JP6944244B2 - Fluorine-containing polymerizable compounds, fluorine-containing polymers, and surface treatment agents - Google Patents

Description

The present invention relates to fluorinated polymerizable compounds, fluorinated polymers, and surface treatment agents.

As a method for preventing oil stains on an article, a method of coating the surface of the article with an oil-repellent surface coating material is known. As the surface coating material having oil repellency, a fluororesin which is a polymer of a hydrocarbon containing fluorine such as polytetrafluoroethylene (PTFE) and polychlorotrifluoroethylene is widely used. However, since fluororesin has high water repellency, there is a problem that it is difficult to wash away oil stains adhering to the surface of an article by washing with water. Therefore, a surface coating material having oil repellency for preventing oil stains and hydrophilicity for washing the adhered oil stains with water is desired.

Patent Document 1 describes, as a resin composition having hydrophilicity, oil repellency and water-sliding property, a copolymer containing a perfluoroalkyl (meth) acrylic acid ester having 1 to 18 carbon atoms and a hydrophilic group-containing monomer as constituent components. The resin composition blended in is disclosed.

Japanese Unexamined Patent Publication No. 2008-297482

Since the copolymer disclosed in Patent Document 1 contains a hydrophilic group-containing monomer as a constituent component, hydrophilicity is improved, but it is oil-repellent as compared with a fluororesin typified by polytetrafluoroethylene (PTFE). Tended to be low.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a novel material and a surface treatment agent having excellent hydrophilicity and oil repellency.

The inventor of the present invention has a fluoropolymerizable group having a polymerizable group containing an ethylenically unsaturated bond, a perfluoroalkyl group, and a betaine-type functional group in which a cationic group and an anionic group are bonded in one molecule. The present invention has been completed by finding that the compound and the fluorine-containing polymer having a structural unit derived from this fluorine-containing polymerizable compound have excellent hydrophilicity and oil repellency.

That is, the present invention has the following configuration.
[1] A fluorine-containing polymerizable compound represented by the following general formula (1).

In the above general formula (1), R represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and Rf is a linear or branched perfluoro having 1 to 6 carbon atoms. Represents an alkyl group, X represents a divalent linking group having one or more oxygen atoms, L represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and an oxygen atom. , A carbonyl group, an imino group which may have a substituent, or a divalent linking group consisting of a combination thereof, M represents a cationic group having one or more nitrogen atoms, and Q represents an anionic group. Represents.

[2] The fluorine-containing polymerizable compound according to item 1 above, wherein X is a linking group represented by the following general formula (2).

In the above general formula (2), * ¹ represents a bond that binds to C of C = O of the general formula (1), and * ² binds to C of CH of the general formula (1). A bond is represented, m represents an integer of 0 to 4, and n represents an integer of 0 or 1.

[3] The above item 1, wherein the M is a cationic group represented by any one of the following general formulas (3), (4), (5) and (6). Fluorine-containing polymerizable compound.

In the above general formulas (3), (4), (5) and (6), R ¹ represents a linear or branched alkyl group having 1 to 12 carbon atoms, and * ³ is the general formula. _{The bonder that binds to C of CH 2} of (1) is represented, and * ⁴ represents the bonder that binds to Q of the general formula (1).

[4] The fluorine-containing polymerizable compound according to item 1 above, wherein the Q is an anionic group represented by the following general formula (7).

In the above general formula (7), Y represents a divalent hydrocarbon group which may have a substituent group having 1 to 10 carbon atoms, Z _is, ^-CO 2 -, -SO ₃ ^-, or −PO ₃ ^{− −} R ² , where R ² represents a linear or branched alkyl group having 1 to 12 carbon atoms, and * ⁵ is a bond that binds to M in the general formula (1). Represents.

[ 5 ] The first constitutional unit having a first constitutional unit derived from the fluoropolymerizable compound according to any one of the above items 1 to 4 and a constitutional unit other than the first constitutional unit. The structural unit other than the unit is one of a polymerizable group containing an ethylenically unsaturated bond , an anionic hydrophilic group, a cationic hydrophilic group, an amphoteric hydrophilic group, and a nonionic hydrophilic group. of I binary copolymer der a structural unit derived from a polymerizable compound having a hydrophilic group, the contact angle with water is 40 degrees or less, the contact angle with hexadecane 30 ° or more fluoropolymer, characterized in der Rukoto.

[ 6 ] A surface treatment agent containing the fluorine-containing polymer according to item 5 above and a liquid medium.

According to the present invention, it is possible to provide a novel material and a surface treatment agent having excellent hydrophilicity and oil repellency.

Hereinafter, a fluorinated polymerizable compound, a fluorinated polymer, and a surface treatment agent, which are embodiments to which the present invention is applied, will be described in detail.

<Fluorine-containing polymerizable compound>
The fluorine-containing polymerizable compound of this embodiment is represented by the following general formula (1).

The fluorine-containing polymerizable compound of the present embodiment represented by the above general formula (1) is _{polymerizable including an ethylenically unsaturated bond represented by H 2} C = C (−R) −C (= O) −. Has a group.

In the above general formula (1), R represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. R is preferably a hydrogen atom or a methyl group.

In the above general formula (1), Rf represents a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms.

