JP5879012B1 - Hydrophilic oil-repellent composite and method for producing the same, surface coating material, coating film, resin composition, oil-water separation filter medium - Google Patents

Abstract

This hydrophilic oil-repellent composite contains one or more nitrogen-containing fluorine-based compounds and an inorganic compound having a charge or an ionic group. The nitrogen-containing fluorine-based compound contains any one hydrophilic imparting group selected from the group consisting of an anionic type, a cationic type and an amphoteric type in the molecule.

Description

The present invention relates to a hydrophilic oil-repellent composite, a method for producing the same, a surface coating material, a coating film, a resin composition, and an oil-water separation filter medium.
This application is Japanese Patent Application No. 2014-155553, Japanese Patent Application No. 2014-155554, which was filed in Japan on July 30, 2014, and Japanese Patent Application No. 2015 filed in Japan on May 20, 2015. Claims priority based on -103238, the contents of which are incorporated herein.

  In general, as an antifouling technique, it is desirable to impart to a substrate oil repellency for making it difficult for dirt to adhere and hydrophilicity for easily removing the attached dirt by washing with water. As a technique for imparting hydrophilicity to the substrate surface, a method is known in which a photocatalyst such as titanium oxide is immobilized on the substrate surface to form a photocatalyst film, and the attached dirt is washed away by superhydrophilization by the action of the photocatalyst. (Patent Document 1).

  However, when a photocatalytic film is used, the function of easily removing dirt is obtained, but there is a problem that the characteristic of preventing the adhesion of dirt is not sufficient. In particular, in an environment where sufficient light required for the expression of the photocatalytic function cannot be obtained, sufficient antifouling properties may not be obtained.

  On the other hand, as a technique for imparting oil repellency to a substrate surface, a method using mainly a fluorine-based compound as a surface processing agent is known. Known fluorine-based compounds include fluorine resins such as polytetrafluoroethylene (PTFE) and compounds having a perfluoroalkyl group in the molecule. When these fluorine-based compounds are used, the water repellency is high, but there is a problem that oil stains adhering to the surface are difficult to remove by wiping or washing with water as in the case of a general hydrophobic coating film. In particular, when used in an environment where water is applied, there is a problem that oil stains are easily attached.

  A fluororesin that has been hydrophilized by subjecting the surface to plasma surface treatment, flame treatment, ozone treatment, etc. has been proposed (Patent Document 2), but the above-mentioned special treatment is necessary, and the resulting hydrophilicity is not sufficient. It was. Moreover, when hydrophilicity was provided, the subject that an oil-repellent function was not acquired occurred. Furthermore, the fluororesin has a problem that it is difficult to apply and process the substrate surface.

  From the above, in order to impart a sufficient antifouling function to an object to be treated such as a substrate, a hydrophilic oil repellent that simultaneously exhibits excellent hydrophilicity and oil repellency has been desired. An excellent hydrophilic oil repellent is useful in a wide range of applications such as quick-drying of water accompanying improvement in wettability, anti-fogging property, and oil-water separation property in addition to an antifouling function. Among these, it is particularly useful in oil / water separation applications.

  However, there is no compound that exhibits excellent hydrophilicity and oil repellency at the same time in the conventional compound and maintains these characteristics, and imparts sufficient antifouling function, oil / water separation function and durability. It was difficult.

JP 09-227160 A Japanese Patent Laid-Open No. 05-177766

  The present invention solves the above-mentioned conventional problems, and provides a novel hydrophilic oil-repellent composite having excellent hydrophilicity and oil repellency and excellent durability of those effects, and a method for producing the same. . The present invention also provides a surface coating material, a coating film, a resin composition, and an oil / water separation filter medium containing the hydrophilic oil-repellent composite.

  By the way, when a fluorine compound is used as a surface treating agent, the treated surface usually exhibits water and oil repellency, and the water repellency generally increases as the carbon number of the fluorine structure increases. However, as a result of intensive studies by the inventors of the present application, a complex of a specific nitrogen-containing perfluoro compound and an inorganic compound having a charge or an ionic group simultaneously exhibits excellent hydrophilicity and oil repellency, and these As a result, the present invention was completed.

  The present invention relates to a hydrophilic oil-repellent composite that has solved the above-described problems with the following configuration, a production method thereof, a surface coating material including the same, a coating film, a resin composition, and an oil-water separation filter medium.

[1] A hydrophilic oil-repellent composite containing one or more nitrogen-containing fluorine-based compounds represented by the following formulas (1) to (4) and an inorganic compound having a charge or an ionic group.

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 , Rf ^5, and Rf ⁶ are the same or different from each other, each having 1 to 6 carbon atoms and a linear or branched perfluoroalkylene group. Z includes any of an oxygen atom, a nitrogen atom, a CF ₂ group, and a CF group.
Moreover, in said formula (2) and (4), R is a coupling group which is a bivalent organic 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 hydrophilic oil-repellent complex according to [1], wherein the inorganic compound is any one kind or a mixture of two or more kinds selected from the group consisting of fumed silica, colloidal silica, mullite, alumina, and zeolite. .
[3] The hydrophilic oil-repellent complex according to the above [1], wherein the inorganic compound is one or a mixture of two or more of the group consisting of bentonite, organic bentonite, smectite, and kaolinite.
[4] The hydrophilic oil-repellent complex according to the above [1], wherein the inorganic compound is one or a mixture of two or more of the group consisting of polyaluminum chloride, polyferric sulfate, and aluminum sulfate. .

[5] The water repellent according to any one of [1] to [4], wherein a mass composition ratio of the nitrogen-containing fluorine-based compound and the inorganic compound is in a range of 1 to 99 to 99 to 1. Oil repellent composite.

[6] The method for producing a hydrophilic oil-repellent composite according to [1] above,
After applying a coating solution in which the nitrogen-containing fluorine-based compound and the inorganic compound are dissolved or dispersed in any one of water, an organic solvent, or a mixed solvent of water and an organic solvent, A method for producing a hydrophilic oil-repellent complex, wherein the complex is obtained by removing water, the organic solvent or the mixed solvent.
[7] The method for producing a hydrophilic oil-repellent composite according to [1] above,
A solid was obtained by filtration from a solution in which the nitrogen-containing fluorine-based compound and the inorganic compound were dispersed in any one of water, an organic solvent, or a mixed solvent of water and an organic solvent. A method for producing a hydrophilic oil-repellent composite, wherein the solid is dried to obtain the composite.
[8] A method for producing a hydrophilic oil-repellent composite according to [1] above,
After dissolving or dispersing the nitrogen-containing fluorine-based compound and the inorganic compound in any one of water, an organic solvent, or a mixed solvent of water and an organic solvent, the water, the organic solvent, or the mixed solvent A method for producing a hydrophilic oil-repellent complex, wherein the residue obtained by distilling off is dried to obtain the complex.

[9] The hydrophilic oil-repellent composite according to [1] above,
Any one of water, an organic solvent, or a mixed solvent of water and an organic solvent,
The surface covering material whose mass composition ratio of the nitrogen-containing fluorine-type compound in the said hydrophilic oil-repellent complex and the said solvent is the range of 0.2-50 to 50-99.8.
[10] Furthermore, a binder is included,
The mass composition ratio between the nitrogen-containing fluorine-based compound and the binder in the hydrophilic oil-repellent composite is in the range of 0.2 to 99.9 to 99.8 to 0.1, as described in [9] above. Surface coating material.
[11] The surface covering material according to [10], wherein the binder includes any of a resin, a water-soluble resin, and water glass.

[12] A coating film comprising the hydrophilic oil-repellent complex according to [1].

[13] Furthermore, a binder is included,
The mass composition ratio between the nitrogen-containing fluorine-based compound and the binder in the hydrophilic oil-repellent composite is in the range of 0.2 to 99.9 to 99.8 to 0.1, as described in [12] above. Coating film.
[14] The hydrophilic oil-repellent complex according to [1] above and a resin.
The resin composition whose mass composition ratio of the nitrogen-containing fluorine-type compound in the said hydrophilic oil-repellent complex and the said resin is the range of 0.2-99.9 vs. 99.8-0.1.

[15] An oil-water separation filter medium comprising the coating film according to [12] or the resin composition according to [14].

  In addition, the 1 type, or 2 or more types of nitrogen-containing fluorine-type compound shown by said Formula (1)-(4) is carboxylate halogen which has a nitrogen-containing perfluoroalkyl group shown by following formula (5) or (6). Or a sulfonic acid halide can be used as a raw material.

In the above formula (5), Rf ¹ and Rf ² are the same or different, 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 formula ^{(6), Rf 4, Rf} 5 and Rf ⁶ is different the same or mutually a a 1 to 6 carbon atoms straight or branched perfluoroalkylene group. Z includes any of an oxygen atom, a nitrogen atom, a CF ₂ group, and a CF group.
In the above formulas (5) and (6), Y is CO or SO ₂ .
Further, in the above formulas (5) and (6), A is any one halogen atom selected from the group consisting of fluorine, chlorine, bromine and iodine.

  The hydrophilic oil-repellent complex of the present invention is a nitrogen-containing fluorine-based compound having in its molecule an oil-repellent imparting group comprising a nitrogen-containing perfluoroalkyl group and any one of anionic, cationic and amphoteric hydrophilic imparting groups. And an inorganic compound having a charge or an ionic group, it is a material having both excellent hydrophilic oil repellency and sustained effect. Moreover, since this hydrophilic oil-repellent composite is a material excellent in durability, it can be applied to a wide variety of uses, and is particularly suitable for oil-water separation uses and oil-proof coating agents.

  Hereinafter, a hydrophilic oil-repellent complex which is one embodiment to which the present invention is applied will be described in detail together with a production method thereof, a surface coating material including the same, a coating film, a resin composition, and an oil-water separation filter medium.

