JP2016060816A - Coating film forming composition and method for producing the same, and coating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating film forming composition capable of forming a coating film having high water repellency and excellent stain resistance without containing a linear perfluoroalkyl group having 8 or more carbon atoms which is problematic in terms of bioaccumulation or environmental adaptability.SOLUTION: There is selected a coating film forming composition which comprises a fluorine-containing silane compound having a perfluoroamine structure, a hydrolysate of a silicon alkoxide and an organic solvent.SELECTED DRAWING: None

Description

  The present invention relates to a film-forming composition, a method for producing the same, and a film.

  A material having transparency (for example, glass, plastic, etc.) is excellent in optical properties, lightness, and processability, and therefore there are many demands in the optical-related market such as liquid crystal-related members and the film market. In particular, it is used as a main material in a display screen such as a liquid crystal display.

  On the other hand, a display screen such as a liquid crystal display is desired to have various functions such as an antireflection effect and an antifouling effect. Therefore, as a material used for a display or the like, a material in which films having various functions are combined and laminated on a base material is known.

  Moreover, as a technique for imparting an antifouling effect to a substrate, for example, Patent Document 1 is known. Patent Document 1 discloses an antifouling film-coated resin article in which an antifouling layer made of a water-repellent coating is provided on the surface of a transparent resin substrate such as an antireflection film. Specifically, in Patent Document 1, a coating liquid prepared by mixing a silicon alkoxide, a silane compound containing a linear perfluoroalkyl group having 8 carbon atoms, and an acid over a period of about 12 hours is included. An antifouling layer comprising a water-repellent coating obtained by applying a surface of an undercoat layer of a siliceous resin or an inorganic compound and drying it is disclosed.

Japanese Patent No. 3342170

  By the way, conventionally, various silane compounds have been used as silane coupling agents in order to improve the adhesion at the interface between an organic material and an inorganic material. Silane coupling agents are also used as surface treatment agents for organic materials or inorganic materials, and it is known that various functions can be imparted to the material surface.

  Among them, fluorine-based silane coupling agents such as fluoroalkyl group-containing silane compounds are used in various fields as imparting agents such as water repellency and oil repellency, and in particular, linear perfluoroalkyl groups having 8 or more carbon atoms. What it contains has been used.

  However, in recent years, perfluorooctane sulfonic acid (PFOS) and perfluoroctanic acid (PFOA) have a stable structure and are not easily decomposed in the environment (hardly decomposable), and have high toxicity, environment and bioaccumulation potential. It became clear. Therefore, there has been a problem that the use of a compound having a linear perfluoroalkyl group having 8 or more carbon atoms is being restricted. Therefore, the actual situation is that a material having a perfluoroalkyl group having a carbon number of 6 or less and a short chain length as much as possible is desired in the market without having a PFOS or PFOA structure.

  The present invention has been made in view of the above circumstances, and does not contain a linear perfluoroalkyl group having 8 or more carbon atoms, which is problematic in terms of bioaccumulation and environmental adaptability. It is an object to provide a film-forming composition capable of forming a film having excellent antifouling properties.

  Moreover, this invention makes it a subject to provide the manufacturing method of the composition for film formation which can prepare the said composition for film formation simply and safely.

  Furthermore, an object of the present invention is to provide a film having high water repellency and excellent antifouling properties.

In order to solve the above problems, the present invention employs the following configuration.
[1] A fluorine-containing silane compound having a perfluoroamine structure represented by the following general formula (1);
A hydrolyzate of silicon alkoxide;
A film-forming composition comprising an organic solvent.

In the above formula (1), m and n are the same or different integers of 1 to 6, respectively. Rf ¹ is a C 1-6 perfluoroalkylene group, and may be linear or branched.
Moreover, in said formula (1), X is a bivalent organic group, is a C2-C10 hydrocarbon group, Comprising: One or more types selected from an ether bond, an ester bond, an amide bond, and a urethane bond May be included.
Furthermore, in the above formula (1), ^{R 1} is a lower alkyl group or a phenyl group, Z is a hydrolyzable group (wherein, a is an integer of 0 to 3).

[2] The film forming composition according to claim 1, wherein the hydrolyzable group Z is an alkoxy group.
[3] The film forming composition according to claim 1 or 2, wherein the hydrolyzate of the silicon alkoxide has an average molecular weight of 1 × 10 ³ or more and 2 × 10 ⁴ or less.

[4] A method for producing the film-forming composition according to item 1 above,
A composition for forming a film, wherein after producing a hydrolyzate of the silicon alkoxide from the silicon alkoxide, the fluorine-containing silane compound and the produced hydrolyzate of the silicon alkoxide are added to and mixed with the organic solvent. Manufacturing method.

[5] A method for producing the film-forming composition according to item 1,
The method for producing a film-forming composition, wherein the silicon alkoxide and the fluorine-containing silane compound are simultaneously added to and mixed with the organic solvent.

[6] A film formed using the film-forming composition described in item 1 above.

  The film-forming composition of the present invention has high water repellency and excellent antifouling properties without containing a linear perfluoroalkyl group having 8 or more carbon atoms, which is problematic in terms of bioaccumulation and environmental adaptability. It is possible to form a film having the same.

  The method for producing a film forming composition of the present invention can prepare the film forming composition simply and safely.

  The film of the present invention has high water repellency and excellent antifouling properties.

  Hereinafter, a film forming composition according to an embodiment to which the present invention is applied will be described in detail together with the production method and a film formed using the same.

<Coating composition>
First, the structure of the film forming composition of the present embodiment (hereinafter sometimes simply referred to as “composition”) will be described.
The composition of the present embodiment comprises (A) a fluorine-containing silane compound having a perfluoroamine structure (hereinafter sometimes simply referred to as “fluorine-containing silane compound” or “component (A)”), and (B) silicon alkoxide. And a hydrolyzate (hereinafter also referred to as “component (B)”) and (C) an organic solvent (hereinafter also referred to as “component (C)”).

[(A) Fluorine-containing silane compound]
The (A) fluorine-containing silane compound having a perfluoroamine structure applicable to the composition of the present embodiment is particularly limited as long as it has at least one nitrogen-containing perfluoroalkyl group and alkoxysilyl group in the molecule. Is not to be done. Specifically, the structure of such a fluorine-containing silane compound can be represented by the following general formula (1).

Here, in said formula (1), m and n are the same or mutually different integers of 1-6 respectively. Rf ¹ is a C 1-6 perfluoroalkylene group, and may be linear or branched.

  Moreover, in said formula (1), X is a bivalent organic group, is a C2-C10 hydrocarbon group, Comprising: One or more types selected from an ether bond, an ester bond, an amide bond, and a urethane bond May be included.

Furthermore, in the above formula (1), ^{R 1} is a lower alkyl group or a phenyl group, Z is a hydrolyzable group (wherein, a is an integer of 0 to 3).

  Here, more specifically, examples of the nitrogen-containing perfluoroalkyl group in the above formula (1) include perfluoroamine structures represented by the following formulas (2) to (13).

  Moreover, as X in said Formula (1), the structure shown by following formula (14)-(17) can be mentioned. The following formula (14) is an ether bond, the following formula (15) is an ester bond, the following formula (16) is an amide bond, and the following formula (17) is an example including a urethane bond.

Here, in the above formulas (14) to (17), R ² and R ³ are hydrocarbon groups having 0 to 10 carbon atoms, and R ⁴ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.

In the above formula (1), R ¹ is a lower alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group or a phenyl group, and among these, a methyl group is more preferable.