In the above general formula (1), X is a divalent linking group having one or more oxygen atoms. The divalent linking group is a divalent hydrocarbon group which may have a substituent having 1 to 10 carbon atoms, a carbonyl group, an imino group which may have a substituent, or a combination thereof, or a combination thereof. It may have a combination of these with an oxygen atom. The divalent hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Further, the divalent hydrocarbon group may be a chain hydrocarbon group or a cyclic hydrocarbon group. Examples of the divalent hydrocarbon group include an alkylene group, an alkenylene group, an alkynylene group, an arylene group and a combination thereof. Examples of the substituent that the hydrocarbon group and the imino group may have include a hydroxy group, an alkyl group, and an alkoxy group. The alkyl group and the alkoxy group preferably have 1 to 4 carbon atoms.

Examples of X in the above general formula (1) include an oxygen atom alone (ether bond: −O−), a combination of an alkylene group and an oxygen atom, and a combination of an oxygen atom and a carbonyl group (ester bond: −OC (ester bond: −O−). = O)-), combination of carbonyl group and imino group (amide bond: -C (= O) -NH-), combination of carbonyl group, imino group and oxygen atom (urethane bond: -C (= O) -NH -O-) can be mentioned. Further, two or more of these combinations may be further combined.

It is preferable that X in the above general formula (1) is a divalent linking group represented by the following general formula (2).

In the above general formula (2), * ¹ represents a bond that binds to C of C = O of the general formula (1), and * ² binds to C of CH of the general formula (1). Represents a bond.
m represents an integer of 0 to 4, and n represents an integer of 0 or 1.

In the above general formula (1), L may have a divalent hydrocarbon group which may have a substituent having 1 to 10 carbon atoms, an oxygen atom, a carbonyl group, and an imino which may have a substituent. Represents a divalent organic group consisting of a group or a combination thereof. Examples of the substituents that the hydrocarbon group, the hydrocarbon group and the imino group may have are the same as in the case of X described above. L is preferably an alkylene group which may have a substituent having 1 to 10 carbon atoms, or a combination of an alkylene group which may have a substituent having 1 to 10 carbon atoms and an oxygen atom. .. The combination of the alkylene group and the oxygen atom, which may have a substituent having 1 to 10 carbon atoms, is particularly preferably a combination of -alkylene group-oxygen atom-alkylene group-.

In the above general formula (1), M represents a cationic group having one or more nitrogen atoms. Q represents an anionic group. The cationic group represented by M and the anionic group represented by Q are bonded to form a betaine-type functional group.

The cationic group represented by M in the above general formula (1) means a group that becomes a cation when dissolved in water. The nitrogen atom of the cationic group forms a cation. M is preferably a cationic group represented by any one of the following general formulas (3), (4), (5) and (6).

In the above general formulas (3), (4), (5) and (6), R ¹ represents a linear or branched alkyl group having 1 to 12 carbon atoms. R ¹ is preferably a methyl group.
* ³ represents a bond that binds to C of CH of the general formula (1), and * ⁴ represents a bond that binds to Q of the general formula (1).

The anionic group represented by Q in the general formula (1) above means a group that becomes an anion when dissolved in water. The anionic group may include −CO ₂ ⁻ , _{− SO 3} ⁻ , or −PO ₃ ^{− −} R ² (R ² represents a linear or branched alkyl group having 1 to 12 carbon atoms). preferable. Q is preferably an anionic group represented by the following general formula (7).

In the above general formula (7), Y represents a divalent hydrocarbon group which may have a substituent having 1 to 10 carbon atoms.

In the above general formula (7), Z is −CO ₂ −, − SO ₃ ⁻ , or −PO ₃ ^{− −} R ² , and R ² is a linear or branched form having 1 to 12 carbon atoms. Represents the alkyl group of.
* ⁵ represents a bond that binds to M in the general formula (1).

Specific examples of the fluorine-containing polymerizable compound of the present embodiment include compounds represented by the following formulas.

Next, a method for synthesizing the fluorine-containing polymerizable compound of the present embodiment will be described.
The fluorine-containing polymerizable compound of the present embodiment can be synthesized, for example, by the following method.

A perfluoroalkyl group-containing epoxy compound represented by the following general formula (22) is prepared.

In the above general formula (22), Rf and L are the same as the above general formula (1).

The above-mentioned perfluoroalkyl group-containing epoxy compound is reacted with an amine compound having at least one secondary amino group to obtain a group containing a perfluoroalkyl group and a tertiary amino group represented by the following general formula. The alcohol compound (A) having the above is obtained. Examples of amine compounds include 1-methylpiperazine, 3- (dimethylamino) pyrrolidine, dimethylamine, 1-methyl-4- [1- (4-piperidyl) -4-piperidyl] piperazine.

In the general formula of the alcohol compound (A), Rf and L are the same as those in the general formula (1), and M ¹ represents a group containing a tertiary amino group.

Next, the above alcohol compound (A) is reacted with a quaternary chloride agent to quaternarily chloride the tertiary amino group of the alcohol compound (A), whereby a perfluoroalkyl group represented by the following general formula is formed. An alcohol compound (B) having (Rf) and a betaine-type functional group to which a cationic group (M) and an anionic group (Q) are bonded is obtained. Examples of the quaternary chloride agent include 1,3-propane sultone, 1,4-butane sultone, and sodium chloroacetate.

In the general formula of the alcohol compound (B), Rf, L, M and Q are the same as the general formula (1).

Finally, the object is achieved by reacting the above alcohol compound (B) with a polymerizable compound having a polymerizable group containing an ethylenically unsaturated bond and reacting with the hydroxy group of the alcohol compound (B). The fluorine-containing polymerizable compound represented by the general formula (1) can be obtained. Examples of the polymerizable group of the polymerizable compound include an acryloyl group. The acryloyl group may be substituted with an alkyl group having 1 to 4 carbon atoms. Examples of polymerizable compounds include isocyanates, carboxylic acids and carboxylic acid halides.