<Hydrophilic oil repellent composite>
First, the structure of the hydrophilic oil-repellent complex which is one embodiment to which the present invention is applied will be described.
The hydrophilic oil-repellent composite of this embodiment comprises (A) a nitrogen-containing fluorine-based compound having a perfluoroamine structure (hereinafter sometimes simply referred to as “nitrogen-containing fluorine-based compound”), and (B) charge or ionicity. It is a composite in which an inorganic compound having a group (hereinafter sometimes simply referred to as “inorganic compound”) is combined.

(A) Nitrogen-containing fluorine-based compound The (A) nitrogen-containing fluorine-based compound applicable to the hydrophilic oil-repellent composite of the present embodiment includes an oil repellency-imparting group and a hydrophilicity-imparting group in the molecule, and is hydrophilic. And a compound that simultaneously exhibits oil repellency (that is, a compound having hydrophilic oil repellency) is not particularly limited. Specifically, such nitrogen-containing fluorine compounds can be represented by the following general formulas (1) to (4).

Here, in the above formula (1) and ^(2), Rf 1, Rf ² are different the same or mutually a a 1 to 6 carbon atoms straight or branched perfluoroalkyl group. Rf ³ is a linear or branched perfluoroalkylene group having 1 to 6 carbon atoms.
Rf ¹ and Rf ² are each preferably the same or different from each other and each having 1 to 4 carbon atoms and is a linear or branched perfluoroalkyl group. Rf ³ has 1 to 4 carbon atoms, and is preferably a linear or branched perfluoroalkylene group.

Further, in the above formula (3) and ^(4), Rf 4, Rf ⁵ and Rf ⁶ is different the same or mutually a a 1 to 6 carbon atoms straight or branched perfluoroalkylene group. Z includes any of an oxygen atom, a nitrogen atom, a CF ₂ group, and a CF group. When Z contains a nitrogen atom or a CF group, a perfluoroalkyl group branched from Z may be bonded to Z.
Rf ⁴ , Rf ⁵ and Rf ⁶ are each preferably the same or different from each other and each having 1 to 4 carbon atoms and a linear or branched perfluoroalkylene group.

  Moreover, in said formula (2) and (4), R is a coupling group which is a bivalent organic group. Here, R may be a linear or branched organic 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.

  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 hydrophilic oil-repellent complex of this embodiment is from the nitrogen-containing fluorine-type compound shown by said Formula (1)-(4), or the nitrogen-containing fluorine-type compound shown by said Formula (1)-(4). You may use the mixture containing 2 or more types of nitrogen-containing fluorine-type compounds chosen from the group which becomes as (A) nitrogen-containing fluorine-type compound.
Hereinafter, (A) the nitrogen-containing fluorine-based compound will be described in detail.

(Linear nitrogen-containing fluorine compound)
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 that it is the range of these. 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 structures of the following formulas (7) to (24).

(Cyclic nitrogen-containing fluorine-based compound)
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 The range is preferably 18, and more preferably 5-12. 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 above formula (3) or the above formula (4) include the structures of the following formulas (25) to (49).

Here, in said formula (2) and said formula (4), R is a coupling group which connects an oil repellency provision group and a hydrophilicity provision group in a molecular chain. The structure of the linking group R is not particularly limited as long as it is a divalent organic group. Specific examples of the linking group R include, for example, an oxygen atom [—O—], a carbonyl group [—C (═O) —], an imino group [—NH—], and a sulfonyl group [—S (═O). _2— ], —OP (═O) (O ⁻ ) O— group, hydrocarbon group having 1 to 20 carbon atoms, and combinations thereof. The linking group R may contain one or more selected from a polyoxyalkylene group and an epoxy group. The hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. The hydrocarbon group may be a chain hydrocarbon group or a cyclic hydrocarbon group. The chain hydrocarbon group may be linear or branched. Examples of the hydrocarbon group include an alkylene group, an alkenylene group, and an arylene group. The imino group and the hydrocarbon group may have a substituent.

  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. The amide bond includes a carboxylic acid amide bond and a sulfonamide bond. The ester bond includes a carboxylic acid ester bond, a sulfonic acid ester bond, and a phosphate ester bond.

  In addition, it is preferable to select and introduce the linking group R as appropriate depending on the characteristics to be imparted to the nitrogen-containing fluorine-based compound. Specifically, for example, when it is desired to adjust the solubility in a solvent, when it is desired to improve the durability by improving the adhesion with the base material, or when it is desired to improve the compatibility with the resin component, etc. It is done. 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 (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.
Hereinafter, the structure of the (A) nitrogen-containing fluorine-based compound will be described by dividing the hydrophilicity imparting group X into cases.

(Anion type)
When the hydrophilicity-imparting group X is an anion type, the above X is “—CO ₂ M ¹ ”, “—SO ₃ M ¹ ”, “—OSO ₃ M ¹ ”, “—OP (OH) O _{2” at the terminal.} “M ¹ ”, “—OPO ₃ M ¹ ₂ ”, “═O ₂ PO ₂ M ¹ ” or “—PO (OH) _y (OM ¹ ) _{2 -y} ” (M ¹ is an alkali metal or alkaline earth metal) , Mg, Al, R ¹ R ² R ³ R ⁴ N ⁺ ; R ^{1 to} R ⁴ are each a hydrogen atom or an independent straight chain or branched chain having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. An alkyl group, and y is an integer of 0 to 2. The example of the terminal structure described above shows a case where M ¹ is monovalent. When M ¹ is divalent, two identical anions may be bonded to M ¹ , or two different types of anions may be bonded.

  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 +), up R 1 to R ⁴ is from 1 to 20 carbon atoms which independently hydrogen atom or each, preferably up to 10 carbon atoms There is no particular limitation as long as it is a linear or branched alkyl group. Here, it is preferable that the alkyl group has 20 or less carbon atoms because the hydrophilic oil repellency is not impaired. 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, in the hydrophilic oil-repellent composite of this embodiment, it is desirable that the (A) nitrogen-containing fluorine-based compound is a hardly soluble compound having low solubility in water. That is, in (A) the nitrogen-containing fluorine-based compound, 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 and Mg are preferable because they have excellent hydrophilic oil repellency and low solubility in water.

Here, when the hydrophilic imparting group X is an anionic type, a specific example of the structure of the linear nitrogen-containing fluorine compound represented by the above formula (1) or the above formula (2) (however, it is a counter ion) the excluding structure of M ^1), for example, the structure of the following formula (50) - (117).

On the other hand, as a specific example of the structure of the cyclic nitrogen-containing fluorine compound represented by the above formula (3) or the above formula (4) (excluding the structure of M ¹ as a counter ion), for example, And structures of the following formulas (118) to (189).

(Cation type)
When the hydrophilic imparting group X is a cation 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 · R 7 SO 4 - "," ^{-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 are each a hydrogen atom or an independent linear or branched alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms). Here, it is preferable that the number of carbon atoms is 20 or less because the hydrophilic oil repellency is not impaired.

  Here, when the hydrophilic imparting group X is a cationic type, specific examples of the structure of the linear nitrogen-containing fluorine-based compound represented by the above formula (1) or the above formula (2) include, for example, The structure of Formula (190)-(223) is mentioned.

  In contrast, specific examples of the structure of the cyclic nitrogen-containing fluorine-based compound represented by the above formula (3) or the above formula (4) include, for example, the structures of the following formulas (224) to (258). It is done.

(Bisexual)
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 ⁻ ”, amine oxide type“ —N ⁺ R ⁸ R ⁹ O ⁻ ”, or phosphobetaine type“ —OPO ₃ ^— (CH ₂ ) _n N ⁺ R ⁸ R ⁹ R ”. ¹⁰ "(n is an integer of 1 to 5, R ⁸ and R ⁹ are a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ¹⁰ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms. Alkylene group). Here, it is preferable that the number of carbon atoms is 10 or less because the hydrophilic oil repellency is not impaired.

  Here, when the hydrophilic imparting group X is an amphoteric type, specific examples of the structure of the linear nitrogen-containing fluorine-based compound represented by the above formula (1) or the above formula (2) include, for example, The structure of Formula (259)-(309) is mentioned.

  In contrast, specific examples of the structure of the cyclic nitrogen-containing fluorine-based compound represented by the above formula (3) or the above formula (4) include, for example, the structures of the following formulas (310) to (375). It is done.

  In addition, the specific example of the structure of the (A) nitrogen-containing fluorine-type compound applicable to the hydrophilic oil-repellent complex of this embodiment mentioned above is an example, and the technical scope of this invention is limited to the said specific example. is not. That is, the (A) nitrogen-containing fluorine-based compound applicable to the present embodiment includes an oil repellency-imparting group composed of a nitrogen-containing perfluoroalkyl group, and a hydrophilic imparting group of any one of anionic, cationic and amphoteric types, In the molecule may be at least one each.

  In addition, the above-mentioned (A) nitrogen-containing fluorine-based compounds each sufficiently exhibit hydrophilic oil repellency, but the practical environment includes various acids, alkalis, oils, etc., and has a wide range of practical durability. In view of the above, it is desirable to appropriately combine nitrogen-containing fluorine-based compounds to enhance durability against the actual environment.

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

  In addition, the (A) nitrogen-containing fluorine-based compound may have two or more oil repellency-imparting groups that are the same or different in the molecule. Further, when two or more oil repellency-imparting groups are present in the molecule, they may be provided at both ends of the molecule or in the molecular chain.

  In addition, the (A) nitrogen-containing fluorine-based compound may have two or more hydrophilic imparting groups that are the same or different in the molecule.

  In addition, the (A) nitrogen-containing fluorine-based compound 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.

