CN114402048B - Coating composition and article having coating - Google Patents

Coating composition and article having coating Download PDF

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CN114402048B
CN114402048B CN202080064645.5A CN202080064645A CN114402048B CN 114402048 B CN114402048 B CN 114402048B CN 202080064645 A CN202080064645 A CN 202080064645A CN 114402048 B CN114402048 B CN 114402048B
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alkoxysilane compound
compound
coating composition
perfluoropolyether
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CN114402048A (en
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市原豊
榎並翼
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Neos Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/10—Block or graft copolymers containing polysiloxane sequences
    • C09D183/12—Block or graft copolymers containing polysiloxane sequences containing polyether sequences
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • 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
    • 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
    • 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

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Abstract

The purpose of the present invention is to provide a novel coating composition which is capable of forming a light-transmitting coating layer that has excellent stain resistance, is resistant to scratching, has durability against common chemicals, and does not lose these properties even under high temperature and high humidity. The present invention provides a coating composition comprising at least: a 1 st alkoxysilane compound having a perfluoropolyether portion in the molecule; a 2 nd alkoxysilane compound having a perfluoro group in a molecule and having no perfluoropolyether portion; and a 3 rd alkoxysilane compound having at least 4 or more alkoxy groups in the molecule and having no perfluoropolyether moiety and no perfluoro group. The present invention also provides a coated article formed by reacting the coating composition with an inorganic substrate.

Description

Coating composition and article having coating
Technical Field
The present invention relates to a coating composition and a coated article obtained by reacting the coating composition with an inorganic substrate.
Background
In optical members such as displays and touch panels, which require light transmittance and transparency, coating agents for covering the surface are used. Such a coating agent is required to have not only light transmittance and transparency but also high levels of durability against scratches, stain resistance against stains such as fingerprints, and chemical resistance including alkali resistance and acid resistance.
Japanese patent JP2014-218639A discloses a silane compound containing a perfluoropolyether group. Silane compounds containing a perfluoropolyether group have been proposed as surface treatment agents, particularly antifouling coating agents, since they provide excellent water repellency, oil repellency, antifouling properties, and abrasion resistance.
Disclosure of Invention
[ problems to be solved by the invention ]
The surface treatment layer formed using the surface treatment agent of japanese patent JP2014-218639A has abrasion resistance, a large water contact angle, and excellent sliding properties. However, the present inventors have evaluated how long the good performance of the surface treatment layer formed by the surface treatment agent of japanese patent JP2014-218639A can be maintained, and as a result, found that the performance of the surface treatment layer is significantly lowered if it is brought into contact with an alkaline substance. Further, it has been found that the surface treatment layer formed by the surface treatment agent of JP2014-218639A is significantly deteriorated in performance under high-temperature and high-humidity conditions. Accordingly, an object of the present invention is to provide a novel coating composition capable of forming a coating layer having excellent antifouling properties, scratch resistance, and durability against common chemicals at the same time, which coating layer does not lose these properties even under high temperature and high humidity.
[ means for solving problems ]
An embodiment of the present invention is a coating composition comprising at least: a 1 st alkoxysilane compound having a perfluoropolyether portion in the molecule; a 2 nd alkoxysilane compound having a perfluoro group in a molecule and having no perfluoropolyether portion; and a 3 rd alkoxysilane compound having at least 4 or more alkoxy groups in the molecule and having no perfluoropolyether portion and no perfluoro group.
Another embodiment of the present invention is a coated article formed by reacting a coating composition with an inorganic substrate, the coating composition comprising at least: a 1 st alkoxysilane compound having a perfluoropolyether moiety in the molecule; a 2 nd alkoxysilane compound having a perfluoro group in a molecule and having no perfluoropolyether portion; and a 3 rd alkoxysilane compound having at least 4 or more alkoxy groups in the molecule and having no perfluoropolyether portion and no perfluoro group.
[ Effect of the invention ]
The coating composition of the present invention can form a coating layer having a large water contact angle, excellent antifouling properties, and having oil repellency, scratch resistance, and chemical resistance at the same time, and the coating layer does not lose these properties even under high temperature and high humidity.
Detailed Description
Hereinafter, embodiments of the present invention will be described. One embodiment of the present invention is a coating composition comprising at least: a 1 st alkoxysilane compound having a perfluoropolyether portion in the molecule; a 2 nd alkoxysilane compound having a perfluoro group in a molecule and having no perfluoropolyether portion; and a 3 rd alkoxysilane compound having at least 4 or more alkoxy groups in the molecule and having no perfluoropolyether moiety and no perfluoro group.
In the present embodiment, the coating composition is a composition that exists in a liquid state at normal temperature and is applied to form a coating film mainly intended for protecting the surface of an article or for polishing. That is, the coating composition is mainly used as a coating material, and is required to satisfy various required properties in response to a construction site or an article. The coating film (coating layer) formed from the coating composition of the present embodiment is mainly used for coating, processing, and decorating the surface of an inorganic substrate such as metal or glass, and is also used for coating, processing, and decorating the surface of a resin or plastic article as the case may be. The coating composition of the embodiment forms a coating layer which adheres to the surface of these articles, is hardly peeled off, is light-transmitting, and is transparent as a whole.
The coating composition of the present embodiment contains a 1 st alkoxysilane compound having a perfluoropolyether moiety in the molecule. The alkoxysilane compound is one of silicon compounds having silicon (Si) in the molecule, and is a compound having 1 OR more alkoxysilyl groups having 1 to 3 substituents — OR (R represents an alkyl group) bonded to silicon. In the present embodiment, it is particularly preferable to use, as the 1 st alkoxysilane compound, an alkoxysilane compound having 1 OR 2 trialkoxysilyl groups in which 3 substituent groups — OR (R represents an alkyl group) are bonded to silicon.
