JPH0420781B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a water- and oil-repellent coating film formed by treating the surface of various base materials, and more specifically to a coating film consisting of at least two layers,
The upper layer relates to a water- and oil-repellent coating film comprising a thin film of a compound containing a polyfluorinated group and having excellent water- and oil-repellency performance and durability. The surfaces of various base materials, such as glass, ceramics, metals, plastics, and wood, are susceptible to moisture condensation due to the influence of atmospheric humidity and temperature.
It is well known that when wetted with water, components are eluted or deteriorated by the moisture, thereby causing damage. For example, in glass, water elutes the glass components and becomes alkaline, and this alkaline water corrodes the glass, causing so-called "scorching", and in iron and alloys, it causes physical and chemical non-uniformity on the surface. Depending on the situation, moisture can cause local potential differences that promote corrosion, or wet corrosion.In plastics, moisture can affect various properties such as electrical properties, mechanical properties, dimensions, or appearance; In wood, many properties change due to shrinkage, expansion, etc., which causes practical disadvantages. Under such circumstances, various water and oil repellents such as fluorine-based, silicon-based, zirconia-based, and metal soaps are used as water- and oil-repellent agents that can be applied to the surface of various base materials to impart water- and oil-repellent properties to the base materials. type is known. Fluorinated solids are the most difficult to wet due to their low free surface energy, so coatings made of fluorine-containing compounds or polymers of these compounds are formed on the surfaces of various substrates. It is known that this can impart water and oil repellency. Among such fluorine-containing compounds, polyfluorinated group-containing compounds have a low critical surface tension of 20 dyn/cm ² , which is lower than that of water as well as oil. Therefore, it can be mentioned as a preferred water and oil repellent that can impart water and oil repellency. Treatment methods for imparting water and oil repellency to the surface of various base materials include applying the water and oil repellent described above or immersing the base material in the water and oil repellent to contact or react with the base material. This method is performed by curing the coating film formed by the process. However, although the above-mentioned water and oil repellents generally have a strong cohesive force to the base material, their adhesion to the base material is weak due to their low free surface energy, making it difficult to maintain water and oil repellency for a long time. There is a problem with durability. Therefore, in known treatment methods, in order to firmly adhere the coating film of the water and oil repellent to the surface of the substrate to be treated, the surface of the substrate is coated with the water and oil repellent before treatment such as coating or dipping. roughened or
It requires special treatment. In addition, when forming a coating film by directly applying or dipping a water and oil repellent onto the surface of the substrate to be treated,
There are problems in that the water and oil repellent agent tends to be unevenly applied and becomes non-uniform, and the formed coating film has poor water and oil repellency and low durability. In particular, even if a coating film of a water- and oil-repellent agent made of a polyfluorinated group-containing compound is formed on the surface of a substrate to be treated by a known treatment method, the formed coating film has low hardness;
It is easily scratched, which is one of the reasons for reducing the durability of the paint film. The hardness of a coating film made of a polyfluorinated group-containing compound depends on the thickness of the coating film, and the hardness can be improved by increasing the film thickness. However, there are limits to obtaining sufficient hardness to maintain durability by increasing the film thickness. Moreover, increasing the film thickness in order to increase the hardness of the coating film is inevitably disadvantageous in terms of cost. Based on the recognition of the above-mentioned problems, the present inventor has developed a water- and oil-repellent coating that is formed on the surface of a substrate to be treated by a known method such as coating, spraying, or dipping. Regarding films, we conducted various studies and studies on coating films made of polyfluorinated group-containing compounds that have excellent water and oil repellency and durability. As a result, in coating films made of polyfluorinated group-containing compounds that have excellent water and oil repellency, in order to maintain the durability of the coating film, it is necessary to adhere to the surface of the substrate to be treated. A water- and oil-repellent coating film with excellent water- and oil-repellent performance and coating hardness by forming a coating film made of a material with high strength and hardness, and forming a thin film of a polyfluorinated group-containing compound on the coating film. We found that it is possible to obtain Based on this knowledge, the present inventor found that silane compounds or synthetic resin materials are suitable as materials that can firmly adhere to the surface of the substrate to be treated and form a coating film with high hardness, and form the underlying coating film of these materials. Therefore, a coating film consisting of at least two layers formed by forming a thin film of a polyfluorinated group-containing compound on the coating film has high hardness and is therefore durable even if the upper layer of the polyfluorinated group-containing compound is a thin film. The present invention was completed by discovering the fact that it is possible to obtain a water- and oil-repellent coating film having properties. The present invention provides a water- and oil-repellent multilayer film formed on the surface of a substrate to be treated, wherein the multilayer film consists of at least two layers, and the lower layer film on the base material side of the multilayer film has the following polyfluorinated group. A coating film formed by coating a silane compound other than the containing silane compound, or a coating film of synthetic resin material with a thickness of 0.1μ or more, and the upper layer is a coating film formed by coating a silane compound containing a polyfluorinated group. , a water- and oil-repellent multilayer film characterized by comprising a thin film formed by plasma polymerization of a compound containing a polyfluorinated group, or a coating film made of a reaction product of an alcohol containing a polyfluoroalkyl group and a melamine derivative. In the present invention, the substrate to be treated is glass, ceramics, metal, plastic, wood, etc., and may be a composite of an organic material and an inorganic material, for example, even if it is wholly or partially, There are no limitations as long as they can be treated to form a coating film for the purpose of imparting water and oil repellency to them. Therefore, the water- and oil-repellent coating film of the present invention has a particularly effective effect on substrates to be treated such as glass, plastic, and metal. In the silane compound or synthetic resin material used as the material for the lower coating film on the side of the substrate to be treated, the silane compound is a silane compound that has a reactive group in its molecule that chemically bonds with an inorganic substance such as glass, ceramics, or metal. Coupling agents can be suitably used. Among such silane coupling agents, a silane coupling agent represented by the general formula {X(A) _c } _a Si(Z) _b Y _4-ab is preferred. In the above general formula, X is