Next, the manufacturing method of (A) nitrogen-containing fluorine-type compound applicable to the hydrophilic oil-repellent complex of this embodiment is demonstrated.
The method for producing (A) a nitrogen-containing fluorine compound applicable to this embodiment is a carboxylic acid halide or sulfonic acid halide having a nitrogen-containing perfluoroalkyl group represented by the following formula (5) or (6). As described above, nitrogen-containing fluorine-based compounds represented by the above formulas (1) to (4) are produced. More specifically, using a carboxylic acid halide or sulfonic acid halide having a nitrogen-containing perfluoroalkyl group represented by the following formula (5) as a raw material, the nitrogen-containing fluorine represented by the above formula (1) or the above formula (2) A system compound is produced. Moreover, the nitrogen-containing fluorine-type compound shown to the said Formula (3) or the said Formula (4) is manufactured from the carboxylic acid halide or sulfonic-acid halide which has a nitrogen-containing perfluoroalkyl group shown by following formula (6). To do.

Here, in the above formula (5), Rf ¹ and Rf ² are the same or different from each other, and each is a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms. Rf ³ is a linear or branched perfluoroalkylene group having 1 to 6 carbon atoms.
Rf ¹ and Rf ² are each preferably the same or different from each other and each having 1 to 4 carbon atoms and is a linear or branched perfluoroalkyl group. Rf ³ has 1 to 4 carbon atoms, and is preferably a linear or branched perfluoroalkylene group.

Further, in the above formula ^{(6), Rf 4, Rf} 5 and Rf ⁶ is different the same or mutually a a 1 to 6 carbon atoms straight or branched perfluoroalkylene group.
Rf ⁴ , Rf ⁵ and Rf ⁶ are each preferably the same or different from each other and each having 1 to 4 carbon atoms and a linear or branched perfluoroalkylene group.
Z includes any of an oxygen atom, a nitrogen atom, a CF ₂ group, and a CF group. When Z contains a nitrogen atom or a CF group, a perfluoroalkyl group branched from Z may be bonded to Z.

In the above formulas (5) and (6), Y is CO or SO ₂ .
Further, in the above formulas (5) and (6), A is any one halogen atom selected from the group consisting of fluorine, chlorine, bromine and iodine.

  In addition, the manufacturing method of (A) nitrogen-containing fluorine-type compound applicable to this embodiment turns into a manufacturing method which changes with types of X shown in said formula (1)-(4). In the following, description will be made for each case.

(In the case of anion type)
First, the case where the nitrogen-containing fluorine-type compound shown to the said Formula (1) or the said Formula (3) is manufactured is demonstrated.
Of the raw materials shown in the above formula (5) or formula (6), 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 for monovalent cations such as Li, Na, K, 2 for divalent cations such as Ca, Mg, and 3) for trivalent cations such as Al, and Y is SO ₂ In the case (in the case of a sulfonic acid type), M (OH) _m (M is Li, Na, K, R ¹ R ² R ³ R ⁴ N ⁺ , Ca, Mg, Al, etc., m is Li, Na 1 for a monovalent cation such as K, K, 2 for a divalent cation such as Ca and Mg, 3 for a trivalent cation such as Al, and R ^{1 to} R ⁴ are hydrogen atoms or independent carbon numbers 1 to 20 To the linear or branched alkyl group) until it is neutralized and then dried to dryness. M (A) to melt-One by-product, extracting the desired product from the M (A) ₂ or M (A) ₃ is obtained by dryness using a solvent insoluble individuals, further the extraction solvent to dryness As a result, the object can be obtained. 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 the said Formula (2) or the 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 (5) or the above formula (6), an amide bond is formed between nitrogen-containing perfluoroalkylcarbonyl fluoride or sulfonyl fluoride and N, N-dialkylaminoalkyleneamine. To a terminal tertiary amine and then quaternized with an alkylating agent such as methyl iodide (CH ₃ I), methyl bromide (CH ₃ Br), or dimethyl sulfate ((CH ₃ ) ₂ SO ₄ ). Thus, a nitrogen-containing fluorine-based compound having a cationic hydrophilic group is obtained.

Further, for example, among the raw materials represented by the above formula (5) or the above formula (6), a nitrogen-containing perfluoroalkylcarbonyl fluoride or a sulfonyl fluoride and an N, N-dialkylaminoalkylene alcohol are ether-bonded to form a terminal group. By making it a tertiary amine and then quaternizing with an alkylating agent such as methyl iodide (CH ₃ I), methyl bromide (CH ₃ Br), dimethyl sulfate ((CH ₃ ) ₂ SO ₄ ), A nitrogen-containing fluorine-based compound having a cationic hydrophilic group is obtained.

(In the case of bisexual type)
Specifically, for example, in the case of the carboxybetaine type, first, among the raw materials represented by the above formula (5) or the above formula (6), nitrogen-containing perfluoroalkylcarbonyl fluoride or sulfonyl fluoride, and N, N-dialkyl Amido bond with aminoalkyleneamine or ether bond with N, N-dialkylaminoalkylene alcohol to make terminal tertiary amine, then react with sodium monochloroacetate to give amphoteric hydrophilicity A nitrogen-containing fluorine-based compound having a group is obtained.

  In addition, 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.

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

  Also, for example, in the case of the phosphobetaine type, a nitrogen-containing perfluorocarbonyl fluoride is reduced to an alcohol form, or a nitrogen-containing perfluoroalkylsulfonyl fluoride is sulfonamidated with an amino alcohol and a hydroxyl group is introduced at the terminal. Is reacted with phosphorus oxychloride in the presence of a base such as trimethylamine to obtain a dichlorophosphate ester having a nitrogen-containing perfluoroalkyl group. Next, the resulting dichlorophosphate ester having a nitrogen-containing perfluoroalkyl group is reacted with bromoethanol, then reacted with trimethylamine in the presence of a silver carbonate catalyst to form a quaternary ammonium salt, and finally hydrolyzed. A nitrogen-containing fluorine-based compound having a hydrophilicity-imparting group of the type is obtained.

(B) Inorganic compound The inorganic compound (B) applicable to the hydrophilic oil-repellent complex of the present embodiment is not particularly limited as long as it is an inorganic compound having a charge or an ionic group. Specific examples of such inorganic compounds include inorganic particles, clay minerals, and flocculants.

The inorganic particles are not particularly limited as long as they have a charge. Specific examples include fumed silica, colloidal silica, mullite, alumina, and zeolite. Moreover, as an inorganic particle, any one of these may be used independently and a 2 or more types of mixture may be used.
The inorganic particles may be aggregates of primary particles.
(B) When inorganic particles are used as the inorganic compound, a composite in which at least a part of the (A) nitrogen-containing fluorine-based compound is complexed by noncovalent bonding on the surface of the inorganic particles is obtained.

The clay mineral is not particularly limited as long as it has a charge. Specific examples include bentonite, organic bentonite, smectite, and kaolinite. As the clay mineral, any one of these may be used alone, or a mixture of two or more may be used.
(B) When a clay mineral is used as the inorganic compound, a composite is obtained in which (A) a nitrogen-containing fluorine-based compound is incorporated between the clay mineral layers to form a composite.

The flocculant is not particularly limited as long as it has an ionic group. Specific examples include polyaluminum chloride, polyferric sulfate, and aluminum sulfate. Moreover, as a flocculant, any one of these may be used independently and 2 or more types of mixtures may be used. Further, those obtained by dissolving these flocculants in water and liquefying them may be used.
(B) When the above-mentioned flocculant is used as the inorganic compound, a composite in which (A) at least a part of the nitrogen-containing fluorine-based compound and the flocculant are bonded by a non-covalent bond is obtained.

  As described above, the hydrophilic oil-repellent complex of this embodiment is a complex in which (A) a nitrogen-containing fluorine-based compound and (B) an inorganic compound having a charge or an ionic group are complexed. In other words, the hydrophilic oil-repellent complex of this embodiment is obtained by supporting (A) a nitrogen-containing fluorine-based compound at least partially on (B) an inorganic compound having a charge or an ionic group.

  Here, in the hydrophilic oil-repellent composite of this embodiment, the combination of (A) the nitrogen-containing fluorine compound and (B) the inorganic compound is not particularly limited, and (A) the nitrogen-containing fluorine compound It can be appropriately selected according to the molecular structure or the charge or ionic group of the (B) inorganic compound.

  Further, in the hydrophilic oil-repellent composite of the present embodiment, the mass composition ratio of (A) the nitrogen-containing fluorine-based compound and (B) the inorganic compound is not particularly limited, and the hydrophilic oil-repellent characteristic value, It can select suitably according to the sustainability of the said characteristic. Specifically, the mass composition ratio of (A) the nitrogen-containing fluorine-based compound and (B) the inorganic compound can be selected from the range of 1 to 99 to 99-1.

  Furthermore, since the hydrophilic oil-repellent composite of this embodiment includes a composite of (A) a nitrogen-containing fluorine-based compound and (B) an inorganic compound having a charge or ionic group, filter paper, nonwoven fabric, cartridge filter, etc. By fixing to the surface of the base material, hydrophilicity and oil repellency are improved, and more excellent oil / water separation performance can be obtained. In addition, (A) the nitrogen-containing fluorine-based compound and (B) the inorganic compound having a charge or ionic group have a non-covalent bond, thus reducing the elution of (A) the nitrogen-containing fluorine-based compound during oil-water separation. And durability can be improved. For fixing to the substrate, it is possible to use a resin or glass that will be described later.

  The hydrophilic oil-repellent complex of the present embodiment is configured to contain as a main component a complex in which (A) a nitrogen-containing fluorine-based compound and (B) an inorganic compound having a charge or an ionic group are combined. ing. For this reason, the hydrophilic oil-repellent composite of this embodiment is used for various applications and is a component that exhibits hydrophilicity and oil repellency even when used in a real environment with moisture (A) a nitrogen-containing fluorine-based compound The outflow of the compound can be suppressed. Therefore, according to the hydrophilic oil-repellent composite of this embodiment, effects such as antifouling performance and oil / water separation performance due to the hydrophilic oil repellency can be maintained (that is, excellent in durability).