In the present specification, the perfluoropolyether portion refers to a portion in which a perfluoro group is bonded via an ether bond. The perfluoropolyether moiety has a structure represented by formula I:
[ solution 1]
Figure GDA0003547089620000031
(wherein a, b, c, d are each independently an integer of 0 to 200 inclusive, and a, b, c, d are not all 0, and the repeating units in each parenthesis may be bonded in any order). The 1 st alkoxysilane compound having a perfluoropolyether portion in the molecule used in the present embodiment preferably has 1 or 2 alkoxysilyl groups. The 1 st alkoxysilane compound having a perfluoropolyether moiety in the molecule used in the present embodiment is preferably a compound represented by the following formula II:
[ solution 2]
Figure GDA0003547089620000032
(wherein Rf is a perfluoropolyether moiety represented by the formula I, R 1 Each independently represents an alkyl group having 1 to 4 carbon atoms, X represents a substituent having an alkoxysilyl group or a perfluoroalkyl group having 1 to 3 carbon atoms, and e represents an integer of 1 to 4). In the formula II, when X is a substituent having an alkoxysilyl group, the 1 st alkoxysilane compound having a perfluoropolyether portion in the molecule used in the present embodiment may be a compound represented by the following formula III:
[ solution 3]
Figure GDA0003547089620000033
(wherein Rf is a perfluoropolyether moiety represented by the formula I, R 1 Each independently is an alkyl group having 1 to 4 carbon atoms, R 2 Each independently an alkyl group having 1 to 4 carbon atoms, e is an integer of 1 to 4, and h is an integer of 1 to 4). In the formula II, when X is a perfluoroalkyl group having 1 to 3 carbon atoms, the 1 st alkoxysilane compound having a perfluoropolyether moiety in the molecule used in the present embodiment may be a compound represented by the following formula IVa:
[ solution 4]
Figure GDA0003547089620000034
(wherein Rf is a perfluoropolyether moiety represented by the formula I, R) 1 Each independently an alkyl group having 1 to 4 carbon atoms, e is an integer of 1 to 4); a compound represented by the following formula IVb:
[ solution 5]
Figure GDA0003547089620000035
(wherein Rf is a perfluoropolyether moiety represented by the formula I, R 1 Each independently an alkyl group having 1 to 4 carbon atoms, e is an integer of 1 to 4); or a compound represented by formula IVc below:
[ solution 6]
Figure GDA0003547089620000041
(wherein Rf is a perfluoropolyether moiety represented by the formula I, R) 1 Each independently an alkyl group having 1 to 4 carbon atoms, and e is an integer of 1 to 4).
The coating composition of the present embodiment contains a 2 nd alkoxysilane compound having a perfluoro group in the molecule and no perfluoropolyether portion. The 2 nd alkoxysilane compound used in the embodiment is one of silicon compounds having silicon (Si) in the molecule, and is a compound having 1 OR more silicon atoms to which an alkoxysilyl group having 1 to 3 substituents — OR (R represents an alkyl group) is bonded, similarly to the 1 st alkoxysilane compound. In the present embodiment, it is particularly preferable to use, as the 2 nd alkoxysilane compound, an alkoxysilane compound having 1 trialkoxysilyl group in which 3 substituents-OR (R represents an alkyl group) are bonded to silicon. The 2 nd alkoxysilane compound having a perfluoro group in the molecule and no perfluoropolyether moiety used in the present embodiment may be a compound represented by the following formula V:
[ solution 7]
Figure GDA0003547089620000042
(wherein R is 3 Is 1c in carbon number4, f is an integer of 1 to 6, and g is an integer of 0 to 5). Examples of the 2 nd alkoxysilane compound include: an alkoxysilane compound having a perfluoro group in the molecule, such as trifluoropropyltrimethoxysilane, trifluorobutyltrimethoxysilane, pentafluoroethyltrimethoxysilane, heptafluoroethyltrimethoxysilane, trifluoropropyltriethoxysilane, and trifluorobutyltriethoxysilane.
The coating composition of the embodiment contains a 3 rd alkoxysilane compound having at least 4 or more alkoxy groups in the molecule and having no perfluoropolyether portion and no perfluoro group. The 3 rd alkoxysilane compound used in the embodiment is one of silicon compounds having silicon (Si) in the molecule, and is a compound having 1 OR more silicon to which an alkoxysilyl group having 1 to 3 substituents — OR (R represents an alkyl group) is bonded, similarly to the 1 st alkoxysilane compound OR the 2 nd alkoxysilane compound described above. In the present embodiment, an alkoxysilane compound having 4 OR more substituents — OR (R represents an alkyl group) in the molecule is particularly preferably used as the 3 rd alkoxysilane compound. The 3 rd alkoxysilane compound does not have the perfluoropolyether portion and perfluoro group. The 3 rd alkoxysilane compound having at least 4 or more alkoxy groups in the molecule and having no perfluoropolyether moiety and no perfluoro group used in the present embodiment may be a compound represented by the following formula VI:
[ solution 8]
Figure GDA0003547089620000051
(in the formula, R 4 、R 5 Each independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms, R present in the molecule of the compound represented by the formula VI 4 And R 5 At least 4 of them are alkyl groups having 1 to 5 carbon atoms, and i is an integer of 1 to 5). Examples of the 3 rd alkoxysilane compound include: tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetramethoxysilane hydrolyzed polycondensate, tetraethoxysilane hydrolyzed polycondensate, tetrapropoxysilane hydrolyzed polycondensate, tetrabutoxysilane hydrolyzed polycondensate, methyl silicate tetramer, silicic acidAnd alkoxysilane compounds such as methyl ester heptamer, ethyl silicate pentamer, and ethyl silicate decamer.
In an embodiment, the number average molecular weight of the 1 st alkoxysilane compound (the compound represented by the formula II, III, IVa, IVb, IVc) is particularly preferably larger than the molecular weight of the 2 nd alkoxysilane compound (the compound represented by the formula V). In particular, the number average molecular weight of the 1 st alkoxysilane compound is preferably 10 times or more the molecular weight of the 2 nd alkoxysilane compound. The number average molecular weight of the 1 st alkoxysilane compound is 2000 or more, preferably 3000 or more, and more preferably 4000 or more. The molecular weight of the 2 nd alkoxysilane compound may be selected according to the number average molecular weight of the 1 st alkoxysilane compound, and for example, when the number average molecular weight of the 1 st alkoxysilane compound is 3,000, the molecular weight of the 2 nd alkoxysilane compound may be 300 or the like. The technical meaning of setting the ratio of the number average molecular weight of the 1 st alkoxysilane compound to the molecular weight of the 2 nd alkoxysilane compound in the above-described manner will be explained later.
In the coating composition of the embodiment, it is preferable that the weight ratio of 10:1 to 10:40 contains a 1 st alkoxysilane compound and a 2 nd alkoxysilane compound. The coating composition is particularly preferably applied in a weight ratio of 10:1 to 10:20 contains a 1 st alkoxysilane compound and a 2 nd alkoxysilane compound. That is, the weight of the 2 nd alkoxysilane is preferably at most about 2 times the weight of the 1 st alkoxysilane compound. In the coating composition of the embodiment, it is preferable that the weight ratio of 10:0.5 to 10:5 contains a 1 st alkoxysilane compound and a 3 rd alkoxysilane compound. The coating composition is particularly preferably applied in a weight ratio of 10:1 to 10:4.5 contains a 1 st alkoxysilane compound and a 3 rd alkoxysilane compound.
