JPWO2016136399A1 - Water and oil repellent - Google Patents

Abstract

As an active ingredient, formula (I): (wherein R1 is a hydrogen atom or a methyl group, R2 is a hydrogen atom or a fluorine atom, m is 0 or an integer of 1 to 4, and n is an integer of 1 to 12) Fluorine atom-containing monomer represented by formula (II): (wherein R3 is a hydrogen atom or a methyl group, R4 and R5 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, p is 1 to 4) And a polymer formed by polymerizing a monomer component containing a betaine monomer represented by the formula (1) and q (an integer of 1 to 4) and an alkyl (meth) acrylate having an alkyl group having 1 to 22 carbon atoms. Water and oil repellent characterized by

Description

  The present invention relates to a water / oil repellent. More specifically, the present invention includes, for example, inorganic materials such as stone and brick, fibrous base materials such as woven fabric, nonwoven fabric, and paper, water-based paints, fire extinguishing agents, electronic components, car chemical wax, mold release The present invention relates to a water and oil repellent that can be suitably used for applications such as an agent, a release film, and a lens. The water / oil repellent of the present invention is excellent in water repellency, oil repellency and oil repellency, so it is excellent in antifouling property against oily stains such as sebum stains and aqueous stains such as sweat stains. Therefore, it is expected to be used particularly for textile products among the above applications.

  In recent years, various water and oil repellents have been proposed, and fluorine-based monomers have been used as raw materials for the water and oil repellents to improve oil repellency (see, for example, Patent Documents 1 to 4). ).

  However, the conventional water and oil repellents tend to be excellent in either water repellency or oil repellency. In recent years, not only are both water repellency and oil repellency excellent, The development of a water and oil repellent agent that is excellent in oil repellency is desired since it is difficult to remove oil stains attached to fibers and the like.

JP 2014-129532 A JP 2014-169449 A JP 2014-172979 A Japanese Patent Application Laid-Open No. 2014-237827

  The present invention has been made in view of the prior art, and provides a water and oil repellent agent that is excellent not only in both water repellency and oil repellency but also in oil repellency sustainability. Let it be an issue.

The present invention
(1) A water / oil repellent having water repellency and oil repellency, and as an active ingredient,
(A) Formula (I):

(Wherein R ¹ is a hydrogen atom or a methyl group, R ² is a hydrogen atom or a fluorine atom, m is 0 or an integer of 1 to 4, and n is an integer of 1 to 12)
A fluorine atom-containing monomer represented by:
(B) Formula (II):

Wherein R ³ is a hydrogen atom or a methyl group, R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, p is an integer of 1 to 4 and q is 1 to 4 Indicates an integer)
A water- and oil-repellent agent characterized by containing a polymer obtained by polymerizing a monomer component containing (C) an alkyl (meth) acrylate having 1 to 22 carbon atoms of (C) an alkyl group,
(2) The water / oil repellent according to (1), wherein the monomer component further contains a sulfonic acid group-containing monomer,
(3) The water / oil repellent according to (2), wherein at least a part of the sulfonic acid group of the sulfonic acid group-containing monomer is neutralized,
(4) The water / oil repellent according to any one of (1) to (3) above, wherein the monomer component further contains a crosslinking agent, and (5) the crosslinking agent is represented by formula (III):

(Wherein R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group, R ⁸ is an alkylene group having 2 or 3 carbon atoms, and r is an integer of 1 to 40)
The water / oil repellent agent according to (4), which is a crosslinking agent represented by

  In the present invention, “(meth) acrylate” means “acrylate” or “methacrylate”.

  According to the present invention, there is provided a water / oil repellent which is excellent not only in both water repellency and oil repellency but also in excellent oil repellency.

As described above, the water / oil repellent of the present invention is an active ingredient,
(A) Formula (I):

(Wherein R ¹ is a hydrogen atom or a methyl group, R ² is a hydrogen atom or a fluorine atom, m is 0 or an integer of 1 to 4, and n is an integer of 1 to 12)
A fluorine atom-containing monomer represented by:
(B) Formula (II):

Wherein R ³ is a hydrogen atom or a methyl group, R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, p is an integer of 1 to 4 and q is 1 to 4 Indicates an integer)
And (C) a polymer obtained by polymerizing a monomer component containing an alkyl (meth) acrylate having 1 to 22 carbon atoms in an alkyl group.

In the fluorine atom-containing monomer represented by the formula (I), R ¹ is a hydrogen atom or a methyl group, R ² is a hydrogen atom or a fluorine atom, m is 0 or an integer of 1 to 4, and n is 1 It is an integer of ~ 12. m is 0 or an integer of 1 to 4, but from the viewpoint of improving water repellency, oil repellency and oil repellency, it is preferably an integer of 1 to 4, more preferably an integer of 2 to 4. n is an integer of 1 to 12, and is preferably an integer of 2 to 10, more preferably an integer of 4 to 8, from the viewpoint of improving water repellency and oil repellency.

As the fluorine atom-containing monomer represented by the formula (I), for example, in the formula (I), a fluorine atom-containing monomer in which R ¹ is a hydrogen atom, R ² is a fluorine atom, m is 2, and n is 6 [for example, Manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name: Biscote 13F, etc.], fluorine atom-containing monomer wherein R ¹ is a hydrogen atom, R ² is a hydrogen atom, m is 1 and n is 1 [for example, Osaka Organic Chemical Industry ( Co., Ltd., trade name: Biscote 4F, etc.], R ¹ is methyl group, R ² is hydrogen atom, m is 1, n is 3 fluorine atom-containing monomer [for example, product made by Osaka Organic Chemical Industry Co., Ltd. Name: Biscote 8FM, etc.], etc., may be mentioned, but the present invention is not limited to such examples.

  The content of the fluorine atom-containing monomer represented by the formula (I) in the monomer component is preferably 1 to 30% by mass, more preferably 1 to 25% by mass from the viewpoint of improving water repellency, oil repellency and oil repellency. %, More preferably 2 to 20% by mass.

In the betaine monomer represented by the formula (II), R ³ is a hydrogen atom or a methyl group, R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and p is 1 Is an integer of -4, and q is an integer of 1-4.

  Examples of the betaine monomer represented by the formula (II) include N- (meth) acryloyloxymethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine, N- (meth) acryloyloxyethyl-N, N. -Dimethylammonium-α-N-methylcarboxybetaine, N- (meth) acryloyloxypropyl-N, N-dimethylammonium-α-N-methylcarboxybetaine, N- (meth) acryloyloxymethyl-N, N-diethyl Ammonium-α-N-methylcarboxybetaine, N- (meth) acryloyloxyethyl-N, N-diethylammonium-α-N-methylcarboxybetaine, N- (meth) acryloyloxypropyl-N, N-diethylammonium- α-N-methylcarboxybetaine etc. Although mentioned, this invention is not limited only to this illustration. These betaine monomers may be used alone or in combination of two or more.

  The betaine monomer represented by the formula (II) can be easily prepared, for example, by the methods described in JP-A-9-95474, JP-A-9-95586, JP-A-11-222470, and the like.

  The betaine monomer represented by the formula (II) can be easily obtained commercially, for example, as trade name: GLBT manufactured by Osaka Organic Chemical Industry Co., Ltd.

  Among the betaine monomers represented by the formula (II), from the viewpoint of improving water repellency, oil repellency and oil repellency, the oxyalkyl group has 1 to 4 carbon atoms and an N, N-dialkyl group alkyl. N- (meth) acryloyloxyalkyl-N, N-dialkylammonium-α-N-alkylcarboxybetaines in which the group has 1 to 4 carbon atoms and the N-alkyl group has 1 to 4 carbon atoms are preferred, N- (meth) wherein the carbon number of the oxyalkyl group is 1 or 2, the carbon number of the alkyl group of the N, N-dialkyl group is 1 or 2, and the carbon number of the N-alkyl group is 1 or 2 More preferred is acryloyloxyalkyl-N, N-dialkylammonium-α-N-alkylcarboxybetaine, N- (meth) acryloyloxyethyl-N, N-dimethyl. More preferably ammonium-.alpha.-N-methyl carboxy betaine, N- methacryloyloxyethyl -N, N- dimethylammonium-.alpha.-N-methyl carboxy betaine is even more preferred. From the viewpoint of improving water solubility and water dilutability, the oxyalkyl group has 1 to 2 carbon atoms, the N, N-dialkyl group has 1 to 2 carbon atoms, and the N-alkyl group. N- (meth) acryloyloxyalkyl-N, N-dialkylammonium-α-N-alkylcarboxybetaines having a carbon number of 1 to 2 are preferred.

  The content of the betaine monomer represented by the formula (II) in the monomer component is preferably 3 to 80% by mass, more preferably 3 to 75% by mass, from the viewpoint of improving water repellency, oil repellency and oil repellency. More preferably, it is 5-70 mass%.

  Examples of the alkyl (meth) acrylate having 1 to 22 carbon atoms in the alkyl group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl ( (Meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, sec-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, Isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate The carbon number of the alkyl group constituting the ester such as tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, isostearyl (meth) acrylate, eicosyl (meth) acrylate, behenyl (meth) acrylate, etc. Although the alkyl (meth) acrylate which is 1-22 is mentioned, this invention is not limited only to this illustration. These alkyl (meth) acrylates may be used alone or in combination of two or more. Among these alkyl (meth) acrylates, from the viewpoint of improving water repellency, alkyl (meth) acrylates having an alkyl group having 10 to 22 carbon atoms are preferred, and alkyl groups having 12 to 22 carbon atoms are preferred. (Meth) acrylate is more preferred.

  From the viewpoint of improving water repellency, oil repellency and oil repellency, the content of the alkyl (meth) acrylate having 1 to 22 carbon atoms of the alkyl group in the monomer component is preferably 10 to 80% by mass, more preferably It is 15-75 mass%, More preferably, it is 20-70 mass%.

  From the viewpoint of improving oil repellency, the monomer component preferably contains a sulfonic acid group-containing monomer.

  Examples of the sulfonic acid group-containing monomer include 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamide-2-methylpropanesulfonic acid, 2-acrylamido-2-ethylpropanesulfonic acid, and 2-methacrylamide-2. -Ethyl propane sulfonic acid, 2-acrylamido-2-propyl propane sulfonic acid, 2-methacrylamido-2-propyl propane sulfonic acid etc. are mentioned, However, this invention is not limited only to this illustration. These sulfonic acid group-containing monomers may be used alone or in combination of two or more. Among these sulfonic acid group-containing monomers, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylic acid are used from the viewpoint of improving the balance between water repellency and water repellency and improving the water solubility of the polymer. Amido-2-methylpropanesulfonic acid, 2-acrylamido-2-ethylpropanesulfonic acid and 2-methacrylamideamido-2-ethylpropanesulfonic acid are preferred, 2-acrylamido-2-methylpropanesulfonic acid and 2-methacrylamide- 2-methylpropanesulfonic acid is more preferred.

  The sulfonic acid group contained in the sulfonic acid group-containing monomer is preferably at least partially neutralized from the viewpoint of improving oil repellency. The sulfonic acid group of the sulfonic acid group-containing monomer can be neutralized using a neutralizing agent. Examples of the neutralizing agent include inorganic basic compounds such as sodium hydroxide and potassium hydroxide; monoethanolamine, dimethylethanolamine, diethylethanolamine, triethanolamine, morpholine, aminomethylpropanol, aminomethylpropanediol, octyl Examples include organic basic compounds such as amine, tributylamine, and aniline, but the present invention is not limited to such examples. Neutralization of the sulfonic acid group contained in the sulfonic acid group-containing monomer may be performed on the sulfonic acid group-containing monomer, or may be performed on a polymer obtained by polymerizing the monomer component.

