WO2014021135A1 - Liquide résistant à l'eau, pièce résistant à l'eau, et procédé de production d'un liquide résistant à l'eau et d'une pièce résistant à l'eau - Google Patents

Liquide résistant à l'eau, pièce résistant à l'eau, et procédé de production d'un liquide résistant à l'eau et d'une pièce résistant à l'eau Download PDF

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WO2014021135A1
WO2014021135A1 PCT/JP2013/069860 JP2013069860W WO2014021135A1 WO 2014021135 A1 WO2014021135 A1 WO 2014021135A1 JP 2013069860 W JP2013069860 W JP 2013069860W WO 2014021135 A1 WO2014021135 A1 WO 2014021135A1
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water
repellent
repellent liquid
water repellent
liquid
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PCT/JP2013/069860
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English (en)
Japanese (ja)
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濱口　滋生
宏紀 深澤
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セントラル硝子株式会社
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/76—Hydrophobic and oleophobic coatings

Definitions

  • the present invention relates to a water-repellent liquid used for forming a water-repellent film on various glass articles, a water-repellent article obtained using the water-repellent liquid, and a method for producing them.
  • Water repellent glass with excellent water repellency and durability is useful as a water repellent glass for various glass articles in various fields such as window materials for automobiles, as well as windows for ships as well as for buildings. It can be used, and various studies have been made so far.
  • fluoroalkylsilane compounds those having a large number of fluorocarbon units, for example, fluoroalkylsilane compounds having 8 or more fluorocarbon units (hereinafter referred to as “long-chain fluoroalkylsilane compounds”).
  • EPA US Environmental Protection Agency
  • PFOA perfluorooctanoic acid
  • the present applicant provides a base film having a surface with a unique fine uneven surface layer controlled with a high specific surface area on the glass surface, such as the water-repellent glass described in Patent Document 1, It discloses that by improving the adhesion efficiency and adhesion of the water-repellent film to be coated, it is possible to maintain excellent water-repellent performance, abrasion resistance, weather resistance and the like over the long term.
  • the present applicant uses a water repellent glass manufacturing method described in Patent Document 2 to hydrolyze a starting raw material fluoroalkylsilane compound or alkylalkoxysilane compound in a dilute solvent with an acid catalyst,
  • a dehydrating agent to increase the degree of polycondensation and controlling and adjusting the water repellent liquid, which is controlled and prepared to form a film on the glass substrate, it exhibits excellent wear resistance and weather resistance. Disclosure.
  • the present applicant when forming a water-repellent film like the water-repellent glass described in Patent Document 3, the surface of the glass substrate is in a state where the temperature of the glass substrate is about 90 to 200 ° C. Depending on the direction, a water-repellent layer is formed on the surface of a fine concavo-convex glass substrate with streak-like wrinkles, which makes the water-repellent remarkably excellent in weather resistance, abrasion resistance, scratch resistance and durability. A method of forming a water repellent film that exhibits performance and maintains its effect over a long period of time is disclosed.
  • each of linear polydimethylsiloxane having 30 to 400 dimethylsiloxane units (—Si (CH 3 ) 2 O—) and fluoroalkylsilane has disclosed in Japanese Patent Application Laid-Open No. H11-284, each of linear polydimethylsiloxane having 30 to 400 dimethylsiloxane units (—Si (CH 3 ) 2 O—) and fluoroalkylsilane.
  • a method for producing a water-slidable article that is chemically bonded to the surface of a material to form a water-sliding layer is disclosed.
  • a fluorine compound represented by the following general formula (1) is provided for the purpose of providing a PFOA-free water- and oil-repellent agent, an antifouling agent and the like that have no environmental impact. Disclosure.
  • Z represents an aromatic hydroxyl group, an aromatic amino group, a carboxyl group or a sulfonic acid group (and neutralized salts or esters of these functional groups).
  • the water-repellent glass described in Patent Document 1 is a technique that can answer the above-mentioned needs, but has a two-layer structure consisting of a specific base film and a water-repellent layer, and the film formation process of the base film and the water-repellent layer is complicated. Therefore, the film forming facility becomes large and tends to be expensive. For this reason, a water-repellent glass which is not a two-layer film but a single-layer film and excellent in water-repellent performance, abrasion resistance, weather resistance and the like is desired.
  • the water-repellent glass obtained by the method described in Patent Document 2 is a water-repellent glass whose water-repellent performance and durability are improved and approaches the desired performance even with a single layer film, but the number of fluorocarbon units is less than 8.
  • a fluoroalkylsilane compound for example, a fluoroalkylsilane compound having 4 to 6 fluorocarbon units
  • the amount of water and the water repellent performance, and the durability performance has not been fully examined, and there is room for improvement.
  • the water-repellent glass described in Patent Document 3 is a water-repellent glass that improves the water-repellent performance and durability and approaches the desired performance even if it is a single layer film, as in Patent Document 2.
  • the substrate is heated or the surface of the glass substrate is uneven, the operation is complicated, and it may be difficult to say that the workability during production, particularly the handling thereof is simple and highly efficient.
  • the water-slidable article disclosed in Patent Document 4 has good weather resistance and durability
  • a treatment agent using a fluoroalkylsilane compound having less than 8 fluorocarbon units is used as the treatment agent.