The coating composition of an embodiment may further contain a solvent. As the solvent for diluting the coating composition of the embodiment, a solvent capable of dissolving the 1 st alkoxysilane compound, the 2 nd alkoxysilane compound, and the 3 rd alkoxysilane compound is preferable, and a fluorine-based solvent called a so-called next-generation fluorine-based solvent (fluorochlorocarbon compound) such as Perfluorocarbon (PFC), hydrofluoroolefin (HFO), hydrofluoroether (HFE), and Hydrofluorochlorocarbon (HCFC) is preferably used. Examples of the solvent that can be used in the embodiment include: AMOLEA (AGC corporation), ASAHIKLIN (AGC corporation), NOVEC (3M Japan corporation), CELEFIN (Central Glass corporation), zeorora (japanese ruiwenya corporation), DIPSOL (DIPSOL corporation), and these solvents can be used by appropriately selecting them from commercially available solvents.
The amount of the solvent used is 100 times or more, preferably 150 times or more, more preferably 200 times or more, and still more preferably 500 times or more based on the total weight of the 1 st alkoxysilane compound, the 2 nd alkoxysilane compound, and the 3 rd alkoxysilane compound. The coating composition of the embodiment in which the 1 st alkoxysilane compound, the 2 nd alkoxysilane compound, and the 3 rd alkoxysilane compound are dissolved in a solvent can be spread well on an inorganic substrate in particular.
The coating composition of the embodiment can be produced by mixing the 1 st alkoxysilane compound, the 2 nd alkoxysilane compound, and the 3 rd alkoxysilane compound and then dissolving them in a solvent. In addition to the above components, the coating composition of the embodiment may further contain additives (matting agent, antistatic agent, ultraviolet absorber, light stabilizer, inorganic particles, and the like) which are generally contained in conventional coating agents, as necessary.
Next, a production example of the 1 st alkoxysilane compound which is a component of the coating composition of the embodiment will be described. The 1 st alkoxysilane compound is preferably a perfluoropolyether compound capable of being represented by the following formula VIIa:
[ solution 9]
HO-CH 2 CF 2 -Rf-CF 3 (VIIa)
(wherein Rf is a perfluoropolyether moiety represented by formula I), or a perfluoropolyether compound represented by formula VIIb:
[ solution 10]
HO-CH 2 CF 2 -Rf-CF 2 CF 3 (VIIb)
(wherein Rf is a perfluoropolyether moiety represented by the formula I), or a perfluoropolyether compound represented by the following formula VIIc:
[ solution 11]
HO-CH 2 CF 2 -Rf-CF 2 CF 2 CF 3 (VIIc)
(wherein Rf is a perfluoropolyether moiety represented by formula I), and the following formula VIII:
[ solution 12]
Figure GDA0003547089620000061
(in the formula, R 1 Each independently an alkyl group having 1 to 4 carbon atoms, and e is an integer of 1 to 4) and an isocyanate compound having an alkoxysilyl group. Here, the compounds represented by formulas VIIa to VIIc and the compound represented by formula VIII are theoretically in a molar ratio of 1:1, the reaction was carried out. Obtaining a 1 st alkoxysilane compound represented by the following formula IVa by reacting a compound represented by the formula VIIa to formula VIIc with a compound represented by the formula VIII:
[ solution 13]
Figure GDA0003547089620000071
(wherein Rf is a perfluoropolyether moiety represented by the formula I, R 1 Each independently an alkyl group having 1 to 4 carbon atoms, e is an integer of 1 to 4); a 1 st alkoxysilane compound represented by the following formula IVb:
[ solution 14]
Figure GDA0003547089620000072
(wherein Rf is a perfluoropolyether moiety represented by the formula I, R 1 Each independently an alkyl group having 1 to 4 carbon atoms, e is an integer of 1 to 4); or a 1 st alkoxy group represented by the following formula IVcSilane compound:
[ chemical 15]
Figure GDA0003547089620000073
(wherein Rf is a perfluoropolyether moiety represented by the formula I, R 1 Each independently an alkyl group having 1 to 4 carbon atoms, and e is an integer of 1 to 4).
Further, the 1 st alkoxysilane compound is preferably a compound capable of reacting a compound represented by the following formula IX:
[ solution 16]
HO-CH 2 CF 2 -Rf-CF 2 CH 2 OH (IX)
(wherein Rf is a perfluoropolyether moiety represented by formula I), and the following formula VIII:
[ solution 17]
Figure GDA0003547089620000074
(in the formula, R 1 Each independently an alkyl group having 1 to 4 carbon atoms, and e is an integer of 1 to 4) and an isocyanate compound having an alkoxysilyl group. Here, the compound represented by formula IX and the compound represented by formula VIII are theoretically in a molar ratio of 1:2, the reaction was carried out. Obtaining a 1 st alkoxy compound represented by the following formula III by reacting a compound represented by the formula IX with a compound represented by the formula VIII:
[ solution 18]
Figure GDA0003547089620000081
(wherein Rf is a perfluoropolyether moiety represented by the formula I, R 1 Each independently an alkyl group having 1 to 4 carbon atoms, R 2 Each independently an alkyl group having 1 to 4 carbon atoms, e is an integer of 1 to 4, and h is an integer of 1 to 4).
Although the 2 nd alkoxysilane compound can be synthesized, commercially available products such as: KBM-7103 (Trifluoropropyltrimethoxysilane, shin-Etsu chemical Co., ltd.), trifluoropropyltriethoxysilane (Tokyo Kasei Industrial Co., ltd.), nonafluorohexyltrimethoxysilane (Tokyo Kasei Industrial Co., ltd.), nonafluorohexyltriethoxysilane (Tokyo Kasei Industrial Co., ltd.), and the like.
The 3 rd alkoxysilane compound can also be synthesized, but commercially available products such as: ethyl silicate 28, ethyl silicate 28P, propyl orthosilicate, butyl orthosilicate, methyl silicate 51, methyl silicate 53A, ethyl silicate 40, ethyl silicate 48 (all of cockkon gmbh); MKC Silicate MS51, MS56, MS57, MS56S (all Mitsubishi chemical corporation); salicide methyl ester, salicide ethyl ester (all from polymol chemical industries, ltd.) and the like.