[Formula] NH ₂ −, NH ₂ CH ₂ CH ₂ NH−, HS−, Cl−, CH ₂ =
CH−,

[Formula] NCO-, A is an alkylene group, Z is a lower alkyl group having 1 to 4 carbon atoms, Y is selected from a halogen or an alkoxy group, and a is selected from 1 to 4.
An integer of 3, b is an integer of 0, 1 to 2 (however, a+
b is an integer of 1 to 3), and c is an integer of 0 or 1. Examples of silane coupling agents represented by the above general formula are:

[Formula] NH ₂ (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , NH ₂ (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , CH ₂ =CHSi
( _OCH3 ) ₃ , _CH2 =CHSi( _{OC2H5 ) 3} , _CH2 = _CHSiCl3 ,

[Formula] HS (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , NCO (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ , Cl (CH ₂ ) ₃ Si (OCH ₃ ) ₃ ,

[Formula] can be mentioned. In addition to the silane coupling agent, it may also be a hydrolyzate of tetraalkoxysilane, alkylalkoxysilane, or allylalkoxysilane. Such silane compounds may be used in combination of two or more, or in combination with other additives, such as fine particulate silica sol, for the purpose of improving physical properties such as adhesion and durability, or imparting dyeability. Good too. Silane compounds can be suitably used for substrates to be treated such as glass, ceramics, metals, plastics, and wood. The synthetic resin material may be either a thermoplastic resin or a thermosetting resin, and is not particularly limited as long as it can form a coating film. Such synthetic resin materials include, for example, polyacrylate,
Examples include thermoplastic resins such as polymethacrylate, polyamide, and polyurethane, and thermosetting resins such as epoxy resins, melamine resins, and urea resins. Therefore, the synthetic resin material preferably has high hardness after curing. In the synthetic resin material, other additives such as fine particulate materials such as silica and titania can be added, if necessary, for the purpose of improving or adding various physical properties. Synthetic resin materials can be suitably used for substrates to be treated such as glass, metal, and wood. The upper layer thin film consists of a coating film or thin film of the following polyfluorinated group-containing compound. The first is a coating film formed by applying a polyfluorinated group-containing silane compound, the second is a thin film formed by plasma polymerization of a polyfluorinated group-containing compound, and the third is a coating film formed by applying a polyfluorinated group-containing compound. It is a coating film made of a reaction product of alcohol and melamine derivative. The polyfluorinated group-containing compound forming these upper thin films preferably has a fluorine content of 20% by weight or more.
The silane compound in the lower coating film is different from the polyfluorinated group-containing silane compound described below, and particularly does not have a fluorine atom. As polyfluorinated group-containing silane compounds,
For example, R _f (CH ₂ ) ₂ SiCl ₃ , R _f (CH ₂ ) ₂ Si (CH ₃ ) Cl ₂ , (R _f CH ₂ CH ₂ ) ₂ SiCl ₂ , R _f (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , R _f CONH (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ , R _f CONH (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ , R _f SO ₂ N (CH ₃ )(CH ₂ ) ₂ CONH(CH ₂ ) ₃ Si
(OC ₂ H ₅ ) ₃ , R _f (CH ₂ ) ₂ OCO (CH ₂ ) ₂ S (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , R _f (CH ₂ ) ₂ OCONH (CH ₂ ) ₃ Si (OC _{2 H5} ) ₃ , R _f (CH ₂ ) ₂ NH (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , R _f (CH ₂ ) ₂ NH (CH ₂ ) ₂ Si (OCH ₂ CH ₂ OCH ₃ ) ₃ , (However, R _f is a polyfluoroalkyl group having 4 to 16 carbon atoms, and m is an integer of 1 or more.) A silane compound containing a polyfluoroalkyl group, or a silane compound in which the polyfluoroalkyl group has an ether bond, and such silane mixture of the compound with other silane compounds, _Cl3Si ( _CH2 ) ₂ ( _CF2 ) _o ( _CH2 ) _{2SiCl3 ,} (H ₃ CO) ₃ Si(CH ₂ ) ₂ (CF ₂ ) _o (CH ₂ ) ₂ Si(OCH ₃ ) ₃ , (However, n is an integer of 4 to 16, the same applies hereinafter.) There are polyfluoroalkylene group-containing silane compounds such as. The thin film formed by plasma polymerization is, for example, C ₈ H ₁₇ CH=CH ₂ , CF ₃ −C≡C−
There is a thin film formed by plasma polymerizing a plasma polymerizable polyfluorinated group-containing compound such as CF ₃ or C ₈ F ₁₈ . As a coating film made of a reaction product of a polyfluoroalkyl group-containing alcohol and a melamine derivative, there is a coating film obtained by applying and reacting a mixture of _{the two} . ) ₂ OH and Examples include reaction products of polyfluoroalkyl group-containing alcohols and melamine derivatives. The water- and oil-repellent coating film of the present invention consists of at least two coating layers formed on the surface of the substrate to be treated, and the thickness of the lower coating film must be 0.1 μm or more. If the thickness of the lower layer coating is less than 0.1μ, the entanglement of the molecules of the coating material will be insufficient, and the strength of the coating will not be maintained. It is no longer possible to improve the hardness of the thin film containing the compound. As the thickness of the lower layer coating increases, the hardness of the thin film of the polyfluorinated group-containing compound formed on the coating increases; however, from the viewpoint of workability or cost in forming the lower layer thin film, it is made to be thicker than necessary. is not appropriate. The required hardness can be obtained as long as the thickness of the coating film formed by normal coating, spraying, dipping, etc. (hereinafter these methods are collectively referred to as coating) on the surface of the substrate to be treated is applied. . The film thickness is 0.1μ or more, preferably in the range of 0.5 to 5μ. The method of forming the lower layer coating film on the surface of the substrate to be treated is not particularly limited. However, the preparation method for these materials differs depending on the underlying coating material used. When using a silane compound, the silane compound is dissolved in an organic solvent such as acetone, tetrahydrofuran, lower alcohol, etc., and the solution is adjusted to 5 to 50% by weight, preferably 15 to 40% by weight. Thereafter, the adjustment solution is applied to the surface of the substrate to be treated using a conventional coating method, and cured at room temperature or by heating if necessary. However, when the silane compound is partially cured, the polyfluorinated group-containing compound of the upper thin layer is applied onto the coating film to form a thin film, which is difficult due to the adhesive properties of the polyfluorinated group-containing compound and the thin film. preferred from the viewpoint of hardness. When using two or more silane compounds together or other additives such as silica sol, mix and stir them to react, then add an organic solvent to adjust the viscosity, and apply in the same manner as above. , forming a cured, preferably partially cured coating film. When using synthetic resin materials, methods include applying a monomer and polymerizing, applying a prepolymer and polymerizing, or applying a solvent solution of the polymer dissolved in an organic solvent that dissolves the polymer and drying. Any method can be used, such as the method of In thermoplastic resins, for example, polyacrylate or polymethacrylate is a relatively low-temperature resin obtained by solution polymerization, in which the monomer is dissolved in an organic solvent, benzoyl peroxide is added as a polymerization catalyst, and the mixture is heated and polymerized. Emulsify the polymerized product or monomer in water with an emulsifier,
