JP2016210821A - Composition for forming coating film and method of producing the same, and coating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for forming a coating film, enabling a coating film having high hydrophilic property and oil repellency and excellent antifouling property to be formed without containing a linear perfluoroalkyl group having 8 or more carbon atoms which becomes a problem in terms of bioaccumulation potential and environmental adaptability.SOLUTION: The composition for forming a coating film is provided which contains: one or more kind of nitrogen-containing fluorine-based compound having a perfluoroalkyl group; an oxide fine particle having an average primary particle diameter of 2 to 50 nm, hydrolysate of silicon alkoxide and an organic solvent. In the composition for forming a coating film, a composition ratio of the nitrogen-containing fluorine-based compound in all solid component contained in the nitrogen-containing fluorine-based compound, the oxide fine particle and the hydrolysate of silicon alkoxide is 6 to 40 mass%, a composition ratio of the oxide fine particle is 40 to 90 mass% and a composition ratio of the hydrolysate of silicon alkoxide is 4 to 40 mass%.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 workability, and therefore, there is a great demand in the optical 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.

  By the way, conventionally, many techniques and materials for imparting hydrophilic oil repellency to the surface have been proposed in order to make it difficult for dirt to adhere to the surfaces of various substrates and to easily remove dirt by washing with water.

  For example, Patent Document 1 discloses an additive or coating agent that contains a fluorine-based compound and a silane coupling agent, is excellent in water / oil repellency and hydrophilic / oil repellency, and exhibits a high antifouling effect. ing.

Japanese Patent No. 3342170

  By the way, conventionally, fluoroalkyl group-containing fluorine-based compounds have been used in various fields as imparting agents such as oil repellency, and in particular, those containing a linear perfluoroalkyl group having 8 or more carbon atoms have been used. It was.

  However, in recent years, perfluorooctane sulfonic acid (PFOS) and perfluoroctanic acid (PFOA) are stable in the environment because of their stable structures (hardly decomposable), and have high toxicity and high environmental / bioaccumulative 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 of the present invention to provide a film-forming composition capable of forming a film having oil repellency and excellent antifouling properties and transparency.

  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, this invention makes it a subject to provide the film which has high hydrophilic property and oil repellency, and the outstanding antifouling property and transparency.

In order to solve the above problems, the present invention employs the following configuration.
[1] One or more nitrogen-containing fluorine-based compounds represented by the following formulas (1) to (4);
Oxide fine particles having an average primary particle diameter of 2 to 50 nm;
A hydrolyzate of silicon alkoxide;
An organic solvent,
In all solid components contained in the hydrolyzate of the nitrogen-containing fluorine-based compound, the oxide fine particles and the silicon alkoxide,
The composition ratio of the nitrogen-containing fluorine compound is 6 to 40% by mass,
The composition ratio of the oxide fine particles is 40 to 90% by mass,
The composition for film formation whose composition ratio of the hydrolyzate of the said silicon alkoxide is 4-40 mass%.

In the above formulas (1) and (2), Rf ¹ and Rf ² are the same or different from each other, each having 1 to 6 carbon atoms and a linear or branched perfluoroalkyl group. Rf ³ is a linear or branched perfluoroalkylene group having 1 to 6 carbon atoms.

In the above formulas (3) and (4), Rf ⁴ and Rf ⁵ are the same or different, each having 1 to 6 carbon atoms and a linear or branched perfluoroalkylene group. Rf ⁶ has 1 to 6 carbon atoms and is a linear or branched perfluoroalkylene group. Z is an oxygen atom, a nitrogen atom, a CF ₂ group or a CF group.

  In the above formulas (2) and (4), R is a divalent organic group and is a linear or branched linking group.

  Moreover, in said formula (1)-(4), X is any one hydrophilicity imparting group selected from the group which consists of an anionic type, a cationic type, and an amphoteric type.

[2] The film forming composition according to item 1, wherein the hydrolyzate of silicon alkoxide has an average molecular weight of 1 × 10 ³ or more and 2 × 10 ⁴ or less.
[3] The preceding item 1 or 2, wherein the oxide fine particles are one or a mixture of two or more selected from the group selected from silica, ITO, and oxides of In, Sn, Zn, Ti, or W. The composition for film formation as described in 2.

[4] A method for producing a film-forming composition according to any one of items 1 to 3,
After producing a hydrolyzate of the silicon alkoxide from the silicon alkoxide, the nitrogen-containing fluorine-based compound, the oxide fine particles, and the produced hydrolyzate of the silicon alkoxide are added to the organic solvent. The manufacturing method of the composition for film formation to mix.

[5] A method for producing a film-forming composition according to any one of items 1 to 3,
The method for producing a film-forming composition, wherein the silicon alkoxide, the nitrogen-containing fluorine-based compound, and the oxide fine particles are simultaneously added to and mixed with the organic solvent.

[6] A film formed using the composition for forming a film according to any one of items 1 to 3.

The film-forming composition of the present invention has high hydrophilicity and oil repellency 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 antifouling properties.
Moreover, the film formed using the film forming composition of the present invention has a low haze value and excellent transparency.

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

  The coating film of the present invention has high hydrophilicity and oil 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 this embodiment is also referred to as (A) a nitrogen-containing fluorine compound having a perfluoroamine structure (hereinafter simply referred to as “nitrogen-containing fluorine compound” or “component (A)”, or “hydrophilic oil repellent”). And (B) oxide fine particles having an average primary particle diameter of 2 to 50 nm (hereinafter sometimes referred to as “component (B)” or “oxide nanoparticles”), and (C) hydrolysis of silicon alkoxide Product (hereinafter also referred to as “component (C)”) and (D) an organic solvent (hereinafter also referred to as “component (D)”).

(A) Nitrogen-containing fluorine-based compound (A) The nitrogen-containing fluorine-based compound that can be applied to the composition of the present embodiment is a hydrophilic oil-repellent agent that includes an oil-repellent group and a hydrophilic group in the molecule. There is no particular limitation. Specifically, such nitrogen-containing fluorine compounds can be represented by the following general formulas (1) to (4).

In the above formulas (1) and (2), Rf ¹ and Rf ² are the same or different perfluoroalkyl groups having 1 to 6 carbon atoms, and Rf ³ is a perfluoroalkylene group having 1 to 6 carbon atoms. It may be linear or branched.
Rf ¹ and Rf ² are preferably the same or different from each other, and are each a linear or branched perfluoroalkyl group having 1 to 4 carbon atoms. Rf ³ is preferably a linear or branched perfluoroalkylene group having 1 to 4 carbon atoms.

In the above formulas (3) and (4), Rf ⁴ and Rf ⁵ are the same or different perfluoroalkyl groups having 1 to 6 carbon atoms, and Rf ⁶ is a perfluoroalkylene group having 1 to 6 carbon atoms. It may be linear or branched. Z is an oxygen atom, a nitrogen atom, a CF ₂ group or a CF group. When Z is a nitrogen atom or a carbon atom, a perfluoroalkyl group branched from Z may be bonded to Z.
Rf ⁴ and Rf ⁵ are preferably the same or different from each other, and are each a linear or branched perfluoroalkylene group having 1 to 4 carbon atoms. Rf ⁶ has 1 to 4 carbon atoms, and is preferably a linear or branched perfluoroalkylene group.

  In the above formulas (2) and (4), R is a divalent organic group, which is a linear or branched linking group, and an ether bond, ester bond, amide bond and One or more bonds selected from urethane bonds may or may not be included.

  Moreover, in said formula (1)-(4), X is any one hydrophilicity provision group selected from the group which consists of an anionic type, a cationic type, and an amphoteric type.

Moreover, the composition of this embodiment is a mixture containing one or more selected from the group consisting of nitrogen-containing fluorine-based compounds represented by the above formulas (1) to (4). It may be used as a compound (hydrophilic oil repellent).
Hereinafter, (A) the nitrogen-containing fluorine-based compound will be described in detail.

"Linear nitrogen-containing fluorine compounds"
In the linear (or branched) nitrogen-containing fluorine-based compound represented by the above formula (1) or (2), a nitrogen-containing perfluoroalkyl group composed of Rf ¹ and Rf ² and a nitrogen-containing perfluoro composed of Rf ³ The alkylene group constitutes an oil repellency imparting group.
Further, in the above formula (1) or the formula nitrogen-containing fluorine compound shown in (2), in Rf ¹ ~Rf ³ is the oil repellency imparting group, the total carbon number of fluorine is bonded is 4 to 18 pieces It is preferable to be in the range. If the number of carbons to which fluorine is bonded is less than 4, it is not preferable because the oil repellent effect is insufficient.

  Specific examples of the structure of the oil repellency-imparting group in the formula (1) or the formula (2) include the structures of the following formulas (5) to (22).

  Here, in the above formula (2), R is a linking group that connects the oil repellency-imparting group and the hydrophilicity-imparting group in the molecular chain. The structure of the linking group R is not particularly limited as long as it is a linear or branched divalent organic group. The linking group R may or may not contain one or more types of bonds selected from ether bonds, ester bonds, amide bonds and urethane bonds in the molecular chain.

  Specifically, for example, the linking group R may be a hydrocarbon group having 1 to 20 carbon atoms, or may contain one or more selected from a polyoxyalkylene group and an epoxy group.

  Further, the linking group R may have a polymer of a binary copolymer or a terpolymer in the molecular chain.

  Here, in the above formula (2), an example in the case of having a terpolymer in the molecular chain of the linking group R is shown in the following general formula (23).

In the general formula (23), R ¹⁰ is a hydrogen atom or a methyl group. Further, o, p, and q are independent integers of 1 or more. X ₁ and X ₂ are different hydrophilicity-imparting groups. Furthermore, R ¹¹ is a divalent organic group that connects the main chain of the copolymer and the oil repellency-imparting group, and includes at least one bond selected from an ether bond, an ester bond, an amide bond, and a urethane bond. . Furthermore, there may be R ¹² and R ¹³ which are divalent organic groups that connect the main chain of the copolymer and the hydrophilicity-imparting group, and may be selected from an ether bond, an ester bond, an amide bond, and a urethane bond. One or more types of bonds may or may not be included.