  From the viewpoint of improving oil repellency, the content of the sulfonic acid group-containing monomer in the monomer component is 0% by mass or more, preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more. From the viewpoint of improving water repellency, it is preferably 40% by mass or less, more preferably 35% by mass or less, and further preferably 30% by mass or less.

  The monomer component may contain other monomers as long as the object of the present invention is not impaired.

  Examples of other monomers include aliphatic monocarboxylic acids such as acrylic acid, methacrylic acid, itaconic acid and maleic anhydride; 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl Hydroxyalkyl (meth) acrylates such as acrylate and hydroxybutyl methacrylate; cycloalkyl (meth) acrylates such as cyclohexyl acrylate and cyclohexyl methacrylate; aryl (meth) acrylates such as benzyl acrylate and benzyl methacrylate; methoxyethyl acrylate, methoxyethyl methacrylate, methoxy Alkoxyalkyls such as butyl acrylate and methoxybutyl methacrylate (Meth) acrylates; alkyl carbitol (meth) acrylates such as ethyl carbitol acrylate and ethyl carbitol methacrylate; N-methyl acrylamide, N-methyl methacrylamide, N-ethyl acrylamide, N-ethyl methacrylamide, N-propyl acrylamide N-propylmethacrylamide, N-isopropylacrylamide, N-isopropylmethacrylamide, N-tert-butylacrylamide, N-tert-butylmethacrylamide, N-octylacrylamide, N-octylmethacrylamide, N, N-dimethylacrylamide Alkyl (meth) acrylamides such as N, N-dimethylmethacrylamide, N, N-diethylacrylamide, N, N-diethylmethacrylamide Alkoxy (meth) acrylamides such as N-butoxymethylacrylamide and N-butoxymethylmethacrylamide; (meth) acryloylmorpholines such as acryloylmorpholine and methacryloylmorpholine; diacetone (meth) acrylamides such as diacetoneacrylamide and diacetone methacrylamide; styrene Styrene monomers such as methyl styrene; alkyl groups such as methyl itaconate and ethyl itaconate having 1 to 4 carbon atoms, fatty acid alkyl esters other than (meth) acrylic acid alkyl esters; vinyl acetate, vinyl propionate, etc. Fatty acid vinyl esters of

N-acryloyloxymethyl-N, N-dimethylammonium methyl-α-sulfobetaine, N-methacryloyloxymethyl-N, N-dimethylammoniummethyl-α-sulfobetaine, N-acryloyloxymethyl-N, N-dimethylammonium Ethyl-α-sulfobetaine, N-methacryloyloxymethyl-N, N-dimethylammonium ethyl-α-sulfobetaine, N-acryloyloxymethyl-N, N-dimethylammoniumpropyl-α-sulfobetaine, N-methacryloyloxymethyl -N, N-dimethylammoniumpropyl-α-sulfobetaine, N-acryloyloxymethyl-N, N-dimethylammoniumbutyl-α-sulfobetaine, N-methacryloyloxymethyl-N, N-dimethylammonium Butyl-α-sulfobetaine, N-acryloyloxyethyl-N, N-dimethylammonium methyl-α-sulfobetaine, N-methacryloyloxyethyl-N, N-dimethylammoniummethyl-α-sulfobetaine, N-acryloyloxyethyl -N, N-dimethylammoniumethyl-α-sulfobetaine, N-methacryloyloxyethyl-N, N-dimethylammoniumethyl-α-sulfobetaine, N-acryloyloxyethyl-N, N-dimethylammoniumpropyl-α-sulfo Betaine, N-methacryloyloxyethyl-N, N-dimethylammoniumpropyl-α-sulfobetaine, N-acryloyloxyethyl-N, N-dimethylammoniumbutyl-α-sulfobetaine, N-methacryloyloxyethyl N, N-dimethylammonium butyl-α-sulfobetaine, N-acryloyloxypropyl-N, N-dimethylammonium methyl-α-sulfobetaine, N-methacryloyloxypropyl-N, N-dimethylammonium methyl-α-sulfobetaine N-acryloyloxypropyl-N, N-dimethylammoniumethyl-α-sulfobetaine, N-methacryloyloxypropyl-N, N-dimethylammoniumethyl-α-sulfobetaine, N-acryloyloxypropyl-N, N-dimethyl Ammoniumpropyl-α-sulfobetaine, N-methacryloyloxypropyl-N, N-dimethylammoniumpropyl-α-sulfobetaine, N-acryloyloxypropyl-N, N-dimethylammoniumbutyl-α-sulfo Tyne, N-methacryloyloxypropyl-N, N-dimethylammonium butyl-α-sulfobetaine, N-acryloyloxybutyl-N, N-dimethylammonium methyl-α-sulfobetaine, N-methacryloyloxybutyl-N, N- Dimethylammonium methyl-α-sulfobetaine, N-acryloyloxybutyl-N, N-dimethylammoniumethyl-α-sulfobetaine, N-methacryloyloxybutyl-N, N-dimethylammoniumethyl-α-sulfobetaine, N-acryloyl Oxybutyl-N, N-dimethylammoniumpropyl-α-sulfobetaine, N-methacryloyloxybutyl-N, N-dimethylammoniumpropyl-α-sulfobetaine, N-acryloyloxybutyl-N, N-dimethyl N- (meth) acryloyloxyalkyl-N, N-dimethylammonium alkyl-α-sulfobetaine such as ammonium butyl-α-sulfobetaine, N-methacryloyloxybutyl-N, N-dimethylammoniumbutyl-α-sulfobetaine Monofunctional monomers such as nitrogen atom-containing monomers such as sulfobetaine monomer, N-vinylpyrrolidone, N-vinylcaprolactam, and the like, but the present invention is not limited to such examples. These other monomers may be used alone or in combination of two or more.

  The monomer component preferably contains a crosslinking agent from the viewpoint of improving water repellency, oil repellency and oil repellency persistence. Further, when the monomer component contains a crosslinking agent, the balance between water repellency and water repellency persistence can be improved.

  Examples of the crosslinking agent include carbon-carbon double compounds such as (meth) acrylate compounds having two or more (meth) acryloyl groups, (meth) acrylamide compounds having two or more (meth) acryloyl groups, diallylamine, triallylamine and the like. Examples include amine compounds having two or more bonds, and aromatic compounds having two or more carbon-carbon double bonds such as divinylbenzene and diallylbenzene, but the present invention is not limited to such examples. . These crosslinking agents may be used alone or in combination of two or more.

  Among the crosslinking agents, from the viewpoint of improving water repellency, oil repellency and oil repellency, a (meth) acrylate compound having two or more (meth) acryloyl groups is preferred, and the formula (III):

(Wherein R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group, R ⁸ is an alkylene group having 2 or 3 carbon atoms, and r is an integer of 1 to 40)
The crosslinking agent represented by is more preferable.

In the formula (III), R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group, R ⁸ is an alkylene group having 2 or 3 carbon atoms, and r is an integer of 1 to 40. Among these, from the viewpoint of improving oil repellency and its sustainability, r is preferably an integer of 1 to 20, more preferably an integer of 2 to 18.

  Examples of the crosslinking agent represented by the formula (III) include ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, (Poly) ethylene glycol di (meth) acrylates such as tetraethylene glycol dimethacrylate, polyethylene glycol diacrylates other than the above, polyethylene glycol dimethacrylates other than the above; propylene glycol diacrylate, propylene glycol dimethacrylate, dipropylene glycol diacrylate, Dipropylene glycol dimethacrylate, tripropylene glycol (Poly) propylene glycol di (meth) acrylates such as coal diacrylate, tripropylene glycol dimethacrylate, tetrapropylene glycol diacrylate, tetrapropylene glycol dimethacrylate, other polypropylene glycol diacrylates, and other polypropylene glycol dimethacrylates, etc. However, the present invention is not limited to such examples. These crosslinking agents may be used alone or in combination of two or more.

  The content of the crosslinking agent in the monomer component is preferably 0.3 to 15% by mass, more preferably 0.5 to 15% by mass, and still more preferably from the viewpoint of improving water repellency, oil repellency and oil repellency. 1 to 10% by mass.

  Moreover, when polymerizing a monomer component, you may use a chain transfer agent in order to adjust the molecular weight of the polymer obtained. Examples of the chain transfer agent include compounds having a mercaptan group such as lauryl mercaptan, dodecyl mercaptan, and thioglycerol, and inorganic salts such as sodium hypophosphite and sodium bisulfite. It is not limited to. The amount of the chain transfer agent per 100 parts by mass of the monomer component is preferably about 0.01 to 10 parts by mass.

  Polymerization of the monomer component can be performed by a polymerization method such as a homogeneous solution polymerization method, a heterogeneous solution polymerization method, an emulsion polymerization method, a reverse phase emulsion polymerization method, a bulk polymerization method, a suspension polymerization method, or a precipitation polymerization method. .

  A solvent is used when the monomer component is polymerized by a solution polymerization method. Examples of the solvent include alcohol solvents such as methanol, ethanol, propyl alcohol, isopropyl alcohol, and butyl alcohol; hydrocarbon solvents such as hexane, heptane, octane, isooctane, decane, and liquid paraffin; dimethyl ether, diethyl ether, and tetrahydrofuran. Ether solvents such as acetone; methyl solvents such as methyl ethyl ketone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate; chloride solvents such as methylene chloride, chloroform, carbon tetrachloride; dimethylformamide, diethylformamide, Although dimethyl sulfoxide, dioxane, etc. are mentioned, this invention is not limited only to this illustration. These solvents may be used alone or in combination of two or more. Since the amount of the solvent varies depending on the type of the solvent, it cannot be generally limited, but it is usually preferably about 100 to 1000 parts by mass per 100 parts by mass of the monomer component.

  When the monomer component is polymerized, a polymerization initiator can be used. Examples of the polymerization initiator include a thermal polymerization initiator and a photopolymerization initiator.

  Examples of the thermal polymerization initiator include dimethyl-2,2′-azobis (2-methylpropionate), 2,2′-azobisisobutyronitrile, dimethyl 2,2′-azobisisobutyrate, and azobisdimethyl. Examples thereof include azo polymerization initiators such as valeronitrile, peroxide polymerization initiators such as benzoyl peroxide, potassium persulfate, and ammonium persulfate, but the present invention is not limited to such examples. These polymerization initiators may be used alone or in combination of two or more.

  Examples of the photopolymerization initiator include 2-oxoglutaric acid, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl [4- (methylthio) phenyl]- 2-morpholinopropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, benzophenone, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl -1-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl Although pentylphosphine oxide etc. are mentioned, this invention is not limited only to this illustration. These polymerization initiators may be used alone or in combination of two or more.

  The amount of the polymerization initiator varies depending on the type of the polymerization initiator and cannot be determined unconditionally, but it is preferably about 0.01 to 10 parts by mass per 100 parts by mass of the monomer component.

  The atmosphere for polymerizing the monomer component is not particularly limited, and may be air or an inert gas such as nitrogen gas or argon gas.