  Moreover, in said formula (1), Z will not be specifically limited if it is a hydrolysable group which can be hydrolyzed and can form a Si-O-Si bond. Specific examples of such hydrolyzable groups include alkoxy groups such as methoxy group, ethoxy group, propoxy group and butoxy group, halogen groups such as chloro group, bromo group and iodo group, phenoxy group and naphthoxy group. And aryloxy groups such as benzyloxy group, aralkyloxy groups such as benzyloxy group and phenethyloxy group, acyloxy groups such as acetoxy group, propionyloxy group, butyryloxy group, valeryloxy group, pivaloyloxy group and benzoyloxy group. Among these, it is preferable to apply a methoxy group, an ethoxy group, and a chloro group.

Here, specific examples of the fluorine-containing silane compound having a perfluoroamine structure represented by the above formula (1) include structures represented by the following formulas (18) to (65).
In the following formulas (18) to (65), R is a methyl group or an ethyl group.

  As described above, the fluorine-containing silane compound applicable to the composition of the present embodiment has a structure having at least one nitrogen-containing perfluoroalkyl group and one alkoxysilyl group in the molecule. More specifically, it has a nitrogen-containing perfluoroalkyl group in which a plurality of short-chain perfluoroalkyl groups having 6 or less carbon atoms are bonded to a nitrogen atom, and has a high fluorine content in the molecule, so that it has excellent repellency. Water and oil repellency can be imparted. On the other hand, since no perfluoroalkyl group having 8 or more carbon atoms is contained in the molecule, the chemical structure has no problem in terms of bioaccumulation and environmental adaptability. Thus, the fluorine-containing silane compound used for the composition of the present embodiment is a novel compound having excellent characteristics. That is, the fluorine-containing silane compound used in the composition of the present embodiment is designed to achieve both excellent water and oil repellency and environmental adaptability, and is not easily conceivable from conventional compounds. .

  Moreover, the fluorine-containing silane compound applicable to the composition of the present embodiment has a plurality of short-chain-length perfluoroalkyl groups branched on nitrogen atoms, that is, a perfluoroamine structure, as a nitrogen-containing perfluoroalkyl group. Since this perfluoroamine structure is bulky, it has higher water and oil repellency than a fluorine-containing silane compound having a linear perfluoroalkyl structure with a short carbon number, even though it has only a perfluoroalkyl group with a short chain length structure. High properties attributable to fluorine groups such as antifouling property, fingerprint resistance, mold release property, moisture resistance, water resistance and heat resistance can be imparted.

[(A) Fluorine-containing silane compound production method]
Next, an example of the manufacturing method of the (A) fluorine-containing silane compound mentioned above is demonstrated.
The method for producing a fluorinated silane compound that can be used in the composition of the present embodiment is a method in which a carboxylic acid halide having a nitrogen-containing perfluoroalkyl group represented by the following general formula (66) is reduced to an alcohol, It is obtained by reacting with an isocyanate in the presence of a catalyst.

In the above formula (66), m and n are the same or different integers of 1 to 6, respectively. Rf ¹ is a C 1-6 perfluoroalkylene group, and may be linear or branched. Further, Y is any one halogen atom selected from the group consisting of fluorine, chlorine, bromine and iodine.

  The carboxylic acid halide having a nitrogen-containing perfluoroalkyl group represented by the above formula (66) can be obtained, for example, by electrolytic fluorination of the corresponding carboxylic acid ester or halide in hydrogen fluoride. Moreover, when using what said Y is halogen atoms other than a fluorine atom, for example, the carboxylic acid fluoride which has the perfluoroalkyl group obtained by the said electrolytic fluorination is hydrolyzed, and corresponding carboxylic acid is used. After formation, a suitable halogenating agent (eg thionyl chloride, oxalyl chloride, phosphoryl chloride, sulfuryl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus tribromide, phosphorus pentabromide, hydrogen bromide, hydrogen iodide Etc.) can be reacted to derive the corresponding carboxylic acid halide.

  Hereinafter, in the general formula (1), the case where X is a compound having an ether bond, an amide bond and a urethane bond will be described.

"When X is a compound having a urethane bond"
In this case, for example, it can be synthesized by the following two-step reaction.

(Reduction reaction of carboxylic acid halide)
The carboxylic acid halide represented by the above formula (66) is dropped into an organic solvent in which a reducing agent such as lithium aluminum hydride (LiAlH ₄ ) or sodium borohydride (NaBH ₄ ) is dissolved or dispersed. Then, the reduction reaction is performed. By this reduction reaction, an alcohol represented by the following formula (67) is obtained.

In the above formula (67), m and n are the same or different integers of 1 to 6, respectively. Rf ¹ is a C 1-6 perfluoroalkylene group, and may be linear or branched.

(Reaction with isocyanate)
By reacting the alcohol represented by the above formula (67) obtained by the above reduction reaction with a trialkoxysilane, which is a silane coupling agent having an isocyanate group, in an organic solvent, the content represented by the above formula (1) is obtained. A fluorine silane compound is obtained.

  Examples of the silane coupling agent having an isocyanate group include triethoxysilylpropyl isocyanate and trimethoxysilylpropyl isocyanate.

  In the above reaction, a catalyst may be added to promote the reaction. Specifically, metal catalysts such as dibutyltin dilaurate, dibutyltin diacetate, tin octylate, bismuth octylate, bismuth decanoate, lead naphthenate, and potassium acetate, triethylamine, tripropylamine, triethylenediamine, diazabicyclone Examples thereof include amine catalysts such as decene, and trialkylphosphine catalysts.

“When X is a compound having an ether bond”
(Formation of allyl ether)
In this case, first, as in the case of the compound having a urethane bond, an alcohol represented by the above formula (67) obtained by reducing a carboxylic acid halide having a fluoroalkyl group and an allyl halide (for example, By reacting with allyl bromide, allyl chloride, etc., an allyl ether compound represented by the following general formula (68) is obtained.

(Hydrosilylation reaction)
Next, by reacting the obtained allyl ether and a silane compound (for example, trimethoxysilane, triethoxysilane, trichlorosilane, etc.) (hydrosilylation reaction using a platinum catalyst), the above formula (1) is obtained. A fluorine-containing silane compound is obtained.

"When X is a compound having an amide bond"
(Formation of allylamide)
In this case, first, by reacting a carboxylic acid halide having a nitrogen-containing perfluoroalkyl group represented by the above formula (66) with allylamine (for example, allylamine, N-methylallylamine, etc.), the following general formula ( 69) is obtained. In addition, R shown in the following general formula (69) is (R is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms or the like).

(Hydrosilylation reaction)
Next, by reacting the obtained allylamide body with a silane compound (for example, trimethoxysilane, triethoxysilane, trichlorosilane, etc.) (hydrosilylation reaction using a platinum catalyst), the inclusion shown in the above formula (1) is achieved. A fluorine silane compound is obtained.

[(B) Hydrolyzate of silicon alkoxide]
As the hydrolyzate of (B) silicon alkoxide applicable to the composition of the present embodiment, the reactivity of the film formation using the film forming composition and the hardness of the obtained film are maintained. If it can do, it will not specifically limit. Specific examples of the hydrolyzate of silicon alkoxide include those produced by hydrolysis (condensation) of silicon alkoxide represented by the following general formula (70). In the following formula (70), R ⁵ represents an alkyl group having 1 to 5 carbon atoms.
Si (OR ⁵ ) ₄ (70)

  Here, in the composition of this embodiment, the reason for using the hydrolyzate of (B) silicon alkoxide is that, as described above, the reactivity during film formation and the hardness of the film obtained from this composition are maintained. It is to do. For example, a hydrolyzate of a silicon alkoxide having an alkyl group having 6 or more carbon atoms has a slow hydrolysis reaction, takes a long time for production, and decreases the hardness of a film obtained by applying the obtained composition. Since there is a case, it is not preferable.

  Specific examples of the silicon alkoxide represented by the above formula (70) include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, Examples include vinyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane. Of these, tetramethoxysilane and tetraethoxysilane are preferable because a film having high hardness is obtained when the coating is formed.

