (B)] ⁇ 100.
- the mass percentage of the compound (B) with respect to the total mass of (B) is preferably 10 to 90% by mass, more preferably 10 to 60% by mass, and particularly preferably 10 to 30% by mass. .
- the content ratio of the compound (A) in the composition for forming a water-repellent film of the present invention is 90 to 10 as a mass percentage of the compound (A) with respect to the total mass of the compound (A) and the compound (B).
- % By weight is preferable, 90 to 40% by weight is more preferable, and 90 to 70% by weight is particularly preferable.
- the mass percentage here means a composition ratio calculated by the amount of the compound (A) and the compound (B) before the reaction.
- the composition for forming a water repellent film of the present invention comprises the compound (A) and the compound (B), or the compound represented by the general formula (1a) and / or a partial hydrolysis condensate thereof and the general formula (2a). And / or a partially hydrolyzed cocondensate with the partially hydrolyzed condensate thereof (which may contain the compound (A) and / or the compound (B) if necessary).
- an organic solvent is usually included.
- the organic solvent is not particularly limited as long as it dissolves essential components.
- organic solvent alcohols, ethers, ketones, aromatic hydrocarbons, paraffin hydrocarbons, acetate esters and the like are preferable, and organic solvents containing fluorine atoms (for example, fluoroalcohols, fluorohydrocarbons) are particularly preferable. Is preferred.
- the organic solvent is not limited to one kind, and two or more kinds of solvents having different polarities and evaporation rates may be mixed and used.
- the composition for forming a water-repellent film of the present invention contains a partially hydrolyzed condensate or a partially hydrolyzed cocondensate, it may contain a solvent used for producing these, and the solvent and the water-repellent film.
- the organic solvent of the composition for forming a water film may be the same.
- the composition for forming a water-repellent film may contain components such as a catalyst used in partial hydrolysis condensation.
- the composition for forming a water-repellent film containing the partially hydrolyzed cocondensate is preferably a solution of the partially hydrolyzed cocondensate obtained by the production of the partially hydrolyzed cocondensate.
- the proportion of the organic solvent in the composition for forming a water-repellent film of the present invention is preferably 100,000 parts by mass or less, particularly 10,000 based on 100 parts by mass of the total mass of the compound (A) and the compound (B).
- the mass part or less is preferable. If an amount exceeding 100,000 parts by mass is used, processing unevenness may occur in the resulting water-repellent film.
- the composition for forming a water repellent film of the present invention may contain a functional additive as an optional component depending on the purpose within a range not impairing the effects of the present invention.
- the functional additive is preferably selected in consideration of reactivity or compatibility with essential components, and non-fluorinated water repellent materials such as one-end reactive polydimethylsiloxane and both-end reactive polydimethylsiloxane.
- Preferred examples include ultrafine particles of metal oxides such as silica, alumina, zirconia, and titania, coloring materials such as dyes or pigments, antifouling materials, curing catalysts, and various resins.
- the amount of the functional additive added is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the solid content of the water repellent film-forming composition (components excluding volatile components such as organic solvents). Excessive addition of a functional additive to the composition for forming a water-repellent film may lead to a decrease in performance such as water droplet removability of the resulting water-repellent film.
- a catalyst such as an acid catalyst.
- a catalyst may be added.
- the catalyst is preferably an acid catalyst. The presence of the catalyst makes it possible to form a water-repellent film having good wear resistance and weather resistance.
- the composition is applied to the surface of the substrate by a method such as brush coating, flow coating, spin coating, dip coating, squeegee coating, spray coating, or hand coating, and in air or nitrogen atmosphere, as necessary.
- a water-repellent film can be formed by curing after drying. The curing conditions are appropriately controlled depending on the type and concentration of the water-repellent film forming composition to be used. Preferred conditions include a temperature of 20 to 50 ° C. and a humidity of 50 to 90% RH.
- the time for curing depends on the type, concentration, curing conditions, and the like of the water-repellent film forming composition to be used, but is generally preferably 1 to 72 hours. Depending on the treatment method, an excess component may be generated and the appearance quality may be impaired. However, the appearance may be adjusted by removing the excess component by solvent wiping or empty wiping.
- the thickness of the water-repellent film formed from the composition for forming a water-repellent film of the present invention is not particularly limited. However, in consideration of economy, the thickness is preferably 50 nm or less, and the lower limit is the thickness of the monomolecular layer. is there.
- the substrate with a water repellent film of the present invention is a substrate with a water repellent film having a substrate and a water repellent film on at least a part of the surface of the substrate, and the water repellent film is composed of one or more layers, and The outermost layer has a water-repellent layer formed by using the water-repellent film forming composition of the present invention.
- the substrate used for the substrate with a water-repellent film of the present invention is not particularly limited as long as it is a substrate made of a material that is generally required to impart water repellency.
- Metal, plastic, glass, ceramic, or a combination thereof (composite material, A substrate made of a laminated material or the like is preferably used.
- a transparent substrate such as glass or plastic is particularly preferable.
- the glass include ordinary soda lime glass, borosilicate glass, non-alkali glass, and quartz glass. Among these, soda lime glass is particularly preferable.
- the plastic include acrylic resins such as polymethyl methacrylate, aromatic polycarbonate resins such as polyphenylene carbonate, and aromatic polyester resins such as polyethylene terephthalate (PET). Among these, polyethylene terephthalate (PET) ) Is preferred.
- the shape of the substrate may be a flat plate, or the entire surface or a part thereof may have a curvature.
- the thickness of the substrate can be appropriately selected depending on the use of the substrate with a water-repellent film, but is generally preferably 1 to 10 mm.
- the substrate used in the present invention may have an acid treatment (treatment with diluted hydrofluoric acid, sulfuric acid, hydrochloric acid, etc.), alkali treatment (treatment with an aqueous sodium hydroxide solution) or discharge depending on the purpose. Those subjected to treatment (plasma irradiation, corona irradiation, electron beam irradiation, etc.) or the like may be used. Further, the substrate may have a surface provided with various films formed by vapor deposition film, sputtered film, wet method or the like. When the substrate is soda lime glass, it is preferable in terms of durability to provide a film that prevents elution of Na ions. In the case where the substrate is glass manufactured by the float process, it is preferable in terms of durability to provide a water-repellent film on the top surface with a small amount of tin on the surface.
- the water-repellent film formed on at least a part of the surface of the substrate is composed of one or more layers, and the composition for forming a water-repellent film of the present invention is used for the outermost layer.
- a layer made of a water-repellent film (water-repellent layer).
- the water-repellent film in the present invention may be composed of only the water-repellent layer, and may have a layer other than the water-repellent layer in addition to the water-repellent layer depending on the purpose.
- the water repellent layer of the substrate with a water repellent film of the present invention is formed on the outermost layer of the water repellent film.
- the water repellent layer that the water repellent film has as the outermost layer can be formed on the substrate as the outermost layer of the water repellent film by the above-described method using the water repellent film forming composition of the present invention. It is.
- the method for producing a substrate with a water-repellent film when the water-repellent film is composed only of a water-repellent layer is the formation of the water-repellent film of the present invention on the substrate surface.
- cure is mentioned.
- Examples of the method include a step of applying a water-repellent film-forming composition to the surface of a layer that is a lower layer of the layer (outermost layer) in the same manner as described above, and curing the composition to form a water-repellent layer.
- it is a method having a step of forming a water-repellent layer by applying and curing a water-repellent film-forming composition on the surface of a layer that is formed in advance on the surface of the substrate and that is the lowermost layer of the water-repellent film. .
- the thickness of the water-repellent layer in the substrate with a water-repellent film of the present invention is not particularly limited as long as sufficient water droplet removal property and durability such as wear resistance and weather resistance are compatible.
- the thickness of such a water-repellent layer is preferably 2 to 30 nm, more preferably 5 to 20 nm when the water-repellent film is composed of only the water-repellent layer. Even when the water-repellent film has a layer other than the water-repellent layer, such as the following intermediate layer, the thickness of the water-repellent layer is preferably 2 to 30 nm, and more preferably 5 to 20 nm.
- the thickness of the water repellent layer can be appropriately controlled depending on the concentration of the water repellent film forming composition to be used, coating conditions, heating conditions, and the like.
- the water-repellent film preferably further includes an intermediate layer mainly composed of silica between the substrate and the water-repellent layer as a layer other than the water-repellent layer. .
- an intermediate layer mainly composed of silica between the substrate and the water-repellent layer as a layer other than the water-repellent layer.
- the intermediate layer mainly composed of silica of the water-repellent film is at least one selected from the group consisting of a compound represented by the following general formula (3), a partially hydrolyzed condensate thereof, and perhydropolysilazane. It can form using the composition for intermediate
- X 3 represents a halogen atom, an alkoxy group or an isocyanate group, and may be the same or different. Among these, X 3 is preferably a chlorine atom, an alkoxy group having 1 to 4 carbon atoms, or an isocyanate group, and four X 3 are preferably the same.
- Si (NCO) 4 , Si (OCH 3 ) 4 , Si (OC 2 H 5 ) 4 and the like are preferably used as the compound represented by the general formula (3).
- These partial hydrolysis condensates are obtained by the same method as described in the production of the compound represented by the general formula (1a) and the partial hydrolysis condensate of the compound represented by the general formula (2a). be able to.
- Perhydropolysilazane is a linear or cyclic oligomer having a structure represented by —SiH 2 —NH—SiH 2 —, and the number of silicon atoms per molecule is preferably 2 to 500.
- the compound having a structure in which all of the groups bonded to the silicon atom and the nitrogen atom are hydrogen atoms.
- perhydropolysilazanes There are commercially available perhydropolysilazanes, and such commercially available products can be used in the present invention.
- one type of compound (C) may be used alone, or two or more types may be used in combination.
- the intermediate layer forming composition for forming the intermediate layer of the water-repellent film is a compound represented by the general formula (1a) in addition to the compound (C).
- Specific examples of the compound (A) in the composition for forming an intermediate layer include the same compounds as the compound (A) described in the composition for forming a water repellent film. Examples thereof include the same compounds as the preferred compounds used for the composition.
- 1 type of a compound (A) may be used independently, and 2 or more types may be used together.
- the compound (C) and the compound (A) may be contained in the composition for forming an intermediate layer as they are as described above, and more specifically, both, more specifically, the compound (C).
- a partially hydrolyzed cocondensate may be contained.
- the partially hydrolyzed cocondensate is contained in the intermediate layer forming composition instead of the compound (C).
- the intermediate layer forming composition contains the compound (C) together with the partially hydrolyzed cocondensate. You may contain.
- the compound (A) may be contained together with this partially hydrolyzed cocondensate.
- the partially hydrolyzed cocondensate of the compound (C) and the compound (A) is the same as the partially hydrolyzed cocondensate of the compound (A) and the compound (B), and the general formula as the compound (C) is used. It can be produced from the compound represented by (3) and / or its partial hydrolysis condensate and the compound represented by the above general formula (1a) as the compound (A) and / or its partial hydrolysis condensate. it can.
- the concept of the water-repellent film in the present invention is not a state in which the boundary line can be strictly drawn, and some or all of the interfaces may be intermingled with each other as viewed in the micro.
- the intermediate layer obtained has an adhesive property between the substrate and the water-repellent layer formed from the water-repellent film-forming composition. Further, the effect of the reactive group of the compound (C) increases the denseness of the obtained intermediate layer, and the denseness of the entire water-repellent film also increases, which contributes to the improvement of the durability. It is done.
- the content ratio of the compound (A) in the composition for forming an intermediate layer used in the present invention is represented by [compound (A)] / [compound (A) + compound (C)] ⁇ 100.
- the mass percentage of the compound (A) with respect to the total mass of (C) is preferably 5 to 70 mass%, more preferably 5 to 50 mass%.
- the content ratio of the compound (C) in the composition for forming an intermediate layer of the present invention is 95 to 30% by weight as the mass percentage of the compound (C) with respect to the total mass of the compound (A) and the compound (C). %, And more preferably 95 to 50% by mass.
- the mass percentage here is a case where the composition for forming an intermediate layer contains a partially hydrolyzed cocondensate as in the content ratio of the compound (A) and the compound (B) in the water repellent film forming composition. Means the mass percentage calculated using the amount of the compound (C) and the compound (A) before the hydrolysis cocondensation reaction for the partial hydrolysis cocondensation reaction product.
- the intermediate layer forming composition may consist of only the compound (C), or the compound (C) and the compound (A), or the compound represented by the general formula (3) and / or the compound Partially hydrolyzed condensate and compound represented by general formula (1a) and / or partially hydrolyzed condensate of the partially hydrolyzed condensate (compound (C) and / or compound (A) if necessary)
- an organic solvent is included in consideration of economic efficiency, workability, ease of controlling the thickness of the treatment layer, and the like.