After adjusting the viscosity of an emulsion polymer obtained by adding benzoyl peroxide and polymerizing it by heating, the emulsion polymer is applied to the surface of the substrate to be treated, and then the polymerization is accelerated at room temperature or by heating. A coating film is formed. In addition, polyacrylate, polymethacrylate, polyamide, etc. are dissolved in an organic solvent that dissolves these polymers, and a coating film is formed by applying a solvent solution whose viscosity is adjusted, and then evaporating the organic solvent at room temperature. to form. Polyurethane is urethane paint grade 1-component type and 2-component type.
Any liquid type can be used. Among the two-component types, two-component polyol-curing types consisting of polyisocyanate and hydroxyl group-containing polyester or polyether, or two-component chain extender-curing types consisting of polyurethane prepolymer and a chain extender such as polyamine or polyol, etc. are cured immediately before use. When the viscosity has been appropriately increased, it is applied to the surface of the substrate to be treated, and a coating film is formed at room temperature or by heating. Among the one-component types, the moisture-curing type is applied and then cured by moisture in the air to form a coating film. As for the thermosetting resin, for example, epoxy resin can be either a room temperature curing type or a heat curing type. For the room temperature curing type, an aliphatic amine catalyst is mixed and adjusted with a liquid general-purpose epoxy resin, applied to the surface of the substrate to be treated, and then cured at room temperature to form a coating film. For the heat curing type, an aromatic amine catalyst is mixed and adjusted, and after application, it is cured by heating to form a coating film. For melamine derivatives, urea resins, etc., prepare a prepolymer and apply it to the surface of the substrate to be treated.
It is heated and cured to form a coating film. The coating film formed using such a synthetic resin material is obtained by applying the polyfluorinated group-containing compound of the upper layer thin film material onto the coating film in a partially cured or partially polymerized state during the curing process. preferable. In a completely cured state, the adhesive strength of the polyfluorinated group-containing compound of the upper layer thin film and the hardness of the formed thin film will be low. Especially when the substrate to be treated is plastic and the same type of synthetic resin material is used, Since this is similar to applying the polyfluorinated group-containing compound directly to the plastic surface of the treated substrate, the effect of the two-layer coating is low. The substrate to be treated is not particularly limited, but if the substrate to be treated is plastic and a synthetic resin material is used for the lower layer coating, it is particularly necessary to bring the lower layer coating into a partially cured state. be. In the present invention, the lower coating film is not limited to only one layer. For example, a coating film of a synthetic resin material may be formed, a coating film of a silane compound may be formed on the coating film, and a thin film of a polyfluorinated group-containing compound may be formed on the coating film. A coating film imparting the function may be formed, and a coating film of a silane compound or a synthetic resin material may be formed on the coating film. In the present invention, the thin film of the polyfluorinated group-containing compound, which is the thin upper layer formed on the lower coating film, can be formed by any known coating method. However, methods for preparing the compound suitable for coating the compound vary depending on the compound used. That is, in order to facilitate coating workability and adjustment of coating film thickness, it is preferable to use a solvent solution diluted with various volatile solvents. For example, in the case of the polyfluoroalkyl group-containing silane compound, a silane compound in which the polyfluoroalkyl group has an ether bond, a hardened product of such a silane compound and another silane compound, and a polyfluoroalkylene group-containing silane compound, the compound Alternatively, the mixture is made into a 1 to 15% by weight solvent solution, preferably a 3 to 10% by weight solvent solution using one or more mixed organic solvents such as acetone, tetrahydrofuran, chlorine-based or fluorine-based solvents, and the lower layer is prepared. Apply on the paint film. After application, curing is performed by heating, but heating can be done in stages. As a heating method, hot air infrared rays or the like can be used. The heating temperature is determined by the above-mentioned polyfluorinated group-containing compound and the type of substrate to be treated, but is usually 100°C.
It is carried out under heating conditions of 20 minutes or more at a temperature of ℃ or higher. The temperature is preferably 120°C to 160°C, but higher temperatures than necessary are not preferred because the polyfluorinated group-containing compound may thermally decompose or the substrate to be treated may be deformed. To the reaction product of the polyfluoroalkyl group-containing alcohol and the melamine derivative, 1% by weight of P-toluenesulfonic acid was added as a catalyst component based on the solid component, and the mixture was heated to obtain a reaction product. Similar to the above-mentioned compounds, such a reaction product is applied to the lower coating film as a solvent solution using a solvent, and then cured under the same conditions as above to form a thin film. Further, the plasma polymerizable compound can be formed into a thin film on the lower coating film by performing a polymerization reaction within the apparatus using a plasma polymerization apparatus. The form in which the polyfluorinated group-containing compound is used is not limited to the above-mentioned solvent solution, but may be prepared in any form such as a solvent dispersion, emulsion, or aerosol. Further, additives such as inorganic fillers, antistatic agents, crosslinking agents, etc. may be added to the polyfluorinated group-containing compound as appropriate. Practically sufficient water and oil repellency and coating hardness can be obtained when the thickness of the upper thin film formed by the above method