Moreover, in the composition of this embodiment, it is preferable that the average molecular weight of the hydrolyzate of (B) silicon alkoxide is 1 × 10 ³ or more and 2 × 10 ⁴ or less. Here, when the average molecular weight is less than 1 × 10 ^3, it is difficult to obtain a film thickness when a film is formed on the surface of the substrate using the composition, and an adhesion force to the substrate cannot be obtained. Therefore, it is not preferable. On the other hand, when the average molecular weight exceeds 2 × 10 ⁴ , the composition has a high viscosity, which is not suitable for coating film formation. On the other hand, when the average molecular weight of the hydrolyzate of silicon alkoxide is within the above range, it is easy to adjust the film thickness of the coating, and sufficient adhesion between the substrate and the coating can be obtained. It is preferable because it is excellent in coating properties and can be easily handled during the formation of a coating film.

In addition, the average molecular weight of the hydrolyzate of silicon alkoxide can be confirmed by measuring the molecular weight by GPC (Gel Permeation Chromatography). Specifically, LC10AD (manufactured by Shimadzu Corporation) is used, a guard column and LF804 (manufactured by Showa Denko KK) are used as the measurement column, the measurement temperature is 40 ° C., the mobile phase is THF, and the molecular weight is measured. Standard materials of polystyrene (PS) have molecular weights (5.0 × 10 ² , 1.99 × 10 ³ , 5.97 × 10 ³ , 9.11 × 10 ³ , 3.79 × 10 ⁴ , 9. The molecular weight is measured using 64 × 10 ⁴ ).

[(B) Method for producing hydrolyzate of silicon alkoxide]
Next, an example of a method for producing the hydrolyzate of (B) silicon alkoxide described above will be described. In order to produce a hydrolyzate of silicon alkoxide represented by the above formula (70), these are hydrolyzed (condensed) in an organic solvent. Specifically, in the case of a hydrolyzate of silicon alkoxide, water is preferably 0.5 to 2.0 parts by mass, and inorganic acid or organic acid is 0.005 to 0.5 parts per 1 part by mass of silicon alkoxide. It is obtained by mixing a mass part and an organic solvent in the ratio of 1.0-5.0 mass parts, and advancing the hydrolysis reaction of a silicon alkoxide.

  Here, the reason why the ratio of water is preferably within the above range is that if the ratio of water is less than the lower limit value, the hydrolysis reaction may not proceed sufficiently, and the hardness of the coating will decrease. On the other hand, if the upper limit value is exceeded, problems such as gelation of the reaction solution may occur during the hydrolysis reaction. In addition, the adhesion with the substrate may be reduced. Among these, it is especially preferable that the ratio of water shall be 0.8-3.0 mass parts. Moreover, as water, it is desirable to use ion exchange water, pure water, etc. in order to prevent mixing of impurities.

  Examples of the inorganic acid or organic acid include inorganic acids such as hydrochloric acid, nitric acid, and phosphoric acid, and organic acids such as formic acid, oxalic acid, and acetic acid. Of these, it is particularly preferable to use formic acid. This is because the inorganic acid or organic acid functions as an acidic catalyst for promoting the hydrolysis reaction of silicon alkoxide, but by using formic acid as the catalyst, it is easy to form a film having excellent transparency. In addition, when formic acid is used as a catalyst, the effect of preventing the promotion of non-uniform gelation in the film after film formation is higher than when using other catalysts.

  In addition, the reason why the ratio of the inorganic acid or organic acid is preferably within the above range is that the ratio of the inorganic acid or organic acid is less than the lower limit value, and thus the film having high hardness is difficult to be formed. This is because even if the upper limit is exceeded, there is no effect on the reactivity, but problems such as corrosion of the coated substrate due to residual acid may occur. Among these, it is particularly preferable that the ratio of the inorganic acid or the organic acid is 0.008 to 0.2 parts by mass.

  As the organic solvent, alcohol, glycol ether, or glycol ether acetate is preferably used. The reason why it is preferable to use these alcohols, glycol ethers or glycol ether acetates as the organic solvent is to improve the applicability of the composition and to facilitate mixing with, for example, silicon alkoxide.

  Examples of the alcohol include methanol, ethanol, propanol, isopropyl alcohol (IPA) and the like. As glycol ethers, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether Etc. As glycol ether acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monoethyl ether Examples include acetate and dipropylene glycol monoethyl ether acetate.

  Of these, the hydrolysis reaction is easy to control and good coating properties can be obtained during film formation, so ethanol, IPA, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether or propylene glycol monomethyl Ether acetate and the like are particularly preferable.

  The reason why the ratio of the organic solvent is preferably within the above range is that when the ratio of the organic solvent is less than the lower limit, the reaction solution is likely to be gelled during the hydrolysis reaction, and it is difficult to obtain a film with excellent transparency. Because. In addition, the adhesion to the substrate may be reduced. On the other hand, if the upper limit is exceeded, problems such as a decrease in hydrolysis reactivity occur, and a film having sufficient hardness cannot be obtained. Among these, the ratio of the organic solvent is particularly preferably 1.5 to 3.5 parts by mass.

[(C) Organic solvent]
The composition of the present embodiment includes (C) an organic compound for adjusting the viscosity suitable for coating and for suppressing the reaction between (A) a fluorine-containing silane compound and (B) a hydrolyzate of silicon alkoxide. It is comprised including a solvent. In the system in which the film-forming composition does not contain (C) an organic solvent, the hydrolysis rate of the silicon alkoxide is high, and a solid material due to gelation is immediately generated.

  The organic solvent (C) applied to the composition of the present embodiment is highly compatible with (B) hydrolyzate of silicon alkoxide and (A) fluorine-containing silane compound, and can be handled as a composition for film formation. Therefore, it is preferable to use the same organic solvent as that used when the hydrolyzate of (B) silicon alkoxide described above is used, or the organic solvents listed above.

  Among the organic solvents described above, ethanol, IPA, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and the like are particularly preferable.

  Here, in the composition of the present embodiment, the solid component ratio of the (A) fluorine-containing silane compound that is a film forming component and the hydrolyzate of (B) silicon alkoxide is 100% by mass based on the total amount of the solid component. Component (A): Component (B) = preferably in the range of 95: 5 to 2:98, more preferably in the range of 80:20 to 5:95, and in the range of 40:60 to 10:90 More preferably.

  When the solid component ratio of the fluorine-containing silane compound (A) in the solid component is less than 2% by mass (that is, the component (B) exceeds 98% by mass), sufficient water repellency can be obtained when a film is formed. It is not preferable because it is not. On the other hand, when the solid component ratio of the component (A) exceeds 95% by mass (that is, the component (B) is less than 5% by mass), the film strength of the coating film decreases and the adhesion to the substrate becomes insufficient. It is not preferable. On the other hand, when the solid component ratio is within the above range, high water repellency and excellent film characteristics can be obtained, which is preferable. Especially, in the range whose solid component ratio of a component (B) is 60-90, since a film exhibits the outstanding durability, it is preferable.

  In particular, from the viewpoint of the solid component ratio and water repellency of the coating, in the range of component (A): component (B) = 95: 5 to 2:98, the contact angle of water with respect to the formed coating is 110 ° or more, It is preferable for showing high water repellency. Further, by setting the component (A): component (B) in the range of 20:80 to 10:90, the contact angle of water with respect to the formed film becomes 115 ° or more, and very high water repellency is obtained. preferable.

  In the composition of this embodiment, the concentration of (C) the total solid component (that is, component (A) + component (B)) in the organic solvent is not particularly limited, and is applied to the substrate. It can be appropriately selected depending on the method. Specifically, the concentration of the total solid component may be, for example, 1 to 50% by mass, and preferably 2 to 20% by mass.

<Manufacturing method of film forming composition>
Next, the manufacturing method of the composition for film formation of this embodiment is demonstrated in detail below.
As an example of the manufacturing method of the film forming composition of this embodiment, after producing | generating the hydrolyzate of (B) silicon alkoxide from silicon alkoxide, (C) organic solvent, (A) fluorine-containing silane compound, and production | generation And (B) a hydrolyzate of silicon alkoxide, and a method of adding and mixing (first method).

[First method]
Specifically, in the first method, silicon alkoxide and an organic solvent are mixed to prepare a first liquid (first step), silicon alkoxide, water, and an inorganic acid are mixed. Then, the step of preparing the second liquid (second step), the second liquid is added to the first liquid maintained at the required temperature, and the mixture is mixed while maintaining the temperature, so that the silicon alkoxide is hydrolyzed. Including a step of obtaining a decomposition product (third step) and a step of adding a hydrolyzate of the obtained silicon alkoxide after adding the fluorine-containing silane compound to the organic solvent (fourth step). It is configured.

(First step)
First, in the first step, a silicon alkoxide and an organic solvent are mixed to prepare a first liquid. Specifically, when silicon alkoxide is charged into the reaction vessel and made into 1 of this silicon alkoxide, an organic solvent in an amount of 1.0 part by mass with respect to 1 part by mass is added. Then, for example, the first liquid is prepared by stirring at a temperature of about 30 ° C. for about 15 minutes.

(Second step)
Next, in the second step, silicon alkoxide, water, and an inorganic acid are mixed to prepare a second liquid. Specifically, first, ion exchange water in an amount of 1.0 part by mass with respect to 1 part by mass of silicon alkoxide and an inorganic acid in an amount of 0.01 part by mass are put into a container and mixed. To do. Next, the second liquid is prepared by, for example, stirring at a temperature of about 30 ° C. for about 15 minutes.

(Third step)
Next, in the third step, the second liquid is added to the first liquid maintained at a required temperature and mixed while maintaining the temperature to obtain a hydrolyzate of silicon alkoxide. Specifically, the first liquid prepared in the first step is maintained at a temperature of, for example, about 55 ° C. using a constant temperature liquid bath (water bath) or the like, and then the second liquid described above is added to the first liquid. The liquid is added and stirred for about 60 minutes while maintaining the above temperature. Thereby, a hydrolyzate of silicon alkoxide is obtained.

(4th process)
Next, in a 4th process, after adding a fluorine-containing silane compound to an organic solvent, the hydrolyzate of the silicon alkoxide obtained in the 3rd process is added. Specifically, a required amount of an organic solvent is prepared, and a required amount of a fluorine-containing silane compound having a perfluoroamine structure is added to the organic solvent. Next, a required amount of the hydrolyzate of silicon alkoxide prepared in advance in the third step is added to the organic solvent. Thereby, the composition for film formation of this embodiment is obtained.

Further, as another example of the method for producing the film forming composition of the present embodiment, (C) a method in which silicon alkoxide and (A) a fluorine-containing silane compound are simultaneously added and mixed in an organic solvent (first method) 2 method).
Here, the first method described above is (B) a method of preparing a hydrolyzate of silicon alkoxide in advance, whereas the second method has a perfluoroamine structure simultaneously with the hydrolysis of silicon alkoxide. In this method, a fluorine-containing silane compound is mixed to obtain a film-forming composition.

[Second method]
Specifically, the second method includes a step of preparing a first liquid (first step) by mixing silicon alkoxide, (A) a fluorine-containing silane compound, and (C) an organic solvent. ), Water and an inorganic acid are mixed to prepare a second ′ liquid (second ′ process), and the second ′ liquid is added to the first ′ liquid maintained at a required temperature, And a step of mixing while maintaining the temperature (third step).

(First step)
First, in the first 'step, silicon alkoxide, a fluorine-containing silane compound having a perfluoroalkylamine structure, and an organic solvent are mixed to prepare a first' solution. Specifically, first, silicon alkoxide is charged into a reaction vessel, and when the mass of the silicon alkoxide is set to 1, an organic solvent that is 1.1 parts by mass is added. Further, the fluorine-containing silane compound is added to 1 part by mass of the silicon alkoxide previously charged so as to be, for example, 0.5 to 1 part by mass, and, for example, at a temperature of about 30 ° C. for about 15 minutes. Prepare the 1 'liquid by stirring.

(Second step)
Next, in the 2 ′ step, water and an inorganic acid are mixed to prepare a 2 ′ solution. Specifically, first, ion exchange water in an amount of 0.85 parts by mass with respect to 1 part by mass of silicon alkoxide and an inorganic acid in an amount of 0.01 parts by mass are put into a container and mixed. To do. Next, the second ′ liquid is prepared, for example, by stirring for about 15 minutes at a temperature of about 30 ° C.

(3rd step)
Next, in the third ′ step, the second ′ liquid is added to the first ′ liquid maintained at a required temperature and mixed while maintaining the temperature. Specifically, the first ′ liquid prepared in the first ′ process is maintained at a temperature of about 60 ° C. using a constant temperature bath (water bath) or the like, and then the first ′ liquid is added to the first ′ liquid. 2 'liquid is added and it stirs for about 60 minutes, maintaining the said temperature. Thereby, the composition for film formation of this embodiment containing the fluorine-containing silane compound which has a perfluoroamine structure, and the hydrolyzate of a silicon alkoxide in an organic solvent is obtained.

<Usage method of film forming composition>
Next, a method for using the film forming composition of the present embodiment, that is, a method for forming a film will be described. The film forming composition of the present embodiment can be applied as it is on a workpiece such as a substrate.

  Specifically, for example, the film is formed on the surface of the base material by applying the film-forming composition of the present embodiment to the surface of the base material and then baking and curing. be able to.

  The substrate is not particularly limited, but glass, plastic, metal, ceramics, stainless steel, aluminum, wood, stone, cement, concrete, fiber, fabric, paper, leather, combinations thereof, structures, laminates, and the like. Can be used.

  In the coating step, the coating method on the surface of the substrate is not particularly limited. Specifically, for example, a dipping method in which the substrate is dipped in the film-forming composition, a method using an application means such as spray, spin coating, brush, roller, or a method using a printing method may be mentioned.

  Firing conditions can be appropriately selected depending on the type and content of the organic solvent contained in the film-forming composition. As a calcination temperature, it can be set as 60-200 degreeC, for example. Moreover, as baking time, it can be 5 to 60 minutes, for example. When selecting the baking conditions, a film having the same hardness can be obtained by setting the baking temperature for a long time at a low temperature and for a short time at a high temperature.

<Coating>
The film of this embodiment is formed using the film forming composition described above. Specifically, as described above, a coating liquid containing a fluorine-containing silane compound having a perfluoroamine structure, a hydrolyzate of silicon alkoxide, and an organic solvent is applied to the substrate, and then baked and cured. Is obtained.

  The coating according to the present embodiment is coated with a composition containing a novel fluorine-containing silane compound having a perfluoroamine structure, which is a fluorine material having a low environmental load, a hydrolyzate of silicon alkoxide, and an organic solvent, and is fired. Since the film is obtained by curing the film, it has higher water repellency than a film obtained from a single fluorine-containing silane compound having a perfluoroamine structure. Therefore, the coating film of this embodiment has excellent antifouling properties that prevent dirt from adhering to the surface of the substrate and can be easily wiped even when adhering.

  In addition, since the coating film of this embodiment contains a hydrolyzate of silicon alkoxide that contributes to curing, the coating film of this embodiment is obtained from a fluorine-containing silane compound alone having high scratch resistance and high hardness, and having a perfluoroamine structure. It is more excellent in adhesion and durability to the substrate than the coated film.

  Furthermore, when the coating film of this embodiment is a cured film of a hydrolyzate using TEOS as the raw material silicon alkoxide and formic acid as the acidic catalyst, the transmittance is 95 to 98% and the haze is 0.1 or less. , Has excellent transparency. Therefore, even when a film is formed on a transparent substrate, excellent antifouling properties can be imparted while maintaining visibility.

  In addition, the water repellency of the film of this embodiment can be evaluated by the contact angle of water and the contact angle of oil. The contact angle can be measured using a commercially available measuring device (for example, “Drop Master M-700” manufactured by Kyowa Interface Science Co., Ltd.). Specifically, ion exchange water is prepared in a syringe, and a value obtained by analyzing a contact angle after 1000 msec after water touches the membrane surface in a stationary state by the 2 / θ method can be used as the water contact angle. . Moreover, n-hexadecane is prepared for a syringe, a contact angle is measured, and the value analyzed similarly can be made into the contact angle of oil.

  The antifouling property of the film of this embodiment can be evaluated by, for example, the repellent property of an oil pen. Specifically, a film is formed on a substrate using the film-forming composition, a straight line having a length of 1 cm is written on the surface of the film using an oil-based pen, and the ease of repelling is visually determined according to a predetermined standard. Can be evaluated.

  The transmittance | permeability of the film of this embodiment can be measured about the film formed on the glass base material using a commercially available measuring apparatus (For example, Hitachi High-Tech make, spectrophotometer "U-4100"). Specifically, the transmittance of the film containing the glass substrate is measured in the range of 240 to 2600 nm. About the transmittance | permeability, the value in 550 nm which is a visible light range is confirmed.

  The haze of the film of this embodiment can be measured using a commercially available measuring device (for example, haze meter “HZ-V3” manufactured by Suga Test Instruments Co., Ltd.) for the film formed on the glass substrate. The haze is a numerical value represented by the diffuse transmittance of the film / the total light transmittance × 100, and the haze value increases as the film becomes cloudy.

  The adhesion of the film of this embodiment is determined by using a commercially available adhesive tape (for example, “Cello Tape CT-24” manufactured by Nichiban Co., Ltd.) for the film formed on the glass substrate. Cut method) It can be measured based on the test method. In addition, when the transparency of the film is high and it is difficult to confirm the peeled state, the value after the adhesion test is changed as compared with the transmittance and haze value before the adhesion test. The presence or absence can be confirmed.

  The durability of the coating film of this embodiment can be evaluated by the change rate of the transmittance before and after the high temperature and high humidity environment test. Specifically, first, a film is formed on a glass substrate using the film forming composition, and the transmittance of the substrate and the transmittance of the substrate including the film are measured for the formed film. Next, the substrate after forming the film is stored in an environmental tester (for example, “PL-1K” manufactured by Espec Co., Ltd.) in a high-temperature and high-humidity state at 85 ° C. and 85% RH, and a durability test of 1000 hours is performed To do. Subsequently, it can evaluate by measuring the transmittance | permeability about the base material with a film after 1000 hours, and confirming the change rate.

  By the way, since there are four alkoxy groups in a general silicon alkoxide, the reactivity with a base material such as glass is high, and a hydrolysis reaction occurs with a hydroxy group on the base material surface. Thereby, it is known that a hydrolyzate of silicon alkoxide can be easily formed as a film on the surface of the substrate. However, silane coupling agents substituted with other functional groups (for example, alkyl groups) among the four alkoxy groups possessed by silicon alkoxide are known to decrease the reactivity of alkoxy groups. It is believed that the reactivity decreases as the number of groups decreases.

  Here, the fluorine-containing silane compound having a perfluoroamine structure contained in the film forming composition of the present embodiment described above has one perfluoroamine group with respect to three alkoxy groups. For this reason, it is thought that the reactivity of (A) a fluorine-containing silane compound and substrates, such as glass, is lower than the silicon alkoxide which has four general alkoxy groups. Further, the (A) fluorine-containing silane compound has a very bulky perfluoroamine group on the opposite side in the molecule (on the opposite side) with respect to an alkoxy group highly reactive with a substrate such as glass. Therefore, it is considered that the opportunity to contact the substrate and the reaction with the substrate are further reduced.

  Therefore, in the film obtained from the film-forming composition containing only the fluorine-containing silane compound having a perfluoroamine structure as a solid component (that is, the film obtained from the fluorine-containing silane compound having a perfluoroamine structure alone), Since the reactivity between the fluorosilane compound and the substrate is insufficient, it is assumed that sufficient perfluoroamine groups do not exist on the surface of the coating, and that high water repellency cannot be obtained. Furthermore, it is guessed that the adhesiveness to the base material of the film formed becomes low.

  In contrast, the film of the present embodiment is obtained from the film-forming composition of the present embodiment described above, which contains a fluorine-containing silane compound having a perfluoroamine structure as a solid component and a hydrolyzate of silicon alkoxide. Coating. Here, it is thought that the hydrolyzate of silicon alkoxide contained as a solid component in the composition for forming a film functions so as to increase the reactivity with the substrate and the like.

  Specifically, when a film is formed on the surface of the substrate, a hydrolyzate of silicon alkoxide is present on the substrate side, and the fluorine-containing silane compound having a highly reactive alkoxy group and a perfluoroamine structure has Since the alkoxy group reacts, it is assumed that the adhesion to the base material is increased. Furthermore, in the film formed using the film forming composition of the present embodiment, silicon alkoxide exists between the substrate and the reaction point with the fluorine-containing silane compound having a perfluoroamine structure is increased. From this, it is presumed that the film has higher water repellency than the film obtained from the above-mentioned fluorine-containing silane compound alone.

  As described above, according to the film forming composition of the present embodiment, it is high without containing a linear perfluoroalkyl group having 8 or more carbon atoms, which is a problem in terms of bioaccumulation and environmental adaptability. It is possible to form a film having water repellency and excellent antifouling properties.

  In particular, in the film forming composition of the present embodiment, as the nitrogen-containing perfluoroalkyl group, there are a plurality of short-chain long structure perfluoroalkyl groups branched on the nitrogen atom, that is, a fluorine-containing silane compound having a perfluoroamine structure. include. Since this perfluoroamine structure is bulky, it has a high repellency compared to a fluorine-containing silane compound having a linear perfluoroalkyl structure having 8 or more carbon atoms, although it has only a short-chain-length perfluoroalkyl group. It is possible to impart high characteristics due to the above-described fluorine group such as water / oil repellency.

  According to the method for producing a film forming composition of the present embodiment, the film forming composition can be prepared easily and safely.

  The film of this embodiment has higher water repellency and excellent antifouling properties than a film obtained from a fluorine-containing silane compound having a perfluoroamine structure. It also has excellent transparency, adhesion to the substrate and durability.

  The technical scope of the present invention is not limited to the above embodiment, and various modifications can be made without departing from the spirit of the present invention. Specifically, in the above-described embodiment, an example in which only one kind of each of the fluorine-containing silane compound and the silicon alkoxide is included in the film forming composition is described, but the present invention is not limited to this. For example, the film forming composition may contain two or more fluorine-containing silane compounds, or may contain a hydrolyzate of two or more silicon alkoxides.

  Hereinafter, the effects of the present invention will be described in more detail by way of examples. In addition, this invention is not limited at all by the Example.

<Synthesis example>
(Fluorine-containing silane compound 1)
Sodium borohydride (14.1 g) (manufactured by Tokyo Chemical Industry Co., Ltd.) and tetrahydrofuran (310 ml) were charged into a three-necked flask equipped with a dropping funnel. In the dropping funnel, (CF ₃ CF ₂ CF ₂ CF ₂ ) ₂ NCF ₂ CF ₂ COF (371.3) obtained by electrolytic fluorination of (CH ₃ CH ₂ CH ₂ CH ₂ ) ₂ NCH ₂ CH ₂ CO ₂ CH ₃ . 0 g, purity 70%) was added and gradually added dropwise at room temperature.