- the organic solvents described in the composition for forming a water-repellent film can be preferably used.
- the amount of the organic solvent used in the intermediate layer forming composition can be the same as in the case of the water repellent film forming composition. That is, the amount of the organic solvent used in the composition for forming an intermediate layer is, for example, compound (C) when only the compound (C) is contained as a solid content with respect to 100 parts by mass of the solid content contained in the composition. ), Or in the case where only the compound (C) and the compound (A) are contained as a solid content, the amount is 100,000 parts by mass or less with respect to 100 parts by mass of the total mass. The amount is preferable, and the amount that is 10,000 parts by mass or less is more preferable. If an amount exceeding 100,000 parts by mass is used, processing unevenness may occur in the resulting water-repellent film.
- the amount of the organic solvent used in the composition for forming an intermediate layer is more preferably 3,500 parts by mass or less with respect to 100 parts by mass of the total mass of solids contained in the composition, and 2,000. It is particularly preferable that the amount is not more than part by mass.
- the film thickness of the intermediate layer formed using this can be easily increased, and the water repellent film It is possible to contribute to the improvement of alkali resistance, salt water resistance and the like.
- the lower limit of the amount of the organic solvent used in the intermediate layer forming composition is not particularly limited, but as described above, considering the economy, workability, ease of controlling the thickness of the treatment layer, etc., the composition It is preferable that 500 mass parts is made into a minimum with respect to 100 mass parts of total mass of solid content which a thing contains.
- the composition for forming an intermediate layer may contain a functional additive depending on the purpose as long as the effects of the present invention are not impaired.
- the functional additive those described in the composition for forming a water-repellent film are preferably mentioned.
- the composition for forming an intermediate layer may contain components such as an acid catalyst as necessary, similarly to the composition for forming a water-repellent film.
- the method for forming the intermediate layer using the intermediate layer forming composition is preferably the same method as the water repellent film forming method described in the water repellent film forming composition of the present invention.
- the thickness of the intermediate layer formed from the composition for forming an intermediate layer is not particularly limited, but if it is too thick, damage is likely to be noticeable, and therefore it is preferably 50 nm or less.
- the lower limit is the thickness of the monomolecular layer.
- the thickness of the intermediate layer can be appropriately controlled by the concentration of the intermediate layer forming composition, coating conditions, heating conditions, and the like.
- the thickness of the entire water-repellent film is the maintenance of the function of the water-repellent film in the present invention, that is, considering sufficient economics such as having sufficient water droplet removal properties, wear resistance, weather resistance, etc. 2 to 100 nm is preferable, and 5 to 20 nm is more preferable.
- the intermediate layer forming composition is applied to the substrate surface and cured to form an intermediate layer mainly composed of silica, and the water repellent film forming composition of the present invention is formed on the surface of the intermediate layer.
- the intermediate layer forming composition is applied to the surface of the substrate and held for a certain period of time to form a coating film.
- the water repellent film forming composition After the water repellent film forming composition is applied to the surface and the coating film is formed, an appropriate layer is formed.
- an appropriate layer By performing the curing process under conditions, it is possible to simultaneously perform the curing process for forming the intermediate layer and the curing process for forming the water-repellent layer.
- the thus obtained water-repellent film of the substrate with a water-repellent film of the present invention has sufficient water droplet removal properties and durability such as wear resistance and weather resistance.
- fluoroalkylene-based carbon —CF 2 —
- fluoroether-based carbon —CF 2 O-
- Abundance ratio of fluoroether carbon to fluoroalkylene based carbon in the water-repellent film is measured by X-ray photoelectron spectrometer [-CF 2 O -] / [ - CF 2 -] It can be expressed in peak ratio.
- the [—CF 2 O —] / [— CF 2 —] peak ratio measured by an X-ray photoelectron spectrometer is 0.1 to 10.0. It is preferable that it is 0.1 to 5.0.
- the —CF 2 — structure in the water-repellent film appears as a peak around 291.5 eV when the C1sNarrow spectrum on the surface of the water-repellent film is measured using an X-ray photoelectron spectrometer.
- the —CF 2 O— structure appears as a peak in the vicinity of 293 eV of the C1sNarrow spectrum. Therefore, the [—CF 2 O —] / [— CF 2 —] peak ratio was obtained by measuring the C1sNarrow spectrum on the surface of the water-repellent film of the sample to be obtained using an X-ray photoelectron spectrometer.
- the peak around 291.5 eV derived from —CF 2 — and the peak around 293 eV derived from —CF 2 O— are separated from each other by the curve fitting function of an X-ray photoelectron spectrometer.
- the resulting, from that value [peak height around -CF 2 O-derived 293EV] / is can be calculated as [- - CF 2 peak heights around 291.5eV derived.
- the water droplet removability on the surface of the water repellent film of the substrate with the water repellent film of the present invention is a property that the adhesion of water droplets is small and the adhered water droplets can be easily removed.
- X-ray photoelectron spectroscopy (ESCA) It can be evaluated by the peak ratio of F1s / Si2p measured by the surface roughness Ra measured by a scanning probe microscope (SPM).
- the peak ratio of F1s / Si2p on the surface of the water-repellent film measured by X-ray photoelectron spectroscopy is used as an index indicating the ratio of fluorine atoms and silicon atoms present on the surface of the water-repellent film.
- the larger the peak ratio value the higher the proportion of fluorine atoms present on the surface of the water-repellent film, which means better water drop removal.
- the F1s / Si2p peak ratio measured by X-ray photoelectron spectroscopy (ESCA) is preferably 1.5 to 7.0. More preferably, it is 0 to 6.0.
- the surface roughness (Ra) on the surface of the water-repellent film measured by a scanning probe microscope (SPM) means that the smaller this value is, the more difficult the water is to adhere to the surface of the water-repellent film and the easier it is to remove.
- the Ra is preferably 0.1 to 5.0 nm, more preferably 0.1 to 2.0.
- both the peak ratio of F1s / Si2p and the surface roughness Ra are within the above preferred range, that is, the peak ratio of F1s / Si2p is More preferably, it is 1.5 to 7.0, and the surface roughness (Ra) is 0.1 to 5.0 nm.
- the substrate with a water-repellent film of the present invention is suitably used for use as an article for transportation equipment.
- Preferred examples of the article for transportation equipment include bodies in trains, automobiles, ships, aircrafts, window glass (front glass, side glass, rear glass), mirrors, bumpers, and the like.
- the substrate with a water-repellent film of the present invention or an article for transportation equipment comprising this substrate has excellent water droplet removal properties on the surface of the water-repellent film, so that there is little adhesion of water droplets to the surface, and the adhered water droplets are immediately repelled. It is.
- the attached water droplets move rapidly on the surface and do not accumulate as water droplets. For this reason, the bad influence which a water induces can be excluded.
- the water-repellent film is excellent in abrasion resistance and weather resistance. For example, the water-repellent film retains the water droplet removability even in long-term use under various use conditions including outdoor use as an article for transport equipment. be able to.
- the substrate with a water-repellent film of the present invention or an article for transport equipment comprising this substrate is particularly easy to secure a field of view by scattering of water droplets in applications such as various types of window glass, such as vehicles. Safety can be improved in operation. Further, it is difficult to freeze even in an environment where water droplets freeze, and even if it freezes, thawing is extremely fast. Furthermore, since there is almost no adhesion of water droplets, the number of cleaning operations can be reduced, and the cleaning operation can be easily performed.
- Examples of the present invention are shown below, but the present invention is not limited to these examples.
- Examples 1 to 17, Examples 22 to 53, and Examples 58 to 60 are examples, and Examples 18 to 21 and Examples 54 to 57 are comparative examples.
- SA Water drop angle
- Test conditions Muddy water spray (muddy water containing 5% by mass of one test powder described in JISZ8901, sprayed to the surface of the sample at 5.5 mL / m 2 ⁇ hr) with a weather strip under a load of 1 N / cm 2 Slide and wear frequency 4000 reciprocations
- C1s Narrow spectrum analysis was performed on the water-repellent film surface of the substrate with the water-repellent film obtained in each example using an X-ray photoelectron spectrometer in the same manner as described above.
- the C1sNarrow spectrum of each example obtained was converted into a peak derived from -CF 2 O-, a peak derived from -CF 2- , And separated into CF 3 -derived peaks.
- -CF 2 O by dividing by the peak height of from - - a peak height of -CF 2 O-derived -CF 2 / - CF 2 - was calculated.
- the reaction crude liquid was recovered.
- the recovered reaction crude liquid was filtered under reduced pressure, and then the filtrate was dried for 12 hours with a vacuum dryer (50 ° C., 5.0 torr) to obtain a crude liquid.
- the crude liquid was dissolved in 100 mL of R-225 and washed with 1000 mL of saturated aqueous sodium bicarbonate three times to recover the organic phase. After adding 1.0 g of magnesium sulfate to the organic phase and stirring for 12 hours, the magnesium sulfate was removed by filtration under pressure.
- Example 1 In a glass container in which a stirrer and a thermometer are set, 8.27 g of isopropyl alcohol (manufactured by Junsei Kagaku), 7.24 g of hydrofluoroether (AE3000, manufactured by Asahi Glass Co., Ltd.), 0.34 g of compound (A1) and 0.74 g of compound (B11) was added and stirred at 25 ° C. for 30 minutes. Next, 0.07 g of a 10% by mass nitric acid aqueous solution was added and stirred at 25 ° C. for 2 hours to obtain a liquid composition (H1) as a composition for forming a water-repellent film.
- AE3000 hydrofluoroether
- Example 2 In a glass container in which a stirrer and a thermometer are set, 14.34 g of isopropyl alcohol (manufactured by Junsei Co., Ltd.), 1.02 g of hydrofluoroether (AE3000, manufactured by Asahi Glass Co., Ltd.), 1.06 g of compound (A2) and 0.12 g of compound (B11) was added and stirred at 25 ° C. for 30 minutes. Subsequently, 0.13g of 10 mass% nitric acid aqueous solution was added, and it stirred at 25 degreeC for 2 hours, and obtained the liquid composition (H2) as a composition for water-repellent film formation.
- isopropyl alcohol manufactured by Junsei Co., Ltd.
- hydrofluoroether AE3000, manufactured by Asahi Glass Co., Ltd.
- compound (A2) and 0.12 g of compound (B11) was added and stirred at 25 ° C. for 30 minutes.
- Example 3 In a glass container in which a stirrer and a thermometer are set, 8.26 g of isopropyl alcohol (manufactured by Junsei Kagaku), 7.23 g of hydrofluoroether (AE3000, manufactured by Asahi Glass Co., Ltd.), 0.35 g of compound (A2) and 0.74 g of compound (B11) was added and stirred at 25 ° C. for 30 minutes. Next, 0.08 g of a 10% by mass nitric acid aqueous solution was added and stirred at 25 ° C. for 2 hours to obtain a liquid composition (H3) as a composition for forming a water-repellent film.
- H3 liquid composition
- Example 4 In a glass container in which a stirrer and a thermometer are set, 6.21 g of isopropyl alcohol (manufactured by Junsei Kagaku), 9.32 g of hydrofluoroether (AE3000, manufactured by Asahi Glass Co., Ltd.), 0.12 g of compound (A2) and 0.96 g of compound (B11) was added and stirred at 25 ° C. for 30 minutes. Subsequently, 0.06g of 10 mass% nitric acid aqueous solution was added, and it stirred at 25 degreeC for 2 hours, and obtained the liquid composition (H4) as a composition for water-repellent film formation.
- AE3000 hydrofluoroether
- Example 5 In a glass container in which a stirrer and a thermometer are set, 10.30 g of isopropyl alcohol (manufactured by Junsei Co., Ltd.), 5.15 g of hydrofluoroether (AE3000, manufactured by Asahi Glass Co., Ltd.), 0.59 g of compound (A2) and 0.53 g of compound (B11) was added and stirred at 25 ° C. for 30 minutes. Subsequently, 0.09 g of 10 mass% nitric acid aqueous solution was added and stirred at 25 ° C. for 2 hours to obtain a liquid composition (H5) as a composition for forming a water-repellent film.
- AE3000 hydrofluoroether
- compound (B11) 0.59 g of compound (A2) and 0.53 g of compound (B11) was added and stirred at 25 ° C. for 30 minutes.
- 0.09 g of 10 mass% nitric acid aqueous solution was added and stirred
- Example 6 In a glass container in which a stirrer and a thermometer are set, 12.40 g of isopropyl alcohol (manufactured by Junsei Kagaku), 3.10 g of hydrofluoroether (AE3000, manufactured by Asahi Glass Co., Ltd.), 0.74 g of compound (A2) and 0.32 g of compound (B11) was added and stirred at 25 ° C. for 30 minutes. Next, 0.10 g of a 10% by mass nitric acid aqueous solution was added and stirred at 25 ° C. for 2 hours to obtain a liquid composition (H6) as a composition for forming a water-repellent film.