  • water repellency may be lowered in a relatively short period of time.
  • Patent Document 5 the performance is improved by devising the fluoroalkylsilane compound itself having less than 8 fluorocarbon units.
  • the fluoroalkylsilane compound itself having less than 8 fluorocarbon units.
  • Sufficient technical know-how and knowledge are required, and compound production facilities are also required at the time of production. It is difficult to say that the process up to the production of water-repellent glass is simple.
  • the compound represented by General formula (1) of patent document 5 is generally difficult to obtain, there exists a problem that implementation is difficult.
  • the present invention uses a fluoroalkylsilane-based compound having a number of fluorocarbon units of less than 8 that is generally available and conventionally used, does not require any special film-forming equipment, and the film to be formed is a single-layer film.
  • a water-repellent liquid that improves and achieves both durability, particularly weather resistance and abrasion resistance of the water-repellent article obtained, and a method for preparing the same, a water-repellent article obtained using the water-repellent liquid, and a method for producing the same. The task is to do.
  • the present inventors have studied in detail about the composition of a water-repellent liquid containing a fluoroalkylsilane compound having a number of fluorocarbon units of less than 8, a solvent, an acid catalyst, and water, using a specific acid catalyst, and A water-repellent article (water-repellent glass) that solves the above-mentioned problems by improving the blending amount of each raw material within a specific range and improves weather resistance and wear resistance even in a short-chain fluoroalkylsilane compound. It was found that can be easily obtained.
  • the durability such as weather resistance and abrasion resistance is the level required for water-repellent articles such as those used outdoors, especially water-repellent glass, and the durability of water-repellent articles is actually Outdoor exposure tests that evaluate the durability of water repellency by exposing the water-repellent article to the outdoor environment for a specified period of time, and durability such as water repellency by irradiating the water-repellent article with a strong UV light for a predetermined period of time It can be evaluated by a light resistance test for accelerating evaluation.
  • the present invention mixes at least a fluoroalkylsilane compound in which m, which is the number of fluorocarbon units represented by CF 3 (CF 2 ) m ⁇ 1 , is an integer less than 8, an organic solvent, and an organic sulfonic acid.
  • a water repellent liquid for forming a water repellent layer wherein the fluoroalkylsilane compound is added in an amount of 1 to 20% by mass relative to a total amount of 100% by mass of the water repellent liquid raw material.
  • the water repellent liquid is characterized in that the addition amount of the organic sulfonic acid is 0.1 to 29 mol times the addition amount of the alkylsilane compound.
  • the water repellent liquid of the present invention may contain water as a component other than the fluoroalkylsilane compound, the organic solvent, and the organic sulfonic acid.
  • the fluoroalkylsilane compound which may contain a product obtained by hydrolysis and / or polycondensation of the compound
  • the substrate surface By bonding, a solid coating (water repellent layer) having both excellent durability, particularly weather resistance and wear resistance, can be formed on the surface of the substrate.
  • the water repellent liquid of the present invention is a water repellent for forming a water repellent layer obtained by mixing a fluoroalkylsilane compound in which m of the fluorocarbon unit is an integer of less than 8, an organic solvent, and an organic sulfonic acid.
  • the addition amount of the fluoroalkylsilane compound is 1 to 20% by mass with respect to the total amount of the water-repellent liquid raw material of 100% by mass, and the addition of the organic sulfonic acid to the addition amount of the fluoroalkylsilane compound The amount is preferably 0.45 to 26 mol times.
  • a water repellent liquid obtained by mixing a fluoroalkylsilane compound in which m of the fluorocarbon unit is an integer of less than 8, an organic solvent, and an organic sulfonic acid is referred to as a “first water repellent liquid”. To do.
  • the amount of the organic sulfonic acid added is preferably 2.5 to 26 mol times the amount of the fluoroalkylsilane compound added.
  • the water repellent liquid of the present invention forms a water repellent layer obtained by mixing a fluoroalkylsilane compound in which m of the fluorocarbon unit is an integer of less than 8, an organic solvent, an organic sulfonic acid, and water.
  • the amount of the fluoroalkylsilane compound added relative to the total amount of the water repellent liquid material of 100% by mass is 1 to 20% by mass, and the organic sulfone relative to the amount of the fluoroalkylsilane compound added It is preferable that the addition amount of the acid is 0.15 to 2.8 mol times, and the addition amount of the water is 0.04 to 290 mol times the addition amount of the fluoroalkylsilane compound.
  • a water repellent liquid obtained by mixing a fluoroalkylsilane compound, an organic solvent, an organic sulfonic acid, and water, wherein m of the fluorocarbon unit is an integer less than 8, is referred to as “second water repellent liquid”.
  • the addition amount of the organic sulfonic acid is 0.2 to 2.5 mol times the addition amount of the fluoroalkylsilane compound, and the water is added to the addition amount of the fluoroalkylsilane compound.
  • the addition amount of is preferably 0.1 to 200 mol times.
  • the water repellent liquid preferably contains a compound obtained by hydrolyzing and / or polycondensing a fluoroalkylsilane compound in which m of the fluorocarbon unit is an integer of less than 8.