  After completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour, and then the reaction solution was quenched with water and an aqueous hydrochloric acid solution, and chloroform was added to separate the layers. The obtained chloroform layer was washed with an aqueous hydrochloric acid solution and water and dried over magnesium sulfate, and then the obtained solution was concentrated by a rotary evaporator. Furthermore, the obtained solution was distilled under reduced pressure to obtain an alcohol form (171.0 g, yield 68%).

  In a three-necked flask equipped with a dropping funnel, the obtained alcohol (129.1 g), t-butanol (129.0 g) (manufactured by Tokyo Chemical Industry Co., Ltd.), potassium t-butoxide (32.3 g) (Wako Pure Chemical Industries, Ltd.) Company). Allyl bromide (53.6 g) (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the dropping funnel and gradually dropped at 0 ° C.

  After completion of dropping, the mixture was stirred at room temperature for 1 hour. After filtering the reaction solution, chloroform was added to the obtained filtrate, washed with water and dried over magnesium sulfate, and then the obtained solution was concentrated by a rotary evaporator. Furthermore, the obtained solution was distilled under reduced pressure to obtain an allyl ether (56.5 g, yield 41%) isomer.

  Next, the obtained allyl ether (23.9 g) and toluene (50 ml), 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum complex xylene solution (0.3 ml) (Sigma Aldrich) Product) and trimethoxysilane (5.6 g) (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and reacted at 60 ° C. for 4 hours. The resulting solution was concentrated with an evaporator and distilled under reduced pressure to obtain a fluorinated silane compound (A) represented by the following general formula (71) (15.0 g, yield 53%).

(Fluorine-containing silane compound 2)
In a three-necked flask equipped with a dropping funnel, an alcohol (200.0 g) obtained in the same manner as the fluorine-containing silane compound 1, 3-isocyanatopropyltriethoxysilane (70.7 g) (manufactured by Tokyo Chemical Industry Co., Ltd.), acetonitrile (300 ml) and dibutyltin dilaurate (3 drops) (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed and stirred at 70 ° C. for 4 hours. The obtained solution was concentrated with an evaporator and dried at 140 ° C. under reduced pressure (2 Torr) to give a fluorinated silane compound (A) represented by the following general formula (72) (233.5 g, yield 98%). Got.

(Fluorine-containing silane compound 3)
Allylamine (19.4 g) (manufactured by Wako Pure Chemical Industries, Ltd.) and diisopropyl ether (200 ml) were charged into a three-necked flask equipped with a dropping funnel. In a dropping funnel, (CF ₃ ) ₂ NCF ₂ CF (CF ₃ ) COF (63.3 g, purity 50%) obtained by electrolytic fluorination of (CH ₃ ) ₂ NCH ₂ CH (CH ₃ ) CO ₂ CH ₃ And gradually added dropwise at 0 ° C.

  After completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour, washed with an aqueous sodium hydroxide solution and water, and dried by adding magnesium sulfate. After magnesium sulfate was filtered off, the resulting solution was concentrated by a rotary evaporator. Furthermore, the allylamide body (21.0 g, yield 60%) was obtained by distilling the obtained solution under reduced pressure.

  Next, the obtained allylamide (14.7 g) and toluene (50 ml), 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum complex xylene solution (0.3 ml) (manufactured by Sigma-Aldrich) ) And trimethoxysilane (5.6 g) (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and reacted at 60 ° C. for 4 hours. The obtained solution was concentrated with an evaporator and distilled under reduced pressure to obtain a fluorinated silane compound (A) represented by the following general formula (73) (15.1 g, yield 78%).

(Hydrolyzed silicon alkoxide)
Of the composition for film formation, a hydrolyzate of silicon alkoxide was prepared by the following method.
Specifically, first, tetraethoxysilane (TEOS) was prepared as a silicon alkoxide and charged into a separable flask. When the mass of the silicon alkoxide is 1, the amount of ethanol to be 1.0 part by mass is added as an organic solvent with respect to 1 part by mass, and the mixture is stirred at a temperature of 30 ° C. for 15 minutes. A liquid was prepared.

  Separately from the first solution, 1.0 part by mass of ion-exchanged water with respect to 1 part by mass of silicon alkoxide and 0.01 parts by mass of nitric acid are used as inorganic acids in the beaker. The second liquid was prepared by charging and mixing and stirring at a temperature of 30 ° C. for 15 minutes.

Next, the prepared first liquid was maintained at a temperature of 55 ° C. in a water bath, the second liquid was added to the first liquid, and the mixture was stirred for 60 minutes while maintaining the temperature. Thereby, a hydrolyzate of silicon alkoxide (B) (average molecular weight: 4 × 10 ³ ) having a solid content of 10% by mass in terms of SiO ₂ was obtained.

Similarly, hydrolysates (B) (average molecular weights: 1 × 10 ³ , 2 × 10 ⁴ ) of silicon alkoxides having different average molecular weights having a solid content of 10% by mass in terms of SiO ₂ were prepared.

Example 1
As an organic solvent, 42.7 g of ethanol is prepared, and 0.3 g of a compound represented by the above formula (71) is weighed and added as a fluorinated silane compound (A) having a perfluoroamine structure. Thereafter, 7 g of the hydrolyzate (average molecular weight: 4 × 10 ³ ) of the above-mentioned (B) silicon alkoxide prepared in advance was added to prepare a film-forming composition.

(Example 2)
As an organic solvent, 41.8 g of isopropyl alcohol is prepared, and 0.2 g of a compound represented by the above formula (72) is weighed and added as a fluorine-containing silane compound (A) having a perfluoroamine structure. Thereafter, 8 g of the silicon alkoxide hydrolyzate (B) (average molecular weight: 4 × 10 ³ ) prepared in advance was added to prepare a film-forming composition.

(Example 3)
As an organic solvent, 44.5 g of isopropyl alcohol is prepared, and 0.5 g of a compound represented by the above formula (73) is weighed and added as a fluorinated silane compound (A) having a perfluoroamine structure. Thereafter, 5 g of the silicon alkoxide hydrolyzate (B) (average molecular weight: 4 × 10 ³ ) prepared in advance was added to prepare a film-forming composition.

Example 4
First, tetraethoxysilane (TEOS) is prepared as a silicon alkoxide and charged into a separable flask. When the mass of the silicon alkoxide is 1, the fluorine-containing silane compound (A) having a perfluoroamine structure represented by the above formula (71) is 0.5 parts by mass with respect to 1 part by mass, and An amount of ethanol of 1.1 parts by mass was added as an organic solvent and stirred at a temperature of 30 ° C. for 15 minutes to prepare a first liquid.

Separately from this first liquid, ion exchange water in an amount of 0.85 parts by mass and nitric acid in an amount of 0.01 parts by mass with respect to 1 part by mass of silicon alkoxide are charged into the beaker as inorganic acids. And a second liquid was prepared by stirring at a temperature of 30 ° C. for 15 minutes. Next, after maintaining the prepared first liquid at a temperature of 60 ° C. in a water bath, the second liquid was added to the first liquid and stirred for 60 minutes while maintaining the temperature. This obtained the hydrolyzate (B) (average molecular weight: 4 * 10 < ³ >) of silicon alkoxide containing the fluorine-containing silane compound (A) which has a perfluoroamine structure shown to the said Formula (71).

  Next, 45 g of ethanol was prepared as an organic solvent, and 5 g of hydrolyzate of silicon alkoxide (B) containing the fluorinated silane compound (A) represented by the above formula (71) was weighed and added to form a film-forming composition. Prepared.

(Example 5)
In the same manner as in Example 4, a hydrolyzate of silicon alkoxide (B) (average molecular weight: 4 × 10 ³ ) containing a fluorine-containing silane compound (A) having a perfluoroamine structure represented by the above formula (72). Obtained.
Next, 45 g of propylene glycol monomethyl ether was prepared as an organic solvent, and 5 g of hydrolyzate of silicon alkoxide (B) containing the fluorine-containing silane compound (A) represented by the above formula (72) was added to form a film. A composition was prepared.