As described above, the fluorine-containing polymerizable compound of the present embodiment is a betaine type in which a polymerizable group containing an ethylenically unsaturated bond, a perfluoroalkyl group, and a cationic group and an anionic group are bonded in one molecule. It has a functional group of. The fluorine-containing polymerizable compound of the present embodiment exhibits excellent hydrophilicity and oil repellency by the perfluoroalkyl group acting as an oil-repellent group and the betaine-type functional group acting as a hydrophilic group. It can be used as an oil repellent. In addition, the fluorine-containing polymerizable compound of the present embodiment can be used as a material for the fluorine-containing polymer described later.

<Fluorine-containing polymer>
The fluorinated polymer of the present embodiment has a first structural unit derived from the above-mentioned fluorinated polymerizable compound. That is, it has a structural unit in which the ethylenically unsaturated bond of the fluorine-containing polymerizable compound represented by the above general formula (1) is cleaved.

The fluorine-containing polymer of the present embodiment may have a structural unit other than the above-mentioned first structural unit. That is, the fluorine-containing polymer is a copolymer having a structural unit (second structural unit) derived from a polymerizable compound copolymerizable with the fluorine-containing polymerizable compound represented by the above general formula (1). There may be. The copolymer may be a block copolymer, a random copolymer, or an alternating copolymer.

The second structural unit may be a structural unit derived from a fluorine-containing polymerizable compound other than the fluorine-containing polymerizable compound represented by the above-mentioned general formula (1), or may be a non-fluorine-containing non-fluorine-containing compound containing no fluorine atom. It may be a structural unit derived from a polymerizable compound.

Examples of the fluoropolymerizable compound other than the fluoropolymerizable compound represented by the above general formula (1) include a polymerizable compound having a polymerizable group containing an ethylenically unsaturated bond and a perfluoroalkyl group. can. Examples of polymerizable groups containing ethylenically unsaturated bonds include (meth) acryloyl groups and (meth) acryloyloxy groups. The perfluoroalkyl group may be linear or branched. The perfluoroalkyl group preferably has 1 to 6 carbon atoms. The polymerizable group containing an ethylenically unsaturated bond and the perfluoroalkyl group may be directly linked or may be bonded via a linking group. Examples of the linking group include an alkylene group having 1 to 10 carbon atoms, an oxygen atom, a carbonyl group, an imino group which may have a substituent, and a combination thereof.

Examples of the non-fluorine-containing polymerizable compound containing no fluorine atom include a polymerizable compound having a polymerizable group containing an ethylenically unsaturated bond and a hydrophilic group. Examples of polymerizable groups containing ethylenically unsaturated bonds include (meth) acryloyl groups and (meth) acryloyloxy groups. As the hydrophilic group, an anionic type hydrophilic group, a cationic type hydrophilic group, an amphoteric type hydrophilic group, and a non-ionic type hydrophilic group can be used.

Examples of anionic hydrophilic groups are groups represented by _{"-CO 2} M ¹ " or "-SO ₃ M ^{1 " (where M 1} is an alkali metal, alkaline earth metal, Mg, Al, R ³ R ⁴ R ⁵ R ⁶ N ⁺ : R ³ , R ⁴ , R ⁵ and R ⁶ are independently hydrogen atoms or linear or branched alkyl groups having 1 to 20 carbon atoms). be able to.
Examples of hydrophilic cationic, ^{"- N + R 7 R 8 R} 9 · Cl - ," ^{"- N + R 7 R 8 R} 9 · Br - ," ^{"- N + R 7 R 8 R} 9・ I ⁻ ”,“ −N ⁺ R ⁷ R ⁸ R ⁹ · CH ₃ SO ₃ ⁻ ”,“ −N ⁺ R ⁷ R ⁸ R ⁹ · NO ₃ ⁻ ”,“ (−N ⁺ R ⁷ R ⁸ R ⁹ ) ₂ CO ₃ ^2- "or" (-N ⁺ R ⁷ R ⁸ R ⁹ ) ₂ SO ₄ ^2- "(where R ⁷ , R ⁸ and R ⁹ are independent hydrogen atoms, respectively. Alternatively, it is a linear or branched alkyl group having 1 to 20 carbon atoms).
Examples of the hydrophilic group of the amphoteric type, carboxy betaine type _{^{"-N + R 10 R 11 (CH}} 2) a CO 2 - ", sulfobetaine type _{^{"-N + R 10 R 11 (CH}} 2) a SO ₃ ^- "or amine oxide type" ^-N + ^R 10 ^{R 11} O ^- group represented by "(where, a is an integer of ^{1-5, R 10} and ^{R 11} are each independently a hydrogen atom Alternatively, it is an alkyl group having 1 to 10 carbon atoms).
Examples of nonionic hydrophilic groups _{include polyoxyethylene groups represented by "-(CH 2-} CH _2- O) _b- R ¹² " and "-(CH _2- CH ((CH ₃ ) -O) -O". ) polyoxypropylene group represented by _c -R ^{12 '(wherein,} a linear or branched alkyl group of ^{R 12} a hydrogen atom or a c 1 to 20, b is an integer of 2 to 20, c Is an integer of 2 to 20).