  The polymerization temperature of the monomer component is not particularly limited, and is usually preferably about 5 to 80 ° C. The time required for the polymerization of the monomer component is arbitrary because it cannot be determined unconditionally because it varies depending on the polymerization conditions. Usually, the polymerization reaction can be arbitrarily terminated when the amount of the remaining monomer becomes 10% by mass or less. The amount of the remaining monomer can be determined, for example, by adding oxalic acid to the double bond of the monomer and measuring the double bond content.

  A polymer is obtained by polymerizing the monomer component as described above. The weight average molecular weight of the polymer is not particularly limited, but is preferably about 3000 to 100,000. The weight average molecular weight of the polymer is a value measured by gel permeation chromatograph (GPC). In addition, when the crosslinking agent is contained in the monomer component, since the obtained polymer has a crosslinked structure, it is difficult to measure the weight average molecular weight of the polymer.

  If necessary, the polymer may be neutralized as described above. Examples of the neutralizing agent include inorganic basic compounds such as sodium hydroxide and potassium hydroxide; monoethanolamine, dimethylethanolamine, diethylethanolamine, triethanolamine, morpholine, aminomethylpropanol, aminomethylpropanediol, octyl Examples include organic basic compounds such as amine, tributylamine, and aniline, but the present invention is not limited to such examples. These neutralizing agents may be used alone or in combination of two or more.

  The polymer may be used as it is depending on its application, but may be purified by a purification method such as distillation or extraction, if necessary, in order to remove the solvent, unreacted monomers and the like. .

  The water / oil repellent of the present invention contains the polymer as an active ingredient, may be composed of only the polymer, and contains a solvent, an additive, etc. within a range that does not impair the object of the present invention. May be.

  Examples of the solvent include the solvent used in solution polymerization of monomer components, but the present invention is not limited to such examples.

  Examples of additives include surfactants, colorants, penetrants, antifoaming agents, water absorbing agents, antifungal agents, texture modifiers, film-forming aids, water-soluble polymer compounds, thermosetting resins, insecticides. And dye stabilizers, and the like, but the present invention is not limited to such examples.

  The water / oil repellent agent of the present invention obtained as described above is not only excellent in both water repellency and oil repellency, but also excellent in oil repellency, for example, stone, brick, etc. It is expected to be used for applications such as inorganic materials, fibrous base materials such as woven fabrics, non-woven fabrics, and papers, water-based paints, and fire extinguishing agents.

  Next, the present invention will be described in more detail based on examples. However, the present invention is not limited to such examples.

Example 1
In a 500 mL five-necked flask equipped with a stirrer, an inert gas inlet, a reflux condenser, and a thermometer, 70 g of N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine, Octyl acrylate [Osaka Organic Chemical Co., Ltd.] 20 g and 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate [Osaka Organic Chemical Industry Co., Ltd., product number: V-13F] A monomer component consisting of 10 g and 234 g of ethyl alcohol were added. After heating the contents of the flask to 75 ° C., 0.6 g of dimethyl-2,2′-azobis (2-methylpropionate) [manufactured by Wako Pure Chemical Industries, Ltd., product number: V-601] was added to the flask. The reaction solution containing the polymer composed of the monomer components was obtained by putting in the solution and carrying out the polymerization reaction with stirring for 8 hours under reflux conditions.

  Using the reaction solution obtained above as a water / oil repellent, a glass plate having a smooth surface (vertical: 50 mm, horizontal: 20 mm) so that the thickness of the film after drying the water / oil repellent with a bar coater is 10 μm. , Thickness: 3 mm) and dried in air at 60 ° C. to obtain a test piece. In addition, the thickness of the film after drying was measured using a stylus type step gauge [manufactured by KLA-Tencor Corporation, product number: P-10] (the same applies hereinafter).

  Next, the water repellency and water repellency, oil repellency and oil repellency, and water solubility of the coating were examined based on the following methods using the test pieces obtained above. Moreover, water dilution property was evaluated based on the following method using the water / oil repellent agent obtained above. As a result, the water repellency (contact angle) was 107.5 °, the water repellency persistence was 43.0%, the oil repellency (contact angle) was 69 °, and the oil repellency persistence was 87.0%. Evaluation of water solubility was B, and evaluation of water dilutability was A.

[Water repellency and water repellency]
A water droplet was dropped on the film of the test piece, and the contact angle A with respect to water was quickly measured in the atmosphere at 25 ° C. using an automatic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., product number: DM-SA). The water repellency is based on the acceptance criteria that the contact angle A with respect to water is 100 ° or more, but it is practically preferable that the contact angle A is 102 ° or more.

Further, the contact angle B was measured in the same manner as described above after 120 seconds had elapsed since the water droplet was dropped. Based on contact angle A and contact angle B, the formula:
[Water repellency] = [Contact angle B (°)] ÷ [Contact angle A (°)] × 100
The water repellency persistence was evaluated according to The water repellency persistence varies depending on the use of the water / oil repellent of the present invention. Depending on the application, the water repellency persistence may be preferably low, and depending on other applications, the water repellency persistence may be high. It may be preferable.

[Oil and oil repellency]
Liquid paraffin droplets are dropped on the coating film of the test piece, and the contact angle with liquid paraffin is quickly measured in an atmosphere at 25 ° C. using an automatic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., product number: DM-501Hi). Based on the measured contact angle X, oil repellency was evaluated. Note that the oil repellency is based on an acceptance standard that the contact angle with respect to liquid paraffin is 50 ° or more.

Further, the contact angle Y was measured in the same manner as described above after 120 seconds had passed since the liquid paraffin droplet was dropped. Based on contact angle X and contact angle Y, the formula:
[Oil repellency] = [Contact angle Y (°)] ÷ [Contact angle X (°)] × 100
According to the evaluation, the oil repellency was evaluated. The oil repellency persistence is 85% or more as a criterion for acceptance.

〔Water soluble〕
After immersing the test piece in water at 40 ° C. for 10 seconds, pulling it up from the water, gently wiping off the water with Kimwipe (manufactured by Nippon Paper Crecia Co., Ltd., product number: S-200), re-drying after dissolution and the membrane weight before dissolution. The area was measured from the weight of the film so that water solubility was evaluated based on the following evaluation criteria.
(Evaluation criteria)
A: The area of the dissolved film is 80% or more.
B: The area of the dissolved film is 60% or more and less than 80% C: The area of the dissolved film is 20% or more and less than 60% D: The area of the dissolved film is less than 20%

[Water reducibility]
A polymer solution having a polymer concentration of 20% by mass was prepared by diluting the water / oil repellent with ethanol. 100 g of the polymer solution obtained above and 100 g of purified water were mixed at each liquid temperature of 25 ° C., and the obtained mixed solution was sufficiently stirred and then allowed to stand, and the mixed solution was cooled to a liquid temperature of 25 ° C. Was visually observed and evaluated based on the following evaluation criteria.
(Evaluation criteria)
A: The polymer is completely dissolved B: The polymer is accelerated or suspended C: The polymer is precipitated

Example 2
N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine, lauryl in a 500 mL five-necked flask equipped with a stirrer, an inert gas inlet, a reflux condenser and a thermometer 20 g of acrylate [Osaka Organic Chemical Co., Ltd.] and 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate [Osaka Organic Chemical ( Co., Ltd., product number: V-13F] A monomer component consisting of 10 g and 234 g of ethyl alcohol were added. After heating the contents of the flask to 75 ° C., 0.6 g of dimethyl-2,2′-azobis (2-methylpropionate) [manufactured by Wako Pure Chemical Industries, Ltd., product number: V-601] was added to the flask. The reaction solution containing the polymer composed of the monomer components was obtained by putting in the solution and carrying out the polymerization reaction with stirring for 8 hours under reflux conditions.

  Using the reaction solution obtained above as a water / oil repellent, a glass plate having a smooth surface (vertical: 50 mm, horizontal: 20 mm) so that the thickness of the film after drying the water / oil repellent with a bar coater is 10 μm. , Thickness: 3 mm) and dried in air at 60 ° C. to obtain a test piece.

  Next, the water repellency and water repellency, oil repellency and oil repellency, and water solubility of the coating were examined in the same manner as in Example 1 using the test pieces obtained above. Further, the water dilution of the water / oil repellent was examined in the same manner as in Example 1. As a result, the water repellency (contact angle) was 103.1 °, the water repellency persistence was 60.4%, the oil repellency (contact angle) was 69 °, and the oil repellency persistence was 87.0%. Evaluation of water solubility was B, and evaluation of water dilutability was A.

Example 3
N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine, lauryl in a 500 mL five-necked flask equipped with a stirrer, an inert gas inlet, a reflux condenser and a thermometer 28 g of acrylate [Osaka Organic Chemical Co., Ltd.] and 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate [Osaka Organic Chemical ( Co., Ltd., product number: V-13F] A monomer component consisting of 2 g and 234 g of ethyl alcohol were added. After heating the contents of the flask to 75 ° C., 0.6 g of dimethyl-2,2′-azobis (2-methylpropionate) [manufactured by Wako Pure Chemical Industries, Ltd., product number: V-601] was added to the flask. The reaction solution containing the polymer composed of the monomer components was obtained by putting in the solution and carrying out the polymerization reaction with stirring for 8 hours under reflux conditions.

  Using the reaction solution obtained above as a water / oil repellent, a glass plate having a smooth surface (vertical: 50 mm, horizontal: 20 mm) so that the thickness of the film after drying the water / oil repellent with a bar coater is 10 μm. , Thickness: 3 mm) and dried in air at 60 ° C. to obtain a test piece.

  Next, the water repellency and water repellency, oil repellency and oil repellency, and water solubility of the coating were examined in the same manner as in Example 1 using the test pieces obtained above. Further, the water dilution of the water / oil repellent was examined in the same manner as in Example 1. As a result, the water repellency (contact angle) was 117.3 °, the water repellency persistence was 61.5%, the oil repellency (contact angle) was 60 °, and the oil repellency persistence was 91.7%. Evaluation of water solubility was B, and evaluation of water dilutability was A.

Example 4
N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine, lauryl in a 500 mL five-necked flask equipped with a stirrer, an inert gas inlet, a reflux condenser and a thermometer Acrylate [manufactured by Osaka Organic Chemical Industry Co., Ltd.] 10 g and 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate [Osaka Organic Chemical Industry ( Co., Ltd., product number: V-13F] A monomer component consisting of 20 g and 234 g of ethyl alcohol were added. After heating the contents of the flask to 75 ° C., 0.6 g of dimethyl-2,2′-azobis (2-methylpropionate) [manufactured by Wako Pure Chemical Industries, Ltd., product number: V-601] was added to the flask. The reaction solution containing the polymer composed of the monomer components was obtained by putting in the solution and carrying out the polymerization reaction with stirring for 8 hours under reflux conditions.

  Using the reaction solution obtained above as a water / oil repellent, a glass plate having a smooth surface (vertical: 50 mm, horizontal: 20 mm) so that the thickness of the film after drying the water / oil repellent with a bar coater is 10 μm. , Thickness: 3 mm) and dried in air at 60 ° C. to obtain a test piece.

  Next, the water repellency and water repellency, oil repellency and oil repellency, and water solubility of the coating were examined in the same manner as in Example 1 using the test pieces obtained above. Further, the water dilution of the water / oil repellent was examined in the same manner as in Example 1. As a result, the water repellency (contact angle) was 102.6 °, the water repellency persistence was 74.6%, the water repellency persistence was 74.6%, and the oil repellency (contact angle) was 80 °. The oil repellency persistence was 93.8%, the water solubility was evaluated as B, and the water dilution property was evaluated as A.