  • the fluoroalkylsilane compound is preferably fluoroalkyltrialkoxysilane in which m of the fluorocarbon unit is an integer of less than 8.
  • At least m of the fluorocarbon unit is an integer less than 8
  • a fluoroalkylsilane compound, an organic solvent, and an organic sulfonic acid are mixed to hydrolyze the fluoroalkylsilane compound
  • a method for preparing a water repellent liquid characterized in that the above water repellent liquid is prepared by polycondensation.
  • the hydrolysis may proceed due to moisture contained in the water repellent liquid raw material, or may proceed due to moisture taken in from the atmosphere during preparation of the water repellent liquid. Moreover, it may progress by the water added as a water repellent liquid raw material.
  • the hydrolysis and polycondensation do not need to proceed completely, and a part of the fluoroalkylsilane compound may be hydrolyzed or polycondensed.
  • the water repellent liquid is prepared by mixing a fluoroalkylsilane compound, an organic solvent, an organic sulfonic acid, and water in which m of the fluorocarbon unit is an integer of less than 8 to add water to the fluoroalkylsilane compound. Decomposition and / or polycondensation is preferred.
  • the water repellent liquid is preferably prepared by hydrolyzing and / or polycondensing the fluoroalkylsilane compound and then adding a dehydrating agent to the water repellent liquid.
  • the present invention provides a method for producing a water-repellent article in which a water-repellent layer is formed on a substrate, wherein the above-mentioned water-repellent liquid is applied on the surface of the substrate and heated at 50 to 350 ° C. for 1 to 60 minutes.
  • a water-repellent article is formed by forming a water-repellent layer.
  • the present invention is a water-repellent article obtained by the method for producing a water-repellent article described above.
  • the base material of the water-repellent article is preferably glass.
  • a fluorocarbon silane-based compound in which m of the fluorocarbon unit that is generally available and used in the past is an integer of less than 8 is used, and a film to be formed can be formed without requiring a special film forming facility.
  • the durability of the resulting water-repellent article, in particular the weather resistance and the abrasion resistance, is improved even if it is not a two-layer film structure such as a unique base film and a water-repellent layer, but a single-layer film consisting of only a single composition.
  • a compatible water-repellent liquid and water-repellent article can be easily obtained.
  • the image figure which put together the ratio (mol times) of the addition amount of an acid with respect to the addition amount of the fluoroalkylsilane type compound (FAS) in the 1st water repellent liquid of this invention, and a comparative example.
  • (1) on the straight line in the figure is Examples 1-1 and 1-2, Comparative Examples 1-1 to 1-4, 1-6, 1-8, 1-13, and (2) are Examples.
  • (13) shows Examples 2-1, 2-2, 2-10, 2-12 to 2-14, Comparative Examples 2-1 to 2-8, 2-11, and (14)
  • Examples 2-3, 2-15, (15) are Examples 2-4, (16) are Examples 2-5, (17) are Examples 2-6, (18) are Examples 2 ⁇ 7, (19) is Example 2-8, (20) is Example 2-9, (21) is Example 2-11, (22) is Example 2-16, (23) Are Example 2-17, (24) is Example 2-18, (25) is Example 2-19, (26) is Example 2-20, (27) is Example 2- 21, (28) is Example 2-22, (29) is Example 2-23, (30) is Example 2-24, (31) is Comparative Example 2-9, (32) is The ratio of Comparative Example 2-10 is shown.
  • a fluoroalkylsilane represented by the following general formula [1] is preferably used.
  • Y 1 is a monovalent hydrolyzable functional group.
  • m is an integer less than 8, and represents the number of fluorocarbon units (total number of CF 2 and CF 3 ).
  • p is an integer of 1 to 3, and represents the number of functional groups that can be hydrolyzed.
  • the number of fluorocarbon units improves the weather resistance and abrasion resistance of the resulting water-repellent film.
  • the number of fluorocarbon units is less than 8.
  • the addition amount of the fluoroalkylsilane compound is 1 to 20% by mass with respect to the total amount of the water repellent liquid. If it is less than 1% by mass, the initial water repellency (contact angle), weather resistance and abrasion resistance are significantly lowered. On the other hand, if it exceeds 20% by mass, the handling property at the time of preparing the water repellent liquid and the pot life of the water repellent liquid become worse, and the water repellent liquid becomes expensive, so the addition amount is 1 to 20% by mass. It is preferable.
  • fluoroalkylsilane compound a generally available fluoroalkylsilane compound in which m in the general formula [1] is less than 8 can be used.
  • CF 3 (CF 2 ) 5 CH 2 CH 2 Si (OCH 3 ) 3 CF 3 (CF 2 ) 5 CH 2 CH 2 SiCH 3 (OCH 3 ) 2
  • CF 3 (CF 2 ) 5 CH 2 CH 2 SiCl 3 CF 3 (CF 2 ) 5 CH 2 CH 2 SiCH 3 Cl 2
  • CF 3 (CF 2 ) 5 CH 2 CH 2 Si (CH 3 ) 2 Cl CF 3 (CF 2) 3 CH 2 CH 2 Si
  • a fluoroalkylsilane compound having a hydrolyzable functional group at one end is preferably used as the fluoroalkylsilane compound.