The polymerizable group containing an ethylenically unsaturated bond and the hydrophilic group may be directly linked or may be bonded via a linking group. Examples of the linking group include an alkylene group having 1 to 10 carbon atoms, an oxygen atom, a carbonyl group, an imino group which may have a substituent, and a combination thereof. Specific examples of the polymerizable compound having a polymerizable group containing an ethylenically unsaturated bond and a hydrophilic group include sodium (meth) acrylate, potassium (meth) acrylate, and potassium 3-sulfopropyl (meth) acrylate. , Methyl chloride quaternary ammonium salt of dimethylaminoethyl (meth) acrylate, Methyliodide quaternary ammonium salt of dimethylaminoethyl (meth) acrylate, [2- (methacryloyloxy) ethyl] dimethyl- (3-sulfopropyl) ammonium Hydroxide, [3- (methacryloylamino) propyl] dimethyl- (3-sulfobutyl) ammonium hydroxide, N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-carboxybetaine, polyethylene glycol (meth) acrylate, Examples thereof include, but are not limited to, methoxypolyethylene glycol (meth) acrylate.

Further, as the non-fluorine-containing polymerizable compound, a polymerizable compound having a group for improving adhesion to an article to which a fluorine-containing copolymer is applied, and a polymerizable compound having a group for improving solubility in an organic solvent can be used. can. Examples of the group that improves the adhesion to the article and the solubility in the solvent include a hydroxyl group, an amino group, a carboxyl group, a glycidyl group, a silyl group and an isocyanato group. Examples of polymerizable compounds are 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl vinyl ether, diethylaminoethyl (meth). Acrylate, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, maleic anhydride, citraconic anhydride, glycidyl (meth) acrylate, allylglycidyl ether, 3- (trimethoxysilyl) propyl (meth) acrylic acid, ( Examples thereof include 3- (triethoxysilyl) propyl acrylate, 2-isocyanate ethyl (meth) acrylate and the like.

The fluorinated polymer of the present embodiment may have a structural unit derived from a polyfunctional (meth) acrylate and / or a polyfunctional urethane (meth) acrylate. The building blocks derived from the polyfunctional (meth) acrylate and / or the polyfunctional urethane (meth) acrylate have the effect of cross-linking the other building blocks two-dimensionally or three-dimensionally. Therefore, a hydrophilic oil-repellent copolymer having a structural unit derived from a polyfunctional (meth) acrylate and / or a polyfunctional urethane (meth) acrylate has adhesion to a substrate, elution resistance to a solvent, and hydrophilicity. The durability of oil repellency and antifouling property can also be improved as needed by various properties such as hardness and feel.

The polyfunctional (meth) acrylate is an organic compound having two or more, preferably 2 to 4 (meth) acryloyloxy groups in one molecule. Examples of polyfunctional (meth) acrylates include 2-hydroxy-3-acryloyloxypropyl methacrylate, polyethylene glycol diacrylate, ethoxylated bisphenol A diacrylate, 9,9-bis [4- (2-acryloyloxyethoxy)]. Phenyl] Fluorene, Tricyclodecanedimethanol Diacrylate, 1,10-Decandiol Diacrylate, 1,6-Hexanediol Diacrylate, Dipropylene Glycol Diacrylate, Pentaerythritol Triacrylate, Trimethylol Propanetriacrylate, Pentaerythritol Tetra Acrylate, N, N'-methylenebisacrylamide, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, glycerin dimethacrylate, polypropylene glycol dimethacrylate, trimethyl propantrimethacrylate, Examples thereof include ethoxylated isocyanuric acid triacrylate.

The polyfunctional urethane (meth) acrylate has two or more, preferably 2 to 4 (meth) acryloyloxy groups and one or more urethane bonds (-O-CO-NH-) in one molecule. It is an organic compound. Examples of polyfunctional urethane (meth) acrylates include phenylglycidyl ether acrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate toluene diisocyanate urethane prepolymer, and dipentaerythritol pentaacrylate hexa. Examples thereof include methylene diisocyanate urethane prepolymer. These polyfunctional (meth) acrylates and polyfunctional urethane (meth) acrylates may be used alone or in combination of two or more. These polyfunctional (meth) acrylates and polyfunctional urethane (meth) acrylates are commercially available from Shin-Nakamura Chemical Co., Ltd., Kyoeisha Chemical Co., Ltd., and the like.

The content of the structural unit derived from the polyfunctional (meth) acrylate and / or the polyfunctional urethane (meth) acrylate is preferably in the range of 0.1 mol% or more and 10 mol% or less, preferably 0.1 mol%. It is more preferably in the range of 5 mol% or more. If the content of this structural unit is too small, the above-mentioned effects may not be obtained. On the other hand, if the content of this structural unit is too large, the content of other structural units may be relatively small, and properties such as hydrophilicity and oil repellency may be deteriorated.

Next, a method for synthesizing the fluorine-containing polymer of the present embodiment will be described.
The fluorine-containing polymer of the present embodiment is, for example, a fluorine-containing polymerizable compound represented by the above-mentioned general formula (1) in the presence of a polymerization initiator (catalyst), and, if necessary, other polymerizable compounds. Can be synthesized by polymerizing. As the polymerization method, any method such as a suspension polymerization method, an emulsion polymerization method, and a solution polymerization method can be used.