Example 5
40 g of N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine, lauryl in a 500 mL five-necked flask equipped with a stirrer, an inert gas inlet, a reflux condenser and a thermometer 50 g of acrylate [Osaka Organic Chemical Co., Ltd.] and 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate [Osaka Organic Chemical ( Co., Ltd., product number: V-13F] A monomer component consisting of 10 g and 234 g of ethyl alcohol were added. After heating the contents of the flask to 75 ° C., 0.6 g of dimethyl-2,2′-azobis (2-methylpropionate) [manufactured by Wako Pure Chemical Industries, Ltd., product number: V-601] was added to the flask. The reaction solution containing the polymer composed of the monomer components was obtained by putting in the solution and carrying out the polymerization reaction with stirring for 8 hours under reflux conditions.

  Using the reaction solution obtained above as a water / oil repellent, a glass plate having a smooth surface (vertical: 50 mm, horizontal: 20 mm) so that the thickness of the film after drying the water / oil repellent with a bar coater is 10 μm. , Thickness: 3 mm) and dried in air at 60 ° C. to obtain a test piece.

  Next, the water repellency and water repellency, oil repellency and oil repellency, and water solubility of the coating were examined in the same manner as in Example 1 using the test pieces obtained above. Further, the water dilution of the water / oil repellent was examined in the same manner as in Example 1. As a result, the water repellency (contact angle) was 111.6 °, the water repellency persistence was 82.0%, the oil repellency (contact angle) was 69.2 °, and the oil repellency persistence was 99. The evaluation of water solubility was B, and the evaluation of water dilution was A.

Example 6
20 g of N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine, lauryl in a 500 mL five-necked flask equipped with a stirrer, an inert gas inlet, a reflux condenser and a thermometer 70 g of acrylate [Osaka Organic Chemical Co., Ltd.] and 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate [Osaka Organic Chemical ( Co., Ltd., product number: V-13F] A monomer component consisting of 10 g and 234 g of ethyl alcohol were added. After heating the contents of the flask to 75 ° C., 0.6 g of dimethyl-2,2′-azobis (2-methylpropionate) [manufactured by Wako Pure Chemical Industries, Ltd., product number: V-601] was added to the flask. The reaction solution containing the polymer composed of the monomer components was obtained by putting in the solution and carrying out the polymerization reaction with stirring for 8 hours under reflux conditions.

  Using the reaction solution obtained above as a water / oil repellent, a glass plate having a smooth surface (vertical: 50 mm, horizontal: 20 mm) so that the thickness of the film after drying the water / oil repellent with a bar coater is 10 μm. , Thickness: 3 mm) and dried in air at 60 ° C. to obtain a test piece.

  Next, the water repellency and water repellency, oil repellency and oil repellency, and water solubility of the coating were examined in the same manner as in Example 1 using the test pieces obtained above. Further, the water dilution of the water / oil repellent was examined in the same manner as in Example 1. As a result, the water repellency (contact angle) was 120.7 °, the water repellency persistence was 91.0%, the oil repellency (contact angle) was 67.8 °, and the oil repellency persistence was 98. The water solubility was B, and the water dilutability was A.

Example 7
In a 500 mL five-necked flask equipped with a stirrer, an inert gas inlet, a reflux condenser and a thermometer, 70 g of N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine, stearyl 20 g of methacrylate and 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate [manufactured by Osaka Organic Chemical Industry Co., Ltd., product number: V-13F] A monomer component consisting of 10 g and 234 g of ethyl alcohol were added. After heating the contents of the flask to 75 ° C., 0.6 g of dimethyl-2,2′-azobis (2-methylpropionate) [manufactured by Wako Pure Chemical Industries, Ltd., product number: V-601] was added to the flask. The reaction solution containing the polymer composed of the monomer components was obtained by putting in the solution and carrying out the polymerization reaction with stirring for 8 hours under reflux conditions.

  Using the reaction solution obtained above as a water / oil repellent, a glass plate having a smooth surface (vertical: 50 mm, horizontal: 20 mm) so that the thickness of the film after drying the water / oil repellent with a bar coater is 10 μm. , Thickness: 3 mm) and dried in air at 60 ° C. to obtain a test piece.

  Next, the water repellency and water repellency, oil repellency and oil repellency, and water solubility of the coating were examined in the same manner as in Example 1 using the test pieces obtained above. Further, the water dilution of the water / oil repellent was examined in the same manner as in Example 1. As a result, the water repellency (contact angle) was 119.0 °, the water repellency persistence was 96.7%, the oil repellency (contact angle) was 51.3 °, and the oil repellency persistence was 97.degree. The evaluation of water solubility was B, and the evaluation of water dilutability was B.

Example 8
70 g of N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine in a 500 mL 5-neck flask equipped with a stirrer, inert gas inlet, reflux condenser and thermometer, -20 g of ethylhexyl acrylate and 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate [manufactured by Osaka Organic Chemical Industry Co., Ltd., product number: V- [13F] A monomer component consisting of 10 g and 234 g of ethyl alcohol were added. After heating the contents of the flask to 75 ° C., 0.6 g of dimethyl-2,2′-azobis (2-methylpropionate) [manufactured by Wako Pure Chemical Industries, Ltd., product number: V-601] was added to the flask. The reaction solution containing the polymer composed of the monomer components was obtained by putting in the solution and carrying out the polymerization reaction with stirring for 8 hours under reflux conditions.

  Using the reaction solution obtained above as a water / oil repellent, a glass plate having a smooth surface (vertical: 50 mm, horizontal: 20 mm) so that the thickness of the film after drying the water / oil repellent with a bar coater is 10 μm. , Thickness: 3 mm) and dried in air at 60 ° C. to obtain a test piece.

  Next, the water repellency and water repellency, oil repellency and oil repellency, and water solubility of the coating were examined in the same manner as in Example 1 using the test pieces obtained above. Further, the water dilution of the water / oil repellent was examined in the same manner as in Example 1. As a result, the water repellency (contact angle) is 100 °, the water repellency persistence is 35.5%, the oil repellency (contact angle) is 71.4 °, and the oil repellency persistence is 100.0%. Evaluation of water solubility was B, and evaluation of water dilutability was A.

Example 9
40 g of N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine in a 500 mL five-necked flask equipped with a stirrer, an inert gas inlet, a reflux condenser and a thermometer, -50 g of ethylhexyl acrylate and 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate [manufactured by Osaka Organic Chemical Industry Co., Ltd., product number: V- [13F] A monomer component consisting of 10 g and 234 g of ethyl alcohol were added. After heating the contents of the flask to 75 ° C., 0.6 g of dimethyl-2,2′-azobis (2-methylpropionate) [manufactured by Wako Pure Chemical Industries, Ltd., product number: V-601] was added to the flask. The reaction solution containing the polymer composed of the monomer components was obtained by putting in the solution and carrying out the polymerization reaction with stirring for 8 hours under reflux conditions.

  Using the reaction solution obtained above as a water / oil repellent, a glass plate having a smooth surface (vertical: 50 mm, horizontal: 20 mm) so that the thickness of the film after drying the water / oil repellent with a bar coater is 10 μm. , Thickness: 3 mm) and dried in air at 60 ° C. to obtain a test piece.

  Next, the water repellency and water repellency, oil repellency and oil repellency, and water solubility of the coating were examined in the same manner as in Example 1 using the test pieces obtained above. Further, the water dilution of the water / oil repellent was examined in the same manner as in Example 1. As a result, the water repellency (contact angle) was 109.1 °, the water repellency persistence was 56.1%, the oil repellency (contact angle) was 69.2 °, and the oil repellency persistence was 99.degree. The evaluation of water solubility was B, and the evaluation of water dilution was A.

Example 10
20 g of N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine in a 500 mL five-necked flask equipped with a stirrer, an inert gas inlet, a reflux condenser and a thermometer, -70 g of ethylhexyl acrylate and 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate [manufactured by Osaka Organic Chemical Industry Co., Ltd., product number: V- [13F] A monomer component consisting of 10 g and 234 g of ethyl alcohol were added. After heating the contents of the flask to 75 ° C., 0.6 g of dimethyl-2,2′-azobis (2-methylpropionate) [manufactured by Wako Pure Chemical Industries, Ltd., product number: V-601] was added to the flask. The reaction solution containing the polymer composed of the monomer components was obtained by putting in the solution and carrying out the polymerization reaction with stirring for 8 hours under reflux conditions.

  Using the reaction solution obtained above as a water / oil repellent, a glass plate having a smooth surface (vertical: 50 mm, horizontal: 20 mm) so that the thickness of the film after drying the water / oil repellent with a bar coater is 10 μm. , Thickness: 3 mm) and dried in air at 60 ° C. to obtain a test piece.

  Next, the water repellency and water repellency, oil repellency and oil repellency, and water solubility of the coating were examined in the same manner as in Example 1 using the test pieces obtained above. Further, the water dilution of the water / oil repellent was examined in the same manner as in Example 1. As a result, the water repellency (contact angle) was 121.6 °, the water repellency persistence was 71.3%, the oil repellency (contact angle) was 67.8 °, and the oil repellency persistence was 98. The water solubility was A, and the water dilution evaluation was A.

Example 11
5 g of N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine in a 500 mL 5-neck flask equipped with a stirrer, an inert gas inlet, a reflux condenser and a thermometer, -Acrylamide-2-methylpropanesulfonic acid 5 g, 2-ethylhexyl acrylate 80 g and 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate [Osaka Monomer component consisting of 10 g of organic chemical industry, product number: V-13F] and 234 g of ethyl alcohol were added. After heating the contents of the flask to 75 ° C., 0.6 g of dimethyl-2,2′-azobis (2-methylpropionate) [manufactured by Wako Pure Chemical Industries, Ltd., product number: V-601] was added to the flask. The reaction solution containing the polymer composed of the monomer components was obtained by putting in the solution and carrying out the polymerization reaction with stirring for 8 hours under reflux conditions.

  Using the reaction solution obtained above as a water / oil repellent, a glass plate having a smooth surface (vertical: 50 mm, horizontal: 20 mm) so that the thickness of the film after drying the water / oil repellent with a bar coater is 10 μm. , Thickness: 3 mm) and dried in air at 60 ° C. to obtain a test piece.

  Next, the water repellency and water repellency, oil repellency and oil repellency, and water solubility of the coating were examined in the same manner as in Example 1 using the test pieces obtained above. Further, the water dilution of the water / oil repellent was examined in the same manner as in Example 1. As a result, the water repellency (contact angle) was 119.8 °, the water repellency persistence was 86.8%, the oil repellency (contact angle) was 76.1 °, and the oil repellency persistence was 98. The evaluation of water solubility was B, and the evaluation of water dilution was B.

Example 12
5 g of N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine in a 500 mL 5-neck flask equipped with a stirrer, an inert gas inlet, a reflux condenser and a thermometer, -Acrylamide-2-methylpropanesulfonic acid 5 g, 2-ethylhexyl acrylate 80 g and 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate [Osaka Monomer component consisting of 10 g of organic chemical industry, product number: V-13F] and 234 g of ethyl alcohol were added. After heating the contents of the flask to 75 ° C., 0.6 g of dimethyl-2,2′-azobis (2-methylpropionate) [manufactured by Wako Pure Chemical Industries, Ltd., product number: V-601] was added to the flask. The reaction solution containing the polymer composed of the monomer components was obtained by putting in the solution and carrying out the polymerization reaction with stirring for 8 hours under reflux conditions.