Another embodiment of the present invention is a coated article formed by reacting a coating composition with an inorganic substrate, the coating composition comprising at least: a 1 st alkoxysilane compound having a perfluoropolyether portion in the molecule; a 2 nd alkoxysilane compound having a perfluoro group in a molecule and having no perfluoropolyether moiety; and a 3 rd alkoxysilane compound having at least 4 or more alkoxy groups in the molecule and having no perfluoropolyether moiety and no perfluoro group. In the present embodiment, the coated article refers to an article having a coating layer formed using the coating composition. The coating layer is formed by bringing a coating composition according to an embodiment of the present invention into contact with an inorganic substrate by a method such as coating, and reacting the inorganic substrate with a 1 st alkoxysilane compound, a 2 nd alkoxysilane compound, and a 3 rd alkoxysilane compound contained in the coating composition to form a film. Here, the inorganic substrate usable in the embodiment refers to all substrates made of inorganic materials such as glass, metal, calcium carbonate, talc, mica, glass fiber, aluminum hydroxide, calcium carbonate, carbon black, potassium titanate, kaolin, graphite, ferrite, sepiolite, zeolite, nepheline syenite, and the like.
The inorganic base material and the coating composition can be brought into contact with each other by a conventional coating (application) method such as a doctor blade method, a bar coating method, a dipping method, an air spraying method, a roll brush method, and a roll coating method. For example, in order to apply the coating composition by a roll coating method or the like, the coating composition can be diluted with a solvent in an amount of 600 times or more of the total weight of the 1 st alkoxysilane compound, the 2 nd alkoxysilane compound, and the 3 rd alkoxysilane compound. As the solvent for diluting the 1 st, 2 nd and 3 rd alkoxysilane compounds, a fluorine-based solvent called a next-generation fluorine-based solvent (fluorochlorohydrocarbon compound) such as Perfluorocarbon (PFC), hydrofluoroolefin (HFO), hydrofluoroether (HFE), hydrofluorochlorocarbon (HCFC) and the like is preferably used.
Here, the 1 st alkoxysilane compound having a perfluoropolyether portion in the molecule contained in the coating composition is preferably a compound represented by the following formula II:
[ solution 19]
Figure GDA0003547089620000091
(wherein Rf is a perfluoropolyether moiety represented by the formula I, R 1 Each independently an alkyl group having 1 to 4 carbon atoms, X is a substituent having an alkoxysilyl group or a perfluoroalkyl group having 1 or 2 carbon atoms, and e is an integer of 1 to 4). In the formula II, when X is a substituent having an alkoxysilyl group, the 1 st alkoxysilane compound having a perfluoropolyether portion in the molecule used in the present embodiment may be a compound represented by the following formula III:
[ solution 20]
Figure GDA0003547089620000092
(wherein Rf is a perfluoropolyether moiety represented by the formula I, R 1 Each independently is an alkyl group having 1 to 4 carbon atoms, R 2 Each independently an alkyl group having 1 to 4 carbon atoms, e is an integer of 1 to 4, and h is an integer of 1 to 4). In the formula II, X is perfluoroalkyl group having 1 or 2 carbon atomsIn this case, the 1 st alkoxysilane compound having a perfluoropolyether portion in the molecule used in the present embodiment may be a compound represented by the following formula IVa:
[ solution 21]
Figure GDA0003547089620000093
(wherein Rf is a perfluoropolyether moiety represented by the formula I, R) 1 Each independently an alkyl group having 1 to 4 carbon atoms, e is an integer of 1 to 4); a compound represented by the following formula IVb:
[ solution 22]
Figure GDA0003547089620000094
(wherein Rf is a perfluoropolyether moiety represented by the formula I, R 1 Each independently an alkyl group having 1 to 4 carbon atoms, e is an integer of 1 to 4); or a compound represented by formula IVc below:
[ solution 23]
Figure GDA0003547089620000095
(wherein Rf is a perfluoropolyether moiety represented by the formula I, R) 1 Each independently is an alkyl group having 1 to 4 carbon atoms, and e is an integer of 1 to 4).
On the other hand, the 2 nd alkoxysilane compound having a perfluoro group in the molecule and no perfluoropolyether moiety may be a compound represented by the following formula V:
[ solution 24]
Figure GDA0003547089620000101
(in the formula, R 3 An alkyl group having 1 to 4 carbon atoms, f is an integer of 1 to 6, and g is an integer of 0 to 5).
On the other hand, the 3 rd alkoxysilane compound having at least 4 or more alkoxy groups in the molecule and having no perfluoropolyether portion and no perfluorofluoro group may be a compound represented by the following formula VI:
[ solution 25]
Figure GDA0003547089620000102
(in the formula, R 4 、R 5 Each independently represents hydrogen or alkyl having 1 to 5 carbon atoms, R present in the molecule of the compound represented by the formula VI 4 And R 5 At least 4 of them are alkyl groups having 1 to 5 carbon atoms, and i is an integer of 1 to 5).
By bringing the inorganic substrate into contact with the coating composition of the present embodiment, the inorganic substrate can be reacted with the 1 st alkoxysilane compound, the 2 nd alkoxysilane compound, and the 3 rd alkoxysilane compound contained in the coating composition. The 1 st, 2 nd and 3 rd alkoxysilane compounds contain an alkoxysilyl group. The alkoxysilyl group is hydrolyzed to be able to bond to the inorganic substrate. That is, the 1 st alkoxysilane compound imparts a perfluoropolyether moiety to the surface of the inorganic substrate via-SiO-, while the 2 nd alkoxysilane compound imparts a perfluoro group to the surface of the inorganic substrate via-SiO-. The 3 rd alkoxysilane compound bridges the 1 st and 2 nd alkoxysilane compounds to form a high-order structure on the surface of the inorganic substrate. These alkoxysilane compounds are also commonly referred to as silane coupling agents. The coating composition of the embodiment contains 3 or more silane coupling agents, and these silane coupling agents react with the inorganic base material to form a coating layer capable of modifying the characteristics of the surface of the inorganic base material.
The number average molecular weight of the 1 st alkoxysilane compound (the compound represented by the formula II, the formula III, the formula IVa, the formula IVb, the formula IVc) is particularly preferably larger than the molecular weight of the 2 nd alkoxysilane compound (the compound represented by the formula V). In particular, the number average molecular weight of the 1 st alkoxysilane compound is preferably 10 times or more the molecular weight of the 2 nd alkoxysilane compound. As described above, the 1 st alkoxysilane compound functions to react with an inorganic substrate to impart a perfluoropolyether moiety to the surface of the inorganic substrate. On the other hand, the 2 nd alkoxysilane compound functions to react with the inorganic substrate to impart a perfluoro group to the surface of the inorganic substrate. In this case, it is very preferable to mix a relatively long perfluoropolyether portion derived from the 1 st alkoxysilane compound with a relatively short perfluoro group derived from the 2 nd alkoxysilane compound on the surface of the inorganic base material, particularly in terms of improving the antifouling property of the inorganic base material. The number average molecular weight of the 1 st alkoxysilane compound is 2000 or more, preferably 3000 or more, and more preferably 4000 or more. Therefore, the molecular weight of the 2 nd alkoxysilane compound can be selected depending on the number average molecular weight of the 1 st alkoxysilane compound, and can be 200, 300, 400, or the like.