- AE3000 hydrofluoroether
- compound (B11) 0.74 g of compound (A2) and 0.32 g of compound (B11) was added and stirred at 25 ° C. for 30 minutes.
- 0.10 g of a 10% by mass nitric acid aqueous solution was added and stirred at 25
- Example 7 In a glass container in which a stirrer and a thermometer are set, 10.30 g of isopropyl alcohol (manufactured by Junsei Co., Ltd.), 5.15 g of hydrofluoroether (AE3000, manufactured by Asahi Glass Co., Ltd.), 0.59 g of compound (A2) and 0.53 g of compound (B12) was added and stirred at 25 ° C. for 30 minutes. Subsequently, 0.09 g of 10 mass% nitric acid aqueous solution was added and stirred at 25 ° C. for 2 hours to obtain a liquid composition (H7) as a composition for forming a water-repellent film.
- AE3000 hydrofluoroether
- compound (B12) 0.59 g of compound (A2) and 0.53 g of compound (B12) was added and stirred at 25 ° C. for 30 minutes.
- 0.09 g of 10 mass% nitric acid aqueous solution was added and stirred
- Example 8 In a glass container in which a stirrer and a thermometer are set, 10.30 g of isopropyl alcohol (manufactured by Junsei Co., Ltd.), 5.15 g of hydrofluoroether (AE3000, manufactured by Asahi Glass Co., Ltd.), 0.59 g of compound (A2) and 0.53 g of compound (B13) was added and stirred at 25 ° C. for 30 minutes. Next, 0.09 g of a 10% by mass nitric acid aqueous solution was added and stirred at 25 ° C. for 2 hours to obtain a liquid composition (H8) as a composition for forming a water-repellent film.
- AE3000 hydrofluoroether
- compound (B13) 0.59 g of compound (A2) and 0.53 g of compound (B13) was added and stirred at 25 ° C. for 30 minutes.
- 0.09 g of a 10% by mass nitric acid aqueous solution was added and stirred
- Example 9 In a glass container in which a stirrer and a thermometer are set, 10.27 g of isopropyl alcohol (manufactured by Junsei Chemical Co., Ltd.), 5.13 g of hydrofluoroether (AE3000, manufactured by Asahi Glass Co., Ltd.), 0.62 g of compound (A3) and 0.53 g of compound (B11) was added and stirred at 25 ° C. for 30 minutes. Subsequently, 0.12g of 10 mass% nitric acid aqueous solution was added, and it stirred at 25 degreeC for 2 hours, and obtained the liquid composition (H9) as a composition for water-repellent film formation.
- isopropyl alcohol manufactured by Junsei Chemical Co., Ltd.
- hydrofluoroether AE3000, manufactured by Asahi Glass Co., Ltd.
- compound (A3) and 0.53 g of compound (B11) was added and stirred at 25 ° C. for 30 minutes.
- Example 10 In a glass container in which a stirrer and a thermometer are set, 8.26 g of isopropyl alcohol (manufactured by Junsei Chemical Co., Ltd.), 7.23 g of hydrofluoroether (AE3000, manufactured by Asahi Glass Co., Ltd.), 0.36 g of compound (A4) and 0.74 g of compound (B11) was added and stirred at 25 ° C. for 30 minutes. Next, 0.08 g of 10% by mass nitric acid aqueous solution was added and stirred at 25 ° C. for 2 hours to obtain a liquid composition (H10) as a composition for forming a water-repellent film.
- AE3000 hydrofluoroether
- Example 11 In a glass container in which a stirrer and a thermometer are set, 10.32 g of isopropyl alcohol (manufactured by Junsei Kagaku), 5.16 g of hydrofluoroether (AE3000, manufactured by Asahi Glass Co., Ltd.), 0.57 g of compound (A1) and 0.53 g of compound (B11) was added and stirred at 25 ° C. for 30 minutes. Next, 0.08 g of 10% by mass nitric acid aqueous solution was added and stirred at 25 ° C. for 2 hours to obtain a liquid composition (H11) as a composition for forming a water-repellent film.
- AE3000 hydrofluoroether
- Example 12 In a glass container in which a stirrer and a thermometer are set, 0.31 g of butyl acetate (manufactured by Junsei Chemical Co., Ltd.), 12.38 g of hydrofluoroether (AE3000, manufactured by Asahi Glass Co., Ltd.), 1.08 g of compound (A6) and 0.12 g of compound (B11) was added and stirred at 25 ° C. for 30 minutes to obtain a liquid composition (H12) as a composition for forming a water-repellent film.
- AE3000 hydrofluoroether
- compound (B11) 1.08 g of compound (A6) and 0.12 g of compound (B11) was added and stirred at 25 ° C. for 30 minutes to obtain a liquid composition (H12) as a composition for forming a water-repellent film.
- Example 13 In a glass container in which a stirrer and a thermometer are set, 0.31 g of butyl acetate (manufactured by Junsei Kagaku), 12.39 g of hydrofluoroether (AE3000, manufactured by Asahi Glass Co., Ltd.), 0.936 g of compound (A6) and 0.234 g of the compound (B11) was added and stirred at 25 ° C. for 30 minutes to obtain a liquid composition (H13) as a composition for forming a water-repellent film.
- AE3000 hydrofluoroether
- Example 14 In a glass container in which a stirrer and a thermometer are set, 0.31 g of butyl acetate (manufactured by Junsei Kagaku), 12.40 g of hydrofluoroether (AE3000, manufactured by Asahi Glass Co., Ltd.), 0.812 g of compound (A6) and 0.348 g of the compound (B11) was added and stirred at 25 ° C. for 30 minutes to obtain a liquid composition (H14) as a composition for forming a water-repellent film.
- AE3000 hydrofluoroether
- Example 15 In a glass container in which a stirrer and a thermometer are set, 0.31 g of butyl acetate (manufactured by Junsei Kagaku), 12.42 g of hydrofluoroether (AE3000, manufactured by Asahi Glass Co., Ltd.), 0.690 g of compound (A6) and 0.460 g of the compound (B11) was added and stirred at 25 ° C. for 30 minutes to obtain a liquid composition (H15) as a composition for forming a water repellent film.
- AE3000 hydrofluoroether
- Example 16 In a glass container in which a stirrer and a thermometer are set, 0.31 g of butyl acetate (manufactured by Junsei Chemical Co., Ltd.), 12.43 g of hydrofluoroether (AE3000, manufactured by Asahi Glass Co., Ltd.), 0.565 g of compound (A6) and 0.565 g of the compound (B11) was added and stirred at 25 ° C. for 30 minutes to obtain a liquid composition (H16) as a composition for forming a water-repellent film.
- AE3000 hydrofluoroether
- Example 17 In a glass container in which a stirrer and a thermometer are set, 0.31 g of butyl acetate (manufactured by Junsei Chemical Co., Ltd.), 12.44 g of hydrofluoroether (AE3000, manufactured by Asahi Glass Co., Ltd.), 0.448 g of compound (A6) and 0.672 g of the compound (B11) was added and stirred at 25 ° C. for 30 minutes to obtain a liquid composition (H17) as a composition for forming a water repellent film.
- AE3000 hydrofluoroether
- Example 18 In a glass container in which a stirrer and a thermometer are set, 5.18 g of isopropyl alcohol (manufactured by Junsei Kagaku), 10.37 g of hydrofluoroether (AE3000, manufactured by Asahi Glass Co., Ltd.) and 1.06 g of compound (B11) are placed. And stirred at 25 ° C. for 30 minutes. Next, 0.05 g of a 10% by mass nitric acid aqueous solution was added and stirred at 25 ° C. for 2 hours to obtain a liquid composition (H18) as a composition for forming a water-repellent film.
- isopropyl alcohol manufactured by Junsei Kagaku
- hydrofluoroether AE3000, manufactured by Asahi Glass Co., Ltd.
- Example 19 In a glass container in which a stirrer and a thermometer were set, 15.42 g of isopropyl alcohol (manufactured by Junsei Kagaku Co., Ltd.) and 1.14 g of compound (A1) were added and stirred at 25 ° C. for 30 minutes. Next, 0.11 g of a 10 mass% nitric acid aqueous solution was added and stirred at 25 ° C. for 2 hours to obtain a liquid composition (H19) as a composition for forming a water-repellent film.
- isopropyl alcohol manufactured by Junsei Kagaku Co., Ltd.
- compound (A1) 1.14 g
- 0.11 g of a 10 mass% nitric acid aqueous solution was added and stirred at 25 ° C. for 2 hours to obtain a liquid composition (H19) as a composition for forming a water-repellent film.
- Example 20 In a glass container in which a stirrer and a thermometer were set, 15.36 g of isopropyl alcohol (manufactured by Junsei Chemical Co., Ltd.) and 1.17 g of compound (A2) were added and stirred at 25 ° C. for 30 minutes. Next, 0.14 g of a 10% by mass nitric acid aqueous solution was added and stirred at 25 ° C. for 2 hours to obtain a liquid composition (H20) as a composition for forming a water-repellent film.
- isopropyl alcohol manufactured by Junsei Chemical Co., Ltd.
- compound (A2) 1.17 g of compound (A2) were added and stirred at 25 ° C. for 30 minutes.
- 0.14 g of a 10% by mass nitric acid aqueous solution was added and stirred at 25 ° C. for 2 hours to obtain a liquid composition (H20) as a composition for forming a water-repellent film.
- Example 21 In a glass container in which a stirrer and a thermometer were set, 15.32 g of isopropyl alcohol (manufactured by Junsei Chemical Co., Ltd.) and 1.19 g of compound (A4) were added and stirred at 25 ° C. for 30 minutes. Next, 0.15 g of a 10 mass% nitric acid aqueous solution was added and stirred at 25 ° C. for 2 hours to obtain a liquid composition (H21) as a composition for forming a water-repellent film.
- isopropyl alcohol manufactured by Junsei Chemical Co., Ltd.
- compound (A4) 1.19 g of compound (A4) were added and stirred at 25 ° C. for 30 minutes.
- 0.15 g of a 10 mass% nitric acid aqueous solution was added and stirred at 25 ° C. for 2 hours to obtain a liquid composition (H21) as a composition for forming a water-repellent film.
- Preparation Example 5 9.50 g of butyl acetate (manufactured by Junsei Co., Ltd.), 0.40 g of compound (C1) and 0.10 g of compound (A5) are placed in a glass container in which a stirrer and a thermometer are set. Stirring for a minute gave a liquid composition (E5) for forming the intermediate layer.
- the liquid composition (E5) has the same composition as the liquid composition (E3) prepared in Preparation Example 3, and the composition of the solid content (compound (C1) and compound (A5)) is also the same. However, the amount of organic solvent is different.
- the amount of the organic solvent with respect to 100 parts by mass of the solid is 3,200 parts by mass
- the amount of the organic solvent with respect to 100 parts by mass of the solid is 1,900 parts by mass. Part.
- a substrate with water-repellent film is formed by forming a water-repellent film on various substrates as follows. Manufactured. The obtained substrate with a water-repellent film was evaluated by the above evaluation method. Table 1 shows the types of substrates and liquid compositions used in each example, and Table 2 shows the results obtained in the above evaluations.
- Example 22 to 24 As a substrate, a clean soda lime glass substrate (water contact angle 5 °, 300 mm ⁇ 300 mm ⁇ thickness 3 mm), which was polished and cleaned with cerium oxide, was used for each of the examples shown in Table 1. 2 g of any one of the liquid compositions H1 to H3 obtained in Examples 1 to 3 was applied to the surface of the substrate by a squeegee coating method. Thereafter, a water-repellent layer was formed by holding for 48 hours in a thermo-hygrostat set to 50 ° C. and 60% RH, and a substrate with a water-repellent film having a water-repellent film composed of the water-repellent layer was obtained.
- Examples 25 to 34 As a substrate, a clean soda lime glass substrate (water contact angle 5 °, 300 mm ⁇ 300 mm ⁇ thickness 3 mm), which was polished and cleaned with cerium oxide, was used for each of the examples shown in Table 1. 2 g of the liquid composition E1 obtained in Preparation Example 1 was applied to the surface of the substrate by a squeegee coating method and held at 25 ° C. for 1 minute to form an intermediate layer. Next, 2 g of any one of the liquid compositions H2 to H11 obtained in Examples 2 to 11 was applied to the surface of the formed intermediate layer for each example shown in Table 1 by the squeegee coating method.
- a water-repellent layer was formed by holding for 48 hours in a thermo-hygrostat set to 50 ° C. and 60% RH to obtain a substrate with a water-repellent film having a water-repellent film composed of an intermediate layer and a water-repellent layer. .