Examples of the polymerization initiator include azobisisobutyronitrile, 2,2'-azobis (propane-2-carboamidine) / dihydrochloride, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, and cumene. Hydroperoxide, t-butylperoxypivalate, diisopropylperoxydicarbonate, benzoyl peroxide, lauroyl peroxide, t-butylperbenzoate, 1-hydroxycyclohexylhydroperoxide, 3-carboxypropionyl peroxide, peroxide Examples thereof include acetyl oxide, sodium peroxide, potassium persulfate, and ammonium persulfate. One of these polymerization initiators may be used alone, or two or more thereof may be mixed and used in an arbitrary ratio.

When an organic solvent is used for the polymerization, the organic solvent is not particularly limited as long as it is inert to the polymerizable compound and dissolves them. Examples of such an organic solvent include alcohols such as methanol, ethanol, isopropyl alcohol and trifluoroethanol, acetone, chloroform, HCHC-225, isopropyl alcohol, pentane, hexane, heptane, octane, cyclohexane, benzene and toluene. Xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichlorethylene, perchloroethylene, Examples thereof include tetrachlorodifluoroethane and trichlorotrifluoroethane. One type of organic solvent may be used alone, or two or more types may be mixed and used in an arbitrary ratio. The organic solvent is preferably used in the range of 50 to 2000 parts by mass, and more preferably in the range of 50 to 1000 parts by mass with respect to 100 parts by mass of the total amount of the monomer.

A chain transfer agent may be added to the organic solvent as an optional component. Examples of chain transfer agents include thiol-based agents such as mercaptoethanol, mercaptoacetic acid, stearyl mercaptan, and t-dodecyl mercaptan, phosphite, hypophosphoric acid and salts thereof (sodium hypophosphate, potassium hypophosphite, etc.). ) Etc., and secondary alcohols such as isopropyl alcohol can be mentioned.

The fluorine-containing polymer of the present embodiment is a first structural unit derived from the fluorine-containing polymerizable compound represented by the above-mentioned general formula (1), that is, an oil-repellent group having a perfluoroalkyl group in the side chain. And a hydrophilic group having a betaine structure. Therefore, the fluorine-containing polymer of the present embodiment has excellent oil repellency and hydrophilicity.

<Surface treatment agent>

The surface treatment agent of the present embodiment includes the above-mentioned fluorine-containing polymer and a liquid medium. Examples of the liquid medium include organic solvents, water, and mixtures thereof. Examples of organic solvents include alcohol solvents such as methanol, ethanol, isopropyl alcohol and trifluoroethanol, ketone solvents such as acetone and methyl ethyl ketone, ester solvents such as ethyl acetate and butyl acetate, α, α and α-tri. Fluorosolvents such as fluorotoluene, 1,3-bistrifluoromethylbenzene, 1,4-bistrifluoromethylbenzene, perfluorooctane, and perfluorohexane can be mentioned. The surface treatment agent is preferably in the form of a solution, emulsion, or aerosol. The concentration of the nitrogen-containing copolymer of the surface treatment agent is generally in the range of 0.01 to 50% by weight.

Next, a method of using the surface treatment agent of the present embodiment, that is, a method of surface treatment on the object to be treated (base material) will be described.

(Processed object)
The objects to be treated with the surface treatment agent of the present embodiment include fibers or textile products, asbestos, filters (for example, electrostatic filters), dustproof masks, fuel cell parts (for example, gas diffusion electrodes and gas diffusion supports). Body), wood, leather, fur, asbestos, metals and oxides, ceramic products (eg, glass, brick, cement), plastics, paints or plastered coated surfaces.

Various examples can be given as the fiber. Specifically, for example, animal and vegetable natural fibers such as cotton, hemp, wool and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride and polypropylene, and semi-synthetic fibers such as rayon and acetate. Inorganic fibers such as glass fibers and carbon fibers, or mixed fibers thereof can be mentioned. The textile product may be in any form of woven fabric, knitted fabric or non-woven fabric, and specific products include paper, carpet, filter cloth, clothing and the like.

(Surface treatment method)
The surface treatment agent of the present embodiment is applied to an object to be treated to form a coating film, and then the coating film is dried to form a film containing a fluorine-containing polymer. The method for applying the surface treatment agent is not particularly limited, and known methods such as immersion coating, spray coating, and foam coating can be used. A method of adhering to the surface of the object to be treated and drying it is adopted. If necessary, it may be applied together with a suitable cross-linking agent for curing.

As described above, the surface treatment agent of the present embodiment contains the fluorine-containing polymer of the present embodiment. Therefore, according to the surface treatment agent of the present embodiment, the surface of the object to be treated has high hydrophilicity and oil repellency. It is possible to form a coating film having. The coating preferably has a water contact angle of 40 degrees or less and a hexadecane contact angle of 30 degrees or more.

The film containing the fluorine-containing polymer can be produced by using a coating liquid containing a fluorine-containing polymerizable compound and a liquid medium. Specifically, this coating liquid is applied to an object to be treated to form a coating film, and then a fluorine-containing polymerizable compound in the coating film is polymerized to form a film, thereby containing a fluorine-containing polymer. A coating may be produced. As a method for polymerizing the fluorine-containing polymerizable compound, a method such as heating or ultraviolet irradiation can be used.

Although the embodiments of the present invention have been described above, the technical scope of the present invention is not limited to the above-described embodiments, and various modifications can be made without departing from the spirit of the present invention.