is 1 μm or less. The hardness of the polyfluorinated group-containing compound in the upper layer thin film improves as it becomes thicker, but there is a limit to this, and it is difficult to exceed the hardness of the lower layer coating. No significant improvement in hardness can be obtained. The hardness of the water- and oil-repellent coating film of the present invention is achieved by effectively utilizing the lower coating film, and even if the upper coating film is thin, the coating hardness is maintained, and it is advantageous in terms of cost. . The thickness of the coating film of the present invention can be adjusted by adjusting and coating conditions for the lower coating film and the upper thin film. The water- and oil-repellent coating film of the present invention can be combined in various ways depending on the type of substrate to be treated, the lower layer coating material, and the upper layer thin film material. Therefore, from the viewpoints of water and oil repellency, coating hardness, workability of coating film formation, cost, etc.
To illustrate the most preferable combination, in the substrate to be treated - lower coating film - upper coating film, glass - silane coupling agent - polyfluoroalkyl group-containing silane compound, glass - synthetic resin material (epoxy resin,
melamine resin, a type of polyurethane) - polyfluoroalkyl group-containing silane compound, plastic (polycarbonate, polymethacrylate, etc.)
Alternatively, a metal (aluminum)-silane coupling agent-polyfluoroalkyl group-containing silane compound may be mentioned. In these combinations, the silane coupling agent is preferably a mixture of two types, or a mixture with silica sol, and the polyfluoroalkyl group silane compound is preferably a mixture of two types, or the polyfluoroalkyl group has an ether bond. Examples include silane compounds. In the water- and oil-repellent coating film of the present invention, the water- and oil-repellency performance of the coating film formed on the base material is determined by dropping water or hexadecane onto the coating film and measuring the contact angle thereof. Desired. For example, the contact angle of water in a coating film formed on glass is 70° to 112°, the contact angle of hexadecane is 42° to 62°, and the contact angle of water and hexadecane on untreated glass is 30° or less. Therefore, excellent effects are recognized. Furthermore, the hardness of the coating film formed on the base material was determined by pencil hardness using a pencil scratch tester (JIS-K5401).
For example, the coating film formed on glass shows 2B to 5H or more, and it is recognized that the hardness is significantly improved compared to 4B, which is a coating film formed on glass and consisting only of a polyfluorinated group-containing compound. The present invention will be specifically explained below with reference to Examples. The thickness of the coating film is defined as the thickness of the coating film formed on the surface of the substrate to be treated (the sum of the lower coating film and the upper thin film). ” (Manufactured by Rank Taylor Hobson)
The thickness of the lower coating film was not measured in each example because the polyfluorinated group-containing compound of the upper layer thin film was applied while the coating film was in a partially cured state. However, the thickness of the lower coating film was confirmed in advance to be 0.1 to 2 μm when completely cured under the same conditions as in the examples. Note that the present invention is not limited only to these examples. Synthesis example 1 R _f CH=CH ₂ (However, R _f :C _o F _2o+1 , n: 6, 8,
A mixture of 10 and 12 has an average value of 9.0) 49.6 g (0.1 mol),
_HSiCl3 15.9g ₍ 0.12 mol), _{H2PtCl6.6H2O 50}
Pour 0.2 g of % isopropanol solution into a 100 ml glass pressure-resistant ampoule and heat at 85°C while shaking.
The reaction was allowed to proceed for 20 hours. After the reaction was completed, a reaction product was obtained by distillation under reduced pressure. When the reaction product is analyzed by gas chromatography, the R _f
(CH ₂ ) ₂ SiCl ₃ (bp 85°C to 100°C/3 to 5 mmHg), and the conversion rate thereto was 95%. Synthesis Example 2 Reaction product of Synthesis Example 1 R _f (CH ₂ ) ₂ SiCl ₃ 50.3g
(0.08 mol) and 15 g of methanol were mixed, and the mixture was reacted while bubbling dry nitrogen to remove generated HCl. The end point of this reaction was confirmed by quantifying the amount of HCl produced. After the reaction was completed, excess methanol was distilled off to obtain a reaction product. When the reaction product is analyzed by gas chromatography, it is found to be R _f (CH ₂ ) ₂ Si
(OCH ₃ ) ₃ and the conversion rate thereto was 100%. Synthesis example 3 R _f COOCH(CH ₃ ) ₂ (where, R _f :C _o F _2o+1 , n:
A mixture of 6, 8, 10, 12 with an average value of 9.0) 111.2g
(0.2 mol), H ₂ N (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ 44.2 g (0.2
mole), 150 g of dry tetrahydrofuran with a thermometer,
The mixture was placed in a 300 ml four-necked flask equipped with a stirrer and a condenser, and reacted at reflux temperature (approximately 80°C) for 5 hours with gentle stirring under a stream of dry nitrogen. Tetrahydrofuran was distilled off to obtain a reaction product. The reaction product was analyzed by gas chromatography to be R _f CONH (CH ₂ ) ₃ Si (OC ₂ H ₅ ) _{3 and} the conversion rate thereto was 100%. Synthesis example 4 69.0g (0.1 mol), H ₂ N (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ 22.1
(0.1 mol) and 150 g of dry tetrahydrofuran were reacted in the same manner as in Synthesis Example 3. The reaction products are analyzed using gas chromatography. The conversion rate was 1000%. Synthesis Example 5 CH ₂ =CHC ₆ F ₁₂ CH=CH ₂ 22.6g (0.06 mol),
_HSiCl3 25.9 (0.19 mol), ₅₀ % _{of H2PtCl6.6H2O}
0.2 g of isopropanol solution was reacted in the same manner as in Synthesis Example 1. After the reaction is completed, Freon (R-
113: a product of Asahi Glass Co., Ltd. (hereinafter the same) was added, filtered, and low boiling point substances were distilled off from the liquid to obtain a reaction product. The reaction product was analyzed by gas chromatography to be Cl ₃ Si (CH ₂ ) ₂ C ₆ F ₁₂ (CH ₂ ) ₂ SiCl ₃ and the conversion rate thereto was 97%. Synthesis Example 6 Reaction product of Synthesis Example 5 Cl ₃ Si (CH ₂ ) ₂ C ₆ F ₁₂
(CH ₂ ) ₂ SiCl ₃ 35g (0.056 mol), methanol 15g
were mixed and reacted in the same manner as in Synthesis Example 2 to obtain a reaction product. When analyzed by gas chromatography, the reaction product is (H ₃ CO) ₃ Si (CH ₂ ) ₂ C ₆ F ₁₂
(CH ₂ ) ₂ Si(OCH ₃ ) ₃ and the conversion rate to it is 100
It was %. Synthesis example 7 13g (0.33 mol) R _f C ₂ H ₄ OH (However, R _f :C _o F _2o+1 , n: 6, 8,
A mixture of 10 and 12 with an average value of 9.0) 34.3g (0.67 mol)
was placed in a 100 ml three-necked flask, heated to 120°C, and reacted for 22 hours while distilling off the methanol produced to form a mixture in which the reaction product with R _f C ₂ H ₄ OH and melamine were partially condensed. I got it. Synthesis example 8