- Examples 35 to 37 As a substrate, a clean soda lime glass substrate (water contact angle 5 °, 300 mm ⁇ 300 mm ⁇ thickness 3 mm), which was polished and cleaned with cerium oxide, was used for each of the examples shown in Table 1. 2 g of any one of the liquid compositions E2 to E4 obtained in Preparation Examples 2 to 4 was applied to the surface of the substrate by a squeegee coating method, and kept at 25 ° C. for 1 minute to form an intermediate layer. Next, 2 g of the liquid composition H5 obtained in Example 5 was applied to the surface of the formed intermediate layer by the squeegee coating method for each example shown in Table 1.
- a water-repellent layer was formed by holding for 48 hours in a thermo-hygrostat set to 50 ° C. and 60% RH to obtain a substrate with a water-repellent film having a water-repellent film composed of an intermediate layer and a water-repellent layer. .
- Example 38 A clean PET film (water contact angle 15 °, 210 mm ⁇ 297 mm ⁇ thickness 100 ⁇ m, HS-100, manufactured by Teijin DuPont Films), whose surface was washed with acetone and treated with UV ozone gas, was used as the substrate.
- 2 g of the liquid composition E1 obtained in Preparation Example 1 was applied to the surface of the film by a squeegee coating method and held at 25 ° C. for 1 minute to form an intermediate layer.
- 2 g of the liquid composition H5 obtained in Example 5 was applied to the surface of the formed intermediate layer by a squeegee coating method.
- a water-repellent layer was formed by holding for 48 hours in a thermo-hygrostat set to 50 ° C. and 60% RH to obtain a substrate with a water-repellent film having a water-repellent film composed of an intermediate layer and a water-repellent layer. .
- Examples 39 to 41 As a substrate, a clean soda lime glass substrate (water contact angle 5 °, 300 mm ⁇ 300 mm ⁇ thickness 3 mm), which was polished and cleaned with cerium oxide, was used for each of the examples shown in Table 1. 2 g of any one of the liquid compositions E1, E2, and E3 obtained in Preparation Examples 1, 2, and 3 was applied to the surface of the substrate by the squeegee coating method, and held at 25 ° C. for 1 minute to form an intermediate layer. did. Next, 2 g of the liquid composition H5 obtained in Example 5 was applied to the surface of the formed intermediate layer by the squeegee coating method for each example shown in Table 1.
- the substrate was provided with a water-repellent film having a water-repellent film formed of an intermediate layer and a water-repellent layer by holding in a constant temperature and humidity chamber set at 25 ° C. and 50% RH for 1 hour. .
- Example 42 to 47 As a substrate, a clean soda lime glass substrate (water contact angle 5 °, 300 mm ⁇ 300 mm ⁇ thickness 3 mm), which was polished and cleaned with cerium oxide, was used for each of the examples shown in Table 1. 2 g of the liquid composition E1 obtained in Preparation Example 1 was applied to the surface of the substrate by a squeegee coating method and held at 25 ° C. for 1 minute to form an intermediate layer. Next, 2 g of any of the liquid compositions H12 to H17 obtained in Examples 12 to 17 was applied to the surface of the formed intermediate layer for each example shown in Table 1 by the squeegee coating method.
- a water-repellent layer was formed by holding for 48 hours in a thermo-hygrostat set to 50 ° C. and 60% RH to obtain a substrate with a water-repellent film having a water-repellent film composed of an intermediate layer and a water-repellent layer. .
- Example 48 to 53 As a substrate, a clean soda lime glass substrate (water contact angle 5 °, 300 mm ⁇ 300 mm ⁇ thickness 3 mm), which was polished and cleaned with cerium oxide, was used for each of the examples shown in Table 1. 2 g of the liquid composition E5 obtained in Preparation Example 5 was applied to the surface of the substrate by a squeegee coating method and held at 25 ° C. for 1 minute to form an intermediate layer. Next, 2 g of any of the liquid compositions H12 to H17 obtained in Examples 12 to 17 was applied to the surface of the formed intermediate layer for each example shown in Table 1 by the squeegee coating method.
- a water-repellent layer was formed by holding for 48 hours in a thermo-hygrostat set to 50 ° C. and 60% RH to obtain a substrate with a water-repellent film having a water-repellent film composed of an intermediate layer and a water-repellent layer. .
- Example 54 to 57 As a substrate, a clean soda lime glass substrate (water contact angle 5 °, 300 mm ⁇ 300 mm ⁇ thickness 3 mm), which was polished and cleaned with cerium oxide, was used for each of the examples shown in Table 1. 2 g of the liquid composition E1 obtained in Preparation Example 1 was applied to the surface of the substrate by a squeegee coating method and held at 25 ° C. for 1 minute to form an intermediate layer. Next, 2 g of any of the liquid compositions H18 to H21 obtained in Examples 18 to 21 was applied to the surface of the formed intermediate layer for each example shown in Table 1 by the squeegee coating method.
- a water-repellent layer was formed by holding for 48 hours in a thermo-hygrostat set to 50 ° C. and 60% RH to obtain a substrate with a water-repellent film having a water-repellent film composed of an intermediate layer and a water-repellent layer. .
- Example 58 As a substrate, a clean automotive door glass that was polished and cleaned with cerium oxide and dried, and the liquid compositions E1 to E3 obtained in Preparation Examples 1 to 3 were applied to the glass surface by the squeegee coating method. And kept at 25 ° C. for 1 minute to form an intermediate layer. Next, the liquid composition H5 obtained in Example 5 was applied to the surface of the formed intermediate layer by a squeegee coating method. Thereafter, the water-repellent layer was formed by holding in an atmosphere of 25 ° C. and 50% RH for 1 hour to obtain a water-repellent glass for automobiles having a water-repellent film composed of an intermediate layer and a water-repellent layer.
- the water contact angle and the water falling angle were measured by the above-mentioned methods at 20 locations on the surface of the water-repellent film of the door glass obtained, they were in the range of 110 to 112 ° and 10 to 12 °, respectively.
- the film thicknesses of the intermediate layer and the water repellent layer measured with a transmission electron microscope JEM-2010F (manufactured by JEOL Ltd.) were 5 to 15 nm and 10 to 15 nm, respectively.
- Example 59 The door glass in Example 58 was changed to a front laminated glass or a rear glass to obtain a water-repellent front laminated glass for automobiles and a water-repellent rear glass for automobiles.
- these water-repellent glasses for automobiles were mounted on an automobile and a running test similar to that of Example 58 was performed, the same effect as Example 58 was confirmed.
- Example 60 An automotive door glass that has already been used for 5 years has been polished with calcium carbonate, washed with water, and dried for 1 hour. A water repellent film was formed on the glass in the same manner as in Example 58. When the same running test as in Example 58 was performed using this vehicle, the same effect as in Example 58 was confirmed.