[Example 1]
(1) Synthesis of Fluorine-Containing Polymerizable Compound 35.8 g of 1-methylpiperazine is placed in a 300 mL flask, heated to 80 ° C., and then 3- (2-perfluorohexylethoxy) -1,2-epoxypropane (Mitsubishi). Material Electronic Chemicals Co., Ltd., product name: MF-120) 100.0 g was added in 3 portions. After adding MF120, the mixture was heated to 100 ° C., stirred for 1.5 hours, and then allowed to cool to room temperature. After allowing to cool, chloroform and water were added to the reaction solution, the reaction solution was extracted into chloroform, and then the chloroform layer was separated. The separated chloroform layer was washed with brine, dried over magnesium sulfate, and the obtained solution was concentrated to obtain an alcohol compound (A-1) represented by the following formula (A-1). (111.5 g, yield 90%). The purity of the obtained alcohol compound (A-1) was measured by gas chromatography and found to be 96.7%.

^{1 1} H NMR (CDCl ₃ ): δ 2.29 (s, CH ₃ , 3H) 2.35-2.50 (m, 9H), 2.53-2.73 (m, 2H) 3.38- 3.48 (m, 2H), 3.50-3.55 (m, 1H), 3.75-3.82 (m, 2H), 3.83-3.91 (m, 1H)
_{^{19 F NMR (CDCl 3):}} δ -80.9 (CF 3, 3F), - 113.4 (CF 2, 2F), - 121.9 (CF 2, 2F), - 122.9 (CF 2, 2F), -123.7 (CF ₂ , 2F), -126.1 (CF ₂ , 2F)

Next, 29.3 g of the alcohol compound (A-1), 6.5 g of 1,3-propane sultone, and 100 mL of acetonitrile were placed in a 200 mL flask, heated to 80 ° C., and stirred for 4 hours. Then, it was allowed to cool to room temperature to precipitate crystals. Then, 100 mL of diisopropyl ether was added, and the mixture was stirred at room temperature for 15 minutes, and then the crystals were collected by filtration. The recovered crystals were dried under reduced pressure to obtain crystals (31.6 g, yield 88%) of the alcohol compound (B-1) represented by the following formula (B-1).

^{1 1} H NMR (CD ₃ OD): δ 2.17-2.26 (m, 2H) 2.40-2.65 (m, 4H) 2.80-3.01 (m, 6H), 3. 12 (s, CH ₃ , 3H), 3.42-3.58 (m, 6H), 3.58-3.66 (m, 2H), 3.75-3.83 (m, 2H), 3 .86-3.93 (m, 1H)
_{^{19 F NMR (CD 3 OD)}} : δ -82.4 (CF 3, 3F), - 114.4 (CF 2, 2F), - 122.9 (CF 2, 2F), - 123.9 (CF 2 , 2F), -124.7 (CF ₂ , 2F), -127.3 (CF ₂ , 2F)

Next, in a 200 mL flask, 30.0 g of the alcohol compound (B-1), 10.9 g of 2-isocyanatoethyl methacrylate (Showa Denko KK, Karens MOI), 75 mL of dimethylformamide, and dibutyltin dilaurate (dibutyltin dilaurate) as a catalyst. Two drops (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.3 g of dibutylhydroxytoluene as a polymerization inhibitor were added, heated to 90 ° C., stirred for 1 hour, and then allowed to cool to room temperature. After allowing to cool, the reaction solution was added to 300 mL of toluene to reprecipitate the crystals. The precipitated crystals were filtered and dried under reduced pressure to obtain a fluorine-containing polymerizable compound (M-1) represented by the following formula (M-1) (34.7 g, yield 93%).

^{1 1} H NMR (CD ₃ OD): δ 1.94 (s, CH ₃ , 3H), 2.16-2.28 (m, 2H), 2.65-2.72 (m, 2H), 2. 73-3.05 (m, 6H), 3.12 (s, CH ₃ , 3H), 3.32-3.52 (m, 6H), 3.52-3.69 (m, 4H), 3 .70-3.86 (m, 2H), 4.12-4.32 (m, 2H), 4.95-5.10 (m, 1H), 5.61-5.66 (m, 1H) , 6.10-6.15 (m, 1H), 7.12-7.20 (m, 1H)
_{^{19 F NMR (CD 3 OD)}} : δ -82.4 (CF 3, 3F), - 114.3 (CF 2, 2F), - 122.9 (CF 2, 2F), - 123.9 (CF 2 , 2F), -124.6 (CF ₂ , 2F), _{-127.3 (CF 2} , 2F)

(2) Synthesis of Fluorine-Containing Polymer In a 200 ml flask, 0.5 g of the fluorinated polymerizable compound (M-1) obtained in (1) above, [2- (methacryloyloxy) ethyl] dimethyl- (3-). Add 2.5 g of sulfopropyl) ammonium hydroxide (manufactured by Aldrich), 0.03 g of azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd.) and 16.7 g of trifluoroethanol (manufactured by TCI Co., Ltd.), and add 80. After heating to ° C. and reacting for 20 hours, the mixture was allowed to cool to room temperature. After allowing to cool, the obtained reaction solution was put into methanol to precipitate a solid. The precipitated solid was filtered and dried under reduced pressure to obtain a fluorine-containing polymer.

(3) Production of Surface Treatment Agent The fluorine-containing polymer obtained by the synthesis of the fluorine-containing polymer (2) above and trifluoroethanol are mixed at a mass ratio of 1:99 to a concentration of 1% by mass. A fluorine-containing polymer solution was prepared and used as a surface treatment agent.

[Example 2]
(1) Synthesis of Fluorine-Containing Polymerizable Compound In the same manner as in Example 1 except that 3- (dimethylamino) pyrrolidine was used instead of 1-methylpiperazine, it is represented by the following formula (M-2). A fluorine-containing polymerizable compound was obtained.