  To the reaction solution obtained above, 7.2 g of triethanolamine and 178 g of ethyl alcohol were added and mixed to obtain a water / oil repellent. The water / oil repellent obtained as described above was applied to a glass plate (length: 50 mm, width: 20 mm, thickness: 3 mm) having a smooth surface so that the thickness of the film after drying with a bar coater was 10 μm. A test piece was obtained by drying in the atmosphere of ° C.

  Next, the water repellency and water repellency, oil repellency and oil repellency, and water solubility of the coating were examined in the same manner as in Example 1 using the test pieces obtained above. Further, the water dilution of the water / oil repellent was examined in the same manner as in Example 1. As a result, the water repellency (contact angle) was 112.7 °, the water repellency persistence was 84.7%, the oil repellency (contact angle) was 102.1 °, and the oil repellency persistence was 96. The evaluation of water solubility was A, and the evaluation of water dilution was A.

Example 13
10 g of N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine in a 500 mL five-necked flask equipped with a stirrer, an inert gas inlet, a reflux condenser and a thermometer, -Acrylamide-2-methylpropanesulfonic acid 5 g, 2-ethylhexyl acrylate 75 g and 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate [Osaka Monomer component consisting of 10 g of organic chemical industry, product number: V-13F] and 234 g of ethyl alcohol were added. After heating the contents of the flask to 75 ° C., 0.6 g of dimethyl-2,2′-azobis (2-methylpropionate) [manufactured by Wako Pure Chemical Industries, Ltd., product number: V-601] was added to the flask. The reaction solution containing the polymer composed of the monomer components was obtained by putting in the solution and carrying out the polymerization reaction with stirring for 8 hours under reflux conditions.

  Using the reaction solution obtained above as a water / oil repellent, a glass plate having a smooth surface (vertical: 50 mm, horizontal: 20 mm) so that the thickness of the film after drying the water / oil repellent with a bar coater is 10 μm. , Thickness: 3 mm) and dried in air at 60 ° C. to obtain a test piece.

  Next, the water repellency and water repellency, oil repellency and oil repellency, and water solubility of the coating were examined in the same manner as in Example 1 using the test pieces obtained above. Further, the water dilution of the water / oil repellent was examined in the same manner as in Example 1. As a result, the water repellency (contact angle) was 116.5 °, the water repellency persistence was 78.5%, the oil repellency (contact angle) was 56.8 °, and the oil repellency persistence was 100. The evaluation of water solubility was B, and the evaluation of water dilution was B.

Example 14
10 g of N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine in a 500 mL five-necked flask equipped with a stirrer, an inert gas inlet, a reflux condenser and a thermometer, -10 g of hydroxyethyl acrylate, 70 g of 2-ethylhexyl acrylate and 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate [Osaka Organic Chemical Co., Ltd. ), Product number: V-13F] A monomer component consisting of 10 g and 234 g of ethyl alcohol were added. After heating the contents of the flask to 75 ° C., 0.6 g of dimethyl-2,2′-azobis (2-methylpropionate) [manufactured by Wako Pure Chemical Industries, Ltd., product number: V-601] was added to the flask. The reaction solution containing the polymer composed of the monomer components was obtained by putting in the solution and carrying out the polymerization reaction with stirring for 8 hours under reflux conditions.

  Using the reaction solution obtained above as a water / oil repellent, a glass plate having a smooth surface (vertical: 50 mm, horizontal: 20 mm) so that the thickness of the film after drying the water / oil repellent with a bar coater is 10 μm. , Thickness: 3 mm) and dried in air at 60 ° C. to obtain a test piece.

  Next, the water repellency and water repellency, oil repellency and oil repellency, and water solubility of the coating were examined in the same manner as in Example 1 using the test pieces obtained above. Further, the water dilution of the water / oil repellent was examined in the same manner as in Example 1. As a result, the water repellency (contact angle) was 123.6 °, the water repellency persistence was 64.3%, the oil repellency (contact angle) was 95.7 °, and the oil repellency persistence was 89.degree. The evaluation of water solubility was B, and the evaluation of water dilution was B.

Example 15
20 g of N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine in a 500 mL five-necked flask equipped with a stirrer, an inert gas inlet, a reflux condenser and a thermometer, -20 g of hydroxyethyl acrylate, 50 g of 2-ethylhexyl acrylate and 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate [Osaka Organic Chemical Co., Ltd. ), Product number: V-13F] A monomer component consisting of 10 g and 234 g of ethyl alcohol were added. After heating the contents of the flask to 75 ° C., 0.6 g of dimethyl-2,2′-azobis (2-methylpropionate) [manufactured by Wako Pure Chemical Industries, Ltd., product number: V-601] was added to the flask. The reaction solution containing the polymer composed of the monomer components was obtained by putting in the solution and carrying out the polymerization reaction with stirring for 8 hours under reflux conditions.

  Using the reaction solution obtained above as a water / oil repellent, a glass plate having a smooth surface (vertical: 50 mm, horizontal: 20 mm) so that the thickness of the film after drying the water / oil repellent with a bar coater is 10 μm. , Thickness: 3 mm) and dried in air at 60 ° C. to obtain a test piece.

  Next, the water repellency and water repellency, oil repellency and oil repellency, and water solubility of the coating were examined in the same manner as in Example 1 using the test pieces obtained above. Further, the water dilution of the water / oil repellent was examined in the same manner as in Example 1. As a result, the water repellency (contact angle) was 123.7 °, the water repellency persistence was 23.1%, the oil repellency (contact angle) was 92 °, and the oil repellency persistence was 93.8%. Evaluation of water solubility was B, and evaluation of water dilution was B.

Example 16
10 g of N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine in a 500 mL five-necked flask equipped with a stirrer, an inert gas inlet, a reflux condenser and a thermometer, -20 g of hydroxyethyl acrylate, 60 g of 2-ethylhexyl acrylate and 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate [Osaka Organic Chemical Co., Ltd. ), Product number: V-13F] A monomer component consisting of 10 g and 234 g of ethyl alcohol were added. After heating the contents of the flask to 75 ° C., 0.6 g of dimethyl-2,2′-azobis (2-methylpropionate) [manufactured by Wako Pure Chemical Industries, Ltd., product number: V-601] was added to the flask. The reaction solution containing the polymer composed of the monomer components was obtained by putting in the solution and carrying out the polymerization reaction with stirring for 8 hours under reflux conditions.

  Using the reaction solution obtained above as a water / oil repellent, a glass plate having a smooth surface (vertical: 50 mm, horizontal: 20 mm) so that the thickness of the film after drying the water / oil repellent with a bar coater is 10 μm. , Thickness: 3 mm) and dried in air at 60 ° C. to obtain a test piece.

  Next, the water repellency and water repellency, oil repellency and oil repellency, and water solubility of the coating were examined in the same manner as in Example 1 using the test pieces obtained above. Further, the water dilution of the water / oil repellent was examined in the same manner as in Example 1. As a result, the water repellency (contact angle) was 131.3 °, the water repellency persistence was 32.7%, the oil repellency (contact angle) was 91.4 °, and the oil repellency persistence was 93. The water solubility was B, and the water dilutability was B.

Example 17
20 g of N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine in a 500 mL five-necked flask equipped with a stirrer, an inert gas inlet, a reflux condenser and a thermometer, -10 g of hydroxyethyl acrylate, 60 g of 2-ethylhexyl acrylate and 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate [Osaka Organic Chemical Co., Ltd. ), Product number: V-13F] A monomer component consisting of 10 g and 234 g of ethyl alcohol were added. After heating the contents of the flask to 75 ° C., 0.6 g of dimethyl-2,2′-azobis (2-methylpropionate) [manufactured by Wako Pure Chemical Industries, Ltd., product number: V-601] was added to the flask. The reaction solution containing the polymer composed of the monomer components was obtained by putting in the solution and carrying out the polymerization reaction with stirring for 8 hours under reflux conditions.

  Using the reaction solution obtained above as a water / oil repellent, a glass plate having a smooth surface (vertical: 50 mm, horizontal: 20 mm) so that the thickness of the film after drying the water / oil repellent with a bar coater is 10 μm. , Thickness: 3 mm) and dried in air at 60 ° C. to obtain a test piece.

  Next, the water repellency and water repellency, oil repellency and oil repellency, and water solubility of the coating were examined in the same manner as in Example 1 using the test pieces obtained above. Further, the water dilution of the water / oil repellent was examined in the same manner as in Example 1. As a result, the water repellency (contact angle) was 121.6 °, the water repellency persistence was 53.0%, the oil repellency (contact angle) was 93.9 °, and the oil repellency persistence was 87.degree. The evaluation of water solubility was B, and the evaluation of water dilution was B.

Example 18
20 g of N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine in a 500 mL five-necked flask equipped with a stirrer, an inert gas inlet, a reflux condenser and a thermometer, -5 g of hydroxyethyl acrylate, 65 g of 2-ethylhexyl acrylate and 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate [Osaka Organic Chemical Co., Ltd. ), Product number: V-13F] A monomer component consisting of 10 g and 234 g of ethyl alcohol were added. After heating the contents of the flask to 75 ° C., 0.6 g of dimethyl-2,2′-azobis (2-methylpropionate) [manufactured by Wako Pure Chemical Industries, Ltd., product number: V-601] was added to the flask. The reaction solution containing the polymer composed of the monomer components was obtained by putting in the solution and carrying out the polymerization reaction with stirring for 8 hours under reflux conditions.

  Using the reaction solution obtained above as a water / oil repellent, a glass plate having a smooth surface (vertical: 50 mm, horizontal: 20 mm) so that the thickness of the film after drying the water / oil repellent with a bar coater is 10 μm. , Thickness: 3 mm) and dried in air at 60 ° C. to obtain a test piece.

  Next, the water repellency and water repellency, oil repellency and oil repellency, and water solubility of the coating were examined in the same manner as in Example 1 using the test pieces obtained above. Further, the water dilution of the water / oil repellent was examined in the same manner as in Example 1. As a result, the water repellency (contact angle) was 121.2 °, the water repellency persistence was 72.0%, the oil repellency (contact angle) was 94.5 °, and the oil repellency persistence was 92.degree. The water solubility was B, and the water dilutability was B.

Example 19
60 g of N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine in a 500 mL 5-neck flask equipped with a stirrer, inert gas inlet, reflux condenser and thermometer, -10 g of hydroxyethyl acrylate, 20 g of stearyl methacrylate and 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate [manufactured by Osaka Organic Chemical Industry Co., Ltd. , Product number: V-13F] A monomer component consisting of 10 g and 234 g of ethyl alcohol were added. After heating the contents of the flask to 75 ° C., 0.6 g of dimethyl-2,2′-azobis (2-methylpropionate) [manufactured by Wako Pure Chemical Industries, Ltd., product number: V-601] was added to the flask. The reaction solution containing the polymer composed of the monomer components was obtained by putting in the solution and carrying out the polymerization reaction with stirring for 8 hours under reflux conditions.

  Using the reaction solution obtained above as a water / oil repellent, a glass plate having a smooth surface (vertical: 50 mm, horizontal: 20 mm) so that the thickness of the film after drying the water / oil repellent with a bar coater is 10 μm. , Thickness: 3 mm) and dried in air at 60 ° C. to obtain a test piece.