- the substrate with a water-repellent film of the present invention has excellent water droplet removal property on the surface of the water-repellent film, and is also excellent in wear resistance and weather resistance, so that it can be used in transportation equipment such as trains, automobiles, ships and airplanes. It is suitable for applications as articles such as bodies, window glass (front glass, side glass, rear glass), mirrors, and bumpers.
- articles such as bodies, window glass (front glass, side glass, rear glass), mirrors, and bumpers.
Abstract
Description
本発明の撥水膜形成用組成物は、下記化合物(A)と化合物(B)とを含む、あるいは、下記一般式(1a)で表される化合物および/またはその部分加水分解縮合物と下記一般式(2a)で表される化合物および/またはその部分加水分解縮合物との部分加水分解共縮合物を含む、ことを特徴とする。
化合物(A):下記一般式(1a)で表される化合物、その部分加水分解縮合物、および下記一般式(1b)で表される化合物からなる群から選ばれる少なくとも1種のエーテル性酸素を含有しない含フッ素有機ケイ素化合物
Rf1-Y-Si(R11)r(X1)3-r …(1a)
Rf2-W-Z-Si(R12)p(X2)3―p …(2a)
<撥水膜形成用組成物>
本発明の撥水膜形成用組成物は、上記一般式(1a)で表される化合物、その部分加水分解縮合物、および上記一般式(1b)で表される化合物からなる群から選ばれる少なくとも1種のエーテル性酸素を含有しない含フッ素有機ケイ素化合物である化合物(A)と、上記一般式(2a)で表される化合物、上記一般式(2b)で示される化合物、およびその部分加水分解縮合物からなる群から選ばれる少なくとも1種のエーテル性酸素を含有する含フッ素有機ケイ素化合物である化合物(B)とを含む。あるいは、本発明の撥水膜形成用組成物は、上記一般式(1a)で表される化合物および/またはその部分加水分解縮合物と上記一般式(2a)で表される化合物および/またはその部分加水分解縮合物との部分加水分解共縮合物を含む。
Cy F-(CF2)m-、
Ad F-(CF2)n-。
式(1b)においてbは、1~100の整数を表す。bは式(1b)で示される化合物が有するケイ素-窒素結合の単位数を示すものであり、本発明においては、塗布性の点から、1~50が好ましい。
本発明の撥水膜形成用組成物において、化合物(A)は1種を単独で用いてもよく、2種以上を併用してもよい。
F(CF2)e(CH2)fSiX1 3、
F(CF2)e(CH2)fSi(R1)X1 2、
F(CF2)eCONH(CH2)gSiX1 3、
F(CF2)eCONH(CH2)gSi(R1)X1 2、
F(CF2)eCONH(CH2)hNH(CH2)5-hSiX1 3、
F(CF2)eCONH(CH2)hNH(CH2)5-hSi(R1)X1 2
Cy F-(CF2)m-、
Ad F-(CF2)n-。
式(2a)におけるpは、0~2の整数であるが、密着性、は形成された層の耐久性などに優れることから0または1が好ましい。
(一般式(2a)で表される化合物)
Rf2-O-(CF2CF2O)a-CF2-CONHC3H6Si(R2)p(X2)3-p …(B1)
Rf2-O-(CF2CF2O)a-CF2-CH2OCONHC3H6Si(R2)p(X2)3-p …(B2)
Rf2-O-(CF2CF2O)a-CF2-CH2OC3H6Si(R2)p(X2)3-p …(B3)
Rf2-O-(CF2CF2O)a-CF2-CF2OC3H6Si(R2)p(X2)3-p …(B4)
Rf2-O-(CF2CF2O)a-CF2-C2H4Si(R2)p(X2)3-p …(B5)
Rf2-O-(CF2CF2O)a-CF2-C3H6Si(R2)p(X2)3-p …(B6)
CF3-O-(CF2CF2O)a-CF2-CONHC3H6Si(OCH3)3
CF3-O-(CF2CF2O)a-CF2-CONHC3H6Si(OC2H5)3
CF3-O-(CF2CF2O)a-CF2-CONHC2H4Si(OCH3)3
CF3-O-(CF2CF2O)a-CF2-CONHC2H4Si(OC2H5)3
CF3-O-(CF2CF2O)a-CF2-C2H4Si(OCH3)3
CF3-O-(CF2CF2O)a-CF2-C2H4Si(OC2H5)3
(ただし、上記の全ての化合物(B)において、a=7~8であり、aの平均値は7.3である(以降、「a=7~8・平均値:7.3」と記載する。)。)
ここで、上記化合物(A)および化合物(B)は、本発明の撥水膜形成用組成物に、上記説明した化合物をそのままの状態で含有していてもよい。本発明の撥水膜形成用組成物は、化合物(A)を一般式(1a)で表される化合物および/またはその部分加水分解縮合物として、化合物(B)を一般式(2a)で表される化合物および/またはその部分加水分解縮合物として含有することが好ましく、その場合には、化合物(A)と化合物(B)の部分加水分解共縮合物として含有することがより好ましい。
本発明の撥水膜付き基体は、基体と、前記基体の少なくとも一部の表面に撥水膜とを有する撥水膜付き基体であって、前記撥水膜は1層以上で構成され、かつ最外層に上記本発明の撥水膜形成用組成物を用いて形成された撥水層を有する。
Si(X3)4 …(3)
なお、中間層形成用組成物を基体表面に塗布し、一定時間保持して塗膜を形成させ、その表面に撥水膜形成用組成物を塗布し、塗膜を形成させた後に、適当な条件で硬化処理を行うことで、中間層形成のための硬化処理と撥水層形成のための硬化処理を同時に行うことも可能である。
本発明の撥水膜付き基体は、輸送機器用物品としての用途に好適に用いられる。輸送機器用物品とは、電車、自動車、船舶、航空機等におけるボディー、窓ガラス(フロントガラス、サイドガラス、リアガラス)、ミラー、バンパー等が好ましく挙げられる。
<水滴除去性>
水滴除去性は以下の方法で測定した水接触角(CA)および水転落角(SA)の値で評価した。まず、以下の各試験を行う前に初期値を測定した。なお、水接触角(CA)が90°以上かつ水転落角(SA)が20°以下であれば、実使用に十分耐える水滴除去性を有するといえる。
[水接触角(CA)]
撥水膜付き基体の撥水膜表面に置いた、直径1mmの水滴の接触角をCA-X150(協和界面科学社製)を用いて測定した。撥水膜表面における異なる5ケ所で測定を行い、その平均値を算出した。
[水転落角(SA)]
水平に保持した撥水膜付き基体の撥水膜表面に50μLの水滴を滴下した後、基体を徐々に傾け、水滴が転落しはじめた時の撥水膜付き基体と水平面との角度(転落角)をSA-11(協和界面科学社製)を用いて測定した。転落角が小さいほど水滴除去性に優れる。
撥水膜付き基体の撥水膜表面に対し、下記試験条件にて磨耗試験を行った後、上記方法により水接触角および水転落角を測定した。
[耐布摩耗性試験]
JISL0849に準拠して下記試験機を用いて下記試験条件で耐布摩耗性試験を行った。
試験機:往復式トラバース試験機(ケイエヌテー社製)
試験条件:綿布(JISL0803に準拠)、荷重1kg、摩耗回数3000往復
[ドア昇降耐性試験]
ドア昇降試験機を用いて以下の試験条件でドア昇降耐性試験を行った。
試験条件:泥水噴霧(JISZ8901に記載された試験用粉体1種を5質量%含む泥水、試料表面に5.5mL/m2・hr噴霧)、1N/cm2負荷のもとウエザストリップで摺動、摩耗回数4000往復
[屋外暴露試験]
JISZ2381に準拠して屋外暴露試験を行った。すなわち、撥水膜付き基体を、撥水膜表面が水平に対して30度の角度で南向きになるよう屋外に設置し、試験開始から3ヶ月後、上記方法により水接触角および水転落角を測定した。
[SWOM(Sunshine Weather Meter)試験]
JISD0205に準拠してSWOM試験を行った。すなわち、撥水膜付き基体の撥水膜表面に対し、紫外線を1500時間照射した後、上記方法により水接触角および水転落角を測定した。
上記耐摩耗性および耐候性の4試験について、試験後における水接触角(CA)の全てが90°以上かつ水転落角(SA)の全てが20°以下である場合を合格「○」、それ以外を不合格「×」とした。
撥水膜付き基体の撥水膜表面の特性を評価するために、以下の方法で、フルオロアルキレン系炭素に対するフルオロエーテル系炭素の存在比(-CF2O-/-CF2-)、ケイ素原子に対するフッ素原子の存在比(F1s/Si2p)および表面粗さ(Ra)を測定した。
標準試料として、以下の比較例において作製した例54~例57の撥水膜付き基体の撥水膜表面について、X線光電子分光装置(XPS、Quantum2000、アルバックファイ社製)を用いて、X線(AlKα線)によりC1sのNarrowスペクトル解析を実施した。そのスペクトル測定結果から、-CF2O-に由来するピークは293eV付近に、CF3-に由来するピークは294eV付近に、-CF2-に由来するピークは291.5eV付近に発現することを確認した。
〔F1s/Si2p〕
撥水膜付き基体の撥水膜表面について、走査型X線光電子分光装置(ESCA、QuanteraSXM、アルバックファイ社製)を用いて、X線(AlKα線)により測定し、F1sのピーク高さとSi2pのピーク高さの比をF1s/Si2pとして算出した。
撥水膜付き基体の撥水膜表面について、走査型プローブ顕微鏡(SPM、SPA-400、エスアイアイ・ナノテクノロジー社製)を用いて、DFMモードにて、測定面積4μmにおける表面粗さ(Ra)を測定した。
<化合物(A)>
A1:C8F17C2H4Si(OCH3)3(シンクエスト社製)
A2:C6F13C2H4Si(OCH3)3(シンクエスト社製)
A3:C4F9C2H4Si(OCH3)3(Gelest社製)
A4:C4F9CONHC3H6Si(OCH3)3
A5:C6F13C2H4Si(NCO)3
A6:C6F13C2H4SiCl3(シンクエスト社製)
なお、上記化合物(A1)~化合物(A3)、および化合物(A6)については市販品を用い、化合物(A4)および化合物(A5)については以下の合成例により得られた化合物をそれぞれ使用した。合成例で得られたA4およびA5の確認は、1H-NMRにより行った。
撹拌機、および温度計がセットされたガラス容器に、C4F9CO2(C2H5)(シンクエスト社製)を50.00g、およびNH2C3H6Si(OCH3)3(KBM903、商品名、信越化学工業社製)を30.69g入れ、25℃にて12時間撹拌した。その後、未反応化合物と副生したエタノールを減圧蒸留して留去し、室温で液体のA4を79.2g得た。
参考文献(Journal of Fluorine Chemistry 79 (1996) 87-91)に基づいて、原料としてC6F13C2H4SiCl3の21.5gとシアン酸銀の25.0gを用い、ベンゼン溶媒中で、80℃にて1時間撹拌することで合成し、精製して室温で液体のA5を17.3g得た。
B11:CF3O[CF2CF2O]aCF2CONHC3H6Si(OCH3)3
B12:CF3O[CF2CF2O]aCF2CH2OCONHC3H6Si(OCH3)3
B13:CF3O[CF2CF2O]aCF2CH2OC3H6Si(OCH3)3
(ただし、上記B11、B12、B13の全てにおいて、a=7~8・平均値:7.3である。)
R-225:ジクロロペンタフルオロプロパン
Rf:-CF(CF3)OCF2CF(CF3)OCF2CF2CF3
R-113:CCl2FCClF2
CFE-419:CClF2CClFCF2OCF2CF2Cl
DBTDL:ジブチル錫ジラウレート
フラスコ内に、CH3O[CH2CH2O]aCH2CH2OH(市販のポリオキシエチレングリコールモノメチルエーテル、a=7~8・平均値:7.3。)の25g、R-225の20g、NaFの1.2g、およびピリジンの1.6gを入れ、内温を10℃以下に保ちながら激しく撹拌し、窒素をバブリングさせた。フラスコ内に、FC(O)-Rfの46.6gを、フラスコ内温度を5℃以下に保ちながら3.0時間かけて滴下した。滴下終了後、50℃にて12時間撹拌し、さらに室温にて24時間撹拌した後、反応粗液を回収した。回収した反応粗液を減圧濾過した後、濾過液を真空乾燥機(50℃、5.0torr)で12時間乾燥し、粗液を得た。粗液を100mLのR-225に溶解し、1000mLの飽和重曹水で3回水洗し、有機相を回収した。有機相に硫酸マグネシウムの1.0gを加え、12時間撹拌した後、加圧濾過して硫酸マグネシウムを除去した。その後、濾過液からエバポレータにてR-225を留去し、室温で液体である化合物(CH3O[CH2CH2O]aCH2CH2OC(O)-Rf(a=7~8・平均値:7.3))の56.1gを得た。
スターラーチップを投入した300mLのナスフラスコを充分に窒素置換した。その後、ナスフラスコ内に、2-プロパノールの30g、R-225の50.0g、および、NaBH4の4.1gを入れた。ナスフラスコ出口は窒素雰囲気とした。次いで、上記のナスフラスコ内に、化合物(B11)の製造方法で用いたのと同様にして、得られたCF3O[CF2CF2O]aCF2C(O)OCH2CH3(a=7~8・平均値:7.3)の26.2gをR-225の30gで希釈して滴下し、室温にて激しく撹拌した。8時間反応した後、冷却管に真空ポンプを設置して系内を減圧に保ち、溶媒を留去した。24時間後、ナスフラスコ内にR-225の100gを入れ、撹拌を行いながら、0.2規定塩酸水溶液の500gを滴下した。滴下後、反応溶液を6時間撹拌した。次いで、反応溶液を水相と有機層に分離し、有機相を蒸留水の500gにて3回水洗し、二層分離にて有機相を回収した。その後、有機相に硫酸マグネシウムの1.0gを加え、12時間撹拌した。その後、加圧濾過にて硫酸マグネシウムを除去し、濾過液からエバポレータにてR-225を留去して、室温で液体の化合物(CF3O[CF2CF2O]aCF2CH2OH(a=7~8・平均値:7.3))の24.8gを得た。
250mLの丸底フラスコ内に、窒素雰囲気下で水素化ナトリウムの0.36gを入れ、ヘキサンの25mLで洗浄し、ヘキサンを回収した。該操作をさらに2回繰り返した後、残留するヘキサンを減圧留去した。次いで、丸底フラスコ内に、CFE-419の25.0gを入れ、内温を5℃以下に保持した。その後、丸底フラスコ内に、上記化合物(B12)の製造でも用いたCF3O[CF2CF2O]aCF2CH2OH(a=7~8・平均値:7.3)の10gをCFE-419の25.0gに溶解した溶液を1時間かけて穏やかに滴下し、約10時間撹拌した。次いで、丸底フラスコ内に、CClH2CH2CH2Si(OCH3)3の0.85gを滴下して室温で2時間撹拌した後、72時間加熱還流した。加熱還流が終了した後、室温まで冷却し、未反応の水素化ナトリウムおよび副生した塩化ナトリウムを加圧濾過し、濾過液からCFE-419および過剰のCClH2CH2CH2Si(OCH3)3を減圧留去し、室温で液体の化合物(B13)の10.70gを得た。
C1:Si(NCO)4(SI-400、松本製薬工業社製)
C2:Si(OC2H5)4(アルドリッチ社製)
上記化合物(C1)および化合物(C2)としては市販品を用いた。
以下に本発明の撥水膜形成用組成物の作製の実施例を示す。例1~17が実施例であり、例18~21が比較例である。以下の各例で得られた液状組成物(H)を、後述の撥水膜付き基体の製造の実施例において、撥水層の形成用として用いた。
[例1]
撹拌機および温度計がセットされたガラス容器に、イソプロピルアルコール(純正化学社製)を8.27g、ハイドロフルオロエーテル(AE3000、旭硝子社製)を7.24g、化合物(A1)を0.34gおよび化合物(B11)を0.74g入れ、25℃にて30分間撹拌した。次いで、10質量%硝酸水溶液を0.07g添加し、25℃にて2時間撹拌して、撥水膜形成用組成物として液状組成物(H1)を得た。