  • a fluoroalkylsilane-based compound having a hydrolyzable functional group at both ends tends to proceed with condensation, and it tends to be difficult to keep the properties of the water repellent liquid stable.
  • the condensed water-repellent liquid tends to become an excess after the water-repellent liquid is applied to the substrate and dried, and this excess tends to adhere firmly to the substrate, making it difficult to remove the excess after drying. There is. Considering this point, it is preferable to use a fluoroalkylsilane compound having a hydrolyzable functional group only at one end.
  • the number of hydrolyzable functional groups is preferably 3. If the number is less than 3, the amount of silanol groups to be produced is insufficient, so that the bond between the substrate and the resulting water repellent film is not sufficient, and the durability of the water repellent film may be lowered.
  • an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a chloro group or an isocyanate group
  • an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a chloro group or an isocyanate group
  • the hydrolyzable functional group if the reactivity of the hydrolyzable functional group is too high, handling at the time of water repellent liquid preparation becomes difficult, and the pot life of the water repellent liquid may be shortened.
  • the reactivity is too low, the hydrolysis reaction will not proceed sufficiently, and the amount of silanol groups produced will not be sufficient, so the bond between the substrate and the resulting water repellent film will not be sufficient, and the weather resistance of the water repellent film will be insufficient.
  • the hydrolyzable functional group is preferably an alkoxy group, and particularly preferably a methoxy group or an ethoxy group.
  • an organic solvent that dissolves the fluoroalkylsilane compound and the acid catalyst can be used.
  • the organic solvent include lower alcohols such as ethyl alcohol and isopropyl alcohol, methyl ethyl ketone, and methyl isobutyl ketone. It is preferable to use ketones, esters such as ethyl acetate and butyl acetate, hydrocarbon solvents such as hexane, toluene, benzene and xylene, ethers such as diethyl ether and diisopropyl ether, and mixtures thereof.
  • fluorine-type solvents such as hydrofluorocarbon, perfluorocarbon, perfluoroether, hydrofluoroether
  • lower alcohols such as isopropyl alcohol have high solubility of fluoroalkylsilane compounds and acid catalysts, and furthermore, the applicability (ease of spreading) of water repellent liquid and the drying time (working time) become appropriate. Particularly preferred.
  • organic sulfonic acid used in the water repellent liquid examples include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, 2-propanesulfonic acid, butanesulfonic acid, 2-butanesulfonic acid, nonafluoro-1-butanesulfonic acid, and pentane.
  • Sulfonic acid trifluoromethanesulfonic acid, 2-hydroxyethane-1-sulfonic acid, 2-hydroxypropane-1-sulfonic acid, 2-hydroxybutane-1-sulfonic acid, 2-hydroxypentanesulfonic acid, 1-carboxyethanesulfone Acid, 1,3-propanedisulfonic acid, arylsulfonic acid, 2-sulfoacetic acid, 2- or 3-sulfopropionic acid, benzenesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, nitrobenzenesulfonic acid, sulfobenzoic acid, Sulfosalicylic acid, benzal Hidosuruhon acid, p- phenolsulfonic acid, phenol-2,4-disulfonic acid.
  • methanesulfonic acid methanesulfonic acid, ethanesulfonic acid and p-toluenesulfonic acid are easily available, and are particularly preferable from the viewpoints of safety (hard to volatilize) and handling (hard to absorb moisture).
  • FIG. 1 the ratio (mol times) of the addition amount of the acid to the addition amount of the fluoroalkylsilane compound (FAS) in the water repellent solution based on the data of Examples and Comparative Examples for the first water repellent solution. It is shown. It is important that the addition amount of the organic sulfonic acid is 0.1 to 29 mol times the range of the addition amount of the fluoroalkylsilane compound (range from point A to point E). If the amount is less than 0.1 mol, the protonation of the fluoroalkylsilane compound is not sufficient, and the initial contact angle, weather resistance and wear resistance are reduced due to the low activity of the substrate and the fluoroalkylsilane compound. To do.
  • the addition amount of the organic sulfonic acid is 0.1 to 29 mol times the addition amount of the fluoroalkylsilane compound.
  • the addition amount of the organic sulfonic acid is 0.45 to 26 mol times the addition amount of the fluoroalkylsilane compound ( The range from point B to point D) is preferred. Further, in order to obtain a higher initial contact angle, weather resistance and abrasion resistance, the amount of the organic sulfonic acid added is 2.5 to 26 mol times the amount of the fluoroalkylsilane compound added (point C). To the range of point D) is preferable.
  • FIG. 2 shows the ratio (mol times) of the addition amount of acid to the addition amount of the fluoroalkylsilane compound (FAS) in the water repellent solution based on the data of Examples and Comparative Examples for the second water repellent solution. And the ratio (mol times) of the addition amount of water is illustrated.
  • the addition amount of the organic sulfonic acid is 0.15 to 2.8 mol times the addition amount of the fluoroalkylsilane compound. (Range [F]) is preferable.
  • the amount of the organic sulfonic acid added is 0.2 to 2.5 mol times the amount of the fluoroalkylsilane compound added ( [G] range) is preferred.
  • the amount of water added relative to the amount of the fluoroalkylsilane compound added is preferably 0.04 to 290 mol times (in the range [F]). It is preferable that the amount is ⁇ 200 mol times (in the range [G]) because a higher initial contact angle, weather resistance, and wear resistance can be obtained.