^{1 1} H NMR (CD ₃ OD): δ 1.93 (s, CH ₃ , 3H), 2.14-2.96 (m, 13H), 3.04 (s, CH ₃ , 3H), 3.04 -3.30 (m, 4H), 3.32-3.89 (m, 9H), 4.10-4.26 (m, 3H), 4.92-5.05 (m, 1H), 5 .60-5.65 (m, 1H), 6.10-6.15 (m, 1H), 7.14-7.22 (m, 1H)
_{^{19 F NMR (CD 3 OD)}} : δ -82.4 (CF 3, 3F), - 114.3 (CF 2, 2F), - 122.9 (CF 2, 2F), - 123.9 (CF 2 , 2F), -124.6 (CF ₂ , 2F), _{-127.3 (CF 2} , 2F)

(2) Synthesis of Fluorine-Containing Polymer and Production of Surface Treatment Agent Fluorine-containing polymer in the same manner as in Example 1 except that the fluorinated polymerizable compound (M-2) obtained in (1) above was used. Was synthesized. Then, a surface treatment agent was produced in the same manner as in Example 1 except that this fluorine-containing polymer was used.

[Example 3]
(1) Synthesis of Fluorine-Containing Polymerizable Compound The fluorine-containing polymerizable compound represented by the following formula (M-3) is the same as in Example 1 except that dimethylamine is used instead of 1-methylpiperazine. (M-3) was obtained.

^{1 1} H NMR (CD ₃ OD): δ 1.93 (s, CH ₃ , 3H), 2.16-2.34 (m, 2H), 2.42-2.58 (m, 2H), 2. 78-2.91 (m, 2H), 3.16 (s, CH ₃ , 6H), 3.36-3.49 (m, 2H), 3.50-3.72 (m, 5H), 3 .72-3.87 (m, 3H), 4.19-4.31 (m, 2H), 5.32-5.39 (m, 1H), 5.60-5.65 (m, 1H) ), 5.32-5.39 (m, 1H), 6.10-6.13 (m, 1H)
_{^{19 F NMR (CD 3 OD)}} : δ -82.4 (CF 3, 3F), - 114.3 (CF 2, 2F), - 122.9 (CF 2, 2F), - 123.9 (CF 2 , 2F), -124.6 (CF ₂ , 2F), _{-127.3 (CF 2} , 2F)

(2) Synthesis of Fluorine-Containing Polymer and Production of Surface Treatment Agent Fluorine-containing polymer in the same manner as in Example 1 except that the fluorinated polymerizable compound (M-3) obtained in (1) above was used. Was synthesized. Then, a surface treatment agent was produced in the same manner as in Example 1 except that this fluorine-containing polymer was used.

[Example 4]
(1) Synthesis of Fluorine-Containing Polymerizable Compound In the same manner as in Example 1 except that 1-methyl-4- [1- (4-piperidyl) -4-piperidyl] piperazine was used instead of 1-methylpiperazine. , A fluorine-containing polymerizable compound represented by the following formula (M-4) was obtained.

^{1 1} H NMR (CD ₃ OD): δ 1.47-1.60 (m, 4H), 1.80-1.97 (m, 4H), 1.93 (s, CH ₃ , 3H), 2. 00-2.58 (m, 12H), 2.82-3.08 (m, 10H), 3.10 (s, CH ₃ , 3H), 3.35-3.85 (m, 12H), 4 .15-4.22 (m, 2H), 4.95-5.03 (m, 1H), 5.60-5.65 (m, 1H), 6.10-6.14 (m, 1H)
_{^{19 F NMR (CD 3 OD)}} : δ -82.4 (CF 3, 3F), - 114.3 (CF 2, 2F), - 122.9 (CF 2, 2F), - 123.9 (CF 2 , 2F), -124.6 (CF ₂ , 2F), _{-127.3 (CF 2} , 2F)

(2) Synthesis of Fluorine-Containing Polymer and Production of Surface Treatment Agent Fluorine-containing polymer in the same manner as in Example 1 except that the fluorinated polymerizable compound (M-4) obtained in (1) above was used. Was synthesized. Then, a surface treatment agent was produced in the same manner as in Example 1 except that this fluorine-containing polymer was used.

[Example 5]
(1) Synthesis of fluorine-containing polymerizable compound Methacryloyloxyethoxyethyl isocyanate (Showa Denko KK, Karens MOI-EG) was used instead of 2-isocyanatoethyl methacrylate (Showa Denko KK, Karens MOI). A fluorine-containing polymerizable compound represented by the following formula (M-5) was obtained in the same manner as in Example 1 except for the above.

^{1 1} H NMR (CD ₃ OD): δ 1.93 (s, CH ₃ , 3H), 2.16-2.26 (m, 2H), 2.38-2.53 (m, 2H), 2. 67-2.76 (m, 2H), 2.78-3.05 (m, 6H), 3.12 (s, CH ₃ , 3H), 3.28-3.32 (m, 2H), 3 .40-3.69 (m, 10H), 3.70-3.86 (m, 4H), 4.27-4.30 (m, 2H), 4.92-5.08 (m, 1H) 5.60-5.65 (m, 1H), 6.10-6.15 (m, 1H), 6.89-6.95 (m, 1H)
_{^{19 F NMR (CD 3 OD)}} : δ -82.4 (CF 3, 3F), - 114.3 (CF 2, 2F), - 122.9 (CF 2, 2F), - 123.9 (CF 2 , 2F), -124.7 (CF ₂ , 2F), -127.3 (CF ₂ , 2F)

(2) Synthesis of Fluorine-Containing Polymer and Production of Surface Treatment Agent Fluorine-containing polymer in the same manner as in Example 1 except that the fluorinated polymerizable compound (M-5) obtained in (1) above was used. Was synthesized. Then, a surface treatment agent was produced in the same manner as in Example 1 except that this fluorine-containing polymer was used.