<Method for producing hydrophilic oil-repellent composite>
Next, the manufacturing method of the hydrophilic oil-repellent complex of this embodiment is demonstrated.
The method for producing a hydrophilic oil-repellent complex of the present embodiment is a method in which (A) a nitrogen-containing fluorine-based compound and (B) an inorganic compound having a charge or an ionic group are complexed, that is, formation of the complex. Is the method. The method of forming the composite is different depending on the combination of (A) a nitrogen-containing fluorine-based compound and (B) an inorganic compound. Specifically, there are the following three methods.

  As a first method, first, a coating liquid is prepared by dissolving or dispersing a nitrogen-containing fluorine-based compound and an inorganic compound in any one of water, an organic solvent, or a mixed solvent of water and an organic solvent. obtain. Subsequently, after apply | coating the obtained coating liquid to a base material, it is made to dry and the solvent component of a coating liquid is removed. In the drying process, a complex of a nitrogen-containing fluorine-based compound and an inorganic compound having a charge or an ionic group can be obtained.

  As a second method, first, a solution in which a nitrogen-containing fluorine-based compound and an inorganic compound are dispersed in any one of water, an organic solvent, or a mixed solvent of water and an organic solvent is obtained. Subsequently, after separating a solid substance from the obtained solution by filtration, a composite can be obtained by drying the solid substance.

  As a third method, first, a solvent component after dissolving or dispersing a nitrogen-containing fluorine-based compound and an inorganic compound in any one of water, an organic solvent, or a mixed solvent of water and an organic solvent. The water or organic solvent is distilled off. Subsequently, a composite can be obtained by drying the obtained residue.

  The organic solvent used for forming the complex is not particularly limited as long as it can dissolve or disperse the (A) nitrogen-containing fluorine-based compound, but from the viewpoint of environmental impact and the like. Water, alcohol, or a mixture of water and alcohol can be used. Further, the alcohol is not particularly limited, and examples thereof include methanol, ethanol, IPA and the like.

  It should be noted that an inorganic compound having a charge or ionic group opposite to that of the nitrogen-containing fluorine-based compound is added in the above-described composite formation method. However, when the nitrogen-containing fluorine-based compound has amphoteric ions, either may be used.

  Here, the nitrogen-containing fluorine-based compound described above is hardly soluble in water and can be dispersed in water. When an inorganic compound is added to water in which a nitrogen-containing fluorine-based compound is dispersed, the charge of the nitrogen-containing fluorine-based compound and the inorganic compound are complexed by a non-covalent bond such as a hydrogen bond, and the nitrogen-containing fluorine-based compound And a composite of an inorganic compound can be obtained.

  On the other hand, if the nitrogen-containing fluorine-based compound is dissolved in an organic solvent, it will not form a complex with an inorganic compound as it is, but in the process of evaporating the solvent component to dryness, each charge is canceled and aggregated And a complex of a nitrogen-containing fluorine-based compound and an inorganic compound can be obtained. In this composite, both (A) the nitrogen-containing fluorine-based compound and (B) the inorganic compound are partially charged due to the influence of moisture in the atmosphere in the actual use environment, so that a stronger bond can be obtained. Occur.

  According to the method for producing a hydrophilic oil-repellent composite of this embodiment, it is a method for easily forming a composite that is a main component of the hydrophilic oil-repellent composite. In other words, (A) a nitrogen-containing fluorine-based compound and (B) an inorganic compound having a charge or an ionic group can be reliably combined by a simple method.

<Surface coating material>
A surface coating material for the hydrophilic oil-repellent composite can be formed by incorporating the hydrophilic oil-repellent composite of the present embodiment into the solvent. In addition, as the hydrophilic oil-repellent complex, a complex in which a nitrogen-containing fluorine compound and an inorganic compound are combined may be used. As described above, a nitrogen-containing fluorine-based compound is used as a solvent for forming the complex. You may use the thing of the solution state which each melt | dissolved or disperse | distributed the compound and the inorganic compound. When the solution is used, a complex of the nitrogen-containing fluorine-based compound and the inorganic compound is formed in the process of evaporating the solvent component.

  Here, examples of the solvent include water, an organic solvent, or a mixed solvent of water and an organic solvent. Moreover, as an organic solvent, methanol, ethanol, IPA, tetrahydrofuran, hexane, chloroform, toluene, ethyl acetate, DMSO, DMF, acetone, a fluorine-type solvent etc. are mentioned, for example. In particular, water, alcohols such as methanol, ethanol, and IPA, or a mixture of water and alcohol are preferable from the viewpoint of easy drying and use, and environmental impact. It is also possible to mix a solvent compatible with these solvents. For example, ether solvents such as tetrahydrofuran, aliphatic hydrocarbon solvents such as hexane, halogenated hydrocarbon solvents such as chloroform, aromatic hydrocarbon solvents such as toluene, ester solvents such as ethyl acetate, ketones such as acetone, etc. And fluorine-based solvents such as hexafluoroxylene.

  Here, in the surface coating material, the mass composition ratio of the nitrogen-containing fluorine-based compound and the solvent in the hydrophilic oil-repellent composite is preferably 0.2 to 50.0 to 99.8 to 50.0, more preferably. The range is 1.0 to 30.0 to 99.0 to 70.0, and more preferably 2 to 10 to 98 to 90. It is preferable that the mass composition ratio of the nitrogen-containing fluorine-based compound contained in the hydrophilic oil-repellent composite in the surface coating material is 0.2 or more because the entire base material can be sufficiently hydrophilic and oil-repellent when treated. On the other hand, when the mass composition ratio of the nitrogen-containing fluorine-based compound contained in the hydrophilic oil-repellent composite in the surface coating material is 50 or less, it is preferable because the solution dispersion stability of the surface coating material is excellent. In consideration of applicability and durability of the product, the mass composition ratio between the nitrogen-containing fluorine-based compound and the solvent in the hydrophilic oil-repellent composite is preferably in the range of 2 to 10 to 98 to 90.

  Moreover, it is preferable to add a binder to the surface coating material. Thereby, the adhesiveness to a base material can be improved. Moreover, since it has the function of enclosing the nitrogen-containing fluorine-based compound and reducing the area in contact with the environment of the nitrogen-containing fluorine-based compound itself, the durability and durability of the characteristics can be improved.

  Specific examples of the binder include resin and inorganic glass. Examples of the resin include a thermoplastic resin, a thermoplastic elastomer, a thermosetting resin, a UV curable resin, and more specifically, for example, polyvinyl chloride, polyethylene, polypropylene, polycarbonate, polyester, polystyrene, silicone resin, polyvinyl Acetal, polyvinyl alcohol, acrylic polyol resins, polyester polyol resins, urethane resins, fluororesins, thermoplastic resins such as thermoplastic acrylic resins, thermosetting resins such as epoxy resins, phenol resins, thermosetting acrylic resins, etc. Is mentioned.

  Furthermore, in order to maximize the hydrophilic oil repellency, it is preferable to use a hydrophilic polymer as a binder. Further, among the hydrophilic polymers, those containing a hydroxyl group that brings about an adhesion such as adhesion to a base material and an interaction such as hydrogen bonding with a hydrophilic oil-repellent complex are preferable.

  Specific examples of the hydrophilic polymer include polysaccharides such as polyvinyl alcohol, polyvinyl butyral, cellulose, and derivatives thereof. These may be used alone or in combination of two or more. The hydrophilic polymer may be crosslinked with a crosslinking agent. Such crosslinking improves the durability of the coating film described later.

  The crosslinking agent is not particularly limited and can be appropriately selected depending on the purpose. Specific examples include an epoxy compound, an isocyanate compound, an aldehyde compound, an aldehyde compound, an ultraviolet crosslinking compound, a leaving group-containing compound, a carboxylic acid compound, and a urea compound.

Specifically, as the inorganic glass, for example, trialkoxysilane represented by the chemical formula [R ¹⁴ Si (OR ¹⁵ ) ₃ ], chemical formula [Si (OR ¹⁶ ) ₄ ] (R ^{14 to} R ¹⁶ are independent carbons, respectively. And silane compounds such as tetraalkoxysilane, water glass, and the like. Among these, water glass is preferable because the effect of improving durability is high.

  In the surface coating material, the mass composition ratio of the nitrogen-containing fluorine-based compound and the binder in the hydrophilic oil-repellent composite is preferably in the range of 0.2 to 99.9 to 99.8 to 0.1, More preferably, it is the range of 2-98 to 98-2, More preferably, it is the range of 10-90 to 90-10. A mass composition ratio of the nitrogen-containing fluorine-based compound in the hydrophilic oil-repellent composite is preferably 0.2 or more because hydrophilic oil-repellent properties can be sufficiently obtained.

  As a mixing method for forming a surface coating material, a hydrophilic oil-repellent complex such as a ball mill, roll mill, sand mill, paint shaker, homogenizer, impeller stirrer, ultrasonic disperser, or magnetic stirrer is dispersed or dissolved in a solvent. It is not particularly limited as long as it can be performed.

  In addition to the hydrophilic oil-repellent complex, the solvent, and the binder, the surface coating material further includes an additive as an optional component in order to impart functions other than hydrophilic oil-repellent properties such as pigments, conductivity-imparting agents, and leveling agents. May be included.

<Coating film>
By using the surface covering material described above, at least a part of the surface of the substrate can be covered with a coating film. The coating film may be made of only a hydrophilic oil-repellent complex or may contain a binder. When the coating film contains a binder, the mass composition ratio between the nitrogen-containing fluorine-based compound and the binder in the hydrophilic oil-repellent complex is in the range of 0.2 to 99.9 vs. 99.8 to 0.1. Preferably there is. Here, it is preferable that the mass composition ratio of the nitrogen-containing fluorine-based compound in the hydrophilic oil-repellent composite is 0.2 or more because sufficient hydrophilic oil-repellency can be obtained. In consideration of adhesion to the substrate and durability of the coating film, a range of 2 to 98 to 98 to 2 is more preferable, and a range of 10 to 90 to 90 to 10 is particularly preferable.