撹拌機および温度計がセットされたガラス容器に、イソプロピルアルコール(純正化学社製)を14.34g、ハイドロフルオロエーテル(AE3000、旭硝子社製)を1.02g、化合物(A2)を1.06gおよび化合物(B11)を0.12g入れ、25℃にて30分間撹拌した。次いで、10質量%硝酸水溶液を0.13g添加し、25℃にて2時間撹拌して、撥水膜形成用組成物として液状組成物(H2)を得た。
撹拌機および温度計がセットされたガラス容器に、イソプロピルアルコール(純正化学社製)を8.26g、ハイドロフルオロエーテル(AE3000、旭硝子社製)を7.23g、化合物(A2)を0.35gおよび化合物(B11)を0.74g入れ、25℃にて30分間撹拌した。次いで、10質量%硝酸水溶液を0.08g添加し、25℃にて2時間撹拌して、撥水膜形成用組成物として液状組成物(H3)を得た。
撹拌機および温度計がセットされたガラス容器に、イソプロピルアルコール(純正化学社製)を6.21gおよびハイドロフルオロエーテル(AE3000、旭硝子社製)を9.32g、化合物(A2)を0.12gおよび化合物(B11)を0.96g入れ、25℃にて30分間撹拌した。次いで、10質量%硝酸水溶液を0.06g添加し、25℃にて2時間撹拌して、撥水膜形成用組成物として液状組成物(H4)を得た。
撹拌機および温度計がセットされたガラス容器に、イソプロピルアルコール(純正化学社製)を10.30g、ハイドロフルオロエーテル(AE3000、旭硝子社製)を5.15g、化合物(A2)を0.59gおよび化合物(B11)を0.53g入れ、25℃にて30分間撹拌した。次いで、10質量%硝酸水溶液を0.09g添加し、25℃にて2時間撹拌して、撥水膜形成用組成物として液状組成物(H5)を得た。
撹拌機および温度計がセットされたガラス容器に、イソプロピルアルコール(純正化学社製)を12.40g、ハイドロフルオロエーテル(AE3000、旭硝子社製)を3.10g、化合物(A2)を0.74gおよび化合物(B11)を0.32g入れ、25℃にて30分間撹拌した。次いで、10質量%硝酸水溶液を0.10g添加し、25℃にて2時間撹拌して、撥水膜形成用組成物として液状組成物(H6)を得た。
撹拌機および温度計がセットされたガラス容器に、イソプロピルアルコール(純正化学社製)を10.30g、ハイドロフルオロエーテル(AE3000、旭硝子社製)を5.15g、化合物(A2)を0.59gおよび化合物(B12)を0.53g入れ、25℃にて30分間撹拌した。次いで、10質量%硝酸水溶液を0.09g添加し、25℃にて2時間撹拌して、撥水膜形成用組成物として液状組成物(H7)を得た。
撹拌機および温度計がセットされたガラス容器に、イソプロピルアルコール(純正化学社製)を10.30g、ハイドロフルオロエーテル(AE3000、旭硝子社製)を5.15g、化合物(A2)を0.59gおよび化合物(B13)を0.53g入れ、25℃にて30分間撹拌した。次いで、10質量%硝酸水溶液を0.09g添加し、25℃にて2時間撹拌して、撥水膜形成用組成物として液状組成物(H8)を得た。
撹拌機および温度計がセットされたガラス容器に、イソプロピルアルコール(純正化学社製)を10.27g、ハイドロフルオロエーテル(AE3000、旭硝子社製)を5.13g、化合物(A3)を0.62gおよび化合物(B11)を0.53g入れ、25℃にて30分間撹拌した。次いで、10質量%硝酸水溶液を0.12g添加し、25℃にて2時間撹拌して、撥水膜形成用組成物として液状組成物(H9)を得た。
撹拌機および温度計がセットされたガラス容器に、イソプロピルアルコール(純正化学社製)を8.26g、ハイドロフルオロエーテル(AE3000、旭硝子社製)を7.23g、化合物(A4)を0.36gおよび化合物(B11)を0.74g入れ、25℃にて30分間撹拌した。次いで、10質量%硝酸水溶液を0.08g添加し、25℃にて2時間撹拌して、撥水膜形成用組成物として液状組成物(H10)を得た。
撹拌機および温度計がセットされたガラス容器に、イソプロピルアルコール(純正化学社製)を10.32g、ハイドロフルオロエーテル(AE3000、旭硝子社製)を5.16g、化合物(A1)を0.57gおよび化合物(B11)を0.53g入れ、25℃にて30分間撹拌した。次いで、10質量%硝酸水溶液を0.08g添加し、25℃にて2時間撹拌して、撥水膜形成用組成物として液状組成物(H11)を得た。
撹拌機および温度計がセットされたガラス容器に、酢酸ブチル(純正化学社製)を0.31g、ハイドロフルオロエーテル(AE3000、旭硝子社製)を12.38g、化合物(A6)を1.08gおよび化合物(B11)を0.12g入れ、25℃にて30分間撹拌して、撥水膜形成用組成物として液状組成物(H12)を得た。
撹拌機および温度計がセットされたガラス容器に、酢酸ブチル(純正化学社製)を0.31g、ハイドロフルオロエーテル(AE3000、旭硝子社製)を12.39g、化合物(A6)を0.936gおよび化合物(B11)を0.234g入れ、25℃にて30分間撹拌して、撥水膜形成用組成物として液状組成物(H13)を得た。
撹拌機および温度計がセットされたガラス容器に、酢酸ブチル(純正化学社製)を0.31g、ハイドロフルオロエーテル(AE3000、旭硝子社製)を12.40g、化合物(A6)を0.812gおよび化合物(B11)を0.348g入れ、25℃にて30分間撹拌して、撥水膜形成用組成物として液状組成物(H14)を得た。
撹拌機および温度計がセットされたガラス容器に、酢酸ブチル(純正化学社製)を0.31g、ハイドロフルオロエーテル(AE3000、旭硝子社製)を12.42g、化合物(A6)を0.690gおよび化合物(B11)を0.460g入れ、25℃にて30分間撹拌して、撥水膜形成用組成物として液状組成物(H15)を得た。
撹拌機および温度計がセットされたガラス容器に、酢酸ブチル(純正化学社製)を0.31g、ハイドロフルオロエーテル(AE3000、旭硝子社製)を12.43g、化合物(A6)を0.565gおよび化合物(B11)を0.565g入れ、25℃にて30分間撹拌して、撥水膜形成用組成物として液状組成物(H16)を得た。
撹拌機および温度計がセットされたガラス容器に、酢酸ブチル(純正化学社製)を0.31g、ハイドロフルオロエーテル(AE3000、旭硝子社製)を12.44g、化合物(A6)を0.448gおよび化合物(B11)を0.672g入れ、25℃にて30分間撹拌して、撥水膜形成用組成物として液状組成物(H17)を得た。
撹拌機および温度計がセットされたガラス容器に、イソプロピルアルコール(純正化学社製)を5.18g、ハイドロフルオロエーテル(AE3000、旭硝子社製)を 10.37gおよび化合物(B11)を1.06g入れ、25℃にて30分間撹拌した。次いで、10質量%硝酸水溶液を0.05g添加し、25℃にて2時間撹拌して、撥水膜形成用組成物として液状組成物(H18)を得た。
撹拌機および温度計がセットされたガラス容器に、イソプロピルアルコール(純正化学社製)を15.42gおよび化合物(A1)を1.14g入れ、25℃にて30分間撹拌した。次いで、10質量%硝酸水溶液を0.11g添加し、25℃にて2時間撹拌して、撥水膜形成用組成物として液状組成物(H19)を得た。
撹拌機および温度計がセットされたガラス容器に、イソプロピルアルコール(純正化学社製)を15.36gおよび化合物(A2)を1.17g入れ、25℃にて30分間撹拌した。次いで、10質量%硝酸水溶液を0.14g添加し、25℃にて2時間撹拌して、撥水膜形成用組成物として液状組成物(H20)を得た。
撹拌機および温度計がセットされたガラス容器に、イソプロピルアルコール(純正化学社製)を15.32g、および化合物(A4)を1.19g入れ、25℃にて30分間撹拌した。次いで、10質量%硝酸水溶液を0.15g添加し、25℃にて2時間撹拌して、撥水膜形成用組成物として液状組成物(H21)を得た。
後述の撥水膜付き基体の製造の実施例において用いた中間層形成用液状組成物(E)の調製例を以下に示す。
〔調製例1〕
撹拌機および温度計がセットされたガラス容器に、酢酸ブチル(純正化学社製)を9.70gおよび化合物(C1)を0.30g入れ、25℃にて30分間撹拌して、中間層形成用の液状組成物(E1)を得た。
撹拌機および温度計がセットされたガラス容器に、酢酸ブチル(純正化学社製)を97.00g、化合物(C1)を2.85gおよび化合物(A5)を0.15g入れ、25℃にて30分間撹拌して、中間層形成用の液状組成物(E2)を得た。
撹拌機および温度計がセットされたガラス容器に、酢酸ブチル(純正化学社製)を9.70g、化合物(C1)を0.24gおよび化合物(A5)を0.06g入れ、25℃にて30分間撹拌して、中間層形成用の液状組成物(E3)を得た。
撹拌機および温度計がセットされたガラス容器に、イソプロピルアルコール(純正化学社製)を9.70g、化合物(C2)を0.24g、化合物(A2)を0.06gおよび10質量%硝酸水溶液を0.27g入れ、25℃にて1時間撹拌して、中間層形成用の液状組成物(E4)を得た。
撹拌機および温度計がセットされたガラス容器に、酢酸ブチル(純正化学社製)を9.50g、化合物(C1)を0.40gおよび化合物(A5)を0.10g入れ、25℃にて30分間撹拌して、中間層形成用の液状組成物(E5)を得た。
なお、液状組成物(E5)は、上記調製例3で調製した液状組成物(E3)と配合成分は同様であり、固形分(化合物(C1)と化合物(A5))の組成も同様であるが、有機溶媒量が異なる。すなわち、液状組成物(E3)においては固形分100質量部に対する有機溶媒量は3,200質量部であり、液状組成物(E5)においては固形分100質量部に対する有機溶媒量は1,900質量部である。
上記各例および調製例で得られた各種液状組成物を用いて、以下のようにして各種基体に撥水膜を形成して撥水膜付き基体を製造した。得られた撥水膜付き基体について上記の評価方法により評価を行った。各例に用いた基体、液状組成物の種類を表1に、また上記各評価で得られた結果を表2に示す。
基体として、酸化セリウムで表面を研磨洗浄し、乾燥した清浄なソーダライムガラス基板(水接触角5°、300mm×300mm×厚さ3mm)を用い、表1に示すそれぞれの例毎に、該ガラス基板の表面に、上記例1~3で得た液状組成物H1~H3のいずれかの2gをスキージコート法によって塗布した。その後、50℃、60%RHに設定された恒温恒湿槽で48時間保持して撥水層を形成し、撥水層からなる撥水膜を有する撥水膜付き基体を得た。
基体として、酸化セリウムで表面を研磨洗浄し、乾燥した清浄なソーダライムガラス基板(水接触角5°、300mm×300mm×厚さ3mm)を用い、表1に示すそれぞれの例毎に、該ガラス基板の表面に上記調製例1で得た液状組成物E1の2gをスキージコート法によって塗布して、25℃で1分間保持し、中間層を形成した。次いで、形成した中間層表面に、表1に示すそれぞれの例毎に、上記例2~11で得た液状組成物H2~H11のいずれかの2gをスキージコート法によって塗布した。その後、50℃、60%RHに設定された恒温恒湿槽で48時間保持して撥水層を形成し、中間層および撥水層からなる撥水膜を有する撥水膜付き基体を得た。
基体として、酸化セリウムで表面を研磨洗浄し、乾燥した清浄なソーダライムガラス基板(水接触角5°、300mm×300mm×厚さ3mm)を用い、表1に示すそれぞれの例毎に、該ガラス基板の表面に上記調製例2~4で得た液状組成物E2~E4のいずれかの2gをスキージコート法によって塗布して、25℃で1分間保持し、中間層を形成した。次いで、形成した中間層表面に、表1に示すそれぞれの例毎に、上記例5で得た液状組成物H5の2gをスキージコート法によって塗布した。その後、50℃、60%RHに設定された恒温恒湿槽で48時間保持して撥水層を形成し、中間層および撥水層からなる撥水膜を有する撥水膜付き基体を得た。
基体として、アセトンで表面を洗浄し、UVオゾンガス処理を行った清浄なPETフィルム(水接触角15°、210mm×297mm×厚さ100μm、HS-100、帝人デュポンフィルム社製)を用い、該PETフィルムの表面に上記調製例1で得た液状組成物E1の2gをスキージコート法によって塗布して、25℃で1分間保持し、中間層を形成した。次いで、形成した中間層表面に、上記例5で得た液状組成物H5の2gをスキージコート法によって塗布した。その後、50℃、60%RHに設定された恒温恒湿槽で48時間保持して撥水層を形成し、中間層および撥水層からなる撥水膜を有する撥水膜付き基体を得た。
基体として、酸化セリウムで表面を研磨洗浄し、乾燥した清浄なソーダライムガラス基板(水接触角5°、300mm×300mm×厚さ3mm)を用い、表1に示すそれぞれの例毎に、該ガラス基板の表面に上記調製例1、2および3で得た液状組成物E1、E2、およびE3のいずれかの2gをスキージコート法によって塗布して、25℃で1分間保持し、中間層を形成した。次いで、形成した中間層表面に、表1に示すそれぞれの例毎に、上記例5で得た液状組成物H5の2gをスキージコート法によって塗布した。その後、25℃、50%RHに設定された恒温恒湿槽で1時間保持して撥水層を形成し、中間層および撥水層からなる撥水膜を有する撥水膜付き基体を得た。
基体として、酸化セリウムで表面を研磨洗浄し、乾燥した清浄なソーダライムガラス基板(水接触角5°、300mm×300mm×厚さ3mm)を用い、表1に示すそれぞれの例毎に、該ガラス基板の表面に上記調製例1で得た液状組成物E1の2gをスキージコート法によって塗布して、25℃で1分間保持し、中間層を形成した。次いで、形成した中間層表面に、表1に示すそれぞれの例毎に、上記例12~17で得た液状組成物H12~H17のいずれかの2gをスキージコート法によって塗布した。その後、50℃、60%RHに設定された恒温恒湿槽で48時間保持して撥水層を形成し、中間層および撥水層からなる撥水膜を有する撥水膜付き基体を得た。
基体として、酸化セリウムで表面を研磨洗浄し、乾燥した清浄なソーダライムガラス基板(水接触角5°、300mm×300mm×厚さ3mm)を用い、表1に示すそれぞれの例毎に、該ガラス基板の表面に上記調製例5で得た液状組成物E5の2gをスキージコート法によって塗布して、25℃で1分間保持し、中間層を形成した。次いで、形成した中間層表面に、表1に示すそれぞれの例毎に、上記例12~17で得た液状組成物H12~H17のいずれかの2gをスキージコート法によって塗布した。その後、50℃、60%RHに設定された恒温恒湿槽で48時間保持して撥水層を形成し、中間層および撥水層からなる撥水膜を有する撥水膜付き基体を得た。
基体として、酸化セリウムで表面を研磨洗浄し、乾燥した清浄なソーダライムガラス基板(水接触角5°、300mm×300mm×厚さ3mm)を用い、表1に示すそれぞれの例毎に、該ガラス基板の表面に上記調製例1で得た液状組成物E1の2gをスキージコート法によって塗布して、25℃で1分間保持し、中間層を形成した。次いで、形成した中間層表面に、表1に示すそれぞれの例毎に、上記例18~21で得た液状組成物H18~H21のいずれかの2gをスキージコート法によって塗布した。その後、50℃、60%RHに設定された恒温恒湿槽で48時間保持して撥水層を形成し、中間層および撥水層からなる撥水膜を有する撥水膜付き基体を得た。
上記表1および表2から、例1~例17で得られた本発明の撥水膜形成用組成物を用いて形成された撥水層を有する例22~例53の撥水膜付き基体については、いずれも初期から耐久性試験後においても水滴除去性に優れることがわかる。一方、例18~例21で得られた化合物(A)と化合物(B)のいずれかしか含まない比較例の撥水膜形成用組成物を用いて形成された撥水層を有する例54~例57の比較例の撥水膜付き基体については、いずれも初期の水滴除去性には問題はないが、耐久性試験後の水滴除去性に問題があることがわかる。
基体として、酸化セリウムで表面を研磨洗浄し、乾燥した清浄な自動車用ドアガラスを用い、該ガラスの表面に上記調製例1~3で得た液状組成物E1~E3をスキージコート法によって塗布して、25℃で1分間保持し、中間層を形成した。次いで、形成した中間層表面に、上記例5で得た液状組成物H5をスキージコート法によって塗布した。その後、25℃、50%RHの雰囲気で1時間保持して撥水層を形成し、中間層および撥水層からなる撥水膜を有する自動車用撥水性ガラスを得た。