[Comparative Example 1]
In the synthesis of the fluorinated polymer of Example 1 (2), the non-fluorinated polymer, that is, [2- (methacryloyloxy) ethyl] was obtained in the same manner as in Example 1 except that the fluorinated polymerizable compound was not used. A homopolymer of dimethyl- (3-sulfopropyl) ammonium hydroxide was synthesized. Then, a surface treatment agent was produced in the same manner as in Example 1 except that this non-fluorine-containing polymer was used.

[Comparative Example 2]
In the synthesis of the fluorine-containing polymer of Example 1 (2), Examples except that a compound represented by the following general formula (M-6) (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the fluorine-containing polymerizable compound. A fluorine-containing polymer was synthesized in the same manner as in 1. Then, a surface treatment agent was produced in the same manner as in Example 1 except that this fluorine-containing composite was used.

[evaluation]
The contact angle between water and hexadecane and the falling angle of hexadecane were measured for the coating films prepared using the surface treatment agents produced in Examples 1 to 5 and Comparative Examples 1 and 2. The results are shown in Table 1.

The coating film was prepared by applying a surface treatment agent to the surface of the slide glass by spin coating and then heating the slide glass at a temperature of 80 ° C. for 15 minutes.
The contact angle between water and hexadecane and the falling angle of hexadecane were measured using a CA-A type contact angle meter manufactured by Kyowa Interface Science Co., Ltd.
The contact angle was measured 1 second after dropping 2 μL each of water and hexadecane on the surface of the coating film. The contact angle was measured at any 5 points on the surface of the coating. Table 1 shows the average of the measured contact angles.
The fall angle of hexadecane was determined by dropping 5 μL of hexadecane onto the surface of the coating, tilting the slide glass, measuring the angle of the slide glass plate when the hexadecane droplets began to fall, and using that angle as the tilt angle. ..

The coating film prepared using the surface treatment agents obtained in Examples 1 to 5 has a water contact angle of 40 degrees or less and excellent hydrophilicity, and a hexadecane contact angle of 30 degrees or more and is oil repellent. Excellent for. On the other hand, the coating film prepared by using the surface treatment agent obtained in Comparative Example 1 has a contact angle with hexadecane of 10 degrees or less and is inferior in oil repellency. Further, the coating film prepared by using the surface treatment agent obtained in Comparative Example 2 has a contact angle with water of 60 degrees or more and is inferior in hydrophilicity.

From the above results, it was confirmed that according to this example, it is possible to provide a novel fluorine-containing polymerizable compound, fluorine-containing polymer and surface treatment agent having excellent hydrophilicity and oil repellency. ..

Claims (6)

Fluorine-containing polymerizable compound represented by the following general formula (1):

In the above general formula (1), R represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and Rf is a linear or branched perfluoro having 1 to 6 carbon atoms. Represents an alkyl group, X represents a divalent linking group having one or more oxygen atoms, L represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and an oxygen atom. , A carbonyl group, an imino group which may have a substituent, or a divalent linking group consisting of a combination thereof, M represents a cationic group having one or more nitrogen atoms, and Q represents an anionic group. Represents. The fluorine-containing polymerizable compound according to claim 1, wherein X is a linking group represented by the following general formula (2).

In the above general formula (2), * ¹ represents a bond that binds to C of C = O of the general formula (1), and * ² binds to C of CH of the general formula (1). A bond is represented, m represents an integer of 0 to 4, and n represents an integer of 0 or 1. The fluorine-containing compound according to claim 1, wherein M is a cationic group represented by any one of the following general formulas (3), (4), (5) and (6). Polymerizable compound:

In the above general formulas (3), (4), (5) and (6), R ¹ represents a linear or branched alkyl group having 1 to 12 carbon atoms, and * ³ is the general formula. _{The bonder that binds to C of CH 2} of (1) is represented, and * ⁴ represents the bonder that binds to Q of the general formula (1). The fluorine-containing polymerizable compound according to claim 1, wherein Q is an anionic group represented by the following general formula (7).

In the above general formula (7), Y represents a divalent hydrocarbon group which may have a substituent group having 1 to 10 carbon atoms, Z _is, ^-CO 2 -, -SO ₃ ^-, or −PO ₃ ^{− −} R ² , where R ² represents a linear or branched alkyl group having 1 to 12 carbon atoms, and * ⁵ is a bond that binds to M in the general formula (1). Represents. It has a first structural unit derived from the fluoropolymerizable compound according to any one of claims 1 to 4, and further has a structural unit other than the first structural unit, other than the first structural unit. The constituent unit of the above is a polymerizable group containing an ethylenically unsaturated bond , an anionic hydrophilic group, a cationic hydrophilic group, an amphoteric hydrophilic group, or a nonionic hydrophilic group. What binary copolymer der a structural unit derived from a polymerizable compound having a sex group, the contact angle with water is 40 degrees or less, der contact angle with hexadecane is at least 30 degrees A fluorine-containing polymer characterized by the above. A surface treatment agent comprising the fluorine-containing polymer according to claim 5 and a liquid medium.