  The linking group R is preferably selected and introduced as appropriate depending on the properties desired to be imparted to the hydrophilic oil repellent. Specifically, for example, to adjust the solubility in a solvent, to improve the durability by improving the adhesion between the surface coating material and the base material, the compatibility between the hydrophilic oil repellent and the resin component, etc. The case where it wants to improve is mentioned. The methods include adjusting the chain length of hydrocarbon groups in a linear or branched structure, adjusting the presence or type of polar groups that affect intermolecular interactions, and the chemicals contained in the substrate and resin components. For example, a structure similar to a part of the structure is introduced.

In the formula (1) or the formula (2), X is any one hydrophilicity-providing group selected from the group consisting of an anionic type, a cationic type and an amphoteric type.
Hereinafter, the structure of the hydrophilic lube repellant will be described by dividing the hydrophilicity imparting group X into cases.

[Anion type]
In the case where the hydrophilicity-imparting group X is an anionic type, the above X is “—CO ₂ M ¹ ”, “—SO ₃ M ¹ ”, “—OSO ₂ M ¹ ”, “—OP (OH) O _{2” at the terminal.} M ¹ ”,“ —OPO ₃ M ¹ ₂ ”or“ ═O ₂ PO ₂ M ¹ ”(M ¹ is an alkali metal, an alkaline earth metal, Mg, Al, R ¹ R ² R ³ R ⁴ N ⁺ ; R ^{1 to} R ⁴ each have a hydrogen atom or an independent linear or branched alkyl group having 1 to 20 carbon atoms.

  Examples of the alkali metal include lithium (Li), sodium (Na), potassium (K), and cesium (Cs). Examples of the alkaline earth metal include calcium (Ca), strontium (Sr), and barium (Ba).

As the quaternary ammonium salt ^{(R 1 R 2 R 3 R} 4 N +), a straight-chain or branched alkyl group R 1 to R ⁴ is up to 1 to 20 carbon atoms which independently hydrogen atom or each If there is, it will not be specifically limited. More specifically, examples of the compound in which R ¹ R ² R ³ R ⁴ are all the same include (CH ₃ ) ₄ N ⁺ , (C ₂ H ₅ ) ₄ N ⁺ , and (C ₃ H ₇ ) ₄ N ^+. , (C ₄ H ₉ ) ₄ N ⁺ , (C ₅ H ₁₁ ) ₄ N ⁺ , (C ₆ H ₁₃ ) ₄ N ⁺ , (C ₇ H ₁₅ ) ₄ N ⁺ , (C ₈ H ₁₇ ) ₄ N ⁺ , (C ₉ H ₁₉ ) ₄ N ⁺ , (C ₁₀ H ₂₁ ) ₄ N ^{+ and the} like. In addition, when R ¹ R ² R ³ is all a methyl group, for example, R ⁴ is (C ₂ H ₅ ), (C ₆ H ₁₃ ), (C ₈ H ₁₇ ), (C ₉ H ₁₉ ), Examples of the compound include (C ₁₀ H ₂₁ ), (C ₁₂ H ₂₅ ), (C ₁₄ H ₂₉ ), (C ₁₆ H ₃₃ ), and (C ₁₈ H ₃₇ ). Further, when all of R ¹ R ² are methyl groups, for example, all of R ³ R ⁴ are (C ₈ H ₁₇ ), (C ₁₀ H ₂₁ ), (C ₁₂ H ₂₅ ), (C ₁₄ H ₂₉ ). , (C ₁₆ H ₃₃ ), (C ₁₈ H ₃₇ ) and the like. Furthermore, examples of the case where R ¹ is a methyl group include compounds in which R ² R ³ R ⁴ are all (C ₄ H ₉ ), (C ₈ H ₁₇ ), and the like.

By the way, in an application that is used in contact with water, it is desired to have durability against water and durability of a hydrophilic oil repellent effect. From the above viewpoint, the hydrophilic oil repellent of the present embodiment is desirably a hardly soluble compound having low solubility in water. That is, in the hydrophilic oil repellent of the present embodiment, when the hydrophilicity imparting group X is an anion type, the M ^{1 as} a counter ion is preferably an alkaline earth metal, Mg, or Al, particularly Ca, Ba. Mg is preferred because of its excellent hydrophilic oil repellency and low solubility in water.

Here, when the hydrophilicity-imparting group X is an anionic type, a specific example of the structure of the nitrogen-containing fluorine-based compound represented by the above formula (1) or the above formula (2) (however, the structure of M ¹ which is a counter ion) For example, the structures of the following formulas (24) to (80) may be mentioned.

[Cation type]
In the case where the hydrophilicity-imparting group X is a cationic type, the above X has “—N ⁺ R ⁵ R ⁶ R ⁷ .Cl ⁻ ”, “—N ⁺ R ⁵ R ⁶ R ⁷ .Br ⁻ ”, “— ^{N + R 5 R 6 R 7} · I - "" ^{- N + R 5 R 6 R} 7 · CH 3 SO 3 - , "" ^{- N + R 5 R 6 R} 7 · NO 3 - "," (- ^{N + R 5 R 6 R 7} ) 2 CO 3 2- "or" ^{(-N + R 5 R 6 R} 7) 2 SO 4 2- ^"(R 5 to R ⁷ is C 1 -C independent hydrogen atom or each Up to 20 linear or branched alkyl groups).

  Here, when the hydrophilicity imparting group X is a cationic type, specific examples of the structure of the nitrogen-containing fluorine-based compound represented by the above formula (1) or the above formula (2) include, for example, the following formulas (81) to The structure of (109) is mentioned.

[Bisexual type]
When the hydrophilicity-imparting group X is an amphoteric type, the above X is at the end of the carboxybetaine type “—N ⁺ R ⁸ R ⁹ (CH ₂ ) _n CO ₂ ⁻ ”, and the sulfobetaine type “—N ⁺ R”. ⁸ R ⁹ (CH ₂ ) _n SO ₃ ⁻ ”or“ —N ⁺ R ⁸ R ⁹ O ⁻ ”of the amine oxide type (n is an integer of 1 to 5, R ⁸ and R ⁹ are a hydrogen atom or a carbon number of 1 to 10 alkyl groups).

  Here, when the hydrophilicity imparting group X is an amphoteric type, specific examples of the structure of the nitrogen-containing fluorine-based compound represented by the above formula (1) or the above formula (2) include, for example, the following formulas (110) to 110 The structure of (121) is mentioned.

The hydrophilic oil repellent used in the present invention can be variously modified without departing from the gist of the present invention. For example, in the specific example of the structure of the nitrogen-containing fluorine-based compound described above, Rf ¹ and Rf ² shown in Formula (1) and Formula (2) are symmetrical as the oil repellency-imparting group composed of a nitrogen-containing perfluoroalkyl group. Although a certain case has been described, the present invention is not limited to this and may be asymmetric.

Next, the manufacturing method of the nitrogen-containing fluorine-type compound shown to the said Formula (1) or the said Formula (2) is demonstrated.
The method for producing a nitrogen-containing fluorine-based compound represented by the above formula (1) or the above formula (2) uses a carboxylic acid halide or sulfonic acid halide having a nitrogen-containing perfluoroalkyl group represented by the following formula (122) as a raw material. The nitrogen-containing fluorine-type compound shown to the said Formula (1) and the said Formula (2) is manufactured.

Here, in the above formula (122), Rf ¹ and Rf ² are the same or different C 1-6 perfluoroalkyl groups, and Rf ³ is a C 1-6 perfluoroalkylene group, It may be chain or branched.
Rf ¹ and Rf ² are preferably the same or different from each other, and are each a linear or branched perfluoroalkyl group having 1 to 4 carbon atoms. Rf ³ is preferably a linear or branched perfluoroalkylene group having 1 to 4 carbon atoms.
Y is CO or SO ₂ .
Furthermore, A is any one halogen atom selected from the group consisting of fluorine, chlorine, bromine and iodine.

  In addition, the manufacturing method of the said nitrogen-containing fluorine-type compound becomes a different manufacturing method by the kind of X shown in the said Formula (1) and said Formula (2). In the following, description will be made for each case.

[In case of anion type]
First, the case where the nitrogen-containing fluorine-type compound shown to said Formula (1) is manufactured is demonstrated.
Among the raw materials represented by the above formula (122), when Y is CO (in the case of carboxylic acid), M (OH) _m (M is Li, Na, K, Ca, Mg, Al, etc.), m is , 1 in the case of monovalent cations such as Li, Na, K, 2 in the case of divalent cations such as Ca, Mg, and 3 in the case of trivalent cations such as Al, and when Y is SO ₂ (sulfonic acid type In the case) M (OH) _m (M is Li, Na, K, R ¹ R ² R ³ R ⁴ N ⁺ , Ca, Mg, Al, etc.), m is a monovalent cation such as Li, Na, K, etc. In the case of 1, 2 in the case of divalent cations such as Ca and Mg, 3 in the case of trivalent cations such as Al, R ^{1 to} R ⁴ are each a hydrogen atom or an independent straight chain or branched chain having 1 to 20 carbon atoms. Each alkyl group) is added dropwise to the neutralization reaction, and then dried to dryness, so that the target product is soluble and by-product That M (A), by M (A) ₂ or M (A) ₃ extracts the desired product from an individual obtained by dryness using a solvent-insoluble, yet the extraction solvent to dryness, the purpose You can get things. If necessary, this salt can be converted to carboxylic acid or sulfonic acid using an acid such as sulfuric acid, and after distillation, the salt can be purified again with M (OH) _m to obtain a high purity. is there.

Next, the case where the nitrogen-containing fluorine-type compound shown to said Formula (2) is manufactured is demonstrated.
Specifically, for example, when a linking group R having an amide bond is introduced between an oil repellency-imparting group (nitrogen-containing perfluoroalkyl group) and an anionic hydrophilicity-imparting group, first, nitrogen-containing perfluoroalkylcarbonyl is introduced. An alkali metal salt of a carboxylic acid or sulfonic acid having an amide bond is obtained by reacting fluoride or sulfonyl fluoride with aminoalkyl carboxylic acid or aminophenyl sulfonic acid and then reacting with alkali hydroxide. It is done.