[Formula] 83.4 g and 66.6 g of H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ were placed in a 500 ml four-necked flask equipped with a thermometer, stirrer, and cooling tube. After reacting at 80° C. for 2 hours, the mixture was cooled to room temperature, and 170 g of tetrahydrofuran was added to prepare a silane compound solution containing a silane coupling agent with a viscosity of 6.7 cp. Synthesis example 9

[Formula] 139g, 0.1N-HCl 27g with a stirrer, inner volume 500ml
After reacting at room temperature for 48 hours, add 150 g of 30% methanol solution of silica sol,
51 g of methanol was added to prepare a silane compound solution consisting of a silane coupling agent with a viscosity of 3.5 cp. Example 1 Reaction product R _f (CH ₂ ) ₂ Si(OCH ₃ ) ₃ 25 of Synthesis Example 2
A solvent solution of the polyfluorinated group-containing compound was prepared by diluting 500 g of the polyfluorinated compound in a mixed solvent of chlorofluorocarbon:acetone=3:1 (weight ratio). Prepare a glass plate (soda lime glass 5 x 5 cm) that was washed separately with a detergent, immersed in a 2% hydrofluoric acid solution, washed with water, and dried, and immersed in the silane compound of Synthesis Example 8 at a pulling rate of 5 cm/min. After pulling it up, it was dried at room temperature to form a lower coating film. Next, the glass plate treated in this way was immersed in the solvent solution of the polyfluorinated group-containing compound prepared earlier, pulled up at a pulling speed of 4.5 cm/min, and then cured at 160°C to remove the upper layer. A thin film was formed. The film thickness of the coating film formed on the glass plate surface by this treatment method is 1.1μ, and the contact angle of water is
The contact angle of hexadecane was 64.0°, and the pencil hardness was 2B. Examples 2 to 4 The polyfluorinated group-containing compound of Example 1 was combined with the reaction product R _f (CH ₂ ) ₂ SiCl ₃ C of Synthesis Example 1, and the reaction product R _f CONH (CH ₂ ) ₃ Si of Synthesis Example 3. (OC ₂ H ₅ ) ₃ and reaction product of Synthesis Example 4 A coating film was formed on the surface of a glass plate using the same treatment method as in Example 1, except that the film thickness, contact angle, and pencil hardness were measured. The measurement results are shown in Table 1.