  As a method for forming the coating film, specifically, for example, the surface coating material described above is applied to at least a part of the surface of the base material, and dried to remove the solvent. A coating film can be formed at least partially.

  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 immersed in the surface coating material, a method using an application means such as a spray, a brush, or a roller, or a method using a printing method may be used.

  In the formation process, the conditions for the drying treatment of the coating film vary depending on the type and content of the solvent contained in the surface coating material, but for example, drying at room temperature for 1 to 24 hours or affecting the substrate. Drying by heating to a certain extent is mentioned.

<Resin composition>
The hydrophilic oil-repellent composite of this embodiment described above can be used as an additive for imparting a hydrophilic oil-repellent function to various resins.

  Examples of the resin include a thermoplastic resin, a thermoplastic elastomer, a thermosetting resin, and a UV curable resin. The resin is not particularly limited as long as the hydrophilic oil-repellent composite can be dispersed or dissolved. Specifically, as such a resin, for example, polyvinyl chloride, polyethylene, polypropylene, polycarbonate, polyester, polystyrene, silicone resin, polyvinyl acetal, polyvinyl alcohol, acrylic polyol resin, polyester polyol resin, urethane resin, Examples thereof include thermoplastic resins such as fluororesins and thermoplastic acrylic resins, and thermosetting resins such as epoxy resins, phenol resins, and thermosetting acrylic resins.

  Furthermore, in order to maximize the hydrophilic oil repellency, it is preferable to use a hydrophilic polymer as the resin. As the hydrophilic polymer, those containing a hydroxyl group are preferred. Specific examples include polysaccharides such as polyvinyl alcohol, polyvinyl butyral, and cellulose, and derivatives thereof. These may be used alone or in combination of two or more. The hydrophilic polymer may be crosslinked with a crosslinking agent. Such cross-linking improves the durability of the resin composition.

  The crosslinking agent is not particularly limited and can be appropriately selected depending on the purpose. Specific examples include an epoxy compound, an isocyanate compound, an aldehyde compound, an aldehyde compound, an ultraviolet crosslinking compound, a leaving group-containing compound, a carboxylic acid compound, and a urea compound.

  In addition to the hydrophilic oil-repellent complex and resin, the resin composition is added to impart functions other than hydrophilic oil-repellent properties such as fluidity improvers, surfactants, flame retardants, conductivity-imparting agents, and fungicides. An agent may further be included.

  The method for forming the resin composition is not particularly limited as long as it is a method capable of dispersing or dissolving a hydrophilic oil-repellent complex appropriately selected according to the type of resin. Specifically, for example, as a method of mixing the hydrophilic oil-repellent complex with the thermoplastic resin, there is a method of mixing by kneading by an extrusion method or a roll method.

  The resin composition can be further processed into a molded resin molded product. Specific examples include injection molded products such as films, sheets, threads, and housings.

  In the resin composition, the mass composition ratio of the nitrogen-containing fluorine-based compound and the resin in the hydrophilic oil-repellent composite is preferably in the range of 0.2 to 99.9 to 99.8 to 0.1, more Preferably it is the range of 2-98 to 98-2, More preferably, it is the range of 10-90 to 90-10. A mass composition ratio of the nitrogen-containing fluorine-based compound in the hydrophilic oil-repellent composite is preferably 0.2 or more because the hydrophilic oil-repellent function can be sufficiently exhibited. On the other hand, if the mass composition ratio of the nitrogen-containing fluorine-based compound in the hydrophilic oil-repellent composite is 90 or less, it is preferable because it becomes easy to maintain moldability without impairing the resin physical properties.

  Applications of the coating film and the resin composition described above include application to a member that is expected to be quick-drying such as water, a member that is expected to have an antifouling effect, a member that is expected to have an antifogging effect, and oil removability. Can be mentioned.

  More specific applications where quick drying of water and the like are expected include building materials, building exteriors such as outer walls and roofs, building interiors, window frames, window glass, automobiles, rail vehicles, aircraft, ships, bicycles, motorcycles Exterior and painting of vehicles such as, machinery and equipment exteriors, dust covers and coatings, signs, traffic signs, various display devices, advertising towers, road noise barriers, railway noise barriers, bridges, guard rail exteriors and coatings , Tunnel interior and painting, insulators, solar cell covers, solar water heater heat collection covers, heat exchanger radiating fins, plastic houses, vehicle lighting cover, housing equipment, toilets, bathtubs, washstands, lighting fixtures, lighting covers , Kitchen utensils, tableware, dishwashers, tableware dryers, sinks, cooking ranges, kitchen hoods, ventilation fans, and films for attaching to the surface of the article.

  More specific applications where antifouling effects are expected include building exteriors such as exterior walls and roofs, building interiors, window frames, window glass, signs, traffic signs, noise barriers, automobiles, rail cars, Exteriors and paintings of vehicles such as aircraft, ships, bicycles and motorcycles, exteriors of machinery and equipment, dustproof covers and coatings, various display devices, advertising towers, soundproof walls for roads, soundproof walls for railways, bridges, guardrails And painting, tunnel interior and painting, insulator, solar battery cover, solar water heater heat collection cover, plastic house, vehicle lighting cover, housing equipment, toilet bowl, bathtub, wash basin, lighting fixture, lighting cover, kitchenware, Tableware, dishwasher, dish dryer, sink, cooking range, kitchen hood, ventilation fan, etc. Examples of the optical member include a cover glass or a cover sheet of a touch panel, an icon sheet, a screen protection film, and an optical disk. In particular, it has excellent characteristics in terms of removability against oil contamination in canteens and kitchenware. Furthermore, the film etc. for making it stick on the surface of these articles | goods are mentioned. It can also be applied to snow country roofing materials, antennas, power transmission lines, etc., and in that case, characteristics excellent in snow accretion prevention can be obtained.

  More specific applications where anti-fogging effects are expected include glass for automobiles and building materials, rear mirrors for vehicles, mirrors for bathrooms, mirrors for toilets, mirrors such as road mirrors, eyeglass lenses, optical lenses, Examples include photographic lenses and films for attaching to the surfaces of these articles.

<Oil-water separation filter media>
When a mixed liquid of water and oil is passed through a filter paper, nonwoven fabric, cartridge filter, inorganic or organic porous material or porous membrane treated with the surface coating material described above, water passes through the filter, etc. On the other hand, since oil cannot pass through, it can be used as a hydrophilic oil-repellent separation membrane or filter that can separate oil and water only by gravity (collectively referred to as “separation filter medium”). This separation membrane and filter can be used, for example, as an oil-water separation membrane or an oil-water separation filter (that is, “oil-water separation filter medium”) for separating water and oil during oil extraction or recovery of spilled oil. is there.

  Moreover, since the oil-water separation filter medium described above is imparted with hydrophilic oil repellency, it is difficult for organic molecules and soil mud contaminated with oil to adhere, and excellent fouling resistance is obtained. Further, dirt attached by physical treatment such as back pressure cleaning is easily removed, and easy cleaning is excellent.

  As described above, the hydrophilic oil-repellent complex of this embodiment includes an oil-repellent imparting group composed of a nitrogen-containing perfluoroalkyl group in the molecule, and a hydrophilic imparting group of any one of anionic, cationic and amphoteric types. Since it has a compound having nitrogen (nitrogen-containing fluorine-based compound) and has excellent hydrophilic oil repellency, it has applicability to a wide variety of uses.

  Further, the hydrophilic oil-repellent complex of this embodiment does not contain a continuously bonded perfluoroalkyl group having 8 or more carbon atoms, and PFOS or PFOA, which is problematic in terms of bioaccumulation and environmental adaptability, is used. There is no concern to generate.

  In addition, the hydrophilic oil-repellent complex of the present embodiment is configured to include as a main component a complex in which a nitrogen-containing fluorine-based compound and an inorganic compound having a charge or an ionic group are complexed. For this reason, even if it is a case where the hydrophilic oil-repellent complex of this embodiment is used for various uses and it is used in the real environment with moisture, it suppresses the outflow of the nitrogen-containing fluorine compound component which expresses hydrophilic oil-repellency. Can do. Therefore, according to the hydrophilic oil-repellent composite of this embodiment, effects such as antifouling performance and oil / water separation performance due to hydrophilic oil repellency can be sustained.

  Moreover, according to the manufacturing method of the hydrophilic oil-repellent complex of this embodiment, it is a method of forming easily the complex which is a main component of a hydrophilic oil-repellent complex. In other words, the nitrogen-containing fluorine-based compound and the inorganic compound having a charge or ionic group can be reliably combined by a simple method.

  In addition, the surface coating material, coating film, resin composition, and oil-water separation filter medium including the present embodiment are mainly composed of a complex in which a nitrogen-containing fluorine-based compound and an inorganic compound having a charge or an ionic group are combined. Since the hydrophilic oil-repellent complex contained as is used, it is possible to suppress the outflow of the nitrogen-containing fluorine-based compound component that exhibits hydrophilic oil-repellency even when used in an actual environment with moisture. Therefore, various effects such as antifouling performance and oil / water separation performance due to hydrophilic oil repellency can be sustained. That is, it has excellent durability.

  The hydrophilicity and oil repellency of the hydrophilic oil-repellent complex of this embodiment can be evaluated by contact angle measurement (droplet method).

  For contact angle measurement, the surface coating material was measured using a bar coater no. 3 is applied to a PET film, and the solvent is removed by natural drying at room temperature to form a coating film.

  Next, water and n-hexadecane are dropped on this coating film, and the contact angles between the coating film and the droplets are measured. The contact angle can be measured using a commercially available measuring device (for example, “Drop Master DM-701” manufactured by Kyowa Interface Science Co., Ltd.). Specifically, ion-exchanged water is prepared in a syringe, and the contact angle after 1000 msec after the water touches the membrane surface in a stationary state is the water contact angle (static contact angle) analyzed by the θ / 2 method. Unit: ° (degrees), 1 ° = (π / 180) rad). 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.