  • the water repellent liquid is a mixture of the fluoroalkylsilane compound and the organic solvent, the organic sulfonic acid for causing a hydrolysis reaction, and water, when water is added, mixed, and the fluoroalkylsilane compound. Can be obtained by hydrolysis and / or polycondensation.
  • the reason why the fluoroalkylsilane compound and the organic solvent are mixed first is to allow the fluoroalkylsilane compound to be mixed homogeneously in the water repellent liquid. However, you may mix said raw material simultaneously.
  • a dehydrating agent may be added to the water repellent liquid and dehydrated for a predetermined time.
  • the dehydrating agent silica gel, synthetic zeolite, activated alumina, or the like can be used, but is not limited thereto.
  • the application method for applying the water-repellent liquid obtained above to the substrate surface is brush coating, hand coating, nozzle flow coating method, dipping method, spray method, reverse coating method, flexo method, printing method, flow coating method.
  • Various coating methods such as spin coating, roll coating, and combinations thereof can be appropriately employed.
  • the base material to be used is not particularly limited.
  • a plate glass having an inorganic transparency such as a window glass for automobiles, a float plate glass usually used for a window glass for buildings, or soda-lime glass produced by a roll-out method can be used.
  • a translucent to opaque glass substrate such as a reflective substrate such as a mirror formed by using these plate glasses, rubbed glass, or glass with a pattern engraved thereon can be used.
  • plastic base materials such as polycarbonate resin, polyethylene terephthalate resin, polymethyl methacrylate resin, polyethylene resin, polyvinyl chloride resin, other plastic bases Materials may be used.
  • a treatment for improving the adhesive strength between the base material and the water repellent film can be performed on the base material surface in advance.
  • the treatment include polishing / washing / drying with various polishing liquids, surface modification treatment with acidic solution or basic solution, primer treatment, plasma irradiation, corona discharge, high-pressure mercury lamp irradiation, etc. Generation.
  • the primer treatment is performed, for example, by applying a solution to which a silicon compound having four functional groups on a substrate is added to the substrate, bonding the silicon compound and the substrate, and silanol groups derived from the silicon compound. (Active group) can be formed, and this is preferable because the number of silanol groups on the surface to which the water repellent liquid is applied can be increased.
  • the treatment after applying the water repellent liquid to the substrate After applying the water repellent liquid to the substrate, it is heated at 50 to 350 ° C. for 1 to 60 minutes, so that the silanol group derived from the hydrolyzable functional group of the fluoroalkylsilane compound exists on the surface of the substrate.
  • a bonding group such as a hydroxyl group
  • a solid coating having both excellent durability, particularly weather resistance and wear resistance, can be formed on the surface of the substrate. Heating may be performed under normal pressure, increased pressure, reduced pressure, or an inert atmosphere.
  • the water repellent film can be removed by wiping the surplus with a paper towel or cloth dampened with an organic solvent and / or a dry paper towel or cloth. An article in which is formed is obtained.
  • a water-repellent liquid for forming a water-repellent layer was prepared and applied on a substrate to produce a water-repellent article.
  • the method for preparing the water-repellent liquid and the method for producing the water-repellent article are as described below.
  • quality evaluation was performed by the method shown below about the water-repellent layer of the obtained water-repellent article.
  • the present invention is not limited to these examples.
  • Lamp M0155-L312 made by Eye Graphics
  • Lamp intensity 1.5kW
  • Illuminance The measured value under the following conditions is 128 mW / cm 2
  • Measuring device UV intensity meter (Konica Minolta Sensing, UM-10) -Light receiving part: UM-360 (light receiving wavelength range: 310 to 400 nm, peak wavelength: 365 ⁇ 5 nm)
  • Measurement mode Irradiance measurement
  • initial contact angle ⁇ (111 °)
  • light resistance ⁇ (105 °)
  • traverse resistance ⁇ (105 °)
  • outdoor exposure Durability: ⁇ (90 °)
  • excellent water repellency weather resistance and abrasion resistance, long-lasting water repellency and high durability.
  • Example 1-2 About 5 g of molecular sieve (4AXH5 8X12, manufactured by Union Showa) was added as a dehydrating agent to the water repellent liquid obtained in the same manner as in Example 1-1, and the mixture was immersed for about 16 hours to adjust the polycondensation reaction and dehydrated. After that, the mixture was filtered using a filter paper (Whatman, glass fiber filter paper: GF / A), and the molecular sieve 4A was separated and removed to obtain a colorless, transparent and homogeneous water repellent liquid.
  • the water repellent liquid corresponds to the water repellent liquid indicated by (1) in FIG. Table 1 shows the components and preparation conditions of the water repellent liquid.
  • Example 1-1 a sample having a water-repellent film was prepared in the same manner as in Example 1-1 and evaluated in the same manner.
  • initial contact angle ((111 °)
  • light resistance ((105 ° )
  • Traverse resistance ⁇ (105 °)
  • outdoor exposure durability ⁇ (90 °)
  • exhibiting excellent water repellency, weather resistance and wear resistance, maintaining long-term water repellency and durability was expensive.