In the coating layer formed by reacting the coating composition containing the 1 st alkoxysilane compound and the 2 nd alkoxysilane compound with the inorganic substrate, a relatively long perfluoropolyether portion (derived from the 1 st alkoxysilane compound) and a perfluoro group (derived from the 2 nd alkoxysilane compound) shorter than the perfluoropolyether portion are mixed. If a coating composition containing only the 1 st alkoxysilane compound is prepared and a coating layer having only a relatively long perfluoropolyether portion is formed on the surface of an inorganic substrate, the antifouling property of the inorganic substrate can be improved. However, the present inventors have made extensive studies and found that the alkali resistance of such a coating layer is deteriorated. On the other hand, if a coating composition containing only the 2 nd alkoxysilane compound is prepared and a coating layer having only a short perfluoro group is formed on the surface of the inorganic base material, it is found that it is difficult to form a coating layer having excellent antifouling property and sliding property on the surface of the inorganic base material. That is, the coating composition of the embodiment preferably contains both the 1 st and 2 nd alkoxy compounds, and in the coating layer formed on the coated article of the embodiment, it is highly preferable that a relatively long perfluoropolyether portion and a perfluoro group shorter than the perfluoropolyether portion are present in a mixed state.
The phenomenon is explained in detail, but it is not limited by a particular theory. Since the 1 st alkoxysilane compound has a relatively long perfluoropolyether group in the molecule, many 1 st alkoxysilane compounds cannot react with an inorganic substrate. That is, even if a coating composition containing only the 1 st alkoxysilane compound is prepared and the coating composition is reacted with an inorganic substrate, it is considered difficult to react the 1 st alkoxysilane compound to such an extent that all surfaces of the inorganic substrate are covered. If the coated article in this state is exposed to a basic substance, a basic hydrolysis reaction occurs at the bonding portion of the inorganic substrate and the 1 st alkoxysilane compound, and the 1 st alkoxysilane compound is detached from the inorganic substrate. Therefore, it is considered that the coating layer formed from the coating composition containing only the 1 st alkoxysilane compound has poor alkali resistance.
On the other hand, the 2 nd alkoxysilane does not have a perfluoropolyether moiety as long as the 1 st alkoxysilane, and therefore can react relatively well with an inorganic substrate. Therefore, if the coating composition contains both the 1 st alkoxysilane compound and the 2 nd alkoxysilane compound, the 2 nd alkoxysilane compound will bond to the surface of the inorganic substrate so as to fill in the gaps between the bonding portions of the 1 st alkoxysilane compound, and as a result, the entire surface of the inorganic substrate can be uniformly coated with the perfluoropolyether portion from the 1 st alkoxysilane compound and the perfluoro group from the 2 nd alkoxysilane compound.
As described above, in the coating composition of the embodiment, it is preferable that the weight ratio of 10:1 to 10:40 contains a 1 st alkoxysilane compound and a 2 nd alkoxysilane compound. The coating composition is particularly preferably applied in a weight ratio of 10:1 to 10:20 contains a 1 st alkoxysilane compound and a 2 nd alkoxysilane compound. If the number average molecular weight of the 1 st alkoxysilane compound is 10 times the molecular weight of the 2 nd alkoxysilane compound, and the ratio of the number average molecular weight of the 1 st alkoxysilane compound to the number average molecular weight of the 2 nd alkoxysilane compound in the coating composition is 10: in the case where 10 contains the 1 st alkoxysilane compound and the 2 nd alkoxysilane compound, the molar ratio of the 1 st alkoxysilane compound to the 2 nd alkoxysilane compound is 1:10. in the coating composition of the embodiment, in order to improve the antifouling property and alkali resistance of the coated article, the following two points are important: a balance of the number average molecular weight of the 1 st alkoxy compound having a relatively long perfluoropolyether moiety and the molecular weight of the 2 nd alkoxy silane compound having a relatively short perfluoro group; and blending the 1 st alkoxysilane compound and the 2 nd alkoxysilane compound in an appropriate molar ratio.
On the other hand, the 3 rd alkoxysilane compound (the compound represented by the formula VI) functions to provide a bridging structure to the 1 st alkoxysilane compounds, the 2 nd alkoxysilane compounds, between the 1 st alkoxysilane compound and the 2 nd alkoxysilane compound, between the 1 st alkoxysilane compound and the inorganic substrate, between the 2 nd alkoxysilane compound and the inorganic substrate, and the like. By including the 3 rd alkoxysilane compound in the coating composition of the embodiment, the coating layer formed from the coating composition of the embodiment may have a high-order structure. That is, the coating layer has a high-order structure in which the perfluoropolyether portion derived from the 1 st alkoxysilane compound and the perfluoro group derived from the 2 nd alkoxysilane compound uniformly cover the entire surface of the inorganic substrate, and these perfluoropolyether portion and perfluoro group are bridged with each other. By having such a complicated structure for the coating layer, the coating layer does not fall off from the inorganic base material even if the coated article of the embodiment is placed under severe conditions of high temperature and high humidity.
As described above, in the coating composition of the embodiment, it is preferable that the ratio of the weight of the coating composition of the embodiment is 10:0.5 to 10:5 contains a 1 st alkoxysilane compound and a 3 rd alkoxysilane compound. The coating composition is particularly preferably applied in a weight ratio of 10:1 to 10:4.5 contains a 1 st alkoxysilane compound and a 3 rd alkoxysilane compound. In the coating composition of the embodiment, in order to improve the antifouling property, alkali resistance and durability under high temperature and high humidity of the coated article, the following two points are important: a balance of the number average molecular weight of the 1 st alkoxy compound having a relatively long perfluoropolyether moiety and the molecular weight of the 2 nd alkoxy silane compound having a relatively short perfluoro group; and further 1 st, 2 nd and 3 rd alkoxysilane compounds in an appropriate molar ratio.