  Next, the water repellency and water repellency, oil repellency and oil repellency, and water solubility of the coating were examined in the same manner as in Example 1 using the test pieces obtained above. Further, the water dilution of the water / oil repellent was examined in the same manner as in Example 1. As a result, the water repellency (contact angle) was 111.8 °, the water repellency persistence was 98.0%, the oil repellency (contact angle) was 74.8 °, and the oil repellency persistence was 100. The evaluation of water solubility was B, and the evaluation of water dilution was B.

Example 20
5 g of N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine in a 500 mL 5-neck flask equipped with a stirrer, an inert gas inlet, a reflux condenser and a thermometer, -Acrylamide-2-methylpropanesulfonic acid 10 g, 2-ethylhexyl acrylate 75 g and 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate [Osaka Monomer component consisting of 10 g of organic chemical industry, product number: V-13F] and 234 g of ethyl alcohol were added. After heating the contents of the flask to 75 ° C., 0.6 g of dimethyl-2,2′-azobis (2-methylpropionate) [manufactured by Wako Pure Chemical Industries, Ltd., product number: V-601] was added to the flask. The reaction solution containing the polymer composed of the monomer components was obtained by putting in the solution and carrying out the polymerization reaction with stirring for 8 hours under reflux conditions.

  Using the reaction solution obtained above as a water / oil repellent, a glass plate having a smooth surface (vertical: 50 mm, horizontal: 20 mm) so that the thickness of the film after drying the water / oil repellent with a bar coater is 10 μm. , Thickness: 3 mm) and dried in air at 60 ° C. to obtain a test piece.

  Next, the water repellency and water repellency, oil repellency and oil repellency, and water solubility of the coating were examined in the same manner as in Example 1 using the test pieces obtained above. Further, the water dilution of the water / oil repellent was examined in the same manner as in Example 1. As a result, the water repellency (contact angle) was 120.6 °, the water repellency persistence was 91.7%, the oil repellency (contact angle) was 99.4 °, and the oil repellency persistence was 96. The water solubility was B, and the water dilutability was B.

Example 21
5 g of N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine in a 500 mL 5-neck flask equipped with a stirrer, an inert gas inlet, a reflux condenser and a thermometer, -Acrylamide-2-methylpropanesulfonic acid 10 g, 2-ethylhexyl acrylate 75 g and 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate [Osaka Monomer component consisting of 10 g of organic chemical industry, product number: V-13F] and 234 g of ethyl alcohol were added. After heating the contents of the flask to 75 ° C., 0.6 g of dimethyl-2,2′-azobis (2-methylpropionate) [manufactured by Wako Pure Chemical Industries, Ltd., product number: V-601] was added to the flask. The reaction solution containing the polymer composed of the monomer components was obtained by putting in the solution and carrying out the polymerization reaction with stirring for 8 hours under reflux conditions.

  To the reaction solution obtained above, 7.2 g of triethanolamine and 178 g of ethyl alcohol were added and mixed to obtain a water / oil repellent. The water / oil repellent obtained as described above was applied to a glass plate (length: 50 mm, width: 20 mm, thickness: 3 mm) having a smooth surface so that the thickness of the film after drying with a bar coater was 10 μm. A test piece was obtained by drying in the atmosphere of ° C.

  Next, the water repellency and water repellency, oil repellency and oil repellency, and water solubility of the coating were examined in the same manner as in Example 1 using the test pieces obtained above. Further, the water dilution of the water / oil repellent was examined in the same manner as in Example 1. As a result, the water repellency (contact angle) was 107.4 °, the water repellency persistence was 71.1%, the oil repellency (contact angle) was 71.4 °, and the oil repellency persistence was 98. The evaluation of water solubility was A, and the evaluation of water dilution was A.

Example 22
5 g of N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine in a 500 mL 5-neck flask equipped with a stirrer, an inert gas inlet, a reflux condenser and a thermometer, -Acrylamide-2-methylpropanesulfonic acid 20 g, 2-ethylhexyl acrylate 65 g and 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate [Osaka Monomer component consisting of 10 g of organic chemical industry, product number: V-13F] and 234 g of ethyl alcohol were added. After heating the contents of the flask to 75 ° C., 0.6 g of dimethyl-2,2′-azobis (2-methylpropionate) [manufactured by Wako Pure Chemical Industries, Ltd., product number: V-601] was added to the flask. The reaction solution containing the polymer composed of the monomer components was obtained by putting in the solution and carrying out the polymerization reaction with stirring for 8 hours under reflux conditions.

  Using the reaction solution obtained above as a water / oil repellent, a glass plate having a smooth surface (vertical: 50 mm, horizontal: 20 mm) so that the thickness of the film after drying the water / oil repellent with a bar coater is 10 μm. , Thickness: 3 mm) and dried in air at 60 ° C. to obtain a test piece.

  Next, the water repellency and water repellency, oil repellency and oil repellency, and water solubility of the coating were examined in the same manner as in Example 1 using the test pieces obtained above. Further, the water dilution of the water / oil repellent was examined in the same manner as in Example 1. As a result, the water repellency (contact angle) was 112.2 °, the water repellency persistence was 85.9%, the oil repellency (contact angle) was 59.7 °, and the oil repellency persistence was 99. The evaluation of water solubility was B, and the evaluation of water dilutability was B.

Example 23
5 g of N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine in a 500 mL 5-neck flask equipped with a stirrer, an inert gas inlet, a reflux condenser and a thermometer, -Acrylamide-2-methylpropanesulfonic acid 10 g, 2-ethylhexyl acrylate 74 g, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate [Osaka A monomer component consisting of 10 g of Organic Chemical Industry Co., Ltd., product number: V-13F] and 1 g of tripropylene glycol diacrylate and 234 g of ethyl alcohol were added. After heating the contents of the flask to 75 ° C., 0.6 g of dimethyl-2,2′-azobis (2-methylpropionate) [manufactured by Wako Pure Chemical Industries, Ltd., product number: V-601] was added to the flask. The reaction solution containing the polymer composed of the monomer components was obtained by putting in the solution and carrying out the polymerization reaction with stirring for 8 hours under reflux conditions.

  To the reaction solution obtained above, 7.2 g of triethanolamine and 178 g of ethyl alcohol were added and mixed to obtain a water / oil repellent. The water / oil repellent obtained as described above was applied to a glass plate (length: 50 mm, width: 20 mm, thickness: 3 mm) having a smooth surface so that the thickness of the film after drying with a bar coater was 10 μm. A test piece was obtained by drying in the atmosphere of ° C.

  Next, the water repellency and water repellency, oil repellency and oil repellency, and water solubility of the coating were examined in the same manner as in Example 1 using the test pieces obtained above. Further, the water dilution of the water / oil repellent was examined in the same manner as in Example 1. As a result, the water repellency (contact angle) was 101.9 °, the water repellency persistence was 70.4%, the oil repellency (contact angle) was 91.9 °, and the oil repellency persistence was 98. The evaluation of water solubility was A, and the evaluation of water dilution was A.

Example 24
5 g of N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine in a 500 mL 5-neck flask equipped with a stirrer, an inert gas inlet, a reflux condenser and a thermometer, -Acrylamide-2-methylpropanesulfonic acid 10 g, 2-ethylhexyl acrylate 72 g, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate [Osaka Monomer component consisting of 10 g of organic chemical industry, product number: V-13F] and 3 g of tripropylene glycol diacrylate and 234 g of ethyl alcohol were added. After heating the contents of the flask to 75 ° C., 0.6 g of dimethyl-2,2′-azobis (2-methylpropionate) [manufactured by Wako Pure Chemical Industries, Ltd., product number: V-601] was added to the flask. The reaction solution containing the polymer composed of the monomer components was obtained by putting in the solution and carrying out the polymerization reaction with stirring for 8 hours under reflux conditions.

  To the reaction solution obtained above, 7.2 g of triethanolamine and 178 g of ethyl alcohol were added and mixed to obtain a water / oil repellent. The water / oil repellent obtained as described above was applied to a glass plate (length: 50 mm, width: 20 mm, thickness: 3 mm) having a smooth surface so that the thickness of the film after drying with a bar coater was 10 μm. A test piece was obtained by drying in the atmosphere of ° C.

  Next, the water repellency and water repellency, oil repellency and oil repellency, and water solubility of the coating were examined in the same manner as in Example 1 using the test pieces obtained above. Further, the water dilution of the water / oil repellent was examined in the same manner as in Example 1. As a result, the water repellency (contact angle) was 111.9 °, the water repellency persistence was 68.7%, the oil repellency (contact angle) was 92.9 °, and the oil repellency persistence was 97. The evaluation of water solubility was A, and the evaluation of water dilution was A.

Example 25
5 g of N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine in a 500 mL 5-neck flask equipped with a stirrer, an inert gas inlet, a reflux condenser and a thermometer, -Acrylamide-2-methylpropanesulfonic acid 10 g, 2-ethylhexyl acrylate 70 g, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate [Osaka Monomer component consisting of 10 g of organic chemical industry, product number: V-13F] and 5 g of tripropylene glycol diacrylate and 234 g of ethyl alcohol were added. After heating the contents of the flask to 75 ° C., 0.6 g of dimethyl-2,2′-azobis (2-methylpropionate) [manufactured by Wako Pure Chemical Industries, Ltd., product number: V-601] was added to the flask. The reaction solution containing the polymer composed of the monomer components was obtained by putting in the solution and carrying out the polymerization reaction with stirring for 8 hours under reflux conditions.

  To the reaction solution obtained above, 7.2 g of triethanolamine and 178 g of ethyl alcohol were added and mixed to obtain a water / oil repellent. The water / oil repellent obtained as described above was applied to a glass plate (length: 50 mm, width: 20 mm, thickness: 3 mm) having a smooth surface so that the thickness of the film after drying with a bar coater was 10 μm. A test piece was obtained by drying in the atmosphere of ° C.

Next, the water repellency and water repellency, oil repellency and oil repellency, and water solubility of the coating were examined in the same manner as in Example 1 using the test pieces obtained above. Further, the water dilution of the water / oil repellent was examined in the same manner as in Example 1. As a result, the water repellency (contact angle) was 112.3 °, the water repellency persistence was 77.8%, the oil repellency (contact angle) was 90.3 °, and the oil repellency persistence was 96. The water solubility was A, and the water dilution evaluation was A.

Example 26
5 g of N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine in a 500 mL 5-neck flask equipped with a stirrer, an inert gas inlet, a reflux condenser and a thermometer, -Acrylamide-2-methylpropanesulfonic acid 10 g, 2-ethylhexyl acrylate 65 g, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate [Osaka A monomer component consisting of 10 g of organic chemical industry, product number: V-13F] and 10 g of tripropylene glycol diacrylate, and 234 g of ethyl alcohol were added. After heating the contents of the flask to 75 ° C., 0.6 g of dimethyl-2,2′-azobis (2-methylpropionate) [manufactured by Wako Pure Chemical Industries, Ltd., product number: V-601] was added to the flask. The reaction solution containing the polymer composed of the monomer components was obtained by putting in the solution and carrying out the polymerization reaction with stirring for 8 hours under reflux conditions.

  To the reaction solution obtained above, 7.2 g of triethanolamine and 178 g of ethyl alcohol were added and mixed to obtain a water / oil repellent. The water / oil repellent obtained as described above was applied to a glass plate (length: 50 mm, width: 20 mm, thickness: 3 mm) having a smooth surface so that the thickness of the film after drying with a bar coater was 10 μm. A test piece was obtained by drying in the atmosphere of ° C.