  • Examples 1-3 to 1-10 A water repellent liquid was prepared in the same manner as in Example 1-2 except that the amount of organic sulfonic acid added relative to the amount of fluoroalkylsilane compound added in Example 1-2 was changed. A sample having a water film was prepared and evaluated in the same manner.
  • the water repellent liquids of Examples 1-3 to 1-10 correspond to the water repellent liquids indicated by (2) to (9) in FIG. 1, respectively. Table 1 shows the components and preparation conditions of the water repellent liquid and the evaluation results.
  • Example 1-1 A water repellent liquid was prepared in the same manner as in Example 1-1 except that trifluoroacetic acid was used instead of organic sulfonic acid, and a sample having a transparent water repellent film with a uniform surface was obtained by visual observation. .
  • the water repellent liquid used in this comparative example corresponds to the water repellent liquid indicated by (1) in FIG.
  • initial contact angle ⁇ (107 °)
  • light resistance ⁇ (90 °)
  • traverse resistance ⁇ (69 °)
  • outdoor Exposure durability ⁇ (78 °)
  • Example 1-2 A water repellent liquid was prepared in the same manner as in Example 1-2 except that trifluoroacetic acid was used instead of organic sulfonic acid, and a sample having a transparent water repellent film with a uniform surface was obtained by visual observation. .
  • the water repellent liquid used in this comparative example corresponds to the water repellent liquid indicated by (1) in FIG.
  • initial contact angle ⁇ (107 °)
  • light resistance ⁇ (86 °)
  • traverse resistance ⁇ (71 °)
  • outdoor Exposure durability ⁇ (78 °)
  • Comparative Examples 1-3 to 1-13 In Comparative Example 1-2, the addition amount of the fluoroalkylsilane compound relative to the total amount of the water-repellent liquid raw material of 100% by mass, the type of acid, and the addition amount of acid relative to the addition amount of the fluoroalkylsilane compound were changed.
  • a water repellent liquid was prepared in the same manner as in Comparative Example 1-2 and evaluated in the same manner.
  • the water repellent liquid used in Comparative Examples 1-3, 1-4, 1-6, 1-8, 1-13 corresponds to the water repellent liquid shown in (1) of FIG.
  • the water repellent liquid used in 1-7 and 1-9 corresponds to the water repellent liquid shown in (5) of FIG.
  • water repellent liquids of the present invention those that do not contain water are added 1 to 20% by mass of a fluoroalkylsilane compound having an integer of less than 8 fluorocarbon units with respect to 100% by mass of the total amount of the water repellent liquid material.
  • a fluoroalkylsilane compound having an integer of less than 8 fluorocarbon units with respect to 100% by mass of the total amount of the water repellent liquid material.
  • organic sulfonic acid the ratio (mol times) of the addition amount of the acid to the addition amount of the fluoroalkylsilane compound is shown in the range of points A to E in FIG.
  • a water repellent article water repellent glass excellent in weather resistance and wear resistance could be obtained.
  • water repellent liquids having a ratio (mol times) of the addition amount of the acid to the addition amount of the fluoroalkylsilane compound in the range of points B to D in FIG.
  • a water-repellent article water-repellent glass
  • weather resistance and abrasion resistance could be obtained.
  • water repellent liquids having a ratio (mol times) of the addition amount of the acid to the addition amount of the fluoroalkylsilane compound in the range of points C to D in FIG. 1 were used.
  • a water-repellent article water-repellent glass particularly excellent in weather resistance and abrasion resistance could be obtained.
  • the water repellent liquids of Comparative Examples 1-1 to 1-9 using an acid other than sulfonic acid have a problem that the water repellent liquid itself is opaque, and the weather resistance and wear resistance of the obtained water repellent article. There was a problem that was insufficient.
  • the water repellent liquid of Comparative Example 1-13 in which the addition amount of the fluoroalkylsilane compound deviates from 1 to 20 mass% with respect to 100 mass% of the total amount of the water repellent liquid raw material is the weather resistance of the obtained water repellent article.
  • the wear resistance is insufficient.
  • Example 2-1 C6FAS; 1.00 g and iPA; 25.00 g were mixed and stirred for about 3 minutes. Subsequently, methanesulfonic acid [manufactured by Kishida Chemical Co., Ltd., molecular weight: 96]; 0.14 g and purified water [manufactured by Kishida Chemical Co., Ltd.]; 0.11 g were added and stirred at room temperature for about 2 hours to hydrolyze C6FAS, and / or Alternatively, a colorless, transparent and homogeneous water repellent liquid was obtained by polycondensation.
  • the addition amount of C6FAS with respect to the total amount of water repellent liquid raw material of 100 mass% is 3.8 mass%
  • the addition amount of methanesulfonic acid with respect to the addition amount of C6FAS is 0.75 mol times
  • water with respect to the addition amount of C6FAS. Is 3.00 mol times and corresponds to the water repellent liquid shown in (13) of FIG. Table 2 shows the components and preparation conditions of the water repellent liquid.
  • Example 1-1 a sample having a water-repellent film was prepared in the same manner as in Example 1-1 and evaluated in the same manner.
  • the initial contact angle: ⁇ (110 °), light resistance: ⁇ (100 ° ), Traverse resistance: ⁇ (97 °), outdoor exposure durability: ⁇ (81 °) exhibits excellent water repellency, weather resistance and wear resistance, maintains water repellency for long term and durability Was expensive.
  • Example 2-2 About 5 g of molecular sieve (4AXH5 8X12, manufactured by Union Showa) was added as a dehydrating agent to the water repellent liquid obtained in the same manner as in Example 2-1, and the mixture was left to stand for about 16 hours to dehydrate while adjusting the polycondensation reaction. After that, the mixture was filtered using a filter paper (Whatman, glass fiber filter paper: GF / A), and the molecular sieve 4A was separated and removed to obtain a colorless, transparent and homogeneous water repellent liquid.
  • the water repellent liquid corresponds to the water repellent liquid indicated by (13) in FIG. Table 2 shows the components and preparation conditions of the water repellent liquid.
  • Example 2-1 a sample having a water-repellent film was prepared in the same manner as in Example 2-1, and evaluated in the same manner. As shown in Table 2, initial contact angle: ⁇ (110 °), light resistance: ((100 ° ), Traverse resistance: ⁇ (96 °), outdoor exposure durability: ⁇ (81 °), excellent water repellency, weather resistance and abrasion resistance, maintaining water repellency over the long term and durability was expensive.
  • Example 2-2 the addition amount of the fluoroalkylsilane compound relative to the total amount of the water repellent liquid raw material of 100% by mass, the type of the organic sulfonic acid, the addition amount of the organic sulfonic acid relative to the addition amount of the fluoroalkylsilane compound, A water-repellent solution was prepared in the same manner as in Example 2-2 except that the amount of water added relative to the amount of alkylsilane-based compound was changed, and a sample having a water-repellent film was prepared in the same manner. Was evaluated.
  • the water repellent liquids of Examples 2-3 and 2-15 correspond to the water repellent liquid shown in (14) of FIG.
  • FIG. 2 corresponds to the water repellent liquid represented by (15) to (20), and the water repellent liquids of Examples 2-10, 2-12, 2-13, and 2-14 are represented by (13) in FIG.
  • the water repellent liquid of Example 2-11 corresponds to the water repellent liquid shown in (21) of FIG. 2, and the water repellent liquids of Examples 2-16 to 2-24 are respectively This corresponds to the water repellent liquid indicated by (22) to (30) in FIG. Table 2 shows the components and preparation conditions of the water repellent liquid and the evaluation results.
  • Example 2-1 A water repellent liquid was prepared in the same manner as in Example 2-1, except that nitric acid was used instead of organic sulfonic acid, and a sample having a transparent water repellent film having a uniform surface by visual observation was obtained.
  • the water repellent liquid used in this comparative example corresponds to the water repellent liquid indicated by (13) in FIG.
  • initial contact angle ⁇ (107 °)
  • light resistance ⁇ (72 °)
  • traverse resistance ⁇ (61 °)
  • outdoor Exposure durability x (74 °)
  • Example 2-2 A water repellent liquid was prepared in the same manner as in Example 2-2 except that nitric acid was used in place of the organic sulfonic acid, and a sample having a transparent water repellent film having a uniform surface by visual observation was obtained.
  • the water repellent liquid used in this comparative example corresponds to the water repellent liquid indicated by (13) in FIG.
  • initial contact angle ⁇ (107 °)
  • light resistance ⁇ (78 °)
  • traverse resistance ⁇ (74 °)
  • outdoor Exposure durability x (74 °)
  • Comparative Examples 2-3 to 2-11 In Comparative Example 2-2, the addition amount of the fluoroalkylsilane compound relative to the total amount of the water repellent liquid raw material of 100% by mass, the type of acid, and the addition amount of acid relative to the addition amount of the fluoroalkylsilane compound were changed.
  • the water repellent liquid used in Comparative Examples 2-3 to 2-8 and 2-11 corresponds to the water repellent liquid shown in (13) of FIG. 2, and the water repellent liquid used in Comparative Example 2-9 is shown in FIG.
  • the water repellent liquid represented by (31) corresponds to the water repellent liquid used in Comparative Example 2-10 and corresponds to the water repellent liquid represented by (32) in FIG.
  • Table 2 shows the components and preparation conditions of the water repellent liquid and the evaluation results.
  • water-repellent liquids of the present invention those containing water are added with 1 to 20% by mass of a fluoroalkylsilane-based compound whose number of fluorocarbon units is an integer less than 8 with respect to 100% by mass of the total amount of the water-repellent raw material.
  • the ratio of the addition amount of the acid to the addition amount of the fluoroalkylsilane compound (mol times) was 0.1 to 29 mol times, and the water repellent liquid satisfying the above was used.
  • a water-repellent article (water-repellent glass) excellent in weather resistance and abrasion resistance could be obtained.
  • the ratio of the addition amount of the acid (mol times) to the addition amount of the fluoroalkylsilane compound and the ratio of the addition amount of water (mol times) are shown in FIG.
  • a water-repellent article (water-repellent glass) superior in weather resistance and abrasion resistance could be obtained.
  • the ratio of the addition amount of the acid to the addition amount of the fluoroalkylsilane compound (mole times) and the ratio of the addition amount of the water (mole times) are shown in FIG.