  Generally, the case where the static contact angle of water is 40 ° or less is referred to as hydrophilicity, and the case where the static contact angle of n-hexadecane is 40 ° or more is referred to as oil repellency. Also in the present application, as a result of contact angle measurement, when the static contact angle of water with respect to the coating film is 40 ° or less and the static contact angle of n-hexadecane is 40 ° or more, the hydrophilic oil-repellent composite of this embodiment Suppose that it has hydrophilic oil repellency.

  In the contact angle measurement (droplet method), water and n-hexadecane are dropped using the following conditions.

(Contact angle measurement)
Drop volume: 2 μL / drop (water)
Drop volume: 2 μL / drop (n-hexadecane)
Measurement temperature: Room temperature (22 ± 1 ° C)

  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.

  Examples of the present invention are shown below together with comparative examples. The present invention is not limited to these examples.

<Synthesis of nitrogen-containing fluorine-based compounds>
(Synthesis Example 1)
“Synthesis of 2- [3-[[perfluoro (2-methyl-3-dibutylaminopropanoyl)] amino] propyl-dimethyl-ammonium] acetate”
120 g of perfluoro (2-methyl-3-dibutylaminopropionic acid) fluoride obtained by electrolytic fluorination of methyl 2-methyl-3-dibutylaminopropionate was dissolved in a solution of 39 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, IPE was distilled off and further distilled to obtain 64 g of (C ₄ F ₉ ) ₂ NCF ₂ CF (CF ₃ ) CONHC ₃ H ₆ N (CH ₃ ) ₂ as a crude product (yield 47 %).
Next, 8 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 overnight under stirring in ethanol, filtered, After concentration, 9 g of a dimethylbetaine compound represented by the following formula (376) was obtained (yield 99%).

(Synthesis Example 2)
“Synthesis of 2- [3-[[perfluoro (2-methyl-3-piperidinonopropanoyl)] amino] propyl-dimethyl-ammonium] acetate”
20 g of perfluoro (2-methyl-3-piperidinopropionic acid) fluoride obtained by electrolytic fluorination was dropped in a solution of 9 g of dimethylaminopropylamine in 110 ml of IPE solvent 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, and after separating and washing with water, IPE was distilled off to obtain a crude product. , CF ₂ (CF ₂ CF ₂ ) ₂ NCF ₂ CF (CF ₃ ) CONHC ₃ H ₆ N (CH ₃ ) ₂ was obtained (crude yield 76%).
Next, 10 g of the obtained crude product CF ₂ (CF ₂ CF ₂ ) ₂ NCF ₂ CF (CF ₃ ) CONHC ₃ H ₆ N (CH ₃ ) ₂ was mixed with 3 g of sodium monochloroacetate under stirring in ethanol. The mixture was refluxed overnight to obtain 11 g of a dimethylbetaine compound represented by the following formula (377) (99% yield).

(Synthesis Example 3)
“Synthesis of calcium perfluoro (3-dibutylaminopropionate)”
Perfluoro (3-dibutylaminopropionic acid) fluoride obtained by electrolytically fluorinating methyl 3-dibutylaminopropionate was charged with 352 g of an aqueous solution of 12.5% (mass percent concentration, hereinafter the same) sodium hydroxide in a 2 L glass flask. 837g was dripped and it reacted. After the dropwise addition, 500 mL of ethyl acetate was added to extract sodium perfluoro (3-dibutylaminopropionic acid). After separating the ethyl acetate layer and water, the ethyl acetate was distilled off with a rotary evaporator to obtain 488 g of light yellow solid sodium perfluoro (3-dibutylaminopropionate).

  Next, 488 g of sodium perfluoro (3-dibutylaminopropionic acid) and 280 g of 95% sulfuric acid were charged in a 1 L glass flask, mixed, and distilled under reduced pressure, to obtain 436 g of perfluoro (3-dibutylaminopropionic acid) solid at room temperature Obtained (note that the yield from the sodium salt was 93%).

23.5 g of perfluoro (3-dibutylaminopropionic acid) was neutralized with 1.5 g of calcium hydroxide in a methanol / water mixture. The precipitated crystals were separated by filtration and dried at 100 ° C. to obtain 23.5 g of perfluoro (3-dibutylaminopropionic acid) calcium represented by the following formula (378) (yield 97%). The solubility of this compound in water at room temperature (25 ° C.) was 2 [g / 100 g-H ₂ O].

(Synthesis Example 4)
“Synthesis of 3-[[perfluoro (3-dibutylaminopropanoyl)] amino] propyl-trimethyl-ammonium iodide”
10 g of perfluoro (3-dibutylaminopropionic acid) fluoride obtained by electrolytic fluorination of methyl 3-dibutylaminopropionate was added dropwise to a solution of 4 g of dimethylaminopropylamine in 50 ml of IPE solvent 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, it was distilled off IPE, as a crude product _was obtained 7g of _{(C 4 F 9) 2 NC} 2 F 4 CONHC 3 H 6 N (CH 3) 2 (62% yield).
Subsequently, methyl iodide was added to the obtained crude product in methyl ethyl ketone, and the mixture was stirred overnight at room temperature. After completion of the reaction, the product was collected by filtration to obtain 6 g of a quaternary ammonium iodide compound represented by the following formula (379) (yield 71%).

(Synthesis Example 5)
“Synthesis of 3- [3-[[perfluoro (2-methyl-3-dibutylaminopropanoyl)] amino] propyl-dimethyl-ammonium] propanesulfonate”
120 g of perfluoro (2-methyl-3-dibutylaminopropionic acid) fluoride obtained by electrolytic fluorination of methyl 2-methyl-3-dibutylaminopropionate was dissolved in a solution of 39 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, IPE was distilled off and further distilled to obtain 64 g of (C ₄ F ₉ ) ₂ NCF ₂ CF (CF ₃ ) CONHC ₃ H ₆ N (CH ₃ ) ₂ as a crude product (yield 47 %).
Subsequently, 1.5 g of the obtained (C ₄ F ₉ ) ₂ NCF ₂ CF (CF ₃ ) CONHC ₃ H ₆ N (CH ₃ ) ₂ was stirred with 1,3-propane sultone for 23 hours in acetonitrile. After refluxing, reprecipitation was performed in a fluorine-based solvent (Asahi Glass Co., Ltd .: AK225) and an IPE mixed solvent to obtain 1.3 g of a sulfobetaine compound represented by the following formula (380) (yield 75%).

(Synthesis Example 6)
“Synthesis of 4- [3-[[perfluoro (2-methyl-3-dibutylaminopropanoyl)] amino] propyl-dimethyl-ammonium butanesulfonate”
120 g of perfluoro (2-methyl-3-dibutylaminopropionic acid) fluoride obtained by electrolytic fluorination of methyl 2-methyl-3-dibutylaminopropionate was dissolved in a solution of 39 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, IPE was distilled off and further distilled to obtain 64 g of (C ₄ F ₉ ) ₂ NCF ₂ CF (CF ₃ ) CONHC ₃ H ₆ N (CH _{3) 2} as a crude product (yield 47%). ).
Next, 15 g of the obtained (C ₄ F ₉ ) ₂ NCF ₂ CF (CF ₃ ) CONHC ₃ H ₆ N (CH ₃ ) ₂ was stirred with acetonitrile in an amount of 4.2 g of 1,4-butane sultone for 18 hours. After refluxing, reprecipitation was performed in a fluorine-based solvent (Asahi Glass Co., Ltd .: AK225) and an IPE mixed solvent to obtain 13.3 g of a sulfobetaine compound represented by the following formula (381) (yield 75%).

(Synthesis Example 7)
“Synthesis of 3- [3-[[perfluoro (2-methyl-3-dibutylaminopropanoyl)] amino] propyl-dimethyl-ammonium] 2-hydroxypropane-1-sulfonate”
120 g of perfluoro (2-methyl-3-dibutylaminopropionic acid) fluoride obtained by electrolytic fluorination of methyl 2-methyl-3-dibutylaminopropionate was dissolved in a solution of 39 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, IPE was distilled off and further distilled to obtain 64 g of (C ₄ F ₉ ) ₂ NCF ₂ CF (CF ₃ ) CONHC ₃ H ₆ N (CH ₃ ) ₂ as a crude product (yield 47%). ).
Next, 5.0 g of the obtained (C ₄ F ₉ ) ₂ NCF ₂ CF (CF ₃ ) CONHC ₃ H ₆ N (CH ₃ ) ₂ , 2.0 g of sodium 3-chloro-2-hydroxypropanesulfonate, ethanol 10 ml and 2.1 g of water were mixed and refluxed for 20 hours. Thereafter, 0.7 g of sodium carbonate was added, and the mixture was further refluxed for 4 hours. After completion of the reaction, the reaction solution was poured into water, and the precipitated solid was reprecipitated in a fluorine-based solvent (Asahi Glass Co., Ltd .: AK225) and an IPE mixed solvent to obtain 3.5 g of a sulfobetaine compound represented by the following formula (382). Obtained (yield 59%).

<Production of surface coating material>

Example 1
As a nitrogen-containing fluorine-based compound, 4 parts by mass of “2- [3-[[perfluoro (2-methyl-3-dibutylaminopropanoyl)] amino] propyl-dimethyl-ammonium] acetate obtained in Synthesis Example 1, 4 parts by mass of fumed silica (manufactured by Nippon Aerosil Co., Ltd., “AEROSIL 300”) as an inorganic compound, 15 parts by mass of polyvinyl butyral (Sekisui Chemical Co., Ltd., “ESREC BL-1”) as a binder, and 77 mass of ethanol as a solvent A surface coating material blended at a ratio of parts was prepared.

(Example 2)
As a nitrogen-containing fluorine-based compound, 2 parts by mass of “2- [3-[[perfluoro (2-methyl-3-dibutylaminopropanoyl)] amino] propyl-dimethyl-ammonium] acetate obtained in Synthesis Example 1 was used as water. It was uniformly dispersed in 400 mL, and 2 parts by mass of fumed silica (Nippon Aerosil Co., Ltd., “AEROSIL300”) was added as an inorganic compound. The precipitated solid was collected by vacuum filtration and dried to obtain 4 parts by mass of a hydrophilic oil-repellent complex. A surface coating material was prepared by blending 4 parts by mass of the obtained composite and 2 parts by mass of polyvinyl butyral (Sekisui Chemical Co., Ltd., “ESREC BL-1”) into 94 parts by mass of methyl ethyl ketone as a binder.

(Example 3)
As a nitrogen-containing fluorine-based compound, 48 parts by mass of “2- [3-[[perfluoro (2-methyl-3-dibutylaminopropanoyl)] amino] propyl-dimethyl-ammonium] acetate obtained in Synthesis Example 1, inorganic 1 part by mass of fumed silica (manufactured by Nippon Aerosil Co., Ltd., “AEROSIL50”) as a compound, 1 part by mass of polyvinyl butyral (manufactured by Sekisui Chemical Co., Ltd., “ESREC BL-1”) as a binder, and 50 parts by mass of ethanol as a solvent A surface coating material blended at the ratio was prepared.

Example 4
As a nitrogen-containing fluorine-based compound, 5 parts by mass of “2- [3-[[perfluoro (2-methyl-3-dibutylaminopropanoyl)] amino] propyl-dimethyl-ammonium] acetate obtained in Synthesis Example 1, 5 parts by mass of organic bentonite (“Esven W” manufactured by Hojun Co., Ltd.) as an inorganic compound, 18 parts by mass of polyvinyl butyral (manufactured by Sekisui Chemical Co., Ltd., “ESREC BL-1”) as a binder, and 72 parts by mass of ethanol as a solvent A surface coating material blended at a ratio was prepared.

(Example 5)
As a nitrogen-containing fluorine-based compound, 4 parts by mass of “2- [3-[[perfluoro (2-methyl-3-dibutylaminopropanoyl)] amino] propyl-dimethyl-ammonium] acetate obtained in Synthesis Example 1, 4 parts by mass of bentonite (“Bengel”, manufactured by Hojun Co., Ltd.) as an inorganic compound, 19 parts by mass of polyvinyl butyral (Sekisui Chemical, “ESREC BL-1”) as a binder, and 73 parts by mass of ethanol as a solvent A blended surface coating material was prepared.

(Example 6)
As a nitrogen-containing fluorine-based compound, 0.2 mass of “2- [3-[[perfluoro (2-methyl-3-dibutylaminopropanoyl)] amino] propyl-dimethyl-ammonium] acetate obtained in Synthesis Example 1 was used. 4 parts by mass of zeolite (Union Showa Co., Ltd., “Molecular Sieve 13X Powder”) as an inorganic compound, 19 parts by mass of polyvinyl butyral (Sekisui Chemical Co., Ltd., “S-Lec BL-1”) as a binder, and ethanol as a solvent A surface coating material blended at a ratio of 76.8 parts by mass was produced.

(Example 7)
As a nitrogen-containing fluorine-based compound, 4 parts by mass of “2- [3-[[perfluoro (2-methyl-3-dibutylaminopropanoyl)] amino] propyl-dimethyl-ammonium] acetate obtained in Synthesis Example 1, 4 parts by mass of silica sol (“methanol silica sol MA-ST”, manufactured by Nissan Chemical Co., Ltd.) as an inorganic compound, 16 parts by mass of polyvinyl butyral (Sekisui Chemical, “ESREC BL-1”) as a binder, and 66 as ethanol as a solvent A surface coating material containing 10 parts by mass of methanol and methanol was prepared.

(Example 8)
As a nitrogen-containing fluorine-based compound, 5 parts by mass of “2- [3-[[perfluoro (2-methyl-3-dibutylaminopropanoyl)] amino] propyl-dimethyl-ammonium] acetate obtained in Synthesis Example 1, 5 parts by mass of acrylic resin (manufactured by Toa Gosei Co., Ltd., “ARUFON UC-3000”) as a binder, 5 parts by mass of fumed silica (manufactured by Nippon Aerosil Co., Ltd., “AEROSIL 300”) as an inorganic compound, and 85 ethanol as a solvent A surface coating material blended at a mass part ratio was produced.

Example 9
As a nitrogen-containing fluorine-based compound, 4 parts by mass of “2- [3-[[perfluoro (2-methyl-3-dibutylaminopropanoyl)] amino] propyl-dimethyl-ammonium] acetate obtained in Synthesis Example 1, 93 parts by mass of a 6% aqueous solution of polyvinyl alcohol resin (manufactured by Nippon Gosei Chemical Co., Ltd., “Gosenex Z-410”) as a binder, and 3 parts by mass of fumed silica (manufactured by Nippon Aerosil Co., Ltd., “AEROSIL 300”) as an inorganic compound A surface coating material blended at the ratio was prepared.

(Example 10)
As a nitrogen-containing fluorine-based compound, 10 parts by mass of “2- [3-[[perfluoro (2-methyl-3-dibutylaminopropanoyl)] amino] propyl-dimethyl-ammonium] acetate obtained in Synthesis Example 1 was used. 1 L was uniformly dispersed, and 3 parts by mass of fumed silica (manufactured by Nippon Aerosil Co., Ltd., “AEROSIL300”) and 3 parts by mass of polyferric sulfate (“Polytec”, manufactured by Nittetsu Mining Co., Ltd.) were added. The precipitated solid was collected by filtration under reduced pressure and dried to obtain 9.6 parts by mass of a hydrophilic oil-repellent complex. A surface coating material was prepared by blending 2 parts by mass of the obtained composite and 1 part by mass of polyvinyl butyral (Sekisui Chemical Co., Ltd., “ESREC BL-1”) as a binder with 97 parts by mass of chloroform.

(Example 11)
As a nitrogen-containing fluorine-based compound, 2 parts by mass of 2- [3-[[perfluoro (2-methyl-3-piperidinonopropanoyl)] amino] propyl-dimethyl-ammonium] acetate obtained in Synthesis Example 2 was added to water. Uniformly dispersed in 400 mL, 7 parts by mass of silica sol (“organosilica sol IPA-ST”, manufactured by Nissan Chemical Co., Ltd .: 30% silica) was added. Water was distilled off from the dispersion, and the residue was dried to obtain 4 parts by mass of a hydrophilic oil-repellent complex. A surface covering material was prepared by blending 4 parts by mass of the obtained composite and 2 parts by mass of polyvinyl butyral (Sekisui Chemical Co., Ltd., “ESREC BL-1”) into 94 parts by mass of chloroform as a binder.

(Example 12)
As a nitrogen-containing fluorine-based compound, 2 parts by mass of perfluoro (3-dibutylaminopropionic acid) calcium obtained in Synthesis Example 3, 4 parts by mass of organic bentonite (“Esben W” manufactured by Hojun Co., Ltd.), polyvinyl as a binder A surface coating material was prepared by blending 4 parts by mass of butyral (Sekisui Chemical Co., Ltd., “ESREC BL-1”) and 90 parts by mass of ethanol as a solvent.

(Example 13)
As a nitrogen-containing fluorine-based compound, 4 parts by mass of 3-[[perfluoro (3-dibutylaminopropanoyl)] amino] propyl-trimethyl-ammonium iodide obtained in Synthesis Example 4, fumed silica (manufactured by Nippon Aerosil Co., Ltd.) , “AEROSIL300”), 4 parts by weight of polyvinyl butyral (Sekisui Chemical Co., Ltd., “ESREC BL-1”) as a binder, and 88 parts by weight of ethanol as a solvent were prepared. .

(Example 14)
As a nitrogen-containing fluorine-based compound, 0.5 mass of 3- [3-[[perfluoro (2-methyl-3-dibutylaminopropanoyl)] amino] propyl-dimethyl-ammonium] propanesulfonate obtained in Synthesis Example 5 was used. Parts, 0.5 parts by mass of organosilica sol (manufactured by Nissan Chemical Co., “IPA-ST”) as an inorganic compound, and 1 part by mass of polyvinyl butyral (manufactured by Sekisui Chemical Co., Ltd., “S-Rec BL-1”) as a binder. A surface coating material was prepared by blending 55 parts by mass of hexafluoro-m-xylene as a solvent, 37 parts by mass of ethanol, 5 parts by mass of n-butanol, and 1 part by mass of isopropyl alcohol.

(Example 15)
As a nitrogen-containing fluorine compound, 0.5 part by mass of 4- [3-[[perfluoro (2-methyl-3-dibutylaminopropanoyl)] amino] propyl-dimethyl-ammonium butanesulfonate obtained in Synthesis Example 6 was used. In addition, 0.5 part by mass of organosilica sol (manufactured by Nissan Chemical Co., "IPA-ST") as an inorganic compound, 1 part by mass of polyvinyl butyral (manufactured by Sekisui Chemical Co., Ltd., "S Lec BL-1") as a binder, A surface coating material was prepared by mixing 55 parts by mass of hexafluoro-m-xylene as a solvent, 37 parts by mass of ethanol, 5 parts by mass of n-butanol, and 1 part by mass of isopropyl alcohol.

(Example 16)
As a nitrogen-containing fluorine-based compound, 3- [3-[[perfluoro (2-methyl-3-dibutylaminopropanoyl)] amino] propyl-dimethyl-ammonium] 2-hydroxypropane-1- obtained in Synthesis Example 7 was used. 0.5 parts by mass of sulfonate, 0.5 parts by mass of organosilica sol (manufactured by Nissan Chemical Co., “IPA-ST”) as an inorganic compound, and polyvinyl butyral (Sekisui Chemical Co., Ltd., “ESREC BL-1” as a binder) 1) parts by mass, 55 parts by mass of hexafluoro-m-xylene as a solvent, 37 parts by mass of ethanol, 5 parts by mass of n-butanol, and 1 part by mass of isopropyl alcohol are produced. did.