The inorganic substrate coated with the coating composition of the embodiment is placed in an atmosphere of about room temperature to 300 ℃, and the 1 st alkoxysilane, the 2 nd alkoxysilane, and the 3 rd alkoxysilane compound are reacted with the inorganic substrate, whereby a coating layer can be formed on the surface of the inorganic substrate. In order to reliably react the 1 st, 2 nd and 3 rd alkoxysilane compounds with the inorganic substrate to form a coating layer in which the entire surface of the inorganic substrate is covered with perfluoropolyether moieties and perfluoro groups and the perfluoropolyether moieties and the perfluoro groups are bridged, it is preferable to heat the inorganic substrate coated with the coating composition in an atmosphere of about 150 to 250 ℃.
The coated article having a coating layer formed by reacting the coating composition of the embodiment with an inorganic base material has excellent stain resistance, abrasion resistance, and durability to alkali. In addition, even in a coated article in which a coating layer is formed by reacting the coating composition of the embodiment with an inorganic base material, these favorable characteristics are not degraded even under severe conditions of high temperature and high humidity. The coating composition of the embodiment can be applied to in-vehicle displays, mobile terminals, personal computers, various display devices, and the like, and can impart excellent antifouling property, abrasion resistance, alkali resistance, and high-temperature high-humidity durability to these devices.
[ examples ]
(1) Synthesis of 1 st alkoxysilane compound having perfluoropolyether moiety within the molecule
Synthesis example 1-1 Synthesis of perfluoropolyether moiety-containing alkoxysilane Compound (1 a)
11.82g (3.0 mmol) of Fluorolink D-4000 (Solvay Co., ltd.), 1.48g (7.2 mmol) of 3-isocyanatopropyltrimethoxysilane (Kanto chemical Co., ltd.), 0.015g (0.15 mmol) of triethylamine (Kanto chemical Co., ltd.) as a catalyst and 12.0g of m-ditrifluorotoluene (Tokyo chemical industry Co., ltd.) as a reaction solvent were weighed and placed in a 30mL eggplant-shaped flask equipped with a stirrer. The reaction solution was stirred at 50 ℃. Methanol was added to the reaction solution after the reaction to separate the reaction solution into layers, thereby stopping the reaction. The upper layer was removed and only the lower layer was washed 3 times with methanol. The washed liquid was dried under reduced pressure to remove the solvent, thereby obtaining (10.2 g, yield 87%) of a perfluoropolyether group-containing alkoxysilane compound (1 a). Further, fluorolink D-4000 is a perfluoropolyether compound having a number average molecular weight of 4000 represented by the following formula,
[ solution 26]
Figure GDA0003547089620000131
Accordingly, the number average molecular weight of the perfluoropolyether moiety-containing alkoxysilane compound (1 a) is about 4,400.
Synthesis example 1-2 Synthesis of perfluoropolyether moiety-containing alkoxysilane Compound (1 b)
Fluorolink ZMF-402 (Solvay Co., ltd.) 11.82g (3.0 mmol), 3-isocyanatopropyltrimethoxysilane (Kanto chemical Co., ltd.) 0.74g (3.6 mmol), triethylamine (Kanto chemical Co., ltd.) 0.015g (0.15 mmol) as a catalyst, and m-ditrifluorotoluene (Tokyo chemical industry Co., ltd.) 12.0g as a reaction solvent were weighed and placed in a 30mL eggplant-shaped flask with a stirrer. The reaction solution was stirred at 50 ℃. Methanol was added to the reaction solution after the reaction to separate the reaction solution into layers, thereby stopping the reaction. The upper layer was removed and only the lower layer was washed 3 times with methanol. The washed liquid was dried under reduced pressure to remove the solvent, thereby obtaining perfluoropolyether moiety-containing alkoxysilane compound (1 b) (10.2 g, yield 87%). Further, fluorolink ZMF-402 is a perfluoropolyether compound having a number average molecular weight of 4,000 represented by the following formula,
[ solution 27]
Figure GDA0003547089620000141
Accordingly, the number average molecular weight of the perfluoropolyether moiety-containing alkoxysilane compound (1 b) is about 4,200.
Synthesis examples 1 to 3 Synthesis of perfluoropolyether moiety-containing alkoxysilane Compound (1 c)
18.00g (3.0 mmol) of Fluorolink D-6000 (Solvay Co., ltd.), 1.48g (7.2 mmol) of 3-isocyanatopropyltrimethoxysilane (Kanto chemical Co., ltd.), 0.015g (0.15 mmol) of triethylamine (Kanto chemical Co., ltd.) as a catalyst and 18.0g of m-ditrifluorotoluene (Tokyo chemical industry Co., ltd.) as a reaction solvent were weighed and placed in a 30mL eggplant-shaped flask equipped with a stirrer. The reaction solution was stirred at 50 ℃. Methanol was added to the reaction solution after the reaction to separate the reaction solution into layers, thereby stopping the reaction. The upper layer was removed and only the lower layer was washed 3 times with methanol. The washed liquid was dried under reduced pressure to remove the solvent, thereby obtaining (17.31 g, yield 90%) of a perfluoropolyether group-containing alkoxysilane compound (1 c).
Furthermore, fluorolink D-6000 is a perfluoropolyether compound having a number average molecular weight of 6000 represented by the following formula,
[ solution 28]
Figure GDA0003547089620000142
Accordingly, the number average molecular weight of the perfluoropolyether moiety-containing alkoxysilane compound (1 c) is about 6,400.
(2) Preparation of coating composition
(2-1) example 1
0.1g of the perfluoropolyether group-containing alkoxysilane compound (1 a) synthesized in Synthesis example 1-1, 0.05g of KBM-7103 (KBM-7103, inc.) which is an alkoxysilane compound having a perfluoro group in the molecule and no perfluoropolyether group, 0.01g of methyl silicate 51 (Konkokang Co., ltd.) which is an alkoxysilane compound having at least 4 or more alkoxy groups in the molecule and no perfluoropolyether group and a perfluoro group, and 99.84g of NOVEC HFE-7200 (3M Japan Co., ltd.) as a solvent were weighed and placed in a 200mL beaker and stirred at room temperature for 1 hour to prepare a coating composition.
(2-2) example 2
0.1g of the perfluoropolyether group-containing alkoxysilane compound (1 a) synthesized in Synthesis example 1-1, 0.05g of KBM-7103 (KBn chemical industries, ltd.) as an alkoxysilane compound having a perfluoro group in the molecule and no perfluoropolyether group, 0.01g of ethyl silicate 28 (KBn chemical industries, ltd.) as an alkoxysilane compound having at least 4 or more alkoxy groups in the molecule and no perfluoropolyether group and a perfluoro group, and 99.84g of NOVEC HFE-7200 (3M Japan, ltd.) as a solvent were weighed and placed in a 200mL beaker and stirred at room temperature for 1 hour to prepare a coating composition.