  Further, for example, when a linking group R having an ester bond is introduced between an oil repellency-imparting group (nitrogen-containing perfluoroalkyl group) and an anionic hydrophilicity-imparting group, first, nitrogen-containing perfluoroalkylcarbonyl fluoride or A sulfonyl fluoride is reacted with a hydroxyphenyl organic acid and then reacted with an alkali hydroxide to obtain an alkali metal salt of a carboxylic acid or sulfonic acid having an ester bond.

For example, when a linking group R having an ether bond is introduced between an oil repellency-imparting group (nitrogen-containing perfluoroalkyl group) and an anionic hydrophilicity-imparting group, first, a nitrogen-containing perfluoroalkylcarbonyl fluoride is introduced. Reduction with lithium aluminum hydride (LiAlH ₄ ) or sodium borohydride (NaBH ₄ ) produces an alcohol having a nitrogen-containing perfluoroalkyl group. Next, after converting to potassium alcoholate with t-butoxypotassium or the like and reacting with a metal salt of a halogenated organic acid, an alkali metal salt of a carboxylic acid having an ether bond is obtained.

[Cation type]
Specifically, for example, among the raw materials represented by the above formula (122), a nitrogen-containing perfluoroalkylcarbonyl fluoride or sulfonyl fluoride and an N, N-dialkylaminoalkyleneamine are amide-bonded to form a terminal tertiary amine. And then quaternized with an alkylating agent such as methyl iodide (CH ₃ I), methyl bromide (CH ₃ Br), dimethyl sulfate ((CH ₃ ) ₂ SO ₄ ), and the like. A nitrogen-containing fluorine-based compound having a hydrophilicity imparting group is obtained.

Further, for example, among the raw materials represented by the above formula (122), after nitrogen-containing perfluoroalkylcarbonyl fluoride or sulfonyl fluoride and N, N-dialkylaminoalkylene alcohol are ether-bonded to form a terminal tertiary amine Quaternization with an alkylating agent such as methyl iodide (CH ₃ I), methyl bromide (CH ₃ Br), dimethyl sulfate ((CH ₃ ) ₂ SO ₄ ), etc. to impart cationic hydrophilicity A nitrogen-containing fluorine-based compound having a group is obtained.

[Bisexual type]
Specifically, for example, in the case of the carboxybetaine type, first, among the raw materials represented by the above formula (122), nitrogen-containing perfluoroalkylcarbonyl fluoride or sulfonyl fluoride and N, N-dialkylaminoalkyleneamine are amides. Nitrogen-containing fluorine having an amphoteric hydrophilicity-imparting group by bonding or ether-bonding with N, N-dialkylaminoalkylene alcohol to form a terminal tertiary amine and then reacting with sodium monochloroacetate Series compounds are obtained.

  Also, for example, in the case of sulfobetaine type, after forming a terminal tertiary amine as described above, it is reacted with a cyclic sulfonic acid ester compound typified by 1,3-propane sultone, etc. A nitrogen-containing fluorine-based compound having an imparting group is obtained.

  In addition, for example, in the case of an amine oxide type, a nitrogen-containing fluorine-based compound having an amphoteric hydrophilicity-imparting group can be obtained by making a terminal tertiary amine as described above and then reacting with hydrogen peroxide.

"Cyclic nitrogen-containing fluorine compounds"
In the cyclic nitrogen-containing fluorine-based compound represented by the above formula (3) or the above formula (4), a nitrogen-containing perfluoroalkylene group composed of Rf ⁴ , Rf ⁵ and Rf ⁶ and further Z constitutes an oil repellency-imparting group. To do.
Further, in the above formula (3) or the formula (4) nitrogen-containing fluorine compound shown, of the repellent Rf ⁴ ~Rf ⁶ and wherein Z is an oily imparting group, the total carbon number of fluorine is bonded is 4 A range of 18 is preferred. If the number of carbons to which fluorine is bonded is less than 4, it is not preferable because the oil repellent effect is insufficient.

  Specific examples of the structure of the oil repellency-imparting group in the formula (3) or the formula (4) include structures of the following formulas (123) to (141).

  Here, in the above formula (4), R is a linking group that connects the oil repellency-imparting group and the hydrophilicity-imparting group in the molecular chain. The structure of the linking group R is not particularly limited as long as it is a linear or branched divalent organic group. The linking group R may or may not contain one or more types of bonds selected from ether bonds, ester bonds, amide bonds and urethane bonds in the molecular chain.

  Specifically, for example, the linking group R may be a hydrocarbon group having 1 to 20 carbon atoms, or may contain one or more selected from a polyoxyalkylene group and an epoxy group.

  Further, the linking group R may have a polymer of a binary copolymer or a terpolymer in the molecular chain.

  Here, in the above formula (4), an example in the case of having a terpolymer in the molecular chain of the linking group R is shown in the following formula (142).

In the formula ^{(142), R 10} is a hydrogen atom or a methyl group. Further, o, p, and q are independent integers of 1 or more. X ₁ and X ₂ are different hydrophilicity-imparting groups. Furthermore, R ¹¹ is a divalent organic group that connects the main chain of the copolymer and the oil repellency-imparting group, and includes at least one bond selected from an ether bond, an ester bond, an amide bond, and a urethane bond. . Furthermore, there may be R ¹² and R ¹³ which are divalent organic groups that connect the main chain of the copolymer and the hydrophilicity-imparting group, and may be selected from an ether bond, an ester bond, an amide bond, and a urethane bond. One or more types of bonds may or may not be included.

  The linking group R is preferably selected and introduced as appropriate depending on the properties desired to be imparted to the hydrophilic oil repellent. Specifically, for example, to adjust the solubility in a solvent, to improve the durability by improving the adhesion between the surface coating material and the base material, the compatibility between the hydrophilic oil repellent and the resin component, etc. The case where it wants to improve is mentioned. The methods include adjusting the chain length of hydrocarbon groups in a linear or branched structure, adjusting the presence or type of polar groups that affect intermolecular interactions, and the chemicals contained in the substrate and resin components. For example, a structure similar to a part of the structure is introduced.

Moreover, in said formula (3) or said formula (4), X is any one hydrophilicity imparting group selected from the group which consists of an anionic type, a cationic type, and an amphoteric type.
Hereinafter, the structure of the hydrophilic lube repellant will be described by dividing the hydrophilicity imparting group X into cases.

[Anion type]
In the case where the hydrophilicity-imparting group X is an anionic type, the above X is “—CO ₂ M ¹ ”, “—SO ₃ M ¹ ”, “—OSO ₂ M ¹ ”, “—OP (OH) O _{2” at the terminal.} M ¹ ”,“ —OPO ₃ M ¹ ₂ ”or“ ═O ₂ PO ₂ M ¹ ”(M ¹ is an alkali metal, an alkaline earth metal, Mg, Al, R ¹ R ² R ³ R ⁴ N ⁺ ; R ^{1 to} R ⁴ each have a hydrogen atom or an independent linear or branched alkyl group having 1 to 20 carbon atoms.

  Examples of the alkali metal include lithium (Li), sodium (Na), potassium (K), and cesium (Cs). Examples of the alkaline earth metal include calcium (Ca), strontium (Sr), and barium (Ba).

As the quaternary ammonium salt ^{(R 1 R 2 R 3 R} 4 N +), a straight-chain or branched alkyl group R 1 to R ⁴ is up to 1 to 20 carbon atoms which independently hydrogen atom or each If there is, it will not be specifically limited. More specifically, examples of the compound in which R ¹ R ² R ³ R ⁴ are all the same include (CH ₃ ) ₄ N ⁺ , (C ₂ H ₅ ) ₄ N ⁺ , and (C ₃ H ₇ ) ₄ N ^+. , (C ₄ H ₉ ) ₄ N ⁺ , (C ₅ H ₁₁ ) ₄ N ⁺ , (C ₆ H ₁₃ ) ₄ N ⁺ , (C ₇ H ₁₅ ) ₄ N ⁺ , (C ₈ H ₁₇ ) ₄ N ⁺ , (C ₉ H ₁₉ ) ₄ N ⁺ , (C ₁₀ H ₂₁ ) ₄ N ^{+ and the} like. In addition, when R ¹ R ² R ³ is all a methyl group, for example, R ⁴ is (C ₂ H ₅ ), (C ₆ H ₁₃ ), (C ₈ H ₁₇ ), (C ₉ H ₁₉ ), Examples of the compound include (C ₁₀ H ₂₁ ), (C ₁₂ H ₂₅ ), (C ₁₄ H ₂₉ ), (C ₁₆ H ₃₃ ), and (C ₁₈ H ₃₇ ). Further, when all of R ¹ R ² are methyl groups, for example, all of R ³ R ⁴ are (C ₈ H ₁₇ ), (C ₁₀ H ₂₁ ), (C ₁₂ H ₂₅ ), (C ₁₄ H ₂₉ ). , (C ₁₆ H ₃₃ ), (C ₁₈ H ₃₇ ) and the like. Furthermore, examples of the case where R ¹ is a methyl group include compounds in which R ² R ³ R ⁴ are all (C ₄ H ₉ ), (C ₈ H ₁₇ ), and the like.

By the way, in an application that is used in contact with water, it is desired to have durability against water and durability of a hydrophilic oil repellent effect. From the above viewpoint, the hydrophilic oil repellent of the present embodiment is desirably a hardly soluble compound having low solubility in water. That is, in the hydrophilic oil repellent of the present embodiment, when the hydrophilicity imparting group X is an anion type, the M ^{1 as} a counter ion is preferably an alkaline earth metal, Mg, or Al, particularly Ca, Ba. Mg is preferred because of its excellent hydrophilic oil repellency and low solubility in water.