(Example 6)
In the same manner as in Example 4, a hydrolyzate of silicon alkoxide (average molecular weight: 4 × 10 ³ ) containing a fluorine-containing silane compound (A) having a perfluoroamine structure represented by the above formula (73). Obtained.
Next, 40 g of isopropanol was prepared as an organic solvent, 10 g of a hydrolyzate of silicon alkoxide (B) containing the fluorine-containing silane compound (A) represented by the above formula (73) was added, and a film-forming composition was formed. Was prepared.

(Example 7)
As an organic solvent, 40.9 g of ethanol is prepared, and 0.1 g of a compound represented by the above formula (71) is weighed and added as a fluorinated silane compound (A) having a perfluoroamine structure. Then, 9 g of the hydrolyzate (B) (average molecular weight: 4 × 10 ³ ) of the silicon alkoxide prepared in advance was added to prepare a film forming composition.

(Example 8)
As an organic solvent, 43.6 g of isopropanol is prepared, and 0.4 g of a compound represented by the above formula (71) is weighed and added as a fluorine-containing silane compound (A) having a perfluoroamine structure. Thereafter, 6 g of the silicon alkoxide hydrolyzate (B) (average molecular weight: 4 × 10 ³ ) prepared in advance was added to prepare a film-forming composition.

Example 9
As an organic solvent, 46.3 g of isopropanol is prepared, and 0.7 g of a compound represented by the above formula (73) is added as a fluorine-containing silane compound (A) having a perfluoroamine structure. Thereafter, 3 g of the silicon alkoxide hydrolyzate (B) (average molecular weight: 4 × 10 ³ ) prepared in advance was added to prepare a film-forming composition.

(Example 10)
As an organic solvent, 45.85 g of isopropanol is prepared, and 0.65 g of a compound represented by the above formula (73) is weighed and added as a fluorine-containing silane compound (A) having a perfluoroamine structure. Thereafter, 3.5 g of the silicon alkoxide hydrolyzate (B) (average molecular weight: 4 × 10 ³ ) prepared in advance was added to prepare a film-forming composition.

(Example 11)
In the same manner as in Example 4, a hydrolyzate of silicon alkoxide (B) (average molecular weight: 4 × 10 ³ ) containing a fluorine-containing silane compound (A) having a perfluoroamine structure represented by the above formula (72). Obtained.
Next, 40 g of propylene glycol monomethyl ether was prepared as an organic solvent, and 10 g of hydrolyzate of silicon alkoxide (B) containing the fluorine-containing silane compound (A) represented by the above formula (73) was added to form a film. A composition was prepared.

(Example 12)
As an organic solvent, 49.32 g of ethanol is prepared, and 0.65 g of a compound represented by the above formula (73) is weighed and added as a fluorine-containing silane compound (A) having a perfluoroamine structure. Thereafter, 0.34 g of the silicon alkoxide hydrolyzate (B) (average molecular weight: 4 × 10 ³ ) prepared in advance was added to prepare a film-forming composition.

(Example 13)
Fluorine-containing silane having a perfluoroamine structure represented by the above formula (72), which is 0.01 parts by mass with respect to 1 part by mass when the mass of silicon alkoxide is 1 by the same method as in Example 4 above. A compound (A) is added and a hydrolyzate of silicon alkoxide (B) (average molecular weight: 4 × 10 ³ ) containing a fluorine-containing silane compound (A) having a perfluoroamine structure represented by the above formula (72). Obtained.
Next, 40 g of propylene glycol monomethyl ether was prepared as an organic solvent, and 10 g of hydrolyzate of silicon alkoxide (B) containing the fluorine-containing silane compound (A) represented by the above formula (73) was added to form a film. A composition was prepared.

(Example 14)
As an organic solvent, 42.7 g of ethanol is prepared, and 0.3 g of a compound represented by the above formula (71) is weighed and added as a fluorinated silane compound (A) having a perfluoroamine structure. Thereafter, 7 g of the hydrolyzate (B) (average molecular weight: 1 × 10 ³ ) of the silicon alkoxide prepared in advance was added to prepare a film forming composition.

(Example 15)
As an organic solvent, 41.8 g of isopropyl alcohol is prepared, and 0.2 g of a compound represented by the above formula (72) is weighed and added as a fluorine-containing silane compound (A) having a perfluoroamine structure. Thereafter, 8 g of the silicon alkoxide hydrolyzate (B) (average molecular weight: 2 × 10 ⁴ ) prepared in advance was added to prepare a film-forming composition.

(Comparative Example 1)
As an organic solvent, 48 g of ethanol was prepared, 2 g of a fluorine-containing silane compound (A) represented by the following formula (74) (C6FAS: manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the prepared film forming composition was Comparative Example 1. It was.
_{CF 3 - (CF 2) 5} -CH 2 -CH 2 -Si (OCH 3) 3 ··· (74)

(Comparative Example 2)
As an organic solvent, 48 g of ethanol was prepared, 2 g of a fluorine-containing silane compound (A) represented by the following formula (75) (C8FAS: manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the prepared film forming composition was compared with Comparative Example 2 did.
_{CF 3 - (CF 2) 7} -CH 2 -CH 2 -Si (OCH 3) 3 ··· (75)

(Comparative Example 3)
As an organic solvent, 48 g of ethanol was prepared, 2 g of a fluorinated silane compound (A) having a perfluoroamine structure represented by the above formula (72) was added, and the prepared film forming composition was set as Comparative Example 3.

(Comparative Example 4)
As an organic solvent, 42 g of ethanol was prepared, 8 g of hydrolyzate of silicon alkoxide (B) (average molecular weight: 4 × 10 ³ ) was added, and the prepared film forming composition was set as Comparative Example 4.

(Comparative Example 5)
As an organic solvent, 47.6 g of ethanol is prepared, and 2 g of a compound represented by the above formula (71) is weighed and added as a fluorine-containing silane compound (A) having a perfluoroamine structure. Then, 0.4 g of the hydrolyzate (B) (average molecular weight: 4 × 10 ³ ) prepared in advance was added to prepare a film-forming composition.

(Comparative Example 6)
As an organic solvent, 20 g of ethanol is prepared, and 0.03 g of a compound represented by the above formula (71) is weighed and added as a fluorinated silane compound (A) having a perfluoroamine structure. Thereafter, 29.97 g of the previously prepared hydrolyzate of silicon alkoxide (B) (average molecular weight: 4 × 10 ³ ) was added to prepare a film-forming composition.

(Comparative Example 7)
As an organic solvent, 42.7 g of ethanol was prepared, and 0.3 g of a fluorine-containing silane compound (A) represented by the above formula (74) (C6FAS: manufactured by Wako Pure Chemical Industries, Ltd.) was added. Thereafter, 7 g of the silicon alkoxide hydrolyzate (B) (average molecular weight: 4 × 10 ³ ) prepared in advance was added, and the film-forming composition was defined as Comparative Example 7.

(Comparative Example 8)
As an organic solvent, 42.7 g of ethanol was prepared, and 0.3 g of a fluorine-containing silane compound (A) represented by the above formula (75) (C8FAS: manufactured by Tokyo Chemical Industry Co., Ltd.) was added. Thereafter, 7 g of the silicon alkoxide hydrolyzate (B) (average molecular weight: 4 × 10 ³ ) prepared in advance was added, and the film-forming composition was defined as Comparative Example 8.

<Evaluation method>
(Water repellency evaluation of coating)
About the film using the composition for film formation prepared in the said Examples 1-15 and the said Comparative Examples 1-8, the contact angle measurement at the time of making water adhere was performed, and water repellency was evaluated. In addition, the member for evaluation was obtained by using a glass slide for the object to be processed (base material), applying the film-forming composition by a spin coating method, and baking the obtained film at 120 ° C. for 30 minutes. It was. The contact angle was measured using a CA-700 contact angle meter manufactured by Kyowa Interface Science Co., Ltd., the amount of water droplets was 2 μl, the contact angle was measured at any five points on the surface treatment member, and the average value was obtained. Was calculated. The evaluation results are shown in Table 1.