(2-3) example 3
0.1g of the perfluoropolyether group-containing alkoxysilane compound (1 b) synthesized in Synthesis example 1-2, 0.05g of KBM-7103 (KBt chemical industries, ltd.) as an alkoxysilane compound having a perfluoro group in the molecule and no perfluoropolyether group, 0.01g of methyl silicate 51 (Konkon Chemicals, ltd.) as an alkoxysilane compound having at least 4 or more alkoxy groups in the molecule and no perfluoropolyether group and a perfluoro group, and 99.84g of NOVEC HFE-7200 (3M Japan, ltd.) as a solvent were weighed and placed in a 200mL beaker and stirred at room temperature for 1 hour to prepare a coating composition. KBM-7103 is trifluoropropyltrimethoxysilane (molecular weight: 218) represented by the following formula,
[ solution 29]
Figure GDA0003547089620000151
In addition, NOVEC HFE-7200 is a hydrofluoroether (a mixture of ethyl nonafluorobutyl ether and ethyl nonafluoroisobutyl ether). Further, methyl silicate 51 is a methyl silicate tetramer (average) represented by the following formula,
[ solution 30]
Figure GDA0003547089620000152
The ethyl silicate 28 is an alkoxysilane compound (tetraethoxysilane) represented by the following formula,
[ solution 31]
Figure GDA0003547089620000153
(2-4) example 4
0.1g of the perfluoropolyether group-containing alkoxysilane compound (1 c) synthesized in Synthesis examples 1 to 3, 0.05g of KBM-7103 (KBM-7103, co., ltd.) as an alkoxysilane compound having a perfluoro group in the molecule and no perfluoropolyether group, 0.01g of methyl silicate 51 (Koncokang Co., ltd.) as an alkoxysilane compound having at least 4 or more alkoxy groups in the molecule and no perfluoropolyether group and a perfluoro group, and 99.84g of NOVEC HFE-7200 (3M Japan Co., ltd.) as a solvent were weighed and placed in a 200mL beaker and stirred at room temperature for 1 hour to prepare a coating composition.
(2-4) comparative example 1
A coating composition was prepared in the same manner as in example 1 except that methyl silicate 51 was not added and the amount of NOVEC HFE-7200 was changed to 99.85 g.
(2-5) comparative example 2
A coating composition was prepared in the same manner as in example 3 except that methyl silicate 51 was not added and the amount of NOVEC HFE-7200 was changed to 99.85 g.
(2-6) comparative example 3
A coating composition was prepared in the same manner as in example 1 except that KBM-7103 was not added, and that 0.1g of methyl silicate 51 was added to adjust the amount of NOVEC HFE-7200 to 99.8 g.
(2-7) comparative example 4
A coating composition was prepared in the same manner as in example 1 except that 0.5g of KBM-7103 and 0.1g of methyl silicate 51 were added and the amount of NOVEC HFE-7200 was changed to 99.3 g.
(3) Formation of the coating
The coating compositions prepared in examples and comparative examples were applied to one surface of a cleaned glass plate (water contact angle of about 10 ℃ C., dimension: 100 mm. Times.100 mm) by means of a spray, and the coating composition was cured by heating in an oven at 170 ℃ for 30 minutes to form a coating layer.
(4) Evaluation of coating appearance
The appearance of the coating was visually observed. The coating layer formed to be transparent and smooth was evaluated as "good", the coating layer was evaluated as "uneven", and the coating layer was evaluated as "white".
(5) Measurement of Water contact Angle
The measurement of the static water contact angle of the coated glass plate was carried out by a contact angle measuring apparatus (Kyowa interface science Co., ltd.) according to the static drop method of JIS R3257. A large water contact angle indicates a low wettability of the coating, that is to say a high water repellency. It is known that the coating layer generally causes its surface to be contaminated by contact with water containing various dusts or impurities. Therefore, the coating layer is not easily wetted with water as a criterion for the stain resistance of the coating layer in the present specification.
(6) Evaluation of alkali resistance
The glass plate on which the coating layer was formed was immersed in a 0.1 wt% aqueous solution of sodium hydroxide and allowed to stand at 25 ℃ for 24 hours. The glass plate was taken out, and the surface of the glass plate was cleaned with pure water to remove the aqueous sodium hydroxide solution, and after drying the glass plate at room temperature, the water contact angle was measured using a contact angle measuring apparatus (Kyowa interface science Co., ltd.).
(7) Evaluation of durability in high temperature and high humidity Environment
The glass plate with the coating layer formed thereon was allowed to stand for 1000 hours in a high-temperature and high-humidity environment at a temperature of 85 ℃ and a humidity of 85%. The glass plate was taken out from the environment and left to stand at normal temperature, and then the water contact angle was measured using a contact angle measuring apparatus (coyote interfacial science co.
(8) Evaluation of durability in high temperature Environment
The glass plate on which the coating layer was formed was allowed to stand at a high temperature of 90 ℃ for 1000 hours. The glass plate was taken out from the environment and left at normal temperature, and then the water contact angle was measured using a contact angle measuring apparatus (coyote interface science ltd).
The results of examples and comparative examples are shown in tables 1 and 2. In tables 1 and 2, the units of the numbers described in the compositions of the coating compositions are "parts by weight". In comparative examples 3 and 4, since the coating layers were opaque, the water contact angle of the coating layer after standing in a high-temperature and high-humidity environment and the water contact angle of the coating layer after standing in a high-temperature environment were not measured in the following.
[ Table 1]
[ Table 1]: coating composition and evaluation of coating (examples)
Figure GDA0003547089620000171
[ Table 2]
[ Table 2]: coating composition and evaluation of coating layer (comparative example)
Figure GDA0003547089620000181
Using the coating compositions of the examples, substantially transparent coatings were successfully formed. The coating compositions of the examples form coatings that reduce the wettability of the surface of the glass sheet. On the other hand, the coating compositions of comparative examples 1 and 2 succeeded in forming substantially transparent coatings which reduced the wettability of the glass plate surface and did not increase the wettability even when immersed in an alkaline aqueous solution, but if these glass plates were placed in a high-temperature and high-humidity environment or a high-temperature environment, the wettability of the coating surface increased. When the compositions of the coating compositions of example 1 and comparative example 1, and example 2 and comparative example 1 were compared, respectively, the coating composition of comparative example 1 did not contain methyl silicate 51 or ethyl silicate 28 corresponding to the "3 rd alkoxysilane compound", that is, an alkoxysilane compound having at least 4 or more alkoxy groups in the molecule and having no perfluoropolyether portion and no perfluoro group. In addition, when the compositions of the coating compositions of example 3 and comparative example 2 were compared, the coating composition of comparative example 2 did not contain methyl silicate 51 or ethyl silicate 28 corresponding to the "3 rd alkoxysilane compound", that is, an alkoxysilane compound having at least 4 or more alkoxy groups in the molecule and having no perfluoropolyether portion and no perfluoro group. From the results of comparative examples 1 and 2, it was found that a water-repellent coating layer which can withstand an alkaline aqueous solution can be formed on the glass surface by only the alkoxysilane compound (1 a, 1b, or 1 c) having a perfluoropolyether portion in the molecule corresponding to the 1 st alkoxysilane compound and the 2 nd alkoxysilane compound having a perfluoro group in the molecule and no perfluoropolyether portion, but if these coating layers are once left in a high-temperature high-humidity environment or a high-temperature environment, the alkoxysilane compound comes off the glass plate.