Here, when the hydrophilicity-imparting group X is an anionic type, a specific example of the structure of the nitrogen-containing fluorine compound represented by the above formula (3) or the above formula (4) (however, the structure of M ¹ which is a counter ion) For example, the structures of the following formulas (143) to (196) may be mentioned.

[Cation type]
In the case where the hydrophilicity-imparting group X is a cationic type, the above X has “—N ⁺ R ⁵ R ⁶ R ⁷ .Cl ⁻ ”, “—N ⁺ R ⁵ R ⁶ R ⁷ .Br ⁻ ”, “— ^{N + R 5 R 6 R 7} · I - "" ^{- N + R 5 R 6 R} 7 · CH 3 SO 3 - , "" ^{- N + R 5 R 6 R} 7 · NO 3 - "," (- ^{N + R 5 R 6 R 7} ) 2 CO 3 2- "or" ^{(-N + R 5 R 6 R} 7) 2 SO 4 2- ^"(R 5 to R ⁷ is C 1 -C independent hydrogen atom or each Up to 20 linear or branched alkyl groups).

  Here, when the hydrophilicity imparting group X is a cation type, specific examples of the structure of the nitrogen-containing fluorine-based compound represented by the above formula (3) or the above formula (4) include, for example, the following formulas (197) to (197): The structure of (219) is mentioned.

[Bisexual type]
When the hydrophilicity-imparting group X is an amphoteric type, the above X is at the end of the carboxybetaine type “—N ⁺ R ⁸ R ⁹ (CH ₂ ) _n CO ₂ ⁻ ”, and the sulfobetaine type “—N ⁺ R”. ⁸ R ⁹ (CH ₂ ) _n SO ₃ ⁻ ”or“ —N ⁺ R ⁸ R ⁹ O ⁻ ”of the amine oxide type (n is an integer of 1 to 5, R ⁸ and R ⁹ are a hydrogen atom or a carbon number of 1 to 10 alkyl groups).

  Here, when the hydrophilicity imparting group X is an amphoteric type, specific examples of the structure of the nitrogen-containing fluorine-based compound represented by the above formula (3) or the above formula (4) include, for example, the following formulas (220) to The structure of (242) is mentioned.

The hydrophilic oil repellent used in the present invention can be variously modified without departing from the gist of the present invention. For example, in the specific example of the structure of the nitrogen-containing fluorine-based compound described above, Rf ⁴ and Rf ⁵ shown in formulas (3) and (4) represent Z as the oil repellency imparting group composed of a nitrogen-containing perfluoroalkyl group. Although the description has been made with respect to the case of being symmetric, it is not limited to this and may be asymmetrical.

Next, the manufacturing method of the nitrogen-containing fluorine-type compound shown to the said Formula (3) or the said Formula (4) is demonstrated.
The method for producing a nitrogen-containing fluorine-based compound represented by the above formula (3) or the above formula (4) uses a carboxylic acid halide or sulfonic acid halide having a nitrogen-containing perfluoroalkyl group represented by the following formula (243) as a raw material. The nitrogen-containing fluorine-based compound represented by the above formula (3) or the above formula (4) is produced.

Here, in the above formula (243), Rf ⁴ , Rf ⁵ and Rf ⁶ are the same or different C 1-6 perfluoroalkylene groups, and may be linear or branched.
Rf ⁴ and Rf ⁵ are preferably the same or different from each other, and are each a linear or branched perfluoroalkylene group having 1 to 4 carbon atoms. Rf ⁶ has 1 to 4 carbon atoms, and is preferably a linear or branched perfluoroalkylene group.
Z is an oxygen atom, a nitrogen atom, a CF ₂ group or a CF group. When Z is a nitrogen atom or a carbon atom, a perfluoroalkyl group branched from Z may be bonded to Z.
Y is CO or SO ₂ .
Furthermore, A is any one halogen atom selected from the group consisting of fluorine, chlorine, bromine and iodine.

  In addition, the manufacturing method of the said nitrogen-containing fluorine-type compound becomes a manufacturing method which changes with kinds of X shown in the said Formula (3) and said Formula (4). In the following, description will be made for each case.

[In case of anion type]
First, the case where the nitrogen-containing fluorine-type compound shown to said Formula (3) is manufactured is demonstrated.
Among the raw materials represented by the above formula (243), when Y is CO (in the case of a carboxylic acid type), M (OH) _m (M is Li, Na, K, Ca, Mg, Al, etc.), , 1 in the case of monovalent cations such as Li, Na, K, 2 in the case of divalent cations such as Ca, Mg, and 3 in the case of trivalent cations such as Al, and when Y is SO ₂ (sulfonic acid type In the case) M (OH) _m (M is Li, Na, K, R ¹ R ² R ³ R ⁴ N ⁺ , Ca, Mg, Al, etc.), m is a monovalent cation such as Li, Na, K, etc. In the case of 1, 2 in the case of divalent cations such as Ca and Mg, 3 in the case of trivalent cations such as Al, R ^{1 to} R ⁴ are each a hydrogen atom or an independent straight chain or branched chain having 1 to 20 carbon atoms. Each alkyl group) is added dropwise to the neutralization reaction, and then dried to dryness, so that the target product is soluble and by-product That M (A), by M (A) ₂ or M (A) ₃ extracts the desired product from an individual obtained by dryness using a solvent-insoluble, yet the extraction solvent to dryness, the purpose You can get things. If necessary, this salt can be converted to carboxylic acid or sulfonic acid using an acid such as sulfuric acid, and after distillation, the salt can be purified again with M (OH) _m to obtain a high purity. is there.

Next, the case where the nitrogen-containing fluorine-type compound shown to said Formula (4) is manufactured is demonstrated.
Specifically, for example, when a linking group R having an amide bond is introduced between an oil repellency-imparting group (nitrogen-containing perfluoroalkyl group) and an anionic hydrophilicity-imparting group, first, nitrogen-containing perfluoroalkylcarbonyl is introduced. An alkali metal salt of a carboxylic acid or sulfonic acid having an amide bond is obtained by reacting fluoride or sulfonyl fluoride with aminoalkyl carboxylic acid or aminophenyl sulfonic acid and then reacting with alkali hydroxide. It is done.

  Further, for example, when a linking group R having an ester bond is introduced between an oil repellency-imparting group (nitrogen-containing perfluoroalkyl group) and an anionic hydrophilicity-imparting group, first, nitrogen-containing perfluoroalkylcarbonyl fluoride or A sulfonyl fluoride is reacted with a hydroxyphenyl organic acid and then reacted with an alkali hydroxide to obtain an alkali metal salt of a carboxylic acid or sulfonic acid having an ester bond.

For example, when a linking group R having an ether bond is introduced between an oil repellency-imparting group (nitrogen-containing perfluoroalkyl group) and an anionic hydrophilicity-imparting group, first, a nitrogen-containing perfluoroalkylcarbonyl fluoride is introduced. Reduction with lithium aluminum hydride (LiAlH ₄ ) or sodium borohydride (NaBH ₄ ) produces an alcohol having a nitrogen-containing perfluoroalkyl group. Next, after converting to potassium alcoholate with t-butoxypotassium or the like and reacting with a metal salt of a halogenated organic acid, an alkali metal salt of a carboxylic acid having an ether bond is obtained.

[Cation type]
Specifically, for example, among the raw materials represented by the above formula (243), a nitrogen-containing perfluoroalkylcarbonyl fluoride or sulfonyl fluoride and an N, N-dialkylaminoalkyleneamine are amide-bonded to form a terminal tertiary amine. And then quaternized with an alkylating agent such as methyl iodide (CH ₃ I), methyl bromide (CH ₃ Br), dimethyl sulfate ((CH ₃ ) ₂ SO ₄ ), and the like. A nitrogen-containing fluorine-based compound having a hydrophilicity imparting group is obtained.

Also, for example, among the raw materials represented by the above formula (243), after nitrogen-containing perfluoroalkylcarbonyl fluoride or sulfonyl fluoride and N, N-dialkylaminoalkylene alcohol are ether-bonded to form a terminal tertiary amine Quaternization with an alkylating agent such as methyl iodide (CH ₃ I), methyl bromide (CH ₃ Br), dimethyl sulfate ((CH ₃ ) ₂ SO ₄ ), etc. to impart cationic hydrophilicity A nitrogen-containing fluorine-based compound having a group is obtained.

[Bisexual type]
Specifically, for example, in the case of the carboxybetaine type, first, among the raw materials represented by the above formula (243), nitrogen-containing perfluoroalkylcarbonyl fluoride or sulfonyl fluoride and N, N-dialkylaminoalkyleneamine are amides. Nitrogen-containing fluorine having an amphoteric hydrophilicity-imparting group by bonding or ether-bonding with N, N-dialkylaminoalkylene alcohol to form a terminal tertiary amine and then reacting with sodium monochloroacetate Series compounds are obtained.

  Also, for example, in the case of sulfobetaine type, after forming a terminal tertiary amine as described above, it is reacted with a cyclic sulfonic acid ester compound typified by 1,3-propane sultone, etc. A nitrogen-containing fluorine-based compound having an imparting group is obtained.

  In addition, for example, in the case of an amine oxide type, a nitrogen-containing fluorine-based compound having an amphoteric hydrophilicity-imparting group can be obtained by making a terminal tertiary amine as described above and then reacting with hydrogen peroxide.

  In addition, the specific example of the structure of the hydrophilic oil repellent mentioned above used for the filter medium of this embodiment is an example, Comprising: The technical scope of this invention is not limited to the said specific example. That is, the hydrophilic oil repellent used in this embodiment may have at least one or more of various oil repellency imparting groups and one or more hydrophilic imparting groups of anionic type, cationic type or amphoteric type in the molecule. That's fine.

  In addition, the above-described hydrophilic oil repellents each exhibit sufficient hydrophilic oil repellency, but the practical environment includes a variety of acids, alkalis, oils, and the like, and when considering practical durability, It is desirable to increase durability against the actual environment by appropriately combining hydrophilic oil repellents.

The hydrophilic oil repellent described above can be variously modified without departing from the gist of the present invention. For example, the hydrophilic oil repellent of this embodiment may have two or more oil repellency imparting groups in the molecule. Further, when the molecule has two or more oil repellency-imparting groups, it may be provided at the end of the molecular chain or may be provided in the molecular chain.
The hydrophilic oil repellent may have two or more hydrophilicity imparting groups that are the same or different in the molecule.
Furthermore, the hydrophilic oil repellent may have two or more bonds that are the same or different in the linking group. Furthermore, when the linking group is a polymer type, the number of repeating units and the bonding order are not particularly limited.

(B) Oxide fine particles (B) Oxide fine particles applicable to the composition of the present embodiment are not particularly limited as long as they are oxide fine particles (oxide nanoparticles) having an average primary particle diameter of 2 to 50 nm. It is not something. Specific examples of such oxide fine particles include silica, ITO (Indium Tin Oxide), and oxides of In, Sn, Zn, Ti, or W. More specifically, indium oxide (In ₂ O ₃ ), tin oxide (SnO, SnO ₂ , SnO ₃ ), zinc oxide (ZnO), titanium oxide (TiO ₂ ), tungsten oxide (WO ₃ ), and the like can be given. .

  Here, for example, when silica is used as the oxide fine particles, the film formed using the composition of the present embodiment has high hardness and transparency of the coating film, and the film has a low refractive index so that light transmission is possible. Will improve.

  When titania is used, the film formed using the composition of the present embodiment has a self-cleaning function based on a photocatalytic function and becomes a high refractive index film.

  Moreover, when ITO is used, the antistatic function by electroconductivity can be provided to the film formed using the composition of this embodiment.

  In this specification, the average primary particle diameter of the oxide fine particles is an average of 200 particle sizes measured by image analysis among particle shapes observed with a transmission electron microscope (TEM). Value.

  The shape of the oxide fine particles may be spherical, an anisotropic flat shape, a shape connected in a bead shape, a shape in which spherical particles are connected to an indeterminate shape, or the like. At that time, the average primary particle diameter of the oxide fine particles refers to a size approximated to a spherical shape by the image analysis in the above-described TEM observation.

  The average primary particle diameter of the oxide fine particles is preferably in the range of 2 to 50 nm, and more preferably in the range of 5 to 35 nm. It is preferable that the average primary particle diameter of the oxide fine particles is 2 nm or more, because oxide fine particles that exist stably can be obtained. Moreover, when the average primary particle diameter of the oxide fine particles is 50 nm or less, the transparency of the film when the composition is formed is preferably increased.

  On the other hand, if the average primary particle diameter of the oxide fine particles exceeds 50 nm, the secondary particle diameter when the aggregated particles are formed easily exceeds 200 nm. It is not preferable because it is observed.

  In addition, as the oxide fine particles, a mixture containing one or more selected from the group listed above may be used as (B) oxide fine particles (oxide nanoparticles).

(C) Hydrolyzate of silicon alkoxide As a hydrolyzate of (C) silicon alkoxide applicable to the composition of the present embodiment, the speed of reactivity during film formation using the film-forming composition, There is no particular limitation as long as the hardness of the resulting coating can be maintained. Specific examples of such a hydrolyzate of silicon alkoxide include those produced by hydrolysis (condensation) of silicon alkoxide represented by the following general formula (244). In the following formula (244), R ¹⁴ represents an alkyl group having 1 to 5 carbon atoms.
Si (OR ¹⁴ ) ₄ (244)

  Here, in the composition of the present embodiment, the reason for using the hydrolyzate of (C) 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 (244) 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 (C) 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 ).

“Method for producing hydrolyzate of silicon alkoxide”
Next, an example of a method for producing the hydrolyzate of (C) silicon alkoxide described above will be described. In order to produce a hydrolyzate of silicon alkoxide represented by the above formula (244), 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.

  An inorganic acid or an organic acid functions as an acidic catalyst for promoting the hydrolysis reaction of silicon alkoxide. 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. Among these, it is particularly preferable to use nitric acid as the inorganic acid and formic acid as the organic acid.

  Unlike other inorganic acids such as hydrochloric acid and sulfuric acid, nitric acid is preferred because there are few components that can adversely affect electronic components such as chlorine and sulfur components in mineral acids. When nitric acid is used as a catalyst, an effect that it is easy to form a film having excellent transparency can be obtained because of high reactivity in a small amount.

  It is preferable to use formic acid as a catalyst because a film having excellent transparency can be easily formed. 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, dipropylene glycol monoethyl ether acetate, polyethylene glycol monomethyl ether, triethylene glycol monobutyl ether, tetraethylene glycol dimethyl ether, polyethylene glycol dimethyl ether, diethylene glycol monobenzyl ether and the like.

  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.

In addition, the average molecular weight of the hydrolyzate of silicon alkoxide is the amount of silicon alkoxide (that is, the solid content of SiO ₂ ), the amount of water, the amount of nitric acid, the amount of solvent such as ethanol, and the first and second liquids are mixed. The temperature can be controlled by appropriately selecting conditions such as the temperature after holding and the holding time at a high temperature.

(D) Organic solvent The composition of this embodiment is used for adjusting the viscosity suitable for coating, (A) for maintaining the dispersion state of the nitrogen-containing fluorine-based compound and (B) oxide fine particles, and (C). In order to suppress the hydrolysis reaction of the hydrolyzate of silicon alkoxide, (D) an organic solvent is included. In addition, in the system which does not contain the organic solvent (D) in the composition for film formation, the hydrolysis rate of silicon alkoxide is quick, and the solid substance by gelatinization will produce | generate immediately. Moreover, when a film is formed using the film forming composition, there is a possibility that (A) the nitrogen-containing fluorine-based compound and (B) oxide fine particles may not be in a favorable dispersed state.

  The organic solvent (D) applied to the composition of the present embodiment is highly compatible with the components (A) to (C) and is easy to handle as a film-forming composition. ) The same organic solvent used when preparing a hydrolyzate of silicon alkoxide, or (B) the same organic solvent used when preparing a dispersion of oxide fine particles, or the organic listed above. It is preferable to use a solvent.

  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 this embodiment, each solid component ratio of the hydrolyzate of (A) nitrogen-containing fluorine-based compound, (B) oxide fine particles and (C) silicon alkoxide, which are film forming components, It is preferable that it is a required range with respect to the total amount (total solid component) of the solid component of A), component (B), and component (C), respectively. In other words, when a film is formed using the composition of the present embodiment, it is preferable that the contents of the components (A) to (C) in the film (all solid components) are in the required ranges.

The lower limit of the solid component ratio of the (A) nitrogen-containing fluorine-based compound in all the solid components may be 6% by mass or more, and may be 10% by mass or more.
By the way, when (A) component is not included in the film forming component (that is, when only (B) component and (C) component are included in the film forming component), the formed film is hydrophilic and lipophilic, The contact angle of oil (n-hexadecane) is 5 ° or less.
Here, it is preferable that the solid component ratio of the component (A) is 6% by mass or more based on the total amount of the solid component because hydrophilic oil repellency can be imparted to the coating film. Moreover, it is preferable that it is 10 mass% or more since the contact angle of oil (n-hexadecane) with respect to the formed film becomes 70 ° or more, and high oil repellency can be imparted while maintaining hydrophilicity.

  On the other hand, the solid component ratio of the component (A) may be an upper limit of 40% by mass or less, or 30% by mass or less. Here, it is preferable that the solid component ratio of the component (A) is 40% by mass or less because the film strength of the coating and the adhesion to the substrate can be sufficiently obtained. Moreover, it is preferable that it is 30 mass% or less because there is no unevenness at the time of film formation and a highly transparent film can be obtained.

  Moreover, it is preferable that the solid component ratio of (B) oxide fine particle in a solid component is 40 mass% or more with respect to the whole quantity of a solid component, and it is preferable that it is 90 mass% or less. Here, it is preferable that the solid component ratio of the component (B) is 40% by mass or more because oil repellency is further improved. On the other hand, when the solid component ratio of the B component is 90% by mass or less, the film strength of the coating and the adhesion to the substrate are sufficiently obtained, which is preferable.

  The solid component ratio of the hydrolyzate of (C) silicon alkoxide in the solid component is preferably 4% by mass or more, and preferably 40% by mass or less, based on the total amount of the solid component. Here, when the solid component ratio of the component (C) is 1% by mass or more, the film strength of the coating and the adhesion to the substrate are preferable. On the other hand, when the solid component ratio of the component (C) is 40% by mass or less, the oil repellency of the coating is further improved. On the other hand, when the solid component ratio of the component (C) exceeds 40% by mass, the particle unevenness effect of the component (B) (that is, the hydrophilic film is more hydrophilic and the oil repellency film is more This is not preferable because the effect of oil repellency is reduced.

  The solid component ratio of the hydrolyzate of (C) silicon alkoxide in the solid component is determined by the mass of the silicon alkoxide. Moreover, a temperature increase test etc. are mentioned as a method of confirming the solid content density | concentration of the hydrolyzate of the (C) silicon alkoxide in a solid component. Specifically, for example, the weight after the silicon alkoxide hydrolyzate is calcined at 650 ° C. for 2 hours is divided by the weight of the silicon alkoxide hydrolyzate before the firing furnace is charged.

  In the composition of the present embodiment, the concentration of (D) the total solid component (that is, component (A) + component (B) + component (C)) in the organic solvent is not particularly limited, It can select suitably by the coating method to a base material. 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 (C) silicon alkoxide from silicon alkoxide, (A) nitrogen-containing fluorine-type compound and ( Examples thereof include a method (first method) in which B) oxide fine particles and the produced hydrolyzate of (C) silicon alkoxide are added and mixed.

"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. A step of obtaining a decomposition product (third step), a step of adding a hydrolyzate of the obtained silicon alkoxide after adding a nitrogen-containing fluorine-based compound and oxide fine particles to an organic solvent (fourth step), It is constituted roughly including.

(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 nitrogen-containing fluorine-type compound and oxide microparticles | fine-particles 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 nitrogen-containing fluorine-based compound having a perfluoroamine structure and oxide fine particles are 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. A dispersion of oxide fine particles in which oxide fine particles are dispersed in a solvent may be prepared in advance, and a required amount of a nitrogen-containing fluorine-based compound having a perfluoroamine structure may be added to the dispersion.

In addition, as another example of the method for producing the film forming composition of the present embodiment, (D) an organic solvent, silicon alkoxide, (A) a nitrogen-containing fluorine-based compound, and (B) oxide fine particles are simultaneously used. A method of adding and mixing (second method) may be mentioned.
Here, the first method described above is a method of preparing a hydrolyzate of (C) silicon alkoxide in advance, whereas the second method has a perfluoroamine structure simultaneously with the hydrolysis of silicon alkoxide. In this method, a film-forming composition is obtained by mixing a nitrogen-containing fluorine-based compound and oxide fine particles.

"Second method"
Specifically, the second method comprises mixing silicon alkoxide, (A) a nitrogen-containing fluorine-based compound and (B) oxide fine particles, and (D) an organic solvent, and A step of preparing (first 'step), a step of mixing water and an inorganic acid to prepare a second' solution (second 'step), and a step of adding the first' solution held at a required temperature. And a step of adding the 2 ′ liquid and mixing the mixture while maintaining the temperature (step 3 ′).

(First step)
First, in the 1 'step, a silicon alkoxide, a nitrogen-containing fluorine-based compound having a perfluoroalkylamine structure and oxide fine particles, and an organic solvent are mixed to prepare a 1' solution. Specifically, first, silicon alkoxide is put into a reaction vessel, and when the mass of the silicon alkoxide is set to 1, an organic solvent that is 0.4 parts by mass is added. Furthermore, with respect to 1 part by mass of the silicon alkoxide previously charged, for example, the nitrogen-containing fluorine-based compound is, for example, 0.2 to 1 part by mass, and the oxide is, for example, 0.2 to 5 parts by mass. The first 'liquid is prepared by adding each of the microparticles and stirring, for example, at a temperature of about 30 ° C for about 15 minutes.

(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 hydrolyzate of the nitrogen-containing fluorine-type compound which has a perfluoroamine structure, oxide microparticles | fine-particles, and 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 coating film of this embodiment is formed using the film forming composition described above. Specifically, as described above, a coating solution containing a nitrogen-containing fluorine-based compound having a perfluoroamine structure, oxide fine particles, a hydrolyzate of silicon alkoxide, and an organic solvent is applied to the substrate, followed by baking and curing. Is obtained.

  The coating of this embodiment is applied with a composition containing a nitrogen-containing fluorine-based compound having a perfluoroamine structure, which is a fluorine material having a low environmental load, oxide fine particles, a hydrolyzate of silicon alkoxide, and an organic solvent, followed by baking. It is obtained by curing, and the uneven shape of the oxide fine particles appears on the surface of the coating. In the coating of this embodiment, a nitrogen-containing fluorine-based compound is attached to the surface of oxide fine particles on the surface of the coating.

  By the way, it is known that a film formed using fine particles having an average primary particle diameter of 100 nm or less and having a hydrophilic surface generally exhibits a hydrophilic and lipophilic surface.

  On the other hand, the coating film of this embodiment has an average primary particle diameter of about 2 to 50 nm, a surface containing hydrophilic oxide fine particles, and a nitrogen-containing fluorine-based system having a perfluoroamine structure as a hydrophilic oil repellent. Due to the synergistic effect with the compound, the water contact angle is lower than that of the film obtained from the nitrogen-containing fluorine compound alone. That is, the coating film of this embodiment has high hydrophilicity.

  Furthermore, since the nitrogen-containing fluorine-based material, which is a hydrophilic oil repellent, adheres to the oxide fine particles on the surface of the coating according to the present embodiment, high oil repellency is also exhibited at the same time. 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 in the component, it has high scratch resistance, high hardness, and a nitrogen-containing fluorine-based compound having a perfluoroamine structure. It is more excellent in adhesion and durability with the substrate than the obtained coating.

  Furthermore, when the coating film of this embodiment is a cured film of a hydrolyzate using TEOS as the raw material silicon alkoxide and using nitric acid or formic acid as the acidic catalyst, the transmittance is 95 to 98%, and the haze is 0.1. It becomes the following and 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 hydrophilicity and oil 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 DM-700” manufactured by Kyowa Interface Science Co., Ltd.). Specifically, ion exchange water is prepared in a syringe, and a value obtained by analyzing the contact angle after 1000 msec after water touches the membrane surface in a stationary state by the θ / 2 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.
Moreover, easy-cleaning property was confirmed by confirming whether the line written on the surface of the film using an oil-based pen could be dropped by flowing with water.

  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 coating film of this embodiment can be measured using a commercially available measuring device (for example, haze meter “HZ-2” manufactured by Suga Test Instruments Co., Ltd.) for the coating 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.

  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. A film having hydrophilic oil repellency and excellent antifouling property can be formed.

  In particular, the film-forming composition of the present embodiment includes a nitrogen-containing fluorine-based compound having a plurality of short-chain-length perfluoroalkyl groups branched on nitrogen atoms, that is, a perfluoroamine structure, as the nitrogen-containing perfluoroalkyl group. It is included. Since this perfluoroamine structure is bulky, it has a high repellency similar to a nitrogen-containing fluorine-based compound having a linear perfluoroalkyl structure having 8 or more carbon atoms even though 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 oiliness.

  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 coating of this embodiment has higher hydrophilic oil repellency and excellent antifouling properties than a coating obtained from a nitrogen-containing fluorine-based compound alone 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, the example in which only one type each of the nitrogen-containing fluorine-based compound, the oxide fine particles, and the silicon alkoxide is included in the film forming composition has been described. It is not a thing. For example, two or more types of each may be contained in the film forming composition.

  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.

<Nitrogen-containing fluorine-based compounds>
(Synthesis Example 1)
“Synthesis of 2- [3- [perfluoro (3-dibutylaminopropanoyl)] aminopropyl-dimethyl-ammonium] acetate”
20 g of perfluoro (3-dibutylaminopropionic acid) fluoride obtained by electrolytic fluorination of methyl 3-dibutylaminopropionate was added dropwise in an ice bath to a solution of 4 g of dimethylaminopropylamine in 50 ml of IPE solvent. After stirring at room temperature for 2 hours, filtration was performed, and the IPE layer of the filtrate was washed with an aqueous NaHCO ₃ solution and an aqueous NaCl solution, separated, and then washed with water. Thereafter, it was distilled off IPE, as a crude _product, a _{(C 4 F 9) 2 NC} 2 F 4 CONHC 3 H 6 N (CH 3) 2 was obtained 14 g (60% yield).

Subsequently, 3 g of the obtained (C ₄ F ₉ ) ₂ NC ₂ F ₄ CONHC ₃ H ₆ N (CH ₃ ) ₂ was refluxed with sodium monochloroacetate in ethanol overnight with stirring to obtain the following general formula (245). 3 g of the carboxybetaine compound shown in (2) was obtained.

(Synthesis Example 2)
“Synthesis of 2- [3- [perfluoro (3-dibutylamino-2-methylpropanoyl)] aminopropyl-dimethyl-ammonium] acetate”
To a solution of 160 g of perfluoro (3-dibutylamino-2-methylpropionic acid) fluoride obtained by electrolytic fluorination of methyl 3-dibutylamino-2-methylpropionate in a solution of 50 g of dimethylaminopropylamine in 500 ml of IPE solvent. The solution was added dropwise in an ice bath. After stirring at room temperature for 2 hours, filtration was performed, and the IPE layer of the filtrate was washed with an aqueous NaHCO ₃ solution and an aqueous NaCl solution, separated, and then washed with water. Thereafter, was distilled off IPE, as a crude product _was obtained 94g of _{(C 4 F 9) 2 NCF} 2 CF (CF 3) CONHC 3 H 6 N (CH 3) 2 (52% yield).

Next, 66 g of the obtained (C ₄ F ₉ ) ₂ NCF ₂ CF (CF ₃ ) CONHC ₃ H ₆ N (CH ₃ ) ₂ was refluxed with sodium monochloroacetate in ethanol overnight with stirring, and the above formula ( 36 g of the carboxybetaine compound shown in 36) was obtained (91% yield).

(Synthesis Example 3)
“Synthesis of 2- [3- [perfluoro (3-dibutylamino-2-methylpropanoyl)] aminopropyl-dimethyl-ammonium] acetate”
To a solution of 160 g of perfluoro (3-dibutylamino-2-methylpropionic acid) fluoride obtained by electrolytic fluorination of methyl 3-dibutylamino-2-methylpropionate in a solution of 50 g of dimethylaminopropylamine in 500 ml of IPE solvent. The solution was added dropwise in an ice bath. After stirring at room temperature for 2 hours, filtration was performed, and the IPE layer of the filtrate was washed with an aqueous NaHCO ₃ solution and an aqueous NaCl solution, separated, and then washed with water. Thereafter, was distilled off IPE, as a crude product _was obtained 94g of _{(C 4 F 9) 2 NCF} 2 CF (CF 3) CONHC 3 H 6 N (CH 3) 2 (52% yield).

Next, 66 g of the obtained (C ₄ F ₉ ) ₂ NCF ₂ CF (CF ₃ ) CONHC ₃ H ₆ N (CH ₃ ) ₂ was refluxed with sodium monochloroacetate in ethanol overnight with stirring, and the above formula ( 119) was obtained in an amount of 65 g (91% yield).