(Evaluation of film transparency)
The transmittance | permeability and haze were measured about the film using the composition for film formation prepared in the said Examples 1-15 and the said Comparative Examples 1-8, and transparency was evaluated.
"Transmissivity"
The evaluation member was adjusted in the same manner as the water repellency evaluation member, and the transmittance of the evaluation member (coating containing the substrate) was measured in the range of 240 to 2600 nm using a spectrophotometer U-4100 manufactured by Hitachi High-Tech. did. About the transmittance | permeability, the value in 550 nm which is a visible light range was confirmed. The evaluation results are shown in Table 1 below.

"Haze"
The evaluation member was adjusted in the same manner as the water repellency evaluation member, and the haze measurement of the evaluation member (coating containing the substrate) was performed using a haze meter HZ-V3 manufactured by Suga Test Instruments Co., Ltd. The evaluation results are shown in Table 1 below. The haze is a numerical value represented by the diffusion transmittance of the film / total light transmittance × 100.

(Evaluation of coating strength)
About the film using the composition for film formation prepared in the said Examples 1-15 and the said Comparative Examples 1-8, adhesiveness and durability were measured and the intensity | strength of the film was evaluated.
"Adhesion"
The evaluation member was prepared in the same manner as the water repellency evaluation member, and the adhesive tape was brought into contact with the surface of the evaluation member using an adhesive tape (manufactured by Nichiban Co., Ltd., cello tape CT-24). The degree of peeling was evaluated visually according to the following criteria. The evaluation results are shown in Table 1 below.
◎: When the adhesion of the coating is high and there is no adhesion on the tape side ○: When adhesion is confirmed on the tape side only at the end face or corner position of the base material △: Tape side at half or less of the test range ×: When adhesion is confirmed on the tape side over almost the entire test range

"durability"
The evaluation member was adjusted in the same manner as the water repellency evaluation member, and the transmittance of the evaluation member (base material including the film after forming the film) was measured as an initial evaluation. Thereafter, the evaluation member was stored in an environmental tester in a high-temperature and high-humidity state at 85 ° C. and 85% RH, and a 1000 hr durability test was performed. As the environmental tester, PL-1K manufactured by Espec was used. The transmittance of the evaluation member after 1000 hours was measured, and the rate of change was confirmed.
Transmittance after 1000 hr / transmittance of initial evaluation × 100 = change rate (%)
The evaluation results are shown in Table 1 below.

(Evaluation of antifouling properties of coating)
"Evaluation of repellency of oil pen"
Evaluation of repellency when an oil-based pen ("Magic Ink" manufactured by Uchida Yoko Co., Ltd.) is attached to the film using the film forming composition prepared in Examples 1 to 15 and Comparative Examples 1 to 8. (Evaluation of repellency of oil-based pen) was performed to evaluate the antifouling property of the coating. The evaluation member was prepared in the same manner as the above-described water repellency evaluation member, and a straight line having a length of 1 cm was written on the surface of the member using an oil-based pen. The evaluation results are shown in Table 1 below.
○: Repelled △: Partially repelled ×: Not repelled at all

  As shown in Table 1, the films formed using the film-forming compositions of the present invention (Examples 1 to 15) do not contain perfluoroalkyl groups having 8 or more carbon atoms, but are conventional fluorine-containing. Since the contact angle of water (110 ° or more) and the repellency (evaluation: ◯) of oil-based pens are superior to those when using silane compounds (Comparative Examples 1, 2, 7, 8) It was found to have properties (high water repellency and excellent antifouling properties).

  Moreover, since the film formed using the film forming composition of the present invention (Examples 1 to 15) contains a hydrolyzate of silicon alkoxide in the film forming composition, excellent transparency (transmission) Rate and haze) and excellent film strength (adhesion and durability).

  On the other hand, as shown in Table 1, in the film formed using the film forming composition of Comparative Examples 1 to 3, the film forming composition does not contain a hydrolyzate of silicon alkoxide. The contact angle was less than 110 °, and the repellency of the oil pen was evaluated as “Δ”. Moreover, durability was 85% or less, and it turned out that all are lower than the film formed using Examples 1-15.

  Moreover, in the film formed using the film forming composition of Comparative Example 7 and Comparative Example 8, since the hydrolyzate of silicon alkoxide is contained in the film forming composition, the durability is 90% or more. However, since it was formed using a conventional fluorine-containing silane compound, the contact angle of water was less than 110 °, and the evaluation of the repellency of the oil-based pen was “Δ”.

  It was also found that the film formed using the film forming composition of Comparative Example 4 was excellent in transparency and adhesion. However, since the film-forming composition does not contain a fluorine-containing silane compound having a perfluoroamine structure, the contact angle of water is 45 °, the oil repellency is low, and the repellent evaluation of the oil-based pen is also “x”. I understood it.

  Moreover, in the film formed using the film forming composition of Comparative Example 5, the fluorine-containing silane compound having a perfluoroamine structure is 1% and less than 2% in the solid component ratio in the film forming composition. Therefore, it was found that the contact angle of water was less than 110 °, the oil repellency was low, and the evaluation of the repellent property of the oil pen was “Δ”. Moreover, since the content of the hydrolyzate of silicon alkoxide in the film forming composition is small, it was found that the adhesion evaluation of the film was also “Δ”.

  Further, in the film formed using the film forming composition of Comparative Example 6, the fluorine-containing silane compound having a perfluoroamine structure in the solid component ratio in the film forming composition was 98%, exceeding 95%. As a result, the water contact angle was 90 °, the oil repellency was low, and the evaluation of the repellent property of the oil pen was “x”.

  The film-forming composition of the present invention is a coating agent that imparts various properties such as antifouling properties, fingerprint resistance, water and oil repellency, release properties, moisture resistance, water resistance, lubricity, and heat resistance, and heat resistance. It is useful in a wide range of applications such as a surface treatment agent such as a paint additive for imparting properties.

Claims (6)

A fluorine-containing silane compound having a perfluoroamine structure represented by the following general formula (1);
A hydrolyzate of silicon alkoxide;
A film-forming composition comprising an organic solvent.

In the above formula (1), m and n are the same or different integers of 1 to 6, respectively. Rf ¹ is a C 1-6 perfluoroalkylene group, and may be linear or branched.
Moreover, in said formula (1), X is a bivalent organic group, is a C2-C10 hydrocarbon group, Comprising: One or more types selected from an ether bond, an ester bond, an amide bond, and a urethane bond May be included.
Furthermore, in the above formula (1), ^{R 1} is a lower alkyl group or a phenyl group, Z is a hydrolyzable group (wherein, a is an integer of 0 to 3).   The film forming composition according to claim 1, wherein the hydrolyzable group Z is an alkoxy group. The film forming composition according to claim 1 or 2, wherein the hydrolyzate of the silicon alkoxide has an average molecular weight of 1 x 10 ³ or more and 2 x 10 ⁴ or less. A method for producing a film-forming composition according to any one of claims 1 to 3,
A composition for forming a film, wherein after producing a hydrolyzate of the silicon alkoxide from the silicon alkoxide, the fluorine-containing silane compound and the produced hydrolyzate of the silicon alkoxide are added to and mixed with the organic solvent. Manufacturing method. A method for producing a film-forming composition according to any one of claims 1 to 3,
The method for producing a film-forming composition, wherein the silicon alkoxide and the fluorine-containing silane compound are simultaneously added to and mixed with the organic solvent.   The film formed using the film forming composition as described in any one of Claims 1 thru | or 3.