この撥水性ガラスの2枚を自動車のドアに装着し、雨天時の走行テストを行ったところ、どの撥水ガラスも撥水膜表面の水滴が弾かれ、走行による風圧との相互作用によって水滴がすみやかに移動し、側方の視野が確保できた。
さらに、日中2時間の走行テストを3か月間行い、撥水性ガラスの撥水膜表面への水滴付着状況を肉眼で観察したところ、どの撥水ガラスにおいても、水滴の付着はほとんど観察されなかった。
上記例58におけるドアガラスをフロント合わせガラスまたはリアガラスに変更して自動車用撥水性フロント合わせガラスおよび自動車用撥水性リアガラスを得た。これらの自動車用撥水性ガラスを自動車に装着し、例58と同様の走行テストを行ったところ、例58と同じ効果が確認できた。
既に常用して5年間が経過した自動車用ドアガラスを、炭酸カルシウムで研磨した後、水洗し、1時間乾燥した。該ガラスに例58の方法と同様の方法で撥水膜を形成した。この自動車を用いて、例58と同様の走行テストを行ったところ、例58と同じ効果が確認できた。
なお、2009年8月3日に出願された日本特許出願2009-181047号の明細書、特許請求の範囲、及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。
Claims (12)
- 下記化合物(A)と化合物(B)とを含む、あるいは、下記一般式(1a)で表される化合物および/またはその部分加水分解縮合物と下記一般式(2a)で表される化合物および/またはその部分加水分解縮合物との部分加水分解共縮合物を含む、ことを特徴とする撥水膜形成用組成物。
化合物(A):下記一般式(1a)で表される化合物、その部分加水分解縮合物、および下記一般式(1b)で表される化合物からなる群から選ばれる少なくとも1種のエーテル性酸素を含有しない含フッ素有機ケイ素化合物
Rf1-Y-Si(R11)r(X1)3-r …(1a)
化合物(B):下記一般式(2a)で表される化合物、その部分加水分解縮合物、および下記一般式(2b)で示される化合物からなる群から選ばれる少なくとも1種のエーテル性酸素を含有する含フッ素有機ケイ素化合物
Rf2-W-Z-Si(R12)p(X2)3-p …(2a)
- 前記組成物における[化合物(B)]/[化合物(A)+化合物(B)]×100で表される化合物(A)と化合物(B)の合計質量に対する化合物(B)の質量百分率(ただし、組成物が部分加水分解共縮合物を含む場合は、部分加水分解共縮合反応物分については、加水分解共縮合反応前の化合物(A)と化合物(B)の量を用いて、計算される質量百分率)が、10~90質量%であることを特徴とする、請求項1に記載の撥水膜形成用組成物。
- 前記一般式(1a)および一般式(1b)におけるRf1が、環構造を有していてもよい炭素数3~8の炭素-炭素原子間にエーテル性酸素原子を含まないペルフルオロアルキル基であることを特徴とする、請求項1または2に記載の撥水層形成用組成物。
- 基体と、前記基体の少なくとも一部の表面に撥水膜とを有する撥水膜付き基体であって、前記撥水膜は1層以上で構成され、かつ最外層に請求項1~3のいずれか1項に記載の撥水膜形成用組成物を用いて形成された撥水層を有することを特徴とする、撥水膜付き基体。
- 前記撥水膜が、前記基体と前記撥水層との間に、シリカを主体とする中間層をさらに有することを特徴とする、請求項4に記載の撥水膜付き基体。
- 前記中間層が、下記一般式(3)で示される化合物、その部分加水分解縮合物、およびペルヒドロポリシラザンからなる群から選ばれる少なくとも1種の化合物(C)を含む中間層形成用組成物を用いて形成された層であることを特徴とする、請求項5に記載の撥水膜付き基体。
Si(X3)4 …(3)
(ただし、式(3)中、X3はそれぞれ独立して、ハロゲン原子、アルコキシ基またはイソシアネート基を表す。) - 前記中間層形成用組成物が、さらに前記化合物(A)を含有するか、あるいは、前記化合物(C)に代わって、前記一般式(3)で示される化合物および/またはその部分加水分解縮合物と前記一般式(1a)で表される化合物および/またはその部分加水分解縮合物との部分加水分解共縮合物を含有し、前記組成物における[化合物(A)]/[化合物(A)+化合物(C)]×100で表される化合物(A)と化合物(C)の合計質量に対する化合物(A)の質量百分率(ただし、組成物が部分加水分解共縮合物を含む場合は、部分加水分解共縮合反応物分については、加水分解共縮合反応前の化合物(A)と化合物(C)の量を用いて、計算される質量百分率)が、5~70質量%であることを特徴とする、請求項6に記載の撥水膜付き基体。
- 前記撥水膜表面における、X線光電子分光装置により測定される[-CF2O-]/[-CF2-]ピーク比が0.1~10.0であることを特徴とする、請求項4~7のいずれか1項に記載の撥水膜付き基体。
- 前記撥水膜表面における、X線光電子分光法(ESCA)により測定されるF1s/Si2pのピーク比が、1.5~7.0であり、走査型プローブ顕微鏡(SPM)により測定されるRa(表面粗さ)が、0.1~5.0nmであることを特徴とする、請求項4~8のいずれか1項に記載の撥水膜付き基体。
- 前記基体表面、または前記基体表面に予め形成された、前記撥水膜において最外層の下層をなす層の表面に、請求項1~3のいずれか1項に記載の撥水膜形成用組成物を塗布し、硬化させて撥水層を形成する工程を有することを特徴とする、請求項4~9のいずれか1項に記載の撥水膜付き基体の製造方法。
- 前記中間層形成用組成物を基体表面に塗布し硬化させてシリカを主体とする中間層を形成する工程と、前記中間層の表面に請求項1~3のいずれか1項に記載の撥水膜形成用組成物を塗布し、硬化させて撥水層を形成する工程と、を有することを特徴とする、請求項5~9のいずれか1項に記載の撥水膜付き基体の製造方法。
- 請求項4~8のいずれか1項に記載の撥水膜付き基体からなることを特徴とする、輸送機器用物品。
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011525897A JP5741435B2 (ja) | 2009-08-03 | 2010-08-03 | 撥水膜形成用組成物、撥水膜付き基体およびその製造方法並びに輸送機器用物品 |
CN201080034943.6A CN102471669B (zh) | 2009-08-03 | 2010-08-03 | 拒水膜形成用组合物、带拒水膜的基体及其制造方法以及运输机械用物品 |
BR112012002509A BR112012002509A2 (pt) | 2009-08-03 | 2010-08-03 | composição para formação de película repelente de água, substrato com uma película repelente de água e processo para sua produção, e artigo para equipamento de transporte |
EP10806457.7A EP2463348B1 (en) | 2009-08-03 | 2010-08-03 | Composition for formation of water-repellent film, base material having water-repellent film attached thereto and process for production thereof, and article for transport device |
IN940DEN2012 IN2012DN00940A (ja) | 2009-08-03 | 2010-08-03 | |
US13/365,437 US20120135252A1 (en) | 2009-08-03 | 2012-02-03 | Composition for forming water repellent film, substrate with a water repellent film and process for its production, and article for transport equipment |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009-181047 | 2009-08-03 | ||
JP2009181047 | 2009-08-03 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/365,437 Continuation US20120135252A1 (en) | 2009-08-03 | 2012-02-03 | Composition for forming water repellent film, substrate with a water repellent film and process for its production, and article for transport equipment |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011016458A1 true WO2011016458A1 (ja) | 2011-02-10 |
Family
ID=43544353
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2010/063118 WO2011016458A1 (ja) | 2009-08-03 | 2010-08-03 | 撥水膜形成用組成物、撥水膜付き基体およびその製造方法並びに輸送機器用物品 |
Country Status (8)
Country | Link |
---|---|
US (1) | US20120135252A1 (ja) |
EP (1) | EP2463348B1 (ja) |
JP (1) | JP5741435B2 (ja) |
KR (1) | KR20120038991A (ja) |
CN (1) | CN102471669B (ja) |
BR (1) | BR112012002509A2 (ja) |
IN (1) | IN2012DN00940A (ja) |
WO (1) | WO2011016458A1 (ja) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013510931A (ja) * | 2009-11-11 | 2013-03-28 | エシロール アンテルナシオナル (コンパニー ジェネラル ドプティック) | 表面処理組成物、その製造方法および表面処理された物品 |
WO2013061747A1 (ja) * | 2011-10-27 | 2013-05-02 | 旭硝子株式会社 | 被膜付き基板の製造方法 |
WO2014126064A1 (ja) | 2013-02-15 | 2014-08-21 | 旭硝子株式会社 | 撥水膜形成用組成物及びその使用 |
WO2019049754A1 (ja) * | 2017-09-05 | 2019-03-14 | Agc株式会社 | 含フッ素化合物、組成物および物品 |
WO2019203320A1 (ja) * | 2018-04-20 | 2019-10-24 | Agc株式会社 | 組成物および物品 |
JP2020531319A (ja) * | 2017-08-24 | 2020-11-05 | エージーシー オートモーティヴ アメリカズ アールアンドディー,インコーポレイテッド | 疎水性、及び耐久性を備える処理基板 |
WO2021131960A1 (ja) * | 2019-12-26 | 2021-07-01 | Agc株式会社 | 含フッ素エーテル化合物、表面処理剤、含フッ素エーテル組成物、コーティング液、物品、及び物品の製造方法 |
JPWO2021075569A1 (ja) * | 2019-10-18 | 2021-11-11 | ダイキン工業株式会社 | 表面処理剤 |
WO2022163319A1 (ja) * | 2021-01-28 | 2022-08-04 | ダイキン工業株式会社 | フルオロポリエーテル基含有シラン化合物を含有する組成物 |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9523004B2 (en) | 2009-11-11 | 2016-12-20 | Essilor International | Surface treatment composition, process for producing the same, and surface-treated article |
WO2014175124A1 (ja) * | 2013-04-24 | 2014-10-30 | 旭硝子株式会社 | 反射防止層付き基材 |
JP6209226B2 (ja) * | 2014-01-24 | 2017-10-04 | 日華化学株式会社 | 撥水剤組成物、撥水性繊維製品及び撥水性繊維製品の製造方法 |
US20170335137A1 (en) * | 2014-10-30 | 2017-11-23 | Beckman Coulter, Inc. | Compositions and Methods for Coating Surfaces |
CN105385349B (zh) * | 2015-12-10 | 2018-08-31 | 广州弘海化工科技有限公司 | 一种疏水防污有机聚硅氮烷涂料及其制备方法和应用 |
CN106279733B (zh) * | 2016-08-30 | 2019-06-11 | 张玉峰 | 涂料、疏水性硅质膜及疏水性硅质膜的制备方法 |
WO2019044481A1 (ja) | 2017-08-28 | 2019-03-07 | Agc株式会社 | 積層体およびその製造方法 |
KR20210106426A (ko) * | 2018-12-26 | 2021-08-30 | 에이지씨 가부시키가이샤 | 발수 발유층 형성 기재, 증착 재료 및 발수 발유층 형성 기재의 제조 방법 |
US20220243071A1 (en) * | 2019-05-14 | 2022-08-04 | Shin-Etsu Chemical Co., Ltd. | Water repellent and oil repellent member, and method for producing water repellent and oil repellent member |
CN115838320B (zh) * | 2023-02-28 | 2023-06-20 | 山东东岳化工有限公司 | 一种制备一氟甲烷的方法 |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001009266A1 (fr) | 1999-08-02 | 2001-02-08 | Nippon Sheet Glass Co., Ltd. | Article revetu d'une pellicule hydrophobe, composition liquide pour l'application de ladite pellicule hydrophobe, et procede de production d'article revetu d'une pellicule hydrophobe |
JP2001508120A (ja) * | 1997-10-06 | 2001-06-19 | サン−ゴバン・ヴイトラージユ | 特にグレージングのための疎水性付与塗料 |
JP3228085B2 (ja) | 1994-08-12 | 2001-11-12 | 信越化学工業株式会社 | 撥水処理剤 |
JP2002506887A (ja) * | 1998-01-27 | 2002-03-05 | ミネソタ マイニング アンド マニュファクチャリング カンパニー | 反射防止面の汚れ防止コートおよびその製法 |
JP2002226838A (ja) | 2001-02-01 | 2002-08-14 | Asahi Glass Co Ltd | 撥水性組成物、表面処理された基材、その製造方法および輸送機器用物品 |