<Oxide fine particles, oxide fine particle dispersion>
As an example of oxide fine particles, the following (1) to (5) were used as oxide fine particles or a dispersion of oxide fine particles.
(1) Silica particles having an average primary particle size of about 15 nm (2) Dispersion liquid in which colloidal silica particles having an average primary particle size of about 12 nm are dispersed in an IPA solvent (3) Colloidal silica having an average primary particle size of about 10 nm Dispersion in which particles are dispersed in a propylene glycol monomethyl ether solvent (4) Dispersion in which zirconia particles having an average primary particle size of about 20 nm are dispersed in ethanol (5) Titania particles having an average primary particle size of 10 nm are solid Ethanol dispersion containing 10% by mass

<Hydrolysate of 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, 46.9 g of ethanol is prepared, and 0.1 g of a compound represented by the general formula (245) described in Synthesis Example 1 described above is added as a nitrogen-containing fluorine-based compound (A) having a perfluoroamine structure. . Thereafter, (B) 1.8 g of an IPA dispersion containing silica particles having an average primary particle size of 12 nm as oxide fine particles at a solid content of 15% by mass, and a hydrolyzate of the above (C) silicon alkoxide prepared in advance 1.2 g of (average molecular weight: 4 × 10 ³ ) was added to prepare a film forming composition. Table 1 shows the component composition.

(Example 2)
As an organic solvent, 33.0 g of IPA is prepared, and 0.3 g of a compound represented by the general formula (245) described in Synthesis Example 1 is added as a nitrogen-containing fluorine-based compound (A) having a perfluoroamine structure. . Thereafter, (B) 10.0 g of a propylene glycol monomethyl ether dispersion containing silica particles having an average primary particle size of 10 nm as solid oxide particles at a solid content of 15% by mass, and the above-prepared (C) silicon alkoxide prepared above. 6.7 g of hydrolyzate (average molecular weight: 4 × 10 ³ ) was added to prepare a film-forming composition. Table 1 shows the component composition.

Example 3
As an organic solvent, 37.9 g of propylene glycol monomethyl ether is prepared, and 0.4 g of a compound represented by the above general formula (36) is weighed and added as a nitrogen-containing fluorine-based compound (A) having a perfluoroamine structure. Thereafter, (B) 3.2 g of a propylene glycol monomethyl ether dispersion in which zirconia particles having an average primary particle diameter of 20 nm as an oxide fine particle are contained at a solid content of 40% by mass, and the above-prepared (C) silicon alkoxide prepared in advance 8.5 g of hydrolyzate (average molecular weight: 4 × 10 ³ ) was added to prepare a film-forming composition. Table 1 shows the component composition.

Example 4
As an organic solvent, 44.4 g of ethanol is prepared, and 0.2 g of a compound represented by the general formula (245) described in Synthesis Example 1 described above is added as a nitrogen-containing fluorine-based compound (A) having a perfluoroamine structure. . Then, 3.6 g of an ethanol dispersion containing (B) titania particles having an average primary particle diameter of 10 nm as solid oxide particles at a solid content of 10% by mass, and a hydrolyzate of the above (C) silicon alkoxide prepared in advance 1.8 g of (average molecular weight: 4 × 10 ³ ) was added to prepare a film forming composition. Table 1 shows the component composition.

(Example 5)
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 compound represented by the general formula (119) is added as 0.5 parts by mass as a nitrogen-containing fluorine-based compound (A) with respect to 1 part by mass. Further, 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. Furthermore, when the mass of this silicon alkoxide was 1, the amount of oxide fine particles (silica particles having an average primary particle diameter of about 15 nm) in an amount of 4 parts by mass was added. Table 1 shows the component composition.

  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. As a result, a hydrolyzate (C) of silicon alkoxide containing a nitrogen-containing fluorine-based compound (A) having a perfluoroamine structure represented by the above formula (119) was obtained.

  Next, 40 g of ethanol was prepared as an organic solvent, and 10 g of a hydrolyzate of silicon alkoxide (C) containing a nitrogen-containing fluorine compound (A) represented by the above formula (119) was weighed and added to form a film-forming composition. Was prepared. Table 1 shows the component composition.

(Example 6)
Similar to Example 5 above,
As an organic solvent, 45 g of IPA is prepared, and includes a nitrogen-containing fluorine-based compound (A) represented by the general formula (245) described in Synthesis Example 1 and silica particles (B) having an average primary particle size of 12 nm. 5 g of hydrolyzate of silicon alkoxide (C) was weighed and added to prepare a film forming composition. Table 1 shows the component composition.

(Comparative Example 1)
47 g of ethanol was prepared as an organic solvent, and (B) 1.8 g of an IPA dispersion containing silica particles having an average primary particle size of 12 nm as solid oxide particles at a solid content of 15% by mass was prepared in advance ( C) 1.2 g of hydrolyzate of silicon alkoxide (average molecular weight: 4 × 10 ³ ) was added to prepare a film-forming composition. Table 1 shows the component composition.

(Comparative Example 2)
As an organic solvent, 46.9 g of ethanol was prepared, and as the nitrogen-containing fluorine compound (A) having a perfluoroamine structure, the nitrogen-containing fluorine compound represented by the general formula (245) described in Synthesis Example 1 described above was set to 0.0. Add 1g weigh. Thereafter, (B) 1.8 g of an ethanol dispersion containing silica particles having an average primary particle size of 100 nm as solid oxide particles at a solid content of 15% by mass, and a hydrolyzate of the above (C) silicon alkoxide prepared in advance 1.2 g of (average molecular weight: 4 × 10 ³ ) was added to prepare a film forming composition. Table 1 shows the component composition.

(Comparative Example 3)
As an organic solvent, 48 g of ethanol was prepared, and 2 g of a nitrogen-containing fluorine-based compound represented by the general formula (245) described in Synthesis Example 1 described above was added as a nitrogen-containing fluorine-based compound (A) having a perfluoroamine structure. The film-forming composition thus prepared was designated as Comparative Example 3. Table 1 shows the component composition.

(Comparative Example 4)
As an organic solvent, 46.8 g of ethanol was prepared, and a nitrogen-containing fluorine-based compound represented by the general formula (245) described in Synthesis Example 1 described above as a nitrogen-containing fluorine-based compound (A) having a perfluoroamine structure was set to 0.0. Add 012 g weigh. Thereafter, (B) 2.0 g of an ethanol dispersion containing silica particles having an average primary particle size of 12 nm as oxide fine particles at a solid content of 15% by mass, and a hydrolyzate of the above (C) silicon alkoxide prepared in advance 1.2 g of (average molecular weight: 4 × 10 ³ ) was added to prepare a film forming composition. Table 1 shows the component composition.

(Comparative Example 5)
As an organic solvent, 48.0 g of ethanol was prepared, and as the nitrogen-containing fluorine-based compound (A) having a perfluoroamine structure, a nitrogen-containing fluorine-based compound represented by the general formula (245) described in Synthesis Example 1 described above was set to 0.0. Add 185 g weigh. Then, (B) 1.3 g of an ethanol dispersion containing silica particles having an average primary particle size of 12 nm as oxide fine particles at a solid content of 15% by mass, and a hydrolyzate of the above (C) silicon alkoxide prepared in advance 0.55 g of (average molecular weight: 4 × 10 ³ ) was added to prepare a film forming composition. Table 1 shows the component composition.

(Comparative Example 6)
As an organic solvent, 47.4 g of IPA was prepared, and a nitrogen-containing fluorine-based compound represented by the general formula (245) described in Synthesis Example 1 described above was set to 0. Add 13g weigh. Then, 1.0 g of an IPA dispersion containing silica particles having an average primary particle diameter of 10 nm as oxide fine particles (B) at a solid content of 15% by mass, and a hydrolyzate of the above (C) silicon alkoxide prepared in advance 1.5 g of (average molecular weight: 3 × 10 ³ ) was added to prepare a film forming composition. Table 1 shows the component composition.

(Comparative Example 7)
As the organic solvent, 47.2 g of IPA was prepared, and the nitrogen-containing fluorine-based compound represented by the general formula (245) described in Synthesis Example 1 described above was set to 0. Add 02 g weigh. Thereafter, (B) 2.7 g of an IPA dispersion containing silica particles having an average primary particle size of 10 nm as solid oxide particles at a solid content of 15% by mass, and a hydrolyzate of the above (C) silicon alkoxide prepared in advance 0.15 g of (average molecular weight: 3 × 10 ³ ) was added to prepare a film forming composition. Table 1 shows the component composition.

(Comparative Example 8)
As an organic solvent, 47.5 g of ethanol was prepared, and a nitrogen-containing fluorine-based compound represented by the general formula (245) described in Synthesis Example 1 described above as a nitrogen-containing fluorine-based compound (A) having a perfluoroamine structure was reduced to 0.00. Add 08g weigh. Thereafter, (B) 2.3 g of an ethanol dispersion containing silica particles having an average primary particle size of 12 nm as oxide fine particles at a solid content of 15% by mass, and a hydrolyzate of the above (C) silicon alkoxide prepared in advance 0.05 g of (average molecular weight: 4 × 10 ³ ) was added to prepare a film forming composition. Table 1 shows the component composition.

(Comparative Example 9)
As an organic solvent, 46.7 g of ethanol was prepared, and a nitrogen-containing fluorine-based compound represented by the general formula (245) described in Synthesis Example 1 described above as a nitrogen-containing fluorine-based compound (A) having a perfluoroamine structure was added in an amount of 0.0. Add 045 g weigh. Then, (B) 1.3 g of an ethanol dispersion containing silica particles having an average primary particle size of 12 nm as oxide fine particles at a solid content of 15% by mass, and a hydrolyzate of the above (C) silicon alkoxide prepared in advance 1.95 g of (average molecular weight: 4 × 10 ³ ) was added to prepare a film forming composition. Table 1 shows the component composition.

<Evaluation method>
(Evaluation of hydrophilic oil repellency of coating)
About the film using the film forming composition prepared in Examples 1-6 and Comparative Examples 1-9, the contact angle is measured when water and n-hexadecane are adhered, and hydrophilicity and oil repellency are obtained. Each 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 by using a CA-700 contact angle meter manufactured by Kyowa Interface Science Co., Ltd., and the droplet volume of water and n-hexadecane was 2 μl, and the contact angle was measured at any five points on the surface treatment member. The average value was calculated. The evaluation results are shown in Table 2.

(Evaluation of film transparency)
The transmittance | permeability and the haze were measured about the film using the composition for film formation prepared in the said Examples 1-6 and the said Comparative Examples 1-9, and transparency was evaluated.
"Transmissivity"
The evaluation member was adjusted in the same manner as the hydrophilic oil repellency evaluation member, and the transmittance of the evaluation member (coating containing the base material) was in the range of 240 to 2600 nm using a spectrophotometer U-4100 manufactured by Hitachi High-Tech. It was measured. About the transmittance | permeability, the value in 550 nm which is a visible light range was confirmed. The evaluation results are shown in Table 2 below.

"Haze"
The evaluation member was adjusted in the same manner as the hydrophilic oil repellency evaluation member, and the haze measurement of the evaluation member (coating containing the substrate) was performed using a haze meter HZ-2 manufactured by Suga Test Instruments Co., Ltd. The evaluation results are shown in Table 2 below. The haze is a numerical value represented by the diffusion transmittance of the film / total light transmittance × 100.

(Evaluation of antifouling properties of coating)
"Evaluation of repellency of oil pen"
Evaluation of repellency when an oil-based pen (manufactured by Hiroyuki Uchida, “Magic Ink”) is attached to the coatings using the coating-forming compositions prepared in Examples 1-6 and Comparative Examples 1-9. (Evaluation of repellency of oil-based pen) was performed to evaluate the antifouling property of the coating. The evaluation member was adjusted in the same manner as the hydrophilic oil 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, and the ease of repelling was visually evaluated according to the following criteria. The evaluation results are shown in Table 2 below.
○: Repelled △: Partially repelled ×: Not repelled at all

"Easy-cleanability evaluation"
The straight line written using the oil-based pen was directly subjected to ion-exchanged water in a bottle on the substrate, and its easy-cleanability was visually evaluated according to the following criteria. The evaluation results are shown in Table 2 below.
○: All removed by washing Δ: Partially removed ×: Not removed by washing at all

  As shown in Table 2, the film formed using the film forming composition of the present invention (Examples 1 to 6) exhibits high hydrophilicity, high oil repellency, and oil pen repellency (evaluation: ◯). ing. That is, according to the film forming composition of the present invention, it contains a nitrogen-containing fluorine-based compound not containing a linear perfluoroalkyl group having 8 or more carbon atoms and oxide fine particles having an average primary particle diameter of 2 to 50 nm. Thus, it was found that a film having high hydrophilic oil repellency and excellent antifouling property can be formed.

  Moreover, the film formed using the film-forming composition of the present invention (Examples 1 to 6) is composed of oxide fine particles having an average primary particle diameter of 2 to 50 nm and silicon alkoxide in the film-forming composition. Since the hydrolyzate was contained, it turned out that it has the outstanding transparency (low haze).

  In Examples 1, 2, 5, and 6, silica particles are used as the oxide fine particles as the component (B), and the refractive index effect of the particles results in a low refractive index. For this reason, as shown in Table 2, it was lower than the glass of the base material (transmittance 92%), and the effect of increasing the transmittance was obtained.

  In Examples 3 and 4, high refractive index zirconia particles and titania particles are coated on the glass substrate as oxide fine particles as component (B), and the refractive index is higher than that of the original substrate glass. Rises and the reflectance is improved. For this reason, as shown in Table 2, it was confirmed that the transmittance was slightly lower than the glass of the base material (transmittance of 92%).

  As described above, the film-forming composition of the present invention increases the transmittance of the formed film by about 1 to 4% when a low-bending material is used as the oxide fine particles (B). On the other hand, it was confirmed that, when a highly bent material was used, an effect of reducing it by several percent was obtained.

  On the other hand, since the composition for forming a film of Comparative Example 1 does not contain the component (A), the evaluation of the formed film shows high hydrophilicity as shown in Table 2, but low oil repellency. . For this reason, in the evaluation of the antifouling property of the formed film, the evaluation of the repellency and easy cleaning property of the oil-based pen was “x”, indicating that the antifouling property was not sufficient.

  Moreover, since the particle size of the oxide fine particles as the component (B) exceeds 50 nm in the film forming composition of Comparative Example 2, in the evaluation of the formed film, as shown in Table 2, hydrophilicity and All of the oil repellency was moderate. For this reason, in the evaluation of the antifouling property of the formed film, the repellency of the oil-based pen was “Δ” and the evaluation of easy cleaning property was “x”, indicating that the antifouling property was not sufficient. Also, in the evaluation of transparency, the “transmittance” was low and the “haze” was high at the same time, which indicated that the transparency was not sufficient.

  Moreover, since the film forming composition of Comparative Example 3 does not contain the component (B) and the component (C), high hydrophilicity and oil repellency are obtained as shown in Table 2 in the evaluation of the formed film. There wasn't. For this reason, in the evaluation of the antifouling property of the formed film, the evaluation of the repellency and easy cleaning property of the oil-based pen was “x”, indicating that the antifouling property was not sufficient. Moreover, also in evaluation of transparency, the haze value was 0.28, and it was changed that transparency was not enough.

  Moreover, since the composition for coating film formation of Comparative Example 4 has a composition ratio of the component (A) in the total solid component of less than 6% by mass, as shown in Table 2, in the evaluation of the formed film, oil repellency Was insufficient. For this reason, in the evaluation of the antifouling property of the formed film, the repellency of the oil-based pen was “x” and the evaluation of easy cleaning property was “x”, indicating that the antifouling property was not sufficient.

  Moreover, since the composition ratio of the component (A) in the total solid component exceeds 40% by mass in the film forming composition of Comparative Example 5, in the evaluation of the formed film, as shown in Table 2, “Transmittance” "Is low, and at the same time" haze "is high, the transparency was not enough.

  Moreover, since the composition ratio of the component (B) in the total solid component of the composition for forming a film of Comparative Example 6 is less than 40% by mass, in the evaluation of the formed film, as shown in Table 2, the oil repellency Was insufficient. For this reason, in the evaluation of the antifouling property of the formed film, the repellency of the oil-based pen was “Δ” and the evaluation of easy cleaning property was “x”, indicating that the antifouling property was not sufficient.

  In the composition for forming a film of Comparative Example 7, the composition ratio of the component (B) in all solid components exceeds 90% by mass, the composition ratio of the component (A) is less than 6% by mass, and the component (C). The composition ratio was less than 4% by mass. For this reason, in the evaluation of the antifouling property of the formed film, the repellency of the oil-based pen was “x” and the evaluation of easy cleaning property was “x”, indicating that the antifouling property was not sufficient.

  Moreover, the composition for film formation of the comparative example 8 had a composition ratio of the component (C) in the total solid components of less than 4% by mass. For this reason, since there was little hydrolyzate of silicon alkoxide and there was no adhesiveness, at the time of description with an oil-based pen, the film | membrane peeled and evaluation was not able to be performed.

  Moreover, since the composition for film formation of the comparative example 9 has a composition ratio of the component (C) in the total solid component exceeding 40% by mass, as shown in Table 2, in the evaluation of the formed film, oil repellency Was insufficient. For this reason, in the evaluation of the antifouling property of the formed film, the repellency of the oil-based pen was “Δ” and the evaluation of easy cleaning property was “x”, indicating that the antifouling property was not sufficient. Moreover, also in evaluation of transparency, the haze value was 0.24, and it was changed that transparency was not enough.

  The film-forming composition of the present invention is an antifouling film, particularly a building outer wall or roof, an aircraft, a ship, a body such as an automobile, a glass, a wheel, a side mirror of a passenger car, a heat exchanger of an air conditioner, an electric wire, Applicability to antennas. Moreover, it has the applicability as an antifouling film | membrane to the display surface where visibility is requested | required.

Claims (6)

One or more nitrogen-containing fluorine-based compounds represented by the following formulas (1) to (4);
Oxide fine particles having an average primary particle diameter of 2 to 50 nm;
A hydrolyzate of silicon alkoxide;
An organic solvent,
In all solid components contained in the hydrolyzate of the nitrogen-containing fluorine-based compound, the oxide fine particles and the silicon alkoxide,
The composition ratio of the nitrogen-containing fluorine compound is 6 to 40% by mass,
The composition ratio of the oxide fine particles is 40 to 90% by mass,
The composition for film formation whose composition ratio of the hydrolyzate of the said silicon alkoxide is 4-40 mass%.

In the above formulas (1) and (2), Rf ¹ and Rf ² are the same or different from each other, each having 1 to 6 carbon atoms and a linear or branched perfluoroalkyl group. Rf ³ is a linear or branched perfluoroalkylene group having 1 to 6 carbon atoms.
In the above formulas (3) and (4), Rf ⁴ and Rf ⁵ are the same or different, each having 1 to 6 carbon atoms and a linear or branched perfluoroalkylene group. Rf ⁶ has 1 to 6 carbon atoms and is a linear or branched perfluoroalkylene group. Z is an oxygen atom, a nitrogen atom, a CF ₂ group or a CF group.
In the above formulas (2) and (4), R is a divalent organic group and is a linear or branched linking group.
Moreover, in said formula (1)-(4), X is any one hydrophilicity imparting group selected from the group which consists of an anionic type, a cationic type, and an amphoteric type. The film forming composition according to claim 1, wherein the hydrolyzate of the silicon alkoxide has an average molecular weight of 1 × 10 ³ or more and 2 × 10 ⁴ or less.   The said oxide microparticles | fine-particles are 1 type, or 2 or more types of mixtures among the groups chosen from the oxide chosen from silica, ITO, and the oxide of In, Sn, Zn, Ti, or W. A film-forming composition. It is a manufacturing method of the composition for film formation as described in any one of Claims 1 thru | or 3, Comprising:
After producing a hydrolyzate of the silicon alkoxide from the silicon alkoxide, the nitrogen-containing fluorine-based compound, the oxide fine particles, and the produced hydrolyzate of the silicon alkoxide are added to the organic solvent. The manufacturing method of the composition for film formation to mix. It is a manufacturing method of the composition for film formation as described in any one of Claims 1 thru | or 3, Comprising:
The method for producing a film-forming composition, wherein the silicon alkoxide, the nitrogen-containing fluorine-based compound, and the oxide fine particles 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.