When the compositions of the coating compositions of example 1 and comparative example 3 were compared, the coating composition of comparative example 3 contained no KBM-7103 as the "2 nd alkoxysilane compound" and a large amount (same amount as the 1 st alkoxysilane compound) of methyl silicate 51 as the "3 rd alkoxysilane compound". The coating composition of comparative example 3 successfully formed a coating layer that could also withstand an alkaline aqueous solution, but the coating layer was cloudy and was not suitable for use in coating articles. When the compositions of the coating compositions of example 1 and comparative example 4 were compared, the coating composition of comparative example 4 contained a large amount (5 times the amount of the 1 st alkoxysilane compound) of the "2 nd alkoxysilane compound" and also contained a large amount (the same amount as the 1 st alkoxysilane compound) of methyl silicate 51 as the "3 rd alkoxysilane compound". The coating composition of comparative example 4 successfully formed a coating layer having a large water contact angle, but the coating layer was clouded and was not suitable for use in coating an article.
From the results, it is found that it is important for a coating layer excellent in antifouling property, alkali resistance and resistance to high temperature and high humidity environment to have a high-order structure in which a relatively long perfluoropolyether portion derived from a 1 st alkoxysilane compound and a relatively short perfluoro group derived from a 2 nd alkoxysilane compound are mixed in a well-balanced manner, and these perfluoropolyether portion and perfluoro group are bridged by a 3 rd alkoxysilane. That is, it can be said that it is important to study the composition of the coating composition containing these 3 alkoxysilanes in a balanced manner.

Claims (6)

1. A coating composition comprising at least:
a 1 st alkoxysilane compound having a perfluoropolyether portion in the molecule;
a 2 nd alkoxysilane compound having a perfluoro group in a molecule and having no perfluoropolyether moiety; and
a 3 rd alkoxysilane compound having at least 4 or more alkoxy groups in the molecule and having no perfluoropolyether portion and no perfluoro group,
the 1 st alkoxysilane compound is a compound represented by the following formula II:
Figure FDA0003831577530000011
wherein Rf is a perfluoropolyether moiety represented by formula I:
Figure FDA0003831577530000012
wherein a, b, c and d are each independently an integer of 0 to 200, a, b, c and d are not all 0, the repeating units in the brackets may be bonded in any order, and R is 1 Each independently an alkyl group having 1 to 4 carbon atoms, X is a substituent having an alkoxysilyl group or a perfluoroalkyl group having 1 to 3 carbon atoms, e is an integer of 1 to 4,
the 2 nd alkoxysilane compound is a compound represented by the following formula V:
Figure FDA0003831577530000013
in the formula, R 3 Is an alkyl group having 1 to 4 carbon atoms, f is an integer of 1 to 6, g is an integer of 0 to 5,
the 3 rd alkoxysilane compound is a compound represented by the following formula VI:
Figure FDA0003831577530000014
in the formula, R 4 、R 5 Each independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms, R present in the molecule of the compound represented by the formula VI 4 And R 5 At least 4 of which are C1-5 alkyl groups, i is an integer of 1-5,
the weight ratio of 10:1 to 10:40 contains the 1 st alkoxysilane compound and the 2 nd alkoxysilane compound, and
the weight ratio of 10:0.5 to 10:5 contains the 1 st alkoxysilane compound and the 3 rd alkoxysilane compound.
2. The coating composition of claim 1, wherein the number average molecular weight of the 1 st alkoxysilane compound is greater than the molecular weight of the 2 nd alkoxysilane compound.
3. The coating composition according to claim 1 or 2, wherein the number average molecular weight of the 1 st alkoxysilane compound is 10 times or more the molecular weight of the 2 nd alkoxysilane compound.
4. The coating composition of claim 1 or 2, further comprising a solvent.
5. The coating composition of claim 3, further comprising a solvent.
6. A coated article formed by reacting a coating composition with an inorganic substrate, the coating composition comprising at least:
a 1 st alkoxysilane compound having a perfluoropolyether moiety in the molecule;
a 2 nd alkoxysilane compound having a perfluoro group in a molecule and having no perfluoropolyether portion; and
a 3 rd alkoxysilane compound having at least 4 or more alkoxy groups in the molecule and having no perfluoropolyether portion and no perfluoro group,
the 1 st alkoxysilane compound is a compound represented by the following formula II:
Figure FDA0003831577530000021
wherein Rf is a perfluoropolyether moiety represented by formula I:
Figure FDA0003831577530000022
wherein a, b, c and d are each independently an integer of 0 to 200, a, b, c and d are not all 0, the repeating units in the brackets may be bonded in any order, and R is 1 Each independently an alkyl group having 1 to 4 carbon atoms, X is a substituent having an alkoxysilyl group or a perfluoroalkyl group having 1 to 3 carbon atoms, e is an integer of 1 to 4,
the 2 nd alkoxysilane compound is a compound represented by the following formula V:
Figure FDA0003831577530000023
in the formula, R 3 Is an alkyl group having 1 to 4 carbon atoms, f is an integer of 1 to 6, g is an integer of 0 to 5,
the 3 rd alkoxysilane compound is a compound represented by the following formula VI:
Figure FDA0003831577530000031
in the formula, R 4 、R 5 Each independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms, R present in the molecule of the compound represented by the formula VI 4 And R 5 At least 4 of which are C1-5 alkyl groups, i is an integer of 1-5,
the weight ratio of 10:1 to 10:40 contains the 1 st alkoxysilane compound and the 2 nd alkoxysilane compound, and
the weight ratio of 10:0.5 to 10:5 contains the 1 st alkoxysilane compound and the 3 rd alkoxysilane compound.
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