JP2002256258A (ja) | 2001-03-01 | 2002-09-11 | Nippon Sheet Glass Co Ltd | 撥水膜被覆物品 |
JP3342170B2 (ja) | 1994-04-18 | 2002-11-05 | 日本板硝子株式会社 | 撥水被膜の形成方法 |
JP2003138210A (ja) | 2001-11-05 | 2003-05-14 | Nippon Sheet Glass Co Ltd | 被覆用組成物、被覆物品を製造する方法および被覆物品 |
JP2005509708A (ja) * | 2001-11-15 | 2005-04-14 | スリーエム イノベイティブ プロパティズ カンパニー | フッ素化シランを水性送達するための組成物 |
WO2009008380A1 (ja) | 2007-07-06 | 2009-01-15 | Asahi Glass Company, Limited | 表面処理剤、物品、および新規含フッ素エーテル化合物 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0641309A (ja) * | 1992-07-21 | 1994-02-15 | Toray Dow Corning Silicone Co Ltd | ジオルガノシロキサン・ジオルガノシラザン共重合体の製造方法 |
JP3414504B2 (ja) * | 1994-07-20 | 2003-06-09 | 東燃ゼネラル石油株式会社 | 撥水性セラミックス被膜の製法 |
CN1097626C (zh) * | 1995-02-20 | 2003-01-01 | 大金工业株式会社 | 污染附着防止剂及含有该防止剂的非水性涂料用组合物 |
US6743516B2 (en) * | 2000-09-29 | 2004-06-01 | Guardian Industries Corporation | Highly durable hydrophobic coatings and methods |
JP4862992B2 (ja) * | 2006-04-14 | 2012-01-25 | 信越化学工業株式会社 | 防汚性付与剤、防汚性コーティング剤組成物、防汚性被膜及びその被覆物品 |
JP5250813B2 (ja) * | 2007-03-25 | 2013-07-31 | 国立大学法人徳島大学 | 撥水処理方法および撥水性シリカ層を有する基材 |
JP2009143743A (ja) * | 2007-12-11 | 2009-07-02 | Mitsubishi Materials Corp | 合成シリカ粉の製造方法 |
-
2010
- 2010-08-03 KR KR1020127002762A patent/KR20120038991A/ko active IP Right Grant
- 2010-08-03 EP EP10806457.7A patent/EP2463348B1/en active Active
- 2010-08-03 CN CN201080034943.6A patent/CN102471669B/zh active Active
- 2010-08-03 BR BR112012002509A patent/BR112012002509A2/pt not_active IP Right Cessation
- 2010-08-03 JP JP2011525897A patent/JP5741435B2/ja active Active
- 2010-08-03 IN IN940DEN2012 patent/IN2012DN00940A/en unknown
- 2010-08-03 WO PCT/JP2010/063118 patent/WO2011016458A1/ja active Application Filing
-
2012
- 2012-02-03 US US13/365,437 patent/US20120135252A1/en not_active Abandoned
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3342170B2 (ja) | 1994-04-18 | 2002-11-05 | 日本板硝子株式会社 | 撥水被膜の形成方法 |
JP3228085B2 (ja) | 1994-08-12 | 2001-11-12 | 信越化学工業株式会社 | 撥水処理剤 |
JP2001508120A (ja) * | 1997-10-06 | 2001-06-19 | サン−ゴバン・ヴイトラージユ | 特にグレージングのための疎水性付与塗料 |
JP2002506887A (ja) * | 1998-01-27 | 2002-03-05 | ミネソタ マイニング アンド マニュファクチャリング カンパニー | 反射防止面の汚れ防止コートおよびその製法 |
WO2001009266A1 (fr) | 1999-08-02 | 2001-02-08 | Nippon Sheet Glass Co., Ltd. | Article revetu d'une pellicule hydrophobe, composition liquide pour l'application de ladite pellicule hydrophobe, et procede de production d'article revetu d'une pellicule hydrophobe |
JP2002226838A (ja) | 2001-02-01 | 2002-08-14 | Asahi Glass Co Ltd | 撥水性組成物、表面処理された基材、その製造方法および輸送機器用物品 |
JP2002256258A (ja) | 2001-03-01 | 2002-09-11 | Nippon Sheet Glass Co Ltd | 撥水膜被覆物品 |
JP2003138210A (ja) | 2001-11-05 | 2003-05-14 | Nippon Sheet Glass Co Ltd | 被覆用組成物、被覆物品を製造する方法および被覆物品 |
JP2005509708A (ja) * | 2001-11-15 | 2005-04-14 | スリーエム イノベイティブ プロパティズ カンパニー | フッ素化シランを水性送達するための組成物 |
WO2009008380A1 (ja) | 2007-07-06 | 2009-01-15 | Asahi Glass Company, Limited | 表面処理剤、物品、および新規含フッ素エーテル化合物 |
Non-Patent Citations (2)
Title |
---|
JOURNAL OF FLUORINE CHEMISTRY, vol. 79, 1996, pages 87 - 91 |
See also references of EP2463348A4 |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013510931A (ja) * | 2009-11-11 | 2013-03-28 | エシロール アンテルナシオナル (コンパニー ジェネラル ドプティック) | 表面処理組成物、その製造方法および表面処理された物品 |
WO2013061747A1 (ja) * | 2011-10-27 | 2013-05-02 | 旭硝子株式会社 | 被膜付き基板の製造方法 |
CN103889596A (zh) * | 2011-10-27 | 2014-06-25 | 旭硝子株式会社 | 带被膜的基板的制造方法 |
JPWO2013061747A1 (ja) * | 2011-10-27 | 2015-04-02 | 旭硝子株式会社 | 被膜付き基板の製造方法 |
WO2014126064A1 (ja) | 2013-02-15 | 2014-08-21 | 旭硝子株式会社 | 撥水膜形成用組成物及びその使用 |
US20150315443A1 (en) * | 2013-02-15 | 2015-11-05 | Asahi Glass Company, Limited | Composition for forming water repellent film, and its use |
JP2020531319A (ja) * | 2017-08-24 | 2020-11-05 | エージーシー オートモーティヴ アメリカズ アールアンドディー,インコーポレイテッド | 疎水性、及び耐久性を備える処理基板 |
JPWO2019049754A1 (ja) * | 2017-09-05 | 2020-10-08 | Agc株式会社 | 含フッ素化合物、組成物および物品 |
WO2019049754A1 (ja) * | 2017-09-05 | 2019-03-14 | Agc株式会社 | 含フッ素化合物、組成物および物品 |
WO2019203320A1 (ja) * | 2018-04-20 | 2019-10-24 | Agc株式会社 | 組成物および物品 |
JPWO2021075569A1 (ja) * | 2019-10-18 | 2021-11-11 | ダイキン工業株式会社 | 表面処理剤 |
JP7083921B2 (ja) | 2019-10-18 | 2022-06-13 | ダイキン工業株式会社 | 表面処理剤 |
WO2021131960A1 (ja) * | 2019-12-26 | 2021-07-01 | Agc株式会社 | 含フッ素エーテル化合物、表面処理剤、含フッ素エーテル組成物、コーティング液、物品、及び物品の製造方法 |
WO2022163319A1 (ja) * | 2021-01-28 | 2022-08-04 | ダイキン工業株式会社 | フルオロポリエーテル基含有シラン化合物を含有する組成物 |
JP2022115807A (ja) * | 2021-01-28 | 2022-08-09 | ダイキン工業株式会社 | フルオロポリエーテル基含有シラン化合物を含有する組成物 |
Also Published As
Publication number | Publication date |
---|---|
KR20120038991A (ko) | 2012-04-24 |
IN2012DN00940A (ja) | 2015-04-03 |
EP2463348A4 (en) | 2013-01-09 |
JPWO2011016458A1 (ja) | 2013-01-10 |
CN102471669A (zh) | 2012-05-23 |
EP2463348B1 (en) | 2015-10-07 |
JP5741435B2 (ja) | 2015-07-01 |
BR112012002509A2 (pt) | 2019-09-24 |
US20120135252A1 (en) | 2012-05-31 |
EP2463348A1 (en) | 2012-06-13 |
CN102471669B (zh) | 2014-11-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5741435B2 (ja) | 撥水膜形成用組成物、撥水膜付き基体およびその製造方法並びに輸送機器用物品 | |
JP6881458B2 (ja) | 撥水膜形成用組成物、撥水膜、撥水膜付き基体及び物品 | |
KR20010034441A (ko) | 반사 방지 표면용 얼룩 방지 코팅 및 이것의 제조 방법 | |
JP5999096B2 (ja) | 被膜付き基板の製造方法 | |
JP2012233157A (ja) | フルオロオキシアルキレン基含有ポリマー組成物および該組成物を含む表面処理剤並びに該表面処理剤で表面処理された物品 | |
WO2014126064A1 (ja) | 撥水膜形成用組成物及びその使用 | |
WO2012081524A1 (ja) | 含フッ素化合物、コーティング用組成物、撥水層付き基材およびその製造方法 | |
JP2014024288A (ja) | 撥水膜付き基板 | |
JP2014234506A (ja) | 新規化合物、撥水膜形成用組成物、撥水膜付き基体および輸送機器用物品 | |
US20210230735A1 (en) | Substrate with water-and-oil repellent layer, vapor deposition material, and method for producing substrate with water-and-oil repellent layer | |
JP6036132B2 (ja) | 撥水膜付き基体および輸送機器用物品 | |
JP2002121286A (ja) | 含フッ素有機ケイ素化合物、それを含む撥水性組成物、ならびに表面処理基材およびその製造方法 | |
CN109563338B (zh) | 组合物 | |
JP2014156061A (ja) | 下地層及び撥水膜を有する基体、及びこの下地層及び撥水膜を有する基体を含む輸送機器用物品 | |
JP2013091047A (ja) | 防汚性基板の製造方法 | |
US11873415B2 (en) | Substrate with water repellent oil repellent layer, vapor deposition material, and method for producing substrate with water repellent oil repellent layer | |
JP2016222869A (ja) | フルオロオキシアルキレン基含有ポリマー変性ホスホン酸誘導体、該誘導体を含む表面処理剤、該表面処理剤で処理された物品及び光学物品 | |
US20210284867A1 (en) | Substrate with water and oil-repellent layer, vapor deposition material, and method for producing substrate with water and oil-repellent layer | |
JP7428142B2 (ja) | 蒸着材料、およびそれを用いた下地層付き基材、撥水撥油層付き基材の製造方法 | |
JP2021172842A (ja) | 撥水撥油層付き基材、蒸着材料および撥水撥油層付き基材の製造方法 | |
JP2013129695A (ja) | 撥水膜形成用組成物、撥水膜付き基体および輸送機器用物品 | |
JP2023054698A (ja) | 硬化性組成物キット、膜付き基体および物品 | |
WO2023022038A1 (ja) | 表面処理された物品、並びに撥水性を有する物品の耐uvc性を向上させる方法 | |
WO2023032817A1 (ja) | 表面処理剤 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201080034943.6 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 10806457 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2011525897 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2010806457 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 20127002762 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 940/DELNP/2012 Country of ref document: IN |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112012002509 Country of ref document: BR |
|
ENP | Entry into the national phase |
Ref document number: 112012002509 Country of ref document: BR Kind code of ref document: A2 Effective date: 20120203 |