(Comparative Example 1)
As a nitrogen-containing fluorine-based compound, 4 parts by mass of “2- [3-[[perfluoro (2-methyl-3-dibutylaminopropanoyl)] amino] propyl-dimethyl-ammonium] acetate obtained in Synthesis Example 1, A surface coating material was prepared by blending 16 parts by mass of polyvinyl butyral (Sekisui Chemical Co., Ltd., “ESREC BL-1”) as a binder and 80 parts by mass of ethanol as a solvent.

(Comparative Example 2)
4 parts by mass of fumed silica (manufactured by Nippon Aerosil Co., Ltd., “AEROSIL300”), 16 parts by mass of polyvinyl butyral (Sekisui Chemical Co., “ESREC BL-1”) as a binder, and 80 parts by mass of ethanol as a solvent A liquid mixture was prepared by mixing and fully dispersing.

(Comparative Example 3)
Bentonite (“Bengel”, manufactured by Hojun Co., Ltd.) 1.5 parts by mass, 8 parts by mass of Eslec B (BL-1) as a binder, and 90.5 parts by mass of ethanol as a solvent are sufficiently dispersed. A mixed liquid was prepared.

<Evaluation by contact angle measurement>
The contact angle measurement (droplet method) was performed on the coating films obtained from the surface coating materials of the examples and comparative examples.
Specifically, an automatic film applicator (Yasuda Seiki) was applied to the surface coating materials of Examples 1 to 16 and Comparative Examples 1 to 3 on a PET film (TORAY, “Lumirror 100T60”) having a width of 240 mm × length of 297 mm × thickness of 100 μm. Seisakusho, “No. 542-AB”) and After coating using a 6 bar coater (“R.D.S. Webster”, manufactured by NY), the coating film was obtained by drying at 60 to 70 ° C. for 5 to 10 minutes.

  Water and n-hexadecane (hereinafter referred to as oil) are dropped on the obtained coating film, and the angle formed at the contact portion between the coating film and the droplet on the PET film (static contact angle, unit) : ° (degree), 1 ° = (π / 180) rad) was measured with an automatic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., “Drop Master 701”).

In addition, the following conditions were used as a dripping method of water and n-hexadecane.
Drop volume: 2 μL / drop (water)
Drop volume: 2 μL / drop (n-hexadecane)
Measurement temperature: Room temperature (22 ± 1 ° C)

Here, it can be said that the lower the static contact angle value of water is, the better the hydrophilicity is, and the higher the static contact angle value of oil is, the easier it is to play oil, that is, excellent oil repellency.
Therefore, in the evaluation of hydrophilic oil repellency, when the contact angle measurement shows that the static contact angle of water with respect to the coating film (coating film) is 40 ° or less and the static contact angle of n-hexadecane is 40 ° or more. The nitrogen-containing fluorine-based compound has hydrophilic oil repellency (that is, the complex of the nitrogen-containing fluorine-based compound and the inorganic compound is a hydrophilic oil-repellent complex). The results are shown in Tables 1 and 2 below.

  Furthermore, flowing water was directly applied to the coating film, and the contact angle between water and oil after 1 hour was measured to evaluate the durability (durability) of hydrophilic oil repellency. The results are shown in Tables 1 and 2 below.

  As shown in Table 1 and Table 2, as a result of the contact angle measurement in Examples 1 to 16, the static contact angle of water is 40 ° or less in the initial performance for any coating film (coating film), and As for the static contact angle of n-hexadecane, excellent oil repellency of 60 ° or more was exhibited, and almost no deterioration from the initial performance was observed even after 1 hour of flowing water. Therefore, it was confirmed that the hydrophilic and oil-repellent coating films obtained by the surface coating materials of Examples 1 to 16 have excellent hydrophilic and oil-repellent properties and durability.

  On the other hand, since Comparative Example 2 and Comparative Example 3 did not contain a nitrogen-containing fluorine-based compound that exhibits hydrophilic oil repellency, hydrophilic oil repellency was not obtained from the initial performance stage.

  Moreover, since Comparative Example 1 contains a nitrogen-containing fluorine-based compound that exhibits hydrophilic oil repellency, the initial static contact angle of water is 40 ° or less and the static contact angle of n-hexadecane is 40 ° or more. Showed performance. However, since the nitrogen-containing fluorine-based compound is not complexed with the inorganic compound, it was confirmed that the hydrophilicity after 1 hour of flowing water decreases.

<Evaluation by oil-water separation test>
2.1 g of 2- [3-[[perfluoro (2-methyl-3-dibutylaminopropanoyl)] amino] propyl-dimethyl-ammonium] acetate obtained in Synthesis Example 1 and polyvinyl butyral (manufactured by Sekisui Chemical, “ A solution obtained by dissolving 2.0 g of ESREC BL-1 ") in a mixed solvent of 240 g of hexafluoroxylene, 160 g of ethanol and 20 g of n-butanol was obtained. Next, 7.1 g of silica sol (manufactured by Nissan Chemical Co., “IPA-ST”: solid content 30%) was added to the obtained solution and dispersed uniformly to prepare a surface coating material. Next, a circular polypropylene non-woven fabric (weight per unit: 20 g / m ² , thickness: 0.21 mm) having a diameter of 47 mm is immersed in the adjusted surface covering material, dried at 60 ° C., and then an atmospheric pressure filtration device. The oil-water separation test was conducted in As a test solution, a mixed solution of 30 mL of water and 5 mL of n-hexadecane was used.

  As a result of supplying the test solution to the atmospheric pressure filtration apparatus by shaking well, water passed through the nonwoven fabric vigorously, but n-hexadecane could not pass through the nonwoven fabric, and the oily water was completely separated in about 60 seconds.

  The hydrophilic oil-repellent composite of the present invention, its dispersion and solution can impart hydrophilic oil-repellency. Therefore, it can be applied to a coating film having an antifouling function, an oil-water separation filter medium, and the like, and has industrial applicability.

Claims (15)

A hydrophilic oil-repellent complex comprising one or more nitrogen-containing fluorine-based compounds represented by the following formulas (1) to (4) and an inorganic compound having a charge or an ionic group.




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 , Rf ^5, and Rf ⁶ are the same or different from each other, each having 1 to 6 carbon atoms and a linear or branched perfluoroalkylene group. Z includes any of an oxygen atom, a nitrogen atom, a CF ₂ group, and a CF group.
Moreover, in said formula (2) and (4), R is a coupling group which is a bivalent organic 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 hydrophilic oil-repellent complex according to claim 1, wherein the inorganic compound is one or a mixture of two or more of the group consisting of fumed silica, colloidal silica, mullite, alumina, and zeolite.   The hydrophilic oil-repellent complex according to claim 1, wherein the inorganic compound is one or a mixture of two or more of the group consisting of bentonite, organic bentonite, smectite, and kaolinite.   The hydrophilic oil-repellent complex according to claim 1, wherein the inorganic compound is one or a mixture of two or more of the group consisting of polyaluminum chloride, polyferric sulfate, and aluminum sulfate.   The water / oil repellent composite according to any one of claims 1 to 4, wherein a mass composition ratio of the nitrogen-containing fluorine-based compound and the inorganic compound is in a range of 1 to 99 to 99-1. It is a manufacturing method of the hydrophilic oil-repellent complex according to claim 1,
After applying a coating solution in which the nitrogen-containing fluorine-based compound and the inorganic compound are dissolved or dispersed in any one of water, an organic solvent, or a mixed solvent of water and an organic solvent, A method for producing a hydrophilic oil-repellent complex, wherein the complex is obtained by removing water, the organic solvent or the mixed solvent. It is a manufacturing method of the hydrophilic oil-repellent complex according to claim 1,
A solid was obtained by filtration from a solution in which the nitrogen-containing fluorine-based compound and the inorganic compound were dispersed in any one of water, an organic solvent, or a mixed solvent of water and an organic solvent. A method for producing a hydrophilic oil-repellent composite, wherein the solid is dried to obtain the composite. It is a manufacturing method of the hydrophilic oil-repellent complex according to claim 1,
After dissolving or dispersing the nitrogen-containing fluorine-based compound and the inorganic compound in any one of water, an organic solvent, or a mixed solvent of water and an organic solvent, the water, the organic solvent, or the mixed solvent A method for producing a hydrophilic oil-repellent complex, wherein the residue obtained by distilling off is dried to obtain the complex. The hydrophilic oil-repellent composite according to claim 1,
Any one of water, an organic solvent, or a mixed solvent of water and an organic solvent,
The surface covering material whose mass composition ratio of the nitrogen-containing fluorine-type compound in the said hydrophilic oil-repellent complex and the said solvent is the range of 0.2-50 to 50-99.8. Further including a binder,
The mass composition ratio between the nitrogen-containing fluorine-based compound and the binder in the hydrophilic oil-repellent composite is in the range of 0.2 to 99.9 to 99.8 to 0.1. Surface covering material.   The surface covering material according to claim 10 in which said binder contains either resin, water-soluble resin, or water glass.   A coating film comprising the hydrophilic oil-repellent complex according to claim 1. Further including a binder,
The mass composition ratio between the nitrogen-containing fluorine-based compound and the binder in the hydrophilic oil-repellent complex is in the range of 0.2 to 99.9 to 99.8 to 0.1. Coating film. A hydrophilic oil-repellent complex according to claim 1 and a resin,
The resin composition whose mass composition ratio of the nitrogen-containing fluorine-type compound in the said hydrophilic oil-repellent complex and the said resin is the range of 0.2-99.9 vs. 99.8-0.1.   An oil-water separation filter medium comprising the coating film according to claim 12 or the resin composition according to claim 14.