[Table] Example 5 Reaction product of Synthesis Example 5 Cl ₃ Si (CH ₂ ) ₂ C ₆ F ₁₂
(CH ₂ ) ₂ SiCl ₃ 21.2g, acetone 150g, Freon 128
g and 0.6 g of a 1% acetic acid aqueous solution were mixed and stirred at room temperature for 12 hours to prepare a polyfluorinated group-containing compound solution. Separately, a glass plate on which a silane compound was formed as a lower coating film was prepared in the same manner as in Example 1, immersed in the polyfluorinated group-containing compound solution, pulled up, and then cured in the same manner as in Example 1. Then, an upper thin film was formed. After such treatment, film thickness, contact angle, and pencil hardness were measured. The measurement results are shown in Table 2. Example 6 Reaction product of Synthesis Example 6 (H ₃ CO) ₃ Si
A glass plate was treated to form a coating film in the same manner as in Example 5 except that (CH ₂ ) ₂ C ₆ F ₁₂ (CH ₂ ) ₂ Si(OCH ₃ ) ₃ was used. Corner and pencil hardness were measured. The measurement results are shown in Table 2. Example 7 Reaction product of Synthesis Example 6 (H ₃ CO) ₃ Si
(CH ₂ ) ₂ C ₆ F ₁₂ (CH ₂ ) ₂ Si(OCH ₃ ) ₃ 17.0g, and R _f
(CH ₂ ) ₂ Si (OCH ₃ ) ₃ 3.4g (However, R _f is C _o F _2o+1 , n
was a mixture of 6, 8, 10, and 12 with an average value of 9.0). After forming a coating film on a glass plate in the same manner as in Example 5, the film thickness, contact angle, and pencil hardness were measured. was measured. The measurement results are shown in Table 2. Example 8 Reaction product of Synthesis Example 6 (H ₃ CO) ₃ Si
(CH ₂ ) ₂ C ₆ F ₁₂ (CH ₂ ) ₂ Si(OCH ₃ ) ₃ 19.1g and

A coating film was formed on a glass plate in the same manner as in Example 5, except that 2.5 g of the formula was used, and the film thickness, contact angle, and pencil hardness were measured. The measurement results are shown in Table 2.

【table】

[Table] Example 9 To the mixture of Synthesis Example 7, 1% P-toluenesulfonic acid was added, and Freon:acetone=
A 5% by weight solvent solution of the polyfluorinated group-containing compound was prepared by diluting with a mixed solvent at a weight ratio of 3:1. A glass plate was treated with this solvent solution in the same manner as in Example 1 to form a coating film, and then the film thickness, contact angle, and pencil hardness were measured. The measurement results are shown in Table 3.

[Table] Examples 10 to 12 A glass plate on which a lower coating film of a silane compound was formed in the same manner as in Example 1 was prepared, and polyfluorinated group-containing compounds such as CF ₃ -C≡C-CF ₃ ,
After forming a thin film by plasma polymerization of C ₈ F ₁₇ CH=CH and C ₈ F ₁₈ diluted with argon, the film thickness, contact angle, and pencil hardness were measured. The measurement results are shown in Table 4.

[Table] Examples 13 to 18 The silane compound of the lower coating film formed by treating the glass plate in Example 1 was changed to the silane compound of Synthesis Example 9, and the glass plate was immersed and pulled up.
It was dried at ℃ for 10 minutes to form a lower coating film. After forming a thin film on this lower coating film by treating the same polyfluorinated group-containing compound as in Examples 1 to 4 and 6 to 7 in the same manner, the film thickness, contact angle, and pencil hardness were measured. The measurement results are shown in Table 5.

【table】

[Table] Examples 19 to 23 The silane compounds in the lower coating film formed by treating the glass plate in Example 1 were changed to the silane compounds shown in Table 6, and 75 g of each was diluted with tetrahydrofuran to make 500 g of the solution. Example 1
A lower coating film was formed in the same manner as above. A thin film was formed on this lower coating film by treating the polyfluorinated group-containing compound of Example 7 in the same manner, and then the film thickness, contact angle, and pencil hardness were measured. The measurement results are shown in Table 6.

[Table] Examples 24 to 26 The silane compound of the lower coating film formed by treating the glass plate in Example 1 was mixed with epoxy resin "Epicote 1001" (trade name: Yuka Ciel Co., Ltd. product): triethylenetetramine = 90:10 (weight ratio),
Melamine resin “Cymel-35” (product name: Mitsui Toatsu Chemical Co., Ltd. product): “Catalyst 6000” (product name:
75g each of a partial polymer heated at 100℃ for 10 minutes (weight ratio) = 99:1 (weight ratio) and polyurethane "Olestar M75-50E" (product name: Mitsui Toatsu Chemicals product) A lower coating film was formed in the same manner as in Example 1 except that the solution was diluted with tetrahydrofuran to make 500 g. After forming an upper layer thin film by treating the polyfluorinated group-containing compound of Example 7 on this lower layer coating film in the same manner, the film thickness, contact angle, and pencil hardness were measured. The measurement results are shown in Table 7.