  • a water-repellent article (water-repellent glass) particularly excellent in weather resistance and abrasion resistance could be obtained.
  • the water repellent liquids of Comparative Examples 2-1 to 2-8 using an acid other than sulfonic acid had a problem that the obtained water repellent article had insufficient weather resistance and abrasion resistance.
  • the water repellent liquids of Comparative Examples 2-9 and 2-10 in which the ratio of the addition amount of the acid to the addition amount of the fluoroalkylsilane compound (mol times) was out of the range of 0.1 to 29 mol times were obtained. There was a problem that the weather resistance and abrasion resistance of the water-repellent article obtained were insufficient.
  • the water repellent liquid of Comparative Example 2-11 in which the addition amount of the fluoroalkylsilane compound deviates from 1 to 20 mass% with respect to 100 mass% of the total amount of the water repellent liquid raw material is the weather resistance of the obtained water repellent article.
  • the wear resistance is insufficient.

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  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
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  • Surface Treatment Of Glass (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
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Abstract

[Problème] Cette invention a pour objectif de fournir un liquide résistant à l'eau obtenu en utilisant un composé silane à fonctions fluoroalkyle généralement disponible et traditionnellement utilisé et comportant moins de huit unités fluorocarbone; le liquide résistant à l'eau est appliqué sur une pièce résistant à l'eau sans nécessiter d'équipement particulier de formation de film, et confère à ladite pièce une meilleure durabilité, en particulier une meilleure résistance aux conditions météorologiques et une meilleure résistance à l'usure, même lorsque le film formé est un film monocouche; l'invention concerne un procédé de préparation associé, une pièce résistant à l'eau obtenue en utilisant ledit liquide résistant à l'eau, et un procédé de production associé. [Solution] Cette invention concerne un liquide résistant à l'eau permettant de former une couche résistant à l'eau, ledit liquide étant obtenu en mélangeant au moins un composé silane à fonctions fluoroalkyle, la valeur (m) des unités fluorocarbone dans CF3(CF2)m-1 étant un nombre entier inférieur à 8, avec un solvant organique et un acide sulfonique organique. Le liquide résistant à l'eau est caractérisé en ce que la quantité de composé silane à fonctions fluoroalkyle ajoutée représente 1 à 20 % en masse par rapport au total de 100 % en masse des matières premières constituant le liquide résistant à l'eau, et en ce que la quantité d'acide sulfonique organique ajoutée représente de 0,1 à 29 fois en mole la quantité du composé silane à fonctions fluoroalkyle ajoutée.
PCT/JP2013/069860 2012-08-03 2013-07-23 Liquide résistant à l'eau, pièce résistant à l'eau, et procédé de production d'un liquide résistant à l'eau et d'une pièce résistant à l'eau WO2014021135A1 (fr)

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JP2016098306A (ja) * 2014-11-20 2016-05-30 株式会社ソフト９９コーポレーション コーティング組成物
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JPH02233535A (ja) * 1989-03-06 1990-09-17 Three Bond Co Ltd 車両ガラス用表面処理剤
JPH04144940A (ja) * 1990-10-05 1992-05-19 Asahi Glass Co Ltd 撥水撥油剤組成物
JPH08277388A (ja) * 1995-02-10 1996-10-22 Sofuto Kyukyu Corp:Kk 長期持続型ガラス用撥水処理剤
JPH09104861A (ja) * 1995-10-06 1997-04-22 Soft Kyukyu Corp:Kk 長期持続型ガラス用撥水処理剤
JPH1059745A (ja) * 1996-08-19 1998-03-03 Central Glass Co Ltd 撥水性ガラス及びその製法
JPH10194784A (ja) * 1996-11-18 1998-07-28 Nippon Sheet Glass Co Ltd 撥水性ガラス
JP2001207162A (ja) * 1999-11-04 2001-07-31 Nippon Sheet Glass Co Ltd 撥水撥油防汚処理液、および撥水撥油防汚処理方法
JP2002121286A (ja) * 2000-10-12 2002-04-23 Asahi Glass Co Ltd 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

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Publication number Priority date Publication date Assignee Title
JPH02233535A (ja) * 1989-03-06 1990-09-17 Three Bond Co Ltd 車両ガラス用表面処理剤
JPH04144940A (ja) * 1990-10-05 1992-05-19 Asahi Glass Co Ltd 撥水撥油剤組成物
JPH08277388A (ja) * 1995-02-10 1996-10-22 Sofuto Kyukyu Corp:Kk 長期持続型ガラス用撥水処理剤
JPH09104861A (ja) * 1995-10-06 1997-04-22 Soft Kyukyu Corp:Kk 長期持続型ガラス用撥水処理剤
JPH1059745A (ja) * 1996-08-19 1998-03-03 Central Glass Co Ltd 撥水性ガラス及びその製法
JPH10194784A (ja) * 1996-11-18 1998-07-28 Nippon Sheet Glass Co Ltd 撥水性ガラス
JP2001207162A (ja) * 1999-11-04 2001-07-31 Nippon Sheet Glass Co Ltd 撥水撥油防汚処理液、および撥水撥油防汚処理方法
JP2002121286A (ja) * 2000-10-12 2002-04-23 Asahi Glass Co Ltd 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

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