  Next, the water repellency and water repellency, oil repellency and oil repellency, and water solubility of the coating were examined in the same manner as in Example 1 using the test pieces obtained above. Further, the water dilution of the water / oil repellent was examined in the same manner as in Example 1. As a result, the water repellency (contact angle) was 121.5 °, the water repellency persistence was 96.1%, the oil repellency (contact angle) was 97.2 °, and the oil repellency persistence was 99. The evaluation of water solubility was A, and the evaluation of water dilution was A.

Example 27
5 g of N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine in a 500 mL 5-neck flask equipped with a stirrer, an inert gas inlet, a reflux condenser and a thermometer, -Acrylamide-2-methylpropanesulfonic acid 10 g, 2-ethylhexyl acrylate 70 g, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate [Osaka A monomer component consisting of 10 g of Organic Chemical Industry Co., Ltd., product number: V-13F] and 5 g of polyethylene glycol (4) dimethacrylate and 234 g of ethyl alcohol were added. After heating the contents of the flask to 75 ° C., 0.6 g of dimethyl-2,2′-azobis (2-methylpropionate) [manufactured by Wako Pure Chemical Industries, Ltd., product number: V-601] was added to the flask. The reaction solution containing the polymer composed of the monomer components was obtained by putting in the solution and carrying out the polymerization reaction with stirring for 8 hours under reflux conditions.

  To the reaction solution obtained above, 7.2 g of triethanolamine and 178 g of ethyl alcohol were added and mixed to obtain a water / oil repellent. The water / oil repellent obtained as described above was applied to a glass plate (length: 50 mm, width: 20 mm, thickness: 3 mm) having a smooth surface so that the thickness of the film after drying with a bar coater was 10 μm. A test piece was obtained by drying in the atmosphere of ° C.

  Next, the water repellency and water repellency, oil repellency and oil repellency, and water solubility of the coating were examined in the same manner as in Example 1 using the test pieces obtained above. Further, the water dilution of the water / oil repellent was examined in the same manner as in Example 1. As a result, the water repellency (contact angle) was 122.9 °, the water repellency persistence was 90.5%, the oil repellency (contact angle) was 98.3 °, and the oil repellency persistence was 97. The evaluation of water solubility was A, and the evaluation of water dilutability was A.

Example 28
5 g of N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine in a 500 mL 5-neck flask equipped with a stirrer, an inert gas inlet, a reflux condenser and a thermometer, -Acrylamide-2-methylpropanesulfonic acid 10 g, 2-ethylhexyl acrylate 70 g, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate [Osaka A monomer component consisting of 10 g of Organic Chemical Industry Co., Ltd., product number: V-13F] and 5 g of polyethylene glycol (14) dimethacrylate and 234 g of ethyl alcohol were added. After heating the contents of the flask to 75 ° C., 0.6 g of dimethyl-2,2′-azobis (2-methylpropionate) [manufactured by Wako Pure Chemical Industries, Ltd., product number: V-601] was added to the flask. The reaction solution containing the polymer composed of the monomer components was obtained by putting in the solution and carrying out the polymerization reaction with stirring for 8 hours under reflux conditions.

  To the reaction solution obtained above, 7.2 g of triethanolamine and 178 g of ethyl alcohol were added and mixed to obtain a water / oil repellent. The water / oil repellent obtained as described above was applied to a glass plate (length: 50 mm, width: 20 mm, thickness: 3 mm) having a smooth surface so that the thickness of the film after drying with a bar coater was 10 μm. A test piece was obtained by drying in the atmosphere of ° C.

  Next, the water repellency and water repellency, oil repellency and oil repellency, and water solubility of the coating were examined in the same manner as in Example 1 using the test pieces obtained above. Further, the water dilution of the water / oil repellent was examined in the same manner as in Example 1. As a result, the water repellency (contact angle) was 125.3 °, the water repellency persistence was 96.9%, the oil repellency (contact angle) was 99.2 °, and the oil repellency persistence was 97.degree. The evaluation of water solubility was A, and the evaluation of water dilution was A.

Example 29
20 g of N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine in a 500 mL five-necked flask equipped with a stirrer, an inert gas inlet, a reflux condenser and a thermometer, n -70 g of butyl acrylate and 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate [manufactured by Osaka Organic Chemical Industry Co., Ltd., product number: V- [13F] A monomer component consisting of 10 g and 234 g of ethyl alcohol were added. After heating the contents of the flask to 75 ° C., 0.6 g of dimethyl-2,2′-azobis (2-methylpropionate) [manufactured by Wako Pure Chemical Industries, Ltd., product number: V-601] was added to the flask. The reaction solution containing the polymer composed of the monomer components was obtained by putting in the solution and carrying out the polymerization reaction with stirring for 8 hours under reflux conditions.

  Using the reaction solution obtained above as a water / oil repellent, a glass plate having a smooth surface (vertical: 50 mm, horizontal: 20 mm) so that the thickness of the film after drying the water / oil repellent with a bar coater is 10 μm. , Thickness: 3 mm) and dried in air at 60 ° C. to obtain a test piece.

  Next, the water repellency and water repellency, oil repellency and oil repellency, and water solubility of the coating were examined in the same manner as in Example 1 using the test pieces obtained above. Further, the water dilution of the water / oil repellent was examined in the same manner as in Example 1. As a result, the water repellency (contact angle) was 102 °, the water repellency persistence was 33.3%, the oil repellency (contact angle) was 72.0 °, and the oil repellency persistence was 98.6%. Evaluation of water solubility was C, and evaluation of water dilutability was B.

Example 30
20 g of N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine in a 500 mL five-necked flask equipped with a stirrer, an inert gas inlet, a reflux condenser and a thermometer, methyl 70 g of methacrylate and 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate [manufactured by Osaka Organic Chemical Industry Co., Ltd., product number: V-13F] A monomer component consisting of 10 g and 234 g of ethyl alcohol were added. After heating the contents of the flask to 75 ° C., 0.6 g of dimethyl-2,2′-azobis (2-methylpropionate) [manufactured by Wako Pure Chemical Industries, Ltd., product number: V-601] was added to the flask. The reaction solution containing the polymer composed of the monomer components was obtained by putting in the solution and carrying out the polymerization reaction with stirring for 8 hours under reflux conditions.

  Using the reaction solution obtained above as a water / oil repellent, a glass plate having a smooth surface (vertical: 50 mm, horizontal: 20 mm) so that the thickness of the film after drying the water / oil repellent with a bar coater is 10 μm. , Thickness: 3 mm) and dried in air at 60 ° C. to obtain a test piece.

  Next, the water repellency and water repellency, oil repellency and oil repellency, and water solubility of the coating were examined in the same manner as in Example 1 using the test pieces obtained above. Further, the water dilution of the water / oil repellent was examined in the same manner as in Example 1. As a result, the water repellency (contact angle) was 101 °, the water repellency persistence was 22.8%, the oil repellency (contact angle) was 73.0 °, and the oil repellency persistence was 98.6%. Evaluation of water solubility was C, and evaluation of water dilutability was B.

Comparative Example 1
In a 500 mL five-necked flask equipped with a stirrer, an inert gas inlet, a reflux condenser and a thermometer, 10 g of 2-acrylamido-2-methylpropanesulfonic acid, 80 g of 2-ethylhexyl acrylate and 3,3,4 , 4, 5, 5, 6, 6, 7, 7, 8, 8, 8-tridecafluorooctyl acrylate [manufactured by Osaka Organic Chemical Industry Co., Ltd., product number: V-13F] 10 g monomer component and ethyl alcohol 234 g was added. After heating the contents of the flask to 75 ° C., 0.6 g of dimethyl-2,2′-azobis (2-methylpropionate) [manufactured by Wako Pure Chemical Industries, Ltd., product number: V-601] was added to the flask. The reaction solution containing the polymer composed of the monomer components was obtained by putting in the solution and carrying out the polymerization reaction with stirring for 8 hours under reflux conditions.

  Using the reaction solution obtained above as a water / oil repellent, a glass plate having a smooth surface (vertical: 50 mm, horizontal: 20 mm) so that the thickness of the film after drying the water / oil repellent with a bar coater is 10 μm. , Thickness: 3 mm) and dried in air at 60 ° C. to obtain a test piece.

  Next, the water repellency and water repellency, oil repellency and oil repellency, and water solubility of the coating were examined in the same manner as in Example 1 using the test pieces obtained above. Further, the water dilution of the water / oil repellent was examined in the same manner as in Example 1. As a result, the water repellency (contact angle) was 126.7 °, the water repellency persistence was 65.0%, and the oil repellency (contact angle) was 101.8 °, but the oil repellency persistence was 75. Since it was 7%, it was confirmed that it was not suitable for actual use.

Comparative Example 2
10 g of acrylic acid, 80 g of 2-ethylhexyl acrylate and 3,3,4,4,5,5,6 in a 500 mL 5-neck flask equipped with a stirrer, inert gas inlet, reflux condenser and thermometer , 6,7,7,8,8,8-tridecafluorooctyl acrylate [manufactured by Osaka Organic Chemical Industry Co., Ltd., product number: V-13F] 10 g of a monomer component and 234 g of ethyl alcohol were added. After heating the contents of the flask to 75 ° C., 0.6 g of dimethyl-2,2′-azobis (2-methylpropionate) [manufactured by Wako Pure Chemical Industries, Ltd., product number: V-601] was added to the flask. The reaction solution containing the polymer composed of the monomer components was obtained by putting in the solution and carrying out the polymerization reaction with stirring for 8 hours under reflux conditions.

  Using the reaction solution obtained above as a water / oil repellent, a glass plate having a smooth surface (vertical: 50 mm, horizontal: 20 mm) so that the thickness of the film after drying the water / oil repellent with a bar coater is 10 μm. , Thickness: 3 mm) and dried in air at 60 ° C. to obtain a test piece.

  Next, the water repellency and water repellency, oil repellency and oil repellency, and water solubility of the coating were examined in the same manner as in Example 1 using the test pieces obtained above. Further, the water dilution of the water / oil repellent was examined in the same manner as in Example 1. As a result, the water repellency (contact angle) was 118.2 °, the water repellency persistence was 59.9%, and the oil repellency (contact angle) was 93.2 °, but the oil repellency persistence was 73. It was confirmed that it was not suitable for actual use since it was .9%.

Comparative Example 3
20 g of polyethylene glycol monoacrylate (CAS No .: 26403-58-7), 70 g of 2-ethylhexyl acrylate and a 500 mL five-necked flask equipped with a stirrer, an inert gas inlet, a reflux condenser and a thermometer 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate [manufactured by Osaka Organic Chemical Industry Co., Ltd., product number: V-13F] 10 g A monomer component and 234 g of ethyl alcohol were added. After heating the contents of the flask to 75 ° C., 0.6 g of dimethyl-2,2′-azobis (2-methylpropionate) [manufactured by Wako Pure Chemical Industries, Ltd., product number: V-601] was added to the flask. The reaction solution containing the polymer composed of the monomer components was obtained by putting in the solution and carrying out the polymerization reaction with stirring for 8 hours under reflux conditions.

  Using the reaction solution obtained above as a water / oil repellent, a glass plate having a smooth surface (vertical: 50 mm, horizontal: 20 mm) so that the thickness of the film after drying the water / oil repellent with a bar coater is 10 μm. , Thickness: 3 mm) and dried in air at 60 ° C. to obtain a test piece.