[Table] Example 27 The silane compound of the lower coating film formed by treating the glass plate in Example 1 was dissolved to 5% by weight by dissolving polymethacrylate "Acrypet" (product name: Mitsubishi Rayon Co., Ltd. product) in acetone. A lower coating film was formed in the same manner as in Example 1, except for using the solvent solution obtained above. On this lower layer coating film, the polyfluorinated group-containing compound of Example 7 was treated in the same manner to form an upper layer thin film. The thickness of this coating film is 0.5μ, and the contact angle of water is
The contact angle of hexadecane was 53.1, and the pencil hardness was 3H. Examples 28-31 Reaction product of Synthesis Example 6 (H ₃ CO) ₃ Si
(CH ₂ ) ₂ C ₆ F ₁₂ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ 17.0g and R _f
A polyfluorinated group-containing compound solution was prepared by mixing and stirring 3.4 g of (CH ₂ ) ₂ Si(OCH ₃ ) ₃ , 150 g of acetone, 128 g of Freon, and 0.6 g of a 1% acetic acid aqueous solution at room temperature for 12 hours. Separately wash with detergent, rinse with water, and then dry aluminum plate, polycarbonate plate (Asahi Glass Co., Ltd. product, hereinafter the same), polymethyl methacrylate plate (Mitsubishi Rayon Co., Ltd. product, hereinafter the same), cypress board (all 5
x 5 cm) was prepared, immersed in the silane compound of Synthesis Example 10, pulled up at a pulling rate of 9 cm/min, and dried at room temperature to form a lower coating film. Next, each plate treated in this way was immersed in the solution of the polyfluorinated group-containing compound prepared earlier, finished at a pulling speed of 4.5 cm/min, and cured at 110°C to form an upper thin film. Afterwards, the film thickness, contact angle, and pencil hardness were measured. The measurement results are shown in Table 8.

[Table] Due to low surface hardness.
Examples 32-34 A polyfluorinated group-containing compound solution similar to Examples 28-31 was prepared, separately washed with a detergent, and after washing with water,
Prepare a dry polycarbonate plate (5 x 5 cm) and coat it with epoxy resin “Epicote 1001” (product name:
Yuka Ciel Co., Ltd. product): Triethylenetetramine =
90:10 (weight ratio), melamine resin "Cymel-35"
(Product name: Mitsui Toatsu Chemical Co., Ltd. product): “Catalyst
6000” (Product name: Mitsui Toatsu Chemical Co., Ltd. product) = 99:1
Partial polymer (weight ratio) heated at 100℃ for 10 minutes, and polyurethane "Orestar M75-50E"
(Product name: Mitsui Toatsu Chemical Co., Ltd. product) 75g each
A solution of 500 g of diluted with tetrahydrofuran was treated in the same manner as in Example 1 to form a lower coating film. On this lower layer coating film, the polyfluorinated group-containing compound solution prepared earlier was treated in the same manner as in Examples 28 to 31 to form an upper layer thin film, and then the film thickness, contact angle, and pencil hardness were measured. . The measurement results are shown in Table 9.

[Table] Comparative Examples 1 to 8 Table 10 shows the contact angles of water and hexadecane on glass plates, aluminum plates, polycarbonate plates, and polymethyl methacrylate plates similar to those used in Examples. In Examples 1, 4, 7, and 9, only a thin film of the polyfluorinated group-containing compound was formed by the same method except that the lower coating film was not formed.
Contact angle and pencil hardness were measured. The measurement results are shown in Table 10.

【table】

【table】

Claims (1)

[Claims] 1. In a water- and oil-repellent multilayer film formed on the surface of a substrate to be treated, the multilayer film consists of at least two layers, and the lower layer film on the substrate side of the multilayer film is made of the following polyfluorinated group-containing silane compound. The upper layer is a coating film formed by coating a silane compound containing a polyfluorinated group, or a coating film of synthetic resin material with a thickness of 0.1μ or more, and the upper layer is a coating film formed by coating a silane compound containing a polyfluorinated group, or a coating film formed by coating a silane compound containing a polyfluorinated group. A water- and oil-repellent multilayer film comprising a thin film formed by plasma polymerization of a chemical group-containing compound, or a coating film made of a reaction product of a polyfluoroalkyl group-containing alcohol and a melamine derivative.