  Next, the water repellency and water repellency, oil repellency and oil repellency, and water solubility of the coating were examined in the same manner as in Example 1 using the test pieces obtained above. Further, the water dilution of the water / oil repellent was examined in the same manner as in Example 1. As a result, the water repellency (contact angle) was 133.1 °, the water repellency persistence was 76.3%, and the oil repellency (contact angle) was 92.2 °, but the oil repellency persistence was 13 Since it was 7%, it was confirmed that it was not suitable for actual use.

Comparative Example 4
In a 500 mL five-necked flask equipped with a stirrer, an inert gas inlet, a reflux condenser and a thermometer, 20 g of 2-hydroxyethyl acrylate, 70 g of 2-ethylhexyl acrylate and 3,3,4,4,5, A monomer component consisting of 10 g of 5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate [manufactured by Osaka Organic Chemical Industry Co., Ltd., product number: V-13F] and 234 g of ethyl alcohol were added. After heating the contents of the flask to 75 ° C., 0.6 g of dimethyl-2,2′-azobis (2-methylpropionate) [manufactured by Wako Pure Chemical Industries, Ltd., product number: V-601] was added to the flask. The reaction solution containing the polymer composed of the monomer components was obtained by putting in the solution and carrying out the polymerization reaction with stirring for 8 hours under reflux conditions.

  Using the reaction solution obtained above as a water / oil repellent, a glass plate having a smooth surface (vertical: 50 mm, horizontal: 20 mm) so that the thickness of the film after drying the water / oil repellent with a bar coater is 10 μm. , Thickness: 3 mm) and dried in air at 60 ° C. to obtain a test piece.

  Next, the water repellency and water repellency, oil repellency and oil repellency, and water solubility of the coating were examined in the same manner as in Example 1 using the test pieces obtained above. Further, the water dilution of the water / oil repellent was examined in the same manner as in Example 1. As a result, the water repellency (contact angle) was 113.3 °, the water repellency persistence was 39.0%, and the oil repellency (contact angle) was 98.9 °, but the oil repellency persistence was 22 It was confirmed that it was not suitable for actual use since it was .8%.

Comparative Example 5
In a 500 mL five-necked flask equipped with a stirrer, an inert gas inlet, a reflux condenser and a thermometer, 40 g of 2-hydroxyethyl acrylate, 50 g of 2-ethylhexyl acrylate and 3,3,4,4,5, A monomer component consisting of 10 g of 5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate [manufactured by Osaka Organic Chemical Industry Co., Ltd., product number: V-13F] and 234 g of ethyl alcohol were added. After heating the contents of the flask to 75 ° C., 0.6 g of dimethyl-2,2′-azobis (2-methylpropionate) [manufactured by Wako Pure Chemical Industries, Ltd., product number: V-601] was added to the flask. The reaction solution containing the polymer composed of the monomer components was obtained by putting in the solution and carrying out the polymerization reaction with stirring for 8 hours under reflux conditions.

  Using the reaction solution obtained above as a water / oil repellent, a glass plate having a smooth surface (vertical: 50 mm, horizontal: 20 mm) so that the thickness of the film after drying the water / oil repellent with a bar coater is 10 μm. , Thickness: 3 mm) and dried in air at 60 ° C. to obtain a test piece.

  Next, the water repellency and water repellency, oil repellency and oil repellency, and water solubility of the coating were examined in the same manner as in Example 1 using the test pieces obtained above. Further, the water dilution of the water / oil repellent was examined in the same manner as in Example 1. As a result, the water repellency (contact angle) was 121.3 °, the water repellency persistence was 21.5%, and the oil repellency (contact angle) was 97.2 °, but the oil repellency persistence was 59. Since it was 4%, it was confirmed that it was not suitable for actual use.

Comparative Example 6
50 g and 3 N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine in a 500 mL 5-neck flask equipped with a stirrer, inert gas inlet, reflux condenser and thermometer , 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 8-tridecafluorooctyl acrylate [manufactured by Osaka Organic Chemical Industry Co., Ltd., product number: V-13F] 50 g monomer Ingredients and 234 g of ethyl alcohol were added. After heating the contents of the flask to 75 ° C., 0.6 g of dimethyl-2,2′-azobis (2-methylpropionate) [manufactured by Wako Pure Chemical Industries, Ltd., product number: V-601] was added to the flask. The reaction solution containing the polymer composed of the monomer components was obtained by putting in the solution and carrying out the polymerization reaction with stirring for 8 hours under reflux conditions.

  Using the reaction solution obtained above as a water / oil repellent, a glass plate having a smooth surface (vertical: 50 mm, horizontal: 20 mm) so that the thickness of the film after drying the water / oil repellent with a bar coater is 10 μm. , Thickness: 3 mm) and dried in air at 60 ° C. to obtain a test piece.

  Next, the water repellency and water repellency, oil repellency and oil repellency, and water solubility of the coating were examined in the same manner as in Example 1 using the test pieces obtained above. Further, the water dilution of the water / oil repellent was examined in the same manner as in Example 1. As a result, the water repellency (contact angle) was 76 °, and it was confirmed that the water repellency was extremely inferior.

Comparative Example 7
80 g and 3 N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine in a 500 mL 5-neck flask equipped with a stirrer, inert gas inlet, reflux condenser and thermometer , 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 8-tridecafluorooctyl acrylate [manufactured by Osaka Organic Chemical Industry Co., Ltd., product number: V-13F] 20 g monomer Ingredients and 234 g of ethyl alcohol were added. After heating the contents of the flask to 75 ° C., 0.6 g of dimethyl-2,2′-azobis (2-methylpropionate) [manufactured by Wako Pure Chemical Industries, Ltd., product number: V-601] was added to the flask. The reaction solution containing the polymer composed of the monomer components was obtained by putting in the solution and carrying out the polymerization reaction with stirring for 8 hours under reflux conditions.

  Using the reaction solution obtained above as a water / oil repellent, a glass plate having a smooth surface (vertical: 50 mm, horizontal: 20 mm) so that the thickness of the film after drying the water / oil repellent with a bar coater is 10 μm. , Thickness: 3 mm) and dried in air at 60 ° C. to obtain a test piece.

  Next, the water repellency and water repellency, oil repellency and oil repellency, and water solubility of the coating were examined in the same manner as in Example 1 using the test pieces obtained above. Further, the water dilution of the water / oil repellent was examined in the same manner as in Example 1. As a result, the water repellency (contact angle) was 61 °, the water repellency persistence was 32.8%, the oil repellency (contact angle) was 88 °, and it was confirmed that the water repellency was extremely inferior.

Comparative Example 8
20 g of N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine in a 500 mL five-necked flask equipped with a stirrer, an inert gas inlet, a reflux condenser and a thermometer, -A monomer component consisting of 10 g of hydroxyethyl acrylate and 80 g of 2-ethylhexyl acrylate and 234 g of ethyl alcohol were added. After heating the contents of the flask to 75 ° C., 0.6 g of dimethyl-2,2′-azobis (2-methylpropionate) [manufactured by Wako Pure Chemical Industries, Ltd., product number: V-601] was added to the flask. The reaction solution containing the polymer composed of the monomer components was obtained by putting in the solution and carrying out the polymerization reaction with stirring for 8 hours under reflux conditions.

  Using the reaction solution obtained above as a water / oil repellent, a glass plate having a smooth surface (vertical: 50 mm, horizontal: 20 mm) so that the thickness of the film after drying the water / oil repellent with a bar coater is 10 μm. , Thickness: 3 mm) and dried in air at 60 ° C. to obtain a test piece.

  Next, the water repellency and water repellency, oil repellency and oil repellency, and water solubility of the coating were examined in the same manner as in Example 1 using the test pieces obtained above. Further, the water dilution of the water / oil repellent was examined in the same manner as in Example 1. As a result, the water repellency (contact angle) was 110.0 °, but since the oil repellency (contact angle) was 45 °, it was confirmed that the oil repellency was extremely inferior.

Comparative Example 9
90 g of 2-ethylhexyl acrylate and 3,3,4,4,5,5,6,6,7 in a 500 mL five-necked flask equipped with a stirrer, inert gas inlet, reflux condenser and thermometer , 7, 8, 8, 8-tridecafluorooctyl acrylate [manufactured by Osaka Organic Chemical Industry Co., Ltd., product number: V-13F] 10 g of a monomer component and 234 g of ethyl alcohol were added. After heating the contents of the flask to 75 ° C., 0.6 g of dimethyl-2,2′-azobis (2-methylpropionate) [manufactured by Wako Pure Chemical Industries, Ltd., product number: V-601] was added to the flask. The reaction solution containing the polymer composed of the monomer components was obtained by putting in the solution and carrying out the polymerization reaction with stirring for 8 hours under reflux conditions.

  Using the reaction solution obtained above as a water / oil repellent, a glass plate having a smooth surface (vertical: 50 mm, horizontal: 20 mm) so that the thickness of the film after drying the water / oil repellent with a bar coater is 10 μm. , Thickness: 3 mm) and dried in air at 60 ° C. to obtain a test piece.

  Next, the water repellency and water repellency, oil repellency and oil repellency, and water solubility of the coating were examined in the same manner as in Example 1 using the test pieces obtained above. Further, the water dilution of the water / oil repellent was examined in the same manner as in Example 1. As a result, the water repellency (contact angle) is 68 °, the water repellency persistence is 25.0%, the oil repellency (contact angle) is 41 °, and the oil repellency persistence is 24.4%. Therefore, it was confirmed that the water repellency, oil repellency, and oil repellency persisted significantly.

  From the above results, it can be seen that the water / oil repellent obtained in each Example is excellent not only in water repellency and oil repellency but also in oil repellency persistence. Therefore, the water / oil repellent agent is, for example, an inorganic material such as stone or brick, a fibrous base material such as woven fabric, non-woven fabric or paper, water-based paint, fire extinguishing agent, electronic component, car chemical wax, mold forming separation. It turns out that it can be used conveniently for uses, such as a mold agent, a release film, and a lens. Further, the water / oil repellent is excellent in water repellency, oil repellency and oil repellency, and therefore has excellent antifouling properties against dirt such as sebum stains and sweat stains. It is expected to be used for textile products.

Claims (5)

Water and oil repellent having water and oil repellency, and as an active ingredient,
(A) Formula (I):

(Wherein R ¹ is a hydrogen atom or a methyl group, R ² is a hydrogen atom or a fluorine atom, m is 0 or an integer of 1 to 4, and n is an integer of 1 to 12)
A fluorine atom-containing monomer represented by:
(B) Formula (II):

Wherein R ³ is a hydrogen atom or a methyl group, R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, p is an integer of 1 to 4 and q is 1 to 4 Indicates an integer)
And (C) a polymer obtained by polymerizing a monomer component containing an alkyl (meth) acrylate having an alkyl group having 1 to 22 carbon atoms in an alkyl group.   The water / oil repellent according to claim 1, wherein the monomer component further contains a sulfonic acid group-containing monomer.   The water / oil repellent according to claim 2, wherein at least a part of the sulfonic acid group of the sulfonic acid group-containing monomer is neutralized.   The water / oil repellent according to any one of claims 1 to 3, wherein the monomer component further contains a crosslinking agent. The crosslinking agent is of formula (III):

(Wherein R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group, R ⁸ is an alkylene group having 2 or 3 carbon atoms, and r is an integer of 1 to 40)
The water / oil repellent according to claim 4, which is a crosslinking agent represented by the formula: